Process Calculation

Electromagnetic (Theory)
GATE & ESE MADE EASY
GATE & ESE PREPARATION
OCTOBER 2020

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Contents
Chapter 1 Process Calculation 4 - 95

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Process Calculation

Dimensions:

Physical variables required to define the nature & characteristics of the system or
object.

Primary (Fundamental):

Independent dimensions, memorable time, length etc.

Secondary (Derived):

Combination of fundamental dimensions: - volume, speed, density.

Units:

Physical variables required to characterize (define) the dimensions.

Time-Sec., Min, Hours, Days, Years.

Mass - Kg, g, lb.

Temp - 0K, 0R, 0C,0F.

Unique units are associated with unique dimensions.

System of units Mass Time Temperature Length

MKS (Meter kilogram Second) kg Sec °C m

EPS (Foot Pound Second) g Sec °F ft

CGS (Centimeter Gram Second) 1b sec °C cm

SI (International system) Kg Sec °C or °K m

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 Process Calculation

Derived Units:

Units which are combinations of the primary units.

Force:

According to Newton’s second law of motion, the force acting on a body is directly
proportional to the time of rate of change of momentum.

F = ma

F = kg m/s2 (Unit) = [MLT-2] (Dimension)

1N Force

Force required to displace the 1 kg of mass with acceleration of 1 m/sec2

1N = 1 kg. 1 m/s2

In C.G.S. System

1 kgm  103 g   100 cm 

= 1 kg.m / S2  * 
 1 kg   1 m 
2
S

1 N = 1 kg m/s2 =105 g.cm/s2

1 N=105 dyne

1 dyne = 1 g.cm/s2

1 kg.m/s2 = lb. ft/s2

1 1b = 0.4536 kg 1 ft = 12 inch

1 ft = 0.3048 m inch = 2.54 cm

Mass (Kg, lb.):

Mass is both a property of a physical body and a measure of its resistance to

acceleration when a net force is applied.

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 Process Calculation

Weight:

The weight of an object is the force acting on the object due to gravity.

Weight = Mass x g = kg x m/s2 =N=lbf

For an object of 80 kg.

WEarth = 80kg x 9.81 m/s2

WMoon = 80kg x 1/6 x9.81 m/s2

Pressure:

The normal component of the force per unit area exerted by the fluid on a real or
imaginary boundary.

P = FN/A = N/m2

1 Pa=1N/m2

P = ρhg

P = kg/m3x m x m/s2

Work:

The measure of the energy transfer that occurs when an object is moved over a
distance by an external force, at least part of which is applied in the direction of the
displacement.

W= F * d

1 J= 1 N*m = kg.m/s2 x m [ML2T-2]

1 J = 1 Nm = 1 kgm2/s2 = 103g x(102cm)2/s2 = 107 gcm2 /s2

1 erg = 1g cm2/s2

1 J = 107erg

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 Process Calculation

Power:

Power is the rate at which work is done (or energy is transferred).

Power = Work / time

1watt = 1 J/sec =1. Nm/sec 1hp = 745.7 watt

 Kgm 
 2 m 2
 s  = kgm = ML2T −3 
s s3  

Energy:

Energy is “the ability to do work”. It may exist in potential, kinetic, thermal, electrical,
chemical, nuclear, or various other forms

Potential Energy = mgh = kg.m/s2.m = kgm2.s2 = N/m = Joule.

Kinetic Energy = 1/2 mv2 = kg (m/s)2 = kg m2/s2 = N/m = Joule.

Solved Examples

Question:

The flow rate of water through a pipe is reported as 15 ft3/min. The density of water is
1g/cm3. Calculate the mass flow rate kg/s?

Solution:

ft 3
m° = 15 × 1g / cm3
min

=15
ft 3
×
g
×
1min
×
1kg
×
(
28316.8cm3 )
min cm3 60sec 1000g 1ft 3

= 7.079kg / sec.

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 Process Calculation

Question:

In an SI System, thermal conductivity has the unit of w/MK for a solid material. Thermal
conductivity is given by

k = x.Q/A∆T.

Here Q = Rate of heat transfer,

x = Thickness of material,

A = Cross sectional area,

∆T = Temp diff.

For an experiment, the values are found to be Q = 1000 kJ/hr, A = 1m2 , X = 1000mm, ∆T =
800K. Calculate

W
1. K in .
MK

2. K in kcal/ Mh℃ .

Solution:

100mm×1000kJ / h
1.) K=
1 m2 ×800K

106 mm × kj 10−3m 1hr 1000J

= . × × ×
800 n × m2 × k 1mm 3600sec 1kJ

= 0.347 W / MK.

J  1cal   3600 sec   1K 

2.) K = 0.347 ×  ×  
sMK  4.1818J   1 hr  ℃ 

= 0.29862 kcal/ Mh℃

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 Process Calculation

Question:

The potential energy of a body at a height of 15 m is 2 kJ. If the body is moving with a
velocity of 20 m/sec, what is the KE.

g = 9.8067 m/sec

Solution:

PE = mgh

m
2kJ = m × 9.8067 ×15m
s2

2 J × s2 × 103
= Mass
9.8067 ×m×15m

Js2
0.0135× 103 =m
m2

1
KE = mv 2
2

1 JS2 m2
= × 0.0135× 103 2 ×50 × 50
2 m sec2

= 16.99 J× 103

= 16.99kJ

Dimensional Consistency:

In any algebraic relation or equation, the units of L.H.S. = R.H.S.

→ Addition of two quantities is possible only when they have the same dimension & same unit.

Q.) E = mc2
2
m
N.m = J = kg.  
s
2
 kgm  m
 2  m = kg 2
 s  s

ML2T −2 =ML2T −2

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 Process Calculation

 
 
D  X  2aX
Q.) =
DX  9  
2
 1 +  9
 X   1 + X 
 

m ≠ m2

Dimensionally not consistent

Dimensional Analysis:

• To relate the dependent and independent variable for any system.

• Rayleigh Method

• Buckingham Pi Theorem

Rayleigh’s Method:

This method is based on the fundamental principle of dimensional homogeneity of

physical variables involved in a problem.

Procedure:

• The dependent variable is identified and expressed as a product of all the

independent variables to an unknown integer exponent.

• Equating the indices of n fundamental dimension of the variable involved, n

independent equations are obtained.

• These n equations are solved to obtain the dimensionless groups.

Q = f (ρ , µ , v)

Q ∝ fa µb v c

Q = Cfa µb v c

a b C
M°L3T −1 = C ML−3 T0  ML−3T −1  LT −1 
     

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 Process Calculation

M: a + b = 0

L: 3a + b + c = 3

T: b – c = -1
a = -2
b=2
c = -1

Q = CF−2µ2 v −1

Cµ 2
Q=
f2 v

Buckingham Pi Theorem: -

Let q1, q2, q3...qn be n dimensional variables that are physically relevant in a given
problem and that are inter-related by an (unknown) dimensionally homogeneous set of
equations. These can be expressed via a functional relationship of the form:

First convert them to dimensional variables (π)

No. of π terms = N-M

N → total no. of variables

M → total no. of repeating fundamental dimensions.

Π 1 = f ( Π 2 , Π 3 __ _ _ Πn−m )

Π 1 = f (dependent variables)

Q∝ = f (ρ, d, µ , v, g)

(s, d, v)

N = 6 N = 3 N = 6-3 = 3

Π 1 = F ( Π2 , Π3 )

Π 1 = ρa1Db1Vc1 Q

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Π 2 = ρa2 Db2Vc2 µ

Π 3 = ρa3 Db3Vc3 G

Π 1 = ρa1Db1Vc1 Q

( ) (L ) (LT ) (ML )
a2 B2 C2 1
M°L° T° = ML−3 −1 −1
T −1

M : a2 + 1 = 0

L : c2 – 1 = 0

T : - 3a2 + b2 + c2 – 1 = 0

u 1
Π2 = =
svd Re

Π 1 = f ( Π2 , Π3 )

Q  1 
= f ,Π3 
 Re
2
dv 

G – Atom

mass in g
=
atom wt.

K – atom

mass in kg
=
atom wt.

No. of g. molecules

mass in g
=
molecular weight

Solved Examples

Question:

1000 lb/min. of a gas (MW = 30.24) is being sent to an absorption column. What will be
the molar flow rate in kmol/hr?

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 Process Calculation

Solution:

lb 0.4536 60min
Mass flow rate=1000 × kg ×
min 1lb 1 hour

Mass flow rate = 27216 kg/hr

kg
mass 27216 hr
Molar flow rate= =
molar wt 30.24 kg
kmol
Molar flow rate = 900 kmol/hr

Question:

How many molecules are present in 691kg of K2CO3?

Solution:

Molecular Weight of K2CO3= 138

691
Moles= =5.0072 moles of K2CO3
38

= 5.0072×6.023× 1023

= 3.015× 1024 molecules

= 30.1536 × 1023

Question:

How much N2 and H2 are required to produce 100kgs of NH3?

Solution:

(Molar Calculation)

N2 + 3H2 → 2NH3

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Basis 100kg of NH3

2 Kmoles of NH3 Produced by = 1k moles of N2

100
No. of moles of NH3 = kg=5.888 kmol.
17

1
1 Kmol of NH3 = kmol N2
2

1
5.88 Kmol of NH3 = ×5.88 kmol N2
2

= 2.94 Kmol N2

 kg 
N2 in Kg = 2.94 Kmol ×  28  = 82.35 Kg of N2
 kmol 

(Mass Calculation)

Basis: 100kg of NH3

N2 + 3H2 → 2NH3

34 Kg of NH3 Producing by = 28 kg of N2

28
100g of NH3 = = ×100 of N2
34

28kg of N2
×100kg of NH3 =82.35 Kg Of N2
34 kg of NH3

Question:

Calculate the amount of NaOH & HCl required to produce 108kgs of H2O.

NaOH + HCl → NaCl + H2O

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 Process Calculation

Solution:

Basis: 108kg of H2O

108
No. of moles of H2O = =6 kmol
18

1 Kmol of NaOH = 1 Kmol of H2O

6 Kmol of NaOH = 6 Kmol Of H2O

= 6 × 40

= 240 Kg of NaOH

1 Kmol Of H2O is producing → 1 Kmol of NaCl

6 Kmol of H2O = 6 Kmol Of NaCl

58.5kg
Mass of NaCl Produced = 6 kmol ×
kmol

= 351 kg.

OR

According to mass conservation: -

Mass of reactant = mass of product

MNaOH + MHCl = MNaCl + MH2O

MNaCl = MNaOH + MHCl - MH2O

= 240 + 219 – 108= 351 Kg

Concentration:
The concentration of a solution is a measure of the amount of solute that has been
dissolved in a given amount of solvent or solution.

mass of solute in ( g )
C=
volume of solution (l )

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 Process Calculation

Molarity(M):

It is defined as the number of moles of the solute per liter (10–3 m3) of solution.

No. Of gram moles of Solute

Molarity (M) =
Vol of soln (in lquid)

Molality(m):

It is the number of moles of the solute present per 1 kg of solvent

No. Of gram moles of Solute

Molality (m) =
kg of solvent

Normality (N):

It is the ratio of the number of gram equivalents of the solute per liter of solution

No. Of gram equivalents

Normality (N) =
Vol of soln (in liquid)

Equivalent Weight:

The equivalent weight of an element is the number of parts by weight of the element
which can be combined with or displace 1.008 parts by weight of hydrogen or the
equivalent weight of any other element.

Molecular wt.
Equivalent Weight =
valency

Gram equivalent weight:

Gram equivalent weight is equal to mass in grams numerically equal to Equivalent

Weight.

mass in ( g )
No. Of g. equivalent =
equivalent weight

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 Process Calculation

Valency:

Valency is the measure of the combining capacity of atoms or molecules. Therefore, it

is the capacity of an atom of a single element to react and combine with a number of
atoms of another element.

Valency = No. of hydrogen ions accepted or OH− ions donated

or

No. of election (e-) transfer.

CaCO3 + H₂O → Ca (OH)2 + H₂CO3

CaCO₃ Equivalent weight = Molecular weight/Valance

= 100/2 = 50 Equivalent weight

Solved Examples

Question:

98g of H₂SO4 has to be dissolved in water to prepare 1L of solution. Find out the
normality, and molarity of solution.

Solution:

98
M = = 1M
98x1

N = M × 2 = 2N

Question:

If 500 ml of H₂SO4 solution has the density 1.0759/ cm3 then calculate the H₂SO4
required for 1 N of Soln , 1M of Soln & 1m of Soln .

Solution:

x ×1000
1M=
500 ×98

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 Process Calculation

x = 49g.

x ×1000
1 N= ×2
500 ×98

x = 24.5g.

g mol of H2SO4
1m=
kg of solvent

Solution = Solute + Solvent

Kg solvent = Kg Solution − Kg solute.

9 1kg 103cm3
Kg of Soln =0.5l× 1.075 × ×
cm3 103g 1l

Kg of soln = 0.5375 kg

let x kg of solute required.

Kg of solvent = 0.5375 – x

g mol of solute
m=
kg of solvent

 g 
x kg  1000 
mass in g  kg  1000x
g mole of solvent = = = gmole
m.wt 98 98

1000x
1=
98 ( 0.5375 − x )

x = 47.97g

Question:

How many kg of S will be required to form 100 kg of Na2SO4?

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 Process Calculation

Solution:

Basis: 100 kg of Na2SO4

100
Moles of Na 2SO4 = = 0.704 kmoles
142

kg
Kg of S required = 0.704kmol ×32 = 22.53kg
kmol

Question:

How many g-atoms of S will be required to form 100 kg of Na2SO4?

Solution:

 103g 
22.53 kg× 
 1kg 
=   = 704.22 atom of S
32

1 Kmol of Na2SO4 = 1 Kmol atom of S

= 2Kmol atom of Na = 4 Kmol atom of O

= 0.704 Kmol= 0.704 Kmol atom of S

=704g atom of S

Mass Fraction (wA):

The mass fraction of a component in a mixture is the ratio of the mass of the component
to the total mass of the mixture.

wA, mass fraction of A

mA mass of A
= =
N
total mass
∑m
i= 1
i

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Volume Fraction:

The volume fraction of a component in a solution is the ratio of its pure-component

volume to the total volume of solution, both at the same temperature and pressure.

volume fraction of A

volume of A V V
= = Ni = i
total volume Vtotal
∑
Vi
i= 1

Mole Fraction: -

The mole fraction is the ratio of the moles of the constituent to the total moles in the
mixture.

Mole fraction of A

moles of i n
xA = = Ni
total mass
∑ ni
i= 1

Parts per million (ppm): -

It is used to represent extremely small amounts of solutes present in solutions. It is the

ratio of the number of parts by weight of the solute to 106 parts by weight of solution.

1 g of solute 1g. of solute 1 mg of solute

1ppm = = =
6
10 g of solution 3
10 l of solution 1l ofsolution

Solved Examples

Question:

Aqueous Solution of NaCl is prepared by dissolving 25kg of NaCl in 100 kg of H₂O. Find
out weight. %; mole %.

wi
Weight fraction =
∑ wi

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 Process Calculation

Weight percentage = weight fraction × 100

Volume percentage = volume fraction × 100 ,

Mole percentage = mole fraction × 100

Solution:

25 1
Weight fraction= = =0.2
125 5

wt % = 20%

100 4
wt. fraction H2O= = =0.8
125 5

wt % = 80%

Mol %

 25 
 
 58.5 
NaCl = = 7.14%.
 25   100 
 + 
 58.5   18 

H2O = 0.928 = 92.8 %

→
Wt. fractn Mole fractn
←

wt. fractn of NaCl

0.2
=
0.2 + 0.8

 0.2 
 
=  58.5  = 0.0714 = 7.14 %
 0.2   0.8 
 + 
 58.5   58.5 

Mole = Mass/Molecular Weight

Mole % × M.w. =Mass%

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 Process Calculation

Question:

A solution contains 50% NaOH & 50% H2O (by mol). Find out their wt%.

Solution:

W
WNaOH
NaOH
==0.5
0.5××40
40====20
20gg

WH = 0.5 X 18 = 9 g
2O

20
WtNaOH = = 0.6896 = 68.96 %
29

9
WtH = = 0.3103 = 31.03%
2O 29

OR

Basis: -100 mol of soln

NaOH = 50mol , H2O = 50 mol

Mass of NaOH = 50 X 40 = 2000 g

Mass of H2O = 50 × 18 = 900 g

2000
WtNaOH = ×100 = 68.96%
2000 + 1900

9000
WtH = × 100 = 31.03%
2O 2000 + 900

Calculations for Ideal Gas:

Ideal gas:

On a molecular level, an ideal gas may be treated as the one for which (a) the size of
the molecules is very small compared to the distance between them so the volume of
the molecules is negligible in comparison with the total volume of the gas and (b) the
intermolecular forces are negligibly small.

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 Process Calculation

Boyle’s Law

For a fixed quantity of a gas the volume is inversely proportional to pressure at constant
temperature.

PV = Constant (at fixed T and n)

Charles’ Law

Charles’ Law states that the volume of a fixed quantity of gas at constant pressure varies
directly with temperature.

(At fixed P and n)

Y
= conc.
T

PV = nRT

Ideal gas Equation / Equation of state: -

PV ∝ constant

PV
=R
T

R at STP (Standard Temperature & Pressure): -

T = 0°C = 273.15K , P = 1atom.

n=1 kmol , V=22.4143 m3

PV
R=
nT

N
101326 × 22.4143 m3
m 2 J
R= =8.314
1 kmol × 273.15 K molk

Solved Examples

Question:

m3 cal
Find the value of gas constant R in mm Hg and .
mol k mol k

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 Process Calculation

Solution:

PV
R=
nt

760mmHg
1 atm ×22.4143 m3 × 3
= 1 atm =0.06236 mmHgm
103 mol mol k
1 kmol× ×273.15k
1 kmol

1cal
8.314 J ×
= 4.1858J =1.9862 cal
mol k mol k

Question:

Calculate the molar volume in l/mol of air at 350 K & 1 Bar.

Solution:

PV = nRT

V RT
=
n P

1.01325 bar ×22.4143 l

R= =0.08314
1 mol ×273.15k

bor.l
0.08314 × 350K
V mol.k l
= =29.629
n 1 bar mol

Ideal Gas Mixtures:

Consider a mixture of different gases A, B, C, etc. at temperature T and pressure P and

let the total volume of the mixture be V. Let nA, nB, nC, etc. be the number of moles of
the different components. If all the component gases are ideal, then the behavior of the
individual species is not influenced in the presence of other gases in the mixture. This is
because of the absence of intermolecular forces in an ideal gas.

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 Process Calculation

The pressure exerted by nA moles of A in the mixture will be the same as the pressure
exerted when nA moles of A alone occupy a volume V at temperature T. This is true
for the other constituents B, C, etc. as well. The pressure exerted by a constituent in
a mixture of gases when it alone occupies the total volume at a given temperature is
called the partial pressure of that constituent in the mixture.

Dalton’s Law

Dalton’s Law states that the total pressure of a mixture of gases is equal to the sum of
the partial pressures of the individual components. Dalton’s law is strictly true only for
ideal gases.

Ptotal = ∑ Pi

PV = nRT

For component ‘i’,

PV
i
= nRT
i
− − − − − − ( 1)

For total mixture,

Ptotal V = ntotal .RT − − − − − ( 2 )

equation ( 1) ÷ ( 2 )

Pi
Ptotal
=
ni
ntotal
(
= yi mol fracn )
Pi = yi Ptotal

pressure% = mol%

Amagat’s Law

Amagat’s law states that the total volume of a mixture of gases at a given temperature
and pressure is equal to the sum of the pure component volumes of the constituents at
the same temperature and pressure. This law is strictly true only for ideal gases.

Vtotal = ∑ vi (at Const. T&P)

PV = nRT

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 Process Calculation

For component i,

Pvi = ni RT − − − − ( 3 )

For total mixture,

PVtotal = ntotal RT − − − − ( 4 )

EQn ( 3 ) ÷ ( 4 )

vi ni
= = yi
Vtotal ntotal

Vol% = mol%

For ideal gas mixture

vol = mole% = pr%

Avg. Molecular: - (Mixture)

mtotal ∑ mi ∑ ni × Mi
Mavg = = =
ntotal ntotal ntotal

Mavg = ∑(xi ×mi )

Solved Examples

Question:

An analysis of the vent gases in a plant shows that it contains 70% HCL, 20% Cl2& rest
CCl4 by vol. Determine the % component by wt., Avg. mole wt. of gas & at std state
(kg/m3)

Solution:

Basis: 100 Kmol of gas

% Component by wt. →

26
 Process Calculation

Component ni Mi = ni X mi wt%

HCI 40 Kmol 70 X 365 = 2555 kg 2555 X 100 = 46.328%

5515

C12 20 Kmol 20 X 71 = 1420 kg 1420 X 100 = 25.74%

5515

CC14 10 Kmol 154 X 10 = 1540 kg 1540 X 100 = 27.923%

5515

= 5515 KG

mtotal 5515 kg
i) Mavg = = = 55.15
ntotal 100 kmol

Mavg = ∑ ximi = (0.70 × 36.5 = 0.2 × 71 + 154 × 0.1 )

= 55.15

m
ii) f=
v

at STP V = 22.4140m3 for 1 kmol.

For 100 kmol gas, Vtotal = 100 × 22.4143 = 2241.43m3

5515 kg kg
ρ= = 2.4604 3
2241.43 m3
m

ρ at 350 k & 2 bar

nRT
V=
P

bar m3
100 km × 0.8314 × 350 k
Vtotal = kmol k
2 bar

Vtotal = 1621.23m3

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 Process Calculation

5515 kg
ρ= = 3.4 3
1621.23 m

PV = nRT

m
PV = RT
Mw

P.Mw m
= =ρ
RT V

General Mass Balance Eqn

Accumulation = input - output

Accumulation = (input + generation) − ( output + disappearance )

Steady State Process → Condition of System does not change with time.

Unsteady State Process → Condition within the system changes with time

M2 (Pure A)

M1 (40% A, 60% B) M3 (70% A, 30% B)

Overall Mass Balance

M1 + M2 = M3

Component Mass Balance

total mass of component in = total mass of component out

For B → M1 ×0.6 = M3 × 0.3

For A → M1 × 0.4 + M2 = M3 ×0.7

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 Process Calculation

Material Balance for unit Operation (Without Chemical reaction):

Tie Component:

The amount of the tie component does not change during the process.

Solved Examples

Question:

A piece of coal containing 15% Ash & 85% C is burned in a combustion Chamber and the
residue is found to contain 80% Ash & 20% Carbon. Find out the art of residue formed for
100 kg of coal.

Solution:

Basis: 100 kg of coal Gas

Coal Combustion Residue

Chamber

C + O2 → CO2

C → 100 × 0.85 = 85kg

Ash → 100 × 0.15 = 15kg

Tie component → ash

Component Balance for tie component /ash

Total ash input = total ash output

F × 0.15 = R × O.80

100 × 0.15 = R × 0.80

R = 18.75kg.

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 Process Calculation

G → Gas Leaving

F = G+R

100 = G − 18.75

G = 81.25kg

Drying:

In drying, a wet solid or slurry comes into contact with dry gas so that water is vaporized
from the solid and is carried away by the gas. When the vapor pressure exerted by the
moisture in the solid equals the partial pressure of water in the gas exposed to the solid,
the solid is said to have attained its equilibrium moisture content, and drying stops.

Drying operations are done to reduce the cost of transportation of the product, to give
some useful properties to the product like the free-flowing nature of salt, and to prepare
the product in a form that is suitable for handling and use.

Vapor V (kg/hr)

Drying
West solid W (kg/hr) Dried solid (kg/hr)
(dry solid + moisture) (dry solid + moisture)

Overall Mass Balance

W = V +D

Dry Solid Mass Balance

W * x w = 0 + D * xd

Moisture Mass Balance

W * xm = V * 1 + d * (1 − xd )

30
 Process Calculation

Solved Examples

Question:

Some wood containing 40% moisture is dried till it contains only 5% moisture. What
mass of water evaporated per kg of dry wood?

Water evaporated V

Drying
Wood F (moisture Wood P (5% moisture
40%, 60% dry wood) 95% dry wood)

Solution:

Basis: - 1kg of wood

Dry wood = 1 * 0.6 = 0.6kg

Moisture = 1 × 0.4 = 0.4kg

Overall M.B.

F =P+V

P+V = 1

Component mass balance of dry wood,

F × 0.6 = P × 0.95

0.6 = 0.95P

0.6
P= = 0.6315kg
0.95

31
 Process Calculation

Water vaporized

V = 1−P

V = 1 − 0.6315

V = 0.3685Kg

kg of water evp 0.3685kg

=
kg of dry wood 0.6kg

= 0.614

Basis: -

1 kg of dry wood

Mass of dry wood in feed = F × 0.6 = 1 kg

1
F= = 1.666
0.6

Water in feed of = 1 kg of dry.

= 1.667 − 1 = 0.667kg

Dry wood in product = P × 0.95 = 1 Kg

1
P= = 1.0526Kg
0.95

water in product = 1.0526 − 1 = 0.0526kg

water evaporated = 0.667 −0.0526

= 0.6144kg

Question:

A wet solid containing 60% moisture is dried till it contains only 15% of moisture by wt. If
30 kg of water has evaporated, find the mass of the wet solid.

Solution:

Basis: 30kg of water evaporated.

32
 Process Calculation

Water evaporated V=30 kg

Wood F (moisture Wood P (15% moisture

40%, 60% dry wood) 85% dry wood)

Overall Mass Balance,

F = V +P

F − P = 30kg

Component MB,

H₂O→

F × 0.6 = V + P ×0.15

0.6F = 30 + 0.15P

0.6 ( 30 + P ) = 30 +0.15P

18 +0.6P = 30 +0.15P

P = 26.66

F = P + V = 56.666Kg

Evaporation:

Evaporation is used in industries for concentrating aqueous solutions by vaporizing the

solvent water and removing it as vapor.

Solvent evaporated (V)

Feed solution (F) Evaporation Concentrated solution (P)

33
 Process Calculation

Overall MB

F =P+V

Solute MB

F.x = Pxp

Solvent MB

Fx = V + Pxp

Evaporator Capacity → Kg water vapor produced per hour

Evaporator Economy → Kg of water vapor produced / Kg of Steam feed

Solved Examples

Question:

A single effect evaporator is fed with 10 tons/hr feed solution containing 15% NaOH by
wt. and is concentrated to 40%. NaOH solution. Calculate the amount of thick liquid and
water vapor produced.

Solution:

Solvent evaporated (V)

Feed Evaporation Concentrated

(F = 10 tons/hr, solution P
15% NaOH) (40% NaOH).

Overall MB

F = V +P

10 = V + P

34
 Process Calculation

Solute MB

0.15×10 = 0.40P.

1.5 = 0.40 ( 10 − V )

1.5 = 4 − 0.4V

ton
V = 6.25 .
hr

P = 3.75hr / m

Mixing & Blending:

The purpose of Mixing & Blending operations is to produce products of uniform

properties.

F2 C%

F1 Mixing F4
A% A%
B% B%
C%

F3
A%
C%

Overall Mass Balance: -

F1 + F2 + F3 = F4

Component Mass Balance: -

A → F1xA1 + F3x3A = F4 x4A

B → F1 × xB1 = F4 xB4

35
 Process Calculation

Solved Examples

Question:

1000 kg of mixed acid of composition 40% H2SO4, 45% HNO3 and the rest being water is
to be produced by mixing waste acid of 30% H2SO4, 36% HNO3 and 34% H2O solution with
95% H2SO4 solution and 80% HNO3 solution. How many kgs of these acids will be required
to prepare the desired (by weight %)?

Solution:

F2 80% HNO3
20% H2O

F1 Mixing F4
=1000 kg 10% H2SO4
30% H2SO4 45% HNO3
36% HNO3 15% H2O
34% H2O
F3
95% H2SO4
5% H2O

Overall Mass Balance: -

F1 + F2 + F3 = F4

1000 = F4 − (F2 + F3 )

For H2SO4

1000 × 0.3 + 0.95F3 = F4 ×0.4

For HNO3

1000 × 0.36 +0.80F2 = F4 × 0.45

For H2O

1000 × 0.34 = 0.15F4 − 0.20F2 − 0.05F3

300 + 0.95F3 = ( 1000 + F2 + F3 ) 0.4

36
 Process Calculation

300 + 0.95F3 = 400 + 0.4F2 + 0.4F3

0.55F3 − 0.4F2 = 100

360 + 0.8F2 = 450 + 0.45F2 + 0.45F3

0.35F2 − 0.45F3 = 90

340 = 150 + 0.15F2 + 0.15F3 − 0.2F2 − 0.05F3

190 = 0.1 F3 - 0.05 F2

F2 = 264.7,F3 = 374.33

Question:

The waste acid from the nitration process contains 30% of H2SO4, 25% HNO3 & the rest
being water is mixed with 98% H2SO4 and 72% HNO3 solution. To concentrate the acid
up to 39% H2SO4, 42% HNO3 & the rest to be water, calculate the quantities of the three
acids required to produce 1000 kg of mixed acid.

Solution:

F2 72% HNO3
28% H2O

F1 Mixing F4 = 1000
30% H2SO4 39% H2SO4
35% HNO3 42% HNO3
35% H2O 19% H2O

F3
98% H2SO4
02% H2O

F1 + F2 + F3 = 1000

For H2SO4.

0.30F1 +0.98F3 = 0.39×1000

For HNO3

0.35F1 +0.72F2 = 0.42 × 1000

37
 Process Calculation

For H2O

0.35F1 + 0.28F2 +0.02F3 = 0.19×1000

feed F1 = 90.04kg

HNO3 F2 = 539.56kg

H2S04 F3 = 370.39kg

Question:

A feed to a continuous distillation column contains 28% C6H6 and 72% Toluene. The mass
fraction of benzene in the distillate is found to be 52 & in the bottom it is 5%. Calculate
the amount of distillate & bottom product for a feed rate of 1000 kg/hr.

Solution:

D
0.52 C6H6

F = 1000
Dist
Colimn

XF
0.28% C6H6
B
0.72 Toluene
0.05 C6H6

F =D+B

1000 = D + B

0.28 × 1000 = 0.52D + 0.05B

280 = 0.52 ( 1000 − B) + 0.05B

280 = 320 − 0.52B + 0.05B

Kg
D = 510.64
hr

Kg
B = 489.36
hr

38
 Process Calculation

% Recovery: -

Amt of Benzene in distillate

= x 100
Amt of Benzene in feed

0.52 * 510.64
= x 100
280

= 94.88 %

% Loss: -

Amt of Benzene in Residue

= x 100
Amt of Benzene in feed

0.05 * 489.36
= x 100
280

= 5.12%

Question:

10,000kg/h of solution containing 20% MeOH, is continuously fed to a distillation column.

The distillate contains 98% methanol and the waste product contains 1% MeOH only.
Calculate the mass flow rate of the distillate and the bottom product as well as % loss
of MeOH.

Solution:

D
0.98 MeOH

F = 10000
Dist
Colimn

XF
0.20 MeOH
D
0.01 MeOH

Overall mass balance: -

10000 = D+B

39
 Process Calculation

For MeOH: -

FxF = xDD + xBB

2000 = 9800 – 0.98 B + 0.01B

B = 8041.24 Kg/hr.

D = 1958.76 Kg/hr.

Amt of MeOH in bottom product

% loss = x 100
Amt of MeOH in feed

8041.24 × 0.01
= × 100
10000 × 0.20

= 4.02%

Absorption:

In absorption, the soluble constituents of a gas mixture are separated by absorbing in a

suitable liquid solvent. The reverse process—the removal of certain constituents of a liquid
mixture by bringing it into contact with a gas phase—is known as desorption or stripping.

Example:

Ammonia is absorbed from a mixture of ammonia and air by bringing the gas into contact
with water using a device called the absorption column.

Gas Out L2 kg/hr

G2 2
y2 (kg/hr) Liq In
x2

Gas In Liq Out x1

G1 (kg/hr) L1 (kg/hr)
y1

40
 Process Calculation

Overall MB

G1 + L2 = G2 + L 1

Component MB

G 1y 1 + L2x2 = G 2 y2 +L 1x 1

Solved Examples

Question:

Acetone is recovered from an acetone air mixture containing 25% Acetone by volume.
It is scrubbed with water. Assume that the air is insoluble in water. Determine the % of
acetone absorbed if the gas leaving the column contains 5% acetone.

Solution:

G2 Water In
5% acrtone L2

A.L

25% acetone Water Out

G1 L1

% Acetone absorbed:-

Amt of Acetone transferred to liq

= x 100
Amt of Acetone feed

Acetone out from gas stream = Acetone into the liquid stream

Basis: 100 kmol of gas mixture fed. ( G1 )

41
 Process Calculation

Acetone in feed gas: -

=G 1
× 0.25

= 100 × 0.25

kmol
= 25
hr

kmol
Air in feed gas = 100-25 = 75
hr

Acetone present in outlet gas Stream =G 2

× 0.05

Air in gas leaving outlet =G 2

× 0.95

75 = G 2
×0.95

Kmol
G2 = 78.947
hr

Acetone in outlet stream = G2 × 0.05

= 78.947 * 0.05

kmol
= 3.947 .
hr

%. Acetone absorbed

25 − 3.947
= × 100
25

kmol
= 84.21 .
hr

Inert Go
+ Solute G2 Inert Liq Lo
Gas Out + Solute L2
G2 2
y2 (kg/hr) Liq In
x2

Gas In Liq Out x1

Solute G1 (kg/hr) L1 (kg/hr)
y1 Inert Liq Lo
Inert Gas Go + Solute L1

42
 Process Calculation

mass of solute
Y=
mass of Inert Gas

L2 = L0 + L'2

L 1 = LO + L'1

G1 = GO + G'1

G2 = GO + G'2

Overall Mass Balance: -

G1 + L2 = G2 + L 1

Component Mass Balance: -

G o
.Y1 + LO . X2 =G Y + Lo X 1
O 2

Question:

An NH3-air mixture containing 0.2 kg NH3 per kg of air enters an absorption column where
the NH3 absorbs into water. The gas leaving the system is found to contain 0.004 kg NH3 /
kg of air. Find % recovery of air.

Solution:

G2 L2
0.004 (Water In)
kg NH3
kg of air

A.C

G1
0.2 kg NH3 L1
kg of air (Water Out)

43
 Process Calculation

Basis: - 1kg of air feed

NH3 in gas inlet: -

= 1kg air x 0.2 kg NH3 /Kg of air

= 0.2 kg NH3

NH3 in gas outlet: -

= 1 kg of air x 0.004 kg NH3 /kg of air.

= 0.004 kg NH3

%.Recovery : −

NH3 inlet − NH3 outlet

= × 100
NH3 feed

0.2Kg − 0.004Kg
= × 100 = 98%
0.2Kg

Extraction:

The liquid–liquid extraction operation involves bringing the feed liquid in intimate
contact with an immiscible or partially miscible solvent, allowing the solute to get
distributed between the phases, and finally allowing the phases to separate from each
other.

The resulting solvent-rich phase is called the extract and the residual solution from
which the solute is extracted is known as the raffinate. The mutually insoluble extract
and raffinate phases are then separated from one another by settling and gravity
separation.

F feed soln (xF) Extraction phase yE

Solute C E
Solute A
Extraction Column

Solute C
R
Solute B
Raffinate phase xR
S yS

44
 Process Calculation

Overall Mass Balance: -

F+ S =E+ R

Component Mass Balance: -

Solute C

F.xF + S.yS = E.yE + R.XR

Solvent A

F.xFA + S.ySA = E.yEA + R.XRA

Solvent B

F.xFB + S.ySB = E.yEB + R.XRB

% Recovery: -

E × yE
= × 100
F × xF

Filtration:

In filtration, the suspended solid particles in a fluid, either a gas or a liquid, are removed
by passing the fluid through a filtering medium such as a canvas cloth that retains the
particles as a separate phase or cake and allows the passage of the clear filtrate.

Solid pahse/filtercake
(solid + small amt of liquid
W xWs xWL)

F feed soln

Filtration

S+L
XFS
XFL

Filtercake
P (liquid + small amt of s)
xPs
xPL

45
 Process Calculation

Overall Mass Balance: -

F=W+P

Component Mass Balance: -

Solid

xFS .F = WxWS + P.xPS

Liquid

xFL .F = WxWL + P.xPL

Crystallization:

Crystallization is the process in which solid particles are formed from a liquid solution
by evaporating and/or cooling of a saturated solution.

Crystallization occurs when the solution is concentrated and usually cooled until the
solute concentration becomes greater than its solubility at that temperature. Equilibrium
is said to be attained when the solution is saturated.

Water Vapourized
V

Feed F
Crystallization C
S+L Crystals
xC

M (Mother Liquor)

Pure Crystal → Na2CO3

Hydrate Crystal → Na2CO3. 5H2O

kg of solute
xM =
kg of solute + kg of solvent

Overall Mass Balance: -

F=C+M+V

46
 Process Calculation

Component Mass Balance: -

Solute

F.xF = C.xC + MxM

Water

F.xFW = V + C.xCW + MxMW

2kg of NaCl
Solubility of NaCl =
100 kg of H2O

2
Mass fraction of NaCl =
100+2

Solved Examples

Question:

A crystallizer is charged with 100kg of a solution containing 25% Ba (NO3)2 in water. On

cooling, 10% of the original water is evaporated. Calculate the yield of crystal produced,
when the solution is cooled to 253 K.

The solubility of Ba(NO3)2 at 253 K is given 7 kg Ba(NO3)2 / 100kg of H2O.

Solution:

Water Vapourized
V

F = 100 kg
Crystallization C
S = 0.25 Crystals
L = 0.75 xC

M (Mother Liquor)
xm = 7 = 0.065
100+7

Basis: 100 kg of solution.

F= C+M+V
100= C+M+V

47
 Process Calculation

Water in feed = F × 0.75 = 75

V = 10% of 75kg = 7.5kg .

C + M + 7.5 = 100

C + M = 92.5 ( 1)
Solute Balance

F × 0.25 = C × 1 + M × 0.065

25 = C + ( 92.5 − C ) 0.065

18.9875 = 0.935C

C = 20.307kg

M = 72.193kg

Question:

An aqueous solution containing 15% Na2CO3 & 85% water is cooled to a temperature
of 278 K and hydrated crystals of Na2CO3 .10H2O are recovered. The solubility of Na2CO3
at 278 K is 9% by wt/mass feed for 100 kg of feed solution. Find the amount of crystal
produced & water evaporated, if 80% of Na2CO3 is recovered as hydrated crystals.

Solution:

Water Vapourized
V

F = 100 kg
Crystallization C
Na2CO3.10H2O
S = 15% Na2CO3
L = 85% H2O

M (Mother Liquor)
xm = 9 = 0.0825
109

Overall mass balance: -

F= C+M+V

48
 Process Calculation

Solute: -

106
F × 0.15 = M × 0.09 + C ×
286

Na2CO3 Initially: -

= F × 0.15 = 15kg

80 % Na2CO3 = 12 kg.

106
C× = 12
286

C = 32.37 Kg.

M= 33.36 kg

V= 34.26 Kg

Question:

A drier is fed with a wet solid to reduce the moisture content from 50% to 15%. The
product leaving the drier is admitted into an oven which further brings down the
moisture to 2%. If the drier can handle 1000 kg wet solid per day,

Calculate

i) The product leaving the drier & the oven, respectively.

ii) % of original water removed in the drier & the oven, respectively.

Solution:

VD VO

F = 1000 kg
Dryer Oven

0.50 H2O MD MO
0.50 dry solid 0.15 H2O 0.02 H2O
0.85 dry solid 0.99 dry solid

49
 Process Calculation

Dryer: -

F = VD + MD

1000 = VD + MD

Moisture: -

500 = VD + 0.15MD

500 = 1000 − MD + 0.15MD

Kg
MD = 588.235
day

VD = 411.76

MD = VO + MO

588.235 = VO + MO

588.235 × 0.15 = VO + MO × 0.02

MO = 510.203

Kg
VO = 78.03
day

% Water recover from dryer: -

FxF − MDxD
= × 100
FxF

= 82.35

% Water recovered from oven: -

MDxD − MO xO
= × 100
FxF

= 15.606%

50
 Process Calculation

Bypass:

Bypass is employed mainly for affecting relatively small changes in a fluid stream. This
is effectively achieved by introducing large changes in a small portion of the original
stream and diverting the other portion without passing it through the unit accomplishing
this change. The portion so diverted is known as the bypass stream. The stream that is
passed through the process unit is later mixed with the bypassed stream to get the final
desired change in the combined stream.

B By passing
4
D
Feed 3
Process
A C Product

At 1

Overall Mass Balance: -

A=P+V

Over 2 (Splitting point)

Overall Mass Balance: -

A=B+C

At splitting point, the composition is the same.

Over 3 (Mixing point)

Overall Mass Balance: -

B+D=P

Component Mass Balance

BxB + DxD = PxP

On processing unit 4

51
 Process Calculation

Overall Mass Balance: -

C Process D

C =D+V

CxC = DxD + VxV

Solved Examples

Question:

Fresh juice containing 15% solid & 85% water is to be concentrated up to 40% solid in a
single evaporation system. It is found to have a bad taste. So to make it taste better, a
part of the fresh juice is bypassed from the evaporator and added to the product stream.

The operation is shown as

B By passing

D
C E
Evaporation
pdt
pdt A 55% Product 40% S
15% S solid
60% W
85% W
Evaporation

Calculate the fraction of juice that bypasses the evaporator & the concentrated juice
produced per 100 kg of fresh juice.

52
 Process Calculation

Solution:

Bypass Ratio =
( Amt of Bypass stream) = B
Amt of fresh feed A

Basis: 100kg of fresh juice

Overall Mass Balance: -

A=V+E

Solid: -

AxA = ExE

15 = E*0.40

E=37.5

At mixing

D+B=E

D*0.55 + B*0.15 = E*0.40

D*0.55 +(37.5-D) *0.15 =15

0.55D + 5.625 – 0.15D = 15

0.4D = 9.375

D = 23.437

B = 14.0625

14.0625
Bypass ratio = = 0.140625
100

Question:

In a textile industry, it is desired to produce 24% NaOH solution by wt. (w/w). Because
of the heat of the solution of NaOH in water, the above solution is prepared by a 2-step
process. First, NaOH is dissolved in the correct quantity of water in a dissolution tank to
prepare 50% solution by wt (w/w). After dissolution, cooling is complete. This solution
is then taken to a dilution tank where some more water is added for producing 24%
solution. Assuming no evaporation loss of water in any tank, calculate the wt. ratio of
water fed to the dissolution tank to bypass water from the dilution tank.

53
 Process Calculation

Solution:

Water Water
W1 W2
NaOH
Dissolution
Dilution Tank
Tank
A
50% NaOH 24% NaOH
50% Water 76% Water

Basis: - 100kg of 24% NaOH solution.

Over dilution tank

P1 + W2 = P2

NaOH balance

P1 × 0.5 = P2 ×0.24

P1 = 48kg

W2 = 52kg

Mass Balance over dissolution tank

F + W1 = P1

Component Mass Balance

NaOH

F × 1 = P1 × 0.5

F = 24kg

W1 = 24kg.

W1 24
= = 0.4615
W2 52

54
 Process Calculation

Recycle Operation:

A system with a recycle is one in which a stream leaving a processing unit is partly
returned to the same unit for reprocessing or reusing.

The recycling of the fluid stream in a chemical processing unit is used to increase yields,
to increase purity, to enrich a product, to conserve heat, or to improve operations.

Gross
Mixed Feed pdt

Feed M G N
Net
Process pdt
F

2
R
1
Recycle

• To improve conversion.

• To improve the purity of product.

• To conserve energy.

1. Overall Mass Balance:

F=N

Component Mass Balance:

FxF = NxN

2. Over processing Unit

M=G

Component Mass Balance:

MxM = G xG

3. Mixing

R+F= M

55
 Process Calculation

Component Mass Balance:

RxR + FxF = MxM

4. Splitting

G =N+R

Recycling Ratio (R):

The ratio of the quantity of a substance in the recycled stream to the quantity of the
same substance in the fresh feed is known as the recycle ratio.

Amt of stream recycled

=
Amt of stream in fresh feed

Material Balance with Chemical Reaction:

Rate of Mass Accumulated = Rate of Mass In - Rate of Mass Out

At Steady State:

Rate of Mass In = Rate of Mass Out

In terms of mole:

Rate of Moles Accumulated = Rate of Moles In – Rate of Moles Out + Rate of moles
generated – Rate of Moles consumed

Stoichiometric coefficient:

aA +bB → cC + dD

rA A + rBB + rCC + rDD = 0

( −a ) A + ( −b) B + cC + dD = 0
aA + bB = cC + dD

Stoichiometric ratio for A & C : -

a
=
c

56
 Process Calculation

Stoichiometric proportion:

When the reactants are present in their Stoichiometric ratio

N2 + 3H2 → 2NH3

N2 1
=
H2 3

N2
If is given in 1/3 ratio then they are in Stoichiometric proportion.
H2

Limiting Reactant:

When the reactants are not in stoichiometric quantities, the reactants that are present in
less quantities than the stoichiometric quantities are termed as limiting reactants.

The component which is exhausted first in the reaction.

N2 + 3H2 → 2NH3

If 5 mol N2, 12 mol H2 is given.

1 mol N2 = 3 mol H2

3 mol H2
5 mol N2 = × 5 mol H2
1 mol N2

= 15 mol H2

Excess Reactant:

The component which remains in excess & is also available in the product mixture after
the reaction is complete.

Excess reactants may be necessary in certain cases to prevent the occurrence of

undesired side reactions or to ensure the complete use of costly reactants. When the
reactants are not in stoichiometric quantities, the reactant present in more quantities
than the stoichiometric quantities is termed the excess reactant

57
 Process Calculation

Percent Excess:

Moles of reactant fed-Moles of reactant required

% Excess= X100
Moles of reactant required

Percent Conversion:

a). Overall Conversion: -

A in fresh feed – A in net pdt

= x 100
A in fresh feed

b). Perpass / Single Pass Conversion: -

A in mixed feed – A in gross pdt

= x 100
A in mixed feed

Yield (Y):

Moles of desired product formed

=
Total moles of A reacted

Selectivity (SB/C):

Moles of B formed
=
Moles of C formed

If SB/C = 3.2

Means 1 mole of C is formed then, 3.2 mole of B is formed.

Solved Examples

Question:

CO reacts with H2 to produce methanol. Calculate

1. Stoichiometry ratios of CO & H2

58
 Process Calculation

2. Kmol of methanol produced per kmol of CO reacted

3. Wt ratio of CO to H2 if both are fed Stoichiometric proportions

4. Quantity of CO required for 1000kg MeOH production.

Solution:

CO + 2H2 → CH3OH

1. ½

2. 1 Kmol

CO 1 28 7
3. = x =
H2 2 2 1

4. 875 Kg

Molar calculation

Basis: - 1000 Kg of CH3OH

1000Kg
nCH OH =
3 32Kg / mol

= 31.25k mol

1 Kmol of CH3OH produced = 1 kmol of CO reacted

31.25 of CH3OH produced by = 31.25 kmol of CO reacted

mass of CO required = 31.25 x 28 Kg/Kmol

= 875Kg

Molal Calculation:

Basis: 1000 kg of CH3OH

CO + 2H2 → CH3OH

28 2x2 32

32 Kg CH3OH produced = 28 Kg of CO required

28
1000 Kg CH3OH produced = x 1000
32
= 875 Kg of CO required

59
 Process Calculation

Question:

Ethylene C2H4O oxide is prepared by 100 kmol of C2H4 (ethylene) & 100 kmol of O2 are fed
to a reactor. The % conversion of ethylene is 85% & % yield of C2H4O is 94.12%. Calculate
the composition of the product stream on the mole basis.

Solution:

1
C2H4 + O → C2H4O − − − ( 1)
2 2

C2H4 +3O2 → 2CO2 + 2H2O − − − ( 2 )

Basis: - 100 kmol of C2H4

100 kmol of O2

Moles of C2H4 reaction = 85= 100 x 0.85

Moles of C2H4O formed = 85 x 0.9412

= 80.0002 Kmol

For Reaction (1)

1 kmol C2H4O require = 1 kmol C2H4

80.002 C2H4O require = 80.002 kmol C2H4

1 kmol C2H4O require = 0.5 kmol O2

80.002 C2H4O require = 40.001 kmol O2

For Reaction (2)

C2H4 reaction = 85 – 80.002

= 4.998 Kmol

1 kmol C2H4 produce = 2 kmol CO2

4.998 kmol C2H4 produce = 9.096 kmol CO2

4.998 kmol C2H4 produce = 9.096 kmol H2O

60
 Process Calculation

1 kmol C2H4 = 3 kmol O2

4.998 kmol C2H4 = 3 x 4.998

= 14.994 Kmol O2

O2 remaining = 100 – 40.001 — 14.994

= 45.005 Kmol

Component Mole remains

C2H4 15

C2H4O 80.002

O2 45.005

CO2 9.996

H2O 9.996

Question:

In a manufacturing of CH3COOH by oxidation of CH3CHO which is fed to a reactor per

hour, the product leaving the reactor contains 14.81% CH3CHO, 59.26% CH3COOH and the
rest is oxygen of mole basis. Find out of % conversion of CH3COOH.

Solution:

1
CH3CHO + O → CH3COOH
2 2

Basis: 100 moles of product.

CH3CHO → 14.81 mol

CH3COOH → 39.26 mol

O2 → 25.93 mol

1 mol of CH3COOH produced = 1 mol CH3CHO reacted

59.26 mol of CH3COOH produced by = 59.26 mol CH3CHO reacted

total acetaldehyde = 14.81 + 59.26

= 74.07 mol

61
 Process Calculation

Percent conversion:

59.26
X= x 100
74.07

= 80.005 %

OR

Basis: -

100 mol CH3CHO

Initial: -

1
CH3CHO + O → CH3COOH
2 2

100 y 0

Finally: -

Let ‘x’ mol reacted acetaldehyde

 x
( 100 − x ) y − 
2
x


x
Total final moles = (100-x) + ( y − ) + (x)
2

x
ntotal = 100 + y −
2

For CH3CHO

nCH CHO
3
= 0.1481
ntotal

100 − x
= 0.1481 − ( 1)
x
100 + y −
2

62
 Process Calculation

For CH3COOH

x
2 = 0.5926 − ( 2)
x
100 + y −
2

x = 80.005mol

Question:

A combustion chamber is fed with butane and excess air. Combustion of butane is
complete. The composition of combustion gases on volume basis is given as CO2 - 9.39%,
H2O - 11 73%, O2 - 4.7%.; N2 -74.18. Find the % excess of used & moles air per mole of air.

Solution:

C4H10 + 6.5O2 → 4CO2 + 5H2O

In gases, the volume % is same as the mole%

Air (79% N2, 21% O2)

Basis: - 100 mol of combustion gases

CO2→ 9.39%

O2→ 4.7mol

H2O →11.73 mol

N2 → 74.18 mol

13
C4H10 + O → 4 CO + 5H2O
2 2

4 mol CO2 produced = 1 mol C4H10 reacted

9.39 mol CO2 produced = 1/4 x 9.39 = 2.3475 mol C4H10 reacted

4 mol CO2 produced = 15/2 mol O2 reacted

15
9.39 mol CO2 produced = × 9.39 = 15.2587 mol O2 reacted
2×4

63
 Process Calculation

O2 supplied = 15.2587 + 4.7

= 19.9587 mol O2

O2 mol in = air x 0.21

moles of O2
Moles of air =
21

O2 required 15.2587
air required = =
0.21 0.21

= 72.6604 kmol

O2supplied 19.9587
Air supplied = = = 95.041
0.21 0.21

% Excess

95.041-72.6604
= ×100
72.604

= 30.80%

nair 95.04
= % × 40.486
nbut 23475

% Excess air = % Excess O2

air fed – air required

= X 100
air required

air fed* 0.21 – air required* 0.21

=
air required * 0.21

O2 fed – O2 required
=
O2 required

Question:

A feed containing 60% A, 30% B, 10% inert enters a reactor. The product stream leaving
the reach contains 2% A. Find the percentage conversion of A if the reaction takes place
as 2A + B → C

64
 Process Calculation

Solution:

Basis: - 100 mol of feed

A → 60 mol

B → 30mol

I → 10 mol

Initially: -

2A + B → C

60 + 30 + 0

Let x mol of A reacted

Finally

 
(60 − x ) +  30 − 2x  + 2x + 10mol = 100 − x
 

nA
yA =
ntotal

60 − x
0.02 =
100 − x

x = 59.18mol

60 − ( 60 − 59.18)
XA = × 100
60

= 98.63%

Question:

Limestone mixed with Coke is being burnt in a kiln and the avg. analysis of limestone
is 84.5% CaCO3, 11.5%. MgCO3 & rest inert, Coke contains 76% C, 21% ash, and rest
moisture content. The calcination of CaCO3 is only 95% & MgCO3 is 90%. The C in coke is
completely burnt into CO2. The kiln is fed with 1 kg coke and 5 kg of Limestone. Calculate
the wt % of CaO in the product leaving the kiln. Assume that the moisture present in the
feed is completely vaporized.

Molecular weight MgCO3 → 84 & CaCO3 →100

65
 Process Calculation

Solution:

Coke

Limestone gas (CO2, H2O vapourised)

Reactor
pdt
CaO
MgO
CaCO3
MgCO3
ash
Inert

Basis: - 1 kg Coke of & 5 kg limestone

Coke

C →0.76kg

Ash → 0.21 kg

moisture → 0.03 kg

Limestone

CaCO3 → 5 x 0.845 = 4.225 kg

MgCO3 →5 x 0.115 = 0.575kg

Inert → 5 x 0.04 = 0.2kg

CaCO3 reacted = 4.225kg ×0.95

= 4.01375 kg

CaCO3 unreacted = 4.225 – 4.01375

= 0.21125 kg

MgCO3 unreacted = 0.575kg – 0.575 x 0.9

= 0.0575kg

4.01375
CaCO3 reacted = kg
100

= 0.0401375 kmol

66
 Process Calculation

0.575×0.9
MgCO3 unreacted = kg
84

= 0.00616 kmol

CaO produced = 0.0401375 kmol.

= 0.0401375 × 56

= 2.2477 kg

MgO produced = 0.00616 k mol

= 0.00616 kmol x 40 kg / kmol

= 0.2464 Kg

Component Weight

CaCO3 0.21125

MgCO3 0.0575

CaO 2.2477

MgO 0.2464

Ash 0.21

Inert 0.1

Total =3.17285

2.2477
Cao = = 0.7084
3.17285

= 70.84%

Question:

Pure CO may be prepared by treating limestone with aqueous H2SO4. The limestone used
contains CaCO3 & MgCO3 & the rest is inert. The aqueous acid used contains 12% H2SO4
by wt & the rest is water. The residue from the process is found to contain CaSO4 9%,
MgSO4 5%, H2SO4 1.2%, Inert 0.5%, CO2 0.2% & H2O 84.1%

67
 Process Calculation

During the process, the mass was heated up and CO2 & H2O vapor was removed

i) Calculate analysis of limestone used (composition).

ii) Percentage of excess of acid used.

iii) Mass of water vaporized per 100 kg limestone.

Solution:

CO2 =
H2O =

Limestone

Reactor Residue

CaCO3
MgCO3 CaSO4 MgSO4
Inert H2SO4 0.12 H2SO4 Inert
H2O 0.88 H2O

aq H2SO4

CaCO3 + H2SO4 → CaSO4 + CO2 + H2O − − − ( 1)

MgCO3 + H2SO4 → MgSO4 + CO2 + H2O − − − ( 2 )

100 Kg CaCO3 → 136 kg CaSO4

100
0.09 kg CaSO4 → × 0.09 CaCO3
136

CaCO3 = 0.0661 kg

84 Kg MgCO3 → 120 kg MgSO4

84
0.05 Kg MgSO4 → × 0.05 MgCO3
120

MgCO3 =0.035 kg

inert = 0.005 kg

68
 Process Calculation

Basis: - 100 kg of Residue

Inert = 0.5kg, CaSO4 = 9kg, MgSO4 = 5 kg

H2SO4 = 1.2kg, CO2 = 0.2kg, H2O = 84.1kg

1 kmol CaSO4 produced by = 1 kmol CaCO3

0.06617 kmol CaSO4 produced by = 0.06617 kmol CaCO3

1 kmol MgSO4 produced by = 1 kmol Mg CO3

0.0416 kmol MgSO4 produced by = 0.0416 kmol Mg CO3

CaCO3 required = 0.06617 kmol x 100 kg / kmol

= 6.617 kg

MgCO3 required

kg
=0.0416 kmol ×84
kmol

= 3.5kg

Limestone required

= 6.617 kg CaCO3 + 3.5 kg MgCO3 + 0.5 inert

=10.617 kg.

Limestone

• CaCO3 - 62.32%

• MgCO3 - 32.96%.

• Inert - 4.71%

From reaction (1)

1 mol CaSO4 required = 1 kmol H2SO4

0.06617 Kmol CaSO4 required = 0.06617 kmol H2SO4

69
 Process Calculation

From reaction (2)

1 kmol MgSO4 required = 1 kmol H2SO4

0.0416 Kmol MgSO4 required = 0.0416 kmol H2SO4

Total H2SO4 required = 0.06617 + 0.0416

= 0.1077 kmol H2SO4

H2SO4 required = 0.1077 x 98 Kg / Kmol

= 10.561 kg

Acid required = 10.561 / 0.12

= 88.0083 kg

H2SO4 fed = (10.561 +1.2) kg

= 11.761 kg

11.761
Acid fed =
0.12
= 98.0083 kg

amt feed – amt required

Percent excess acid = * 100
amt required

98.0083 – 88.0083
= * 100
88.0083

= 11.36 %

Amount of limestone = 10.6176 kg

Acid fed = 99.0083 kg

Water fed = 98.0083 x 0.88

= 86.247 kg

For reaction (1)

1 kmol CaSO4 produced by = 1 kmol of H2O

0.06617 kmol CaSO4 produced by = 0.06617 kmol of H2O

70
 Process Calculation

For reaction (2)

1 kmol MgSO4 produced by = 1 kmol of H2O

0.0415 kmol MgSO4 produced by = 0.0415 kmol of H2O

Total H2O produced = 0.06617 + 0.04161

= 0.10777 Kmol

= 0.10777 Kmol X 18 Kg/kmol

= 1.939 kg

Total H2O present in process = H2O fed + H2O produced

= 86.247 + 1.939

= 88.186 kg

H2O vaporized = 88.186 – 84.1

= 4.086 Kg

With 10.617 kg limestone = 4.085 kg H2O produced

With 100 kg limestone

4.083
X100 = 38.485 kg H2O produced
10.617

Question:

It is proposed to produce acetaldehyde by oxidation of EtOH in the gas phase reaction.

The ratio of air to EtOH in the fresh feed is 10:1. The conversion of EtOH on a single
pass is 25%. The unreacted EtOH is completely separated from the reaction product
& recycled. What is the ratio of recycle stream to fresh feed & the composition of the
outlet stream from the reactor? (in mol % & wt.%).

Solution:

1
C2H5OH + O → CH3CHO + H2O
2 2

71
 Process Calculation

E
Xps = 25% C2H5OH
Freshfeed M CH3CHO P1 Net
Reactor Seperator pdt
H2O
NAir O2 N2 CH3CHO
nE+OH =10/1 H2O
EtOH O2
N2
R

Basis: - 1 mol EtOH & 10 mol air

Fresh feed air, (N2 = 7.9 mol and O2 = 2.1 mol)

Mixed feed

Overall Mass Balance: -

F+R=M

O2 – 2.1 mol, N2 - 79mol

EtOH = (1+R) mol

XPS = 0.25

EtOH reacted = (1+R) x 0.25 mol

EtOH unreacted = (1+R) x 0.75 mol

EtOH in Recycle stream = EtOH entering in separator

R = ( 1 + R ) × 0.75

R=3

F = 11

R 3
=
F 11

Component Mole Mol% Wt%

N2 7.9 54.48 46.82%
CH3CHO 1 6.89 9.314%
C2H5OH 3 20.68 29.314%
O2 2.1 –0.5 = 1.6 11.03 10.83%
H2O 1 6.89 3.78%
= 14.5

72
 Process Calculation

Purging:

A major limitation sometimes encountered in the recycling operation is the gradual

accumulation of inert materials or impurities in the recycled stock. The impurities may
accumulate to such a level that the process automatically comes to a stop. This difficulty
can be overcome by bleeding off a fraction of the recycled stock.

E
F M N
Reactor Prod.

R P
Purge

1. Recycle Ratio R/F

2. Purge Ratio P/R

 NPr 
3. Recovery (Recovered amounts.  
 feed 
4. % Conversion

a) Overall Conversion: -

A in fresh feed – A in net pdt

x 100
A in fresh feed

b) Perpass / Single pass Conversion: -

A in mixed feed – A in gross pdt

x 100
A in mixed feed

At steady state,

F×xF = P.xP1

Solved Examples

Question:

For the reaction, A → B. The process flow diagram is given below. The fresh feed of A
contains 0.5% inert materials by mole, 60% conversion of A per pass is achieved and the
concentration of inert matrials going into the reactor must be held at 2% by mol.

73
 Process Calculation

2
1 E
M P2
Reactor Separator Net pdt
Freshfeed 2% I B
A, I
T
0.5% I 3
R A, I Purge A, I

If the process is at steady state, calculate

i. How many moles must be recycled per mole of total feed at point 1 to the reactor?

ii. How many moles need to be purged?

iii. Overall conversion of A?

Solution:

Basis: - 1 mol of mixed feed at 1,

A in Mixed Feed = 0.98 mol

Inert in Mixed Feed = 0.02 mol

At Reactor outlet

A reacted = 0.98 x 0.60

= 0.588 mol

A unreacted = 0.98 - 0.588

= 0.392 mol

I = 0.02 mol

B = 0.588 mol

Over separator: -

Overall Mole Balance: -

E = T + P2

(0.392 + 0.02 + 0.588) = T+ 0.588

T = 0.412 mol.

74
 Process Calculation

xA in T

0.392
xA = = 0.9514
0.412

xI = 1 - 0.9514 = 0.0485.

At splitting point (3): -

Overall mole Balance

P + R = T = 0.412

Over mixing point: -

F+R=M=1 F=1-R

Inert Balance

F x 0.005 +R x 0.0485 = 0.02 x 1

F = 0.655 mol

R = 0.344 mol

P + R + T = 0.412

P = 0.068 mol

F * 0.995 – P * 0.9514
XA = *100
F * 0.995

XA = 90.19%

Energy Balance:

Law of Energy Conservation:

The law of conservation of energy states that although energy may be converted from
one form to another, it cannot be created or destroyed. Whenever a quantity of one form
of energy is produced, an exactly equivalent amount of another kind must be used up.

75
 Process Calculation

Potential energy:

The energy stored within the system due to its position above some arbitrary reference
plane and is referred to as its potential energy (PE). If a body of mass m is at an
elevation z above the ground, the potential energy of the mass is

PE = mgz

Kinetic energy:

The energy possessed by a body by virtue of its motion is called its kinetic energy (KE). If
a body of mass m is moving at a velocity u, the kinetic energy of the body is

K.E. = (½)mu 2

Solved Examples

Question:

A body of mass 75 kg is lifted through 10m, what is the work done if it takes 2.5 mins for
lifting the mass.

Solution:

W = F×∆z

F = mg

W = mg ∆z

= 75 × 981 × 10

= 7357.5 Kg m/ s2 .m = N.m = J

W
Power =
t

7357.5  1min 
= J ×  
2.5 min  60 sec 

= 49.05 Watt

76
 Process Calculation

Question:

Potential Energy of a body of mass 10 kg is 15 kJ. What is the height of the body from
the ground in ft.? If a body of mass 10 kg has Kinetic Energy of 12 kJ. What will be the
momentum then?

Solution:

PE = mgh

15 kJ = 10 kg × 9.81 × h

15 × 103
= h
10 × 9.81

1 ft
h = 152.90 m ×
0.3048 m

= 501.65 ft

1
KE = mv 2
2

1
12 KJ = × 10 × V2
2

V = 48.9897

Momentum = MV = 489.89 kgm / sec

Heat Capacities:

The heat capacity of a substance is the quantity of heat to be supplied to cause a

temperature rise of one degree.

Specific heat (KJ / KgK):

The heat capacity of the unit mass of a substance is also known as specific heat of the
substance. Heat capacity depends on the way the heat is supplied.

→CP for constant Pressure

→CV for constant Volume

77
 Process Calculation

Enthalpy:

The heat supplied at constant pressure can be measured as the change in another
thermodynamic property of the system which we call enthalpy.

H = U + PV

At const pressure →

Q = ∆U + P∆V

T2
Q = ∆H = ∫ T1
Cp .dT

dH = CpdT

T2
∆H = ∫ T1
Cp .dT

dU = CVdT

For constant volume

T2
Q = ∆U = ∫ T1
CV .dT

If Cp = f ( T )

Cp = a + bT + cT2 + dT3 + …

For unit mass

dH = CpdT

∫ (a + bT + cT )
T2 T2
∫
2
∆H = H2 − H1 = Cp .dT = + dT3 dT
T1 T1

∆H = a ( T2 − T1 ) +
b 2
2
(
T2 − T12 +
c 3
3
) (
T2 − T13 + )
d 4
T − T14
4 2
( )
If Cp ≠ f ( T )

For unit amount

dH = CpdT

∆H = Cp ( T2 − T1 )

78
 Process Calculation

Mean heat Capacity: - For constant composition & varying temperature

T2
∫ T1
Cp .dT
Cp = T2
∫
mean
dT
T1

If temperature is constant then the mean heat capacity for a mixture is,

Cp
mix
= ∑ xC i pi

KJ
If cP → molal heat capacity
i Kg.K

xi → mass fraction

KJ
If Cpi → molar heat capacity
Kmol.K

xi → mol fraction

Solved Examples

Question:

The molal heat capacity of CO is given by Cp = 26.586 + 7.582 x 10-3 T– 1.12x10-6 T2, where
Cp = kJ/KgK & T in K. Calculate mean heat capacity for the temp range of 500 - 1000k.

CO enters a heat exchanger at the rate of 500m3 / hr at STP. Calculate the heat supply to
gas to raise its temp from 500 to 1000K.

Solution:

Cp = 26.586 +7.582×10−3 T − 1.12 × 10−6 T2

dH = CpdT

T2
∆H = H2 − H1 = ∫ T1
Cp .dT

79
 Process Calculation

7.582×10−3 1.12×10−6
= 26.586 * 500 +
2
( )
10002 − 5002 −
3
( 1000
3
− 5003 )
= 13293 + 2843.25 - 326.666

T2
∫ T1
Cp .dT
Cp = T2
∫
mean
dT
T1

13293 + 2843.25 −326.666

Cp =
mean 1000 − 500

KJ
= 31.6191
Kg.K

For 1 mol

T2
∆H = ∫ c .dT
T1 p

For m moles

T2
∆H = m ∫ T1 p
c .dT

At STP

PV
n=
RT

1 × 500
=
8.314 × 273

22.4m3 = 1kmol

1 Kmol
500m3 = × 500
22.4 hr

kmol
n = 22.32
hr

Q = ∆H

m = n × Mw

80
 Process Calculation

= 22.32 × 28

kg
= 625
hr

kg KJ
Q = ∆H = 625 × 31.6191 × ( 1000 − 500 ) K
hr kg.K

KJ
= 9880968.75
hr

MJ
= 9880.96
hr

Question:

Calculate the heat that must be removed for cooling up 32 kg O2 from 488K to 313K
using theheat capacity equation CP = (a + bT + cT2 + dT3),

Constant a b x 103 c x 106 d x 109

O2 26.025 11.755 -2.3426 -0.5223

Solution:

T2
∫ T1
Cp .dT
Cp = T2
∫
mean
dT
T1

=
a ( T2 − T1 ) +
b 2
2
( ) c
(
T2 − T12 + T23 − T13 +
3
d 4
4
T2 − T14 ) ( )
T2 − T1

11.755×10−3 2.3426 × 10−6

Cp .dT = 26.025 ( 488 − 313  + ( ) ( )
0.5223 × 1
T2
∫ T1 2
4882 − 3132 −
3
4883 − 3133 −
4

755×10−3 2.3426 × 10−6 0.5223 × 10−9

2
(

4882
− 3132 −
3
) 4883 − 3133 −
4
( 4884 − 3134 ) ( )
= 4554.375 + 823.878 − 66.803 − 6.15199

81
 Process Calculation

4554.375 + 823.878 − 66.803 − 6.15199

Cp =
175

= 30.3159

T2
∆H = m ∫ c .dT
T1 p

= 169769.372KJ / K

= −169.769MJ / K

-Ve as energy is released

Energy balance for phase change

Change of state from solid to liquid occurs at constant temperature and constant
pressure. The enthalpy change accompanying this process is known as heat of fusion or
latent heat of fusion

∆H3

∆H2 ∆Hv

∆H1 ∆Hf

H1

250 K 273.15 373.15 400 K

∆HF → Latent heat of fusion

Heat water from 273K until it becomes equal to 373 K, the normal boiling point of water.
The heat absorbed by the water that resulted in its temperature rise is its sensible heat.

The heat required to change the state of unit mass of a substance from the liquid to the
vapor state is known as the heat of vaporization or the latent heat of vaporization. The
heat given out when a unit mass of vapor condenses to liquid is known as the heat of
condensation. The heat of vaporization is numerically equal to the heat of condensation,
but the sign is opposite.

82
 Process Calculation

∆HV → Latent heat of vaporization

(Latent heat of condensation) = - (Latent heat of Vaporization)

Saturated L @ 1atm & 100°C

Subcooled L @ 1atm & < 100°C

Saturated V @ 1atm & 100°C

Superheated V @ 1atm > 100°C

Saturation Heat = mCp ∆ T

Latent Heat = m λ

Solved Examples

Question:

1 kg of water is heated from 250k - 400k, at 1atm pressure. How much heat does this
require? Mean heat capacity of ice = 2.037 kJ / Kgh for the temperature range of 250k -
273.15 k. The mean heat capacity of water 75.726 KJ / KmolK for the temperature range
of 273.15k - 373.15 k & the heat capacity of water vapor is given by

Cp = 30.475 + 9.652 x 10-3 T+ 1.189 x 10-6T2, KJ / KmolK.

At 1atm - λ fusion = 601.2 kJ/kmol, λ evaporation = 40608 KJ / kmol

Solution:

T2
∫ T1
Cp .dT
Cp = T2
∫
mean vapor
dT
T1

a ( T2 − T1 ) + (
b 2
) c
(
T − T12 + T23 − T13
2 2 3
)
=
T2 − T1

83
 Process Calculation

9.652×10−3 1.184 × 10−6

C .dT = 30.475 ( 400 − 373.15  + ( ) ( )
T2
∫ T1 p 2
4002 − 373.142 −
3
4003 − 373.153

2×10−3 1.184 × 10−6

2
( 2
400 − 373.142 − )3
(
4003 − 373.153 )
= 818.25375 + 100.183 + 4.7727

818.25375 + 100.183 + 4.7727

Cp =
mean vapor
( 400 − 373.15)
KJ
= 34.3839
KmolK

∆H3

∆H2 ∆Hv

∆H1 ∆Hf

H1

250 K 273.15 373.15 400 K

Q = ∆H1 + ∆Hf + ∆H2 + ∆Hv + ∆H3

1 1 1 KJ 1
Q= × 2.037 × 18 × ( 273.15 − 250 ) + × 6012 + Kmol ×75.726 × ( 373.15 − 273.15 ) + × 406
18 18 18 Kmol 18

1 KJ 1 1 KJ
Kmol ×75.726
× ( 373.15 − 273.15 ) + × 40608 + × 34.3839 ( 400 − 373.15)
18 Kmol 18 18 Kmol

= 2.6198 + 334 + 420.7 + 2256 + 51.2893

= 3064.609KJ

Question:

A high boiling organic fluid at 650 k is mixed with CCl4 at 295k in the wt. ratio of 1:1. The
pressure is 1atm. What will the equilibrium temperature of the mixture be?

84
 Process Calculation

The heat capacity of organic fluid CPOf = 0.16 + 4.78 x 10-3T KJ / KgK

CPCCl4 liq. = 0.79435 + 1.298 x 10-4T KJ / KgK

bp of CCl4 = 349.9K & λVCCl4 = 195 KJ / KgK, CpCCl vp

= 0.4623 KJ / KgK
4

Solution:

Heat released by organic fluid = Heat gained by CCl4

∆Hof = ∆HCCl
4

First, we assume the liquid phase

T T
− ∫ 650
cPofdT = ∫ c
295 PCCl 4
dT

0.16(650-T) + 4.78*0.5*10-3(6502-T2) = 0.79435(T-295) + 1.298*0.5*10-4(T2-2502)

T = 573.15K

Our approximation is wrong because the boiling point of CCl4 =349.9K, so let us assume
that resultant CCl4 is in the vapor phase

∆Hof = ∆HCCl
4

T 349.9 T
− ∫ 650
cpofdT = ∫ 295
cpdT + ∆Hv + ∫ c
349.9 pCCl 4
dT

0.16(650-T) + 4.78*0.5*10-3(6502-T2) = 0.79435(349.9-295) + 1.298*0.5*10-4(349.92-2502) +

0.4623(T-349.9)

104-0.16T - 2.39*10-3T2 + 1009.775= 43.6 + 2.297 + 0.4623T- 161.75

104-0.16T - 2.39*10-3T2 + 1009.775= 43.6 + 2.297 + 0.4623T- 161.75

1229.628 - 0.6223T- 2.39*10-3T2 = 0

T = 540 K

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 Process Calculation

Energy balance for chemical Reaction

R→P

Heat of Reaction:

The amount of heat that must be added or removed during a chemical reaction to keep
all the substances present at the same temperature.

If the pressure in the vessel containing the reacting system is kept at a constant value,
the measured heat of reaction also represents the change in the thermodynamic
quantity called enthalpy.

By heat of reaction, we mean the change in enthalpy of the system for the reaction
proceeding at constant temperature. It is the difference between the enthalpy of
products and the enthalpy of reactants and is denoted by ∆H.

The reactions in which heat is absorbed are called endothermic reactions and those in
which heat is evolved are called exothermic reactions.

∆H = ∑H pdt
− ∑H react

∆Hreaction = ∑ V ∆H i i

∆Hreaction = ∑ vi Hpdt − ∑ vi Hreactant

2A + 3B → 4C + 5D,

∆H > 0 endothermic

∆H < 0 exothermic

∆Hreaction = ( 4HC + 5HD ) − ( 2HA + 3HB )

Total : −

∆Hreaction = n.∆Hreaction

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Standard heat of reaction (∆H°rxn):

The standard heat of reaction is the enthalpy change accompanying a reaction when
both the reactants and products are at their standard states at constant temperature T.

∆H°rxn = ∑ vi H°Pdt − ∑ H° react

Heat of formation (Hf):

The heat of formation is the heat evolved or absorbed in the formation of one mole of
a substance from its constituent elements or the change in enthalpy accompanying the
formation of one mole of a substance from the constituent elements.

When the reactants and products are at their standard states, the heat of formation is called
standard heat of formation. The enthalpy of formation of the elements is taken as zero.

2A + B → C, ∆Hreaction = 20KJ / mol

HfC = 20KJ

Heat of Combustion (Hc):

When the reaction under consideration is a combustion reaction, the heat of reaction is
known as heat of combustion.

The heat of combustion is usually expressed per mole of the substance reacted. The
negative of the heat of combustion of a fuel is frequently referred to as its heating value.
This is the energy exchanged with the surroundings when the unit mass of fuel is burnt
in oxygen.

A + 3B → C, ∆H = 40KJ / mol

Hc = −40KJ / mol
A

At STP

∆H°rxn = ∑ vi H°fProd − ∑ vi H°f

reactant

∆H°rxn = ∑ vi H°creactant − ∑ vi H°c

prod

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Solved Examples

Question:

A gas mixture analyzing 20 mole% CO, 30 mole% H2 & 50 Mole % N2 is completely burned
and the heat of reaction is available

1
CO + O → C02 , ∆H°rxn = −282.9kJ / mol
2 2

1
H2 + O → H2O , ∆H°rxn = −241.83KJ / mol
2 2

Calculate

i. Amount of heat liberated for 100mol of gas mixture

ii. Amount of heat liberated for 100mol of gas if 90% CO & 80% H2 is converted only.

Solution:

Basis: -100 mol of gas mixture.

CO − 20mol

H2 − 30mol

N2 − 50mol

1 mol CO = 282.91

20 mol CO = 20 × 282.91KJ / mol

= 5658.2 KJ

1 mol H2 = 241.83

30 mol H2 = 30 × 241.83 KJ / mol

= 7254.9 KJ

Total heat liberated = 7254.9 + 5658.2 = 12913.1 KJ

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 Process Calculation

(ii)

CO reacted = 20 x 0.9

= 18 mol

H2 reacted = 30 x 0.8.

= 24 mol.

Total heat liberated = 18 x 282.91 + 24x241.83 = 10920.3 KJ

Hess’s Law: -

Heat of reaction represents the difference between the enthalpy of products and the
enthalpy of reactants. Enthalpy as we know, is a state function and the heat of reaction,
therefore, depends only on the initial and final states, no matter how this change is
carried out.

The net heat evolved or absorbed in a chemical reaction is the same whether the
reaction takes place in a single step or in a series of steps. This is known as Hess’s law.

T1 ∆Hrxn T2
R P

∆H1
∆H2

298K ∆Hrxn 298K

R P

∆Hrxn = ∆H1 + ∆H°rxn + ∆H2

Solved Examples

Question:

Pure CO is mixed with 100% excess air and completely burns at constant pressure. The
reactants are originally at 400 K. Determine the heat added or removed if the products
leave at 600 K. At standard state, heat of reaction is given as 282.99 kJ / mol of CO
burned. Cpmean applicable in the temperature range are

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 Process Calculation

CPmean 29.10 29.70 29.10 41.45

(KJ/Kmol.K)

Component CO O2 N2 CO2

1
CO + O → C02
2 2

Solution:

Basis: -

1 kmol CO = 0.5 kmol O2

O2 fed = 0.5 + 0.5 = 1 kmol (100% excess)

N2 fed = 1/0.21 x 0.79 = 3.7619 kmol

CO2 ∆Hrxn P CO2

O2
O2 N2
N2

∆H1
∆H2

∆Hrxn
CO2 CO2 298K
O2 N2 O2 N2

298K

 KJ 
∆H1 =  1 × 29.10
KmolK
( CO ) + 3.762 × 29.10 (N2 ) + 1 × 29.70 ( O2 )  ( 298 − 400 )
 

∆H1 = −17163.9684KJ

KJ  103 mol 
∆H°rxn = 1 Kmol × 282.99 × 
mol  1 Kmol 

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 Process Calculation

= 282.99 × 103 KJ

∆H2 =  1 × 41.45 ( CO2 ) + 3.762 × 29.10 (N2 ) + 0.5 × 29.70 ( O2 )  ( 600 − 298)

∆H2 = 50063.80KJ

 + ∆H
∆Hrxn = ∆H1 + ∆Hrxn 2

= 315889.84KJ

= 315.889 MJ

Orsat Analysis:

Orsat analysis is a dry basis analysis. All components are considered except H2O.

CH4 + O2 → CO2 + H2O

Solved Examples

Question:

CH4 is completely burned with air. Find volume % of CO2 in the flue gas on wet basis as
well as dry basis.

CH4 +202 → CO2 + 2H2O

1mol 2mol 0mol 0mol

Solution:

O2 supplied = 2 mole

N2 Supplied = 7.52 mole

product (wet basis):

CO2 = 1 mol

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 Process Calculation

N2 = 7.52 mol

H2O = 2mol

product (dry basis): −

CO2 = 1 mol

N2 = 7.52 mol

1
CO2 % in dry basis = × 100 = 11.73%
8.52

1
CO2 % in wet basis = × 100 = 9.5%
10.52

Gross Calorific Value & Net Calorific Value:

Gross calorific value indicates how much energy can be released during the complete
combustion of a given amount of fuel. It comprises net calorific value plus the energy
contained in the exhaust gases and in the water-vapor produced during combustion. The
gross calorific value is always higher than the net calorific value.

If the water remains in the exhaust gas as water vapor, the net calorific value is
specified. But if the exhaust gases are cooled below the condensation point of water
vapor the gross calorific value is given.

The gross calorific value is denoted by Hs (s = superior, Latin for “higher”), previously it
was also called higher heating value. Net calorific value is denoted with Hi (i = inferior,
Latin for “lower”), formerly it was also known as lower heating value.

→GCV - Gross Calorific Value H2O(L)

→NCV - Net Calorific Value H2O(V)

• Net calorific value (Hi) = gross calorific value (Hs) – condensation heat

• Gross calorific value (Hs) = net calorific value (Hi) + condensation heat

NCV = GCV − nλ

GCV = NCV + nλ

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 Process Calculation

Solved Examples

Question:

Crude oil is analyzed to contain 87%C, 12.5% H2 & 0.5% S by wt. Calculate the NCV of crude
oil at 298K, if GCV of crude oil at 298K = 45071 KJ/Kg oil & at 298K λ w = 2442.5 kJ/kg

Solution:

Basis: -1 kg crude oil.

C = 0.87 kg

H2 = 0.125kg

C + 02 → CO2

1
H2 + O → H2O
2 2

2 kg H2 produce = 18 kg H2O

0.125 H2 produce = 18/2 x 0.125

= 1.125 kg H2O

NCV = GCV – mλ

= 45071 – 1.125 x 2442.5

= 42323.18 KJ / kg

Question:

A hydrocarbon mixture is burned with excess air. The orsat analyses of flue gas
shows 10.81% CO2, 378% O2 & 85.4%. N2 by mole. Calculate the atomic ratio of C/H in
hydrocarbon mixture & % excess of air

Solution:

CH4 + 2O2 → CO2 + 2H2O

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 Process Calculation

Basis: - 100 mol of product gases to based on orsat analysis

CO2 → 10.81 mol

O2 → 3.78 mol

N2 → 85.4 mol

C + O2 → CO2 − − − − ( 1)

1
H2 + O → H2O − − − − ( 2 )
2 2

1 mol of CO2 required = 1g-atom C

10.81 mol of CO2 required = 10.81 g-atom C

1 mol of CO2 required = 1 mol O2

10.81 mol of CO2 required = 10.81 mol O2

Air fed = 85.4/0.79 = 108.101 mol

O2 fed = 108.101 x 0.21 = 22.7012 mol

O2 consumed in reaction (2) = 22.7012 — 10.18 – 3.78

= 8.1112 mol

1/2 mol O2 react with = 2g-atom of H

8.1112 mol O2 react with = 2/0.5 x 8.1112

= 32.4448 g-atom of H

C 10.81
= = 0.3331
H 32.448

O2 fed- O2 red
% excess air = x 100
O2 red

22.7012 − 18.921
= x 100
18.921

= 19.97 %.

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 Process Calculation

Degrees of Freedom:

The difference between the number of unknown variables and the number of equations
is known as the number of degrees of freedom.

If the number of degrees of freedom is positive it means that the number of variables
is more than the number of equations, and we should try to get additional equations or
variable specifications to get a unique solution to the problem.

If the number of degrees of freedom is negative, we have too many equations than there
are variables. This may arise if we have not included some variables in the flow diagram.

If the number of degrees of freedom is zero, it means that the material balance problem
is properly specified, and we can proceed to solve the equations for evaluating the
unknown variables.

F = C − π (P ) + 2 − r − s

C = No. of components

r = No. of independent Chemical reaction

S-z = No. of constraints

π /P = No. of phases.

* For azeotrope S = 1, as x = y

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 Practice Questions

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Practice Questions

97