Cyclic Voltammetry

CV
• CV is a qualitative method for electrochem reactions. • It provides fast determination of redox potentials of electroactive species

Cyclic Voltam
• Similar to linear sweep voltammetry • Voltage is swept from V1 to V2 then V2 to V1. • Shows if a electrochemical rxn is reversible or not based on its symmetry • Variation of peak position as function of scan rate gives estimate of electron transfer rate constant

RedOx
• Redox reactions are affected by the electronegativity of the elements. • Electrode reactions are involves transfer of electrons between electrode and species in the solution.

Kinetics of electron transfer
• Volt = joule/coulomb • Energy required to move a charge • Varying the applied potential changes the oxidizing/reducing ability of the electrode • Normally used in organic molecules with extended pi electrons conjugation and transition metal complexes

Equipment
• Potentiostat- controlling the applied voltage • Current to voltage converter- for measuring current • Electrochemical cell– Working- electrode where you alter the voltage – Reference- reference of the working electrode – Auxiliary- balances the rxn in the working electrode

• User interface

Stirred not shaken
• Stirring affects current response • Mass transport (diffusion) • Stationary solutions give a tailed peak shape for CV • In some expt, stirring is done by rotating electrode or stir bar

• CYCLIC VOLTAMMETRY

A. Generating a cyclic voltammogram

Methodology
Purge with N2 (5mins) Set Eo = 600 mV and scan limits at 600 mV and -600 mV

Fill assembled cell with 1 M KNO3

Initiate scan from negative direction at scan rate of 100 mV/s

Switch on working electrode after deoxygenation

Allow current flow until constant value (10 s), then initiate potential scan

Turn off working electrode. Clean cell and refill with 4 mM K3[Fe(CN)6] in 1 M KNO3

Repeat with E range: 600 to -800 mV to obtain the voltammogram of [FeIII(CN)6]-3/[FeII(CN)6]-4 couple

B. Effect of scan rate variation
Observe the effect of scan rate on the voltammogram using 4 mM K3[Fe(CN)6] in 1 M KNO3. Record the CV’s at the rates of 50, 80, 100, and 200 mV.

C. Effect of electroactive species concentration variation
Obtain the cylic voltammograms on 2, 6, 8, and 10 mM K3[Fe(CN)6] using a scan rate of 100 mV/s. Record also the voltammogram of the unknown K3[Fe(CN)6] solution.

D. Effect of supporting electrolyte variation
Investigate the effect of supporting electrolyte. Record the voltammograms of 4 mM K3[Fe(CN)6] in 1 M Na2SO4.

RESULTS AND DISCUSSION

Randles-Sevcik equation:
iP = (2.69x105) n3/2 AC D1/2 v1/2 where: n = # of moles of electrons transferred in the reaction A = area of the electrode C = analyte concentration (in moles/cm3)‫‏‬ D = diffusion coefficient v = scan rate of the applied potential

VOLTAMMOGRAM
• Reversible process E = Ep,a – Ep,c = 59 mV ; n=1 E = Ep,a – Ep,c = 30 mV ; n=2 Ipa/ipc = 1

Epc & Epa  cathodic and anodic peak potential Ipc & Ipa cathodic and anodic peak current Ipa/ipc  peak current ratio

Interpretting CVs
1. draw a single line connecting the two ends of the graph. 2. measure the height from the base line to the peaks (Ip) of the graph (2 per graph)‫‏‬ 3. get the average of the two Ips. 4. plot Ip vs concentration (at constant scan rate) and Ip vs Square root of scan rate (√v, at constant concentration)‫‏‬ 5. get slope, y-intercept and equation of the line. 6. solve for the concentration of unknown. 7. compare the results of Ip upon changing the kind of electrolyte used

A. Generating a cyclic voltammogram

Fig. 1. Cyclic voltammogram of 1 M KNO3 supporting electrolyte

Fig. 2. Cyclic voltammogram of 4 mM K3[Fe(CN)6] in 1 M KNO3

B. Effect of scan rate variation

Fig. 3. Cyclic voltammogram of 4 mM K3[Fe(CN)6] in 1 M KNO3 at 50 mV/s

Fig. 4. Cyclic voltammogram of 4 mM K3[Fe(CN)6] in 1 M KNO3 at 80 mV/s

Fig. 5. Cyclic voltammogram of 4 mM K3[Fe(CN)6] in 1 M KNO3 at 100 mV/s

Fig. 6. Cyclic voltammogram of 4 mM K3[Fe(CN)6] in 1 M KNO3 at 200 mV/s

C. Effect of electroactive species concentration variation

Fig. 7. Cyclic voltammogram of 6 mM K3[Fe(CN)6] in 1 M KNO3 at 100 mV/s

Fig. 8. Cyclic voltammogram of 8 mM K3[Fe(CN)6] in 1 M KNO3 at 100 mV/s

Fig. 9. Cyclic voltammogram of 10 mM K3[Fe(CN)6] in 1 M KNO3 at 100 mV/s

Fig. 10. Cyclic voltammogram of unknown concentration of K3[Fe(CN)6] in 1 M KNO3 at 100 mV/s

D. Effect of supporting electron variation

Fig. 11. Cyclic voltammogram of 1 M Na2SO4 supporting electrolyte

Fig. 12. Cyclic voltammogram of 4 mM K3[Fe(CN)6] in 1 M Na2SO4

RESULTS MAD CLASS

Table 1. Effect of scan rate. *system is 4 mM K3[Fe(CN)6] in 1 M HNO3
v (mV/s)
50 80 100 200

Epa (V)
-0.1140 -0.0940 -0.1000 -0.0640

Epc (V)
-0.4200 -0.4380 -0.4700 -0.4780

ΔEp (V)
0.3060 0.3440 0.3700 0.4140

Eave (V)

ipc (μA)
7.407 9.091 9.259 12.222

ipa (μA)
-7.407 -8.727 -9.259 -11.111

-0.267 -0.266 -0.285

-0.271

Dependence of the peak current on the scan rate
13 R² = 0.9865 12

11

10 ip (μA)

R² = 0.9855

9

ipc ipa

8

7

6 7 8 9 10 11 sqrt(v) 12 13 14 15

Table 2. Dependence of concentration on peak current *System is in 1 M KNO3 at a scan rate of 100 mV/s
Conc. (mM) 0 2 4 6 8 10 Eave (V) -

Epa (V)
-0.0900 -0.1000 -0.0620 -0.0020 0.0220

Epc (V)
-0.4520 -0.4700 -0.4720 -0.5200 -0.5440

ΔEp (V)
0.3620 0.3700 0.4100 0.5180 0.5660

ipc (μA)
0 4.815 9.259 13.333 14.074 16.296

ipa (μA)
0 4.444 9.259 13.333 17.407 20.370

-0.271
-0.285

-0.267
-0.261

-0.261

Calibration Curve
25.000 R² = 0.9951 20.000

15.000 ip (μA)
R² = 0.946 10.000 ipc ipa

5.000

0.000 0 2 4 6 8 10 Concentration (mM)

A calibration curve of CV apparatus for the Fe(CN)63-/4- couple can thus be made to quantify an unknown sample in the same electrolyte measured at the same scan rate.

Determination of concentration of unknown:
Using the ipa: Plot of ipa versus Concentration: slope = 1.619014 μA/mM y-int = 1.534429 μA r = 0.9726 Using the ipa: Plot of ipa versus Concentration: slope = 2.068757 μA/mM y-int = 0.458381 μA r = 0.9975 ipa (unknown) = 14.444 μA ipa = (2.068757 μA/mM) C + 0.458381 μA = 14.444 μA C = 6.7604 mM ipa (unknown) = 14.444 μA ipa = (1.619014 μA/mM) C + 1.534429 μA = 14.444 μA C = 7.9737 mM

Table 3. Effect of supporting electrolyte *System is 4 mM K3[Fe(CN)6] at a scan rate of 100 mV/s

Supporting Electrolyte
1M KNO3 1M Na2SO4

Epa (V)

Epc (V)

ΔEp (V)

Eave (V)

ipc (μA)

ipa (μA)

-0.1000 0.0560

-0.4700 -0.6020

0.3700 0.6580

-0.285 -0.273

9.259 3.636

9.259 5.818

Sources of error
• Equilibrium
– Nernst eqn assumes the rxn is at equilibrium

• Current and pH
– Varying current density due to mass transport of ions

• Potential drop
– Potential gradient due to resistivity of electrolytes

Sources of error
• Cracks
– Cracks in the electrodes, size and area of electrodes

• Passivity
– Protective film that coats the electrode

• Corrosion
– Corrosion products affect the reading

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