Citation: 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 Physico-Chimica Sinica, ;2016, 32(11): 2671-2677. doi: 10.3866/PKU.WHXB201608122 shu

A Comparative Study on theNMR Relaxation of Methanol in Sub-and Super-Critical Mixtures of CO₂ and Methanol

College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. China

Received Date: 14 July 2016
Revised Date: 3 August 2016

Fund Project: 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).

¹H NMR longitudinal relaxation times (T_1,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/T_1,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.
- CO₂-methanol mixture,
- Dipole-dipole interaction mechanism,
- Subcritical and supercritical fluid,
- Spin-lattice relaxation rate,
- Spin-rotation mechanism
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A Comparative Study on theNMR Relaxation of Methanol in Sub-and Super-Critical Mixtures of CO2 and Methanol

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通讯作者: 陈斌, bchen63@163.com

A Comparative Study on theNMR Relaxation of Methanol in Sub-and Super-Critical Mixtures of CO₂ and Methanol