University of the Philippines – Diliman

Department of Chemical Engineering

Material Balance with Chemical Reactions

ChemE 101
Chemical Engineering Process Analysis I
AY 2018 – 2019
MSPDEANG
October 10, 2018

MSPDEANG 2018
Chemical Reaction Engineering
In Chemistry

In Chemical Engineering

REACTOR

MSPDEANG 2018
Chemical Reactors

MSPDEANG 2018
Review of Basic Stoichiometry
Stoichiometry
 To quantify all the state quantities in the reactor
 To determine the number of design equations necessary
to describe the reactor operation. (in ChemE 128)

MSPDEANG 2018
Stoichiometry
 Consider the chlorination of
methane to trichloromethane
CH4 + 3Cl2 →CHCl3+ 3HCl
 This particular reaction does not
actually occur but may be
expressed by the sum of the
following chemical reactions
CH4 + Cl2 →CH3Cl+ HCl
CH3Cl + Cl2 →CH2Cl2+ HCl
CH2Cl2 + Cl2 →CHCl3 + HCl

 Does not take into account rates

of reaction

 Stoichiometry allows us to see

and evaluate the overall picture

MSPDEANG 2018
Stoichiometry
𝜈𝐴 𝐴 + 𝜈𝐵 𝐵 → 𝜈𝑐 𝐶 + 𝜈𝐷 𝐷
 Sign conventions
 – Left of arrow: reactants (–)
 – Right of arrow: products (+)
 – Inert species: (0)
 Sum of stoichiometric coefficients
   j   A   B   C   D
j

 The stoichiometric coefficient (νj) is dimensionless.

 For a balanced chemical reaction

MSPDEANG 2018
Exercise
 Balance the Following Chemical Reactions

3 𝐻2 + 𝑁2 → 2 𝑁𝐻3
𝐶𝐻3 𝑂𝐻+ 1.5𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂

2 𝐹𝑒𝑆2 + 7.5 𝑂2 → 𝐹𝑒2 𝑂3 + 4 𝑆𝑂3

MSPDEANG 2018
Stoichiometric Ratios
 Consider the reaction

3𝐻2 + 𝑁2 → 2𝑁𝐻3
 The following stoichiometric ratios are all valid

3𝑚𝑜𝑙 𝐻2 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 2 𝑚𝑜𝑙 𝑁𝐻3 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑

1 𝑚𝑜𝑙 𝑁2 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 1 𝑚𝑜𝑙 𝑁2 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑
2 𝑚𝑜𝑙 𝑁𝐻3 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑
3𝑚𝑜𝑙 𝐻2 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

MSPDEANG 2018
Reactor Feed
The contents of a batch reactor (at time t), or the outlet
composition of a flow reactor depends on
-- initial contents of batch reactor, or the inlet
stream of flow reactor
-- stoichiometric parameters of the chemical
reactions that take place in the reactor
>> limiting reactant
>> excess reactant

MSPDEANG 2018
Limiting Reactant
Let A and B be two reactants of a chemical reaction

𝜈𝐴 𝐴 + 𝜈𝐵 𝐵 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠

If reactant A is indeed the limiting reactant

𝑁𝐴 0 𝑁𝐵 0
≤
𝜈𝐴 𝜈𝐵
𝐹𝐴,𝑖𝑛 𝐹𝐵,𝑖𝑛
≤
𝜈𝐴 𝜈𝐵

MSPDEANG 2018
 Excess Reactant
 Reactants are usually not always fed in stoichiometric
amounts
 One reactant is usually fed in excess (example:
combustion)
 A quantity indicating the surplus amount of a reactant
over the stoichiometric amount.
 Usually used in combustion reactions to indicate the
surplus amount of oxygen provided, which characterizes
the combustion conditions.

𝑎𝑚𝑜𝑢𝑛𝑡 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑓𝑒𝑑 − 𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑎𝑚𝑜𝑢𝑛𝑡 𝑛𝑒𝑒𝑑𝑒𝑑

𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑒𝑥𝑐𝑒𝑠𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 =
𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑎𝑚𝑜𝑢𝑛𝑡 𝑛𝑒𝑒𝑑𝑒𝑑

MSPDEANG 2018
Conversion
 Fraction of a reactant that has been consumed
Let A = reactant

𝑁𝐴,𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑁𝐴,𝑡 − 𝑁𝐴,0 𝐹𝐴,𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝐹𝐴,𝑖𝑛 − 𝐹𝐴,𝑜𝑢𝑡

𝑋𝐴 = = 𝑋𝐴 = =
𝑁𝐴,0 𝑁𝐴,0 𝐹𝐴,𝑖𝑛 𝐹𝐴,𝑖𝑛

 Conversion is defined only for reactants; and its value is

between 0 to 1.
 It is related to the composition (or flow rate) of a reactant,
and it is not defined on the basis of any specific chemical
reaction.
 It depends on the initial state selected (batch reactors),
or on the boundaries of the system (flow reactors).
 One of the measures of reactor performance

MSPDEANG 2018
Exercise
In the manufacture of ammonia, pure hydrogen and nitrogen
gas is fed at a temperature and pressure of 500°C and 100
bar respectively. Hydrogen is fed at a rate of 100lbmol/hr,
while nitrogen is fed at 40 lbmol/hr.

a. Determine the limiting reactant

b. What is the percent excess reactant?
c. If the reactor effluent was found to have 25lbmol of H2,
determine the flowrate of the other species exiting the
reactor, and determine the conversion of both reactants.

MSPDEANG 2018
Material Balance in Reacting
Systems
Material Balance with Reactions
 Material balances on processes involving chemical
reactions may be solved by applying
 Molecular Species Balance
-- A material balance equation is applied to
each chemical compound appearing in the
process
 Extent of Reaction
-- Expressions for each reactive species is
written involving the extent of reaction
 Atomic Species Balance
-- The balance is applied to each element
appearing in the process

MSPDEANG 2018
Molecular Species Balance

IN – OUT + GEN – CONS = ACC

 Assume Steady State: Acc = 0

IN – OUT + GEN – CONS = 0

IN = mass/moles going inside the boundary

OUT = mass/moles going out the boundary
GEN = mass/moles generated inside the boundary
CONS = mass/moles consumed inside the boundary
This is known as the molecular species balance
MSPDEANG 2018
Exercise
Selective oxidation of hydrocarbons is a known method to
produce alcohols. However, the alcohols react with the
oxygen to produce aldehydes, and the latter react with
oxygen to produce organic acids.
1
𝐶2 𝐻6 + 𝑂2 → 𝐶2 𝐻5 𝑂𝐻
2
1
𝐶2 𝐻5 𝑂𝐻 + 𝑂2 → 𝐶𝐻3 𝐶𝐻𝑂 + 𝐻2 𝑂
2
1
𝐶𝐻3 𝐶𝐻𝑂 + 𝑂2 → 𝐶𝐻3 𝐶𝑂𝑂𝐻
2
Write the general balance equation for each species present
in the system

MSPDEANG 2018
Extent of Chemical Reaction
 Quantification of the progress of a chemical reaction
(reaction coordinate)
 Units: mole extent
 Analogous to moles of reaction
 Denoted by the Greek letter xi (ξ)

 In other words, per mole of reaction, how many moles of

each species is produced/consumed?

MSPDEANG 2018
Stoichiometric Ratios
 Consider the reaction

3𝐻2 + 𝑁2 → 2𝑁𝐻3
 The following stoichiometric ratios are all valid using the
extents of reaction

3 𝑚𝑜𝑙 𝐻2 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 1 𝑚𝑜𝑙 𝑁2 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

1 𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 1 𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

2 𝑚𝑜𝑙 𝑁𝐻3 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑

1 𝑚𝑜𝑙 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

MSPDEANG 2018
Extent of Reaction
Batch Reactors Flow Reactors
For a single reaction

For multiple independent reactions

For total number of moles

MSPDEANG 2018
Exercise
In the manufacture of ammonia, pure hydrogen and nitrogen
gas is fed at a temperature and pressure of 500°C and 100
bar respectively. Hydrogen is fed at a rate of 100lbmol/hr,
while nitrogen is fed at 40 lbmol/hr. The reactor effluent was
found to have 25 lbmol of hydrogen gas.

a. Calculate the extent of reaction

b. Determine the flowrates of the other species exiting the
reactor

MSPDEANG 2018
Exercise
Ethylene oxide is produced by catalytic oxidation on a silver
catalyst according to the following chemical reaction:

A gaseous stream consisting of 60% C2H4, 30% O2, and

10% N2 is fed at a rate of 40 mol/min into a flow reactor
operating at steady state. If the mole fraction of oxygen in
the reactor effluent stream is 0.08, calculate the
production rate of ethylene oxide

MSPDEANG 2018
Exercise
Write the extent equation for each species and the total
moles
𝐹𝐶2𝐻4 ,𝑜𝑢𝑡 = 𝐹𝐶2𝐻4 ,𝑖𝑛 + −1 𝜉1
C2H4:
O 2: 𝐹𝑂2,𝑜𝑢𝑡 = 𝐹𝑂2,𝑖𝑛 + −0.5 𝜉1

C2H4O: 𝐹𝐶2 𝐻4𝑂,𝑜𝑢𝑡 = 𝐹𝐶2 𝐻4𝑂,𝑖𝑛 + 1 𝜉1

N2 𝐹𝑁2 ,𝑜𝑢𝑡 = 𝐹𝑁2,𝑖𝑛 + 0 𝜉1

Total moles: 𝐹𝑡𝑜𝑡,𝑜𝑢𝑡 = 𝐹𝑡𝑜𝑡,𝑖𝑛 + −0.5 𝜉1

MSPDEANG 2018
Exercise
Substitute known values
C2H4: 𝐹𝐶2 𝐻4,𝑜𝑢𝑡 = 0.60(40) + −1 𝜉1

O 2: 𝐹𝑂2,𝑜𝑢𝑡 = 0.30(40) + −0.5 𝜉1

C2H4O: 𝐹𝐶2 𝐻4𝑂,𝑜𝑢𝑡 = 0 + 1 𝜉1

N2: 𝐹𝑁2,𝑜𝑢𝑡 = 0.10(40) + 0 𝜉1

Total moles: 𝐹𝑡𝑜𝑡,𝑜𝑢𝑡 = 40 + −0.5 𝜉1

Other information:
mole fraction of oxygen in the reactor effluent stream is 0.08
𝐹𝑂2,𝑜𝑢𝑡
0.08 =
𝐹𝑡𝑜𝑡,𝑜𝑢𝑡

MSPDEANG 2018
Exercise

𝐹𝑂2,𝑜𝑢𝑡 𝐹𝑂2,𝑜𝑢𝑡 = 0.30(40) + −0.5 𝜉1

0.08 =
𝐹𝑡𝑜𝑡,𝑜𝑢𝑡
𝐹𝑡𝑜𝑡,𝑜𝑢𝑡 = 40 + −0.5 𝜉1
Substituting
0.30(40) + −0.5 𝜉1
0.08 = 𝜉1 = 19.13 𝑚𝑜𝑙
40 + −0.5 𝜉1

Calculate production rate of ethylene oxide

𝐹𝐶2 𝐻4𝑂,𝑜𝑢𝑡 = 𝐹𝐶2 𝐻4𝑂,𝑖𝑛 + 1 𝜉1

𝐹𝐶2𝐻4 𝑂,𝑜𝑢𝑡 = 0 + 1 19.13 = 19.13 𝑚𝑜𝑙 𝐶2 𝐻4 𝑂

MSPDEANG 2018
Exercise
Selective oxidation of hydrocarbons is a known method to
produce alcohols. However, the alcohols react with the
oxygen to produce aldehydes, and the latter react with
oxygen to produce organic acids.
1
𝐶2 𝐻6 + 𝑂2 → 𝐶2 𝐻5 𝑂𝐻 ∆= −0.5
2
1
𝐶2 𝐻5 𝑂𝐻 + 𝑂2 → 𝐶𝐻3 𝐶𝐻𝑂 + 𝐻2 𝑂 ∆= 0.5
2
1
𝐶𝐻3 𝐶𝐻𝑂 + 𝑂2 → 𝐶𝐻3 𝐶𝑂𝑂𝐻 ∆= −0.5
2
Write the balances of each species, and the total moles in
terms of the extents of reaction.

MSPDEANG 2018
Exercise
C2H6: 𝐹𝐶2 𝐻6,𝑜𝑢𝑡 = 𝐹𝐶2 𝐻6,𝑖𝑛 + −1 𝜉1 + 0 𝜉2 + 0 𝜉3

O2: 𝐹𝑂2,𝑜𝑢𝑡 = 𝐹𝑂2,𝑖𝑛 + −0.5 𝜉1 + −0.5 𝜉2 + −0.5 𝜉3

C2H5OH: 𝐹𝐶2 𝐻5𝑂𝐻,𝑜𝑢𝑡 = 𝐹𝐶2𝐻5 𝑂𝐻,𝑖𝑛 + 1 𝜉1 + −1 𝜉2 + 0 𝜉3

CH3CHO: 𝐹𝐶𝐻3 𝐶𝐻𝑂,𝑜𝑢𝑡 = 𝐹𝐶𝐻3 𝐶𝐻𝑂,𝑖𝑛 + 0 𝜉1 + 1 𝜉2 + −1 𝜉3

CH3COOH: 𝐹𝐶𝐻3𝐶𝑂𝑂𝐻,𝑜𝑢𝑡 = 𝐹𝐶𝐻3 𝐶𝑂𝑂𝐻,𝑖𝑛 + 0 𝜉1 + 0 𝜉2 + 1 𝜉3

H2O: 𝐹𝐻2 𝑂,𝑜𝑢𝑡 = 𝐹𝐻2𝑂,𝑖𝑛 + 0 𝜉1 + 0 𝜉2 + 1 𝜉3

N2: 𝐹𝑁2,𝑜𝑢𝑡 = 𝐹𝑁2 ,𝑖𝑛 + 0 𝜉1 + 0 𝜉2 + 0 𝜉3

Total moles: 𝐹𝑡𝑜𝑡,𝑜𝑢𝑡 = 𝐹𝑡𝑜𝑡,𝑖𝑛 + −0.5 𝜉1 + 0.5 𝜉2 + 0.5 𝜉3

MSPDEANG 2018
Exercise
A 50 mol/s stream consisting of 90% ethane and 10%
nitrogen is mixed with a 40 mol/s airstream and fed into a
catalytic reactor. The following reactions take place in the
reactor:
1
𝐶2 𝐻6 + 𝑂2 → 𝐶2 𝐻5 𝑂𝐻
2
1
𝐶2 𝐻5 𝑂𝐻 + 𝑂2 → 𝐶𝐻3 𝐶𝐻𝑂 + 𝐻2 𝑂
2
1
𝐶𝐻3 𝐶𝐻𝑂 + 𝑂2 → 𝐶𝐻3 𝐶𝑂𝑂𝐻
2
80% of the oxygen is consumed, and the concentration of
the ethanol in the product stream is three times that of the
aldehyde and four times that of the acetic acid. Calculate:
a. Percent of ethane consumed
b. Production rate of ethanol in mol/s
MSPDEANG 2018
Exercise
C2H6: 𝐹𝐶2 𝐻6,𝑜𝑢𝑡 = 0.90(50) + −1 𝜉1

O2: 0.2(0.21 40 ) = 0.21(40) + −0.5 𝜉1 + −0.5 𝜉2 + −0.5 𝜉3

C2H5OH: 𝐹𝐶2 𝐻5𝑂𝐻,𝑜𝑢𝑡 = 1 𝜉1 + −1 𝜉2

CH3CHO: 𝐹𝐶𝐻3 𝐶𝐻𝑂,𝑜𝑢𝑡 = 1 𝜉2 + −1 𝜉3

CH3COOH: 𝐹𝐶𝐻3 𝐶𝑂𝑂𝐻,𝑜𝑢𝑡 = 1 𝜉3

H2O: 𝐹𝐻2 𝑂,𝑜𝑢𝑡 = 1 𝜉3

N2: 𝐹𝑁2,𝑜𝑢𝑡 = 0.10 50 + 40 0.79

Total moles: 𝐹𝑡𝑜𝑡,𝑜𝑢𝑡 = (40 + 50) + −0.5 𝜉1 + 0.5 𝜉2 + 0.5 𝜉3

MSPDEANG 2018
Exercise
The concentration of the ethanol in the product stream is
three times that of the aldehyde and four times that of the
acetic acid
𝐹𝐶2 𝐻5𝑂𝐻,𝑜𝑢𝑡 𝐹𝐶𝐻3 𝐶𝐻𝑂,𝑜𝑢𝑡 𝐹𝐶2𝐻5 𝑂𝐻,𝑜𝑢𝑡 𝐹𝐶𝐻3𝐶𝑂𝑂𝐻,𝑜𝑢𝑡
=3 =4
𝐹𝑡𝑜𝑡,𝑜𝑢𝑡 𝐹𝑡𝑜𝑡,𝑜𝑢𝑡 𝐹𝑡𝑜𝑡,𝑜𝑢𝑡 𝐹𝑡𝑜𝑡,𝑜𝑢𝑡

1 𝜉1 + −1 𝜉2 = 3 1 𝜉2 + −1 𝜉3 1 𝜉1 + −1 𝜉2 = 4 𝜉3

0.2(0.21 40 ) = 0.21(40) + −0.5 𝜉1 + −0.5 𝜉2 + −0.5 𝜉3

MSPDEANG 2018
Exercise
The gas phase decomposition reaction of ethane(C2H6) into
ethyne(C2H2) is being investigated in a constant volume,
isothermal batch reactor. The reactor is charged with 20mol
ethane and the initial pressure is 2atm. When the reaction is
stopped, the pressure is 5atm. Assuming ideal gas behavior,
calculate:

a. The extent of the reaction

b. The partial pressure of the products

MSPDEANG 2018
Exercise
At low to moderate pressures the equilibrium state of of the water
gas shift reaction is described by the relation:
𝑦𝐶𝑂 2 𝑦𝐻 2
𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐶𝑂2 + 𝐻2 𝐾𝑒𝑞 =
𝑦𝐻2𝑂 𝑦𝐶𝑂

Where Keq is a function of temperature: 4020

𝐾𝑒𝑞 = 0.0247 exp
𝑇 𝐾

An isothermal reactor operating at 1123 K initially contains

20%CO,10% CO2, 40% H2O and the balance an inert gas.
On the basis of 100 moles of feed, calculate the composition of
the gases at equilibrium, and the equilibrium conversion of CO.

If the temperature was lowered to 800K, would the conversion

increase or decrease?

MSPDEANG 2018
Basis: 100 mol reactor feed
20 mol CO, 10mol CO2, 40 mol H2O, 30mol Inerts
𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐶𝑂2 + 𝐻2
𝑦𝐶𝑂 2 𝑦𝐻 2
Reaction is brought up to equilibrium 𝐾𝑒𝑞 =
𝑦𝐻2𝑂 𝑦𝐶𝑂

Calculate for value of equilibrium constant

4020 4020
𝐾𝑒𝑞 = 0.0247 exp = 0.0247 exp = 0.8858
𝑇 𝐾 1123

Express mole fractions in terms of moles

𝑛𝐶𝑂 2,𝑜𝑢𝑡 𝑛𝐻2
,𝑜𝑢𝑡
𝑛𝑇 𝑛𝑇 𝑛𝐶𝑂 2,𝑜𝑢𝑡 𝑛𝐻2,𝑜𝑢𝑡
𝐾𝑒𝑞 = 𝑛 𝐾𝑒𝑞 =
𝐻2 𝑂,𝑜𝑢𝑡 𝑛𝐶𝑂 ,𝑜𝑢𝑡 𝑛𝐻2𝑂,𝑜𝑢𝑡 𝑛𝐶𝑂 ,𝑜𝑢𝑡
𝑛𝑇 𝑛𝑇

MSPDEANG 2018
Express effluent in terms of extents of reaction
𝑛𝐶𝑂 2,𝑜𝑢𝑡 𝑛𝐻2,𝑜𝑢𝑡
𝐾𝑒𝑞 = = 0.8858
𝑛𝐻2𝑂,𝑜𝑢𝑡 𝑛𝐶𝑂 ,𝑜𝑢𝑡

𝑛𝐶𝑂 2,𝑜𝑢𝑡 = 10 + 𝜉 𝑛𝐻2,𝑜𝑢𝑡 = 0 + 𝜉 𝑛𝐻2𝑂,𝑜𝑢𝑡 = 40 − 𝜉 𝑛𝐶𝑂 ,𝑜𝑢𝑡 = 20 − 𝜉

(10 + 𝜉 )(0 + 𝜉 )
𝐾𝑒𝑞 = = 0.8858
(40 − 𝜉 )(20 − 𝜉 )

𝜉 = 11

𝑛𝐶𝑂 ,𝑜𝑢𝑡 = 20 − 11 = 9 𝑚𝑜𝑙 𝐶𝑂

20 𝑚𝑜𝑙 𝐶𝑂 𝑓𝑒𝑑 − 9 𝑚𝑜𝑙 𝐶𝑂 𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑

𝑋𝐶𝑂 = = 0.55
20 𝑚𝑜𝑙 𝐶𝑂 𝑓𝑒𝑑

MSPDEANG 2018
Exercise (HW)
Consider the catalytic oxidation of sulfur dioxide to sulfur
trioxide

An isothermal catalytic reactor operating at 700K and 1 atm

is used to react a feed stream of 12% SO2, 8% O2, and
80% N2 up until equilibrium. The equilibrium relation for the
reaction is as such:

(Partial pressures should be in atm)

Determine the conversion of SO2 at equilibrium.

MSPDEANG 2018
Reactor Performance
 Extents of reaction are expressed in extensive
properties.
 Reactor performance may be measured using
dimensionless properties instead

 Conversion
 Product Yield
 Product Selectivity

MSPDEANG 2018
Yield and Selectivity
 When several simultaneous reactions take place, it is
convenient to define parameters that indicate what
portion of the reactant was converted to valuable
products.
 Product Yield
 Product Selectivity

MSPDEANG 2018
Product Yield
 Yield is a measure of the portion of a reactant converted
to the desired product by the desirable chemical reaction.
 It indicates the amount of the desirable product,
produced relative to the amount that could have been
produced if only the desirable reaction took place.
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑓𝑜𝑟𝑚𝑒𝑑
𝜂=
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑣𝑎𝑙𝑢𝑎𝑏𝑙𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑓𝑜𝑟𝑚𝑒𝑑 𝑖𝑓 𝑎𝑙𝑙 𝑡ℎ𝑒 𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑤𝑒𝑟𝑒
𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

MSPDEANG 2018
Product Selectivity
Product selectivity indicates the amount of desired product
produced relative to the theoretical amount of that could be
produced if all reactant A consumed were only reacted by
the desirable chemical reaction.
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑓𝑜𝑟𝑚𝑒𝑑
𝜎=
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑓𝑜𝑟𝑚𝑒𝑑 𝑖𝑓 𝑎𝑙𝑙 𝑡ℎ𝑒 𝒄𝒐𝒏𝒔𝒖𝒎𝒆𝒅 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑤𝑒𝑟𝑒
𝑜𝑛𝑙𝑦 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

Measure of how effective a reaction is in producing the

desired product relative to the undesired products that
result from the side reactions
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑓𝑜𝑟𝑚𝑒𝑑
𝑆=
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑢𝑛𝑑𝑒𝑟𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑓𝑜𝑟𝑚𝑒𝑑

MSPDEANG 2018
Exercise
Isomerization reactions are reactions where the original molecule
transforms to another molecule of the same atomic composition, but
different molecular orientations. Consider the isomerization of n-
pentane(A) to isopentane(B) and neopentane(C) in a fixed bed catalytic
reactor, where isopentane is the desired product. 50mol/s of pure n-
pentane is fed to the reactor. The reactor effluent is found to have
10mol/s n-pentane and 30 mol/s isopentane. Determine the conversion
of n-pentane, and the selectivity and yield of isopentane.
𝐴 →𝐵
𝐴 →𝐶
𝐹𝐴,𝑜𝑢𝑡 = 𝐹𝐴,𝑖𝑛 − 𝜉1 − 𝜉2 10 𝑚𝑜𝑙 𝐴 = 50𝑚𝑜𝑙 𝐴 − 𝜉1 − 𝜉2
𝜉1 = 30𝑚𝑜𝑙
𝐹𝐵,𝑜𝑢𝑡 = 𝐹𝐵,𝑖𝑛 + 𝜉1 30 𝑚𝑜𝑙 𝐵 = 0𝑚𝑜𝑙 𝐵 + 𝜉1
𝜉2 = 10𝑚𝑜𝑙
𝐹𝐶𝑜𝑢𝑡 = 𝐹𝐶,𝑖𝑛 + 𝜉2 𝐹𝐴,𝑜𝑢𝑡 = 0 𝑚𝑜𝑙 𝐶 + 𝜉2

MSPDEANG 2018
Exercise
𝐹𝐴,𝑜𝑢𝑡 = 10 𝑚𝑜𝑙 𝐴 𝐹𝐵,𝑜𝑢𝑡 = 30 𝑚𝑜𝑙 𝐵 𝐹𝐶𝑜𝑢𝑡 = 10 𝑚𝑜𝑙 𝐶 𝑚𝑜𝑙 𝐴 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 = 40 𝑚𝑜𝑙
𝑚𝑜𝑙 𝐴 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑
𝑋𝐴 = 𝐹𝐴,𝑖𝑛 − 𝐹𝐴,𝑜𝑢𝑡
𝑚𝑜𝑙 𝐴 𝑓𝑒𝑑 𝑋𝐴 =
𝐹𝐴,𝑖𝑛
50 − 10
𝑋𝐴 = = 0.80
50
𝑚𝑜𝑙 𝐵 𝑓𝑜𝑟𝑚𝑒𝑑 𝐹𝐵,𝑜𝑢𝑡
𝜎= 𝜎=
𝑚𝑜𝑙 𝐵 𝑓𝑜𝑟𝑚𝑒𝑑 𝑖𝑓 𝑎𝑙𝑙 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝐴 𝑤𝑒𝑟𝑒 𝑡𝑜 𝑓𝑜𝑟𝑚 𝐵 𝜈
(𝐹𝐴,𝑖𝑛 −𝐹𝐴,𝑜𝑢𝑡 ) 𝜈𝐵
𝐴
30 𝑚𝑜𝑙 𝐵
𝜎= = 0.75
1 𝑚𝑜𝑙 𝐵
40 𝑚𝑜𝑙 𝐴 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 ×
1 𝑚𝑜𝑙 𝐴
𝐹𝐵,𝑜𝑢𝑡
𝑚𝑜𝑙 𝐵 𝑓𝑜𝑟𝑚𝑒𝑑 𝜂=
𝜂= 𝜈
𝑚𝑜𝑙 𝐵 𝑓𝑜𝑟𝑚𝑒𝑑 𝑖𝑓 𝑎𝑙𝑙 𝐴 𝑓𝑒𝑑 𝑤𝑒𝑟𝑒 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑡𝑜 𝑓𝑜𝑟𝑚 𝐵 (𝐹𝐴,𝑖𝑛 ) × 𝜈𝐵
𝐴

30 𝑚𝑜𝑙 𝐵
𝜂= = 0.60
1 𝑚𝑜𝑙 𝐵
50 𝑚𝑜𝑙 𝐴 𝑓𝑒𝑑 ×
1 𝑚𝑜𝑙 𝐴
𝜂 = 𝜎𝑋
MSPDEANG 2018
Exercise
Consider the following pair of reactions:
A  2B  desired 
A  C  undesired 
Suppose 100 moles of A are fed to a batch reactor and the
final product contains 10 moles of A, 160 moles of B, and 10
moles of C. Calculate the following:
a) The fractional conversion of A
b) The percentage yield of B
c) The selectivity of B
d) The extents of the first and second reactions

MSPDEANG 2018
Atomic Species Balance
 Atoms are conserved throughout the system (unless it is
a nuclear reaction)
 Atomic Species Balance would then be
Sum of Atomic species in = Sum of Atomic species out

MSPDEANG 2018
Exercise
Consider the dehydrogenation of ethane in a steady-state
continuous reactor where 100 mol of pure ethane is fed. If
40mol of hydrogen gas is found in the reactor effluent,
determine the flowrate of the other two components using
atomic species balances.

C2H6  C2H4  H2

MSPDEANG 2018
Exercise
In the Deacon process for the manufacture of chlorine, HCl
and O2 react to form Cl2 and H2O. Sufficient air is fed to
provide 35% excess oxygen and the fractional conversion of
HCl is 0.85.
Determine the amount of air required per mole of HCl fed
into the process. Calculate the mol product stream
components using:
a) Atomic species balances
b) Molecular species balances (Practice on your own)
c) Extents of reaction (Practice on your own)

MSPDEANG 2018
 1
2𝐻𝐶𝑙 + 𝑂2 → 𝐶𝑙2 + 𝐻2 𝑂
2
Basis: 1 mol HCl feed
Oxygen is supplied 35% in excess

0.5 𝑚𝑜𝑙 𝑂2
𝑚𝑜𝑙 𝑂2 𝑓𝑒𝑑 = 1 𝑚𝑜𝑙 𝐻𝐶𝑙 × × 1.35 = 0.3375 𝑚𝑜𝑙 𝑂2
2 𝑚𝑜𝑙 𝐻𝐶𝑙
79 𝑚𝑜𝑙 𝑁2
𝑚𝑜𝑙 𝑁2 𝑓𝑒𝑑 = 0.3375𝑚𝑜𝑙 𝑂2 × = 1.2696 𝑚𝑜𝑙 𝑁2
21 𝑚𝑜𝑙 𝑂2

85% HCl conversion

0.85 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
1 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑓𝑒𝑑 × = 0.85 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
1 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑓𝑒𝑑
1 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑓𝑒𝑑 − 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑
0.85 = → 0.15 𝑚𝑜𝑙 𝐻𝐶𝐿 𝑢𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑
1 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑓𝑒𝑑

MSPDEANG 2018
Atomic Species
Cl: 𝑛𝐻𝐶𝑙,𝑖𝑛 11𝑚𝑜𝑙 𝐶𝑙
𝑚𝑜𝑙 𝐻𝐶𝑙
= 𝑛𝐻𝐶𝑙,𝑜𝑢𝑡
1𝑚𝑜𝑙 𝐶𝑙
1 𝑚𝑜𝑙 𝐻𝐶𝑙
+ 𝑛𝐶𝑙2,𝑜𝑢𝑡
2𝑚𝑜𝑙 𝐶𝑙
1 𝑚𝑜𝑙 𝐶𝑙2

1𝑚𝑜𝑙 𝐻 1𝑚𝑜𝑙 𝐶𝑙 2𝑚𝑜𝑙 𝐻

𝑛𝐻𝐶𝑙,𝑖𝑛 = 𝑛𝐻𝐶𝑙,𝑜𝑢𝑡 + 𝑛𝐻2𝑂,𝑜𝑢𝑡
H: 1 𝑚𝑜𝑙 𝐻𝐶𝑙 1 𝑚𝑜𝑙 𝐻𝐶𝑙 1 𝑚𝑜𝑙 𝐻2 𝑂

2 𝑚𝑜𝑙 𝑂 2 𝑚𝑜𝑙 𝑂 1𝑚𝑜𝑙 𝑂

𝑛𝑂2,𝑖𝑛 = 𝑛𝑂2,𝑜𝑢𝑡 + 𝑛𝐻2 𝑂,𝑜𝑢𝑡
O: 1 𝑚𝑜𝑙 𝑂2 1 𝑚𝑜𝑙 𝑂2 1 𝑚𝑜𝑙 𝐻2 𝑂

2 𝑚𝑜𝑙 𝑁 2 𝑚𝑜𝑙 𝑁
N: 𝑛𝑁2,𝑖𝑛
1 𝑚𝑜𝑙 𝑁2
= 𝑛𝑁2,𝑜𝑢𝑡
1 𝑚𝑜𝑙 𝑁2

From conversion of HCl: 𝑛𝐻𝐶𝑙,𝑜𝑢𝑡 = 0.15 𝑚𝑜𝑙 𝐻𝐶𝑙

Solving: 𝑛𝐶𝑙2,𝑜𝑢𝑡 = 0.425 𝑚𝑜𝑙 𝐶𝑙2
𝑛𝐻2𝑂,𝑜𝑢𝑡 = 0.425 𝑚𝑜𝑙 𝐻2 𝑂

𝑛𝑂2,𝑜𝑢𝑡 = 0.125 𝑚𝑜𝑙 𝑂2

𝑛𝑁2,𝑜𝑢𝑡 = 1.2696 𝑚𝑜𝑙 𝑁2

MSPDEANG 2018
Molecular Species
HCl: 𝑛𝐻𝐶𝑙,𝑜𝑢𝑡 = 𝑛𝐻𝐶𝑙,𝑖𝑛 − 𝑛𝐻𝐶𝑙,𝑐𝑜𝑛𝑠 𝑛𝐻𝐶𝑙,𝑜𝑢𝑡 = 1 𝑚𝑜𝑙 𝐻𝐶𝑙 − 0.85 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑐𝑜𝑛𝑠

Cl2: 𝑛𝐶𝑙2,𝑜𝑢𝑡 = 𝑛𝐶𝑙2,𝑖𝑛 + 𝑛𝐶𝑙2,𝑝𝑟𝑜𝑑

H2O: 𝑛𝐻2𝑂,𝑜𝑢𝑡 = 𝑛𝐻2𝑂,𝑖𝑛 + 𝑛𝐻2𝑂,𝑝𝑟𝑜𝑑
O2: 𝑛𝑂2,𝑜𝑢𝑡 = 𝑛𝑂2,𝑖𝑛 − 𝑛𝑂2,𝑐𝑜𝑛𝑠
N2: 𝑛𝑁2,𝑜𝑢𝑡 = 𝑛𝑁2,𝑖𝑛
1 𝑚𝑜𝑙 𝐶𝑙2 𝑝𝑟𝑜𝑑
𝑛𝐶𝑙2,𝑜𝑢𝑡 = 0.85 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑐𝑜𝑛𝑠 × = 0.425 𝑚𝑜𝑙 𝐶𝑙2
2 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑐𝑜𝑛𝑠
1 𝑚𝑜𝑙 𝐻2 𝑂 𝑝𝑟𝑜𝑑
𝑛𝐻2𝑂,𝑜𝑢𝑡 = 0.85 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑐𝑜𝑛𝑠 × = 0.425 𝑚𝑜𝑙 𝐻2 𝑂
2 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑐𝑜𝑛𝑠
0.5 𝑚𝑜𝑙 𝐶𝑙2 𝑐𝑜𝑛𝑠
𝑛𝑂2,𝑜𝑢𝑡 = 0.3375 𝑚𝑜𝑙 𝑂2 𝑖𝑛 − 0.85 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑐𝑜𝑛𝑠 × = 0.125𝑚𝑜𝑙 𝑂2
2 𝑚𝑜𝑙 𝐻𝐶𝑙 𝑐𝑜𝑛𝑠
𝑛𝑁2 ,𝑜𝑢𝑡 = 1.2696 𝑚𝑜𝑙 𝑁2

MSPDEANG 2018
Extent of Reaction Method

𝑛𝐻𝐶𝑙,𝑜𝑢𝑡 = 𝑛𝐻𝐶𝑙,𝑖𝑛 − 2𝜉 𝑛𝐻𝐶𝑙,𝑜𝑢𝑡 = 1 − 2𝜉

𝑛𝑂2,𝑜𝑢𝑡 = 𝑛𝑂2,𝑖𝑛 − 0.5𝜉 𝑛𝑂2 ,𝑜𝑢𝑡 = 0.3375 − 0.5𝜉

𝑛𝐶𝑙2,𝑜𝑢𝑡 = 𝑛𝐶𝑙2,𝑖𝑛 + 𝜉 𝑛𝐶𝑙2,𝑜𝑢𝑡 = 0 + 𝜉

𝑛𝐻2𝑂,𝑜𝑢𝑡 = 𝑛𝐻2𝑂,𝑖𝑛 + 𝜉 𝑛𝐻2 𝑂,𝑜𝑢𝑡 = 0 + 𝜉

𝑛𝑁2,𝑜𝑢𝑡 = 𝑛𝑁2,𝑖𝑛 + 0𝜉 𝑛𝑁2 ,𝑜𝑢𝑡 = 1.2696 + 0𝜉

From HCl conversion, 0.85 mol HCl reacted, 0.15 mol HCl
unreacted. 𝑛𝑂2,𝑜𝑢𝑡 = 0.3375 − 0.5 0.425 = 0.125 𝑚𝑜𝑙 𝑂2
0.15 𝑚𝑜𝑙 𝐻𝐶𝑙 = 1𝑚𝑜𝑙 𝐻𝐶𝑙 − 2𝜉
𝑛𝐶𝑙2,𝑜𝑢𝑡 = 0 + 0.425 = 0.425 𝑚𝑜𝑙 𝐶𝑙2
𝜉 = 0.425 𝑚𝑜𝑙
𝑛𝐻2𝑂,𝑜𝑢𝑡 = 0 + 0.425 = 0.425 𝑚𝑜𝑙 𝐻2 𝑂

𝑛𝑁2 ,𝑜𝑢𝑡 = 1.2696 𝑚𝑜𝑙 𝑁2

MSPDEANG 2018
Balances with Reactions
 Atomic species balances generally lead to
the most straightforward solution procedure, especially
when more than one reaction is involved. These are
also useful since the stoichiometry of the reactions need
not be considered.
 Extents 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.

MSPDEANG 2018
Exercise
TiO2 – Complete Problem Statement
Titanium dioxide (TiO2) is extensively used as a white pigment. It
is produced from an ore that contains ilmenite (FeTiO3) and ferric
oxide (Fe2O3). The ore is digested with an aqueous sulfuric acid
solution to produce an aqueous solution of titanyl sulfate
[(TiO)SO4] and ferrous sulfate (FeSO4). Water is added to
hydrolyze the titanyl sulfate to H2TiO3, which precipitates, and
H2SO4. The precipitate is then roasted, driving off water and
leaving a residue of pure titanium dioxide.

Suppose an ore containing 24.3% Ti by mass is digested with an

80% H2SO4 solution, supplied in 50% excess of the amount
needed to convert all the ilmenite to titanyl sulfate and all the ferric
oxide to ferric sulfate [Fe2(SO4)3]. Further suppose that 89% of the
ilmenite actually decomposes. Calculate the masses (kg) of ore
and 80% sulfuric acid solution that must be fed to produce 1000
kg of pure TiO2. Assume that the ore is made entirely of ilmenite
and ferric oxide.

MSPDEANG 2018
QUESTIONS?