Spectroscopic and thermodynamic investigations of clathrate hydrates of methacrolein

Ahn, Young‐Ho; Youn, Yeobum; Cha, Minjun; Lee, Huen

doi:10.1039/c6ra28434e

Cited by 11 publications

(5 citation statements)

References 31 publications

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“…The measured data for the phase equilibria are shown and tabulated in Figure and Table . The binary CPM + CH 4 hydrate was less thermodynamically stable than the binary tetrahydrofuran or methacrolein + CH 4 hydrates and had a stability similar to that of the pure CH 4 hydrate. , In addition, the equilibrium temperatures of binary CPM + CH 4 hydrate at given pressure were slightly lower than those of 2-propanol + CH 4 hydrate at given pressures but could be comparable with those of 1-propanol + CH 4 hydrate at given pressures. , …”

Section: Results and Discussionmentioning

confidence: 92%

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Spectroscopic Observations of Host–Guest Hydrogen Bonding in Binary Cyclopropanemethanol + Methane Hydrate

2019

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Herein, we report a new structure II (sII) hydrate with cyclopropanemethanol (CPM) in the presence of methane (CH4) gas for the first time and investigate the host–guest hydrogen bonding in the binary CPM + CH4 hydrate via solid-state NMR, Raman spectroscopy, and synchrotron X-ray powder diffraction analysis. The crystal structure and guest distribution of the binary CPM + CH4 hydrate were characterized using solid-state 13C NMR and powder diffraction analyses, which confirmed the formation of the binary sII CPM + CH4 hydrate. The CPM in the large cages of sII hydrate was predicted to be present in the dynamic Anti (Anti I or Anti II) form based on the measured- and calculated- NMR spectra. The inclusion of CH4 molecules in both the large and small cages of the sII hydrate was observed from the 13C NMR and Raman spectra. No free OH signals of the CPM guest were observed in the Raman spectra of the binary CPM + CH4 hydrate, which indicated that the CPM guest participated in host–guest hydrogen bonding with the water framework. The powder diffraction pattern of the binary CPM + CH4 hydrate was refined using Rietveld analysis with the direct space method, and the results supported the hydrogen bonding of the hydroxyl group of the CPM guest to the host water molecules. The phase equilibrium temperature and pressure conditions of the binary CPM + CH4 hydrate were also measured, and the binary CPM + CH4 hydrate was found to be less stable than the binary tetrahydrofuran + CH4 hydrate.

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Section: Results and Discussionmentioning

confidence: 92%

“…Phase equilbrium curve of cyclopropanemethanol (5.6 mol %) + CH 4 (●), pure CH 4 (black line), tetrahydrofuran (5 mol %) + CH 4 (○), methacrolein (5.56 mol %) + CH 4 (△), 1-propanol (5.56 mol %) + CH 4 (□), and 2-propanol (5.56 mol %) + CH 4 (▽) hydrates.…”

Section: Results and Discussionmentioning

confidence: 99%

Spectroscopic Observations of Host–Guest Hydrogen Bonding in Binary Cyclopropanemethanol + Methane Hydrate

2019

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“…Notably, the thermodynamic stability of CH 4 hydrate was significantly enhanced by the addition of CPeA to the hydrate systems. Compared with binary (large guest molecule + CH 4 ) hydrates, the equilibrium temperatures of the binary (CPeA + CH 4 ) hydrate were higher than those of (cyclobutanemethanol + CH 4 ) and (methacrolein + CH 4 ) hydrates but were lower than those of the binary (isobutylaldehyde + CH 4 ) and (tetrahydrofuran + CH 4 ) hydrates. ,− In our previous study, we examined the CH 4 storage capacity of the binary of (cyclobutanemethanol + CH 4 ) hydrate for the potential applications of gas hydrates to gas storage, and the CH 4 storage content of the binary of (cyclobutanemethanol + CH 4 ) hydrate was ∼113.3 mmol-CH 4 /mol-H 2 O . The unit cell formula of the binary (CPeA + CH 4 ) hydrate was 7.889 CPeA·14.849 CH 4 ·136 H 2 O, as shown in Table , and we could expect that the CH 4 storage capacity of the binary (CPeA + CH 4 ) hydrate was ∼109.2 mmol-CH 4 /mol-H 2 O.…”

Section: Resultsmentioning

confidence: 99%

“…Phase equilibria of (cyclopropylamine + CH 4 ), (cyclopentylamine + CH 4 ), methacrolein (5.56 mol %) + CH 4 (◇), isobutylaldehyde + CH 4 (△), cyclobutanemethanol + CH 4 (□), THF (5 mol %) + CH 4 (○) hydrates, and pure CH 4 hydrate. ,,− …”

Section: Resultsmentioning

confidence: 99%

Phase Equilibria and Spectroscopic Identification of Structure II Hydrates with New Hydrate-Forming Agents (Cyclopropylamine and Cyclopentylamine)

2022

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In this study, the phase equilibria of binary (cyclopropylamine (CPrA) + methane (CH 4 )) and (cyclopentylamine (CPeA) + CH 4 ) hydrates were investigated using a conventional isochoric pressure−temperature trace method. The equilibrium temperatures of the binary (CPrA + CH 4 ) and (CPeA + CH 4 ) hydrates were higher than those of pure CH 4 hydrate. The guest conformation and inclusion behaviors of the binary (CPrA + CH 4 ) and (CPeA + CH 4 ) hydrates were also examined through 13 C solid-state nuclear magnetic resonance spectroscopy, and the results confirmed the formation of structure II hydrates with new hydrate-forming agents, CPrA and CPeA, in the presence of CH 4 . The crystal structures and possible host−guest interactions of the proposed hydrate systems were investigated through Rietveld analysis using the direct space method, and the results demonstrated the formation of sII hydrates (with cubic Fd-3m) and the possibility of host−guest interactions in the binary (CPrA + CH 4 ) and (CPeA + CH 4 ) hydrates. These observations provide an improved understanding of the unique nature of host−guest inclusion phenomena.

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“…Numerous organic compounds can act as hydrate formers and are not limited to hydrocarbons. Diverse sII and sH formers contain various functional groups have been reported thus far, including hydroxyl, − ether, − ketone, ,,− amine, − nitro, , and others. − The ability of a compound to act as a hydrate former and the specific hydrate structure it forms primarily depends on its size, although other factors also influence it. For example, diisopropyl amine is an sH former, whereas 2,4-dimethylpentane and diisopropyl ether are not, despite being isoelectric and exhibiting similar structures and size.…”

Section: Introductionmentioning

confidence: 99%

Geometric and Hydrophilic Effects of Oxirane Compounds with a Four-Carbon Backbone on Clathrate Hydrate Formation

Seol

2023

ACS Omega

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The physicochemical properties of clathrate hydrates are influenced by the chemical nature and three-dimensional (3D) geometry of the added molecules. This study investigates the effects of five oxirane compounds: cis-2,3-epoxybutane (c23EB), trans-2,3-epoxybutane (t23EB), 1,2-epoxybutane (12EB), 1,2,3,4-diepoxybutane (DEB), and 3,3-dimethylepoxybutane (33DMEB) on CH4 hydrate formation. Despite having a four-carbon backbone, these compounds differ in their 3D geometries. The structures and stabilities of CH4 hydrates containing each compound were analyzed using high-resolution powder diffraction, solid-state 13C NMR, and phase equilibrium measurements. The experimental results revealed that c23EB, 12EB, and 33DMEB act as sII/sH hydrate formers and thermodynamic promoters, whereas t23EB and DEB have opposite roles. These results were analyzed in relation to the 3D geometries and relative stabilities of various rotational isomers using DFT calculations. Hydrate structure was influenced by both the length and thickness of the added compounds. Moreover, an appropriate level of (not excessive) hydrophilicity induced by an oxirane group appeared to enhance the thermodynamic stability of the hydrates. This study provides insights into how the chemical nature of additives influences the structure and stability of clathrate hydrates.

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Spectroscopic and thermodynamic investigations of clathrate hydrates of methacrolein

Abstract: This study characterized new structure II (sII) clathrate hydrates, consisting of 136 H2O molecules with 8 large 51264 cages and 16 small 512 cages, with methacrolein for the first time.

Cited by 11 publications

References 31 publications

Spectroscopic Observations of Host–Guest Hydrogen Bonding in Binary Cyclopropanemethanol + Methane Hydrate

Spectroscopic Observations of Host–Guest Hydrogen Bonding in Binary Cyclopropanemethanol + Methane Hydrate

Phase Equilibria and Spectroscopic Identification of Structure II Hydrates with New Hydrate-Forming Agents (Cyclopropylamine and Cyclopentylamine)

Geometric and Hydrophilic Effects of Oxirane Compounds with a Four-Carbon Backbone on Clathrate Hydrate Formation

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