16/08/2013

Practical details and

electrochemical techniques

Common techniques

Cyclic Voltammetry
Bulk Electrolysis
Chronoamperometry, chronocoulometry
Square wave, staircase voltammetry
Differential pulse voltammetry
Electrochemical Quartz Crystal
Microbalance
Impedance spectroscopy

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Cyclic voltammetry (CV)

The most widely used electrochemical
technique
Simple to perform and extremely
informative

Principles
Practical considerations
Examples

Switching potential

Sweep rate

Edc = Einitial + t

Initial potential
Switching potential

A = B + e-

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What does this actually represent?

Point A: Only R is present in solution :
still below the redox potential of solution
species
Increase the electrode potential towards
the redox potential : R is converted to O.
As R is converted to O a concentration
gradient is setup at the electrode
Point B: R is instantaneously converted
to O
Take the oxidation
of species R to O

After point B the current is dependent on

the rate of mass transfer to the electrode
surface

What does this actually represent?

Point C: Reverse the scan direction
R is still being converted to O
Decrease the electrode potential towards
the redox potential
Species O which is present near the
electrode surface is reduced back to R
Point D: a maximum is reached as in the
forward sweep
Take the oxidation
of species R to O

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Classic example 1 electron oxidation process

Reversible process
The peak potential separation (Epa - Epc) is equal to 57 mV
The peak current ratio (ipa/ipc) is equal to 1 for all scan rates
The peak current increases linearly as a function of the square root of v
The peak current is proportional to concentration

Analysis
Oxidation of ferrocene
40

20

I [A]

-20

Fe is in a 2+
oxidation state

-40

Reduction of cobaltocenium

-60
-1.2

-0.9

-0.6

-0.3

0.0

0.3

0.6

0.9

E [V] vs Ag ref

Both one electron processes what looks strange here?

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ferrocene
Data1B

0.000030

40

20

0.000025

I [A]

0.000020

ip [A]

-20

0.000015
-40

0.000010

-60
-1.2

-0.9

0.000005

-0.6

-0.3

0.0

0.3

0.6

0.9

E [V] vs Ag ref

0.000000
0.0

0.1

0.2

0.3

0.4

0.5

0.6

-1 1/2

sweep rate [V s ]

Randles Sevcik Equation

ip = 2.69 x 105 n3/2 A D1/2 v1/2 C

n : no of electrons
A : electrode area

D : diffusion coefficient
v : sweep rate

C : concentration

Electrochemical cell
CE

REF

WE

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How does it really look?

Reference Electrode

Counter Electrode
Working Electrode

RMIT University

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Practical details
Nearly every experiment requires the presence of a supporting
electrolyte minimises solution resistance
For CV experiments we use a 3 electrode setup
WE : working electrode : process of interest occurs
Typically Pt, Au, carbon, ITO, boron doped diamond
CE : counter electrode : Pt wire/coil/mesh, graphite rod
REF : Reference electrode
Dependent on solvent system
A potential is applied between WE and REF while current is
recorded between WE and CE.
Therefore a stable REF electrode is essential

Reference electrodes
Reference electrode is an electrode which has a stable and wellknown electrode potential
Therefore to form a basis for comparison with all other electrode
reactions, Hydrogen's standard electrode potential (E0) is declared
to be zero at all temperatures.
Potentials of any other electrode is compared with that of the SHE
at the same temperature.
Common reference electrodes : Ag/AgCl,
saturated calomel electrode (SCE)

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Reference electrodes
Ag/AgCl (3M NaCl) is one of the most commonly used
Based on
AgCl(s) + e- = Ag(s) + Cl-(aq)

E = 0.220 V vs SHE
Unit activity at standard conditions
Ideal non-polarizable
electrode

For Ag/AgCl (3M KCl)

E = 0.196 V

Cell Design
Electrodes (Working, Reference, Auxiliary)
material
geometry (available theory?)
size
location

Quiescence- no adventitious stirring caused by

Source of vibration - fumehoods
gas flow through or over solution
density gradients (electrochemically induced)
temperature gradients

Temperature Control
Integrity (air tight; vacuum tight)

Solvent
Supporting Electrolyte (excess assumed)
Choose analyte concentration

selection and purification;

maximize relevant electrochemical window.

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Develop a protocol
Find a suitable solvent for your analyte
Find a suitable supporting electrolyte (SE)
Run a background - SE + whatever (e.g., buffer, ligand,
acid, base..) with no analyte present
Run a simple CV with the analyte
Chosen a value of typically 50 or 100 mVs-1

Change voltage ranges within the voltage window

for the system
See what happens when ncycles = 2, 3, 450
Run CVs over a range of v consistent with
working electrode size & geometry
Change the concentration of analyte
Look at T-dependence
Re-evaluate requirements and consider

optimizing/modifying cell/electrodes
using different solvent, SE, etc.
variations addressing specific interests

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Some examples
Cyclic voltammetry is very powerful in determining reaction mechanisms
Seen previously a one electron transfer reaction
The peak potential separation (Epa - Epc) is equal to 57 mV
What if more than 1 electron is transferred
The peak potential separation (Epa - Epc) is equal to 57/n mV
However much more information can be gathered

Some examples

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Oxidation product
unstable
Consumed chemically to an
electrochemically inactive
species

Less oxidised
product available for
reduction

Example of an EC mechanism

EC mechanism

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EC mechanism

Increase
Sweep rate

ECE mechanism

Increase
Sweep rate

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ECE mechanism

Many mechanisms
Identify some basic mechanisms

E
EE
EC
EC
EC2
CE
ECE

A+e=B
A + e = B; B + e = C;
A1 + e = B1; B1 = B2
A + e = B; B + P = A + Q
A + e = B; 2B = B2
Y = A; A + e = B
A1 + e = B1; B1 = B2; B2 + e = C2;

Use DigiSim or a simulator of choice to explore the behavior of

selected basic mechanisms.

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Several Electrode Types

Macrodisk electrodes : typically 1 3 mm in diameter
Rotating disk electrodes : as above but rotated
Rotating ring disk electrodes
Microelectrodes : typically < 100 m in diameter
Microelectrode arrays
Mercury drop electrode

Several ElectrodeTypes

Stationary Macrodisk

Rotating Macrodisk Electrode

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Rotating Disk Electrode (RDE)

Levich Equation
iL = 0.62nFACD2/3-1/61/2
= 2f : angular rotation rate of
electrode (rad s-1)
= kinematic viscosity (cm2 s-1)
viscosity (g cm-1 s-1 ) / density (g cm-3)

This equation applies if the current

is limited by diffusion and not
electron transfer

Microelectrodes
10 m Pt UME
25
1 mM ferrocene methanol + 0.1 M KNO3
-1

10 mV s

1.4
1.2
1.0

ibulk = 4nFDca

I [nA]

0.8
0.6
0.4
0.2
0.0
-0.2

0.0

0.1

0.2

0.3

0.4

0.5

0.6

E [V] vs Ag/AgCl

Hemispherical diffusion of mediator to the microelectrode

Limiting current in bulk solution
Ibulk = 4nFDca
n: no of electrons
F : Faradays constant (C mol-1)
D : diffusion coefficient (cm2 s-1)
C : concentration (mol cm-3)
A: radius of electrode (cm)

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Microelectrode Uses
Scanning electrochemical microscopy (SECM)

Dark regions highly doped/conducting

SEM image

Electrochemical map

Chronoamperometry

In this technique the potential of the working electrode is stepped, and the
resulting current from faradic processes occurring at the electrode (caused
by the potential step) is monitored as a function of time.
Remember the case in cyclic voltammetry for a reversible cyclic
voltammogram

A = B + e-

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Chronoamperometry
E2
Stationary electrode
Solution must be stationary and unstirred =
mass transport by diffusion

E
E1

Constant potential
Measure current vs time (t)

t (time)

Theory
Assume A = B + e- Both A and B are soluble
- Reversible reaction (electrochemically)
- Potential (E) set so oxidation or reduction goes
to completion at the electrode surface

Chronoamperometry
Other processes occurring at the electrode can perturb the response from
Cottrellian behaviour
Capacitive Current charging current is exponential in nature
However, only influences the beginning of the transient as the capacitive
current decreases more rapidly than Faradaic current so at longer times the
ratio IFar/Icap is very large
Occurrence of a coupled chemical
reactions e.g. A B + e- followed by
2B = C where C is electroactive and can also be oxidised
C B + eThese can affects the shape of the current-time curve and is a good first step in
identifying coupled reactions

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Using chronoamperometry

We can model electrodeposition process to determine mechanism of

growth, we do this by holding the potential at a certain value for a
specified period of time

Peak
maximum
shifts to
earlier times

-4

Current (x 10 Amps)

4.0

2.0

0.0

-0.5

0.0

0.5

1.0

Potential (V)

0.0

-4

Current (x 10 Amps)

0.2

-0.2

-0.4

-0.6
-0.5

0.0

0.5

1.0

Potential (V)

Can analyse it profile to

elucidate mechanism

Hills and
Scharifker model

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What do these mechanisms of growth mean for

electrodeposition?

Increase deposition time

Progressive nucleation and growth

What do these mechanisms of growth mean for

electrodeposition?
30 s

50 s

Analysis shows instantaneous nucleation

90 s

1.3 mM AgClO4 in CH3CN + 0.1 M LiClO4

Note: Still silver deposition but now in organic solvent the
growth is affected!

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The Randles-Sevcik equation can be used to determine the

diffusion coefficient of a species in solution. Use this
equation to determine the diffusion coefficient of a redox
active species, with the transfer of one electron, from the
information provided below.

Electrode area: 0.1963 cm2

Faradays constant: 96,485 C mol-1
Universal gas constant: 8.314 J mol-1 K-1
Concentration: 2.55 mM

For the following electrochemical reaction, B C + e-, a rotating disk

electrode study was carried out to determine the diffusion co-efficient of B.
Illustrated here is a plot of the limiting current versus 1/2.
What is the name of the equation used to plot this data?
From this plot calculate the diffusion co-efficient of B. The electrode used
had an area of 0.1963 cm2, [B] = 2.55 x 10-6 mol cm-3, kinematic viscosity of
solution = 0.00916 cm2 s-1 and Faradays constant = 96,485 C mol-1.

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