Engineering Chemistry – CHM 1071

Dr. Maddasani Srinivasulu (MS)

s.maddasani@manipal.edu

1 March 2023 CHM - 1071 1

 My Classes

Wednesday 3.30 pm – 4.30 pm

Saturday 10.30 – 11.30 am

1 March 2023 CHM - 1071 2

 Contents

• Electrochemistry
• Corrosion and Control
• Modern methods of Chemical Analysis
• Chemical Fuels / Water Technology
• Materials Chemistry

1 March 2023 CHM - 1071 3

 Reference books
Jain P.C. Jain M.
Engineering Chemistry. 16th Edn., Dhanpat Rai and Sons,
New Delhi (2015)
Gadad R. V., and Shetty A. N.,
Engineering Chemistry
Kuriacose J.C., Rajaram J.,
Chemistry in Engineering and Technology, Vol. I & II ,
Tata Mc. Graw-Hill, New Delhi (2001)
Fischer T.
Materials Science for Engineering Students, Academic
Press, London (2009)
1 March 2023 CHM - 1071 4
 Course outcomes

• Describe the fundamentals of electrochemistry

and apply it in battery technology and other
energy sources
• Apply the principles of various analytical
chemical methods
• Identify the corrosion types and demonstrate
the corrosion control techniques
• Predict the applications of various modern
engineering materials by analyzing their
properties
1 March 2023 CHM - 1071 5
 Engineering Chemistry Lab (CHM 1061)
1. Alkalimetric titration
2. Total hardness of water
3. Estimation of percentage of copper in brass
4. Estimation of weight of iron in haematite
5. Estimation of percentage of manganese dioxide in pyrolusite
6. Estimation of ammonia nitrogen in a fertilizer
7. pKa value of a weak acid by potentiometric titration
8. Conductometric acid-base titrations
9. Determination of concentration of copper using colorimer
10.Determination of coefficient of viscosity of liquid.
11.Chloride content of water
12.Analysis of lead pigment
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 Assessment Plan

Engineering
Chemistry
(CHM 1071)
In Semester 50%
End Semester 50%

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 Electrochemistry - contents
• Introduction
• Electrochemical Cells
• Representation of galvanic cells
• Electromotive Force
• Single Electrode Potential
• Liquid Junction Potential & Salt Bridge
• Calomel Electrode & Glass electrode
• Batteries – 10 & 20
• Lead acid, Ni-Cd and Li ion batteries
• AFC & PEM fuel cells
• Metal finishing – Electroplating, factors, electroplating
of Cu and Cr, electro-less plating of Cu.
1 March 2023 CHM - 1071 8
 Electrochemistry

Electrochemistry is a branch of chemistry which deals

with the properties and behavior of electrolytes in
solution and inter-conversion of chemical and electrical
energies

1 March 2023 CHM - 1071 9

 Electrochemistry

• Electrochemical cell:
A single arrangement of two electrodes in one or
two electrolytes which converts chemical energy
into electrical energy or electrical energy into
chemical energy

• Classification:
 Galvanic Cells / Voltaic cells
(Chemical to electrical)
 Electrolytic Cells (Electrical to Chemical

1 March 2023 CHM - 1071 10

 Electrochemistry
GALVANIC CELLS:
It is an electrochemical cell that produces electricity as a
result of the spontaneous reaction occurring inside it

Galvanic cell generally consists of two electrodes dipped

in two electrolyte solutions which are separated by a
porous diaphragm or connected through a salt bridge.
Example: Daniel cell

1 March 2023 CHM - 1071 11

Galvanic Cell - Daniel Cell

https://youtu.be/xDITrdbajAs
Galvanic Cell - Daniel Cell
 Electrolytic cell

An electrolytic cell is
an electrochemical cell
in which a non -
spontaneous reaction
is driven by an
external source of
current although the
cathode is still the site
of reduction, it is now
the negative electrode
whereas the anode, the
site of oxidation is
positive.

1 March 2023 14
CHM - 1071
 Electrolytic cell

https://youtu.be/HQ9Fhd7P_HA
1 March 2023 CHM - 1071 15
 Comparison
Differences:
Galvanic cell Electrolytic cell
Cell reaction is spontaneous Cell reaction is non-spontaneous

Converts chemical energy into Converts electrical energy into

electrical energy chemical energy
Anode is (-)ve; Cathode is (+)ve Anode is (+)ve; Cathode is (-)ve
Two electrodes and two Two electrodes and single
electrolytes electrolyte
Used as a portable source of Used for electrolysis
electrical energy in cars, flash applications like electroplating
lights and calculators (Au), electroanalysis (Ni),
electrorefining (Cu)
e.g., Daniel cell e.g., electroplating of Ni
1 March 2023 CHM - 1071 16
 Comparison
Similarities
• Involves oxidation at anode and reduction at cathodeI
• Equivalent oxidation & reduction in the separate
regions
• Electrons flow from anode to cathode in the external
circuit
• Reactions occur on electrode surface only

1 March 2023 CHM - 1071 17

 Electrochemistry
Anode:
• Electrode at which oxidation occurs
• is where electrons are produced
• is what anions migrate toward
• has a negative sign

Cathode:
• Electrode at which reduction occurs
• is where electrons are consumed
• is what cations migrate toward
• has a positive sign
Oxidation is losing electrons, reduction is gaining electrons; OIL RIG
1 March 2023 CHM - 1071 18
 Representation of a galvanic cell

• Anode Representation:
Zn│Zn2+ or Zn;Zn2+
Zn│ZnSO4(1M) or Zn;ZnSO4(1M)

• Cathode Representation:
Cu2+│Cu or Cu2+;Cu
Cu2+(1M);Cu or CuSO4(1M)│Cu

• Cell Representation:
Zn│ZnSO4 (1M) ││ CuSO4(1M)│Cu

1 March 2023 CHM - 1071 19

 Galvanic Cell - Daniel Cell
Two different ways to construct the galvanic cells

With porous diaphragm With salt bridge

20
 Liquid Junction potential

With Porous disc

• Difference between the
electric potentials
developed in the two
solutions across their
interface .
• Ej = Ø soln, R − Ø soln,L
Eg: Contact between:
 Two different electrolytes
(ZnSO4/ CuSO4).
 Same electrolytes of
different concentrations.
 Salt Bridge - Elimination of LJP
A device that permits electrical contact between two solutions,
while preventing direct reaction between the reactants/mixing.

Cell: Zn/Zn2+(0.01M) // Cu2+(0.1M)/Cu

 Functions of salt bridge
 It maintains electrical neutrality in the two half cells
 It provides electrical contact between the two electrolytic solutions
of a cell
 It minimizes LJP in galvanic cells containing two dissimilar
solutions in contact

salts used in salt

bridge: potassium nitrate,

potassium chloride, ammonium
nitrate etc.
 Origin of single electrode potential

Electron rich Electron poor

+ - - + Zn+2 -+ +-
Zn+2 Cu+2 - + + - Cu
+2
+- -+
+- -+ +2 Cu+2- + +-
Zn+2 + - - + Zn -+ +-
+- -+ -+ + - Cu+2
+ - - + +2 Cu+2 - + +-
Zn+2 Zn
Cu+2
CuSO4 solution
ZnSO4 solution

Zn2+ ions moves in to Cu2+ ions gets deposited as Cu

solution, leaving behind leaving behind free (-)ly
electrons making it an charged sulphate ions in
electron rich solution, making it an electron
poor
1 March 2023 CHM - 1071 24
 Helmholtz electrical double layer

The rate of the reaction depends on the

• nature of metal
• temperature
• concentration of the metal ions in the solution
 Single electrode potential

• Electric layer on the metal has a potential, ɸ (M)

• Electric layer on the solution has a potential, ɸ (aq.)
• Electric potential difference between the electric
double layer existing across the electrode / electrolyte
interface of a single electrode or half cell.

1 March 2023 CHM - 1071 26

 Measurement of electrode potential

 It is not possible to determine experimentally the

potential of a single electrode.
 It is only the difference of potentials between two
electrodes that we can measure by combining them
to give a complete cell.
 By arbitrarily fixing the potential of reversible
hydrogen electrode as zero, it is possible to assign
numerical values to potentials of the various other
electrodes. Single electrode potentials of electrodes
are referred to as potentials on the hydrogen scale.

1 March 2023 CHM - 1071 27

 Measurement of electrode potential
Zn
electrode

Ecell = Ecathode- Eanode

Cu electrode
 Measurement of electrode potential
• All voltage measuring devices gives differences in
potential
• Voltmeter has 2 knobs (EPs cannot be measured with one
wire!)
• one contact – test electrode
• other contact – with the soln. in the electrode compartment
through another conductor
• Second contact is between solid/soln. interface, which acts
as second half cell
• Potential is associated with this second reaction also
• Ultimately, we measure the difference between the half-
cell potential of test electrode & a half cell made up of the
second contact & the soln.
• Hence, Absolute half-cell potential is not obtained
• Redox reaction must occur if charge is to flow & potential
is1 March
to be2023measured CHM - 1051 29
 Sign of electrode potential
When the electrode is coupled with the SHE, if the
electrode reaction is reduction then EP is given a (+)ve
sign.
e.g., copper with hydrogen electrode
Cu2+ + 2e- → Cu; reduction (cathode)
H2(g) → 2H+ + 2e− oxidation (anode)
E0 = + 0.34 v
When the electrode is coupled with the SHE, if the
electrode reaction is oxidation then EP is given a (-)ve sign.
e.g., Zn with hydrogen electrode
Zn → Zn2+ + 2e−
2H+ + 2e− → H2 E0 = − 0.74 v
1 March 2023 CHM - 1071 30
 Standard electrode potentials
E0 is the electrode potential when electrode is in contact with a
solution of unit concentration at 298 K involving pure solids and
liquids
 Nernst equation
• It is a quantitative relationship between electrode
potential and concentration of the electrolyte species.

• Consider a general redox reaction:

Mn+ (aq) + ne- → M (s) --- (1)

We know that,
ΔG = -nFE --- (2)

ΔGo = -nFEo --- (3)

1 March 2023 CHM - 1071 32

 Nernst equation
o
G  G  RT ln K
[M]
G  G  RT ln n
o
[M ]

[M]
 nFE   nFE  RT ln n
o
[M ]
RT 1
E E 
o
ln n
nF [M ]
1 March 2023 CHM - 1071 33
 Nernst equation
RT 1
E  E  2.303
o
log n
nF [M ]
At T  298K,

0.0592 1
E E  o
log n
n [M ]

0.0592 n
E E  o
log [M ]
n
1 March 2023 CHM - 1071 34
 Nernst equation
.From Nernst equation,
If concentration of solution (Mn+) and temperature is increased, the
electrode potential increases and vice versa.

 RT Conc of species at Cathode

E cell  E cell  2.303 nF log Conc of species at anode 
0

 

For Daniel cell


  2.303
RT  
Cu 2 
 
0 o
 cell
E E - E log 
zn 2 
A

C
nF
 Significance of Nernst equation

• To calculate the potential of a cell that operates under non-standard

conditions.
• To measure the equilibrium constant for a reaction, when the
overall cell potential for the reaction is zero
• At equilibrium the overall cell potential for the reaction is zero. i.e.
E=0
Nernst equation,
E=E° - (RT/nF)lnKc
0 = Eo - RT/nF lnKc
Eo = RT/nF lnKc
RTlnKc = nFE°
Kc = e nFE° / RT
 Emf of a galvanic cell

• The difference of potential, which causes a current to

flow from the electrode of higher potential to one of
the lower potential

Ecell = Ecathode − Eanode

• Ecell depends on
 the nature and composition of the electrodes
 temperature
 concentration of the electrolytic solutions

1 March 2023 CHM - 1071 37

 Emf of a galvanic cell
The emf cannot be measured accurately using a
voltmeter

 Part of the cell current is drawn to deflect the

needle

 Part of the emf is used to overcome the internal

resistance of the cell.

Measured emf < actual emf of the cell

1 March 2023 CHM - 1071 38
 Standard emf of a galvanic cell

• The emf of a cell when the reactants & products of the

cell reaction are at unit concentration or unit activity,
at 298 K and at 1 atmospheric pressure.

• This is represented with E0cell

E0cell = E0cathode − E0anode

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 Measurement of emf
Poggendorff’s compensation method
(+) (-)

E xAD
ESAD '

Ex AD

Es AD'
1 March 2023 CHM - 1071 40
 Standard cell

 It is one which is capable of giving constant emf

for longer periods of time
 Capable of giving highly reproducible emf.
 It has a negligible temperature coefficient of the
emf.
 The cell reaction should be reversible.
 It should have no liquid junction potential.
 It should not be subject to permanent damage due
to passage of current thro’ them

Eg: Weston Cadmium Cell. The emf of the cell is

1.0183 V at 293 K and 1.0181 V at 298 K.

1 March 2023 CHM - 1071 41

 Weston Cadmium Cell
Sealed wax

Cork
Saturated solution of
CdSO4. 8/3H2O

CdSO4. 8/3H2O
crystals
Paste of Hg2SO4
and Hg

Cd-Hg
Mercury (Hg)
12-14% Cd

(-) (+)
1 March 2023 CHM - 1071 42
 Energetics of cell reactions

• Free energy (G) of a system is a measure of its

capacity to do useful work
• The decrease in free energy of a system during a
process is a measure of the maximum useful work
done during the process
• Greater the free energy change (G), greater is the
amount of work that can be obtained from a process
• The decrease in free energy in an electrochemical cell
produces the electrical energy due to a redox reaction

1 March 2023 CHM - 1071 43

 Energetics of cell reactions

In an electro chemical cell,

Electric work done = Quantity of current produced × emf
W = QE --- (1)
Charge on 1mole of electrons = F (96,500 Coulombs)
When ‘n’ moles of electrons are involved in the cell
reaction,
the total charge (Q) on ‘n’ moles of electrons = nF
Q = nF
Substituting for Q in eqn. (1)
W = nFE ---(2)
1 March 2023 CHM - 1071 44
 Energetics of cell reactions
The cell does net work at the expense of the free
energy change (ΔG)
i.e., Net electrical work = Decrease in free energy
w = G
ΔG = − nFE --- (3)

E
H  nFT [ ]P  nFE
T
E
S  nF [ ]P
T
1 March 2023 CHM - 1071 45
 Energetics of cell reactions
Emf of Weston Cadmium cell is 1.0183 V at 293 K
and 1.0l81 V at 298 K. Calculate ∆G, ΔH and ΔS
of the cell reaction at 298 K.

Solution:-
∆G:
∆G = - n FE
n = 2 for the cell reaction;
F = 96,500 C
E = 1.0181 V at 298 K
∆G = -2 x 96,500 x 1.0181 J
= -196.5 KJ
1 March 2023 CHM - 1071 46
 Energetics of cell reactions
H :
E
H  nFT [ ]P  nFE
T
E 1.0181  1.1083
[ ]P 
T 298  293
 0.00004 VK 1
AT T  298 K,
H  2(96500) 298(-0.000 04) - 1.0181
 - 198.8 KJ
S :
E
S  nF [ ]P
T
 2(96500)( 0.00004)
 7.72 JK -1
1 March 2023 CHM - 1071 47
 Numerical problems

1. A galvanic cell consists of copper plate

immersed in 10 M solution of CuSO4 and iron
plate immersed in 1M FeSO4 at 298K. If E0cell =
0.78 V, write the cell reaction and calculate
E.M.F. of the cell.

1 March 2023 CHM - 1071 48

 Numerical problems
Solution:

Cell reaction:

Fe + Cu2+ ↔ Fe2+ + Cu

RT [products]
E cell  E 0cell  ln
nF [reactants]

Ecell = E0Cell - 0.0592/2 log [Fe2+ ]/[Cu2+]

Ecell = 0.78 + 0.0296 log 10/1
= 0.8096V

1 March 2023 CHM - 1071 49

 Numerical problems

Calculate E.M.F. of the zinc – silver cell at 25˚C

when [Zn2+] = 1.0 M and [Ag+] = 10 M (E0cell =
1.56V at 25˚C). Write the cell representation and
cell reactions

1 March 2023 CHM - 1071 50

 Numerical problems
Solution:
Cell representation
Zn│Zn2+(1M) ║ Ag+(10M)│Ag
Cell reaction:
Zn + 2Ag+ ↔ Zn2+ + 2Ag
0.0592 [Zn 2 ]
Ecell  Ecell  2 log [Ag  ]2
0

0.0592 1
Ecell  1.56  2 log 102
0.0592
Ecell  1.56  log 10 -2

2
0.0592
Ecell  1.56  2 (-2)(1)
E cell
 1.6192 V
1 March 2023 CHM - 1071 51
 Numerical problems

The emf of the cell

Mg│Mg2+(0.01M)║Cu2+(1M)│Cu is measured to
be 2.78 V at 298K. The standard electrode
potential of magnesium electrode is -2.37 V.
Calculate the electrode potential of copper
electrode

1 March 2023 CHM - 1071 52

 Numerical problems

Cell reaction:
Mg + Cu2+ ↔ Mg2+ + Cu
E= Eo-0.0592/n log 1/[Mn+]
EMg= EoMg-0.0592/2 log 1/[Mg2+]
=-2.4291V
Ecell=ECu-EMg
2.78 = ECu-[-2.429]
ECu =2.78-2.429
=0.3509 V

1 March 2023 CHM - 1071 53

 Numerical problems

The emf of the cell

Cu│ Cu 2+ (0.02M)║ Ag+ (0.1M) │Ag is measured to

be 0.46V at 298K. The standard electrode potential of
copper electrode is 0.34V. Calculate the electrode
potential of silver electrode

1 March 2023 CHM - 1071 54

 Classification of Electrodes

References Electrodes
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag│AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1071 55
References Electrodes
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1071 56
References Electrodes maintain a fixed reference potential
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1071 57
References Electrodes maintain a fixed reference potential
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1002 58
References Electrodes maintain a fixed reference potential
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1071 59
References Electrodes maintain a fixed reference potential
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1002 60
References Electrodes maintain a fixed reference potential
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1071 61
References Electrodes maintain a fixed reference potential
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes respond to analyte activity

Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1071 62
References Electrodes maintain a fixed reference potential
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1071 63
References Electrodes maintain a fixed reference potential
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1071 64
References Electrodes maintain a fixed reference potential
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1071 65
References Electrodes maintain a fixed reference potential
Standard Hydrogen Electrode (SHE)
Silver-Silver Chloride Electrode (Ag/AgCl)
Saturated Calomel Electrode (SCE)

Indicator Electrodes
Ion-Selective Electrodes (ISE’s)
Glass Electrode (pH electrode)
Fluoride Electrode (solid-state ISE)
Calcium Electrode (liquid-based ISE)
1 March 2023 CHM - 1071 66
 Gas electrode

• It consists of gas bubbling over an inert metal wire or foil

immersed in a solution containing ions of the gas.
• Standard hydrogen electrode is the primary reference electrode,
whose electrode potential at all temperature is taken as zero
arbitrarily.

Platinum
 Gas electrode
• Representation: Pt,H2(g)/ H+
• Electrode reaction: H+ + e- 1/2 H2(g)
The electrode reaction is reversible as it can undergo either
oxidation or reduction depending on the other half cell.
• If the concentration of the H+ ions is 1M, pressure of H2 is 1atm
at 298K it is called as standard hydrogen electrode (SHE).

Limitations
 Construction and working is difficult.
 Pt is susceptible for poisoning.
 Cannot be used in the presence of oxidizing agents.
 Gas electrode applications
• Primary reference electrode: To determine electrode potential of
other unknown electrodes
• Electrode potential of Hydrogen Electrode is given as follows:
• H+ + e- 1/2 H2(g)
• E = Eo - 2.303 RT/nF log [H2]1/2/[H+]
E = 0 - 0.0591 log 1/[H+]
E = - 0.0591pH
To determine the pH of a solution. Cell Scheme: Pt,H2,H+(x)// SHE
• The emf of the cell is determined.
• E (cell) = E (C) – E(A)
E (cell) = 0 – (- 0.0592 pH)
E (cell) = 0.0592 pH
pH = E(cell)/ 0.0592
 Metal – metal salt ion electrode

• These electrodes consist of a metal and

a sparingly soluble salt of the same
metal dipping in a solution of a soluble
salt having the same anion

Eg: Calomel electrode

Ag|AgCl electrode

1 March 2023 CHM - 1071 70

 Metal – metal salt ion electrode

1 March 2023 CHM - 1071 71

 Pt(s)|Hg(l)|Hg,Hg2Cl2,KCl(paste)|KCl(aq)
Hg2Cl2 (s) + 2e─ 2Hg (l) + 2Cl─(aq)
E = Eo – 2.303 RT/2F log [Cl ─]2

= Eo - 0.0591 log [Cl ─] at 298 K

Its electrode potential depends on the
concentration of KCl.

Conc. of Cl ─ Electrode potential

0.1 M 0.3335 V
1.0 M 0.2810 V
Saturated soln. 0.2444 V

1 March 2023 CHM - 1071 72

1 March 2023 CHM - 1071 73
 Applications
• Since the electrode potential is a constant it can
be used as a secondary reference electrode

• To determine electrode potential of other

unknown electrodes.

• To determine the pH of a solution,

Pt|H2|H+(X) ||KCl|Hg2Cl2|Hg

pH = (Ecell – 0.2444) / 0.0592

1 March 2023 CHM - 1071 74
 Ion Selective Electrode

• It is sensitive to a specific ion present in an

electrolyte.
• The potential of this depends upon the
activity of this ion in the electrolyte.
• Magnitude of potential of this electrode is
an indicator of the activity of the specific
ion in the electrolyte.
*This type of electrode is called indicator
electrode.

1 March 2023 CHM - 1071 75

 Glass Electrode

1 March 2023 CHM - 1071 76

 Scheme of typical pH glass electrode
1. a sensing part of electrode,
2. a bulb made from a specific glass
sometimes electrode contain small amount
of AgCl precipitate inside the glass
electrode
3 internal solution, usually 0.1M HCl for pH
electrodes
4.internal electrode, usually silver chloride
electrode or calomel electrode
5.body of electrode, made from non-
conductive glass or plastics.
6.reference electrode, usually the same type
as 4
7.junction with studied solution, usually
made from ceramics or capillary with
1 March 2023 asbes51s or quartz fiber. 77
 • The hydration of a pH sensitive glass
membrane involves an ion-exchange
reaction between singly charged
cations in the interstices of the glass
lattice and protons from the solution.

H+ + Na+ ↔ Na+ + H+
(soln.) (glass) (soln.) (glass)

1 March 2023 CHM - 1071 78

 Electrode Potential of glass electrode
The overall potential of the glass electrode has
three components:

 The boundary potential Eb, - due to the

difference in response of the inner and outer
surface of the glass bulb to changes in [H+].
 Internal reference electrode potential Eref.
 Asymmetric potential Easy.
Eg = Eb + Eref. + Easy.

1 March 2023 CHM - 1071 79

 • Eb = E1 – E2
= (RT/nF) ln C1 – (RT/nF) ln C2
= L + (RT/nF) ln C1
Eb depends upon [H+]

Eg = Eb + EAg/AgCl + Easy.
= L + (RT/nF) ln C1 + EAg/AgCl + Easy.
= Eog + (RT/nF) ln C1
= Eog + 0.0592 log [H+]

Eg = Eog – 0.0592 pH.

1 March 2023 CHM - 1071 80

1 March 2023 CHM - 1071 81
1 March 2023 CHM - 1071 82
 Applications

• Determination of pH:
Cell: SCE ║Test solution | GE
Ecell = Eg – Ecal
Ecell = (Eog – 0.0592 pH) – 0.2444

pH = (Eog - Ecell – Ecal.) / 0.0592

1 March 2023 CHM - 1071 83
 Advantages:
1. It can be used without interference in
solutions containing strong oxidants, strong
reductants, proteins, viscous fluids and
gases as the glass is chemically robust.
2. It can be used for solutions having pH
values 2 to 10. With some special glass (by
incorporation of Al2O3 or B2O3)
measurements can be extended to pH
values up to 12.
3. It is immune to poisoning and is simple to
operate
4. The equilibrium is reached quickly & the
response is rapid
1 March 2023 CHM - 1071 84
5. It can be used for very small quantities of
the solutions. Small electrodes can be
used for pH measurement in one drop of
solution in a tooth cavity or in the sweat
of the skin (micro determinations using
microelectrodes)
6. If recently calibrated, the glass electrode
gives an accurate response.
7. The glass electrode is much more
convenient to handle than the
inconvenient hydrogen gas electrode.
1 March 2023 CHM - 1071 85
 Disadvantages:

The bulb of this electrode is very fragile and

has to be used with great care.

The alkaline error arises when a glass

electrode is employed to measure the pH of
solutions having pH values in the 10-12 range
or greater. In the presence of alkali ions, the
glass surface becomes responsive to both
hydrogen and alkali ions. Low pH values arise
as a consequence and thus the glass pH
electrode gives erroneous results in highly
alkaline solutions.
1 March 2023 CHM - 1071 86
 The acid error results in highly acidic solutions.
Measured pH values are high.

Dehydration of the working surface may cause

erratic electrode performance. It is crucial that
the pH electrode be sufficiently hydrated before
being used. When not in use, the electrode
should be stored in an aqueous solution
because once it is dehydrated, several hours are
required to rehydrate it fully.

1 March 2023 CHM - 1071 87

 As the glass membrane has a very high
electrical resistance (50 to 500 mΩ), the
ordinary potentiometer cannot be used for
measurement of the potential of the glass
electrode. Thus special electronic
potentiometers are used which require
practically no current for their operation.

1 March 2023 CHM - 1071 88

 Standardization has to be carried out
frequently because asymmetry potential
changes gradually with time. Because of an
asymmetry potential, all glass electrodes in
a particular assembly will not have the same
value of EoG . For this reason, it is best to
determine EoG for each electrode before
use.

The commercial version is moderately

expensive

1 March 2023 CHM - 1071 89

 Problems
The cell SCE ΙΙ HCl (0.1M) Ι AgCl(s) Ι Ag
gave an emf of 0.24 V and 0.26 V with a
buffer having pH value 2.8 and unknown
pH value respectively. Calculate the pH
value of unknown buffer solution. Given
ESCE= 0.2444 V

1 March 2023 CHM - 1071 90

 Ecell = Ecathode – Eanode
= Eg – Ecal
= E0g – 0.0592pH - Ecal

Eog= 0.0592 pH + Ecell + Ecal

= 0.0592x2.8 + 0.24 + 0.2422
= 0.648 V
pH = (Eog - Ecell – Ecal) / 0.0592
= (0.648 - 0.26 - 0.2422) / 0.0592
= 2.46
1 March 2023 CHM - 1071 91
Objectives:

 Describe the major features of

commercial cells.
 Know the two major types of batteries.
 Distinguish between primary & secondary
battery types.
 Know the chemistry and applications of
Lead acid cell, Ni-Cd cell, Li ion
 Alkaline, CH3OH–O2, and PEM Fuel Cells
Components of a Battery

* Container
* Separator
* Electrolyte
* Current Collectors
* Active materials
*Terminals
Current:
Current is a measure of the rate at which the battery
is discharging
Capacity:
The capacity is the charge or the amount of
electricity that may be obtained from the battery and
is given in ampere hours (Ah).
Electricity storage density:
Electrical storage density is the amount of electricity
per unit weight which can be stored or it is the
capacity per unit weight of the battery
Power density:
Power density is the power per unit weight of the
battery (W/kg)
Cycle life:
The cycle life is the number of complete
charge/discharge cycles that the battery is able to
support before its capacity falls below 80% of its
original capacity.
Shelf life:
It is the length of the time that a commodity may be
stored without becoming unfit for use / consumption.
For rechargeable batteries, this the period between
recharge cycles.
Design life:
It is the elapsed time before a battery becomes
unusable whether it is in active use or inactive.
Energy released on disch arg e
Energy efficiency = Energy released on ch arg e x 100
 Commercial Cells:
Galvanic cells used as source of electric energy for
various consumer, industrial and military
applications.

Classification:
 Primary Cells e.g., Dry cell,
LiCuS cell
 Secondary Cells e.g., Lead acid cell,
Ni – Cd cell,
Lithium ion cells
 Primary Cells
• Produce electricity from chemicals that are sealed
into it.
• Cannot be recharged as the cell reaction cannot
be reversed efficiently by recharging.
• The cell must be discarded after discharging.
e.g. Zinc - manganese dioxide cell (Dry cell)
Mercuric oxide – Zinc cell.
Silver oxide – zinc cell.
Basic Requirements of Primary Cell

 Compactness and lightweight.

 Fabricated from easily available raw materials.
 Economically priced.
 High energy density and constant voltage.
 Benign environmental properties
 Longer shelf life and discharge period.
 Leak proof containers and variety of design
options.
Secondary Cells
• Generation of electric energy, that can be restored to
its original charged condition after its discharge by
passing current flowing in the opposite direction.
• These cells have a large number of cycles of
discharging and charging.
• They are known as rechargeable cells, storage cells, or
accumulators.
e.g. Lead storage cell.
Nickel- cadmium cell.
Lithium- ion batteries.
Basic Requirements of Secondary Cell

• Long shelf-life and cycle life.

• High power to weight ratio
• Short time for recharging
• Tolerance to service conditions.
• High voltage & high energy density
 Differences
Primary Batteries
 Cell reaction is irreversible
 Must be discarded after use.
 Have relatively short shelf life
 Function only as galvanic
cells .
 They cannot be used as
energy storage devices
 They cannot be recharged
e.g.Dry cell.
Secondary Batteries
Cell reaction is reversible.
Can be recharged
Have long shelf life.
Functions both galvanic
Cell & as electrolytic cell.
They can be used as
storage devices
(e.g. solar / thermal energy
converted to
electrical energy)
They can be recharged.
(e.g. Li-MnO2battery
Lead acid,
Ni-Cd battery)
Lead-acid battery
Lead-acid battery
• Anode:

Spongy lead on lead grid

• Cathode:

Porous PbO2

• Electrolyte:

H2SO4(aq)(20%) (density 1.21 - 1.30 g/ml)

• Cell Scheme:

Pb | PbSO4;H2SO4(aq);PbSO4;PbO2 | Pb

O.C.V. = 2 V (Pair of plates)

 Reactions during discharging
• At Anode:
Pb (s) → Pb2+(aq) + 2e-
Pb2+(aq) + SO42-(aq) → PbSO4(s)
Pb(s) + SO42-(aq) → PbSO4(s) + 2e-
• At Cathode:
PbO2(s) + 4H+(aq) + 2e- → Pb2+(aq) + 2H2O(l)
Pb2+(aq) + SO42-(aq) → PbSO4(s)
PbO2(s) + 4H+(aq) + SO42-(aq) + 2e- →
PbSO4(s) + 2H2O(l)
• Overall:
Pb(s) + PbO2(s) + 4H+(aq) + 2SO42-(aq)

2PbSO4 (s) + 2H2O(l)

Charging the Lead-acid battery:
 Charging reactions

• At (−) terminal (anode) of discharged cell:

PbSO4 (s) + 2e- → Pb(s) + SO42-(aq)
• At (+) terminal (cathode) of discharged cell:
PbSO4(s) + 2H2O(l) → PbO2(s) + SO42-(aq) + 4H+(aq) + 2e-
• Net Cell Reaction:
2PbSO4 (s)+ 2H2O(aq) → Pb(s) + PbO2(s) + 2H2SO4
 Effect of overcharging
• 2H2O (l) + electrical energy → 2H2 (g) + O2(g)

Consequences:

(i)Reduce the acid level and damage the exposed

electrode grids

(ii)Dangerous high-pressure build-up that can lead to a

serious risk of explosion.

Modern maintenance-free batteries:

• without a gas – release vent.

• Gassing is controlled by using

1. Pb-Ca (0.1 % ) as the anode which inhibits the electrolysis of

water.

2. a catalyst (e.g. a mixture of 98% ceria (cerium oxide) & 2%

platinum) that combines the hydrogen & oxygen produced during

discharge back into water

 Limitations
• Self discharge: They are subject to self discharge with H2
evolution at negative plates and O2 evolution at positive
plates.

Pb +H2SO4 PbSO4 + H2
PbO2 + H2SO4 PbSO4 +H2O +1/2 O2

SO42- +2 H+(From dissociation of water) H2SO4

H2O H+ + OH-

• Loss of Water: Due to evaporation, self discharge and

electrolysis while charging. Hence water content must be
regularly checked and distilled water must be added.
• Sulphatation: If left in uncharged state, for a
prolonged period, or operated at too high
temperatures or at too high acid concentrations,
transformation of porous PbSO4 into dense and
coarse grained form by recrystallization.

* This results in passivation of negative plates

inhibiting their charge acceptance.
• Corrosion of Grid: Can occur due to overcharging
when grid metal gets exposed to the electrolyte.
This weakens the grid and increases the internal
resistance of the battery.

• Effectiveness of battery is reduced at low

temperature due to increase in the viscosity of
electrolyte.
 Applications
*Automative: For starting, lighting and
ignition of IC engine driven vehicles.
*Consumer Applications: Emergency
lighting, security alarm system.
*Heavy duty Application: Trains, lift
trucks, mining machines etc.
Advantages:
A lead storage battery is highly efficient. The
voltage efficiency of the cell is defined as
follows.
Voltage efficiency = average voltage during discharge
average voltage during charge
The voltage efficiency of the lead – acid cell is
about 80 %.
The near reversibility is a consequence of the
faster rate of the chemical reactions in the cell
i.e. anode oxidizes easily and cathode reduces
easily leading to an overall reaction with a high
negative free energy change.
 A lead – acid battery provides a good service
for several years. Its larger versions can last
20 to 30 years, if carefully attended (i.e. longer
design life)
 It can be recharged. The number of recharges
possible range from 300 to 1500, depending
on the battery’s design and conditions. The
sealed lead-acid batteries can withstand upto
2000 – rechargings. Generally the most
costly, largest, heaviest cells are the longest–
lived.
 The battery’s own internal self – discharging is
low.
 The length of time that is generally required for
re-charging process is less i.e. recharge time
is 2-8 hours depending on the status of
battery.
Low environmental impact of constituent
materials is an added advantage
It has sensitivity to rough handling and
good safety characteristics.
Ease of servicing as indicated by several
local battery service points.
It is a low - cost battery with facilities for
manufacture throughout the world using
cheap materials.
 Lead Storage Battery
Advantages
• Highly efficient
• Good service for several
years
• Low internal self –
discharge
• Provide a large current
Disadvantages
• Sulphatation
• Low energy storage to weight ratio
• CP decreases with decrease in conc.
of sulfuric acid
• Not efficient at low temp.s
• Overcharging may damage the
exposed electrodes & may also
lead to explosion in extreme cases
• Sulfuric acid is highly corrosive
liquid
• Lead is toxic & hence
environmental & health problems
• Corrosion of the lead grid at the
lead dioxide electrode
NICKLE- CADMIUM CELL
 NICKLE- CADMIUM CELL
Anode:
Porous cadmium powder compressed to cylindrical
pellets.

Cathode:
NiO(OH) mixed with 20% graphite powder

Electrolyte:
20 - 28% Aq. KOH jelled with a jelling agent.

Cell Scheme:
Cd|Cd(OH)2,KOH,Ni(OH)2, NiO(OH)|Ni

O.C.V. = 1.25V
 NICKLE- CADMIUM CELL
Discharging reaction:

Anode:
Cd(s)+2OH-(aq) → Cd(OH)2(s) + 2e-
Cathode:
2NiO(OH) (s) + 2 H2O + 2 e- →
2Ni(OH)2(s) + 2OH-(aq)
Net Reaction:
Cd(s) + 2NiO(OH) (s) + 2H2O →
2 Ni(OH)2 (s) + Cd(OH)2(s)
 NICKLE- CADMIUM CELL

Charging reactions:
At anode (-ve pole):
Cd(OH)2 (s) + 2e-→ Cd(s) + 2OH-(aq)
At cathode (+ve pole):
2 Ni(OH)2(s) + 2OH-(aq) → 2 NiO(OH) (s)
+ 2H2O+2e-
Overall reaction:
2 Ni(OH)2 (s) + Cd(OH)2(s) →
2 NiO(OH) (s) + Cd(s) +2H2O(l)
 NICKLE- CADMIUM CELL

ADVANTAGES DISADVANTAGES
• Long cycle life • Environmental
• Constant voltage pollution hazard
• Long shelf life • Increased weight
• No gassing • High overall capital
cost
• Long design life
• KOH is a corrosive
• Good performance at LT
hazardous chemical
• Produce large
instantaneous currents
 Applications

In flash lights, photoflash units and

portable electronic equipments.
In emergency lighting systems, alarm
systems.
In air crafts and space satellite power
systems.
For starting large diesel engines and gas
turbines etc.,
 Advantages

Can be recharged many times.

They maintain nearly constant voltage level throught
their discharge. There is no change in the electrolyte
composition during the operation.
It can be left unused for long periods of time at any
state of charge without any appreciable damage (i.e.
long shelf life).
It can be encased as a sealed unit like the dry cell
because gassing will not occur during nominal
discharging or recharging.
They exhibit good performance ability at low
temperatures.
They can be used to produce large
instantaneous currents as high as 1000-8000
A/ sec.

It is a compact rechargeable cell available in

three basic configurations – button, cylindrical
and rectangular.

They have low internal resistance.

 Disadvantages

 It poses an environmental pollution hazard due

to higher toxicity of metallic cadmium than
lead.
 Cadmium is a heavy metal and its use
increases the weight of batteries, particularly in
larger versions.
 Cost of cadmium metal and hence the cost of
construction of NiCad batteries is high.
 The KOH electrolyte used is a corrosive
hazardous chemical.
 Tutorial – 1 questions
Answer the following questions:

1. Differentiate between the two types of electrochemical cells (2M)

2. The EMF of the cell having Ni and Cu as the electrodes in contact with their
respective electrolytes NiCl2 and CuCl2 is 0.5735 V at 298 K and 0.5951 V at
273 K. Calculate ΔG, ΔH and ΔS for the reaction at 298 K. Write the cell
representation. (2M)
3. What are the conditions for an electrochemical cell to act as a standard cell?
Give an example. Describe the Poggendorff’s method of determination of
EMF of a cell using a standard cell. (3M)
4. Derive Nernst equation for the following cell and calculate its EMF at 298 K
Mg | Mg2+ (2 M) || Ag+ (1 M) | Ag (3M)

1 March 2023 CHM - 1051 128

 Li ion cells
Anode:
Lithium-carbide type intercalate (LixC6)
Cathode:
Transition metal oxide MO2 of variable oxidation state
(MnO2, CoO2, NiO2) which can intercalate lithium
(usually cobalt dioxide, CoO2).
Electrolyte:
Inert polar dry ether or carbonate (diethyl carbonate or
propylene carbonate), in which a conductivity salt such as
LiPF6 or LiBF4 is dissolved
Li ion cells
At anode:-
LixC6  xLi+(solv) + 6C(s) + ne−

At cathode:-
CoO2(s)+ xLi+(solv) + ne −  LixCoO2(s)

Net cell reaction:-

discharging
LixC6 (s) + CoO2 LixCoO2(s)+ 6C
charging
 Lithium - ion Cell
Advantages Disadvantages
• Designed to overcome the
• Poor charge retention
safety problems • Self discharge rate is
• Long cycle life (400-1200 about 10% per month
cycles) • High cost
• Small, light & provide high
energy density
• Can be operated in a wide
temperature range
• High average voltage
 Fuel Cells

A fuel cell is a galvanic cell in which chemical

energy of a fuel – oxidant system is converted
directly into electrical energy in a continuous
electrochemical process.
• Cell Schematic Representation:
Fuel│electrode│electrolyte│electrode│oxidant.
e.g. H2 - O2; CH3OH - O2
• The reactants (i.e. fuel + oxidant) are constantly
supplied from outside and the products are
removed at the same rate as they are formed.

• Anode:

Fuel + oxygen → Oxidation products + ne-

• Cathode:

Oxidant + ne- → Reduction products.

 Requirements of Fuel Cell

• Electrodes:
Must be stable, porous and good conductor
• Catalyst:
Porous electrode must be impregnated with
catalyst like Pt, Pd, Ag or Ni, to enhance
otherwise slow electrochemical reactions
• Temperature:
Optimum
• Electrolyte:
Fairly concentrated
 Advantages of Fuel Cell

 High fuel to electricity conversion efficiency of 70 – 75%.

 Produce a steady electric current as long as fresh reactants

are available.

 Absence of harmful waste products - environment

friendly.

 High reliability and low maintenance.

 Individual fuel cells can be stacked and connected in series

(fuel battery) to produce higher voltages.
 Classification of fuel cells

S. No. Fuel cell type Electrolyte used

1 Polymer electrolyte Polymer membrane
2 Direct methanol Polymer membrane
3. Alkaline Potassium hydroxide
4. Phosphoric acid Phosphoric acid
5. Molten carbonate Lithium/potassium
carbonate
6. Solid oxide Yittria stabilized zirconia
 Alkaline Fuel Cell(AFC)

 One of the first fuel cell technologies developed

 First type widely used in the U.S. space program to

produce electrical energy and water onboard spacecraft.
• Anode & Cathode: Porous carbon plates
impregnated with Pt

• Fuel: Hydrogen

• Oxidant: Pure Oxygen

• Electrolyte: potassium hydroxide (30%-45% KOH). .

• Operating Temperature: 80 °C

• OCV = 1.10 V
Anode : H2 + 2OH- → 2H2O + 2e-
Cathode: 1/2 O2 + H2O + 2e- → 2OH-
Net Reaction: H2 + 1/2 O2 → H2O
Advantages:
• Excellent performance on hydrogen (H2) and oxygen (O2) compared
to other fuel cells due to its active O2 electrode kinetics
• Flexibility to use a wide range of electro-catalysts
Disadvantages:
 The sensitivity of the electrolyte to CO2 requires the use of highly
pure oxidant and fuel.
 Use of a reformer would require a highly effective CO and CO2
removal system.
 If ambient air is used as the oxidant, the CO2 in the air must be
removed. While this is technically not challenging, it has a
significant impact on the size and cost of the system.
Proton Exchange Membrane Fuel cell (PEMFC)

Construction
• Electrodes: Typical gas diffusion electrodes,
made up of porous ‘C’ impregnated
with Pt catalyst
• Electrolyte: Ion exchange polymeric membranes
• Fuel: Hydrogen
• Oxidant: Air
• Catalyst: Platinum
• Operating temp.: around 80°C
• Charge-carrier: H+
Proton Exchange Membrane Fuel cell (PEMFC)

Working:
Anodic reaction:
H2 2H+ + 2e−
Cathodic reaction:
½ O2 + 2H+ + 2e− H2 O
Net cell reaction:
H 2 + ½ O2 H2O

Power output is in the

range of 5 - 200 KW
Perflourinated membrane by DuPont
F F F F F F F F F

C C C C C C C C C

F F F F O F F F F

F C F

F C F

F C F

F C F

O=S=O
-
O
+
H
 Advantages Disadvantages
• solid electrolyte provides• The low and narrow operating
excellent resistance to gas temperature range makes thermal
crossover. management difficult
• Dehydration of the membrane
• low operating temperature reduces the proton conductivity
allows rapid start-up and excess water can lead to the
flooding of the electrolyte. Both
the conditions leading to poor
• capable of high current performance.
densities
• Perflourinated membranes have
high cost
• quite sensitive to poisoning by
trace levels of contaminants
including CO, sulfur species and
ammonia.
 Fuel cells Galvanic Cells
• Do not store chemical energy  Store chemical energy
• Reactants fed from outside the cell  Reactants are an integral part of
continuously its construction.
• Need expensive noble metal  These special conditions are not
catalysts & optimum operative required
conditions
• Do not get discharged & no need of  Get discharged when stored up
charging energy is exhausted.
• Never become dead as long as fresh  Limited life span
reactants are available
• Useful for long-term electricity  Useful as portable power
generation. services.
• Reaction products must be  No product removal problem
continuously removed
• No pollutants generated  Pollutants are generated after
their useful life
• Produce power from fuels  cannot generate power from fuels
• Significantly higher power densities  Lower power density
Metal Finishing
Process of electro deposition of an
adherent metallic film of uniform
thickness on the surface of the
substrate for the purpose of modifying
its surface properties.
Metal finishing was introduced as a
decorative finish, but the increasing
demand for parts with prescribed
specifications has led to vast
technological developments in the field.
 OBJECTIVES
In general a metal or alloy used for a purpose does not
meet all the requirements
Metal finishing is one of the methods employed to
improve their lacking properties
Improving resistance to corrosion, scratch or abrasion and
wear
Enhancing decorative appearance (bright and shiny)
Improving solderability
Enhance thermal and electrical conductivity
Increase hardness of surface
Reducing frictional loss etc.
Produce reflectivity and appearance
Chemical resistance
 Techniques of metal finishing

• Electroplating
• Electroless plating and immersion
coating
• Thermal spray coating
• Vapour deposition technology of
coating
• CVD
• Chemical conversion coatings
 ELECTROPLATING

• The process by which coating metal is

deposited on the base metal by passing
direct current through an electrolytic
solution, containing the soluble salt of
the coating metal.
• Common metals used in industries for
producing metal coatings are Cu, Ni,
Zn, Au, Pt etc.
 Theory Of Electroplating

• The electroplating device is essentially

an electrolytic cell, in which two
electrodes, anode and cathode are
dipped in an electrolyte solution.
 Essential Components

• A d.c. electrical power source.

• Anode : Inert material / coating metal
• Cathode : Article to be plated.
• Electrolytic bath: Solution of conducting
salt, metal to be
plated in a soluble
form, buffer and
additives.
• Container: Made up of rubber lined steel,
wood or concrete.
 Theory Of Electroplating
• Anode : Made of coating metal.
• Cathode : Article to be plated.
• Electrolyte : CuSO4 solution.
CuSO4 Cu2+ + SO42-
On passing current,
Cu2+ + 2e− Cu (Cathode)
Cu + SO42- CuSO4 + 2e − (Anode)

Thus there is a continuous replenishment of

electrolytic salt during electrolysis.
1 March 2023 CHM - 1051 156
• If the anode is made of some inert material
like graphite, then electrolytic salt/solution
is added continuously in order to maintain
proper coating metal ion concentration in
the bath.
• The process of electroplating goes on
nonstop, since the anode is not
consumed.
Factors Governing Electroplating

 Decomposition Potential (ED)

 Polarization

 Over voltage
DECOMPOSITION POTENTIAL (ED)
• The minimum voltage required for the
continuous electrolysis of an electrolyte in an
electrolytic cell
• In the electrolysis of water, a pair of Pt
electrodes is immersed in a solution of an
acid. It is found experimentally that a
potential of about 1.7V must be applied to the
cell before there sets in a continuous
evolution of O2 and H2
• During electrolysis accumulation of
products of electrolysis around the
electrodes causes a back emf which
opposes the applied emf.
• To overcome the back emf, the applied
emf will have to be increased; then only
electrolytic deposition starts again.
 Measurement of ED

• Gradually increasing the applied voltage

between the electrodes.
• Milli ammeter reading is noted down for every
voltage applied.
Measurement of ED
 Factors Influencing ED

Decomposition potentials of different

electrolytes are different
• Strength of the current flowing through
the cell
• Chemical nature of the electrodes
• Physical nature of the electrodes
• Activity of the electrolyte
• Absolute temperature
 Uses of decomposition potential

• Used to carry out all electrolytic

processes. (electroplating, electro refining
etc.)
• Used in the separation of ions from a
solution by electrolysis.
• Helps in predicting the sequence of
discharge process to occur
 OVER VOLTAGE

• The decomposition of an electrolyte is

expected to start as soon as applied potential
reaches the value of reversible emf of the cell.
• But when products discharged at the
electrodes are gases, then the actual
decomposition potential is invariably much
higher than its theoretical reversible electrode
potential.
• The excess voltage is referred to as over
voltage of the gas.
 OVER VOLTAGE
• Over voltage is the difference between the
actual applied emf to bring about continuous
electrolysis and the theoretical emf needed for
such electrolysis.
• For instance the reversible potential of oxygen
gas with smooth Pt electrode is 1.23 V. But
actual gas evolution takes place at a potential
of 1.68 V. The excess 0.45 V is the over
voltage of oxygen on smooth Pt surface.
Factors Affecting Over voltage
 Electrode surface
 Nature of the electrolyte
 Temperature
 Current density
• Of the many steps involved in gas
evolution at electrodes, at least one is
rather a slow process and requires high
energy.
• Electrolysis of water:
(i) H+ + e- H (fast)
(ii) H + H H2(slow)
The step (ii) being slow, consumes
energy and accounts for over voltage.
 POLARIZATION
• Development of over voltage in an
electrolytic cell is called polarization.
• Electrolytic processes occur at the
electrodes of the cell.
• Polarization sets in the cell when the
electrode processes become slow and
irreversible.
• Magnitude of over potential is directly
proportional to the extent of polarization.
 Types Of Polarization:
The observed polarization can be of two
types.
Concentration polarization.
kinetic or activation polarization.
CONCENTRATION POLARIZATION

• An electrochemical reaction occurs only

at the surface of the two electrodes.
• Adjacent to the electrode surface
reactant concentration decreases.
• The reactant species are transported to
the electrode surface by processes like
diffusion, migration and convection from
the bulk of the solution.
• Current flowing through the cell drops
when the rate of transport is insufficient
to match the electrode reaction.

• A potential higher than the theoretical

value is required to maintain the current
at the necessary level.

This phenomenon is called concentration

polarization.
• Steps:
Diffusion of reactant species towards
the electrode.
Diffusion of product away from the
electrode cause concentration
polarization.
• This can be minimized by:
* Increasing the convection.
* By raising the temperature.
* Mechanical agitation of the solution.
 ACTIVATION POLARIZATION
• This is caused when any of the following steps
become slow and need activation energy.
• Adsorption of the reactant on the electrode.
• Charge transfer across the metal -solution
interface.
• Desorption of the product from the electrode
• A higher potential than the theoretical value is
to be applied to maintain current at the
necessary level.
• It is not possible to eliminate or minimize
kinetic polarization by any means.
• Activation polarization is
*Low: When metal deposition or metal
dissolution is the electrode
process.
*High: When the electrode process is a
gas (H2 ,O2, etc.,) evolution
Factors influencing the polarization

 Size and nature of the electrode

 Nature of ions accumulated on electrodes
 Electrolytic concentration
 Temperature
 Conductivity of electrolytic solution
 Stirring of electrolytic solution
 Use of depolarizer
1 March 2023 CHM - 1051 176
Importance of polarization effect:
• An impervious or non-porous film, contributes
to the increase of polarization at an electrode.
• Considerable polarization effect can also be
seen where loosely adhering and even porous
films are formed.
• Such films either formed naturally (during
manufacturing) or artificially (by the application
of special coatings or products of corrosion) are
important in determining the rate of corrosion of
a metal or an alloy and also for the protection
from corrosion.
1 March 2023 CHM - 1051 177
 Applications of electroplating

 Plating for aesthetic appearance

 Plating for protection

 For electroforming

 Plating on non-metals

1 March 2023 CHM - 1051 178

 Characteristics of A Good Deposit

• The deposit should be bright and lustrous.

• The deposit should be continuous, uniform,
non porous and adhesive.
• It should be hard and ductile.
• It should be of fine grained nature.
Factors Influencing The Nature of Deposit
• Current Density:
An optimum current density should be applied.

If low - leads to slow process

results in coarse grained deposit.

If high - leads to rough and treed deposit.

results in burnt and spongy deposit.
Metal ion concentration:
Low metal ion concentrations give low
crystal size, smaller and fine adherent
coating films.
• This can be achieved by:
addition of a compound with a common
ion.
formation of complex compounds.
Eg: Double cyanides of Na or K.
Temperature:
• It should be between 350C and 650C.
• Lower temperature:
reduces the solubility of the metal salt.
reduces the mobility of the ions.
• Higher temperature:
affects the lining of the equipment,
electrode surface and the substrate.
Agitation:
• Agitation of the solution brings up a fresh
supply of metal salts to the cathode.
• It also sweeps away gas bubbles which may
otherwise cause pits.
• Rapid agitation may
detach the particles.
stir up the sludge.
results in rough and porous deposits.
pH of the electrolytic bath:
Suitable pH is maintained using appropriate
buffers.
• In Ni plating borate buffer is used to
maintain pH 4.5.
• At low pH more H2 evolution takes place on
the cathode.
• At higher pH precipitation of hydroxides of
metal takes place.
Addition agents:
The wide range of additives are added in
low concentrations, serve to electroplating
bath to modify the structure and properties
of the electrodeposits.
 Function:
Makes the deposit smooth, fine grained,
hard and adherent.
Types of additives:
• Complexing agent:
Eg: Cyanide, sulphamate ions.
• Brightners:
Eg: Aromatic sulphonates, thiourea.
• Wetting Agents:
Eg: Sodium lauryl sulphate.
Levelers:
Produce a level deposit by getting adsorbed
at places where rapid deposition of metal
takes place.
Structure Modifiers:
These additives change the structure of the
deposit.
Throwing power:
It is used as a measure of the distribution of
the deposit .
• This property is particularly important when
the article is of an irregular shape.
• This can be improved by:
separating the distances between the
electrodes.
agitating the solution to minimize high
local electrolytic resistance.
 Methods of cleaning the metal surface
• A good, adherent deposit is obtained only if
the base metal surface is free from grease, oil,
oxide layer, and extraneous matter.
• The following methods are employed to clean
the metal surfaces.
Physical (Solvent) cleaning: To dissolve oils
and greases. Eg: CCl4,CH2Cl2,CHCl=CCl2
(OLD)
ethyl lactate, D-Limonene, Methyl Soyate
Chemical (Alkali) cleaning: To remove minute
organic residues. Eg: NaOH, Na2CO3, Na3PO4.
Mechanical Cleaning: Involves
removal of the oxide layer or rust
and other inorganic deposits. Eg:
Impact tools like sandpaper, chisels,
knife scrapers, wire brushes etc.

Pickling: Removal of oxide films by

means of an acid. Eg: 10 - 30%
sulphuric acid is used for this acid
dip. It is again rinsed with hot water.
Electropolishing: The metal to be
cleaned is made as anode in a suitable
acid solution.
*A surface layer of the metal gets
dissolved along with the impurities.
*This helps to remove surface
irregularities.
*The metal is then thoroughly rinsed
with water, dried and used for
electroplating.
 Electroplating of Chromium

Two types of chromium plating:

Decorative Chromium:- A thin deposit of Cr (0.25 -

0.75 mm ) is applied over either copper-nickel or
nickel undercoat.

Hard Chromium:- Involves deposition of a thick

coating of chromium directly over the substrate.
The usual thickness range of hard chrome is 2.5
– 300 mm.
 Decorative chromium
• Bath composition:
250 g chromic acid +
2.5 g H2SO4 per liter of the
solution and 1g trivalent
chromium
• Operating temperature : 45 – 550C
• Current density : 145 - 430 A/ft2
• Anode: Insoluble anodes like Pb or
Pb - 6%Sb or Pb - 7%Sn.
• Cathode: Article to be plated
 Hard chromium
• Bath composition:
250 g chromic acid +
2.5 g H2SO4 per liter
of the solution and 1g
trivalent chromium
• Operating temperature: 50 – 55 oC.
• Current density: 290 - 580 A/ft2
• Anode: Insoluble anodes like Pb or
Pb - 6%Sb or Pb-7%Sn.
• Cathode: Article to be plated
 In the case of chromium plating, inert anodes are
used

 The metal going into the solution is five times of the

metal getting deposited, resulting in the building up
of excessive chromic acid (Cr3+) concentration.

 This leads to imbalance of bath composition.

 Chromium metal becomes passive in the strongly

acidic bath and a black deposit is formed on the
cathode.
• Chromium plating produces an attractive, wear
resistant and abrasion resistant surface.

• Chromium plating is not continuous; it is micro

porous. Hence an undercoat of copper and/or nickel is
essential.

• Applications:
 Decorative chromium provides a durable finish
(on automobiles, furniture, surgical & dental
instruments).
 Hard chromium is applied to many components
in almost every industry.
 Electroless Plating

• It is a method of depositing a metal or alloy

over a substrate (conductor or
nonconductor) by controlled chemical
reduction of the metal ions by a suitable
reducing agent without using electrical
energy.
Metal ions + Reducing agent

Metal + Oxidized product.

It is also termed as autocatalytic plating.

 Process of electroless plating:

• Preparation of active surface

• Preparation of plating bath
• Reduction step

1 March 2023 CHM - 1051 198

The surface to be plated should be catalytically
active
• The catalytic metals like Ni, Co, Steel, Pd etc.,
do not require any surface preparation.
• Non catalytic metals such as Cu, brass, Ag
etc., need activation.
Surface activation can be done by
• Etching – by acid treatment
• Electroplating with a thin layer of metal
• Alternate treatment with SnCl2 and PdCl2.
 Composition of Electroless bath
• Soluble salt of the metal to be plated
• Reducing agent
• A buffer for pH control
• A complexing agent
• Stabilizer is added to prevent
decomposition of plating bath
• Accelerator to increase the rate of
plating
 Advantages of Electroless Plating

• No electrical energy is required

• Better throwing power
• Plating on articles made of insulators
and semiconductors
• Electroless plated coatings possesses
unique mechanical and chemical
properties
 Electroless Plating of Copper
Composition of bath:
• Coating solution : CuSO4 solution (12 g/l)
• Reducing agent : HCHO (8 g/l)
• Buffer : NaOH (15 g/l) and Rochelle salt(14 g/l)
• Complexing agent : EDTA di sodium salt (20 g/l)
• Optimum pH : 11
• Optimum temperature : 25 0C.
Reactions:

Cu2+ + 2e− Cu (S) (at Cathode)

2HCHO + 4OH− 2HCOO− + 2H2O + H2+ 2e− (Anode)

Cu2+ + 2HCHO + 4OH− 2HCOO− +2H2O + H2 + Cu

*Plating rate is 1 - 5 mm h-1.

 Applications

• Used for metalizing printed circuit

boards (PCBs).
• Used as a base coating for
subsequent conventional electroplating
• For producing through hole
connections and for decorative plating
on plastics
Property Electroplating Electroless plating
Driving force Electric current Autocatalytic redox reaction
Cathode Article to be plated Article to be plated with a
catalytic surface
Anode Separate anode Article to be plated
Reducing agent Electrons bring Chemical reagents bring
about about reduction reaction
Anode reactant M or H2O R, the reducing agent in
solution
Nature of Pure metal or alloy Usually metal contaminated
deposit with species derived from
the redox reaction
Thickness (µm) 1 - 100 1 – 100
Applicability Applicable to Can be used for conductors
conductors only and non-conductors
Throwing power Less throwing More throwing power and
power; cannot be can be used for irregular
used for irregular and uneven shaped objects
1 March 2023 shapes andCHMintricate
- 1002 205
parts
THANK YOU
Answer the following questions:
1. Distinguish between electrolytic and galvanic
cells.
2. Explain the origin of electrode potential. What
are the sign conventions for electrode
potential?
3. Give reasons for the following.
(i) The glass electrode changes its emf over a
period of time.
(ii) KCl is preferred instead of NaCl as an
electrolyte in the preparation of salt bridge
4. What is meant by a standard cell? Give an
example
1 March 2023 CHM - 1002 207
 5. Quote any four limitations of glass
electrode
6. Define liquid junction potential. How it can
be eliminated or minimized?
7.Derive Nernst equation for the single
electrode potential.
8.Describe potentiometric determination of
emf of a cell.
9. Explain the construction and working of
Calomel Electrode

1 March 2023 CHM - 1002 208