Handbook of solvents

1694 Pages·2001·19.25 MB·English

by  George Wypych

HANDBOOK OF
SOLVENTS
George Wypych, Editor
ChemTecPublishing
Toronto - New York 2001
Published by ChemTec Publishing
38 Earswick Drive, Toronto, Ontario M1E 1C6, Canada
Co-published by William Andrew Inc.
13 Eaton Avenue, Norwich, NY 13815, USA
© Chem Tec Publishing, 2001
ISBN 1-895198-24-0
All rights reserved. No part of this publication may be reproduced, stored or
transmitted in any form or by any means without written permission of copyright
owner. No responsibility is assumed by the Author and the Publisher for any injury
or/and damage to persons or properties as a matter of products liability, negligence,
use, or operation of any methods, product ideas, or instructions published or
suggested in this book.
Canadian Cataloguing in Publication Data
Handbook of Solvents
Includes bibliographical references and index
ISBN 1-895198-24-0 (ChemTec Publishing)
ISBN 0-8155-1458-1 (William Andrew Inc.)
Library of Congress Catalog Card Number: 00-106798
1. Solvents--Handbooks, manuals, etc. I. Wypych, George
TP247.5.H35 2000 661’.807 C00-900997-3
Printed in Canada by Transcontinental Printing Inc., 505 Consumers Rd.
Toronto, Ontario M2J 4V8
Preface
Althoughthechemicalindustrycantraceitsrootsintoantiquity,itwasduringtheindustrial
revolutionthatitstartedtobecomeanactualindustryandbegantousetheincreasedknowl-
edge of chemistry as a science and technology to produce products that were needed by
companionindustriesandconsumers.Thesecommercialeffortsresultedinthesynthesisof
manynewchemicals.Quitequickly,intheseearlydays,previouslyunknownmaterialsor
materialsthathadbeenpresentonlyinlowconcentrations,werenowincontactwithpeople
inhighlyconcentratedformsandinlargequantities.Thepeoplehadlittleornoknowledge
of the effects of these materials on their bodies and the natural biological and physical
processesintheriversandoceans,theatmosphere,andintheground.
Until the end of the nineteenth century these problems were not addressed by the
chemicalindustryanditisonlyrecentlythattheindustrybegantorespondtopubliccriti-
cismandpoliticalefforts.Legalrestrictionsaimedatpreservingthequalityoflifehavebeen
directedathealth,safetyandlongevityissuesandtheenvironment.Solventshavealways
beenmainstaysofthechemicalindustryandbecauseoftheirwidespreaduseandtheirhigh
volume of production they have been specifically targeted by legislators throughout the
world.Therestrictionsrangefromtotalprohibitionofproductionanduse,tolimitsplaced
onvaporconcentrationsintheair.Aswithanyarbitrarymeasuressomesolventshavebeen
damnedunfairly.However,thereisnoquestionthatitisbesttoerronthesideofsafetyifthe
risksarenotfullyunderstood.Itisalsotruethatsolventsshouldbedifferentiatedbasedon
theirindividualproperties.
Thisbookisintendedtoprovideabetterunderstandingoftheprinciplesinvolvedin
solventselectionanduse.Itstrivestoprovideinformationthatwillhelptoidentifytherisks
andbenefitsassociatedwithspecificsolventsandclassesofsolvents.Thebookisintended
tohelptheformulatorselecttheidealsolvent,thesafetycoordinatortosafeguardhisorher
coworkers,thelegislatortoimposeappropriateandtechnicallycorrectrestrictionsandthe
student to appreciate the amazing variety of properties, applications and risks associated
withthemorethanonethousandsolventsthatareavailabletoday.
Bytheirverynature,handbooksareintendedtoprovideexhaustiveinformationonthe
subject.Whileweagreethatthisisthegoalhere,wehaveattemptedtotempertheimpactof
information,whichmaybetoonarrowtomakedecision.
Manyexcellentbooksonsolventshavebeenpublishedinthepastandmostofthese
arereferencedinthisbook.Butofallthesebooksnonehasgivenacomprehensiveoverview
ofallaspectsofsolventuse.Accesstocomprehensivedataisanessentialpartofsolvent
evaluationandithasbeenahallmarkofsuchbookstoprovidetablesfilledwithdatatothe
pointatwhich50to95%ofthebookisdata.Thisapproachseemstoneglectafundamental
requirementofahandbook-toprovidethebackground,explanationsandclarificationsthat
areneededtoconvertdatatoinformationandassistthereaderingainingtheknowledgeto
makeadecisiononselectingaprocessorasolvent.Unfortunately,tomeetthegoalofpro-
vidingboththedataandthefundamentalexplanationsthatareneeded,abookof4,000to
5,000pagesmightberequired.Evenifthiswaspossible,muchofthedatawouldfalloutof
datequitequickly.Forexample,afactorthatdefinessolventsafetysuchasthresholdlimit
xxviii Preface
values (TLVs) for worker exposure or some single toxicity determinants may change
frequently.Thisbookwouldbehugeanditwouldhavetobeupdatedfrequentlytocontinue
toclaimthatitiscurrent.
Whatwehaveattemptedtodohereistogiveyouabookwithacomprehensiveandex-
tensiveanalysisofallcurrentinformationonsolventsthenuseothermediatopresentthe
supporting data on individual solvents. These data are provided on a CD-ROM as a
searchabledatabase.Dataareprovidedonmorethan1140solventsin110fieldsofdata.
Themediumpermitsfrequentupdates.Ifthesamedatawerepresentedinbookform,more
than2,000pageswouldbeneededwhichexceedsthesizeofanydatainhandbookform
offeredtodate.
Thebestapproachinpresentinganauthoritativetextforsuchabookistohaveitwrit-
ten by experts in their fields. This book attracted well-known experts who have written
jointly47booksandauthoredorcoauthoredhundredsofpapersontheirareasofexpertise.
The authors have made their contributions to this book in late 1999 and early 2000
providingthemostcurrentpictureofthetechnology.Theirextremefamiliaritywiththeir
subjectsenablesthemtopresentinformationindepthanddetail,whichisessentialtothe
reader(cid:146)sfullunderstandingofthesubject.
Theauthorswereawareofthediversityofpotentialreadersattheoutsetandoneof
theirobjectiveswastoprovideinformationtovariousdisciplinesexpressedinawaythatall
wouldunderstandandwhichwoulddealwithallaspectsofsolventapplications.Weexpect
professionalsandstudentsfromawiderangeofbusinesses,alllevelsofgovernmentsand
academetobeinterestedreaders.Thelistincludessolventmanufacturers,formulatorsof
solventcontainingproducts,industrialengineers,analyticalchemists,governmentlegisla-
torsandtheirstaffs,medicalprofessionalsinvolvedinassessingtheimpactonhealthofsol-
vents, biologists who are evaluating the interactions of solvents with soil and water,
environmental engineers, industrial hygienists who are determining protective measures
againstsolventexposure,civilengineerswhodesignwastedisposalsitesandremediation
measures, people in industries where there are processes which use solvents and require
theirrecoveryand,perhapsmostimportant,becauseunderstandingbringsimprovements,
thosewhoteachandlearninouruniversities,collegesandschools.
Agrowingspiritofcooperationisevidentbetweenthesegroupsandthiscanbefos-
teredbyprovidingavenuesofunderstandingbasedonsharingdataandinformationoncom-
mon problems. We hope to provide one such avenue with this book. We have tried to
presentabalancedpictureofsolventperformancebydealingnotonlywithproductperfor-
manceandeaseofprocessingbutalsobygivingenvironmentalandhealthissuesfullcon-
sideration.
Dataandinformationonknownproductsandprocessesshouldbecornerstonesofthe
understandingofatechnologybutthereisanotheraspectoftechnology,whichcanleadto
advances and improvements in utility, safety and in safeguarding the environment. This
mustcomefromyou,thereader.Itisyourideasandcreativethinkingthatwillbringthese
improvements.Theauthorshavecrammedtheirideasintothebookandwehopethesewill
stimulateresponsibleandeffectiveapplicationsofsolvents.FrancisBaconwrote,(cid:147)Theend
ofourfoundationistheknowledgeofcauses,andthesecretmotionofthings,andtheen-
largingoftheboundofhumanEmpire,totheeffectingofallthingspossible.(cid:148)
Todaytherearefewtechnicalactivitiesthatdonotemploysolvents.Almostallindus-
tries,almostallconsumerproducts,almosteverythingweusecan,ifanalyzed,beshownto
Preface xxix
contain or to have used in its processing, a solvent. Solvent elimination need never be a
technicalobjective.Rather,weneedtouseourincreasingunderstandingandknowledgeto
findthesafestandthemosteffectivemeansofmeetingourgoals.
Iwouldliketothanktheauthorsfortheirrelentlesseffortstoexplainthedifficultinan
interestingway.Inadvance,Iwouldliketothankthereaderforchoosingthisbookanden-
courageherorhimtoapplytheknowledgetomakeourworldabetter,morelivableplace.
GeorgeWypych
Toronto,August3,2000
Table of Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxvii
GEORGEWYPYCH
1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
CHRISTIANREICHARDT
2 FUNDAMENTALPRINCIPLESGOVERNINGSOLVENTSUSE . . . . 7
2.1 Solventeffectsonchemicalsystems. . . . . . . . . . . . . . . . . . . . . . . 7
ESTANISLAOSILLA,ARTUROARNAU,I(cid:209)AKITU(cid:209)(cid:211)N
2.1.1 Historicaloutline. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1.2 Classificationofsolute-solventinteractions . . . . . . . . . . . . . . . . . . . 10
2.1.2.1 Electrostatic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.2.2 Polarization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.1.2.3 Dispersion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.1.2.4 Repulsion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.1.2.5 Specificinteractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.1.2.6 Hydrophobicinteractions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1.3 Modellingofsolventeffects . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.1.3.1 Computersimulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.1.3.2 Continuummodels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.1.3.3 Cavitysurfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.1.3.4 Supermoleculemodels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.1.3.5 Applicationexample:glycineinsolution . . . . . . . . . . . . . . . . . . . . 23
2.1.4 Thermodynamicandkineticcharacteristicsofchemicalreactionsinsolution . 27
2.1.4.1 Solventeffectsonchemicalequilibria . . . . . . . . . . . . . . . . . . . . . . 27
2.1.4.2 Solventeffectsontherateofchemicalreactions. . . . . . . . . . . . . . . . . 28
2.1.4.3 Exampleofapplication:additionofazideaniontotetrafuranosides. . . . . . . 30
2.1.5 Solventcatalyticeffects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.2 Moleculardesignofsolvents. . . . . . . . . . . . . . . . . . . . . . . . . . . 36
KOICHIRONAKANISHI
2.2.1 Moleculardesignandmolecularensembledesign. . . . . . . . . . . . . . . . 36
2.2.2 Frompredictiontodesign . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.2.3 Improvementinpredictionmethod. . . . . . . . . . . . . . . . . . . . . . . . 38
2.2.4 Roleofmolecularsimulation. . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.2.5 Modelsystemandparadigmfordesign . . . . . . . . . . . . . . . . . . . . . 40
Appendix.Predictiveequationforthediffusioncoefficientindilutesolution . 41
2.3 Basicphysicalandchemicalpropertiesofsolvents . . . . . . . . . . . . . . . 42
GEORGEWYPYCH
2.3.1 Molecularweightandmolarvolume. . . . . . . . . . . . . . . . . . . . . . . 43
2.3.2 Boilingandfreezingpoints. . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.3.3 Specificgravity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.3.4 Refractiveindex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2.3.5 Vapordensityandpressure. . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.3.6 Solventvolatility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.3.7 Flashpoint . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.3.8 Flammabilitylimits. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.3.9 Sourcesofignitionandautoignitiontemperature . . . . . . . . . . . . . . . . 52
2.3.10 Heatofcombustion(calorificvalue). . . . . . . . . . . . . . . . . . . . . . . 54
2.3.11 Heatoffusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
2.3.12 Electricconductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
2.3.13 Dielectricconstant(relativepermittivity) . . . . . . . . . . . . . . . . . . . . 54
2.3.14 Occupationalexposureindicators . . . . . . . . . . . . . . . . . . . . . . . . 56
2.3.15 Odorthreshold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
ii HandbookofSolvents
2.3.16 Toxicityindicators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.3.17 Ozone-depletionandcreationpotential . . . . . . . . . . . . . . . . . . . . . 58
2.3.18 Oxygendemand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.3.19 Solubility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.3.20 Othertypicalsolventpropertiesandindicators . . . . . . . . . . . . . . . . . 60
3 PRODUCTIONMETHODS,PROPERTIES,
ANDMAINAPPLICATIONS. . . . . . . . . . . . . . . . . . . . . . . . . 65
3.1 Definitionsandsolventclassification . . . . . . . . . . . . . . . . . . . . . . 65
GEORGEWYPYCH
3.2 Overviewofmethodsofsolventmanufacture . . . . . . . . . . . . . . . . . . 69
GEORGEWYPYCH
3.3 Solventproperties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
GEORGEWYPYCH
3.3.1 Hydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.3.1.1 Aliphatichydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.3.1.2 Aromatichydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.3.2 Halogenatedhydrocarbons. . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.3.3 Nitrogen-containingcompounds(nitrates,nitriles) . . . . . . . . . . . . . . . 79
3.3.4 Organicsulfurcompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
3.3.5 Monohydricalcohols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.3.6 Polyhydricalcohols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.3.7 Phenols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.3.8 Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.3.9 Ethers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.3.10 Glycolethers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.3.11 Ketones. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.3.11 Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.3.12 Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.3.13 Esters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.3.14 Comparativeanalysisofallsolvents. . . . . . . . . . . . . . . . . . . . . . . 94
3.4 Terpenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
TILMANHAHN,KONRADBOTZENHART,FRITZSCHWEINSBERG
3.4.1 Definitionsandnomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.4.2 Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.4.3 General. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.4.4 Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
3.4.5 Thresholdlimitvalues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4 GENERALPRINCIPLESGOVERNINGDISSOLUTION
OFMATERIALSINSOLVENTS. . . . . . . . . . . . . . . . . . . . . . . 101
4.1 Simplesolventcharacteristics . . . . . . . . . . . . . . . . . . . . . . . . . . 101
VALERYYU.SENICHEV,VASILIYV.TERESHATOV
4.1.1 Solventpower . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4.1.2 One-dimensionalsolubilityparameterapproach. . . . . . . . . . . . . . . . . 103
4.1.3 Multi-dimensionalapproaches. . . . . . . . . . . . . . . . . . . . . . . . . . 110
4.1.4 Hansen(cid:146)ssolubility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4.1.5 Three-dimensionaldualisticmodel. . . . . . . . . . . . . . . . . . . . . . . . 116
4.1.6 Solubilitycriterion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
4.1.7 Solventsystemdesign . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
4.2 Effectofsystemvariablesonsolubility . . . . . . . . . . . . . . . . . . . . . 124
VALERYYU.SENICHEV,VASILIYV.TERESHATOV
4.2.1 Generalconsiderations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4.2.2 Chemicalstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
4.2.3 Flexibilityofapolymerchain . . . . . . . . . . . . . . . . . . . . . . . . . . 127
4.2.4 Crosslinking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.2.5 Temperatureandpressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
4.2.6 Methodsofcalculationofsolubilitybasedonthermodynamicprinciples. . . . 130
Tableofcontents iii
4.3 Polarsolvationdynamics:Theoryandsimulations . . . . . . . . . . . . . . . 132
ABRAHAM NITZAN
4.3.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
4.3.2 Continuumdielectrictheoryofsolvationdynamics . . . . . . . . . . . . . . . 133
4.3.3 Linearresponsetheoryofsolvationdynamics. . . . . . . . . . . . . . . . . . 136
4.3.4 Numericalsimulationsofsolvationinsimplepolarsolvents:
Thesimulationmodel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
4.3.5 Numericalsimulationsofsolvationinsimplepolarsolvents:
Resultsanddiscussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
4.3.6 Solvationincomplexsolvents . . . . . . . . . . . . . . . . . . . . . . . . . . 144
4.3.7 Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
4.4 Methodsforthemeasurementofsolventactivityofpolymersolutions. . . . . 146
CHRISTIANWOHLFARTH
4.4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
4.4.2 Necessarythermodynamicequations. . . . . . . . . . . . . . . . . . . . . . . 149
4.4.3 Experimentalmethods,equipmentanddatareduction. . . . . . . . . . . . . . 154
4.4.3.1 Vapor-liquidequilibrium(VLE)measurements . . . . . . . . . . . . . . . . . 154
4.4.3.1.1 ExperimentalequipmentandproceduresforVLE-measurements. . . . . . . . 155
4.4.3.1.2 Primarydatareduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
4.4.3.1.3 ComparisonofexperimentalVLE-methods . . . . . . . . . . . . . . . . . . . 175
4.4.3.2 Othermeasurementmethods. . . . . . . . . . . . . . . . . . . . . . . . . . . 178
4.4.3.2.1 Membraneosmometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
4.4.3.2.2 Lightscattering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
4.4.3.2.3 X-rayscattering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
4.4.3.2.4 Neutronscattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
4.4.3.2.5 Ultracentrifuge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
4.4.3.2.6 Cryoscopy(freezingpointdepressionofthesolvent) . . . . . . . . . . . . . . 188
4.4.3.2.7 Liquid-liquidequilibrium(LLE). . . . . . . . . . . . . . . . . . . . . . . . . 189
4.4.3.2.8 Swellingequilibrium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
4.4.4 Thermodynamicmodelsforthecalculationofsolventactivitiesof
polymersolutions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
4.4.4.1 Modelsforresidualchemicalpotentialandactivitycoefficientin
theliquidphase. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
4.4.4.2 Fugacitycoefficientsfromequationsofstate . . . . . . . . . . . . . . . . . . 207
4.4.4.3 Comparisonandconclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . 214
Appendix4.4A. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
5 SOLUBILITYOFSELECTEDSYSTEMSANDINFLUENCE
OFSOLUTES. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
5.1 Experimentalmethodsofevaluationandcalculationofsolubility
parametersofpolymersandsolvents.Solubilityparametersdata . . . . . . . . 243
VALERYYU.SENICHEV,VASILIYV.TERESHATOV
5.1.1 Experimentalevaluationofsolubilityparametersofliquids. . . . . . . . . . . 243
5.1.1.1 Directmethodsofevaluationoftheevaporationenthalpy . . . . . . . . . . . 243
5.1.1.2 Indirectmethodsofevaluationofevaporationenthalpy. . . . . . . . . . . . . 244
5.1.1.3 Staticandquasi-staticmethodsofevaluationofpairpressure. . . . . . . . . . 245
5.1.1.4 Kineticmethods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
5.1.2 Methodsofexperimentalevaluationandcalculationofsolubility
parametersofpolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
5.2 Predictionofsolubilityparameter . . . . . . . . . . . . . . . . . . . . . . . . 253
NOBUYUKITANAKA
5.2.1 Solubilityparameterofpolymers . . . . . . . . . . . . . . . . . . . . . . . . 253
5.2.2 Glasstransitioninpolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
5.2.2.1 Glasstransitionenthalpy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
5.2.2.2 C jumpattheglasstransition . . . . . . . . . . . . . . . . . . . . . . . . . . 256
p
5.2.3 Predictionfromthermaltransitionenthalpies . . . . . . . . . . . . . . . . . . 258
5.3 Methodsofcalculationofsolubilityparametersofsolventsandpolymers . . . 261
VALERYYU.SENICHEV,VASILIYV.TERESHATOV
iv HandbookofSolvents
5.4 Mixedsolvents,awaytochangethepolymersolubility. . . . . . . . . . . . . 267
LIGIAGARGALLOANDDEODATORADIC
5.4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
5.4.2 Solubility-cosolvencyphenomenon . . . . . . . . . . . . . . . . . . . . . . . 268
5.4.3 Newcosolventseffects.Solubilitybehavior. . . . . . . . . . . . . . . . . . . 273
5.4.4 Thermodynamicaldescriptionofternarysystems.Associationequilibria
theoryofpreferentialadsorption. . . . . . . . . . . . . . . . . . . . . . . . . 274
5.4.5 Polymerstructureofthepolymerdependenceofpreferentialadsorption.
Polymermolecularweightandtacticitydependenceofpreferentialadsorption. 277
5.5 Thephenomenologicaltheoryofsolventeffectsinmixedsolventsystems. . . 281
KENNETHA.CONNORS
5.5.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
5.5.2 Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
5.5.2.1 Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
5.5.2.2 Theintersoluteeffect:solute-soluteinteractions. . . . . . . . . . . . . . . . . 282
5.5.2.3 Thesolvationeffect:solute-solventinteraction . . . . . . . . . . . . . . . . . 283
5.5.2.4 Thegeneralmediumeffect:solvent-solventinteractions . . . . . . . . . . . . 284
5.5.2.5 Thetotalsolventeffect. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
5.5.3 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
5.5.3.1 Solubility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
5.5.3.2 Surfacetension. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
5.5.3.3 Electronicabsorptionspectra. . . . . . . . . . . . . . . . . . . . . . . . . . . 290
5.5.3.4 Complexformation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
5.5.3.5 Chemicalkinetics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
5.5.3.6 Liquidchromatography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
5.5.4 Interpretations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
5.5.4.1 Ambiguitiesandanomalies. . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
5.5.4.2 Amodifiedderivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
5.5.4.3 Interpretationofparameterestimates. . . . . . . . . . . . . . . . . . . . . . . 300
5.5.4.4 Confoundingeffects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Solute-soluteinteractions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Couplingofgeneralmediumandsolvationeffects . . . . . . . . . . . . . . . 301
Thecavitysurfacearea. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Theroleofinterfacialtension . . . . . . . . . . . . . . . . . . . . . . . . . . 302
6 SWELLING. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
6.1 Modernviewsonkineticsofswellingofcrosslinkedelastomersinsolvents . . 305
E.YA.DENISYUK,V.V.TERESHATOV
6.1.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
6.1.2 Formulationofswellingforaplaneelastomerlayer. . . . . . . . . . . . . . . 306
6.1.3 Diffusionkineticsofplanelayerswelling . . . . . . . . . . . . . . . . . . . . 310
6.1.4 Experimentalstudyofelastomerswellingkinetics . . . . . . . . . . . . . . . 314
6.1.5 Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
6.2 Equilibriumswellinginbinarysolvents . . . . . . . . . . . . . . . . . . . . . 318
VASILIYV.TERESHATOV,VALERYYU.SENICHEV
6.3 Swellingdataoncrosslinkedpolymersinsolvents . . . . . . . . . . . . . . . 327
VASILIYV.TERESHATOV,VALERYYU.SENICHEV
6.4 Influenceofstructureonequilibriumswelling. . . . . . . . . . . . . . . . . . 331
VASILIYV.TERESHATOV,VALERYYU.SENICHEV
7 SOLVENTTRANSPORTPHENOMENA . . . . . . . . . . . . . . . . . . 339
7.1 Introductiontodiffusion,swelling,anddrying . . . . . . . . . . . . . . . . . 339
GEORGEWYPYCH
7.1.1 Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
7.1.2 Swelling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344
7.1.3 Drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348
7.2 Bubblesdynamicsandboilingofpolymericsolutions. . . . . . . . . . . . . . 356
SEMYONLEVITSKY,ZINOVIYSHULMAN
7.2.1 Rheologyofpolymericsolutionsandbubbledynamics . . . . . . . . . . . . . 356
Tableofcontents v
7.2.1.1 Rheologicalcharacterizationofsolutionsofpolymers. . . . . . . . . . . . . . 356
7.2.1.2 Dynamicinteractionofbubbleswithpolymericliquid . . . . . . . . . . . . . 363
7.2.2 Thermalgrowthofbubblesinsuperheatedsolutionsofpolymers . . . . . . . 372
7.2.3 Boilingofmacromolecularliquids. . . . . . . . . . . . . . . . . . . . . . . . 377
7.3 Dryingofcoatedfilm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
SEUNGSUKIMAND JAECHUNHYUN
7.3.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
7.3.2 Theoryforthedrying. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
7.3.2.1 Simultaneousheatandmasstransfer. . . . . . . . . . . . . . . . . . . . . . . 388
7.3.2.2 Liquid-vaporequilibrium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
7.3.2.3 Heatandmasstransfercoefficient . . . . . . . . . . . . . . . . . . . . . . . . 390
7.3.2.4 Predictionofdryingrateofcoating . . . . . . . . . . . . . . . . . . . . . . . 392
7.3.2.5 Dryingregimes:constantdryingrateperiod(CDRP)andfalling
dryingrateperiod(FDRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
7.3.3 Measurementofthedryingrateofcoatedfilm. . . . . . . . . . . . . . . . . . 396
7.3.3.1 Thermo-gravimetricanalysis. . . . . . . . . . . . . . . . . . . . . . . . . . . 396
7.3.3.2 RapidscanningFT-IRspectrometeranalysis . . . . . . . . . . . . . . . . . . 399
7.3.3.3 High-airflowdryingexperimentusingflameionizationdetector(FID)
totalhydrocarbonanalyzer. . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
7.3.3.4 Measurementofdryingrateintheproductionscaledryer. . . . . . . . . . . . 404
7.3.4 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
7.3.4.1 Dryingofcoatedfilmwithphaseseparation. . . . . . . . . . . . . . . . . . . 407
7.3.4.2 Dryingdefects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
7.3.4.2.1 Internalstressinduceddefects . . . . . . . . . . . . . . . . . . . . . . . . . . 409
7.3.4.2.2 Surfacetensiondrivendefects . . . . . . . . . . . . . . . . . . . . . . . . . . 412
7.3.4.2.3 Defectscausedbyairmotionandothers. . . . . . . . . . . . . . . . . . . . . 414
7.3.4.3 Controloflowerexplosivelevel(LEL)inamultiplezonedryer . . . . . . . . 414
8 INTERACTIONSINSOLVENTSANDSOLUTIONS . . . . . . . . . . . 419
JACOPOTOMASI,BENEDETTAMENNUCCI,CHIARACAPPELLI
8.1 Solventsandsolutionsasassembliesofinteractingmolecules . . . . . . . . . 419
8.2 Basicsimplificationsofthequantummodel. . . . . . . . . . . . . . . . . . . 420
8.3 Clusterexpansion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
8.4 Two-bodyinteractionenergy:thedimer. . . . . . . . . . . . . . . . . . . . . 424
8.4.1 Decompositionoftheinteractionenergyofadimer:variationalapproach . . . 426
Theelectrostaticterm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
Theinductionterm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428
Theexchangeterm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428
Thechargetransferterm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
Thedispersionterm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
Thedecompositionoftheinteractionenergythroughavariational
approach:asummary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
8.4.2 Basissetsuperpositionerrorandcounterpoisecorrections . . . . . . . . . . . 433
8.4.3 Perturbationtheoryapproach. . . . . . . . . . . . . . . . . . . . . . . . . . . 436
8.4.4 ModelingoftheseparatecomponentsofD E. . . . . . . . . . . . . . . . . . . 441
Theelectrostaticterm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 441
Theinductionterm. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 445
Thedispersionterm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 446
Theexchange(orrepulsion)term . . . . . . . . . . . . . . . . . . . . . . . . 447
Theotherterms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
Aconclusiveview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 448
8.4.5 Therelaxationoftherigidmonomerconstraint . . . . . . . . . . . . . . . . . 449
8.5 Three-andmany-bodyinteractions . . . . . . . . . . . . . . . . . . . . . . . 451
Screeningmany-bodyeffects. . . . . . . . . . . . . . . . . . . . . . . . . . . 453
Effectiveinteractionpotentials. . . . . . . . . . . . . . . . . . . . . . . . . . 454
8.6 Thevarietyofinteractionpotentials . . . . . . . . . . . . . . . . . . . . . . . 456
8.7 Theoreticalandcomputingmodelingofpureliquidsandsolutions. . . . . . . 461
8.7.1 Physicalmodels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461