Seminar: Current Efficiency and Its Control

Prepared by:
Dhairya Dixit Roll no.904 B.E VI Metallurgical and materials engineering Faculty of technology and engineering M.S.University Vadodara November 2011

Electrolytic Cell

Non-spontaneous electrochemical process occurs in an electrolytic cell i.e. free energy change is positive, G>0. Here, Electrical energy is converted into Chemical energy i.e. Current is supplied from external source to carry out chemical reactions. Electrolytic cells are used for all electrodepositing and dissolution processes.

Components and Parameters of Electrolytic cell

Components of electrolytic cell are:

1 Electrodes. (anode and cathode) 2 Electrolyte. (ionic conductors) 3 D.C power supply. 4 Wires. (electronic conductors)

Parameters of electrolytic cell are:

1 Current and current density. 2 Temperature, composition, pH value, state (moving or stationary) of electrolyte. 3 Potential required across the electrodes.

Electrolysis

Electrolysis can be defined as a process in which chemical reactions are carried out by the means of external electromotive force, on the surface of the electrodes. Electrolysis Anodic Electro-dissolution (exception Anodizing) Cathodic Electro-deposition.

Faradays Laws of electrolysis

First law: For a same electrolyte amount of substance liberated by electrolytic process is proportional to the quantity of electricity passed through the electrolyte. Statement: W=Zit.

Second law: Weight of various substances deposited by same quantity of electricity is proportional to its equivalent weight. Statement: W E.

Combined Statement of Faradays Law: W= Ait nF Here W=Weight of metal deposited. F=Faradays constant. i=Current. =96500coulomb. t=Time. n=valence electrons. A=Atomic mass E=Equivalent weight of atom. Z=Electrochemical equivalent

Deviations of Faradays Law

Faradays law, loses its significance in calculating the actual yield of metal deposited at an electrodes surface due to following deviations:
Mechanical losses. Evaporation losses. Dissolution of electrodes. Formation of compounds at electrodes. Discharge of other ions near the surface of electrodes. Regeneration of primary products.

Current Efficiency is the term which reflects the deviations of Faradays laws.

Current Efficiency

Current Efficiency can be defined in two ways It is the ratio of theoretical quantity of current required for particular reaction to the actual amount of electric current consumed (to deposit the same amount of metal). C.E.= theoretical amount of electricity required actual amount of electricity consumed

It is the ratio of actual amount of metal deposited to the theoretical amount of metal deposited for the same amount of current. C.E.= actual amount of metal deposited theoretical amount of metal deposited

Classification
Current Efficiency Anodic C.E.

Cathodic C.E.

Cathodic and Anodic Current Efficiencies need not be same, but they become identical as loses of electrolysis product reduces to minimum. Both can be > 100% but can never be <0%.

Factors affecting current efficiency

Temperature. Current Density. Separation between electrodes. Composition of electrolyte. Current distribution over electrode. Solubility of metal in electrolyte. Electrode material and shape.

Temperature:
Rise in temperature leads to decrease in current efficiency due to following reasons: -With increase in temperature metal electrodes solubility into electrolyte increases. -Also chemical reactions of product and electrolyte occurs at high temperatures i.e. recombination of products and formation of original salts.

Current Density:
Current efficiency decreases with increase in current density. But in some cases polarization increases with increase in current density and this in turn improves the current efficiency as the amount of desired deposited product increases

Separation Between electrodes:

Wider the separation i.e. greater the distance between electrodes more will be the current efficiency. As the distance between electrode increases chances of recombination of product decreases.

Current distribution over electrode:

Uniform current distribution over the electrode area increases the current efficiency.

Solubility of metal in electrolyte:

As solubility of meta in electrolyte increases, Current efficiency decreases.

Composition of electrode:
Current efficiency also depends up to certain extent upon the composition of electrolyte. For example: During electrolysis of fused MgCl2 , current efficiency increases with % MgCl2 only up to certain extent after which current efficiency starts decreasing.

Electrode Material:
Current efficiency can decrease or decrease depending upon the material. For example: In electro-deposition of Cr from chromic acid, Current efficiency is near to zero when we use Pb as anode. But when Cr is used as anode current efficiency is more than 100%.

Steps to increase Current efficiency

The temperature should be as low as possible or electrolysis must be carried out at minimum required temperature. Electrolysis must be carried out at minimum required current density. Separation between anode and cathode must be more. Electrolyte of suitable composition must be used. Solubility of metal in electrolyte should be as minimum as possible and solubility can be decreased by addition of certain salts in electrolyte. Current distribution must be uniform over the entire cross-section of electrode and hence electrodes shape must be adequate. Adequate electrode material must be selected. Mechanical and evaporation losses of the deposited metal must be minimized. Current losses must be minimized by using electrolytes in which discharge of ions (like Hydrogen ions) near the surface of electrode is minimum

References:

Corrosion Engineering.( By Mars Fontana) Introduction to Electrometallurgy.( By Sharan and Narain) www.corrosiondoctor.com Wikipedia

Thank You