CHE 205

CHE 205
Chemical Engineering Calculations

Week 9
Spring 2022

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Elementary Principles of Chemical Processes, 4th edition,
2017, Wiley & Sons, Inc.
By: Richard M. Felder, Ronald W. Rousseau, & Lisa G. Bullard.

3
Chapter 4 Fundamentals of Material Balances
4.7c. Molecular species balances
4.7d. Atomic species balances
4.7e. Extent of reaction
4.7f. Product separation and recycle
4.7g. Purging

4
 4.7c. Molecular Species Balances
Degree of Freedom Analysis

No. unknown labeled variables

+ No. independent chemical reactions
− No. independent molecular species balances components in the process

− No. other equations relating unknown variables

__________________________________________

= No. DOF

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.
5
 Example: C2H6 → C2H4 + H2 C2H6: Ethane
C2H4: Ethylene
Reactor
100 kmol C2H6 / min 40 kmol H2 / min
𝑛̇ kmol C2H6 / min
𝑛̇ kmol C2H4 / min

Degree of Freedom Analysis

No. unknown labeled variables 2 unknown labeled variables (𝑛̇ , 𝑛̇ )

+ No. independent chemical reactions + 1 independent chemical reaction (C2H6 → C2H4 + H2)
− No. independent molecular species balances − 3 independent molecular species balances (C2H6, C2H4, H2)
− No. other equations relating unknown variables − 0 other equations relating unknown variables
__________________________________________ __________________________________________

=No. DOF = 0 DOF

6
 C2H6 → C2H4 + H2

Reactor
100 kmol C2H6 / min 40 kmol H2 / min
𝑛̇ kmol C2H6 / min
Balance on Molecular Species
𝑛̇ kmol C2H4 / min
Input + Generation = Output + Consumption (continuous steady-state process)

Molecular H2 Balance: generation = output

𝑘𝑚𝑜𝑙 𝐻 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑
𝐺𝑒𝑛 = 40 𝑘𝑚𝑜𝑙 𝐻 /𝑚𝑖𝑛
𝑚𝑖𝑛
C2H6 Balance: input = output + consumption cofficentaAz
same
100 𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑘𝑚𝑜𝑙 𝐶 𝐻 40 𝑘𝑚𝑜𝑙 𝐻 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 1 𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑
= 𝑛̇ + → 𝒏̇ 𝟏 = 𝟔𝟎 𝒌𝒎𝒐𝒍 𝑪𝟐 𝑯𝟔 ⁄𝒎𝒊𝒏
𝑚𝑖𝑛 𝑚𝑖𝑛 𝑚𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝐻 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑
C2H4 Balance: generation = output
40 𝑘𝑚𝑜𝑙 𝐻 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 1 𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝑘𝑚𝑜𝑙 𝐶 𝐻
= 𝑛̇ → 𝒏̇ 𝟐 = 𝟒𝟎 𝒌𝒎𝒐𝒍 𝑪𝟐 𝑯𝟒 ⁄𝒎𝒊𝒏
𝑚𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝐻 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝑚𝑖𝑛
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 4.7d. Atomic species balances
Degree of Freedom Analysis
gift

No. unknown labeled variables

− No. independent atomic species balances Atoms in the process
Non reactive components
− No. independent molecular species balances on nonreactive species in the process
− No. other equations relating unknown variables
__________________________________________

= No. DOF

Important Balances on atomic species can be written as input=output, since

atoms can neither be created (generation = 0) nor destroyed
(consumption = 0) in a chemical reaction.

Atomic species balances generally lead to the most straightforward

solution procedure, especially when more than one reaction is involved.
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 Example: C2H6 → C2H4 + H2 C2H6: Ethane
C2H4: Ethylene
if
Reactor
ai 100 kmol C2H6 / min 40 kmol H2 / min

as
added 𝑛̇ kmol C2H6 / min
then only react
𝑛̇ kmol C2H4 / min

Degree of Freedom Analysis N2wont

No. unknown labeled variables
− No. independent atomic species balances
− No. independent molecular species balances on
nonreactive species
− No. other equations relating unknown variables
__________________________________________
2 unknown labeled variables (𝑛̇ , 𝑛̇ )
− 2 independent atomic species balances (C and H)
− 0 independent molecular species balances on nonreactice
species
− 0 other equations relating unknown variables
__________________________________________

= No. DOF = 0 DOF

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 C2H6 → C2H4 + H2

Reactor
100 kmol C2H6 / min 40 kmol H2 / min
𝑛̇ kmol C2H6 / min
Balance on Atomic Species
𝑛̇ kmol C2H4 / min
Input = Output (continuous steady-state process)
Atomic C Balance: input = output
100 𝑘𝑚𝑜𝑙 𝐶 𝐻 2 𝑘𝑚𝑜𝑙 𝐶 𝑘𝑚𝑜𝑙 𝐶 𝐻 2 𝑘𝑚𝑜𝑙 𝐶 𝑘𝑚𝑜𝑙 𝐶 𝐻 2 𝑘𝑚𝑜𝑙 𝐶
= 𝑛̇ + 𝑛̇
𝑚𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑚𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑚𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝐶 𝐻

200 𝑘𝑚𝑜𝑙 𝐶 ⁄min = 2𝑛̇ + 2𝑛̇

Atomic H Balance: input = output
100 𝑘𝑚𝑜𝑙 𝐶 𝐻 6 𝑘𝑚𝑜𝑙 𝐻 40 𝑘𝑚𝑜𝑙 𝐻 2 𝑘𝑚𝑜𝑙 𝐻 𝑘𝑚𝑜𝑙 𝐶 𝐻 6 𝑘𝑚𝑜𝑙 𝐻 𝑘𝑚𝑜𝑙 𝐶 𝐻 4 𝑘𝑚𝑜𝑙 𝐻
= + 𝑛̇ + 𝑛̇
𝑚𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑚𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝐻 𝑚𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑚𝑖𝑛 1 𝑘𝑚𝑜𝑙 𝐶 𝐻

600 𝑘𝑚𝑜𝑙 𝐻 ⁄min = 80 𝑘𝑚𝑜𝑙 𝐻⁄𝑚𝑖𝑛 + 6𝑛̇ + 4𝑛̇

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Solve simultaneously: 𝒏̇ 𝟏 = 𝟔𝟎 𝒌𝒎𝒐𝒍 𝑪𝟐 𝑯𝟔 ⁄𝒎𝒊𝒏 and 𝒏̇ 𝟐 = 𝟒𝟎 𝒌𝒎𝒐𝒍 𝑪𝟐 𝑯𝟒 ⁄𝒎𝒊𝒏
 4.7e. Extent of Reaction
Degree of Freedom Analysis

No. unknown labeled variables

+ No. independent reactions (one unknown ξ for each reaction) Reactions in process

− No. independent reactive species (one eqn for each species in terms of ξ)
− No. independent nonreactive species (one balance equation for each)
− No. other equations relating unknown variables
__________________________________________

= DOF

Extents of reaction are convenient for chemical equilibrium problems

and when equation solving software is to be used.

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 Example: C2H6 → C2H4 + H2 C2H6: Ethane

Reactor
C2H4: Ethylene
100 kmol C2H6 / min 40 kmol H2 / min
𝑛̇ kmol C2H6 / min
𝑛̇ kmol C2H4 / min

Degree of Freedom Analysis

No. unknown labeled variables
+ No. independent reactions
− No. independent reactive species
− No. independent nonreactive species
− No. other equations relating unknown variables
__________________________________________
= No. DOF
2 unknown labeled variables (𝑛̇ , 𝑛̇ )
+ 1 independent reaction
− 3 independent reactive species (C2H6, C2H4, H2)
− 0 independent nonreactive species
− 0 other equations relating unknown variables
__________________________________________
= 0 DOF
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 C2H6 → C2H4 + H2

Reactor
100 kmol C2H6 / min 40 kmol H2 / min
𝑛̇ kmol C2H6 / min
𝒏̇ 𝒊 = 𝒏̇ 𝒊𝟎 + ν̇ 𝒊 ξ 𝑛̇ kmol C2H4 / min

𝑘𝑚𝑜𝑙 𝐻 𝑘𝑚𝑜𝑙 𝐻 𝑘𝑚𝑜𝑙 𝐻 𝑘𝑚𝑜𝑙 𝐻

𝐻 ν̇ = 1 : 40 =0 + 1 ξ → ξ = 40
𝑚𝑖𝑛 𝑚𝑖𝑛 𝑚𝑖𝑛 𝑚𝑖𝑛

𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑘𝑚𝑜𝑙 𝐶 𝐻

𝐶 𝐻 ν̇ = −1 : 𝑛̇ = 100 − ξ → 𝑛̇ = 60
𝑚𝑖𝑛 𝑚𝑖𝑛 𝑚𝑖𝑛

𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑘𝑚𝑜𝑙 𝐶 𝐻 𝑘𝑚𝑜𝑙 𝐶 𝐻

𝐶 𝐻 ν̇ = 1 : 𝑛̇ = ξ → 𝑛̇ = 40
𝑚𝑖𝑛 𝑚𝑖𝑛 𝑚𝑖𝑛

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Example 1
Ammonia is burned to form nitric oxide. Fractional conversion of O2 is
0.5. The inlet molar flow rates of NH3 and O2 are 5 mol/h. Calculate the
exit component molar flow rates using:

a) Extent of reaction method.

b) Atomic balance approach.

4 NH3 + 5 O2  4 NO + 6 H2O

Reactor
5 mol/h NH3 𝑛̇ NH3
5 mol/h O2 fO2 = 0.5 𝑛̇ O2
𝑛̇ H2O
𝑛̇ NO
halfofOzwill react 14
 Solution
a) Extent of reaction method
• Unknowns: 4 (𝑛̇ , 𝑛̇ , 𝑛̇ , 𝑛̇ )
• Reactions: 1 (4 NH3 + 5 O2  4 NO + 6 H2O)
• Reactive species: 4 (NH3 , O2 , NO , H2O)
• Independent species? Yes DOF analysis
• Extent equations: 4 (one per species) 4 unknown variables
• Additional equations? Yes (conversion) +1 + indep reactions
-4 - indep reactive species
-0 - indep nonreactive species
Extent of reaction balances
Product -1 - other equations
𝒏̇ 𝒊 = 𝒏̇ 𝒊𝒐 ± ν̇ 𝒊 𝝃
reactant
ν̇ = −4, ν̇ = −5, ν̇ = 4, ν̇ =6 0 = DOF

aint • Balance of NH3: 𝑛̇

0
=5 −4𝜉 1 We can’t solve without  … find it.

Treats
• Balance of O2: 𝑛̇ =5 −5𝜉 2 Conversion: 0.50 = 1 − 𝑛̇ /5 5

• Balance of H2O: 𝑛̇ =0+6𝜉 3 restwont

Find 𝑛̇ 1 from (5) then  from (2)
•
WE
Balance of NO: 𝑛̇ =0+4𝜉 4 then continue react
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 05
55 total
7
5

2
Conversion:
y
0.50 = 1 − 𝑛̇ /5

Balance of O2: 𝑛̇ = 5 − 5 𝜉  2.5 = 5 − 5 𝜉

 𝑛̇ = 2.5 mol/h O

 𝜉 = 0.5 mol/h
2

input
1 Balance of NH3 : 𝑛̇ = 5 − 4 𝜉  𝑛̇ = 5 − 4 × 0.5  𝑛̇ = 3.0 mol/h NH3

3 Balance of H2O : 𝑛̇ = 0 + 6 𝜉  𝑛̇ = 0 + 6 × 0.5  𝑛̇ = 3.0 mol/h

4 Balance of NO: 𝑛̇ = 0 + 4 𝜉  𝑛̇ = 0 + 4 × 0.5  𝑛̇ = 2.0 mol/h

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 Solution
b) Atomic balance method
• Unknowns: 4 (𝑛̇ , 𝑛̇ , 𝑛̇ , 𝑛̇ )
• Atomic species: 3 ( N , H , O ) 2km2 Ixh3
• Independent atoms? Yes I Inn
• # indep atomic balances: 3 (one per atom) DOF analysis
• Non reactive species? None 4 unknown variables
• Additional equations? Yes (conversion) -3 - indep atomic species balances
-0 - indep nonreactive species
Atomic balances: 𝑰𝒏𝒑𝒖𝒕𝒊 = 𝑶𝒖𝒕𝒑𝒖𝒕𝒊 -1 - other equations

• N balance: 1 × 5 = 1 × 𝑛̇ + 1 × 𝑛̇ 0 = DOF

According 𝑛̇ + 𝑛̇ = 5 1

• H Balance: 3 × 5 = 3 × 𝑛̇ + 2 × 𝑛̇ Additional equation(s)

to the • Conversion:
Lowmass 3 𝑛̇ + 2 𝑛̇ = 15 2

• O Balance: 2 × 5 = 2 × 𝑛̇ + 1 × 𝑛̇ + 1 × 𝑛̇ 0.50 = 1 − 𝑛̇ /5 4

unthig 2 𝑛̇ + 𝑛̇ + 𝑛̇ = 10 3
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𝑛̇ + 𝑛̇ = 5 1 Solving 4 simultaneous equations:
𝑛̇ = 3.0 mol/h NH3
3 𝑛̇ + 2 𝑛̇ = 15 2
𝑛̇ = 2.5 mol/h O2
2 𝑛̇ + 𝑛̇ + 𝑛̇ = 10 3
𝑛̇ = 3.0 mol/h H2O

0.50 = 1 − 𝑛̇ /5 4 𝑛̇ = 2.0 mol/h NO

Same answers to extent of

reaction method

18
4.7f. Product separation and recycle
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 − 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑜𝑢𝑝𝑢𝑡 𝑓𝑟𝑜𝑚 𝑝𝑟𝑜𝑐𝑒𝑠𝑠
Overall Conversion:
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑝𝑟𝑜𝑐𝑒𝑠𝑠

𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑟𝑒𝑎𝑐𝑡𝑜𝑟 − 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑜𝑢𝑝𝑢𝑡 𝑓𝑟𝑜𝑚 𝑟𝑒𝑎𝑐𝑡𝑜𝑟

Single-Pass Conversion:
𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑟𝑒𝑎𝑐𝑡𝑜𝑟

19
4.7g Purging

Why Purging is needed.

 Inert gases (e.g., nitrogen, argon, etc.) are used in processes because
they do not undergo chemical reactions under given conditions.
 Using inert gas in a system prevents undesirable chemical reactions from
occurring (e.g., oxidation, hydrolysis, combustion).
 Purging with nitrogen (N2) minimizes hazards of residual solvents or
process fluids.
 If an inert gas is introduced to the system and it doesn’t react, it has to
exit the system somewhere – otherwise, it builds up and would shut
down the process.
20
Chapter 4 Fundamentals of Material Balances
4.8 Combustion Reactions

21
 4.8 Combustion Reactions
4.8 a. Combustion Chemistry

O
Combustion : is the rapid reaction of a FUEL with OXYGEN that
produces tremendous quantities of ENERGY
O
0

Type of fuels 1. Solid fuels

Coal, oil shale, biomass (carbon, some hydrogen and sulfur, and
various noncombustible materials)
2. Liquid fuels
Fuel oil (mostly high molecular weight hydrocarbons, some sulfur)
3. Gaseous fuel
Natural gas, which is primarily methane, or liquefied petroleum
gas, which is usually propane and/or butane.

When a fuel is Carbon, C CO2 or CO

burned Hydrogen, H H2O
Sulfur, S Sulfur, SO2 22
 At temperatures greater than approximately 1800°C, some of
the nitrogen (N) in the air reacts to form nitric acid (NOx).
combustion
Complete vs. Incomplete combustion or partial
 A combustion reaction in which CO is formed from a
hydrocarbon is referred to as partial combustion or incomplete
combustion of the hydrocarbon.
𝐶 + 𝑂 → 𝐶𝑂
𝐶 𝐻 + 5𝑂 → 3𝐶𝑂 + 4𝐻 𝑂
Complete combustion of carbon
Complete combustion of propane
cuz of
O
𝐶 𝐻 + 𝑂 → 3𝐶𝑂 + 4𝐻 𝑂
𝐶𝑆 + 5𝑂 → 𝐶𝑂 +2𝑆𝑂
Partial combustion of propane
f
Complete combustion of carbon disulfide
the
balanced

ego complete
the rim is
23
Air in combustion
Air is the source of oxygen in most combustion reactors
Dry air has the following molar composition

𝑁 78.03 % For simplicity, assume that the air

𝑂 20.99 % consists of: 79% N2, 21% O2
𝐴𝑟 0.94 % 79 𝑚𝑜𝑙𝑒𝑠 𝑁 𝑚𝑜𝑙𝑒𝑠 𝑁
𝐶𝑂 0.03 %
0.01 %
21 𝑚𝑜𝑙𝑒𝑠 𝑂 O
= 3.76
𝑚𝑜𝑙𝑒𝑠 𝑂
Average molecular weight of air = 29
𝑁 , 𝐻𝑒, 𝑁𝑒, 𝐾𝑟, 𝑋𝑒
100.0 %

 Composition on a wet basis is commonly used to denote the component mole

fractions of a gas that contains water,
 Composition on a dry basis signifies the component mole fractions of the same
gas without the water
 It is important to be able to convert a composition on a dry basis to its
corresponding composition on a wet basis
 Stack gas, exhaust gas or flue gas: is the product gas that leaves a combustion
furnace
24
 Example 4.8-1 Composition on Wet and Dry Bases
A stack gas contains 60.0 mole% N2, 15.0% CO2, 10.0% O2, and the balance
H2O. Calculate the molar composition of the gas on a dry basis.

Basis: 100 mol Wet Gas

60.0 mole N2,
60.0 𝑚𝑜𝑙 𝑁
dry
68 J
15.0 𝑚𝑜𝑙 𝐶𝑂
15.0 mole CO2,
wet 10.0 mole O2, ⟹ 10.0 𝑚𝑜𝑙 𝑂
85.0 𝑚𝑜𝑙 𝑑𝑟𝑦 𝑔𝑎𝑠

Mif
15.0 mole H2O
pasis wet dry
.
% mole N2 = = 0.706 = 70.6 % 𝑁
Infidel % mole CO2 =
O = 0.176
.
.

= 17.6 % 𝐶𝑂

8
.
.
% mole O2 = = 0.118 = 11.8 % 𝑂
.

Dry Gas 25
 4.8b. Theoretical and Excess Oxygen and Air
 Combustion reactions are usually run with more air than is needed to
supply oxygen in stoichiometric proportion to the fuel.
 This has the effect of increasing the conversion of the valuable
reactant at the expense of the cost of the excess reactant and
additional pumping costs.
Theoretical Oxygen:
The moles (batch) or molar flow rate (continuous) of O2 needed for
complete combustion of all the fuel fed to the reactor, assuming that all
carbon in the fuel is oxidized to CO2 and all the hydrogen is oxidized to H2O.
Amount of (O2 or air) needed for complete combustion of the full amount of fuel.
Theoretical = stoichiometric 3
Theoretical Air:
The quantity of air that contains the theoretical oxygen.
26
 Excess Air:
The amount by which the air fed to the reactor exceeds the theoretical air

𝑚𝑜𝑙𝑒𝑠 𝑎𝑖𝑟 − 𝑚𝑜𝑙𝑒𝑠 𝑎𝑖𝑟

𝑷𝒆𝒓𝒄𝒆𝒏𝒕 𝑬𝒙𝒄𝒆𝒔𝒔 𝑨𝒊𝒓: × 100%
𝑚𝑜𝑙𝑒𝑠 𝑎𝑖𝑟

𝑛 =𝑛 = 𝑛∗

𝑛 − 𝑛∗ 𝑛 𝑛∗ 𝑛 𝑛
 𝐸𝑥 = − ∗  𝐸𝑥 = ∗ − 1  1 + 𝐸𝑥 =
𝐸𝑥 =
𝑛 ∗ 𝑛 ∗ 𝑛 𝑛 𝑛∗

If 50% excess air is supplied  𝑚𝑜𝑙𝑒𝑠 𝑎𝑖𝑟 = 1.5 𝑚𝑜𝑙𝑒𝑠 𝑎𝑖𝑟

Excess air = Excess O2

27
Example 4.8-2 Theoretical and Excess Air
100 mol/h of butane (C4H10 ) and 5000 mol/h of air are fed into a
combustion reactor. Calculate the percent excess air.
The stoichiometric equation for complete combustion of butane:
13
𝐶 𝐻 + 𝑂 → 4𝐶𝑂 + 5𝐻 𝑂
2
The theoretical air from the feed rate of fuel and the stoichiometric equation

100 𝑚𝑜𝑙 𝐶 𝐻 6.5 𝑚𝑜𝑙 𝑂 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑚𝑜𝑙 𝑂

𝑛̇ = = 650
ℎ 𝑚𝑜𝑙 𝐶 𝐻 ℎ

476
𝑛̇ =
650 𝑚𝑜𝑙 𝑂 4.76 𝑚𝑜𝑙 𝑎𝑖𝑟
ℎ 𝑚𝑜𝑙 𝑂
= 3094
𝑚𝑜𝑙 𝑎𝑖𝑟
ℎ
129
𝑛̇ − 𝑛̇ 5000 − 3094
% 𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 = × 100% = × 100% = 61.6%
𝑛̇ 3094
𝑚𝑜𝑙 𝑚𝑜𝑙

for checking
𝑛̇ = 1.616 𝑛̇ = 1.616 × 3094 = 5000
ℎ ℎ 28
 4.8c. Material Balances on Combustion Reactions
 Procedure for writing and solving material balance on combustion
reactor is same as that for any reactive system.

 In labeling flowchart, the outlet stream (stack gas) should include

• Unreacted fuel 7
• Unreacted oxygen 𝐶 𝐻 + 𝑂 → 2𝐶𝑂 + 3𝐻 𝑂
2
• CO2, CO, and H2O
5
• N2 if air is used instead of pure O2 𝐶 𝐻 + 𝑂 → 2𝐶𝑂 + 3𝐻 𝑂
2
 O2 feed rate is calculated from specified %Excess O2 or %Excess air
(both has same value). Theoretical amounts are calculated from
reaction assuming complete combustion of the fuel.

 If one reaction is given follow extent or atomic balance method. If

more than one reaction, use atomic method. The molecular balance
method should be avoided.
29
30
Example 1 – Extent of reactiontofindprodutonf
Phosgene gas is probably most famous for being the first toxic gas used offensively in
World War I, but is also used extensively in the chemical processing of a wide variety of
materials. Phosgene can be made by the catalytic reaction between CO and chlorine gas
(Cl2) in the presence of a carbon catalyst (catalyst is not a reactant).

CO + Cl2  COCl2

The reaction products from the given reactor contain 3.00 Ib-moles of Cl2, 10.00 Ib-
moles of phosgene (COCl2), and 7.00 Ib-moles of CO.

a) Calculate the extent of reaction[ans. 10 Ib-mole].

b) Determine the initial amounts of CO and Cl2 that were used in the reaction
[ans. CO = 17 Ib-mol, Cl2= 13 Ib-mole]

31
 a) Calculate the extent of reaction.

Solution Basis: 10 lb moles phosgene

For phosgene: ξ = = = 10 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑚𝑜𝑙𝑒𝑠
a

b) Determine the initial amounts of CO and Cl2 that

were used in the reaction.
nichtatibenseitsaradond
Solution 𝑛 , =𝑛 , −ν ξ = 7 − −1 10 = 17 𝑙𝑏 𝑚𝑜𝑙
𝑛 , =𝑛 , −ν ξ = 3 − −1 10 = 13 𝑙𝑏 𝑚𝑜𝑙

32
Example 2 – Limiting reactant, conversion and extent
A well known reaction to generate hydrogen (H2) from steam (H2O vapor) is the so

PECOR
called gas shift reaction:
O
CO + H2O 2 + H2

If the gaseous feed to reactor consists of 30 moles of CO per hour, 12 moles of CO2 per
hour, and 35 moles of steam per hour at 800C, and 18 moles of H2 are produced per
hour. Calculate

a) The limiting reactant [ans. CO].

Just for gaseous
reaction
b) The excess reactant.
c) The fraction of conversion of steam [ans. 0.514]
d) The degree of completion of the reaction (hint: Degree of completion is the fraction
of the limiting reactant converted into products) [0.6]
e) The kg of H2 yielded per kg of steam fed. [ans. 0.0576 kg H2 ].
f) The moles of CO2 produced by the reaction per mole of CO fed. [ans. 0.6 mol CO2
produced / mole CO fed]

high
g) The extent of reaction. [ans. 18 mol ]

there will
be
unless if
liquid and high 33
 volum ftemperature
r
there is
Solution Basis: 30 mol CO, 12 mol CO2, 35 mol H2O feed = 1 hr
and
stirrer
inside the
a

reactor
𝐶𝑂 + 𝐻 𝑂 ↔ 𝐶𝑂 + 𝐻
MW: 28 18 44 2
fed stoichiometry

a) = = 0.86 < = =1 CO is limiting reactant bytheE.R

G overall forsteam will get
b) 𝐻 𝑂 is the excess reactant
consumed
34
Solution

c) = 0.514

d)
8 = 0.60 (for each mol of H2 produced, 1 mol CO reacts

e) 18 kmol 𝐻 = 0.0571 𝑘𝑔 𝐻

f) 1 mol of 𝐶𝑂 is produced for each mol of 𝐻

= 0.60 reactens
Prod we dont home Ha in
f) ξ = as
= 18 𝑟𝑒𝑎𝑐𝑡𝑖𝑛𝑔 𝑚𝑜𝑙𝑒𝑠 𝑢𝑠𝑖𝑛𝑔 𝐻

35
Example 4.7-1 Incomplete Combustion of Methane

Methane is burned with air in a continuous steady-state combustion reactor to yield a mixture of
carbon monoxide, carbon dioxide, and water. The reactions taking place are

3
𝐶𝐻 + 𝑂 → 𝐶𝑂 + 2𝐻 𝑂 𝟏
2

𝐶𝐻 + 2𝑂 → 𝐶𝑂 + 2𝐻 𝑂 (𝟐)

The feed to the reactor contains 7.80 mole% CH4, 19.4% O2, and 72.8% N2. The percentage
conversion of methane is 90.0%, and the gas leaving the reactor contains 8 mol CO2/mol CO. Carry
out a dgree-of-freedom analysis on the process. Then calculate the molar composition of the
product stream using molecular species balances, atomic species balances, and extents of reaction.

36
 Basis: 100 mol Feed

Degree-of-Freedom Analysis

• Molecular species balances: 5 unknown variables + 2 independent reactions – 6 independent molecular

species balances (CH4, O2, N2, CO, CO2, H2O) – 1 specified methane conversion = 0 degrees of freedom

• Atomic species balances: 5 unknown variables – 3 independent atomic species balances (C, H, O) – 1
nonreactive molecular species balance (N2) – 1 specified methane conversion = 0 degrees of freedom

• Extents of reaction: 5 unknown variables + 2 independent reactions – 5 expressions for ni (ξ) (i = CH4, O2,
CO, CO2, H2O) – 1 nonreactive molecular species balance (N2) – 1 specified methane conversion = 0
degrees of freedom 37
 The specified methane conversion can be used to determine nCH4:

90% CH4 Conversion: 10% remains unconverted

𝑛 = 0.100 7.80 𝑚𝑜𝑙 𝐶𝐻 𝑓𝑒𝑑 = 0.780 𝑚𝑜𝑙 𝐶𝐻

 Nitrogen balance to determine the nonreactive species in the process, nN2:

N2 Balance: input = output

𝑛 = 72.8 𝑚𝑜𝑙 𝑁

 It remains to determine nCO, nH2O and nO2 by each of the indicated methods.

38
 Molecular Species Balances
This is the most cumbersome method when multiple reactions are involved. We strongly recommended against using it.

Each balance on a reactive species will contain generation and/or consumption terms.

𝐶 , (𝑚𝑜𝑙 𝐶𝐻 ) → 𝑡ℎ𝑒 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 𝑜𝑓 𝑚𝑒𝑡ℎ𝑎𝑛𝑒 𝑖𝑛 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 1

𝐺 , 𝑚𝑜𝑙 𝐻 𝑂 → 𝑡ℎ𝑒 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑖𝑛 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 2

Example:

2 𝑚𝑜𝑙 𝐻 𝑂 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑
𝐺 , 𝑚𝑜𝑙 𝐻 𝑂 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 𝑖𝑛 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 1 = 𝐶 , (𝑚𝑜𝑙 𝑂 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑 𝑖𝑛 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛 1) ×
1.5 𝑚𝑜𝑙 𝑂 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

CO Balance: output = generation

𝑛 =𝐺 , (𝟑)

CO2 Balance: output = generation

8𝑛 =𝐺 , (𝟒) 39
CH4 Balance: input = output + consumption

𝑛 =𝐺 , = 0.780 𝑚𝑜𝑙 𝐶𝑂 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 (𝟓)

8𝑛 =𝐺 , = 6.24 𝑚𝑜𝑙 𝐶𝑂 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒𝑑 (𝟔)

40
41
 Atomic Species Balances
We will write the C and H balances first (only one unknown), then the O balance to determine the remaining unknown.

All atomic species balances have the form input = output.

42
Same: 43
Extents of Reaction

44
Same:

Which method is easy?

45