Professional Documents
Culture Documents
Introduction
The connection between chemistry and electricity is a very old one, going back
to Alessandro Volta's discovery, in 1793, that electricity could be produced by
placing two dissimilar metals on opposite sides of a moistened paper.
Voltas words on his discovery:
I have the pleasure of communicating to you, Sir, and through you to the Royal
Society, some striking results at which I have arrived in pursuing my
experiments on the electricity excited by the simple mutual contact of metals of
different sorts...
Electrode, galvanic cell, electrolysis cell
Electrode
An electronic conductor (charge carriers are electrons), the electrode metal and
an ionic conductor, electrolyte solution form an interface at which the electrode
process takes place. This two or more phase system is called electrode. An
electrohemical cell contains two electrodes anode and cathode. In general, a
liquid liquid junction separates the two electrodes.
The anode is the electrode where oxidation occurs.
The cathode is the electrode where reduction occurs.
In an actual cell, the identity of the electrodes (anode or cathode) depends on the
direction in which the net cell reaction is occurring.
Liquid liquid junction: (llj)
Serves as a galvanic contact between the electrodes. Llj can be a porous
membrane or a salt bridge.
Salt bridge is an intermediate compartment filled e.g. saturated solution of KCl
and fitted with porous barrier at each end. The two solutions are joined by a salt
bridge, which consists of an inverted U-shaped glass tube filled with a saturated
solution of a salt (for technical reasons, usually KCl) that is thickened with a gel
such as agar (the salt solution should remain in the U-tube).
L02Elchem
L02Elchem
rG 0
L02Elchem
always be positive. Cell diagram is constructed to show the cell reaction running
in spontaneous direction, i.e. the positive ion drifts from left to right.
If electrons flow from the left electrode (Zn/Zn2+) to the right electrode
(Cu/Cu2+) in metal leads when the cell operates in its spontaneous direction, the
potential of electrode on the right will be higher than that of the left.
Zn(s) ZnSO4(aq) CuSO4(aq) Cu(s)
In the cell diagram components are marked with their phases, vertical bars
simbolize the phase boundaries.
Dashed vertical line for liquid junction means that diffusion potential is not
eliminated.
Zn(s) ZnSO4(aq) CuSO4(aq) Cu(s)
Double vertical line for liquid junction: , means that diffusion potential has
been eliminated.
Cell reaction potential
zFEcell r G
1.
Ecell, the cell reaction potential is the potential difference between electrodes, and
zFEcell is the maximum work can be done by the cell.
The thermodynamic sign convention for spontaneous (natural) processes:
r G 0 thus
Ecell 0.
That is why we place positive electrode on the right. Subtracting from positive
potential the negative one Ecell becomes positive.
The conditions of Ecell measurement,
1. Current flowing between electrodes approximates zero I 0 in the
measuring electric circuit, so system does not do any work on
surroundings.
2. diffusion potential, d has been eliminated
3. cell reaction is reversible.
At the conditions given Ecell is a measure of maximum work the cell could do.
From the measured Ecell, knowing the cell reaction itself, the reaction Gibbs free
energy can be calculated. If diffusion current should be taken into account
E MF Ecell d
L02Elchem
2.
4
electromotive force EMF is measured instead of Ecell. In this case a nonthermodynamic quantity is added to Ecell.
In many case d can be minimized down to several milli-volts by the application
of a salt bridge, and Ecell and EMF can be taken equal.
When the cell reaction is in chemical equilibrium (at dT = 0, dp = 0)
r G 0 and Ecell 0
3.
In general, the electrode placed on the right in the cell diagram should be the
cathode, than subtraction
Ecell Right Left
3a.
will give positive result. The real spontaneous direction depends on the actual
concentration/activity values in the cell. The cell reaction can change its
direction and consequently Ecell its sign. The proper sign can be determined by
polarity measurement, by using high input resistance voltmeter.
To measure EMF of a galvanic cell we use a high input resistance voltmeter. It
does not load the cell, and only current in nano-Amper range flows.
The Nernst equation
L02Elchem
4.
rG0
r G 0 RT
ln(Q )
zF
zF
5.
rG0
0
, the standard cell reaction potential
Ecell
zF
0
Ecell Ecell,1
RT
ln(Q )
zF
6.
For the cell reaction Zn + Cu2+ Cu + Zn2+ in Daniell cell reaction quotient can
be given,
Q
aCu a Zn
,
a Zn aCu
2
for pure and homogeneous phases aCu = constant and aZn = constant, thus they
are involved in standard term
0
0
Ecell
Ecell,1
0
Ecell Ecell
RT
a
ln( Cu )
zF
aZn
a 2
RT
ln( Zn )
zF
aCu 2
7.
0
When activity values in a galvanic cell are set as Q = 1, than Ecell Ecell
, the
standard cell reaction potential.
Table 1.
Electrode potentials
Ecell can be given as the difference of electrode potentials (see Eq. 3.):
Ecell Cu 2 Zn 2 0Cu 2
RT
RT
ln aCu 2 ( 0Zn 2
ln aZn 2 )
zF
zF
8.
Electrode potential is the difference between potential in the metal and the bulk
of solution. Individual electrode potentials can not be measured, owing to
formation of double layer at the interface.
L02Elchem
0
0 Ecell
ln K a
Q = Ka
and
rG 0 ,
therefore
RT
ln K a
zF
0
zFEcell
RT
9.
0
The measured data for Ecell
at a given temperature serves for the calculation of
equilibrium constant.
Cell types
Electrolyte concentration cell
Electrode concentration cell (liquid state metal containing dissolved metal
component, e. g. mercury containing copper)
Electrode types
L02Elchem
Electrode
type
Example
Description
2+
Metal metal-ion
electrode
Ion ion
(redox)
electrode
Metal insoluble
salt electrode
Cu(s)Cu (aq)
Gas electrode
Pt(s)H2(g) H+
(aq)
Pt(s)Fe3+,Fe2+(aq)
Hg(s) Hg2Cl2(s)
KCl(aq)
reduction direction)
Metal bathed in electrolyte Cu2+(aq)+2eCu(s)
containing its own ions.
Noble metal in contact
Fe3+(aq)+eFe2+(aq)
with solution of a redox
couple
Metal in contact with its
Hg2Cl2(s)+2e2Hg+2Clinsoluble salt (i.s.) and a
solution containing a
soluble anion of the i.s.
Noble metal in contact
H+(aq)+e1/2H2(g)
with a saturated solution
for a gas and contains the
reduced or oxidized form
of the gas
Me Me+(a1) + e
Cell reaction:
Me+(a2) Me+(a1)
Nernst equation:
Ecell
a
RT
ln( 1 )
F
a2
1
If a1 = a2 than F ln( a ) 0 , there is no driving force of the process, and
2
system is in chemical equilibrium: Ecell = 0.
0
0.
From Nernst equation Ecell
a1
1
a2
L02Elchem
ln
a1
0
a2
ln
Ag
ln
F
a Ag
F
a Ag
10.
RT
ln a Ag
F
10
11.
RT
ln a
Cl
F
Metal insoluble salt electrodes are used as reference electrodes because they can
not be polarized easily. A reference electrode should maintain a constant
potential in the presence of small currents. A small current flowing through the
reference electrode causes no change in activity of electroactive components.
The solubility equilibrium of insoluble salt of metal stabilizes activities. E.g. for
Ag/AgCl/KCl electrode the value of solubility product constant, Ksp=[Ag+]
[Cl-]=1.8 x 10-10. The chloride activity is maintained either by dissolution or
deposition of AgCl when polarization would consume or produce excess amount
of Ag+ ions.
Ion ion (redox) electrode
A single liquid phase contains both the oxidized and reduced forms of electrode
reaction. A noble metal electrode, e.g. Pt senses the potential difference between
the bulk of solution and the metal. The electron exchange occurs in the liquid
phase.
The electrochemical process which determines the electrode potential of
redox electrode Pt(s)cFe2+(aq), cFe3+(aq)
Fe3+ + e = Fe2+
0
Fe 2 / Fe3 Fe
2
/ Fe3
RT aFe 2
ln
F aa 3
12.
Fe
L02Elchem
11
If
a ( Fe 3 )
1
a ( Fe 2 )
RT
a ( Fe 3 )
ln(
)0
zF
a ( Fe 2 )
If
a ( Fe3 )
1
a( Fe2 )
V at T = 293 K.
RT
a( Fe3 )
ln(
)0
zF
a( Fe2 )
L02Elchem
12
and the electrode reaction between the adsorbed hydrogen atoms and hydrogen
ions in solution occurs.
Half cell reaction or electrode reaction
2H+ + 2e- = H2
The electrode potential:
M s
H H0
pH
RT
ln 2 2 0
2F a p
13.
The Nernst equation represents that the electrode potential of a hydrogen gas
electrode depends on the activity of H+ and the pressure of H2 gas at constant
temperature. p0 is the standard pressure which is 1 bar.
The electrochemical potential scale
The reference point of potential scale: the standard hydrogen electrode. Its
electrode potential is regarded as the zero Voltage of the scale.
0
If the pressure of H2 over the liquid is the standard pressure pH 2 p 1 bar , we
have
H 0H
RT
1
ln
F
aH
14.
1
EMF EMF
15.
Cl
aHg = 1, aHg2Cl2 = 1
solid phases
p0 = pH2 = 1 bar
By taking into account the facts above, Equation 15 simplifies
0
EMF EMF
RT
ln a a
H
Cl
F
0
E MF E MF
ln10
RT
pH ln a Cl
F
ln10 = 2.303
0
0
0
H0 cal
cal
The standard cell reaction potential: EMF
RT
pH
F
16.
For reduction of problems with liquid junction and unknown activities we use
reference standard pH electrodes.
The same platinized platinum is immersed into both solutions, and joined to the
same secondary reference electrode.
Cell with unknown pH
L02Elchem
14
Eu cal 2.303
RT
pH u
F
RT
pH r
F
RT
RT
pH u 2.303
pH r
F
F
Eu Er
RT
2.303
F
15
Ag+ + e = Ag
2.
H+ + e = 1/2H2
Ag+ + 1/2H2 = Ag + H+
1. - 2.:
H 0
Ecell Ag H ,
0
Ecell Ag
When aAg = 1,
RT
1
ln
F
a Ag
0
Ecell Ag
RT c Ag
ln 0
F
c
0
Ecell Ag
RT
RT c Ag
ln
ln 0
F
F
c
RT
ln f0
F
Ecell f0
where
0f
RT cAg
ln 0
F
c
L02Elchem
r S
p
16
r G
rG r H T
r G zFE MF
E MF
zFE MF r H zFT
E MF
1
E MF
r H T
zF
T
E MF
r H zF E MF T
T
r S
rG r H
T
T
L02Elchem
17