Chemical Engineering

Calculations
Atlas Adonis V. Cerbo, R.ChE, MSc
November 18, 2023
STOICHIOMETRY
• Study of how reactants are consumed and
products are produced in a chemical reaction

A+B→C+D
left side: reactants
right side: products

• No atoms are produced (in a non-nuclear

reaction), so the equation should be balanced,
and all atoms present in the reactant/s should be
accounted for in the products
 TYPES OF
CHEMICAL REACTIONS
1) Synthesis – combination of 2 or more compounds
 TYPES OF
CHEMICAL REACTIONS
2) Decomposition – opposite of synthesis, breaking down of a
compound into simpler one
 TYPES OF
CHEMICAL REACTIONS
3) Single displacement – transfer of 1 element / component
from 1 compound to form a new compound
 TYPES OF
CHEMICAL REACTIONS
4) Double displacement – atoms / components of 2
compounds switch to form 2 different compounds
Mass Changes in Chemical Reactions

1. Write balanced chemical equation

2. Convert quantities of known substances into moles
3. Use coefficients in balanced equation to calculate the
number of moles of the sought quantity
4. Convert moles of sought quantity into desired units
Theoretical Yield is the amount of product that would
result if all the limiting reagent reacted.

Actual Yield is the amount of product actually obtained

from a reaction.

Actual Yield
% Yield = x 100
Theoretical Yield

3.10
A solution of that contains 41.6 grams silver nitrate
was reacted with a solution containing 35.4 grams
of barium chloride. Which is limiting reactant?
How many grams of which reactant will be left
over? How many grams of AgCl will be formed?

Answer: 9.9 g BaCl2 and 35.1 g AgCl

Sample Problem
One of the steps in the manufacture of nitric acid is the oxidation of
ammonia shown in the equation:

NH3 + O2 → NO + H2O

If 43.0 kg of NH3 react with 35.4 kg of O2, what mass of NO forms a)

100% yield and b) 88 % yield?

Answers: 26.55 grams of NO, 23.36 grams of NO

CHEMICAL ENGINEERING
CALCULATIONS
MATERIAL BALANCE
for reactive processes
Methods of solving material balances on
reactive systems

• Extent of reactions
• Molecular species balances
• Atomic species balances
Extent of Reaction
• The extent of reaction ξ is based on a balanced chemical equation and
denotes how much a reach occurs.

ni − ni0
ξ=
𝑣𝑖
where:
ni = moles of species i present in the system after the reaction
ni0 = moles of species i present in the system when the reaction starts
νi = stoichiometric number for species i in the balanced chemical equation

Thus, to determine final amount of a species i in a reacting system:

ni = ni0 + 𝑣𝑖 ξ
Extent of Reaction

• For the complete combustion of heptane:

C7H16 (l) + 11O2(g) → 7CO2(g) + 8H2O(g)

The following equations can be written:

nC7 H16 = nC7 H16 ,0 − ξ
nO2 = nO2 ,0 − 11ξ
nCO2 = nCO2,0 + 7ξ
nH2O = nH2O,0 + 8ξ
Maximum extent of reaction

• A straightforward method of determining the limiting reactant

for a given reaction is by calculating the maximum extent of
reaction ξ𝑚𝑎𝑥 . This extent is based on assuming the complete
reaction of each reactant.
• The reactant with the smallest maximum extent of reactant is
the limiting reactant.
Maximum extent of reaction
• 12 moles of oxygen is used to burn 1 mole of heptane in a
combustion chamber. Assuming complete combustion of
heptane, what is the limiting reactant?
Reaction: C7H16 (l) + 11O2(g) → 7CO2(g) + 8H2O(g)
Assuming complete reaction of C7H16:
max
0 − 1 mol
ξ = = 1.00 mol
−1
Assuming complete reaction of O2:
max
0 − 12 mol
ξ = = 1.09 mol
−11
Thus, heptane is the limiting reactant and oxygen is in excess.
Fractional and percentage excess
• The fractional excess of the reactant is the ratio of the excess to the
stoichiometric requirement.
nA feed − nA stoich
fractional excess of A =
nA stoich

• The percentage excess is 100 times the fractional excess.

nA feed − nA stoich
% excess = x100
nA stoich
Fractional and percentage excess
• 12 moles of oxygen is used to burn 1 mole of heptane in a combustion
chamber. Assuming complete combustion of heptane, what is the fractional
excess of the excess reactant?
C7H16 (l) + 11O2(g) → 7CO2(g) + 8H2O(g)
Recall: C7H16 is the limiting reactant. Thus, 1 mole of heptane is totally
consumed. To calculate the amount of oxygen consumed:
11 mol O2
1 mol C7 H10 = 11 mol O2
1 mol C7 H10
Calculating the fractional excess of the excess reactant:
12 − 11 mol
fractional excess of O2 = = 0.091
11 mol
Conversion
• The fractional conversion f is the fraction of the limiting
reactant in the feed that is converted into products. Percentage
conversion is 100 times the fractional conversion.

moles or mass of limiting reactant reacted

f=
moles or mass of limiting reactant fed

In terms of the actual extent of the reactant and the maximum

extent, the fractional conversion is given by:
ξ
f = max
ξ
Example
• Acrylonitrile is produced in the reaction of propylene, ammonia,
and oxygen:
C3H6 + NH3 + 3/2O2 → C3H3N + 3H2O
The feed contains 10.0 mole% propylene, 12.0 mole% ammonia,
and 78.0% air. A fractional conversion of 30.0 mole% of the
limiting reactant is achieved. Taking 100 mole of feed as a basis,
determine which reactant is limiting, the percentage excess of the
excess reactants, and the molar amounts of product gas that will
constitute 30% conversion of the limiting reactant
• Assumptions: (1) steady-state operation
(2) air is an ideal gas mixture
Basis: 100 moles of feed
Process Flowchart:

nC3H6 mol
100 mol feed gas PROCESS
10% C3H6 nNH3 mol
UNIT
12% NH3 nO2 mol
78% air (79% N2, 21% O2) nN2 mol
• Determination of the limiting reactant:
If consumption C3H6 is complete:
max
0 − 10
ξ = = 10 mol
−1
If consumption of NH3 is complete:
max
0 − 12
ξ = = 12 mol
−1
If consumption of O2 is complete:
21
0 − 78
max 100
ξ = = 10.92 mol
3
−
2
Thus, C3H6 is the limiting reactant and NH3 and O2 are in excess.
• Determining the percentage excess of NH3 and O2:
1 mol NH3
nNH3 = 10.0 mol C3 H6 = 10.0 mol NH3
stoich 1 mol C3 H6
3
mol 𝑂2
nO2 = 10.0 mol C3 H6 2 = 15.0 mol 𝑂2
stoich 1 mol C3 H6

NH3 − NH3 stoich

0 12 − 10
% excess NH3 = x100 = x100 = 20%
NH3 stoich 10
21
O2 0 − O2 stoich 78 − 15
100
% excess O2 = x100 = x100 = 9.3%
O2 stoich 15
• Calculating product composition at 30% conversion
mole C3 H6 reacted nC3 H6 − (nC3 H6 ) 10 − nC H
0 3 6
f= = 0.3 = =
mole fed nC3 H6 10
0
nC3H6 = 7.0 mol C3 H6
7 − 10
ξ= = 3 mol
−1

nNH3 = 12 − ξ = 9.0 mol NH3

21 3
nO2 = 78 − ξ = 11.9 mol O2
100 2
nC3 H3N = ξ = 3.0 mol C3 H3 N
nH2 O = 3ξ = 9.0 mol H2 O
79
nN2 = 78 = 61.6 mol N2
100
Gravimetric factors
• For reactions involving solids or liquids, conversion from the mass of
one chemical species involved in a reactant to another requires the
use of gravimetric factors.
• In the general reaction:
aA + bB = cC + dD
The following mass relationships hold:
mass A a(MWA )
=
mass C c MWC

mass D d(MWD )
=
mass B b MWB
and so on.
Gravimetric factors
• Example: In the reaction for the roasting of pyrites:
4FeS2 + 11O2 → 2Fe2 O3 + SO2
Basis: 100 kg FeS2
To calculate the mass of O2 needed:
11MWO2 11 32.00 kg O2
100 kg FeS2 = 100 kg FeS2
4MWFeS2 4 119.98 kg FeS2
= 73.34 kg O2
To calculate the mass of Fe2O3 produced
11MWFe2O3 2 64.05 kg O2
100 kg FeS2 = 100 kg FeS2
4MWFeS2 4 119.98 kg FeS2
= 66.55 kg O2
Example
• Sodium nitrite is manufactured based on the reaction represented
by the following chemical equation:
Na2CO3(s) + 2NO(g) + ½ O2(g) → 2 NaNO2(s) + CO2(g)
The Na2CO3 used is first dissolved in water to form a 40% solution.
The NO and O2 used are 10% in excess of the theoretical requirement
and the reaction is 90% complete. On a basis of 100 kg of Na2CO3,
calculate:
a) The mass of NaNO2 obtained
b) The composition of the resulting solution (in mass percent)
c) The composition of the issuing gas (in mole percent)
Use MW: Na2CO3= 105.99, NO = 30.01, O2 = 32.00, NaNO2 = 69.00
• Basis: 100 kg of Na2CO3
• Process Flowchart
𝑛𝑂2 mol (10% excess)
0
𝑛𝑁𝑂 0 mol (10% excess)

100 kg Na2CO3 𝑛𝑂2 mol

40% Na2CO3 Reactor 𝑛𝑁𝑂 mol
60% H2O
𝑛𝐶𝑂2 mol

mNa2CO3 kg
mNaNO2 kg
mH2O kg
• Using % conversion of Na2CO3, the mass of NaNO2 formed can be
calculated:
2 69.00 kg NaNO2
mNaNO2 = 0.9 100 kg Na2 CO3 = 117.2 kg
105.99 kg Na2 CO3
The amount of unreacted Na2CO3 is calculated as follows:
mNa2CO3 = 1 − 0.9 100 kg Na2 CO3 = 10 kg Na2 CO3
The amount of H2O in the solution is calculated as follows:
60 kg H2 O
mH2 O = 100 kg Na2 CO3 = 150 kg
40 kg Na2 CO3
The composition of the resulting solution is summarized as follows:

Component kg Mass %
NaNO3 117.17 42.28
Na2CO3 10 3.61
H2O 150 54.11
Total 277.3 100
• Assuming complete conversion of Na2CO3, the stoichiometric amount of
O2 and NO required are calculated as follows:
1 kmol Na2 CO3 0.5 kmol O2
nO2 = 100 kg Na2 CO3
stoich 105.99 kg Na2 CO3 1 kmol Na2 CO3
nO2 = 0.472 kmol O2
stoich
1 kmol Na2 CO3 2 kmol NO
nNO stoich = 100 kg Na2 CO3
105.99 kg Na2 CO3 1 kmol Na2 CO3
nNO stoich = 1.887 kmol NO
Using the 10% fractional excess, the amount of influent gas can be
calculated:
nO2 = 1.1 nO2 = 1.1 0.472 = 0.519 kmol O2
0 stoich
nNO 0 = 1.1 nNO stoich = 1.1 1.887 = 2.076 kmol NO
• Based on 90% conversion, the amount of O2 and NO consumed
are calculated as follows:
1 kmol Na2 CO3 0.5 kmol O2
nO2 = 90 kg Na2 CO3
reacted 105.99 kg Na2 CO3 1 kmol Na2 CO3
nO2 = 0.424 kmol O2
reacted
1 kmol Na2 CO3 2 kmol 𝑁𝑂
nNO reacted= 90 kg Na2 CO3
105.99 kg Na2 CO3 1 kmol Na2 CO3
𝑛𝑁𝑂 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 1.698 kmol NO
The amount of O2 and NO in the product stream are calculated
from the difference of the initial amount and the amount reacted:
nO2 = 0.519 − 0.424 = 0.095 kmol O2
nNO = 2.076 − 1.698 = 0.378 kmol NO
The amount of CO2 produced is calculated as follows:
1 kmol Na2 CO3 1 kmol CO2
nCO2 = 90 kg Na2 CO3
105.99 kg Na2 CO3 1 kmol Na2 CO3
nCO2 = 0.849 kmol

The following table summarizes the composition of the issuing

gas:
Component kmol Mole %
NO 0.378 28.79
O2 0.095 6.82
CO2 0.849 64.39
Total 1.322 100
Multiple Reactions
• In most industrial reactors, other reactions called side reactions
other than the main reaction typically occur. This reduces the
amount of desired product from the reactor effluent.
Example: In the production of ethylene via dehydrogenation of
ethane (main reaction):
C2 H6 → C2 H4 + H2
Other side reactions such as the reaction of ethane with hydrogen
to produce methane can occur:
C2 H6 + H2 → 2CH4
Ethylene can also react with ethane to form propylene and
methane.
C2 H4 + C2 H6 → C3 H6 + CH4
Yield and Selectivity
• The selectivity is the ratio of the moles of the desired product
formed to the moles of an undesired or by-product produced in
a reaction or a group of reactions.
• The yield is the ratio of the moles of the desired product formed
in an actual reaction to the moles of the desired product that
would have been formed if the limiting reactant is consumed
completely.
• Both yield and selectivity are used to determine the degree at
which a desired reaction proceeds relative to competing side
reactions.
Multiple reactions

• The concept of extent of reactions can be extended to multiple

reactions with each independent reaction having its own extent.
In a batch or continuous steady-state reactor, the amount of
substance i in the reactor is given by:

ni = ni0 + ෍ vij ξj
j
Multiple reactions
• Example: Consider the pair of reactions in which ethylene is oxidized to
either ethylene oxide (desired) or to carbon dioxide (undesired):
1
C2 H4 + O2 → C2 H4 O
2
C2 H4 + 3O2 → 2CO2 + 2H2 O
The moles (or molar flow) of each species can be expressed as follows:
𝑛𝐶2 𝐻4 = 𝑛𝐶2 𝐻4 − ξ1 − ξ2
0
nO2 = n𝑂2 − 0.5ξ1 − ξ2
0
nC2 H4 O = nC2 H4 O + ξ1
0
nCO2 = nCO2 + 2ξ2
0
nH2 O = nH2 O + 2ξ
0
Example

• The reactions
Reaction 1: C2 H6 → C2 H4 + H2
Reaction 2: C2 H6 + H2 → 2CH4
take place in a continuous reactor at steady state. The feed
contains 85.0 mole% ethane (C2H6) and the balance inerts (I). The
fractional conversion of ethane is 0.501, and the fractional yield of
ethylene is 0.471. Calculate the molar composition of the product
gas the selectivity of ethylene to methane production.
• Assumption: steady-state operation
• Basis: 100 mole of feed
• Process Flowchart:

nout mol
100 mole nC2H6 mol
85.0% C2H6
REACTOR nC2H4 mol
15.0% I
nH2 mol
nCH4 mol
nI mol
• The outlet component amount in terms of extents of reaction are
as follows:
nC2H6 = 85 − ξ1 − ξ2
nC2 H4 = ξ1
nH2 = ξ1 − ξ2
nCH4 = 2ξ2
nI = 15 mol
Using the fractional conversion of ethane:
nC2 H4 − nC2 H6 85 − nC2 H6
0
f= = 0.501 =
nC2 H6 85
0
nC2 H6 = 42.4 = 85 − ξ1 − ξ2
• Using ethylene yield:
nC2 H4 nC2 H4
Yield = = 0.471 =
nC2 H4 1 mol C2 H4
max 85 mol C2 H6
1 mol C2 H6
nC2H4 = 40.0 mol C2 H4 = ξ1
Substituting ξ1 to the equation obtained from ethane conversion:
42.4 = 85 − ξ1 − ξ2 = 85 − 40 − ξ2
ξ2 = 2.6 mol
Getting the amount of the other components and the total product:
𝑛𝐻2 = ξ1 − ξ2 = 37.4 mol H2
nCH4 = 2ξ2 = 5.2 mol CH4

nout = 42.4 + 40.0 + 37.4 + 5.2 + 15.0 = 140.0 mol

• Calculating the composition of the product gas
42.4
% C2 H6 = x100 = 30.3%
140
40.0
% C2 H4 = x100 = 28.6%
140
37.4
% H2 = x100 = 26.7%
140
5.2
% CH4 = x100 = 3.7
140
15
%I= x100 = 10.7%
140

• Calculating ethylene-to-methane selectivity:

40 mol C2 H4
Selectivity = = 7.7
5.2 mol CH4
Methods of solving material balances on
reactive systems

• Extent of reactions
• Molecular species balances
• Atomic species balances
Molecular species balances
• Can be written for each species involved in a reactive system.
• Based on the general balance equation for each component in a
reactive system.
Accumulation of
component i in the = Input of component i – Output of component I
in the system in the system
system
Generation of component i Consumption of component i
+ – by the reaction(s)
by the reaction(s)

• This method is generally preferred only for single reaction systems.

Multiple reaction system solutions using this method is usually more
complicated compared to the other methods.
Molecular species balances
• Example
The dehydrogenation of ethane occurs in a steady-state
continuous reactor. The reaction is
C2 H6 → C2 H4 + H2
One hundred kmol/min of ethane is fed to the reactor. The molar
flow rate of H2 in the product stream is 40 kmol. Determine the
flow rates of ethylene and ethane in the effluent stream.
40 kmol H2
100 kmol/min nC2H6 kmol
Reactor nC2H4 kmol
100% C2H6
• Assumption: steady-state operation
• Basis: 1 min of operation (100 kmol of feed)
H2 balance: generation = output
kmol H2 generated kmol H2
= 40
min min
C2H6 balance: input = output + consumption
kmol C2 H6 kmol H2 1 kmol C2 H6
100 = nC2 H6 + 40
min min 1 kmol H2
kmol C2 H6
nC2 H6 = 60
min
C2H4 balance: generation = output
kmol H2 1 kmol C2 H4
40 = nC2 H4
min 1 kmol H2
kmol C2 H4
nC2 H4 = 40
min
Atomic species balances
• Can be written for each atomic species (C, H, O, etc.) involved in
a reactive process
• All balances on atomic species take the form input = output
since atomic species can neither be generated nor consumed in
chemical reactions.
Atomic species balance: Single reaction

• The dehydrogenation of ethane occurs in a steady-state

continuous reactor. The reaction is
C2 H6 → C2 H4 + H2
One hundred kmol/min of ethane is fed to the reactor. The
molar flow rate of H2 in the product stream. Determine the
flow rates of ethylene and ethane in the effluent stream.

100 kmol/min 40 kmol H2

Reactor 60C2H6 kmol
C2H6
40C2H4 kmol
• Assumption: steady-state operation
• Basis: 1 min of operation (100 kmol of feed)
C balance: input = output
kmol C2 H6 2 kmol C
100
min 1 kmol C2 H6
2 kmol C 2 kmol C
= nC2 H6 + nC2 H4
1 kmol C2 H6 1 kmol C2 H4
H balance: input = output
kmol C2 H6 6 kmol H
100
min 1 kmol C2 H6
6 kmol H 4 kmol H
= nC2 H6 + nC2 H4
1 kmol C2 H6 1 kmol C2 H4
Solve the system of equations simultaneously for nC2 H6 and nC2 H4 :
kmol C2 H6 kmol C2 H4
nC2 H6 = 60 nC2 H4 = 40
min min
Atomic species balance: Multiple reaction

• Methane is burned with air in a continuous steady-state

combustion reactor to yield a mixture of carbon monoxide,
carbon dioxide, and water. The reactions taking place are
3
CH4 + O2 → CO + 2H2 O
2
CH4 + 2O2 → CO2 + 2H2 O
The feed to the reactor contains 7.80 mole% CH4, 19.4% O2 and
72.8% N2. The percentage conversion of methane is 90.0% and the
gas leaving the reactor contains 8 mole CO/mole CO2. Calculate
the molar composition of the product stream using atomic species
balances.
• Assumptions: (1) steady-state operation
• Basis: 100 moles of feed
• Process Flowchart

nCH4 mol
100 mol nCO mol
7.80% CH4 Reactor
nCO2 = 8nCO mol
19.4% O2
nH2O mol
72.8% N2
nO2 mol
nN2 mol
Using the 90% CH4 conversion:
nCH4 − nCH4 7.80 − nCH
0 4
0.90 = =
nCH4 7.80
0
nCH4 = 0.78 mol CH4
No nitrogen was involved in the reaction. Thus, the amount entering
the reactor must be equal to the amount exiting.
nN2 = 72.8 mol N2
C balance: in = out
1 mol C
7.8 mol CH4
1 mol CH4
1 mol C 1 mol C 1 mol C
= 0.78 mol CH4 + nCO + nCO2
1 mol CH4 1 mol CO 1 mol CO2
Solving: nCO = 0.780 mol CO
nCO2 = 8nCO = 8 0.780 = 6.24 mol CO2
 nC𝐻4 = 7.80 mol CO
nCO = 0.780 mol CO
nCO2 = 6.24 mol CO2
H balance: in = out H in CH4 = H in CH4 unreacted + H in H20
4 mol H 4 mol H 2 mol H
7.80 mol CH4 = 0.78 mol CH4 + nH2 O
1 mol CH4 1 mol CH4 1 mol H2 O
nH2O = 14.0 mol H2 O
O balance: in = out
2 mol O
19.4 mol O2
1 mol O2
2 mol O 1 mol O 2 mol O
= nO2 + 0.78 mol CO + 6.24 mol CO2
1 mol O2 1 mol CO 1 mol CO2
1 mol O
+ 14 mol H2 O
1 mol H2 O
nO2 = 5.75 mol O2
Reactive Processes with Product Separation
and Recycle
• Recycle stream refer to a process stream wherein part of the material from the
downstream of a process unit is returned and mixed with the fresh feed entering
the process unit.
• Purpose of using a recycle stream
(1) Recovery and re-use of unconsumed reactants
(2) Recovery of catalysts
(3) Dilution of a process stream
(4) Control of a process variable
(5) Circulation of a working fluid
Reactive Processes with Product Separation
and Recycle

PRODUCT
REACTOR SEPARATION
UNIT
Reactive Processes with Product Separation
and Recycle
• Two definitions of reactant conversion are used in the analysis of chemical reactors with
product separation and recycle of unconsumed reactants:

𝐎𝐯𝐞𝐫𝐚𝐥𝐥 𝐜𝐨𝐧𝐯𝐞𝐫𝐬𝐢𝐨𝐧
reactant input to process − reactant output from process
=
reactant input to process

𝐒𝐢𝐧𝐠𝐥𝐞 − 𝐩𝐚𝐬𝐬 𝐜𝐨𝐧𝐯𝐞𝐫𝐬𝐢𝐨𝐧

reactant input to reactor − reactant output from reactor
=
reactant input to reactor
Reactive Processes with Product Separation
and Recycle
• Example: Consider a chemical process with reaction A → B

25 mol A/min PRODUCT 75 mol B/min

75 mol A/min 100 mol A/min
REACTOR SEPARATION
75 mol B/min UNIT

25 mol A/min
Reactive Processes with Product Separation
and Recycle

(75 mol A/min − 0 mol A/min)

𝐎𝐯𝐞𝐫𝐚𝐥𝐥 𝐜𝐨𝐧𝐯𝐞𝐫𝐬𝐢𝐨𝐧 = = 100%
75 mol A/min

(100 mol A/min − 0 mol A/min)

𝐒𝐢𝐧𝐠𝐥𝐞 − 𝐩𝐚𝐬𝐬 𝐜𝐨𝐧𝐯𝐞𝐫𝐬𝐢𝐨𝐧 = = 75%
75 mol A/min
Example
• Propane is dehydrogenated to form propylene in a catalytic
reactor according to the following chemical equation:
C3 H8 → C3 H6 + H2
The process is to be designed for a 95% overall conversion of
propane. The reaction products are separated into two streams;
the first which contains H2, C3H6, and 0.555% of the propane that
leaves the reactor is taken off as product; the second stream which
contains the balance of the unreacted propane and 5% of the
propylene in the first stream, is recycled to the reactor. Calculate
the composition of the product, the recycle ratio, and the single-
pass conversion.
 • Assumption: (1) steady-state operation
• Basis: 100 moles of fresh feed

Fresh feed
100 mol C3H8
PRODUCT
REACTOR SEPARATION
n1 mol C3H8 n3 mol C3H8 n6 mol C3H8 (0.555% of n3)
n2 mol C3H6 n4 mol C3H6 UNIT n7 mol C3H6
n5 mol H2 n8 mol H2

n9 mol C3H8
n10 mol C3H6(5% of n7)
Using 95% overall conversion of C3H8 (5% unconverted):
n6 = 0.05 100 mol = 5 mol C3 H8
Overall C balance:
3 mol C 3 mol C 3 mol C
100 mol C3 H8 = n6 + n7
1 mol C3 H8 1 mol C3 H8 1 mol C3 H6
Substituting n6:
n7 = 95 mol C3 H6
Overall H balance:
8 mol H 8 mol H 6 mol H 2 mol H
100 mol C3 H8 = n6 + n7 + n8
1 mol C3 H8 1 mol C3 H8 1 mol C3 H6 1 mol H2
Substituting n6 and n7:
n8 = 95 mol H2
Based on the computed values of n6, n7, and n8, the composition of product is:
2.6 mole % C3 H8 , 48.7 mole% C3 H6 , 48.7% H2
Relations among Separator Variables
n6 = 0.00555n3
n3 = 900 mol C3 H8

n10 = 0.0500n7
n10 = 4.75 mol C3 H6
Propane Balance around the Separator
n3 = n6 + n9
n9 = 895 mol C3 H8
Propane Balance around the Mixing Point
100 + n9 = n1
n1 = 995 mol C3 H8
Recycle ratio
n9 + n10 895 + 4.75
Recycle ratio = = = 9.00
100 100

Single-pass conversion
n1 − n3 995 − 900
Single − pass conversion = x100 = x100 = 9.6%
n1 995
CHEMICAL ENGINEERING
CALCULATIONS
Multiphase systems
Phase
• A phase of a substance is a form of matter that is uniform
throughout in chemical composition and physical state, and is
separated from other phase by a distinct physical boundary. The
physical state can be solid, liquid, gas, etc.

a) Consider the following system on a closed

Air container at 1 bar and 25oC, enclosing a two-
layer liquid of oil and water, and air un-
evacuated air above both layers. How many
phases are present in the described system?
Oil b) Suppose salt is dissolved in the water layer of
the given system, how many phases would be
Water there?
Phase diagrams
• At most temperatures and pressures, a single pure substance at
equilibrium exists as a solid, liquid or gas; but at certain
temperatures and pressures, two and even all three phases may
coexist.
• A phase diagram of a pure substance shows its physical state at
different conditions.
• The most phase diagram is a pressure-temperature (P-T)
diagram which illustrates the phase(s) of a substance at various
combinations of pressure and temperature.
Phase diagrams

• The follow phase diagram displays

the regions of pressure and
temperature at which various phases
of a substance are
thermodynamically stable.
• The regions are separated by lines
called phase boundaries; showing
the values of pressure and
temperature at which two (or more)
phases coexist in equilibrium.
 Phase diagrams
melting • The spontaneous conversion of a
substance from one phase to
another is called phase
freezing transition/change.
vaporization • Phase changes:
condensation (1) Melting: solid → liquid
(2) Freezing: liquid → solid
sublimation (3) Vaporization: liquid → vapor
(4) Condensation: vapor → liquid
deposition
(5) Sublimation: solid → vapor
(6) Deposition: vapor → solid
 Phase diagrams
melting
• The transition temperature (at a
given pressure) is the temperature at
which given phases are in
freezing equilibrium.
vaporization • The melting/freezing point at a
condensation given pressure is the temperature at
which the solid phase of a
substance is in equilibrium with its
sublimation liquid phase.
• The melting point at 1 atm is called
deposition the normal melting point.
 Phase diagrams
melting
• The boiling point at a given pressure
is the temperature at which the
liquid phase of a substance is in
freezing equilibrium with its vapor phase.
vaporization • The boiling point at 1 atm is called
condensation the normal boiling point.
• The sublimation point at a given
pressure is the temperature at which
sublimation the solid phase of a substance is in
equilibrium with its vapor phase.
deposition
 Phase diagrams

melting • At the triple point, the solid, liquid,

and vapor phases of a substance
coexist in equilibrium.
freezing
• The vapor-liquid phase boundary
vaporization terminates at the critical point. The
condensation temperature at this point is referred
to as the critical temperature and
the pressure is referred to as the
sublimation critical pressure.
• Above the critical point, the liquid
deposition phase of a substance cannot exist.
Critical point
• Consider a liquid heated in a rigid closed,
vessel. As the temperature increases, the
density of the vapor phase increases and
the density of the liquid phase decreases.
No boiling occurs.
• Gradually, the density of the liquid and
vapor phases are equal and the phase
boundary disappears. The substance in the
container has reach its critical point.
• Above the critical point, the substance
exists as a non-condensable gas.
Vapor Pressure

• Consider a system containing only liquid

water in a sealed container at a temperature
T. Initially, the partial pressure of water in
the space above the container is zero.
• Gradually, the partial pressure of water in the
container rises as water molecules enter the
vapor phase (evaporation). At the same time,
some vapor molecules condense back into
the liquid phase.
Vapor Pressure

• Eventually, the rates of condensation equals

the rate of evaporation. The system is said to
have reach phase equilibrium.
• The partial pressure of water at phase
equilibrium is referred to as the vapor
pressure of water at the system
temperature.
• The vapor pressure is a measure of the
volatility of a species, the degree at which
the species tend to transfer from the liquid
phase to the vapor phase.
Antoine equation
• The Antoine equation is an empirical equation that relates the
vapor pressure of substances as a function of temperature.
Various forms of the Antoine equation are listed as follows:

sat
B
log10 P mmHg = A − o
T( C) + C

sat
B
ln P (kPa) = A −
T(K) + C
Exercises

a) What is the vapor

pressure of acetone at
25oC?
b) What is the boiling point
of n-butanol at 1 atm?
Gibb’s Phase Rule

• The degree of freedom of a system in equilibrium is the

number of intensive variables that need be specified to
completely define a system.
• For a non-reacting system in equilibrium, the Gibb’s phase rule
gives the number of degrees of freedom for a system in
equilibrium.
F=2−P+N
where F: degrees of freedom
P: number of phases in a system at equilibrium
N: number of chemical species at equilibrium
Example
• Determine the degrees of feed for each of the following system at
equilibrium:
(1) Pure liquid water
F=2–P+N=2–1+1=2
(2) Water at its triple point
F=2–P+N=2–3+1=0
(3) A vapor-liquid mixture of methanol and water
F=2–P+N=2–2+2=2
Vapor-liquid Mixtures (Volatile components)

• Consider a liquid and vapor phases in a

closed container with each phase containing
components A and B, both of which are
volatile.
• Liquid molecules are continually vaporizing
and vapor molecules are continually
condensing. Initially, the rates of evaporation
and condensation are different.

Question: When is equilibrium achieved?

Vapor-liquid Mixtures (Volatile components)
• Equilibrium is achieved in the closed system
when the following conditions are met:
(1) Thermal equilibrium
Heat transfer between the two phases stops and
the temperature of the two phases are equal.
(2) Mechanical equilibrium
Forces between the vapor and liquid phases are
balanced and the pressure in the liquid and vapor
phase are equal.
(3) Phase equilibrium
Rates of evaporation is equal to the rates of
composition. There is no microscopic change in
the composition of both phases.
Vapor-liquid Mixtures (Volatile components)

• Consider a mixture of methanol (64.7oC) and

water (100oC) in a container at 1 bar and 25oC.
At this condition, the mixture is a subcooled
liquid.
• The liquid mixture is heated slowly at constant
Subcooled liquid Saturated liquid pressure. At some point, the first vapor bubble
(T < Tbubble) (T = Tbubble) forms. This is called the bubble point. The
temperature of the mixture at the bubble point
is called the bubble point temperature. At
this point, the mixture is a saturated liquid.
 Vapor-liquid Mixtures (Volatile components)
• Continuous heating of the mixture at constant
pressure results to a two-phase (vapor-liquid)
Saturated vapor mixture in equilibrium.
(T = Tdew)
• When the last drop of liquid vaporizes, the
Two phase mixture reaches its dew point. The
(Tbubble < T < Tdew)
temperature at which the dew point occurs is
called the dew point temperature. At this
point, the mixture is a saturated vapor.
Superheated • Heating the mixture above the dew point
vapor results to a superheated vapor.
(T > Tdew)
T-x-y diagram
• A T-x-y diagram is a phase diagram illustrating
the composition of the liquid and(or) vapor
phases of a mixture at various temperatures
on a constant pressure.
• Bubble curve (Tbubble vs. x, blue curve)
Below bubble curve – subcooled liquid
Within bubble curve – saturated liquid
• Dew curve (Tbubble vs. y, blue curve)
Above dew curve – superheated vapor
Within dew curve – saturated vapor
Between bubble curve and dew curve – two
phase region
T-x-y diagram
• How do you determine vapor and liquid
compositions for a two-phase mixture in
the T-x-y diagram?
Create a horizontal tie line to the bubble
curve and the dew curve. Projecting
vertically the intersection of the tie line
with the bubble curve gives the liquid
composition. Projecting vertically the
intersection of the tie line with the dew
curve gives the vapor composition.

x y
Vapor mixture (volatile components)

• Consider a vapor-liquid mixture of

methanol and water at 0.800 bar in a
piston-cylinder assembly. At this
Superheated
Saturated vapor condition, the mixture is a superheated
vapor vapor.
(P = Pdew)
(P > Pdew)
• The mixture is compressed at constant
temperature. Once the dew point is
reached, the first drop of liquid condenses
from the mixture. The pressure at which
this occurs is called the dew point
pressure At this point, the mixture is a
saturated vapor.
 Vapor mixture (volatile components)

• Further compression of the mixture results

to a two-phase (vapor-liquid) mixture in
Two-phase Saturated liquid
equilibrium.
(Pbubble >P > Pdew) (P = Pbubble)
• Once the bubble point of the mixture is
reached, the last drop of liquid condenses
from the vapor phase. The pressure at
which this occurs is called the bubble
point pressure of the mixture. At this
point, the mixture is a saturated liquid.
• Further compression of the liquid above
Subcooled liquid
(P > Pbubble)
the bubble point pressure results to
subcooled liquid mixture.
P-x-y diagram
• A P-x-y diagram is a phase diagram
illustrating the composition of the liquid
and(or) vapor phases of a mixture at
various pressures on a constant
temperature.
• Bubble curve (P vs x, blue curve)
Above the bubble curve – subcooled
liquid
Within the bubble curve – saturated liquid
• Dew curve (P vs y, red curve)
Below the dew curve – superheated vapor
Within the dew curve – saturated vapor
Between the bubble curve and dew curve
– two phase region
Raoult’s Law
Question: How do we described compositions in the liquid and vapor phase of
the system in equilibrium?
• Certain models are used to describe the composition of the vapor and liquid
phases for a system in equilibrium.
• One of the most simple of these models for vapor-liquid equilibrium is Raoult’s
law which is based on the assumption that the vapor phase is an ideal gas and
the liquid phase is an ideal solution.
yi P = xi Pisat
where xi: mole fraction of species i in the liquid phase
yi: mole fraction of species i in the vapor phase
P: total pressure of the vapor phase
Pisat: vapor pressure of species i at temperature T of the system
Raoult’s Law
Bubble point calculations
• The composition of the liquid phase is known, with the pressure or temperature
of the system.
• Bubble point pressure: Calculate yi and P, given xi and T.
• Bubble point temperature: Calculate yi and T, given xi and P.

yi P = xi Pisat
xi Pisat
yi =
P
Taking the summation of both sides of the equation.
P = ෍ xi Pisat
i
Example
• What is the bubble point pressure of a liquid mixture consisting of 10 mole%
propane, 10% n-butane, 30% n-pentane 10% n-hexane, and 40% n-octane at 10oC?
At 10oC, the vapor pressure of the components are (using Antoine equation):
Propane: 4600 mmHg
n-butane: 1000 mmHg
n-pentane: 250 mmHg
n-hexane: 68 mmHg
n-octane: 5.5 mmHg
P = ෍ xi Pisat = 600 0.1 + 1000 0.1 + 250 0.3 + 68 0.1 + 5.5 0.5
i
P = 644 mmHg
Raoult’s Law
Dew point calculations
• The composition of the vapor phase is known, with the pressure or temperature
of the system.
• Dew point pressure: Calculate xi and P, given yi and T.
• Dew point temperature: Calculate xi and T, given yi and P.

yi P = xi Pisat
yi P
sat = x i
Pi
Taking the summation of both sides of the equation.
1
P= yi
σi sat
Pi
Example
• What is the dew point pressure of a vapor mixture consisting of 10 mole%
propane, 10% n-butane, 30% n-pentane 10% n-hexane, and 40% n-octane at
10oC?
At 10oC, the vapor pressure of the components are (using Antoine equation):
Propane: 4600 mmHg
n-butane: 1000 mmHg
n-pentane: 250 mmHg
n-hexane: 68 mmHg
n-octane: 5.5 mmHg
1 1
P= yi = 0.10 = 13 mmHg
σi sat 0.10 0.30 0.10 0.40
Pi + + + +
4600 1000 250 68 5.5
Raoult’s Law
Flash calculation
• A liquid mixture feed is charged into a flash drum after decreasing its pressure,
resulting to the formation of a two-phase (vapor-liquid) product in equilibrium.

Vapor product V
yi

Feed F Flash
zi drum

Liquid product L
xi
 Example
• A liquid mixture consists of 65 mole% n-pentane (1) and 35% n-
hexane (2). It is place in a closed container and heated to 100oC
and pressure of 4 atm. What is the resulting composition of the
vapor and liquid phase in equilibrium? What percent of the original
liquid is vaporized?
Basis: 100 moles of liquid feed Vapor product V
y1, y2

Feed F T = 100oC
z1 = 0.65 P = 4 atm
z2 = 0.35
Liquid product L
x1, x2
• Overall mole balance:
100 = V + L
• n-pentane mole balance:
0.65 100 = y1 V + x1 L
The vapor pressures of the n-pentane and n-hexane at 100oC are calculated
using the Antoine equation:
P1sat = 4700 mmHg
P2sat = 1700 mmHg
The compositions of n-pentane and n-hexane are expressed using Raoult’s law:
x1 P1sat 4760
y1 = = x1
P 4(760)
sat
x2 P2 1700
y2 = = x1
P 4(760)
• The composition of the vapor and liquid phases are related as follows:
x1 + x2 = 1
y1 + y2 = 1
Substituting the equations obtained from Raoult’s law:
4700 1700
x1 + x2 = 1
3040 3040

4700 1700
x1 + (1 − x1 ) = 1
3040 3040
Solving
𝑥1 = 0.4467, 𝑥2 = 0.55333
Substituting to the equations obtained from Raoult’s law:
y1 = 0.6906, y2 = 0.3094
• From the n-pentane balance
0.65 100 = 0.6906V + 0.4467(100 − V)

V = 83.36 moles
L = 16.63 moles

Calculating the percent of the liquid feed that vaporizes:

V 83.36
% vaporized = = x100 = 83.36%
F 100
Vapor-liquid Mixtures: with Condensable and
Non-condensable Component
• Systems containing several components, of which only one is
capable of existing as liquid are common in industrial processes.
• Separation processes such as evaporation, drying, and
humidification involves the transfer of liquid into gas phase.
• Separation processes such as condensation and dehumidification
involves the transfer of the condensable species from the gas to the
liquid phase.
• The most commonly encountered system with one condensable
component and one non-condensable component is the air-water
system.
Vapor-liquid Mixtures: with Condensable and
Non-condensable Component
• Consider a chamber initially containing dry
air and the temperature and pressure of the
Air + water vapor system is kept constant at 75oC and 1 atm.
• Liquid water is introduced to the chamber.
Initially, the gas phase contains no water.
Thus, the partial pressure of water is in the
Water chamber is initially zero.
• Gradually, water molecules evaporate and
the partial pressure of the water in the gas
phase increases.
Vapor-liquid Mixtures: with Condensable and
Non-condensable Component
• Eventually, the increase in the partial
pressure of water in the gas phase stops. At
Air + water vapor this point, the gas phase is said to be
saturated with water vapor – it contains the
maximum amount of water it can hold at the
system temperature and pressure.
Water • The water vapor in the gas phase is a
saturated vapor.
Vapor-liquid Mixtures: with Condensable and
Non-condensable Component
• Raoult’s law can be used to describe vapor-liquid equilibrium for a
system with a single condensable species:

yi P = Pisat

In the air-water system described, the composition (in mole fraction)

of water vapor in the gas phase is given as:
PHsat
2O
yH2 O =
P
Example: Saturation
• Air and liquid water are contained at equilibrium in a closed chamber
at 75oC and 760 mmHg. Calculate the composition of the gas phase.
The vapor pressure of water 75oC can be obtained using Antoine
equation:
PHsat
2O
= 289 mmHg
The mole fraction of water in the gas phase is obtained from Raoult’s
law.
PHsat
2O
289
yH2 O = = = 0.38
P 760

yd.air = 1 − yH2 O = 0.62

Vapor-liquid Mixtures: with Condensable and
Non-condensable Component
• A gas in equilibrium with a liquid must be saturated with the volatile
components of the liquid.
• The partial pressure of a vapor at equilibrium in a gas mixture
containing a single condensable component cannot exceed the
vapor pressure of the pure component at the system temperature.
• Any attempt to increase the partial pressure of the condensable
component in a saturated vapor – either via addition of more vapor
or increasing the total pressure at constant temperature – must lead
to condensation.
Vapor-liquid Mixtures: with Condensable and
Non-condensable Component
• A vapor present in a gas in less than its saturation amount is referred
to as a superheated vapor.
• If a gas containing a single superheated vapor is cooled at constant
pressure, the temperature at which vapor becomes saturated is
referred to as the dew point. The difference between the
temperature of a superheated vapor and the dew point temperature
at its pressure is called the degrees of superheat of the gas.
Example: Condensation
• A stream of air at 100oC and 5260 mmHg contains 10.0% water
by volume. Calculate the percentage of the vapor that
condenses and the final composition of the gas phase if the air
is cooled to 80oC at constant pressure.
Example: Condensation
• A stream of air at 100oC and 5260 mmHg contains 10.0% water
by volume. Calculate the percentage of the vapor that
condenses and the final composition of the gas phase if the air
is cooled to 80oC at constant pressure.

Question: Is the air superheated or saturated with water?

The partial pressure of water in the system is given by:
P = 0.100 5260 = 526 mmHg
The vapor pressure of water at 100oC is 760 mmHg. Since the
partial pressure of water is less than saturation, the air is
superheated.
Using Antoine’s equation, the dew point temperature at the given
pressure is:
Tdew = 90o C
The air has 10oC of superheat.
The air becomes saturated at 90oC. Further cooling must lead to
condensation. Since the products are liquid water in equilibrium
with a gas phase, the gas must remain saturated.
Basis: 100 moles of feed

100 mole n2 mol

10% H2O y mol H2O/mol
90% dry air
Condenser
(1 – y) mol dry air/mol
T = 100oC T = 80oC P = 5260 mmHg
P =5260 mmHg Saturated with H2O

n1 mol H2O
• The outlet air is saturated with water, its water-content can be determined
from Raoult’s law. The vapor pressure of water at 80oC is 355 mmHg.
Therefore
355
y= = 0.0675
5260
Dry air balance around the condenser:
mol dry air
100 mol 0.900 = n2 1 − 0.0675
mol
n2 = 96.5 mol
Total mole balance:
100 = n1 + n2
n2 = 3.5 mol H2 O condensed
Percentage condensation:
3.5 mol H2 O condensed
% condensed = x 100 = 35%
0.100 100 mol H2 O fed
Humidity
• Humidity is used to indicate the concentration of the
condensable species in a gas-vapor mixture. In the air-water
vapor system, humidity is defined as the amount of water present
per unit quantity of dry air.
• The molal humidity is defined as the ratio of the mole of vapor
present per mole of vapor-free gas. Denoting A as the vapor and B
as the non-condensable gas:
nA yA
Y= =
nB 1 − yA
Assuming ideal gas behavior:
PA
Y=
P − PA
Humidity
• The absolute humidity or mass humidity is the mass of vapor
present per unit mass of vapor-free gas. In the air-water vapor
mixture:
′
yA MA PA MA
Y = x = x
1 − yA MB 1 − PA MB
• The molal saturation humidity is the moles of water vapor per
mole of vapor-free gas at saturation.
sat
PA
Y sat =
P − PAsat
Humidity
• The relative humidity is the ratio of the partial pressure exerted
by the vapor pressure to its vapor pressure at the same
temperature, expressed in percentage.
PA
% RH = sat x 100%
PA
• The percentage humidity is the ratio of the molal humidity to the
saturation molal humidity, expressed in percentage.
𝑌
% H = 𝑠𝑎𝑡 𝑥100%
𝑌
Example
• Two hundred grams of steam is injected into a large enclosed
container containing 50 kg of air. If the temperature is 30oC and
pressure is 1.2 atm. Calculate the:
a) Mass humidity
b) Molar humidity
c) Percentage humidity
d) Percent relative humidity
a) Mass humidity
′
mH2O 200 g H2 O g H2 O
Y = = = 0.004
mair 50 1000 g air g air
b) Molal humidity
1 mol H2 O
200 g H2 O mol H2 O
18 g H2 O
Y= = 0.00644
1 mol air mol air
50 1000 g air
29 g air
c) Percentage humidity
At 30oC, the vapor pressure of water is 31.85 mmHg.
sat
sat
PH2 O 31.85
Y = sat = 1.2 760 − 31.85 = 0.036
P − PH2O
Y 0.00644
%H = sat x 100 = x100 = 17.9%
Y 0.036
d) Percent relative humidity
200
PH2O = 18 1.2 760 = 5.84 mmHg
200 50 100
+
18 29
5.84
%RH = x100 = 18.34%
31.85
Wet-bulb temperature
• A porous material like cloth or cotton is
soaked in water and wrapped around the
bulb of a thermometer to form a wick and
thermometer is placed in a stream of flowing
air.
• Evaporation of water from the wick to the air
transfers heat from the bulb causing a drop
in the bulb temperature. The final
temperature of the bulb is called the wet-
bulb temperature Twb.
• This is opposed to the actual temperature of
air as read by the thermometer, called the
dry-bulb temperature Tdb.
Psychrometric chart

• A psychrometric chart or also known as humidity chart is a

graph used to assess the physical and thermodynamic
properties of gas-vapor mixtures at a constant pressure.
• The most common psychrometric chart is that of air-water
system at 1 atm, which is extensively used for analysis of drying,
humidification, and air-conditioning processes.
Example
• Air at 41oC and a relative humidity of 10% is blown to a process
stream. Find
a) Absolute humidity
b) Wet-bulb temperature
c) Dew point temperature
d) Humid volume
e) Calculate the amount of water in 150 m3 of air at these
conditions.
• From the psychrometric chart:
a) Y’ = 0.048 kg H2O/kg dry air
b) Twb = 19oC
c) Tdew = 3oC
d) V = 0.897 m3/kg dry air
e) The amount of water in the humid
air is calculated from the humid
volume and absolute humidity.
3
1 kg air 0.0048 kg H2 O
150 m
0.897 m3 1 kg air
= 0.803 kg H2 O
Applications of Psychrometric Chart to
Material Balances
Application of Psychrometric Chart in Material
Balances
Example
A rotary drier dries a crystalline organic solid. The solid enters with 20% water
and leaves with a water content of 0.3%. Conditioned air is used for drying.
Air at 28oC and 85% RH is first chilled to 10oC and then reheated to 88oC, and
fed to the drier countercurrent with the solids. It goes out of the drier at 40oC dry
bulb and 32oC wet bulb.
a) For every 100 kg of dried product, what volume of fresh air (28oC, 85% RH) is
required?
b) How much water condenses at the chiller?
A rotary drier dries a crystalline organic solid. The solid enters with 20% water
and leaves with a water content of 0.3%. Conditioned air is used for drying.
Air at 28oC and 85% RH is first chilled to 10oC and then reheated to 88oC, and
fed to the drier countercurrent with the solids. It goes out of the drier at 40oC dry
bulb and 32oC wet bulb.
a) For every 100 kg of dried product, what volume of fresh air (28oC, 85% RH) is
required?
b) How much water condenses at the chiller?

1 2 3 4
Tdb = 40oC
Chiller Heater
Tdb =
28oC Tdb = 10oC Tdb = 88oC Twb = 32oC
Drier
85% RH

Solids out 0.3% H2O Solids in 20% H2O

Condensed H2O
• The humidity of air from each specified
conditions were first taken from the
psychrometric chart:
kg H2 O
Y1 = 0.022
kg dry air

kg H2 O
Y2 = Y3 = 0.008
kg dry air

kg H2 O
Y4 = 0.030
kg dry air
 • Basis: 100 kg of dried product
The dry solid and dry air are tie components. The drier can be divided into an upper
and lower part.

Air in Air out

Y3 = 0.008 kg H2O/kg dry air Y4 = 0.030 kg H2O/kg dry air

Water evaporated E
100% H2O
Solids out
Solids in, S kg
100 kg 20% H2O
0.3% H2O

Total balance in lower part:

S = 100 + E
H2O balance in lower part:
0.2 S = 100 0.003 + E
Solving:
S = 124.62 kg, E = 24.62 kg
Air in Air out
Y3 = 0.008 kg H2O/kg dry air Y4 = 0.030 kg H2O/kg dry air

Water evaporated E = 24.62 kg

100% H2O
Solids out
Solids in, S kg
100 kg 20% H2O
0.3% H2O

• The amount of dry air entering the drier is fixed. The mass of dry air fed to the drier is
calculated as follows:
kg dry air
mair = 24.62 kg H2 𝑂 = 1090.91 kg dry air
0.030 − 0.008 kg H2 O
Assuming air to be an ideal gas, the volume of entering fresh air is calculated as follows:
1 kmol 1000 mol m3 − Pa
1090.91 kg 8.314 (28 + 273 K)
nRT 29 kg 1 kmol K − mol
V= =
P 101325 Pa

V = 929 m3
 1 2

Y1 = 0.022 kg dry air/kg H2O Y1 = 0.008 kg dry air/kg H2O

Chiller

Condensed H2O

• The same amount of dry air will pass through the chiller and the
water condensed will depend on the change in humidity.

0.022 − 0.008 kg H2 O
Condensed H2 O = 1090.91 kg dry air
kg dry air
= 15.27 kg H2 O
 CHEMICAL ENGINEERING
CALCULATIONS
Combustion of Gaseous fuels
Combustion
• Combustion is a unit process in which oxidation of a fuel with
oxygen takes place. The process is commonly employed for heat
generation.
• Fuel can either be gaseous, liquid, or solid. Some fuels occur
naturally while the majority are products or by-products of
industrials processes.
Complete combustion
• The complete combustion of a fuel means that all combustible
components are gasified: all carbon (whatever form it may exist in the
fuel) is burned to CO2; all hydrogen is converted to water and all sulfur
to SO2.
• The following reactions are considered for complete combustion:
C + O2 → CO2
1
H2 + O2 → H2 O
2
S + O2 → SO2

• The general combustion of any organic fuel (CwHxOySz) is given by

1 x x
Cw Hx Oy Sz + 2w + + 2z − y O2 → wCO2 + H2 O + zSO2
2 2 2
Theoretical Oxygen and Theoretical Air
• Theoretical oxygen is the stoichiometric amount of oxygen
required for complete combustion of a fuel.
• Theoretical air is the amount of air that contains the exact
amount of theoretical O2. For most calculations, air is assumed to
be 21% by mole O2 and 79% N2. N2 is non-combustible and acts
as diluent to O2 in air.
Example

• Determine the theoretical moles of dry air required for the

combustion of 100 moles of refinery gases containing 6% H2S,
5% H2, 57% C3H8, 2% CO2, and 30% C4H10.
 Approach 1
• Basis: 100 mole of gas
• Write individual reaction of each combustible gas and relate stoichiometric
amount of O2:
H2S + 3/2O2 → SO2 + H2O
1.5 mol O2
6 mol H2 S = 9 mol O2
1 mol H2 S
H2 + 1/2O2 → H2O
0.5 mol O2
5 mol H2 = 2.5 mol O2
1 mol H2
C3H8 + 5O2 → 3CO2 + 4H2O
5 mol O2
57 mol C3 H8 = 285 mol O2
1 mol C3 H8
C4H10 + 13/2O2 → 4CO2 + 5H2O
6,5 mol O2
30 mol H2 = 195 mol O2
1 mol H2
Approach 1
• Add the stoichiometric amounts of O2 from each reaction to get
the theoretical O2. Get the theoretical air from its assumed
composition (21% O2, 79% O2).

Theo O2 = 9 + 2.5 + 285 + 195 = 491.5 mol O2

100 mol air

Theo air = 491.5 mol O2 = 2340.48 mol air
21 mol O2
Approach 2
• Basis: 100 mole of gas
• Break down fuel into corresponding atoms of C, H, S, and O. One
mole of C requires 1 mole of O2, one mole of S requires 1 mole of
O2 and one mole of H require ¼ mole of O2. The total moles of O2
in the fuel is subtracted from the O2 requirements to give the
theoretical O2.
moles of H
Theo O2 = moles of C + moles of S + − moles O2
4
Gas Mole Mole C Mole H Mole S Mole O2

H2S 6 0 12 6 0

H2 5 0 10 0 0

C3H8 57 171 456 0 0

C4H10 30 120 300 0 0

CO2 2 2 0 0 2

Total 100 293 778 6 2

Approach 2

• Using the formula for theoretical air on the given fuel:

778
Theo O2 = 293 + + 6 − 2 = 491.5 mol O2
4
Get the theoretical air from its assumed composition (21% O2,
79% O2).
100 mol air
Theo air = 491.5 mol O2 = 2340.48 mol air
21 mol O2
Excess Air
• In actual practice, theoretical air is not sufficient to get complete
combustion. Excess air is the amount of air supplied over that is
theoretically needed for complete combustion. Excess O2 is the
corresponding amount of O2 in the excess air.

Excess O2 = 𝑆upplied O2 − Theo O2

• Percentage excess air is the ratio of excess O2 over the theoretical O2,
expressed in percentage. It is equivalent to percentage excess O2.

Excess O2 Supplied O2 − Theo O2

% Excess Air = x100 = x100
Theo O2 Theo O2
Example
• One hundred mol/h of butane (C4H10) and 5000 mol/h of air are fed into
a combustion reactor. Calculate the percent excess air.
Basis: 1 hr of operation (100 moles C4H10 and 5000 moles air)
Reaction: C4H10 + 13/2 O2 → 4CO2 + 5H2O

6.5 mol O2 100 mol air

Theo air = 100 mol air = 3095.24 mol air
1 mol C4 H10 21 mol O2
5000 − 3095.24
% excess = x100 = 61.5%
5000
Incomplete combustion

• Incomplete combustion occurs when the carbon is not

completely burnt to CO2, sulfur is not completely burnt to SO2,
and there are unburned combustibles from the fuel. During
incomplete combustion, the following combustion reactions are
also occurring
C + 1/2O2 → CO
S + 3/2O2 → SO3
• Incomplete combustion represent loss of heat from the fuel
since this should have been given off for additional power use
had the fuel been completely burnt.
Gaseous Fuels

• Gaseous fuels of value in commerce include natural

hydrocarbon gases manufactured solely for use as fuels and
gases obtained as by-products of some industries.
• Classification of gaseous fuels
a) Natural gas
b) Manufacture gas
Natural gas

• Natural gas are naturally-occurring gases associated with

petroleum oil deposits, with coal seams or with the decay of
organic matter.
• Common composition of natural gas includes hydrocarbons like
methane, ethane, and propane.
Manufacture gases
■ Manufacture gases are obtained as by- (4) From petroleum and oil
product from industrial processes. shale
(1) From wood – by distillation or carbonization (i) by cracking (refinery
(wood gas) gas)
(2) From peat – by distillation or carbonization (ii) by hydrogenation (oil
(peat gas) gas)
(3) From coal – by carbonization (coal gas) (iii) by water gas reaction
(oil gas)
By gasification:
(iv) by partial oxidation (oil
(i) in air (producer gas) gas)
(ii) in air and steam (water gas) (5) From carbides with water
(acetylene)
(iii) in O2 and steam (Lurgi gas)
(6) From electrolysis of water
By hydrogenation: as by-product of ore reduction (H2 gas)
– (blast furnace gas)
Combustion of gaseous fuel
• Fuel gas enters the combustion chamber and is burned with air
supplied in excess. The product gas leaving the chamber is
called a flue gas or stack gas.
• Composition of flue gas may be reported on a wet or dry basis.

Air

Combustion
chamber
Fuel gas Flue/stack gas
Dry and wet basis

• Gas composition can be reported on a dry or wet basis.

• Composition in wet basis reports the component mole fraction
of each component, including water.
• Composition in dry basis (also referred to as Orsat analysis)
reports the composition mole fraction of each component,
excluding water.
Orsat gas analyzer
• An Orsat gas analyzer is an instrument
used to analyze gas samples for its O2, CO,
and CO2 content.
• The apparatus consists of calibrated water-
jacketed glass burette connected to three
absorption pipettes by glass tubing.
• The absorbents used are:
(1) Potassium hydroxide (for CO2)
(2) Pyrogallol (for O2)
(3) Ammoniacal cuprous chloride (for CO)
Example
• An Orsat analysis yield the following dry basis composition:
Gas Mole percent
N2 65
CO2 14
CO 11
O2 10

A humidity measurement shows that the mole fraction of H2O in the

stack gas is 0.0700. Calculate the stack gas composition on a wet basis.
• Basis: 100 moles of dry gas
mol H2 O mol dry gas
0.0700 → 0.930
mol wet gas mol wet gas
Thus,
0.0700 mol H2 O mol wet gas mol H2 O
= 0.0753
0.930 mol dry gas mol wet gas mol dry gas
Hence the gas in the assumed basis contains:

mol H2 O
100 mol dry gas 0.0753 = 7.53 mol H2 O
mol dry gas
mol N2
100 mol dry gas 0.650 = 65.0 mol N2
mol dry gas
100 0.140 = 14.0 mol CO2
100 0.110 = 11.0 mol CO
100 0.100 = 10.0 mol O2
• Getting the total moles of wet gas:
mol wet gas = 7.53 + 65.0 + 14.0 + 11.0 + 10.0 = 107.5 mol wet gas
The mole fraction of each component in the flue gas is calculated as follows:
7.53
yH 2 O = = 0.070
107.5

65.0
yN2 = = 0.605
107.5

14.0
yCO2 = = 0.130
107.5

11.0
yCO = = 0.102
107.5

10.0
yO2 = = 0.093
107.5
Calculations Based on Fuel Analysis

a) From the complete analysis of the fuel, the theoretical oxygen

and the calorific value can be determined.
b) If data on air (% excess air or amount of air supplied) is given
together with the degree if completion, the following can be
calculated:
(1) Composition analysis (wet or dry basis)
(2) Air-fuel ratio
(3) Stack gas-fuel ratio
Example

• Pure ethane (C2H6) is burned completely in 20% excess air. Air is supplied
at 25oC and 740 mmHg and is substantially dry. Calculate:
a) the Orsat analysis of the flue gas
b) kg dry air supplied/kg of fuel gas
c) m3 of air/kg ethane
d) m3 of flue gases measured at 400oC and 100 kPa/kg ethane
e) partial pressure of water in the flue gas
• Basis: 1 kmol C2H6 (30 kg C2H6)
• Process Flowchart:

Air
20% excess
25oC, 740 mmHg Combustion Flue gas
chamber 400oC, 100 kPa

Fuel gas
1 kmol C2H6

1 kmol O2 1 kmol O2
Theo O2 = 2 kmol C + 6 kmol H = 3.5 kmol O2
1 kmol C 4 kmol H
Supplied O2 = 3.5 1.2 = 4.2 kmol O2
79
Supplied N2 = 4.2 = 15.8 kmol N2
21
Free O2 = Excess O2 = 4.2 − 3.5 = 0.7 kmol O2
1
CO2 formed = 2 = 2 kmol CO2
1
a) Orsat analysis of the flue gas
Gas Moles Mole percent
CO2 2 10.81
O2 0.7 3.78
N2 15.8 85.41
Total 18.5 100.00

b) kg dry air/kg fuel

kg dry air 4.2 + 15.8 29 kg dry air
= = 19.33
kg fuel 30 kg fuel
c) m3 dry air/kg ethane
760 273 + 25
m3 dry air 4.2 + 15.8 22.4 m3 dry air
740 273
= = 16.74
kg ethane 30 kg ethane
d) m3 of flue gases measured at 400oC and 100 kPa/kg ethane
101.325 273 + 400
3
m flue gas 21.5 22.4 m3 flue gas
100 273
= = 40.1
kg ethane 30 kg ethane
e) partial pressure of water in the flue gas
1
mole H2 O = 6 = 3 kmol H2 O
2
3
PH2O = yH2 O P = 100 = 13.953 kPa
18.5 + 3
Example

• Coal gas at 15oC, 760 mmHg and saturated with water vapor is burned in a
furnace. Air with 60% RH is supplied at a rate of 5.7 m3/m3 coal gas and
enters at the same temperature and pressure as the coal gas. The coal gas
analyzes 1.4% CO2, 2.7% C2H2, 0.7% O2, 5.8% CO, 53.2% H2, 29.6% CH4,
and 6.6% N2. The molar ratio of CO2 to CO in the stack gas is 10:1. All the H2
in the fuel is burned to water. The stack gas leaves at 400oC and 100 kPa.
Calculate
a) % excess air
b) Orsat analysis of the stack gas
c) m3 stack gas/m3 of coal gas
• Basis: 10000 m3 coal gas
• Process Flowchart:

Air
m3/m3 coal gas
60% RH
23oC, 758 mmHg Combustion Flue gas
chamber 400oC, 100 kPa

Coal gas
15oC,
760 mmHg (saturated)
1.4% CO2
2.7% C2H2
0.7% O2
5.8% CO
53.2% H2
29.6% CH4
Basis: 10000 m3 coal gas
air volume = 57000 m3
The vapor pressure of water in air at 15oC is calculated from the Antoine
equation:
sat
1668.21
log10 Pw mmHg = 7.96683 −
sat
228 + 15
Pw = 12.64 mmHg

1 760 − 12.64 273

moles dry coal gas = 10000
22.4 760 273 + 15
= 416.14 kmol

12.64
moles H2 O from coal gas = 416.14 = 7.04 kmol H2 O
760
 Gas Mole Mole C Mole H Mole O2
CO2 5.83 0 0 5.82
C2H2 11.24 22.48 22.48 0
O2 2.91 0 0 2.91
CO 24.14 24.14 0 12.07
H2 221.39 0 442.78 0
CH4 123.18 123.18 492.72 0
N2 27.47 0 0 0
Total 100 175.63 957.98 20.81
957.98
Theo O2 = 175.63 + − 20.81 = 394.32 kmol O2
4
1 273
Moles wet air = 57000 = 2412.11 kmol wet air
22.4 273 + 15
760 − 12.64 0.6
Moles dry air = 2412.11 = 2388.04 kmol dry air
760
mol O2 from air = 0.21 2388.04 = 501.49 kmol O2
mol N2 from air = 0.79 2388.04 = 1886.55 kmol N2
mol H2 O from air = 2412.11 − 2388.04 = 24.07 kmol H2 O
a) % excess O2
501.49 − 394.32
% excess = 𝑥100 = 27.18%
394.32

10
mole CO2 formed = 175.63 mol C = 159.66 kmol CO2
11
1
mole CO formed = 175.63 = 15.97 kmol CO
11
15.97
Free O2 = 501.49 − 394.32 + = 115.16 kmol O2
2
moles N2 = 27.47 + 1886.55 = 1914.02 kmol N2
b) Orsat analysis
 Gas Moles (kmol) Mole percent
CO2 159.66 7.24
CO 15.97 0.72
O2 115.16 5.23
N2 1914.02 86.81
Total 2204.81 100.00

957.82
moles H2 O from combustion = = 478.99 kmol H2 O
2

moles H2 O total = 478.99 + 24.07 + 7.04 = 510.1 kmol H2 O

c) m3 stack gas/m3 coal gas

101.325 273 + 400
m3 flue gas 2204.81 + 510.1 22.4 100 273
3
= = 15.19
m coal gas 10000
 Calculations Based on Flue Gas Analysis

a) If the N2 in the fuel is negligible, the N2 in the flue gas may be assumed to be all
coming from air.
mole CO mol H2
b) Excess O2 may be calculated as: Excess O2 = mole free O2 − −
2 2
c) An O2 balance will determine the unaccounted O2. This O2 is used to burn H2 to
water and is not included in the Orsat analysis.
d) When losses of combustible matter such as soot are small, all carbon in the fuel
are accounted for in the stack gas.
e) The net hydrogen is the hydrogen in the fuel that uses O2 from air for combustion.
The net hydrogen is equal to the total hydrogen in the fuel if no O2 is present in the
fuel.
Example

• A pure saturated hydrocarbon (CnH2n+2) is burned with excess air. Orsat

analysis of the products of combustion shows 9.08% CO2, 1.63% CO,
5.28% O2 and no free H2. Calculate:
a) the formula of the hydrocarbon
b) % excess air
c) kg dry air/kg of hydrocarbon
• Basis: 1 kmol flue gas Air Flue gas, 100 kmol
• Process Flowchart: Combustion 9.08% CO2
1.63% CO
chamber 5.28% O2
Fuel gas
CnH2n+2

mol N2 = 100 − 9.08 − 1.63 − 5.28 = 84.01 kmol N2

21
mol O2 from air = 84.01 = 22.33 kmol O2
79
1.63
unaccounted O2 = 22.33 − 9.08 + + 5.28 = 7.16 kmol O2
2
net H2 = H2 in the fuel = 7.16 2 = 14.32 kmol H2
total mol H in the fuel = 14.32 2 = 28.64 kmol H
total mole C in the fuel = 9.08 + 1.63 = 10.71 kmol C
mol C 10.71 n
= =
mol H 28.64 2n + 2

n=3
a) Formula of the hydrocarbon
Since n = 3, the formula of the hydrocarbon is C3H8 (propane).

1.63
Excess O2 = 5.28 − = 4.465 mol O2
2
b) % excess air

4.465
% excess air = x100 = 25%
22.33 − 4.465

c) kg dry air/kg hydrocarbon

kg dry air (84.01 + 22.33)(29)

= = 19.62
kg hydrocarbon 10.71 12 + 28.64
• Basis: 100 moles of dry flue gas
• Process Flowchart:
Air
26oC, 765 mmHg Flue gas (dry basis)
70% RH Combustion 9.82% CO2
1.37% CO
chamber
Fuel gas 0.69% H2
C2H2 5.43% O2
CH4 82.69% N2

21
a) O2 from air = 82.69 = 21.98 mol O2
79
1.37 0.69
Excess O2 = 5.43 − − = 4.4 mol O2
2 2
1.37
Unaccounted O2 = 21.98 − 9.82 + + 5.42 = 6.045 mol O2
2
Net mole H2 burned to H2 O = 6.045 2 = 12.09 mol H2
Total moles H2 in fuel = 12.09 + 0.69 = 12.78 mol H2
Total moles H in fuel = 12.78 2 = 25.56 mol H
Total mole C in fuel = 9.82 + 1.37 = 11.19 mol C
b) Let x = moles C2H2, y = mole CH4
C balance:
2x + y = 11.19
H balance:
2x + 4y = 25.56
Solving these equations simultaneously
x = 3.2 mol C2 H2 , y = 4.79 mol CH4

3.2
% C2 H2 = x100 = 40.05%
3.2 + 4.79

4.79
% CH4 = x100 = 59.95%
3.2 + 4.79
The vapor pressure of water 26oC is calculated from the Antoine equation:
sat
1668.21
log10 Pw mmHg = 7.96681 −
sat
228 + 26
Pw = 25.06 mmHg

25.06(0.7)
moles of H2 O from air = 21.98 + 82.69 = 2.457 moles H2 O
765 − 25.06(0.7)
c) m3 wet air/kg fuel
760 273 + 26
m3 wet air 21.98 + 82.69 + 2.457 22.4
765 273
= = 16.335
kg fuel 4.79 16 + 3.2(26)
Calculations Based on Partial Analysis of
Flue Gas
a) From the complete analysis of the fuel, the theoretical O2 can be
determined: O2 and N2 from air can be expressed in terms of the
theoretical O2 and the unknown excess O2.
b) Carbon is used as a tie substance to relate the fuel with the stack gas.
Example 1

• The burning of pure butane with excess air gives a stack gas which analyzes
11.55% CO2 on a dry basis. Assuming complete combustion, calculate:
a) % excess air
b) Orsat analysis of the stack gas
• Basis: 100 moles C4H10
• Process Flowchart:
Air Combustion Flue gas (dry basis)
chamber 11.55% CO2
Fuel gas
C4H10

1000
Theo O2 = 400 + = 650 mol O2
4
Let x = excess O2
O2 from air = x + 650
79
N2 from air = x + 650
21
Free O2 in flue gas = x
The tie substance is C:
400 = (0.1155)(mol dry flue gas)
mol dry flue gas = 3463.2 mol dry flue gas
Dry flue gas balance:
79
3463.2 = 400 + 𝑥 + 650 + 𝑥
21
𝑥 = 129.77 mol O2
a) % excess O2
129.77
% excess air = 𝑥100 = 19.96%
650
b) Orsat analysis

Gas Moles Mole percent

CO2 400 11.55
O2 129.77 3.75
N2 2933.43 84.70
Total 3463.2 100.00
Example 2

• A gaseous fuel at 22oC, 763 mmHg and saturated with water vapor is burned
with excess air. Air with 60% RH is supplied at the same temperature and
pressure as the fuel. The composition of the fuel shows 9.2% CO2, 0.4%
C2H4, 20.9% CO, 15.6% H2, 1.9% CH4, and 52% N2. The stack gas leaves at
400oC and 735 mmHg and contains 13.6% CO2 and 1.84% CO on a dry basis.
Calculate:
a) % excess air
b) complete analysis of the stack gas
• Basis: 100 kmol of gaseous fuel
• Process Flowchart:
Air
22oC
Combustion Flue gas (dry basis)
chamber 13.16% CO2
Fuel gas 1.84% CO
22oC, 763 mmHg (sat’d) 400oC, 735 mmHg
9.2% CO2
0.4% C2H4
20.9% CO Gas Mole Mole C Mole H Mole O2
15.6% H2
CO2 9.2 9.2 0 9.2
1.9% CH4
52.0% N2 C2H4 0.4 0.8 1.6 0
CO 20.9 20.9 0 10.45
H2 15.6 0 31.2 0
CH4 1.9 1.9 7.6 0
N2 52 0 0 0
Total 100 32.8 40.4 19.65
 Theo O2 = 32.8 + 40.4 − 19.65 = 23.25 mol O2
Let y = excess O2
O2 from air = y + 23.25
79
N2 from air = y + 23.25
21
C balance of dry flue gas:
0.15 mol dry flue gas = 32.8
mol dry flue gas = 218.67 mol
mol CO2 in flue gas = 0.1316 218.67 = 28.77 mol
mol CO in flue gas = 0.0184 218.67 = 4.023 mol
4.023
Free O2 = y +
2
79
mol N2 = 52 + y + 23.25
21
Dry flue gas balance:
4.023 79
218.67 = 28.77 + 4.023 + 𝑦 + + 52 + 𝑦 + 23.25
2 21
𝑦 = 9.324 mol O2
b) % excess air
9.324
% excess air = x100 = 40.1%
23.25

The vapor pressure of water at 22oC is obtained from the equation:

sat
1668.21
log10 Pw mmHg = 7.96681 −
𝑠𝑎𝑡
228 + 22
𝑃𝑤 = 19.6775 mmHg
19.6775
mole H2 O from fuel = 100 = 2.647 mol H2 O
763 − 19.6775
9.324+23.25 19.6775 0.65
mole H2 O from air = = 2.438 mol H2 O
0.21 763− 19.6775 0.65
40.4
H2 O from combustion = = 20.2 mol
2
mol H2 O in flue gas = 20.2 + 2.438 + 2.647 = 25.285 mol H2 O
c) Complete analysis of stack gas

Gas Moles Mole percent

CO2 28.77 11.79
CO 4.023 1.65
O2 11.336 4.64
N2 174.54 71.52
H2O 25.285 10.4
Total 243.954 100.00