Professional Documents
Culture Documents
Electrochemistry Lecture 4 - Notes
Electrochemistry Lecture 4 - Notes
Common techniques
Cyclic Voltammetry
Bulk Electrolysis
Chronoamperometry, chronocoulometry
Square wave, staircase voltammetry
Differential pulse voltammetry
Electrochemical Quartz Crystal
Microbalance
Impedance spectroscopy
16/08/2013
Principles
Practical considerations
Examples
Switching potential
Sweep rate
Edc = Einitial + t
Initial potential
Switching potential
A = B + e-
16/08/2013
16/08/2013
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
16/08/2013
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 ]
D : diffusion coefficient
v : sweep rate
C : concentration
Electrochemical cell
CE
REF
WE
16/08/2013
Reference Electrode
Counter Electrode
Working Electrode
RMIT University
12
16/08/2013
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)
16/08/2013
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
Cell Design
Electrodes (Working, Reference, Auxiliary)
material
geometry (available theory?)
size
location
Temperature Control
Integrity (air tight; vacuum tight)
Solvent
Supporting Electrolyte (excess assumed)
Choose analyte concentration
16/08/2013
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
optimizing/modifying cell/electrodes
using different solvent, SE, etc.
variations addressing specific interests
16/08/2013
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
10
16/08/2013
Oxidation product
unstable
Consumed chemically to an
electrochemically inactive
species
Less oxidised
product available for
reduction
Example of an EC mechanism
EC mechanism
11
16/08/2013
EC mechanism
Increase
Sweep rate
ECE mechanism
Increase
Sweep rate
12
16/08/2013
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;
13
16/08/2013
Several ElectrodeTypes
Stationary Macrodisk
14
16/08/2013
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)
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
15
16/08/2013
Microelectrode Uses
Scanning electrochemical microscopy (SECM)
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-
16
16/08/2013
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
17
16/08/2013
Using chronoamperometry
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)
Hills and
Scharifker model
18
16/08/2013
50 s
90 s
19
16/08/2013
20