In-situ Thermoelectrochemistry: Working with Heated Electrodes

153 Pages·2015·4.435 MB·English

by  Peter Gründler

Monographs in Electrochemistry
Series Editor: F. Scholz
Peter Gründler
In-situ
Thermoelectrochemistry
Working with Heated Electrodes
In-situ Thermoelectrochemistry
Monographs in Electrochemistry
SeriesEditor:FritzScholz,UniversityofGreifswald,Germany
Surprisingly,alargenumberofimportanttopicsinelectrochemistryisnotcovered
by up-to-date monographs and series on the market, some topics are even not
covered at all. The series Monographs in Electrochemistry fills this gap by pub-
lishing indepth monographs written by experienced and distinguished
electrochemists,coveringboththeoryandapplications.Thefocusissetonexisting
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These fields will range – among others – from analytical and environmental
sciencestosensors,materialssciencesandbiochemicalresearch.
More information about this series at
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Peter Gru¨ndler
In-situ
Thermoelectrochemistry
Working with Heated Electrodes
PeterGru¨ndler
InstituteforSolidStateResearch
LeibnizInstituteforSolidStateandMaterialsResearchDresden(IFW)
Dresden
Germany
ISSN1865-1836 ISSN1865-1844(electronic)
ISBN978-3-662-45817-4 ISBN978-3-662-45818-1(eBook)
DOI10.1007/978-3-662-45818-1
SpringerHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2015932767
©Springer-VerlagBerlinHeidelberg2015
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Preface of the Editor
Ihadthefortunetoknowtheauthorofthisbooksinceabout45years,whenPeter
Gru¨ndlerwas still adocent at the Universityof Leipzig andgave talks on confer-
ences on coulometry and stripping voltammetric detection of the end point of
titrations.Irememberthathisresearchalwaysshowedthathecouldtakeadvantage
ofaprofoundabilitytobuilduphisownelectronicmeasuringequipment.Thiswas
especiallyimportantattimeswhenmoderninstrumentationfromWesterncompa-
nieswasverydifficult,ifnotimpossible,topurchaseinEastGermany.Then,after
thereunificationofGermany,whenPeterGru¨ndleralreadywasfullProfessoratthe
UniversityofRostock,IhavewitnessedfromtheverybeginningPeterGru¨ndler’s
ingeniousdevelopmentsofwhathehascalledatthattime“hot-wireelectrochem-
istry”.Duringthefollowingyearsofveryhardwork,hehas,togetherwithanumber
ofdedicatedco-workers,achievedtheestablishmentofacompletelynewtechnique
forelectrochemicalinvestigations,whichhenowdescribesinthisbookentitled“In
situThermoelectrochemistry–WorkingwithHeatedElectrodes”.Iamveryhappy
thatPeterGru¨ndlerhasdecidedtodescribethebackground,thefoundationsandthe
experimental achievements of his technique in book form, because not only this
willhelptopopularizethisimportantnewdirectioninelectrochemistry,butitwill
also efficiently help to convince more electrochemists, analytical chemists and
maybe also physicists and biologists to apply the technique for solving their own
problems.Theprospectsforapplicationsofheatedelectrodesarealmostlimitless,
andwecanexpectanavalancheofnewresearchworkwiththisnewexperimental
means.
Greifswald,Germany FritzScholz
October2014
v
ThiSisaFMBlankPage
Preface of the Author
Theyear1989wasatimeofgreatchangeandgreatopportunitiesinGermanyand
the whole of Europe. When the author of this book—then a freshly appointed
professor at an old university in Eastern Germany (the GDR)—became aware of
these great opportunities to conduct research freely, he remembered some older
ideaswhichhadnotbeenviabletoworkonbeforethefalloftheBerlinwall.Oneof
theseideaswasthequestion“whatwouldhappenifIdippedthefilamentofalight
bulb into a solution, heated it, and used it as an electrode?” After some short
experiments,itbecameclearthatitwasnotaproblemtomakeaheatedelectrode
thisway,evenamicroelectrode.WhenasuitablePhDstudenthadbeenfoundand
fundinghadbeenarranged,thefirstquestiontobeansweredwaswhetherthehigh
frequencyalternatingcurrentnecessaryfortheheatingwouldallowsensitivesignal
measurement inthe electrochemicalcell.At thispoint,we sufferedacatastrophic
setback. It was nearly impossible to follow the tiny electrolysis current when,
simultaneously, a very strong alternating current flowed through the electrode
wireandgeneratedmassivedistortions.Furthermore,itturnedoutthatothergroups
hadpreviouslytriedtouseanidenticalarrangementforelectrochemicalpurposes,
obviouslyencounteringthesameproblem.Whatnext?
Fortunately,therewasasolution—compensatetheACdistortionsbymeansofa
symmetricelectrodewirearrangement.Thisworkedperfectly,andtheresultwasa
technique that enabled, with negligible effort, the heating of an electrode in situ,
openingupmanyusefulpossibilities,suchasefficientmicrostirringandtheability
to work in overheated solvents, excite kinetically hindered substances to react,
studyvolatilesubstancesathightemperatureswithoutanyloss,etc.Intheinterna-
tionalscientificcommunity,theterm“hot-wireelectrochemistry”becamepopular
forthistechnique.Thus,thesimpletechniquementionedabovemarkedthestartof
afruitful,innovativedevelopmentinelectrochemistry.Thishasbeenverysatisfy-
ing for the author of this book, who has been able to work on a subject of
longstanding interest with a group of highly talented young people in a friendly
atmosphere ofpoliticalfreedom.
vii
viii PrefaceoftheAuthor
Afterbeingusedinmanydifferentregions oftheworldanddiscussedatmany
conferences, hot wire electrochemistry has become part of a larger field. It has
therefore been decided to summarize all the effort made to apply temperature
changestothesurfaceofanelectrodeasanintentionallyvariedexternalparameter.
Thehistoryofallthatisknownasthermoelectrochemistryisalsorelated,andthese
areas represent the main subjects covered in this book. Experimental experiences
arealsorelated,togetherwithmanyuseful“tricks”.
The author hopes that this book leads to wider application of modern
thermoelectrochemicalmethods.
Dresden,Germany PeterGru¨ndler
Acknowledgements
Ithankallmyyoungfriendswhoworkedtogetherwithmeduringoneofthemost
fruitful and happy periods of my life, when we worked out together the hot-wire
electrochemistry.Thankyou,Tadesse,Andreas,Torsten,Andre´,MarkusandBello!
I am happy and grateful that there are, among my scientific friends, such
outstanding people as Joe Wang, Richard Compton, Christopher Brett and Danny
Mandler.Theirinterest,thediscussionswiththemandtheirencouragementwereof
invaluableuseforme.
IamverygratefultomylatefriendLotharDunschwhoofferedmethechanceto
continue to work with hot-wire electrochemistry after my retirement from the
university,inthewonderfulatmosphereofhisgroup.
Ihavetothankalsotheeditoroftheseries“MonographsinElectrochemistry”,
Fritz Scholz, for his invitation to publish this monograph and for his
encouragement.
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