Physical Chemistry of Ionic Materials Ions

Defects play an important role in determining the properties of solids. This book provides an introduction to chemical bond, phonons, and thermodynamics; treatment of point defect formation and reaction, equilibria, mechanisms, and kinetics; kinetics chapters on solid state processes; and electrochemical techniques and applications. Offers a coherent description of fundamental defect chemistry and the most common applications. Up-to-date trends and developments within this field. Combines electrochemical concepts with aspects of semiconductor physics.

Joachim Maier is Director at the Max Planck Institute for Solid State Research in Stuttgart and heads the department of Physical Chemistry. Maier studied chemistry in Saarbrücken, made his Masters and PhD in Physical Chemistry there. He received his professorial degree at the University of Tübingen.

1 Introduction

11

(12)

1.1 Motivation

11

(3)

1.2 The defect concept: Point defects as the main actors

14

(9)

2 Bonding aspects: From atoms to solid state

23

(42)

2.1 Chemical bonding in simple molecules

23

(12)

2.1.1 Ideal covalent bonding

23

(4)

2.1.2 Polar covalent bonding

27

(3)

2.1.3 The ionic bonding

30

(1)

2.1.4 Metallic bonding

31

(1)

2.1.5 Further intermediate forms of chemical bonding

32

(1)

2.1.6 Two-body potential functions

33

(2)

2.2 Many atoms in contact: The solid state as a giant molecule

35

(30)

2.2.1 The band model

36

(14)

2.2.2 Ionic crystals

50

(6)

2.2.3 Molecular crystals

56

(1)

2.2.4 Covalent crystals

57

(2)

2.2.5 Metallic crystals

59

(1)

2.2.6 Mixed forms of bonding in solids

60

(1)

2.2.7 Crystal structure and solid state structure

61

(4)

3 Phonons

65

(7)

3.1 Einstein and Debye models

65

(4)

3.2 Complications

69

(3)

4 Equilibrium thermodynamics of the perfect solid

72

(36)

4.1 Preliminary remarks

72

(1)

4.2 The formalism of equilibrium thermodynamics

72

(14)

4.3 Examples of equilibrium thermodynamics

86

(22)

4.3.1 Solid-solid phase transition

86

(2)

4.3.2 Melting and evaporation

88

(1)

4.3.3 Solid-solid reaction

89

(1)

4.3.4 Solid-gas reaction

89

(4)

4.3.5 Phase equilibria and mixing reactions

93

(7)

4.3.6 Spatial equilibria in inhomogeneous systems

100

(3)

4.3.7 Thermodynamics of elastically deformed solids

103

(1)

4.3.8 The thermodynamic functions of state of the perfect solid

104

(4)

5 Equilibrium thermodynamics of the real solid

108

(160)

5.1 Preliminary remarks

108

(1)

5.2 Equilibrium thermodynamics of point defect formation

109

(16)

5.3 Equilibrium thermodynamics of electronic defects

125

(9)

5.4 Higher-dimensional defects

134

(21)

5.4.1 Equilibrium concentration

134

(2)

5.4.2 Dislocations: Structure and energetics

136

(4)

5.4.3 Interfaces: Structure and energetics

140

(6)

5.4.4 Interfacial thermodynamics and local mechanical equilibria

146

(9)

5.5 Point defect reactions

155

(22)

5.5.1 Simple internal defect equilibria

155

(6)

5.5.2 External defect equilibria

161

(16)

5.6 Doping effects

177

(23)

5.7 Interactions between defects

200

(17)

5.7.1 Associates

201

(9)

5.7.2 Activity coefficients

210

(7)

5.8 Boundary layers and size effects

217

(51)

5.8.1 General

217

(6)

5.8.2 Concentration profiles in the space charge zones

223

(5)

5.8.3 Conductivity effects

228

(5)

5.8.4 Defect thermodynamics of the interface

233

(8)

5.8.5 Examples and supplementary comments

241

(27)

6 Kinetics and irreversible thermodynamics

268

(131)

6.1 Transport and reaction

268

(15)

6.1.1 Transport and reaction in the light of irreversible thermodynamics

269

(6)

6.1.2 Transport and reaction in the light of chemical kinetics

275

(8)

6.2 Electrical mobility

283

(11)

6.2.1 Ion mobility

283

(9)

6.2.2 Electron mobility

292

(2)

6.3 Phenomenological diffusion coefficients

294

(13)

6.3.1 Ion conduction and self-diffusion

295

(1)

6.3.2 Tracer diffusion

296

(4)

6.3.3 Chemical diffusion

300

(5)

6.3.4 A comparison of the phenomenological diffusion coefficients

305

(2)

6.4 Concentration profiles

307

(5)

6.5 Diffusion kinetics of stoichiometry change

312

(7)

6.6 Complications of matter transport

319

(19)

6.6.1 Internal interactions

319

(13)

6.6.2 Boundary layers and grain boundaries

332

(6)

6.7 Surface reactions

338

(24)

6.7.1 Elementary processes

338

(2)

6.7.2 Coupled reactions

340

(7)

6.7.3 Phenomenological rate constants

347

(14)

6.7.4 Reactivity, chemical resistance and chemical capacitance

361

(1)

6.8 Catalysis

362

(5)

6.9 Solid state reactions

367

(15)

6.9.1 Fundamental principles

367

(11)

6.9.2 Morphological and mechanistic complications

378

(4)

6.10 Nonlinear phenomena

382

(17)

6.10.1 Irreversible thermodynamics and chemical kinetics far from equilibrium, and the special role of autocatalysis

382

(6)

6.10.2 Nonequilibrium structures in time and space

388

(5)

6.10.3 The concept of fractal geometry

393

(6)

7 Solid state electrochemistry: Measurement techniques and applications

399

(101)

7.1 Preliminary remarks: Current and voltage in the light of defect chemistry

399

(5)

7.2 Open circuit cells

404

(14)

7.2.1 Equilibrium cells: Thermodynamic measurements and potentiometric sensors

404

(9)

7.2.2 Permeation cells and chemical polarization: Measurement of transport parameters and chemical filters

413

(5)

7.3 Cells under current load

418

(63)

7.3.1 Electrochemical pumps, conductivity sensors and other applications

418

(6)

7.3.2 Measurement cells

424

(2)

7.3.3 Bulk and phase boundary effects

426

(18)

7.3.4 Stoichiometry polarization

444

(16)

7.3.5 Coulometric titration

460

(2)

7.3.6 Impedance spectroscopy

462

(11)

7.3.7 Inhomogeneities and heterogeneities: Many point measurements and point electrodes

473

(8)

7.4 Cells generating current

481

(19)

7.4.1 General

481

(1)

7.4.2 Fuel cells

482

(5)

7.4.3 Batteries

487

(8)

7.4.4 Tables

495

(5)

8 Bibliography

500

(27)

Index

527

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Physical Chemistry of Ionic Materials Ions and Electrons in Solids

Summary

Author Biography

Table of Contents

Supplemental Materials

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Rent More, Save More! Use code: BBRENTAL

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Physical Chemistry of Ionic Materials Ions and Electrons in Solids

Summary

Author Biography

Table of Contents

Supplemental Materials

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