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Chapter 3: Kinetics of Electrode Reactions: Dynamic Equilibrium
Chapter 3: Kinetics of Electrode Reactions: Dynamic Equilibrium
Dynamic Equilibrium
kf
A B
kb s-1
k = A exp(-Ea/RT)
k = A exp(-G /RT)
Chapter 3: Kinetics of Electrode Reactions
E = Eo + (2.303RT/nF)log(Co*/CR*)
0.059/n
In many systems, it has been found that the current varies exponentially
with the potential according to the following relationships (Tafel)
i = aexp(/b)
= E Eo
= a + b log i
Chapter 3: Kinetics of Electrode Reactions
k = cm/s C = mol/cm3
Chapter 3: Kinetics of Electrode Reactions
kf = ko exp(-nF/RT) kb = ko exp((1-)nF/RT)
Butler-Volmer Relationship
f = F/RT
At E0, =0 so kf,b = ko
Chapter 3: Kinetics of Electrode Reactions
io = nFAk0CO*(1-)CR* io = A jo = A/cm2
Lower ko need significant
overpotential to deliver
same current.
Chapter 3: Kinetics of Electrode Reactions
Gc = Go + F(E-E0)
Ga = Go - (1-)F(E-E0)
Chapter 3: Kinetics of Electrode Reactions
CO (0, t ) CR (0, t )
i i0 *
exp( nf ) *
exp((1 )nf )
CO (red rxn) CR
(oxid rxn)
Ox + e- Red
Chapter 3: Kinetics of Electrode Reactions
= a + b log i RT RT
ln i0 ln i
nF nF
{cathodic rxn}
RT
RCT
nFi0 Plot i vs. E
el(x) = el0exp(-x)
Microscopic Models of Electron Transfer
Outer-sphere Inner-sphere
M M
Ox + e- Red
Rate = kf,h[Reactant]
Chapter 3: Electrode Kinetics Marcus Theory
The transition state is the position where O and R have the same
configuration , denoted by the reaction coordinate, q.
Gf = (/4) (1 + (F(E-Eo))/)2
In general, there are also free energy changes associated with bringing
the reactants and products from the average environment in the
medium to the special environment where the ET occurs. These include
the energy of ion pairing and the electrostatic work needed to reach the
reactive position.
Chapter 3: Electrode Kinetics Marcus Theory
Gf = (/4) (1 + (F(E-Eo))/)2
= (k/2)(qR-qO)2 = i + o
i = inner sphere, reorganization of species O.
o = outer sphere, reorganization of species O.
= 1/F(Gf/E) = + F(E-Eo)/2
(kex/Aex)1/2 = ko/Ael
Relationship between homo and heterogeneous ET. Ael (10-4
to 10-5 cm/s) and Aex (1011 to 1012 M-1s-1) are the pre-
exponential factors.
Ox
e-
Red
SAMs - Distance effects on ET
x0
Slope = -
What happens ln ket 1-1.2 -1
structurally to get the
reactant ready for ET?
Activated complex. x
Chapter 3: Electrode Kinetics Energy States
Gerischer Model
O + e- R
kf,h = red(E)WO(,E)f(E)(E)E