CHE32ADB and CH32SPB Room 451

ELECTROCHEMISTRY

Electrochemistry

DR. CONOR HOGAN

La Trobe University
Dr Conor Hogan
2011
 Outline
• Where electrochemistry fits in the grand scheme
of things.
• Applications of electrochemistry.
• Electron transfer, how and why.
• Voltammetric techniques – Principles and
Applications.
• Electrode Materials Glassy carbon etc
semiconductor electrochemistry
• Future trends in electrochemistry: Electro-
materials, Nanotech devices, Sensors,
molecular electronics.
 References
• Electrochemical Methods - Bard & Faulkner. (The bible)
• Fundamentals of Electroanalytical Chemistry – Monk
• Electroanalytical methods : guide to experiments and apps –
Scholz
• Introduction to Electrochemistry - Hibbert
• Electrode Dynamics – Fisher (Oxford Primer Series).
• Quantitative Chemical Analysis 6th ed - Harris
• Principles of Instrumental analysis - Skoog.
• Physical Chemistry – Levine & Physical Chemistry – Atkins.
• Multitude of www sites, e.g. http://www.consultrsr.com/index.htm
http://www.currentseparations.com/issues/index.html , http://www-
biol.paisley.ac.uk/marco/Enzyme_Electrode/Chapter1/electrochemistry_is_fun.htm
• Electrochemistry simulation: www.digielch.de (excellent) and
http://www.drhuang.com/ (quite good).
• Introduction to voltammetric analysis : theory and practice /
F. G. Thomas and G. Henze. (Bundoora General 543.0871
T456i)
• M. J. Blandamer and J. C. R. Reis, Notebook in
Thermodynamics, University of Leicester, UK;
http://www.le.ac.uk/chemistry/thermodynamics/ (See topic 0991
for electrochemical units).
 Electrochemistry
• Electricity was not well
understood until the late 18th
– early 19th century
• Galvani and Volta
established the science of
electrochemistry
• Electrolysis of water into
hydrogen and oxygen first
electrochemical process
• Linear sweep voltammetry
was developed in 1947 by
Randles (of Randles–
Sevcik’s fame)

INTERFACE 2008,17(3), 31-39

 hn

Electrochemistry
A central discipline
e-

Chemistry

Electricity Biology

Electro-
chemistry

Physics Mathematics
D‡G = (  4)(1 + DGo  )2
Material
Science
 Electrochemistry - Applications

Thermo-
dynamics
Fuel
Kinetics
cells

Batteries
Electro-
analysis
Electro-
chemistry

Corrosion Sensors

Solar Nano-
conversion technology
micro-
electronics
 Electrochemistry Applications
Batteries
Lead acid car battery
Electrochemistry Applications

Fuel Cells
Photoelectrochemistry
Dye Sensitized
Solar cells

Electroanalytical Chemistry
The Glucose Sensor
 The Basics

Why Electrons Transfer

 Equilibrium electrochemistry
Take a typical redox / electron transfer reaction:
Fe3+(aq) + e-(m) ↔ Fe2+(aq)
Reaction wants to proceed in a forward or reverse direction
(depending on the relative concentrations of Fe2+ and
Fe3+).
But, needs source or sink for e- in order to proceed. An
inert metal, e.g. Pt, will do.

e- Fe3+

Fe2+
• Since, in this reaction a charged particle (e-) is
transferred between 2 distinct phases, charge
separation occurs resulting in a potential difference
between the metal and solution.
Df = fm - fs
• This potential drop is determined by
the relative concentrations of Fe2+
fs and Fe3+. (See Nernst eqn later).
Potential

• Not feasible to measure Df with just

fm one electrode, (one hand clapping!).
Metal Solution Introduce reference electrode with it’s
own Df which is known and constant.
Distance from
electrode surface • Measure Df relative to Df(ref).
• We will call this measured potential
Ecell or just E.
 The Nernst equation
relates this potential to the concentration of oxidised
and reduced species in solution. So, by measuring
the potential we can measure concentration.
(Equilibrium electrochemistry:
Zero current techniques, e.g. Potentiometry)

2.3RT [Red]
E = E0 – log
nF [Ox]
or (at 250 C)

[Red]
E = E0 – 0.0592 log
n [Ox]
 Dynamic Electrochemistry
Controlled potential techniques
What if, instead of simply measuring the Potential,
we connect the electrode to an external voltage
source. Electrolysis occurs and current flows.
voltage
By controlling the potential source
we could DRIVE the redox
reaction in what ever
direction we wished.
Eapplied > E° for oxidation
Eapplied < E° for reduction
Examples of electrochemically driven
reactions: Metal deposition

Copper deposition at an electrode

Examples of
electrochemically
driven reactions:
Electrosynthesis.
(EC reaction =
Electron transfer
followed by chemical
reaction).
Examples of electrochemically driven reactions:
Amperometric detection in FIA, HPLC, etc.
 Controlled potential techniques
• The Current that flows as a result of driving this
redox or electron transfer reaction, is called
Faradaic current. It can be measured and
related to the concentration for quantitative
purposes.
Fe3+ Fe2+
Electrode

Flow of electrons

• This dynamic electrochemistry forms the basis of

the other branch of electroanalysis: Controlled
potential techniques e.g. Voltammetry,
amperometry, coulometry.
• In practice a three electrode cell is usually used,
(why?), but the principle is the same.
Three-electrode electrochemical cell
Three-electrode electrochemical cell
•Potentiostat: controls the electrical potential between the
working and reference electrodes at a preset value and forces
whatever current is necessary to flow between the working and
counter electrodes to keep the desired potential.

•Working Electrode: redox electrode where electrode

processes occur; measured against suitable reference electrode.

•Reference Electrode: has well known and stable

equilibrium electrode potentials and serves as a reference point
against which the potential of other electrodes can be measured. eg
Ag/AgCl or SCE (saturated calomel electrode).

•Counter (auxiliary) Electrode: serves to make an electrical

connection to the electrolyte so that a current can be applied to the
working electrode. (Also called the auxiliary electrode).
DYNAMIC ELECTROCHEMISTRY
• We apply a potential to the electrode in order
to alter the position of the equilibrium and drive
the redox reaction in which ever direction we
wish. Typically we measure the resulting
current.
The Metal Electrode
 The Metal Electrode
unfilled states • Convenient to visualize in
the context of band
theory.
EF • Ef = Fermi level; highest
E occupied electronic
filled states

energy level in a metal.

• Changing the applied
potential to the metal
changes Ef.
 Why Electrons Transfer
Reduction Oxidation

EF Eredox
E E (HOMO)

Eredox EF
(LUMO)

• Net flow of electrons from • Net flow of electrons from

M to solute solute to M
•Ef more negative than Eredox • Ef more positive than Eredox
• more cathodic • more anodic
• more reducing • more oxidizing
Why Electrons Transfer
 Kinetics and Mass transport
The current which flows as a result of electrolysis depends on the
quantity of solute reacting at the electrode per unit time. It can
therefore be governed by one of two main processes:
• The rate of heterogeneous electron transfer (k0). (Rate
determining electrode kinetics). (See kinetic control later)
• The rate at which the solute is transported to the electrode. (Rate
determining mass transport). (See diffusion control later).

Fe3+ Fe2+
Electrode

Flow of electrons
 Mass Transport
The rate of electron transfer at the electrode / solution interface
is frequently not the rate limiting process. For example, in
order for electrolysis to proceed, often the reactant molecule
must first be transported from the bulk solution. Mass transport
in voltammetric experiments can occur by:

•Diffusion: The movement of species under the influence

of a concentration gradient.

•Convection: Movement of the medium, e.g via stirring,

rotating the electrode or from temperature gradients.

•Electro-migration: Movement of ions under the

influence of an electric field. (Not normally important
because we use a large excess of supporting electrolyte).
What is Diffusion?
 Diffusion
Consider an electrode (in an unstirred solution) poised at a suitable potential such
that the reduction reaction Fe3+ + e- → Fe2+ occurs at the surface.

Because the concentration of

Fe3+ is greater in the bulk than in
the diffusion layer, it will be
transported by diffusion toward Fe3+ 3+
Fe3+ Fe
the electrode. Similarly the Fe2+ Fe3+ Fe3+ Fe3+ Fe3+
species will diffuse away. Fe3+
Fe3+ Fe3+ Fe3+ Fe
3+
Bulk solution Fe3+ Fe3+
The rate of diffusion of a Fe3+
Fe3+ Fe3+ Fe3+
species depends on parameters Fe3+ Fe3+ Fe3+ Fe3+
such as it’s size and the Fe3+
Fe3+ Fe2+ Fe2+ Fe3+
viscosity of the medium. it is Diffusion Layer
characterised by the diffusion (1 – 1000mm) Fe2+ Fe3+ Fe2+ Fe2+ Fe2+
coefficient (D), measured in
cm2s-1. Electrode

Flow of electrons
The distance (cm) a species will
diffuse in a given period of time
(s) is given by: x = (2Dt)
 C0 C0 (bulk)

0
0.1 ms

r
O + ne- → R
1 ms

Distance from electrode (x)

increasing time
5 ms

Electrode
Concentration profiles

9 .0 0

0 .9 1
8 .0 0
0.8 0 .8 4

0 .7 7
7 .0 0
0 .7 0

6 .0 0 0.6 0 .6 3

0 .5 6
T

5 .0 0 0 .4 9
Z A x is

0.4 0 .4 2
4 .0 0
0 .3 5

0 .2 8
3 .0 0
0.2 0 .2 1

2 .0 0 0 .1 4

0 .0 7
1 .0 0 0 .0 0
50 100 150
2 5 .0 0 5 0 .0 0 1 0 0 .0 0
7 5 .0 0W avelength 1 2 5 .0 0
(nm) 1 5 0 .0 0
32

W a v e le n g t h (n m )
d
 Distance / um

9 .0 0 0.5
0 .4 8
8 .0 0
0 .4 5
0.4
C = 1 mM

0 .4 1
7 .0 0
0 .3 7

6 .0 0 0 .3 3
0.3
0 .3 0

T
D = 10-5 cm2s-1

5 .0 0 0 .2 6

Z A x is
0.2 0 .2 2
4 .0 0

0.01 s
0 .1 9

0 .1 5
3 .0 0
0.1 0 .1 1

Electrode surface
2 .0 0 0 .0 7

0 .0 4
0.0
1 .0 0 0 .0 0
50 100 150
2 5 .0 0 5 0 .0 0 7 5 .0 0W avelength 1 0 0 .0 0 1 2 5 .0 0
(nm) 1 5 0 .0 0
W a v e le n g t h (n m )

9 .0 0
0.8
0 .8 0
8 .0 0
0 .7 4

0 .6 8
7 .0 0
0.6 0 .6 2

6 .0 0 0 .5 5

0 .4 9

T
5 .0 0 0.4 0 .4 3

Z A x is
0 .3 7

0.1 s
4 .0 0
0 .3 1

0 .2 5
3 .0 0 0.2
0 .1 8

Electrode surface
2 .0 0 0 .1 2

0 .0 6
0.0
1 .0 0 0 .0 0
50 100 150
2 5 .0 0 5 0 .0 0 1 0 0 .0 0
7 5 .0 0W avelength 1 2 5 .0 0
(nm) 1 5 0 .0 0
W a v e le n g t h (n m )

9 .0 0

0 .9 1
8 .0 0
0.8 0 .8 4

0 .7 7
7 .0 0
0 .7 0

6 .0 0 0.6 0 .6 3

0 .5 6

T
5 .0 0 0 .4 9

Z A x is
0.4 0 .4 2

1.0 s
4 .0 0
0 .3 5

0 .2 8
3 .0 0
0.2

Electrode surface
0 .2 1

2 .0 0 0 .1 4

0 .0 7
1 .0 0 0 .0 0
50 100 150
2 5 .0 0 5 0 .0 0 1 0 0 .0 0
7 5 .0 0W avelength 1 2 5 .0 0
(nm) 1 5 0 .0 0
W a v e le n g t h (n m )

9 .0 0

0 .9 4
8 .0 0
0 .8 8
0.8
0 .8 1
7 .0 0
0 .7 5

6 .0 0 0 .6 8
0.6 0 .6 1
T

5 .0 0 0 .5 5
Z A x is

0 .4 8
4 .0 0
5.0 s

0.4 0 .4 2

0 .3 5
3 .0 0
0 .2 8
Electrode surface

0.2 0 .2 2
2 .0 0
0 .1 5
Visualisation of Concentration profiles

1 .0 0 0 .0 9
33

50 100 150
2 5 .0 0 5 0 .0 0 1 0 0 .0 0
7 5 .0 0W avelength 1 2 5 .0 0
(nm) 1 5 0 .0 0
W a v e le n g t h (n m )
 Problems
1. The Diffusivity (D) of Ru(NH3)63+ in 0.09 M
phosphate aqueous solution is 5.3 x 10-6 cm2s-1
at room temperature. Calculate the thickness of
the diffusion layer at an electrode in an
unstirred solution when this species is reduced
by electrolysis for a period of 1 min.
2. How long would it take Ru(NH3)63+ under the
above conditions to diffuse a distance of 1 cm?
 Diffusion: Implications of √ t dependence
70000
1.3 cm / day
60000

50000

40000
Time / s

30000

1mm / 8 min
20000

10000 90m m / 4 s

1m m / 0.5 ms
0
1.E-06 1.E-05 1.E-04 1.E-03 1.E-02 1.E-01
Distance / m
 Convection
• Achieved by stirring the solution or rotating
the electrode (rotating disc voltammetry).
• Natural convection can play a role at very
long timescales.
• Results in faster mass transport and
therefore higher currents.
Rotating Disc Voltammetry
Effect of Convection

0 rpm

500 rpm

2500 rpm

5000 rpm

10000 rpm
- steady state type response
due to faster mass transport.
 Migration
/ Electromigration

• Acts on charged species only.

• Usually try to minimize migration by using
a large excess of supporting electrolyte.
• At low electrolyte concentration, a large
fraction of the total current is due to
migration - currents due to electrostatic
attraction of ion for electrode
 Cyclic Voltammetry
The electrode potential is cycled between two values, and the resulting current is
monitored as a function of applied potential.

1.2
E/V

-0.2

time / s
dE/dt is Scan rate (v) in V s-1
 IUPAC convention for plotting
voltammetric data
(oxidation)
ANODIC

ELECTRODE BECOMES STRONGER OXIDANT

ia
Current / A

0
CATHODIC
(reduction)

ELECTRODE BECOMES STRONGER REDUCTANT

ic

(-) 0 (+)

Potential / V (vs reference electrode)

Cyclic voltammetry
Cyclic voltammetry
Ep,ox

Fe2+ → Fe3+ + e-

Ip,ox

Ip,ox

Fe3+ + e- → Fe2+

Ep,red

5 x 10 -3 M Ferrocene /
acetonitrile / 0.1 M electrolyte
 CYCLIC VOLTAMMETRY
Concentration Profiles during a potential scan
3 Only 1st ½ of cycle shown
I 4
2 R → O + ne-
5
E 6
• From 1 to 3, current
1
increases as dCR/dx gets
larger - kinetic control.
Bulk
conc. 1
2
3 • From 3 to 6 current
4
5 decreases as conc. profile
CR 6 extends further and further
into solution - diffusional
control.

X (distance from electrode surface)

 Concentration Profiles during a potential scan

0.00E+00
3.50E-03

-5.00E-06 3.00E-03

2.50E-03

Concentration / M
-1.00E-05
Current /µA

2.00E-03
-1.50E-05
1.50E-03
-2.00E-05
1.00E-03

-2.50E-05
A- ← e- + A 5.00E-04

-3.00E-05 0.00E+00
-1.2 -1 -0.8 -0.6 -0.4 -0.2 0 0.2 0 0.002 0.004 0.006 0.008 0.01
Potential /V Distance /cm

Numerical Simulation of single scan and conc profiles for 3mM

Solution of A at 1 Vs-1
D = 1 e-5 cm2s-1; A = 0.011 cm2 46
x1/2 = x

Cyclic voltammetry

Capacitive (background) current: ic = Cdl n

(due to double layer charging)
Cdl is electrode capacitance (~10mF)
n is scan rate (Vs-1)

The Randles-Sevčik equation

Faradaic current: i p = 2.69  105 n 3/ 2 AD 1/ 2

n1/ 2 C
(due to oxidation / reduction)
Analytical
no. of electrons Concentration
transferred Electrode (mol cm-3)
Area Diffusion
(cm2) Coefficient
(cm2 s-1)
 Cyclic voltammetry
Characteristics of a reversible n electron transfer:
E°, the potential half way between
Ep,ox and Ep,red is called the formal
 Ep,o x + Ep,red
1. E = potential. Characteristic for a
2 particular species in a particular
medium. Can aid in qualitative
identification.

59
2. DE p = (E p, o x − E p, red ) = mV
n
The peak to peak splitting can be used to
determine the number of electrons (n) or
to quantify the heterogeneous electron
transfer rate (k) if the process is
electrochemically irreversible.
 Cyclic voltammetry
Characteristics of a reversible n electron transfer:

3. Ip,o x = Ip,red Both peaks will be the same height if

the reaction is chemically reversible.

The peak heights scale linearly with scan

rate for a diffusion controlled process. Use
4. Ip  n Randles-Sevčik plot to evaluate diffusion
coefficent. Randles-Sevčik equation:

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

5. Ep,o x and Ep,red are independent of n.

But if you scan fast enough the peaks will

begin to diverge (electrochemical
irreversibility)
 Cyclic Voltammetry - Effect of Scan Rate
Only 1st ½ of cycle shown
Deducing mass transport information from CV
60

40

20

ip / uA
0
0.0 0.2 0.4 0.6 0.8

-20 v 1/2 / Vs-1/2

-40

-60

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

Evaluate diffusion coefficient (D)

from slope. Watch the units!
 G animation

http://staff.bath.ac.uk/chsjdmc/Electrochem_web/New%20pages/l2kin.htm