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Atkins, Solution, 7th Ed

Atkins, Solution, 7th Ed

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Atkins, 7th edition solutions manual
Atkins, 7th edition solutions manual

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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 isj ;j0 is the exchange current density;\u03b1 is the transfer
coef\ufb01cient;f is the ratioF /RT ; and\u03b7 is the overpotential.

(a)j= j0f\u03b7is the current density in the low overpotential limit.
(b)j= j0e(1\u2212\u03b1)f \u03b7 applies when the overpotential is large and positive.
(c)j=\u2212j0e\u2212\u03b1f \u03b7 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 approachesE\u2212
\ue000
\u2212(Ox, Red) for a solution that contains the reduced component
(Red), current begins to \ufb02ow as Red is oxidized. When the potential difference is swept beyondE\u2212
\ue000
\u2212

(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 throughE\u2212

\ue000
\u2212(Ox, Red), current \ufb02ows 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\u2212
\ue000
\u2212(Ox, Red), so the species present can be identi\ufb01ed. 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 bereversible. In this case, the peak separation is independent of the sweep rate and equal to(59 mV)/n at room temperature, wheren is the number of electrons transferred. If the rate of electron transfer is low, the voltammetry is said to beirreversible. 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\u2212\u2192Fe(s)
E\u2212
\ue000
\u2212=\u22120.44 V
with the values for one of the following half-reactions
In acidic solution
(a)2 H+(aq)+2 e\u2212\u2192H2(g)
E\u2212
\ue000
\u2212=0V
(b)4 H+(aq)+ O2(g)+ 4 e\u2212\u2192 2H2O(l)
E\u2212
\ue000
\u2212=+1.23 V
In basic solution:
(c)2H2O(l)+ O2(g)+4 e\u2212 \u21924OH\u2212(aq)
E\u2212
\ue000
\u2212=+0.40 V
DYNAMICS OF ELECTRON TRANSFER
467
Because all three redox couples have standard potentials more positive thanE\u2212
\ue000
\u2212(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 \ufb01rst two
E(a)= E\u2212
\ue000
\u2212(a)+ (RT /F )ln a(H+)=\u2212(0.059 V)pH
E(b)= E\u2212
\ue000
\u2212(b)+ (RT /F )ln a(H+)=1.23 V\u2212 (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 signi\ufb01cant rate. The effect of the exchange current density on the corrosion rate can be seen by considering the speci\ufb01c case of iron in contact with acidi\ufb01ed 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\u221214A cm\u22122, whereas for (a) it is 10\u22126A cm\u22122. 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 whenE 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 eitherA orA\ue001is 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\u2019s standard potential is\u22120.76 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,\u22122.36 V). The magnesium acts as a sacri\ufb01cial 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\u2013acceptor pair separated by a constant distance, assuming that the
reorganization energy is constant:
lnket=\u2212(\ue000r G\u2212
\ue000
\u2212)2
4\u03bbRT\u2212\ue000r G\u2212
\ue000
\u2212
2RT+constant,
or equivalently
lnket=\u2212(\ue000r G\u2212
\ue000
\u2212)2
4\u03bbkT
\u2212\ue000rG\u2212
\ue000
\u2212
2kT+constant,
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\u2019S MANUAL
two unknowns:\u03bb and the constant.
lnket, l+(\ue000r G\u2212
\ue000
\u2212
1)2
4\u03bbkT
+\ue000rG\u2212
\ue000
\u2212
1
2kT=constant =lnket,2 +(\ue000r G\u2212
\ue000
\u2212
2)2
4\u03bbkT
+\ue000rG\u2212
\ue000
\u2212
2
2kT,
so(\ue000rG\u2212
\ue000
\u2212
1)2\u2212 (\ue000r G\u2212
\ue000
\u2212
2)2
4\u03bbkT
=lnket,2
ket,1
+\ue000rG\u2212
\ue000
\u2212
2\u2212\ue000r G\u2212
\ue000
\u2212
1
2kT
and\u03bb=
(\ue000rG\u2212
\ue000
\u2212
1)2\u2212 (\ue000r G\u2212
\ue000
\u2212
2)2
4
\ue000kTlnket,2
ket,1+\ue000rG\u2212
\ue000
\u22122\u2212\ue000r G \u2212
\ue000
\u22121
2
\ue001
,
\u03bb=
(\u22120.665 eV)2\u2212 (\u22120.975 eV)2
4(1.381\u00d710\u221223 J K\u22121)(298 K)
1.602\u00d710\u221219 J eV\u22121
ln3.33\u00d7106
2.02\u00d7105\u22122(0.975 \u22120.665) eV
=1.531 eV
If we knew the activation Gibbs energy, we could use eqn 29.12 to compute\ue002HDA\ue003 from either rate
constant, and wecan compute the activation Gibbs energy from eqn 29.4:
\ue000\u2021 G=(\ue000r G\u2212
\ue000
\u2212+\u03bb)2
4\u03bb
=[(\u22120.665+ 1.531)eV]2
4(1.531 eV)
=0.122 eV.
Now
ket
=2\ue002HDA\ue0032
h
\ue002
\u03c03
4\u03bbkT
\ue003
1/2
exp
\ue002
\u2212\ue000\u2021G
kT
\ue003
,
so
\ue002HDA\ue003=
\ue000
hket
2
\ue001
1/2
\ue000
4\u03bbkT
\u03c03
\ue001
1/4
exp
\ue002
\ue000\u2021G
2kT
\ue003
,
\ue002HDA\ue003=
\ue002
(6.626\u00d7 10\u221234J s)(2.02\u00d7 105s\u22121)
2
\ue0031/2
\u00d7
\ue002
4(1.531 eV)(1.602\u00d7 10\u221219 J eV\u22121)(1.381\u00d7 10\u221223 J K\u22121)(298 K)
\u03c03
\ue003
1/4
\u00d7exp
\ue002
(0.122 eV)(1.602\u00d7 10\u221219J eV\u22121)
2(1.381\u00d7 10\u221223 J K\u22121)(298 K)
\ue003
=9.39 \u00d710\u221224J
E29.6(b)Equation 29.13 applies. In E29.6(a), we found the parameter\u03b2 to equal 12 nm\u22121, so:
lnket /s\u22121=\u2212\u03b2r +constant so constant= lnket /s\u22121+\u03b2 r,
and constant= ln 2.02\u00d7 105+(12 nm\u22121)(1.11 nm)=25.
Taking the exponential of eqn 29.13 yields:
ket=e\u2212\u03b2r+constant s\u22121 =e\u2212(12/nm)(1.48 nm)+25 s\u22121 =1.4 \u00d7103 s\u22121.
E29.7(b)Disregarding signs, the electric \ufb01eld is the gradient of the electrical potential
E=d\ue000\u03c6
dx\u2248\ue000\u03c6
d=\u03c3\u03b5=\u03c3
\u03b5r \u03b50
=
0.12 C m\u22122
(48)\u00d7 (8.854\u00d7 10\u221212 J\u22121 C2m\u22121)=2.8 \u00d7108 V m\u22121

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