Laboratory Methods of Inorganic Chemistry
Laboratory Methods of Inorganic Chemistry
Laboratory Methods of Inorganic Chemistry
OF
LNOKGANIC OHEMISTET
BY
HEINRICH BILTZ AND WILHELM BILTZ
UNIVERSITY KIEL UNIVERSITY GOTTINGEN
SECOND EDITION
NEW YORK
JOHN WILEY & SONS
LOJTDON: CHAPMAN & HALL, LIMITED
1928
COPYRIGHT, 1909, 1928,
BY
WILLIAM T. HALL AND ARTHUR A. BLANCHARD
Printed in U. S. A.
Printing Composition and Plates Binding
P. H . GILSOH CO. TECHNICAL COMPOSITION CO. STANHOPE B I N D E R ?
BOSTON CAMBRIDGE BOSTON
AUTHORS' PREFACE.
PAGE
INTRODUCTORY REMARKS ON LABORATORY PRACTICE 1
CHAPTER I.
The Periodic Classification of the Elements 9
The Elements 14
REDUCTION OF OXIDES WITH CARBON 15
1. Lead from Lead Oxide 15
ALUMINOTHERMY 16
2. Manganese from Pyrolusite 17
3. Chromium from Chromic Oxide 18
4. Crystallized Silicon 19
5. "Crystallized Boron" 20
REDUCTION WITH POTASSIUM CYANIDE 20
6. Tin from Cassiterite; Melting-Point Determination 20
7. Pure Antimony from Basic Antimony Chloride 22
REDUCTION WITH AQUEOUS REDUCING AGENTS 23
8. Selenium Dioxide and Pure Selenium from Crude Selenium... 23
9. Extraction of Gold 23
DESULPHURIZATION OF SULPHIDES BY THE PRECIPITATION PROCESS. 25
10. Antimony from Stribnite 25
11. Mercury from Cinnabar; Sodium and Ammonium Amalgams. 25
ROASTING PROCESSES 26
12. Lead from Galena 26
CUPELLATION 26
13.. Pure Silver from Coin Metal 26
METALS BY ELECTROLYSIS 28
14. Lithium from Fused Lithium Chloride 28
CHAPTER II.
Changes of Condition 32
POLYMERIZATION AND DISSOCIATION 32
ALLOTROPY 33
15. Allotropy of Silver Sulphide ' 34
16. Allotropic Modifications of Sulphur 35
17. Transformation Point of Cuprous Mercuriiodide and of Silver
Mercuriiodide 37
ix
X TABLE OF CONTENTS.
PAGE
THE PASSIVE CONDITION 38
18. Passive Iron 38
AMORPHOUS STATE 38
19. Amorphous Sulphur 39
COLLOIDAL STATE 39
ADSORPTION COMPOUNDS 41
20. Colloidal Platinum, according to Bredig 42
21. Colloidal Antimony Sulphide 43
22. Adsorption of Iodine by Charcoal; Adsorption Curve 44
23. Lanthanum Blue 45
24. Molybdenum Blue 46
25. Colloidal Gold Solutions; Precipitating Colloids and Protec-
tive Colloids 47
26. Hydrogels as Semipermeable Membranes 49
CHAPTER III.
Simple Compounds 51
OXIDES 56
27. Liquid Sulphur Dioxide 56
28. Sulphur Trioxide by the Contact Process 58
Oxidation of Naphthalin with Sulphuric Acid 59
29. Nitrogen Dioxide — Detection of its Association and Dis-
sociation 61
30. Chromic Oxide in the Dry Way from a Chromate 63
31. Cuprous Oxide 63
HYDRIDES 63
32. Cerium Hydride 64
33. Copper Hydride 65
ACIDS, BASES, AND SALTS 65
(a) Acids and Bases 69
34. Physico-chemical Detection of Electrolytic Dissociation 69
35. Hydrobromic Acid — Hydriodic Acid 70
36. Thallous and Thallic Hydroxides 72
(6) Halogen Compounds 73
37. Cupric and Cuprous Bromides 73
38. Cuprous Chloride 74
39. Potassium Iodide — Iodine from Iodide Residues 74
40. Barium Chloride from Witherite 77
41. Manganous Chloride from Waste Manganese Liquors 77
42. Anhydrous Ferric Chloride; Preparation of Chlorine 77A
43. Anhydrous Ferrous Chloride; Preparation of Hydrogen
Chloride 77C
44. Anhydrous Chromium Trichloride 77D
45. Sulphur Chloride, S2C12 77E
46. Chlorides of Phosphorus 77F
47. Chlorides of Antimony 77H
TABLE OF CONTENTS XI
PAGE
48. Iodides of Bismuth 771
49. Bismuth Tribromide; Boiling-Point Determination 77J
50. Tin Tetraohloride 79
51. Silicon Tetrachloride 80
52. Titanium Tetrachloride from Rutile 81
53. Anhydrous Titanium Trichloride 84
(c) Sulphides 85
54. Phosphorus Pentasulphide; Thermoelectric Determination
of the Boiling-Point 85
55. Black Mercuric Sulphide; Transformation into Cinnabar 88
56. Sulphides of Tin 88
57. Green Manganese Sulphide 89
58. Titanium Disulphide 90
(d) Nitrides 91
59. Hydrogen Cyanide, Mercuric Cyanide, Cyanogen, and Dithio-
oxamide 91
60. Boron Nitride 94
61. Magnesium Nitride; Ammonia from the Atmosphere 94
62. Chromium Nitride 96
(e) Phosphides 96
63. Magnesium Phosphide 96
(/) Carbides 97
64. Calcium Carbide; Acetylene from Calcium Carbide; Benzene
from Acetylene 97
CHAPTER IV.
Compounds Containing a Complex Negative Component 99
COMPOUNDS WITH HOMOGENEOUS COMPLEXES 101
(o) Peroxides 101
65. Sodium Peroxide 101
66. Barium Peroxide 102
67. Hydrogen Peroxide 103
(b) .Polysulphides 106
68. Ammonium Pentasulphide 106
(c) Polyhalides 107
69. Ammonium Tribromide 107
70. Law of Distribution; Proof of the Existence of Potassium
Tribromide and Potassium Tri-iodide 108
71. Rubidium Iodine Tetrachloride; Rubidium Tri-iodide; Potas-
sium-iodine Tetrachloride Ill
(d) Polynitrides 112
72. Sodium Hydrazoate from Sodamide 112
OXYACIDS AND THEIR SALTS 113
(o) Cyanates 113
73. Potassium Cyanate; Urea from Ammonium Cyanate 113
XU TABLE OF CONTENTS
PAGE
(b) Oxy-halogen Acids and their Salts 114
74. Electrolytic Production of Sodium Hypochlorite and Potas-
sium Chlorate 114
75. Potassium Perchlorate 118
76. Iodic Acid and Iodic Anhydride; "Time Reaction" 119
77. Potassium Iodate from Potassium Chlorate 120
78. Potassium Bromate and Potassium Bromide 121
(c) Nitrites and Nitrates 121
79. Sodium Nitrite from Sodium Nitrate 121
80. Potassium Nitrate from Sodium Nitrate 122
81. Silver Nitrate 123
82. Bismuth Nitrate and Basic Bismuth Nitrate 124
(d) Manganates and Ferrates 124
83. Potassium Permanganate by the Fusion Method 124
84. Electrolytic Preparation of Potassium Permanganate 125
85. Barium Ferrate 126
(e) Oxyacids of Sulphur and their Salts 126
86. Sulphuric Acid from Pyrite by the Chamber Process 128
87. Reduction of Barium Sulphate and Preparation of Barium
Nitrate 129
88. Antimony Sulphate 129
89. Alum from Kaolin 130
90. Sodium Thiosulphate 131
91. Barium Dithionate 131
92. Sodium Tetrathionate 132
93. Hyposulphurous Acid 132
94. Potassium Persulphate, Electrolytically 133
(f) Carbonates 134
95. Sodium Carbonate (Ammonia-Soda Process) 134
(g) Acids and Salts of Phosphorus 135
96. Barium Hypophosphite 135
97. Phosphorous Acid 136
THIOACIDS AND THEIE SALTS 137
98. Potassium Trithiocarbonate Solution (Reagent for N i c k e l ) . . . . 137
99. Barium Trithiocarbonate 137
100. Sodium Thioantimonate 138
101. Potassium Ferric Sulphide 139
102. Ammonium Copper Tetrasulphide 139
COMPLEX HALOGEN ACIDS AND THEIR SALTS. COMPLEX CYANOGEN
COMPOUNDS 140
103. Hydrofluosilicic Acid 142
104. Potassium Titanium Fluoride 143
105. Ammonium Plumbic Chloride. Lead Tetrachloride 143
106. Potassium Lead Iodide 144
107. Potassium Mercuric Iodide 145
108. Potassium Cobalticyanide 146
TABLE OF CONTENTS. xili
PAGE
109. Hydroferrocyanic Acid 146
110. Cobaltous Salt of Hydromercurithiocyanic Acid 147
111. Potassium Cobaltothiocyanate 147
112. Cadmium Iodide (Autocomplex Compound) 148
NITBITO ACIDS AND THEIB SALTS 149
113. Potassium Mercurinitrite 149
114. Sodium Cobaltinitrite; Potassium Cobaltmitrile 149
115. Potassium Tetranitrito-diammine-cobaltate 150
HETEBOPOLY ACIDS AND THEIB SALTS 151
116. Ammonium Phosphomolybdate 152
117. Silicotungstic Acid 152
OBGANOCOMPLEX C O M P O U N D S 153
118. Potassium Ferric Oxalate; Platinotypes 153
119. Optical Rotation of Uranyl Lsevo-malate 154
CHAPTER V.
CHAPTER VI.
Complex Non-Electrolytes 201
ACID CHLORIDES 201
149. Sulphuric Acid Dichloride and Sulphuric Acid Monochloride. 201
150. Pyrosulphuric Acid Chloride 204
151. Sulphurous Acid Chloride (Thionyl Chloride) 204
152. Nitrosylsulphuric Acid 206
ESTERS 207
153. Ethyl Nitrate 208
154. Amyl Nitrite and Methyl Nitrite 209
155. Symmetrical Diethyl Sulphite 209
156. Unsymmetrical Diethyl Sulphite 211
157. Triethyl Phosphate. 212
158. Tetraethyl Silicate 213
METAL-ORGANIC COMPOUNDS 213
159. Zinc Ethyl 214
160. Lead Tetraphenyl by Grignard's Reagent; Diphenyl-lead
Iodide 215
161. Nickel Carbonyl 217
CHAPTER VII.
Preparation of Compounds of the Rare Elements from Their
Minerals 219
162. Lithium Carbonate from Lepidolite, Petalite or Spodumene.
Spectroscopic Tests for Rubidium and Other Metals 219
163. Beryllium Hydroxide from Beryl 221
164. Basic Beryllium Acetate 222
165. Columbium and Tantalum Compounds from Columbite 223
166. Molybdenum Compounds from Molybdenite 224
167. Tungsten Compounds from Wolframite 229
168. Working up of Pitchblende and Testing for Radioactivity.... 231
169. Uranium Compounds 234
170. Thorium Compounds from Monazite 236
TABLE OP CONTENTS. XV
PAGE
171. Separation of the Rare Earths 239
Cerium Compounds 242
Lanthanum Compounds 244
Didymium Compounds 246
INDEX 247
LABOKATOBY METHODS
OF
INORGANIC CHEMISTRY.
Kg. 1.
Fig. 2. Fig. 3.
Fig. 4. ;. 6.
2. Evaporation.
Large quantities of solutions are concentrated in evaporating
dishes, which give a large surface for the escape of vapors from
the liquid. They should be heated, unless otherwise directed,
with a free flame without wire gauze or asbestos; but the flame
should never be allowed to come in contact with the dry upper
part of the dish, as in that case superheating would ensue which
might result in the breaking of the dish or in the decomposition
of the solid material that separates on the sides. Thus as the
concentration progresses the flame must be lowered or the evap-
oration finished on the water bath. Small quantities of liquid can
also be boiled down in beakers; but if this is done it is advisable
to avoid bumping by stirring or by adding to the liquid such
substances as small splinters of wood, bits of unglazed porcelain, or
of pumice, or, best of all, some of Siwoloboff's capillaries.1
3. Crystallization.
When crystals are to be obtained from a solution, it is often
necessary before the evaporation is finished to filter from impuri-
ties. For this purpose an ordinary plaited filter* is used
which is placed in a short-stemmed funnel. In case the crystals
separate rapidly, a Buchner funnel with suction is employed.
For strongly corrosive liquids, hardened filter paper must be
used or, often better still, a felt of asbestos fibers; the latter is
made by suspending the asbestos in water and pouring the sus-
pension on to the perforated bottom of a Buchner funnel, or
Gooch crucible, and drawing firmly in place by suction. Crys-
tallization will take place on cooling if the solubility of the
material decreases with sinking temperature, otherwise by
evaporation at a moderate heat, or at the room temperature in
a desiccator. Impure crusts tend to form around the sides of
the dish at the surface of the liquid; to prevent this as much as
possible, dishes with perpendicular walls (beakers or glass crystal-
lizing dishes) should be used. If this expedient is not success
ful, the crystals are collected by themselves and the crusts dis-
5. Distillation.1
For distilling ordinary liquids, flasks are used; for substances
which solidify easily retorts are more suitable and these in the case
of high-boiling materials, may be covered with folded asbestos
paper in order to keep in the heat. The use of a condenser is
usually superfluous when distilling high-boiling substances from
retorts; in distilling low-boiling materials a condenser of suit-
able length should be joined to the distilling flask with a cork
stopper (Fig. 6), although sometimes the connection is left open;
or a short condenser may be slipped over the neck of the
distilling flask itself and made tight with corks or with pieces
of rubber tubing (Fig. 7). In the case of substances that boil
1
For fuller details regarding distillation, especially of organic liquids,
see text-books on Organic Chemical Preparations.
INTRODUCTORY.
Fig. 6.
Fig. 7.
Fig. 8.
in the tubulus of the retort, in such a way that its bulb will be
entirely surrounded by the vapors (Figs. 6 and 8); thus with a
distilling flask the bulb should reach to the lower part of the
neck. It is best to use thermometers so short that the mercury
column will remain entirely within the vapor. The thermome-
ter shows at the beginning a temperature somewhat too low
because some time is necessary to heat it to the temperature
of the vapor; toward the end the reading becomes a little too
high on account of the vapor in the nearly empty flask becoming
superheated. Both of these facts are to be borne in mind when
judging of the purity of a substance. Concerning fractional
distillation, which is seldom of importance in making inorganic
preparations, see the preparation of acid chlorides and esters,
Chap. VI.
For vacuum distillation, use an apparatus similar to that shown
in Fig. 6 on page 6. The rubber stopper of the distilling flask,
besides carrying the thermometer, should be provided with a
8 INTRODUCTORY.
narrow piece of glass tubing, open at the top where it rises above
the stopper, and at the bottom ending in a long capillary reaching
nearly to the bottom of the flask. During the distillation, tiny
bubbles of air enter the flask, pass through the liquid and prevent
bumping. The stream of air is regulated by means of a screw
clamp on a short piece of rubber tubing which is placed at the top
end of the open tube. The arm of the heavy suction flask which
is used as receiver should be connected with a manometer and with
a suction pump. In spite of the fact that a little air is constantly
entering the flask during the distillation, it is easy to get the
pressure reduced to 10-18 mm. by the use of a good water pump.
Very volatile substances, such as sulphur dioxide, can be con-
densed in common gas wash bottles, with ground-glass joints,
by means of a freezing mixture. When enough liquid has con-
densed in the wash bottle so that the entrance tube dips beneath
its surface, the further condensation takes place very readily. If
the preparation is to be preserved, it is distilled into a thick-walled
glass tube, of the shape of a test tube, which is drawn down at
its upper end so that when filled it can be sealed by the blast
flame (Fig. 12, p. 58). Or, the substance can be poured into a
sealing flask the neck of which is of about the thickness of a lead
pencil, and can be readily melted together.
6. Pulverizing.
Minerals that are to serve as the raw materials for the various
preparations should, if possible, be bought in powdered form,
since the crushing of large masses in the laboratory is extremely
laborious. If the pulverizing must be undertaken, the material
should be ground in small portions and from time to time the fine
powder should be sifted from the coarse by means of wire gauze or
a sieve.
7. Drying of Rinsed Vessels.
When directions call for a dry vessel, it is sometimes the practice
to rinse the vessel with water, then with alcohol and finally with
ether, assuming that the ether will evaporate quickly and leave
a dry vessel. This method is unsatisfactory. It is far better to
dry the vessel, after rinsing it with several small portions of al-
cohol, by moving it back and forth over a small flame while
applying suction through a tube reaching to the bottom of the
vessel. Instead of suction, a gentle air blast can be used.
CHAPTER I.
THE ELEMENTS.
2 3 4 5 6 7 8 9 10
He 2 He Li Be B C N 0 Ne
F
10 11 12 13 14 15 16 17 18
Ne 2-8 Mg Al P Cl
Ne Na Si S A
Ni/3
2-8-8
2-8-18
18
A
28
19
K
29
20
Ca
30
21
Sc
31
22
Ti
32
23
V
33
24
Cr
34
25
Mn
35
26
Fe
36
27
Co
28
Ni 1
Ni/3 Cu Zn Ga Ge As Se Br Kr
Kr
Pd/3
2-8-18-8
2-8-18-18
36
Kr
46
37
Rb
47
38
Sr
48
39
Y
49
40
Zr
50
41
Cb
51
42
Mo
52
43
53
•44
Ru
54
45
Rh
46
Pd 1
Pd/3 Ag Cd In Sn Sb Te I Xe
54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 1
Xe 2-8-18-18-8
Xe Cs Ba La Ce Pr Nd Sa Eu Gd Tb Ho Dy Er Tm Yb
68 71 72 73 74 75 76 77 78
Er/3 2-8-18-32-8 Lu Hf Ta W Os Ir Pt
Er/3
78 79 80 81 82 83 84 85 86
Pt/3 2-8-18-32-18 Pt0 Au Tl Pb Bi RaF
Hg Nt
86 87 88 89 90 91 92
Nt 2-8-18-32-18-8 Ra Ac Th Ux2 U
Nt
Symbol enclosed in heavy lines —the kernel never acquires the form of an inert gas or a beta kernel
Symbol enclosed in light double lines — the kernel sometimes acquires the form of an inert gas or a beta kernel
Symbol enclosed in a light single line — the kernel is usually or invariably of the form of an inert gas or a beta kernel
PERIODIC CLASSIFICATION OP THE ELEMENTS. 11
multiple of the charge of the proton. Speculations regarding the
structure of the nucleus have been made in abundance but have
shed little light as to the nature of the incredible forces that hold
the nucleus together, — for the nuclei are almost immutable, or
at least just as immutable as the elements. The nucleus possesses
practically the entire mass of the atom but its bulk is excessively
minute. It occupies a space in the center of the atom much as
the sun does in the center of the solar system and the relative bulk
is comparable.
Surrounding the nucleus are "planetary" electrons, equal in
number in the neutral atom to the number of unit charges of the
nucleus. These electrons are relatively as far removed from the
nucleus as the planets are from the sun.
The properties of the elements, both physical and chemical, with
the exception of mass, are believed to depend entirely on the
arrangement of the electrons around the nucleus. Mass depends
on the number of protons in the nucleus.
The arrangement of the planetary electrons is restricted to
conditions imposed by the so-called "quantum" theory which
deals with the relation between the emission and absorption of
radiant energy and the structure of matter. There is no known
law of physics which would determine the radius of the orbit of a
planet. A planet might fall into any orbit whatever, depending
solely on the energy it might happen to possess. Apparently the
atom differs from the solar system in this respect; the quantum
requirements limit the number of orbits into which the electrons
may fall so that the radii (or major axes of elliptic orbits) of the
possible orbits are to each other in proportion to the squares of the
simple integral numbers, that is, 1 : 4 : 9 : 16 : 25 . . .
Although physicists today are rather strongly committed to the
orbital theory, it may still be better to refer to the possible positions
of the electrons as levels (i.e., measured out from the nucleus).
The number of electrons which can occupy each level is what
determines the configuration of the atom and this in turn deter-
mines all the physical and chemical properties of the atom.
The maximum number of electrons which can occupy the suc-
ceeding levels is twice the square of the successive whole numbers
or 2, 8, 18, 32, 50 . . . . The mutual repulsion of electrons, how-
ever, counteracts the tendency for the nucleus to pull the maximum
12 THE ELEMENTS.
number into the various levels. To take a concrete example:
Xenon has an atomic number of 54, that is, the nucleus has 54
unit charges and the number of planetary electrons in the neutral
atom is 54. If the attraction of the nucleus were unopposed the
first three levels would be filled to 2, 8 and 18 electrons respec-
tively and the fourth layer would hold 26. Actually the first
three layers are held by the strong nuclear charge, but a fourth
layer of 26 is unstable and eight are driven out into a fifth layer
so that the configuration becomes XeM 2-8-18-18-8.
Now there is something inherently stable in layers having the
numbers 2, 8, 18, 32 . . . and to acquire these numbers very con-
siderable counter forces can be overcome in atom and molecule
building. The Xenon atom with layers all containing the stable
numbers and with the nuclear charge to just neutralize the elec-
trons in these layers, is an extremely stable structure. This
accounts for the chemical inertness of Xenon. Likewise the in-
ertness of the other rare gases is accounted for.
Elements are known with practically all the atomic numbers
from 1 to 92. With elements other than the inert gases the tend-
ency is to acquire layers in conformity to the nearest inert gas
atom, thus upsetting the electrical neutrality of the atom and
giving us an "ion." Thus cesium, Cs66, loses an electron and
becomes a cesium ion Cs+ when some atom such as chlorine is at
hand to take on the electron.
Chlorine Cli7 by taking on the electron acquires the structure
of argon A« 2-8-8 and thus becomes a negative ion Cl~.
The tendency for atoms to acquire an outer layer of eight where
this is in any way possible is very strong. This is often accom-
plished as just indicated through the formation of ions, but there
is another way which was first recognized by G. N. Lewis in 1916,
and which in fact smooths out most of the previously irreconcilable
differences between the conceptions of valence held by inorganic
and organic chemists. This is that the two layers of eight may be
filled by a small number of electrons simultaneously holding posi-
tions in the outer layers, or "octets," of two atoms. For example,
in the chlorine molecule CU we have the two atoms Cln 2-8-7 with
only 14 electrons out of which to make two octets. If two elec-
trons are held jointly in the outer layer or "sheath" of each atom,
the two octets are completed.
PERIODIC CLASSIFICATION OF THE ELEMENTS. 13
These electrons held in common occupy a position between the
"kernels" of the two atoms and by their joint attraction for the
kernels hold the molecule together.
The kernel of an atom consists of the nucleus and all of the
layers except the outer layer. Those electrons in the outer layer
which belong to the neutral atom itself are usually referred to as
the "valence electrons."
The periods of the Periodic Classification comprise the elements
coming between any two of the successive inert gases. The first
two periods are short periods and comprise 8 elements each. The
properties of all elements of these periods are clearly seen to be
due to the tendency to revert to the structure of one or the other
of the nearest inert gases. The kernels of these elements are
invariable.
The elements near the beginning and end of the long periods
show clearly marked similarity to elements in the similar positions
in the short periods, their properties being derived from the ability
of the atom to acquire the configuration of the inert gas atom. In
the middle of the long periods, however, the number of electrons
to be gained or lost to acquire the inert gas structure is too great.
The number of electrons in the valence layer usually drops to two
or three and the rest of the electrons enter some one of the kernel
layers. For example, praseodymium Pr69 might be expected to
revert to the form of Xe64 2-8-18-18-8 and become quinque-
valent. As a matter of fact two electrons pass into the fourth
kernel layer to give Pr69 2-8-18-20-8-3, the 3 electrons of the
outer layer determining the valence. The tervalent ion Pr+++
is formed when three electrons are given to an element like chlo-
rine. The elements praseodymium to lutecium, 59-71, constitute
the so-called rare earth series. All have the nearly invariable
valence of three. They differ from one another simply by one
additional electron in the fourth kernel layer for each successive
element. They constitute what is called a "transition series."
With lutecium, however, the transition is complete and we have
the structure LU71 2-8-18-32-8-3 with stable kernel layers. In
the next element hafnium Hf72, the additional electron has to
remain in the valence layer as it cannot get into the layers con-
taining the stable numbers of 32 or 8. Hafnium has an invariable
valence of 4. Within the long periods are clearly recognizable
14 THE ELEMENTS.
subordinate periods which are spaced from the elements Ni, Pd,
Er, Pt, in the same way that the two short periods are spaced
from He and Ne. The number of electrons in each of these
elements is such as might give the following structures:
Ni28 2-8-18
Pd46 2-8-18-18
Er68 2-8-18-32-8
Pt78 2-8-18-32-18
These structures possess layers of inherent stability but the nuclear
charge is not great enough to hold the large outer layer of 18 or
the next to last of 32 against the repulsive forces. Given the
greater nuclear charge of the following atoms and these structures
become stable and consequently the succeeding elements revert
to those forms which are known as the beta forms or Ni/3, Pd/3,
Er/3 and Pt/3, respectively, and the subordinate periods are based
on these beta atoms in the same way that the major periods are
based on the inert gases.
THE ELEMENTS.
OCCUBBENCE. The relative amounts of the more common elements which
occur in the earth's surface, including the oceans and the atmosphere, are
shown by the following table compiled from statistics by F. W. Clarke:
atmosphere have been isolated, and sulphur is obtained from the associated
minerals. In other cases, the elements are dissolved out from mixtures by
means of suitable solvents, e.g., gold and silver by mercury.
OXIDES ABB REDUCED. The usual reducing agents are hydrogen, car-
bon or carbon monoxide (No. 1), aluminium (Nos. 2 to 5), magnesium,
sodium, potassium cyanide (Nos. 6 and 7), substances in solution, such as
sulphurous acid (No. 8) and finally the cathodic action of the electric current,
an agent of very general application. Sulphides are either changed to oxides
by roasting, or they are smelted with iron whereby the metal is formed in
the presence of a slag consisting chiefly of ferrous sulphide (Nos. 10, 11).
Halides may be decomposed by metallic sodium or the fused salts may be
electrolyzed (No. 14).
From salts containing oxygen, the elements are usually obtained by an
indirect method, as for example by first forming the oxides. Examples
of direct reduction, however, are the deposition of copper from copper sul-
phate solution by means of iron, the corresponding precipitation of silver
by copper, and the preparation of phosphorus by the reduction of acid cal-
cium phosphate with carbon at a high temperature.
ALUMINOTHERMY.
Metallic aluminium resists the action of water and the atmosphere, not
because the metal is difficult to oxidize, but on account of the fact that its
surface becomes covered with a thin, coherent layer of oxide which protects
it from further attack. If the formation of this layer of oxide upon the
aluminium is prevented by amalgamation, then the aluminium is rapidly
attacked. Aluminium vessels disintegrate quickly if they are amalgamated
with even a trace of mercury.
Remove the oil from 2 to 5 g. of aluminium powder by boiling
it with a little alcohol; pour off the latter, and cover the alu-
minium with a | % solution of mercuric chloride. After a few
minutes decant off the liquid and wash the powder several times
with water. Then cover the amalgamated metal with water and
allow it to stand. Within a short time there is an evolution
of hydrogen, the mass becomes heated until finally vapors of
steam arise, and white hydrated aluminium oxide is formed.
1
Cf. No. 13.
4
Cf. Tables of specific gravity.
MANGANESE FROM PYROLUSITE. 17
It is upon this strong tendency of aluminium to oxidize that the
processes of aluminothermy are based.
Mixtures of aluminium and oxides react together energetically, whereby
the aluminium is converted into oxide and the metal which originally was in
the form of the oxide is set free. Since one gram of aluminium on com-
bustion yields over 7000 calories, almost as much as carbon, and because
there are no gaseous products of combustion formed which would, carry
away heat from the reaction mixture, the temperature is raised to considerably
above 2000° C.
A mixture of ferric oxide and aluminium, the "thermite" of commerce,
is used for the rapid production of high temperatures in a small space, thus
in welding, riveting, etc., by the Goldschmidt process. The aluminium
oxide separates out from the reaction in the form of a very hard crystalline
substance which can be used as an abrasive; often well-formed needle-like
crystals are to be found in the hollow spaces of the slag. Metals like man-
ganese (No. 2), chromium (No. 3), molybdenum (No. 166) and vanadium,
which were formerly difficult to prepare, or could at best be obtained only in
an unfused state and very impure, can now be prepared without difficulty as
fused masses, free from carbon, by the reduction of their oxides with aluminium.
Even silicon and boron can be obtained by an alumino-thermic process,
if sulphur as well as an excess of aluminium powder is added to the oxides.
The sulphur unites with aluminium and forms a slag of aluminium sulphide,
by which reaction the high temperature required for the reduction of the
oxides is reached; under the slag a fused mass of metal is formed from which,
after dissolving away the excess of aluminium, crystals of silicon, or boron,
are obtained. Magnesium, if used in these reactions instead of aluminium,
produces similar results.
Cut the tin into a few small pieces and place it in a test tube
of 1 cm. diameter which dips 4 cm. into a small beaker filled with
sulphuric acid. Cover the beaker with a disk of asbestos board
provided with a hole into which the test tube fits. Heat the
sulphuric acid until the tin just melts; then heat a thermometer
cautiously over a flame to about 200° and dip it into the molten
metal. Lower the flame under the beaker so that the temperature
of the bath falls slowly, and, while stirring, observe the changes
of the thermometer reading. At the solidification point the tern-
22 THE ELEMENTS.
perature remains constant for from 10 to 20 minutes. In deter-
mining this temperature, a supercooling occurs regularly; i.e.,
the thermometer at first falls a few degrees below the solidification
point while the mass still remains perfectly liquid. Then, as the
crystals of the solid begin to separate, the temperature rises
rapidly to the solidification point, where it remains perfectly sta-
tionary while the mass is crystallizing. After this point is deter-
mined, increase the flame a little and find the melting-point in an
exactly corresponding manner. Tin melts at 232° C.
In using a long, ordinary thermometer the observed tempera-
ture is always a few degrees too low because the entire thread of
mercury is not at the desired temperature. Such an observed
reading gives the " unconnected melting-point." It may be cor-
rected by adding the value, 0.000,16 • a (t — t0), in which a is
the length in scale degrees of the exposed thread of mercury, t
is the observed reading, and U the average temperature of the
exposed mercury. This last value is obtained by a second ther-
mometer, the bulb of which is placed at about the middle of the
exposed mercury column. The correction is usually spoken of as
the "correction for stem exposure." Another method for applying
the correction for stem exposure has been proposed by E. Rim-
bach; 1 see also Preparation No. 49.
ROASTING PROCESSES.
12. Lead from Galena.
By the "roasting process" galena is first partly oxidized at a relatively
low temperature to lead oxide or lead sulphate; then without any intro-
duction of air the mass is heated more strongly, whereby the oxygen of the
lead oxide and lead sulphate accomplishes the oxidation of all the sulphur
present to sulphur dioxide. Only those ores are suitable for roasting which
contain but small amounts of silicates and of sulphides of other metals.
Silicates are harmful, since they give rise to the formation of lead silicate.
As it is difficult to conduct the partial roasting satisfactorily upon a small
scale, it is better in the following experiment to start with a mixture of galena
and litharge:
PbS + 2 PbO = 3 Pb + SO2,
PbS + PbSO4 = 2 Pb + 2 SO2.
CUPELLATION.
13. Pure Silver from Coin Metal.
If an alloy of impure precious metal, such as gold, silver or platinum, is
melted on a cupel in an oxidizing atmosphere, the lead and other base metals
present are oxidized and are absorbed by the porous material of which the
PURE SILVER FROM COIN METAL. 27
cupel is made. This process is made use of technically for obtaining pure
silver from the impure metal, and for working up argentiferous lead which is
obtained in the metallurgy of certain lead ores; the process is likewise used
on a small scale in the rapid and accurate quantitative estimation of silver
and gold in ores or metallurgical products (fire-assay).
METALS BY ELECTROLYSIS.
14. Lithium from Fused Lithium Chloride.
Fused lithium chloride, like the aqueous solution of this salt, is largely-
ionized and consequently can act as an electrolyte. According to the present
theory, the passage of an electric current represents a movement of tiny
particles of negative electricity called electrons (cf. p. 9). If an electric current
passes through an electrolyte there is always chemical decomposition at each
electrode, an oxidation at the anode and a reduction at the cathode. Thus
the electrolysis of fused lithium chloride results in the simultaneous formation
of metallic lithium at the cathode and chlorine gas at the anode. At the
cathode, where the negatively-charged electrons pass from the wire to the
electrolyte, the positively-charged lithium ions are neutralized and neutral,
or free, lithium is formed. At the anode, where electrons leave the fused salt
and pass to the anode and thence to the conducting wire, each negatively-
charged chloride ion gives up one electron and neutral, or free, chlorine results.
These reactions of reduction (lithium) and oxidation (chlorine) can be ex-
pressed by the following equations in which the symbol e is used to represent
the electron, or unit charge of negative electricity
2 Li+ + 2 e = 2 Li 2 Cl~ .= CI2 + 2 t.
The electron, therefore, represents one unit negative charge, such as is repre-
sented by the negative charge on one atom of chlorine in the chloride ion.
Although it seems probable from the results of several methods of experimen-
tation that there are about 6.1 X 1023 atoms of lithium in one gram atom, so
that we have a fairly good idea as to the actual magnitude of the unit charge
of electricity, it is more advantageous to think in terms of the gram atom
which, in the case of lithium or any other univalent ion, bears a charge of
6.1 X 1023 units of electricity. This larger value corresponds to 96,500
coulombs or 26.82 ampere hours and represents the quantity of electricity
required to set free 6.940 grams of lithium and 35.46 grams of chlorine when
all of the electrical current passing through fused lithium chloride is utilized
for producing lithium at the cathode and chlorine at the anode. Thus, with
100% current yield, a current of one ampere passing through lithium chloride
a 04.0 v QAOO
for one hour (3600 seconds) will set free *" * n = °- 2 5 8 9 S- o f lithium
y Oj ouu
35 4 6
and " - ,^-. 3 6 0 0 = 1.322 g. of chlorine. Or, since at 0° and 760 mm.
pressure, one molecule of chlorine or any other gas occupies a volume of about
22.4 liters, one can say that 96,500 coulombs will liberate 11.2 liters of chlorine
gas. This quantity of electricity, 96,500 coulombs, is called one Faraday,
because Michael Faraday recognized about the year 1835 that the quantities
of different elements liberated by a given quantity of electricity were propor-
tional to the atomic weights, or simple multiples of the atomic weights, of
the elements (Faraday's law).
LITHIUM BY ELECTROLYSIS. 29
In carrying out electrolytic preparations, the apparatus is usu-
ally arranged in accordance with the following scheme (Fig. 9),
which is, in principle, identical with that employed in electro-
analysis. The decomposition cell, an ammeter, and a regulating-
resistance are introduced in series into an electric circuit. The
binding clamps of the cell may also be connected with wires from
a voltmeter in order to determine the difference in potential
between the two poles during the electrolysis. The ammeter
should remain in the circuit throughout the whole of the elec-
trolysis; the voltage is measured only from time to time, and
has less value for determining the course of the reaction when
h
Battery
Resistance
Decomposition Cell
Fia. 9.
CHANGES OF CONDITION.
CHANGES in the state of aggregation of substances have already been men-
tioned in the preceding chapter; but under changes in condition are included
also polymerization and dissociation, as well as the formation of allotropic,
passive; amorphous, and colloidal modifications. These phenomena are, with
few exceptions, not confined to any particular class of substances.
32
ALLOTROPY. 33
ALLOTROPY.1
Many solid substances appear, under different conditions, in two or more
distinct forms (known as allotropic modifications), which are distinguished
from one another by color, density, crystalline form, solubility, and other
physical properties. The best known instances of this are shown by carbon
and phosphorus.
In the same way that different states of aggregation are separated by a
temperature boundary which is dependent on the pressure, so also for the
mutual transformation of numerous allotropic forms, there is a definite tem-
perature, dependent only on the pressure, below which the one, above which
the other form is stable. This is known as the transition temperature.
In addition to this sort of allotropy, which, because the two forms can
change simultaneously into one another and can exist in equilibrium at the
transition temperature, is known as enantiotropy, there is also a second sort
known as monotropy. Two modifications of a substance are monotropic
when the one changes into the other, but the latter cannot change back
directly into the first. They possess no transition temperature; one form is
under all conditions less stable than the other, and therefore is only to be
observed in virtue of the extreme slowness with which the transformation
takes place. i
An example of enantiotropy is shown by sulphur, which above 96° is
monoclinic, below 96° rhombic. An example of monotropy is furnished by
iodine chloride, IC1, the labile form of which melts at 14° and the stable
form at 27°. (Cf. No. 55.)
The energy difference between allotropic modifications corresponds entirely
with that existing between the solid and the liquid states and, like the latter,
is measured by the heat of transformation.
For determining the transition point of allotropic forms, the following
methods are chiefly used:
(1) The THERMIC METHOD. The point on the heating or cooling curve is
determined at which, in consequence of the absorption or setting free of the
heat of transition, a retardation in the otherwise steady rise or fall of tem-
perature occurs; compare the determination of the melting-point of tin,
No. 6, alao Nos. 15 and 16.
(2) The DILATOMETRIC METHOD, which depends on a comparison of the
densities (or of the volumes) on both sides of the transition point.
(3) The OPTICAL METHODS, which frequently permit a very sharp observa-
tion of a change in crystalline form, or in color, at the transition point.
(No. 17.)
(4) ELECTRICAL METHODS, (a) The electrical conductivity of a substance
is plotted graphically against the temperature and the point of inflection of
the curve determined.
1
Concerning allotropy, see also B. Roozeboom, Heterogene Gleichge-
wichte, Vol. 1, p. 109 (1901).
34 CHANGES OF CONDITION.
240° 220°
S30° 210°
210° 190°
200° \ 180° / /
190° 170°
180° 160°
170° 160°
160° 140°
150° 130°
100 200 300 400 500 100 200 800 400 600 000
Seconds Seconds
AMORPHOUS STATE.
As already stated, the phenomenon of supercooling is very generally observed
when melted substances solidify. This can often be obviated by means of
"seeding" with small fragments of the crystallized substance. In other
cases the supercooling persists far below the true temperature of crystalli-
zation, and a gradual changing into the crystalline form takes place only very
slowly, or perhaps not even to a detectable extent. Such strongly super-
cooled fluids are designated as amorphous substances when they, like glass
AMORPHOUS SULPHUR. 39
COLLOIDAL STATE.
A large number of substances are capable of apparently dissolving in water
to form what may be termed pseudo-solutions; such pseudo-solutions are
characterized by an extremely small diffusive power, a low osmotic pressure,
and an inability to undergo dialysis; in these respects they differ from true
solutions of crystalloids, and are thus called colloidal solutions (Graham, 1862).
Colloidal solutions are distinguished, according to the nature of the solvent,
as hydrosols, alcosols, etc. If the dissolved, or, more correctly, the pseudo-
dissolved substance is separated from the solvent, it is often found not to
have lost the power of again passing into colloidal solution (reversible colloids).
On the other hand, there are numerous substances, particularly inorganic ones,
40 CHANGES OF CONDITION.
which are unable of themselves to pass directly into colloidal solution, but
can by suitable means be brought into that state; if such substances are
separated from the solution, they do not possess the power of dissolving
again unaided (irreversible colloidals).
Solutions of irreversible colloids can be obtained by disintegrating the
substance in the electric arc under water (Bredig's method; see No. 20), by
forming the substance in aqueous solution by double decomposition and
preventing its precipitation by suitable means (Nos. 21; 24, Note on zircon
oxide hydrosol; No. 25), or by previously imparting to the solid the ability
to dissolve by treatment with small quantities of alkali or acid. The last
method was compared by Graham with the process of digestion and called
by him peptonization (No. 25, tin-oxide hydrosol).
By means of optical methods (ultramicroscopic investigation), it has been
proved that many of these colloidal solutions consist really of suspensions of
extremely small particles the size of which can be estimated down to a diam-
eter of about 6 MM- In this manner the formerly-very-puzzling fact of the
existence of solutions of substances that are ordinarily insoluble, such as gold,
platinum, and the sulphides of the heavy metals, finds its explanation.
Modern views concerning the nature of colloids indicate that any substance
under proper conditions can be obtained in the colloidal state. There is no
sharp distinction between mechanical suspensions of a finely powdered sub-
stance in a liquid, a colloidal solution and a true solution. It seems to be
merely a matter of size of the individual particles of the substance. By
employing micro-photographic methods and working with the short waves of
ultra-violet light, the limit of microscopic vision with an ordinary microscope
is reached at diameters of about 0.001 mm. or 1 micron (symbol M). The
pores of the best grades of hardened filter paper are about 1 M in diameter.
Clay and porcelain filters have pores about 0.2-0.4 M in diameter. The size
of the average molecule varies from 0.0001 to 0.001 M or, using the term
micro-micron or amicron to represent one-millionth of a millimeter (symbol MM),
the diameter is 0.1-1 nfx. A very large molecule such as starch has a diam-
eter of about 5 ij.fi..
On the basis of the size of the particles which a powdered substance assumes
when it is shaken with a liquid, it is possible to distinguish arbitrarily between
suspensions, colloidal solutions and true solutions. If the particles have diam-
eters of 0.1 M or more, so that they may be removed by filtration and can be
seen under the microscope, the solid substance is said to be in suspension. If
the diameters of the particles of solid lie between 0.1 M and 1 fn/j., the mixture of
solid and liquid is said to be a colloidal solution. If the substance dissolves,
as we say, in the liquid and assumes dimensions corresponding to those of
individual molecules, having diameters of 1 fj.fi. or less, we say that the sub-
stance is in a state of molecular dispersion, or true solution.
Colloidal solutions, as a rule, appear clear when viewed by transmitted
light, i.e., looking straight through the solution in a test tube, but appear
turbid when viewed by reflected light, i.e., with the test tube held above or
below the level of the eye. The particles can be seen with the aid of the ultra-
microscope and show a lively movement to and fro (Brownian movement).
ADSORPTION COMPOUNDS. 41
The laws of their motion have been studied and found to correspond to that
expected from the kinetic molecular theory. Colloidal chemistry, therefore,
has served to bring the molecular hypothesis out of the realms of theory into
the field of positive fact.
Many irreversible colloids separate out from their solutions as volumi-
nous precipitates containing a large amount of water (hydrogels). Such
hydrogels as, for example, those of ferric oxide, aluminium oxide, and silicon
oxide, can also be obtained directly by chemical precipitation from solution.
These precipitates contain a great deal more water than would correspond to
their hydroxide formulas (Fe(OH)3, A1(OH)3, Si(OH)4, etc.), and since the
water thus contained does not show the characteristics of chemically com-
bined water (compare the theoretical section on Hydrates preceding No. 144),
these precipitates should be designated, according to van Bemmelen, as oxide
hydrogels, or by their old name of hydrated oxides.
The change from the hydrosol to the hydrogel state is most simply brought
about by the addition of an electrolyte. Many colloidal solutions are ex-
ceedingly sensitive to electrolytes (gold solution, No. 25); the most essential
condition for the preparation of the solution must therefore be the absence
of any unnecessary electrolyte. Even reversible colloids can be separated
from their solutions by the addition of large amounts of an electrolyte; the
process is termed "salting out," and is employed in the precipitation of pro-
teins and dyestuffs (No. 24).
ADSORPTION COMPOUNDS.
Adsorption is the phenomenon shown by certain substances having a
large surface (for example, wood-charcoal) of condensing gaseous or dis-
solved substances upon themselves. Adsorption is a special kind of natural
phenomenon which is quite distinct from the process of solution.
It has been shown, especially by van Bemmelen, that the typical col-
loids exhibit a particularly high power of adsorption; and also that organized
matter, such as plant fibers and decayed material like humus, possesses the
same power. The latter classes of substances are, therefore, included among
colloids, especially since in contrast to crystalloids they lack a definite form,
bounded by rigid surfaces.
Among other instances in which adsorption may occur, the following are
of especial importance. It may take place: (1) between liquids and solid
substances (as when moisture is retained by many solid substances and par-
ticularly by hydrogels); (2) between dissolved substances and solids (as in
the dragging down of dissolved salts by precipitates and in the adhering of
fertilizer salts in the soil; cf. Nos. 22 and 23); (3) between dissolved reversible
colloids and solid materials (as in numerous dyeing processes; No. 24).
The combinations so produced are known as adsorption compounds.
For many adsorption processes, definite relations exist between the con-
centration in the solution of the substance adsorbed and the composition of
the adsorption compound. Adsorption acts relatively more strongly the
less concentrated the solution (cf. No. 22). Many adsorption compounds
42 CHANGES OF CONDITION.
are of so specific a nature (for example, iodo-starch) that it has been only
after the investigation of the quantitative relations between their com-
position and the conditions under which they are formed that their
difference from true chemical compounds has been established. Such an
exhibition of adsorptive power as this has also been designated as affinity of
condition.
Different dissolved colloids can also mutually combine to form adsorption
compounds: gold hydrosol, which is so exceedingly sensitive toward elec-
trolytes, can, by the addition of a non-sensitive colloid such as gelatin, be
itself made stable toward electrolytes; this would tend to show that a com-
bination had taken place between the two kinds of dissolved colloids (cf.
No. 25). Substances which act as gelatin does in this case are known as
protective colloids.
Again, other colloids are capable of mutually precipitating one another
out of solution.1 Thus arsenic-sulphide-hydrosol and iron-oxide-hydrosol
when mixed in the right proportions are both precipitated as a common
adsorption compound (cf. No. 24, 4). This precipitating power arises from
the same cause as another characteristic property which pseudo-dissolved
substances have in common with suspensions', if suspensions or colloids are
subjected to the action of a strong electric potential, a passage of the suspended
material through the solution occurs, but this is of a very different nature
from ionic migration. (Convective transference.) While, with electrolytes, the
dissociated parts possess opposite electrical charges, here the opposite charges
reside upon the pseudo-dissolved material and the solvent itself, respectively.
It is a rule that two such colloids in order to precipitate each other must
have charges of opposite sign when referred to that of the common solvent.
(Example, zircon-gold-purple, No. 25.)
Finally, adsorption compounds can be produced by precipitating two col-
loids out of a common solution by the addition of an electrolyte. (Example,
Purple of Cassius, No. 25.)
and the contents will differ only in the amount of iodine. After
24 hours, during which time the bottles should be frequently
shaken, take 10 c.c. of the clear solution from each and determine
the iodine content by titration with 0.1-normal sodium thio-
sulphate solution. The difference between the original weight
present and the amount of iodine thus determined gives the quan-
tity adsorbed by the charcoal. Arrange the results in a table and
plot them on coordinate paper with the adsorbed amounts as or-
dinates and the corresponding amounts left in solution as abscissas.
It is found that from dilute solutions relatively more iodine is
adsorbed than from concentrated ones. This relation is quite
general for adsorption equilibria, and can frequently be represented
by the equation — = k, in which ci is the concentration of the
adsorbed iodine, c2 that of the unadsorbed iodine, and n and k are
constants.1 Since in these experiments the same volume and the
same amount of charcoal are taken each time, the quantities of
iodine determined may be used directly in place of cx and c2 in the
equation. Find by trial what value of n makes the quotient
remain most nearly constant; n is greater than 1.
tion has been obtained, the ether can be driven off completely and
air introduced to oxidize the excess phosphorus, without injury
to the gold colloid (hydrosol). This preparation of colloidal gold
solution is very sensitive to external conditions; it is not possible
to produce equally good solutions in all laboratories.
2. Colloidal Gold by Reduction with Carbon Monoxide. Prepare
carbon monoxide by heating oxalic acid crystals with concentrated
sulfuric acid, and passing the gas through sodium hydroxide solu-
tion to remove carbon dioxide. Pass a slow stream of the carbon
monoxide into 120 cc. of 0.03% chlorauric acid. There is pro-
duced a violet color which changes to violet-red and later to a dark
red. Do not carry the reduction too far, as the solution will then
assume a permanent violet color.
3. Colloidal Gold by Reduction with the Hydrogen Flame.1 I t is
easy to prepare a colloidal gold solution by merely directing a
pointed hydrogen flame, 1 to 2 cm. long, against a 0.03% solution
of chlorauric acid contained in a wide, porcelain dish. After
about five minutes the solution begins to be colored; soon a rich
red color is produced. Occasional stirring hastens the formation
of the colloidal gold.
Use a gold solution prepared by any one of these methods in the
following experiments.
I. Synthesis of Purple of Cassius. From a mixture of colloidal
stannic oxide and colloidal gold, the gold-stannic oxide adsorption
compound is precipitated on the addition of electrolytes. In order
to prepare the colloidal stannic acid solution, allow 5 cc. of tin
tetrachloride (No. 50) to become hydrolyzed by the addition of
150 to 200 cc. of water, and pour this solution into 500 cc. of
water to which a few drops of ammonia have been added. Dialyze
the clear mixture for five days (cf. No. 21), changing the outside
water two or three times daily, until it shows no test for chlorides.
If during this process a hydrogel separates in the dialyzing tube,
it may be peptonized (see p. 40) in a beaker by the addition of
about three drops of ammonia, whereupon, after a time, the jelly
will go over into a perfectly clear hydrosol. A mixture of this
hydrosol with an equal volume of gold solution remains unchanged,
but on addition of a salt (ammonium chloride) a beautiful deep-
1
J. Donau, Monatsh. 34, 949 (1913). Colloidal solutions of silver, platinum
and molybdenum blue can be prepared by this method.
SEMIPERMEABLE MEMBRANES. 49
reddish-purple precipitate is formed which can be filtered off; the
compound is characterized by its solubility in ammonia.
II. Zircon-gold-purple. Treat 130 c.c. of a boiling colloidal gold
solution with 28 c.c. of a boiling colloidal zircon solution (see foot-
note to No. 24). A precipitation of zircon-gold-purple takes place
even without the addition of an electrolyte. In the cold the pre-
cipitate forms slowly. If the deposition is incomplete, preliminary
tests must be made with small portions to find the right propor-
tions in which to mix the above solution.
III. Gold Solution and Protective Colloids. Treat 10 c.c. of col-
loidal gold solution with a few drops of dilute hydrochloric acid; a
blue coloration is first produced, later sedimentation of the metal.
Repeat the experiment after first adding one drop of a dilute
gelatin solution (0.2 per cent) to the colloidal gold; no change
whatever in the color or the stability of the gold solution is observed.
26. Hydrogels as Semipermeable Membranes.
The separation of colloids and electrolytes by dialysis depends on the
colloidal nature of the parchment wall, which is impervious to other colloids.
Certain colloids are impervious even to truly dissolved substances but still
pervious to water. By means of membranes of such semipermeable material
a solute can be separated from its solvent, and thus the osmotic pressure of
the dissolved substance can be both demonstrated and measured. Cupric
ferrocyanide has been found especially suitable as a semipermeable colloid.
(Pfeffer, 1877.)
entrance of water, the cell rises to the surface of the solution, and
remains there until, after ten or fifteen minutes, the constant
thickening of its walls so increases its weight as to make it once
more sink, and this time permanently.
2. Membranes of Colloidal Silicates of the Heavy Metals. Dilute
some commercial water-glass solution until a specific gravity of 1.1
is obtained. Into about 100 c.c. of this solution in a narrow
beaker, drop small particles of various salts, such as copper sulphate,
aluminium sulphate, ferric chloride, nickel nitrate, cobalt nitrate,
manganous sulphate, lead nitrate, and uranyl nitrate. Within a
few minutes the particles begin to swell and to send out shoots
which branch and grow toward the surface of the liquid until the
whole beaker is filled with what appear to be bright colored algse
growths. The salt, on being thrown into the solution, begins at
once to dissolve, and at the surface of contact between this solu-
tion and the silicate solution, an insoluble semi-permeable film of
metal silicate is formed. The dissolved salt within exerts an
osmotic pressure against this film, and forces it to expand, while
the water which is thereby drawn in through the film dissolves
more of the salt. The osmotic pressure is thus maintained and
the film is continuously forced to expand until it bursts in places
and forms outgrowths and side-arms.
CHAPTER III.
SIMPLE COMPOUNDS.
UNDER the designation simple compounds are included all compounds con-
taining but two elements, with the exception, however, of the persulphides,
peroxides, polyhalides, etc., which are considered to have complex cations
(Chap. IV). The metal hydroxides and cyanides, in which the radicals OH
and CN behave as single elements, are also classed as simple compounds.
METHODS OF PREPARATION. Simple compounds are prepared:
(1) Synthetically from the elements:
Br2 + H2 = 2 HBr (No. 35a).
Cf. also Cerium Hydride (No. 32); Fel 2 (No. 39); FeCl3 (No. 42); CrCl3 (No. 44);
S2C12 (No. 45); PC13 (No. 46); Bil 3 (No. 48); BiBr3 (No. 49); SnCl4 (No. 50);
SiCl4 (No. 51); PjS, (No. 54); HgS (No. 55); Mg3N2 (No. 61); Mg3P2 (No. 63).
Frequently the synthetic preparation of compounds between two elements
takes place in stages:
P + 3 Cl = PCI,,
PC13 + 2 Cl = PC15. (No. 46)
Cf. also SO3 (No. 28); SbCl5 (No. 47); SnS2 (No. 56).
(2) By the interaction of two substances, each containing one of the ele-
ments which are to be combined:
(a) By the action of an element upon a compound:
Fe + 2 HC1 = FeCl2 + H2. (No. 43)
Cf. also A1C1, (No. 43).
(6) By the chemical reaction between two compounds (double decomposi-
tion or metathesis), as, for example, in the precipitation of a sulphide from the
solution of a metallic salt by means of hydrogen sulphide:
CuCl2 + H ^ = CuS + 2 HC1.
Cf. MnS (No. 57); TiS2 (No. 58); CrN (No. 62); and BrH (No. 35b).
(3) By the breaking down of more complicated compounds:
2 HNO3 = H2O + N2O4 + O (No. 29)
Cf. also Cr2O3 (No. 30); Cu2O (No. 31); copper hydride (No. 33); cyanogen
(No. 59); BaS (No. 87).
Certain simple compounds which were formerly prepared by double decom-
position, or by the breaking down of more complicated compounds, are now
most advantageously obtained directly from the elements, even industrially;
both because the requisite conditions for their formation are now better
understood and because some elements are far more accessible than formerly.
51
52 SIMPLE COMPOUNDS.
Thus sulphuric acid anhydride is now prepared directly by the contact process
(No. 28), nitric oxide from the elements in the atmosphere (combustion of air),
ammonia from nitrogen and hydrogen, and aluminium chloride from the
metal (cf. No. 43.)
REACTIVITY AND DEGREE OP DISSOCIATION. It is a general principle that
the reactivity of a substance is determined by a previous breaking down
(dissociation), to a greater or less extent, in the same sense as that in which
the reaction in question takes place. Phosphorus pentachloride, for example,
has a chlorinating effect, and sulphur trioxide an oxidizing effect, only when
under the prevailing conditions the one is partly dissociated into free chlorine,
the other into free oxygen, even in the absence of any substance to be chlo-
rinated or oxidized. Conversely, a tendency shown by substances to enter
into reaction may be considered as an indication of the preexistence of a
corresponding dissociation. The dissociation of binary substances, which in
fact often takes place in stages, is essentially the reverse of their synthesis.
PC16 = PC13 + Cl2
PC13 = P + 3 Cl
2 SO3 = 2 SO2 + O2 (No. 28 )
DISSOCIATION AND STATE OF EQUILIBRIUM. If it is true that reactivity is
dependent upon a certain ability to dissociate, it becomes important to study
the conditions favoring the formation and those favoring the decomposition
of substances. To take a concrete example, — When does the reaction
2 SO2 + O3 = 2 SO3
take place, and when
2 SO3 = 2 SO2 + O2?
In this connection, another principle which is likewise of very general
importance has been established, — namely, that a reaction never takes place
completely in one direction; at most the chemical change may proceed chiefly
in a definite direction until when the reaction comes to a standstill (i.e., when
equilibrium is reached) the products of dissociation and the undissociated
compound exist together side by side, forming the so-called equilibrium-
mixture. The percentage composition of an equilibrium-mixture is charac-
terized by the fact that the same values are obtained irrespective of whether
at the start a mixture of the pure components or the pure compound itself is
present. Thus, for example, the same mixture of SO3, SO2, and O2 is obtained
whether equivalent amounts (e.g.! formula weights) of SO2 and O2 are allowed
to react, or an equivalent quantity of SO3 is allowed to decompose under the
same conditions of temperature and volume.
2 SO3 <=> 2 SO2 + 0 2
should be read: sulphur trioxide "in equilibrium with" sulphur dioxide and
oxygen.
Inasmuch as all reactions are, strictly speaking, reversible, it is theoretically
impossible to prepare perfectly pure compounds; for a compound can only
exist as a stable substance when it is in equilibrium with its products of disso-
ciation. For practical purposes, however, it is true that (1) in the equilibrium
mixture the percentage content of dissociation products, or in the other case
the fraction of undissociated substance, is frequently so extremely small that it
SIMPLE COMPOUNDS. 53
becomes negligible, and that (2) the rate at which certain substances decom-
pose after they have once been prepared "pure" is often so extremely slow
that measurable quantities of the dissociation products are formed only after a
very long time.1
MASS-ACTION LAW. The state of equilibrium which combining or decom-
posing substances reach is dependent (1) upon the nature of the reacting
substances, (2) upon their masses, and (3) upon the temperature. The influ-
ence exerted by the masses upon the state of equilibrium can be expressed
mathematically by the so-called Law of Mass Action (Guldberg and Waage,
1867). According to this law, the product of the concentrations of the sub-
stances which are upon the right-hand side of the sign of equilibrium, divided
by the product of the concentrations of the substances on the left-hand side,
is a constant at a given temperature. The concentration is usually expressed
as the number of gram-molecules of substance which are contained in a unit
of volume. If A is the formula of a substance, it is customary to express the
concentration of A by inclosing it in brackets [A]; then if (A) represents the
actual amount of substance present expressed in gram-molecules, and v
the volume, we have c. \
[A] - £ >
If A and B are two substances which by reacting together form two new
substances C and D, with which they finally come to equilibrium,
A + B <=> C + D,
then the mass-action law is expressed as follows:
[C] [D] _ K
[A] [B] *•
If, however, two or more molecules (a, 6, etc., being the numbers) of any of
the substances enter into the reaction, then the concentration of these sub-
stances must be taken a, b, etc., times in the mass-action-law equation. Thus
if a molecules of A react with b molecules of B to form c molecules of C and d
molecules of D, the equation becomes:
[C]c [T>f R
[A]° [Bf
APPLICATION OP THE MASS-ACTION LAW. The value of the mass-action
law for the manufacturing chemist becomes apparent when with its aid the
yields are predicted that can be obtained in the preparation of a substance at
a given temperature but with varying proportions of the reacting materials.
This is particularly well illustrated by measurements of Bodenstein and Pohl
with regard to the contact-process for the manufacture of sulphuric acid.
Sulphur dioxide and oxygen react within a reasonable interval of time to form
sulphur trioxide only when in the presence of catalyzers; the presence of the
catalyzer, however, has no effect upon the equilibrium which is finally reached.
2 SO2 + 0 2 <=> 2 SO3.
1
In old collections of organic preparations, the amount of impurities which
have arisen from a self-decomposition of the material is often very considerable.
64 SIMPLE COMPOUNDS.
If, as before, i> represents the volume of the gas-mixture, and the formulas
inclosed in parentheses the number of gram-molecules of substance present
when equilibrium is reached, then for a given temperature the mass-action
law gives the relation:
(SO3)'
V V3
from which it follows that when T2 > 7\, and the value of Q is positive (exo-
thermic reactions), Ki becomes smaller than K\, and for negative values of Q
(endothermic reactions) K% is greater than Ki. This is based upon the assump-
tion that Q is independent of the temperature at which the reaction takes
place. Whether this is true or not must be ascertained in the case of each
56 OXIDES.
reaction studied. In the synthesis of sulphuric anhydride this has been found
to be practically true; and it is therefore possible, when the analysis of the
equilibrium mixture at a given temperature is known, to compute the com-
position of the equilibrium mixture at any other temperature. The equi-
librium-constants, as above defined, for the sulphuric acid contact-process
have been found to be as follows:
(. K. t. K.
It is, therefore, more important that the process should be carried out at a
relatively low temperature than that an excess of oxygen should be employed.
On the other hand, the temperature cannot be made too low, as then the rate
at which the reaction takes place, even in the presence of a catalyzer, becomes
too small.
The so-called "blast-furnace equilibrium," 2 CO + 02 <=± 2 CO2, is displaced
with increase of temperature, and the reaction proceeds more in the direction
from right to left, because here again the heat of reaction is positive; cf. No. 1.
OXIDES.
27. Liquid Sulphur Dioxide.
Sulphur dioxide is prepared technically by burning either sulphur or
pyrite. On a small scale, it is obtained by the reduction of concentrated
sulphuric acid, or its anhydride, which when hot has a strong oxidizing power:
SO3 + Cu = SO2 + CuO.
The reduction with copper takes place also to a slight extent, according to the
equation:
SO3 + 4 Cu = CuS -I- 3 CuO.
LIQUID SULPHUR DIOXIDE. 57
After the evolution of gas from the flask has ceased, pass a cur-
rent of oxygen through the condensed liquid in the wash-bottle,
still keeping it surrounded with ice, until the color becomes a
pure yellowish brown; only a small amount of the nitrous gases
are lost during this operation. If it is desired to preserve the
preparation, heat the flask containing the liquid nitrogen dioxide
cautiously by means of lukewarm water and distil the liquid
into a sealing tube, in exactly the same manner as with sulphur
dioxide (p. 57). Boiling-point 22° C.
Cork stoppers and rubber tubing are energetically attacked
by the oxides of nitrogen. Therefore, in fitting up the above
apparatus, select corks which fit tightly and protect them with
a coating of vaseline; where the use of rubber connections is
unavoidable, bring the ends of the glass tubing close to-
gether.
Gaseous nitrogen dioxide is always mixed with considerable nitrogen tetrox-
ide, N2O4, formed by association of the dioxide molecules. The mixture is
light brown at room temperature; on being heated it becomes darker as a
result of progressive dissociation: N»O4 —> 2 NO2, but on being heated more
strongly (above 130°) it becomes lighter in color owing to the decomposition
of the dioxide into nitric oxide, NO, and oxygen. These changes in color can
be shown by a simple experiment. Take a 25-30 cm. long glass tube of
difficultly-fusible glass, with about 1 cm. outside diameter, and introduce a
small amount of liquid nitrogen dioxide by the method described for sulphur
dioxide in Preparation No. 27. After all the liquid has been allowed to evapo-
rate, seal the tube filled with the vapor. For the nitrogen dioxide to be com-
pletely dry at this point, phosphorous pentoxide should have been added to the
liquid in the wash bottle before distilling it into the experimental tube. Clamp
the tube in a horizontal position and heat it in the middle with a broad flame
from a Bunsen burner until the gas in this part of the tube appears color-
less (NO + O2); the gas will be dark brown on both sides of the colorless
zone (NO2), while the outer portions of the gas will appear light brown
(NO2 + N2O4).
HYDRIDES.
A few metals combine directly with hydrogen at definite temperatures to
form hydrides (e.g., cerium hydride No. 32).
Copper hydride is formed in aqueous solution by treating cupric salts with
very strong reducing agents (No. 33).
64 HYDRIDES.
Certain products which are formed by the occlusion of hydrogen on
the part of some of the heavy metals, and are to be regarded as solid
solutions, should not be confused with the true hydrides; e.g., palladium-
hydrogen.
AB <=> A+ + B-
[cation] [anion]
= k.
[undissociated compound]
The corresponding dissociation constants, K\, Ki, K3, Kt, may be given as
follows:
[M+] [R-] , [H+] [R-]. _ [M+] [OH-], [H+] [0H~]
1 2 3 l
[MR] ' [HR] ' [MOH] ' [HOH] '
If, in the above equations of hydrolysis, the values for the concentration of
undissociated MR, HR, MOH, and HOH obtained respectively from the last
four expressions are inserted, the equation
K — ^ ' ' Kt
K K
fact that the velocity at which compact substances enter into reaction is often
very slight. (Cf. TiS2, No. 58.)
If the phosphides, nitrides, and certain carbides are regarded as the metal
salts of phosphine, ammonia, and the hydrocarbons, that is to say, as the salts
of hydrogen compounds the acid nature of which is almost infinitesimal (the
acidic constants, K2, of which are therefore extremely small), it then becomes
easy to understand why these substances can be prepared only in the absence
of water (best by direct union of the elements themselves). The readiness
with which the preparation of phosphine from calcium or magnesium phos-
phide (No. 63), of acetylene from calcium carbide (No. 64), and of ammonia
from magnesium or boron nitride (Nos. 60, 61), is carried out, depends on the
ease with which the salts of such extremely weak acids hydrolyze.
dish over the free flame in order to expel the excess of hydro-
chloric acid. Dissolve the residue, which solidifies on cooling, in
3 to 4 liters of water. Dilute one-tenth of this solution in a flask
with a large amount of water, and add caustic soda, avoiding an
excess, in order to precipitate manganese hydroxide. After
settling, siphon off the clear solution, shake up the precipitate
with pure water, and wash it repeatedly by decantation until, at
the end of three or four days, all of the sodium salt has been
removed. Add the manganese slime thus obtained to the remain-
ing nine-tenths of the first solution, and allow the mixture to stand
for several days in a thick-walled, five-liter flask which is placed
in a warm place. Shake the mixture frequently until all of the
iron has been precipitated by means of the manganese hydroxide.
This usually requires about two days, and at the end a little of
the filtered solution should give no test with potassium thiocya-
nate. Filter the solution through a plaited filter and evaporate it
until crystals begin to separate. Then transfer it to a flask and
cool rapidly while rotating under the water tap. Drain the crystal
meal in a suction-funnel and wash it first with 50%, and then with
pure alcohol. By evaporating the mother liquor a further yield
is obtained. Allow the light pink crystals, which are still moist
with alcohol, to dry in contact with the air.
Preparation of Chlorine.
Large quantities of chlorine may be prepared by the oxidation
of hydrochloric acid with pyrolusite. Half fill a round-bottomed
flask of from 1.5 to 2 liters capacity (cf. Fig. 14, p. 77F) with lumps
of pyrolusite, and close the flask with a two-holed stopper;1
through one hole insert a thistle tube, which serves as a safety
tube, and must extend 20 to 30 cm. above the top of the flask
and nearly to the bottom inside. Through the other hole insert
a short delivery tube bent at a right angle. To cause the evolu-
tion of chlorine, pour concentrated commercial hydrochloric acid
through the thistle tube until the pyrolusite is just covered, and
heat the mixture gently on a Babo funnel; regulate the rate at
which the gas is generated by altering the height of the flame
under the evolution flask. A single charge of pyrolusite is suffi-
cient to react with several refillings of the acid. Wash the gas
with water, and dry it (if necessary) by passing it through one or
two bottles containing concentrated sulphuric acid.
It is very convenient to use the dry liquid chlorine which
can be purchased in steel cylinders under pressure; but this
is only to be recommended when large amounts are frequently
used.
When it is desired to prepare a definite amount of chlorine, an
excess of hydrochloric acid can be decomposed by means of a
1
Cork stoppers can be made air tight by immersing them in molten paraffin
at about 150°. Such a paraffined stopper should be tightly wired in place to
prevent it from popping out when the flask is heated.
77C HALOGEN COMPOUNDS.
Fig. 14
troduce a glass tube one-half meter long and about 1 cm. in diam-
eter, and make the joint tight with a piece of rubber tubing around
the glass. This long tube is to serve as a condenser, and to lead
the excess of bromine into the hood.
After starting the current of carbon dioxide, heat the bismuth
gently by means of a Bunsen burner with a flame spreader, and
warm the bromine by placing
the wash bottle in warm water
and renewing the latter as it
cools. Dark-red vapors of
bismuth bromide form and
condense as yellow flakes in
the bulb of the retort, and
to some extent in the glass
tube.
Break the retort, collect
the product, and let it stand
over night in a vacuum desic-
cator to remove any adhering
bromine; or, distil it from a
FIG. 15. smaller plain retort. The
neck of the latter should be
about 8 cm. long and the whole should be suspended in a double
loop of wire (cf. No. 48). Yield, nearly theoretical.-
Boiling-point of Bismuth Bromide. Use a thermometer filled
under pressure, which measures temperatures as high as 5400.1
Place the bismuth bromide in a Jena glass test-tube, 20 cm. long
and 2.5 cm. wide, and heat until the substance boils; suspend
the thermometer so that it reaches well into the vapor. When the
vapors first begin to reach the mercury bulb, lower or remove the
flame for a while so as to avoid heating the thermometer too
suddenly; then heat strongly again. Correct the boiling-point as
thus determined either as directed in No. 6, or by means of finding
the apparent boiling-point of pure sulphur under exactly the same
conditions. The difference between the latter observed reading
and 448° (the true boiling-point of sulphur) is to be applied as a
correction to the apparent boiling-point of the bismuth tribromide.
This very simple method of making the correction for stem expo-
1
Cf. No. 54 for the thermoelectric measurement of temperatures.
TIN TETRACHLORIDE. 79
sure gives good results, provided the two temperatures compared
are not far from one another. Boiling-point of bismuth bromide,
4660.1
50. Tin Tetrachloride.
Make use of the same apparatus as described under the prep-
aration of sulphur chloride (Fig. 14, p. 77F). Place 60 g. of tin
in the retort, and heat it by placing a Bunsen flame underneath.
After the tin is melted pass a rapid current of chlorine, allowing
it to play directly on the surface of the metal. Liquid tin tetra-
chloride, which is colored yellow by dissolved chlorine, collects
in the receiver. When the metal in the retort has all disappeared,
add some tinfoil to the distillate in the receiving flask, stopper the
latter, and allow it to stand until the next day in order that the
dissolved chlorine may all react with the tin.
Place the crude product together with a little tinfoil in a 100 c.c.
distilling flask, provided with a side-arm condenser (Fig. 7).
Fit a thermometer in the neck of the flask, and distil the liquid at
the hood, rejecting the first few drops which pass over. If the
distillate is not perfectly colorless, allow it to stand over night with
more tinfoil and repeat the distillation. Boiling-point, 113.5° to •
114°. Preserve the preparation in a sealed vessel.
When exposed to the atmosphere, tin tetrachloride absorbs
water and soon becomes changed to the solid white hydrate.
Tin tetrachloride can, like titanium tetrachloride, be transformed
into the corresponding sulphide (cf. Titanium Disulphide, No. 58).
The formation of colloidal stannic acid from tin tetrachloride is
discussed under Purple of Cassius, No. 25.
A very convenient method for making tin tetrachloride at room
temperatures from tin and dry chlorine has been described by
R. Lorenz.2 Fill a test tube, about 4 cm. wide and 40 mm. long,
about one-quarter full of dry granulated zinc. Place a cork in the
tube, carrying tubing for the introduction of dry chlorine and also
for the escape of gas. Fasten the tube in an upright position and
introduce chlorine with the tube reaching nearly to the bottom of
the test tube. At fir'st introduce the gas slowly, and later, when
liquid stannic chloride has formed, increase the rate of flow.
1
Author's observation: Victor Meyer found 453° with an air thermometer.
Ann. 364, 122 (1891).
2
R. Lorenz, Z. anorg. Chem., 10, 44 (1895).
80 HALOGEN COMPOUNDS.
From time to time raise the tubing through which the gas is flow-
ing but never let it reach above the top of the liquid chloride.
Purify the stannic chloride as described above.
This method of preparation corresponds to the method used
technically for the recovery of tin from waste tin plate.
Combustion Furnace
PIG. 16.
Combustion Furnace
FIG. 17.
100 c.c. retort, and on the other side with a receiver of twice that
size. Rest the receiver in a dish filled with ice, and add 40 to 50 g.
of titanium tetrachloride to the retort.
Fill the entire apparatus with hydrogen which is conducted
through the inlet tube of the retort. As soon as the gas escaping
at the other end is shown, on testing, to consist of pure hydrogen,
heat the combustion tube to bright redness and heat the tita-
nium tetrachloride nearly to the boiling-point by means of a small
flame, meanwhile passing a rapid stream of hydrogen continuously
through the apparatus. Regulate the temperature of the titanium
tetrachloride so that, as nearly as possible, all of it is decomposed
and none condenses unchanged in the receiver. If, however, this
is not accomplished, pour back the distillate into the retort and
repeat the process. Finally, disconnect the receiver (close the
end of the tube with a cork carrying a short delivery tube bent
downward) and heat the part of the tube projecting beyond the
furnace by fanning it with a flame, until no more white vapors
PHOSPHORUS PENTASULPHIDE. 85
(d) Nitrides.
59. Hydrogen Cyanide, Mercuric Cyanide, Cyanogen, and
Dithio-oxamlde.
Carbon combines with nitrogen, absorbing heat, and forms the nitride,
cyanogen:
2 C + N2 + 7100 cal. = C2N2.
The endothermic nature of this substance (cf. p. 55) accounts for the
formation of cyanogen compounds in the blast furnace, and for its presence in
92 NITRIDES.
the sun, as shown by the spectroscope. When cyanogen is once formed, its
rate of decomposition at a lower temperature is so small that it may be pre-
pared pure in an indirect manner from its compounds and preserved undecom-
posed; cf. No. 64, Acetylene, and No. 67, Hydrogen Peroxide.
Free cyanogen gas which has the formula C2N2 should not be confused with
the univalent radical CN. The radical CN forms a stable atomic grouping
which behaves in the same manner as the halogen atoms in halides, and it
bears the same relation to uncombined cyanogen as the chlorine ion, for
example, bears to free chlorine.
For the preparation of cyanogen gas, hydrogen cyanide (hydrocyanic acid)
is first prepared by Wohler's method of treating either sodium or potassium
ferrocyanide with sulphuric acid. The hydrogen cyanide, together with the
residues, is worked over into mercuric cyanide and the latter decomposed by
heat.
(/) Carbides.
64. Calcium Carbide; Acetylene from Calcium Carbide;
Benzene from Acetylene.
Calcium Carbide. Heat 0.5 g. of lampblack strongly in a
porcelain crucible for a few minutes; after it has cooled mix with
it 0.5 g. of thin shavings of metallic calcium, and heat the mixture
strongly with the blast lamp for a few minutes. After cooling
there is found in addition to lampblack a sintered white mass
which contains some calcium carbide; on testing it with water,
acetylene is formed.
Acetylene from Calcium Carbide. Allow water to drop slowly
from a dropping funnel upon a few pieces of commercial calcium
carbide in a half-liter flask. Pass the acetylene evolved through
a solution of sodium plumbite in order to remove any hydrogen
sulphide, and through an acid solution of copper sulphate to take
out any phosphine. Acetylene burns with a brilliantly luminous
and, unless in a special burner, very smoky flame. Before igniting
the gas it should be tested to see whether all the air has been
removed from the apparatus.
At the temperature of the electric arc, acetylene can be formed from its
elements with absorption of heat. At a bright red heat it decomposes, but at
lower temperatures, although it is likewise unstable, its rate of decomposition
98 CARBIDES.
is extremely slow. (Compare with the similar relations which exist for
cyanogen, No. 59, and hydrogen peroxide, No. 67.)
At a dull red heat acetylene polymerizes to a considerable extent, forming
benzene: 3 C2H2 = CeH6. The presence of benzene in coal-tar may be
attributed to this reaction; indeed, this supposition is supported by the fact
that the yield of benzene in the tar sinks if the temperature of the gas retorts
is raised.
the ordinary oxygen-acids are formed by the union of water and acid anhy-
dride, and the salts of the oxygen-acids by the union of metal oxide and
non-metal oxide. Here also there are produced, quite in accord with the
interpretation of complex salts, new ions, the separate constituents of which
are incapable of entering into independent chemical reactions:
H2O + SO3 = H2[SOJ,
H2[SO4] = 2 H + + [SO4]—.
Thus the sulphate radical does not show the reactions of sulphur any more than
the ferrocyanide radical exhibits those of iron.
Since manifestly every compound containing more than two elements can
under certain conditions behave in such a manner as to indicate the grouping
of two of its constituents into a complex, it appears more rational to include
under complex compounds all substances which are produced from simple com-
pounds by the addition of one or several elements; in most cases the complex
radical behaves, like the hydroxyl group, as a unit, and can thus be treated as
a substituent of an atom.
The most essential difference between the complex and the simple com-
pounds lies in the great variety of ways in which the former can react or dis-
sociate, and this is more evident in proportion to the number of constituents.
There is but one way in which electrolytic and non-electrolytic dissociation can
take place in simple compounds. With complex compounds, on the other
hand, the point of division is usually not the same by the electrolytic as by the
non-electrolytic dissociation:
CaCO3 = Ca + + CO3 (electrolytic dissociation).1
CaCO3 = CaO + CO2 (non-electrolytic dissociation).1
Non-electrolytic dissociation may be of very different types:
KC103 = KC1 + 3 0 (Nos . 74 and 75)
NaNO 3 = NaNO2 + 0 (No. 79).
Na 2 S 2 O 3- Na2SO3 + S (No. 90).
KPbI 3 = KI + Pbl 2 (No. 105).
NH44C1 = NH33++ HC1 (No. 120).
(No. 10).
Ni(NH3)6Br2 = NiBr2 + 6 NH 3 (No. 128).
CLASSIFICATION OF COMPLEX COMPOUNDS. Of the various ways in which
complex compounds can dissociate, the electrolytic dissociation exceeds all others
as regards frequency of occurrence. We may classify the complex compounds,
therefore, as: 1. Those with a complex radical which yields an ion of negative
charge (Chapter IV); 2. Those with a complex radical which yields an ion of
positive charge (Chapter V); 3. Those characterized by very little or no
capacity for electrolytic dissociation (Chapter VI).
1
According to whether the one or the other possibility of dissociation is to
be brought especially to notice, two methods of writing the name and symbol
have been devised: CO2 • CaO, " carbonate of lime "; CaCO3, " calcium car-
bonate "; but it would be just as biased to defend the older name as being the
only satisfactory one as it would be to reject it as " unscientific."
SODIUM PEROXIDE. 101
(c) Polyhalides.
Polysulphides and polyhalides are very closely related. The latter likewise
occur chiefly as salts of the alkali and alkaline earth metals and as the free
halogen acids. The stability of the compounds increases very rapidly in the
series of the alkali metals with the increase in the atomic weight of the metal.
From caesium and rubidium a large number of both simple and mixed polyha-
lides of the type MHa3 and MHa5 (Ha = Cl, Br, or I) have been obtained. As
regards the stability of its polyhalogen compounds, ammonium comes next to
the higher alkali metals; still more stable are the substituted ammonium salts,
namely, the polyhalides of the complicated alkaloids, such as coniin, nicotin,
atropin, narkotin, and of the diazonium salts.
[Br,-]
The three concentrations which are in equilibrium according to the above
equation may be determined by preparing a concentrated solution of bro-
mine in carbon bisulphide and shaking one portion of it with water, and a
second portion with a potassium bromide solution of known molecular con-
centration,1 A. In each experiment the molecular quantities of bromine,
D and B, which pass into the aqueous layer are determined; the excess of
bromine in the second case is equal to that combined in the complex: thus,
[Br3-] = B - D.
Furthermore, [BrJ = D; according to the distribution law, the amount
of free bromine existing in the potassium bromide solution, as well as that
1
The molecular concentration is the amount of substance dissolved in
one liter divided by its molecular weight.
110 LAW OF DISTRIBUTION.
(d) Polynitrides.
72. Sodium Hydrazoate NaN,,, from Sodamide NaNH2.
Sodamide reacts with nitrous oxide to form sodium hydrazoate, the salt
of hydrazoic acid, HN 3 ; from an aqueous solution of sodium hydrazoate,
silver nitrate precipitates the difficultly soluble silver salt, a substance which
like, the pure hydrazoic aeid is extremely explosive. Hydrazoic acid, or
azoimide, was discovered by Curtius in 1890; the method of preparation given
below was devised by W. Wislicenus, in 1892. The relationship between
hydrazoic acid, iodo-hydriodic and brom-hydrobromic acids was pointed out
by Hantzsch in 1895, as well as by others.
Sodamide. Place an aluminium boat containing about 3 g. of
sodium (cf. Sodium Peroxide, No. 65) in a combustion tube;
support the tube on a row burner and heat the sodium to 300-400°
in a current of dry ammonia. Generate this gas by heating
100 c.c. of concentrated ammonia solution and dry it by passing
through a tube containing soda-lime. Hydrogen escapes from
the end of the combustion tube together with the excess of am-
monia, and the mixture can be made to burn. Sodamide must
be preserved in a well-stoppered bottle.
Sodium Hydrazoate. Place a porcelain boat containing 0.5 g.
sodamide in a combustion tube which is inclosed in an asbestos
chamber (Fig. 4, p. 3). Prepare nitrous oxide by heating 10 g. of
ammonium nitrate in a small flask; dry the gas by passing it
through a calcium chloride tube, and conduct it over the sodamide.
Then heat the combustion tube to 250° until the reaction is finished,
after which moist litmus paper is no longer turned blue by the
escaping gases.
NaNH2 + N2O = NaN3 + H2O,
NaNH2 + H2O = NaOH + NH3.
Silver Hydrazoate. Dissolve the sodium hydrazoate in 10 c.c. of
water; a portion of the solution, when treated with a little ferric
chloride, gives a deep brownish-red color. Acidify another and
very small portion of the solution with nitric acid, add silver
nitrate, collect the precipitate on a filter, wash it with water,
alcohol and then ether, and while the filter is still moist with ether,
POTASSIUM CYAN ATE. 113
tear it into several small pieces. After drying in the air the
small amounts of the preparation adhering to the bits of paper will
explode violently when heated or struck. It is very dangerous to
prepare any larger amount of silver hydrazoate than that indicated.
Another simple method for obtaining silver hydrazoate is given
by Sabanejeff. Heat gently 1.5 g. of hydrazine sulphate (No. 122)
with 4 c.c. of nitric acid, d. 1.3, in a test-tube which isprovided
with a gas exit tube bent at right angles. Pass the escaping gas
into a little silver nitrate solution in a second test-tube; silver
hydrazoate is obtained in the form of a white, curdy precipitate.
Filter and test the salt as before, but do not preserve it.
I. C1^H II. Cl
%
O \ 0 H
but the second is undoubtedly the correct one for free hypochlorous acid in
aqueous solution.
The potassium cyanide required for the production of the cyanate is formed,
together with some cyanate, by heating potassium ferrocyanide with an alkali:
K4[Fe(CN)6] + K2O = Fe + KCNO + 5 KCN.
In the presence of an oxidizing agent (CrO3) the cyanide is oxidized to cyanate.
Dehydrate 130 g. of coarsely broken potassium ferrocyanide by
stirring it in a shallow iron dish over a rather low Fletcher burner
flame. When no more dark yellow particles can be detected in
the lumps, grind the mass to a fine powder and remove the last
traces of moisture by reheating. While still warm, triturate 100 g.
114 OXY-HALOGEN ACIDS.
of the powder thus obtained with 75 g. of potassium dichromate
which has been dried by being melted. Heat the mixture in the
iron dish already used, whereupon the reaction will begin in spots
and spread with incandescence throughout the mass. Pulverize
the loose black product while still warm, cover it in a flask with a
warm mixture of 450 c.c. 80% ethyl alcohol and 50 c.c. of methyl
alcohol and boil it with a return condenser on the water bath for
two minutes. Decant the hot solution through a plaited filter into
a beaker, which is cooled with ice, and allow the salt to crystallize
while stirring. Using the mother-liquor from this crystallization
as a solvent, extract the black mass again in the same manner as
before; filter, and repeat the extraction three or four times.
Collect all of the cyanate crystals on the same suction filter, and
after washing with ether, dry them in a vacuum desiccator over
sulphuric acid. Yield, 30-40 grams. The product may be used
in the preparation of urea, or of semicarbazid, No. 123.
Urea from Ammonium Cyanate.
Ammonium cyanate when heated in aqueous solution undergoes a trans-
formation into urea (Wohler, 1828).
NH4CNO = CO(NH2)2.
To carry out this classic reaction, evaporate a solution of 8.1 g.
potassium cyanate and 8.0 g. ammonium nitrate to dryness on the
water bath. Boil the powdered residue in a flask twice with alco-
hol, and concentrate the extract until a crystallization in fine, long
needles is obtained. Yield, about 5 g.
Heat a pinch of dry urea in a test-tube until it just melts, and
keep it at this temperature for about a minute; ammonia escapes.
Dissolve the residue in a little water and add a drop of copper sul-
phate solution and some sodium hydroxide, whereupon a rose-
violet coloration appears; this is the so-called biuret reaction.
and the latter being a much stronger oxidizing agent than sodium hypochlo-
rite, or the hypochlorite ion, it oxidizes chlorite and hypochlorite ions into
chorate ions:
2 HC10 + CIO" = C1O3- + 2 HC1,
3 HC10 + Cl- = C1O3- + 3 HC1.
Heating accelerates these reactions.
The raw materials necessary for these experiments can be prepared more
conveniently by the electrolysis of alkali chloride solution than by purely
chemical means. At the anode, chlorine is the primary product; sodium is
the primary product at the cathode, but it immediately decomposes water
to give sodium hydroxide and hydrogen. The products formed at the elec-
trodes react together in the manner shown above when they are allowed to
mix by diffusion.
The process as outlined above is, however, interfered with somewhat by
the progress of certain secondary reactions. First, the hydrogen produced
at the cathode reduces the hypochlorite, and to some extent the chlorate,
to chloride. Since only the discharged hydrogen atoms, which have not
yet combined to form molecules, cause the reduction, it is advantageous
to restrict the formation of hydrogen to as small an area as possible; by
this means the formation and escape of gaseous hydrogen is favored. In
other words, the current density at the cathode must be kept high. To
further avoid cathodic reduction, the deposition of a thin skin — a "dia-
phragm" — of hydrated chromic oxide on the metal of the cathode works
excellently; this can be most simply accomplished by the electrolytic reduc-
tion of a little alkali chromate which is added to the electrolyte.
Second, the C1O~ and C1O3~ ions, that are formed in the process, carry a
part of the current, and when they become discharged at the anode, they
then react with water to form the free acids and oxygen. The current which
serves to discharge these ions is, therefore, wasted. The loss can be lessened
by using a high anodic current density.
Both of these secondary reactions become more pronounced as the elec-
trolysis progresses, i.e., as the concentration of the chlorate or the hypochlo-
rate becomes greater. This explains why the yield for a given amount of
current gradually grows less with a long-continued electrolysis.
Sodium Hypochlorite. A. The arrangement of the electrical
connections, the external resistance, and the measuring instru-
ments is that described in No. 14 (cf. Fig. 9). Place the beaker
containing the electrolyte, which is a solution of 88 g. of sodium
chloride in 500 c.c. of water (3-normal), inside a larger beaker
containing ice water. For electrodes use two sheets of platinum
of known area, e.g., 30 sq, cm. The anode reaches only into the
upper part of the solution, the cathode nearly to the bottom with
the attached wire insulated by being passed through a glass tube.
The hydrogen bubbles rising from the cathode cause stirring. The
116 OXY-HALOGEN ACIDS.
current density should be the same at the anode as at the cathode
and about 15 amperes per 100 sq. cm. of electrode surface (con-
sidering only one side of the electrodes, since it is chiefly between
the inside surfaces that the current passes). The current strength
holds fairly constant and does not need to be regulated much by
changing the resistance. The minimum potential necessary for
the electrolysis of a normal sodium chloride solution is 2.3 volts,
but for obtaining the desired current density at least 6 volts will
be required. The temperature of the electrolyte should not be
allowed to exceed 20°. Follow the extent of the hypochlorite
formation by an analysis every 10 to 20 minutes. For this pur-
pose, remove 15 c.c. of the electrolyte with a pipette, let it stand in
a beaker a short time until the gas bubbles have escaped, and then
pipette 10 c.c. of it into a solution of potassium iodide which is
slightly acid with hydrochloric acid. Titrate the iodine set free
with 0.1-normal thiosulphate solution, and from the amount
required calculate the entire amount of hypochlorite present in
the whole solution. To determine the current yield,1 find the total
number of ampere-seconds used at the time of taking the samples,
then calculate from this the theoretical yield, on the basis that
96,540 amperes flowing for one second would set free one equivalent
each of sodium and of chlorine and thus produce one-half mol. of
NaClO. The observed data and the calculated values can be
arranged advantageously in a table as follows:
0 500 10 6. 0 0 0 0
10 500 11 6.6
20 500 13 6.3 2.91 12.6 2.34 80.4%
40 485 18 6.2 2.89 ' 19.8 1.30 45.0%
At 10°. At ioo°.
Thus the interaction of the salts used depends entirely upon the solu-
bility relations.
This method has had an important application in the manufacture of
potassium nitrate for the gunpowder industry.
SILVER NITRATE. 123
Dissolve 190 g. of crude Chile saltpeter in 200 c.c. of boiling
water in a previously weighed flask. To the boiling solution
add 150 g. of powdered potassium chloride and boil for half an
hour longer, replacing any water lost by evaporation. The con-
tents of the flask should at the end weigh 520 to 540 g. While still
hot, filter rapidly through a Biichner funnel and rinse the residue
with a test-tubeful of hot water. Cool the filtrate rapidly while
shaking, whereby a crystalline meal of potassium nitrate is formed.
Evaporate the mother-liquor; remove the sodium chloride by
filtering while hot; and cool the1 filtrate rapidly to obtain more
potassium nitrate. If sufficient mother-liquor still remains, work
it up in the same manner to obtain a further yield. Unite all of
the crystals of potassium nitrate and purify them by recrystalliza-
tion until they are free from chloride. The yield is from 60 to
70% of the calculated.
81. Silver Nitrate.
The nitrates of the alkali metals break down into nitrites when heated;
those of all the other metals dissociate into metallic oxide and nitric anhy-
dride or its decomposition products:
Cu(NO3)2 = CuO + N2O4 + O.
This dissociation begins to take place at very different temperatures with
the various metals. Silver nitrate can be melted without decomposition,
while, at the same temperature, the nitrates of metals with a higher valence,
for example, copper nitrate, are decomposed; thus by melting a mixture of
these two nitrates and dissolving the fusion, silver nitrate can be obtained
free from copper.
By carefully regulating the temperature and repeating the process, mix-
tures of very closely related nitrates can be separated; the "nitrate method"
for separating the metals of the rare-earths depends upon this principle.
A completely analogous behavior is shown by the sulphates, as in the
Ziervogel process for obtaining silver from argentiferous pyrite. By roasting,
the sulphates of the metals are first formed, all of which, however, with the
exception of silver sulphate, decompose at a somewhat higher temperature
into metal oxide and sulphur trioxide; by leaching, the silver is obtained in
the solution.
Dissolve a silver coin in 30% nitric acid, evaporate the solution
to dryness, and transfer the residue to a porcelain crucible. Place
this crucible upon a wire triangle inside a larger crucible, and
gradually heat the outer crucible to a dull red heat. When the
decomposition is completed, extract the black residue with water,
concentrate the filtrate and test it for copper. Should any copper
124 NITRITE AND NITRATES.
be present, which will frequently be the case, evaporate the solu-
tion to dryness and heat the silver nitrate carefully until it just
begins to melt. In this way the remainder of the copper nitrate
is decomposed. Repeat the extraction with water.
The copper oxide residues should contain very little silver.
83. Bismuth Nitrate and Basic Bismuth Nitrate.
Bismuth nitrate may be obtained from the solution of the metal in nitric
acid in the form of large, colorless crystals with 5 molecules of water. The
salt is strongly hydrolyzed by water, and, according to the temperature and
the concentration of the acid, basic salts of various compositions are pro-
duced.1 The following directions yield a precipitate of approximately the
composition, 4 Bi2O3 • 3 N2O6 • 9 H2O, which is not, however, to be regarded as
a homogeneous compound. This is the so-called bismuth subnitrate so much
used in medicine and often called bismuth by physicians.
Dissolve 100 g. of coarsely pulverized bismuth by heating it in
a flask with 500 g. of nitric acid (sp. gr. 1.2). Filter through a
hardened filter, using suction, and evaporate in a porcelain dish
until crystallization begins. Collect the crystals on a suction-
filter, wash with a little nitric acid (sp. gr. 1.2) and dry in a desic-
cator. Evaporate the mother-liquor to obtain more crystals.
To prepare the above mentioned basic salt, triturate one part of
the bismuth nitrate with four parts of water and stir this mixture
into 21 parts of boiling water. Allow the precipitate to settle,
wash by decantation, collect on a suction-filter and dry the prepa-
ration at a temperature not exceeding 30°.
(d) Manganates and Ferrates.
83. Potassium Permanganate by the Fusion Method.
By fusing manganese compounds in an oxidizing-alkaline flux a man-
ganate is formed, and this, when it is dissolved in water and the free alkali
is neutralized, changes into permanganate and manganese dioxide:
MnO2 + K2CO3 + O = CO2 + K 2 Mn0i,
3 K 2 Mn0 4 + 2 H2O = MnO2 + 4 KOH + 2 KMnO4.
Melt together 80 g. of potassium hydroxide and 40 g. of potas-
sium chlorate in a sheet iron crucible 6 to 8 cm. in diameter.
Remove the flame and while stirring with an iron spatula (a heavy
wire or an old file), add 80 g. of finely powdered pyrolusite, quite
rapidly but not all at once. The fusion effervesces somewhat.
1
Cf. A. Findlay: The Phase Rule.
ELECTROLYTIC PREPARATION. 125
1
Concerning the various hydrates of SO3, see R. Knietsch, Ber. 34, 4100
(1901). Notice particularly the curves.
128 OXY-ACIDS OF SULPHUR.
FIG. 20.
rate at which air is drawn through the apparatus. The total air
admitted is regulated by a screw clamp placed between the safety-
bottle and the water-pump, and the proportion passing over the
pyrite and through the nitric acid is governed by the clamp shown
at the end of the combustion tube.
First heat the pyrite in a slow stream of air until it takes fire.
Then warm the nitric acid and, by partially closing the clamp at
the end of the " pyrite-burner," cause air to enter also through the
capillary in the distilling flask, and thus carry nitric acid vapors
into the large bottle. Heat the pyrite strongly and continuously;
regulate the current of air laden with nitric acid so that red fumes
are always present in the bottle. If insufficient nitric acid is pro-
vided, the walls of the flask become coated with colorless crystals
of nitrosyl sulphuric acid (" chamber crystals "; cf. No. 152).
When the pyrite is completely burned, disconnect the apparatus,
and wash the contents of the bottle into a beaker with a little
water. Test the solution qualitatively, and determine by titration
the yield of sulphuric acid.
O=P-OH HO-P-0-P-OH
HO/ X
OH
Metaphosphoric acid. Pyrophosphoric acid.
HYPOPHOSPHOHIC ACID, H2PO3, which was formerly written H4P2O6, has
recently been found to have a molecular weight corresponding to the smaller
molecule, and is presumably derived from quadrivalent phosphorus.
piece of linen laid in a large Biichner funnel, and return the fil-
trate to the beaker.
When the reaction is complete remove the silicic acid, as above,
with a linen filter, and estimate the yield by analyzing a sample of
the filtrate. Either titrate hot with 0.1-normal sodium hydroxide,
using phenolphthalein as indicator, whereby the reaction is
H2SiF6 + 6 NaOH = 6 NaF + H4Si04 + 2 H2O,
or else add to the solution an excess of neutral calcium chloride
and titrate the hydrochloric acid set free, using methyl-orange as
indicator:
H2SiF6 + 3 CaCl2 + 4 H2O = 3 CaF2 + 6 HC1 + H4Si04.
Add some potassium chloride solution to another sample of the
product; the difficultly soluble potassium salt separates, and,
although the precipitate is barely visible at first, the liquid is
eventually left in a jelly-like condition.
solution is placed between a heated slide and cover glass under the
microscope.
If it is desired to obtain the dry salt, it should be collected on a
filter, and, without washing, pressed between filter papers and
dried in a vacuum desiccator.
Potassium lead iodide possesses the remarkable property of
being extremely soluble in acetone. If the preparation is treated
while still moist with 10 to 15 c.c. of acetone, there is produced,
even in the cold, a yellow solution from which the salt can be
precipitated by addition of two or three volumes of ether. On
evaporating the acetone solution, no well-formed crystals are
obtained. If a few drops of this solution are allowed to evaporate
on filter paper the salt is obtained in a state of very fine subdivision,
in which condition it is extremely sensitive to the least traces of
moisture. Even the moisture of the air suffices to decompose
the salt in a short time; the yellow color of lead iodide which
thereby appears indicates in the sharpest manner the presence of
traces of water. If another paper prepared in the same manner
is left in a vacuum desiccator over sulphuric acid, no noticeable
yellow color appears; on opening the desiccator, however, it
develops immediately.
drain off the liquid, and wash the crystals with the ether. Bring
the ether-hydroferrocyanic-acid compound into an Erlenmeyer
flask, which is provided with an inlet and an outlet tube, and heat
it in an atmosphere of dry hydrogen at 80° to 90° on the water
bath. The ether is removed in this way in about an hour. Yield,
about 12 g. The hydroferrocyanic acid is nearly colorless at first,
but it quickly develops a light-blue color by contact with the air.
Copaux assumes that two atoms of hydrogen can also act as the central
atom. In this way the hypothetical acid H2 « or H^H^Oe) is obtained,
from which metatungstic acid, Hio[H2(W207)6], is derived.
bottom layer into a dry beaker, free it from drops of water by pour-
ing it back and forth into dry beakers, and remove the ether by
warming it for some time upon the water bath. Dissolve the resi-
due in a little water, filter the solution, concentrate it to a small
volume, and bring it to crystallization by surrounding the beaker
with ice. If no crystals separate, the solution must be concen-
trated still further. Drain the crystals quickly from the liquid; do
not wash this product, but free it from mother-liquor by spreading
it on an unglazed plate. After the crystals have become white on
the porous plate, dry them completely by letting them remain in
a vacuum desiccator over sulphuric acid. Yield, 13 to 14 g.
When working with larger amounts of silicotungstic acid, large
characteristic crystals can be obtained by slow evaporation in a
vacuum desiccator.
ORGANOCOMPLEX COMPOUNDS.
118. Potassium Ferric Oxalate, K3[Fe(C2O4)3]; Platinotypes.
Oxidize a solution of 35 g. of crystallized ferrous sulphate in
100 c.c. of water by boiling it with just the necessary amount of
nitric acid (test with potassium ferricyanide). Dilute the liquid
to 2 liters, add ammonia and wash the precipitate of hydrated ferric
oxide by decantation for several days, then collect it on a large,
plaited filter and wash it with hot water.
To a hot solution of 44 g. of crystallized acid potassium oxalate
in 100 c.c. of water add the ferric oxide hydrogel a little at a time
until no more will dissolve. Such a solution is sensitive to direct
sunlight. Filter and concentrate the filtrate to crystallization,
wash the emerald-green crystals with water and alcohol, and dry
them in a vacuum desiccator over sulphuric acid.
Platinotypes.
Potassium ferric oxalate is changed by the action of light to potassium
ferrous oxalate, and the latter reduces platinum salts to metallic platinum.
Soak a piece of filter paper, the size of a photographic plate,
with potassium ferric oxalate solution and dry it in the hot closet.
Then place the paper in a shallow glass tray; wet it uniformly with
about 2 c.c. of a 5% chloroplatinic acid solution, whereupon it
turns yellowish red; and dry it again, avoiding any strong illumi-
nation. Then expose it for about an hour to a medium light under
154 ORGANOCOMPLEX COMPOUNDS.
H—N-H- -Cl.
H^ J
Compounds with complex cations dissociate according to reactions which
are the raverse of the reactions of their formation; naturally both formation
and dissociation may take place in stages.
In the production of complex cations, ammonia and water come most
frequently into consideration. Among the ammonia compounds, those in
which ammonia, or a substituted ammonia, is joined to hydrogen (ammonium
or substituted ammonium compounds) are to be distinguished from those
in which ammonia, or a substituted ammonia, is joined to metal. The classi-
fication which follows is based upon this distinction.
Other complex-producing substances than those mentioned are less often
met with. As representative of the compounds which they form, the nitric-
oxide-metal compounds (cf. the well-known test for nitric acid with ferrous
sulphate) may be mentioned, as well as the addition products with alcohol,
ether, and ethyl acetate, which are similar in nature to the hydrates.
155
156 AMMONIUM COMPOUNDS.
Hydrazine (No. 122) and semicarbazid (No. 123) show a similar behavior:
(CH3)2CO + H 2 NNH 2 = (CH3)2C : N-NH 2 + H2O
hydrazine acetone-hydrazone
2 (CH 3 ) 2 CO + H 2 N - N H 2 = (CH3)2C : N - N : C(CH 3 ) 2 + 2 H 2 O
acetone-azine
(CH3)2CO + H 2 N-NH-CO-NH 2 = (CH3)2C : N-NHCONH 2 +H 2 O
semicarbazide acetone-semicarbazone
thus formed breaks down with water, essentially into sulphur dioxide, carbon
dioxide, and hydrazine sulphate:
H.N
I ^ C(SO3H)2 + H2O = (H 2 N.NH a )H£O 4 + CO2 + 2 SO,.
C= 0
METAL-AMMONIA COMPOUNDS.
The importance of the metal-ammonia compounds lies in their great
number,1 in their stability, and in the significance of the theoretical questions
pertaining to them. Among the best known of these compounds are those
containing tervalent cobalt, chromium, rhodium and iridium. Metal-ammonia
compounds are formed by the addition of gaseous ammonia to the solid salts,
or by the union of the two components in solution.
The first method, inasmuch as it represents the combination of two sub-
stances of widely different volatility (very difficultly volatile metal salt and
200
1
Werner estimates the number of compounds of the general formula
MXB(NH3)m as 1700.
164 METAL-AMMONIA COMPOUNDS.
4. Undissociated Compound.
Trinitritotriammine Cobalt [Co(NH 3 ) 3 (NO 2 ) 3 ] . . . . Triamminecobaltic Nitrite of Gibbs or of Erd-
mann (No. 139).
1
Recently Werner has designated the group NO2 in the complex as nilro (1907).
i '
2
See Introductory part to No. 138. Oi
O5
00
Tetrammineplatinous Salts [Pt(NH 3 )JX 2 Platodiammine Salts: Salts of the first Reiset Base
(Nos. 141 and 142.) g
Chlorotriammineplatinous Salts. . . . [Pt(NH 3 ) 3 Cl]X . . . . Platomonodiammine.
>
1.3 Dichlorodiammine Platinum! . . .
1.2 Dichlorodiammine Platinum} . . . [ t( p NH
3) 2 Cl 2 ]
Platosammine Chloride; Chloride of the second Reiset
Base (No. 143).
Platosemidiammine Chloride; Salt of Peyrone (No.
r>
143).
o
TABLE 3. — PLATINIAMMONIA COMPOUNDS.1
Rational Name. Formula. Old Name. o
o
Hexammineplatinic Chloride [Pt(NH3)6]Cl4 Chloride of Drechsel's Base. g
Dichlorotetrammineplatinic Salts .
Trichlorotriammineplatinic Salts .
.
.
. [Pt(NH3)4Cl2] X2 . . . . Platindiammine; Salt of Gros's Base.
. [Pt(NH3)3Cl3]X . . . . Platinmonodiammine Salts.
a
1.6 Tetrachlorodiammine Platinum [ . ._ „__ . „. ( Platiniammine Chloride; Gerhardt's Salt.
1.2 Tetrachlorodiammine Platinum ) . " f Platinisemidiammine Chloride.
1
The use of the discoverer's name is less customary in the more recent literature; but on the other hand, the old rational designations,
which originated with Biomstrand, and are given in the same column in the above tables, are still often employed. This leads to confusion because
according to the Biomstrand momenclature " ammine " usually signifies two ammonia molecules.
SILVER-AMMONIA SULPHATE. 169
tion that the constutuents of the "inner sphere" which surrounds the central
metal atom are actually situated at the corners of a square or of an octahedron.
Two different pairs of substituents are manifestly capable of two different
arrangements at the corners of a square;
NH3X /Cl NH,v, /Cl
NH3X X
C1 CK X
NH3
1.2 or cis-position 1.3 or trans-position.
If, however, three substituents in a square are the same and the fourth
different, such an isomerism is impossible. The actual lack of isomers in the
latter case and their existence in the former, strongly support the above
assumption.
Similarly, the isomerism of the two dinitritotetramminecobaltic series is
explained by the use of the corresponding octahedral formulas (cf. No. 138).
As has already been stated, the external valence of the complex is equal to
the difference between the valence of the metal and the total valence of the
acid radicals contained in the complex. This external valence may become
zero, or even negative when the valence of the acid part of the complex
preponderates. In the following series of seven cobalt compounds, the valence
of the complex changes progressively from three positive to three negative:
[Co(NH3)6]Cl3 [Co(NH3)6NO2]Cl2 [Co(NH3)4(NO2)2]Cl [Co(NH3)3(NO2)J
K[Co(NH3)2(NO2)4] (No. 115) K2[Co(NH3)(NO2)5]
K3[Co(NOa)6] (No. 114).
The binding power for potassium, or in other words the affinity for nega-
tive electrons, is occasioned by the valences of the nitrite radicals. The bind-
ing of these nitrite groups within the complex takes place in part by means of
the secondary valences (cf. pp. 141 and 155).
2^ ,..-NO2-l-K
N02-Co-N02- -K
^ --NO 2 -J-K
so that of the six nitrite groups attached to the cobalt, three are held by the
principal valences and three by the secondary valences of the metal. Inas-
much as the secondary valences are weaker than the principal ones, this view
corresponds well with the formation of potassium cobaltinitrite from potas-
sium nitrite and cobaltic nitrite, and with its manner of ionizing. For
the further development of this theory, which leads to the conception of
"indirect combination," the work of Werner already cited should be consulted.
the carbonatotetrammine salt with hydrochloric acid, there is formed, for the
most part, chloroaquotetramminecobaltic chloride. This is changed, on being
heated in an ammoniacal solution, into aquopentamminecobaltic chloride, and
the latter on being acidified with hydrochloric acid is converted into chloro-
pentamminecobaltic chloride. This is one of the best and longest-known mem-
bers of the entire series, and has, on account of its color and chlorine content,
been called chloropurpureocobaltic chloride. It may also be prepared by
thermal decomposition of luteocobalt chloride.
dilute nitric acid, filter, and dilute the solution to 100 c.c. Add
200 c.c. of concentrated ammonia, heat the solution to boiling,
and oxidize the salt by adding 25.4 g. of iodine, which must be
introduced slowly at first. A vigorous reaction takes place and a
pale yellowish-brown precipitate of luteo salt is formed. All the
iodine should be added in the course of half an hour. Allow the
liquid to cool and after it has stood about two hours filter off
the precipitate and wash it with water containing ammonia. Then
boil the salt with 200 c.c. of approximately 56% nitric acid, where-
by iodine is set free which can be recovered to some extent by
means of two funnels, one placed in the flask and the other inverted
over it to form a double cone. When all the iodine has been
expelled, filter off the precipitate, drain it with suction, wash it
with water containing nitric acid and finally with alcohol, and dry
it in the hot closet. Yield, about 22 grams.
number of times, and, after it has stood for 24 hours, filter off the
slime of hydrated manganese dioxide. Neutralize the nitrate with
dilute hydrochloric acid, and, while keeping it cold by surround-
ing the vessel with ice, precipitate the product by the gradual
addition of a mixture of three volumes of concentrated hydro-
chloric acid and one volume of alcohol. Wash the precipitate
with alcohol. Yield, 12 to 15 grams.
3. Purification of Aquopentamminecobaltic Chloride. Dissolve
the crude product, prepared according to either 1 or 2, in cold,
2% ammonia, using 75 c.c. for each 10 g. of the salt; filter off the
slight residue of luteo salt, and, while keeping the solution cold
with ice, precipitate the roseo salt by the gradual addition of con-
centrated hydrochloric acid. Drain the precipitate and wash
it with a mixture of equal parts concentrated hydrochloric acid
and water, then with alcohol, and dry it in a warm place.
4. Aquopentamminecobaltic Oxalate. Dissolve 10 g. of chloro-
pentamminecobaltic chloride in a flask with 75 c.c. of water and
50 c.c. of 10% ammonia, heating on the water-bath. After cool-
ing the deep-red solution to the room temperature, filter it and
treat with a solution of oxalic acid until a precipitate begins to
form, then continue to add the reagent very carefully until the
solution is just acid. Filter, and wash the salt with water.
To purify the product, dissolve it as directed under 3, and re-
precipitate the salt by the careful addition of oxalic acid solution.
Drain the precipitate, wash it with water, then with alcohol, and
dry it in a warm place. Yield, 9 grams of pure1 substance.
5. Aquopentamminecobaltic Chloride from Aquopentammineco-
baltic Oxalate. Cover 10 g. of aquopentamminecobaltic oxalate
at room temperature with 30 c.c. of water and dissolve the salt by
the addition of 50 c.c. of normal hydrochloric acid. Cool the solu-
tion with ice to about 0° and precipitate it very slowly by allow-
ing 100 c.c. of concentrated hydrochloric acid to flow upon it
drop by drop. Drain off the bright red precipitate and wash it
first with hydrochloric acid diluted to one-half and then with
alcohol. Yield, about 8 g. of perfectly pure aquopentammineco-
baltic chloride.
1
The separation of luteo salt present as impurity is here more complete
than according to procedure 3, because its oxalate is much more insoluble
than its chloride.
DINITBITOTETRAMMINECOBALTIC SALTS. 179
Aquopentamminecobaltic chloride changes slowly on long keep-
ing into chloropurpureocobaltic chloride.
I X X
6 X NH 3
1, 6: trans-position 1, 2 : cis-position
X,
Co / / C o
HYDRATES.
The hydrates formed by crystallization from aqueous solutions vary in
composition with the temperature and concentration of the solution. A
systematic determination of the hydrates which a compound can form, as
well as of the conditions under which they can exist, can be carried out in
the light of the principles of heterogeneous equilibrium.
HYDRATES. 189
1. THERMIC ANALYSIS. If the freezing-point of an aqueous solution of a
salt is determined at various concentrations and the results are plotted with
the temperatures as ordinates and with the concentrations in per cent as
abscissas, a curve AC is obtained which starts at the freezing-point of pure
water and descends in accordance with the law of Raoult and van't Hoff
(Fig. 23). The highly concentrated solutions, on the other hand, are to be
regarded as solutions of water in the salt; the curve CB shows the region in
which the freezing-point rises as the amount of water diminishes until finally
the freezing-point (or melting-point) of the pure salt is reached. In the
region of the first curve, that part of the mixture which acts as solvent
crystallizes out on freezing, — in this case pure ice; in the region of the sec-
ond curve, the solid salt is deposited as the solution cools. The point where
these two curves intersect is called the eutectic point, and is characterized by
the fact that salt and ice crystallize simultaneously in an intimate, eutectic
mixture. Such mixtures, which are also known as cryohydrates, possess
freezing (or melting) points which are constant, and are lower than the freez-
ing-point of pure water; they are on this account used for maintaining uniform
temperatures of below zero centigrade.
If the salt employed forms a chemical compound with water, then the two
systems water/hydrate on the one hand and hydrate/anhydrous salt on the
other hand are each to be considered independently, according to the principle
just outlined. If, as before, the concentrations are plotted as abscissas and
the temperatures as ordinates, a double pair of curves is obtained with two
eutectic points. The two inside curves unite in a common maximum which
is the freezing-point of the pure hydrate (Fig. 24). Conversely it is clear
that by determining the freezing-points of a complete series of mixtures of
the salt and water, the presence of a hydrate can be detected by the appear-
ance of a maximum on the curve, and its composition can be read by dropping
a perpendicular from the maximum point to the horizontal axis. Several
maximum points indicate the presence of several hydrates. In this way
Roozeboom has, for example, proved in the case of ferric chloride the existence
of the hydrates 2FeCl 3 -4H 2 O. 2FeCl3-5H2O, 2FeCl 3 -7H 2 O, 2FeCl3-12H2O.
190 HYDRATES.
This method of analysis does not apply solely to the mixtures of a salt
and water, but it can be used very generally to prove the existence of com-
pounds. It has acquired a high importance in the study of alloys (Tammann
and his students: see articles in Z. anorg. Chem. mostly later than 1903).
2. VAPOR TENSION ANALYSIS. When a hydrated crystallized salt is in
equilibrium with water vapor, its water of hydration can be progressively with-
drawn in the same manner that ammonia is withdrawn from the metal ammo-
nia compounds (cf. p. 163). Two methods are available by which salts can be
investigated from this point of view. According to the first the vapor pressure
of the salt is determined for varying water content, and a curve is constructed
with the aqueous tensions as ordinates and the corresponding percentages of
water as abscissas; if the salt forms a number of different hydrates, the vapor
pressure above any given mixture of the hydrates remains constant, when water
is slowly withdrawn, as long as any of the hydrate richest in water is still pres-
ent. When this hydrate is entirely exhausted, the pressure sinks abruptly,
and a second, and lower, horizontal line on the plot corresponds to the tension
of the next lower hydrate, etc. (cf. Fig. 25). The tension of aqueous vapor in
the case of hydrated cupric sulphate is given in the following table:
CuSO4 + 4.5 H2O 46.3 mm. CuSO4 + 1.5 H2O 29.7 mm.
CuSO4 + 3.5 H 2 0 47.1 " CuSO4 + 0.5 H 2 0 4.4 "
CuSO4 + 2.5 H2O 29.9 "
From this we may conclude that the following hydrates exist: CuSO4 • 5H 2 O;
CuSO4 • 3 H2O; CuSO4 • 1 H2O. The vapor pressure of the pentahydrate is
about 46 mm. and remains constant, irrespective of the amount present,
until the pentahydrate has entirely disappeared. Then the pressure drops to
that of the trihydrate (about 30 mm.), and again remains constant until
this is completely changed into monohydrate (vapor pressure about 4.5 mm.).
The other method of vapor tension analysis consists in determining the
decomposition temperature under a constant pressure of aqueous vapor
(cf. p. 163). Approximate values for the decomposition temperature can
be obtained, however, by finding the point at which
Preset) re — water is given up when the salt is heated in any
40 mm- indifferent atmosphere. In this way crystallized
copper sulphate loses the last molecule of water at
80 " •
220° to 240°, and from this and the fact that the
!0 " - other molecules of water escape at much lower tem-
peratures, the existence of a definite monohydrate
10 " .
has been recognized for a long time.
0 " 1 •jBo I n the cases where the water is not chemically
p I G 25 bound in a compound, but is merely adsorbed (cf.
pp. 41 and 44), either of these methods of investi-
gation shows merely a continuous loss of water with rising temperature, or
diminishing pressure.
The question as to how the water is united with the components of the
MELTING-POINT MAXIMUM. 191
24% and about 33%, it rises from - 8.4° to above 70°. If the
eutectic point itself is not actually obtained in one of the experi-
ments, it is easily found as the intersection point of the two curves.
water at 32°, filter, and divide the solution equally among five
small, clean flasks which have been freshly rinsed with distilled
water. In filling the flasks take care not to wet the necks with
the solution. Immediately stopper each flask with a loose plug
of cotton. Allow two of the flasks to stand in the ice-chest over
night, or longer, until the heptahydrate has crystallized out in
large, closely packed crystals which fill about one-third the vol-
ume of the liquid. Allow the three other flasks to cool to room
temperature; a thick, oily solution is obtained from which,
although it is supersaturated, no crystals separate even when
the liquid is gently rotated. Inoculate the first flask with a
minute fragment of sodium sulphate, whereupon crystals at once
begin to form at the point inoculated and grow rapidly until the
whole contents of the flask have solidified. Place a trace of
sodium sulphate upon a piece of filter paper, then brush it
off as completely as possible. Tear off a piece of this filter
paper and use it to inoculate the contents of the second flask.
Open the third flask, and close it with the thumb, which has
first been well rinsed with distilled water. If the thumb is per-
fectly clean and free from crystals of the salt and particles of
dust, the solution will bear shaking without the appearance of
crystals.
Introduce a trace of decahydrate into each of the two flasks
which contain the deposited heptahydrate. The supernatant
solution then crystallizes into the decahydrate so that the two
hydrates are obtained together in the flask one above the other.
After standing a long time, the more soluble heptahydrate goes
over into the less soluble decahydrate.
COMPLEX NON-ELECTROLYTES.
IN this chapter are brought together a number of different kinds of sub-
stances, many of them containing organic radicals, and all of them showing
very little, if any, tendency to undergo electrolytic dissociation. The ability
of these substances to dissociate otherwise than electrolytically is slight, and
most of them can, like many of the pure organic compounds, be distilled with-
out undergoing decomposition. It is characteristic of them, however, that in
the presence of water they suffer hydrolysis (saponification) instead of elec-
trolytic dissociation (cf. p. 60). Here, as in the case of organic substances, it
is permissible to develop structural formulas, and thus the probable structure
of the products of hydrolysis can be derived. For example, it is possible to
deduce the structure of certain inorganic acids from the graphic formulas of
their chlorides and esters. Cf. Cyanic Acid, p. 113; Oxy-acids of Sulphur,
p. 126; Acids of Phosphorus p. 135.
ACID CHLORIDES.
149. Sulphuric Acid Dichloride (Sulphuryl Chloride), SO2C12, and
Sulphuric Acid Monochloride (Chlorosulphonic Acid), HO.SO2C1.
By the term add chloride is understood a substance which is converted
into an oxy-acid when its chlorine atoms are replaced with hydroxyl groups.
Sulphuryl chloride, SO2C12 is the chloride of sulphuric acid:
SO2C12 + 2 H2O = SO2(OH)2 + 2 HC1.
It is produced by the direct union of sulphur dioxide and chlorine in the sun-
light; the combination takes place more readily, however, in the presence of
catalyzers such as anhydrous acetic acid, porous charcoal, or, most efficient
of all, camphor.
Sulphuric acid monochloride is formed by the partial hydrolysis of sul-
phuryl chloride, but it can also be prepared from sulphuric acid and phos-
phorus pentachloride by a reaction which is of very general applicability.
Phosphorus pentachloride acts upon substances which contain hydroxyl in
such a way that phosphorus oxychloride, hydrogen chloride, and a chloro-
substitution product of the original material are formed:
R.OH + PC15 = RC1 + POC13 + HC1
In certain cases the phosphorus oxychloride itself also acts as a chlorinating
agent.
201
202 ACID CHLORIDES.
ESTERS.
Esters are derived from acids by the replacement of the acid hydrogen
atoms by hydrocarbon radicals; they are often called "etherial salts," but are
to be distinguished from ordinary salts by their inability to dissociate elec-
trolytically.
HNO3 CH3NO3
Nitric Acid. Methyl nitrate (methylester of nitric acid).
Of the methods of forming such substances the following three will be con-
sidered here:
1. From an acid and an alcohol with elimination of water:
C2H6OH + HNO3 = H2O + C2H5NO3 (No. 153)
Ethyl Alcohol Ethyl Nitrate
mass action. This law requires that at a constant temperature the relation
expressed in the following equation shall hold true:
[Ester] . [Water] _
[Acid] • [Alcohol] ~
It is evident from this equation that to obtain a favorable yield of ester the
concentration of the water should be kept as low as possible. This can be
accomplished in practice by adding concentrated sulphuric acid to the reac-
tion mixture. On the other hand, saponification is favored by the removal
of the acid, and this can be brought about by the addition of a base.
few drops of alcohol, drive off the latter by boiling a short time,
cool, and acidify the solution with dilute sulphuric acid. Sul-
phur dioxide escapes and can be recognized by its odor.
Saponify a second portion in like manner by adding barium
hydroxide together with a few drops of alcohol; boil off the
alcohol and acidify the cooled solution with nitric acid. At first
no change is noticed, but on boiling a cloudiness appears which
is caused by the precipitation of barium sulphate.
METAL-ORGANIC COMPOUNDS.
The metal in the metal-organic compounds is bound directly to hydro-
carbon radicals or to carbon monoxide: Zn(C2H5)2, zinc ethyl (No. 159);
Pb(C6H6)4, lead tetraphenyl (No. 160); Ni(CO)4, nickel carbonyl (No. 161).
The low boiling-points of these compounds, which would scarcely lead one to
suspect the presence of a metal, permit in most cases a ready determination
of the vapor density and thus of the molecular weight. In this respect, as
in fact in almost their entire chemical behavior (e.g. the ready solubility in
organic solvents), these compounds show themselves to be closely related to
the purely organic compounds. It is, therefore, not surprising that the
theory which has found its most specific application, as well as its greatest
success, in the field of organic chemistry — namely the valence theory in its
214 METAL-ORGANIC COMPOUNDS.
original form — should have originated in the discovery of these very metal-
organic compounds. It was not until Frankland (1853) had recognized that
the saturation capacity of the metals in these compounds could be measured
by the number of univalent organic radicals which are joined directly to the
metal atom that this combining capacity began to be regarded as a funda-
mental property of the metals — as well as of all other elements — which
governs their behavior in all of their compounds.
Spectroscopic Analysis.
The hydrogen lines are very sharp and easy to observe; ready
prepared tubes filled with hydrogen under diminished pressure
can be used, and are to be excited by means of an induction coil.
Plot the scale readings as abscissas and the corresponding wave
BERYLLIUM HYDROXIDE. 221
drawn out a little at one end, and fill the tube with hydrogen
which has been washed successively with caustic soda solution,
silver nitrate, potassium permanganate, and sulphuric acid.
Heat in the atmosphere of hydrogen for 15 minutes to moder-
ate redness so that the temperature surely exceeds 470°. When
cold, determine the loss in weight, and if necessary repeat the
heating until finally the change in weight corresponds to the
change from the trioxide to the dioxide. In this way a reddish-
brown glistening powder is obtained.1 Stronger ignition in
hydrogen causes the formation of metallic molybdenum.
I Hood
_ B a
Jj=» IP Z3
702->n . p-aBSS-^ Burner
Fig. 26.
abundant source was sought.1 This was found in the mineral monazite, a
phosphate of the rare earths and of thorium, which contains 4 to 7% of thorium
oxide and 50 to 60% of the rare earths, about one-half of the latter being
cerium oxide. This mineral occurs frequently, although only in small
amounts, in primary rocks; but it is found in some places concentrated in
secondary deposits.
ness on the water bath, dissolve the residue in hot water, and
precipitate thorium hydroxide from the boiling solution by add-
ing sodium thiosulphate.1
To precipitate the rare earths, add sodium carbonate to the
filtrate from the thorium hydroxide, drain and wash the pre-
cipitate, and dry it in the hot closet. This product may be
worked up according to No. 171.
Purification of the Thorium. Dissolve the thorium precipi-
tates in hydrochloric acid, adding, if necessary, a little nitric
acid; evaporate the solution to dryness, take up the residue in
water, filter if necessary, and treat the solution at 60° with a
solution of sodium thiosulphate. Collect the precipitate on a
filter, wash it with water containing some ammonium nitrate (as
it has a tendency to pass into colloidal solution), and ignite it to
thorium dioxide.
Thorium Sulphate. Heat the thorium oxide with concen-
trated sulphuric acid in a porcelain crucible until the excess of
acid has been expelled, moisten the residue with a few drops
more of sulphuric acid and heat it as before, but avoid bringing
it to a red heat. Pulverize the thorium sulphate, which should
be free from acid salt, and add it gradually, with vigorous
stirring, to five times its weight of ice-water. If, after a little
while, a considerable residue remains undissolved, remove it and
subject it again to the treatment with concentrated sulphuric
acid.
By warming the filtered solution to 30 — 35°, thorium sulphate
octohydrate, Th(SO4)2 • 8 H2O, together with a little enneahydrate,
Th(SO4)2 • 9 H2O, is caused to separate. Maintain the solution
at this temperature, and allow it to evaporate until all of the
salt has separated. Drain the crystals, wash them with a
1
The salts of quadrivalent thorium are more easily hydrolyzed than those
of the tervalent rare-earth metals. Thus thorium hydroxide is precipitated
while the salts of the trivalent metals remain unchanged. The principle of
this separation is similar to that of the basic acetate method used in analyti-
cal chemistry.
According to another method, the solution is warmed to 60 to 70° together
with an excess of a 10% hydrogen peroxide solution; the thorium and some
cerium are thrown down in the form of a flocculent precipitate which can be
easily filtered.
SEPARATION OF THE RARE EARTHS. 239
little water, then with alcohol, and dry them at the room
temperature.
Atomic Weight Determination of Thorium. In order to illus-
trate the principle of an atomic weight determination by the sul-
phate method, prepare first some anhydrous thorium sulphate
from about 2 g. of the above hydrated salt. Heat the crystallized
salt to 400° in a weighed platinum crucible which is supported by
a platinum triangle within a larger crucible. When the weight
has become constant, the amount of the anhydrous thorium sul-
phate, a, is given by subtraction. Then ignite the crucible over the
blast lamp until the weight has again become constant. This gives
the weight of thorium dioxide, b. If the atomic weight of oxygen
is taken at 16.00 and that of sulphur as 32.06, the atomic weight
of thorium is obtained by solving for x in the expression:
x +2 '32.06 + 8 -16.00 a
' x + 2 • 16.00 ~ I"
potassium double sulphates than the yttrium earths. Cerium itself occu-
pies a characteristic position, as it is the only member of the group from
which two series of salts are derived: the cerous salts with tervalent cerium;
and the eerie salts containing quadrivalent cerium.
For the qualitative characterization of the earths, the color of their salts
is first of all of importance. Lanthanum and cerous salts are colorless, eerie
salts are yellowish-red, erbium salts pink, didymium salts violet. It marked
then the beginning of a new era in the history of the rare earths, when, in
1861, through the application of spectrum analysis, it became possible to
measure exactly the color of salt solutions by means of their absorption spec-
tra, and the color of glowing vapors by means of emission spectra. It was in
this epoch that the discovery of the periodic system of the elements was
made (1869), by the aid of which Mendelejeff first recognized the tervalency
of the rare-earth metals and predicted the existence of the element scandium,
which was later discovered by Nilson. Further investigation and the exami-
nation of new minerals has since that time added a number of elements to
the group. In the presence of didymium Lecoq de Boisbaudran discovered
samarium. In the group of the yttrium earths, which since the time of
Mosander was studied especially by Bahr and Bunsen, ytterbium was dis-
covered by Marignac, while Cleve added the elements holmium and thulium.
Marignac also discovered gadolinium, which together with terbium and europ-
ium occupies an intermediate position between the cerium and yttrium earths.
Finally, didymium was separated by von Welsbach in 1885 into praseodymium,
the salts of which are green, and neodymium, whose salts are violet.
The most recent epoch dates from the technical application by von Wels-
bach of thorium and cerium oxides in the incandescent gas-lighting industry.
The following table gives a summary of the rare earths and their atomic
weights:
Cerium earths. Terbium earths. Yttrium earths.
phate is thereby formed, but this is partially hydrolyzed, and an insoluble basic
salt precipitates. By neutralizing the acid set free by the hydrolysis, a com-
plete precipitation is made possible, but on the other hand, it is necessary to
keep the liquid slightly acid to prevent the other rare earths from precipi-
tating with the cerium. All of the cerium is thrown down in this way, but
it is contaminated with some lanthanum and didymium.
Lanthanum and didymium are thrown out of the nitrate as potassium
double sulphates; the yttrium earths remain in solution and can be precipi-
tated as oxalates by adding ammonium oxalate.
The products of this separation are then each further separated and
purified.
Cerium Sulphides.
Sulphides of cerium can be prepared by igniting cerous sulphate in a
stream of hydrogen sulphide. If the temperature remains below 720° the
dark-brown disulphide CeS2 is formed; but if it is kept at a bright red heat,
dark cinnabar-red cerous sulphide, Ce2S3, is produced.
Decomposition potential 67
pressure 163
Decomposition temperature 163
Density determination of solid substances 16, 30
Deville, H. St. Claire 103
Devitrification of glass 39
Dialysis 44, 46
Diazomethanedisulphonic acid 158, 159
Dibrompraseo salts '. 179
Dibromotetramminecobaltic salts 179
Dichloropraseo salts 182
Dichlorotetramminecobaltic salts 167
Didymium compounds 246
Diethyl sulphite, symmetrical 209
unsymmetrical 211
Dilution law 67
Dimercuriammonium hydroxide 162
Dinitritotetramminecobaltic salts 180
Diphenyl 217
Diphenyl lead iodide 216
Dissociation, electrolytic 65, 100
detection of 69
Dissociation of carbon dioxide 15
of complex compounds 100, 156
Dissociation, thermic 32, 52, 156
Distillation 5
fractional 205, 211, 213
Dithio-oxamide 93
Double salts 99
Drying of rinsed vessels 8
Efficiency of reactions 54
Electroaffinity 67
Electrode surface 116
Electrolysis 28
Electrolytes 65
precipitating action of, on colloids 41, 43
Electrons 9, 28, 66
Electrons, planetary 11
valence 13
Elements, periodic classification of 9
252 INDEX.
PAGE
Elements, extraction of 14
occurrence of 14
rare 219
Enantiotropy 33
Endothermic reactions 55, 91, 103
Equilibrium, state of 52
in blast furnace 56
E3ter equilibrium 208
Esters 207
of nitric acid 208
of nitrous acid 209
Esters of phosphoric acid 212
of silicic acid 213
of sulphurous acid 209, 211
Ether, compounds of complex acids with 151
Ethyl nitrate 208
Eutectic of barium-chloride-dihydrate /water 194
Eutectic point 189, 193
Evaporation 4
of inflammable liquids 216
Exothermic reactions 55
Kaolin 130
Kernel of an atom 13
Kuhne's dialyzing tube 43
Lakes 46
Lanthanum blue 45
compounds 244
Lead from galena 26
from lead oxide 15
Lead tetrachloride 143
Le Chatelier pyrometer 86
Lepidolite 217
Lithium 28
Lithium carbonate from minerals 219
Luteochromic salt 184
Luteocobaltic salts 167, 175
Neutralization 67
Nickel, finely divided 217
cobalt-free 174
Nickel air bath 3
carbonyl 217
oxalate 217
Nitrate method 123
Nitrates and nitrites 121
Nitric oxide-metal compounds 155
Nitrides 92
Nitrilosulphonate of sodium 156
Nitrito-acids 149
Nitrogen dioxide 61
trioxide 61
Nitrososulphonates 156
Nitrosylsulphuric acid 129, 206
Nitrous oxide 112
Non-electrolytes, complex 201
Nuclei, atomic 9;
256 INDEX.
PAGE
Octets of atoms 12
Oersted 81
Optical isomers 182
rotation 154
Organo-complexes 153
Osmotic pressure 49
Ostwald's dilution law 67
Oxide hydrogels 41
Oxides 56
Oxides, hydrated 41
Oxydimercurammonium hydroxide 162, 163
Oxycobaltammine chloride 173
Palladium-hydrogen 64
Passive condition 38
Peptonization 40
Periodic classification of the elements 9
Periods in the classification of the elements 13
Perchloric acid 118
Peroxides 101
Petalite 219
Peyrone, Salt of 168
Phosphides 96
Phosphorous acid 136
Phosphorus, constitution of acids of 135
oxychloride 77H
pentachloride 77G
as a chlorinating agent , 201, 203
pentasulphide 85
Phosphorus residues, disposal of 77o
trichloride 77G
Phosphine 97
Phthalic acid from naphthaline 60
acid anhydride 61
Pitchblende 231
Platinized asbestos 59
Platino-ammonia compounds 168
Platinotypes 153
Platinum ammonia compounds 166 et seq.
as catalyzer 43, 59, 70
colloidal 42
Platosammine chloride 168
Poisoning of catalyzers 43
Polyhalogen compounds 107
Polymerization 32
Polynitrides 112
INDEX. 257
PAGE
Polysulphides 106
Potassium bromate 121
bromide 121
chlorate 117
eobalticyanide 146
cobaltinitrite 150
cobaltothiocyanate 147
columbium oxyfluoride 223
cyanate 113
didymium sulphate 242
ferric oxalate 153
ferric sulphide 139
iodate from potassium chlorate 120
iodide 74
iodine tetrachloride Ill
lanthanum sulphate 242, 245
lead iodide 144
mercuriiodide 145
mercurinitrite 149
nitrate from sodium nitrate 122
perchlorate 118
permanganate 124-126
persulphate, electrolytically 133
tantalum heptafluoride 223
tribromide 108, 109
triiodide 110
trithiocarbonate solution 137
Potential series 67
Praseo salts 179, 182
Precipitating colloids 47
Precipitation process 25
Protective colloids 42, 47
Protons 9
Prussic acid residues 92
Pseudo solutions 39
Pulverizing 8
Pure compounds 45, 46
Purple of Cassius 19, 35, 42
Pyrometer 86
Pyrosulphuric acid dichloride 202
Quantum theory 11
Ultramicroscopic investigation 40
Uranium compounds 234
Uranyl lsevo-malate 154
Urea 114
INDEX. 261
PAGE
Valence electrons 13
Valencies, principal and secondary 141
van't Hoff, J. H , 55
Vapor tension analysis 164, 190
Waage, P 53
Washing precipitates 5, 136
Water, detection of traces of 145
of constitution 189
Werner, A 141, 155, 166, 180
Williamson's violet '. 93
Winkler, Cl 58
Wohler, F , 63, 96