Hydrogen Sulfide, Deuterium Sulfide _ Hydrogen Selenide-Pergamon Press (1988)

SOLUBILITY DATA SERIES

Editor-in-Chief

A. S. KERTES The Hebrew University

Jerusalem, Israel

EDITORIAL BOARD

A. F. M. Barton (Australia)

R. Battino(USA)

R.W. Cargill(UK)

H. L. Clever (USA)

Rosa Crovetto (Argentina)

W. Gerrard (UK)

L. H. Gevantman (USA)

W. Hayduk (Canada)

J . W. Lorimer (Canada)

A. E. Mather (Canada)

M. Salomon (USA)

D. G. Shaw (USA)

T. Tominaga (Japan)

R. P. T. Tomkins(USA)

Managing Editor

P. D. GUJRAL IUPAC Secretariat, Oxford, UK

INTERNATIONAL UNION OF PURE AND APPLIED CHEMISTRY IUPAC Secretariat: Bank Court Chambers, 2-3 Pound Way,

Cowley Centre, Oxford 0X4 3YF, UK

NOTICE TO READERS

Dear Reader

If your library is not already a standing-order customer or subscriber to the Solubility Data Series, may we recommend that you place a standing order or subscription order to receive immediately upon publication all new volumes published in this valuable series. Should you find that these volumes no longer serve your needs, your order can be cancelled at any time without notice.

Robert Maxwell Publisher at Pergamon Press

A complete list of volumes published in the Solubility Data Series will be found on p. 352.

SOLUBILITY DATA SERIES

Editor-in-Chief A.S. KERTES

Volume 32

HYDROGEN SULFIDE, DEUTERIUM SULFIDE AND HYDROGEN SELENIDE

Volume Editors

PETER G. T. FOGG COLIN L. YOUNG Polytechnic of North L ondon University of Melbourne

Holfoway, London, UK Parkville, Victoria, Australia

Contributors

H. LAWRENCE CLEVER ELIZABETH L. BOOZER Emory University Emory University

Atlanta, Georgia, USA Atlanta, Georgia, USA

WALTER HAYDUK University of Ottawa

Ottawa, Ontario, Canada

PERGAMON PRESS OXFORD NEW YORK BEIJING FRANKFURT SAO PAULO SYDNEY TOKYO TORONTO

U.K.

U.S.A.

PEOPLE'S REPUBLIC OF CHINA FEDERAL REPUBLIC OF GERMANY BRAZIL

AUSTRALIA

JAPAN

CANADA

Pergamon Press pic, Headington Hill Hall, Oxford 0X3 OBW, England Pergamon Press, Inc., Maxwell House, Fairview Park, Elmsford, New York 10523, U.S.A. Pergamon Press, Room 4037, Qianmen Hotel, Beijing, People's Republic of China Pergamon Press GmbH, Hammerweg 6, D-6242 Kronberg, Federal Republic of Germany Pergamon Editora Ltda, Rua Eca de Queiros, 346, CEP 04011, Paraiso, Sao Paulo, Brazil Pergamon Press Australia Pty Ltd., P.O. Box 544, Potts Point, N.S.W. 2011, Australia Pergamon Press, 5th Floor, Matsuoka Central Building, 1-7-1 Nishishinjuku, Shinjuku-ku, Tokyo 160, Japan Pergamon Press Canada Ltd., Suite No. 271, 253 College Street, Toronto, Ontario, Canada M5T 1R5

Copyright 1988 International Union of Pure and Applied Chemistry

All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic tape, mechanical, photocopying, recording or otherwise, without permission in writing from the copyright holders. First edition 1988

The Library of Congress has catalogued this serial title as follows: Solubility data series.Vol. 1 Oxford; New York; Pergamon, c 1979-v.; 28 cm. Separately cataloged and classified in LC before no. 18. ISSN 0191-5622 = Solubility data series. 1. SolubilityTablesCollected works. QD543.S6629 541.3'42/05-dc19 85-641351 AACR 2 MARC-S

British Library Cataloguing in Publication Data Hydrogen sulfide, deuterium sulfide and hydrogen selenide. 1. Hydrogen compounds. Solubility I. Fogg, P. G. T. II. Young, Colin L. III. Clever, H. Laurence IV. Boozer, Elizabeth L. V. Haydak, Walter IV. Series 546.2642

ISBN 0-08-032481-9

Printed in Great Britain by A. Wheaton & Co. Ltd., Exeter

FOREWORD

If the knowledge is undigested or simply wrong,

more is not better

How to communicate and disseminate numerical data effectively in chemical science and technology has been a problem of serious and growing concern to IUPAC, the International Union of Pure and Applied Chemistry, for the last two decades. The steadily expanding volume of numerical information, the formulation of new interdisciplinary areas in which chemistry is a partner, and the links between these and existing traditional subdisciplines in chemistry, along with an increasing number of users, have been considered as urgent aspects of the information problem in general, and of the numerical data problem in particular.

Among the several numerical data projects initiated and operated by various IUPAC commissions, the Solubility Data Project is probably one of the most ambitious ones. It is concerned with preparing a comprehensive critical compilation of data on solubilities in all physical systems, of gases, liquids and solids. Both the basic and applied branches of almost all scientific disciplines require a knowledge of solubilities as a function of solvent, temperature and pressure. Solubility data are basic to the fundamental understanding of processes relevant to agronomy, biology, chemistry, geology and oceanography, medicine and pharmacology, and metallurgy and materials science. Knowledge of solubility is very frequently of great importance to such diverse practical applications as drug dosage and drug solubility in biological fluids, anesthesiology, corrosion by dissolution of metals, properties of glasses, ceramics, concretes and coatings, phase relations in the formation of minerals and alloys, the deposits of minerals and radioactive fission products from ocean waters, the composition of ground waters, and the requirements of oxygen and other gases in life support systems.

The widespread relevance of solubility data to many branches and disciplines of science, medicine, technology and engineering, and the difficulty of recovering solubility data from the literature, lead to the proliferation of published data in an ever increasing number of scientific and technical primary sources. The sheer volume of data has overcome the capacity of the classical secondary and tertiary services to respond effectively.

While the proportion of secondary services of the review article type is generally increasing due to the rapid growth of all forms of primary literature, the review articles become more limited in scope, more specialized. The disturbing phenomenon is that in some disciplines, certainly in chemistry, authors are reluctant to treat even those limited-in-scope reviews exhaustively. There is a trend to preselect the literature, sometimes under the pretext of reducing it to manageable size. The crucial problem with such preselection - as far as numerical data are concerned - is that there is no indication as to whether the material was excluded by design or by a less than thorough literature search. We are equally concerned that most current secondary sources, critical in character as they may be, give scant attention to numerical data.

On the other hand, tertiary sources - handbooks, reference books and other tabulated and graphical compilations - as they exist today are comprehensive but, as a rule, uncritical. They usually attempt to cover whole disciplines, and thus obviously are superficial in treatment. Since they command a wide market, we believe that their service to the advancement of science is at least questionable. AdditionallyT the change which is taking place in the generation of new and diversified numerical data, and the rate at which this is done, is not reflected in an increased third-level service. The emergence of new tertiary literature sources does not parallel the shift that has occurred in the primary literature.

VII

VIII Foreword

With the status of current secondary and tertiary services being as briefly stated above, the innovative approach of the Solubility Data Project is that its compilation and critical evaluation work involve consolidation and reprocessing services when both activities are based on intellectual and scholarly reworking of information from primary sources. It comprises compact compilation, rationalization and simplification, and the fitting of isolated numerical data into a critically evaluated general framework.

The Solubility Data Project has developed a mechanism which involves a number of innovations in exploiting the literature fully, and which contains new elements of a more imaginative approach for transfer of reliable information from primary to secondary/tertiary sources. The fundamental trend of the Solubility Data Project is toward integration of secondary and tertiary services with the objective of producing in-depth critical analysis and evaluation which are characteristic to secondary services, in a scope as broad as conventional tertiary services.

Fundamental to the philosophy of the project is the recognition that the basic element of strength is the active participation of career scientists in it. Consolidating primary data, producing a truly critically-evaluated set of numerical data, and synthesizing data in a meaningful relationship are demands considered worthy of the efforts of top scientists. Career scientists, who themselves contribute to science by their involvement in active scientific research, are the backbone of the project. The scholarly work is commissioned to recognized authorities, involving a process of careful selection in the best tradition of IUPAC. This selection in turn is the key to the quality of the output. These top experts are expected to view their specific topics dispassionately, paying equal attention to their own contributions and to those of their peers. They digest literature data into a coherent story by weeding out what is wrong from what is believed to be right. To fulfill this task, the evaluator must cover all relevant open literature. No reference is excluded by design and every effort is made to detect every bit of relevant primary source. Poor quality or wrong data are mentioned and explicitly disqualified as such. In fact, it is only when the reliable data are presented alongside the unreliable data that proper justice can be done. The user is bound to have incomparably more confidence in a succinct evaluative commentary and a comprehensive review with a complete bibliography to both good and poor data.

It is the standard practice that the treatment of any given solute-solvent system consists of two essential parts: I. Critical Evaluation and Recommended Values, and II. Compiled Data Sheets.

The Critical Evaluation part gives the following information:

(i) a verbal text of evaluation which discusses the numerical solubility information appearing in the primary sources located in the literature. The evaluation text concerns primarily the quality of data after consideration of the purity of the materials and their characterization, the experimental method employed and the uncertainties in control of physical parameters, the reproducibility of the data, the agreement of the worker's results on accepted test systems with standard values, and finally, the fitting of data, with suitable statistical tests, to mathematical functions;

(ii) a set of recommended numerical data. Whenever possible, the set of recommended data includes weighted average and standard deviations, and a set of smoothing equations derived from the experimental data endorsed by the evaluator;

(iii) a graphical plot of recommended data.

The Compilation part consists of data sheets of the best experimental data in the primary literature. Generally speaking, such independent data sheets are given only to the best and endorsed data covering the known range of experimental parameters. Data sheets based on primary sources where the data are of a lower precision are given only when no better data are available. Experimental data with a precision poorer than considered acceptable are reproduced in the form of data sheets when they are the only known data for a particular system. Such data are considered to be still suitable for some applications, and their presence in the compilation should alert researchers to areas that need more work.

Foreword IX

The typical data sheet carries the following information: (i) components - definition of the system - their names, formulas and

Chemical Abstracts registry numbers; (ii) reference to the primary source where the numerical information is

reported. In cases when the primary source is a less common periodical or a report document, published though of limited availability, abstract references are also given;

(iii) experimental variables; (iv) identification of the compiler; (v) experimental values as they appear in the primary source.

Whenever available, the* data may be given both in tabular and graphical form. If auxiliary information is available, the experimental data are converted also to SI units by the compiler.

Under the general heading of Auxiliary Information, the essential experimental details are summarized:

(vi) experimental method used for the generation of data; (vii) type of apparatus and procedure employed; (viii) source and purity of materials; (ix) estimated error; (x) references relevant to the generation of experimental data as

cited in the primary source. This new approach to numerical data presentation, formulated at the

initiation of the project and perfected as experience has accumulated, has been strongly influenced by the diversity of background of those whom we are supposed to serve. We thus deemed it right to preface the evaluation/compilation sheets in each volume with a detailed discussion of the principles of the accurate determination of relevant solubility data and related thermodynamic information.

Finally, the role of education is more than corollary to the efforts we are seeking. The scientific standards advocated here are necessary to strengthen science and technology, and should be regarded as a major effort in the training and formation of the next generation of scientists and engineers. Specifically, we believe that there is going to be an impact of our project on scientific-communication practices. The quality of consolidation adopted by this program offers down-to-earth guidelines, concrete examples which are bound to make primary publication services more responsive than ever before to the needs of users. The self-regulatory message to scientists of the early 1970s to refrain from unnecessary publication has not achieved much. A good fraction of the literature is still cluttered with poor-quality articles. The Weinberg report (in 'Reader in Science Information', ed. J. Sherrod and A. Hodina, Microcard Editions Books, Indian Head, Inc., 1973, p. 292) states that 'admonition to authors to restrain themselves from premature, unnecessary publication can have little effect unless the climate of the entire technical and scholarly community encourages restraint...' We think that projects of this kind translate the climate into operational terms by exerting pressure on authors to avoid submitting low-grade material. The type of our output, we hope, will encourage attention to quality as authors will increasingly realize that their work will not be suited for permanent retrievability unless it meets the standards adopted in this project. It should help to dispel confusion in the minds of many authors of what represents a permanently useful bit of information of an archival value, and what does not.

If we succeed in that aim, even partially, we have then done our share in protecting the scientific community from unwanted and irrelevant, wrong numerical information.

A. S. Kertes

PREFACE

This volume of The Solubility Data Series is concerned with the solubility of hydrogen sulfide and of hydrogen selenide in aqueous and non-aqueous solvents. Data on the solubility of deuterium sulfide in deuterium oxide are also included. The editors believe that all relevant data published before January 1987 have been included but will be grateful for details of significant omissions.

Solubilities of hydrogen sulfide in a wide range of aqueous and non-aqueous solvents have been reported in the chemical literature. Much of this work is of a high standard. Reliance may be placed on data if there is consistency between measurements by different workers. In the case of some systems, however, there are wide divergences of data. As far as possible the evaluator has indicated which he considers to be reliable data where there are discrepancies but some systems merit re-examination using modern techniques. It is hoped that the publication of this, and similar volume will stimulate further experimental work on systems for which data is in doubt or is lacking.

In aqueous solutions of hydrogen sulfide equilibria involving hydrosulfide and sulfide ions play an important role in determining the solubility of the gas. If other weak acids and bases are also present there will be other equilibria established. Literature references to the theoretical treatment of some such complex systems are included but there has been no attempt to analyse the merits of different theoretical models for prediction of solubility which have been published. Similar equilibria exist in aqueous solutions of hydrogen selenide but these have received little study.

The editors recommend that all published reports of experimental measurements of the solubility of gases should include a complete record of primary experimental observations of temperature, pressure, composition of the phases etc. If such full publication is not possible then authors should endeavour to deposit such a record in an accessible data store.

The editors are grateful for support and encouragement from fellow members of the I.U.P.A.C. Commission on Solubility Data. In particular we wish to acknowledge help and advice given by Prof. A.L. Mather and we are grateful for the provision of data awaiting publication by Prof. W. Hayduk and by Prof. S. Lynn. In addition we would like to express our appreciation for the opportunity to use a daisy-wheel printer owned by Pergamon Press and to Lesley Flanagan for help in preparing the manuscript.

Peter Fogg Colin Young London Melbourne

August 1987

x

THE SOLUBILITY OF GASES IN LIQUIDS

R. Battino, H. L. Clever and C. L Young

INTRODUCTION The Solubility Data Project aims to make a comprehensive search of the literature for data on the solubility of gases, liquids and solids in liquids. Data of suitable accuracy are compiled into data sheets set out in a uniform format. The data for each system are evaluated and where data of sufficient accuracy are available values recommended and in some cases a smoothing equation suggested to represent the variation of solubility with pressure and/or temperature. A text giving an evaluation and recommended values and the compiled data sheets are published on consecutive pages.

DEFINITION OF GAS SOLUBILITY The distinction between vapor-liquid equilibria and the solubility of gases in liquids is arbitrary. It is generally accepted that the equilibrium set up at 300K between a typical gas such as argon and a liquid such as water is gas liquid solubility whereas the equilibrium set up between hexane and cyclohexane at 350K is an example of vapor-liquid equilibrium. However, the distinction between gas-liquid solubility and vapor-liquid equilibrium is often not so clear. The equilibria set up between methane and propane above the critical temperature of methane and below the critical temperature of propane may be classed as vapor-liquid equilibrium or as gas-liquid solubility depending on the particular range of pressure considered and the particular worker concerned. The difficulty partly stems from our inability to rigorously distinguish between a gas, a vapor, and a liquid, which has been discussed in numerous textbooks. We have taken a fairly liberal view in these volumes and have included systems which may be regarded, by some workers, as vapor-liquid equilibria.

UNITS AND QUANTITIES The solubility of gases in liquids is of interest to a wide range of scientific and technological disciplines and not solely to chemistry. Therefore a variety of ways for reporting gas solubility have been used in the primary literature and inevitably sometimes, because of insufficient available information, it has been necessary to use several quantities in the compiled tables. Where possible, the gas solubility has been quoted as a mole fraction of the gaseous component in the liquid phase. The units of pressure used are bar, pascal, millimeters of mercury and atmosphere. Temperatures are reported in Kelvin.

EVALUATION AND COMPILATION The solubility of comparatively few systems is known with sufficient accuracy to enable a set of recommended values to be presented. This is true both of the measurement near atmospheric pressure and at high pressures. Although a considerable number of systems have been studied by at least two workers, the range of pressures and/or temperatures is often sufficiently different to make meaningful comparison impossible. Occasionally, it is not clear why two groups of workers obtained very different sets of results at the same temperature and pressure, although both sets of results were obtained by reliable methods and are internally consistent. In such cases, sometimes an incorrect assessment has been given. There are several examples where two or more sets of data have been classified as tentative although the sets are mutually inconsistent. Many high pressure solubility data have been published in a smoothed form. Such data are particularly difficult to evaluate, and unless specifically discussed by the authors, the estimated error on such values can only be regarded as an "informed guess".

XI

XII The Solubility of Gases in Liquids Many of the high pressure solubility data have been obtained in a more general study of high pressure vapor-liquid equilibrium. In such cases a note is included to indicate that additional vapor-liquid equilibrium data are given in the source. Since the evaluation is for the compiled data, it is possible that the solubility data are given a classification which is better than that which would be given for the complete vapor-liquid data (or vice versa). For example, it is difficult to determine coexisting liquid and vapor compositions near the critical point of a mixture using some widely used experimental techniques which yield accurate high pressure solubility data. For example, conventional methods of analysis may give results with an expected error which would be regarded as sufficiently small for vapor-liquid equilibrium data but an order of magnitude too large for acceptable high pressure gas-liquid solubility. It is occasionally possible to evaluate data on mixtures of a given substance with a member of a homologous series by considering all the available data for the given substance with other members of the homologous series. In this study the use of such a technique has been very limited. The estimated error is often omitted in the original article and sometimes the errors quoted do not cover all the variables. In order to increase the usefulness of the compiled tables estimated errors have been included even when absent from the original article. If the error on any variable has been inserted by the compiler this has been noted.

PURITY OF MATERIALS The purity of materials has been quoted in the compiled tables where given in the original publication. The solubility is usually more sensitive to impurities in the gaseous component than to liquid impurities in the liquid component. However, the most important impurities are traces of a gas dissolved in the liquid. Inadequate degassing of the absorbing liquid is probably the most often overlooked serious source of error in gas solubility measurements.

APPARATUS AND PROCEDURES In the compiled tables brief mention is made of the apparatus and procedure. There are several reviews on experimental methods of determining gas solubilities and these are given in References 1-7.

METHODS OF EXPRESSING GAS SOLUBILITIES Because gas solubilities are important for many different scientific and engineering problems, they have been expressed in a great many ways:

The Mole Fraction, x (g) The mole fraction solubility for a binary system is given by:

n(g) + n(l)

= W(g)/M(g) [W(g)/M(g)] + [W(l)/M(l)]

here n is the number of moles of a substance (an amount of substance), VI is the mass of a substance, and M is the molecular mass. To be unambiguous, the partial pressure of the gas (or the total pressure) and the temperature of measurement must be specified. The Weight Per Cent Solubility, wt% For a binary system this is given by

wt% = 100 W(g)/[W(g) + W(l)]

The Solubility of Gases in Liquids XIII

where W is the weight of substance. As in the case of mole fraction, the pressure (partial or total) and the temperature must be specified. The weight per cent solubility is related to the mole fraction solubility by

x{g) = [wt%/M(g)] [wt%/.M(g)] + [(100 - Wt%)/M(l)]

The Weight Solubility, C The weight solubility is the number of moles of dissolved gas per gram of solvent when the partial oressure of gas is 1 atmosphere. The weight solubility is related to the mole fraction solubilitv at one atmosphere partial pressure by

CWM(1) x{q) (oartial pressure 1 atm) = 1 + C M(l) w

where M(l) is the molecular weight of the solvent. The Moles Per Unit Volume Solubility, n Often for multicomponent systems the density of the liquid mixture is not known and the solubility is quoted as moles of gas per unit volume of liquid mixture. This is related to the mole fraction solubility by

n v(l) 1 + n v(l)

where v (1) is the molar volume of the liquid component. The Bunsen Coefficient,ex The Bunsen coefficient is defined as the volume of gas reduced to 273.15K and 1 atmosphere pressure which is absorbed by unit volume of solvent (at the temperature of measurement) under a partial pressure of 1 atmosphere. If ideal gas behavior and Henry's law is assumed to be obeyed,

V(g) 273.15 a = 2

V(l) T where V(g) is the volume of gas absorbed and V(l) is the original (starting) volume of absorbing solvent. The mole fraction solubility is related to the Bunsen coefficient by

a x{g, 1 atm) =

a + 173^15 y ^ g ! T v(l)

where v(g) and v(l) are the molar volumes of gas and solvent at a pressure of one atmosphere. If the gas is ideal,

a x(q) a + 273.15R

v(l) Real gases do not follow the ideal gas law and it is important to establish the real gas law used for calculating a in the original publication and to make the necessary adjustments when calculating the mole fraction solubility. The Kuenen Coefficient, S This is the volume of gas, reduced to 273.15K and 1 atmosphere pressure, dissolved at a partial pressure of gas of 1 atmosphere by 1 gram of solvent.

XIV The Solubility of Gases in Liquids

The Ostwald Coefficient, L The Ostwald coefficient, L, is defined at the ratio of the volume of gas absorbed to the volume of the absorbing liquid, all measured at the same temperature:

V(l) If the gas is ideal and Henry's Law is applicable, the Ostwald coefficient is independent of the partial pressure of the gas. , It is necessary, in practice, to state the temperature and total pressure for which the Ostwald coefficient is measured. The mole fraction solubility, x, is related to the Ostwald coefficient by

x(g): RT + 1 P(g) L v(l)

where P is the partial pressure of gas. The mole fraction solubility will be at a partial pressure of P(g). The Absorption Coefficient,(3 There are several "absorption coefficients", the most commonly used one being defined as the volume of gas, reduced to 27 3.15K and 1 atmosphere, absorbed per unit volume of liquid when the total pressure is 1 atmosphere. 3 is related to the Bunsen coefficient by

3 = a (l-P(D) where P(l) is the partial pressure of the liquid in atmosphere. The Henry's Law Contant A generally used formulation of Henry's Law may be expressed as

P(g) = KR x{g) where K is the Henry's Law constant and x the mole fraction solubility. Other formulations are

P(g) = K2C(1)

C(g) = KCC(1) where K~ and K are constants, C the concentration, and (1) and (g) refer to the liquid and gas phases. Unfortunately, K , K~ and K are all sometimes referred to as Henry's Law constants. Henry's Law is a limiting law but can sometimes be used for converting solubility data from the experimental pressure to a partial gas pressure of 1 atmosphere, provided the mole fraction of the gas in the liquid is small, and that the difference in pressures is small. Great caution must be exercised in using Henry's Law. The Mole Ratio, N The mole ratio, N, is defined bv

N = n(g)/n(l) Table 1 contains a presentation of the most commonly used inter-conversions not already discussed.

For gas solubilities greater than about 0.01 mole fraction at a oartial pressure of 1 atmosphere there are several additional factors which must be taken into account to unambiguously report gas solubilities. Solution densities or the partial molar volume of gases must be known. Corrections should be made for the possible non-ideality of the gas or the non-applicability of Henry's Law.

The Solubility of Gases in Liquids xv TABLE 1. Interconversion of parameters used for reporting solubility.

L = a(T/273.15)

Cw = a/voP = 17.033 x lOMsoln) + 7 6 Q

H a M(l) L = C v, p w t,gas

where v0 is the molal volume of the gas in cm3 mol'1 at 0C, p the density of the solvent at the temperature of the measurement, P i the density of the solution at the temperature of the measurement, and v, the

c t,gas molal volume of the gas (cm3 mol 1) at the temperature of the measurement.

REFERENCES

1. Battino, R.; Clever, H. L. Cham. Rev. 1966, 66, 395. 2. Clever, H. L.; Battino, R. in Solutions and Solubilities, Ed. M. R. J.

Dack, J. Wiley & Sons, New York, 1975, Chapter 7. 3. Hildebrand, J. H.; Prausnitz, J. M.; Scott, R. L. Regular and

Related Solutions, Van Nostrand Reinhold, New York, 1970, Chapter 8. 4. Markham, A. E.; Kobe, K. A. Chem. Rev. 1941, 62, 449. 5. Wilhelm, E.; Battino, R. Chem. Rev. 197.3, 73' l ' 6. Wilhelm, E.; Battino, R.; Wilcock, R. J. Chem. Rev. 1977, 77, 219. 7. Kertes, A. S.; Levy, 0.; Markovits, G. Y. in Experimental Thermo

chemistry Vol. II, Ed. B. Vodar and B. LeNaindre, Butterworth, London, 1974, Chapter 15.

Revised: December 1984 (CLY)

XVI The Solubility of Gases in Liquids

APPENDIX I, Conversion Factors k and k~

1 (non-SI Unit) k (SI Unit)

k"1 1 (SI Unit) =

C1 (non-SI Unit) LENGTH SI Unit, m

A (angstrom cm (centimeter) in (inch) ft (foot)

1 1

254 048

10"1C 10"2 10"'+ 10"4

(*) (*) (*) (*)

1 x 1010 (*) 1 x 102 (*)

3 937 008 x 10"5 3 280 840 x 10-6

AREA SI Unit, m2

in' ft2

1 x i(T4 64 516 x 10"8

9 290 304 x 10"8 (*) (*) (*)

1 x 10* 1 550 003 x 10"3 1 076 391 x IO"5

(*)

VOLUME SI Unit, md

in ft3 1 (litre) UKgal (UK gallon) USgal (US gallon)

16 387 064 2 831 685

1 45 461 37 854

106 io- 1 2 10"8 10"3 IO"7 IO"7

(*) (*) (*)

6 102 374 3 531 467

1 21 997 26 417

x 106 x IO"2 x IO"5 x 103 x 10 2 x IO"2

(*)

(*)

MASS SI Unit, kg

g (gram) t (tonne) lb (pound)

1 x 10~3 1 x 103

45 359 237 x 10"8 (*) (*) (*)

1 x 103 (*) 1 x 10"3 (*)

2 204 623 x io"6

DENSITY SI Unit, kg m"

g cm lb in 3 lb ft"3 lb UKgal"1 lb USgal"1

2 767 1 601

99 1 198

1 x io3 1

991 x IO"2 847 x IO-5 776 x IO"3 264 x IO"1*

(*) (*)

3 6 8

1 x io"3 (*) 1 (*)

612 728 x IO-11 242 795 x IO""8 100 224 x IO-7 345 406 x IO"9

PRESSURE SI Unit, Pa (pascal, kg m"

dyn cm at (kgf cm"2) atm (atmosphere) bar lbf in"2 (p.s.i.) lbf ft"2 inHg (inch of mercury) mmHg (millimeter of

mercury, torr)

980 101 894 47

386 333

1 665 325

1 757 880 388 224

X X

X X X X X

IO"1 IO"1

IO5 IO"3 IO"3 IO"3 10""

(*) (*) (*) (*)

1 9 1 2 7

019 869 450 20

952 500

1 716 233

1 377 886 999 617

X X X X X X X X

10 (*) IO"11 IO"12 IO-5 (*) IO"10 IO"6 IO'10 IO-9

ENERGY SI Unit, J (joule, kg m2 s 2)

erg cal IT (I.T. calorie) cal (thermochemical calorie) kW h (kilowatt hour) 1 atm ft lbf hp ti (horse power hour) Btu (British thermal unit)

41 868 4 184

36 101 325 355 818 684 519 055 056

x 10" x 10" x 10" x 10' x 10' x 10"

10'

(*) (*) (*) (*) (*)

388 459 390 057 777 778

IO7 IO"7 IO"7 IO"13

(*)

869 233 x 10"9 IO"7

1 3 375 622 725 062 478 172 x

10 10" l o

An asterisk (*) denotes an exact relationship.

Hydrogen Sulfide in Aqueous Solvents 1

COMPONENTS:

1 . H y d r o g e n s u l f i d e ; H 2 S ; [ 7 7 8 3 - 0 6 - 4 ]

2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

EVALUATOR: Peter G.T. Fogg, Department of Applied Chemistry and Life Sciences, Polytechnic of North London, Holloway, London N7 8DB, U.K. February 1987

CRITICAL EVALUATION: The solubility of hydrogen sulfide in water has been investigated by numerous workers since the nineteenth century. Some of this early work (1-3) is in good agreement with more recent work. Hydrogen sulfide exists, in aqueous solution, in equilibrium with its ions. Solubilities which have been compiled correspond to bulk solubilities. For this purpose the number of moles of hydrogen sulfide in solution has been taken to be the sum of the number of moles of the uncharged H2S plus those of HS- and those of S--. Measurements have been made at pressures from 0.02 to 207 bar and temperatures from 273.2 to 603.2 K. The most extensive series of measurements over a pressure range were carried out by Lee & Mather (4) and by Selleck et al. (5). Above 344 K the mole fraction solubilities found by Lee & Mather tend to be higher than those found by Selleck et al. but there is better agreement at lower temperatures. However measurements indicate that, for many purposes, the mole fraction solubility can be considered to be close to a linear function of pressure to mole fraction solubilities of about 0.02. i.e. Henry's law is a useful approximation. The higher the concentration of hydrogen sulfide the greater the deviation from linear behaviour. The measurements of solubilities at partial pressures of hydrogen sulfide less then 1.013 bar made by Clarke & Glew (6) are consistent with the earlier measurements by Wright & Maass (7). When values for 298.2 K are extrapolated down to about 0.1 bar there is good agreement with solubilities measured by McLauchlan (1). Many values of mole fraction solubilities for a partial pressure of hydrogen sulfide of 1.013 bar (1 atm) at temperatures in the range 273.2 K to 453.2 K have been published or may be obtained by extrapolation from published solubilities (1-13). Measurements published by Kozintseva (8) are the only set of measurements made in the range 453.2 K to 603.2 K. Available values indicate that mole fraction solubilities for a partial pressure of 1.013 bar decrease with increase in temperature to about 450 K but at higher temperatures values increase. Although there is no reason to doubt the reliability of the measurements reported by Kozintseva these high temperature values must be considered to be tentative until they are confirmed by other workers.

Mole fraction solubilities for a partial pressure of hydrogen sulfide of 1.013 bar, based upon measurements made since 1930, may be represented by the equation: In x = -24.912 + 3477.1/(T/K) + 0.3993 In (T/K) + 0.015700 T/K H2S

The standard deviation for x is given by: n2 o

6x H2S 0.000065 This equation is valid for temperatures from 283.2 K to 603.2 K. The variation of xu with T/K corresponding to this equation and the values of xu _ from

rl 2 o rl 2 o experimental measurements made since 1930 are plotted in fig 1. Values in the range 273.2 to 283.2 are better fitted by the equation:

In x _ = -14.761 + 2507.2/(T/K) rl2 b 6x H2S 0.000030

The average value of x _ for a partial pressure of 1.013 bar at 298.15 K is n2 o

0.001830 0.000007. This is based upon five sets of measurements (6,9, 11-13).

2 Hydrogen Sulfide in Aqueous Solvents

COMPONENTS:


2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

EVALUATOR: Peter G.T. Fogg, Department of Applied Chemistry and Life Sciences, Polytechnic of North London, Holloway, London N7 8DB, U.K. February 1987

250 300 350 400 450 500 T/K

550 600 650

Fig. 1. Variation with temperature of the mole fraction solubility of hydrogen sulfide in water at a partial pressure of 1.013 bar from experimental measurements published since 1930

Experimental points have been superimposed upon the curve corresponding to the equation: In x H2S -24.912 + 3477.1/(T/K) + 0.3993 In (T/K) + 0.015700 T/K


COMPONENTS: EVALUATOR:

Peter G.T. Fogg, 1. Hydrogen sulfide; H2S; [7783-06-4] Department of Applied Chemistry

and Life Sciences, Polytechnic of North London,

2. Water; H20; [7732-18-5] Holloway, London N7 8DB, U.K. February 1987

CRITICAL EVALUATION:

References 1. McLauchlan, W.H. Zeit. physik. Chem. 1903, 44, 600-633. 2. Winkler, L.W. Zeit. physik. Chemie, (Leipzig) 1906, 55, 344-354.

3. Pollitzer, F. Zeit. anorg. Chem. 1909, 64, 121-148. 4. Lee, J.I.; Mather, A.E. Ber. Bunsenges. phys. Chem. 1977, 81, 1020-3. 5. Selleck, F.T.; Carmichael, L.T; Sage, B.H.

Ind. Eng. Chem. 1952, 44, 2219-2226. 6. Clarke, E.C.W.; Glew, D.N. Can. J. Chem. 1971, 49, 691-698. 7. Wright, R.H.; Maass, D. Can. J. Research 1932, 6, 94-101. 8. Kozintseva, T.N.; Geokhimiya 1964, 8, 758-765. 9. Kapustinsky, A.F.; Anvaer, B.I.

Compt. Rend. Acad. Sci . URSS 1941, 30, 625-628. 10. Byeseda, J.J. Proc. Laurance Reid Gas. Cond. Conf. 1985. 11. Gamsjager, H.; Rainer, W.; Schindler, P.

Monatsh. Chem. 1967, 98, 1782-1802. 12. Douabul, A.A.; Riley, J.P. Deep-Sea Res. 1979, 26A, 259-268. 13. Kiss, A. v.; Lajtai, I.; Thury, G.

Zeit. anorg. allgem. Chem. 1937, 233, 346-352.


1 COMPONENTS: T


2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

VARIABLES:

P r e s s u r e

ORIGINAL MEASUREMENTS: 1

M c L a u c h l a n , W.H.

Z . physik. Chem. 1 9 0 3 , 44, 6 0 0 - 6 3 3 .

PREPARED BY: I

P . G . T . F o g g

[EXPERIMENTAL VALUES: I

I * I PTT 0 /mmHg P u J b a r C o n e , o f H 2 S i n s o l u t i o n

H 2 0 r l 2 ^ 3 / m o l dm

7 4 . 7 0 . 0 9 9 6 0 . 0 1 0 0 8 8 . 7 0 . 1 1 8 3 0 . 0 1 1 9 4

9 9 . 8 0 . 1 3 3 1 0 . 0 1 3 5

1 0 1 . 4 0 . 1 3 5 2 0 . 0 1 4 0 0

1 0 5 . 5 0 . 1 4 0 7 0 . 0 1 4 4

T/K = 2 9 8 . 2

* c a l c u l a t e d b y c o m p i l e r .

AUXILIARY INFORMATION

METHOD /APPARATUS /PROCEDURE:

S o l u t i o n s o f h y d r o g e n s u l f i d e w e r e

p r e p a r e d b y d i l u t i o n o f a s t o c k

s o l u t i o n . T h e c o n c e n t r a t i o n o f H 2 S

i n s o l u t i o n w a s d e t e r m i n e d b y

i o d i m e t r y . H y d r o g e n , g e n e r a t e d b y

e l e c t r o l y s i s o f w a t e r , w a s p a s s e d

t h r o u g h a s o l u t i o n u n d e r t e s t . T h e

H2S i n t h e e m e r g e n t g a s s t r e a m w a s

a b s o r b e d i n c o p p e r s u l f a t e s o l u t i o n

a n d e s t i m a t e d f r o m t h e c h a n g e i n

e l e c t r i c a l c o n d u c t i v i t y o f t h i s

s o l u t i o n . T h e p a r t i a l p r e s s u r e o f

H 2 S w a s c a l c u l a t e d f r o m t h e v o l u m e

o f h y d r o g e n a n d t h e t o t a l p r e s s u r e

o f t h e e m e r g e n t g a s s t r e a m .

ISOURCE AND PURITY OF MATERIALS: I

1 . p r e p a r e d f r o m F e S .

ESTIMATED ERROR:

REFERENCES:


[COMPONENTS:

1 . Hydrogen s u l f i d e ; [ 7 7 8 3 - 0 6 - 4 ]

2 . Wa te r ; H 2 0 ; [7732-

VARIABLES:

T e m p e r a t u r e

[EXPERIMENTAL VALUES:

T / K

273 .2 283 .2 293 .2 303 .2 313 .2 323 .2 333 .2

*

H 2 S ;

- 1 8 - 5 ]

ORIGINAL MEASUREMENTS: I

W i n k l e r , L.W.

Zeit, phys, Chem, (Leipzig) 1906, 55, 3 4 4 - 3 5 4 .

PREPARED BY: I P . G . T . Fogg

Bunsen a b s o r p t i o n Mole f r a c t i o n s o l u b i l i t y , | c o e f f . a

c a l c u l a t e d by t h e

METHOD/APPARATUS/PROCEDURE

No i n f o r m a t i o n

4 .621 3 .362 2 .554 2 .014 1 .642 1 .376 1 .176

c o m p i l e r .

AUXILIARY

xR s , (1 .013 b a r )

0 .003747 0 .002729 0 .002078 0 .001643 0 .001345 0 .001132 0 .000972

INFORMATION

ISOURCE AND PURITY OF MATERIALS:

No i n f o r m a t i o n

ESTIMATED ERROR:

REFERENCES:


COMPONENTS:

1 . H y d r o g e n s u l f i d e ; H 2 S [ 7 7 8 3 - 0 6 - 4 ]

2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

VARIABLES: Temperature, concentration

METHOD /APPARATUS /PROCEDURE: A measured quantity of water was run into the a cell of known volume attached to a glass diaphragm manometer. Dissolved air was removed by repeated freezing and melting in vaouo. A measured amount of H2S was condensed in the cell by liquid air and the cell sealed. The temperature of the cell and manometer were then controlled to 0.1C. pH2s w a s taken to be P-total ~ PH20 where PH20 ^s the v a P o r pressure of pure water. The weight of H2S in the gas phase was calculated from ^H2S and the volume of the gas phase. The difference between this weight and the total weight of H2S used gave the weight of H2S in solution.

ORIGINAL MEASUREMENTS: W r i g h t , R . H . ; M a a s s , 0 .

Can. J. Research, 1 9 3 2 , 6, 9 4 - 1 0 1 .

PREPARED RYr P . G . T . F o g g

SOURCE AND PURITY OF MATERIALS; 1 . From a c y l i n d e r ; p u r i f i e d by

f r a c t i o n a l d i s t i l l a t i o n a s d e s c r i b e d i n r e f . ( 1 ) .

2 . L a b o r a t o r y d i s t i l l e d a n d d e g a s s e d .

ESTIMATED ERROR: 6T = 0 . 1 K ( a u t h o r s )

REFERENCES:

1. Wright, R.H.; Maass, 0.; Can. J. Research, 1931, 5, 436.

EXPERIMENTAL VALUES: T/K

278.15

283.15

288.15

Total pressure /mmHg

274.5 560 838 1176 303.8 615 914 1279 1567 2112 333.3 670 991 1382 1692 2284

PE s/mmHg 2

268.0 553 831 1169 294.7 606 905 1270 1558 2103 320.6 657 978 1369 1679 2271

H2S in vapor /mol dm""3

0.0155 0.0321 0.0484 0.0685 0.0168 0.0346 0.0518 0.0731 0.0900 0.1221 0.0179 0.0369 0.0551 0.0774 0.0953 0.1297

H2S in liquid /mol dm"b

0.0635 0.1302 0.1910 0.2682 0.0597 0.1220 0.1801 0.2511 0.3060 0.4099 0.0560 0.1144 0.1693 0.2346 0.2877 0.3866

Mole fraction in liquid Xs

0.00114 0.00234 0.00343 0.00481 0.00107 0.00219 0.00324 0.00450 0.00548 0.00733 0.00101 0.00206 0.00304 0.00421 0.00516 0.00692

* calculated by compiler on the assumption that dissolution of H2S caused negligible change in the volume of the liquid phase.



COMPONENTS: 1. Hydrogen su

[7783-06-4] 2. Water; H20;

Lfide; H2S ; [7732-18-5]

[EXPERIMENTAL VALUES: T/K

1

293.15

298.15

303.15

313.15

323.15

333.15

Total pressure /mmHg

362.8 724

1067 1483 1817 2454 392.6 778 1144 1581 1935 2622 422.8 830 1219 1672 2052 2785 486.5 934

1370 1853 2278 3095 562.4

1040 1522 2033 2505 3402 652.2 1162 1681 2213 2731 3707

PTT c/roniHg H 2

345.4 707 1050 1466 1800 2437 369.1 754 1120 1557 1911 2598 391.3 798 1187 1640 2020 2753 431.6 879 1315 1798 2223 3040 470.4 948 1430 1941 2413 3310 503.3 1013 1532 2064 2582 3558

calculated by compiler on the negligible change

Values oJ

in the volume

ORIGINAL MEASUREMENTS: Wright, R.H.; Maas Can.

2S in vapor H /mol dm"3

0.0190 0.0390 0.0581 0.0816 0.1005 0.1371 0.0199 0.0409 0.0610 0.0851 0.1049 0.1437 0.0208 0.0425 0.0636 0.0882 0.1091 0.1498 0.0222 0.0454 0.0682 0.0937 0.1162 0.1603 0.0235 0.0474 0.0719 0.0979 0.1223 0.1690 0.0243 0.0492 0.0747 0.1010 0.1269 0.1762

J. Research,

2S in liquid /mol dm"3

0.0528 0.1074 0.1594 0.2188 0.2696 0.3642 0.0497 0.1010 0.1499 0.2050 0.2544 0.3437 0.0470 0.0955 0.1413 0.1932 0.2398 0.3247 0.0426 0.0858 0.1260 0.1722 0.2149 0.2921 0.0387 0.0789 0.1139 0.1560 0.1937 0.2647 0.0359 0.0730 0.1045 0.1440 0.1777 0.2424

assumption that dissolution of the liquid

E x c from interpolated values of xrr tt2b * H

T/K 278 283 288 293 298 303 313 323 333

760 mmHg

.15

.15

.15

.15

.15

.15

.15

.15

.15 = 1 atm

P H 2 S = 1 a t m ' 0.00321 0.00275 0.00239 0.00209 0.00185 0.00166 0.00136 0.00116 0.00102

= 1.01325 bar

phase.

s, 0. 1932, 6, 94-101.

Mole fraction * in liquid

X H2S

0.00095 0.00193 0.00287 0.00393 0.00484 0.00653 0.00090 0.00182 0.00270 0.00369 0.00458 0.00617 0.00085 0.00173 0.00255 0.00348 0.00432 0.00584 0.00077 0.00156 0.00229 0.00312 0.00389 0.00529 0.00071 0.00144 0.00207 0.00284 0.00352 0.00480 0.00066 0.00134 0.00191 0.00263 0.00325 0.00442

of H2S caused

c/P-n csupplied by authors: 2b n 2^ >

PH2S=2 atm. P ^ 0.00626 0.00543 0.00473 0.00416 0.00368 0.00330 0.00271 0.00228 0.00199

0 0 0 0 0 0 0 0 0

=3 atm. .00921 .00807 .00707 .00620 .00549 .00492 .00404 .00340 .00296


COMPONENTS:

1 . Hydrogen s u l f i d e ; H2S [ 7 7 8 3 - 0 6 - 4 ]

2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

ORIGINAL MEASUREMENTS:

K a p u s t i n s k y , A . F . ; A n v a e r , B . I .

Compt.Rend.Acad.Sci.URSS 1 9 4 1 , 30, 6 2 5 - 8 .

VARIABLES: PREPARED BY:

P . G . T . F o g g

EXPERIMENTAL VALUES:

T/K

2 9 8 . 2

P u c /mmHg t l 2 0

760

Concn. of H2S in liquid / mol dm""3

0 .1013

M o l e f r a c t i o n i n l i q u i d *

X H 2 S

0 . 0 0 1 8 2 6

c a l c u l a t e d b y t h e c o m p i l e r

760 mmHg = 1 . 0 1 3 2 5 b a r


METHOD/APPARATUS /PROCEDURE:

H y d r o g e n s u l f i d e , s a t u r a t e d w i t h w a t e r v a p o r , w a s b u b b l e d t h r o u g h a 3 0 0 cm3 t h e r m o s t a t t e d a b s o r p t i o n v e s s e l f o r 3 - 4 h o u r s . S a m p l e s o f s o l u t i o n w e r e t h e n w i t h d r a w n f o r a n a l y s i s b y i o d i m e t r y . A l l o w a n c e w a s m a d e f o r t h e v a p o r p r e s s u r e o f w a t e r .

SOURCE AND PURITY OF MATERIALS;

1 . f r o m c h e m i c a l l y p u r e h y d r o c h l o r i c

a c i d a n d NaHS; C 0 2 r e m o v e d b y

B a ( O H ) 2 .

ESTIMATED ERROR:

6T/K = 0 . 1 ( a u t h o r s )

REFERENCES:

Hydrogen Sulfide in Aqueous Solvents 9 COMPONENTS:


2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]


S e l l e c k , F . T . ; C a r m i c h a e l , L . T . ; S a g e , B . H .

Ind. Eng. Chem. 1 9 5 2 , 44, 2 2 1 9 - 2 2 2 6

VARIABLES:

T e m p e r a t u r e , p r e s s u r e

PREPARED BY:

P . G . T . F o g g


T/F T/K Total pressure /(Lb/Sq.Inch Absolute)

Total pressure

/bar* Mole fraction of H2S

Gas phase Liquid phase

100

160

310.93

344.26

100 150 200 250 300 390. 100 150 200 250 300 400 500 600 700 759.

It

4t

6.89 10.34 13.79 17.24 20.68 26.90 6.89 10.34 13.79 17.24 20.68 27.58 34.47 41 .37 48.26 52.36

0.9894 0.9925 0.9940 0.9949 0.9954 0.9960 0.9493 0.9643 0.9726 0.9771 0.9801 0.9837 0.9856 0.9865 0.9868 0.9869

0.0082 0.0123 0.0165 0.0207 0.0250 0.0333 0.0050 0.0076 0.0102 0.0128 0.0154 0.0206 0.0258 0.0310 0.0364 0.0395

, calculated by the compiler; three-phase equilibria involving aqueous liquid, H2S-rich liquid, & gas.

AUXILIARY INFORMATION METHOD/APPARATUS/PROCEDURE:

The measurements were obtained as part of a study of the complete phase behaviour of the H2S/H20 system. The apparatus consisted of a spherical pressure vessel from which samples of gas or liquid phases could be withdrawn for analysis. The vessel was fitted with a metal diaphragm which responded to pressure differentials. The pressure within the system was measured by a pressure balance calibrated against the vapor pressure of C02 at the ice point (1).

SOURCE AND PURITY OF MATERIALS: 1. prepared by hydrolysis of Al2S3;

dried and fractionated. 2. distilled; deaerated at low

pressure.

ESTIMATED ERROR: 6P = 0.1% or 0.07 bar, whichever

the greater. 6T = 0.02 K; 6xv c/xv = 0.0015

(authors) H2 S H2 S REFERENCES:

1. Sage, B.H.; Lacey, W.N. Trans.Am.Inst.Mining Met.Engrs. 1948, 174, 102.


COMPONENTS:

1. Hydrogen sulfide; H2S; [7783-06-4]

2. Water; H20; [7732-18-5]

ORIGINAL MEAASUREMENTS:

Selleck, F.T.; Carmichael, L.T.; Sage, B.H.

Ind. Eng. Chem. 1952, 44, 2219-2226.

T/F T/K Total pressure Total /(Lb/Sq.Inch pressure Absolute) /bar*

Mole fraction of H2S Gas phase Liquid phase

220 377.59

280 410.93

200 400 600 800 1000 1250 1500 1750 2000 2250 2500 2750 3000 200 400 600 800 1000 1250 1500 1750 2000 2250 2500 2750 3000 200 400 600 800 1000 1250 1500 1750 2000 2250 2500 2750 3000

calculated by the compiler;

340 444.26

1 3 . 7 9 2 7 . 5 8 41 .37 5 5 . 1 6 6 8 . 9 5 8 6 . 1 8

1 0 3 . 4 120 .7 1 3 7 . 9 155 .1 1 7 2 . 4 189 .6 2 0 6 . 8

1 3 . 7 9 2 7 . 5 8 41 .37 5 5 . 1 6 6 8 . 9 5 8 6 . 1 8

1 0 3 . 4 120 .7 1 3 7 . 9 155 .1 1 7 2 . 4 189 .6 2 0 6 . 8

1 3 . 7 9 2 7 . 5 8 41 .37 5 5 . 1 6 6 8 . 9 5 8 6 . 1 8

1 0 3 . 4 120 .7 1 3 7 . 9 155 .1 1 7 2 . 4 189 .6 2 0 6 . 8

0 .9046 0 .9477 0 .9597 0 .9647 0 .9664 0 .9665 0 .9651 0 .9630 0 .9602 0 .9568 0 .9531 0 .9491 0 .9451 0 .7375 0 .8589 0 .8984 0 .9155 0 .9248 0 .9307 0 .9330 0 .9327 0 .9303 0 .9263 0 .9213 0 .9159 0 .9104 0 .3981 0 .6828 0 .7772 0 .8224 0 .8466 0 .8646 0 .8742 0 .8788 0 .8797 0 .8779 0 .8740 0 .8681 0 .8606

0 .0077 0 .0156 0 .0230 0 .0301 0 .0371 0 .0463 0 .0577 0 .0690 0 .0823 0 .0973 0 .1145 0 .1346 0 .1586 0 .0057 0 .0127 0 .0191 0 .0250 0 .0308 0 .0382 0 .0463 0 .0550 0 .0647 0 .0750 0 .0860 0 .0978 0 .1106 0 .0029 0 .0094 0 .0155 0 .0214 0 .0273 0 .0351 0 .0435 0 .0520 0 .0610 0 .0705 0 .0805 0 .0910 0 .1024

at this temperature the authors obtained the composition of aqueous layers at all higher pressures by extrapolation.


COMPONENTS:

1 . Hydrogen sulfide; H2S; [7783-06-4]

2. Water; H20; [7732-18-5]

VARIABLES: Temperature, concentration


METHOD/APPARATUS/PROCEDURE:

A special bomb, from which samples of either gas phase or liquid phase could be withdrawn, was used. The bomb was flushed with oxygen-free nitrogen, water (50 cm3) added and the apparatus saturated with H2S (pressure not stated). The bomb and contents were then heated in a 'stirrer-furnace1 to the required temperature for 25 to 50 hrs. A sample of the liquid phase was then analysed iodimetrically. A sample of the hot gas phase was passed through traps to collect the condensed water and through iodine solution. The H2S in the hot gas phase was determined iodimetrically and the water content found from the weight of condensate.

ORIGINAL MEASUREMENTS: Kozintseva, T.N. Geokhimiya 1964, 8, 758-765.

PREPARED BY: P.G.T. Fogg

SOURCE AND PURITY OF MATERIALS; No information

ESTIMATED ERROR: 6T/K = 2 (author)

REFERENCES:

T/K Composition of gas phase Composition of liquid phase Henry const

Cone.of Mole P g Cone.of Mole Mole ^ /atm H2S ratio 2 H2S ratio fraction /mol dm"3 H2S/H20 /atm /mol dm"3 H2S/H20 x

433.2 475.2 502.2 502.2 502.2 535.2 535.2 535.2 535.2 535.2 574.2 574.2 603.2 603.2 * calcu t Henry

0.00831 0.00618 0.00507 0.00419 0.00725 0.00792 0.00507 0.00583 0.00677 0.00675 0.00740 0.00531 0.00860 0.00746 lated by

0.224 0.0663 0.0325 0.0269 0.0465 0.0283 0.0181 0.0208 0.0242 0.0241 0.0138 0.0099 0.0098 0.0085

compiler. 1 s constant = PTT H2

1 .44 1 .17 1 .02 0.84 1 .46 1 .69 1 .08 1 .25 1 .45 1 .44 1 .70 1 .22 2.07 1 .80

S/xH2S

0.0440 0.0339 0.0296 0.0234 0.0423 0.0494 0.0319 0.0368 0.0432 0.0428 0.0585 0.0428 0.0884 0.0756

0.00078 0.00061 0.000532 0.000422 0.000762 0.000887 0.000575 0.000660 0.000778 0.000770 0.00105 0.000767 0.00159 0.00136

0.00078 0.00061 0.000532 0.000422 0.000761 0.000886 0.000575 0.000660 0.000777 0.000769 0.00105 0.000766 0.00159 0.00136

1850 1920 1920 2000 1910 1910 1890 1890 1860 1880 1620 1590 1300 1320

1 atm = 760 mmHg = 1.01325 bar



[COMPONENTS: T

1 . Hydrogen s u l f i d e ; H 2 S; [7783-06 -4 ]

2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

VARIABLES:


ORIGINAL MEASUREMENTS: 1

C l a r k e , E . C . W . ; G l e w , D . N .

Can. J. Chem. 1 9 7 1 , 4 3 , 6 9 1 - 6 9 8

PREPARED BY: 1

C . L . Young

1 EXPERIMENTAL VALUES: MOLE FRACTIONS 1 T o t a l P r e s s u r e H 2 S i n g a s H 2 S i n l i q u i d H S " i n l i q u i d

T/K P / a t m P / k P a y ^ s 1 0 ^ H 2 S 10"XES~

1 2 7 3 . 1 5 1 0 . 5 3 9 8 5 5 4 . 7 0 0 0 . 9 8 9 6 4 2 . 0 1 8 9 1 . 1 4 1 2 7 3 . 1 5 1 0 . 6 4 6 6 3 6 5 . 5 2 0 0 . 9 9 0 4 8 2 . 4 1 9 8 1 . 2 5 2 7 3 . 1 5 0 0 . 8 1 4 9 6 8 2 . 5 7 6 0 . 9 9 2 4 0 3 . 0 4 9 7 1 . 4 0 2 7 8 . 1 0 6 0 . 4 9 2 0 5 4 9 . 8 5 7 0 . 9 8 2 2 8 1 . 5 5 1 5 1 . 1 1 2 7 8 . 1 0 8 0 . 5 7 4 5 7 5 8 . 2 1 8 0 . 9 8 4 7 8 1 . 8 1 4 6 1 . 2 0 2 7 8 . 1 0 5 0 . 6 9 5 3 3 6 9 . 5 3 3 0 . 9 8 7 3 8 2 . 1 9 8 8 1 . 3 2 2 7 8 . 1 0 5 0 . 8 9 0 3 2 9 0 . 2 1 2 0 . 9 9 0 0 8 2 . 8 1 7 1 1 . 5 0 2 8 3 . 1 6 9 0 . 4 6 1 5 4 4 6 . 7 6 6 0 . 9 7 3 3 4 1 . 2 3 6 5 1 . 0 9 2 8 3 . 1 6 8 0 . 5 4 0 4 1 5 4 . 7 5 7 0 . 9 7 7 1 7 1 . 4 5 2 2 1 . 1 8 2 8 3 . 1 6 9 0 . 6 5 6 6 7 6 6 . 5 3 7 0 . 9 8 1 1 5 1 . 7 6 9 7 1 . 3 1 2 8 3 . 1 6 9 0 . 8 4 6 5 4 8 5 . 7 7 6 0 . 9 8 5 2 9 2 . 2 8 6 4 1 . 4 9 2 8 8 . 1 5 8 0 . 5 7 2 6 5 5 8 . 0 2 4 0 . 9 7 0 1 0 1 . 3 2 3 4 1 . 2 4 2 8 8 . 1 5 8 0 . 7 0 0 4 4 7 0 . 9 7 2 0 . 9 7 5 4 6 1 . 6 2 5 5 1 . 3 7 2 8 8 . 1 5 6 0 . 9 1 2 7 5 9 2 . 4 8 4 0 . 9 8 1 0 5 2 . 1 2 5 8 1 . 5 7 2 9 3 . 1 6 0 0 . 4 9 4 5 6 5 0 . 1 1 1 0 . 9 5 2 6 5 0 . 9 8 4 7 1 . 1 6 2 9 3 . 1 6 1 0 . 5 8 3 2 5 5 9 . 0 9 8 0 . 9 5 9 7 5 1 . 1 6 8 9 1 . 2 7 2 9 3 . 1 6 1 0 . 7 1 6 7 3 7 2 . 6 2 2 0 . 9 6 7 1 2 1 . 4 4 5 6 1 . 4 1 2 9 3 . 1 5 9 0 . 9 4 1 1 5 9 5 . 3 6 2 0 . 9 7 4 7 9 1 . 9 0 9 1 1 . 6 2 2 9 8 . 1 6 8 0 . 5 5 2 4 4 5 5 . 9 7 6 0 . 9 4 2 5 0 0 . 9 6 1 6 1 . 2 5 2 9 8 . 1 6 6 0 . 6 6 7 6 6 6 7 . 6 5 1 0 . 9 5 2 2 7 1 . 1 7 2 9 1 . 3 8 2 9 8 . 1 6 5 0 . 8 5 3 1 9 8 6 . 4 4 9 0 . 9 6 2 4 5 1 . 5 1 2 2 1 . 5 6 2 9 8 . 1 6 8 0 . 5 8 1 9 2 5 8 . 9 6 3 0 . 9 4 5 3 6 1 . 0 1 6 2 1 . 2 8 2 9 8 . 1 6 7 0 . 7 1 8 3 4 7 2 . 7 8 6 0 . 9 5 5 5 7 1 . 2 6 6 3 1 . 4 3 2 9 8 . 1 6 7 0 . 9 5 0 3 9 9 6 . 2 9 8 0 . 9 6 6 2 0 1 . 6 9 0 4 1 . 6 5 2 9 8 . 1 8 0 0 . 5 5 3 7 7 5 6 . 1 1 1 0 . 9 4 2 5 9 0 . 9 6 4 5 1 . 2 5 2 9 8 . 1 7 9 0 . 6 8 4 4 2 6 9 . 3 4 9 0 . 9 5 3 3 8 1 . 2 0 4 2 1 . 3 9



S t a t i c e q u i l i b r i u m c e l l d e s c r i b e d i n s o u r c e . V a p o r p r e s s u r e s o v e r s a t u r a t e d a q u e o u s s o l u t i o n s w e r e m e a s u r e d w i t h a f u s e d q u a r t z p r e c i s i o n B o u r d o n g a u g e . G r e a t c a r e w a s t a k e n t o m a k e t h e n e c e s s a r y c o r r e c t i o n f o r w a t e r i n t h e v a p o r p h a s e .

ISOURCE AND PURITY OF MATERIALS: 1

1 . P r e p a r e d by t h e a c t i o n of d i s t i l l e d w a t e r on a lumin ium s u l f i d e (pu re g r a d e K and K Lab) .

2 . D i s t i l l e d .

ESTIMATED ERROR:

6T/K = 0 . 0 0 1 5 ; SP/P = 0 . 0 0 0 2 ; 6 * H 2 S / * H 2 S = 0 - 0 0 2

REFERENCES:


COMPONENTS: 1. Hydrogen sulfide; H2S;

[7783-06-4] 2. Water; H20; [7732-18-5]

ORIGINAL MEASUREMENTS: Clarke, E.C.W.; Glew, D.N. Can. J. Chem. 1971,43, 691-698

EXPERIMENTAL VALUES: Total Pressures

T/K P/atm P/kPa Mole fractions

H2S in gas H2S in liquid HS y H2S 10

3tf. H2S in liquid

1 0 ^ H S -298.181 303.145 303.142 303.145 313.141 313.141 313.142 323.137 323.134 323.135

0.90833 0.56822 0.70403 0.93731 0.49072 0.61249 0.82651 0.54699 0.68605 0.93305

92.036 57.575 71.336 94.973 49.722 62.061 83.746 55.424 69.154 94.541

0.96465 0.92521 0.93942 0.95421 0.84998 0.87943 .91016 .77499 .82000 .86687

6137 8680 0907 4719 5616

0.7245 0100 4801 6364

0.9132

61 27 43 66 17 33 57 22 40 68

Values of #Hc- were calculated from the equation logio K 0 = 55.06

ll 2 O 3760 (T/K) - 20 log(T/K)


I COMPONENTS:

1 . H y d r o g e n s u l f i d e ; [ 7 7 8 3 -

2 . W a t e r

VARIABLES:

- 0 6 - 4 ] ; H 2 0 ; [ 7 7 3 2


I EXPERIMENTAL

T/K

2 8 3 . 2

2 9 3 . 2

VALUES:

H 2 S ;

- 1 8 - 5 ]

T o t a l M o l e f r a c t i o n p r e s s u r e

/ k P a

1 5 4 . 8 1 8 2 . 4 2 0 0 . 3 2 6 5 . 8 271 . 8 2 8 3 . 0 2 9 2 . 4 2 9 2 . 8 361 . 7 1 7 3 . 4 3 2 3 . 7 4 5 2 . 6 5 6 9 . 8 6 8 4 . 7 7 8 3 . 3 8 2 4 . 7 8 3 5 . 0 9 5 5 . 9 9 7 6 . 6

1 0 4 5 . 6

o f H 2 S i n l i q u i d

0 . 0 0 4 0 5 0 . 0 0 5 0 0 0 . 0 0 5 5 6 0 . 0 0 6 9 2 0 . 0 0 7 1 6 0 . 0 0 6 9 7 0 . 0 0 7 6 2 0 . 0 0 7 4 7 0 . 0 0 8 9 4 0 . 0 0 3 2 8 0 . 0 0 6 4 9 0 . 0 0 9 1 6 0 . 0 1 1 3 7 0 . 0 1 3 4 0 0 . 0 1 5 0 0 0 . 0 1 5 7 7 0 . 0 1 6 0 5 0 . 0 1 8 1 7 0 . 0 1 8 2 1 0 . 0 1 9 8 6

* N a t i o n a l D e p o s i t o r y o f U n p u b l i s h e d N a t i o n a l R e s e a r c h C o u n c i l , O t t a w a ,


L e e , J . I . ; M a t h e r , A.E Ber. Bunsenges. phys. 1 9 7 7 , 81 , 1 0 2 0 - 1 0 2 3 . ( N u m e r i c a l d a t a d e p o s i N a t i o n a l D e p o s i t o r y of D a t a , O t t a w a , C a n a d a ) *

PREPARED BY:

P . G . '

T/K

2 9 3 . 2

3 0 3 . 2

D a t a , N a t O n t a r i o ,

r . F o g g

T o t a l p r e s s u r e

/ k P a

1 0 7 3 . 1 1 0 8 6 . 9 1 1 8 3 . 5 1 2 7 3 . 1 1 3 5 5 . 8

2 1 4 . 5 3 5 2 . 4 5 0 7 . 5 6 1 4 . 4 7 2 4 . 6 9 3 4 . 8

1 0 2 4 . 6 1 1 9 6 . 8 1 2 7 3 . 4 1 2 7 8 . 9 1 4 6 6 . 4 1 5 6 9 . 8 1 5 9 0 . 5 1 6 2 3 . 4 1 6 4 5 . 7

i o n a l S c i e n c e

. I Chem.

t e d i n t h e U n p u b l i s h e d

M o l e f r a c t i o n o f H 2 S

i n l i q u i d

0 . 0 2 0 5 8 0 . 0 2 0 6 8 0 . 0 2 2 1 2 0 . 0 2 4 0 9 0 . 0 2 5 1 9 0 . 0 0 3 2 6 0 . 0 0 5 5 6 0 . 0 0 7 9 2 0 . 0 0 9 3 6 0 . 0 1 1 2 4 0 . 0 1 4 3 3 0 . 0 1 5 9 0 0 . 0 1 7 9 0 0 . 0 1 9 2 3 0 . 0 1 9 4 5 0 . 0 2 2 0 3 0 . 0 2 3 3 7 0 . 0 2 3 5 5 0 . 0 2 4 3 0 0 . 0 2 4 2 6

L i b r a r y , K1A O S 2 , C a n a d a

AUXILIARY INFORMATION METHOD/APPARATUS/PROCEDURE: A recirculating equilibrium cell was used. It consisted of a high pressure liquid level gauge and vapor reservoir. The gas phase was circulated by a magnetic pump. Samples of the liquid phase could be withdrawn. The total quantity of H2S in a sample was found from the volume of gas evolved when the pressure over the sample dropped to atmospheric and the residual gas in solution, as measured by gas-liquid chromatography.

SOURCE AND PURITY OF MATERIALS: 1. Matheson C.P. grade.

2. Laboratory distilled.

ESTIMATED ERROR: 6T/K = 0.5 below 403 K; 6T/K = 0.7 above 403 K (authors)

REFERENCES:

Hydrogen Sulfide in Aqueous Solvents 15 COMPONENTS: 1. Hydrogen sulfide; H2S;

[7783-06-4] 2. Water; H20; [7732-18-5]

EXPERIMENTAL VALUES: T/K Total Mole fraction

pressure of H2S /kPa in liquid

1659.5 1758.9 1900.5 1945.3 1955.9 1997.0 2034.3 2059.1 2079.1 2106.7 2169.0 2262.1 2265.5 472.0 730.4 970.8 1070.6 1133.0 1235.8 1469.9 1534.6 1583.1 1609.1 1636.8 1671 .4 1671 .5 1707.2 1788.3 1892.8 1934.1 1981 .9 1983.1 2052.2 2059.9 2061 .3 2100.7 2100.8 2128.3 2227.0 2417.4

0.02453 0.02582 0.02806 0.02873 0.02833 0.02956 0.02993 0.03054 0.03063 0.03077 0.03195 0.03275 0.03292 0.00620 0.00915 0.01249 0.01373 0.01434 0.01565 0.01810 0.01950 0.01979 0.01941 0.01975 0.02013 0.02061 0.02077 0.02126 0.02282 0.02334 0.02347 0.02398 0.02408 0.02498 0.02517 0.02526 0.02546 0.02529 0.02612 0.02826

ORIGINAL MEASUREMENTS: Lee, J.I.; Mather, A.E. Ber. Bunsenges. phys. Chem. 1977, 81, 1020-1023. (Numerical data deposited in the National Depository of Unpublished Data, Ottawa, Canada)*

T/K Total Mole fraction pressure of H2S /kPa in liquid

2452.9 2458.9 2479.4 2561.6 718.3 892.9

1005.5 1165.5 1510.9 1510.9 1683.2 1848.4 1928.1 1940.1 1976.3 2010.1 2048.1 2133.8 2178.0 2265.8 2383.1 2482.5 2518.3 2637.1 2637.1 2658.1 2711 .2 2737.2 2744.5 2755.4 2806.1 2808.4 2816.5 2893.7 240.6 406.1 575.0 836.9 1195.4 1541 .7

0.02822 0.02926 0.02873 0.02983 0.00783 0.00963 0.01090 0.01231 0.01542 0.01525 0.01750 0.01878 0.01997 0.01996 0.01975 0.02022 0.02048 0.02114 0.02210 0.02327 0.02383 0.02458 0.02437 0.02588 0.02594 0.02564 0.02640 0.02663 0.02743 0.02710 0.02779 0.02742 0.02722 0.02822 0.00211 0.00365 0.00530 0.00769 0.01100 0.01425

* National Depository of Unpublished Data, National Science Library, National Research Council, Ottawa, Ontario, K1A OS2, Canada.


COMPONENTS: 1. Hydrogen sulfide; H2S;

[7783-06-4] 2. Water; H20; [7732-18-5]

EXPERIMENTAL VALUES: T/K Total Mole fraction

pressure of H2S /kPa in liquid

1650.4 1762.3 1914.0 2015.6 2077.6 2105.2 2148.4 2284.5 2325.8 2346.5 2348.4 2444.0 2546.5 2554.3 2560.3 2567.4 2569.0 2679.6 2692.0 2693.1 2843.2 2871 .3 3038.1 3098.6 3174.7 3210.5 3250.0 3257.1 3326.1 3415.7 3457.1 3498.7 3601 .6 3651 .5 3652.0 3734.2 3844.7 3877.9 3892.9 3899.7

0.01546 0.01626 0.01779 0.01858 0.01913 0.01951 0.01967 0.02118 0.02141 0.02168 0.02127 0.02221 0.02322 0.02304 0.02292 0.02333 0.02328 0.02436 0.02454 0.02438 0.02562 0.02615 0.02717 0.02765 0.02821 0.02863 0.02922 0.02885 0.02974 0.03046 0.03052 0.03102 0.03184 0.03175 0.03204 0.03281 0.03358 0.03407 0.03397 0.03380

ORIGINAL MEASUREMENTS: Lee, J.I.; Mather, A.E. Ber. Bunsenges. phys. Chem. 1977 , 81, 1 0 2 0 - 1 0 2 3 . (Numerical data deposited in the National Depository of Unpublished Data, Ottawa, Canada)*

T/K Total Mole fraction pressure of H2S /kPa in liquid

3961 .9 4003.6 4111 .8 4160.6 4160.7 4217.2 4223.6 4224.1 374.8 546.3 760.9 802.2 829.0 1022.9 1050.5 1132.4 1450.3 1492.0 1518.5 1780.5 1905.7 2181 .4 2214.9 2511 .3 2636.5 2877.5 2919.2 3091 .5 3215.4 3381 .1 3546.3 3911 .7 4194.4 4711 .5 4757.3 5091 .7 5112.3 5126.1 238.2 514.0

0.03402 0.03425 0.03487 0.03497 0.03516 0.03557 0.03553 0.03525 0.00277 0.00421 0.00583 0.00622 0.00647 0.00783 0.00814 0.00914 0.01147 0.01184 0.01210 0.01429 0.01478 0.01720 0.01735 0.01981 0.02012 0.02230 0.02280 0.02406 0.02515 0.02622 0.02646 0.03029 0.03196 0.03546 0.03518 0.03662 0.03694 0.03715 0.00126 0.00317



I COMPONENTS: 1. Hydrogen sulfide;

[7783-06-4] 2. Water; H20; [7732-


H2S;

-18-5]

T/K Total Mole fraction pressure /kPa

363.2 896.5 1217.1 1530.8 1834.2 2120.3 2341.0 2616.6 2733.6 2774.9 2850.8 2988.9 3216.4 3264.4 3436.4 3532.7 3533.3 3698.4 3843.2 4029.3 4222.4 4256.9 4470.6 4574.0 4733.5 4939.4 4954.2 5091.1 5126.5 5229.0 5264.4 5277.3 5526.0 5608.8 5609.2 5622.5 5642.7 5712.6 5828.8 6043.1 6332.7

* National Depository

of H2S in liquid

0.00577 0.00793 0.01012 0.01217 0.01370 0.01522 0.01729 0.01786 0.01823 0.01855 0.01959 0.02092 0.02142 0.02231 0.02299 0.02300 0.02403 0.02481 0.02620 0.02749 0.02756 0.02841 0.02925 0.03006 0.03132 0.03129 0.03205 0.03223 0.03311 0.03323 0.03317 0.03438 0.03456 0.03469 0.03500 0.03500 0.03533 0.03610 0.03709 0.03804

ORIGINAL Lee, J.I

MEASUREMENTS: . ; Mather, A.E

Ber. Bunsenges. phys. 1977, 81 1020-1023. (Numerical data deposi National Depository of Data, Ottawa, Canada)*

T/K

363.2 393.2

423.2

Total pressure /kPa

6574.0 496.2 858.2 1154.7 1499.4 1762.1 2072.3 2427.4 2617.0 2941.2 3196.3 3527.2 3610.0 3891.9 3954.7 4023.6 4205.6 4643.4 4849.8 4919.2 4953.2 5518.6 5746.5 5863.3 5987.4 6049.5 6194.7 6208.5 6228.7 6394.6 6394.7 6491.1 6573.9 6587.3 6670.4 692.5 933.8 1154.4 1388.8 1471.4

of Unpublished Data, National Science L National Research Council, Ottawa, Ontario, K1A OS2, Canada

Ghem,

ted in the Unpublished

Mole fraction of H2S in liquid

0.03943 0.00164 0.00375 0.00547 0.00707 0.00860 0.01050 0.01236 0.01367 0.01536 0.01666 0.01831 0.01887 0.02043 0.02073 0.02116 0.02199 0.02426 0.02545 0.02571 0.02590 0.02879 0.02984 0.03050 0.03099 0.03168 0.03206 0.03177 0.03223 0.03317 0.03315 0.03332 0.03359 0.03388 0.03416 0.00095 0.00216 0.00333 0.00442 0.00499

ibrary,


COMPONENTS 1 Hydrogen sulfide; H S;

[7783-06-4] l

Water; H20; [7732-18-5]

ORIGINAL MEASUREMENTS: Lee, J.I.; Mather, A.E. Ber. Bunsenges. phys, Chem. 192Z, 81, 1020-1023. (Numerical data deposited in the National Depository of Unpublished Data, Ottawa, Canada)*

EXPERIMENTAL VALUES: T/K Total

pressure /kPa


T/K Total pressure /kPa

5560.2 5863.6 6277.3 6339.3 6401 .4 6601 .3 1071 .3 1422.9 1865.1 2154.7 2354.6 2451.1 2540.8 2629.3 3229.2 3484.3 3911.7 4242.7 4615.0 5076.9 5421 .7 5918.1


0.02520 0.02650 0.02822 0.02896 0.02897 0.02993 0.00032 0.00199 0.00397 0.00531 0.00621 0.00657 0.00700 0.00742 0.01033 0.01158 0.01356 0.01497 0.01650 0.01866 0.02029 0.02257

423.2 1568. 1741 . 1768. 1898. 2031 . 2078. 2223. 2230. 2376. 2575. 2775. 2980, 3051 . 3202, 3450, 3739. 4105. 4256. 4403, 4623, 4691 , 5133, 5222,

0.00552 0.00635 0.00626 0.00749 0.00787 0.00816 0.00863 0.00877 0.00957 0.01036 0.01147 0.01268 0.01283 0.01364 0.01498 0.01644 0.01846 0.01893 0.01978 0.02056 0.02109 0.02324 0.02347

423.2

453.2

T/K Total pressure /kPa

Mole fraction of H2S in vapour

T/K Total pressure

/kPa

1942 2196 2624 2699 3003 3079

Mole fraction of H2S in vapour

0.7409 0.7812 0.8199 0.8373 0.8292 0.8356

3 6 3 . 2

3 9 3 . 2

1921 201 1 2 3 8 9 1486 2 5 0 0 3161 3 1 7 4 3 2 3 0 3401

0 . 9 6 1 4 0 . 9 6 0 6 0 . 9 7 0 9 0 . 8 8 6 5 0 . 9 2 9 8 0 . 9 4 1 5 0 . 9 5 2 9 0 . 9 3 1 4 0 . 9 5 2 6

423.2



COMPONENTS: ~ [

1 . Hydrogen s u l f i d e ; H 2 S; [7783 06 4]

2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

VARIABLES:


B y e s e d a , J . J . ; D e e t z , J . A . ; M a n n i n g , W . P .

Proc.Laurance Reid Gas Cond.Conf. 1 9 8 5 .

PREPARED BY: I

P . G . T . F o g g

I EXPERIMENTAL VALUES: I

T/K P U c / p s i a P u e / b a r * O s t w a l d c o e f f . M o l e f r a c t i o n L i n l i q u i d *

X H 2 S

2 9 7 . 1 1 4 . 7 3 1 . 0 1 6 2 . 5 0 . 0 0 1 9

* c a l c u l a t e d b y c o m p i l e r



T h e H 2 S w a s c o n t a i n e d i n a

t h e r m o s t a t t e d m e t a l c y l i n d e r

c o n n e c t e d t o a p r e s s u r e g a g e , v a c u u m

pump a n d s u p p l y o f g a s . A t i g h t

f i t t i n g i n t e r n a l p i s t o n s e a l e d w i t h

a n O - r i n g f i t t e d i n t o t h e c y l i n d e r

s o t h a t t h e v o l u m e o f g a s c o u l d b e

c h a n g e d b y c o n t r o l l e d m o v e m e n t o f

t h e p i s t o n . A m e a s u r e d v o l u m e o f

s o l v e n t w a s i n j e c t e d i n t o t h e

c y l i n d e r b y a s y r i n g e . T h e

a b s o r p t i o n o f g a s w a s f o u n d f r o m t h e

m o v e m e n t o f t h e p i s t o n w h i c h w a s

n e c e s s a r y t o m a i n t a i n c o n s t a n t

p r e s s u r e .

L

ISOURCE AND PURITY OF MATERIALS: I

No i n f o r m a t i o n .

ESTIMATED ERROR:

REFERENCES:


COMPONENTS: EVALUATOR: Peter G.T. Fogg,

1. Hydrogen sulfide; H2S; [7783-06-4] Department of Applied Chemistry and Life Sciences, Polytechnic of North London,

2. Aqueous solutions of weak or Holloway, London N7 8DB, U.K. non-electrolytes

July 1987


C a r b o n d i o x i d e ; C 0 2 ; [ 1 2 4 - 3 8 - 9 ] P h e n o l ; C 6 H 6 0 ; [ 1 0 8 - 9 5 - 2 ] 1 , 2 , 3 - P r o p a n e t r i o l , (glycerol); C 3 H 8 0 3 ; [ 5 6 - 8 1 - 5 ] Ethanol; C2H60; [64-17-5] Urea; C H ^ O ; [57-13-6]

The solubility of hydrogen sulfide in water containing carbon dioxide was measured by Golutvin, Malysheva & Skorobogatova (1). It was part of a study of the ratios of concentrations of H2S/C02 in the gas phase to that in the liquid phase, in the presence of aqueous solutions. Water at 293.2 K was saturated with various mixtures of hydrogen sulfide and carbon dioxide. The total pressure of gas (C02 + H2S + H20) was equal to barometric pressure. Within the limits of the experimental error the molar concentration of hydrogen sulfide in the saturated solution was proportional to the partial pressure of the hydrogen sulfide. The varying partial pressure of carbon dioxide did not cause any deviation from this linear relationship between solubility and partial pressure of hydrogen sulfide. Extrapolation of the solubility to a partial pressure of 1.013 bar gives a solubility of 0.098 mol dm"3 at 293.2 K. This may be compared with the solubility of 0.112 mol dm-3 calculated from the recommended value of the mole fraction solubility for H2S in pure water (see Critical Evaluation - pure water).

In addition, Golutvin et al . (1) measured solubilities of mixtures of carbon dioxide and hydrogen sulfide in aqueous solutions of ammonia and of ammonia and phenol. There is no obvious inconsistency between these measurements of solubility in ammonia solutions and measurements made by other workers (see Critical Evaluation - aqueous solutions of ammonia). No other measurements of solubilities in the presence of phenol are available for comparison.

Kiss, Lajtai & Thury (2) measured solubilities of hydrogen sulfide in pure water and aqueous solutions of ethanol, glycerol and of urea in the temperature range 273.2 K to 298.15 K. The total pressure was barometric but the reported solubilities were corrected to a partial pressure of hydrogen sulfide of 1.013 bar. Solubilities in pure water are within a standard deviation of the recommended solubilities (see Critical Evaluation - pure water) and are therefore consistent with measurements by other workers.

Concentrations of ethanol ranged from 2 mol dm-3 to 16 mol dm"3. Concentrations of glycerol and of urea ranged from 2 mol dm"3 to 8 mol dm"3. The solubilities in ethanol solutions show a self-consistent variation with temperature and concentration of ethanol. They may be extrapolated to give estimated solubilities3in pure ethanol. i.e, ethanol at a concentration of approximately 17.6 mol dm"3. The extrapolated value for 273.2 K is about 6% lower than the solubility calculated from direct measurements of the solubility in pure ethanol made by Gerrard (3). The extrapolated solubility for 285.5 K is about 40% greater and the extrapolated value for 298.15 K about 100% greater than solubilities estimated from Gerrard's data.

Solubility measurements for aqueous solutions of glycerol are self-consistent but, in this case, the concentrations of glycerol do not extend high enough to enable extrapolation to pure glycerol (approx. 13.7 mol d m " 3 ) . Comparison with other systems is not possible for this system or for the urea-water-hydrogen sulfide system.

References

1. Golutvin, Yu. M.; Malysheva, T.V.; Skorobogatova, V.I. Izvest. Sibir. Otdel. Akad. Nauk. SSSR 1958, No.8, 83-87.

2. Kiss, A.; Lajtai, I.; Thury, G. Z. anorg, allgem. Chew. 1937, 233, 346-352.

3. Gerrard, W. J. Appl. Chem. Biotechnol. 1972, 22, 623-650.


I COMPONENTS: ' T


2 . C a r b o n d i o x i d e ; C 0 2 ; [ 1 2 4 - 3 8 - 9 ]

3 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

VARIABLES: [

C o n c e n t r a t i o n o f a m m o n i a

[EXPERIMENTAL VALUES:

L i q u i d p h a s e


G o l u t v i n , Yu . M . ; M a l y s h e v a , T . V . ; S k o r o b o g a t o v a , V . I .

Izvest. Sibir. Otdel. Akad. Nauk. S.S.S.R. 1 9 5 8 , No.8, 8 3 - 7 .

PREPARED BY:

P . G . T . F o g g

G a s p h a s e

C o n e , o f H 2 S C o n e , o f C 0 2 P u c / Pnr, Pu c / b a r Pnn / b a r / T J 3 / -i J 3 ri 2 o L,U 2 n 2 o L,U 2 I / m o l dm 6 / m o l dm d *

0 . 0 0 0 0 0 0 0 . 0 3 0 1 7 0 0 . 0 0 0 0 0 . 0 0 0 0 0 . 9 8 9 9 0 . 0 0 1 4 2 5 0 . 0 2 5 9 7 9 0 . 0 3 3 8 0 . 0 3 2 4 0 . 9 5 7 5 0 . 0 0 3 3 7 7 0 . 0 2 0 6 8 0 0 . 0 3 7 8 0 . 0 3 6 1 0 . 9 5 3 8 0 . 0 1 1 3 1 0 0 . 0 1 8 7 7 5 0 . 1 2 6 3 0 . 1 1 1 0 0 . 8 7 8 9 0 . 0 1 2 3 1 0 0 . 0 1 8 0 7 0 0 . 2 2 0 8 0 . 1 7 9 0 0 . 8 1 0 9 0 . 0 1 5 3 8 0 0 . 0 2 1 0 5 0 0 . 1 9 2 7 0 . 1 5 9 9 0 . 8 3 0 0 0 . 0 1 7 6 9 0 0 . 0 1 9 1 7 5 0 . 3 0 4 4 0 . 2 3 1 0 0 . 7 5 8 9 0 . 0 1 8 5 0 0 0 . 0 1 7 3 4 0 0 . 4 0 0 0 0 . 2 8 2 8 0 . 7 0 7 1 0 . 0 2 0 4 0 0 0 . 0 1 7 3 4 2 0 . 3 8 7 1 0 . 2 7 6 2 0 . 7 1 3 7 0 . 0 2 1 1 0 0 0 . 0 1 9 9 7 0 0 . 3 9 7 3 0 . 2 8 1 5 0 . 7 0 8 4 0 . 0 3 8 7 2 0 0 . 0 1 4 5 5 0 0 . 7 0 8 4 0 . 4 1 0 5 0 . 5 7 9 4 0 . 0 4 0 2 0 0 0 . 0 1 4 5 4 0 0 . 6 8 8 1 0 . 4 0 3 5 0 . 5 8 6 4 0 . 0 4 3 3 8 0 0 . 0 1 1 9 8 0 0 . 8 1 3 3 0 . 4 4 4 0 0 . 5 4 5 9 0 . 0 4 8 6 3 0 0 . 0 1 1 8 1 0 0 . 7 7 4 0 0 . 4 3 1 9 0 . 5 5 8 0 | 0 . 0 5 2 4 0 0 0 . 0 0 6 8 2 7 1 0 . 0 5 6 9 2 0 0 . 0 1 0 0 8 8 1

. 6 6 5 0 0 . 6 1 8 4 0 . 3 7 1 5

. 2 2 2 0 0 . 5 4 4 4 0 . 4 4 5 5 0 . 0 7 2 7 4 6 0 . 0 0 4 2 9 5 3 . 7 3 5 0 0 . 7 8 0 8 0 . 2 0 9 1 I 0 . 0 8 2 1 8 0 0 . 0 0 2 2 7 4 3 . 9 9 3 0 0 . 7 9 1 6 0 . 1 9 8 3 0 . 0 9 1 1 8 0 0 . 0 0 1 4 9 1 1 6 . 4 5 1 0 0 . 9 3 3 1 0 . 0 5 6 8

T/K = 2 9 3 . 2 ; c a l c u l a t e d b y t h e c o m p i l e r o n t h e a s s u m p t i o n t h a t t h e sum o f t h e p a r t i a l p r e s s u r e o f H 2 S , C 0 2 & H 2 0 i s 1 . 0 1 3 b a r .

C o n c e n t r a t i o n s o f H 2 S a n d o f C 0 2 i n c l u d e a l l i o n i c s p e c i e s d e r i v e d f r o m | t h e s e c o m p o u n d s .

AUXILIARY


P r e m i x e d h y d r o g e n s u l f i d e a n d c a r b o n d i o x i d e w e r e b u b b l e d t h r o u g h w a t e r i n a t h e r m o s t a t t e d s a t u r a t o r f o r 4 . 5 t o 5 h r s . T h e g a s a n d t h e l i q u i d p h a s e s w e r e a n a l y s e d b y c h e m i c a l m e t h o d s .

T h e s o l u b i l i t y o f H 2 S , i n t h e a b s e n c e o f C 0 2 , w a s m e a s u r e d b y t h e

a u t h o r s b u t t h e r e i s c l e a r l y a m i s t a k e i n t h e f i g u r e s w h i c h w e r e

p u b l i s h e d .

INFORMATION

[SOURCE AND PURITY OF MATERIALS:

1 . f r o m a K i p p ' s a p p a r a t u s .

2 . b y a c t i o n o f h y d r o c h l o r i c a c i d o n m a r b l e c h i p s .

ESTIMATED ERROR:

6T/K = 0 . 1 ( a u t h o r s )

REFERENCES:


COMPONENTS:


2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

3 . U r e a ; C H 4 N 2 0 ; [ 5 7 - 1 3 - 6 ]


Kiss, A. v.; Lajtai, I.; Thury, G. Zeit. anorg. allgem. Chem. 1937, 233, 346-352.

VARIABLES: T e m p e r a t u r e , c o n c e n t r a t i o n o f

u r e a .

PREPARED BY: P . G . T . F o g g


C o n e , o f C o n e , o f H 2 S i n l i q u i d / m o l d m - 3 O s t w a l d c o e f f i c i e n t , L u r e a

/mol dm"3 273.20 K 285.65 K 298.15 K 273.20 K 285.65 K 298.15 K

H2S

0.2079 0.2095 0.2110 0.2129

= 1 . 0 1 3 b a r

0 .1410

0 .1445

0 .1462

0 .1487

0 .1497

0 .1014

0 .1055

0 .1081

0 .1103

0 .1117

4 . 6 6 2

4 . 6 9 8

4 . 7 3 2

4 . 7 7 4

3 .307

3 .389

3 .424

3 .487

3 .511

2 . 4 8 2

2 . 5 8 2

2 . 6 4 6

2 . 6 9 8

2 . 7 3 4

AUXILIARY INFORMATION METHOD APPARATUS/PROCEDURE: H2S was bubbled through about 100 cm of water & urea in an absorption vessel at barometric pressure for 1 to 1.5 h. Dissolved H2S was estimated iodimetrically. Allowance was made for the partial pressure of water and the head of liquid in the absorption vessel in the calculation of the partial pressure of H2S. Solubilities were corrected to a partial pressure of 1.013 bar by use of Henry's law.

SOURCE AND PURITY OF MATERIALS: 1. From iron sulfide (ex Merck) and dilute H2S04; washed with H20 and solvent mixture.

2. Distilled. 3. p.a, or puriss. from Merck or Kahlbaum-Schering;

ESTIMATED ERROR: Quoted values are averages from several measurements with a maximum deviation from the mean of 0.2% (authors) REFERENCES:


COMPONENTS:


2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

3 . E t h a n o l ; C 2 H 6 0 ; [ 6 4 - 1 7 - 5 ]


K i s s f A. v . ; L a j t a i , I . ; T h u r y , G.

Zeit. anorg. allgem. Chem, 1 9 3 7 , 2 3 3 , 3 4 6 - 3 5 2 .

VARIABLES: T e m p e r a t u r e , c o n c e n t r a t i o n o f

e t h a n o l .

PREPARED BY: P . G . T . F o g g


C o n e , o f C o n e , o f H 2 S i n l i q u i d / m o l dm" e t h a n o l

/mol dm"

Ostwald coefficient, L

273.20 K 285.65 K 298.15 K 273.20 K 285.65 K 298.15 K

0 2 4 5 6 7 8 10 12 1 4 16

H2S

0.2079 0.1881 0.1680 0.1590 0.1632 0.1761 0.2030 0.2832 0.3982 0.5435 0.7115

= 1 . 0 1 3 b a r

0 .1410

0 .1320

0 .1276

0 .1285

0 .1345

0 .1513

0 .1709

0 .2350

0 . 3 1 8 2

0 .4255

0 .5650

0 .1014

0 .0994

0 .1034

0 .1074

0 .1155

0 .1324

0 .1470

0 .1970

0 .2621

0 .3431

0 .4469

4 . 6 6 2

4 . 2 1 8

3 . 7 6 7

3 . 5 6 6

3 . 6 6 0

3 . 9 4 9

4 . 5 5 2

6 . 3 5 1

8 . 0 2 9

2 . 1 9

5 . 9 5

3 . 3 0 7

3 . 0 9 6

2 . 9 8 8

3 . 0 1 3

3 . 1 5 4

3 . 6 3 1

3 . 9 8 9

5 . 5 0 0

7 . 4 6 2

9 . 9 7 8

1 3 . 2 5

2 . 4 8 2

2 . 4 3 3

2 . 5 3 1

2 . 6 2 9

2 . 8 2 7

3 . 2 4 0

3 . 5 9 8

4 . 2 8 1

6 . 4 1 5

8 . 3 9 7

1 0 . 9 4


METHOD 'APPARATUS/PROCEDURE:

H2S w a s b u b b l e d t h r o u g h a b o u t

100 cm o f w a t e r & e t h a n o l i n a n

a b s o r p t i o n v e s s e l a t b a r o m e t r i c

p r e s s u r e f o r 1 t o 1 . 5 h . D i s s o l v e d

H2S w a s e s t i m a t e d i o d i m e t r i c a l l y .

A l l o w a n c e s w e r e m a d e f o r t h e

p a r t i a l p r e s s u r e o f w a t e r , t h e

p a r t i a l p r e s s u r e o f e t h a n o l a n d t h e

h e a d o f l i q u i d i n t h e a b s o r p t i o n

v e s s e l when t h e p a r t i a l p r e s s u r e o f

H 2 S w a s c a l c u l a t e d . S o l u b i l i t i e s

w e r e c o r r e c t e d t o 1 . 0 1 3 b a r b y u s e

o f H e n r y ' s l a w .

SOURCE AND PURITY OF MATERIALS:

1 . F rom i r o n s u l f i d e ( e x M e r c k )

a n d d i l u t e H2SOi+; w a s h e d w i t h

H 2 0 a n d s o l v e n t m i x t u r e .

2 . D i s t i l l e d .

3. p.a. or puriss. from Merck or Kahlbaum-Schering; distilled

ESTIMATED ERROR: Quoted values are averages from several measurements with a maximum deviation from the mean of 0.2% (authors)

REFERENCES:


COMPONENTS:


2 . W a t e r ; H 2 0 ; [ 7 7 3 2 - 1 8 - 5 ]

3 . 1 , 2 , 3 - P r o p a n e t r i o l (glycerol); C 3 H 8 0 3 ; [ 5 6 - 8 1 - 5 ]

VARIABLES:

Temperature, concentration of glycerol


H2S was bubbled through about 100 cm3 of water & glycerol in an absorption vessel at barometric pressure for 1 to 1.5 h. Dissolved H2S was estimated iodimetrically. Allowance was made for the partial pressure of water and the head of liquid in the absorption vessel in the calculation of the partial pressure of H2S. Solubilities were corrected to a partial pressure of 1.013 bar by use of Henry's law.

ORIGINAL MEASUREMENTS: Kiss, A. v.; Lajtai, I.; Thury, G. Zeit. anorg. allgem. Chem, 1937, 233, 346-352.

PREPARED BY:

P . G . T . F o g g

SOURCE AND PURITY OF MATERIALS;

1 . F rom i r o n s u l f i d e ( e x M e r c k )

a n d d i l u t e H 2 S 0 4 ; w a s h e d w i t h

H 2 0 a n d s o l v e n t m i x t u r e .

2 . D i s t i l l e d . 3. p.a. or puriss. from Merck or Kahlbaum-Schering; distilled.

ESTIMATED ERROR: Quoted values are averages from several measurements with a maximum deviation from the mean of 0.2% (authors)

REFERENCES:


C o n e , o f C o n e , o f H 2 S i n l i q u i d / m o l dm" O s t w a l d c o e f f i c i e n t , L glycerol /mol dm"

0 2 4 6 8

^ o o = 1

273.20 K

0.2079 0.1752 0.1514 0.1311 0.1165

.013 bar

285.65 K

0.1410 0.1180 0.1066 0.0967 0.0913

298.15 K

0.1014 0.0930 0.0850 0.0793 0.0770

273.20 K

4.662 3.929 3.396 2.940 2.613

285.65 K

3.307 2.768 2.500 2.267 2.140

298.15 K

2.482 2.276 2.080 1 .938 1 .885

H 2 S



COMPONENTS: EVALUATOR: Peter G.T. Fogg,

1. Hydrogen sulfide; H2S? [7783-06-4] Department of Applied Chemistry and Life Sciences, Polytechnic of North London,

2. Strong electrolytes Holloway, London N7 8DB, U.K. July 1987


Several workers have reported the solubilities of hydrogen sulfide in solutions of salts and of acids and, as part of the same work, the solubility of the gas in pure water. If such measurements using pure water are in accord with values given by other workers then measurements of solubilities in the presence of electrolytes which have been carried out as part of the same research are likely to be reliable. The published solubilities indicate that addition of an acid to water usually increases the solubility of hydrogen sulfide whereas addition of a salt often has the opposite effect. Experimental values for low electrolyte concentrations sometimes approximately obey empirical equations based upon the Sechenov relation (1). i.e.

s = s'exp (- kc)

where s is the solubility of the gas in solution, s' the solubility in pure water, c the concentration of the electrolyte and k an empirical constant specific for the electrolyte. Concentrations may be expressed as molarities, molalities or mole fractions. When the equation is expressed in a form such as:

In (s/mol dm"3) = In (s'/mol dm"3) - kc the effects of different electrolytes are approximately additive i.e.

In (s/mol dm" ) = In (s'/mol dm" ) - (k\C\ + /M2C2 + )

where k\, k2 etc. are appropriate constants for electrolyte 1,2, etc. at concentrations ci, c2r etc. Better agreement with experimental data is obtained if additional terms depending on concentrations raised to a higher power, are introduced. Solubilities in hydrochloric acid solutions at 298.15 K and a partial pressure of 1.013 bar have been reported by Kendall & Andrews (2), Kapustinsky & Anvaer (3) and by Gamsjager & Schindler (4). Solubilities in pure water at the same temperature and pressure, which were reported by each group, are within 1% of the recommended value. Gamsjager & Schindler investigated the solubilities in the concentration range of hydrochloric acid of 0 to 3 mol dm"3. Values are within about 2% of solubilities reported by Kendall & Andrews who made measurements at acid concentrations to 4.9 mol dm-3. Kapustinsky & Anvaer measured solubilities in hydrochloric acid of concentrations from 5 to 11.4 mol dm"3. Extrapolation of these^measurements to lower concentrations of hydrochloric acid confirms that Gamsjager's experimental measurements are likely to be reliable. However the empirical equation for the ratio of solubility in acid to that in pure water as a function of acid concentration, reported by Gamsjager, does not appear to be applicable to the acid concentration range investigated by Kapustinsky. Measurements reported by Gamsjager & Schindler (4) for solutions containing sodium chloride are self-consistent. The solubility at 298.15 K for a partial pressure of 1.013 bar in sodium chloride of concentration 3.0 mol dm"3 is 0.062 mol dm" which is greater than the value of 0.0548 reported by Kapustinsky & Anvaer (3). The evaluator considers that data given by Gamsjager & Schindler are likely to be the more reliable and these should be accepted on a tentative basis. Kapustinsky and Anvaer (3) also reported the solubility at 298.15K and 1.013 bar in a solution of potassium chloride (1.0 mol dm"3) to be 0.0877 mol dm"3 which is close to the value of the value of 0.089 estimated from measurements by McLauchlin (5). In view of the uncertainty over the solubility in sodium chloride solution this value for potassium chloride solutions can only be accepted on a tentative basis. K

Documents

Hydrogen Sulfide, Deuterium Sulfide _ Hydrogen Selenide-Pergamon Press (1988)