Citation: Meng Qingguo, Liu Changling, Li Chengfeng, Hao Xiluo, Hu Gaowei, Sun Jianye, Wu Nengyou. Effect of Common Guest Molecules on the Lattice Constants of Clathrate Hydrates[J]. Acta Physico-Chimica Sinica, ;2020, 36(11): 191001. doi: 10.3866/PKU.WHXB201910010 shu

Effect of Common Guest Molecules on the Lattice Constants of Clathrate Hydrates

Meng Qingguo ^1,2,3 ,
Liu Changling ^1,2,, ,
Li Chengfeng ^1,2 ,
Hao Xiluo ^1,2 ,
Hu Gaowei ^1,2 ,
Sun Jianye ^1,2 ,
Wu Nengyou ^1,2

1.
The Key Laboratory of Gas Hydrate, Ministry of Natural Resources, Qingdao Institute of Marine Geology, Qingdao 266071, Shandong Province, P. R. China
2.
Laboratory for Marine Mineral Resources, Pilot National Laboratory for Marine Science and Technology, Qingdao 266237, Shandong Province, P. R. China
3.
Chinese Academy of Geological Sciences, Beijing 100037, P. R. China

Corresponding author: Liu Changling, qdliuchangling@163.com
Received Date: 8 October 2019
Revised Date: 6 December 2019
Accepted Date: 9 December 2019
Available Online: 11 December 2019
Fund Project: National Natural Science Foundation of China 41876051National Natural Science Foundation of China 41976074National Key R & D Program of China 2017YFC0307600National Natural Science Foundation of China 41302034the National Marine Geological Survey projects DD20190221The project was supported by the National Marine Geological Survey projects (DD20190221), National Natural Science Foundation of China (41876051, 41976074, 41302034) and National Key R & D Program of China (2017YFC0307600)

Natural gas hydrates are considered as ideal alternative energy resources for the future, and the relevant basic and applied research has become more attractive in recent years. The influence of guest molecules on the hydrate crystal lattice parameters is of great significances to the understanding of hydrate structural characteristics, hydrate formation/decomposition mechanisms, and phase stability behaviors. In this study, we test a series of artificial hydrate samples containing different guest molecules (e.g. methane, ethane, propane, iso-butane, carbon dioxide, tetrahydrofuran, methane + 2, 2-dimethylbutane, and methane + methyl cyclohexane) by a low-temperature powder X-ray diffraction (PXRD). Results show that PXRD effectively elucidates structural characteristics of the natural gas hydrate samples, including crystal lattice parameters and structure types. The relationships between guest molecule sizes and crystal lattice parameters reveal that different guest molecules have different controlling behaviors on the hydrate types and crystal lattice constants. First, a positive correlation between the lattice constants and the van der Waals diameters of homologous hydrocarbon gases was observed in the single-guest-component hydrates. Small hydrocarbon homologous gases, such as methane and ethane, tended to form sI hydrates, whereas relatively larger molecules, such as propane and iso-butane, generated sⅡ hydrates. The hydrate crystal lattice constants increased with increasing guest molecule size. The types of hydrates composed of oxygen-containing guest molecules (such as CO₂ and THF) were also controlled by the van der Waals diameters. However, no positive correlation between the lattice constants and the van der Waals diameters of guest molecules in hydrocarbon hydrates was observed for CO₂ hydrate and THF hydrate, probably due to the special interactions between the guest oxygen atoms and hydrate "cages". Furthermore, the influences of the macromolecules and auxiliary small molecules on the lengths of the different crystal axes of the sH hydrates showed inverse trends. Compared to the methane + 2, 2-dimethylbutane hydrate sample, the length of the a-axis direction of the methane + methyl cyclohexane hydrate sample was slightly smaller, whereas the length of the c-axis direction was slightly longer. The crystal a-axis length of the sH hydrate sample formed with nitrogen molecules was slightly longer, whereas the c-axis was shorter than that of the methane + 2, 2-dimethylbutane hydrate sample at the same temperature.
- Natural gas hydrate,
- PXRD,
- Structure characteristic,
- Lattice constant,
- Guest molecule size
1. [1]
  Li, J. F.; Ye, J. L.; Qin, X. W.; Qiu, H. J.; Wu, N. Y.; Lu, H. L.; Xie, W. W.; Lu, J. A.; Peng, F.; Xu, Z. Q.; et al. China Geology 2018, 1, 5. doi: 10.31035/cg2018003 doi: 10.31035/cg2018003
2. [2]
  Meng, Q. G. Research on the Multi-Component Gas Hydrates: Structure Characteristics, Formation and Dissociation Process. Ph.D. Dissertation, Chinese Academy of Geological Sciences, Beijing, 2019.
3. [3]
  Liu, C. L.; Meng, Q. G. Gas Hydrates Experiment and Testing Technologies; Science Press: Beijing, 2016.
4. [4]
  Chen, H. L.; Wei, C. F.; Tian, H. H.; Wei, H. Z. Acta Phys. -Chim. Sin. 2017, 33, 1599. doi: 10.3866/PKU.WHXB201704194
5. [5]
  Sloan, E. D. Nature 2003, 426, 353. doi: 10.1038/nature02135 doi: 10.1038/nature02135
6. [6]
  Liu, C. L.; Meng, Q. G. Rock & Mineral Anal. 2014, 33, 468. doi: 10.3969/j.issn.0254-5357.2014.04.003
7. [7]
  Lu, H.; Seo, Y.; Lee, J.; Moudrakovski, I.; Ripmeester, J. A.; Chapman, N. R.; Coffin, R. B.; Gardner, G.; Pohlman, J. Nature 2007, 445, 303. doi: 10.1038/nature05463 doi: 10.1038/nature05463
8. [8]
  Liu, C. L.; Meng, Q. G.; He, X. L.; Li, C. F.; Ye, Y. G.; Zhang, G. X.; Liang, J. Q. Mar. Pet. Geol. 2015, 61, 14. doi: 10.1016/j.marpetgeo.2014.11.006 doi: 10.1016/j.marpetgeo.2014.11.006
9. [9]
  Kida, M.; Jin, Y.; Yoneda, J.; Oshima, M.; Kato, A.; Konno, Y.; Nagao, J.; Tenma, N. Mar. Pet. Geol. 2019, 108, 471. doi: 10.1016/j.marpetgeo.2018.10.012 doi: 10.1016/j.marpetgeo.2018.10.012
10. [10]
  Liu, C. L.; Meng, Q. G.; Hu, G. W.; Li, C. F.; Sun, J. Y.; He, X. L.; Wu, N. Y.; Yang, S. X.; Liang, J. Q. Interpretation 2017, 5, SM13. doi: 10.1190/INT-2016-0211.1 doi: 10.1190/INT-2016-0211.1
11. [11]
  Tian, M.; Meng, Q. G.; Liu, C. L.; Li, C. F; Hu, G. W.; Feng, J.; Zhao, Q. S. Rock Miner. Anal. 2017, 36, 43. doi: 10.15898/j.enki.11-2131/td.201703160033
12. [12]
  Chen, Y. F.; Zhou, X. B.; Liang, D. Q.; Wu, N. Y. Spectrosc. Spect. Anal. 2019, 39, 2889. doi: 10.3964/j.issn.1000-0593(2019)09-2889-05
13. [13]
  Takeya, S.; Hori, A.; Uchida, T.; Ohmura, R. J. Phys. Chem. B 2006, 110, 12943. doi: 10.1021/jp060198v doi: 10.1021/jp060198v
14. [14]
  Takeya, S.; Nagaya, H.; Matsuyama, T.; Hondoh, T.; Lipenkov, V. Y. J. Phys. Chem. B 2000, 104, 668. doi: 10.1021/jp993344o doi: 10.1021/jp993344o
15. [15]
  Shin, K.; Moudrakovski, I. L.; Davari, M. D.; Alavi, S.; Ratcliffe, C. I.; Ripmeester, J. A. CrystEngComm 2014, 16, 7209. doi: 10.1039/c3ce41661e doi: 10.1039/c3ce41661e
16. [16]
  Kim, D. Y.; Lee, H. J. Am. Chem. Soc. 2005, 127, 9996. doi: 10.1021/ja0523183 doi: 10.1021/ja0523183
17. [17]
  Takeya, S.; Ripmeester, J. A. Angew. Chem. 2008, 120, 1296. doi: 10.1002/ange.200703718 doi: 10.1002/ange.200703718
18. [18]
  Takeya, S.; Uchida, T.; Kamata, Y.; Nagao, J.; Kida, M.; Minami, H.; Sakagami, H.; Hachikubo, A.; Takahashi, N.; Shoji, H.; et al. Angew. Chem. 2005, 117, 7088. doi: 10.1002/anie.200501845 doi: 10.1002/anie.200501845
19. [19]
  Tezuka, K.; Murayama, K.; Takeya, S.; Alavi, S.; Ohmura, R. J. Phys. Chem. C 2013, 117, 10473. doi: 10.1021/jp4005899 doi: 10.1021/jp4005899
20. [20]
  Daghash, S. M.; Servio, P.; Rey, A. D. Mol. Simul. 2019, 45, 1524. doi: 10.1080/08927022.2019.1660326 doi: 10.1080/08927022.2019.1660326
21. [21]
  Kondori, J.; Zendehboudi, S.; James, L. Chem. Eng. Res. Des. 2019, 149, 81. doi: 10.1016/j.cherd.2019.05.048 doi: 10.1016/j.cherd.2019.05.048
22. [22]
  Zhou, X. B.; Liu, C. J.; Luo, J. Q.; Liang, D. Q. CIESC J. 2019, 70, 1042. doi: 10.11949/j.issn.0438-1157.20180821
23. [23]
  Meng, Q. G.; Liu, C. L.; Ye, Y. G.; Li, C. F. Nat. Gas Ind. 2015, 35, 135. doi: 10.3787/j.issn.1000-0976.2015.03.022
24. [24]
  Udachin, K. A.; Ratcliffe, C. I.; Ripmeester, J. A. J. Supramol. Chem. 2002, 2, 405. doi: 10.1016/S1472-7862(03)00049-2 doi: 10.1016/S1472-7862(03)00049-2
25. [25]
  Stern, L. A.; Susan, C.; Stephen, H. K. J. Phys. Chem. B 2001, 105, 1756. doi: 10.1021/jp003061s doi: 10.1021/jp003061s
26. [26]
  Jin, Y.; Kida, M; Nagao, J. J. Phys. Chem. C 2013, 117, 23469. doi: 10.1021/jp403430z doi: 10.1021/jp403430z
27. [27]
  Lee, J. W.; Lu, H.; Moudrakovski, I. L.; Ratcliffe, C. I.; Ohmura, R.; Alavi, S.; Ripmeester, J. A. J. Phys. Chem. A 2011, 115, 1650. doi: 10.1021/jp1118184 doi: 10.1021/jp1118184
28. [28]
  Udachin, K. A.; Ratcliffe, C. I.; Ripmeester, J. A. J. Phys. Chem. B 2001, 105, 4200. doi: 10.1021/jp004389o doi: 10.1021/jp004389o
29. [29]
  Jin, Y.; Kida, M.; Nagao, J. J. Phys. Chem. C 2015, 119, 9069. doi: 10.1021/acs.jpcc.5b00529 doi: 10.1021/acs.jpcc.5b00529
1. [1]
  Hongwei Ma , Hui Li . Three Methods for Structure Determination from Powder Diffraction Data. University Chemistry, 2024, 39(3): 94-102. doi: 10.3866/PKU.DXHX202310035
2. [2]
  Wei Li , Guoqiang Feng , Ze Chang . Teaching Reform of X-ray Diffraction Using Synchrotron Radiation in Materials Chemistry. University Chemistry, 2024, 39(3): 29-35. doi: 10.3866/PKU.DXHX202308060
3. [3]
  Yuqiao Zhou , Weidi Cao , Shunxi Dong , Lili Lin , Xiaohua Liu . Study on the Teaching Reformation of Practical X-ray Crystallography. University Chemistry, 2024, 39(3): 23-28. doi: 10.3866/PKU.DXHX202303003
4. [4]
  Liang TANG , Jingfei NI , Kang XIAO , Xiangmei LIU . Synthesis and X-ray imaging application of lanthanide-organic complex-based scintillators. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1892-1902. doi: 10.11862/CJIC.20240139
5. [5]
  Jinghua Wang , Yanxin Yu , Yanbiao Ren , Yesheng Wang . Integration of Science and Education: Investigation of Tributyl Citrate Synthesis under the Promotion of Hydrate Molten Salts for Research and Innovation Training. University Chemistry, 2024, 39(11): 232-240. doi: 10.3866/PKU.DXHX202402057
6. [6]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060
7. [7]
  Pingping Zhu , Yongjun Xie , Yuanping Yi , Yu Huang , Qiang Zhou , Shiyan Xiao , Haiyang Yang , Pingsheng He . Excavation and Extraction of Ideological and Political Elements for the Virtual Simulation Experiments at Molecular Level: Taking the Project “the Simulation and Computation of Conformation, Morphology and Dimensions of Polymer Chains” as an Example. University Chemistry, 2024, 39(2): 83-88. doi: 10.3866/PKU.DXHX202309063
8. [8]
  Hongwei Ma , Fang Zhang , Hui Ai , Niu Zhang , Shaochun Peng , Hui Li . Integrated Crystallographic Teaching with X-ray,TEM and STM. University Chemistry, 2024, 39(3): 5-17. doi: 10.3866/PKU.DXHX202308107
9. [9]
  Xuanzhu Huo , Yixi Liu , Qiyu Wu , Zhiqiang Dong , Chanzi Ruan , Yanping Ren . Integrated Experiment of “Electrolytic Preparation of Cu₂O and Gasometric Determination of Avogadro’s Constant: Implementation, Results, and Discussion: A Micro-Experiment Recommended for Freshmen in Higher Education at Various Levels Across the Nation. University Chemistry, 2024, 39(3): 302-307. doi: 10.3866/PKU.DXHX202308095
10. [10]
  Wenliang Wang , Weina Wang , Sufan Wang , Tian Sheng , Tao Zhou , Nan Wei . “Schrödinger Equation – Approximate Models – Core Concepts – Simple Applications”: Constructing a Logical Framework and Knowledge Graph of Atom and Molecule Structures. University Chemistry, 2024, 39(8): 338-343. doi: 10.3866/PKU.DXHX202312084
11. [11]
  Haitang WANG , Yanni LING , Xiaqing MA , Yuxin CHEN , Rui ZHANG , Keyi WANG , Ying ZHANG , Wenmin WANG . Construction, crystal structures, and biological activities of two Ln^Ⅲ₃ complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1474-1482. doi: 10.11862/CJIC.20240188
12. [12]
  Ji Qi , Jianan Zhu , Yanxu Zhang , Jiahao Yang , Chunting Zhang . Visible Color Change of Copper (II) Complexes in Reversible SCSC Transformation: The Effect of Structure on Color. University Chemistry, 2024, 39(3): 43-57. doi: 10.3866/PKU.DXHX202307050
13. [13]
  Tianyun Chen , Ruilin Xiao , Xinsheng Gu , Yunyi Shao , Qiujun Lu . Synthesis, Crystal Structure, and Mechanoluminescence Properties of Lanthanide-Based Organometallic Complexes. University Chemistry, 2024, 39(5): 363-370. doi: 10.3866/PKU.DXHX202312017
14. [14]
  Shuying Zhu , Shuting Wu , Ou Zheng . Improvement and Expansion of the Experiment for Determining the Rate Constant of the Saponification Reaction of Ethyl Acetate. University Chemistry, 2024, 39(4): 107-113. doi: 10.3866/PKU.DXHX202310117
15. [15]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
16. [16]
  Jingjing QING , Fan HE , Zhihui LIU , Shuaipeng HOU , Ya LIU , Yifan JIANG , Mengting TAN , Lifang HE , Fuxing ZHANG , Xiaoming ZHU . Synthesis, structure, and anticancer activity of two complexes of dimethylglyoxime organotin. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1301-1308. doi: 10.11862/CJIC.20240003
17. [17]
  Feng Zheng , Ruxun Yuan , Xiaogang Wang . “Research-Oriented” Comprehensive Experimental Design in Polymer Chemistry: the Case of Polyimide Aerogels. University Chemistry, 2024, 39(10): 210-218. doi: 10.12461/PKU.DXHX202404027
18. [18]
  Xin MA , Ya SUN , Na SUN , Qian KANG , Jiajia ZHANG , Ruitao ZHU , Xiaoli GAO . A Tb₂ complex based on polydentate Schiff base: Crystal structure, fluorescence properties, and biological activity. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1347-1356. doi: 10.11862/CJIC.20230357
19. [19]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
20. [20]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(981)
HTML views(148)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142