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Nucleation and Growth of Hydrates on Ice Surfaces: New Insights from 129Xe NMR Experiments with Hyperpolarized Xenon
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Section:Abstract
The nucleation and growth of hydrate on the surface of ice was followed by NMR spectroscopy using hyperpolarized Xe. From the ice surface area and Xe pressure drop, the thickness of the hydrate film formed was 
500−1000 Å before the reaction became extremely slow. The cage occupancy ratio θL/θS was measured as a function of time from the Xe spectrum and was used to monitor the nature of the material formed. The ratio changed from values close to 1 during the early part of the reaction (induction time) to its equilibrium value of 3−4 after nucleation processes were finished and rapid growth commenced. The low value can be seen as evidence of a precursor phase that is quite different from the equilibrium hydrate. The induction time was found to be a reproducible function of temperature and pressure for the conditions studied. The kinetics of gas uptake was analyzed according to the Avrami−Erofeyev equation used to describe solid−gas reactions. A surface memory effect was noted on successive cycles of xenon adsorption−desorption−readsorption, as the induction time was absent on the readsorption cycle. The new results are discussed in terms of models for nucleation and growth of hydrate and the various experiments that have been carried out in the past. It is essential to differentiate between later-stage diffusion-limited hydrate formation processes and the initial steps of hydrate formation at a surface, as they have opposite temperature coefficients.
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This article has been cited by 28 ACS Journal articles (5 most recent appear below).
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Hiroshi Ohno, Igor Moudrakovski, Raimond Gordienko, John Ripmeester, and Virginia K. WalkerThe Journal of Physical Chemistry A2012 116 (5), 1337-1343The formation of hydrates from a methane–ethane-propane mixture is more complex than with single gases. Using nuclear magnetic resonance (NMR) and high-pressure powder X-ray diffraction (PXRD), we have investigated the structural properties of natural gas ...
Methane Hydrate Nucleation Rates from Molecular Dynamics Simulations: Effects of Aqueous Methane Concentration, Interfacial Curvature, and System Size
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Matthew R. Walsh, Gregg T. Beckham, Carolyn A. Koh, E. Dendy Sloan, David T. Wu, and Amadeu K. SumThe Journal of Physical Chemistry C2011 115 (43), 21241-21248Methane hydrate nucleation rates are reported from over 200 μs of molecular dynamics simulations across a range of thermodynamic conditions and varying degrees of methane–water interfacial curvature. Calculated nucleation rates increase with aqueous phase ...
13C NMR Studies of Hydrocarbon Guests in Synthetic Structure H Gas Hydrates: Experiment and Computation
Jong-Won Lee, Hailong Lu, Igor L. Moudrakovski, Christopher I. Ratcliffe, Ryo Ohmura, Saman Alavi, and John A. RipmeesterThe Journal of Physical Chemistry A2011 115 (9), 1650-165713C NMR Studies of Hydrocarbon Guests in Synthetic Structure H Gas Hydrates: Experiment and Computation
Jong-Won Lee, Hailong Lu, Igor L. Moudrakovski, Christopher I. Ratcliffe, Ryo Ohmura, Saman Alavi, and John A. RipmeesterThe Journal of Physical Chemistry A2011 115 (9), 1650-165713C NMR chemical shifts were measured for pure (neat) liquids and synthetic binary hydrate samples (with methane help gas) for 2-methylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylpentane, 3-methylpentane, methylcyclopentane, and ...
High-Pressure Differential Scanning Calorimetry Measurements of the Mass Transfer Resistance across a Methane Hydrate Film as a Function of Time and Subcooling
Simon R. Davies, Jason W. Lachance, E. Dendy Sloan, and Carolyn A. KohIndustrial & Engineering Chemistry Research2010 49 (23), 12319-12326High-Pressure Differential Scanning Calorimetry Measurements of the Mass Transfer Resistance across a Methane Hydrate Film as a Function of Time and Subcooling
Simon R. Davies, Jason W. Lachance, E. Dendy Sloan, and Carolyn A. KohIndustrial & Engineering Chemistry Research2010 49 (23), 12319-12326High pressure differential scanning calorimetry was utilized to study the mass transfer rates across methane hydrate films grown at hydrocarbon−water interfaces in a quiescent system, as a function of subcooling and the age of the film. Gas hydrate films ...
Equilibrium Data of Methane, Carbon Dioxide, and Xenon Clathrate Hydrates below the Freezing Point of Water. Applications to Astrophysical Environments
Nicolas Fray, Ulysse Marboeuf, Olivier Brissaud, and Bernard SchmittJournal of Chemical & Engineering Data2010 55 (11), 5101-5108Equilibrium Data of Methane, Carbon Dioxide, and Xenon Clathrate Hydrates below the Freezing Point of Water. Applications to Astrophysical Environments
Nicolas Fray, Ulysse Marboeuf, Olivier Brissaud, and Bernard SchmittJournal of Chemical & Engineering Data2010 55 (11), 5101-5108This work reports new measurements of the three-phase (ice + clathrate hydrate + vapor) equilibrium in the systems of water and each of the following guest species: xenon from (167.20 to 246.16) K, carbon dioxide from (172.28 to 182.15) K, and methane ...
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History
- Published In Issue December 13, 2001
- Received June 26, 2001
Revised September 13, 2001
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