Controlled Current Techniques

Basic Terminology
Electrolyte: Medium that contain free ions making it electrically conductive Typically ionic solutions, but molten and solid electrolytes too exist Solute dissociates into ions, and its tendency to dissociate governs the strength of the electrolyte Electrolyte drinks contain Na, K replenish body waters

Electrode: A electric conductor through which electric current is passed. A collector or emitter of electric charge. Used in forms of plates, rods, wires, etc. Metals like Cu, Ag, Pb, Zn and nonmetals like Carbon

1. Working Electrode: At which prinicple electrochemical reaction (oxidation/reduction) takes place Cathodic/Anodic depending on the nature of the reaction Behavior (Potential) is studied with respect to a standard reference electrode

2. Counter/Auxiliary Electrode: Closes the current circuit in the cell Works as complimentary to WE Surface area larger in order not to limit process at WE Supplies the current required by WE Current carrying electrode that completes cell circuit Prone to corrosion - safe 3. Reference Electrode: Provides fixed potential that doesn't vary during operation and against which other potentials are measured.

Controlled Current Techniques

Current (WE CE) is the controlling parameter and potential (WE RE) is measured with time Also called Chronopotentiometry Techniques differentiated based on the pattern the current is controlled

Potentiostat: Electrical instrument that controls and measures voltage. Accurately control the potential between WE and CE

Galvanostat:
Electrical instrument that controls and measures the current flow through electrolytic cell Capable of maintaining constant current flow even when under load variations itself Controls current flow between WE and CE Consists of a high voltage source producing a constant voltage V with a resistor Rx connected in series . To maintain almost constant current through load , this resistor shall be much higher than the load resistor Rload = +

Types of Controlled Current Techniques:

Constant current CP CP with linearly increasing current Current reversal CP Cyclic CP

(1)

First consider constant-current chronopotentiometry for anthracene (An). The steady current, i, applied to the electrode causes the (An) to be reduced at a constant rate to the anion radical An- .

The potential of the electrode varies with time as the An/Anconcentration ratio changes at the electrode surface.
The process can be regarded as a titration of the An in the vicinity of the electrode by the continuous flux of electrons, resulting in an E-t curve like that obtained for a potentiometric titration . The time after application of the constant current till this potential transition occurrence is called the transition time, .

The shape and location of the E-t curve is governed by the reversibility, or the heterogeneous rate constant, of the electrode reaction.

(2) apply a current that varies as a known function of time (e.g., i

=t, a current ramp). this technique, called programmed current chronopotentiometry . (3) If The current is reversed after some time (current reversal chronopotentiometry) at, or before the transition time, the An formed during the forward step will start oxidizing. The potential will move in a positive direction as the An/An concentration ratio increases. When the An concentration falls to zero at the electrode surface, a potential transition toward positive potentials occurs, and a reverse transition time can be measured. (4) if the current continuously reversed at each transition. it is resulting in cyclic chronopotentiometry .

Mathematics of Semi-infinite Linear Diffusion:

Consider simple electron transfer reaction occurring at an electrode where semi-infinite linear diffusion applies: +

- Boundary conditions involving the concentration gradient allows the diffusion problem to be solved without reference to the rate of electron transfer reaction, in contrast with the concentration-potential boundary conditions required for controlled potential methods. - On applying Laplace transform yields,

- These integrals forms are convenient for solving controlled current problems

Constant Current Electrolysis Sand Equation

Concentration profile of O and R various values of t/ during constant current electrolysis are shown in graph.

- The measured value of at known i can be used to determine C0* or D0. A lack of constancy of the transition time constant, i1/2/C*, with i or C0* indicates complications to the electrode reaction from coupled homogeneous chemical reactions, adsorption etc.

- This equation is known as Nernst equation

Response Function:

= Any response R is a function of the input (controlled current, ) and the system properties S. For the semi infinite linear diffusion scenario, response function at x=0 can be given as

Reversal Techniques: i. Consider a situation where current i is supplied for a time t1. At t=t1, the direction of current is reversed to i. Response function at x = 0 thus turns out to be

If 2 is the time at which CR at the R electrode falls to 0, relation between t1 and 2 can be derived as follows:

At t = t1 + 2 , CR = 0, which gives

Multicomponent systems: Consider a system containing two reducible substances O1, O2 1 + 1 1 1 + 2 2 Response functions can be written individually as:

Adding up both equations and rearranging,

From 0 < t < t1, i2 = 0 (due to insufficient negative potential), during which O1 reduces alone,

t > t1, C1(0,s) = 0,

At t = 1 + 2 , C2(0,s) = 0. So, for a constant current = ,

Applying Laplace Inverse,

Derivative Method: By rather straightforword in instrumental approach the deriative of the chronopotonetiogram that is a curve of dE/dt vs. t

While finding from the maximum of the derative curve is possible . for the Nernstian process occur at t= 4 /9

 Determination of the by this approach is free from problem of double layer charging because it evaluated at a position in the curve before the transition time region where an appreciable charging current contribution exist However the large charging current contribution at salt of the chronopotentiogram still contributes The derative approach does suffer from need for knowledge about the degree of thr reversibility of the electrode reaction and it is the reversible knowing the

Controlled Current Techniques

Applications EC mechanisms are especially amenable to study by this technique.
Ex. Oxidation of p-aminophenol (PAP)

CHEM 5390

Controlled Current Techniques

Applications
Ex. Oxidation of p-aminophenol (PAP)

CHEM 5390

Controlled Current Techniques

Applications
Ex. Oxidation of p-aminophenol (PAP)

CHEM 5390

Controlled Current Techniques

Cyclic Chronopotentiometry
Current is continually reversed at potentials corresponding to the forward and reverse transition times. Not used much.

CHEM 5390

Charge Step (Coulostatic) Methods

In the charge step (or coulostatic) method a very shortduration(eg., 0.1 to 1 sec) current pulse is applied to the cell, and the variation of the electrode potential with time after the pulse is recorded. The current-pulse length is chosen to be sufficiently short that it only causes charging of the electrical double layer. The charge can be injected by discharging a small capacitor across the electrochemical cell as shown in fig. or with a pulse generator connected to the cell by a capacitor or switching diodes.

 Cinj is charged by the voltage source, Vinj

Capacitor is charged by the amount: Eg. Vinj=10V and Cinj =10-9 F
q= Cinj Vinj

q=0.01C

 The time required for this charge injection will depend on the cell resistance, R. This injected charge causes the potential of the electrode to deviate from its original value Eeq to a value E(t = 0),
The charge on Cd now discharges through the faradaic impedence, and the open circuit potential moves back towards as decreases to zero. If no faradaic reaction reaction is possible, Cd remains charged and the potential will not decay.

Large Steps-Coulostatic Analysis

Consider the application of a charge step sufficiently large that the potential changes from Eeq to a value, E(t=0) Assumption: double layer capacity, Cd is independent of potential in this region.

 is linear with a zero intercept. This method has been suggested for the determination of small concentrations of electroactive materials, but not been widely applied because it requires recording of E-t curve.

Application of charge-Step Methods

Advantages in the study of electrode reactions, since the measurement is made at open circuit with no net external current flow Measurements in highly resistive area can be made