Table Of ContentMonographs in Electrochemistry
Series Editor: F. Scholz
Aleksandr A. Andriiko
Yuriy O. Andriyko
Gerhard E. Nauer
Many-electron
Electrochemical
Processes
Reactions in Molten Salts,
Room-Temperature Ionic Liquids
and Ionic Solutions
Many-electron Electrochemical Processes
For furthervolumes:
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Monographs in Electrochemistry
Surprisingly,alargenumberofimportanttopicsinelectrochemistryisnotcovered
by up-to-date monographs and series on the market, some topics are even not
coveredatall.TheseriesMonographsinElectrochemistryfillsthisgapbypublish-
ingindepthmonographswrittenbyexperiencedanddistinguishedelectrochemists,
covering both theory and applications. The focus is set on existing as well as
emergingmethodsforresearchers,engineers,andpractitionersactiveinthemany
and often interdisciplinary fields, where electrochemistry plays a key role. These
fields will range – among others – from analytical and environmental sciences to
sensors,materialssciencesandbiochemicalresearch.
Informationaboutpublishedandforthcomingvolumesisavailableat
http://www.springer.com/series/7386
SeriesEditor:FritzScholz,UniversityofGreifswald,Germany
Aleksandr A. Andriiko • Yuriy O. Andriyko •
Gerhard E. Nauer
Many-electron
Electrochemical Processes
Reactions in Molten Salts,
Room-Temperature Ionic Liquids
and Ionic Solutions
AleksandrA.Andriiko YuriyO.Andriyko
KyivPolytechnicInstitute CentreofElectrochemicalSurface
ChemicalTechnologyDepartment Technology(CEST)
NationalTechnicalUniversityofUkraine WienerNeustadt
Kyiv Austria
Ukraine
GerhardE.Nauer
ViennaUniversity
InstituteofPhysicalChemistry
Vienna
Austria
ISSN1865-1836 ISSN1865-1844(electronic)
ISBN978-3-642-35769-5 ISBN978-3-642-35770-1(eBook)
DOI10.1007/978-3-642-35770-1
SpringerHeidelbergNewYorkDordrechtLondon
LibraryofCongressControlNumber:2013932472
#Springer-VerlagBerlinHeidelberg2013
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Dedicated to the memory of
Professor Yu. K. Delimarskiy
.
Preface of the Editor
Bothinnature,e.g.inphotosynthesisandrespiration,andinindustrialelectrochem-
istry,multi-electronprocessesbyfaroutnumbersingle-electronprocesses.Hence,
their significance is indisputable, but this is also true for their complexity with
respect to theory and experiments. The authors of this monograph have a strong
background in high-temperature molten salt electrochemistry, which concerns
especially the transition metals and their ions. These elements have a rich redox
chemistry and their electrochemical reactions can only be understood considering
rather complex multi-electron processes. The senior Ukrainian author Aleksander
AndriikoisapupilofJuriyKonstantinovichDelimarskiy(1904–1990),theformer
head oftheKiev schoolof(high-temperature)moltensalt electrochemistry which
flourished over many decades. Unfortunately, the scientific treasures of wisdom
gatheredduringthatperiodarebadlyaccessibletoWesternscientists.Henceitisa
veryluckyconstellationthattheseniorauthorAleksanderAndriikowasjoinedby
the young Ukrainian electrochemist Yuriy Andriyko, by the way his son, and the
Austrian electrochemist Gerhard Nauer to compile this monograph. High-
temperaturemoltensaltelectrochemistryoftransitionmetalsandotherpolyvalent
metals offers a great amount of relevant information, especially for the room-
temperature ionic liquid electrochemistry which blossoms nowadays. Preserving
and disseminating the precious knowledge and experience of people who have
activelytakenpartinthedevelopmentofmoltensaltelectrochemistryare thusan
investmentinthefutureofelectrochemistry.
Greifswald,Germany FritzScholz
June2012
vii
.
Preface of the Authors
“Allthingsrun,allthingschange”(Heraklit)
The main ideas of this book originate from Electrochemistry of Molten Salts.
The two of us (AA and GN) belong to the generation of electrochemists who
worked in this branch of science in times of its blossoming and evidenced its
rapid degradation. Once powerful, this field of chemistry had fallen in a state of
deepdeclinetillthemid-1990s.
Howandwhycouldithappen?
Alexander Andriiko, a former Soviet Union scientist who worked in this field
sincetheendof1970sforabout25years,knowsthattheSovietSciencehadbeen
shakeninthemid-1980s.“Remembermyword,fellows,thisisnotforgood”—that
was the comment relating to the situation of science given at the beginning of
perestroika (1986) by his (i.e., Andriiko’s) Maitre, Academician Prof. Yu.
Delimarskiy. This prophecy became a reality very soon. A last nail in the coffin
ofhissciencehadbeenthrustafterColdWarwasover.Indeed,thestreamsfromthe
mighty river of Military Industries that fed this science—it is not a secret
anymore—driedoutverysoonafterthecollapseofSU.
Hardlyeverhe,theformerSovietscientist,regretsaboutthis.Freedomisgreat
thing.However,everythingmustbepaidinthisworld.Thepricewasasevereloss
ofscienceon1/6partofourworld.
As for the Electrochemistry of Molten Salts, it was lost worldwide—not in the
FSU countries only. The diagram below gives an idea about the scale of this
catastrophe. It represents the structure of electrochemical researches in the world
throughthepublicationsinarepresentativeinternationaljournalin1995–1996,just
a few years after these events. As we can see, Molten Salts electrochemistrytook
thelastplaceamongothervariousbranchesofelectrochemistry.Nothinghasbeen
changedsincethen.
Deplorable situation—especially taking into account leading positions of Mol-
tenSaltElectrochemistrysome20–25yearsago.
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