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KosukeIzutsuElectrochemistryinNonaqueousSolutionsElectrochemistryinNonaqueousSolutions.KosukeIzutsuCopyright©2002Wiley-VCHVerlagGmbH&Co.KGaAISBNs:3-527-30516-5(Hardback);3-527-60065-5(Electronic)RelatedTitlesfromWILEY-VCHBard,A.J.,Stratmann,M.,Licht,S.(Eds)EncyclopediaofElectrochemistry,VolumeVI2001.ISBN3-527-30398-7Kaifer,A.E.,Gómez-Kaifer,M.SupramolecularElectrochemistry1999.ISBN3-527-29597-6Memming,R.SemiconductorElectrochemistry2000.ISBN3-527-30147-XGünzler,H.,Williams,A.(Eds)HandbookofAnalyticalTechniques2001.ISBN3-527-30165-8ElectrochemistryinNonaqueousSolutions.KosukeIzutsuCopyright©2002Wiley-VCHVerlagGmbH&Co.KGaAISBNs:3-527-30516-5(Hardback);3-527-60065-5(Electronic)ElectrochemistryinNonaqueousSolutionsK.IzutsuElectrochemistryinNonaqueousSolutions.KosukeIzutsuCopyright©2002Wiley-VCHVerlagGmbH&Co.KGaAISBNs:3-527-30516-5(Hardback);3-527-60065-5(Electronic)ProfessorDr.K.Izutsu3-8-23MotomachiMatsumoto390-0803JapanLibraryofCongressCardNo.:appliedforBritishLibraryCataloguing-in-PublicationData:AcataloguerecordforthisbookisavailablefromtheBritishLibrary.DieDeutscheBibliothek–CIP-Cataloguing-in-PublicationDataAcataloguerecordforthispublicationisavailablefromDieDeutscheBibliothek.©WILEY-VCHVerlagGmbHD-69469Weinheim,2002Allrightsreserved(includingthoseoftranslationinotherlanguages).Nopartofthisbookmaybereproducedinanyform–byphotoprinting,mi-crofilm,oranyothermeans–nortransmittedortranslatedintomachinelanguagewithoutwrittenpermissionfromthepublishers.Registerednames,trademarks,etc.usedinthisbook,evenwhennotspecificallymarkedassuch,arenottobeconsideredunprotectedbylaw.TypesettingK+VFotosatzGmbH,BeerfeldenPrintingbetz-druckgmbh,DarmstadtBookbindingJ.SchäfferGmbH&Co.KG,GrünstadtprintedintheFederalRepublicofGermanyprintedonacid-freepaperISBN3-527-30516-5Thisbookwascarefullyproduced.Nevertheless,authorandpublisherdonotwarranttheinforma-tioncontainedthereintobefreeoferrors.Rea-dersareadvisedtokeepinmindthatstatements,data,illustrations,proceduraldetailsorotheritemsmayinadvertentlybeinaccurate.ElectrochemistryinNonaqueousSolutions.KosukeIzutsuCopyright©2002Wiley-VCHVerlagGmbH&Co.KGaAISBNs:3-527-30516-5(Hardback);3-527-60065-5(Electronic)Amajorityofchemicalreactionsarecarriedoutinsolution.Theuseofasolventasreactionmediummakesiteasytocontrolreactionconditionssuchastempera-ture,pressure,pH,rateofmasstransfer,andconcentrationofreactant.Wateristhemostpopularsolvent.However,byusingappropriatenon-aqueoussolvents,substancesthatareinsolubleinwatercanbedissolved,substancesthatareun-stableinwaterremainstable,andchemicalreactionsthatareimpossibleinwaterbecomepossible.Thereactionenvironmentsaremarkedlywiderinnon-aqueoussolventsthaninwater.Thewidespreaduseofnon-aqueoussolvents,especiallydipolaraproticsolvents,beganinthe1950sinvariousfieldsofpureandappliedchemistryandhascon-tributedgreatlytolateradvancesinchemicalsciencesandtechnologies.Fromtheverybeginning,electrochemistryinnon-aqueoussolutionshasplayedanimpor-tantroleinexploringnewchemicalpossibilitiesaswellasinprovidingthemeth-odstoevaluatestaticsolventeffectsonvariouschemicalprocesses.Moreover,manynewelectrochemicaltechnologieshavebeendevelopedusingnon-aqueoussolvents.Recently,electrochemistryinnon-aqueoussolutionshasmadeenormousprogress:thedynamicsolventeffectsonelectrochemicalprocesseshavebeengreatlyelucidatedandsolventeffectsarenowunderstoodmuchbetterthanbe-fore.Ontheotherhand,however,itisalsotruethatsomeusefulsolventshavepropertiesthatareproblematictohumanhealthandtheenvironment.Today,ef-fortsarebeingmade,undertheframeworkof‘greenchemistry’,tofindenviron-mentallybenignmediaforchemicalprocesses,includingharmlessnon-aqueoussolvents,immobilizedsolvents,ionicliquids,supercriticalfluids,aqueoussys-tems,andevensolventlessreactionsystems.Forelectrochemicalpurposes,replac-inghazardoussolventsbyharmlesssolvents,ionicliquidsandsupercriticalfluidsappearstobepromising.Thisbookwaswrittentoprovidereaderswithsomeknowledgeofelectrochem-istryinnon-aqueoussolutions,fromitsfundamentalstothelatestdevelopments,includingthecurrentsituationconcerninghazardoussolvents.Thebookisdi-videdintotwoparts.PartI(Chapters1to4)containsadiscussionofsolventprop-ertiesandthendealswithsolventeffectsonchemicalprocessessuchasionsolva-tion,ioncomplexation,electrolytedissociation,acid-basereactionsandredoxreac-tions.Suchsolventeffectsareoffundamentalimportanceinunderstandingchem-VPrefaceElectrochemistryinNonaqueousSolutions.KosukeIzutsuCopyright©2002Wiley-VCHVerlagGmbH&Co.KGaAISBNs:3-527-30516-5(Hardback);3-527-60065-5(Electronic)istryinnon-aqueoussolutions;furthermore,theirquantitativeevaluationsareof-tencarriedoutbymeansofelectrochemicaltechniques.PartII(Chapters5to12)mainlydealswiththeuseofelectrochemicaltechniquesinnon-aqueoussolu-tions.InChapter5,thefundamentalsofvariouselectrochemicaltechniquesareoutlinedinpreparationforthefollowingchapters.InChapters6to9,theapplica-tionsofpotentiometry,conductimetry,polarography,voltammetry,andothernewelectrochemicaltechniquesinnon-aqueoussolutionsarediscussedbyfocusingonthe