THROWING POWER AND COVERING POWER

OF AN ELECTROCHEMICAL REACTIONS

PREPARED BY: JAIMIN PANCHAL.V.

GUIDED BY: Dr.V.V.MATHANE SIR

Metallurgical & Materials Engineering Department, Faculty of Technology & Engineering, The M.S. University of Baroda, Vadodara

ELECTROLYTIC CELL & ELECTROLYSIS:

Electrolytic cell is reverse of electrochemical cell.current is supplied to carry out the chemical reactions.

Electrolytic cell consists of following four main components: (1) electrolyte (2) anode (3) cathode (4) external power supply
An electrolytic cell should be design to meet following requirement: (1) it should consume little energy per unit weight of metal. (2) it should have a high output for a small volume and working area. (3) it should be corrosion resistant to the electrolyte. (4)it should be resistant to heat.

ELECTROLYSIS may be defined as a process in which chemical reaction are brought about on the electrode in contact with an electrolyte by means of external electromotive force.

during electrolysis positive charged ions (cation) are attracted towards the negatively charged electrodes (cathode) while the negatively charged ions are attracted towards the positively charged electrodes (anode).

THROWING POWER:

The closeness with which the complete uniformity is approached in the deposit over the whole area of the cathode is assigned to a characteristic of system known as throwing power.

It describes the ability to balance the current density on different parts of cathode.

The throwing power is complex property and is influenced by many factors given below.

Primary current distribution : this expresses the way in

which the current varies over different parts of the surface.

In a working cell the concentration of the electrolyte immediately adjacent to the cathode is weaker than in the bulk of the solution due to incomplete replacement of the discharged ions. the concentration overpotential arises. Thus in corners and deep crevices, the combined effect of local high electrolytic resistance and concentration overpotential hinders the electrodeposition at these plates. There is another factor known as activation overpotential at the electrodes counteracting the effect of electrolytic resistance and concentration overpotential. As activation overpotential is dependent on current density, activation overpotential will be least in the recessed area and greatest on the prostrusions of the cathode , thus due to this factor there should be uniform deposition because current distribution is better than theoretical value.

The third factor is the cathode efficiency which may either increase or decrease with increasing current density . In the second case in the recessed area having lower density , the rate of deposition will be higher as compared to protrusions , increasing the tendency to have a uniform electrodeposit.

Thus throwing power is not specific or inherent property of a solution but is the resultant effect of the three factors mentioned above.

PHYSICAL FACTORS AFFECTING DISTRIBUTION OF METAL :

Position of the electrode in relation to each other and the plating tank : it should be properly controlled . Shape of the anode : the shape should follow the main contours of the cathode. Agitation : the electrolyte should be sufficiently agitated so as to minimize both local high electrolytic resistance and high concentration overpotential over recessed areas of the cathode. Temperature : the throwing power can also be improved by variation in the temperature .for example in case of chromium plating solution , the throwing power decreases slightly with rise in temperature.

CHEMICAL FACTOR :

Composition of electrolyte : the throwing power can be improved by altering the composition of the electrolyte. Greater is the difficulty to obtain the metal ion from the bath , greater is the throwing power.

For example by adding the h2so4 to cuso4 bath , because of common ion effect of so42- , the amount of cu ion in the solution is expressed and thus h2so4 increases throwing power.

ELECTRICAL FACTOR :

The solutions exhibiting higher cathode potentials have higher throwing power. From current density and current efficiency two cases may arise.

Case(1) : cathode efficiency may increase with increasing current density. Case(2) : cathode efficiency may decrease with increasing current density.

Solution of 2nd type will have a higher throwing power . A very good example is chromium plating solution , the throwing power of which is negative , and it is inferior to the majority of other plating solutions.

COVERING POWER :

It refers to the ability of the solutions to cover a cathode completely with deposited metal.

The term covering power should not be confused with covering power.

It is the ability of a solution to initiate metal deposition at low current density areas. It is the minimum current density at which the metal deposition will start to form and with a lower current density than the minimum , no point of the specimen will be plated.

THIS CHARACTERISTIC CAN BE CONTROLLED BY CONTROLLING THE FOLLOWING FACTORS

Attainment of deposition potential at low current density areas .

Concentration of metal ions in the solutions .

Over voltage of the metal .

over voltage of hydrogen on the basis metal : this differs for various metals. The covering power is favored in the order steel, brass, copper and nickel.

Presence of carbon : carbon has an adverse effect. This explains why high current densities are required for depositing chromium on cast iron surface.

Composition of the electrolyte : covering power can also be controlled by controlling composition of the bath. It has been seen that the throwing power is favored by high chromic : sulphuric acid ratio . but for covering power the reverse is true. For example for good throwing power the ratio accepted is 125:1 . But for covering passive surface such as nickel, ratios of 90:1 or even 75:1 are preffered.

Flashing the basis metal with metal of high over voltage : tin has higher over voltage than iron. Thus in the zinc plating process if malleable cast iron is flushed with tin , the higher hydrogen over voltage of tin will enable the zinc to cover the surface more completely including recesses.

pH value : covering power of acid baths is generally poor , covering power of alkaline bath is usually good .

Effect of roughness and polishing : better deposit on a rough surface can be obtained if the sharp points are rounded off by polishing . Any polishing operation which has the effect of removing high points will be advantageous.

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