Jinka University

College of Natural and Computational Science

Department of Chemistry

Course Title: Chemical Kinetics and Electrochemistry

Course Code: Chem 2062

For 2nd year chemistry students

Jinka University

Jan- 2021
Chemical Kinetics and Electrochemistry
  What is Electrolytic solutions
An electrolyte is a compound which produced an ionic solution when dissolved in an aqueous
solution. For example, a salt like KCl would produce an electrolyte solution. Those
compounds which produced a large number of ions in solution are called strong electrolyte.
KCl, b/c it is highly soluble, would be a strong electrolyte. On the other hand, those
compounds which produce a small number of ions in solution are weak electrolyte. Notice
that non-ionic compounds can produce electrolyte solution too.
Mobility of ions
 Is the absolute value of the velocity of field ratio being known as the mobility ui (with
m2s-1v-1) of the carrier.
 Ion movement in solution is random. However, a migrating flow can be on set upon
applying an electric field
∆ϕ
E=
L
ze ∆ ϕ
Ffield = zeE =
L
Where-: ∆ ϕ is the potential d/c b/n two electrodes separted by a distance L.
z number of ion charges
e elementary charge (1.6 x 10-19 c)
 Force accelerates cations to the negatively charged electrode and anions in the
opposite direction. Through this motion, ions experience a frictional force in the
opposite direction. Taking the expression derived by stoke relating frictional and the
viscosity of the solvent ( Ƞ¿ , it follows
Ffric = 6 πȠrs stoke’s law
Where-: Ƞ viscosity
r hydrodynamic radius
s drift velocity
When the accelerating and retarding force balance each, s is defined by F fric = Ffield or when
the ion has reached its diraft velocity both force are equal.
zeE = 6 πȠrs
zeE ze
s = 6 πȠr = uE where u =
6 πȠr

u is high for anion that is:-

  Highly charged
 In a solution of low viscosity
 Of small radius r
Example:- taking a conductometer cell with electrodes separated by 1 cm and an applied
voltage of 1 v, calculate the drift speed in water at 298 k.
Given Required
r = 170 pm = 170 x 10-12 m 1. u
Ƞof H2O = 0.891 x 10-3 kgm-1s-1 2. E
L = 1 cm = 0.01 m 3. S
∆ϕ =1V
e = 1.602 x 10-19 C
Solution
ze 1 x 1.602 x 10−19C
u= =
6 πȠr 6 x 3.14 x 0.891 x 10−3 kgm−1 s−1170 x 10−12 m
u = 5 x 10-19 m2V-1s-1
∆ϕ 1V
E= = = 100 Vm-1
L 0.01 m
S = uE = 5 x 10-19 m2V-1s-1 x 100 Vm-1
S = 5 x 10-6 ms-1
Transport number
 Is the fraction of the total current carried by one particular charged carrier.
qi
ti = Where qi = ci|zi|ui
Q
c i∨z i∨u i ∞
ti =
∞
Q = ∑ qi
∑ c i∨z i∨u i i=1
i=1

c +¿ z ¿ ¿
t+ = +¿
c+¿ z
+¿ u
+¿ +c
u+¿

−¿ ∨z ¿
¿
¿
¿ ¿
¿

−¿∨u ¿
−¿

c−¿∨z ¿ ¿
t- = −¿∨
c +¿ z
+¿ u
+¿ +c
u−¿

−¿ ∨z ¿
¿
¿
¿ ¿
¿

−¿ ∨u ¿
−¿

ti = t + + t -
t++ t- = 1
Activity: - from the above relations drive the relationship b/n transport number and mobility
for a single (1 mole electrode) univalent electrolyte.
Example:- the drift velocity of Ag + and NO3- ion in a solution of AgNO 3 electrolytes b/n
electrodes is 0.916. Find tAg+ and tNO3-
Given Required
v Ag +¿
¿ = 0.916 tAg+ and tNO3-
v NO3−¿ ¿
v Ag+¿
uAg+ = ¿
E
v NO3−¿
uNO3- = ¿
E
uAg+ E = vAg+
uNO3- E = vNO3-
v Ag +¿
¿ = 0.916
v NO3−¿ ¿

u Ag+ E v Ag +¿
= ¿
u NO 3−E v NO3−¿ ¿

¿ ¿ v Ag +¿
u Ag+ = ¿ = 0.916
u NO 3 v NO3−¿ ¿

uAg+ = uNO3- 0.916

u Ag+ ¿
Then tAg+ = ¿
u Ag++u NO 3−¿ ¿
u NO 3−0.916
tAg+ =
u NO 3−0.916 +u NO 3−¿ ¿
u NO 3−0.916
tAg+ =
u NO 3−(0.916+1)
0.916
tAg+ =
1.916
tAg+ = 0.5219
tAg+ + tNO3- = 1

0.5219 + tNO3- = 1

tNO3- = 0.4781
Fugacity activity and activity coefficient
 Define the term Fugacity activity and activity coefficient
Answer:- maybe defined as the substitute for the concentration to explain to behavior of real
gas.
Activity
Maybe defined as the substitute for the concentration to explain to behavior of a non-ideal
solution.
 Is the measure of the effective concentration of a species in a mixture.
Thus in a mixture of real gas:- the chemical potential (µi) of any constituent is given by
µi = µio + RTlnFi for real gas Fi indicate real gas and Pi indicate ideal gas
Where:- Fi is the fugacity of the constituent i in the mixture.
Similarity in a non-ideal solution the chemical potential of any component i is given by
µi = µio + RTlnai non ideal solution
where:- ai is the activity of component i in the solution thus to explain to behavior of real gas.
The pressure has to be corrected by multiplying with a suitable factor to get the fugacity.
i.e F = r x p if it have mixture of real gas effective pressure (correction).
Where:- r is called the activity coefficient of the gas.
Activity coefficient
 Is a measure of deviation from ideality hence activity coefficient o a gas to the
pressure of the gas in the same state i.e r = F/P
 Similarity in a non-ideal solution the concentration has to be corrected to give the
activity as follows where a – activity
 a= r x c if it has mixture of non-ideal effective concentration (correction)
 Where r represents the activity coefficient of the component in the solution whose
concentration is c. hence activity coefficient of any component in the solution may be
defined as the activity of that component in the solution to the concentration of the
same component in the solution.
 For an ideal solution (i.e for every dilute solution)
r = 1 so that a = c
For other solution greater is the departure in the value of “r” from 1 more non-ideal is
the solution. An ideal solution has r = 1 and a non-ideal solution has r > 1
¿T, P, n1, n2
Thus quantity is called partial molar free energy or chemical potential and is usually
represented by the symbol µ
This µi = Gi = ¿T,P n1 n2 if the dni = 1 mole µi = (dG )T, P, n1, n2
The chemical potential of constituent in a mixture is increase in free energy which takes place
at constant temperature and pressure when 1 mole of that constituent is added to the system
kepping the amounts of all other constituents’ constant i.e when 1 mole of the constituents is
added to such a large quantity of the system that is composition remains almost unchanged
(dG)T, P = µ1dn1 + µ2dn2 +…………..
For a system of definite compositions represented by the number of moles n1, n2, ……. etc
G,T, P,N (constant composition) = n1 C + n2 µ2 + ………..
 For electrolyte solution that is stated interims of the chemical potential, activity and
activity coefficients of the individual ionic species, consider the Gibbs free energy of
the solution which can be write as
G = nsolvent µsolvent + nsolute µsolute 1
Au+ + Bu- that dissociates completely
i.e Av+ + Bv- → v+Az+ (aq) + v-Bz- (aq) one can also write an equivalent expression for G
G = nsolvent µsolvent + nsolute µsolute (v+µ+ + v- µ-) 2
Where v+ and v- are the stoichiometric coefficient of the cations and anions respectively
produced upon dissociation at the electrolyte b/c eqn (1) and eqn (2) describe the same
solution are equivalent
µsolute = v+ µ+ + v- µ- 3 for strong electrolyte
Mean ionic chemical potential (µ±) for the solute
µ solute v ¿
µ± = = + ¿µ −¿+ v ¿ ¿ 4
v
µ
−¿ −¿ ¿
v

where:- v = v+ + v-
Relate the chemical potential of the solute and its individual ions to the activities of these
species for the individual ions.
µ+ = µ+o + RTlna+ and µ- = µ-o + RTlna- 5
Where:- µ+o & µ-o are the standard chemical potential of cations and anions respectively
Substituting eqn (5) in eqn (4) an equation for mean ionic chemical potential is obtained (µ±)
i.e µ±= v+ ¿¿¿ ¿ ¿
v+ ¿µ ¿
µ±= o
+¿ + v +¿ +v
−¿ µ
o
+¿ +v
a−¿
¿
¿
¿ ¿
¿
since vµo± = v+ ¿µ o
+¿ ¿
¿ + v−¿µ o
+¿ ¿
¿
−¿ RTln ¿
v
+¿ RTlna ¿

µ± = vµo± + RT ¿ ¿
o V
vµ + RTln a±
µ± = ± since a V± = a +¿v +¿ ¿
¿ + a−¿ v −¿ ¿
¿
v
o
vµ ± vRTln a ±
µ± = + since ln a V± = vlna ±
v v
µ± = µo± + RTlna ± 6
The mean ionic activity a ±is related to the individual ion activity by
V
a ± = a +¿ v +¿ ¿
¿ . a−¿ v −¿ ¿
¿ or since a+ = v+a+ and a- = v-a-
a ± =¿ ¿ 7
Example:- write the mean ionic activities of NaCl, K 2SO4 and H3PO4 interms of the ionic
activity of the individual anions and cations. Assume complete dissociation.
Solution a) NaCl (s) → Na+ (aq) + Cl- (aq) v+ = 1, v- = 1 Vtotal = 2
V
a ± = a +¿ v +¿ ¿
¿ . a−¿ v −¿ ¿
¿

2
a NaCl = a Na+¿¿ + a Cl−¿¿
¿
b) K2SO4 → 2K+ (aq)+ SO 2−¿
4 (aq) v+ = 2, v- = 1 Vtotal = 3
= a SO
3
aK 2
SO4 2−¿
4
+aK ¿ ¿
¿

a± = ¿ ¿
3−¿(aq )¿
c) H3PO4 → 3H+ (aq)+ PO 4 v+ = 3, v- = 1 Vtotal = 4

= a H ¿ + a PO
3
aK 2
SO4 ¿ 3−¿
4
¿

a± = ¿ ¿
Exercise:- for MgSO4, Na2SO4 and Al(NO 3)3 write mean ionic activity interms of individual
anion and cation.
If ionic activities are referenced to the concentration units of molality, then
mi
ai = ri o where:- mi the molality of the ion in mol/kg
m
mo is the standard molality in mol/kg 1 mol/kg
ri is the activity coefficient of the ion
Since mo = 1 mol/kg
ai = rimi
a+ = r+m+ and a- = r-m- 8
where m+ = v+m and m- = v-m where m:- total molality substituting eqn(8) in eqn(7)
V
a ± = a +¿ v +¿ ¿
¿ . a−¿ v −¿ ¿
¿ =
V
a ± = ¿ ¿+ ¿ ¿
V
a ± = r +¿ v +¿ ¿
¿ + r −¿ v −¿ ¿
¿ . m+¿ v+ ¿ ¿
¿ + m−¿ v−¿ ¿
¿

V v v
a ± = r ± m± 9
To simplify this notation, we define the mean ionic molality, m ± and mean ionic activity
coefficient r± by
 v
m ± = m+¿ v+ ¿ ¿
¿
m−¿ v−¿ ¿
¿

1
m± = ¿ ¿ (mv ) v

m± = ¿ ¿ m mean ionic molality

v
r ± = r +¿ v +¿ ¿
¿
r −¿ v −¿ ¿
¿

r± = ¿ ¿ (10) mean ionic activity coefficient therefore a V±

= r ±v m±v
V v v
a ± = r ± m±
V
a ± = r +¿ v +¿ ¿
¿
r −¿ v −¿ ¿
¿
m+¿ v+ ¿ ¿
¿ . m−¿ v−¿ ¿
¿

a± = ¿ ¿ 11
Or a ± = r± ¿ ¿ m
µ± = µo± + RTln r±m± mean ionic chemical potential interms of ionic molality and ionic
activity coefficient
Example:- calculate the mean ionic activity in 0.1 M of:-
a) AgNO3 (r± = 0.72)
b) CuSO4 (r± = 0.16)
Solution
−¿¿
a) AgNO3 (s) → Ag+ (aq) + NO 3 (aq)
V+ = 1 & V- = 1 V = 2
Using a ± = r± ¿ ¿ m
= 0. 72 ¿ 0.1
= 0.072
¿
b) CuSO4 → Cu2+ + SO 2−¿
4

Using a ± = r± ¿ ¿ m
= 0. 16¿ 0.1
= 0.016
Ionic Strength
 Ionic strength of a solution is a measure of the concentration of ions in solution.
 Is the total ion concentration in solution
 Is a function which takes in to account the electrostatic interaction b/n ions.
I = ½∑ ci zi2
= ½∑ mi zi2 where:- mi = molality of ion (i)
 zi = charge on the ion
I = ionic strength
Example:- calculate the ionic strength of 1 M solutions of KNO3, K2SO4
a) Solution
−¿¿
KNO3 → K+ + NO 3
I = ½∑ mi zi2
=½¿
=½¿
= ½ (1.1 M (1)2 + 1.1 M (-1)2)
= ½(1 M + 1 M)
=1M
b) Solution
¿
K2SO4 → 2K+ + SO 2−¿
4

I = ½∑ mi zi2
=½¿
=½¿
= ½ (2.1 M (1)2 + 1.1 M (-2)2)
= ½(12M + 14M)
=3M
Example 2:-calculate the ionic strength of a mixed 0.05 M in Na 2SO4 and 0.02 M in
KCl solution?
Solution
I = IKcl + INa2SO4
I = 0.15 M + 0.02 M
I = 0.17 M
Activity coefficients

 Can be calculated from the Debye–Huckel limiting law (at lower I), Debye-Huckel
law (at intermediate I) or the Debye-Huckel extended law (at higher I).
 Those calculated the activity coefficient from the charge on the ion and the ionic
strength.
Deby-Huckel Law
−A∨Z +Z −¿ √ I / I °
log r ± = for 10-3< I < 10-1 law
1+B √ I /I °
  Which can generally be applied to solution of I < 0.01 mol/dm 3 (for which this
assumption of relatively weak electrostatic interaction holds)
Where:- A– is a constant for a given solvent ( 0.509 for water at 298 K)
B- is a constant for a given ion in a given solvent ( conveniently B is often
approximately equal to 1 for most ions in water.
I 0- is the standared ionic strength (defined as 1.5 x 10 -4 – 0.0015 being to 1
mol/dm3)
 When I ≤ 0.001 mol/dm3 the first term in the denominator of the equation dominate
the second term and produces the simplified Debye- Huckel limiting law (which
removes the ion dependent parameter B from the expression.
log r ±= -A|Z+Z-| √ I /I ° for 0 < I ≤10-3 mol/dm3
 At higher values of I < 1 mol/dm3
log r ±= -A|Z+Z-| √ I /I ° + c|z+z-| I/I°
Where c – is an empirical parameter

 This equation is the Debye-Huckel extended law

Example 1. What is the activity coefficient of a solution CuSO 4 OF Concentration 10-2
mol/dm3?
Solution:- CuSO4 +H2O → Cu2+ (aq)+ SO42- (aq) (2:2 electrolyte) I = 4C, I = 4 x 10 -2
mol/dm3
−A∨Z +Z −¿ √ I / I °
log r ± =
1+B √ I /I °
−0.509∨2 x−2∨√ 0.04
log r ± = for ionic strength in the range of 10-3 < I < 10-1
1+1 √ 0.04
−0.509 ( 4 ) 0.2 −0.4072
log r ±= =
1+0.2 1.2
log r ±=−0.3393
r ±=¿ 10-0.3393
r ± = 0.458
2. What is the activity coefficient of a solution of CuSO4 OF concentration 10-4 mol/dm3.
Solution:- Solution:- CuSO4 +H2O → Cu2+ (aq)+ SO42- (aq) (2:2 electrolyte) I = 4C, I = 4
x 10-4 mol/dm3 is found in the rang 0 < I < 10-3 so apply simplified Debye- Huckel law
i.e log r ±= -A|Z+Z-| √ I /I ° for 0 < I ≤10-3 mol/dm3
log r ±=¿ -0.509 |2x -2|√ 0.0004
log r ±=−0.04072
 r ±=¿ 10-0.04072
r ± = 0.91

Theory of Electrolytic conductance

What is conductivity?
 Is the ability of a solution to pass current
 Is the ability of a solution a metal to pass an electric current
 In solution the current is carried by cations and anions where as in metal it is carried
by electrons
 A solution conducts electricity depends on a number of factors:-
 Concentration
 Mobility of ions
 Valence of ions and
 Temperature
How conductivity measured?
 Conductivity may be measured by applying an alternating electrical current (I) to two
electrodes immersed in a solution and measuring the resulting voltage (V).
 During this process, the cations migrate to the –ve electrode, the anions to the +ve
electrode and the solution acts as electrical conductor.
Figure 1. Migration of ions through electrolytic solution to opposite electrodes.
What is conductive solution?
 Conductivity is typically measured in aqueous solution of electrolyte.
 Electrolyties are substance containg of ions, i.e solution of ionic salts or solution of
compound that ionize in solution.
 The ions formed in solution are responsible for carring the electric current.
 Electrolytes include acids, bases and salts can be either strong or weak.
Strong Electrolytes
 Are substances that are fully ionized in solution
Weak Electrolytes
 Are substance that are not fully ionized in solution
 For example:- acetic acid partially dissociates in to ions and hydrogen ions, so that an
acetic acid solution contains both molecules and ions.
 A solution of a weak electrolyte can conduct electricity but usually not as well as a
strong electrolyte b/c there are fewer ions to carry the change from one electrode to
the other.
Conductance (G)
 It is the reciprocal of resistance
1
i.e G= where R is the resistance
R
 It’s unit is ohm-1 or mho or Siemens
 The resistance of uniform conductor is directly proportional to its length (l) and
inversely proportional to the cross- sectional area (A). thus
L L
R= or R=ρ
A A
 The proportionality constant (ρ) is called the specific resistance.
If L = 1 cm A = 1 cm2 then R = ρ
 Specific resistance (ρ) is defined as the resistance of a electrolyte solution of 1 cm in
length and 1 cm2 cross sectional area of the electrolyte solution.
 The unit of specific resistance is ohm centimeter
A
ρ=R unit of ρ = ohm cm
L
 The reciprocal of specific resistance (ρ) is called specific conductance. This may be
defined as the conductance of one centimeter cube of material and is denoted by K
 1 L
Thus K = =
ρ RA
 It’s unit is ohm-1 cm-1. IN SI units the unit of specific conductance (K) are Sm-1 where
S stands for siemene

Equivalent conductance (λ)

 Is defined as the conductances of an electrolyte solution containing one gram

equivalent of the electrolyte bin 1 cm electrode. It is usually denoted by λ
 The relationship b/n equivalent conductance and specific conductance is given as
Λ = VK where V volume
1000 K 1000 K 1000 ml
Λ= = if V= where N =
C N C
no of equivalent
volume (L)
K
Λ= if unit of Concentration is mol/10-3 m3
1000C
 The unit of equivalent conductance is ohm-1 cm2 eq-1 or Scm2/eq
Molar conductance

 Is defined as the conductance of electrolyte solution containing one mole of

electrolyte.
 It is denoted by λm
 If Vm ml is the volume of the solution containing one gram of electrolyte
Then λm = Vm x K
 If m is the concentration of the solution in moles per liters there λm = 1000K/m
 The unit of λm is Sm2mol-1 and m- is molarity
Cell constant

 It is a constant, characteristic the cell in which the electrolytic is taken and its value
depends on the distance b/n the electrodes and area of cross section of the electrode.
distance b /nthe electrodes
Cell constant =
area of cross sectionof each electrode

L L
Kcell = and specific conductance K= or K= GKcell
A RA
Example 1. The conductance of 0.0075 M solution of KCl is 1.49 x 103 micro moh. If the
cell constant (L/A) is 105 m-1 calculate the specific conductance as well as molar
conductance.
Given Required
C = 0.0075 M K, λm
G = 1.49 x 103 micro moh or 1.49 x 10-3 moh
Cell constant (Kcell) = 105 m-1
Solution
G = K/Kcell
K = G Kcell substituting the given in this equation
K = 1.49 x 10-3 moh X 105 m-1 = 0.1565 moh m-1
λm = K/1000C
0.1565
λm = Smol-1m2 = 0.021 Smol-1 m2
1000 x 0.0075
Activity
1. The resistance of 0. 1 M KCl solutions in a conductance cell is 325 ohm and the
specific conductance of the same solution is 1.29 moh m -1. If the resistance of 0.05 M
NaCl solution in same cell constant is 752.4 ohms (R). Calculate the molar
conductance of the same solution.
2. Show that λm= λ x z Where λm – molar conductance
λ – Equivalent conductance
z – Number of transfer ion
 Chapter Two
Electrochemical Cells
Introduction: -
Electrochemistry:- is the branch of chemistry deals with transformation of electrical energy
into chemical energy and vice versa.
Electrochemical cell is a system or arrangement in which two electrodes are fitted in the
same electrolyte or in two different electrolytes, which are joined by a salt bridge.
Electrochemical cell is of two types.
(1) Galvanic Cell or Voltaic Cell
(2) Electrolytic Cell
1. Galvanic cell or Voltaic cell
 Is cell which free energy of the chemical reaction within the cell changed to
electrical energy
i.e converts chemical energy to electrical energy
 the reaction is spontaneous
 cathode is +ve with respect anode (cathode +ve and anode –ve)
 is made upon two half cells i,e Anodic and cathodic
 the cell reaction is redox kind of ( there is transfer of electron)
 oxidation takes place at anode and reduction at cathode
 The two half reactions:- like Daniell cell,
 Zn(s) → Zn2+ (aq) + 2e- ( loss of electron:- oxidation) (oxidation takes place
at anode)
 Cu2+ (aq) + 2e- → Cu (s) (gaing of electron:- reduction) (reduction takes
place at cathode)
 Over all process (cell reaction)
  Zn (s) + Cu2+ (aq) →Zn2+ (aq) + Cu (s)
 In galvanic cell like daniell cell:- electrons follow from anode (Zn electrode) to the
cathode (Cu electrode) through external circuit zinc dissolves as Zn 2+, Cu2+ ion in the
cathode cell picks up two electron and becomes deposited at cathode.

Figure 1. Schematic diagram of the Daniell cell. and half-cells are connected through
a salt bridge in the internal circuit.
 Zinc rod immersed in ZnSO4 behaves as anode and copper rod immersed in CuSO 4
behaves as cathode
 Electrical neutrality is preserved in the electrolytes by the flow of cations and anions
in opposite directions through the salt bridge.
 Example:- saturated solution salt like KCl, KNO 3, NH4C and NH4NO3 etc used in salt
brige.
 KCl is mostly used as salt bridge since K + and Cl- ions have the same speed. Hence,
salt bridge with uniform and same mobility of cations and anions minimize the liquid
junction potential and permits the ions to migrate.
Function of salt bridge:
(a) It connects the solutions of two half cells and complete the cell circuit.
(b) It prevents transference or diffusion of the solutions from one half cells to the other.
(c) It keeps the solutions in the two half-cells, electrically neutral. In anodic half-cell, positive
ions pass into solution and there shall be accumulation of extra positive charge in the solution
around the anode, which will prevent flow of electrons from anode. Similarly in the cathodic
half cell accumulate around cathode due to deposition of positive ions by reduction. To
neutralize these ions, sufficient numbers of positive and negative ions are provided by salt
bridge. Thus salt bridge maintains electrical neutrality of the solution.
(d) It prevents liquid-liquid junction potential i.e. the potential difference which arises
between two solutions when contact with each other.
2. Electrolytic cell
 Is cell in which converts electrical energy to chemical energy
 Supply external force, it used battery
 The reaction is non-spontaneous reaction(∆ G = +ve)e.g. refrigerator
 Anodes are +ve with respect of cathode –ve

Figure 2. the flow of electrons and ions in an electrolytic cell

at anode: oxidation occurs
2Cl– →Cl2↑+ 2e–
at cathode: reduction occurs
2Na+ + 2e– →2Na
● Flow of electron from anode to cathode in outer circuit.
● Flow of current from anode of cathode through the solution.
● For the working of electrolytic cell, minimum voltage required is slightly more than the
Ecell.
 An electrolytic cell usually consists of a single compartment, but a number of
industrial versions have two compartments.
Types of Electrodes (Half Cells)
1. Metal-metal ion electrode
This type of cell consists of a metal M in contact with a solution containing M n+ ions and in
equilibrium with it.

Mn+ (aq) + ne- ⇄ M (s)

 0.0591 1
EMn+/M = E0Mn+/M - log ¿
n ¿¿
For example Zn2+ (aq) + 2e- ⇄ Zn (s)
0.0591 1
EZn2+/Zn = E0Zn2+/Zn - log ¿
2 ¿¿
2. Gas electrodes
In such a half cell, an inert collector of electrons Pt or graphit is contact with gas and solution
containing a specified ion.
One of the most important gas– ion half-cell is the hydrogen- gas- hydrogen ion half-cell. In
this half-cell purified H2 gas at constant pressure is passed over a platinum electrode which is
in contact with an acid solution.
H+ (aq) + e- ⇄ ½H2 (g) (Electrode reaction)
Pt|½H2 (g)/ H+ (aq): cell representation

Figure 3. Hydrogen electrode

3. Metal- metal insoluble electrode
In this half-cell, a metal coated with its insoluble salt is in contact with a solution containing
the insoluble salt.
Example 1. Ag|AgCl|Cl-
In this electrode, silver wire is coated with AgCl then, dipped into chloride ion solution.

Figure 4. Silver-silver chloride electrode

The equilibrium reaction that occurs at the electrode is-:
AgCl (s) + e- ⇄ Ag (s) + Cl- (aq)
Example 2. Hg|Hg2Cl2|Cl- (Calomel (Hg2Cl2) Electrode)
 Figure 5. calomel electrode
The reduction half reaction
Hg2Cl2 (s) + 2e- ⇄ 2Hg (l) + 2Cl-
0.0591
ECl-|AgCl|Ag = E0Cl-|AgCl|Ag - log [Cl-]
n
Potential of such cells depends upon the concentration of anions, such cell used as reference
electrode.
4. Oxidation – Reduction electrode
This type of half-cell is made by using an inert metal collector; usually platinium, immersed
in a solution which contains two ions of the some element in different states of oxidation.
Example Pt| Fe2+| Fe3+
Fe3+ (aq) + e- ⇄ Fe2+ (aq)
0.0591
EFe3+/Fe2+ = E0 Fe3+/Fe2+ - log ¿ ¿
n
Thermodynamics of Electrochemical Cells
If the cell reaction of Galvanic cell produces EMF (cell potential is the potential difference
b/n two electrodes) when Z faradays or ZF Columbus of electricity is passed. Then the work
done by the cell is-: W = |z| FE (1)
But work done is equal to decrease in Gibbs free energy
i.e. W = -∆ G
∆ G = -|z| FE or ∆ G = -nFE (2)
From thermodynamics, ∆ G = -ve (∆ G<0) for spontaneous process
E > 0 spontaneous
∆ G = +ve and E< 0 the cell process will be non-spontaneous
Reaction ∆G E
Spontaneous (-) (+)
Non spontaneous (+) (-)
Equilibrium 0 0
If the cell reaction given by-:
aA +bB ⇄ cC + dD
c d
aC a D
∆G = ∆G 0
+ RTln a b
a A aB
(3)
Where-: ∆ G0 free energy at unit activity
a activity of reactant or product
Substituting eqn (2) in eqn (3) becomes
c d
aC a D
-|z|FE = ∆ G0 + RTln a b
a A aB
c d
−∆ G
0
RT aC a D
E= - ln a b by dividing both side of the equation with -|z|F
¿ z∨F ¿ z∨F a A a B
Since ∆ G0 = -|z|FE0 (4)
0
−∆ G
E0 =
¿ z∨F
c d
RT
0
aC a D
E=E - ln a b (5) Nernst
¿ z∨F a A a B

equation
At equilibrium eqn (3) becomes where ∆ G = 0
∆ G0 = -RTlnKa (6)
c d
aC a D
where Ka = a b
a A aB
By substituting eqn (4) in eqn (6) becomes
-|z|FE0 = -RTlnKa
RTlnKa
E0 =
¿ z∨F
(7)
Enthalpy and Entropy of cell reaction
∆G = -|z|FE (1) and ∆G = ∆H -T∆ S
(2)
Taking the T0 derivative of ∆ G at constant pressure
∂(∆G) ∂(∆ H −T ∆ S)
=
∂T ∂
∂(∆G)
= -∆ S
∂T
∆S = - ∆G
∂(−¿ z∨FE)
∆S =
∂T

∆S = |z|F ( ∂∂ TE ) P

(3)
∆ H = ∆ G+ ∆ TS

∆ H = -|z|FE + T(|z|F ( ∂∂ TE ) )
P (4)

Where ( ∂∂ TE ) P is called temperature coefficient of cell potential. Its unit Volt/Kelvin

Representation of a cell (IUPAC convention)

Example-: for daniell cell
i) Anodic half-cell is written on left and cathodic half-cell on the right hand side
Zn (s)/ZnSO4 (aq) // CuSO4 (aq)|Cu(s)
ii) Two half cells are separated by double vertical lines. Double vertical lines
inducted salt bridge.
iii) EMF (electromotive force) written on the right hand side of the cell.
iv) Single vertical lines indicate the phase separation b/n electrode and electrolyte
solution.
Zn/Zn2+//Cu2+/Cu
Electrons flows from anode to cathode in external circuit due to a pushing effect called
electromotive force (E.M.F)
EMF- sometimes called as cell potential
Its unit is volt and calculated as-:
Ecell = reduction potential of cathode – reduction potential of anode
Ecell = Eright – Eleft
Similarity standared emf of the cell (E0) maybe calculated as
E0cell = E0right – E0left
EMF of cell should be positive otherwise it will not be feasible in the given direction
 Zn/ZnSO4 //CuSO4/Cu,
E0Cu2+/Cu = 0.34 and E0Zn2+/Zn = -0.76
E0cell = E0Cu2+/Cu - E0Zn2+/Zn
E0cell = 0.34 – (-0.76) = +1.1 volt since E0 +ve hence the cell will be feasible and zinc will
displace copper from its salt solution. In the other words zinc will reduce copper.
Example 1. For the cell reaction 2Ce4+ +Co → 2Ce3+ + Co2+
E0cell is 1.89 V if E0Co2+/Co is -0.28 V
What is the value of E0Ce4+/Ce3+
E0cell = E0r – E0l
1.89 V = E0Ce4+/Ce3+ - E0Co2+/Co
1.89 V = E0Ce4+/Ce3+ -(-0.28 V)
E0Ce4+/Ce3+ = 1.61 V
Writ the half-cell reaction
Ce4+ + e- → Ce3+ is half reaction of reduction
Co (s) → Co2+ is half reaction of oxidation
Example 2. The EMF of the cell which determined by Pb (s)/PbSO4 /Na 2SO4.10H2O
(saturated)

Hg2SO4 (s)/Hg (l) (+) is 0.9647 V at 25 ℃ , if T0 coefficient ( ∂∂ TE ) = 1.74 x 10

-4
V/K

a) Write the cell reaction

b) Determine ∆ G , ∆ S and ∆ H
Given Required
T = 25 ℃ = 298 k a) net reaction
E = 0.967 V b) ∆ G , ∆ S and ∆ H

( ∂∂ TE ) = 1.74 x 10
P
-4
V/K

Solution a.
Anodic reaction Pb (s) + SO4-2 → PbSO4 + 2e-
Cathodic reaction Hg2SO4 (s) + 2e- → Hg (l) + SO4
Net reaction Pb (s) + Hg2SO4 (s) → PbSO4 + Hg (l)
b. ∆ G = -|z|FE z = 2, F = 96500 C/mol and E = 0.9647 V
∆ G = -2 x 96500C/mol x 0.9647 = -186.19 kJ/mol

∆ S = |z|F ( ∂∂ TE ) = 2 x 96500 x 1.74 x 10

P
-4
V/k
∆ S = 33.6 J/molk
∆ H = ∆ G + T∆ S
∆ H = -186.19 Kj/mole + 298(33.6 J/molk)
∆ H = -176.2 KJ/mol