Chemistry of the Non-Metals: Syntheses - Structures - Bonding - Applications (De Gruyter Textbook) (De Gruyter STEM)

744 Pages·2020·7.531 MB·English

by  Ralf Steudel

RalfSteudel
ChemistryoftheNon-Metals
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Ralf Steudel
Chemistry
of the Non-Metals
Syntheses – Structures – Bonding – Applications
In cooperation with David Scheschkewitz
Authors
Prof.Dr.RalfSteudel
Grethe-Weiser-Weg11
D-14055Berlin,Germany
[email protected]
Prof.Dr.DavidScheschkewitz
SaarlandUniversity
Krupp-ChairofGeneralandInorganicChemistry
D-66123Saarbrücken,Germany
[email protected]
ISBN978-3-11-057805-8
e-ISBN(PDF)978-3-11-057806-5
e-ISBN(EPUB)978-3-11-057831-7
LibraryofCongressControlNumber:2019947567
BibliographicinformationpublishedbytheDeutscheNationalbibliothek
TheDeutscheNationalbibliothekliststhispublicationintheDeutscheNationalbibliografie;
detailedbibliographicdataareavailableontheInternetathttp://dnb.dnb.de.
©2020WalterdeGruyterGmbH,Berlin/Boston
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Preface
HowwouldourplanetEarthlooklikewithoutnonmetals?Nowater,noair,nolife!
Not evenrocks and sand sinceoxygenand silicon are responsiblefor 72.7%of the
mass of crustal rocks on the Earth. The human body consists of 96.6% of oxygen,
carbon,hydrogenandnitrogen.Ifalltheothernonmetallicelementsareadded,we
endupwith98.0%.Nonmetalcompoundsplayacrucialroleinourdailylifeandin
industry as you will see in this book. It is therefore obvious that the chemistry of
the nonmetals is a major part of the chemical education at all levels, from high
schooltouniversity.
Thebookyouareholdinginyourhandsisveryspecialtome.Iwrotethefirst
German edition at the very early stage of my academic career, shortly ahead of
my one-year sabbatical leave at M.I.T., Cambridge (Massachusetts). It originated
frommylecturesattheTechnicalUniversityBerlin,theplaceknownasahotspot
of nonmetal chemistry research. With the years, the book became my lifetime
project.Iwasfortunateenoughtosharemypassionandinterestinthechemistry
of the nonmetals (and the yellow element in particular) with many friends and
colleagues in academia and industry all over the world. Thus, the book was al-
ways nourished with the modern developments in fundamental and industrial
research.
Five editions of this monograph have been published by de Gruyter, Berlin/
Boston, each time completely modernized and extended. This newest interna-
tionaleditionisanupdatedtranslationofthelatestGermaneditionof2013.Iam
grateful tomy twoyounger colleagues whoshare the same passion – Prof. David
Scheschkewitz at Saarland University (Germany) who contributed in translating
andupdatinghalfofthepresentedition;andProf.IngoKrossingattheUniversity
of Freiburg (Germany) whose know-how enriched several chapters of a previous
Germanedition.
The book presents an infinite variety and marvelous chemical subtlety of the
22elementsoccupyingtheupper-rightsectionofthePeriodicTableandofhydro-
gen,whichwasattheoriginoftheuniversewhenitstarted13.8billionyearsago
andfromwhichallotherelementswereformedbynuclearreactions.Theworkis
organized in two parts: Part I explains the basic theoretical concepts needed to
understand the structures and reactions of (nonmetallic) molecules and crystals.
ThelargerPartIIpresentsthesyntheses,structuresandapplicationsofthecorre-
sponding compounds and materials. We also address their significance in daily
life, chemical industry, environment, material science and farming wherever
possible.
Numerous review articles and original publications are cited in footnotes and
encouragethereaderstostudycertaintopicsmoreextensively.Tokeepthesizeof
thefootnoteswithnearly1000referencesundercontrol,however,onlyoneauthor
is given if there are more than three. In addition, well-established handbooks of
https://doi.org/10.1515/9783110578065-202
VI Preface
inorganic chemistry (e.g., GMELIN1) and chemical technology (e.g., ULLMANN2
WINNACKER-KÜCHLER3BÜCHEL-MORETTO-WODITSCH4andKIRK-OTHMER5)maybeconsulted
asausefulsourceofinformation.Literatureclosingdatewasspring2019.
In recommending the book to its readers, I like to acknowledge the advice by
Profs.SebastianHasenstab-RiedelandChristianMülleroftheFreeUniversityBerlin
and the help by Dr. Anja Wiesner who assisted with the graphics. Furthermore, I
ammostgratefultomywifeDr.YanaSteudelformanyyearsofsupportandcooper-
ationonthevariouseditionsofthisbook.DeGruyterPublisherinBerlinsupported
this project from day 1, so that many people who worked with me all these years
shouldbeacknowledged.
Many colleagues, coworkers and students contributed to the success of this
book with their comments and suggestions and I will be happy to hear from the
readersofthiseditiontoo.
Berlin-Charlottenburg,
June2019
RalfSteudel
1 GmelinHandbookofInorganicandOrganometallicChemistry–8thedition,Springer,bookseries
with185volumes(partlyinEnglish),publishedin1936–1995.
2 Ullmann’sEncyclopediaofIndustrialChemistry,Wiley-VCH,Weinheim,2006;manyvolumesand
onlineedition.
3 Winnacker-Küchler: Chemische Technik, Vol. 3: Anorganische Grundstoffe, 5th ed., Wiley-VCH,
Weinheim,2005.
4 K.H.Büchel,H.-H.Moretto,D.Werner(eds.),IndustrialInorganicChemistry,2nded.,Wiley-VCH,
Weinheim,2008.
5 Kirk-Othmer(eds.),EncyclopediaofChemicalTechnology,5thed.,Wiley,NewYork,2004;book
serieswith27volumes.
Contents
Preface V
Part I:ChemicalBonds andPropertiesof Molecules
1 Introduction 3
2 TheChemicalBond 11
2.1 TheIonicBond 13
2.1.1 General 13
2.1.2 TheIonizationEnergyE 13
i
2.1.3 TheElectronAffinityE 15
ea
2.1.4 IonicCrystalsandIonicRadii 17
2.1.5 LatticeEnergyandLatticeEnthalpy 19
2.1.6 DeterminationofLatticeEnergiesandEnthalpies 21
2.1.7 SignificanceoftheLatticeEnthalpy 23
2.1.7.1 ComplexFormationofMetalHalides 26
2.1.7.2 WeaklyCoordinatingAnions 27
2.1.8 PolarizationofAnionsbyCations 27
2.2 MolecularGeometry 30
2.2.1 StructureDetermination 30
2.2.2 TheVSEPRModelforEstimationofMolecularGeometries 32
2.2.2.1 LoneElectronPairs 38
2.2.2.2 SingleElectronDomains 40
2.2.2.3 SubstituentsofDifferingElectronegativity 40
2.2.2.4 MultipleBonds 41
2.2.2.5 FinalRemarksontheVSEPRModel 41
2.3 MolecularSymmetryandPointGroupSymbols 43
2.4 TheCovalentBond 48
2.4.1 TheMolecularIon[H ]+ 49
2
2.4.1.1 TheLCAOApproximation 50
2.4.2 TheMoleculeH 57
2
2.4.2.1 TheCation[He ]+ 59
2
2.4.2.2 TheRoleofAntibondingMolecularOrbitals 59
2.4.3 HomonuclearDiatomicMolecules 60
2.4.4 PhotoelectronSpectroscopyofSmallMolecules 68
2.4.5 HeteronuclearDiatomicMolecules 70
2.4.5.1 GeneralRulesfortheConstructionofMOs 72
2.4.6 Three-AtomicMoleculesofD∞hSymmetry 73
2.4.6.1 TheMoleculeBeH 75
2
VIII Contents
2.4.6.2 TheMoleculeCO 76
2
2.4.7 Three-AtomicMoleculesofC Symmetry 77
2v
2.4.8 Four-AtomicMoleculesofD Symmetry 80
3h
2.4.9 Four-AtomicMoleculesofC Symmetry 83
3v
2.4.10 Five-AtomicMolecules 87
2.5 TheCoordinateBond 89
2.6 HypercoordinateMolecules 93
3 VANDERWAALSInteraction 101
3.1 TheDipoleEffect 101
3.2 InducedDipoleEffect 104
3.3 TheDispersionEffect 104
3.4 VANDERWAALSRadii 107
3.5 VANDERWAALSMolecules 109
4 BondProperties 113
4.1 Introduction 113
4.2 BondEnthalpyandDissociationEnthalpy 114
4.2.1 DiatomicMolecules 114
4.2.2 PolyatomicMolecules 117
4.2.3 WhyIsOxygenaGasandSulfuraSolid? 122
4.3 TheInternuclearDistance 124
4.4 TheValenceForceConstant 127
4.4.1 DiatomicMolecules 127
4.4.2 DiatomicGroups 128
4.4.3 Three-AtomicMolecules 129
4.5 RelationshipsBetweenDifferentBondProperties 132
4.6 PolarityofCovalentBondsandElectronegativity 134
4.6.1 Introduction 134
4.6.2 Electronegativities(χ) 136
4.6.2.1 ThermodynamicElectronegativitiesbyPAULING 136
4.6.2.2 ElectronegativitiesaccordingtoALLREDandROCHOW 138
4.6.2.3 SpectroscopicelectronegativitiesaccordingtoALLEN 141
4.6.2.4 GroupElectronegativities 142
4.6.3 TheDipoleMoment 143
4.7 ElectronDensityDistributioninMoleculesandCrystals 147
4.7.1 PromoleculeandDeformationDensity 147
4.7.2 HalogenBonding 149
Contents IX
Part II:Chemistry oftheNon-Metals
5 Hydrogen 157
5.1 ElementalHydrogen 157
5.1.1 ProductionandUses 157
5.1.2 IsotopesofHydrogen 161
5.1.3 PropertiesofHydrogen 164
5.2 HydrogenIonsH+ 165
5.3 Acids 168
5.3.1 OxoniumSalts 169
5.3.2 LiquidAmmonia 171
5.3.3 AnhydrousSulfuricAcid 172
5.4 Bases 172
5.5 TheRelativeStrengthofAcidsandBases 174
5.5.1 DiluteSolutions 174
5.5.1.1 BinaryCovalentHydrides 175
5.5.1.2 Oxoacids 176
5.5.2 ConcentratedandNonaqueousAcids 177
5.6 HydrogenBonds(H-Bonds) 181
5.6.1 Introduction 181
5.6.2 GeneralPropertiesofHydrogenBonds 182
5.6.3 ExperimentalDetectionofHydrogenBonds 183
5.6.3.1 PhysicalConstants 183
5.6.3.2 StructureDetermination 185
5.6.3.3 MolecularSpectroscopy 185
5.6.4 ExamplesofSpecialHydrogenBonds 187
5.6.4.1 HydrogenFluoride 187
5.6.4.2 IceandWater 188
5.6.4.3 GasHydratesandClathrateHydrates 194
5.6.4.4 AmmoniaandAmines 195
5.6.5 TheoryofHydrogenBondFormation 198
5.7 HydrogenCompounds(Hydrides) 202
5.7.1 Introduction 202
5.7.2 CovalentHydrides 203
5.7.2.1 ActivationofH Molecules 203
2
5.7.3 H asLigandinCoordinationCompounds 204
2
5.7.4 Salt-LikeHydrides 206
5.7.5 Metal-andAlloy-LikeHydrides(InsertionHydrides) 209
5.7.5.1 BondingofHydrogeninAlloy-LikeHydrides 211