Adv. Analytical Chmeistry Lecture 19_2012.ppt

* * * * * * * Lecture 19 Common Electrochemical Methods Nernst Equation: reduced oxidized Anode: Zn2+ + 2 e- ? Zn(s) E0 = -0.763 Cathode: Cu2+ + 2 e- ? Cu(s) E0 = +0.337 =1 Ecu= E0Cu Ecell = Ecathode – Eanode anode cathode Often Deal in Half-cell Reactions: Potentiometry Measurement of a POTENTIAL between an indicator/test electrode and a reference electrode NO CURRENT shall Pass! Comparison to an indicator (known) enables determination of the analyte solution Reference Electrodes A Good reference will… obey the Nernst equation with respect to some species of electrolyte have a stable potential with time have a potential that returns to its initial value after small amounts of current have passed have a low temperature hysteresis Common reference electrodes: Saturated Calomel Electrode Ag/AgCl Ag or Pt metal wire (quasi-reference electrode)* * A QRE must be calibrated against a known redox couple Fc/Fc+ Potential is a relative What is zero potential? Fermi Energy – electrochemical potential of electrons on the electrode Absolute scales - energy required to bring a unit positive charge into the conducting phase of the electrode from a point in vacuo just outside the system REFERENCE ELECTRODES provide a convenient reference point Metallic Indicator Electrodes Ideal Indicator Electrodes Rapid response Selective response Electrodes of the First kind: Direct Electrodes of the Second kind: Indirect Electrodes of the Third kind: Doubly indirect Inert Redox Electrodes Electrodes of the First kind: Direct Ag+ + e- ?? Ag (s) For a real Cell, include the Reference Electrode Measure Ecell ? obtain the [Ag+] Electrodes of the Second kind: Indirect AgCl (s) + e- ?? Ag (s) + Cl- We already did this for Ag/AgCl reference electrodes Metallic phase in equilibrium with its sparingly soluble metal salt. Response depends on Anion concentration Electrodes of the Third kind: Doubly Indirect Indirect response to a different cation than one being monitored directly