Handbook of Reference Electrodes

351 Pages·2013·4.43 MB·English

by  György Inzelt (auth.)

György Inzelt
Andrzej Lewenstam
Fritz Scholz Editors
Handbook
of Reference
Electrodes
Handbook of Reference Electrodes
.
Gyo¨rgy Inzelt (cid:129) Andrzej Lewenstam (cid:129) Fritz Scholz
Editors
Handbook of Reference
Electrodes
With contributions by
F.G.K. Baucke, A.I. Bhatt, Z. Galus, G. Gritzner, G. Inzelt, K. Izutsu,
H. Kahlert, T. Kakiuchi, V.V. Kharton, A. Kisiel, A. Lewenstam,
K.Maksymiuk, A. Michalska,J.Migdalski, M.Rohwerder, F. Scholz,
G.A.Snook,P.Spitzer,G.Tauber,E.V.Tsipis,G.Tsirlina,S.Wunderli
Editors
Gyo¨rgyInzelt AndrzejLewenstam
DepartmentofPhysicalChemistry CenterforProcessAnalyticalChemistry
Eo¨tvo¨sLora´ndUniversity andSensorTechnology‘ProSens’
Budapest ProcessChemistryCenter
Hungary A˚boAkademiUniversity
A˚bo,Finland
FacultyofMaterialsScienceandCeramics
FritzScholz AGHUniversityofScienceandTechnology
InstituteofBiochemistry Krakow,Poland
UniversityofGreifswald
Greifswald
Germany
ISBN978-3-642-36187-6 ISBN978-3-642-36188-3(eBook)
DOI10.1007/978-3-642-36188-3
SpringerHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2013936741
#Springer-VerlagBerlinHeidelberg2013
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In Memoriam,
The editors dedicate this book to the memory
of Dr. Friedrich G. K. Baucke (October30th,
1930–March 4th, 2013), famed expert in the
study of solid glasses and glass melts, and
elucidator of the mechanism of the glass
electrode. He was a fine scholar, thoughtful
scientist,andsincerefriend.Chapter8ofthis
handbook, written by Dr. F. G. K. Baucke at
the age of 82, testifies to his indefatigable
search for truth.
.
Preface
One of the fundamental problems of the electrochemistry is that the Galvani
potential difference across an interface, i.e., the difference of inner potentials of
twoadjacent phases,isnotexperimentallyaccessible.Consequently,thepotential
ofasingleelectrode,i.e.,aso-calledhalf-cellconsistingofoneelectronconductor
and at least one ionic conductor cannot be determined. By combining two
electrodes to a complete galvanic cell or electrolytic cell, potential difference
between the two metallic terminals can be measured. The two metallic terminals
should be identical for any meaningful potential measurement, and under certain
conditions the measured potential is characteristic to the electrode potential
intended to determine. For this purpose we use reference electrodes. Reference
electrodes are galvanic half-cells which are designed to provide a stable and
reproducibleGalvanipotentialdifference,eitherasaprimarystandard(thestandard
hydrogenelectrode)orassecondarystandards.Inordertoproducereliableexperi-
mental data, reference electrodes have to fulfill many, partly contradictory
conditions, which practically never can be met to full satisfaction. For the choice
and application of a particular reference electrode it is of utmost importance to
knowitspropertiesasdetailedaspossible.
It is of great theoretical interest to relate a Galvani potential difference to the
absolutepotentialofaclearlydefinedspecies,e.g.,thepotentialofafreeelectronin
vacuum. This defines an absolute potential scale (see Chap. 15), for which the
preciserelationtotheconventionalstandardhydrogenelectrodescaleforaqueous
solutionsisstilldebated.Hence,aconsistentsystembasedonthestandardhydro-
genelectrode(SHE)definitionstillservesthefundamentalneedsofmeasuringand
calculating redox equilibria, and coupled chemical equilibria in aqueous systems.
The relation of the electrode potentials in nonaqueous systems, be they liquid or
solid, to the (aqueous) SHE, is of fundamental importance in chemistry because
nonaqueous systems play an important role in modern technologies and research,
andinmanycasesaqueousandnonaqueoussystemsareevendirectlycoupled,as,
e.g.,inionpartitionsystems.
Therefore,theauthorsofthisHandbookofReferenceElectrodeswereguidedby
theideatoprovideallnecessaryandreliabledata.Thelastandonlyhandbookon
vii
viii Preface
reference electrodes was published in 1961 [Ives DJG, Janz GJ (1961) Reference
electrodes. Theory and practice. Academic, New York]. Although the progress in
thisfieldofresearchandtechnologywasrathersteadyandnotrevolutionaryinthe
last half century, a lot of information vital for modern electrochemistry has been
addedduringthattime.Naturally,theIves/Janzbookcouldnotcontaininformation
onreferenceelectrodesforsolid-stateelectrolytesystemsandnothingaboutroom
temperature ionic liquids, glass melts, reference electrodes based on conducting
polymers,etc.,sincethesetopicsstronglydevelopedinthelastdecades.
Inthefirstsectionthishandbookprovidesthefundamentalsofthermodynamics
and kinetics of reference electrodes, and then liquid junction potentials and salt
bridges are discussed, as they are involved in almost all reference systems. The
followingchapterspresentthevariousreferenceelectrodesandsystemsastheyare
presently used. A final chapter is devoted to the Kelvin probe and discusses this
instrumentasareferenceelectrodeforcontactpotentialmeasurements.
Budapest,Hungary Gyo¨rgyInzelt
A˚bo,FinlandandKrakow,Poland AndrzejLewenstam
Greifswald,Germany FritzScholz
Aug2012
Contents
1 ElectrodePotentials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Gyo¨rgyInzelt
2 ReferenceRedoxSystemsinNonaqueousSystemsandtheRelation
ofElectrodePotentialsinNonaqueousandMixedSolventsto
StandardPotentialsinWater. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
GerhardGritzner
3 LiquidJunctionPotentials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
GalinaTsirlina
4 SaltBridgesandDiaphragms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
FritzScholzandTakashiKakiuchi
5 ReferenceElectrodesforAqueousSolutions. . . . . . . . . . . . . . . . . . 77
PetraSpitzer,SamuelWunderli,KrzysztofMaksymiuk,
AgataMichalska,AnnaKisiel,ZbigniewGalus,andGu¨nterTauber
6 ReferenceElectrodesforUseinNonaqueousSolutions. . . . . . . . . . 145
KosukeIzutsu
7 ReferenceElectrodesforIonicLiquidsandMoltenSalts. . . . . . . . 189
AnandI.BhattandGraemeA.Snook
8 ReferenceElectrodesinOxidicGlassMelts. . . . . . . . . . . . . . . . . . 229
FriedrichG.K.Baucke
9 ReferenceElectrodesforSolid-ElectrolyteDevices. . . . . . . . . . . . . 243
VladislavV.KhartonandEkaterinaV.Tsipis
10 DirectSolidContactinReferenceElectrodes. . . . . . . . . . . . . . . . . 279
AndrzejLewenstam
11 Micro-referenceElectrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
HeikeKahlert
ix