SOIL COLLOIDS PROPERTIES AND ION RINDING. CRC Press. University of Bueno Aires Buenos Aires, Argentina. Taylor & Francis Croup
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1 SOIL COLLOIDS PROPERTIES AND ION RINDING Fernando V. Molina University of Bueno Aires Buenos Aires, Argentina CRC Press Taylor & Francis Croup Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Croup, an informa business
2 Contents Preface List of Common Greek Symbols List of Common Symbols List of Common Acronyms xxi xxiii xxv xxvii PART I Foundations Chapter 1 Introduction Soil Soil Chemistry, Soil Colloids, and Metal Ions Book Contents 4 References 5 Chapter 2 Colloidal Particles and Colloidal Suspensions Colloidal Particles Soil Colloids Colloidal Suspensions: General Properties and Classification Importance of Surface in Colloidal Systems Surface Energy Fundamentals of Interfacia) Thermodynamics Surface Excesses i Gibbs Equation Summary 24 References 25 Chapter 3 Electrified Interface Basic Principles Electrochemical Equilibrium Poisson and Poisson-Boltzmann Equations Poisson Equation Poisson-Boltzmann Equation Application of the Poisson-Boltzmann Equation Linearization of the PB Equation and the Debye-Huckel Theory Gouy-Chapman Theory 3s xiii
3 (jv Contents Analytical Solutions for Other Cases Cylindrical Coordinates Other Cases Numerical Solutions to the Poisson-Boltzmann Equation Interfacial Capacitance and the Stern and Grahame Models Interfacial Capacitance Stern Modification Grahame Modification of the Gouy-Chapman- Stern Theory Beyond the Poisson-Boltzmann Equation Approximate Solutions of the PB Equation Summary 56 References 56 Chapter 4 Sorption onto Colloidal Particles General Concepts Sorption Isotherms Gas Phase Isotherm Types Isotherm Classification for Sorption from Solution Physical Nature of Adsorption Adsorption from Gas Phase Adsorption from Solution Interaction between a Molecule or Ion and a Surface Intermolecular Interactions Interactions with a Macroscopic Particle Theory of Adsorption Isotherms Limiting (Henry) Isotherm Ideal Monolayer: Langmuir Isotherm Competitive and Multisite Langmuir Isotherms Ideal Multilayer (BET) Isotherm Beyond Ideal Isotherms Adsorption with Interactions: The Fowler- Guggenheim Isotherm Surface Heterogeneity Sips Distribution Function Langmuir-Freundlich and Freundlich Isotherms Other Isotherm Equations Isotherm Comparison and Assignment Summary 106 References 106
4 Contents xv Chapter 5 Surface Charge of Colloidal Particles Contributions to Surface Charge Permanent Charge Ill Protonic and Intrinsic Charge Inner and Outer Sphere Complex Charges Particle Charge Balance Soil Charge Ion Sorption and Surface Charge Development Ion Exchange Thermodynamics of Ion Exchange: Vanselow Convention Other Conventions and Selectivity Coefficient Expressions Kerr Convention Gaines and Thomas Convention Krishnamoorthy and Overstreet Convention Gapon Selectivity Coefficient Cerniketal. Convention Other Aspects Ion Exchange Analysis and Parameter Computation Argensinger Method Rothmund-Kornfeld Method Ion Exchange in Soils Examples of Ion Exchange in Soils Ion Preference Determination of Surface Charge Electrophoretic Methods Titration Methods Charge Contributions and Points of Zero Charge Indifferent Electrolytes Charge in the Presence of Specific Adsorption Summary 153 References '54 Chapter 6 Interparticle Interactions and Colloid Stability Thermodynamics of Particle-Particle Interaction van der Waals Particle-Particle Interactions Energies and Forces of Interaction Eleciroslatic Interactions 16H Constant Potential Conditions Linear Approximation: The Hogg- Healy-Fuerstenau Theory 170
5 xvi Contents Identical Particles: Verwey-Overbeek Results Derjaguin Theory Constant Charge Conditions and Comparison with Constant Potential Charge Regulation Total Long-Range Interactions Similar Surfaces: Classic DLVO Theory Dissimilar Particles Colloidal Suspension Stability Beyond DLVO DLVO Theory Limitations DLVO Extensions Alternative Models Summary 192 References 193 PART II Soil Components Chapter 7 Soil Composition and Characterization General Characteristics Soil Structure Gas, Liquid, and Solid Soil Phases Soil Particles Soil Solution Soil Composition Soil Minerals Primary Minerals Secondary Minerals Structural Elements of Soil Minerals 2! Soil Organic Matter Humic Substances Nonhumic Substances X-Ray-Based Characterization Methods X-Ray Diffraction X-Ray Absorption-Based Methods X-Ray Fluorescence X-Ray Photoelectron Spectroscopy Other Spectroscopic Methods UV-Visible Molecular Spectrometries UV-Visible Atomic Spectrometry Infrared Spectroscopy Nuclear Magnetic Resonance 232
6 Contents xvii 7.5 Microscopies Optical Microscopy Electron Microscopy Atomic Force Microscopy Miscellaneous Methods Neutron Activation Analysis Electrophoretic Separations Field-Flow Fractionation Surface Area Measurement Physical Methods Positive Adsorption Methods Negative Adsorption Methods Thermal Analysis Methods Differential Thermal Analysis Differential Scanning Calorimetry Thermogravimetry Chemical Characterization Soil Analysis Summary 255 References 255 Chapter 8 Silicate-Based Minerals Structure and Classification of Silicate-Based Minerals Kaolin-Serpentine Group (1:1) Clays Low Permanent Charge 2:1 Phyllosilicates: Pyrophyllite- Talc Group Permanently Charged 2:1 Phyllosilicate Minerals Micas Vermiculites Smectites Chlorites Interstratified Phyllosilicates Other Aluminosilicate Minerals Allophane and Imogolite Palygorskite and Sepiolite Zeolites Characterization of Silicate Minerals Identification and Crystalline Structure Ion Exchange Specific Surface Area Ion Binding to Silicate-Based Minerals Summary 293 References 295
7 xvjjj Contents Chapter 9 Oxide Minerals Silica Minerals Aluminum (Hydr)Oxides Iron (Hydr)Oxides.' Manganese Oxides Titanium and Zirconium Oxide Minerals Titanium Oxides Zirconium Minerals Characterization of Oxides Identification and Crystalline Structure Spectroscopic Studies Specific Surface Area and Surface Charge Miscellaneous Methods Ion Binding to Oxide Minerals Cation Binding Anion Binding Summary 332 References 332 Chapter 10 Humic Substances Nature and Classification of Soil Humic Substances Extraction of HS Alkaline Extraction Mild Extractants Na4P207 and Other Neutral Salts Formic Acid (HCOOH) Organic Chelating Agents Sequential Extractions Characterization, Composition, and Structure of HS Elemental Composition Molecular Weight and Size Distributions Colligative Properties Light Scattering Size-Exclusion Chromatography Ultracentrifugation Viscosimetry Microscopic Observation Other Techniques Spectroscopic Methods Infrared Spectroscopy Nuclear Magnetic Resonance UV-Visible and Fluorescence Spectroscopy 352
8 Contents xix Functional Groups and Acid-Base Properties Functional Group Analysis Structural Studies by Chemical Degradative Methods Structural Studies by Thermal Degradation Molecular Structure of HS Ion Binding to Hs Summary 373 References 373 PART III Ion Binding to Soil Colloids Chapter 11 Modeling Ion Binding: General Concepts General Problem Chemical Modeling Modeling Bases Affinity Spectra Discrete Affinity Spectra Proton-Binding Equilibrium Competitive Binding Continuous Affinity Spectra Proton Binding Competitive Metal Binding Extraction of Affinity Spectra Intrinsic and Conditional Equilibrium Constants Semianalytical Methods Modified Least Squares Methods Maximum Entropy Formalism Kinetic Aspects Summary 408 References 408 Chapter 12 Ion Binding to Minerals: Discrete Site Modeling Ion Binding to Mineral Components Generic Surface Description: Classical Electrostatic Models Triple-Layer Model Model Statement Applications of the Triple-Layer Model Further Advances: Extended Triple-Layer Model 422
9 XX Contents Simplified Modeling: Basic Stern and Constant Capacitance Models Stern Extended or Quad Layer Model Detailed Surface Description: CD-MUSIC Model Model Formulation Application of the CD-MUSIC Model Comparison between Models Application to Charge Regulation between Particles Summary 441 References 442 Chapter 13 Ion Binding to Humic Substances: Distributed Site Modeling Ion Binding to Soil Organic Matter Affinity Spectra of Humic Substances Discrete Affinity Spectra Continuous Affinity Spectra Structure-Based Affinity Spectra Electrostatic Modeling of Ion Binding to Humic Particles Particle Models Donnan Phase Models Models for Ion Binding to Humic Substances Windermere Humic Models Stockholm Humic Model NICA-Donnan Model NICA-EPN Model Comparison of the Different Models Summary 472 References 473 Chapter 14 Ion Binding to Soils State of Soil Components in Natural Soils Ion Binding to Several Soil Components Additivity Rule Sorption to Binary and Ternary Component Systems Sorption in Complex Systems and Whole Soils Models for Ion Sorption to Soils Assemblage Models Incorporation of HS-Mineral Interaction: LCD Model Summary and Perspectives 495 References 496 Index 501
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