CHM578/674 2020

Experiment 5: Cyclic Voltammetry (20 marks)

Name: Nurul Husna binti Ibrahim ID: 2018226626 Group: AS2224M1

(Refer Lab manual Exp. 5 CHM674 prior to answering the following Post-Lab
Questions)

The important parameters obtained from a cyclic voltammograms are the anodic peak current
(Ipa), cathodic peak current (Ipc), anodic peak potential (Epa) and cathodic peak potential (Epc).
All of these values can be readily obtained from the voltammogram. Measuring Ip's involve
the extrapolation of the base-line current.

The peak current for an electrochemically reversible system (rapid transport of electrons on the
surface within the framework of the experiment) is described by the Randles-Ševcík equation:

Ip = (2.69x105)n3/2AD1/2 v1/2c

Where: Ip = peak current (in A)

n = electron stoichiometry
D = diffusion coefficient (cm2/s)
c = concentration (mol/cm3)
A = electrode area (cm2)
v = potential scan rate (V/s)

Oxidation: Reduction :

Reversible reactions may be diagnosed using the following criteria:

 Peak separation ∆E = Epa - Epc = 59 mV (2.303 RT/F = 59 at 298K)

 Ip,a / Ip,c = 1

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 Ip,a and Ip,c α v1/2

 Ep, a and Ep,c independent of v

Results - CV Parameters (8 marks)

Table 1 : Effect of FeCN64- Concentration

Concentration Epa (mV) Ip,a (μA) Epc (mV) Ip,c (μA) ∆E (mV)
of Fe(II)
Solution

2 mmol +280 18 +220 -18 60

4 mmol +280 26 +220 -28 60

6 mmol +280 45 +220 -47 60

8 mmol +280 58 +190 -52 90

10 mmol +310 62 +120 -52 190

unknown +300 32 +240 -30 60

Area of gold electrode (ie: working electrode) = 0.078 cm 2, ∆E = Epa - Epc

Scan potential: -0.2 V to +0.65 V back to -0.2 V

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Scan rate : 25 mV/s

Table 2 : Effect of scan rate (Constant Concentration: 4 mmol)

Scan rate, ν Epa Ip,a Epc Ip,c ∆E scan rate

(mV) (μA) (mV) (μA) (mV) (v ½ )

25 mV/s (0.025 V/s) +280 27 +220 -28 +60 0.158

50 (0.050) +280 42 +220 -42 +60 0.224

75 (0.075) +280 54 +220 -52 +60 0.274

100 (0.100) +280 58 +220 -60 +60 0.316

125 (0.125) +280 66 +220 -68 +60 0.354

200 (0.200) +280 84 +220 -88 +60 0.447

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Plot of Ipa versus v ½ = 1.85 x 10-4

Reference Electrode used: Ag/AgCl (KCl saturated) Ecell = +0.195 V vs SHE

Post-laboratory Questions (12 marks)

1. From Table 1, estimate the concentration of the unknown.

- Ip,q = 3.2×10-5 A, concentration of the unknown is 4.9 mmol

2. Based on CV results in Table 2, determine diffusion coefficient,D of Fe2+ ions and compare
it with the literature value (ie: DFe2+ = 7.0 x 10-6 cm2/s).

(Hint: use Randles-Servcik Equation to find D, c = mol/cm 3, slope Ipa/v½ = 1.85 x 10-4, n=1,
A = 0.078 cm2)
1
Answer: ¿ graph I vs V 2
p, q

I p, q
: 1
=slope=1.85 ×1 0−4
2
V
3 1 1
Ip=(2.69 × 10¿¿ 5)n 2 AD 2 V 2 c ¿

1
Ip
D2= 3 1
(2.69 ×10¿ ¿5) n 2 A V 2 c ¿

1.85× 10−4
¿ 3
( 2.69× 105 ) ( 1 2 ) ( 0.078 ) ( 4 ×10−6 )

D=¿

( 7.0 ×10−6 ) ( 4.86 ×10−6 )

Percentage error : | 7.0 ×10−6 |×100 %

¿ 30.57 %

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3. Define the following terms:

Standard Electrode Potential (Eo) : The measure of the individual potential of reversible
electrode at standard state which is 1 mol dm-3 at 1 atm.

Cell Potential (E cell) : The measure of potential difference between two half cells in an
electrochemical series

Formal Electrode Potential (E’) : The reduction potential that applies to a half reaction under
specified conditions

Half-wave Potential (E ½) : The potential exactly in the middle of the two peaks where there
is forward and reverse wave.

5. Based on the CV results in Table 2, determine the formal reduction potential (E’) of the
ferro/ferricyanide couple. Correct for the potential of the reference electrode and compare it
to the standard potential for the couple (Eo Ferro/Ferriccyanide = +0.436 V vs SHE).
Comment on any observed difference.

(E ¿ ¿ p , a+ E p ,c )
Answer: ¿
2

280+220
2

¿ 250 mV =0.250 V

Emeasured =E °−E reference

E °=0.250+ 0.195

0.445 V

0.436−0.445
Percentage error =¿ ∨×100
0.436

¿ 2.06 %

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6. From the CV results, identify the reversibility of Fe(CN) 64-/Fe(CN)63- redox reaction (either
reversible, irreversible or quasi-reversible). Justify your answer.

- The redox reaction is reversible because the redox system remains in equilibrium
throughout the potential scan