Galvanic and Electrolytic Cells

Electrochemistry and electrochemical cells were introduced in our unit on diabetes monitoring. You can review that page here. Electrochemical cells are in a circuit that allows the transfer of electrons through it. The cell includes:

an anode, the electrode where oxidation takes place a cathode, the electrode where reduction takes place an electrolyte, to allow conduction of ions within the solution in each half cell a salt bridge or semipermeable membrane, to allow conduction of ions between half cells the external circuit that connects the two electrodes includes wires, a load, and meters

Galvanic Cells
An electrochemical cell that releases energy is called a galvanic cell. The electrochemical reaction has a negative value of the Gibbs free energy and a positive cell potential difference. Below is a galvanic cell in which the reaction between A+ and B is exothermic, with a standard conditions and a value of E0 of 0.10 V. G of -10 kJ/mol under

Hydrogen Electrode and Half Reactions

We have tables that show reduction half reactions. How are these obtained? An electrochemical reaction in an electrochemical cell requires both a reduction half reaction and an oxidation half

reaction. A voltmeter in the circuit shows the total cell voltage (Etot = Ered + Eox). We can determine a half cell potentials by measuring the voltage of a cell that includes that half cell along with a standard half cell of known potential. The accepted standard electrode is the hydrogen electrode. This consists of a half cell with an unreactive metal electrode, H2(g) at 1 atmosphere pressure, and a 1 M aqueous solution of acid. In the reduction mode:

2H+ + 2eH2 Ered = 0.00 V In the oxidation mode: H2 2H+ + 2eEred = 0.00 V You can see here that the potential of a half cell in which Cu+2 is reduced to Cu is 0.34 V. reduction oxidation net Cu+2 + 2eH2 Ered = x Eox = 0.00 V Etot = 0.34 V

Cu

2H+ + 2eCu + 2H+

Cu+2 + H2

Electrolytic Cells
An electrolytic cell has an endothermic chemical reaction. The reaction is not spontaneous so a power source is required. Energy is stored in an electrochemical cell. That energy can be released when the cell is allowed to run in a galvanic mode.

Above right is the galvanic cell that we saw previously. The molecules A and B+ are produced and energy is released. The electrode on the left side of the cell is the cathode because A+ is reduced to A at that electrode. Above left is the same cell in an electrolytic mode. An energy source causes the reaction to go in the direction opposite to the spontaneous direction. Now, A+ and B are produced. The electrode on the right is the cathode because B+ is reduced to B there.

Professor Patricia Shapley, University of Illinois, 2012