Synthesis and characterization of clathrate hydrates containing carbon dioxide and ethanol

Makiya, Takeshi; Murakami, Takashi; Takeya, Satoshi; Sum, Amadeu K.; Alavi, Saman; Ohmura, Ryo

doi:10.1039/c002187c

Cited by 45 publications

(27 citation statements)

References 48 publications

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“…Recently, several kinds of alcohol molecules were reported as structure II (sII) or structure H (sH) hydrate formers 8. 9 It was reported that large alcohol guest molecules (LAGMs), such as ethanol,10 1‐propanol9b and 2‐propanol,9c,d could be enclathrated in a hydrate cavity structure in the presence of a help gas, such as methane and carbon dioxide. In addition, possible host–guest hydrogen‐bonding interactions between alcohol guest and water were extensively examined through single crystal X‐ray diffraction and molecular dynamic simulations, and the results revealed that there could be possible hydrogen‐bonding interactions or incorporation of hydroxy groups into hydrate cages 9a.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic Observation of the Hydroxy Position in Butanol Hydrates and Its Effect on Hydrate Stability

2015

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In this study, we investigate the crystal structures and phase equilibria of butanols+CH +H O systems to reveal the hydroxy group positioning and its effects on hydrate stability. Four clathrate hydrates formed by structural butanol isomers are identified with powder X-ray diffraction (PXRD). In addition, Raman spectroscopy is used to analyze the guest distributions and inclusion behaviors of large alcohol molecules in these hydrate systems. The existence of a free OH indicates that guest molecules can be captured in the large cages of structure II hydrates without any hydrogen-bonding interactions between the hydroxy group of the guests and the water-host framework. However, Raman spectra of the binary (1-butanol+CH ) hydrate do not show the free OH signal, indicating that there could be possible hydrogen-bonding interactions between the guests and hosts. We also measure the four-phase equilibrium conditions of the butanols+CH +H O systems.

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Section: Introductionmentioning

confidence: 99%

Spectroscopic Observation of the Hydroxy Position in Butanol Hydrates and Its Effect on Hydrate Stability

2015

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“…4 size. The discrepancy between the experimentally observed and MD predicted dihedral angle might be related to the approximate nature of the intramolecular dihedral potential in the force field.…”

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confidence: 97%

Communication: Single crystal x-ray diffraction observation of hydrogen bonding between 1-propanol and water in a structure II clathrate hydrate

Udachin¹,

Alavi²,

Ripmeester³

2011

The Journal of Chemical Physics

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Single crystal x-ray crystallography is used to detect guest-host hydrogen bonding in structure II (sII) binary clathrate hydrate of 1-propanol and methane. X-ray structural analysis shows that the 1-propanol oxygen atom is at a distance of 2.749 and 2.788 Å from the closest clathrate hydrate water oxygen atoms from a hexagonal face of the large sII cage. The 1-propanol hydroxyl hydrogen atom is disordered and at distances of 1.956 and 2.035 Å from the closest cage water oxygen atoms. These distances are compatible with guest-water hydrogen bonding. The C-C-C-O torsional angle in 1-propanol in the cage is 91.47° which corresponds to a staggered conformation for the guest. Molecular dynamics studies of this system demonstrated guest-water hydrogen bonding in this hydrate. The molecular dynamics simulations predict most probable distances for the 1-propanol-water oxygen atoms to be 2.725 Å, and the average C-C-C-O torsional angle to be ~59° consistent with a gauche conformation. The individual cage distortions resulting from guest-host hydrogen bonding from the simulations are rather large, but due to the random nature of the hydrogen bonding of the guest with the 24 water molecules making up the hexagonal faces of the large sII cages, these distortions are not observed in the x-ray structure.

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“…At low temperatures, ethanol forms hydrate phases with water or binary hydrate phases with air as the help gas. 7 It has recently been observed that in the presence of small help gas molecules such as methane [8][9][10] and carbon dioxide, 11 water-soluble ethanol, 1-propanol, and 2-propanol form stable sII clathrate hydrates, presumably because the hydrophobic portion of the guest molecules is larger than methanol. On their own, these alcohols are miscible in water and disrupt the water-water hydrogen-bonding network in such a way as to prevent formation of stable pure alcohol clathrate hydrates.…”

Section: Introductionmentioning

confidence: 99%

Hydrogen-bonding alcohol-water interactions in binary ethanol, 1-propanol, and 2-propanol+methane structure II clathrate hydrates

Alavi

Takeya

Ohmura

et al. 2010

The Journal of Chemical Physics

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114

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The small alcohols ethanol, 1-propanol, and 2-propanol are miscible in water, form strong hydrogen bonds with water molecules, and are usually known as inhibitors for clathrate hydrate formation. However, in the presence of methane or other help gases, clathrate hydrates of these substances have been synthesized. In this work, molecular dynamics simulations are used to characterize guest-host hydrogen bonding, microscopic structures, and guest dynamics of binary structure II clathrate hydrates of methane (small cages) with ethanol, 1-propanol, and 2-propanol in the temperature range of 100–250 K to gain insight into the stability of these materials. We observe that these alcohols form structures with dynamic long-lived (∼10 ps) guest-host hydrogen bonds in the hydrate phases while maintaining the general cage structure of the sII clathrate hydrate form. The hydroxyl groups of ethanol, 1-propanol, and 2-propanol act as both proton acceptors and proton donors and there is a considerable probability of simultaneous hydrogen bonding between O and H hydroxyl atoms with different cage water molecules. The presence of the nonpolar methane molecule and the hydrophobic moieties of the alcohols stabilize the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The effect of the alcohol molecules on the structural properties of the hydrate and the effect of guest-host hydrogen bonding on the guest dynamics are studied.

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Synthesis and characterization of clathrate hydrates containing carbon dioxide and ethanol

Cited by 45 publications

References 48 publications

Spectroscopic Observation of the Hydroxy Position in Butanol Hydrates and Its Effect on Hydrate Stability

Spectroscopic Observation of the Hydroxy Position in Butanol Hydrates and Its Effect on Hydrate Stability

Communication: Single crystal x-ray diffraction observation of hydrogen bonding between 1-propanol and water in a structure II clathrate hydrate

Hydrogen-bonding alcohol-water interactions in binary ethanol, 1-propanol, and 2-propanol+methane structure II clathrate hydrates

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