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NERNEST EQUATION

FOR ELECTRODE
POTENTIAL (E):
Et = E0 + RT/nF ln [Mn ] where;
+

Et = electrode potential at temperature t.


E0= standard electrode potential (constant
depend on the system)
R= gas constant , 8.314 JK-1mol-1
T = the temperature in Kelvins

F = faraday (96500 Coulombs)


ln = (natural logarithm = 2.303log)
n = number of moles of electrons that
appear in the half reaction
[Mn+] = molar concentration of metal ions in
solution .
This formula can be simplified by
introducing known values as follows:
E = E + 0.0591 / n log [ Mn+]
E = E0
if [Mn+] equals one , (i.e.
molar solution)

Standard electrode potential


(E0):
( Is electrode potential when all reactants
and products of half-reaction have unit
activity )
E0 is defined as the electromotive force
(e.m.f) produced when a half cell
(consisting of the elements immersed in a
molar solution of its ions) is coupled with a
standard hydrogen electrode
(E0 = zero)
Table 1 lists the E0 values of some
common metals

Notes:
The arrangement of metals in order of
their standard electrode potential
gives the electrochemical series
(Table 1).
A metal with a more ve potential will
displace any other below it in the
series from its salt solution , thus iron
will displace copper or mercury from
their salt solutions.

Table 1 : Standard electrode


potential at 250 C :

System E0(volts)
Li/Li+
K/K+
-2.92
Mg/Mg2+ -2.37
Al/Al3+ -1.33
Zn/Zn2+ -0.44
Fe/Fe2+ -0.44

System E0(volts)
Cd/Cd2+
-0.40
Sn/Sn2+ -0.13
H2(pt)/H+
0.00
Cu/Cu2+
+0.34
Hg/Hg2+
+0.79
Ag/Ag+
+0.80

Silver tree

Standard Oxidation potential


(E0):
E25C = E0+ 0.0591/n log [M n+]
It is the e.m.f. produced when a half
cell consisting of an inert electrode
(as platinum) dipped in a solution of
equal concentration of both the
oxidized and reduced forms (such as
Fe3+/Fe2+) is connected with a NHF ,
Figure 2.

Figure 2 : Apparatus for determination


of the standard oxidation potential of
the system Fe3+/Fe2+
1,2: glass vessel,3: electrolyte bridge ,
4: tube for hydrogen gas ,
5: potentiometer
Table 2: lists the E0 of some common
redox couples.

Table 2: standard oxidation


potentials at 25
System
E0(volts)
System
E0(volts)
MnO4-/Mn2+
+1.52
AsO43-/AsO33+0.57
Ce4+/Ce3+
+1.45
I2/2I+0.54
ClO3-/Cl+1.45
Fe(CN)63-/Fe(CN)64- +0.36
Cr2O7 2-/2Cr3+ +1.33
Cu2+/Cu+
+0.16
IO3-/I2
+1.19
Cl2/Cl+1.36V
S4O62-/2S2O3 2+0.09
Fe3+/Fe2+

+0.77

H2/2H+
Fe2+/Fe

0.00
-0.44

Notes:
The higher E0 , the stronger the oxidizing power
of its oxidant and the weaker the reducing
power of its reduced form.
The most powerful oxidizing agent are those at
the top (highly +ve) and the most powerful
reducing agent are at the bottom (highly
ve)
If any two redox systems are combined , the
stronger oxidizing agent gains electrons from
the stronger reducing agent with the
formation of weaker reducing and oxidizing
agents.

Cl2/Cl-=(E0+1.36V), Fe3+/Fe2+(E0=+0.77V)

Cl2

strong
oxidizing agent

reducing

2 Fe2+

Fe3+

+ 2 Cl-

Strong
reducing agent

weak oxid weak reducing

agent

agent

Nernest equation for oxidation


potential:
E25c = E0 + 0.0591/n log [Ox]/
[Red]
[Ox] & [red] = molar concentration of
the oxidized and reduced forms,when
[Ox] = [Red] , then E=E0.

Phosphoric acid lowers the potential of


Fe3+/Fe2+ system by complex with
Fe3+ as [Fe(PO4)2]3- .
E= E0 +.0591/1log[Fe3+]/
[Fe2+]
Sulphuric acid is used for acidification.

Effect of [H+]
The oxidation potential of an oxidizing agent containing
oxygen increases by increasing acidity and vice versa
Potassium permenganate:
MnO4- + 8H+ +5e
Mn2+ + 4H2O
EMnO4-/Mn2+=E0 + 0.0591 log [MnO4-[H+]8/[Mn2+]
5
Potassium dichromate:
Cr2O72- + 14H+ + 6e
2Cr3+ + 7H2O
E = E0 + 0.0591/6 log [Cr 2O72-][H+]14 / [Cr3+]2
(Cr2O7/Cr3+)

Arsenate/ Arsenite system:


HCO3 -

AsO43- + 2I- + 2H +

AsO3

3-

+I2 + H2O

H+

In presence of much acid , arsenate will


oxidize iodide to iodine. If E is reduced by
decreasing [H+] , arsenite is oxidized with
iodine (in presence of sodium bicarbonate)

Effect of complexing agents:


E (I2/21-) system increases by the addition of
HgCl2 since it complexes with iodide ions .
Hg2+ + 4I[HgI4]2- low dissociation complex
E (Fe /Fe ) is reduced by the addition of F- or PO43due to the formation of the stable complexes
[FeF6] 3- and [Fe(PO4)2]3respectively.
Thus ferric ions in presence of F- or PO43- cannot
oxidize iodide although
E0(Fe3+/Fe2+) = 0.77 while
E0(I2/2I-) = 0.54
3+

2+

(4) Effect of precipitating


agents:
Addition of Zn2+ salts which precipitates
ferrocyanide increases the oxidation
potential of ferri/ferrocyanide system to
oxidize iodide to iodine, although the
oxidation potential of I2/2I- system is
higher.
[Fe (CN)6]4- +Zn2+
Zn2 [Fe(CN)6]
Eferri/ferro =E0 + 0.0591/1 log[Fe(CN)6]3-/Fe(CN)6]4-