CHEN 211-Principles of

Chemical Engineering
Dr. Husain Baaqel
Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Stoichiometry
The occurrence of a chemical reaction in a process brings several
complications into material balance:

• The stochiometric equation imposes constraints on the relative amounts

of reactants and products in the input and output steams (if AB, for
example, then you can only get 1 mol of B for every mol of A).
• A material balance on a reactive substance does not have the simple form
input = output, but must include a generation and or consumption term.

The stochiometric equation of a chemical reaction is a statement of the

relative amounts of reactants and products that participate in the reaction. A
stochiometric equation is valid only if the number of atoms of each atomic
species is balanced.
Dr. Husain Baaqel
Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Stoichiometry
SO2 + O2  SO3 2SO2 + O2  2SO3
N2 + H2  NH3 N2 + 3H2  2NH3

A stochiometric coefficients (vi) of the ith species in a balanced chemical

reaction is the number written in front of this species to balance the number
of each element on both the reactant and product sides of the equation,
combined with a sign that is negative for reactants and positive for products.

vSO2 = -2 vO2 = -1 vSO3 = 2

A stochiometric ratio of two molecular species participating in a reaction is

the ratio of their stochiometric coefficients without the sign (|vi |).
Stochiometric ratio of SO3 generated to O2 consumed = 2/1 = 2
Stochiometric ratio of SO3 generated to SO2 consumed = 2/2 = 1 Dr. Husain Baaqel
 Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Limiting and Excess Reactants, Fractional

Conversion, and Extent of Reaction
Concept of limiting and excess reactants:

Missing tires

Reactant Product
• Since there are only 4 tires and two car bodies, only one car can be completely manufactured.
Likewise with chemistry, if there is only a certain amount of one reactant (limiting) available, i.e. the
other reactant in excess, the reaction must stop when the reactant is fully consumed whether or not
the other reactant has been used up.
• It limits the amount of the product.
Dr. Husain Baaqel
Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Limiting and Excess Reactants, Fractional

Conversion, and Extent of Reaction
Limiting reactant: the reactant that would run out first if a reaction proceeded to
completion. (the reaction will stop when all the limiting reactant is consumed)

Excess reactant: the reactant that is present in excess of the limiting reactant. (the
reactant in a chemical reaction that remains when a reaction stops when limiting
reactants is completely consumed, i.e. what is left over after the reaction stops because
the limiting reactant got all used up.

• To determine the limiting reactant for a certain feed divide the number of moles of
each reactant in the feed by its stochiometric coefficient without the sign (ni/|vi|).
• The limiting reactant is the species with the smallest ratio.

Dr. Husain Baaqel

Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Limiting and Excess Reactants, Fractional

Conversion, and Extent of Reaction
% Excess = (moles fed – moles required)/moles required x 100%
= (Nf – Ns)/Ns x 100%

Where moles required is based on the moles required to react completely with the limiting
reactant.

Nf : Number of moles of an excess reactant present in the feed.

Ns : Stoichiometric requirement or the amount needed to react completely with the limiting
reactant.

Dr. Husain Baaqel

Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Limiting and Excess Reactants, Fractional

Conversion, and Extent of Reaction
The extent of reaction (ξ) – an extensive quantity describing the progress of a chemical
reaction.
We define the extent of reaction ξ (the Greek letter xi, which is pronounced as zai) as follows:
n − n (moles i)
ξ = i io
vi (moles i)
The extent of reaction is clearly dimensionless. Other key properties of ξ are that it starts at
zero when the reaction commences, increases as the reaction proceeds, and has the same
value for all species.
A + 2B  C

n − n (moles i) nA − nAo (moles A) nB − nBo (moles B) nC − nCo (moles C)

ξ = i io = = =
vi (moles i) −1 mole A −2 mole B 1 mole C
Dr. Husain Baaqel
Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Stoichiometry, and Limiting and Excess

Reactants
Exercise:
If 1 kg of benzene (C6H6) is oxidized with oxygen, how many kilograms of O2 are needed to convert all
of the benzene to CO2 and H2O?

kmore GHG
6 0.0128
1KSC6
61 1 1 from E 0.096
0.0128 Kmore GHG kmore

3 07 19 02
0.096 kmore 0
MEEE Dr. Husain Baaqel
Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Stoichiometry, and Limiting and Excess

Reactants a ExcessMat
7
211
413521 12 is 2.2
Exercise: at
which means nzinex.es
inIthIteffgmfd
For the following cases, determine which reactant is limiting and which is in excess as well as the
percent excess for that component:

(a) 2 mol of nitrogen (N2) reacts with 4 mol of hydrogen (H2) to form ammonia (NH3) via the reaction:
N2 + 3H2  2NH3
(b) 100 kg ethanol (C2H5OH) reacts with 100 kg of acetic acid (CH3COOH) to form ethyl acetate:
C2H5OH + CH3COOH CH3COOHC2H5 + H2O
(c) 64 g of methanol (CH3OH) reacts with 0.5 mol of oxygen (O2) to form formaldehyde:
CH3OH + 1/2O2  HCHO + H2O

22H50 H looks 1 Excess

2.12 kmore
b
CH COOH 1009 11
67
9121511 15 29.9
Dr. Husain Baaqel
Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Stoichiometry, and Limiting and Excess

Reactants
Exercise:
Ammonia is oxidized to nitric oxide in the following reaction:

4NH3 + 5O2  4NO + 6H2O

(a) Calculate the ratio (lb-mole O2 reacted/lb-mole NO formed).

(b) If ammonia is fed to a continuous reactor at a rate of 100.0 kmol NH3/h, what oxygen feed rate
(kmol/h) would correspond to 40.0% excess O2?
(c) If 50.0 kg of ammonia and 100.0 kg of oxygen are fed to a batch reactor, determine the limiting
reactant, the percentage by which the other reactant is in excess, and the extent of reaction and mass
of NO produced (kg) if the reaction proceeds to completion.

100 Req
Dr. Husain Baaqel
Excess
Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Limiting and Excess Reactants, Fractional

Conversion, and Extent of Reaction
Chemical reactions do not take place instantaneously, and they are usually slow. In
such cases, it is not practical to design the reactor for complete conversion of the
limiting reactant; the reactor effluent emerges with some of the limiting reactant still
present and is then usually separated from the product and recycled to the reactor
inlet.
• The fractional conversion of a reactant is the ratio of the amount of reactant
reacted to the amount fed.
moles reacted (ni )fed −(ni )out
f= =
moles fed (ni )fed
• % conversion of a reactant = fractional conversation x 100%
• Fractional unreacted = 1-f

Dr. Husain Baaqel

 Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Limiting and Excess Reactants, Fractional

Conversion, and Extent of Reaction
Exercise: a 5 no 1 25 5 0 8 Hi25
Ethylene oxide (C2H4O) is produced by the reaction of ethylene (C2H4) with oxygen:
ne2Hy
ne 895
n 0 25 5 2

0y
b n
g 2C2H4 + O2  2C2H4O
noczHYO.gg
The feed to the reactor contains 5 mol/h of ethylene, 3 mol/h of oxygen, and 2 mol/h of ethylene oxide.
Set up the compound balances in general, and then use these to solve the cases suggested as follows:

a. Suppose the amount of C2H4 coming out of the reactor is 5 mol/h, how much reaction has occurred?
b. How much reaction has occurred if ṅ C H O = 6 mol/h?
2 4

t.isg
c. How much reaction has occurred if if nC H = 0 mol/h?
̇
2 4
d. Which component is the limiting reagent?
e. What is the theoretical yield if fractional conversion is 1?
f. What is the fractional conversion if ṅ C H = 2 mol/h?
2 4
Dr. Husain Baaqel
Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Stoichiometry, Limiting and Excess

Reactants, Fractional Conversion, and
Extent of Reaction
Exercise:
The reaction between ethylene and hydrogen bromide to form ethyl bromide is carried out in a
continuous reactor. The product stream is analyzed and found to contain 51.7 mole% C2H5Br and
17.3% HBr. The feed to the reactor contains only ethylene and hydrogen bromide. Calculate the
fractional conversion of the limiting reactant and the percentage by which the other reactant is in
excess. If the molar flow rate of the feed stream is 165 mol/s, what is the extent of reaction?

Dr. Husain Baaqel

Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Multiple Reactions, Yield, and Selectivity

• Normally, recants are brought together to produce a desired product in a single reaction.
Unfortunately, reactants can usually combine in more than one way and produce
something less desirable. The result of these side reactions is an economic loss.
• An example is the production of ethylene (desired product) from ethane:
C2H6  C2H4 + H2 main reaction
• A side reaction can occur to produce methane (undesired by-product):
C2H6 + H2  2CH4 side reaction
• The designer concern is how to maximize the production of the desired product and to
minimize the production of undesired by-products. In this regard, the following terms are
used:

mole of desired product formed

yield =
moles formed at 100% conversion with no side reactions
(moles that would have been formed if there were no side reactions and the limiting reactant had reacted completely)

moles of desired product formed

selectivity =
moles of undesired product formed
Dr. Husain Baaqel
Fundamentals of Material Balances | Chemical Reaction Stoichiometry Dr. Husain Baaqel

Multiple Reactions, Yield, and Selectivity

• The concept of extent of reaction can be extended to multiple reactions, only now each
independent reaction has its own extent (𝝃𝟏 , 𝝃𝟐 , 𝝃𝟑 , …….).
• If a set of reactions takes place in a reactor and 𝑣 is the stochiometric coefficient of
substance 𝑖 in reaction 𝑗, we may then write:

ni = nio + vij ξj
j
Fundamentals of Material Balances | Chemical Reaction Stoichiometry

Multiple Reactions, Yield, and Selectivity

Exercise:
The following reactions take place in a reactor, where CO is the undesired product:

C2H6 + 3.5O2  2CO2 + 3H2O

C2H6 + 2.5O2  2CO + 3H2O

The feed to a reactor consists of 100 mol C2H6 and 500 mol O2. The product stream was analyzed and
found to contain 20 mol C2H6, 120 mol CO2, 40 mol CO, 240 mol O2, and 240 mol H2O. The reactor
conversion is 80%. Calculate the yield and selectivity.

yield E1fis.at 2 1 06

1
3
selectivity E 128 Dr. Husain Baaqel
Conversion Factors

Dr. Husain Baaqel