Name - ​Akshay Kaushik 

Group No. - ​4th 

Assignment
(Cyclic voltammetry)
AIM : 
Record the CV of aqueous solution of sulphuric acid (0.5 M) at Pt  
electrode as working electrode and counter electrode. 
(a) Interpret and explain various peaks and regions of the CV and 
their significance. 
(b) Determine the area and roughness factor of the electrode by H- 
adsorption and H- desorption. 
(c) Determine the area and roughness factor of the electrode by Pt 
oxide region. 
 

THEORY : 
Cyclic voltammetry (CV) is a powerful and popular electrochemical 
technique commonly employed to investigate the reduction and 
oxidation processes of molecular species. CV is also invaluable to 
study electron transfer-initiated chemical reactions, which 
includes catalysis. As inorganic chemists embrace 
electrochemistry, papers in the literature often contain figures like 
Figure 1. 
  
The traces in Figure 1 are called voltammograms or cyclic 
voltammograms. The x-axis represents a parameter that is 
imposed on the system, here the applied potential (E), while the 
y-axis is the response, here the resulting current (i) passed. 
The current axis is sometimes not labeled (instead a scale bar is 
inset to the graph). 
 
Understanding the “Duck” Shape: Introduction to the 
Nernst Equation : 
Why are there peaks in a cyclic voltammogram? Consider the 
equilibrium between metal ion (M​+​) and metal(M). 
This equilibrium is described by the Nernst equation . 
The Nernst equation relates the potential of an electrochemical cell 
(E) to the standard potential of a species (E0) and the relative 
activities16 of the oxidized (Ox) and reduced (Red) analyte in the 
system at equilibrium. In the equation, F is Faraday’s constant, 
R is the universal gas constant, n is the number of electrons, and T 
is the temperature 

 
In application of the Nernst Equation to the one-electron 
reduction of M​+​ to M, the activities are replaced with their 
concentrations, which are more experimentally accessible, the 
standard potential E0 is replaced with the formal potential E0′, 
and n is set equal to 1: 

 
 
The formal potential is specific to the experimental conditions 
employed and is often estimated with the experimentally 
determined E​1/2​ value .The Nernst equation provides a powerful way 
to predict how a system will respond to a change of concentration 
of species in solution or a change in the electrode potential. 
To illustrate, if a potential of E = E°′ ≈ E​1/2​ is applied to our 
example M​+​ solution, the Nernst equation predicts that M+ will 
be reduced to M until [M​+​] = [M], and equilibrium is achieved. 
Alternatively, when the potential is scanned during the CV 
experiment,the concentration of the species in solution near the 
electrode changes over time in accordance with the Nernst 
equation. 

 
When a solution of M+ is scanned to negative potentials, M+ 
is reduced to M locally at the electrode, resulting in the 
measurement of a current and depletion of M+ at the electrode 
surface. The resulting cyclic voltammogram is presented in 
Figure 2 as well as the concentration−distance profiles for M+ 
(blue) and M (green) at different points in the voltammogram. 
Crucially, the concentrations of M+ vs M relative to the distance 
from the surface of the electrode are dependent on the potential 
applied and how species move between the surface of the 
electrode and the bulk solution (see below). These factors all 
contribute to the “duck”-shaped voltammograms. 
As the potential is scanned negatively (cathodically) from 
point A to point D (Figure 2), [M+] is steadily depleted near the 
electrode as it is reduced to M. At point C, where the peak 
cathodic current (ip,c) is observed, the current is dictated by the 
delivery of additional M+ via diffusion from the bulk solution. 
The volume of solution at the surface of the electrode containing 
the reduced M, called the diffusion layer, continues to grow 
throughout the scan. This slows down mass transport of M+ to the 
electrode. Thus, upon scanning to more negative potentials, the 
rate of diffusion of M+ from the bulk solution to the electrode 
surface becomes slower, resulting in a decrease in the current as 
the scan continues (C → D). When the switching potential (D) 
is reached, the scan direction is reversed, and the potential 
is scanned in the positive (anodic) direction. While the 
concentration of M+ at the electrode surface was depleted, the 
concentration of M at the electrode surface increased, satisfying 
the Nernst equation. The M present at the electrode surface is 
oxidized back to M+ as the applied potential becomes more 
positive. At points B and E, the concentrations of M+ and M at 
the electrode surface are equal, following the Nernst equation, 
E = E​1/2​. This corresponds to the halfway potential between the 
two observed peaks (C and F) and provides a straightforward 
way to estimate the E0′ for a reversible electron transfer, as noted 
above. The two peaks are separated due to the diffusion of the 
analyte to and from the electrode. 
If the reduction process is chemically and electrochemically 
reversible, the difference between the anodic and cathodic peak 
potentials, called peak-to-peak separation (ΔEp), is 57 mV at 
25 °C (2.22 RT/F), and the width at half max on the forward scan 
The peak is 59 mV. Chemical reversibility is used to denote 
whether the analyte is stable upon reduction and can subsequently 
be reoxidized. Analytes that react in homogeneous 
chemical processes upon reduction (such as ligand loss or 
degradation) are not chemically reversible (see discussion below 
on EC Coupled Reactions). Electrochemical reversibility refers 
to the electron transfer kinetics between the electrode and 
the analyte. When there is a low barrier to electron transfer 
(electrochemical reversibility), the Nernstian equilibrium is 
established immediately upon any change in applied potential. 
By contrast, when there is a high barrier to electron transfer 
(electrochemical irreversibility), electron transfer reactions are 
sluggish and more negative (positive) potentials are required 
to observe reduction (oxidation) reactions, giving rise to larger 
ΔEp. Often electrochemically reversible processes were the 
electron transfers are fast and the processes follow the Nernst 
equations are referred to as “Nernstian.” 
 
Importance of the Scan Rate : 
The scan rate of the experiment controls how fast the applied 
potential is scanned. Faster scan rates lead to a decrease in the 
size of the diffusion layer; as a consequence, higher currents 
are observed. For electrochemically reversible electron 
transfer processes involving freely diffusing redox species, the 
Randles−Sevcik equation describes how the peak current 
ip (A) increases linearly with the square root of the scan rate 
υ (V s​−1​), where n is the number of electrons transferred in the 
redox event, A (cm​2​) is the electrode surface area (usually treated 
as the geometric surface area), D​o​ (cm​2​ s​−1​) is the diffusion 
coefficient of the oxidized analyte, and C​0​ (mol cm​−3​) is the bulk 
concentration of the analyte 

 
 
The Randles−Sevcik equation can give indications as to 
whether an analyte is freely diffusing in solution. As analytes can 
sometimes adsorb to the electrode surface,it is essential to assess 
whether an analyte remains homogeneous in solution prior to 
analyzing its reactivity. In addition to verifying that the analyte is 
freely diffusing, the Randles−Sevcik equation may be used to 
calculate diffusion coefficients. 
 
 
 
 
Adsorption/Desorption of Hydrogen on Pt electrodes: 
The electrolysis of water, which was first observed by Volta in the 
beginning of the 19th century, is probably the best studied 
electrochemical process. At a Pt working electrode, water can be 
either oxidized at positive potentials to produce oxygen or reduced 
at negative potentials to produce hydrogen. Extensive studies of 
both hydrogen and oxygen evolution reactions focused on their 
kinetics, catalysis, and numerous applications including energy 
storage. Adsorption of hydrogen and oxygen species occurs at less 
negative (hydrogen) and positive (oxygen) potentials than their 
evolution processes. Voltammetry in acidic solution is a standard 
technique used for electrode characterization, and a typical cyclic 
voltammogram (CV) at a large (i.e., millimeter-sized) Pt electrode 
exhibits several pairs of peaks corresponding to 
adsorption/desorption of hydrogen and oxygen containing species. 
The characteristic value of charge density associated with a 
monolayer of hydrogen adsorbed on polycrystalline platinum (210 
µC/cm2 ) is widely used to determine the true (microscopic) surface 
area of Pt electrodes. The ratio of the microscopic surface area to 
the geometric area (Am/Ag) gives the roughness factor (F). 
 

PLOTS FROM THE GIVEN DATA : 

 
 
SCALE : 
X-AXIS :​0.2 mV 
Y-AXIS :​0.0002 μA 
 
FOR SET 2: 

 
 
SCALE : 
X-AXIS :​0.2 mV 
Y-AXIS :​0.0005 μA 
 
 

CALCULATION FOR 0.5M H​2​SO​4 : ​

SET 1 : 
FOR H-DESORPTION : 
● 1 square cm of ECSA is equal to 210 μC 
● Area =area under the curve / ν 
 ● Area = (17 x 0.00004 x 0.04 )/ (100 x 0.001 ) = 272 μC 
● AREA = 272/210 = 1.29 cm​2 
● Roughness factor (R​*​) = 1.29 / 0.08 = 16.125 
 
FOR H-adsorption: 
● 1 square cm of ECSA is equal to 210 μC 
● Area =area under the curve / ν 
● Area = (23 x 0.00004 x 0.04 )/ (100 x 0.001 ) = 368 μC 
● AREA = 368/210 = 1.75 cm​2 
● Roughness factor (R​*​) = 1.75 / 0.08 = 21.875 
 
 
FOR Pt-oxide region : 
● 1 square cm of ECSA is equal to 420 μC 
● Area =area under the curve / ν 
● Area = (97 x 0.00004 x 0.04 )/ (100 x 0.001 ) = 1552 μC 
● AREA = 1552/420 = 3.69 cm​2 
● Roughness factor (R​*​) = 3.69 / 0.08 = 46.175 
 
SET 2 : 
FOR H-DESORPTION : 
● 1 square cm of ECSA is equal to 210 μC 
● Area =area under the curve / ν 
● Area = (14 x 0.00001 x 0.04 )/ (100 x 0.001 ) = 56 μC 
● AREA = 56/210 = 1.29 cm​2 
● Roughness factor (R​*​) = 1.29 / 0.08 = 16.125 
 
FOR H-adsorption: 
● 1 square cm of ECSA is equal to 210 μC 
● Area =area under the curve / ν 
● Area = (22 x 0.00001 x 0.04 )/ (100 x 0.001 ) = 88 μC 
 ● AREA = 88/210 = 0.419 cm​2 
● Roughness factor (R​*​) = 0.419 / 0.08 = 5.237 
 
 
FOR Pt-oxide region : 
● 1 square cm of ECSA is equal to 420 μC 
● Area =area under the curve / ν 
● Area = (96 x 0.00001 x 0.04 )/ (100 x 0.001 ) = 384 μC 
● AREA = 384/420 = 0.914 cm​2 
● Roughness factor (R​*​) = 0.914/ 0.08 = 11.425 
 

RESULTS : 
1.THE CV OF Aq. SOLUTION OF H​2​SO​4​SHOWED 4 DIFFERENT 
REGIONS(MENTIONED IN PLOT) : 
1. HYDROGEN ATOM DESORPTION  
2. HYDROGEN ATOM ADSORPTION 
3. OXIDE FORMATION  
4. OXIDE REDUCTION  
 
 
2.THE AREA AND ROUGHNESS FACTOR OF THE ELECTRODE BY 
H-DESORPTION AND H-ADSORPTION : 
SET 1- 
 
H-DESORPTION: 
● Area = 1.29 cm​2 
● Roughness factor (R​*​) = 1.29 / 0.08 = 16.125 
 
H-ADSORPTION: 
● AREA = 1.75 cm​2 
 ● Roughness factor (R​*​) = 1.75 / 0.08 = 21.875 
 
SET -2 : 
 
H-DESORPTION: 
● AREA = 1.29 cm​2 
● Roughness factor (R​*​) = 1.29 / 0.08 = 16.125 
 
H-ADSORPTION: 
● AREA = 0.419 cm​2 
● Roughness factor (R​*​) = 0.419 / 0.08 = 5.237 
 
 
3.THE AREA AND ROUGHNESS FACTOR OF THE ELECTRODE BY 
Pt-OXIDE REGION : 
SET -1 : 
● AREA = 3.69 cm​2 
● Roughness factor (R​*​) = 3.69 / 0.08 = 46.175 
 
SET -2 : 
● AREA = 0.914 cm​2 
● Roughness factor (R​*​) = 0.914/ 0.08 = 11.425