MEDIUM EFFECTS IN THE ELECTROREDUCTION OF BENZOPHENONE IN APROTIC-SOLVENTS

被引：51

作者：

FAWCETT, WR

FEDURCO, M

机构：

[1] Department of Chemistry, University of California, Davis

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1993年 / 97卷 / 27期

关键词：

D O I：

10.1021/j100129a025

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：

The kinetics of electroreduction of benzophenone have been studied at a mercury ultramicroelectrode in seven aprotic solvents. In addition, the temperature dependence of the standard rate constant was determined in three solvents, and the effect of tetraalkylammonium cations on the kinetic parameters was assessed in acetonitrile. On the basis of an analysis of the solvent effects, it is shown that this fast electron-transfer reaction is adiabatic. A model for solvation of the activated complex based on three contiguous spheres corresponding to the two phenyl rings and the carbonyl group is described and used to assess the outer-sphere contribution to the Gibbs activation energy for electron transfer.

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页码：7075 / 7080

页数：6

相关论文

共 32 条

[1]

AREVALO MC, 1989, B ELECTROCHEM, V5, P786

[2] NEW EXPERIMENTAL-EVIDENCE CONCERNING THE MAGNITUDE OF THE ACTIVATION PARAMETERS FOR FAST HETEROGENEOUS ELECTRON-TRANSFER REACTIONS [J].

BARANSKI, AS ;

WINKLER, K ;

FAWCETT, WR .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1991, 313 (1-2) :367-375

[3] CLASSICAL SOLVENT DYNAMICS AND ELECTRON-TRANSFER .1. CONTINUUM THEORY [J].

CALEF, DF ;

WOLYNES, PG .

JOURNAL OF PHYSICAL CHEMISTRY, 1983, 87 (18) :3387-3400

[4] GLASSY-CARBON SURFACE EFFECTS ON THE ELECTROREDUCTION OF AROMATIC CARBONYL-COMPOUNDS .2. BENZOPHENONE [J].

CHANDRASEKARAN, M ;

NOEL, M ;

KRISHNAN, V .

COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, 1991, 56 (10) :2055-2066

[5] ON NEGATIVE FARADAIC ADMITTANCE IN REGION OF POLAROGRAPHIC MINIMUM OF IN(3) IN AQUEOUS NASCN SOLUTION [J].

DELEVIE, R ;

HUSOVSKY, AA .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1969, 22 (01) :29-&

[6] POLAROGRAPHY OF THIOKETONES [J].

ELOFSON, RM ;

GADALLAH, FF ;

GADALLAH, LA .

CANADIAN JOURNAL OF CHEMISTRY, 1969, 47 (21) :3979-&

[7] COMPARISON OF HETEROGENEOUS AND HOMOGENEOUS ELECTRON-TRANSFER RATES FOR SOME NITROALKANES AND DIKETONES [J].

EVANS, DH ;

GILICINSKI, AG .

JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (06) :2528-2533

[8] THE INHIBITING EFFECTS OF TETRAALKYLAMMONIUM CATIONS ON SIMPLE HETEROGENEOUS ELECTRON-TRANSFER REACTIONS IN POLAR APROTIC-SOLVENTS [J].

FAWCETT, WR ;

FEDURCO, M ;

OPALLO, M .

JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (24) :9959-9964

[9] APPLICATION OF THE MEAN SPHERICAL APPROXIMATION TO DESCRIBE THE ENTROPY OF SOLVATION OF SPHERICAL IONS IN POLAR-SOLVENTS [J].

FAWCETT, WR ;

BLUM, L .

JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1992, 88 (22) :3339-3344

[10] ESTIMATION OF FREE-ENERGY OF ACTIVATION FOR ELECTRON-TRANSFER REACTINS INVOLVING DIPOLAR REACTANTS AND PRODUCTS [J].

FAWCETT, WR ;

KHARKATS, YI .

JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1973, 47 (03) :413-418

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