Content: Simulating liquid water near mineral surfaces : current methods and limitations / David J. Mulla --
Behavior of water on the surface of kaolin minerals / R.F. Giese Jr. and P.M. Costanzo --
Reactions at the oxide-solution interface : chemical and electrostatic models / John C. Westall --
Surface potential-pH characteristics in the theory of the oxide-electrolyte interface / Luc Bousse and J.D. Meindl --
Free energies of electrical double layers at the oxide-solution interface / Derek Y.C. Chan --
Mechanism of lead ion adsorption at the goethite-water interface / Kim F. Hayes and James O. Leckie --
Characterization of anion binding on goethite using titration calorimetry and cylindrical internal reflection-Fourier transform infrared spectroscopy / W.A. Zeltner ... [et al.] --
Macroscopic partitioning coefficients for metal ion adsorption : proton stoichiometry at variable pH and adsorption density / Bruce D. Honeyman and James O. Leckie --
Sorption of hydrophobic organic compounds by sediments / Gary P. Curtis, Martin Reinhard, and Paul V. Roberts --
Distinguishing adsorption from surface precipitation / Garrison Sposito --
Adsorption-desorption kinetics at the metal-oxide-solution interface studied by relaxation methods / Tatsuya Yasunaga and Tetsuya Ikeda --
Highly selective ion exchange in clay minerals and zeolites / A. Maes and A. Cremers --
Potassium fixation in smectite by wetting and drying / Dennis D. Eberl, Jan Środoń, and H. Roy Northrop --
Potassium-calcium exchange equilibria in aluminosilicate minerals and soils / Keith W.T. Goulding --
Adsorption of metal ions and complexes on aluminosilicate minerals / B.A. Goodman --
Paramagnetic probes of layer silicate surfaces / Murray B. McBride --
Applications of surface techniques to chemical bonding studies of minerals / Dale L. Perry --
In situ Mössbauer studies of metal oxide-aqueous solution interfaces with adsorbed cobalt-57 and antimony-119 ions / F. Ambe ... [et al.] --
Photoredox chemistry of colloidal metal oxides / T. David Waite --
Adsorption of organic reductants and subsequent electron transfer on metal oxide surfaces / Alan T. Stone --
Abiotic organic reactions at mineral surfaces / Evangelos A. Voudrias and Martin Reinhard --
Mn(II) oxidation in the presence of lepidocrocite: the influence of other ions / Simon H.R. Davies --
Interaction of Co(II) and Co(III) complexes on synthetic birnessite : surface characterization / John G. Dillard and Catherine V. Schenck --
Ionic solid solutions in contact with aqueous solutions / Ferdinand C.M. Driessens --
Approach to equilibrium in solid solution-aqueous solution systems : the KCl-KBr-H₂O system at 25°C / L. Niel Plummer --
Modes of coprecipitation of Ba² and Sr² with calcite / Nicholas E. Pingitore Jr. --
Near-surface alkali diffusion into glassy and crystalline silicates at 25°C to 100°C / Art F. White and Andy Yee --
Mechanisms and rate laws in electrolyte crystal growth from aqueous solution / Arne E. Nielsen --
Influence of surface area, surface characteristics, and solution composition on feldspar weathering rates / Michael Anthony Velbel --
Dislocation etch pits in quartz / S.L. Brantley ... [et al.] --
The growth of calcium phosphates / S.J. Zawacki ... [et al.].
Author(s): James A. Davis and Kim F. Hayes (Eds.)
Series: ACS Symposium Series 323
Publisher: American Chemical Society
Year: 1987
Language: English
Pages: 684
City: Washington, DC
Title Page......Page 1
Half Title Page......Page 3
Copyright......Page 4
ACS Symposium Series......Page 5
FOREWORD......Page 6
PdftkEmptyString......Page 0
PREFACE......Page 7
1 Geochemical Processes at Mineral Surfaces: An Overview......Page 9
Physical Properties of the Mineral-Water Interface......Page 10
Adsorption......Page 12
Ion Exchange......Page 14
Surface Spectroscopy......Page 16
Dissolution, Precipitation, and Solid Solution Formation......Page 17
Transformation Reactions at the Mineral/Water Interface......Page 20
Literature Cited......Page 21
2 Simulating Liquid Water near Mineral Surfaces: Current Methods and Limitations......Page 26
General Simulation Approaches......Page 27
Interaction Potentials......Page 29
Simulations of Interfacial Water......Page 34
Summary......Page 38
Literature Cited......Page 40
3 Behavior of Water on the Surface of Kaolin Minerals......Page 43
Clay Mineral Structures......Page 44
Experimental Studies of Water on Kaolin Minerals......Page 49
Application of Results to other Silicate Minerals......Page 56
Summary......Page 57
Literature Cited......Page 58
4 Reactions at the Oxide-Solution Interface: Chemical and Electrostatic Models......Page 60
The Oxide-Electrolyte Interface in Geochemistry......Page 61
Conceptual Model of an Adsorption Reaction......Page 63
Surface Complexation Models......Page 65
Electrostatic Models for the Electric Double Layer......Page 70
Interpretation of Data......Page 74
Concluding Remarks......Page 81
Legend of Symbols......Page 82
Literature Cited......Page 83
5 Surface Potential-pH Characteristics in the Theory of the Oxide-Electrolyte Interface......Page 85
Model for an Amphoteric Surface without Complexation......Page 86
Model for an Amphoteric Surface with Complexation......Page 92
Determination of Surface Equilibrium Constants......Page 95
Conclusions......Page 100
Legend of Symbols......Page 102
Literature Cited......Page 103
6 Free Energies of Electrical Double Layers at the Oxide-Solution Interface......Page 105
a . The Oxide Surface......Page 106
b . The Diffuse Double Layer......Page 108
c . The Equilibrium Point......Page 109
Free Energy of Formation of One Surface......Page 112
Interaction Free Energy Between Two Plates......Page 115
Literature Cited......Page 118
7 Mechanism of Lead Ion Adsorption at the Goethite-Water Interface......Page 119
Experimental Materials and Methods......Page 120
Equilibrium Model......Page 122
Triple Layer Model......Page 123
Equilibrium Results......Page 126
Kinetic Model......Page 130
Kinetic Results......Page 132
Summary......Page 137
Pressure-Jump Apparatus with Conductivity Detection......Page 138
Net Proton Release and Ligand Number......Page 141
Derivation of the Time Constant Relationship of Equation 35......Page 143
Legend of Symbols......Page 144
Literature Cited......Page 145
8 Characterization of Anion Binding on Goethite Using Titration Calorimetry and Cylindrical Internal Reflection-Fourier Transform Infrared Spectroscopy......Page 147
Titration Calorimetry......Page 148
Cylindrical Internal Reflection - Fourier Transform Infrared (CIR-FTIR) Spectroscopy......Page 155
Acknowledgments......Page 163
Literature Cited......Page 164
9 Macroscopic Partitioning Coefficients for Metal Ion Adsorption Proton Stoichiometry at Variable pH and Adsorption Density......Page 167
Determination of χ(ρΗ,Γ) as a Macroscopic Model Parameter......Page 174
Summary......Page 191
APPENDIX I THE MATHEMATICAL DEVELOPMENT OF ISOTHERM ANALYSIS FOR THE MACROSCOPIC PROTON COEFFICIENT, Xp......Page 192
Literature Cited......Page 194
10 Sorption of Hydrophobic Organic Compounds by Sediments......Page 196
Adsorption Mechanisms......Page 197
Partitioning Thermodynamics......Page 199
Nonidealities in Humic Polymers......Page 202
Aqueous-Phase Nonidealities......Page 205
Limitations of Partitioning Theory......Page 208
Sorption Kinetics......Page 213
Summary and Conclusions......Page 216
Symbols:......Page 217
Acknowledgments......Page 218
Literature Cited......Page 219
11 Distinguishing Adsorption from Surface Precipitation......Page 222
Solubility Methods......Page 223
Kinetics Methods......Page 227
Surface Spectroscopy......Page 229
Literature Cited......Page 231
12 Adsorption-Desorption Kinetics at the Metal-Oxide-Solution Interface Studied by Relaxation Methods......Page 234
Experimental Methods and Materials......Page 235
Surface Reaction Kinetics......Page 236
Intercalation Kinetics......Page 248
Literature Cited......Page 256
13 Highly Selective Ion Exchange in Clay Minerals and Zeolites......Page 258
Thermodynamic background......Page 259
Influence of interlayer charge density and interlayer hydration......Page 260
Exchange of cations of high polarizability......Page 269
Highly selective exchange in illite and modified montmorillonites......Page 278
Reversibility......Page 284
Highly selective exchange as related to the presence of crystallographically different site groups......Page 287
Exchange of transition metal ion uncharged ligand complexes......Page 292
Literature Cited......Page 294
14 Potassium Fixation in Smectite by Wetting and Drying......Page 300
Previous Work......Page 301
Aims of the Present Study......Page 302
Materials and Methods......Page 303
Experimental Results......Page 307
Conclusions......Page 326
Literature Cited......Page 328
15 Potassium-Calcium Exchange Equilibria in Aluminosilicate Minerals and Soils......Page 331
Methods......Page 332
Results and Discussion......Page 334
Conclusions......Page 342
Literature Cited......Page 343
16 Adsorption of Metal Ions and Complexes on Aluminosilicate Minerals......Page 345
The nature of clay surfaces......Page 347
Adsorption of metal ions on minerals......Page 349
Characterization of chemical forms of adsorbed metal ions......Page 351
Adsorption and characterization of complex species on minerals......Page 356
Reactions involving metal ions adsorbed on minerals......Page 358
Conclusions......Page 360
Literature Cited......Page 361
17 Paramagnetic Probes of Layer Silicate Surfaces......Page 365
Materials and Methods......Page 368
Results and Discussion......Page 369
Literature Cited......Page 390
18 Applications of Surface Techniques to Chemical Bonding Studies of Minerals......Page 392
X-Ray Photoelectron Spectroscopy (XPS)......Page 394
Auger Electron Spectroscopy (AES)......Page 398
Combined X-Ray Photoelectron/X-Ray-Induced Auger Spectroscopy(XPS/XAES)......Page 400
Literature Cited......Page 404
Principles......Page 406
Experimental Section......Page 408
Experimental Results......Page 409
Analysis of the Mossbauer Data......Page 417
Discussion......Page 422
Future Prospect......Page 426
Literature Cited......Page 427
20 Photoredox Chemistry of Colloidal Metal Oxides......Page 428
Light Absorption by the Metal Oxide Bulk......Page 429
Light Absorption by Surface-Located Chromophores Incorporating the Metal of the Oxice Lattice......Page 431
Effect of Metal Oxide Surface Properties on Photoinduced Redox Reactions......Page 443
Literature Cited......Page 445
21 Adsorption of Organic Reductants and Subsequent Electron Transfer on Metal Oxide Surfaces......Page 448
Reductive Dissolution: Overall Reaction Scheme......Page 449
Surface Chemical Reaction Mechanism......Page 450
Description of Reductive Dissolution on a Molecular Level......Page 453
Conclusions......Page 461
Literature Cited......Page 462
22 Abiotic Organic Reactions at Mineral Surfaces......Page 464
Reactions Promoted by the Lewis and Bronsted Acidity of Clay Minerals......Page 466
Oxidation of Organic Compounds by Oxides and Primary Minerals......Page 482
Acknowledgments......Page 485
Literature Cited......Page 486
23 Mn(II) Oxidation in the Presence of Lepidocrocite: The Influence of Other Ions......Page 489
Objectives......Page 490
Experimental......Page 491
Results and Discussion......Page 492
Mn(II) Oxidation in Natural Waters: Implications of Experimental Studies......Page 499
Acknowledgments......Page 502
Literature Cited......Page 503
24 Interaction of Co(II) and Co(III) Complexes on Synthetic Birnessite: Surface Characterization......Page 505
Methods and Materials......Page 507
XPS Studies/Characterization......Page 509
SIMS Analysis......Page 516
Summary......Page 521
Literature Cited......Page 523
25 Ionic Solid Solutions in Contact with Aqueous Solutions......Page 525
The Roozeboom Classification......Page 526
DISTRIBUTION LAWS AND SUBSTITUTIONAL DISORDER......Page 534
Application In Analytical And Inorganic Chemistry......Page 536
The System CaCO3 - MqCO3......Page 541
The System Hydroxyapatite - Fluorapatite......Page 545
Literature Cited......Page 559
26 Approach to Equilibrium in Solid Solution-Aqueous Solution Systems: The KCl-KBr-H2O System at 25°C......Page 562
KCl-KBr-H2O System at 25°C......Page 563
Theory......Page 564
Equilibrium Constants......Page 567
Test for Equilibrium......Page 568
Conclusion......Page 573
Literature Cited......Page 574
27 Modes of Coprecipitation of Ba2+ and Sr2+ with Calcite......Page 575
The Incorporation of Sr(II) into Calcite: A Review......Page 576
Experimental Methods for Coprecipitation of Ba(II) with Calcite......Page 577
Ba(II) Experiments:Results and Discussion......Page 578
EPR Studies of Sr(II) and Ba(II) in Calcite......Page 584
Implications......Page 585
Literature Cited......Page 586
Experimental Results......Page 588
Experimental Results......Page 589
Calculation of Diffusion Parameters......Page 593
Discussion......Page 596
Acknowledgments......Page 598
Literature Cited......Page 599
29 Mechanisms and Rate Laws in Electrolyte Crystal Growth from Aqueous Solution......Page 600
Transport Controlled Kinetics......Page 601
Surface Controlled Kinetics......Page 604
Estimates of Parameters......Page 606
Prediction of Growth Rates......Page 607
Discussion......Page 610
Conclusion......Page 611
Legend of Symbols......Page 612
Literature Cited......Page 613
30 Influence of Surface Area, Surface Characteristics, and Solution Composition on Feldspar Weathering Rates......Page 615
Parabolic Kinetics......Page 616
Petrographic Observations......Page 620
Surface Composition......Page 623
Laboratory Studies of Feldspar Weathering - A Summary......Page 625
Rates of Feldspar Weathering in the Laboratory......Page 626
Rates of Feldspar Weathering in Natural Weathering Profiles from Geochemical Mass Balance of Small Watersheds......Page 627
Summary and Evaluation......Page 629
Conclusions......Page 631
Literature Cited......Page 632
31 Dislocation Etch Pits in Quartz......Page 635
Theory of Etch Pit Formation......Page 636
Etch Pits in Quartz: A Test of the Theory......Page 639
Conclusions and Implications for Future Research......Page 645
Legend of Symbols......Page 647
Literature Cited......Page 648
32 The Growth of Calcium Phosphates......Page 650
Experimental......Page 653
Results and Discussions......Page 654
Literature Cited......Page 661
Author Index......Page 663
A......Page 664
C......Page 666
D......Page 668
E......Page 669
G......Page 671
I......Page 672
K......Page 673
M......Page 674
O......Page 676
P......Page 677
R......Page 679
S......Page 680
T......Page 683
Z......Page 684
