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.
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.
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页码:1423 / &
相关论文
共 58 条
[21]  
HEYROVSKY J, 1966, PRINCIPLES POLAROGRA, P393
[22]  
HEYROVSKY J, 1966, PRINCIPLES POLAROGRA, P77
[23]   ALTERNATING CURRENT POLAROGRAPHY WITH MULTI-STEP CHARGE TRANSFER .2. THEORY FOR SYSTEMS WITH QUASI-REVERSIBLE 2-STEP CHARGE TRANSFER [J].
HUNG, HL ;
SMITH, DE .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1966, 11 (06) :425-&
[24]   TIME DEPENDENCE OF AC POLAROGRAPHIC CURRENTS [J].
HUNG, HL ;
SMITH, DE .
ANALYTICAL CHEMISTRY, 1964, 36 (04) :922-&
[25]  
JAENICKE W, 1962, Z ELEKTROCHEM, V66, P814
[26]  
JAENICKE W, 1962, Z ELEKTROCHEM, V66, P808
[27]  
KOOPMANN R, 1966, BERICH BUNSEN GESELL, V70, P121
[29]   MEASUREMENT OF CHEMICAL REACTION RATES FOLLOWING ELECTRON TRANSFER AN EMPIRICAL APPROACH USING RING-DISK ELECTRODES [J].
MALACHE.PA ;
PRATER, KB ;
PETRIE, G ;
ADAMS, RN .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1968, 16 (01) :41-&