The Chemical Reaction Equation and Stoichiometry: Objectives

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Chapter 9

The chemical reaction equation and stoichiometry


Objectives:
1. Write and balance chemical reaction equations.

2. Determine the stochiometric quantities of reactants and products in


moles or mass given the chemical reaction.

3. Define excess reactant, limiting reactant, conversion, degree of


completion, selectivity, yield, and extent of a reaction.

4. Identify the limiting and excess reactants in a reaction, and calculate


the fraction or percent excess reactant(s), the percent conversion or
completion, the yield, and the extent of reaction with the reactants
given in nonstoichiometric proportions.

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Material Balances on Reactive Processes

What does a reaction do to the general balance equation?

Accumulation = In – Out + Generation – Consumption

For a reactive process at steady-state, the general balance equation becomes:

Accumulation = In – Out + Generation – Consumption


0 = In – Out + Generation – Consumption

Accounts for material produced


or consumed within the system

The stoichiometric equation of the reaction imposes constraints on the


relative amounts of reactants and products in the input and output
streams.

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Material Balances on Reactive Processes
What quantities are conserved?

Type of Balance Without Rxn With Rxn

Total mass
Total moles
Mass of a chemical compound

Moles of a chemical compound

Mass of an atomic species


Moles of an atomic species

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Stoichiometry Definitions
Stoichiometry:
Theory of the proportions in which chemical species combine with one
another in a reaction
2 SO2 + O2 → 2 SO3

Stoichiometric Equation: An equation that relates the relative number of


molecules or moles of reactants and products (but not mass!) that participate
in a chemical reaction. To be valid, the equation must be balanced.

For example,
Are the following stoichiometric equations balanced?
C2H5OH + O2 → CO2 + H2O
(NH4)2Cr2O7 → Cr2O3 + N2 + H2O

C4H10 + 13/2 O2 → 4CO2 + 5 H2O

» Stoichiometric Coefficients: -1, -13/2, 4, 5

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Stoichiometry Definitions
Stoichiometric Coefficients ( ν i) : values preceding each molecular species (i) in a
balanced stoichiometric equation. Values are defined to be positive for products
and negative for reactants.
» -νe for reactants
» +νe for products
For the reaction:
2 SO2 + O2 → 2 SO3
νSO2 = -2 , νO2 = -1 , νSO3 = 2

Stoichiometric Ratio : ratio of stoichiometric coefficients in a balanced


stoichiometric equation. For the above reaction for example,

2mol SO3 generated


1mol O2 consumed

Two reactants, A and B, are in stoichiometric proportion if the ratio (moles of A


present)/(moles of B present) equals their stoichiometric ratio determined from
the balanced stoichiometric equation. 5
Limiting and Excess Reactants
If the reactants are not present in stoichiometric proportions, the reactant that is
completely consumed when a reaction is run to completion is known as the
limiting reactant. The other reactant(s) are termed excess reactant(s).

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

where, (nA)feed is the number of moles of an excess reactant, A, present


in the feed to a reactor and (nA)stoich is the stoichiometric requirement of
A, or the amount needed to react completely with the limiting reactant.

Percentage excess of A is 100 times the fractional excess.

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Identifying the Limiting Reactant
1. Balance the stoichiometric equation

2. Identify the reactant with the lowest stoichiometric coefficient. If there are two such
reactants, for example, A + B + 2C → D, select the reactant with the smallest number of moles
fed.

3. Set up stoichiometric ratios for each reactant using the reactant identified in Step 2 as the
denominator.

4. Set up corresponding ratios for each reactant using actual feed values, using the actual feed
value of the reactant identified in Step 2 as the denominator.

5. Compare the ratios

If, reactant x is not the limiting reactant

If, reactant x is the limiting reactant

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Conversion
Chemical reactions do not occur instantaneously, but rather, often proceed quite slowly.
Therefore, it is often not practical to design a reactor for complete conversion of the
limiting reactant. Instead, the reactant is separated from the reactor outlet stream and
recycled back to the reactor inlet. The Fractional conversion of a reactant is the ratio of
the amount reacted to the amount fed:

% Conversion= 100 Moles of feed that react or fA = (nA)reacted


Moles of feed introduced (nA)fed

Fractional conversion is unitless.

Conversion is related to the degree of completion of a reaction namely the percentage


or fraction of the limiting reactant converted into products.

Moles of the limiting reactant that react


degree of completion = 100
Moles of the limiting reactant introduced

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Extent of Reaction

The extent of reaction is a quantity that characterizes the reaction and can simplify
calculations. 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 stochiometric coefficient.

ni  nio
Extent of reaction  
vi
Where:   extent of reaction
ni = moles after reaction
nio = moles before reaction
νi = stoichiometric coefficient

The extent of reaction has the same units as n.

Another method to Identify the limiting reactant:


As a straight forward way of determining the limiting reactant, you can determine the
maximum extent of reaction, ξmax , for each reactant based on the complete reaction of the
reactant. The reactant with the smallest maximum extent of reaction is the limiting reactant.
 nio
imax 
vi
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Multiple Reactions
Generally, the synthesis of chemical products do not involve a single reaction but rather
multiple reactions. The goal is to maximize the production of the desirable product and
minimize the production of unwanted byproducts. For example, ethylene is produced by
the dehydrogenation of ethane:

C2H6 → C2H4 + H2
C2H6 + H2 → 2CH4
undesirable side
C2H4 + C2H6 → C3H6 + CH4
reactions
This leads to the following definitions:
moles of desired product formed
Yield =
moles of desired product formed if there were no side rxns and
limiting reactant reacted completely

moles of desired product formed


Selectivity =
moles of undesired product formed
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Multiple Reactions – Extent of Reaction
The concept of extent of reaction can also be applied to multiple reactions, with each
reaction having its own extent.
If a set of reactions takes place in a batch or continuous steady-state reactor, we can
write:

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


is the extent of reaction for reaction j.

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Example: Calculation of Various terms in reactions
Consider the following reactions:

Cl2(g) + C3H6 (g) C3H5Cl (g) + HCl (g) (a)

Cl2(g) + C3H6 (g) C3H6Cl2(g) (b)

C3H6 is propylene (MW= 42.08)


C3H5Cl (3-chloropropene) (MW= 76.53)
C3H6Cl2 is (1,2-dichloropropane) (MW= 112.99)

The species recovered after the reaction takes place for some time are
listed in this Table:
Species gmol
Cl2 141
C3H6 651
C3H5Cl 4.6
C3H6Cl2 24.5
HCl 4.6 12
Example: Calculation of Various terms in reactions
Based on the product distribution assuming that no allyl cholorides were present in the
feed, calculate the following:

a) How much Cl2 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 C3H5Cl?
e) What was the selectivity of C3H5Cl relative to C3H6Cl2?
f) What was the yield of C3H5Cl expressed in g of C3H5Cl to the g of C3H6 fed to the
reactor?
g) What was the extent of reaction of the first and second reactions?
h) In this example the waste is HCl (g). What is the mole efficiency for cholorine, (i.e., the
fraction of an element in the entering reactants that emerges in the exiting products,)?

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Test yourself: Limiting and excess reactants

Acetylene is hydrogenated to form ethane. The feed to the reactor contains 1.5 mol H2/mol
C2H2.
a) Calculate the stoichiometric reactant ratio (mol H2 react/mol C2H2 react) and the yield
ratio (kmol C2H6 formed/kmol H2 react).
b) Determine the limiting reactant and calculate the percentage by which the other reactant
is in excess.
c) Calculate the mass feed rate of hydrogen (kg/s) required to produce 4 × 106 metric tons of
ethane per year, assuming that the reaction goes to completion and that the process
operates for 24 hours a day, 300 days a year.
d) There is a definite drawback to running with one reactant in excess rather than feeding
the reactants in stoichiometric proportion. What is it?

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Example: Limiting reactant
Acrylonitrile is produced in the reaction of propylene, ammonia, and oxygen:

C3H6 + NH3 + 3/2 O2 C3H3N + 3H2O

The feed contains 10.0 mole% propylene, 12.0 mole% ammonia, and 78.0 mole% air. A
fractional conversion of 30.0% of the limiting reactant is achieved. Taking 100 mol of feed as a
basis, determine which reactant is limiting, the percentage by which each of the other
reactants is in excess, and the molar amounts of all product gas constituents for a 30%
conversion of the limiting reactant.

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Example: Yield and selectivity
The reactions
C2H6 → C2H4 + H2
C2H6 + H2 → 2 CH4

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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