Inorganic chemistry: Principles of structure and reactivity

920 Pages·1978·46.119 MB·English

by  James E. Huheey

second edition
Principles of structure
and
reactivity
James E.Huheey
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INORGANIC
CHEMISTRY

INORGANIC
CHEMISTRY
principles
of structure
and
reactivity
SECOND EDITION
James Huheey
E.
UNIVERSITY OF MARYLAND
Harper & Row, Publishers
New York, Hagerstown, San Francisco, London
©
Figures from the followingjournalsarecopyright to the American Chemical Society: Accountsof
Chemical Research, Chemical and Engineering News, Inorganic Chemistry, Journal of Chemical
Education,Journalofthe American ChemicalSociety.
Permission for the publication herein ofSadtlerStandard Spectra'* has been granted, and all rights
are reserved, by Sadtler Research Laboratories, Inc.
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Inorganic Chemistry: Principles ofStructure and Reactivity,SecondEdition
©
Copyright 1978 by James E. Huheey
All rights reserved. Printed in the United States ofAmerica. No part ofthis book may be used or
reproducedinanymannerwhatsoeverwithoutwrittenpermissionexceptinthecaseofbriefquotations
embodied in critical articles and reviews. For information address Harper & Row, Publishers,Inc.,
10 East 53rd Street, New York, N.Y. 10022.
Library ofCongress Cataloging in Publication Data
Huheey, James E.
Inorganic chemistry.
Bibliography: p.
Includes index.
1. Chemistry, Inorganic. I. Title.
QD151.2.H84 1978 546 77-19014
ISBN 0-06-042986-0
1
Contents
Preface to the Second Edition ix
Preface to the First Edition xi
To the Student xv
Introductory Survey of Inorganic Chemistry
1 l
What Is Inorganic Chemistry? I
2 The Structure of the Atom 9
The Wave Equation
1
The Hydrogen Atom 13
The Polyelectronic Atom 25
3 Ionic Bonding and the Nature of Solids 51
Lattice Energy 54
Size Effects 65
The Predictive Power ofThermochemical Calculations on Ionic
Compounds 87
Covalent Character in Predominantly Ionic Bonds 90
Solids Held Together by Covalent Bonding 101
4 The Covalent Bond: Theory and Energetics ill
Valence Bond Theory 112
Molecular Orbital Theory 115
Symmetry and Overlap 119
Comparison of Valence Bond and Molecular Orbital Theory 132
Hybridization 138
Multiple Bonding 148
Derealization 150
Experimental Measurement of Charge Distribution in Molecules 174
5 The Covalent Bond: Structure and Reactivity 192
Hybridization 192
Structures of Molecules 197
Bond Lengths 213
Experimental Determination of Molecular Structure 215
Some Simple Reactions ofCovalently Bonded Molecules 219
CONTENTS
vi
6 Chemical Forces 230
Internuclear Distances and Atomic Radii 230
Types of Chemical Forces 237
Effects of Chemical Forces 248
7 Acid-Base Chemistry 258
Acid-Base Concepts 258
Measures ofAcid-Base Strength 271
Hard and Soft Acids and Bases 276
8 Chemistry in Aqueous and Nonaqueous Solutions 291
Nonaqueous Solvents 292
Molten Salts 305
Electrode Potentials and Electromotive Forces 310
9 Coordination Chemistry: Theory 332
The Effective Atomic Number Rule and the Chemistry of Organometallic
Compounds 336
Valence Bond Theory 342
Crystal Field Theory 348
Molecular Orbital Theory 390
A Closer Look at Spectra 412
10 Coordination Chemistry: Structure 425
Coordination Number 2 425
Coordination Number 3 427
Coordination Number 4 428
Coordination Number 5 432
Coordination Number 6 442
Coordination Number 7 461
Coordination Number 8 464
Higher Coordination Numbers 466
Coordination Number Zero 468
Linkage Isomerism 468
Other Types ofIsomerism 478
Structural Equilibria ofComplexes 480
The Chelate Effect 481
11 Coordination Chemistry: Reactions, Kinetics, and
Mechanisms
489
The trans Effect 491
Kinetics and Reaction Rates of Octahedral Substitution 498
I