CHEM 123

Winter Term 2004

Intermolecular forces, Chemical Kinetics, Equilibrium, and Electrochemistry

Course (Section, class #) Lecture Time & Room Instructor (Office, Extension and e-mail address)
CHEM 123 (001, #3757) 8:30 am MWF in DC 1350 C. Chieh (C2-263, ext. 5816, cchieh@scimail)
CHEM 123 (002, #3758) 9:30 am MWF in DC 1350 M. Barra (C2-380, ext. 5948, mbarra@scimail)
CHEM 123 (003, #3759) 1:30 pm MWF in DC 1350 K. Walker (C2-065, ext. 6517, kwalker@acebox)
P. Sheridan (DC-2602, ext. 6066, psheridan@acebox)
CHEM 123 (004, #4514) 10:30 am MWF in AL 116 G. Dmitrienko (ESC-343, ext. 6296, dmitrien@muskie)
CHEM 123 (005, #4787) 11:30 am MWF in MC 2066 C. Bissonnette (C2-274, ext. 2434, cbissonn@scimail)
CHEM 125 (001, #3668) 12:30 pm MWF in DC 1350 C. Bissonnette (C2-274, ext.2434, cbissonn@scimail)
(Note: CHEM 125 is an enriched version of CHEM 123.)
When sending e-mail to your instructor from a
Course Coordinator: C. Bissonnette (C2-274, ext. 2434, cbissonn@scimail) computer off-campus, add “.uwaterloo.ca” to
Lab Coordinator: H. Flatt (ESC 149, ext. 3868, hwflatt@scimail) the e-mail address given above.

Text: R.H. Petrucci, W.S. Harwood and F.G. Herring, General Chemistry (Principles and Modern Applications),
Prentice Hall, Eighth Edition, 2002. The text comes with a full Solutions Manual. Several copies of the text and
the solutions manual have been placed on Reserve in the Davis Centre Library. Use the call numbers UWD 1532
(for the text) and UWD 1534 (for the solutions manual).

Approximate
Chapter Topic(s) # of Lectures Comments
13 Liquids, Solids and 6 You will not be expected to remember or use the
Intermolecular Forces equation n  2 d sin  .
15 Chemical Kinetics 6 The integrated rate laws will always be provided
on all tests and exams. Learn how to use them.
16 Chemical Equilibrium (including the 4 The Van’t Hoff equation will always be provided.
Van’t Hoff equation – see page 7.) Learn how to use this equation.
17 Acids and Bases 5
18 Acid-Base Equilibria 4
19 Solubility and Complex Ion Equilibria 4 You are not responsible for section 19-9.
21 Electrochemistry 5 Ignore Gibbs free energy aspects in Chapter 21. You
are not responsible for memorizing any of the half-
reactions in sections 21-5, 21-6 or 21-8.
During lectures, your instructor will focus on topics that require the most explanation. He/she cannot devote time to all topics
discussed in the text. However, you are responsible for all of the material in the text (plus the additional material on page 7 of
this handout) unless your instructor indicates otherwise. You are expected to learn much of the material on your own. To
help you plan your time, a list of homework problems is provided. (See pages 3-7 of this handout.) You do not have to hand
in solutions to these problems, but we expect you to do them and keep up with the course material.
Lectures end April 2. The examination period runs from April 5 through April 22. There is not much time between the end
of lectures and the start of exams. It is imperative that you keep up with the course material during the term. Do not make
plans to leave campus before you know the date of your last exam. The exam schedule is usually posted in early March.

Grade Calculation
10% Quizzes: on-line quizzes accessed via http://sciborg.uwaterloo.ca/~cchieh/cact/cact.html
20% Term Test: 50-minute test on Wed., Feb. 25th held during your lecture time. (Rooms will be announced.)
70% Exam: 3-hour exam, scheduled by the Registrar's office. (The exam schedule is posted in March.)
Important Websites
The following web-based resources are available. Bookmark these sites.
Chem 123 Home Page http://www.science.uwaterloo.ca/course_notes/chemistry/chem123/
This is where we post useful information, announcements and links. You will also find extra problems, sample tests and
sample exams. Some of the information we provide here cannot be found anywhere else, so please have a look.
Cyberspace Chemistry http://www.science.uwaterloo.ca/~cchieh/cact/cact.html
This is a web-based software package developed by one of the instructors (Prof. C. Chieh, C2-263, ext. 5816,
cchieh@uwaterloo.ca). This is where you’ll access the on-line quizzes but there are many other useful features (e.g.
information pages, web links and reference material, as well as many sample problems taken from previous tests and
exams). Prof. Chieh’s web-site is tailored to the content of CHEM 123 without reference to text we are using.
Companion Website for General Chemistry (8th Edition) http://cwx.prenhall.com/petrucci/
This website is designed for courses that use the text by Petrucci, Harwood and Herring. Here you will find practice
quizzes, helpful web links, tools for visualizing molecules in 3D, and a reference centre containing useful tables and data.
There is also a tutorial centre.
Handbook of Chemistry & Physics http://www.hbcpnetbase.com/
This web-site provides on-line access to physical and chemical properties of all known substances, as well as accurate
values of all fundamental physical constants.

CHEM 123 Tutorials

Each student in the course is registered in a tutorial section that meets once every two weeks. Attendance is strongly
recommended. The tutorials are run by Tutors who are highly-qualified graduate or senior
Need extra help?
undergraduate students. The Tutors are available to provide help and guidance throughout
If you need extra help, you can
the term. During your tutorial periods, the Tutor will answer questions and work through
attend more than one tutorial
some examples.
session. Tutorial periods are
The Tutors will also administer a practice quiz during the tutorial period and then held at 8:30 am, 9:30 am,
work through the solution. These practice quizzes will help you assess your 10:30 am, 2:30 pm, 3:30 pm
understanding of the course material. Practice quizzes and solutions to the practice quizzes and 4:30 pm in RCH 204 every
will not be made available outside of the tutorial periods. Tuesday and Thursday!

Important Dates
Jan. 5 Lectures start. No CHEM 123 tutorials during the first week.
Jan. 9 CHEM 123/125 Early Exam (optional – see CHEM 123 web-site)
CHEM 123L/125L: Labs
Jan. 12 CHEM 123 tutorials start in the second week.
start during the first week of
Jan. 17 Last day to add a course to your schedule.
term!
Jan. 24 Last day to drop a course.
Feb. 16-20 Reading Week (for Science)
Feb. 25 CHEM 123 Term Test (held during your regular lecture period.)
Feb. 27 Last day to withdraw from a course.
Apr. 2 Lectures end
Apr. 5 Exams begin. The exam schedule will be posted in March.
Apr. 9 Good Friday (University Holiday)
Apr. 22 Exams end.

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CHEM 123 Practice Problems
Work (and learn) from your text book and stay ahead of your instructor throughout the term. This will help you get the most
out of the lectures. By working ahead, you can identify topics you find difficult before they come up in lectures. (See if your
instructor’s discussion helps you understand these difficult concepts. If not, ask for clarification during lectures.)

The week-by-week schedule outlined on the next few pages encourages you to build your problem-solving skills gradually.
When doing the problems, write down all of your steps as if you were going to hand in your solutions for marking. A clear,
organized approach will help you think through a problem. Hints to help you with the Part b problems are available
through the course websites.

Note: CHEM 123 is the continuation of CHEM 120. There are a number of concepts from CHEM 120 which you must know
(and should review, if necessary). These include:

 SI base units and SI prefixes

 reaction and solution stoichiometry (e.g. mass-to-moles conversions, molarity calculations, using the ideal gas
equation and partial pressures)
 thermochemistry and Hess’ Law
 basic organization of the periodic table (e.g. valence electrons, relationship between the group number and the
number of valence electrons for s and p block elements, electronegativity)
 drawing Lewis structures and predicting molecular geometry. You must also be able to assign formal charges.
Always show non-zero formal charges in any structure you draw!
 bonding concepts (e.g. ionic vs. covalent bonding, polar covalent bonds)
 oxidation-reduction (redox) concepts (e.g. oxidation numbers, balancing redox reactions)

Week 1, January 5-9

Problems: (from Chapter 13) 3, 4, 13, 17, 19, 40, 52, 56, 61, 64

Week 2, January 12-16

Problems: (from Chapter 13) 21, 24, 71, 77, 79a, 79b, 109, 118
Part b:

1. Consider a simple cubic lattice of identical hard spheres of radius R.

a) How many spheres are contained within one unit cell? What is the coordination number of each sphere?
b) What is the coordination number of any sphere in the lattice?
c) Show that the edge length a of the unit cell is a  2 R .
d) Calculate the packing efficiency (Vspheres / Vcell) for the simple cubic lattice. (i.e. What fraction of unit cell volume is
occupied by the spheres?

2. Consider a body-centred cubic lattice of identical hard spheres of radius R.

a) How many spheres are contained within one unit cell? What is the coordination number of each sphere?
a R
4

b) Show that the edge length a of the unit cell is 3 .

c) Calculate the packing efficiency for the body-centred cubic lattice.

3. Consider a face-centred cubic lattice of identical hard spheres of radius R.

a) How many spheres are contained within one unit cell? What is the coordination number of each sphere?

b) Show that the edge length a of the unit cell is a  2 2 R .

c) Calculate the packing efficiency for the face-centred cubic lattice.

4. Calcium crystallizes in a face-centred cubic lattice. The edge length of one unit cell is 557 pm. Calculate the radius of a
calcium atom and the density of solid calcium.

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Week 3, January 19-23
Part a: (from Chapter 13) 81, 83, 86, 88, 90, 116
Part b:
1. Show that the following data are consistent with the fact that silver metal crystallizes in a face-centred cubic lattice:
Edge length of unit cell, a = 408 pm Density of silver, 10.6 g cm3
Atomic weight of silver, 107.9 g mol1, Avogadro's number, NA = 6.022  1023
(Use any three quantities to calculate the fourth. Compare the calculated value with the given value.)
2. Let ro be the radius of the sphere that just fits into an octahedral hole formed by six identical hard spheres of radius R.

Show that o
r   
2 1 R
. See Figure 13-47 of the text for a diagram that will help you get started. (Note: The size of
the hole depends upon R because the larger the spheres, the larger the octahedral hole.)
3. A tetrahedral site can be generated by placing four spheres of radius R at alternate corners of a cube. Let rt be the radius
r 
of the sphere that just fits into the tetrahedral site. Show that t
1
2
 
6 2 R
. (Hint: Since the spheres are in contact
at the centre of each cube face, the length of the face diagonal of this cube is equal to 2R. What is the length of the body
diagonal (BD) of the cube? Since the centre of the tetrahedral site is located at the centre of the cube, the sum of rt and R
must equal to one-half the length of the body diagonal.)
4. Describe where the octahedral holes are located within the face-centred cubic unit cell. How many octahedral holes lie
entirely within one unit cell? (Hint: In Figure 13-48 of the text, the sodium ions occupy octahedral sites in the face-
centred cubic lattice of chloride ions.)
5. Describe where the tetrahedral holes are located within the face-centred cubic unit cell. How many tetrahedral holes lie
entirely within one unit cell? (Hint: See Figure 13-46 of the text.)

Week 4, January 26-30

Part a: (from Chapter 15) 8, 10, 13, 14, 26, 32, 34, 41, 46, 48, 52
Part b:
1. The partial pressure of a compound A changes as follows:
time 0 10 20 30 40 50 min
PA 4.00 2.94 2.32 1.92 1.64 1.42 Pa
Make a graph of PA versus time. Use your graph to evaluate (i) the average reaction rate (in Pa min1) over the first 40
minutes, and (ii) the instantaneous reaction rate (in Pa min1) at time = 40 min.
2. Define and distinguish between the terms rate and rate constant. Give the units of k for 1st order, 2nd order, 1.5 order,
and zeroth order reactions.

Week 5, February 2-6

Part a: (from Chapter 15) 59, 62, 65, 87, 102, 103
Part b:
1. From the following initial rate data for the reaction, A + B + C  products,
Expt 1 Expt 2 Expt 3 Expt 4
[A]o 0.0184 M 0.0368 M 0.0184 M 0.0184 M
[B]o 0.0225 M 0.0225 M 0.0384 M 0.0225 M
[C]o 0.0141 M 0.0141 M 0.0141 M 0.0365 M
Initial rate: 0.000145 M s1 0.000205 M s1 0.000145 M s1 0.000375 M s1
(a) Deduce the differential rate law.
(b) Calculate the value of the rate constant (include units).
(c) Calculate the initial rate for the conditions, [A]o = 0.0307 M, [B]o = 0.0228 M, [C]o = 0.0183 M.
2. The concentration of a compound A varies with time as follows:
time 0 5 10 15 20 min
[A] 1.82 1.65 1.49 1.35 1.22 M
(a) Plot [A], ln [A], and [A]1 versus time, and determine the order of the reaction with respect to [A].
(b) Calculate the rate constant.

4
Week 6, February 9-13
Part a: (from Chapter 16) 3, 4, 7, 14, 19, 21, 31, 34, 38, 41, 47, 48, 51, 58, 72, 77, 82
Part b:
1. In the following cases, you are given equilibrium constants for the two indicated reactions at 25°C, using atm for partial
pressures of the gases. Use the data to calculate Kp for the third reaction.

N2(g) + 1/2 O2 (g)  N2O(g) Kp, = 7.1  1019

N2(g) + O2 (g)  2 NO(g) Kp = 4.23  1031
2 N2O(g) + O2 (g)  4 NO(g) Kp = ?

2. An equilibrium mixture of CO(g), H2O(g), H2(g) and CO2(g) is kept at constant temperature in a cylinder capped by a
piston. These gases react as follows: CO(g) + H2O(g)  CO2(g) + H2(g). Show that if the piston is raised so that the
volume of the mixture is now three times its original value, the equilibrium is not affected by this change; that is the
equilibrium does not shift, even though the total pressure drops to one third of its original value.

3. For the reaction CO(g) + 2H2(g)  CH3OH(g), H = 90.2 kJ (per mole of CO) and Kp = 2.2104 at 298 K (when the
pressures are expressed in atmospheres). What is Kp at 500 K?

4. For the reaction CO(g) + 3H2(g)  CH4(g) + H2O(g), Kp is 2.151011 at 200oC and 4.56108 at 260oC. What is H
for the reaction?

Winter Study Week (for Science), February 16-20

Important!
Week 7, February 23-27
For an acid-base reaction, most
Part a: (from Chapter 17) 6, 7, 9, 11, 17, 19, 24, 28, 32, 40, 45, 46
chemists draw an arrow pointing
Part b:
from the lone pair to the proton
1. What are the concentrations of H+, OH, benzoic acid and the benzoate ion in: (i.e. from the lone pair of electrons
(a) 0.12 M benzoic acid, C6H5COOH, Ka = 6.3105? on the base to the proton of the acid).
(b) 1.2103 M benzoic acid? This is the convention we prefer you
For each case calculate the degree of ionization, . What do your answers for  to follow. For example, in Figs. 17-3
in (a) and (b) suggest about the relationship between  and the stoichiometric and 17-4, we prefer that you draw the
(or label) concentration? arrows in the opposite direction from
2. Trimethylamine, (CH3)3N, is a weak base that ionizes in aqueous solution: that shown in the text.

(CH3)3N(aq) + H2O(l)  (CH3)3NH + (aq) + OH (aq)

A 0.120 M solution of (CH3)3N is 2.29% ionized at 25°C.
(a) Calculate [OH], [(CH3)3NH+ ], [(CH3)3N], [ H3O+ ], and the pH for 0.120 M (CH3)3N solution at 25°C.
(b) Calculate Kb for (CH3)3N at 25°C.
(c) Calculate the degree of ionization, , of a 0.0960 M solution of trimethylamine. Does the degree of ionization
increase, decrease, or remain unchanged as the initial concentration of (CH3)3N decreases? Give the reasons for
your answer.

Week 8, March 1-5

Part a: (from Chapter 17) 48, 60, 64, 68, 69, 74, 75, 76, 77
Part b:
1. Write down material balance equations and charge balance (i.e. electroneutrality) equations for each of the following
solutions. (a) 0.100 mol L1 H2C2O4(aq) (b) 0.100 mol L1 Na2C2O4(aq)

2. Calculate [H3O+ ], [OH ], [H2C2O4], [HC2O4 ] and [C2O42 ] in 0.0117 mol L1 H2C2O4(aq). What is the pH of the
solution? State and justify your approximations. Look up the Ka values in Appendix D of the text.
3. Use the Ka values of oxalic acid, H2C2O4, to decide whether an aqueous solution of NaHC 2O4 will be acidic, basic or
neutral. Look up the Ka values in Appendix D of the text. Note: It is not necessary to do any pH calculations.
4. Calculate the equilibrium concentrations of all species, except water, in a solution prepared by dissolving 0.0125 mol
Al(NO3)3(aq) in water to make 1.0 L of solution. (Hint: In aqueous solution, the aluminum ion exists as Al(H2O)63+
which behaves as a monoprotic acid with pKa = 4.85. See page 699 of the text.)

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Week 9, March 8-12
Part a: (from Chapter 18) 11, 27, 39, 45, 53, 74, 81
Part b:
1. How many grams of sodium acetate, NaC2H3O2, must be added to 250 mL of 0.100 M acetic acid, HC2H3O2, to give a
solution with a pH of 6.50? Look up the Ka value in Appendix D of the text.
2. (a) How many grams of NH4Cl (a solid) must be added to 500 mL of 0.137 M NH3 to give a buffer of pH 10.34 ?
Assume no change in volume. Take Kb(NH3) = 1.7610 5.
(b) By how much would this pH change if 1 mL of 0.1 M HCl were added to 10 mL of the buffer?
(c) By how much would the pH change if 1 mL of 0.1 M HCl were added to 10 mL of pure water?
(d) By how much would the pH of the solution in part (a) change if 500 mL of water were added to it? Explain.
3. Piperidine, C5H11N, is an organic base with Kb = 1.30103. A 50.0 mL sample of 0.0800 M piperidine is titrated with
0.1000 M HCl. Calculate the pH of the solution
(a) at the start of the titration,
(b) when 35.0 mL of HCl have been added,
(c) when the titration is at the equivalence point.
Select a suitable indicator for this titration. Justify your choice.
4. Consider the titration of 25.0 mL of 0.120 M (CH 3)3N with 0.100 M HCl. Trimethylamine, (CH 3)3N, is a weak base in
water (Kb = 6.3105 at 25°C).
(a) Calculate the pH of the (CH3)3N solution. State and justify any approximations.
(b) Calculate the pH after adding 5.00 mL of HCl solution. State and justify any approximations.
(c) Calculate the pH at the half neutralization point.
(d) Calculate the pH at the equivalence point. State and justify any approximations.
(e) Use the results from parts (a) through (d) to sketch the titration curve. (i.e. Plot pH vs. the volume of HCl added.)
(f) Choose an indicator and explain why it would be suitable.

Week 10, March 15-19

Part a: (from Chapter 19) 4, 7, 8, 13, 14, 17, 20, 22, 27, 35
Part b:
1. What is the molar solubility of silver sulfate, Ag2SO4, in a 0.40 M AgNO3 solution? Justify any approximations that you
use. Note: Ksp(Ag2SO4) = 1.7x105

2. Soluble lead nitrate, Pb(NO3)2, solid is slowly dissolved in a solution which is 0.10 M with respect to each of iodide ion,
I, and carbonate ion, CO32. (Assume that the solution volume does not change throughout the experiment.)
(a) Which substance begins to precipitate first, PbCO3 (Ksp = 1.51013 ) or PbI2 (Ksp = 1.0109) ?
(b) What is the concentration of iodide ion in the solution when PbCO3 just begins to precipitate?
(c) What is the concentration of carbonate ion in the solution when PbI2 just begins to precipitate?

Week 11, March 22-26

Part a: (from Chapter 19) 45, 50, 51, 67, 68
(from Chapter 21) 1, 3, 7, 8, 11, 16, 17
Part b:
1. When 125 mL of 0.014 M Ca(NO3)2 is added to 195 mL of 0.038 M Na3PO4, a precipitate is formed. What is the
precipitate, and what are the concentrations of the ions from these salts in the supernatant solution (i.e., the solution
above the precipitate) at equilibrium? Find the Ksp value in Appendix D of your text.

2. Given that Eo = +0.04 V for the reaction: Cd2 + Fe(s)  Fe2 + Cd(s)
what is the standard reduction potential for Cd2 + 2e  Cd(s)? (Find Eo for the Fe2/Fe half-reaction in Appendix D.)

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Week 12, March 29-April 2
Part a: (from Chapter 21) 21, 28, 43, 49, 51, 52, 53, 71
Part b:
1. Consider the following reactions:
(1) Pb(s) + Co2(aq)  Pb2(aq) + Co(s)
(2) PbSO4(s) + Ni(s)  Ni2(aq) + Pb(s) + SO42(aq)
(3) IO3(aq) + 6H(aq) + 5Ag(s)  ½ I2 (s) + 3H2O(l) + 5Ag(aq)
(a) What is Eo for each of the reactions? Look up standard reduction potentials in Appendix D.
(b) In which direction does each reaction proceed spontaneously at standard state conditions?
(c) What is the equilibrium constant in each case?

2. (a) Calculate Eo for the reaction Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s). Look up standard reduction potentials
in Appendix D.
(b) Consider the galvanic cell Cu(s) | Cu2+ (aq, 0.50 M) || Ag+ (aq, 1.0106 M) | Ag(s) . What is the equation for the
spontaneous cell reaction? What is E for this cell?

Supplementary Topic: The Van’t Hoff Equation

(Background material can be found in Chapters 15 and 16.)

The equilibrium constant (Kc or Kp) for a reaction is essentially constant provided the temperature is held constant. (In reality, the
equilibrium constant does vary slightly with pressure and composition, but the variation with temperature is much greater.) The
temperature dependence of the equilibrium constant is modelled reasonably well by the Van’t Hoff equation:

 K2  H o  1 1 
ln     
 K1  R  T2 T1 
.

In the equation above, K1 is the value of K at T1, K2 is the value of K at T2 and H

o
is the enthalpy change for the reaction.
Please note carefully:
Always use H in joules and R = 8.3145 J K1 mol1.
o

 When applying the Van’t Hoff equation to a gas-phase reaction, K1 and K2 represent Kp values. When dealing
with a reaction in solution, K1 and K2 represent Kc values.

There are different ways to justify the Van’t Hoff equation but we will focus on a simple kinetic explanation.

Consider the elementary reaction 2 A + B  3C for which

[ C ]3 k
Kc= 2
= 1
[ A ] [ B ] k −1 .
If the rate constants each obey the Arrhenius form, k = A exp(Ea /RT), then the equilibrium constant Kc satisfies
A1 E −Ea , rev
Kc=
( ) (
A−1
exp − a , for
RT ) =
o
B e−ΔH / RT (where B is a constant).
Using the equation above to construct the ratio K2 / K1 (and taking the logarithm), we obtain the Van’t Hoff equation.
Note:
1. Recall from chapter 15 that Ea,for  Ea,rev = H.
2. In justifying the Van’t Hoff equation, we assumed that the reaction occurred in a single step for convenience only. If the
reaction occurs via an n-step mechanism, then we have Kc = (k1 / k1) (k2 / k2)  (kn / kn). Assuming each rate constant
obeys the Arrhenius form, we obtain the same final result.