UNIT – II

Redox Reactions and

Electrochemistry
Electrochemistry
Nernst equation, Electrochemical series and
its applications.
Energy devices
Battery, Supercapacitor, Fuel cells
Corrosion and its control
Chemical and electrochemical corrosion,
Microbial induced concrete corrosion and
biofouling.
Corrosion control - Design, Anodic and
 Introduction to electrochemistry

Electrochemistry - chemical reactions produce electricity

-changes associated with the passage of electrical

The reactions involve electron transfer – Redox reactions.

Many metals – purified, electroplated using the methods

Devices - automobiles, smartphones, electronic tablets, watches,

pacemakers, and many others use batteries for power.

Batteries - chemical reactions for electricity spontaneously

All electrochemical systems involve the transfer of electrons in a
reacting system. In many systems, the reactions occur in a region
known as the cell, where the transfer of electrons occurs at
electrodes
 Introduction to electrochemistry

The SI unit of electrical

The flow of charge - electric current potential - volt (V).
An electric current flows in a path - electric Unit of charge - charge of a
circuit proton (1.602 × 10−19 C)
Electric charge – generates electric field
When 1 coulomb of charge
Ability of the electric field to do work on moves through a potential
the charge - Electrical potential difference of 1 volt, it gains or
loses 1 joule (J) of energy
 Introduction to electrochemistry

Electrochemistry studies oxidation-reduction

reactions
oxidation was the loss of electrons and
reduction was the gain of electrons
Balancing the cell reaction
half-reaction method – To make finding the overall
equation easier
splits+oxidation-reduction
MnO −(aq) Fe2+(aq) ⟶ Mn2+(aq)reactions
+ Fe3+
4
(aq)
unbalanced oxidation half-reaction Unbalanced reduction half-
reaction.
oxidation (unbalanced): Fe2+(aq) ⟶ Fe3+(aq)

reduction (unbalanced): MnO4−(aq) ⟶ Mn2+(aq)

 Balancing Oxidation-Reduction Reactions

Consider Hydrogen ions - in acidic solutions

either in reactants or products contain H or O

oxidation (unbalanced): Fe2+(aq) ⟶ Fe3+(aq)

reduction (unbalanced): MnO4−(aq) ⟶ Mn2+(aq)

•reduction half-reaction does involve oxygen//hydrogen ions

•Convert this oxygen to water.

MnO4 −(aq) + 8H+(aq) ⟶ Mn2+(aq) + 4H2 O(l)

mass balance charge not balanced

the charge is unbalanced
 Balancing Oxidation-Reduction Reactions

oxidation (unbalanced): Fe2+(aq) ⟶ Fe3+(aq)

Charge balancing: Fe2+(aq) ⟶ Fe3+(aq) + e−

Reduction (unbalanced): MnO4 −(aq) + 8H+(aq) ⟶ Mn2+(aq) +

4H2O(l)
•total charge on the left of the reaction arrow is [(−1) × (1) + (8) × (+1)],
or +7
•Right side is [(1) × (+2) + (4) × (0)], or +2.

Reduction (balanced): MnO4 −(aq) + 8H+(aq) + 5e− ⟶ Mn2+(aq) +

4H2O(l)

check this half-reaction for each atom type and for the
charge
 Balancing Oxidation-Reduction Reactions

oxidation: Fe2+(aq) ⟶ Fe3+(aq) + e−

reduction: MnO4−(aq) + 8H+(aq) + 5e− ⟶ Mn2+(aq) +

4H2O(l) combine the two halves to produce a whole reaction

key - the electrons
(e-)
e- from the [O] half-reaction = the [R] half-reaction

[O] half-reaction
produce = 1 e-
[R] half-reaction
needs
= 5 e-
 Balancing Oxidation-Reduction Reactions

owest common multiple of one and five is five

oxidation: 5 × (Fe2+(aq) ⟶ Fe3+(aq) + e−)
reduction: MnO4−(aq) + 8H+(aq) + 5e− ⟶ Mn2+(aq) + 4H2O(l)

overall: 5Fe2+(aq) + MnO4−(aq) + 8H+(aq) ⟶ 5Fe3+(aq) + Mn2+(aq)

+ 4H2O(l)
Fe: Does (5 × 1) = (5 × 1)?
Mn: Does (1 × 1) = (1 × 1)?
H: Does (8 × 1) = (4 × 2)?.
O: Does (1 × 4) = (4 × 1)?.
Charge: Does [5 × (+2) + 1 × (−1) + 8 × (+1)] = [5 × (+3) + 1 ×
(+2)]?.
 Balancing Oxidation-Reduction Reactions
basic solution
hydrogen ion concentration is lower and the hydroxide ion
concentration is higher.
hydroxide ions will react with hydrogen ions to produce water

start with the balanced equation in acidic solution, then

“convert” it to the equation for basic solution

to convert to a basic reaction, it is necessary to add the same

number of hydroxide ions to each side of the equation so
that all the hydrogen ions (H+) are removed and mass
balance is maintained. Hydrogen ion combines with
hydroxide ion (OH−) to produce water
 Balancing Oxidation-Reduction Reactions

Cl−(aq) + MnO4−(aq) ⟶ ClO3−(aq) + MnO2(s)

Balancing this as acid gives

Cl−(aq) + 2MnO4−(aq) + 2H+(aq) ⟶ ClO3−(aq) + 2MnO2(s) + H2O(l)

add two hydroxide ions to each

side

Cl−(aq) + 2MnO4−(aq) + (2H+ + 2OH−)(aq) ⟶ ClO3−(aq) + 2MnO2(s) + H2O(l) +

2OH−(aq)
Cl−(aq) + 2MnO4−(aq) + (2H2O)(l) ⟶ ClO3−(aq) + 2MnO2(s) + H2O(l) + 2OH−(aq)

Cl−(aq) + 2MnO4−(aq) + H2O(l) ⟶ ClO3−(aq) + 2MnO2(s) + 2OH−(aq)

 Balancing Oxidation-Reduction Reactions

Cl−(aq) + 2MnO4−(aq) + H2O(l) ⟶ ClO3−(aq) + 2MnO2(s) + 2OH−(aq)

Cl: Does (1 × 1) = (1 × 1)?

Mn: Does (2 × 1) = (2 × 1)?
H: Does (1 × 2) = (2 × 1)?
O: Does (2 × 4 + 1 × 1) = (3 × 1 + 2 × 2 + 2 × 1)? .
Charge: Does [1 × (−1) + 2 × (−1)] = [1 × (−1) + 2
× (−1)]? .
 Balancing Oxidation-Reduction Reactions

Example 1
Balancing Acidic Oxidation-Reduction Reactions
Balance the following reaction equation in acidic solution:
MnO4−(aq) + Cr3+(aq) ⟶ Mn2+(aq) + Cr2O72−(aq)

10Cr3+(aq) + 11H2 O(l) + 6MnO4 −(aq) ⟶ 5 Cr2 O7 2−(aq) + 22H+(aq) +

6Mn2+(aq)
Example 2 (in acidic condition)
Hg22+ + Ag ⟶ Hg + Ag+

Hg22+(aq) + 2Ag(s) ⟶ 2Hg(l) + 2Ag+(aq)

 Balancing Oxidation-Reduction Reactions

Example 3
Balance the following reaction equation in basic solution:
MnO4 −(aq) + Cr(OH)3(s) ⟶ MnO2(s) + CrO42−(aq)

OH−(aq) + MnO4−(aq) + Cr(OH)3(s) ⟶ CrO42−(aq) + MnO2(s) +

2H2O(l)
Example 4
Balance the following in the type of solution indicated.
(a) H2 + Cu2+ ⟶ Cu (acidic solution)
(b) H2 + Cu(OH)2 ⟶ Cu (basic solution)
(c) Fe + Ag+ ⟶ Fe2+ + Ag
(d) Identify the oxidizing agents in reactions (a), (b), and (c).
(e) Identify the reducing agents in reactions (a), (b), and (c).
 Oxidation-Reduction Reactions

• Oxidation is loss of e-
causes reduction ; “reducing agent”

• Reduction is gain of e-
causes oxidation; “oxidizing agent”
 Types of cells

Voltaic (galvanic) cells:

A spontaneous reaction generates electrical energy

Electrolytic cells:
absorb free energy from an electrical source to drive a
nonspontaneous reaction
The basic components of galvanic cells

• Electrochemical cells,

• Spontaneous oxidation-reduction

• Produce electrical energy

 Galvanic Cell: Common Components
Electrodes:
Conduct electricity between cell and surroundings

Electrolyte:
Mixture of ions involved in reaction or carrying charge

Salt bridge:
Completes circuit (provides charge balance)

Anode:
Oxidation occurs at the anode

Cathode:
Reduction occurs at the cathode
Galvanic Cell: Reaction setup
 Galvanic Cell: Electrochemical cell

anode (oxidation): Zn(s) ⟶ Zn2+(aq) + 2e−

cathode (reduction): Cu2+(aq) + 2e− ⟶ Cu(s)

overall: Zn(s) + Cu2+(aq) ⟶ Zn2+(aq) + Cu(s)

Zn gives up electrons to Cu
• “pushes harder” on e-
• greater potential energy
• greater “electrical potential”

Spontaneous reaction
• due to relative difference in metals’ abilities
to give e-
 Galvanic Cell: Electrochemical cell - cell notation
Cell Notation (Cell Diagram)
Information about various species involved in the reaction
1. On the left hand side =
A vertical line │ = phase boundary Information of anode
2. the anode solution
Double vertical line ││ = the salt 3. the salt bridge (when present)
4. the cathode solution,
bridge
5. information about the cathode to
the right
 Galvanic Cell: Electrochemical cell - cell notation

anode (oxidation): Zn(s) ⟶ Zn2+(aq)+2e−

cathode (reduction):Cu2+(aq)+2e− ⟶

Cu(s)

overall: Zn(s)+Cu2+(aq) ⟶ Zn2+(aq)+Cu(s)

Using cell notation:

Zn(s)│Zn2+(aq)║Cu2+

(aq)│Cu(s).
 Galvanic Cell: Electrochemical cell - cell notation

The cell notation for the galvanic cell

= Cu(s)│Cu2+(aq, 1M)║Ag+(aq,
1M)│Ag(s)
 Galvanic Cell: Electrochemical cell - cell notation

Consider a galvanic cell consisting of

2Cr(s)+3Cu2+(aq) ⟶ 2Cr3+(aq)
+ 3 C u the
Write ( s ) oxidation and reduction half-reactions and write the
reaction using cell notation. Which reaction occurs at the anode?
The cathode?
oxidation: 2Cr(s) ⟶ 2Cr3+(aq)+6e−
reduction:3Cu2+(aq)+6e− ⟶ 3Cu(s)
overall: 2Cr(s)+3Cu2+(aq) ⟶ 2Cr3+(aq)

No + 3 C u ( s )
concentrati Cr(s)│Cr3+(aq) ║ Cu2+(aq)│Cu(s).
ons were
specified
 Cell Potential, Ecell

Ecell = +1.10 V

Ecell = Ecathode – Eanode

 Cell Potential, E0cell
To find out the cell potential

E0cell
cell potential under standard conditions

elements in standard states (298

K)

solutions: 1M

gases: 1 atm
If you know about the cell potential at standard condition, one
can find the cell potential at various conditions using Nernst
 E0cell and Δ G0

• E0cell > 0 ΔG0 < 0 Spontaneous

• E0cell < 0 Δ G0 > 0 Not

• E0cell = 0 Δ G0 = 0 Equilibrium

Nernst Equation
 Cell Potential, E0cell - standard hydrogen electrode (SHE).

• It is impossible to determine the electrical potential of a single

electrode

• We can assign an electrode the value of zero and then use it as a

• reference
The electrode chosen as the zero is shown and is called the standard
hydrogen electrode (SHE).
• The SHE consists of 1 atm of hydrogen gas bubbled through a 1 M HCl
solution, usually at room temperature. Platinum, which is chemically
inert, is used as the electrode.
• The reduction half-reaction chosen as the reference is

2H+(aq, 1M)+2e− ⇌H2(g, 1 atm) E°=0 V

 Cell Potential, E0cell - standard hydrogen electrode (SHE).

E° is the standard reduction potential. The superscript “°” on the E

denotes standard conditions (1 bar or 1 atm for gases, 1M for solutes).
The voltage is defined as zero for all temperatures
 Cell Potential, E0cell – standard reduction potential

The standard reduction potential (Single electrode potential)

• subtracting the standard reduction potential for the reaction
occurring at the anode from the standard reduction potential for the
reaction occurring at the cathode.
• sign is necessary because oxidation is the reverse of reduction

E 0c e l l = E0cathode −E0anode

+0.34 V = E0Cu2+/Cu −E0H+/H2

= E0Cu2+/Cu −0
The standard reduction potential (Single electrode
potential)

A galvanic cell consisting of a

SHE and Cu2+/Cu half-cell can

be used to determine the

standard reduction potential

The standard reduction potential (Single electrode
potential)
A galvanic cell can be used to

determine the standard reduction

potential
 The standard reduction potential (Single electrode
potential)
Cell notation

Pt(s)│H2(g, 1 atm)│H+(aq, 1M)║Cu2+(aq, 1M)│

Cu(s)

Electrons flow from the anode to the

cathode.

Anode (oxidation): H 2 ( g ) ⟶ 2 H + ( a q ) +
2e−
Cathode (reduction): C u 2 + ( a q ) + 2 e − ⟶
Cu(s)
 The standard reduction potential (Single electrode
potential)
Pt(s)│H2(g, 1 atm)│H+(aq, 1M)║Ag+(aq, 1M)│Ag(s)

Electrons flow from left to right, Reduction potential

anode (oxidation): H2(g) ⟶ 2H+(aq) E0cell ° = E0cathode −E0anode

+2e−
+0.80 V = E0 Ag+/Ag − E0
cathode (reduction):2Ag+(aq)+2e− ⟶
2Ag(s) H+/H2

overall: 2Ag+(aq)+H2(g) ⟶ 2H+(aq) = E 0 Ag+/Ag − 0

+2Ag(s)
= E0Ag+/Ag
The standard reduction potential (Single electrode
potential)
Electrochemical
series
 Practice problems
What is the standard cell potential for a galvanic cell that consists of
Au3+/Au and Ni2+/Ni half-cells? Identify the oxidizing and reducing agents.
Au3+(aq) + 3e− ⟶ Au(s) E°Au3+ /Au = + 1.498 V

Ni2+(aq) + 2e− ⟶ Ni(s) E° Ni2+ /Ni = − 0.257 V

Galvanic cells have positive cell potentials

Anode (oxidation): Ni(s)⟶Ni2+(aq) + 2e− E°anode = E° Ni2+ /Ni = −0.257 V

Cathode (reduction): Au3+(aq) + 3e− ⟶Au(s) E°cathode = E° Au3+ /Au =

+1.498 V 3 N i ( s ) + 2 A u ( a q ) ⟶ 3 N i ( a q ) + 2 A u ( s )
3+ 2+

E°cell = E°cathode − E°anode = 1.498 V − (−0.257 V) = 1.755

V
From the half-reactions, Ni is oxidized, so it is the reducing agent,
and Au3+ is reduced, so it is the oxidizing
Practice problems
 Practice problems

A galvanic cell consists of a Mg electrode in 1 M Mg(NO 3)2 solution and a

Ag electrode in 1 M AgNO3

Mg(s) + 2Ag+(aq)⟶Mg2+(aq) + 2Ag(s)

E°cell = 0.7996 V − (−2.372 V) = 3.172 V

 Cell Potentials at Nonstandard
Conditions
Consider the following reaction at room temperature:
C o ( s ) + Fe 2 + ( a q , 1 . 9 4 M ) ⟶ C o 2 + ( a q , 0 . 1 5 M ) +
Fe ( s )
Is the process spontaneous?
If the cell potential is positive, the process is
spontaneous.

Anode (oxidation): Co(s) ⟶ Co2+(aq) + 2e− E ° Co2+ /Co =

−0.28 V
Cathode (reduction): Fe2+(aq) + 2e− ⟶ Fe(s) E° Fe2+ /Fe = −0.447 V
 Practice problems
E°cell = E°cathode − E°anode = −0.447 V − (−0.28 V) =
−0.17 V
The process is not spontaneous under standard conditions.

Using the Nernst equation and the concentrations stated in the problem and
n = 2,
− n F E c e l l = − n F E ° c e l l + RT l n Q

E c e l l = E ° c e l l − ( RT / n F ) l n Q
This is the Nernst equation. At standard temperature (298.15 K), it is
possible to write the above equations as
E c e l l = E ° c e l l − ( 0.0257 V / n ) l n Q

E c e l l = E ° c e l l − ( 0.0592 V / n ) l o g Q
 Practice problems

Q = [Co2+] / [Fe2+]
= 0.15 M / 1.94 M
= 0.077
E c e l l = E ° c e l l − ( 0.0592 V / n ) l o g Q

E c e l l = E ° c e l l − ( 0.0592 V / 2 ) l o g 0 . 0 7 7

Ecell = −0.17 V + 0.033 V = −0.014 V

The process is (still) nonspontaneous.

 Practice problems

What is the cell potential for the following reaction at room temperature?

Al(s) │ Al3+(aq, 0.15 M) ║ Cu2+(aq, 0.025 M) │ Cu(s)

What are the values of n and Q for the overall reaction? Is the reaction

spontaneous under these conditions?

Answer: n = 6; Q = 1440; Ecell = +1.97 V,

spontaneous
 Galvanic cells vs Electrolytic cells

Galvanic cells

chemical energy
is converted into
electrical energy.

The opposite is
true for
electrolytic cells
 Electrolysis

Electrolytic cells

• Electrical energy causes nonspontaneous reactions to occur in a

process known as electrolysis

• Electrical energy is converted into the chemical energy in the battery

as it is charged.

• Once charged, the battery can be used to power the automobile.

 The Electrolysis of Water

Water into hydrogen and oxygen gas by electrolysis

Acids are typically added to increase the

concentration of hydrogen ion in solution

Anode:
2H2O(l) ⟶ O2(g) + 4H+(aq) + 4e−
E°anode = +1.229 V
Cathode:
2H+(aq) + 2e− ⟶ H2(g)
E°cathode = 0 V

Overall:
2H2O(l) ⟶ 2H2(g) + O2(g)
E°cell = −1.229 V
 The Electrolysis of Water

• Sulfuric acid is not consumed and that the volume of

hydrogen gas produced is twice the volume of oxygen gas

produced.

• The minimum applied voltage is 1.229 V.

 Electroplating
Significance of electroplating:
Chrome plating:
Shiny Ni coating for
appearance and reducing friction in
not corroding connectors and for
Steel Bolts, nuts increasing
and washers are conductivity
coated with zinc -
Anticorrosion

Aesthetic gold on
the surface of
Silver, copper and
silver and copper
brass for electrical
connectors
 Electroplating
Materials required for the experiment

Cu –Wire/Plate Fe – Nail/rod Glass Beaker DC Power Source

Electrolyte

Ni Cu Au

Ni Soln. Cu Soln. Au Soln.

Electrolyte - various metal Various Metal coated on the

salt solution electrode surface
 Electroplating
DC Power Source
e- e-

e- e-

e- e-

Electrolysis e- e-

Copper Metal
e- e-
(Anode) Iron Nail
Oxidation of the metal (Cathode)
Reduction
e-

Electrolyte
0.1 M Solution of CuSO4.5 H2O

Changing the concentration of the electrolyte

Rate of electroplating
Changing the current flow through the circuit
 Electroless plating

Metal Reducing Oxidized

ions (Mn+)(aq) + agent (ne-) Metal (M) + Product
Deposited over
any solid surf ace
 Electroplating

• An important use of electrolytic cells - electroplating.

• Results in a thin coating of one metal on top of a conducting surface

• Use of coating - corrosion resistant, strengthening the surface,

producing a more attractive finish, or for purifying metal.

• Metal in use for coating - cadmium, chromium, copper, gold, nickel,

silver, and tin.

• Common consumer products - silver-plated or gold-plated tableware,

chrome-plated automobile parts, and jewelry.
Electroplating

anode: Ag(s) ⟶ Ag+(aq) + e−

cathode: Ag+(aq) + e− ⟶ Ag(s)

 Batteries and Fuel Cells

• Classify batteries as primary or secondary

• Some of the characteristics and limitations of batteries

• Provide a general description of a fuel cell

 Batteries

• Battery - Electrochemical cell or series of cells - Electric current

• Galvanic cell - Battery

• Batteries - particular application, keeping things like the mass

of the battery, its cost, reliability, and current capacity in

mind.
 Batteries

Primary Batteries Secondary Batteries

Single-use batteries because they Secondary batteries are

cannot be recharged rechargeable. These are the
types of batteries found in
devices such as smartphones,
electronic tablets, and
automobiles.
 Primary Batteries
Zinc–carbon battery (Leclanche cell)/ Dry Cell

Single-use batteries because they cannot be recharged

 Primary Batteries - Zinc–carbon battery
• The zinc can serves as both a container and the negative
electrode.

• The positive electrode is a rod made of carbon that is surrounded by

a paste of manganese(IV) oxide,
zinc chloride,
ammonium chloride,
carbon powder, and
a small amount of water.

Cell notation: Zn(s)/ZnCl2(aq), NH4Cl(aq)/MnO2/C(s)

Primary Batteries - Zinc–carbon battery

Crystals of [Zn(NH3)2]Cl2(s)
formed by the interaction
of free NH3 precipitate out
shielding the active
material of both the
electrodes. This leads to
the deterioration of the
cell parameters
and the cell voltage drops
 Primary Batteries - Zinc–carbon battery

Anode Zn(s) ⟶ Zn2+(aq) + 2e− E ° Zn2+ /Zn = − 0.7618 V

Cathode 2MnO2(s) + 2NH4Cl(aq) + 2 e− ⟶ Mn2O3(s) + 2NH3(aq) +

H2O(l) + 2Cl−
Overall
2MnO2(s) + 2NH4Cl(aq) + Zn(s) ⟶ Zn2+(aq) + Mn2O3(s) + 2NH3(aq) + H2O(l)
+ 2Cl−
overall cell potential at initial 1.5 V

As the zinc container oxidizes, its contents eventually leak

out, so this type of battery should not be left in any electrical
device
 Primary Batteries - Alkaline battery

• Alkaline batteries - 1950s

• To address some of the

performance issues with zinc–
carbon dry cells.

• They are manufactured to be exact

replacements for zinc-carbon dry
cells

• Use alkaline electrolytes, often

 Primary Batteries - Alkaline battery

anode:

Zn(s) + 2OH−(aq)⟶ZnO(s) + H2O(l) + 2e−

E°anode = −1.28 V

cathode:

2MnO2(s) + H2O(l) + 2e− ⟶Mn2O3(s) + 2OH−(aq)

E°cathode = +0.15 V

overall:

Zn(s) + 2MnO2(s)⟶ZnO(s) +Mn2O3(s) E°cell = +1.43 V

 Primary Batteries - Alkaline battery

• An alkaline battery can deliver about three to five times the energy of

a zinc-carbon dry cell of similar size.

• Alkaline batteries are prone to leaking potassium hydroxide.

• So these should also be removed from devices for long-term storage.

 Secondary Batteries

Lead acid battery Nickel-cadmium Lithium ion batteries

 Secondary Batteries
Lead acid battery

• Used in your automobile

• Inexpensive and capable of producing the high current required by

automobile starter motors

• A lead acid battery consists of a rectangular ebonite Or polymeric

case which contains 5 m sulphuric acid (37 per cent).

Lead acid battery
 Secondary Batteries
Lead acid battery
The main active materials required to construct a lead acid battery are

Lead Peroxide (PbO2)

The positive plate is made of lead peroxide. This is dark brown,

hard and brittle substance.

Sponge Lead (Pb)

The negative plate is made of pure lead in soft sponge condition.

Dilute Sulfuric Acid (H2SO4)

Cell notation Pb–PbSO4 / H2SO4 (5 M) / Pb – PbSO4–PbO2

Discharge
(Voltaic)

Recharge
(Electrolytic)
 Secondary Batteries
Lead acid battery
• Voltage of each cell 2 V; Total voltage of six cells in series 12 volts

discharging
• overall: Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) +
2H2O(l)
charging

• Sulphuric acid gets diluted during

discharging

Hydromete
r
Charge
 Secondary Batteries
Nickel-cadmium, or NiCd

Anode: spongy cadmium with cadmium hydroxide

Cathode: paste of nickeloxyhydroxide NiO(OH) (s) and small

amount of graphite to increase electrical conductivity

Electrolyte : 5 M KOH solution

Cell Reaction :
C d ( s ) / C d ( O H ) 2 / KO H ( 5 M ) / N i O ( O H ) ( s ) /
Ni(OH)2(s)
 Secondary Batteries
Nickel-cadmium, or NiCd

NiCd batteries use a

“jelly-roll” design that
significantly
increases the amount
of current the battery
can deliver as
compared to a
similar-sized alkaline
battery
 Secondary Batteries
Nickel-cadmium, or NiCd

Anode: Cd(s) + 2OH– (aq) → Cd(OH)2 (s) + 2e–

Cathode: 2NiO(OH)(s) + 2H2O (l) +2e– → 2Ni(OH)2 (s) + 2OH– (aq)

Overall reaction: Cd (s) + 2NiO(OH) (s) + 2H2O(l) → 2Ni(OH)2 (s) +

Cd(OH)2 (s)

Voltage is ~ 1.35 V
 Secondary Batteries
Nickel-cadmium, or NiCd

• NiCd battery can be recharged about 1000 times

• Cadmium is a toxic heavy metal

• voltage is fairly constant

• No deterioration as no gases

• light, portable and rechargeable

 Secondary Batteries
lithium ions

• Charge flows between the electrodes as the lithium ions move

between the anode and cathode.
 Secondary Batteries
lithium ions

• Most popular rechargeable batteries and are used in many portable

electronic devices.

• Reduction takes place at the cathode. There, cobalt oxide combines

with lithium ions to form lithium-cobalt oxide (LiCoO 2).

CoO2 + Li+ + e- → LiCoO2

 Secondary Batteries
lithium ions

Oxidation takes place at the anode. There, the graphite intercalation

compound LiC6 forms graphite (C6) and lithium ions. The half-reaction is:

LiC6 → C6 + Li+ + e-

Here is the full reaction (left to right = discharging, right to left =

charging):

LiC
The 6 + CoO
battery 2 ⇄ C6 +is
voltage LiCoO
about
2 3.7 V
 Supercapacitors (SC’s)

• Supercapacitors (SC’s) are energy storages having similarities with

batteries

• Unlike batteries, SC’s store electrical energy, not chemical energy.

• Supercapacitors have many names:

• electrochemical capacitor (EC Capacitor),

• Electric double-layer capacitor (EDLC),

• ultracapacitor, ... All meaning the same thing.

 Supercapacitors (SC’s)

• Supercapacitors can be fully charged and discharged in seconds

• SC’s can be charged and discharged even up to a million times

• SC’s have very low energy densities vs. batteries

• SC’s have very high self-discharge vs. batteries

Supercapacitors (SC’s)
 • Supercapacitors (SC’s)

• In discharged state all the ions are distributed randomly within the
cell.

• In charged state all the positive ions travel to the negative terminal
and vice versa

• The higher the carbon electrode surface area is, the higher the cell
capacitance is
Fuel Cells
 General Functional diagram of fuel cell

• hydrogen enters at the anode where it loses

electrons.
• electrons travel to the cathode

• Oxygen enters at the cathode

It picks up electrons and either

• Combines with the hydrogen ions that

travel from the anode through the
electrolyte or

• Travels to the anode through the

electrolyte and combines with
hydrogen ions.
 General Functional diagram of fuel cell

• The electrolyte plays a vital role in a fuel cell. It permits

appropriate ions to pass between the anode and cathode.

• Depending on the type of electrolyte used, there can be

different types of fuel cells.

Alkali fuel cell
 Alkali fuel cell

• H2 – O2 fuel cell

• Alkali (aqueous 25% kOH at 200 °c) is used as an electrolyte

• Electrodes consists of two inert porous electrodes made up of either

graphite impregnated with finely divided platinum

• or a 75/25 alloy of palladium (pd) with silver (ag) or nickel (ni)

• Hydrogen and oxygen are bubbled through the anode and cathode
respectively.
 Alkali fuel cell

The cell reactions

Anodic reaction

H2+ 2OH– → 2H2O + 2e–

Cathodic reaction

½ O2 + H2O + 2e– → 2OH–

Net cell reaction

H2 + ½ O2 → H2O

The EMF of the cell is nearly 1.23 volts.

Proton Exchange Membrane (PEM)
 Proton Exchange Membrane (PEM)

Hydrogen–oxygen fuel cell consists of porous screens of graphite

coated with a layer of platinum catalyst

Electrode reactions

Anodic reaction H 2 → 2 H + + 2 e –

Cathodic reaction ½ O 2 + 2 H + + 2 e – → H 2 O

Overall cell reaction H 2 + ½ O 2 → H 2 O

The EMF : 1.2 V.

Solid electrolyte - solid polymer electrolyte cell.

Useful in spacecrafts.
Proton Exchange Membrane (PEM)
 Proton Exchange Membrane (PEM)

Hydrogen–oxygen fuel cell consists of porous screens of graphite

coated with a layer of platinum catalyst

Electrode reactions

Anodic reaction H 2 → 2 H + + 2 e –

Cathodic reaction ½ O 2 + 2 H + + 2 e – → H 2 O

Overall cell reaction H 2 + ½ O 2 → H 2 O

The EMF : 1.2 V.

Solid electrolyte - solid polymer electrolyte cell.

Useful in spacecrafts.
 Solid oxide fuel cells (SOFC)

• Cell – Completely Solid mateials

• Anode: nickel–zirconium oxide or nickel–yttrium oxide

• Cathode is made up of lanthanum manganate LaMnO3

• Electrolytes : ceramic compounds

• Operating Temp. around 1000 °C

• Hydrogen and carbon monoxide - fuel

• Oxygen - an oxidizing agent

 Solid oxide fuel cells (SOFC)

Cell reactions:

At anode
H2(g) + CO(g) + O22– → H2O + CO2 + 2e–

At cathode O2 + 2e– → O22–

Overall cell reaction O2 + H2 + CO → H2O + CO2

corrosion
 Why does corrosion occur?

most familiar example of corrosion is the formation of rust on

iron
anode: Fe(s) ⟶ Fe2+(aq) + 2e−

The electrons reduce oxygen in the air in acidic solutions.

cathode: O2(g) + 4H+(aq) + 4e− ⟶ 2H2O(l)

overall: 2Fe(s) + O2(g) + 4H+(aq)⟶2Fe2+(aq) + 2H2O(l) E°cell = +1.67 V

rust is hydrated iron(III) oxide,

which forms when iron(II) ions react further with oxygen.

4Fe2+(aq) + O2(g) + (4 + 2x) H2O(l) ⟶ 2Fe2O3 ·xH2O(s) + 8H+(aq)

Corrosion is defined as degradation or destruction of metal or an alloy

because of chemical or electrochemical reaction with the surrounding

environment or medium.

Rusting is the corrosion related to iron and iron-based alloys.

Nonferrous metals corrode but do not rust.

 Four requirements of corrosion

Anode

Cathode

Current flow

Electronic path
 Economic factors

Direct loss Indirect loss

 Shutdown
 Replacing corroded structure and equipment

 Loss of product
 Adding corrosion inhibitors

 Contamination of product
 Cost for corrosionresistant metals

 Loss of efficiency
 Consequences of corrosion

• Waste of metals

• 25% of annual world production of iron is wasted due to

corrosion

• Decrease in efficiency of machineries

• Failure of machineries

• Leakage in the process

• Health & fire hazard

• Causes contamination
 Types of corrosion

The two basic theories of corrosion are

• Dry or chemical corrosion.

• Wet or electrochemical corrosion.

 Dry or chemical corrosion

 Simplest case of corrosion.

 Corrosion takes place due to direct chemical attack.

 Oxygen, halogens, hydrogen sulphide, nitrogen etc.

 Corrosion product may be insoluble, soluble or liquid product

 Classificatio
n
Takes place by
Oxidation direct action of O2
corrosion Absence of
moisture

Chemical or Dry
corrosion Corrosion due CO2, SO2, Cl2,
To gases H2S, F2

Corrosion due Flowing liq at

To liquid-metal high temp.
 Chemical or Dry
corrosion
Oxidation corrosion
Chemical reactions involved

2M  2 Mn+ + 2n e– (loss of electrons – oxidation)

n/2 O2 + 2 ne–  nO2– (Gain of electrons – reduction)

2M + n/2 O2  2 Mn+ + nO2–

Metal oxide
 The nature of the oxide film

Stable

It is fine grained, tightly sticking and impervious

Al, Sn, Pb and Cu - protective layer and prevents further corrosion

 The nature of the oxide film

Exposed surface Stable oxide formation

O2 No corrosion
 The nature of the oxide film
Unstable

decomposes back into metal and oxygen

Ag, Pt and Au. As a result, there is no corrosion

Exposed surface Stable oxide formation

decomposition
O2

+ O2
 The nature of the oxide film
Volatile

volatilizes as soon as it is formed

This causes rapid and continuous corrosion

2Mo + 3O2 2MoO3

Exposed surface Exposed surface

O2 Oxide volatilize
 The nature of the oxide
film
Porous
The oxide film is porous, that is, having pores or cracks. Here the O2 penetrate
inside and attacks the underlying metal and hence continuous corrosion occurs
for example, iron and steel

Exposed Porous oxide layer continuous corrosion

surface

O2
 Wet or electrochemical corrosion

• under wet or moist conditions

• corrosion cell

(i) separate anodic and cathodic areas.

(ii) electrode potential between the anode and cathode.

(iii) metal path connecting the anode and cathode.

(iv) Conducting liquid between the two electrodes.

 Wet or electrochemical corrosion

Anodic reactions

corrosion always occurs at the anodic

areas

• M  Mn+ + ne–

(Metal) Metal ion

• Mn+ = Dissolves in solution.

(Metal ion)
 Wet or electrochemical corrosion
Cathodic reactions Evolution of hydrogen

cathodic reactions are of two types

Absorption of oxygen

Evolution of hydrogen
anodic areas are large and cathodic neutral and alkaline medium
areas are small
2H2O + 2e– H2 + 2OH–
oxygen is absent.

environment is acidic, H+ ions

2H+ + 2e– H2
 Wet or electrochemical corrosion

Cathodic reactions

Evolution of hydrogen
• anodic areas are large and cathodic areas are small

• oxygen is absent.
• neutral and alkaline medium
 Examples

In acid

In neutral or alkaline medium

Wet or electrochemical corrosion
Wet or electrochemical corrosion
bsorption of oxygen (Cathodic reactions)

• Anodic areas are small and cathodic areas are large.

• Oxygen is present and the environment is neutral or alkaline.

 Chemical corrosion vs Electrochemical corrosion

Chemical corrosion Electrochemical corrosion.

1. Takes place in dry condition. 1. Takes place in presence on wet
2. Takes place by direct chemical condition.
attack. 2. Takes place through the formation
3. Can take place on of cell.
heterogeneous or 3. Can take place only on
homogeneous metal surface. heterogeneous metal surface.
4. Uniform corrosion. 4. Non-uniform corrosion.
5. Corrosion product accumulates 5. Corrosion product accumulates at
at the spot. the
 Types of
electrochemical
corrosion

Differential aeration or Differential metallic

concentration cell corrosion (DMC)
corrosion (DAC)

• Galvanic corrosion
• Pitting corrosion
• Waterline corrosion
• Stress corrosion
• Corrosion under a drop of water, leaf, stone, block of
wood, etc.
• Caustic embrittlement, etc
 Differential metallic corrosion (DMC)
Galvanic Corrosion

• Two dissimilar metals (eg., Zinc and copper) electrically connected

and exposed to an electrolyte,

• The Metal Higher In Electrochemical Series Undergoes Corrosion.

• In this process, the more active metal (with more negative electrode
potential) acts as a anode

• While the less active metal (with less negative electrode potential)
acts as cathode.
Differential metallic corrosion (DMC)
Galvanic Corrosion
 Differential metallic corrosion (DMC)
Galvanic Corrosion (Zn and Cu)

Zn  Zn2+ + 2e–

Acidic environment 2H+ + 2e–  H2 (evolution of

hydrogen)

Alkaline or neutral environment ½ O2 + H2O + 2e–  2OH–

(absorption of oxygen)

Zn2+ and 2OH– ions interact to form Zn(OH)2.

Hence, Zn dissolves and Cu is protected

Differential metallic corrosion (DMC)

Galvanic Corrosion (Fe and Sn)

 Galvanic Corrosion – Galvanic series
Most cathodic, noble, or resistant to Most anodic or easy to corrode
corrosion • Chlorimet 2
• Platinum • Hastelloy B
• Gold • Inconel (active)
• Graphite • Nickel (active)
• Titanium • Tin
• Silver • Lead
• Chlorimet 3 • Lead-tin solders
• Hastelloy C • 18-8 Mo stainless steel (active)
• 18-8 Mo stainless steel (passive) • 18-8 stainless steel (active)
• 18-8 stainless steel (passive) • Ni-resist
• Chromium steel >11 % Cr (passive) • Chromium steel >11 % Cr (active)
• Inconel (passive) • Cast iron
• Nickel (passive) • Steel or iron
• Silver solder • 2024 aluminum
• Monel • Cadmium
• Bronzes • Commercially pure aluminium
• Copper • Zinc
• Brasses • Magnesium and its alloys
 Differential metallic corrosion (DMC)
Galvanic Corrosion
The common examples of galvanic corrosion are as follows

• Use of Cu pipes in conjunction with iron pipes in water

distribution system.

• A steel propeller shaft in a bronze bearing.

• Steel screw in brass marine hardware.

• Lead–antimony solder around Cu wire.

 Differential aeration or
concentration cell corrosion
(DAC)
• electrochemical attack on the metal surface, exposed to an
electrolyte of varying concentrations or of varying aeration

• when one part of metal is exposed to a different air concentration from

the other part

• difference in potential between differently aerated areas

• poor-oxygenated parts are anodic

 Differential aeration or
concentration cell corrosion
Example : (DAC)
The metal part immersed in water or in a conducting liquid is
called water line corrosion.

• metal : partially immersed in a conducting solution

• metal part above the solution : more aerated & cathodic

• metal part inside the solution : less aerated & anodic and suffers
corrosion
 Differential aeration or
concentration cell corrosion
(DAC)
 Differential aeration or
concentration cell corrosion
(DAC)

At anode:

M M2+ + 2e-

At cathode: OH- ions are produced (more aerated)

½ O2 + H2O + 2e- 2OH-

 Differential aeration or
concentration cell corrosion
Examples (DAC)
1) Pitting or localized corrosion

2) Crevice corrosion (under a washer or bolt head, the space between plates

or flanges, gaps between poorly welded joints – basically any small gaps)

3) Pipeline corrosion

4) Corrosion on wire fence

Identify the type of corrosion taking place in the following systems (i and ii) and discuss its
causes.
 Biofouling and biocorrosion
Biofouling
• Undesirable accumulation of microorganism, plant, algae
on wetted structures

• Ship hulls, navigation instruments, aquaculture net cages, and

sea water holding pipes, iron pipes used in underground
applications
 Biofouling -Disadvantages

• Fuel consumption increases

• Slow speed of ship

• More manpower

• Increased cost for shipping

• Poor quality of water

• Health issues for many livelihoods

 biocorrosion

• At microbial adsorption : less exposure of oxygen acts = anode

• Other locations : with relatively higher exposure to oxygen =

cathode.

• With different oxygen concentration forms differential aeration

corrosion.
• The microbial species release organic or inorganic acids lead to
undergo higher corrosion.

Some of the bacteria

Shewanella sp.

Desulfuromonas sp.and Desulfobactor

sp.
 biocorrosion
Anodic reaction
Fe → Fe2+ +2e-
Cathodic reaction
2e- + 2 H+ → H2
Overall:
Fe + 2 H+ → Fe2+ + H2 (Acidic)

Fe + 2 H2O → Fe(OH)2 + H2
(Neutral)
4 H2 + SO42− → HS− + 3 H2O +
OH −
Fe2+ + HS− → FeS + H+

4 Fe + SO42− + H+ + 3 H2O → FeS + 3 Fe(OH)2 + OH−

 Microbial induced concrete corrosion

• A special case of biocorrosion is the corrosion of metals (especially iron

and steel) and cement used in construction applications.

• iron used in concrete applications can corrode when microorganisms

are present.

• Chemical ingredients present in cement such as calcium carbonate,

silicate and aluminate reacts with water and the products released by
microorganisms.
 Microbial induced concrete corrosion

Products
produced due to
biocorrosion
occupy more
volume compared
to the bare metal
that leads to
mechanical stress
in metal,
enhancing the
corrosion
reaction.
 Corrosion control
CHOICE OF METALS AND ALLOYS

PROPER DESIGNING

CATHODIC PROTECTION:

ANODIC PROTECTION:

PROTECTIVE COATINGS

INHIBITORS
 Choice of metals and alloys

1 noble metals such as gold and platinum; resistant to corrosion but

precious

2. purest possible metal; difficult to produce a metal of high chemical purity.

3. use of corrosion resistant alloys

a) Stainless steel containing chromium

b) Cupro-nickel (70% Cu + 30%Ni) in oil refineries
c) Highly stressed Nimonic alloys (Ni-Cr-Mo alloys) used in gas
 Corrosion control
CHOICE OF METALS AND ALLOYS

PROPER DESIGNING

CATHODIC PROTECTION:

ANODIC PROTECTION:

PROTECTIVE COATINGS

INHIBITORS
 Proper Designing

 Simple design and structure

 Avoid complicated shapes having more angles, edges, corners etc.

 Avoid the contact of dissimilar metals - galvanic type corrosion

 Avoid gap or crack adjacent parts

 Replace bolts and rivets by welding

 Avoid metal washers or use rubber or plastic washers

 annealing minimizes the stress corrosion

https://gfycat.com/blindangryechidna
 Corrosion control
CHOICE OF METALS AND ALLOYS

PROPER DESIGNING

CATHODIC PROTECTION:

ANODIC PROTECTION:

PROTECTIVE COATINGS

INHIBITORS
 CATHODIC PROTECTION:

• prevention of corrosion by making metallic structure as cathode in the

electrolytic cell is called cathodic protection.

• Since there will not be any anodic area on the metal, corrosion does not
occur.
• There are two methods of applying cathodic protection to metallic
structures.

a. Sacrificial anodic protection (galvanic

protection)
b. Impressed current cathodic protection
 CATHODIC PROTECTION:

i) Sacrificial anodic protection (galvanic protection)

• metallic structure to be protected is made cathode by

connection it with more active metal (anodic metal).

• all the corrosion will concentrate only on the active metal

• parent structure is thus protected

• more active metal so employed is called sacrificial anode

• corroded sacrificial anode block is replaced by a fresh one

(magnesium, zinc, aluminium and their alloys)
CATHODIC PROTECTION (Sacrificial anodic protection
(galvanic protection))
CATHODIC PROTECTION (Sacrificial anodic protection (galvanic protect

Applications:

1. Protection as buried pipelines, underground cables from soil corrosion.

2. Protection from marine corrosion of cables, ship hulls, piers etc.

3. Insertion of magnesium sheets into the domestic water boilers to

prevent the formation of rust.

4. Calcium metal is employed to minimize engine corrosion

CATHODIC PROTECTION (Sacrificial anodic protection (galvanic protect

Advantages:

1. Low installation and operating cost.

2. Capacity to protect complex structures.

3. Applied to wide range of severe corrodents.

Limitations:

1. High starting current is required.

2. Limited driving potential, hence, not applicable for large objects.

 CATHODIC PROTECTION
ii. Impressed current cathodic protection
 CATHODIC PROTECTION
ii. Impressed current cathodic protection

• impressed current is applied in opposite direction to nullify the corrosion

current and convert the corroding metal from anode to cathode

• derived from a direct current sources (like battery or rectifier on AC

line)

• imsoluble, inert anode (like graphite, scrap iron, stainless steel,

platinum or high silica iron)

• anode is, usually, a back fill, composed of coke breeze or gypsum, so as

to increase the electrical contact with the surrounding soil.
 CATHODIC PROTECTION
ii. Impressed current cathodic protection

Common applications are:

•Steel water and fuel pipelines
•Steel storage tanks
•Steel pier piles
•Ships and boat hulls
•Offshore Oil platforms
•Offshore wind farm foundations
•Onshore oil well castings
•Metal reinforcement bars in concrete buildings and structures
 Comparison of Sacrificial anode method with Impressed
current cathodic method
Sacrificial anode Impressed current cathodic method

• External power supply is not • External power supply is

required required
• The cost of investment is low • The cost of investment is high

• This requires periodic • Replacement is not required as

replacement of sacrificial anodes are stable
anode
• This is the most economical • This is well suited for large
method especially when short structures and long term
term protection is required operations
• This is a suitable method when • This is a suitable method even
the current requirement and when the current requirement
the resistivity of the and the resistivity of the
 Anodic protection

 Useful for metals like aluminium and Titanium

 Al metals become passive by oxide films

 Titanium becomes passive in Chloride ions (present in acid like HCl)

 By externally anodic current, a protective passive film is deposited

on the metal surface.

 Fe, Cr, Ti and their alloys become passive by the application of

controlled anodic currents and the corrosion rate can be decreased.

 Not valid for zinc, magnesium, cadmium, silver, copper or copper

based alloys
Anodic protection
 Anodic protection

Applications:
• Used in acid coolers in dilute sulphuric acid plants
• used in storage tanks for sulphuric acid
• used in chromium in contact with hydrofluoric acid

Limitations:
• This method cannot be applied in the case of corrosive medium
containing aggressive chloride.
• This cannot be applied if protection breaks down at any point, it is
difficult to reestablish
 Proton Exchange Membrane (PEM)

Hydrogen–oxygen fuel cell consists of porous screens of graphite

coated with a layer of platinum catalyst

Electrode reactions

Anodic reaction H 2 → 2 H + + 2 e –

Cathodic reaction ½ O 2 + 2 H + + 2 e – → H 2 O

Overall cell reaction H 2 + ½ O 2 → H 2 O

The EMF : 1.2 V.

Solid electrolyte - solid polymer electrolyte cell.

Useful in spacecrafts.
 Corrosion control
CHOICE OF METALS AND ALLOYS

PROPER DESIGNING

CATHODIC PROTECTION:

ANODIC PROTECTION:

PROTECTIVE COATINGS

INHIBITORS
 Protective coatings

1. Inorganic coatings 2. Organic coatings

• Galvanization,
• Tinning,
• Electrodeposition,
• Anodization
 Protective coatings - Galvanizing

Galvanizing
coating iron or steel sheets with a thin coat of
zinc
Process
a) iron or steel article cleaned with dil.
Sulphuric acid
b) washed with distilled water and dried
c) the dried metal is dipped in bath of
molten zinc
d) formation of thin layer of zinc
Protective coatings - Galvanizing
 Protective coatings - Tinning

Tinning:

coating tin over the iron or steel articles

Process
A) sheet in dilute sulphuric acid and
B) passed through a flux (ZnCl2),
C) next steel passes through a tank of molten tin
D) a series of rollers from underneath (bottom of) the surface of
a
Protective coatings - Tinning
 Electroplating
Significance of electroplating:
Chrome plating:
Shiny Ni coating for
appearance and reducing friction in
not corroding connectors and for
Steel Bolts, nuts increasing
and washers are conductivity
coated with zinc -
Anticorrosion

Aesthetic gold on
the surface of
Silver, copper and
silver and copper
brass for electrical
connectors
 Electroplating
Materials required for the experiment

Cu –Wire/Plate Fe – Nail/rod Glass Beaker DC Power Source

Electrolyte

Ni Cu Au

Ni Soln. Cu Soln. Au Soln.

Electrolyte - various metal Various Metal coated on the

salt solution electrode surface
 Electroplating
DC Power Source
e- e-

e- e-

e- e-

Electrolysis e- e-

Copper Metal
e- e-
(Anode) Iron Nail
Oxidation of the metal (Cathode)
Reduction
e-

Electrolyte
0.1 M Solution of CuSO4.5 H2O

Changing the concentration of the electrolyte

Rate of electroplating
Changing the current flow through the circuit
 Electroless plating

Metal Reducing Oxidized

ions (Mn+)(aq) + agent (ne-) Metal (M) + Product
Deposited over
any solid surf ace
 Anodization
• Anodised oxide coating is carried out by electrochemical method

• wherein the metal is connected as anode and lead or steel is used

as cathode.

• The electrolytic bath normally consists of acids such as sulfuric,

phosphoric, chromic or oxalic acid.

• Upon application of DC bias, oxygen evolution take place at anode,

which combine with the metal and form metal oxide.

• Thickness of the oxide film may be optimised although it may

porous in nature. The porosity can be reduced by further exposing
the film to boiling water or dilute alkali, which convert the metal
oxide to hydrated metal oxide, that occupy more volume than
simple metal oxide. The method is very useful for protecting
metals such as Al, Zn or Mg.
 2. Organic coatings

Constituents of paint:

a) Pigment

b) Vehicle or medium or drying oil

c) Thinner

d) Driers

e) Fillers or Extenders

f) Plasticizers

g) Antiskinning agents
 2. Organic coatings

a) Pigment
The most commonly used pigments in paints and the

compounds required as as follows:

White pigments - White lead, ZnO, BaSO4, TiO2, ZrO2

Blue pigments - Prussian blue, ultramarine blue

Black pigments - Graphite, carbon black, lamp black

Red pigments - Red lead, Fe3O4, carmine

Green pigments - Chromium oxide, chrome green

Brown pigments - Burnt umber, ochre

 2. Organic coatings

b) Vehicle or drying oil or medium:

Vehicle is a liquid substance and film forming material. It holds all the
ingredients of a paint in liquid suspension.

Eg., linseed oil, tung oil.

Functions:

i) To hold the pigment on the metal surface

ii) to form the protective film by evaporation or by other means.

iii)to impart water repellency, durability and toughness to the film

iv)to improve the adhesion of the film

 2. Organic coatings

c) Thinners: Thinners are volatile substances which evaporate easily

after application of the paint. They are added to the paints for reducing
the viscosity of the paints so that they can be easily applied to the metal
surface.
Eg., Dipentine, turpentine, toluol, xylol.
Functions:
i) To reduce the viscosity of the paint
ii) To dissolve vehicle and the additives in the vehicle
iii)To suspend the pigments
iv)To increase the penetration power of the vehicle
v)To increase the elasticity of the paint film
 2. Organic coatings

d) Driers:
These are the substances used to accelerate the process of drying. They are
oxygen carrier catalysts.

Eg., Naphthenates, linoleates, borates, resonates and tungstates of

heavy metals (Pb, Zn, Co, Mn).

Functions:
i) To accelerate the drying of the oil film through oxidation,
polymerization andcondensation
ii) To improve the drying quality of the oil film.
 2. Organic coatings

e) Extenders or Fillers:
These are the inert materials which improve the properties of the paint.
Eg., Gypsum, chalk, silica, talc, clay, CaCO3, CaSO4.
Functions:
i) To fill the voids (empty space or any curved area) in the film
ii) To act as a carrier for the pigment color.
iii)To reduce the cost of the paint
iv) To increase the durability of the paint
v) To reduce the cracking of dry paint
vi) To increase random arrangement of pigment particles.
 2. Organic coatings

f) Plasticisers:
These are added to the paint to provide elasticity to the film and to
minimize its crack.
Eg.,Triphenyl phosphate, dibutyl tartarate, tributyl phthalate,
tricresyl phosphate, diamyl phthalate.

g) Antiskinning agents:
These are sometimes added to some paints to prevent gelling and
skinning of the finished product.
Eg., Polyhydroxy phenols.
 Corrosion control
CHOICE OF METALS AND ALLOYS

PROPER DESIGNING

CATHODIC PROTECTION:

ANODIC PROTECTION:

PROTECTIVE COATINGS

INHIBITORS
 Corrosion Control: Inhibitors

Inhibitors - decrease the rate of corrosion

Inhibitors are classified

1) Anodic inhibitors (chemical passivators)

2) Cathodic inhibitors (adsorption inhibitors)

3) Vapour phase inhibitors (volatile corrosion inhibitors)

 Corrosion Control: Inhibitors
Anodic Inhibitors
• Formation of sparingly soluble compound

• newly produced metal cations in contact with the sparingly soluble

compound

• Then adsorb on the corroding metal surface

• Thus forming a passive film or barrier

• Application: Used to repair

a) the crack of the oxide film over the metal surface

b) the pitting corrosion

c) the porous oxide film formed on the metal surface.

 Corrosion Control: Inhibitors
Cathodic Inhibitors

a) In an acidic solution:

slowing down the diffusion of H+ ions through the cathode.

Eg., Amines, Mercaptans, Thiourea etc.

2 H + + 2 e-  H2
b) In a neutral solution
Controlled either by eliminating oxygen from the corroding
medium or by retarding its diffusion to the cathodic area
Eg., Na2SO3, N2H4, Salts of Mg, Zn or Ni

½ O2 + H2O + 2e-  2OH-