CHAPTER 6 CYCLIC VOLTAMMETRY DETERMINATION OF DIFFUSION COEFFICIENTS Electrochemical transient techniques were used in determining the diffusion coefficients

of electrochemical active species. The key to extracting information from electrochemical data is to use a system where the mass-transfer is well described in terms of operating parameters. The techniques that meet this criteria and that will be used to determine the diffusion coefficient of Fe(CN)6-3 in 1 M KCl are Linear sweep voltammetry and Limiting current studies at a rotating electrode. The reduction reaction of interest is Fe(CN)6-3 + e- ⇔ Fe(CN)6-4 Below is the description of two techniques. 6.1 Linear Sweep Voltammetry Linear sweep voltammetry (LSV) is a transient technique in which the potential difference between the working and reference electrode is changed linearly with time. The competing effects of an increasing potential driving force and an increasing diffusion layer thickness results in a peak current (see figures 1 and fig 2). For fast Charge-transfer kinetics, the peak current is related to the sweep rate by the following equation .(Randles-sevcik equation)

ip = 0.4463NFAC0* nfυD0


where ip is the peak current , n is the number of electrons transferred in the electrochemical reaction , F is the Faradays constant, A is the electrode area, C0* is the

Pt-disc (working) and Pt. Deoxygenate the solution by passing Nitrogen gas through a sparging tube for 10 minutes. Polishing material Procedure 1. 250 mL Beaker 6. Equation (1) indicated that a plot of the peak current versus the square root of the sweep rate would result in a straight line. Shake the working electrode in order to destroy the diffusion layer . Transfer approximately 150mL to 250mL beaker and deoxygenate for another 2 minutes. Repeatedly scan the potential (i. and sweep the potential in the negative direction at 225 mV/s. X-Y recorder or data acquisition facility 3. .gauze (Counter) electrodes 7.bulk concentration of the oxidized species.75 V to the working electrode relative to the Ag/AgCl reference electrode. 7. and D0 is the diffusion coefficient of the oxidized species . Ag/AgCl electrode 8. 6. Scanning Potentiostat 2. K3Fe(CN)6 and KCl 4.15 V versus Ag/AgCl at a sweep rate of 100 mV/s . Polish the Pt disc to a mirror finish and thoroughly rinse it with DI water. 5. 3. set the initial potential to 1 V versus Ag/AgCl . υ is the sweep rate. Connect the three electrodes to the potentiostat and apply 0. Required Equipment and Supplies 1. Deionized (DI) water 5. Use DI water to prepare a 0. f ≡ F/RT. The slope of the line can be used to extract the diffusion coefficient of Fe(CN)63-.e cycle) between 0.01 M solution of K3Fe(CN)6 IN 1 M KCl 2. 4.75 V and 0.

Plot ip versus √ υ and obtain D0 from the slope of the resulting straight line. The slope of the line can be used to extract the diffusion coefficient of the ferricyanide ion. 2. Draw conclusions on the reversibility of the system.8. Lower the rotation speed to 64 rpm and record the steady state current. Repeat item 7 at different convenient scan rates (196. Procedure 1. Choose a potential in the plateau region and hold the potential at the value. 2.75 V versus the Ag/AgCl reference electrode towards more negative values until the current reaches a plateau. and ϑ is the viscosity of the electrolyte. 4. Limiting Current at a Rotating -Disc electrode Introduction Limiting current at a rotating -disc electrode is a steady state technique in which the potential is held at a value where the current has reached a limiting value. . 3.169. The limiting current is related to the electrode by the following equation. ω is the rotation speed of the electrode. Equation (2) indicates that a plot of the limiting current versus the square root of the rotation speed will result in a straight line. Required Equipment and supplies Same as previous with a Rotating -disc Assembly .144. scan the potential from 0. At 10 mV/s and 400 rpm. iL = 0.121….620NFAC0*D02/3 ω 1/2 1 ϑ 1/ 6 (2) Where iL is the limiting current.9). 10. 9. Repeat items 1-5 of the LSV experiment.

Plot iL versus line. EPA . EP .EP/2 = 59/n mV 3. EP is independent of υ DIAGNOSTIC TESTS FOR IRRREVERSIBILITY: 1. Ep . IpA/IpC =1 4. ω and obtain D0 from the slope of the resulting straight DIAGNOSTIC TESTS FOR REVERSIBILITY: 1. Ip is proportional to υ 5. No reverse peak 2.EPC = 59/n mV 2. IpC is proportional to υ 1/2 3.196…784) and 900 rpm 6.5.Ep/2 = 48/αcnα mV . EpC shifts -30/αcnα for each decade increase in υ 4.144. Repeat item 4 at convenient scan rates (100.

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