Chemistry of the Solid-Water Interface

Provides an introduction to the chemistry of the solid-water interface, progressing from the simple to more complex and applied. Discusses the important interfaces in natural systems, especially geochemistry, in natural waters, soils and sediments. The processes occurring at mineral-water, particle-water and organism-water interfaces play critical roles in regulating the composition and ecology of oceans and fresh waters, the development of soils and plant nutrient's supply, preserving the integrity of water repositories and in such applications as water technology and corrosion science.

WERNER STUMM is Professor and Head of the Institute for Water Resources and Water Pollution Control associated with the Swiss Federal Institute of Technology in Zurich, Switzerland. He received the Tyler Prize for Environmental Achievement, the Albert Einstein World Award of Science, the Monsanto Prize for Pollution Control, and has been awarded numerous international honorary degrees. He is the author of Aquatic Chemistry and Gewasser als Okosysteme, and has edited four other books. Dr. Stumm received his PhD in chemistry from the University of Zurich; he was a professor of applied chemistry at Harvard University until 1970.

Preface

ix

Introduction - Scope of Aquatic Surface Chemistry

1

(12)

Appendix: The International Units, some useful Conversion Factors, and numerical Constants

9

(3)

Reading Suggestions

12

(1)

The Coordination Chemistry of the Hydrous Oxide-Water Interface

13

(30)

Introduction

13

(2)

The Acid-Base Chemistry of Oxides; pH of Zero Point of Charge

15

(6)

Surface Complex Formation with Metal Ions

21

(3)

Ligand Exchange: Surface Complex Formation of Anions and Weak Acids

24

(6)

Affinities of Cations and Anions for Surface Complex Formation with Oxides and Silicates

30

(7)

The Coordinative Unsaturation of Non-Hydrous Oxide Surfaces

37

(6)

Problems

39

(2)

Reading Suggestions

41

(2)

Surface Charge and the Electric Double Layer

43

(44)

Introduction - Acquiring Surface Charge

43

(4)

The Net Total Particle Charge; Surface Potential

47

(4)

The Relation between pH, Surface Charge and Surface Potential

51

(5)

A Simplified Double Layer Model; (Constant Capacitance)

56

(11)

Correcting Surface Complex Formation Constants for Surface Charge

67

(8)

Some Thermodynamic Aspects of Interactions on Oxide Surfaces

75

(12)

Appendix: A.3.1 The Gouy-Chapman Theory

79

(3)

A.3.2 The solid Phase; References

82

(1)

Problems

83

(3)

Reading Suggestions

86

(1)

Adsorption

87

(70)

Introduction - Intermolecular Interaction between Solute and Solid Phase

87

(1)

Gibbs Equation on the Relationship between Interfacial Tension and AdsorptionK

88

(2)

Adsorption Isotherms

90

(7)

Adsorption Kinetics

97

(10)

Fatty Acids and Surfactants

107

(5)

Humic Acids

112

(2)

The Hydrophobic Effect

114

(2)

The ``Sorption'' of Hydrophobic Substances to Solid Materials that contain Organic Carbon

116

(4)

The Sorption of Polymers

120

(6)

Reversibility of Adsorption

126

(3)

Ion Exchange

129

(5)

Transport of Adsorbable Constitutents in Ground Water and Soil Systems

134

(23)

Appendix: A.4.1 Contact Angle, Adhesion and Cohesion

142

(5)

A.4.2 Electrocapillarity

147

(6)

Problems

153

(2)

Reading Suggestions

155

(2)

The Kinetics of Surface Controlled Dissolution of Oxide Minerals; an Introduction to Weathering

157

(54)

Introduction - Chemical Weathering

157

(5)

A General Rate Law for Surface Controlled Dissolution

162

(3)

Ligand Promoted Dissolution

165

(4)

The Proton-Promoted Dissolution Reaction

169

(6)

Some Case Studies

175

(4)

Case Study: Kaolinite

179

(6)

Experimental Apparatus

185

(2)

Incongruent Dissolution as a Transient to Congruent Dissolution

187

(2)

Weathering and the Environmental Proton Balance

189

(2)

Comparison between Laboratory and Field Weathering Results

191

(6)

Case Study: Chemical Weathering of Crystalline Rocks in the Catchment Area of Acidic Ticino Lakes, Switzerland

197

(2)

Inhibition of Dissolution; Passivity

199

(12)

Appendix: Akalinity, a ``Product of Weathering''

206

(3)

Reading Suggestions

209

(2)

Precipation and Nucleation

211

(32)

Introduction - The Initiation and Production of the Solid Phase

211

(3)

Homegeneous Nucleation

214

(3)

Heterogeneous Necleation

217

(2)

The Interfacial Energy and the Ostwald Step Rule

219

(5)

Enhancement of Heterogeneous Nucleation by Specific Adsorption of Mineral Constituents

224

(5)

Surface Precipitation

229

(4)

Crystal Growth

233

(10)

Appendix: A.6.1 Solubility of Fine Particles

235

(1)

A.6.2 Solid Solution Formation

236

(6)

Reading Suggestions

242

(1)

Particle-Particle Interaction

243

(46)

Introduction - Aquatic Particles as Adsorbents and Reactants

243

(4)

Kinetics of Particle Agglomeration

247

(4)

Colloid-Stability; Qualitative Considerations

251

(2)

Colloid-Stability; Effects of Surface Chemistry on Surface Potential

253

(9)

A Physical Model for Colloid Stability

262

(5)

Filtration compared with Coagulation

267

(4)

Coagulation in Lakes

271

(5)

Some Water-Technological Considerations in Coagulation and Floation

276

(4)

Bacterial Adhesion; Hydrophobic and Electrostatic Parameters

280

(2)

Colloids; The Use of (Memberane) Filtration to seaprate ``Particulate'' from ``Dissolved'' Matter

282

(7)

Appendix: Distribution Coefficients, Possible Artefacts

286

(2)

Reading Suggestions

288

(1)

Carbonates and their Reactivities

289

(20)

Introduction

289

(1)

Dissolution and Crystal Growth of Carbonates

290

(3)

The Crystal Growth of CaCO3 (Calcite)

293

(1)

Saturation State of Lake Water and Seawater with Respect to CaCO3

294

(3)

Some Factors in the Diagenesis of Carbonates

297

(1)

Coprecipitation Reactions and Solid Solutions

298

(3)

Magnesian Calcite

301

(8)

Appendix: Carbonate Solubility Equilibria

304

(3)

Reading Suggestionsk

307

(2)

Redox Processes Mediated by Surfaces

309

(28)

Specific Adsorption of Oxidants and Reductions

309

(2)

Some Thermodynamic Considerations

311

(2)

Catalysis of Redox Reactions by Surfaces

313

(12)

Oxidation of Transition Ions; Hydrolysis and Surface Binding Enhance Oxidation

325

(4)

Mediation of Redox Reactions of Organic Substances by the Hydrosus Freric Oxide Surface and Fe(II)-Survaces

329

(2)

Redox Reactions of Iron and Managanese at the Oxic Anoxic Boundary in WEaters and Soils

331

(6)

Reading Suggestions

335

(2)

Heterogeneous Photochemistry

337

(32)

Heterogeneous Photosynthesis

337

(5)

Semiconducting Minerals

342

(5)

Kinetics of Heterogenesous Photoredox Reactions and the Role of Surface Complexiation

347

(5)

Case Studies on Heterogeneous Photoredox Reactions

352

(9)

The Cycling of Iron in Natural Systems; Some Aspects Based on Heterogeneous Redox Processes

361

(8)

Reading Suggestions

367

(2)

Regulation of Trace Elements by the Solid-Water Interface in Surface Waters

369

(28)

Introduction

369

(1)

The Particle Surface as a Carrier of Functional Groups

369

(5)

Titrating Metal Ions with Particles

374

(4)

Regulation of Dissolved Heavy Metals in Rivers

378

(3)

Regulation of Trace Elements in Lakes

381

(12)

Oceans

393

(4)

Reading Suggestions

396

(1)

References

397

(22)

Index

419

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Chemistry of the Solid-Water Interface Processes at the Mineral-Water and Particle-Water Interface in Natural Systems

Summary

Author Biography

Table of Contents

Supplemental Materials