29 Dynamics of electron transfer

Solutions to exercises
Discussion questions
E29.1(b) No solution.
E29.2(b) The net current density at an electrode is j ; j0 is the exchange current density; α is the transfer
coefficient; f is the ratio F /RT ; and η is the overpotential.
(a) j = j0 f η is the current density in the low overpotential limit.
(b) j = j0 e(1−α)f η applies when the overpotential is large and positive.
(c) j = −j0 e−αf η applies when the overpotential is large and negative.
E29.3(b) In cyclic voltammetry, the current at a working electrode is monitored as the applied potential differ-
ence is changed back and forth at a constant rate between pre-set limits (Figs 29.20 and 29.21). As the
potential difference approaches E − 
−
(Ox, Red) for a solution that contains the reduced component
(Red), current begins to flow as Red is oxidized. When the potential difference is swept beyond E − 
−

(Ox, Red), the current passes through a maximum and then falls as all the Red near the electrode is
consumed and converted to Ox, the oxidized form. When the direction of the sweep is reversed and the
potential difference passes through E − −
(Ox, Red), current flows in the reverse direction. This current
is caused by the reduction of the Ox formed near the electrode on the forward sweep. It passes through
the maximum as Ox near the electrode is consumed. The forward and reverse current maxima bracket
E− 
−
(Ox, Red), so the species present can be identified. Furthermore, the forward and reverse peak
currents are proportional to the concentration of the couple in the solution, and vary with the sweep
rate. If the electron transfer at the electrode is rapid, so that the ratio of the concentrations of Ox and
Red at the electrode surface have their equilibrium values for the applied potential (that is, their relative
concentrations are given by the Nernst equation), the voltammetry is said to be reversible. In this case,
the peak separation is independent of the sweep rate and equal to (59 mV)/n at room temperature,
where n is the number of electrons transferred. If the rate of electron transfer is low, the voltammetry
is said to be irreversible. Now, the peak separation is greater than (59 mV)/n and increases with
increasing sweep rate. If homogeneous chemical reactions accompany the oxidation or reduction of
the couple at the electrode, the shape of the voltammogram changes, and the observed changes give
valuable information about the kinetics of the reactions as well as the identities of the species present.
E29.4(b) Corrosion is an electrochemical process. We will illustrate it with the example of the rusting of iron,
but the same principles apply to other corrosive processes. The electrochemical basis of corrosion
in the presence of water and oxygen is revealed by comparing the standard potentials of the metal
reduction, such as

Fe2+ (aq) + 2e− → Fe(s) E−


−
= −0.44 V

with the values for one of the following half-reactions

In acidic solution
(a) 2 H+ (aq) + 2 e− → H2 (g) E−

−
= 0V
(b) 4 H+ (aq) + O2 (g) + 4 e− → 2H2 O(l) E−

−
= +1.23 V
In basic solution:
(c) 2H2 O(l) + O2 (g) + 4 e− → 4OH− (aq) E−

−
= +0.40 V
DYNAMICS OF ELECTRON TRANSFER 467

Because all three redox couples have standard potentials more positive than E − 
−
(Fe2+ /Fe), all three
can drive the oxidation of iron to iron(II). The electrode potentials we have quoted are standard values,
and they change with the pH of the medium. For the first two

E(a) = E −

−
(a) + (RT /F ) ln a(H+ ) = −(0.059 V)pH
E(b) = E −

−
(b) + (RT /F ) ln a(H+ ) = 1.23 V − (0.059 V)pH

These expressions let us judge at what pH the iron will have a tendency to oxidize (see Chapter 10).
A thermodynamic discussion of corrosion, however, only indicates whether a tendency to corrode
exists. If there is a thermodynamic tendency, we must examine the kinetics of the processes involved
to see whether the process occurs at a significant rate. The effect of the exchange current density on
the corrosion rate can be seen by considering the specific case of iron in contact with acidified water.
Thermodynamically, either the hydrogen or oxygen reduction reaction (a) or (b) is effective. However,
the exchange current density of reaction (b) on iron is only about 10−14 A cm−2 , whereas for (a) it is
10−6 A cm−2 . The latter therefore dominates kinetically, and iron corrodes by hydrogen evolution in
acidic solution. For corrosion reactions with similar exchange current densities, eqn 29.62 predicts
that the rate of corrosion is high when E is large. That is, rapid corrosion can be expected when the
oxidizing and reducing couples have widely differing electrode potentials.
Several techniques for inhibiting corrosion are available. First, from eqn 62 we see that the rate
of corrosion depends on the surfaces exposed: if either A or A is zero, then the corrosion current is
zero. This interpretation points to a trivial, yet often effective, method of slowing corrosion: cover
the surface with some impermeable layer, such as paint, which prevents access of damp air. Paint
also increases the effective solution resistance between the cathode and anode patches on the surface.
Another form of surface coating is provided by galvanizing, the coating of an iron object with
zinc. Because the latter’s standard potential is −0.76 V, which is more negative than that of the iron
couple, the corrosion of zinc is thermodynamically favoured and the iron survives (the zinc survives
because it is protected by a hydrated oxide layer).
Another method of protection is to change the electric potential of the object by pumping in electrons
that can be used to satisfy the demands of the oxygen reduction without involving the oxidation of
the metal. In cathodic protection, the object is connected to a metal with a more negative standard
potential (such as magnesium, −2.36 V). The magnesium acts as a sacrificial anode, supplying its
own electrons to the iron and becoming oxidized to Mg2+ in the process.

Numerical exercises
E29.5(b) Equation 29.14 holds for a donor–acceptor pair separated by a constant distance, assuming that the
reorganization energy is constant:

(r G−

− )2 r G −

−
ln ket = − − + constant,
4λRT 2RT

or equivalently

(r G−

− )2 r G −

−
ln ket = − − + constant,
4λkT 2kT

if energies are expressed as molecular rather than molar quantities. Two sets of rate constants and
reaction Gibbs energies can be used to generate two equation (eqn 29.14 applied to the two sets) in
468 INSTRUCTOR’S MANUAL

two unknowns: λ and the constant.

(r G1−

− 2
) r G1−

−
(r G2−

− 2
) r G2−

−
ln ket, l + + = constant = ln ket,2 + + ,
4λkT 2kT 4λkT 2kT

(r G1−

) − (r G2−
− 2 
− 2
) ket,2 r G2−

−
− r G1−

−
so = ln +
4λkT ket,1 2kT

(r G1−

− 2
) − (r G2− − 2
)
and λ =
,
k r G2 −r G−
−− −
4 kT ln ket,2
et,1
+ 2
1

(−0.665 eV)2 − (−0.975 eV)2

λ = = 1.531 eV
4(1.381×10−23 J K−1 )(298 K) 3.33×106
1.602×10−19 J eV−1
ln 2.02×10 5 − 2(0.975 − 0.665) eV

If we knew the activation Gibbs energy, we could use eqn 29.12 to compute HDA from either rate
constant, and we can compute the activation Gibbs energy from eqn 29.4:
(r G−

− + λ)2 [(−0.665 + 1.531)eV]2
‡ G = = = 0.122 eV.
4λ 4(1.531 eV)

 1/2  
2 HDA 2 π3 −‡ G
Now ket = exp ,
h 4λkT kT


  
hket 1/2 4λkT 1/4 ‡ G
so HDA = exp ,
2 π3 2kT
 1/2
(6.626 × 10−34 J s)(2.02 × 105 s−1 )
HDA =
2
 1/4
4(1.531 eV)(1.602 × 10−19 J eV−1 )(1.381 × 10−23 J K−1 )(298 K)
×
π3
 
(0.122 eV)(1.602 × 10−19 J eV−1 )
× exp = 9.39 × 10−24 J
2(1.381 × 10−23 J K−1 )(298 K)

E29.6(b) Equation 29.13 applies. In E29.6(a), we found the parameter β to equal 12 nm−1 , so:
ln ket /s−1 = −βr + constant so constant = ln ket /s−1 + βr,
and constant = ln 2.02 × 105 + (12 nm−1 )(1.11 nm) = 25.
Taking the exponential of eqn 29.13 yields:

ket = e−βr+constant s−1 = e−(12/nm)(1.48 nm)+25 s−1 = 1.4 × 103 s−1 .

E29.7(b) Disregarding signs, the electric field is the gradient of the electrical potential
dφ φ σ σ 0.12 C m−2
E= ≈ = = = = 2.8 × 108 V m−1
dx d ε εr ε0 (48) × (8.854 × 10−12 J−1 C2 m−1 )
DYNAMICS OF ELECTRON TRANSFER 469

E29.8(b) In the high overpotential limit

j1 F 1
j = j0 e(1−α)f η so = e(1−α)f (η1 −η2 ) where f = =
j2 RT 25.69 mV
The overpotential η2 is

  
1 j2 25.69 mV 7255 mA cm−2
η2 = η1 + ln = 105 mV + × ln
f (1 − α) j1 1 − 0.42 17.0 mA cm−2

= 373 mV

E29.9(b) In the high overpotential limit

j = j0 e(1−α)f η so j0 = j e(α−1)f η

j0 = (17.0 mA cm−2 ) × e{(0.42−1)×(105 mV)/(25.69 mV)} = 1.6 mA cm−2

E29.10(b) In the high overpotential limit

j1
j = j0 e(1−α)f η so = e(1−α)f (η1 −η2 ) and j2 = j1 e(1−α)f (η2 −η1 ) .
j2
So the current density at 0.60 V is

j2 = (1.22 mA cm−2 ) × e{(1−0.50)×(0.60 V−0.50 V)/(0.02569 V)} = 8.5 mA cm−2

Note. The exercise says the data refer to the same material and at the same temperature as the previous
exercise (29.10(a)), yet the results for the current density at the same overpotential differ by a factor
of over 5!
E29.11(b) (a) The Butler–Volmer equation gives
 
j = j0 e(1−α)f η − e−αf η
 
= (2.5 × 10−3 A cm−2 ) × e{(1−0.58)×(0.30 V)/(0.02569 V)} − e−{(0.58)×(0.30 V)/(0.02569 V)}

= 0.34 A cm−2
(b) According to the Tafel equation
j = j0 e(1−α)f η

= (2.5 × 10−3 A cm−2 )e{(1−0.58)×(0.30 V)/(0.02569 V)} = 0.34 A cm−2

The validity of the Tafel equation improves as the overpotential increases.
E29.12(b) The limiting current density is
zF Dc
jlim =
δ
but the diffusivity is related to the ionic conductivity (Chapter 24)
λRT cλ
D= 2 2 so jlim =
z F δzf
(1.5 mol m−3 ) × (10.60 × 10−3 S m2 mol−1 ) × (0.02569 V)
jlim =
(0.32 × 10−3 m) × (+1)

= 1.3 A m−2
470 INSTRUCTOR’S MANUAL

E29.13(b) For the iron electrode E − 

−
= −0.44 V (Table 10.7) and the Nernst equation for this electrode
(Section 10.5) is


−

− RT 1
E=E − ln ν=2
νF [Fe2+ ]
Since the hydrogen overpotential is 0.60 V evolution of H2 will begin when the potential of the Fe
electrode reaches −0.60 V. Thus
0.02569 V
−0.60 V = −0.44 V + ln[Fe2+ ]
2
−0.16 V
ln[Fe2+ ] = = −12.5
0.0128 V
[Fe2+ ] = 4 × 10−6 mol L−1

Comment. Essentially all Fe2+ has been removed by deposition before evolution of H2 begins.
E29.14(b) The zero-current potential of the electrode is given by the Nernst equation

RT 1 a(Fe2+ ) 1 a(Fe2+ )
E = E−

−
− ln Q = E −

−
− ln = 0.77 V − ln
νF f a(Fe3+ ) f a(Fe3+ )
The Butler–Volmer equation gives

j = j0 (e(1−α)f η − e−αf η ) = j0 (e(0.42)f η − e−0.58f η )

where η is the overpotential, defined as the working potential E  minus the zero-current potential E.

1 a(Fe2+ ) 1
η = E  − 0.77 V + ln = E  − 0.77 V + ln r,
f a(Fe )
3+ f
where r is the ratio of activities; so

j = j0 (e(0.42)E /f e{(0.42)×(−0.77 V)/(0.02569 V)} r 0.42

− e(−0.58)E /f e{(−0.58)×(−0.77 V)/(0.02569 V)} r −0.58 )

Specializing to the condition that the ions have equal activities yields
 
j = (2.5 mA cm−2 ) × [e(0.42)E /f × (3.41 × 10−6 ) − e(−0.58)E /f × (3.55 × 107 )]

E29.15(b) Note. The exercise did not supply values for j0 or α. Assuming α = 0.5, only j/j0 is calculated.
From Exercise 29.14(b)
 −−  −−
j = j0 (e(0.50)E /f e−(0.50)E /f r 0.50 − e(−0.50)E /f e(0.50)E /f r −0.50 )
 
= 2j0 sinh 21 f E  − 21 f E −
− + 1 ln r ,
2

so, if the working potential is set at 0.50 V, then

 
j = 2j0 sinh 21 (0.91 V)/(0.02569 V) + 21 ln r
 
j/j0 = 2 sinh 8.48 + 21 ln r
 
At r = 0.1: j/j0 = 2 sinh 8.48 + 21 ln 0.10 = 1.5 × 103 mA cm−2 = 1.5 A cm−2
DYNAMICS OF ELECTRON TRANSFER 471

At r = 1: j/j0 = 2 sinh(8.48 + 0.0) = 4.8 × 103 mA cm−2 = 4.8 A cm−2

 
At r = 10: j/j0 = 2 sinh 8.48 + 21 ln 10 = 1.5 × 104 mA cm−2 = 15 A cm−2
E29.16(b) The potential needed to sustain a given current depends on the activities of the reactants, but the
overpotential does not. The Butler–Volmer equation says

j = j0 (e(1−α)f η − e−αf η )
This cannot be solved analytically for η, but in the high-overpotential limit, it reduces to the Tafel
equation

1 j 0.02569 V 15 mA cm−2
j = j0 e(1−α)f η so η = ln = ln
(1 − α)f j0 1 − 0.75 4.0 × 10−2 mA cm−2
η = 0.61 V

This is a sufficiently large overpotential to justify use of the Tafel equation.

E29.17(b) The number of singly charged particles transported per unit time per unit area at equilibrium is the
exchange current density divided by the charge
j0
N=
e
The frequency f of participation per atom on an electrode is

f = Na

where a is the effective area of an atom on the electrode surface.

For the Cu, H2 |H+ electrode

j0 1.0 × 10−6 A cm−2

N= = = 6.2 × 1012 s−1 cm−2
e 1.602 × 10−19 C
f = N a = (6.2 × 1012 s−1 cm−2 ) × (260 × 10−10 cm)2

= 4.2 × 10−3 s−1

For the Pt|Ce4+ , Ce3+ electrode

j0 4.0 × 10−5 A cm−2

N= = = 2.5 × 1014 s−1 cm−2
e 1.602 × 10−19 C
The frequency f of participation per atom on an electrode is

f = N a = (2.5 × 1014 s−1 cm−2 ) × (260 × 10−10 cm)2 = 0.17 s−1

E29.18(b) The resistance R of an ohmic resistor is

potential η
R= =
current jA
where A is the surface area of the electrode. The overpotential in the low overpotential limit is
j 1
η= so R =
fj0 fj0 A
472 INSTRUCTOR’S MANUAL

0.02569 V
(a) R= = 5.1 × 109 & = 5.1 G&
(5.0 × 10−12 A cm−2 ) × (1.0 cm2 )
0.02569 V
(b) R= = 10 &
(2.5 × 10−3 A cm−2 ) × (1.0 cm2 )

E29.19(b) No reduction of cations to metal will occur until the cathode potential is dropped below the zero-
current potential for the reduction of Ni2+ (−0.23 V at unit activity). Deposition of Ni will occur at
an appreciable rate after the potential drops significantly below this value; however, the deposition of
Fe will begin (albeit slowly) after the potential is brought below −0.44 V. If the goal is to deposit pure
Ni, then the Ni will be deposited rather slowly at just above −0.44 V; then the Fe can be deposited
rapidly by dropping the potential well below −0.44 V.
E29.20(b) As was noted in Exercise 29.10(a), an overpotential of 0.6 V or so is necessary to obtain significant
deposition or evolution, so H2 is evolved from acid solution at a potential of about −0.6 V. The
reduction potential of Cd2+ is more positive than this (−0.40 V), so Cd will deposit (albeit slowly)
from Cd2+ before H2 evolution.
E29.21(b) Zn can be deposited if the H+ discharge current is less than about 1 mA cm−2 . The exchange current,
according to the high negative overpotential limit, is

j = j0 e−αf η

At the standard potential for reduction of Zn2+ (−0.76 V)

j = (0.79 mA cm−2 ) × e−{(0.5)×(−0.76 V)/(0.02569 V)} = 2.1 × 109 mA cm−2

much too large to allow deposition . (That is, H2 would begin being evolved, and fast, long before
Zn began to deposit.)
E29.22(b) Fe can be deposited if the H+ discharge current is less than about 1 mA cm−2 . The exchange current,
according to the high negative overpotential limit, is

j = j0 e−αf η

At the standard potential for reduction of Fe2+ (−0.44 V)

j = (1 × 10−6 A cm−2 ) × e−{(0.5)×(−0.44 V)/(0.02569 V)} = 5.2 × 10−3 A cm−2

a bit too large to allow deposition . (That is, H2 would begin being evolved at a moderate rate before
Fe began to deposit.)
E29.23(b) The lead acid battery half-cells are

Pb4+ + 2e− → Pb2+ 1.67 V

and Pb2+ + 2e− → Pb −0.13 V,

for a total of E −

−
= 1.80 V . Power is

P = I V = (100 × 10−3 A) × (1.80 V) = 0.180 W

if the cell were operating at its zero-current potential yet producing 100 mA.
DYNAMICS OF ELECTRON TRANSFER 473

E29.24(b) The thermodynamic limit to the zero-current potential under standard conditions is the standard
potential E −

−
, which is related to the standard Gibbs energy by

−r G−

−
r G −

−
= −νF E −

−
so E=
νF
The reaction is

C3 H8 (g) + 7O2 (g) → 3CO2 (g) + 4H2 O(l) with ν = 14

r G−

−
= 3f G−

−
(CO2 ) + 4f G−

−
(H2 O) − f G−

−
(C3 H8 ) − 7f G−

−
(O2 )
= (3 × (−394.36) + 4 × (−237.13) − (−23.49) − 0) kJ mol−1 = −1319.4 kJ mol−1

1319.39 × 103 J mol−1

so E −

−
= = 0.97675 V
14 × (96485 C mol−1 )
E29.25(b) Two electrons are lost in the corrosion of each zinc atom, so the number of zinc atoms lost is half the
number of electrons which flow per unit time, i.e. half the current divided by the electron charge. The
volume taken up by those zinc atoms is their number divided by their number density; their number
density is their mass density divided by molar mass times Avogadro’s number. Dividing the volume
of the corroded zinc over the surface from which they are corroded gives the linear corrosion rate;
this affects the calculation by changing the current to the current density. So the rate of corrosion is

jM (1.0 A m−2 ) × (65.39 × 10−3 kg mol−1 )

rate = =
2eρNA 2(1.602 × 10−19 C) × (7133 kg m−3 ) × (6.022 × 1023 mol−1 )
= 4.8 × 10−11 m s−1
= (4.8 × 10−11 m s−1 ) × (103 mm m−1 ) × (3600 × 24 × 365 s y−1 )

= 1.5 mm y−1

Solutions to problems
Solutions to numerical problems
RT
P29.3 E = E−

−
+ ln a(M+ )
zF
Deposition may occur when the potential falls to below E and so simultaneous deposition will occur
if the two potentials are the same; hence the relative activities are given by

RT RT
E−

−
(Sn, Sn2+ ) + ln a(Sn2+ ) = E −−
(Pb, Pb2+ ) + ln a(Pb2+ )
2F 2F


a(Sn2+ ) 2F (2) × (−0.126 + 0.136) V
or ln = {E −
−
(Pb, Pb2+ ) − E −
−
(Sn, Sn2+ )} = = 0.78
a(Pb2+ ) RT 0.0257 V

That is, we require a(Sn2+ ) ≈ 2.2a(Pb2+ )

1/2
εRT
P29.8 rD = [22.50]
2ρF 2 I b −

−

1 2
where I = z (bi /b −

−
), b −

−
= 1 mol kg−1 [10.18]
2 i i
474 INSTRUCTOR’S MANUAL

For NaCl: I b −

−
= bNaCl ≈ [NaCl] assuming 100 per cent dissociation.
 
For Na2 SO4 : I b −

−
= 21 (1)2 (2bNa2 SO4 ) + (2)2 bNa2 SO4

= 3bNa2 SO4 ≈ 3[Na2 SO4 ] assuming 100 per cent dissociation.

 1/2
−12 J−1 C2 m −1 ) × (8.315 J K −1 mol−1 ) × (298.15 K)
1/2
78.54 × (8.854 × 10 1
rD ≈   −3  6 3  ×
2 × (1.00 g cm−3 ) × 10 g kg × 10mcm × (96485 C mol−1 )2 I b−
−
3

3.043 × 10−10 m mol1/2 kg−1/2

≈
(I b −

− )1/2

304.3 pm mol1/2 kg−1/2

≈
(I b −

− )1/2

These equations can be used to produce the graph of rD against bsalt shown in Fig. 29.1. Note the
contraction of the double layer with increasing ionic strength.

–
5000

4000

3000

2000

1000

0
0 20 40 60 80 100
Figure 29.1

P29.9 This problem differs somewhat from the simpler one-electron transfers considered in the text. In
place of Ox + e− → Red we have here

In3+ + 3e− → In

namely, a three-electron transfer. Therefore eqns 29.25, 29.26, and all subsequent equations including
the Butler–Volmer equation [29.35] and the Tafel equations [29.38–29.41] need to be modified by
DYNAMICS OF ELECTRON TRANSFER 475

including the factor z (in this case 3) in the equation. Thus, in place of eqn 29.26, we have

‡ Gc = ‡ Gc (0) + zαF φ

and in place of eqns 29.39 and 29.41

ln j = ln j0 + z(1 − α)f η anode

ln(−j ) = ln j0 − zαf η cathode

We draw up the following table

j/(A m−2 ) −E/V η/V ln(j/(A m−2 ))
0 0.388 0
0.590 0.365 0.023 −0.5276
1.438 0.350 0.038 0.3633
3.507 0.335 0.053 1.255

We now do a linear regression of ln j against η with the following results (see Fig. 29.2)

1.5

1.0

0.5

0.0

–0.5

–1.0
0.020 0.025 0.030 0.035 0.040 0.045 0.050 0.055
Figure 29.2

z(1 − α)f = 59.42 V−1 , standard deviation = 0.0154

ln j0 = −1.894, standard deviation = 0.0006
R = 1 (almost exact)

Thus, although there are only three data points, the fit to the Tafel equation is almost exact. Solving
for α from z(1 − α)f = 59.42 V−1 , we obtain
59.42 V−1 59.42 V−1
α =1− =1− × (0.025262 V)
3f 3

= 0.4996 = 0.50
476 INSTRUCTOR’S MANUAL

which matches the usual value of α exactly.

j0 = e−1.894 = 0.150 A m−2

The cathodic current density is obtained from

ln(−jc ) = ln j0 − zαf η η = 0.023 V at − E/V = 0.365

= −1.894 − (3 × 0.4996 × 0.023)/(0.025 262)
= −3.259
−jc = e−3.259 = 0.0384 A m−2

jc = −0.038 A m−2

P29.12 At large positive values of the overpotential the current density is anodic.
 
j = j0 e(1−α)f η − e−αf η [29.35]

≈ j0 e(1−α)f η = ja [29.34]
ln j = ln j0 + (1 − α)f η

Performing a linear regression analysis of ln j against η, we find

ln(j0 /(mA m−2 )) = −10.826, standard deviation = 0.287

−1
(1 − α)f = 19.550 V , standard deviation = 0.355
R = 0.999 01

j0 = e−10.826 mA m−2 = 2.00 × 10−5 mA m−2

19.550 V−1 19.550 V−1
α =1− =1−
f (0.025693 V)−1
α = 0.498

The linear regression explains 99.90 per cent of the variation in a ln j against η plot and standard
deviations are low. There are no deviations from the Tafel equation/plot.

Solutions to theoretical problems

P29.14 (a) First, assume that eqn 4 applies to the bimolecular processes under consideration in this problem.
(Cf. P29.1.) Thus,
−
− −
− −
−
(r G11 + λ11 )2 r G22 + λ22 )2 (r G12 + λ12 )2
‡ G11 = , ‡ G22 = , ‡ G12 =
4λ11 4λ22 4λ12
Because the standard free energy for elctron self-exchange is zero, these simplify to:

λ211
‡ G11 = = λ11 /4 and ‡ G22 = λ22 /4.
4λ11
−
− 2 −
−
(r G12 ) + λ212 + 2λ12 r G12
‡ G12 =
4λ12
DYNAMICS OF ELECTRON TRANSFER 477

−
−
(b) If r G12  λ12 , then we may drop the quadratic term in the numerator, leaving:
−
−
‡ G12 ≈ λ12 /4 + r G12 /2.
Assume that λ12 = (λ11 + λ22 )/2, so
λ12 /4 = (λ11 /4 + λ22 /4)/2 = (‡ G11 + ‡ G22 )/2.
Thus, we have:
−
−
‡ G12 ≈ (‡ G11 + ‡ G22 + r G12 )/2.

(c) According to activated complex theory, we can write for the self-exchange reactions:
   
−‡ G11 −‡ G22
k11 = κ11 ν11 exp and k22 = κ22 ν22 exp .
RT RT

(d) According to activated complex theory, we can write:

   
−
−
−‡ G12 −‡ G11 − ‡ G22 − r G12
k12 = κ12 ν12 exp ≈ κ12 ν12 exp .
RT 2RT

(e) Finally, we simplify by assuming that all κν terms are identical, so:
      1
−

−
−‡ G11 −‡ G22 −r G12
k12 ≈ κν exp κν exp exp /2.
RT RT RT

The final exponential is the equilibrium constant; the first two exponentials with their factors of κν
are electron self-exchange rate constants, so:

k12 ≈ (k11 k22 K)1/2 .

P29.16 Let η oscillate between η+ and η− around a mean value η0 . Then η− is large and positive (and
η+ > η− ),
j ≈ j0 e(1−α)ηf = j0 e(1/2)ηf [α = 0.5]
and η varies as depicted in Fig. 29.3(a).

Figure 29.3(a)

Therefore, j is a chain of increasing and decreasing exponential functions,

j = j0 e(η− +γ t)f/2 ∝ e−t/τ
2RT
during the increasing phase of η, where τ = , γ a constant, and
γF

j = j0 e(η+ −γ t)f/2 ∝ e−t/τ

478 INSTRUCTOR’S MANUAL

during the decreasing phase. This is depicted in Fig. 29.3(b).

Figure 29.3(b)


cF D
× (1 − ef η )[29.51; z = 1] = jL (1 − eF η /RT )
c c
P29.17 j=
δ

The form of this expression is illustrated in Fig. 29.4.

For the anion current, the sign of ηc is changed, and the current of anions approaches its limiting
value as ηc becomes more positive (Fig. 29.4).

Cations

Anions Figure 29.4

P29.19 Does eqn 29.13

ln ket = −βr + constant

apply to these data? Draw the follwing table:

r/nm ket /s−1 ln ket /s−1
0.48 1.58 × 1012 28.1
0.95 3.98 × 109 22.1
0.96 1.00 × 109 20.7
1.23 1.58 × 108 18.9
1.35 3.98 × 107 17.5
2.24 6.31 × 101 4.14

and plot ln ket vs. r

30

20
ln (ket / s–1)

10

0
0 1 2 3
r/nm Figure 29.5
DYNAMICS OF ELECTRON TRANSFER 479

The data fall on a good straight line, so the equation appears to apply . The least squares linear fit
equation is:
ln ket /s = 34.7 − 13.4r/nm r 2 (correlation coefficient) = 0.991

so we identify β = 13.4 nm−1 .

P29.20 The theoretical treatment of section 29.1 applies only at relatively high temperatures. At temperatures
above 130 K, the reaction in question is observed to follow a temperature dependence consistent
with eqn 29.12, namely increasing rate with increasing temperature. Below 130 K, the temperature-
dependent terms in eqn 29.12 are replaced by Frank–Condon factors; that is, temperature-dependent
terms are replaced by temperature-independent wavefunction overlap integrals.
P29.21 (a) The electrode potentials of half-reactions (a), (b), and (c) are (Section 29.8)
(a) E(H2 , H+ ) = −0.059 V pH = (−7) × (0.059 V) = −0.14 V
(b) E(O2 , H+ ) = (1.23 V) − (0.059 V)pH = +0.82 V
(c) E(O2 , OH− ) = (0.40 V) + (0.059 V)pOH = 0.81 V


0.059 V 0.35 V
E(M, M+ ) = E − 
−
(M, M+ ) + log 10−6 = E − 
−
(M, M+ ) −
z+ z+
Corrosion will occur if E(a), E(b), or E(c) > E(M, M+ )
(i) E −

−
(Fe, Fe2+ ) = −0.44 V, z+ = 2
E(Fe, Fe2+ ) = (−0.44 − 0.18) V = −0.62  V < E(a, b, and c)
> E(a)
(ii) E(Cu, Cu+ ) = (0.52 − 0.35) V = 0.17 V
< E(b and c)

2+ > E(a)
E(Cu, Cu ) = (0.34 − 0.18) V = 0.16 V
< E(b and c)

2+ > E(a)
(iii) E(Pb, Pb ) = (−0.13 − 0.18) V = −0.31 V
< E(b and c)
(iv) E(Al, Al3+ ) = (−1.66 − 0.12) V = −1.78V < E(a, b, and c)
> E(a)
(v) E(Ag, Ag+ ) = (0.80 − 0.35) V = 0.45 V
< E(b and c)
(vi) E(Cr, Cr 3+ ) = (−0.74 − 0.12) V = −0.86 V < E(a, b, and c)
(vii) E(Co, Co2+ ) = (−0.28 − 0.15) V = −0.43 V < E(a, b, and c)

Therefore, the metals with a thermodynamic tendency to corrode in moist conditions at pH = 7

are Fe, Al, Co, Cr if oxygen is absent, but, if oxygen is present, all seven elements have a
tendency to corrode.
(b) A metal has a thermodynamic tendency to corrosion in moist air if the zero-current potential for
the reduction of the metal ion is more negative than the reduction potential of the half-reaction
4H+ + O2 + 4e− → 2H2 O E−

−
= 1.23 V
The zero-current cell potential is given by the Nernst equation
RT RT [Mz+ ]ν/z
E = E−

−
− ln Q = E −

−
− ln + ν
νF νF [H ] p(O2 )ν/4
We are asked if a tendency to corrode exists at pH 7 ([H+ ] = 10−7 ) in moist air (p(O2 ) ≈
0.2 bar), and are to answer yes if E ≥ 0 for a metal ion concentration of 10−6 , so for ν = 4
480 INSTRUCTOR’S MANUAL

and 2+ cations

−

− 0.02569 V (10−6 )2 −

−
E = 1.23 V − EM − ln = 0.983 V − EM
ν (1 × 10−7 )4 × (0.2)

In the following, z = 2
For Ni: E −

−
= 0.983 V − (−0.23 V) > 0 corrodes
−

−
For Cd: E = 0.983 V − (−0.40 V) > 0 corrodes
−

−
For Mg: E = 0.983 V − (−2.36 V) > 0 corrodes
−

−
For Ti: E = 0.983 V − (−1.63 V) > 0 corrodes
−

−
For Mn: E = 0.983 V − (−1.18 V) > 0 corrodes
P29.22 Icorr = Aj0 ef E/4 [29.62]

with E = −0.62 − (−0.94) V = 0.32 V [as in Problem 29.21]

Icorr ≈ (0.25 × 10−6 A) × (e0.32/4×0.0257) ) ≈ 6 µA