Lecture 4

Material Balances with Chemical Reaction

Chemical Reaction Stoichiometry

The occurrence of a chemical reaction in a process bring

several complications into the material balance
procedures. The stoichiometric equation of the reaction
imposes constraints on the relative amounts of
reactants and products in the input and output streams,
for example: if A  B
you cannot start with 1 mol of pure A and end with 2
mol of B.

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 Stoichiometry
The stoichiometry is the theory of the proportions in
which chemical species combine with one another. The
stoichiometric equation of a chemical reaction in a
statement of the relative number of molecules or moles
of reactants and products that participate in the
reaction. For example the stoichiometric equation:

2SO2  O2  2SO3

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 Stoichiometry
This indicates that for every two molecules (g-moles, lb-
mole) of SO2 that react, one molecule (g-mole, lb-mole) of
O2 reacts to produce two molecules (g-moles, lb-moles) of
SO3. the numbers that precede the formulas for each
species are the stoichiometric coefficients of the reaction
components.
A valid stoichiometric equation must be balanced, that is,
the number of atoms of each atomic species must be the
same on both of the equation, since atoms can neither be
created not destroyed in chemical reactions. The equation:

2SO2  O2  2SO3
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 Stoichiometry
Cannot be valid, for example, since it indicates that three
atoms of atomic oxygen (O) are produced for every four
atoms that enter into the reaction, for a net loss of one
atom, but:
1  1S  1S 
SO2  O2  SO3  
2  3O  3O 
And

 2S  2S 
2SO2  O2  2SO3  
 6O  6O 

Are balanced.

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

2SO2  O2  2SO3
You can write the stoichiometric ratio :
2 moles SO3 generated 2 moles SO 2 consumed
,
1 mole O2 consumed 2 moles SO3 generated
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 Limiting and Excess Reactions
Limiting Reactant - The reactant in a chemical reaction that limits
the amount of product that can be formed. The reaction will stop
when all of the limiting reactant is consumed.
Excess Reactant - The reactant in a chemical reaction that remains
when a reaction stops when the limiting reactant is completely
consumed. The excess reactant remains because there is nothing
with which it can react.

No matter how many tires there are, if there are only 8 car bodies,
then only 8 cars can be made. Likewise with chemistry, if there is
only a certain amount of one reactant available for a reaction, the
reaction must stop when that reactant is consumed whether or not
the other reactant has been used up.
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 Limiting and Excess Reactions
Tow reactant, A and B, are said to be present in stoichiometric
proportion if the ratio (moles A present) (moles B present) equals the
stoichiometric ratio obtained from the balanced reaction equation. For
the reactants in the reaction:
2SO2  O2  2SO3
To be present in stoichiometric proportion, there must be 2 moles of SO2
for every mole of O2 (so that 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 are
consumed. In the above reaction, for example, if 200 mol of SO2 and 100
mol of O2 are initially present and the reaction proceeds to completion,
the SO2 and O2 would disappear at the same instant. It follows that if
you start with 100 mol of O2 and less than 200 mol of SO2 (i.e., if the SO2
is present in less than its stoichiometric proportion), the SO2 would run
out first, while if more than 200 mol of SO2 is initially present the O2
would run out. 8
 Limiting and Excess Reactions

The reactant that would run out if a reaction proceeded to

completion is called the limiting reactant, and the other
reactants are termed 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.

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 Limiting and Excess Reactions
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 of the reaction goes to completion. The
fractional excess of the reactant is the ratio of the excess to
the stoichiometric requirement:

 nA  feed -  nA  stoich
fractional excess of A= Eq.1
 nA  stoich
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 Limiting and Excess Reactions
The percentage excess of A is 100 times the fractional excess.
Consider, for example, the hydrogenation of acetylene to form ethane:
C2 H2  2H2  C2 H6
And suppose that 20.0 kmol/h of acetylene and 50.0 kmol/h of
hydrogen are fed to a reactor. The stoichiometric ratio of hydrogen to
acetylene is 2:1 (the ratio of coefficients in the stoichiometric
equation), and since the ratio of H2 to C2H2 in the feed is 2.5:1 (50:20),
hydrogen is fed in a greater-than-stoichiometric proportion to
acetylene. Acetylene is therefore the limiting reactant. Since it would
take 40.0 kmol H2/h to react completely with all the acetylene fed to
the reactor, (n)stoich = 40.0 kmol/h, and from equation Eq.1 :
 50.0-40.0  kmol/h
fractional excess of H 2 =  0.25
40.0 kmol / h
We say that there is 25 % excess hydrogen in the feed.
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 Fractional conversion
Chemical reactions do not take place instantaneously, and indeed
often proceed rather slowly. In such cases, 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 the recycled to the reactor inlet. The fractional conversion
of a reactant is the ratio:
moles reacted
f= Eq. 2
moles fed
The fraction unreacted is accordingly (1 –f). If 100 moles of a reactant
are fed and 90 moles react, the fractional conversion is 0.90 (the
percentage conversion is 90 %) and the fraction unreacted is 0.10.
If 20 mol/min of a reactant is fed and the percentage conversion is 80
%, then (20)(0.80) = 16 mol/min has reacted and (20)(1-0.80) =
4mol/min remains unreacted. 12
Exercise
Consider the reaction H2O2 + O3  H2O + 2O2 . If you start with 50 g
of H2O2 and 25 grams of O3, and 25 % of the moles of are
consumed, find the molar extent of reaction and the changes in the
other components.

Solution
First we need to convert to moles, since stoichiometry is not valid
when units are in terms of mass.
50 g H2O2 * (1 mol/34 g) = 1.471 moles H2O2
25 g O3 * (1 mol/48 g) = 0.5208 moles O3
Clearly ozone is the limiting reactant here. Since 25 % is consumed,
we have that:
n (O3) = 0.25 * 0.5208 = 0.1302 moles O3
X = (0.1302/1) = 0.1302
Hence, by definition, And then we have
n (H2O2) = 0.1302 ; n (H2O) = 0.1302 ; n (O2) = 2* 0.1302 =0.2604 ,
all in moles of the appropriate substrate.

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 Limiting and Excess Reactions
Example Limiting Reactant Calculation:
A 2.00 g sample of ammonia is mixed with 4.00 g of oxygen. Which is
the limiting reactant and how much excess reactant remains after the
reaction has stopped?
First, we need to create a balanced equation for the reaction:

4 NH3(g) + 5 O2(g)  4 NO(g) + 6 H2O(g)

Next we can use stoichiometry to calculate how much product is
produced by each reactant.
NOTE: It does not matter which product is chosen, but the same
product must be used for both reactants so that the amounts can be
compared.

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 Limiting and Excess Reactions
The reactant that produces the lesser amount of product in
this case is the oxygen, which is thus the "limiting reactant."
Next, to find the amount of excess reactant, we must
calculate how much of the non-limiting reactant (ammonia)
actually did react with the limiting reactant (oxygen).

We're not finished yet though. 1.70 g is the amount of

ammonia that reacted, not what is left over. To find the
amount of excess reactant remaining, subtract the amount
that reacted from the amount in the original sample.

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 Limiting and Excess Reactions
Problems:
1. A sample contains 27.1 g of calcium oxide. How many
moles of calcium oxide are in the sample?
NOTE: Use the Periodic Table to find the molecular mass
(grams per mole)

2. How many atoms are in 0.652 mol of iron?

NOTE: A mole is by definition 6.0220 x 1023 particles which
can generally be rounded to 6.02 x 1023.

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3. How many liters does 3.8 moles of O2 occupy at STP (standard
temperature and pressure)?
NOTE: At STP, 1 mole of any gas = 22.4 L. STP is 273K (0°C) and
1 atm.

4. A solution of NaCl has a molarity of 0.549 M. How many moles

are in 350. mL of this solution?
NOTE: Molarity is MOLES per LITER. The volume in milliliters
must be converted to Liters.

5. How many grams of sodium hydroxide are needed to make

250. mL of a 0.200 M solution?

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6. How many grams of carbon dioxide are there in a container
with a volume of 4.50 L at STP?

7. How many moles of nitrogen are there in a 7.45 mol sample

of ammonium phosphate?

8. If 120. g of propane, C3H8, is burned in excess oxygen, how

many grams of water

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9. 90.0 g of FeCl3 reacts with 52.0 g of H2S.

- What is the limiting reactant?

- What is the mass of HCl produced?

- What mass of excess reactant remains after the reaction?

NOTE: The limiting reactant is the reactant that limits the amount of

product that can be formed and is completely consumed during

the reaction.

The excess reactant is the reactant that is left over once the

reaction has stopped due to the limiting reactant.

2FeCl3 + 3H2S = 6HCl + Fe2S3

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First step: 90 g FeCl3
grams of FeCl3  moles of FeCl3  moles of HCl  grams of HCl
Moles of HCl =
90 g FeCl3 x (1 mole FeCl3 / 162 g FeCl3) x (6 moles HCl / 2 moles FeCl3) x
(36.5 g HCl / 1 mole HCl) = 60.8 g HCl

Second step: 52 g H2S

Moles of HCl =
52 g H2S x (1 moles H2S/34.1 g H2S) x (6 moles HCl/3 moles H2S) x (36.5
g H2S / 1 mole HCl) = 111 g HCl
The Limitting reactant is FeCl3
The mass of HCl produced is : 60.8 g HCl
The mass of excess reactant ( H2S) after reaction:
Mass H2S reacted = 90 g FeCl3 x (1 mole FeCl3 / 162 g FeCl3) x
(6 moles H2S / 2 moles FeCl3) x (34.1 g H2S / 1 mole H2S) = 28.4 g H2S
H2S excess = 52 – 28.4 = 23.6 g 20
Example

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Solution