CHAPTER FOUR

MATERIAL BALANCE INVOLVING REACTION

 MATERIAL BALANCE INVOLVING REACTION

Learning Outcomes:

It is expected that Students would to able to:

1. Explain Stoichiometry, stoichiometric ratio and apply them in material balance.

2. Explain Limiting and Excess Reactants, Fractional Conversion, and Extent of

Reaction and apply them in material balance calculations.

3. Conduct balances on Molecular and Atomic Species.

4. Conduct balances using Extent of Reaction.

 MATERIAL BALANCE INVOLVING REACTION

• Stoichiometry is the theory of the proportions in which chemical

species combine with one another.

• The stoichiometric equation of a chemical reaction is a statement of

the relative number of molecules or moles of reactants and products
that participate in the reaction.

• The stoichiometric ratio of two molecular species participating in a

reaction is the ratio of their stoichiometric coefficients in the balanced
reaction equation.
For the reaction;
2SO2 + O2 → 2SO3

• The stoichiometric ratios can be written as ;

2 mol SO3 generated 2 lb − moles SO2 consumed
,
1 mol O2 consumed 2lb − moles SO3 generated

For example,

If 1600 kg/h of SO3 is to be produced. you can calculate the amount of oxygen
required as
1600 𝑘𝑔 𝑆𝑂3 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 1 𝑘𝑚𝑜𝑙 𝑆𝑂3 1 𝑘𝑚𝑜𝑙 𝑂2 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑘𝑚𝑜𝑙 𝑂2
× × = 10
ℎ 80 𝑘𝑔 𝑆𝑂3 2 𝑘𝑚𝑜𝑙 𝑆𝑂3 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 ℎ

𝑘𝑚𝑜𝑙 𝑂2 32 𝑘𝑔 𝑂2 𝑘𝑔 𝑂2
⇒ 10 × = 320
ℎ 1 𝑘𝑚𝑜𝑙 𝑂2 ℎ
❖ Limiting and Excess Reactants

• Two reactants, A and B, are said to be present in stoichiometric proportion if the

ratio (moles A present)/(mole B present) equals the stoichiometric ratio obtained
from the balanced reaction equation.
2SO2 + O2 → 2SO3

• For every mole of O2 there must be 2 moles of SO2 so that;

𝑛𝑆𝑂2 2
= = 2: 1
𝑛𝑂2 1

• A reactant is limiting if it is present in less than its stoichiometric

proportion relative to every other reactant.
• Suppose (nA)feed is the number of moles of an excess reactant, A, present in the
feed to a reactor and that (nA)stoich is the stoichiometric requirement of A,

• Then (nA)feed - (nA)stoich is the amount by which the A in the feed exceeds the
amount needed to react completely if the reaction goes to completion.

• 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 of A is 100 times the fractional excess.

❖Fractional Conversion
• The fractional conversion of a reactant is the ratio’;
moles reacted
f=
moles fed
Note; The fraction unreacted is accordingly 1 - f.

• If 100 moles of a reactant are fed and 90 moles react, the fractional conversion is;
𝑚𝑜𝑙𝑒𝑠 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 90
= = 0.90
𝑚𝑜𝑙𝑒𝑠 𝑓𝑒𝑑 100

• The fraction unreacted;

1 − 𝑓 =1−0.90 = 0.10.

• If 20 mol/min of a reactant is fed and the percentage conversion is 80%.Find the

fraction of conversion.
❖ Extent of Reaction

Let us define a quantity vi to be the stoichiometric coefficient of the ith species in a

chemical reaction, making it negative for reactants and positive for products. For
example,

C2H2 + 2H2 – C2H6 → vC2H2 = -1, vH2 = -2, vC2H6 = +1

Then if niO (or all i) is the moles (batch) or molar flow rate (continuous) of species i in
the feed to a batch or continuous steady-state process,
𝑛𝑖 = 𝑛𝑖0 + 𝜐𝑖 𝜉 ≡ 𝑛𝑖ሶ = 𝑛ሶ 𝑖0 + 𝜐𝑖 𝜉ሶ

ሶ which has the same units as n (or 𝑛),

The quantity ξ (or 𝜉), ሶ is called the extent of
reaction.
• For example, consider the ammonia formation reaction:

• N2 + 3H2 = 2NH3

• Suppose the feed to a continuous reactor consists of 100 mol/s of nitrogen, 300
mol/s of hydrogen, and 1 mol/s of argon (an inert gas). we may write for the reactor
outlet flow rates

• nN2= 100 mol/s - ξ

• nH2 = 300 mol/s - 3ξ

• nNH3 = 2ξ

• nA = 1 mol/s

• For a fractional hydrogen conversion of 0.60, calculate the outlet flow rate of hydrogen, the
extent of reaction, and the outlet flow rates of nitrogen and ammonia.
Figure 10.1 shows a flowchart for the dehydrogenation of ethane in a steady-state continuous
reactor. The reaction is
𝐶2 𝐻6 → 𝐶2 𝐻4 + 𝐻2

Figure 10.1 Dehydrogenation of ethane.

100 kmol/min of ethane is fed to the reactor. The molar flow rate of H2 in the product
stream is 40 kmol/min.
The general balance equation for a steady-state process is;
input + generation = output + consumption
Solution
❖Independent Equations, Independent Species, and Independent Reactions
• To carry out degree-of-freedom analyses of reactive systems you must first
understand the concepts of independent equations, independent species, and
independent chemical reactions.
• Consider a process in which a stream of liquid carbon tetrachloride is vaporized
into a stream of air.
❖Independent Equations, Independent Species, and Independent Reactions

• Since nitrogen and oxygen are shown as being in the same ratio wherever they
appear on the flowchart (3.76 mol N2/mol O2),

• We cannot count them as two independent species and so you may count only
two independent molecular species balances in a degree-of-freedom analysis -
one for either O2 or N2 and one for CCI4.
• Similarly, atomic nitrogen (N) and atomic oxygen (O) are always in the
same proportion to each other in the process (again 3.76:1) as are atomic
chlorine and atomic carbon (4 mol Cl/1 mol C).

• Consequently, even though four atomic species are involved in this

process, you may count only two independent atomic species balances in
the degree-of-freedom analysis-one for either O or N and one for either C
or Cl.
❖ Molecular Species Balances

• For molecular species balances the degree-of-freedom analysis is as follows:

No. unknown labeled variables

+ No. independent chemical reactions
- No. independent molecular species balances
=No. degrees of freedom

• The dehydrogenation of ethane will be used to illustrate the required

procedures.
❖ Atomic Species Balances
• The number of degrees of freedom is determined directly by
subtracting equations from labeled unknowns: no additional degrees
of freedom are contributed by the reactions.

No. unknown labeled variables

- No. independent atomic species balances

- No. molecular balances on independent non reactive species

- No. other equations relating unknown variables

= No. degrees of freedom

❖ Extent of Reaction
• The third way to determine unknown molar flow rates for a reactive process is to
write expressions for each product species flow rate (or molar amount) in terms of
extents of reaction:
No. unknown labeled variables
+ No. independent reactions (one extent of reaction for each)
- No. independent reactive species (one equation for each species in terms of
extents of reaction)
- No. independent non-reactive species (one balance equation for each)
- No. other equations relating unknown variables
= No. degrees of freedom

In the dehydrogenation process, DF = 2 unknown variables ( 𝑛ሶ 1 , 𝑛ሶ 2 ) + 1

independent reaction - 3 independent reactive species (C2H6, C2H4, H2) = 0. For
the same process, (𝑛ሶ 1 = 𝑛ሶ 2 + viξ) for the three species in the process becomes,
NOTE; Atomic species balances generally lead to the most straightforward solution
procedure, especially when more than one reaction is involved.
• Extents of reaction are convenient for chemical equilibrium problems and when
equation solving software is to be used.
• 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
 TUTORIALS
• Q1 Stoichiometry - Consider the combustion of heptane:

1. Make sure the chemical equation is correctly balanced. How can you tell if
the reaction equation is balanced? Make sure the total quantities of each of
the elements on the left-hand side equal those on the right-hand side.

2. Use the proper degree of completion for the reaction. If you do not know how
much of the reaction has occurred, you may assume a reactant reacts
completely.
 TUTORIALS

3. Use molecular weights to convert mass to moles for the reactants and
moles to mass for the products.

4. Use the coefficients in the chemical equation to obtain the relative molar
amounts of products produced and reactants consumed in the reaction.

• The stoichiometric coefficients in the chemical reaction equation (1 for

C7H16, 11 for O2, and so on) tell you the relative amounts of moles of
chemical species that react and are produced by the reaction.
 TUTORIALS

• The stoichiometric coefficients in the chemical reaction equation (1 for

C7H16, 11 for O2, and so on) tell you the relative amounts of moles of
chemical species that react and are produced by the reaction.
• In taking ratios of coefficients, the denominators cancel, and you are left
with the ratio of the moles of one species divided by another. For example,
for the combustion of heptanes:
 TUTORIALS

• You can conclude that 1 mole (not lbm or kg) of heptane will react with 11
moles of oxygen to give 7 moles of carbon dioxide plus 8 moles of water.
• Another way to use the chemical reaction equation is to conclude that 1
mole of CO2 is formed from each 1/7 mole of C7H16 and 1 mole of H2O is
formed with each 7/8 mole of CO2.
• The ratios indicate the stoichiometric ratios that can be used to determine
the relative proportions of products and reactants.
 TUTORIALS
Q1. How many kilograms of CO2 will be produced as product if 10 kg of
C7H16 react completely with the stoichiometric quantity of O2?

Solution:
• On the basis of 10 kg of C7H16:
 TUTORIALS
• Q2 Calculate the amount of oxygen required to produce 1600 kg/h of SO3, for
the following reaction:

• Solution:
 TUTORIALS
• Use of the Chemical Reaction Equation to Calculate the Mass of Reactants
Given the Mass of Products:
Q3. In the combustion of heptane with oxygen, CO2 is produced. Assume that
you want to produce 500 kg of dry ice per hour, and that 50% of the CO2 can be
converted into dry ice, as shown in the Figure. How many kilograms of heptane
must be burned per hour?
 TUTORIALS
• Solution:
• From the problem statement you can conclude that you want to use the
product mass of CO2 to calculate a reactant mass, the C7H16
• The procedure is first to convert kilograms of CO2 to moles, apply the
chemical equation to get moles of C7H16, and finally calculate the kilograms
of C7H16.
• Basis: 500 kg of dry ice (equivalent to 1 hr)
 TUTORIALS
• Solution:
• Basis: 500 kg of dry ice (equivalent to 1 hr)
• The calculation of the amount of C7H16 can be made in one sequence:
 TUTORIALS
• Balances on Reactive Processes: Balances on Molecular and Atomic
Species:
• Que: The Figure shows a flowchart for the dehydrogenation of ethane in a
steady-state continuous reactor. The reaction is

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.
 TUTORIALS
• Balances on Reactive Processes: Balances on Molecular and Atomic
Species:
• Que: The Figure shows a flowchart for the dehydrogenation of ethane in a
steady-state continuous reactor. The reaction is
 TUTORIALS
• Balances on Reactive Processes: Balances on Molecular and Atomic
Species:
• Que: The Figure shows a flowchart for the dehydrogenation of ethane in a
steady-state continuous reactor. The reaction is