Electroanalytical Techniques

(chronoamperometry/
chronocoulometry)
Vedasri Vedharathinam

Center for Electrochemical Engineering

Research
Department of Chemical and Biomolecular
Engineering

ABC’s of Electrochemistry
July 12, 2011
 Overview
1. Electrochemistry basics
2. Electrochemical techniques
– Sweep method
• Cyclic voltammetry
– Step method (current or potential)
• Chronoamperometry
• Double step chronoamperometry
• Chronocoulometry
Electrochemical
• Double step chronocoulometry
Engineering 2
 Basic concepts in electrochemistry

• Chemistry that deals with chemical reactions in a metal (e-

conductor) – solution (ion conductor) interface.
• Involves e- transfer between the elctrode and the elecrolyte or
species in solution.
• This transfer creates a current, the magnitude of which can
give us clues about the active species.
• Electrochemistry is based on Electron transfer reactions:
oxidation-reduction (redox) reactions.
• These reactions result in the generation of an electric current
(electricity) or caused by the application of an electric current.
– Chemical rection driven by an external voltage – electrolysis
– Chemical reaction producing voltage - battery
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 Applications

• Batteries
• Fuel cells
• Electrolysis
• Corrosion
• Industrial production of chemicals such as Cl2,
NaOH, F2 and Al
• Biological redox reactions
• Redox reactions employed in biological sensing
• Amperometric sensors

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 Terminology

• OXIDATION—loss of electron(s) by a species;

increase in oxidation number;
Fe2+  Fe3+ + e-
• REDUCTION—gain of electron(s); decrease in
oxidation number; decrease in oxygen;
Fe3+ + e-  Fe2+
• OXIDIZING AGENT—electron acceptor; the
reagent is reduced
• REDUCING AGENT—electron donor; the reagent
is oxidized.
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Electrochemical behavior of an electrode in
solution

When a piece of metal is placed in a solution containing ions,

there is a charge separation across the boundary between the
metal and the solution. This sets up a potential , which cannot
be measured directly but requires a second half cell.

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Electrochemical cell

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 Electrochemical cell
2-electrode vs. 3-electrode systems
2 – electrode cell 3 – electrode cell

• Used where measurement of the whole cell •
voltage is significant (e.g. batteries, fuel cells,
super caps).
• where the counter electrode potential can be
expected not to drift over the course of the
experiment. E.g. systems with very low
currents and/or relatively short timescales •
and which also have a well poised counter,
e.g. a micro working electrode and a much • Consistent, reliable and accurate.
larger silver counter electrode.
Interested in only one of the reactions, and
the electrode at which it occurs is called the
working (or indicator) electrode, coupled with
an electrode that approaches an ideal
nonpolarizable electrode of known potential,
called the reference electrode.
Current is passed between the WE and CE
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 Three electrode cell

• Requires a precise control of the

potential at the electrode.
• Three electrodes:
– Working electrode (WE),
– Counter electrode (CE)
– Reference electrode (RE).
• No current through RE ideally.
• RE is used to provide precise
control of potential at the WE, and
the current from WE to CE is
measured.

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 Faradaic process

Faradiac process: Electron transfer causes oxidation and

reduction to occur. This process is governed by Faraday’s law.
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 Mass transport due to diffusion

Electrochemical
Engineering 11
 Mass transport in electrochemistry

In order to react a species at an electrode it needs to be

transported from bulk to surface.

Three principal mechanisms:

• Diffusion is the movement of molecules along a concentration

gradient, from an area of high concentration to an area of low
concentration.

• Migration is the transport of a charged species under the

influence of an electric field.

• Convection is the transport of species by hydrodynamic

transport (e.g. natural thermal motion and/or stirring).
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 Mass transport in electrochemistry
Diffusion
Current flow at Electrode Surface

The current that flows from a surface electrochemical

reaction can be defined as (using the example of reduction
of O): dq
i ic  nFAk red [Oelectrode ]
dt
F = 96485 Cmol-1. The amount of charge in C transferred for 1 mole of
reactant.

To understand an electrochemical reaction it is necessary to have a feeling

for the concentration of the reactant [O] as a function of distance from
electrode and with respect to time as a reaction progresses.

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 Diffusion limited electrode reaction & Fick’s law

Fick’s first law quantifies the movement of a species (under diffusion

control) with respect to distance x from an electrode with the flux, J.

[O]
J o   Do 1st law
x
More important is to understand how surface concentration changes as
function of time:
[O]   [O]
2

 Do   2nd law
t  x 2 
 

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Diffusion limited electrode reaction & Fick’s law

Solving Fick’s second law (for planar electrode boundary

conditions), and then substituting ic  nFAk red Oelect  gives the

Cotrell equation:

nFA[O] D
i 
 t

[O] is now the bulk concentration of O.

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Diffusion limited electrode reaction & Fick’s law
Current behavior with time

Concentration verses distance Concentration verses distance

above the electrode before voltage step above the electrode just after pulse

[O]
Fe3+ + e- → Fe2+ J o   Do
x
(reduction)
i∝J
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Electrochemical techniques -
Voltammetry

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Electrochemical techniques

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 Electrochemical techniques
Voltammetry
Voltammetry: measurement of current (I)
as a function of applied potential (E) over
a time. Under condition with polarization
(η). Negligible consumption of analyte.

– Amperometry: measure I at a fixed E

– Potentiometry: measure E when I 0,
no polarization
– Coulometry: measure C, polarization is
compensated, all analyte is consumed.

Commonly uses three electrodes

- Working electrode
- Auxillary electrode
- Reference electrode

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 Electrochemical techniques
Why use voltammetry?

• Handles high salt concentrations better than

chromatographic instrumentation

• Can differentiate between ionic species

Example: Ni2+  Ni3+

• Extremely low detection limits – high sensitivity

• Can detect a wide range of species

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Electrochemical techniques
Types of Voltammetry

1. Sweep methods
• Cyclic voltammetry
• Linear sweep voltammetry
• Rotating disk electrode

2. Step and pulse methods

• Step voltammetry
a. Chronoamperometry
b. Chronocoulometry
c. Chronopotentiometry

• Pulse voltammetry
a. Normal pulse voltammetry
b. Differential pulse voltammetry
c. Square wave voltammetry

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 What can be learnt from voltammetry?

• Mechanism of electrode reaction.

• Concentration of oxidative or reductive
species: useful for making a sensor.
• Determination of Diffusion coefficent of
electroactive species, D.
• Rate constant.
• Type of reaction mechanism

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 Cyclic Voltammetry

Electrochemical
Engineering 23
Electrochemical techniques – Sweep method
Cyclic voltammetry

Applied waveform
Resulting voltammogram

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 Electrochemical techniques – Sweep method
Cyclic voltammetry
For a reversible electrochemical reaction the CV recorded has certain
well defined characteristics.

I. The voltage separation between the current peaks is

I. The positions of peak voltage do not alter as a function of voltage

scan rate
II. The ratio of the peak currents is equal to one
Ia / ic = 1

I. The peak currents are proportional to the square root of the scan
rate

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 Step methods

a. Chronoamperometry
b. Double step chrono amperometry
c. Chronocoulometry
d. Double step chronocoulometry

Electrochemical
Engineering 26
 Electrochemical techniques – Step method
Types
WE potential

Current
t=0 Chronoamperometry
time time
WE potential

Charge

Chronocoulometry
t=0

time time
WE potential
Current

Chronopotentiometry
t=0

time time

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 Electrochemical techniques – Step method
Chronoamperometry

V2

WE potential
V1

Stable R species
time

Voltage applied to cell begins at V1 where no reaction occurs

and is stepped up to V2 causing electrode process to begin
and a current spike results.
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 Electrochemical techniques – Step method
Chronoamperometry

Faradaic current under diffusion controlled conditions is related directly to the

concentration gradient, ∂Ci / ∂x, evaluated at x = 0. Thus, as the slope of the
concentration profile for Ox decreases with time following the potential step, so will the
observed current.

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 Electrochemical techniques – Step method
Chronoamperometry

i ∝ 1 / √t
WE potential

i
V1

time time

Current drops off with time according to the Cottrell nFA[O]bulk D

equation since material must diffuse to the i
electrode surface in order to react.  t
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 Electrochemical techniques – Step method
Chronoamperometry - estimation of diffusion co-efficient
• Perform a potential step measurement.
Cottrell plot
• Ignore current before potential step.
• Linearise Cottrell equation

1  .t

i, A
nFA[O]bulk D
i 2
 2 2 2 2
 t i n F A [O]bulk D

Plot 1 / i2 vs t
Slope = /n2F2A2[O]2D
t-1/2, s-1/2
• Slope will give the value of ―D”

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 Electrochemical techniques – Step method
Chronoamperometry - estimation of diffusion layer thickness
• If the diffusion coefficient of an electroactive species is known, or
has been calculated, the diffusion layer thickness can be estimated
using this equation:
l  Dt
• The diffusion layer extends into the bulk solution more and more
slowly after application of a potential step. Hence for a molecule with
a diffusion coefficient of 1 x 10-10 m2s-1, the diffusion layer thickness
is around 20 mm after 1 second.

• The fraction of molecules oxidised or reduced can also be estimated

by calculating the volume of a hemispherical diffusion layer around a
circular electrode as a fraction of the total solution.

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 Electrochemical techniques – Step method
Double potential step Chronoamperometry
To study the chemical reactions which follow electron transfer

E: O + e  R
Unstable R species
C: R  X

E: X + e  P

FORWARD STEP

REVERSE STEP

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Electrochemical techniques – Step method
Double potential step Chronoamperometry

Oxidised species

Reduced species

FORWARD STEP REVERSE STEP

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 Electrochemical techniques – Step method
Double potential step Chronoamperometry

t = 400ms t = 300ms

kt

t = 200ms

Kinetic plot
t
for double potential
Theoretical working curves for double
potential chronoamperometry applied to EC chronoamperometry
mechanism
Slope = rate constant
J. Phys. Chem., 1965, 69 (1), pp 30–40 35
Electrochemical techniques – Step method
Chronoamperometry - Applications

nFA[O]bulk D
i 
 t
– Measurement of surface area
– Measurement of diffusion co-efficient
– Determination of heterogeneous rate constant
– Determination of diffusion layer thickness
– Evaluation of ECE mechanisms

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 Electrochemical techniques – Step method
Chronocoulometry
Measuring instantaneous currents is not easy.

Ef
 dt
i Q
Ei

0 t t t

1/ 2
CO*  2nFADO1/ 2CO t 1/ 2
i t  
nFADO dt
 Q
 1 / 2t 1 / 2  1/ 2

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 Electrochemical techniques – Step method
Chronocoulometry

Potential
E2 1/2
bæ Dö
Q ( t ) = ò FnAC ç ÷ dt + ò ic dt
E1 è pt ø

Cottrell current
Current

2nFADO1/2CO* t1/2
Q (t ) = + Qc
0
ic
p 1/2

Linear plot with Qc intercept, slope

Charge

proportional to concentration of
reactant
Qc
Qc – response in the absence of reactant
0 (i.e only supporting electrolyte)
0 time 38
 Electrochemical techniques – Step method
Chronocoulometry
For O + n e- R, plot Q vs. t1/2

Charge due to cottrell current

2nFADO1/2CO* t1/2
QDL Q (t ) = + Qc
QDL p 1/2

t1/2 Interfacial capacitance charge

If plot linear, the reaction is Diffusion Controlled

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 Electrochemical techniques – Step method
Chronocoulometry
What if redox species (O) is adsorbed on electrode surface?

Qads QDL (blank - only S.E)

Charge flowing into the interfacial
Qads  nFAO
t1/2 capacitance when the electrode
potential is stepped from E1 to E2
O the quantity of adsorbed reactants

2nFADO1/2CO* t1/2
Q (t ) = + Qc + Qads
p 1/2

Extra charge produced by the

adsorbed reactant
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 Electrochemical techniques – Step method
Double potential step Chronocoulometry

Potential
E2
• Measuring Qc is not a problem –
tr
E1
tf adsorbed species produces little or no
change in the value of Qc
• But, adsorbed species produces
Current significant Qc values, so that the
evaluated Qc in the absence of reactant
0 (blank) do not apply.

SOLUTION
Charge

Double potential chronocoulometry

Qr

time 41
Electrochemical techniques – Step method
Double potential step Chronocoulometry

Forward
Q
reverse

 2

2nFADO1/2CO* t1/2
Qt<t = Qc + nFAG O +
p 1/2
Qt>t = Qc +
2nFADO1/2CO* 1/2
p 1/2
t (+ ( t - t )1/2
- t 1/2
) 
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Electrochemical techniques – Step method
Double potential step Chronocoulometry
For adsorption:
Qf vs. t

Qads + Qc

Qc sec1/2

If R Qt  vs. 
not (Qr )
adsorbed!
Get Qads by subtraction.

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Thank you !

Questions????