CHEE1047

Process Engineering Principles

Lecture 8:

MASS BALANCE
WITH
CHEMICAL REACTION

Component MB’s for Reacting Systems

General MB for any system:

Input + Generation
=
Output + Consumption + Accumulation ... (1)

For a reactant (Gen.=0 ) in a steady-state (Acc.=0 ) system,

Output – Input + Consumption = 0 ...(2)

For a product (Con.=0 ) in a steady-state (Acc.=0 ) system,

Output - Input - Generation = 0 ...(3)

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 Simplification of General MB Using ξ
Recall that:

Rearrange:

Comparing this with Eq(2) and Eq(3)

for steady-state systems:

Moles of cpn i
generated
or consumed
3

Example 1
Consider the following steady-state reaction:
N2 + 3H2 « 2NH3

15 mol N2 12 mol N2
18 mol H2 Reactor 9 mol H2
6 mol NH3

NH3 Balance: Input + Generation = Output + Consumption

Generation = 6 mol

or

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 N2 + 3H2 « 2NH3

15 mol N2 12 mol N2
18 mol H2 Reactor 9 mol H2
6 mol NH3

H2 Balance: Input + Generation = Output + Consumption

Consumption = Input – Output
= 18 – 9 = 9 mol
or

N2 + 3H2 « 2NH3
15 mol N2 12 mol N2
18 mol H2 Reactor 9 mol H2
6 mol NH3

N2 Balance: Input + Generation = Output + Consumption

Consumption = 15 - 12 = 3 mol

or

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 Example 2
The chlorination of methane occurs by the reaction:
CH4 + Cl2 → CH3Cl + HCl
Determine the product composition if the conversion of the
limiting reactant is 67%, and the feed composition is as follows:

Feed, F=100 mol/h Reactor Product, P

40% CH4 67% Conversion CH4 = ?
50% Cl2 Cl2 = ?
10% N2 HCl = ?
CH3Cl = ?
Step 5: Basis: F=100 mol/h
N2 = ?
Step 4: To find the limiting reactant:

limiting reactant
= CH4

CH4 + Cl2 → CH3Cl + HCl ξ=?

Feed, F=100mol/h Product, P =?
40% CH4 Reactor CH4 = ?
67% Conversion
50% Cl2 Cl2 = ?
10% N2 HCl = ?
CH3Cl = ?
N2 = ?

Steps 6&7: DOF

Unknowns : ξ P nCH4,out nCl2,out nHCl,out nCH3Cl,out nN2,out

N=____
Equations:
MB’s = 5 (CH4, Cl2, HCl, CH3Cl, N2 )
DOF=_____
Spec. = 1 (conversion=67%) ➾ A unique
Implicit eqn = 1 (Σni,out=P ) M=____ solution exists

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Steps 8&9: Formulate MB’s in moles and solve

CH4 + Cl2 → CH3Cl + HCl Product, P

F=100 mol/h CH4 = ?
CH4=40 mol/h Reactor Cl2 = ?
67% Conversion HCl = ?
Cl2 = 50 mol/h
N2 = 10 mol/h CH3Cl = ?
N2 = ?

Moles reacted = _____

Fractional conversion of CH4 = ______________
Moles fed

Þ Moles reacted = 0.67 x 40 = ______ mol/h

\ Moles of CH4 unreacted = 40 – 26.8 = ______ mol/h nCH4

out

Chemical equation: CH4 + Cl2 → CH3Cl + HCl

Note the
direct solution

How should
you check the
solution?
Total P = 100 mol/h 10
Systems Involving Multiple Reactions
• In multiple reaction systems, there are the
main reaction which form the
desired products and the
side reactions creating
by-products (undesired)

• Stoichiometry concepts are valid for any

number of reactions occurring in a reactor,
but as the no. of reaction grows, so does
the complexity of the calculation.

• For multiple reactions, use cpn balances

for a set of independent chemical
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reaction equations.

Example 3
Two reactions occur in a process:
C2H6 ® C2H4 + H2 (1)

C2H6 + H 2 ® 2CH4 (2)

The feed is 85 mol% ethane with the

balance being inerts. The conversion of
ethane is 50% and the yield is 47%.

The yield can be taken as the ratio of the

moles of C2H4 produced to the moles of
C2H6 fed to the process.

Determine the composition of the product.

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Solution:
Reactor Product, P=?
Feed, F=?
50% Conversion C2H6 = ?
85% C2H6
47% Yield C2H4 = ?
15% Inerts
CH4 = ?
C2H6 → C2H4 + H2 ξ1 =? H2 = ?
C2H6 + H2 → 2CH4 ξ2 =? Inerts = ?

Step 5: Basis: F=100 mol/h

Steps 6&7: DOF

Unknowns: ξ1 ξ2 F P nC2H6,out nC2H4,out nCH4,out nH2,out nInerts,out

N=___
Equations :
MB’s = 5 (C2H6, C2H4, CH4, H2, Inerts)
Basis = 1 (F=100 mol/h) DOF=____
➾ A unique
Spec. = 2 (conversion=50%, yield=47%)
solution exists
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Implicit eqn = 1 (P = Σni,out) M=___

Steps 8&9: Formulate MB’s and solve

Product, P=?
F=100 mol/h Reactor
50% Conversion C2H6 = ?
C2H6 =85 mol/h 47% Yield C2H4 = ?
Inerts =15 mol/h CH4 = ?
C2H6 → C2H4 + H2 …(1) ξ1 = ? H2 = ?
Inerts = ?
C2H6 + H2 → 2CH4 …(2) ξ2 = ?
Spec. 1: Moles reacted
Fractional conversion = _____________ = 0.50
Moles fed (85 )

Þ Moles of C2H6 reacted = 0.50 x 85 = _____ mol/h

\ Moles of C2H6 unreacted = 85 – 42.5 = _____ mol/h nC2H6

out

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Process Specification 2:

Moles C2H4 produced

Yield = 0.47 = ________________
Moles C2H6 fed (85)

Þ Moles C2H4 produced = 0.47 x 85 = 39.95 =_____mol/h

From reaction (1), C2H6 → C2H4 + H2 …(1) ξ1

40 40 40

Substitute into Eq (3):

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Component balances: C2H6 → C2H4 + H2 …(1) ξ1=40 mol/h

C2H6 + H2 → 2CH4 …(2) ξ2=2.5 mol/h

Composition of P :
30.4% C2H6
28.6% C2H4
26.8% H2
3.6% CH4
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Þ P = 140 mol/h 10.7% Inerts
 Atomic (or Element) Mass Balance
The general MB in terms of the an atom (or element) :

Moles of Moles of Moles of Moles of Moles of

atom i + atom i = atom i + atom i + atom i
Input Generated Output Consumed Accum.

terms involving reaction

How should the reaction terms be handled?
They are zero!
Atoms are neither generated nor consumed.

Atomic balance (in moles):

Atom INPUT = Atom OUTPUT

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Example 4
(Solve Example 2 by Atomic Balances)

Product, P=?
F=100 mol/h
Reactor CH4 = ?
40% CH4 67% Conversion Cl2 = ?
50% Cl2
HCl = ?
10% N2 CH4 + Cl2 → CH3Cl + HCl
CH3Cl = ?
N2 = ?
Basis: F=100 mol/h
Limiting reactant = CH4

Steps 6&7: DOF

Unknowns : P nCH4,out nCl2,out nHCl,out nCH3Cl,out nN2,out
N=___
Equations:
Atomic balances = 4 (C, H, Cl, N ) DOF=___
Specification =1 (conversion = 0.67) ➾ A unique
solution exists18
Implicit eqns =1 (Σni,out=P ) M=___
 Product, P
F=100 mol/h
Reactor CH4 = ?
CH4=40 mol/h
67% Conversion Cl2 = ?
Cl2 = 50 mol/h
HCl = ?
N2 = 10 mol/h
CH4 + Cl2 → CH3Cl + HCl CH3Cl = ?
N2 = ?

Steps 4: Get more data

Moles reacted = 0.67

Fractional conversion of CH4 = ______________
Moles fed (40)

Þ MOLES REACTED = 0.67 x 40 = ______ mol/h

\ Moles of CH4 UNREACTED = 40 – 26.8 = _____ mol/h

nCH4
out
= _____ mol/h 19

Product, P
F=100 mol/h
Reactor CH4 = 13.2 mol/h
40 mol/h CH4
67% Conversion Cl2 = w
50 mol/h Cl2
HCl = x
10 mol/h N2
CH3Cl = y
N2 = z
Steps 8&9: Atomic balances in moles

Atom: Input = Output

y=26.8 mol/h; x=26.8 mol/h; w=23.2 mol/h 20

 Example 5
(Solve Using Atomic Balances)

Consider the following reactions:

CH4 + 4S → CS2 + 2H2S
CH4 + 2S → CS2 + 2H2
CH4 + 2H2S → CS2 + 4H2

For a feed containing 4 mol of S per mol of CH4,

calculate the composition of the product if 90%
conversion of CH4 and 70% conversion of S are
obtained. 10% of the H2S generated by the
first reaction reacts by the third reaction.

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Solution: Feed, F1 = ?
CH4
CH4 = ?
Product, P = ?
S=?
Reactor
Feed, F2 = ? CS2 = ?
S(g) H2S = ?
H2 = ?

Step 5: Basis F1=1 mol/h CH4

Steps 6&7: DOF analysis

Specifications:
Unknowns:
(1) 4 mol S/1 mol CH4
F1 F2 P nCH4 nS nCS2 nH2S nH2 Þ N=____ (2) f = 0.90
CH4

Equations: (3) fS = 0.70

Atomic balances = 3 (C, H, S) (4) 10% rxn H2S
Basis =1 (F=1 mol/h CH4)
Specifications = 3 No.(4) not used as the rxn eqns are not used
Implicit eqn =1 (Σni = P)
M=___
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DOF=_________ . Thus, a unique solution exists
Step 4: Getting data
Specifications:
(1) 4 mol S/1 mol CH4
1. If F1=1 mol/h CH4 so, F2=4x1=4 mol/h
(2) fCH4 = 0.90
(3) fS = 0.70
2. 90% conversion of CH4
(4) 10% rxn H2S
Moles reacted = 0.90
____________
Moles fed (1)

Þ moles of CH4 reacted = 0.9 mol/h

\ moles of CH4 unreacted = 1 - 0.9 = 0.1 mol/h nCH4

out

3. 70% conversion of S

Moles reacted = 0.70

_____________
Moles fed (4)
Þ moles of S reacted = 0.7 x 4 = 2.8 mol/h
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\ moles of S unreacted = 4 – 2.8 = 1.2 mol/h nSout

Find:
CH4 =1 mol/h Product P
Reactor CH4 = 0.10 mol/h
S = 4 mol/h S = 1.20 mol/h
CS2 = x mol/h
H2S = y mol/h
H2 = z mol/h
Steps 8&9: Atomic balances (in moles)

Atom: In = Out

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P=Σni = 0.10 + 1.20 + 0.90 + 1.0 + 0.80 = 4.0 mol/h
 Combustion
Combustion is the reaction of a substance
with oxygen to form product gases
(H2O, CO2, CO, SO2) and energy (heat)

E.g. combustion of coal, heating oil,

natural gas used in electricity generation

E.g. combustion of diesel fuel,

gasoline in engines

AIR is a common source of O2 in combustion processes

Þ composition: 21 % O2 and 79 % N2
Þ average MWT: 28.8 kg/kmol
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Þ N2 is inert

Additional Terms for Combustion

Flue gas: All gaseous combustion products
(stack gas) including the water (wet basis)

Orsat analysis: All gaseous combustion products

excluding the water (dry basis)

Complete combustion: Complete reaction of C, H and S

to CO2, H2O and SO2 , respectively.

Partial combustion: Less than complete combustion.

(Incomplete combustion) C reacts to form CO

Theoretical air (oxygen): Minimum amount of air (oxygen)

required for complete combustion

Excess air (oxygen): Air (oxygen) in excess of that

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required for complete combustion
 Percent Excess Air

Or

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Example 6
40 kg/h of methane and 280 kg/h of oxygen are
reacted to produce water and carbon dioxide.
If methane is completely oxidised, what is the
percent excess of oxygen? Find the molar
composition of the product stream.

Solution:

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 Example 7
Propane is burned with 60% excess air. The conversion
of the propane is 98%. The selectivity between the
CO2 and CO in the products is 5. Calculate the
product flue gas analysis and its Orsat analysis.

Solution:
Air F2
Steps 1 -4:
N2 79%
C3H8 = a
O2 21%
N2 = b
Feed, F1 Product, P
Reactor O2 = c
C3H8
CO2 = d
CO = e
C3H8 + 5O2 → 3CO2 + 4H2O H2O = f
C3H8 + 7/2O2 → 3CO + 4H2O

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Step 5: Basis F1 = 100 mol/h C3H8

Air F2
N2 79% C3H8 = a
Feed, F1 O2 21% N2 = b
C3H8 100% Product, P
O2 = c
Reactor
CO2 = d
CO = e
H2O = f
Steps 6&7: DOF analysis

Unknowns: F1 F2 P a b c d e f N=____

Equations:
Atomic balances = 4 (C, H, O, N)
Basis =1 (F=100 mol/h C3H8 )
Implicit eqn. =1 (P = a + b + c + d + e + f)
Specifications =3 (Excess air=0.6, f=0.98, selectivity nCO2/nCO=5)
M=_____
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DOF=0 Thus, the problem has a unique solution
Steps 4: Spec.(1) 98% conversion of C3H8

Moles reacted
_______________ = 0.98
Moles fed (100)

Þ Moles of C3H8 reacted = 98 mol/h

\ Moles of C3H8 unreacted = 100 - 98 = ____ mol/h a

Spec.(2) 60% excess O2 : C3H8 + 5O2 → 3CO2 + 4H2O

O2 Input – Theoretical O2 (500) = 0.60

Excess O2 = ___________________________
Theoretical O2 (500)

\ O2 Input = 1.6(500) =______ mol/h

Þ N2 Input = 79 (800) = ______ mol/h 31

21

Air F2
Product, P
21% O2=800 mol/h
79% N2=3010 mol/h C3H8 = a =2mol/h
Feed, F1=100mol/h N2 = b =3010mol/h
C3H8 100% Reactor O2 = c
CO2 = d
Steps 8&9: CO = e
H2O = f
Atom: In = Out
Solve these eqns
C : 3x100 = (3x2) + d + e …(1) in the sequence
of 2, 1+4, 3, 5:
H : 8x100 = (8x2) + 2f …(2)
c = 335 mol/h
O : 2x800 = 2c + 2d + e + f …(3) d = 245 mol/h
e = 49 mol/h
nCO2
Selectivity, = 5 Þ d = 5e …(4) f = 392 mol/h
nCO
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P = 2 + 3010 + c + d + e + f …(5)
 Air nO2 =800 mol/h
nN2 =3010 mol/h

F=100 mol/h
Reactor Product P
C3H8
Wet Basis Dry Basis
mol/h % mol/h %
C3H8 2 0.05 2 0.05
N2 3010 74.6 3010 82.7
O2 335 8.3 335 9.2
CO2 245 6.1 245 6.7
CO 49 1.2 49 1.3
H2O 392 9.7 - -
P 4033 100 3641 100

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Step 10: How to check the results?

Reaction with Recycle

Fractional conversion is defined as:

Moles reacted
Fraction conversion =
Moles fed

For reacting systems with recycle stream,

there are two different types of conversion:

1. Overall Conversion
- based on the overall process
or the fresh feed
2. Single-pass Conversion
- also known as once-through conversion
or reactor conversion
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- based on the reactor feed
 1. Overall Conversion = ________________
Moles reacted
Conversion of the limiting Moles in Fresh Feed
reactant entering the overall
process

Recycle

Fresh Reactor Reactor Overall

Feed Feed Product Products
Reactor Separator

2. Single-pass Conversion Moles reacted

= ___________________
Conversion of the limiting reactant Moles in Reactor Feed
which enters the reactor 35

For illustration:

Recycle 140 mol A

Product
Fresh Reactor 10 mol A
Feed Feed 150 mol A
200 mol A Reactor 50 mol B 50 mol B
60 mol A Separator
A→B

Overall conversion of A Single-pass conversion of A

moles reacted
= _____________________ moles reacted
=
moles fed to overall process moles fed to reactor

=
60 - 10 = ______ = 200 - 150 = _____
60 200 36
 Example 8
In a reactor, the following reaction occurs: A ® B.
A separator places all the B from the reactor
output into the product stream (no B is recycled)
and a portion of the unreacted A back to the
reactor. Determine the recycle-to-feed ratio if
the overall conversion is 90%, conversion per pass
is 20%, and the fresh feed is 100% A.

Recycle R ?A

Fresh Product
?A ?A
Feed Fo Reactor
Reactor ?B ?B
100% A Feed Separator
?A A→ B
? mol/h A

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Basis: Fo=100 mol/h

Finally
• The steady-state MB problems were solved
using 2 different techniques:
- component balance
- atom (or element) balance

• Both methods will solve problems involving

reaction.

• MB’s involving combustion processes

demonstrated the application of the two
concepts.

• MBs for reacting systems with recycle and

purge streams are covered. It is crucial to
choose the right basis of calculation.
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