Chemical vapor transport reactions PDF
Preview Chemical vapor transport reactions
Binnewies ⋅ 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 LibraryofCongressCataloging-in-PublicationData ACIPcatalogrecordforthisbookhasbeenappliedforattheLibraryofCongress BibliographicinformationpublishedbytheDeutscheNationalbibliothek TheDeutscheNationalbibliothekliststhispublicationintheDeutscheNationalbibliografie; detailedbibliographicdataareavailableintheinternetathttp:..dnb.dnb.de. ©2012byWalterdeGruyterGmbH&Co.KG,Berlin.Boston Thepublisher,togetherwiththeauthorsandeditors,hastakengreatpainstoensurethatall informationpresentedinthiswork(programs,applications,amounts,dosages,etc.)reflectsthe standardofknowledgeatthetimeofpublication.Despitecarefulmanuscriptpreparationand proofcorrection,errorscanneverthelessoccur.Authors,editorsandpublisherdisclaimall responsibilityandforanyerrorsoromissionsorliabilityfortheresultsobtainedfromuseof theinformation,orpartsthereof,containedinthiswork. Typesetting:MetaSystemsGmbH,Wustermark Printingandbinding:Hubert&Co.GmbH&Co.KG,Göttingen PrintedinGermany ♾Printedonacid-freepaper www.degruyter.com 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.
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