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Double occupancy of large cavity of diethylamin+methane sH hydrate at low pressures

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Abstract

New data on the composition of hexagonal structure III (sH) diethylamine+methane double hydrate are presented. The hydrate was synthesized from methane and aqueous solutions of diethylamine with the molar ratio of diethylamine to water 1:17, 1:20, 1:30, 1:40, and 1:50. In the first case, pure sH hydrate was obtained; in other cases, the mixtures of sH hydrates and methane hydrate were formed. The content of each of the hydrates in mixture as well as the total content of methane in these samples were determined experimentally. The compositions of the formed sH hydrates in all samples were calculated on the basis of these data. It turned out that in all samples, substantial part of large cavities of sH hydrate framework was filled with two diethylamine molecules. To the best of our knowledge, this is the first example of double occupancy of hydrate cavities for gas hydrate synthesized at comparatively low (100 bar) pressure. Multiple filling of the hydrate cavities by guest molecules was previously observed only at pressures above 1000 bar.

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References

  1. Sloan ED, Koh CA (2008) Clathrate hydrates of natural gases3rd edn. Boca Raton, London, New York

    Google Scholar 

  2. Manakov AY, Kosyakov VI, Solodovnikov SF (2017) Structural chemistry of clathrate hydrates and related compounds. Compr Supramol Chem II 7:161–206

    Google Scholar 

  3. Ripmeester JA, Ratcliffe CI, Tse JS, Powell BM (1987) A new clathrate hydrate structure. Nature 325:135–136

    Article  CAS  Google Scholar 

  4. Takeya S, Udachin KA, Moudrakovski IL, Susilo R, Ripmeester JA (2010) Direct space methods for powder X-ray diffraction for guest−host materials: applications to cage occupancies and guest distributions in clathrate hydrates. J Am Chem Soc 132(2):524–531

    Article  CAS  Google Scholar 

  5. Sinehbaghizadeh S, Javanmardi J, Roosta A, Mohammadi AH (2019) Estimation of the dissociation conditions and storage capacities of various sH clathrate hydrate systems using effective deterministic frameworks. Fuel 247:272–286

    Article  CAS  Google Scholar 

  6. Kim E, Lee S, Lee JD, Seo Y (2015) Influences of large molecular alcohols on gas hydrates and their potential role in gas storage and CO2 sequestration. Chem Eng J 267:117–123

    Article  CAS  Google Scholar 

  7. Kim E, Seo Y (2019) A novel discovery of a gaseous sH clathrate hydrate former. Chem Eng J 359:775–778

    Article  CAS  Google Scholar 

  8. Kuhs WF, Chazallon B, Radaelli PG, Pauer F (1997) Cage occupancy and compressibility of deuterated N2-hydrate by neutron diffraction. J Incl Phenom 29:65–77

    Article  CAS  Google Scholar 

  9. Chazallon B, Kuhs WF (2002) In situ structural properties of N2-, O2-, and air-clathrates by neutron diffraction. J Chem Phys 117(1):308–320

    Article  CAS  Google Scholar 

  10. Manakov AY, Voronin VI, Kurnosov AV, Teplych AE, Komarov VY, Dyadin YA (2004) Structural investigations of argon hydrates at pressures up to 10 kbar. J Incl Phenom 48:11–18

    Article  CAS  Google Scholar 

  11. Ogienko AG, Kurnosov AV, Manakov AY, Larionov EG, Ancharov AI, Sheromov MA, Nesterov AN (2006) Gas hydrates of argon and methane synthesized at high pressures: composition, thermal expansion, and self-preservation. J Phys Chem B 110:2840–2846

    Article  CAS  Google Scholar 

  12. Manakov AY, Ogienko AG, Tkacz M, Lipkowski J, Stoporev AS, Kutaev NV (2011) High-pressure gas hydrates of argon: compositions and equation of state. J Phys Chem B 115:9564–9569

    Article  CAS  Google Scholar 

  13. Loveday JS, Nelmes RJ, Guthrie M (2001) High-pressure transitions in methane hydrate. Chem Phys Lett 350:459–465

    Article  CAS  Google Scholar 

  14. Ogienko AG, Tkacz M, Manakov AY, Lipkowski J (2007) First determination of volume changes and enthalpies of the high-pressure decomposition reaction of the structure H methane hydrate to the cubic structure I methane hydrate and fluid methane. J Phys Chem B 111:12795–12798

    Article  CAS  Google Scholar 

  15. Dyadin YA, Larionov EG, Manakov AY, Zhurko FV, Aladko EY, Mikina TV, Komarov VY (1999) Clathrate hydrates of hydrogen and neon. Mendeleev Commun 9(5):209–210

    Article  Google Scholar 

  16. Mao WL, Mao HK, Goncharov AF, Struzhkin VV, Guo Q, Hu J, Zhao Y (2002) Hydrogen clusters in clathrate hydrate. Science 297(5590):2247–2249

    Article  CAS  Google Scholar 

  17. Lu H, Wang J, Liu C, Ratcliffe CI, Becker U, Kumar R, Ripmeester J (2012) Multiple H2 occupancy of cages of clathrate hydrate under mild conditions. J Am Chem Soc 134(22):9160–9162

    Article  CAS  Google Scholar 

  18. Shin W, Park S, Lee JW, Seo Y, Koh DY, Seol J, Lee H (2012) Structure transition from semi- to true clathrate hydrates induced by CH4 enclathration. J Phys Chem C 116(31):16352–16357

    Article  CAS  Google Scholar 

  19. Manakov AY, Sizikov AA (2014) Double gas hydrate of isopropanol and methane. Fluid Phase Equilib 371:75–81

    Article  Google Scholar 

  20. Sizikov AA, Manakov AY, Aladko EY (2016) Pressure dependence of gas hydrate formation in triple systems water-2-Propanol-methane and water-2-Propanol-hydrogen. Fluid Phase Equilib 425:351–357

    Article  CAS  Google Scholar 

  21. Roisnel T, Rodríquez-Carvajal J (2001) WinPLOTR: a Windows tool for powder diffraction patterns analysis. Material Science Forum, Proc. Europian Powder Diffraction Conference (EPDIC7) 378-381:118-123

  22. Alavi S, Udachin K, Ripmeester JA (2009) Effect of guest-host hydrogen bonding on the structures and properties of clathrate hydrates. Chem Eur J 16(3):1017–1025

    Article  Google Scholar 

  23. Moon S, Park SO, Ahn YH, Kim H, Shin E, Hong S, Park Y (2018) Distinct hydrophobic–hydrophilic dual interactions occurring in the clathrate hydrates of 3,3-dimethyl-1-butanol with help gases. Chem Eng J 348:583–591

    Article  CAS  Google Scholar 

  24. Dobrzycki Ł, Pruszkowska K, Boese R, Cyrański MK (2016) Hydrates of cyclobutylamine: modifications of gas clathrate types sI and sH. Cryst Growth Des 16(5):2717–2725

    Article  CAS  Google Scholar 

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We thank the Ministry of Science and Higher Education of the Russian Federation for the financial support.

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Correspondence to Andrey Y. Manakov.

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Chashchin, D.D., Manakov, A.Y. & Yunoshev, A.S. Double occupancy of large cavity of diethylamin+methane sH hydrate at low pressures. Struct Chem 31, 1113–1118 (2020). https://doi.org/10.1007/s11224-020-01492-1

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