Chemistry And Technology Of Explosives - T.Urbanski Vol I-IV.pdf

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Chemistry and Technology
of Explosives
Vol. I
by
TADEUSZ URBANSKI
Department of Technology, Politechnika
Warszawa
Authorized translation by
IRENA JECZALIKOWA
and
SYLVIA LAVERTON
PERGAMON PRESS
OXFORD - LONDON. NEW YORK - PARIS
PWN-POLISH SCIENTIFIC PUBLISHERS
WARSZAWA
1964
PERGAMON PRESS LTD
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3 & 5 Fitzroy Square, London W. I.
PERGAMON PRESS
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GAUTHIER-VILLARS ED.
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Distributed in the Western Hemisphere by
THE MACMILLAN COMPANY NEW YORK
pursuant to a special arrangement with
PERGAMON PRESS LIMITED
Copyright © 1964
by
PANSTWOWE WYDAWNICTWO NAUKOWE
PWN - Polish Scientific Publishers
Warszawa
Scan and OCR by Amenf
v1.00
Title of the original volume
Chemia i technologia
materialów wybuchowych
Library of Congress Card. No. 63-10077
Printed in Poland (WDN)
CONTENTS
Page
preface .................................
Classification of explosives ........................
Literature ..............................
XIII
1
3
CHAPTER I. NITRATION AND NITRATING AGENTS
General information ...........................
Nitric acid ...............................
Nitric acid in admixture with other mineral acids . . . . . . . . . . . . .
Earlier works ............................
More recent studies. .........................
Application of kinetic studies to elucidate the structure of nitrating mixtures . . . .
Conclusions .............................
Literature ..............................
4
6
9
9
14
33
47
49
CHAPTER II. NITRATION THEORIES
Nitration as an addition reaction ....................
Nitration as a double exchange reaction . . . . . . . . . . . . . . . . .
Orientation of nitro groups .....................
Side reactions in the nitration process . . . . . . . . . . . . . . . . . .
Literature .............................
53
60
63
74
78
CHAPTER III. NITRATION AGENTS AND METHODS MORE RARELY USED
Nitration of alkenes and alkynes with concentrated nitric acid. ............
Nitration with dilute nitric acid. ....................
Electrolytic nitration ..........................
Nitration with nitric acid vapour ....................
Nitrogen dioxide ...........................
Nitration with nitrogen dioxide alone . . . . . . . . . . . . . . . .
Nitration with nitrogen dioxide in the presence of sulphuric acid .. . . . ...
Nitration with nitrogen dioxide in the presence of Friedel-Crafts catalysts
Nitration with nitrogen dioxide in the presence of activated silica .. . . . . ..
Photonitration with nitrogen dioxide . . . . . . . . . . . . . . . . .
Nitrogen pentoxide (nitric anhydride) . . . . . . . . . . . . . . . . . .
Nitryl chloride (nitronium chloride, NO 2 Cl) . . . . . . . . . . . . . . .
Nitryl fluoride (nitronium fluoride, NO 2 F) . . . . . . . . . . . . . . . .
Nitrogen trioxide (nitrous anhydride) . . . . . . . . . . . . . . . . . .
Nitric acid in the presence of mercuric nitrate . . . . . . . . . . . . . .
Nitrating mixtures with strong oxidizing agents . . . . . . . . . . . . .
81
83
86
86
90
92
102
103
105
105
105
107
109
109
110
115
[VI
vi
CHEMISTRY AND TECHNOLOGY OF EXPLOSIVES
Nitrous acid as a nitrating catalyst and as a nitrating agent............
Nitrous acid in the presence of hydrogen peroxide .... . . . . . . . ...
Organic compounds as nitrating agents .... . . . . . . ........
Nitric acid esters . . . . . . . . . . . . . . . . . . . . . . .
Acyl nitrates (mixed anhydrides) .
116
120
122
122
123
124
124
126
126
126
127
129
131
133
Nitrates of some organic bases .
Aliphatic nitro compounds .
Nitration under influence of gamma radiation .
Indirect methods of introducing a nitro group .
Substitution of sulphonic groups .
Substitution of halogen .
Other nitration reactions by substitution .
Introducing the nitro group by oxidation .
Literature . . . . . . . . . . . . . . . . . . . . . . .
CHAPTER IV. NITRATION WITH NITRATING MIXTURES
Nitrating mixtures ................................. 139
Composition of nitrating mixtures ........................ 139
Utilization of spent acid ............................142
Enthalpy of nitrating mixtures .......................... 146
Heats of dilution ................................ 149
Mixing the acids ................................150
Temperature of nitration ............................151
Mixing of reagents during nitration ....................... 152
Solubility of nitro compounds ..........................153
Design of nitrators ................................155
Heat exchange devices ............................. 156
Stirrers ...................................156
Product separation and discharge of the nitrator .................159
Waste water. ...................................161
Literature ................................... 164
CHAPTER V. GENERAL INFORMATION ON NITRO COMPOUNDS
Constitution of the nitro group. .....................
Visible and ultra-violet absorption spectra. . . . . . . . . . . . . . . .
Infra-red absorption spectra ......................
Nuclear magnetic resonance and X-ray examination of nitro compounds. .............
Chemical properties of nitro compounds. .................
Primary, secondary and tertiary compounds. . . . . . . . . . . . . . .
Heterocyclic nitro compounds .....................
Nitro compounds as explosives ....................
Literature ..............................
165
168
175
179
181
181
187
188
189
CHAPTER VI. AROMATIC NITRO COMPOUNDS
Reactivity of the nitro group . . . . . . . . . . . . . . . . . . . . . . . . 192
Influence of nitro groups on reactivity of hydrogen atoms and substituents. Nucleophilic
reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 197
Free radical reactions . . . . . . . . . . . . . . . . . . . . . 212
Inhibiting action of nitro compounds on polymerization . . . . . . . . . . . . . . . . 214
Vulcanization of rubber with aromatic nitro compounds . . . . . . . . . . . . 216
CONTENTS
vii
Influence of nitro groups on some physico-chemical properties of phenols and amines .....
Behaviour of nitro compounds in concentrated acids .................
Addition compounds of aromatic polynitro compounds ............
Other reactions of nitro compounds . . . . . . . . . . . . . . . . . .
Literature .............................
217
218
220
225
225
CHAPTER VII. NITRO DERIVATIVES OF BENZENE
Nitrobenzene .
230
230
231
231
232
233
234
236
240
242
242
248
249
249
253
254
256
257
259
259
262
Physical properties .
Chemical properties. .
Toxicity of nitrobenzene. .
Preparation of nitrobenzene .
Dinitrobenzenes .
Physical properties .
Chemical properties. .
Toxicity of dinitrobenzene .
Explosive properties of dinitrobenzene .
Preparation of dinitrobenzene .
Trinitrobenzenes . . . . . . . . . . . . . . . . . . . .
Physical properties of sym-trinitrobenzene . . . . . . . . . . . . .
Chemical properties of sym-trinitrobenzene .... . . . . . . ...
Explosive properties of sym-trinitrobenzene . . . . . . . . . . .
Preparation of sym-trinitrobenzene . . . . . . . . . . . .
Preparation of unsymmetrical isomers of trinitrobenzene ............
Tetranitrobenzenes .
Hexanitrobenzene . . . . . . . . . . . . . . . . . . .
Thermochemical properties of nitro derivatives of benzene.. . . . . . . . . . .
Literature ................................
CHAPTER VIII. NITRO DERIVATIVES OF TOLUENE
Nitration of toluene .
265
268
268
269
269
270
271
275
277
281
282
282
283
284
285
288
289
290
291
299
Mononitrotoluenes .
Physical properties .
Thermochemical properties. .
Chemical properties. .
Toxicity .
Preparation of mononitrotolucnes .
Industrial methods of nitration of toluene. .
Separation of isomers .
Dinitrotoluenes .
Physical properties .
Thermochemical properties .
Chemical properties .
Toxicity .
Preparation of dinitrotoluenes .
Industrial methods of preparation of dinitrotoluene . . . . . . . . . . . .
Preparation of pure isomers .
a- Trinitrotoluene (TNT) .
Physical properties .
Thermochemical properties. .

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