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Title: 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:
 [1];  [2];  [2];  [2];  [2]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. 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:
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. Fri . "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},
journal = {Surface Science},
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}
}

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Cited by: 2 works
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Works referenced in this record:

A review of the geochemistry of methane in natural gas hydrate
journal, November 1995


Global estimates of hydrate-bound gas in marine sediments: how much is really out there?
journal, August 2004


The Occurrence of gas Hydrates in the Solar System
journal, November 1961


Physico-chemical phenomena in comets—I
journal, May 1970


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
  • DOI: 10.1021/je1006604

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
  • DOI: 10.1086/191050

Peculiarities of Methane Clathrate Hydrate Formation and Solid-State Deformation, Including Possible Superheating of Water Ice
journal, September 1996


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
  • DOI: 10.2138/am-2004-8-902

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
  • DOI: 10.1021/jp061060f

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
  • DOI: 10.1016/j.ces.2008.10.017

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
  • DOI: 10.1021/i160051a012

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
  • DOI: 10.1021/jp1084229

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
  • DOI: 10.1021/jp310972b

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
  • DOI: 10.1021/jp806643e

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
  • DOI: 10.1029/2000JE001362

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
  • DOI: 10.1063/1.4793311

A molecular mechanism for gas hydrate nucleation from ice
journal, September 1991


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
  • DOI: 10.1021/jp037900x

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
  • DOI: 10.1039/b807455k

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
  • DOI: 10.1039/b913898f

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
  • DOI: 10.1021/ja309117d

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
  • DOI: 10.1021/jp2086544

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
  • DOI: 10.1021/ja400521e

Gas hydrates-geological perspective and global change
journal, May 1993

  • Kvenvolden, Keith A.
  • Reviews of Geophysics, Vol. 31, Issue 2
  • DOI: 10.1029/93RG00268

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
  • DOI: 10.1021/jp952670a

Observation of Surface Self-Diffusion on Ice
journal, March 2009


Measurement and prediction of dissociation pressures of isobutane and propane hydrates below the ice point
journal, November 1982


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
  • DOI: 10.1073/pnas.1303001110

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
  • DOI: 10.1088/0953-8984/24/12/124103

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
  • DOI: 10.1063/1.4896300

Adsorbed water-molecule hexagons with unexpected rotations in islands on Ru(0001) and Pd(111)
journal, April 2012


Growth of multilayer ice films and the formation of cubic ice imaged with STM
journal, May 2008


Nucleation-Limited Dewetting of Ice Films on Pt(111)
journal, May 2008


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
  • DOI: 10.1063/1.2177658

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
  • DOI: 10.1063/1.2790432

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
  • DOI: 10.1063/1.1350580

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
  • DOI: 10.1063/1.2060691

Crystalline Ice Growth on Pt(111): Observation of a Hydrophobic Water Monolayer
journal, October 2005


Evolution of proton order during ice-film growth: An analysis of island shapes
journal, July 2011


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
  • DOI: 10.1063/1.2672869

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
  • DOI: 10.1063/1.2400235

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
  • DOI: 10.1021/jp110297q

The Molecular Volcano: Abrupt CC l 4 Desorption Driven by the Crystallization of Amorphous Solid Water
journal, August 1997


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
  • DOI: 10.1021/jz201648g

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
  • DOI: 10.1021/la00013a025

Clathrate Hydrates Formation in Short-Period Comets
journal, December 2009


The distribution of methane in Titan’s stratosphere from Cassini/CIRS observations
journal, March 2014


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
  • DOI: 10.1029/2000JE001425

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
  • DOI: 10.1093/mnras/stw1632

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
  • DOI: 10.1063/1.5098481

Cometary ices in forming protoplanetary disc midplanes
text, January 2016

  • Thiabaud, Amaury; Walsh, Catherine; Van Dishoeck, Ewine F.
  • Oxford University Press
  • DOI: 10.7892/boris.89101