Plan
1. Electrode processes. Electrode potential.
2. Different types of electrodes.
3. Cell potential.
4. Galvanic cells. Cell potential or EMF.
5. The kinetics of electrochemistry
processes.
Assistant Kozachok S.S prepared
N.B. The galvanic cells which consists of the zinc rod dipping
into a ZnSO4 solution and the copper electrode dipping
into a CuSO4 solution is Daniell cell.
Its formula is:
Salt bridge and its function. Its usually an inverted U-tube
filled with concentrated solution of inert electrolyte. The
essential requirements of electrolyte are:
a) The mobility of the anion and cation of the electrolyte
should be almost same.
b) The ions of the electrolyte are not involved in
electrochemical change.
c) The ions do not react chemically with the species of the
cell.
Generally, salts like KCl, KNO3, etc. are used. The seturated
solutions of these electrolytes are prepared in agar agar
jelly or gelatin. The jelly keeps the electrolyte in semisolid phase and thus prevents mixing.
The important functions of the salt bridge are:
a) Salt bridge completes the electrical circuit.
b) Salt bridge maintains electrical neutrality of two half cell
solution.
The accumulation of charges in the two half cells
(accumulation of extra positive charge in the solution
around the anode according to the realizing of Zn2+ in
excess and accumulation of extra negative charge in the
solution around the catode due to excess of SO42- ) is
prevented by using salt bridge, which provides a passage
for the flow of the charge in the internal circuit.
Cu
1- metal
2 - solution
+
-
+
+
+
+
+
+
(-)
- - - --CuSO4
or
E E0
0.059
log [ Mn (aq) ]
n
Nerst equation
Ox / Re d
0
Ox / Re d
RT
ln a
nF
RT
2.3
0.059, that
F
Ox / Re d
0
Ox / Re d
0.059
lg a
n
aA bB cC dD
The Nerst equation may be written as:
Where
is the standard free energy for the reaction.
Significance. The above equation helps us to predict the
feasibility of the cell reaction. For a cell reaction to be
spontaneous,
must be negative. This means that E must
be positive for a spontaneous cell reaction.
0.059
E E
log [ Mn z (aq) ]
n
0
0.059
E E
log a Mn z
n
0
0.059
[Mn(s) ]
E E
log
n
[Mn z (aq) ]
0
a Mn(s)
0.059
E E
log
n
a Mn z
0
aH
Electrochemical potential of this electrode depends on the hydrogen
ions concentration. However the standard potential of this electrode
equals o and the valency of hydrogen equals 1 (n=1) Nernst
equation is:
Ecell = 0,059 log [H+] = - 0,059 pH
Measuring of pH to use potentiometric method of the determination
of hydrogen ions concentration.
This method is based on the measuring of e.m.f of the cell which
consists of the reduction electrode (calomel) and the electrode
which has dependence on the hydrogen ions concentration (gasion electrode, glass electrode, quinonhydrone electrode )
0.059
E E
log a A z
n
An example is the so-called silver - silver chloride electrode,
0
KCl, AgCl | Ag
Fe3+ , Fe2+ | Pt
Fe3+ + e = Fe2+
FeCl3 + FeCl2
E Fe3 / Fe 2 E
0
Fe 3 / Fe 2
0.059 lg
aFe3
aFe 2
Quinonhydrone electrode
(the third reference electrode)
642, 64()2, H+ | Pt
642 + 2+ + 2 = 64()2
Ecell
aC6 H 4 (OH ) 2
0.059
E
lg
2
2
C6 H 4O2
0
Ecell E 0.059 lg aH
0
Quinonhydrone
H+
ClEcell
u Kt u An 0.059 a1
lg
u Kt u An n
a2
where a1 > a2
HCl 0.1
-
+
+
+
+
+
+
+
+
+
(+)
>
AgNO3, C1