Comments on the Infrared Spectra of SO2 Clathrate-hydrate Formed by Vapor Condensation

1971 ◽  
Vol 49 (24) ◽  
pp. 4114-4115 ◽  
Author(s):  
A. H. Hardin ◽  
K. B. Harvey

Gaseous mixtures having clathrate-hydrate stoichiometries were condensed at 83 °K into an amorphous phase. Infrared spectra were recorded at a series of temperatures up to 180 °K in order to determine the transformation temperature and the nature of the annealed phase. Bands associated with the H2O molecules began to shift position at 125 °K while those attributed to guest molecules decreased to null intensity. There was no evidence of a unique clathrate-hydrate H2O spectrum nor of free or hindered rotation of the guest molecules.

1982 ◽  
Vol 60 (7) ◽  
pp. 881-892 ◽  
Author(s):  
Russell G. Ross ◽  
Per Andersson

Solid phases in the tetrahydrofuran–water (THF–H2O) system were investigated in the temperature range 100–260 K and at pressures up to 1.5 GPa. Thermal conductivity, λ, and heat capacity per unit volume, ρcp, were measured, using the transient hot-wire method. We made measurements on solid phases having nominal compositions THF•17H2O, THF•7•1H2O, and THF•4•6H2O, which we refer to as phases α, β, and γ, respectively. Phase α is known to be a structure II clathrate hydrate, and λ for this phase was found to be similar to other crystalline solids which are glass-like in relation to their thermal properties. Low-energy excitations are known to be relevant to the properties of glass-like solids, and, in the case of phase α, were probably rotational vibrations of the THF guest molecules. Phase β was similar, and we inferred that it was probably a structure I clathrate hydrate. Phase γ behaved nearly like a normal crystal phase at low temperatures, but λ became almost independent of temperature near melting. At 1.1 GPa and 130 K, we found evidence that phase α transformed, on pressurization, to a metastable modification which may be a new high-density form of clathrate hydrate. The astrophysical implications of our results were mentioned briefly.


1975 ◽  
Vol 53 (17) ◽  
pp. 2642-2645 ◽  
Author(s):  
John E. Bertie ◽  
Marco Solinas

The far infrared spectra of four isotopic modifications of the partially orientationally ordered clathrate hydrate hexamethylenetetramine hexahydrate at 95 K are reported. The spectra are assigned to absorption allowed under the diffraction factor group, and to disorder-allowed absorption, following the theory for absorption by translational vibrations in orientationally disordered solids. Three phases formed primarily by hydrogen-bonded water molecules are known to be significantly, but only partially, orientationally ordered, hexamethylenetetramine hexahydrate, ice V, and ice VI. Of these phases, only ice VI fails to show sharp absorption in its far infrared spectrum in addition to the broad, disorder-allowed absorption.


Author(s):  
Ziyue Li ◽  
Mengjie Lyu ◽  
Hannes Jónsson ◽  
Christoph Rose-Petruck

2018 ◽  
Vol 212 ◽  
pp. 533-546 ◽  
Author(s):  
David M. Benoit ◽  
David Lauvergnat ◽  
Yohann Scribano

In this study, we examine the effect of a flexible description of the clathrate hydrate framework on the translation–rotation (TR) eigenstates of guest molecules such as molecular hydrogen.


2020 ◽  
Author(s):  
Minjun Cha

<p>Recently, several alkylamine hydrates have been studied in an effort to reveal the structural transitions from semi- to ‘canonical’ clathrate hydrate in the presence of secondary guest molecules. Trimethylamine (TMA) is known to form the semi-clathrate hydrate, and it has been reported that the structural transition of the TMA semi-clathrate hydrate may not occur in the presence of hydrogen gas as a secondary guest molecule. This paper reports the structural transition of trimethylamine(TMA) hydrate induced by the type of guest molecules. Powder X-ray diffraction patterns of (TMA + H<sub>2</sub>) hydrates show the formation of hexagoanl P6/mmm hydrate, but those of (TMA + CH<sub>4</sub>) hydrates indicate the formation of cubic Fd3m hydrate. Without gaseous guest molecule, the crystal structure of pure TMA hydrate is identified as hexagonal P6/mmm. Therefore, inclusion of gaseous methane in TMA hydrate can induce the structural transition from hexagonal to cubic hydrate or the formation of metastable cubic hydrate. To clearly reveal this possibility, we also check the time-dependent structural patterns of binary (TMA + CH<sub>4</sub>) hydrates from 1 to 14 days, and the results show that the structural transition of TMA hydrate from hexagonal P6/mmm to cubic Fd3m hydrate structure can occur during the methane inclusion process.</p>


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