4 CLASS Electrochem Part II Prof. Corton

How to identify the redox potential of a compound?
Our previous
example
O2 as redox entity H2O2 as redox entity

Common voltammetry techniques:
 Linear Sweep Voltammetry (LSV)
 Cyclic Voltammetry (CV)
Some other voltammetric techniques used in developing biosensors are differential pulse
voltammetry, square wave voltammetry etc.
In voltammetry, information about an analyte is obtained by measuring the current as the
potential is varied.
Linear Sweep Voltammetry:
A fixed voltage range is scanned from a lower to an upper limit:
The characteristics of the linear sweep voltammogram recorded depend on a number
of factors including:
*The rate of the electron transfer reaction(s)

*The chemical reactivity of the electroactive species
*The voltage scan rate
Let us consider the Fe3+/Fe2+ system:
Following voltammogram would be seen for a single voltage scan

using an electrolyte solution containing only Fe3+ resulting from a
voltage sweep.
V1 V2
As the voltage is sweept from V1 to V2 the equilibrium position shifts

from no conversion at V1 to full conversion at V2 of the reactant at the
electrode surface.
As the voltage is swept to the right (to more reductive values) a
current begins to flow and eventually reaches a peak before dropping.
The Nernst equation can be used to determine the relative

3+ 2+
concentration of Fe to Fe at the electrode at every electrode
potential (E) encountered on the sweep (if the wave is reversible).
The requirement that the electron transfer be reversible (fast) is to
ensure that electrons are transferred rapidly and equilibrium is
always maintained at the electrode. In other words, the
3+ 2+
concentrations of Fe to Fe at the electrode change immediately
as the electrode potential changes
The Nernst equation predicts the relationship between concentration
and voltage (potential difference), where E is the applied potential
difference and Eo is the standard electrode potential.
Cyclic Voltammetry
In addition to forward scan as in LSV, a reverse scan is also done.
The direction of the potential scan is reversed at the end (often referred
to as a switching potential).
The same potential window is scanned in the opposite direction, hence

the term cyclic.
Hence, the species formed by oxidation on the first (forward) scan can
be reduced on the second (reverse) scan.
The reverse scan is simply moving back through the equilibrium positions gradually
converting electrolysis product (e.g. Fe2+ back to reactant Fe3+).
Formal potential (an approximation to the standard potential) of the species is
(Ep(ox)+Ep(red) )/2
Randles–Sevcik equation (effect of scan rate on the peak current ip ).
i p = 2.68 x 105 n3 /2 A D1/ 2 C v1/2 (If the solution is at 25 °C)

Randles-Sevcik Plot, displays the peak
currents of the redox reactions versus the
square root of the scan-rate.
It can be used to calculate the
electrochemical active area and diffusion
coefficient.
ip = current maximum in amps
n = no. of electrons transferred in
the redox event
A = electrode area in cm2
D = diffusion coefficient in cm2/s
C = concentration in mol/cm3
ν = scan rate in V/s
R = Gas constant in J K−1 mol−1
T = temperature in K
F = Faraday constant in C mol−1

Chronoamperometry:
The potential of the working electrode is stepped, and the resulting
current from faradaic processes occurring at the electrode (caused by
the potential step) is monitored as a function of time.
First, the electrode is poised at Einit, well negative with respect of E0´ (for the redox
couple), so only Red is presented in solution.
At time 5 s the potential is stepped to a value significantly positive for the redox
couple (Eappl), so all Red in the vicinity of the electrode is immediately converted
to Ox, showing an exponential current decay
Valid for reversible reaction limited by diffusion (no stirring)
Cottrell equation
i = current, in unit A
n = number of electrons (to reduce/oxidize one • Describes the change
molecule of analyte) in i with respect to t in a
controlled step potential
F = Faraday constant, 96485 C/mol
experiment, such
A = area of the (planar) electrode in cm2 as chronoamperometry.
C0 j = initial concentration of the reducible • The i response shows a

analyte in mol/cm3; dependence with the t-1/2.
D = diffusion coefficient for species in cm2/s
• describes the case for a
t = time in s. planner electrode
DPV - Differential pulse voltammetry
(just to show you a technique that uses pulses) (next slide one
example of an immunobiosensor using this method).
In DPV, a base potential value is chosen at which there is no faradaic reaction and is applied to
the electrode. The base potential is increased between pulses with equal increments. The
current is immediately measured before the pulse application and at the end of the pulse, and
the difference between them is recorded. It gives better signal to noise ratio in comparison to
other amperometric technique.
Magnetic beads combined with carbon black-based screen-printed
electrodes for COVID-19: A reliable and miniaturized electrochemical
immunosensor for SARS-CoV-2 detection in saliva.
doi.org/10.1016/j.bios.2020.112686
Fig. 2. Schematic representation of the electrochemical immunosensors for SARS-CoV-2 detection proposed by Fabiani et al.
[32]. List of abbreviations: CB = carbon black; SPE = screen printed electrode; MBs = magnetic beads; MAb = monoclonal
antibodies; PAb = polyclonal antibodies anti-S = antibodies against Spike protein; anti-N = antibodies against Nucleocapsid
protein; AP = alkaline phosphatase.
AP as the label of enzyme-linked bioassays- (with 4-
nitrophenyl phosphate as substrate)
J. Munoz, R. Montes, M. Baeza. Trends in electrochemical impedance spectroscopy involving nanocomposite transducers:
characterization, architecture surface and Bio-Sensing
TrAC, Trends Anal. Chem., 97 (2017), pp. 201-215, 10.1016/j. trac.2017.08.012

4 CLASS Electrochem Part II Prof. Corton

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How to identify the redox potential of a compound?

O2 as redox entity H2O2 as redox entity

*The rate of the electron transfer reaction(s)

Let us consider the Fe3+/Fe2+ system:

Following voltammogram would be seen for a single voltage scan

As the voltage is sweept from V1 to V2 the equilibrium position shifts

The Nernst equation can be used to determine the relative

In addition to forward scan as in LSV, a reverse scan is also done.

The same potential window is scanned in the opposite direction, hence

i p = 2.68 x 105 n3 /2 A D1/ 2 C v1/2 (If the solution is at 25 °C)

n = no. of electrons transferred in

the redox event

A = electrode area in cm2

D = diffusion coefficient in cm2/s

ν = scan rate in V/s

R = Gas constant in J K−1 mol−1

F = Faraday constant in C mol−1

C0 j = initial concentration of the reducible • The i response shows a

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