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ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 2016,Vol.32>> Issue(11)>> 2671-2677     doi: 10.3866/PKU.WHXB201608122         中文摘要
A Comparative Study on theNMR Relaxation of Methanol in Sub-and Super-Critical Mixtures of CO2 and Methanol
CHENG Xiao-Meng, LI Yu, CHEN Zong, LI Hong-Ping, ZHENG Xiao-Fang
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. China
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1H NMR longitudinal relaxation times (T1,exp of the hydroxyl and methyl group) of methanol in supercritical and subcritical gas-like and liquid-like CO2+methanol mixtures were obtained as a function of pressure up to 25 MPa and at 293.15 and 308.15 K, respectively. This study was designed to investigate the mechanism of the spin-lattice relaxation (SLR) time T1 in different phase regions of CO2+methanol as homogenous gas-like, and liquid-like mixtures, and the influence of pressure, temperature, and composition on the relaxation rate was examined. Moreover, the density dependent isotherms of the SLR rates 1/T1,exp were comparatively studied between gas-like and liquid-like binary mixtures. There exists an obvious phase dependent SLR mechanism within the temperature and pressure range carried out herein, that is, the SLR process is dominated by the dipole-dipole (DD) interaction mechanism for both liquid-like mixture and methanol, whereas by the spin-rotation (SR) mechanism for gas-like mixture. Measurement of nuclear magnetic relaxation times can offer micro-dynamic and micro-structural information and are very useful for the study of fluids of strongly interacting molecules. Mutual influence of electric dipoles as well as hydrogen bonds helps determine the structure of the fluid and its molecular dynamics. The present work increases our knowledge of molecular dynamics of alcohols in sub-and supercritical CO2.



Keywords: CO2-methanol mixture   Dipole-dipole interaction mechanism   Subcritical and supercritical fluid   Spin-lattice relaxation rate   Spin-rotation mechanism  
Received: 2016-07-14 Accepted: 2016-08-03 Publication Date (Web): 2016-08-12
Corresponding Authors: LI Hong-Ping Email: lihongping@zzu.edu.cn

Fund: The project was supported by the National Natural Science Foundation of China (21543009, 21073167, J1210060), and Innovative Research Grant for Undergraduate Students of National/Zhengzhou University, China (201410459047, 201510459046, 2016xjxm259).

Cite this article: CHENG Xiao-Meng, LI Yu, CHEN Zong, LI Hong-Ping, ZHENG Xiao-Fang. A Comparative Study on theNMR Relaxation of Methanol in Sub-and Super-Critical Mixtures of CO2 and Methanol[J]. Acta Phys. -Chim. Sin., 2016,32 (11): 2671-2677.    doi: 10.3866/PKU.WHXB201608122

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