Electrochemistry in Nonaqueous Solutions

352 Pages·2002·3.246 MB·English

by  Kosuke Izutsu

ElectrochemistryinNonaqueousSolutions.KosukeIzutsu
Copyright©2002Wiley-VCHVerlagGmbH&Co.KGaA
ISBNs:3-527-30516-5(Hardback);3-527-60065-5(Electronic)
KosukeIzutsu
Electrochemistry in
Nonaqueous Solutions
ElectrochemistryinNonaqueousSolutions.KosukeIzutsu
Copyright©2002Wiley-VCHVerlagGmbH&Co.KGaA
ISBNs:3-527-30516-5(Hardback);3-527-60065-5(Electronic)
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ElectrochemistryinNonaqueousSolutions.KosukeIzutsu
Copyright©2002Wiley-VCHVerlagGmbH&Co.KGaA
ISBNs:3-527-30516-5(Hardback);3-527-60065-5(Electronic)
K. Izutsu
Electrochemistry in Nonaqueous Solutions
ElectrochemistryinNonaqueousSolutions.KosukeIzutsu
Copyright©2002Wiley-VCHVerlagGmbH&Co.KGaA
ISBNs:3-527-30516-5(Hardback);3-527-60065-5(Electronic)
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Preface
A majority of chemical reactions are carried out in solution. The use of a solvent
as reaction medium makes it easy to control reaction conditions such as tempera-
ture, pressure, pH, rate of mass transfer, and concentration of reactant. Water is
the most popular solvent. However, by using appropriate non-aqueous solvents,
substances that are insoluble in water can be dissolved, substances that are un-
stable in water remain stable, and chemical reactions that are impossible in water
become possible. The reaction environments are markedly wider in non-aqueous
solventsthan in water.
The widespread use of non-aqueous solvents, especially dipolar aprotic solvents,
began in the 1950s in various fields of pure and applied chemistry and has con-
tributed greatly to later advances in chemical sciences and technologies. From the
very beginning, electrochemistry in non-aqueous solutions has played an impor-
tant role in exploring new chemical possibilities as well as in providing the meth-
ods to evaluate static solvent effects on various chemical processes. Moreover,
many new electrochemical technologies have been developed using non-aqueous
solvents. Recently, electrochemistry in non-aqueous solutions has made enormous
progress: the dynamic solvent effects on electrochemical processes have been
greatly elucidated and solvent effects are now understood much better than be-
fore. On the other hand, however, it is also true that some useful solvents have
properties that are problematic to human health and the environment. Today, ef-
forts are being made, under the framework of ‘green chemistry’, to find environ-
mentally benign media for chemical processes, including harmless non-aqueous
solvents, immobilized solvents, ionic liquids, supercritical fluids, aqueous sys-
tems, and even solventless reaction systems. For electrochemical purposes, replac-
ing hazardous solvents by harmless solvents, ionic liquids and supercritical fluids
appears to bepromising.
This book was written to provide readers with some knowledge of electrochem-
istry in non-aqueous solutions, from its fundamentals to the latest developments,
including the current situation concerning hazardous solvents. The book is di-
videdintotwoparts. PartI (Chapters 1to4) containsadiscussionofsolventprop-
erties and then deals with solvent effects on chemical processessuch as ion solva-
tion, ion complexation, electrolyte dissociation, acid-base reactions and redox reac-
tions.Such solventeffectsareoffundamental importanceinunderstanding chem-
VI Preface
istry in non-aqueous solutions; furthermore, their quantitative evaluations are of-
ten carried out by means of electrochemical techniques. Part II (Chapters 5 to 12)
mainly deals with the use of electrochemical techniques in non-aqueous solu-
tions. In Chapter 5, the fundamentals of various electrochemical techniques are
outlined in preparation for the following chapters. In Chapters 6 to 9, the applica-
tions of potentiometry, conductimetry, polarography, voltammetry, and other new
electrochemical techniques in non-aqueous solutions are discussedby focusing on
the chemical information they provide. Chapters 10 and 11 examine methods of
selecting and purifying the solvents and electrolytes of electrochemical impor-
tance. Finally, in Chapter 12, some practical applications of non-aqueous solvents
in modern electrochemical technologies are discussed. These include their use in
batteries, capacitors and display devices, and such processes as electrolytic refin-
ing, plating, synthesis and polymerization. The applicability of ionic liquids and
supercritical fluids as environmentally benign media for electrochemical technol-
ogy isalsodealt with.
Most chemists are familiar with chemistry in aqueous solutions. However, the
common sense in aqueous solutions is not always valid in non-aqueous solutions.
This is also true for electrochemical measurements. Thus, in this book, special
emphasis is placed on showing which aspects of chemistry in non-aqueous solu-
tions are different from chemistry in aqueous solutions. Emphasis is also placed
on showing the differences between electrochemical measurements in non-aque-
oussystems and those in aqueous systems. The importance of electrochemistry in
non-aqueous solutions is now widely recognized by non-electrochemical scientists
– for example, organic and inorganic chemists often use cyclic voltammetry in
aprotic solvents in order to determine redox properties, electronic states, and reac-
tivities of electroactive species, including unstable intermediates. This book will
thereforealsobeofuse to such non-electrochemicalscientists.
I obtained most of the information included in this book from the publications
of many scientists in this field. I would like to express my sincere thanks to all of
them. I also would like to thank my coworkers for their cooperation, the editorial
and production staff of Wiley-VCH for their help and support, and my wife for
her assistanceand patience.
Matsumoto, December2001 Kosuke Izutso
Books, reviews and data compilations relating to non-aqueous solution chemistry
and/ornon-aqueoussolvents:
1 Lagowski,J.J.(Ed.)TheChemistryof 3 Bard,A.J.(Ed.)ElectroanalyticalChemis-
Non-AqueousSolvents,AcademicPress, try,MarcelDekker,NewYork,Vol.3,
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3,1970;Vol.4,1976;Vol.5A,1978;Vol. 4 Coetzee,J.F.,Ritchie,C.D.(Eds)So-
5B,1978.Includesmanyreviews. lute-SolventInteractions,MarcelDekker,
2 Charlot,G.,Trémillon,B.Chemical NewYork,Vol.I,1969;Vol.II,1976.In-
ReactionsinSolventsandMelts,Pergamon cludesreviews.
Press,Oxford,1969.
Preface VII
5 Mann,C.K.,Barnes,K.K.Electrochemi- 18 Burger,K.Solvation,IonicandComplex
calReactionsinNonaqueousSolvents,Mar- FormationReactionsinNonaqueousSol-
celDekker,NewYork,1970. vents,Elsevier,Amsterdam,1983.
6 Janz,G.J.,Tomkins,R.P.T.(Eds)Non- 19 Marcus,Y.IonSolvation,Wiley&Sons,
aqueousElectrolytesHandbook,Academic NewYork,1985.Includeslargeamounts
Press,NewYork,Vol.1,1972;Vol.2, ofdata.
1973. 20 Riddick,A.,Bunger,W.R.,Sakano,
7 Covington,A.K.,Dickinson,T.(Eds) T.K.OrganicSolvents,PhysicalProperties
PhysicalChemistryinOrganicSolventSys- andMethodsofPurification,4thedn,Wi-
tems,PlenumPress,NewYork,1973.In- ley&Sons,NewYork,1986.Includesde-
cludesreviewsanddatacompilations. taileddataonsolventpropertiesand
8 Fritz,J.S.Acid-BaseTitrationsinNon- methodsofsolventpurification.
aqueousMedia,Allyn&Bacon,Needham 21 Safarik,L.,Stransky,Z.Titrimetric
Heights,MA,1973. AnalysisinOrganicSolvents,Comprehen-
9 Trémillon,B.ChemistryinNonaqueous siveAnalyticalChemistry,Vol.22,Else-
Solvents,D.Reidel,Dordrecht,the vier,Amsterdam,1986.
Netherlands,1974. 22 Reichardt,C.SolventsandSolventEffects
10 Sawyer,D.T.,Roberts,J.L.,JrExperi- inOrganicChemistry,2ndedn,VCH,
mentalElectrochemistryforChemists,Wiley Weinheim,1988.
&Sons,NewYork,1974;Sawyer,D.T., 23 Izutsu,K.Acid-BaseDissociation
Sobkowiak,A.,Roberts,J.L.,JrElectro- ConstantsinDipolarAproticSolvents,IU-
chemistryforChemists,2ndedn,Wiley& PACChemicalDataSeriesNo.35,Black-
Sons,NewYork,1995.Usefulreferences wellScience,Oxford,1990.Datacompila-
onelectrochemicaltechniquesinnon- tion.
aqueoussolutions. 24 Krestov,G.A.ThermodynamicsofSolva-
11 Meites,L.,Zuman,P.(Eds)CRCHand- tion,SolutionandDissolution,Ionsand
bookSeriesinOrganicElectrochemistry, Solvents,StructureandEnergetics,Ellis
CRCPress,BocaRaton,FL,VolsI–VI, Horwood,NewYork,1991.
1977–83;CRCHandbookSeriesinInor- 25 Lund,H.,Baizer,M.M.(Eds)Organic
ganicElectrochemistry,CRCPress,Boca Electrochemistry,3rdedn,MarcelDekker,
Raton,FL,VolsI–VIII,1981–1988.Com- NewYork,1991.Detailedtreatmentsof
pilationsofpotentialdata. electrochemicaltechniquesandelectrode
12 Burgess,J.MetalIonsinSolutions,Ellis processesoforganicsubstances.
Horwood,Chichester,1978. 26 Mamantov,G.,Popov,A.I.(Eds)Chemis-
13 Gutmann,V.Donor-AcceptorApproachto tryofNonaqueousSolutions,CurrentPro-
MolecularInteractions,PlenumPress, gress,VCH,Weinheim,1994.
NewYork,1978. 27 Galus,Z.,inAdvancesinElectrochemical
14 Kolthoff,I.M.,Elving,P.J.(Eds)Trea- ScienceandEngineering,Vol.2(EdsH.
tiseonAnalyticalChemistry,2ndedn,Part Gerischer,C.W.Tobias),VCH,Wein-
I,Vol.2,Wiley&Sons,NewYork,1979, heim,1994,pp.217–295.Thermody-
Chapter19.Excellentreviewsonacid-base namicsandkineticsofelectrodereac-
reactionsinnon-aqueoussystems. tionsinnon-aqueousandmixedsol-
15 Popovych,O.,Tomkins,R.P.T.Nonaque- vents.
ousSolutionChemistry,Wiley&Sons, 28 Gutmann,V.,Resch,G.LectureNoteson
NewYork,1981.Treatselectrochemical SolutionChemistry,WorldScience,Singa-
aspectsindetail. pore,1995.
16 Coetzee,J.F.(Ed.)RecommendedMethods 29 Kissinger,P.T.,Heineman,W.R.(Eds)
forPurificationofSolventsandTestsforIm- LaboratoryTechniquesinElectroanalytical
purities,PergamonPress,Oxford,1982. Chemistry,MarcelDekker,NewYork,
ReportsfromIUPAC. 1996.Includesmanychaptersonelectro-
17 Marcus,Y.IntroductiontoLiquidState chemicaltechniquesinnon-aqueousso-
Chemistry,Wiley&Sons,NewYork, lutions.
1977.
VIII Preface
30 Marcus,Y.IonProperties,MarcelDekker, 35 Aurbach,D.(Ed.)NonaqueousElectro-
NewYork,1997. chemistry,MarcelDekker,NewYork,
31 Trémillon,B.ReactionsinSolution:An 1999.Mainlyconcernedwithlithiumbat-
AppliedAnalyticalApproach,Wiley& teries.
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ChemistryVol.5,Springer,Berlin,1998. ChemTecPublishing,Toronto,2001.
33 Marcus,Y.ThePropertiesofSolvents,Wi- 38 Lund,H.,Hammerich,O.(Eds)Organic
ley&Sons,NewYork,1998. Electrochemistry,4thedn,MarcelDekker,
34 Chipperfield,J.R.Non-AqueousSolvents, NewYork,2001.
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1 Rossiter,B.W.,Hamilton,J.F.(Eds) plications,MarcelDekker,NewYork,
ElectrochemicalMethods,PhysicalMethods 1995.
ofChemistry,Vol.II,2ndedn,Wiley& 8 Fisher,A.C.ElectrodeDynamics,Oxford
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6 Bruce,P.G.(Ed.)SolidStateElectrochem- calMethods,FundamentalsandApplica-
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chemistry,Principles,Methods,andAp-
ElectrochemistryinNonaqueousSolutions.KosukeIzutsu IX
Copyright©2002Wiley-VCHVerlagGmbH&Co.KGaA
ISBNs:3-527-30516-5(Hardback);3-527-60065-5(Electronic)
Contents
Preface V
PartI FundamentalsofChemistry inNon-AqueousSolutions:
Electrochemical Aspects
1 PropertiesofSolventsandSolventClassification 3
1.1 Propertiesof Solvents 4
1.1.1 Physical Propertiesof Solvents 4
1.1.2 Chemical Propertiesof Solvents 13
1.1.3 Structural Aspects of Solvents 16
1.1.4 Toxicity and HazardousPropertiesofSolvents 18
1.2 Classification ofSolvents 19
1.3 EffectsofSolvent Propertieson Chemical Reactions(an Outline) 21
1.4 References 23
2 Solvation andComplex Formation ofIonsandBehaviorofElectrolytes 25
2.1 Influence ofIon Solvation onElectrolyte Dissolution 25
2.2 Some Fundamental Aspects of Ion-Solvation 27
2.2.1 Ion-SolventInteractionsAffecting Ion Solvation 27
2.2.2 Structure ofSolvated Ions 34
2.2.3 Ultrafast Ion-SolvationDynamics 37
2.3 ComparisonofIonic Solvation Energiesin DifferentSolvents
and Solvent Effectson IonicReactionsand Equilibria 38
2.3.1 GibbsEnergies ofTransferand TransferActivity Coefficients
ofIons 38
2.3.2 Predictionof Solvent Effectsby the UseofTransfer
Activity Coefficients 42
2.4 Solvent Effectsonthe Complexation ofMetal Ions 44
2.5 SelectiveSolvationof Ionsin MixedSolvents 47
2.6 Ion Associationand SolventPermittivities 50
2.7 References 56
X Contents
3 Acid-BaseReactionsinNon-AqueousSolvents 59
3.1 Solvent EffectsonAcid-BaseReactions 59
3.1.1 Acid-BaseReactionsin Amphiprotic Solvents
ofHigh Permittivit 61
3.1.2 Acid-BaseReactionsin AproticSolventsofHigh Permittivity 64
3.1.3 Acid-BaseReactionsin Amphiprotic SolventsofLow Permittivity 75
3.1.4 Acid-BaseReactionsin AproticSolventsofLowPermittivity 75
3.2 pH-Scalesin Non-AqueousSolutions 76
3.2.1 Definition ofpHin Non-AqueousSolutions 76
3.2.2 pH Windows in Non-AqueousSolventsand pH ScalesCommon
to Multi Solvents 78
3.3 References 82
4 RedoxReactions inNon-AqueousSolvents 85
4.1 Solvent EffectsonVariousTypes of RedoxReactions 85
4.1.1 Fundamentals of RedoxReactions 85
4.1.2 Solvent EffectsonRedox Potentials
and Redox ReactionMechanisms 88
4.1.3 Dynamical Solvent Effectson the KineticsofRedox Reactions 96
4.2 RedoxPropertiesofSolventsand Potential Windows 99
4.3 RedoxTitrations in Non-AqueousSolutions 102
4.3.1 Titrationswith Oxidizing Agents 102
4.3.2 Titrationswith Reducing Agents 105
4.4 References 106
PartII Electrochemical TechniquesandTheirApplications
inNon-AqueousSolutions
5 OverviewofElectrochemical Techniques 109
5.1 Classification ofElectrochemical Techniques 109
5.2 Fundamentals of ElectrodeReactionsand Current-Potential
Relations 110
5.2.1 Current-Potential Relation forElectron Transfer
at the Electrode 111
5.2.2 Current-Potential Relations and MassTransport 114
5.3 DC Polarography – Methodsthat Electrolyze ElectroactiveSpecies
Only Partially (1) 117
5.4 New Types ofPolarography –Methodsthat Electrolyze Electroactive
SpeciesOnly Partially (2) 125
5.4.1 AC Polarography 125
5.4.2 SWPolarography 127
5.4.3 Pulse Polarography 127
5.5 Voltammetry and Related New Techniques– Methods that Electrolyze
ElectroactiveSpeciesOnly Partially (3) 129