Practical Inorganic Chemistry

304 Pages·1984·11.417 MB·English

by  O. I. Vorobyova, K. M. Dunaeva, E. A. Ippolitova, N. S. Tamm

OJ.VOROBYOVA, K.M. DUNAEVA, E.A. IPPOLITOVA,
and N.S. TAMM
PR4CTI01L
Inorganic
Chemistry
Edited by Academician
V. 1. SPITSYN
MIR PUBLISHERS . MOSCOW

Translated from the Russian by
G. LEIB
First published 1987
Revised from the 1984Russian edition
TO THE READER
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Mir Publishers
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© English translation, Mir Publishers, 1987

PREFACE
Practical Inorganic Chemistry is aimed at assisting students to sys
tematically study the basic properties of the chemical elements
and their compounds from the standpoint of D. Mendeleev's Periodic
System and also to gainskillin performing laboratory experiments.
The textbook covers the most important sections of general and
inorganic chemistry.
Substantial changes have occurred in organizing laboratory work
in inorganic chemistry during the last decades. Great attention is
being given to modern preparative techniques. Students using the
present textbook will acquaint themselves with procedures of work
in a modern laboratory. The latter include the carrying out of opera
tions in vacuum, synthesis in non-aqueous solvents, the conducting
of reactions in a gaseous medium (a fluidized bed, "transport" reac
tions) or in liquefied gases, photolyticreduction and oxidation, and
the preparation of pure substances (sublimation, recrystallization,
extraction, chromatography, and distillation). Students will acquire
skill in handling glass and quartz ware on standard joints, cryostats,
thermostats, "dry" chambers, and simple measuring instruments.
The first chapter of the book includes sections that describe in
detail the procedures for dehydrating organic solvents and drying
solids, the fundamental principles of operation of vacuum installa
tions and the technique of vacuum measurement, and work with
chemical ware using joints. How to assemble apparatuses used most
frequently in a laboratory is described in detail. This chapter also
describes working procedures (the handling of electrical furnaces,
temperature control, etc.) which, although being simple, are ex
ceedingly important for students who are beginning to work inde
pendently in a chemical laboratory.
The present book devotes a lot of space to the synthesis of the
most important inorganic compounds and the chemistry of the
elements. Since the book contains a large number of experiments and
syntheses, they cannot be performed by the students during the time
allotted for practical work, and the authors have divided the labora
tory works of each chapter into two parts. The first describes the
obligatory experiments, and the second, supplementary experiments
and syntheses.
The large number of diverse syntheses in the book enable the in
structor to vary the assignments to the students and thus expand
their chemical outlook.
6 Preface
Modern inorganic chemistry is a quantitative science. Consequent
ly, when performing experimental work, students must determine
the yield of the substances obtained and certain constants such as
the boiling points, solubility, and cryohydrate points, and also
perform the required calculations with the use of the fundamentals
of thermodynamics.
Appendix 1 presents numerous reference tables containing most
important data on the solubility of inorganic compounds in water,
the density, dissociation constants, solubility products, ionization
potentials of variousatoms, etc., as well asthermochemical constants
because many laws of inorganic chemistry cannot be explained with
out these quantities.
The book presents no theoretical explanations, but does contain
many questions relating to the technique of an experiment and its
theory. The student must answer them, using the relevant textbooks
and supplementary literature, and also the materials of lectures.
Theneedto findananswerto aquestioninthebookwillteachastudent
studying inorganic chemistry to work independently and thought
fully with chemical literature from his very first steps, and, in
addition, will relate the theoretical course and experimental work.
which will help mastering the subject as a whole.
CONTENTS
Preface 5
1 Work in a Laboratoryand Techniqueof anExperiment t6
1.1 Procedure of Work in a Laboratory 16
Laboratory Notebook (17). Safety (18). First Aid (18). Labo
ratory Ware (19). Heating Equipment (22).
1.2 Technique of Laboratory Work 26
Temperature Control (26). Temperature Measurement and Hea
ting Procedures (26). Filtration (28). Work with Laboratory
Ware on Ground Joints (32). Drying of Solids (33). Drying of
Organic Solvents (34). Balances and Weighing (36). Work with
Glass (39). Stoppers (40). Producing a Vacuum (41). Vacuum
Measurement (44). Apparatus Assembly (45).
2 Purificationof Substances 47
2.1 Solids 47
Recrystallization (47). Sublimation (48).
2.2 Purification and Distillation of Liquids 49
2.3 Gases 50
2.4 Separation and Purification of Inorganic Compounds by Ion
Exchange Chromatography 51
2,5 Separation and Purification of Inorganic Compounds by Extrac
tion 52
3 Determination of Molecular and Atomic Masses and of Chemical
Equivalents 53
3.1 Molecular Masses of Gaseous Substances 53
3.2 Determination of Molecular Masses of Volatile Liquids from
Their Vapour Density 56
3.3 Determination of Chemical Equivalents and Atomic Masses
of Metals 58
Determination of the Atomic Mass of Lead (60).
4 Oxygen 62
4.1 Preparation 63
4.2 Properties 64
Supplementary Experiments 64
Ozone (64).
B Contents
5
Hydrogen 66
5.1 Preparation 66
5.2 Properties 68
5.3 Hydrogen Peroxide 69
6
Rateof Chemical Readions 70
6.1 Rate of Homogeneous Reactions 70
Effect of Reactant Concentration on Reaction Rate (70). Effect
of Catalyst on Reaction Rate (71). Effect of Temperature on
Reaction Rate (72).
6.2 Rate of Heterogeneous Reactions 73
Effect ofthe Degree ofReactant Mixing on the Reaction Rate (73).
Supplementary Experiments 74
1. Effect of the Surface Area on the Reaction Rate (74). 2. Effect
of Light on the Decomposition of Silver Chloride (74).
7 Chemical Equilibrium 74
7.1 Effect of Reactant Concentration 74
7.2 Effect of Temperature 75
Supplementary Experiment 75
Reaction of Potassium Chloride with Nitric Acid (75).
8 Solutions 76
8.1 Solubility of Salts 76
8.2 Effect of Temperature on Salt Solubility 77
8.3 Preparation of Supersaturated Solutions 78
8.4 Thermal Phenomena in Dissolution of Salts 78
Supplementary Experiments 78
1. Change in Volume in Dissolution (78). 2. Determining Solu-
bility of Air in Water (79). 3. Osmosis (80). 4. Determining the
Freezing Point of Water (81). 5. Determining the Temperature
of Water Crystallization from Aqueous Sugar and Sodium
Chloride Solutions (82). 6. Determining the Cryohydrate Point
(82).
9
Electrolytic Dissociation 82
9.1 Electrical Conductance of Solutions 83
9.2 Comparison of the Strength of Acids and Bases 83
9.3 Change in the Hydrogen and Hydroxyl Ion Concentration 86
9.4 Hydrolysis of Salts 87
9.5 Solubility Product 87
Contents
10 Electrochemical Properties ofSolutions 88;
10.1 Electrochemical Series 88-
10.2 Electrolysis 88
11 Halogens. Preparation andProperties 90·
H.1 Chlorine 9()·
Preparation Methods (90). Preparation and Studying of
Properties (91).
H.2 Bromine 93,
Preparation (94). Properties (94).
11.3 Iodine 9:>·
Preparation (95). Properties (96).
11.4 Fluorine 9&-
11.5 Hydrogen Compounds of the Halogens 96
Hydrogen Chloride (97). Hydrogen Bromide (97). Hydrogen
Iodide (98). Hydrogen Fluoride (98).
11.6 Oxygen Compounds of the Halogens 100-
Chlorinated Lime (Bleaching Powder) (100). Potassium Chlorate
(100). lodic Acid (101).
11.7 Comparison of Oxidizing Properties of the Halogens 101
Supplementary Experiments and Syntheses 102:
1. Preparation of Chlorine by Reacting Oxygen with Hydrogen
Chloride (102). 2. Preparation of Purified Iodine (103). 3. Prepa-
ration of Iron(III) Chloride(104). 4. PreparationofNickel, Cobalt,
or Chromium Chloride (105). 5. PreparationofAmmonium Iodide
(106). 6. Preparation of Potassium Iodide (107). 7. Preparation
of Cadmium Iodide (107). 8. Preparation of Potassium Bifluo-
ride (108). 9. Preparationof PotassiumBromate (108). 10. Prepa-
ration of lodic Acid (109). 11. PreparationofIodine Trichloride
(109). 12. Preparation of Tetrachloroiodic Acid Tetrahydrate
(110). 13. Preparation of Potassium Tetrachloroiodate Dihy-
drate (110).
12 Sulphur, Selenium, Tellurium 11~
12. 1 Sulphur and Its Compounds 111
Properties of Sulphur (111). Hydrogen Sulphide (111). Metal
Sulphides (112). Sulphurous Acid Anhydride (113). Sulphuric
Acid and Its Salts (114). Sodium Thiosulphate (115).
12.2 Selenium and Tellurium 116·
Selenium(IV) and Tellurium(IV) Oxides (116).
Supplementary Experiments and Syntheses 11T
1. Preparation of Hydrogen Sulphide from Its Elements (117).
2. Preparation of Sodium Bisulphide (118). 3. Preparation of
Sodium Sulphide (119). 4. Preparation of Sulphur Chlorides
(119). 5. Preparation and Purification of Sulphur Monochloride
(120). 6. Preparation of Thionyl Chloride (121). 7. Preparation
of Sulphuryl Chloride (122). 8. Preparation of Sulphuric Acid
10 Contents
by the Contact Process (123). 9. Preparation of Sulphuric ,Acidby
the Chamber Process (124). 10. Preparation of Copper Sulphate
Pentahydrate (Copper Vitriol) (125). 11. Preparation of Potas
sium Persulphate (125). 12. Preparation and Properties of Sele
nium(IV) Oxide (126). 13. Preparation and Properties of Tel
lurium(IV) Oxide (127).
13 Nitrogen 128
13.1 Preparation and Properties 128
~J.3.2 Compounds 128
Ammonia (128). Ammonium Salts (129). Hydrazine and Hydro
xylamine (130). Oxygen Compounds (130). Nitrous Acid (132).
Nitric Acid (133).
Supplementary Experiments and Syntheses 134
1. Liquefaction of Ammonia and Studying of Its Properties (134).
2, 3. Preparation of Magnesium Nitride by Reacting Magnesium
with Nitrogen (136) and Ammonia (137). 4. Preparation of Li
thium Nitride by Reacting Lithium with Nitrogen (138). 5. Pre
parationof Hydrazine Sulphate (139).6. Preparation of Hydrazine
Hydrate (139).7. PreparationofHydrazine (140).8. Preparationof
Hydroxylamine Chloride (141). 9. Preparation of Nitrogen(IV)
Oxide and Nitrous Acid Anhydride (141). 10. Preparation of
Nitrosyl Chloride by Reacting Nitrogen(II) Oxide with Chlorine
in the Presence of an ActivatedCarbonCatalyst (142). 11. Prep
aration of Nitrosyl-Sulphuric Acid (Nitrosonium Bisulphate)
(143). 12. Preparation of Nitrosyl Chloride by Reacting Nitrosyl
Sulphuric Acid with Sodium Chloride (143). 13. Preparation of
Nitric Acid by Oxidizing Ammonia (144). 14. Preparation of
Anhydrous Nitric Acid (144). 15. Preparation of Potassium
Nitrite (145). 16. Preparation of Anhydrous Copper Nitrate (146).
"14 Phosphorus 147
-14.1 Allotropy 148
'14.2 Properties 149
:14.3 Compounds 149
Hydrogen Phosphide (149). Phosphorous Anhydride and Phos
phorous Acid (149). Phosphoric Anhydride (150). Phosphoric
Acids (151). Salts of Phosphoric Acids (153). Phosphorus Halides
(153).
Supplementary Experiments and Syntheses 155
1. Burning of Phosphorus under Water (155). 2. Preparation
of Hydrogen Phosphide (155). 3. Preparation of Phosphonium
Iodide (155). 4. Preparation of Hypophosphorous Acid (156).
5. Preparation and Separation of Phosphorus 'I'ri- and Penta
chlorides (157). 6, 7. Preparation of Phosphorus Tribromide by
Reacting White Phosphorus with Bromine (159), Red Phosphorus
with Bromine (161). 8. Preparation of Phosphorus Iodide P214
(161). 9. Preparation of Phosphorus 'I'hiochloride (162).