TAILIEUCHUNG - Voltammetry

Voltammetry techniques measure current as a function of applied potential under conditions that promote polarization of a working electrode. Polarography: Invented by J. Heyrovsky (Nobel Prize 1959). Differs from voltammetry in that it employs a dropping mercury electrode (DME) to continuously renew the electrode surface. Amperometry: current proportional to analyte concentration is monitored at a fixed potential | 4 30 2012 VILLANOVA UNIVERSITY Voltammetry Lecture Date April 28th 2008 Reading Material Skoog Holler and Crouch Ch. 25 Cazes Chapter 17 For those using electroanalytical chemistry in their work see A. J. Bard and L. R. Faulkner Electrochemical Methods 2nd Ed. Wiley 2001. 1 4 30 2012 Voltammetry Voltammetry techniques measure current as a function of applied potential under conditions that promote polarization of a working electrode Polarography Invented by J. Heyrovsky Nobel Prize 1959 . Differs from voltammetry in that it employs a dropping mercury electrode DME to continuously renew the electrode surface. Amperometry current proportional to analyte concentration is monitored at a fixed potential Polarization Some electrochemical cells have significant currents. - Electricity within a cell is carried by ion motion - When small currents are involved E IR holds - R depends on the nature of the solution next slide When current in a cell is large the actual potential usually differs from that calculated at equilibrium using the Nernst equation - This difference arises from polarization effects - The difference usually reduces the voltage of a galvanic cell or increases the voltage consumed by an electrolytic cell 2 4 30 2012 Ohmic Potential and the IR Drop To create current in a cell a driving voltage is needed to overcome the resistance of ions to move towards the anode and cathode This force follows Ohm s law and is governed by the resistance of the cell IR Drop Electrodes More on Polarization Electrodes in cells are polarized over certain current voltage ranges Ideal polarized electrode current does not vary with potential

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