SECOND HARMONIC ALTERNATING CURRENT POLAROGRAPHY - A GENERAL THEORY FOR SYSTEMS WITH COUPLED FIRST-ORDER HOMOGENEOUS CHEMICAL REACTIONS

被引：20

作者：

MCCORD, TG

SMITH, DE

机构：

[1] Department of Chemistry, Northwestern University, Evanston

来源：

ANALYTICAL CHEMISTRY | 1968年 / 40卷 / 13期

关键词：

D O I：

10.1021/ac60269a022

中图分类号：

O65 [分析化学];

学科分类号：

070302 ; 081704 ;

摘要：

A general theory for the second harmonic ac polarographic response of systems characterized by first-order homogeneous chemical reactions coupled to a single heterogeneous charge transfer step is presented. Based on an approach recently outlined in detail for the fundamental harmonic case, the theory accounts for rate control by diffusion, a single heterogeneous charge transfer step, and any number or type of coupled first-order homogeneous chemical reactions, within the framework of the expanding plane model of the dropping mercury electrode. The solution of the boundary value problem is modeled after the method of Matsuda, which invokes just two minor limitations on the magnitudes of the rate parameters. The final master equation allows one to deduce theoretical expressions for the second harmonic ac polarographic wave associated with a particular mechanistic scheme in this class simply by inspection of readily available surface concentration expressions. © 1968, American Chemical Society. All rights reserved.

引用

页码：1967 / &

共 9 条

[1]

BARD AJ, 1966, ELECTROANALYTICAL ED, V1, pCH1

[2]

DELAHAY P, 1961, ADV ELECTROCHEMISTRY, V1, P279

[3]

DELAHAY P, 1951, ADVANCES ELECTROCHEM, V1, P279

[4]

MATSUDA H, 1958, Z ELEKTROCHEM, V62, P977

[5] ALTERNATING CURRENT POLAROGRAPHY - AN EXTENSION OF GENERAL THEORY FOR SYSTEMS WITH COUPLED FIRST-ORDER HOMOGENEOUS CHEMICAL REACTIONS [J].