I.

UNIT II ELECTROANALYTICAL TECHNIQUES

Summary of the learning activity At the End of this unit the student will be able to: Recall the theory on which potentiometry is based Explain the application of potentiometry to pH measurement, ion selective electrode and automatic titration stations Recall the theory of Voltammetry Interpret Voltammetric data quantitatively and qualitatively Explain the concept of on which polarographic analysis is based Interpret polarographic data to identify and quantify chemical Species

List of REQUIRED readings http://en.wikipedia.org/wiki/Electroanalytical_methods http://www.chem.vt.edu/chem-ed/echem/electroc.html http://www.chem.vt.edu/chem-ed/echem/potentio.html http://electrochem.cwru.edu/ed/encycl/art-a03-analytical.htm http://ull.chemistry.uakron.edu/analytical/Voltammetry/ http://ull.chemistry.uakron.edu/analytical/index.html

List of relevant useful links

Detailed Description of the activity Potentiometry Potentiometry involves measuring activities or concentrations of materials by measuring potential differences between a measuring (indicator) electrode and a reference electrode in an electrochemical cell. VOLTAMMETY

Introduction to Voltammetry
Voltammetry is concerned with application of voltage current time relations during electrolysis in a cell which has two electrodes one of electrodes is extremely small called a micro electrode and the large one is called the counter electrode. The micro electrode is usually polarized i.e. the concentration of the ions at the surface electrode is different from the concentration of the ions from the bulk of the solution. Therefore the diffusion of the ions from the bulk of the solution to the micro electrode becomes an important phenomenon. The total current I= Im+ Id

Im=Migration current Id=diffusion current

In order to maintain a constant migration current another electrolyte is added to the solution of the electrolyte this second electrolyte is called a supporting electrolyte. Usually KCl is used this provides the migration current.

The different voltammetric techniques that are used are distinguished from each other primarily by the potential function that is applied to the working electrode to drive the reaction, and by the material used as the working electrode. Common techniques to be discussed here include i. ii. Polarography Anodic Stripping Voltammetry

Polarography
In Polarography the micro electrode is a succession of mercury drops (falling slowly from a capillary tube) and is usually the cathode. The anode is usually a pool of mercury. The electrolyte is the solution of the analyte which must be electro active material to which is added and excess of a supporting electrolyte. This type of micro electrode is called a dropping mercury electrode (DME) If a voltage is imposed on the DME a It current will flow that is composed of the following It=Id +Im +Ir Residual current Ir A small current will flow due to the capacitive charging of the mercury drops and reducible impurities in the supporting electrolyte. Migration Current Im The electro active material reaches the DME by two mechanisms by migration and by diffusion. If the concentration of the supporting electrolyte is high more than 100 times the analyte then all the migration current will be carried by the supporting electrolyte.

Diffusion Current Id

With the excess of the supporting electrolyte the electro active material will reach the DME by diffusion. As the voltage at the DME is increased this diffusion current increases until it reaches a limiting value Id From theory D is a constant from diffusion theory, n is the number of electrons involved in the electrochemical reaction, m is the mass of mercury drops, t is the interval between mercury drops It can clearly be seen that the diffusion current is proportional to the concentration of the electro active analyte.

Id

Current

E 1/2

Voltage

On application of an increasing voltage to the DME the current changes as shown in the diagram initially there will be only the residual current which is small and constant. On increasing the voltage further a point will be reached when the reduction potential of the analyte is reached and starts to increase with the increasing voltage until the limiting current Id is reached. E

is called the half wave potential and it uniquely identifies the

electro active material in the analyte.