Module-7: Industrial applications

Water purification methods

• zeolites (principle, process, advantages and disadvantages),

• ion-exchange resins ( double /mixed bed (principle, process,

advantages and disadvantages),
• Reverse osmosis (principle, process, advantages and
disadvantages),
Fuels and combustion
• -LCV, HCV, Bomb calorimeter (numerical)
Corrosion
• Prevention of Corrosion, cathodic protection (Sacrificial anodic
protection and Impressed current cathodic protection).
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 Water Softening Methods
❖ Zeolite (Permutit process)

❖ Ion-exchange

❖ Mixed bed ion-exchange

❖ Reverse Osmosis

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 Permutit or Zeolite Process
o Zeolite is hydrated sodium aluminium silicate having a general formula, Na2OAl2O3.xSiO2.yH2O.
o It exchanges Na+ ions for Ca2+ and Mg2+ ions.
o Common Zeolite is Na2OAl2O3.3SiO2.2H2O known as natrolith.
o Other gluconites, green sand (iron potassium phyllosilicate with characteristic green colour, a mineral
containing Glauconite)etc. are used for water softening.
o Artificial zeolite used for water softening is Permutit.
o These are porous, glassy particles having higher softening capacity compared to green sand.
o They are prepared by heating china clay (hydrated aluminium silicate), feldspar (KAlSi3O8-NaAlSi3O8 –
CaAl2Si2O8) are a group of rock-forming tectosilicate minerals which make up as much as 60% of the
earth’s crust) and soda ash (Na2CO3)

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 Natural Zeolites:

1. Natrolite - Na2O. Al2O3 4SiO2 .2H 2O

2. Laumontite - CaO. Al2O3 4SiO2 .4H 2O

3. Harmotome - (BaO.K2O). Al2O3 5SiO2 .5H 2O

- Capable of exchanging its Na ions

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 Permutit or Zeolite Process
o Method of softening:

Na2Ze + Ca(HCO3)2 2 NaHCO3+CaZe

Na2Ze + Mg(HCO3)2 2 NaHCO3+ MgZe
Na2Ze + CaSO4 2 Na2SO4+CaZe
Na2Ze + CaCl2 2 NaCl+CaZe

o Regeneration of Zeolite:

CaZe (or) MgZe + 2 NaCl Na2Ze + CaCl2 or MgCl2

Brine solution

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 Zeolite Process
o Advantages:
o Residual hardness of water is about 10 ppm only
o Equipment is small and easy to handle
o Time required for softening of water is small
o No sludge formation and the process is clean
o Zeolite can be regenerated easily using brine solution
o Any type of hardness can be removed without any modifications to the process

o Disadvantages:
o Coloured water or water containing suspended impurities cannot be used
without filtration
o Water containing acidic pH cannot be used for softening since acid will destroy
zeolite.

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 Ion-Exchange Process
o Ion-exchange resins are cross linked long chain polymers with
microporous structure
o Functional groups present are responsible for ion-exchange
properties
o Acidic functional groups (-COOH, -SO3H etc.) exchange H+ for
cations &
o Basic functional groups (-NH2, =NH etc.) exchange OH- for
anions.

A. Cation-exchange Resins(RH+):
- Styrene divinyl benzene copolymers
- When sulphonated, capable of exchange H+

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 Ion-Exchange Process
B. Anion-exchange resins (R’OH):
- Styrene divinyl benzene copolymers or amine formaldehyde copolymers with
NH2, QN+, QP+, QS+, groups.
- On alkali treatment, capable of exchange of OH-

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 Ion-Exchange Process
The Process of Ion-exchange is:
2 RH+ + Ca2+/Mg2+ R2Ca2+/R2Mg2+ + 2 H+ (Cation exchange)

R’OH- + Cl- R’+ Cl- + OH- (anion exchange)

2 R’OH- + SO42- R’2 SO42- + 2 OH- (anion exchange)

2 R’OH- + CO32- R’2 CO32- + 2 OH- (anion exchange)

Finally, H+ + OH- H2O
Regeneration of exhausted resins:
Saturated resins are regenerated:
R2Ca2+/R2Mg2+ + 2H+ 2 RH+ + Ca2+/Mg2+ (cation) (Strong acid)
(washings)
R’2 SO42- + 2 OH- 2 R’OH- + SO42- (Strong base)
(washings)

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 Ion-Exchange Process

Note: Hard water should be first passed through the cation exchanger and then
Anion exchanger to avoid hydroxides of Ca2+ and Mg2+ getting formed

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 Mixed Bed Deionizer

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 Advantages & Disadvantages

o Advantages:
- Can be used for highly acid and highly alkaline water
- Residual hardness of water is as low as 2 ppm.
- Very good for treating water for high pressure boilers

o Disadvantages:
- Expensive equipment and chemicals
- Turbidity of water should be < 10 ppm. Otherwise output will
reduce; turbidity needs to be coagulated before treatment.
- Needs skilled labour

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 Reverse Osmosis
oWhen two solutions of unequal
concentrations are separated by a
Semipermeable membrane,
solvent will flow from lower
conc. to higher conc.

oThis phenomenon can be reversed

(solvent flow reversed) by
applying hydrostatic pressure on
the concentrated side

oIn reverse osmosis, pressure of

15-40 kg/cm2 is applied to sea
water.

oThe water gets forced through the

semipermeable membrane leaving
behind the dissolved solids.

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 Fuels and Combustion

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• Fuel is a combustible substance, which on combustion produces a large amount of
heat, which can be used for various domestic and industrial purposes.

Combustion:
• The process of combustion involves oxidation of carbon, hydrogen etc. of the fuels to
CO2, H2O, and the difference in the energy of reactants and the products are liberated
as large amount of heat energy which is utilized.

Fuel + O2 Products + Heat

• The primary or main source of fuels are coal and petroleum oils, the amounts of
which are dwindling day by day. These are stored fuels available in earth's crust and
are generally called "fossil fuels".

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 Calorific value of fuels
• The most important property of fuel to be taken into account is its
calorific value or the capacity to supply heat.

• The calorific value of a fuel can be defined as "the total quantity of

heat liberated when a unit mass or volume of the fuel is burnt
completely".

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 Units of heat

• Calorie - Calorie is the amount of heat required to raise the

temperature of one gram of water through one degree centigrade.
• Kilocalorie (or) kilogram centigrade unit - This is the unit of metric
system and is equal to 1000 calories. This may be defined as "the
quantity of heat required to raise the temperature of one kilogram of
water through one degree centigrade".
• Thus 1 kcal = 1000 cal.

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 Units of heat

3. British thermal unit (B. Th. U.) - This is defined as "the quantity of
heat required to raise the temperature of one pound of water through
one degree Fahrenheit". This is English system unit.
1 B. Th. U. = 252 cal = 0.252 k cal.
1 k cal = 3.968 B. Th. U.

4. Centigrade Heat Unit (C. H. U.) - This is the "quantity of heat required
to raise the temperature of one pound of water through one degree
centigrade".
Thus, 1 k cal = 3.968 B. Th. U. = 2.2 C. H. U.

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Units
Amount of heat required to raise the temp. of

• Calorie: 1g of water through 1oC

• Kilocalories : 1Kg of water through 1oC
• British Thermal
Unit (B. Th. U) : 1pound of water through 1oF
• Centigrade
Thermal Unit (C.T.U) : 1pound of water through 1oC

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 Characteristic of a good fuel,

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 Determination of Calorific Value
Bomb calorimeter

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 Calculation

m = mass of fuel pellet (g)

W = mass of water in the calorimeter (g)
w = water equivalent of calorimeter (g)
t1 = initial temperature of calorimeter.
t2 = final temperature of calorimeter.
HCV = gross calorific value of fuel.

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 Corrections
• Fuse wire correction. Heat liberated during sparking should be
subtracted from heat liberated.

• Acid correction. Fuels containing Sulphur and Nitrogen if oxidized,

the heats of formation of H2SO4 and HNO3 should be subtracted (as
the acid formations are exothermic reactions).

• Cooling correction. The rate of cooling of the calorimeter from

maximum temperature to room temperature is noted. From this rate of
cooling (i.e., dt°/min) and the actual time taken for cooling (t min) then
correction (dt × t) is called cooling correction and is added to the (t2 .
t1) term.

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Corrections: For accurate results the following corrections are also
incorporated:
(a) Fuse wire correction: As Mg wire is used for ignition, the heat generated by
burning of Mg wire is also included in the gross calorific value. Hence this
amount of heat has to be subtracted from the total value.
(b) Acid Correction: During combustion, sulphur and nitrogen present in the fuel
are oxidized to their corresponding acids under high pressure and
temperature.

S + O → SO ΔH= -144,000 cal

2 2
2SO + O + 2H O → 2H SO
2 2 2 2 4
2 N + 5O + 2H O → 4HNO
2 2 2 ΔH= 3
-57,160,000 cal

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The corrections must be made for the heat liberated in the bomb by the formation of H2SO4
and HNO3. The amount of H2SO4 and HNO3 is analyzed by washings of the calorimeter.
For each ml of 0.1 N H2SO4 formed, 3.6 calories should be subtracted.
For each ml of 0.1 HNO3 formed, 1.429 calories must be subtracted.

(C) Cooling correction: As the temperature rises above the room temperature, the
loss of heat does occur due to radiation, and the highest temperature recorded will be
slightly less than that obtained. A temperature correction is therefore necessary to get
the correct rise in temperature.
If the time taken for the water in the calorimeter to cool down from the maximum
temperature attained, to the room temperature is x minutes and the rate of cooling is
dt/min, then the cooling correction = x  dt. This should be added to the observed rise in
temperature

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1. 0.72 gram of a fuel containing 80% carbon, when burnt in a bomb
calorimeter, increased the temperature of water from 27.3o to 29.1oC. If the
calorimeter contains 250 grams of water and its water equivalents is 150
grams, calculate the HCV of the fuel. Give your answer in kJ/kg.

Here m= 0.72 g, W = 250g, w= 150g, t1 = 27.3oC, t2 =

29.1oC.

HCV of fuel (Q) = (W + w) (t1 - t2) x specific heat of water

m
= (250 + 150) × (29.1-27.3)x4.2/0.72
=400g x1.8 0cx 4.2joule.g-1. c-1/0.72g
=4200 joule/gram ( 1000g= 1kg)
=4200kJ/kg
Specific heat of water = s (1 calorie/gram °C = 4.2 joule/gram °C)
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A sample of coal has C=93%, H=6% and ash=1%. When coal is tested in bomb calorimeter, the following
are the data:
• Weight of burnt coal=0.92g,
• weight of water taken=550g,
• water equivalent to bomb calorimeter=2200g,
• rise in temperature=2.42 0C,
• fuse wire correction=10 cal,
• acid correction=50 cal.
Calculate gross and net calorific value of the coal assuming the latent heat of condensation of steam as
587 cal/g

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2. On burning 0.83 of a solid fuel in a bomb calorimeter , the temperature of 3,500g of water
increased from 26.5oC to 29.2oC. Water equivalent of calorimeter and latent heat of steam
are 385g and 587.0 cal/g respectively. If the fuel contains 0.7% hydrogen, calculate its gross
and net calorific value.

Gross calorific value = (W + w) (t2 – t1)x specific heat of water

x
= (3500 +385) × 2.7x1 cal.g-1 = 12,638 cal/g
0.83

NCV = [GCV – 0.09 H(%) × 587]

= (12,638– 0.09 × 0.7 × 587) cal/g
= (12,638 – 37) cal/g
= 12,601 cal/g

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 Dulongs Formula
The approximate calorific value of a fuel can be determined by knowing the amount of
constituents present:

Gross or higher calorific value (HCV) from elemental constituents of a fuel.

H = 34500 kcal/kg; C = 8080 kcal/kg; S = 2240 kcal/kg

Oxygen present in the fuel is assumed to be present as water (fixed hydrogen).

Available Hydrogen = Total hydrogen - Fixed hydrogen
= Total hydrogen - 1/8 mass of oxygen in fuel.

Dulongs formula for calorific value from the chemical composition of fuel is,

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 Dulongs Formula
The approximate calorific value of a fuel can be determined by knowing the
amount of constituents present:

Gross or higher calorific value (HCV) from elemental constituents of a fuel.

H = 34500 kcal/kg; C = 8080 kcal/kg; S = 2240 kcal/kg

Oxygen present in the fuel is assumed to be present as water (fixed

hydrogen).
Available Hydrogen = Total hydrogen - Fixed hydrogen
= Total hydrogen - 1/8 mass of oxygen in fuel.

Dulongs formula for calorific value from the chemical composition of fuel
is,

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 Corrosion

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Corrosion
Any process of deterioration and consequent loss of solid
metallic material, through an unwanted chemical or electrochemical attack by
its environment

Types

• Dry or Chemical Corrosion

• Electrochemical Corrosion

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 Dry or Chemical Corrosion

1.Oxidation Corrosion

1.Corrosion by other gases

1.Liquid Metal Corrosion

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 Oxidation Corrosion
Oxygen present in the atmosphere attacks the metal surface

– formation of oxide layers

Mechanism
Nature of the Oxide
– When oxidation starts, a thin layer of oxide film will be formed on the surface
and the nature of the film decides the further action!
i.e. Porous film or non-porous film

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 Factors Influencing Corrosion
Nature of the

Metal Environment
Position in galvanic series Temperature
Humidity
Overvoltage
Presence of impurities in atmosphere
Relative areas of anode and cathode Suspended particles
Purity of the metal
pH
Physical state of the metal
Silicates
Nature of the surface film
Conductance
Passive character of the metal
Formation of O2 conc. cell
Solubility of corrosion products
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 Forms of Corrosion

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 Control of Corrosion
Corrosion can be controlled by:

a) Proper designing
b) Proper selection of metal or alloy
c) Use of pure metals
d) Use of alloys
e) Cathodic protection
f) Anodic protection
g) Use of inhibitors
h) Changing the environment
i) Application of protective coatings

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 Cathodic Protection
Cathodic protection:
Principle is to make the base metal to be protected as cathode by
connecting to a highly anodic metallic plate.
Two methods of cathodic protection are known:
i) Sacrificial anodic protection
ii) Impressed current cathodic protection

i) Sacrificial anodic protection:

o The metallic structure to be protected is connected through a metal

wire to a more anodic metal.
o This will induce corrosion at the anodic metal.
o Thus the more anodic metal sacrifices itself and gets corroded
protecting the metallic structure.
o Sacrificial anodes known are Zn, Mg, Al and their alloys.
o Applications are: protection of underground pipelines, ship hulls and
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other marine devices, water tanks. 55
 Sacrificial anodic protection
Sacrificial anodic protection - concept

e-

Mg

Mg2+

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 Sacrificial Anodes
• Galvanization of Steel
• Dip steel sheet in molten zinc. Get a pretty thin coating.
• Zinc will be anode. Steel exposed by crack is the cathode.
Since we have a huge anode having to be served by a
small cathode, corrosion rate will be slow.

Tiny cathode (steel)

Larger Area
Large area
(Zinc)
anode (zinc)

An example of a unfavorable area ratio. Bad deal: huge cathode, tiny anode
An example of a favorable area ratio. Bad deal: huge cathode, tiny anode
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 Another Example

Zinc is attached to the steel hull of the vessel

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 Sacrificial Anode for a Pipeline

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 Aluminium anodes mounted on a steel jacket
structure – using galvanic corrosion for
corrosion control! Called cathodic protection
(aka sacrificial anode)
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ii) Impressed current cathodic protection:
o Impressed direct current is applied in the opposite direction to the corrosion current to nullify
it.
o Usually, one terminal of a battery is connected with an insoluble anode e.g. graphite electrode
is immersed in black fill containing coke, gypsum, bentonite and sodium sulphate for good
electrical conductivity.
o The other terminal is connected to the metallic structure to be protected.
o Since the current is impressed on the metallic structure, it acts as cathode and thus gets
protected.
o This method is usually used to protect underground water pipe lines, oil pipe lines,
transmission lines, ships etc.

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 Impressed current cathodic protection

Corrosion current of equal magnitude but opposite in direction applied to nullify corrosion current

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 See Exxon Mobil example

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▪ Copper plating:
• Anode reaction: Cu (s) → Cu2+ (aq.) + 2 e
• Cathode reaction: Cu2+ (aq.) + 2 e → Cu (s)
• Electrolyte: Aqueous CuSO4 solution
▪ Nickel plating:
• Anode reaction: Ni (s) → Ni2+ (aq.) + 2 e
• Cathode reaction: Ni2+ (aq.) + 2 e → Ni (s)
• Electrolyte: Aqueous NiSO4 solution

▪ Gold plating:
• Anode reaction: Au (s) → Au+ (aq.) + e
• Cathode reaction: Au+ (aq.) + e → Au (s)
• Electrolyte: Aqueous K[Au(CN)2] solution
▪ Silver plating: ▪ Silver plating:
• Anode reaction: Ag (s) → Ag+ (aq.) + e • Anode reaction: Ag (s) → Ag+ (aq.) + e
• Cathode reaction: Ag+ (aq.) + e → Ag (s) • Cathode reaction: Ag+ (aq.) + e → Ag (s)
• Electrolyte:
12/15/2023 Aqueous AgNO3 solution • Electrolyte: Aqueous K[Ag(CN)2] solution
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