Che 1103

Elements of Chemical engineering

Material Balance

Dr. Rajesh Kumar Chanda

Assistant Professor
Department of Chemical Engineering
E-mail: [email protected]

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Balances on Reactive Systems
Stoichiometry:
When chemical reactions occur, in contrast with physical changes of material such as
evaporation or dissolution, you want to be able to predict the mass or moles required for the
reaction(s), and the mass or moles of each species remaining after the reaction has occurred.
Reaction stoichiometry allows you to accomplish this task. The word stoichiometry
(stoi-ki-om-e-tri) derives from two Greek words: stoicheion (meaning "element") and metron
(meaning "measure"). Stoichiometry provides a quantitative means of relating the
amount of products produced by chemical reactions to the amount of reactants.
The following expressions are widely used in stoichiometry:
1. Stoichiometric coefficients:
The numbers that are precede the chemical substances involved in the chemical reaction
equation are known as " stoichiometric coefficients". These coefficients represent
quantity of any reactant that is theoretically required for complete conversion of other
reactants.
2. Stoichiometric ratios:
The ratio between any stoichiometric coefficients in a balanced chemical equation is
known as " stoichiometric ratio".
As an example the reaction of nitrogen and hydrogen to produce ammonia:
N2 + 3H2 → 2NH3
The stoichiometric ratios of N2/H2 =1/3, N2/NH3= 1/2 and H2/NH3=3/2
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Example: Use of the Chemical Equation to Calculate the Mass of Reactants Given
the Mass of Products
In the combustion of heptane, 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
Figure. How many kilograms of heptane must be burned per hour?

Solution:
The chemical equation is:
C7H16 + 11O2 → 7CO2 + 8H2O
Basis: 500 kg dry ice (equivalent to 1 hr)
M.wt. of CO2 = 44 kg/kgmol & C7H16 = 100.1 kg/kgmol

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Homework:
Example: Application of Stoichiometry When More than One Reaction Occurs
A limestone analyses (weight %)
CaCO3 92.89%
MgCO3 5.41%
Inert 1.70%
By heating the limestone you recover oxides known as lime.
(a) How many pounds of calcium oxide can be made from 1 ton of this limestone?
(b) How many pounds of CO2 can be recovered per pound of limestone?
(c) How many pounds of limestone are needed to make 1 ton of lime?
The chemical reactions are:
CaCO3 → CaO + CO2
MgCO3 → MgO + CO2

Notes:
Limestone contains inert which is not converted to any products

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Balances on Reactive Systems
If proportion of chemical species fed to a reactor is same as the stoichiometric ratio, then
chemical species combine in stoichiometric proportion, otherwise one or more species will
be in excess of the other. The chemical compound which is present less than its
stoichiometric amount, will disappear first. This reactant will be the limiting reactant and all
the others will be excess reactants. Fractional and percentage excess are given by the
following formulas.

where
n = number of moles fed
ns = number of moles corresponding to stoichiometric amount

In many cases, chemical reactions do not go to completion and only a fraction will be converted.
Therefore, fractional and percentage conversions are used. They are defined as follows,

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Balances on Reactive Systems
Extent of Reaction ( ):
The extent of reaction is calculated by dividing the change in the number of moles of a species
that occurs in a reaction, for either a reactant or a product, by the related stoichiometric
coefficient.

When the chemical reaction proceeds in one direction only, we call it irreversible. If the
reaction proceeds in forward and backward directions then it is reversible. When forward
reaction rate and reverse reaction rate becomes equal, reaction is said to be in equilibrium.
Equilibrium constant (K) for a gas phase reaction, A(gas) + B(gas)<=> C(gas) + D (gas), is
given by

where y is the mole fraction of the components in the gas phase.

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Example:
Determine the extent of reaction for the following chemical reaction:
N2 + 3H2 → 2NH3
given the following analysis of feed and product:

Solution:
Based on NH3:

Based on N2:

Based on H2: (Homework)

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EXAMPLE: Reaction Stoichiometry
Acrylonitrile is produced by the reaction of propylene, ammonia, and oxygen.

The feed contains 10 mole% propylene, 12% ammonia, and 78% air. A fractional conversion
of 30% of the limiting reactant is achieved. Determine which reactant is limiting, the
percentage by which each of the other reactants is in excess, and the molar flow rates of all
product gas constituents for a 30% conversion of the limiting reactant, taking 100 mol of feed
as a basis.

Solution
Basis : 100 mol Feed

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From given data, (step 1) Identify limiting and excess reactant (step 2)

Since propylene is fed in less than the stoichiometric proportion relative to the two other
reactants, propylene is the limiting reactant.
To determine the percentages by which ammonia and oxygen are in excess, you must first
determine the stoichiometric amounts of these reactants corresponding to the amount of
propylene in the feed (10 mol) (step 3).

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 Homework

Note:

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Balances on Reactive Systems
In a chemical process, our objective is to produce a certain product (desired product), but
there may be several unwanted reactions which will produce undesirable by products.
Therefore, we must maximize the production of a desired product in the process. Two
quantities, yield and selectivity, are used for this purpose and they are defined as follows,
Selectivity:
Is the ratio of the moles of a particular (usually the desired) product to the moles of
another (usually undesired or by-product) product produced in a set of reactions.

Yield:
(based on feed): The amount (mass or moles) of desired product obtained divided by the
amount of the key (frequently the limiting) reactant fed.

(based on reactant consumed): The amount (mass or moles) of desired product obtained
divided by the amount of the key (frequently the limiting) reactant consumed.

*It is important to know that incomplete reactions and side reactions reduce the yield.
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Example:
We have two reactions:
Cl2 (g) + C3H6 (g) → C3H5Cl (g) + HCl ......…………….. (a)
Cl2 (g) + C3H6 (g) → C3H6Cl2 (g) …………………..(b)
The species recovered after the reaction takes place for some time are listed in table below:

Based on the product distribution assuming that no ally chlorides were present in the feed,
calculate the following:
a. How much C12 and C3H6 were fed to the reactor in gmol?
b. What was the limiting reactant?
c. What was the excess reactant?
d. What was the fraction conversion of C3H6 to C3H5C1?
e. What was the selectivity of C3H5C1 relative to C3H6C12?
f. What was the yield of C3H5CI expressed in g of C3H5C1 to the g of C3H6 fed to the reactor?
g. What was the extent of reaction of the first and second reactions?

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Solution:

First calculate the gmol fed to the reactor (even if the amounts were not asked):

From the chemical equations you can see that if 29.1 gmol Cl2 reacts by reaction (a) and (b),
the same quantity of 29.1 gmol of C3H6 must react.
C3H6 in the product = 651.0 gmol
Total C3H6 fed = 651.0 + 29.1 = 680.1 gmol C3H6

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Solution:

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 Try to this at Home. It is an example from book.

The reactions

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 and
the selectivity of ethylene to methane production

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Material Balances for Processes Involving Reaction
If proportion of chemical species fed to a reactor is same as the stoichiometric ratio, then
chemical species combine in stoichiometric proportion, otherwise one or more species will
be in excess of the other. The chemical compound which is present less than its
stoichiometric amount, will disappear first. This reactant will be the limiting reactant and all
the others will be excess reactants. Fractional and percentage excess are given by the
following formulas.

where
n = number of moles fed
ns = number of moles corresponding to stoichiometric amount

In many cases, chemical reactions do not go to completion and only a fraction will be converted.
Therefore, fractional and percentage conversions are used. They are defined as follows,

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Atomic and Molecular Balances
In a chemical process, molecules are either generated (produced) or consumed. Therefore,
one should take into account the amounts (moles) generated, consumed, fed and remaining in
molecular balances.

The general balance equation

For simplification, in this course there would be no accumulation. So you can

assume this term to zero.
However, in real life, there may be accumulation depending on process
(Example: Batch process
According to conservation principle, atoms can neither be created (produced) nor destroyed
(consumed). Therefore, in atomic balances there is no generation or consumption terms.
Simply, input = output.
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Example:
In a steady state process, 100 moles ethane (C2H6) react to produce ethylene
(C2H4) and hydrogen (H2) according to C2H6→C2H4 + H2. Product gas shows
40 moles of hydrogen remaining. Perform molecular balances for all species.
Solution: Molecular Balances

Then, the molecular balance of H2 is as follows,

input + generated (produced) = output + consumed (reacted) The general balance equation
input = 0.0, output = 40, consumed = 0
0 + generated (produced) = 40+ 0 ⇒ H2 (generated) = 40 moles.

Molecular balance of C2H6 is as follows,

input + generated (produced) = output + consumed (reacted) The general balance equation
input = 100, generated = 0, output = 𝑛ሶ 1
100 + 0 = 𝑛ሶ 1 + consumed ⇒ C2H6 (consumed) = 100-𝑛ሶ 1
H2 (generated) = 40 moles=C2H6 (consumed) = 100- 𝑛ሶ 1 ⇒ 𝑛ሶ 1 = 60 moles

Molecular balance of C2H4 is as follows,

input + generated (produced) = output + consumed (reacted) The general balance equation
input = 0, output = 𝑛ሶ 2, consumed = 0
0 + generated = 𝑛ሶ 2 + 0 ⇒ C2H4 (generated) = 𝑛ሶ 2
C2H4 (generated) = 𝑛ሶ 2 = H2 (generated) = 40 moles ⇒ 𝑛ሶ 2 = 40 moles 18
Solution: Atomic Balances
Remainder:
According to conservation principle, atoms can neither be created (produced) nor destroyed
(consumed). Therefore, in atomic balances there is no generation or consumption terms.
Simply, input = output.

Solving this two equation gives you the solution

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Moral story: you can solve a problem as you like!!! Both are correct!!!
Try to this at Home. It is an example from book.

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