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CELL EMF

Electromotive Force (EMF) The electromotive force (EMF) is the maximum potential difference between two electrodes of a galvanic or voltaic cell.

This quantity is related to the tendency for an element, a compound or an ion to acquire (i.e. gain) or release (loss) electrons.

For example, the maximum potential between Zn and Cu of a well known cell Zn(s) | Zn2+ (1 M) || Cu2+(1 M) |Cu (s) has been measured to be 1.100 V. A concentration of 1 M in an ideal solution is defined as the standard condition, and 1.100 V is thus the standard electromotive force, DEo, or standard cell potential (keupayaan elektrod piawai) for the Zn-Cu galvanic cell.

To allow prediction of the cell potential, tabulations of standard electrode potential are available. Such tabulations are referenced to the standard hydrogen electrode (SHE). The standard hydrogen potential undergoes the reaction: 2H+(aq) + 2e H2
which is shown as reduction but, in fact, the SHE can act as either the anode or the cathode, depending on the relative oxidation/reduction potential of the other electrode/electrolyte combination.

The term standard in SHE requires a supply of hydrogen gas bubbled through the electrolyte at a pressure of 1 atm and an acidic electrolyte with H+ activity equal to 1 (usually assumed to be [H+] = 1 mol/liter).

The SHE electrode can be connected to any other electrode by a salt bridge to form a cell. If the second electrode is also at standard conditions, then the measured cell potential is called the standard electrode potential for the electrode.

The standard electrode potential for the SHE is zero, by definition. The polarity of the standard electrode potential provides information about the relative reduction potential of the electrode compared to the SHE.
If the electrode has a positive potential with respect to the SHE, then that means it is a strongly reducing electrode which forces the SHE to be the anode (an example is Cu in aqueous CuSO4 with a standard electrode potential of 0.337 V). Conversely, if the measured potential is negative, the electrode is more oxidizing than the SHE (such as Zn in ZnSO4 where the standard electrode potential is 0.76 V).

Standard Reduction Potential (Keupayaan Penurunan Piawai)


equilibrium E (volts) -3.03 -2.92 -2.87 -2.71 -2.37 -1.66 -0.76 -0.44 -0.13 0 +0.34 +0.80

+1.50

Attaching a sign to the cell voltage The convention is that you show the sign of the right-hand electrode (as you have drawn it) when you quote the Ecell value. For example:

In copper case

A standard cell potential can be determined by looking up the standard electrode potentials for both electrodes (sometimes called half cell potentials). The one that is smaller will be the anode and will undergo oxidation. The cell potential is then calculated as the sum of the reduction potential for the cathode and the oxidation potential for the anode. Ecell = Ered(cathode) Ered(anode)
For example, the standard electrode potential for a copper electrode is: Cell diagram Pt(s) | H2(1 atm) | H+(1 M) || Cu2+ (1 M) | Cu(s) Ecell = Ered(cathode) Ered(anode)

At standard temperature, pressure and concentration conditions, the cell's emf (measured by a multimeter) is 0.34 V. By definition, the electrode potential for the SHE is zero. Thus, the Cu is the cathode and the SHE is the anode giving Ecell = E(Cu2+/Cu) E(H+/H2) Or, E(Cu2+/Cu) = 0.34 V
Changes in the stoichiometric coefficients of a balanced cell equation will not change Ered value because the standard electrode potential is an intensive property.

Example
Determine Eo for the reduction half reaction : Ce4+(aq) + e Ce3+(aq)

given the cell voltage for the following cell Co(s)|Co2+(1M)||Ce4+(1M),Ce3+(1M)|Pt(s) and EoCo/Co2+) = -0.277V Eo = 1.887 V

Solution Eocell = Eo(cathode) Eo(anode) = Eo(Ce4+/Ce3+) - Eo(Co/Co2+)

1.887V = EoCe4+/Ce3+ - (-0.277V)


Eo(Ce4+/Ce3+) = 188.7V-0.277V = 1.610V

Exercise
1. Eocell = 1.47V for the voltaic cell V(s)|V2+(1M)||Cu2+(1M)|Cu(s) Determine the value of EoV2+/V

2. Eocell = 3.73V for the voltaic cell Y(s)\Y3+(1M)||Cl-(1M)|Cl2(g,1 atm)|Pt Determine the value of EoY3+/Y

3. Each of the following reactions takes place in a voltaic cell. Write equations for the half reactions and the overall cell reaction. Write a cell diagram for the voltaic cell and calculate the value of Eocell. (a) Zn(s) + Ag+(aq) Ag(s) + Zn2+(aq) Fe3+(aq) + H2O(l) (b) Fe2+(aq) + O2(g) + H+(aq)