Clathrate Hydrates, 2 Volumes

Volume 1 Preface xiii 1 An Introduction to Clathrate Hydrate Science 1 John A. Ripmeester, Saman Alavi, and Christopher I. Ratcliffe 1.1 Introduction 1 1.2 Selected Highlights of Clathrate Hydrate Science Research Up to the Present 4 1.3 Clathrate Hydrate Research at the NRC Canada 10 1.4 Contributors to NRC Clathrate Hydrate Research 21 1.5 Review Articles and Books on Clathrate Hydrates 23 1.6 Conference Proceedings 25 1.6.1 Canadian Permafrost Conference 25 1.6.2 Physics and Chemistry of Ice 25 1.6.3 International Conference on Gas Hydrates (IGCH) Proceedings 26 2 An Introduction to Clathrate Hydrates 27 John A. Ripmeester and Saman Alavi 2.1 Introduction 27 2.2 The First Gas Hydrates 28 2.3 The Phase Rule 34 2.4 de Forcrand and Villard – Career Gas Hydrate Researchers 38 2.5 Nikitin and von Stackelberg 48 2.6 Solving the Gas Hydrate Puzzle 50 2.7 Clathrate Hydrate Science – A New Era 54 2.8 Clathrate Hydrates in Engineering 54 2.9 Clathrate Hydrates in Nature 55 2.10 Summary and Observations 56 References 57 3 Classification of Clathrate Hydrates 65 John A. Ripmeester, Satoshi Takeya, and Saman Alavi 3.1 Introduction 65 3.2 Hydrates as Clathrates 65 3.3 Clathrate and Related Hydrates – Guest Chemistry 66 3.4 The Canonical Clathrate Hydrates 72 3.4.1 Polyhedra and Filling Three-Dimensional Space 73 3.4.2 Filling the Polyhedra 75 3.5 Phase Equilibria 85 3.5.1 Simple Hydrates 85 3.5.2 Double and Mixed Hydrates, Natural Gas Hydrates 90 3.6 Tabulation of Hydrate Properties 97 3.6.1 Simple Clathrate Hydrates 97 3.6.2 CS-II (sII) Double Hydrates (Guests that Require a Help Gas for Stability) 98 3.6.3 HS-III (sH) Hydrate Guests 98 3.7 Summary 98 References 98 4 Synthesis of Clathrate Hydrates 123 John A. Ripmeester and Saman Alavi 4.1 Introduction 123 4.2 General Considerations in the Synthesis of Clathrate Hydrates 123 4.2.1 A Complex Process 123 4.2.2 Air Entrainment 124 4.3 Synthesis of Hydrates with Water-Soluble Guests Near Ambient Conditions 125 4.3.1 Hydrates with Congruent Melting Points 125 4.3.2 Hydrates with Incongruent Melting Points 125 4.4 Synthesis of Hydrates of Guests with Low Solubility in Water 126 4.4.1 Low-Pressure Methods: Water–Liquid Guest and Water–Gaseous Guest Reactions 126 4.4.2 Powdered Ice Reactions with Liquid or Gaseous Guests 127 4.5 Synthesis of Clathrate Hydrates of Strongly Hydrated or Reactive Guests 128 4.6 Pure Hydrates – Kinetic and Thermodynamic Control 128 4.7 High-Pressure Reactors 131 4.7.1 Stirred Reactors 131 4.7.2 Stationary (Non-stirred) Reactors 131 4.7.3 Other Setups for Hydrate Synthesis – Bubble Columns, Spray Reactors 131 4.8 Synthesis of Single Crystals 134 4.9 Summary 137 References 138 5 Structures of Canonical Clathrate Hydrates 141 John A. Ripmeester, Satoshi Takeya, and Saman Alavi 5.1 Introduction 141 5.2 The Canonical Clathrate Hydrates 141 5.2.1 General Structural Properties 141 5.2.2 Geometry of Unit Cells and Cages: CS-I, CS-II, and HS-III 147 5.2.2.1 Structural Features CS-I, CS-II, and HS-III Clathrate Hydrates 147 5.2.2.2 Correlation of Guest Size with Unit Cell Dimensions 151 5.2.2.3 Flexible Guest Molecules Showing Conformational Isomerism 152 5.2.2.4 Location of Guest Molecules in the Cages 153 5.2.2.5 Effects of Hydrogen Bonding on Cage Structure and Guest–Water Interactions 158 5.2.2.6 Halogen–Water Interactions in Clathrate Hydrates (Chlorine) 160 5.2.2.7 Polymorphism 161 5.2.3 Geometry of Unit Cell and Cages: Tetragonal Bromine Hydrate (TS-I) 164 5.2.4 Geometry of Unit Cell and Cages: Dimethyl Ether Hydrate (TrS-I) 165 5.2.5 Geometry of Unit Cell and Cages: Xe Hydrate (HS-I) 166 5.3 Some General Structural Considerations 168 5.3.1 Tiling in Three-Dimensional Space – Frank–Kasper and Weaire–Phelan Polyhedra 168 5.3.2 Schlegel Diagrams 177 5.3.3 Polytypism 178 5.3.3.1 Hydrate Structures as Layered Polytypes 178 5.3.4 Materials with Structural Features in Common with Clathrate Hydrates 181 References 182 6 Structures of Noncanonical Clathrates and Related Hydrates 189 John A. Ripmeester, Satoshi Takeya, and Saman Alavi 6.1 Introduction 189 6.2 Amine Hydrates 189 6.3 Ionic Clathrate Hydrates 194 6.3.1 Salt Hydrates 194 6.3.1.1 Salt Hydrates – Cations as Large Cage Guests 194 6.3.1.2 Salt Hydrates – Cations as Large Cage Guests, Neutral Small Cage Guests 199 6.3.1.3 Salt Hydrates – Cations as Small-Cage Guests 201 6.3.2 Hydrates of Strong Acids 202 6.3.3 Hydrates of Strong Bases 204 6.3.4 Ionic Clathrate Hydrates with Heterogeneous Frameworks 209 6.3.5 Clathrates with H2O–NH4F Solid Solution Frameworks 209 References 211 7 Thermodynamics and Statistical Mechanics of Clathrate Hydrates 219 John A. Ripmeester and Saman Alavi 7.1 Introduction 219 7.2 Clathrate Hydration Numbers and Cage Occupancies 219 7.2.1 Direct Measurement of Hydration Numbers 220 7.2.2 Thermodynamic Methods to Determine Guest Occupancy 228 7.2.2.1 The Clapeyron and Clausius–Clapeyron Equations and the Use of Phase Equilibria 228 7.2.2.2 The Miller–Strong Method and Effects of Solutes on Phase Equilibria 230 7.2.2.3 Calorimetry and Other Instrumental Methods in Conjunction with Thermodynamic Methods 230 7.3 Enthalpy of Dissociation of Hydrate Phases 231 7.4 Statistical Mechanics of Clathrate Hydrates: The van der Waals–Platteeuw Solid Solution Model for Clathrate Hydrate Formation 232 7.5 Application of the van der Waals–Platteeuw Theory to Determining Hydrate Equilibrium Composition 237 7.5.1 Using van der Waals–Platteeuw Theory to Determine Cage Occupancies 237 7.5.2 Instrumental Methods in Conjunction with the van der Waals–Platteeuw Theory to Determine Occupation Fractions 239 7.5.2.1 Solid-State NMR 240 7.5.2.2 Raman Spectroscopy 243 7.5.2.3 Diffraction Methods 243 7.5.3 Some General Conclusions and Nonstoichiometry of Clathrate Hydrates 246 7.6 Computational Predictions of Hydrate Dissociation Pressures Using the van der Waals–Platteeuw Theory 247 7.7 Extensions of the van der Waals–Platteeuw Theory 254 7.7.1 Multiple Cage Occupancies and Guest Mixtures 254 7.7.2 Relaxing Some Position Restraints on Cage Water Molecules 255 7.7.3 Relaxing the Constraint of Constant Volume on the Hydrate Phase 255 7.7.4 Validity of the Basic van der Waals–Platteeuw Theory 258 7.8 Other Thermodynamic Topics 260 7.8.1 Encagement Enthalpy 260 7.8.2 Thermodynamic Inhibitors to Hydrate Formation 263 7.8.3 Compositional Tuning in Clathrate Hydrates 265 7.8.4 Transitions Between Binary CS-II and HS-III Binary Hydrates to Pure CS-I Hydrates for Small Guest Molecules 266 7.8.5 A Lower Critical Decomposition Temperature 270 7.9 Conclusions 271 References 272 Volume 2 Preface xv 8 Molecular Simulations of Clathrate Hydrates 283 Saman Alavi and John A. Ripmeester 9 X-ray and Neutron Diffraction and Scattering of Clathrate Hydrates 369 John S. Tse, Dennis D. Klug, and Satoshi Takeya 10 Characterization of Clathrate Hydrates Using Nuclear Magnetic Resonance Spectroscopy 417 Christopher I. Ratcliffe, Igor L. Moudrakovski, and John A. Ripmeester 11 Specialized Methods of Nuclear Magnetic Resonance Spectroscopy and Magnetic Resonance Imaging Applied to Characterization of Clathrate Hydrates 467 Igor L. Moudrakovski, Christopher I. Ratcliffe, and John A. Ripmeester 12 Reorientation and Diffusion in Clathrate Hydrates 513 John A. Ripmeester, Christopher I. Ratcliffe, Igor L. Moudrakovski, and Saman Alavi 13 IR and Raman Spectroscopy of Clathrate Hydrates 569 Tsutomu Uchida and Amadeu K. Sum 14 Kinetics of Clathrate Hydrate Processes 631 Peter Englezos, Saman Alavi, and John A. Ripmeester 15 Mechanical and Thermal Transport Properties of Clathrate Hydrates 717 John S. Tse and Dennis D. Klug 16 Applications of Clathrate (Gas) Hydrates 749 Peter Englezos Index 783