61 01 PDF

JANUAR11984
JOURflPIL O f
Gilbert Newlon Lewis

1875-1946
Report of the Symposium
THE AMERICAN CHEMICAL SOCIETY

s an instructor who has class-
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Interchapters. The authors have very successfully
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—Forrest C. Hentz, Jr., Ph.D.
e
North Carolina Stale University
BRING YOUR STUDENTS FACE-TO-FACE WITH

THE VISUAL DRAMA OF CHEMISTRY
m e r a l
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Donald McQuarrie and Peter Rock

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The result?
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J. J. LAGOWSKt, Editor JANUARY 1984 Volume 61, Number 1
University of Texas at Austin
Austin, Texas 76712
Assistant Editor: JOURflflL OF

Debora Ann Bittaker
Editorial Assistants
Linda Davis Kyle
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Chemical Education
Owned ana Published by the DIVISION OF CHEMICAL EDUCATION OF THE AMERICAN CHEMICAL SOCIETY
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(203)226-7131 The G. N. Lewis Symposium
(For list of offices, see page AS) 2 Gilbert Newton Lewis: 1875-1946 Derek A. Davenport
NEW PRODUCTS 3 A Pioneer Spirit from a Pioneer Family Richard N. Lewis
Shirley Sleratzkt
Journal of Chemical EOucaiion
5 G. N. Lewis: The Disciplinary Setting John W. Servos
Centcom. Ltd. 11 The College of Chemistry in the G. N. Lewis Era: 1912-1946
60 East 42nd St. Melvin Calvin and Glenn T. Seaborg
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SECONDARY SCHOOL EDITOR

Articles of General Interest
Mickey Sarquis
Miami Unlversity-Middietown
Middietown, OH 45042 22 Enduring Distributions that Deny Boltzmann Leonard K. Nash
51 Single-Pan Balances, Buoyancy, and Gravity or "A Mass of Confusion"
ASSOCIATIONS EDITORS
VasuDev Robin Battino and Arthur G. Williamson
California Association ot Chemistry Teachers
Percy Ehrlich
New England Association of Chemistry
Teachers Features
BOARD OF PUBLICATION
Division of Chemical Education 1 Editorially Speaking
J. A. Bell 26 Computer Series, 48: Will Computers Replace TA's? Professors?
D. W. Brooks
W. B. Cook Labs? Should They?—A Symposium Report edited by John W. Moore
G. A. Crosby 48 2YC3 Viewpoint: Coping with Shifting Student Expectations
D. A. Davenport
M. H. Gardner Tamar Y. Susskind
D. Koto
W. J. Stfatton 89 Letters
The Cover A13 Safety In the Chemical Laboratory edited by Malcolm A. Renfrew
This month's cover portrait of G, H. Lewis Good Practices lor Hood Use
Introduces the publication of the sympo- William G. Mikell and William C. Drinkard
sium which was held in his honor al the Las A16 Out of the Editor's Basket edited by James A. Goldman
Vegas ACS meeting in March 1982. The A27 Book Reviews
proceedings will begin in this Issue and be
completed in the subsequent two issues.
Secondary School Chemistry

36 Chem I Supplement: Geochemica) Exploration ol the Moon
Isidore Adler
40 Goals
Why Teach Kinetics to High School Students? William G. Lamb
Kinetics—Rates and Mechanisms J. Arthur Campbell
43 A High School Biochemistry Course George B. Powers
44 Implementation ol the Thai High School Chemistry Curriculum
Nida Sapianchai and Thongchai Chewprecha
47 Thumbnail Sketches: Metal Substitutions in Wartime Coinages
Hugh A. Akers
49 Safety Tips: Risk Assessment Miriam C. Nagel
58 Profiles in Chemistry: Jean Rey: Unsung Prophet? Sidney Rosen
68 Filtrates and Residues: Analysis of Alcohols
Brother Thomas McCulSough
(Continued an page A4)
73 Something New from the Past edited by Joseph S. Schmuckler
T h e 80 Inventory Control edited by David L. Byrum
88 What's Happening In Your Part of the Country?
P a r r 1 3 4 1
P l a i n
Laboratory Experiments
J a c k e t
53 Qualitative Analysis, with Periodicity, for "Real" Solutions
O x y g e n
Ronald L. Rich
60 Qualitative Determination of Nitrate with Triphenylbenzylphosphortlum
B o m b
Chloride Donna A. Berry and Jerry J . Cole
C a l o r i m e t e r 62 Qualitative Analysis by Gas Chroroatography: GC versus the Nose in
A reliable calorimeter in a Formulating Artificial Frutt Flavors P. W. Rasmussen
plain insulated jacket for 70 Performance Characterization of an Instrument Eric D. Salin
measuring heats of combus- 74 The Density and Apparent Molecular Weight of Air: A Simple
tion of any solid or liquid fuel Introductory Experiment Arlo D. Harris
For Occasional 76 Solution Calorlmetry In the Advanced Laboratory: A Study Guide of
Calorific Tests
For users whose work load does Glycine Proton-Transfer Enthalpies R. W. Rameite
not justify the purchase of a 78 Reactions of Thiocyanate Ions with Acid: A Laboratory Experiment
more elaborate automatic mod- Christopher Gfldeweli, James S. McKechnie, and Peter J. Pogorzelec
el, the Parr 1341 Plain Calori- 83 Electrode Potential Diagrams and their Use in the HIII-Bendali
meter is a reltabie instrument
that will determine the calorific or Z-Scheme for Photosynthesis Peter Sorrel! and Denis T. Dlxon
value of solid or liquid fuels a n d 87 The Prototype Compound for Oral Anticoagulants:
foodstuffs with a precision com- 3,3'-Methylene bfs(4-hydroxycoumarin) Rodney C. Hayward
parable to that of other P a n
calorimeters, but at a slower
speed a n d with considerably
less invested in equipment It Notes
requires n o permanent con-
nections and can be set u p
and ready to operate in a few 4 The Southwest Chemistry Lecture Exchange Program A. G. Pirtkus
minutes. When not in use, it is 42 Use of Photocopying (or Non-Destructive Leaf Area Measurements
easily disassembled for storage. Marian L. Lyman, Donald E. Campbell, and J. Corse
For Student Instruction 68 An Addendum on Measuring the Entropy of Mixing of a Two-Ion System
In addition to its general J. D. Pulfer
applications, the 1341 Calori- 77 A Kugeirohr Oven from a Rotary Evaporator R. Somanathan and I , Hellberg
meter has equally important uses 82 A Convenient Glassware Cleaning Bath
in college a n d university labora- Tom Lyons Fisher and Phyllis M. McGinnis
tories where instruction in heat
measurement techniques is an
essential part of f he basic training
for all fields of science a n d
engineering. «.
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COLLEGE CHEMISTRY GENERAL CHEMISTRY
WITH QUALITATIVE ANALYSIS Seventh Edition
Seventh Edition 1984 Cloth 932 pages
1984 Cloth 996 pages
Henry F. Holtzclaw, Jr., University of Nebraska Lincoln
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Seventh Edftion CHEMISTRY
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1984 Paper 221 pages 1984 Cloth 1163 pages
This student oriented and highly
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STUDY GUIDE FOR ORGANIC CHEMISTRY
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IN COLLEGE CHEMISTRY WITH Marjorie L.C. Carter
SEMIMICRO QUALITATIVE 1984 Paper 1100 pages est.
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Circle ND. 21 on Readers' Inquiry Card

/Qfety in the edited by
chemical laboratory
MALCOLM M. RENFREW
University of tdaho
Moscow, Idaho 83843
Good Practices for Hood Use

William G. Mlkell and William C. Drinkard
Central Research and Development Department, E. I. du Pont de Nemours, Experimental Station, Wilmington, DE 19898
Laboratory fume hoods are important

safety devices. They are provided to protect
personnel from chemicals that are being
handled or stored which are potentially in-
jurious to health. In addition to protection
from chemical fumes they provide some de-
gree of protection from fires and explosions. BRINGS CHEMISTRY
Hoods, however, are secondary or "back-up"
safety devices. Training of personnel, proper
design of experiments, and careful operation To the Liberal Arts . . .
of equipment are the primary controls. Even Available January, 1984. the fourth edition of ihis popular text
the best hoods cannot overcome poor work has been updated and revised to reflect the changing issues and
practices by the user. Studies U, 2) have
shows that when good work practices are interests of today's chemical world. Incorporating a more effective
employed with a properly installed and format, additional topics such as "Sports, the Ghemical
functioning hood, the user is protected. The Connection" and "The Risks and Benefits of Science and
purpose of this brief article is to outline these Technology" are discussed.
good practices for hood use. Supplements include an Instructor's Guide, Test Ban* and
Student Study Guide.
Assumptions on Hood Design The Laboratory manual. Chemical Investigations for Changing
and Performance Times, not only complements the text but can also be used on its
A properly designed, installed, and func- own to supplement whatever text you may prefer
tioning laboratory hood is a complex device C'lwmittry For Changing Time\. Fourth Edition, John W. Hill, Cnivetmy of
which requires many design and operating \\'i<k-mt\in-River Falls. January, 19/14. 57ft jip, highly illuvmitfd, tHitth. ISRS;
compromises such as size, opening, materials 0 7 3 8
of construction, fire and explosion protection,
location in lab, air Oow, air distribution, ser-
vices, convenience, cost of operation. To
stress some design parameters or to overlook To College Prep . . .
others may seriously affect the performance
of tiie installation. For example, there is a Designed for the student with little background in chemistry,
great tendency among hood users to place this unique text ts written in an informal style, conveying facts and
primary emphasis on face air velocity (or face theories in a non-threatening manner. The contems and
velocity) as being ihe single most important organization are reinforced by over 250 diagrams, graphs, and
charts and lend themselves to a flexible presentation to fit
(Continued on page A14) individual lesson plans.
Supplemental material available includes a Student Study
Guide instructor's Guide, Test Bank, and free Transparency
WilHam MikeH is the Environmental Control Masters to adopters
Manager at the du Pont Experimental Station (n
Wilmington. Delaware. He served with Hie Nations! Introduction to Chrmfctiy. /' fiuwetl Hardwkk, Inhervty of Catiftmiia, lot
Research Council Committees which developed the Angela, February, I9S4. 654pages. ?"•" x 9'-;', doth, iltutfrared, ttro color. ISB\:
reports on "Prudent Practices tor Handling Hazard- 0-X087-4740-1.
ous Chemicals In Laboratories" and "Prudent
Tc. ruquest -l uunpi-mo'ttary copy of any of these ti'ies <O' adoption consider&uan,
Practices tor Disposal ot Chemicals From Labora- Otoase write ni Department JCFJ3* Bur/jess Publishing Coivpany Please i
tories." yaw cow so }<tte btrf eiirjtityeni present text, and txiok n,^wiSif'on riafo
W. C. Orlrtkard joined du.Pont In 1960 and Is

ourreniiy Manager, Facilities and Safety in the \ Burgess Publishing Company
Central Research and Development Department a! j7108OhmsLane
the Experimental Station In Wilmington, Dela- Minneapolis MN 55345 {612) 831-1344
ware.
Circle No, 1 on Readers' Inquiry Card

Volume 61 Number 1 January 19S4 A13
COLUMN GONEDRY?
Keep AIR out of
Liquid Chromatography
/afety A sufficient volume of nonturbulent air
should flow through the hood at all times.
Thus, storage of chemicals and equipment in
the hood should be kept to a minimum, and
items should not be placed so that they block
C o l u m n s . . . Justus© a exhaust ports from the hood. Since air must
THERM-O-WATCH be supplied to the hood for proper operation
Controller... it is important that make-up air vents in the
clip its sensing head onto laboratory not be blocked by furniture or
the plaslic tubing carrying equipment of any kind, in addition, pedes-
liquid to the column . . .
plug your pump and other
m p
o a
p r
a
erm
a n it g et
r. pT
arahme r e e t
rsm a
y
of b
e
qeuao
lht
oe
r
r d
g
re
g
s
ei
n
ae
t
r or
trian traffic in front of the hood should be
minimized and laboratory doors kept closed
tofviorm paoth
rn atcn ce s
uc h a s t
he r
o
m ar
i ds
i
t
rb
iuot
i
n
a c c e s s o r i e s into the to reduce air turbulence.
e al bo ra t
o ry . T he h oo
ds' um
i
t
l ae
t per-
THERM-O-WATCH am-
plifier.
e is u
j d g ed by t
he p r
ot
ec
o
Materials, such as paper, entering the ex-
Now, if your reservoir
runs dry and air enters
trie tubing, THERM-
ith
b d
e es m the
o
nvi
g u se
or
v e r n o
t
hte t
i
n it pro-
haust ducts can lodge in the ducts or fan and
b
y ho
w r
apd
iy
l t
h e ar
i
reduce hood efficiency. For example, when
be
nc
h t
op. M u
h
c exs
it
s m
n
i a
y
eracetitd
eiler,sah
tuothrw
eateve(r2,th-5eth)atcoh
nn t
h s
i s
u b
trouble shooting a poorly performing hood,
O-WATCH will turn
off power to the
pump, fraction col-
lector and other ac- ssp
uam j
ect
. It i
s as-
it is not unusual to find paper towels and/or
i ds
i
cusn
ig s
tissues in the airducts and on the fan.
e
m s
ti has ava
af
e
l
ibe
lw o
r
k
a
cessories before air
can reach the col-
umn.
Result: iroubta-free hood. t
si
f
a c t
o ry
l
i n
i s
ta el d a nd W p
-l
e
ir
o
fr
m ni
g
Traps, scrubbers, or incinerators should be
used as primary devices to prevent toxic
and/or noxious material from being vented
into the hood. This is particularly true when
operation, no repack- working with highly toxic or odiferous ma-
ing necessary. terials such as earciMgens and environmental
Write lot lii«ra!ufe To-
dav! pollutants.
!rt conclusion, it is worth repeating that
laboratory hoods are secondary safety devices
whose effectiveness can be compromised by
improper or poor work practices. Primary
Preparation for Work attention should be focused on the funda-
Before beginning work, the user should mentals of training personnel, proper design
make sure that all of the sashes are in place of experiments and careful operating tech-
and movable as required. The need for any niques.
i > instruments lor additional safety shields to be used within the
hood should be anticipated and they should
Research and industry be obtained.
10* Franklin kit., CheltenHam. Pa, 19C112
Users are responsible for hood operation
and should be aiert to signs of malfunctions
such as unusual sounds or reduced draft. Any Literature Cited
suspected inadequacy should be checked
immediately. Hoods can be checked by a (1) Mitell, W. G., and Honbs, L. R, "Laboratory Hood
Easiest way smoke test, a bit of yarn on a wand, or by Studies," J. CHEM. EDUC., S*. A165 (1981).
(21 Fuller, P. H., and Ettheila, A. W., ""toe Rating of Lab-
to control observing an air flow gauge if the hood is
equipped with one. The user should be alert
oratory Hood Performance," ASHRAE Journal,
(October 1979).
temperature for any air flow changes or shift in operation (3) Chamberiin, RI., and Leahy, J.E.. "LaboratoryFume
and stop work to check it out should either Hood Standard," Recommended for V3- Environ-
occur. mental Protection Agency, Contract No. 68-4)1-4661,
Clip Sensing head onto your January 1978.
thermometer (4) Hiigbes, D., "A Literature Survey and Design Study of
A plan of action should be prepared for a
littsrt thermometer into your ventilation or power failure; time may be Fumecapboards and Fume-Dispersal Systems," Oc-
apparatus cupational Hygiene Monograph No. 4, Science Re-
critical in preventing a serious incident. views Ltd, London, November 1980.
Plug your heater into the {5) Csplan, K. J., and Knutson, G. W.. "Development of
"Therm-O-Watch" Controller. Criteria for Design, Selection and Jn-place Testing of
It's that simple.
Laboratory Fume Hoods and Laboratory Room
Ventilation Air Supply: Final Report," ASHRAB
in less than 2 minuses your apparatus RP-70, March 1978.
is under control! Therm-0-Watch
can control tfis temperature of re-
actions, baths, distillations as weil as
other operations (titjuld level
control, etc.). Hood Practices
Efficient and safe operation in a well-con-
structed hood requires good work practices. Good Hood Practices
At ali times during operation in the hood sash Sash openings should be fiept to a minimum.
openings should be kept to a minimum. This Sources of emission should be kept at least 6 in.
is important to minimize operator exposure. inside the hood.
In addition, all sources of emission should be Users should keep their laces outside the plans
kept as far back in the hood as possible (6 in. of the hood sash.
from the plane of the sash is a good rule of
thumb). Recent studies!/, 2) have confirmed Storage In the hood should be kept to a min-
the importance of this rule; the degree of imum,
protection provided the user has been shown Exhaust ports from hood and supply air vents to
to improve by orders of magnitude when room should not be blocked.
emission sources are placed into the hood Traps, scrubbers or incinerators should be used
away from the plane of the sash. In addition, to prevent toxic and noxious materials from
the user's face should be kept outside the being vented into the hood exhaust system.
Send lor Bulletin T100.
hood while performing chemical operations. Remain alert to changes in air How.
£> instruments for Leaning into the hood to adjust equipment
when it is operating can result in a significant
Prepare a plan of action in case of an emergency,
e.g., powei failure.
Research and Industry air turbulaace with a corresponding loss in To save energy, turn off blower and close sashes
101 Franklin »•>.. Cheltenham, Pa. 19012 protection. when hood Is not in use.
Circle Ho< 25 on R e a d e r s ' Fnquiry Card
A14 journal of Chemical Education

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The Scintag PAD V x-ray diffraction system
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MISTRY
SECOND EDITION RAYMOND CHANG Williams
Coliege
CHEMISTRY
IN ACTION
What is Chemistry in Action? —End-of-book glossary —Important topics such as
• it's the reorganization of the Table —CHEMISTRY IN ACTION BOXES stoichiometry that relate to
ol Dontontl to reflect ihe topic order illustrate how chemicai principles laboratory work are introduced early
prelerred by mosi instructors: apply to everyday experience and clearly
—Inorganic nomenclature and —Biographical footnotes oi chemists —Formal charge is used in writing
stoichiometry are introduced early io discussed in the text. Lewis structures
coordinate with laboratory work —Color Plates
(Chs 2 & 35 • it's the ancillary package you need
—Gases are discussed early (Ch 4) • it's t h e ! • « ! and approach instruc today, complete with a microcomputer
—Bonding 15 divided into 2 chapters tors need to teach a mainstream floppy disk system for your students'
(Chs 7 & 8), in which the basics are general chemistry course to today's tutorial use:
discussed first and more detailed, in- students: STUDENT STUDY GUIDE
depth material follows —Difficult topics such as entropy are INSTRUCTOR'S MANUAL
—An entire chapter is devoted to explained in stmpte terms SOLUTIONS MANUAL
thermochemistry (Ch 9) —All advanced topics have detailed, TRANSPARENCY ACETATES
—An entire chapter is devoted io low-level introductions in earlier "INTRODUCTION TO GENERAL
REDOX reactions {Ch. 12) chapters. (See how thermochemistry, CHEMISTRY/' by Professor Stanley
—Acids & Bases are discussed in 2 Ch. 9, provides the basis for ther- Smith (University of Illinois), Dr. Ruth
consecutive chapters (Chs. 15 & 16) modynamics, Ch. 18, and how Chabay, and Dr. Elizabeth Kean (Univer-
—A separate chapter on solubility REDOX reactions, Ch. 12, lays a firm sity of Wisconsin), a U-diSk program
equilibrium is inducted (Ch 17) foundation for Electrochemistry, covering a complete range of topics in
—Inorganic Descriptive Chemistry is Ch. 19) General Chemistry, available January,
located in one integrated series ot —Interesting asides, cautions, and 1984. ("Introduction to Genera!
chapters (Chs 20-23) cross-references are included in the Chemistry," is available through a
—A new chapter on metallurgy is margins special arrangement with COMPress,
included (Ch. 21) Inc., a division of Van Nostrand
—Organic Chemistry has been moved Reinhold). For more information regar-
back in the text (Ch 24), immediately, ding this program, please call Heidi
preceding biochemistry. Udell at 212-572^2453.
To receive your comphmentaty copy of
• it's the pedagogical featurat your Charsg's Chemistry, please write to:
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grouped by topic. oidor code *329fl3-X
—SI units used consistently throughout Circle No. n unfiedd&rs' Inquiry Card
the text.
—Important terms in bold face type ior
easy reference.
—End-of-cha0ier lists of key terms,
including page numbers.
—End-of-chapter numbered summaries
—Chapter opening remarks connect Random Mouse
topics and explain the relevance of 301 E. SOih St.
new chapters. New York, N.Y. 10022
T h e out of the Autosampler for AA
Instrumentation Laboratory (\L) is offering a
P a r r 1 4 5 1 editor> ba/ket 6-page report on the )L FAST AC (I autosam-

pler. The FASTAC II is the only AA autosam-
pler which employs aerosol deposition of the
sample for furance atomlzation. Because It is
S o l u t i o n a nebulizer based system, the FASTAC II
Multidimentional Gas Chromatography provides automated analyses for both flame
C a l o r i m e t e r and furance atomization. This dual capability
A convenient bench-top instru- minimizes purchase cost, space requirements,
ment for measuring enthalpy and changeover time. Unlike any other furnace
changes produced by chemical autosampier, the FASTAC ii converts the
reactions in solution, with sample to an aerosol and deposits it Into the
provision for conversion to a furnace cuvette, where it dries immediately on
semimicro bomb calorimeter. contact. This technique has many advantages:
1. It saves time and simplifies methods de-
A Multi-Purpose velopment by eliminating the lengthy and
Calorimeter complex furnace drying step. 2. It works
Utilizing a unique rotating equally well with aqueous and organic sol-
sample cell and a sensitive vents. 3. tt eliminates many analytical inter-
electronic thermometer, the ferences. 4. It simplifies preparation of stan-
1451 Solution Calorimeter pro- dard solutions. 5. It can be set to produce al-
vides a moderately priced and ES Industries, the exclusive U.S. representa- most any desired analytical sensitivity. 6. it can
easily operated instrument for tive for Siemens Gas Chromatographs, has be used with samples that are too viscous to
measuring: announced the availability of the Siemens Si- pipette. 7. The same system is usable for
• Heats of Reaction Chromat 2 Gas Chromatograph. According to flame and furance. fn comparison to the pre-
• Heats of Solution a company spokesman, the SiChromat 2 is a viously offered IL FASTAC autosampler, the
* Heats of Mixing double oven S.C. which features a patented FASTAC II offers approximately 10X higher
vaiveless "live" column switching system. sampling efficiency, and is easier to use.
• Heats of Dilution With this system, multidimentional chroma- Circle #47 on Readers' Inquiry Card
• Heats of Wetting tographic procedures such as heart cutting
with a precision adequate for sample components for transfer to a second
most analytical and exploratory column and bat*flushing the precolumn can
research applications. Energy improve resolution and save valuable analysis
changes ranging from 2 to 1000 time. Valveless means the sample does not
calories in either liquid-liquid Zimmermann Cell Fusion System
come into contact with any valves and the
or liquid-solid systems can be 'live" principle means that the switching times
measured in a straightforward can be determined directly.
manner with results plotted on a
strip chart for easy interpretation. Circle #45 on Readers' Inquiry Card
Convertible to a Semimicro
Bomb Calorimeter
Taking advantage of its com-
pact case and precise electronic fR Gas Anafyzer
thermometer, the 1451 calori-
meter is easily converted to a
Parr 1421 Semimicro Bomb
Calorimeter for measuring heats
of combustion of small samples.
The semimicro bomb and ail
parts needed for this conversion
are provided in a 1425 Conver- The Zimmermann Cell Fusion system that
electrically fuses cells, including fusing hy-
sion Set. bridomas for monoclonal antibody production
For details,write or phone: and fusing cells for plant genetics, yeast
transformations and other biotechnology and
cell research applications, is now available
The Binos Infrared Gaa Analyzer makes pre-

cise and accurate determinations of changes
in CO2 and H2O vapor levels in plant cham-
bers. A measurement range of ±25 ppm CO?
at a nominal reference point value of 330 ppm
CO2 is possible with this equipment. The in-
strument also measures absolute CO2 (typi-
cally 0 to 600 ppmj as well as absolute and
differential HSO {typically 0 to 1 % as an ab-
solute range and 0 to 5000 ppm as a differ-
ential range). Four standard models of the
BfNOS Infrared Gas Analyzer are available from GCA/Precision Scientific Group. With the
from Tekmar Co., and all have appropriate Zimmermann Ceil Fusion system, ce!!s are
infrared optics to maximize accuracy anil exposed to a low level electrical field, orienting
PARR sensitivity for their specific applications. Each the ceils end to end. Alignment voltages can
INSTRUMENT model is portable and works on 12 V dc or 120 be varied from zero to 40 voits at a frequency
V ac; heated optics are not required. These of 10KHz to 5MHz. A short, direct current pulse
COMPANY models feature analog or digital display of the is then applied, which opens micropores ir>
measured component and provide a 0 to 1 voit adjoining call membranes, allowing mixing of
recorder output signal over the measured
211 Fifty-third Slteeu MoHne, IL 61265 range.
309-762-7716 {Continued on page A20)
Circle #46 on Readers' inquiry Card

F o r m u l a
f o r s u c c e s s .
B a s i c C o n c e p t s o f C h e m i s t r y
T h i r d E d i t i o n
A l a n S h e r m a n , S h a r o n J. S h e r m a n , a n d
Leonard Russikoff
All o f M i d d l e s e x C o u n t y C o l l e g e
A b o u t 5 7 6 p a g e s • c l o t h • S t u d y G u i d e b y J a m e s R.
B r a u n , Clayton Junior College • Laboratory Manual
Instructor's Manual • Transparency Masters
Just published
A clear narrative style and a supportive approach m a k e
t h e S h e r m a n / S h e r m a n / R u s s i k o f f text highly w o r k a b l e for
s t u d e n t s w i t h little o r n o b a c k g r o u n d in c h e m i s t r y a n d
mathematics. T h e Third Edition features a n e x p a n d e d
problem-solving program: the n u m e r o u s worked-out
e x a m p l e s are followed immediately with practice exer-
c i s e s f o r t h e s t u d e n t t o s o l v e . A n d t h e e n d - o f - c h a p t e r self-
test exercises have b e e n doubled to provide an average
of 6 5 p r o b l e m s p e r c h a p t e r .
A n e w chapter o n kinetics a n d equilibrium r o u n d s out a
c o m p l e t e c o v e r a g e of t o p i c s f o r t h e i n t r o d u c t o r y
chemistry course.
For adoption consideration, request an examination package from your regional

Houghton rttfUin office.
Houghton Mifflin
19304000SM
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B aaytavaiRdA . vD
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v a. I7523640134
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out of the automatic system for determining pore size,
volume, surface area, bulk density and particle
size. Six examples demonstrate the Porosi-
editor)" bo/het meter's results reported In the field of cata-
lysts, ceramics and cements. Also included is
information pertaining to ink-bottle pores and
ultramacro porosity.
cellular contents and resulting in their fusion. Circle #50 on Readers' inquiry Card
Each electrical pulse can be precisely con-
trolled from zero to 250 volts. Up to nine sep-
arate pulses can be applied, with durations to Multipoint Ambient Air Monitoring
99.9 microseconds. By providing a number of System
separate small pulses, the Zimmerman Cell
Fusion system gives the biologist precise "Hie Miran 981 Multipoint Ambient Air Moni-
data. The Instruments Include a demonstration toring System, that helps to ensure protection
control over the cell fusion technique and is program listing for the IBM PC at no additional
less destructive to the celis than other fusion of personnel by monitoring the concentration
charge. Now data can be presented in tabular in air of up to 5 gases or vapors at up to 24
techniques. The benchtop Zimmermann Cell and graphic formats. Analysis data can be
Fusion system is also designed to be user- remote locations, is featured in a 6-page data
stored and retrieved for analysis comparison. sheet recently published by The Foxboro Co.
friendty. Major process parameters are con- Sample pore size distributions, total pore area,
trolled by large, easily accessible dials with The Miran 981 can monitqr more than 200 of
median pore volume and area, average pore the approximately 400 gases declared haz-
digital LED readouts of their values. In addition diameter, bulk and apparent density can be
to the power supply and an assortment of fu- ardous by the Occupational Safety and Health
stored and manipulated to suit individual lab- Administration (OSHA). This system can be
sion chambers, the system includes art ex- oratory requirements. The Pore Slzer Is de-
tensive protocol manual. The manual, which used to monitor air quality in hospitals and
signed to measure the porosity of powder or medical supply manufacturing plants, power
is based on the work of Dr, Ulrich Zimmer- solid samples, Trie data from porosity analyses
mann and his colleagues at the Nuclear Re- plant control rooms, industrial environments,
represents the intrusion and extrusion of a and other locations as far as 300 m {1000 ft.)
search Center of West Germany and by GCA non-wetting liquid (mercury) into sample void
biotechnology scientists, details sample pro- from its enclosure. The operating principle of
volumes under pressures that are ramped to the Miran 981, cjiscussed in the data sheet, is
tocols for fusing yeast cells, plant cells, 30,000 psi.
erythrocytes and hybrldomas. A technical based on infrared speotroscopy. The system's
description of the Zimmermann Ce!i Fusion Circle #49 on Readers' Inquiry Card microprocessor controls the infrared spec-
process is also provided. trometer, signal averages the infrared trans-
mission measurements at each programmed
Circle #48 on Readers' Inquiry Card wavelength, calculates absorbance, and uses
Mercury Pressure Porosimeter a stored coefficient matrix to determine the
Erba Instruments, the U.S. safes and service concentrations of components in the air
organization of Carlo Erba Strumentazione of sample. This microprocessor-based system
Porosimeter Italy, provides a detailed analysis of their au- provides a printed report with eight hour and
Mlcromerilics' Pore Steer 9305 porosimeter tomatic Mercury Pressure Porosimeter—2000 monthly time weighted averages (TWA) of the
features an RS232 port that allows automailc Series. The 8-page brochure details and il- toxic gas concentrations in parts per million
acquisition, reduction and reporting of porosity lustrates the complete, fully-programmable (ppm) and alarm conditiqns at each remote
location. An Interactive keyboard combined
with user oriented programs makes the oper-
ation of the 981 simple and virtually error
free.
p H E L E C T R O D E Circle #51 on Reactors' Inquiry Card
UV-Vis Absorbance Delector

S T U D E N T P R O O F ? The Spectroflow 757, available from Kratos
Analytical Instruments, is a logical alternative
. . . W E L L , A L M O S T ! to single wavelength detectors because of its
price and sensitivity. It is ideally suited for use
with analytical scale HPLC, "fast LC", prep and
ITS p H R E S P O N S I V E GLASS
mlcrobore. A touch-sensitive membrane pane!
BULB IS R E C E S S E D INTO operates instrument functions, while a rear
ITS 1 / 1 6 " THICK EPOXY panel connector permits comprehensive
BODY SO BREAKAGE IS computer control using any existing controller.
MINIMIZED. The Detector incorporates important features
like auto-zero and digital noise suppression.
ITS SEALED, GEL-FILLED Circle §92 an Readers' tnquiry Card
REFERENCE NEVER MODEL
N E E D S REFILLING. S200C
COMBINATION Digital Colorimeter
NO PERFORMANCE pH ELECTRODE
SACRIFICE; FAST 12mm D1A BY
FULL RANGE 150mra LONG
NERSTIAN $40
RESPONSE. When ordering,
specify type of
connector 01
make and model
of pH merer
U 6fil Seaboaid Circle

Station. Catifomta
90680 USA
714-895-4344
TELEX- 183123
(Continued on page A22)
Circle Mo. 22 on Readers' Inquiry Card

C h e m i s t r y i s t h e
c o m p l e x s u b j e c t
m a n y s t u d e n t s f a i l
f o r a s i m p l e r e a s o n .
Many of the 60,000 students who fail CHEMESTRY TUTOR. The program
introductory Chemistry each year fail for instantly recognizes where the problem
one simple reason: they never learn how lies, and asks questions designed to lead
to balance equations. The first time they students back on the track to the right
get stuck, and no one's there to get them answer—and an understanding of where
OUT of trouble, they just skip over the prob- they went wrong in the first place.
lem . And because stoichiometry is funda-
mental to an understanding of Chemistry, Flexibility for the instructor, too.
as the course progresses they fail further The equations on THE CHEMISTRY
and further behind. TUTOR represent the gamut of stoi-
chiometric problems, from the simplest to
W i l e y just t o o k the most rigorous. And you can change
or add to the equations at any time, with-
t h a t s i m p l e out endangering the disk's integrity. So
you can put your own choices right into
r e a s o n away. the program-and also choose the char-
acter style {bold or normal), sound, and
THE CHEMISTRY TUTOR: color. Also, as an owner of THE CHEM-
Stoichiometry & Balancing ISTRY TUTOR, you have unlimited
Equations access to the Wiley Educational Software
Help-Line.
Frank P. Rinehart
THE CHEMISTRY TUTOR nips confu- THE CHEMISTRY TUTOR runs on the
sion in the bud—before it has a chance to Apple Ii + /ile with one disk drive, DOS
threaten a students work, it's an interac- 3.3
tive tutorial program that teaches students
how to balance chemical equations the Available October 1983
same way you teach them: in careful, 047188808-7 $75.00 instructor's package
step-by-step detail. 0 47180274-3 $25.00 Student's package
047180273-5 $ 4.00 Sam pie diskette
The secret lies in THE CHEMISTRY
TUTOR'S amazing flexibility. It actually
gives specific responses to any answer For further information, or to order, write to
your students enter—no matter how close Bill Rosen, Dept. 4-1517
or off-base that answer is. For example, if
a studenl were confused between coeffi-
WILEY EDUCATIONAL SOFTWARE
cients and subscript, you wouldn't say:
605 Third Avenue
"Wrong. Try again!' Neither does THE New York, N.Y. 10158
4-1517
Apple® is a registered trademark of Apple Computer. Inc.
ÊDUCATIONAL
Unlocking the power of computing ^SOFTWARE _
Circle No, 16 on Readers' Enquiry Card
out of the five simple function keys. Simply labeled for
quick calibration, the new Corning pH meters
are designed for rugged durability in a labora-
plays and an accessory drawer for convenient
storage for forceps and weights. The separate
weighing unit allows right or left-handed ac-
editor)- bo/het tory or field setting. Cases are made of molded
structural foam with keypads of polyvlnyl
cess and unique pan arrests make sample
handling easy. Die AD-6 Autobalance has a 5
chloride especially coated to withstand gram capacity with 0.1 ftg sensitivity. An
chemical spills. A!! Coming meters are sup- BS232C accessory allows the addition of a
plied with a plastic barrel combination elec- Perkin-Elmer Model 660 printer or interface
Chemtrix, Inc., announces its Type 24 Digital
trode with Coming's exclusive replaceable capability into a computer.
Colorimeter that features readouts directly in
Junction feature. In addition, complete lines of Circle #56 on Readers' Inquiry Card
two concentrator! ranges, 0-199.9 and 0~
accessories and test electrodes are offered by
1999; absorbance and transmittance readouts;
Corning.
plus, a universal cuvette holder. Ideal for water,
pollution control, clinical and industrial anal- Circle #54 on Headers' Inquiry Card Analog Interface
yses, it has eight analytical wavelengths from VOTEM Is a complete package, available from
350 to 660 nanometers which are adjustable Down East Computers, consisting of hardware
by a front panel thumbwheel control. Ab- and software that enables your computer to
sorbance, % transmittartce and concentration
fevefs are easily read (ram the instrument's
pH Electrodes measure, display and record "real world"
analog signals. Your computer can monitor any
high-contrast liquid crystal display (LCD). The physical phenomenon (pressure, light, tem-
universal cuvette holder permits the use of perature, etc.) that can be represented by a DC
square cuvets up to 12.5 mm and round tubes voltage. A probe is provided for air and liquid
up to 19 mm diameter. Additionally, a famine temperature measurements. Your computer
of water test kits are available for use with tile becomes a "smart" digital voltmeter and
Type 24. thermometer witti storage capability. Just think
Circle #53 <"• Readers' Inquiry Card of the possible applications. Use VOTEM and
your computer to monitor the temperature in
a home energy conservation project to save
pH Meters money and possibly qualify for an energy tax
credit on the entire system. VOTEM also am-
IITI'RA -11 f.li Ei,c£7Ri:m plifies and cleans up the tape signal for reliable
program LOADing. The tape signal conditioner
circuit will allow you to LOAD tapes with a
lower volume setting on your tape recorder,
The Futura-ll pH electrode line from Beckman resulting In less noise and more dependable
Instruments, Inc., a family of 21 electrodes, is LOADs. You will be able to LOAD from tapes
designed for high performance and maximum which would previously not comply. VOTEM
reliability In any kind of environment. Each requires no modifications to your computer
Futura-ll electrode has a connector/cable and does not use the computer's expansion
system for quick interchanging of 1-, 2- and connector, leaving it free for other add-ons
6-meter cables. The gasketed connector seals such as the memory pack and printer.
off the electrical contacts from the external Circle #57 on Readers' tnqtdiy Card
environment to protect them against the ef-
fects of steam, chemical vapors, liquids and
other substances that can produce inaccurate
Corning Science Products has introduced a measurements. A self-aligning screw-on
line of five easy-to-operate pH meters with a connector prevents misalignment. The low- Multiple Manifold Dispenser
unique "delta" shape and unified display which noise, high-rejection design of the cable as-
allow easy use and quick reading from the sures accurate and repeatabie results. The
laboratory benchtop. Beginning with the Model Futura-H line of electrodes includes glass,
120, a lightweight, battery-operated meter for reference and combination electrodes to meet
use in the lab or in the fieid, the fine ranges the requirements of particular applications.
upward to the Mode! 155, a pH/ion meter for The internal design of the electrodes enhances
all research applications which features known accuracy, repeatability, speed of response and
and sample addition/subtraction modes, long iife, even under adverse measuring con-
step-by-step alphanumeric prompting In five ditions.
languages, automatic buffer recognition,
three-decimal accuracy, a digital clock and Circle #55 on Readers' Inquiry Card
timer, and activity and memory functions ca-
pable of accommodating a five-electrode
testing system. Other models in the line in-
clude; Model 140—Ideal for quality assurance Autobalance
or education applications where speed of Labindustries' adjustable manifold dispenses
analysis over a quantity of samples is impor- simultaneously into microtiter plates with 6, 8
tant. Its four-button control panel is unequalled or 12 wells, or info test tubes in a rack. Avail-
for ease of use. Model 145—Incorporates all able as a complete instrument with Labin-
features of the Model 140, plus a sharp, dustries' micropipettor and sampling systems,
eight-digit alphanumeric LED display that it can be attached to any repetitive dispenser
prompts users through calibration and mea- or pipettor with a Luer tip outlet. This trans-
surements in automatic or manual operations parent, autoclavabie manifold dispenser has
mode. The Mode! 145 is ideal for basic re- interchangeable glass capillary outlets and
search functions, containing a micropro- closures, which adjust to match rows of wells
cess-operated lookup table Via! automatically in plates, or rows of test tubes in a rack. This
matches buffer and temperature calibrations. instrument is designed for ELISA, rCA, tissue
Model 150—The Model 150 offers all the typing, cell feedings, simple inoculations and
features of the Model 145 plus direct measure chemistries. Dispenser volumes are adjustable
Perkin-Elmer's AD-6 Autobalance offers fea- from very few microliters to several milliliters,
of activity/concentration, clock and timing tures ihat simplify weighing tasks. Standard
modes, automatic endpolnt sensing, set points, with ± 3 % reproduclblity. A unique feature of
features include automatic zeroing and taring, the multiple manifold dispenser is that it can
five-language alphanumeric prompting and a simple calibration, safe memory for 899
five-electrode memory for use with Coming's samples, additive or multiplicative factoring of
Multi-Electrode Selector—all operable through weights and statistics routine. The control unit Continued on page A24)
includes a keyboard panel with dual LCD dis-

T o t a l
i n f o r m a t i o n
r e t r i e v a l
f o r
o r g a n i c c h e m i s t s
I n t r o d u c i n g organic compounds which were Like its popular print equiv-
Index Chemicus® Online:

first reported as new from 1962 alent, Current Abstracts of
. . . the first in a series of

to the present. Chemistry and Index Chem-
icus®, the data-base provides
Chemical Information Data-
Substructure searching a c c e s s t o : analytical techniques,
bases from the Institute for
Scientific Information®!
Full graphic input and output, such as column chromato-
Chemical Information Divi-

plus DARC's easy-to-use text graphy and nuclear magnetic
sion (ISfiCID). The initial

structure input, facilitate fast, resonance, when presented in
v e r s i o n of this n e w o r g a n i c s u b -
complete substructure search- detail in t h e article • biological
structure data-base will be

ing. In addition to substructure activities, aH p o t e n t i a l a n d test-
available online in early 1984

searching, compounds may also e d activities r e p o r t e d in t h e ar-
through Questel, using the

be retrieved using molecular ticle • a new synthetic methods
DARC system.
formulae or Wiswesser Line indicator • the amount of ex-
Notation. . perimental detail • as well as
E x t e n s i v e c o v e r a g e detailed bibliographic informa-
Index Chemicus Online of- tion.

Precise searching
fers fast, a c c u r a t e access to
Index Chemicus Online helps With t h e total information In-
new organic chemistry as re-
you identify articles of interest dex Chemicus Online provides,
ported in the chemical journal
quickly, and precisely, as well you can easily m a k e an immedi-
l i t e r a t u r e . T h e initial v e r s i o n of
. . . because you get enough to- ate, well-informed decision
t h e d a t a - b a s e will c o n t a i n com-
tal information to distinguish ar- whether to obtain the original
pounds, with their related bib-
ticles of specific value to you— article.
liographic data, reported from before you order and read them. T o find o u t h o w Index Chem-
1977 to date a n d from 1962 to
m t m m m t m ^ m j c u s Online can
1965 — giving ~" """
I Please send me more information on: I help you get the
access to infor-
I Q Index Chemicus® Online • QmsteliDARC Oniine training sessions I precise informa-
mation not read-
I tion you n e e d
ily available on-
line from any
I NameiTitie I from the chemi-
I cal j o u r n a l litera-
other source. Organisation/Department
When completed
I I ture, fill out and
in 1984, the full

I Address City I mail t h e coupon,
Slate/Province Country or call toll-free

file will contain
I 1 800-5234857.
over 3,000,000
I Sp'Kistal Code Telephone
I ® Institute for Scientific Information* Chemical
1
Chemical Information Division Marketing
Information I Circle No. 29
on Readers' Inquiry Card
I 3501 Market Street. Philadelphia. Pennsylvania 19104 U.S.A.
Telephone: (215) 386-0100, Cable: SCINFO, Telex: 84-5305 Division
iS-3373 - ™ >s>J
surfaces. Column cooling is possible by using
o u t o f t h e a recirculatlng refrigerating bath with precise
counter-heating by the Delta Temp. Up to 4
e d i t o r y b a s k e t columns may be operated at any one time.
Maximum column size is % in. dia. X 30 cm
long. Computer control is practical via built-in
interfaces.
be used T-styte (center operation) or offset Circle #63 on Readers' inquiry Card
style (side operation). Three models are different ratios regardless of temperature,
available. pressure or flow variations. This unit features
Circle §58 on Readers' Inquiry Card up to four channel blending capability, a digital Chromatography Refrigerators
display and separate controls for each chan-
nel. It also offers costs savings and space
Chtorinator Alarm Switch savings over modular systems without com-
F T £ E •
Fischer S Porter announces an economical promising controi, accuracy and precision.
switch which can be used in an atarm circuit Each of the four channels can be Controlled,
to advise operating personnel that the chlorine remain independent with a constant flow, or
gas supply feeding a Chiorinator has been remain idle with no flow. Controi of the channel
depleted. The switch serves io prevent un- can be by an external ratio of another f!ow-
chiorinated water from reaching consumers stream, by internal manual adjustment, or by
or uncbJorinated wastewater from being dis- an external 0-5 VDC signal. The digital LED
charged info receiving bodies of water. Al- display and the four channel set-read switch
ternately, the switch may be used with auto- allow the operator to monitor each channel,
matic chlorine changeover systems to inform one at a time, as desired.
operators that the Chlorination system is op- Circle #61 on Readers' Inquiry Card
erating from a standby source. The switch Is
available in kit form for use with ail Chlorlna-
tors having capacities up to 2000 Ib/day, and The Jewett Refrigerator Co., Inc. has an-
may also be used to retrofit Chlorinators which
Armored Sheath Thermistor nounced two refrigerator models designed to
are presently in service. Assemblies meet the exacting demands and specific needs
of liquid chromatography. This line of refrig-
Circle #59 on Readers' Inquiry Card erators compliments their diverse range of
hospital, laboratory and pharmaceutical re-
frigerators and freezers. Available in either
Specialty Gas Regulator single door (25-cubic ft) or double door (55-
cubic ft) models, both models consistently
maintain a dependable uniform cabinet tem-
perature of 4°C. Exterior fronts are provided
in a contemporary blue trim with beige cabinet
and white enamel Interior. Standard features
on boih units include: triple Thermopane glass
door (s); the security of key-locking doors; two
convenient vapor-proof covered access port-
holes; two interior vapor-proof covered duplex
outlets; adjustable stainless steel cantilevered
and four-position support shelves; and external
Armored sheath thermistor assemblies. Series
switches for interior light and lower outlet
A800, are available for Thermometrics for
shut-off. Optional accessories offered are
measuring temperatures in arduous atmo-
Jewett's 7-Day Recording Thermometer which
spheres where extreme temperatures and
monitors temperature variations of stored
rough service conditions are encountered.
product with the Mark-A-Matic II continu-
These assemblies are most often used for
Scott Sprcinlty Gases ."trodiice1. The Pro- ous—flow inking system. In the event of a
monitoring or controlling the temperature of
tector," a high purity two stage regulator de- power failure, its spring wound mechanism
hot, corrosive liquids, air or semi-soifds; and
signed by Scott Specialty Gases to protect the provides a complete record of the temperature
in process controls. A series A800 assembly
quality of high purity noncorrosive specialty of stored items. Jewett's Temperature Power
consists of a thermistor sealed at the tip of a
gases. The Protector is the answer to four Monitor System is an AC /battery operated
glass rod, which is then encapsulated into a
non-corrosive, high purity delivery system monitor abte to warn of dangerous temperature
stainless steel enclosure with a flexible, pro-
problems. Performance—The Protector has variations or power failure.
tective armor sheath over the extension leads,
two pressure reduction stages for accurate and
and are available with a variety of matrlals and
sensitive pressure control—from full cylinder Circle #64 on Readers' Inquiry Card
insulations based upon the specific applica-
pressure to 200 psi—"Just set it and ieave it."
tions. The housing may be a straight tube, or
Contaminant Prevention—The Model 18 has
may have an adaptor collar or threaded hex
a non-contaminating stainless steel diaphragm
body as desired. The closed end tube is 1.0 T e m p F r e e z e r
in both stages to prevent diffusion and out-
available in lengths from 1 inch to 6 in.; the The Harris Lo Temp 25LS Freezer is a sturdy,
gassing; It also have Viton and nylon seats and
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editorially /peaking
Facts and Their Roles in Chemistry

rFieanPdcasectsm o,ruw ohbcihservaaretiond,"efinoecdcupyasa"truunthiqsueknopw o snitonbyinacctuhaelm O
a c ehtihxsotrepyrres.-w haasvethnooutghstototdo thbee taenst im ofptim o rt
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t
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f ac t
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s-ore analytical skils. Students should be encouraged to
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S o m e f ac t
s a re w ro n g , b u t us e
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inert gases are now caled "rare gases". t o g eivssew m oorkres w a telntitoonhetoiphsetulpdinegntsstuacdqeunirtes afaccqtus;irebuthteweskinlesed
e
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e r a ti ol n asnipinuvlaotelvedthesine tfhacetisr am ndantipoulaatirotincus.late the ideas and op-
relationshipsorisobw serithvoautiotn.qT uehsetionim, peo.grta.,ncemooflecusolam rewoefigthht.ese JJL
Volume 61 Number 1 January 1984

in thf/ iz/ue
Gilbert Newton Lewis:
GILBERT NEWTON LEWIS
1875-1946 1875-1946
tchheIenfmw G e.yN ie].dLJ.ewW s

i m ilarudstG su ibreblys troanktheasmthaethegm re aaticteasltpohfyA sicm istsercian
dofidthheeistesy.am cChpieeovrstauieim
nlygrehaet thhiansgshehenimtsheelf, m b u otstheinflw ueanstiaal.lsoN , oatsom nlyany,
aMnoerextrtahoarndinaanryyongeropuaepplseeorsfhesbtueadlerdenwtsA ,itnm aesssseo,rciacaniatem sch,aeaojm
nrdisintrycspoilfrreoaam tigounes.to
pro-
vinciality to world leadership.
a"nG T
dilhbeeervretenN wlaesssnoinstihgneificloanccaetionin, Lthaes V dateeg,as,30fo-3r1theMsayrcm hpo1s9uim 82,
neewotthsnuechLinesw aigish:sytsm18p7o5su-i1m 946".indItefm erleylyifsew em edwuernewtisoe
by the pioneer physical-organic chemist Gerald E. K, Branch
tboenepfoitstpfroom in i
t
e e (page 18).
pHrinapcpipilyalthseuyrvivaorersleagnidon.suSacnhcdeosrstlyothrsebeom fforeethm oreiG s.ofNs.om eewosif era. the

Exigences of space precluded the publication of all the
ew ediom L
symposium papers in this one issue of the JOURNAL SO it's well
we,t iM n aL ryasH V.egas

that we list what is yet to come.
tL heewisfo;lowing note arrived from Lewis' w February 1984
Glenn T. Seaborg, "The Research Style of G. N. Lewis: Acids
DIeaarm . Drd.elD i
g h atevdenpthoart,t Gilberts' memoyr has been kept alive al and Bases."
Leo Brewer, "The Generalized Lewis-Acid-Base Theory:
hthoenseor.yT eahrasnkandyouthaaitlaverysymm pousuichmforisynoouw r p baertinginhit.eldIinwohudils

Surprising Recent Developments."
Kenneth S. Pitzer, "Gilbert N. Lewis and the Thermody-
htraavveel.olvIedsendto m bey pbreesstenw t, sihbeust fuonrfothrtuenatesluycceam s s o nothteabsleymtopo-
fnamics of Strong Electrolytes."
Jacob Bigeleisen, "Gilbert N. Lewis and the Beginnings of
sium. SMaryH.
incerely yours, Lewis Isotope Chemistry."
March 1984
S
L im
e w ilaisr' ognrlyeetindgasugw h t
e erre. G reiclbeeivretdandfromMaM y
t rL
s.ew Misa'rgw t eryo Scheeibm y,ist
Anthony N. Stranges, "Reflections on the Electron Theory
of the Chemical Bond: 1900-1925."
-bsoapcnrkesg,sreoR nutnicdhinaridnLaahsnisdV"A eEgdasw ,Piaoarndnd,eetroR geicthhearrdwLithewtishetirracw iveths,ew em

reily
Linus Pauling, "G. N. Lewis and the Chemical Bond."
Spirit from a Pioneer Family" e s Rule."

fa
William B. Jensen, "Abegg, Lewis, Langmuir, and the Octet
(page 3). Michael Kasha, "The Triplet State: An Example of G. N.
oJhmonhsnHSoeprkvinoss,U anhiviesrtosityrianwaosftsitcleiednce"Phwyhsoicsael P hD thistryesisinat

Lewis' Research Style."
JA C h e m
otufretheefroricm ad:isO prliignIT ines,ofGprohwyhtsicaalndcheD eisftriynitiopnri,"ortetolsLoefwthise' dstepaater- In the Bancroft Library of the University of California there
ciM faosr toCablifeocornm m
iaeinpe1rs9o1n2al(preasgeaerch5).asM
is a strange box of miscellaneous odds and ends labelled
uachnt ltaoter
simply "G. N. Lewis." Among them we find visiting cards,
G G e
l n n S e a b o rg w s i s t
several receipted bills, a military order from the time Lewis
bSahs.oerN ttlyh.eoaLrfyteew siyinday193w 7,hilewom rkinogonliw ittihnghm iin nouneleagrencehraelim zedistrya.cid-

served under General Pershing, and the manuscript of a
b
rdjoL ineinw gsi thinethsetaffdeinveloB g h erkeenletyofinthe19th3e7o,ryM
speech given on some unknown occasion to an obviously
evlcniolor
general audience. This latter concludes:
C
of orgaBa l
v i
n a s s i
s t
e
noicthsuSbesatabnocrgesaannddC thaelvinparahm p m aegnkentisom ofallthebuttripfoluert of o f
i have attempted to give you a glimpse.. .of what there irtay be
of soul m chemistry. But it may have been in vain. Perchance
state.
tphheotopgerrm anicenetsscahye,m"T istryhefaC cuoltylegeatoB a v eC w n
rkheleeymisstryincein1t9h1e2!G the chemist is already damned and the guardian of the peariy
T.heN.
gates has decreed that of all the black arts, chemistry is the
a p h
LeewsibuEtroa:ve1rla9p1p2in-1g946a"cco(puangtes. T f
11h)e, isfacaescpoelaertiiongn forofmthethiresseepa-
blackest. But if the chemist has lost his soui, he will not have
lost his courage and as he descends into the inferno, sees the
rat
odeldvelopphm otoegnratpohfsm coondterirbnutecdhem faristrm orT ehthisanfirsttheinirstaslhm
rows of glowing furnaces and sniffs the homey fumes of brim-
areenttoofthe
stone, he will call out:—:
t"hG eilbsyem pNosuiem proLceew y .

edisin:gsHisconInclfuludeenscewoithnM eylvsinical-O Carglvaninics'
"Asroodeus, hand me a test-tube."
C rt w ot n P h That last phrase might well serve as Lewis' epitaph.
hishem papistseratisB anerkuenleyp"ubli(sphaegdem 14em ). oA rinofim Lepw orsitanw t ariptepnendinix1t9o53 Derek A. Davenport
Pufdue University
West Lafayette, !N 47907
Journal of Chemical Education

> *
A Pioneer Spirit from a Pioneer Family
Richard N. Lewis
P.O. Box 233, Inverness, CA 94937
Anyone who knew Gilbert Newton Lewis is aware of his One of the five, my grandfather, Frank Wesley Lewis, waa
ability to strike out into a new field of chemistry, but few are born in 1840. He became a lawyer and specialized in insurance.
aware of the breadth of his pioneering activities. We will hear He died in 1910 and I know very little about him, except that
of several areas of his chemical interests in this symposium. he wrote a book, "State Insurance" (Houghton Mifflin, 1909),
But his interests also included such areas as relativity, the that was a forerunner of our present Social Security system.
reversibility of time, origins of the elements, economic theory, He was at least 25 years ahead of his time, undoubtedly a
glaciology, and anthropology. radical, certainly a pioneer. I wish I knew whether this book
had any direct influence on President Franklin D. Rooseveit.
My purpose is to investigate the antecedents and back-
I have a photograph (1890) of him and three of his brothers,
ground of Gilbert Newton Lewis in the hope of shedding some
all very distinguished-looking men, but I have no information
light on how such a remarkable man could arise. He himself
on them or their children.
did not talk much about his ancestors, though he did make an
effort to track them down. He was stymied, however, when he Frank married Mary Burr White, the daughter of Newton
got as far back as Barnstable, Massachusetts in the 1700's, White of Hoi brook, Massachusetts—a "great and good
where he found all previous records had been destroyed by man"—according to Aunt Poily. The name Burr possibly in-
fire. I have been only slightly more successful. dicates some relation to Aaron Burr, but then we probably all
The first ancestral Lewis of record was George Lewis, who have some black sheep in our families. Mary had been edu-
came from East Greenwich in Kent to the Plymouth Colony cated in a ladies' seminary near Boston; both she and Frank
in 1632, with his wife, the former Sarah Jenkins. He became had definite ideas on education and were sure that the avail-
a farmer in Scituate, took the freeman's oath in 1635, and in able schools were not for their children. She taught Gilbert to
1639 was one of the founders of the town of Barnstable, the read at the age of three; he read Robinson Crusoe at age five
first English settlement on Cape Cod. He was a constable and, thereafter, every book he could get his hands on. Frank
there, and a member of the militia. A Congregational Church taught him his mathematics, a good teacher with an apt pupil.
was established in 1639; the Church building, now the Sturgis Somewhere, Gilbert received a'thorough knowledge of Latin,
Library, was completed in 1646. We do not know George's Greek, German, and French.
religion, although his (probable) brother, John, who arrived Aunt Polly was born in 1871, Gilbert in 1.875, and Roger in
in Scituate in 1635, is described as a man of some property and 1884, the year the family moved to Lincoln, Nebraska, where
a devout Anglican. John's son, Joseph, lived in New London Prank was a lawyer and broker. They lived on the outskirts
and Windsor, Connecticut. of town on a small farm. I believe this is where Gilbert ac-
George had five sons, of whom three, Ephraim, George, and quired a lo%re of nature. He noted that birds would gather there
Thomas, were born in England. His son, John, was among six as it was one of the few places in the area that had trees. (His
men from Barnstable killed in the bloody "King Philip's War" favorite was the catbird, a bird of unassuming appearance but
with the Indians in 1676. Marriage records indicate a Sarah great virtuosity of voice.) I believe Polly had a strong influence
Lewis, probably a daughter, was married to James Cobb in on Gilbert. She apparently acquired some of her parents' ideas
Barnstable in 1663; John Lewis, probable grandson, was on education and set up a private school in Buffalo where she
married to Alice Bishop, a widow, in 1695. could teach the way she thought children should be taught.
My parents carried on in the same vein. Their three children
The census of 1790 listed no fewer than 34 Lewises as heads
were taught at home until their late high school years.
of households in Barnstable, probably all descendants of
George through five or six generations, including a Jabez I have looked with little success for any scientific back-
Lewis, our ancestor. Jabez waa an Anglican (Episcopalian) ground in the family. I once received from Giibert's cousin,
and, therefore, most likely suspected of being a Tory (whether Dr. Marian Bugbee of White River Junction, a battered
he was or not). Perhaps life became uncomfortable for him, chemistry text from about 1840 that seemed incapable of in-
or the town was now overpopulated. In any case he pulled up spiring anyone, but someone in the family must have got some
stakes with his wife, Mary, son, Wilca, teen-age daughter, use out of it.
daughter-in-law (former Betsey Stuart), and one grandchild. Undoubtedly the most powerful influence in Gilbert's
(Dad used to say, "There's royal blood in my veins." I suppose chemical career was that of T. W. Richards, who joined the
he was thinking of the Stuarts.} They joined a party of pi- staff at Harvard in 1894, the year after Gilbert transferred
oneers under the leadership of John Leet and traveled to the from the University of Nebraska. It seems that Richards was
wilds of western New Hampshire, settling in what is now West involved both in Gilbert's undergraduate and graduate edu-
Claremont. cation. His thesis, published with Richards was, "Some
Wilca had eight children between 1796 and 1804, but times Electrochemical and Thermochemical Relations of Zinc and
were hard and several died in an epidemic of scarlet fever, Cadmium Amalgams."
along with his first wife and his young sister, whose portrait Other men who influenced his career were the physical
hung in my Aunt Polly's house for many years. George Gilbert chemists Walter Nernst in Leipzig and Wilhelm Ostwald in
Lewis, born in 1800, survived. He grew up in West Claremont Goettingen, under whom he studied in 1900-1901. He was
and married Adeline Labaree, a descendant of the early certainly influenced by A. A. Noyes, with whom he worked for
French trapper, Pierre Labaree. He fathered five strong boys seven years at M.I.T. Although he had little, if any, direct
and promptly died, leaving Adeline to manage alone. She was contact with Albert Einstein, he was excited by Einstein's
made of stem stuff, however, and raised them all successfully, ideas of relativity and published four articles on it, including
single-handed. Not only that, but she put them all through one with R. C. Tolman and another with E, B. Wilson, Sr. In
Dartmouth College. one respect he differed totally with Einstein; that was in his

insistence on the role of chance in the natural world, especially Through his own pursuit of learning, I believe that he in-
in regard to quantum mechanics and entropy. Einstein had fected all who came near him with the spirit of inquiry. His
great difficulty accepting this. associates and his students have gone on to spread the Lewis
While at M.I.T. he had room and board with Edward S. attitudes toward research and education. His influence con-
Sheldon, Professor of Romance Languages at Harvard, whom tinues and will continue.
he greatly admired. Lat«r he married Sheldon's daughter, I am glad al! of you have been able to honor him by your
Mary Hinckley Sheldon—another remarkable woman in presence today.
Gilbert's life. She still survives at age 91. Both she and her
daughter, Margery Selby, are very sorry not to be able to be Sources
here today. So is his grandson, also Gilbert Newton Lewis, (1) Personal rominisrenses of Gilbert Newton I-ewis and Mary Hammond Lewie (Aunt
Professor of Mathematics at Michigan Technological Uni- Polly).
versity. (2) "The Lewis Family," The American Genealogical Research Institute, J60I Wilson
Boulevard, Arlington, VA 2231)9.
Ever the student, even while teaching, he learned from ev- (3) Records and gr&v<istonen of the West Cl&remnnS. (N.H J Union Church (Episcopal).
eryone around him, especially his associates and his students, H) Arthur Lochraan, "Borderland of the Unknown-The Life Stosy of Gilbert Newton
Lewis»One of the World's Great Scientists," Pageant Press, New York, 19S5.
among whom may be mentioned especially Joel Hildebrand, (5) "In Honor of Gilbert Nflwton Lewis on hia Seventieth Birthday," University of California
Gerald Branch, Ernest Gibson, Harold Urey, Glenn Seaborg, Press, Berkeley, 19J5.
(+3) Giauque, Wr F., "Gilbert Mewlon Lewis/' Year Boot of The American Philosophical
Melvin Calvin, and Jacob Bigeleisen. Society, Biographical Memoirs, pp. 317-322,1M6.
The Southwest Chemistry Lecture Exchange Program

A recentnote' concerning the organization of a chemistry lecture exchange inspires the author to relate the formation
of the very successful Southwest Chemistry Lecture Exchange Program which has been in continuous operation for an ex-
tended period oftime. The mode of operation of this program may be usefultotiiose in other areas of the country that might
desire to set up a similar program.
The current program was organized by the author at the Southwest Regional Conference on Graduate Studies in
Chemistry at The Southwest Regional Meeting of the ACS in Shreveport, Louisiana.2 Of the 1.6 institutions3 offering doctoral
degrees in chemistry in the states ofArkansas, Louisiana, New Mexico, Oklahoma, and Texas, one or more representatives
from each of 13 institutions participated in the formation of a iecture exchange program among their schools. The main
features of the exchange were the following:
(1) Lists of topicsand speakers from each department were exchanged. A list of all of the participating institutions was
sent to all of the doctoral-granting institutions so that eaeh school in turn coti)d send a list of topics and speakers to all
of the others on the list. Some of the lists were sent out. so that they were ready for lecturer invitationsforthe following
spring semester.
(2) In order to simplify the problem of travel expenses it was agreed that the school from which the speaker originated would
pay travel costs if this was allowed by the particular institution.
(3) New iists of available speakers and topics were exchanged each year (preferable in the summer or eariy fall). The list
for the preceding year would be used for inviting speakersforprojected seminar programs for the following academic
year.
Under this particular setup, the Exchange Program "runs itself without anyone being responsible for the overall di-
rection.
Several benefits have come from theSouthwest Chemistry Lecture Exchange Program.
(1) The Exchange has been a source of speakersforseminars, coiioquia, and for ACS meetings. This has particularly been
beneficial to the smaller institutions and ones that are "off the beaten path."
(2) Benefits to the larger schools are the opportunitytorecruit graduate students, to organize and present new material,
and to become acquainted with smaller institutions in theSouthwest and their faculty.
(3) The visit of a speaker to an institution has afforded opportunities for the speakertobecome acquainted with the members
of the department and also to see what facilities are available. This has resulted in a number of cooperative research
projects throughout the area.
{4) Since the members of the department become acquainted with thearea of the visitor's research interests, they have
frequently been able to recommend the visitor to undergraduate students contemplating graduate study.
(5) Some departments have given the speaker an opportunity to meet with undergraduatechemistrymajors and present
to them opportunitiesforgraduate study at their respective schools. This has been particularly convenient at the author's
institution since graduate seminars are scheduled at 3:15 p.m. on Fridays whereas an undergraduate seminar for seniors
is scheduled each semester on Fridays at 2:00 p.m.
(6) Lists of names and addresses of senior chemistry majors are being exchanged among some of the schools as potential
graduate students.
Since the beginning of the Lecture Exchange Program, a number of schools that have instituted doctoral programs
or which have developed viable master's degree programs have joined the Exciiange Program. These are East Texas Stale
University, Southern Methodist University, University of Texas at Arlington, University of Texas at Dallas, and University
of Texas at El Paso. Since lecture exchanges havetendedto occur more frequently between institutions that are closer in
terms of distance, some of the schools in the outermost areas of the Southwest region have extended their range of schools
beyond the Southwest region.
1
Chem. & Eng. News, 34 (Sept 20,1982). The lecture exchange being organized by Erwin Bosehmann of Indiana University
is on
! a quite different basis than the one described in the present paper.
s The 20tii Southwest Regional ACS Meeting, Washington Youree Hotel, Shreveport, Louisiana, Dec. 5,1964.
The 16 institutions were: University of Arkansas, Louisiana State University (Baton Rouge),* Louisiana State University
(New Orleans) (now University of New Orleans), Tulane University, University of New Mexico, Oklahoma State University,
University of Oklahoma,' Baylor University, North Texas State University, Rice University, Texas A&M University, Texas
Christian University, Texas Technological College (now Texas Tech University), Texas Woman's University,* University
of Houston, and University of Texas at Austin. Representatives who did not attend the meeting but participated in the Lecture
Exchange Program are indicated by an asterisk. A_ Q_ pjn|(0B
Baylor University
Waco, TX 76793

GILBERT NEWTON LEWIS
G. N. Lewis: The Disciplinary Setting

John W. Servos
Department of History, Amherst College, Amherst, MA 01002
I s h o u l d like to begin w i t h a text, a s h o r t p a s s a g e f r o m a t h a t was often narrowly defined by t h e problems of dilute

letter t h a t G. N . Lewis w r o t e in F e b r u a r y 1922 to his colleague a q u e o u s s o l u t i o n s h a d b e c o m e a s e t of t e c h n i q u e s a n d w a y o f
at Iâfayette College, E u g e n e C. B m g h a m . " T h e fact is," Lewis t h i n k i n g a b o u t c h e m i s t r y t h a t defied any simple definition.
w r o t e {1), A s u b j e c t t h a t w a s s o c l o s e l y i d e n t i f i e d w i t h t h e s t u d y of
c h e m i c a ! processes t h a t t a l k of a t o m s a n d molecules w a s often
that physical chemistry n o longer exists. T h e m e n w h o have been c e n s u r e d for b e i n g s u b v e r s i v e h a d g i v e n w a y t o o n e i n w h i c h
called physical c h e m i s t s h a v e developed a iacge n u m b e r of useful
it w a s i n c r e a s i n g l y u n d e r s t o o d t h a t s t r u c t u r e w a s r e l a t e d t o
m e t h o d s b y w h i c h t h e concrete p r o b l e m s of inorganic chemistry,
process. A subject t h a t was, despite the good intentions and
organic chemistry, biochemistry, and technical chemistry m a y be
c k i m s of i t s f o u n d e r s , v e r y r e m o t e f r o m m e e t i n g t h e n e e d s o f
attacked, a n d asl.be applications of these m e t h o d s grow m o r e nu-
m e r o u s , it b e c o m e s increasingly difficult to adhere to our older
other scientists h a d been supplanted by a vigorous n e w
classification. p h y s i c a l c h e m i s t r y that; t r e a t e d r e a l a s well a s i d e a l s t a t e s a n d
h e n c e w a s of u s e t o c h e m i c a l e n g i n e e r s , p e t r o l o g i s t s , b i o -
W h e n L e w i s w r o t e this h e w a s in his mid-forties. H e h a d b e e n c h e m i s t s , a n d s c i e n t i s t s of m a n y o t h e r s t r i p e s . A n d a s u b j e c t
a t t h e U n i v e r s i t y of California for a l m o s t ten y e a r s a n d h a d t h a t h a d b e e n t h e p r e s e r v e of a s m a l l a n d w e l l - d e f i n e d g r o u p
built t h e r e a center for chemical research a n d training t h a t w a s of practitioners, s o m e t i m e s called " t h e ionists," h a d b e c o m e
w i t h o u t parallel in this c o u n t r y . H e w a s t h e n dictating his t h e c o m m u n a l p r o p e r t y of a l l c h e m i s t s .
treatise o n t h e r m o d y n a m i c s to M e r l e R a n d a l l a n d w a s p r e -
p a r i n g a s e c o n d b o o k o n valence, b o t h of w h i c h w o u l d a p p e a r T h i s t r a n s f o r m a t i o n of classical p h y s i c a l c h e m i s t r y t o o k
t h e following year. A s m u c h as a n y m a n , L e w i s h a d b e e n replace d u r i n g Lewis's early m a t u r i t y , a n d it w a s a transfor-
s p o n s i b l e for d e v e l o p i n g a vigorous tradition of p h y s i c o - m a t i o n t o w h i c h Lewis himself m a d e vital c o n t r i b u t i o n s . Y e t
c h e m i c a l r e s e a r c h in t h e U n i t e d States. T h a t he, w h o w a s d e s p i t e t h e significance of L e w i s ' s w o r k , w e k n o w v e r y little
w i d e l y r e g a r d e d as A m e r i c a ' s p r e e m i n e n t p h y s i c a l c h e m i s t , about the formative years during which he began to m a k e
should h a v e s u g g e s t e d t h a t t h e field n o l o n g e r e x i s t e d is, t o say those contributions to chemical thermodynamics and the
t h e least, s o m e w h a t ironic. t h e o r y of v a l e n c e f o r w h i c h h e is b e s t r e m e m b e r e d . W h a t 1
s h o u l d l i k e t o d o i n t h i s e s s a y is t o c o n s t r u c t a p i c t u r e of t h e
I t is p o s s i b l e o f c o u r s e t h a t Lewis w a s e n g a g i n g in his well- e a r l y s t a g e of L e w i s ' s c a r e e r — t h e a p p r e n t i c e s h i p t h a t h e
k n o w n t e c h n i q u e of c o n f r o n t i n g his r e a d e r w i t h a s u r p r i s i n g served before arriving a t B e r k e l e y in 1 9 1 2 — a n d t o set t h a t
p a r a d o x , b u t I d o n o t t h i n k so. T h i s w a s n o t t h e oniy occasion p i c t u r e a g a i n s t t h e b a c k - d r o p of t h e t r a n s f o r m a t i o n t h e n
o n w h i c h L e w i s e x p r e s s e d his d i s c o m f o r t w i t h t h e label u n d e r w a y in physical chemistry. W h a t w a s physical c h e m i s t r y
"physical c h e m i s t " (2). M o r e i m p o r t a n t , Lewis w a s in a sense w h e n L e w i s e n t e r e d t h e field in t h e l a t e 1890's? H o w d i d h i s
q u i t e correct w h e n h e said t h a t physical c h e m i s t r y n o longer t r a i n i n g a n d e a r l y e x p e r i e n c e m o l d his c o n c e p t i o n of t h e
existed, for t h e physical c h e m i s t r y of his y o u t h , t h a t of Ost- subject? A n d to w h a t degree did t h e teachers and colleagues
wald, A r r h e n i u s , a n d van't Hoff, h a d b e e n t r a n s f o r m e d in s u c h w i t h w h o m he w o r k e d in t h o s e early y e a r s s h a p e Lewis's in-
f u n d a m e n t a l w a y s a s to b e a l m o s t u n r e c o g n i z a b l e . A subject t e r e s t s a n d t h e d i s t r i b u t i o n of his efforts? L e w i s ' s a c h i e v e -
m e n t s , of c o u r s e , c a n n o t b e f u l l y u n d e r s t o o d i n t e r m s of h i s
training, for h e possessed a n originality t h a t could n o t b e
t a u g h t , h u t e v e n m e n of g e n i u s b e a r d e b t s t o t h e i r t e a c h e r s ,
a n d it is t h e s e t h a t I s h o u l d l i k e t o a s s e s s .
Let us begin by better defining Lewis' starting point, t h e

physical c h e m i s t r y he e n c o u n t e r e d as a s t u d e n t in t h e 1890's.
T h e s u b j e c t was, in fact, y o u n g e r t h a n L e w i s himself, a t l e a s t
if o n e t h i n k s o f i t a s a d i s t i n c t a n d w e l l r e c o g n i z e d s p e c i a l t y .
W h e r e a s L e w i s w a s b o r n in 1 8 7 5 , p h y s i c a l c h e m i s t r y w a s a
c r e a t u r e of t h e 1880's. T h a t was, of course, t h e d e c a d e t h a t saw
t h e p u b l i c a t i o n of v a n ' t H o f f s s t u d i e s in c h e m i c a l d y n a m i c s
a n d t h e o r y o f o s m o t i c p r e s s u r e ( F i g . 1 ) , of A r r h e n i u s ' t h e o r y
o f e l e c t r o l y t i c d i s s o c i a t i o n { F i g . 2 ) , of O s t w a l d ' s m a s s i v e
"Lehrbuch der allgemeinen Chemie" a n d his famous dilution
l a w ( F i g . 3 ) , a n d of N e r n s t ' s t h e o r y o f t h e c o n c e n t r a t i o n c e l l .
Et w a s a l s o t h e d e c a d e i n w h i c h a n i n s t i t u t i o n a l b a s i s f o r
p h y s i c a l c h e m i s t r y w a s c r e a t e i i . T h e Zeitschrift fiir physi-
kaUsche Chemie b e g a n publication in 1887, a n d , in t h a t s a m e
year, O s t w a l d w a s called t o a chair a t t h e U n i v e r s i t y of Leipzig,
w h e r e h e q u i c k l y b u i l t u p t h e p r e m i e r c e n t e r for t r a i n i n g i n
t h e n e w d i s c i p l i n e [3],
B u t s t a r t l i n g a s t h i s r e c o r d of a c c o m p l i s h m e n t w a s a n d is,
it s h o u l d b e r e m e m b e r e d t h a t w h e n O s t w a l d , A r r h e n i u s , a n d
v a n ' t H o f f c a m e t o g e t h e r in t h e 188Q's t h e y faced s e r i o u s o b -
Figure t . J . H. van'1 Hoff in 1904. Photo courtesy of the Center (or the History s t a c l e s in t h e i r e f f o r t s t o w i n t h e r e c o g n i t i o n o f t h e i r f e l l o w
of Chemistry. scientists. Physical c h e m i s t r y was b o r n a m i d conflicts, a n d

Figure 2. Svante Airhenius. Photo courtesy of iiie Center lor the History of
Chemistry. Figure 3. W. Ostwatd. Photo Courtesy of the Center for the History of Chem-
istry.
t h e s e ieft d u r a b l e i m p r i n t s o n t h e y o u n g s p e c i a l t y . I n t h e first T h i r d , t h e d e v e l o p m e n t o f p h y s i c a l c h e m i s t r y in i t s e a r l y
place, t h e f o u n d e r s of t h e n e w discipline h a d t o o v e r c o m e t h e years was entwined with the debate over a t o m i s m t h a t raged
tendency, especially p r o n o u n c e d in G e r m a n y , t o identify or- a m o n g p h y s i c a l s c i e n t i s t s a t t h e e n d of t h e n i n e t e e n t h c e n t u r y
g a n i c r e s e a r c h as t h e c u t t i n g e d g e of c h e m i s t r y . T h i s m e a n t {7). D u r i n g t h e 1 8 9 0 ' s , O s t w a l d c o m m e n c e d h i s p u b l i c a t t a c k s
c o m p e t i n g w i t h o r g a n i c c h e m i s t s for c h a i r s , i n s t i t u t e s , a n d t h e o n t h e d o c t r i n e of a t o m i s m , c h a r g i n g t h a t i t w a s a h y p o t h e s i s
p a t r o n a g e of i n d u s t r i a l c o n c e r n s . I t also e n t a i l e d c o m p e t i t i o n w i t h o u t v a l u e , e i t h e r as a g e n u i n e d e s c r i p t i o n of n a t u r e or as
o v e r goals a n d p r i o r i t i e s . I n t h e c o u r s e of a s s e r t i o n a n d a guide to research. N a t u r a l science, h e argued, would b e
counter-assertion, Ostwald a n d his cohorts c a m e to define b e t t e r s e r v e d if i n v e s t i g a t o r s r e j e c t e d u n o b s e r v a b l e e n t i t i e s
p h y s i c a l c h e m i s t r y a s t h e s t u d y o f t h e p r o c e s s of c h e m i c a l a n d m e c h a n i c a l m o d e l s a n d i n s t e a d g r o u n d e d t h e i r w o r k in
c h a n g e — o f t h e a r r o w or e q u a l s i g n i n c h e m i c a l r e a c t i o n s — t h e t h e s u r e a n d g e n e r a l p r i n c i p l e s of t h e r m o d y n a m i c s . H i s col-
a n t i t h e s i s of o r g a n i c c h e m i s t r y w h i c h d e a l t w i t h t h e c o m p o - l e a g u e s , A r r h e n i u s , v a n ' t Hoff, a n d N e r n s t , d i d n o t e n t i r e l y
s i t i o n a n d s t r u c t u r e of r e a c t a n t s a n d p r o d u c t s . T h e o r g a n i c subscribe t o t h i s view, b u t Ostwald, as t h e p u b l i c s p o k e s m a n
c h e m i s t , O s t w a l d c h a r g e d , w a s like t h e m i n e r of '49 w h o h a d for p h y s i c a l c h e m i s t r y a n d a s t h e o u t s t a n d i n g t e a c h e r in t h e
b u t o n e t h o u g h t , t o d i s c o v e r g o l d e n n u g g e t s (4). I n h i s h a s t e n e w d i s c i p l i n e , w o n a w i d e h e a r i n g for h i s i d e a s a n d e x e r t e d
to seek out new c o m p o u n d s , he neglected the questions fun- considerable influence over y o u n g recruits.
d a m e n t a l t o all c h e m i c a l c h a n g e : h o w do physical c o n d i t i o n s
T h e o u t c o m e of t h e s e c o n t r o v e r s i e s w a s t h a t , b y t h e t u r n
a f f e c t t h e e q u i l i b r i u m a n d y i e l d of r e a c t i o n s , a n d h o w m a y t h e
of t h e c e n t u r y , p h y s i c a l c h e m i s t s w e r e a v o w e d l y o r i e n t e d
f o r c e of c h e m i c a t a f f i n i t y b e d e f i n e d a n d q u a n t i f i e d . O s t w a l d
t o w a r d t h e s t u d y of p r o c e s s r a t h e r t h a n s t r u c t u r e . S o l u t i o n s ,
saw himself as a reformer, working to m a k e chemistry an an-
t h e s i t e s of m o s t c h e m i c a l c h a n g e s , w e r e t h e i r c e n t r a l o b j e c t s
alytical r a t h e r t h a n a t a x o n o m i c s c i e n c e , a s c i e n c e of p r o c e s s
of investigation, a n d a m o n g solutions, d i l u t e a q u e o u s solutions
r a t h e r t h a n o n e of c o m p o s i t i o n a n d s t r u c t u r e . H e i n c u l c a t e d
of e l e c t r o l y t e s a t t r a c t e d t h e g r e a t e s t a t t e n t i o n . F i n a l l y , m a n y
t h i s a t t i t u d e in m a n y of his p u p i l s t o g e t h e r w i t h a c e r t a i n
physical chemists shared Ostwald's aversion to molecular-
c o n t e m p t for o r g a n i c c h e m i s t r y (5). I n s o d o i n g , h e o p e n e d a
k i n e t i c t h e o r y . H e h a d s u c c e e d e d in s e n s i t i z i n g a g e n e r a t i o n
g a p between organic a n d physica! chemists t h a t did not begin
of p h y s i c a l c h e m i s t s t o t h e d i s t i n c t i o n b e t w e e n fact a n d h y -
to heal until the twentieth century.
pothesis, a n d even t h o s e w h o disagreed w i t h his e x t r e m e view
of a t o m i s m o f t e n s h o w e d g r e a t h e s i t a n c e b e f o r e s e e k i n g t o
S e c o n d , t h e t h e o r y of electrolytic dissociation w a s t h e object
e x p l a i n p h e n o m e n a i n t e r m s of t h e s t r u c t u r e a n d p r o p e r t i e s
o f w i d e s p r e a d a n d g e n e r a ! d e b a t e f r o m i t s s t a t e m e n t in 1 8 8 7
of u n o b s e r v a b l e e n t i t i e s .
u n t i l well into t h e t w e n t i e t h c e n t u r y . A t first it w a s e x p o s e d
t o t h e s k e p t i c i s m of s c i e n t i s t s w h o s i m p l y c o u l d n o t a c c e p t t h e L e w i s of c o u r s e w a s still a b o y in t h e 1880's, a n d b y t h e t i m e
notion that stable molecules might spontaneously dissociate he r e a c h e d H a r v a r d in t h e m i d - n i n e t i e s , i n f o r m a t i o n a b o u t
in w a t e r . L a t e r , as t h e l i m i t a t i o n s a n d i m p e r f e c t i o n s of the new physical chemistry was only beginning to reach the
A r r h e n i u s ' t h e o r y b e c a m e clearer- -for e x a m p l e , a s t h e be- United States, carried primarily by Americans who h a d
h a v i o r of s o l u t i o n s of s t r o n g e l e c t r o l y t e s w a s r e c o g n i z e d as a worked with Ostwald and then returned to teaching positions
problem—physical chemists themselves began to question t h e in A m e r i c a n colleges a n d universities. Lewis h a d his i n t r o -
a d e q u a c y of t h e p r i n c i p l e . T h e t h e o r y o f e l e c t r o l y t i c d i s s o - d u c t i o n to t h e s u b j e c t in his senior y e a r a t H a r v a r d — 1 8 9 6 -
c i a t i o n h a d b e e n c o n s i d e r e d t h e Jewel i n t h e p h y s i c a l c h e m i s l s ' w h e n h e e n r o l l e d in a c o u r s e g i v e n b y o n e o f t h e s e v e t e r a n s of
c r o w n b e c a u s e o f t h e i n s i g h t i t a f f o r d e d i n t o t h e n a t u r e of Leipzig, T h e o d o r e W i l l i a m R i c h a r d s (Pig. 4) ( 8 ) .
s o l u t i o n s , t h e s i t e s o f m o s t c h e m i c a l p r o c e s s e s . I t is n o w o n d e r
Richards was t h e n a 28-year-old assistant professor, widely
that research on aqueous solutions should have dominated
regarded by his colleagues as being America's brightest u p -
physical c h e m i s t s ' concerns w h e n it t u r n e d o u t t h a t t h e jewel
a n d - c o m i n g c h e m i s t (9). H i s s t u d i e s o f a t o m i c w e i g h t s , f o r
was flawed (6).
w h i c h he w o u l d win t h e N o b e l P r i z e in 1914, w e r e a l r e a d y
6 Journal of Chemicai Education

b y his exposure to Ostwald's injunctions against confusing
h y p o t h e s e s w i t h facts. A l t h o u g h R i c h a r d s s p e n t m u c h of h i s
l i f e m e a s u r i n g a t o m i c w e i g h t s , a t t h e t u r n of t h e c e n t u r y h e
r e f r a i n e d from placing M l confidence in t h e a t o m i c t h e o r y ,
a t l e a s t in h i s p u b l i c s t a t e m e n t s . I n h i s p a p e r s f r o m t h a t p e r i o d
h e repeatedly cautioned his readers t h a t t h e atomic theory a n d
t h e e d i f i c e of m o l e c u l a r - k i n e t i c h y p o t h e s e s b u i l t u p o n i t
m i g h t , after all, p r o v e e p h e m e r a l (12). T h e real n e e d , h e s u g -
g e s t e d , w a s for d a t a t h a t w o u l d b e of l a s t i n g v a l u e d e s p i t e
c h a n g e s in scientific fashion. "Believing in F a r a d a y ' s m e t h -
o d s , " h e w r o t e , " I c a n n o t h e l p t h i n k i n g t h a t f a c t is m o r e i m -
p o r t a n t t h a n t h e o r y , a n d t h a t if o n e i n d u l g e s in t h e o r y , i t
vshould h e i n p h y s i c a l t h e o r y , c l o s e l y r e l a t e d t o f a c t a n d n o t a
metaphysical t h e o r y which seems able t o bear b u t little fruit
i n e x p e r i m e n t " (13). R i c h a r d s a p p e a r s to h a v e c o n s i g n e d t a l k
of c h e m i c a l b o n d s t o t h e r e a l m of m e t a p h y s i c s . I n his l e c t u r e
n o t e s t h e r e is a n e n t r y w h i c h r e a d s : " T w a d d l e a b o u t b o n d s :
A v e r y c r u d e m e t h o d of r e p r e s e n t i n g c e r t a i n k n o w n f a c t s
a b o u t c h e m i c a l r e a c t i o n s . A m o d e of r e p r e s e n t a t i o n ] n o t a n
e x p l a n a t i o n " (34).
It was while Lewis was a t H a r v a r d — i n d e e d , while he was

assisting in t h e course in which Richards m a d e these re-
m a r k s — t h a t L e w i s d e v e l o p e d his first r o u g h m o d e l of t h e
c u b i c a l a t o m a n d t h e c h e m i c a l b o n d {15), W e m a y w e l l
imagine t h e reception t h a t R i c h a r d s gave to his y o u n g assis-
t a n t ' s ideas. Y e a r s later, in 1919, L e w i s himself d e s c r i b e d h i s
e x p e r i e n c e d u r i n g this p e r i o d in very h a r s h t e r m s . " I w e n t
Figure 4. T. W. Richards, circa 1905. f r o m t h e M i d d l e - w e s t t o s t u d y a t H a r v a r d , " h e w r o t e (16), •
believing t h a t a t t h a t t i m e it r e p r e s e n t e d t h e highest scientific

ideals. B u t now I very m u c h d o u b t w h e t h e r e i t h e r t h e physics or
t h e c h e m i s t r y d e p a r t m e n t a t t h a t t i m e f u r n i s h e d real incentive t o
beginning to attract international attention, and the author- r e s e a r c h . In 1897 I wrote a p a p e r on t h e t h e r m o d y n a m i c s of t h e
ities a t H a r v a r d were grooming h i m to s t e p i n t o a professor- hohlraurn which was read hy several m e m b e r s of t h e chemistry a n d
s h i p . A s p a r t of t h a t g r o o m i n g , t h e u n i v e r s i t y s e n t R i c h a r d s p h y s i c s d e p a r t m e n t s . T h e y agreed u n a n i m o u s l y t h a t t h e w o r k w a s
t o E u r o p e in 1895 t o work w i t h N e r n s t a n d O s t w a l d . T h e r e n o t w o r t h d o i n g , especially as I p o s t u l a t e d a p r e s s u r e of light, of
R i c h a r d s u n d e r t o o k r e s e a r c h o n t h e e l e c t r o m o t i v e force of w h i c h t h e y all derided t h e existence. T h e y advised m e strongly n o t
t o s p e n d t i m e on s u c h fruitless i n v e s t i g a t i o n s , all b e i n g e n t i r e l y
a m a l g a m c e l l s a n d o t h e r topics i n t h e n e w p h y s i c a l c h e m i s t r y .
u n a w a r e of t h e similar work t h a t Wiert was t h e n doing. A few y e a r s
T h e course t h a t Lewis t o o k from h i m t h e following year n o
l a t e r I h a d very m u c h t h e s a m e i d e a s of a t o m i c a n d molecular
d o u b t r e f l e c t e d R i c h a r d s ' n e w - f o u n d e n t h u s i a s m for elec- s t r u c t u r e as I now hold, a n d I h a d a m u c h greater desire t o expound
t r o c h e m i s t r y a n d solution theory. It was a small course, at- t h e m , b u t I could n o t find a soul sufficiently interested t o hear t h e
t r a c t i n g b u t n i n e s t u d e n t s , a n d t h e l a b o r a t o r y in w h i c h ex- t h e o r y . T h e r e w a s a g r e a t d e a l of r e s e a r c h work b e i n g d o n e a t t h e
p e r i m e n t a l work w a s d o n e consisted of one small r o o m i n u n i v e r s i t y , b u t , a s I see i t now, t h e s p i r i t of r e s e a r c h was d e a d .
B o y l e s t o n H a l l , t h e a l l - p u r p o s e c h e m i s t r y b u i l d i n g (JO). B u t
t h e subject c a u g h t Lewis' interest, as did t h e professor who C l e a r l y t h e i m a g i n a t i v e a n d iconoclastic L e w i s h a d differ-
t a u g h t it, a n d a f t e r t e a c h i n g a t t h e P h i l l i p s A c a d e m y , A n d o - e n c e s w i t h t h e c a u t i o u s R i c h a r d s , w h o h e d g e d a l l of h i s b e t s .
ver, d u r i n g t h e y e a r following g r a d u a t i o n , L e w i s r e t u r n e d t o B u t whatever Lewis later j u d g e d H a r v a r d to have been, he
Harvard to obtain a doctorate under Richards. r e t u r n e d t o it r e p e a t e d l y , f i r s t f o r h i s g r a d u a t e e d u c a t i o n , a n d
t h e n , a f t e r a b r i e f a n d u n p r o d u c t i v e t r i p t o E u r o p e , for h i s f i r s t
T h e t r a i n i n g t h a t Iêwis r e c e i v e d a s a g r a d u a t e s t u d e n t w a s
j o b a s a n i n s t r u c t o r . T h e r e w e r e in fact t h i n g s to l e a r n t h e r e ,
first a n d f o r e m o s t a t r a i n i n g in e x p e r i m e n t a l t e c h n i q u e .
things t h a t Richards could teach. First, there was discipline.
Richards was a perfectionist in t h e laboratory, d e t e r m i n e d t o
If R i c h a r d s p u t t h e b r a k e s o n L e w i s ' e n t h u s i a s m f o r a t o m i c
s e a r c h o u t e v e r y l a s t s o u r c e o f e r r o r in h i s m e a s u r e m e n t s ,
a n d m o l e c u l a r s t r u c t u r e , it m a y well h a v e b e e n t o L e w i s '
w h e t h e r t h o s e m e a s u r e m e n t s w e r e o f a t o m i c w e i g h t s o r of
b e n e f i t , for h i s e a r l y m o d e l w a s a c r u d e a n d s p e c u l a t i v e affair
h e a t s of r e a c t i o n . H e w o r k e d closely w i t h his g r a d u a t e s t u -
w h i c h w o u l d , in a l l l i k e l i h o o d , h a v e c a u s e d h i m c o n s i d e r a b l e
dents, often treating t h e m as assistants. And, like m a n y per-
e m b a r r a s s m e n t if p u b l i s h e d . S e c o n d , t h e r e w a s t h e r m o d y -
fectionists, R i c h a r d s f o u n d it difficult t o delegate responsi-
namics. It was Richards m o r e t h a n anyone w h o fostered Lewis'
bilities to his co-workers- " I n m y experience," h e once wrote
i n t e r e s t in t h e r m o d y n a m i c s , a n d it w a s while h e w a s a t H a r -
v a r d , w o r k i n g closely w i t h R i c h a r d s , t h a t Lewis d e v e l o p e d t h e
c o n c e p t of e s c a p i n g t e n d e n c y or fugacity, from w h i c h h e l a t e r
a s s i s t a n t s who a r e n o t carefully s u p e r i n t e n d e d m a y b e worse t h a n
d e r i v e d t h e n o t i o n of a c t i v i t y . T h e p a p e r s t h a t R i c h a r d s a n d
n o n e , for o n e has t o discover in t h e i r w o r k n o t only t h e laws of n a -
L e w i s w r o t e d u r i n g t h e y e a r s from 1899 t o 1902 c o n v e y t h e
t u r e , b u t a l s o t h e a s s i s t a n t s ' insidious if well m e a n t m i s t a k e s . T h e
less b r i l l i a n t ones often faii t o u n d e r s t a n d tJie force of one's sug- distinct impression t h a t here were two chemists who were
gestions, a n d t h e tnore brilliant ones often s t r i k e o u t on b l i n d p a t h s teaching themselves a n d each other chemical thermodynamics
of t h e i r own if n o t carefuiiy w a t c h e d . b y e x p l o r i n g n e w m e t h o d s of o r g a n i z i n g t h e s c a t t e r e d , u n -
connected, a n d often imprecise equations which t h e n con-
Presumably, Richards placed the young a n d imaginative s t i t u t e d t h e f i e l d . A l t h o u g h t h e y w e r e j o i n t a u t h o r s of b u t o n e
L e w i s in t h e second category, a n d t h i s Lewis m u s t h a v e felt paper, they frequently cited one another's work, they shared
confining. a c o m m o n i n t e r e s t in r e f i n i n g t h e n o t i o n of c h e m i c a l a f f i n i t y ,
Confining, too, m u s t have been Richards' professed em- a n d i n t h i s c o n n e c t i o n t h e y b o t h r e c o g n i z e d t h e s i g i f i c a n c e of
p i r i c i s m . H e w a s of t h a t g e n e r a t i o n of A m e r i c a n s c i e n t i s t s w h o i n t e g r a t i n g t h e G i b b s - H e l m h o i t z e q u a t i o n (77). T h i r d , t h e r e
identified good science with careful m e a s u r e m e n t s a n d who is n o q u e s t i o n b u t t h a t L e w i s b e n e f i t t e d f r o m h i s w o r k i n t h e
t h o u g h t t h a t t h e o r y s h o u l d flow f r o m p r e c i s e e x p e r i m e n t s . I n l a b o r a t o r y w i t h this m a s t e r of e x p e r i m e n t a l t e c h n i q u e . W h e n
R i c h a r d s ' case, t h e n a t i v e s t r a i n of e m p i r i c i s m w a s reinforced

clear h e a d , a s o u n d k n o w l e d g e of t h e r m o d y n a m i c s , a n d t h e
a b i l i t y t o i d e n t i f y i m p o r t a n t q u e s t i o n s (19).
At s o m e p o i n t during t h e 1890's, Noyes conceived the
a m b i t i o n o f d u p l i c a t i n g a t M I T t h e k i n d of r e s e a r c h s c h o o l
in w h i c h h e h a d w o r k e d a t Leipzig, a n i n s t i t u t e w h e r e , as h e
told a friend, he m i g h t h a v e "associates . . . t o work on
i o n s — o n e for e a c h ion . . . " ( 2 0 ) . I n 1 9 0 3 , after a y e a r of n e -
g o t i a t i o n s w i t h t h e p r e s i d e n t of M I T , N o y e s o b t a i n e d w h a t
he wanted, an institute which he called t h e R e s e a r c h L a b o -
r a t o r y of Physical Chemistry. T h i s w a s t h e site w h e r e Lewis
worked during his years at M I T .
I t w a s a n u n u s u a l e n t i t y . I n t h e first p l a c e , m o r e t h a n h a l f
of i t s o p e r a t i n g b u d g e t c a m e f r o m N o y e s ' o w n p o c k e t a n d f r o m
a g r a n t which he h a d been recently awarded by the new Car-
negie I n s t i t u t i o n of W a s h i n g t o n . M I T s u p p l i e d a s m a l l a n n u a l
subsidy a n d agreed to erect a temporary building to house
N o y e s a n d his associates. S e c o n d , it w a s c r e a t e d as a n a u t o -
Flgure5. A physical chemistry OUlIng in 1917; Irom hit 10 ilylit: Diivki A. Srviilii, n o m o u s d e p a r t m e n t ; a s d i r e c t o r N o y e s r e p o r t e d to t h e p r e s -
Arthur A. Noyes, G. N. Lewis (on running board). [?], Mrs. G. N. Lewis, James i d e n t of M I T r a t h e r t h a n t o t h e h e a d of t h e c h e m i s t r y d e -
£. Bell, [?{. Photo oourlesy of the Archives, California institute of Tech- partment. He had an independent budget and the power to
nology. h i r e a n d f i r e . T h i r d , t h e l a b o r a t o r y w a s i n t e n d e d to b e a r e -
s e a r c h c e n t e r r a t h e r t h a n a s i t e for i n s t r u c t i o n . A h a n d f u l of
doctoral candidates would be admitted, b u t Noyes wished to
Lewis arrived at H a r v a r d , he was an inexperienced novice;
fill m o s t of t h e d o z e n o r s o s p o t s i n t h e f a c i l i t y w i t h c h e m i s t s
w h e n h e left h e w a s a n i n v e n t i v e a n d skillful e x p e r i m e n -
who already possessed P h D ' s . This was perhaps t h e most
talist.
s t r i k i n g f e a t u r e of N o y e s ' s c h e m e ; in effect h e w a s o p e n i n g u p
I n 1 9 0 4 , L e w i s m a d e h i s b r e a k w i t h H a r v a r d in a r a t h e r
a n e w o p t i o n for y o u n g , r e s e a r c h - m i n d e d c h e m i s t s b y c r e a t i n g
d r a m a t i c f a s h i o n b y m o v i n g t o t h e o t h e r s i d e o f t h e g l o b e to
s o m e of t h e first o p p o r t u n i t i e s i n t h i s c o u n t r y f o r p o s t - d o c t o r a l
b e c o m e s u p e r i n t e n d e n t of w e i g h t s a n d m e a s u r e s i n t h e P h i i -
s t u d y . T h e s e post-docs, or research associates as N o y e s called
ippines. In his surviving letters, Lewis makes no reference to
t h e m , would have limited teaching responsibilities; their
h i s m o t i v e s for g o i n g t o t h i s n e w A m e r i c a n c o l o n y , a n d w e c a n
tenure would d e p e n d upon research a c c o m p l i s h m e n t Finally,
o n l y g u e s s a s t o h i s r e a s o n s for a c c e p t i n g t h e p o s t . I t is p e r h a p s
Noyes instituted a research colloquium at the laboratory, a
w o r t h n o t i n g t h a t h e h a d f a i l e d to p u b l i s h a s i n g l e p a p e r
regular staff s e m i n a r at which workers discussed b o t h t h e
d u r i n g t h e two years preceding his d e p a r t u r e from H a r v a r d ,
current literature a n d their work in progress. T h i s too was a n
t h e only e x t e n d e d d r o u g h t in Lewis' career. T h e s e were t h e
i n n o v a t i o n , for a l t h o u g h r e s e a r c h c o l l o q u i a w e r e c o m m o n i n
years in which he was assuming significant teaching respon-
G e r m a n y , t h e y w e r e still q u i t e r a r e in t h e U n i t e d S t a t e s . T h e
s i b i l i t i e s , a n d it is n o t u n r e a s o n a b l e to s u p p o s e t h a t L e w i s
p o s t - d o c a n d t h e staff s e m i n a r w o u l d , of c o u r s e , l a t e r b e c o m e
f o u n d t h e s e c l a s s r o o m d u t i e s t a x i n g a n d w i s h e d t o b e free of
e s s e n t i a l p a r t s of t h e c h e m i s t r y p r o g r a m a t B e r k e l e y ( 2 / ) .
t h e m . I n a n y e v e n t , h e d i d n o t t a r r y l o n g i n M a n i l a , for i n 1 9 0 5
h e a c c e p t e d a n i n v i t a t i o n to j o i n t h e f a c u l t y a t M I T .
Lewis spent seven productive years at M I T . W h e n he ar-
W h e n Lewis arrived at "Boston T e c h " ( M I T then occupied rived, h e h a d already completed his p a p e r s on t h e potential
its original site in B a c k B a y ) h e found w h a t w a s lacking a t o f t h e o x y g e n e l e c t r o d e , a n d in N o y e s h e f o u n d a c h e m i s t w h o
H a r v a r d — a b a n d of t a l e n t e d , y o u n g p h y s i c a l c h e m i s t s w h o was alive to t h e benefits t h a t m i g h t accrue from a s y s t e m a t i c
e x h i b i t e d n o t o n l y t h e f o r m , b u t a l s o t h e s p i r i t of r e s e a r c h . s t u d y o f t h e f r e e e n e r g i e s of f o r m a t i o n of c h e m i c a l s u b s t a n c e s .
A m o n g those working w i t h h i m t h a t first year a t M I T were I n J u n e 1905, several m o n t h s before Lewis' arrival, N o y e s h a d
C h a r l e s A. K r a u s , l a t e r t o b e c o m e p r o f e s s o r o f c h e m i s t r y a t a l r e a d y b e g u n t o d i s c u s s t h e p o s s i b i l i t y of o r g a n i z i n g a c o o p -
B r o w n University, E d w a r d W . W a s h b u r n , w h o went on t o e r a t i v e p r o g r a m of e x p e r i m e n t a l w o r k o n t h e p r o b l e m , i n -
p r o f e s s o r s h i p a t t h e U n i v e r s i t y of Illinois, R i c h a r d C h a c e volving chemists a r o u n d t h e country (22). B u t after Lewis
Tolman, who would work with Lewis again at Berkeley a n d arrived, a n d p e r h a p s with his advice, N o y e s decided t h a t t h e
who e n d e d his distinguished career at Caltech, a n d William e x p e r i m e n t a l w o r k w a s so d e l i c a t e a s t o m a k e a c o o p e r a t i v e
C. Bray, whose future would be linked with Lewis' a t the s c h e m e i m p r a c t i c a b l e . I n s t e a d , L e w i s , w i t h t h e h e l p of s t u -
U n i v e r s i t y of C a l i f o r n i a . K r a u s , w h o h a d j u s t t u r n e d 30, w a s d e n t s a n d colleagues, u n d e r t o o k t h e systematic d e t e r m i n a t i o n
t h e o l d e s t in t h e g r o u p ; e v e r y o n e of t h e s e c h e m i s t s w a s l a t e r of e l e c t r o d e p o t e n t i a l s himself. T h i s w o r k , b e g u n a t M I T a n d
e l e c t e d to m e m b e r s h i p i n t h e N a t i o n a l A c a d e m y . I t w a s a r e - c o n t i n u e d a t t h e U n i v e r s i t y o f C a l i f o r n i a , w a s t h a t p a r t of h i s
m a r k a b l e c o n c e n t r a t i o n of t a l e n t for a n y A m e r i c a n u n i v e r s i t y r e s e a r c h i n w h i c h L e w i s t o o k t h e g r e a t e s t p r i d e . " I t is o n e
of t h a t p e r i o d , a n d i t w a s a l l t h e m o r e r e m a r k a b l e t h a t i t e x - thing," he wrote, " t o learn an experimental m e t h o d and apply
isted a t M I T , a school t h a t h a d n o t y e t a w a r d e d its first P h D it w i t h g r e a t e x a c t n e s s t o all t h e p r o b l e m s w h i c h c o m e t o h a n d ;
{18). it is a n o t h e r t h i n g t o h a v e a definite p r o b l e m w h i c h r e q u i r e s
t h e u s e a n d o f t e n t h e i n v e n t i o n of m a n y d i f f e r e n t m e t h o d s "
T h e i r presence in B a c k B a y w a s d u e largely t o t h e efforts (23). T h i s , of c o u r s e , w a s t h e t a s k h e f a c e d i n d e t e r m i n i n g t h e
of o n e s c i e n t i s t , A r t h u r A m o s N o y e s ( F i g , 5 ) . N o y e s , t h e n e l e c t r o d e p o t e n t i a l s of t h e e l e m e n t s .
a p p r o a c h i n g t h e age of 40, h a d b e e n a m o n g t h e first a n d m o s t
t a l e n t e d of O s t w a l d ' s A m e r i c a n s t u d e n t s . H e h a d o b t a i n e d L e w i s c o n s i d e r e d his w o r k o n free e n e r g i e s of f o r m a t i o n t o
his d o c t o r a t e a t Leipzig in 1890, a n d t h e n h a d r e t u r n e d t o h i s b e p a r t of a larger t a s k of w e a v i n g t o g e t h e r t h e a b s t r a c t
u n d e r g r a d u a t e a l m a mater, M I T , as an instructor. During the e q u a t i o n s of t h e r m o d y n a m i c s a n d t h e c o n c r e t e d a t a of
' n i n e t i e s , N o y e s p e r f o r c e d e d i c a t e d m u c h o f h i s e n e r g y to c h e m i s t r y , a n d d u r i n g h i s y e a r s a t M I T h e m a d e otheT c o n -
undergraduate instruction; young faculty m e m b e r s at the t r i b u t i o n s t o t h i s g o a l , in p a r t i c u l a r , h i s i n v e n t i o n o f t h e u s e f u l
i n s t i t u t e w e r e e x p e c t e d t o s p e n d u p w a r d s of 20 h o u r s a w e e k n o t i o n of a c t i v i t y . B u t t h e r m o d y n a m i c s w a s n o t h i s o n l y
in c o n t a c t w i t h s t u d e n t s . B u t in his free t i m e , often w o r k i n g c o n c e r n d u r i n g this p e r i o d . H e r e a d widely in p h y s i c s as well
with undergraduate assistants, Noyes h a d managed to do an a s i n c h e m i s t r y , a s is c l e a r f r o m h i s p a p e r s o n r e l a t i v i t y (24).
i m p o s i n g a m o u n t of o r i g i n a l r e s e a r c h . H e w a s n o t as skillful H e also a u d i t e d a t least o n e course in organic chemistry. Y e a r s
a n experimentalist as Richards, nor did h e display the creative l a t e r , a f t e r t h e p u b l i c a t i o n of " V a l e n c e , " t h e teacher i n t h a t
i n s t i n c t s o f h i s teachers, O s t w a l d a n d N e r a i s t , b u t h e h a d a course, F . J . M o o r e , w r o t e t o L e w i s a n d c o m p l i m e n t e d h i m on

his concern with, and knowledge of, organic chemistry. "We were together moving toward the conclusion that molecular
seldom expect this," Moore wrote, "from a person BO deep in considerations deserved an important place in their work.
physical chemistry as yourself (25). Hypotheses regarding the fine structure of matteT and the
It is unlikely that Lewis took this course purely for its en- nature of the chemical bond might afford insight into tradi-
tertainment vahie. Any comprehensive theory of valence tional problems in physical chemistry. As Kraus put it in 1907,
would have to take account of the evidence of organic chem- "The study of the conduction process cannot be successfully
istry, and valence was still very much in Lewis' thoughts. Al- carried out until the molecular state of the system has been
though he published nothing on the subject while at MIT, his established, even in the case of electrolytes the progress of
interest muat have been stimulated by his coworkers, who investigation is governed by this condition" {31).
themselves were abuzz with talk of atomic and molecular This observation seems trite today, but at the time it rep-
structure. Thomson's work on the electron was read in semi- resented an important shift in the thinking of physical
nars. The absolute size of the atom, tautomerism, and Wer- chemists. It was a shift away from a specialty defined in terms
ner's coordination theory were discussed at the staff collo- of the study of process toward one in which considerations of
quium (26). Charies A. Kraus spent the years from 1907 to structure and bonding would hold a legitimate place. The shift
1909 studying solutions of metals in liquid ammonia in an occurred in part because physicists, such as J. J. Thomson,
effort to test the theory that free electrons were the carriers were developing chemically interesting models of the atom
of electrical charges in metals (27), And it ia striking how many and, in part, because physical chemists themselves were
of the important papers on valence written during the 'teens finding it increasingly difficult to treat problems, such as those
were by chemists who had worked at this laboratory. K. G. posed by strong electrolytes, using their traditional repertoire
Falk was still on the staff when, in 1910, he collaborated with of concepts and techniques. Talk of bonds was not so much
John M. Nelson on an influential essay that marshalled the twaddle, but serious business.
evidence for an electron transfer theory of valence. One year
after leaving MIT, W. C. Bray together with G. E. K. Branch At the Research Laboratory of Physical Chemistry one sees
developed a dualistic theory of valence, positing two types of classical physical chemistry evolving into the newer physical
bonds, polar and nonpolar. W, C. Arsem, a young physical chemistry of which Lewis would become a leading proponent.
chemist who had gone to General Electric after working With The electrode potentials of the elements were being deter-
Bray at MIT, suggested in 1914 that bonds resulted from the mined with a new degree of accuracy, and the data so gathered
sharing of a single electron. And of course Lewis himself would soon become indispensable to chemists of all sorts. The
published papers both in 1913 and in 1916, the former devel- theory of solutions was being enriched and its field of appli-
oping Bray's dualistic concept and the latter outlining his own cation broadened by the introduction of the concept of ac-
theory of the shared pair bond {28), The variety of these tivity. And not least important, constraints on molecular in-
theories indicates that there was no consensus among the terpretations were being loosened and a new generation of
chemists at Noyes' research laboratory, but their number physical chemists was coming to see the fine structure of .
testifies to the intensity of the discussion underway there matter as an essential subject of study. When Lewis went to
between 1905 and 1912. Berkeley in 1912, he carried with him the benefit of this ex-
perience, His apprenticeship had ended, but the transition
to the new physical chemistry had just begun.
There is something surprising about all of this, for the
proprietor of this Research Laboratory, A. A. Noyes, was a Acknowledgment
physical chemist trained in the classical mode. His research
dealt primarily with the phenomena of dilute aqueous solu- Students of Lewis's work will recognize my debts to Robert
tions and especially the puzzling behavior of solutions of F, Kohler and Erwin N. Hiebert, whose papers, cited above,
strong electrolytes. His basic conceptual tool was thermody- constitute the starting point for any study of I.*wis and his era.
namics, and he shared that reluctance to speak in terms of I thank Jeffrey L. Sturchio, Larry Owens, and Gerald L.
atoms and molecules so common among Ostwald's students. Geison for valuable comments on earlier drafts of this paper,
As late as 1902, he could write a textook on the general prin- and the Archives of the University of California, Cornell
ciples of physical science without once mentioning the electron University, and Harvard University for permission to quote
(29). But Noyes never went so far as his teacher, who denied from letters in their possession. I also acknowledge the gen-
the existence of atoms altogether, and as physical evidence erous support of the National Science Foundation and of the
for atomism mounted after 1902, Noyes dropped many of his American Council of Learned Societies.
inhibitions. By 1907, when he published the results of his
five-year investigation of the electrical conductivity of aqueous Literature Cited
solutions, Noyes had reached the point where he could suggest (1) G, N. Lewis io Eugene 0. Bingha in, 21 Feb. 1922, copy in 1921.1922 Bo*, Wilder D.
that the discrepencies between the behavior of strong and Bancroft Papers, Cornell University Archives,
(Z) When Lewis accepted a posil ion at the University of California he insisted that lilies
weak electrolytes might well be owing to differences in their such as "Professor of Physical Chemiatry' be aboliohed so that there should he the
modes of combination. Ions, he stated, might unite in two greatest possible mobility in Ihe- department. See, G. N. l^v/h (o Benjamin Ihde
ways. They might combine to form electrical molecules in Wheeler, 5 Jan. 1912, CD-S, Bos 61, Archives of ihe University of California,
Berkeley.
which the constituents retained their electric charges and {3! OlUheorijiJ[isof physicai chemistry, see Root-Bernmein, Robert ScolE. "The lonisis:
characteristic properties, or they might combine in a more Founding Physical Chemistry," Pli.D, dissertation, Princeton University, 1980.
intimate fashion to form chemical molecules in which the (4) Ostsvalrt, Wilhelni, "Die Aufgaben der physikalischen Cheinie," Humboldt, Mon-
constituents lost their identities. Strong electrolytes tended attaehtift /. d.geaamlim Natuniaseiaekaften, 6,249 (1881), on p. 252.
to form electrical molecules; weak electrolytes tended to form (5) See, for example, Loei>, Morris. "The Fimdamoniai ideas of Physical Chemistry," in
"The Scientific Work of Morris Loeb,™ {Edilar: Richards, T. W.J, Harvard University
chemical molecules. Whereas chemical molecules dissociated Press, Cambridge, MA, 1913, p. 5, Loeb was the first of Ostivaid's American studenta
in solution in accordance with the law of mass action, electrical to return to the Unjjed Slates,
(6) W(ilfendiin,JohnH.,TheAi!oi™iyofaironj|Electrolylps,"Anibiil9,175 (1973),and
molecules obeyed an entirely distinct principle whose theo- Dulby, R. G,, "Dtbates Over the Theory of Solution." Hitioncal Studies in the
retical basis was not understood (30). Noyes' molecular in- Physical Sdences,7,2ff? {Idm
terpretation of his evidence wag a significant departure from (7) See Hiebert, Erwin N,, "The Energetics Conlroversy and the New Thermodynamics,"
the tradition in which he had been trained, but it was of a piece in "Perspectives in the History of Science and Technology." {Editor: Roiter, Ooane
H. D.|, University of Oklahoma Press, Norman, OK, 1971, pp. 67-86, and Clark, Peter.
with much of the other work underway in his laboratory, "Atomism versus Thermodynamics," rn "Method and Appraisal in the Physical
Sciences: The Critira) Background !i, Modem Science, 1S0Q-1905," {Editor: Hmraon,
Colin), Cambridge University Press, Cambridge. England. 197S, pp. 41-105.
Our sources do not permit conclusions to be drawn re- (Si On Lewis' career, see Calvin, Melvin, "Gilbert Newton Lewis," in "Proceedings of the
garding the question of who was influencing whom at MIT, Robert A, Welch Foundation Conferences on Chemical Research, XX, American
Chemistry—Bicentennial," {Ediw. Milligan, W. O,), Houston, 1977, pp. 116-150;
but this question is perhaps less important than the fact that Hildebrand, Joel Henry, "Gilbert Newton heviis" Natitwal Academy of Sciences,
here a group of physical chemists trained in the classical mode Hitigraphiail Memoirs, 31, 210 (1958); and Lacbman, Arthur, '• Borderlands of the

Unknown: The Life Story of Giltart Newton Lewis," Pageant PTKSB, New York. Chemistry in America, 1890-1933," Ph.D. dissertation, The Johns Hopkins Uni-
3S55. versity, 1979, chapter 3.
(9) On Richards, see Kupneri, Sheldon J., "The Scientific Work of Theodore William (22) A. A. Noyee to George Ellery Hale, 5 June 1906, Holi 27, microfilm edition of the Gauge
Richards," Ph.D. dissertation, University of Wisconsin, 197% Conani,. James B.r Ellery Hale Papers (Edittn-. Daniel J. Keries). See aleo "Report, of The National
"Theodure William Richards," NQtir/rwl Acadentv of Sciences, Biographical Academy of Sciences for the Year 1906, Government Printing Office, Washington,
Memoirs, 44, 251 (1974); ami Hartley, Mil Harold, "Thendore William Richardu," D.C., 1907,pp. 19-20.
Journal of the Chemical Society, 138,1937 (1930). (23) G. N. Lewis to J. R. ParUngtofl, 7 Dee. 1928, Bos 3, Coilege of Chemistry Records, Ar-
(10! Harvard University, "President's Report," 1885-1896. p. 71. chives of the University of California.
(11) T. W. Richards to Julius Stiegliiz, 17 Nov. 1916, Professional and Persona! Corre- (24) 13. H. Lewis, "A Revision of the Fundamental Lews of Metier and Snergy,"iûi. Waff,
spondence, I91G BE™, T. W. Richards Papers. Harvard University Archives. 16,70S (1908); toww, R. N., and Tohnan, H. C, "The Principle of Relativity and
(12) See, for example, Richards, T, W., "The Possible Significance of Changing Atwuk Non-Newionian Mechanics," Prix. Anier. Atori.,44,711, (1909); Lewis, G, N., and
Volume," Proceedings a/ the American Academy of Arts and Sciences,Wilson, H7,1 R B.. "The Spacs-Tinie Manifold of Balativity," Prix. Amsr. Acad., 48,389
onpu.Sand 16-16. (1912).
(13) T, W. Richards tu Wilhelm Palmaef, 13 Jan, 1914, Professional and Personal Corre- (25) F. J. Moore to G. N. Ijewis, 6 Dec. 1923, Boi 3, College of Chemistry Records, Archives
spondence, 1602-1914 Box, T. W. Ridiariia Papers. of the University of California, Berkeley.
(14) Richards, T. W., Chemistry a Notebook, Harvard University Archives, quoted by (2S) "General Inslituls News—Research Labotstory of Physical Chemistry," Teth. Rev.,
Kopperi in "The Scientific Work of Theodore William Richards," p. 226. iO, (
(15) K(diler,Robet[F.,Jr.r"TheOriBinofC.N.I,ewie'sThswyoftheSharfldPairBonii," (27) Krau
Historical Studies in the Physical Sciences, 3,343 (1971). 1373 (1908).
(16) G. N. Lewis to Robert A. Miilikan. 38 Oct. 1919, Box 3, College of Chemistry Records,(28) Falk, K.G., and Nelson, J.M.,J.Amsr.Ch<:m. Sue., Z2,1837 (1910)iB«si,W.C. and
Llnive/aity of California, quoted by Kohler in "The Origin of Lewis's Theory," ppL Branch, G. E. K, J. Amer. Chern. Sot:, 36,1655 (1914); Lewie,G. N., J. Amer. Cnem.
351-352. Sue., 35,1448 (1913); and LewiB, G. N.. J- Amer. Chen. Soc. 38,762 (1916). Robert
(17) Biwin N. Hiebert diaciiaea the nork of Lewis and Richards on this problem in his sketch Kohkr discusses all of these papers in "The Origin of Lewis's Theory."
of Walther Nemat in the "Dictionary of Scientific Biography," Supplement L (29) Noyes, ArShur Amos, "The Genetai Principles of Physical Science. An Introduction
US) On MIT, BG?i Servos, John W.h "The Industrial Relations of Science; Chemical Enf>i- to the Study of Ihe General principles a! Chemistry," Henry Holt, New Yof k, 1902.
neerin«at MIT, 1900-1939," Isis, 71,531 (1980). Linua Pauling made this observation Li his essay on Noyes in "Proceedings of the
(19) On Noyos, see Pauling, Linus, "Arthyir AtEosNvyes," National Academy of Sciences, Robert A. Welch Foundation Conferences on ChamicHl Research. XX. American
Biographical Memoirs, 81 32? (195S). and Servoa, John W,, "The Knowledge Cot. Chemislry—Bicentennial," {Editor: Milligan, W. O.), Houston, ISJT, pp. 80-91.
poration: Chemistry at Caltech, l&lfl-1930," Ambit, 23,178 (1976). (30) Noyes, Arthur A., etal., 'HThe Electrical Conductivity of Aqueous Solutions," Carnegie
(21) A. A. Nnyestn H.M.Goodwin, IS Jan. 1891, H.M.Goodwin Papers, MIT Archives, Institution of Washington, WashinsUin, DC, 1907, pp. 851-362.
quoted by Wiae. George, "lonists in Indtsliy: Physical Chemislry al General Electtk, (31) Kraus, Charles A., "Solutions of Metals in Non-Metallic Solvents; L General Properties
1900-191S," his, !4, 7 (1983), on p. 11. of Solutions of Metals in Liquid Ammonia," J. Amer. Chem. Sot:-, 29,1553 (19117).
(20) On the Research Laboratory of Physical Chemistry, see Servos. John W., "Physical
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10 Journal of Chemical Education

The College of Chemistry
in the G. N. Lewis Era: 1912-1946
Melvin Calvin and Glenn T, Seaborg
Department of Chemistry and Lawrence Berkeley Laboratory,
University of California, Berkeley, CA 94720
Gilbert K. Lewis of the Massachusetts Institute of Tech- The accompanying photographs are notable in that they
nology accepted the position of Dean of the ColSege of are among the very few substantial ones of the College of
Chemistry and moved to Berkeley in the Fall of 1912. When Chemistry faculty, including Lewis, that have survived from
Lewis arrived the chemistry faculty already had four mem- the G. N. Lewis era. Soon after the Chemistry Annex was
bers: Edward Booth who served until he died in 1917, Edmund completed in 1915, a number of people moved there from the
O'Neill who retired in 1925, Walter C. Blasdale who retired larger old building which had been completed in 1890. The
in 1940, and Henry C. Biddle who left Berkeley in 1916. From first photograph (Pig. 1) was taken in front of the Chemistry
MIT Lewis brought with him William C. Bray, Merle Randall, Annex on 14 May 1917. It shows Lewis and his graduate stu-
and Richard C. Tolman, together with several graduate students William L. Argo (at this time an instructor); Axel R.
dents. Bray and Randall were to stay at Berkeley but Tolman Olson; Thomas B. Brighton; Parry Borgstrom; Asa L.
left in 1916. George Ernest Gibson from England and Ger- Caulkins; Orville E. Cushman; Guy W. Clark; and George S.
many and Joel H. Hildebrand from the University of Penn- Parks; Randall and his graduate student, Charles S. Bisson;
sylvania joined the faculty in 1913. These proved to be the last Bray; Constance Gray, secretary to Lewis; William J.
non-Berkeley PhD's appointed to the faculty until Calvin's Cummings, glassblower; and Svend Holmstrup, shopman.
appointment in 1937 (see table). Of the permanent chemistry
The second picture (Fig. 2) was taken in front of Gilman
faculty from 1912 to the present we have known all but Booth,
Hall in the fall of 1917, at about the time this building was
O'Neill, and Biddle.
completed. This photograph includes faculty members
n
Figure 1 . Picture t a k e n o n May 14, 9 l # T'.fi •_•' ( " h - r o "i> A M e * .
Back row (teft to right)

William C. Bray, William L. Argo. Gilbert N. Lewis, Constance Gray, Parry Borgslrorn, George S. Parks, Merle Randall, Charles S, Bisson, Asa L Caulkins, Svend
Hoimstrup (shopman), William J. Cummings (glassblower).
Front row {seated left to right)

Axel R. Ofson, Tiiomas B. Brighton, Orviiie E. Cushman, Guy W. Clark.
Volume 61 Number 1 January 1984 11

Eastman, Blasdale, Bray, Randall, Gibson, Porter, Stewart, (wife of Gerald Branch), Charles S. Bisson, Wendell M. Lat-
O'Neill, Argo, and Lewis (Branch was away in the Canadian imer, Charles C. Scalione, Roy F. Newton, William G. Horsch,
Armed Services while Hildebrand was apparently out of William H, Hampton, John M. McGee, George S. Parks, Parry
town); Lewis' secretary, Constance Gray, and clerk M. J. Borgstrom, Albert G. Loomis, Angier H. Foster, and Axel R.
Fisher; graduate students Esther Kittredge, Esther Branch Olson; undergraduate students Carl Idrjings, William D.
University of California, Berkeley—Chemistry Faculty
Year Degree Year Degree
Joined Name Dale Where Taken/With Whom Joined Name Date Where Taken/With Whom
Faculty on hand at time Gilbert N. Lewis arrived in Berkeley 1921 Olson, Axel R. 1918 UC Berkeley, Lewis
Booth, Edward 1877 DC Berkeley Hogness. Thorftn R. 1921 UC Berkeley, Hildebrand
O'Neill, Edmonfl 1S79 UC Berkeley
Biasdale, Walter C, 1892 UC Berkeley 1922 Giauque, William F. 1922 UC Berkeley, Gibson
Bfddie, Henry C. 1900 University of Chicago (Nobel Prize, 1949}
1912 Lewis, Gilbert Newton 1B99 Harvard, T. W, Richards
Tolman, Richard C. 1910 MIT 1923 Roflefson, Gerhard K. 1923 UC Berkeley, Lewis
Bray, William C. 1905 Leipzig, Luther
Randall, Merle 1912 MIT, G. N. Lewis 1933 Littby, Willard F. 1933 UC Berkeley, Latimer
(Nobel Prize, 1960)
1313 Hildebrand, Joel C. 1906 Pennsylvania, Edgar Fahs
Smith 1937 Pitzer. Kenneth S. 1937 UC Berkeley, Latimer
Gibson, G. Ernest 1911 Breslau, Lummer Catvin, Mefvin 1935 Minnesota, Glockler (UC
1915 Branch, Gerafd E. K. 1915 UC Berkeley. Lewis (Nobel Prize, 19611 Berkeley. 19S3, Gibson)
Argo. Wilflam C. 1915 UC Berkeley, Lewis
1917 Porter, C. Walter 1915 UC Berkeley. Biddle 1938 Ruben, Samuel C. 1938 UC Berkeley, Latimer/
Eastman, Ermon D. 1917 UC Berkeley, Lewis Llbby
Latimer, Wendell M. 1917 UC Berkeley, Gibson
Stewart, T. Dale 1916 UC Berkeley, Tolman 1939 Seaborg, Glenn T. 1937 UC Berkeley, Gibson
(Nobel Pftee, 1951)
Figure 2, University of Californ.j Cer.tse o" Chorv.s'ry Si^'l ».* »i'-'. '•_ i ' l " ) • " at NRA > C M s'rJCIC QITI-." i.s r-i •<>' "91 ?).
Front rowt,right to left)
Ermon D. Eastman, Walter C. Biasdale, William C. Bray, Merle Randafl, G. Ernest Gibson, C. Walter Porter, T. Dale Stewart, Edmund O'Neilf, William L. Argo, Gilbert
N. Lewis, Constance Gray, Esther Kittredge, Esther Branch, and M. J. Fisher, (bookkeeper).
Ascending Stairs (left to right)
Charles S. Bisson, Wendell M. Latimer, WilSiem J, Cummings (glassblower), Carl iddings, Reginald B. Rule. J. T. Rattray (woodworker), Charles C. Scalione. Hal
D. Draper, Wifliam O. Horsch, William H. Hampton, Wlflard G. Baboock, John M. McGee, George S. Parks, Parry Borgstrom, Albert G. Loomis, George A. Llnhart,
William D. Ramage, and Harry N. Cooper.
Seated {left to right)
Alex R. Olson and Angier H. Foster.

Figures. University of California College of Chemistry Staff Members In fronf of the north end of GHman Hall, November 1920.
From left to right, seated, first row

Philip S. Danner, H. W. Chapman, James T. Rattray, Hal D, Draper, Nelson W. Taytor, TheophJI F. Buehrer, Allyn M. Shaffer, fioscoe H. Gerke, Francis R Bichowsky,
Reynold C. Fuson, T, Fraser Young, Thomas E. Phipps, and Roy M. Bauer.
Seated, second row

George F. Netson, Wendell M Lattmer, Gerald E, K. Branch, T. Dale Stewart, WNSlam C. Bray, Edmund O'Neill, Gilbert N. Lewis, Merte Randall, Joel H. Hildebrand,
Walter C. Blasdale, and Ermon D. Eastman.
Standing, third row

Eustace J. Cuy, Robert M. Evans, Wiltiam M. Hoskins, Roy F. Newton, Atbert P. Vanselow, MaybeHo J. Fisher, Constance Gray, Edna R. Bishop, Anna L. Elliott,
Clarence A. Jenks, and Gustav E. Ostrom.
Standing, fourth row

Wiiliam J. Cummings, John A. Afmqulst, Busselt W. Millar, W. Albert Noyes, Jr., Albert M. Williams, Maurice L Hugging, Evaid Anderson, Dwight C. Bardwetl, Harry
K, ffsrig, Bruner M. Burchfiei, William F. Giautjue, Sherwin Maesar, Karl R. Edlund, Thorfln R. Bogness. James B. Ramsey, and Manuel L. Zavala.
R a m a g e , W i l i a r d G, B a b c o c k , a n d R e g i n a l d B . R u l e ; a s s i s t a n t Blasdale, a n d E a s t m a n (Gibson, Olson, a n d Porter are miss-

G e o r g e A. L i n h a r t ; g i a s s b l o w e r W i l l i a m J . C u m m i n g s a n d ing). Also i n c l u d e d are C o n s t a n c e G r a y (secretary t o Lewis),
woodworker James T. Rattray and curator Harry N, M . J. Fisher (secretary to O'Neill), R a t t r a y (woodworker),
Cooper. C u m m i n g s (glassblower), H. W. C h a p m a n (machinist),
T h e t h i r d p i c t u r e {Fig. 3) w a s t a k e n o u t s i d e G i l m a n H a l l p o s t d o c t o r a l fellows F r a n c i s R. B i e h o w s k y a n d W . A l b e r t
i n N o v e m b e r , 1 9 2 0 . S e a t e d in t h e s e c o n d r o w front a r e G e o r g e N o y e s , Jr., a n d R o y F . N e w t o n ( i n s t r u c t o r ) . All t h e o t h e r s a r e
F. N e l s o n (chief m a c h i n i s t ) , a n d faculty m e m b e r s L a t i m e r , graduate students and are identified in t h e caption.
B r a n c h , Stewart, Bray, O'Neill, Lewis, Randall, H i l d e b r a n d ,

Gilbert Newton Lewis
His Influence on Physical-Organic Chemists at Berkeley
Melvin Calvin
Department of Chemistry and Lawrence Berkeley Laboratory,
University of California, Berkeley, CA 94720
My task is to describe the influence of G. N. Lewis on my definition by B r a y and B r a n c h in 1913, which w a s confirmed
own research and to indicate how Lewis (Fig. 1) influenced b y L e w i s w h o r e l a t e d t h e t e r m " p o l a r n u m b e r " to t h e e l e c t r o n s
physical-organic chemistry research at Berkeley during the t a k e n a w a y o r g i v e n to a n a t o m , w a s a " b r e a k t h r o u g h " w h i c h
period 1912-46.1 was the last of the non-Berkeley-graduate led Lewis t o t h e idea t h a t t h e w a y in w h i c h a t o m s were actually
faculty members whom Lewis brought to the Berkeley campus h e l d t o g e t h e r w a s b y v i r t u e of t h e e l e c t r o n s b e t w e e n t h e m . Of
and the first one in 22 years. The first of Lewis' Berkeley ap- course, it was recognized t h a t there were extreme cases in
which t h e electrons were transferred completely from one
pointees was Gerald E. K. Branch who played a central role
a t o m to another, a s in lithium chloride. T h e r e were also other
in the subject I am to discuss. "Jerry" Branch took his first
cases in w h i c h e l e c t r o n s w e r e s h a r e d b e t w e e n t w o a t o m s , t o
degree in 1911 in Liverpool, England. He came to Berkeley in
fulfill t h e o r b i t a l r e q u i r e m e n t s o f b o t h a t o m s b e t w e e n w h i c h
1912 on the advice of his professor, P. G. Donnan. Clearly, by t h o s e e l e c t r o n s lay, giving rise t o t h e c o n c e p t of t h e shared
that time, Lewis' reputation had already reached Europe. electron pair bond. T h e s e t w o p a p e r s u n i f i e d t h e i d e a s o n
Branch took hia PhD with Lewis in 1915 on "The Free Energy b o n d i n g of i n o r g a n i c c h e m i s t r y ( l i t h i u m c h l o r i d e ) a n d t h o s e
of Formic Acid". of organic chemistry (methane).
Lewis' Electron Pair Bond Concept Initiates Theoretical
Organic Chemistry at Berkeley The Shared Electron Pair Bond
In 1913, whiie a graduate student of only one year's stand- In the early days probably the most important concept that
ing, Gerald Branch published a paper in the Journal of the Lewis developed was that of the shared electron pair bond,
American Chemical Society with William C, Bray entitled which eventually gave rise to some coherence in the theory of
"Valence and Tauiomerism" (2). The authors acknowledge organic chemistry. I would like to quote from Robert Kohler
discussions with Lewis, and their paper is immediately fol- (3) concerning the significance of that particular develop-
lowed by one written by Lewis himself which carries the same ment
title and was submitted on the same day (2). At that time the
term "valence" was used without sign—it was simply a The first satisfactory picture of the chemical bond was proposed
number. Bray and Branch introduced the terms maximum in early 1916 by Gilbert Newton Lewis. His book, Valence and
the Structure of Atoms and Molecules published in 1923 \(4)],
valence number (with sign) and maximum coordination which elaborated the picture of the bond and its shared pair of
number. In his follow-up paper Lewis pointed out that the electrons, was the textbook of the new generation of organic
qualifier "maximum" was inappropriate. Those two terms chemists. Without Lewis' conception of the shared pair bond tie
ultimately evolved into "oxidation number," as later defined interpretation of reaction mechanisms already begun by the Brit-
by Wendell Latimer, and "coordination number." The oxi- ish school of Lapworth, Lowry, ingold and Robinson, would not
dation number was defined as the number of electrons re- have gotten very far. The shared electron pair concept was really
moved from (or added to) the atom in the particular com- the foundation of physical-organic chemistry. Likewise, without
pound, and this number had either a plus or minus sign at- the idea of the shared pair bond, then being used with, increasing
tached to i t The coordination number was defined simply as competence and success by organic chemists, the application of
quantum mechanics to the chemical bond in the late I920's by
an integer, the tola! number of atoms or groups bound to a London, Schroedinger and Pauling, would have begun on far Jess
center. The introduction of these two terms and their precise certain grounds.
At that time most organic chemists were trying to do

mechanistic studies using a line to represent a bond, which,
while perfectly adequate for structural chemistry, was not at
all adequate when discussions of chemical change were at-
tempted. The English chemists (Lapworth, Ixiwry, Ingold, and
Robinson) were beginning to wrestle with organic reaction
mechanisms, and the first theoretical organic chemist in the
United States (actually an Englishman!) to try to do the same
was Gerald Branch at Berkeley. In this connection, I'd like to
read from a letter from Col. A. H. Foster, Air Force (Ret.) who
was a student in the College of Chemistry from 1913-17. In
my correspondence with Col, Foster some years ago, he listed
the faculty he knew here in Berkeley. He talked about Lewis,
O'Neill, Tolman, Blasdale, Hildebrand, Randall, and then he
came down to "Jerry" Branch, "whose status I never under-
stood, although he and his lovely wife were both evident in the
laboratories. Dr. Branch had one of the quickest minds of any
person I ever knew, and I have often wondered what he made
of his life".
Professor Branch wrote an essay on Gilbert Lewis in 1951
and presented it at the History of Science Dinner Club in
Berkeley in 1953 (for text of this essay, see Appendix). I'd like
Figure 1. Gilbert N. Lewis, 1912.
to quote from that document, because it shows how close

Branch and Lewis were, and how conscious they were of the One last excerpt is given to illustrate Lewis' way of de-
transition that chemistry was undergoing under the influence scribing this and to show you he really understood what
of the electron pair bond mesomerism, or resonance hybrids, were, He was trying to
draw the structure of ethylene (7).
Lewis became interested in the nature of the atom very early in
his career. His notebook of 1902 contains the first formulation of Now if we have two formulae such as (b> and (c) which differ only
his theory, but he published nothing in this field until his interest in their electronic arrangement and are of the same spectral
was revived by the publication of a short article on the nature of type,
bonds by W. C. Bray and the author (G. E. K. Branch) in 1913.
This was followed almost immediately by a publication on the H H H H H H
same subject by Lewis, and the revival of hia ideas of !902, which
Were thrown to that den of lions, tie research conference. The H:C:C:H H : C: : C: H II : C : C : H
theory was not published until three years afterwards [in 1916,
under the title of The Atom and the Molecule (5)]. <a> (b) <c)
[he means multiplicity, he recognised the difference between
Another essay (6) many years later, also confirmed the long- these two and (a>j and same gauge [Lewis had used the image of
term interest of Lewis in the nature of the atom. electrons running on tracks) then these two formulae (b) and (c)
cannot be regarded as two possible separate states of the mole-
The reference to the research conference by Branch was cule. They must rather be regarded as two different representa-
very significant. It was the way Lewis tried out his ideas. The tions of a single structural state, which ordinarily has lower ener-
research conference, when I came to Berkeley in 1937, was gy than would be predicted if we should assume that there are
held on Thursday afternoons. Lewis would either try out hia two separate states and that some of the molecules are in one
own ideas, or look around at the faculty members and grad- state and some in tbe other.
uate students and ask "What are you doing?", and that was This is the phenomenon which has been called by Ingold the
the start of the discussion. This was where the research ideas T-effect and which has been studied recently by Pauling under
of the faculty and students were honed, and where the in- the name of resonance. We must not think that this phenomenon
consistencies of the theories were thrashed out (6). This in- is due to the fact that we can write two or more different formulae
terpiay of ideas was the reason why Bray and Branch could to represent the same structure, but rather we must think that we
write an article {1) defining the oxidation number and coor- can write two or more formulae because there has been a consid-
dination number and have it followed immediately in the same erable loosening, without fracture, of the skeletal structure, so
tiiat within the skeletal structure there is far more freedom from
issue by an article by Gilbert Lewis on the same subject (2). the effects of quantum restrictions than in a saturated molecuie
The research conference had been the arena, so to speak, to such as ethane.
clear up any arguments which might have existed, and by the
time the papers were published, the various inconsistencies Color of Substances
had been overcome.
It turns out that Lewis arrived at his concept of the color
The two 1913 papers, for example, gave rise to the possi- of substances by constantly asking the same rather obvious
bilities of describing the mechanistic way in which atoms questions from 1902 to 1933. He asks, for example, why is a
change their bonds. The whole basis for theoretical organic substance colored, what causes the color? And the attempt
chemistry was laid during those years when Branch and to answer the question of why a substance is colored gave rise
Lewis were working so closely together. to the concept of the loose electron, and what we now call
polarizabiHty. Lewis recognized that those molecules which
Tautomerism bad deep color, such as dyestuffs, had many loose electrons,
and these electrons can be distributed over a rather large
In the 3 918 paper by Lewis on "The Atom and the Mole- skeleton of atoms. T h a t idea gave rise to his notion of what he
cule" he used the terms valence and tautomerism in a special called tautomerism, but what we now recognize as mesomer-
way. In order for you to understand the importance, I'd like ism OT resonance. Those two things taken together—questions
to quote directly from the paper (5). This shows how far Lewis about the color of molecules, questions of polarity of moleculeB
had gone in his thinking about how to describe the electron versus nonpolarity (sodium chloride versus ethane, for ex-
distribution in the molecule. ample) seem like rather sroail questions. Lewis, however, was
able to put them into the context of the larger question of all
I wish to emphasize once more the meaning that must be ascribed of chemistry.
to the term tautomerism. In the simplest case where we deal with
a single tautomeric change we speak of the two tautomers and The ability to do this was the heart of Lewis' genius and was
sometimes write definite formulae to express the two. But we something which most people could not do, then or now, Most
must not assume that all of the molecules of the substance pos-
sess either one structure or the other, but rather that these forms people can ask a small question and answer a small question,
represent the two limiting types, and that the individual mole- but they are not abie to ask a small question and from that
cules range all the way from one limit to the other. In certain answer derive a larger idea. When Lewis asks a question, he
cases, where the majority of molecules lie very near to one limit or asks a question that has some depth to it and that has rele-
to the other, it is very convenient and desirable to attempt to ex- vance to the entire structure of chemistry and of science. For
press the percentage of the molecules belonging to the one or to example, when Lewis asked the question about color he got
the other tautomeric form; but in a case where the majority of into the subject of the nature of light, which has many other
moEecuies iie in the intermediate range and relatively few in tie permutations. Lewis did not limit the scope of his thoughts
immediate neighborhood of the two limiting forms, such a calcu- to the particular question, but he always had in the back of his
lation loses most of its significance.
mind the relevance of the question to science.
What Lewis is describing here is what Branch, following In- I made my first contact with Gilbert Lewis when I arrived,
gold, later called "mesomerism" and what Pauling was to call in Berkeley in 1937, and I was not then aware of the things that
"resonance." we have been discussing here about Lewis and his work. Since
In the 1933 paper (7) Lewis uses the term tautomerism I was the first non-Berkeley faculty member since 1913, Lewis
where we would use mesomec or resonance hybrid. The En- naturally had a little bit of uncertainty about me, and only in
glish school of Lowry, Lapworth, Ingold, and Robinson, the retrospect am I able to see what he did. (Incidentally, it was
school from which Branch came, was developing a whole Joel Hildebrand who was responsible for my coming to
theory of electron reaction mechanisms. Their terms-— Berkeley. We had met in the laboratory of Michael Polanyi
mesomeric effects, electron* eric effects, polar effects—con- at the University of Manchester, England, where I was a
stituted the language of physical organic chemistry in the postdoctoral fellow working on porphyrin chemistry. Hiide-
middle 1930's. brand discussed with me the possibility of coming to Berkeley,

electronic energy into vibrational-rotational modes (energy
loss as heat). If such is the case, it should be possible to reduce
that energy loss by freezing the molecule in a rigid medium
so it cannot rotate and vibrate. Then it would have to emit
light.
We made up a mixture of ether-pentane-alcohol, which
could be frozen in liquid nitrogen to give a glass. If the dye-
stuffs are dissolved in this mixture and frozen in liquid air,
they all fluoresce. In fact, some of them phosphoresce, that
is, they emit light long after the exciting light is turned off.
Lewis wanted to know the reason for that and also wanted to
know the reason for the color change of the emitted light.
When the emission lasted for a long time, it was of a different
color from when it lasted a short time. In other words, the
phosphorescence and fluorescence were different colors;
usually the phosphorescence had a redder color.
Lewis did not really know much quantum theory (he did not
really want to know very much), but he did know one selection
rule, i.e., you cannot have a radiation transition between two
states of different momentum. It is necessary to provide for
Figure 2. Gilbert N. Lewis, circa 1940.
the change in angle of momentum. !f you have an excited state
that has two electrons each with spin (by that time, spin had
been discovered, even though Lewis had only postulated it in
and when he returned to Berkeley he "convinced" Gilbert 1916), Lewis thought that perhaps the excited state that
L e w i s t o h i r e m e . ) L e w i s ( s h o w n in his G i l m a n H a l l Office, normally fluoresces had a way to get into another kind of ex-
F i g u r e 2) w a s l o o k i n g for a c o m m o n i n t e r e s t b e t w e e n u s , t o s e e cited state, by thermal degradation, in which the two electrons
if h e c o u l d g e t m e c l o s e r t o h t m a n d h i s r e s e a r c h , t o f i n d o u t are parallel instead of antiparallel as they normally are. This
whether I could stay at Berkeley or not. H e found a way means the spin angular momentum will be different in the two
t h r o u g h his favorite subject, n a m e l y , w h y a r e m o l e c u l e s col- states. The only way for the excited electron to get back down
o r e d , t h e q u e s t i o n h e h a d repeatedly a s k e d f r o m 1 9 0 2 t o 1 9 3 3 . again is by vibrational interaction, which would allow the net
A l m o s t e v e r y o n e of h i s p a p e r s w h i c h w e r e c o n c e r n e d w i t h momentum to return to zero; without this occurring it would
v a l e n c e a n d s t r u c t u r e of m o l e c u l e s h a d a little s e c t i o n in it o n have to wait in the new excited state for a long time. This is
t h e c o l o r of o r g a n i c m o l e c u l e s . the prohibition of the singlet-triplet transition. Lewis sur-
mised that the long-lived state is a triplet state, which is the
W e b e g a n w i t h t h a t — " l e t ' s w r i t e a p a p e r o n t h e c o l o r of reason it lasted so long.
organic s u b s t a n c e s , " h e said. In o r d e r t o d o t h a t , we h a d t o
r e v i e w t h e s u b j e c t of c o l o r , w h i c h m e a n t f i n d i n g o u t w h a t t h e Magnetism and color were his two "bugs." In all his papers,
s t a t u s o f t h e k n o w l e d g e o f t h i s field w a s a t t h e t i m e ( 1 9 3 7 ) . W e Lewis always asks about the color and then asks what are the
laid o u t i n t h e s e m i n a r r o o m in G i l m a n H a l l all t h e r e f e r e n c e s magnetic consequences of the color. This led Lewis to feel, for
t o t h e color of o r g a n i c s u b s t a n c e s w h i c h w e r e a v a i l a b l e . T h e example, that ethylene was less diamagnetic than it should
best reference was the large dyestuff c o m p e n d i u m , the dye be (or a little more paramagnetic than it should be) because
index, w h i c h listed t h o u s a n d s of dyestuffs m a d e t h r o u g h o u t of the mobility of the electrons. He used Pascal's magnetism
t h e w o r l d . I t c o n t a i n e d p a r a g r a p h s o n t h e p r o p e r t i e s of t h e constants to confirm theoretical notions that he had evolved
various dyestuffs. Lewis read t h e references, which took sev- when he asked the question concerning color. The same ideas
e r a l m o n t h s . It w a s a l s o n e c e s s a r y t o h a v e t h e s t r u c t u r a l for- were recurring in 1938, 20 years after he had first proposed
m u l a s . T h i s s e a r c h i n g a n d l i t e r a t u r e e x a m i n a t i o n w e n t o n for them. If the material is a triplet it has to be magnetic since the
m o n t h s , perhaps a year. Lewis e x a m i n e d the material a n d electrons are unpaired. If this is true, then the molecule should
a b s o r b e d it a n d t h e n , in h i s u s u a l c h a r a c t e r i s t i c fashion, felt be paramagnetic and it should be possible to confirm it. This
it was t i m e t o write. ( O t h e r p e o p l e in t h e p r o g r a m t o d a y h a v e led to an elegant experiment which has been described in
h a d e x p e r i e n c e s of w r i t i n g w i t h L e w i s — S e a b o r g , K a s h a , B i - detail elsewhere (6). After Lewis was satisfied that the results
g e l e i s e n — a n d t h e y c a n c o n f i r m t h e m e t h o d I will d e s c r i b e t o were correct, the paper on the paramagnetism of the phos-
you.) Lewis w o u l d walk a r o u n d t h e t a b l e in t h e s e m i n a r r o o m phorescent state was published (9). Lewis had satisfied him-
a n d dictate, and I would write. It went quite smoothly and self once more that this "outlander" from the Midwest who
very, very nicely. Lewis d i c t a t e d very carefully, a n d little re- had come to Berkeley was satisfactory.
vision was necessary. O n e t i m e he spoke his sentence a n d I
didn't write anything. Lewis !ooked over m y shoulder to see
Gerald Branch and Organic Chemistry at Berkeley
w h a t h a p p e n e d , a n d it w a s a l r e a d y w r i t t e n d o w n ! T h a t w a s n 't
difficult, b e c a u s e we h a d discussed t h e subject so m u c h , a n d At that stage (about 1939), Lewis gave me the clear im-
I had heard t h a t s e n t e n c e before. W h e n t h e p a p e r on " T h e pression that I should work with Gerald Branch (Fig. 3) and
C o l o r of O r g a n i c S u b s t a n c e s " (8) w a s f i n i s h e d , it w a s p u b - collaborate with him in the preparation of a book on theo-
lished in Chemical Reviews in 1939. Lewis h a d d e c i d e d by t h a t retical organic chemistry. Lewis told me that Jerry Branch had
t i m e t h a t 1 c o u l d stay in B e r k e l e y . it all in his head, but he couldn't seem to get it written down.
Therefore, it was my task, according to Lewis, to write down
what was in Branch's head. He must have said something to
Phosphorescent State and Paramagnetism Branch as well, because he (Branch) invited me to come to
As a result of writing the color paper we did another ex- work with him in that area.
periment (which you will hear more about from other partic- In any case, we worked out an arrangement by which I
ipants). We found in examining some of the dyestuff infor- would come to Branch's house for dinner once or twice a week.
mation that we had assembled for the color paper that char- Esther Branch, his wife (also a chemist with a PhD from
acteristics such as fluorescence were described. Lewis got the Berkeley) would cook dinner, and we would then go to work.
idea to find out why all dyes did not tiuoresce, why did all dyes Branch would have written some material during the week,
not re-emit the light they absorbed. He recognized the reason and I was supposed to write some more. We would rewrite and
for this was that a molecule in an excited electronic state can then plan next week's task. That's how the book was written.
either emit the light directly (fluorescence) or transfer that I must have had fifty dinners at the Branch's house, and the

s e r i e s . T h e t o t a l e f f e c t i s g i v e n i n t e r m s o f a p r o p e r t y of t h e
s u b s t i t u e n t ( / n + Ra) a n d a p r o p e r t y o f t h e s k e l e t o n u p o n
w h i c h t h e s u b s t i t u e n t is p l a c e d {AJ. ( T h i s s a m e t y p e of ex-
p l a n a t i o n w a s u s e d l a t e r b y H a m m e t t (a a n d p ) a t C o l u m b i a . )
O n e c o n s t a n t h a d to d o w i t h t h e e f f e c t o f s u b s t i t u e n t (a) a n d
t h e o t h e r c o n s t a n t h a d t o d o w i t h t h e e f f e c t o f s t r u c t u r e (t>)
upon which the substituent was placed.
T h e p u b l i c a t i o n of " T h e T h e o r y of O r g a n i c C h e m i s t r y " i n
1941 b y B r a n c h a n d C a l v i n w a s t h e b e g i n n i n g of t h e o r e t i c a l
o r g a n i c c h e m i s t r y i n t h e U n i t e d S t a t e s , a n d i t is r e l a t e d n o t
only to t h e w o r k of G i l b e r t L e w i s b u t also t o t h e E n g l i s h school
which began with Lapworth, Lowry, Ingold, and Robinson.
B r a n c h , b e c a u s e of h i s E n g l i s h b a c k g r o u n d a s a n u n d e r g r a d -
u a t e a t L i v e r p o o l , h a d b r o u g h t t h e s e e d s of t h e s e i d e a s t o
Berkeley. T h e s e concepts evolved, u n d e r t h e stimulus of
L e w i s ' i d e a s of t h e e l e c t r o n p a i r b o n d , i n t o r e s o n a n c e , coor-
dination theory, etc.
W e c a n t r a c e t h e effect of L e w i s ' s t y l e a n d h i s t h i n k i n g , n o t
only on chemistry as a whole, b u t particularly on theoretical
organic chemistry which was really founded on t h e Lewis
e l e c t r o n p a i r b o n d a n d all of t h e t h i n g s t h a t flowed from it,
s u c h a s of Pauling's resonance q u a n t u m theory a n d m o d e r n
m o l e c u l a r o r b i t a l t h e o r y . T h e i n i t i a t i o n of t h i s n e w p h a s e of
dynamic organic chemistry began with Lewis' invention, or
r e c o g n i t i o n , of t h e e l e c t r o n p a i r b o n d a n d h o w it c o u l d b e
modified a n d used.
B r a n c h ' s a n t i c i p a t i o n of t h i s p h e n o m e n o n h a s n e v e r b e e n
properly realized or acknowledged. Branch came to Berkeley
in 1912 as a g r a d u a t e s t u d e n t , t h e y e a r t h a t L e w i s c a m e t o
Figure 3. Gerald 6. K. Branch, 1936. B e r k e l e y , a t t h e v e r y b e g i n n i n g of t h e s e m i n a r d i s c u s s i o n s o n
t h e s u b j e c t o!' h o w t h e m o l e c u l e is p u t t o g e t h e r . B r a n c h p a r -
b o o k w a s w r i t t e n a n d finally p u b l i s h e d in 1 9 4 1 (10). It w a s t h e t i c i p a t e d in t h e discussions a n d w a s influential in t h e d e v e l -
first book on theoretical organic c h e m i s t r y t h a t h a d ever b e e n o p m e n t of L e w i s ' i d e a s . T h e y i n t e r a c t e d w i t h e a c h o t h e r .
w r i t t e n in t h e U n i t e d S t a t e s t h a t c o n t a i n e d q u a n t u m m e - W h e n L e w i s g o t t h r o u g h w i t h m e on t h e color a n d m a g n e t i s m
chanical language in it (those were t h e c h a p t e r s I w r o t e ) . T h e efforts, h e t h o u g h t t h a t t h e p r o p e r p l a c e for m y n e x t efforts
c h a p t e r s w r i t t e n b y B r a n c h c o n t a i n e d a d e t a i l e d a n a l y s i s of w o u l d b e w i t h G e r a l d B r a n c h in t h e p r e p a r a t i o n of t h e t r e a t i s e
t h e effect of s t r u c t u r e o n t h e a c i d i t y of h u n d r e d s of o r g a n i c o n t h e o r e t i c a l o r g a n i c c h e m i s t r y . T h i s book, in effect, orga-
( a n d i n o r g a n i c ) a c i d s . ( A c i d i t y w a s a n o t h e r of t h e r e c u r r e n t n i z e d all of o r g a n i c c h e m i s t r y in t e r m s of e l e c t r o n t h e o r y .
L e w i s t h e m e s : color, m a g n e t i s m , a n d a c i d i t y . T h e t h e o r y of P h y s i c a l - o r g a n i c c h e m i s t r y a t B e r k e l e y a n d in t h e U n i t e d
a c i d s a n d b a s e s h a d b e e n f o r m u l a t e d m u c h e a r l i e r [2,4), but S t a t e s d e p e n d s u p o n L e w i s ' i n i t i a l s t i m u l u s i n t h e c o n c e p t of
Lewis e x p a n d e d these notions, with G l e n n Seaborg as his the electron pair bond and Branch's evolution and develop-
p e r s o n a l assistant t o d o this.) B r a n c h h a d a l r e a d y in his m i n d m e n t of t h a t c o n c e p t a n d s t i m u l u s .
g o n e o v e r t h e e f f e c t of s t f u c t u r e o n a c i d s t r e n g t h , a s m e a s u r e d
b y p H a n d p K a , a n d h e u s e d t h a t a s t h e f o u n d a t i o n of t h e Lewis' Administrative Concepts at Berkeley
a n a l y s i s of m e s o m e r i c ( r e s o n a n c e , R,,) e f f e c t s a n d i n d u c t i v e
(polar, /„) effects. T h e s e c o n c e p t s a r e u s e d t o describe t h e
I'd like to touch briefly on some of the particular methods
e f f e c t s of s u b s t i t u e n t s a n d s t r u c t u r e o n a c i d i t y of a n y g i v e n
that Gilbert Lewis used in establishing the department at
Berkeley, shown in 1951 in Figure 4 on the occasion of Joel
Figure 4. Chemistry Department, 1951. Left to right tront row: Latimer, Stewart, 8lasdale, Hildebrand, Gibson, Giauque, Branch, and Rotlefaon. Pitzer and Calvin
immediately behind Rolfefson.

Hildebrand's seventieth birthday. (Note that even though Conclusion
Lewis himself is not in this photograph—he died in 1946— Let thermal words he Lewis' own, delivered on Charter Day,
Latirner, Stewart, Hildebrand, Giauque, and Branch are ev- University of California, Los Angeles, March 22,1935 (12):
ident, as well as Pitzer, Calvin, and Seaborg.)
The department of chemistry at Berkeley was (and is) one Society is becoming increasingly aware of the power of science to
of the most highly regarded in the United States and world- bring weal or woe to mankind. But now when it is seen that the
wide. The reason for this is perhaps best expressed by Gerald same science that brings prosperity and comfort may lead to de-
Branch in his essay on Gilbert Lewis (see Appendix). As a pression and discomfort, men are beginning to look with mixed
teacher and administrator, Lewis opposed the tendency feelings at this monster which society may exalt or persecute, but
cannot view with indifference. Perhaps my topic today should
toward specialization in curriculum, and he kept the number have read 'Ought Scientists to be Burnt at the Stake?' I shaii not
of undergraduate courses to a minimum with the purpose of attempt to decide this question, but only to present in a cursory
preparing students with a thorough grasp of fundamentals way some of the pros and cone But if scientists are to be de-
rather than a mass of facts. Also, segregation of students was stroyed, let them not alone be the victims; every creative thought
made early, in the freshman year, and the better students, must be extirpated. A philosopher's epigram may kindle a world
were assigned the better instructors. To quote Branch, war. So scientist, inventor, artist, poet and every sort of troublous .
enthusiast must together be brought before the bar of the new in-
Lewis believed that for a chemist to be useful to the world he quisition.
should have a superior mind. In consequence, he preached that
the department use its time and energy on good rather than aver- Acknowledgment
age students. This somewhat undemocratic principle was often The preparation of this paper was supported, in part, by
harshly criticized.
The Director, Office of Energy Research, Office of Basic En-
For graduate students, Lewis' methods were also not ortho- ergy Sciences, Division of Chemical Sciences of the U.S. De-
dox, but successful, the genera! principle being to allow the partment of Energy under Contract No. DE-AC03-
graduate student the greatest possible latitude. The students 76SP00098.
acquired initiative, morale, and a fine spirit of cooperation
among themselves and the faculty. The weekly research Literature Cited
conference (described in Reference (6) and Appendix) was the 0) Bray, W. C, and Branch. G. E. K., J. Amer. Chem.. Soc. 86,1440 (1913).
most important medium through which Lewis educated the (2) Lewis, G. N, J- Am*'- Chem. Soo.,85, ]448 0913).
(3) Kahtoi, Ji- R, K., "The Origin of G. N. Lewis' TWy of the Shared Pair Bond," m
graduate students, staff, and himself. "Historical Studies in ths Physical Sciences," Vol 3, (pp 343-376), {Editor:
McCorromach, R.), tMv, of Pennsylvania Press* Philadelphia, 1971.
(4) Lewis. G. N., "Valence and the Sliucture of Atoms and Molecules," Chemical Catalog
Co., New Yotl, 1923; reprinted by Dover Pablicatiuna, New York, (966.
(5) Lewis, G.K.J-Amer.Chzm. Sue., 38,762 (1916).
Evaluation of Gilbert Lewis as a Scientist (6) Calvin. Melvin, "Essay on Gilbert Newton lame," in Proc. Robert A. Welch Found.
Conf. Chsm.Res.,20,116(1976}.
The success of Lewis and his education of graduate students <T) Lewie. G. N-, J- Chem. Pkys., 1,17 (1933).
(8) Lewis, G. N,and Calvin, Melvin, Chem. RED. 25,273 (1B3»).
and faculty is mirrored in the worldwide achievements of those <9) Lewis, C. N., and Calvin, Melvin, J. Amer. Chem. Soc, 67,1232 (194S).
students and staff. As an example, the following people, either (10) Branch. G. E. K., and Calvin, Melvin, "The Theory of Organic Chemists," Pnsntice-
students of Lewis or faculty members at Berkeley under HalL Engiewood Cliffs, NJ, IM1.
(11) Mildebtand, J. H., "Gilbert Newton Lewis." Obil. Nat. Feliotos of The Royal Society
Lewis, have received the Nobel Prize in Chemistry: Harold K, 491 (1947).
C. Urey (1933), William F. Giauque (1949), Glenn T. Seaborg (12) Thia talk wns cited in the book by Atthur Lachman, "Borderland of the Unknown: The
(1951), Wiliard F. Libby (1960), and Melvin Calvin (1961). No Life Slory of Gilbert Newton Lewis," Pageant Press, New York, I95S.
other single teacher has such a record of students.
There is no doubt that the pre-eminence of the department
of chemistry at Berkeley was largely due to Gilbert Lewis' Appendix;
direction for 29 years. The Lewis school of chemistry, with its Gilbert Newton Lewis, 1875-1946
concepts of intellectual vigor and excellence, has spread
throughout the world, as his students, and their students, have
created ever-widening circles of teaching and research. G&raid E. K. Branch
The following quotation concerning the effect that Gilbert
Lewis had on chemistry (and science) is taken from the reso-
lution read before the Academic Senate of the University of Gilbert Newton Lewis was born in Massachusetts on the 25th
California, Berkeley after the death of Lewis in 1946. It was of October, 1875, but migrated to Lincoln, Nebraska while stili a
written by Professor G. E. Gibson (11): child. When 13 yearB old he went to the preparatory school for the
University of Nebraska. On graduating from this school he went
The half-century which terminated with the death of Gilbert to the University of Nebraska for two years and then to Harvard
Newton Lewis wiil always be regarded as one of the roost brilliant College, where he obtained a &A. in 1896.
in the history of scientific discovery, an<j his name ranks among After graduation he taught for a yeas at PhiEips Academy in
the highest in the roster of those that made it great. The electron Andover. He then returned to Harvard and obtained the MA and
theory of chemical vabnce, the advance of chemical thermody- PhD degrees in 1898 and 1899, respectively. After obtaining his
namics, the separation of isotopes . . . . the unravelling of the doctorate he was appointed an instructor in Harvard. With a break
complex phenomena of the adsorption, fluorescence and phos- of a year of study in Germany, he remained an instructor at Har-
phorescence of the organic dyes are among the achievements vard until 1904.
which will always be associated with his name. Why Lewis' career at Harvard came to an end is not clear. In
The methods he chose were always simple and to the point. He later life he boasted that he was fired. As an instructor he pub-
was impatient of unnecessary elaboration.. .. When the point at lished three papers of high quality in quick succession, and then
issue seemed to him sufficiently important, he would not hesitate published nothing for three years. For one who published, on an
to employ apparatus requiring skill and delicacy of manipulation, average, four papers a year for the rest of his life, this lack of
as in the beautiful hut difficult experiment by which he and Cal- publications suggests a serious maladjustment to his environment
vin demonstrated the paramagnetisro of the phosphorescent trip- The break with Harvard may well have been fortunate for science,
let state (9). for on leaving that college Lewis resumed publication, although
As a man he was a great soul whose inspiration will never be
forgotten by those who knew and loved him. He was one of those
rare scientists , . . who are also great teachers and leaders of a Reprinted From History of Science Dinner Club Papers, July 13, 1953.
school, so that their influence is multiplied by the many they This essay was written In Maich 1951.
have inspired.

his next job might have been expected to quench the fire of his that a curriculum is apt to become gargantuan. Lewis strongly
budding genius, as it took him far from any center of research. The opposed suchtendenciesand kept the number of undergraduate
position was Superintendent of Weights and Measures in the courses in chemistry to a minimum. These courses were aimed to
Philippine laiands and Chemist of the Bureau of Science at Ma- give a thorough grasp of the fundamentals rather than a mass of
nila. Somehow he found time for research in pure chemistry and facts. Thus at a tune when many chemistry departments in the
published three papers while at Manila. country had no undergraduate courses in thermodynamics, Cali-
After a year in the Philippines he returned to Massachusetts fornia had two. On the other hand there was no course on petro-
as a member of the staff of the Institute of Technology, which at leum chemistry in the department, although oil was a major in-
that time was a lively center of scientific thought- He remained dustry in the state.
at M.I.T. from 1905 to 1912, during which time he started his great The aim of getting the student to think for himself was attained
contributions to thermodynamics. He also worked in other fields by free discussion between student and teacher and the large use
including relativity. The article he published with E. B. Wilson of problems. The value of the former was probably increased by
(i) was an outstanding contribution to the theory of relativity. the circumstance that the teacher was often a graduate student
In the seven years Lewis was at M.I.T. he became famous both The graduate student is usually not as learned as the professor,
at home and abroad. In 1912 F. G. Donnart of Liverpool advised but the student is less shy with his instructor when the latter is a
the author of this article to accept an opportunity to go to the graduate student. It may be noted that such contact between
University of California for graduate study, because he thought undergraduate and graduate student is educational to both
that Lewis was the moat brilliant young physical chemist at that parties.
time. Lewis' belief in the effectiveness of problem sets spread even
In 1912 Lewis was appointed Chairman of the Department of to so factual a subject as organic chemistry. At the present time
Chemistry and Dean of the College of Chemistry at the University manytextbooksin organic chemistry contain problem sets that
of California. These positions he held until he was 65. He contin- challenge the ingenuity i>f both student and instructor. This might
ued as professor and professor emeritus until he died suddenly well be traced back to Lewis' influence.
while working in his laboratory on the 23rd of March, 1948. Segregation of students was made as early as the freshman year.
Just before coming to California, Lewis was married to Mary The freehman laboratory was divided into rooms that could hold
Sheldon, the daughter of a Harvard professor. Three children, no more than 25. Efforts were made to assign rooms to the better
Margery, Richard, and Edward, were born to this marriage. Mrs. students and the better instructors to these rooms. Many of the
Lewis and the children are still alive. The two boys followed their upper division courses were restricted to the better students. At
father's footsteps in becoming chemists. one time undergraduate courses were divided into three classes,
Lewis' work in California was interrupted by World War I. courses restricted to honor students, those attended by the better
Shortly after America's entry into the war, he received a com- students but not restricted to honor students, and finally unre-
mission. He arrived in Prance in January 1918, and after a visit to stricted courses. All honor students were required to do some re-
the front during the German offensive of that year, he was ap- search. The laboratory course in physical chemistry was divided
pointed Chief of the Defense Division of the Chemical Warfare into two sections, one of which was restricted to honor students.
Service. For his work in this capacity he received the Distinguished These complicated rules aimed at giving the better teaching to the
Service Medal from his owe country and the Cross of the Legion better students.
of Honor from France. In training graduate students Lewis' methods were unorthodox,
During the nineteenth century America was definitely inferior but on tiie whole successful. The general principle was to allow the
to Western Europe in pure science. At the turn of the century a graduate student the greatest possible latitude. They were given
wave of progress in science started in this country and after 50 the run of the storerooms and laboratory facilities. They chose
years the United States leads the world in pure science. These their own instructors for their research work, and could change
great movements are common in the histories of civilizations. In horses in the middle of the stream. Lewis was careful to limit the
such a movement, a man may be a contributor because of his sci- number of graduate students working for him, thus preventing his
entific research and its consequent inspiration to others or because eminence in chemistry from depriving the other members of the
of histeaching.We do not limit the latter to conducting classes, staff of assistance in their work.
but include the organization and leadership which enable others The freedom given to the graduate students to obtain apparatus
to be successful teachers. In both respects Lewis was a historical and materials no doubt led to some unwarranted expenditure, but
figure in the great movement that brought America to the foremost theavoidanceofdelaysandred tape more than compensated for
place in chemistry. this. Further, the students acquired initiative, morale, and a fine
The effect of a man's research is not restricted to his own cooperation amongst themselves. This spirit of cooperation was
country; it is primarily an advance of science throughout the world. not limited to the graduate students, but included the staff. No
But the effect of histeachingis to a large extent localized. Further, one was ever too busy to help the research of another. No one, not
a man's scientific discoveries are widely known, but his teaching even Lewis, wastooproud to seek assistance.
is known only to a few. For these reasons we shall first consider The choice of graduate students was carefully made by Lewis,
Lewis as a teacher and the founder of a great department of with the assistance of members of the staff. In this choice natural
chemistry in Berkeley. gifts were considered more important than knowledge of chem-
Lewis felt that a chemistry department should both teach the istry. In many cases the lacunae in the students' education had to
science and advance it But in both functions the emphasis should be filled by undergraduate courses. Generally the deficiency was
be on the fundamental principles of the subject rather than on its readily made up. Thus Herman C. Rarosberger took junior year
industrial applications. There is always some conflict between pure courses in chemistry, yet he readily obtained his doctorate, and
and applied chemistry, and the proper balance between them in went on to contribute much to the advancement of chemistry, until
a university varies with the conditions in the country. In a young an untimely death put an end to what, promised to be a brilliant
and rapidly developing country the danger is that the applied career.
chemistry will devour the pure one and will in its turn lose origi- Having chosen a candidate for the PhD, he next made sure that
nality from being out of contact with fundamental principles. Thus the choice was a happy one. The aim was to obtain this knowledge
Lewis' emphasis on the pure science was fortunate for California, early. Constant oral examinations were used. As the number of
even though it might have been deleterious to a more developed graduate students increased, the burden of the examinations to
country. the staff became serious. The problem was never solved satisfac-
Lewis believed that for a chemist to be useful to the world he torily. In some cases it was doubtful whether the recipient of the
should have a superior mind. In consequence he preached that the degree was really worthy. Still worse, some failed to get the degree
department use its time and energy on good rather than average yet in later life contributed much to chemistry and became emi-
students. This somewhat undemocratic principle was often harshly nent scientists.
criticized. That some success was achieved in obtaining a more One good result of Lewis' efforts to ascertain the worth of the
than average ability amongst the students in chemistry is shown student as soon as possible was the abolition of the final exami-
by the unduly high percentage of chemists among the valedicto- nation for the PhD. This examination was either a farce or an
rians. evil.
Chemistry is a subject where specialization is rife, with the result The weekly research conference was the most important me-
Volume61 Number 1 January 1984

dium through which Lewis educated the graduate students, the modynamics to be applicable to chemical equilibrium it is neces-
staff, and himself. In this meeting papers were presented by sary that some relationship be found between some quantity
graduate students, staff, and distinguished visitors. These papers measured by analysis and some quantity related to work or energy.
included work in progress in the laboratory, work planned, and This connection was the empirical law of the proportionality be-
excerpts from the current literature. Each paper was followed by tween the partial pressure of a substance and its concentration.
an active discussion, in which everyone could have his say, irre- However, this law is not exact. Lewis' chief contribution to the
spective of his rank or the orthodoxy of his idfcaa. application of thermodynamics to chemical equilibrium was to use
In these discussions Lewis displayed a depth of insight and the proportionality between pressure and concentration only for
brilliance of thought that were an education to all who heard him. infinitely dilute concentrations, where the proportionality is exact
He accepted with good grace the harsh criticisms that were char- as far as is known. To do this he introduced two quantities, the
acteristic of the conferences. Needless to say his remarks were fugaeity and the activity. For infinitely dilute conditions these
enlivened by his wit. This wit often pierced to the heart of a quantities are equal to the pressure and concentration, respec-
problem. One of the old graduate students has said that he never tively.
fully understood entropy until he heard Lewis define the entropy In reality only one of these quantities is necessary. Although
of a system as what we do not know about it. Before publishing fugaeity is perhaps the more fundamental, activity is the one that
Lewis frequently submitted his ideas to the criticism of the re- has survived. This is because it is more nearly related to the con-
search conference, or to similarly conducted special seminars. centration of a solution as obtained by analysis, and the deviations
The success of Lewis' education of graduate students is mirrored between activity and concentration in solutions are normally
in the success of the students. Fourteen of those who obtained their greater than those between fugacities and pressures in gases.
doctorate during his regime are or have been heads of departments The introduction of tbis more exact application of thermody-
or deans in reputable universities. Three have received the Nobel namics to chemical equilibrium necessitated a change in the
prize, namely, W. F. Giauque, G. T. Seaborg and H. C. Urey. equilibrium constant of the oid mass law. These equilibrium
Strange to say, many have achieved outstanding success in in- constants are now expressed in activities instead of concentrations
dustrial chemistry. if the activities have been measured. The new equilibrium con-
Naturaiiy I-ewis owed much of his success in California to the stants are really constant as long as the temperature is constant,
other members of the department. Since it is at the beginning of whereas the older constants often varied greatly at the same
things that contributions are most important, we shall mention temperature.
William C. Bray, Joel H. Hildebrand, George E. Gibson, and One can measure an extensive property, say volume, of a ho-
Richard C. Tohnan as those to whom Lewis owed most. Of the later mogeneous mixture, but how much of this property is to be as-
additions to the department, Wendell M. Latimer contributed signed to a particular component is indefinite. Yet for thermo-
most and succeeded to the deanship. dynamic application it is sometimes necessary to assign a certain
If Lewis had done nothing else but build a peat department of amount of this property to a mole of some component. Lewis
chemistry in the University of California, he would have been an surmounted this hurdle by using the increase of the property re-
illustrious Californian; but from a wider viewpoint this achieve- sulting from the addition of a mole of the substance to so Sarge an
ment is trivial beside his contributions to science. These contri- amount of the mixture that the proportions of the components are
butions covered a wide field, even extending beyond the confines not affected materially. These properties were called partial molal
of chemistry. Nevertheless, two-thirds of his published work re- quantities.
lates to the application of thermodynamics to chemical equilib- Lewis introduced the term ionic strength into thermodynamics.
rium, a theory of atoms, molecules and chemical bonds, isotopes, In solutions of electrolytes the activities of electrolytes are greatly
especially deuterium, and the interaction of light with substances, affected by the electrical charges of ions. So the effects of ions
in describing Lewis' contributions to science we shall limit our- depend on their concentrations and charges. To combine the two
selves to these four fieSds. effects Lewis introduced the quantity called by him the ionic
At the time when thermodynamics wasfirstapplied to chemical strength, and defined as one-half the sum of all the products Z, 2m.,
equilibrium in Europe, J. Willard Gibbs did the same thing in where Z; is the charge and mi the molality, of fheith species of ion.
America independently. In a sense, at that time there were two He discovered the empirical law that the activity coefficient of a
chemical thermodynamics, European and American. In its second salt in dilute solution is fixed by the ionic strength. The depen-
phase of development W. Nernst became the leading figure in dence of the activities on the ionic strength was later deduced from
Europe and Lewis in America, though somewhat later. Both men electrostatics and statistical mechanics by Debye and Htickei, and
wrote textbooks that became standard works, one for Europe, the gave rise to the famous Debye-Hiickel equation.
other for America. Lewis' experimental work on thermodynamics consisted chiefly
Lewis was quite familiar with European thermodynamics. In in the determination of standard free energies of substances and
fact, he had spent a semester at Gottingen with Nernst in 1901. ions. More than half of the free energies determined were those
Nevertheless, he considered himself a disciple of Gibbs, whom he of ions. In consequence his chief tool was electromotive force de-
greatly admired. Fundamentally the two thermodynamics do not terminations.
differ from each other. In the European system equilibrium is tied Calorimetry at very low temperature is another powerful
to the maximum work obtainable, which is usually represented weapon in. the determination of free energies. Lewis therefore
by the symbol AA. In the American system it is tied to the maxi- instigated the development of low temperature calorimetrical
mum useful work obtainable, which is usually represented by the technique in Berkeley. Although he himself did not publish many
symbol AF. The AF and AA differ by work done against a uniform papers involving low temperatures, the laboratory has become
pressure by the change of volume resulting from the reaction. To famous for this kind of investigation. The most shining worker in
some extent the use of AF is simpler than that of AA, but both are this field at the University of California has been W. F. Giauque,
perfectly permissible. Had Lewis' contribution to thermodynamics who lately has been awarded the Nobel Prize for his achieve-
merely been the rescue of AF, it would have had only academic ments.
value. But as we shall see it was much more than this. I/ewis became interested in the nature of the atom very early
Lewis was introduced to thermodynamics by T. W. Richards, in his career. His notebook of 1902 contains his first formulation
with whom he published his first paper on the subject {2). Bight of his theory, but he published nothing in this field until his in-
years later he published "The Outlines of a New System of terest was revived by the publication of a short article on the na-
Thermodynamics" (3) which contains the seeds of his later work. ture of bonds by W. C.Bray and the author in 1913 (5). This was
The fruition of his work on thermodynamics was reached in 1923 followed almost immediately by a publication on the same subject
with the publication with Merle Randall of "Thermodynamics and by Lewis (6) and the revival of his ideas of 1902, which were thrown
the Free Energy of Chemical Substances" (4). This book is one of to that den of lions, the research conference. The theory was not
the masterpieces of chemical literature and has been translated published until three years afterwards (7). In the same year, a very
into many languages, including Russian. similar theory was published by W. Kossel in Germany (8).
Thermodynamics is logically deduced from axioms concerning Jjewis' paper was entitled "The Atom and the Molecule." As its
energy, work, heat, and entropy. Corrected for the interchange- title suggests it was essentially two theories. The first part came
ability of mass and energy, these axioms are exact as far as is immediately into conflict with the Bohr atomic theory, for in the
known. Chemical equilibrium is measured by analysis. For ther- Lewis theory the constituents of the atom were quiescent while

in the Bohr theory there was constant motion of electrons within the acid which has room for such a pair. Lewis' definition of an acid
the atom. It was for this reason that the Lewis theory became was therefore based o» phenomena as well as on theory. Thus an
known as that of the static atom. Actually the essence of both acidic hydrogen compound was classed as an acid, not only for its
theories was the central location and greater mass of the positive ability to form an addition compound with a base by a hydrogen
nucleus of the atom, and the classification of its constituent elec- bond, but also because it gives its proton to a base in an almost
trons. In the Bohr theory the classification was by orbit, and it instantaneous process.
achieved the astounding success of predicting the spectrum of tiie Lewis also applied his theory to show the necessity of param-
hydrogen atom. In the Lewis theory the classification was by shell. agnetism in free radicals. This has led to the magnetic method for
It established the nature of the periodic table as based on the noble analyzing for free radicals. It is somewhat amusing to note that
gases (helium, argon, etc.) and the dependence of the etecteopos- this phase of the theory led Lewis to assign a new and indubitably
itivities and electronegativities of the elements on their positions correct formula to so simple a substance as oxygen.
in the periodic table. At the present time the two theories have in the early thirties Lewis started work on deuterium. The in-
been reconciled, or if one prefers, superseded by quantum me- spiration came from Harold C. Urey, one of the most famous of
chanics. the men who have obtained the PhD from Berkeley. During 1933
Actually neither Lewis' nor Bohr'a theory conformed to the laws and 1934 Lewis published 26 papers on this subject. This phase
of physics as then known. For this reason Lewis sought for varia- of his work tasted a very short time, as nothing about deuterium
tion in these laws to fit his theory. In nothing that he published appears in his writings after 1934.
was there anything of this nature that was worthwhile, but actually He was the first to prepare pure deuterium and its compounds.
he often tampered with thoughts that might have led to something Many of the chemical and physical properties of these were mea-
similar to quantum mechanics. sured. One of the important discoveries made by Lewis was that
Lewis' and Kossel's theory of the atom were essentially the the chemical properties of deuterium compounds differ from those
same, but Lewis' theory of the molecule was not shared with of the corresponding hydrogen compounds. Theory requires that
anyone, nor was it contained in his early notebooks. The essence there shouid be a difference in the aero point energies of deuterium
of this theory was that a bond between atoms was made by their and hydrogen bonds, and hence difference in the chemical prop-
sharing a pair of electrons of opposite magnetisms. Hence com- erties of their compounds.
bination decreases Use paramagnetism of atoms or radicals and To fully appreciate Lewis' work on deuterium one has to realize
their compounds are diamagnetic unless unpaired electrons lie that at the time it was done deuterium compounds could not be
below the vaiettee shell of electrons. obtained in bulk, and microchemical technique was in its in-
This formation of bonds by sharing electrons and atoms was an fancy.
anathema to the laws of physics of 191.6. Iêwis' attempts to explain The last phase of Lewis' work was on the relationship between
it by magnetic forces inherent in the electrons were unsuccessful, chemical constitution, absorption of light, and its re-emission in
although the inherent magnetism of electrons was shown shortly fluorescence and phosphorescence. Actually this subject had in-
afterwards. Although the theory was very successful in organic terested him for many years. He had written a paper concerning
chemistry, it almost received its+ death blow with the discovery of the color and hydration of ions in 1906. In 1920 when he gave the
a moiecule with the formula H2 , for in this molecule the hydrogen Faculty Research Lecture of the University of California the
atoms cannot be bonded together by sharing a pair of electrons subject was the relationship between color and chemical consti-
between them for the very good reason that it has only one elec- tution.
tron. But the theory of the electron pair bond was saved by His serious work on this subject began when he was 64 years old
quantum mechanics, for from the postulates of the latter it was and continued until his death at the age of 71. Leaving out post-
shown to be deducible (9) that two atoms or radicals would be humous work, he published 18 papers in this field. The first of
bonded together by a pair of electrons of opposite magnetism. these papers and the last before his death were in collaboration
Further, quantum mechanics showed that two equivalent units, with Melvin Calvin. !t is fitting that this last publication was about
as for instance the two protons of H2*, would be bonded by sharing an outstanding piece of work, in which it was experimentally
a single electron. This limitation to the equivalence of the bonded shown that the phosphorescent state is paramagnetic.
particles makes the single electron bond a rarity.
Needless to say, Lewis was showered with honors at home and
Lewis theory of the chemical bond is one of the most important abroad. The moat appropriate of these was the Richards Medal,
contributions to structural theory and hence to organic chemistry. for he was the most famous of Richards' students. To the regret
Linus Pauling in his book "The Nature of the Chemical Bond" {10) of all his friends he was not awarded the Nobel priê. His contri-
expresses a similar opinion. It is a striking coincidence that organic butions to thermodynamics and his theory of the chemtca! bond
chemistry owes so much to the two physical chemists, Van't Hoff deserved this honor.
and Lewis.
Quantum mechanics not only freed Lewis' theory of the stigma
of unorthodoxy which it had carried at first, but also increased its Literature Cited
value by allowing electrons to be used in more than one way at a
ijme. This made possible the ready explanation of the body of facts (1> Lewis. G. N, and Wiiaja. E. B., Prnc. Araer. /lead., IS, 389 (1912).
(2) Richards. T. W.. and Lewis, C. H.,Prt>r- Amer. Acad., 34, 87 (IB99).
which in the older structural theory were explained by the some- (3) Lewis, G. N., P™. Amrr. Acod., 43, 258 (19071.
what unsatisfactory concept of residual affinity. It also solved the (4) I^wis, G. N., and Randall, Merio; "Thermodynamics and Ihe Ftfle Energy of
problem of the benzene ring, a problem that had led to the parti- Chemical Substances," McGraw-Hill, New York. 1923.
tion of books and courses on organic chemistry into aliphatic and (5) 8ray.W.C.,andBranch,G.E.K.rJ.Amei- Chem.Sac,38,1440(1913).
aromatic sections. (fit Lewis. G.N., J. Amer. Chsm. Sot, SB, 1449(1913).
(7) Lewis, G. N., J. Amer. Chem. Sue, 38,762 (1916).
Among Lewis' own applications of this theory of the electron (S) Kobsei, W., Ann. Physik.,49,229 (1916).
pair bond to chemistry was his generalized concept of acids and (9) Heitler,W.,and London, t\Z.Physik, U,465 (1927).
(10) PauKnf, Linus, 'The Nature uftiie Chemical Bond," Cornell Univ. Press, Ithaca,
bases. In this theory the base has a pair of electrons to share with New York. 1S39.
Symposium Honoring Debye to be Held

On March 22,1984, the Cornel) University Department of Chemistry and the Cornell Section of the American Chemical
Society will hold a symposium to commemorate the 100th anniversary of Peter J. W. Debye's birth. Lectures will be presented
by Manse! Davies, Manfred Eigen, PautJ. Flory, Mark Kac, Linus Pauling, and E. Bright Wilson; in addition, Hans A. Bethe
will speak at the evening banquet. Those interested in attending this symposium should contact: Dr. Earl Peters, Executive
Director, Department of Chemistry, Cornell University, Baker Laboratory, It&aea, NY 14853.

Enduring Distributions that Deny Boltzmann
Leonard K. Nash
Harvard University, Cambridge, MA 02138
Equilibrium distributions of atoms and molecules are or-

dinarily Boltzmann distributions (i), while nonequilibrium P V* T P V T
distributions that escape the rule of Boltzmann usually eiude
also any other comparably simple description. We examine
here two steady-state distributions that are (a) at least ap-
proximately describable, and (b) of substantial practical in-
terest.
P If
The Atmosphere and Ks Lapse Rate
Imagine a homogeneous atmosphere of ideal gas with mo-
lecular weight (M) approximating 29, i.e., the weighted av-
erage molecular weight of air, Writing the idea! gas law in the
form PM = (nM/V}RT, we see t h a t the local density (6) will
be expressible, in terms of the local temperature and pressure, P.V.T
as
5 = PM/RT
To establish the variation of pressure with altitude ih), con-
sider an infinitesimal slice of the atmosphere, with cross- Figure 1. Two routes that link sea-levei conditions {PQ, VO, TO) with the condltfons
sectional area A, height dfe, and mass dm. Consequent to the {P, V, T) at any linal altitude.
decrement in superincumbent mass, passage from the lower
to upper surface of the slice is reflected in a difference of
pressure
parcel r e m a i n s t h r o u g h o u t in p r e s s u r e e q u i l i b r i u m with t h e
s u r r o u n d i n g a t m o s p h e r e , t h e d i s p l a c e m e n t m u s t also be a p -
proximately reversible. T h e qualitative situation is then quite
where g symbolizes the gravitational acceleration. The mass clear. As it ascends i n t o regions of d i m i n i s h i n g a t m o s p h e r i c
decrement is in turn expressible in terms of the local density p r e s s u r e , a rising m a s s of air e x p a n d s a n d d o e s work o n t h e
and the volume of the slice, as dm = (Adh)S. Substitution of s u r r o u n d i n g a t m o s p h e r e . In an a d i a b a t i c process t h i s work
our expression for 5 then produces m u s t be d o n e a t t h e e x p e n s e of t h e i n t e r n a l energy of t h e air
dP Mg p a r c e l , which m u s t therefore cool as it rises.
(i) M o s t simply t o q u a n t i f y this effect, we observe t h a t a re-
P '
versible adiabatic displacement m u s t be isentropic. Along t h e
Over the lower reaches of the atmosphere (troposphere) at p a t h of t h e actual displacement (HI in Fig. 1), expansion from
which our analysis is aimed, g is effectively constant. Hence, sea-level c o n d i t i o n s (PQ, Vih To) t o t h e c o n d i t i o n s ( P , V, T)
if this part of the atmosphere were isothermal, integration of c h a r a c t e r i s t i c of any final a l t i t u d e m u s t yield
the last equation would give
In /'//'{, = -MghiRT
A n o t h e r r o u t e b e t w e e n t h e s a m e original a n d final s t a t e s in-
where P» is the pressure at altitude h = 0 {e.g., sea level). Since volves (I) c o n s t a n t - p r e s s u r e cooling t o t h e final t e m p e r a t u r e ,
in an isothermal atmosphere the number of molecules (JV) per followed b y (II) i s o t h e r m a l e x p a n s i o n t o t h e final p r e s s u r e
unit volume is directly proportional to the local pressure, the ( a n d v o l u m e ) . W i t h e n t r o p y a function of s t a t e , necessarily
last equation is equivalent to the Boltzmann distribution law
in the form
I n s e r t i o n of familiar expressions for ASj a n d A S n p r o d u c e s
where m is the molecular (not the molar) mass and f is the nCP In ~ - + nR in -r = 0
excess gravitational potential energy of a molecule at altitude
h>0. T
Though a fair approximation in the troposphere, this simple i) n ~ -R
law does not properly apply to our atmosphere---a nonequi-
librium system that, far from being isothermal, displays a large r CP
S i n c e Pi, a n d T o a r e c o n s t a n0t s , t h e y v a n i s h i n a d i f f e r e n t i a t i o n
vertical temperature gradient. One striking manifestation of t h a t yields
this gradient is the well-known fact that it is much colder on
a mountain's peak than at its base. How does it happen that, _ = _ _. (2)
closer to the sun and with less of the atmosphere to shield it

from that luminary, mountain peak is much colder than F r o m t h e g e n e r a l e q u a t i o n ( I ) w e s u b s t i t u t e for d P / P , a n d
mountain base? so find
As glider pilots well know, large bodies of air are constantly
rising or sinking through the atmosphere. With air a very poor X l
T ~ CP RT
conductor, the displacement of these large air masses must
be approximately adiabatic. And because the moving air A f t e r c a n c e l l a t i o n o f J ? ' s a n d T's, by integration we obtain
journal of Chemical Education

greater atmospheric pressure? Already dried by orographic
AT-- •Ah (3) precipitation during its ascent of the windward slopes, air that
CP
reaches the summit cold now undergoes a reversible adiabatic
Insertion of M =s 0.029 kg/mole, g <* 9,8 m/a 2 , a n d CP ^ 7R/2 compression that vigorously reheats it {up to 1.0°K/km) as it
= ( 7 / 2 ) 8 . 3 1 4 j o u l e / m o l e - ° K n o w gives AT/A.H = descends the leeward slopes. (The ehinook wind, or foehn, is
- 0 . 0 0 9 8 ° K / m . W h a t meteorologists call t h e dry adiabatk a spectacular special case.) The leeward slopes are thus bathed
lapse rate is t h u s e s t a b l i s h e d as in dried air heated well above its dew point, and in this region
there can be scant prospect of rain. And that "rain shadow"
ATiAh^- -10°K/km
stretches further to leeward the greater the altitude and extent
T h i s is a very l a r g e effect w e c a n m e a s u r e a g a i n s t t h e c o n - of the mountain(s) concerned. On a major scale, in California
d i t i o n s on, say, M t . K i l i m a n j a r o — a 5.9-km p e a k close t o t h e (where the prevailing wind blows from the West, across the
e q u a t o r . T h a t e q u a t o r i a l setting n o t w i t h s t a n d i n g , conditions Pacific) the windward slopes of the several mountain ranges
a t t h e t o p of M t . K i l i m a n j a r o a r e q u i t e literally a r c t i c , char- are well watered, while off to leeward lie the deserts of Nevada.
a c t e r i z e d b y all-season snow a n d ice fields. If we s u p p o s e a On a minor scale, a modest peak on the small Caribbean island
b a s e t e m p e r a t u r e of 38°C ( ^ 100°F), our calculated lapse r a t e of St. Croix produces tropical rain forest on its windward
i m p l i e s a c r e s t temperature of 38 - 58 = - 2 0 ° C = - 4 ° F , slopes, and also a desert landscape that stretches leeward to
w h i c h is q u i t e low e n o u g h t o explain t h e p e r m a n e n c e of t h e the end of the island.
s n o w s of K i l i m a n j a r o .
O u r analysis h a s justifiably ignored kinetic-energy effects: The Ocean and Its Vertical Quasi-Uniformlty
e v e n w i t h a n a i r p a r c e l moving a t 3 0 m p h , t h e k i n e t i c e n e r g y
is e q u i v a l e n t t o n o m o r e t h e r m a l e n e r g y t h a n is r e q u i r e d t o Consider an ocean vertically uniform in temperature
w a r m t h a t a i r by 0.1 ° K , T h u s all b u t exceedingly high air ve- ( ~ 2 ° C ) and in salinity (=^35) i.e., ca. 35 g of mixed sea salts
locities will h a v e only a negligible effect. O n t h e o t h e r h a n d , per 1000 g of water. Levenspiel and de Nevers indicate {4)
t h e s e vertical d i s p l a c e m e n t s d o p r o c e e d r a p i d l y e n o u g h t h a t that, apart from a surface "skin" that extends to a depth of
we c a n also p r o p e r l y ignore b o t h c o n d u c t i o n effects a n d all only a few hundred meters in oceans with depths running as
t h o s e d u e t o a b s o r p t i o n o r emission of r a d i a t i o n b y a d r y a i r great as some 10,000 m, a real-world ocean can be significantly
t h a t is comparatively t r a n s p a r e n t to both solar a n d terrestrial approximated as a uniform ocean (5). Such a uniform ocean
radiation. A n d more generally, in t h e steady-state a t m o s p h e r e may plausibly be supposed an equilibrium ocean; but the
t h e vertical d i s p l a c e m e n t s t h a t e n g e n d e r t e m p e r a t u r e dif- falsity of t h a t conclusion is demonstrated by some striking
ferences are m u c h swifter t h a n t h e equilibrative processes t h u s incongruities to which Levenspiel and de Nevers have drawn
r e n d e r e d i n c o m p e t e n t t o d i s s i p a t e t h e temperature g r a d i - attention.
e n t — w h i c h is t o s a y insufficient t o r e t u r n t h e a t m o s p h e r e t o Between our uniform ocean and fresh water, the osmotic
t h e r u l e of B o l t z m a n n . pressure difference (IT) is calculable from the standard rela-
tion
A t a c i t a s s u m p t i o n of t h e foregoing analysis h a s b e e n d r y -
n e s s of t h e d i s p l a c e d a i r m a s s e s . Recognizing t h a t t h e y m a y RT. 1
c o n t a i n water v a p o r , we c a n give a t l e a s t a z e r o - o r d e r (2) ex- T-=-1H —
p l a n a t i o n of a n enlarged roster of striking facts (3). Consider
for example a n y m o u n t a i n ( s ) on o n e face of which a prevailing Here Xv and Vv symbolize respectively the mole fraction and
w i n d blows a i r r e n d e r e d h u m i d b y p a s s a g e over a w a r m sea. t h e molar volume of the solvent in the solution. We make no
W i t h t h e arrow indicating t h e prevailing direction of t h e wind, great error if we approximate Vv as the same as in pure water.
t h e observed c o n s t e l l a t i o n of c o n d i t i o n s a r o u n d t h e m o u n - In that case V v = M v //i v , where M v and pv symbolize respec-
tairj(s) is likely t o b e as i n d i c a t e d in F i g u r e 2, n o t wholly u n - tively the known molecular weight and density of water. With
r e m i n i s c e n t of a n alchemical d i a g r a m . As t h e h u m i d influent this substitution, the last equation assumes the form
air is driven u p t h e w i n d w a r d slopes, it is cooled a s before b y
adiabatic expansion. B u t when a t last t h e dew point is reached, ihB'f
In (4)
p r e c i p i t a t i o n of rain discharges a l a t e n t h e a t of c o n d e n s a t i o n
i n t o t h e air. T h i s checks t h e fall of t e m p e r a t u r e , a n d as t h e a i r
As t o X v , s u m m a t i o n over a s t a n d a r d recipe (6) for seawater
continues its ascent t h e r a t e a t which its temperature declines
yields Sw;m,-, where V; is t h e n u m b e r of moles of ions freed b y
is d i m i n i s h e d b y t h e release of f u r t h e r h e a t of c o n d e n s a t i o n
o n e mole of t h e i t h salt p r e s e n t a t molality m.;. B u t w h e n we
c o n s e q u e n t t o f u r t h e r p r e c i p i t a t i o n of rain a n d , u l t i m a t e l y ,
assign t o e a c h ^ its limiting i n t e g e r value, o u r neglect of ac-
snow. W h e n a t last t h e s u m m i t is a t t a i n e d , initially m o i s t a i r
tivity effects m e a n s t h a t , from t h e s u m Si»,-m,- = 1.16 mole/kg,
will have declined in t e m p e r a t u r e r a t h e r less t h a n initially d r y
we c a n o b t a i n for it n o m o r e t h a n a maximum estimate by
air. ( T h e a v e r a g e observed lapse rate approximates
writing
— 6 . 5 ' K A m . ) B u t if t h e p e a k is sufficiently high, t h e a i r will
be cooled enough to precipitate virtually all its original charge 1.00 (kg/1) 0.0821 (l-atm/mnle-°K) 275 (°K) 1.16 4-1000/18
of m o i s t u r e . T h i s m e a n s a b u n d a n t rainfall o n t h e w i n d w a r d
0.0180 (kg/mole) " 1000/18
s l o p e s ( a p t also to b e enveloped i n c o n d e n s a t i o n clouds).
= 25.9 atm
W h a t h a p p e n s w h e n , o n t h e leeward s i d e of t h e m o i ii- T h e o s m o t i c coefficient {4> =« 0.9) a p p r o p r i a t e t o s e a w a t e r (7)
t a i n ( s ) , t h e a i r m a s s b e c o m e s free t o d e s c e n d i n t o regions of p e r f e c t l y reconciles t h i s u p p e r l i m i t w i t h t h e = 23 a t m cited
b y Levenspiel a n d de Nevers as t h e observed osmotic pressure
of s e a w a t e r .
COLD I n t o a u n i f o r m ocean let us sink a very long p i p e closed a t
its lower e n d by a m e m b r a n e selectively p e r m e a b l e t o w a t e r
only. T h e interior of t h e pipe remains d r y until t h e m e m b r a n e
r e a c h e s s u c h a d e p t h t h a t t h e ocean's h y d r o s t a t i c p r e s s u r e a t
last rises t o 23 a t m . A t t h i s p o i n t reverse osmosis yields a thin
film of p u r e w a t e r o n t h e inner surface of t h e m e m b r a n e . A n d
a t still g r e a t e r d e p t h s , w h e r e t h e s e a w a t e r p r e s s e s ever m o r e
WARM s t r o n g l y a g a i n s t t h e o u t s i d e of t h e m e m b r a n e , o s m o t i c equi-
l i b r i u m is a t t a i n e d only after a l e n g t h e n e d c o l u m n of p u r e
Figure 2. Observed conditions around a mountain. The arrow Indicates direction
w a t e r h a s b u i i t u p inside t h e p i p e . A l i t t l e algebra b a s e d o n
of the prevailing wind.
Volume 6 1 Number 1 January 1984 23

7T
Sea water
Sea water
Fresh'
water
T
Figure 3. Hypothetical device that produces an upwellrng of pure wafer in s
uniformly salty sea.
Figure 4. Hypothetical device that extracts useful w o * from a uniformly satty
F i g u r e 3 s u p p l i e s a n explicit expression for t h e e q u i l i b r i u m sea.
d i s t a n c e (z) of t h e p u r e water from t h e surface w h e n t h e
m e m b r a n e is a t a n y d e p t h (/). W i t h p v t h e d e n s i t y of t h e p u r e s u m p t i o n t h a t t h e u n i f o r m m o d e ! o c e a n is a n e q u i l i b r i u m
w a t e r o n t h e inside, let p s symbolize t h e d e n s i t y of t h e sea- o c e a n . F o r s u r e l y a wholly s p o n t a n e o u s welling u p of fresh
w a t e r o u t s i d e t h e p i p e . A t osmotic e q u i l i b r i u m w e m u s t n o w w a t e r in t h e m i d s t of a s a l t s e a is no small incongruity. A n d
from this first incongruity arises a second n o less startling. F o r
find
r e m i x i n g of t h i s fresh w a t e r , w i t h t h e saline ocean w h e n c e it
- gpv(l c a m e , is a n obviously s p o n t a n e o u s c h a n g e from which a work
o u t p u t is i n principle recoverable; a n d Levenapiel a n d de
(5) N e v e r s s k e t c h a direct recovery of work from such a n osmotic
p u m p . W h e r e a b e t t e r k n o w n a l t e r n a t i v e a p p r o a c h (9) t o e n -
U n d e r 1 a t m p r e s s u r e a t t h e surface, pv = 1000 k g / m 3 , a n d ergy recovery exploits t h e d i s p a r i t y of t e m p e r a t u r e b e t w e e n
p s = 1028 kg/m 3 . A rise of pressure from 1 t o 1000 a t m (i.e., t h e surface " s k i n " a n d ocean d e e p , t h e Levenspie! a n d d e N e v e r s
p r e s s u r e a t a d e p t h of =s 10,000 m ) increases t h e d e n s i t y of a p p r o a c h i s r e m a r k a b l e precisely b e c a u s e it a i m s t o e x p l o i t
p u r e w a t e r b y r a t h e r less t h a n 5%, a n d t h e c o r r e s p o n d i n g t h e uniformity of real-world oceans. B u t is n o t a n y such ex-
d e n s i t y increase for s e a w a t e r is c o m p a r a b l y small (8). M u t u a l p l o i t a t i o n of uniformity itself a t h e r m o d y n a m i c incon-
cancellation of t h e s e small c h a n g e s t h u s e n s u r e s t h a t , a t all gruity?
d e p t h s i n a uniform ocean, t h e ratio pjpv m u s t retain a value Away from uitracentrifuges, all o u r e v e r y d a y l a b o r a t o r y
very close t o t h e 1.028 prevailing n e a r t h e surface. T h e o t h e r e x p e r i e n c e t e a c h e s c h e m i s t s t o t h i n k of equilibrium s y s t e m s
k e y ratio, 7r/p v , is similarly insensitive t o t o t a l a p p l i e d pres- a s h o m o g e n e o u s b o t h in t e m p e r a t u r e a n d composition, A n d
sure, a s is a t once demonstrable b y r e a r r a n g e m e n t of equation o n e is t h u s strongly predisposed t o view t h e uniform ocean as
(4). A t all d e p t h s in a s e a uniform i n T a n d X v , t h e r a t i o x / p v a n e q u i l i b r i u m ocean. B u t in t h e e x t e n d e d l a b o r a t o r y of a n
m u s t t h e n retain its surface value—which, in convenient units, ocean deep, t h e variation of gravitational potential energy m a y
18 b e big e n o u g h t o m a k e a n e q u i l i b r i u m ocean significantly
n o n u n i f o r m . T h e s p o n t a n e o u s p r o d u c t i o n of p u r e w a t e r a n d
2 3 ( a t m ? 101325 ( n e w t o n / m 2 - a t m ) useful work from a uniform ocean will t h e n cease t o b e in-
= 2330 mW
1000 (kg/m*) congruities precisely when w e can d e m o n s t r a t e t h a t a uniform
ocean is not a n e q u i l i b r i u m ocean.
For a uniform ocean, substitution in equation (5) of ap-
T h i s conclusion is established by Levenspiel a n d d e N e v e r s
propriate numerical values yields (in meters) the relation:
with a chemical-potential argument t h a t therm odynamic
z = 237.6 - 0.028 / novices m a y f i n d o p a q u e . A wholly t r a n s p a r e n t b u t still
compelling a l t e r n a t i v e analysis d r a w s o n t h e r m o d y n a m i c s
Two special cases are of particular interest. First, a t t h a t only for t h e proposition t h a t , b y itself, n o s y s t e m a t equilib-
critical depth where reverse osmosis fh-st produces a film of r i u m can s p o n t a n e o u s l y yield a work o u t p u t . T h e a r g u m e n t
pure water inside the membrane, with z - * I we easily calculate is similar i n style t o a classic d e r i v a t i o n of e q u a t i o n (4) from
the critical depth as t h e B o l t z m a n n law (10).
( = 237.6/1.028 = 231 m Into a d e e p i s o t h e r m a l column of s e a w a t e r — n o w s u p p o s e d
wholly a t equilibrium—we lower t h e device s k e t c h e d in Figure
in agreement with the figure obtained by Levenspiel and de 4. T w o m e m b r a n e s selectively p e r m e a b l e t o t h e solvent w a t e r
Nevers. Second, at that depth where pure water wells right up provide access t o a p u r e - w a t e r s h u n t of l e n g t h d/. A t t h e level
t o the surface, with 2 ^ 0 w e find of t h e u p p e r m e m b r a n e let t h e e q u i l i b r i u m o s m o t i c p r e s s u r e
difference b e ?r; a t t h e level of t h e lower m e m b r a n e let t h e
I = 237.6/0.028 = 8500 m osmotic pressure b e x + dir. (This does n o t a t all d i s c o u n t t h e
in acceptable agreement with the 8750 m that Levenspiel and possibility t h a t t h e uniform m o d e l ocean m a y y e t p r o v e a n
de Nevers draw from a far more difficult analysis. e q u i l i b r i u m ocean, since in t h a t e v e n t w e would s i m p l y find
Here is the first striking incongruity arising from the pre- dir = 0.) W h a t e v e r m a y b e t h e c h a r a c t e r of t h e e q u i l i b r i u m

ocean, however, it must exclude the possibility of any con- buoyancy correction. The density of the pure water being less
tinuous cyclic flow through the pure-water shunt-—because than the density of the salt solution, the solvent is found more
such a flow could be yoked by the paddlewheel to a continuous abundantly in the upper levels of the sea where / is small.
production of work no equilibrium system can supply. Flouted in the (real) uniform ocean that is not at equilibrium,
If p symbolizes the pressure on the outer face of the upper the Boltzmann distribution thus duly commands the (purely
membrane, the salt-water pressure on the outer face of the hypothetical) equilibrium ocean that is not uniform.
lower membrane must be Finally, we should demonstrate that the equilibrium ocean
supports no spontaneous weliing up to the surface of pyre
water, of the sort we found so incongruous in the uniform
On the inner face of that lower membrane the pure-water ocean. Under the familiar condition of constant p v and ps,
pressure is similarly expressible as differentiation of equation (5) gives
rk_J_
dl gpv dl \ pv,
A continuous, work-producing flow through the pure-water
shunt will be excluded if, and oniy if, the difference between Elimination of dir/d/ between this and equation (6) now
the two above pressures matches the equilibrium osmotic yields
pressure at the lower membrane—which entails dz /p, _\ L A
JT + dw = (P + gpsdl) - (P
In a n e q u i l i b r i u m ocean, therefore, t h e d i s t a n c e z is n o t a
, , IPo (6) function of t h e d e p t h {1} of t h e m e m b r a n e , a n d at all d e p t h s
r
= g(ih ~ pv) = g(h j t h e t o p of t h e p u r e - w a t e r column r e m a i n s a c o n s t a n t 231 m
T h e r i g h t side being positive, t h e osmotic p r e s s u r e m u s t in- below t h e ocean surface.
crease w i t h d e p t h (I) in t h e s e a — a n d we d i s s i p a t e all in-
congruities b y t h u s showing t h a t a u n i f o r m ocean c h a r a c t e r - Acknowledgment
ized b y c o n s t a n t ir cannot b e a n e q u i l i b r i u m o c e a n .
F o r m u c h useful criticism I a m i n d e b t e d t o D . E. C a r r i t t ,
W h y does v increase w i t h d e p t h in a n e q u i l i b r i u m o c e a n ?
C. M . D e l a n e y , a n d W . H . E b e r h a r d t .
P r e s u m a b l y because t h e solute c o n c e n t r a t i o n h e r e increases
W h i l e this essay a w a i t e d p u b l i c a t i o n , t h e lapse r a t e of
with d e p t h , which is t o Bay t h a t t h e mole fraction of t h e solvent
planetary atmospheres h a s been discussed by Blanck (11), a n d
water decreases with d e p t h . T h a t t h e r e is j u s t s u c h a decrease
a delightful p a p e r by B a c h h u b e r (12) touches lightly o n both
is easily d e m o n s t r a t e d . Observing t h a t t h e d e r i v a t i v e in
e x a m p l e s discussed in t h i s essay.
e q u a t i o n (6) refers t o t h e variation of TT in a s e a where pv ( a n d
ps) remain constant over t h e short span dl, we impose t h e s a m e
condition i n d r a w i n g from e q u a t i o n (4) t h e c o r r e s p o n d i n g Literature Cited
derivative: ft) Nash, L. K.. "ChemThermo," Addis™-Wesley, Reading, MA, 11972, p. 25,
{2} Fora full treatment see Irihame, J. VândsGoodson, WrL,,* Atmospheric Thermo-
oV PyRTdllXXy dynamics," Ueidei, Boston, MA, 1973.
(3) The full complexity of dimaiologicai phenomena is indicated hy Barry. R. G.. and
dt ' JT dl ChorleyT Rr Jr, "Atmosphere, Weather, and Climate," 3rd ed., Met!wenT Londtni,
1976.
E l i m i n a t i o n of dir/d/ b e t w e e n t h i s a n d e q u a t i o n (6) p r o - (4> LevenspieI,O.,ancid<>Nev(>rs,N.,Science, 183.157 (1974J.
duces (5) See For example the data for the Mindanao Trench cited by Groen.P., "The Wjj!m
of the Sea," Van Nostrand, Printelon, NJ, 196V, p. S6.
dlllXy I fig _ (6) Layendekkera, J. V,. "Tfrermodynamiai ofSeawaler," Marml Dekker. Netv Yurk. 1976,
(7) p. i%.
dl O) Reference (6>. p. 108.
C o m p a r i n g this with e q u a t i o n ( I ) , we see t h a t in a n e q u i l i b - (S> Home, R. A., "Marine Chemistry," Wiley-InterscioniK, New York, 1969, pp. 479-80.
(9) Marland, G.. Endeavour, N.S., 1,165 (1979).
r i u m s e a t h e d i s t r i b u t i o n of w a t e r c o n f o r m s t o a simple (10) Nash, L. K., "8foi<!hion.ettyr" Addison - Wesley, ReadiRf. MA. 1966, pp. 177-79.
B o l t z m a n n d i s t r i b u t i o n modified only b y t h e i n s e r t i o n of a (11! Blanck, K. F, J. CHEM. Ewe, &>> 637 (1983).
{12} Baehliuher,0., Amur. J. Phys... Si, 259 (1983).
Summer Employment Program Polymer Science
The Industrial Sponsors Group of the Ilivision of Polymer Chemistry of the American Chemical Society announces
a itew summer employment program. Outstanding junior are provided the opportunity to work in thefieSdof polymer science
with one of a select number of U.S.-based chemical companies.
Thefirstphase of the program involves a unique opportunity offered by the Plastics and Coatings Division of Mobay
Chemkai Corporation for the summer of 1984. The selected candidate will be sent to Uerdingen, West Germany for a
work/training assignment in the Research Laboratories of Bayer AG, Mobay's parent company. All transportation and lodging
expenses along with a monthly salary will be paid by Mobay.
Program announcements will be mailed to a large number of colleges and universities this fall. Interested students should
send a letter outlining their academic and personal interests and goals along with a.transcript or equivalent listing courses
and grades before February 1,1984toDr. G. E. Reinert, Mobay Chemical Corporation, Pittsburgh, PA 15205.
Additional industrial participants are currently being sought for ther summer of 1984. Program details will vary according
to the interests of the individual companies.

computer /erie/, 48
edited by
JOHN W. MOORE
Eastern Michigan University, Ypsilanti, Ml 4619?
Will Computers Replace TA's? Professors? Labs?

Should They?
A Symposium Report
Introduction
John W. Moore and Elizabeth A. Moore
Eastern Michigan University
Ypsilanti, Ml 48197
T h e n u m b e r a n d variety of applications of c o m p u t e r s in
chemical education have grown a t a n ever-in creasing pace
s i n c e t h e i n t r o d u c t i o n of t h e A i t a i r m i c r o c o m p u t e r i n1 9 7 6 .
I t is b e c o m i n g c o m m o n p l a c e for s t u d e n t s t o h a v e t h e i r o w n
computers, a n d most chemistry departments have micros
a v a i l a b l e f o r s t u d e n t s t o u s e .T h e r e h a s b e e n a t r e m e n d o u s
g r o w t h i n t h e n u m b e r of c o m p u t e r p r o g r a m s a v a i l a b l e f o r
instructional p u r p o s e s , a l t h o u g h t h e old b u g a b o o of re-in-
v e n t i n g t h e w h e e l i s still e v i d e n t . C o m m e r c i a l p u b l i s h e r s h a v e
p r o d u c e d e x t e n s i v e s e t s of l e s s o n s to c o v e r e n t i r e c o u r s e s , a n d
N S F - s u p p o r t e d p r o j e c t s like S E R A P H I M 1 c a n s u p p l y b o t h
p r o g r a m s a n d i n f o r m a t i o n a b o u t n e a r l y a l l s o u r c e s of i n -
s t r u c t i o n a! s o f t w a r e .
T h e r e f o r e , t h e t i m e s e e m s ripe for assessing w h e r e w e a r e

a n d m o r e i m p o r t a n t l y w h e r e w e o u g h t t o b e going i n t h i s field \tdrow
of c h e m i c a l e d u c a t i o n . Collectively w e h a v e b y n o w h a d Qfld -the. mat
enough experience t o a t least begin t o m a k e some j u d g m e n t s
a b o u t w h i c h applications of c o m p u t e r s a r e m o s t valuable a n d
a p p r o p r i a t e . W e c a n consider carefully h o w c o m p u t e r - b a s e d
i n s t r u c t i o n o u g h t t o affect o u r a p p r o a c h e s t o t h e subject
m a t t e r of c h e m i s t r y a n d t h e pedagogical a p p r o a c h e s w ec a n
t a k e t o o u r subject. W e c a n develop n e w ideas a b o u t h o w t o
u s e t h i s n e wt o o l , p a y i n g a t t e n t i o n i n t h i s p r o c e s s t o t h e r e s u l t s
of e d u c a t i o n a l research. W e c a n d o t h e s e t h i n g s , b u t for t h e
most part we have n o tbeen doing them, a n d we arein danger
o f g e t t i n g i n t o t h e s i t u a t i o n d e p i c t e d i n F i g u r e 1. A n e w t o o l
t h a t is n o t u s e d i n n o v a t i v e l y a n d i m a g i n a t i v e l y m a y s i m p l y Figure 1. Cartoon by M. Sancters, Stale University of New Yojk, College at Old
p e r p e t u a t e a n d a m p l i f y a l l t h a t is less t h a n s a t i s f a c t o r y w i t h Wsstbuiy end taken from "Margtnaiia," The Chronicle of Higher Education.
t h e o l d - f a s h i o n e d w a y of d o i n g t h i n g s . Reprinted with the kind permission of The Chronicle of Higher Education.
Copyright © 1983.
In h o p e s of o p e n i n g discussion of m a n y of t h e points listed
above, Project S E R A P H I M organized a symposium a t t h e Fall
1983 A C S National M e e t i n g in Washington, D C . Speakers is a p r o p o n e n t of i n s t r u c t i o n a l s i m u l a t i o n s ; J . J . L a g o w s k j
w e r e selected w i t h a n e y et o b r o a d coverage of various t y p e s is a n o l d h a n d in h a n d l i n g large f r e s h m a n c h e m i s t r y courses
o f c o m p u t e r a p p l i c a t i o n s : S t a n l e y S m i t h is a c o m m e r c i a l l y w i t h c o m p u t e r a s s i s t a n c e ; a n d D e r e k D a v e n p o r t is a devil's
p u b l i s h e d a u t h o r w i t h n e a r l y 2 0 y e a r s of e x p e r i e n c e i n t u t o r i a l advocate whose spicy c o m m e n t s c a n b e expected t o keep ev-
C A I ; A l l a n S m i t h is a f a c u l t y m e m b e r c h a r g e d w i t h t r a i n i n g e r y o n e else o n t h e i r toes. T h i s r e p o r t consists of m a n u s c r i p t s
c o l l e a g u e s i n a u n i v e r s i t y w h e r e e v e r y f r e s h m a n will h a v e a s u b m i t t e d b y t h e s p e a k e r s a n d a s u m m a r y of t h e p a n e l d i s -
c o m p u t e r t h i s y e a r ; S t a n l e y B u r d e n i s o n e w h oh a s d e v e l o p e d cussion t h a t closed t h e symposium. Speakers were charged
a n d t e s t e d a b a t t e r y of analytical e x p e r i m e n t s involving o n - a t t h e b e g i n n i n g of t h e s y m p o s i u m t o c o n s i d e r t h e c h a l l e n g e
l i n e d a t a c o l l e c t i o n a n d a n a l y s i s ; J e f f D a v i s is a j a c k - o f - a l l - m a d e i n a n e d i t o r i a l i n T H I S J O U R N A L l a s t s u m m e r (1):
trades with respect t o instructional technology; J o h n M o o r e
F u l f i l l m e n t o£ t h e t r u e p r o m i s e of t h e a p p l i c a t i o n of c o m p u t e r -
o r i e n t e d h i g h technology t o e d u c a t i o n r e q u i r e s a n u n c o m m o n
' Project SERAPHIM—A Model System for Dissemination of Mi- q u a l i t y of t h o u g h t a n d b r e a d t h of vision. S u c h vision implies high
crocomputer-Based Instructional Materials, J. W. Moore and J. J. La- costs a n d h i g h risks, b u t t h e s t a k e s a r e s o high t h a t t h e y w a r -
gowski, principal Investigators; sponsored by NSF-OISE, SED 81-07568. r a n t — i n d e e d d e m a n d — a n answer formulated by t h e m o s t creative
Opinions expressed in this article are not necessariiy those of NSF. m i n d s we h a v e available.

The title of the symposium was made provocative in order to A c o m p u t e r is n o t a l a b .
attract the attention of many who have not yet considered the
Y o u can d o a simulated laboratory experiments on the com-
promise or the limitations of computers. We hope that many
p u t e r , b u t t h a t isn't real laboratory work. Y o u can't b u r n your
who read this article will be challenged to take on some of the
fingers o n h o t glass or discover w h a t s o m e t h i n g smells like o n
costs and risks inherent in experimenting with a new medium
of instruction, and will contribute to the discussion we hope a computer. And remember,
the symposium began. The greater the number of creative A c o m p u t e r is n o t a book.
minds applied to the problems of chemical education, the
better. There are certainly plenty of intellectual challenges It is easy t o tell t h e difference b e t w e e n a c o m p u t e r a n d a
for those who attempt to apply computers to the task of b o o k — t h e y are very different media. A c o m p u t e r requires new
teaching. pedagogical approaches.
T h e e f f e c t i v e n e s s of c o m p u t e r - a s s i s t e d i n s t r u c t i o n , a s w i t h
all t y p e s of i n s t r u c t i o n , d e p e n d s o n t h e c o n t e n t , t h e w a y i t is
Teaching with a Microcomputer: The Current p r e s e n t e d , a n d t h e i n s t r u c t i o n a l design. S t u d e n t s s e e m t o like
working a n d learning with a c o m p u t e r (5), a n d , although
Status and What's in Store for the Future s t u d i e s a r e still limited, t h e available d a t a suggests t h a t C A I
Stanley G. Smith is a n e f f e c t i v e t e a c h i n g t o o l (8,9,10). Thus there appear to
University of Illinois b e m a n y c i r c u m s t a n c e s u n d e r w h i c h a c o m p u t e r can r e p l a c e
Urbana.IL 61801 a professor.
W h e n c o n s i d e r i n g t h e c u r r e n t s t a t u s of c o m p u t e r u s e in Should Computers T e a c h ?
t e a c h i n g a n d w h a t ' s i n s t o r e f o r t h e f u t u r e o n e c a n a s k : Can
p r o f e s s o r s b e r e p l a c e d ? should t h e y b e r e p l a c e d ? a n d will t h e y If a c o m p u t e r c a n t e a c h t h e s a m e m a t e r i a l in less t i m e a n d
b e r e p l a c e d ? T o a n s w e r t h e s e q u e s t i o n s , i t is n e c e s s a r y t o with greater long-term retention by students t h a n couid b e
define w h a t a c o m p u t e r c a n d o for b o t h t h e professor a n d t h e a c h i e v e d b y a t e a c h e r , t h e n t h e r e is a r e a s o n a b l e a r g u m e n t for
student. T h e ability of a computer to p u t t e s t a n d graphics replacing the teacher.
on t h e screen, accept a n d interpret student input, store a n d
A n y o n e w h o cafl b e r e p l a c e d b y a c o m p u t e r s h o u l d b e .
recall data, a n d d o calculations c a n b e m o l d e d into a n inter-
active instructional system (2). T h e major limitation on t h e H o w e v e r , we should also recognize t h a t
a b i l i t y o f s u c h a s y s t e m in i n s t r u c t i o n is t h e i m a g i n a t i o n o f t h e
lesson designers a n d p r o g r a m m e r s . Typical applications (3) A c o m p u t e r is a toot:
good t e a c h e r s cannot be replaced by a computer.
include tutorial dialogs, simulations of e x p e r i m e n t s , practice
p r o b l e m s , d a t a collection, control of e x p e r i m e n t s , a n d A c o m p u t e r will o n l y r e p l a c e t h o s e T A ' s , professors, a n d l a b s
c h e m i c a ! g a m e s (4). T h e s e t y p e s of p r o g r a m s h a v e b e e n u s e d t h a t a r e l i m i t e d t o t h o s e t y p e s of t h i n g s t h a t c a n b e d o n e
t o s u p p l e m e n t l e c t u r e s ( 5 ) ,p r o v i d e interactive h o m e w o r k , a n d b e t t e r o n a c o m p u t e r . A g o o d t e a c h e r will n o t b e r e p l a c e d b y
p r e p a r e s t u d e n t s for l a b o r a t o r y work (6, 7). a c o m p u t e r ; a g o o d t e a c h e r will u s e t h e c o m p u t e r t o b e e v e n
b e t t e r . T h e o b j e c t i v e is n o t t o r e p l a c e a n y b o d y , b u t t o d o a
Can Computers Teach? b e t t e r j o b of t e a c h i n g . T h e c o m p u t e r , a s d e m o n s t r a t e d b y
B e c a u s e of its h i g h l y i n t e r a c t i v e n a t u r e a n d t h e ability t o e x p e r i m e n t s , d o e s serve t h a t role.
do animations, the instructional approach used with a com-
Wlft Computers Teach?
p u t e r c a n a n d s h o u l d b e v e r y d i f f e r e n t from t h a t i n a t e x t b o o k
o r a l e c t u r e . F o r e x a m p l e , i n s t e a d of e x p l a i n i n g a p h e n o m e n o n The extent to which computers will be used for teaching is
t h e c o m p u t e r c a n ailow t h e s t u d e n t t o experience it t h r o u g h critically dependent on the cost of the hardware and the
simulations t h a t are designed to illustrate t h e important availability of suitable programs. The rapid proliferation of
features. W h e n coupled with tutorial material designed to relatively inexpensive microcomputers that have the capa-
assure that t h e student understands the simulation and bility of supporting high quality instructional material is
suitable practice problems t h e computer becomes a new kind making CAI generally available {11). In 1975 one had to have
of i n s t r u c t i o n a l m e d i u m t h a t s u p p l e m e n t s t h e a p p r o a c h e s access to a powerful mainframe computer just to try to do
available in printed matter, discussions, a n d laboratory work. something with computers in instruction. In 1.976 if you could
In a textbook, for example, words m a y be used to describe put together an Altair kit you could have your own computer
w h a t h a p p e n s if y o u c o m p r e s s a g a s i n a c y l i n d e r . T h e p r o c e s s for a few thousand dollars. Now, in 1983, for a few hundred
can also b e described in lecture along with pictures. B u t o n a dollars you can purchase a computer that is able to support
computer each student can, through a simulation, push the a wide range of instructional techniques. Furthermore, it is
p i s t o n i n a n d o u t a n d collect d a t a on various pressures a n d likely that in the near future students will have their own
volumes. T h e experiments can be monitored by'the computer
a n d i n d i v i d u a l i z e d h e l p p r o v i d e d t o t h e s t u d e n t o n l y if
needed. Even with something as simple as balancing equations
t h e c o m p u t e r c a n h e l p b y giving a t a b l e w i t h t h e n u m b e r of
a t o m s of e a c h of t h e e l e m e n t s in t h e r e a c t a n t s a n d t h e p r o d - U s * Ui« k e y s : * - * 1 2 3 « 5 6 7
ucts. As you start to balance the equation computer updates to balance t h i s •quation.
the table dynamically so you can see what balancing an
e q u a t i o n r e a l l y m e a n s ( F i g . 2). I t is c l e a r t h a t : HjO
R28O|| * H*0tt - +
A c o m p u t e r is n o t a book,
A b o o k is p a s s i v e ; a c o m p u t e r is i n t e r a c t i v e . I t is a l s o c l e a r
E lsx«nt Rnactants Product*
H 3 2
that:
S 1 1
A c o m p u t e r is n o t & l e c t u r e . 0 3 S
Ha 1 2
Lectures t e n d to be passive. A n d :
Figure 2. Computer display during equal ion-balancing drili. Note fhe tabte of
A c o m p u t e r is n o t a b o o k .
mimber of atoms of each type. This is updated as each coefficient is en-
B o o k s h a v e lots of t e x t . C o m p u t e r s h a v e a n i m a t i o n s . Also, tered.

computers, just as they used to have their own slide rules. m o n i t o r , a disk drive, a n d software, will b e sold t o s t u d e n t s
But, will we have software for ail of those millions of com- for $1,000 w h i c h c a n b e f i n a n c e d .
puters? In 1980 there was hardly any software for teaching A n i m p o r t a n t p a r t of D r e x e l ' s p r e p a r a t i o n f o r u s i n g m i -
chemistry on a microcomputer. Now, in August 1983, John crocomputers in the undergraduate curriculum has been a
Moore and I have figured out that there are probably about faculty d e v e l o p m e n t effort m a d e possible b y a $2.8 million
400 individual microcomputer programs for use in teaching grant from t h e P e w Foundation, administered by t h e Glen-
chemistry and the curve is going up very rapidly (Figure 3). m e d e T r u s t . S o m e of t h e p r o j e c t s { w o r k s h o p s , m i c r o c o m p u t e r
The ultimate impact of the computer on instruction de- s e m i n a r s , s u p p o r t for c o u r s e w a r e a n d software d e v e l o p m e n t ,
pends on how it is used. If the existing course content and etc.) a r e described elsewhere (12,14).
instructional techniques are simply programmed into the
computer, then it will become just another way to do the same Using Microcomputers in Chemistry
thing. Unfortunately, a reasonable prediction for the future A recent issue of the Computers in Chemical Education
(defined as the the next two years) is NewsleMer contained a description of some projected uses of
microcomputers in our chemistry curriculum (15). Because
11 more titaation simulations microcomputers will be phased in class-by-class over the next
57 more nomenclature drills few years, most of our thought so far has been on how to use
113 more multiple-choice quizzes
1 new way to use computers to microcomputers in freshman chemistry.
help students learn The most immediate use for micros will be of the standard
applications packages provided with the system: word-pro-
The challenge for teachers who do not want to be replaced by cessing, an electronic spreadsheet, and graphics capabilities.
a microcomputer is not just to write more nomenclatural drilk For example, we are considering requiring all general chem-
or multiple choice quizzes but to develop ways to use this new istry students to write up portions of their lab reports using
tool to enhance the content and quality of their courses (7) and the word-processor, thus enabling us to ask for revisions of
to find new ways to help students learn chemistry. both the scientific content and t h e prose of the report. Ob-
viously insisting on good writing as well as good science re-
quires careful thought and commitment on the part of both
Suppose Every General Chemistry Student had a faculty and teaching assistants.
Microcomputer... Another application I have been interested in is the use of
Allan L. Smith electronic spreadsheets as a computational tool in general
Drexel University chemistry. Much of the content of today's general chemistry
Philadelphia. PA 19104 course involves calculations—and it should remain that way.
While there are many wonderful chemical ideas whose essence
T h e s u p p o s i t i o n in t h e title of this piece will d e s c r i b e reality can be stated without using mathematics—molecular struc-
for a l l 1 8 0 0 e n t e r i n g f r e s h m e n a t D r e x e ! i n t h e a c a d e m i c y e a r ture, for example-—many of these ideas can profitably be
s t a r t i n g i n t h e fall o f 1 9 8 3 a n d , t h u s , f o r t h e 1 2 0 0 s t u d e n t s elaborated with well-chosen computations.
enrolled in general c h e m i s t r y . T h e decision t o r e q u i r e m i - Ideally solving problems, for example those involving
crocomputer ownership wasnot the Chemistry Department's aqueous equilibria, requires t h a t students be aware of what
b u t w a g m a d e a f t e r s t u d y a n d p l a n n i n g a t t h e u n i v e r s i t y Jevel chemical species are present and what chemical reactions are
(12). I chaired t h e faculty c o m m i t t e e t h a t was charged with taking place. Then the student can "set up the problem," that
t h e r e s p o n s i b i l i t y of e x p l o r i n g p r e s e n t n e e d s f o r a n d p o s s i b l e is, find a logical structure that makes the solution straight-
uses of a student-owned microcomputer in t h e undergraduate forward. Once this is done, a linear sequence of instructions
c u r r i c u l u m , developing a s e t of specifications for t h e p e r s o n a ! can be given to any calculating device to find the answer.
microcomputer, and identifying commercially available mi- Unfortunately, most people don't think in a sequential man-
c r o c o m p u t e r s t h a t m e t or exceeded.these specifications. A n ner, and the structure imposed on the problem by the linear
abridged version of t h e M i c r o c o m p u t e r Selection C o m m i t t e e ' s medium of a programmable calculator with its single-line
r e p o r t i s b e i n g p u b l i s h e d e l s e w h e r e {13). T h e c o m p u t e r s e - display often hides from students the key relationships be-
l e c t e d is a n e w A p p l e p r o d u c t n o t o n t h e m a r k e t a s of t h i s tween quantities and procedures so important in under-
w r i t i n g ( S e p t e m b e r , 1983). I t o p e r a t e s w i t h a 16-bit m i c r o - standing the problem.
p r o c e s s o r a n d h a s a m i n i m u m of 6 4 K b y t e of u s e r - a v a i l a b l e
R A M . T h e computer system, including the C P U , video Enter the stand-alone personal computer and an electronic
spreadsheet program like VisiCalc* (a trademark that is an
abbreviation for "visible calculator"). The spreadsheet or-
ganizes numeric data in tabular form and allows the use of this
data to calculate new rows or columns. If a value in the table
is changed, all other values that depend on the first one are
immediately recalculated and the table on the screen is
updated. Rows and columns can be labelled to show clearly
CheMistry PrograHs what they contain, it is easy to enter or change numeric values,
and once a useful table has been devised it can be saved as a
template for later use.
90*
These spreadsheet features are quite attractive for many
typica! general chemistry calculations. The computational
capacities of the typical spreadsheet eliminate t h e need for
f>ro«r*HS ad-hoc approximations along the way to solutions of even
complex equilibrium problems. For example, I have developed
a spreadsheet template to solve for equilibrium concentrations
of the general chemical reaction
oA + 6B = cC + dD
'•0 '82 >8H
given initial concentrations and the equilibrium constant. A
Figure 3, Graph of number of Instructional programs versus time. Data from special case of this template solves the weak acid dissociation
S. G. Smith and J. W. Moore. problem. The immediate updating of the whole sheet after

changing an initial concentration or an extent of reaction s t r a t e t i t r a t i o n c u r v e s f r o m a v a r i e t y of t i t r a t i o n s y s t e m s . I t
permits "what if" exploration on the student's part, which ia h a s also b e e n u s e d effectively w i t h high school s t u d e n t s . In
quite useful when he or she is trying to understand how a n a l y t i c a l c h e m i s t r y t h e t i t r a t o r is u s e d in a n e x p e r i m e n t t h a t
changing the initial concentration of the conjugate base in a a t t e m p t s t o give s t u d e n t s s o m e i n t r o d u c t o r y e x p e r i e n c e w i t h
buffer solution might affect the pH, for example. e x p e r i m e n t a l design. S t u d e n t s are given t h r e e commercial
The first uses of microcomputers in general chemistry were a n t a c i d s a n d a r e a s k e d to d e t e r m i n e t h e acid neutralizing
as programmable calculators: the "let's write a BASIC pro- c a p a c i t y o f e a c h . D i r e c t i o n s for a s i m i l a r e x p e r i m e n t a r e
gram" syndrome. It would be a major mistake, however, to a v a i l a b l e c o m m e r c i a l l y a n d in t h e l i t e r a t u r e , b u t t h e s t u d e n t s
view today's personal computer as a glorified calculator. A h a v e n o initial k n o w l e d g e of this; t h e y m u s t rely o n then- o w n
calculator displays a single line of 10-20 characters, while a ingenuity in designing and carrying out the procedure. T h e y
microcomputer has a screen which holds two-thirds as many m u s t work alone b u t are encouraged to use t h e literature a n d
lines as a piece of paper. A calculator has a numeric keypad, m a k e a p p r o p r i a t e c i t a t i o n s i n t h e i r final r e p o r t . N o s p e c i f i c
while a computer has a full keyboard and often other inter- d i r e c t i o n s a r e given b u t a list of q u e s t i o n s l e a d s t h e s t u d e n t
active devices (e.g., a "mouse" for moving a cursor on the to t h i n k a b o u t some of t h e practical details of designing ex-
screen). Microcomputer programming languages are struc- p e r i m e n t s . Answers are h a n d e d in prior t o laboratory, a n d t h e
tured, powerful, and often use effectively the full graphics instructor c o m m e n t s on these individually. T h i s assignment
capability of the screen, whereas calculator languages are is m a d e while t h e s t u d e n t s a r e s t u d y i n g a c i d - b a s e t i t r a t i o n
rather limited. It behooves us to expend some thought, effort, curves. Generally, the students decide to m a k e titration curves
and creativity in developing ways to use these new features of e a c h of t h e i r s a m p l e s a n d u s e t h e s e t o d e t e r m i n e w h a t
effectively. e n d p o i n t is a p p r o p r i a t e . If d e s i r e d , t h e s t u d e n t s c a n a l s o b e
a s k e d t o i d e n t i f y s o m e of t h e m a j o r s p e c i e s b e i n g t i t r a t e d by
At Drexel we have been working to capitalize on the op- identifying their p K ' s . Since the students normally discover
portunities personal computers afford. By this time next year t h a t t h e y m u s t dissolve t h e samples in acid, they are led to
we will also be able to report on the results of our students* consider using the back-titration technique. This encourages
creative applications of the new tools they all will have. t h e m to think a b o u t w h a t species are formed w h e n t h e acid
is a d d e d a n d w h i c h a r e b e i n g t i t r a t e d . W h i l e a l l o f t h i s c o u l d
be done manually, running the titrations and plotting the ti-
Improving Undergraduate Experiments with tration curves using the computer-controlled titrator speeds
On-line Microcomputers t h e process greatly. S t u d e n t s are a s k e d t o t a k e sufficient d a t a ,
d o t h e a p p r o p r i a t e statistics, a n d p r e s e n t t h e r e s u l t s in a n
Stanley L. Burden appropriate fashion to support a n y conclusions they draw.
Taylor University After s o m e d i s c u s s i o n of f o r m a t s , t h e s t u d e n t s a r e a s k e d t o
Upland, IN 46989
r e p o r t r e s u l t s a s if t h e y w e r e b e i n g s u b m i t t e d f o r p u b l i c a t i o n .
F r o m one to t h r e e 3-hr laboratory periods are required, d e -
D u r i n g the past several years, assisted by an N S F L O C I
p e n d i n g o n h o w m u c h direction t h e i n s t r u c t o r chooses t o give
grant, we have been developing software, h a r d w a r e , a n d
the students.
c o u r s e w a r e t o use m i c r o c o m p u t e r s o n - l i n e in t h e u n d e r g r a d -
u a t e c h e m i s t r y l a b o r a t o r y . T h e p r i m a r y goal of t h e s e s y s t e m s
is t o i n c r e a s e s t u d e n t s ' p r o f i c i e n c y i n t h e l a b o r a t o r y . T h i s is P r i n c i p l e s t h a t a r e b r o u g h t t o t h e s t u d e n t s ' a t t e n t i o n in a
achieved by permitting the s t u d e n t to perform functions t h a t n e w or different way as t h e y design a n d carry o u t their ex-
would be inconvenient or too time-consuming to perform p e r i m e n t s i n c l u d e : (a) l i t e r a t u r e s e a r c h i n g ; (b) s a m p l e p r e p -
m a n u a l l y in n o r m a l l a b o r a t o r y t i m e b l o c k s . a r a t i o n ; (c) b a c k t i t r a t i o n ; ( d ) u s e o f t i t r a t i o n c u r v e s f o r s e -
W e c h o s e s y s t e m s t h a t s p a n a v a r i e t y of e x p e r i m e n t a l l e c t i o n o f e n d p o i n t , c h o i c e of i n d i c a t o r , a n d / o r i d e n t i f i c a t i o n
techniques and principles. W e tried to minimize sample of t h e s p e c i e s b e i n g t i t r a t e d ; (e) u s e o f s m a l l - s c a l e p r e l i m i n a r y
p r e p a r a t i o n t i m e , k e e p t h e t i m e p e r t r i a l s h o r t ( s o if a m i s t a k e runs to determine general behavior a n d appropriate sample
was m a d e t h e trial could be easily r e p e a t e d ) , a n d choose ex- s i z e ; (f) s t a t i s t i c a l a n a l y s i s ; a n d ( g ) r e p o r t i n g .
periments in which a u t o m a t i o n was really needed. T h e s e c o n d major on-line s y s t e m assists s t u d e n t s in u s i n g
Specific proficiencies t h a t we focus o n include e x p e r i m e n t a l i o n s e l e c t i v e e l e c t r o d e s . T h e s y s t e m is a l s o u s e d i n o u r S c i -
d e s i g n , i n t e r p r e t a t i o n of d a t a , a n d r e p o r t i n g . T h e s e a r e in entific I n s t r u m e n t a t i o n c o u r s e after d i s c u s s i n g c o n c e p t s of
a d d i t i o n t o t h e m o r e c o m m o n l a b o r a t o r y t e c h n i q u e skills. e x p e r i m e n t a l design such as t h e " p a i r e d - d a t a " a n d " t w o -
F r e q u e n t l y , e x p e r i m e n t a l design a n d i n t e r p r e t a t i o n of d a t a g r o u p " d e s i g n s . I n o n e of t h e p r o j e c t s , s t u d e n t s a r e a s k e d t o
proficiencies a r e less well-developed in u n d e r g r a d u a t e labo- design a n d carry out a set of experiments to compare analyses
ratory experiments because inordinately long time blocks are by multiple s t a n d a r d additions with those using t h e direct
n e e d e d to collect a n d analyze sufficient d a t a to give statisti- c a l i b r a t i o n c u r v e a p p r o a c h . S t u d e n t s m u s t d e c i d e w h i c h of
cally m e a n i n g f u l r e s u l t s . U s e of o n - l i n e m i c r o c o m p u t e r s y s - t h e t w o e x p e r i m e n t a l d e s i g n p r o c e d u r e s is m o s t a p p r o p r i a t e
t e m s can improve this situation significantly. for t h i s p r o b l e m a n d t h e n s e t u p t h e i r e x p e r i m e n t s t o u s e i t .
For multiple standard additions the same Sargent constant-
A p p l i c a t i o n s for w h i c h on-line s y s t e m s h a v e b e e n d e v e l o p e d
r a t e b u r e t a s is u s e d i n t h e c o m p u t e r - c o n t r o l l e d t i t r a t o r d e -
o r a r e i n t h e p r o c e s s o f b e i n g d e v e l o p e d i n c l u d e (a) c o m -
l i v e r s a u s e r - s p e c i f i e d n u m b e r of a l i q u o t s o f s t a n d a r d s o l u t i o n
puter-controlled titrations; (b) computer-assisted generation
into an unknown. T h e computer then calculates the concen-
of c a l i b r a t i o n c u r v e s a n d d a t a l o g g i n g f o r u s e w i t h i o n - s e l e c t i v e
t r a t i o n of t h e u n k n o w n a f t e r e a c h a d d i t i o n a n d a v e r a g e s t h e
e l e c t r o d e s ; (c) c o m p u t e r - c o n t r o l led m u l t i p l e s t a n d a r d a d d i -
r e s u l t s . T h i s s a m e s y s t e m c a n b e u s e d to e v a l u a t e v a r i o u s
tion a n a l y s i s using ion-selective electrodes; (d) c o m p u t e r -
i o n - s e l e c t i v e e l e c t r o d e s b y u s i n g i t to d e t e r m i n e e l e c t r o d e
a s s i s t e d l o g g i n g a n d a n a l y s i s of g a s c h r o m a t o g r a p h i c d a t a f o r
slope or e l e c t r o d e r e s p o n s e t i m e u n d e r v a r y i n g c o n d i t i o n s .
studying t h e stepwise kinetics of a reaction; (e) c o m p u t e r -
T h e s e are experiments t h a t would be extremely time-con-
a s s i s t e d l o g g i n g , p l o t t i n g , a n d a n a l y s i s of s p e c t r o p h o t o m e t r i c
suming and tedious to run by manual methods.
d a t a u s e d in a L i n e w e a v e r - B u r k a n a l y s i s of e n z y m e k i n e t i c s
d a t a ; a n d (f) l o g g i n g t e m p e r a t u r e a n d p y r o n o m e t e r d a t a f o r
A t h i r d on-line s y s t e m assists s t u d e n t s in p r e p a r i n g a series
solar collector performance studies. F o r brevity, we describe
of s t a n d a r d s o l u t i o n s . I t t h e n a u t o m a t i c a l l y l o g s d a t a f r o m a n
o n l y t w o of t h e s e a p p l i c a t i o n s in d e t a i l . E m p h a s i s will b e
ion-selective electrode i m m e r s e d in e a c h s t a n d a r d a n d m a k e s
p l a c e d o n t h e u s e of t h e s y s t e m s r a t h e r t h a n t h e d e t a i l s of t h e
a r e a l - t i m e p l o t of millivolts v e r s u s log c o n c e n t r a t i o n . T h e
systems themselves.
s t u d e n t t h e n s e l e c t s e i t h e r a l i n e a r o r c u b i c fit t o t h e d a t a a n d
T h e c o m p u t e r - c o n t r o l l e d t i t r a t o r is u s e d i n s e v e r a l c o u r s e s . a r e - s c a i e d , l a b e l l e d p l o t is a u t o m a t i c a l l y m a d e o f t h e d a t a
I n f r e s h m a n c h e m i s t r y it i s u s e d b y t h e i n s t r u c t o r t o d e m o n - with t h e fitted curve. T h e user t h e n merely immerses t h e

electrodes in the samples to be analyzed. The potential is eventually into discouragement when students have not re-
automatically logged and the concentration is computed from sponded to having t h a t tool thrust upon t h e m at every turn.
the fitted equation and printed. In this system, as wel! as the In T a b l e 1 i have included some c o m m e n t s regarding the ad-
multiple standard addition system, user attention is mini- v a n t a g e s a n d d i s a d v a n t a g e s of t h e v a r i o u s m e d i a listed.
mized during the typical 40-150 s equilibration period of the W e are seeing t o d a y a wave of excitement generated by t h e
electrode with each new sample since the system will not log availability of r e m a r k a b l y powerful p e r s o n a l m i c r o c o m p u t e r s .
potentials until equilibrium is reached. This frees the user to This excitement extends throughout the business a n d edu-
do other things during this interval. This same system is used c a t i o n a l world t o s a y n o t h i n g of t h o s e e n g a g e d in technological
in a separate experimental design project in which the stu- a p p l i c a t i o n s a n d e n t e r t a i n m e n t . T h e r e is n o d o u b t t h a t i n t h e
dents are asked to evaluate the reproducibility of the cali- y e a r s a h e a d t h i s e x c i t e m e n t w i l l w e a r t h i n a n d m a n y of t h e
bration curve for a given electrode. For this they discover that rogy p r o m i s e s will n o t b e realized. N e v e r t h e l e s s w e c a n easily
they should use the "paired-data" design in contrast to the r e c o g n i z e e d u c a t i o n a l a p p l i c a t i o n s f o r w h i c h t h e c o m p u t e r is
"two-group" design. The "two-group" design is more appro- ideal a n d provides t h e b e s t tool to accomplish our goals. In
priate for the previously mentioned problem of comparing the o t h e r a p p l i c a t i o n s , a m a r r i a g e of t h e c o m p u t e r w i t h o t h e r
multiple standard additions method with the direct calibra- m e d i a will b e f a r m o r e e f f e c t i v e for i n s t r u c t i o n t h a n e i t h e r t h e
tion curve method. computer or the audio-visual m e d i u m alone.
In general, we have found that when properly used, these O n e of t h e m o s t s t r i k i n g e d u c a t i o n a l a p p l i c a t i o n s f o r w h i c h

on-line systems significantly improve the experiences un- t h e c o m p u t e r i s i d e a l l y s u i t e d i s t h e g e n e r a t i o n of o b j e c t i v e
dergraduate students can have in the chemistry laboratory. examinations, scoring examinations a n d recording scores,
Students' laboratory experiences are closer to the situations a n a l y s i s of t h e e x a m i n a t i o n i t e m s , a n d m a n i p u l a t i o n a n d
they will encounter in the real world, and students can be a n a l y s i s of s t u d e n t scores a n d g r a d e s . W h i l e it is clear t h a t
made to think about experimental design, interpretation of subjective essay a n d problem-solving tests m u s t be designed
data, and preparation of adequate reports much more than a n d graded by the instructor, we also should recognize t h a t
they would in a conventional laboratory course. t h e t i m e h a s c o m e w h e n t h e r e is n o r e a s o n f o r a n i n s t r u c t o r
t o p u t t o g e t h e r a l l t h e i t e m s for a n o b j e c t i v e e x a m , g r a d e t h e m ,
a n d analyze s t u d e n t a n d class performance by hand. T r e -
Let the Medium Fit the Message m e n d o u s savings in t i m e o b t a i n e d b y h a v i n g t h e s e j o b s d o n e
b y a c o m p u t e r a r e o b v i o u a . P e r h a p s l e s s o b v i o u s is t h e a d d i -
Jeff C. Davis, Jr.
tional information about exam items and about students that
University of South Fiorida b e c o m e s a v a i l a b l e . E q u a l l y v a l u a b l e a r e t h e n e w m e a n s for
Tampa, FL 33620
communication between instructor and student. Table 2
C o n s c i e n c i o u s t e a c h e r s h a v e l o n g u s e d a v a r i e t y of s u p - s u m m a r i z e s some of t h e aspects of m a n a g i n g objective ex-
p l e m e n t a l tools t o s t i m u l a t e t h e i r s t u d e n t s a n d t o c l a r i f y t h e a m i n a t i o n s . T w o d e c a d e s of d e v e l o p m e n t m a k e i t c l e a r t h a t
c o n c e p t s t h e y a r e t e a c h i n g . T a b l e I Hats s o m e of t h e m e d i a t h e r e is t r e m e n d o u s v e r s a t i l i t y i n w h a t k i n d of c o m p u t e r s w e
m o s t u s e d in t h e c l a s s r o o m t o s u p p l e m e n t t h e s p o k e n w o r d can use, w h e t h e r we develop printed e x a m i n a t i o n s or use the
a n d c h a l k b o a r d i l l u s t r a t i o n . M a n y of t h e s e h a v e p r o v e n p a r - c o m p u t e r terminal d i r e c t l y , w h e t h e r e x a m s a r e i n d i v i d u a l i z e d
t i c u l a r l y useful for s u p p l e m e n t a r y i n s t r u c t i o n o u t s i d e t h e for e a c h s t u d e n t , w h e t h e r responses are multiple-choice or not,
c l a s s r o o m a s well. I t s h o u l d s e e m o b v i o u s t h a t a p a r t i c u l a r a n d w h a t k i n d of r e p o r t s a r e g e n e r a t e d f o r t h e i n s t r u c t o r a n d
t e c h n o l o g y is n o t n e c e s s a r i l y b e s t s u i t e d f o r e v e r y e d u c a t i o n a l for t h e s t u d e n t . W h i l e c o m p l e t e versatility r e q u i r e s imagi-
g o a l o r s i t u a t i o n . Y e t m o s t of u s h a v e e x p e r i e n c e d t h e e u p h o r i a n a t i v e a n d s o p h i s t i c a t e d p r o g r a m m i n g skills, m o r e a n d m o r e
a n d e x c i t e m e n t of d i s c o v e r i n g a v a l u a b l e n e w tool o n l y t o slip t o o l s a r e b e c o m i n g a v a i l a b l e for t h e n o n - p r o g r a m m i n g
teacher.
Tabfe 1. Instructional Media I n m a n y o t h e r applications t h e c o m p u t e r clearly is a useful

t o o l . H o w e v e r , it o f t e n is n o t a a e f f e c t i v e b y i t s e l f a s w h e n
Technique Advantages Disadvantages m e r g e d w i t h o t h e r a u d i o - v i s u a l t e c h n i q u e s . W e h a v e c o m e to
Clarity, detail Static, remote a p p r e c i a t e t h e fact t h a t tutorial lessons can b e p r o g r a m m e d
Siides
equipment w i t h c o n s i d e r a b l e f l e x i b i l i t y for i n d i v i d u a l s t u d e n t d i f f e r e n c e s
Overhead Projection Clarity, detail' Static o f u n d e r s t a n d i n g . T h e l i m i t a t i o n s to a c c o m p l i s h i n g t r u e
Slide/audio Cassette as above plus True tutorial t u t o r i a l i n s t r u c t i o n a r e less in t h e c a p a b i l i t y of t h e c o m p u t e r
sound difficult t h a n in t h e a b i l i t y of t h e a u t h o r t o d e s i g n a t r u l y effective
Film as above plus Sequences fixed, instructional plan.
motion equipment
W i t h m a n y topics, h o w e v e r , t h e m o s t serious limitation is
Film Loop Motion, short as above, no sound
Static t h a t t h e c o m p u t e r c a n n o t p o r t r a y r e a l t h i n g s a s Well a s p h o -
Microfiche/Cassette Size, semi-
interactive t o g r a p h s , film, or v i d e o t a p e . O n typical low-cost m i c r o c o m -
Videocassette Clarity, motion, Sequences fixed p u t e r s , e v e n t h e b e s t h i g h resolution d i s p l a y is o n l y a n a p -
sound p r o x i m a t e r e p r e s e n t a t i o n in w h i c h i m p o r t a n t a s p e c t s a n d
Computer Interactive, liata, Visual i imitations d e t a i l s m a y b e l o s t . A n i m a t i o n of m o t i o n is d i f f i c u l t a n d o f t e n
computation unrealistic.
Computer-Video as above plus Speed of visual T h e m o s t o b v i o u s e x a m p l e s of t h i s v i s u a l l i m i t a t i o n a r e t h e
visual access p o r t r a y a l of a c t u a l s u b s t a n c e s , r e a c t i o n s , a n d t h e m a n i p u l a -
Table 2. Objective Exams on Computers
Exam Types Exam Formats Exam Construction Computer Advantages
Fill-in • Computer-Printed Forms: Response forms • Select items randomly from stored Time and Effort Savings
Response batch scored by computer. question-answer sets. Fast Response for
Student
Multiple-Choice • On-Screen Query: Typerf-in response • Generate random or sequential Flexibility
Response scored and stored by computer. numbers for data in items. Instructor-Student
Feedback
Item Analysis

t i o n of l a b o r a t o r y a p p a r a t u s . T h i s l i m i t a t i o n is easily over- chemist/programmer and on the computer. T h e situation to
come, however, by utilizing videocassette or videodisk m a t e r i a l b e s i m u l a t e d m u s t be well e n o u g h u n d e r s t o o d t h a t m o d e l
o n t h e s a m e m o n i t o r as a n i n t e g r a l p a r t of t h e c o m p u t e r - equations are available a n d provide a reasonable approxi-
controlled tutorial program. T h i s technique permits the dis- m a t i o n of r e a l i t y . T h e s i t u a t i o n c h o s e n f o r s i m u l a t i o n s h o u l d
play of "live" action w h e n n e e d e d in t h e lesson, including re- b e o n e w h e r e r e a l - l i f e e x p e r i m e n t s a r e t o o d a n g e r o u s , too s l o w ,
p e a t viewing of t h e a p p r o p r i a t e scenes as d e t e r m i n e d by stu- t o o fast, t o o c o m p l e x , or t o o e x p e n s i v e for t h e s t u d e n t t o d o .
d e n t responses to questions in the program. I n s o m e c a s e s , s u c h a s d i s p l a y of e l e c t r o n d e n s i t i e s f r o m
T a b l e 3 s u g g e s t s s o m e of t h e k i n d s of t u t o r i a l p r o g r a m s in q u a n t u m calculations, there may not even be a real experi-
which interactive computer programming combined with ment that could produce the simulated output. T h e pro-
video illustrations c a n be m o s t effective. F r o m t h e s t a n d p o i n t g r a m m e r m u s t m a k e s t u d e n t / c o m p u t e r i n t e r a c t i o n s flexible
of s p e e d of a c c e s s a n d v o l u m e of v i d e o m a t e r i a l a v a i l a b l e , i t a n d convenient—the c o m p u t e r should not get in the way, but
is c l e a r t h a t v i d e o d i s k o f f e r s t h e g r e a t e s t p o t e n t i a l . T h e r e is rather m u s t be an essentially t r a n s p a r e n t m e d i u m t h a t lets
no reason, however, why a n y instructor should hesitate to t h e s t u d e n t focus o n c h e m i s t r y a n d c h e m i c a l m o d e l s . Finally,
d e v e l o p v i d e o m a t e r i a l s u i t a b l e for h i s o r h e r n e e d s a n d t o the c o m p u t e r m u s t calculate rapidly enough so t h a t almost
utilize it in t u t o r i a l p r o g r a m m i n g via v i d e o c a s s e t t e u n t i l t h e i n s t a n t a n e o u s results c a n be g o t t e n from realistically c o m p l e x
costs for videodisk p r o d u c t i o n b e c o m e m o r e realistic. m o d e l s . C u r r e n t l y t h i s l a s t is o f t e n a s t u m b l i n g b l o c k , b u t
faster, more powerful microprocessors are j u s t down t h e road,
a n d n u m e r i c c o p r o c e s s o r s , s u c h a s t h e 8087 n o w a v a i l a b l e for
I B M Personal C o m p u t e r s , can achieve considerable speed-up
Exploring Chemistry's Mathematical Models with i n c a s e s w h e r e o v e r a l l r e s p o n s e o f a s i m u l a t i o n is l i m i t e d b y
Computer Simulations calculation speed.
John W. Moore
S e v e r a l e x a m p l e s will s e r v e t o i l l u s t r a t e t h e d i v e r s e w a y s
i n w h i c h s i m u l a t i o n s a r e a l r e a d y a p p l i e d . G o r d o n B a r r o w (16)
, Ml 48197
has described t h e possibility t h a t physical chemistry could b e
In many cases what I call "instructional simulations" can m a d e a " p l a y g r o u n d " w i t h a n a p p r o p r i a t e collection of s i m -
provide a new pedagogic approach to teaching chemistry. Such u l a t i o n s , a n d h e h a s w r i t t e n a l a r g e n u m b e r of t h e s e . I n o n e ,
simulations can place students in a role similar to that of a t h e t r a j e c t o r y of t h e c e n t e r of m a s s o f o n e g a s m o l e c u l e is
research chemist, requiring the student to formulate signifi- p l o t t e d as i t collides w i t h a n o t h e r u n d e r t h e i n f l u e n c e of a
cant questions, design appropriate simulated experiments, L e n n a r d - J o n e s potential. S t u d e n t s can vary relative velocity
and interpret intelligently the data obtained from such ex- a n d i m p a c t p a r a m e t e r a n d t h e n w a t c h t h e t r a j e c t o r y as it is
periments. At-the same time the computer can provide a set d r a w n on a video screen. T h i s sample graphic illustration
of tools for dealing with experimental data (e.g., software for p r o v i d e s a g r e a t d e a l o f i n s i g h t i n t o w h a t is m e a n t b y t h e s i z e
plotting or transforming data) that compresses time, bringing of a n a t o m a n d h o w collisions o c c u r .
the satisfaction of successfully probing nature's secrets much A n o t h e r g o o d e x a m p l e of a s i m u l a t i o n t h a t c o n t a i n s m u c h
more quickly than is usual in real life. Curiosity and discip- information t h a t can be discovered by s t u d e n t s was provided
lined inquiry can be rewarded rapidly, and students are af- t o m e b y C h r i s B i g u m of M e l b o u r n e S t a t e C o l l e g e in A u s t r a l i a .
forded the opportunity to play with our models of how nature Bigum has p r o g r a m m e d a n A p p l e so t h a t the user can take a
works, thereby discovering implications of the models that single a t o m a n d a d d or r e m o v e s u b a t o m i c particles. T h u s a
even experienced chemists may not be aware of, s t u d e n t could tell t h e c o m p u t e r " a d d 4 p r o t o n s " or " s u b t r a c t
The student user of an instructional simulation is able to
interact with a mathematical model through the medium of
a computer. The student chooses parameters and the com-
puter responds by calculating results on the basis of model
Table 4. Some Sources of Computer-Controlled Videotape/
Videodisk Hardware and Software.
Table 3. Computer-Video instructional Topics
Allen Productions IT AT, Inc
Operation of Analytical Baiance 500 Lakeside Plaza 2 20010 Century Blvd.
Use of Buret 5225 Wiley Post Way Suite 101
Use of Pipe! Sail Lake City, UT 84116 Germantown, MD 20874
Technique of Filtering
BCD Associate New Media Graphics
Use of Separfltory Funnel 5809 S.W. 5th 145 Main St.
Handling of Solid and Liquid Chemicals Suite 101 Cambridge. MA 02142
Accident Procedures Okiahoma City, OK 7312B Pioneer
Simple Stereochemistry
CAVRI Interactive Video Systems 200 W. Grand
Principles of Specirophotomelry
26 Trumbul! St. Montvale, NJ 07645
Prepartlon ot Samples for Speciiophotometry
Operation of pH-mv Meter Mew Haven, CT 06511 Reactive Systems, Inc.
Principles of Crystal Structure Colony Productions 40 N. VanBrant
1248 Biourttstown Hwy. Englewood, NJ 07631
Tallahassee, FL 32304 Regency Systems, Inc.
Digital Controls P.O. Box 3590
equations. T h e s e results are usually displayed graphically or 1610 Interstate Dr.
2551 Blairstone Pines
hi s o m e o t h e r n o n - n u m e r i c format, a n d t h e y are available Tallahassee, FL 32301 Champaign, !L 61820
a l m o s t i m m e d i a t e l y . O n t h e b a s i s of o n e r o u n d of s i m u l a t i o n Gentech Texas Instruments
the student can modify parameter choices a n d experiment 1101 N. Fulton P.O. Box 10508
f u r t h e r , p l a y i n g w i t h t h e m o d e l to s e e w h a t will h a p p e n . S u c h Evansviile, IN 47710 Lubbock, TX 79408
p l a y c a n b e m o t i v a t e d solely b y c u r i o s i t y , b y t h e c h a l l e n g e of Whitney Educational Services
Informational Technologies, Inc.
u n d e r s t a n d i n g a n d controlling t h e m o d e l s y s t e m , or b y a n P.O. Box 72 1777 SOfal Place
a s s i g n m e n t from a t e a c h e r . S u c h a n a s s i g n m e n t c a n be in e s - PuMaGorda, FL 33951 Suite 40 S
s e n c e a r e s e a r c h p r o b l e m , c a n elicit research-like behavior, Interactive Video Corp. San Mateo, CA 94402
a n d can include t h e r e q u i r e m e n t of oral a n d / o r written pre- 7500 San Felipe
s e n t a t i o n of r e s u l t s a n d c o n c l u s i o n s . Suite 100
Instructional simulations m a k e several d e m a n d s on the Houston, TX 77063

2 electrons" or "add 1 neutron," and the simulated atom would b e s u c c e s s f u l ; t h e r e is a m p l e e v i d e n c e , b o t h o b j e c t i v e a n d
be changed accordingly. If the resulting atom is unstable it will subjective, to support these suggestions.
decompose by an appropriate process, such as electron cap- T h e m o d u l a r n a t u r e of c o m p u t e r p r o g r a m s leads t o
ture, producing a more stable structure. AH processes that pedagogical a n d administrative benefits. A p r o g r a m t h a t has
occur in the simulation are those that are found in a table of b e e n d e s i g n e d c a r e f u l l y t o a c h i e v e a s p e c i f i c o b j e c t i v e , e.g., t o
nuclides. In simulated time a student has about 10 s to add or simulate a chemical p h e n o m e n o n , probably can be used to
remove more subatomic particles; if he does not, decomposi- a d v a n t a g e a t n u m e r o u s places in t h e c u r r i c u l u m ; i n d e e d , it
tion will occur. When a student achieves a stable atomic m a y be used several times to help achieve a different overall
configuration he is rewarded with some information about the i m p r e s s i o n of t h e s u b j e c t . P r o g r a m s m a y b e m a d e a v a i l a b l e
history and discovery of the element formed. t o different students in different sequences, depending u p o n
A third example is a program under development by Robert differing s t u d e n t b a c k g r o u n d characteristics a n d career goals.
Rittenhouse of Walla Walla College for the SERAPHIM/ T h e e x i s t e n c e of m o d u l a r p r o g r a m s l e a d s t o a n e d u c a t i o n a l
ChemCom Interface Project. This program is based on flexibility t h a t encourages self-paced a n d personalized in-
Rutherford's equation for scattering of a particles by metal struction. Finally, such computer m e t h o d s are easily adapt-
foils. A student is supplied with several experimental tools: a b l e to d e t a i l e d r e c o r d - k e e p i n g f o r a v a r i e t y o f p u r p o s e s , i n -
an re-particle scattering apparatus; several metal targets; a cluding student evaluation or counseling, program improve-
detector and pulse-height analyzer; a digital microscope for ment, a n d pacing the course to the student's needs.
viewing things on the atomic level; a data-disk notebook; a All t o o f r e q u e n t l y , t e a c h e r s b e c o m e o v e r l y i n v o l v e d in l o -
data analyzer that can perform mathematical operations such g i s t i c a l a n d a d m m i s t r a t i v e f u n c t i o n s t o t h e d e t r i m e n t of
as squaring all X values in a set of X,Y pairs; and a data t e a c h i n g ; t h a t is, t h e y h a v e t h e b u r d e n o f a s s i g n i n g , g r a d i n g ,
plotter. With these tools at his disposal the student can be a n d giving feedback on h o m e w o r k a n d tests, helping s t u d e n t s
assigned simple or complex research projects. For example: with their assignments, conducting tutorial/remedial drill
"Show that the number of a particles scattered at 30° is pro- group interactions, a n d organizing individual laboratory work.
portional to the number of particles that strike that target;" Successful c o m p u t e r p r o g r a m s have b e e n written t h a t engage
or "Find the relationship between angle of scattering and s t u d e n t s in a t u t o r i a l i n t e r a c t i o n w h i c h c a n b e u s e d for drill,
number of <v particles that strike the detector at that angle." r e v i e w , o r r e m e d i a l p u r p o s e s ; w h i c h s i m u l a t e p o r t i o n s of
In the first case the student is told what to look for and the laboratory experiences; a n d which p r o d u c e interactive ex-
relationship is direct proportionality, so a simple plot will do. a m i n a t i o n s o r q u i z z e s o n d e m a n d . I t is a p p a r e n t t h a t s u c h
The second case is much tougher and should only be assigned p r o g r a m s m i m i c m a n y of t h e t a s k s i n w h i c h t e a c h e r s n o r m a l l y
to a good student. By tailoring assignments to students' engage. T o a large e x t e n t t h e c o m p u t e r can p e r f o r m t h e s e
abilities one can use the same simulation at several levels. t a s k s {on a n i n d i v i d u a l b a s i s ) a s w e l l a s , or b e t t e r t h a n , t h e
instructor, since p r o g r a m s are infinitely patient. Indeed, we
The last example involves an environmental simulation, can imagine a learning system incorporating such programs
where the real experiment would involve potential harm to as e x t e n d i n g t h e capabilities of t h e t e a c h e r in s p a c e a n d t i m e .
people and the rest of the biota. It is being developed for the I n s u c h a s y s t e m , t h e teacher r e t a i n s h i s / h e r u s u a l t e a c h i n g
SERAPHIM/ChemCom Interface Project by John K. Estell, r o l e b u t t r a d e s t h e r o l e s of b o o k k e e p e r , g r a d e r , a n d a l l - a r o u n d
a computer science student at the University of Toledo. The p a p e r s h u f f l e r for t h e roles of c o u n s e l o r , g u i d e , a n d m e d i -
program casts the student into the role of an operator of a ator.
sewage treatment plant who must decide what percentages
of sewage flow to treat by primary, secondary, and tertiary
methods. The student must stay within a budget while Tutorial/Drill Programs
maintaining water quality. Taxes and fines are levied for In chemistry, as in all subjects, there are many pedagogical
polluting, and the incompetent student's stimulation will end situations t h a t require a patient tutor to guide the student
with his being fired. Students compete to see who can achieve through a logical sequence of steps in a (relatively) closed
the greatest budget surplus. subject with respect to information content. Usually the point
The simulations described here all make use of the com- is driven home by the use of numerous examples that are
puter's ability to store, process, and recall data, to calculate variations on a theme. Classically, such situations have been
quickly and accurately, and to display results in non-numeric exploited by recitation or discussion periods and the use of
or graphic forms. They allow us to invert the normal process homework problems. It is possible to write highly sophisti-
of learning about models. Students can vary parameters, ob- cated programs for interactive computer systems that capture
serve the effects almost immediately, and become familiar the detailed strategy that an individual teacher would use in
with the outcomes of realistically complex models. Students a tutorial session. In essence, that teacher (in the form of the
can be placed in the positions of real-life chemists and can program) is unbounded in space and time since the program
learn the insight* and modes of thought those chemists use can be run at any time of day and can be transmitted to any
in their work. The challenge to us as teachers is to devise a geographic point the communications system permits. The
broad range of such interactive, instructional simulations that alleviation of the logistic constraints imposed by the avail-
combine flexibility and convenience of use with general and ability of rooms and/or instructors is obvious.
realistic models. Such programs will not replace TA's, pro-
fessors, or labs, but they will challenge all of us to replace Laboratory Simulation Programs
time-honored but less-than-optimal pedagogic approaches
to many aspects of chemistry. Laboratory courses are usually designed to provide expe-
rience in experimental techniques as well as to develop a fa-
cility for manipulating raw experimental data. Computer
methods can provide experience in the latter phase of labo-
Computers in lite Freshman Course; Where Bo ratory work but do little with respect to the former unless the
They Perform Best? computer is treated as a laboratory tool interfaced between
the student and the experiment, Basically, simulation pro-
J. J. Lagowski grams can be designed to have a student engage in all the de-
University of Texas at Austin cision-making he or she normally would do in a real experi-
Austin, TX 78712 ment, i.e., collect data and draw conclusions based on the data.
It is possible to introduce experimental errors in the results
O v e r t h e p a s t 20 y e a r s t h e e x p e r i e n c e of a few g r o u p s in
of computer-simulated experiments which reflect the accuracy
using academic computing in mainstream chemical education
expected from the equipment normally used in the laboratory
has indicated the modes where computer-based methods can

as well as gross random errors. Thus, the students' experience Successful methods are those in which computing is sup-
in manipulating experimental results can he extended by plemental to the normal teaching functions rather than those
simulating experiments that (a) might he conceptually simple in which attempts are made to try to replace them.
but which require apparatus too complex for them to ma-
nipulate at a given educational level (e.g. atomic spectroscopy.
X-ray diffraction at the general chemistry level), (b) consume
a disproportionate amount of time if performed in their en-
tirety, (c) are potentially dangerous, and/or (d) involve ex-
Of Babbages and Strings
pensive equipment or chemicals which cannot be supplied for Derek A. Davenport
large numbers of students on an individual basis. Simulated Purdue University
experiments can be used in various ways, e.g., as extensions West Lafayette, IN 47907
of laboratory work as well as supplements to conventional
T h e t i m e h a s come o u r Chairman says
lecture material. T o t a l k of m a n y t h i n g s ,
!t should be pointed out that the terminals on which stu- Of c h e r u b i m s a n d S E R A P H I M S ,
dents might perform simulated experiments need not be lo- Of B a b b a g e s a n d S t r i n g s ,
cated in a laboratory; they may be placed in study rooms, li- A n d if t h e A p p l e ' s w o r m is bit,
brary carrels, or even in dormitories. Further, simulated ex- Will we b e u n d e r l i n g s ?
periments need not be performed at the conventional labo- I n d e e d will we b e t h e r e a t all,
ratory periods, nor do the programs need to be available in an W h e n t o t h e D e a n ' s delight,
interactive mode. Thus, a part of a student's laboratory ex- Professors a r e superfluous
perience can be provided in a more flexible manner than is And students spend the night
now possible under the logistic constraints imposed by con- T r a n s f i x e d before t h e i r l i n y s c r e e n s ,
ventional laboratory work. The savings in costs for equipment P r e p r o g r a m m e d to be bright?
and chemicals using computer-based methods is obvious. T h e laboratory a cenotaph.
T h e T . A / s o n relief,
N o n e e d for b o o k s or c h e m i c a l s ,
Homework Problems
S a v i n g s b e y o n d belief.
Homework problems have been used traditionally to pro- 0 b r a v e new w o r l d of A c a d e m e ,
vide the student with practice in problem-solving, but there Ail I n d i a n s , n o chief!
are several difficulties with such strategy. First, grading and Yet s t u d e n t s ' minds take random walks,
record-keeping become important considerations in classes Spelling t e n d s t o frolic,
with large numbers of students. Second, feedback on problems A n d c h e m i s t r y m o s t often is
(grading) is generally slow and individual error analysis vir- M o r e c o n c r e t e t h a n symbolic;
tually non-existent when a large number of problem sets are S o m a y t h e y b o t h s m a l l q u a r t e r give,
hand-graded. Many of the programs written for tutorial/drill T o s i m p l e t w o - b i t logic!
mode or laboratory simulation contain drivers or subroutines B u t if t h e y m i n d their p ' s a n d q ' s ,
well suited for generating problems. Separate homework- A n d k e e p t h e i r whiskers clean,
generating programs have also been developed as well as C o m p u t e r s surely have a place
programs to grade the homework, for a program that can U p o n t h e college scene,
generate problems can contain information on the details T h e i r gentle flips a n d muffled flops.
associated with common student errors. Thus, it is possible E c h o i n g o'er t h e green,
to give not only full credit for a problem, but also partial credit F o r u n l i k e aging F a c u l t y ,
if intermediate steps are correct but the final answer is wrong. W h o s e lids a r e a p t t o flip,
In addition, such grading programs usually incorporate sub- T h e i r p a t i e n c e is q u i t e a w e s o m e ,
routines that automatically yield appropriate statistical T h e i r floppy discs d o n ' t slip,
analysis of the student's performance on individual prob- S o let u s h e a r a g u a r d e d cheer,
lems. Hip, chip, hooray, hip, chip!
T o a n s w e r t h e first t h r e e q u e s t i o n s i n C h a i r m a n M o o r e ' s l i t -
tle r e d c a t e c h i s m : " n o ,n o , a n d again, n o . W h a t I tell y o u t h r e e
Examinations t i m e s is t r u e . "
An important element of computer-based techniques is the
development of programs and data bases that generate ex- Should Computers Replace Professors?
aminations. The ability to generate a large number of exam- Only in selected cases, but the AAUP won't allow even those
inations that are statistically equivalent gives the instructor few replacements to occur. If only the pious hope "anyone who
a very powerful teaching device. With such programs avail- can be replaced by a computer, should be" were true! As for
able, it is possible to create self-paced courses for relatively the competent majority, the teaching professoriate will hap-
large numbers of students; such flexible courses generally pily remain indispensable in the computer age, Man is, after
depend upon the availability of a "readiness test" on a stu- all, a tool-making animal and the computer is merely the latest
dent-demand basis. Input of the marked examinations into tool, though just possibly one of an entirely new kind. Around
the grading program can be either in a batch mode using in- 1450 Johann Gutenberg was advanced 800 guilders for the
expensive mark-sense readers or interactively. The latter development of new "tools" and within a few years those tools
operation permits immediate feedback to the student. It is had produced his unsurpassed Latin Bible. In the case of
apparent that for larger numbers of students at various points computers in chemical education, even Stan Smith has not
in a self-paced course the logistics of creating, administering, yet got past "in the beginni..." though to listen to some of the
grading, and maintaining security for a Urge number of dif- apocalyptic advertising one might think we had already pro-
ferent examinations becomes virtually unmanageable using grammed the Book of Revelations. My prejudice is best stated
conventional methods. Computer-based methods not only in the language of PascaL "Vhomme n'est qu'un roseau, le
expedite all aspects of examination-taking, but they can also plus foible de la nature; maise'est un roseau peasant" which
incorporate relatively sophisticated record-keeping and sta- for those still struggling with enbasic English may be trans-
tistical routines with little additional difficulty. Most of the lated as "Man is only a reed, the weakest thing in nature; but
successful applications of computer-based methods have oc- he is a thinking reed." It might however be well to remember
curred at the learning-teaching interface. Programs either help that L. S. B. Leakey has claimed that in the hands of the great
students learn and/or expand the functions of teachers. apes a reed is one of the most useful of tools.

Should Computers Replace TA's? As designated devil's advocate for Project S E R A P H I M m y
In recitations/tutorials perhaps hut my research-minded final c o m m e n t o n t h i s l a t e s t w o n d e r o f e d u c a t i o n a l t e c h n o l o g y
colleagues are not about to let it happen. After all, thefirsttwo is s h o w n . i n F i g u r e 6 .
or three years of chemistry graduate school may be defined T h e i m m e m o r i a l p r o b l e m s o ft e a c h i n g e n d u r e b u t a t l e a s t
as a work-study program financed not by the federal govern- we have b e e n vouchsafed a marvelous n e w tool with which t o
ment but by the involuntary subsidy of the parents of un- chip away a tthe darkness.
dergraduates. It is hard to envision any chemistry department
head in the near future responding to a newly redundant
graduate student in the terms a French king used to a lowly
petitioner: "II faut que je vive." "Je n'en uois pas la nec-
essity. " If be made such a response, he would not remain de-
partment head for very long.
Should Computers Replace Labs?
Certainly, if fact abdicates in favor of fiction, which fortu-
nately nature is unlikely to allow to happen. There are times,
however, when my faith wavers. Only today, I saw the latest
P h D prelim examination written by illustrious physical
chemistry colleagues. Two things struck me: physical chemists
still use ergs and dynes and in none of the twelve questions is
any specific chemical species invoked nor any set of chemical
data cited. One is reminded of Donald Hall's two-line poem
Figure 5, Cartoon by John Caldwell from "Animals, Animate, Animate," {Editors:

Gsorge Booth, Gahan Wilson, and Ron Wolln) and used with the kind permission
of Harper G Row Publishers, Inc., New York. Copyright © 1979 by The Car-
toonists Guild, inc.
PETS
SOUGHT Summary and Conclusions
SOL.D John W. Moore
Ypsiianti, Mt 48197
Summarizing and drawing conclusions about the remarks

o f a s d i v e r s e a g r o u p o f e x p e r t s a sw e r e i n v o l v e d i n t h i s s y m -
p o s i u m i sa t a l l o r d e r . H o w e v e r , t h e r e w e r e a n u m b e r o f p a r -
a l l e l s i n t h e t a l k s p r e s e n t e d , a n dI t h i n k t h e s y m p o s i u m a t
least began t odelineate where a n d h o w c o m p u t e r s c a n con-
t r i b u t e t oc h e m i c a l e d u c a t i o n .
T h e r e w a s a g r e e m e n t t h a t t h e c o m p u t e r p r o v i d e s new ways
PETS of approaching problems, f o rf a c u l t y , f o rs t u d e n t s , a n d f o r
SOUGHT chemists in general. Examples a r eS t a n Smith's equation-
•£
SOL.D b a l a n c i n g e x e r c i s e i nw h i c h t h e s c r e e n i sc o n s t a n t l y u p d a t e d
t o show how m a n y a t o m s are present and Allan Smith's use
Figu'B 4. Drawing by 0 . Sogtow: © 1947, 1975, The New Yorker Magazine,

Inc.
P o e t i c a l Philander o n l y t h o u g h t t o love
H e w e n t t o b e d w i t h w h a t h e t h o u g h t t h e girls w e r e syraboia of.
J e a n Martin Charcot h a d some rather odd ideas but h e was

o n t h e r i g h t t r a c k w h e n h ec l a i m e d , a g a i n i n t h e l a n g u a g e o f
P a s c a l : "La theorie c'est bon, mais ca n' empeche pas d'ex-
ister." T h e o r y i s f i n e b u t i t d o e s n ' t p r e v e n t t h i n g s f r o m h a p -
p e n i n g . A s a p r e p a r a t i o n for, s u p p l e m e n t t o , a n d e x t e n s i o n
of t h e t e a c h i n g l a b o r a t o r y , c o m p u t e r s c l e a r l y h a v e a g r e a t
f u t u r e . B u t w i t h t h e p o s s i b l e e x c e p t i o n o ft h e c h e m i s t r y ( o r
a t l e a s t t h e p h y s i c s ) o fp h o s p h o r s , b e g i n n i n g s c i e n c e c a n n o t
b e done o n a T V m o n i t o r . W o r d s , s y m b o l s , m a t h e m a t i c a l "Lotik—if you havQJivt! pockel rakitlaters alul I take lwc
away, how many have you got kfi?"
formulae, and graphics m a y b e manipulated on the screen with
m a r v e l o u s d e x t e r i t y , b u t i t i sw o r d s , s y m b o l s , m a t h e m a t i c a l
Figure 6. Cartoon from "Cartoons from Punch," (Editor: William Hewlston) and
formulae, a n dgraphics t h a t a r e being manipulated—-not
used with the kind permission of St. Martin's Press, Inc., New York. Copyright
chemical substances, © 1979 by Punch Publications Limited.

cases a teacher has examined the problem of teaching a par- cannot be done on a TV monitor." Of course it is hard to do
ticular concept or procedure and devised a method of showing chemistry on a book, too, unless you burn it or take it to lab,
the student a different aspect than would be shown in a book, and the same is true of most other media.
or in a non- computer! zed lecture. Simulations such as those Computers seem to be especially good at teaching ideas and
I described can be used to induce students to approach concepts and at manipulating symbols; they are less well
mathematical models in a different way, and automated lab- suited to situations where real-life experience is necessary,
oratories like Stan Burden's expose students to experimental except in the case where the experience is to be with handling
design and data analysis aspects of laboratory work that would a computer/instrument combination or with handling and
be difficult to access any other way. In designing computer- manipulating symbols and ideas.
baaed materials we should be constantly on the alert for new Finally let's summarize the answers that were given to the
approaches to the problems of teaching or learning that the four questions in the title of the symposium. Not everyone
computer allows us to try. addressed the questions explicitly, but there was consensus.
Nearly every sneaker alluded to the computer as a tool. At Joe Lagowski said, "Yes, Yes, Yes, NO!" and Derek Davenport
the end of Stan Smith's talk we heard,"... we have added one said, "No, No, No," but then he qualified the first two no's as
more thing to the list of tools that we have for teaching." Derek being for the wrong reasons in some cases. Actually these two
Davenport closed with, "The immemorial problems of responses were probably in much better agreement than a
teaching endure, but at least we have been vouchsafed a computer analysis of the symbols on the page would reveal.
marvelous new tool with which to chip away at the darkness." The consensus was stated by Stan Smith, "A computer is a
In between we heard from Jeff Davis about how that tool tool: good teachers cannot be replaced by a computer." And
might be linked with others we are more familiar with, and so there was agreement that the answer to "Should computers
from Joe Lagowski and Jeff about many of the logistic and replace...?" was a resounding no. But there was also agree-
administrative burdens from which that tool might release us. ment that we are nowhere near using that tool to its capacity.
Stan Burden uses the computer as a timesaving tool for stu- Perhaps the reason lies in a statement that Stan Smith made
dents, and puts the students' time to use on thinking instead when he visited Allan Smith and Drexel University.
of collecting data. Allan Smith alluded to several uses of this "The world is overpopulated with programmers who can
new tool that parallel those popular in the business world. We get the computer to do anything, but who don't know what
would do well to examine the many applications that have they want it to do. The greatest limitation of the use of com-
made microcomputers the success story they are in business, puters in education is the creativity of the people trying to use
with an eye k> how these can be adapted to the specific prob- them."
lems of chemistry teachers.
Several speakers identified the computer as a new medium
of instruction and attempted to describe how the character- Literature Cited
istics of the computer make it more or less useful for different (0 f i , J. J., J. CHBM. EDUC, BO, 529 (1983).
kinda of instructional tasks. Patience in drill and practice {«
situations, rapid and error-free calculations and handling of (.1) Smith, S. G., J. CHBM. EUUC, tl,608 (1970).
Lower, S.. Oethotd, G., Smith, S. G., Johnson, K Jeffrey, and Moore, J. W., J. CHBM.
textual or numeric data, ability to interact with students and (4) StWCSe, 219 (1979).
take account of previous input from a student, graphics and 15) Smith, S, G,, and Ohabay, R., J. CHEM. EDUC., 5*. 699 (1977).
animation, and ability to keep records and analyze large

(6) Chabay, R., and Smith, S. G., J. CHKM. EDUC, 54,745 (1877).
{",) Cavin, C. S, Cavin. E. D., and Ugowaki, J. J., J. CHEM. EDUC, 55,61)2 (1978).
quantities of data were all mentioned as positive character- (8) Wiegcrs, K. &, and Smith, S. G-., J. CHEM. EDUC, 57,454 (1980).
istics we ought to take advantage of. The main negative (9) Smith, S. 0., Ghesquieie, J. R, and Avnor. E, A., S. CHBM. EDUC., 51,243 [1974).
(10! Moore, C, Smith, S. G, and Avner, K. A., J. CHEM. EDUC, 57,190 (1980!.
characteristic can be generalized as: the computer is not (11! Francis, L.D..J. CHEM. EDUC.,50,55SU373).
chemistry, and to learn chemistry one needs to do chemistry. (12) Trfuore, J. W., ami Moore. E. A., J. CHBM. EDUC, 60, SS3 (1983],
According to Stan Smith, "You can do simulated laboratory Smith, A. I.,, "Suppose EueFy Freshman Owned a Microcomputer," Proceedings of
113) the IKRR CompCom Fall '83 Conference, September 28,1983 (tft be published).
experiments on the computer, but that isn't real laboratory "On Selecting a Microcomputer for laOO Freshmen at DrBHfl," Drexei Microcomputer
work: you can't do real laboratory work on a computer." And Selection Committee Report, submitted for pubiicalion in Collegiate Microcom-
puter.
according to Derek Davenport, "But with the possible ex- Smith, A. L., "The Persona! Computer Project at DTSKBI; Selection of the System and
ception of the chemistry.. .of phosphors, beginning science Development of the Family," SIAM Nen-a, July, 131a.
(J5) Smith, A. L., Computers in Chemical Educalion Newsletter, September. 1983.
Barrow. G. M., J- CHEM. EDUC.57,697 (1980).
Pre-Test Volunteers N e e d e d for A G S / N S T A T e s t in High S c h o o l C h e m i s t r y
T h e e x a m i n a t i o n c o m m i t t e e n e e d s v o l u n t e e r s t o g i v e a p r e - l e s t for t h e F o r m 1 9 8 5 e x a m i n a t i o n . T h e t e s t w i l l p r o v i d e s t a t i s t i c a l d a t a
for t h e s e l e c t i o n o f i t e m s t o b e u s e d o n t h e 1 9 8 5 t e s t .
T h e p r e - t e s t will b e r e a d y b y M a y 1,1984. T e a c h e r s m a y a d m i n i s t e r t h e t e a t a t a n y l i m e . H o w e v e r , it is i m p e r a t i v e t h a t t h e a n s w e r
s h e e t s b e r e t u r n e d b e f o r e J u n e 1 5 , 1 9 8 4 . A l s o , i n o r d e r f o r t h e d a t a to b e s t a t i s t i c a l l y valid, it is i m p o r t a n t t h a t ail s t u d e n t s a t t e m p t all
q u e s t i o n s g i v e n to t h e m . T h e r e f o r e , s u f f i c i e n t t i m e n e e d s to b e p r o v i d e d f o r t h e a d m i n i s t r a t i o n o f t h e test. I t i s n o t n e c e s s a r y , h o w e v e r ,
t h a t t h e total t e s t b e g i v e n a t o n e s i t t i n g . T h e t e s t m a y b e s e p a r a t e d a n d administered in two parts.
F r o m v o l u n t e e r s r e s p o n d i n g , a s a m p l e r e p r e s e n t a t i v e o f h i g h s c h o o l c h e m i s t r y w i i i b e s e l e c t e d . A l l will b e n o t i f i e d w h e n t h e s a m p l e
has been selected.
Chemistry teachers interested in pre-testing the F o r m 1985test should respond b y February 15,1984 to: William Arnold, 1328 Beilbrook
Avenue, Xenia, O H 45385. P h o n e : (513)372-7385.

edited by:
MICHAEL R. SLABAUGH
chem I supplement
HELEN J . JAMES
Weber Stale College
OgOen, Utah 84408
Geochemical Exploration of the Moon

Isidore Adfer
University of Maryland, College Park, MD 20742
The most important keys to understanding the formation quilitatis, Surveyor 6 a t Sinus Medii, and Surveyor 7 on t h e
of the solar system and its subsequent evolution lie in the r i m of t h e very large crater Tycho. T h e i n s t r u m e n t deployed
chemical composition of the planetary surfaces and interiors, t o t h e l u n a r s u r f a c e u s e d t h e p r i n c i p l e of a l p h a - p a r t i c l e
the meteorites, the comets, and the asteroids. An exhaustive back-scattering developed decades earlier by Rutherford and
study of the geochemical exploration of the planets would others (2). This provided chemical information about the
require a very lengthy text. This paper is based on examples landing sites.
from my own experience in the Apollo program. These ex- T h e first r e a s o n a b l y successful a t t e m p t a t c h e m i c a l analysis
amples represent only a small part of the findings of the space f r o m o r b i t w a s d u r i n g t h e f l i g h t o f L u n a 10 (3) w h i c h o r b i t e d
program. t h e m o o n a n d carried a g a m m a - r a y s p e c t r o m e t e r . I n 1969 t h e
The abundance of certain elements relative to cosmic A p o l l o 3.1 m i s s i o n l a n d e d m e n o n t h e m o o n f o r t h e f i r s t t i m e ;
abundances, their mode of condensation, and condensation t h e site, M a r e T r a n q u i l i t a t i s . T h i s w a s t h e first i n s t a n c e in
temperatures are important clues. For example, the evolu- h u m a n history t h a t d o c u m e n t e d samples from another body
tionary processes that have occurred in our solar system can in t h e solar s y s t e m h a s b e e n o b t a i n e d . B y t h e e n d of t h e Apollo
be studied by examining the abundances of potassium and 17 m i s s i o n , a s t r o n a u t s h a d r e t u r n e d a b o u t 4 0 0 k g of soil a n d
thallium relative to uranium. These elements are indicators r o c k s . T h e s t u d y of t h e s e s a m p l e s e m p l o y e d a g r e a t v a r i e t y
of the abundance of volatile elements relative to refractory of t h e m o s t s o p h i s t i c a t e d a n a l y t i c a l m e t h o d s . T h e s a m p l e s
elements, Such studies also provide important information from the large lunar basins were essentially basalts, while
about the pre- and post-accretionary stages in the evolution those from t h e highlands were essentially feldspathic anor-
of the soiar system. t h o s i t e s . T h e h i g h l a n d s w e r e f o u n d t o b e t h e m o s t a n c i e n t of
t h e l u n a r features, s o m e w h a t over four billion years old. T h e
Since we have yet to penetrate even the Earth's mantle, it
basalts were found to range b e t w e e n t h r e e a n d four billion
is obvious that information about planetary interiors can be
y e a r s o l d . T h e y a p p a r e n t l y c a m e t o fill t h e l a r g e b a s i n s a f t e r
obtained only by inference. On the other hand, for surface
t h e i r f o r m a t i o n , w h i c h likely o c c u r r e d a s a r e s u l t of t h e i m p a c t
investigations one can employ classical methods such as
of e n o r m o u s m e t e o r i t e s a n d p l a n e t e s i m a l s s o m e four billion
geological sampling, mapping, and laboratory analysis.
years ago.
Space-age technology using remote analytical techniques,
mainly spectroscopic and photographic, are also used. An T h e d a t a m e n t i o n e d a b o v e w a s o b t a i n e d f r o m a n a l y s i s of
example of the latter involved the use of photogeologic t h e s a m p l e s c o l l e c t e d a t a few c h o s e n s i t e s o n t h e m o o n , O u r
methods in the Landsat program. We are presently con- v i e w o f t h e w h o l e m o o n is a n e x t r a p o l a t i o n f r o m t h e s e f a c t s .
strained to the use of remote techniques when dealing with T h e r e a r e m a n y r e a s o n s , h o w e v e r , for s e e k i n g c h e m i c a l i n -
celestial bodies other than our moon. Study of our own moon f o r m a t i o n f r o m o t h e r s i t e s ( m a n y o f w h i c h will b e b e y o n d t h e
is unique in that we have been able, because of the samples p o s s i b i l i t y of m a n n e d l a n d i n g s for y e a r s t o c o m e ) . G l o b a l
collected, to employ a largely classical approach under de- c o m p o s i t i o n a l m a p s c o u l d be of g r e a t value in u n d e r s t a n d i n g
cidedly new circumstances. Remote methods have also been t h e m o o n . T h u s a s e r i e s of o r b i t a l e x p e r i m e n t s w a s p r o p o s e d
used. w h i c h b e g a n w i t h t h e A p o l l o 15 m i s s i o n . T h e s e e x p e r i m e n t s
h a v e h e l p e d c o n s i d e r a b l y in a n s w e r i n g a n u m b e r of q u e s t i o n s
Questions about the Moon relating t o t h e early history a n d origin of t h e m o o n .
Prior to space travel, our knowledge of the moon rested on
earth-based telescopic studies. With the advent of space ex- Of bJtai Remote Sensing
ploration, numerous programs carried out by the United How does one plan experiments to give compositional in-
States and the Soviet Union have provided a wealth of new formation about a celestial body which can be conducted from
information. Among the various programs were the Ranger an orbiting satellite? There are only a limited number of ob-
fly bys and impacters, Surveyor landers, Lunas, Orbiters, and servational phenomena from which one can infer unique ele-
the Apollo and Luankhod flights. The first truly remarkable mental identifications and concentrations. A survey of the
in-situ chemical analysis of the lunar surface resulted from electromagnetic and particulate spectrum yields only a few
the Surveyor missions (1}. Surveyor 5 landed at Mare Tran- possibilities. Certainly one cannot expect to obtain results
which are precise by laboratory standards. Nevertheless, such
techniques as garnma-ray or X-ray spectroscopy can provide
This feature presents relevant applications of chemistry to everyday life. much useful information.
The information presented might be used directly in class, posted on
tnilletln boards, or otherwise used to stimulate student involvement In A summary of the radiation environment a t the lunar sur-
activities related to chemistry. Contributions shoukj be sent to the feature face is shown in Figure 1. Based on this view of the lunar am-
editors. bient radiation, a series of orbital experiments were designed
to supply chemical information. As we can see, both natural

ftMMTISN ENVIRONMENT AT LUNUf SUHFOCE IB 1
1 ~ ^-——j.
SOIARX-.AYS
MS
X-RAY
O, NB, MB, At,

Si, K, Ca, Mr.
No K EDGE
F., — ( U , Tf.)
10"
Mg A EDGE
AT I EDGE
MtSOS, HY? ERON, S AKTI-PABTICU MQ DUCHON
Sr K EDGE
Figure 1. The radialion environment at the lunar surface. Particularly important

Is the ratura! raSloactfvtiy, Ihe solar X-rays, the gamma rays produced by the
LrJ
cosmic rays and perhaps the alpha particle emission.
£ to1
a n d i n d u c e d s o u r c e s of r a d i a t i o n a r e p r e s e n t . A m o n g t h e
principle naturally occurring radioactive constituents are t h e FIT ID SDUAD DAIA WITH
long-lived nuclides « K , 3;l2Th, a n d 2 3 8 U a n d their d e c a y
products. T h e s e sources emit alpha, beta, a n d g a m m a radia-
t i o n of v a r i o u s energies. I m p o r t a n t l y , t h e g a m m a r a d i a t i o n
IN I-SA 1AND
I
is c h a r a c t e r i s t i c a n d c a n b e u s e d for identification of t h e ele- IQ> - rtt S'20 A (AND
ments that emit them. Special processes such as radon a n d COMMNfO $KCT«UM OF
t h o r o n d i f f u s i o n m a y a l s o o c c u r (4). B o m b a r d m e n t o f t h e I.SO . 10*'K WIHl
l u n a r s u r f a c e b y c o s m i c r a y s a n d e n e r g e t i c p r o t o n s will a l s o
p r o d u c e a v a r i e t y of s h o r t - l i v e d n u e l i d e s a n d , a s a c o n s e q u e n c e ,
• 3.W . Kl'*K rtft
induced radioactivity. Cosmic r a y interactions with the lunar
surface will also p r o d u c e a p r o m p t e m i s s i o n of n e u t r o n s a n d
protons. us* r
E v e n u n d e r " q u i e t " c o n d i t i o n s , t h e a u n is a c o p i o u s e m i t t e r
o f s o f t X - r a y s . B e c a u s e of t h e f i l t e r i n g n a t u r e o f o u r a t m o -
s p h e r e , i t h a s b e e n p o s s i b l e to d e t e r m i n e t h e s p e c t r a l d i s t r i -
b u t i o n of t h e s e X - r a y s o n l y b y flights a b o v e t h e a t m o s p h e r e .
T h e s e solar X-rays are absorbed b y t h e lunar surface a n d
produce secondary (fluorescent) X-rays which again are »» 0.3 0.1 0.» 1.2 ),S 1.1 J.I 2.4 1.7 3.0
c h a r a c t e r i s t i c of s o m e o f t h e e l e m e n t s m a k i n g u p t h e l u n a r EME1GV ( m l
surface. O n e c a n t h e n p r e d i c t t h e yield of t h e s e c o n d a r y X - Figure 2. The "Qutet" sun X-ray output.
rays, which depends on the intensity a n d spectra! character
of t h e s o l a r X - r a y flux a n d t h e a b u n d a n c e of t h e e l e m e n t s in
the lunar surface. Finally, t h e radon a n d thoron which are
diffusing t h r o u g h t h e l u n a r surface would b e expected t o
p r o d u c e a l p h a particles h a v i n g energies c h a r a c t e r i s t i c of t h e PROPORTIONAL
various decay processes. COUNTER
0 0 1 " BE WINDOW
Lunar X-Ray Experiment

CALIBRATION SOURCES
We see that the "quiet sun" is energetically capable of
producing measureable amounts of characteristic X-rays from
all the abundant elements with atomic numbers of approxi-
mately 14 (Si) or smaller (Fig. 2). During brief periods of
heightened solar activity, one can expect characteristic X-rays A(-90%
from higher atomic number elements. COj-95%
COL LIMA TEH
As for the design of the X-ray experiment, calculations had ±30 He 0.5%
shown that the moon's X-ray brightness was low, and it was
therefore necessary to design a highly efficient system for
detecting the X-rays from the lunar surface. Not only was the
orbiting X-ray spectrometer required to have a high efficiency, Figure 3. An exploded view of the X-ray spectrometer.
but it also had to provide spectral information that could be
reduced to chemical quantities. Therefore, an assembly was r a t i o s of AS/Si, M g / S i , a n d M g / A l . T h e d e t e c t o r s v i e w e d t h e
built which consisted of three large proportional counters with m o o n t h r o u g h m e c h a n i c a l collimators s o t h a t t h e field of view
thin windows of beryllium. One detector was operated "bare" w a s 6 0 ° . T h i s m e a n t t h a t a t o r b i t a l a l t i t u d e s of 100 k m , res-
and the other two had selected X-ray filters consisting of a o l u t i o n o n t h e l u n a r surface p e r m i t t e d a n a l y s i s of f e a t u r e s
magnesium foil and an aluminum foil, respectively. Further, a b o u t 1 0 k m a c r o s s . A v i e w o f t h e X - r a y s p e c t r o m e t e r is s h o w n
the X-ray output from the detectors was energy-analyzed by in F i g u r e 3.
eight energy discriminator channels which covered in equal
intervals 0.5 to 2.75 keV X-rays. In this manner, three dif- Gamma-Ray Experiment
ferential X-ray spectra were obtained from the lunar surface
which, by simple mathematics, could be reduced to intensity From the very beginning of the lunar program it was as-
sumed that -K, Th, and U would be key elements in the un-

APOLLO 12
1 V
Figure 5. The alpha-particle experiment
SHIR COMMAND
001 FROM CLOCK
10' 103 10s 10° SURFACE BARRIER DFTECTOft
K in ppm OUROS-KNSIItV!
Figure 4. Pofassfum versus uranium in various materials.
d e r s t a n d i n g of l u n a r e v o l u t i o n . I n t e r r e s t r i a l p r o c e s s e s t h e
r a d i o a c t i v e d e c a y of t h e s e e l e m e n t s is c o n s i d e r e d t o b e a m a j o r
Figure 6. The Science Instrument Module iSIM).
s o u r c e o f t h e e n e r g y l e a d i n g t o v o l c a n i s m a n d m a g m a t i c dif-
f e r e n t i a t i o n . F u r t h e r , t h e a b u n d a n c e of t h e s e e l e m e n t s b e -
c o m e s a n i n d i c a t o r o f t h e e x t e n t of c h e m i c a l d i f f e r e n t i a t i o n
since K , T h , a n d U t e n d to c o n c e n t r a t e in t h e late s t a g e c r y s - e x p e c t e d t o d e c a y n e a r its source. T h e n e c e s s a r y e q u i p m e n t
t a l l i n e r o c k s s u c h a s g r a n i t e s . B y t h e A p o l l o 15 f l i g h t , e x c e l l e n t f o r a l p h a p a r t i c l e m e a s u r e m e n t s i s s h o w n i n F i g u r e 5. T h e
d e t e r m i n a t i o n s of K, T h , a n d U h a d b e e n m a d e i n v a r i o u s d e t e c t o r s are solid-state surface barrier types. T h e flight in-
returned lunar samples. As an example, K versus U values s t r u m e n t which was contained in t h e s a m e housing a s t h e
h a v e b e e n p l o t t e d for v a r i o u s l u n a r m a t e r i a l s (Fig. 4). A s a X - r a y e x p e r i m e n t c o n s i s t e d of a s e r i e s of d e t e c t o r s a n d
c o m p a r i s o n , a l i n e is d r a w n f o r t e r r e s t r i a l m a t e r i a l s r a n g i n g
alpha-processing electronics.
f r o m b a s a l t s t o g r a n i t e s . T h e r e l a t i v e p o s i t i o n of t h e a c h o n -
d r i t i c s t o n y m e t e o r i t e s is a l s o s h o w n . T h e d i a g o n a l s o n t h e The Apollo Science instrument Module (SIM)
graph represent K / U ratios. N o t e that the lunar materials
Figure 6 shows the Apollo SIM bay. The SIM bay was part
have lower K / U ratios t h a n terrestrial m a g m a t i e rocks. T h i s
of the Apollo Command-Service Module (CSM). Beginning
h a s b e e n traced t o h i g h U values a n d low K values, A similar
with the Apollo 15 flight, the CSM was used for the first time
s i t u a t i o n . e x i s t s w i t h r e g a r d t o K / T h r a t i o s . F u r t h e r m o r e , ft
to carry an ambitious array of instruments for orbital surveys
w a s f o u n d t h a t t h e r e w a s a d i s t i n c t v a r i a t i o n f r o m o n e col-
of a variety of lunar characteristics of which surface chemistry
lection site to another. Because K, T h , a n d U are such im-
was a prominent part. The instrumental complement con-
p o r t a n t i n d i c a t o r s of c h e m i c a l p r o c e s s e s , t h e a t t e m p t t o m a p
sisted of an X-ray fluorescence spectrometer, an alpha-particle
t h e g l o b a l d i s t r i b u t i o n of t h e s e e l e m e n t s a r o u n d t h e m o o n w a s
spectrometer, a mass spectrometer, a panoramic camera, a
c o n s i d e r e d of v e r y g r e a t i m p o r t a n c e .
laser altimeter, and a suhsatellite. (The latter was launched
T h e g a m m a - r a y assembly flown on Apollo 15 a n d 16 was
into an orbit of its own for the purpose of making geophysical
c o m p o s e d of t h r e e m a j o r s u b a a s e m b l i e s : t h e s c i n t i l l a t i o n d e -
measurements.) The X-ray, gamma-ray, and alpha-particle
t e c t o r fa t h a l l i u m - a c t i v a t e d s o d i u m i o d i d e c r y s t a l ) , t h e e l e c -
spectrometers were used for obtaining chemical information
tronics, a n d t h e t h e r m a l shield. In flight t h e g a m m a - r a y
about the moon's surface. The mass spectrometer was em-
s p e c t r o m e t e r w a s d e p l o y e d a t t h e e n d o f a 7 . 5 m b o o m in o r d e r
ployed in a study of the moon's tenuous atmosphere at orbital
t o r e m o v e it a s far as possible from t h e radioactivity, h o t h
altitudes. It is noteworthy that the X-ray and gamma-ray
n a t u r a l a n d c o s m i c r a y i n d u c e d , in t h e spacecraft. W h i l e t h e
instruments were also used to obtain astronomical data during
X - r a y e x p e r i m e n t d e s c r i b e d w a s u s e f u l o n l y f o r t h e a r e a s il-
the trans-Earth coast.
luminated by the sun, the gamma-ray experiment supplied
d a t a for t h e e n t i r e f l i g h t p a t h . Results
The orbital experiments described thus far proved to be
Alpha-Particle Experiment successful and informative. Before detailing the X-ray results,
There are a number of possible sources for alpha-particles it is important to describe some of the constraints that entered
from the lunar surface. The principal ones are alpha radio- into the interpretation of the data. Since the sun is not a stable
active decay of radon and thoron (and their daughter prod- X-ray source, it was necessary to devise methods of correcting
ucts) which, if circumstances are suitable, would have diffused for solar flux variation. Instru mentally, a small proportional
out of the first few meters of lunar soil. As on the Earth, this counter was pointed towards the sun while the large detectors
is a reflection of subsurface activity. If one assumes thermal were pointed towards the lunar surface. In this manner, the
velocities for the escaping radon and thoron, then nearly all sun's X-ray output was monitored during surface measure-
the molecules would be trapped in the moon's gravitational ments. Other sources of variation included the sample matrix
field. Radon with its 3.8-day half-life should travel a consid- effects, the solar illumination angle, and surface roughness.
erable distance before undergoing radioactive transformation. These factors were minimized by the use of intensity ratios
Thoron on the other hand, with a 55-sec half-life, would be (5). In view of the near constancy of the silicon abundance, the

of c e n t i m e t e r s . T h e d a t a g a t h e r e d b y s u c h e x p e r i m e n t s o n t h e
A p o l l o 15 a n d 16 m i s s i o n s y i e l d e d i n f o r m a t i o n a b o u t t h e r e l -
HAPPING OWESA
a t i v e i n t e n s i t i e s of t h e n a t u r a l r a d i a t i o n of t h e m o o n . F o r
MAPPING CAMERA
FILM CASSETTE example, the regions within a n d bounding the western maria
( O c e a n u s P r o c e l l a r u m ) s h o w h i g h e r levels of r a d i o a c t i v i t y
t h a n a n y o t h e r s on t h e l u n a r s u r f a c e . T h e r e is, in fact, a
s t r i k i n g c o n t r a s t b e t w e e n t h i s region a n d t h e r e s t of t h e m o o n ,
p a r t i c u l a r l y t h e e a s t e r n m a r i a . F u r t h e r , t h e r e is a d e t a i l e d
G N , CON'HOIS s t r u c t u r e in t h e d i s t r i b u t i o n or r a d i o a c t i v i t y w i t h i n t h e h i g h
radioactive regions. T h e highlands showed a relative radio-
a c t i v i t y e x c e p t o n t h e b o r d e r s of t h e w e s t e r n m a r i a w h e r e
PANOHAM1C CAMERA l a t e r a l m i x i n g is a g o o d p o s s i b i l i t y . O n e i n t e r e s t i n g r e s u l t i s
t h e o b s e r v e d r a t i o of K / T h . ( P o t a s s i u m is r e p r e s e n t a t i v e o f
v o l a t i l e e l e m e n t s w h i l e t h e t h o r i u m is r e p r e s e n t a t i v e of t h e
refractory ones.) T h e s e m e a s u r e m e n t s h a v e b o r n e o u t t h e fact
t h a t t h e m o o n is d e p l e t e d of v o l a t i l e e l e m e n t s r e l a t i v e t o t h e
refractory ones, a n i m p o r t a n t fact w h i c h m u s t be c o n s i d e r e d
m a n y t h e o r y of t h e m o o n ' s f o r m a t i o n a n d e v o l u t i o n .
A l p h a - p a r t i c l e d a t a t a k e n d u r i n g t h e A p o l l o 15 a n d 16
flights s h o w e d t h a t t h e o b s e r v e d a l p h a activity was q u i t e
s m a l l , o n t h e o r d e r of 1 0 ~ a c o u n t s / c m 2 - s e c . T h e n a t u r e of t h e
MASS e x p e r i m e n t was t o seek three t y p e s of signals: alpha-particles
SHCTftOMSTER
SPECTBOHnEB h a v i n g e n e r g i e s c o n s i s t e n t w i t h t h e d e c a y of 2 2 2 R n a n d i t s
daughter products, alpha-particles from 220Rn a n d t h e
d a u g h t e r p r o d u c t s , a n d finally, a l p h a - p a r t i c l e s from 2 l 0 P o .
T h e first t w o c a n b e associated only w i t h c u r r e n t activity
Figure 7. Al/Si intensity ratio along the ApoSlo 15 trajectory. ( b e c a u s e of t h e i r s h o r t h a l f - l i v e s ) a n d t h e l a s t w i t h e v e n t s
having occurred days t o years ago. (2I0Po comes from the
d e c a y o f 2 1 0 P b w i t h a half-life o f 21 y e a r s . ) T w o f e a t u r e s w e r e
o t h e r e l e m e n t s , s u c h a s M g a n d AI, w e r e r e f e r e n c e d t o t h e o b s e r v e d in t h e Apollo 15 d a t a . T h e r e a p p e a r e d t o b e a general
silicon. T h e r e w e r e o t h e r b o u n d a r y c o n d i t i o n s s u c h as t h e b u t small increase in c o u n t r a t e over O c e a n u s P r o c e l l a r u m a n d
d e p t h o f t h e s u r f a c e s a m p l e s ( i n t h e X - r a y c a s e a b o u t 10 ^ m ) , M a r e Imbrium. T h e trend appears to parallel the U and T h
t h e r e s o l u t i o n o f s u r f a c e s a m p l i n g w a s a b o u t 10 k m a n d , o f o b s e r v e d b y t h e g a m m a - r a y e x p e r i m e n t . O n e of t h e m o s t
c o u r s e , t h e o b s e r v a t i o n s w e r e o n l y f r o m t h e s u n l i t p o r t i o n s of d r a m a t i c f e a t u r e s w a s t h e i n c r e a s e i n 2 1 0 P o a t t h e e d g e of s o m e
the moon. of t h e m a r i a . A n a d d i t i o n a l c o r r e l a t i o n w a s t h e f i n d i n g o f
T h e c o m p o s i t i o n a l profile in t e r m s of Al/Si along t h e Apollo heightened activity in t h e Ariatarchus region where transient
1 5 t r a j e c t o r y is s h o w n i n F i g u r e 7. T h e r a t i o s for v a r i o u s a n - lunar p h e n o m e n a h a d been observed. T h i s last observation
alyzed l u n a r materials are shown on t h e r i g h t - h a n d axis. A is particularly interesting because t h e s e t r a n s i e n t glows which
n u m b e r of conclusions h a v e b e e n d r a w n b a s e d o n s u c h results: h a v e b e e n o b s e r v e d telescopically in t h e p a s t h a v e b e e n at-
t h e Ai/Si r a t i o s a r e g r e a t e r in t h e h i g h l a n d s ( c h a r a c t e r i s t i c of t r i b u t e d b y Borne i n v e s t i g a t o r s t o s o l a r e x c i t a t i o n of e s c a p i n g
f e l d s p a t h i c m a t e r i a l s ) a n d c o n s i d e r a b l y lower in t h e m a r e gases.
a r e a s ( t y p i c a l o f b a s a l t s ) ; t h e r e is a g e n e r a ! t e n d e n c y for A l / S i
values to increase from t h e western maria to t h e eastern iimb
h i g h l a n d s ; t h e r e w a s g o o d a g r e e m e n t b e t w e e n t h e AI2O3 v a l u e s
Summary
d e t e r m i n e d b y c l a s s i c a l t e c h n i q u e s o b t a i n e d f r o m a n a l y s i s of The results obtained from the remote analysis of the moon
l u n a r s a m p l e s g a t h e r e d d u r i n g t h e Apollo 17 m i s s i o n a n d f r o m by speetroscopic techniques have contributed substantially
t h a t inferred from t h e X - r a y m e a s u r e m e n t s . T h i s latter fact to a unified view of the chemistry of the lunar surface. Further
s h o w e d u s t h a t the X - r a y m e a s u r e m e n t s w e r e i n d e e d a r e l i a b l e important principles have been established for future plane-
g u i d e t o a t l e a s t t h i s a s p e c t of t h e l u n a r c h e m i s t r y . tary studies. The lunar investigations give us reason to believe
that such studies can he done on other surfaces many millions
T h e X - r a y results clearly d e m o n s t r a t e d t h a t t h e m o o n ' s of miles from Earth.
c r u s t is chemically differentiated. O n a global scale, o n e could
define t h e e x t e n t of differentiation a n d clearly t h e m a r e ba- Literature Cited
salts from the highland anorlhosites. T h e X-ray results have
also been correlated with optical albedos (the way in which (1) Turkevicii, A. L-, Anderson, W. A., Evonomou. T. E-.FranzgrutE, E. J., Griffin, H. E.,
(.retch, S. L., Patterson, .1. H., and Sowinaki, Kr Pr. The alpha-Seatlerinn Chemical
t h e lunar surface reflects light). It was clearly d e m o n s t r a t e d Analysis Experiment nn the Surveyor Lunar Missions," NASA Tech, Report 32-1265,
t h a t t h e reflectivity was a good clue to t h e chemical c o m p o - 1968.
sition. H i g h reflectivity w a s positively correlated t o m a t e r i a l s
(2> RuUier fold, E, Chadwick, J., end Ellia C. D,. "Radiation From Radioactive Substances,"
Cambridge University Press. iflÛ.
of h i g h A l / S i . S3) Vinogradov, A. P..5urjiov, I, A,, Chernov, G. M., and Kirnozov, F. F.. "MBastirerneiitB
of Gamma Radiation of the Moi>n's Surface by the Coarnte Station Luna 10,'' Geo-
T h e g a m m a - r a y experiment performed in two areas pro- chemistry No. 8, VernarMy Institute of Geochemistry and Analytical Chemistry,
v i d e d b o t h a s u r v e y of n a t u r a l r a d i o a c t i v i t y a s well a s c o n - Moscow, USSR, 1966,
s i d e r a b l e i n f o r m a t i o n a b o u t t h e c h e m i s t r y of t h e s u r f a c e . D a t a
(i) Kraner. H, W., Schroedcr, G. £.., Davidson, G.. and Carpenter, J. W,, "Radioactivity of
the Lunar Surfece," Science, 15*, m i (1966).
was g a t h e r e d from a belt a r o u n d t h e m o o n . In t h e X - r a y ex- (5) Adler,i..Tromhba,J.,C^rard,.i.,Schmade!iedi,Ii.,Lowman,P.,Blodjelt,H.. Yin,L-.
p e r i m e n t , s a m p l e s w e r e t a k e n a t a d e p t h o f a b o u t 10 ftm. T h e Eller, E,, Latnuthe, R., Goreostsin, p., Biorkholm, P., Harris, B,, end Gursky, H., X-ray
Fluorescence Experiment," Apnllo 15 Preliminary Science Report, NASA Sp-289,
g a m m a - r a y e x p e r i m e n t p r o b e d t o d e p t h s of t h e o r d e r of t e n t h s 972

edited by:
DAVID A. PHILLIPS
Wabash College
Crawfordsvllle. IN 47933
Goal/ PRUDENCE PHILLIPS

Crawfordsvltie High School
Crawfordsville, IN 47933
Introduction to "Goafs"
In planning a chemlslry course, some of the moat important decisions a teacher must make involve the selection of material !o be covered
and the time to be devoted to each topic. For each column in this new series, a high school and a coilege teacher have been Invited to discuss
why they feel a particular topic is Important and how it contributes to the students' understanding of chemistry.
About the Editors...

David A. Phillips received his BS in chemistry from the University of Red-
lands and his PhD from the University o! Washington. After directing the General
Chemistry program at Middle East Technical University In Ankara, Turkey for
two years, he came to Wabash College, where his primary teaching interests
are in general and inorganic chemistry.
Prudence K. Phillips received her AB In chemistry from Brown University
and her MS from the University ol Washington. She has been teaching nigh
school chemistry for 11 years and Is presently at Crawlordsviile High
School.
Both Hie Philllpses have participated In a variety of Division o! Chemical
Education and ACS activities.
Why Teach Kinetics to High School Students? Kinetics—Rates and Mechanisms

High school students often avoid chemistry because it de- Probably 90% of chemistry teaching deals with chemical
mands mathematical reasoning. For that reason, high school equations using an arrow or equal sign to connect the formulas
teachers generally deemphasize math in first-year courses of products and reactants. Without such highly informative
except where it is necessary for understanding- Nevertheless, (at least to some) equations, treatments of stoichiometry,
I stress kinetics, a topic that demands at least a bit of math. equilibrium, thermodynamics, synthesis, and analysis would
Consequently, I must justify annually the time spent on ki- be quite impossible. However, there is one subject in which
netics at the expense of other topics in the curriculum. the equation for the net reaction has only a limited use. That
We chemists do a great deal of theoretical hand-waving, subject is kinetics and its main sub-areas—rates and mecha-
and, after a while, chemical theory seems like fantasyland to nisnis of reaction.
most high school students. I stress kinetics because collision Using only the equation for the net reaction and the for-
theory seems fairly easy for high school students to under- mulas it contains, there is no way of confidently predicting
stand. In my course, they understand kinetic-molecular theory either a reaction rate or a reaction mechanism. Even the effect
pretty wel! because it has been supported clearly by student of temperature on the rate cannot be told with certainty. In-
experiments and instructor demonstrations, we have also telligent control of a reaction requires knowledge of the vari-
thoroughly covered the behavior of solid spheres prior to the ables which aff&et its rate. A knowledge of reaction mecha-
introduction of kinetics, which gives them all they need for nisms is in turn essential to the understanding of reactions at
a primitive understanding of the topic. the atomic-molecular level. Most introductory teaching of
From their knowledge of theory, the students practice sci- kinetics starts (and often stops) with a determination of the
entific reasoning by predicting the effects of concentration and factors affecting the rate. So let's start there (but also let's not
temperature on reaction rate. They then have the exciting stop at the standard places).
experience of confirming their predictions in lab. With this Rates are most commonly discussed in terms of three,
information and their prior grounding in theory, they can variables: the nature of the system, its temperature, and the
understand reaction mechanisms, rate laws, activation energy concentrations of the reactants. Even changes resulting from
and catalysts. They have gone into the lab to answer real stirring, altering surface areas, or adding catalysts can be
questions rather than to demonstrate some principle ex- handled in terms of variations in systems, temperatures, and
plained in advance. Is the acid a catalyst? If so, an+ extrapo- concentrations. Reasons cited for studying these effects in-
lation of the rate versus concentration graph to fH j = Gwill clude providing a deeper understanding of the nature of the
show a finite reaction rate. Does the fast step in a reaction reactions and an enhanced ability to control their rates. Yet
involve one molecule or two? Altering concentrations of re- few standard treatments really do either successfully.
acting species will clearly indicate which is the case.
The lab work also helps the students to develop a host of Concentration Effects
important skills. Careful measurements of volumes, times, and Almost all chemical systems studied are found t o involve
first-and second-order reactants, most often with orders equal
(Continued in col. 1, page 41) {Continued in col. 2, page 41)

temperatures must be made. Correct calculations of concen- t o t h e coefficients in t h e n e t e q u a t i o n . N o m a t t e r h o w m a n y
trations, logs, etc. must be made and the results accurately a d m o n i t i o n s (even in h o l d face) t h e r e m a y b e a g a i n s t d e d u c i n g
plotted. This plethora of calculations seems much more pal- orders from coefficients, t h e s t u d e n t s n o t e t h e correlations
atable to my students when they are using calculations to help and remember them. W h y not use examples where this ap-
solve a real lab problem, than when they are just manipulating parent, b u t untrue, correlation does not exist?
math formulas. When the data from different lab groups from F e w t r e a t m e n t s d i s c u s s t h e i m p o r t a n c e of z e r o - o r d e r
all classes are pooled, the necessity for replication is obvious; reactants, which commonly occur. For example, m o s t physi-
although individual runs often don't work well, the combined ological r e a c t i o n s a r e zero-order w i t h r e s p e c t t o t h e s u b s t r a t e ,
data always yield clear relationships. e.g., g l u c o s e . C o n s i d e r t h e p r o b l e m s h u m a n s w o u l d h a v e w i t h
The Jabs help the students to discover for themselves the t h e i r e a t i n g r a t e s if t h i s w e r e n o t t r u e . A n y v a r i a t i o n i n l o c a l
idea that a reaction can have several plausible mechanisms. glucose concentration would cause a variation in physiological
Before they do the experiments, I discuss nucleophilic sub- rates. M a n y living s y s t e m reactions c i r c u m v e n t this p r o b l e m
stitution reactions and physically model first- and second- by operating with a simple first-order kinetics involving a n
order mechanisms, being careful not to tip off the results to e n z y m e c o n c e n t r a t i o n which t h e y can control to give an a p -
them. Consequently, the students develop a feeling for the role p r o p r i a t e r a t e of r e a c t i o n . S i m i l a r l y , m a n y e n v i r o n m e n t a l
of physical models in predicting reactions. p r o b l e m s h a v e r a t e s w h i c h a r e zero-order in c e r t a i n possible
reactants. S o m e bodies of w a t e r have algal growths which a r e
Once a mechanism has been determined in lab, I introduce
first-order in n i t r a t e , zero-order in p h o s p h a t e . O t h e r b o d i e s
several reactions for which the mechanisms are unknown. I
h a v e t h e o r d e r s r e v e r s e d . C o n t r o l is p o s s i b l e b y r e g u l a t i n g j u s t
stress that this is a major field of chemistry in which the stu-
o n e o f t h e c o n c e n t r a t i o n s , but first i t m u s t b e d e t e r m i n e d
dents might make contributions. In fact, many of them end
which concentration affects t h e rate. Seattle h a d a p r o b l e m
up doing research projects in kinetics.
w i t h this s o m e years ago a n d initially tried controlling t h e
I also stress kinetics because I've found clear understanding zero-order reactant. Unsuccessful.
of the effects of concentration on reaction rates helps my
students understand dynamic equilibrium. O n e o f t h e m o s t u s e f u l d e f i n i t i o n s of a c a t a l y s t ( b y H . B e l l )
To summarize, my course includes art emphasis on kinetics is a r e a c t a n t w h o s e c o n c e n t r a t i o n a p p e a r s i n t h e r a t e e q u a t i o n
because: (1) tlie theory is qualitatively simple; (2) students are w i t h a n e x p o n e n t higher t h a n its coefficient in t h e c h e m i c a i
able to practice their scientific reasoning in a meaningful way; e q u a t i o n . T h i s is a h i g h l y o p e r a t i o n a l d e f i n i t i o n w h i c h g i v e s
(3) the experiments make palatable the repetitious practice insight into w h y a catalyst affects a rate.
of important lab, calculation, and graphing skills; (4) students A m o s t i m p o r t a n t , b u t s e l d o m d e v e l o p e d , r e a s o n for
develop a feet for the importance of molecular structure and s t u d y i n g c o n c e n t r a t i o n e f f e c t s is t h a t t h e o r d e r o f a r e a c t i o n
action at the molecular level; (5) I can introduce the idea that often gives d i r e c t i n s i g h t i n t o t h e f o r m u l a of t h e a c t i v a t e d
there are still questions in chemistry which the students may c o m p l e x f o r m e d in t h e r a t e - d e t e r m i n i n g s t e p . 1 k n o w of n o
be able to answer; and (6) the ideas developed in studying m o r e p o w e r f u l m e t h o d for g a i n i n g p e r s p e c t i v e o n h o w m o l e -
kinetics are important for understanding equilibrium. cules a c t u a l l y i n t e r a c t t h a n writing p r o b a b l e s t r u c t u r a l for-
Finally, I stress kinetics because the students and I enjoy m u l a s of t h e activated complexes. Y e t few t r e a t m e n t s provide
clock reactions immensely. Teaching kinetics gives me Jots of g u i d a n c e h e r e . T h e f o r m u l a of t h e a c t i v a t e d c o m p l e x is u s u a l l y
excuses for demonstrating these reactions while 1 lecture. j u s t t h e s u m of t h e f o r m u l a s of t h e s u b s t a n c e s in t h e r a t e
e q u a t i o n . If t h e r a t e e q u a t i o n i s :
WIHtam G. Lamb
Oregon Episcopal School rate = k[X}mmn
6300 SW Nicol Road t h e n t h e f o r m u l a o f t h e a c t i v a t e d c o m p l e x is X m Y u . I t is o f t e n
Portland. OR 97223
p o s s i b l e t o w r i t e a r e a s o n a b l e s t r u c t u r a l f o r m u l a for t h e
c o m p l e x a n d t h u s p r e d i c t w h i c h m o l e c u l e s collide in t h e r a t e
determining step, what bonds form, what bonds break, and
w h a t p r o d u c t s r e s u l t . T h i s is a g r e a t d e a l of i n f o r m a t i o n a n d
it p r o v i d e s excellent i n s t r u c t i o n as t o w h a t is a c t u a l l y con-
c e a l e d in t h a t e q u a l s i g n or a r r o w in t h e e q u a t i o n for t h e n e t
r e a c t i o n . T h e f o r m u l a of t h e a c t i v a t e d c o m p l e x a l s o gives in-
About the Authors sight into catalytic behavior.
J. Arthur Campbell is Professor of Chemistry al Harvey Mudd Coifege, Temperature Effects

where he teaches freshman and physical ctiemislry. He has an AB in
Almost every treatment presents the Arrhenius equation
Chemistry from Oberlin College, an MS from Purdue University, and a
PhD from the University of California, Berkeley. He has had a tons and
and discusses activation energies, but there are often three
illustrious career teaching and consulting at institutions around the world. serious deficiencies, all easy to remedy with a little additional
He is a past chairman of the Division of Chemical Education and has theory. The most obvious is the failure to mention the mini-
nerved ort many national and international committees. He has numerous mum, but appreciable, effect due to the increased rate of
honors Including the Manufacturing Chemists' Award for the Teaching molecular collisions with temperature, which the student
of Chemistry. learned about earlier in the course. True, this is a small effect
compared to the exponential Arrhenius effect, but a clear
discussion of their relative sizes clarifies the issue.
WilHam G. Lamb holds the Witiningstad Chair of Physical Sciences More serious is the error of telling the student that a catalyst
at the Oregon Episcopal School, where he teaches chemistry and operates by lowering the activation energy. This is just not
physics and serves as department head. He earned his MA and PiiD In true. A catalyst provides a new mechanism. The old mecha-
science education from the University of Texas a! Austin and participated nism continues with its activation energy unchanged. There
in the first Dreyfus Institute on High School Chemistry. His recent ac- must be an increase in rate simply because there are now at
tivities include directing a state science fair, development of a descriptive least two mechanisms operating, not just the one of the orig-
physics course which will serve as a prerequisite for chemistry, and the inal reaction. The most fascinating problem here is that, for
initiation of a high school studem research program in chemistry (for many systems (especially those involving enzymes), the cat-
example, some of his students are doing projects on semiconductor alyzed reaction may actually have a higher activation energy
photochemistry).
(Continued in col. 1, page 42)

than the uncatalyzed one, yet its rate may be thousands of equal sign or arrow of the net equation conceals much of the
times faster at comparable concentrations of substrate. It most interesting part of chemistry, (2) control of a reacting
seems a shame to include such an important point so late in system necessitates determination of reaction orders, (3)
an essay, but better late than never. knowledge of reaction orders allows a good guess at the for-
Of course, this problem of an increased rate despite the mula of the activated complex, (4) knowledge of this formula
greater activation energy is solved by considering the free reveals a great deal about the rate determining step and the
energy of activation, a decrease in which does increase the rate. role of any catalyst involved, and (5) study of the temperature
Thus we make a marvelous tie between thermodynamics and effect may be coupled with entropy of activation effects to
kinetics and a most useful extension of the entropy principle provide deep insight into the energetics of reactions and a
to reaction mechanisms. If the activated state is less organized correlation of thermodynamic ideas with kinetics. Doesn't it
than reactants and products, the entropy of activation is high. seem short-sighted to stop with simple rate equations and
This lowers the free energy of activation, even though the leave mechanisms as dark secrets?
energy of activation may be larger. A knowledge of the factors affecting rates {as in the
Arrhenius rate equation) allows engineering control of a
AGfl = AEa - T&Sa chemical system. Knowledge of mechanisms (such as formulas
with AEH ca AHS for most systems. Thus, the rate is increased. of activated complexes and free energies of activation) allows
It is interesting that some organic texts are ahead of many insights into the chemistry a t the molecular level. Shouldn't
physical chemistry texts in this area. chemistry students achieve such insights?
Why Teach Kinetics?

There are so many reasons for teaching kinetics early and J, Arthur Campbell
often. If it is done just a bit more thoroughly than is now Harvey Mudd College
common, the students (with iittle extra effort) see that (1) the C!aramont,CA91711
Use of Photocopying for Non-Destructive Leaf Area Measurements

Planar measurements of area are frequently required for very
diverse applications. General methods include planimetry, grids, dot
counting, established correlation1formulas, shadow or photographic
prints, and various area meters. '2 In our work on plant growth and
metabolism, it is often necessary to determine leaf shape as well as
area. To study continuous growth and change in development, the
method of measurement must be applicable to intact plants, non-
destructive, and should provide a permanent record of linear di-
mensions. Preferably, the method should also be adaptable to fragile
leaves of intricate shape and variable size, e.g., the compound leaf of
tomato. A method combining genera! practices used in blueprinting
and photocopying serves very well for this purpose.
The method consists of four steps. The first step utilizes a stage
made from two Plexiglas® sheets separated at the corners by small
squares of 1.3-mm thick foam mounting tape to hold a sheet of stan-
dard weight Diazo paper OVa X 13 in. blueprint, rapid speed 11). An
additionalPiexigiassiieet, hinged at one end to the other two and spaced appropriately with foam tape (3.9 mm), is placed
over the undetached leaf. After the leaf is positioned, bayonet forceps (e.g., Lucae ear forceps) can be used to gently separate
any overlapping or curled leaves. Dia?,o paper is inserted and subsequently exposed with a photospotlamp(G.E. PH/RSP
2, 500 W) applied from a fixed distance of 12-15 in. above the stage for 10-15 s untiltfiepaper blanches. Second, the leaf
print is developed in a hood by passing aa inverted glass funnel connected with tubing to a tank of NH3 gas over the exposed
paper. If NHS gas is not available, a print may be held over a shallow dish of concentrated NH4OH for development. Third,
a photocopy (e.g., Kodak Ektaprint ISO copier-duplicator) is made of the leaf print to provide a clean, permanent record.
From the photocopy, afinalprint is reproduced on a transparency (e.g., Kodak Ektaprint), Fourth, from the transparency
print, area measurement is obtained by a grid, planimetry, or an area meter. In our use, measurements from the transparency
prints by a LiCor 3000 area meter are within ±0.5% of compared direct measurements of detached leaves. The use of trans-
parencies, which can be cut into strips, allows measurement of leaf sizes larger than can be accommodated by a portable
area meter.
Since lamp intensity decreases with use, replacement of the lamp in the system will require adjustment of either the
exposure time (decreased) and/or distance above the stage (increased) in order to maximise the clarity of the print and to
avoid thermal damage to plant tissue dueto-the increased intensity. Our measurement of leaf temperature, under the described
conditions, indicates a maximum expected increase of 5-6"C during exposure.
Reference to a company and/or product named by the Department is only for purposes of information and does not imply
approval
! or recommendation of the product to the exclusion of others which may also be suitable.
2 Marshall, J. K, Photosynthetka, 2,41 11968).
Kyet, J., and Marshall, J. K, "Plant Photo-synthetic Production. Manual of Methods," {Editor. Sestak, Z.), Dr. W. Junk
N.V. Publishers, The Hague, 1971, p. 517.
Marian L. Lyman
Donald E. Campbell
J. Corse
Western Regional Research Center
Agricultural Research Service
U.S. Department of Agriculture
Berkeley, CA 94710

A High School Biochemistry Course
George B. Powers
Old Town High School, Old Town, ME 04468
The first-year chemistry courses at Old Town High School Course Outline
were described in a previous article in THIS JOURNAL 1 . This
Weeks Topic Chapter Laboratory
article will describe a senior-ievel, advanced course in bio-
chemistry. This biochemistry course was designed for students 1 Matter and Measurement 1 None
planning to pursue careers in nursing, engineering, and agri- 1 Elements, Atoms, and Compounds 2 Worksheet
culture. T h e author, before he began teaching at the high 1 Atoms and their Elements 3 Worksheet
school level, was a graduate assistant in the Biochemistry 1 Compounds and Bonding 4 Worksheet
Department at the University of Maine a t Orono where he 1 Chemical Reactions 5 Worksheet
assisted in the teaching of the biochemistry classes as well as 1 Organic Chemistry 9 Carbon
their laboratories. This experience led to the conviction that 1.5 Saturated Hydrocarbons 10 Hydrocarbons
2 Unsaturateii Hydrocarbons 11
high school students need to see what college courses are like.
1 Stereoisomerism and Optical 12 None
Therefore, the course is taught in a manner as close to the
Activity
college course as possible. The students are given a syllabus 1.5 Alcohols, Phenols, and Ethers 13 AScohols and Ethers
at the start of the course containing all the reading assign- 1 Aldehydes and Ketones 14 Aldehydes and
ments. Most general assignments are neither collected nor Ketones
graded (as on the university level in biochemistry). 1 Carboxylic Acids 15 Preparation ot
Asperir
Course Description and Outline 1 Functional Derivatives of Acids 16 None
1 Amines 17 isolation of Caifeine
Our second-year chemistry course includes general, organic, 0.6 Intermofecular Forces None None
and biological chemistry. The prerequisites are first-year 1 Introduction to Biochemistry 7 (parts), Acidity of Vinegar
chemistry and instructor approval. The course is scheduled o
O
for three 42-min lecture periods and two 84-min laboratory 2 Carbohydrates ie' Carbohydrates
periods per week. The student takes the course for a full year isolation of Starch
for 1 credit. 1.5 Uplds 19 Isolation of
The format of the course is primarily lecture, but handouts Cliolester
3 Amino Acids and Proteins 20 Paper
are used liberally. Demonstrations and a few laboratory tests
Chromatograph of
are also done during lecture. The laboratories have been
Amino Acids
chosen to follow the lecture topics. Many of the experiments 2 Enzymes 21 Enzyme Kit"
are t h e same as those done on the college level, e.g., Isolation Production of
of Caffeine, Isolation of Cholesterol, Preparation of Aspirin Cheese
and Preparation of Soap. 2 NucSeic Acids (Protein Syn.l 23 Protein Synthesis Kit
The textbook used for the course is "General, Organic and 0.5 Minerals None None
Biochemistry" by Rogers and Brown.2 A college text must be 1 Vitamins and Coenzymes None None
chosen since, to my knowledge, no high school biochemistry 1 Nutrition None None
textbooks are available. Therefore, some of the textbook 1 Flow o( Energy in Biol. World 23 None
3 Carbohydrate Metaboiism 24 Metabolism Game
material must be omitted or simplified. The course outline is
1 Upid Metabolism 25 None
given in the table, 1 None
Amino Acid Metabolism 26
2 Integration of Metabolism None Worksheets
Other Material
One of the favorite activities of the course is the seminars. * Experimental Enzymology Kit #20-2275 Carolina Biological SiîpSy Company, Burlington,
N.C. 27216
Each student is required to present a 15-min seminar in a bi-
ological area of his or her choice. The students use the high
school library, the University of Maine, or other sources to Scientific American. C a r o l i n a Biological S u p p l y offers a n
research their topics. Some of the topics covered are: Death o u t s t a n d i n g series of s h o r t m o n o g r a p h s o n biochemical topics.
and Dying, Biolumineacence, Sleep and Dream States, and S t u d e n t s also read a n d practice with a k i t called " E l e m e n t s
Birth Control. of P r o t e i n S y n t h e s i s " b y T h o m a s P e t e r B e n n e t t . 3
At several points in the course, professors from the Uni-
versity of Maine a t Orono come and talk to the class. They T h e best-liked a n d m o s t utilized outside materialia a game,
cover such areas as nucleic acids, genetic engineering, bio- p r o d u c e d f r o m a n a r t i c l e i n The Biology Teacher.4 T h e article
chemistry of aging, and photosynthesis. describes h o w t o m a k e a n d play t h e m e t a b o l i s m game, cov-
The students also are given selected outside readings where' ering glycolysis, citric acid cycle, c o e n z y m e s , a n d t h e electron
they coincide with class materials; several are reprints from t r a n s p o r t system. T h e s t u d e n t s learn Teactante, products,
energies, a n d e n z y m e s r e q u i r e d for t h e m a j o r m e t a b o l i c cy-
cles.5
1
Powers, George B., J. CHEM. EDUC., 58,1015 (1981).
2
Rogers, E. P. and Brown, W. H., "General, Organic and Biochem- Conclusion
istry, Willard Grant Press, Boston, 1980.
3
Bennett, Thomas Peter, "Elements of Protein Synthesis," W. H.
In general, the students who have taken this course have
Freeman and Company, 1969. found it to be a great help. Not only do the college chemistry
4
Goodman, Richard E., The Biology Teacher, 34[2], 78 (February, courses they eventually take cover many areas included in this
1972). biochemistry course, b u t t h e course also serves as a n intro-
5
The game is now available from the Carolina Supply Company. duction to the college level approach to teaching.

Implementation of the Thai High School
Chemistry Curriculum
Nlda Sapianchai and Thongchai Chewprecha
Institute for the Promotion of Teaching Science and Technology (IPST)
924 Sukhumvit Road, Bangkok 10110, Thailand
Thailand, with a population of 48 million, is one of the The Institute for the Promotion of Teaching Science and
oldest countries in Southeast Asia. Before 1963, Thailand Technology
required four years of compulsory education. In 1978 the Thai The nationwide chemistry curriculum at the upper secon-
government promulgated a new, 6-3-3 educational system (six dary school level prior to 1976 in Thailand had been very
years of elementary level, three years of lower secondary level, traditional hi comparison to many other countries. Theoretical
and three years of upper secondary level) with six years of chemistry and laboratory chemistry were taught separately
compulsory education required for all children. Educational with little relationship between them. Laboratory was not a
administration in Thailand is a centralized system: all schools required part of the course. Some topics were out of date;
throughout the country must use the same curriculum au- others, such as calculations and descriptive chemistry, were
thorized by the Ministry of Education. presented in too much detail. On the other hand, many im-
Since secondary education is not compulsory, study at that portant chemistry topics, such as bonding, rate of reaction,
levei depends on the parents' financial status and the student's and equilibrium, were ignored.
own ability. In 1975, about 31% of the 14-16-year-old group Teaching strategies, emphasizing memorization, were based
was enrolled in the lower secondary level and about 12% of the entirely upon a teacher's teaching rather than a student's
17-19-year-old group was enrolled in the upper secondary learning. Teachers were not familiar with investigative or
level. The number of students desiring to enrol! in the public inquiry teaching techniques. High level questions were seldom
school exceeds space available; therefore, an entrance exam- asked. Students were not encouraged to ask questions, think,
ination is required. Private schools can enroll some of the present ideas, or participate in a class discussion.
unadmitted students, but this still is not sufficient to ac-
For a long time, this approach to chemistry had been criti-
commodate all who desire secondary education. Education
cized by many science teachers and science educators in
after the secondary level leads to one of two programs: the
Thailand. They agreed that new chemistry courses was needed
four-year bachelor degree program or the one-to-three year
for the upper secondary school, However, no attempt was
diploma program. There are 40 institutions which now offer
made to do this until 1972, when the Institute for the Pro-
the bachelor's degree, including 17 small teachers' colleges,
motion of Teaching Science and Technology (IPST) was es-
10 private colleges, 12 public universities, and I open uni-
tablished through cooperative action of the Roya! Thai Gov-
versity. Entrance to any public university is very competitive;
ernment, the United Nations Development Program (UNDP)
only about 20-30% of the applicants can be accepted. In 1976,
and its executing agency, the United Nations Educational
for example, the institutions of higher learning accepted only
Scientific, and Cultural Organization (UNESCO). The main
. 12,502 applicants. An entrance examination is the main pro-
purpose of the Institute has been to develop modern science
cedure used to select applicants. Private colleges also admit
and mathematics curricula at every level below the university.
some students t o limited areas of study but their enrollment
Chemistry at the upper secondary school level was one of the
is small since these institutions are expensive.
first of the curricula to be developed, and its the nationwide
The one-to-three year programs of study, including training implementation began in 1976 after three years of trial
of technicians and skilled workers, are offered in over 100 teaching from 1973 to 1975.
technical institutions. These programs are, however, much less
popular than the four-year bachelor degree programs.
Graduate programs are offered only in a few universities in tPST Chemistry Curriculum
limited areas. The enrollment of the graduate programs is The IPST chemistry curriculum is very different from the
small due to the limitations of subject specialists and facili- earlier traditional chemistry curriculum. Theory and labo-
ties. ratory are integrated within the same course. Students are
required to perform the experiments, observe, measure, gather
Science Teaching in the Secondary Schools data, organize data, interpret, make predictions, and draw
The three years in the lower secondary education program, conclusions from their own data. Inquiry and investigative
M.I, M.2, and M.3 are roughly equivalent to grades 7,8, and teaching approaches were introduced to the teachers and they
9 in the U.S. Science is studied in each of these grades, four were encouraged to use these approaches in their teaching.
periods a week. An integrated science program is presented The unique characteristics of the IPST chemistry curric-
rather than separate disciplines such as chemistry, biology, ulum can be described as follows; It is inquiry-oriented (ex-
or physics. pecting students to think and to explain why), investigative
Students at the upper secondary level who plan to further (more doing chemistry), student-centered (stimulating their
their education in science or science-related fields would be interests, ability, and ultimate use of chemistry), relevant
guided to take up to 60 semester credits in specific scientific (meaningful to everyday living), and innovative (new exper-
courses such as chemistry, biology, and physics. They are also iments, new equipment, new style of teaching, and new
allowed to choose several elective courses. Nonscience stu- scheme of evaluation). Experiments play a large part, and the
dents and those who plan to terminate their study upon curiosity of the student is aroused. The student is placed in
graduation would be required to take only 12 semester credits the role of discoverer, and the exciting, creative implications
of science. A new modular physical science course is recom- of this adventure encourage the student to become involved
mended for this purpose. in his (her) own learning. Learning by inquiry, however, does

not necessarily mean that a whole curriculum will consist of Instructors of the inservice program used the techniques
experiments and problems. Curriculum developers in IPST and methods which they wanted the teachers to use in their
science subjects have attempted to obtain a balance between classroom. Although few special lectures on content or
factual content and inquiry activity. The criteria for selection methology were given, through this role-playing technique
of contents include the following: teachers were exposed simultaneously to both. Teachers also
had an opportunity to (1) perform, all experiments which they
Content selected should would have to supervise in the classroom, (2) observe and use
1) lead up to modern science and reflect the basic ideas and videotapes, audio slide-tapes, audio filmstrips, and pro-
structures of the most recently accepted advances. grammed instruction booklets about the classroom manage-
2) show continuity and follow a logical conceptual scheme. ment of experiments, laboratory safety, etc., and (3) discuss
3) have a capacity for unifying and explaining the widest variety the IPST philosophy and objectives of chemistry teaching,
of phenomena and data.
4) be teachable within the time allocated and be suitable for the and participate in its evaluation.
students' intellectual maturity and interests. To date, over 90% of the chemistry teachers have completed
5! be within the capability and experiences of theteachersand the at least two 90-hr IPST training sessions. In addition, elabo-
adequacy of resources. rate teacher guides have been produced by the IPST to assist
6) contain examples ofimportant applications to technology, ag- the trained teachers. In follow-up meetings, they report that
riculture, medicine, industry, and social science in Thailand. these teacher guides have been of tremendous help.
7) bring out the relationships to other fields of study, especially
to the natural science and mathematics.
8) contribute to the growth and development of the individual as Equipment and Chemicals
well as society and stimulate the proper utilization of natural In addition to the need to train teachers in new techniques,
resources and the preservation of the environment. school budgets for equipment and chemicals, teaching load,
The IPST chemistry contents can be summarised as shown and class size pose other problems to the implementation of
in Figure 1, IPST. At the present time about 600 schools, 54,000 students,
and 750 teachers are learning or teaching chemistry at the
The iPST tnservice Training Program upper secondary school level. The average number of students
The teachers who would teach IPST chemistry were the in a class is 45. The average teaching load is 20 periods per
same teachers who formerly had taught traditional chemistry. week. Students study 3 periods of chemistry per week.
They were familiar with traditional chemistry topics and Because no laboratory assistants are available, teachers
traditional teaching styles. This created the most difficult have to prepare all their own teaching aids needed for student
problem in implementing the new curriculum a t IPST. Cur- experiments. Most schools do not have enough laboratory
riculum developers at IPST realized that the success of their rooms; very often students have to do experiments in a regular
work depended upon how well they could train these teachers. classroom in which electricity and water are not installed.
Thus an IPST inservice training program was developed with Students often have to carry a bowl of water and equipment
three main purposes: (1} to ensure that teachers have a sym- from room to room. IPST has had to design experiments and
pathetic attitude to the new teaching approach; (2) to ensure equipment so that they can be used in such circumstances.
that teachers understand the subject matter; (3) to ensure that Altogether, students have to perform about 90 experiments
teachers know how to use the new materials including the within 6 semesters; some representative examples of the ex-
visual aids and new laboratory equipment. periments performed as listed below.
• Environment
Gas Reactions-Conservation of Mass • Organic -
Compounds-
Matter Chemistry and Industry
Gas Laws Law of Chemical „, ' ...

Combination Changes of Matter Equilibrium
/
Elements,
Kinetic Theory Compounds,
Solutions Bate of Reaction
Avogadro's Law
Properties of Solution Collision Theory
Mole Concept Periodicity Structure of Activation Energy

atoms, molecules,
and crystals
Electrical Periodic Table"
Nature of Matter
' lonization Potential

Electron Affinity
Atomic Theories Electro negativity
• Bonding
Latest concept of atom
Figure 1. Concepluat scheme of the IPST chemistry course (six-semeslei course, three periods a week].

Matter and Changes: d e v e l o p m e n t of local chemical a n d science e q u i p m e n t i n -
boiling of solutions and substances d u s t r i e s . U p t o t h i s p o i n t I P S T e q u i p m e n t is lower in cost
solvent extraction w h e n c o m p a r e d w i t h i m p o r t e d m a t e r i a l s , a n d a l m o s t all
steam distillation extraction e q u i p m e n t uses local m a t e r i a l . Several p r i v a t e l y - o w n e d ,
separation by ehiomatography small-scale factories for t h e production of e q u i p m e n t , a n d o n e
energy and solubility science e q u i p m e n t p l a n t h a s been organized b y a commercial
energy and chemical reaction
Stoichiometry (1): e n t e r p r i s e of t h e T e a c h e r ' s Association.
the study of mass in the system T h e I P S T e q u i p m e n t is classified i n t o four g r o u p s : (1) t h e
reactions between copper and sulphur s t u d e n t ' s kit, (2) kits for special s t u d e n t e x p e r i m e n t s . (3) kits
mass ratio of elements in lead f II) iodide for t e a c h e r d e m o n s t r a t i o n , (4) e q u i p m e n t for t e a c h e r p r e p a -
gas evolved from tiie reaction between oxygen and nitrogen mon- r a t i o n , T h e s t u d e n t ' s k i t is s h o w n o n F i g u r e 2, a n d selected
oxide e x a m p l e s of t h e e q u i p m e n t d e v e l o p e d locally a r e i l l u s t r a t e d
approximation of molecular size of oiek acid in Figures £ - 4 .
Stoichiometry (II):
preparation of solutions 1} The student's kit. This contains all the basic laboratory
heat energy of chemical reaction equipment needed by the student and should be ail that he or she
requires for at least 75% of the experiments in the course. There are
All the equipment used in chemistry courses at the upper two different kinds of storage: the wooden kit box and the open mesh
secondary level except some glassware and balances has been plastic tray. T h e items in t h e kit are the same in both cases. T h e kit
designed by IPST and produced by local industries. Oniy some was designed so that experiments in the new curriculum couSd be
sophisticated equipment parts are imported; these are then performed in any room in the school where there was a table for the
assembled within the country. It is the IPST's goal to design student to put the box on.
low-cost equipment using local materials, thus encouraging 2} Kits for special student experiments. There are some pieces
of equipment which are used several times during the course but not
often enough to be included in the student's kit. This type of equip-
ment includes t h a t for the conductivity test, the electrolysis appa-
ratus, and the insulated beaker (calorimeter). These will be supplied
by the teacher when they are needed.
3) Kits for teacher demonstration. There is a small amount of
equipment for teacher demonstration. It includes the ion migration
set and the molecular and crystal models.
4) Equipment for teacher preparation. To assist the teacher in
the task of preparing chemicals and solutions for the experimental
workin the course, a set of additional equipment has been assembled.
It includes additional glassware, storage bottles, volumetric flasks,
pipet, and a buret.
Conclusion
Teachers are the most important Sink in the educational
system. The training conducted to help these teachers acquire
Figure 2. KB containing student experimental equipment.
Figure 3. Apparatus for boiling-poln! determination. Figure 4. Acid-base reaction carried out using a syringe.

the necessary teaching skills and confidence is of utmost im- achieve its goal, if the teachers are not provided with necessary
portance, In this connection, equipment and teaching mate- materials to sustain their program. With the demands on their
rials must be readily available so that the schools can purchase time being what they are, teachers can not expect to produce
them at reasonable prices. Even the best curriculum will not very much of their own equipment or materials,
edited by
thumbnail /ketche/ MARY VIRGINIA ORNA,

College of New Rocheile
New Rocheile. NY 10801
O.S.U
Metal Substitutions in Wartime Coinages Coinage Metal Changes Brought About by World Wars I and II s
Hugh A. Akere Coinage Metal
Lamar University Country Denomination War Prior During
Beaumont, TX 77710
Austria 2 Helier I Cu Fe
W i t h t h e t r e n d t o w a r d s i n c l u s i o n of m o r e d e s c r i p t i v e m a - 20 Heller 1 Ni fe
terial in chemistry, m a n y t e s t s h a v e , in addition t o m e n t i o n i n g Belgium 5, 10, 25 Centime l.il Cu-Ni Zn
u s e s of specific elements, also included information on t h e 50 Centime 1 A3 Zn
1 Franc II Ni Zn
s o u r c e s a n d d i s t r i b u t i o n of t h e a p p r o p r i a t e r a w m a t e r i a l s .
Bulgaria 10, 20 Stcrtinki i Cu-Ni Zn
T h e r e a r e o f t e n c o m m e n t s o n t h e effects of s t r a t e g i c s u p p l y
1Lev 1! Cu-Ni Fe
i n t e r r u p t i o n s , u s i n g t h e r e c e n t oil e m b a r g o a s a n e x a m p l e . F o r
Canada ECent 11 Ni Cu-Zn, Fe
i n s t r u c t o r s i n t e r e s t e d in t h i s a r e a t h e r e a r e a c t u a l p h y s i c a l 1 Fe
Denmark 1,2, 3 Ore bronze
e x a m p l e s of t h e effects of s u p p l y i n t e r r u p t i o n s p r e s e r v e d in 1,2, 5 (Ore 11 bronze Zn.AI
t h e coinage of m a n y c o u n t r i e s . C u r r e n t s t u d e n t s a r e t o o y o u n g 10, 25 Ore II Cu-Ni Zn
t o r e m e m b e r t h a t b e c a u s e of w a r t i m e m e t a l d e m a n d s , U n i t e d France (several) 11 (various) AI,Zn
S t a t e s c e n t s of 1 9 4 3 w e r e m a d e of z i n c - c o a t e d s t e e l a n d five- Germany 1 Pfennig 1 Cu Al
c e n t pieces (called "five-cent p e a c e s " in s o m e circles) d u r i n g 5,10 Pfennig 1 Cu-Ni Fe
W o r l d W a r II w e r e m a d e of a c o p p e r - s i l v e r - m a g n e s i u m 1 Pfennig 1! bronze 2n
alloy. 5.10 Plennlg 1! AHyonze Zn
Hungary 2 Filler ! bronze Fe
U n d e r n o r m a l c i r c u m s t a n c e s a n u m b e r of f a c t o r s s u c h as 2 Filler II bronze Zn
cost, inertness, availability, appearance, a n d hardness are 20 Filler 1,11 Ni Fe
i n v o l v e d in t h e s e l e c t i o n of a m e t a l or a l l o y u s e d for c o i n a g e . Japan 1,5, 10 Sen II bronze Al, Sn-Zn
During wartime, with supply interruptions and armament Netherlands 1Cent II bronze Zn
production taking precedence over domestic requirements, 6 Cent II Cu-Ni Zn
t h e r e w a s a r e d e f i n i n g of t h e r e l a t i v e v a l u e s of t h e v a r i o u s 10,25 Cent II Ag Zn
metals. M e t a l price changes often complicated the situation; Norway 1, 2, 5 tBre Ml bronze Fe
h o w e v e r , in m o s t i n s t a n c e s t h e prices of d o m e s t i c a l l y p r o d u c e d 10.25,50 Ore !l Cu-Ni Zn
m e t a l s were " f i x e d " d u r i n g w a r t i m e . T h e enclosed t a b l e lists Romania 2 Lei II Cu-Ni Zn
s o m e of t h e s i g n i f i c a n t c o i n a g e c h a n g e s b r o u g h t a b o u t b y 20 Lei II Nl-brass Zn
Sweden 1. 2, 5 Ore Ml bronze Fe
W o r l d W a r s I a n d II. N u m e r o u s o t h e r c h a n g e s h a d a less sig-
10, 25. 60 Ore Ml Ag N!-bronze, Ag
n i f i c a n t effect of t h e circulating coinage as j u d g e d b y m i n t a g e
Switzerland 1,2 Centime i\ bronze Zn
figures. I n m o s t o f t h e e x a m p l e s l i s t e d , t h e r e w a s a r e t u r n a f t e r
t h e war to the pre-war coinage metal. a Data and metal descriptions (rora; Hare, R. P.. "A Guide Book of Modern Emopean
Coins," Wtiitman PtM. Co., Racine, Wl. 196B; Krause, C. L. and MlsWer. C. "Standard
For m a n y countries wartime adaptations included making Catalog of World Coins," Krause Publications, tola, Wl, 1972,
smaller, thinner, or holed coins t o save vital supplies, while
in other cases t h e r e were n o w a r t i m e coins m i n t e d or t h e r e was
a shift t o p a p e r c u r r e n c y , inflation was a major factor in t h e E u r o p e p r o d u c e s s o m e c o p p e r while m o s t of t h e world's nickel
c h o i c e of c o i n a g e m e t a l in s e v e r a l c o u n t r i e s . G r a d u a l d e - c o m e s f r o m C a n a d a . I r o n is r e a d i l y a v a i l a b l e i n C e n t r a l E u -
b a s e m e n t of t h e coinage d i d n o t occur d u r i n g t h e W o r l d W a r s ; r o p e , a s is z i n c f r o m d e p o s i t s i n P o l a n d a n d G e r m a n y , C o n -
r a t h e r , t h e r e w a s a c o m p l e t e switch in m e t a l c o n t e n t from t h e sequently, areas d o m i n a t e d by the Central a n d Axis powers
s t r a t e g i c a n d / o r i m p o r t e d m e t a l s t o less strategic, d o m e s t i c a l l y h a d iron a n d zinc coinages d u r i n g t h e W o r l d W a r s . T h e s e
p r o d u c e d metals. Significant d e b a s e m e n t was often a postwar c h a n g e s w e r e s u i t a b l e for e m e r g e n c y c o i n a g e s only. M a n y of
p h e n o m e n o n , as in G r e a t Britain in 1920 a n d 1947. D u r i n g t h e t h e i r o n a l l o y s u s e d for W o r l d W a r I c o i n a g e s o x i d i z e d r e a d i l y ,
W o r l d W a r s t h e r e a c t u a l l y w a s a n i n c r e a s e in m i n t a g e of s i l v e r w h i l e zinc coins w e r e r a t h e r soft. W o r l d W a r II c r e a t e d t i n
coins in Canada, G r e a t Britain, and the United States. Be- s h o r t a g e s i n m u c h of t h e w o r l d , b u t b e c a u s e J a p a n c o n t r o l l e d
c a u s e of l i m i t e d s u p p l i e s , S w e d e n p r o d u c e d o n l y a p o r t i o n of t h e m a j o r tin sources in s o u t h e a s t Asia t h i s m e t a l was less
i t s w a r t i m e c o i n a g e from s i l v e r ( s e e t a b l e ) . S c r a p m a t e r i a l w a s s t r a t e g i c t o t h e J a p a n e s e , w h o u s e d it a s a m a j o r c o m p o n e n t
f r e q u e n t l y u s e d for c o i n a g e : t h e U n i t e d S t a t e s p r o d u c e d i n alloys for w a r t i m e c o i n a g e .
o n e - c e n t pieces during 1944 a n d 1945 from salvaged shel!
casings,
P r e w a r coinages were often p r o d u c e d from various combi- Brief descriptions of phenomena, topics, facis. etc., which chemical
n a t i o n s of c o p p e r , n i c k e l , a n d t i n . D u r i n g w a r t i m e t h e s e ele- educators have found to be of interest in their leaching, are presented
m e n t s a l s o f o u n d i n c r e a s e d i m p o r t a n c e as c o m p o n e n t s of tnihis column In a "note type" format.
n u m e r o u s steels a n d alloys used for shell casings. C e n t r a l

edited by:
2VC3 Viewpoint TAMAR Y. SUSSKIND

Oakland Community College
Auburn Heights, M! 48057
A Note from the Chair of 2YC3

Today, more than ever before, the two-year college with its unprecedented growth and its highly diversified program has
become an extremely important segment of higher education. Although two-year colleges in their transfer programs provide
academic preparation comparable to that offered in the first two years of four-year institutions, there are many aspects
of two-year college chemistry teaching that are unique.
This new column, The 2Y03 Viewpoint, hopes to address issues, problems, and points of view that are of particular interest
to two-year college chemistry teachers and of general interest to all chemistry educators.
The following paper was presented to a group of community college teachers from Delta College, Michigan, at their Spring
Professional Growth Development Conference. The theme of the conference was "Striving for Excellence" and the special
topic was "Coping with Shifting Student Expectations." The point of view expressed here may be a provocative one, at least
in the context of the two-year college.
Coping with Shifting Student Expectations

Tamar Y. Susskind
Oakland Community College, Auburn Heights, Ml 48057
The title, "Coping with Shifting Student Expectations" educator once commented on "the infinite capacity of the
implies that students now in higher education have expecta- undergraduate to resist the intrusion of knowledge." This
tions different from previous students. Do we have evidence infinite resistance to knowledge applies more than ever now,
of this? Is it an impression that we have? Could it be that our especially to the fields of science and, in particular, chemistry.
expectations of the students is what has changed? We can I have spoken with students who take pride in telling me that
assess ourselves but in the absence of adequate data we cannot they have never had a chemistry course, and furthermore
presume to assess the students. If for a moment we turn this hoped they never would. Other students who have had one
topic around, we may get a little perspective, at least, on disastrous chemistry course in high school tell me they would
ourselves. never consider taking another. When I meet a class for the first
time I'm apologetic. I try to convince them that chemistry is
Everyone who has been teaching for more than five years
not something dreadful; that it can be exciting, challenging,
is aware that, for a variety of reasons, the way we feel about
and even stimulating. I tell them that learning itself is a
our students begins to change. We often feel about our stu-
chemical process and although taking the course may not lead
dents the way we fee! about ourselves. When we are young,
directly to immediate employment or a "pot of gold," it may
new in the profession, vigorous and enthusiastic we demand
come in handy some day when they least expect i t It may help
a great deal of ourselves and assume that we can also demand
them make informed choices on scientific and technological
a great deal of our students. As we continue to teach is it
issues facing our society.
possible that we put out iess energy and that our students
therefore achieve Jess? Because of that, we ascribe to our We are caught in the compromising position of having to
students a lowering of expectations. If we mean the opposite, teach skills without abandoning the development of the kind
I have yet to hear it. Are the student expectations shifting of mind that can think logically and reason effectively.
upward or downward? Somewhere in my education I've come to believe in learning,
If the shift of expectation occurs in what is expected of us in questioning, and in the human spirit. 1 owe it to my students
as instructors that is one issue and a big one. But if the shift to let them know how much there is which goes beyond im-
is one that includes the goal of an entire college education then mediate gratification- In coping with these waves of dualistic
we have yet another issue. Judging from the flurry of students tension—pragmatism versus theory, vocation versus aca-
taking business courses, data processing, computer courses, demics, experience versus homework, now versus yesterday
and robotics one would think that the ultimate goal of edu- or tomorrow—I feel that the teacher must have the pervasive
cation was to enable a person to enter the job market com- conviction that learning is in and of itself a highly valuable
petitively, The students seem to look upon education more activity; a goal worthy of everyone's pursuit and one that
vocationally and to be more goal-oriented than ever before. draws a variety of rewards.
We are expected as teachers to show them how to "make The economic climate of the 80's, in which teachers must
it"—that is, have a marketable skill. The question I would like worry about enrollment, combined with our egalitarian open
to pose is; how do ! (and maybe some of you) having been door policy has forced us to make certain adjustments. I'm
raised in a tradition of knowledge for its own sake face stu- aware, for example, that it has become increasingly important
dents who are not interested in the very values that drove me for me not to fail too many students. Because of that, our de-
to find my own education? How do I bridge the gap between mands are lowered and there is an erosion of student expec-
the value systems: vocational skills versus pursuit of knowl- tations. It is known that people perform at a level at which you
edge? Thomas Ixnmsbury, that great turn-of-the-century Yale assume they are going to perform. Perhaps we tend to sell our

adoem
lngandwh tiofrstum deak nu
e-tsp' shtfn tisgts, eexxtrpaectaoh
e tinepls,esg .es,.oin thes, enixcrtraea
students short by descending to a lower level of expectation.
Before long, they inevitably come to share our expectation of
rmequ u p
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l s eanrsew sitaen
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them. We know that students never, or hardly ever espect
enough of themselves. Don't you think they know where the
easy A's are? They can get by with a minimum of work, hut arMeyrealexpperoreib em
nlceshaan s datucgoh pn
igm
t we h
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r y t
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in so doing they deprive themselves of an education. It is our
job to expect the best of them and I suspect we can get it. It
m bayyl astu ndd en nitsrofm wrn tigth,ereastsilatcirt.gIoaslexp w a
lnh
tii m reyasiltcipodceilm eia
is the only way the students will find the best in themselves,
Teachers must find their own way of expecting the best of gthraednigsu td s y
eeln st
em
th , m a k e
u
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, a b
avredyltoeverbetrvieesrytospecmsen c e s
, e t c . W
aken h t i
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their students. Most of us don't even know how little we espect
of them. Getting back to my earlier point: do I find myself sapctecaia(ln p as
dbuthtereI aaw h a lloaysmsean m satorm ai l
be direc i d e
one), I try n
expecting less of my students as a trade-off so that they will
expect less of me? After all, I can pay them off fairly well. cen A e
t
r
h ed
tlouogfu hndsu thd ent etovaus i a
t
labotienshepn
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Haven't we all been a little guilty of grade inflation? The result
w h av e te
m i i
ouIh tgihtstu den tsn
.d T heyh areessu p rsanietgdylyl ceaxnpdrdiesedandtherIen b
seems to be that students want better grades for less input.
The question we face is shall we continue to acquiesce in the
lowering of expectations by accepting the diminished demands
ne. Ictonccu to c o si
lnsoin,bIeme r tem uetsdadn r
e
mp e
tivtharaoitusthsiwatoyp ciW isean i .
of our students, a reflection of our own lowered estimate of
their abilities? I beiieve we have permitted it to happen and o n
etiatecrhtw ern a
re.spIonsw bityilou v
ew
i
ask w i
eltoaselavstu deyn si.'T heh s.
yi aw reon i
we have the ability to turn it around. Although we are involved
in a crisis where headcount in the classroom looms large and
some of our jobs may be at stake, I feel that we must do a
ncu lsoins: i e d dl i
l e e o u w t t
tiu12d))eh Be realistic—make
balancing job. We must offer courses with substance and re-
ward excellence and not mediocrity. A faculty member's en-
thusiasm and commitment to his or her subject will have the
greatest impact on students and they will in turn be motivated sn tn ets .
Acknowledge
p roc e s o
l s e agih t o f h
t e p e a t v ah
t
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ac
oft e lah
t
rnan
to dig in.
Further, how do we cope with behavioral patterns that go self.
edited by
/ofety tip/ MIRIAM C. NAGEL

Avon High School
Avon, CT 06001
Risk Assessment exposures are totally risk free?" It quotes from a S u p r e m e

C o u r t d e c i s i o n w h i c h s a i d t h a t " s a f e " is n o t t h e e q u i v a l e n t o f
Miriam C. Nage! "risk free." Additional c o m m e n t s on t h e decision were, " S o m e
Avon High School risks are plainly acceptable a n d others plainly unacceptable.
Avon, CT 06001
If, f o r e x a m p l e , t h e o d d s a r e o n e in a b i l l i o n t h a t a p e r s o n w i l l
" Z e r o R i s k ' U n a t t a i n a b l e , ' C M A S a y s " is t h e t h o u g h t - d i e f r o m c a n c e r b y t a k i n g a d r i n k of c h l o r i n a t e d w a t e r , t h e r i s k
p r o v o k i n g t i t l e of a n a r t i c l e i n t h e M a r c h 1 9 8 2 i s s u e o f c o u l d n o t b e c o n s i d e r e d s i g n i f i c a n t . O n t h e o t h e r h a n d , if t h e
ChemEcology, published by the Chemical Manufacturers o d d s a r e o n e in a t h o u s a n d t h a t r e g u l a r i n h a l a t i o n o f g a s o l i n e
A s s o c i a t i o n (1). T h e a r t i c l e o p e n s w i t h t h e s t a t e m e n t , " O n e v a p o r s t h a t a r e t w o p e r c e n t b e n z e n e will b e fatal, a r e a s o n a b l e
c h a l l e n g e n o w f a c i n g s c i e n t i s t s a n d r e g u l a t o r s is t o a s s e s s t h e person m i g h t well consider t h e risk significant a n d t a k e a p -
s i g n i f i c a n c e t h a t s m a l l q u a n t i t i e s of c o n t a m i n a n t s m a y h a v e p r o p r i a t e s t e p s t o d e c r e a s e or e l i m i n a t e i t . "
for h u m a n h e a l t h a n d t o s t e e r t h e n e c e s s a r y c o u r s e t h a t p r o - L e t u s look a t t h e t w o c h e m i c a l s c i t e d in t h e q u o t e d c o m -
tects society's health while m e e t i n g society's n e e d s . " I t further m e n t s from t h e S u p r e m e C o u r t decision. T h e risks associated
s t a t e s , " T o d a y , a d v a n c e s in a n a l y t i c a l skills a n d toxicology with t h e u s e of chlorine i n water are "plainly acceptable" by
have improved detection a n d identification. Substances t h a t t h e C o u r t ' s d e f i n i t i o n of t h e term. O n t h e o t h e r h a n d , b e n z e n e
pose potential h u m a n h e a l t h h a z a r d s in higher concentrations is u n a c c e p t a b l e i n h i g h s c h o o l l a b s a n d s t o r e r o o m s . I t is h i g h l y
c a n n o w be d e t e c t e d in p a r t s p e r billion." toxic a n d a suspected carcinogen. T h e Permissible Exposure
W i t h t h e s e i m p r o v e d m e t h o d s of d e t e c t i o n , lists of p o t e n - L i m i t ( P E L ) , t h e m a x i m u m t i m e - w e i g h t e d a v e r a g e level for
tially toxic chemicals a n d carcinogens are growing longer. a n 8 - h r e x p o s u r e , is 1 p p m w i t h a ceiling of 5 p p m , a c c o r d i n g
S t r a n g e a n d p r e v i o u s l y u n k n o w n s u b s t a n c e s I r a k even in a to the N 1 O S H / O S H A P o c k e t Guide to Chemical Hazards. T h e
b e a k e r of l a b o r a t o r y t a p w a t e r . " F o r e x a m p l e , in a r e c e n t I m m e d i a t e l y D a n g e r o u s t o Life or H e a l t h ( I D H L ) concen-
a n a l y s i s of w a t e r t a k e n f r o m a t a p i n C i n c i n n a t i , O h i o , o v e r t r a t i o n , r e p r e s e n t i n g a m a x i m u m level for a 3 0 - m i n e x p o s u r e ,
7 0 0 s e p a r a t e c o m p o u n d s w e r e f o u n d , of w h i c h o n l y 4 6 0 o r s o is 2000 p p m (3).
c o u l d b e i d e n t i f i e d . O f t h o s e identified, few h a d ever b e e n B e n z e n e is a l s o a f l a m m a b l e l i q u i d , h a v i n g a f l a s h p o i n t o f
r e p o r t e d before in r a w or t r e a t e d w a t e r s u p p l i e s . M a n y a r e 1 2 ° F ( ~ 1 1 ° C ) . V a p o r s f o r m e x p l o s i v e m i x t u r e s in air. T h e
k n o w n or s u s p e c t e d carcinogens, t h o u g h p r o b a b l y n o t a t t h e explosive limits are 1,3-7.1%. L i q u i d b e n z e n e h a s a specific
extremely low c o n c e n t r a t i o n s reported in t h e s t u d y " (2). g r a v i t y o f 0 . 8 a n d is i n s o l u b l e i n w a t e r . T h e v a p o r is h e a v i e r
T h e ChemEcology a r t i c l e (1) p o s e s t h e q u e s t i o n , " E v e n t h a n air a n d m a y travel considerable distances to a h e a t source
t h o u g h h u m a n experience tells us t h a t low-level exposures r e s u l t i n g in a flash b a c k , a d d i n g t o t h e h a z a r d s .
n e e d n o t b e harmful, does this lead to t h e conclusion t h a t such A l t h o u g h b e n z e n e s h o u l d n o t b e f o u n d in t h e h i g h school
lab, teachers a n d s t u d e n t s m a y b e exposed to t h e toxic fumes
"Safely Tips" la a source of safety Information and practical suggess- of b e n z e n e w h e n t h e y p a t r o n i z e t h e n e a r e s t self-service g a s
tionsto meet the special needs of high school chemistry teachers, tt is s t a t i o n . B e n z e n e is o f t e n u s e d a s a s u b s t i t u t e f o r l e a d in u n -
a<so intended to be a forum for teachers to share Iheif experiences and leaded gasoline. " I n the general public, benzene exposures
seek solutions to safety related problems. r a r e l y exceed t h e p a r t s - p e r - b i l l i o n level, a n d a r e o r d i n a r i l y

not risky. However, some health authorities note that the tinue to permit buik sales of saccharin in tablet and powder
benzene fumes that collect at the top of a car's gas tank are form, but would ban its use in prepared food and beverages.
often released in a whoosh when the cap is removed for a fill- Later in the month, the FDA announced a two-month delay
up, and that ambient benzene levels as high as 250 ppb.have in enforcing the ban to evaluate new data Sinking saccharin
been recorded at gaa stations" (4). It is to be hoped that owners to bladder cancer. In May the New Jersey Medical Society
and attendants at busy full-service gas stations are aware of opposed the ban on saccharin, and a World Health Organi-
the possible health hazard. zation report indicated that saccharin does not increase risk
The safety of food additives come under the jurisdiction of of bladder cancer.
the Pood and Drug Administration (FDA) in much the same Proponents of the FDA stand were vastly outnumbered by
way that the Environmental Protection Agency (EPA) is re- opponents of the ban who continued their efforts through the
sponsible for enforcing Jaws passed by Congress to protect the summer and fall. The Congressional Technical Office which
environment from toxic substances. Food additives are rarely bad begun a study of the risks of saccharin and the adequacy
encounted in high, school chemistry labs, but a brief survey of of animal testing reported in November that it is one of the
saccharin, an artificial sweetener, will show how possible risks weakest cancer causing agents ever detected. After months
from its use have been evaluated by the FDA, Congress and of hearings and legislative maneuvering, Congress passed and
the public. President Carter signed the Saccharin Study and Labelling
Saccharin was discovered accidentally in a chemistry lab Act late in November 1977.
in 1879. It ia noncaloric and, in dilute aqueous solutions, it is Under terms of the act, the National Academy of Sciences
300-500 tiroes as sweet as sugar. Since 1900 it has been used would review the data on which the proposed saccharin ban
as a sugar substitute by diabetics and in weight-control was based, and the FDA would develop procedures and reg-
diets. ulations for warning labels on saccharin products about the
Amendments to the 1938 Food, Drug and Cosmetic Act risk of cancer. In November 1978 the National Academy re-
brought food additives under regulation by the FDA in 1958 ported to Congress that saccharin must be considered a danger
and 1960. Before 1958, it was the responsibility of the FDA to to humans, both because it is a weak carcinogen and it may
prove that a food product was potentially dangerous. After- be a promoter of other cancers. Despite the Academy's
wards it became the responsibility of the manufacturer to warning, opposition to the FDA's proposed ban on saccharin
prove that a new product was free of risk to the public. In re- did not diminish. As far as its opponents were concerned, it
gard to carcinogens, the Delaney Clause (part of the 1958 and was an "acceptable" risk to use saccharin. In 1979 and again
1960 amendments) states that " . . . no additive shall be in 1981, Congress voted to forbid the FDA to impose the ban
deemed to be safe if it is found to induce cancer when ingested for successive two-year periods.
by man or animal, or if it is found, after tests which are ap- In 1983 the FDA announced approval of the use of aspar-
propriate for the evaluation of the safety of food additives, to tame, a new low-caiorie sweetener. The newspaper story (.5)
induce cancer in man or animal..." (1). about the announcement reported that before the approval
The ChemEcology article on zero risk states (i), of aspartame, saccharin had had a monopoly in the soft drink
market which accounted for 70% of its saies, or about $115
Animal testing is an important step in assessing the potenti&J carci- million a year. Not bad for a product which nearly came under
nogenic risk of a substance, . .Although uncertainties exist with the ban in 1977.
animal feeding studies and the mathematical extrapolation of the
dose-responses, the greatest uncertainty lies with the direct transla- A new publication, "Risk Assessment in the Federal Gov-
tion of animal response to human response. Risk assessment is the ernment," is now available from the Committee on the Insti-
only means available to quantify the probable risk associated with tutional Means for Assessment of Risk to Public Health,
a specific food or food additive. It also permits comparison to other National Research Council (6). The test, prepared at the re-
societal risks. quest of Congress, evaluates past efforts to develop and use
guidelines and proposals for changes in risk assessment pro-
Which brings us to the saccharin controversy. cedures for carcinogens in the environment. The authors
Responding to a Canadian study which indicated that recognize there are no quick answers, but do present an ob-
saccharin causes malignant bladder tumors in rats, the FDA jective analysis of the problems. Another new publication,
in March 1977 proposed a ban on the use of saccharin. There "Identifying and Estimating the Genetic Impact of Chemical
was immediate and continuing public outcry against the ban Mutagens," from the Committee on Chemical Environmental
from users of the product. The president of the Calorie Control Mutagens, Board on Toxicology and Environmental Health
Council maintained that saccharin had been used for 80 years Hazards, National Research Council (6), provides information
with MO evidence that it had produced cancer in humans. Some on assessing genetic risks.
manufacturers of products containing saccharin claimed that
the FDA ban was based on "flimsy scientific evidence" and
would destroy the diet beverage industry and deprive dia-
betics of sweets. Producers of soft drinks and other low-calorie Literature Cited
products began using substitute sweetners to lessen the eco- {1} ChemEtalagy, Chemical Manufacturera' Association, 2501 M Street NW, Washington,
nomic impact of the ban. A Congressman announced plans to DC 20037, Match 1982.
(8 Skjei, E., and Whnrion. M. I)., "Of Mice and Molecules," The Dial Press. New York,
introduce legislation to stop the FDA action and to modernize 19S3, p. 132. ©ata credit W. R. Coleraan et a!-, "Identifiaatio!! of Organic Compounds
the Delaney Clause. Within the month the FDA considered in zt Mutagemc Kxtj-uct of a Surface Drinking Water by a Computerized GasCliro-
classifying saccharin as a drug instead of a food additive so raatography/Mass Spectrojnetry Syatern {GC/MS/COM}." Environmental faienc
end Teeknalagy, 14,576, May 1980.}
doctors could prescribe it for diabetics and weight disor- |3) DHEW (NIOSH) Publication No. 78-210, Superintendent of Documents, U.S. Gov-
ders. eminent Printing Office, Washington, Iffi 20402
i4) Ref.(2),p. 103.
(5) HoJIie. Pamela G.,"SearIeSweotner Wins Approval for Soft Drinks," New Yarh'nmes,
Opponents of the ban in April 1977 included the president July 2,1933, p. 31.
of the American Cancer Society. The FDA said it would con- (S) National Academy Press. 201 Constitution Avenue NW, Washington, DC 30418.

Single-Pan Balances, Buoyancy, and Gravity
or "A Mass of Confusion"
Rubin Battino
Wright State University, Dayton, OH 45435
Arthur G. Williamson
Department of Chemical Engineering, University of Canterbury, Chrlstchurch, 1, New Zealand
The advertising literature on single-pan balances (both (perhaps, because the weights are protected, i.e., untouched
mechanical and electronic) ia a commentary on the gullibility by human hands), or to consult them in case of trouble. None
of consumers and the apparently confused ideas many man- supplied directions for calibration. The calibration of the
ufacturers have about weighing. For example, one manufac- weights in such a balance is fully described by a publication
turer of single-pan electronic balance lists for a dual weighing of the American Society for Testing Methods (1}. An alter-
range of 1500/150 g, "readabilities" of 0.1/0.01 g, "precisions" native approach which examines the internal consistency of
of 0.05/0.007 g, and "linearities" of 0.1/0.01 g. The readout the weights but does it without checking their absolute values
displays five digits which accounts for the readability. We and which has been used as a laboratory exercise by one of us
certainly hope the linearity is of the same order. As to how is described in the Appendix.
they determine precisions which are better than the "read- Most manufacturers of single-pan electronic balances in-
ability" or "linearity" we can only guess. cluded directions for calibration. The procedure was to put
Most single-pan electronic balances display five digits, some a "standard" weight, usually unspecified as to density or NBS
show six, and one company even offers eight (0.1 mg for the class (2), on the balance pan and then turn a calibrating screw
1-kg range). The single-pan mechanical balances of the ana- until the read-out gave the nominal weight. The Mettler In-
lytical type {load 160-200 g, "readability" of 0.1 mg and strument Corporation supplies a calibrator weight with its
"precision" of 0.05 mg) generally deliver seven significant balances and also sells them. The Sartorius balance has a
figures. This wealth of "readabilities, precisions, and linear- built-in calibration weight To calibrate any electronic balance
ities" is offered along with oodles of significant figures despite one needs to use a standard weight of adequate accuracy. For
the fact that {we fondly hope) any sophomore taking quanti- a 100-g weight (a typical calibration weight) the class S tol-
tative analysis could tell the manufacturers that due to erance is 0.25 mg, the class S-l tolerance is 1.0 mg, and the
buoyancy effects (if, indeed, this arcane topic is still discussed) class P tolerance is 2.0 mg. Thus, strictly from the viewpoint
the accuracy is often of the order of one part per thousand or of accuracy, it is difficult to understand the extra digits these
0.1%. If an accuracy of 0.1 mg is required in a mass of 100 g balances display. How can an analytical balance be accurate
then buoyancy corrections must be made to 0.i%! to 0.1 mg when a class S weight is only accurate to 0,25 mg?
(The tolerance of a class M 100 rag weight is 0.50 mg.)
Being mightily intrigued by the foregoing and the manu-
facturers' literature, we sent out a brief questionnaire to all Let us now turn to the interesting problem of the density
companies which we could identify as manufacturers of sin- of the weights used inside single-pan mechanical balances. A
gle-pan balances. We asked the following questions of their standard for weights used in analytical balances was pro-
research directors mulgated in 1973 by the Organisation Internationale de
Metrologie Legate. Their recommendation is to use weights
A. Single-Pan Mechanical Balances of density 8.0 g em" 3 at 20°C. All of the Mettler balances built
1. What are your "weights" made of and what is their den-
sity? since 1973 have weights made of stainless steel with a density
2. Do you have a set of instructions for calibrating the of 7.96 g cm""3 but "adjusted" to 8.0 g cm""3 for a standard air
"weights", oy must this check be done by you? density of 1.2000 g cm" 3 , Eariier Mettler balances used
3. Do you have a set of instructions applying to buoyancy cor- stainless steel weights of 8.4 g cm""3. We do not know how
rections? Mettler accomplishes this "adjustment". Ainsworth uses
nickel-plated brass weights of density 8.4 g cm""3 in some
B. Single-Pan Electronic Balances balances and stainless steei ones of density 7.8 g cm" 3 in
1. Do you have a set of instructions for calibrating the accuracy others. Sartorius balances use weights of 7.88 g cm" 3 density.
of your balance over its fail range? Whatever the original reasons for this multiplicity of weights
2. Since your balances will only read correctly when weighing of different densities, there can be no real excuse for not
objects of a certain density, what is the density of the stan-
dard weights against which your balances were cali- standardizing on weights of a density of 8 g cm""3.
brated? Recently an entire new technology of weighing has been
3. Do you have a set of instructions appfying to buoyancy cor- developed in the form of the all-electronic balance. (A tran-
rections? sition period included mechanical/electronic hybrid balances.)
The responses to these queries were mast disheartening With these devices we have in effect returned to the spring
since almost all of the manufacturers just sent us more liter- balance. The object to be weighed is placed on a pan and
ature in return. Moreover, it was quite evident from the re- downward force is given by
sponses that most manufacturers either do not understand
the idea of buoyancy corrections or believe them to be irrele- Calr
mg
vant (which they sometimes are). This ignorance of buoyancy
corrections is not limited to manufacturers—one of us recently where m is the mass of the object, g, the acceleration of gravity,
heard a colleague complaining that the top loading single-pan and <r is the density (c a i r =« 0.0012 g cm" 3 ). This downward
balance in his laboratory had had a "systematic" error of ap- force is automatically balanced exactly by the interaction of
proximately 1 g/kg ever since it had been bought. the magnetic field from a coil and that of a permanent magnet.
The manufacturers of single-pan mechanical balances ex- The current in the coil is converted electronically to a weight
pect you to accept their original calibrations indefinitely reading and then displayed digitally. It is possible to make the

scale much more linear than that of a mechanical spring bal- Appendix: Intercallbration of Weights on a Single-Pan
ance, and precisions of a few parts per million or better are Weight Loading Satance Using Dummy Weights
possible. For measurements where only relative masses are of Approximately Known Mass Only
important (and using the same balance in the same place for 1) Set balance leve!
all weighings) no calibration point is necessary (within the 2) Release beam
"linearity" of the balance!). The apparent mass scale is ob- 3) Set optical scale zero (this is useful but not necessary)
viously a function of the local gravitational field. Although 4) Head optical scale: Sv
Portland, Oregon and Charleston, South Carolina have es- 5) Arrest beam
sentially the same altitude, g differs by 0.11%; between New 6) Dial up 1 unit: M%
York, New York and Denver, Colorado this difference is 7) Release beam
0.07%. 8) Read opticai scale: Si
When one calibrates single-pan electronic balances one is, Mj = (Si — S») (optical scale units)
in effect, determining the force constant of the electromag-
netic nulling system against a standard weight of a particular 9) Arrest beam
density, if one knows that density (or the one the manufac- 10) Add external weight: ff,{aMi)
turer used), then one can reasonably apply buoyancy correc- 111 Release beam
tions and also calibrate the balance for the density of weight* 12) Head optical scale: SB
the manufacturer designed it for. Mettler supplies a standard
weight of 8.0 g cm~3 density with its instruments (and also
seHs them separately). Sartorius calibrates all of their balances 13) Airestbeam
against weights with a specific gravity of 7.88 g cm""3. AH of 14) DialM:
the other manufacturers we contacted gave no information 15) Release beam
on this matter. Basically, they tell you where the calibration 16) Read scaie: Sa'
screw is and to use it in conjunction with a "standard" 17) Wa = Sa'-So
Wa = M, + < S a ' - S )
weight. 18} Arrest beam
Buoyancy corrections for singie-pan mechanical balances 19) Remove M±
have been dealt with before in THIS JOURNAL {3-5). The most 20) Remove Ws and add Wb ( a l f j
complete analysis was given by Winward, Wooliey, and Butler. 21) Release beam
But, no matter how one approaches it, if one weighs an object 22) ReadS b
of density 10 g cm~3, the buoyancy corrections are of the order Wb = (S,, - So)
of 0.1% or one part per thousand. Mettler gives charts on how 23) Arrest beam
to handle this for their mechanical balances, and Sartorius 24) Add Mi
gives directions in their instruction manuals. 25) Release beam
26)
Air buoyancy corrections for single-pan electronic balances
are the same as for two-pan equal-arm mechanical balances
or 27) Arrest beam
2$) Add Wa
Pair 29) DialupM2(^
Pwt 30) Release beam
where Wo is the in vacua weight of the object, Wwt is the 31) ReadSc
weight read on the read-out device, and p^, po, and p w t are,
respectively, the densities of air, the object, and the weights 32) Now;
used to calibrate the balance. The buoyancy correction for
M 2 = <SC - Sa)
weighing 1 kg of water is about 1 g!
W a = M, +• (S u ' So)
While the manufacturers of balances are to be congratu- W b » Mi + (Sb'
lated on their achievements in providing both very high pre- .' + Sb' - 2Sa)
<Se Wb = 2Af i
cision and great convenience in the use of their products, it
is unfortunate that these advances have not been accompanied and hence
by corresponding advances in the education of balance users, Sc~ Sv)
particularly with respect to the precautions necessary to use
these fine devices. A standard 100-g weight ts of such smali It is always necessary to examine the way in which the removal of
cost relative to the cost of a balance t h a t they should be sup- interval weights from the beam is related t o the dial readings. For
plied with the balance. example the Mettler H5 balance has the weights: 1,1,2,5,10,20,40,
80 g. The Mettler H10 has 1,2,3,6,10,10, 20,40,80. It is important
Beware of being bedazzled by all of those bright red digits. to order the measurements so that the proper inlereompamons are
If all else fails, re-read the section in a good quantitative made. By the carefui choice of dummy weights and their combinations
analysis book on balances and their errors, or even choose to all the weights can be expressed in terms of each other and some
work with the siower equal-arm balances where one can easily (small) ierm in optical scale units. This latter can, of course, in its turn
calibrate the weights and tare with real objects. Of course, if be expressed in terms of M , if desired. Usually the error in the optical
you never work beyond precisions of 1 ppt, feel free to ignore scale makes only a small contribution to the error in determining the
this paper. But, then, why are you using such an expensive relationship between the weights, but it can make a significant error
in an actual weighing.
balance?
A logical extension of the procedure described in steps 1-32 is used
Literature Cited to dea5 with ail the other weights. Finally all weights can then, if de-
sired, be expressed as fractions of the largest weight in the set which
(11 A.N.S.I., E 318-&I, Standard Method of Testing SINGLE ARM BALANCES. is the one likely to have the smallest percentage error.
(21 ANSI/ASTM, E 617-78, Standard Specification for Laboratory Weights and Precision
Mass Standards; NationaS Bureau oi1 Standards, Circular S47. Precision Laboratory As has been pointed out in the text, if all weighings for a chemical
Standards of Mass and Laboratory Weights, Laahof, T. W., and Macurdy, L. B., experiment are doae on the same balance there is usually no case for
1954. requiring anything other than a linear mass scale because gravimetric
(3) Burg, W. R., and Veilii, D, A., J. CsiEM. EDVC, «, 192 (1970). chemical experiments are concerned with the ratios of masses at
(4) Lewis, J. E.. and Woolf, I, A., j . CHEM. EDUC 18,639 (1871 i.
(5) Wiiward, M. E., Woolley, E. M., and Butler, E. A., Anal Chcm., 4% 2128 (1977). various stages of the experiment.

Qualitative Analysis, with Periodicity, for "Real
Solutions
Ronald L Rich
Blufftort College, Bluffton, OH 45817
The outline of group separations for a non-H 2 S analytical M a n y basic Hgands, such as c a r b o n a t e , c o o r d i n a t e t o m e -
scheme applicable to all metallic elements is presented here, t a l l i c cations, j u s t as w a t e r does, t h r o u g h oxygen a t o m s . I t is
along with an outline of an abbreviated and otherwise modi- t h e r e f o r e n o t s u r p r i s i n g t h a t n o n c h e l a t i n g oxy~ligands t h a t
fied version designed for some emphasis on nutritionally im- can displace w a t e r from some cations will probably react with
portant metals, with special attention to 10 cations. The more m o s t of t h e m . T h i s leads t o p o o r selectivity for initial sepa-
complete scheme will be referred to as the Bromide Scheme rations. We d o well t o start, consequently, with reagents acting
and the shorter one as the Iodide Scheme. A survey of the t h r o u g h (nonmetallic) a t o m s far from oxygen in t h e periodic
relevant literature from about the last 50 years is included. c h a r t a n d correspondingly different chemically. (Even nearby
chloride, in t h e s t a n d a r d p r o c e d u r e s , r e m o v e s several of t h e
Major Features few m e t a l s in t h e first g r o u p q u i t e incompletely.) A good
O n e p r o b l e m in basing teaching o n s y s t e m s of q u a l i t a t i v e g e n e r a l s t r a t e g y , t h e n , is t o u s e oxy-ligands, a n d p e r h a p s
analysis is t h e i n c o m p l e t e correlation between m e m b e r s h i p fluoride, only after m a n y m e t a l s h a v e been r e m o v e d from
of a n e l e m e n t in a n analytical g r o u p a n d its position in t h e u n k n o w n s b y m e a n s of m o r e polarizable a n d selective re-
periodic table. As stated by S o r u m a n d Lagowski ( i ) , " . . . a g e n t s , s u c h a s b r o m i d e a n d iodide.
since t h e periodic table provides t h e b e s t available organized F i g u r e 1 outlines t h e m a i n B r o m i d e S c h e m e s e p a r a t i o n s .
p i c t u r e of t h e properties of t h e elements a n d their compounds, Figure 2 shows t h e resulting organization of t h e periodic chart.
we s h o u l d e x p e c t t h e periodic t a b l e t o serve as a useful g u i d e T h e n u m b e r s a r e analytical g r o u p n u m b e r s . M n , Fe, Co, a n d
in m a n y phases of qualitative analysis." T h e Bromide S c h e m e N i , for e x a m p l e , a r e in G r o u p 2. T h e n u m b e r s with a s t e r i s k s
is p a r t l y t h e result of a long effort t o a c c e n t u a t e t h a t useful- designate t h e nonmetals t h a t coordinate directly t o t h e cations
ness. in t h e c o r r e s p o n d i n g groups. T h e 2* over N , for e x a m p l e ,
A n o t h e r p r o b l e m with q u a l i t a t i v e analysis h a s been t h e shows t h a t t h e N a t o m s in c y a n o c o b a l t a t e a r e directiy at-
interference of various organic and inorganic substances. Even t a c h e d t o t h e p r e c i p i t a t e d cations in G r o u p 2. T h e Iodide
p h o s p h a t e causes t h e calcium (carbonate) group, in s t a n d a r d S c h e m e o u t l i n e is in F i g u r e 3. W e n o t e t h a t t h e simplified
s y s t e m s , t o p r e c i p i t a t e t o o early. C i t r a t e , sugar, E D T A , a n d procedures of Figure 3, without solvent extraction, p u t Zn into
p o l y p h o s p h a t e s a r e a few of t h e c o m m o n ligands t h a t can a n a l y t i c a l G r o u p 2 r a t h e r t h a n G r o u p 1.
p r e v e n t precipitation of t h e a l u m i n u m (hydroxide) a n d o t h e r A n y specific set of d i r e c t i o n s raises t h e q u e s t i o n of using a
groups. B r o m i d e a n d iodide can prevent precipitation of some cookbook a p p r o a c h . T h i s a u t h o r also p r e a c h e s a n d claims t o
sulfides, even t h a t of m e r c u r y . As a result we either d i s p e n s e practice a strong emphasis on thinking. We should certainly
artificial u n k n o w n s w i t h o u t t h e s e i m p o r t a n t s u b s t a n c e s , or recognize, t h o u g h , t h a t s t u d e n t s n e e d t h e m o s t h e l p a t t h e
i n c l u d e t e d i o u s ways of dealing w i t h t h e m . S t u d e n t s can still beginning of any systematic analysis, partly because t h e y t h e n
learn a great deal, p e r h a p s even because of t h i s , b u t one value h a v e t o work w i t h t h e largest n u m b e r of p o t e n t i a l l y p r e s e n t
of t h e Bromide a n d Iodide Schemes is t h a t each can overcome m e t a l s . R e a d e r s will see some of our ways of dealing with t h i s .
m o s t , t h o u g h n o t q u i t e all, of t h e s e difficulties. W e m a y a d d t h a t t h e p r o p e r a n d i m p r o p e r use of fixed in-
s t r u c t i o n s is n o t confined t o q u a l i t a t i v e analysis.
Presented at the 6th International Conference on Chemical Education, A d d i t i o n a l c o m m e n t s a n d procedural details a r e available.
College Park. MD, August 9-14.1981, and at the 7th Biennial Confer- E x p e n s i v e r e a g e n t s h a v e been avoided, b u t information on
ence on Chemical Education, stillwater, OK, August 8-12, 1982. costs p e r u n k n o w n is also available. (See s u m m a r y . )
A d d HBr Add PH—*-3 Add Gr. 5

red-agt. K3Co(CN)6 Add NH,Cfr KF Met*
MtpBr (orK3HP0a)
GHjCli
Heat.
K I
I
Gr. 1 Gr. 2 Gr. 3 Gr. 4
MtpxMetBry KMetCo(CN) 6 MetCfrx MetFs
M t p l in CrCfr,
solvent (orCrPO, etc.).
C6HSNO
Figure 1. Group separations in the Bromide Scheme.
After each group precipitation {or striven! extraction! the remaining aqueous solution Is treated by the next procedure to the fight. The resufttng precipitates and
extracts are shown below the corresponding procedures.
Notes: The reducing agent, reiJ-agt.. can be ascorbic acid. Mfp is methyltriphenyiphosphonium. Mel is a metal in Hie group. Cfr is cupierrate.
Bromides of Ge, As, and Se can be distilled out (2) as Subgroup 1a before extraction of the bromo-complexes in Group 1 (or 1£>), for which ffie [HBr] Is made 3
M.

The Role of Organic Reagents B o t h t h i o a c e t a m i d e , widely u s e d in sulfide s y s t e m s , a n d
One notable feature of Figure I is its inclusion of some or- c u p f e r r a t e a r e s u s p e c t e d a s possible mild carcinogens. W e
ganic reagents. Does this mean that the student is over- m i g h t n o t e t h a t zinc salts (required n u t r i e n t s ) also h a v e been
whelmed with rote procedures and " incomprehensible" reso classified (5). W h e t h e r m e t h y l e n e chloride poses arty s i m -
actions? By no means! Since that may be a misleading first ilar significant health hazard at all is disputed, b u t it certainly
impression, however, let us briefly discuss the role of organic does so less t h a n chloroform (6). In any case, we can p r o b a b l y
reagents in this work before we go further. u s e o t h e r cationic e x t r a c t a n t s with o t h e r solvents. 1 O « r re-
Dimethylglyoxime and aluroinon are accepted almost m a i n i n g r e a g e n t s a p p e a r t o call for no u n u s u a l concern.
universally in confirmatory tests. More recently thioacetamide
and benzoate (3) also have been accepted as group reagents. Periodicity
One criterion for adopting each group reagent in the present Figure 4 shows the distribution of elements in a common
case has been that it can be interpreted to students. form of the hydrogen-sulfide analytical scheme. This reveals
A reducing agent is needed in procedure 1, especially for clearly the problems of explaining the relationships among
Fe(III) and Cu(II). Ascorbic acid works wel! and is widely the traditional analytical groups. We must also recall that even
known, Ite structure is a bit complicated, but the active part the inter-group boundaries shown are further drastically
is quite comprehensible. Its formula is easily remembered if modified if unknowns contain various common interfering
written as HaCgHgOe- Mercaptoacetic acid is also effective, substances.
very simple structurally, and not too malodorous, The inor- Several points in partial defense of the sulfide scheme,
ganic reductants sulfite and hypophosphite could be used, in however, are needed for a full and fair appraisal. The HC1
fact, but the oxidized products could then precipitate some precipitation of Ag, W, Hg, Ti, and P b could be omitted,
metallic ions from later groups. (The original presence of especially since the last three are not completely removed
sulfatfi and phosphate in unknown solutions is perfectly ac- anyway, and these metals would then be well-behaved mem-
ceptable, however, since incompatible cations obviously bers of the acid sulfide group (7-9), The Iodide Scheme pro-
cannot also be present.) duces a somewhat similar first group, but it does remove Tl
To help extract the bromo-complexes into methylene and P b essentially completely from solution, and it puts Cu,
chloride we can use a large cation (Cat + in Table 5) in a Ag, and Au together. This scheme is not ready at present,
moderately priced salt Methyl triphenyiphosphonium (Mtp + , however, to handle all the metals in the periodic table.
CH3(C6H5)sP+) can be viewed as an analog of ammonium ion. We can illustrate the pedagogical value of periodicity with
Unlike some specific organic reagents, but like the reductants one condensed interpretation: The heavy-metal cations on the
just mentioned, its effectiveness is largely independent of any right side of the periodic chart, compared to the cations on the
mysterious details of structure. 1 The students should already left, have large nuclear charges, and large effectiue (poorly
have encountered the benzene ring. shielded) nuclear charges. These act on the loosely held, easily
Cyanocobaltate is similar to the well-known cyanoferrates polarizable electron clouds of large negatively charged atoms
and is scarcely organic. It also lacks the toxicity of cyanide (4). such as Br~ and I", and bind them relatively strongly (10). In
Cupferrate, C6H5—N2O2~" (not quite a mtrosamine), should our analytical Group 3 we thus have such reactions as:
be considered as simply a phenyl derivative of the hyponitrite
ion, NaOa2"- Moreover, students can benefit here from Cd s+ +• 4 Br- -* CdBr 4 2 -
learning about a reagent important in practical analysis. (or Cd[HBOjn2+ + 4 Br~ - CdBr43~ + n
Phosphate, however, can be substituted for cupferrate for
most, but not all, members of this group (not vanadium). It
also is used a t a p H of 3 (hot) b u t is somewhat less effective S u c h qualitative considerations, t a k e n alone, a r e sometimes
in competing against interfering chelating agents. fallible a n d t h e y m a y a t t i m e s h a v e t o serve only as r a t i o n a l -
izations. Y e t t h e y c o n n e c t us w i t h f u n d a m e n t a l causes in a
For separations within the groups we have used a great way t h a t is possible n e i t h e r w i t h t h e m o r e precise l a n g u a g e
variety of procedures, but always with few organic reagents. of t h e r m o d y n a m i c s , w h i c h d e m a n d s t h e p r i o r m e a s u r e m e n t
1
of q u a n t i t i e s similar t o those t o b e p r e d i c t e d , n o r w i t h t h e
Methyltrioctylammonium ion, i.e. CH3(C8H,7)3N+, appears at this u p p e r reaches of q u a n t u m mechanics, which would elude m o s t
writing to be at least as effective it used as an extractant in CH3CCI3 beginning s t u d e n t s .
or diisobutyl ketone. However, it has not yet been tested thoroughly.
Mexadecyltrimethylammonium appears likewise to be an excellent A discussion of t h i s sort, d e e p e n e d , qualified, a n d b r o a d -
precipitant. The author wouirj welcome collaboration on further ened, can give t h e s t u d e n t a n idea of w h a t t o e x p e c t for a n y
testing. e l e m e n t , w i t h o u t a d e t a i l e d s t u d y of each one. W h e n , o n t h e
4 3 2* 3* 4*
Li Be B C N O F
5 4 r 3
Na Mg A! a, P s CI
2 1 _ — — -._* 1*
K Ca Sc Ti V Cf Mn Fe Co Ni Cu Zn Ga (Ge As Se) Br
1*
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd rn Sn Sb Te I
Cs Ba Ld HE Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At
Ft Ra Ac Th Pa U
Figure 2. Groups in the Bromide Scheme.
Lti = Santhanoids or rare earths. 3. Cupferrates: MetCfr,; MelQsCfr,. (Or phosphates.! Cfr = C^-i s —NjO 2 .
Groups separated: 4. Fluorides, MeiF,.
1. Mainly bromo-compfexes, MetBr,?"; Met!,*~; Met. 5. (Soluble).
2. Cyanocobaltates, approx.

other hand, the membership of several analytical groups ap- using both bromide and iodide. (Cyanocobaltate is also non-
pears to be distributed somewhat randomly around the peri- basic, but does not interfere in the sulfide schemes.)
odic table, even in the absence of interfering agents, useful Various interfering, basic, organic and inorganic ligands,
correlations may seem less convincing to students. on the other hand, can be inactivated with high concentrations
Soon enough, of course, we must introduce the other part of hydrogen ion. Unfortunately, however, some desirable
of the real world, the exceptions. But this may be more ef- precipitants are also inactive in acidic solution. Still, we can
fective if we can show first that some generalizations do work exploit some basic reagents, such as cupferrate and fluoride
fairly well in practice. (3), for which the metal ions remaining in solution can nev-
In the present schemes Mn, of the "common" elements, is ertheless compete against high or moderate acidities. The net
slightly exceptional. Smal! amounts of it, less than millimolar, result is that we can use acidic conditions throughout our
remain after separating Group 2. These do not interfere sub- schemes to eliminate most sources of interference. (Oxalate
sequently, and they are much less than the amounts of Tl, Pb, can still precipitate calcium prematurely in Group 3. Bromate
and Hg(II) left after the usual chloride group, but they might can be added, however, to oxidize some HBr to bromine,
justify assigning Mn partly to our Group 5. At that point they which, when hot, destroys oxalate.)
could be removed with Fe{CN>64~. In the Iodide Scheme, Zn We tested the effectiveness of this approach. Half of a class
behaves similarly. of 36 students (at International Christian University in
No tests have been done with Po, Fr, Ra, Ac, Pa, the Tokyo) received the usual variety of unknowns. The other half
trans-uranium elements, or some rare earths. The other rare received the same unknowns, but with half the water con-
metals including Tc, however, have been checked experi- sisting of filtered orange juice. There was no difference at all
mentally at least to a limited extent. The general literature in the accuracy of results.
contributes to confidence about the unchecked group classi- This was the only test of this sort, however, partly because
fications. the possible variety of such unknowns is limitless. It seems
preferable to continue the exploratory checking of many po-
interference tential improvements than to concentrate too much on any
Interfering species can be classified as basic and non-basic one version, which we expect to supersede anyway. Students
(with respect to H + ). Bromide and iodide ions, which can benefit by knowing that this is not a finished science. We have
prevent the precipitation of various sulfides, are non-basic. nevertheless done great numbers of tests on synthetic mix-
High levels of acidity, such as required for separation of the tures, checking each of a large variety of "interfering" sub*
first sulfide group from the others, therefore do not inhibit this stances with metals that might be problematic. Difficulties
interference. One thing we can do, however, is to follow the that arose in earlier versions appear to be largely solved..
rule, "If you can't lick 'em, join 'em," as we have done here by How does the students' accuracy, using "realistic" un-
+ 4-
Add HC1 as in as in as in Gr. 5
KI Table 1 Table 1 Table 1 Na* e t c .
red-agt. (Check N I C
separately.)
Gr. 1 Gr. 2 Gr. 3 Gr. 4

Cul AlCfr,
Pbl, KZnCo(CN)fi CrCfr, CaFs
etc. etc. etc. (or etc.
phosphates).
Figure 3. Group separations in the Iodide Scheme.
r
5 3 3,4*
Li j Be B C N 0 F
3 2,3* 1*
Na Mg Al Si P S Cl
4 2 3 a
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br
2 1 2
Rb Sr Y Zr Nb Mo Tc Ru Kh Pd Ag cd In Sn Sb Te I
1.2
Cs Ba Ld Hf Ta W j Ee Os Ir Pt Au Hg Tl Pb - Po At
Fr Ra Ac Th Pa U
Figure 4. Groups in the HjS Scheme.

Ld = lanlfianoids or rare earths.
Groups separated:
1. Chlorides; tungstic add.
2. SuJfides.
3. SutiiOes; hydroxides.
4. Carbonates.
S. (Soluble).

cr° t u Or d l^tf. I HS"C HCO,"B Classical Scheme, Modern Forms
HBr distill etc. Bc" H,S NH3 HS" HC0re (2)
ci- H!S NHa HPO4*- | HS" CH,CO,H C,O,'- a ill, 12)
ci- CH.CO,- H,S* so4'- c,o, 2 - NH 3 HPO42-
HSOv A g " Cl H,S CO 3 '-« (14)
Ci" CO3!- OH" Ss" HC1 co3l- ,HC0 3 etc. {15)
C!" NH 3 /HCOr h HS7S,- (I6-I8),(19)J
cr so.1-" i 8,0,'- NH, HCO3- OH- (20,21)

B
cr I- Ag° HSO,- H:S NHa etc. HS" (22)
ci- HSOr* H^ NHa/oxy-an'/OH- (23-25), (26)f
cr HSO,- OH- s=- U1 tl Oy (27)'

1
HNOj-evaporate" i Cl" HS0 4 -° NHS | oxy-an'/OH" (28-33)
i
Cr jHN03-evapofate° HSO4- OH- (XV-" H' [ NHj | oxy-an'/HS"" (33-39),
i ! I (40-42)f
I
......... I I
NaNO3 NaOH Na,CO3 H'CHJCO," NHj HcOr OH (43)"*
fuse'
Cl" CH3CHOHCO,H H2PO,- NH, SCN-CHsNfpyridioe) (45)
ci- CH.CO,- SO.- OH- {46)

i
CI- ! I'(47) RCO,1'" F" OH- (3, 47, 48), (49)1
i
a 3N)63" C.H.N.O.H/H.Pa- HF Bromide, lodidei Schemes
Figure 5. Actual key reagents in various major-group separations.
" Omitted in some oases. ' For only 10 or fewer metals.

0
j represents a ptia§e separation omitted in some schemes.
c
Or CH3CSNH2, C3H5OCS5- (24), or S ! * + H + . etc. ' Fusion destroys organics well but vaporizes Hg: several separations are in-
a
Various osiflanls and reetuctants used here and etsewhere are omitted tor complete; uses CH3CSNH2 on Die fusion solution. Or fuse KNO3 KOH K2CO3
simplicity. (44).
0 m
Plus C^HBOH in some cases. Claims to periodicity are questioned.
' Glve(s) considerably less Interference. " C B H 6 COr'CH3GO ? -/o-C£rt4(C03-)j (48).
0
B With removal and analysis of volatile acids (initially! or other anions. HBr distill (oniy for Ge, As, Se); normally omitted.
* X'Y means X and/or Y, sometimes with phase separation^). P See text.
' Basic oxy-anions: HC0 3 -/C03 ! ""/H J P0 4 -"/HP04 i ".
knowns, c o m p a r e w i t h t h e results, for conventional unknowns, The Iodide Scheme

from t h e suifide s c h e m e ? T h e last class, 35 atudente, using t h e
B r o m i d e S c h e m e h a d p e r f e c t r e s u l t s for 6 o u t of t h e 8 m e t a l s Most American schools allow limited time, if any, for
s t u d i e d . ( G r o u p 5 w a s o m i t t e d . ) A n y j u d g m e n t is d i f f i c u l t , qualitative analysis. Some extra attention will therefore be
however, because we haven't made extensive comparative given now to a short version, recently devised, which focuses
s t u d i e s , b e c a u s e t h e r e a r e m a n y varieties of t h e aulfide s c h e m e , on 10 cations (in Figure 3). In each of the five groups just two
b e c a u s e t h e B r o m i d e S c h e m e a l s o ia s t i l l b e i n g i m p r o v e d , a n d cations are selected for possible use in students' unknowns.
because the interest generated by any novelty m a y provide (The selections can be varied occasionally, or from student to
a temporary advantage. s t u d e n t ) This obviously shortens separations within the
Optimization of t h e B r o m i d e S c h e m e , incidentally, o u g h t
groups. In fact, we can give the students some information on
t o t a k e l o n g e r t h a n t h a t of t r a d i t i o n a l o n e a , a n d p r o v i d e m o r e
chemical properties and let them devise separations and
o p p o r t u n i t i e s for s t u d e n t r e s e a r c h , w h i l e p o s s i b l y y i e l d i n g
identifications for each pair. One way is to give a list of
technically better results, because there are m o r e variables
chemical equations (available from the author) as a starter.
in the m o s t crucial group separation. Corresponding to the
The absence of the unpleasant hydrogen suifide in group
f o r m e r c h o i c e s of p r e c i p i t a n t (suifide) a n d p H ( t o c o n t r o l i t s
separations, incidentally, is no reason to exclude completely
c o n c e n t r a t i o n ) , w e h a v e t h e c h o i c e s of l i g a n d ( b r o m i d e ) , c a t -
sodium suifide, for example, from every later separation.
i o n i c e x t r a c t a n t , s o l v e n t , a n d c o n c e n t r a t i o n s of t h e first Our list of 10 ions was chosen to emphasize somewhat those
two. which are important in our nutrition. Na, Mg, Ca, Cr(III), Fe,

Cu, and Zn are essential metals. Pb, and potentially Cr(VI), Three of the many papers on solvent extraction seem par-
is included aa a poison. Even with our environmental concerns, ticularly interesting and/or useful: one on inorganic com-
or because of them, students ought to have some scientific plexers plus quaternary ammonium extractants (58), one on
acquaintance with toxic elements, especially one that they halides and organic chelons for separating 18 groups (59), and
meet every day on the streets. The Bromide and Iodide one on 5 chelons for 8 groups (6'0). Separations can be done
Schemes can handle low concentrations of the dangerous in acetic acid instead of water, with, for example, CH3COCI
heavy metais, and it is recommended to dispense them at the to precipitate an enlarged group of metailic chlorides (61).
millimolar level. In this way the dangers of handling them, Finally, we should note some cautions about the reliability
which may have induced some professors to omit qualitative of published qualitative analytical data (62).
analysis entirely, are greatly reduced. The solvent extraction
in the Bromide Scheme could, unlike ordinary precipitation, Summary
separate even individual hazardous atoms from the aqueous The Bromide Scheme now proposed begins with the solvent
solution for possible detection by special methods. extraction of a group of bromo-complexes from a highly acidic
To study some other toxic elements, e.g. cadmium, we can solution, with several major and minor advantages. Teaching
simply precipitate (or extract) Mtp2CdI*, for example. is promoted because the analytical groups make sense in the
periodic table. Realistic unknowns can be used because most
Other Schemes organic and inorganic "interfering" substances no longer in-
We are at last seeing in this country a resurgent recognition terfere. The need to look for some elements in two different
of the teaching potential in qualitative analysis, and various groups is reduced, and H^S is not needed. Some attention is
systems are proposed. Sometimes, however, the wheel is re- given to handling small amounts of the more toxic elements.
invented, and too frequently without acknowledgment of the Students have good exposure to complexation, solvent ex-
earlier contributions. (Normally, of course, some modifications traction, and such a practical analytical reagent as cupferron.
are made.) Also, a look at the relationships of the present They may also have more opportunity to make significant
schemes to the others may help put all of them into perspec- improvements in the scheme.
tive. Figure 5 is therefore presented as a condensed survey, The goals pursued here have been under exploration for
mainly of the last 50 years, and mainly of non-HgS systems several decades, but their expression in the Bromide Scheme
unless other features have special interest. Some schemes are is only about 10 years old, and this lack of experience is a
omitted where later improvements by the same authors are disadvantage. Also, some reagents are currently unfamiliar
included. Also omitted are many non-HaS schemes using other to beginning students. Of the few organic compounds used in
sulfur compounds with rather similar results. Systems showing group separations, however, none is specifically required and
substantially improved periodicity are rare, but various ap- none depends for its essential function on any impenetrable
proaches toward somewhat less interference are available aa structural complexities.
listed, even without the tedious classical procedures.
The Iodide Scheme is a more recent, somewhat simplified
The order of listing in Figure 5 depends more on similarity form, without initial solvent extraction, and not developed for
than on chronology. The main reagents for the separation of all the metais. Students may be asked to work out separations
each major group, usually as precipitates but sometimes as a for a pair of elements within each of the five groups. Elements
solution, are shown in successive boxes from left to right. important in nutrition may be emphasized.
Generally, only the predominant species of a reagent in Some further information is available from the author.
solution is shown here, partly to reveal essential similarities. Please send $2 for expenses.
Thus, in acidic and sometimes alcoholic solutions where some
writers call for H2SO4, others call for ( N H ^ S O ^ both, rep- Acknowledgment
resented here as HSO4-, actually yield mainly HSO4" (or Special recognition for major contributions must go to the
SO4 2 -, depending on the exact conditions). And in solution late Charles Kauffman and to John Buhr and Yung-Kuo
the usual "<NH 4 ) 2 CO 3 " is reaily mostly NH 3 , NH 4 +, HCO3-, Chao, former students at Bethel College, North Newton,
and CO^NEfe*"* with HCO3" actually providing most of the Kansas, as well as to Albert Sun-Chi Chan and Tai-Wai David
carbonate ions used for precipitation. The representation Chan, former students at International Christian University,
chosen here also gives useful information about pH; H2PO4™, Mitaka, Tokyo, Japan. The author also carried out parts of
for example, is known to predominate at pH's from 2 to 7. this work at the Universities of Kansas and Illinois, at Harvard
Many fascinating papers depend heavily on spot tests, and Stanford Universities, and at home and Bluffton College.
various sorts of chromatography, etc., but these sometimes H. W. Berky at Bluffton suggested the original project.
bypass pedagogically valuable chemistry and they are slighted
here, though several such techniques can well be presented
as parts of any broader system. Some of trie most original ideas Literature Cfied
listed in Figure 5, by the way, have appeared in relatively
(1) Soritjn. Cr H., and Lagow6ki. J, J-, "Introduction to SeiBimicro Qualitative Analysis,"
obscure journals, Sfhed, Pren lice-Hall, Englewood Cliffs. NJ, 1977, p. 121.
A few additional papers, excluded from Figure 5, wil! be (2) Nuyea, A. A., and Bray. W. C, "Qualitative Analysis for the Koire Elements," Maraiilian,
New Vorfe, 1948, pp. S, 12, 16-17, 37-39.
mentioned here. Cr 2 O7 2 " has been used to separate the ele- (3) West, P. W.,and Vlclt, M M., "Qualitative Analysis and Analytical Chemical Separa-
ments of sulfide groups II and III (50). Reducing agents may tions," Macmilkn, Mew Yoifc, 1939, p. 18.
also be used to precipitate members of the sulfide groups, as (4) Rich, R., J. CHEM. EDUC, 39,403 (1963).
(5) Melnikow, J,,Keeffe,J. IL, and Bernstjsin, R. L.,J. CHEM. EDUC. 58, A12 (1981k
with reagent Mg (51), Al or Zn (52,53), or with the product NiOSH, "Suspected Carcinogens," 2nd ed.r Pub. #77 -149, US Dept, HEW, Wash-
of the reaction of S 2 O 4 2 - and HCO 2 H (54); also see (22). An- ington, 197fi.
<6> Cai-lion, T. S.. J. CHEM. EDUC, 59,530 (1982).
other interesting non-H^S approach uses a separate portion (7) G*Jbach,R.W.,J.CJMiM. E D U C , 10,821 (1933).
of unknown solution for each group of cations, but sometimes (8) Seheier.G. A., Scftuoi Sri. Maid., 50,6400950).
with separate preliminary removal of the same (non-member) (9) Swift, & H., "A System of Chemical Analysis," Prentice-Hall, Englewood Cliffs, NJ,
1939, p. 197.
cations from the various portions (55). (10) Rich, it., "Periodic Correlations," W. A. Benjamin. New York, 1965, Chapter 8.
(11) Scheinkmann, A., Z. anal Chem., 9!,415 (1933).
A survey of methods applied to the alkaline earths is one (12) Kreshkov, A. P.. J. Gen. Chem. (USSR), 2,593 (1932).
article (56) in a valuable series especially on classical quali- (13) Cornog, •}., "'Semimicro Qualitative Analysis," Houghwn Miffin, Boston, 1948.
(E4) Saredo, J - F , Analeaasoc. qutm.farm- Uruguay, 51, no. 2,5&(195ii;Anate$fac. qtum.
tative analysis. A Dutch book (57) includes a detailed sum- y/arm., 4,123 {19551
mary of four non-J^S methods (for cations), two of which are (15) Vortmann, 0., see C h ™ . Abstr., lfi.2458 (1832).
outside the scope of this article. The others (15,52) have been (16) Sefbinovskaya, E. L , see Chem.. Abstr., 49,3731!) !19B5).
(17) Meanard, P.. Collel*r, J. C . and Bernard, H.. Bull. Sec. Pharm. Bordeaux. 100. l a s
touched on here. (1961).

(18) Baudot, P., Monal, J. L.Lejailte, M. F., ondMarUn.J. A..Sci Pherm, Bin!. Lorraine,
(42) Bienchi, P., Arch. farm, bioqulm. Tucuman, 5,263 (i951).
1.121 (1973), (43) Swift, E. H,, end Scoaefer, W, P., "Qualitative Elemental Analysis," Freeman, San
(19) RaUinamma, D. V.r J. CHBM. EDUO., S7.287 (1980). Francis™, 1962,
(20) Dtfranra, E.,J. pharm. Belg., 13,771 (1931). (44) NaB8mi, S,, and Kato, T., J. Chen. Sot. Japan, S3,237 (1932),
(21) Tougarinoff, B., J. pharm. Beig., IS, m + preced. (1933). (45! Dobbins, J. T., and Gilreath, E. S., J, CHEM. EDUC., 22,119 (1945).
(22) H6nrytA.J.,Ano(3'sl,89,255(19641. (46) Prokopov, T. S., MiknKhim. Aaa, im, 694.
(23) Chao, T. P., and Hwang, S. C, J. Chinese Chem. Sue., 8.31 (1941). (471 Johar.G.S., Sei. Res. News., 1,135 (1979).
(24) Wenger,P.,Buckert,R.,andAnkajdi,E.,Htln.Chim. Atia.lt, 15929945], MS} Lurome, P., and Tummavuori, J., 4cio Chem. Scand., 27, S61 (1973).
(25) GaIidfe,P,J.,/l//m!ind,2S,lS4[lB61). (491 Lambert, J. L., and Meban, C. E..S. CHEM. EDL'C, 54,249 (1977),
(26) Poonifl, R S-, and Bhagwat, V. W.. Mikmchim. Ada, IMS, 1008. (50) Efroa, S, M, and Golynko, N, %., see Chem. Abatr., IS, SaiOg (1956).
(27! Ambas Jimenii, S., and Alvaraz Bartolome. M. L., Inform. Quim. Anal., 17, (511 146 Hnaentbalcr, L;1 Pharm. Acta Heto., 19,96 (1944).
(1963). (52) Schoori, "Qualitalieve Analyse der Metalen zonder Toepaesbg van Zwavelwaterstof,"
(S8I Kichier, H., Oesterr. Chem,-Ztg., 39,185 (1D36). O. B. Centen'g, Amsterdam, 1941,
(29| Petraschenj, W. J,, Z. anal. Chem., 106,330 (1936). (631 Kiba, T,, J. Chem. Sac. Japan, 79,323 (1949).
(30| Rane, M. B,, and Knndaiah,K., J. Indian Chem. Sac, 14,48 (1937), IM) Viieilio, C>., ha. Ahad. Nauk SSSR, Ssr. Khim., 1964,2245.
(31) Khnroahkin, M, N., Aela Umii. Voraneg., 10, no. 4, Sect. Chem.,98 (1939).(55) Upcbinaki,A.?..GodishnihKhim.-Telihntti.In&t. (Sofia),I,59(1954);ovorabednuw
(32) Ok4f, A., Pufis. /acuM us. unto. Masnryi.no. 311,25 pp. (1948), charts facing p. 126; Russ, summaty, p, 128.
(33) Bioekrafln, C. J., "Qualitative Analysis," Ginn, Boston, 1930, (561 J™ea,W.F.,Mj*™fcim. Ac(o, 196V, 1004.
(34) Uwin, A. B,, Z. anal, Chem., IBS, 328 [1936). (S7) Van Nieuwenbiirg, C. J., and Van Ligten, J. W. L., "KwaHtatieve Oh^niacbe Anaiyse,"
(36) Valeni* de Couto, A., Quim. e ind. (Sfe Paulo), 8,1601 (1940). D. B. Cental's, Amsterdam, 1951,
(38) Beskov, S. D,, and Sliakovataya, 0. A., see Chem. Abstr., 46, i911s (1952). (581 Maeck, W. J., Boosnan,fi.L., Kusay, M. E, and Kein, J. R, Anal. Chem., 33,1775
(37) Cotnog, J., "Seaimicro Qualitative Analysis," Hoiighton Mifflin, Boston, 1961. (1961).
(SB) Handler, B. L,, Cnol, R., and Siemioncow, G.. J. CHEM, EDUC, S9,33S (1982). (59| Toeh,ti.,Z. anal. Chem., 190,161(1982).
(39) Matauolin, K.,J. Nippon Unit. School Dentistry, 5.157 (1963). (60} ChaSmers, R. A., and Bici, D. M., Anal Chim. Aaa, Si,520 (196«,
(40) Geisttmaine, E, M.,J. CHEM. EDUC, 11,369 (19341. (61) Hardt, H. D., and Ectlo, M,, Z. ami. CW., 197,160 (1963).
(411 ZBlada, P.. Anales asac. quim. argentina, 30,29 (1942). (821 Belcher, R.,.*^!!, 99,302(1974),
edited by
profile/ in chemi/try
ROGER R. FESTA
School ot Education, Son U-33
The University ot Connecticut
Storrs, CT 06268
Jean Rey: Unsung Prophet? a n d a r c a n a of t h a t p r o f e s s i o n , B y 1 6 0 0 , a l c h e m y i n E u r o p e w a s

a l m o s t c o m p l e t e l y u n d e r t h e influence of t h e followers of
Sidney Rosen P a r a c e l s u s . T h e a b s t r a c t c o n c e p t s of S a l t , S u i f u r , a n d M e r c u r y
341 Astronomy Department h a d been a d d e d t o t h e original Aristotelian elements: E a r t h ,
University ot Illinois
Urbana,IL61801 W a t e r , Air, a n d Fire.
N o w h e r e i n h i s b o o k , d o e s R e y a d m i t t o doing t h e a c t u a l
In J a n u a r y 1775,A n t o i n e Lavoisier sent t o t h e A c a d e m i e e x p e r i m e n t s of calcining t i n a n d lead a n d m e a s u r i n g c h a n g e s
dea Sciences in Paris h i s now-famous m e m o i r o n t h e calcina- in weight. T h e e s s a y s a r e i n t r o d u c e d b y a l e t t e r t o R e y f r o m
t i o n o f m e t a l s t h a t w a s t o r e d u c e t h e p h l o g i s t o n t h e o r y to M o n s i e u r B r u n , a n apothecary from Bergerac, w h o h a d d o n e
a s h e s in t h e h i s t o r y of science. T w o m o n t h s later, a n o t h e r t h e experiments a n d w h o essentially challenged R e y t o p r o -
chemist wrote a letter to t h e Academie, pointing o u t t h a t v i d e a n e x p l a n a t i o n of t h e results, B r u n h e a t e d 2 l b s 6 oz of
L a v o i s i e r ' s s o l u t i o n t o t h e q u e s t i o n of w h a t h a p p e n s w h e n a t h e p u r e s t English t i n (from Cornwall) m a n iron container
h e a t e d m e t a l b e c o m e s a calx h a d already b e e n suggested s o m e for 6 hr; u p o n weighing t h e resulting w h i t e calx, h e found 2 lbs
1 4 5 y e a r s e a r l i e r (1), 13 oz. D o i n g t h e s a m e e x p e r i m e n t w i t h 6 l b s of lead, B r u n
T h a t second chemist was Pierre Bayen, Apothecary to the f o u n d t h e c a l x d i m i n i s h e d i n w e i g h t . " I b e g o f y o u i n a l l af-
King's Army; t h e person to w h o m h e referred was a 17th- f e c t i o n , " B r u n e n d s his letter, " t o go t o w o r k o n t h e cause of
c e n t u r y F r e n c h p h y s i c i a n n a m e d J e a n R e y . O n t h e f i r s t of s u c h a r a r e e f f e c t ; a n d I w i l l b e w h o l l y o b l i g a t e d if, b y y o u r
J a n u a r y 1630,a little book, privately printed, h a d a p p e a r e d m e a n s , t h i s m a r v e l o u s r e s u l t is m a d e c l e a r t o m e " ( J ) .
in t h e B o r d e a u x area of s o u t h w e s t Prance, T h e title w a s r a t h e r T h e first 15 essays a r e d e v o t e d t o proving t h a t t h e e l e m e n t
long: " E s s a y s b y J e a n R e y ,D o c t o r of M e d i c i n e , o n t h e S e a r c h A i r h a s w e i g h t . T h e b a s i c a r g u m e n t u s e d b y R e y is t h a t A i r i s
for t h e C a u s e of t h e I n c r e a s e in W e i g h t of T i n a n d L e a d w h e n c o m p o s e d of p a r t s of different d e n s i t i e s . U p o n h e a t i n g Air,
t h e y a r e Calcined." W i t h i n its 144 pages w e r e 28 s h o r t es- t h e l i g h t e r d e n s i t i e s a r e d r i v e n off, l e a v i n g t h e d e n s e r p a r t s
says. of t h e e l e m e n t a r o u n d t h e m e t a l w h i c h is b e i n g t r a n s f o r m e d
N o t m u c h i s k n o w n a b o u t J e a n R e y ' s life. H e w a s b o r n into a calx b y t h e same heat. Rey's a r g u m e n t s tell u s t h a t he
a b o u t 1 5 8 2 i n t h e l i t t l e t o w n o f L e B u g u e , t h e s o n o f a greffier w a s quite familiar with alchemical e q u i p m e n t , procedures,
( o n e w h o c o l l e c t e d t a x e s f r o m l a n d s p u t in h i s n a m e a n d and language (2).
farmed). Jean's parents died when he was a boy, a n d he was T h e p o i n t of t h i s d i s c u s s i o n b e c o m e s c l e a r i n E s s a y 1 6 ,
raised b y h i s elder brother. I n 1609 h e g r a d u a t e d from t h e w h e r e R e y p o i n t s o u t t h a t t h e reason t h e calx is heavier t h a n
University of Montpellier with a n M . D .degree a n d set u p a t h e original t i n m e t a l is t h a t d u r i n g t h e h e a t i n g process, t h e
medical practice in his home town. Rey was, apparently, d e n s e r , a n d t h e r e f o r e h e a v i e r , a i r in t h e a l c h e m i c a l f u r n a c e
c o n s i d e r e d a n e x c e l l e n t p h y s i c i a n ; t h e r e is a r e c o r d of h i s a d h e r e s p h y s i c a l l y to t h e a l r e a d y f o r m e d c a l x . H e u s e s t h e
h a v i n g b e e n r e q u e s t e d t o visit a n o b l e p a t i e n t a t T o u l o u s e , a n a l o g y of w a t e r m a k i n g s a n d h e a v i e r b y m o i s t e n i n g a n d
a b o u t a h u n d r e d m i l e s a w a y . I t is s u p p o s e d t h a t R e y d i e d i n c l i n g i n g t o e a c h g r a i n ( 2 ) . W h i l e R e y ' s e x p l a n a t i o n is m a d e in
1 6 4 5 , b u t t h e y e a r i s n o t c e r t a i n (1). physical t e r m s , r a t h e r t h a n chemical, i t w a s close enough t o
W h i l e t h e r e is l i t t l e e v i d e n c e t h a t R e y w a s a p r a c t i c i n g a l - t h e t r u t h to interest a famous c o n t e m p o r a r y F r e n c h intel-
chemist, h e was m o s t certainly acquainted with t h e language lectual, F a t h e r M a r i n M e r s e n n e , a n d later to influence L a -
voisier.
"Profiies In Chemistry" is a biographical ieature, highlighting the con- I n h i s first p a p e r p r e s e n t e d t o t h e A c a d e m i e , L a v o i s i e r m a d e
tributions of distinguished chemists In the context of their lives. The n o m e n t i o n of R e y . H o w e v e r , a f t e r h e r h u s b a n d ' s d e a t h , M m e .
column is designed for curriculum enrichment, allowing the secondary
Lavoisier p u b l i s h e d a m e m o i r in w h i c h Lavoisier writes t h a t
school teacher to enhance the vitality of chemistry with the sense of
t h e discovery a n d r e a d i n g of J e a n R e y ' s s i x t e e n t h e s s a y h a d
scholarship and adventure shared by chemists throughout history.
s o m e i n f l u e n c e u p o n h i s t h i n k i n g (1). I t s e e m s a m a z i n g t h a t

Rey's b»ok should have been ignored for so many years; Rey's thermoscope was closer to the modern thermometer
however, it was published without the privilege du roi and than Galileo's, which used a column of air.
apparently in amail quantity. Thus, even though Professor Mersenne replied to Rey's letter a few months later, but Rey
Spielman, a chemist at the University of Strasbourg in 1770, did not answer until March of 1643, eleven years later! His
recommended Rey's book to his students, the chances are that letter apologized for the delay, which he blamed on domestic
they were unable to find a copy available (/). Another reason troubles. Mersenne had already published in 1632 an approval
for the eclipsing of Rey's work may have been the publication of Rey's essays in a book entitled, "Les Questions Theologi-
in 1673 of Sir Robert Boyle's "Essays of Effluvium." In this ques, Physiques, Morales, et Mathematiques" (J).
work, Boyle proposed that the gain in weight of a calx was Looking back, it seems amazing that the hypothesis of
caused by the absorption of "corpuscles of fire" passing phlogiston, proposed by George Stahl in his "Fundamenta
through the wails of the sealed container in which the calx was Chymiae" (1700), should have gained such popularity. Stahl
formed. Boyle's explanation became widely accepted; un- got the idea of a principle of burning from his teacher, Joa-
doubtedly, the popularity of Isaac Newton's view of both light chim Becher, who invented the term, terra pinguis—the
and matter as "corpuscles" helped. combustible element. But the evidence that was to give the
In his last essay, Rey makes it quite clear that Brun's result phlogiston theory the kiss of death was already available! Yet
(in which the calx was lighter) is inaccurate (as the book title the major chemists of the 18th century tended to ignore that
indicated). Rey declares that the experiments of other well- evidence for over 75 years, even after Pierre Bayen brought
known alchemists (he names Cardan, Scaliger, and Caesai- Rey's essays to their attention in 1775. Of course, the path to
pinus) bear out the conclusion that the calx of lead gains the formulation and acceptance of oxygen theory was a iong
weight just like that of tin (2). Rey proposes that M. Brun and difficult one. Even Lavoisier's tight-knit evidence was not
made the error of using impure lead and that the loss of weight immediately accepted by all chemists. Joseph Priestly died
was caused by vaporization of the impurities (2). in 1804, a self-exile in America, still believing in phlogiston
and still calling oxygen "de-phlogistieated air."
There are extant two letters to Jean Rey from Father Marin
Mersenne, the intellectual priest who gathered scientific In his classic "History of Chemistry," F. J. Moore mentions
pen-pals like flowers from a garden. In the first letter, dated Jean Rey in a footnote that concludes: "No one who reads [his
1631, Merseene mentions having read the "Essays" and goes charmingly written and amazing paper)... will be likely to
off on a wide tangent, discussing Copernicus and Giordano believe the author capable of making any serious discovery"
Bruno. Eventually he gets around to discussing the idea of Air (3). While Moore's evaluation of Rey may be well-founded,
having parts of different densities. Rey answered Mersenne Jean Rey's work remains as a reminder of how easily clues to
the following year (but six months later); in his letter, Rey scientific truths can be overlooked.
describes a thermoscope he had invented to measure tem-
perature (Galileo was inventing one in Italy, too). Rey's Literature Cited
thermoscope consisted of a glass bulb with a long hollow neck. (I) McKie, Douglas, "The Essays of'Jean fley,"EdwardArnisld, London, A95L
The bulb was filled with water and the temperature of a sub- 12) Rey, Jean. "The Increase in Weight of Tin and Lead™ Caidnatoon." Alembic Oub
stance was measured by observing the expansion of the water. Reprints, No. li, Edinburgh, 1963.
(3) Moore, *\ J., "A History of Chemistry," McGraw-Hill. New YorSi, 1916,
The History of Science in China: A Summer Science History Tour

Temple University in Philadelphia and Tianjin Normal University in the People's Republic of China are again offering
their summer study torn on The History of Science in China in 1984.
The 21-day program will cost approximately $3,000, including air fare to and from San Francisco, all food and lodgings,
and travel to historically important sites within China. Graduate credit is availabte, and aide trips to Hong Kong, Japan,
and Hawaii can be arranged.
Participants will receive a current bibliography for background use well in advance of departure.
The last summer history tour of Chins was described by Benfey and others in a report in THIS JOURNAL {60,371 (1983)].
The article is an excellent documentary of the 1982 exchange between Temple and the host institution, Tianjin Normal
University.
For futher details, contact: Dr. Joseph S. Schmuekler, 452 Ritter Hall, Temple University, Philadelphia, PA 19122,
Office: (215) 787-6137, Home (215) 649-3607.

Qualitative Determination of Nitrate
with Triphenylbenzylphosphonium Chloride
Donna A. Berry
Shaker Heights H.S., Shaker Heights, OH 44120
Jerry J. Cole
Ashland College, Ashland, OH 44805
The general procedure for the identification of nitrate is the Permanganates interfere because of their color.
anion group separation which is made with barium and silver The triphenylbenzylphosphonium chloride (TPBPC) re-
solutions (1), or by division into three main groups: AgNOg agent was tested to see if it precipitated any anions other than
group, BaCl 2 group, and the soluble group (which are the nitrate, or would interfere with the standard qualitative teats
anions t h a t do not precipitate with AgNO 3 or BaCla), NO 3 ~ (6), (7), for anions other than nitrate. As a result of the tests,
is in this group (2). The separation procedures are then fol- a new qualitative scheme had to be written, since TPBPC
lowed by the individual tests for the aniona. precipitated the anions: Br~, NO2"", I~, and MnXV".
The standard test for nitrate wili be referred to as the
"Brown Ring" test. Since the dependability of the"Brown New Qualitative Procedure
Ring" test is questionable, a new qualitative scheme was
(This Procedure follows the laboratory manual by Hered
written using the reagent, triphenylbenzylphosphonium
chloride (TPBPC). and Nebergail) (8):
Procedure 6
if*! Identification of NOS~ in the absence of NOi~,Br~,andI~.
To 1 ml of the prepared solution add 5-8 dropa of the prepared
reagent (TPBPC). A white crystalline precipitate confirms the
, — P — O C I presence of NO3~.
Procedure 7
Identification of NOS" in the presence of NO-i~,
T r i p h e n y l b e n z y l p h o a p h o n i u m c h l o r i d e is a slightly c r y s - If the NOs~ is between 0.3 and 0.1 M there is no interference with
talline solid t h a t is soluble in alcohol, b u t only slightly soluble TPBPC.
in w a t e r a n d a c e t o n e . I t is soluble in a l i p h a t i c a n d a r o m a t i c Removal of NO2".
h y d r o c a r b o n s . I t h a s a molecular weight of 388.9, m i n i m u m To 8 drops of the prepared solution add 4 M H$Ot until acidic,
p u r i t y of 9 5 % a s supplied, a n d a m e l t i n g p o i n t of 3 2 5 - 3 3 3 ° C
and then add 4 drops of 1M {NHjJaSC^ solution. Place the mixture
in a casserole and slowly evaporate to a moist residue (not dryness).
(3). W h e n a d d e d t o a solution c o n t a i n i n g n i t r a t e , t h e t r i - Add 4 drops of H2SO4 and evaporate to a moist residue a second
p h e n y l b e n z y l p h o s p h o n i u m chloride f o r m s t r i p h e n y l b e n z y l - time. Dissolve the residue in 10 drops of H2O and transfer the
p h o s p h o n i u m n i t r a t e , a w h i t e crystalline solid. mixture to a small test tube. Repeat the test for the confirmation
of NOg- (as described in Procedure 6 with the TPBPC reagent) on
Standard Qualitative Test for Nitrate (4) the sample resulting from the removal of NO^-.
The "Brown Ring" test for nitrate is made by adding ferrous
sulfate to the unknown in a test tube and then carefully adding Three different trials were run to see if the elimination process
concentrated sulfuric acid in such a manner that it does not interfered with nitrate samples.
mix but forms a separate layer at the bottom of the tube. If 1) Sample of NO2": removed N<V; no precipitate with reagent
TPBPC when tested for NO3~.
nitrate is present, a fine, brown ring wil! be formed at the 2) Sample of NO2"" and NOs~: removed NO3"; tested positive with
junction of the acid and the solution. reagent TPBPC for NO 3 ".
3) Sample of NO3"~: followed procedure to remove NO2 ; tested
NO3 + 3Fe 2+ + 4H -* 3Fe 3+ 4- NO +2HjO positive for NO 3 " with reagent TPBPC.
Fe 2+ + NO -* [Fe(N0)] a+ Thus, the method of eliminating NOs™ and testing for NCV with the
reagent TPBPC was successful.
In the first reaction the nitrate ion is reduced to nitric oxide
by the ferrous sulfate. The nitric oxide then combines with Procedure 8
excess ferrous ion to form a brown complex, [Fe(NO)] 2 + . Identification of WOa~ in the presence of Br~ and I~,
Removal of Br~ and I". To a test tube containing 6 drops of the pre-
Interferences in the Brown Ring Test pared solution, add 10 drops of H2O. Acidify the solution with 4 M
The reaction only occurs at the junction of the solution and HOAc and then 80 rag of powdered AgaSO* (NOa~ free). Stir and
the H2SO4, where the acidity is high. If the solution is mixed, grind the mixture in the test tube for 2-3 mm. Separate and transfer
no test is obtained. the solution to fl test tube. Repeat the test as described in Procedure
6 on the solution obtained from the removal of Br" and I".
Bromides and iodides react with the concentrated H2SQ4 Of follow procedures 13 and 14 as follows:
to liberate free iodine or bromine.
Dilute 6 drops of the prepared solution with 12 drops of HaO. Add
Sulfides, suifites, and other reducing agents interfere with HOAc until the solution is acidic and then add 2 drops in excess.
the reaction or ferrous sulfate and nitric acid (5). Addlmlof CCI4 and 5-10 drops of prepared chlorine water to the
Chromates are reduced by ferrous sulfate to chromium prepared solution. If Br~ and 1~ are present, they must be removed
suifate, which will appear as a green layer a t the place where by separating the aqueous and COI4 layers and repeating the pro-
the brown ring should form. cess of adding CCL, and chlorine water until the solution is colotless.

Table 1. Comparison of the "Brown Ring" Test Tabte 2. Summary of Test Results
and the "TPBPC" Test
••Brown Ring" Test "TPBPC" Tesl
Brown Ring Test TPBPC Test
positive 42% 100%
UNKNOWN (7) UNKNOWN
negative 58% 0%
t Acidify with HOAc n =" 100 sludenis (Collage—-general cftemtsiryl
Acidify with HOAc
Lead acetate Stiver sulfate
Table 3. Limits of TPBPC
• I
TPBPC TPBPC Final Concentration
Saturated sliver sultale
White ppt. Indicates KNO 3 (Saturated Solution) of nitrate ion
and 5 drops H2SO4
presence of NOa~
* 1.0 M ppt. 0.1 M
solid ferrous sulfate 0.1 M ppt. 0.01 M
\ 0.05 M 0.035 M
Cone. (B) UNKNOWN ppt.
• 0.025
0.012S
M
M
ppt.
slight ppt.
0.00625 M
1.5625 X 1 ( T 4 M
Acidify with H s SOj
0.010 M slight ppt. 1.0 X 10™" M
0.001 M no ppt.
Siown ring forms at the
0.0001 M no. ppt.
junction of the two Ammonium suiiale
solutions of NOj~ is Note:
present HjO 1. A saturated solution ol TPBPC was made w«h 95% alcohol to see i! the snblfan could
I increase ihs limits and It was found that ttiere was 00 precipitation with even 0.1 M
KNO3.
H3O
2. A saiiffated solution 0* TPBPC was also mads with acetone and There was no pre-
I dpitato wtth 0.1
TPBPC
\
d i s t i l l e d w a t e r . T w o m i l l i l i t e r s of e a c h d i l u t i o n w a s p i p e t e d
White ppt, indicates tiw
presence of NOa~ i n t o a test t u b e a n d t h e n 2 m l o f T P B P C w a s a d d e d ( p i p e t e d
also). T h e p r e c i p i t a t i o n of t r i p h e n y l b e r a y l p h o s p h o n i u m n i -
trate denotes the limits t h a t t h e reagent possessed. T h e d a t a
After all of t h e B r a n d I a r e r e m o v e d , a d d t h e T P B P C r e a g e n t , f r o m t h e d e t e r m i n a t i o n is f o u n d i n T a b l e 3 . T h e l i m i t o f d e -
a m i if t h e r e is a white precipitate, NQg~" is present. If n o precipitate
t e c t i o n w a s d e t e r m i n e d t o b e 1.0 X W* M in n i t r a t e i o n i n t h e
forms, t h e N O S ~ is a b s e n t .
Note t o t a l s o l u t i o n ; a n d f o r b e s t r e s u l t s a s a t u r a t e d s o l u t i o n of
1) A s a t u r a t e d s o l u t i o n of T P B P C w a s u s e d . T P B P C should be used.
2) In t h e p r e p a r a t i o n of t h e chlorine w a t e r — t e s t t h e solution with
Summary
t b e T P B P C reagent. If t h e r e is a p r e c i p i t a t e , tlie chlorine w a t e r
m u s t be d i l u t e d u n t i l n o p r e c i p i t a t e f o r m s . Triphenyibenzylphosphoniura chloride { T P B P C ) forms
3) W h e n m a k i n g a s o l u t i o n acidic or p u t t i n g a solid i n t o solu- a slightly soluble salt with n i t r a t e ion. A satisfactory m e t h o d
t i o n — d o not use H N O 3 t o acidify it. w a s f o u n d u s i n g T P B P C for t h e q u a l i t a t i v e a n a l y s i s o f n i t r a t e
4) In P r o c e d u r e 8, if t h e b r o m i d e a n d i o d i d e a r e n o t r e m o v e d ion, b u t certain precautions h a d to b e observed, since t h e re-
completely t h e r e will be a cloudiness or even a w h i t e p r e c i p i t a t e a g e n t a l s o r e a c t e d w i t h B r ~ , \~, M n O 4 ~ , a n d N O a ~ -
w h e n t h e T P B P C r e a g e n t is a d d e d . B e s u r e t o r e m o v e all of t h e
Br~ a n d I". O n e h u n d r e d general c h e m i s t r y college s t u d e n t s p e r f o r m e d
both the standard "Brown R i n g " test and the " T P B P C " test
A c o m p a r i s o n of t h e " B r o w n R i n g " a n d t h e " T P B P C " for n i t r a t e . C o m p a r i s o n of t h e t w o m e t h o d s s h o w s n o m a j o r
m e t h o d s i s s h o w n i n t h e flow c h a r t s i n T a b l e 1. T h e flow c h a r t s differences in procedure, a n d from t h e s t u d e n t s ' results t h e
i n d i c a t e t h e s i m i l a r i t y of t h e t w o m e t h o d s , w i t h t h e e x c e p t i o n T P B P C m e t h o d proved to be m o r e sensitive and accurate. It
of t h e sulfurie addition being replaced by t h e direct addition ia e a s i e r t o i d e n t i f y a w h i t e p r e c i p i t a t e t h a n a b r o w n r i n g , f o r
of t h e T P B P C r e a g e n t . t h e " B r o w n R i n g " t e s t g a v e p o s i t i v e r e s u l t s o n l y 4 2 % of t h e
F o r t h e last few y e a r s s a m p l e s of college s t u d e n t s p r o c e e d e d time, and the T P B P C worked every time. T h e good detection
t o r u n t h e q u a l i t a t i v e t e s t s (9), {70). S o i i d a n d l i q u i d u n - c a p a b i l i t y o f 1.0 X 1 0 " * M n i t r a t e i o n i n t o t a l s o l u t i o n a l s o
k n o w n s w e r e p r e p a r e d , e a c h c o n t a i n i n g two a n i o n s (N(>3~ a n d l e a d s t o s e l e c t i o n o f t h e T P B P C m e t h o d e s p e c i a l l y for h i g h
a n o t h e r a n i o n ( s o m e i n t e r f e r i n g o n e s : B r ~ , N O 2 " " , a n d I"")). school a n d general c h e m i s t r y college s t u d e n t s .
A f t e r following t h e p r o c e d u r e for q u a l i t a t i v e i d e n t i t y , t h e
u n k n o w n solutions were divided into two portions a n d t h e Literature Cited
students ran both the "Brown Ring" and the " T P B P C " test
(1) Maktrorn, William B.. Flosdorf, Burl W-, and Daggfctt, Albert ?., "Semimiero Qualitative
for n i t r a t e . Analysis of Inyfgiink Material," AroerieaJi Buolt Ceropanyh NVh 1939, p. 253.
T h e d a t a c o n c e r n i n g t h e s e t e s t s is listed in T a b l e 2. I t w a s
(2) Barker, John W., and Glao, Paul K.T "Laboratory Manual fop FErat Year College
Chemistry," McGraw-Hill Book Company, Inc., NY, i9Sl,p. in.
found t h a t the " B r o w n R i n g " test gave positive results only (3) Carlisle Chemical Works, Inc., "DHU Sheets on Phoaphoniuni Salts," 19SS.1
4 2 % of t h e t i m e , w h i l e t h e " T P B P C " t e s t g a v e positive r e s u l t s (4) Hahn, Hichard R, and Welcher, Frank J., "Inorganic Qualitative Analysis. ' D. Van
Nostrand Company, inc., New Jersey, ISB8, pp. 181,188.
everytime. (5) "InoFganic Qualitative Analysis," p. lfil.
(6) Cheronis, Nicholas D., and Stein, Hormsn, "SemiLnicru Experiments in General
Determination of the Limits of TPBPC Chemistry and Qjjaiitative Analysis," John De Graff, Inc., NY, lafifl.
(7) "Inorganic Qualitative Analysis," p. ISfl.
Dilutions were made from a solution of 0.1 M KNO3 and (a) Hered, William, and Nebergall, William U., "Basic laboratory Studies in College
Chemistry," 3rd Ed., Raytheon Education Company, NY, IMS.
placed in 100-m! volumetric flasks. A saturated solution of (9) "flasic Laboratory Studies in College Chemistry."
triphenylbenzylphosphonium chloride was prepared with (10) "Enorgajiie Qualitative Analysis," p. 198.

Qualitative Analysis byGas Chromatography
GC versus the Nose in Formulating Artificial Fruit Flavors
P. W, Rasmussen1
Universiti Kebangsaan Malaysia, Bangi, Malaysia
It ia sometimes forgotten that, besides being a very powerful CH2CI2. T h e c o m b i n e d CH2CI2 e x t r a c t s a r e d r i e d over N a C l
technique of quantitative analysis, GC can also be used a n d distilled t o a small volume.
qualitatively {/). This is especially true if, as is often the case, A l t h o u g h b a n a n a is a fruit t h a t c o n t a i n s a relatively high
considerable information is already available on the sample p e r c e n t a g e of volatile flavoring c o m p o u n d s , still only a b o u t
to be identified. Examples would he in monitoring environ- 20 p p m i s n o r m a l l y p r e s e n t (3). T h i s m e a n s t l i a t if a kilogram
mental samples for a suspected contaminant, or the identifi- of fruit is used in t h e distillation, t h e final e x t r a c t will c o n t a i n
cation of one or more of a restricted set of compounds such as only a b o u t 20 m g of volatile m a t e r i a l . T h i s will b e sufficient
drugs in a biological sample, or volatile compounds in an ar- if t h e v o l u m e of t h e e x t r a c t is r e d u c e d t o 100-200 <ul a n d if a
tificai flavoring. In these cases, a direct coupling of the GC G C w i t h flame ionization d e t e c t o r s is used. I t will p r o b a b l y
with other instrumentation, especially MS, gives good quali- n o t b e e n o u g h if a t h e r m a l c o n d u c t i v i t y i n s t r u m e n t is t o b e
tative and quantitative results but such expensive and dedi- used, a n d it m a y t h e n b e necessary t o c o m b i n e t h e e x t r a c t s of
cated instrumentation is often not necessary for nearly un- several s t u d e n t s ; in fact, i t would b e an a d v a n t a g e t o h a v e a
ambiguous identification. At the very least, proper use of the small group of s t u d e n t s d o t h e e x p e r i m e n t as a project a n d use
GC alone can limit the use that needs to be made of other in- a pooled e x t r a c t . T h e e x t r a c t s h o u l d h a v e a n odor similar t o
strumentation. t h e original b a n a n a s ; t h e residual CHjClg d o e s n o t c o n t r i b u t e
significantly t o t h e odor.
The following experiment is intended for the undergraduate
laboratory as an illustration of the use of GC retention indexes
for the identification of unknown compounds, specifically, the Preparation of Standards
identification of the volatile compounds responsible for the Although it is possible to look up retention indices in the
odor of the banana. This complex sample was chosen to show literature (4), not very satisfactory results are obtained since
the limitations as weli as the usefulness of identification by the GC columns used will probably differ considerably from
retention index only, and because of student interest in such those in the literature. Therefore, it is necessary to prepare
a sample. In addition, other common laboratory procedures standards. This is made easier by the fact that by far the
are illustrated: preparation of the sample illustrates steam majority of volatile compounds present in banana are low-
distillation and solvent extraction, and the preparation of molecular-weight alcohols, esters, and ketones (5). In fact, the
standards requires an ester synthesis. The experiment can be C2-C6 alcohols {including isobutyl and isoamyl), esters of these
extended so that individual components of banana are isolated alcohols with C 2 -C 6 acids (including isobutyric and isovaleric),
and their identity confirmed by infrared, nuclear magnetic and the Cj-Ce 2-alkanones are those most commonly found
resonance, and/or mass spectrometry. Finally, from the results in most fruits (6). In banana, 2-pentano! and esters of 2-pen-
of the GC analysis, an artificial banana flavor can be prepared tanol are also common, while propanoates are rare and can be
and compared (by GC and by nose) to the natural flavor and omitted. The propyl esters can be omitted as well, but to in-
to a commercially available artificial banana flavor. clude them requires no extra time, and it helps in the assign-
ment of GC peaks (vide infra). Later they may be deleted.
Extraction of the Volatile Compounds from Banana Thus, 59 standards must be measured, but they may be run
There are two main problems in the analysis of any fruit by as only nine samples by combining them in series that will give
GC; large amounts of non-volatile material are present and
can clog the injector port and column; and the main volatile
component is water, which obliterates the very small quan- (o)
tities of other volatile compounds present. The usual methods •Cftora
of dealing with these problems are distillation to separate the
non-volatile material and solvent extraction to separate the
water (2). These two methods can be carried out in either
order, but the extraction-distillation sequence involves ex-
tracting a pulpy mass with the attendant difficulties of non-
separating immiscible layers and distillation of very small
amounts of volatile material. Thus, the distillation-extraction
sequence is easier.
A quantity of banana pulp is liquefied in a blender with
approximately twice its weight of distilled water and is steam
distilled. {The slurry will rapidly turn to a greyish-brown color
due to oxidation.) The best extract is obtained if the co-dis-
tillation is carried out at reduced pressure to avoid the poss-
iblity of a "cooked" flavor developing. Under aspirator pres-
sure, the banana slurry need only be heated to 40-50°C and
about lk of it should be distilled. The distillate is saturated 100 200
50 ISO
with NaCi and extracted four times with small portions of
10
' Presenl address: Department of Chemistry, University of Calgary, Figure 1. Gas chromafograms on Apleion L liquid phase, (a) Mixture of vaierate
2500 University Drive, NW, Calgary, Alberta, Canada T2N 1N4. eslers. (b) Mixture ol n-alkanes.

separate peaks on the GC. All other things being equal, re- (X) which falls between the peaks for the rc-alkane with N
tention time on any GC column will increase with molecular carbons and t h e «-alkane with M carbons (M > N), t h e Ko-
weight and decrease with chain branching (7). Therefore, a vats Index (Kx) is given by (7):
mixture of the C^-Cg straight chain alcohols plus 2-methyl- log V x - log VN
1-propanol (isobutyl alcohol) and 3-methyl ~l-butaniol (iso- Kx + 100(M - N) (1)
amy1 alcohol) will give separate peaks on any GC column, and Uog VM - log VN
esters prepared from this mixture and a carboxylic acid will for isothermal operation, where V is t h e r e t e n t i o n volume (or
also give separate peaks. This is illustrated in Figure I.(a), corrected r e t e n t i o n t i m e ) for t h e t h r e e p e a k s .
which shows a regular series of rc-alkyl compounds, inter- For linear-temperature-programmed operation, t h e Kovats
spersed with a two-member isoalkyl series. The regularity of I n d e x c a n b e a p p r o x i m a t e d b y (11):
the series makes assignment of peaks easy, and it was for that tN\
reason that the propyl group was included. Figure l{a) actually lOOAf = lOOfM - JV) (2)
shows the mixture of valerate (pentanoate) esters, which is
prepared as follows: w h e r e t is t h e u n c o r r e c t e d r e t e n t i o n t i m e .
T h e usual m e t h o d for calculating K o v a t s I n d i c e s is t o
About 0.1 ml of the mixture of alcohols mentioned above,
c o m b i n e a m i x t u r e of re-alkanes with t h e c o m p o u n d s t o b e
0.2 ml of valeric (pentanoic) acid and 2 drops of concentrated
measured, b u t this c a n b e difficult with complex mixtures such
sulfuric acid are raised in a small test tube or vial and the test
as fruit e x t r a c t s because of t h e extensive overlapping of p e a k s
tube put in a water bath at 75°C. After about 1 min, when the
{vide infra). A faster a n d only slightly less a c c u r a t e m e t h o d
tube contents have warmed up, the tube is stoppered with a
is t o r u n t h e u n k n o w n c o m p o u n d s a n d m i x t u r e of a l k a n e s
cork to prevent evaporation of the more volatile alcohols and
separately, a n d keep conditions a s nearly a s possible t h e same
esters. Heating is continued, with occasional shaking, for about
d u r i n g t h e t w oc h r o m a t o g r a m s . T h u s , a l k a n e s n e e d n o t b e
one hour, then the tube is cooled and the contents shaken with
m i x e d with a n y s a m p l e , a n d only 11 s a m p l e s n e e d b e r u n o n
two 1-ml portions of 10% NaOH and then dried over a small
each c o l u m n (9 s t a n d a r d solutions, t h e a l k a n e m i x t u r e , a n d
quantity of NaaSC^ or NaCl. The supernatant liquid can be
t h e b a n a n a e x t r a c t ) . T h e s t a b i l i t y of i s o t h e r m a l c o n d i t i o n s
decanted and used directly or diluted with a volatile solvent
or t h e reproducibility of t e m p e r a t u r e p r o g r a m m i n g m u s t b e
such as acetone.
checked b y c o m p a r i n g t w o r u n s of t h e n - a l k a n e s . I s o t h e r m a l
The esters of the other acids can be prepared in the same operation should p r e s e n t n o p r o b l e m s , b u t p r o g r a m m i n g m a y
way. The esters of 2-pentanol can be included in the same or m a y n o t b e a c c e p t a b l e . F o r i n s t a n c e , i n o u r laboratory, a
mixtures by adding 2-pentanol to the mixture of alcohols, but H e w l e t t - P a c k a r d 5710A G C with t h e 5702A oven temperature
it may be difficult to interpret the GC. It is better to combine p r o g r a m m e r is r e p r o d u c i b l e t o w i t h i n ±2 K o v a t s U n i t s ; a
0.1 ml of 2-pentanol with 0.2 ml of a mixture of acids (C2, H P 5840A-microprocessor-con trolled G C gives u n a c c e p t a b l e
C4-Ce, including isobutyric and isovaleric acids) and 2 drops results f u p t o ± 2 0 K o v a t s Units), when t h e y a r e p r o g r a m m e d
of concentrated H2SO4 and react as above to get a mixture of from 50-170 D C a t 4 ° / m i n . T h e d a t a given h e r e were o b t a i n e d
2-pentyl esters. The final standard mixture consists of 2- o n t h e former i n s t r u m e n t .
pentanol combined with the 2-alkanones (CvCe).
When reproducible G C conditions cannot beattained, t h e
Gas Chromatography of Standards a l k a n e m i x t u r e m u s t b e c o m b i n e d w i t h a p o r t i o n of e a c h of
the samples to b e run.T h e n , in a n y chromatogram where
The nine standard mixtures (alcohols, acetates, isobutyr- o v e r l a p p i n g occurs b e t w e e n s a m p l e p e a k s a n d a l k a n e p e a k s ,
ates, butyrates, isovalerates, valerates, hexanoates, 2-pentyl t h e clearly s e p a r a t e d alkane p e a k s a r e u s e d t o calculate t h e
esters, 2-alkanones plus 2-pentanol) and t h e banana extract indices for t h e clearly s e p a r a t e d s a m p l e p e a k s , using e q n s . 1
must be run on a t least two different GC columns in order t o or 2. A c h r o m a t o g r a m of t h e s a m p l e w i t h o u t a l k a n e s is t h e n
obtain reliable identification. These columns should be chosen o b t a i n e d , a n d t h e s a m p l e p e a k s w i t h a l r e a d y c a l c u l a t e d in-
so that they have widely differing characteristics. If two col- dices are used a s references t o calculate t h e indices for t h e r e s t
umns are used, the most logical choice is a column with a of t h e p e a k s , using slightly modified f o r m s of e q n s . 1 or 2:
non-polar liquid phase and one with a polar liquid phase or
one which has a special affinity for esters. Apiezon, squalane, log
and silicone are examples of the former, and Carbowax, FFAP, (3)
log V], - log Vg
and DEGS are examples of the latter (8). A listing of the
McReynoId constants for liquid phases is useful in choosing (4)
columns (9). The actual choice will probably depend mainly
on availabiiity in the individual laboratory, and it is not crit-
w h e r e S a n d L a r e t h e reference p e a k s (sample p e a k s w i t h
ical, T h e two columns chosen here are Apiezon L and Carbo-
k n o w n indices) n e a r e s t t o , a n d o n e i t h e r side of, t h e p e a k t o
wax 1540, both 3 mm X 2.5 m stainless steel with 10% loading
b e m e a s u r e d ( K L > Kx > Ks) (11). T h u s , w h e n e v e r a l k a n e
on Chromosorb W. T h e GC is dual column with flame ion-
p e a k s overlap with s a m p l e p e a k s , t w o c h r o m a t o g r a m s a r e
ization detectors and is oven-temperature-programmed from
necessary for c o m p l e t e a s s i g n m e n t of indices. A m i x t u r e of
50"C at 4 D /min, This gives excellent separation of t h e major
alkanes with t h e b a n a n a extract will h a v e overlapping p e a k s ,
constituents of t h e banana extract, but the analysis can be
b u t m a n y of t h e s t a n d a r d solutions m a y n o t . F o r i n s t a n c e , a
carried out isothermally with slightly less good separations.
m i x t u r e of t h e v a i e r a t e s w i t h a l k a n e s will n o t h a v e a n y over-
In fact, isothermal operation may give better reproducibility
l a p p i n g p e a k s o n either t h e Apiezon or t h e CaTnowax l i q u i d
of retention times, unless the temperature programming is
p h a s e s (see Fig. 1).
carried out carefully and is reproducible.
For t h e banana extract a n d t h e standards used here, a
It is possible to do qualitative analysis by using retention m i x t u r e of C S - C M /i-alkanes is sufficient for t h e Apiezon L
times only, but it is more meaningful to use one of t h e calcu- c o l u m n . T h i s is s h o w n i n Figure l ( b ) . F o r t h e p o l a r c o l u m n
lated retention indices which appear in t h e literature since a (Carbowax 1540), C9-C17 alkanes will cover t h e d e s i r e d
retention time is characteristic of an individual instrument range.
and set of operating conditions while a retention index is in- T h e Kovate Indices for t h e 52 s t a n d a r d s (the seven n - p r o p y l
dependent of instrument variables and essentially charac- c o m p o u n d s were o m i t t e d ) are m e a s u r e d on b o t h G C c o l u m n s
teristic only of the compound being measured. Any retention (Apiezon a n d Carbowax), a n d a r e listed i n T a b l e 1. T h e t a b l e
index may be used (7) but t h e commonest, and the one used is a r r a n g e d in o r d e r of increasing Apiezon index; t h i s facili-
here, is the Kovats Index (10), which is the retention time t a t e s m a t c h i n g u n k n o w n indices w i t h t h e series of k n o w n
relative to the retention times of the n-alkanea. For a GC peak values.

Table 1. Kovats Indices of Standard Compounds
Kovats Index Kovats Index

No. Compound Apiezon Carbowax No. Compound Apiezon Carbowax
1 ethanol <600 957 27 Isobutyl iaovalerafe 965 1214

2 2-bulanona <600 928 28 isoamyi Isobutyrate 968 1215
3 isobutyl alcohol 637 1105 23 hexyt aceiate 974 1290
4 ethyl acetate 645 905 30 2-peniyl butyrate B78 1232
5 2-pentanone 666 1005 31 amyl isobutyrate 1003 1261
630 butyl isovalerate 1005 1272
e rMxityl ateohol 1162 32
7 2-penfanol 712 1133 33 isobutyl valerate 1012 1275
e ethyl Isobutyrate 716 979 34 Isoamyl butyrate 1015 1286
9 Isobutyl acetate 732 1029 35 2-pentyl isovaierate 1029 1263
10 Isoamy] alcohol 747 1224 36 butyl valerate 1054 1334
ii ethyl butytate 764 1052 37 amyl butyrate 1057 1338
12 2-hexanone 766 1110 38 isoamyl Isovalerate 1067 1318
13 butyl acetate 775 1088 33 2-pentyl valerate 1073 132fl
u amyl alcohof 781 1269 40 amyt Isovalerate 1101 1370
15 2-pentyl acetate 808 1090 41 r»xyS isobutyrate 1101 1359
16 ethyl isovalerate 818 1090 42 isobutyl ftexanoate 1108 1372
17 isoamyi acetate 836 1140 43 Isoamyf valerate 1115 1385
ie ethyl valerate 859 1153 44 amy! valerate 1150 1432
IB isobutyl isobutyrate 868 1108 45 butyl hexanoate 1152 1434
20 amy! acetate 874 1190 46 hexyl butyrafe 1155 1438
21 n-riexyl alcohol 878 1370 47 2-pentyl hexanoate 1168 14S3
22 butyl isobtrtyrate 905 1165 48 ftexyl Isovalerate 1199 1467
23 isobutyl butyrate 916 1176 49 isoamyl hexanoate 1211 1482
24 2-pantyl isobutyrate 928 1152 50 amy! hexanoate 1248 1535
25 butyl butyfate 95B 1236 51 iiexyl vaterate 1252 1534
26 elhyf htsxanoate 953 1254 52 hexyl hexanoate 1347 1631
Table 2. Retention Data and Relative Peak Heights for the Gas
Chromafogtams of Natural Banana Extract
Apiezon Carbowax
Chromatogram Chromatogram
Peatc Kovats Peak Peak Kovats Peak •
No. Index Height Mo. Index Height
A1 638 34 C1 1007 54
A2 672 46 C2 1029 4
A3 684 22 C3 1046 6
A4 711 143 C4 1051 4
AS 743 98 C5 1088 30
A6 761 18 C6 1105 43
A7 806 28 C7 1136 174
A8 841 16 CB 1162 29
A9 853 20 C9 1176 21
A10 876 50 C10 1195 3
A11 888 40 C11 1215 6
A12 915 25 C12 1230 160
A13 957 16 C13 1268 30
A14 979 61 C14 1288 133
A15 987 13 C15 1317 14
A16 1010 124 C16 1332 18
A17 1042 3 C17 1370 100
A18 1065 16 C18 1388 4
A19 1077 9 C19 1418 21
Figure 2. Gas chromatograms of natural banana extract, (A) Apiezon L column.
A20 1093 3 C20 1436 26
(B| Carbowax 1540 column.
A21 1106 9 C21 1451 4
A22 1137 4 CE2 1469 52
A23 1153 30 C23 1479 47
Identification of the Compounds in Natural Banana Extract A24 1163 103 C24 1545 17
A25 1196 13
The gas chromatograms of the natural banana extract on A26 1209 34
the Apiezon and Carbowax columns are shown in Figure 2. A27 1347 22
The major peaks are numbered in both chromatograms so that
each peak can be identified with a letter (A or C for the two
columns) and a number. Also, for each chromatogram, the 1,2, a n d 3 of T a b l e 3 . W r i t e in c o l u m n 4 all of t h e s t a n d a r d s
heights of all peaks are measured and normalized to a sum of that have an Apiezon Kovats Index that matches the Kovats
1000. The listing of peak number, Kovats Index and relative I n d e x o f t h e p e a k . A m a t c h is t a k e n t o b e w i t h i n 6 K o v a t e
peak height for both chromatograms is given in Table 2. The I n d e x U n i t s , T h i s r a n g e reflects t h e r e p r o d u c i h i l i t y of t h e gaa
components of the banana extract can now be identified as c h r o m a t o g r a p h u s e d a n d is c h o s e n large e n o u g h s o t h a t n o
follows: p o s s i b l e m a t c h will b e m i s s e d . I n c l u d e i n c o l u m n s 5 a n d 6 t h e
(I) For each peak in the Apiezon cbromatogram, write its t w o K o v a t s I n d i c e s of t h e s t a n d a r d c o m p o u n d s ( t a k e n f r o m
number, Kovats Index and relative peak height in columns T a b l e 1).

Table 3. Identification of the Major Components of Natural Banana Extract
Apie*on Chromatogram Reference Compounds Carbowax Cbromatogram
Peak Kovats Peak Kovets index Peak Kovats Peak
No. Index Height Name ApieEon Carbowax No. Index Height
(1) (2) (3) W (5) (6| (7) (8) (9)
A1 638 34 Isobutyi alcohol 637 1105 ce 1105 43

A2 672 46 2-penfanone 666 1005 C1 1007 54
A3 684 22 1-butanoi 680 1162 C8 1162 29
A4 711 143 12-pentanol 712 1133 C7 1138 174
(ethyl Isobutyrate 718 979
AS 743 98 isoamyi alcohol 747 1224 C12 1230 160
(ethyl butyrale 764 1052 C4 1051 4
A6 761 -jfi
JO
12-hexanone 766 1110 C6 1105 43
A7 806 28 2-penlyl acetate 808 1O90 C5 1088 30
A8 841 16 Isoamyi acetate 836 1140 C7 1136 174
A9 S53 20 ethyl valerate 859 1153
en famyl acetate 874 1190 C10 1195 3
AID 876 878 1370
•U 11-hexanol C17 1370 100
A11 888 40
A12 915 isobutyi butyrate 916 1176 C9 1176 21
1 butyl Butyrate 958 1236 C12 1230 160
A13 957 16
1 ethyl hexanoate 959 1254
J hexyl aceiaie 974 1290 C14 1288 133
A14 979 fii
D 1
(2-penty! butyrate 978 1232 C12 1230 160
A15 987 13
/butyl isovalerate 1005 1272 C13 1268 30
A16 1010 124 j isobutyi valarate 1012 1275
1 losamyi butyrate 1015 1286 C14 1288 133
A17 1042 3
A18 1065 16 Isoamyi isovaierale 1067 1318 C15 1317 14
A19 1077 9 2-pentyl valerate 1073 1328 C18 1332 18
A20 1092 O
(amyl isovalerate 1101 1370 C17 1370 100
A21 1106 9 j hexyt tsobutyrate 1101 1359
I isobutyi hexanoate 1108 1372 C17 1370 100
A22 1137 4
f amyl vaterate 1150 1432 C20 1436 26
A23 1153 30 I butyl hexanoate 11S2 1434 C20 1436 26
Ihexylbutytafe 1155 1438 C20 1436 26
A24 1163 103 2-peoty) hexanoate 1168 1423 C19 1418 21
A25 1196 13 hexyl Isovaleraie 1199 1467 C22 1469 52
A26 1209 34 tsoamyl hexanoate 1211 1482 C23 1479 47
A27 1347 22 hexyl hexanoate 1347 1631
Table 4. Major Volatile Components of Natural Banana Extract (3) F i n a l l y , for e a c h r o w i n T a b l e 3 , c o m p a r e t h e r e l a t i v e

p e a k h e i g h t s i n c o i u m n s 3 a n d 9, T h e y s h o u l d m a t c h t o w i t h i n
Peak Peak Average Synthetic
experimental error.
Compound Number Height Percent Mixture
U s i n g t h i s p r o c e d u r e , a n u m b e r of t h e volatile c o n s t i t u e n t s
isobutyi alcohol A1 ce 34 43 4 4 of b a n a n a c a n b e i d e n t i f i e d . T h e r e l i a b i l i t y of t h e i d e n t i f i c a -
2-pentanone A2 C1 46 54 5 9 t i o n will of c o u r s e differ for t h e v a r i o u s p e a k s . F o r i n s t a n c e ,
1-butanoi A3 C8 22 29 3 1 t h e p r e s e n c e o f i s o b u t y i a l c o h o l is q u i t e u n a m b i g u o u s ; p e a k s
2-pentanoi A4 C7 143 174a 15 16 A l a n d C 6 m a t c h in p e a k h e i g h t (within e x p e r i m e n t a l error)
isoamyl alcohol A5 C12 98 160" 10 10
a n d closely m a t c h t h e t w o k n o w n K o v a t s Indices. However,
ethyl butyrate A6 C4 18 4 1 1
t h e r e may b e r o o m i n t h e C S p e a k f o r a s m a l l a m o u n t o f
2-pentyl acetate A7 CS 28 30 3
s o m e t h i n g else (C6 h a s a slightly higher p e a k h e i g h t t h a n A l ) .
isoamyi acetate AS C7 16 174a 2 2
A10 C17 50 100° 5 3 T h i s i e a d s t o a m b i g u i t y w h e n p e a k A 6 is e x a m i n e d , b e c a u s e
1-tiexanol
isobutyf butyrate A12 C9 25 21 2 2 t h e p e a k h e i g h t of 18 for A 6 m a y b e m a d e u p of a h e i g h t of 4
butyl butyrate A13 C12 16 160° 2 2 f r o m e t h y l b u t y r a t e ( p e a k C 4 ) a n d a h e i g h t of 14 f r o m 2 - h e x -
2-pentyl butyrate A14 C12 61 160" e 6 anone (peak C6j. Thus, peaks A l a n d A6 m a y contain a total
Isoamyi butyrate A16 C14 124 133 13 12 of t h r e e c o m p o n e n t s ( t o t a l h e i g h t 5 2 ) w h i c h a p p e a r i n a dif-
isoamyi isovalerate A18 C15 16 14 2 1 ferent c o m b i n a t i o n at p e a k s C 4 a n d C 6 (total h e i g h t 47) in t h e
2-pentyl valerate A19 C16 9 18 1 Carbowax chromatogram; on the other hand, 2-hexanone m a y
isoamyi hexanoate A26 C23 34 47 4 not be present at all
" Contains 2-pentanol and isoamyi acetate. I t m u s t b e r e m e m b e r e d t h a t t h e s i m p l i c i t y of t h e r e s u l t s in

0 T a b l e 3 is m a i n l y d u e t o a j u d i c i o u s c h o o s i n g of t h e r e f e r e n c e
Contains isoamyi alcohol, butyl butyrate, and 2-pentyl buiyrate.
c c o m p o u n d s , b u t s u c h a c h o i c e is n o r m a l p r a c t i c e i n s o l v i n g
May contain small amounts of other compounds.
m o s t analytical problems. Furthermore, in general, the use
of a n e x p a n d e d s e t of k n o w n i n d i c e s u s u a l l y d o e s n o t l e a d t o
(2) C o m p a r e t h e C a r b o w a x K o v a t s I n d i c e s i n c o l u m n 6 i n c o r r e c t a s s i g n m e n t s , r a t h e r it leads t o g r e a t e r c o m p l e x i t y
w i t h t h e listing o f t h e p e a k s for t h e C a r b o w a x c h r o m a t o g r a m and therefore fewer unambiguous assignments.
of b a n a n a e x t r a c t ( T a b l e 2). W r i t e i n c o l u m n s 7 , 8 , a n d 9 t h e Table 4 summarizes t h e major c o m p o u n d s in b a n a n a ex-
p e a k n u m b e r , K o v a t s I n d e x a n d r e l a t i v e p e a k h e i g h t of e a c h t r a c t which can b e identified with reasonable confidence using
peak with a matching Index (±6 units). T a b l e 3 . T h e p e r c e n t of e a c h c o m p o n e n t i s c a l c u l a t e d f r o m t h e

Table 5. Major Components of Commercial Banana Flavor Extract
Apeiion Chromatogram Carbowax Chromatogram Reference Compounds

Peak Kovals Peak Peak Kovats Peak Kovais Indices
No. Index . Height No. Index Height Name Apeison Carbowax
1 718 12 1 976 14 elhyl isobutyrate 716 978

2 754 2 2 1031 5
3 767 48 3 1055 48 ethyl twbyate 764 1052
4 840 590 4 1148 654 isoamyl acetate 836 1140
J Isoarnyi isovaieraie 1067 1318
5 1068 347 5 1323 270
1073
(2-pentyl valerate 1328
t w o relative p e a k heights (which a r e in p a r t s p e r t h o u s a n d of

the total mixture).
Synthetic Banana Flavor

Using the peak height data in Table 4 a synthetic banana
flavor is constructed, Most of the compounds identified in
banana fall into three groups: butyrates, isoamyl esters, and
non-esters. The esters are synthesized using the above pro-
cedure.
A 1:3:3:17:8 mixture (by volume) of ethyl, isobutyl, butyl,
isoamyl, and 2-penty! alcohols is reacted with excess butyric
scid to form the butyrates (solution A), and a 5:2 mixture of
acetic and isovaleric acids is reacted with excess isoamyl al-
cohol to form the isoamyl esters (solution B). Isobutyl, butyl,
ieoamyl, hexyl and 2-pentyl alcohols, and 2-pentanone are
mixed in a 3:1:7:2:1:6 volume ratio (solution C). Then solutions
A, B, and C are combined in a 8:1:15 volume ratio i*> give a
synthetic banana flavor with the composition given in the last
column of Table 4 (the percentages were adjusted to a total
of 70 to match the total percentage of the compounds in the
natural banana extract). A little dichloromethane is added to
match that present in the original banana extract.
The GC (on the Carbowax column) of the synthetic mixture
is compared to banana extract in Figure 3. It shows a fairly
good match for the major components present in banana; a
similarly good match is obtained on the Apiezon column.
However, the odor of the synthetic mixture is not a good im-
itation of banana odor, thus indicating that there is more to
the synthesis of artificial extracts than the identification of
100
the major components present in the natural extract. In fact,
the very minor components often play a disproportionately
large role in fruit aromas {12), and this makes it very difficult T 20 30
to construct a satisfactory artificial extract by reproducing the

Figure 3. Gas chromatogtams on Cartowax 1540 liquid phase, (a) Commercial
natural composition. Therefore commercially available ex- banana flavor, (b) Mixture of volatile compounds identified in natural banana
tracts are not usually made in this way; rather the nose is used extract, lei Natural banana extract.
instead of the GC (13).
A highly trained nose is of course necessary. Such a nose (for
instance, one belonging to a flavorist who constructs com- p o r t i o n s of s a t u r a t e d N a C l , d r y o v e r N a C l o r N a a S O 4 , a n d
mercial artificial extracts) can identify various "notes" present r e d u c e i n v o l u m e t o a b o u t 1 m l . I t is b e s t t o u s e a n o n - a l c o h o l i c
in an odor and then suggest certain compounds that will re- e x t r a c t o r t h e f i n a l s o l u t i o n will c o n t a i n a l a r g e q u a n t i t y of
produce these "notes." For example, banana odor has a a l c o h o l . I n a n y c a s e , a G C of t h i s e x t r a c t c a n b e r u n a t t h e s a m e
prominent "fruity" note, and fruity notes can be provided by time as the standards and natural extract. A British-made
esters, and the particular quality of the banana fruity note can b r a n d available worldwide, a n d a Malaysian-made b r a n d b o t h
be approximated by isoamyl acetate (13). As most chemists g a v e t h e s a m e G C , a n d a n e x a m p l e o f a G C o n C a r b o w a x is
know, isoamyl acetate does not quite smell like banana, so the s h o w n in F i g u r e 3. T h e K o v a t e I n d i c e s for t h e p e a k s in t h i s G C
flavorist will add small quantities of other compounds to a n d t h o s e o b t a i n e d on t h e Apiezon c o l u m n a r e given in T a b l e
modify the odor slightly, until he has a product which will be 5, a l o n g w i t h t h e i d e n t i f i c a t i o n s t h a t c a n b e m a d e u s i n g t h e
acceptable as a banana substitute, when used in the intended s t a n d a r d s l i s t e d i n T a b l e 1. A s p r e d i c t e d , i s o a m y l a c e t a t e is
manner. This last qualification is important because the fla- the major component, a n d all three major components are
vorist will usually design a flavor for its ultimate use, so that o n l y m i n o r c o m p o n e n t s of t h e n a t u r a l e x t r a c t (see T a b l e 3).
a banana flavor in the bottle may not smell at all like banana T h u s , t h e c o m m e r c i a l e x t r a c t is m u c h s i m p l e r t h a n t h e o n e
but may given an excellent flavor in a banana cake. c o n s t r u c t e d t o i m i t a t e t h e G C of n a t u r a l f l a v o r . O n t h e o t h e r
h a n d , n e i t h e r is a v e r y f a i t h f u l i m i t a t i o n o f t h e n a t u r a l
A commercial artificial extract can be examined easily by flavor.
GC, b u t first it should be extracted into dichloromethane t o
leave behind any non-volatile insoluble material (which, of
course, also contributes to the overall flavor). Dilute 10 ml of Conclusions
extract with 5 ml water, extract 3 tiroes with 10-ml portions A d e t a i l e d r e p o r t o n t h e p r e p a r a t i o n of a b a n a n a e x t r a c t b y
of CH2C1& wash the combined extracts three times with 10-mi v a c u u m distillation-solvent extraction, a n d the identification

of the major volatile components by GC/MS, has appeared Finally, two difficulties arise in this experiment. First, be-
elsewhere (14). The author will be glad to supply a copy of the cause a dilute organic extract is reduced to a very small volume
paper to anyone interested, although it is not concerned with containing the banana volatiles, the purity of the extracting
identification by GC retention index. The banana used was solvent is important. This is one reason for using dichloro-
a variety found in Malaysia, "pisang emas" or Musa acutni- methane. Reagent grade probably can be used directly or after
nata (Colla), var. Sucrier. However, any banana should give a simple distillation. However, this should be checked: the
equivalent results, and in fact would be easieT to check in the reagent grade CH2CI2 available in Malaysia shows consider-
literature, since most published work has been on the common able amounts of two impurities identified by MS as a tri-
varieties found in the markets of North America and Europe chloroethylene {Kovats Indices 721 and 1005) and tetra-
(5). • chloroethylene {Kovats Indices 842 and 1041). These two
It should be emphasized that due to the complexity of the couid not be removed by distillation and are present in the
natural banana extract, all identifications by retention data banana extract. The former is quite small and is under peak
are tentative only. Nevertheless, with the heip of relative peak Cl in Figure 2, while the latter is peak C3 in Figure 2. Second,
heights for identifying the position of a compound in the GC's Kovats Indices may change slightly with time and if the same
on both columns, results are quite reliable and would be even values are to be used for longer than a few weeks, they should
more reliable on a less complex mixture. In fact most of the be checked by running one of the ester mixtures and the al-
identifications listed in Tables 4 and 5 are correct, as checked cohol mixture. If there is significant difference, the average
by GC/MS and comparison with mass spectra of the reference difference in the ester values can be used to correct all of the
compounds (14). other ester values {and probably the ketone values as well)
This experiment would take a single student quite a number since all will change to the same degree. As an example: over
of laboratory sessions to complete and is best used as an ex- a six-month period, the Kovats Indices of all the esters in
tended laboratory project which would include synthesis of Table 1 increased from 6 to 13 units (average 9) on the Apiezon
the standards, extraction of the samples, and identification column, and 36 to 44 unite (average 39) on the Carbowax
by GC. In addition, the student could trap sufficient of the column. During the same time interval, the alcohols increased
major components of banana to obtain MS and perhaps also an average of 40 units on both columns. These changes were
IR and NMR spectra, although the small quantities of extract probably due to gradual deterioration of the columns, since
obtained may preclude the latter two. However, mass spectra they were used continuously during the six months.
are easy to obtain by inserting a ahort length of glass tubing Acknowledgment
packed with a suitable absorbent in the GC exit (2) and then
putting the tube directly into the solid-liquid inlet port of the I thank the Universiti Kebangsaan Malaysia for financial
mass spectrometer. Some of the likely standard compounds support as grant No. 10/77.
also could be trapped and the mass spectra compared. Mass Literature Cited
spectra in the literature also could be consulted iJ5). (1) (a) Kovte, E., Advaa. Chromteogr., 1,2B9O965). (b) Sehomburg, a., and Dielmann,
G.. J. Ckromatagr- S«.. It, 151 (1973).
On the other hand, the time required to carry out this ex- (23 Tnranishi, B-, IssenbBrg, P., Hornstein, I., and Wick. E. Ln "Flavor Research: Principles
periment could be reduced considerably by reducing the most and Techniques," Marcd Dekker, Inc., New York, 1971, pp. 37, 333.
(3) fssenbeig. P., and Wick, E. L..J. Agrk. Food Chem... 11, % (1363).
time consuming step—the obtaining of the reference Kovats (4) (a) McReynotds, W, 0.T'GflsChjomat0graphicKe£entionI)a[a,''PreslonTechrtica!
Indices. The 52 reference compounds used here are probably Abstracts Co.. Evanatan. 1L, (966. On) Schupp, 0. E, Hi, and Lewis, J. S., Res./Devel.,
a minimal set for demonstration purposes (restriction to this 21(51,24(1970).
set can be justified on a priori grounds), so the time required 15) (a) Wick. E. L., Yaroanishi, T, Kobayashi, A., Valerauela, S,, end Issenberg,?•>J Ael"'c-
Food Chem., 17, 751 (1968). (b) Dupaignp. P., Fruits, 30, 783 119751.
can be reduced by having several students each do one or two (6) See, for example; Silvetetein R. M-, in Schulli, H. W.,I>ay. E. A,, and Ubbey, L. M.,
of the nine standard mixtures along with the banana extract {Editors),' 'Symposium on Foods: The Chemistry and Physiology of Flavors," AVI,
Westpon.CT, lW7,p.45G.
and the alkane mixture, using either or both of the GC col- (7) Kaken, .1 K., Advan. Chmmal^r., 14,367 (1976).
umns. AH reference data can then be pooled and each student (3) Baiulescu, G. K, and Hie, V. A., "Stationary Phases in Gas Cliromatogisphy," Pergamon,
can carry out his own analysis. Alternatively, the reference Oxford, 1975,
(9) (a) McHeynolds, W. 0., J Chromatagr. Sci, 8,685 (1970). (b) Zweig, G., and Sherma,
values listed in Table 1 or found in the literature can be used j., {Editors), "Handbook of Chromatugrnphy," Vni. 2, CSC Press, Cleveland, 197E,
(4). If Table 1 is used the columns must be Apiezon L and p. 270.
(10) Kovats. E.,tfeiu.Ckim. Ada, 41,1915 (1958).
Carbowax 1540. If the literature is used, appropriate columns (J1) van den Dool, H., and Krata. P. D.,J. Chrvmatogr., 11,463 (1963).
must be selected. Neither alternative is very satisfactory, (12) See, fore*8nip!e: Parliment, T. H.,andSear|»llino,R..t/- Agric. Food Chem., 2S, 97
because Kovats Indices will differ sufficiently between labo- (1977).
(13) Brodeiick, J..'., Flaneur Ind. ,Wi (1974).
ratories so that a peak in the banana extract may match a (14) Rasrausaen, P., Nordin, Azia. and Omar, Muhamat, Sains Malaysiana, in press.
reference peak to within ±15 or 20 Kovats Index Unite, and il5) (a) Stenhogen, E.. Abtaiiamsson, S., and McLaflerty, F. W.r "Begiauy of Mass Spectral
this difference.may lead to great confusion in assigning peaks Data," Wiley-Interscience, New York, 1974. (b> Cornu, A., and Maraot, R, "Com-
pilation of Mass Spectra! Data," 2nd ed., Heyden and Sun, Ltd.. London, 1975. (c)
of a mixture as complex as the banana extract. National Bureau of Standards, "EPA/NfH Meaa Spectral Data Boas," NBS National
Standard Reference Data Service publications no. 63 (1#78).
Royal Society Continuing Education Program

The Royal Society of Chemistry has organized a number of residential courses for practicing chemists who have a
knowledge of the field being covered but are seeking a deeper understand in g of the subject. Many courses are practically
based to acquaint participants with the latest developments and techniques. Thefollowingresidential schools are scheduler!
for 1984: March 26-30, Metailo-Organic Chemical Vapor Deposition; April 9-13, Inorganic Polymers; April 9-13, Equilibrium
and Nonecjuilibrium Aspects of Food Structure and Behavior; July 2-6, Organc-metalUe Reagents in Organic Synthesis;
July 16-20, Water Soluble Polymers: Chemistry and Application Technology; September 10-14, High Performance Liquid
Chroroatography. Further details are available from Miss L. Hart, Royal Society of Chemistry, 30 Russell Square, London
WC IB 5DT.

edited by
ROBERT REEVES
filtrate/ A re/idue/ Marlborough School

250 S. Rossmore Avenue
Los Angeles, CA 90004
Analysis of Alcohols
Brother Thomas McCullough

St. Edward's University Capillary
Austin, TX 7B704 taped to the
board
T h i s e x p e r i m e n t p r e s e n t s a n o v e l a p p r o a c h to i d e n t i f i c a t i o n
of u n k n o w n alcohols using e x p e r i m e n t a l m e a s u r e m e n t s of
boiling p o i n t a n d viscosity which are easily o b t a i n e d w i t h o u t
expensive e q u i p m e n t or i n s t r u m e n t a t i o n . S t u d e n t s or teachers
can carry o u t t h e necessary glass b e n d i n g . T h e s e p r o c e d u r e s
have been u s e d q u i t e successfully a t t h e a u t h o r ' s institution
for o v e r t w o d e c a d e s . Board
Purpose
In this experiment u n k n o w n alcohois are identified by
m e a s u r e m e n t of t h e i r b o i l i n g p o i n t s a n d viscosities.
Equipment
test tube thermometer
ring stand 6-mm soft glass tubng
two rings stri&g
wire gauze burner
clamp natural gas
boiling chip capillary viscometer The assembled capillary vlscomeler.
The capillary viscometer is prepared by pulling a section Sample Data

of 6-mm soft glass tubing; then a 30-cm length with a bore as
Flow Time,
uniform as possible is c u t A short right angle bend is made at Seconds
each end of the capillary which is then taped to a smali board {Time to Flow
having marks 15-20 cm apart inscribed on it. Both ends of the 15 cm in a
capillary should extend beyond the same side of the board (see Alcohol 8P, °C Capillary Tube}
figure).
Ethyl (95 %| 8.1
The Experiment Isopropyl 81-81,4 10.5
f-Butyl 79-80 19.6
1-Propanol 97.0 10.6
Boiling Point
2-Butanol 99.0 13.7
Place 1 ml of alcohol and a boiling chip in the test tube which is f-Pentyf 102 16.9
clamped to the ring stand. Clamp a ring and wire gauze immediately
below the test tube and place a second ring above tfle test tube. Tie
a string holding the thermometer to the ring so that the thermometer Results
dangles in the test tube with the bulb about 20 mm above the liquid. Results for a typical set of experiments are given in the ta-
The thermometer should not touch the sides of the test tube. bles.
Heat the bottom of the test tube (through the wire gauze) gently
so that the liquid boils slowly. When drops begin to fall from the bulb Pre-Laboratory Assignment
of the thermometer start to take temperature readings. Three or four
readings, 10 or 15 s apart and with an agreement of ±0.1, should give 1) What is meant by boiling point?
the boiling point of the alcohol. 2) What part of today's data can be found in a reference book?
3) What part of today's data will not be found in a handbook? Why
Viscosity not?
Introduce, by capiliary action, a liquid sample, 15- or 20-mra long, Post-Laboratory Assignment
into one open end of the viscometer and use gravity to force it to flow
back and forth between the two marks in order to wet the inside sur- 1) Draw the structures for the alcohols whose boiling points are
face. Move the. sample above the marks. Hold the board vertically. similar to yours.
Activate a stopwatch when the leading edge of the sample reaches the 2) Is your thermometer accurate? How can you tell if it is or not? If
closer mark, A. Terminate the timing when the same leading edge it is not accurate (to within one or two degrees) should it be thrown
passes the second mark, B. away?
3) How closely can your thermometer be read?
4) Is there any correlation between structures of the alcohols and the
New lectures and laboratory experiments and directions In teaching flow times?
chemistry through Hie use ot the laboratory are provided In this feature.
Experiments will be fully detailed and wflt be field tested before they are References
published. Contributions should be sent to the feature editor. Boiling points of all common alcohols can be found in
"Lange's Handbook of Chemistry," "CRC Handbook of

Chemistry and Physics," or any textbook of organic chem- 4) The flame and test tube should be shielded from drafts and breezes
istry. during the BP determination.
5) Capillary tubing must be used, never 1,5,6 or larger ID (mm). The
Special Notes capillary is formed from 5 or 6 mm soflgiass tubing and a very hot
1) The glassware, including the thermometer, must be dry, as water flame by gentle pulling.
and most alcohols form azeotropes that lower boiling poinla by 6} In viscosity measurements, room temperature can be an important
I0-15°C. Is the alcohol being used free from water? variable as a difference of several degrees Celsius wiM cause a sig-
2) Temperatures can be taken only when drops of liquid are con- nificant change in the flow time. A more obvious variable is the
densing and falling from the bulh of the thermometer. If the al- angle at which the hoard and capillary are maintained during the
cohol has been boiled away, a lowering of the temperature will be flow. The fastest time wiii be obtained when the board is heid
observed by your students. Increasing the amount of sample from vertically. Smaller angles wili increase the flow time and increase
1 to 2 ml (or even more) should help eliminate this difficulty. the sensitivity of the procedure.
3) On the other hand, higher boiling points than warranted can be 1) The best way to standardize the viscometer is to carry out the
obtained if the sides of the test tube are heated too much. The procedure using known alcohols. The actual lenjjth of the liquid
vapors become superheated and, rather than condense on the bulb, sample in the capillary should be the same for all alcohols, knowns
heat it above the true boiling point. A low, low flame and a wire and unknowns alike.
gauze usually prevent this phenomenon.
An Addendum on Measuring the Entropy

of Mixing off a Two-ion System
J. D. Puffer
National University of Lesotho, Roma, Lesotho, South Africa
As Selley points out 1 , concentration cells provide an accu- a g a i n s t ni g i v e s a n o n l i n e a r c u r v e . T h i s g r a p h i s t h e n e x -

rate, direct method for measuring the entropy of mixing of a t r a p o l a t e d t o t h e origin t o find t h e m a x i m u m a m o u n t of
two ion system. The purpose of this note is to develop a rela- e l e c t r i c a l w o r k . S u c h a n e x t r a p o l a t i o n g i v e s r i s e t o some u n -
tively simple data handling procedure which has the effect of c e r t a i n t y . T h e r e is n o n e e d for t h i s a m b i g u i t y . W i t h i n S e l l e y ' s
cutting experimental effort in half and making it considerably a s s u m p t i o n s , a t h e o r e t i c a l p l o t o f l(ni) v e r s u s \tnln[n±/(l —
easier for students to obtain good results. « i ) j -1- l n ( l - n-i)} w i l l g i v e a s t r a i g h t l i n e w i t h s l o p e 2RT a n d
Observe 1 that a plot of the integral intercept mmax.
A p l o t w h i c h i s supposed t o be a straight line is easier t o
(ill) = I U) e x t r a p o l a t e a n d , i n genera!, will b e less p r o n e t o e x p e r i m e n t a l
i n a c c u r a c i e s . I n a d d i t i o n , s t u d e n t s n e e d o n l y find t h e p o t e n t i a l
$ a t four values of n , ( T a b l e 1) t o achieve t h e s a m e results a s
1
Seiley, N. J., J. CHEM. EOUC., 49, 212 (1972). reported1. F o r example, when t h e experimental integrals Iitii)
{ T a b l e 2 ) , e v a l u a t e d b y " c o u n t i n g s q u a r e s " o n a g r a p h of 6
v e r s u s rij, w e r e p l o t t e d i n t h e s u g g e s t e d m a n n e r , wmiX w a s
found t o b e 3250 J rnol"1. T h i s w a s 6.9% lower t h a n » i m i
theoretical { 3 4 9 0 J mol"1)-—well w i t h i n t h e r a n g e of Selley's
values1.
Table 1. Celt Potentials for 0.100 M Hexacyanoferrates (II) and

(HI) Mixtures
Observed cell Seltey's observed cell
n,/mo! potential/abs V potential/afis V
0.0500 0.145 0.148

0.100 0.10S 0.104
0.200 0.069 0.073
0.300 0.034 0.046 a
H
Tola! conoanliation of the cslt was 0.02S w.
Table 2. Experimentally Estimated a Integra) Values of f(n 1 )
i>/(J mor'i
0.0500 2280
0.100 1670
0.200 818
0.300 324
Variation of maximum eiecirlcal work as a (unction of )n ( ln[n,/(1 — n,)] +
hid - " , ) ] . * Counting gfjuaces ona graph at & versus n 3 .

Performance Characterization of an Instrument
Eric D. Sallrt
McGIH University, Montreal, P.O., Canada H3A 2K6
There is a tendency among certain students to have un- Symbols and Terms
questioning faith in instrumentation. This is particularly true
Symbol Definition
of modern instrumentation with digital readout These stu-
dents report data to a phenomenal number of significant fig- d darK signal (no light falling on detector}
ures while expecting a corresponding accuracy. An apprecia- m slope of the analytical calibration curve in units
tion of the power of modern instrumentation must be tem- of volts/concentration units
pered with an awareness of its limitations. Students should n number of measurements
apply to instrumentation the same statistical awareness that s analytical signal (£ a = £AEF) used in figures
is so conveniently and commonly applied t o classical tech- I f statistic value from Student's tTest
niques. Propagation of error techniques can be used to pin- S background
C concentration
point instrumental limitations and breakdowns as well as they
G* the concentcation at the limit of detection
can be used to demonstrate the capabilities and ultimate
E voNage
limitations of volumetric and gravimetric methods. With this noise (RMSi
N,z
in mind, an experiment has been developed for use in our S signal
second analytical chemistry course. We have used an atomic AFE analyte flame emission
emission apparatus as the experimental vehicle; however, the AS tola! analytical emission signal
techniques are generally applicable. 6A biank aspiration
8E total blank emission signal
Alt instruments have limitations over their entire perfor- BFE blank flame emission
mance range. The experiment to be discussed introduces the
student to the terms "detection limit," "signal-to-noise ratio,"
"dynamic range" and "linear dynamic range" as well as pro-
viding the student with a step-by-step procedure for the de-
termination of experimental noise sources in the instrumental time recording their data a n d m a yintroduce unnecessary long
operating ranges. Flame atomic emission (FAE) was used due t e r m drift {low-frequency noise) into their e x p e r i m e n t . T i m e
to the simplicity of the apparatus and data handling. c o n s t a n t s t h a t a r e t o o s m a l l will allow u n n e c e s s a r y n o i s e
through t h e electronic bandpass.
Experimental Procedures and Equipment S t u d e n t s a r e n o wr e a d y t o begin d e t e r m i n a t i o n of instru-
A FAE apparatus with a digital readout is most convenient m e n t a l noises. All noises a r e d e t e r m i n e d b y acquiring 10
for this experiment. A meter "needle" type of readout usually readings a t 5 T C or greater intervals a n d taking t h e standard
cannot provide the readout resolution required to quantize d e v i a t i o n , z, of t h o s e v a l u e s . W h i l e i t m i g h t b e a r g u e d t h a t 3 2
the experimental noise. A strip chart recorder is somewhat o r s o m e i n t e r m e d i a t e v a l u e is m o r e a p p r o p r i a t e , t h e inclusion
better if it has multiple ranges; however, we have found that of m o r e v a l u e s m a yi n t r o d u c e l o w - f r e q u e n c y n o i s e c o n t r i b u -
an inexpensive 3%-digit digital multimeter (DMM) is excel- t i o n s a s well a s s t u d e n t fatigue. F o r p u r p o s e s of later reference
lent, because it usually provides voltage ranges so that a w e w i l !refer t o t h e following p o r t i o n s of t h e e x p e r i m e n t a s
change in amplifier settings is unnecessary throughout the steps.
entire experiment. We have found it convenient to use calcium
<Ca) as an analyte for this experiment. It can be seen visually Step 1.
in the flame, has both elemental and molecular bands, is The first noise to be determined is the "dark" noise, z&. E$
subject to the classic phosphate chemical interference, and is measured by blocking the entrance to the spectrometer so
provides good performance. that no light can pass in. Ed can be broken down further into
The student's first task is to adjust the spectrophotometer other components, many of which can be predicted from
so that the 422.7-nm Ca atomic emission line is observed, The fundamental principles and the reader is encouraged to ex-
wavelength dial usually does not readout the wavelength amine the excellent series of papers by Ingle and Bower {2-7);
precisely thus providing a convenient first contact with reality. however, this is not necessary at this educational level and
While aspirating a high concentration (around 10* ppm) of would not necessarily even be implemented by a researcher
Ca the student must set the gain of the instrument to provide interested in the evaluation of his or her apparatus. The dark
a readout of 5.0 V on the DMM with appropriate initial op- noise, ad. is the minimum noise that can appear in the appa-
erating parameters {gas flows, slit, etc.). This is the highest ratus.
concentration that will be aspirated and the gain must be
adjusted on our system to avoid saturation of our external Step 2.
operational amplifiers. The student must now optimize the spectrometer slit width
The student is expected to determine the electronic time and burner position. This is carried out by optimizing the
constant (1) of the entire apparatus by blocking a high-in- signal-to-background (S/B) ratio. This is a common and
tensity signal and then quickly removing the block. Students sometimes fallacious technique popular in emission spec-
use the guideline that 99% of the final value will be reached troscopy. The S/B is calculated by
in 5 time constants (TC's). The students are then encouraged
to use the general rule that digital observations should be S/B =
made every 5 TC or farther apart BO that the values will be Em
statistically independent. I t is best if the time constant of the and EAFK = # A S ~ -EBE where SAFE is the desired voltage such
system is from 0.1 to 1 s. This range normally will be available that E A P E = mC, E\s is the total voltage measured when as-
on both modern and old equipment. If the time constant ex- pirating a sample solution, and E B E is the voltage of the blank
ceeds 1 s then the students will spend inordinate amounts of solution. The table contains a list of terms and symbols.

Step 3.
- 7
The students are then required to make a calibration curve
over four orders of magnitude. Solution concentrations range
from 10° to 10* ppm Ca and there is one solution per order of 240
magnitude. E^s and IS BE a r e each recorded 10 times. T h e
blank must be recorded so as to ensure that no memory effect
is introduced by the use of high analyte concentrations. This ZOO •
calibration curve is called the gross calibration curve and ex-
tends well beyond the normal operating regions of FAE with
Ca. 160
z
10
Step 4.
120 . -3 w
Another calibration curve called the fine calibration curve
is recorded in what is normally the linear region, 1 to 20 ppm.
To save time, only 5 readings each of £ A S a n ( * ^ ' B E are made BO .
for the fine calibration curve. Students are given an unknown
solution which is to be run immediately after the fine cali-
bration curve. T h e concentration of the unknown should be 40 •
between 5 and 20 ppm in our system, because t h e detection
limit is around 0.1 ppm.
Step 5.
The final solutions analyzed are 5 ppm Ca, 5 ppm Ca with Los cone Ca (ppm)
excess phosphate and 5 ppm Ca with excess phosphate and Figure 1. Typical student resutts plotted1 as S/N versus log C (curve Aland EA
EDTA. versus log C (curve B).
Experimental Report
Before writing up the experiment, students are instructed
to scrutinize carefully a set of notes on signal-to-noise-ratio
theory provided by J. D. Ingle, Jr. of the Chemistry Depart-
ment of Oregon State University (8). From these notes,
propagation of error theory (available in their text (9)) and
lecture notes it is straightforward for them to derive the fol-
lowing expressions.
(2). /
(4)
(5)
The information provided in Steps 1 and 3 provide the basis
for determination of the variance of the other major noise
contributors in the system. Using eqns. (1} and (2) as building
t
blocks it is easy to estimate the magnitude of the blank flame
emission noise, 2BFE> and the noise due to the flame emission
of the analyte, SAFE- The student is asked to carry out several
graphing and writing exercises. We will discuss the more im-
portant of these.
Students are asked to plot the following data and label the
curves A, B, C, D, and E, respectively. Log cone
S/N versus log C Figure 2. Typical plot ot student results tor log Et&e versus log C {discussed as
pkit C in text).
E/,FE versus log C
log EAFE versus log C Exercise 2
£APE versus C
Plots A and B aie made <m the same graph. A typical graph is pre-
£ A re versus C for Step 3 data sented in Figure 1. Clearly the intensity of tiie radiation as measured
by J&AKE (° r by S/B) is constantly increasing; however, the actual
performance of the instrument, aa measured correctly by S/N, ia not
improving (Al) or degrading (A2). This is an important point; "bigger"
Exercise 1 is not necessaniy "better." Indeed, in curve A it can be seen that under
The student is asked what the optimal height and slit settings were certain circumstances the S/N ratio degenerates at higher concen-
based on his data from Step 2. The important point here is that the trations. This is due, in our case, to clogging of the nebulizer, a com-
students used S/B, which is very easy to determine, rather than the mon malfunction with high sait solutions.
more demanding S/N ratio. Assuming that the noise in the blank, ;BE> Plots C and D demonstrate the convenience of logarithmic plots
is the dominant noise is an analysis, this is the correct procedure; for data that covers orders of magnitude. It becomes quite clear to tthe
however, usually this is the case only when data is collected near the students that plot D is very difficult to use in any but the highest
detection limit. When higher intensities are observed, other noise concentration range. The students are instructed U> examine closely
sources become dominant as S » B. Under these conditions the op- Plot C (Fig. 2). It is a 3og/log plot of a relationship wliich should, ide-
timization procedure may not be valid. ally, be linear and follow the general Corcnuia

to estimate the value of their unknown solution, provide confidence
limits and detection limits. Usually the slopes and calculated unknown
then concentrations are significantly different using the two data sets. It
then becomes apparent to the student that the data derived from the
log JEAFE = log m + iog C information collected in Step 3 is far more useful due to the close
Plot C should then have a siope of 1.00 in the region where this rela- bracketing of the analyte signal by standards. The regression coeffi-
tionship holds and an intercept of log m. Students are required to do cient of the data from Plot D may be very dose to 1.00; however, this
a linear least-squares regression analysis of the data using the pro- is due in large part to the fact that the linear regression can be very
cedures described in reference (10). deceptive when used with data values which extend over orders of
magnitude. This serves as a valuable warning against mathematical
Exercise 3 "black bos" solutions.
The students have sufficient data provided in Steps 1 and 3 to
calculate the magnitudes of the various noises in the system. This Exercise 5
information can be combined with the graphical data provided in Plot Step 5 is a demonstration of a classical chemical (rather than
A to provide an estimate of the type of noise and what might be done spectral) interference. EAFE with the phosphate solution is signifi-
to improve the experiment. If the S/N improves directly with increase cantly lower (often 40%) than that of the original 5 ppm Ca solution.
in S, then the system is "background noise limited." This should be This is due to the creation of CastPOJs, a very stable compound which
confirmed by the student's calculated values of the magnitudes of the is only partially decomposed in an air-acetylene flame of the type used
various noises. If tjbe S/N ratio improves as (S)1'8 then the system may in this laboratory. The EDTA/Ca/P(>4 solution JEAFE is usually 5 to
be "shot noise limited," and one is then governed by Poisson counting 10% higher than the pure Ca solution. Students have been instructed
statistics of the type commonly encountered in radiochemical photon that EDTA selectively complexes with the Ca and yet the complex
counting experiments. If the S/N is independent of S, then one is is easily broken down in the flame. White this would justify a return
usually "flicker noise limited." to the original signal, it does not explain the significant increase in
The discovery of the limiting noise source is critical to system im- signal. The students are asked to explain any anomalies in their data,
provement. Close to the detection limit one is usuaily background and how they would do an analysis for Ca which may be in a phosphate
noise limited and anything which will increase £AFE without in- environment.
creasing EBJJ wiii usually result in a direct improvement in perfor- There are two reasonable explanations for the increase in JBAFE in
mance. This could be an increase in emission caused by a change of the final solution. The EDTA may act as a fuel, thereby increasing
fuels or a more efficient nebuiization system. The total blank emission the flame temperature, or the EDTA may be emitting as it is'bumed
signal noiBe (ZBB) is the major source of noise, and anything which will in the fiame. The good student will suggest one or both of these as
lower this noise will also result in an improvement in the S/N ratio. possible solutions and will offer a simple experiment which might
IE z& is significant, then it is appropriate for the students to suggest indicate which is the source of deviation. An EDTA solution could be
that an improvement in the electronics or detector will enhance the aspirated after a water blank. If the intensity increased, then it would
performance in this concentration region. In the second concentration be due to EDTA combustion. An alternative would be to shift slightly
region, the performance improvement expected would be proportional off the Ca line. If the signal is due to EDTA combustion, it is most
to the square root of the S increase if one were shot noise limited; likely a broad band molecular emission or stray light (from the Na in
however, Plot A invariably goes through a concentration region where the Na-EDTA salt) and a shift to a slightly different wavelength
the slope would indicate a shot noise limited condition. This is to be should not reduce the signal back to the level of a water blank. In ei-
expected as the conditions are changing toward a slope of 0 as a flicker ther case, the student should suggest the use of either the standard
noise limited situation is approached. An additional experiment would addition technique or standards and blanks with EDTA at the same
have to be performed to determine whether the instrument were in- concentration level for analyses of this type.
deed shot noise limited in this concentration region. A reduction of
intensity can be achieved by partially blocking the beam from the
flame or, preferably, the insertion of neutral density filters. A re- Conclusion
duction of intensity by a factor of 4 would cause a degradation in the Using equipment available in many teaching labs, it is
S/N by a factor of 2. The students have not done this, because they possible to provide students with a simplified but powerful
always process their data after the experiment They cannot then state introduction to Signal-to-Noise-Ratio Theory. The techniques
emphatically that they are shot noise limited in this situation, but are generally applicable and can be used for instrumental
simply, that the slope of the S/N curve may imply that this is true. In
the final case, the S/N cannot be improved by increasing S but must design and modification as well as day to day diagnostic per-
be improved by decreasing N. One must then examine the compo- formance analysis. The experiment described above provides
nents otN. In the flicker noise dominated region the primary source an insight into some of the conveniences of logarithmic data
of noise is z AFE and only changes which improve the stability of £AFE presentation as well as some of the pitfalls. Basic principles
will have an enhancing effect. Stabilization of the flame by the use of good data handling are encouraged throughout the exper-
of sheathing or improvements in nebuJker design are reasonable iment as they should be in all laboratories regardless of
improvements to suggest. equipment or environment.
Plot A provides a final benefit in that it demonstrates tile some-
times complex nature of reality. In the middle portion of the S/N Literature Cited
curve, it is not trivial to state exactly what the situation is. Several (1) Malntsladt, Hr Vr, Bake. Cr G-. and Crouch, S, R,, "Electronics and Instrumentation
noise sources may be significant and more experiments would be for Scientists,'*The Benjami^/Cummin^s Publishing Co., Ine., 198I,P)>- 142-Wh.
necessary for the students to state that the experimental precision (2) Ingle, Jr., J. 0., Anal. Chela., 16,2161 (1974).
was shot noise limited. While this might sound initially like "hand (3) Sower, N. W., slid Ingle, Jr., J. D., Anal. Chem., 49,574 (1977).
(4) Sower, N. W., and Ingle. Jr., J. I>.. Anal Ckem., 48, BS6 (1976).
waving," instrumental evaluation can be a complex iterative pro- (5) Bower, N. W., and Ingle, Jr., J.ft..Anal. Chein., SO. 544 (1976).
(6) Bower. N. W.. and Ingle, Jr., ,1.1)., Anal. Ckem., 51.7a (1979).
(7) Bower, N. W., PhD Thesis, Oregon State University, Corvallis, Oregon, 197B.
{&) Ingle,Jr., J.D., "Notes on Basics of Spectrometde Measurements," i$>77,
Exerclse 4 (9) Skoug, Dr A., anrf West, D, M-, "Principles of Instrument Analysis," 2ndfid..Sounders
Plot E, the fine calibration curve, is plotted using linear axes. The College, 198ft.
students must apply linear regression techniques (3) to this data. They (10) Peters, 15. C, Hayea. J. M., and Hieftje. G., "Chemical Separations and Measure-
ment—Theory and Practice of Analytical Chemistry," W.B. Sawidera Co., 1974,
are asked to use the linear regression data from both Plots D and E Chapter 2.

/omething neuu JOSEPH S. SCHMUCKLER
Edited by:
Chairman of Science Education

•rest
from the part Temple University

34S Hitter Halt
Philadelphia, PA 19122
Gas Laws and Gas Behavior S o m e of u s h a v e h a d s t u d e n t s in o u r classes w h o s e fortes w e r e n o t

i n c h e m i s t r y . T h e s e " h a r d s " w e r e t h e s t u d e n t s w h o a d d e d o t h e r di-
m e n s i o n s to t h e ciass. I recall t h e delightful s u r p r i s e I h a d on r e a d i n g
Gas Laws and Syringes Revisited: Boyle's Law
o n e s t u d e n t ' s l a b r e p o r t s w r i t t e n in t h e s t y l e of C o l e r i d g e ' s " K u b l a
In the December, 1980 issue of THIS J O U R N A L , p. 885, the K h a n , " or Lord Macauly, or Horatius.
work of Derek A. Davenport involving the use of the hypo- C a n y o u i m a g i n e y o u r s e l f i n t r o d u c i n g A v o g a d r o ' s n u m b e r in t h e
dermic syringe to study gaseous behavior was reviewed. His s t y l e of a S h a k e s p e a r e a n t h e s b i a n ? N o ? T r y i t . B o t h y o u a n d y o u r
work and similar demonstrations and experiments developed classes m i g h t enjoy it.
by others are wonderfui sources for fun with gases in the
" N e w Device for D e t e r m i n i n g Molecular W e i g h t of a G a s , "
classroom. Add to this collection Davenport's syringe exper-
H o w a r d N e c h a m k i n . The Science Teacher, 35. 47-48
iments of Boyle's Law that appeared in "Tested Demonstra- (April 1968).
tions," J. CHEM. E D U C , 56, p. 322 (May 1979). T h e experi-
ments are easy t o do, and typical data fall obtained in 5 min- W i t h today's d i s p o s a b l e b u t a n e l i g h t e r s , t h i s e x p e r i m e n t i s e v e n
utes) are given. easier t o d o t h a n it was using t h e m e t h o d suggested by
Nechamkin.
Gauge Pressure and Absolute Pressure " R e a c t i o n K i n e t i c s " B r i a n M o a r , The Science Teacher, 44,
On the same page as the Boyle's Law experiment mentioned 48 ( M a y 1977).
above, Davenport describes some interesting (and fun) gas T h i s is a " m a c r o - d e m o n s t r a t i o n " of k i n e t i c m o l e c u l a r t h e o r y in-
behavior using a standard tire pressure gauge and a side-arm volving s t u d e n t s as m o l e c u l e s i n a confined v o l u m e ( a r e a ) .
test tube. Various pressure readings are made which show,
"The sum of the gauge pressure and the residual pressure (in " K i n e t i c s T e a c h i n g M o d e l , " W i i l i a r a W . S a d l e r , The Science
the same units) is sensibly constant" "When the test tube haa Teacher, 38, 41 ( N o v e m b e r 1971).
been completely evacuated, the gauge reading will be found I n p r e v i o u s c o l u m n s w e h a v e cited a r t i c l e s on p h y s i c a l m o d e l s to
to have increased by an amount equal to the atmospheric d e m o n s t r a t e t h e effects of m o l e c u l a r a c t i v i t y . S a d l e r d e s c r i b e s a
pressure." simple inexpensive device t h a t h e h a s c o n s t r u c t e d from c o m m o n i t e m s
found in m o s t h i g h schools a n d w h i c h c a n b e u s e d w i t h a n o v e r h e a d
Who's Law? p r o j e c t o r . I t d e m o n s t r a t e s r a n d o m m o t i o n a n d t r a n s f e r of e n e r g y a s
s p h e r e s " t h e size of b a s k e t b a l l s " collide o n t h e p r o j e c t i o n screen. I t
"Boyle's/Hooke's/Towneley and Power's/Mariotte's Law," s h o w s g a s e o u s diffusion t h r o u g h a m e m b r a n e , a n d effects of tem-
Robert M. Hawthorne, Jr., J. C H E M E D U C , 11, p . 741 perature changes a n d concentration changes.
(November 1979).
"Chemistry, like all the sciences, is filled with constants, principles, " A n a l y s i s of t h e U p p e r A t m o s p h e r e , " W i l l i a m B . J e n s e n , J .
and mathematical laws, many of which have someone's name attached C H E M . E D U C , 5 4 , 7 4 ( F e b r u a r y 1977).
to them." The student of chemistry, knowing no hetter, is apt to as- I h a v e r e p r o d u c e d t h i s s h o r t article t h a t c a n b e u s e d a s a n a n e c d o t e
sume that t i e person named is the person who actually produced the i n y o u r classes. Y o u will h a v e t o g o t o t h e j o u r n a l for t h e a c t u a l illus-
number or formula that's on the page hef'ore him, an assumption often tration.
far from the truth. Probably no great harm is done in this way, as the " T h e illustration shows t h e balloon ascent m a d e o n August 20,
substance of the law is more important than its provenance. None- 1804, b y t h e F r e n c h c h e m i s t , G a y - L u s s a c , a n d t h e F r e n c h p h y s i -
theless, there are some interesting anecdotes connected with the cist, B i o t , t o t e s t , a m o n g o t h e r t h i n g s , a n e a r l i e r R u s s i a n c l a i m
formulation of laws, or the determination of constants, that can be t h a t t h e e a r t h ' s m a g n e t i c field d e c r e a s e d w i t h a l t i t u d e . T h e i r r e -
used to enliven classroom presentations. In some cases the background s u l t s i n d i c a t e d t h a t it w a s c o n s t a n t . T h e y aiso t e s t e d t h e a t m o -
of these stories can. lead to a deeper understanding of the principle s p h e r e ' s c h e m i c a l c o m p o s i t i o n a s a f u n c t i o n of h e i g h t a n d found
itself. i t to b e u n i f o r m . G a y - L u s s a c is a t t h e left w i t h t h e t o p h a t , glass-
A case in point is the gas pressure-volume relationship that we know es, a n d a i r s a m p l e b o t t l e .
as Boyle's Law, which haa a very tangled origin indeed. " G a y - L u a s a c l a t e r m a d e a s e c o n d flight a l o n e , r e a c h i n g a n a l t i -
It is from articles such as this one that the "spice" of the story of t u d e of 7016 m e t e r s . I n o r d e r t o gain h e i g h t h e t h r e w several
chemistry comes. The significance of the priority of publication and i t e m s o u t of t h e balloon, i n c l u d i n g t h e o l d w h i t e k i t c h e n c h a i r h e
of keeping a lab hook is stressed by the author, read the entire article was s i t t i n g o n . I t l a n d e d n e a r a p e a s a n t giri w h o w a s m i n d i n g
to get the rest of the story. s h e e p . T h e local vilfagers a n d t h e p r i e s t , after m u c h d e b a t e , final-
ly d e c i d e d t h e i n c i d e n t w a s a m i r a c l e . T h e y r e m a i n e d , however,
"The Fable: Iâws are Mature Theories," Jack K. Homer and p u z z l e d as t o w h y G o d o w n e d s u c h s h a b b y f u r n i t u r e . "
Peter A. Rubba, The Science Teacher, 46, 31 (February
1979). " I l l u s t r a t i n g P r i n c i p l e s of K i n e t i c T h e o r y of G a s e s , " R o b e r t
C. P l u m b , J . C H E M . E D U C , 47, 175 ( M a r c h 1970), 4 8 ,
"At the heart of this fable is a fatal assumption about the rela-
tionship between laws and related theories: namely, that theories 1 1 9 - 1 2 0 ( F e b r u a r y 1971), a n d 5 0 , 5 5 9 (August, 1973).
mature into laws by constant testing and confirmation." The authors Sea-Lab Experiment
present three familiar examples that show the fallacy of this common,
naive misconception. Boyle's and Charles'laws are used as one of the "The ocean floor is one of our unexplored geographical frontiers."
examples showing "... that the relationship between theories and laws To extend exploration of the ocean, scientists and engineers are de-
is an explanatory one—not, as the fable insists, a maturational one." veloping hardware and procedures to permit people to iive for days
One reading of this article and many of you wiil change your teaching, or weeks in chambers on the ocean floor. In these chambers oxygen
especially for your beginning chemistry classes. and helium are used as an atmosphere. A strange physiological effect
is noted when a person lives in an atmosphere in which nitrogen has
"On Avogadro's Number: as Shakespeare's Prospero might been replaced by helium. If the temperature in the chamber is a
write," S. R. Scholes, J. CHEM. EDUC., 42, 126 (March normal, comfortable 70DP such as is used in buiJdiags on the earth's
1965). surface, the aijuanauts feel decidedly chilly. Why?

Space Vehicle Reentry and Thermal Effects of High Winds vationist, then keeping fish alive and healthy La of concern to you. You
will see in this exemplum how a simple chemical process is a common
"If a person is exposed to a cold wind, he loses body heat more cause of fish kills; knowing the chemistry leads directly to solutions
rapidly than he does under circumstances where heat loss is controlled to the problem.
by diffusion—it may even lead to a tragedy such as on Mt. Washing-
ton in New Hampshire when two persons "froze to death" on Ju!y 20, In each of the above examples of chemical principles you
1959, even though the temperature did not go below 38°F, but the should read the articles in their entirety in order to answer the
wind was as high as 65 mph. questions posed by the authors.
"Why, then, does a space vehicle, in passing at high speed through
the atmosphere, tend to get hotter thaa the gas? Why doesn't it get A Lab Experiment
cooled to tiie temperature of the atmosphere? At what wind velocity
wouid a person standing on a high mountain tend to heat up instead "Does Pressure of a Gas Depend on the Number of Mole-
of cooling off, and why in terms of molecular behavior would this
occur?" cules?" James V. DeRose, Chemistry, 38, 26-28 (June
1965).
Gas-Bubble Disease of Fish
"The problem of counting molecules in a gas sample would seem
"A bright-eyed child brings some goldfish and a fishbowl h o m e - to be insurmountable. However, it is not necessary actually to count
conscientiously feeds and changes the water—the fish sicken and die." molecules to conduct an investigation which provides data relative
A river is dammed, heavy runoff of water occurs, and the fxsh popu- to this question." DeRose gives a detailed introduction and procedure
lation downstream—e.g., salmon or trout^—suffers great losses. If you to this "Lab Bench" experiment. He presents expected data and a
own a goldfish bow! or home aquarium or are a fisherman or conser- series of good questions that will challenge the students to think.
The Density and Apparent Molecular Weight of Air

A Simple Introductory Experiment
Ario D. Harris
California Slate College, San Bernardino, San Bernardino, CA 92407
Fundamental to a study of chemistry is ais understanding RUBBER TUBING
AND PINCH CLAMP
of both extensive and intensive properties. Most inroductory
courses utilize mass and volume as examples of the former.
The ratio of mass to volume equalling density is most often ONE HOLE RUBBER STOPPER
used as an example of the latter. These concepts are quite
easily defined and described in lecture materials, hence they 250 ml ERLENMEYER FLASK
require little effort on the part of the student for under-
standing.
800 ml BEAKER
Generally speaking, the first experiment done in most in-
troductory laboratory courses deals with physical measure-
ments. The aforementioned concepts and definitions lend
themselves readily to simple measurements to confirm them
as basic tenets of chemical science. A variety of measurements
of mass and volume are used to demonstrate the density of BUNSEN BURNER
solids and liquids, both pure and solutions. These can be found
published in many commercially available laboratory manu-
als. Some institutions use modular units or use hand-out ex-
periments of their own.
Few, if any, programs incorporate a measurement of the
density of a gas at this early stage in a laboratory sequence.
Possibly there is the idea of a need to include a discussion of APPARATUS FOR DETERMINING THE DENSITY
AND APPARENT MOLECULAR WEIGHT OF AIR
gas laws which, of course, comes later in most courses. In fact,
many experimental programs use the classical Dumas method Apparatus used so determine the density and apparent molecular weight of
later in the course to determine the molecular weight of a
volatile liquid or even a gas itself.
flush w i t h t h e b o t t o m a n d will n o t e x t e n d i n t o t h e flask. T h e r u b b e r
The experiment described herein can be used by beginning t u b i n g slips over t h e extending e n d . T h e stopper is pushed very tightly
students without the mention of gas laws. It relys solely on i n t o t h e m o u t h of t h e E r l e t i m e y e r flask. T h e p i n c h c l a m p is placed
mass, volume, and temperature. The variables are mass and snugly a b o u t t h e r u b b e r t u b i n g b u t n o t lightly closed, so t h a t air can
temperature while the volume of the system remains constant easily e s c a p e a t t h e higher t e m p e r a t u r e . T h i s a p p a r a t u s is weighed
Although this experiment uses the ideal gas iaw in deriving to four d e c i m a l piaces a t r o o m t e m p e r a t u r e . T h e t e m p e r a t u r e m u s t
the working equation, students need not be burdened with it. b e m e a s u r e d to within 0.1°C.
It is sufficient to instruct the student in simple concepts which T h e a p p a r a t u s is t h e n c l a m p e d in s u c h a way t h a t a s m u c h of t h e
are presented at the end of the derivation. E r l e n m e y e r flask is inside t h e large b e a k e r a s is possible (see figure).
T h e b e a k e r is filied w i t h w a t e r t o t h e very top allowing oniy e n o u g h
r o o m for b u b b l i n g d u e to r a p i d boiling. T h e w a t e r is b r o u g h t to a boil
Apparatus (as shown in the figure) a n d allowed to boil vigorously for 10 tnin. T h e t e m p e r a t u r e of t h e
250-ml Erlenmeyer flask w a t e r is r e c o r d e d t o within O . P C .
1-hole rubber stopper W h i l e t h e w a t e r is still boiling, t h e r u b b e r t u b i n g is folded over a n d
1 short piece of glass tubing (about 10 cm long) t h e p i n c h c l a m p is c l a m p e d very tightjy s h u t a r o u n d it. T h e d o s e d
1 short piece of rubber tubing (about 8 cm long) system is quickiy removed from t h e boiling water, placed on a folded
1 pinch damp p a p e r towel, a n d d r i e d t h o r o u g h i y w i t h a s e c o n d p a p e r towel. After
1 800-1000-ml beaker c o m p l e t e d r y i n g , t h e closed s y s t e m is reweighed. E x p e r i e n c e h a s
s h o w n t h a t i t n e e d n o t h e cooled t o rocini t e m p e r a t u r e t o d o t h i s . In
Experimental Procedure fact, a l e n g t h y cooling period m a y aliow s o m e a i r to seep into t h e
The glass tubing must go through the rubber stopper so that it is system.

Remove the stopper and fill the flask with water. Push the stopper Discussion
in, forcing water up to fill the glass and rubber tubing. Pour this into The result obtained using this simple experimental proce-
a graduate cylinder to measure the total volume of the system. dure was 12.66 X 10~4 g/ml. The accepted value 1 is 12.05 X
10~ 4 g/ml, The percent error is 5%. For this simple approach
Derivation of the Working Equation this is a reasonable error since no case was taken to assure a
The experiment is performed using two temperatures. The good seal of the closed system, the volume was estimated using
lower will be designated by a subscript (1) while the higher will a very large graduated cylinder, and the thermometers were
be designated by the subscript (2). The derivation is based not calibrated.
upon the ideal gas equation in the form The procedure gives an answer well within an acceptable
range of error for an introductory experiment. It allows the
student to determine the density of air without relying on the
gas law. The student need only realize that as the system is
for low temperature heated, the gas expands and some of it is lost. This physical
fact is familiar to most students.
Using this experiment in conjunction with the determina-
for high temperature tion of densities of solids and liquids gives students a better
understanding of changes in intensive properties inherent in
changes of physical phase.
Under the conditions of the experiment the molecular weight Further Considerations
of air is unknown. However, the homogeneous concentrations The experiment as presented here is directed toward the
of the mixture present will remain the same, and for this incoming first-year student. It is designed to be part of an
reason the apparent molecular weight wiil remain constant. experiment concerning physical measurements of mass, vol-
Gathering together those parameters which remain constant ume, and density. A student will be able to understand it with
in the above equations is shown as follows. no reference being made to gas laws or the ideal gas equa-
tion.
Pi Vt M.W.
The essential characteristic of the experiment is a combi-
nation of the Avogadro law and the Dumas method of deter-
P2V2M.W. mining the molecular weight of a gas. The experiment could
R therefore be used later in an introductory course when gas iaws
are being studied. Since the experiment presents a simple
The left sides of both equations are equal, hence combining method of finding the mass of a gas in a discrete volume,
them yields: measuring the prevailing atmospheric pressure will allow use
giTi = g2T'i of the ideal gas law
but #2 — {g\ — x) where* is the mass of air driven out at the
U W
higher temperature. Substitution into the above equation - --*PV-V t* ~ d P
yields to obtain the apparent molecular weight of air.
The concept of an apparent molecular weight of a mixture
of gases is useful and a brief discussion can be found in a recent
textbook aimed at the introductory level.2 It would be very
instructive to the student to go through the derivation of the
operant equation if the experiment is, in fact, used in con-
junction with the study of gas laws. Very careful manipulation
in the experimental procedure will yield an answer within
(1) ±1-2% of the accepted value of 28,96 g/app. M.W.
This experiment may be used to determine the density and
This equation is used to calculate the grams of air present at molecular weight of a pure gas. The only change would be to
the lower temperature. Since flush completely the system with the gas whose density is to
be determined and clamp the rubber tubing shut while
weighing at room temperature. While heating the gas to the
boiling point of water, the clamp would be opened. At the
the density of air will be boiling point of water and after a 10-min period, the clamp
Mi would be tightly shut.
vol of system The same operant equations would be used and both the
density and molecular weight may be calculated. This works
Equations (1) and (2) are the operant equations of this ex- well for gases such..as nitrogen and carbon dioxide. Other
periment. gases would be used as long as they are not flammable
Results and Calculations since safety considerations would preclude these.
Note Added in Proof
The results of a typical experiment are as follows:
David S. Moore of Dover College, Dover, England has suc-
Weight of apparatus at 7\ 138.2235 g cessfully adapted this experiment by replacing the described
Weight of apparatus at T2 138.1525 g stopper system with an appropriately prepared Bunsen
Weight loss (=*) 0.0710 g Valve. 3 The author is grateful for his suggested improve-
ment.
20.5° C Ti = 1OO.5°C Vol ~ 262 mi 1
Norbert Adolph Lange (&/to), "Handbook of Chemistry," Handbook
(0.071) (373,65) Publishers, Inc., Sartdusky, Ohio, 19S6, p. 1411.
2
gi Petrucci, B. H., "General Chemistry, Principles and Modem Ap-
80 plications," 3rd ed., Uacmillan Publishing Co., Inc., New York, 1982,
/fs = 0.3316 s p. 105.
3
Linstead, B. P., ESvidge, J. A., and Whalley, M., "A Course in Modem
Techniques of Organic Chemistry," Butterworths Scientific Publications,
262 ml London, 1355, p. 143.

Solution Calorimetry in the Advanced Laboratory
A Study of Glycine Proton-Transfer Enthalpies
R. W. Ramelie
Carleton College, Northfield, MN 55057
Heat effects accompanying chemical reactions are among T h e e q u i l i b r i u m c o n s t a n t values for t h e a b o v e r e a c t i o n s

the most fundamental and informative phenomena encoun- w e r e r e p o r t e d for a r a n g e of t e m p e r a t u r e s by K i n g (2) w h o
tered by chemists, both in the classroom and in the laboratory. u s e d precise m e a s u r e m e n t s of galvanic cells b a s e d on t h e
Yet, except for numerous general chemistry experiments, hydrogen electrode. L e a s t - s q u a r e s fits for results o b t a i n e d a t
typically involving expanded-polystyrene-cup reaction vessels ionic s t r e n g t h 0.30 a r e as follows:
and relatively insensitive thermometers, students gain little
experience with solution calorimetry. A major reason for this pKi = -46.7920 + 2378.22/r + 16.64 iogT (3)
in the past has been the unavailability of reliable calorimetric
pK2 = -16.1083 + 3165.76/T -t- 6.09 IogT (4)
equipment that is both reasonable in cost and high in accu-
racy. The introduction of a moderately priced solution calo- V a l u e s for AH a r e r e a d i l y inferred from t h e s e e q u a t i o n s b y
rimeter (1) has made it convenient to use this technique m the using t h e t h e r m o d y n a m i c relationship:
advanced laboratory. In our experience over a few years, the
Parr Model 1451 calorimeter has performed reliably and in dlnK/df = AH/RT1 (5)
accord with its high specifications. The experiment described
S u c h values m a y t h e n b e c o m p a r e d with t h e calorimetric re-
in this paper requires precise measurement of temperature
s u l t s of t h i s e x p e r i m e n t .
changes of a few tenths of a degree- The Model 1451 generates
a voltage output with a sensitivity of 100 m V per degree, and
a strip chart recorder provides a convenient record.
In addition to a variety of acid-base reactions we have used Experimental Procedure
powdered zinc metal in the rotating glass cell with copper This experiment requires three separate runs, using 0.300
perchlorate solution in the Dewar flask to determine the en- M solutions of sodium chloride, hydrochloric acid, and sodium
thalpy change for the redox reaction. We have also measured hydroxide. Step-by-step details for instrument operation are
the heat of complexation when a solution of ethylenediamine provided in a separate handout.
is added in excess to a solution of nickel chloride and the heat
of reaction between permanganate and ferrous ion. A variation Study of Reaction (1)
is to use the cell compartment as a titration vessel, using a Set up the calorimeter cell with 100 mL of 0.3 M hydro-
dispensing pipet to add titrant. A plot of temperature versus chloric acid in the Dewar compartment, and with about 20
volume added may be used to find the titration endpoint. mmol of glycine (HGly) in the solid sample compartment.
This paper discusses a fairly rigorous investigation of the Upon mixing, a temperature change will be observed because
heat effects accompanying the acid-base reactions of giycine. of the reaction:
Adaptation to studies of other amino acids should be
straightforward. A good reason for using glycine is that the HGly(s) + H + - • HaGly+(aq) (6)
calculated enthalpy values may readily be compared with Note that reaction (6) is not simply the reverse of the desired
those derived entirely from Gibbs free-energy measurements. reaction (1), because the glycine is added as a solid rather than
This has the value of encouraging physical chemistry students being in the aqueous state. Therefore, it is necessary to make
to see key relationships in an integrated way. The entire ex- another calorimetric run, using 100 mL of 0.3 M sodium
periment can be performed by a pair of students in one af- chloride. This will provide a similar ionic strength effect on
ternoon, and in our experience the results have been quite the heat of solution of glycine, but there will be no proton-
good. transfer reaction:
Stock solutions of 0.300 M hydrochloric acid, sodium hy-
droxide, and sodium chloride are needed. Glycine, recrystal- HG!y(s) - HGlyiaq) (7)
lized from water and dried overnight at 80°C, is finely ground If t h e o b s e r v e d m o l a r e n t h a l p y c h a n g e for r e a c t i o n (6) is
before use. What follows is an abridged version of the handout
s u b t r a c t e d from t h a t for reaction (7), t h e result is t h e e n t h a l p y
for students. Complete details on the experimental procedure
c h a n g e for reaction (1).
are available from the author.
The purpose of this experiment is to determine the molar Study of Reaction (2)
enthalpies for the two stages of glycine proton-transfer: Set up the calorimeter cell with 100 mL of 0.3 M sodium
H2Giy+ » H+ + HGly+ hydroxide, and again add solid glycine. The reaction is
iwitter ion (1)
<+H3NCH2COO-> HGly(e) + OH* — Gly-faq) + H 2 0 (8)
To obtain the enthalpy change for reaction (2) it is necessary
HGJy+- = H + + Giy" (2) not only to use the heat of solution determined for reaction
T h e c a l o r i m e t e r will b e u s e d t o find t h e q u a n t i t i e s of h e a t {7), but also to introduce the heat of formation of water:
a b s o r b e d or l i b e r a t e d w h e n k n o w n a m o u n t s of glycine a r e H + + OH' H2O (9)
mixed with s o d i u m chloride, with hydrochloric acid, a n d with
s o d i u m h y d r o x i d e . T h e calculated e n t h a l p y c h a n g e s will n o t Note that A # 2 = AH$ - AH 7 - AH$. The enthalpy change
b e t h e s t a n d a r d values b e c a u s e t h e e x p e r i m e n t s a r e carried for reaction (9) is -13,340 cal at zero ionic strength (3), and
o u t a t electrolyte concentrations of a b o u t 0.3 M. However, t h e —13,550 cal at ionic strength 0.5 (4). An interpolated value of
effect of ionic s t r e n g t h on t h e values is n o t large. —13,465 may be used.

step beating The Problem of Incomplete Protonation of Glycine
prB-reaction When solid giycine is added to a slight excess of hydro-
baseline pojt-hooting
ba&ellna chloric acid the reaction HGly + H + -*• H^GIy* does not
Msosure A/ ol [joinI proceed quantitatively because the protonated species is not
where tne change i t
Q bom 6 3 % Gomt>!«>< Measure fl( at point
a very weak acid (pKa about 2.3). This means that the heat
where chanoe is change observed for reaction (6) should be interpreted as
about 5 0 % complete
Qe - Qi — Q\
= n-AH7 - on-AHi (12)
+
start heating
where a is the fraction of the glycine present as H2Gly in the
equilibrium mixture.
Given the initial (pre-reaction) concentrations of hydro-
chloric acid arid glycine, 0.300 and w/0.1, respectively, the
value of a can be estimated from the stoichiometric/equiiib-
Typica! fhermogtam for an endotherrnic reaction.
rium relationship, which the reader should derive
= [H+][HG!yl/lH2Gly+l
Interpretation of Data = (0.3 - Wi/0.l))((ii/G.l) • • (W0.1))/(cW0.1)
Each thermogram has five parts: pre-reaetion baseline, = (0.3 - n/O.OU-<*)/« (13)
temperature change due to reaction, post-reaction baseline,
temperature rise due to heating calibration, and post-heating The appropriate value for K\ can be found from King's results
baseline. T o determine the precise temperature changes it is (eqn. (3)), and then this expression can be simplified and
necessary to extrapolate the baselines as shown in the solved by the quadratic formula. The value for Ar?! then
figure. foliows from rearrangement of equation (12).
The purpose of the electrical heating is to determine the Report
heat capacity, C p , of the calorimeter under conditions iden-
tical to those used for the chemical reaction. The current and Prepare a tabular summary of glycine masses, At values
voltage through a heater is monitored to calibrate the calo- deduced from thermograms, vaiues of Q, Qj,, Cp and AH.
rimeter and its contents. Calculate the enthalpy changes for the acid dissociation re-
actions (1) and (2), and compare your results with those in-
The heat change associated with the chemical reaction is ferred from the pK(T) studies by King. Look up the enthalpy
calculated by using the temperature change At observed for of formation of solid glycine, and calculate the enthalpy of
the reaction thermogram: formation of glycinefaq). Calculate the entropy changes for
Q = -CBAt (10) reactions (1) and (2) and suggest an explanation for their al-
gebraic signs. Make suggestions for improvement of the ex-
where the minus sign is used to satisfy the convention that periment.
heat evolved is given a negative sign.
Finally, to find the enthalpy change per mole of glycine Literature Cited
AH = Q/n (ID (1) Bulletin 1451, Part Inattumnnt Co., 211 Fifty-Third St., Moline. II. 61265.
(2) Kiasj,E,J.,J-Ainer.Chem. Sot, 74,156 0961).
where n is the amount f moles) of solid glycine used for the (31 GlofasonrG., and Hepler, L..J. Salution Chsm., t, 127 (1975).
run. (4) Christens™, J. 3. Hsnaen, L. D. and Izatt. R M., "Handbook of Proton ionizaiion Heats,"
John Wiley & Sons, Nsw York, tB7fi.
A Kugelrohr Oven from a Rotary Evaporator

A simple modification of the rotary evaporator transforms it into a Ku-
geirohr iiven, an extremely useful apparatus for distilling smaSl volumes of high
boiling compounds from bulb to bulb. Although this apparatus comes in dif-
ferent price ranges, tiie Aldrich version is simple and inexjiensive; unfultimately,
the motor has to be operated by vacuum or pressure and can be inconvenient
at times.
Here we report a simple method of converting the normal rotary evaporator
bearing a 24/10 or 24/14 adapter. Moving the evaporator into a horizontai po-
sition transforms it into a simple Kugalrohr-oven-like device (see figure). Dis-
tillation is performed by operating the rotation at the lowest speed possibie. With
this setup we have been able to attain a pressure as low as 1 mm Hg.
R. Somanarrtrtan and L. Heliberg
San Diego State University
SanDiego.CA 92182

Reactions of Thiocyanate Ions with Acid
A Laboratory Experiment
Christopher Glidewell, James S, McKechrtte, and Peter J. Pogorzelec
University of St. Andrews, St. Andrews, Fife KY16 9ST, U.K.
The reaction of solid ionic thioeyanates, such as KNCS and may be placed around the flask. After ^30 min, replace the —78°C
NHUNCS, with concentrated sulfuric acid to produce carbonyl hath by liquid N2, evacuate the system, and then pump away the
suifide, OCS, along with CO 2 , SO 2 and traces of HCN has been contents of the further U-trap. Transfer the contents of tiie nearer
known for many years as a convenient, small-scale preparation trap to tie coid finger. Record its vapor pressure at —78°C and its
infrared spectrum and determine its molecular weight {6,9).
of OCS (1): of greater antiquity is the reaction of concentrated
sulftsric acid with aqueous solutions of ionic thiocyanates to Here we have followed the published procedure (6) except that we
yield the solid product xanthan hydride (2) C2H 2 N a S 3 , first run the reaction under a pressure of 25 cm Hg air since this generally
gives an easier separation of COa from the remainder of the volatile
prepared by W6h3er (3) as long ago as 1821. Xanthan hydride products, and use different concentrations of H2SO4 in the range of
has been characterised in the solid state by X-ray analysis (4) 60%-96%. Students are provided with vapor pressure data (-78°C)
as 5-anibio-l,2,4-dithiazol-3-thione, (I), and this constitution and infrared data, and they must identify the principal components
persists in solution also (5). of the reaction products from the IR spectrum and assign as many of
the bands as possible to fundamentals and combination bands.
S—-5 (ft) Reaction of aqueous KNCS with 96% H2SOA

\ {To be performed in a fume cupboard) Place in a 260-ml flask fitted
The mechanism of formation of xanthan hydride from thio- with a dropping funnel and a magnetic stirrer, 9.7 g (0.1 mol) of KNCS
cyanate ions and acid has recently been elucidated by means dissolved in 50 ml water. Add 96% H2SO4 dropwise until a persistent
of concurrent, and synergistic, experimental and theoretical yellow precipitate is produced: cool, filter off the product, denoted
investigations (5). X, wash with water, and dry in vacuo. Note the yield and record an
The reaction which forms carbonyl sulfide and other gas- IR spectrum. (This product has no melting point: 13C and 15N NMR
eous products is widely used as a safe introduction to vacuum and mass spectral data are provided, together with the empirical
formula,
line preparations in laboratory courses in inorganic chemistry
(6). We have developed a more extended investigation of the Spectral Data
reactions between ionic thiocyanates and sulfuric acid, which
not only includes the usual vacuum line experiment, but also NMR; 6(13€)/p.p.m., +183.5, +208.6 (both quaternary) relative to
involves the elucidation of the structure of xanthan hydride TMS: S(15N)/p.p.m., - 1 16.9 (n.O.e. positive), -273.1 (n.O.e. negative)
from a combination of infrared, mass-spectral, and I3 C and relative to CHS16N(>2. Mass spectrum contains major ions at m/z: 150
15 (49%), 86 (17%), 85 (41%), 76 (96%), 74 (11%). 73 (100%), 64 (56%), 60
N NMR data, together with the testing of xanthan hydride (52%), and 59 (97%). infrared spectrum (KBr disc): p/cm"*; 3220 s,
as a possible intermediate in the formation of carbonyl sulfide. 3040 s, 2915 m, 2700 w, 2340 vw, 2175 m>, 1630 s, 1515 us, 1335 us,
We use this exercise in our third (i.e., penultimate) year lab- 1320us, 1155 MI, 1088 m, 1019s, 1005 s, 750 w, 648 m, 630 m, 616m,
oratory, where the emphasis throughout is on students 5381!>, 510 uat, 410 w, 393 mw.
learning the use of a wide range of techniques to solve real The infrared spectrum and the mass spectrum have been analyzed
chemical problems (7,8). This laboratory represents the final (10,11).
stage of structured experimental work before the students
undertake research projects during their final year. (c) Reaction of X with 96 % H2SO4
Set up a 250-ml quickfit flask with a double surface reflux con-
The experiment falls into three parts. The students have denser and equipped for magnetic stirring and oil bath healing. Add
no prior knowledge of the nature of any of the reaction prod- to the flask 1.5 g of X and 5 ml of 96% H2SO4: connect the top of the
ucts, all of which must he identified: condenser to the end of the vacuum system by means of pressure
(a) reaction of solid KNCS with sulfuric acid (identification of the tubing and evacuate the system. When the system is leak free, piace
reaction products); liquid Ng round the two traps. Heat the reaction flask (a time of =30
(b) reaction of aqueous KNCS solution with 96% sulfuric acid min, at an oil-bath temperature of 150°C is suggested) and collect the
(isolation and identification of the invoiatile product); volatile products. Pump away any non-condensible gases which form.
(c) reaction of the soiid product from (b) with 96% sulfuric acid When the reaction is complete allow the reaction flask to cool, and
(identification of volatile products). continue pumping as it does so. The subsequent identification of the
volatile products is made as in part (a).
Experimental
For pans (a) and (c) the apparatus is a simple vacuum system (9) Spectral Interpretation for X
consisting of a rotary oil pump and cold-trap; a manifold equipped The students are given the empirical formula C^HaN^S?,: with this
with a coid finger, a take-off for an 1R cell or molecular weight bulb, and the infrared, mass spectral, and I3C and ISN NMR data the
and a mercury manometer; and finally two U-traps to which reaction structural formula can be established.
vessels can be connected. The infrared spectrum indicates the presence of NH2, C=N, and
C=S, but not CH or SH bonds (10). The 13C NMR spectrum contains
(a) Reaction of solid KNCS with sulfuric acid only two quaternary resonances, confirming the absence of CH bonds;
Attach a 250-m! two-necked flask equipped with an L-shaped the low field 13C resonance at +208.8 p.p.m. is characteristic of C=S.
sidearm to the end of the vacuum system, and pEace in it 5 m? of sul- The I5N NMR spectrum which contains one resonance with a positive
furic acid: add 4 g of KNCS to the sidearm and evacuate the system. nuclear Overhauser effect (n.O.e.) and one with a negative n.O.e, in-
When the system is leak free, admit air to a pressure of 25 cm Hg to dicates that only one of the nitrogen atoms is bonded to hydrogen.
the apparatus, place a ~78°C hath (ethanol/COj) around the U-trap The mass spectrum UJ) contains no ions having mlz > 150, con-
nearer the reaction vessel and a -196°C bath (liquid N2) around the firming C3H2N2S3 as the molecular formula: the ions at m/z values
further U-trap. Place a bath of ice water around the reaction iiask and of 86, (M—S2)+, and at 64, (Sal* indicate two sulfur atoms bonded
gradually add the KNCS to the sulfuric acid by rotating the sidearm. together, those at 74, (M—CSj)+, and 76, (CS2I+, indicate a carbon
As the reaction proceeds, allow the reaction vessci to warm up grad- bonded to two sulfur atoms, so that the molecule probably contains
ually. Toward the end of the reaction, a warm water bath (^(SO"C) a fragment SCSS. In addition, the ions at m/z 60 and 59 suggest the
78 Journal of Chemicai Education

fragment HaNOS. Three major fragmentations (II) accommodate ail c o m p o u n d u n k n o w n b u t also the molecular formula then ac-
the observed ions. c e p t e d was incorrect: x a n t h a n hydride was believed (2) to be
All the spectral data together are consistent with the molecular a l o w p o l y m e r of C ^ H a N ^ . T h e r e a c t i o n o f x a n t h a n h y d r i d e
structure (I) for the product X. w i t h c o n c e n t r a t e d sulfuric acid, o n t h e o t h e r h a n d , yields COs,
SO2 a n d O C S . T h e SO2 p r o b a b l y arises from t h e oxidizing
action of t h e h o t c o n c e n t r a t e d sulfuric acid. As t h e m o i a r ratio
H a S O ^ H a O d e c r e a s e s , t h e p r o p o r t i o n of S O 2 in t h e p r o d u c t
d e c r e a s e s , a s t h e m o r e d i l u t e a c i d is a p o o r e r o x i d i z i n g a g e n t .
T h e p r o p o r t i o n of O C S d e c r e a s e s a l s o as t h e m o r e a q u e o u s
This has been confirmed by an X-ray analysis 1,4): the same structure m e d i u m can effect its hydrolysis.
persists in solutions (5) and in the gas phase (11).
Since ionic thiocyanate reacts rapidly with concentrated
Identity of Volatile Reaction Products sulfuric acid a t r o o m t e m p e r a t u r e to give COa a n d O C S w i t h
very little SOa, a n d x a n t h a n h y d r i d e reacts r a t h e r slowly w i t h
From part (a), the volatile reaction products are primarily OCS and
CO2, with lesser quantities of SO2 and HCN. If thoCOais removed h o t c o n c e n t r a t e d sulfuric acid, yielding m u c h SO3, it is con-
effectively, the remaining product is almost pure OCS which has a c l u d e d t h a t x a n t h a n h y d r i d e is n o t a s i g n i f i c a n t i n t e r m e d i a t e
mean apparent molecular weight usually in the range 60-62. Variation in t h e f o r m a t i o n of c a r b o n y l sulfide f r o m M I N C S / H a S O 4
of the concentration of the sulfuric acid within the range 60%-96% mixtures, T h i s raises interesting questions concerning t h e
causes little significant change in the volatile products except that m e c h a n i s m s of t h e v a r i o u s r e a c t i o n s of t h i o c y a n a t e i o n s w i t h
at the lowest concentration employed (60%) no sulfur dioxide is de- acids.
tected. The solid residue contains elemental sulfur and mixed ionic
sulfates, but no xanthan hydride. T h e pKB o f H N C S is - 1 . 8 5 {12), s o t h a t o n l y i n v e r y a c i d i c
m e d i a is t h e t h i o c y a n a t e i o n e x t e n s i v e l y p r o t o n a t e d . T h e
In part (c) the principal volatile products when 96% sulfuric acid m e c h a n i s m ( 5 , 1 3 ) for t h e f o r m a t i o n o f x a n t h a n h y d r i d e (I)
reacts with santhan hydride are CO3 and SOa with only small quan-
tities of OCS and a trace of HCN. As the concentration of the acid is in a q u e o u s a c i d s o l u t i o n of o v e r a l l s t o i c h i o m e t r y ,
decreased, the proportions of both OCS and SOgdecrease. The solid
residue contains elemental sulfur, ammonium aulfate, and thiourea 3 N C S - + 3H+ - * ( ! } + H C N
(5). is s h o w n in t h e s c h e m e . T h e i n t e r m e d i a t e ( V I ) ia a d o u b l y
Discussion p r o t o n a t e d f o r m of t h e N - c y a n o c a r b o n i m i d o d i t h i o a t e a n i o n ,
w h i c h m a y be formed either from x a n t h a n h y d r i d e a n d alkali
Xanthan hydride does not react at room temperature with {14), w h e n t h e b y - p r o d u c t is e l e m e n t a l s u l f u r , o r f r o m t h e
water or with aqueous sulfuric acid of concentrations up to c y a n a m i d e a n i o n w i t h c a r b o n d i s u l f i d e (15): a l l s t e p s u p t o t h e
965. Chattaway and Stevens reported (2) that superheated f o r m a t i o n o f (VII.) a r e r e v e r s i b l e , a n d t h e c o n v e r s i o n of ( V I I )
water hydrolyzes the compound to CO2, H^S, elemental sulfur, i n t o ( I ) via a t a u t o m e r o f (I) d e p e n d s o n t h e h u g e d i f f e r e n c e
and ammonium thiocyanate, but they suggested that the b e t w e e n t h e pKa v a l u e s of H N C S ( - 1 . 8 4 ) a n d o f H C N ( 9 . 2 1 ) .
primary hydrolysis products were OCS, thiourea, and sulfur. I n t h e m e d i u m e m p l o y e d , H C N is e n t i r e l y u n - i o n i z e d a n d s o
Further hydrolysis converts OCS to H2S and COa while the i s a g o o d l e a v i n g g r o u p f o r t h e p r o t o n a t i o n of ( V I I ) , w h e r e a s
high temperature of the reaction (a:200 o C) converted the H N C S is p a r t l y i o n i z e d , a n d , i n f a c t , f o r m a t i o n of ( V I I ) r e -
thiourea to ammonium thiocyanat«. These products are en- q u i r e s f r e e N C S ' ~ a n i o n s t o r e a c t w i t h ( V I ) . If t h e m e d i u m is
tirely intelligible in terms of the structure (4) of xanthan hy- insufficiently acidic, p r o t o n a t i o n o f (VII) will n o t b e effected,
dride as we now know it, but at the time (1897) of Chattaway a n d n o ( I ) will f o r m . 1 If t h e m e d i u m is t o o a c i d i c t h e r e w i l l b e
and Stevens 1 investigation not only was the structure of the insufficient free t h i o c y a n a t e ion p r e s e n t t o f o r m (VII), so a g a i n
n o ( I ) w i l l f o r m : i t i s u n d e r j u s t t h e s e c o n d i t i o n s t h a t O C S is
f o r m e d . T h e r e a p p e a r s t o b e a critical r a n g e of a c i d i t y for t h e
f o r m a t i o n o f x a n t h a n h y d r i d e f r o m t h i o c y a n a t e i o n s in
1 a q u e o u s s o l u t i o n . B e y o n d t h e u p p e r l i m i t of t h i s r a n g e , t h i o -
1n the preparation of (I) described in the Experimental part, a 2 M
solution of KNCS is used: if the added sulfuric acid is of concentration cyanate ions are merely bydrolyzed and/or oxidized yielding
iess than 90%, no (!) is formed: 96% acid is recommended. O C S a n d o t h e r gases; b e y o n d t h e lower limit of this range,
essentially no detectable reaction occurs.
H+ + SC8" HNCS
Literature Cited
SH
2 HNCS C (1) Vanino. L., "Hatidbueli <lei Praparativen Chemie," Ferdinand Enke, Stuttgart, 1321,
Hand],p. 271.
<2) Cl>attaway,)\D.,andStpvens, H.I'.. J. Chum S o r . L X X f , 607! 1891).
(VI) (3) Wtihlef, F,,Ann. /Ihy.s-..e91273 (1821).
14) HwdviiL, A., Aeta « ™ . Stand,, 17,2575 (1963).
(5) Butler, A. R., and Giidewell. C , J Cham, flewoi-en, !S) 6ft, (M; 0801 (1982).
Hi) M H O , G., and Roekelt, B. W , "Practical Imtpraic Chemistry." Van ftalrani) fteinhdd,
London, 197J, p. 338.
(7) (iSidewt'Sl, C, J. C H K M . Suva, 57,23i> 0980).
15) Cfidewel), C-, and P<>j;oizelec. P..!., J. ClIEM. E D U C , 57,740 (1980).
(Vtf) T9) For ttescFiptuin&o! standard varuEim-Jineinamputatiuns, seenSully, W . L . , " T h e S y n -
thexj.s rtnd CharacleiizHtiurs of (storgmiic ComptHmrts," JVntire-Hatl. Eiigtowixx]
aii'ls,NJ.,1970.
-HCPl fiO) EnuHera, H..!., Haas. A.,ami S h e p p a r d . R . J . Chtm Sac ,3165(1963).
(11) Bews.J. K., and Oiidcwell, C-> J- A M Sow-tore, 86,377 (1982).
(12) Mnigan, T. n . B., Siedman, O.,and Wiiiimip, P. A. E..J. Chem-Soc ,4813(1%5).
1 (13) Hall, W. H., and Wilaoii, I. S., Aunt. J. Chfm.. 22,513 (1369).
""-S (14) Cotton. P. A., and McCIeveity, .T. A., fnorg. Chem. S, 223 (18fi7).
(I) (15) Fecfcler, Jr., J. P., and Coucouvnnis, D.,J. Amet. Chew. Son., SS. 3913 (1966).

edited by
Inventory Control
DAVID L. BYRUM
Globe High School
501 Ash
Globe, AZB53G1
Potentiomeiric Titrations Using Pencil and

Graphite Sensors
Walter S. Selig
Lawrence Liwermote Natlonai Laboratory
University of California
Uvsrmore, CA 94550
T h e c o s t of v a r i o u s c o m m e r c i a l i n d i c a t i n g e l e c t r o d e s r a n g e s
f r o m a b o u t $ 4 0 for p H e l e c t r o d e s t o a s m u c h a s § 3 5 5 for a
p o t a s s i u m ion-selective electrode.1 T h i s cost can b e r e d u c e d
t o less t h a n $1.50, a n d in s o m e cases t o m e r e p e n n i e s b y
m a k i n g sensors from g r a p h i t e r o d s a n d pencils for u s e in p o -
t e n t i o m e t r i c t i t r a t i o n s . T h e s a m e s e n s o r c a n b e u s e d for m a n y
t y p e s of t h e s e t i t r a t i o n s ( a c i d / b a s e , c o m p l e x ! m e t r i c , p r e c i p -
itation, a n d redox).
Background
Hoke and Collins (J) recently used a membrane of polyvi-
nyl(chloride) (PVC) piastieized with dioctylphtha&te (DOP)
as a sensor in the potentiometric titration of altyl aromatic
sulfonate with a cationic surfactant We have found {2,3) that
a spectroscopic graphite rod and various pencils can serve as
inexpensive support materials for this membrane. This sensor
can be considered a variant of the "coated-wire" electrodes
introduced by Cattrall and Freiser (4) in 1971.
Preparation of Coaied-Graphlie Electrodes

The graphite rods {Spectroscopic graphite, UF-4S, Ultra
Carbon Corp., Bay City, Michigan) were 152.4 mm (6 in.) long
and 6.35 mm (V4 in.) in diameter. They cost $1.29 each and Table 1. Some Feasible Potentiometric Titrations Using a
were purchased in 12 in. lengths. Other grades of graphite such Graphite Sensor Coated with PVC-DOP
as Ultra carbon U-7 and Poeo graphite AXF will serve equally Endpoint
well, and the diameter is not critical. Ion measured Titrant Titration type break, mV
The coating solution is prepared by dissolving 1 g of low-
Perchlorate CetyipyrSdlnium Precipitation 120
molecular weight PVC and 1 g of DOP in 30 ml of tetrahy-
Hexafluorophosphate Cetylpyrldinlum Precipitation 220
drofuran in an Erlenmeyer flask, applying heat, and occa- 120
Peroxydtsulfate Cetylpyridlnium Precipitation
sionally shaking to promote solution. The graphite rod is Nitroform Cetylpyrldinlum Precipitation 190
dipped for a few seconds to a depth of about 13 mm {'/a in.) Picrate Cetylpyrldinium Precipitation 170
into the cooled coating solution and air-dried. This coating Tetiaphenyl- Cefylpyrldlnium Precipitation 450
process is repeated 3-5 times. The cost of the coating solution borate
is less than $0.01 per electrode; one hatch of the PVC/DOP Dodecylsulfate Ceiylpyrldinium Precipitation 310
solution will coat many electrodes and will keep indefinitely Tbalious Tetraphenyl- Precipitation 310
in a stoppered glass vessel. borate
Bromide + Iodide Silver (!) Prectpltatton
When the coating deteriorates, as indicated by decreasing Lanthanum (III) Precipitation 30
Fluoride
and/or less steep endpoint breaks, it can be entirely removed Lead (II) Precipitation 25
Tungsiale
with hot tetrahydrofuran. The graphite rod can then be re- Add phthatate Sodium Acid-base 70
coated and reused.
nyovxrae
Ferrous Oxidation-reduction 250
Measurements Chromate
Ethylenediamlne Lead (II) Complexlmetric
Any convenient reference electrode can be used in con- tetraacetate
junction with the PVC/DOP-coated sensor. We have used a
plastic, single-junction, silver/silver-chloride reference elec-
trode containing a salt-bridge of 0.1 N sodium nitrate. The g r a p h i t e s e n s o r is c o n n e c t e d t o t h e m e t e r b y m e a n s o f a n a l -
electrodes are connected to the measuring instrument, which l i g a t o r clip. A t y p i c a l t i t r a t i o n cell is s h o w n in t h e figure.
can be any convenient pH/raillivolt meter. The coated
What Type of Titrations can be Monitored?
A list of titrations we have monitored with the coated
Work performed under the auspices of the U.S. Department of Energy at graphite sensor ia given in Table 1. Full details on these ti-
Lawrence Llvermore National Laboratory under coniract number W-740S- trations are presented in reference {2) which gives represen-
£NG. tative titration curves, magnitudes of endpoint breaks, and
1
These prices were valid in spring 1983. standard deviations. No doubt many more are possible, and

Table 2. Comparison of Sensors in the Pofentiometrlc THraHon of an Aqueous Nltroform Solution versus 0.05 N Celytpyritiinlum Chloride.
Source of Mean endpoint Standard Number ol

Senses- supporting material break (mV! deviation replicates
Fluoroborale Orion Research 165 0.10

PVC/DOP-ooated graphite Ultra Carbon UF-4-S 190 0.04
PVC/DOP-coated mechanical pencil Turquoise Eagle Drawing lead 110 O.OB
PVC/DOP-coaled No, 2 pencil Astro 155 Bondexed lead 30 0.03
Tttration ceil with a coaled no. 2 pencil sensor and a slngie-junctlon reference electrode.
t h e w r i t e r w i s h e s t o l e a r n o f t i t r a t i o n s w h i c h cannot be p e r - State Street, Decatur, Texas 76204). However, this material

f o r m e d . A l i m i t a t i o n o f t h e s e n s o r is i t s a p p l i c a b i l i t y i n is somewhat more costly, S6.31 for a 6-in. rod of lfa-'m. diameter
aqueous m e d i a only ( a d d s and bases are alright), because (but still inexpensive compared to the $295 fluoride ion-se-
o r g a n i c solvents wil! a t t a c k t h e m e m b r a n e . lective electrode).
In summary, pencils can be used not only to write with or
Pencil Electrodes chew on, but also to monitor various potentiometric titra-
The next obvious reduction in cost is to use leas expensive tiona.
graphite-contain ing materials such as pencils. For one titra-
PfiKtalmor: This document waa prepared as an account of won* sponsored by an agency o l iha Hulled
tion, nitroform, C(NO 2 ) 3 H, versus cetylpyridinium chloride, States Govemuienr. Neither fhe Unlled States Government nor Hie IJnlveralty of California nor any of Ihalr
we have used the following sensors: employees, mgttes any warranty, express or implbait or assumes any JegaF (lability or reaportefcllily tor
Ihe accuracy. corcpleleiiess, or usefulness of any inlorfrtal-on, apparatus, produc!, or process dscksed,
or raprflsejits Ihat He use would not Infringe prfvalely owned rights. Reference herein to any specific
(1) A mechanical pencil "load" (Turquoise Eagie drawing lead) sealed commercial product, process, or service by trace name, trademark. msiKifflcTurar, or oHwrw&e. dose
nol necessarily constitute or Imply Ite endorsement, recommendation, or favoring By tha UnJled STstas
into a glass capillary for mechanical strength. The cost of each Oovemmenl or the University of Ca^SomJa. The views and opinions o l authors expressed herein do nol
"lead" is $0.07. It needs to be crimped into a support because it neces3ariJy ST&te or reflect those of the United Steles Government Iharear, Bid ah&fl not He u&ed far ad-
vertising or product endorsement purposes.
breaks easily.
(2) A No. 2 Astro Bondexed "lead" pencil from which the eraser waa
removed and the resulting cavity filled with solder to make elec- Literature Cited
trical contact with the graphite core. The coat of the pencii is (1) Hoke, S, H.. and Collins, A. G, Report 1979, 8BTC/KI-79A0; of. Cliem. Abstr., 93:
1964 lq (1980).
B o t h variants were coated with. P V C / D O P as described above. (2) Soiig.W..Anulyt.Letters, 1S[A3),309(19£&
A c o m p a r i s o n of m e a n e n d p o i n t b r e a k s a n d s t a n d a r d devia- 13) Selig. W. S,,I<!nerfiy& Technology n?£t»tei>i Lawrence Livennore National Liibora)oryh
August 1982, p. ii.
t i o n s for t h i s p a r t i c u l a r t i t r a t i o n is p r e s e n t e d in T a b l e 2. In- (4) Cattrall, R. W,,and Freiser, H., Anal Chem., 43,1305 (1371).
c l u d e d a r e previously o b t a i n e d d a t a u s i n g a f l u o r o b o r a t e 15) SEME, W., Mikrtichim. Ada, II, 437 (1979).
16) Sel«,W.8.,Microchem.J. (in press).
commercial sensor (5). T h e largest b r e a k s were o b t a i n e d w i t h 17) Selig, Wr S., work in progress.
t h e P V C / D O P - c o a t e d g r a p h i t e sensor, followed b y t h e com- 18) Bercik, J., Htadky, Z., and Cakrt, M.. Z. ftial- Cham., 261, 1
mercial fluorofaorate sensor. T h e smallest b r e a k was o b t a i n e d
w i t h t h e coated N o . 2 pencil. I t seems t h a t t h e surface a r e a in
contact w i t h t h e solution, as well as t h e presence of impurities
(the wood of t h e N o . 2 pencil was in c o n t a c t w i t h t h e solution)
have a significant effect. AH P V C / D O P - c o a t e d sensors yielded
lower s t a n d a r d d e v i a t i o n s t h a n t h e c o m m e r c i a l s e n s o r .
Although we have, as a t o u r de force, tested t h e N o . 2 pencil
electrodes in only one t y p e of t i t r a t i o n , we h a v e n o d o u b t t h a t Rubber Bulb Modification for Pipetting
m a n y o t h e r t i t r a t i o n s can be monitored in this m a n n e r . In fact, Joe B. Davis
t h i s idea m a y lend itself t o a r e s e a r c h p r o j e c t for s t u d e n t s . Winthrop College
Rook Hiil, SC S9733
Slmpier Yet—No Costing at Ail
. L e a r n i n g t o u s e a r u b b e r b u l b w i t h a p i p e t p r o p e r l y is f r e -
It is well known that some titrations yield better endpoint
q u e n t l y f r u s t r a t i n g for a l l c o n c e r n e d . P l a c e m e n t o f t h e n e c k
breaks in partially nonaqueous media because of reduced
of t h e b u i b f i r m l y a n d s q u a r e l y a g a i n s t t h e e n d of t h e p i p e t
solubilities of the precipitated species. Thia is particularly true
is d i f f i c u l t f o r m a n y s t u d e n t s t o m a s t e r . T h e i r u s u a l t e n d e n c y
for the titration of fluoride versus lanthanum{IIIJ or thori-
is t o f o r c e t h e e n d of t h e p i p e t i n t o t h e n e c k o f t h e b u l b , r e -
um(IV), and of sulfate versus lead or barium nitrate. All of the
s u l t i n g i n i m p r o p e r f i l l i n g a n d c o n t a m i n a t i o n of t h e s o l u t i o n
variants described above, minus the PVC/DOP coatings, can
b y contact with the bulb. Worse yet, they sometimes become
be used for the following titrations
so frustrated with the pipet bulb t h a t they resort to the d a n -
g e r o u s p r a c t i c e of p i p e t t i n g b y m o u t h . A s i m p l e m o d i f i c a t i o n
1) fluoride versua La 3+ in 60% methanol (6),
2) fluoride versus Th 4+ in 60% methanol {6),
3) sulfate versus Pb2-*1 in 80% methanol (7),
4| sulfate versus Baa+ in 80% methanoi (7).
The magnitude of the endpoint break can be improved by
dipping the bare sensors for several minutes into a neutral 0.2
M potassium permanganate solution. The increased activity
resulting from this treatment was explained by Bercik et al.
(8) as resulting from either the formation of a quinone-hy-
droquinone redox system on the electrode surface during the
activation process, or from the establishment of a mixed po-
tential between separated manganese dioxide on the electrode
surface and the solution.
While any graphite rod can be used, including the pencils,
we have obtained the largest endpoint breaks with Poco
graphite, grade AXF-9QBG1 (Poco Graphite Inc., 1601 S. Diagram showing proper procedure tor bulb modifIcatson.

of rubber buibs used in my quantitative analysis laboratory towel was sufficient to prevent "walking"). The router bit
has alleviated these problems. The straight opening in the should be in the retracted position and the wrist should be
neck was routed to a conical shape with a 45° bit (total in- supported on the router base or table. Use of a portable drill
cluded angie-90a). The simplest method is to press the bulb is NOT recommended. Suction can be applied to the pipet in
neck against the rotating bit of an inverted router until the the usual manner by lightly pressing the self-centering neck
desired depth is reached (see figure). Only light pressure, of the bulb against the end of the pipet. Pipet aids employing
applied intermittently to prevent overheating and meiting of a polyethylene fitting with a conical opening are available from
the rubber, is required. CAUTION: Router speeds are about Dynalab Corp., Interex Corp., Cole-Parmer and others. Bulbs
25,000 rpm. Preferably, the rotiter should be mounted on modified as described have proved satisfactory for a number
a router table. Alternately, it may be firmly held or damped of years.
on a bench top with a vibration-damping surface (a folded
A Convenient Glassware Cleaning Bath

Over the last few years a method has evolved in our laboratory which provides tiuly clean glassware with minima! effort
and apparatus. Although originaiiy designed for a biochemical research laboratory where traces of metallic ions could not
be tolerated, the method has become favored in student laboratories as well.
The procedure involves mechanically removing any bulk dirt from the glassware, completely immersing the glassware
in 0.25% PEX cleaner, heating for several hours, rinsing several times in tap water and then in deionized water, and drying
in an oven. A major drawback of this procedure has been the lack of a convenient, reliable heating bath. A vertically mounted
eiectiical immersion heater requires a stirrer, often melts pf asticware whidifloatsinto the heater, and sometimes even damages
the heating tub. A steam immersion heater constructed of heat-resistant nonmetallic tubing avoids these problems but is
very expensive and Saste only a few months. An external heater, such as a hotplate, cannot be used with a plastic tub. Con-
struction of a heating bath which avoids the shortcomings of previous designs is described here.
M l STOPPER
CAP
CHROMEL WIRE
" TUBE 3/8

AMP
CORD
CONNECTOR
Scaie [tawing of the horizontal immersion heater for the glassware cleaning bath.
The bath consists of a 30-gal. polyethylene tub, a homemade 1000-W immersion healer, and a 24-hr timer.
Six inches of insulation are removed from a 5-ft section of 18/2 heater ("lamp") cord (with plug). An uninsulated, sol-
derless connector is used to attach one end of an 11-ft piece of 22-gauge Chrome! wire (total resistance = 10.7 ofcma) to one
of the heater cord wires. The connected wires are slipped into a 12 X % in. O.D. Vycor tube and the majority of the Chromei
wire wound around the outside of the tube to form a 6-ia.-long heater coil. The other end of the Chromel wire is then attached
to the other heater cord wire and the solderless connector pounded.flat. The entire heater assembly is then slipped inside
an i l X %-in. O.D. Vyc«r tube which has been sealed at one end. This assembly, in turn, is inserted into a hole ( # 1 0 borer)
in a # 1 1 Neoprene stopper as shown in the figure. Note that the Vycor tubes are arranged so that the uninsulated portions
of the heater cord wires cannot touch. The heater is pushed firmly into a 2-in. -diameter hole which is drilled just above the
bottom of the tube. A cap of PVC pipe fittings is notched to accommodate the heater cord and pushed onto the Neoprene
stopper to protect the bare wires. To protect the Vycor tubes from heavy giassware, a rigid plastic grill (a refrigerator pop
can dispenser manufactured by Rubbermaid) ia epoxied to the bottom of the tub. Setting the time to heat for 2.5 hr provides
a maximum temperature of about 75"C {except for a region within \ in. of the tub bottom) and yields truly clean glass-
ware.
Tom Lyons Fisher

Phyilie M. McGinnis
Juniala College
Huntingdon, PA 18652

E l e c t r o d e P o t e n t i a l D i a g r a m s a n d t h e i r U s e
in the Hill-Bendail or Z-Scheme for Photosynthesis

Peter Borrell and Denis T. Dixon
University of Keete, Staffordshire, England
Electrode potential diagrams provide a common way of

representing biochemical electron-transfer processes in
photosynthesis (1-3) and respiration (4). However, we have
found that when students approach these diagrams from the
viewpoint of physical chemistry or photochemistry they be-
come confused by their apparent similarity to molecular en-
ergy-level diagrams such as the Jablonski diagram.
Also, the diagrams are difficult to understand in themselves,
and confusions arise for several reasons: the use of a reverse
scale; the use of the term "oxidation/reduction potential" to
describe the ordinate; the depiction of single substances on
the diagram rather than reactions; misunderstanding of the
meaning of various arrows; and misunderstanding of the na-
ture of the "energy" which can he calculated from the
height.
The aim of this article is to help clear away some of the Figure 1. (a| An electrode potential diagram for the Zn/Cu system, showing the
confusions by providing a description of electrode potential levels, half reactions ana BIB effect of a hundredfold ctiange in concentration.
(t>) The diagram showing the spontaneous reaction with electron transfer from
diagrams in terms of a simple and probably familiar example, Zn to Cu (note the directions of the arrows). The height gives the maximum work
that for zinc and copper sulfate. Various cautions are offered available from the reaction, (c) The nonspontaneous reaction: w o * is required
and then a brief description of the Hill-Bendall or Z-scheme to drive the reaction and the height gives the minimum quailty needed. Again
for photosynthesis is given to emphasize the main points. note the direction of the arrows.
While we have used an up-to-date diagram for photosyn-
thesis, it is not the aim here to provide a current view of the
topic; our object is simpiy to present a correct physical-
chemica! description of the diagram. so t h a t extra work must always he done on t h e system to
a+ a c h i e v e a given increase in t h e G i b b s function.
An Electrode Potential Diagram for the Zn/Cu System
F o r a s p o n t a n e o u s r e a c t i o n A G is n e g a t i v e s o t h a t if a n y
The example chosen to illustrate the principles is the Zn/ w o r k is o b t a i n e d f r o m t h e p r o c e s s , i t w i l l b e less t h a n t h a t
CuSOj system, It will be recalled that zinc reacts with aqueous g i v e n b y t h e v a l u e o f A G ; i.e., f o r r e a c t i o n ( 1 ) w i t h s t a n d a r d
copper(Ii) sulfate to give metallic copper and zinc sulfate: a c t i v i t i e s , t h e w o r k o b t a i n e d ( = —to) will b e l e s s t h a n 2 1 2 . 8 k J
mol"1.
Zn{s) + Cus+(aq> - Cu(s) + 2n3+(aq) (1)
R e a c t i o n (1) c a n b e d r i v e n b a c k w a r d s i n a n e l e c t r o c h e m i c a l
In the laboratory the reaction goes to completion for all ceil
ordinary concentrations of Cu2+. The standard change in the
Gibbs function1 for the reaction, AG e , is -212,8 kJ mol"1. C u t s ) + Z n s + ( a q ) •-* C s 2 + ( a q ) + Zn(s) (2)
If the system is set up as an electrochemical cell (the Daniell b y applying a higher opposing voltage, in other words b y doing
Cell) work o n t h e cell. Now t h e c a l c u l a t e d work r e q u i r e d ,
Zn(s) | Zna+(aq) j | Cu(s) "Wn =
minimum work required = AC
is a m i n i m u m q u a n t i t y a n d in practice, m o r e work would be
then the EMF for the standard activities is +1.103 V, the n e e d e d t o drive t h e reaction back,
copper electrode being positive. In this case, with unit ac- F i g u r e l a shows an electrode p o t e n t i a l d i a g r a m for t h e
tivities of reactants and products, the EMF would be E°, the Z n / C u s + s y s t e m . T h e reactions a r e shown as half-cell reac-
standard EMF of the reaction, which in turn is related to the tions; values of E e , t h e s t a n d a r d e l e c t r o d e p o t e n t i a l s , a r e
standard change in free energy by t a k e n from t a b l e s of s t a n d a r d values (7).
E a c h p o t e n t i a l refers t o t h e E M F of a cell in which t h e
l e f t - h a n d electrode is a h y d r o g e n electrode, e.g.,
where F is the Faraday constant and n is the number of elec-
trons exchanged in the reaction. Using such a cell, work could H 2 (g: I atm)Pt j H+(aq) | Zn 2 + (aq)| Zn{s)
be obtained from the reaction. for which t h e overall reaction is
Now the work, w, in a process is related to the change in
Gibbs function, at constant temperature and pressure, by the H s (g) 2H + (aq) + Zn(s)
inequality
T h e half-ceil reaction is an a b b r e v i a t e d form of this e q u a -
w> AG tion.
T h e actual value of E9 given refers only to this reaction and
so, w h e n using t h e d i a g r a m , oniy differences in t h e values of
1 t h e EMF a r e i m p o r t a n t . A b s o l u t e values h a v e no special sig-
The Gibbs Function is now the recommended name (5, 6) for the
more commonly used "free energy." nificance o t h e r t h a n for t h e reaction w i t h h y d r o g e n .

Figure 1b shows a representation of the spontaneous reac- are given. The processes by which the work is obtained, be
tion (1). The vertical arrow shows the direction of electron they direct such as drawing electric current, or indirect such
transfer, from zinc to copper. With reversible reactions at the as the coupling between this reaction and another via an en-
top and bottom of the vertical arrow there is an ambiguity in zymic mechanism, are subject to the limitations of the second
the direction of the overall reaction. This is eliminated if it is law of thermodynamics. All real processes involve loss of work
noticed that the reaction at the arrow head is proceeding in as heat and so to drive a reaction more work than that indi-
the normal direction (left to right) depicted here by a single cated by the height of the arrow will be needed, whereas for
arrow, while that at the tail is in the reverse direction, a spontaneous reaction less work would be obtained.
So, when electron transfer occurs, the electrons are pro- Another problem arises in how the work which is available
duced in the (tail) reaction <2n -* Zn 2+ + 2e~) and consumed from a spontaneous reaction is used to drive another reaction.
in the (head) reaction (Cu 2 + + 2e~ ~* Cu). If reaction takes An example of this will appear with the synthesis of ATP in
place in an electrochemical cell, electrons flow from the neg- the photosynthetic scheme. Imagine we have one reaction
ative electrode to the positive electrode.
The downward direction of the vertical arrow shows that A-B
the reaction is spontaneous. The convention in physical which is spontaneous, with a large decrease in the Gibbs
chemistry is to use a downward arrow in an energy diagram function, and another
to represent energy evolved and thus, usually, a spontaneous
reaction, C-D
The EMF of the cell, for reactants and products at standard which has a small increase in the Gibbs function.
activity, is £ e ( h e a d ) - £ e ( t a i l ) ; i.e., If both are independent of one another so t h a t energy can
only be transferred from one to another in the form of heat,
EMF = £ e (head) = 0.3402 - {-0.7628} = +1.103 V then, even if the reactions are occurring together in the same
which is the standard electrode potential for the overall re- pot, the second cannot proceed since no work has been pro-
action. vided.
For a spontaneous reaction (downward arrow), the work is If, however, there is a mechanism, such as
then
A + C — [AC) - B + D
w = AGe = -nFE*> in which both steps are spontaneous, then both B and D will
or for two-electron transfer in reaction fl), be formed.
In particular, if the reactions are coupled enzymically
w = -212.8 kJ mol-' through a membrane so there is some sort of common inter-
The negative sign indicates that work is available and the mediate, then both the reactions will proceed. It is in this sense
equality between w and AGe shows that the maximum work that biochemical reactions are coupled so that reactions which
available has been calculated. are not spontaneous can be driven by those that are.
The reverse process is shown in Figure lc by an upward Also there is the effect of concentration. The values in
arrow. Again electron transfer is shown by the arrow direction Figure I obtained from the tables are those for the hypo-
with the reaction at the head proceeding normally, i.e., left to thetical standard state with standard molaiity and fugacity.
right, consuming electrons, and that at the tail proceeding In using such values in qualitative discussion, the effect of
right to left, producing electrons. The EMF however is now non-ideality may be small so that activity can be replaced by
negative (£ e (head) - JSe{tail) = -1.103 V) and so w is a concentration, but the effect of concentration can be appre-
positive quantity (4212.8 kJ mol""1). Thus work must be done ciable. Thus for the reaction
on the system to drive the reaction in the direction indicated
by the arrow and the value of w, calculated from the change oxidized form •— reduced form + H +
in Gibbs function, is the minimum work required.
then if H + and H^ are in their standard states,
The Electrode Potential Diagram in Teaching
Electrochemistry nF [oxidized]
Diagrams such as those shown in Figure 1 could be of much T h e s h a d e d portion in Figure 1 a shows t h e effect of decreasing
help in teaching electrochemistry where sign conventions t h e Z n 2 + c o n c e n t r a t i o n b y a factor of 100.
often seem to be a stumbling block to understanding. The P r o v i d e d t h e half-cell r e a c t i o n s h a v e large differences in
conventions are, of course, implied in the diagram and in the s t a n d a r d e l e c t r o d e p o t e n t i a l s , valid q u a l i t a t i v e conclusions
reaction directions assumed for head and tail of the elec- as t o t h e feasibility of a particular reaction can b e d r a w n from
tron-transfer arrow, but the correct sign is yielded easily and t h e d i a g r a m . If, however, t h e t w o half-cell reactions h a v e
the treatment seems to operate in a more natural way. similar p o t e n t i a l s , t h e n c h a n g e s in c o n c e n t r a t i o n can r e n d e r
The principal disadvantage is the scale, which is reversed, a s p o n t a n e o u s reaction impossible.
with the positive end at the bottom. The diagram is con-
structed in the same sense as we use for energy diagrams, with Photosynthesis
the notion of "energy in," represented by an upward arrow. The overall process in photosynthesis in green plants is the
The electrode potential diagram is thus essentially a free en- absorption of CO2 and HaO in the presence of light to give
ergy diagram with the upward arrow representing minimum carbohydrates and oxygen
work required as weil as electron transfer. Since A6" e and E0
have opposite signs the standard electrode potential scale CO2(g) + HjOO) (CH 2 O) + O2(g) (4}
must be a reverse scale.
(CH 2 O) represents a "proto-carbohydrate."
Free energy diagrams are met with elsewhere in physical Photosynthesis can be divided in three steps (7),
chemistry, for example in the EHingham diagram representing
the reduction of metal oxides to metals (8). 1) Light collection via chlorophyll and other pigments and
conveying the energy to a reaction center.
Cautions in Using the Diagram 2) The oxidation of H2O to O2 and the reduction of NADP+ to
One difficulty that has been mentioned already is that when NADPH (nicotinamide adenine dinucleotide phosphate). The
the height is used to calculate the work for a given reaction overall equation is
then minimum (upward) or maximum (downward) quantities 2NADP+ + 2HSO + Sight -* 2NADPH + 2H+ + O2 (5)

presumably because the reactions are reversible. In fact, a
scale of standard electrode potentials is used.
3) For those reactions which are well-characterized (e.g.,
O2/H2O) the values given in the diagram are E& values rather
than Ee values. Because it is usual in biochemical systems {4,
JO) to determine quantities at the physiologically convenient
pH of 7, Ee' and AG& values refer to standard quantities at
I this pH.
ft
c ——n 4) For the remaining reactions (e.g., Qox/Qred, etc.) the
2 values are known approximately from practical measurements
•a
o and are therefore simply electrode potentials, E values, for the
unknown concentrations in the cell.
In a complicated system, under active study, the mixing of
Figure 2. A Hiil-Bendail or Z-diagraro for electron transport in a ohloroplast. The precise and imprecise information is unavoidable in order to
details are discussed in the text together with some suggestions tor improving gain the overall understanding which the diagram gives,
the ciarlty. See also the addendum concerning the pheo&hytin intermediate. 5) The vertical arrows represent two things: (a) the direc-
tion of electron transport between the reduced form of one
substance and that of another; (b) the quantity of work re-
ATP (adenosine triphosphate) ia also formed from the rjiphos- quired to effect the transfer in the upward direction or the
phate, ADP, in this step. work available from a transfer in the downward, spontaneous,
3) The absorption of CO3, oxidation of NADPH and formation of direction as indicated in. Figure 1, In particular, the upward
<CH2O): arrows do not represent the difference in energy between
molecular energy levels in the chlorophyll molecule such as
2NADPH + 2H + + COS -- fCH2O) + 2NADP+ + (6) would be found in a Jablonski diagram (11). The energy ab-
sorbed by the chlorophyll certainly provides the work to effect
The process requires three molecules of ATP. the transformations in photosystems I and II but the energy
used must be greater than the work required.
P r o c e s s ( 3 ) is t h e C a i v i n - B a s s h a m c y c l e , w h i c h i n v o i v e s a
l a r g e n u m b e r of c a r b o h y d r a t e s a n d t h e i r v a r i o u s m o n o - a n d
d i p h o s p h a t e s . P r o c e s s ( 1 ) , t h e l i g h t - c o l l e c t i o n s t e p , is t h e An Outline Mechanism
subject of m u c h c u r r e n t w o r k since t h e n a t u r e of t h e energy The Z-scheme is a suggested mechanism for the overall
transfer steps a n d the m e c h a n i s m by which the photorecep- reaction. It is simplest to follow an electron through the se-
t o r s a c t is still n o t w e l l - u n d e r s t o o d . quence but it must be understood that in the dark all the
I t is p r o c e s s (2) t o f o r m N A D P H w h i c h w e a r e c o n c e r n e d various reactants and products are at concentrations deter-
w i t h h e r e . T h e m e c h a n i s t i c s c h e m e w a s first s u g g e s t e d b y Hill mined by the equilibrium constants for the reactions (in the
a n d B e n d a l l ( 9 ) , a n d i t is o f t e n k n o w n a s t h e H i l l - B e n d a l l absence of side processes). Illumination shifts the equilibria
s c h e m e o r as t h e Z - s c h e m e b e c a u s e of its g e n e r a l s h a p e . to steady state values which will depend on the light intensity.
The process can be looked at sequentially as follows.
The Hill-Bendall or Z-scheme 1) Light is entrapped by photosystem (I (PSII) in which
A simplified but recent version of the diagram is shown in it is thought a complex of the photo-receptor, P680, with a
Figure 2. It can be seen that Figure 2, like Figure 1, is an quinone electron acceptor, Q, is excited and undergoes charge
electrode potential diagram. transfer
Immediately, several points can be made.
1) The majority of the substances are depicted as single (P680rcd-Qo*} + hv - P68GO, + Qred
entities. In the electrode potential diagram, Figure 1, each The oxidized form, P680OX undergoes, via intermediate reac-
level represents not a single species but a half reaction between tions, a reaction with water
at least two species.
In Figure 2, most of the materials are not completely char- P680o, + %H2O - P680red + H + + V4O2
acterized chemically, and so presumably, from the viewpoint
of those familiar with field, for the electron acceptor in pho- So the net effect is the transfer of an electron as water is
tosystem II, the term Q represents both the reduced and oxi- oxidized
dized forms. However, from a novice's viewpoint, single sub- H + + V4O5! +
stances with an arrow between them represent a chemical
transformation, but this is not the case at all here, The vertical and C ^ reduced
arrows represent electron transfer in the sense of Figure 1.
Ideally each level should show the reaction with hydrogen
but, practically it would seem preferable to depict Q as As the diagram shows, this requires work to be done on the
system, the minimum work being
o r p e r h a p s a s Q o s / Q r e d w h e n t h e p o s i t i o n o f t h e c h a r g e s is s t i l l
n o t c l e a r a n d a s Q + / Q or Q / Q ~ w h e n t h e p o s i t i o n of t h e
c h a r g e s is k n o w n . I t s h o u l d n o t b e s h o w n a s s i m p l y Q . It is the photon which provides the energy for the work to be
F u r t h e r , in some representations, t h e reductions are written done.
i n t h e w r o n g s e n s e , i.e., 2) The reduced quinone (Q^red) reacts with a plastocyanin
via a series of reactions involving a quinone, a plastoquinone
H2O - V2O2 + 2 H + + 2 e - and a cytochrome; again an electron is transferred .
T h i s is t o c o n v e y t h e p a r t i c u l a r d i r e c t i o n o f t h e r e a c t i o n d u r i n g
e l e c t r o n t r a n s f e r b u t it c a n lead t o difficulties in calculation
if t h e Ee v a l u e is t a k e n , m i s t a k e n l y , t o r e f e r t o t h i s d i r e c -
tion. The transfer is a downhill process so it is a spontaneous step
2) T h e a x i s is labelled " o x i d a t i o n / r e d u c t i o n p o t e n t i a l , " and work is available
Vofume 61 Number 1 January 1984 85

Three moles of ATP are also required to fix 1 mole COa in
= -38.6 kJ mot"1. the Calvin cycle. The passage of 4 electrons will produce 2
molecules of ATP in step (2) above, so a further molecule is
Some of the available work is thought to be used for the required. Ideas on where this is formed have varied; one sug-
conversion of adenosine diphosphate (ADP) to the triphos- gestion is t h a t it is formed in an alternative pathway to the
phate production of NADPH in a cycle which includes photosystem
1. The second possibility would require extra photons so the
ADP + P •-' ATP requirement would then be more than 8. The actual value is
for which the standard change in Gibbs function is difficult to measure but is thought {12) to lie between 8 and
12.
AGe' = 30.5 U niol- 1
The value of 8 can he used to calculate the maximum energy
It is known that half a mole of ATP is formed per mole of yield for the Z-scheme. The 8 photons at 700 nm provide an
electrons transferred and so it appears that less than half of equivalent energy of 1368 kJ mol~. The minimum work re-
the available work is used in this conversion. quired to reduce H2O and form NADP is given by
The synthesis of ATP presents a further problem in using 2H2O + 2NADP+ ••- 2NADPH + 2H+ + Oa
the electrode potential diagram: it is not a redox reaction and
so cannot be represented by electron transfer or by a standard
electrode potential and so cannot be shown by a level on the
diagram. for 4 electrons and so the maximum yield is 32%.
3) In photosystem I, the photoreceptor P700 reacts in an Some of the energy is used in the formation of ATP. The
electron-transfer reaction with the substance, X, remainder appears as heat, with losses occurring at every
stage: in the rapid vibrational relaxation in the excited singlet
• X M ) + hP — P700OS + X rsd state of chlorophyll, in the energy transfer to the reaction
center, and in all the various reactions which, because they
and the oxidized, P700O!1 reacts with the reduced plasto-
occur in an actual system, are subject to second law losses.
cyanin
There will also be substantial further losses in the Calvin
P700el - P70<W + PCOS Cycle.
Conclusion
so t h a t the overall process is electron transfer from PQ re d to
X r e i j. This article has outlined the use of electrode potential di-
The minimum work required i& agrams in a simple system, and in the Hill-Bendal! scheme for
photosynthesis, for which the diagram provides a basis for
understanding the mechanism.
=* + 96-5 kJ mol-i Emphasis has been placed (1) on the use of arrows to depict
electron transfer, with a rule to give the correct direction of
which is provided by the photon. the coupled reactions; (2) on the fact that the diagram is a
4) The final steps involve the reduction of NADP + and free-energy diagram and not an energy diagram, and (3) on
oxidation of X re a again through a sequence involving a ferri- the fact that the energy quantities corresponding to heights
doxin represent the maximum work available or the minimum work
required for particular processes.
XQ, + e~ It has been suggested that to help people less familiar with
+ e- — %NADPH these diagrams, the scales should be labelled as electrode
potentials and that each level should be shown as a redox re-
The work here is action rather than as a single substance.
While the mechanism has been described in outline, the
purpose has not been to give the experimental evidence or the
= -26.6 k.J mol"!. fine details which are well described elsewhere (1-3).
The process is spontaneous but the work available is not ap- The various conclusions could also be applied to the de-
parently used. scription of the cytochrome electron-transport scheme in
The mechanism has been described sequentially in a respiration (4).
chemist's way, but, in fact, all the reactants and products to- Addendum
gether with the enzymes which catalyse the reactions are part The referee has kindly pointed out a recent suggestion thai a
of a membrane in the chloropiast which absorbs light thus pheophytin (Phi acts as a further intermediate between P680 and Q
providing the energy for proton transfer through the mem- in photosystem II. Two measurements have indicated that electrode
brane. The protons are used to synthesize ATP. The NADPH potential for the reduction of the pheophytjn (e~ + Ph~ -* Ph) is
—§10 mV. The implication of these findings is that the presently ac-
produced is used in CO2 fixation. cepted mechanism, outlined in Figure 2, may need substantial revi-
sion. However, the conclusions of the present article are still valid
Quantum Requirement and Energy Yield since it is concerned with the interpretation of electrode potential
The diagram can be used to calculate the minimum quan- diagrams rather than with the detailed mechanism.
tum requirement and the maximum energy yield.
Literature Cited
To produce 1 mole of Oa and 2 moles of NADPH at an in- (1) Govindjee and Jursink, P. A., Pholochem- Photubiol. Rev. 4, lib (1979).
termediate stage and absorb 1 mole of CO2, 4 moles of elec- <Z) Araon.O. L,Proi;. NntLAead. So". <l.'.S.A).«8.288a (1971).
trons are required, and these must pass through the sequence (3) Liwine, R. P., Sd. Amer., f}8 (Dec. I960).
of reactions outlined. At the wavelength corresponding to the 141 Lehninger, A. L., "'Sh'irtOmrse wRiochemiss.ry," Word!, N&w York, 1375.
(3) MfGbshan.M. I,,, "Chemical Thertnutlynamics," Academic Press, London 1079.
threshold for photosynthetic activity <~700 nm) the energy ffi) Alliiiis, P. W., "Physical Chemistry," Oxford Press 1373.
absorbed (171 kJ mol""1) for each photon is more than suffi- 17) Weast, H. C, "Handbimk of Chemistry and Phjsics," Chem. Ruhhor Puhi. Co.,
cient to raise 1 electron in either photosystem. Much of the Cleveland. I97S.
(8) Dannal, C. W.. anrf EllinKham, H. •>• T., Disamt. Faraday Set, 4,526 (1948).
energy is lost in the initial steps by vibrational relaxation and (9) Hill. It,ami Bendall. P., Nature, 1S6, !3fi (1960).
by second law effects, but, if we assume that 1 photon per (10) Sober, H.," Handtookof Biwheroiatiy," Chan. Rubber Pub!. Co., Cleveland, 137fi.
(11) Calvert,.!. G., and Pitts, .1M., "Photochemistry," John Wiley. Now York, 1H66.
electron is required, then there is a minimum quantum re- (IS) Fong, P. K..J. Amer. Chem. Soc.38,7M0 (1976).
quirement of 8 for the passage of 4 electrons through the two (IS) Kulherford, A. W., Mullet, ,1. E.,ano1 Croft*, A. R., F.E.B.S. Letter*. 123, £35 (1981).
photosysteras. (H) Klimov, V. V.. AMaltverdiev. S. I., Denieter, 5.. and Krasnovakii, A. A., DokL Ahad,
Nauk. SSSft Wi<iiihyt.),2

The Prototype Compound for tho Oral Anticoagulants
3,3'-Methylene bis(4-hydroxycoumarin)
Rodney C. Hayward
School of Pharmacy, C.I.T., Private Bag, Trentham P.O., New Zealand
The coumarin anticoagulants provide illustrative, carb-

anion-mediated, bond-forming reactions and interesting
target heterocycles for the undergraduate laboratory. The
story of the introduction of the title bishydroxycoumarin
(Dieumarol, USP) (la, Pig. 1) into therapeutics is a particu-
larly interesting one {1). Dieumarol was established (2) as the
cause of the hemorrhagic sweet clover disease 1 in cattle fed (la) (Dicumarol, USP)
spoiled hay made from the sweet clovers, Melilotus alba or
M. officinalis. This compound provided the leading structure «b)R --H
for the family of oral anticoagulants shown in Figure 1. A series <Ic> E - -CH(Ph)CH,COCH3 (Warfarin, USP)
of similarly acidic 1,3-indandiones has been found to consti- <Id) R - -CH(Ph)CH,CH3 (Phenp roe oilman, USP)
tute an additional class of anticoagulants. (Ic) E = -CH(p-NO3Ph)CHsCOCH3 (Acetocouinarol)
Dicumarol was usefully introduced into medicine (4) to
lower blood coagulability in, for example, the treatment and
prophylaxis of thromboembolic disorders in veins and, to a
lesser extent, arteries. However, a slow onset of action and an
idiosyncratic variation in adsorption and metabolism made
dieumarol a lesa-than-ideal drag. Of the many analogues (e.g., (Ila) E = -H
(lib) R = -Ph (Phenindione, USP)
structures Ic-e) ultimately synthesized, the most useful has (lie) R = -CH 2 CH(Ph) s (Diphenadiane. USP)
been racemic warfarin 2 (1c) as its sodium salt (6). The high
activity of warfarin as an anticoagulant caused it to be origi-
nally proposed for rodent control. It became the world's most Figure 1. Structural families of Hie oral anticoagulants.
useful rodenti cide.
Pivotal to an open-ended synthetic laboratory schedule on
the coumarin anticoagulants 3 was a facile synthesis of 4-
hydroxycoumarin (Ib). The published strategies in this area
fall roughly into two categories: (1) condensation of a phenol
with a derivative of malonic acid (7), and (2) a carbanion-
mediated condensation effected in a phenoiic ester or ketone
(8). From the latter group, we have found that condensation
of o-hydroxyacetophenone with diethyl carbonate in the
presence of sodium hydride as a base {8d) to be an easily (la)
manipulated and high-yield reaction. The reaction could
conceivably proceed by either a /3-keto ester or alternatively
via the O-acyl derivative: cyclization will afford the same Figure 2. Reaction pathway producing Oicumarol.
product.
Dicumarol was simply prepared by condensation of the
4-hydroxycoumarin with aqueous formaldehyde solution (Fig.
2) (2). 4-Hydroxycoumarin and its derivatives have many of Experimental Procedure
the chemical properties of /i-keto esters. The reactions develop
in a straightforward way from ethyl acetoacetate. 4-Hydroxycoumarin {Ib)
A soSution of o-hydroxyacetophenone (0.022 mole) and diethyl
carbonate (0.055 moie)4 (Fumehood) in dry toluene (30 ml) ts added
dropwise over 20 mm to a stirred suspension of sodium hydride (0.033
1
The administration of vitamin K can reverse the dlcumarol-lnduced mole)s in dry toluene (30 ml) held in an oil bath maintained at 110°C.
hypoprothrombinemia. Anticoagulants such as the coumarin derivatives The ethanul formed during the reaction is removed by distillation.
are indirect in action, depressing Ihe hepatic vitamin-K-depenc jnt When ail the ethanol has been removed, the thick mixture is allowed
biosynthesis of prothrombin and other clotting factors. See, for example, U> cool and is extracted with water. The aqueous layer and washings
ret (3). are combined, treated with a iittie charcoaE, filtered, and the chilled
2 filtrate acidified by the dropwise addition of hydrochloric acid to
Warfarin is an acronym for the patent holder Wisconsin Alumni precipitate the product The product is filtered off, washed with cold
Research Foundation, plus the suffix derived from coumarin (5). water and sucked as dry as possible. It is recrystallized from 50%
3
For example, warfarin can be synthesized by a Michael addition aqueous ethanoi to give the product in 90-91% yield (two crops) as
of the 4-hydroxycoumarin enoiate anion to (£H-prienyi-3-t>uten-2-one needles, m.p. 2!3-2I4°C (ref. 10): ra.p. 21.3-2I4°C).
(benzalacetone).
4
Purified for procedure see ref. (9).
6
The sodium hydride was used as a 50% dispersion in oil and as
3,3'-Methylene bis{4-hydroxycoumarin) {la)
such is an easy-to-use, powerful base. Safety In using sodium hydride 4-Hydroxycoumarin (1-0 g) is dissolved in boiling water (300 ml).
must be emphasized. Provided that normal care Is taken and all ap- The solution is allowed to cool to 70°C and 40% aqueous formaldehyde
paratus is dry, use of an inert atmosphere for weighing the dispersion solution (10 ml) (Fumehood) quickiy added with stirring. The mix-
or for the subsequent reaction is not necessary. Any dispersion adhering ture is then chilled, the crude product filtered off and washed well with
to spatulas, etc., can be safely destroyed by submerging them in ab- water, dried and recrystallized from eyclohexanone/toluene as prisms,
solute ethanol. 0.89g (85.8%), m.p. 292-295°C (ref. II): m.p. 287-293°C>.

Literature Cited and Shah. R. C., J. Org. C/uro., 2S 677 |I960); Gordon, J. p.. Hayes, N. 1'., and
Thomson, R. H., J. Chem. Sot-., 3315 (1956).
(1) tink1K.P,CiircufBtisR, 19,97 (1959); Hunwy Lect. Ser., 39,162 (1943-44). (8) (al Pauly, H., and I.ockemann, K,. Chem. her., 40, Si (1915); (b| Bojd. J,, RoberlsaD,
<2i Stahraann, M. A., Huebner, C. F., and Link, K. P., J. Biol. Ch™., 138,613 (1941). A., and Whaliey, W. B., J. Chem. Sot, 174 (1948); (c) Dickenson, H., U.S. Patent
(3) Silvercnan, R. B., •]. Amer. Chem. Sot, 103,3910 (1881). 2,449,162 (INS); Chem. Absir., 43,694. id) Abbott Laboratories British Patent
(4) Bult, H. R., Alien, E. V.. ami Bollman, J. L., Mayo Clinic Prtx., 16,388 (1941). 70S.31B (1954); Chem. Abstr.. 30, 1086d.
(5) Ikana, M., Stahmaon, M. A., and Link. K. P., J. Amer. Chem. Sue., 6S, 902 (1944). (9) Voge], A, L, "A TextJjoofc of Practical Organic Chemistry," 4lii ed., Longman, Inc^ New
(6> O'Reilly, R. A., in 'The PharmanJogksi Basis of Therapeutics." 6th ed. Oilman, A. Yoik, 1978, p, 372.
G., Goodman, L. S., and Giimsn, A. {Editors), Mecmillan, New York, 1980. (10) "CRC Handbook of Chemistry and Physks," 59th Ed., CRC Press 1977-78.
(?) Ziegler, E., and Junek, H., Mcnatsh Chem., 86,2B JI955I; Mentaet.C, Vercier.P., (11) "The Merck Index." 9th ed., Merck & Co., Railway, NJ, tOTS.
Beaudet. C, and Ville. A., Bull. Soc. Chin. Fr., 480 (1957); Shah, V. S., Hose, J. L,,
Southeast edited by
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NEW YORK ACADEMY OF SCIENCES CONFERENCE ON MACRO- THE 83RD 2YC3 CONFERENCE at (he SI. Louis Community College
MOLECULES AS DRUGS AND AS CARRIERS FOR BIOLOGICALLY at Florissant Valley, 3400 Pafshall Road, Si, Louis, MO 63135, in
ACTIVE MATERIALS to be held at the Roosevelt Hotel, New York, conjunction with the 187th ACS National Meeting April 8-13,
NY. 1984.
To be presented by David A Tirrell. Carnegie-Melton University and L. Theme: "Chemistry Instruction: Content, Strategies and Materials".
Guy Donaruma, Polytechnic Institute of Hew York. For further information, contact: Ralph Burns, St. Louis Community Col-
Fof further information, contact Ellen A. Marks, New York Academy o l lege, Meramec, 11333 BiQ Bend Blvd., St. Louis, MO 63132, (314) 966-
Sciences, 2 East 63rd Street, New York, NY 10021. 7718.

April 8-13, 1984 TEACHER WORKSHOPS sponsored by the Colorado
187TH ACS NATIONAL MEETING, St. Lotils, MO. ACS Section, Regis College, Room 312 Science
Topics include: Bfdg., Denver, CO 80221. 8:00 A.M.-5:00 P.M.
• State-oMhe-Art for Chemical Educators IX: Chemical Education for the
BO's. George Bodner. Invited Papers Only, February 4,19a 4
• Industrial Applications of Genetic Engineering, j . Fayerman, Eli Lilly S A.M. Crystallography
Co. P.M. Problem Solving and Sharing
• Research in Chemical Education. Rick Stetner, Dept. of Chemistry,
University of Utah. Speaker R. D. Witters, Colorado Schoot of Mines, GoMen, CO
• Cosmochemislry. Michael Lipschutz. Dept. of Chemistry, Purdue Uni- March 3,19S4
versity.
• Workshop on the Use of the Microscope in the Chemistry Laboratory. Metallurgy—to be heW at Hill Hat), Colorado Schoot of Mines.
W. McCrone. McCrone Research Institute. Speaker: Dr. Copland and Staff, Colorado School of Mines, Golden. CO
• Breakthrough Lecture. "Research in Chemical Education." Alex John-
April 7, 1984
stone, Dept. of Chemistry, University of Glasgow, Scotland.
For further Information on the ACS National Meeting contact: George Descriptive Chemistry of Metals
Bodner, Meeting Chair, Dept. of Chemistry, Purdue University, West La-
fayette, 9* 47907, (317) 494-5313. May S, 1984
Descriptive Chemistry of Nonmetals
April 9, 1984 For further information, contact: Evelyn Bank, Chairman of the Colorado
ACS Section, Westminster, CO 80030, (303) 428-9541 Ext. 243 or |303|
"HIGH SCHOOL DAY" AT THE ACS NATIONAL MEETING, St. Louis, 424-3162.
MO.
Theme: "Curriculum Developments—Dreyfus Institutes 1982 and WEDNESDAY AFTERNOON LECTURES being held at
1983".
For further Information, contact: Kathleen J. Oombrink, McCluer North California Institute of Technology, 3rd floor, Baxter
High School, 705 Waiertord Drive, Florissant, MO 63Q33, (314] 595- Hall, Pasadena, CA
2300. These leclures begin at 3:30 P.M. and are free for secondary school stu-
dents and teachers. They are as follows:
March 7, 1984
Southcentral edited by
Very Large Scale Integrated Circuits—Technical & Design
JAN HARRIS
Cypress-Fairbanks High School Speaker: R. E. Bryant, Asst. Professor of Computer Design, California in-
Houston, TX 77064 Stitute Of Technology.
March 2-3, 1984 April 4, 1984
S2ND TWO-YEAR COLLEGE CONFERENCE, Tarrant County Junior The Crack: the Most Expensive "Nothing"
College, Northeast Campus, Hurst, TX 76053. Speaker: W. T. Krtauss, Professor of Aeronautics 8 Applied Mechanics.
For further information, see the December 19S3 issue of THIS JOURNAL.
May 2, 1984
The Atomic Nucleus: Quantum Physics on a Grand Scale
edited by Speaker: S. C. Koonln, Professor of Theoretical Physics.
Southwest
ERIC STREITBERGER For further Information on the above lectures, contact t e e f. Browne, or
University of California-Fulierton Phyllis Brewater, California institute of Technology, Pasadena. CA
Fullerton, CA 96231 91125,(213)356-6624.
February 18-19, 1984 SUMMER 1984

MID-WINTER MEETING OF THE NATIONAL ASSOCIATION OF EDUCATIONAL BRIDGES TO OPTIONS IN HIGH TECHNOLOGY EM-
CHEMISTRY TEACHERS, California Polytechnical Institute San Lute PLOYMENT at San Diego State University, San Dtego, CA
Obispo, CA. For furtiier information see the December 1983 issue of THIS JOURNAL.
Program includes water pollution, chemical safety In the academic
classroom and cooperative education programs between chemistry and March 24, 1984
industry. CALIFORNIA STATE TEACHERS ASSOCIATION SPRING CONFER-
For further information, contact: Rod Oksen, Northern Section of the Caf- ENCE, Redding, CA
Ifomla Association of Chamistry Teachers (CACTI, Dept. of Chemistry, For further information, contact this editor.
San Jose City Coitege, 2100 Moore Park Avenue, San Jose, CA9521S.
LETTER;
electric field intensity or strength and not battery voltage
which was being described. In the experimental portion of this
paper, Millikan describes the distance between the parallel
plates as 1.600 cm. A simple calculation shows that the battery
voltage was much greater than 8000 V. (SI units are used.)
Clearing-up Misconceptions about Millikan's Oil Drop 8000 V

- X 1.600 X 10"2 m = 12,800 V
Experiment 1.000 X 10-s m
To the Editor: If 12,800 V potential difference is placed across 1.600 X 10~ 2
m, we obtain the maximum electric field strength, 8000 V/cm
I wish to correct some misconceptions incorporated in t h e or 8 X 10 5 V/m. Millikan used a voltage divider-to bring his
article entitled, "Some Misunderstandings about Miilikan's lowest electric field intensity to 3000 V/cm or 3 X 10 s V/m. A
Oil Drop Experiment," Castellion, M. E. and Bailar, Jr,, J. C , similar calculation shows t h a t at the lowest electric field in-
J. CHEM. EDUC-, 59,970 (1982). tensity, the voltage divider had reduced the o u t p u t voltage
It is stated t h a t the parallel plates in Millikan's experiment to 4,800 V (Harris, S. P., J. CHEM. E D U C , 59,988 (1982)).
were charged 3000-8000 V but usually close to 8000 V. Ex- A further quotation from the same sentence used previously
amination of the article, Millikan, R. A., Physical Review, 32, follows: "if the droplet had received a fractional charge of the
349 (1911) shows t h a t Millikan stated "an electrical field proper sign and strength as it was blown out from t h e atom-
strength between 3000 V and 8000 V per cm is created between izer, it is puiled up by this field against gravity, toward t h e
the plates by means of battery, B . " This shows t h a t it was upper plate." Evidently, the charge was fractional in origin.

A charge cannot be produced from the electric field. CHO
There is a uniform electric field between the parallel plates -OR R
except at the edges. The electric force, Fe, is directly propor-
tional to the electric field intensity, t, and to the charge, q, on OK- -H S
the oil drop. H— -OH R
£\ = qt (l) -OH
Everywhere between the charged and parallel plates, the CHOjH
electric field intensity is the same, a maximum of 8 x 105 V/m Before incorporating the above adjunct method into a dis-
OT 8 X 105 nt/coulomb. Within this uniform field, the charged cussion of stereochemistry, it is besttopresent the traditional
body moves with uniformly accelerated motion toward the three dimensional representations for chiral molecules. The
plate having an opposite sign. The net force accelerating the required restrictions for using the planar Fischer projection
charged oil drop is the difference between Fe, the electric force formula also should be stressed.
and the gravitational force, on the oil drop, F%.
1
Millikan states that the frictionaliy charged oil drops were 2 Idoux, J. P., J. CHEM. EDUC, 59,553 (1982).
blown out of the atomizer and fall into the viewing chamber. Natta, G.. Farina, M., "Stereochemistry," Harper and Row, New
At the same time he states that the parallel plates are short- York, 1972, pp. 241-242.
circuited by means of a switeh, S. The oil drop is timed in its Justin W. Dieht
fall. Following this procedure, the electric field is switehed on St. Bonauenture University
and the rate at which the droplet moves upward under the St. Bonaventure, NV 14778
influence of the electric field is timed for the same distance
between two cross hairs. If the droplet meets an ion, the speed To the Editor:
of travel between the two cross hairs is increased. Milltkan was
able to calculate from this kind of experiment "the sign and In the July 1982 issue of the JOURNAL, John P. Idoux wrote
exact value of the charge carried by the captured ion." an article, "A Simple Method for Specifying the R / S Config-
Sometimes, Millikan produced ions in the viewing chamber uration about a Chiral Center," in which he outlines a proce-
"by any of the usual ionizing agents like radium or x-rays." dure for identifying the R/S configuration of a chiral center
Millikan observed some drops for periods as long as an hour via Fisher projection. He also suggests that this method has
by utilizing a switch to reverse the polarity of the parallel not been presented in undergraduate organic texts or chemical
plates. education journals.
However, Carl R. Johnson has written and published a
Millikan realized that his results were "limited in accuracy book, "Organic Nomenclature: A Programmed Study Guide,"
only by that attainable in the measurement of the coefficient Worth Publishers, Inc., 1976, devoting almost an entire
of viscosity of air." The error in air viscosity was eventually chapter to finding the R/S configuration of a chiral center
shown to be the cause of the 2.50% error in Millikan's mea- using Fisher projections. I have been using his manual in un-
surements. dergraduate organic chemistry for several years.
Sidney P. Harris
Queens College Louis Mllakofsky
Flushing. NY 11367
Pennsylvania State University-Beiks Campus
Reading, PA 19608
To the Editor:
Specification of R/S in a Muiiichiral Molecule Two communications have appeared [J. CHJ5M. EDUC., 56,
To the Editor: 451 (1979), 57, 528 (1980); Biochem. Educ, 8,105 (1980)] in
which simple ways to relate R, S stereochemical designations
The recent note 1 describing the specification of R or S to to Fischer projections were presented. Any system, simple or
a chiral molecule by an even number of group exchanges be- complex, cannot be used successfully to relate the R, S des-
comes extremely difficult for a multichiral molecule. Since an ignations to Fischer projections if an incorrect two-dimen-
odd number of interchanges is equivalent to inversion, 2 the sional projection is made of the three-dimensional model of
following method might be useful regardless of the number the structure [Appendix 2, IUPAC Tentative Rules for the
of involved chiral centers. Nomenclature of Organic Chemistry, Section E. Fundamental
Stereochemistry, J. Org. Chem., 35,2849 (1970)). These Rules
1) If the Fischer projection formula has the lowest priority (Section E-7.1) point out that one cannot rotate a Fischer
group, generally hydrogen, to the top or bottom, then projection 90° in the plane without changing the projection
R or S is specified in the usual manner. For example, of the vertical bonds to in front of the plane. In many bio-
chemistry textbooks the standard projection rules are not
COOH being applied to the amino acids, but are being used as if the
rotated vertical bonds project forward. T h e amino acid in
H Dietzel's note {.}. CHEM. E D U C , 56,451 (1979)1 is indeed (R),
but is frequently assumed to be L(S)—see below. This as-
2) I f t h e F i s c h e r p r o j e c t i o n f o r m u l a h a s t h e h y d r o g e n t o t h e sumption is only acceptable when it is clearly stated that it is
left o r t o t h e r i g h t , t h e n t h e R o r S is d e t e r m i n e d a n d being used [Biochem. Educ. ,2,76 (1974)].
then inverted. For example,
!
NH, 'S{H,
\ ! v
I — CO,H ss 'CHj- - -C- - -5CO5H
S
OH original inverted and now H5N—C—H 1 A
correct confisura-
CIHs H H
tional assignment
S -alanine
For a multichiral molecule, each chiral center can be quickly
I. -alanine
John N. Aronson
and correctly assigned without the possible confusion asso- State University of New York at Atbany
ciated with the switching of groups. For example, Albany, NV 12222

BOOK REVIEW
Genera), Organic and Biological The authors fulfil! very well their stated measurements yield numbers with dimen-
Chemistry: Foundations of Life goals of presenting the principles of chemis- sions. The dimension is given with the num-
try and relating them to life. This reader ber. Examples: 6 feet, In addition and
Dorothy M. Feigiand John W. Hill, Burgess found the text clearly written with good subtraction all numbers must have the same
Publishing Company, .Minneapolis, MN, content at the eicroentary level. The text is dimensions and the result will have this di-
1983. xiv + 383. Figs, and tables. 19.5 X highly recommended for consideration for mension. Example: You cannot add !6 grams
24.5 cm. $21.95. those desiring an elementary text, designed to 2 ounces without converting one quantity
for one semester that presents the principles to the other." The authors are confusing di-
"General, Organic, Biological Chemis- of general, organic, and biological chemistry mensions and units. Measurement is an op-
try— Foundations of Life" by Dorothy Fiegi with applications to life. eration of comparison; thus, 6 feet ia the re-
and John Hill is a text designed to introduce suit of a measurement of length in which the
J. L. Kirsch unit of comparison is the foot; 16 grams and
the student to elementary chemistry and to
Butler University 2 ounces are quantities having the same di-
relate the chemistry to living, life, and the real
Indianapolis, JN 46208 mension and therefore the masses may be
world.
expressed in ihe some unit.
The text starts with a chapter on matter
and measurements. The next seven chapters On page 40, paragraph 2, it is stated that
cover the general chemistry bioek of material: "Atoms of the elements combine with each
atomic structure, chemical bonding, nuclear other and themselves in definite combina-
processes, gases, chemical reactions, solutions called compounds. .. . Chlorine com-
tions, and acid-base chemistry. Chapters nine bines with itself forming molecules of chlo-
through thirteen discuss the structure, the The Elements of Style in Chemistry, A rine, Cla-" When two atoms of the same ele-
nomenclature, the physical properties, and Computer-assisted Instruction ment unite to form molecules the product is
the chemistry of the different classes of or- not a compound! In paragraphs 4 and 5, re-
ganic compounds. The final five chapters Supported Text spectively, on page 40 one reads "the atomic
cover the topics of carbohydrates, lipids, James W. Beatty, and James J, Beatty, mass of an element is the mass of the element
amino acids, proteins, nucleic acids, vitamins, University Press of America, Lanham, MD, relative to the other elements. .. the atomic
minerals, and hormones. 1982. v + 104 pp. Figs, and tables. 13.5 X mass is the mass of one atom of the element"
20.5 cm. $7.25 PB. "In laboratory units, the atomic weight is the
The elementary level of the text is the re- weight in grams of the same number of atoms
sult of the size of the text, three hundred as there are in 12.000 grams of the isotope of
fifty-three pages, compared to the large According to the preface, "The book is carbon mass 12." These statements are not
number and variety of topics covered. The the text for a two-hour course entitled "Pre- good enough; the atomic weight of an ele-
material is covered in a complete but de- requisites for Chemistry." The course is in- ment, or better, the relative atomic mass of
scriptive manner with an emphasis on its tended for students who, because of prior an element is a dimensionless quantity. The
application to practical and real problems. experience or iack of experience in problem actual mass of an individual atom, however,
This interface between the basic chemistry solving, have difficulty in solving problems is expressed in terms of the atomic mass unit,
and the real world is enhanced by the use of which are important to survival and satis- u, and by definition of the latter, the average
numerous well-chosen pictures, excellent factory performance in an introductory mass of the atoms of an element in atomic
figures and diagrams, and tables of relevant course." mass units is numerically equal to the reia-
data. A series of clever cartoons is used Given the purpose of the book and the tive mass of those atoms; i.e., their atomic
throughout the text to help the student audience to which it is directed, quality of weight. At thii top of page 21 is the statement,
visualize and clarify chemical concepts. content is important; yet lack of quality is one "one mo3e of a compound is defined as one
The following selected topics represent- the of the major failings of this book. This lack of molecular weight of a compound." This will
manner in which the authors integrate the quality is exhibited by statements that are come as a surprise to IUPAC. There is no
real world and the basic principles of chem- either unclear, confusing, or just plain in- reason why beginning students of chemistry
istry: nuclear medicine, respiration and par- correct. Because of limitations of space, it is should not be taught that mole ia the amount
tial pressure, oxidation and antiseptics, blood not possible to go into full detail to support
and pH, polymers, physiological properties this assertion and so attention is called to the
of alcohols and amines, digestion and carbo- following examples which are chosen at ran-
hydrates, and digestion and proteins. dom. On page 26 one reads that "Physical (Continued on page A2S)
-Reviewed in this Issue-

Reviewer
DorothyM. Feigland John W. Hill, General, Organic and Biological Chemistry:
Foundation of Life J. L. Kirsch A27
James W. Beatty and James J. Beatty, The Elements of Style in Chemistry: A
Computer-Assisted instruction Supported Text Victor A. Crawford A27
Arthur M. Lesk, Introduction to Physical Chemistry Dewey K. Carpenter A28
Robin K. Harris, Nuclear Magnetic Resonance Spectroscopy Nancy S. True A28
Titles of Interest A29

BOOK REVIEW; convincingly and non-trivjaily, and I fear that
frequently only mature students will be able
to follow him. A case in point is the way in
sented in accompanying problems. Each
chapter contains excellent illustrations,
useful tables, up-to-date specific and general
osyfsetm subsatn t
h caet S (cootn
m
ftan i esngea,sn im G ermaen ) eonfatrya
which such a large number of topics (e.g.,
any l
m
solids, liquids, gases, phase transitions,
references and problems of varying difficulty.
The chapter sequence is somewhat arbitrary;
eofnticeasrboans. W theree adroe n carobtondoaotm st

u dsennits a0.12servk
thermodynamics, quantum mechanics, and
c
igif
e
statistical mechanics) are introduced in an
. for example, chemical shifts and coupling
constants are discussed in the final chapter
w
m eutsteachhehtem u nel
a ru
nfedndam o
r enareitled ieasO
arned. th
n atpalagteer65
overview of physical chemistry in chapters 2
and 3, As a book for graduate students re-
although this material logically follows topics
covered in the introductory chapters.
ooithn neep lam sm thoae"l.t "W h

tehatN O
aisHmh ans,toofnylcou onrese,OH~
viewing the subject these chapters will be
atN e
r
thaOerH
e.isSotocih noeimm oel iosf O e
Ha ~esoiennstailper moel
they will probably bewilder. i
s
very helpful; as a first exposure to neophytes
Basic principles, spectral analysis of iso-
tropic systems, chemical shifts and coupling
o
ccoom f ponen tdofaacnelyarb er
ty engnin a n
nisatgndnigchem srtiythe con-
There are other problems with the orga-
constants are thoroughly covered at a level
appropriate for the advanced undergraduate
u rse an u d er of
nization. (1) If the statistical mechanics of student who has some prior exposure to basic
acm oetmpts,am otm cciualrww egihegtihtororreraletvialetviem asasofofan

ideal gases is treated before quantum me- principles of quantum mechanics. The
o e
lc u e
l, a o
oe
tl m ci m as, m o
e l
cual
r m m
a s, a
nd a
chanics, there are too many formulas for ei-
genvalues which must be pulled out of the
mathematical level is elementary and density
matrix formalism ia not utilized. For example,
m
ceT soehlen iisexsacom rvlun icgap
il foprrobelu fmrh
tse.r su tdy and ofr suc-
hat. (2) A more serious matter concerns the
division of thermodynamics into two blocks
of material. After a conventional introduction
t h e chapter on analysis of complex spectra
begins with a discussion of operator algebra
and proceeds through the formulation and
c"om ni g s ni a eslbogk vienwhaoresepserreoaficuescalm sihosrt-that

to thermodynamics and some of its applica-
tions, there is an intrusion of eight chapters
solution of spin matrices for complex coupled
systems. Time-dependent perturbation
m exp a erresincetheshom
s
e
t wsaetraith l an
t ththesi sltu
i it d
tle entbokwhogoes
before thermodynamics is applied in chapters
15,16, and 17 to real gases, binary solutions,
theory and selection rules appear in an ap-
pendix.
niceitn oceis" c.oelgeGviecnhem t

hsrtiye w p uh
tirp
ou t seorfoiuth sedebf-iook,
and Galvanic cells, respectively. This will
o se
present a problem to those of us who prefer
Relaxation measurements and mecha-
b
a n ascim i copnecceapbystl m c
o rur tsctbemastn
e an eld
er
, a nced
larylthsiandthen
before moving on to molecular phenomena i
to treat thermodynamics and its applications
nisms, multiple-pulse experiments, double
resonance, spin decoupling, the nuclear Ov-
auuseh tfuolrspuhrapvoesefatheliadt ctooudldob,eIserdvoednobtysetehsiany

because chapters 15, 16, and 17 utilize ma-
terial from the intervening chapters and
erhauser effect, and Fourier transform tech-
niques are discussed in detail in early chap-
text and 1 cannot recommend it. Victor A. Crawford

chapter 17 also contains non-therraodynamic
topics; e.g., conductance.
Although the exposition is generally very
ters in the book. Time domain spectroscopy
is emphasized not only for its signal en-
hancement capability but also for the struc-
tural and dynamical information multiple
clear, Lesk occasionally falters in defining pulse sequence experiments can provide. The
Rockford Coliege latter is an especially unique and important
Rockfora. IL 61101
basic quantities; e.g., although the First Law
is clearly stated and expertly applied, I find feature of the text. Spin echoes and selective
the definitions of work, heat, and tempera- pulso sequences are discussed with emphasis
Introduction to Physical Chemistry on I N E P T experiments and heteronuclear
ture to be somewhat vague.
Arthur M, Lesk, Prentice-Hali Inc., Engle- and homonuciear 2D J-resolved spectros-
At the beginning of each chapter "learning
wood Cliffs, 14), 1982. vii + 746 pp. Figs, copy.
goals" are stated and a study guide is pro-
and tabies. 18 X 24 cm. $38.95 HB. vided which gives a good summary of the A chapter combining material on chemical
Here is a fine treatment of all the main chapter. exchange and quadrupolar effects is also in-
topics of physical chemistry. The writing is On balance, there is more good than bad cluded and its coverage is greatly expanded
ciear, the illustrations are appropriate, and here. I would expect the book to be most from the earlier book. Topics include line-
the problems are excellent. It would be a successful in situations where the majority of shapes for uncoupled equally populated site
sensible choice as a text for use with well- the students are highly motivated. If there exchange, exchange rates from spin-lattice
prepared and motivated students. It suffers were such a thing as a second-level course in relaxation and saturation transfer, as well as
from some organinational peculiarities, oc- physical chemistry, this would be a good text exchange involving paramagnetic species.
casional haziness regarding definitions, and to use. Effects of coupling of spin % nuclei to quad-
a level of exposition which demands a Sevei of rupolar nuclei are discussed.
Dswey K. Carpenter
physical insight which is unfortunately not The author has included a thorough and
Louisiana State University
common in undergraduates. timely discussion of NMR of solids including
Baton Rouge,-LA 70803
To elaborate on these remarks, consider magic angle rotation, a discussion of second
first the really good things. Lesk shows a Nuclear Magnetic Resonance moment effects, motional effects on relaxa-
concern both for overall perspective and for tion time, cross polarization, shielding an-
Spectroscopy isotropy, obtaining high resolution NMR
attention to details. Throughout the book
there is no mathematical pedantjy, and there Robin K. Harris, Pitman Publishing Inc., spectra in the solid state including CP/MAR
are many fine examples of clear explanation Marshfield, MA, 1983. xx + 250. Figs, and techniques. In contrast, applications of NMR
which do not allow the distance between tables. 19 X 24. $34.95. spectroscopy to gases is completely omitted.
theory and experiment to become very great. Other areas not covered include biological
Robin K. Harris has written a physically applications, CIDNP, spin imaging and re-
Among these are the chapters on applications oriented introductory NMR text directed
of thermodynamics, statistical mechanics, lated topics.
toward the advanced undergraduate and
solids, X-ray crystallography, the fluid state, beginning graduate student which should also Although this test would be most suitable
and electrochemistry. Topics are treated prove useful for chemists who use NMR as a for an undergraduate special topics course in
thoroughly and amply illustrated by nu- structural tool. The organization of this ex- NMR spectroscopy most chemistry depart-
merical examples, figures, and tables. The use cellent book reflects the increased experiments in the U.S. do not provide such a
of actual literature data in the latter as well mental emphasis on time domain NMR course and a special strength of this book is
as in many problems is to be commended. spectroscopy which has occurred over the last its amenability to self-directed study. The
There are several places in the book where decade while retaining the principal features author's style is concise and clear. The book's
important compilations of data and bibliog- of an earlier text by the same author ("Nu- contents allow interested individuals to
raphies are presented; e.g., in chapters 1,6, clear Magnetic Resonance Spectroscopy" by master the basic principles of NMR spec-
14, and 17. No other physical chemistry test R. Lynden-Bcli and R. K. Harris, Thomas troscopy and gain an appreciation of the
does as good a job in relating itself to the Nelson and Sons, Ltd., 1969). present capabilities of this powerful tech-
chemical literature. The book rewards close nique, and extensive references and a bibli-
attention with numerous new ways of think- Material is presented in eight largely aelf- ography provide direction for further study
ing about familiar topics. containing chapters preceded by a complete in specific areas.
symbol and abbreviation list which facilitates
This leads to some critical observations. easy reference. Emphasis is on theoretical Nancy S. True
Although the mathematical level is low, t i e aspects with many practical applications University of California
conceptual level is not. Lesk argues his case discussed with the aid of figures and pre- Davis, CA 95616

Titles of Interest Baum, H. Ito, and G. S. Roth; Microscopic
Localization of Adrenoceptors, J. M. Palacios
and J. K. Wamsley, C a p t u r e a
Monographs
T e a c h e r
Advances in Physical Chemistry: Biosynthesis of Indote Alkaloids
Current Developments in Atta-ur-flahman and Anwer Basha, Oxford a n d y o u
Electrochemistry and Corrosion University Press, New York, NY, 19S3. 0
+ 270 pp. Figs, and tables. 16 X 24 cm.
Ya. M. Kolotyrkin (Editor), Mir PubHshers, $49.00.
Moscow, Russia, 1982. 0 + 191 pp. Figs, c a p t u r e a
and tables. 14 X 21.5 cm. $6.45.
G e n e r a t i o n
Chemistry and Technology of Water-
Soluble Polymers T h e half-biilion dollar a c a d e m -
ic m a r k e t for scientific p r o d u c t s
Adrenoceptors & Catecholamine C. A. Finch (Editor), Plenum Publishing
is c o m p o s e d of p r o f e s s o r s w h o
Action, Part B Corporation, New York, NY, 1983. xvl +
358 pp. Figs, and tables. 17 X 25.5 cm. t e a c h , w h o b u y in v o l u m e , a n d w h o
George Kunos (Editor), John Wiley & Sons, read...
Somerset, NJ, 1983. vii + 327 pp. Figs, $55.00.
and labies. 16.5 X 24 cm. $75-00.
List of contents and contributors: Struc- Chemisiry of Pesticides

ture-Activity Relationships of Aipha-Adre- K. H. Buchel (Editor), John Wiley & Sons,
noceptor Agonists, E. R. Ruffoki, Ji.; Phos- Somerset. NJ, 1983. xii + 518 pp. Figs,
phalidyimosilol Metabolism and a-adreno- and labies. 17 X 24 cm. $90.00.
ceptor Mechanisms, ,1. W. Putney, Jr.; Re-
lease-Modulating Adrenoceptors, E. S. Vizi;
Adrenergic-Cholmerglc Interactions, W. R.
Roe6ke and H. I. Yamamura; Adrenoceptors
The interpretation of Analytical
in Skeletal Muscle, I, W. Rodger and W. C-
Bowman; Adrenergic Influence on Peripheral Chemical Data by the Use of Cluster
Hormone Secretion, J. B. Young and L. Analysis
Landsberg; Adrenoceptors and Centra! D. Luc Massart and Leonard Kaufman,
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JANUAR11984

Gilbert Newlon Lewis

THE AMERICAN CHEMICAL SOCIETY

—Forrest C. Hentz, Jr., Ph.D.

BRING YOUR STUDENTS FACE-TO-FACE WITH

Donald McQuarrie and Peter Rock

Assistant Editor: JOURflflL OF

SECONDARY SCHOOL EDITOR

Secondary School Chemistry

A4 Journal of Chemical Education

Brady & Hof urn's FUNDAMENTALS OF CHEMISTRY,

A Better How of Topits

Circle No. 15 on Readers' Inquiry Card

Volume 61 Number 1 January 1984 A5

A6 Journal of Chemical Education

Volume 61 Number 1 January 1984 A7

INDEX TO ADVERTISERS IN THIS ISSUE

18 Brinkmann Instruments OBC xx Spectrex Corporation A30

Flamm Advertising, Inc. CENTCOM, LTD.

xx Klinger Educational Products Corp A30 ADVERTISING PRODUCTION MANAGER

A8 Journal of Chemical Education

Carolina Biological Supply company

Cfrefe Mo. 3 on Headers' Inquiry Card

Bgenenergies ol Methyl Fluoride

Circle ND. 21 on Readers' Inquiry Card

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Circle No, 1 on Readers' Inquiry Card

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A14 journal of Chemical Education

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"Mortimer's texts have all been good,

758pages. 8x10. Casebound. gogy you'll find i n t h i s careful revision o f a p o p u l a r text.

S t u d e n t S e l f - S t u d y G u i d e . S o l u t i o n s M a n u a l . A n s w e r B o o k l e t . Test- 656pages. 7%x9'A Casebound. Study G u i d e Solutions Manual.

For m o r e information o n t h e s e texts, write: Jack Carey, C h e m i s t r y Editor, B o x JCE-184:

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Volume 61 Number 1 January 1884 A15

A rugged and highly retentive dual-purpose

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A16 Journal of Chemical Education

P a r r 1 4 5 1 editor> ba/ket 6-page report on the )L FAST AC (I autosam-

The Binos Infrared Gaa Analyzer makes pre-

A18 Journal of Chemical Education

For adoption consideration, request an examination package from your regional

p H E L E C T R O D E Circle #51 on Reactors' Inquiry Card

UV-Vis Absorbance Delector

U 6fil Seaboaid Circle

A20 Journal of Chemical Education

A22 Journal of Chemical Education

I n t r o d u c i n g organic compounds which were Like its popular print equiv-

Index Chemicus® Online:

. . . the first in a series of

Chemical Information Divi-

sion (ISfiCID). The initial

structure data-base will be

available online in early 1984

through Questel, using the