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Lecture XXVI Chem 002 Angel C. de Dios Electrochemistry

Electrochemistry and Thermodynamics Gibbs' Free Energy and the Potential are related in the following manner:

n is the number of moles of electrons transferred in the reaction and F is Faraday's constant the quantity of charge per mole of electrons: 96,500 Coulombs / mole of electrons. The superscript o corresponds to values at standard conditions (T = 298 K, all gases are at 1 atm, concentrations of all relevant species = 1.0 M). When E > 0, D G < 0, we have a spontaneous electrochemical reaction (galvanic cell) When E < 0, D G > 0, we have a nonspontaneous electrochemical reaction (electrolytic cell)

At nonstandard conditions :

Q is the reaction quotient (This has the same terms found in the equilibrium expression except that the system
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does not have to be at equilibrium, that is, DG does not have to be equal to zero.). The third equation written above which relates the actual potential to the standard potential and the reaction quotient is called the Nernst equation. The Nernst equation is very useful as it describes the potential in cells that are not at equilibrium (In other words, the battery is still alive!)

Applications pH meter - The following can be used to measure the pH of a solution: Zn / Zn2+ // H+, H2 / Pt The anode compartment is composed of a Zn electrode immersed in an aqueous solution of known concentration of Zn2+. The standard potential for this cell (at 298 K, [Zn2+] = 1.0 M, [H+] = 1.0 M and PH2 = 1.0 atm is given by: Eo cell = Eo reduction (H+/H2) - Eo reduction (Zn2+/Zn) = 0.00 V - (-0.76 V) = 0.76 V The overall reaction (This is needed so that we can assign the proper value for n (the number of electrons)) is: Zn (s) + 2H+ (aq) --> Zn2+ (aq) + H2 (g) so n = 2, and

This cell could be used to indirectly measure the pH in the cathode compartment provided that the partial pressure of H2 over the cathode compartment and the concentration of Zn2+ in the anode compartment are known:

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Thus, we have a nice linear equation that relates the potential that we measure (using a voltmeter, for example) to the pH of the solution in the cathode compartment. For example, if we measure a potential of 0.720 V with this described setup, this means: pH = (0.79 V - E) / 0.0592 = (0.79V - 0.72V) / 0.0592 = 1.2 At pH = 13 we can also predict that the cell potential: 13 = (0.79 V - E) / 0.0592 E = 0.02 V The above cell, however, is an inconvenient way of measuring the pH since a gas, H2, is required. Handling gases and keeping the pressure at 1.0 atm is a major inconvenience. The pH meter usually employed in the laboratory consists of the following cell: Ag, AgCl / H+ // KCl / Hg2 Cl2 , Hg The salt bridge here, is, in fact, a very thin glass membrane and the potential measured across the two electrodes is dependent on the pH difference across the thin glass membrane.

Measuring equilibrium constants - At equilibrium, we expect the following relationship to hold. Thus, by knowing the standard potential for any electrochemical cell, we can calculate the equilibrium constant.

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Concentration cell - This is similar to a pH meter. The two compartments are identical in terms of the reacting species. An example is the following cell: Cr / Cr3+ 0.040 M // Cr3+ 2.0 M / Cr Since the reaction at the cathode is just the reverse of the reaction at the anode, the standard potential for this cell is zero. The actual potential of the cell will therefore vary according to the difference in the Cr3+ concentrations between the two compartments. The Nernst equation for the above cell is given by:

Thus, by knowing the concentration of Cr3+ either at the cathode or at the anode, one can determine the unknown concentration of Cr3+ in the other compartment by simply measuring the actual potential and using the above equation. Commercial voltaic cells An automobile battery is described by the following notation: Pb, PbSO4 / / PbSO4 , PbO2 with the overall reaction, + PbO2 (s) + Pb (s) + 2H (aq) + 2 HSO4- (aq) ---> 2PbSO4 (s) + 2H2O (l) The standard potential, Eo , for this cell is 2.041 V. To get 12 V, six cells are placed in series. One advantage of the above cell is that when the car is running, the battery becomes an electrolytic cell and the reverse reaction occurs (recharging the battery): 2 PbSO4 (s) + 2H2O (l) --> Pb (s) + PbO2 (s) + 2H+ (aq) + 2HSO4- (aq)
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This is possible since the product (when the battery is acting like a battery) is PbSO4, which adheres to the electrodes. E will depend on the concentration of H+ and HSO4-. Dry cell, Leclanche cell Zn / Zn2+ // MnO2 , Mn2 O3 / C(graphite) Anode: Zn (s) --> Zn2+ (aq) + 2eCathode: 2 NH4+ (aq) + 2 MnO2 (s) + 2e- --> Mn2O3 (s) + 2 NH3 (aq) + H2O (l) Eo = 1.5 V but the actual E will depend on the concentration of NH4+ and NH3 Alkaline battery (similar to the above except KOH is used instead of NH4Cl as the electrolyte) The advantage here is that Zn lasts longer under alkaline conditions. Nickel-Cadmium battery Cd, Cd(OH)2 // NiO2 , Ni(OH)2 all are solids, so E = Eo Anode: Cd (s) + 2OH-(aq) --> Cd(OH)2 (s) + 2e- Eo = 0.76 V Cathode: NiO2 (s) + 2H2O + 2e- --> Ni(OH)2 (s) + 2 OH- (aq) Eo = 0.76 V Overall: Cd (s) + NiO2 (s) + 2H2O (l) --> Cd(OH)2 (s) + Ni(OH)2 (s) Eo = 1.52V E = Eo = 1.52 V

Go back to Chem 002 syllabus page

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