SECOND HARMONIC AC POLAROGRAPHY . THEORETICAL PREDICTIONS FOR SYSTEMS WITH FIRST-ORDER CHEMICAL REACTIONS FOLLOWING CHARGE TRANSFER STEP

被引：70

作者：

MCCORD, TG

SMITH, DE

机构：

[1] Department of Chemistry, Northwestern University, Evanston

[2] General Electric Corp., Materials and Processes Laboratory, Schenectady, N. Y.

来源：

ANALYTICAL CHEMISTRY | 1969年 / 41卷 / 11期

关键词：

D O I：

10.1021/ac60280a006

中图分类号：

O65 [分析化学];

学科分类号：

070302 ; 081704 ;

摘要：

Theoretical predictions for the second harmonic ac polarographic response of systems involving rate control by diffusion, first-order following chemical reactions, and/or heterogeneous charge transfer kinetics are presented and discussed. The theoretical formulation is based on a rigorous solution of the expanding plane boundary value problem by the Matsuda method. The calculated second harmonic behavior, including both amplitude and phase characteristics, is examined for a wide range of kinetic conditions encompassing both nernstian and non-nern-stian behavior. Characteristics of the second harmonic response which make its observation eminently useful in quantitatively studying the kinetics of homogeneous chemical reactions following heterogeneous charge transfer are made apparent. Approaches to data analysis are recommended. © 1969, American Chemical Society. All rights reserved.

引用

页码：1423 / &

共 58 条

[1] RING-DISC ELECTRODES .8. TRANSIENT CURRENTS AND FIRST-ORDER KINETICS [J].