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SYLLABUS
AIM
Every chemical reaction involves consumption of Materials and energy. The reactions are to be
balanced with correct quantity of materials and energy to achieve good percentage of conversion for
products. The aim of this course is to give fundamental knowledge on such material and energy
balances.
OBJECTIVES
To make them understand different types of laws of chemistry of materials and also prepare the
students to accurately calculate the Stoichiometric relations between the materials involved in a
physical and chemical reaction.
TEXT BOOKS
1. Bhatt, B.L., Vora, S.M., “Stoichiometry”, Tata McGraw-Hill, 1976.
2. Himmelblau, D.M., “Basic Principles and Calculations in Chemical Engineering”,
EEE Sixth Edition, Prentice Hall Inc., 2003 (with CD containing programmes and problems).
REFERENCES
1. Process Calculation for Chemical Engineering, Second Revised Edition, Chemical Engineering
Education Development Centre, I.I.T., Madras, 1981.
2. Process Calculations, Venkataramani, V and Anantharaman, N, Prentice Hall of India Pvt. Ltd.,
2003.
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UNIT – I
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For example, length is a physical quantity. The metre is a unit of length that represents a
definite predetermined length. When we say 10 metres (or 10 m), we actually mean 10 times
the definite predetermined length called "metre".
The definition, agreement, and practical use of units of measurement have played a crucial
role in human endeavour from early ages up to this day. Different systems of units used to be
very common. Now there is a global standard, the International System of Units (SI), the
modern form of the metric system.
Principle of stoichiometry:
The mass and the gas volumetric relationships in chemical reactions are presented together
with the basic units for expressing charging in mass and composition.
1) 100g of chlorine gas is mixed with 10g of hydrogen gas. Calculate the mole fractions
of the two gases in the mixture.
Ans. Basis: 110g of gas mixture.
Component Gmmole Mol.Wt. Gm Mole Mole Fr.
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Mole fraction:
Mole fraction of a component in a mixture is defined as the ratio of the number of moles of
that component to the total number of moles.
No. of moles of A
Mole fraction of a component A in (A+B) mixture = -------------------------
No. of moles of (A+B)
Volume occupied by A
Volume % of component A in (A+B) mixture = ------------------------------------
Volume occupied by (A+B)
Pbm: A solution of caustic soda contains 30% NaOH (by weight).The density of the solution
is 1.196 g/cc. Find the molarity and normality of the solution.
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Pbm: A sample of wine contains 20% alcohol on volume basis. Find the weight percent of
alcohol in the wine. The density of alcohol and alcohol-free liquid are 0.79 g / cc and 1 g / cc
respectively.
Ans. Basis: 100 cubic metre of wine.
DEGREE TWADELL
Degree Twadell = 200 ( (S.G.( 288.7 / 288.7) – 1)
Pbm: Convert the diffusion coefficient of 0.87 ft^2 / hr into MKS unit.
Ans. 1 ft = 0.3048 m
1 hr = 60 * 60 s = 3600 s
0.87t^2/ hr = 0.87 * 0.3048 ^ 2 / 3600 = 2.24 * 10 ^(-5) m^2 / s
0.88
Pbm: The available nitrogen in an urea sample is found to be 45% (by mass). Find the actual
urea content in the sample.
Ans. Basis: 100 kg of urea.
Urea molecular formula: NH2CONH2
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Problems – Tutorials:
1) A limestone analysis CaCO3 - 94.52% , MgCO3- 4.16% and inert- 1.32%. Calculate (a)
kgs of calcium oxide could be obtained from 4 tons of limestone.
(b) How many kgs of CO2 are given off per kg of limestone?
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4) Two different persons calculate the average molecular weight of a flue gas sample.
One person used the correct molecular weight for nitrogen and found that that average
molecular weight as 30.08. The other person by mistake in the atomic weight for
nitrogen and found the value as 18.74. Calculate the composition of flue gases, if the
other gases are CO2 and O2.
N2 x 28 28x 14x
CO2 y 44 44y 44y
O2 z 32 32z 32z
--------- --------- ---------
100 3008 1874
--------- ---------- -----------
x+y+z = 100 --- (1)
28x + 44y + 32z = 3008 --- (2)
14 x + 44y + 32z = 1874 ---(3)
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16 * 81 +12z = 1392 z = 8%
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UNIT – II
GAS CALCULATIONS
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RaOult’s Law.
Rault’s law holds good for ideal and dilute solutions. According to this law, the vapour
pressure of the solvent in a solution is directly proportional to the mole fraction of the solvent
pi = Pi xi
Henry’s law.
According to this, for non-ideal solution (low concentration of gas in liquid), the partial
pressure of solute gas is proportional to the mole fraction of the solute in the solution
pi = Hi xi
By Pass Stream
It is a ream that skips one or more stages of the process and goes directly to another
stage with the purpose of controlling the composition of a final exit stream.
Purge Stream
A stream bled off to remove an accumulation of certain inerts or unwanted materials
that might otherwise build up in the Recycle Stream is called a Purge Stream.
Calculate the volume occupied by 30 lb of Chlorine at a pressure 743 mm Hg and
70F.
Solution:-
Volume of S.C. = 0.423 359 = 152 Cu.ft.
P1 T2
V2 = V1
P2 T1
70 F = 530R
760 530
Volume of 743 MMHg, 70F = 152
743 492
= 167 Cu.ft.
Calculate the weight of 100 cu. Ft. at water vapour, measured at a pressure of 15.5 mm
Hg and 23C.
Solution:-
15.5 273
Volume of S.C. = 100 1.88 Cu.ft.
760 296
Calculate weight of 100 Cu.ft. of water vapour. Measured at a pressure of 15.5 mm Hg.
and 23C.
Solution:-
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15.5 273
Volume of S.C. = 100 1.88 cu.ft.
760 296
Solution:-
V1 T2
P2 T1
V2 T1
30C 303K
81.7 303
Pressure at 20 Cu.ft. = 14.7
20 273
= 66.6 psi
Assuming the applicability of the ideal gas law. Calculate the maximum temperature
to which 10 lb of T2, enclosed in 30 cu.ft. chamber.
Solution:-
Volume at S.C. = 0.307 359
= 128.1 Cu.ft.
P2 V2
T2 T1
T1 V1
150 30
= 273
14.7 128.1
The actual volume occupied by each of there components will always be exactly the
same as that of the entire mixture.
A volume of moist air 30m3 at a total pressure of 101.325 kPa and a temperature of
303K (30C) contains water vapor in such proportions that its partial pressure is 2.933
kPa. Without total pressure being changed the temperature is reduced to 288K (15C)
and some of water vapour is removed by condensation. After cooling it is found that
the partial pressure of water vapour is 1.693 kPa. Calculate (a) volume of air at 288K
(15C) and (b) weight of water condensed.
Solution:-
Basis: 30m3 of moist air at 303K.
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P = 101.325 kPa
R = 8.31451 m3.kPa/kmol.K.
V = 30m3
T = 303K
101.325 30
n = moles of moist air =
8.31451 303
= 1.2066 kmol.
= 101.325 – 2.933
= 98.392 kPa
= 2.933 kPa
Pressure % = mole %
For air
98.392 n1
101.325 n
98.392
n1 1.2066
101.325
2.933 n
2
101.325 n
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2.933
n2 = 1.2066
101.325
At 288K,
Partial pressure of water vapour = 1.693 kPa
Let n3 be the moles of water vapour at 288K.
Moles moist air = 1.172 + n3
1.693 n3
101.325 1.172 n3
n3 = 0.02 kmol
PV = n’RT
n’ = 1.192 kmol
R = 8.31451 m3.kPa/kmol.K
T = 288K
P = 101.325 kPa
n'RT
V=
P
= 0.035 – 0.02
= 0.015 kmol.
= 0.27 kg.
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Calculate the density in pounds per cubic foot at 29 in. Hg and 30C of a mixture of
hydrogen and oxygen that contains 11.1% of H2 by weight.
Solution:-
H2 = 0.111 lb
O2 = 0.889 lb
Total Quantity
Volume of SC = 0.0833 359 = 29.9 cu.ft.
29.92 303
Volume of 29 inches 30 C = 29.9
29.0 273
= 34.2 Cu.ft.
A mixture of CH4 and C2H6 has density 1.0 kg/m3 at 273K (0C) and 101.325 kPa
pressure. Calculate the mole % and weight % CH4 and C2H4 in the mixture.
Solution:-
P Mave
Density of gas mixture = =
RT
RT
Mave = .
P
where = 1 kg/m3
T = 273 K
P = 101.325 kPa
R = 8.31451 m3. kPa/kmol. K
8.31451 273
Mavg. = 1
101.325
= 22.4
Let x CH4 and x C2H6 be the mole fractions of CH4 and C2 H6 respectively.
xi = 1
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xCH4 xC2H6 1
….(2)
xC2H6 1 xCH4
….(3)
Put the value of x c 2H6 from equation (3) in equation (1) and solve for x CH4 .
xC2H6 = 0.457
= 54.3
Mole % of C2H6= 0.457 100
= 45.7
Weight of CH4 in 1 kmol mixture = 0.543 16
= 8.69 kg
Weight of C2H6 in 1 kmol mixture = 0.457 30
= 13.71 kg.
Weight of gas mixture = 22.4 kg
8.69
Weight % of CH4 in mixture = 100
22.4
= 38.8
Weight % of C2H6 in mixture = 100 – 38.8
= 61.2
In one case 26.6 litres of NO2 at 80 kPa and 298K (25C) is allowed to stand until the
equilibrium is reached. At equilibrium the pressure is found to be 66.662 kPa.
Calculate the partial pressure of N2O4 in the final mixture.
Solution:-
P1V1 = n1RT1
P1V1
n1 = Initial moles =
RT1
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V1 = 0.0266 m3
80 0.0266
n1 = 8.6 104 kmol
8.31451 298
n1 = 0.86 mol
2 NO2 = N2O4
= 0.86 – x mol
P1 n1
P2 n2
80 0.86
66.662 0.86 x
= 0.20
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A closed vessel contain a mixture of 40% NO2 and 60% N2O4 at a temperature of 311K
(38C) and a pressure of 531.96 kPa. When the temperature is increased to 333K
(60C), some of N2O4 dissociates to NO2 and a pressure rises to 679.95 kPa. Calculate
the composition of gases at 60C by weight.
Solution:-
40
Moles of NO2 = 0.87 kmol
46
60
Moles of N2O4 = 0.652 kmol
92
N2O4 = 2NO2
= 1.522 + x kmol
P1 n1 T1
.
P2 n2 T2
n1 = 1.522, n2 = 1.522 + x
T1 = 311K, T2 = 333K
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Solving we get,
x = 0.295 kmol.
1) A mixture of gases has the following composition by weight Cl2 – 65% Br2 –25% and O2 –
10%.Using ideal gas law calculate i) composition of gas mixture by volume ii) density of the
gas mixture in kg / m3 at 25oC and 740 mmHg iii) Specific gravity of the gas mixture.
Ans. For gases, VOLUME% = MOLE%.
Basis: 100 kg of gas mixture.
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2) In the manufacture of hydrochloric acid , a gas is obtained which contains 25% HCl
and 75% air by volume.This gas is passed through an absorption system in which 98%
HCl is removed. The gas enters the system at a temperature of 49 degree C and a
pressure of 738 mmHg and leaves at 38 degree C and a pressure of 738 mmHg.
Calculate the following i) Volume of gases leaving per 100 m3 entering the system and
ii) weight of HCl removed per 100 m3 of the gas entering the absorption system.
PV = nRT
i) Volume of gas :
P1 V1 / T1 = P2 V2 / T2
738 * 75.5 / 322 = 738 * V2 / 311
V2 = 72.92 m3
ii) Weight of HCl removed :
PV = nRT Moles of HCl n = PV / RT
= 738 * 24.5 / (62.396 * 322) = 0.89 kg mol.
Weight of HCl removed = Moles * Mol.wt. = 0.89 * 36.5 = 32.485 kg.
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Calculate the number of hours of service that can be derived from 1 kg carbide in an
acetylene lamp burning 60 lit per hour of gas at a temperature of 30oC and a pressure of 725
mmHg. Assume ideal gas law obeys.
Ans. Molecular weight of CaC2 = 64
Temperature T = 30 + 273 = 303 K
Pressure of gas P = 725 mmHg
Gas constant R = 62.40 mmHg l / gmol K
No.of Moles of Calcium carbide n = 1000/64=15.63gm-moles
Ideal gas law :
PV = nRT
V = nRT / P = 15.63 * 62.40 * 303 / 725
Volume of carbide V = 407.58 lit.
60 lit. of take 1 hour = 60 min
407.58 lit. would take = ( 60 / 60) * 407.58 = 408 min. = 6hr.48 min.
4) Calculate the total pressure and composition of vapour in contact with the solution at
100oC containing 40% benzene , 35% toluene and the rest ortho-xylene by weight.Vapour
pressure of benzene = 1340 mmHg , toluene = 560 mmHg and ortho-xylene = 210 mmHg.
Ans. Basis : 100 kg of mixture.
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UNIT – III
MATERIAL BALANCE
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The spent acid from a nitrating process contains 33% H2SO4 36% HNO3 and 31%
water by weight. This acid is to be strengthened by the addition of concentrated
sulphuric acid containing 95% H2SO4and concentrated nitric acid containing 78%
HNO3. The strengthened mixed acid is to contain 40% H2SO4 and 43% HNO3.
Calculate the quantities spent and concentrated acids that should be mixed together to
yield 1500 kg of the desired mixed acid. (A.M.I.E. Exam. Summer 1975, Winter 1978
and summer 1979).
Solution:
X+y+z=1500 ….(1)
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600-0.33x
From Eq. (2), y= .....(4)
0.95
645-0.36x
From Eq. (3), z= .....(5)
0.78
Weights of waste (spent) acid, conc. H2SO4 and co. HNO3 required are 217.3, 556.1 and
726.6 kg respectively.
Solution:
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XF=0.13
XC=1.0
0.39 294
xM 0.103
0.39 294 1000
So, C=104kg
F=E+M+C=E+M+104 …..(1)
or M-(F-E-104) =(1000-E-104)=896-E
FxF=MxM+Cxc ….(2)
E=643.6 kg
Solution:
E=evaporated water
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M=mother liquor
F=C+E+M=C+112.5+M
Or, 1000=112.5=C+M
i.e., M=(887.5-C)
106
xC 0.371
286
21.5
xM 0.177
121.5
FxF=MxM+CxC
10000.25=(887.5-C)0.177+0.377C
(i)
Calculate the composition of the original charge.
(ii)
If the decomposition of the phosphate is 90% complete and the reduction of
the phentoxide is 70% complete, calculate the amount of phosphorous
produced per 100 kg of charge.
Atomic weights: P-31.0, Si-28.0, Ca-40.0. (A.M.I.E Exam. 1975 Winter)
Solution:
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Charcoal 84 14.19
142
52.36 0.9 21.58kg.
310
62
15.11 P2O5 produces 15.11 6.6kg.
142
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Bottled liquid gas of the following composition is sold for house – hold use:
Composition, Mole% 50 45 5
Determine (i) the pressure of the system and the equilibrium vapour composition at
30oC and (ii) if all the ethane be removed from the liquid, the pressure of the system and
the vapour composition at 30oC. Assume Rault’s law is applicable. (A.M.I.E. Exam.
Summer 1976).
Solution:
Components Mol frac. In liquid Vapour pr., bar Partial pr., bar
Partial pressure
y
Pr essure of the system
Pbu tan s
ybu tan s
Total pressure
Equilibrium vapour composition:
1.70
= 100 19.12%m
8.89
4.86
Similarly, y propane 100 54.67%m
8.89
2.33
y ethane 100 26.21%m
8.89
=1.0-0.05=0.95 kg mol.
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Components Mol
CCl4 23.3
S2Cl2 23.3
CS2 1.4
Cl2 32.0
In this case CS2 is the limiting reactant and Cl2 is the excess reactant. From the product
analysis, it is seen that 23.3 kg mols of CS2 have been converted.
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= 27.8kg.mol.
27.8
100 37.52
74.1
154
100kg of Cl2 yield 100
3 71.0
=72.3 kg of CCl4
SO2 reacts with pure O2 to form SO3. If the reaction is carried out with 100% excess
oxygen as necessary for complete oxidation, but under such low temperature and
pressure that the reaction goes only 60% to completion, calculate:
Solution:-
1
Reaction : SO2 + O2 SO3
2
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Analysis of reactants:-
O2 100 0.500
Analysis of products:-
SO2 40 0.235
SO3 60 0.353
O2 70 0.412
O2 70 2240 0.233
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= 56.46
100
(e) 100 gm SO2 = 1.56 gm mol
64
170
100 gm mol of SO2 yield 1.56 2.65 gm mol of product
100
nRT
Volume of gas =
P
Two pure organic chemicals A and B are introduced into the apparatus as shown in the
figure below for the purpose of making the compound AB. Stream flows are adjusted so
that mole ratios of A to B in the reactor is 4:1. At the temperature and pressure
employed, this mole ratio effects complete consumption of B, 90% of the B forms AB,
the desired product. The remainder forms A2B, a useless by product. A2B is incapable
of further reaction. The effluent stream from the reactor is cooled to 20 C, at which
temperature A and AB are completely immissible. A2B however is soluble in A and AB.
The distribution coefficient is
CAB
k 6
CA
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CA = mol A2B/mol A.
Calculate the amount of all material flowing in each numbered stream, per 100 mole of
desired product AB in stream 4. (A.M.I.E. Exam. Summer.
1977)
Fig.
Solution:-
A + B
AB
Since, 90% of B forms AB, 90 mol of B reacts with 90 mol of A to give 90 mol AB
2A + B
A2B
110
100 mol AB produced = 100 122 mol A reacted
90
100
100 111
90
The only place that A2B can leave the process is with AB. After start-up, the
recycle stream composition will change constantly until a steady state has been reached.
Under steady state conditions,
10
Mol A2B with stream (4) = 100 11.0
90
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Stream (3) and (4) are in equilibrium with respect to the concentration of A2B.
11
CAB
100
CAB
6 (given)
CA
11 mol A 2B
CA
600 mol A
mol A 4
; mol A = 4 111 = 444
mol B 1
= 11/600
11
Mol. A2B in stream (3) = 322 5.90
600
1000 kg of an impure limestone which analysis 96% CaCO3 and 4% inert material is
reacted with a sulphuric acid solution containing 70% sulphuric acid and 30% water.
The reacting mass is heated and all the CO2 generated is driven off together with some
of the water. The analysis of the final solid ‘cake’ is
CaSO4 – 86.54%
CaCO3 – 3.11%
H2SO4 - 1.35%
H2 O - 6.23%
Inerts - 2.77%
Calculate :-
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Solution:-
Basis : 100 kg of cake formed
Reaction : CaCO3 + H2SO4 CaSO4 + CO2 + H2O
Amount of CaSO4 formed = 86.54 kg.
100
CaCO3 consumed = 86.54 63.63 kg.
136
63.63
95.34
63.63 3.11
98
(b) Acid used = 86.54 62.36 kg.
136
63.71
= 1000 916.56 kg H2SO4
69.51
916.56
Acid solution fed = 1309.37 kg.
0.7
18
Water formed = 63.63
100
11.45
= 1000 164.72 kg.
69.51
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6.23
1000 89.63 kg.
69.51
44
CO2 formed = 63.63 28.00 kg.
100
28
CO2 formed = 1000 402.82 kg.
69.51
= 870.72 kg
Solution:-
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= 2760 mm Hg absolute.
PV mm Hg lit.
nCH4 , R = 62.36
RT gm mol K
14.61
Mol fraction of CH4
14.61 43.82 87.64
14.61
= 0.10
146.07
43.82
Mole fraction of C2H6 0.30
146.07
87.64
Mol fraction of H2 0.60
146.07
14.61 gm mol
1.46 105
1000 1000 cc
43.82 gm mol
Concentration of C2H6 = 4.38 10 5
1000 1000 cc
87.64 gm mol
Concentration of H2 = 8.76 10 5
1000 1000 cc
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146.07 gm mol
(d) Molar density of the mixture = 0.146
1000 lit.
C 2 H6 43.82 30 1314.60
H2 87.64 2 175.28
Total 1723.64
Figure
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Solution:-
= 39 + 35.5 = 74.5
Let F, M, E and C represent the amounts of feed, mother liquor, evaporation and
crystals and xF, xM, xE and xC their solid fractions respectively.
55
xE 0 xF 0.355
100 55
35
x C 1.0 xM 0.259
100 35
F=E+M+C ….(1)
4000
i.e. F= 11,268 kg
0.355
C = 1578 kg.
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UNIT – IV
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The humidity (H) of a gas in generally defined as that of water per unit cut of moisture free gas.
Molar humidity
Relative humidity
It is defined as the ratio of the partial pressure of condensable vapour in gas phase to the vapour
pressure of liquid.
Saturation humidity
Absolute Humidity
This is defined as the weight of water vapour per unit weight of dry air in the mixture.
Percentage humidity
It is the ratio of the molal humidity at unsaturated conditions to the molal humidity at saturation.
%H = Hm /Hms x100 %
Humidification
The operation that is carried out increase the amount of vapour in a gas stream.
Dehumidification
Dew point
If an unsaturated mixture of vapour and gas is cooled the relative amounts of the components and
the percentage composition by volume will at first remain unchanged.
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The dry bulb temperature and dew point of ambient air were found to be 302 K (29oC)
and 291 K(18oC) respectively, Barometer reads 100 kPa. Calculate:
Solution:
PA
Absolute molal humidity = Hm
P PA
2.0624
=
100-2.0624
kmol water vapour
=0.02106
kmol dry air
.....Ans. (a)
Mol.wt.H2O
Absolute humidity =H= Hm
Mol.wt.air
18
=0.02106
19
kg water vapour
=0.0131
kg dry air
.....Ans. (b)
At saturation,
DB=WB=DP=302K
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PA
% RH = 100
P6
2.0624
= 100
4.004
=51.51
.......Ans(c)
P Mol.wt.H2O
Saturation humidity = H8 8
P P6 Mol.wt.air
4.004 18
H8
100 4.004 29
kg water vapour
=0.02589=
kg dry air
H
% saturation = 100
H5
0.0131
= 100
0.02589
….Ans.(d)
=1.006+1.884 0.0131
H 1
Humid volume = VH 22.4136
MA Ms
DB 101.325
273 P
0.0131 1 302 101.325
= 22.4136 100
18 19 273
=0.8846m3 / kg dry air .....Ans.(e)
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2. A mixture of benzene and dry air at a temperature of 303 K(30oC) and a pressure of
101.325 kPa is found to have a dew point of 288 K(15oC).
Calculate:
Solution:
= 7.999 kPa.
PA
Volume % of benzene= 100
P
7.999
= 100
101.325
=7.9
....Ans.(a)
1 mol of mixture
0.079
Moles benzene per mole of air=
0.921
=0.086 ....Ans(b)
Solution:
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15.8
Molfraction of acetone in mixture = y =
100
P= total pressure = 101.325 kPa.
=0.158 101.325
=64.98 …..(Ans)
0.158
1 0.158
0.1876
Consider one mole of saturated mixture at 293 K(20oC) and 101.325 kPa.
= 24.31
24.31
Acetone in saturated mixture = 1
100
=0.2431 mol
=0.7569 mol
0.2431
=
0.7569
= 58.40 …..Ans.
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Solution:
As the mixture is saturated at 323K, the partial pressure of benzene is equal to vapour
pressure of benzene at 323 K.
PA =36.664 kPa
P=101.325 kPa
PA
Hm
P PA
36.664
=
101.325-36.664
kmol benzene vapour
=0.567
kmol nitrogen
Mol wt.C6H6
Absolute humidity = Hm
Mol wt. N2
78
=0.567
28
kg benzene
=1.579 .....Ans.(a)
kg nitrogen
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36.664
=
101.325-36.664
Kmol benzene vapour
=0.567
kmol carbon dioxide
Mol wt. C6H6
Absolutehumidity Hm
Mol wt. CO2
78
=0.567
44
kg benzene
=1.005 ....Ans(b)
kg carbon dioxide
5. The dry bulb temperature and dew point of ambient air were found to be 303
K(30oC) and 289 K(16oC) respectively. Calculate (i) the absolute molal humidity, (ii) the
absolute humidity, (iii) the % RH, (iv) the % saturation and (v) the humid heat.
Solution:
PA =1.818kPa
P=total pressure
=100 kPa
PA
Absolute molal humidity = Hm=
P PA
1.818
100 1.818
kmol water vapour
0.01852 .....Ans.(i)
kmol dry air
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Mol.Wt.H2O
Hm
Mol Wt. air
18
Absolute humidity = H 0.01852
29
kg water vapour
0.0115 ....Ans.(ii)
kg dry air
At saturation,
DB=WB=DP=303K
i.e. at 303 K
Pa = 4.243 kPa
PA
100
Pa
1.818
%RH= 100
4.243
42.85 .....Ans(iii)
4.243 18
Saturation humidity = H8=
100 4.243 29
kg water vapour
0.0275
kg dry air
H
% Saturation = 100
H8
0.0115
= 100
0.0275
=41.82 .....Ans(iv)
=1.006+1.84 0.0115
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6. A mixture of benzene vapour and nitrogen gas at 297 K and 100 kPa has a relative
humidity of 60%. It is desired to recover 80% of benzene by cooling a mixture to 283
K(10oC) and compressing to a suitable pressure. Find out the pressure required for
above duty.
Solution:
PA
%RH 100
P8
=12.2 kPa.
pA
60 100
12.2
pA = 8.32 kPa
at 297 K
pA .MA
Mass of benzene = V
RT
where pA = 7.32 kPa
MA = 78
T =297 K
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7.32 78 1
Mass of benzene=
8.31451 297
=0.31kg
Mass of nitrogen =
100-7.32 28 1
8.31451 297
=1.051 kg
0.231
Hence,humidity=H=
1.051
=0.22kg/kg
PA
Hm
P PA
7.32
=
100-7.32
kmol benzene
=0.07898
Kmol nitrogen
Mol wt.C6H6
Humidity =H=Hm
Mol wt. N2
78
=0.07898
28
kg benzene
=0.22
kg nitrogen
In order to recover 80% of benzene, the humidity must be reduced to 20% of its initial
value. As the vapour will be in contact with liquid benzene, the nitrogen will be saturated with
benzene vapours and hence at 283 K.
20
Ho 0.22
100
kg benzene
=0.044
kg nitrogen
p M
Ho s A
P Ps MB
where Ho=0.44
MA=78, MB=28
P= total pressure
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O8=6kPa at 283 K
(p.p. of benzene vapour in saturated gas is equal to vapour pressure of benzene at 283 K).
6 78
0.044
P 6 28
0.044(P-6)=16.71
0.044P-0.264=16.71
P=385 kPa
Solution:
= 14.8
=0.148
PA=y.P
=0.1488 99.33
=14.7 kPa.
14.8
Acetone in mixture = 1
100
=0.148 kmol
=0.852 kmol.
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0.148
Hm kmols acetone per kmol nitrogen =
0.852
=0.174 ....Ans(b)
pA
% relative saturation = 100
p8
14.7
= 100
24.638
=59.66 ...Ans(c)
Consider one kmol of saturated mixture at 293 K (20oC) and 99.33 kPa.
P3
100
P
24.638
100
99.33
24.80
Mole % acetone = volume % acetone = 24.8
=0.248 kmol
=0.752 k mol
0.248
0.752
=0.329
Hm
% saturation = 100
Hms
0.174
= 100
0.329
=52.9 ....Ans.(d)
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8. An air – water vapour mixture has relative humidity of 80% at 293 K(20oC)
temperature and 100 kPa pressure. Calculate: (a) molal humidity of air, (b) molal
humidity of air if its temperature is reduced to 283 K(10oC) and the pressure is
increased to 174.65 Kpa condensing out some of the water, (c) Calculate the weight of
water condensed from 500 kg of original wet air in the process of part (b), (d) calculate
the final volume of the wet air of the part (c).
Data: Vapour pressure of water at 293 K(20oC) = 2.40 kPa Vapour pressure of water at
283K(10oC) = 1.266 kPa.
Solution:
P8=2.40 kPa
PA
%RH= 100
P8
pA
80 100
2.40
pA = 1.92 kPa
PA
Initial molal humidity Hm
P PA
7.32
Hm =
100-7.32
kmol water vapour
=0.01958 ....Ans(a)
Kmol dry air
Final partial pressure of water vapour (i.e. at 293 K) is equal to the vapour pressure of water
at 283 K (10oC) as air becomes saturated at that stage.
PA at 283K=1.266 kPa
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PA
P PA
1.266
=
174.65-1.266
kmol water vapour
Final molal humidity =0.0073 ....Ans(b)
Kmol dry air
18
on weight basis =0.01958
29
kg water
=0.0122
kg dry air
18
on weight basis =0.0073
29
kg water
=0.00453
kg dry air
At 293 K(20oC), air water vapour mixture contains 0.0122 kg water vapour (moisture) per kg
dry air i.e. per 1.0122 kg of wet air.
0.0122
500
1.0122
=6.026 kg
=493.974 kg
0.00453
water present at 283K (i.e. final)= 493.974
1
=2.238.kg
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=6.026 – 2.238
=3.788kg
=493.974 +2.238
=496.212kg
2.238
Water in wet air at 283 K=
18
=0.1243 kmol
493.974
Dry air in wet air at 283 K=
29
=17.033 kmol
=17.1573 kmol
PV=nRT
nRT
V
P
Where n= 17.1573 kmol, T= 283 K
m3 .kPa
P=174.65 kPa, R= 8.13451
kmol.K
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9. Carbon dioxide contains 0.053 kmol of water vapour per kmol of dry CO2 gas at
temperature of 308 K(35oC) and a total pressure of 100 kPa.
Calculate: (a) Relative saturation of the mixture, (b) Percentage saturation of the
mixture, and (c) The temperature at which the mixture must be heated in order to
achieve the relative saturation of 30%.
Solution:
= 1.053 kmol
0.053
Molfraction of water vapour in gas mixture = y=
1.053
=0.0503
=0.0503 100
=5.03 kPa
PA
Relative saturation at 308 K(35oC)= 100
P8
5.03
100
5.60
=89.82 ….Ans(a)
0.0503
0.0503
1
Consider one kmol of saturated mixture at 308 K(35oC) and 100 kPa.
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5.6
= 100
100
=5.6
5.6
Water vapour in mixture = 1
100
=0.056 kmol
=0.944 kmol
0.056
0.944
=0.0593
Hm
% saturation = 100
Hms
0.053
= 100
0.0593
=89.37 ...Ans(b)
PA
Relative saturation 100
P8
5.03
30 100
P8
Water exerts a vapour pressure of 16.767 kPa (approximately equal to at 330 K(57oC) as
per the data supplied.
Hence, the mixture should be heated to 330 K(57oC) to get the desired relative saturation as
vapour pressure at 330K (57oC).
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10. A gas mixture containing carbon disulphide vapour [CS2] at a temperature of 300K
(27oC) and a pressure of 100 kPa has the percentage saturation of 70. Calculate the
temperature to which gas must be cooled at constant pressure so as to condense
40% of CS2 present.
Solution:
P8=52.662 kpa
P=100 kpa
% saturation =70
% saturation =
pA / P pA 100
P8 / P Ps
70=
pA /100 pA 100
52.662 /100 52.662
Solving we get,
PA=43.778kPa
43.778
CS2 in the mixture 1
100
=0.43778
=0.4378 kmol
=0.5622
=0.1751 kmol
= 0.2627 kmol
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=0.8249 kmol
0.2627
Mol % CS2 = 100
0.8249
=31.85
pA
100 31.85
P
pA
100 31.85
100
p A 31.85kPa.
As the mixture is saturated, the partial pressure of CS2 is equal to vapour pressure at final
temperature, the vapour pressure of CS2=31.85 kPa.
From the data cited the temperature at which the vapour pressure of CS2 is approximately
31.85 kPa is 287 K(14oC).
Solution:
P = 100kPa
pA / P pA
% humidity = 100
P8 / P Ps
60=
pA /100 pA 100
3.565 /100 3 / 565
Solving Pa = 2.170 kPa
2.170
Amount of water vapour in mixture 1
100
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=0.9783 kmol
=0.01953 kmol
=0.98047 kmol
2.17 103
100
Mole % water vapour in the mixture = 0.98047
0.2213
Let PT be the final pressure to which air must be compressed.
The partial pressure of water vapour is equal to the vapour pressure at 300 K(27oC) as the
mixture is saturated at PT.
PA=3.565 kPa
Mole% = pressure %
pA
0.2213 100
PT
3.565
0.2213 100
PT
pT 1610.9kPa(15.90atm). .....Ans.
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UNIT – V
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A fuel is heat evolved in its complete combustion under constant pressure at a temperature of 25C.
It is defined as final state of the water in the system after combustion is taken as vapour at 25C.
The heat of formation of carbon is the form of the diamond in accurately known and is equal to 0.45
32 Kcal per g-atom.
Coal analysis:
It is addition to organic matter it contain minerals constituent of the plants from which it was
formed and inclusion.
The standard heating values at fuel correspond to conditions at complete combustion of all carbon
to carbon dioxide gas.
The total heating value of a fuel is the heat evolved in its complete combustion under constant
pressure at a temperature of 250C when all the water initially present as liquid in the fuel and
present in the combustion products are condensed to the liquid state.
The net heating value is defined except that the final state of the water in the system after
combustion is taken as vapor at 250C.The total heating value is also termed the `gross` heating value.
The net heating value is also termed as the lower heating value.
Rank of Coal:
Fuel ratio of a coal is defined as the ratio of percentage of fixed carbon to that of volatile matter.
The rank of the coal whether bituminous or anthracite, may be estimated from its fuel ratio.
The total heating value of a coal may be determined by direct calorimetric measurement and
expressed as Btu/lb. The net heating value is obtained by subtracting from the total heating value
the heat of vaporization at 250C of the water present in the coal and that formed by the oxidation of
the available hydrogen.
Where H.V. = heating value, H wt. Fr. Of total hydrogen including available H2, H2 in moisture and H2
in combined H2O
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Orsat analysis:
The analysis of flue gases is ordinarily determined by the orsat type of apparatus, yielding the
percentages of carbon dioxide, carbon monoxide, oxygen and nitrogen in the moisture free gases.
Ultimate analysis:
It is a method of analysis of a fuel which gives the complete composition of i) C ii) H 2 iii) N2
iv) S v) Ash
Proximate analysis:
It is determination is made of each of the proximate analysis defined groups of moisture, volatile
matter, ash and fixed carbon (obtained by deducting %moisture, %volatile matter, % ash from 100).
Problem1. The waste acid containing 25% HNO3, 50% H2SO4 and 25% H2O by weight .This acid is
to be concentrated to contain 30% HNO3 and 60% H2SO4, by the addition of concentrated H2SO4
containing 95% H2SO4 by weight and concentrated HNO3 containing 90% HNO3 by weight.
Calculate the weights of waste acid and concentrated acids to obtain 10,000 kg of mixture of desired
composition.
Let ‘x’ be the amount of waste acid Let ‘y’ be the amount of concentrated H2SO4acid
x + y + z =10000 Kg
y=6000-0.5x/0.95=6315.79-0.526x
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x+6315.79-0.526x+3333.33-0.278=10000
x(1-0.526-0.278)=350.88 x=1790.20 kg
Problem 2: 1000 kg of sodium carbonate solution containing 23% Na2CO3 is subjected to evaporative
cooling. During which 15% of the water present in the solution is evaporated. From the concentrated
solution Na2CO3 .10H2O crystallizes out. Calculate how much crystals would be produced if the
solubility Na2CO3 .10H2O be 21.5grams per 100 grams water.
Problem.3:1:3 nitrogen hydrogen mixtures are fed to an ammonia converter resulting in 25%
conversion to ammonia. The unconverted gases are recycled to the reactor. The initial mixture
contains 0.2 parts argon per 100 parts of the nitrogen hydrogen mixture. The toleration limit for argon
is 5 parts per 100 parts by volume. Estimate the fraction of the recycle that must be purged
continuously. Find the recycle and purge ratio
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When a steady state operation is obtained for Ar purged is = Argon in the fresh feed supplied
x – 0.754x=72.01
Problem.4:
10,000 kg of an aqueous solution containing 29.6% Na 2SO4 is cooled. During cooling 5% water in
the solution is lost by evaporation. As a result crystals of Na 2SO4 .10H2O crystallize out. If the
mother liquor is found to contain 18.3% Na 2SO4 .Calculate the weight and percent yield of crystals
and the quantity of mother liquor obtained. All percentages are by weight
Na2SO4 balance:
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Problem.5
Air at a temperature of 200 C and a pressure of 750 mmHg has a relative humidity of 80%. (i)
Calculate the molal humidity of the air.
(ii)Calculate the molal humidity of this air if its temperature is reduced to 100 C and its pressure is
increased to 1810 mm Hg condensing out some of the water.
(iii) Calculate the weight of water condensed from 28,000 Liters of the original wet air in cooling
and compressing to conditions of Part (ii)
(iv) Calculate the final volume of the wet air of Part (iii)
iii) The weight of water condensed = n(H m initial –Hm final ) x18
= (1810-7.36) V2 /283
Problem.6:
Chlorobenzene is nitrated using mixture of nitric acid and sulphuric acid. The reaction is
A charge consisted of 100 Kg of chlorobenzene, 106.5 Kg of 65.5% nitric acid and 108
Kg of 93.6 % Sulphuric acid (by weight). After 2 hrs. of operation the final mixture was
analyzed. It was found that the final product contain 2% unreacted chlorobenzene. Also
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Compts Kg wt%
314.50 100%
-------------- ---------------
314.5 Kg charge314.5x2/100=6.29 Kg
100 Kg 100%
112.5 63 157.5 18
93.71 Kg ? ? ?
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Weight of P-nitrochlorobenzene=131.19x0.66=86.59 Kg
Compts Kg Wt%
____________________
314.50 100%
Problem .7:
Lignite pitch containing 80% carbon, 10% hydrogen, 3% oxygen and 1% nitrogen and remaining
sulphur by weight is completely burnt with 40% excess air. Determine the products of combustion.
O2=118.53 kg N2=1388.80 kg
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Problem.8:
H2 45 -----
CH4 30 30
C2H6 15 30
N2 10 -----
60
CO 0.16 0.16
O2 5.89 ------
N2 86.77 -----
7.34
Carbon Balance
0.690 x = 7.34
x =12.23 kg mol
N2 balance
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=5.89-0.16*1/2=5.81 Kg mole
Problem.9:
A Producer gas made from coke has the following composition by volume. CO= 28% , CO2 = 3.5% ,
O2 = 0.5% , and N2 = 68%. The gas is burnt with such a quantity of air that the oxygen from the air is
20% in excess of the net oxygen required for complete combustion if the combustion is 98 %
complete. Calculate the composition in volumetric % of the gaseous products formed per 100 Kg of
gas burned.
Composition of products
_____________
Total 5082.72kg 5
Dr.K.P.GOPINATH
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Composition of reactants:
Kgmole Mol.wt Kg
CO 28 28 784
O2 0.5 32 16
N2 68 28 1904
____________
Problem 10:
The exhaust from the diesel engine shows 10.2 % CO2 , 7.9 % O2, and the rest nitrogen. The analysis
was made in Orsat apparatus. Calculate (i) C / H ratio in fuel
Carbon balance
O2 Balance
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UNIT – VI
THERMO PHYSICS
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Conservation of energy:
According to law of conservation of energy, energy can neither be created nor be destroyed, but it
can be transferred from one form to another form
1/100 of the energy required to heat one gram of water from 0 to 100 ºC at a pressure of 1 atm is
called mean gram calorie.
Characterization factor:
When a crude oil of supposedly uniform character is fractioned into narrow cuts, the specific gravity
of each cut is approximately proportional to the cube roots of its absolute boiling point at 1 atm
pressure. The proportionality factor is taken as an index of the paraffinicity of the stock. Thus
K=3√TB/G Where K is the characterization factor, TB- average boiling poin, degress rankine at 1 atm
pressure, G-specific gravity at 60ºF
Kopp’s rule: “The standard heat of capacity of a solid compound is approximately equal to the
sum of the heat capacities of its constituent elements.” This generalization is termed as Kopp’s rule.
Hess’s law of heat summation states that the net heat evolved or absorbed in the chemical process
is the same whether the reaction takes place in one or more steps. (i.e.)H0533 (or) (H0
0 0
R+H 298+H P)
Trouton’s rule:
Trouton’s rule state’s that the ratio of the molal heat of vaporisation bof a substance at its
normal boiling point to the absolute temperature .Tb is a constant.b/Tb=K
where k= Trouton’s ratio21 for many substances.
Flame temperature:
When a fuel is burnt, lot of heat is generated since the reaction is exothermic. If the combustion
chamber is sealed from surroundings, the heat produced is utilized to heat the produce (flue gases).
Hence the flue gas comes out at a higher temperature which is called Flame temperature or
Theoretical Flame Temperature.
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1. A stream of nitrogen flowing at a rate of 100 kmol/h is heated from 303 K (30 oC) to
373 K (100 oC). Calculate the heat that must be transferred.
o
Data: Cp for nitrogen = 29.5909-5.141x10-3 + 11.1829 x 10-4 T2 – 4.968 x 10-9 T3.
Solution:
T2
Q n Cpo dT
T1
T2
Q n 29.5909 5.141 10 3 T 11.1829 10 6 T 2 4.968 10 9 T 3 dT
T1
T2 = 373 K
T1 = 303 K
= 202587.2 kJ/h
(As 1 J/s = 1 W)
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2. A stream of carbon dioxide flowing at a rate of 100 kmol/min is heated from 298 K
o
(25 oC) to 383 K (110 oC). Calculate the heat that must be transferred using Cp .
Data: Cp a bT cT dT
o 2 3
Solution:
n Cpo dT
T1
T2
Q n 21.3655 64.2841 103 T 41.0506 106 T 2 9.7999 109 T 3 dT
T1
T2 = 383 K
T1 = 298 K
64.2841 103
Q 100 21.3655 383 298 (383)4 (298)4
2
41.0506 10-6 9.7999 109
-
3
(383)3 (298)3
4
(383)4 (298)4
= 330335.5 kJ/min
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Solution:
Q = Heat added
T2
n Cpo dT
T1
T2
Q n 19.2494 52.1135 103 T 11.973 106 T 2 11.3173 109 T 3 dT
T1
52.1135 103 2
n 19.2494 T2 T1
T2 T12
2
11.973 106 3 11.3173 109 4
3
T2 T13
4
T2 T14
where n = 1 kmo1
T2 = 523K
T1 = 303 K
52.1135 103
Q 119.2494 523 303
(523)2 (303)2
2
11.973 106 11.3173 109
3
(523)3 (303)3 4
(523)4 (303)4
= 9242 kJ
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4. Temperature of pure oxygen is raised from 350 K (77 oC) to 1500 K (1227 oC).
Calculate the amount of heat to be supplied for raising the temperature of 1 kmol
o
oxygen using the following Cp data given below:
Solution:
Q = I eat to be supplied
T2
n Cpo dT
T1
T2
Q n 26.0257 11.7551 103 T 2.3426 106 T2 0.5623 109 T3 dT
T1
3
n 26.0257 T2 T1
11.7551 10
2
T 2
2 T12
2.3426 106 3 0.5623109 4
3
T2 T13 4
T2 T14
where n = 1 kmol
T1 = 350 K
T2 = 1500 K
11.7551 103
Q 126.0257 1500 350
(1500)2 (350)2
2
6 9
2.3426 10 0.5623 10
3
(1500)4 (350)4 4
(1500)4 (350)4
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5. Pure ethylene is heated from 303 K (30 oC) to 523 K (250 oC) at atmospheric
pressure. Calculate the heat added per kmol ethylene using data given below:
Solution:
Q = Heat added
T2
n Cpo dT
T1
T2
n 4.1261 155.0213 103 T 81.5455 106 T 2 16.9755 109 T 3 dT
T1
155.0213 103 2
n 4.1261 T2 T1
T2 T12
2
81.5455 106 3 16.9755 109 4
3
T2 T13 4
T2 T14
where n = 1 kmol
T1 = 303 K
T2 = 523 K
155.0213 103
Q 1 4.1261 523 303
(523)2 (303)2
2
81.5455 106 16.9755 109
3
523)3 (303)3 4
523)4 (303)4
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3 105
C 43.458 10.634 10 T 5.945 2
o
p
T
Calculate the heat required to raise the temperature of 1 kmol pure sulphur dioxide
from 300 K (27 oC) to 1000 K (727 oC).
Solution:
Q = Heat required
T2
n Cpo dT
T1
5.945 105
T2
Q n 43.458 10.634 10 3 T 2 dT
T1 T
10.634 10 3 2 1 1
n 43.458 T2 T1
T2 T12 5.945 105
2 T2 T1
10.634 103 2 1 1
n 43458 T2 T1
T2 T12 5.94 105
2 T1 T2
where n = 1 kmol
T1 = 300 K
T2 = 1000 K
10.634 103 1 1
Q 1 43.458 1000 300 2 2 5.94 105
2 1000 300 300 1000
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UNIT – VII
THERMO CHEMISTRY
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Heat capacity of a substance is defined as the amount of heat required to raise the
temperature of 1 Kg of a substance by 1 Kelvin.
For pure water, heat capacity at 150C =4.1855kJ/Kg.k
Heat capacity can be expressed in kJ/Kg.k (or) cal/g.c
Hess’s law:
Hess’s law of heat summation states that the net heat evolved or absorbed in the chemical
process is the same whether the reaction takes place in one or more steps. (i.e.)H0533 (or)
(H0 R+H0298+H0P)
Consider the reaction CH4 (g) + 2O2(g)CO2 (g) + 2H2O(g)
Heat capacities for the ideal gas state are independent of pressure. However, they are
functions of temperature.
The standard heat of reaction is the change in the enthalpy of a system as a result of the
chemical reaction-taking place at 1 atm and starting and ending with all the components
(reactants & products) at constant temperature of 250C.If stoichiometric number is doubled,
the standard heat of reaction is doubled.
The standard heat of reaction for any reaction can be calculated if the heat of formation (or
heat of combustion) of the compounds taking part in the reaction is known as follows:
H0298= Hf, products -Hf reactants
H0298= Hc reactants -Hc products
Heat of formation:
A formation reaction is defined as s reaction, which forms a single compound form the
elements contained in it.
e.g. C + ½ O2 +2H2CH3OH
The heat of formation is based on 1 mol of the compound formed. The equations should
indicate the physical state of each reactant and product whether it is gas, liquid or solid. The
heat of formation of a chemical compound is the standard heat of reaction where the
reactants are the necessary elements for the formation of compound which is the only
product formed.
Eg. C(s) + +O2 (g)CO2 Hf =94051 cal/g mol
For all the elements, the heat of formation is zero.
Heat of mixing:
When two liquids are mixed, the enthalpy change or heat effect is called the heat of mixing
measured at constant temperature. Usually at 180C or 250C and at the atmospheric
pressure. It is expressed in kJ/kg mol of solution, kJ/kg mol of solute, kJ/kg of solute, kJ/kg
of solution.
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When a liquid is heated from room temperature (say 250C) to a higher temperature (say
600C) and it remains as a liquid at 600C, then the sensible heat absorbed =q= m Cp (60-25)
Where m = mass of liquid Cp= specific heat of liquid.
If the liquid is further heated to 1000C, and it vaporizes, then
Heat absorbed =q= sensible heat + latent heat
= m Cp (100-25) + m Where = latent heat of vaporization.
Enthalpy –concentration diagram is useful for binary solutions. The enthalpy per unit solution
is plotted against concentration for a series of constant temperature and constant pressure
lines. With these charts, calculation effects in involved in changing the concentration and
temperature of the solution become simple and rapid.
*What do you understand by exothermic and endothermic reactions? Give one example in
each.
When heat is evolved in a chemical reaction, the reaction s called exothermic reaction.
For e.g. C(s) + O2(g)CO2 Hf =-94051 cal
When the heat is absorbed in a chemical reaction, the reaction is called endothermic
reaction
For e.g. C2H2OH(l) + CH3COOH(l)C2H5OOCH3(l) + H2O (l) H0298 =3720 cal
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1) Calculate the Enthalpy of one Kg Zinc Vapour at 950oC and atmospheric pressure, relative
to the solid at 30 oC
Data: Cp solid = 0.105 cal./gm.oC
Melting Point = 419 oC
Cp liquid = 0.109 cal./gm.oC
Boiling Point = 907 oC
Latent Heat of Vaporization = 26900 cal/gm.atom
Latent Heat of Fusion = 1660 cal/gm.atom
Cp vapor = 4.97 cal/gm atom oC
Atomic Weight of Zinc = 65.38
Q1=Q3=Q5=m Cp dt Q2=Q4=m λ
Q=Q1+Q2+Q3+Q4+Q5=533.987 Kcal.
Enthalpy of Zinc Vapor=533.987 Kcal.
2) Dry methane is burnt with dry air both being initially at 25oC. The flame temperature is
15700k. If complete combustion is assumed, how much excess air is to be used?
Data Standard heat of reaction = - 801556 J/gmmoles.
Cp data: Mean values:
CO2 51.79 J/gmmoles ok
H2O 40.19 "
N2 32.15 "
O2 32.40 "
Basis: 1 gmmole of CH4
CH4+2O2CO2+2H2O
Products: CO2=1gmmole
H2O=2gmmole
O2=x gmmole
N2=(7.52+3.76x) gmmole
Hr=∆Hr+ ∫∑nCppdT- ∫∑nCprdT Assuming, Hr=0 (AFT)
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