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

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1990年 / 94卷 / 16期

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

页码：6420 / 6425

页数：6

共 32 条

[1] REFRACTIVE INDEXES OF ETHANE, CARBON-DIOXIDE, AND ISOBUTANE [J].

BESSERER, GJ ;

ROBINSON, DB .

JOURNAL OF CHEMICAL AND ENGINEERING DATA, 1973, 18 (02) :137-140

[2]

Canjar LN, 1967, THERMODYNAMIC PROPER

[3] THE DYNAMICS OF POLAR SOLVATION [J].

CASTNER, EW ;

BAGCHI, B ;

MARONCELLI, M ;

WEBB, SP ;

RUGGIERO, AJ ;

FLEMING, GR .

BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1988, 92 (03) :363-372

[4]

ECKART CA, 1986, J PHYS CHEM-US, V90, P2738

[5] PHYSICOCHEMICAL PROPERTIES OF SUPERCRITICAL SOLVENTS [J].

FRANCK, EU .

BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1984, 88 (09) :820-825

[6] THE NATURE OF SIMPLE PHOTODISSOCIATION REACTIONS IN LIQUIDS ON ULTRAFAST TIME SCALES [J].

HARRIS, AL ;

BROWN, JK ;

HARRIS, CB .

ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 1988, 39 :341-366

[7]

Hirschfelder JO, 1954, MOL THEORY GASES LIQ

[8] MOLECULAR THERMODYNAMICS OF FLUID MIXTURES CONTAINING MOLECULES DIFFERING IN SIZE AND POTENTIAL-ENERGY [J].

HU, Y ;

LUDECKE, D ;

PRAUSNITZ, J .

FLUID PHASE EQUILIBRIA, 1984, 17 (02) :217-241

[9] THE MOLECULAR-BASIS FOR LOCAL COMPOSITIONS IN LIQUID-MIXTURE MODELS [J].

HU, Y ;

AZEVEDO, EG ;

PRAUSNITZ, JM .

FLUID PHASE EQUILIBRIA, 1983, 13 (OCT) :351-360

[10] LOCAL COMPOSITION MODELS FOR FLUID MIXTURES OVER A WIDE DENSITY RANGE [J].

JOHNSTON, KP ;

KIM, SW ;

WONG, JM .

FLUID PHASE EQUILIBRIA, 1987, 38 (1-2) :39-62

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