Ch.E.

Calculations
Stoichiometry
Stoichiometry
 A branch of chemistry which deals with a
mass and volume relative in unit operations
and unit processes.
 It is a 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; that is, the number of atoms of

each atomic species must be the same on
both sides of the equation, since atoms can
neither be created nor destroyed in the
chemical equation.
Stoichiometric Coefficient
 Tells the relative amount of moles of
chemical species that reacts and are
produced in a chemical reaction.
a A + bB ----> c C +dD

1 CH4 + 2 O2 ----> 1 CO2 + 2 H 2O

m=(n)(mw)
(1) (16) + (2) (32) (1) (44) + (2) (18)

80 g 80 g
 Stoichiometric Ratio
(mass-mole relationship)
 Mole ratio obtained
1 CH4 + 2 O by using
2 ----> 1 COthe 2 + coefficients
2 H 2O
of the species5 in the 2 (5)chemical 1 (5)equation
2 (5)
--- ---- ---
including both reactants 1 and products.
1 1
 The stoichiometric
a A + ratio
b B ----> of ctwoC molecular
+dD
(n) b (n) c (n) d (n)
species participating----in a reaction -----
is----the ratio
of their stoichiometric a coefficients a ina the
balanced reaction equation.
a (y) (y) c (y) d (y)
--- ---- ----
b b b
n= m ; m = (n) (MW)
--------
MW
Stoichiometric Ratio
 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.
Stoichiometric Ratio
 Mass-mass
Example : relationship
1 CH4 + 2 O2 ----> 1 CO2 + 2 H2O
 Amount substance sought (mx)
Mass of CH4 = 100 grams
◦ = amount of substance given x gravimetric factor
 Gravimetric
Compute :mass O2,Factor
mass CO2, mass H2O
◦ =stoichiometric ratio of the coefficient of substance
sought and given x [ratio of MW/given]
Reaction Stoichiometry
Stoichiometry Involving Chemical
Reactions
 Limiting Reactants (LR)
◦ Reactant supplied in the LEAST stoichiometric amount;
◦ defines the degree of completion of the reaction;
◦ The reactant that would run out if a reaction proceeded to
completion.
 Excess Reactants (ER)
◦ Reactant whose amount supplied for the reaction is
GREATER than the theoretical amount;
 Theoretical Amount (TA)/Stoichiometric Requirement
◦ Amount of reactants or products involved in a complete
reaction.
◦ The amount needed to react completely with the limiting
reactant.
Stoichiometry Involving Chemical
Reactions
 Fractional excess=the ratio of the excess to
the stoichiometric requirement;
 % conversion=[amount of reactant

converted product/amount of reactant

supplied] x 100
 % excess=[supplied amount-theoretical

amount]/theoretical amount] x 100

 Degree of completion=[amount of

converted LR to Product/amount of LR
supplied]
Example Problem No. 1
 Phenol can be manufactured by reacting
chlorobenzene with sodium hydroxide.
 C H Cl + NaOH C H OH + NaCl
6 5 6 5
 To produce 1000 kg of phenol, 1200 kg of
NaOH and 1320 kg chlorobenzene are used.
 Determine :

◦ A). Limiting Reactant (LR) & Excess Reactant (ER)

◦ B). % Excess Reactant (Fractional Excess)
◦ C). Degree of Completion
◦ D). Yield of Phenol
Example Problem No. 2
 Nitrobenzene is produced by nitrating
benzene using a mixed acid, the reaction is:
 1C H + 1HNO  1C H NO + 1H O
6 6 3 6 5 2 2
 The conversion of benzene to nitrobenzene is
90%. 1000 kg of benzene and 2070 kg of
mixed acid are used: 39% HNO3, 53% H2SO4
and 8% H2O. Determine:
◦ A). Limiting Reactant (LR) & Excess Reactant (ER);
◦ B). Amount of Pure Nitrobenzene produced.
Practice Problem No.1
 Himmelbleau: (P2/p 247)
◦ Calcium oxide (CaO) is formed by
decomposing limestone (pure CaCO3). In
one kiln the reaction goes to 70%
completion.
 What is the composition of the solid
product withdrawn from the kiln?
 What is the yield in terms of pounds of
CO2 produced per pound of limestone
fed into the process.
Practice Problems 2
 Himmelbleau: (P3/p 247)
◦ Aluminum sulfate can be made by reacting
crushed bauxite ore with sulfuric acid,
according to the following chemical
equation:
Al2O3 + 3H2SO4  Al2(SO4)3 + 3 H2O
The bauxite ore contains 55.4% by weight
of aluminum oxide, the remainder being
impurities. The sulfuric acid solution
contains 77.7% pure sulfuric acid, the
remainder being water.
◦ To produce crude aluminum sulfate
containing 1798 lb of pure aluminum
sulfate, 1080 lb of bauxite ore and 2510
lb of sulfuric acid solutions are reacted.
 Identify the excess reactant?
 What percentage of the excess reactant
was consumed?
 What was the degree of completion of
the reaction?
Midterm Seatwork No. 1:
 The analysis of limestone gives 60%CaCO3,
33.5% MgCO3 and rest inert. It is treated with
12% aqueous sulfuric acid (by mass) to obtain
pure CO2. An excess of 15% of the acid over
the stoichiometric amounts is used to ascertain
that the reaction goes to completion. Based on
the treatment of 500 kg limestone, calculate:
◦ The amount of 100% (by mass) sulfuric acid required.
◦ The amount of the residue;
◦ The analysis of the residue left in the vessel;
◦ The moles of CO2 produced.
Multiple Reactions, Yield and
Selectivity
 In most chemical processes, reactants are
brought together with the object of
producing a desired product in a single
reaction;
 Unfortunately, reactants can usually combine

in more than one way, and the product once

formed may react to yield something less
desirable.
Multiple Reactions
 Ethylene  dehydrogenation of Ethane
 C2H6C2H4 + H2
 (desired)
 Hydrogen reacts with Ethane  Methane
 C2H6+ H2 2CH4
 (undesired)
 Ethylene reacts Ethane Proplyene +Methane
 C2H4 + C2H6  C3H6+ CH4
 (undesired)
Yield and Selectivity
 Terms are used to describe the degree to
which a desired reaction predominates over
competing side reactions.
 Yield=[moles of desired product
formed/moles that would have been formed
if there were no side reactions and the
limiting reactant had reacted completely]
 Selectivity=[moles of desired product
formed/moles of undesired product formed]
Balances on Reactive Processes
 Balances on Molecular And Atomic Species
◦ The first has the simple form input=output;
◦ Given species all participate in the reaction;
◦ The balance equation for each of them must include a
generation term or consumption term;
◦ Balances on atomic species can be written
input=output;
◦ Since atoms can neither be created (generation=0) nor
destroyed (consumption=0) in a chemical reaction.
◦ Recall that the general balance equation for a steady
state process is input + generation=output +
consumption)
Balances on Reactive Processes
 In general, systems that involve
chemical reactions may be analyzed
using
a) Molecular species balances (the approach
always used for non reactive systems;
b) Atomic species balances;
c) Extent of reaction.
Molecular Species Balances
 If
the molecular species balances are
used to determine unknown stream
variables for a reactive process, the
balances on reactive species must
contain generation and/or
consumption terms.
Atomic Species Balances
 All
balances on atomic species take
the form “input=output” since atomic
species can neither be generated nor
consumed in chemical reactions (as
opposed to nuclear reaction).
Extent of Reaction
 The third way to determine unknown molar
flow rates for reactive processes is to write
expressions for each product species flow
rate (or molar amount) in terms of extent of
reaction, substitute known feed and product
flow rates, solve for the extent of reaction
and the remaining reactive species flow
rates.
Guidelines:
 Atomic species balances generally lead to the
most straightforward solution procedure
especially when more than one reaction is
involved.
 Extent 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.
Practice Problems [4.39-170]
Practice Problems [4.42-172]
Practice Problem [4.49 – 174]