氮气、氧气和空气水合物的合成及其拉曼光谱特征

现代地质 ›› 2008, Vol. 22 ›› Issue (3): 480-484.

氮气、氧气和空气水合物的合成及其拉曼光谱特征

刘昌岭¹,业渝光¹,卢海龙²,Ripmesster A John²

1青岛海洋地质研究所, 山东青岛 266071；
2Steacie Institute for Molecular Sciences, National Research Council Canada, Ontario Ottawa K1A0R6

收稿日期:2007-12-29 修回日期:2008-04-28 出版日期:2008-03-20 发布日期:2008-03-20
作者简介:刘昌岭，男，研究员,博士，1966年出生，海洋地质学专业,主要从事天然气水合物模拟实验技术研究。
基金资助:
中国地质调查局国家天然气水合物专项课题（GZH200200202）

Formation and Raman Spectroscopic Characteristics of Nitrogen,Oxygen and Air Hydrates

LIU Chang-ling¹, YE Yu-guang¹, LU Hai-long², Ripmesster A John²

1 Qingdao Institute of Marine Geology, Qingdao, Shandong 266071, China;
2 Steacie Institute for Molecular Sciences, National Research Council Canada, Ontario Ottawa K1A0R6, Canada

Received:2007-12-29 Revised:2008-04-28 Online:2008-03-20 Published:2008-03-20

摘要/Abstract

摘要：

在-20 ℃和不同的压力下，在实验室内分别合成了氮气水合物（16 MPa）、氧气水合物（13 MPa）和空气水合物（15 MPa）并对其N—N和O—O键伸缩振动的拉曼光谱特征进行了研究。结果表明，人工合成的水合物中的N—N和O—O键的拉曼位移与天然的空气水合物中的数据十分接近。在氮气水合物和空气水合物中，N—N键的拉曼峰值均为2 322.4 cm^-1；O—O键的拉曼峰值在氧气水合物和空气水合物保持一致，均为1 547.8 cm^-1。空气水合物分解的拉曼谱图表明，它不是氮气水合物和氧气水合物组成的混合物，而是由氮分子和氧分子共同生成的单一水合物，氮分子和氧分子同时进入水合物的大笼和小笼中。与空气中的氮、氧比例相比，水合物中氧分子明显富集，氮分子和氧分子的比例为2.4∶1。


关键词: 氮气水合物, 氧气水合物, 空气水合物, 激光拉曼光谱

Abstract:

The nitrogen hydrate, oxygen hydrate and air hydrate samples were synthesized at 16 MPa, 13 MPa and 15 MPa, respectively, at-20 ℃ in laboratory. The Laser Raman spectroscopy was used to investigate the characteristics of N—N and O—O stretching vibration in these samples. The results show that Raman shifts of N—N and O—O in the synthesized samples are very similar to those in natural samples. The Raman peak of N₂ is observed at 2,322.4 cm^-1 both in nitrogen hydrate and in air hydrate, while the Raman peak of O₂ at 1，547.8 cm^-1 in oxygen hydrate and air hydrate. The Raman spectroscopic observations on air hydrate dissociation suggest that air hydrate is a unit clathrate with N₂ and O₂ as guest molecules, rather than mixture of pure nitrogen hydrate and oxygen hydrate. The N₂ and O₂ molecules seem to occupy both the large and small cages of air hydrate together. Compared with the N/O ratio in air, O₂molecule is significantly enriched in the synthesized air hydrate with N₂/O₂ ratio of 2.4：1.

Key words: nitrogen hydrate, oxygen hydrate, air hydrate, Laser Raman spectroscopy

中图分类号:

O621
P73

刘昌岭,业渝光,卢海龙,Ripmesster A John. 氮气、氧气和空气水合物的合成及其拉曼光谱特征[J]. 现代地质, 2008, 22(3): 480-484.

LIU Chang-ling, YE Yu-guang, LU Hai-long, Ripmesster A John. Formation and Raman Spectroscopic Characteristics of Nitrogen,Oxygen and Air Hydrates[J]. Geoscience, 2008, 22(3): 480-484.

参考文献

［1］Sloan E D. Clathrate Hydrates of Natural Gases [M]. New York: Marcel Dekker Incorporation, 1998.

［2］Davidson D W, Handa Y P, Ratcliffe C I, et al. The ability of small molecules to form clathrate hydrates of structure II [J]. Nature, 1984, 311(8):142-143.

［3］Davidson D W, Handa Y P, Ratcliffe C I, et al. Crystallographic studies of clathrate hydrates[J]. Molecular Crystals and Liquid Crystals, 1986, 141(1): 141-149.

［4］Shoji H, Langway Jr C C. Air hydrate inclusions in fresh ice core[J]. Nature, 1982, 298(7): 548-549. 

［5］Champagnon B, Pamczer G, Chazallon B, et al. Nitrogen and oxygen guest molecules in clathrate hydrates:

Different sites revealed by Raman spectroscopy [J]. Journal of Raman Spectroscopy, 1997, 28(9):711-715.

［6］Ikeda T, Fukazawa H, Mae S, et al. Crystal orientation dependence of Raman spectra of natural air hydrate single crystal [J]. Journal of

Physical Chemical B, 1997, 101(32):6180-6183.

［7］雷怀彦, 官宝聪, 刘建辉，等. 笼状水合物拉曼光谱特征与结构水合数的耦合关系 [J]. 现代地质, 2005, 19(1):83-88.

［8］吕万军, Chou I M, Burruss R C, 等. 拉曼光谱原位观测水合物形成后的饱和甲烷浓度[J]. 地球化学, 2005,34(2):187-192.

［9］Pauer F, Kipfstuhl J, Kuhs W F. Raman spectroscopic study on the nitrogen/oxygen ratio in natural ice clathrates in the GRIP ice core[J]. Geophysical Research Letters, 1995, 22(8):969-971.

［10］Pauer F, Kipfstuhl J, Kuhs W F. Raman spectroscopic study on the spatial distribution of nitrogen and oxygen in

natural ice clathrates and their decomposition to air bubbles [J]. Geophysical Research Letters, 1996, 23(2): 177-180.

［11］Pauer F, Kipfstuhl J, Kuhs W F. Raman spectroscopic and statistical studies on natural clathrates from the Greenland

Ice Core Project ice core, and neutron diffraction studies on synthetic nitrogen clathrates[J]. Journal of Geophysical Research, 1997,102,(c12)：26519 -26526.

［12］Hondoh T, Anzai H, Goto A, et al. The crystallographic structure of the natural airhydrate in Greenland Dye3 deep ice core [J]. Journal of Inclusion Phenomena and Molecular Recognition Chemistry, 1990, 8(1-2):17-24.

［13］Van Cleeff A, Diepen A M. Gas hydrates of nitrogen and oxygen [J]. Recueil des Travaux Chimiques des PaysBas, 1960,79(1-2):582-586.［14］Ikeda T, Fukazawa H, Mae S, et al. Extreme fractionation of gases caused by formation of clathrate hydrates in Vostok Antarctic ice[J].Gas Hydrate of Nitrogen and Oxygen Ⅱ,1965,84:1085-1093.

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