Kinetika 3 Castellan

34
Chemical Kinetics
II l. H eterogeneous Reactions,
Electrolysis, Photochemistry
34.1 HETEROGENEOUS REACTIONS

Very early in the development of the art of chemistry finely divided powders of various
sorts were recognized as catalysts for many reactions. Only relatively recently have the
details of the mechanism of reactions on surfaces been elucidated. For a long time it
was thought that the function of the surface was simply to concentrate the reactants on
it; the increased rate was attributed to the increase in "concentration." It can be shown
that this certainly is not correct for the great majority of reactions. Calculation shows
that for a concentration effect of this type to produce the increases in rate ordinarily
observed would require surface areas per gram of catalyst that are impossible to attain.
In the majority of cases the increased rate of reaction on a surface is the result of the
surface reaction having a lower activation energy than that of the homogeneous reaction.
At ordinary temperatures, each kilojoule diflerence between the activation energies
means a factor of 1.5 in the rate. The mode of action of the surface therefore is the same
as that of other catalysts (see Section 32.20)in its provision of an alternative path of lower
activation energy for the reaction.
34.2 STEPS IN THE MECHANISM OF SURFACE REACTIONS

For a reaction to occur on a surface the following sequence of steps is required'
l. Diffusion of reactants to the surface.
2. Adsorption of the reactants on the surface.
3. Reaction on the surface.
4. Desorption of products.
5. Diffusion of products from the surface.
Any one or a combination of these steps may be slow and therefore be rate determining.
868 Chemical Kinetics lll
Figure 34.1 The Nernsl

diffusion layer.
In gaseous reactions the diffusion steps (1) and (5) are very fast and are rarely, if
ever, rate determining. For very fast reactions in solution the rate may be limited by
diffusion to or from the surface of the catalyst. If diffusion is the slow step, then the con-
centration d' of the diffusing species at the surface will differ from the concentration c-
in the bulk. In Fig. 34.1, the concentration is plotted as a function of the distance from the
surface. This curve is conveniently approximated by the two dashed lines. The distance d
is the thickness of the diffusion layer. This approximation was introduced by Nernst,
and the layer in which the concentration differs appreciably from that in the bulk is
called the Nernst diffusion layer. The concentration gradient across the diffusion layer is
given by (E - t')l6,so that the rate of transport per square metre of the surface is
-D(c - V)
,
where D is the diffusion coefficient. This approximation is a simple correction to the
kinetic equations when diffusion is slow enough to matter. The rate of diffusion can be
enhanced considerably by vigorous stirring, which thins the diffusion layer. The thickness
6 in a well-stirred solution is of the order of 0.001 cm. In less well-stirred solutions the
thickness is of the order of 0.005 to 0.010 cm.
It is more commonly observed that the rate of reaction is determined by step (2),
or by a combination of steps (3) and (a). We consider these cases in order.
34.3 SIMPLE DECOMPOSITIONS ON SURFACES

In the case of the simple decomposition of a molecule on a surface, the process can be
represented as a chemical reaction between the reactant A and a vacant site S on the
surface. After adsorption, the molecule A may desorb unchanged or may decompose to
products. The elementary steps are written
Adsorption A+S k' , AS;
Desorption AS k-t, A+S;
Decomposition AS k' ' Products.
If u is the rate of reaction per square metre of surface, then
d(1lA):D:K2c6s,
.. ,. ^ (34.t)
dt
where ca5 is the concentration (mol/m2) of A on the surface.
Simple Decompositions on Surfaces 869
Let c, be the total concentration of surface sites per square metre and let 0 be the
fraction of these sites that are covered by A. Then ca5 : c"0, and c"(l - 0) : cs, the
concentration of vacant sites on the surface. Then the rate of the reaction can be written
u : kzc"0. (34.2)
The value of 0 is obtained by applying the steady-state condition to the rate of formation
of AS:
:0 : k'coc"(l - 0) - k-rc"0 - k2c"0, (34.3)
T
where co is the concentration of the reactant A either in the gas or in solution. From
Eq. (3a.3) we obtain
krco
0: krco 1- k-, + k,
(34.4)
This value of 0 in the rate law, Eq. (34.2), yields

krkrc"co
u: kp1 k-n k'
(34.5)
If Eq. (3a.5) must be considered in full, then it is convenient to invert it:

1 1 .k_r+k2
f- (34.6)
u krc"' krkrc"co
A plot of l/u versus llc,yields If krc"as the intercept and (k- 1 + k)lk2krc" as the slope.
Usually it is more convenient to consider the limiting cases of Eq. (34.5).
Case 1. The rate of decomposition is very large compared with the rates of absorption
and desorption. In this case, k2) kpo* k-r, and the denominator in Eq. (34.5)
is equal to kr; then the rate is given by
u : k1c"co. (34.7)
This is simply the rate of adsorption. Physically, the assumption that k2 is large implies
that an adsorbed molecule decomposes immediately, so that the rate of decomposition
depends on how quickly the molecules can be adsorbed. From Eq. (34.4) and the assump-
tion that k, > krco,it follows that 0 ( 1. The surface is sparsely covered with the reactant.
The reaction is first order in the concentration of the reactant A. This situation is realized
in the decomposition of N2O on gold, and of HI on platinum.
Case The rate of decomposition is very small compared with the rate of absorption
2.
and desorption. In this case, k, is very small so that the denominator of Eqs. (34.4) and
(34.5) is krcol k_r. Introducing the absorption equilibrium constant K: klfk-1,
Eq. (3a.a) becomes
(34.8)
which is the Langmuir adsorption isotherm. The occurrence of the decomposition does
not affect the adsorption equilibrium at all. The rate becomes
krKc"co
- (34.e)
Kc,t I
Chemical Kinetics lll
First-order region
Figure 34.2 Rate of a surface
reaction as a function of
reactant concenlratton.
In this case both the surface coverage d and the rate depend on the concentration ca.
At low concentrations, Kc4 ( 1, and A x Kc"; the coverage is small. Then
u : k2Kc"co, (34.10)
and the reaction is first order in the concentration of A. At high concentrations, Kco - l,
and e x 1; the surface is nearly fully oovered with A. Then
u : k2c" (34.1 1)
and the reaction is zero order with respect to A. Since the surface coverage ceases to vary
significantly with the concentration of A at high concentrations, the reaction rate becomes
independent of the concentration of A. The decomposition of HI on gold and of NH.
on molybdenum are zero order at high pressures of HI and NH..
The typical variation in the rate of reaction as a function of the concentration of
the reactant is shown in Fig. 34.2. This figure should be compared with Fig. 32.12,whjch
shows the same behavior for a homogeneous catalyst. Note that Eq. (34.5) has the same
form as Eq. (32.95), the equation for homogeneous catalysis, which is the same as the
Michaelis-Menten law, Eq. (32.100),far enzymes. Also, Eq. (3a.O has the same form as
the Lineweaver-Burk equation for enzymes.
34.4 BIMOLECULAR REACTIONS ON SURFACES

Two molecules A and B can react on a surface if they occupy neighboring sites of the
surface. Let0 and 06 be the fractions of the surface sites covered by A and B, respectively,
"
and let 0, be the fraction of sites that are vacant; 0, : I - 0o - 0r. We represent the
reaction by
AS+BS & , Products.
The rate per unit area, u, is
v: kc?0,0t. (34.t2)
To evaluate 0" and 0, we consider the two adsorption reactions
A+s + AS and B+S + BS.

Biomolecular Reactions on Surfaces 871
The steady-state equations are

drnr:0: kp"co|u kc!0,06;
dt
- k
- rc"0o -
dtg: : kc! 0'0u.
dt
o k2c"coT, - k - rc,06 -
Since0,:1_0".To,thesetwoequatlonscanbesolvedfor0oand0,.Wewillconsider
:
only thl case for wnicn k is very r-ull; if we set k 0, these
equations reduce to
0": Krco0', 0b : Kzcr?,, (34'13)
where K r: kr,'k - r and K2 -- ktlk - r. Usingthese vatues of 0o and 0rin 0" : t- 0

" - 0,'
we obtain
0u:l-Krco9,-K2c60u,
so that
o- | (34.14)
"u-llKpo*K2c6'
This value of 0" brings Eqs. (34.13) to the form
Kzcr
0t: (34.1 s)
| + Ktc,* K2co
These values used in Eq. Qa.n) yield the rate law

kKrK2c!c,c6
(34.16)
':tl*K;r**Y'
which has some unusual characteristics. We examine each case separately.
Case 1. Both A and B are weakly adsorbed; the surface is sparsely covered. In this case,
Krco 4 I and Krc6 ( l. The denominator of Eq. (34.16) is about equal to unity and the
rate law is
u: kKrKzc?rorr. (34.t7)
The reaction is second order overall, and is first order with respect to both A and B.
Case 2. One reactant, A, more strongly adsorbed than the other. In this case, Ktco * K2c6;
the denominator is about equal to 1 * Krco, and Eq. (3a.16) takes the form
u: kK(l rKrc! coco

+ Krc")2
(34.18)
The rate is first order with respect to the less strongly adsorbed reactant; the dependence
of the rate on the concentration of the more strongly adsorbed reactant is more compli-
cated. At low values of co, the rate increases as ca increases, passes through a maximum
value at co: lf K1,and then decreases with further increase in co. At very high values of
co,the rate becomes inversely proportional to co (see Case 3)'
Case 3. One reactant very strongly absorbed. If A is very strongly adsorbed, we have the
same situation as in Case 2 but with the additional condition that Krco 1, so that the )
denominator of Eq. (34.1S) is (Krc,)2. Then the rare is
,.
u:-
kK rc! cu
(34.19)
K tco
The rate of the reaction is inversely proportional to
the concentration of the strongly
adsorbed species' This is an example or inuuition,
o. polro"lng. tn ,hi, case one of the
reactants itself inhibits the reaction. The reaction
beiween etliylene and hydrogen on
copper is of this type. At low temperatures the rate
is given by
,:k P'' ,
Pcrso
the ethylene being strongly adsorbed. At higher
temperatures the ethylene is less strongly
adsorbed, the surface is sparsely covered,
ind the rate expression reduces to that given
by Eq. (34.17):
u : k,ps.pcrso.
It is one substance is strongly adsorbed on the surface (whether
it rea
be foieign material) the iaie is inversely proportional to the
concentr adsorbed substance; this substance'inhibits the reaction.
34.5 THE ROLE OF THE SURFACE IN CATALYSIS

In homogeneous catalysis the catalyst
to form a compound that reacts ."uiily
acting as a catalyst. One or more of the
equivalent to the formation of the chemica
vide an alternative path of lower activation
reason for the increased rate of reaction.
ation as the reactants pass to products.
tion energy for the forward reaction is
therefore increases the rate of the forward
";wi:":"!,::I::#;rT:Hli:catalvst
I
Lrri uncat
Products
Figure 34.3 Energy surfaces for

uncatalyzed and catalyzed
reacttons.
The Role of the Surface in Catalysis 873
Table 34.1
Activation energies for catalyzed and
uncatalyzed reactions
Decomposition of Surlace E$,/(kJ/mol) Ef."",/(kJlmol)
HI Au 105 184
Pt 59
Nto Au t2t 245
Pt 136
NH. w 163 330
Os t97
Mo I 30-l 80
CHt Pt 230-250 330
By permission from K. J. Laidler, Chemical Kinetics. New York: McGraw-

Hill, 1950.
Table 34.1 lists a few values ofthe activation energies for various reactions on surfaces,
and the corresponding values for the uncatalyzed reaction.
An important fact about surface reactions is that the surface sites on a catalyst
differ in their ability to adsorb the reactant molecules. This is demonstrated by the action
of catalytic poisons. In the preceding section, the effect of strong adsorption of one
reactant was to inhibit reaction or poison the catalyst. Foreign molecules that do not
take part in the reaction can also poison the surface if they are strongly adsorbed. The
algebraic effect on the rate equation is to make the rate inversely proportional to some
power, usually the first power, of the concentration of the poison.
It has been shown that the amount of poison required to stop the reaction is ordinarily
significantly smaller than the amount needed to form a monolayer of poison on the surface.
This observation led H. S. Taylor to postulate that the adsorption and subsequent
reaction takes place preferentially on certain parts ofthe surface, which he called "active
centers." The active centers may constitute only a small fraction of the total number of
surface sites. Ifthese active centers are covered by molecules ofthe poison, the reaction is
unable to proceed except at an extremely slow rate'
Imagine the appearance of a surface on the atornic scale. There are cracks, hills and
valleys, boundaries between individual grains, different crystal faces exposed, edges,
points, and so on. It is not surprising that adsorption takes place more easily in some
places than in others. The chemical kinetic consequences of this lack of uniformity in the
surface have been explored extensively, both from the theoretical and the experimental
standpoints.
The chemical nature of the surface determines its ability to act as a catalyst for a
particular type of reaction. For illustration, two reactions of an alcohol can be considered.
On metals of the platinum group such as Ni, Pd, and Pt, the alcohol is dehydrogenated.
CH3CH2OH + CH3CHO*H:.
On a surface such as alumina, dehydration occurs:
CH3CH2OH 4 CIJ2CH2+H2O.
In the two cases the mode of attachment is different.
Nickel has a strong affinity for hydrogen so that on nickel the attachment is pre-
sumably to the hydrogen atoms:
H H
I I
H.C_C-O
"ll H3C-C:O
tI
tI -
Hfv1--sl----Hz
Ni Ni Ni Ni Ni Ni Ni Ni
on alumina, there are hydroxyl groups at the surface as well as oxide groups. The
surface could be imagined as having the configuration
H
o
to
I I
AI AI
'o'
Then the attachment of the alcohol could be
HH
H- H-C:C-H
tt
HrO
H
-
After desorption of the water molecule the surface is left'unchanged. Note that these
diagrams are intended to represent nothing more than plausible suppositions
about the
surface structure and the mode of attachment of the molicule.
34.6 ELECTROLYSIS AND POLARIZATION

Electrolysis refers to the chemical reaction or reactions that accompany the passage
of a
current supplied by an external source through an electrolytic solution. An el-ectro-
chemical cell through which a current is passing is said to be johrized. polarjzation
is a
general term that refers to any or all of the phenomena associated
with the passage of a
current through a cell.
We can write any electrolytic half-reaction in the general form:
O:Iv;A,+v.e-.
The quantity of charge that passesthe electrode as the reaction advances by d(is de,where
dQ : v"F d(. (34.20\

Electrolysis and Polarization 875
The current is given by 1 : dQ:ldt, so that
I:t"FVdt (34.2t)
The current is proportional to the rate, di dr, of the reaction (or vice versa) so that the
rate is usually expressed in amperes. If ,4 is the area of the electrode, then the current
density, i, is
,: ::,.0(:4;,
i: v"FL.t. (34.22)
where u, is the rate of reaction per unit area.

td( (34.23)
"n- Adt
The significant quantity is the rate per unit area; therefore, we will use current densities to
describe the rates, the usual units being Alcm2 or mA/cm2.
The sign of the current density follows the sign of the stoichiometric coefficient v..
If v" is plus, electrons appear on the product side, and the reaction is an oxidation. The
current is an anodic current and has a positive sign. The symbol for an anodic current
density is i * or i" . If v" is minus, electrons appear on the reactant side, and the reaction is a
reduction. The current is a cathodic current and has a negative sign. The symbol for a
cathodic current density is i- or i..
The total current density at an electrode is the algebraic sum of the anodic and
cathodic current densities for the reaction taking place on that electrode:
i: i. * j". (34.24)
If more than one electrolytic reaction is occurring on the electrode, the total current
density is the algebraic sum of the current densities for all the anodic and cathodic
reactions taking place on that electrode.
The study of electrode reactions is unique in the sense that within li-mits the rate
of the reaction can be controlled by simply increasing or decreasing the current through
the cell. The electrolysis reaction also differs from other chemical reactions in that "half "
ofit occurs at one electrode and the other "half" occurs at the second electrode, which
may be spatially distant from the first. For example, the electrolysis of water,
HrO # Hr+)Or,
can be broken down into two "half " reactions:
At the cathode 2IJ+ + 2e- ------+ Hr,
At the anode HrO + IO'+2H++2e-
Each ofthese reactions is proceeding at the same rate I, the current being passed. Ifthe
area of the cathode is .4" and that of the anode is ,4", then the rate of the cathodic reaction
per unit area of cathode is i": lf A,,and that of the anodic reaction per unit area of
anode is iu : IlA,.The current density at either electrode depends on the concentrations
of reactants and products near the electrode, just as any reaction rate depends on con-
centrations. In addition, the current density depends on the electrode material and
very strongly on the potential of the electrode. The phenomena associated with electrolysis
are properly linked with the kinetics of reactions on surfaces. Because of great experimental
difficulties, particularly the problem of controlling impurities in liquid solutions, the
study of electrode kinetics has become reasonably scientific only relatively recently.
Some olthe earlier work is excellent, but much of it is erroneous.
34.7 POLARIZATION AT AN ELECTRODE

Rather than describe the electrolysis of any solution with any two electrodes, we begin
by considering a single reversible electrode at equilibrium and then ask what happens if
we pass a current into the electrode.
Consider a hydrogen electrode in equilibrium with H+ ion at a concentration c
and hydrogen gas at a pressure p. The equilibrium potential of this electrode is denoted
by Qo. The equilibrium is H, 2H
+ * 2e- .If the potential of the
electrode is increased
=
(made more positive), this equilibrium will be disturbed. The reaction from left to right
will predominate, H, will be oxidized, and a positive current will flow into the solution.
If the potential of the electrode is lowered (made more negative), the equilibrium will be
disturbed. The reaction from right to left will predominate,H2will be liberated, and a
positive current will flow into the electrode or a negative current *ill flow into the solu-
tion. The current that flows to the electrode, thereforg depends on the departure of the
potential from the equilibrium value, @ {e. This difference between the applied po-
-
tential @ and the equilibrium potential @ is the overpotential, or overvolt age,q:
4=Q-Qo. (34.2s)
Since the current varies continuously with the potential, and therefore with the over-
potential, we can expand the current in a Taylor series. Since i : 0 when : O,the series
4
becomes
,: (#),_", .;ffi),=o,'* " (34.26)
We can write this in a slightly different way, using only the first term,
(34.27)
For small values of 4, I is proportional to 4. Note also that the sign of i depends on the sign
of 4. The exchange current density for the reaction, is, defined by Eq. (34.27),is the equi-
librium value of either the anodic or cathodic current density. The value of ie depends on
the concentrations of the electroactive materials, H+ and H, in this case, and on the
composition of the electrode surface.
For the hydrogen evolution reaction on platinum; for example, io x l0-2 Afcm2,
but on mercury, io 10-ra Afcm2.It is, in fact, thesevalues of io that allow us to use
=
platinum as the electron collector for a reversible hydrogen electrode and prevent our
using mercury for this purpose.
In the kinetic sense there is a gradation between what are called reversible electrodes
and irreversible electrodes. The reversible potential of an electrode is measured by
balancing a cell in a potentiometer circuit. This involves detecting the point at which the
current flow to the electrode is zero. Suppose the galvanometer registers "zero current"
for any value of current between i' and i' . The magnitude of i' depends on the sensitivity
-
ofthe galvanometer. The characteristics ofthe "very reversible" electrode and the "very
Measurement of Overvoltage 477
Figure 34.4 Current-potential relation at (a) reversible and (b) irreversible electrodes.
irreversible" electrode are shown in Fig.34.4. The balance will be observed for the re-
versible electrode anywhere in the range between @2 and @1. This uncertainty in the
measurement of {o is very small.
For the irreversible electrode (Fig. 3a.ab), the null point is registered anywhere in
the wide range of potential between @', and Q'r.The slope of the curve is very small; that is,
io very small. An electrode with a large io is therefore "more reversible" than one with a
small io.
34.8 MEASUREMENT OF OVERVOLTAGE

Before considering the theoretical ideas that relate the current to the overvoltage, we
should understand the principle of the measurement of overvoltage. A cell is shown
schematically in Fig. 34.5. A measured current is passed between the two electrodes .4
and B. The reference electrode R is the same kind of electrode as B. Matters are arranged
so that the same electrode equilibrium is established at both B and R. When i : 0, B and R
both have the same potential. When the current passes into B, this electrode has a potential
measured on the potentiometer P that is different from that of R, which carries no current.
This difference in potential is the measured overvoltage,4^:6n - {s. The value of 4.
is measured for various values of the current density.
Figure 34.5 Cell for the measurement

of overvoltage.
As the experiment stands, the measured value contains

an ohmic component from
the ir drop between R and B, a concentration component
resulting from concentration
changes in the vicinity of the electrode, and a component"
denote d by ,l,which is related
to the rate constant ol the reaction. Thus
4m:lohmicJ_4"on"l4. (34.28)
There
negrig u
of the it
s
'1'" ii;#ru;;il#Ti'i" .f";
is the
e rate constant of often
called the actiuation oueruoltage.
* 34.9 THE CURRENT_POTENTIAL RELATTON

To derive the equation connecting the current with the
overpotential we consider the
dissolution of a metal; the reaction is
M(metal) M.*(aq) * ze-(metal)

The reverse reaction is the metal-deposition reaction.
Within the metal, the equilibrium
-
M"+(metal) + ze-(metal) -- M(metal)
is established very rapidly. Adding these two equations
together, we obtain
M"+(metal) + M'*(aq)
as the effective charge transfer reaction. Thus we may regard
the metal dissolution reaction
ses over an activation potential barrier and
. Similarly, the electrodeposition reaction is
phase over a potential barrier to the metal.
al is a consequence of the dependence of the
we consider nrst the hypotheticar lt';jt;[t:1,ili

"",'jloj;T,:l';:.T
difference between the metal and the solution. [?,"",,",
Then the Gibbs energy of activation is
(l - a) zFL
(a) e=0. = o (b)d + o
Figure 34.6 Dependence of Gibbs energy of activation on potential.

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equilibrium,i:0,and
(i*)o: -(i-)o: io, (34.3g)
where (i16and (i-)o are the (equal) rates of the anodic and cathodic
reactions at equi-
librium' They are both equal to ro, the exchange cuwent for the
electrochemical reaction.
Note that
io : k*(c."0) oeazFooiRT : *_(co)6e-(1 -a):F@e:RT,
(34.3e)
whe.re (c."a)o and (c.*)6 are theequilibrium values of the concentrations and
equilibrium value of the potential. If we now divide each @o is the
term in iq-. 1:+.:z) by io, we get
1 : +1 eq:Fto-oottRT co*
- o-tr-dt.Fto- eot
(34.40)
to (c..a)o (c"*)n "
in which the values of io from Eq. (3a.39) have been
used to eliminate the individual rate
constants, k* and k_, on the right_hand side.
Since @ _ Qo: r7 by the definition in
Eq' (3a'25), the current density b" written in terms of the"overpotential and the ex-
change current: "*
,: ,.[,ffi - -,,,,,,^1
"azF4tRr ff"-,, (34.41)
This equation is a typical example of a rate equation
for an electrochemical reaction at an
electrode.
In the particular instance of metal dissolution, the concentration
of metal ion in the
metal is a constant; hence in all circumstances cred : (c,.Jo.
is stirred.well, the passage of the current does
Ii in addition, the solution
not affect the concentration of the metal ion
just outside the double layer; then co, : (coJo.
The equation becomes
i: ioledrFrtlRT _ (34.42)
"-(r-a)zFnlaT1.
We can always write Eq. (34.42) in the form:
i: 2i o e@
- t t 2t zF at Rr r*n (r#r) (34.43)
For many reactions a : L and for many others a is remarkably j.
: j, we have the simple symmetric form close to when
a
i:2iort*(r+) (34.4)
s are shown in Fig. 34.7 for z : I and for several
values of io.
small, a large value of 4 is required to produce even
a small
correct for the Cd -+ ed2 * + 2e- reaction; a : 0.5, jo :
1
.01mol/L.
On the other hand, fgr Ag -* Ag* * e- a. : 0.74 and :
,
0.1 mol/L. Consequently,Eq. (34.43)ls the appropriate
i6 4.5 Alcm2 at [Ag+] :
one foi silver.
*34.9.1 The Tafet Equation

when the overpotential is.rarge (either positively or negatively),
that is, when l4l>
- 75 mv, then one term in the rate equation may be neglecied in c'#parison to the other.
The Current-Potential Relation 881
Very large
/0 Large
l0
Small
r0
Very small
zF4
RT
Figure 34.7 ro versus zFn/RT
Thus Eq. (34.42) becomes

i:iu:ioedzFilRr, (n> - 75mV) (34.4s)
or
-i : -i" - ioe-(r-atzFilRr, @ < - -75mV). (34.46)
If we take the logarithm of both sides of either of these equations we obtain an equation
of the form
lql : -b log,o io * b logto li I
(34.47)
This is the Tafel equation. On the anodic side, b :2.3O3RTlazF, while on the cathodic
side, b : 2.303RT l(l - a)zF. Thus from a Tafel plot, a plot of l4 | against logto I i l, we
obtain the two important parameters, a and io. The a is obtained from the slope and the io
from the intercept on the horizontal axis (Fig. 34.8).
Figure 34,8 Tafel plot for cathodic

logr oro overvoltage.
34.9.2 The Hydrogen Electrode

The hydrogen electrode provides a simple example of an electrode reaction that involves
a two-step mechanism. We write the equations for the anodic oxidation of H2, but keep
the expreisions for the forward and reverse reactions, so that the equations also describe
the cathodic reduction of H+ ion to Hr. Of the several possible mechanisms, we choose
only the most obvious one for illustration. It consists of the two elementary reactions,
(1) Hz(aq) + 2V :2H(ads)
(2) H(ads):H**V*e-
in which V is a vacant site on the surface.
Although the first reaction does not pass electric charge across the interface directly,
each time it occurs the second reaction must pass two electrons across the interface.
Consequently, we can write the rate of reaction (1) in terms of an equivalent current
density, i,
i t: 2F k(u'c2, - 2fk - rczt' (34.48)
At equilibriurl, jr : 0, and the exchange current is given by
i: 2Fk 1(cs,)o("u)B : 2Fk -t(.d3.

Using these equations to eliminate the rate constants in Eq. (34.48) and writing c17: 0c"
and cr, : (1 - 0)c" (where g is the fraction of the surface sites occupied by hydrogen
atoms and c" is the total number of surface sites per unit area), we can reduce Eq. (34.48)
to the form
"
:
"'t-',t.e
(H)'- (,i)']' (34.4e)
where 0e and (cs,)e are the equilibrium values (ir : 0) of 0 and c11,.
Using Eq. (34.41) as a guide, we can write the rate of the second reaction as
,, :,,,[# raF.tRr - ffi t.ft "-,'-',."^'].

We assume that the solution is stirred well enough that the concentration of H+ ion near
the electrode is maintained at the equilibrium value, that is, cs*/(c".)o 1;then, when :
we introduce the value of the surface coverage, this equation becomes
,,: ,r"h1"aF4tRr - He-t-,trunrf. (34.s0)
Since only the second reaction passes an electrical charge to the electrode, we have
for the current, i,
,:lz. (34.s1)
When the electrode reaches a steady state, the values of 4 and i are constant; the steady-
state conditi on is dcJdt : 0. In terms of the currents this condition is
it: iz. (34.52)
Using the values of l, and i2 from Eqs. (34.49) and (34.50), and assuming that the supply
TheCurrent-PotentialRelation 883
of hydrogen or the stirring is such that cr,f(cs,)o : 1, we obtain
r'-
',,[(E, (*a)'] :,,,1:,edFqRr - ft,-"-'''o^']
This equation can be solved for 0 as a function of 4 and the result placed in Eq. (34.50)
to yield the relation between i and 11. In practice this involves a general solution of a
quadratic and the result is cumbersome. Two extreme cases can be easily distinguished.
Case l. iro * izo. In this case reaction (l) is very nearly in equilibrium, thus, we can set
*=o:(H)'-(,i)'
This yields 0 : 0o. Using this value in Eq. (34.50), we obtain
i: i2oledFtttRr _ e-(r-"tFqtR7:), (34.53)
which is the rate equation for the simple charge-transfer reaction.
Case 2. izo * irc. In this case the charge-transfer reaction is essentially in equilibrium
and we have
2 : ? nrnnr - I - ? r-(t-atFntRr.
izo=O 0o l-0o
Solving for 0 yields
0 e- F4lRr
et- t -0o* loe-Fntar'
Using this value in the equation, i : it, yields
1 _ ,-2FtrlRT
i: iro (34.54)
At very small coverages, 0o ( 1, and the equation becomes
i : jro(l _ e-2FatRr). (34.55)
On the cathodic branch, when 4 < -75 mV, we can neglect the fust term in Eqs.
(34.53) and (34.55) to obtain
_i : izoe-(L-a)F4tRr, (slow discharge of H+ ion);
-i - iros-2FntRr, (slow combination of H atoms).
If a : j, the Tafel slope corresponding to each ofthese cases at 25'C is
,:'3#Y:0.118
L- v, (slow discharge);
b -2301Rr : 0.030 v, (slow combination).

F
These Tafel slopes are characteristic of the two limiting cases of this mechanism. Many
metals including Pb, Hg, Ag, Cu, Pt, and Pd exhibit the 0.118 V Tafel slope.
34.10 GENERAL CONSEOUENCES OF THE

CU RR ENT-POTENTIAL R ELATION
Rather than discuss the mechanisms of electrode reactions in further detail, we will
describe some general implications of the current-potential relation.
We ask whether it is possible to plate zinc onto a platinum electrode. Consider a
solution containing HCI and ZnClt in which aH* : I and a7n,t : l. Suppose we electro-
lyze this solution using a platinum cathode. As soon as hydrogen starts to evolve at the
cathode, it behaves as a hydrogen electrode. Since the pressure of H, in the vicinity is
very close to 1 atm and cs* : 1, the potential of the electrode on the conventional scale
is zero if no current flows, and slightly less than zero if current is flowing. The dependence
of the potential of the electrode as a function of current density is shown in Fig. 34.9(a).
Since the hydrogen overvoltage on platinum is very small, the potential decreases verl'
slowly as the current density is increased. If zinc is to deposit on the electrode, the potential
must be more negative than the value of the reversible potential of the Zn2* , Zn couple,
which is -0.763 V in this situation. It is clear from the figure that a very high current
density (-400 Alcm2) will be required to bring the potential to a value below
-0.763 V
and thus permit the deposition of zinc. The current density required is so large that, as a
practical matter, zinc cannot be plated onto a platinum surface.
The electrolysis of this solution proceeds quite differently if a lead cathode is used.
The hydrogen overpotential on lead is much larger than that on platinum at every current
density. The current-potential relation is shown schematically for the system with the
lead electrode in Fig. 34.9(b). Only a very small current density (- 0.4 pAlcm2) is required
to bring the potential down far enough so that zinc will deposit. After this value is reached,
the potential does not drop very much with increase in current density because the over-
voltage for deposition of zinc on a lead (or zinc) surface is very small. (After the lead is
coated with zinc, ofcourse, the electrode is a zinc electrode. The hydrogen overvoltage on
zinc is also quite high, so the shape of the curve is essentially the same as for lead.) Figure
34.9(b) can be interpreted as follows. In the region from.4 to B, all of the current goes inro
hydrogen evolution. Ar B, zinc deposition commences. At any point beyond B, both
l-rl
(a) (b)
Figure 34.9 Current-potential curves for the deposition of zinc on
(a) a platinum electrode and (b) a lead electrode.
General Consequences of the Current-Potential Relation 885
4\'\
l
-lr
-t-,]
-lrj
- (_r -l
-('r 5
- 0.6
i = 0.4 4Alcm2
-l-l r
-0 7b3
- 0.s
logln l-il
Figure 34.10 Current versus potential for
deposition of zinc platinum and on lead.
hydrogen evolution and metal deposition occur. The rate of hydrogen evolution is iB,
and this rate remains nearly constant in the region from B to C, since the potential is
effectively constant in this range. The rate of metal deposition, ir, is therefore
-- i - iB
tM (34.56)
and increases as i increases. The fraction of the current used in metal deposition is
iMli : I - iB,'i. The ratio i*li is the current efficiency for metal deposition. Since i,
is very small, the current efficiency is nearly unity at high values of i. In Fig. 34.10 we
illustrate the situation more realistically by using a logarithmic scale for the current.
A very active metal such as sodium cannot be deposited from aqueous solutions
except under special circumstances. The reversible potential for the reduction of Na+
is -2.714 V. Even with a lead cathode an enormous current density would be required
to bring the cathode below this potential; the current efficiency for sodium deposition
would be exceedingly small. Sodium can be deposited into mercury, which has a high
hydrogen overpotential, if a highly alkaline solution is used. High current densities are
required and the current efficiency is very low. Three factors influence the process.
1. The alkaline solution, which brings the potential at which hydrogen is deposited
closer to the potential for sodium deposition.
2. The high hydrogen overvoltage on mercury.
3. The fact that metallic sodium will dissolve in mercury; this brings the sodium de-
position potential nearer the hydrogen value and also keeps the sodium that has been
deposited from reacting with water.
It is worthwhile mentioning that charging the lead storage battery would not be
possible if it were not for a high hydrogen overvoltage on the negative plate, which permits
the reaction
PbSO4 * 2e- ------------+ Pb + SOl-
to occur with high efficiency. A high oxygen overvoltage on the positive

plate, pbor,
is required so that rhe reaction
PbSO+ + 2H2O pbo2 + SOi- + 4H+ + 2e-

can occur with hi-eh efficiency. If these overvoltages were not large, it would not be
possible to polarize the plates to -the potentials required
for the charging reactions to
occur' and passage of the charging current would only decompose
the waierinto hydrogen
and oxygen.
Corrosion reactions are. another group of reactions that depend
critically on the
presence or absence ofa significant hydrogen overvoltage
on the surface.
* 34.11 CORROSTON
34.11.1 Corrosion of Metals in Acids
To discuss so the cell shown in Fig.
34.11(a).It a immersed in a ZnSOo
solution th ,l ipitation of Zn(OH)1.
If this cell i
Zn+2H+ + Zn2+ ]-Hz
occu is liberated on the platin
that attach a Piece
imm ::'iT!lt
zinc 1131'J?riTi,ii;1,",!fi
zinc is balanced by the cathodic current to the plitinum
I"(Zn)+I"(Pt):0
i^(Zn)Ay^ + i"(pt),4pr : 0.
Zn
(a) (b)
Figure 34'11 (a) short-circuitedzn-Hzceil. (b) zn-pt coupre in acid

sorution.
Corrosion 887
Figure 34.12 Corrosion current for zinc in acid solution. (Adapted from K J vetlet, Electrc
chemical Kinetics, New York: Academic press, .lg67, pp 737_73g.)
If we make the areas of the zinc and platinum equal, Azn: Ar, the current densities
balance.
i,(Zn)+t"(Pt):0.
This requirement is shown graphically in Fig. 34.12, which shows the i versus curves for
4
the zinc dissolution reaction and for the hydrogen evolution reaction. At the potential
@r, the current densities sum to zero. At this point, i, : i"o.,, the corrosion curreni density.
The potential of the zn-Pt composite is a mixed potential,
{ . Since @ n is determined by
"
the relative areas and the kinetics of the two electrode p.oCerres, it ii very sensitive t;
the character of the surface and does not have any thermodynamic signihcance. Note
that at the higher pH, since the equilibrium potentials of the zn2*,zn-and the H1H,
electrodes are closer together, the corrosion current is less. This suggests that *"
control corrosion by controlling the potential of the metal. This is, in fiit, done in certain
"un
industrial situations. If, from an external power source, we impress a potential on the
metal that is more negative than @" then by Fig.34.12, i" will be reduced and i" will be
increased. A sufficiently negative potential can reduce the corrosion current to a negligible
value.
If we remove the platinum and simply immerse a piece of zinc in acid, what is the
mechanism of corrosion? In any single piece of zinc metal there are some regions in
which the crystals are under greater strain than in others. This strain is reflecied in a
higher average Gibbs energy of the zinc atoms. These atoms dissolve to form zinc ions
in solution more readily than the atoms in the low strain areas. Thus there are in any piece
of metal anodic areas in which the anodic reaction
Zn Zn2+ +2e-
takes place more readily than in the other areas, which become cailtodic areas. The H,
-
evolution reaction occurs on the cathodic areas. Since a zinc surface has a much lower io
for hydrogen evolution than does a platinum surface, the rate of corrosion of pure zini
is much smaller than the rate of corrosion when it is in contact with a surface, such as
platinum, which has a low hydrogen overvoltage.
34.11.2 Corrosion by Oxygen

Corrosion by oxygen requires the reaction,
Oz+4H+ +4e- + 2H2O, 6" : 1.23V (acid solution);
02 + 2H2O + 4e- 4OH- d' : 0.401V (basic solution).
at the cathodic areas of the metal. The i versus rl curves for oxygen corrosion in acid solu-
tion are shown schematically in Fig. 34. l3 for several different metals. The figure shows that
the corrosion current for zinc is larger than that for iron, which is larger than that for
copper. If Fig. 34-13 had been drawn to scale, the differences in corrosion current would be
even larger than are shown in the figure. At high overpotentials the cathodic current is
limited by the rate of supply of oxygen to the surface. This is indicated by the plateau in
the oxygen polarization curve in Fig.34.13. The limiting current is proportional to the
oxygen concentration in the solution.
Figure 34.13 Oxygen corrosion in acid solution (Adapted from K. J Vetter, Electrochemical
Kinetics, New York: Academic Press, 1967, pp. 737 -738 )
Iron sheet
Figure 34.14 Differential aeration.

Photochemistry 889
A difference in oxygen concentration is sufficient to set up

a corrosion current'
in an aqueous salt solution (Fig' 34'14)'
Consider a piece of iron partially immersed
of oxygen; this makes the area more postttve
Near the airlnterface there is an abundance
flow in the metal from the deeply immersed
than the deeply immersed portions. Electrons
ions deep- in the solution'
region to the iegion.r"u, ih. air interface. This releases Fe2*
corrode by the reaction Fe - Fe2* + 2e-, while
Thus the deeply immersed portions
pH as the process goes
the oxygen is reduced to oH- near the water line. The increases
Fe(oH), is precipitated at an
n, in. Fe2* and oH- ions diffuse toward each other,
"r.
intermediate position. This is called " oxygen defect corrosion " ; the corrosion occurs where
unusual effects such as corrosion under a bolt head'
there is no oxygen. This results in some
dissolves underneath the bolt head where it is protected from
under a particle of dust or an imperfect coat of paint or
protective
this differential aeration effect.
34.ll.3corrosionbyMetalContact;Corrosionlnhibition
The contact of dissimilar metals commonly results in corrosion.
For example, if a piece
solution that does
of iron in contact with a piece of copper is immersed in a conducting
of the iron will
not contain appreciable amounts of iitn". Fe2* or Cut*, the potential
produced by the oxidation ofthe
be negative (anbalc) relative to the copper; the electrons
rron
Fe Fez* + 2e-
-------+ evolution or by oxygen
move to the copper, where they are removed either by hydrogen
metal, iron' If the two metals
reduction. The result is a rapid corrosion of the less noble
were not connected, both would corrode in an oxygenated
solution; but if the two metals
This is the basis of cor-
are electrically connected, only the more active metal corrodes.
rosion protection using a sacrificial anode' A bar of zinc ot
to the steel that is to be protected' In domestic hot w
magnesium rod is attached to t
"o.rn."Gd :rior of the steel tank' Th
protected. hung
but the steel tank is
over the side ofsteel ships to lessen the attac tal to
be protected is connectei to an external sour tial is
impressed to reduce the corrosion c
Corrosion can also be reduced of coat
effective the coating must be as impermeab sible or
if it is perforated. The protective oxide on m resea
Some anodic inhibitori alkalis, and oxidizing agents inhibit
corrosion by assisting the
and assisting the repair of
formation of a relatively adherent film of oxide on the metal
hand act by poisoning the
breaks in the coating. some cathodic inhibitors on the other
hydrogen evolution or, increasing the
+
,.au"ing tt. corrosion hibitors' Cu2
a film o-n the surface s oxYgen to the
shut offthe corrosion current.
94.12 PHOTOCHEMISTRY
The study of photochemistry embraces all
soc
tion and emission of radiaiion by chemi

des
mainly spectroscopic, such as fluorescence

ce'
reactions, such as flames and the glearn of the firefly; and photostimulated reactions, such
as photographic, photosynthetic, and ph_otolytic reactions of various kinds.
The influence of light on chemical systems may be trivial or profound. If the light
quanta are not energetic enough to produce a profound effect such as the dissociation
of a molecule, the energy may simply be degraded into thermal energy. This latter effect
may be regarded as trivial in a photochemical sense, since the same result could be
achieved by raising the temperature by any mans.
Any effect of light, whether trivial or profound, can be produced only by ligbt that
is absorbed by the system in question- This fact, which today seems obvious, was first
recognized at the beginning of the 19th century by Grotthuss and Draper, and is called
the law of Grotthuss and Draper.
34.13 THE STARK_EINSTEIN tAW OF

PH OTOC H EM ICAL EOI.'IVALEN CE
The Stark-Einstein law of photochemical equivalence is in a sense simply a quantum-
mechanical statement of the Grotthuss-Draper law. The Stark-Einstein law (1905) is
another example of the break with classical physics. It states that each molecule which
takes part in the photochemical reaction absorbs one quantum of the light which induces
the reaction; that is, one molecule absorbs the entire quantum;the energy of the light beam
is not spread continuously over a number of molecules.
If we define the primary act of the photochemical reaction as the absorption of
the quantum, then the quantum efficiency for the primary act is, by the Stark-Einstein
law, equal to unity. For each quantum absorbed, one primary act occurs. For any sub-
stance X taking part in a photochemical reaction, the quantum efficiency or quantum
yield for the formation (or decomposition) of X is @* and is defined by
number of molecules of X formed (or decomposed)
Qx: number of quanta absorbed
(34.s7)
More conveniently, if we measure the rate of formation of X in molecules per second,

dN*Jdt, then the quantum yield is
dN*ldt
Qx: number of quanta absorbed/second '
The number of quanta absorbed per second is the absorbed intensity, so that
dNJdt
Qx: Io
(34.s8)
To determine the quantum yield of the reaction it is necessary to measure the rate
of reaction and the amount of radiation absorbed. The rate of the reaction is measured
in any convenient way. Figure 34.15 shows a typical arrangement for measuring the
absorbed intensity. The reacting system is confined to a cell. The intensity of the trans-
mitted beam is measured with the reaction cell empty and with the cell filled with the
reaction mixture. The detector may be a thermopile, which is a set of junctions of dis-
similar metals covered with a blackened metal foil. All the radiation is absorbed on the
blackened metal and the energy of the radiation is converted to a temperature increase;
the temperature increase is converted to a potential difference by the thermopile. The
device must be calibrated against a standard light source. It has the advantage of being
Photophysical Processes; FluorescenceandPhosphorescence 891
Lens Cell Detector
Figure 34.15 Schematic diagrams ol apparatus

for measurement of light intensity
usable for light of any frequency. Photoelectric cells are convenient detectors but, since
the response varies with frequency, they must be calibrated lor each frequency.
A chemical actinometer can be used as the detector. The chemical actinometer
utilizes a chemical reaction whose photochemical behavior has been accurately in-
vestigated. For example, the compound, K3Fe(CrOo)., dissolved in a sulfuric acid
+
solution decomposes when irradiated; the CrOl- is oxidized to CO2 and Fe3 is reduced
to Fe2*. For wavelengths between 509 nm and254 nm the quantum yield for the pro-
duction of Fe2+ is known as a function of wavelength, varying between 0.86 and 1.25.
The Fe2* formed can be determined very accurately by adding 1,10-phenanthroline,
which forms a complex with Fe2*. The absorbance of the complex is measured colori-
metrically. Two measurements are made, one with the cell empty and one with the reactive
mixture in the cell. The first yields the incident intensity, 1o; the second yields the trans-
mitted intensity, I. The difference, Io - I:1o, is the absorbed intensity.
* 34.14 PHOTOPHYSICAL PROCESSES; FLUORESCENCE

. AND PHOSPHORESCENCE
Much of what is called photochemistry is in fact concerned with the phenomena of
fluorescence and phosphorescence in systems that do not undergo any chemical change.
We will first describe these photophysical phenomena and later discuss photochemical
processes. Since all of the electrons are paired in the ground state of most molecules, the
result of the absorption of a quantum of radiation is to unpair two electrons and produce
an excited electronic state that is either a singlet or a triplet. The energy levels of the
molecule then divide, much like the levels of the alkaline earth atoms, into a system of
singlet levels and a system of triplet levels. Bear in mind that at least some of these excited
states are bound states that will have vibrational and rotational levels associated with
them. A typical arrangement of the molecular levels is shown schematically in a Jablonski
diagram (Fig. 3a.16). The vertical axis measures the energy of the system; the horizontal
axis simply spreads the figure for the sake of clarity.
The singlet and triplet electronic levels are labeled S and T, respectively. Subscripts
indicate the order of increasing energy; the superscript u indicates that a molecule has an
excess vibrational energy; absence of a superscript indicates that the vibrational energy
of the molecule is in thermal equilibrium; a zero superscript indicates that a molecule is
in the lowest vibrational level. For clarity, the vibrational and rotational levelsbre shown
equally spaced.
If the system is initially in the ground state, So, the only quanta that it can absorb are
those which raise it to some level in another singlet state, S1 or S, in the diagram. (Radiative
transitions are indicated by solid lines, nonradiative transitions by wavy lines.) Because
v
lst Singlet
so
Ground state Ground state
Figure 34.1 6 Excited states and photophysical transitions between these states in a
"typical " organic molecule. Radiative transitions between states are given by solid lines,
radiationless processes by wavy lines; lC = internal conversion, ISC = intersystem
crossing. Vertical wavy lines are vibrational relaxation processes. Vibrational and rotational
levels are shown approximately equally spaced for convenience in presentation. (By
permission from J. G. Calvert and James N. Pitts, Jr. Photochemistry, New York: John
Wiley, 1966.)
of the Franck-Condon requirement, the molecule will most likely be in an excited vi-
brational state such as 51 or Si. Let us assume that the molecule is in the Si state and
examine the various possibilities.
The thermal equilibration of the vibrational energy within the electronic level 32
occurs rapidly; this is represented by the wavy arrow ending at Sr. The nonradiative
transition from 52 to Si'is also rapid; this is represented by the wavy horizontal arrow and
is called internal conversion (1C). Note that there is no change in energy in this process,
whereas the equilibration ofthe vibrational energy entails a loss ofenergy and therefore
requires one or more collisions to carry off the excess energy. From the level of S!' there
is again a rapid equilibration of the vibrational energy via collisions. In practice, this means
that after equilibration the system will most 4 obably be in the ground vibrational )eve)
of St since the vibrational level spacing is large enough to keep all but a few of the molecules
from occupying the upper states.
Having reached the lowest level in Sr, the system has three paths available for return
to the ground state, So.
Photophysical Processes; Fluorescence and Phosphorescence 893
path l: Radiative transition with emission of a quantum of fluorescent radiation, hv'.

The fluorescent radiation has a lower frequency than that of the absorbed light which
raised the system from So to S! ' Since the transitioD, S, + S6 ' is permitted by the selection
rules, it is very rapid. Since it drains the excited level very rapidly, it ceases almost im-
mediately after the exciting radiation, which supplies population to the upper state, is
extinguished.
path 2: Nonradiative crossing to Ti followed by rapid vibrational equilibration to Tt.
This is followed by a radiative transition T, --+ So. The radiation emitted is called phos-
phorescence. The nonradiative intersystem crossing (ISC) is much slower than the
vibrational equilibrations, but competes with the fluorescent emission in the molecules
that exhibit phosphorescence. The radiative transition, Tr - So, is usually very slow
since the tripiet-singlet transition is spin-forbidden by the selection rules. Consequently,
the phosphorescence persists for some time after the exciting radiation is turned off.
path 3a: Nonradiative internal conversion to S[' and rapid thermalization of the
vibrational energy to bring the system to So.
3b: Nonradiative quenching of St by collision.
We can describe the system under steady illumination by writing the rate equation for
each process.
Process Reaction Rate
Excitation Se+hv--St Io (34.se)
Fluorescence S, -' So + ftv' IroISt] (34.60)
Fluorescence quenching Sr+M-So*M ktts,l[M] (34.6r)
Internal conversion Sr-So kir[S'] (34,62)
Intersystem crossing Sr*Tr kir.[S'] (34.63)
Phosphorescence T, --+ So 1 ftv" lrr[Tt] (34.64)
Phosphorescence quenching Tr *M-+So+M 4tr,ltMl (34.65)
Intersystem crossing Tr-So kL.[T'] (34.66)
The k's are the rate constants for the various processes ; the ,4 ,o and A75 are the Einstein
coefficients for spontaneous emission. In this mechanism, M is intended to represent any
atom or molecule that may be present. Then [M], the concentration of M, is proportional
to the total concentration of all the species in solution; in the gas phase, [M] is pro-
portional to the total pressure.
The emitted intensity of fluorescence, I!^, is given by
1l' : Iro[St]. (34.67)
If the system is under steady illumination, the [Sr] and [Tt] do not vary with time; the
steady-state conditions are
d[S'] : 0:
dt
ro - .410[51] - /4tslltMl - kfc[sl] - k'l.[s,] (34.68)
and
d[T']
-:'-:
dt
u: kisc[sr] - 1rs[T,] - 4[T'lttnll - ftl'.[T']. (34-69)
We define tr, the fluorescence lifetime, and r", the phosphorescence lifetime, by
1
(34.7o)
-:A,o*Afc*kisc+ftftMl
and
1
Ar, + kL. + k;tMl. (34.11)

+:
These definitions reduce Eqs. (34.68) and (34.69) to
dilrl [S']
At - o: Io- r1
(34.72)
and
d[T,] :U:K7scl)ll-
n rS [T,] (34.73)
d, ,,
Solving these two equations for [St] and [Tr] yields
[S1]: tpl,; [T,]: klrrrrrplo- (34.74)
Using this value of [S,] in the expression in Eq. (34.67), we obtain for the fluorescence
lntenslty,
I!^: AtsrpIo, (34.7 s)
and for the quantum yield,
o, : I+: Arorr- (34.76)
If we invert Eq. (3a.75) and use the value in Eq. (34.70) for ro, we find that
+:] (t*k"'!*"n\*u;'ttt.
' Aro )' Aroto' (34.77)
/;-/,\'
A plot of llI!- versus [M], called a Stern-Volmer plot, should yield a straight line.
From the measurd value of 1o and a value of Aro we can obtain the quenching constant
kl. The constant Aro can be calculated from the measurement of the molar absorption
coefficient of the absorption band.
If we assume that every collision is effective in quenching the fluorescence, then the
rate of quenching is the number of collisions between the excited species, S1, and all other
species, M. The number of collisions is given by Eq. (30.23).
Ztz: *.i,r]|#fr,fr,. (34.78)
Thus we expect kf will have the value

8kT
kf,: nol2
ltu
(34.7e)
Photophysical Processes; Fluorescence and Phosphoresoence 895
in which o' is the average.of the two molecular diameters. The iactor, nolr.is the collision
(3a.79) a-re usually larger than the
cross section. In fact, the values of k[ calculated by Eq.
values- If we define a quenching cross section, zof such that
"*p".i-.ntul
: 8kr (34.80)
(kt)-"". ttozn
np
cross section to the

then the ratio, (kf)^."./(kf)""rr, is equal to the ratio of the quenching
collision cross section:
(k;)_"". _
(kf)*rr
I
no?z
of NO2 are given in

Some values of the ratio lnof)l@o1r) for quenching the fluorescence
ttrit ttre effectiveness of a molecule in quenching fluore-
Table 34.2.These values indicate
scence increases as the number of internal modes of motion increases' For example' if a
energy can only
helium atom or argon atom collides with an activated molecule, the excess
be drained off into translational energy of the colliding atom.
This process is not very
the relative cross sections of He
effective in dissipating the excitation energy and, as a result,
are quite r-ull. Th" value 0.04 can be taken to mean that UO.O4
:25 collisions are
""Jn. to quench the excitation.
required
H2 is relatively
ineffective while O, and N2 are on se molecules do
have a. vibrational mode, ihe vibrational q
not effective in
quenching. Molecules with small spacings e vib
levels are more effective than those with I ngs'

more modes of motion and heavier atoms ar y mo
Table 34.2
Cross sections for quenching NO, fluorescence by
Oitietent gases (excitation waveleingth = 435'8 nm)
fio?
Quenching gas nolllo-to m2 nolrf lo-20 m2 no?z
He 1.6 34.2 0.04

Ar 3.8 44.0 0.08
H2 2.5 38.3 0.06
N2 5.0 48.',| 0. l0
o2 6.0 46.2 0. l3
NO 9.7 47.4 0.20
CHo 7.9 50.2 0.16
NrO l 1.9 50.2 0.24
NO, 13.5 55.3 0.24
CO, l 3.8 5r.5 0.27
'72.5 0.35
SFu 25.7
CFo 24.5 61.9 0.39
Hro 28.3 59.3 0.48
From G. H. Myers, D' M. Silver' and F' Kaufman, J' Chem' Phys
44,7 t8 (1966)
the sizes of the vibrational and rotational energy quanta; similarly, complex molecules
have bending vibrational modes, which have low energy quanta. Polar molecules, such as
water, are particularly eflective.
Note that if the system does not exhibit phosphorescence this implies that kfr. : g.
Then the value of kf. can be determined from the intercept of the Stern-Volmer plot if ,4 , o
is known.
If phosphorescence does occur, then
I'^ : ArtlT tf' (34.81)
The value of [Tr] is given bl' Eq. (34.74), so that
I'^ : Artldtsrprpl'. (34.82)
The quantum yield for phosphorescence is

1P
Qp:?:la A7sks15srptp. (34.83)
Using Eq. (34.76) we can write this in the form
r,: r,(*)o*.,". (34.84)
By inverting this equation and using the value in Eq. (34.71) for r", we have
{Ars*kTrr*k;tMl}
*:#0*) r.S
^r.sc
(34.85)
If both Q, and Qrhave been measured as a function of the total concentration, [M], a
Stern-Volmer plot of ll$, \'ersus [M] can yield the quenching cross section for phos-
phorescence and the ratio, kl5./Cr"., il the Einstein coefficients are known.
* 34.15 FLASH PHOTOLYSIS

While the steady-state measurements made under continuous illumination yield ratios of
rate constants, the absolute values ofthe rate constants can be determined from a study of
the transient phenomena (such as the decay of fluorescence or phosphorescence) that
appear after the interruption of the incident radiation. Flash photolysis is an important
method for studying transients in a photochemical system.
The apparatus for a flash photolysis experiment is shown in Fig. 34.17.The reactive
materials are irradiated with an intense flash of "white" light, which provides a continuum
of wavelengths from the infrared to the vacuum ultraviolet. The energy for the flash is the
energy stored in a large capacitor (- 10 prF) charged to about 10 kV. When the capacitor is
discharged through a tube containing an inert gas (such as krypton) at about 100 mm
pressure, a brilliant flash of light is produced. This intense light falling on the system raises
the material to a variety of ercited states and produces a variety of active intermediates.
The duration of the flash ranges from 1 to 100 ps. The energy is determined by the capacity
and the voltage, g : lCY2;the time of the flash depends on the electrical resistance, which
is proportional to the lengrh of the flash tube, the capacitance, and the inductance of the
circuit. Energies ofthe order of 1000 J per flash are usual.
Flash Photolysis 897
Monitoring flash
(or continuous source)
Photographic
(or photoelectric)
detector
Figure 34.17 Schematic diagram illustratin ple of the flash photolysis

technique. (By permission from G. Porter, Fl sis, Technique of Organic
Chemistry, vol. Vlll part ll. S. L. Friess, E. S. A' Weissburger, eds' New
York: lnterscience, Div. of John Wiley' 1963.)
After the system is exposed to the flash, a time-delay circuit fires a lorv-energy flash
from the monitoring flash tube. This beam of light passes through the excited species
produced by the firsi flash and an absorption spectrum is recorded on the spectrograph.
^By
uarying ih. d"luy time, we can observe the rate of decay of the various species. Alter-
natively, after mating an initial spectrographic study to determine the identity of the
species present, we can choose a particular wavelength and measure the absorption
at
this wavelength as a function of time; we do this by replacing the monitoring flash tube
with a continuous source such as a tungsten filament lamp. When we place a mono-
chromator in the optical path, the transmitted radiation is collected in a phototube
whose output we can monitor on an oscilloscope. By this means we can follow the concen-
tration of a selected species as a function of tlme.
We can interpret ihe transient behavior of Sr by using the mechanism given above but
modifying it by setting I, : O since the source has been extinguished. Then instead of the
steady-state condition, Eq. (34.72), we have
d[S,] _ _ [S'] (34.86)
dt rF
This is the first-order rate law, which on integration yields
[Sr] : [Sr]oe-'l" (34.87)
Using this result in F;q. Q .67), we obtain the expression for the decay of the emitted
fluorescence intensity with time.
tt'F,
I!^ : A.J)lSr) 6e-tt'r : (I:^)oe- (34.88)
where (IL)o is the emitted fluorescence intensity at the time when the incident radiation is
turned off. Measurement of rF as a function of concentration yields the value of kf from the
theplot of lltrversus[M],andthesum, Aro* /Cr.+kfr.,fromtheintercept;seeEq'
(34.70).
We can treat the decayofthe phosphorescence similarly. Instead ofsettingd[T r]ldt : 0

as in Eq. (34.73), we write
+:kf"[S'i-T (34.8e)
Using the value of [Sr] lrom Eq. (3a.87] and rearranging, we have
d[Tr]
-: + [Tr] : . c
fttsc[S,]oe-'i'".
al ;
Since the initial concentration of S, is the steady-state concentration under illumination,
we may use Eq. (34.73) and set kir.[Sr]o : lT rfolrp, so that this equation becomes
d[Tt] ff tl _ [T,]os-"'" (34.e0)

dt - tr- +
This equation can be easily integrated if we substitute for [Tr]:
[Tt] : F(t)e-tt'" (34.er)
It then becomes
dF: ff ,lo e-'l' in which
E t, ' Tp Tp
This equation integrates directly to
r : rr,l.(r + ! -+) : r, tPi#)

since F(0) : [Tr]o.Then Eq. (34.9I) becomes
[r,]: 7r,1"(2t!-:4
\ rP-rr (34.e2)
Inserting this expression in Eq. (34.81), we obtain
I!^: (f.)oPZ!:-::t\,
\ rP-rr /
(34.e3)
in which we have set .4rr[Tr]o : (I!^)a, the initial value of the phosphorescence in-
tensity.
Ordinarily r" is many orders of magnitude smaller than r". Typically, zo < 10-? s,
while r" = 1 to 10 s. This means that r" - rr N 2". It also means that after a few multiples
of r. (a few microseconds) have elasped, the term in exp (- tlt ,) has decayed to a negligible
value and we are left with a simple exponential decay for the phosphorescence:
IP". : (I!^)os-tl'", (r ) r.). (34.e4)

The existence of the nonzero lifetime, rr, introduces a very slight deformation in the curve
of If. versus t at very short times but does not affect the rate of decay at longer times.
Since the flash produces relatively large populations in the excited states, it is possible
to observe the absorption spectrum of some of these excited species ;for example, transitions
899
Absorption and Emission Spectra of Organic Molecules
from the triplet state

from an excited singlet state to higher singlet states, and transitions
ol inlormation about
to the higher triplei states. This method has yielded an abundance
the energy levels of molecules.
34.16 ABSORPTION AND EMISSION SPECTRA OF

ORGANIC MOLECULES
When the molecules in a given electronic state are thermally
equilibrated, most of them are
spectrum consists of a
in the lowest vibrational ievel of that state. Therefore the absorption
UunJ tfrut originates in the lowest vibrational level
of the ground electronic state' Con-
versely, since the internal conversion proc
species are quickly drained down to the I
ernitted originates in the lowest vibratio
vibrational levels of 56. The energy levels
is clear that absorption involves larger ener
the absorption band is in a shorter wavelengt
state to ground-state transition is the same tc
appear to be the mirror image
about the same in the two states, the emission spectrum will
on a frequency scale will
of the absorption spectrum (at least the p rsition of the lines
appear so). Wtrettrei the intensities match depends on the
overlap of the wave functions in
the two states. Figur e 34.19 shows the effect for anthracene
in three different physical
states. The numbers in the fi vibrational quantum numbers
in the upper (prime) and lo 0-0 bands for absorption and
fluorescence are separated cited state has a long enough
energy slightly before the
lifetime to equilibrate with its neighbors and thus lower its
ng
Th
fluorescence occurs.
lid
the absorPtion Process'
phase is tyPical; it is th
s1
so \-J \------Y-
Absorption Emission
Figure 34.18 Transitions in absorption

lncreasing I and emission.
300 nm
O
c
O
O
a
O
o
G
b0
o
J
20.000 25,000_1 30,000
Figure 34.19 Absorption (shaded curves) and fluorescence spectra of

anthracene in vapor, solution, and solid phases. Arrows indicate the 0-0 bands.
Note the red shift and increased separation of the G-0 bands in going ro the solid
phase. Other vibronic bands are shown for the vapor. (From J. G. Calvert and
J. N. Pitts, Jt Photochemlstry New York: John Wiley, 1966.)
34.17 ABSORPTION WITH DISSOCIATION

A common class of photolltic reactions consists of those in which the primary photo-
chemical act is absorption of the quantum by a molecule followed by dissociation of the
molecule:
M+hv + Fragments.
Since the fragments produced are often atoms or free radicals, this primary step frequently
initiates a chain mechanism, whose occurrence may be indicated by quite large values of
the quantum yield, although a chain reaction can occur with very small values of the
quantum yield.
Ordinarily the energy required for an absorbed light quantum to produce dissociation
of a molecule is significantly greater than the thermodynamic dissociation energy of the
molecule. The reason is simply that for radiation to be absorbed there must be an upper
electronic state to which the system can be transported by the absorbed quantum. The
potential energy diagram for I, is shown in Fig. 34.20.The absorption band of I, is due to
the transition from the lowest vibrational level of the rt; state to the levels in the 3flf,, state.
The band converges to a continuum at 499.0 nm. At this wavelength the energy of the
transition is sufficient to bring the molecule to that required to dissociate the molecule into
two iodine atoms, one of which is in the excited state,2 P Ltz. Strictly speaking, the transition
from rI j to 31lf,, should be spin-forbidden, but because of the large number of electrons
in the Ir molecule this prohibition is relaxed. The transitions from the ground state to
3lI and 3X j are very weak. From the diagram we see that the thermodynamic dissociation
r,
energy is only 148.71 kJ/mol while the energy of a 499 nm quantum is 239.13 kfmol. It
Absorption with Dissociation 901
I
-/
t â A "mixed"
o=- state \\'ith
both l>/and 3II;,
t
\ contributing
ô 500
3s+
h aoo "u
O
o
a! tnd,
:E 300
\ zPr,, + 2P*
-'--------
91.02 kJ
zPr,, + 2Pr,,
z,-11ru-------7=-tar--
1s+ Do= 148.71 kJ
Resonance
fluorescence
400
r/pm
Figure 34.20 Potential energy diagram for several states of the lr(9) molecule.
(From J. G. Calvert and J. N. Pitts, Jr. Photochemistry. New York: John Wiley,
1966.)
follows that the excitation energy for an iodine atom from

2P3pto'Pr,ris 91.02 kJ/mol.
The dissociation process can be written
Ir+hv + l('Ptp)+I(Pr2), A<499nm.
More often we would simply write
I2+hv + I+I*, )'<499nm,
indicating by the asterisk that the iodine atom is in an excited state. Table 34.3 shows some
reactions together with the wavelengths below which the dissociation occurs.
In the case of oxygen the continuum begins at 175.9 nm corresponding to a transition
from the 3I; state to the 3X; state. As indicated, the dissociation produces one normal
and one excited oxygen atom.
The case of HI is unusual in the sense that all the upper states of HI are repulsive.
Depending on the wavelength, the iodine atom may or may not be in an excited state. But
in ill instances the product atoms have a large amount of excess kinetic energy. Because of
the great differences in the masses of the H atom and the I atom, most of this excess energy
Table 34.3
Wavelengths required to dissociate
simple molecules
Reaction ).lnm
H" * ftr'- H(ls) + H*(2s cr 2p) < 84.5

01 + fir'' o(3P) + o*('D) < 175.9
Cll + ftr'- Cl + Cl* <478.5
Br, + ht' - Br + Br* <511.0
I7*ht' l('Pr,r) + I*(2Pr,2) <499.0
H[+ftv- H+I <327
NO" * ftr'- NO+O < 366
NH3 + ilrr - NH2+H < -220
H2O + lru - H+OH <242
o
il
R-C-H * hv - R+CHO < -330
o
il
R-C-R I hv + R+RCO < -330
is given to the hydrogen atorl, which is then referred to as a "hot" atom. Figure 34.2 I
shows the transitions from a bound state to two different repulsive excited states. When the
molecule is excited from the ground vibrational state to the state at point B, the excess
energy labeled AE is an amount beyond that needed to dissociate the molecule to normal H
and I atoms. This excess energy winds up as the kinetic energy of a hydrogen atom in its
ground electronic state. Depending on which states are involved,'the excess kinetic energy
can be very large.
E
E
,]i
b0
(.)
tr
O
(d
O
o
p.
S*) + I(2P"6)
Figure 34.21 Potential energy curves for the

lowest electronic states of Hl. (Adapted from J. G.
200 400 600 Calvert and J. N. Pitts, Jr. Photochemrstry. New
Internuclear distance/pm York: John Wiley, 1966.)
Examples of Photochemical Reactions
34.18 EXAMPLES OF PHOTOCHEMICAL REACTIONS

34.18.1 The Photolysis of Hl
The kinetics of two photochemical reactions will be compared with the kinetics of the
thermal reactions. In the absence of light, hydrogen iodide decomposes by the elementary
reagtlon:
2Hr H2 + 12,
or possibly
2HI + H2+2L
In the initial stages the reverse reaction can be iglored. In either case the rate ofreaction
can be written
!d4: dtHrl :
Vdt -!2 dt k[Hr],
In the photochemical reaction, at wavelengths below about 327 nm, the mechanism is
HI+hv H+I, Rate:1o,
H+HI + H2+I, Rate : kr[H][HI],
2I + Ir, Rate : k.[I]t.
Other possible elementary reactions either have much higher activation energies or require
three-body collisions. The rate of disappearance of HI is
-dtHlt I,t kr[H][HI].

-.7:
The steady-state requirement is
+: o: r,- k,[H][Hr].
Corrrbining these two equations, we obtain
-d[Hr] :2Io (34.es)

dt
By definition the quantum yield is O : edlHlllilt)11", so that, from Eq. (34.95) we find
that S : 2. ln a variety of experimental situations, the observed value of $ is 2.
The interesting point about the photochemical reaction is that the rate, by Eq.(34.95),
is simply twice the absorbed intensity and is not directly dependent on the concentration
of HI. This fact implies that the reaction is very slow, since even fairly intense light sources
do not produce a very large number of quanta per second. The dependence of rate on
intensity can be readily verified by altering the distance between the system and the light
source. The incident intensity varies inversely as the square ofthe distance, so for a given
cell and given concentration of HI, the absorbed intensity must vary in the same way.
Indirectly, the rate depends on the concentration of HI, since the absorbed intensity is
dependent on concentration through Beer's law.
34J8.2 The Photochemical Reaction between H, and Br,

The photochemical reaction between H, and Br, follows a kinetic law which resembles that
for the thermal reaction, in contrast to the decomposition of HI, where the kinetics are
quite different. Using light of wavelength less than 51 I nm, the mechanism of the photo-
chemical reaction between H, and Br, is
F ) 2Br,J
Br,+ftv -) 2tn
Br+H, o" HBr+H.t,
H+Br, r'' HBr+Br,J

ko
, Hr+Br,
H+HBr
2Br t' , Brr -
The rate of formation ol HBr is the same as that given in Eq. (32.65) for the thermal
reaction
ry: kz[Br] [H,] + k.[H] [Br,] - kn[H] [HBr]. (34.e6)
The steady-state conditions for H atoms and Br atoms are
4l!] : 0 : kr[Br] [H,] - k.[H] [Brr] - ko[H] [HBr],

dt
dlBrl r/ v
T:0:2t, - kr[Br][Hr] + k.[H][Brr]+ ko[H][HBr] -2krlBrl2.

Addition of these two equations yields 2krlBrf2 : 2lo, so that
rBrt:
e),,,
This result in either of the steady-state equations yields ultimately
I k,\,,,,
rT{l : \{t'"J"
L^^r kr[Brr] + ka[HBr]'
These values in Eq. (34.96) bring it to the form
(34.e7)
The expression in Eq. (34.97) is very similar to that forthe thermal reaction where the factor
Ilt2 is replaced by kll2(Brr;1/2. This means that the bromine atom concentration is main-
tained by the photochemical dissociation of bromine rather than the thermal dissociation.
The dependence on the square root of the intensity is notable, since it has the consequence
Photosensitized Reactions 905
that the quantum yield is inversely proportional to the square root of the intensity:
As the intensity increases, a greater proportion of the bromine atoms formed are converted
to Br, instead of entering the chain;most of the additional quanta therefore are wasted,
and the process is less efficient. Because kt is very small, the quantum yield is less than unity
at room temperature in spite of the fact that the HBr is formed in a chain reaction. As the
temperature increases, the increase in kr increases the quantum yield (kr is nearly inde-
pendent of temperature).
34.19 PHOTOSENSITIZED REACTIONS

Photosensitized reactions make up an important class of photochemical reactions. In these
reactions the reactants are mixed with a foreign gas; mercury or cadmium vapor are often
used. The primary photochemical act is the absorption of the quantum by the foreign atom
or molecule.
If a mixture of hydrogen, oxygen, and mercury vapor is exposed to ultraviolet light, the
mercury vapor absorbs strongly at 253.'7 nm with the formation of an excited mercury
atom, Hg*:
Hg+hv + Hg*.
The energy corresponding to this wavelength is 471.5 kJ/mol. The energy required to
dissociate a molecule of hydrogen in its ground state to two hydrogen atoms in their
ground state is 432.OkJlmol. The dissociation of oxygen requires 49O.2kJlmol. The
energy possessed by the excited mercury atom is more than enough to dissociate H2 but not
enough to dissociate 02. The quenching reactlon
Hg* + Ht Hg+H+H
introduces H atoms into the mixture, which can initiate chains to form HrO by the usual
mechanism. A reaction that is initiated by light in this way is a photosensitized reaction;
the mercury is called a sensitizer.
The importance of photosensitization derives from the fact that reaction is produced in
the presence of the sensitizer in circumstances where the direct photochemical dissociation
is not possible. The example just cited is a case in point. Radiation of wavelength 253.7 nm
was absorbed by a mercury atom. The excited mercury atom dissociated a molecule of
hydrogen by transferring the exciiation energy in a collision. The mercury atom had
47I.5 kJ of this 432.0 kJ were needed for the dissociation; 39.5 kJ are left over and go into
additional translational energy of the two hydrogen atoms and the mercury atom. If the
attempt is made to dissociate H, directly by the process
H2*hv # H+H,
we find that light of 2: 253.7 nm will not produce any dissociation even though it still has
the 471.5 kJ, which is more than enough if we consider only the thermodynamics of the
process. For the direct absorption to produce dissociation, the wavelength must lie in the
absorption continuum; for H2 the continuum begins at 84.9 nm. The absorption of light
in the continuum produces at least one atom in an excited state:

Hr+fir' + H+H*, 7<84.9nm.
As we have seen, the selection rules that govern the absorption of radiation forbid the direct
absorption of a quantum by H2 to yield two H atoms in their ground state;thus a quantum
otlight does not necessarily produce dissociation even though it may have sufficient energy.
The quantum must have enough energy to produce the dissociation in the special way
required by the selection rules. The transfer of energy in a collision is not limited by this
requirement, and so sensitization can produce dissociation.
The decomposition of ozone sensitized by chlorine is another example of photo-
sensitization. Ozone is stable under irradiation by visible light. The absorption continuum
begins at about 290 nm. In the presence of a little chlorine, ozone decomposes rapidly.
rhe chrorine absorbs oll;1,"
'
H'i'n"J"lT ^ 478.5 nm.
The chlorine atoms react with ozone mechanism. Bromine is also

in a complex chain
effective as a sensitizer for this decomposition.
The decomposition of oxalic acid photosensitized by uranyl ion is a common actino-
metric reaction. The light may have any wavelength between 250 and 450 nm. The
absorption of the light quantum activates the uranyl ion, which transfers its energyto a
molecule of oxalic acid, which then decomposes. The reaction may be written
+hv 4
lJO2r* (UO3*)*
(UO3*)* + H2C2O4 + UO|* + H2O + CO2 + CO'
The quantum yield depends on the frequency of the light, varying between about 0.5 and
0.6. After a measured period of tine, the light is turned off and the residual oxalic acid
determined by titration with KMnOo. From these data and knowing the original amount
of oxalic acid, the intensity is calculated using the value of the quantum yield appropriate
to the frequency of light used.
A practical example of photosensitization is in the use of certain dyes in photographic
fi.lm to render the emulsion sensitive to wavelengths that are longer than those to which it
ordinarily responds; for example, infrared photography, which permits photographs of
objects in the absence of visible light.
34.2O PHOTOSYNTHESIS
The synthesis of the compounds required for the structure and function of plants is
sensitized by chlorophyll, the principal constituent of green-plant pigments. Chlorophyll
exhibits two strong absorption bands in the visible region, a band between about 600 and
680 nm and another between 380 and 480 nm; it is the long wavelength region that
apparently is most efficient in photosynthesis. In addition, there is a molecule, apparently
a particular form of chlorophyll-c, which absorbs at 700 nm. This form is crucial to the
photosynthetic mechanism. The other plant pigments such as the carotenes and the phyco-
bilins contribute through their ability to absorb light and transfer the excitation energy to
chlorophyll-a.
The photosynthesis reaction of classical chemistry was written in the form of the over-
all transformation
nCO2 * nHtO + xhv + (CH2O), * nOr.
The Photostationary State 907
The (CH2O), is the general formula for a carbohydrate. It was then assumed that the
energy stored in the carbohydrate was used in other chemical reactions to synthesize
all
the o"ther plant materials (proteins, lipids, fats' and so on). It is now clear that amino acids'
for example, are immediaie products ol the photosynthetic reduction of carbon dioxide'
and that iarbohydrate need not be synthesized first. This is not to minimize the
importance
of com-
of the photosynthesis ol carbohydrate, but only to note that many other types
details
pounds are pioduced photosynthetically. The overall mechanism and many of the
of th" reduction cycle, CO, to carbohydrate, were worked out by Melvin Calvin and
"u.bon
his colleagues. lor which he received the Nobel Prize'
The g"athering of energy occurs via the plant pigments; the energy is transferred
to
water to oxygen and in the
chloroph"ytl-a, which in onJior- transfers th: energy to oxidize
phosphate,
other form ultimately reduces the compound nicotinamide adenine dinucleotide
NADp, to NADpH. It is the reducing ability of NADPH that ultimately brings the CO, to
(cH2o),.
These reactions are mediated through many steps by enzymes, and labile
intermediate
compounds. It is apparent that between 6 and 12 moles of quanta are required to convert
requiring several stages of
one mole of carbon to carbohydrate. It is an intricate mechanism
pumping energy uPhill.
34.21 THE PHOTOSTATIONARY STATE I

The absorp-
Absorbed light has an interesting effect on a system in chemical equilibrium'
tion of light by a reactant can increase the rate of the forward reaction without directly
influenciig the rate o[the reverse action; this distufbs the equilibrium. The concentration
of producti increases somewhat, increasing the rate of the reverse reaction'
In this way the
raGs of the forward and reverse reaction can be brought into balance with the system
having a higher concentration of products than that in the equilibrium system' This
stationary called a photostationary state'
new state is not an equilibrium state but a state,
The dimerization of anthracene offers a convenient example. The reaction
2A41^2
occurs upon irradiation ol a solution of anthracene by ultraviolet light' A plausible
mechanism is
A+hv Rate : 1o,
A*+A + Ar, Rate : k2[A*][A]'
A* + A+hv', Rate : k.[A*], (fluorescence)
A2 + 24" Rate : kn[Ar].
The net rate of formation of ,{2 is

dl{r) : (34.e8)
dt
kz[A*] tAl - knlAr).
In the steady state, d[A*]/dt :0, so that

Io
0 : 1o - kr[A*] tAl - k.[A*] or [A*] kr[A] + kt
(34.ee)
In the photostationary state we have the additional requirement that dlAr]ldt

:0; so
that Eq. (34.98) yields for the concenrrarion of Ar,
ft'z[A*] [A]
[A'] : k4
Using the value for [A*] from Eq. (3a.99), we obtain
k2l{ll, I
[A']: k4(k2l{l + kl k4{1 +
o
(ulkrl l)}
If the concentration of monomer, [A], is very large, then this becomes
b,t: + K4
(34.100)
The difference between Eq. (3a.100) and the usual equilibrium elplgssion [42] :__5IA-12,
should be noted.In the photostationary state in the condition for whic[E{. (34.100) is
appropriate, the concentration of dimer is independent of the concentration of monomer.
Many other examples of the photostationary states are known. The decomposition of
NO2 occurs photochemically below - 400 nm.
NO2*ftv NO+]Or,
while the reverse reaction is a dark reactio
-
The maintenance of a certain amount ofozone in the upper atmosphere is the result of
a complex photostationary state. The ozone filters the sun's rays so that no radiation of
wavelength shorter than about 290 nm reaches the earth's surface. Ozone absorbs strongly
at wavelengths shorter than this. This fortunate circumstance of the ozone layer makes life
possible on earth. Radiation of wavelengths shorter than this produces severe damage and
in many cases has a lethal effect on living cells The effective thickness of the ozone layer is
estimated at about 3 mm if the gas were at standard pressure and temperature. Since
halogen atoms catalyze the decomposition ofozone, the accumulation of halogen atoms in
the upper atmosphere from the photolytic decomposition of fluorocarbons has prompted
grave concern over the massive commercial use of these compounds. A significant depletion
of the ozone layer could have serious adverse effects on life forms on earth.
34.22 CHEMILUMINESCENCE
Reactions of the ordinary thermal type in which some intermediate or the product itself are
formed in an electronically excited state exhibit chemiluminescence.The excited molecule
emits a quantum of light, usually in the visible spectrum. Since the reaction may be pro-
ceeding at ordinary temperatures, the light emitted is sometimes called "cold light,"
presumably to contrast it with the "hot light" emitted by a flame or incandescent body.
The oxidation of 3-amino phthalic cyclic hydrazide, luminol, in alkaline solution by
hydrogen peroxide is a classic example. A bright green light is emitted.
The greenish glow of slowly oxidizing phosphorus is apparently due to the formation
of an oxide in an excited state. The light of the firefly and the light emitted by some micro-
organisms in the course of metabolism, bioluminescence, are other examples of chemilum-
inescence. The phosphorescence observed in rnarshy areas, the will o'the wisp, is apparently
due to a slow oxidation of rotting organic material.
Problems 909
OUESTIOi.IS
34.1 Discuss the similarities and differences between the surface decomposition rate law, Eq. (34.5),
and the Lindemann rate law, Eq. (32.61).
3.2 Discuss the Case 3 surface decomposition rate, Eq. (34. I9), in terms ol the competition ol
reactants A and B for the available surface sttes.
34.3 Estimate the activation energy decrease by a catalyst required to triple a reaction rate at 300 K.
}4.4 Argue that the Eq. (34.31), when applied at equilibrium, is consistent with the Nernst equation.
34.5 Why doesn't the exchange current io vanish at equilibrium?
3.6 What is the meaning of z in Eqs. (34.29) and (34.30)? Il the potential @ is approximately linear
in the separation of a metal ion from the metal through the double layer, '*'hat does the typical
ralue a: 1/2 suggest about the symmetry of the chemical Gibbs energy (AG|) behavior as a
function of this separation?
34.7 Contrast fluorescence and phosphorescence in terms ol(a) routes available to relevant electronic
states, (b) the wavelengths involved, and (c) radiative lifetimes.
3.8 Would the fluorescence emission spectrum of a molecule depend on time if internal conversion
processes were not rapid? Explain.
34.9 How could absorption with dissociation of a diatomic combined with fragment energy measure-
ments be used to determine dissociation energies?
34.10 Organic singlet S, and triplet Tr states olten undergo different reactions. T, can sometimes be
produced directly from So by a so-called triplet sensitizer. What advantage does this have over
irradiation of So if only the product from T, is desired ?
PROBLEMS
34.1 The diffusion coefficient of many species in aqueous solutions is of the order of l0-e m2/s. In a
well-stirred solution, ti : 0.001 cm. If the concentration of the reactant molecule is 0.01
mole/litre, what will be the rate of the reaction if the slow step is diffusion of the reactant to the
surface? The concentration ofthe reactant at the surface may be taken as zero, since it reacts
very rapidly on arrival at the surface.
34.2 a) Using data from Table 34.1, compare the relative rates of the uncatalyzed decomposition
of HI at 400 K and 500 K.
b) Compare the relative rates of the catalyzed decomposition of HI on platinum at 400 K and
500 K.
34,3 What conclusions can be reached about absorption on the surface from each of the following
lacts ?
a) The rate of decomposition of HI on platinum is proportional to the concentration of HI.

b) On gold the rate of decomposition of HI is independent of the pressure of HI.
c) On platinum, the rate of the reaction SO2 * lOz - SOr is inversely proportional to the
pressure o[ SO. .
d) OnplatinumtherateofthereactionCO, * H2 * H2O + COisproportionaltothepressure
of CO, at low CO, pressures and is inversely proportional to the pressure of CO, at high
CO, pressures.
3.4 The galvanometer in a potentiometer circuit can detect t l0-6 A. The io for hydrogen evolution
is 10-la A/cm2 on mercury and l0-2 A/cm2 on platinum. If the electrode area is I cm2, over
what range of potential will the potentiometer appear to be in balance (a) if platinum is used as
a hydrogen electrode? (b) if mercury is used as a hydrogen electrode? (Assume that the relation
between i and 4 is linear: r: 20 "C.)
34.5 By passing a current through a lerric sulfate solution, l5 cm3 of O, at STP is liberated at the
anode and the equivalent quantity ol ferric ion is reduced to ferrous ion at the cathode. Il the
anode area is 3.0 cmz and the cathode area is 1.2 cm2, what are the rates of the anodic and
cathodic reactions in Ai cm2'l The current passes lor 3.5 min.
34.6 The exchange current measures the rate at which the forward and reverse reactions occur at
equilibrium. The exchan-ee current lor the reaction ] H2 H * + e- on platinum is l0 2 A cm2.
=
a) How many hydrogen ions are formed on I cm2 of a platinum surlace per second?
b) If there are l0t s sites/cm2 for absorption of H atoms, how many times is the surface occupied
and vacated in I second?
34.7 Consider the oxidation reaction Fe - Fe*2 I 2e-.
a) By how much does the activation Gibbs energy change from its equilibrium value if an over-
:
potential of +0.100 V is applied to the anode? Assume s j, and t 25'C. :
b) By what factor does this increase i* over the io?
34.8 Silverisdepositedlroma0.l0mollLAg* solution.ForthereactionAg* + e- - Ag,a :0.74,
io:4.5A/cmr when [Ag*]:0.l0mol/L at 20"C. Calculate tbe overpotential for current
densities of 10-3. l0 'z, l0-t, and I Alcm2.
34.9 Asolutioncontains0.0lmol/LCd2*and0.l0mol/LH*.Forhydrogendepositiononcadmium,
Eq.(34.42) represents the situation if io : 1g- t2 A1cm2,z : *1, and q : J; the same equation
represents the current voltage curve for cadmium deposition if a : I and io : 1.5 mArcm2.
Theequilibriurnpotentialof theCd2* +2e-=Cdreactionis -0.462V,in0.0lmol/LCdr*
solution and the equilibrium potential ol the 2H+ + 2e- couple is -0.060V in 0.10
mol/L H+ solution at 25'C. =H,
a) At what current density will cadmium deposition commence?
b) When the current density is - 1.0 x l0- 3 A/cm2 what fraction of the current goes into h1'dro-
gen evolution?
34.10 Suppose that a piece of cadmium is touched to a piece of platinum, and the metals are immersed
in a 0.1 mol/L acid solution. Calculate the corrosion potential and the rate ol dissolution of the
cadmium for various ratios of the areas'. Ar,f Aca : 0.01, 0.10, 1.0, 10, and 100. For hydro-een
evolution on platinum, Eq.(34.42) may be used with io:0.10mA/cm2, z: *1, and e: j.
For cadmium dissolution io : 1.5 mA /cm2 and a : j. The equilibrium potentials are: @o,n -. ,r., :
-0.060 V; do,co....o, : -0.462 V at 25'C.
3.ll Use the data in Problems 34.9 and 34. l0 and suppose that a piece of cadmium is immersed in an
acid solution. What is the corrosion potential and what is the rate of dissolution of the cadmium
if the area ratios are: A.lA,: 1.0, 103, 106, and l0e'l
y.l2 A 0.01 molar solution ola compound transmits 2O/"of the sodium D line when the absorbing
parh is 1.50 cm. What is the molar absorption coefficient of the substance? The solvent is
assumed to be completely transparent.
34.f3 Il l0\ of the energy of a 100 W incandescent bulb goes into visible light having an avera-qe
wavelength o1600 nm, how many quanta of light are emitted per second?
34.14 The temperature of the sun's surface is 6000 K. What proportion of the sun's radiant energf is
contained in the spectrum in the wavelength range 0 <,1 < 300nm?(See Problem 19.3.)
34.15 The ozone layer is estimated to be 3 mm thick if the gas were at I atm and 0 'C. Given the
absorption coefficient a (defined by 1 : 16 I 0
opr
where p is the pressure in atm and / is the length
in cm). What is the transmittance to the earth's surface at each of the following wavelengths ?
ilnm 340 320 310 300 290 280 260 240 220
a/cm-r atm-r 0.02 03 12 44 t2 48 130 92 20

34.5 By passing a current through a ferric sullate solution, l5 cm3 olOr at STP is liberated at the
anode and the equivalent quantity ol lerric ion is reduced to lerrous ion at the cathode. If the
anode area is 3 0 cm2 and the cathode area is 1.2 cm2. what are the rates olthe anodic and
cathodic reactions in Arcm2'l The current passes lor 3.5 min
34.6 The exchange current measures the rate at which the forward and reverse reactions occur at
equilibrium.Theexchangecurrentlorthereaction jH, H* * e- onplatinumis l0-2A cm2.
=
a) How many hydrogen on I cm2 of a platinum surlace per second?
ions are lormed
b) Iftherearel0rssites/cm2forabsorptionofHatoms,howmanytimesisthesurfaceoccupied
and vacated in I second?
34.7 Consider the oxidation reaction Fe - Fe*2 * 2e-.
a) By how much does the activation Gibbs energy change from its equilibrium value if an over-
potential of +0.100 V is applied to the anode? Assume a : l,and r : 25'C.
b) By what factor does this increase i * over the io'?
34.8 Silverisdepositedfroma0.l0mol/LAg+ solution. ForthereactionAg* + e- ' Ag,a : 0.74,
jo:4.5A/cmr when [Ag*]:0.l0mol/L at 20"C. Calculate the overpotential for current
densities ol l0 r. 10- 10- r, and 1 A/cm2.
'z,
3.9 Asolutioncontains0.0lmol/LCd2*and0.l0mol/LH*.Forhydrogendepositiononcadmium,
Eq.Qa.a\ representsthesituation if io : 19-tt A1cm2.z: *l,anda: J, thesameequation
represents the current voltage curve for cadmium deposition il a:i and io: l.5mArcm2.
The equilibrium potential of the Cd2* + 2e- Cd reaction is -0.462 V, in 0.01 mol/L Cdr*
solution and the equilibrium potential of the=2H* + 2e-=H, couple is -0.060V in 0.10
mol/L H * solution at 25 'C.
a) At what current density will cadmium deposition commence?
b) When the current density is - 1.0 x l0 I A/cm2 what fraction olthe current goes into h1'dro-
gen evolution?
3.10 Suppose that a piece olcadmium is touched to a piece olplatinum, and the metals are immersed
in a 0. I mol/L acid solution. Calculate the corrosion potential and the rate of dissolution of the
cadmium lor various ratios of the areas: Ar,f A.a : 0.01, 0.10, 1.0, 10, and 100. For hydrogen
evofution on platinum, Eq.(34.42) may be used with io :0.10mA/cm2, z: *1, and t: i.
Forcadmiumdissolution io: mA/cm2and
1.5 a: j.Theequilibriumpotentialsare:@o,n-.n.,:
-0.060 V; @e,q6.-.6.6, : -0.462 at 25 'C.
V
34.11 Use the data in Problems 34.9 and 34. l0 and suppose that a piece olcadmium is immersed in an
acid solution. What is the corrosion potential and what is the rate of dissolution of the cadmium
if the area ratios are : A.l A^ : I .0, 103, 106, and I 0e '?
y,l2 A 0.01 molar solution of a compound transmits 2O/"of the sodium D line when the absorbing
parh is 1.50 cm. What is the molar absorption coefficient of the substance? The solvent is
assumed to be completely transparent.
34.13 Il l0\ of the energy of a 100 W incandescent bulb goes into visible light having an average
wavelength of 600 nm, how many quanta of light are emitted per second?
34.14 The temperature of the sun's surface is 6000 K. What proportion of the sun's radiant energf is
contained in the spectrum in the wavelength range 0 <,1 < 300nm?(See Problem 19.3.)
34.15 The ozone layer is estimated to be 3 mm thick if the gas were at I atm and 0 'C. Given the
absorptioncoefficienta(definedbyl:1610-'erwherepisthepressureinatmand/isthelength
in cm). What is the transmittance to the earth's surface at each of the following wavelengths ?
ilnm 340 320 310 300 290 280 260 240 220
a/cm ratm I
0.02 03 12 44 t2 48 130 92 20
Problems 911
* 2 in the photolysis ol KtFe(C'Oa)t in

34.16 At 480nm. for the production cl Fe
on is 0.94. Alter 20 min irradiation in a cell containing '4
57 cm3
0.05 molil into 25'00 mL
ed thoroughly and a 10'00 mL sample is pipetted a
of solution. to the mark with
is added and the flask filled
volumerric flask. A quantity of l,l0-pherianihroline
i: ;:i.:fl;ilTliJ:1fi:
m2/mor'
:l .
"0."i#ill.,i"'?'
3.1?ThequantumyieldofCointhephotolacetone(p<6kPa)atwavelengths
lightol3l3nmwavelength,l8.4cm3
between 25042onmisunity.Alter20min
ofCo(measuredat1008Paand22"C)ispulatethenumberofquantaabsorbed
and the absorbed intensity in joules per second'
34.18 Asubstancehasl,o:2 x 106s-t andk?"c:4'0 x 106s-r'Assumethatkr":0andthat
there is no quenching' Calculate{, and to '
: I x 106 s-r calc suming that quench-
34.19 If re:2.5 x l0 s and '4,0
?
ing does not occur and that k?.

: 0'
(EPA)'lft't:g'55
34.20Fornapthalene, rp:2'5sinamixtureo-f:ther' k;c : o'
and @" : 0.05, #;;;;;, kl, lA'o' and
"l;., "m
34.21 Forphenanthrene,rp:3.3s,dr: o'12'QP:0^t1i:analcohol--ertherglassat'1'vK'Assume
no quenching und'.ro internal conversion, kf.
: 0. Calculate Arr' kt,"'' and li"lA'o'
ar'77 Kabsorbs light below 315 nm
fluores-
34.22
tum vields are 6' : 0'29 and' $': ifetimes
- Callulate Aro, Arr, kl5.' and kft
that no
ol '21' write the

A.23 a) Using the mechanism for the formation : 0'
ini
expression rotiit qttut"t'm yield in the
fluorescence
b) The observed value of Q = l'What c nc
olA*?
y.24 is:
Alikely mechanism for the photolysis of acetaldehyde
CH3CHO * hv -----------+ CH3 + CHO'
CH3 + CH3CHO CH4 + CH3CO'
cH3co co + cH3,
CH3+CH3 4 C2H6'
DerivetheexpressionsfortherateofformationofCoandthequantumyieldforCo.
(red light) is:
y.25 Asuggested mechanism for the photolysis of ozone in low-energy light
l) O.+hv 02+O,
2) O + Ot ---!z' ZO"
3) o+o2+M --3+ o3+M'

The quant
nce of ozone'
a)Derive
b)Writethedisappearanceofozone'@o'
c) At low
34.26 Apossible mechanism lor the photolysis of CHrO vapor at 313 nm includes the following steps:
l) + ht' +
CH2O CO + Hr'
2) CH2O+ftr'-+ H+CHO,
3) H+CHrO Hr+CHO,
uo
4) CHO+M ' CO+H+M,
5) cHo + wall ---r1+ +co + icHro.
The rate of the last reaction can be written k5[CHO]. The quantum yields for reactions (l) and
(2) arc Q, and Sr, respectively. Derive the expression for dlHtfldt and lor the quantum yield
for Hr.

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34

34.1 HETEROGENEOUS REACTIONS

34.2 STEPS IN THE MECHANISM OF SURFACE REACTIONS

Figure 34.1 The Nernsl

34.3 SIMPLE DECOMPOSITIONS ON SURFACES

This value of 0 in the rate law, Eq. (34.2), yields

If Eq. (3a.5) must be considered in full, then it is convenient to invert it:

34.4 BIMOLECULAR REACTIONS ON SURFACES

A+s + AS and B+S + BS.

The steady-state equations are

0": Krco0', 0b : Kzcr?,, (34'13)

where K r: kr,'k - r and K2 -- ktlk - r. Usingthese vatues of 0o and 0rin 0" : t- 0

These values used in Eq. Qa.n) yield the rate law

u: kK(l rKrc! coco

denominator of Eq. (34.1S) is (Krc,)2. Then the rare is

34.5 THE ROLE OF THE SURFACE IN CATALYSIS

Figure 34.3 Energy surfaces for

Decomposition of Surlace E$,/(kJ/mol) Ef."",/(kJlmol)

By permission from K. J. Laidler, Chemical Kinetics. New York: McGraw-

34.6 ELECTROLYSIS AND POLARIZATION

dQ : v"F d(. (34.20\

The current is given by 1 : dQ:ldt, so that

where u, is the rate of reaction per unit area.

34.7 POLARIZATION AT AN ELECTRODE

,: (#),_", .;ffi),=o,'* " (34.26)

34.8 MEASUREMENT OF OVERVOLTAGE

Figure 34.5 Cell for the measurement

As the experiment stands, the measured value contains

* 34.9 THE CURRENT_POTENTIAL RELATTON

M(metal) M.*(aq) * ze-(metal)

we consider nrst the hypotheticar lt';jt;[t:1,ili

(a) e=0. = o (b)d + o

Figure 34.6 Dependence of Gibbs energy of activation on potential.

(tt'vt) rvleJz(D-rl-?to)-1 - 161qg"ouv"x+4 - !

:fq ue,l6 st fltsuep luerlno leu eql

orvd ,",r,u(r!),qz: -l pu' ,.,r*-"(r!)tz: *1

(Sg'rc) 'tytei,to-.,-a'o?-4- - -1 pue rvletzp?P"rJ*1

Ge've) rv^etz(x -,,."",-r(#n)'oc rz - - -!

(sE'ff) ,' tz: +

,(q ua,rrE eJ? salllsuep lueJJnc JlpoqlsJ pue JIpouB aql

Gz'vt) 'Qizn - {sv : Qt, - Qp@ - r) + {cv : icv

uollelau lellualod-luarrnc aql

*34.9.1 The Tafet Equation

Figure 34.7 ro versus zFn/RT

Thus Eq. (34.42) becomes

Figure 34,8 Tafel plot for cathodic

34.9.2 The Hydrogen Electrode

At equilibriurl, jr : 0, and the exchange current is given by

i: 2Fk 1(cs,)o("u)B : 2Fk -t(.d3.

,, :,,,[# raF.tRr - ffi t.ft "-,'-',."^'].

,,: ,r"h1"aF4tRr - He-t-,trunrf. (34.s0)

it: iz. (34.52)

of hydrogen or the stirring is such that cr,f(cs,)o : 1, we obtain

i: i2oledFtttRr _ e-(r-"tFqtR7:), (34.53)

which is the rate equation for the simple charge-transfer reaction.

At very small coverages, 0o ( 1, and the equation becomes

i : jro(l _ e-2FatRr). (34.55)

-i - iros-2FntRr, (slow combination of H atoms).

If a : j, the Tafel slope corresponding to each ofthese cases at 25'C is

b -2301Rr : 0.030 v, (slow combination).

34.10 GENERAL CONSEOUENCES OF THE

to occur with high efficiency. A high oxygen overvoltage on the positive

PbSO+ + 2H2O pbo2 + SOi- + 4H+ + 2e-

Figure 34'11 (a) short-circuitedzn-Hzceil. (b) zn-pt coupre in acid

M(metal) M.(aq) ze-(metal)

orvd ,",r,u(r!),qz: -l pu' ,.,r-"(r!)tz: 1

r,: r,()o.,". (34.84)