Читать книгу Clathrate Hydrates - Группа авторов - Страница 4

1 Chapter 1Figure 1.1 National Research Council of Canada Building M‐12 on the NRC Mont...Figure 1.2 (a) Donald Davidson observing a clathrate hydrate sample; (b) Wil...Figure 1.3 (a) S. K. Garg at the controls of the Bruker 1.4 T SXP spectromet...Figure 1.4 Clathrate group, Division of Chemistry, National Research Council...Figure 1.5 National Research Council Canada building at 100 Sussex Drive, Ot...

2 Chapter 2Figure 2.1 Pioneers of clathrate science from the early 1800s. From left to ...Figure 2.2 Cailletet apparatus [40] showing the hand‐driven hydraulic pumps ...Figure 2.3 Pioneers of clathrate science in the late 1800s and early 1900s. ...Figure 2.4 The phase diagram of SO₂ and water mixture showing the stability ...Figure 2.5 De Forcrand's results showing (a) octahedral and related crystall...Figure 2.6 Villard's apparatus for hydrate formation and characterization. O...Figure 2.7 von Stackelberg's characterization of the stoichiometry of hydrat...Figure 2.8 Pioneers of clathrate science in the mid‐1900s. From left to righ...Figure 2.9 (a) The body‐centered cubic arrangement of the dodecahedral cages...Figure 2.10 Pioneers of clathrate science in the mid‐1900s. Top row, George ...Figure 2.11 The number of publications related to gas (clathrate) hydrates b...

3 Chapter 3Figure 3.1 The structure of several inclusion compounds with zero‐, one‐, or...Figure 3.2 The polyhedral cages found in clathrate hydrate phases along with...Figure 3.3 Guest size–structure relationships for CS‐I, CS‐II, and HS‐III cl...Figure 3.4 The phase equilibrium of the CO₂–H₂O system over a large pressure...Figure 3.5 The i₁ category P–T phase diagram of methane hydrate shown in two...Figure 3.6 The T–X phase diagram for tetrahydrofuran (THF). The mole fractio...Figure 3.7 The variation of the T–weight % THF phase diagram under isobaric ...Figure 3.8 (a) The P–T phase diagram of DME‐H₂O showing the six quadruple po...Figure 3.9 (a) A partial phase diagram for the Xe–neohexane–water system. (b...

4 Chapter 4Figure 4.1 Cady's apparatus for synthesizing gas hydrates at 0 °C. Water and...Figure 4.2 Schematic diagram of apparatus for the deposition of amorphous ic...Figure 4.3 (a) A schematic diagram of the semi‐batch experimental setup desi...Figure 4.4 Schematic of apparatus for the continuous formation of methane hy...Figure 4.5 Schematic of the experimental apparatus utilizing a bubble column...Figure 4.6 Schematic of spray reactor for hydrate production along with a te...Figure 4.7 (a) The setup of Australia's CSIRO flow loop for hydrate formatio...Figure 4.8 THF clathrate hydrate growth apparatus for observing (a) macrosco...Figure 4.9 (a) High‐pressure cell for optical and Raman spectroscopic observ...

5 Chapter 5Figure 5.1 The polygons in the CS‐I, CS‐II, and HS‐III hydrate phases along ...Figure 5.2 Two views of the unit cell structures of the (a) CS‐I, (b) CS‐II,...Figure 5.3 The variation of the CS‐II lattice constant as a function of the ...Figure 5.4 (a) The spherical THF distribution in the large cage of CS‐II dou...Figure 5.5 (a) Methylcyclohexane–methane HS‐III double hydrate, showing two ...Figure 5.6 (a) Ethane molecules in the small and large cages of the CS‐I hyd...Figure 5.7 (a) The two disordered positions of the ethylene oxide guest mole...Figure 5.8 (a) The single‐crystal X‐ray structure of the CS‐II THF+CH₃OH cla...Figure 5.9 Hydrogen bonding between cage water molecules and (a) CO₂, (b) pi...Figure 5.10 Adjacent D and T cages for: (a) the pure CS‐I Cl₂ clathrate hydr...Figure 5.11 View with full symmetry for the distribution of the 2‐propanol m...Figure 5.12 (a) Detailed structure of HS‐III′ (sH′) hydrate showing the alte...Figure 5.13 The (a) TS‐I hydrate phase (bromine) showing the D (gray), T (gr...Figure 5.14 (a) The structure HS‐I unit cell seen in two views. The relation...Figure 5.15 (a) The truncated octahedral Voronoi cell of an atom in the body...Figure 5.16 Frank–Kasper normal coordination polyhedra with 12 (two views), ...Figure 5.17 (a) The Frank–Kasper A‐15 (β‐tungsten) structure squa...Figure 5.18 (a) The Kagomé net oriented in the {111} direction used to const...Figure 5.19 (a) The Kagomé net used to construct the hexagonal Frank–K...Figure 5.20 (a) The Kagomé‐patterned net used to construct the tetragonal Fr...Figure 5.21 (a) The hexagonal unit cell of the Frank–Kasper μ ‐...Figure 5.22 The Schlegel diagrams for the cages seen in the CS‐I, CS‐II, TS‐...Figure 5.23 The layered structure of the CS‐II clathrate hydrates showing th...Figure 5.24 The stacking pattern of the HS‐II and hexagonal phase. See tex...

6 Chapter 6Figure 6.1 Cages in amine semi‐clathrate structures in (a) trimethylamine, (...Figure 6.2 The cages observed in the five structures of the tert‐butylamine ...Figure 6.3 The cages in the three cyclo‐butylamine (cBA) semi‐hydrate struct...Figure 6.4 Combined cages observed in salt hydrates. (a) The 5⁴⁰6⁴‐hedron (TFigure 6.5 The T₄ cage in TBAB·38H₂O along with adjacent D_A (light gray) and...Figure 6.6 (a) The layered structure of choline hydroxide·(n‐Pr)₄N hydrate, ...Figure 6.7 Strong acid hydrates of (a) the cubic hydrate of HPF₆·HF·5H₂O (...Figure 6.8 The tetragonal I4/mcm unit cell of the Cs[(CH₃)₄N]₂(OH)₃·14H₂O hy...Figure 6.9 The heterogeneous hydrate structures, (a) [(CH₃)₄N]₄[Si₄Al₄O₁₂(OH...Figure 6.10 (a) The variation of the CS‐I Xe clathrate hydrate and CS‐II THF...

7 Chapter 7Figure 7.1 Cady's apparatus for measuring the hydration number of gas hydrat...Figure 7.2 The pressure dependence of the hydration number for the clathrate...Figure 7.3 A schematic diagram of the Tian–Calvet heat flow calorimeter used...Figure 7.4 The dependence of the (a) hydration number n and (b) the cage occ...Figure 7.5 The first ¹²⁹Xe NMR hydrate spectrum recorded was for the xenon d...Figure 7.6 The ¹³C CP/MAS NMR spectra at –80 °C for the ¹³C enhanced methane...Figure 7.7 Solid‐state MAS ¹³C NMR spectra of complex natural gas hydrate. S...Figure 7.8 The Raman spectra of CH₄ in the CS‐I clathrate hydrate (with H₂O ...Figure 7.9 The temperature–composition phase diagram for ethylene oxide hydr...Figure 7.10 (a) Pairs of σ* and ε/k parameters from the Kihara pot...Figure 7.11 Contours of equal average deviation of 82 experimental hydrate p...Figure 7.12 (a) Schematic representation of multilayers first shell model us...Figure 7.13 The equilibrium pressure–temperature three‐phase diagram of pure...Figure 7.14 (a) The three‐phase equilibrium line of CS‐I methane hydrate (bl...Figure 7.15 The three‐ or four‐phase equilibrium boundary lines plotted as l...Figure 7.16 The three‐ or four‐phase equilibrium boundary lines plotted as l...

8 Chapter 8Figure 8.1 (a) The structure of 3,3‐dimethyl‐2‐butanone (pinacolone) illustr...Figure 8.2 The methane C–water OW RDF for the small (S) D cages and large (L...Figure 8.3 The RDFs of the alcohol guest hydroxyl group atoms (O_H and H_O) wi...Figure 8.4 Experimental and molecular dynamics predicted values of the (a) c...Figure 8.5 The angular distribution of CO₂ guests in T cages of the CS‐I cla...Figure 8.6 The unit cell of CS‐I methane clathrate hydrate. Water molecule j Figure 8.7 (a) The initial configuration of a methane clathrate hydrate phas...Figure 8.8 (a) The distribution of the coherence order for liquid water, cub...Figure 8.9 (a) The Bjerrum L‐ and D‐defects in a hydrogen bonded lattice, wh...Figure 8.10 (a) Velocity autocorrelation function for methane carbon, the CS...Figure 8.11 Decreases in the overall system temperature in NVE simulations o...Figure 8.12 One‐dimensional cuts through the potential energy surfaces for HFigure 8.13 Three‐dimensional wavefunction isosurfaces of p‐H₂ in the CS‐II ...Figure 8.14 Three‐dimensional isosurfaces of para‐H₂ in the CS‐II clathrate ...

9 Chapter 9Figure 9.1 Examples of Miller indices (hkl) for illustrated planes in a two‐...Figure 9.2 (a) Schematic representation of the Debye–Scherrer geometry for p...Figure 9.3 Diffraction pattern for a powder sample of CS‐I xenon hydrate rec...Figure 9.4 (a) Single‐crystal diffractometer geometry showing the three rota...Figure 9.5 The simulated powder X‐ray diffraction patterns based on single‐c...Figure 9.6 Neutron powder diffraction pattern of CS‐II Kr clathrate hydrate....Figure 9.7 HS‐III tert‐butyl methyl ether (TBME) + CH₄ binary clathrate hydr...Figure 9.8 (a) In situ powder X‐ray diffraction profiles, using Cu K_α r...Figure 9.9 Neutron scattering length density map of the (001) plane as obtai...Figure 9.10 Charge density difference distribution changes of the Xe atom fo...Figure 9.11 Distortions in the electron distribution around oxygen atoms for...Figure 9.12 Energy‐dispersive X‐ray diffraction results for (a) single‐cryst...Figure 9.13 (a) The orthorhombic MH‐III methane hydrate inclusion compound o...Figure 9.14 Paris–Edinburgh cell of the type used in the discovery of the hi...Figure 9.15 Pressure–volume data for the sequential transformation of the me...Figure 9.16 Result of Rietveld analysis of neutron diffraction on HS‐III met...Figure 9.17 Schematic of a triple‐axis spectrometer employed for neutron dif...Figure 9.18 (a) Incoherent inelastic neutron scattering (IINS) characterizat...Figure 9.19 IINS data showing the low‐frequency‐coupled modes for a Xe guest...Figure 9.20 Inelastic X‐ray spectra of methane hydrate at selected scatterin...Figure 9.21 (a) Schematic of NRIXS facility at the Advanced Photon Source (A...Figure 9.22 Representative QENS spectrum of methyl fluoride clathrate hydrat...Figure 9.23 A schematic drawing of the Compton scattering spectrometer. The ...Figure 9.24 (a) Experimental Compton profiles J(p_z) as a function of momentu...

10 Chapter 10Figure 10.1 (a) Ellipsoidal representation of a shielding tensor indicating ...Figure 10.2 Dipolar Pake doublet powder pattern for a homonuclear ½–½ spin p...Figure 10.3 Conceptual ellipsoid and corresponding NMR line shape for ²H in ...Figure 10.4 Calculated second‐order powder patterns for the central transiti...Figure 10.5 After application of a short duration 90° pulse which rotates th...Figure 10.6 (a) Simple single 90° pulse NMR experiment. After the pulse, the...Figure 10.7 Comparison of low‐temperature ¹⁹F derivative line shapes of soli...Figure 10.8 Line shapes of H₂ molecules in H₂–D₂O sII clathrate as a functio...Figure 10.9 ¹H NMR derivative line shapes of (left) THF‐d₈·15.2H₂O at 93 K a...Figure 10.10 ¹H NMR spectrum of isolated H₂O molecules in a D₂O matrix of lo...Figure 10.11 ¹²⁹Xe NMR spectra of CS‐I Xe hydrate showing broadened features...Figure 10.12 Static ¹H‐decoupled CP ¹²⁹Xe NMR spectra at 77 K of hydrates CS...Figure 10.13 (a) MAS and static ¹²⁹Xe NMR spectra of HS‐III Xe/methyl cycloh...Figure 10.14 ¹²⁹Xe NMR spectra at 77 K of (a) CS‐I Xe hydrate and (b) CS‐II ...Figure 10.15 ¹²⁹Xe CP NMR of metastable Xenon HS‐I hydrate containing a smal...Figure 10.16 ¹²⁹Xe spectra of mixed hydrates of Xe/DME (dimethyl ether) Top:...Figure 10.17 Static ⁷⁷Se CP NMR spectra of H₂Se CS‐I hydrate at three temper...Figure 10.18 The top spectrum shows the dynamically averaged ¹³C CSA line sh...Figure 10.19 ²H NMR line shape of static D₂O in THF·17D₂O CS‐II hydrate at 3...Figure 10.20 ²H NMR line shapes of D₂S in D₂O CS‐I hydrate. 240 K: broad sta...Figure 10.21 ²H NMR line shapes of CS‐I hydrates of cyclopropane‐C₃D₆ (left)...Figure 10.22 ²H NMR spectra of double hydrates with H₂S and large deuterated...Figure 10.23 Static second‐order central transition ¹⁷O NMR line shapes of DFigure 10.24 ¹³¹Xe spin‐echo NMR spectra of a static sample of CS‐I xenon hy...Figure 10.25 ⁸³Kr NMR static spectra of krypton CS‐II hydrates obtained at T Figure 10.26 Stationary ³³S NMR spectrum of CS‐I H₂S hydrate obtained at T =...Figure 10.27 ³³S NMR spectrum of stationary powder of SO₂ CS‐I hydrate obtai...

11 Chapter 11Figure 11.1 ¹³C HP DEC MAS of synthetic CS‐I methane hydrate (a) and natural...Figure 11.2 (a) ¹³C HPDEC MAS NMR spectra of CS‐I hydrate prepared from CH₄/...Figure 11.3 Signal intensities in ¹³C CP MAS NMR spectra as a function of co...Figure 11.4 ¹³C CP MAS and ¹³C HPDEC MAS spectra of CS‐II mixed iso‐butane/C...Figure 11.5 Cross‐polarization with (a) contact time 400 μs, (b) contact tim...Figure 11.6 Signal intensity dependencies on the contact time for this HS‐II...Figure 11.7 ¹³C HPDEC MAS (a) and ¹³C CP MAS (b) NMR at 193 K of ice + metha...Figure 11.8 (a) Time‐resolved ¹³C MAS NMR of CS‐I methane hydrate dissociati...Figure 11.9 ¹²⁹Xe NMR spectra at 77 K of the reaction product of CS‐I hydrat...Figure 11.10 Time development of the ¹²⁹Xe NMR spectrum after exposure of a ...Figure 11.11 Time dependence of the hyperpolarized ¹²⁹Xe spectra following i...Figure 11.12 ¹²⁹Xe NMR spectra at 77 K of a sample produced by co‐deposition...Figure 11.13 ¹²⁹Xe MAS NMR spectra at 183 K of the CS‐I Xe hydrates and CS‐I...Figure 11.14 ¹⁹F spectra of HAsF₆·HF·5H₂O: (a) solid at 298 K, (b) liquid at...Figure 11.15 ²H NMR line shapes of (CH₃)₄NOD·5D₂O: Multiple sites in the sta...Figure 11.16 (a) Spatial encoding with magnetic field gradients. (b) Slice s...Figure 11.17 The schematics of a setup for in situ NMR micro‐imaging in gas ...Figure 11.18 ¹H micro‐imaging data for CO₂ hydrate formation in silica gel p...Figure 11.19 Left panel (in green): Magnetic resonance images of methane and...

12 Chapter 12Figure 12.1 (a) Low‐temperature permittivity, ε′, and loss, ε″, cu...Figure 12.2 Dielectric absorption associated with reorientation of THF guest...Figure 12.3 Line shape or spin–spin relaxation time (T₂) and spin–lattice re...Figure 12.4 Dynamic averaging effects on the ²H NMR line shape of ²H atoms i...Figure 12.5 (a) ¹³C NMR spectra for ¹³CO₂ CS‐I hydrate (top), and a CS‐II do...Figure 12.6 Coordinate system used in the motional averaging calculation. Th...Figure 12.7 (a) Schematic picture of the formation of a Bjerrum defect pair ...Figure 12.8 (a) Arrhenius plots of dielectric relaxation times of water mole...Figure 12.9 (a) Static ¹⁷O NMR ¹H decoupled spin‐echo spectra of the central...Figure 12.10 The 12 possible orientations of a water molecule on any one par...Figure 12.11 (a) Temperature dependence of the second moment of proton absor...Figure 12.12 ²H solid echo spectra of THF‐h₈·17D₂O as a function of temperat...Figure 12.13 The large cage (T, 5¹²6²) of CS‐I hydrate. The left side shows ...Figure 12.14 ¹³C NMR static line shapes of ¹³C‐enriched CO₂ hydrate at 238 (...Figure 12.15 Change of ¹⁹F line shape of SF₆ deuteriohydrate in the region o...Figure 12.16 (a) Second moment or mean square line width, as a function of t...Figure 12.17 Models for the dynamic state of the CO₂ molecule encaged in the...Figure 12.18 (a) Calculated ¹³C line shapes for CO₂ hydrate at 77 K (dashed ...Figure 12.19 Results of calculations for CO₂ guests in the CS‐I large cages:...Figure 12.20 Second moment of the ¹H resonance of THF⋅17D₂O as a function of...Figure 12.21 Solid‐echo spectra of TDF·17H₂O recorded for an interpulse dela...Figure 12.22 Effective ²H quadrupole coupling frequencies of deuterated CS‐I...Figure 12.23 (a) The prochiral TMO molecule (with one labeled hydrogen atom,...Figure 12.24 (a) Time development of the ¹²⁹Xe NMR spectrum after exposure o...Figure 12.25 (a) Temperature dependence of the ¹³C NMR spectrum of the doubl...Figure 12.26 ¹H NMR experimental (below) and calculated (above) line shapes ...Figure 12.27 ¹H spin–lattice relaxation times as a function of inverse tempe...Figure 12.28 A summary of the changes in guest line shape at different tempe...

13 Chapter 13Figure 13.1 Representation of the excitation of molecular states resulting i...Figure 13.2 Schematic of Raman spectrum of carbon tetrachloride (CCl₄) showi...Figure 13.3 Comparison of IR and Raman spectra for (a) liquid water and (b) ...Figure 13.4 Comparison of water Raman spectrum in the liquid, ice, and hydra...Figure 13.5 Schematic diagram of (a) the attenuated total reflection (ATR) m...Figure 13.6 (a) Schematic of a pressure cell suitable for Raman studies at p...Figure 13.7 C–H stretching mode of CH₄ molecules in the vapor phase (2917.6 ...Figure 13.8 C–H stretching mode of CH₄ molecules in natural and synthetic hy...Figure 13.9 The position of a guest molecule ABC in a cage where the C atom ...Figure 13.10 Variation in Raman peak position shift with intramolecular equi...Figure 13.11 Schematic diagram of an in situ Raman spectroscopic observation...Figure 13.12 (A) The O–H stretching mode of the CS‐II (a) and CS‐I (b) CH₄ c...Figure 13.13 Structural changes of gas hydrates under high pressure, in term...Figure 13.14 Raman vibrational spectra of H₂ in known clathrate‐hydrate envi...

14 Chapter 14Figure 14.1 (a) The moles of methane gas consumed as a function of time in a...Figure 14.2 The pressure drop during the hydrate formation from ice exposed ...Figure 14.3 Typical isothermal differential scanning calorimetry experiments...Figure 14.4 Raman spectra of methane in transition from dissolved methane to...Figure 14.5 A typical kinetic run on the formation of methane hydrate from p...Figure 14.6 Time dependence (t in minutes) of methane hydrate formation for ...Figure 14.7 The formation kinetics of CO₂ hydrate at 275 K and 58 bar as det...Figure 14.8 (a) The reactor for synthesis of methane hydrate in a water‐satu...Figure 14.9 (a) A schematic representation of the chemical potential of the ...Figure 14.10 (a) The negative r³ dependence of the volume free energy and th...Figure 14.11 (a) The contributions of the exponential terms from Eq. (14.8) ...Figure 14.12 (a) A spherical cap solid crystal phase nucleus (clathrate hydr...Figure 14.13 (a) Schematic plots of the free energy of heterogeneous and hom...Figure 14.14 (a) A schematic model of the steps involved with hydrate format...Figure 14.15 (a) The simultaneous DSC scans for the cooling (blue) followed ...Figure 14.16 Methane gas consumption, as an indicator of hydrate formation, ...Figure 14.17 (a) A schematic representation of the shrinking core model for ...Figure 14.18 (a) The nucleation (black dots) of phase β into the phase Figure 14.19 (a) Integrated intensity of the ¹²⁹Xe NMR spectral lines for th...Figure 14.20 (a) Pressure drop for the reaction of powdered ice with Xe gas ...Figure 14.21 A schematic representation of the relation between crystal morp...Figure 14.22 (a) Sequential video graphs of the growth of methane hydrate cr...Figure 14.23 Optical images of hydrate single crystals showing different cry...Figure 14.24 The cages where the Miller index planes cut through the CS‐I an...Figure 14.25 The depressurization (vertical) and heating (horizontal) routes...Figure 14.26 Ice coating formed at 220 K and 60 kPa on the CS‐I CO₂ clathrat...Figure 14.27 The two models of growth inhibition are very similar except for...Figure 14.28 Simple model of melting and freezing inhibition operating throu...Figure 14.29 Mechanism of step pinning by adsorbed KHI polymer clumps on a h...Figure 14.30 The partial encapsulation of a hydrophobic pendant methyl group...Figure 14.31 The DSC scans of the decomposition of natural gas hydrate for a...Figure 14.32 Molecular dynamics simulations of growth and decay of hydrate n...Figure 14.33 Molecular dynamics simulations of the mechanism of homogeneous ...Figure 14.34 Simulations the process of hydrate nucleation, the formation of...Figure 14.35 A representation of the multiscale approach for laboratory and ...

15 Chapter 15Figure 15.1 (a) A schematic representation of the Brillouin scattering spect...Figure 15.2 (a) Experimental Brillouin scattering data for polycrystalline x...Figure 15.3 (a) Acoustic longitudinal velocities of clathrate hydrates at 0 ...Figure 15.4 Single crystal of methane hydrate grown in diamond anvil cell....Figure 15.5 (a) Pressure dependence of the longitudinal (LA) and transverse ...Figure 15.6 The pressure dependence of elastic moduli, c₁₁, c₁₂, c₄₄ and bul...Figure 15.7 (a) Elastic moduli for argon and methane hydrate as a function o...Figure 15.8 The temperature dependence of the ice, CS‐I methane clathrate, a...Figure 15.9 The constant pressure thermal expansion of the lattice parameter...Figure 15.10 Temperature dependence for the a (top) and c (bottom) unit cell...Figure 15.11 (a) Thermal conductivity of CS‐II tetrahydrofuran hydrate betwe...Figure 15.12 Thermal conductivity measurement results for tetrahydrofuran hy...Figure 15.13 (a) The “reversal” of the thermal conductivity at T < 100 K and...Figure 15.14 Schematic representation of the phonon scattering process in th...

16 Chapter 16Figure 16.1 Methane hydrate formation in the presence of different weight pe...Figure 16.2 The interaction of the winter flounder AFP (wf‐AFP) with empty h...Figure 16.3 Hydrate growth along the vessel wall and receding gas/water inte...Figure 16.4 Map showing gas hydrate accumulations in the earth.Figure 16.5 Experimental conditions for methane and carbon dioxide hydrate f...Figure 16.6 Timeline of progress on the use of hydrates for water desalinati...Figure 16.7 Schematic of the prototype for the seawater desalination process...Figure 16.8 Dissociation temperatures for different hydrate structures at 0....Figure 16.9 Block flow diagram of a facility for the production and storage ...Figure 16.10 Hydrate phase equilibrium for THF‐H₂‐water.Figure 16.11 Hydrogen storage capacity at different aqueous THF concentratio...Figure 16.12 H₂ storage capacities with semi‐clathrates.Figure 16.13 Post‐combustion capture with hydrates: the CO₂ separation step ...Figure 16.14 Pre‐combustion capture with hydrates: The CO₂ separation step f...Figure 16.15 Temperature (T) composition (w) diagram of the semi‐clathrate h...Figure 16.16 Partial phase diagram for a CO₂/H₂ (39.2/60.8 mol%) fuel gas mi...Figure 16.17 Hydrate phase equilibrium for the fuel gas mixture with or with...Figure 16.18 Comparison of CO₂ capacity of HBGS process with conventional so...