4 vues

Transféré par Anonymous hkDxd8L

It has become common practice to estimate the numbers of electrons transferred in faradaic reactions at rotated disk electrodes from the slope of plots of reciprocal current vs. reciprocal square root ofrotational velocity . This practice is based on the Koutecky¬ -Levich equation derived for a one-step electrontransfer mechanism. Furthermore, the intercept of the Koutecky¬ -Levich plot is assumed to be a reciprocal function of the heterogeneous rate constant for the electron-transfer process. In this review, we examine the validity of the practice of estimating values of n and k for various multi-step mechanisms at RDEs.

- Electrochemical
- projectproposal
- CRE II -29
- Chapter 5 Diffusion
- Mass Tranfer Assignment
- 68056_04.desbloqueado
- Chapter 11
- Transport
- Electrochemistry
- Gas Diffusion
- chem 155 electrochemistry
- projectproposal
- Written Report in Eng.g Materials (1)
- Energy Environ. Sci. 2008 Hamann
- Lyons Bartlett MHC 1
- PEX-01-01
- Electro Chem
- Project Report
- 00835284 DULS
- 05PO_SM_2_5.pdf

Vous êtes sur la page 1sur 7

Review

Diagnoses of Charge-Transfer Mechanisms at Rotated Disk

Electrodes

Stephen Treimer, Andrew Tanga, and Dennis C. Johnson*

Department of Chemistry and Ames Laboratoryb, Iowa State University, Ames, Iowa 50011, USA; email: dcj@iastate.edu.

a

Present Address: PC Computers, 108-5th St., Ames, IA 50011-3111, USA.

b

Ames Laboratory is operated for the U.S. Department of Energy by Iowa State University under Contract W-7405-Eng-82

Final version: June 12, 2001

Abstract

It has become common practice to estimate the numbers of electrons (n, eq mol 1) transferred in faradaic reactions at

rotated disk electrodes (RDEs) from the slope of plots of reciprocal current (1/I) vs. reciprocal square root of

rotational velocity (1/w1/2). This practice is based on the Koutecky¬-Levich equation derived for a one-step electron-

transfer mechanism. Furthermore, the intercept of the Koutecky¬-Levich plot is assumed to be a reciprocal function of

the heterogeneous rate constant (kh, cm s 1) for the electron-transfer process. In this review, we examine the validity

of the practice of estimating values of n and kh for various multi-step mechanisms at RDEs.

Keywords: Koutecky-Levich equation and plots, Charge-transfer mechanisms, Rotating disk electrodes

1. Introduction

electrode surface (x 0) given approximately by the first

two terms of a power series:

1.1. Rotated Disk Electrodes (RDEs) [1 ± 7]

Applications of rotated disk electrodes (RDEs) to studies of vx 0:510w3=2 v x 0:333w2 v 1 x3

1=2 2

3

electrode kinetics and mechanisms are documented [1 ± 7].

Advantages of RDEs include: i) The rate of mass transport

of reactants to a RDE surface is controlled precisely by where u is the kinematic viscosity of the solution (cm2 s 1).

fixing the rotational velocity (w) of the electrode. ii) The second term in Equation 3 is frequently ignored for

Electrode currents (I) quickly achieve steady-state values solutions of electroactive species having low diffusivity [1 ± 7].

(@I/@t 0) following establishment of applied electrode The cathodic electrode current (Ic) for the reduction of the

potential (Eapp) for moderate-to-high rates of rotational oxidized species (A) to its reduced form (B) is written:

velocity (w > ca. 10 rad s 1). As a consequence, voltammet- b

@CA CA CsA

ric response (I ± Eapp) for a species transported from the bulk Ic nFpr2 DA nFpr2 DA 4

@x x0 d

solution to the RDE surface is independent of potential scan

rate for low rates of scan (f < ca. 0.1 V s 1). iii) Current

where n is the number of electrons transferred (eq mol 1), F

response at RDEs is insensitive to incidental vibrations of

is the Faraday constant (96,487 C eq 1), p r2 is the geometric

the apparatus.

disc area (cm2) and CsA is the concentration of A at the

electrode surface (x 0). Also, in Equation 4, d represents

the thickness of the diffusion layer at the electrode surface

1.2. The Levich Response [1 ± 7] and is defined by Equation 5 for species having low

Consider the simple cathodic mechanism: diffusivity.

1

d 0:620 D1=3

A u

1=6

w 1=2

5

A ne > B; E ' 0

(1)

For large negative applied overpotential (h Eapp ± E0× 0),

At steady-state, the rates of diffusional and convective CsA ! 0 and the cathodic response corresponds to that value

transport of A are equal at the electrode surface and limited by the maximum rate of convective-diffusional mass

expressed: transport, as predicted by the so-called Levich equation for

reactant species having low diffusivity [1].

@ 2 CA @CA

DA vx 2 2=3

@x2 x0 @x x0 Ilim;c 0:620nFpr2 DA u 1=6

w1=2 CbA 6

Electroanalysis 2002, 14, No. 3 ¹ WILEY-VCH Verlag GmbH, 69469 Weinheim, Germany, 2002 1040-0397/02/0302-0165 $ 17.50+.50/0

166 S. Treimer et al.

For species having high diffusivity, the form of the Levich Of greatest importance for this review are examples of

equation recommended by Gregory and Riddiford [6] is reactions for which the rates of mass transport and electron

given by Equation 7; see especially p. 365 of [7]. transfer are comparable and 0 < CsA < CbA . These cases are

" # described as having mixed transport-kinetic control. The

0:554 electrode current for such cases is then described by both

Ilim;c 0:36

nFpr2 D2=3

A u

1=6

w1=2 CbA
7 Equations 4 and 11. Combining these equations to eliminate

0:893 0:316
D=u

CsA and solving for Ic produces the so-called Koutecky¬-

Levich equation [8].

Accordingly, for reactant species having high diffusivity, the

thickness of the diffusion layer is given by: nFpr2 DA CbA

Ic
13

" # d DA =kh

1

0:554

d 0:36

D1=3

A u

1=6

w 1=2

8

0:893 0:316
D=u The functionally useful form of Equation 13 is the reciprocal

of Ic, given by:

Evidence that an electrode response corresponds to Equa-

tions 6 and/or 7 is the observation of a linear dependence of 1 d 1

14

Ilim, c on the product w1=2 CbA . Ic nFpr2 DA CbA nFpr2 kh CbA

In the remainder of this review, reactant species will be

considered to have low diffusivity, i.e., Equations 5 and 6 are Substituting Equation 5 into Equation 14 yields:

assumed to define d and Ilim, c.

1 1 1

2=3

15

Ic 0:62 nFpr2 DA v 1=6 w 1=2 C b

A

nFpr2 kh CbA

1.3. Voltammetric Principles

For small values of h in a solution of A, having fast electron Hence, for cathodic reactions governed by mixed transport-

transfer, CsA is defined: kinetic control, plots of 1/Ic vs. 1/w1/2 for constant values of kh,

i.e., fixed h, are predicted to generate straight lines having

CsA CbA expfqg
9 slopes proportional to 1/n and intercepts proportional to 1/

kh. It is important to observe that the slopes of these plots are

where q nFh/RT. The electrode current can then ex- independent of applied overpotential.

pressed: It is tempting to apply Equation 16 for the analyses of all

amperometric and voltammetric data to determine values

nFpr2 DA CbA for n and kh. Indeed, this action appears viable when

Ic
10

d1 expfqg experimental plots of 1/Ic vs. 1/w1/2 exhibit linearity. This

review examines the nature of 1/Ic vs. 1/w1/2 plots predicted

Plots of Ic vs. w1/2 are predicted to be linear at all h with slopes for various mechanisms at RDEs.

proportional to n. At h 0, i.e., Eapp E0×, exp{q} 1 and

Ic 0.5 Ilim, c. For q 0, exp{q} 0 and Ic Ilim, c.

1.4. The Koutecky¬-Levich Response [9]

In the discussion below, electron-transfer and chemical steps

Equation 6 is the ideal response of fast electron-transfer are represented by symbols E and C, respectively. Further-

processes. For systems with slow electron transfer, the more, subscripts r and i qualify the steps as being reversible

electrode current is defined: (kinetically fast) or irreversible (kinetically slow), respec-

tively. Hence, a CiEi designation implies an irreversible

Ic nFpr2 kh CsA 11 chemical step followed by an irreversible electron-transfer

step.

where kh (cm s 1) is the heterogeneous rate constant for It also is assumed that all steps in the mechanism proceed

electron transfer. at comparable rates or that one step is slow, i.e., the rate

determining step (rds). For example, in an EC mechanism,

aFh the E step is assumed to be fast, else the C step does not

kh k0 exp 12

RT proceed significantly and the mechanism exhibits the

characteristics of a single E step. It is also assumed that all

As predicted by Equation 11, CsA ! CbA for kh ! 0 and species in solution have equal values of diffusion coefficient

CsA ! 0 for kh !1 . (D).

Koutechy¬-Lewich Plots 167

2. EE Mechanisms [9, 10] Fpr2 DA CbA DA 2 expfq1 g 1

Ic 2 22

d dkh DA expfq1 g 1

Consider a cathodic mechanism involving two consecutive

2

Fpr DA CA b

DA 2dkh

one-electron steps, i.e., an EE mechanism, as represented

d dkh DA expfq1 g 1

by:

A e > B; E0'1 (16) According to Equation 22, the apparent value of n ap-

proaches 2 eq mol 1 for d kh ! 0, i.e., large negative

B e > C; E02 (17) overpotential. This is equivalent to a convective-diffusional

transport-limited reaction with n 2 eq mol 1. Written in

In deriving equations for the net cathodic electrode current, reciprocal form, Equation 22 becomes:

0 0

it is assumed that the first step is at equilibrium, E01 > E02

1 d dkh DA expfq1 g 1

,and the diffusion coefficients for all species are identical [9].
23

Furthermore, in this mechanism, any reaction between the Ic Fpr2 DA CbA DA 2dkh

reactant and the product, i.e., comproportionation, is

assumed negligible. Sakai et al. present a nice treatment There are two limiting cases for Equation 23: i) For Eapp >

for the current response at an RRDE due to an EE E2, the second step is slow. This corresponds to DA 2dkh,

mechanism [10]. and the current is the same as for Er and is given by

Equation 20. ii) When Eapp < E2, the second step is fast. This

corresponds to DA 2dkh, and the reciprocal current is

given by:

2.1. Special Case of ErEr

1 d expfq1 g

The current for the ErEr mechanism is given by:
24

Ic 2Fpr2 DA CbA 2Fpr2 kh CbA

Fpr2 DA CbA expfq2 g 2 expfq1 q2 g Hence, for the ErEi mechanism, plots of 1/Ic vs. 1/w1/2 exhibit

Ic 2
18

d 1 expfq2 g expfq1 q2 g a slope inversely proportional to the total number of

electrons passed in the step-wise mechanism (1/ntot) and

where q1 Fh1/RT and q2 Fh2/RT. Taking the reciprocal, an intercept inversely proportional to the heterogeneous

Equation 18 becomes: rate constant for the second irreversible step (1/kh). From

this, we conclude that, for a multi-stepwise mechanism, the

1 d 1 expfq2 g expfq1 q2 g apparent number of electrons (napp) determined from the

19

Ic Fpr2 DA CbA 2 expfq2 g plot of 1/Ic vs. 1/w1/2 corresponds to the sum of the electrons

passed for the fast steps plus the rate determining step.

Accordingly, plots of 1/Ic vs. 1/w1/2 are expected to be linear Clearly, this value of napp can be equal to or less than the total

with zero intercepts and slopes that vary as a function of number of electrons (ntot) determined from the coulometric

0

applied overpotential. At very negative potentials (E02 h), result of exhaustive electrolysis.

the exponential terms in Equation 19 are negligible, and the

current is limited by convective-diffusional transport, as

described by: 3. Introduction to EC and CE Mechanisms [11, 12]

20

Ic Ilim;c 0:62nFpr2 D2=3

A v

1=6 w1=2 CbA solution before, after or between electron transfer steps. The

mathematical analyses of these mechanisms are simplified

0

Only in the case where E02 h is the slope of the reciprocal by the use of the reaction layer approach [12, 13], the

plot a reliable measure of the total value of n for the principle of which is illustrated by the following example.

sequential processes. For an EC reaction scheme, we write:

k

2.2 Special Case of ErEi B!C
26

The formation of C from B is assumed to be complete within

kh 0

Be !C; E02 21 a reaction layer at the electrode surface having a thickness of

m defined by:

168 S. Treimer et al.

A small m corresponds to a very short lifetime of B (k 0), which, in the reciprocal form, is written:

e.g., for m d, the contribution from convection can be

ignored and the problem is reduced to a diffusion-controlled 1 d D
1 K mkh

B 2
34

process modified by a chemical reaction. The reaction layer Ic nFpr2 DB Cb nFpr DB Kkh Cb

thickness is also viewed as a parameter that emerges through

the solution of the equations describing the electrochem- For this mechanism, the slopes of reciprocal plots are not a

ical-chemical system [13], where k is a linear combination of function of applied overpotential.

the rate constants of the chemical step.

4. CE Mechanisms [14 ± 16]

Galus [17] first made observations of the EC mechanism

Initial interpretations of CE mechanisms were made by represented by:

Koutecky¬ and Levich [13]. Further contributions were

0

offered by Albery [14], Compton et al. [15], Rebouillat A e > B; E01 (35)

et al. [16]. For the electroinactive species A in equilibrium

with the electroactive B species, the first step in the CE in which species B is converted to an electroinactive species

mechanism is represented by: C via a chemical process. Bard and Faulkner have provided a

kf

general overview of EC processes at RDEs [18].

AB; where K kf/kb and k kf kb (28)

kb

presented below. 5.1. Case of ErCr

The chemical step is reversible, as represented by:

4.1. Case of CrEr

kf

The second step is represented by: B C where K kf/kb and k kf kb (36)

kb

0

B e > C; E01 (29) The current is given by the expression:

For the situation, the electrode current is given by: nFpr2 DA
1 KCbA

Ic
37

d1 K expfq1 g mK expfq1 g

nFpr2 DB KCb

Ic
30

dK
1 K expfq1 g m with the reciprocal being written:

where Cb CbA CbB. Equation 30 is accurate when (DB/u)1/3 1 d1 K expfq1 g mK expfq1 g

38

k/w. When K 1, Ic Ilim, c. Equation 30 can be rear- Ic nFpr2 DA
1 KCbA nFpr2 DA
1 KCbA

ranged to:

For this mechanism, slopes of the reciprocal plots are a

1 dK
1 K expfq1 g m function of applied overpotential.

31

Ic nFpr2 DB KCb nFpr2 KDB Cb

predicted to be linear with intercepts proportional to m/K. 5.2. Case of ErCi

Again, it is important to note that the slopes of reciprocal The second step is irreversible, as represented by:

plots for this mechanism are a function of applied over-

potential. k

B!C 39

4.2. Case of CrEi

The second step is represented by: The current for which is:

B e !C

kh

32 nFpr2 DA CbA

Ic
40

d m expfq1 g

The current is given by: which, in the reciprocal form, is given by:

Ic 33 41

DB 1 K kh m dK Ic nFpr2 DA CbA nFpr2 DA CbA

Koutechy¬-Lewich Plots 169

0

This expression is reasonably accurate for values of d/m > 50. C e > D; E02 , (47)

As noted in Equation 41, slopes of the reciprocal plots are

not a function of applied overpotential.

6.1. Case of ErCrEr

The cathodic current for this sequential mechanism is given

5.3. ECi' Mechanisms by:

McIntyre et al. [19] elucidated the ECi' mechanism. Comp-

2Fpr2 DA KCbA

ton and co-workers have contributed significant recent Ic
48

dK m
1 K expfq1 g d expfq1 q2 g

interpretations for the ECi' mechanism [20, 21]. The

reactant is regenerated from the product by a chemical

step, considered to be catalytic, as indicated by: Rearranging to the reciprocal form, gives:

A e > B; E01 (42) 49

Ic 2Fpr2 DA KCbA 2Fpr2 DA KCbA

k

B!A 43

Again, it is important to note that the slopes of reciprocal

plots for this mechanism are a function of applied over-

potential.

The current is given by:

nFpr2 DA CbA

Ic
44

m1 expfq1 g 6.2. Case of ErCrEi

For such a mechanism, the third step corresponds to:

For this mechanism, Ilim, c nFqr2(DA/m) C bA at q 0.

It is apparent from Equation 44 that the current observed kh

C e !D
50

for ECi' is a factor of d/m times the current due solely to mass

transport and is independent of the rotational speed. This

conclusion assumes kf is large compared to DA/d and, hence,

with the current denoted:

the effect of mass transport is negligible. When this

assumption is no longer valid, the observed current has 2Fpr2 DA Kkh CbA

both mass transport and catalytic components. The ob- Ic
51

dKkh DA m
1 Kkh expfq1 g

served current approaches the transport-limited current for

the A species in the bulk solution as the rotational velocity is

Rearranging to the reciprocal form, we get:

increased. In general, for ECi' mechanisms, plots of Ic vs. w1/2

have non-zero intercepts. The ECi' mechanism at chemically 1 d D m
1 Kkh expfq1 g

modified electrodes, though well documented in the liter- b

A
52

Ic 2Fpr DA CA

2 2Fpr2 DA Kkh CbA

ature, will not be interpreted by this work due to compli-

cations arising from the interpretations of Michaelis-Men-

The slopes of reciprocal plots for this mechanism are not a

ten style kinetics.

function of applied potential.

Filinovskii, made some of the early predictions for various The preceding treatments assume that the electrode surfa-

ECE mechanisms [2]. Subsequent work by Amatore and co- ces are uniformly active and accessible to the reactants.

workers [22, 23] and Compton et al. [24] further developed Landsberg, Scheller, and co-workers brought to light

the theoretical model for the ECE mechanism. In a cathodic significant advances in blocked or inhomogeneous electro-

ECE mechanism, the reactant (A) is reduced to the des; electrodes that are not fully accessible to solution [25 ±

electroinactive species B via electron-transfer. The species 27], possibly the result of the formation of an inert organic

B is chemically transformed in solution to an electroactive film, oxide, adsorbed gas bubbles, or insufficiently clean

intermediate (C) which undergoes further reduction to give surface preparation. There are two types of inhomogeneous

the final product (D). The three steps in the ECE electrodes: macroscopic [28, 29] is when the size of active

mechanism are represented by: regions and the distance between them are similar to the

thickness of the diffusion layer; and microscopic [30, 31] is

0

A e > B; E01 (45) when the size of the active regions and the distance between

kf

them are much smaller than the thickness of the diffusion

B )* C; where K kf/kb and k kf kb (46) layer.

kb

170 S. Treimer et al.

Useful treatments for the diagnosis of mechanisms at electrode. Second, for f 1, the amount of reactant electro-

polymer coated rotated disc electrodes using Koutecky¬- lyzed is sufficiently low relative to the rate of diffusion,

Levich plots have been developed recently, but will not be therefore the concentration near the electrode reaches a

presented in this brief article. steady state and the voltammetric response obtained for a

quiescent solution has the appearance of the response

obtained in stirred solution. The limiting current is given by:

7.1. Macroscopic Inhomogeneity Fpr2 DA CbA

Ilim
54

The response of an inhomogeneous electrode is complicated 2r0 F
1 f

by radial (nonlinear) diffusion and convection mass trans-

port. Let f denote the fraction of the surface that is inactive. where F(1 ± f) is 0.3 (1 ± f) 1/2 for disk type sites and 1 ± (1/p)

For an inhomogeneous RDE with f 0.5, Levart [32] Ln sin{(p/2)(1 ± f)} for stripe-type sites and 2ro is the distance

compared digital simulations of the effect of the radius of between the centers of two adjacent sites.

the active sites (rs) on the ratio (1) of the observed currents Although the results of Amatore et al. were derived for

to the transport-limited currents for a fully active RDE. For diffusion to stationary electrodes, they should apply for

these simulations, the diameter of the active sites was set RDE systems if d 2ro. Therefore a microscopically

equal to distance between these sites. For rs > 10 d, 1 was inhomogeneous RDE with f 1 is equivalent to a fully

independent of d. At rs > d, 1 increased with increasing d. active electrode of the same geometry with a slower electron

Because 1 depends on d, the I ± w1/2 plot exhibited a reaction transfer rate at the same applied potential. When f ! 1, the

under mixed transport-kinetic control. Over the range current is not a function of rotational speed and is not

0.96 f 0.50, 1 was greater than 1 ± f; i.e., the current was necessarily smaller than the diffusion-limited current at a

larger than expected if the total active area behaved as one geometrically identical, fully active electrode.

contiguous surface. The additional current was due to the

contribution of radial convection to mass transport.

Radial diffusion is most significant at small electrodes and 8. Diagnosis of Mechanisms

low rotation speeds. Landsberg and co-workers [25] offered

an analytical approach to the current response due to radial The primary motivation in many electroanalytical studies of

convection, further refined by Scheller and co-workers [26, electrode response at hydrodynamic electrodes is the

27], and summarized by Filinovskii and Pleskov [2, 3]. determination of the value for n (eq mol 1) corresponding

According to the model, active sites were circular with to the charge-transfer component of the response mecha-

radius r1, uniformly distributed on the electrode surface, and nism. A secondary objective is identification of the simplest

concentric with one end of a larger, imaginary cylinder. Mass mechanism that is consistent with observed variations in

transfer between the sites and the solution occurred by electrode response as a function of changes in the rate of

diffusion inside the cylinders, each with length d and radius convective-diffusional mass transport. And, of course,

r2. Given d r2, the model predicted linear plots of 1/I vs. 1/ associated with this mechanistic diagnosis is the evaluation

w1/2, with intercepts as Bessel functions of the quantity r1/r2. of the rate constant corresponding to the rate-determining

This case has been experimentally verified [25 ± 27]. For d step (rds).

r2, a plot of I vs. w1/2 was linear with slope as a different Bessel Linearity of Levich plots of I vs. w1/2 over an extended

function of r1/r2, less than the Levich slope. The model was range of w values, e.g., 5 ± 1000 rad s 1 (50 ± 10000 rev min 1),

not very realistic because each site would have its own is indicative of a response mechanism that can be approxi-

diffusion layer [28], but gave the correct functional depend- mated as a single step resulting in the rapid transfer of n

ence [26]. Caprani and Frayret [33] developed an Equation electrons characterized by a large heterogeneous rate

for a partially blocked surface with independently active constant (kh). For this case, the n value can be reliably

sites, for which the current is summed for each micro- estimated from the slope using literature values of u and D.

electrode over the entire surface. The Equation is: If these values are not available, the estimation u 1.0

10 2 cm2 s 1 is useful for most aqueous media and D 1.0

1 1.1 pr1/3(1 ± f)5/6d1/6 (53) 10 5 cm2 s 1 is a common approximately for small reactant

species in aqueous media. Negative curvature in plots of I vs.

where r is the radius of the RDE and d is the number of w1/2 can be indicative of slow charge-transfer kinetics, as

active sites per unit of geometric area. indicated by Equation 10. Of course, this is the mechanism

presumed in the derivation of the Koutecky¬-Levich equa-

tion and, therefore, the plot of 1/I vs. 1/w1/2 is recommended.

Accordingly, we recommend estimation of n values from

7.2. Microscopic Inhomogeneity

both the linear segment of the Levich plot at low w values

Amatore et al. proposed two sub-cases for diffusion to (< ca. 100 rad s 1) and from the linear segment of the

microscopically inhomogeneous surfaces [30]. First, when Koutecky¬-Levich plot at large w values (> ca. 100 rad s 1).

f 1, the standard rate constant for electron transfer is (1 ± Equality of these two n values can be interpreted as

f) times that of the standard rate constant for a fully active confirmation of the diagnosis of a one-step mechanism

Koutechy¬-Lewich Plots 171

involving the transfer of n electrons with a moderately slow [10] M. Sakai, N. Ohnaka, J. Electrochem. Soc. 1990, 137, 576.

heterogeneous rate constant (kh). Furthermore, kh can be [11] J. Koutecky¬, R. Brdicka, Coll. Czech. Chem. Comm. 1947, 12,

evaluated from the non-zero intercept of the Koutecky¬- 337.

[12] P. Delahay, New Instrumental Methods in Electrochemistry,

Levich plot, as indicated by Equation 15. Wiley-Interscience, New York 1954, p. 92.

Should one observe that the value of n calculated from the [13] J. Koutecky¬, V. G. Levich, Dokl. Akad. Nauk. SSSR 1957,

Levich plot for low w values is larger than that estimated 117, 441.

from the Koutecky¬-Levich plot for large w values can be [14] W. J. Albery, Electrode Kinetics, Clarendon Press, Oxford

interpreted as indicative of two or more consecutive charge 1975, ch. 5.

transfer steps, e.g., ErEi and ErCEi mechanisms, wherein the [15] R. G. Compton, R. G. Harland, J. Chem. Soc., Faraday Trans.

1, 1989, 85, 761.

second charge-transfer step occurs with a kh value much

[16] S. Rebouillat, M. E. G. Lyons, T. Bannon, J. Solid State

smaller than that for the first charge-transfer step. It can be Electrochem. 1999, 3, 215.

helpful in such cases to determine an overall n value from [17] Z. Galus, R. N. Adams, J. Electroanal. Chem. 1962, 4, 248.

coulometric results for an exhaustive electrolysis. [18] A. Bard, L. Faulkner, Electrochemical Methods, 1st ed.,

Partially blocked electrode surfaces usually are the Wiley, New York 1980, p. 466.

undesired consequence of the adsorption of organic impur- [19] J. D. E. McIntyre, J. Phys. Chem. 1967, 71, 1196.

[20] R. G. Compton, M. J. Day, M. E. Laing, R. J. Northing, J. I.

ities from the bulk solution and/or the polymerization of

Penman, A. M. Waller, J. Chem. Soc., Faraday Trans. 1, 1988,

free-radical intermediate products of incomplete electrode 84, 2013.

reactions involving organic reactants. Therefore, electrode [21] R. G. Compton, R. A. Spackman, P. R. Unwin, J. Electroanal.

response under these situations will demonstrate a steady Chem. 1989, 264, 1.

decay with continued use. Electrode response can be [22] C. Amatore, J.-M. Save¬ant, J. Electroanal. Chem. 1977, 85,

restored by mechanical polishing, sonication, and/or appli- 27.

cation of positive-negative potential steps to cause anodic or [23] C. Amatore, M. Gareil, J.-M. Save¬ant, J. Electroanal. Chem.

1983, 147, 1.

cathodic desorption of the films [34 ± 37]. [24] R. G. Compton, R. G. Harland, P. R. Unwin, A. M. Waller, J.

Finally, apply different electrode geometries and/or Chem. Soc., Faraday Trans. 1, 1987, 83, 1261.

chronoamperometry and the corresponding theories to [25] R. Landsberg, R. Thiele, Electrochim. Acta 1966, 11, 1243.

elucidate ambiguous results of the RDE voltammetry to [26] F. Scheller, S. M¸ller, R. Landsberg, H.-J. Spitzer, J.

assist in the unambiguous determination of the mechanism Electroanal. Chem. 1968, 19, 187.

[38]. [27] F. Scheller, R. Landsberg, S. M¸ller, J. Electroanal. Chem.

1969, 20, 375.

[28] Y. M. Povarov, P. D. Lukovtsev, Electrochim. Acta 1973, 18,

13.

9. References [29] V. Y. Filinovskii, Electrochim. Acta 1980, 25, 309.

[30] C. Amatore, J.-M. Save¬ant, D. Tessier, J. Electroanal. Chem.

[1] V. G. Levich, Physicochemical Hydrodynamics, 2nd. ed., Interfacial Electrochem. 1983, 147, 39.

Prentice-Hall, Englewood Cliffs, N. J., 1962, pp. 60 ± 72. [31] O. Contamin, E. Levart, J. Electroanal. Chem. 1982, 136, 259.

[2] Y. V. Pleskov, V. Y. Filinovskii, The Rotating Disc Electrode [32] E. Levart, J. Electroanal. Chem. 1985, 187, 247.

(Ed: H. S. Wroblowa) Consultants Bureau, New York 1976, [33] A. Caprani, J. P. Frayret, J. Electroanal. Chem. 1982, 138, 155.

ch. 2. [34] D. C. Johnson, W. R. LaCourse, Anal. Chem. 1990, 62 589A.

[3] V. Y. Filinovskii, Y. V. Pleskov, Progress in Surface and [35] W. R. LaCourse, D. C. Johnson, in Advances in Ion Chro-

Membrane Science, Vol. 10 (Eds: D. A. Cadenhead, J. F. matography, Vol. 2 (Eds: P. Jandik, R. M. Cassidy), Century

Danielli), Academic Press, New York 1976, p. 27. International, Medfield, MA 1990 353.

[4] Z. Galus, Fundamental of Electrochemical Analysis (Ed: S. [36] W. R. LaCourse, Pulsed Electrochemical Detection in High-

Marcinkiewicz), Halsted, New York 1976. Performance Liquid Chromatography, Wiley, New York

[5] A. J. Bard, L. R. Faulkner, Electrochemical Methods, 1st ed., 1997.

Wiley, New York 1980, ch. 8. [37] S. Ranganathan, T.-C. Kuo, R. L. McCreery, Anal. Chem,

[6] D. P. Gregory, A. C. Riddiford, J. Chem. Soc. 1956, 3756. 1999, 71, 3574.

[7] C. M. A. Brett, A. M. Oliveira Brett, Comprehensive Chem- [38] R. G. Compton, M. E. Laing, D. Mason, R. J. Northing, P. R.

ical Kinetics, Vol. 26 (Ed: C. H. Bamford, R. G. Compton), Unwin, Proc. R. Soc.

Elsevier, Amsterdam 1986, ch. 5. London A 1988, 418, 113.

[8] J. Koutecky¬, V. G. Levich, Zh. Fiz. Khim. 1956, 32, 1565.

[9] Z. Rongfeng, D. H. Evans, J. Electroanal. Chem. 1995, 385,

201.

- ElectrochemicalTransféré parNaeemLatif
- projectproposalTransféré parapi-242285436
- CRE II -29Transféré parMehul Varshney
- Chapter 5 DiffusionTransféré parKhalil Alhatab
- Mass Tranfer AssignmentTransféré parmadhu77
- 68056_04.desbloqueadoTransféré parJhonatan Gerardo Soto Puelles
- Chapter 11Transféré pareimaiokanenas
- TransportTransféré parKashif Mehar
- ElectrochemistryTransféré parSepbeh
- Gas DiffusionTransféré parFunsho Olorunyomi
- chem 155 electrochemistryTransféré parapi-318921527
- projectproposalTransféré parapi-270700888
- Written Report in Eng.g Materials (1)Transféré parJhonie Moran
- Energy Environ. Sci. 2008 HamannTransféré parros4_swe3ty4386
- Lyons Bartlett MHC 1Transféré parmikelyons
- PEX-01-01Transféré parGrace Urbano
- Electro ChemTransféré parMadhavanIce
- Project ReportTransféré parJoel Gray
- 00835284 DULSTransféré parPaul Vince Abe
- 05PO_SM_2_5.pdfTransféré parMarcelo Varejão Casarin
- Electricity generation by a novel design tubular plant microbial fuel cellTransféré parVenessa Damanik
- Redox and Electrochemistry.pdfTransféré parErnest Nsabimana
- Answer of Chapter 23 Page 131Transféré parduannguyenquang
- Durability 3Transféré parGurram Vinay
- filmes oxidos 2.pdfTransféré parbrodriguesbh
- 17 Electrochemistry With Answers[1]Transféré parAgam Mittal
- CSEC Chemistry Syllabus With Specimen Papers and Mark Scheme-KeysTransféré parVanandi
- art%3A10.1007%2FBF02473442Transféré parCivil House
- CV WhitakerTransféré parSsheshan Pugazhendhi
- Redox Reaction!Transféré parJeffreyTran

- Contribuciones de la electrosíntesis orgánica a la química verdeTransféré parHernán Astudillo
- sensors-08-05649Transféré parAnonymous hkDxd8L
- Sigmaplot 8 Programming GuideTransféré parsharkkingking
- 1-s2.0-S0040609015002588-mainTransféré parAnonymous hkDxd8L
- Journal of Applicable Chemistry 2018 7-6-1747-1754 NMI-XRDTransféré parAnonymous hkDxd8L
- Journal of Applicable Chemistry 2018 7-6-1747-1754 NMI-XRDTransféré parAnonymous hkDxd8L
- Review. Removal of synthetic dyes from wastewaters (Environment International 30 (2004) 953 – 971).pdfTransféré parAnonymous hkDxd8L
- Protocolo para manejo de datos y resultados.pdfTransféré parAnonymous hkDxd8L
- Manual EIS IMP UNAM Para EstudiarTransféré parRuben Suarez
- Natural Colorants for Food and Nutraceutical Uses Delgado-Vargas 2002.pdfTransféré parAnonymous hkDxd8L
- Electrochemical studies of Fe(CN)64--Fe(CN)63- on gold ultramicroelectrodes varying the concentrations of KF as supporting electrolyte .pdfTransféré parAnonymous hkDxd8L
- molecules-16-05963Transféré parAnonymous hkDxd8L
- Protection of Works of Art From Atmospheric OzoneTransféré parAnonymous hkDxd8L
- Analysis of Synthetic Indigo by Means of TitanousTransféré parAnonymous hkDxd8L
- Actinometría Determinación de la Intensidad de una Lámpara de UV Utilizando Oxalato FérricoTransféré parAnonymous hkDxd8L
- Several New Aspects of Indigo ChemistryTransféré parAnonymous hkDxd8L
- Electrochemical Routes for Industrial SynthesisTransféré parAnonymous hkDxd8L
- A Search for Novel Chemotherapy Against Tuberculosis Amongst Natural ProductsTransféré parAnonymous hkDxd8L
- Investigation of natural dyes occurring in historical Coptic textiles by high-performance liquid chromatography with UV–Vis and mass spectrometric detectionTransféré parAnonymous hkDxd8L
- Analysis of Anthraquinoid and Indigoid Dyes Used in Ancient Artistic Works by Thermally Assisted Hydrolysis and Methylation in the Presence of Tetramethylammonium HydroxideTransféré parAnonymous hkDxd8L
- Organic DyestuffsTransféré parAnonymous hkDxd8L
- Spectroelectrochemistry of Solid Indirubin and Its Sulfonated FormTransféré parAnonymous hkDxd8L

- Kinetic ApproachTransféré parking76as
- ExerciseTransféré pard anjilappa
- photocatalysisTransféré parEman Abd
- Intermittent_drying_of_food_products_A_c.pdfTransféré parKusal Kanushka Suraweera
- Lecture as 1cTransféré parJosh Go Go
- Modeling of Secondary Reactions of Tar (Srt) Using a Functional Group ModelTransféré parIAEME Publication
- AQA as chemistry new specTransféré parMohit Changani
- Arrehnius Questions.docxTransféré parJol
- Chapter 10 Chemical Kinetics II.pdfTransféré parJuanCarlosVazquezLira
- 1999 HRWTransféré parAhmad Alfian
- BertholletTransféré parAnnittha Thackann
- Aspen Introduction 2013Transféré parJayRyu
- 12 Chemistry Chapter 4 Assignment 1Transféré parsansharmajs
- co2 hydrogenationTransféré parRohitKumar
- Publications%2ftca390Transféré paryemresimsek
- Chemical Kinetics RevisionTransféré parAshwin Balaji
- Chemical Kinetics Part - 2Transféré parsmi_santhosh
- enzymes.pptxTransféré parYing Fei Lim
- Kinetics of Isotopic Exchange and Mechanism of Sorption of Co(II) on Hydrous Stannic Oxide[1]Transféré parsramesh124
- 7-110415154419Transféré parFábio Ramalho
- M Sc Bangalore University SyllabusTransféré parche911
- Developments in the Modelling of Oxygen SteelmakingTransféré parrazor75ap
- Enzyme KineticsTransféré parShrikant Nimbalkar
- Memo 2Transféré parinitiative1972
- Chemical Looping Combustion and ReactionsTransféré parDoctorOberman
- Spring17-CrystalVioletKineticsTransféré parGlen
- 09 Adsorption Influenced Reactions StudentTransféré parLai Ming Yih
- Amatore 1983Transféré parGil Rocha
- CRE Theory QuestionsTransféré parJunaid Parker
- Kinetics of Glass DissolutionTransféré parlsueyin