EQUATION OF VOLTAMMETRIC WAVES CONTROLLED BY DIFFUSION, CHARGE-TRANSFER AND CHEMICAL-REACTIONS AT ULTRAMICROBAND ELECTRODE

The theory of electrochemical processes controlled by diffusion, chemi cal reaction and electrode reaction occurring at ultramicroband electr odes are investigated by means of integral transformations. Multidimen sional integral equations related to the E(q)c(irr), E(q)c(irr) and c( rev) E(q) coupled with quasi-reversible charge transfer are obtained, the results we obtained as follows For E(q)C(irr) process: f(t,x)exp[a nf(E(t) - E(0))]/Lambda + 1 = 1/2 pi integral(-1)(1) du integral(0)(1) exp[-(x-u)(2)/4(t-tau)]/t-tau. {(1 - k(f)/k(b))exp[-k(b)(t-tau)] + k( f)/k(b) + [exp(nf(E(t) - E(0))]}f(tau,u)dr For E(q)C(irr)' process: f( t,x)exp[anf(E(t) - E(0))]/Delta + 1/1 + exp[nf(E(t) - E(0)] = - 1/2 pi integral(-1)(1) du integral(0)(t) exp[- (x - u)(2)/4(t - tau)]/(t - t au) exp[-k(c)(t - tau)]f(tau,u)d tau For C(rev)E(q) process: f(t,x)exp [anf(E(t) - E(0))]/Lambda + 1 = - 1/2 pi integral(-1)(1) du integral(0 )(t) exp[- (x - u)(2)/4(t - tau)]/(t - tau). {1 + exp[- k(b)(t - tau)] }exp[nf(E(t) - E(0)]f(tau,u)d tau where f(t,x) is the dimensionless el ectroactive species flux on electrode surface. The voltammogram can be calculated by numerical method, and the typical i-E curves are shown in this paper.