Section -A

1. Attempt all parts. All parts carry equal marks. Write answer of each part in short.
(10x2=20)

a) Describe sludge and scales.

Ans: In boilers, water evaporates continuously and the concentration of the dissolved salts
increases progressively. When their concentrations reach saturation point, they are thrown out of
water in the form of precipitates on the inner walls of the boiler. If the precipitation takes place in
the form of loose and slimy precipitate, it is called sludge. On the other hand, if the precipitated
matter forms a hard, adhering crust/coating on the inner walls of the boiler, it is called scale.

Sludge is a soft, loose and slimy precipitate formed within the comparatively colder portions of the
boiler and collects in areas of the system, where the flow rate is slow or at bends. Sludge’s are
formed by substances which have greater solubility in hot water than in cold water, e.g., MgCO 3,
MgCl2, CaCl2, MgSO4, etc.
b)Explain when will the value of GCV=NCV?
Ans.NCV=GCV-%H X 0.09 X Latent heat of steam
so when %H = 0 then GCV = NCV

c)Why does magnesium bicarbonate require double amount of lime for softening?

Magnesium bicarbonate,Mg(HCO3)2 is removed by lime ,Ca(OH) 2 according to following equation

Mg(HCO3)2+2Ca(OH)2 react to form 2CaCo3+Mg(OH)2+2H2O

d)Explain why the value of GCV is greater than NCV.

NCV(net calorific value) is the quantity of heat produced by combustion when the water produced by combustion
remains gaseous. Since water releases heat when it condenses, GCV is clearlybigger than NCV.

e)Explain the basic principle of lime-soda process. Calculate the amount of lime and soda required
for softening 30000 liters of water, using 20 ppm of sodium aluminate as coagulant. Impurities in
water are as follows: Ca2+ =160 ppm, Mg2+ = 96 ppm, dissolved CO2 = 34 ppm and HCO3 = 403
ppm.
Ans.
Principle : In this Method, the soluble calcium and Magnesium salts in water are chemically converted
into insoluble Compounds by adding calculated amounts of lime Ca(OH)2 and soda Na2CO3 . All
the calcium salts are precipitated out as calcium carbonate CaCO3 and magnesium salts as
magnesium hydroxide Mg(OH)2 which can be easily filtered off.
f)Calculate the amount of lime and soda required for softening 30000 liters of water, using 20 ppm
of sodium aluminate as coagulant. Impurities in water are as follows: Ca2+ =160 ppm, Mg2+ = 96
ppm, dissolved CO2 = 34 ppm and HCO3 = 403 ppm.
Ans.

Constituent Concn M. factor CaCO3 need

Ca2+ 160 100/40 400 S

Mg2+ 96 100/24 400 L+S

CO2 34 100/44 77.27 L

HCO3- 403 100/122 330.32 L

NaAlO2 20 100/164 12.19 -L

Lime = (74/100) {temporary calcium hardness + (2 × temporary magnesium hardness) + Perm Mg

– 2+ 3+
hardness + CO2 + HCl + H2SO4 + HCO 3 + salts of 100 Fe , Al – NaAlO2} × 100/% purity ×
volume of water
= 74/100 [ 400 + 77.27 + 330.32 -12.19] X 100/100 X 30,000
= 17,657880/106
= 17.65Kg
2+ 3+
Soda = (106/100) {Perm Ca hardness + Perm Mg hardness + salts of Fe , Al + HCl + H2SO4 –
–
HCO 3 } × 100/% purity x volume of water.

= 106/100 [ 400 + 400] X 100/100 X 30,000/106

=
g)What is calgon conditioning? Explain.
Ans: It is used for softening hard water. ... The addition of Calgon to hard water causes the
calcium and magnesium ions of hard water to displace sodium ions from the anion of Calgon.
This results in the removal of calcium and magnesium ions from hard water in the form of a
complex with Calgon.

h)Asampleofcoalcontains60%Carbon,33%Oxygen,6.0%Hydrogen,0.5%Sulphur, 0.2% Nitrogen

and 0.3% Ash. Calculate GCV and NCV of coal.
Ans: GCV = 1 [8080C + 34500 (H-O) + 2240S]
100 8
= 1/100[8080 x 60 + 34500 x (6-33/8) + 2240 x 0.5 ]

= 1/100 [ 484800 + 34500 x 1.875 + 1120]

= 5506.075 J/g
NCV = GCV – 0.09(%H)(2458)
= 5506.075 – 0.09 x 6 x 2458

= 5506.075 – 1327.32

4178.755 J/g

i)A sample of water contains the following impurities:

2+ 2+ - 2-
Ca = 20ppm, Mg = 18 ppm,HCO3 = 183ppmand SO4 =24ppm.Calculate the lime
and soda needed for softening.

Ans.

j)Calculate the minimum weight of air required for complete combustion of 1kg of fuel
containing C=90%,H=3.5%,O=3.0%,S=0.5%,H2O=1%,N
= 0.5% and ash = rest.

weight of C in 1 kg coal = 90 x 1000 g = 900 g

100
H = 3.5x 1000 = 35g
100
O = 3.0 x 1000 = 30g
 100

S= 0.5 x 1000/100 = 5g
(N is not combustible)

O2 quantity = (32C + 8H + S - O) g
12
= (32x900 + 8x35 + 5 - 30) g
12
= 2655 g
Minimum amount of air = Net O2 x 100
23
= 26555 x 100 = 11543.47 g air
23
k)100 ml of water sample has hardness equivalent to 12.5 ml of 0.08 N MgSO4 solutions. Calculate
hardness of this water sample.
Ans. N1V1 of water sample = N2V2 of MgSO4
N1 X 100 = 0.08 X 12.5
N1 = 0.01

l)Define Gross Calorific Value and Net Calorific Value?

Ans: Calorific value of a fuel is "the total quantity of heat liberated, when a unit mass (or volume) of the
fuel is burnt completely."
Higher or gross calorific value:HCVis "the total amount of heat produced, when unit mass/volume of
the fuel has been burnt completely and the products of combustion have been cooled to room
temperature"(i.e., 15°C or 60°F).
Lower or net calorific : LCV is "the net heat produced, when unit mass /volume of the fuel is burnt
completely and the products are permitted to escape".
NCV = GCV - % H x .09 x Latent heat of steam
m)Show with the help of reactions, how scale formation can be prevented by Calgon conditioning?

Calgon conditioning: Involves in adding calgon to boiler water . it prevents the scale and sludge
formation by forming soluble complex compound with CaSO4.
Calgon =Sodium hexa Metaphosphate =(NaPO3)6
Na2[Na4(PO3)6] 2Na++[Na4P6O18]-
-2
2CaSO4[Na4P6O18] [Ca2P6O18]-2+2Na2SO4

n)Calculate GCV of the coal sample having C=80%, H=9%, O=4%, N=1.5%, S=2.5% and
ash=3%.

HCV= 1/100[8080C+34500(H-O/8)+ 2240S] Kcal/Kg or cal/g

HCV= 1/100[8080 x80 +34500 (9 4/8)+ 2240x2.5]cal/g

= 9452.5cal/g
Section - B
2. Attempt any Five questions from this section. (5x10=50)

a)What are ion exchange resins? Discuss their role in ion exchange process of water
softening.
Ans: An ion-exchange resin or ion-exchange polymer is a resin or polymer that acts as a medium
for ion exchange. It is an insoluble matrix (or support structure) normally in the form of small
(0.25–0.5 mm radius) micro beads, usually white or yellowish, fabricated from an organic
polymer substrate. The beads are typically porous, providing a large surface area on and inside
them. The trapping of ions occurs along with the accompanying release of other ions, and thus the
process is called ion exchange
Anion resins and cation resins are the two most common resins used in the ion-exchange process.
While anion resins attract negatively charged ions, cation resins attract positively charged ions.
Anion resins
Anion resins may be either strongly or weakly basic. Strongly basic anion resins maintain their
positive charge across a wide pH range, whereas weakly basic anion resins are neutralized at
higher pH levels. Weakly basic resins do not maintain their charge at a high pH because they
undergo deprotonation. They do, however, offer excellent mechanical and chemical stability. This,
combined with a high rate of ion exchange, make weakly base anion resins well suited for the
organic salts.
For anion resins, regeneration typically involves treatment of the resin with a strongly basic
solution, e.g. aqueous sodium hydroxide. During regeneration, the regenerant chemical is passed
through the resin, and trapped negative ions are flushed out, renewing the resin exchange capacity.
Cation-exchange resin
Cation exchange method removes the hardness of water but induces acidity in it, which is further
removed in next stage of treatment of water by passing this acidic water through anion exchange
process Formula: R−H acidic
Reaction:
R−H + M+ = R-M+ + H+.
Anion-exchange resin
Formula: NR4+OH-
Often these are styrene–divinylbenzene copolymer resins that have quaternary ammonium
cations as an integral part of the resin matrix.
Reaction:
NR4+OH- + HCl = NR4+Cl- + H2O.
When the cation exchange resin in exhausted, it can be regenerated by passing a solution of dil.HCl
or dil.H2SO4.
RCa + 2HCl → RH2 + CaCl2 RNa + HCl → RH + NaCl
Similarly, when the anion exchange resin is exhausted, it can be regenerated by passing a solution
of dil.NaOH.
R'Cl2 + 2 NaOH → R'(OH)2 + 2 NaCl
Advantages
The water is obtained by this process will have very low hardness.
Highly acidic or alkaline water can be treated by this process.
Disadvantages
The equipment is costly.
More explosive chemicals are needed for this process.
Water containing turbidity, Fe and Mn cannot be treated, because turbidity reduces the output and
Fe, Mn form stable compound with the resins
b)Calculate the temporary,permanent and total hardness of a sample of water that is
analyzed as Mg (HCO3)2 =7.3 mg/L,Ca(HCO3)2 = 8.1 mg/L, MgC12 = 9.5 mg/L and CaSO4 =
6.8mg/L.

c)The percentage composition of coal sample is : C = 85%, H= 5%, O = 6%, N=4%, S = 2% ash
= 5% and moisture = 3%.Calculate the minimum amount of air needed in combustion of 1
kg of coal.

d)What is the basic principle of Bomb calorimeter? A 0.80 g sample of solid fuel was completely
combusted in the excess of oxygen using bomb calorimeter. The rise in temperature of water in
calorimeter was 2.5°C. Calculate the High calorific value of the fuel. If water taken in calorimeter
is 2000 g and water equivalent of calorimeter is 2200g. Also calculate low Calorific value. (Given :
% Hydrogen in fuel =2.2)
Ans.
x = 0.80 g, w = 2200 g, W = 2000 g
%H = 2.2, Latent heat of water = 587 cal/g, t2-t1 =2.5oC

HCV = (W+w)(t2-t1)
X
= (2000+2200)(2.5) = 13125 cal/g
0.80
LCV = HCV-0.09(%H)(587)
= 13125 – 0.09(2.2)(587) = 13008.774 cal/g

Bomb calorimeter

Principle: A known amount of the fuel is burnt in excess of oxygen and heat liberated is transferred to a
known amount of water. The calorific value of the fuel is then determined by applying the principle of
calorimetery i.e. Heat gained = Heat lost
e) A sample of water was found to contain 40.5 mg/L Ca(HCO3 )2 , 46.5 mg/L Mg(HCO3)2, 32.1
mg/L CaSO4, 22.45 mg/L MgSO4, 19.0 mg/L CaCl2, 4.8 mg/L MgCl2. Calculate the temporary
hardness of water sample.

Ans:
f)Discuss the process of reverse osmosis.
Ans: Reverse osmosis (RO) is a water purification technology that uses a partially permeable
membrane to remove ions, unwanted molecules and larger particles from drinking water. In
reverse osmosis, an applied pressure is used to overcome osmotic pressure, a colligative property,
that is driven by chemical potentialdifferences of the solvent, a thermodynamic parameter. Reverse
osmosis can remove many types of dissolved and suspended chemical species as well as biological
ones (principally bacteria) from water, and is used in both industrial processes and the production
of potable water. The result is that the solute is retained on the pressurized side of the membrane
and the pure solvent is allowed to pass to the other side. To be "selective", this membrane should
not allow large molecules or ions through the pores (holes), but should allow smaller components
of the solution (such as solvent molecules, i.e., water, H2O) to pass freely.[1]
In the normal osmosis process, the solvent naturally moves from an area of low solute
concentration (high water potential), through a membrane, to an area of high solute concentration
(low water potential). The driving force for the movement of the solvent is the reduction in the free
energy of the system when the difference in solvent concentration on either side of a membrane is
reduced, generating osmotic pressure due to the solvent moving into the more concentrated
solution. Applying an external pressure to reverse the natural flow of pure solvent, thus, is reverse
osmosis. The process is similar to other membrane technology applications.
(ii) Explain the process of scale and sludge formation in boilers. How can this be prevented?
Ans: In boilers, water evaporates continuously and the concentration of the dissolved salts
increases progressively. When their concentrations reach saturation point, they are thrown out of
water in the form of precipitates on the inner walls of the boiler. If the precipitation takes place in
the form of loose and slimy precipitate, it is called sludge. On the other hand, if the precipitated
matter forms a hard, adhering crust/coating on the inner walls of the boiler, it is called scale.

Sludge is a soft, loose and slimy precipitate formed within the comparatively colder portions of the
boiler and collects in areas of the system, where the flow rate is slow or at bends. Sludge’s are
formed by substances which have greater solubility in hot water than in cold water, e.g., MgCO 3,
MgCl2, CaCl2, MgSO4, etc.

Prevention: can be removed by scapper.

By using sodium phosphate as softening agent.

By adding tannin and lignin to the boiler water.
Blow down method is also used for removal of scales.
g)Explain proximate analysis of coal. On burning 0.83 gm of a solid fuel in a bomb
calorimeter, the temperature of 3500 gm of water increased from 26.5° C to 29.2° C. Water
equivalent of calorimeter and latent heat of steam are 385.0 gm and 587.0 cal/ gm,
respectively. If the fuel contains 0.7% hydrogen, calculate its gross and net calorific value.

Ans:
h)A zeolite softener was 90% exhausted by removing the hardness completely when 10,000
litres of hard water sample passed through it. The exhausted zeolite bed required 200 litres of
3% NaCl solution for its complete regeneration. Calculate the hardness of water solution.

Ans:

i)What is hardness of water? What do you mean by term permutit? Describe Zeolite or
Permutit process for softening of hard water.

Hardness:- is defined as soap consuming capacity of water. The water which does not give lather with
soap is called Hard water. The Hard water contains dis-solved calcium & magnesium salts.
Permutit :- Permutit is a manmade zeolite. The chemical formula of a zeolite is Na2. Al2O3. nSiO2.
xH2O. Zeolite is made up of micro-porous minerals which have the capacity of exchanging ions.

ZEOLITE METHOD OF WATER TREATMENT

Zeolites are hydrated sodium alumina silicates having porous structure with molecular formula
Na2O.Al2O3.xSiO2.yH2O (X=2 to 10 and Y=2 to 6). They are represented as Na2Ze where Ze
represents the insoluble framework and Na are the loosely held sodium ions.
Principle of zeolite process: They are capable of exchanging their loosely held sodium ions reversibly
with the hardness producing anions in water (Ca+2 and Mg+2). The two Na+ ions are replaced by one
Ca2+ or Mg2+ ions.

Zeolite process of water softening

Working: It involves two steps:
 1. Water softening: When Ca2+ and Mg2+ ions containing hard water is passed through a bed of
sodium zeolite, the sodium ions are replaced by the calcium and magnesium ions.
Na2Ze + Ca(HCO3)2 → 2NaHCO3 + CaZe
Na2Ze + Mg(HCO3)2 → 2NaHCO3 + MgZe
Na2Ze + CaSO4 → Na2SO4 + CaZe
Na2Ze + MgSO4 → Na2SO4 + MgZe
2. Regeneration: When all sodium ions are replaced by calcium and magnesium ions, the zeolite
becomes inactive. Then the zeolite needs to be regenerated. Brine solution is passed through the bed of
inactivated zeolite. The following reactions are taken place and form Na2Ze is regenerated.
CaZe + 2NaCl → Na2Ze + CaCl2
MgZe + 2NaCl → Na2Ze + MgCl2
Advantages :
1. It produces water with about 10 ppm hardness left behind.
2. There is no danger of sludge formation.
3. Requires less time and operation is clean.
4. Process automatically adjusts itself for variation in hardness of incoming water.
5. Equipment is compact, maintenance and operation is easy.

Disadvantages:
1. This method only replaces cationic impurities; anions are left behind in water.
2. Treated water contains more sodium salts, so this water cannot be used inboilers else it will cause
caustic embrittlement.

Limitations:
1. Turbid water cannot be feeded as it will clog the pores of zeolite
2. Acidic water cannot be feeded as it will destroy the zeolite bed.
3. Hot water cannot be used as zeolite tends to dissolve in it.

j)With the help of a neat diagram, explain the working of bomb calorimeter. A sample of coal
contain C=91%, H=5.5%, N=2.5% and ash=2%. The following data were obtained when the above
coal was tested in bomb calorimeter:
Weight of coal burnt= 1.029g
Weight of water taken= 570 g
Water equivalent of bomb and calorimeter = 2200 g
Rise in temperature = 3.3°C
Fuse wire correction= 3.8 cal
Acid correction= 62.6 cal
Cotton thread correction= 1.6 cal
Cooling correction= 0.047°C
Assuming that the latent heat of condensation of steam is 587cal/gm, Calculate gross and net
calorific values of the coal.
BombCalorimeter: A known amount of the fuel is burnt in excess of oxygen and heat
liberated is transferred to a known amount of water. The calorific value of the fuel is then
determined by applying the principle of calorimeter i.e. Heat gained =Heat lost

Wt. of the coal burnt m=1.029g,

Wt of water, W=570g,
 Waterequivalent of calorimeter= 2200 g,
Riseintemp.= 3.3

GrosscalorificvalueHCV= Cal/g or Kcal/Kg

=(2770) (3.347) (68)= 8943.8

cal/g1.029
NCVor LCV =HCV 0.09Hx587 cal / gm
=8943.8 0.09x5.5x587
=8653.23cal/gm
Section - C
Attempt any two questions from this section. (2x15=30)
b)A sample of coal contains C = 70%,O = 20%, H=8%, S=1 %, N= .5%, ash = .5%Calculate
GCV and NCV of coal.

c)Describe Zeolite process of water softening. A zeolite softener was 90% exhausted by removing
the hardness completely when 10,000 litres of hard water was passed through it. The exhausted
zeolite bed required 200 litres of 3% sodium chloride solution for its complete regeneration.
Calculate the hardness of water sample.
Ans.
Zeolites are hydrated sodium alumina silicates having porous structure with molecular formula
Na2O.Al2O3.xSiO2.yH2O (X=2 to 10 and Y=2 to 6). They are represented as Na2Ze where Ze represents
the insoluble framework and Na are the loosely held sodium ions.
Principle of zeolite process: They are capable of exchanging their loosely held sodium ions reversibly
with the hardness producing anions in water (Ca+2 and Mg+2). The two Na+ ions are replaced by one Ca2+
or Mg2+ ions.
 Zeolite process of water softening

Working: It involves two steps:

2+ 2+
1. Water softening: When Ca and Mg ions containing hard water is passed through a bed of
sodium zeolite, the sodium ions are replaced by the calcium and magnesium ions.
Na2Ze + Ca(HCO3)2 → 2NaHCO3 + CaZe
Na2Ze + Mg(HCO3)2 → 2NaHCO3 + MgZe
Na2Ze + CaSO4 → Na2SO4 + CaZe
Na2Ze + MgSO4 → Na2SO4 + MgZe
2. Regeneration: When all sodium ions are replaced by calcium and magnesium ions, the zeolite
becomes inactive. Then the zeolite needs to be regenerated. Brine solution is passed through the
bed of inactivated zeolite. The following reactions are taken place and form Na2Ze is regenerated.

CaZe + 2NaCl → Na2Ze + CaCl2

MgZe + 2NaCl → Na2Ze + MgCl2

d)What is rank of coal? Describe proximate and ultimate analysis of coal.

Ans.
Ranking of Coal
The extent of maturation of coal is called as its rank.Anthracite is the top rank of the coal.

ANALYSIS OF COAL
In order to assess the quality of coal the following two types of analysis are made: Proximate analysis
and Ultimate analysis.
Proximate Analysis
It includes the determination of moisture, volatile matter, ash and fixed carbon.
● This gives quick and valuable information regarding commercial classification and
determination of suitability for a particular industrial use.
Moisture%
All moisture in coal escapes on heating coal at 110oC for 1h.

Known coal sample

(powdered and C Cool in dessicator Weigh
dried) 1 hour

Moisture % = loss in weight x 100

Weight of coal sample

Volatile matter %
At 925oC in muffle furnace, coal undergoes thermal degradation to form volatile matter.

Moisture free coal left Weigh

Cool the crucible in
in first C
dessicator
experiment 7 min

VM % = weight of volatile matter x 100

Weight of coal sample

If the fresh coal sample is heated directly at 925oC, then the weight loss will be due to both loss of
moisture as well as volatile matter. In that case,

%VM = loss in weight due to moisture and volatile matterx100 - moisture%

Weight of coal sample

Ash %
The residual coal in the above experiment is heated and burned above 750oC for 30 min. The ash is left
behind. Cool and weigh.

Ash % = weight of Ash x 100

Weight of coal sample

%Fixed carbon = 100 – (moisture% + volatile matter% + ash%)

Moisture:
• Excess of moisture is undesirable in coal.
• Moisture lowers the heating value of coal and takes away appreciable amount of the liberated
heat in the form of latent heat of vapourisation.
• Excessive surface moisture may cause difficulty in handling the coal.
• Presence of excessive moisture quenches fire in the furnace.
 Volatile Matter:
• A high percent of volatile matter indicates that a large proportion of fuel is burnt as a gas.
• The high volatile content gives long flames, high smoke and relatively low heating values.
Ash:
• The high percentage of ash is undesirable. It reduces the calorific value of coal.
• In furnace grate, the ash may restrict the passage of air and lower the rate of combustion.
• High ash leads to large heat losses and leads to formation of ash lumps.
• The composition of ash and fusion range also influences the efficiency of coal.
• Apart from loss of efficiency of coal, clinker formation also leads to loss of fuel because some
coal particles also get embedded in the clinkers.
Fixed Carbon:
• Higher the percentage of fixed carbon, greater its calorific value
• The percentage of fixed carbon helps in designing the furnace and shape of the fire-box because
it is the fixed carbon that burns in the solid state.

Ultimate analysis of coal:

Analysis of coal in which % of C, H, O, N, S elements are found out is known as ultimate analysis.

Determination of C and H

Known coal sample C is converted to CO2 Gaseous products are absorbed by pre-
(powderedoxygen
and and H to H2O weighed U-tubes containing
dried) anhydrous CaCl2 which absorbs
H2O and KOH which absorbs CO2.

Increase in weight is calculated

%C= Weight of CO2 formed x 12 x 100

Weight of coal sample x 44

%H= Increase in Weight of CaCl2 tube x 2 x 100

Weight of coal sample x 18

Determination of N (kjeldahl method):

Known coal sample clear solution

(powdered andconc. Alkali is liberated.
dried) in kjeldahl SO4
 flask SO4 Pass through known volume of standard
acid

Unused acid is determined by back

titration with NaOH

% N = Volume of acid x Normality x 1.4

Weight of coal sample

Determination of S:

O2 O2 H2O BaCl2
S SO2 SO3 H2SO4 BaSO4 + 2HCl
BaSO4 is filtered, dried and weighed.

% S = Weight of BaSO4 precipitate x 32 x 100

Weight of coal sample x 233

% Ash
Known coal sample
(powdered and C(heat) Residue left weigh
dried) 30 min in a muffle furnace

% Ash = Weight of residue x 100

Weight of coal sample

% O = 100-(C% + H% + N% + ash% + S%)

Importance of Ultimate Analysis

• Carbon: greater the % carbon in coal, better is the coal quality and calorific value.
• Hydrogen: Hydrogen is in the form of moisture and volatile matter. It decreases the calorific
value and quality of coal.
• Nitrogen: Nitrogen has no calorific value. A good quality coal should have negligible N%.
• Sulphur: Corrosive effect and pollutant. A good quality coal should have low S%.
• Oxygen: Decreases the calorific value of coal, decreases the coal quality.

e)Explain the Zeolite process of watersoftening? The hardness of 10,000L of a sample of water
was removed by passing it through azeolite softener.The zeolite softener then required 200L of
NaCl solution containing 150gm/L of NaCl for regeneration. Find the hardness of water sample.
g)WhatdoyouunderstandbythetermsGCVandNCV?Explaintheconstructionand working of
bombcalorimeter.
Higher or gross calorific value: HCV is "the total amount of heat produced, when unit mass/volume of
the fuel has been burnt completely and the products of combustion have been cooled to room
temperature"(i.e., 15°C or 60°F).

Lower or net calorific : LCV is "the net heat produced, when unit mass /volume of
the fuel is burnt completely and the products are permitted to escape".

NCV = GCV - % H x .09 x Latent heat of steam

Determination of Calorific value: Calorific value of a fuel can be determined experimentally as well as
theoretically.

Experimental Determination of calorific value of solid and non-volatile liquid fuels:

It is determined by bomb calorimeter.

BOMB CALORIMETER

Principle: A known amount of the fuel is burnt in excess of oxygen and heat liberated is transferred to a
known amount of water. The calorific value of the fuel is then determined by applying the principle of
calorimetery i.e. Heat gained = Heat lost
BOMB CALORIMETER
Construction: Bomb calorimeter consists of:
1. A strong stainless steel pot fitted with a lid.
2. Two electrodes
3. One oxygen inlet.
4. One of the electrodes is attached to the crucible having fuel.
5. Fuel sample is weighed and burnt in high pressure oxygen (25-30 atm).
6. Stainless steel or copper calorimeter.
7. Stirrer for uniform circulation of water.
8. Beckmann thermometer (0.01oC changes in temperature can be easily
9. Water and air jackets to avoid heat losses.
10. 6 V battery to start combustion of fuel.
Working of bomb calorimeter:
1. Weigh fuel sample and keep it in crucible.
2. Fix the lid tightly of bomb pot.
3. Fill the bomb with oxygen (25-30 atm pressure).
4. Place the bomb in calorimeter.
5. Add known volume of water in the calorimeter.
6. Keep the thermometer and stirrer in the water.
7. Place the calorimeter in the water jacket.
8. Put the plastic cover on top and make electrical connections.
9. Stir for 5 minutes and note the initial temperature of water.
10. Pass the current to heat the wire so that the fuel catches fire.
11. Note the maximum temperature reached.

Calculations:
Let weight of the fuel sample taken = x g
Weight of water in the calorimeter = W g
Water equivalent of the Calorimeter, stirrer, bomb, thermometer = w g
Initial temperature of water = t1oC
Final temperature of water = t2oC
Heat gained by water = W x dt x specific heat of water
= W (t2-t1) x 1 cal
Net Calorific value:
Let percentage of hydrogen in the fuel = H
Weight of water produced from 1 gm. of the fuel = 9H/100 gm.
Heat liberated during condensation of steam
= 0.09H  587 cal
Net (Lower calorific value) = GCV-Latent heat of water formed
= GCV- 0.09H  587 cal/gm
Corrections: For accurate results the following corrections are also incorporated:
• Acid corrections must be made for the heat liberated in the bomb by the formation of H 2SO4 and
HNO3
• 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.

• Fuse wire correction: Heat liberated by combustion of magnesium wire must be subtracted.
• Cotton thread correction: For the proper combustion of fuel some cotton threads are kept in the
crucible, so heat liberated due to this must be subtracted.

Therefore, Gross calorific value

=(W+w)(t2-t1+Cooling correction)-[Acid+ fuse corrections] / Mass of the fuel.

GCV = (W+w)(t2-t1+Cc) – (CA+Cf+CCT)

CA = Acid correction

Cf = fuse wire correction

CCT = cotton thread correction

CC = cooling correction

h)Explain reverse osmosis with its advantages. A water sample on analysis gives the
following data: Ca2+= 20 ppm, Mg2+ = 25 ppm, CO2= 30 ppm, HCO3-= 150 ppm, K+= 10
ppm. Calculate the lime (87% pure) and soda (91% pure) required to soften 106 liter of
sample water.

The removal of dissolve solids (NaCl) from water is known as desalination process. It can be carried out
by Reverse osmosis.
Reverse Osmosis or super filteration commonly referred to as RO, is a process to
demineralize or deionize water by pushing it under pressure through a semi-permeable Reverse
Osmosis Membrane.
Reverse Osmosis is the process of Osmosis in reverse
In osmosis, if a semi-permeable membrane separates two solutions, solvent from the lower concentration
passes to the higher concentration to equalize the concentration of both. But in the reverse
osmosis,pressure higher than osmotic pressure is applied from the higher concentration side so
that the path of the solvent is reversed, i.e. from higher concentration to lower concentration. This
method is applicable mainly for the desalination of sea water. Sea water and pure water are
separated by a semi-permeable membrane.The process is very easy. It is used to make pure water.
It removes the ionic and non-ionic substances inthe water. It also can remove suspended colloidal
particles. The life of a membrane is nearly 2 years andit should be replaced after this period. By
this process, sea water is made to fit for drinking. Water obtained after being treated by this
process is used in boilers.
i)Describe proximate analysis of fuels. A coal sample has the following
composition by weight: C=90%, O=3%, S=0.5%, N=0.5% and Ash=2.5%. Net
calorific value of the coal was found to be 8,490.5 kcal/kg. Calculate the percentage
of hydrogen and Gross calorific value.

Proximate Analysis It includes the determination of moisture, volatile matter, ash and
fixed carbon. This gives quick and valuable information regarding commercial classification
and determination of suitability for a particular industrial use.
Moisture% All moisture in coal escapes on heating coal at 110oC for 1h.

Known coal sample

(powdered and C Cool in dessicator Weigh
dried) 1 hour

Moisture % = loss in weight x 100

Weight of coal sample

Volatile matter %
At 925oC in muffle furnace, coal undergoes thermal degradation to form volatile matter.

Moisture free coal left Weigh

Cool the crucible in
in first C
dessicator
experiment 7 min

VM % = weight of volatile matter x 100

Weight of coal sample

If the fresh coal sample is heated directly at 925oC, then the weight loss will be due to both loss of
moisture as well as volatile matter. In that case,

%VM = loss in weight due to moisture and volatile matterx100 - moisture%

Weight of coal sample
Ash %
The residual coal in the above experiment is heated and burned above 750oC for 30 min. The ash is left
behind. Cool and weigh.

Ash % = weight of Ash x 100

Weight of coal sample

%Fixed carbon = 100 – (moisture% + volatile matter% + ash%)

j)Calculate the quantities of lime (74%) and soda (92%) required for cold softening of 125,000 L of
water with the following analysis, using 10 ppm of NaAlO2 as coagulant. Analysis of raw water:
Ca2+ = 160 ppm, Mg2+= 48 ppm, CO2= 66 ppm, HCO3-= 264 ppm, H+= 20 ppm, NaCl= 4.7 ppm.

Analysis of treated water: CO32-=45 ppm, and OH-= 68 ppm [5+5]

Hardness due to Mg2+=48x50=200ppmCaCO3eq.

12
Hardness duetoHCO- 3=264 x50=216.3 ppmCaCO3eq.
61
.Hardness duetoH+=20x50=1000 ppmCaCO3eq.
1
2+
Hardness due toCa =160x50=400 ppmCaCO3eq.
20
Hardness due to CO2=66x50=150 ppmCaCO3eq.
22
Hardness due to NaAlO2=10x50= 6.09ppmCaCO3eq.
82

Hardness due toCO2-3 =45x50=75 ppmCaCO3eq30

Hardness due toOH--=68x50=200ppmCaCO3eq17
Lime Req= [ Mg2++HCO3 -
= +H+ + CO2+OH--

=220 kg

3
2+ 2+ -
SodaReq= = [Ca +Mg -HCO 3 +H+ +CO2- +OH--]x
 = 238.8 kg

k) What are ion exchangers? With the help of neat sketch, discuss ion-exchange process for water
softening. Compare its merit over Zeolite process. [2+6+2]

Ionexchangeprocessalsoknownasdemineralizationorde-ionizationprocess.Ion-
Exchangeresinsareinsolublecrosslinked longchainorganicpolymerswitha
microporousstructure,andthe
blefortheion-exchangingproperties.
In De-ionizationprocessall theionspresentinwaterareeliminatedbyusingion-
exchangeresins.Basicallyresins withacidicfunctional
grouparecapableofexchangingH+ionswithothercations.Resinswithfunctionalgroupsarecapableofexch
angingOH-ionswithotheranions.
Resinsareclassifiedas
1. CationExchangeResins
2. AnionExchangeResins
1. CationExchangeResins:Thesearemainlystyrenedivinylbenzeneco-
polymers,whichonsulphonationorcarboxylation.Thesearecapableofexchangingtheirhydrogenionsw
ithcationsinwater.

2. AnionExchangeResins:Anionexchangeresinsarestyrene-divinylbenzeneoramine-
formaldehydecopolymers,whichcontainsamino,quaternaryammoniumorquaternaryphosphoniumorterti
arysulphoniumgroupsasan
internalpartsoftheresinmatrix.TheseaftertreatmentwithdiluteNaOHsolution.Becomecapableofexchangi
ngtheirOH-ionswithanionsinwater.
Inion-exchangeprocess, hardwaterisallowedtopassthrough
+2 +2
cationexchangeresins,whichremoveCa andMg ionsandexchange equivalentamountofH+ions.
Thusbypassinghardwaterthroughcationhardnessisobservedbythefollowingreactions.
CationExchangeResins
2RH++Ca+2 R2Ca+2H+

2RH++Mg+2 R2Mg+2H+(RH+=cationexchangeresin)
-
Aftercationexchangeresin,thewaterispassedthrough anionexchangecolumnwhenall theanionslikeCl
,SO4-2etc.aretakenupbyresinandequivalentamount ofOH- ionisreleasedfromthiscolumntowater.
AnionExchangeResins
- -

+SO4-2 R2SO4+2OH-
-2
2CO3+2OH
-
3

H+andOH-
ions,thusreleasedinwaterfromrespectivecationandanionexchangecolumns,getcombinedtoproducewater
molecules.
H++OH- H2O

Thewatercomingoutfromtheexchanger
isionfreei.e.,freefromanionsandcations.Thuswaterofzerohardnessisobtained.

REGENERATION:
WhencationexchangerlossescapacityofproducingH+ionsandexchangerlossescapacityofproducingOH-
ions,theyaresaidtobeexhausted.Theexhaustedcationexchangerisregeneratedbypassingitthroughdilutesul
phuricacid.
R2Ca+2+2H+ 2RH++Ca+2

-
TheexhaustedanionexchangerisregeneratedbypassingadilutesolutionofNaOH.R2SO4
2
+2OH- -
+SO4-2
 Demineralizationofwater

Merits of Ion-exchange process over zeoliteprocess

a. The process can be used to soften highlyacidicoralkalinewater.
b. Itproduceswaterofverylow hardness(2ppm)
c.Itisverygood for treatingwaterforuseinhigh-pressureboilers.