Electrode Processes and Kinetics

(CHM-513)
(Lectures 15-18)
April 2023
Chapter 1
Electrochemical Methods: Fundamentals and Applications,
Bard A, Faulkner LR. John Wiley New York, 2001.
Chapter 1
Analytical Electrochemistry: Joseph Wang, John Wiley New
York,

.
 Linear Sweep Voltammetry

• In linear sweep voltammetry (LSV) a fixed potential

range is employed, much like potential step
measurements.
• However, in LSV the voltage is scanned from a lower
limit to an upper limit as shown below.

2
 Linear Sweep Voltammetry
• The voltage scan rate (v) is calculated from the slope
of the line.
• Clearly by changing the time taken to sweep the range
we alter the scan rate.
• The characteristics of the linear sweep
voltammogram recorded depend on a number of
factors including:

• The rate of the electron transfer reaction(s)

• The chemical reactivity of the electroactive species
• The voltage scan rate
3
 Linear Sweep Voltammetry
• In LSV measurements the current response is plotted as a
function of voltage rather than time, unlike potential step
measurements.

• For example, if we return to the Fe3+/Fe2+ system; then the following

voltammogram would be seen for a single voltage scan using an
electrolyte solution containing only Fe3+ resulting from a voltage
sweep;

4
 LSV
• The scan begins from the left hand side of the
current/voltage plot where no current flows.

• As the voltage is swept further to the right (to more

reductive values) a current begins to flow and
eventually reaches a peak before dropping.

• To rationalise this behaviour, we need to consider the

influence of voltage on the equilibrium established at
the electrode surface.

5
 LSV
• If we consider the electrochemical reduction
of Fe3+ to Fe2+, the rate of electron transfer is fast in
comparsion to the voltage sweep rate.
• Therefore, at the electrode surface an equilibrum is
established identical to that predicted by
thermodynamics.
• The Nernst equation predicts the relationship between
concentration and voltage (potential difference),

6
 LSV
• E = applied potential difference
• Eo =standard electrode potential.
• As the voltage is swept from V1 to V2 the
equilibrium position shifts from no conversion
at V1 to full conversion at V2 of the reactant at
the electrode surface.
• The exact form of the voltammogram can be rationalized
by considering the voltage and mass transport
effects.

7
 LSV
• As the voltage is initially swept from V1 the equilibrium at
the surface begins to alter and the current begins to
flow:

8
 LSV
• The current rises as the voltage is swept further from
its initial value as the equilibrium position is shifted
further to the right hand side, thus converting more
reactant.
• The peak occurs, since at some point the diffusion layer
has grown sufficiently above the electrode so that the
flux of reactant to the electrode is not fast enough to
satisfy that required by the Nernst equation.
• In this situation the current begins to drop just as it did in
the potential step measurements.
• The drop in current follows the same behavior as
predicted by the Cottrell equation.
9
 Effect of Scan Rate in LSV
• If the scan rate is altered, the current response
also changes.
• The figure below shows a series of linear sweep voltammograms recorded
at different scan rates for an electrolyte solution containing only Fe3+

10
 Effect of Scan Rate in LSV
• Each curve has the same form, but it is apparent that
the total current increases with increasing scan
rate.
• This again can be rationalized by considering the size of
the diffusion layer and the time taken to record the
scan.

• Clearly the linear sweep voltammogram will take

longer to record as the scan rate is decreased.

• Therefore, the size of the diffusion layer above the

electrode surface will be different depending upon the
voltage scan rate used. 11
 Effect of Scan Rate in LSV
• In a slow voltage scan, the diffusion layer will grow much
further from the electrode in comparison to a fast scan.

• Consequently, the flux to the electrode surface is

considerably smaller at slow scan rates than it is at
faster rates.

• As the current is proportional to the flux towards the

electrode, the magnitude of the current will be lower
at slow scan rates and higher at high rates.

12
 Effect of Scan Rate in LSV
• Although there is no time axis on the graph the
voltage scan rate (and therefore the time taken
to record the voltammogram) do strongly effect
the behaviour seen.
• The position of the current maximum, it is clear
that the peak occurs at the same voltage
and this is a characteristic of electrode
reactions which have rapid electron transfer
kinetics.
• These rapid processes are often referred to as
reversible electron transfer reactions.

13
 what would happen if the electron transfer
processes were 'slow' (relative to the
voltage scan rate)?
• For these cases, the
reactions are referred to as
quasi-reversible or
irreversible electron transfer
reactions.

• The figure shows a series of

voltammograms recorded at
a single voltage sweep rate
for different values of the
reduction rate constant (kred)

14
 Continued
• In this situation, the voltage applied will not result in the generation
of the concentrations at the electrode surface predicted by the
Nernst equation.

• This happens because the kinetics of the reaction are 'slow' and
thus the equilibria are not established rapidly (in comparison to
the voltage scan rate).

• In this situation, the overall form of the voltammogram recorded is

similar to that above, but unlike the reversible reaction now the
position of the current maximum shifts depending upon the reduction
rate constant (and also the voltage scan rate).

• This occurs because the current takes more time to

respond to the the applied voltage than the
reversible case. 15
 Potential-Sweep Experiments

• Let us move to a voltammetric experiment involving a linear

potential scan, the reduction of O to R and a quiescent solution.

• The slope of the concentration gradient is given by:

(CO(b, t)- CO(0, t))/δ
where CO(b, t) and CO(0, t) are the bulk and surface
concentrations of O.

• The change in the slope, and hence the resulting current, is due
to changes of both CO(0, t) and δ.
•

16
 Potential-Sweep Experiments
• First, as the potential is scanned negatively, and approaches the
standard potential (Eo) of the couple, the surface concentration
rapidly decreases in accordance to the Nernst equation (equation 1-
2).
• For example, at a potential equal to Eo the concentration ratio is
unity
(CO(0, t)/CR(0, t) = 1)
• For a potential 59 mV more negative than Eo, CR(0, t) is
present at 10-fold excess (CO(0, t)/CR(0, t) = 1/10, n = 1).

• The decrease in CO(0, t) is coupled with an increase in the diffusion

layer thickness, which dominates the change in the slope after CO(0,
t) approaches zero. The net result is a peak-shaped voltammogram

17
Potential-Sweep Experiments

18
• Concentration profiles (left) for different potentials during a linear sweep
voltammetric experiment in unstirred solution.

The resulting voltammogram is shown on the right, along with the points
corresponding to each concentration gradient

• Shrinking the electrode dimension to the micrometer domain

results in a sigmoidal-shaped voltammetric response under
quiescent conditions

19
 Reactions Controlled by the Rate of
Electron Transfer
• Consider experiments in which the current is controlled by the
rate of electron transfer (i.e., reactions with sufficiently fast mass
transport).

The hydrodynamic boundary (Prandtl)

layer. Also shown (as dotted line), is the
diffusion layer.
20
 Reactions Controlled by the Rate of
Electron Transfer
• Consider again the electron-transfer reaction: O + ne- = R; the actual electron
transfer step involves transfer of the electron between the conduction band of
the electrode and a molecular orbital of O or R (e.g., for a reduction, from the
conduction band into an unoccupied orbital in O). The rate of the forward
(reduction) reaction, Vf , is first order in O:

21
 Heterogenous rate constants
• Where
• ko = the standard heterogeneous rate constant
• cx = transfer coefficient.
• The value of ko (in cm s-1) reflects the reaction between the particular reactant and
the electrode material used.
• The value of cx (between zero and unity) reflects the symmetry of the free energy
curve (with respect to the reactants and products).
• For symmetric curves, cx will be close to 0.5; cx is a measure of the fraction of
energy that is put into the system that is used to lower the activation energy
• Overall, equations (1-18) and (1-19) indicate that by changing the applied
potential we influence kf and kb in an exponential fashion.
• Positive and negative potentials thus speed up the oxidation and reduction
reactions, respectively.
• For an oxidation, the energy of the electrons in the donor orbital of R must
be equal or higher than the energy of electrons in the electrode.
• For reduction, the energy of the electrons in the electrode must be higher
than their energy in the receptor orbital of R. 22
Current-potential relationship for reactions
controlled by the rate of electron transfer

23
Current-potential relationship for reactions controlled by
the rate of electron transfer.
• The net current depends on both the operating potential and the surface
concentration of each form of the redox couple.
• For example, Figure 1-7 displays the current-potential dependence for the case
where CO(0, t) = CR(0, t) and cx = 0.50.
• Large negative potentials accelerate the movement of charge in the cathodic
direction, and also decelerate the charge movement in the opposite direction.
• As a result, the anodic current component becomes negligible and the net
current merges with the cathodic component.
• The acceleration and deceleration of the cathodic and anodic currents are not
necessarily as symmetric as depicted in Figure 1.7, and would differ for cx values
different than 0.5.
• Similarly, no cathodic current contribution is observed at sufficiently large
positive potentials.
• When E = Eeq, no net current is flowing. This situation, however, is dynamic,
with continuous movement of charge carriers in both directions, and equal
opposing anodic and cathodic current components.
24
 Fig: 1.7

Current-potential curve for the system O + ne- = R, assuming that electron- transfer is
rate limiting, CO = CR, and cx = 0.5.
The dotted lines show the cathodic (ic ) and anodic (ia) components.

25
Butler-Volmer equation

26
 Tafel Equation

• This logarithmic current-potential dependence was derived by Tafel;

and is known as the Tafel equation.

• By plotting log i vs. ƞ one obtains the Tafel plots for the
cathodic and anodic branches of the current-overvoltage curve
(Figure 1-8).

• Such plots are linear only at high values of overpotentials;

severe deviations from linearity are observed as ƞ approaches zero.

• Extrapolation of the linear portions of these plots to the zero

overvoltage gives an intercept that corresponds to log i0; the slope can
be used to obtain the value of the transfer coefficient cx.
27
•
Tafel plots for the cathodic and anodic branches
of the current-potential curve.

28
 Second form of Tafel Equation

• Another form of the Tafel equation is obtained by

rearrangement of equation (1-28):

• with b, the Tafel slope, having the value of 2.303 RT

/αnF.
• For cx = 0.5 and n = 1, this corresponds to 118 mV (at 25
oC).

• Equation (1-29) indicates that the application of small

potentials (beyond the equilibrium potential) can
increase the current by many orders of magnitude.
• In practice, however, the current could not rise to an infinite value
due to restrictions from the rate at which the reactant reaches the
29
surface.
 Activated Complex Theory
• The effect of the operating potential upon the rate constants (equations 1-18 and
1-19) can be understood in terms of the free energy barrier.

• Figure 1-9 shows a typical Morse potential energy curve for the reaction:
O + ne- = R, at an inert metallic electrode (with O and R being soluble)
• Because of the somewhat different structures of O and R, there is a barrier to
electron transfer (associated with changes in bond lengths and bond angles).
• In order for the transition from the oxidized form to occur, it is thus necessary to
overcome the free energy of activation.
• The frequency with which the electron crosses the energy barrier as it moves from the
electrode to O (i.e., the rate constant) is given by:

30
Free energy curve for a redox process at a potential more positive than the
equilibrium value.

31
Factors affecting rate of reaction

32
 Free energy change in non-equilibirum
situations
• By varying the potential of the working electrode, we can
influence the free energy of its resident electrons, thus making
one reaction more favorable.
• For example, a potential shift E from the equilibrium value moves
the O + ne- curve up or down by ɸ= -nFE. The dotted line in Figure
1-10 displays such a change for the case of a positive E. The dotted
line in Figure 1-10 displays such a change for the case of positive E.

33
Effect of a change in the applied potential on the free
energies of activation for reduction and oxidation.

34
35
 THE ELECTRICAL DOUBLE LAYER
• The electrical double layer is the array of charged
particles and/or oriented dipoles that exists at every
material interface.
• In electrochemistry, such a layer reflects the ionic zones
formed in the solution to compensate for the excess of
charge on the electrode (qe).
• A positively charged electrode thus attracts a layer
of negative ions (and vice versa).
• Since the interface must be neutral, qe + qs = 0 (where
qs is the charge of the ions in the nearby solution).
• Accordingly, such a counter layer is made of ions of
opposite sign to that of the electrode.

36
 THE ELECTRICAL DOUBLE LAYER
• The electrical double layer has a complex structure of several
distinct parts.
• IHP: The inner layer (closest to the electrode), known as the inner Helmholtz
plane, contains solvent molecules and specifically adsorbed ions (which are not
fully solvated). It is defined by the locus of points for the specifically adsorbed ions.
• OHP: The next layer, the outer Helmholtz plane, reflects the imaginary plane
passing through the center of solvated ions at their closest approach to the
surface. The solvated ions are nonspecifically adsorbed and are attracted to the
surface by long- range coulombic forces.
• Both Helmholtz layers represent the compact layer. Such a compact layer of
charges is strongly held by the electrode and can survive even when the electrode is
pulled out of the solution.
• The Helmholtz model does not take into account the thermal motion of ions, which
loosens them from the compact layer.

37
 GUOY LAYER
• The outer layer (beyond the compact layer), referred to as the
diffuse layer (or Gouy layer), is a three-dimensional region of
scattered ions, which extends from the OHP into the bulk solution.
• Such an ionic distribution reflects the counterbalance between
ordering forces of the electrical field and the disorder caused by a
random thermal motion.
• Based on the equilibrium between these two opposing effects,
the concentration of ionic species at a given distance from the
surface, C(x), decays exponentially with the ratio between the
electrostatic energy (zFɸ) and the thermal energy (RT ), in
accordance with the Boltzmann equation:

• The total charge of the compact and diffuse layers equals (and is
38
opposite in sign to) the net charge on the electrode side
Schematic representation of the electrical double
layer
IHP = inner Helmholtz plane; OHP = outer Helmholtz plane.

39
Variation of the potential across the electrical
double layer.

• The potential-distance profile

across the double- layer region
involves two segments, with a
linear increase up to the OHP
and an exponential increase
within the diffuse layer.

• Depending upon the ionic

strength, the thickness of the
double layer may extend to more
than 10nm.

• The electrical double layer

resembles an ordinary (parallel-
plate) capacitor. 40
 Electrical double layer.

• For an ideal capacitor, the charge (q) is directly proportional to

the potential difference:
q = CE (1-44)
• Where C is the capacitance (in farads, F), the ratio of the charge stored to the
applied potential. The potential-charge relationship for the electrical double layer
is
• q = CdlA(E -Epzc) (1-45)
• where Cdl is the capacitance per unit area and Epzc is the potential of zero charge
(i.e., where the sign of the electrode charge reverses, and no net charge exists in the
double layer). Cdl values are usually in the range 10-40 µF cm-2.

41