METAL-ELECTROLYTE INTERFACE

Metals are solid

contain many defects in their crystal structure
inhomogeneities in their chemical composition
May be polycrystalline, monocrystalline or amorphous

Electrolytes have many types of intermolecular forces like

Ion-ion interaction
Ion-solvent interaction
Solvent-solvent interaction

Metal-electrolyte interface
An interface is created when a metal (solid) electrode is

introduced into an electrolyte solution

This interface becomes electrified due to an electron
exchange between the electrode and the ions in solution
potential difference over the metal-electrolyte interface is
generated.
an electrical field leads to the redistribution of mobile ions
and water dipole molecules in the region near the electrode.

 This potential difference across the metal-electrolyte

interface is called electrode potential.

The origin of electrode potential

Chemical potential of ith component in a mixture is given

by

i io RT ln ai

where oi is the chemical potential of ion i in a hypothetical solution

with molality mo in which ion-ion interaction are insignificant
Chemical potential of i is defined as free energy change for 1

mole of i in an infinite amount of the mixture, i.e.

G
i
ni P ,T ,ni n j

 Total free energy in the mixture is given by

G n i i
i

If reaction takes place in a large excess of mixture with

insignificant changes in mole fractions of reactants and

products, then free energy change of reaction is
r G i i
i

i is the stoichiometric number of reactants.

At equilibrium rG equal zero

 Chemical potential of component i present in two

mixtures/solutions in contact with chemical equilibrium

across the interface is given by:

i ( I ) i ( II )
If above equality is not fulfilled, then spontaneous reaction

takes place across the interface.

Free energy of i is lowered when it is transferred from one
phase to another.

When metal (M)is in contact with its ions (Mz+) in solution then the

following equilibrium is expected:

M (0S ) M (zaq ) zem

where (m) refer to the metal
For example
0

Cu( s ) Cu(2aq ) 2e( m)

chemical reaction in either sides is needed to make chemical potential

for copper equal in the two phases

Such reaction consumes or generates electrical charges
Potential difference is formed between the two phases

 The favorable direction of the reaction depends on chemical potential

If

Cu Cu e

then Cu will dissolve

(a)
Solution near Cu metal becomes positively charged
Double layer near metal surface is created
potential difference across metal/solution interface will prevent
further dissolution
the same is true when Cu( s ) Cu(2aq ) e( m )
(b)
(s)

2
( aq)

(m)

Both cases are represented by the figure

(a)

(b)

 With potential difference at metal/solution interface the

free energy will be

i ( I ) zi Fi ( I ) i ( II ) zi Fi ( II )
where i(I)and I(II) are the electrical potential in the interior
of phases (I) and (II)
ziFI the electrical work needed to bring one mole of ions
with z charge from infinity to the region of where the
potential I exists
I is called Galvani potential

i is the electrochemical potential and defined as:

~

i zi Fi i RT ln ai zi Fi
o

For an electrochemical equilibrium then

i 0

0
2
Cu

Cu
For the reaction
(s)
( aq) 2e( m ) we write:
o
o
Cu
RT ln aCu 0FCu Cu
RT ln aCu 2FCu eo RT ln ae 2Fe
2

-ve sign because electrons have negative charge

 Potential on LHS for metal i.e. M

Potential on RHS for solution i.e. sol

Activities of metal atoms and its electrons are constant
The difference between two potentials across interface is

M sol
and called Galvani potential

 By rearrangement

o
o
Cu
2eo Cu
2

2F

RT aCu2

ln
2F
aCu

RT aCu2

ln
2F
aCu
o

This equation is for one interface

o is Galvani standard potential

how much changes if activity increased 10 times?

question
If two different metal/solution interfaces are connected, how the
potential difference is expressed?