ELECTROCHEMISTRY

PREPARED BY:
Dr. ARCHANA P. DAS
ASST.PROFESSOR
MBCET
 TYPES OF ELECTRODES
1. Metal/Metal ion electrode(M/Mn+ )
2. Gas electrode
3. Metal/Insoluble metal salt/ common ion
electrode
4. Redox electrode
5. Ion Selective membrane
1. Metal/Metal ion electrode(M/Mn+ )
• Metal immersed in respective metal salt
solution.
• Electrode potential depends on logarithm of
concentration of the metal ion.
• Eg. Zn/Zn2+ , Cu/Cu2+ etc
2. Gas electrode
• Gas is passed through an inert electrode like
Pt which is immersed in a solution containing
its own ions.
• Eg. Hydrogen electrode (SHE)
• Electrode potential depends on two factors:
 Logarithm of concentration of the ions
 Pressure at which the gas is bubbled.
3. Metal/Insoluble metal salt/ common ion
electrode
• Metal covered with a paste of its insoluble
metal salt.
• In contact with a solution containing a common
ion with the insoluble salt.
• Eg. Calomel electrode
• Electrode potential depends on the logarithm of
concentration of the common ion.
4. Redox electrode
• An electrode like Pt is in contact with a redox
system.
• Eg. Pt/Fe2+/Fe3+
• Electrode potential depends on the ratio of
logarithm of concentration of all the ionic
species involved in the redox reaction.
5. Ion Selective membrane
• Sensing part of the electrode is usually an ion-
specific membrane.
• Membrane can be glass membrane, crystalline
membrane and ion-exchange resin
membrane.
• Eg. Glass membrane
 STANDARD HYDROGEN ELECTRODE(SHE)

• Standard reference electrode.

• Gas electrode.
• Potential taken as zero.
• Consists of an inert Pt electrode dipped in 1M
H+ solution, in contact with hydrogen gas at
1atm pressure, at 298K.
• Electrode representation:
Pt/H2(g) 1 atm /H+(1M)
• Reversible electrode.
• Can act as anode or cathode depending on the
electrode to which it is coupled.
• Cathode (Reduction): H+ + e-  ½ H2 (g)
• Anode (Oxidation): ½ H2 (g)  H+ + e-
MEASUREMENT OF ELECTRODE POTENTIAL USING SHE

Zn/Zn2+//H+(1M)/H2 (1atm)/Pt
E0 cell = E0 cathode – E0 anode
= E0 SHE – E0 Zn/Zn2+
Since E0 of SHE is zero,
0.76V= 0- E0 Zn/Zn2+
E0 Zn/Zn2+ = -0.76V
 LIMITATIONS OF SHE
• Very cumbersome to set up.
• Requires considerable volume of solution.
• Can be poisoned by compounds like Hg, As, S,
MnO4- etc.
• Cannot be used in solutions containing redox
systems.
• Difficult to maintain pressure of H2 gas at 1atm.
• Difficult to maintain the concentration of 1M HCl.
 CALOMEL ELECTRODE
• Calomel is the insoluble compound Hg2Cl2 .
• Secondary reference electrode.
• Most commonly used electrode.
• Consists of a glass tube at the bottom of which a
small amount of Hg is placed.
• Covered with a paste of solid mercurous chloride.
• Further in contact with a solution of KCl.
• Pt wire dipped into the Hg layer is used for
making electrical contact.
• Side tube is used for making electrical contact
with a salt bridge.
• Electrode representation:
Hg/ Hg2Cl2(s) / KCl
• Electrode reaction:
Hg2Cl2(s) + 2e-  2Hg(l) + 2Cl-(aq)
• Can act as anode or cathode depending on the
electrode to which it is coupled.
• Nernst equation for calomel electrode is:
Ecal = Eocal - (2.303RT/2F) log [Cl-]2
= Eocal - (2.303RT/F) log [Cl-]
Eocal = 0.2422V
 GLASS ELECTRODE

• Ion-selective electrode.
• Made of doped glass membrane sensitive to a
specific ion.
• Consists of low melting glass having high
electrical conductivity.
• Composition of Na2O in this glass is slightly
more than ordinary soda glass.
• Universally employed electrode for pH
measurement.
 H + ION SELECTIVE GLASS ELECTRODE

• Consists of low melting glass having high

electrical conductivity.
• Long glass tube with a thin glass
bulb filled with 0.1M HCl.
• Inner surface of glass in contact
with AgCl coated silver electrode or a Pt
contact electrode.
• HCl in the bulb furnishes a constant H+ ion
concentration.
• The glass membrane functions as an ion-selective resin.
• An equilibrium is set up between the Na + ions of glass
and H+ ions in solution.
• H+ + Na+ (glass)  Na+ + H+ (glass)
• For a particular type of glass, the potential difference
varies with the H+ ion concentration of the test
solution.
• Nernst equation for glass electrode :
EG = E0G + 0.0591 log [H+]
- log [H+] = pH
EG = E0G - 0.0591 pH
E0G is a constant for a particular variety of glass.
 POTENTIOMETRIC TITRATIONS
• Important application of EMF measurements.
• The change in electrode potential upon the
addition of titrant is noted.
• Volume of titrant added is plotted against
EMF.
• Rate of change of potential is maximum at the
end point.
 ACID-BASE TITRATIONS
• Neutralization of acid and base is
accompanied by change in concentration of H+
and OH- ions .
• Any electrode whose potential depends on H+
concentration can be used as indicator
electrode. (Hydrogen electrode, glass
electrode etc).
• SCE is usually reference electrode.
• If hydrogen electrode is used as indicator
electrode and SCE is the reference
electrode,then cell representation is:
Pt/H2(g) 1 atm /H+(C=?) // KCl (sat) / Hg2Cl2(s) / Hg
Ecell =E –E
calomel hydrogen

• A known volume of acid taken in beaker

• hydrogen electrode immersed
• coupled with SCE through salt bridge and
digital voltmeter.
• EMF measured after each addition of base from
burette.
• EMF plotted against the volume of base added.

• As titration proceeds, concentration of H+

decreases and pH increases.
• Hence EMF of cell increases.
• Change is slow at first and rapid at the end
point .
 REDOX TITRATION
•Indicator electrode is an inert metal such
as Pt wire immersed in a solution
containing both oxidised and reduced form
of the same species.
•Electrode act as a redox electrode.
•This redox electrode is then combined
with reference calomel electrode to form a
cell.
 CORROSION
•Process of disintegration or deterioration of a metal by chemical or
electrochemical reaction with the environment.
Eg: Rusting of iron, tarnishing of silver etc.
• Metals are converted to metallic compounds at the surface.
•These compounds wear away as corrosion products.
Cause:
•Metals occur in nature in their thermodynamically stable state as
oxides, sulphides, carbonates, chlorides, silicates etc.
•Pure metals are extracted from these ores after expending a lot of
energy
•These metals will be at a higher energy state than its ore.
•These metals will have a natural tendency to revert back to its
thermodynamically stable state. This results in corrosion.
 MECHANISM OF CORROSION

• Corrosion can be explained by two main

theories:
• Dry or chemical corrosion
• Wet or electrochemical corrosion
 WET/ELECTROCHEMICAL CORROSION

• Takes place under moist conditions

• Occurs when a conducting liquid is in contact with a metal
OR
• when two dissimilar metals are immersed or dipped partially in a solution.
• Separate anodic and cathodic areas are formed .
• Oxidation occurs at the anode generating metallic ions and electrons.
• These electrons move through the conducting medium called corrosion
current.
• Reduction takes place at the cathode where dissolved constituents in the
conducting medium accepts the electrons and form non-metallic ions like OH -,
O2-.
• Metallic and non-metallic ions diffuse towards each other through the
conducting medium resulting in the formation of corrosion product
somewhere between anodic and cathodic areas.
 MECHANISM
• Cathodic reaction depends on nature of environment and can proceed in two ways:
• Hydrogen evolution type
• Oxygen absorption type
HYDROGEN EVOLUTION TYPE CORROSION
• Occurs when base metals are in contact with acidic solution in the absence of
sufficient oxygen concentration.
• Cathodes are small areas and anodes are usually large areas.
• Displacement of H+ from acidic solution by metal ions takes place.
• Eg: Fe in contact with HCl
• At anode:
Fe Fe2+ + 2e E0 = -0.44V
• At cathode:
2H+ + 2e  H2 E0 = 0V
• The net reaction:
• Fe + 2H+  Fe2+ + H2
 Hydrogen evolution corrosion in alkaline medium

• Hydrogen electrode potential in alkaline medium is

E0 = -0.828V.
• If the potential of the metal electrode is lower than that of
hydrogen electrode, only then hydrogen evolution will take
place in alkaline medium.
• Will not take place for iron (E0 = -0.44V) in alkaline medium
but possible for aluminium (E0 = -1.66V )
 OXYGEN ABSORPTION TYPE CORROSION
• Occurs when base metals are in contact with water having dissolved oxygen
in neutral or slightly alkaline medium.
• Eg: Rusting of iron.
• Surface of iron is usually coated with a thin film of iron oxide which may
become porous or develop cracks and get exposed. These areas become
anodic and the remaining metal parts behave as cathode.
• At anode:
• Fe Fe2+ + 2e E0 = -0.44V
• At cathode:
• 1/2O2 +H2O + 2e  2OH- E0 = +1.23V
• The liberated ions diffuse and combine to form the corrosion products.
• Fe2+ + 2OH-  Fe(OH)2
• In the presence of excess oxygen :
• 2Fe(OH)2 + ½ O2  Fe2O3.2H2O (Yellow rust)
• In the presence of limited oxygen:
• 3Fe(OH)2 + ½ O2  Fe3O4.3H2O (Black rust)
 GALVANIC SERIES:

• A series in which the metals and alloys are arranged in the

order of their corrosion tendencies
• A metal high in the series is more anodic and undergoes
corrosion faster
• Guide for selecting metals and alloys that can be joined to
make an engineering product
• Also known as electro potential series
• More practical series
• Give real and useful information regarding the corrosion
behaviour of metals and alloys in a given environment
COMPARISON OF ELECTROCHEMICAL AND GALVANIC SERIES:
 CATHODIC PROTECTION
• The metal to be protected is forced to behave
as the cathode so that corrosion is prevented.
• Cathodic protection can be done in two
different ways:
• Sacrificial anodic protection or galvanic
protection
• Impressed current cathodic protection
 SACRIFICIAL ANODIC PROTECTION:

• Metallic structure to be protected is connected by a wire to a

more anodic metal.
• Anodic metal sacrifices and undergoes corrosion.
• Metals like Mg, Zn, Al and their alloys are used as sacrificial
anodes.
APPLICATIONS
Protection of
• buried pipelines
• Underground cables
• Marine structures
• Ship body
IMPRESSED CURRENT CATHODIC PROTECTION:
• An impressed current is applied to convert the
corroding metal from anode to cathode.
• An inert material like graphite is used as anode.
• A direct current from a DC source is applied to the
anode and the metal to be protected.
• APPLICATIONS
• Open water box, coolers, water tanks, buried
pipelines, condensers etc
• Concrete buildings, bridges and similar
structures
• Vessels, pipelines and tanks used to store or
transport liquids
• Protection of harbors, offshore structures etc
 ELECTROLESS PLATING
• Non-galvanic plating method
• Chemical, autocatalytic , metal coating process without the use of
electricity
• The reaction is accomplished when hydrogen is released by a
reducing agent, normally sodium hypophosphite (the hydrogen leaves
as a hydride ion) thus producing a negative charge on the surface of
the part.
• Electroless plating allows a consistant metal ion concentration to
bathe all parts of the object.
• Deposits metal evenly along edges, inside holes and over irregularly
shaped objects which are difficult to plate evenly with electroplating.
• Electroless plating is also applied to deposit a conductive surface on a
nonconductive object to allow it to be electroplated.
• Also known as chemical plating or autocatalytic plating.
• Numerous consumer goods are coated by this method to create
durable and attractive surfaces.
• Advantages:
• Does not use electrical power
• Even coating
• Improved resistance to corrosion
• Flexibility in plating volume and thickness
• Chemical replenishment monitored automatically
• Complex filtration method is not required
• Matte, semi-bright or bright finishes available
 APPLICATIONS
• Plating of printed electronic circuits
• Coating optical surfaces, door knobs, kitchen
utensils, bathroom fixtures etc
• Numerous consumer goods coated by this
method to create durable and attractive
surfaces
 ELECTROLESS NICKEL PLATING
• Nickel sulphate salt and hypophosphate reducing agent
taken in a furnace
• Buffer and complexing agent added
• Air agitation applied
• Catalytic surface to be plated is introduced and heated

• NiSO4 + NaH2PO2.H2O  Ni (plating) + NaHPO3 +H2SO4

• Base metal usually used are iron, steel, aluminium etc .

• Not as bright as electroplating
• easy to solder but difficult to weld.
 ELECTROLESS COPPER PLATING
• Cupric sulphate, formaldehyde (reducing
agent), buffer and complexing agents are
taken in the plating bath.
• Catalysed by an active palladium surface
• 2HCHO + 4OH-  H2(gas) + H2O2 + e
• Cu2+ + 2e  Cu (metal plating)
• Commonly used to render conductivity for
electronic and printed circuit boards
Thankyou