Chapter 3:Basic Principle of electro deposition

Basic Principle of electro deposition

• Electrodeposition, a short version of electrolytic deposition, is
the conventional process of coating a thin layer of one metal
on top of a different metal to modify its surface properties.
• Based on the principle of electrolysis, it is a process that uses
electrical current to reduce the cations of a desired material
from an electrolyte and coat those materials as a thin film onto
a conductive substrate surface.
• This is done to achieve the desired electrical and corrosion
resistance, reduce wear and friction, improve heat tolerance
and for decoration.
• Hence the surface properties of a material can be tailored and
new materials for a variety of applications can be explored
through this technique.
 Cont’d
• Consits of
 Electolyte containg metal ion
 Elctrode or substrate on which the deposit is desired
 Counter Electrode
• When a current folw throught the electrolye, the cations and
anions move towards the cathode and anode respectively
and may deposit on the electrode after going a charge
transfer reaction.
• The deposit of the metal at the electrode requires an electron
so that the rate of deposition depends on electron flow that
is from rectifier.
• The thickness of the deposit, there fore depends on the
current and the length of time the current is applied.
 Cont’d
• This is the result of Farady's law of elctrolysis which relate
weight of the substance by anode or cathode reaction during
electrilysis as being directly proportional to the quntity of
electricity passed through the cell. Michael Faraday
discovered a quantitative relationship between the extent of
electrolysis and the quantities of electricity passed and put
forward two laws.
 Cont’d
• The production of chemical changes by passing and
electric current through a solution or molten salt
(electrolyte) resulting in the migration of ions to the
electrode: positive ions (cations) to the negative
electrode(cathode) and negative ions (anions) to the
positive electrode (anode).
• During electrolysis, the ions react with the electrode,
either receiving or giving up electrons. The resultant
atoms may be liberated as gas or deposit as a solid on
the electrode, in amount that are proportional to the
amount of current passed
 Cont’d
• If negative ions move towards the anode they lose
electrons and become neutral, resulting in an oxidation
reaction. If positive ion move towards the cathode and
gain electron becoming neutral. A reduction reaction
takes place.
 Cont’d
• In an electrolytic cell, a non-spontaneous redox reaction
is made to occur by pumping electrical energy into the
system.
- DC Source
+
Could be Voltaic
cell

+ ANODE
CATHODE 
Oxidation occurs at the
Reduction occurs at the
anode
cathode
X  X + e 
M +e M
+ 
Cont’d
 Cont’d
• Electrolysis is used for many purposes, including the
extraction of metals from ores, the cleaning of
archaeological artefacts, and the coating of materials
with thin layers of metals.
 First law
• It states that the mass of a substance liberated at the
electrode is directly proportional to the quantity of
electricity passed through the electrolyt

• Where z: is the constant calledelectrochemical

equivalent
• I: is the current in ampere and
• t: is the time in seconds.
 Second law
• States that, when the same quantity of electricity is
passed through different electrolytes the masses of
substances formed at theelectrodes are proportional
to their equivalent masses
 Current Efficiency
• Current efficiency is the ratio between the actual amount
of metal depositing (or dissolved) (Ma) to that
calculated theoretically from Faraday’s law (Mt) in %.
• C.E. = (Ma/ Mt) x 100, C.E. indicates the faction of
total current that generates desired products. The overall
amount of chemical change produced by a given
quantity of electricity can be determined.
• Cathode & anode efficiencies -In an ideal situation,
cathode efficiency will be equal to anode efficiency
 Cont’d
• The ratio of the weight of metal actually deposited to
the weight that would have resulted if all the current
had been used for depositing it is called the cathode
efficiency.
• Cathode efficiency in plating depends on:
 Electrolyte or bath Concentration of chemical
component
 pH and agitation
 Current density.
• The current efficiency in Ni plating is close to 100%,
and in Cr plating it is approximately 20%
 Energy Efficiency
• On account of secodary reactions, the volatge actually
for depositionis or libration oe metal is higher than the
theoretical value which increases the actuall energy
required.
TheoreticalEnergy *100
• Energy Efficeincy = ActualEnergy Re quired
Influencing factors in Electro deposition
• The morphology and composition of electrodeposits
vary significantly, and depend on:
 Current density
 The nature of the anions or cationsin the solution Bath
composition and temperature
 Cathodic efficiency
 Temperature
 Agitation
 Solution concentration
 Physical & chemical nature of substrate surface
 Throwing power of elcetrolyte
 Current Density
 It is the application of current (Amperes) per unit area
 Current density for a particular bath are defined on the
basis of bath composition and required deposition
thickness and deposition rates
 Selection of current density is critical as poor selection
will result in defects in deposition quality like porosity,
poor deposition thickness
 Areas of the parts to be plated, must carefully be
calculated and current densities be selected according
 Cont’d
• At low values of current density the ions are released at a slow rate
and the rate of growth of nuclei is more than the rate at which the
new nuclei form themselves.
• Electro-deposition depends upon the rate at which crystals grow
and the rate at which fresh nuclei are formed.
• Therefore, at low current densities the deposit will be coarse and
crystalline in nature.
• At higher values of current density the quality of deposit becomes
more uniform and fine-grained on account of the greater rate of
formation of nuclei.
• If the current density is so high that it exceeds the limiting value for
the electrolyte hydrogen is released and spongy and porous deposit
is obtained
 Cathode Efficiency
• The ratio of the weight of metal actually deposited to
the weight that would have resulted if all the current
had been used for depositing it is called the cathode
efficiency
 Cathode efficiency in plating depends on:
 Electrolyte or bath
 Concentration of chemical composition
 pH and agitation
 Current density
Effects of poor Cathode Efficiency
• If any of the depending factors are disturbed then
cathode efficiency will adversely suffer and result in:
• Poor deposition
• Process will be less cot effective in terms of electricity
consumption, solution composition and early anode
dissolution.
 Temperature
• The temperature of the electrolyte has two contradictory
effects.
• One, at comparatively high temperature there is more
diffusion and even at relatively high current density smooth
deposits may be produced.
• Two, the rate of crystal growth increases the possibility of
coarse deposits.
• At moderate temperatures the deposits are good.
• In chromium plating the temperature is maintained at
35°C, and in nickel between 50°C to 60°C
 Agitation
• In a plating solution
 near the cathode, as metal is depleted, the solution
becomes less dense and tends to rise along the face of
cathode
 Opposite occurs at the face of anode: solution tends to
stream down
 The solution is required to be agitated for homoginaty
• This problem, if not catered (through agitation) wherever
required, will cause
 non-uniform deposition of metal on the substrate
 Cathode efficiency will greatly suffer
 Bath Composition and Solution
Concentration
• Electrolitic concentraion
• Nature of Electrolytes
• Aditional agents
 Electrolytic Concentration
• This is more or less complementary to the first factor,
i.e. current density, since by increasing the oncentration
of the electrolyte higher current density can be
achieved.
• Increase of concentration tends to give better deposits
and some people therefore favour it.
 Addition Agents
• The quality of a deposit is improved by the presence of
an addition agent which may be colloidal matter or an
organic compound, otherwise the metal deposits in the
form of large crystals and the surface becomes rough.
Materials used as addition agents are gelatin, agar, glue,
gums, rubber, alkaloids, sugar etc.
• The addition agents are supposed to be absorbed by
crystal nuclei and prevent their growth into large
crystals.
• The discharged ions start to build up new nuclei and the
deposit of metal is fine-grained
 Nature of electrolyte
• Smooth deposits are obtained from solutions having
complex ions, e.g.,cyanides. Silver from nitrate solution
forms a coarse deposit while from cyanide solution it
forms a smooth deposit.
• Therefore, the formation of smooth deposit largely
depends upon the nature of electrolyte used .
 Throwing Power
• The throwing power of an electrolyte may be regarded as
the quality which produces a uniform deposit on a
cathode having an irregular shape.
• Since the shape is irregular, The distance of the various
parts of the cathode from the anode is not the same and
therefore the conductance of the electrolyte is not the
same for all parts of the cathode.
• The phenomenon of throwing power has not been clearly
understood so far.
• In an electrolyte of low conductance, the current will
concentrate on the parts of the cathode which are nearer
the cathode resulting in poor throwing power.
 Cont’d
• If the electrolyte has good conductance, the throwing
powerwill also be good.
• One way to improve the throwing power is to keep a
good distance between the cathode and the anode
thereby providing more or less the same conductance
for all parts of cathode.
• Presence of colloidal matter improves the throwing
power but increase of temperature may produce the
opposite effect.
 Over potential and overvoltage
 Overpotential is the difference in the electrode potential of an
electrode between its equilibrium potential and its operating
potential when a current is flowing.

 The over potential represents the extra energy needed to force the
electrode reaction to proceed at a required rate (or its equivalent
current density).

 Consequently, the operating potential of an anode is always more

positive than its equilibrium potential, while the operating potential
of a cathode is always more negative than its equilibrium potential
 Cont’d
 Overvoltage is the difference between the cell voltage (with a current flowing)
and the open-circuit voltage (OCV). The overvoltage represents the extra
energy needed to force the cell reaction to proceed at a required rate.

 Consequently, the cell voltage of an electrolytic cell is always more than its
OCV, while the cell voltage of a galvanic cell (e.g., a rechargeable battery
during discharging) is always less than its OCV.
 Occasionally, it is also referred to as polarization of the cell. The overvoltage
is the sum of the overpotentials of the two electrodes of the cell and the ohmic
loss of the cell. Unfortunately, the terms overvoltage and overpotential are
sometimes used interchangeably.
Solved Examples of Faraday’s law
1. What current will deposit 0.155g of silver from a
solution of silver ions in 11.0 minutes ( 660 seconds)?
Ag+(aq) + e  Ag(s)

# moles silver produced = 0.155g  108 g/mol = 1.44  10-3

mol
# moles of electrons = 1.44  10-3 mol
Total charge = 1.44  10-3 mol  96500 Coulombs/mol = 139C

• Current = Charge (Coulombs)  time (seconds)

• Current = 139C  660 seconds = 0.211 Amps
 Cont’d
2. How much copper will be deposited if a current of
0.150A is passed through a solution of copper sulfate for
20.0 minutes?
Cu2+(aq) + 2e  Cu(s)
Two moles of electrons will be required to deposit each mole of
copper
• Total charge (C) = current (A)  time (s)
= 0.150A  1200s = 180 C
• # moles (Faradays) = 180 C  96500 C/mol = 1.87 x 103 mol
• #moles of copper deposited
= ½  1.87  103mol = 9.33 x 104mol
• Mass of copper = 9.33 x 104mol  63.5 g/mol
= 5.92  102g
Thank You