SOLVENT POLARITY PARAMETERS OF SUPERCRITICAL CARBON-DIOXIDE AS MEASURED BY INFRARED-SPECTROSCOPY

被引:55
作者
IKUSHIMA, Y
SAITO, N
ARAI, M
ARAI, K
机构
[1] TOHOKU UNIV, INST CHEM REACT SCI, AOBA KU, SENDAI, MIYAGI 980, JAPAN
[2] TOHOKU UNIV, DEPT BIOCHEM & CHEM ENGN, SENDAI, MIYAGI 980, JAPAN
关键词
D O I
10.1246/bcsj.64.2224
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The solvent polarity parameters of supercritical carbon dioxide were determined as a function of the temperature and pressure within the ranges 318-353 K and 5.85-28.5 MPa. An infrared (IR) spectroscopic technique has been employed to determine the values of pi* dipolarity/polarizability and the Lewis basicity parameter B(MeOD) by measuring the transitions in the IR absorption wavelength of functional groups (such as C = O and O-H...BA, where BA is a hydrogen-bond acceptor), in supercritical carbon dioxide. Ultraviolet/visible (UV/vis) spectroscopy was used to determine the value of the Kamlet-Taft's solvatochromic acidity parameter, alpha. The B(MeOD)-value was enhanced with density, but was very small at the temperatures and pressures examined, almost the same as that for hexane. The alpha-value tended to be dependent on density at lower pressures, but was remarkably smaller compared with those for alcohols. The pi*-value significantly increased with an increase in the density, becoming more negative at higher temperatures above 10 MPa. Furthermore, the E(T)(30)-value was estimated by using the determined pi*-value. A reliable E(T)(30)-value for supercritical carbon dioxide has been obtained.
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页码:2224 / 2229
页数:6
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