Principles of Chemical Engineering | Dr.

Alnaseri, Hayder Part IV

Atomic Species and Molecular Material Balances

Figure below shows a flowchart for the dehydrogenation of ethane 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/min.

100 kmol C2 H6 /min 40 kmol H2 Τmin

𝑛̇ 1 ( kmol C2 H6 /min )
𝑛̇ 2 ( kmol C2 H4 /min )

A number of different balances could be written on this process, including balances on the total mass C2 H6 , C2 H4 , and H2 .
Of these, only the first has the simple form input = output: since the three given species all participate in the reaction, the
balanced equation for each of them must include a generation term (C2 H4 and H2 ) or a consumption term (C2 H6 ).

Notice, however, that balance equations may also be written for atomic carbon and atomic hydrogen, regardless of the
molecular species in which the carbon and hydrogen atoms happen to be found. Balances on atomic species can be written
input = output, since atoms can neither be created (generation = 0) nor destroyed (consumption = 0) in a chemical reaction.
Before illustrating these balances, let us resolve an ambiguity. When we speak of a hydrogen balance, it could mean two
completely different things: a balance on molecular hydrogen (H2 ), existing as an independent species, or a balance on
atomic hydrogen (H), bound and unbound. We will henceforth use the terms molecular hydrogen balance and atomic
hydrogen balance to represent these two types of balances, and it will be important for you to show this distinction in
presenting your work. Some of the balances that can be written for the process shown in the above process are as follows.
(recall that the general balances equation for a batch process or a continuous steady-state process is input + generation
= output + consumption.)

Molecular Balance for 𝐇𝟐 ;

𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 𝑜𝑢𝑡𝑝𝑢𝑡

kmol H2 generated kmol H2

( ) = 40
min min

Molecular Balance for 𝐂𝟐 𝐇𝟔 :

𝑖𝑛𝑝𝑢𝑡 = 𝑜𝑢𝑡𝑝𝑢𝑡 + 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛

100 kmol C2 H6 kmol C2 H6 kmolC2 H6 consumed

= ṅ 1 ( )+( )
min min min

Molecular Balance for 𝐂𝟐 𝐇𝟒 :

𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 = 𝑜𝑢𝑡𝑝𝑢𝑡

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Principles of Chemical Engineering | Dr. Alnaseri, Hayder Part IV

kmol C2 H4 generated kmol C2 H4

( ) = ṅ 2 ( )
min min

Atomic Balance for 𝐂:

1 C2 H6 → 1C2 H4 + 1H2

𝑖𝑛𝑝𝑢𝑡 = 𝑜𝑢𝑡𝑝𝑢𝑡

100 kmol C2 H6 2 kmol C kmol C2 H6 2 kmol C kmol C2 H4 2 kmol C

| = ṅ 1 | + ṅ 2 |
min 1 kmol C2 H6 min 1 kmol C2 H6 min 1 kmol C2 H4

200 = 2𝑛̇ 1 + 2𝑛̇ 2 (1)

Atomic Balance for 𝐇:

𝑖𝑛𝑝𝑢𝑡 = 𝑜𝑢𝑡𝑝𝑢𝑡

100 kmol C2 H6 6 kmol H 40 kmol H2 2 kmol H kmol C2 H6 6 kmol H kmol C2 H4 4 kmol H

| = | + ṅ 1 | + ṅ 2 |
min 1 kmol C2 H6 min 1 kmol H2 min 1 kmol C2 H6 min 1 kmol C2 H4

580 = 6𝑛̇ 1 + 4𝑛̇ 2 (2)

𝑛̇ 1 = 60 𝑘𝑚𝑜𝑙 𝑜𝑓 𝐶2 𝐻6

𝑛̇ 2 = 40 𝑘𝑚𝑜𝑙 𝑜𝑓 𝐶2 𝐻4

Ex:

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 (1)
2

𝐶𝐻4 + 2𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂 (2)

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 mol CO2/mol CO. Calculate the molar composition of the product stream using
molecular species balances, atomic species balances, and extents of reaction.

Solution

Basis: 100 mol feed

nCH4 (mol CH4 )
nCO (mol CO)
8nCO (mol CO2 )
100 mol
nH2O (mol H2 O)
0.078 mol CH4 /mol
0.194 mol O2 /mol nO2 (mol O2 )
0.728 mol N2 /mol nN2 (mol N2 )

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Principles of Chemical Engineering | Dr. Alnaseri, Hayder Part IV

𝒏𝑪𝑯𝟒 = 𝟎. 𝟏𝟎𝟎 × (𝒎𝒐𝒍 𝑪𝑯𝟒 𝒇𝒆𝒅) = 𝟎. 𝟕𝟖𝟎 𝒎𝒐𝒍 𝑪𝑯𝟒

𝒏𝑵𝟐 = 𝟕𝟐. 𝟖 𝒎𝒐𝒍 𝑵𝟐

1. Atomic Species Balances

3
𝐶𝐻4 + 𝑂2 → 𝐶𝑂 + 2𝐻2 𝑂 (1)
2

𝐶𝐻4 + 2𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂 (2)

C balance:

7.8 𝑚𝑜𝑙 𝐶𝐻4 1 𝑚𝑜𝑙 𝐶 0.78 𝑚𝑜𝑙 𝐶𝐻4 1 𝑚𝑜𝑙 𝐶 𝑛𝐶 (𝑚𝑜𝑙 𝐶𝑂) 1 𝑚𝑜𝑙 𝐶 8 𝑛𝐶𝑂 (𝑚𝑜𝑙 𝐶𝑂2 ) 1 𝑚𝑜𝑙 𝐶
| = | + | + |
1 𝑚𝑜𝑙 𝐶𝐻4 1 𝑚𝑜𝑙 𝐶𝐻4 1 𝑚𝑜𝑙 𝐶𝑂 1 𝑚𝑜𝑙 𝐶𝑂2

𝑛𝐶𝑂 = 0.78 𝑚𝑜𝑙 𝐶𝑂

𝑛𝐶𝑂2 = (8 × 0.78)𝑚𝑜𝑙 𝐶𝑂2 = 6.24 𝑚𝑜𝑙 𝐶𝑂2

H Balance:

7.8 𝑚𝑜𝑙 𝐶𝐻4 4 𝑚𝑜𝑙 𝐻 0.78 𝑚𝑜𝑙 𝐶𝐻4 4 𝑚𝑜𝑙 𝐻 𝑛𝐻2 𝑂 (𝑚𝑜𝑙 𝐻2 𝑂) 2 𝑚𝑜𝑙 𝐻
| = | + |
1 𝑚𝑜𝑙 𝐶𝐻4 1 𝑚𝑜𝑙 𝐶𝐻4 1 𝑚𝑜𝑙 𝐻2 𝑂

𝑛𝐻2𝑂 = 14.0 𝑚𝑜𝑙 𝐻2 𝑂

O Balance:

19.4 𝑚𝑜𝑙 𝑂2 2 𝑚𝑜𝑙 𝑂 𝑛𝑂2 (𝑚𝑜𝑙 𝑂2 ) 2 𝑚𝑜𝑙 𝑂 0.78 𝑚𝑜𝑙 𝐶𝑂 1 𝑚𝑜𝑙 𝑂 6.24 𝑚𝑜𝑙 𝐶𝑂2 2 𝑚𝑜𝑙 𝑂 14.0 𝑚𝑜𝑙 𝐻2 𝑂 1 𝑚𝑜𝑙 𝑂
| = | + | + | + |
1 𝑚𝑜𝑙 𝑂2 1 𝑚𝑜𝑙 𝑂2 1 𝑚𝑜𝑙 𝐶𝑂 1 𝑚𝑜𝑙 𝐶𝑂2 1 𝑚𝑜𝑙 𝐻2 𝑂

𝑛𝑂2 = 5.75 𝑚𝑜𝑙 𝑂2

2. Extents of Reaction

3
𝐶𝐻4 + 𝑂2 → 𝐶𝑂 + 2𝐻2 𝑂 (1)
2

𝐶𝐻4 + 2𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂 (2)

𝒏𝒊 = 𝒏𝒊𝒐 + ∑ 𝒗𝒊𝒋 𝝃𝒋

For 𝐶𝐻4:

0.78 𝑚𝑜𝑙 𝐶𝐻4 = 7.8 𝑚𝑜𝑙 𝐶𝐻4 + (−1 𝑚𝑜𝑙 𝐶𝐻4 )𝜉1 + (−1 𝑚𝑜𝑙 𝐶𝐻4 )𝜉2

7.8 = (7.8 − 𝜉1 − 𝜉2 )𝑚𝑜𝑙 𝐶𝐻4 (3)

For 𝐶𝑂:

𝑛𝐶𝑂 = (1 𝑚𝑜𝑙 𝐶𝑂)𝜉1 (4)

𝑛𝐶𝑂2 = 8𝑛𝐶𝑂 = (1 𝑚𝑜𝑙 𝐶𝑂2 )𝜉2 (5)

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Principles of Chemical Engineering | Dr. Alnaseri, Hayder Part IV

𝑛𝐻2𝑂 = (2 𝑚𝑜𝑙 𝐻2 𝑂)𝜉1 + (2 𝑚𝑜𝑙 𝐻2 𝑂)𝜉2 (6)

3
𝑛𝑂2 = 19.4 𝑚𝑜𝑙 𝑂2 − ( 𝑚𝑜𝑙 𝑂2 ) 𝜉1 − (2 𝑚𝑜𝑙 𝑂2 )𝜉2
2

𝑛𝐶𝑂2 𝑚𝑜𝑙 𝐶𝑂2 (1 𝑚𝑜𝑙 𝐶𝑂)𝜉1 𝜉1

=8 = (1 = = 8 …. Substituting the last of these relationships into Eq. 3 and solving:
𝑛𝐶𝑂 𝑚𝑜𝑙 𝐶𝑂 𝑚𝑜𝑙 𝐶𝑂2 )𝜉2 𝜉2

0.78 = 7.8 − 𝜉1 − 8𝜉1

𝜉1 = 0.78, 𝑎𝑛𝑑 𝜉2 = 6.24

𝑛𝐶𝑂 = 0.78 𝑚𝑜𝑙 𝐶𝑂

𝑛𝐶𝑂2 = 6.24 𝑚𝑜𝑙 𝐶𝑂2

𝑛𝐻2𝑂 = 14.0 𝑚𝑜𝑙 𝐻2 𝑂

𝑛𝑂2 = 5.75 𝑚𝑜𝑙 𝑂2

3. Molecular Balances:

3
𝐶𝐻4 + 𝑂2 → 𝐶𝑂 + 2𝐻2 𝑂 (1)
2

𝐶𝐻4 + 2𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂 (2)

Each balance on a reactive species will contain generation and/or consumption terms. We will use the notation
CCH4,1 (mol CH4 ) to denote the consumption of methane in Reaction 1, GH2O,2 (mol H2 O) to denote the generation of water
in Reaction 2, and so on. Note that any G and C term for a specified reaction may be expressed in terms of any other G or C
term for the same reaction directly from the stoichiometric equation. For example, the generation of water in Reaction 1
may be expressed in terms of the consumption of oxygen in that reaction as

𝑪𝑶 Balance:

𝑜𝑢𝑡𝑝𝑢𝑡 = 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛

nCO = GCO,1 (3)

𝑪𝑶𝟐 Balance:

𝑜𝑢𝑡𝑝𝑢𝑡 = 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛

8nCO = GCO2 ,2 (4)

𝑪𝑯𝟒 Balance:

𝑖𝑛𝑝𝑢𝑡 = 𝑜𝑢𝑡𝑝𝑢𝑡 + 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛

7.8 mol CH4 = 0.78 mol CH4 + CCH4,1 + CCH4 ,2

CCH4,1 = 𝐺𝐶𝑂,1 × (1 𝑚𝑜𝑙 𝐶𝐻4 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑Τ1 𝑚𝑜𝑙 𝐶𝑂 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 )

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Principles of Chemical Engineering | Dr. Alnaseri, Hayder Part IV

CCH4,2 = 𝐺𝐶𝑂2,2 × (1 𝑚𝑜𝑙 𝐶𝐻4 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑Τ1 𝑚𝑜𝑙 𝐶𝑂2 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑)

7.02 mol CH4 = GCO,1 + GCO2,2

Sub. Eq.s 3, and 4;

7.02 mol CH4 = nCO + 8nCO = 9nCO

nCO = 0.78 mol CO (5)

nCO2 = 6.24 mol CO2 (6)

Sub. Eq.s 5, and 6 in Eq.s 3, and 4

GCO,1 = nCO = 0.78 mol CO generated

GCO2,2 = nCO2 = 6.24 mol CO2 generated

𝑯𝟐 𝑶 Balance:

𝑜𝑢𝑡𝑝𝑢𝑡 = 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛

nH2O = GH2O,1 + GH2O,2

2 mol H2 O generated 2 mol H2 O generated

nH2O = GCO,1 ( ) + GCO2 ,1 ( )
1 mol CO generated 1 mol CO2 generated

GCO,1 = 0.78 mol CO generated, and GCO2,2 = 6.24 mol CO2 generated

nH2O = 14.0 mol H2 O

𝑶𝟐 Balance:

𝑜𝑢𝑡𝑝𝑢𝑡 = 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛

nO2 = 19.4 mol O2 − CO2,1 − CO2 ,2

1.5 mol O2 generated 2 mol O2 generated

nO2 = 19.4 mol O2 − GCO,1 ( ) + GCO2,1 ( )
1 mol CO generated 1 mol CO2 generated

GCO,1 = 0.78 mol CO generated, and GCO2,2 = 6.24 mol CO2 generated

nO2 = 5.75 mol O2

In summary, the stack gas contains 0.780 mol CH4, 0.780 mol CO, 6.24 mol CO2, 14.0 mol H2O, 5.75 mol

O2, and 72.8 mol N2. The molar composition of the gas is therefore

0.78% CH4, 0.78% CO, 6.2 % CO2, 14.0% H2O, 5.7% O2, and 72.5% N2

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Principles of Chemical Engineering | Dr. Alnaseri, Hayder Part IV

Given that all three methods of carrying out material balances on reactive systems— molecular species balances, atomic
species balances, and extents of reaction—necessarily yield the same results, the question is which one to use for a given
reactive process. There are no hard and fast rules but we suggest the following guidelines:

1. Atomic species balances generally lead to the most straightforward solution procedure, especially when more than
one reaction is involved.
2. Extents of reaction are convenient for chemical equilibrium problems and when equation solving software is to be
used.
3. Molecular species balances require more complex calculations than either of the other two approaches and should
be used only for simple systems involving one reaction.

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