SOLUTE SOLVENT INTERACTION IN NONPOLAR SUPERCRITICAL FLUID - A CLUSTERING MODEL AND SIZE DISTRIBUTION

被引:96
作者
MORITA, A [1 ]
KAJIMOTO, O [1 ]
机构
[1] UNIV TOKYO, COLL ARTS & SCI, DEPT PURE & APPL SCI, TOKYO 153, JAPAN
关键词
D O I
10.1021/j100379a048
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Solubility and solvatochromic shift of 4-(dimethylamino)benzonitrile (DMABN) in supercritical ethane were measured. The bathochromic shifts observed at various densities were much larger than expected from Onsager's reaction field theory. The discrepancy can be attributed to the solvent aggregation around DMABN even in nonpolar ethane. At low densities, the solvatochromic shift was found to be directly proportional to the fugacity of the solvent fluid. This relation was well rationalized by considering the size distribution of the cluster on a statistical mechanical basis using a grand canonical ensemble. With the help of intermolecular potential between ethane and DMABN, the cluster size distribution in low-density supercritical ethane was derived and the bathochromic shift per one solvent molecule was estimated. © 1990 American Chemical Society.
引用
收藏
页码:6420 / 6425
页数:6
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