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Electrode Chem

Electrode Chem



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Published by api-3723664
Author_Dr Revannasiddhapa
Author_Dr Revannasiddhapa

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Published by: api-3723664 on Oct 15, 2008
Copyright:Attribution Non-commercial


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i. Electrochemical Energy Systems
A. Electrode potential and Cells
Definition: The electrical potential developed at the interface of the metal
and its solution due to Helmholtz electrical double layer is called single
electrode potential.
Electrical double layer & its significance: When a metal is in contact with a

solution of its own salt, the positive ions in the metal come into equilibrium with those in the solution; leaving behind an equivalent number of electrons on the metal. Thus, the metal acquires a negative charge, since it is now left with excess number of electrons and a number of positive metallic ions are formed in solution(fig a). Conversely, if the positive metallic ions from the solution enter the metallic lattices, then metal acquires a positive charge (fig b). Thus, following two reactions take place, when a metal is in contact with its salt solution:

1. Positive metallic ions passing into solution.
2. Positive ions depositing on the metal electrode

As the negative or positive charges developed on the metal
attract the positively or negatively charged free ions in the solution,
ultimately the dynamic equilibrium is established. Due to this attraction, the
positive or negative ions remain quite close to the metal. Thus, a sort layer

of positive ions (fig a) or negative ions (fig b) is formed all around the metal.
This layer is called Helmholtz electrical double layer. A difference of
potential is, consequently, set up between the metal and solution. This
potential difference will persist as long as the charge is allowed to remain on
the metal and this will prevent any further passing of the positive ions from
or to the metal. At equilibrium, the potential difference between the metal
and solution becomes a constant value. The equilibrium potential difference
so established is called the electrode potential of the metal.

Standard electrode potential [E\u00ba]: The potential of metal electrode when

dipped into metallic salt solution of unit molar concentration at 25\u00baC 1
atmospheric Pressure [101.3k pa] is called standard electrode potential. The
electrode potential is constant for the given electrode.

E\u00baZn = - 0.76 V
E\u00baCu = + 0.34 V
Free energy [\u2206G]: It is measure of available energy which can be converted
into useful work. It is defined mathematically\u2206G =\u2206H - T\u2206S
\u2206H = enthalpy
\u2206S = entropy
Standard free energy [\u2206G\u00ba]:The free energy change of the reaction when
all the reactants and products are in their standard states of 25\u00baC, 1
atmospheric Pressure,
Derivation of Nerns\u2019t Equation-Equation for single electrode potential:

The electrical potential developed at the interface of the metal and its
solution due to Helmholtz electrical double layer is called single electrode
potential. Single electrode potential can be calculated from Nerns't equation.
Nerns\u2019t equation can be derived on the thermodynamic consideration.
Consider a general redox reaction:

Mn+ + ne-\u2550\u2550\u2550M
Oxidized form
reduced form
For a reversible reaction the relationship between the free energy
change (\u2206 G) and equilibrium constant \u2018k\u2019 is given by Vant Hoff isotherm
[Reduced form]
\u2206G= \u2206Go + RT loge
[Oxidized form]
-\u2206G = -\u2206Go- RT loge K
\u2206G= \u2206G\u00ba + RT loge
Where\u2206G\u00ba = standard free energy

[\u2206G\u00ba = RT logeK]
-\u2206G\u00ba= Decrease in free energy accompanying the same process when the
reactants and

products of the reaction are in their standard states of unit activity. K= Reaction quotient of the activities of the products and reactants at any given stage

of the reaction.
In a reversible reaction, electrical energy is produced at the expense of
free energy. i.e., free energy decreases.

If E is the electrode potential of the electrode and electrode reaction
involves transfer of \u2018n\u2019 electrons, i.e. nF coulombs, Therefore the electrical
work available from the electrode is nFE Volt coulombs (or Joules). Hence
free energy decrease of the system\u2206G is given by the expression, -\u2206G =

nEF = -\u2206G
\u2206G = - nEF,
nE\u00b0F =\u2206G\u00ba\u2206\u00b0G = - n E\u00baF
Substituting in (1)
nE\u00baF = -\u2206G\u00ba
- nEF = - nE\u00ba F + RT loge
n = valency of metal ion E = single electrode potential
E\u00ba = standard electrode potential F= Faraday = 96,500 coulombs

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