Table Of ContentSolvent Mixtures
Solvent Mixtures
Properties and Selective Solvation
Yizhak Marcus
The Hebrew University of Jerusalem Jerusalem, Israel
CRC Press
Taylor & Francis Group
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Preface
Much ofchemistry is carried out in solution, and often mixed solvents
ratherthansinglesolventsareusedforthispurpose.Inthesolutions,the
solutes, whether nonelectrolyte molecules or ions, are solvated. The
extentandstrengthofthissolvationaffecttheirsolubility,reactivity,and
other properties. In mixed solvents, the mutual interactions ofthe sol
vents have to be taken into account in assessing the solvation of the
solutes. Itis therefore ofinterest to learn as much as possible about the
propertiesofthe solventmixtures,first intheabsenceofanysolutesand
thenintheirpresence.Contrarytosolvationinsinglesolvents,insolvent
mixturesthe phenomenonofpreferentialsolvationmaytakeplace.This
addstothedifficultyininterpretingexperimentalresults,but,ontheother
hand, isofinterestinitself. Preferential solvation mayoccurinabinary
solventmixtureintheabsenceofsolutes,inwhichmoleculesofasolvent
may interact preferentially with those ofits own kind or with those of
anotherkind.When solutemoleculesorions are present,these mayalso
bepreferentiallysolvatedbyacertaincomponentofthesolventmixture.
Therefore,the use ofmixedsolventsentailsknowingtheirproperties as
functions ofthe composition as well as an understanding of any pre
ferential solvationthattakesplace. Itis thepurpose ofthisbookto pro
videasolidbasisforthisknowledgeandunderstanding.
iii
iv Preface
Thisbookisthereforeafittingsequeltoapreviousbookofmine:The
PropertiesofSolvents(Wiley,1998),whichpresentedinannotatedtabular
form,thephysical,thermodynamic,andchemicalpropertiesofsome250
single solvents. Itisobviouslyimpossibleto presentpropertiesofallthe
combinations of chemically stable and mutually miscible mixtures of
thesemanysolvents.Adrasticselectionofsystemstobereportedhastobe
made,from the pointofviewofthe availabilityofdataandthe common
employment ofthe mixtures in practice. More than 40 years ago, Jean
Timmermansattemptedtoreport ThePhysico-chemicalConstantsofBin
arySystemsin ConcentratedSolutions(Interscience,1959-60),pertaining
(inVolumes 1and2) to a large numberofbinarysolventmixtures and a
sizable number ofproperties. Most ofthese data are still useful, but of
coursehavebeensupplemented-andin some casesreplaced-bymore
recentdata.Thepresentbookislessexhaustivewithrespecttothenum
berofsolventmixtures treated,butoffersinadditionto the dataa suffi
ciently deep discussion oftheir significance. William E. Acree, Jr., in
Thermodynamic Properties ofNonelectrolyte Solutions (Academic, 1984),
hasmorerecentlydealtwithsomeofthepointsdiscussedherebutreport
edonlyfewdataconcerningbinarysolventmixtures.Thepreviousgapin
knowledgeandunderstandingofthepropertiesofsolventmixturesandof
thesolutionsinthemshouldthereforebenarrowedbythepresentbook.
Therationaleformyundertakingthewritingofbooksinthefieldof
solutionchemistrywaspartlypresentedintheprefaceofThePropertiesof
Solvents, taken inpartfrom myearlierbookIon Solvation (Wiley, 1986).
Gaps in knowledge andunderstanding revealedbythe writingofbooks
could-albeit to only a minute extent-be filled by my own research.
However, in view ofthe intrinsic as well as practical importance ofthe
subject,the scientificcommunityisurgedtodomoreinthisrespect. For
thispurpose,indeed,thetablesofdatacontainblankrowswheredataare
missing,suggestingthattheseshouldbefilledin.Thecomparisonofdata,
presentedhereinauniformmannertofacilitatecomparison,shouldgoa
long way toward aiding comprehension ofthe behavior ofthe systems
alreadystudiedandextrapolationoftheinsightsandknowledgetomany
othersystems.
Thedatapresentedhereintheextensivetablesarefrom secondary
sources as far as available, since such data ought to have already been
critically evaluated and selected by the authors ofsuch sources. These
data have been supplemented by data from recent primary sources in
researchjournals.Accesstothesewasthroughabstracts,electronicjour
nals,andtheWebofScienceuptoandincluding2001.Iamresponsiblefor
Preface v
thechoicesmadeandwillbegratefulforreaders'reportsoferrors, over
sights,andfurtherusefuldataforthesystemsdiscussed.Therationalefor
theselectionofthesesystemsisgiveninChapter1.Ontheotherhand,the
discussion ofthe physical chemistry ofthe mixed solvent systems, the
structures,thermodynamics,andthephysicalandchemicalpropertiesof
these systems isindependentofthe dataactuallyavailable.This discus
sion points to the significance ofthe data as well as the reliability and
accuracywithwhichthesecanbe obtained.Thediscussion isillustrated
byresultsforcertainselectedsystems,butnaturallyisnotcomprehensive
inthisrespect.
IamgratefultoTheHebrewUniversityofJerusalemforitspolicyof
permitting its retired professors-of whom I am now one-to retain
facilities for the continuation oftheir scientific work. It also provides a
fairlygenerousallocationoffundsfordoingso,aslongastheretiredpro
fessors are able to do useful work. This book was conceived before my
retirementbutIhavewrittenitwhilebeinganemeritusprofessor,astatus
thatIkeeponenjoying.
YizhakMarcus
Contents
Preface iii
Solvent Abbreviations ix
Symbols xi
1. Introduction 1
1.1 SolventMixtures 1
1.2 TheConceptofPreferentialSolvation 6
1.3 TheCompositionofMixedSolvents 11
References 15
2. PropertiesofDinarySolventMixtures 16
2.1 RepresentativeSolventMixtures 16
2.2 PhysicalProperties 19
2.3 ThermodynamicProperties 45
2.4 ChemicalProperties 86
2.5 AssociatedMixtures 104
References 118
3. TheStructureofSolventMixtures 121
3.1 DiffractionMethods 122
3.2 ComputerSimulationMethods 128
3.3 SpectroscopicMethods 132
References 139
vii
