Current Efficiency of an

electrochemical Process
• In many electrochemical reactions the actual
amount of product is less than the theoretical
amount of product calculated according to
Faraday's law.
• The % ratio between the actual amount of
product and the theoretical amount is known
as the current efficiency (C.E).
actual amount produced
• C.E = × 100
theoritical amount
• The current efficiency can be also defined as
the % of the current consumed in producing
the main product.
 Causes of current inefficiency
• The occurrence of secondary reaction along
with the main reaction, for instance, H2
evolves simultaneously during the cathodic
deposition of metals such as Ni, Fe, Cd, Pb,
Cr and Zn according to the reactions
• M++ + 2e → M (main reaction)
• 2H+ + 2e → H2 (secondary reaction)
• Reaction of the cathodic product with the
anodic product, for example in the
electrolysis of brine (NaCl) to produce NaOH
and Cl2, the cathodically produced NaOH and
the anodically produced Cl2 react together in
the solution to form sodium hypochlorite
according the reaction:
• 2NaOH + Cl2 = NaOCl + NaCl + H2O
• The occurrence of the above reaction
decreases the current efficiency of chlorine
and sodium hydroxide production.
• To increase the current efficiency of Cl2 and
NaOH production the above reaction should
be prevented by placing a porous diaphragm
between the cathode and anoda to avoid
mixing of NaOH with dissolved Cl2.
 Electrolytic (ionic) Conduction
• The resistance of a cell of two parallel
electrodes separated by a distance L is
given by:
• R =  L/a
•  is defined as the resistance of 1 cm3 of the
electrolyte, a is the cross sectional area of
the solution in the cell
• (1/R) = (1/) (a/l)
• Cത = K (a/l)
• Cത is the conductance of the solution in ohm-1
(Cത =1/R)
• K is the specific conductance of the solution
in ohm-1cm-1, it is defined as the conductivity
of 1 cm3 of the electrolyte. K is the reciprocal
of the specific resistance  (K= 1/)
 Technical importance of the cell
resistance
• Knowledge of the cell resistance R is
essential for calculating the voltage lost in
the cell (IR) due to the internal cell
resistance, the voltage lost which is known
also as the ohmic drop constitutes a part of
the total cell voltage.
• Hence its knowledge is essential for
calculating the total cell voltage.  I = cell
current, R = cell resistance
• Knowledge of the cell resistance is also
essential for calculating the amount of
electrical energy converted into heat because
of the internal cell resistance (I2 R)
 Determination of  and K
• The specific resistance  and the specific
conductance K are determined
experimentally by the wheat stone bridge
shown in figure according to the following
steps
 A

Conductivity cell placed

in solution of unknown Resistance box
 or k R3
Ear phone

solution of unknown
 or k
R3 R4
B C

Platinum disc

~
A. C. Source
Conductivity cell
Wheatstone Bridge
• Calculate the cell resistance R1 from the
equation:
R1 R3
• =
R2 R4
• Since R2, R3 and R4 are known R1 can be
calculated
• Calculated  and K of the solution from R1
• R1 =  l/a
• If the cell constant (l/a) of the conductivity
cell is not known it should be determined by
repeating steps 1 to 4 using a solution of
known specific conductance e.g 0.01 N KCl
whose K is 0.141 ohm-1cm-1
 Factors affecting  or K
• Temperature, increase of solution
temperature leads to decreasing the specific
resistance and increasing the specific
conductance owing to the decrease in
solution viscosity with increasing solution
temperature.
• Nature of the ions present in the electrolyte,
the higher the ionic speed (ionic mobility) the
higher the specific conductance. Electrolytes
containing H+ or OH- have usually a high
specific conductance owing to the high ionic
speed of H+ and OH
• Electrolyte concentration: specific
conductance increase with increasing
electrolyte concentration, reaches maximum
then starts to decrease with further increase
in concentration. The initial increase in k with
electrolyte concentration is attributed to the
increase of the number of ions/cm3 which are
able to carry the electrical current.
• The decrease in k at relatively high
electrolyte concentration is attributed to the
decrease in the speed of the ions as a result
of the retarding force of interionic attraction
(f).
• The magnitude of the retarding force of
interionic attraction is given by Coulomb’s
law
q+ q−
• f=
∈d2
• Where q+ and q- are the charge of the cation
and anion respectively, d is the distance
between the cation and the anion, ∈ is the
dielectric constant of the solution. The above
equation shows that the retarding force
increases with decreasing d i.e. with
increasing electrolyte concentration.
-ve +ve
H2SO4

Retarding force of NaOH

k ohm-1.cm-1
interionic attraction

+ - MgSO4

Accelerating force of
attraction between the
cation and the cathode
Electrolyte concentration M