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Thermodynamics and Electrochemistry

1) Background info:
Cell Potential Electrical Work and Free Energy
emf = potential difference (V) =

Work ( J ) Ch arg e( C )

cell potential=
system.

W q

the negative sign means that work is done by the

Maximum work:

Wmax = -qEmax

But to obtain work, electrons must flow, which causes friction. Inevitably, in any real spontaneous process, some energy is wasted.

The relationship between Gibbs free energy and Ecell


q = nF F= Faradays constant, 96485 Cmol-1 n = # mol of e-1

The change in free energy, G, is equal to the maximum amount of work obtained by the process. Wmax = G

G = -q Emax = -nFEmax
G = -nFE @ standard conditions: Go = -nFEo

The maximum cell potential is directly related to the free energy difference between the reactants and products in the cell. This provides the experimental means to obtain the value for the change in free energy, G, for a reaction. The relationship between Gibbs fee energy and the E the expression above.
o cell

is summarized by

This relationship also serves as a bridge between thermodynamics and electrochemistry.

2. Voltage and Spontaneity:

G = n F E o cell
Where F = Faraday constant = 96500 J mol/V 96500 C/mole n = number of moles of electrons transferred Eo cell = standard reaction potential, V Go = standard free energy, kJ/mol

K >1 =1

Eocell Positive 0

Go Negative 0

Conclusion Spontaneous cell reaction At equilibrium Non-spontaneous cell reaction. Reaction is spontaneous in the reverse direction

<1

Negative

Positive

Example: Calculate the Gibbs free energy for the following reaction: Cu2+ Fe ------- > Cu + Fe2+ Cu 2+ + 2e- ------ Cu Eo = +0.34V 2+ Fe ---- Fe + 2e Eo = 0.44V ----------------------------------------------------------Cu2+ Fe ------- > Cu + Fe2+ Eo cell = 0.78 V

G = n F E cell
Go = - (2mol e-)(9648 Cmol-1)(0.78 J/C) Go = -1.5 x 10 5J - spontaneous since Go is negative, and the Eo cell is positive.

3. Dependance of Cell Potential on Concentration.


Given the following cell: Cu/Cu2+//Ce4+/Ce3+ Eocell=+1.36V

Cu(s) + 2 Ce4+(aq) ----- > Cu2+(aq) + 2 Ce3+(aq)

if the concentration of [Ce4+], Le Chateliers principle says that the forward reaction is favoured. So the cell potential would increase.

Nerst Equation:

equation used to calculate cell potentials dependance on concentration for NON STANDARD CONDITIONS.
Dependance of the cell potential on concentration results directly from the dependance of the free energy on concentration.
G = Go + RT lnQ G = -nFE, and Go = -nFEo -nFE = - nFEo + RT lnQ

Nerst Equation:

E = Eo -

RT lnQ nF

-R is the gas constant (8.314 J/K mol), -T the Kelvin temperature, -n the number of electrons transferred between the species, -F the Faraday constant, -Eocell is the voltage generated IF the conditions WERE standard, -ln represents the natural logarithm -and Q is the reaction quotient.

Note:

At standard state, all concentrations are equal to 1, so E = E o. At 25o C the equation above becomes: E = Eo -

0.0592 logQ n

As the concentration of the products increase, the voltage decreases. As the concentration of the reactants increases, the voltage increases.

Example Calculation If the reaction below is carried out using solutions that are 5M Zn 2+ and 0.3M Cu2+ at 298K, what is the actual cell voltage? Zn(s) + Cu2+(aq) Cu(s) + Zn2+(aq) Firstly, work out the Eocell assuming standard conditions. Zn(s) | Zn2+(aq) || Cu2+ (aq) | Cu(s) Zn2+(aq) + 2eCu2+(aq) + 2e Zn(s) Cu(s) Eo = -0.76V Eo = +0.34V

Eocell = ER EL = +0.34 - -0.76 = 1.1V Then calculate Q. Since zinc and copper metals are solids, they are omitted from Q. Q = [Zn2+]/[Cu2+] = 5/0.3 = 16.7 Two electrons are transferred between the zinc and copper, so n=2. Plug everything in E = 1.1V - (0.0257/2) * ln (16.7) = 1.06V Example Calculation 2 Fe3+ + Sn2+ ----- > 2 Fe2+ + Sn4+

In a galvanic cell, all the products have a concentration of 0.0355M and the reactants are 0.100M. What is the voltage at 25oC. Eocell = - Eosn + EoFe = -0.154V + 0.771V = 0.617V E=0.617V (8.314)(298)/(2) (96485) ln (0.0355^2) (0.0355)/(0.100^2)(0.100) E=0.657V

4. Voltage and equilibrium:


At equilibrium, E=0 and Q=K
E = Eo -

RT lnQ nF
Eo =

0 = Eo -

RT lnK nF

Therefore,

RT lnK nF

This equation allows us to calculate the equilibrium constant for a redox reaction.

Electrochemistry and Thermodynamics Summary

Voltage and Spontaneity:

G = n F E o cell

Nerst Equation:

E = Eo -

RT lnQ nF

Voltage and Equilibrium:

Eo =

RT lnK nF
Conclusion Spontaneous cell reaction At equilibrium Non-spontaneous cell reaction. Reaction is spontaneous in the reverse direction

K >1 =1

Eocell Positive 0

Go Negative 0

<1

Negative

Positive