Principles of Chemical

Engineering

Chapter

4 Fundamentals of
Material Balances:
Part 2
1 Instructor: Prof. Saleh Rawadieh
Email: [email protected]
6. CHEMICAL REACTION STOICHIOMETRY

The occurrence of a chemical reaction in a process brings complications

into material balance procedures described previously.

6.1 Stoichiometry

Stoichiometry is the theory of the proportions in which chemical species

combine with one another.

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.

A valid stoichiometric equation must be balanced (i.e., the number of

atoms of each atomic species must be the same on both sides of the
equation). For example:

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The stoichiometric ratio of two molecular species participating in a
reaction is the ratio of their stoichiometric coefficients in the balanced
reaction equation.

This ratio can be used as a conversion factor to calculate the amount of a

particular reactant (or product) that was consumed (or produced), given a
quantity of another reactant of product that participated in the reaction. For
the reaction

the stoichiometric ratios

and so on. If you know, for example, that 1600 kg/h of SO3 is to be
produced, you can calculate the amount of oxygen required as

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6.2 Limiting and Excess Reactants,
Fractional Conversion, and
Extent of Reaction

Reactants (e.g., A and B) are in stoichiometric proportion if the ratio

(mol A present / mol B present) equal the stoichiometric ratio obtained
from the balanced reaction equation.

For the reactants in the reaction

to be present in stoichiometric proportion, there must be 2 moles of SO2

for every mole of O2 (nSO2/nO2 = 2:1) present in the feed to the reactor.

If reactants are fed to a chemical reactor in stoichiometric proportion and

the reaction proceeds to completion, all of the reactants will disappear at
the same instant.

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The reactant that would run out if a reaction proceeded to completion is
called limiting reactant, and the other reactants are excess reactants.

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

relative to every other reactant.

If all reactants are present in stoichiometric proportion, then no reactant is

limiting.

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, or the amount needed to react completely with the
limiting reactant. 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.

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The fractional excess of the reactant is the ratio of the excess to the
stoichiometric requirement:

The percentage excess of A is 100 times the fractional excess.

Chemical reactions proceed slowly and it is not practical to design the

reactor for complete conversion of the limiting reactant. Instead, the
reactor effluent emerges with some of the limiting reactant still present and
is then usually subjected to a separation process to remove the
unconverted reactant from the product. The separated reactant is then
recycled to the reactor inlet. The fractional conversion of a reactant is
the ratio

The fraction unreacted is (1 – f ). 6

If 100 moles of a reactant are fed and 90 moles react,
Fractional conversion = 0.9
Percentage conversion = 90%
Fraction unreacted = 0.1.

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

20 × 0.8 = 16 mol/min reacted
20 (1 – 0.8) = 4 mol/min unreacted.

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Let us define a quantity vi to be the stoichiometric coefficient of the ith
species in a chemical reaction (negative for reactants and positive for
products). For example,

Then if ni0 (or ṅi0) is the moles (batch) or molar flow rate (continuous) of
species i in the feed to a batch or continuous steady-state process,

The quantity ξ is called the extent of reaction and has the same unit as n.

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Example 10: Acrylonitrile is produced in the reaction of propylene,
ammonia, and oxygen:
C3H6 + NH3 + 1.5 O2 → C3H3N + 3 H2O
The feed contains 10 mole% propylene, 12% ammonia,
and 78% air. A fractional conversion of 30% of the limiting
reactant is achieved. Taking 100 mol of feed as a basis,
determine (1) which reactant is limiting, (2) percentage by
which each of the other reactants is in excess, and (3) the
molar amounts of all product gas constituents for a 30%
conversion of the limiting reactant.
Solution:

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C3H6 + NH3 + 1.5 O2 → C3H3N + 3 H2O
10 mol + 12 mol + 78 mol
f = 30%

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6.3 Chemical Equilibrium

Two of the fundamental questions of chemical reaction engineering are,

given a set of reactive species and reaction conditions:

1. What will be the final (equilibrium) composition of the reaction mixture

(field of chemical equilibrium thermodynamics).
2. How long will the system take to reach a specified state short of
equilibrium (field of chemical kinetics).

Irreversible reaction – reaction proceeds only in a single direction (from

reactants to products) and limiting reactant concentration eventually
approaches zero. Equilibrium composition is the composition
corresponding to complete composition of limiting reactant.

Reversible reaction – reactants from products and products undergo the

reverse reactions to reform the reactants. Eventually a point is
reached at which the rates of the forward and reverse reactions are
equal. At this point NO further composition change takes place and 13
the reaction mixture is in chemical equilibrium.
Example 11: If the water-gas shift reaction,
CO(g) + H2O (g) ⇄ CO2 (g) + H2 (g)
proceeds to equilibrium at a temperature T(K), the mole fractions of the
four reactive species satisfy the relation

where K(T) is reaction equilibrium constant. At T = 1105 K, K = 1.

Suppose the feed to a reactor contains 1 mol of CO, 2 mol of H2O, and
no CO2 or H2, and the reaction mixture comes to equilibrium at 1105 K.
Calculate the equilibrium composition and the fractional conversion of the
limiting reactant.

Solution:

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CO(g) + H2O (g) ⇄ CO2 (g) + H2 (g)
1 mole + 2 mole

T = 1105 K, K = 1

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 CO(g) + H2O (g) ⇄ CO2 (g) + H2 (g)
1 mole + 2 mole

T = 1105 K, K = 1

(nH2O/ nCO )0 = 2/1 = 2

H2O is in excess (2 > 1)
(nH2O/ nCO )stoich = 1/1 = 1

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6.4 Multiple Reactions, Yield, and Selectivity

The engineer designing the reactor and specifying operating conditions for
it must consider not only how to maximize the production of the desired
product, but also how to minimize the production of undesired by-products.

The terms yield and selectivity are used to describe the degree to which
a desired reaction predominates over competing side reactions.

Yield defined above is always a fraction. It may also be expressed as a

percentage by multiplying by 100%. 17
Yield is also defined as moles of desired product divided by either moles of
reactant fed or moles of reactant consumed in the reactor.

For given feed and product compositions, the yields defined in these three
manners may have different values, so that when you see a reference to a
yield it is important to be aware of the working definition.

The concept of extent of reaction can be extended to multiple

reactions, only now each independent reaction has its own extent. If a set
of reactions takes place,

where vij is the stoichiometric coefficient of substance i in reaction j

(negative for reactants, positive for products).

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For example, consider the following reactions:

The extent of reaction is

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Example 12: The reactions,
C 2H 6 → C 2H 4 + H 2
C2H6 + H2 → 2 CH4

take place in a continuous reactor at steady state. The

feed contains 85 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.
Solution:

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C 2H 6 → C 2H 4 + H 2
C2H6 + H2 → 2 CH4

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C 2H 6 → C 2H 4 + H 2
C2H6 + H2 → 2 CH4

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7. BALANCES ON REACTIVE PROCESSES

7.1 Balances on Molecular and Atomic Species

The dehydrogenation of ethane in a steady-state continuous reactor,

C 2H 6 → C 2H 4 + H 2

Different balances could be written:

- Total mass (C2H6, C2H4, and H2): Input = Output, since all species
participate in the reaction.
- The balance equation for each of them include generation term (for C2H4
and H2) or consumption term (for C2H6).
- Balances on atomic species (carbon and hydrogen): Input = Output,
since atoms can neither be created (generation = 0) nor destroyed
(consumption = 0) in a chemical reaction.
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When we speak of a hydrogen balance, it could be:
- Balance on molecular hydrogen (H2): molecular hydrogen balance.
- Balance on total hydrogen (H): atomic hydrogen balance.

C2H6 → C2H4 + H2

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You could solve ṅ1 and ṅ2 either from two atomic balances or by using the
molecular species balances in conjunction with stoichiometric equation
for the reaction. 25
System that involve chemical reactions may be analyzed using:
a) Molecular species balances (approach used for non-reactive system).
b) Atomic species balances.
c) Extent of reaction.
Each approach leads to the same results.

7.2 Independent Equations, Species, and Reactions

Algebraic equations are independent if you cannot obtain any one of

them by adding and subtracting multiples of any of the other. For example,

are not independent, because [2] = 3 × [1]. They are really the same
equation. 26
If two molecular species are in the same ratio to each other wherever they
appear in a process and this ratio is incorporated in the flowchart labeling,
balances on those species will not be independent equations. Similarly, if
two atomic species occur in the same ratio wherever they appear in a
process, balances on those species will not be independent equations.

For example, consider a process in which a stream of liquid carbon

tetrachloride is vaporized into a stream of air.

Since nitrogen and oxygen are in the same ratio wherever they appear on
the flowchart (3.76 mol N2/mol O2), you 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 CCl4).
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Similarly, atomic nitrogen (N) and atomic oxygen (O) are always in the
same proportion to each other in the process (3.76:1) as are atomic
chlorine and atomic carbon (4 mol Cl/1 mol C).

Even though 4 atomic species are involved in this process, you may count
only 2 independent atomic species balances in the degree-of-freedom
analysis (1 for either O or N and 1 for either C or Cl).

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Chemical reactions are independent if the stoichiometric equation of any
one of them cannot be obtained by adding and subtracting multiples of the
stoichiometric equations of the others.

For example,

These three reactions are not all independent, since

Any two of the reactions are independent, since each one involves at least
one species that does not appear in the other one.
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7.3 Molecular Species Balances

If molecular species balances are used to determine unknown stream

variables for a reactive process, the degree-of-freedom analysis is:

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To illustrate the required procedure, consider the dehydrogenation of
ethane shown.

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7.4 Atomic Species Balances

All balances on atomic species (C, H, O, etc.) take the form Input = Output

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7.5 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 in terms
of extents of reaction, substitute known feed and product flow rates, and
solve for the extent of reaction and the remaining reactive species flow
rates. The degree-of-freedom analysis is:

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for the three species in the process becomes

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There are no hard and fast rules but we suggest the following guidelines:

• Atomic species balances lead to most straightforward solution

procedure.
• Extent of reaction are convenient for chemical equilibrium problems.
• Molecular species balances require more complex calculations than
the other two approaches and should be used only for simple system
involving one reaction.

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_______________________________
Homework: Solve Example 4.7-1 p. 131.
7.6 Product Separation and Recycle

Two definitions of reactant conversion are used in the analysis of chemical

reactors with product separation and recycle of unconsumed reactants:

For example,

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7.7 Purging

Suppose a material that enters with the fresh feed or is produced in a

reaction remains entirely in a recycle stream, rather than being carried out
in a process product. If nothing were done about this situation, the
substance would continuously enter the process and would have no way
of leaving; it would steadily accumulate, making the attainment of steady
state impossible. To prevent this buildup, a portion of the recycle stream
must be withdrawn as a purge stream to ride the process of the
substance in question.

Purging here is
to withdraw N2

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Example 13: Methanol is produced in the reaction,
CO2 + 3 H2 → CH3OH + H2O
The fresh feed to the process contains hydrogen, carbon dioxide, and 0.4 mole% inerts (I).
The reactor effluent passes to a condenser that removes essentially all of the methanol and
water formed and none of the reactants or inerts. The latter substances are recycled to the
reactor. To avoid buildup of the inerts in the system, a purge stream is withdrawn from the
recycle.
The feed to the reactor (not the fresh feed to the process) contains 28 mole% CO2, 70
mole% H2, and 2 mole% inerts. The single-pass conversion of hydrogen is 60%. Calculate
the molar flow rates and molar compositions of the fresh feed, total feed to the reactor, the
recycle stream, and purge stream for a methanol production rate of 155 kmol CH3OH/h.
Solution:

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8. COMBUSTION REACTIONS
8.1 Combustion Chemistry

Combustion is the rapid reaction of a fuel with oxygen. Combustion

products include CO2, H2O, and possibly CO and SO2. Fuel used in power
plant combustion furnaces are:

• Coal – carbon, hydrogen and sulfur, and various non-combustible materials.

• Fuel oil – high molecular weight hydrocarbons, some sulfur.
• Gaseous fuel – natural gas (methane).
• Liquefied petroleum gas – propane and/or butane.

A combustion reaction in which CO is formed from a hydrocarbon is

referred to as partial combustion or incomplete combustion of the
hydrocarbon.

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Air is the source of oxygen in most combustion reactors. Dry air has the
following molar composition:

In combustion calculations, it is acceptable to simplify this composition to

79% N2, 21% O2:

79 moles N2 / 21 moles O2 = 3.76 moles N2/mole O2.

Combustion on a wet basis is used to denote the component mole

fractions of a gas that contains water.
Combustion on a dry basis is used to denote the component mole
fractions of the same gas without water.
Stack gas or flue gas is the product gas that leaves a combustion 49
furnace.
Example 14: A stack gas contains 60 mole% N2, 15% CO2, 10% O2,
and the balance H2O. Calculate the molar composition of
the gas on a dry basis.
Solution:

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Example 15: Calculate the following dry basis stack gas composition on
a wet basis:
N2 65%; CO2 14%
CO 11%; O2 10%
A humidity measurement shows that the mole fraction of
H2O in the stack gas is 0.07.
Solution:

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8.2 Theoretical and Excess Air

If two reactants participate in a reaction and one is more expensive than

the other, the less expensive reactant must be fed in excess to increase
the conversion of valuable reactant.

Combustion reactions are run with more air than is needed to supply
oxygen in stoichiometric proportion to fuel.

Theoretical Oxygen: Moles of O2 needed for complete combustion of all

fuel fed to the reactor.
Theoretical Air: Quantity of air that contains the theoretical oxygen.
Excess Air: Amount by which air fed to reactor exceeds theoretical air.

If 50% excess air is supplied, then 53

Example 16: 100 mol/h of butane and 5000 mol/h of air are fed into a
combustion reactor. Calculate the percent excess air.
Solution:

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8.3 Material Balances on Combustion Reactors

The procedure here is the same as for any reactive system, however:

1. When you draw and label flowchart, be sure the outlet stream includes:
a) Unreacted fuel unless all fuel is consumed.
b) Unreacted oxygen.
c) Water and carbon dioxide, and carbon monoxide (if stated).
d) Nitrogen if fuel is burned with air and not pure oxygen.

2. To calculate oxygen feed rate from a specified excess oxygen or

percent excess air (both have same value),
a) First calculate theoretical O2 from fuel feed rate and the reaction
stoichiometry for complete combustion, and
b) Then calculate oxygen feed rate by multiplying theoretical oxygen
by (1 + fractional excess oxygen).

3. All three balance methods are convenient, but if several reactions occur
then atomic species balances are most convenient.
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Example 17: Ethane is burned with 50% excess air. The percentage
conversion of the ethane is 90%; of the ethane burned,
25% reacts to form CO and the balance reacts to form
CO2.
Calculate the molar composition of the stack gas on a dry
basis and the mole ratio of water to dry stack gas.
Solution:

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