Abstract

Using the cyclic voltammogram, calculate the Dep and n for the K3Fe(CN)6 pair in 1.0 M KNO3 and also
ascertain the impact of scan rate on the cyclic voltammogram's peak height and to produce a calibration
graph of concentration vs peak height in order to ascertain the concentration of an unknown K3Fe(CN)6
solution ascertain the cyclic voltammogram's impact on the supporting electrolyte.

Cyclic Voltammetry has a multipurpose electro analytical technique for the study of electroactive
species, the method displays redox behavior of chemical species inside a wide range potential. The
current at the working electrode is observed as a three-cornered excitation potential is applied to the
electrode. The purpose of this paper was to determine the diffusion coefficient (D) of the K3[Fe(CN)6]
and uric acid; electrochemical nature of K3[Fe(CN)6], effects of varying the concentrations analytes on
peak currents and peak splitting and scan rate CV on peak currents and peak splitting. All the reagents
used for this experiment were analytical grade. K3[Fe(CN)6] solutions were prepared. The experiment
has been implemented with the principles of cyclic voltammetry. The relationship between the scan rate
and the peak current were investigated and the result shows that there is a direct relationship between
scan rate and peak current. As articulated on the above voltammograms, the peak current increases
with the augmentation of the concentrations of K3[Fe(CN)6], So that, the researcher conclude the
manifestation of direct relationship between peak current and concentration of analyses. The
experiment of this research shows that the increasing of diffusion coefficient (D) with increasing of
concentrations /and scan rate. The peak currents and peak splitting fluctuate with variation of scan rate
of CV. Similarly, the peak currents and peak splitting vacillate with variation of concentration of the
analytes.CV therefore can be used as an indication of major analytical tool for the determination of the
trace elements which are electro active in nature. The electrochemical nature of K3[Fe(CN)6] were
determined; reversible and irreversible respectively.
Introduction

A technique for examining a system's electrochemical behavior is called cyclic voltammetry. Randies
originally gave a theoretical description of it in 1938. The most used method for gathering qualitative
data regarding electrochemical processes is cyclic voltammetry. The effectiveness of cyclic voltammetry
is due to its speedy capacity to offer significant information on the thermodynamics of redox processes,
on the kinetics of heterogeneous electron-transfer events, and on linked chemical reactions or
adsorption processes.

Since it provides quick identification of the redox potentials of the electroactive species and
straightforward assessment of the impact of media upon the redox process, cyclic voltammetry is
typically the first experimental method used in an electroanalytical research. Applying a linear potential
sweep to the working electrode, or a potential that rises or falls linearly with time, yields a cyclic
voltammogram . Current runs through the electrode that either oxidises or decreases the analyte as the
potential is swept back and forth past the formal potential, E°, of the analyte. Cyclic voltammetry may
be used to provide an analytical determination of analyte concentration since the size of this current is
proportional to its concentration in solution. yclic voltammograms are most often characterized by: a)
the location of the forward and reverse peaks on the potential axis (Ep and ∆Ep, allowing the calculation
of E0’); b) the ratio of currents observed on the reverse and forward scans (ip,rev / ip,fwd); and c) the
dependence of peak currents on the scan rate (ip vs. ν1/2). As before, an uncomplicated, chemically and
electrochemically reversible redox system will first be described. Next, deviations from the reversible
case will be presented, and the resulting changes in the appearance of the voltammograms obtained will
be used as diagnostic criteria for electrode reaction mechanisms of varying types.

Peak Location

n the forward scan of a cyclic voltammogram, the conditions that exist at the surface of the electrode
are the same as those we have previously described for linear scan voltammetry. For conditions that
include an electrode product that is stable on the time scale of the potential scan, the presence of a
return peak in cyclic voltammetry allows us to now determine the formal potential for a redox couple,
, by averaging the two peak potentials

+ )/2

where and represent the forward and reverse peak potentials, respectively. The position of the
E0’ is characteristic of a redox species in much the same way that the wavelength of maximum
absorbance is characteristic of a species in spectroscopic experiments. The separation between the two
peak potentials, can be used determine the electrochemical reversibility for a redox couple, with

for the reversible case ( in volts). This value is independent of the scan rate for fast electron transfer.
Increasing values of as a function of increasing scan rate indicates the presence of electrochemical
irreversibility. The value of ∆ can be used in the calculation of the heterogeneous electron transfer
rate constant (ks) for the redox reaction.

The potential of the working electrode is measured against a reference electrode which maintains a
constant potential, and the resulting applied potential produces an excitation signal such as that of
figure 1. In the forward scan of figure 1, the potential first scans negatively, starting from a greater
potential (a) and ending at a lower potential (d). The potential extrema (d) is call the switching potential,
and is the point where the voltage is sufficient enough to have caused an oxidation or reduction of an
analyses. The reverse scan occurs from (d) to (g), and is where the potential scans positively. Figure 1
shows a typical reduction occurring from (a) to (d) and an oxidation occurring from (d) to (g). It is
important to note that some analyses undergo oxidation first, in which case the potential would first
scan positively. This cycle can be repeated, and the scan rate can be varied. The slope of the excitation
signal gives the scan rate used.
Calculation

Using the data generated from the CV scans of the 4mM in 1 M KN report the

Values of and .

The effect of scan rate (v) on the CV can be described by the Randle-Sevcik euation.

A C

Where is the peak current ( anodic and cathodic)

n is the electron stoichiometry

A is the electrode area ( )

D is the diffusion current

C is the concentration (mol/ )

V is the scan rate (V/s)

Make a plot of and versus and report the diffusion coefficient for the system. The value of A
will be given by the instructor. Evidence of electrochemical reversibility can be ascertained by the
independence of on v. From the experiment, using variable scan rate, show that this system is
electrochemically reversible.

The number of electrons transferred in the electrode reaction (n) for a reversible couple is given by

- = 0.059/n
Now Plots of Different experiment:

Plot of First Experimental data in which 0.000001M in 1M KNO3.

The Plots first decreases and then increases.

Figure 10.000001M in 1M KNO3.

This plot is for experiment 2 in which 0.00001 in 1 M KMNO3.

The plot show same behaour as the above

Figure 2 0.00001 in 1 M KMNO3

This plot is for experiment 3 in which 0.0001 M in 1M of KNO3.

This graph shows some different behavior at different place increases and then decreases.

Figure 3 0.0001 M in 1M of KNO3.

This plot is for experiment 4 in which 0.001M in 1M KNO3.

This plot show different peak on different position first decreases and then increases and finally
decreases,

Figure 4 0.001M in 1M KNO3.

This plot is for experiment 5 in which 0.01M in 1M KNO3.

The plot first constant then decreases then increases and show a peak value finally decreases.

Figure 5 0.01M in 1M KNO3.

This plot is for experiment 6 in which 0.01M in 1M of KNO3.

The plot show same peak as the above.

Figure 6 0.01M in 1M of KNO3

This plot is for experiment 7 in which 0.01M in 1M KNO3 the scan rate (100).

The plot first constant then decreases then increases and show a peak value finally decreases.

Figure 7 0.01M in 1M KNO3 the scan rate (100)

This plot is for experiment 8 in which 0.01M in 1M K NO3 scan rate 200.

The plot is first constant then increases then decreases.

Figure 8 0.01M in 1M K NO3 scan rate 200.

This plot is for experiment 9 in which 0.01M in 1M KNO3 scan rate 250.

Figure 9 0.01M in 1M KNO3 scan rate 250

This plot is for experiment 10 in PH 4 0.01M in KNO3 Scan rate 100.

Figure 10 PH 4 0.01M in KNO3 Scan rate 100.

This plot is for experiment 11 in which PH5 0.01M in KNO3 scan rate 100.

Figure 11 PH5 0.01M in KNO3 scan rate 100.

This plot is for experiment 12 in which PH 6 ,0.01 M in KNO3 scan rate 100.

Figure 12 PH 6 ,0.01 M in KNO3 scan rate 100

This plot is for experiment 13 in which PH =7 , 0.01M in KCL

Figure 13 which PH =7 , 0.01M in KCL

This plot is for experiment 14 in which PH=7, 0.01M in KNO3 Scan rate 100.

Figure 14 PH=7, 0.01M in KNO3 Scan rate 100.

This plot is for experiment no 15 in which PH= 7, 0.01M in NaCL

Figure 15 PH= 7, 0.01M in NaCL

This plot is for experiment 16 in which PH=7,0.01M in NaNO3

Figure 16 PH=7,0.01M in NaNO3

This plot is for experiment 17 in which PH =8, 0.01M in KNO3 Scan rate 100.

Figure 17 PH =8, 0.01M in KNO3 Scan rate 100.

Conclusion:

Half-wave potentials, which are easily obtained from cyclic voltammograms, are unquestionably the
finest representations for E(0), even in situations where partial irreversibility is manifested due to the
created species' sluggish disintegration. Contrarily, all data points to the inflection potentials and the
half-peak potentials as the best sources of estimates for E(0) at moderate scan speeds, such as 100 to
500 mV s-1, While E(i) and E(p/2) often behave similarly, E(i) values naturally tend to be closer to E(1/2)
than E(p/2) values. In order to enhance and increase the usability of electrochemical results, this paper
presents a crucial basis and vital evidence for changing frequently used practices. n E(1/2) is not possible
due to total chemical irreversibility.