2/17/2013

1
Electrochemistry
By
Hamdy H. Hassan
Professor of Physical Chemistry
Faculty of Science
Ain Shams University
c a b
Movement of
charge carriers
in a conductor
Chemical reaction
involves electron
transfer

Oxidation- Reduction
Reactions
Electro-chemistry chemistry
Electricity
Electro
=
c a b
charge = quantity of electricity = Q
Q
e
= 1.6022 x 10
19
C
+ or -
(coulomb, C)
fixed charges
mobile charges
electrons
ions
Insulator (Solids or liquids)
Electronic conductor (Solids)
Ionic conductor (Liquids)
Matter
electronic conductors
metals
graphite
semiconductors
PbO
2

polypyrrole
ionic conductors
Solutions
(seawater) [Na
+
(aq), SO
4
2
(aq), etc.]
Molten Salts [Na
+
, Cl

]
Mixed ( Gases)
plasmas
e

(NH
3
) + Na
+
(NH
3
)
H
2
in Pd [H
+
+ e

]
de
Charge
electrons
A
I
ammeter
electronic conductor
Electronic Conductor
The metals consist of highly ordered array of its ions with valance
electrons delocalized throughout the lattice
(i.e., a static positive cores surrounded by a sea of electrons).
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NaCl
Strong Electrolytes Weak electrolytes
Non-electrolyte
Electrolytes
Conduct electric current via
the motion of (+) and (-) ions
Does not conduct electric current
All ionic cpds
Some covalent cpds
Cpds which are completely
ionized when dissolves in
water
Cpds which are partially
ionized when dissolves in
water
Cpds which are non-ionized
when dissolves in water
Some covalent cpds
Na
+
+ Cl
-
CH
3
COOH CH
3
COO
-
+ H
+
Solutions of chemical
compounds
Chapter I
DOUBLE LAYER:
Theories and Structure

M
e
t
a
l

Electrochemistry deals with the interaction of
ionic conductors ( i.e., electrolyte solutions)
and electronic conductors (i.e., electrodes)

Electrolytic
solution
Upon contact of the two phases,
electrode and electrolyte, the properties
of the bulk of each phase remain
unchanged (e.g., electrical neutrality).

However, at the phase boundary (the
electrode-electrolyte interface), the
phases on either side become charged to
an equal and opposite extent and this
gives rise to a potential difference across
the boundary
There are several ways in which this
potential difference can arise:
1. Electron-transfer reactions can
occur at the boundary and lead to
the development of a potential
difference .

M M
n+
+ ne
M M
n+
Solution
Metal
2. The electrode can be deliberately charged by a flow of
electrons from an external source of electricity. The
electrolyte side of the boundary then responds with an
equal and opposite charge and, therefore, a potential
difference develops across the boundary.
e
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3. Even without an external connection or the
occurrence of electron-transfer reactions, it is possible
for a potential difference to develop across the phase
boundary due to the change of the properties at the
interface than that in the bulk of electrolyte.
M M
n+
Solution
Metal
+
+
+
+
+
+
+
+
Any of the previously mentioned
ways results in the formation of
what is called The Electric
Double Layer at the electrode-
electrolyte interface
The Structure of
the Electrical Double Layer
Helmholtz double layer

Gouy-Chapman diffuse double
layer

Stern diffuse double layer
Helmholtz double layer
Helmholtz in 1879 introduced the
concept of the electrical double
layer.
An electrical double layer of positive and
negative charges one molecule thick which
occurs at a surface where two bodies of
different materials are in contact, or at the
surface of a metal or other substance
capable of existing in solution as ions and
immersed in a dissociating solvent.
Gouy-Chapman diffuse double layer
Gouy proposed that the double layer is diffused,
with the outer ionic layer having an electric density
falling off according to an exponential law.
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Stern diffuse double layer
Stern compromised Helmholtz and
Gouy-Chapman.
The double layer is in two parts:
1. Helmholtz layer - one layer
approximately a single ion in
thickness, remains essentially fixed
to the interfacial surface. In this layer,
there is a sharp drop of potential.
2. Gouy-Chapman layer this layer
extends some distance into the liquid
dispersing phase and is diffuse, with a
gradual fall in potential into the bulk of
the liquid.
The electric double layer
boundary of two dimension at the molecular is a region of
substances across which an electrical field exists.
The substances must each contain electrically charged
particles, such as electrons, ions, or molecules with a
separation of electrical charges (polar molecules).
In the electrical double layer, oppositely charged particles
attract each other and tend to collect at the surface of each
substance but remain separated from one another by the
finite size of each particle or by neutral molecules that
surround the charged particles.
The electrostatic attraction between the two opposite and
separated charges causes an electrical field to be established
across the interface.
Usually Gouy-Chapman-Stern model
(GCS) is widely used to describe the electrical
double layer (EDL). The GCS model consists
of two layers;
1- The Stern layer (SL) is the region next to
the surface, and ions in the SL are bound near
the surface due to specially-adsorbing and
Coulomb interactions.
2- The diffuse layer (DL) is the region next to
the SL and ions in the DL can move freely in
any direction.
Electrical
double layer
The SL has two planes;
1- (IHP) the inner
Helmholtz plane
2- (OHP)the outer
Helmholtz plane as
shown in the figure .
Stern Layer SL
Stern Plane
Stern Layer SL
Stern Plane
<
<
<
<
<
<
-
<
<
<
+
<
+
<
+
<
<
<
<
<
<
+
IHP OHP
M
e
t
a
l

S
u
r
f
a
c
e

Solvated cation at OHP
Cation in diffuse
double layer
Contact adsorbed anion
Adsorbed organic molecule
< H
2
O molecule =
Stern Layer SL thickness

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Electrochemical Potentials

We can analyze the potential at the interface
by separating the electrode from the solution,
but with the charges of the metal and the
solution frozen in position. Think that a
positive charge at great distances from the
isolated electrode experiences a coulomb
potential that varies inversely with distance.
+
Metal with
a charge q
M
+
Metal with
a charge q
M

Galvani or Inner Potential (|) phi

the work needed to bring a charge from infinity to that point.
Outer or Volta Potential () psi
the work required to bring a charge from
infinity to just outside the range of image forces
Image force
fall off
100 nm
Metal with
a charge q
M

Surface or
Dipole
Potential (_)
chi
+
| = + _

A| = A + A_
+
+
+
+
+
+
+
Outer potential
| (Solution)
inner potential

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Electrochemistry involves either

generating electricity by using a spontaneous chemical
reaction (one with AG = - ve)

OR

using electricity to force a chemical reaction to occur
(one that is non-spontaneous, AG = + ve)

Understanding electrochemistry requires a basic
understanding of the processes called oxidation and
reduction.
Chapter II
Electrodes and Electrochemical cells
Oxidation and Reduction
Oxidation is
the loss of electrons
an increase in oxidation
state
the addition of oxygen
the loss of hydrogen

2 Mg + O
2
2 MgO

notice the magnesium is losing
electrons
Reduction is
the gain of electrons
a decrease in oxidation
state
the loss of oxygen
the addition of hydrogen

MgO + H
2
Mg + H
2
O

notice the Mg
2+
in MgO is
gaining electrons
Whats Happening when
A piece of Zinc is added
to a blue solution of
copper(II) sulfate
Plating bath Cu
2+
Zn
The blue colour disappearsthe zinc metal
dissolves, and solid copper metal precipitates
on the zinc strip
Zinc is oxidized (loses electrons)
Copper ions are reduced (gain electrons)
Zn (s) + Cu
2+
(aq) Zn
2+
(aq) + Cu (s)
This reaction is a spontaneous redox reaction
Copper ions (Cu
2+
)
collide with the zinc
metal surface
A zinc atom (Zn)
gives up two of its
electrons to the
copper ion
The result is a
neutral atom of Cu
deposited on the
zinc strip, and a
Zn
2+
ion released
into the solution
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During this spontaneous redox reaction, electrons flow
from the zinc atoms to the copper ions.


Zn Zn
2+
+ 2 e
-
(oxidation)
Cu
2+
+ 2 e
-
Cu (reduction)

Electricity can be thought of as the flow of electric
charge.
How can we make use of the flow of electrons from the
zinc atoms to the copper ions??

Answer: SEPARATE the copper ions from the zinc atoms.
This will force the electrons from the zinc atoms to travel
through an external path to reach the copper ions.
Separate the reactions so that the electrons flow
through an external circuit.
The voltage between the
anode and the cathode
means that the current
passing through the external
circuit can do work.
P =VI
Power = voltage current
Watts = volts amperes
Half-cell (electrode)
In the above cell the two halves of the cell
complete with electrode and electrolyte are
known as half-cells or electrodes
Anode : the electrode where oxidation occurs

Cathode : the electrode where reduction occurs
The question now is..
In other words..
Why Zn electrode acts as anode and undergoes
oxidation reaction, while Cu electrode acts as
cathode and undergoes reduction reaction?
What happen when a piece of Cu is immersed in a
solution containing Zn
2+
ions ??
Cu + Zn
2+
??
The answer is: it is a non spontaneous reaction.
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The reduction potential of an element is a
measure of its tendency to undergo reduction
reaction.
When connecting two electrodes directly to
form an electrochemical GALVANIC cell, the
following spontaneous reactions take place :
The electrode with the higher reduction
potential undergoes reduction reactions
However, the electrode with the lower
reduction potential is obligated to undergo
oxidation reactions

Can We Force
a Non-sponteneous Redox
Reaction To Occur??
The Answer is Yes, this can be
happen by the aid of an external
power supply in the ELECTROLYTIC
cell.
Free Energy and
the Galvanic Cell Potential
The electric work obtained from a cell
W
E
= Q.E
Cell
The charge involved in the cell reaction
Q = n.F
n is the number of moles of electrons transferred
F is the Faraday, the charge on one mole of electrons, 96 500 C/mol
W
E
= n.F. E
cell

the decrease in its
free energy (-AG)
The work performed
by the cell (n.F.E
cell
)
AG = - n.F.E
cell

=
E
cell
= E
cathode
E
anode
Spontaneity and the Sign of EMF
E
cell
AG Reaction
+ - Spontaneous
- + Non-spontaneous
0 0 Equilibrium
The spontaneous cell reaction is that one in which :

AG = - n.F.E
cell
= - ve value
i.e.

the anode is the electrode with more negative reduction
potential

the cathode is the electrode with more positive reduction
potential.
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IN GENERAL,
Electrochemistry involves either
generating electricity by using a
spontaneous redox reaction (one
with AG = - ve)
OR
using electricity to force a redox
reaction to occur (one that is non-
spontaneous, AG = + ve)

two
electrodes
vessel
conductive
medium
Any Electrochemical
Cell Consists of:
Anode : the electrode where oxidation occur
Cathode : the electrode where reduction occurs
Electrochemical Cells
Galvanic
(Voltaic) Cell
Electrolytic
Cell
generating electricity by
using a spontaneous
chemical reaction (one
with AG = - ve)
using electricity to force a
chemical reaction to occur
(one that is non-spontaneous,
AG = + ve).
The two electrodes are
connected with an external
source of potential..
Cu
1.0 M CuSO
4
Zn
1.0 M ZnSO
4
Salt bridge
KCl in agar
Provides conduction
between half-cells
I- Galvanic
(Voltaic) Cell
Observe the
electrodes
to see what
is occurring.
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Cu
1.0 M CuSO
4
Zn
1.0 M ZnSO
4
Cu
plates out
or
deposits
on
electrode
Zn
electrode
erodes
or
dissolves
cathode half-cell
Cu
+2
+ 2e
-
Cu
anode half-cell
Zn Zn
+2
+ 2e
-
- +
What about half-cell
reactions?
What about the sign
of the electrodes?
What
happened
at each
electrode?
Why?
Galvanic cell
cathode half-cell (+)
REDUCTION Cu
+2
+ 2e
-
Cu

anode half-cell (-)
OXIDATION Zn Zn
+2
+ 2e
-

overall cell reaction
Zn + Cu
+2
Zn
+2
+ Cu
Spontaneous reaction that produces electrical current!
battery
+ -
inert
electrodes
power
source
vessel
e
-

e
-

conductive
medium
II-Electrolytic
Cell
Sign or polarity of electrodes
(-) (+)
What chemical species would be present in a
vessel of molten sodium chloride, NaCl (l)?
Na
+
Cl
-
Lets examine the electrolytic cell for molten NaCl.
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+ -
battery
Na (l)
electrode
half-cell
electrode
half-cell
Molten NaCl
Na
+
Cl
-
Cl
-
Na
+
Na
+
Na
+
+ e
-
Na 2Cl
-
Cl
2
+ 2e
-
Cl
2
(g) escapes
Observe the reactions at the electrodes
NaCl (l)
(-)
Cl
-
(+)
+ -
battery
e
-

e
-

NaCl (l)
(-) (+)
cathode
anode
Molten NaCl
Na
+
Cl
-
Cl
-
Cl
-
Na
+
Na
+
Na
+
+ e
-
Na
2Cl
-
Cl
2
+ 2e
-
cations
migrate
toward
(-)
electrode
anions
migrate
toward
(+)
electrode
At the microscopic level
Molten NaCl Electrolytic Cell
cathode half-cell (-)
REDUCTION Na
+
+ e
-
Na

anode half-cell (+)
OXIDATION 2Cl
-
Cl
2
+ 2e
-

overall cell reaction
2Na
+
+ 2Cl
-
2Na + Cl
2

X 2
Non-spontaneous reaction!
Overview of
Electrochemical Cells
Chemistry
produces
electricity.
Anode=oxidation

Cathode =reduction
Electricity
drives
chemistry
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12
galvanic electrolytic
need
power
source
two
electrodes
produces
electrical
current
anode (-)
cathode (+)
anode (+)
cathode (-)
salt bridge vessel
conductive
medium
Comparison of Electrochemical Cells
AG < 0
AG > 0
In this course, we will
be interested in
Galvanic or Voltaic
cells.
Measuring the electrode potential
It is impossible to measure the potential of a single
electrode.
Using a voltmeters (or potentiometers), we can measure
the difference in potential between two electrodes.
We need a standard electrode to make measurements
against!
Chemists arbitrarily assigned a potential of 0 V for the
Standard Hydrogen Electrode (SHE).
By measuring the difference in potential between the
SHE and other electrodes, potentials can then be
assigned to other electrodes.
H
2
input
1.00 atm
inert
metal
The Standard Hydrogen Electrode (SHE)
Pt
1.00 M H
+
25
o
C
1.00 M H
+
1.00 atm H
2
Half-cell
2H
+
+ 2e
-
H
2
e
o
SHE
= 0.0 volts
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2 H
+
+ 2 e
-
H
2
e = 0 V
H
2
1.00 atm
Pt
1.0 M H
+ 1.0 M ZnSO
4
0.76 v
cathode half-cell
2H
+
+ 2e
-
H
2
anode half-cell
Zn Zn
+2
+ 2e
-

KCl in agar
Zn
-
Now lets combine the zinc half-cell with the SHE
e
o
= - 0.76 v
Standard half-cell potentials w.r.t.
standard hydrogen electrode
Zn(s) , Zn
++
(aq) ,, H
3
O
+
(aq) , H
2
(g) , Pt
H
2
1.00 atm
Pt
1.0 M H
+
Cu
1.0 M CuSO
4
0.34 v
cathode half-cell
Cu
+2
+ 2e
-
Cu
anode half-cell
H
2
2H
+
+ 2e
-
KCl in agar
+
Now lets combine the copper half-cell with the SHE
e
o
= + 0.34 v
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Assigning the E
o
Ag
+
+ e
-
Ag e
o
= + 0.80 V

Cu
+2
+ 2e
-
Cu e
o
= + 0.34 V

2H
+
+ 2e
-
H
2
e
o
= 0.00 V

Zn
+2
+ 2e
-
Zn e
o
= - 0.76 V

Al
+3
+ 3e
-
Al e
o
= - 1.66 V
Write a reduction half-cell, assign the voltage
measured, and the sign of the electrode to the
voltage.
I
n
c
r
e
a
s
i
n
g

M
e
t
a
l

a
c
t
i
v
i
t
y

Table of Standard Reduction Potentials
The Spontaneity Rule
Co(s) + Pd
2+
(aq) Co
2+
(aq) + Pd(s)
Pd(s) + Pt
2+
(aq) Pd
2+
(aq) + Pt(s)
Mg(s) + Co
2+
(aq) Mg
2+
(aq) + Co(s)
A student performed the following reactions. Construct a table of relative strengths of
oxidizing and reducing agents.
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Writing Full-Cell Reactions .
These are the rules for making a full cell from two half-cells that
will have the correct potential and will be the spontaneous reaction.
(1)Multiply through the reactions to give the same number of
electrons in each.
(2)Write the reaction with the more positive electrode potential.
(3)Reverse the reaction with the more negative potential and write it
underneath. Dont forget to reverse the sign of the half-cell potential.
(4)Add the two reactions and the two electrode potentials.
E
cell
= e
red
- e
ox


If you have done it correctly, you will have:
no electrons left over
E
cell
= +ve value, i.e., a spontaneous reaction.
Examples:
Since Cu has a higher
reduction potential than Zn,
copper forms the cathode. We
could also argue that Zn has a
lower reduction potentialand
forms the anode.

The overall reaction is:

Zn + Cu
2+
Zn
2+
+ Cu
E
cell
= e
red
- e
ox
= 0.34 + 0.76 = 1.10 V
Cu
Zn
Cathode:
Cu
2+
+ 2e
-
Cu e
red
= +0.34 V
Zn
+2
+ 2e
-
Zn e
ox
= -0.76 V Zn Zn
+2
+ 2e
-
- e
ox
= +0.76 V
Reverse the more -ve
Anode
AG
o
=-2x96500x1.1= - 212300 J/mol

Examples of Calculating the cell potential,

E
o
cell
, at standard conditions
Fe
+2
+ 2e
-
Fe e
o
= -0.44 V
O
2
(g) + 2H
2
O + 4e
-
4 OH
-
e
o
= +0.40 V
Consider a cell consists of an
iron electrode immersed in Fe
2+
solution and a Pt electrode
immersed in oxygenated water
Fe Fe
+2
+ 2e
-
-e
o
= +0.44 V 2x
2Fe + O
2
(g) + 2H
2
O 2Fe(OH)
2
(s) E
o
cell
= +0.84 V
Reverse the more -ve
H
2
O with O
2
Fe
Fe
2+
0.84V
KCl in agar Pt
AG
o
=-4x96500x0.84= - 324240 J/mol (of O
2
)

J/2mol (of H
2
O) J/2mol (of Fe)
Zn
+2
+ 2e
-
Zn e
o
= -0.76 V
Cr
3+
+ 3e
-
Cr e
o
= -0.74 V
Calculate the standard cell
potential of a cell consists of a
chromium electrode immersed in
Cr
3+
solution and a Zinc electrode
immersed in Zn
2+
solution
Zn Zn
+2
+ 2e
-
-e
o
= +0.76 V 3x
2Cr
3+
+ 3Zn 2Cr + 3Zn
2+
E
o
cell
= +0.02 V
1M Cr
3+

Zn
1M Zn
2+
0.02V
KCl in agar Cr
Reverse the more -ve
2x
AG
o
=-6x96500x0.02= - 11580 J/2mol (of Cr)

J/3mol (of Zn)

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AG
o
= -nFE
o
cell
Cu Cu
+2
+ 2e
-
-e
o
= - 0.34 V
Ag
+
+ e
-
Ag e
o
= + 0.80 V 2x
Cu + 2Ag
+
Cu
+2
+ 2Ag E
o
cell
= +0.46 V
AG
o
=-2x96500x0.46= - 88780 J/mol of Cu
What is the free energy for the cell?
Cu
+2
+ 2e
-
Cu e
o
= 0.34 V

J/2mol (of Ag)

Electromotive Force of the Cell (emf)
It is the difference of potential that causes a current
to flow from the electrode of higher potential to the
electrode of lower potential.
It is the difference in potential between the cell
electrodes when no current flows between them.
When current flows, part of the emf is used to
overcome the internal resistance of the cell.
Where flow of current forms reaction products at
the electrodes and changes the electrolyte
concentration around the electrodes. Consequently,
it changes the emf
Measurement of the emf of the Cell
Poggendorff Method
W: cell with known emf E
A
(standard cell)

E
W
= I
o
x (R
ab
)

X: cell with unknown emf
E
W
opposes E
X

The sliding contact C is
moved along ab to a position
S at which the galvanometer
G reads 0
E
X
= I
o
x (R
aS
)
E
W
> E
X

W
ab
aS
X
ab
aS
W
X
E
R
R
E
R
R
E
E
|
|
.
|

\
|
=
=
b vvvvvvvvvvvvvvvvvvvvvvvv
X
G
C
a
S
W
- +
- +
Weston standard cell
Its potential is:
1. Well known
2. Reproducible
3. Constant with time

Saturated
CdSO
4
Solution
CdSO
4
.8/3H
2
O
Cd Amalgam
Hg
Hg+Hg
2
SO
4
+ -
Cork
Cell reaction
Cd(s) + Hg
2
SO
4
(s) + 8/3 H
2
O = CdSO
4
.8/3H
2
O(s) + 2Hg(l)
Cell potential E
W
= 1.01830-4.06x10
-5
(t-20)
2/17/2013
17
Now for a standard cell composed of
Cu/Cu
+2
and Zn/Zn
+2
, the measured
voltage produced by the reaction at
25
o
C is 1.1 V
Standard Conditions
Temperature - 25
o
C
All solutions 1.00 M
All gases 1.00 atm
Cu
1.0 M CuSO
4
Zn
1.0 M ZnSO
4
cathode half-cell
Cu
+2
+ 2e
-
Cu
anode half-cell
Zn Zn
+2
+ 2e
-
- +
1.1 volts
What happens to the electrode potential if
conditions are not at standard conditions?
For the general electrode reaction:
ox + ne red
The electrode potential is dependent on
concentration and on temperature , described
by the Nernst Equation:
AG = G
red
G
ox.
=G
prod
G
react.

But
G = G
o
+ RTln a a is the activity
AG = (G
o
+ RTln a)
red
(G
o
+ RTln a)
ox.
AG = (G
o
+ RTln a)
prod.
(G
o
+ RTln a)
react.
Where e is the standard electrode potential V
R is the Ideal Gas Constant, 8.314 J.mol
-1
.K
-1

T is the absolute temperature of the electrode
n is the number of moles of electrons transferred
F is the Faraday, the charge on one mole of electrons, 96 500 C/mol
e = e
o
RT ln (a
red.
)
nF (a
ox.
)
e = e
o
RT ln (a
Prod.
)
nF (a
react.
)
AG = (G
o
red
- G
o
ox.
) + RT(ln (a)
red.
-ln (a)
ox.
)
AG = AG
o
+ RT(ln (a)
red.
-ln (a)
ox.
)
AG = AG
o
+ RT ln (a
red.
)
(a
ox.
)
But AG = -nFe

,

AG
o
= -nFe
o
-nFe = -nFe
o
+ RT ln (a
red.
)
(a
ox.
)
2/17/2013
18
at 25
o
C: e = e
o
- 0.0591 log (a
Prod.
)
n (a
react.
)
at 25
o
C:

RT ln x = RT 2.303 log x = 0.0591 log x
F F
Concentration (C), Activity (a) and
Activity Coefficient
Activity (a) =Concentration (C) x Activity Coefficient

In dilute solutions,
no ion-ion interaction or solvent effects
(ions behaves ideally)
= 1 a=C

In concentrated solutions,
the interactions between ions and solvent molecules lead
to describing the ions in terms of their activities instead of
concentration
< 1 a<C
Debye-Hckel Equation

- Relates activity coefficients to ionic strength (at 25
o
C)
/305) ( 1
0.51z
log
2
+

=
= activity coefficient
z = ion charge ()
= ion size in picometers (1 pm = 10
-12
m)
= ionic strength
ACTIVITY COEFFICIENT
-The activity coefficient of ions may be estimated by
simple calculations as follows:
ACTIVITY COEFFICIENT
Effects (limited to dilute aqueous solutions)

- Activity coefficient increases with decreasing ionic strength
(approaches unity as ionic strength approaches zero)

- Activity coefficient depends on the magnitude of the charge
but not on the sign
(departs from unity as charge increases)

-Effect of activity on ions increases with decreasing ion size
/305) ( 1
0.51z
log
2
+

=
2/17/2013
19
ACTIVITY COEFFICIENT
Gases, Activity (called fugacity) is written as

a
gas
= P
gas
x
gas


P = pressure in bars,
gas
= fugacity coefficient of a gas


For most gases at or below 1 bar
gas
1
Neutral Molecules

-Activity coefficient is assumed unity
(no charge and no ionic atmosphere)

- Activity is assumed to be equal to its concentration
OR 2H
+
(0.5M) +2e H
2
(0.95 atm)

e = 0 - 0.0591 log (0.95) = - 0.0591 log (0.95)
1/2

2

2 (0.76x0.5)
2
2 (0.76x0.5)


at 25
o
C: e = e
o
- 0.0591 log (red)
n (ox)
H
+
(0.5M) + e 1/2H
2
(0.95 atm)

H2
1,
H+
0.76

e = 0 - 0.0591 log (0.95)
1/2
= -0.0242
1 (0.76x 0.5)
Answer
Calculate the potential for the hydrogen electrode
when immersed in 0.50 M H
+
and 0.95 atm H
2
.
= -0.0242 V
The Nernst Equation is also used to calculate the
cell potentials under non- standard conditions
For the cell reaction:
A + B C + D




where E

cell

is the standard cell potential = e
o
cathode
- e
o
anode

n is the number of moles of electrons transferred in one
of the half cell reactions (after equaling the no. of
electrons in the two half reactions)
( )
[A][B]
[C][D]
cell cell
ln
F n
RT
E E =

Using the Nernst Equation
Calculate E
cell
for the cell described below at 25C

Anode: (oxidation)
Mg Mg
2+
(a=0.005) + 2 e
-
-e = 2.37 V

Cathode: (reduction)
Ag
+
(a=2.0) + e
-
Ag e = 0.80 V

Overall:
Mg + 2 Ag
+
(a=2.0) Mg
2+
(a=0.005) +2 Ag
e = 3.17 V

According to our balanced equation, n = 2 mol of e
-
Substituting into the Nernst Equation:
2/17/2013
20
|
|
.
|

\
|
=
+
+
2
2
cell
) (
) (
log
2
(0.059)
) 17 . 3 ( E
Ag
Mg
V
|
|
.
|

\
|
=
2 cell
) 2 (
.005) 0 (
log
2
(0.059)
) 17 . 3 ( E V
Thus, E
cell
= 3.26 V
Calculating Equilibrium Constants
When an electrochemical cell operates, the
concentrations of the ions change until reaching
equilibrium.
When the cell reaches equilibrium, E
cell
= 0.
Combining these facts with the Nernst equation gives:


Rearranging, we can derive an equation to calculate the
equilibrium constant for a redox reaction:
( ) K log
n
0.059
E 0 E
cell cell
= =

( ) K log
n
0.059
E =

79
If Q < K
eq
, shift to
right (toward product)
If Q > K
eq
, shift to
left (toward reactant)
( ) ( ) Q ln
F n
RT
E ln
F n
RT
E E
cell [A][B]
[C][D]
cell cell
= =

Calculating K for a Redox Reaction
Calculate K for the reaction that occurs when Mg is added to a solution
of AgNO
3
.
The net reaction is:

Mg + 2 Ag
+
Mg
2+
+ 2 Ag







107.46 = log (K) so K = 10
107.46
= HUGE
( ) K log
n
0.059
E =

( ) K log
2
(0.059)
17 . 3 = V
2/17/2013
21
Describing (representing) an electrode
Line Notation of an Electrode
An electrode needs to be described in a more convenient way than
drawing a diagram!
Providing an electrode with a reaction (reduction reaction)
Ox
+(n+y)
+ ne
-
Red
+y

line notation can be use to describe the electrode as follows:
Ox
+(n+y)
| Red
+y

The Oxidizing form is described before the Reducing form.
Concentrations of ions are indicated in brackets.
A vertical line ( | ) represents a phase boundary.
A comma (,) separates two components in the same phase.


Examples
The standard zinc electrode a
Zn
2+=1:

Zn
2+
(1.0 M) + 2 e
-
Zn e = -0.67 V

Zn
2+
(1.0 M) | Zn

1.0 M Zn
2+
Zn
H
2
1.00 atm
Pt
The standard hydrogen
electrode :


2 H
+
+ 2 e
-
H
2
e = 0 V


H
+
(1.0 M) | H
2
| Pt


1.0 M H
+
Line Notation of a Galvanic Cell
An electrochemical cell needs to be described in a more
convenient way than drawing a diagram!

We use line notation to describe a cell. The zinc-copper
standard cell is described:

Zn | Zn
2+
(1.0 M) || Cu
2+
(1.0 M) | Cu

The ANODE is described before the CATHODE.
Reduction (cathode) at Right
Concentrations of ions are indicated in brackets.
A vertical line (|) represents a phase boundary.
A double vertical line (||) represents the salt bridge.
Comma (,) separates two components in the same phase
A dashed line () represent the separation of two liquids by a
semi-permiable membrane (liquid junction pot. is significant)
2/17/2013
22
Line Notation - an example
Write down the half-cell and the overall reactions for
the cell described below:

Mg | Mg
2+
(1.0 M) || Ag
+
(1.0 M) | Ag

Anode: Mg Mg
2+
+ 2 e
-
e = 2.37 V
(oxidation)

Cathode: Ag
+
+ e
-
Ag e = -0.80 V
(reduction)


Overall: Mg + 2 Ag
+
Mg
2+
+ 2 Ag E = 3.17 V
Review: Whats the oxidizing agent? the reducing agent?
Whats E for the reverse reaction?
Classification of Electrodes
Electrodes of
the first kind
Electrodes of
the second kind
Electrodes of
the third kind
The oxidized
form in one phase
and the reduced
form in the other
phase
The two forms are
on the electrode
surface
The two forms are
in the electrolyte
phase
Reference electrodes
Redox electrodes
The general electrode reaction:
ox + ne red
Electrodes of the first kind
1. Metal-metal ion electrodes
( )
] [Zn
1
Zn | Zn Zn | Zn
2 2 2
log
2
0.059
E E
+ + +
=

( )
] [M
1
M | M M | M
n n n
log
n
0.059
E E
+ + +
=

1.0 M Zn
2+
Zn
Equilibrium is established between atoms or
molecules of the substance and the corresponding
ions (cations or anions) in solution
Line notation Zn
2+
| Zn

M
+n
| M
reaction Zn
2+
+ 2e Zn M
+n
+ ne M
2. Gas electrodes
A. Hydrogen electrode

H
2

Pt
H
+
|
|
.
|

\
|
=
+ + + 2
2
2 2 ] [H
H
H | H H | H
P
log
2
0.059
E E

This electrode can be used to measure
the pH of a solution
Calculate the pH of a solution which makes the potential
of the hydrogen electrode -0.01 V when immersed in it
at 1.0 atm.
Line notation H
+
|H
2
| Pt

X
+n
| X
2
, Pt
reaction 2 H
+
+ 2 e
-
H
2
2 X
+
+ 2 e
-
X
2

2/17/2013
23
2. Gas electrodes (continue)
B. Chlorine electrode
Pt | X
2
| X
-n

X
2
+ 2 e
-
2 X
-

Pt | Cl
2
| Cl
-

Cl
2
+ 2 e
-
2Cl
-


Cl
2

Pt
[Cl
-
]
|
|
.
|

\
|
=
2
Cl
2
|Cl Cl |Cl Cl
P
]
-
[Cl
log
2
0.059
E E
-
2
-
2

Calculate the Cl
-
ion conc. Which makes the potential of the
chlorine electrode 1.345 V at 0.1 atm (E
o
Cl2|Cl
- = 1.36 V).
3. Amalgam electrodes
Amalgam = Solution of metal in mercury
The value of amalgam electrodes is that active
metals such as Na can be used in such electrodes.

M
+n
| M, Hg
M
+n
+ne + Hg M (Hg)



Na
+
| Na, Hg
Na
+
+e Na (Hg)



Na
+
Na(Hg)
Pt
( )
] [Na
[Na(Hg)]
Na | Na Na | Na
log
1
0.059
E E
+ + +
=

( )
] [M
[M(Hg)]
M | M M | M
n n n
log
n
0.059
E E
+ + +
=

Electrodes of the second kind
These electrodes consist of three phases.
The metal is covered by a layer of its sparingly soluble salt and is
immersed in a solution containing the anions of this salt.
X
-m
| M
m
X
n
| M
Because of the two interfaces, equilibrium is established between the
metal atoms and the anions in solution through two partial equilibria:
1. between the metal and its cation of the sparingly soluble salt
M
+n
(aq) + (n) e
-
M Redox reaction
2. between the anion in the solid phase of the sparingly soluble salt and
the anion in solution
M
m
X
n
(s) m M
+n
(aq) + nX
-m
(aq) Precipitation reaction
m x
M
m
X
n
(s) +(nxm) e
-
m M + nX
-m
(aq) Electrode reaction
M M
m
X
n
X
-
1. Silver-silver chloride electrode
Ag
+
+ e Ag(s)
AgCl(s) Ag
+
+ Cl
-


( ) ] Cl [ log
1
0.059
E E
Ag AgCl| Ag AgCl|

=

Potential
NHE / V
[Cl
-
]
0.2881 0.1 M
0.205 3.5 M
0.197 Saturated
Ag
AgCl
Cl
-
AgCl(s)+ e Ag(s) + Cl
-
Cl
-
| AgCl | Ag
For [Cl
-
] = 0.01
E
AgCl|Ag
= 0.222 - 0.059 x (-2)
= 0.222 + 0.118
= 0.340 V
It may be used to measure the
chloride concentration.
2/17/2013
24
2. Calomel electrode
(Hg
2
)
2+
+ 2e 2Hg(l)
Hg
2
Cl
2
(s) (Hg
2
)
2+
+ 2Cl
-


( ) ] Cl [ log
1
0.059
E E
Hg | Cl Hg Hg | Cl Hg
2 2 2 2

=

Potential
NHE / V
[Cl
-
]
0.3337 0.1 M
0.2812 1 M
0.2422 Saturated
Hg
2
Cl
2
(s) + 2e 2Hg(l) +2 Cl
-
Cl
-
| Hg
2
Cl
2
| Hg
For [Cl
-
] = 0.001
E
Calomel
= 0.268 - 0.059 x (-3)
= 0.268 + 0.177
= 0.445 V
Hg
Hg
2
Cl
2
+Hg
KCl
3. Metal-metal oxide electrode
Sb
Sb
2
O
3

OH
-
Antimony /Antimony oxide electrode
OH
-
| Sb
2
O
3
| Sb
Sb
2
O
3
+ 3H
2
O +6 e 2Sb + 6OH
-
E=E
o
(0.059/6) log (OH
-
)
6


E=E
o
(0.059) log (OH
-
)

E=E
o
+ (0.059) pOH

E=E
o
+ (0.059) (14-pH)
Electrodes of the third kind
redox electrodes
An inert metal (usually Pt, Au, or Hg) is
immersed in a solution containing two forms of
a single substance in different oxidation states.
The metal merely acts as a medium for the
transfer of electrons between the two forms

Pt
Fe
2+
+ Fe
3+
Fe
3+
, Fe
2+
| Pt

2/17/2013
25
Electrochemical Cells
Galvanic
(Voltaic) Cell
Electrolytic
Cell
generating electricity by
using a spontaneous
chemical reaction (one
with AG = - ve)
using electricity to force a
chemical reaction to occur
(one that is non-spontaneous,
AG = + ve)
Battery: is a combination of two or more galvanic
cells arranged in series or in parallel
The ordinary 12V car battery = six 2V cells connected in series
Chapter III
Galvanic Cells
Reversible cells
Irreversible cells
Conditions of a reversible process
(a) the driving and opposing forces are infinitesimally
different from each others.
(b) it should be possible to reverse any change taking
place by applying a force infinitesimally grater than
the one acting.
Reversible Cells
An applied voltage,
greater than the cell
potential, drives the
reactions in reverse.
Anode and cathode
are interchanged
Charging batteries
Production of
aluminum metal
Production of
chlorine gas from
molten salt.
Irreversible Cells
H
2
SO
4
solution
Zn
Cu
ZnSO
4
solution
Zn
Cu
Zn|H
2
SO
4
(dil)|Cu

Zn + H
2
SO
4
ZnSO
4
+ H
2
even without connection
Cathode: Zn
2+
+ 2e Zn

Anode: Cu Cu
2+
+ 2e
Cell: Zn
2+
+ Cu Zn + Cu
2+

V
2/17/2013
26
Irreversible Cells
H
2
SO
4
solution
Pt
0.0V
Pt
H
2
SO
4
solution
Pt
Pt
No net reaction
Cathode: 2 H
+
+ 2e H
2
Anode: 2H
2
O O
2
+ 4 H
+
+ 4e
Cell: 2H
2
O O
2
+ 2 H
2

Classifying Galvanic cells according
to the nature of the electrode
reaction.
Galvanic Cells
Chemical Cells
Concentration Cells
Physical Cells
Gravitational Cells
Hg(h
1
)|HgA|Hg (h
2
)

Allotropic Cells
M
|
|MA|M
o

Daniel Cells
Zn|ZnSO
4
||CuSO
4
|Cu

Pt, H
2
(P
1
)|HCl|H
2
,(P
2
), Pt
Cells without transport
without Transference
(two electrodes in the
same electrolyte)
Cells with transport
with Transference
(two electrodes in two
different electrolytes)
(with liquid
junction potential)
(without liquid
junction potential )
Any Class
Examples
Zn|ZnSO
4
||CuSO
4
|Cu
Cd, Hg|CdSO
4
|Hg
2
SO
4
|Hg
Pt, H
2
|HCl|AgCl, Ag
Pb|PbSO
4(s)
|H
2
SO
4
|PbSO
4(s)
, PbO
2(s)
|Pb
Pt, H
2
(P
1
)|HCl|H
2
(P
2
), Pt
Pt, H
2
(P)|HCl(a
1
)|HCl(a
2
)|H
2
(P) , Pt
2/17/2013
27