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Clathrate Hydrates
Clathrate Hydrates
Molecular Science and Characterization
Volume 1
Edited by
John A. Ripmeester
Saman Alavi
Clathrate Hydrates
Molecular Science and Characterization
Volume 2
Edited by
John A. Ripmeester
Saman Alavi
Editors All books published by WILEY-VCH are carefully
produced. Nevertheless, authors, editors, and
Dr. John A. Ripmeester publisher do not warrant the information
National Research Council of Canada contained in these books, including this book,
100 Sussex Dr. to be free of errors. Readers are advised to keep
K1A 0R6 NK in mind that statements, data, illustrations,
Canada procedural details or other items may
inadvertently be inaccurate.
Dr. Saman Alavi
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Department of Chemistry and
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10 9 8 7 6 5 4 3 2 1
To my wife Beth and daughters Heather and Wendy who put up with my
science-oriented adventures that sometimes got in the way of family time, to the
memory of my parents, John and Thea, who, while raising their recently emigrated
family, encouraged me to pursue higher education.
To my wife Dorothy for her support and patience during my never-ending scientific
activities, to my mother Zari for her encouragement on our path to higher education,
and to the memory of my father Mohammad who motivated me to become a chemist.
vii
Contents
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
viii Contents
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

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
Contents ix
5 Structures of Canonical Clathrate Hydrates 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
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 H2 O–NH4 F Solid Solution Frameworks 209
References 211
x Contents
7 Thermodynamics and Statistical Mechanics of Clathrate

Hydrates 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
Contents xi
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
vii
Contents
Volume 1
Preface xiii
1 An Introduction to Clathrate Hydrate Science 1

John A. Ripmeester, Saman Alavi, and Christopher I. Ratcliffe
2 An Introduction to Clathrate Hydrates 27

3 Classification of Clathrate Hydrates 65

4 Synthesis of Clathrate Hydrates 123

5 Structures of Canonical Clathrate Hydrates 141

6 Structures of Noncanonical Clathrates and Related

Hydrates 189
7 Thermodynamics and Statistical Mechanics of Clathrate

Hydrates 219
viii Contents
Volume 2
Preface xv
8 Molecular Simulations of Clathrate Hydrates 283

Saman Alavi and John A. Ripmeester
8.2 Molecular Simulations 284
8.2.1 Classical Molecular Dynamics Simulations 284
8.2.2 Monte Carlo Simulations of Clathrate Hydrates 287
8.2.3 Ab Initio Molecular Dynamics Simulations 288
8.2.4 Classical Interaction Potentials for Simulating Clathrate Hydrates 289
8.2.5 Proton Arrangements in the Clathrate Hydrate Simulations 293
8.3 Structural Characterization of Clathrate Hydrates with Simulations 295
8.3.1 Radial Distribution Functions 296
8.3.2 Lattice Constants and Three-Phase Equilibrium Lines 298
8.3.3 Guest Distribution and Structure in Cages 299
8.3.4 Order Parameters and Characterization of Clathrate Hydrate, Ice, and
Water Phases 302
8.3.5 Guest–Host Hydrogen Bonding in Clathrate Hydrate Cages 307
8.4 Dynamic Characterizations of Guest Motion in Cages 308
8.4.1 Velocity and Orientation Autocorrelation Functions 309
8.5 Simulations of Clathrate Hydrates 311
8.5.1 Mechanisms of Hydrate Decomposition, Nucleation, and Growth 312
8.5.2 Enthalpy of Formation, Decomposition, and Encagement from
Molecular Simulations 331
8.6 Ab Initio Quantum Mechanical Calculations of Clathrate Hydrates 334
8.6.1 Stationary Quantum States of Small Guests in Cages 335
8.6.2 Ab Initio Molecular Dynamics 340
8.7 Conclusions and Outlook 341
References 342
9 X-ray and Neutron Diffraction and Scattering of Clathrate

Hydrates 369
John S. Tse, Dennis D. Klug, and Satoshi Takeya
9.2 Crystallography and X-ray Diffraction 370
9.2.1 Comments on Diffraction as Applied to Hydrate Structure
Determination 373
9.2.1.1 Single-Crystal Diffraction 373
9.2.1.2 Powder Diffraction 374
9.3 Instrumentation 375
9.4 Structural Characterization with Diffraction Methods 379
9.4.1 Diffraction and Structure–Guest Size Relationship 380
Contents ix
9.4.2 Unconventional Applications of Diffraction 384

9.5 Neutron Diffraction or Elastic Neutron Scattering 390
9.6 Inelastic Neutron Scattering 396
9.7 Inelastic X-ray Scattering 400
9.8 Summary 407
References 407
10 Characterization of Clathrate Hydrates Using Nuclear

Magnetic Resonance Spectroscopy 417
Christopher I. Ratcliffe, Igor L. Moudrakovski, and John A. Ripmeester
10.2 NMR Interactions 418
10.2.1 The Zeeman Interaction 418
10.2.2 Other Interactions 420
10.2.2.1 The Shielding Interaction (σ) and Chemical Shift (δ) 420
10.2.2.2 The Nuclear Dipole–Dipole Interaction 423
10.2.2.3 The Spin–Spin J-Coupling Interaction 424
10.2.2.4 The Quadrupolar Coupling Interaction 424
10.2.2.5 The Spin–Rotation Coupling Interaction 427
10.2.2.6 Interactions with Unpaired Electrons 427
10.2.3 Units 427
10.3 Experimental Aspects of NMR Spectroscopy 427
10.3.1 The Basic NMR Experiment 427
10.3.2 Techniques for Enhancing Sensitivity and Resolution 428
10.3.2.1 Dipolar Decoupling 428
10.3.2.2 Magic Angle Spinning, MAS 429
10.3.2.3 Cross-Polarization (CP) 430
10.3.2.4 Hyperpolarization of 129 Xe (HP Xe) 430
10.4 The Development of NMR Techniques Over Time 430
10.5 NMR Powder Line Shapes in Clathrate Hydrates 432
10.5.1 Dipolar Line Shapes 432
10.5.1.1 Magnetic Dilution 432
10.5.1.2 Two-Spin Systems 432
10.5.1.3 Three-Spin Systems 433
10.5.1.4 Four-Spin Systems 434
10.5.1.5 Six-Spin Systems 434
10.5.1.6 Multi-Spin Systems 436
10.5.1.7 Effects of Paramagnetic Oxygen on 1 H Line Shapes 436
10.5.2 Chemical Shift Line Shapes 437
10.5.2.1 129 Xe NMR 437
10.5.2.2 Chemical Shift Line Shapes of Other Nuclei: 77 Se, 31 P, 19 F, 13 C 444

10.5.3 Quadrupolar Line Shapes 446
10.5.3.1 Spin 1: Deuterium 2 H 446
10.5.3.2 Half-Integer Quadrupolar Nuclei (131 Xe, 83 Kr, 33 S, 17 O) 450
References 458
x Contents
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
13 C MAS NMR in Compositional and Structural Analysis of Gas
11.2
Hydrates 468
11.2.1 Experimental Considerations 468
11.2.2 Overview of 13 C MAS NMR in Clathrate Hydrates 470
11.2.3 Concluding Remarks and Outlook 482
11.3 129 Xe NMR Applications: Other Topics 482
11.3.1 Transient/Metastable Phases 482

11.3.2 Rapid Scanning of the Formation of CS-I Xe Hydrate from Ice with
Hyperpolarized Xe 483
11.3.3 Annealing of Co-deposits of Xe and H2 O 485
11.3.4 H2 O-NH4 F Solid Solution Frameworks 485
11.4 Ionic Hydrates 486
11.4.1 Hydrates of Alkylammonium Salts 486
11.4.2 Hydrates of Strong Acids 487
11.4.3 Hydrates of Strong Bases 487
11.5 Clathrate Hydrates and Magnetic Resonance Imaging 489
11.5.1 Information About Gas Hydrates Accessible by Magnetic Resonance
Imaging 490
11.5.2 Experimental Conditions and Equipment for MRI in Gas
Hydrates 493
11.5.3 Overview of Current MRI Applications in Gas Hydrate
Research 495
11.5.4 Concluding Remarks and Outlook 502
References 503
12 Reorientation and Diffusion in Clathrate Hydrates 513

John A. Ripmeester, Christopher I. Ratcliffe, Igor L. Moudrakovski, and
Saman Alavi
12.2 Early Work on Clathrates/Inclusion Compounds 514
12.3 Dynamics 515
12.3.1 Dynamics and Timescales 515
12.3.2 Dielectric Relaxation 516
12.3.3 NMR Spectroscopy 519
12.3.3.1 Nuclear Dipolar Coupling 519
12.3.3.2 Nuclear Quadrupolar Interactions 522
12.3.3.3 Chemical Shift Line shapes 524
12.4 Water Dynamics in Ice and Clathrate Hydrates 525
12.4.1 Water Dynamics in Ice Ih 525
12.4.2 Water Dynamics in Clathrate Hydrates 528
Contents xi
12.5 Guest Motions 534

12.5.1 Guest Reorientation: General Considerations 534
12.5.1.1 Reorientation of Spherical Top Guest Molecules 536
12.5.1.2 Reorientation of Symmetric Top Guest Molecules 539
12.5.1.3 Reorientation of Asymmetric Top Guest Molecules 544
12.5.2 Diffusion 550
12.5.3 Nonclassical Dynamics 554
12.5.3.1 Methyl Groups 554
12.5.3.2 Dynamics of Light Tetrahedral Molecules 556
12.6 Summary 557
References 559
13 IR and Raman Spectroscopy of Clathrate Hydrates 569

Tsutomu Uchida and Amadeu K. Sum
13.1 Fundamentals and Quantification 570
13.2 IR Spectroscopy of Clathrate Hydrates 577
13.2.1 Far IR Transmission – FT-IR on Vapor-Deposited Thin Films 577
13.2.2 Recent Studies of Clathrate Hydrates Using IR Spectroscopy 578
13.3 Raman Spectroscopy of Clathrate Hydrates 581
13.3.1 Guest Molecule Information 582
13.3.1.1 Detection of Encapsulation 582
13.3.1.2 Quantification of Raman Peak Positions 585
13.3.1.3 Quantification of Cage Occupancy 588
13.3.1.4 Application of Raman Spectroscopy to Kinetic Processes 591
13.3.1.5 Analysis of Natural Hydrate Samples 593
13.3.2 Noncontact, Non-destructive Measurements of Gas Hydrates Via Visible
Light 596
13.3.2.1 Application of Raman Spectroscopy to Clathrate Hydrate Kinetic
Studies 596
13.3.2.2 Gas Hydrate Phases Obtained under High-Pressure Conditions 600
13.3.2.3 In Situ Analysis of Natural Hydrate Sample Under Deep Sea
Condition 605
13.4 Conclusions 605
References 614
14 Kinetics of Clathrate Hydrate Processes 631

Peter Englezos, Saman Alavi, and John A. Ripmeester
14.2 Experimental Measurement of Hydrate Process Rates 631
14.2.1 Kinetics – Gas Uptake Measurements 631
14.2.2 Kinetics of CS-1 and CS-II hydrates 633
14.2.3 Kinetics of HS-III Hydrates 636
14.2.4 Kinetics Measurements – Other Methods 637
14.2.5 Average and Spatially Localized Kinetics 641
14.3 Modeling the Kinetics of Hydrate Nucleation 645
xii Contents
14.3.1 Hydrate Formation 645

14.3.2 Homogeneous Nucleation 647
14.3.3 Heterogeneous Nucleation 652
14.3.4 Validity and Relevance of Classical Nucleation Theory 655
14.4 Hydrate Phase Transformations 660
14.4.1 Hydrate Growth from Water 660
14.4.2 Hydrate Growth from Ice 664
14.4.2.1 The Shrinking Core Model 665
14.4.2.2 The Avrami Equation 667
14.4.3 Hydrate Crystal Morphology 673
14.4.4 Hydrate Decomposition 676
14.5 Metastability 678
14.6 Kinetic Modifiers 680
14.6.1 Surfactants 680
14.6.2 Defect Generation in the Hydrogen-Bonded Ice and Hydrate
Lattices 682
14.6.3 Kinetic Hydrate Inhibitors 683
14.6.3.1 Macroscopic Descriptions of Hydrate Inhibition 683
14.6.3.2 Mechanism of Kinetic Inhibition 684
14.6.3.3 Complexities of the Hydrate Inhibition Process 688
14.7 Molecular Simulations of Clathrate Hydrate Nucleation and
Growth 690
14.7.1 Simulations of Heterogeneous Nucleation 691
14.7.2 Molecular Simulations of Homogeneous Nucleation 692
14.7.3 Simulations of Hydrate Growth 695
14.7.4 Simulations of Hydrate Growth and Decomposition in the Presence of
Inhibitors 696
14.8 Concluding Remarks 697
References 698
15 Mechanical and Thermal Transport Properties of Clathrate

Hydrates 717
John S. Tse and Dennis D. Klug
15.2 Theoretical Background 718
15.2.1 Elastic Moduli 718
15.2.2 Thermal Conductivity 720
15.3 Mechanical Properties: Acoustic Velocity and Elastic Constants 721
15.4 Thermal Expansion 730
15.5 Transport Properties: Thermal Conductivity 734
15.6 Molecular Dynamics Simulations of Thermal Properties of Clathrate
Hydrates 739
15.7 Summary 742
References 743
Contents xiii
16 Applications of Clathrate (Gas) Hydrates 749

Peter Englezos
16.2 Flow Assurance in Oil and Gas Pipelines 750
16.2.1 Large-Scale Flow Loops 753
16.2.2 Catastrophic Hydrate Formation and Pipeline Plug Potential 754
16.2.3 Oil and Gas Pipelines with Hydrophobic Surfaces 754
16.3 Natural Gas Energy Recovery from the Earth’s Hydrates 755
16.3.1 Extraction of Natural Gas by Injection of CO2 or CO2 /N2 Flue Gas 757
16.4 Desalination 758
16.5 Concentration of Wastewater and Aqueous Organic Solutions 759
16.6 Storage and Transportation of Natural Gas, Hydrogen, and Other
Materials 760
16.6.1 Natural Gas Storage 760
16.6.2 Hydrogen Storage 762
16.7 Gas Separations 765
16.7.1 Metrics 766
16.7.2 Separation of CO2 from Flue Gas Mixtures (Post-Combustion
Capture) 767
16.7.2.1 Impact of SO2 768
16.7.3 Separation of CO2 from Fuel Gas Mixtures (Pre-Combustion
Capture) 768
16.7.4 Other Gas Separations 771
16.8 Conclusions 772
References 772
Index 783
xiii
Preface
Scope
Why write this book? A number of reasons come to mind. Today, a vast number of
publications on clathrate hydrates continue to appear in journals dealing with the
many different, often non-overlapping areas of hydrate research. Increasingly, these
studies focus especially on engineering and geological aspects, as well as potential
applications. Molecular science has provided the fundamental underpinnings for
much of this work; however, the earlier work has become more difficult to find, and
there have not been major comprehensive monographs or books focused on scien-
tific aspects of these substances for some 40 years. It is to fill this gap that preparation
of this book was undertaken. We also feel there are a number of misconceptions or
questionable approaches that have propagated over the years, and this book provides
an opportunity to revisit some of these points.
The 150 years that it took for the first observed phenomenon of gas hydrates to
be properly explained make for a fascinating story of the intertwining of the then
current hydrate science, advances in technology, and the evolution of chemical
concepts. After an Introduction and summary of the “classical period,” the book
presents 16 chapters outlining hydrate science in different areas of specialization
(see below). Each chapter provides a short summary of the respective methodology
and is written with an emphasis on the experience of the authors with significant
feedback from the editors and the other chapter authors. The book also provides
comprehensive tabulated information on the structural, compositional, spectro-
scopic, thermodynamic properties, and molecular simulations of clathrate hydrates.
With this information gathered in one place, it will be a valuable resource for both
experienced researchers, and researchers and graduate students of science and
engineering just starting their studies of these fascinating substances. The authors
have aimed at making each chapter as comprehensive as possible, but in a work of
this scope, valuable work will inevitably not be discussed.
A summary of the chapter contents follows.
Chapter 1 reports the major highlights in the development of clathrate hydrate
knowledge and then highlights contributions of the National Research Council of
Canada group where the authors of this volume have worked or which they were in
close collaboration.
xiv Preface
Chapter 2 gives a more detailed historical outline of the study of clathrate hydrates
from the classical period up to 1970 when the hydrate crystallographic structure
became known and the statistical mechanical model of clathrate hydrates was
developed. We surveyed some of the primary literature of this period to clarify some
of the historical aspects of these substances discovered by the early researchers.
Chapters 3 and 4 introduce the different hydrate cages made of hydrogen-bonded
water molecules and discuss the classification of clathrate hydrates as part of the
larger family of supramolecular compounds, and their techniques of synthesis,
respectively. Hydrates are presented as solid solutions with their stability being a
lattice property. Comprehensive tables are presented of the known guest molecules,
and summaries of their structural and physical properties are given in this chapter.
The different classes of clathrate hydrate phase equilibria are presented.
Chapters 5 and 6 discuss structural aspects of clathrate hydrates, semi-clathrates,
and salt hydrates. The importance of unconventional guest–host interactions
like hydrogen and halogen bonding is introduced. Different ways of looking at
hydrate structures based on layered structures and space filling cages using the
Frank–Kasper approach are presented, and related non-hydrate clathrates are
introduced.
Chapter 7 introduces thermodynamics and statistical mechanics of clathrate
hydrates with discussion of calorimetric methods and the van der Waals–Platteeuw
theory and some of its extensions. Many recent engineering applications and
extensions are not directly discussed as they are discussed in Chapter 16 or are
beyond the scope considered for this book. Tables of hydrate composition and
thermochemical information are presented.
Chapter 8 gives a summary of the application of molecular simulation methods
to study clathrate hydrate properties. Methods of characterizing structural and
dynamic properties of clathrate hydrates are discussed. Most of the emphasis is on
classical molecular dynamics and Monte Carlo results, but quantum mechanical
calculations of confinement effects for small molecules such as hydrogen and
methane in the clathrate hydrate cages are also reviewed. A table is given for
systems studied to date using molecular simulation methods.
Chapters 9, 10, 11, and 13 discuss X-ray and neutron diffraction and scattering,
general and specialized NMR methods and IR/Raman methods for studying
clathrate hydrates, respectively. The techniques are briefly introduced, and the
often complementary information they provide on clathrate hydrates are described.
The use of these methods in unraveling the structure and dynamics of guest–lattice
interactions is summarized.
Chapter 12 presents information, mainly from dielectrics and solid-state NMR, on
the molecular motion of guest and host molecules. The relationship between cage
geometry and guest dynamics is introduced, as is the effect of guest–host hydrogen
bonding on water molecule dynamics.
Chapter 14 presents the rate and mechanisms of hydrate formation and decom-
position from both macroscopic (process) and microscopic (mechanism) points of
view. Classical nucleation theory introduces a number of key parameters that are
pertinent to both homo- and heterogeneous nucleation mechanisms of hydrate
formation. Emphasis is placed on hydrate processes as phase changes occurring
Preface xv
in the presence of mass and temperature gradients rather than chemical reactions
occurring in isotropic and isothermal systems. The various factors that modify
kinetics of hydrate formation are introduced and discussed from results gathered
from both experimental and molecular simulations. The hydrate memory effect and
possible mechanisms of kinetic hydrate inhibition (using both polymeric substances
and antifreeze proteins) are discussed in this chapter.
Chapter 15 deals with mechanical properties of clathrate hydrates, including
acoustic velocity, elastic constants, thermal expansion, and thermal conductivity.
Experimental and theoretical backgrounds for the study of these properties are
given. Some anomalous effects seen in the temperature dependence of the thermal
conductivity of hydrate phases, but absent in ice, are discussed in detail in this
chapter.
Chapter 16 presents with selected potential applications of clathrate hydrate com-
pounds, including flow assurance, natural gas recovery, desalination, concentration
of aqueous solutions, and the storage of natural gas, hydrogen, and gas separation.
This chapter is meant to be an overview of some applications, which will be well
studied in the near future.
The authors’ work described in this book has contributions from many colleagues,
staff, and students at the National Research Council of Canada who are named
in Chapter 1. The contributions of these individuals are gratefully acknowledged.
The work described would not have been possible without the material support of
the National Research Council of Canada from ∼1960 to 2011. As in any field, the
progress in clathrate hydrate research is the result of collaboration and contributions
from researchers in many countries. We hope to have given proper representation
of contributions from researchers from all parts of the world. We apologize for any
omissions, which are the result of the limited scope of some of the discussions in
this book.
We would like to acknowledge the contributions of Donald Davidson (1925–1986)
of the National Research Council of Canada as one of the pioneers in modern
hydrate research in Canada. Don (i) initiated a multi-technique approach to study-
ing gas hydrates; (ii) provided mentorship to generations of hydrate researchers
at the NRC; and (iii) wrote a number of monographs and book chapters, which
are exemplary for their clarity and are still useful today. At the time, the National
Research Council was a fertile multidisciplinary environment where cutting-edge
dielectric, NMR, single-crystal X-ray crystallographic, and simulation techniques
were being developed, and almost immediately being used in understanding these
substances. After Don’s passing, this tradition was maintained at the NRC.
The editors would like to thank the authors of the chapters in this book for their
contributions and their patience with our numerous requests for editorial changes.
We would particularly like to thank Christopher I. Ratcliffe, Amadeu K. Sum, Peter
Englezos, and Dennis D. Klug who also commented extensively on chapters other
than their own.
We would like to thank our wives Beth and Dorothy for support and dealing with
the seemingly unending demands on our time while we worked on this book. We
thankfully acknowledge their indirect, but important contributions in getting this
book project completed.
1
An Introduction to Clathrate Hydrate Science

John A. Ripmeester 1 , Saman Alavi 1,2 , and Christopher I. Ratcliffe 1
1
National Research Council of Canada, 100 Sussex Drive, Ottawa, ON, K1A 0R6, Canada
2
University of Ottawa, Department of Chemistry and Biomolecular Science, STEM Complex, 150
Louis-Pasteur Pvt., Ottawa, ON, K1N 6N5, Canada
1.1 Introduction
The first intersection of clathrate hydrates and human endeavor took place in the late
1700s. A number of researchers (natural philosophers) working on the solubility of
newly discovered airs (gases) observed unexpected ice-like solids formed above the
freezing point of ice when certain gases were passed into cold water or when such
a solution was frozen. Davy identified these solids as two-component water–gas
compounds and named them “gas hydrates.” After some 140 years and much
research, these solids were shown to be clathrates, materials where small molecules
(guests) are trapped in an ice-like lattice (host) consisting of hydrogen-bonded
water cages. During the time between initial discovery and final identification, gas
hydrates confounded researchers by having a number of properties that countered
concepts derived from mainstream chemistry. For instance, the hydrates were
non-stoichiometric, the water-to-gas ratios were not small whole numbers, and they
decomposed upon heating or depressurization to give back the unchanged starting
materials. The lack of chemical bonds between the water and the gas in the hydrates
suggested that these were not real chemical compounds and in fact were the first
examples of “chemistry beyond the molecule” – supramolecular compounds.
From phase equilibrium studies, we now know that when many gases and water
are in contact under appropriate pressure (P) and temperature (T) conditions, a solid
hydrate will form. The gas hydrates store gases, including natural gas, very efficiently
with one volume of solid hydrate storing some 160 volumes of gas at standard tem-
perature and pressure (STP). Since a number of gas hydrates are found naturally, this
class of materials can be taken to be an unusual type of mineral. There are many sites
in the geosphere where natural gas and water are in contact under the conditions
required to form gas hydrate. Locations where this occurs are in sediments offshore
of continental margins, under permafrost, and in some deep freshwater lakes.
Well before the discovery of natural gas hydrate in the geosphere, oil and gas
engineers encountered blocked natural gas pipelines during cold weather operation
Clathrate Hydrates: Molecular Science and Characterization, First Edition.
Edited by John A. Ripmeester and Saman Alavi.
© 2022 WILEY-VCH GmbH. Published 2022 by WILEY-VCH GmbH.
2 1 An Introduction to Clathrate Hydrate Science
which was initially attributed to ice formation from moisture in wet gas. Knowledge
of earlier work on solid methane hydrate led Hammerschmidt in the 1930s to the cor-
rect explanation for the pipeline blocks – they were made of solid methane hydrate
rather than ice. Since then, during the exploration, production and transport phases
of hydrocarbon resources, blockage by natural gas hydrate formation has become a
well-known hazard, resulting in possible serious damage and loss of life, for example
in the Deepwater Horizon oil spill of 2010. Much research has been carried out
to prevent or manage hydrate formation in pipelines. Other problems related to
gas hydrates have been identified, including marine geohazards, such as submarine
landslides, and sudden gas releases from hydrate formations.
Because of the vast amounts of trapped natural gas in hydrate form globally,
gas hydrates have been evaluated to be a significant unconventional natural gas
resource. Hydrate deposits have been mapped in many locations around the world,
usually using geotechnical methods that depend on the location of unexpected
solid hydrate–liquid water interfaces which act as seismic reflectors. Test wells for
gas production have been drilled in the Mackenzie Delta, Canada (Mallik 2L38),
Alaska, the Nankai trough offshore Japan, and offshore China. Many problems
have been encountered in producing gas from hydrate reservoirs, including the
development of the best techniques for destabilizing the solid hydrate and captur-
ing the resulting gas. Some hydrate deposits, often associated with hydrocarbon
seeps or vents, exist as outcrops on the seafloor. Whereas most of the methane
in hydrate reservoirs is of biogenic origin, hydrates associated with seeps or hot
vents are formed from thermally altered hydrocarbons originally residing in deeper
reservoirs. Some hydrate outcrops are home to specialized biological ecosystems
where microbes feed on hydrocarbons and these in turn become a food source for
“ice-worms.”
Besides the marine and terrestrial natural gas hydrates, there are gas hydrates of
air (mainly N2 and O2 ) deep inside glaciers. The hydrate zone starts at pressures
where gas bubbles in the ice disappear. There has been much speculation regarding
the existence of hydrates in extra-terrestrial space, that is, on Mars, Titan, Enceladus,
and the heads of comets. One of the best candidates for finding such a hydrate would
appear to be that of CO2 . Although lots of spectroscopic data exist for free solid
CO2 and ice in extra-terrestrial space, no sign of CO2 hydrate has been found, see
Chapters 3 and 13 for possible reasons.
The large gas capacity and water as cheap working fluid make gas hydrates
interesting materials for industrial applications. Gas hydrates are generally selective
for guest molecule adsorption which allows the separation of gas mixtures. Much
as salt is excluded when brine is frozen in desalination processes, gas hydrates have
the same ability, but now the properties of the solid phase can be adjusted. For
example, depending on the choice of guest, the hydrate freezing point can be well
above the ice point, so saving on refrigeration costs. The same principle applies
to cool energy storage where the freezing point of the hydrate can be tuned to
minimize operational costs. Further applications include dewatering of fruit juices,
1.1 Introduction 3
sewage sludge and wood pulp, and the storage of unstable molecules such as ozone
and chlorine dioxide. A more exotic application was the separation of radioactive
radon gas from a gas mixture.
The gentler conditions required for the formation and storage of methane in
solid hydrate form as compared to the low temperature required for liquid nitrogen
storage of liquefied methane has resulted in the evaluation of transport by these two
means. Indeed, some cost advantages become apparent for solid hydrate transport
if methane has to be transported from stray fields where construction of a liquid
natural gas (LNG) plant is not cost effective. Other applications for storage have
been explored, e.g. for hydrogen as fuel gas and CO2 for greenhouse gas separation
and storage.
Gas hydrates, because of their unique properties, have demonstrated some enter-
tainment value. The “burning snowball” results when methane from decomposing
methane hydrate is ignited and this phenomenon has been admired by many,
both live and in print. In the early 1980s, it was proposed that sudden, massive
decomposition of marine methane hydrates could be the cause of disappearances
of ships and planes in mythically mysterious areas such as the Bermuda triangle.
It appears the mystery novel “Death by gas hydrate” still needs to be written:
hydrates have great potential as difficult to track murder weapons. The media also
have frequently given news coverage of “burning ice” which is rediscovered every
10 years or so.
From the earlier examples, it is clear that gas hydrates are interesting and unusual
materials partly because nature makes them and partly because there are many
potential uses which unfortunately remain largely prospective. This book will
emphasize the molecular chemical, physical, and material aspects of clathrate
hydrates, that is, the many details needed to understand the macroscopic properties
and processes mentioned earlier. Engineering and geological aspects of the gas
hydrates have been covered admirably in a number of previous books mentioned
later.
In Section 1.2 of this chapter, we highlight milestones of clathrate hydrate science
up to the present. The history and context of some of these earlier developments
are discussed in greater detail in Chapter 2 and in chapters that follow and the
relevant references can be found there. From their beginning and in the decades
that followed, many centers of clathrate hydrate research emerged in different
parts of the world. From the early 1960s with the work of Don Davidson and
coworkers, the National Research Council (NRC) of Canada in Ottawa emerged as
one of the active centers of research in this field. In Section 1.3, we give a summary
of the contributions to clathrate hydrate science made in the NRC of Canada
during this time period. Contributors to the clathrate hydrate research at the NRC
are acknowledged in Section 1.4. Some influential books and review articles on
clathrate hydrates that appeared during this period and up to the current time are
introduced in Section 1.5. International conferences focusing on clathrate hydrate
science are listed in Section 1.6.
1.2 Selected Highlights of Clathrate Hydrate Science

Research Up to the Present
In this section, we summarize selected highlights of clathrate hydrate research,

emphasizing contributions to molecular science. Not all engineering and geological
discoveries are covered in detail in this selection. Full author names and references
for most of these highlights are given in the following chapters.
1810 Sir Humphrey Davy correctly identified a solid material, previously thought
to be solid chlorine, as a compound of chlorine and water and called it “gas
hydrate.”
1823 Faraday determined the composition of chlorine hydrate to be Cl2 ⋅10H2 O.
1823 Faraday acting upon a suggestion by Davy, used decomposition of gas
hydrates in confined vessels as a method of liquefying gases.
1828 Löwig prepared bromine hydrate and determined the formula Br2 ⋅10H2 O for
the compound.
1829 de la Rive prepared SO2 hydrate, SO2 ⋅14H2 O, and proposed that all common
gases form hydrates.
1840 Wöhler prepared H2 S hydrate.
1843 Millon prepared chlorine dioxide hydrate, the first example of the
preservation of an unstable chemical species, ClO2 , an explosive-free radical.
1852 Loir prepared solid binary hydrates from water, H2 S, or H2 Se and
halogenated hydrocarbons like chloroform, their composition remained
unknown for some 30 years.
1856 Berthelot prepared the first pure hydrates of organic compounds, namely,
those of methyl chloride and methyl bromide. He also claimed that CS2
formed a hydrate, starting a controversy about its existence that lasted 40
years.
1863 Wurtz prepared ethylene oxide (EO) hydrate, the first example of a
water-soluble guest. Its composition and melting point diagram were not
determined until 1922.
1878 Isambard showed that the equilibrium pressure of chlorine hydrate is
univariant.
1878 Cailletet designed and built apparatus suitable for working at high pressure
and low temperature. This was of great value for the preparation of new gas
hydrates and the determination of phase equilibria. He illustrated this by
preparing new hydrates of acetylene and phosphine.
1882 Wróblewski prepared CO2 hydrate.
1882 de Forcrand prepared and characterized 33 double hydrates of H2 S with a
variety of guests and established similarities of composition, M⋅2H2 S⋅23H2 O.
Studies were extended to double hydrates with H2 Se as well as a simple
hydrate of H2 Se.
1882 Cailletet and Bordet showed that mixed hydrates of CO2 and PH3 were not
simply physical mixtures of simple CO2 and PH3 hydrates but hydrates with
unique properties.
1883 de Forcrand applied calorimetry to gas hydrates and assigned most of the
thermal effects to the dominant presence of water in the hydrate.
1.2 Selected Highlights of Clathrate Hydrate Science Research Up to the Present 5
1883 de Forcrand observed that a number of double hydrates had well-defined

cubic, cubo-octahedral, or truncated octahedral morphologies which were
not acted on by polarized light.
1884–1885 Bakhuis Roozeboom provided hydration numbers for SO2 , Cl2 , and Br2
hydrates and his phase equilibrium diagrams clearly showed the
pressure–temperature fields of hydrate stability. Cailletet, Wróblewski, and
Bakhuis Roozeboom observed a memory effect that increased the
reformation rate of hydrate from solutions of decomposed hydrate.
1884 Le Châtelier used the Clausius–Clapeyron equation for the variation of vapor
pressure of the hydrates with temperature and was the first to use the
equation to determine gas hydrate compositions.
1885 Chancel and Parmentier reported a simple hydrate of chloroform. This was
one of the first so-called “liquid hydrates” whose guest components are
liquids at ambient temperature.
1887–1888 Bakhuis Roozeboom applied the Gibbs phase rule to heterogeneous
equilibria and systematically classified chemical and physical processes
according to number and nature of the components and phases present. He
published on the treatment of the invariant points at which equilibrium lines
meet.
1888 Villard prepared hydrates of CH4 , C2 H6 , C2 H4 , N2 O, and propane (1890).
1890 Villard recognized the stabilizing effect of air on the decomposition of gas
hydrates. In the search for other “help-gases” he identified both hydrogen at
23 atm and oxygen at 2.5 atm as increasing the decomposition temperature of
ethyl chloride.
1897 On the basis of careful measurements on the large number of hydrates then
available, Villard presented a definition of the composition of gas hydrates
(Villard’s law).
1897 de Forcrand and Thomas discovered new help-gases (CO2 , C2 H4 , C2 H2 , and
SO2 ).
1902 de Forcrand used calorimetric data and a generalization of Trouton’s rule to
calculate hydrate compositions for 15 hydrates. About half had compositions
in agreement with Villard’s law.
1923 Bouzat produced summary statements giving the then current definition of
hydrates, their structure, and composition.
1926 Schroeder wrote an influential monograph summarizing the state of
knowledge of gas hydrate to that date.
1934 Hammerschmidt, after reading Schroeder’s book, showed that gas hydrates
are more likely to form plugs in natural gas pipelines than ice.
1936–1937 Nikitin prepared mixed hydrates of noble gases and SO2 and showed that the
noble gases could be separated by partitioning between the solid hydrate and
the gas. His observations were first consistent with the “solid solution”
nature of hydrates.
1946 Deaton and Frost presented experimental data on hydrate phase equilibria of
natural gas components and methods of hydrate prevention.
1946 Miller and Strong proposed natural gas storage in hydrate form.
1947 Powell coined the term “clathrate” for materials having a guest molecule
residing in a cavity formed in a host lattice.
1949 von Stackelberg used X-ray diffraction data to propose a structure for a gas
hydrate of chloroform and H2 S. Although the structure, based on a lattice
with holes for guests, was incorrect, it was a radical departure from the
molecular structure current up until that time. von Stackelberg had studied
the X-ray diffraction of gas hydrates prior to this time, but his original
photographic plates had been destroyed in aerial bombardment during World
War II.
1951 Clausen introduced the pentagonal dodecahedron as a structural component
of gas hydrates, and von Stackelberg and Muller’s X-ray diffraction data
confirmed the crystal structure of the “structure II” (sII or CS-II) hydrate
proposed by Clausen.
1952 Clausen, von Stackelberg, and Pauling and Marsh provided a structure for
“structure I” (sI or CS-I) gas hydrates.
1952 Delsemme and Swings suggested the presence of gas hydrates in comets and
interstellar grains. Delsemme later suggested that the outgassing of comets
on approaching the sun could be due to decomposition of hydrates.
1957–1967 Barrer and coworkers studied hydrate thermodynamics, kinetics, and
separation of gas mixtures with hydrate formation.
1959–1970 Jeffrey and coworkers used single-crystal X-ray diffraction to obtain
structural data for clathrate hydrates, semi-clathrates, and salt hydrates.
1959 van der Waals and Platteeuw presented the “solid solution” statistical
thermodynamics model for clathrate hydrates.
1961 Miller and Pauling hypothesized hydrate formation as a mechanism for
anesthesia arising from inert noble gases, in particular xenon.
1961 Miller suggested the presence of gas hydrates in the planets, planetary rings,
and interstellar space in the solar system.
1963 Davidson used dielectric methods to study clathrate hydrates. He discovered
new water-soluble (polar) guests for clathrate hydrates, measured the
dynamics of guest and host molecules, found that water molecule
reorientation rates depend on the nature of the guest molecule, and
postulated the presence of guest–host hydrogen bonding capable of
generating Bjerrum defects.
1965 Makogon reported on natural gas hydrates found in the Siberian permafrost.
1965 Kobayashi and coworkers applied the Kihara intermolecular potential to van
der Waals–Platteeuw theory to represent the guest–cage interactions.
1965 Davidson and coworkers started nuclear magnetic resonance (NMR)
measurements on clathrate hydrates and demonstrated that the SF6 guest in
sII clathrate rotates isotropically even at 77 K.
1966 Glew and Rath showed that the equilibrium compositions of Cl2 and EO
clathrate hydrates are variable, in accordance with van der Waals–Platteeuw
theory.
1968 Glew and Haggett studied EO hydrate growth kinetics and showed that the
process is governed by heat transfer over a wide range of concentrations.
1969 Miller predicted air hydrates should be present in glacier ice, CO2 hydrates
on Mars, and CH4 hydrates on the outer planets and moons.
1969 Ginsburg studied natural gas hydrates in geological settings.

1971 Stoll, Ewing, and Bryan found that anomalous wave velocities
(bottom-simulating reflectors) are associated with marine offshore natural
gas hydrate deposits.
1972 Parrish and Prausnitz developed convenient computer code for applying the
van der Waals–Platteeuw theory to the calculation of gas hydrate phase
diagrams.
1972 Tester, Bivins, and Herrick performed the first Monte Carlo simulation of gas
hydrates of noble gases, N2 , O2 , CO2 , and CH4 to test some of the
assumptions made regarding guest–cage interactions in using the van der
Waals–Platteeuw approach.
1973–1983 Bertie and coworkers studied clathrate hydrates with infrared spectroscopy at
low temperatures.
1974 Bily and Dick encountered gas hydrates below the permafrost in the
Mackenzie Delta, Northwest Territories, Canada.
1974 Davidson, Garg, and Ripmeester reported broadline and pulsed NMR
experiments on tetrahydrofuran (THF) hydrate from 4 to 270 K, showing
regions of anisotropic and isotropic motions of the guest, relaxation minima
for guest anisotropic rotation, water molecule reorientation, and diffusion.
1974 Davidson et al. showed that polar as well as non-polar guests show
reorientational guest motions that can be described by very broad
distributions in reorientational correlation times at low temperatures. It led
to a model for a guest–host potential determined by short range interactions
between the guest and the disordered hydrogen atoms of the host water
molecules.
1974 Dyadin was appointed to lead a research group that over some 40 years
provided new information on structure, stoichiometry, and stability of
clathrates and high-pressure research on clathrate hydrates.
1975 Sloan and coworkers initiated work on two-phase hydrate equilibria.
1976 Holder calculated that small guests are more likely to form sII (CS-II) hydrate
than sI (CS-I).
1976–1987 Nakayama studied phase equilibria of salt hydrates.
1976 Peng and Robinson developed an accurate equation of state which is widely
used to describe the vapor–liquid equilibria of hydrocarbons and small gases
for hydrate equilibrium calculations.
1977 Ripmeester and Davidson reported 17 new clathrate guests mainly from
NMR measurements.
1979–1993 Bishnoi and coworkers initiated a program of natural gas hydrate kinetic
measurements and modeling and phase equilibrium modeling.
1981–1985 Cady measured hydrate compositions as a function of pressure, obtaining
values which are in agreement with van der Waals–Platteeuw theory.
1981 Ross, Anderson, and Backström measured the anomalously low thermal
conductivity of hydrates of clathrate hydrates.
1983 Tse, Klein, and coworkers initiated molecular dynamics simulations of
clathrate hydrates.
1984 Handa prepared pure hydrocarbon hydrates under equilibrium conditions

and obtained their thermodynamic properties from calorimetry.
1984 Davidson et al. experimentally showed very small guests form CS-II rather
than CS-I.
1986 Davidson et al. provided the first laboratory analysis of recovered gas hydrate
samples obtained from the Gulf of Mexico and identified both CS-I and CS-II
hydrates.
1986 Davidson, Handa, and Ripmeester provided the first measurement of
absolute cage occupancy of Xe hydrate.
1987 Ripmeester and coworkers discovered a new clathrate hydrate family,
structure H (HS-III).
1988 Whalley showed that octahedral melt figures are produced in THF clathrate
hydrate crystals.
1988 Ripmeester and Ratcliffe introduced low-temperature magic angle spinning
13
C NMR spectroscopy to measure the relative occupancy of methane and
methane/propane hydrate and used van der Waals–Platteeuw theory to
obtain hydration numbers.
1988 Makogon and Kvenvolden independently provided estimates of the total
volume of worldwide in situ hydrated natural gas at 1016 m3 . Kvenvolden
recognizes the decomposition of natural gas hydrates as potential contributor
to global climate change.
1990 Collins, Ratcliffe, and Ripmeester used NMR spectral properties of several
different nuclei, including 2 H, 19 F, 31 P, and 77 Se to measure hydration
numbers.
1990 Rodger studied hydrate stabilities with molecular dynamics simulations.
1990 Hallbrucker and Mayer formed clathrate hydrates by vapor deposition of
amorphous solid water.
1990 Ripmeester and Ratcliffe discovered numerous new guests which form
HS-III and CS-II using 129 Xe NMR of xenon co-guest.
1991 Sloan proposed a molecular mechanism for hydrate formation with
implications for inhibition.
1991 Handa et al. applied high pressure at 77 K to amorphize CS-I and CS-II
clathrate hydrates, much as was observed for ice itself. Unlike, the
amorphous ice phase, this amorphous phase recrystallized to the original
hydrate phase when the applied pressure was reduced to ambient at 77 K.
1992 Handa and Stupin investigated hydrate phase equilibria in porous media.
1993 Inelastic incoherent neutron scattering (IINS) experiments on methane, Xe,
and Kr hydrates were initiated at the NRC.
1993 Englezos and Hatzikiriakos used mathematical models to quantify how
global temperature warming affects the stability of methane hydrates in the
permafrost and in ocean sediments.
1993–2020 Tanaka and coworkers began a program of generalizing and improving on
the assumptions of the van der Waals–Platteeuw theory.
1994 Edwards modeled winter flounder antifreeze peptide as a potential kinetic
hydrate inhibitor.
1996 Sum measured clathrate hydration numbers with Raman spectroscopy.
1996 Koga and Tanaka studied the rearrangements of the water hydrogen bonding
network in clathrate hydrates with polar guests using molecular dynamics
simulation.
1997 Kuhs et al. reported double occupancy of large cages in CS-II nitrogen
hydrate.
1997 Udachin et al. reported HS-III (sH) structure from single-crystal X-ray
diffraction.
1997 Udachin et al. determined the tetragonal structure, TS1, of Br2 hydrate from
single-crystal X-ray diffraction.
1999 Dyadin et al. reported that H2 forms a clathrate hydrate at high pressure.
1999 Moudrakovski et al. reported the first magnetic resonance imaging (MRI) of
hydrate formation on ice particles.
2000 Huang, Walker, and Ripmeester showed that antifreeze proteins (AFPs)
inhibit hydrate formation and, in some cases, eliminate the freezing memory
effect for hydrate reformation.
2000–2001 Loveday et al., Hirai et al., Chou et al., and Manakov et al. prepared and
characterized high-pressure phases of water, including a high-pressure
HS-III clathrate phase.
2001 Moudrakovski et al. used hyperpolarized 129 Xe NMR to observe the
nucleation, growth, and decomposition of Xe hydrate in real time.
2001 Udachin et al. determined a new structural type for dimethyl ether clathrate
hydrate.
2001 Moudrakovski et al. observed a metastable CS-II Xe hydrate phase.
2001 Loveday et al. discovered a high-pressure structure of CH4 hydrate using
diamond anvil diffraction methods.
2002 Ballard and Sloan developed CSMGem software for hydrate equilibrium
prediction.
2002 Mao et al. synthesized the CS-II hydrogen hydrate under high-pressure and
low-temperature conditions to observe high H2 :H2 O storage ratios.
2002 Servio and Englezos accurately measure the temperature dependence of the
solubility of CH4 and CO2 gases in the aqueous phase in equilibrium with the
corresponding clathrate hydrate phases.
2004 The mechanism of self-preservation of methane hydrate was studied with
scanning electron microscope (SEM) imaging by Stern and coworkers.
Falenty and Kuhs used SEM to study self-preservation of CO2 hydrate in
2009.
2005 Lee et al. developed a method for tuning the H2 content of the mixed CS-II
hydrate with THF.
2005 Clarke and Bishnoi developed a focused beam reflectance method for in situ,
time-dependent hydrate particle size analysis under conditions of hydrate
nucleation and growth.
2007–2016 Bačić and coworkers performed quantum mechanical calculations to
determine discrete translation-rotational states of H2 and CH4 in different
CS-I and CS-II cages with single and multiple occupancies.
2007 Celli, Ulivi, and coworkers initiated IINS studies on H2 /D2 /HD dynamics in
CS-I and CS-II clathrate hydrates
2007 Linga, Kumar, and Englezos provided the thermodynamic and kinetic basis
for CO2 capture from post-combustion flue gas and pre-combustion fuel gas.
2009 Detailed characterization of hydrogen bonding of hydrates was determined
using molecular dynamics simulations by two groups: Buch et al. and at the
NRC.
2009 Simulation work initiated by Jordan and coworkers determined the stepwise
(layer by layer) decomposition mechanism for methane hydrate.
2010 Walsh et al. carried out millisecond molecular dynamics simulations of CH4
hydrate nucleation and growth.
2010 Following an early proposal by McTurk and Waller, Mori, and coworkers
formed ozone hydrate in an apparatus incorporating in situ ozone generation.
2012–2014 Shin et al. characterized clathrate hydrates incorporating NH3 and CH3 OH
synthesized using vapor deposition.
2013 Udachin et al. performed single-crystal X-ray diffraction and molecular
dynamics simulations on halogen hydrates which indicated the possibility of
halogen bonding between these guests and water molecules of the cages.
2014 Falenty, Hanssen, and Kuhs prepared a metastable ice phase (Ice XVI) with
the structure of the empty CS-II lattice.
2015 NMR spectroscopy gave direct evidence of cage-to-cage transfer of hydrate
guests CO2 in THF-CO2 CS-II hydrate and for CH4 and CH3 F in double
hydrates of THF and tert-butylmethylether.
2015 Molecular dynamics simulations performed at the NRC and University of
British Columbia showed the formation of nanobubbles of methane upon
decomposition of methane hydrate.
1.3 Clathrate Hydrate Research at the NRC Canada
For about 50 years, gas hydrate research was a supported project at the NRC in
Ottawa. It had its start in the early 1960s when Don Davidson, working in the Colloid
Section of the Division of Applied Chemistry (Figure 1.1), took the initiative to fol-
low up on a fundamental question that arose during his investigation of the dielectric
properties of liquids: in the dielectric properties of liquids, is it possible to sepa-
rate the contributions from molecular reorientation and diffusion? This led to the
first studies on clathrate hydrates where molecules are trapped in pseudo-spherical
molecule-sized cages so that one may well expect that contributions from diffusion
should be reduced or eliminated.
Clathrate hydrate science was at a stage of development where two hydrate struc-
tures were known, confirming their clathrate nature. Statistical thermodynamics
had provided a model of clathrate hydrates based on weak guest–host interactions;
however, many of the features of the model remained untested.
Early work on guest dynamics in clathrates at the University of British Columbia
(by Charles McDowell) convinced Don, Figure 1.2a, that NMR spectroscopy would
be another useful technique for the study of guest motion, as it provided the means to
study the effect of polar versus non-polar guests. It was an opportune time to initiate
Figure 1.1 National Research Council of Canada Building M-12 on the NRC Montreal Road
campus in Ottawa, home of the Colloid Chemistry (later Colloid and Clathrate Chemistry)
group until 1990. Source: Reproduced with permission from the National Research Council.
(a) (b)
Figure 1.2 (a) Donald Davidson observing a clathrate hydrate sample; (b) William
Schneider in the official portrait as president of the NRC. Source: Photographs by the
authors.
(a) (b)
Figure 1.3 (a) S. K. Garg at the controls of the Bruker 1.4 T SXP spectrometer as modified
for broadline and pulsed NMR experiments at low temperatures (2 K). (b) J. A. Ripmeester at
the console of the Bruker CXP180 NMR spectrometer. Source: Photographs by the authors.
an NMR capability, as a 12′′ NMR electromagnet became available from William

G. Schneider’s lab. Dr. Schneider, FRS (Figure 1.2b), was an internationally known
pioneer in NMR spectroscopy who had taken on the Directorship of the Division of
Pure Chemistry in 1963 and the Presidency of NRC in 1967.
With his associates S. R. Gough and S. K. Garg, post-doctoral, and technical staff,
Don Davidson designed and built equipment to carry out dielectric and broadline
NMR measurements over a temperature range from 2 to 295 K.
John Ripmeester joined the group (1972), arriving at the same time as a com-
mercial pulsed NMR spectrometer (Bruker Bkr). The instrument was modified and
upgraded (Bruker SXP, see Figure 1.3) so that both broadline and pulsed NMR exper-
iments could be carried out down to 2 K.
During this period, Don Davidson published “Clathrate Hydrates” an overview
of clathrate hydrate science from 1810 to 1972, which appeared in Water, A Com-
prehensive Series, Vol. 2, edited by Felix Franks. This chapter summarized much of
the knowledge on these substances up to that time and is still cited as a source of
fundamental information on clathrate hydrates.
As NMR and dielectric measurements were extended down to 2 K to character-
ize guest molecule motional dynamics, by 1980, dielectric and NMR properties of
clathrate hydrates had been thoroughly investigated and resulted in a good overall
understanding. With these techniques, a considerable number of new guests form-
ing structure I and structure II hydrates were identified.
The first direct measurements of hydrate cage occupancies (129 Xe NMR and
calorimetry) were made, confirming the general correctness of the van der
Waals–Platteeuw solid solution theory. This pioneering development of 129 Xe NMR
spectroscopy which illustrated the sensitivity of NMR chemical shift parameters
to the size and shape of the clathrate cages became a widely used method to
characterize porous materials. A review summarizing the new results “NMR, NQR
and dielectric properties” was published in Inclusion Compounds, Vol. 3, edited by
J. Atwood, J.E.D. Davies, and D. D. MacNicol in 1984.
As natural gas hydrate research advanced, the period of 1970–1980 saw publica-
tion of initial reports with results from both offshore and under permafrost loca-
tions. Davidson was invited to join a committee with members from the Canadian
Federal Departments of Energy, Mines and Resources (EMR) and Indian and North-
ern Affairs (DINA) to learn about the gas hydrate potential of the Canadian Arctic.
At the NRC, this new interest sparked a dielectric and NMR study of a number
of hydrocarbon clathrate hydrates over a broad temperature range. These develop-
ing interests gave the NRC group an entry into the energy research field and the
clathrate group benefited by being able to expand their clathrate hydrate program
with funding from the National Energy Program. In recognition of the importance
of the clathrate hydrate work, the Colloid Section was renamed the Colloid and
Clathrate Section of the Division of Applied Chemistry.
Other members joining the group were John Tse (computation and diffraction,
1980), Chris Ratcliffe (NMR spectroscopy, 1982), and Paul Handa (calorime-
try, 1982), see Figure 1.4. Funds for equipment were also received, leading to
acquisitions of a Tian–Calvet calorimeter, a powder X-ray diffractometer, and a
multinuclear FT NMR instrument dedicated to solid-state experiments. A reor-
ganization of the Chemistry Division (1984) brought Dennis Klug, Ted Whalley,
and Graham McLaurin to the Clathrate Group, bringing with them expertise
in high-pressure techniques and Raman spectroscopy. Yuri Makogon, who docu-
mented the Messoyakha natural gas hydrate deposit, and a delegation from the USSR
became regular visitors to Ottawa to visit the NRC, EMR, and other hydrate labs in
Figure 1.4 Clathrate group, Division of Chemistry, National Research Council Canada circa
1984. Back row, left to right, Tony Antoniou, Ron Hawkins, Gerry McIntyre, John Ripmeester,
Paul Handa, Chris Ratcliffe; front row, left to right, John Tse, Roger Gough, Don Davidson,
Surendra Garg, Michael Collins. Source: Reproduced with permission from the National
Research Council.
Canada to share new findings on natural gas hydrates. In 1986, Don Davidson passed
away after a lengthy illness and John Ripmeester became section head in his place.
With the new group members and capabilities, a number of important contribu-
tions to understanding of hydrate solid-state properties were made, including the
confirmation of the anomalously low thermal conductivity as a general property of
clathrate hydrates. Also, the first lattice dynamics calculations on hydrates, includ-
ing the hydrate of methane, were conducted. To measure thermodynamic properties
of hydrocarbon hydrates, it became necessary to learn how to synthesize the hydrates
under carefully controlled three-phase equilibrium conditions.
In 1987, a new hexagonal clathrate hydrate, structure H (HS-III or sH), was
reported. It was characterized with an early version of an approach now known as
NMR crystallography. It was the first new family of hydrate structures since the
CS-I and CS-II hydrates were recognized. Among the pentagonal and hexagonal
rings that form the sH cages, it also features square faces constructed from four
water molecules with highly strained hydrogen bonds. In 1990, the first inventory
of structure H hydrate formers was created, also extending the number of guests
suitable for sII hydrate and noting guests which did not form ternary hydrates.
The synthesis and characterization of structure I carbon monoxide hydrate were
reported and its clathrate hydrate nature was demonstrated from dielectric and 13 C
NMR measurements. Much later, a CS-II hydrate of CO was reported.
The 1980s saw some further advances in the science of natural gas hydrates. The
success of the multi-technique approach to hydrate characterization led to collab-
oration with the US Geological Survey (USGS), Morgantown WV, to characterize
natural gas hydrate recovered from the Gulf of Mexico. X-ray diffraction confirmed
the existence of structure II hydrate for the natural gas; the calorimetry revealed
delayed melting/decomposition as an example of a self-preservation effect, and 13 C
NMR techniques showed the distribution of methane over large and small cages in
CS-II hydrate. 13 C Magic Angle Spinning (MAS) NMR was used as a means of iden-
tification of structure I and structure II hydrates. Knowledge of cage occupancies
proved to be the key to the determination of better parameters for the guest–host
potential.
In 1990, NRC underwent a major reorganization that saw the disappearance of
the familiar Division and Section structure. Most of the Clathrate Group members
joined a larger group entitled Molecular Structure and Dynamics in the newly
minted Steacie Institute for Molecular Sciences at the Sussex Drive location of
the NRC (Figure 1.5). This group, led by Keith Preston, had a broader outlook on
materials and also brought new expertise and capabilities.
For the hydrate work, the most significant changes were the inheritance of a
single-crystal X-ray diffractometer. Gary Enright (1990) and Konstantin Udachin
(1995) joined the group and developed a high level of expertise in solving highly dis-
ordered crystal structures, including clathrate hydrates. Structures of note included
those of structure H hydrate, confirming the initial structural features determined
from powder diffraction experiments, and that of CS-I CO2 hydrate, giving the
distribution of CO2 over the large and small cages. In 1998, the single-crystal
structure of tetragonal bromine hydrate was reported. Four different crystal
Figure 1.5 National Research Council Canada building at 100 Sussex Drive, Ottawa, the
home of much of the clathrate hydrate research 1990–2015. Source: Reproduced with
permission from the National Research Council.
morphologies were observed depending on synthesis conditions. All crystals had

the same microscopic crystal structure, but with different cage occupancies. This
work was seen as a further vindication of the “solid solution” model. In a paper
published in Nature entitled, “A complex clathrate hydrate structure showing
bimodal hydration,” Udachin and Ripmeester showed that a new hydrate structure
formed which consists of alternating stacks of structure H and structure II hydrates.
This structure is just one example of the many possible hydrate structures that can
be formed from stacked layers.
From phase equilibrium studies, dimethyl ether was known to form two hydrates,
one having the CS-II structure, the second was thought to be isostructural with
bromine hydrate. However, it, was discovered that the second hydrate had a novel,
dense trigonal structure. Unique among the simple hydrate structures, it did not
have any pentagonal dodecahedral cages, although some novel cage geometries
were observed.
In collaboration with Satoshi Takeya, a major advance was made in the diffraction
of powdered hydrate samples (2009). Direct methods for the analysis of powder X-ray
diffraction (PXRD) patterns, dealing with molecular fragments rather than atoms,
reduced the number of parameters to be refined and were able to give detailed struc-
tural information, including cage occupancies.
The NMR facilities were renewed and improved and Igor Moudrakovski, joining
initially as a post-doctoral fellow (1992), was able to develop a number of unique
capabilities suitable for clathrate hydrate work. One of these, MRI, was used to
image hydrate layers on ice particles, which, on melting leave intact water droplets
inside a hydrate coat. Another new technique, NMR spectroscopy with hyperpo-
larized 129 Xe was developed to give unprecedented signal enhancement to allow
the time-dependent studies of structural and compositional changes. Applications
to hydrate formation kinetics showed evidence for a precursor structure before
nucleation of crystalline hydrate with the primacy of a small cage environment.
Also, a transient structure II hydrate of Xe was identified. Time-resolved MRI
studies of hydrate formation kinetics revealed that the formation process is locally
very inhomogeneous even though the spatially averaged kinetics in the bulk system
may look homogeneous. Nucleation and crystal growth are simultaneous rather
than sequential processes, with multiple nucleation sites forming during the crystal
growth process.
The Clathrate Group joined a Canada–Japan project (JAPEX/JNOC/GSC) on the
exploration of natural gas hydrate deposits in the Mallik site in the Canadian Arctic.
The NRC group contributed laboratory analysis of recovered hydrate samples from
the Mallik 2L-38 site: 13 C NMR, Raman, diffraction, calorimetry, gas, and saturation
analyses were conducted on samples. Hailong Lu joined the group, first as a visit-
ing scientist (2002), bringing his expertise on the geochemical analysis of natural
gas hydrates. One outcome was the establishment of a protocol for the character-
ization of hydrate from natural sources, including the determination of structure
and composition. Collaboration with members of a number of hydrate cruises fol-
lowed. Samples from many worldwide hydrate locations were shipped to NRC in
liquid nitrogen containers. One highlight, published in 2007, was the discovery of
naturally occurring structure H hydrate on the Cascadia margin, offshore Vancouver
Island. The synthetic version was first reported 20 years before by the hydrate group.
The structure is capable of trapping large hydrocarbon molecules and is far more sta-
ble than CS-I hydrate. The findings were published in Nature entitled, “Complex gas
hydrate from the Cascadia Margin.”
The van der Waals–Platteeuw theory was developed to describe hydrate formation
from water and small non-polar guests. Potentials to describe guest–host interac-
tions in this case tend to be of the Lennard–Jones or Kihara type. Differences due
to guest chemistry tend to be hidden because of the limited number of potential
parameters which ultimately are obtained by fitting to experimental observables.
This procedure effectively captures all guest–host interactions (e.g. van der Waals
interactions, dipolar interactions, hydrogen bonding interaction, etc.) even though
only the non-directional van der Waals interactions are explicitly taken into account
when developing the approach. At the NRC, efforts to look for explicit effects of
guest chemistry on hydrate properties were spread over many years and involved
a number of techniques and contributions from Davidson, Alavi, Udachin, Ratcliffe,
Moudrakovski, and Ripmeester, among others.
A most evident guest observable is its water solubility, a property enabled by
hydrogen bonding between the water and the guest species. One can then ask:
Does hydrogen bonding just disappear once the guest is incorporated from the bulk
aqueous solution into the hydrate lattice? In the 1960s Don Davidson, using dielec-
tric relaxation to study water motions in hydrates noted that water reorientational
dynamics for hydrates of non-polar guests were very similar to those for ice Ih. On
the other hand, water dynamics for hydrates of water-soluble guests were much
faster with smaller activation energies. He attributed this to transient host–guest
hydrogen bonding. For THF, this would be hydrogen bonding of the oxygen atom
in the rapidly rotating guest with the water molecules forming the cage wall.
Bjerrum defect injection was proposed as a suitable mechanism for this process,
as discussed previously by Onsager and Runnels for water molecule reorientation
in ice. From the relatively small differences in guest reorientational activation

energies for hydrogen-bonded versus non-hydrogen-bonded guests, it can be seen
that the interactions tend to be weak, e.g. for THF ∼3.9 kJ mol−1 as compared to
cyclopentane with ∼2.8 kJ mol−1 . Insight from molecular dynamics computational
studies gave the dependence of the defect concentration for different guest types on
temperature. One effect of guest–host hydrogen bonding is the transfer of electron
density from the host lattice to guest–host units, thus affecting lattice stability.
Another is that in a guest–host O· · ·H—O hydrogen bond, the O· · ·O distance is
less than the sum of the van der Waals radii. This makes some of the guests appear
to be too large for the cage in which they reside, according to calculations of the
free van der Waals volume in the cage, e.g. CO2 in the small cage of CS-I CO2
hydrate. Whereas the oxygen in guests with ether or ketone functions are hydrogen
bond acceptors, guests with OH, NH, or NH2 functions can also be hydrogen bond
donors, giving rise to complex guest–host hydrogen-bonding geometries.
Stronger hydrogen bond formation, such as for methanol in the double CS-II
THF-methanol hydrate and for t-butylamine in the CS-II t-butylamine + H2 S binary
hydrate, can lead to displaced or vacant water positions in the hydrate lattice. It can
be surmised that a sufficient number of such defects can destabilize the hydrate
lattice.
Since water-soluble molecules affect the activity of aqueous solutions, it is
clear that water-soluble guests will also act as inhibitors, as accounted for by a
modified van der Waals–Platteeuw equation. Thus, it is important to recognize
that hydrate instability may have two origins – one from strong liquid water–guest
interactions accounted for by the altered activity, the other by insufficiently strong
guest–hydrate cage interactions as accounted for by the magnitude of potential
function parameters. Note that the first of these effects can be “turned off” by
eliminating the liquid aqueous phase and producing hydrate from an ice–guest
molecule reaction. Clathrate hydrates of formaldehyde and ammonia were made
this way. On the other hand, so far it has not been possible to produce a binary
methanol hydrate. Another interesting observation was the catalyst-like behavior
when small quantities of methanol or ammonia were added to the reaction of
methane and ice. These molecules, while being excluded from bulk ice, function
as catalysts by disrupting the ice surface by hydrogen bonding to surface water
molecules. This greatly enhances the rate of clathrate hydrate formation. This is not
a true “catalytic” effect since a small amount of the methanol or ammonia may be
incorporated into the hydrate phase.
Halogen–water interactions have proven to give chlorine and bromine hydrates
unusual properties. Although the chlorine van der Waals diameter is far too large to
fit into the CS-I hydrate small D cage, cage occupancies of ∼30% have been measured.
Compositional analysis by Cady has shown that chlorine hydrate is more stable than
expected from applications of the van der Waals–Platteeuw equation.
Bromine by forming a unique hydrate structure illustrates the strong
structure-directing effect of the halogen–water interaction. One feature that stands
out is the bromine guest in the tetrakaidecahedral (T) cage of the structure where,
considering the accepted van der Waals diameter of Br2 , this guest is far too large to
fit into the T cage. Another feature is the presence of the pentrakaidecahedral (P)
cage in Br2 hydrate, rarely observed in other hydrate structures. The halogen–water
interaction in bromine hydrate is reminiscent of the electrophilic electron acceptor
Br2 in the bromine-p-dioxane complex reported by Hassel many years ago.
Guest–guest interactions in hydrates with a single guest per cage rarely mani-
fest themselves directly. The best-known example is the guest dipole ordering of
trimethylene oxide in the large CS-I cage. From diffraction, the guest molecules are
sterically constrained so that the guest dipoles lie along the symmetry axis of the
T cages, but in disordered directions. Below ∼105 K the dipole directions order, as
evident from dielectric relaxation, NMR, and calorimetry.
Computational work has shown that longer range interactions exist between THF
guests in the large CS-II cage and small guests in neighboring small cages. The
number of Bjerrum defects generated by THF–water hydrogen-bonding appears to
depend on the electron donating properties and size of the small molecule in binary
THF+small gas CS-II hydrates. Most likely this interaction between guests is medi-
ated by the intervening cage wall.
In the early 2000s, the US Department of Energy (DOE) set a target of 5 mass %
as a target for onboard hydrogen storage in vehicles. In 2002, Mao and cowork-
ers determined that multiple cage occupancies of the CS-II clathrate hydrate cages
with H2 molecules were possible at low-temperature and high-pressure conditions.
In 2003, a paper published in the Proceedings of the National Academy of Sciences
(PNAS) at the NRC by Patchkovskii and Tse examined the stability of the type II
hydrogen clathrate with respect to hydrogen occupancy with a statistical mechanical
model in conjunction with first-principles quantum calculations. These works sug-
gested that the required mass % of H2 gas in the hydrate phase was possible to attain,
but at pressures and temperatures which would not be easily accessible to vehicles.
To lower the pressure required to incorporate substantial amounts of H2 gas into
a clathrate hydrate phase, a joint Korean Advanced Institute of Science and Tech-
nology (KAIST) and NRC study was carried out and published in Nature in 2005.
This study showed hydrogen storage capacity is enhanced by composition tuning
with THF. When aqueous solutions of THF with less than stoichiometric amounts
of THF relative to the pure CS-II phase were exposed to pressures of H2 gas, it was
found that the H2 guests enter both the large and the small cages under milder con-
ditions than the pure CS-II hydrate. These experimental studies were followed by a
series of molecular dynamics simulations where the energies of different H2 guest
occupancies in pure and binary clathrate hydrates were determined.
A further development in this area was that it was experimentally realized that
once pressure is relieved from an H2 containing clathrate hydrate, the hydrogen
content gradually decreases, even though the crystal structure of the hydrate phase
remained intact. In 2007, a quantum chemical study at the NRC, the energy barriers
and diffusion rates of H2 molecules diffusing through the hexagonal and pentagonal
faces of the CS-II cages were determined. The barriers to diffusion from the hexago-
nal faces can be overcome at lower temperatures, making the CS-II phase somewhat
porous to the diffusion of this gas.
A unique method was described for producing high-occupancy hydrogen hydrate

in 2012. Replacement of the nitrogen guest in CS-II nitrogen clathrate by hydrogen
at high pressures was found to result in hydrogen clathrate where small cages are
doubly occupied.
Following earlier work on the observation that organisms in cold climates use
AFPs for protection against destructive freezing by a non-colligative mechanism,
A. R. Edwards and coworkers suggested that such proteins may well have a sim-
ilar action on solid hydrate formation. Because of the difficulty in obtaining sig-
nificant quantities of AFPs, much effort was expended in searching for polymers
that might mimic the antifreeze behavior of AFPs. This led to a burgeoning research
area focused on discovering and testing of low-dosage kinetic inhibitors (LDKIs) and
resulted in some early successes such as polyvinylpyrrolidone (PVP) and polyvinyl-
caprolactam (PVCap) by E. D. Sloan. With the greater availability of AFPs and related
materials from V. Walker’s (2005) group, a collaborative effort with the NRC group
and later with P. Englezos’ group was initiated to characterize the AFP function as a
LDKI. This was carried out on a scale from the size of droplets to that of a stirred reac-
tor with multiple techniques, including gas uptake and release, calorimetry, PXRD,
solid-state NMR spectroscopy and micro-imaging, quartz crystal microbalance, and
Raman spectroscopy. Some findings include there is no correlation between AFP
function on ice or hydrate; some AFPs are as effective as polymers for antifreeze
function; elimination of the memory effect for strong AFPs; and the presence of
multiple decomposition temperatures for hydrate made in the presence of AFPs
in calorimetric measurements. As explained in the chapter on kinetics of hydrate
formation (Chapter 14), it is expected that the supercooling of hydrate forming solu-
tions with inhibitor is mirrored by a superheating effect of the solid hydrate coated
with inhibitor. What these effects have in common is that the processes are limited
by the local radius of curvature of the advancing or retreating solid–liquid interface.
Molecular dynamics simulations were performed at the NRC and University of
British Columbia to determine the mechanism of action of the winter flounder AFP
as an inhibitor of methane hydrate nucleation and growth. These studies showed
that the properly oriented dangling methyl groups on the amino acids of the AFP are
incorporated into the half-formed hydrate cages on the hydrate surface, thus inhibit-
ing local growth of the hydrate and inhibiting global growth of the hydrate through
pinning to the hydrate surface and the action of the Kelvin effect.
In the early part of the twenty-first century, environmental concerns brought
about an interest in the utilization of clathrate hydrates as a working medium for
gas storage and transportation and separation of flue and fuel gases. The groups of
P. Englezos and H. Lee had been active in the engineering research of the afore-
mentioned processes and linked up with the NRC group to provide information
on the molecular aspects using a multi-technique approach, in some cases with in
situ time resolution. Some early results were obtained on “guest-swapping” where
methane was recovered from methane hydrate by exposing the hydrate to CO2 and
“composition tuning” where the composition of binary hydrates can be varied over
a wide range.
Studies reveal that vastly improved kinetics occur for the application of
clathrate-based gas separation studies with water dispersed in stationary beds of
either microporous or low-porosity silica gel. As well spatial resolution shows that
nucleation and growth are simultaneous processes rather than time-separated
events and are spatially highly heterogeneous. A number of experiments showed
that spatially resolved kinetics are needed to develop an understanding of mech-
anisms. Results from spatially averaged experiment like gas uptake and NMR
spectroscopy may be useful for measuring process parameters but cannot give
the molecular scale details required for development of mechanisms. Molecular
dynamics simulations and consideration of classical nucleation theory led to recon-
sideration of some well-established kinetic models. For instance, the assumption of
hydrate processes being isothermal was shown to be incorrect, and taking hydrate
processes to be phase changes are more consistent with observations than the often
assumed chemical reaction – activated process model.
The ability of methane hydrate to exist outside its usual thermodynamic range
of stability was first reported in a calorimetric study of hydrate decomposition
(Davidson et al. studies on the naturally occurring hydrate from Gulf of Mexico,
1986). Later this property became an important feature (self-preservation or
anomalous preservation) of the concept to use methane hydrate as a medium
for the storage and transport of natural gas. Many laboratories contributed to the
development of this concept, including contributions from NRC (Takeya 2001) on
the guest dependence of the preservation process and the nature of the ice formed
during the preservation process. A recent study showed that THF hydrate could be
superheated by coating it with cyclopentane hydrate that has a higher melting point
than THF hydrate.
As described earlier, a combination of powder diffraction and NMR spectroscopic
results led to the characterization of HS-III as a previously unknown clathrate
hydrate family. Another Xe hydrate structure, previously known only hypotheti-
cally, was characterized in a similar way as HS-III. The hydrate, known as HS-I, is
of similar composition as the Xe hydrates CS-I and HS-III and demonstrates that
the synthetic pathway is important in defining the structure of the product.
It is well known that ice Ih and ammonium fluoride are isostructural and form
a solid solution with a maximum NH4 F concentration of ∼22%. The NH4 + and
F– ions replace two water molecules in the ice lattice. It was likely that clathrate
hydrate lattices could be built with some water sites substituted with NH4 + and F–
ions, although it is not possible to build pentagonal rings from only NH4 F. The NMR
spectrum of the xenon guest in the NH4 F-substituted clathrate shows up to five
distinguishable D cages because of different NH4 F distribution patterns, and the
unit cell parameters shrink with increasing NH4 F content (2012). The CS-I version
of the NH4 F-substituted hydrate lattice was shown to be a viable host lattice for
methanol guests, an impossibility for the pure CS-I hydrate lattice. A new help-gas
role for methanol was discovered so that unconventional guests such as alcohols
and diols could be incorporated in the large cages of NH4 F substituted lattices of
CS-I and HS-III hydrates.
1.4 Contributors to NRC Clathrate Hydrate Research 21
Physical aspects of clathrate hydrates as solid-state materials have been studied at

the NRC. In 1986, Don Davidson and coworkers measured the index of refraction of
hydrate for the first time. They measured the index of refractive of water–THF solu-
tions and THF clathrate hydrate crystals that formed upon cooling the solution up
to −20 ∘ C. The refractive index of the THF hydrate, which was greater than ice, was
reproduced fairly accurately using a reactive field model where the THF molecule
was assumed to lie in a cavity with the radius of the CS-II 512 64 cage (Davidson et al.
1986). The elastic constants of ice in the high-pressure range of clathrate hydrate
formation were measured by H. Kiefte and coworkers (Memorial University of New-
foundland) and E. Whalley of the NRC in 1988. Inelastic neutron scattering studies
were performed on methane hydrate under high-pressure conditions in 2000 as a
collaboration between the University of Edinburgh and the NRC. At room temper-
ature and high pressure (0.9 GPa), methane hydrate was found to form a hexagonal
HS-III (MH-II) phase (Loveday et al. 2001, 2003). Further work on methane hydrate
at even higher pressures was carried out by the same group in 2001. The structure of
a new methane hydrate is solved from neutron and X-ray powder diffraction at pres-
sures of 2.0 GPa and higher. A transition from a clathrate to a filled ice structure was
observed and the structure of methane hydrate III was finally uncovered (Loveday
2001). In a follow-up paper published in Nature that year, neutron and synchrotron
X-ray diffraction studies determined the thermodynamic nature of methane hydrate
which probably exists on Saturn’s moon Titan, suggesting that the hydrate phases are
a plausible source for the continuing replenishment of Titan’s methane atmosphere.
High-pressure inelastic X-ray scattering was used to study the elastic properties
of the high-pressure methane hydrate MH-II and MH-III structures in 2005 by the
NRC staff and coworkers from Germany and France. These studies revealed how
guest molecules interact with the cages in clathrates and filled ice structures and
how under high pressures, the water–methane guest repulsive interactions lead to
the elastic properties of the methane hydrate phases becoming significantly different
from the ice phases at the same pressure.
A 2005 Nature Materials paper entitled, “Anharmonic motions of Kr in the
clathrate hydrate,” determined the origins of the low thermal conductivity in
clathrates using incoherent inelastic neutron scattering, nuclear resonant inelastic
X-ray scattering (NRIXS) – a powerful new technique, and molecular dynamics sim-
ulations. The low thermal conductivity in the hydrate phase was related to the cou-
pling of the local anharmonic guest rattling motions in the cages with the host lattice
vibrations. This coupling leads to the scattering of the heat-carrying lattice phonons
resulting in a glass-like anomaly in the clathrate phase thermal conductivity.
1.4 Contributors to NRC Clathrate Hydrate Research

NRC scientific staff
Don Davidson, Surendra K. Garg, Roger Gough, John Ripmeester, John Tse, Paul
Handa, Chris Ratcliffe, Igor Moudrakovski, Gary Enright, Konstantin Udachin,
Hailong Lu, Dennis Klug.
NRC technical staff
Ron Hawkins, Graham McLaurin, Régent Dutrisac, Jamie Bennett, Steve Lang, Jeff
Farnand.
Other collaborators from the NRC
Edward Whalley, B. Morris, Derek Leaist, Michael Collins, Ian Cameron, Mike
Desando, Litao Chen, Xu Zhu, Anivis Sanchez, Darren Brouwer, Marek
Zakrzewski, Chris Tulk, Lee Wilson, Yong Ba, Luy Ding, Eric Brouwer, Andreas
Brinkmann, Erik van Klaveren, Hidenotsuke Itoh, Serguei Patchkovskii, Vladimir
P. Shpakov, Saman Alavi, D. Yu. Stupin.
Scientific collaborators on clathrate hydrates
Alan Judge, Scott Dallimore, Fred Wright, Michael Riedel (Geologic Survey of
Canada).
George Spence, Ross Chapman (University of Victoria).
Peter Englezos, Robin Susilo, Rajnish Kumar, Praveen Linga, Nagu Daraboina,
Alireza Bagherzadeh, Adebola Adeyemo, Hassan Sharifi (University of British
Columbia) Virginia Walker, Huang Zeng, Hiroshi Ohno, Raimond Gordienko
(Queens University), Harry Kiefte, Maynard J. Clouter, Robert E. Gagnon
(Memorial University of Newfoundland), Tom K. Woo (University of Ottawa).
Richard Coffin, John Pohlman (Naval Research Laboratory, Washington), Jamie J.
Molaison, António M. dos Santos, Neelam Pradhan, Bryan C. Chakoumakos, Ling
Yang (Oak Ridge National Laboratory), Wolfgang Sturhahn, Esen E. Alp, Jiyong
Zhao, Charles D. Martin (Argonne National Laboratory) W. F. Lawson (US Depart-
ment of Energy, Morgantown), Peter Brewer (Monterey Bay Aquarium Research
Institute).
Dendy Sloan, Ajay Mehta, Ramesh Kini, Siva Subramanian, Keith Hester, Carolyn
Koh, Amadeu K. Sum (Colorado School of Mines), Lars Ehm, John B. Parise
(Stony-Brook University).
Hirokazu Nakayama (Kobe Pharmaceutical University), Tsutomu Uchida
(Hokkaido University), Satoshi Takeya, Sanehiro Muromachi (AIST), Ryo
Ohmura (Keio University), Takuo Okuchi (Nagoya University).
Huen Lee, Yutaek Seo, Jongwon Lee, Kyuchul Shin (KAIST).
Deqing Liang (Chinese Academy of Sciences, Guangzhou), Changling Liu (China
Geologic Survey, Qingdao).
Anbawaghan Krishnamoorthi (Gas Authority of India, Mumbai).
Cor Peters, Miranda Mooyer-van den Heuvel, Maaike Kroon, Alondra Torres Trueba
(TU Delft), Jan P. J. Michels, Johnannes A. Schouten (University of Amsterdam).
Judith Schicks, Manja Luzi (GFZ Potsdam) Julian Baumert (Universität Kiel).
Werner Press (Institute Laue-Langevin), Micheal Krisch, Herwig Requart (European
Synchroton Radiation facility).
Stefan Janssen (Paul Scherrer Institute).
John S. Loveday, Richard J. Nelmes, Malcolm Guthrie (University of Edinburgh).
1.5 Review Articles and Books on Clathrate Hydrates 23
1.5 Review Articles and Books on Clathrate Hydrates
1926 W. Schroeder. Die Geschichte der Gas Hydrate, Sammlung chemischer und
chemisch-technischen Vorträge. Vol. 29. Stuttgart, Verlag Ferdinand Enke.
1946 W. M. Deaton and E. M. Frost. Gas hydrates and relation to the operation of natural
gas pipelines. United States Department of the Interior, Bureau of Mines. 1949.
1958 J. H. van der Waals, J. C. Platteeuw. Clathrate solutions. In Advances in Chemical
Physics, Vol. II, Wiley.
1959 D. L. D. Katz, P. Cornell, R. Kobayashi, F. H. Poettman, J. A. Vary, J. R. Elenbaas and
C. F. Weinang. Water-hydrocarbon systems in Handbook of Natural Gas
Engineering. McGraw-Hill.
1963 University of Pittsburgh. Bibliography of Publications on Compounds of the Gas
Hydrate Type. United States Department of the Interior, Office of Saline Water.
1967 G. A. Jeffrey, R. K. McMullan. The Clathrate Hydrates. In, Progress in Inorganic
Chemistry, F. A. Cotton, Ed. Vol. 8. Wiley.
1973 D. W. Davidson. Clathrate Hydrates, In Water, A Comprehensive Treatise, F. Franks,
Ed. Vol. 2. Plenum.
1974 Y. F. Makogon. Hydrates of Natural Gas. NEDRA (PennWell, Tulsa, 1981).
1977 E. Berecz, M. Balla-Achs. Gas Hydrates. Elsevier.
1983 J. L. Cox. Natural Gas Hydrates: Properties, Occurrence and Recovery. Butterworth.
1983 V. A. Kuuskraa, E. C. Hammershaimb. Handbook of Gas Hydrate Properties and
Occurrence. Lewin & Associates.
1984 G. A. Jeffrey. Hydrate inclusion compounds, in Inclusion Compounds. J. L. Atwood,
J. E. D. Davies, D. D. McNicol, Eds., Vol. 1. Academic Press.
1984 D. W. Davidson, J. A. Ripmeester. NMR, NQR and dielectric properties of clathrates,
in Inclusion Compounds. J. L. Atwood, J. E. D. Davies, D. D. McNicol, Eds., Vol. 3
Academic Press.
1988 G. D. Holder, S. P. Zetts, N. Pradhan. Phase behaviour in systems containing
clathrate hydrates: A Review. Rev. Chem. Eng. 5: 1–70.
1990 D. L. Katz and R. L. Lee. Gas hydrates and their Prevention. In Natural Gas
Engineering: Production and Storage. McGraw-Hill.
1990 E. D. Sloan, Jr. Clathrate Hydrates of Natural Gases. CRC Press.
1991 J. A. Ripmeester, C. I. Ratcliffe. Solid state NMR Studies of Inclusion Compounds.
In Inclusion Compounds. J. L. Atwood, J. E. D. Davies, D. D. McNicol, Eds. Vol. 5.
Oxford University Press.
1992 P. M. Rodger. Computational Studies of Clathrate Hydrates. In Spectroscopic and
Computational Studies of Supramolecular Systems. J. E. D. Davies, Ed. Springer.
1993 P. Englezos. Clathrate Hydrates. Ind. Eng. Chem. 32: 1251–1274.
1996 G. P. Johari. Dielectric Methods for Studying Supramolecular Clathrate Structures.
In Comprehensive Supramolecular Chemistry, Vol. 8. Physical Methods in
Supramolecular Chemistry. J. E. D. Davies, J. A. Ripmeester. Eds. Chapter 3.
Elsevier.
1996 J. A. Ripmeester, C. I. Ratcliffe. Solid-State NMR Spectroscopy: Applications to

Supramolecular Chemistry. In Comprehensive Supramolecular Chemistry. J. L.
Atwood, J. E. D. Davies, D. D. McNicol, F. Vogtle, J.-M. Lehn Eds. Vol. 8: 323–380.
Pergamon.
1996 G. A. Jeffrey. Hydrate Inclusion Compounds. In Comprehensive Supramolecular
Chemistry. J.-M. Lehn, J. L. Atwood, J. E. D. Davies, D. D. MacNicol, F. Vögtle, Eds.
Vol. 6: 757–788. Elsevier.
1996 Y. A. Dyadin, V. R. Belosludov. Stoichiometry and Thermodynamics of Clathrate
Hydrates. In Comprehensive Supramolecular Chemistry. J.-M. Lehn, J. L. Atwood, J.
E. D. Davies, D. D. MacNicol, F. Vögtle, Eds. Vol. 6: 789–824. Elsevier.
1997 Y. F. Makogon. Hydrates of Hydrocarbons. Pennwell Books.
1999 S. R. Dallimore, T. Uchida, T. S. Collett, Scientific Results from JAPEX/JNOC/GSC
Mallik 2L-38 Gas Hydrate Research Well, Mackenzie Delta, NWT, Canada, Geologic
Survey of Canada Bulletin 544.
2000 B. A. Buffett. Clathrate hydrates. Annu. Rev. Earth Planet. Sci. 2000; 28: 477–507.
2001 C. K. Paull, W. P. Dillon Eds Natural Gas Hydrates: Occurrence, Distribution and
Detection. American Geophys. Union.
2004 C. E. Taylor, J. T. Kwan. Eds. Advances in the Study of Gas Hydrates. Springer.
2006 M. D. Max, A. H. Johnson, W. P. Dillon. Economic Geology of Natural Gas Hydrates.
Springer.
2007 E. D. Sloan, Jr., C. A. Koh, Clathrate Hydrates of Natural Gases. 3rd Ed., CRC Press.
2009 C. A. Koh, A. K. Sum, E. D. Sloan. Gas hydrates: Unlocking the energy from icy
cages. App. Phys. Rev. 2009; 106: 061101.
2010 J. F. Gabitto, C. Tsouris. Physical properties of gas hydrates: A review. J. Thermodyn.
2010; ID: 271291.
2012 S. Alavi, K. A. Udachin, C. I. Ratcliffe, J. A. Ripmeester. Clathrate Hydrates. In
Supramolecular Chemistry: From Molecules to Nanomaterials. J. W. Steed, P. A.
Gales, Eds. Wiley.
2012 Barnes BC, Sum AK. Advances in molecular simulations of clathrate hydrates. Curr.
Opin. Chem. Eng. 2012; 2: 184–190.
2015 Special Issue of Can. J. Chem. 93 Part 1 and 2. Issues Dedicated to J. A. Ripmeester.
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compounds for energy harvesting. MRS Ener. Sustain. Rev. J. 2015;
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2015 P. Babu, P. Linga, R. Kumar, P. Englezos. A review of the hydrate based gas
separation (HBGS) process for carbon dioxide pre-combustion capture. Energy 85:
261–279.
2015 Tse JS. Computational Techniques in the study of the properties of clathrate
hydrates. In Reviews in Computational Chemistry, Vol. 28. Edited by Parrill AL,
Lipkowitz KB. Wiley, New York, 2015: 315–389.
2015 English NJ, MacElroy JMD. Perspectives on molecular simulation of clathrate
hydrates: Progress, prospects and challenges. Chem. Eng. Sci. 2015; 121: 133–156.
2016 J. A. Ripmeester, S. Alavi. Some current challenges in clathrate hydrate science:
Nucleation, decomposition and the memory effect. Current Opinion, Solid State
Mater. Sci. 20: 344–351.
1.6 Conference Proceedings 25
2016 P. Warrier, N. N. Khan, V. Srivastava, C. M. Maupin, C. A. Koh. Overview:

Nucleation of clathrate hydrates. J. Chem. Phys. 2016; 145: 211705.
2017 D. Broseta, L. Ruffine, A. Desmedt. Gas Hydrates 1: Fundamentals,
Characterization, and Modeling. Wiley.
2017 M. Yang, Z. R. Chong, J. Zhang, Y. Song, P. Linga. Advances in nuclear magnetic
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clathrate hydrate based desalination to strengthen energy-water nexus. ACS
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review. J. Supercrit. Fluids 2018; 134: 51–60.
2020 A. Hassanpourouzabad, E. Joonaki, M. Vasheghani Farahani, S. Takeya, C. Rupple,
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1.6 Conference Proceedings
1.6.1 Canadian Permafrost Conference
1981 Proceedings of the 4th Canadian Permafrost Conference, Calgary, H.M French,
Ed., National Research Council of Canada, Ottawa, 1983.
1.6.2 Physics and Chemistry of Ice
1972 Physics and Chemistry of Ice. Royal Society of Canada, Ottawa, 1973.
1986 7th Symposium on the Physics and Chemistry of Ice, Grenoble. J. de Phys. 48
C1-1987.
1992 Physics and Chemistry of Ice. Hokkaido University Press, Sapporo.
1996 Physics and Chemistry of Ice, Hanover, New Hampshire, USA, J. Phys. Chem. B
1997; 101: Issue No. 32.
2002 10th Conference of the Physics and Chemistry of Ice, 2002 St. Johns, Nfld., Can.
J. Phys. 2003; 81: No. 1-2.
2006 11th Conference of the Physics and Chemistry of Ice, 2006 Bremerhaven,
Germany. https://epic.awi.de/id/eprint/26177/1/Wil2007b.pdf
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“Yes, querida.”
Hand in hand, the lovers left the adobe, and the somber echoing
tunnel, with the electric wires seen like a spider’s web across its
farther end, was to them an underground passage to Paradise.
—Copyright, and used by kind consent of the author.
Note.—Spanish words are pronounced according to the continental
pronunciation, and each vowel is given a syllable. “Si Ma-dre,” pronounced See
Ma´dray, yes, mother. “Ma-ma-ci-ta,” pronounced Ma-ma-cee-tah, little mother.
“Sin Ver-gu-en-za,” pronounced Seen Vehr-goo-ain´tha, shameless. “Que-ri-di-ta,”
pronounced Kay-ree-dee´tah, little love. “Por-ta-les,” pronounced Por-tah´lays,
covered sidewalks. “Gente decente,” pronounced Hen´tay day-then´tay, the
aristocracy. “Coch-i-no,” pronounced Co-cheeńo, pig. “Lin-di-ta,” pronounced
Leen-dee´ta, pretty. “Que-ri-da,” pronounced Kay-ree´da, beloved.
THE INTERVENTION OF PETER

By Paul Laurence Dunbar
No one knows just what statement it was of Harrison Randolph’s
that Bob Lee doubted. The annals of these two Virginia families have
not told us that. But these are the facts:
It was at the home of the Fairfaxes that a few of the sons of the old
Dominion were giving a dinner, and a brave dinner it was. The
courses had come and gone, and over their cigars they had waxed
more than merry. In those days men drank deep, and these men
were young, full of the warm blood of the South and the joy of living.
What wonder then that the liquor that had been mellowing in the
Fairfax cellars since the boyhood of their revolutionary ancestor
should have its effect upon them?
It is true that it was only a slight thing which Bob Lee affected to
disbelieve, and that his tone was jocosely bantering rather than
impertinent. But sometimes Virginia heads are not less hot than
Virginia hearts. The two young men belonged to families that had
intermarried. They rode together, hunted together and were friends
as far as two men could be who had read the message of love in the
dark eyes of the same woman. So perhaps there was some thought
of the long-contested hand of Miss Sallie Ford in Harrison
Randolph’s mind when he chose to believe that his honor had been
assailed.
His dignity was admirable. There was no scene to speak of. It was
all very genteel.
“Mr. Lee,” he said, “had chosen to doubt his word, which to a
gentleman was a final insult. But he felt sure that Mr. Lee would not
refuse to accord him a gentleman’s satisfaction.” And the other’s
face had waxed warm and red and his voice cold as he replied: “I
shall be most happy to give you the satisfaction you demand.”
Here friends interposed and attempted to pacify the two. But
without avail.
Each of the young men nodded to a friend and rose to depart. The
joyous dinner-party bade fair to end with much more serious
business.
“You shall hear from me very shortly,” said Randolph, as he strode

to the door.
“I shall await your pleasure with impatience, sir, and give you such
a reply as even you cannot disdain.”
Peter, the personal attendant of Harrison Randolph, stood at the
door as his master passed out, and went on before him to hold his
stirrup. The young master and his friend and cousin, Dale, started off
briskly and in silence, while Pete, with wide eyes and disturbed face,
followed on behind. Just as they were turning into the avenue of
elms that led to their own house, Randolph wheeled his horse and
came riding back to his servant.
“Pete,” said he sternly, “what do you know?”
“Nuffin’, Mas’ Ha’ison, nuffin’ ’t all. I do’ know nuffin’.”
“I don’t believe you.” The young master’s eyes were shining
through the dusk. “You’re always slipping around spying on me.”
“Now, dah you goes, Mas’ Randolph. I ain’t done a thing, and you
got to ’mence pickin’ on me—”
“I just want you to remember that my business is mine.”
“Well, I knows dat.”
“And if you do know anything, it will be well for you to begin
forgetting it right now. Take Bess around and see her attended to.
Leave Dale’s horse here, and—I won’t want you any more to-night.”
Pete turned away with an injured expression on his dark face.
“Bess,” he said to the spirited black mare, as he led her toward the
stables, “you jes’ better t’ank yo’ Makah dat you ain’t no human
bein’, ’ca’se human bein’s is cur’ous articles. Now you’s a horse,
ain’t you? And dey say you ain’t got no soul, but you got sense,
Bess, you got sense. You’s a high steppah, too, but you don’ go to
work an’ try to brek yo’ naik de fus’ chanst you git. Bess, I ’spect you
’ca’se you got jedgment, an’ you don’ have to have a black man
runnin’ aftah you all de time plannin’ his head off jes’ to keep you out
o’ trouble. Some folks dat’s human bein’s does. Yet an’ still, Bess,
you ain’t nuffin’ but a dumb beas’, so dey says. Now, what I gwine to
do? Co’se dey wants to fight. But whah an’ when an’ how I gwine to
stop hit? Doan want me to wait on him to-night, huh! No, dey want to
mek dey plans an’ do’ want me ’roun’ to hyeah, dat’s what’s de
mattah. Well, I lay I’ll hyeah somep’n’ anyhow.”
Peter hurried through his work and took himself up to the big
house and straight to his master’s room. He heard voices within, but
though he took many liberties with his owner, eavesdropping was not
one of them. It proved too dangerous. So, though he lingered on the
mat, it was not for long, and he unceremoniously pushed the door
open and walked in. With a great show of haste, he made for his
master’s wardrobe and began busily searching among the articles
therein. Harrison Randolph and his cousin were in the room, and
their conversation, which had been animated, suddenly ceased
when Peter entered.
“I thought I told you I didn’t want you any more to-night.”
“I’s a-lookin’ fu’ dem striped pants o’ yo’n. I want to tek ’m out an’
bresh ’em; dey’s pintly a livin’ sight.”
“You get out o’ here.”
“But, Mas’ Ha’ison, now—now—look-a-hyeah—”
“Get out, I tell you.”
Pete shuffled from the room, mumbling as he went: “Dah now, dah
now! driv’ out lak’ a dog! How’s I gwine to fin’ out anyt’ing dis way? It
do ’pear lak Mas’ Ha’ison do try to give me all de trouble he know
how. Now he plannin’ and prijickin’ wif dat cousin Dale an’ one jes’
ez scattah-brained ez de othah. Well, I ’low I got to beat dis time
somehow er ruther.”
He was still lingering hopeless and worried about the house when
he saw young Dale Randolph come out, mount his horse, and ride
away. After a while his young master also came out and walked up
and down in the soft evening air. The rest of the family were seated
about on the broad piazza.
“I wonder what is the matter with Harrison to-night,” said the young
man’s father, “he seems so preoccupied.”
“Thinking of Sallie Ford, I reckon,” some one replied; and the
remark passed with a laugh. Pete was near enough to catch this, but
he did not stop to set them right in their conjectures. He slipped into
the house.
It was less than two hours after this when Dale Randolph returned
and went immediately to his cousin’s room, where Harrison followed
him.
“Well?” said the latter, as soon as the door closed behind them.
“It’s all arranged, and he’s anxious to hurry it through for fear some
one may interfere. Pistols, and to-morrow morning at daybreak.”
“And the place?”
“The little stretch of woods that borders Ford’s Creek. I say,
Harrison, it isn’t too late to stop this thing yet. It’s a shame for you
two fellows to fight. You’re both too decent to be killed yet.”
“He insulted me.”
“Without intention, every one believes.”
“Then let him apologize.”
“As well ask the devil to take Communion.”
“We’ll fight then.”
“All right. If you must fight you must. But you’d better go to bed, for
you’ll need a strong arm and a steady hand to-morrow.”
“I’m going to write a couple of letters first,” he said; “then I shall lie
down for an hour or so. And, by the way, Dale, if I—if it happens to
be me to-morrow, you take Pete; he’s a good fellow.”
The cousins clasped hands in silence and passed out. As the door
closed behind them a dusky form rolled out from under the bed and
the disreputable, eavesdropping, backsliding Peter stood up and
rubbed a sleeve across his eyes.
“It ain’t me dat’s gwine to be give to nobody else. I hates to do it;
but dey ain’t no othah way. Mas’ Ha’ison cain’t be spaihed.” He
glided out mysteriously, some plan of salvation working in his black
head.
Just before daybreak next morning three stealthy figures crept out
and made their way toward Ford’s Creek. One skulked behind the
other two, dogging their steps and taking advantage of the darkness
to keep very near to them. At the grim trysting-place they halted and
were soon joined by other stealthy figures, and together they sat
down to wait for the daylight. The seconds conferred for a few
minutes. The ground was paced off, and a few, low-pitched orders
prepared the young men for business.
“I will count three, gentlemen,” said Lieutenant Custis. “At three,
you are to fire.”
At last daylight came, gray and timid at first, and then red and bold
as the sun came clearly up. The pistols were examined and the men
placed face to face.
“Are you ready, gentlemen?”
But evidently Harrison Randolph was not. He was paying no
attention to the seconds. His eyes were fixed on an object behind his
opponent’s back. His attitude relaxed and his mouth began to twitch.
Then he burst into a peal of laughter.
“Pete,” he roared, “drop that and come out from there!” and away
he went into another convulsion of mirth. The others turned just in
time to see Pete cease his frantic grimaces of secrecy at his master,
and sheepishly lower an ancient fowling-piece which he had had
leveled at Bob Lee.
“What were you going to do with that gun leveled at me?” asked
Lee, his own face twitching.
“I was gwine to fiah jes’ befo’ dey said free. I wa’n’t gwine to kill
you, Mas’ Bob. I was on’y gwine to lame you.”
Another peal of laughter from the whole crowd followed this
condescending statement.
“You unconscionable scoundrel, you! If I was your master, I’d give
you a hundred lashes.”
“Pete,” said his master, “don’t you know that it is dishonorable to
shoot a man from behind? You see you haven’t in you the making of
a gentleman.”
“I do’ know nuffin’ ’bout mekin’ a gent’man, but I does know how to
save one dat’s already made.”
The prime object of the meeting had been entirely forgotten. They
gathered around Pete and examined the weapon.
“Gentlemen,” said Randolph, “we have been saved by a miracle.
This old gun, as well as I can remember and count, has been loaded
for the past twenty-five years, and if Pete had tried to fire it, it would
have torn up all this part of the country.”
Then the eyes of the two combatants met. There was something
irresistibly funny in the whole situation, and they found themselves
roaring again. Then, with one impulse, they shook hands without a
word.
And Pete led the way home, the willing butt of a volume of good-
natured abuse.—From “Folks from Dixie,” copyright by Dodd, Mead
& Company, New York, and used by arrangement.
PART THREE
Melodious Reading
Conversational elements: Pitch, Inflection, Color, Stress, Pause,
Movement, Time. Separate discussions and illustrations with number
of exercises for the pupil to practice. Melody in verse and in prose.
EXPRESSIVE SPEECH[9]
By Robert Lloyd
’Tis not enough the voice be sound and clear,

’Tis modulation that must charm the ear.
When desperate heroines grieve with tedious moan,
And whine their sorrows in a see-saw tone,
The same soft sounds of unimpassioned woes
Can only make the yawning hearer doze.
That voice all modes of passion can express

Which marks the proper word with proper stress;
But none emphatic can the reader call
Who lays an equal emphasis on all.
...
He who in earnest studies o’er his part
Will find true nature cling about his heart.
The modes of grief are not included all
In the white handkerchief and mournful drawl.
A single look more marks the internal woe
Than all the windings of the lengthened O!
Up to the face the quick sensation flies,
And darts its meaning from the speaking eyes.
Love, transport, madness, anger, scorn, despair,
And all the passions, all the soul is there.
CHAPTER X
MELODIOUS READING
What charm and delight surround a sweet, melodious voice,

whether of woman or man. Who is there that does not recall such a
voice and its influence upon him? Who does not have clinging
memories of the voice of the mother, crooning over her babe, or
singing a sweet lullaby as it lay at her breast; of a father, softening its
strong and resonant power to soothe the restlessness of his little one
who was sick; of the blushing maiden, who consciously or
unconsciously had learned the immeasurably greater power
exercised over her fellows, whether of her own or the opposite sex,
by a soft, pure, well-controlled voice, rather than the high-pitched,
tense, loud and harsh chatter of her associates. The calm, quiet, soft
and low-pitched, though firm, voice of the teacher, the parent, the
employer, the salesman, the speaker, the statesman, is far more
effective, far more likely to attain its end than the harsh, raucous,
loud, too emphatic and high-pitched voice of the uncontrolled,
untaught, or careless speaker. And to listen to a reader, be he
preacher, lawyer, judge, or orator, reading in public to a large
audience, or for the pleasure and instruction of his own loved ones,
or a few chosen friends, whose voice is melodious in every cadence,
whose every intonation is musical and in good taste, what joy such a
reader is able to bestow. How memory thrills as we recall a few
readers of this type. Why should they be so few? Why should there
be so many harsh, nasal, raucous, high-pitched, unmelodious
voices? The reason is found mainly in lack of training, lack of a little
thought, indifference to the possession of the finer gifts of life. For
every boy and girl has it in his or her power, by the exercise of a little
care, a little thought, a little self-restraint, a little time spent in
discipline to produce the sweet and charming voice, with clean-cut,
distinct, pleasing enunciation and pronunciation that will afford joy
during the whole of a long life.
One’s own ear will tell whether his voice is properly pitched,
pleasing, melodious, or the opposite. A few minutes spent in speech
daily before a looking-glass will forever fix the habit of making the
face pleasing; and an hour a day for a month will fix perfect habits of
pronunciation and enunciation that will remain through life. When
these arts are fixed, then a few hours’ study of the thought of the
author and the inflections and modulations of the voice necessary to
represent, to convey to the ear of the listener, the full power of that
thought, and the reader has equipped himself, herself, to give joy to
countless thousands. Is it not worth while to spend a few hours to
gain such power?
Exercises in Inflection
By inflection is meant the glide of the voice within a word to a
higher or a lower pitch. This glide may be quick and short, or long
and slow. It may be a rising or a falling glide, or both. The value of
inflection rests in its power to make what is said more emphatic, to
aid in clear enunciation, to aid in overcoming monotony. On all
emphasized words we have an intensified inflection. This is
illustrated in Portia’s speech in “The Merchant of Venice.” In studying
this excerpt we discover that all the emphasized words have a
pronounced inflection. In the first group of words, “If to do were as
easy as to know what were good to do,” we find the most intensified
inflection is upon the word “know” because this is the most emphatic
word of the group. This reveals that inflection is one of the most vital
means of emphasis.
In regard to inflection as an aid to clear enunciation, we find that
inflection occurs upon the accented syllable of a long word, and if
due attention is given to the syllable upon which the accent falls, the
word will receive a more perfect utterance. For instance, we can
readily see in the following words, which are often mispronounced,
the important part that inflection plays in the proper pronunciation of
them:
abdomen
abject
acclimate
address
admirable
alias
brigand
caricature
chastisement
chauffeur
combatant
contumely
demoniacal
discourse
exquisite
finance
grimace
herculean
horizon
impious
impotent
incomparable
indisputable
industry
inexplicable
interpolate
inquiry
lyceum
mausoleum
mischievous
obligatory
research
resource
superfluous
traverse
vagary
vehement
vehicle
virago
verbose
virtue
virtually
(For the correct pronunciations see Webster’s New International

Dictionary.)
We readily see that the proper use of inflection cannot help but
give variety and contrast to our speech, and this aids immeasurably
in overcoming the persistent use of monotones.
We shall take up the different kinds of inflection and illustrate them
with appropriate exercises. The student should consider the aim and
value of each kind of inflection and then proceed to practice orally
the exercises, listening intently to his voice to see that it responds.
Kinds of Inflection
Falling Glide in the voice indicates a complete and positive
assertion. For example:
“The Prince’s banner wavered, staggered backward,
hemmed by foes!”
A command, although punctuated with a question mark, is

rendered with a falling glide in the voice. For example:
“Halt! who goes there?” “Speak, what trade art thou?”
Rising Glide in the voice indicates incompleteness and doubt. For

example:
“How ‘the fellow by the name of Rowan’ took the letter,

sealed it up in an oilskin pouch, strapped it over his heart, in
four days landed by night off the coast of Cuba from an open
boat, disappeared into the jungle, and in three weeks came
out on the other side of the island, having traversed a hostile
country on foot, and delivered his letter to Garcia, are things I
have no special desire now to tell in detail.”
Circumflex Glide indicates a twist in the voice which reflects a like

twist in the mind.
Well, I guess I’ll have to, since you say so.
Exercises for Inflectional Agility:
I find earth not gray but rosy, heaven not grim but fair of hue.
Do I stoop? I pluck a posy. Do I stand and stare? All’s blue.
—Browning.
I must have left my book on this table last night. (Read two ways.)
There are three pleasures pure and lasting, and all derived from
inanimate things—books, pictures, and the face of nature.
—Hazlitt.
We are perplexed, but not in despair; persecuted, but not

forsaken; cast down, but not destroyed.
What right have you, O passer by the way, to call any flower a
weed? Do you know its merits? Its virtues? Its healing qualities?
Because a thing is common, shall you despise it? If so, you might
despise the sunshine for the same reason.
Oh, yes, I begin to remember you now. Do you really think it true?
Yes, he’s a millionaire. (Read two ways.)
Breathes there a man, with soul so dead,

Who never to himself hath said,
This is my own, my native land?
Whose heart hath ne’er within him burn’d,
As home his footsteps he hath turn’d
From wandering on a foreign strand?
If such there breathe, go, mark him well.
—Sir Walter Scott.
Now clear, pure, hard, bright, and one by one, like the hailstones,
Short words fall from his lips fast as the first of a shower,
Now in two-fold column: Spondæ, Iamb, Trochee,
Unbroken, firm-set, advance, retreat, trampling along,—
Now with a sprightlier springiness, bounding in triplicate syllables,
Dance the elastic Dactylics in musical cadences on;
Now their voluminous coil intertangling like huge anacondas,
Roll overwhelmingly onward the sesquipedalian words.
—Browning.
Resolve!
To keep my health!
To do my work!
To live!
To see to it that I grow and gain and give!
Never to look behind me for an hour!
To wait in weakness and to walk in power;
But always fronting onward to the light.
Always and always facing toward the right.
Robbed, starved, defeated, wide astray—
On, with what strength I have!
Back to the way!
A very interesting and helpful exercise in the study of inflection is

the use of the one-word dialogue. The following scene, written by a
pupil, is given as an illustration:
Scene: Midnight; and the two are awakened by a noise.

She. Philipe!
He. What?
She. Burglar!
He. Where?
She. Bathroom!
He. Gun?
She. No!
He. Sh-h!
She (fainting). Darling!
He. Huh! Cat! (catching her).
It is by use of tone and inflection that the following exercises are
properly rendered.
How are you to-day? Ha. (inquiry, surprise).

I say how are you to-day? Ha. (rising doubt).
Have you suddenly become deaf? Ha. (indignation).
I have been trying to find out how you are Ha. (satisfaction,
to-day. laugh).
I am glad you heard me. Ha. (short grunt).
I am on my way to the store. Ha. (do not believe it).
Will you go with me? Ha. (glad to).
A Study of Pitch
Pitch is simply the modulation of the voice as high or low. In
natural speech we seldom have more than one word on the same
pitch. Note the constant change of pitch in a good conversationalist.
In listening to such, we discover what?
First: If one idea is expressed on one pitch, its antithesis is
instinctively expressed on another pitch. For example: “When our
vices leave us, we flatter ourselves we leave them.” “The prodigal
robs his heir, the miser robs himself.” “Excess of ceremony shows
want of breeding.”
Second: A quick leap of the mind causes a leap in the voice, or, in
other words, it causes a change of pitch. For example: “So you say
you are going to—Well, hello, John! How did you get here?”
There can be no definite rules laid down governing Changes of
Pitch. If we think progressively, giving ourselves completely to each
successive idea, permitting our movement of tone to be the direct
outcome of the action of the mind we shall have no difficulty in
modulating our pitch.
In reading the following selections, note carefully the natural
tendency of the voice to change pitch as the mind leaps from one
thought to another.
O larks, sing out to the thrushes,
And thrushes, sing to the sky!
Sing from your nests in the bushes,
And sing wherever you fly.
Then sing, O bird in the tree,

Then sing, skylark in the blue,
Sing loud, sing clear, that the King may hear,
And my soul shall sing with you.
I wield the flail of the lashing hail,

And whiten the green plains under:
And then again I dissolve in rain,
And laugh as I pass in thunder.
I slip, I slide, I gloom, I glance.
Away to the hills, to the caves, to the rocks,—

Ere I own a usurper, I’ll couch with the fox;
And tremble, false whigs, in the midst of your glee,
You have not seen the last of my bonnet and me.
If to do were as easy as to know what were good to do, chapels

had been churches, and poor men’s cottages princes’ palaces. It is a
good divine that follows his own instructions. I can easier teach
twenty what were good to be done, than be one of the twenty to
follow mine own teaching. The brain may devise laws for the blood;
but a hot temper leaps over a cold decree: such a hare is madness,
the youth, to skip o’er the meshes of good counsel, the cripple.
—“Merchant of Venice.”
Extremely high: Half a league, half a league, half a league onward!
Very high: Hats off! along the street they come! The flag is passing
by.
High: Sail on, sail on, O ship of state!
Rather high: Now’s the day and now’s the hour!
Middle: In spite of rock and tempest roar.
Rather low: No stir in the air, no stir in the sea.
Low:
Sunset and evening star

And one clear call for me.
Very low: Quoth the raven, “Never more.”

Low as possible: O death, where is thy sting!
Study in Stress
If we read or speak aloud naturally and earnestly, there occurs in
our voice a succession of beats or pulsations. If these pulsations
occur at regular intervals, our speech will be “singsong” and
monotonous. Thus:
a
I wandered lonely cloud
as
and
That floats on high o’er hills,
vales
a
When all at once I crowd
saw
o
A host of golden dills.
daff
The fault is that we are responding to the rhythm of the line

instead of the rhythm of the thought. There should be rhythmic action
of the voice, but, at all times, it should be in perfect harmony with the
rhythmic action of the mind. Therefore, we see again that correct
reading depends upon getting the correct thought.
It is very important that we have control of our voice in stress or
force of utterance. If a teacher requires one pupil out of a class of
twenty to go on an errand for him, there is but one way of clearly
expressing that thought in the following sentence: Thus:
Will you please return this book to the library?
If we make prominent any other word than “you,” we shall not be

clear as to who shall return the book. Read the above sentence in as
many ways as there are different meanings.
Practice reading aloud the following with especial attention to
stress. Be sure that the action of the voice corresponds to the action
of the mind. Stress is indicated by italics.
Rouse, ye Romans! Rouse, ye slaves!
Worcester, get thee gone, for I do see

Danger and disobedience in thine eyes.
You have good leave to leave us; when we need
Your use and counsel, we shall send for you.
—Shakespeare.
Abraham Lincoln used scripture quotations very frequently and
powerfully.

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Clathrate Hydrates: Molecular Science

and Characterization, 2 Volumes John

Molecular Science and Characterization

Molecular Science and Characterization

© 2022 WILEY-VCH GmbH, Boschstr. 12,

All rights reserved (including those of

Print ISBN: 978-3-527-33984-6

Typesetting Straive, Chennai, India

Printed on acid-free paper

1 An Introduction to Clathrate Hydrate Science 1

2 An Introduction to Clathrate Hydrates 27

3 Classiﬁcation of Clathrate Hydrates 65

4 Synthesis of Clathrate Hydrates 123

5 Structures of Canonical Clathrate Hydrates 141

6 Structures of Noncanonical Clathrates and Related

7 Thermodynamics and Statistical Mechanics of Clathrate

8 Molecular Simulations of Clathrate Hydrates 283

9 X-ray and Neutron Diffraction and Scattering of Clathrate

10 Characterization of Clathrate Hydrates Using Nuclear

11 Specialized Methods of Nuclear Magnetic Resonance

12 Reorientation and Diffusion in Clathrate Hydrates 513

13 IR and Raman Spectroscopy of Clathrate Hydrates 569

14 Kinetics of Clathrate Hydrate Processes 631

15 Mechanical and Thermal Transport Properties of Clathrate

16 Applications of Clathrate (Gas) Hydrates 749

1 An Introduction to Clathrate Hydrate Science 1

2 An Introduction to Clathrate Hydrates 27

3 Classiﬁcation of Clathrate Hydrates 65

4 Synthesis of Clathrate Hydrates 123

5 Structures of Canonical Clathrate Hydrates 141

6 Structures of Noncanonical Clathrates and Related

7 Thermodynamics and Statistical Mechanics of Clathrate

8 Molecular Simulations of Clathrate Hydrates 283

9 X-ray and Neutron Diffraction and Scattering of Clathrate

9.4.2 Unconventional Applications of Diffraction 384

10 Characterization of Clathrate Hydrates Using Nuclear

10.5.2.2 Chemical Shift Line Shapes of Other Nuclei: 77 Se, 31 P, 19 F, 13 C 444

11 Specialized Methods of Nuclear Magnetic Resonance

11.3.1 Transient/Metastable Phases 482

12 Reorientation and Diffusion in Clathrate Hydrates 513

12.5 Guest Motions 534

13 IR and Raman Spectroscopy of Clathrate Hydrates 569

14 Kinetics of Clathrate Hydrate Processes 631

14.3.1 Hydrate Formation 645

15 Mechanical and Thermal Transport Properties of Clathrate

16 Applications of Clathrate (Gas) Hydrates 749

An Introduction to Clathrate Hydrate Science

1.2 Selected Highlights of Clathrate Hydrate Science

In this section, we summarize selected highlights of clathrate hydrate research,

1883 de Forcrand observed that a number of double hydrates had well-defined

1969 Ginsburg studied natural gas hydrates in geological settings.

1984 Handa prepared pure hydrocarbon hydrates under equilibrium conditions

1.3 Clathrate Hydrate Research at the NRC Canada

an NMR capability, as a 12′′ NMR electromagnet became available from William

morphologies were observed depending on synthesis conditions. All crystals had

in ice. From the relatively small differences in guest reorientational activation

A unique method was described for producing high-occupancy hydrogen hydrate

Physical aspects of clathrate hydrates as solid-state materials have been studied at

1.4 Contributors to NRC Clathrate Hydrate Research

NRC technical staff

Other collaborators from the NRC

Scientific collaborators on clathrate hydrates

1.5 Review Articles and Books on Clathrate Hydrates