Voltammetry

Voltammetric methods are based on measurement of current as a function of the potential difference applied. Polarography is voltammetry at the dropping mercury electrode. Voltammetry is widely used for oxidation and reduction processes in various media adsorption processes on surfaces electron transfer mechanisms at chemically modified electrode surfaces Several different voltage-time functions can be applied at the electrode... called excitation signals A supporting electrode is a salt added in excess to the analyte solution. Most commonly, it is an alkali metal salt that does not react at the working electrode at the potentials being used. The salt reduces the effect of migration and lowers the resistance of the solution. The working electrode is the electrode at which the analyte is oxidized or reduced. The potential between the working electrode and the reference electrode is controlled. Electrolysis current passes between the working electrode and a counter electrode. One of the three electrodes is the working electrode , whose potential versus a reference electrode is varied linearly with time. The dimensions of the working electrode are kept small to enhance its tendency to become polarized. The third electrode is a counter electrode, which is often a coil of platinum wire or a pool of mercury. The current in the cell passes between the working electrode and counter electrode. The signal source is a variable dc voltage source consisting of a battery in series with a variable resistor. Virtually all current from the source passes between the counter electrode and the working electrode. Voltammetric electrodes: they are often small flat disks of a conductor that are press fitted into a rod of an inert material, such as Teflon or Kel-F. A wire contact is imbedded in the material. The conductor may be an inert material, such as platinum or gold; pyrolytic graphite or glassy (vitreous) carbon; a semiconductor, such as tin or indium oxide; or a metal coated with a film of mercury. Mercury electrodes advantages: 1. They have a relatively large electrode potential range. 2. Many metal ions are reversibly reduced to amalgams at the surface of the mercury electrode, which simplifies the the chemistry. Mercury drop electrodes: 1. A fresh metallic surface is readily formed by simply producing a new drop. Hanging mercury drop electrode Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3

1. Consists of a very fine capillary tube connected to a mercury containing reservoir. 2. The metal is forced out of the capillary by a piston arrangement driven by a micrometer screw. 3. The micrometer permits formation of drops with surface areas that are reproducible to 5% or better. Voltammograms A voltammetric wave is a - shaped wave obtained in current-voltage plots in voltammetry There is a reduction of species A to give product P at the mercury film electrode. Here, the electrode is assumed to be connected to the negative terminal of the linear-sweep generator so that the applied potentials are given a negative sign. By convention, cathodic (reduction) currents are treated as being positive, whereas anodic currents are given a negative sign. Linear-sweep voltammograms under slow sweep conditions (a few millivolts per second) generally have the shape of a sigmoidal curve called a voltammetric wave. The limiting current in voltammetry is the current plateau that is observed at the top of the voltammetric wave. It occurs because the surface concentration of the analyte falls to zero. At this point, the mass transfer rate is at a maximum value. The limiting current plateau is an example of complete concentration polarization. Limiting currents are directly proportional to reactant concentration. The potential at which the current is equal to one half of the limiting current is called the half wave potential and is given the symbol E1/2. To obtain reproducible limiting currents rapidly either 1. the solution must be in continuous or reproducible motion 2. a dropping mercury electrode must be used. Linear-sweep voltammetry in which the solution is stirred is called hydrodynamic voltammetry. Voltammetry with the mercury drop electrode is called polarography. In the linear-sweep thus discussed, the potential is changed slowly enough and mass transfer is rapid enough that a steady state is reached at the electrode surface. Hence, the mass transport rate of analyte A to the electrode just balances the reduction rate at the electrode.

Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3