Peculiarities of methane clathrate hydrate formation and solid-state deformation, including possible superheating of water ice

Science

Volumn 273, Issue 5283, 1996, Pages 1843-1848

  Stern, Laura A ^a   Kirby, Stephen H ^a   Durham, William B ^b  

^a U S GEOLOGICAL SURVEY   (United States)

^b LAWRENCE LIVERMORE NATIONAL LABORATORY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ICE; METHANE; WATER;

ARTICLE; CRYSTALLIZATION; GAS MIXING; HEATING; HYDRATION; HYDROSTATIC PRESSURE; PRIORITY JOURNAL; SHEAR STRESS; SOLID; STOICHIOMETRY; STRESS STRAIN RELATIONSHIP; WATER FLOW; X RAY DIFFRACTION;

EID: 0029744796     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.273.5283.1843     Document Type: Article

References (44)

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2. S. Miller, Proc. Natl. Acad. Sci. U.S.A. 47, 1798 (1961); G. Consolmagno, J. Chem. Phys. 87, 4202 (1983); D. Cruikshank, R. Brown, R. Clark, in Ices in the Solar System, J. Klinger et al., Eds. (Reidel, Dordrecht, The Netherlands, 1985), pp. 817-827; R. G. Prinn and B. Fegley Jr., in Origin and Evolution of Planetary and Satellite Atmospheres, S. K. Atreya et al., Eds. (Univ. of Arizona Press, Tucson, AZ, 1989), pp. 78-136; J. Lunine and D. Stevenson, Astrophys. J. Suppl. 58, 493 (1985).
3. S. Miller, Proc. Natl. Acad. Sci. U.S.A. 47, 1798 (1961); G. Consolmagno, J. Chem. Phys. 87, 4202 (1983); D. Cruikshank, R. Brown, R. Clark, in Ices in the Solar System, J. Klinger et al., Eds. (Reidel, Dordrecht, The Netherlands, 1985), pp. 817-827; R. G. Prinn and B. Fegley Jr., in Origin and Evolution of Planetary and Satellite Atmospheres, S. K. Atreya et al., Eds. (Univ. of Arizona Press, Tucson, AZ, 1989), pp. 78-136; J. Lunine and D. Stevenson, Astrophys. J. Suppl. 58, 493 (1985).
4. S. Miller, Proc. Natl. Acad. Sci. U.S.A. 47, 1798 (1961); G. Consolmagno, J. Chem. Phys. 87, 4202 (1983); D. Cruikshank, R. Brown, R. Clark, in Ices in the Solar System, J. Klinger et al., Eds. (Reidel, Dordrecht, The Netherlands, 1985), pp. 817-827; R. G. Prinn and B. Fegley Jr., in Origin and Evolution of Planetary and Satellite Atmospheres, S. K. Atreya et al., Eds. (Univ. of Arizona Press, Tucson, AZ, 1989), pp. 78-136; J. Lunine and D. Stevenson, Astrophys. J. Suppl. 58, 493 (1985).
5. S. Miller, Proc. Natl. Acad. Sci. U.S.A. 47, 1798 (1961); G. Consolmagno, J. Chem. Phys. 87, 4202 (1983); D. Cruikshank, R. Brown, R. Clark, in Ices in the Solar System, J. Klinger et al., Eds. (Reidel, Dordrecht, The Netherlands, 1985), pp. 817-827; R. G. Prinn and B. Fegley Jr., in Origin and Evolution of Planetary and Satellite Atmospheres, S. K. Atreya et al., Eds. (Univ. of Arizona Press, Tucson, AZ, 1989), pp. 78-136; J. Lunine and D. Stevenson, Astrophys. J. Suppl. 58, 493 (1985).
6. E. Sloan, Clathrate Hydrates of Natural Gases (Dekker, New York, 1990).
7. K. Kvenvolden, Chem. Geol. 71, 41 (1988).
8. 4 by a factor of 165 with respect to standard temperature and pressure gas and as little as 10% of the recovered energy is required for dissociation, hydrate reservoirs are considered a substantial future energy resource; the total amount of gas in this solid form may surpass the energy content of the total fossil fuel reserves by as much as a factor of 2 [(2, 3); G. Claypool and I. Kaplan, in Natural Gases in Marine Sediments, I. Kaplan, Ed. (Plenum, New York, 1974), pp. 99-139].
9. L. Stern, S. Kirby, W. Durham, Lunar Planet. Sci. Conf. XXVII (abstr.), p. 1271 (1996); W. Durham, S. Kirby, L Stern, in Solar System lces, B. Schmitt, Ed., in press.
10. L. Stern, S. Kirby, W. Durham, Lunar Planet. Sci. Conf. XXVII (abstr.), p. 1271 (1996); W. Durham, S. Kirby, L Stern, in Solar System lces, B. Schmitt, Ed., in press.
11. R. Barrer and D. Ruzicka, Trans. Faraday Soc. 58, 2253 (1962); R. Barrer and A. Edge, Proc. R. Soc. London Ser. A 300, 1 (1967); B. Falabella and M. Vanpee, Ind. Eng. Chem. Fundam. 13, 228 (1974); K. Aoyogi, K. Song, R. Kobayashi, E. Sloan, P. Dharmawardhana, Gas Processors Assoc. Res. Rep. No. 45 (Tulsa, OK, 1980); see (2) for review of fabrication techniques.
12. R. Barrer and D. Ruzicka, Trans. Faraday Soc. 58, 2253 (1962); R. Barrer and A. Edge, Proc. R. Soc. London Ser. A 300, 1 (1967); B. Falabella and M. Vanpee, Ind. Eng. Chem. Fundam. 13, 228 (1974); K. Aoyogi, K. Song, R. Kobayashi, E. Sloan, P. Dharmawardhana, Gas Processors Assoc. Res. Rep. No. 45 (Tulsa, OK, 1980); see (2) for review of fabrication techniques.
13. R. Barrer and D. Ruzicka, Trans. Faraday Soc. 58, 2253 (1962); R. Barrer and A. Edge, Proc. R. Soc. London Ser. A 300, 1 (1967); B. Falabella and M. Vanpee, Ind. Eng. Chem. Fundam. 13, 228 (1974); K. Aoyogi, K. Song, R. Kobayashi, E. Sloan, P. Dharmawardhana, Gas Processors Assoc. Res. Rep. No. 45 (Tulsa, OK, 1980); see (2) for review of fabrication techniques.
14. R. Barrer and D. Ruzicka, Trans. Faraday Soc. 58, 2253 (1962); R. Barrer and A. Edge, Proc. R. Soc. London Ser. A 300, 1 (1967); B. Falabella and M. Vanpee, Ind. Eng. Chem. Fundam. 13, 228 (1974); K. Aoyogi, K. Song, R. Kobayashi, E. Sloan, P. Dharmawardhana, Gas Processors Assoc. Res. Rep. No. 45 (Tulsa, OK, 1980); see (2) for review of fabrication techniques.
15. 2 until mechanical testing.
16. Hwang et al. (9) note that a high-P driving force is required for measurable clathrate formation rates, and their experiments verified that for clathrate formation from melting ice, higher gas P yielded higher formation rates. Makogon (20) had earlier suggested that as hydrate formation is an interfacial process, high concentrations of hydrate-forming species are required at the interface.
17. M. Hwang, D. Wright, A. Kapur, G. Holder, J. Inclusion Phenom. 8, 103 (1990).
18. 4 uptake. Samples from previous experiments taken to 273 to 280 K for 4 to 6 hours showed only partial reaction, with roughly equal fractions of clathrate and ice in their XRD patterns.
19. - chiometry and is consistent with (12). ΔP, measured during synthesis is only a 6.4% drop from the starting P, due to the large volume of the gas reservoir that is open to the system throughout synthesis.
20. Gas hydrate number n vaies with P: increasing P maximizes guest-molecule site occupancy. At sample synthesis conditions (≃28 MPa) the hydrate number n for methane clathrate should be 6.1 ± 0.1, and at 100 MPa n = 5.85 ±0.05 [S. Saito, D. Marshall, R. Kobayashi, Am. Inst. Chem. Eng. J. 10, 734 (1964); also see (13), p. 54.]
21. Handbook of Gas Hydrate Properties and Occurrence (U.S. Dept. of Energy Publication DOE/MC/ 19239-1546, 1983).
22. 2O liquid. After refreezing, these samples showed obvious melt textures; they displayed an outer cylindrical ring of clear, nonporous ice, with cloudy, gascharged ice concentrated in the center of the sample as the freezing front progressed from the outside to the interior. Partially dissociated samples also showed large amounts of ice in their XRD patterns. Additional evidence of melting was provided by the loosely fitting top disk (Fig. 2). In samples that leaked P, the disk was found to drop to a midpoint in the molding tube as residual seed ice melted. In fully reacted samples, however, the disk remained at the top of the sample.
23. 2, He, and Ne are too small to form clathrates at our test conditions; we chose Ne because it is the largest of these and hence the easiest to seal.
24. 2O ice is -6.01 kJ/mol, or -36.07 kJ/6.1 mol for comparison with the clathrate-forming reaction.
25. 2O ice is -6.01 kJ/mol, or -36.07 kJ/6.1 mol for comparison with the clathrate-forming reaction.
26. 2O is negligible. The magnitude of the P drop was verified independently from the CH4 equation of state.
27. P. Villard, C. R. Assoc. Fr. Avanc. Sci. 106, 1602 (1888). See also (2,9).
28. 2O than from ice because the heat of formation is partially absorbed by the melting ice.
29. Conceptual models of hydrate growth by diffusion have been discussed previously [Y. Makogon, Hydrates of Natural Gases, W. H. Cielewicz, Transl. (PennWell, Tulsa, OK, 1981 )] and later by Hwang et al. (9).
30. 2O liquidus. It remains possible, however, that such a microlayer actually formed but was at or below our XRD detection levels.
31. 2O liquidus. It remains possible, however, that such a microlayer actually formed but was at or below our XRD detection levels.
32. 2O liquidus. It remains possible, however, that such a microlayer actually formed but was at or below our XRD detection levels.
33. 2O phase is difficult to initiate because of the law solubility of the gas in the bulk liquid (2, 9).
34. Several investigators have reported demonstrating the phenomenon of superheating ice with respect to the vapor phase [E. Roedder, Science 155, 1413 (1967); G. Schubert and R. E. Lingenfelter, ibid. 168, 469 (1970); see also discussion by B. Kamb, ibid. 169, 1343 (1970)] or with respect to the liquid phase, M. Kåss and S. Magun [Z. Kristallogr. 116, 354 (1961)]. See also C. Knight and A. DeVries, Science 245, 505 (1989).
35. Several investigators have reported demonstrating the phenomenon of superheating ice with respect to the vapor phase [E. Roedder, Science 155, 1413 (1967); G. Schubert and R. E. Lingenfelter, ibid. 168, 469 (1970); see also discussion by B. Kamb, ibid. 169, 1343 (1970)] or with respect to the liquid phase, M. Kåss and S. Magun [Z. Kristallogr. 116, 354 (1961)]. See also C. Knight and A. DeVries, Science 245, 505 (1989).
36. Several investigators have reported demonstrating the phenomenon of superheating ice with respect to the vapor phase [E. Roedder, Science 155, 1413 (1967); G. Schubert and R. E. Lingenfelter, ibid. 168, 469 (1970); see also discussion by B. Kamb, ibid. 169, 1343 (1970)] or with respect to the liquid phase, M. Kåss and S. Magun [Z. Kristallogr. 116, 354 (1961)]. See also C. Knight and A. DeVries, Science 245, 505 (1989).
37. Several investigators have reported demonstrating the phenomenon of superheating ice with respect to the vapor phase [E. Roedder, Science 155, 1413 (1967); G. Schubert and R. E. Lingenfelter, ibid. 168, 469 (1970); see also discussion by B. Kamb, ibid. 169, 1343 (1970)] or with respect to the liquid phase, M. Kåss and S. Magun [Z. Kristallogr. 116, 354 (1961)]. See also C. Knight and A. DeVries, Science 245, 505 (1989).
38. Several investigators have reported demonstrating the phenomenon of superheating ice with respect to the vapor phase [E. Roedder, Science 155, 1413 (1967); G. Schubert and R. E. Lingenfelter, ibid. 168, 469 (1970); see also discussion by B. Kamb, ibid. 169, 1343 (1970)] or with respect to the liquid phase, M. Kåss and S. Magun [Z. Kristallogr. 116, 354 (1961)]. See also C. Knight and A. DeVries, Science 245, 505 (1989).
39. H. Heard, W. Durham, C. Boro, S. Kirby, in The Brittle-Ductile Transition in Rocks, Geophysical Monograph 56, A. Duba et al., Eds. (American Geophysical Union, Washington, DC, 1990), pp. 225-228. In our experiments, piston force and displacement rate were recorded, corrected for instantaneous sample area and length changes, and converted to differential stress (σ), axial shortening strain (ε), and strain rate (ε).
40. W. Durham, S. Kirby, L. Stern, J. Geophys. Res. 97, E12, 20883 (1992); S. Kirby, W. Durham, M. Beeman, H. Heard, M. Daley, J. Phys. 48 (suppl.), 227 (1987).
41. W. Durham, S. Kirby, L. Stern, J. Geophys. Res. 97, E12, 20883 (1992); S. Kirby, W. Durham, M. Beeman, H. Heard, M. Daley, J. Phys. 48 (suppl.), 227 (1987).
42. During hydrostatic compaction, confining P was slowly "stepped" up to 100 MPa in increments of about 20 MPa. After each P step, the piston was advanced to touch and square the bottom of the sample, then advanced just sufficiently to lightly compress the sample in order to compact it with minimal plastic deformation. Six of the samples were compacted by means of an internal vent line to eliminate the pore-space gas, and two of the samples were compacted without the venting capability. The two nonvented samples (281 and 282; Table 1) showed equally large fractions of ice in their postdeformation x-ray patterns as the vented samples.
43. Indium jacket replicas of deformed sample surfaces showed evidence of heterogeneous ice precipitation. Areas with exsolved ice appear on jackets of all deformed samples as discrete patches with noticeably finer grain size than the surrounding clathrate.
44. We thank B. Kamb, J. Kargel, K. Kvenvolden, and W. McKinnon for critically reviewing the manuscript and for helpful discussions. This work was supported under NASA order W-18,927 and was performed in part under the auspices of the U.S. Department of Energy by the Lawrence Livermore National Laboratory under contract W-7405-ENG-48.