LECTURE 8 MATERIAL BALANCES FOR PROCESSES INVOLVING REACTION

8.1 Introduction

In the previous lecture we discussed how to make material balances for processes without chemical
reaction. Why is it important to discuss material balances for systems with reaction? The heart of
many plants is the reactor in which products and by-products are manufactured. To be able to
design and operate a reactor economically and safely you have to be able to make valid material
balances for the reactor often in real time.
We begin by discussing material balances based on chemical species, and then examine material
balances made using chemical elements.

8.2 Objectives

By the end of this lecture you will be able to:

1. carry out a degree of freedom analysis for processes involving chemical reaction
2. formulate and solve material balances using (a) species balances and (b) element balances
3. decide when element balances can be used as material balances
4. understand how the extent of reaction is determined for a process and how to apply it in
material balance problems

8.3 Processes involving a chemical reaction

The material balance for a species must be augmented to include generation and consumption
terms when a chemical reaction occurs in a process. In terms of moles of species i we have:
moles of moles of moles of i moles of i moles of i moles of i
i at t2 in i at t1 in entering leaving generated consumed
- = - -
the the the system the system + by reaction by reaction (8.1)
system system between t2 between between t2 between t2
and t1 t2 and t1 and t1 and t1

Take note

The Equation (8.1) is written in moles rather than mass because the generation and consumption
terms are more conveniently represented in moles.

Now let us answer the following question:

Question

How do you include the variables corresponding to the generation and consumption terms in Eq.(8.1)
and still maintain the independence of the species material balances?
Fortunately, you do not have to add an additional variable to account for the generation or
consumption of species i for each species present in the system if you make use of the extent of
reaction. To make the idea clear, let us consider the following example.

Example 8.1
Figure 8.1 presents the process as an open, steady-state system operating for 1 min so that the
accumulation term on the left-hand side of Eq.(8.1) is zero. The data in Figure 8.1 are in g mol.
18 H2 9 H2
Reactor
12 N2
N2 + 3 H2↔2 NH3
15 N2 6 NH3

Figure 8.1. A reactor to produce NH3.

Using Eq (8.1) you can calculate via a value in g mol for the generation or consumption, as the
case may be, for each of the three species involved in the reaction:
NH3 (generation): 6 – 0 = 6 g mol
H2 (consumption): 9 – 18 = - 9 g mol
N2 (consumption): 12 – 15 = - 3 g mol

From the stoichiometry of the chemical reaction equation the three generation and consumption
terms are related by the reaction equation. Thus, the generation and consumption terms are not
independent. If you specify the value for generation or consumption of one of the N species in a
reaction, you are able to calculate the values of the N – 1 other species from the chemical reaction
equation.
Here is where the extent of reaction ξ becomes useful. Recall that for an open system
n i out - n i in
ξ= i = 1, …, N (8.2)
νi
Where ν i is the stoichiometric coefficient of species i in the reaction equation:
ν NH3 = 2
ν H2 = - 3
ν N2 = - 1

Take note
n i out - n i in
The extent of reaction for an open (flow) system is ξ = , where niin is the number of
νi
moles of species i before chemical reaction, and niout is the number of moles of species i after
chemical reaction has taken place.

And the extent of reaction can be calculated via any species:

 n NH3 out - n NH3 in 6-0
ξ= = =3
ν NH3 2

n H2 out - n H2 in 9 - 18
ξ= = =3
ν H2 -3

n N2 out - n N2 in 12 - 15
ξ= = =3
ν N2 -1
The three species balances corresponding to the process in Figure 8.1 above are:

Component Out In = Generation or Consumption

i niout - niin = νiξ

NH3: 6 -0 = 2 (3) = 6
H2: 9 - 18 = - 3 (3) = - 9
N2: 12 - 15 = - 1 (3) = - 3

The term ν i ξ corresponds to the moles of i generated or consumed. For the species that do not
react, ξ = 0.

Take note

For a closed, unsteady-state (batch) system the flows in and out would be zero, and Equation
n i final - n iinitial
(8.1) would become: =ξ
νi

In terms of the total molar flow in and total molar flow out
S
Fout =  n i out
i=1
S
Fin =  n iin (8.3)
i=1

Where S is the total number of species in the system. The material balance for the total molar
flow is
S
Fout = Fin + ξ  νi (8.4)
i=1

Equation (8.4) is not an independent equation, but can be substituted for one of the species
balances. Only S independent equations can be written for the system.

If you add one more unknown, ξ , you will have to add one more piece of information in the
problem statement in order to be able to solve a problem. For example, you might be given the
value of the fraction conversion, f , of the limiting reactant which is related to the extent of
reaction ξ by:
(- f )n in limiting reactant
ξ= (8.5)
ν limiting reactant
Consequently, you can calculate the value of ξ from the fraction conversion (or vice versa).

Take note

Conversion is the fraction of the feed or some key material in the feed that is converted into
products.
Thus, percent conversion is
moles (or mass) of feed (or a compound in the feed) that react
% conversion= 100
moles (or mass) of feed (or a compound in the feed) introduced

Take note

The limiting reactant is the species in a chemical reaction that would theoretically run out first
(would be completely consumed) if the reaction were to proceed to completion according to the
chemical equation — even if the reaction does not proceed to completion! All the other
reactants are called excess reactants.

Example 8.2
The chlorination of methane occurs by the following reaction
CH4 + Cl2 → CH3Cl + HCl

You are asked to determine the product composition if the conversion of the limiting reactant is
67%, and the feed composition in mole % is given as: 40% CH4, 50% Cl2, and 10% N2.

Solution:

Assume the reactor is an open, steady-state process.

Reactor 67% conversion
Feed Product
100 g mol F n CH4
40% CH4 n Cl2
50% Cl2 n HCl
10% N2 n CH3Cl
n N2

Basis: 100 g mol feed

By comparing the maximum extent of reaction for each reactant, you can identify the limiting
reactant.
- n in CH4 - 40
ξ (CH 4 ) =
max
= = 40
ν CH4 (-1)
- n in Cl2 - 50
ξ max
(Cl2 ) = = = 50
ν Cl2 (-1)
Therefore, CH4 is the limiting reactant.
You can now calculate the extent of reaction using the specified conversion rate and Eq. (8.5):
- f  n in l r - (0.67)(40)
ξ= = = 26.8 g moles reacting
νl r -1

The species material balances (in moles) using Equation (8.2) gives a direct solution for each
species in the product:
nout CH4 = 40 – 1 (26.8) = 13.2
nout Cl2 = 50 – 1 (26.8) = 23.2
noutCH3Cl = 0 + 1 (26.8) = 26.8
noutHCl = 0 + 1 (26.8) = 26.8
noutN2 = 10 – 0 (26.8) = 10.0
100.0 = P
Therefore, the composition of the product stream is: 13.2% CH4, 23.2% Cl2, 26.8% CH3Cl, 26.8%
HCl, and 10% N2 because the total number of product moles is conveniently 100 g mol.

Example 8.3
A proposed process to remove H2S from the methane CH4 stream is by reaction with SO2:
2 H2S (g) + SO2 (g) → 3S (s) + 2 H2O (g)

In the rest of the process, a gas stream containing 20% H2S and 80% CH4 was combined with a
stream of pure SO2. The process produced 5000 lb of S(s), and in the product gas the ratio of SO2
to H2S was equal to 3, and the ratio of H2O to H2S was 10. Determine the fractional conversion of
the limiting reactant, and the feed rates of the H2S and SO2 streams.

Solution:
 F
20% H2S Product P
80% CH4 nPSO2
Reactor
F SO2 nPH2S
nPH2O
nPCH4
S
5000 lb
Basis: 5000 lb S (156.3 lb mol S)
Specifications: 4 (3 independent)
xFH2S = 0.20 or xFCH4 = 0.80, (nPSO2/ nPH2S) = 3, (nPH2O/ nPH2S) = 10
The species balances in pound moles after introduction of most of the specifications are:
S: 156.3 = 0 + 3 ξ (a)
H2S: nPH2S = 0.20 F – 2 ξ (b)
SO2: nPSO2 = FSO2 – 1 ξ (c)
H2O: nPH2O = 0 + 2 ξ (d)

CH4: nPCH4 = 0.80 F + 0 ( ξ ) (e)

The remaining specifications are:

nPSO2 = 3 nPH2S (f)

nPH2O = 10 nPH2S (g)

When solving the equations, start by calculating ξ from Equation (a)

156.3 mol
ξ   52.1mol rxn
3

Then Eq. (d) gives: nPH2O = 2 (52.1) = 104.2 lb mol H2O

1 P
Next, Eq. (g) gives: n P H 2S = n H 2O = 10.4 lb mol H 2S
10

And Eq. (f) gives: nPSO2 = 3(10.4) = 31.2 lb mol SO2

If you solve the rest of the equations in the order (b), (c), and (e), you find:
F = 573 lb mol

FSO2 = 83.3 lb mol

nPCH4 = 458 lb mol

Finally, you can identify H2S as the limiting reactant because the molar ratio of SO2 to H2S in the
product gas (3/1) is greater than the molar ratio in the chemical reaction equation (1/2).
The fractional conversion from Eq. (8.5) is the consumption of H2S divided by the total feed
of H2S:
- (- 2) ξ (2)(52.1)
f =   0.91
0.2 F (0.2)(573)

8.4 Element material balances

Elements in a process are conserved, and consequently you can apply Eq.(8.1) to the elements in
a process. Because elements are not generated or consumed, the generation and consumption terms
in Eq.(8.1) can be ignored.

Question

Is it possible to use element balances to solve material balance problems rather than species
balances?

The answer to the above question is, yes, it is possible, but you must first make sure that the
element balances are independent. Species balances are always independent. Here is an
illustration of the issue. Carbon dioxide is absorbed in water in the process shown in Figure below.
The reaction is:
CO2 (g) + H2O (l) → H2CO3 (l)
W (H2O)

Absorber

P mol%
5% H2CO3
95% H2O
F (CO2)

Three unknowns exist: W, F, and P, and the process involves three elements: C, H, and O. It
would appear that you can use the three element balances (in moles) to solve for W, F, and P:

C: W(0) + F(1) = 0.05P (1)

H: W(2) + F(0) = [0.05(2) + 0.95(2)]P = 2P

O: W(1) + F(2) = [0.05(3) + 0.95(1)]P = 1.10P

But you cannot! Try it. The reason is that the three element balances are not independent. Only
two of the element balances are independent. If you pick a basis of P=100 mol, the degrees of
freedom become zero, and then you can solve for W and F. If you are curious as to why the three
element balances are not independent, you can view H2CO3 as H2O.CO2 in which the fixed ratio
of H/O and C/O prevents the O balance from being independent of the H and C balances.

Example 8.5 Solution of Example 8.2 using Element Balances

All of the given data for this example is the same as in Example 8.2.

Solution: The element balances are:

C: 100 (0.40) = noutCH4(1) + noutCH3Cl(1)
H: 100 (0.40)(4) = noutCH4(4) + noutHCl(1) + noutCH3Cl(3)
Cl: 100 (0.50) (2) = noutCl2(2) + noutHCl(1) + noutCH3Cl(1)
2N: 100 (0.10)(1) = noutN2(1)
The solution of the problem will be the same as found in Example 8.2:
C: 40 = 13.2 + 26.8
H: 160 = 13.2 (4) + 26.8 + (26.8)3
Cl: 100 =23.2(2) + 26.8 + 26.8
2N: 10 = 10

Question
When can the Element balances be used?

Element balances are useful when it is not known what kind of reactions occur in a process. The
only information known is about the input and output stream components. This is illustrated in the
next Example 8.5.

Example 8.5
In an experiment for the hydrocracking of octane, the cracked products had the following
composition in mole percent: 19.5% C3H8, 59.4% C4H10, and 21.1% C5H12. Determine the molar
ratio of hydrogen consumed to octane reacted for this process.
Solution:
 F (C8H18) G(H2
))

Lab
Reactor

Product P
19.5% C3H8
59.4% C4H10
The reactions involved in the process are not specified therefore
21.1%weCwill use element balances to
5H12
solve this problem.
Basis : P = 100 g mol

Element balances: 2 H, C

The element balances:

C: F(8) + G(0) = 100[(0.195)(3) + (0.594)(4) + (0.211)(5)]
H: F(18) +G(2) = 100[(0.195)(8) + (0.594)(10) + (0.211)(12)]
And the solution is
F = 50.2 g mol G = 49.8 gmol
The ratio
H2 consumed 49.8 g mol
= = 0.992
C8 H18 reacted 50.2 g mol