Chemistry

Department

CHM 4283
Assignment topic
0
Decomposition Potential
Decomposition Potential

Instructor: Mam Fatima Jabbar

Group Members
Usman Ghani-62 Section: CF3-17
Sajjad Ur Rehman-52 Submission Date: 18th Jan
Faseehullah-70 Due Date: 18th Jan
Soha Israr-55
Mohsina Irshad-69
 Decomposition potential / (decomposition voltage):
When electrolysis is administered, the products of electrolysis accumulate around the
electrodes. This causes a change in concentration around the electrodes and an opposing emf
(called back emf) is produced. For example, when a potential is applied between two platinum
electrodes dipping in dil. the Sulphuric acid solution, at once the electrolysis of water starts
evolving hydrogen and oxygen. But electrolysis halts very soon, because of back emf (produced
by the adsorption of evolved gases on the surface of two electrodes) is greater than the applied
voltage. Now if we increase the applied voltage slowly, the electrolysis proceeds smoothly, when
the applied voltage just exceeds the rear emf. Thus, decomposition potential is adequate to back
emf.

Factors affecting decomposition potential:

The magnitude of decomposition Voltage of the electrolyte depends upon:

 Nature of electrolytes
 Nature of electrodes
 Temperature
 Concentration of electrolytes
 Nature of product of electrolysis
1 Decomposition Potential
Definition: The minimum potential which must be applied between the 2 electrodes immersed
within the given electrolytic solution to cause continuous electrolytic decomposition is named
decomposition potential.

Measurement of Decomposition Potential:

The decomposition voltage / Potential can be determined using an electrolytic cell shown
in Figure 1.

Figure 1-Electrolytic Cell

 The cell consists of two platinum metal electrodes immersed in the electrolyte. The
voltage is varied by moving the contact maker D along with the wire AB and the current passing
through the cell is measured using an ammeter (A).

If a dilute solution of an acid or base is taken within the cell, at low voltages no reaction
is found to occur and there's a slight/little bit increase within the current. On increasing the
potential slightly above 1.7V, a sudden evolution of H2 and O2 at the electrodes is observed. this
is often amid an abrupt increase within the current. The applied voltage of 1.7V is that the
decomposition voltage for dilute acids and bases.

When current is plotted against voltage, a curve of the sort shown in Figure-2 is obtained

2 Decomposition Potential
Figure 2-Curve Showing Decomposition Potential

It is clear from the figure that the rise in current in proportion to the voltage occurs only after a
particular potential (decomposition potential). If the voltage is increased further, the current
value also increases. Below the decomposition potential the rise in current only marginal
indicating that no electrolysis is happening.

Ed = E cathode – E anode
The decomposition potential of an electrolyte process is of the same magnitude as the emf set up
by the cell resulting from electrolysis. This is illustrated with ZnI2 system figure-3.

Figure 3-ZnI2 Electrolysis

 If a 1 Molar solution of ZnI2 is electrolyzed in an electrolytic cell such as that shown in
Figure1, zinc and iodine are liberated at the electrodes. For this concerned electrolysis, the
decomposition voltage is found to be around 1.30Volt. The products formed accumulate on the
electrodes and result in the setting up of the following cell.

Zn | Zn2+ | I2 | I-
This exsert / put a back emf and offers resistance to the flow of current until the applied
voltage overcomes the back emf. To put it another way, the magnitude of the back emf should be
the same as the Ed. The emf of the above cell is given below

E = ER - EL

E = E iodine - E Zinc

= 0.54 – (-0.76)

= 1.30V
Thus, the cell emf (back emf) is a con to the applied voltage. the rear emf arises from the buildup
of zinc and iodine on the electrode surface. To pass the current through this cell, the applied
voltage must be exceeding the back emf of 1.30V. The cell emf is therefore adequate to the
3 decomposition voltage Ed which is experimentally found to be 4.30V for Decomposition
Zn and iodine Potential
cell.

Significance of decomposition Voltage:

Decomposition potential plays a very important role in the following Domains

 Electroplating:
The minimum potential required for electroplating of metal under a given set of
bath conditions is understood by decomposition potential.
 Separation of metals:
A solution containing copper and zinc ions are often separated by electrolysis.
Since the decomposition potential of copper metal is low (1.2V), so at this voltage, only
copper metal is deposited. When all copper is deposited, zinc ions get deposited later at a
better decomposition potential (2.55V).
 Refining of metals:
A particular metal can be made to get deposited on the cathode by applying a
potential equal to its decomposition potential (electrolytic refining).