Bk. Jin et al., EQUATION OF VOLTAMMETRIC WAVES CONTROLLED BY DIFFUSION, CHARGE-TRANSFER AND CHEMICAL-REACTIONS AT ULTRAMICROBAND ELECTRODE, Gaodeng xuexiao huaxue xuebao, 17(7), 1996, pp. 1052-1055
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.