Physics and Chemistry of Ice: Rsc: 311 (Special Publications) - Hardcover

Hardcover

ISBN 10: 0854043500 ISBN 13: 9780854043507

Publisher: Royal Society of Chemistry, 2007

Synopsis

An authoritative summary of state-of the-art research contributions from the world's leading scientists.

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About the Author

The Editor Werner F. Kuhs is a Professor of Crystallography at the University of G÷ttingen, Germany and has a career spanning 25 years of research in the field of water ices and gas hydrates using diffraction methods, neutron and Raman spectroscopy, scanning electron microscopy, atomic force and molecular dynamics simulations. He was the Chair of the 11th International Conference on the Physics and Chemistry of Ice.

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Physics and Chemistry of Ice is an authoritative summary of state-of the-art research contributions from the world's leading scientists. A key selection of submissions from to the 11th International Conference on the Physics and Chemistry of Ice, 2006 are presented here with a foreword by Werner F. Kuhs. An invaluable resource, this book provides researchers and professionals with up-to-date coverage on a wide range of areas in ice science including: " Spectroscopic and diffraction studies " Molecular dynamics simulations " Studies of ice mechanics " Quantum mechanical ab initio calculations " Ice and hydrate crystal growth and inhibition studies " Bulk and surface properties of ice and gas hydrates " Snow physics and chemistry This insight into topical aspects of ice research is a key point of reference for physicists, chemists, galciologists, cryo-biologists and professionals working in the fields of ice and hydrogen bonding. The Editor Werner F. Kuhs is a Professor of Crystallography at the University of G÷ttingen, Germany and has a career spanning 25 years of research in the field of water ices and gas hydrates using diffraction methods, neutron and Raman spectroscopy, scanning electron microscopy, atomic force and molecular dynamics simulations. He was the Chair of the 11th International Conference on the Physics and Chemistry of Ice.

Excerpt. © Reprinted by permission. All rights reserved.

Physics and Chemistry of Ice

By Werner F. Kuhs

The Royal Society of Chemistry

Copyright © 2007 The Royal Society of Chemistry
All rights reserved.

ISBN: 978-0-85404-350-7

Contents

Invited Papers, 
MOLECULAR SIMULATIONS OF GAS HYDRATE NUCLEATION B.J. Anderson, R. Radhakrishnan, B. Peters, G.P. Borghi, J.W. Tester and B.L. Trout, 3, 
EXTRATERRESTRIAL ICE WITH EMPHASIS ON AGGREGATION/ INTERACTION WITH ORGANIC MATTER: COLLISIONAL AND ACCRETIONAL PROPERTIES OF MODEL PARTICLES M. Arakawa, 13, 
INTERACTIONS BETWEEN SNOW METAMORPHISM AND CLIMATE: PHYSICAL AND CHEMICAL ASPECTS F. Domine, A.-S. Taillandier, S. Houdier, F. Parrenin, W.R. Simpson and T.A. Douglas, 27, 
ICE ADHESION AND ICE FRICTION MODIFICATION USING PULSED THERMAL POWER V.F. Petrenko, 47, 
IMPROVING OUR UNDERSTANDING OF GAS HYDRATE FORMATION PROCESSES: THE IMPORTANCE OF MULTI-TECHNIQUE APPROACHES J. Ripmeester, 59, 
FAST THERMAL DESORPTION SPECTROSCOPY AND MICROCALORIMETRY: NEW TOOLS TO UNCOVER MYSTERIES OF ICE V. Sadtchenko, 73, 
SELECTION FOR 'ICE RESISTANCE', ANTIFREEZE PROTEINS AND ICE OR HYDRATE INHIBITION V. K. Walker, S.L Wilson, Z. Wu, E. Huva, G. R. Palmer, G. Voordouw, H. Zeng and J. A. Ripmeester, 87, 
Contributed Papers, 
RAMAN SCATTERING STUDY OF PROTON ORDERED ICE-XI SINGLE CRYSTAL K. Abe, Y. Ootake and T. Shigenari, 101, 
ON THE PERFORMANCE OF SIMPLE PLANAR MODELS OF WATER IN THE VAPOR AND THE ICE PHASES A. Baranyai, A. Bartók and A.A. Chialvo, 109, 
PHASES OF SUPERCOOLED LIQUID WATER I. Brovchenko and A. Oleinikova, 117, 
USING GAUSSIAN CURVATURE FOR THE 3D SEGMENTATION OF SNOW GRAINS FROM MICROTOMOGRAPHIC DATA J.B. Brzoska, F. Flin and N. Ogawa, 125, 
ETHANOL HYDRATES FORMED BY GAS CONDENSATION: INVESTIGATIONS BY RAMAN SCATTERING AND X-RAY DIFFRACTION B. Chazallon, C. Focsa, F. Capet and Y. Guinet , 133, 
DISLOCATION PATTERNING AND DEFORMATION PROCESSES IN ICE SINGLE CRYSTALS DEFORMED BY TORSION J. Chevy, M. Montagnat, P. Duval, M. Fivel and J. Weiss, 141, 
FORMATION OF CARBON DIOXIDE GAS HYDRATES IN FREEZING SEDIMENTS AND DECOMPOSITION KINETICS OF THE HYDRATES FORMED E.M. Chuvilin, S.Yu. Petrakova, O.M. Gureva and V.A. Istomin, 147, 
FIRST-PRINCIPLES STUDY OF BJERRUM DEFECTS IN ICE Ih: AN ANALYSIS OF FORMATION AND MIGRATION PROPERTIES M. de Koning, A. Antonelli, A.J.R. da Silva and A. Fazzio , 155, 
FROM ICE TO CO2 HYDRATES AND BACK – STUDY OF NUCLEATION AND INITIAL GROWTH USING SCANNING ELECTRON MICROSCOPY A. Falenty, G. Genov and W.F. Kuhs, 171, 
THE TEMPERATURE GRADIENT METAMORPHISM OF SNOW: MODEL AND FIRST VALIDATIONS USING X-RAY MICROTOMOGRAPHIC IMAGES F. Flin, J. -B. Brzoska, R. A. Pieritz, B. Lesaffre, C. Coléou and Y. Furukawa, 181, 
SUM FREQUENCY GENERATION ON SINGLE-CRYSTALLINE ICE Ih H. Groenzin, I. Li and M.J. Shultz, 191, 
MODELLING ICE Ic OF DIFFERENT ORIGIN AND STACKING-FAULTED HEXAGONAL ICE USING NEUTRON POWDER DIFFRACTION DATA T.C. Hansen, A. Falenty and W.F. Kuhs, 201, 
FUNDAMENTAL STUDIES FOR A NEW H2 SEPARATION METHOD USING GAS HYDRATES S. Hashimoto, S. Murayama, T. Sugahara and K. Ohgaki, 209, 
SEGREGATION OF SALT IONS AT AMORPHOUS SOLID AND LIQUID SURFACES O. Höfft, U. Kahnert, S. Bahr, V. Kempter, P. Jungwirth and L. X. Dang, 217, 
THEORETICAL STUDY ON GASES IN HEXAGONAL ICE INVESTIGATED BY THE MOLECULAR ORBITAL METHOD A. Hori and T. Hondoh, 225, 
DEVELOPMENT OF IN SITU LOW TEMPERATURE INFRARED SPECTROSCOPY FOR A STUDY OF METHANE HYDRATE K. Ishikawa, A. Tani and S. Nakashima, 233, 
A MECHANISM FOR PHOTOCHEMICAL REACTIONS IN THE QUASI- LIQUID LAYER OF SNOW CRYSTALS IN POLAR REGIONS H.-W. Jacobi, T. Armor, B. Kwakye-Awuah, B. Hilker and E. Quansah, 241, 
TOPOLOGICAL TRANSITIONS BETWEEN ICE PHASES S. Jenkins, S.R. Kirk and P. W. Ayers, 249, 
THE IMPORTANCE OF O — O BONDING INTERACTIONS IN VARIOUS PHASES OF ICE S. Jenkins, S.R. Kirk and P. W. Ayers, 257, 
THE CHEMICAL CHARACTER OF VERY HIGH PRESSURE ICE PHASES S. Jenkins, S.R. Kirk and P. W. Ayers, 265, 
REAL-SPACE STUDY OF MECHANICAL INSTABILITY OF ICE XI ON A BOND-BY-BOND' BASIS S. Jenkins, S.R. Kirk and P. W. Ayers, 273, 
WATER-VAPOR TRANSPORT IN SNOW WITH HIGH TEMPERATURE GRADIENT Y. Kamata and A. Sato, 281, 
EXPERIMENTAL GEOSCIENCE IN A FREEZER: ICE AND ICY COMPOUNDS AS USEFUL EDUCATIONAL ANALOGUES FOR TEACHING EARTH AND PLANETARY MATERIALS SCIENCE AND THE PHYSICAL SCIENCES S.H. Kirby, 289, 
CLASSIFICATION OF LOW-ENERGY CONFIGURATIONS OF POLYHEDRAL WATER CLUSTERS FROM CUBE UP TO BACKMINSTERFULLERENE M.V.Kirov, 305, 
ENERGY OPTIMIZATION OF GAS HYDRATE FRAMEWORKS ON THE BASIS OF DISCRETE MODELS OF INTER-MOLECULAR INTERACTIONS M.V. Kirov, 313, 
MICROSTRUCTURE OF GAS HYDRATES IN POROUS MEDIA A. Klapproth, K.S. Techmer, S. A. Klapp, M. M. Murshed and W. F. Kuhs, 321, 
TACKLING THE PROBLEM OF HYDROGEN BOND ORDER AND DISORDER IN ICE C. Knight and S. J. Singer, 329, 
THEORETICAL STUDY OF A HYDROXIDE ION WITHIN THE ICE-Ih LATTICE C. Knight and S. J. Singer, 339, 
ATOMIC FORCE MICROSCOPY OF REARRANGING ICE SURFACES M. Krzyzak, K.S. Techmer, S.H. Faria, G. Genov and W.F. Kuhs, 347, 
IONISATION OF HCI ON ICE AT VERY LOW TEMPERATURE C. Laffon and Ph. Parent, 357, 
EFFECTS OF LARGE GUEST SPECIES ON THERMODYNAMIC PROPERTIES OF STRUCTURE-H HYDRATES T. Makino, T. Sugahara and K. Ohgaki, 363, 
PREDICTION OF THE CELLULAR MICROSTRUCTURE OF SEA ICE BY MORPHOLOGICAL STABILITY THEORY S. Maus, 371, 
THE PLANAR-CELLULAR TRANSITION DURING FREEZING OF NATURAL WATERS S. Maus, 383, 
CRYSTAL GROWTH OF ICE-I/HYDRATE EUTECTIC BINARY SOLUTIONS C. McCarthy, K.D. Rieck, S.H. Kirby, W.B. Durham, LA. Stern and R.F. Cooper, 391, 
X-RAY TOMOGRAPHIC CHARACTERIZATION OF IMPURITIES IN POLYCRYSTALLINE ICE M. M. Miedaner, T. Huthwelker, F. Enzmann, M. Kersten, M. Stampanoni and M. Ammann, 399, 
EFFECTS OF ADDITIVES AND COOLING RATES ON CRYOPRESERVATION PROCESS OF RAT CORTICAL CELLS J. Motomura, T. Uchida, M. Nagayama, K. Gohara, T. Taira, K. Shimizu and M. Sakai, 409, 
LABORATORY STUDIES OF THE FORMATION OF CUBIC ICE IN AQUEOUS DROPLETS B.J. Murray and A.K. Bertram, 417, 
HYDRATE PHASE TRANSFORMATIONS IMPOSED BY GAS EXCHANGE M. M. Murshed and W. F. Kuhs, 427, 
MECHANISM OF CAGE FORMATION DURING GROWTH OF CH4 AND Xe CLATHRATE HYDRATES: A MOLECULAR DYNAMICS STUDY H. Nada, 435, 
GROWTH KINETICS ON INTERFACE BETWEEN {2021} PLANE OF ICE AND WATER INVESTIGATED BY A MOLECULAR DYNAMICS SIMULATION H. Nada and Y. Furukawa, 443, 
CHOOSING AN APPROPRIATE WATER MODEL FOR USE IN BIOMOLECULAR SIMULATIONS D.R. Nutt and J. C. Smith, 451, 
MICRO-RAMAN STUDY OF AIR CLATHRATE HYDRATES IN POLAR ICE FROM DOME FUJI, ANTARCTICA H. Ohno and T. Hondoh, 459, 
HIGH PRESSURE NMR OF HYDROGEN-FILLED ICES BY DIAMOND ANVIL CELL T. Okuchi, M. Takigawa, H.K. Mao, R.J. Hemley and T. Yagi, 469, 
ON THE USE OF THE KIHARA POTENTIAL FOR HYDRATE EQUILIBRIUM CALCULATIONS N.I. Papadimitriou, I.N. Tsimpanogiannis, A.G. Yiotis, T.A. Steriotis and A.K. Stubos, 475, 
THE RADICAL CHEMISTRY IN IRRADIATED ICE Ph. Parent, S. Lacombe, F. Bournel and C. Laffon, 489, 
SPEEDSKATE ICE FRICTION: REVIEW AND NUMERICAL MODEL - FAST 1.0 A. Penny, E. Lozowski, T. Forest, C. Fong, S. Maw, P. Montgomery and N. Sinha, 495, 
FIRST PRINCIPLES COMPUTATIONAL STUDY OF HYDROGEN BONDS IN ICE Ih P.L.M. Plummer, 505, 
FREEZING OF WATER ON α-Al2O3 SURFACES H.H. Richardson, Z.N. Hickman, A.C. Thomas, K.A. Dendramis, G.E. Thayer and G.E. Ewing, 513, 
NEW HYDROGEN ORDERED PHASES OF ICE C.G. Salzmann, P.G. Radaelli, A. Hallbrucker, E. Mayer and J.L. Finney, 521, 
MICROSCOPIC OBSERVATION AND IN-SITU RAMAN STUDIES ON SOME SINGLE-CRYSTALLINE GAS HYDRATES UNDER HIGH PRESSURE S. Sasaki, T. Kume and H. Shimizu, 529, 
CLATHRATE HYDRATE FORMATION AND GROWTH: EXPERIMENTAL OBSERVATIONS VERSUS PREDICTED BEHAVIOUR J.M. Schicks, M. Luzi, J. Erzinger and E. Spangenberg, 537, 
EFFECT OF SNOW ACCRETION TO THE GPS ANTENNA ON POSITIONING PERFORMANCE M. Shishido, H. Yamamoto, S. Iikura, T. Endo, T. Masunari, T. Fujii and K. Okada, 545, 
GAS HYDRATES IN THE SYSTEM H2-CH4 - H2O AT PRESSURES OF 4.5 TO 220 MPa AND CONCENTRATIONS OF 0 TO 70 MOL % H2 S.S. Skiba, E.G. Larionov, A. Yu. Manakov and B.A. Kolesov, 553, 
CHEMISTRY INDUCED BY IMPLANTATION OF REACTIVE IONS IN WATER ICE G. Strazzulla, G. Leto, F. Spinella and O. Gomis, 561, 
STRUCTURE H HYDRATE KINETICS STUDIED BY NMR SPECTROSCOPY R. Susilo, I.L. Moudrakovski, J.A. Ripmeester and P. Englezos, 569, 
DIELECTRIC RELAXATION OF ICE SAMPLES GROWN FROM VAPOR-PHASE OR LIQUID-PHASE WATER I. Takei, 577, 
ESR OBSERVATION OF SELF-PRESERVATION EFFECT OF METHANE HYDRATE K. Takeya, K. Nango, T. Sugahara, A. Tani and K. Ohgaki, 585, 
INVESTIGATION OF THE STRUCTURAL DISORDER IN ICE Ih USING NEUTRON DIFFRACTION AND REVERSE MONTE CARLO MODELLING L. Temleitner and L. Pusztai, 593, 
INVESTIGATION OF THE STRUCTURAL DISORDER IN ICE Ih USING NEUTRON DIFFRACTION AND REVERSE MONTE CARLO MODELLING L. Temleitner and L. Pusztai, 593, 
EFFECTS OF ADDITIVES ON FORMATION RATES OF CO2 HYDRATE FILMS T. Uchida, I.Y. Ikeda, R. Ohmura and S. Tsuda, 609, 
RIPPLE FORMATION MECHANISM ON ICICLES UNDER A THIN SHEAR FLOW K. Ueno and N. Maeno, 619, 
MOLECULAR SIMULATIONS OF WATER FREEZING: BRINE REJECTION AND HOMOGENEOUS NUCLEATION L. Vrbka and P. Jungwirth, 627, 
IMPLICATIONS FOR AND FINDINGS FROM DEEP ICE CORE DRILLINGS — AN EXAMPLE: THE ULTIMATE TENSILE STRENGTH OF ICE AT HIGH STRAIN RATES F. Wilhelms, S. G. Sheldon, I. Hamann and S. Kipfstuhl, 635, 
ISOTHERMAL AMORPHOUS-AMORPHOUS-AMORPHOUS TRANSITIONS IN WATER K. Winkel, W. Schustereder, I. Kohl, C. G. Salzmann, E. Mayer and T. Loerting, 641, 
MECHANICAL STRENGTH AND FLOW PROPERTIES OF ICE-SILICATE MIXTURE DEPENDING ON THE SILICATE CONTENTS AND THE SILICATE PARTICLE SIZES M. Yasui and M. Arakawa, 649, 
ADSORPTION OF ANTIFREEZE PROTEIN AND A COMMERCIAL LOW DOSAGE HYDRATE INHIBITOR ON HYDROPHILIC AND HYDROPHOBIC SURFACES H. Zeng, V.K. Walker and J.A. Ripmeester, 659, 
DIFFUSION, INCORPORATION, AND SEGREGATION OF ANTIFREEZE GLYCOPROTEINS AT THE ICE/SOLUTION INTERFACE S. Zepeda, H. Nakaya, Y. Uda, E. Yokoyama and Y. Furukawa , 669, 
Subject Index, 677, 

CHAPTER 1

MOLECULAR SIMULATIONS OF GAS HYDRATE NUCLEATION

B.J. Anderson, R. Radhakrishnan, Baron Peters, G.P. Borghi, J.W. Tester, and B.L. Trout

1 INTRODUCTION

We present an overview of cutting edge molecular simulation methods applied to understanding the nucleation of ice and gas hydrates. These methods allow us to probe the molecular details of these complex processes, quantify their kinetics, and engineer new ways of changing the kinetics. Specifically, we first select order parameters, mathematical functions that can describe the nucleation process. We use these order parameters within Monte Carlo and molecular dynamics simulations in order to explore the parts of the free energy surfaces related to nucleation. Along the way, we also test the order parameters for their ability to describe the nucleation process and determine the molecular mechanism for nucleation. We also describe how we have used molecular dynamics simulations to understand the inhibition of clathrate-hydrate formation, of tremendous interest to oil and gas companies, and use that understanding to design new kinetic inhibitors.

2 NUCLEATION OF HYDRATE CLATHRATES

Equilibrium properties of the CO2/sea-water system have been well researched from an experimental standpoint. In particular, the clathrate hydrate forming conditions (T< 285 K and P > 4 MPa) are well established. Several experiments have been performed under conditions mimicking the direct injection process and have attempted to study the dissolution rate of CO2 in seawater. Under direct injection conditions, the injected CO2 is in the form of a liquid droplet and a thin spherical shell of CO2 clathrate hydrate of structure I is observed to form around the CO2 drop, separating it from the sea water. The process of hydrate formation has many similarities with that of crystallization, i.e., it can be divided into a nucleation phase and a growth phase. For CO2 clathrates, the nucleation phase involves the formation of a hydrate nucleus of a critical size at the liquid–liquid interface of CO2 and water. This homogeneous nucleation process is believed to be stochastic in nature, i.e., the critical nucleus is formed because of a local thermodynamic fluctuation in the system. The formation of the critical nucleus is followed by the spontaneous growth of the hydrate phase at the interface.

2.1 Methods

We use an order-parameter formulation, in conjunction with non-Boltzmann sampling to study the nucleation of clathrate hydrates from water–CO2 mixtures, using Monte Carlo simulations. A set of order parameters are defined: Φgg[(i = 1,2,...,n] and gg for guest–guest), which characterize the spatial and orientational order of the CO2 molecules, and Φhh (hh for host–host), which govern the ordering of the water molecules. Tetrahedral and Steinhardt order parameters satisfactorily describe the ordering of the water (host) molecules in the clathrate. The Steinhardt order parameters are bond-orientational order parameters based on the average geometrical distribution of nearest-neighbor bonds. The tetrahedral order parameter measures the degree to which the nearest-neighbour water molecules are tetrahedrally coordinated with respect to a given water molecule. The tetrahedral order parameter, ζhh, is defined as follows:

[MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII] (1)

where N is the number of water molecules, the indices i,j run over the four nearest neighbours of a given water molecule, and ωij is the angle between the nearest-neighbour bond associated with molecule i and that of molecule j. The tetrahedral order parameters are not sufficient to characterize the order of the guest molecules in the clathrate; therefore, we define the order parameter ζggi as the ratio of the area under i-th peak of the guest-guest radial distribution (ggg(r)) function of any given configuration to the same area for the clathrate phase. More details regarding the validation of these order parameters can be found in Radhakrishnan and Trout, 2002.

The free-energy hypersurface as a function of the order parameters is calculated using the Landau–Ginzburg approach. The critical cluster size that leads to the nucleation of the clathrate phase is determined accurately by analyzing the free energy surface. The free energy hypersurface of implanted clusters were mapped as a function of the cluster order parameters to analyze the thermodynamic stability of different cluster implants. The global minimum in the Landau free energy hypersurface of a stable (growing) cluster occurs at values of the cluster order parameters close to that of the clathrate phase. On the other hand, the global minimum in the Landau free energy hypersurface of an unstable cluster occurs at the values of the cluster order parameters close to that of the liquid phase. Figure 1 shows the Landau free energy hypersurface as a function of the ζgg.clusterl order parameter for the implementation of a 14.5 Å cluster. Point 1 corresponds to a liquid-like solution (ζgg.liquidl =0.43) while point 6 corresponds to the clathrate phase (ζgg.clathratel = 1.0).

2.2 Results

We find that the nucleation proceeds via "the local structuring mechanism, i.e., a thermal fluctuation causing the local ordering of CO2 molecules leads to the nucleation of the clathrate, and not by the labile cluster hypothesis, one current conceptual picture. The local ordering of the guest molecules induces ordering of the host molecules at the nearest- and next-to-nearest-neighbor shells, which are captured by a three-body host–host order parameter, ζhh; these thermodynamic fluctuations lead to the formation of the critical nucleus.

Based on the Landau–Ginzburg free energy calculations, the critical cluster size for the nucleation of CO2 clathrate hydrate at the liquid–liquid interface of CO2 and H2O at 220 K and 4 MPA was calculated to be between 9.6 and 14.5 Å. This is to be compared with the result of classical nucleation theory, which Larson and Garside used to estimate a critical size of 32 Å. Classical nucleation theory clearly overestimates the size of the critical nucleus for CO2 clathrates and therefore would underestimate the ability for CO2 hydrates to spontaneously nucleate. A quantitative estimation of the free energy barrier, ΔF, to nucleation was obtained using a path integral method, which samples the four-dimensional order-parameter space. The precise free energy difference between the liquid phase and the transition state (55 kBT), and the transition state and the hydrate phase (58 kBT) was calculated. Teng et al. and Mori et al. have reported that the time scale for the nucleation of the CO2 clathrate hydrate in their experiments to be of the order of 1–5 s. Using transition state theory and our simulation results we predict the time constant, λ = 1/k to be 1.2 s. This result is for the volume available for nucleation around a 1 mm CO2 droplet with an assumed CO2-H2O interface thickness of 10 Å. Therefore our prediction agrees reasonably well with the experimental observations.

(Continues...)

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Edition details

• Publisher: Royal Society of Chemistry
• Publication date: 2007
• Language: English
• ISBN 10: 0854043500
• ISBN 13: 9780854043507
• Binding: Hardcover
• Number of pages: 718
• Editor: Werner Kuhs