VOLTAMMETRY

A.) Comparison of Voltammetry to Other Electrochemical Methods

1.) Voltammetry: electrochemical method in which information about an analyte is

obtained by measuring current (i) as a function of applied potential
- only a small amount of sample (analyte) is used

Instrumentation – Three electrodes in solution

containing analyte

Working electrode: microelectrode whose

potential is varied with time

Reference electrode: potential remains constant

(Ag/AgCl electrode or calomel)

Counter electrode: Hg or Pt that completes

circuit, conducts e- from signal source through
solution to the working electrode

Supporting electrolyte: excess of nonreactive

electrolyte (alkali metal) to conduct current
Apply Linear Potential with Time Observe Current Changes with Applied Potential

2.) Differences from Other Electrochemical Methods

a) Potentiometry: measure potential of sample or system at or near zero
current.

voltammetry – measure current as a change in potential

b) Coulometry: use up all of analyte in process of measurement at fixed current

or potential

voltammetry – use only small amount of analyte while vary potential

 3.) Voltammetry first reported in 1922 by Czech Chemist Jaroslav Heyrovsky
(polarography). Later given Nobel Prize for method.

B.) Theory of Voltammetry

1.) Excitation Source: potential set by instrument (working electrode)

- establishes concentration of Reduced and Oxidized Species at electrode
based on Nernst Equation:

0.0592 (aR)r(aS)s …
E0
Eelectrode = - log
n (aP)p(aQ)q …
- reaction at the surface of the electrode

Apply

Potential
Current is just measure of rate at which species can be brought to electrode surface
Two methods:
Stirred - hydrodynamic voltammetry
Unstirred - polarography (dropping Hg electrode)

Three transport mechanisms:

(i) migration – movement of ions through solution by electrostatic attraction to
charged electrode
(ii) convection – mechanical motion of the solution as a result of stirring or flow
(iii) diffusion – motion of a species caused by a concentration gradient
 Voltammetric analysis
 Analyte selectivity is provided by the applied potential on the working electrode.
 Electroactive species in the sample solution are drawn towards the working electrode
where a half-cell redox reaction takes place.
 Another corresponding half-cell redox reaction will also take place at the counter
electrode to complete the electron flow.
 The resultant current flowing through the electrochemical cell reflects the activity (i.e.
 concentration) of the electroactive species involved

Pt working Ag counter
electrode at -1.0 electrode at
V vs SCE 0.0 V

Pb2+ + 2e- Pb EO = -0.13 V vs. NHE AgCl Ag + Cl-

K+ + e- K EO = -2.93 V vs. NHE SCE

X M of PbCl2
0.1M KCl
Pb2+ + 2e- Pb -1.0 V vs SCE Concentration gradient created
between the surrounding of the
electrode and the bulk solution
K+
Pb2+ Pb2+ K+
K+ Pb2+
Pb2+
K+ K+ Pb2+
K+
K+ K+
Pb2+ K+
Pb2+
Pb2+ K+ Pb2+
K+ Pb2+ K+
K+ K+ Pb2+ K+
K+ Pb2+ Pb 2+ K+ Pb2+
K+Pb2+ migrate to
the electrode
K+
K+ via diffusion Pb2+
Pb2+ Pb2+ K+
Pb2+
Pb2+
K+ Pb2+ Pb2+
K+ K+
K+ K+

Layers of K+ build up around the electrode stop the

migration of Pb2+ via coulombic attraction
 At Electrodes Surface: Mox + e-  Mred

[Mred]s
Eappl = Eo - 0.0592 log at surface of electrode
n [Mox]s
Applied potential

If Eappl = Eo:
0.0592 [Mred]s
0= n log
[Mox]s

[Mox]s = [Mred]s
 Apply

Potential
E << Eo

If Eappl << Eo:

[Mred]s
Eappl = E0 - 0.0592 log
n [Mox]s

\ [Mred]s >> [Mox]s

2.) Current generated at electrode by this process is proportional to concentration at
surface, which in turn is equal to the bulk concentration
For a planar electrode:

measured current (i) = nFADA( dCA )

dx
where:
n = number of electrons in ½ cell reaction
F = Faraday’s constant
A = electrode area (cm2)
D = diffusion coefficient (cm2/s) of A (oxidant)
dCA
dx = slope of curve between CMox,bulk and CMox,s

dCA
dx
As time increases, push banding further and further out.
Results in a decrease in current with time until reach point where convection of analyte
takes over and diffusion no longer a rate-limiting process.
Thickness of Diffusion Layer (d):

i = nFADox (cox, bulk – cox,s)

d
- largest slope (highest current) will occur if:

Eappl << Eo (cox,s . 0)

then nFADox
i= (cox, bulk – 0)
d
where: nFADox
k=
d
so:
i = kcox,bulk

therefore:
current is proportional to bulk concentration

- also, as solution is stirred, d decreases and i increases

Potential applied on the working electrode is usually swept over (i.e. scan)
a pre-defined range of applied potential

0.001 M Cd2+ in 0.1 M KNO3 supporting electrolyte

Electrode become more and more
reducing and capable of reducing Cd2+
All Cd2+ around the electrode has
Cd2+ + 2e- Cd already been reduced. Current at
Current starts to be registered at the the electrode becomes limited by
i (A)
electrode the diffusion rate of Cd2+ from the
Working electrode is E½ bulk solution to the electrode.
no yet capable of Thus, current stops rising and
reducing Cd2+  levels off at a plateauid
Current at the working
only small residual
electrode continue to rise as
current flow through
the electrode become more
the electrode Base line
reducing and more Cd2+
around the electrode are being of residual
reduced. Diffusion of Cd2+ current
does not limit the current yet

-0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4

V vs SCE
3.) Combining Potential and Current Together

Limiting current
Related to concentration

E½ at ½ i

Half-wave potential : E1/2 = -0.5  E0 - Eref

E0 = -0.5 + SCE for Mn+ + me- ↔ M(n-m)+

 4.) Voltammograms for Mixtures of Reactants

[Fe3+]=1x10-4M

[Fe2+]=0.5x10-4M
[Fe3+]=0.5x10-4M

0.2V
0.1V
[Fe2+]=1x10-4M

Two or more species are observed in

voltammogram if difference in separate Different concentrations result in
different currents, but same potential
half-wave potentials are sufficient
 5.) Amperometric Titrations
-Measure equivalence point if analyte or reagent are oxidized or reduced at working
electrode
- Current is measured at fixed potential as a function of reagent volume
• endpoint is intersection of both lines

endpoint endpoint
endpoint

Only analyte is reduced Only reagent is reduced Both analyte and reagent
are reduced
6) Pulse Voltammetry
a) Instead of linear change in Eappl with time use step changes (pulses in Eappl) with time

b) Measure two currents at each cycle

- S1 before pulse & S2 at end of pulse
- plot Di vs. E (Di = ES2 – ES1)
- peak height ~ concentration
- for reversible reaction, peak potential standard potential for ½ reaction

E0
c) differential-pulse voltammetry

concentration

d) Advantages:
- can detect peak maxima differing by as little as 0.04 – 0.05 V
< 0.2V peak separation for normal voltammetry
- decrease limits of detection by 100-1000x compared to normal voltammetry
< 10-7 to 10-8 M
e) Cyclic Voltammetry

1) Method used to look at mechanisms of redox

reactions in solution.

2) Looks at i vs. E response of small, stationary

electrode in unstirred solution using triangular
waveform for excitation

Cyclic voltammogram
 Working Electrode is Pt & Reference electrode is SCE
6 mM K3Fe(CN)6 & 1 M KNO3 A. Initial negative current due to oxidation of H2O to give O2

No current between A & B (+0.7 to +0.4V) no reducible or

oxidizable species present in this potential range

B. At 0.4V, current begins because of the following

reduction at the cathode:

Fe(CN)63- +e-  Fe(CN)64-

B.-D. Rapid increase in current as the surface concentration

of Fe(CN)63- decreases

D. Cathodic peak potential (Epc) and peak current (ipc)

D.-F. Current decays rapidly as the diffusion layer is extended

further from electrode surface

F. Scan direction switched (-0.15V), potential still negative

enough to cause reduction of Fe(CN)63-

F.-J. Eventually reduction of Fe(CN)63- no longer occurs and

anodic current results from the reoxidation of Fe(CN)64-
J. Anodic peak potential (Epa) and peak current (ipa)

K. Anodic current decreases as the accumulated Fe(CN)64- is

used up at the anodic reaction
 Important Quantitative Information

< ipc . ipa

< DEp = (Epa – Epc) = 0.0592/n,
where n = number of electrons in reaction

< E0 = midpoint of Epa  Epc

<ip = 2.686x105n3/2AcD1/2v1/2

- A: electrode area
- c: concentration
- v: scan rate
- D: diffusion coefficient

Thus,
- can calculate standard potential for half-reaction
- number of electrons involved in half-reaction
- diffusion coefficients
- if reaction is reversible
Example 20: In experiment 1, a cyclic voltammogram was obtained from a 0.167 mM
solution of Pb2+ at a scan rate of 2.5 V/s. In experiment 2, a second cyclic
voltammogram is to be obtained from a 4.38 mM solution of Cd2+. What must the scan
rate be in experiment 2 to record the same peak current in both experiments if the
diffusion coefficients of Cd2+ and Pb2+ are 0.72x10-5 cm2s-1 and 0.98x10-5 cm2s-1,
respectively.