Weak interactions between water and clathrate-forming gases at low pressures
Abstract
Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10–1 mbar methane or 10–5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~ 107 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10–5 mbar methane does not alter their morphology, suggesting that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water–gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~ 43 K and isobutane desorbs near ~ 100 K. As a result, similar desorption temperatures were observed for desorption from amorphous solid water.
- Authors:
-
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1236221
- Alternate Identifier(s):
- OSTI ID: 1244762
- Report Number(s):
- SAND-2015-3713J
Journal ID: ISSN 0039-6028; 583780
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Surface Science
- Additional Journal Information:
- Journal Volume: 641; Journal Issue: C; Journal ID: ISSN 0039-6028
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cathrates; water; methane; isobutane; STM; TPD
Citation Formats
Thürmer, Konrad, Yuan, Chunqing, Kimmel, Greg A., Kay, Bruce D., and Smith, R. Scott. Weak interactions between water and clathrate-forming gases at low pressures. United States: N. p., 2015.
Web. doi:10.1016/j.susc.2015.07.013.
Thürmer, Konrad, Yuan, Chunqing, Kimmel, Greg A., Kay, Bruce D., & Smith, R. Scott. Weak interactions between water and clathrate-forming gases at low pressures. United States. https://doi.org/10.1016/j.susc.2015.07.013
Thürmer, Konrad, Yuan, Chunqing, Kimmel, Greg A., Kay, Bruce D., and Smith, R. Scott. 2015.
"Weak interactions between water and clathrate-forming gases at low pressures". United States. https://doi.org/10.1016/j.susc.2015.07.013. https://www.osti.gov/servlets/purl/1236221.
@article{osti_1236221,
title = {Weak interactions between water and clathrate-forming gases at low pressures},
author = {Thürmer, Konrad and Yuan, Chunqing and Kimmel, Greg A. and Kay, Bruce D. and Smith, R. Scott},
abstractNote = {Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10–1 mbar methane or 10–5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~ 107 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10–5 mbar methane does not alter their morphology, suggesting that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water–gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~ 43 K and isobutane desorbs near ~ 100 K. As a result, similar desorption temperatures were observed for desorption from amorphous solid water.},
doi = {10.1016/j.susc.2015.07.013},
url = {https://www.osti.gov/biblio/1236221},
journal = {Surface Science},
issn = {0039-6028},
number = C,
volume = 641,
place = {United States},
year = {Fri Jul 17 00:00:00 EDT 2015},
month = {Fri Jul 17 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
A review of the geochemistry of methane in natural gas hydrate
journal, November 1995
- Kvenvolden, Keith A.
- Organic Geochemistry, Vol. 23, Issue 11-12
Global estimates of hydrate-bound gas in marine sediments: how much is really out there?
journal, August 2004
- Milkov, Alexei V.
- Earth-Science Reviews, Vol. 66, Issue 3-4
The Occurrence of gas Hydrates in the Solar System
journal, November 1961
- Miller, S. L.
- Proceedings of the National Academy of Sciences, Vol. 47, Issue 11
Physico-chemical phenomena in comets—I
journal, May 1970
- Delsemme, A. H.; Wenger, A.
- Planetary and Space Science, Vol. 18, Issue 5
Equilibrium Data of Methane, Carbon Dioxide, and Xenon Clathrate Hydrates below the Freezing Point of Water. Applications to Astrophysical Environments
journal, November 2010
- Fray, Nicolas; Marboeuf, Ulysse; Brissaud, Olivier
- Journal of Chemical & Engineering Data, Vol. 55, Issue 11
Thermodynamics of clathrate hydrate at low and high pressures with application to the outer solar system
journal, July 1985
- Lunine, J. I.; Stevenson, D. J.
- The Astrophysical Journal Supplement Series, Vol. 58
Peculiarities of Methane Clathrate Hydrate Formation and Solid-State Deformation, Including Possible Superheating of Water Ice
journal, September 1996
- Stern, L. A.; Kirby, S. H.; Durham, W. B.
- Science, Vol. 273, Issue 5283
Scanning Electron Microscopy investigations of laboratory-grown gas clathrate hydrates formed from melting ice, and comparison to natural hydrates
journal, August 2004
- Stern, Laura A.; Kirby, Stephen H.; Circone, Susan
- American Mineralogist, Vol. 89, Issue 8-9
Formation of Methane Hydrate from Polydisperse Ice Powders
journal, July 2006
- Kuhs, Werner F.; Staykova, Doroteya K.; Salamatin, Andrey N.
- The Journal of Physical Chemistry B, Vol. 110, Issue 26
Studies of hydrate nucleation with high pressure differential scanning calorimetry
journal, January 2009
- Davies, Simon R.; Hester, Keith C.; Lachance, Jason W.
- Chemical Engineering Science, Vol. 64, Issue 2
Experimental Determination of Gas Hydrate Equilibrium below the Ice Point
journal, August 1974
- Falabella, Benjamin J.; Vanpee, Marcel
- Industrial & Engineering Chemistry Fundamentals, Vol. 13, Issue 3
Kinetics of CO 2 Hydrate Formation from Water Frost at Low Temperatures: Experimental Results and Theoretical Model
journal, February 2011
- Falenty, Andrzej; Genov, Georgi; Hansen, Thomas C.
- The Journal of Physical Chemistry C, Vol. 115, Issue 10
Kinetics of CO 2 -Hydrate Formation from Ice Powders: Data Summary and Modeling Extended to Low Temperatures
journal, April 2013
- Falenty, A.; Salamatin, A. N.; Kuhs, W. F.
- The Journal of Physical Chemistry C, Vol. 117, Issue 16
Interaction of Carbon Dioxide and Hydroxide Ion at the Surface of Ice Films
journal, October 2008
- Kim, Young-Kwang; Park, Seong-Chan; Kim, Jung-Hwan
- The Journal of Physical Chemistry C, Vol. 112, Issue 46
Effect of porosity on the adsorption, desorption, trapping, and release of volatile gases by amorphous solid water
journal, December 2001
- Ayotte, Patrick; Smith, R. Scott; Stevenson, K. P.
- Journal of Geophysical Research: Planets, Vol. 106, Issue E12
The release of trapped gases from amorphous solid water films. I. “Top-down” crystallization-induced crack propagation probed using the molecular volcano
journal, March 2013
- May, R. Alan; Smith, R. Scott; Kay, Bruce D.
- The Journal of Chemical Physics, Vol. 138, Issue 10
A molecular mechanism for gas hydrate nucleation from ice
journal, September 1991
- Sloan, E. D.; Fleyfel, F.
- AIChE Journal, Vol. 37, Issue 9
Molecular Models for the Intercalation of Methane Hydrate Complexes in Montmorillonite Clay
journal, September 2004
- Cygan, Randall T.; Guggenheim, Stephen; Koster van Groos, August F.
- The Journal of Physical Chemistry B, Vol. 108, Issue 39
Gas hydrate nucleation and cage formation at a water/methane interface
journal, January 2008
- Hawtin, Robert W.; Quigley, David; Rodger, P. Mark
- Physical Chemistry Chemical Physics, Vol. 10, Issue 32
Why can water cages adsorb aqueous methane? A potential of mean force calculation on hydrate nucleation mechanisms
journal, January 2009
- Guo, Guang-Jun; Li, Meng; Zhang, Yi-Gang
- Physical Chemistry Chemical Physics, Vol. 11, Issue 44
Homogeneous Nucleation of Methane Hydrates: Unrealistic under Realistic Conditions
journal, November 2012
- Knott, Brandon C.; Molinero, Valeria; Doherty, Michael F.
- Journal of the American Chemical Society, Vol. 134, Issue 48
Molecular Modeling of the Dissociation of Methane Hydrate in Contact with a Silica Surface
journal, March 2012
- Bagherzadeh, S. Alireza; Englezos, Peter; Alavi, Saman
- The Journal of Physical Chemistry B, Vol. 116, Issue 10
Molecular Insights into Clathrate Hydrate Nucleation at an Ice–Solution Interface
journal, May 2013
- Pirzadeh, Payman; Kusalik, Peter G.
- Journal of the American Chemical Society, Vol. 135, Issue 19
Gas hydrates-geological perspective and global change
journal, May 1993
- Kvenvolden, Keith A.
- Reviews of Geophysics, Vol. 31, Issue 2
Surface and Bulk Diffusion of H 2 18 O on Single-Crystal H 2 16 O Ice Multilayers
journal, January 1996
- Brown, D. E.; George, S. M.
- The Journal of Physical Chemistry, Vol. 100, Issue 38
Observation of Surface Self-Diffusion on Ice
journal, March 2009
- Nie, S.; Bartelt, N. C.; Thürmer, K.
- Physical Review Letters, Vol. 102, Issue 13
Measurement and prediction of dissociation pressures of isobutane and propane hydrates below the ice point
journal, November 1982
- Holder, G. D.; Godbole, S. P.
- AIChE Journal, Vol. 28, Issue 6
Formation of hexagonal and cubic ice during low-temperature growth
journal, July 2013
- Thurmer, K.; Nie, S.
- Proceedings of the National Academy of Sciences, Vol. 110, Issue 29
H 2 O on Pt(111): structure and stability of the first wetting layer
journal, March 2012
- Standop, Sebastian; Morgenstern, Markus; Michely, Thomas
- Journal of Physics: Condensed Matter, Vol. 24, Issue 12
Clusters, molecular layers, and 3D crystals of water on Ni(111)
journal, November 2014
- Thürmer, Konrad; Nie, Shu; Feibelman, Peter J.
- The Journal of Chemical Physics, Vol. 141, Issue 18
Adsorbed water-molecule hexagons with unexpected rotations in islands on Ru(0001) and Pd(111)
journal, April 2012
- Maier, Sabine; Stass, Ingeborg; Mitsui, Toshiyuki
- Physical Review B, Vol. 85, Issue 15
Growth of multilayer ice films and the formation of cubic ice imaged with STM
journal, May 2008
- Thürmer, Konrad; Bartelt, Norman C.
- Physical Review B, Vol. 77, Issue 19
Nucleation-Limited Dewetting of Ice Films on Pt(111)
journal, May 2008
- Thürmer, Konrad; Bartelt, Norman C.
- Physical Review Letters, Vol. 100, Issue 18
The effect of the incident collision energy on the phase and crystallization kinetics of vapor deposited water films
journal, March 2006
- Scott Smith, R.; Zubkov, Tykhon; Kay, Bruce D.
- The Journal of Chemical Physics, Vol. 124, Issue 11
Adsorption, desorption, and diffusion of nitrogen in a model nanoporous material. I. Surface limited desorption kinetics in amorphous solid water
journal, November 2007
- Zubkov, Tykhon; Smith, R. Scott; Engstrom, Todd R.
- The Journal of Chemical Physics, Vol. 127, Issue 18
Control of amorphous solid water morphology using molecular beams. I. Experimental results
journal, March 2001
- Kimmel, Greg A.; Stevenson, K. P.; Dohnálek, Z.
- The Journal of Chemical Physics, Vol. 114, Issue 12
The structure and crystallization of thin water films on Pt(111)
journal, November 2005
- Zimbitas, G.; Haq, S.; Hodgson, A.
- The Journal of Chemical Physics, Vol. 123, Issue 17
Crystalline Ice Growth on Pt(111): Observation of a Hydrophobic Water Monolayer
journal, October 2005
- Kimmel, Greg A.; Petrik, Nikolay G.; Dohnálek, Zdenek
- Physical Review Letters, Vol. 95, Issue 16
Evolution of proton order during ice-film growth: An analysis of island shapes
journal, July 2011
- Nie, Shu; Bartelt, Norman C.; Thürmer, Konrad
- Physical Review B, Vol. 84, Issue 3
Crystalline ice growth on Pt(111) and Pd(111): Nonwetting growth on a hydrophobic water monolayer
journal, March 2007
- Kimmel, Greg A.; Petrik, Nikolay G.; Dohnálek, Zdenek
- The Journal of Chemical Physics, Vol. 126, Issue 11
n-alkanes on Pt(111) and on C(0001)∕Pt(111): Chain length dependence of kinetic desorption parameters
journal, December 2006
- Tait, Steven L.; Dohnálek, Zdenek; Campbell, Charles T.
- The Journal of Chemical Physics, Vol. 125, Issue 23
Crystallization Kinetics and Excess Free Energy of H 2 O and D 2 O Nanoscale Films of Amorphous Solid Water
journal, June 2011
- Smith, R. Scott; Matthiesen, Jesper; Knox, Jake
- The Journal of Physical Chemistry A, Vol. 115, Issue 23
The Molecular Volcano: Abrupt CC Desorption Driven by the Crystallization of Amorphous Solid Water
journal, August 1997
- Smith, R. Scott; Huang, C.; Wong, E. K. L.
- Physical Review Letters, Vol. 79, Issue 5
The Molecular Volcano Revisited: Determination of Crack Propagation and Distribution During the Crystallization of Nanoscale Amorphous Solid Water Films
journal, January 2012
- May, R. Alan; Smith, R. Scott; Kay, Bruce D.
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 3
Adsorption and desorption behavior of n-butane and isobutane on Pt(111) and Sn/Pt(111) surface alloys
journal, January 1994
- Xu, Chen; Koel, Bruce E.; Paffett, Mark T.
- Langmuir, Vol. 10, Issue 1
Clathrate Hydrates Formation in Short-Period Comets
journal, December 2009
- Marboeuf, Ulysse; Mousis, Olivier; Petit, Jean-Marc
- The Astrophysical Journal, Vol. 708, Issue 1
The distribution of methane in Titan’s stratosphere from Cassini/CIRS observations
journal, March 2014
- Lellouch, E.; Bézard, B.; Flasar, F. M.
- Icarus, Vol. 231
On the possibility of clathrate hydrates on the Moon
journal, November 2001
- Duxbury, N. S.; Nealson, K. H.; Romanovsky, V. E.
- Journal of Geophysical Research: Planets, Vol. 106, Issue E11
Works referencing / citing this record:
Cometary ices in forming protoplanetary disc midplanes
journal, July 2016
- Drozdovskaya, Maria N.; Walsh, Catherine; van Dishoeck, Ewine F.
- Monthly Notices of the Royal Astronomical Society, Vol. 462, Issue 1
Crystallization growth rates and front propagation in amorphous solid water films
journal, June 2019
- Smith, R. Scott; Yuan, Chunqing; Petrik, Nikolay G.
- The Journal of Chemical Physics, Vol. 150, Issue 21
Cometary ices in forming protoplanetary disc midplanes
text, January 2016
- Thiabaud, Amaury; Walsh, Catherine; Van Dishoeck, Ewine F.
- Oxford University Press