Kinetics of Metal Ion Adsorption from Aqueous Solutions: Models, Algorithms, and Applications

239 Pages·1995·13.355 MB·English

by  Sotira Yiacoumi, Chi Tien (auth.)

KINETICS OF
METAL ION ADSORPTION
FROM AQUEOUS SOLUTIONS
Models, Algorithms, and Applications
KINETICS OF
METAL ION ADSORPTION
FROM AQUEOUS SOLUTIONS
Models, Algorithms, and Applications
by
Sotira Yiacoumi
Georgia Institute of Technology
and
ehi Tien
Syracuse University
SPRINGER SClENCE+BUSINESS MEDIA, LLC
ISBN 978-0-7923-9600-0 ISBN 978-1-4615-2319-2 (eBook)
DOI 10.1007/978-1-4615-2319-2
Library of Congress Cataloging-in-Publication Data
A C.I.P. Catalogue record for this book is available
from the Library of Congress.
Copyright © 1995 by Springer Science+Business Media New York
Originally published by Kluwer Academic Publishers in 1995
Softcover reprint ofthe hardcover lst edition 1995
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, mechanical,
photo-copying, recording, or otherwise, without the prior written permission of
the publisher, Springer Science+Business Media, LLC.
Printed on acid-free paper.
To Julia C. Tien and Costas Tsouris
CONTENTS
PREFACE xvii
ACKNOWLEDGMENTS xix
CHAPTER 1 INTRODUCTION 1
1.1. AdsorptionofMetalIonsfrom Aqueous Solutions l
1.2. ScopeandObjectives .4
1.3. Organization 5
References 6
CHAPTER2 ADSORPTIONOFIONICSOLUTES AT
SOLID-SOLUTIONINTERFACES 9
Scope 9
Notations 9
2.1. ModelsforAdsorptionoflonicSolutesatSolid-SolutionInterfaces...11
2.1.1. Gouy-Chapman-Stem-Grahame(GCSG)ModeL ll
2.1.2. Ion-ExchangeModel. 13
2.1.3. Ion-SolventInteractionModeL 14
2.1.4. SurfaceComplexFormationModeL .17
viii ADSORPTIONOFMETALIONS FROMAQUEOUS SOLUTIONS
2.2. TheSurfaceChargeDensity/SurfacePotential
RelationshipinsidethePorousStructureofaParticle .18
2.2.1. BasicEquations 19
2.2.2. PoresasTwoPlanarPlates 20
2.2.3. LowPotentialsinPores 23
References 27
CHAPTER3 ADSORPTIONOFMETALIONS FROM
AQUEOUS SOLUTIONS: MODELDEVELOPMENT.. 29
Scope 29
Notations 30
3.1. DemonstrationoftheModelingApproach: ASimpleCase 33
3.2. SurfaceCharge .38
3.2.1. ChargebyAdsorptionofProtons: One-pKModel... .38
3.2.2. ChargebyAdsorptionand
DesorptionofProtons: Two-pKModel... .42
3.2.3. ComplexationofBackgroundElectrolytes .43
3.2.4. Representation andPredictionofSurfaceCharge .46
3.3. AdsorptionIsotherms 57
3.3.1. ComplexationReactionsofMetalIons 57
3.3.2. LocationofAdsorptionPlane 59
3.3.3. RepresentationandPredictionofAdsorptionIsotherms 64
3.4. AdsorptionRates 73
3.4.1. Reaction-ControlledCases 74
3.4.2. Transport-ControlledCases 78
References 83
Appendix 3.A. EffectofSiteSpecificityonMetalIon Adsorption 87
Appendix 3.B. RepresentativeElementaryReactionsandRates 89
CONTENTS IX
CHAPTER4 ADSORPTIONOFMETALIONS FROM
AQUEOUS SOLUTIONS: ALGORITHMDEVELOPMENT 95
Scope 95
Notations 96
4.1. Definitions 98
4.1.1. Components 99
4.1.2. Species 100
4.2. MathematicalDescription 103
4.2.1 Reaction-ControlledCases 104
4.2.2 Transport-ControlledCases 115
4.2.3 MethodofSolution 120
4.3. Description oftheProgram 132
4.4. CalculationsforaSimpleCase 137
4.4.1. Reaction-ControlledCase 138
4.4.2. Transport-ControlledCase 143
References 146
Appendix 4.A. ComputationofFixed-ActivitySpeciesinKINEQL.. 147
CHAPTER5 ADSORPTIONOFMETALIONS FROM
AQUEOUS SOLUTIONS: MODELAPPLICATION 151
Scope 151
Notations 152
5.1. Rapid Adsorption Rates 153
5.1.1. SurfaceChargeofTitaniumDioxide 160
5.1.2. AdsorptionofZinc(II)onAluminumOxide 164
5.1.3. AdsorptionofSelenate(II)andSelenite(II)onGoethite 168
5.2. SlowAdsorptionRates 173
5.2.1. AdsorptionofVanadyl(IV)onAluminumOxide 174
5.2.2. AdsorptionofChromium(ill)onAluminumOxide 176
x ADSORPTIONOFMETALIONS FROMAQUEOUS SOLUTIONS
5.3. Transport-ControlledCases 181
5.3.1 AdsorptionofCadmium(ll)onAluminumOxide 183
References 198
CHAPTER6 SUMMARYANDFUTUREDEVELOPMENT 203
6.1. Summary 203
6.2. FutureDevelopment. 206
References 208
COMPUTERPROGRAMS 209
PartI. KINEQLProgram: Description 209
PartII. Reaction-ControlledCase: SampleProgram 215
PartIII. Transport-ControlledCase: SampleProgram 216
INDEX 217
LIST OF FIGURES
Figure Page
2.1 Effectof 'If and K:d/2 on
0
thedimensionlesssurfacechargedensity ((J'~) of
an adsorbentwithporousstructure 23
3.1 Schematicoftheelectricaldoublelayer .40
3.2 Representationofthesurfacechargeof
activatedcarbon(Corapsioglu, 1984):
(a)one-pK,BS modeL 53
(b) two-pK,BS modeL 53
(c)one-pK,electrolytecomplexation,BS model... 54
(d)two-pK, electrolytecomplexation,BS model... 54
(e)two-pK, electrolytecomplexation,TLmodel... 55
3.3 Representationoftheadsorptionisothermsof
copperonactivatedcarbon(Corapsioglu, 1984):
(a)one-pKmodeL 67
(b) two-pKmodeL 67
3.4 Representationoftheadsorptionisothermsof
cadmiumonhydrousferric oxide(DzombakandMorel, 1986):
(a)one-pKmodeL 70
xii ADSORPTIONOFMETALIONS FROMAQUEOUS SOLUTIONS
(b)one-siteand two-sitemodels 70
3.5 Representationofthecompetitiveadsorption isothermsof
cadmiumandcopperonamorphousironhydroxide
(BenjaminandLeckie, 1981a;b) 73
3.6 Idealizedmodelforintraparticlediffusion 79
4.1 TheKINEQLprogramin macroscopicflowcharts:
(a) main program 134
(b) subroutineCHEMEQ 135
(c)subroutineSOLVE 136
4.2 Adsorption historiesforasimplereaction-controlledcase:
(a)effectofpH
(T =IO-5M, Ts=IO-3M, 1=10-2M) 141
M
(b)effectoftotal metal ionconcentration
(Ts=IO-3M, 1=10-2M, pH=5) 141
(c)effectofadsorbentconcentration
(/=10-2M, pH=5, T =IO-5M) 142
M
(d)effectofionicstrength
(pH=5, T =IO-5M, Ts=IO-3M) 142
M
4.3 Adsorption historiesforasimpletransport-controlledcase:
(a)effectofpH
(TM=IO-5M, Ts=IO-3M, 1=10-2M) l44
(b)effectoftotal metalionconcentration
(Ts=IO-3M, 1=10-2M,pH=5) I44
(c)effectofadsorbentconcentration
(/=10-2 M, pH=5, T =IO-5M) 145
M
(d)effectofionicstrength
(pH=5, TM=IO-5M, Ts=10-3M) 145
5.1 Representationofthekineticsof
surfacechargedevelopmentoftitaniumdioxide 165