Table Of ContentBinnewies ⋅ Glaum ⋅ Schmidt ⋅ Schmidt
Chemical Vapor Transport Reactions
MichaelBinnewies⋅RobertGlaum⋅MarcusSchmidt⋅PeerSchmidt
Chemical Vapor
Transport Reactions
DE GRUYTER
Authors
ProfessorDr.MichaelBinnewies ProfessorDr.RobertGlaum
UniversitätHannover InstitutfürAnorganischeChemie
InstitutfürAnorganischeChemie derUniversitätBonn
Callinstr.9 Gerhard-Domagk-Str.1
30167Hannover 53121Bonn
[email protected] [email protected]
Dr.MarcusSchmidt ProfessorDr.PeerSchmidt
Max-Planck-Institut HochschuleLausitz(FH)
fürChemischePhysikfesterStoffe FachrichtungChemie
NöthnitzerStr.40 undLebensmittelchemie
01187Dresden GroßenhainerStr.57
[email protected] 01968Senftenberg
[email protected]
ISBN978-3-11-025464-8
e-ISBN978-3-11-025465-5
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Professor Dr. Dr. h.c. Harald Schäfer
Dedicated to Professor Dr. Dr. h.c. Harald Schäfer
in recognition of his fundamental research to the topic
„Chemical Vapor Transport Reactions“.
Preface
Theoriginofthisbookhasalonghistory.Backin1962,HaraldSchäferpublished
a monograph with the title Chemische Transportreaktionen. It provided a survey
of the complete knowledge on this subject back then. The “transport book” was
translated shortly after its appearance into English and Russian. For more than
halfacenturythebookhasservedasahighlycitedreferenceforbasicprinciples,
understanding, and application of chemical vapor transport reactions.
Research onchemical vaportransport, however, wasnot at allcompleted with
the appearance of Schäfer’s book. During the decades since 1962 the results of
many new investigations in this field of research have been published. These
papers present a plethora of novel examples for the preparative use of chemical
vapor transport. One target of these studies was the synthesis of pure, well de-
fined, and well crystallized solids, frequently with the purpose of a detailed cha-
racterization of their physical properties. Another aim of such experiments was
the preparation of single-crystals for crystal structure analyses. Apart from the
applicationasasynthetictool,duringtheseyearsalargebodyofworkwasdedi-
cated to the development of improved models for the understanding of various
aspectsofchemicalvaportransportexperiments.Buildingonthefoundationslaid
by Harald Schäfer, significant progress in this respect was achieved by Reginald
Gruehn, Gernot Krabbes, and Heinrich Oppermann and their research groups.
Afterbecomingprofessoremeritusinaround1980,HaraldSchäfersummarized
the knowledge accumulated by then, which had drastically grown compared to
1962,intoanewmanuscript.ThismanuscriptwasextendedbyReginaldGruehn,
but never completed. The great interest of many colleagues in chemical vapor
transportreactions,frominorganicandsolidstatechemistryaswellasfrommate-
rial science, caused our decision to restart the publishing project. We drew addi-
tional motivation from the fact that all of us were students of Schäfer, Gruehn,
and Oppermann.
Eventually nucleation and growth of the project was substantially supported
byRüdiger Kniep.Hishospitality attheMax-Planck-Institutfür ChemischePhy-
sik fester Stoffe (Dresden, Germany) allowed frequent meetings in a secluded
and very productive atmosphere. This support allowed us to finish the “new
transport book” within a period of three years. Here we would like to take the
opportunity to express our particular gratitude for this support.
TheauthorshadattheirdisposalGruehnsextendedversionofSchaefersmanu-
scriptfrom1980.Thepresentbookistheresultofvariousre-organizationsofthe
text, substantial extension, and updating, especially for the literature from 1980
to 2010. Thus, for the first time, the models required for an understanding even
ofverycomplexchemicalvaportransportexperimentsarepresentedinauniform
way.Chapter 11“Gas Speciesandtheir Stability”shouldimprove understanding
of the chemical behavior of inorganic compounds in the gaseous phase. Further-
viii Preface
more,wehavebeenparticularlyconcernedtoelucidatethechemicalbackground
and principles of transport reactions, and to document as completely as possible
the preparative benefit that the method is able to provide. In this sense, for
example, chemical vapor transport of intermetallic compounds and of chalco-
genidehalideshavebeenforthefirsttimesystematicallyreviewedanddescribed.
We thank Dr. Werner Marx, Zentrale Informationsvermittlungsstelle der Che-
misch-Physikalisch-Technischen Sektion der Max-Planck-Gesellschaft, for nume-
rous very careful literature surveys on the subject. Support from Mrs. Claudia
Schulze, Hannover, as well as from the library staff at MPI CPfS is gratefully
acknowledged for supplying us with copies of more than 2000 references from
literature. Mrs. Friederike Steinbach, Dresden, is thanked for her support with
the organization and layout of the manuscript. Our particular thanks go to Pro-
fessor Heinrich Oppermann for his critical review of the manuscript.
We would also like to express our thanks to Dr. Ralf Köppe (KIT, Karlsruhe,
Germany)forhiscontributionconcerningthecalculationofthermodynamicdata
with the help of quantum chemical methods.
Last but not least we want to acknowledge the great effort and dedication
Sebastian and Manuela Jüstel and Melanie Ahend put into the translation of
major parts of the manuscript.
Michael Binnewies, Robert Glaum,
Marcus Schmidt, Peer Schmidt
Hints and Suggestions for the Reader
Atthestartofthisbooksomehintsandsuggestionsshouldbegiventothereader
toalloweasieraccesstothesubject.Recommendationsarealsoprovidedonhow
to use the extensive lists of references.
Chapter1providesthereaderwithasummaryofthesubjectofchemicalvapor
transport reactions. Only a basic knowledge of inorganic and physical chemistry
will be required to understand this introduction. Reading this chapter might al-
ready be sufficient for those interested only in chemical vapor transport as a
preparative tool. If the reader wants to acquire an in-depth, state-of-the-art un-
derstanding of the thermodynamic background of chemical vapor transport and
of the processes determining the mass flow within an ampoule exposed to a
temperature gradient, Chapter 2 provides the necessary reading.
In Chapters 3 to 10 the characteristic transport behavior of various classes of
compounds is described on the basis of selected examples. At the end of each
chapterorsectiontables areincluded,whichshowinalphabetical orderasurvey
of transportable solids of the corresponding compound class. In addition, the
tables list, along with the literature references, the transport agents (additives)
and temperature gradients that have been used. To allow easier finding of infor-
mationconcerning particularcompoundsandclasses ofcompounds,aswell asto
simplify handling ofthe very large body of referencesfrom literature, we delibe-
rately avoided setting up just a single reference list at the end of the book. In-
stead, at the end of each chapter the corresponding references are given. Refe-
rences that in our opinion are of particular interest in the context of the given
chapter are set in bold letters.
Foranunderstandingofthechemicalreactionsparticipatinginchemicalvapor
transportsomeknowledgeongaseousinorganiccompoundsisrequired.Asurvey
on this topic can be found in Chapter 11.
Chapter 12 gives some hints on how to deal with thermodynamic data. Ques-
tions concerning thermodynamic tables and databases, experimental origin, as
well as precision and accuracy of data are addressed. A review on estimation of
thermodynamic data completes this chapter.
Computer-aided modeling of chemical vapor transport experiments is de-
scribedinChapter13.Thetwocomputerprogramsdealtwithindetailcanbeob-
tained free of charge. Sources are provided.
Eventually the final chapters, Chapter 14 “Working Techniques” and Chapter
15“SelectedExperimentsforPracticalWorkonChemicalVaporTransportReac-
tions”,aremeantasanintroductiontothepracticalrealizationofchemicalvapor
transport experiments in the laboratory. The examples are carefully chosen and
they should provide insight into the various aspects of chemical vapor transport.
In addition they should lead, even when conducted by less experienced experi-
menters, to well developed, aesthetically appealing crystals.
