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Cyclicvoltammetry Geetha1
Cyclicvoltammetry Geetha1
VOLTAMMETRY
GEETHA KRISHNAN
05/24/11
Center for Electrochemical Engineering Research
Department of Chemical and Biomolecular
Engineering
Controlled Potential
Potential Sweep Methods
(1) Potential sweep methods: Cyclic Voltammetry (CV)
and linear sweep voltammetry (LSV).
increase.
b: onset potential
d,j: Peak Potential
F: Switching Potential
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Cyclic Voltammetry
E0 = (Epa + Epc ) /2 .
Separation of peaks for a reversible
couple is 0.059V/n volts.
A one electron transfer fast reaction
thus gives 59mV separation.
Half-peak potential Ep/2 = E1/2 + 0.028/n
This potential is attained in the interval in
which the rate of the charge-transfer process,
and hence the current, increase
monotonically with time.
10
Cyclic Voltammetry
Effect of Scan Rate
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Randles-Sevcik equation
Reversible systems (Effect of scan rate on peak current)
i p 0.4463nFACnFvD RT
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n = Number of electrons
F = Faradays Constant 96,485 C/mole
A = Electrode Area cm2
D = Analyte Diffusion Coefficient cm2 s-1
Ratio of ipa to ipc should be close to one, but vary with chemical
reactions coupled to electrode process.
If the plot of peak height vs. the square root of the scan rate produces a
linear plot, the diffusion coefficient can be obtained from the slope of the
plot.
Center for Electrochemical Engineering Research 13
UNDERSTANDING REACTION MECHANISMS
At small values of ,
reversible behavior is
found.
For large no current is
observed on scan reversal
and shape of the curve is
similar to that of a totally
irreversible charge
transfer.
1. ErCi mechanism
1. ErCi mechanism
2. ErCr mechanism
3. ErCi mechanism
4.ErCiEr mechanism
r : Reversible I : Irreversible
E r : Ox ne Red Reduction
Ci : Red
kc
Z
Z : Electrochemically inactive in
equilibrium exists.
Complete conversion to Z.
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2. ErCr mechanism
ErCr vs ErCi
E r : Ox + ne- Red
Cr : Red Z
Equilibrium maintained in
the chemical step.
Red conc. in vicinity of
electrode is small as its
converted back to Ox.
Very slow scan rates, the
peak current ratio is 1.0.
Fast scan rate, peak
current decreases.
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3. ErCi Mechanism
In presence of catalyst
E r : Ox ne Red
Ci ' : Red + Z
kc
Ox + Y
Z is present in large
As kc increases, so does
catalytically revived Ox.
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3. ErCi Mechanism
Varying Scan Rate
Cr : Z
kf
Ox
E r : Ox ne- Red
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4. ErCiEr Mechanism
Increasing scan rates fixed kc
Cathodic
E r : Ox ne Red E10 A
Ci : Red
kc
A
E r : A + ne- B E 02 < E10
26
The Legendary Butler-Volmer Equation
28
Butler-Volmer Equation
Limitations
1 nFa
(a) i a ` i 0 exp
RT
at high anodic overpotential
nFc
(b) i c` i 0 exp
RT
at high cathodic overpotential
ia and ic are the exchange current densities for the
anodic and cathodic reactions
ln i i0 or b ln i i0
RT
nF
where
2.303RT
b the Tafel slope
nF
ln i 2.303 log i
ln |i|
High overpotential:
ln I = lnIo + (AnF/RT)
Cathodic Anodic
B
i corr
Rp
B the Tafel constant
R p the measured polarisation resistance
E i
Nernst equation
Randles-Sevcik equation
Electrode reactions with coupled
homogeneous chemical reactions
Butler Volmer Equation
Tafel Behavior
Stern Geary Equation
Center for Electrochemical Engineering Research 34
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