KINETIC-STUDIES ON THE THERMAL CIS TRANS ISOMERIZATION OF AN AZO COMPOUND IN THE ASSEMBLED MONOLAYER FILM

被引：70

作者：

LIU, ZF ^{[1
]}

MORIGAKI, K ^{[1
]}

ENOMOTO, T ^{[1
]}

HASHIMOTO, K ^{[1
]}

FUJISHIMA, A ^{[1
]}

机构：

[1] UNIV TOKYO,FAC ENGN,DEPT SYNTHET CHEM,TOKYO 113,JAPAN

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1992年 / 96卷 / 04期

关键词：

D O I：

10.1021/j100183a066

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 thermal cis-trans isomerization of an amphiphilic azo compound in the assembled monolayer film has been investigated kinetically, with an electrochemical approach being employed to follow the reaction process. Isomerization in the rigid monolayer film was found to follow first-order kinetics as in the liquid phase, at least in the earlier stage of reaction. The rate constant can be expressed by k = 10(8.5 +/- 1.5) exp (-(16.5 +/- 1.0 kcal mol-1)/RT) s-1. Interestingly, in spite of the rigid and highly-oriented film structure, activation parameters such as enthalpy (DELTA-H double-ended dagger) and entropy (DELTA-S double-ended dagger) were quite comparable to those in chloroform solution, whereas they were distinctly smaller than those of azobenzene in crystal. The kinetic behavior observed is attributed to the effects of the assembled monolayer film environment employed and implies an inversion mechanism for the thermal isomerization in the monolayer film.

引用

页码：1875 / 1880

页数：6

共 32 条

[1] MECHANISTIC STUDY OF THERMAL Z-E ISOMERIZATION OF AZOBENZENES BY HIGH-PRESSURE KINETICS [J].