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)