CHEMICAL PROCESS

CALCULATIONS
Balances on Reactive Processes 1
 RECOMMENDED
READIING
1. R. M. Felder, R.W. Rousseau, “Elementary Principles of Chemical Processes”

2. F.S Atalay “Kütle ve Enerji Denklikleri”

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 The presence of a chemical reaction in a process brings several complications into the
material balances.

 A material balance on a reactive substance does not have the simple form input=output,
must include generation and consumption terms.

 In writing material balance equations for the processes involving chemical reaction
stoichiometry should be taken into account.

 Accumulation = input-output+generation -consumption

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STOICHIOMETRY
 Stoichiometry; stoichiometry is the theory of the proportions in which chemical species combine
with one another.
 The 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.

Stoichiometric equation relates the number of moles of reactants and products in a chemical
reaction.

To obtain valid stoichiometric equation, equation must be balanced.

C2H5OH + O2 → CO2 + H2O

The following equation is balanced because the number of atoms (C, H, O) is the same on both
sides of equation.
C2H5OH + 3O2 → 2CO2 + 3H2O

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  For example, let’s look the combustion of heptane.

C7H16 + 11O2 → 7CO2 + 8H2O + Q ↑

We see that 1 mole of heptane will react with 11 moles of O2 to give 7 moles of CO2 and 8 moles of
H2O.
Also, one mole CO2 is formed from each 1/7 mole of C7H6.
So, these ratios are known the stoichiometric ratio and it is the ratio of their stoichiometric
coefficients in the balanced equation.

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 The stoichiometric coefficients are the values preceding each molecular species, i, in a
balanced equation. Values are defined as positive for products and negative for reactants.

For the reaction

2SO2 + O2 → 2SO3

γSO2 = -2, γO2 = -1, γSO3 = 2

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STOICHIOMETRIC RATIO
 For example, if we want to determine the required amount of O2 to produce 1600 kg/h of SO3
from SO2;

2SO2 + O2 → 2SO3
The stoichiometric ratio is employed in solving material balance problems that involves this
chemical reaction.

The stoichiometric ratio = 2 kmole SO3 / 1 kmole O2

kg SO3 1 kmole SO3 1 kmole O2

1600 ( ) = 10 kmol O2/h
ℎ 80 kg SO3 2 kmole SO3

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8
 A reactant is limiting if it is present in less than its stoichiometric proportion relatively to
other reactants.
 Limiting reactant is the reactant that would be the first to be consumed completely, if the
reaction were complete.

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 In order to find the limiting reactant, you balance the equation and then take ratio of the
reactant amount (mole, flow rate) in the feed to reactant stoichiometric coefficient, that is

𝑁𝑖0 𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖

=
𝛾𝑖 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖

The ratio with the lowest value corresponds to the limiting reactant.

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  Consider the following chemical reaction
2SO2 + O2  2SO3

If reactants are fed to a chemical reactor in stoichiometric proportion and the reaction proceeds to
completion, all of the reactants are consumed. For example;

If 200 mol SO2 and 100 mol O2 are initially present, SO2 and O2 would disappear at the same
instant

If you start 100 mol SO2 and 100 mol O2, SO2 disappears before O2.
limiting SO2, excess O2.
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 All reactants, other than the limiting reactant, are termed excess reactants. An excess
reactant is not fully used up when the reaction is complete.

moles of A in feed − stoichiometric amount of A

% Excess of A = x100
stoichiometric amount of A

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For the following cases, determine which reactant is limiting and which is in excess as well as
the percent excess for that component.
 2 mol of nitrogen (N2) reacts with 4 mol of hydrogen (H2) to form ammonia (NH3) via the
reaction:
N2 + 3H2→ 2NH3

(nN2)0 = 2 mol, (nH2)0 = 4 mol,

(𝑛𝑁2 )0 2
= =2
𝛾𝑁2 1
(𝑛𝐻2 )0 4
= H2 is limiting reactant
𝛾𝐻2 3

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 For the following cases, determine which reactant is limiting and which is in excess as well as
the percent excess for that component.
 100 kg ethanol (C2H5OH) reacts with 100 kg of acetic acid (CH3COOH) to form ethyl acetate:
C2H5OH + CH3COOH→ CH3COOHC2H5 + H2O

(nC2H5OH)0 = 100/46= 2.17 kmol, (nCH3COOH)0 = 100/60 = 1.67 kmol

(𝑛C2H5OH )0 2.17 Acetic acid is limiting reactant
= = 2.17
𝛾C2H5OH 1
1
(𝑛CH3COOH )0 1.67 2.17 − 1.67( )
= = 1.67 % Excess of 𝑒𝑡ℎ𝑎𝑛𝑜𝑙 = 1 x100 = 30%
𝛾CH3COOH 1 1
1.67( )
1

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For the following cases, determine which reactant is limiting and which is in excess as well as
the percent excess for that component.
 64 g of methanol (CH3OH) reacts with 0.5 mol of oxygen (O2) to form formaldehyde:
CH3OH +1/2 O2 → HCHO + H2O

(nCH3OH)0 = 64/32= 2 mol, (nO2)0 = 0.5 mol

(𝑛CH3OH )0 2
= =2 Oxygen is limiting reactant
𝛾CH3OH 1

(𝑛O2 )0 0.5 1
= =1 2 − 0.5
𝛾O2 0.5 % Excess of 𝑚𝑒𝑡ℎ𝑎𝑛𝑜𝑙 = 0.5 x100 = 100%
1
0.5
0.5
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Fractional Conversion
 It is not practical to design a reactor for the complete conversion of the limiting reactant. Only
portion of limiting reacts, remaining part of limiting reactant is separated from the reactor
outlet stream and recycled back to the reactor inlet.
 The fractional conversion of a reactant A is the ratio of the amount of reacted to the amount of
to the reactor

moles reacted 𝑛𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑛𝐴 𝑖𝑛− 𝑛𝐴 𝑜𝑢𝑡

f= = =
moles fed 𝑛𝐴 𝑖𝑛 𝑛𝐴 𝑖𝑛

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 If 100 moles of a reactant are fed to the reactor and 90 moles of them are reacted then the
fractional conversion is 0.9 (the percentage conversion is 90%).
 The percentage conversion of component A is

𝑛𝐴 𝑖𝑛− 𝑛𝐴 𝑜𝑢𝑡 𝑛𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑

𝑥100 = 𝑥100
𝑛𝐴 𝑖𝑛 𝑛𝐴 𝑖𝑛

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 The extent of reaction is the amount of a species converted in a reaction divided by the species
stoichiometric coefficient.
 The extent of reaction can be very useful for simplifying the material balance equations.
 Suppose that you start with ni0 moles of a particular reactant (Ai).

 Let’s define γi as the stoichiometric coefficients of the species and ni is the amount of Ai at
reactor outlet.

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Therefore, ni= nin + ξβi

β i= γ i if Ai is product
βi=- γi if Ai is reactant
βi=0 if Ai is inert

and ξ is called extent of reaction (amount of the reacted of limiting reactant)

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Ethylene oxide is produced by the reaction of ethylene with oxygen as in the following reaction;
2C2H4 + O2 ↔ 2C2H4O
The feed to the reactor contains 5 mol ethylene, 3 mol oxygen, and 2 mol ethylene oxide. Draw
and label the process flow sheet. Write the material balance equations as a function of the extent
of reaction.

(nC2H4)0 = 5 mol, (nO2)0 = 3 mol, (nC2H4O)0 = 2 mol

ni= nin + ξβi

(nC2H4)
Reactor (nC2H4)= (nC2H4)0 -2ξ
(nC2H4)0 = 5 mol (nO2)
(nO2)0 = 3 mol (nC2H4O) (nO2)= (nO2)0 -ξ
(nC2H4O)0 = 2 mol (nC2H4O)=(nC2H4O)0 +2 ξ

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Ammonia is burned to form nitric oxide and water:
4NH3 +5 O2 → 4NO + 6 H2O
The fractional conversion of oxygen is 0.5. The inlet molar flow rate is 5 mol/h of NH3 and 5
mol/h of oxygen. Calculate the exit component molar flow rates using the two methods:
a. Extent of reaction method
b. Molecular species balance approach fO2 = 0.5

4NH3 +5 O2 → 4NO + 6 H2O reacted O2

fO2 = = 0.5 =0.5 mol/h
inlet O2
n1 NH3 ni= nin + ξβi
Reactor 5
NH3 5 mol/h fO2 = = 0.5 (nNH3)= (nNH3)0 -4ξ=3 mol/h
n2 O2 5
O2 5 mol/h n3 NO In Out (nO2)= (nO2)0 -5ξ =2.5 mol/h
n4 H2O NH3 5 5-4
O2 5 5-5
(nNO)=(nNO)0 +4ξ = 2
NO 0 4 (nNO)=(nNO)0 +4ξ =2 mol/h
H2O 0 6
(nH2O)=(nH2O)0 +6ξ= 3 21
Total 10 10+
Ammonia is burned to form nitric oxide and water:
4NH3 +5 O2 → 4NO + 6 H2O
The fractional conversion of oxygen is 0.5. The inlet molar flow rate is 5 mol/h of NH3 and 5 mol/h
of oxygen. Calculate the exit component molar flow rates using the two methods:
a. Extent of reaction method
fO2 = 0.5
b. Molecular species balance approach
reacted O2
fO2 = = 0.5
4NH3 +5 O2 → 4NO + 6 H2O inlet O2
reacted O2 = 2.5 mol/h
n1 NH3 Input- output + generation – consumption = accumulation
Reactor
NH3 5 mol/h n2 O2 for NH3 for NO
O2 5 mol/h n3 NO 5-n1+0– (2.5)(4/5)= 0 0-n3+ (2.5)(4/5)– 0= 0
n = 3 mol/h n3 = 2 mol/h
n 4 H2 O 1

for O2 for H2O

5-n2+0– (2.5)= 0 0-n4+ (2.5)(6/5)– 0= 0
n2 = 2.5 mol/h n4 = 3 mol/h 22
Ethylene oxide (C2H4O) is produced by the reaction of ethylene (C2H4) with oxygen:
2C2H4 + O2 ↔ 2C2H4O
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. How much reaction has
occurred?
b. How much reaction has occurred if the amount of C2H4 = 6 mol/h?
c. How much reaction has occurred if the amount of C2H4 = 0?
d. Which component is the limiting reagent?
e. What is the theoretical yield?
f. What is the fractional conversion if the amount of C2H4 =2?

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Acrylonitrile is produced by a reaction of propylene, ammonia and oxygen.
C3H6 + NH3 + 3/2 O2 → C3H3N + 3H2O
The feed contains 10mole% propylene, 12% NH3 and 78% air. A fractional conversion of 30% of
the limiting reactant is achieved. Determine which reactant is limiting; the percentage by
which each of the other reactants is excess; molar flow rates of all product gas taking 100 mol
of feed basis. 12−10
% 𝑒𝑥𝑐𝑒𝑠𝑠 𝑜𝑓 𝑁𝐻3 = 𝑥100 = 20%
10
Limiting reactant is propylene 16.4−15
% 𝑒𝑥𝑐𝑒𝑠𝑠 𝑜𝑓 𝑂2 = 15 𝑥100 = 9.3%
 =10(0.3)=3 mol/h

n1 NH3 ni= nin + ξβi

Reactor
NH3 12 mol/h n2 O2 (n1)= 12-ξ=9 mol/h
air 78 mol/h n3 C3H6 (n2)= 16.4-1.5ξ=11.9 mol/h
C3H6 10 mol/h n 4 H2 O (n3)= 10-ξ=7 mol/h
n5 C3H3N (n4)= 0+3ξ=9 mol/h
(n5)= 0+ξ=3 mol/h

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Methanol is dehydrogenated in a catalytic reactor to form formaldehyde in the reaction:
CH3OH → HCHO + H2
Formaldehyde in the reactor product is separated from the unreacted methanol and hydrogen.
The production rate of formaldehyde is 30 kmol/h. If the conversion is 60%, calculate the
required feed rate of methanol to the process in kmol/h.

In Out
CH3OH F F-
H2 0 
HCHO 0 
n1 CH3OH Total 0 F+
Reactor
CH3OH F kmol/h n 2 H2
n3 HCHO  = 30 kmol/h


= 0.6 𝐹=(30)/0.6=50 kmol/h
𝐹

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Formaldehyde is produced by the dehydrogenation of ethanol in a catalytic reactor. The
following reaction takes place in the reactor:
CH3OH → HCHO + H2
Methanol feed rate to the reactor is 50 kmol/h. If the single pass conversion is 60%, calculate
the production rate of formaldehyde.

In Out
CH3OH 50 50-
H2 0 
HCHO 0 
n1 CH3OH
Reactor Total 50 50+
CH3OH 50 kmol/h n 2 H2 
= 0.6
n3 HCHO 50

 = 30 kmol/h

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The feed to a continuous ammonia formation reactor is 100 mol/s nitrogen, 300 mol/s hydrogen,
and 1 mol/s argon. The ammonia production reaction is
N2 + 3H2 → 2NH3
The percent conversion of hydrogen in the reactor is 60.0%. Find the molar flow rate of ammonia
produced.

In Out
N2 100 100-
N2 + 3H2 → 2NH3 H2 300 300-3
NH3 0 2
Total 400 400-2

fH2 = 0.6 Out Out

n1 N2
Reactor 3 N2 100- 40
N2 100 mol/s n 2 H2 fH2= =0.6
300 H2 300-3 120
H2 300 mol/s n3 NH3
3 = 180 mol/s NH3 2 120
 = 60 mol/s Total 400-2

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Ethylene monomer is the main source for the production of well-known polyethylene polymers.
Ethylene is produced by the catalytic cracking of ethane according to the following reaction:
C2H6 → C2H4 + H2
The inlet molar flow rate to a catalytic reactor is 100 mol/min of C2H6. The amount of hydrogen
in the product stream was found to be 40 mol/min. Calculate the molar flow rates of unreacted
ethane in the reactor exit stream.

C2H6 → C2H4 + H2
C2H6 100 100-
C2H4 
H2 0 
Total 100 100+
n1 C2H6
Reactor =nH2 = 40 mol/min
C2H6 100 n2 C2H4
mol/min 40 mol/min H2 n1 =100-40 = 60 mol/min
n2 =40 mol/min

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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?

C2H4 + HBr → C2H5Br C2H4 n1 n1- n1−56.232

HBr 165- n1 165- n1- 𝑦𝐶2𝐻4 = = 0.310
165−56.232
C2H5Br 0 
𝑛1=89.95 mol/s
Total 165 165-
56.232
165 mol/s 0.310 C2H4 𝑓𝐻𝐵𝑟 = = 0.749
Reactor 75.05
C2H4 n1 0.517 C2H5Br
HBr 165- n1 0.173 HBr 
𝑦𝐶2𝐻5𝐵𝑟 = = 0.517
165−
=56.232 mol/s
89.95−56.232 29
% 𝑒𝑥𝑐𝑒𝑠𝑠 𝑜𝑓 𝐶2𝐻4 = 𝑥100 =60%
56.232
CALCULATION OF EQUILIBRIUM CONSTANT
 For any chemical reaction, the answer of “what will be the final (equilibrium) composition of
the reaction mixture” is very important.

 Some reactions are irreversible; that is the reaction proceeds only in a single direction (from
reactants to products) and the concentration of the limiting reactant eventually approaches to
zero.
 Other reactions are reversible; reactants from products and products undergo the reverse
reaction to reform the reactants

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 Consider the water-gas shift reaction in the production of ammonia from natural gas and
air.
CO (g) + H2O (g)  CO2 (g) + H2 (g) (This is a reversible reaction)

 If this reaction proceeds to equilibrium at a temperature T (in K), the mole fractions of
the four reactive species satisfy the following relationship;
yCO2 yH2
K T =
yCO yH2O
K(T): the reaction equilibrium constant

 For a general reaction, the equilibrium defined;

yCc yDd
aA + bB  cC + dD K T =
yAa yBb

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 If you start with CO and H2O, the forward reaction occurs; then once CO2 and H2 are present,
the reverse reaction begins to take place.

 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 the reaction mixture is in chemical
equilibrium.

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

Let e be the extent of reaction at equilibrium. Data at T= 1105 K K=1

So, the product gas, yCO2 yH2

K T =
yCO yH2O
nCO = 1-e
nCO nH2 nCO2 nH2
nH2O = 2-e yCO = nT
yH2 = nT
yCO2 = nT
yH2 = nT

nCO2 = e e e
3 )( 3 e 2
nH2 = e nT= 3 mol 1= = 𝑒 = 0.6666
1 − e 2 − 1 − e )(2 − e
3 )( 3 e

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nCO = 1-e = 1-0.666 = 0.3334
nH2O = 2-e= 2-0.6666= 1.3334 nCO2 = e = 0.6666
nH2 = e=0.6666

0.6666
𝑓𝐻2 = = 0.3333 33.33% H2 was reacted
2

0.6666
𝑓𝐶𝑂 = = 0.6666 66.66% CO was reacted
1

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 Consider the reaction of methane with oxygen:

2CH4 + O2 ↔ 2CH3OH

At equilibrium, the compositions of the components satisfy the relation

2
𝑦𝐶𝐻3𝑂𝐻
𝐾= 2
𝑦𝐶𝐻4 𝑦𝑂2

If you are given the feed compositions (3 mol CH4 and 1 mol O2) and the equilibrium constant
K(T), how do you determine the equilibrium compositions?

the product gas,

nCH4 = 3-2e yC𝐻4 =
3−2e
yO2 =
1− e
yC𝐻3𝑂𝐻 =
2e
4−e 4−e 4−e
nO2 =1- e
e2
nCH3OH = 2e nT= 4-e 𝐾=
(3−2e )(1− e )
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