Solubility of Gases and Liquids: A Graphic Approach Data — Causes — Prediction

275 Pages·1976·8.03 MB·English

by  W. Gerrard (auth.)

SOLUBILITY OF
GASES AND LIQUIDS
A Graphic Approach
SOLUBILITY OF
GASES AND LIQUIDS
A Graphic Approach
Data - Causes - Prediction
w.
Gerrard
The Polytechnic ofN orth London
London, England
Springer Science+Business Media, LLC
Library of Congress Cataloging in Publication Data
Gerrard, William.
Solubility of gases and liquids.
Bibliography: p.
Includes index.
1. Solubility. 2. Gases. 3. Liquids, I. Title.
QD543.G45 541\342 76-10676
ISBN 978-1-4899-2646-3
© 1976 Springer Science+Business Media New York
Originally Published by Plenum Press, New York 1976
Softcover reprint of the hardcover 1st edition 1976
ISBN 978-1-4899-2646-3 ISBN 978-1-4899-2644-9 (eBook)
DOI 10.1007/978-1-4899-2644-9
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted,
in any form or by any means, electronic, mechanical, photocopying, microfilming,
recording, or otherwise, without written permission from the Publisher
Preface
The solubility of gases and liquids in liquids is of great importance in large areas of
operations based on chemical concepts. Phenomena have appeared to be so varied
that even experts have from time to time remarked on the difficulty of seeing a
consistent pattern. Now for the first time the essential pattern of all known gas
solubility data is set out in a graphic form for all to see. The continuous merging of the
gas-liquid systems and the liquid-liquid systems is also illustrated. The pattern opens
the way to rational predictions.
The new data given for the lower alkanes and alkenes, the three methylamines,
ammonia, bromomethane, and chloroethane, together with my previously reported
data on hydrogen sulfide, dimethyl ether, chloromethane, and sulfur dioxide, have
been obtained by a bubbler-manometer procedure which is fully described. Not
only are these data of significance in many chemical processes, but they have
also been vital to the development of the overall essential pattern covering all
gases.
The book is for chemists, chemical engineers, biotechnologists, certain physi
cists, and teachers and students in these disciplines. It is a book for all those who are
concerned with the use and inculcation of the fundamental, even rudimentary,
principles of chemistry.
With the kind agreement of The Royal Society, I have given a sketch of Henry's
apparatus (1803) based on Henry's original drawing (see Fig. 25). By the kind
agreement of The Faraday Society, I have based my Fig. 48 on the data and part of a
diagram given by F. H. Campbell (1915). Nine of the figures appearing in Chap. 1
and in the early part of Chap. 2 are based on diagrams in my own papers (1972,1973)
by the kind agreement of the Society of Chemical Industry.
I record the pleasure I have enjoyed in the study of the many papers by J. H.
Hildebrand and his co-workers published over a period of some 60 years. In
connection with the measurement of the solubility of the hydrogen halides in many
organic and certain inorganic compounds, I gratefully acknowledge the collabora
tion of my former colleagues W. Ahmed, T. Brennan, J. Charalambous, T. M. Cook,
v
vi Preface
M. J. Frazer, S. V. Kulkarni, E. D. Macklen, R. W. Madden, V. K. Maladkar, A. M.
A. Mincer, C. B. Lines, R. G. Luckcock, J. A. Sandbach, P. H. Tolcher, and P. L.
Wyvill.
w.
The Polytechnic of North London, Gerrard
Holloway, London, N7 8DB, u.K.
Contents
1 The Solubility of Gases in Liquids 1
1.1. Rationalization of Data 1
1.2. Measurement of Gas Solubility . 3
1.3. The Bubbler-Tube and Manometer Techniques for the Determina-
tion of the Solubilities of Gases in the Upper Half of the bp Range 3
2 Presentation of Solubility Data on the Reference-Line
Diagram. . . . . . . . . . . . . .. . . . . . 9
2.1. The Concept ofthe Reference Line, the R-Line . . . . . . 9
2.2. Solubilities of Hydrocarbon Gases ........... 11
2.3. The Basis of the Explanations of the Essential Patterns of Data 25
3 Henry's Law and Raoult's Law 29
3.1. Henry'sLaw . 29
3.2. Raoult'sLaw. . . . . . . . 36
4 Hildebrand's Solubility Parameters 55
4.1. Intermolecular Forces . . 55
4.2. The Solubility Parameter. 55
4.3. Force Constants . . . . 56
5 The Hydrogen-Bonding Structure of Water 59
5.1. The Essential Pattern . . . . . . . . . . 59
5.2. The Situation about 1974 ....... . 60
5.3. Significance of the Solubility of Hydrocarbon Gases in Water 61
vii
viii Contents
5.4. HydrophobicInteractions . . . . . . . . . . . . . . ., 63
5.5. Solubility of Certain Gases in Water and the Influence ofthe bpi!
atm Factor . . . . . . . . . . 64
5.6. Other Aspects of Water Structure . . . . . . . . . . . . .. 74
6 Sources and Form of Data . . . . . . . . . . . . . . . . .. 77
6.1. Review by Markham and Kobe (1941) on "The Solubility of Gases
in Liquids" ....................... 77
6.2. Review by Battino and Clever (1966) on "The Solubility of Gases
in Liquids" ........... 79
6.3. Papers by Hildebrand and Colleagues 80
6.4. Papers by Clever and Battino 80
6.5. Data Reference Books 81
7 Data for the Noble Gases and Other Gases in the Lower
Half of the Boiling Point Range . . 83
7.1. References ......... . 83
7.2. The Noble Gases Helium to Radon 83
7.3. Hydrogen, Nitrogen, Oxygen, Carbon Monoxide 86
7.4. The Three Factors ....... . 87
7.5. Narcotic Effect of Xenon ..... . 87
7.6. Argon in Dioxane and Water Mixtures 88
7.7. Other Items .......... . 88
8 Carbon Dioxide, Nitrous Oxide, Hydrogen Sulfide,
Chlorine, Sulfur Dioxide, and Carbonyl Chloride 89
8.1. Carbon Dioxide and Nitrous Oxide 89
8.2. Hydrogen Sulfide, bp -61°C . . 94
8.3. Chlorine .......... . 97
8.4. Sulfur Dioxide, bp -lOoC/l atm 103
8.5. Carbonyl Chloride, bp 8.2°C/1 atm 113
9 Hydrogen Halides HCl, HBr, HI . . . . . . . . . 115
9.1. Acid-Base Function 115
9.2. Solubility of Hydrogen Halides in Nonaqueous Liquids 120
9.3. Aspect of Electrolytic Conductance 149
9.4. Nitrile-Hydrogen Halide Systems 153
9.5. Solubility in Water ...... . 157
Contents ix
10 Ammonia and the Three Methylamines 161
10.1. Ammonia ............ 161
to.2. Methylamines . . . . . . . . . . . 166
10.3. Appreciation of the Essential Pattern of Data 184
10.4. Recent Studies on the Interaction of Aliphatic Amines with Water
Structure . . . . . . . . . . . . . . . . . . . . . . .. 184
11 Dimethyl Ether 187
12 Halogenoalkanes 191
12.1. Chloromethane, Chloroethane, and Bromomethane and Non-
aq ueous Liquids S 191
12.2. Solubility in Water . . . . . . . . . . . . . . . . . . .. 202
13 Hydrocarbon Gases 205
13.1. Saturated Hydrocarbons . . 205
13.2. Unsaturated Hydrocarbons 208
13.3. Selective Absorption of Gaseous Hydrocarbons 209
13.4. SolubilityinAIcohols 216
13.5. SolubilityinWater 217
13.6. Other Examples . . 218
14 Examples of Certain Other Gases 223
14.1. List of Formulas and bpoC/1 atm 223
14.2. R-Lines . . . . . . . . . . . 223
14.3. Data for Certain Gases Containing Fluorine . 226
14.4. OtherR-LineExamples . . . . . . . . . 228
15 Effect of Temperature 231
15.1. Earlier Aspects 231
15.2. Lannung'sData 232
15.3. Data by Gerrard and Colleagues 232
16 Prediction 235
16.1. Approach to the Problem 235
16.2. Lachowicz'sReview 236
16.3. Other Papers ..... 236
x Contents
16.4. New Data on Propene and the Four Butenes 240
16.5. The R-Line Approach to the Acetylene Systems 244
16.6. The Carbon Dioxide Systems . '. . . . . . . 246
16.7. Solubility of Methane, Hydrogen, and Nitrogen in Liquids at High
Pressures . . . . . . . . . . . . . . . 251
16.8. Solubility of Gases in Nitrate Meits 254
16.9. Solubility of Noble Gases in Molten Fluorides 257
17 Textbook Statements . . . . . . . . . . . 259
17.1. Introduction . . . . . . . . . . . . . . 259
17.2. Illustrative Examples of Textbook Statements 259
References . . . . . . . . . . . . . . . . . . . . . . . . . " 263
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 273