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THE NERNST EQUATION

The Nernst equation is used to calculate the voltage of an electrochemical cell or to find the
concentration of one of the components of the cell. Here is a look at the Nernst equation and
an example of how to apply it to solve a problem.

The Nernst equation relates the equilibrium cell potential (also called the Nernst potential) to
its concentration gradient across a membrane. An electric potential will form is there is a
concentration gradient for the ion across the membrane and if selective ions channels exist so
that the ion can cross the membrane.

The relation is affected by temperature and whether the membrane is more permeable to one
ion over others.

The equation may be written:

Ecell = E0cell - (RT/nF)lnQ

Ecell = cell potential under nonstandard conditions (V)


E0cell = cell potential under standard conditions
R = gas constant, which is 8.31 (volt-coulomb)/(mol-K)
T = temperature (K)
n = number of moles of electrons exchanged in the electrochemical reaction (mol)
F = Faraday's constant, 96500 coulombs/mol
Q = reaction quotient, which is the equilibrium expression with initial concentrations rather
than equilibrium concentrations

Sometimes it is helpful to express the Nernst equation differently:

Ecell = E0cell - (2.303*RT/nF)logQ

at 298K, Ecell = E0cell - (0.0591 V/n)log Q

Nernst Equation Example

A zinc electrode is submerged in an acidic 0.80 M Zn2+ solution which is connected by a salt
bridge to a 1.30 M Ag+ solution containing a silver electrode.

Determine the initial voltage of the cell at 298K.

Unless you've done some serious memorizing, you'll need to consult the standard reduction
potential table, which will give you the following information:

E0red: Zn2+aq + 2e- → Zns = -0.76 V

E0red: Ag+aq + e- → Ags = +0.80 V

Ecell = E0cell - (0.0591 V/n)log Q

Q = [Zn2+]/[Ag+]2
The reaction proceeds spontaneously so E0 is positive. The only way for that to occur is if Zn
is oxidized (+0.76 V) and silver is reduced (+0.80 V). Once you realize that, you can write
the balanced chemical equation for the cell reaction and can calculate E0:

Zns → Zn2+aq + 2e- and E0ox = +0.76 V

2Ag+aq + 2e- → 2Ags and E0red = +0.80 V

which are added together to yield:

Zns + 2Ag+aq → Zn2+a + 2Ags with E0 = 1.56 V

Now, applying the Nernst equation:

Q = (0.80)/(1.30)2

Q = (0.80)/(1.69) Q = 0.47

E = 1.56 V - (0.0591 / 2)log(0.47) E = 1.57 V

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Nernst Equation

 This equation was named after a German physicist Walther Nernst.

 The Nernst Equation empowers the assurance of cell potential under non-standard
conditions and relates the measured cell potential to the reaction quotient and permits
the exact measurement of equilibrium constants.
 Let us consider an electrochemical reaction of the following type:

aA +bB --> cC + dD

 Nernst equation for this can be written as follows:

 In case of daniel cell Nerst equation is as follows:


 The above equation implies that the value increases with the increase in the
concentration of Cu2+ ion and decrease in the concentration Zn2+
 Putting the values of R, F at T= 298 K. the equation becomes

Problem:

Calculate the emf of the cell in which the following reaction takes place: Ni(s) + 2Ag+ (0.002
M) → Ni2+ (0.160 M) + 2Ag(s). Given that Eøcell = 1.05 V.

Solution:

By using Nernst equation

= 1.05 - 0.02955 log 4 × 104

= 1.05 - 0.02955 (log 10000 + log 4)

= 1.05 - 0.02955 (4 + 0.6021)

= 0.914 V

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