CN 2101: Material and Energy

Balances
Lecture 3: Balances on reactive processes and
Combustion reactions

Department of Chemical and Biomolecular Engineering

National University of Singapore

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OVERVIEW FOR THIS SESSION
1.8 Balances on reactive processes
– Balances on Molecular and Atomic species
– Independent Equations, Independent Species, and
Independent Reactions
– Molecular Species Balances
– Atomic Species Balances
– Extent of Reaction
– Product Separation and Recycle
– Purging

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OVERVIEW FOR THIS SESSION
1.9 Combustion reactions
– Combustion Chemistry
– Theoretical and excess oxygen and air
– Material Balances on Combustion Reactors

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1.8 BALANCES ON REACTIVE
PROCESSES

Balances on Molecular and Atomic Species

Systems involving chemical reactions may be analysed

using:
(a) Molecular species balance (e.g 𝑂𝑂2 , 𝐶𝐶𝐻𝐻4 )
(b) Atomic species balances
(c) Extent of reaction

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EXAMPLE
The flowchart for the dehydrogenation of ethane in a
steady-state continuous reactor is shown below:

100kmol 𝐶𝐶2 𝐻𝐻6 /min 40kmol 𝐻𝐻2 /min

𝑛𝑛̇ 1 kmol 𝐶𝐶2 𝐻𝐻6 /min
𝑛𝑛̇ 2 kmol 𝐶𝐶2 𝐻𝐻4 /min

The reaction is 𝐶𝐶2 𝐻𝐻6 → 𝐶𝐶2 𝐻𝐻4 + 𝐻𝐻2

A number of balances can be written on this process:
(1) Total mass
(2) Molecular species 𝐶𝐶2 𝐻𝐻6 , 𝐶𝐶2 𝐻𝐻4 , 𝐻𝐻2
(3) Atomic species

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EXAMPLE
RECALL for CONTINUOUS STEADY STATE process:

For total mass balance: Input = Output

For Molecular species balance:

Input + Generation = Output + Consumption

For Atomic species balance: Input = Output

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 EXAMPLE
𝐶𝐶2 𝐻𝐻6 → 𝐶𝐶2 𝐻𝐻4 + 𝐻𝐻2
Balances for the flowchart
100kmol 𝐶𝐶2 𝐻𝐻6 /min 40kmol 𝐻𝐻2 /min
𝑛𝑛̇ 1 kmol 𝐶𝐶2 𝐻𝐻6 /min
𝑛𝑛̇ 2 kmol 𝐶𝐶2 𝐻𝐻4 /min
Total Mass Balance: Input = Output
100 x 30 kg = 40 x 2 kg + 30 𝑛𝑛̇ 1 + 28 𝑛𝑛̇ 2

Molecular Species Balance: Atomic Species Balance:

Input + Generation = Output + Consumption Input = Output
𝑪𝑪𝟐𝟐 𝑯𝑯𝟔𝟔 : 100 + 0 = 𝑛𝑛̇ 1 + Cons𝐶𝐶2𝐻𝐻6 𝑪𝑪 : 2x100 = 2𝑛𝑛̇ 1 +2𝑛𝑛̇ 2
𝑪𝑪𝟐𝟐 𝑯𝑯𝟒𝟒 : 0 + Gen𝐶𝐶2𝐻𝐻4 = 𝑛𝑛̇ 2 + 0 𝑯𝑯: 6 x 100 = 2 x 40 + 6𝑛𝑛̇ 1 +4𝑛𝑛̇ 2
𝑯𝑯𝟐𝟐 : 0 + Gen𝐻𝐻2 = 40 + 0

How many ways can you solve for unknowns 𝑛𝑛̇ 1 and 𝑛𝑛̇ 2 ???
Simple balance using atomic species  𝑛𝑛̇ 1 = 60kmol and 𝑛𝑛̇ 2 = 40kmol

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INDEPENDENT EQUATIONS, INDEPENDENT
SPECIES AND INDEPENDENT REACTIONS

Independent equations:
Algebraic equations are independent if you cannot
obtain any one of them by adding and subtracting
multiples of any of the others

Example:
𝑥𝑥 + 2𝑦𝑦 = 4 − (1)
3𝑥𝑥 + 6𝑦𝑦 = 12 − (2)
Are not independent because (1) x 3 = (2)

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INDEPENDENT EQUATIONS, INDEPENDENT
SPECIES AND INDEPENDENT REACTIONS
Independent equations:
Example:
𝑥𝑥 + 2𝑦𝑦 = 4 − (1)
2𝑥𝑥 − 𝑧𝑧 = 2 − (2)
4𝑦𝑦 + 𝑧𝑧 = 6 − (3)
Are not independent because (3) = 2x(1) –(2)
*If 2 molecular species are in the same ratio to each other wherever they
appear in a process, and this ratio is incorporated in the flowchart labelling,
balances on these species will not be independent equations (RECALL SPLITTER
EXAMPLE EARLIER)
Similarly, if 2 atomic species occur in the same ratio wherever they appear in
a process, balances on these species will not be independent equations.

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INDEPENDENT EQUATIONS, INDEPENDENT
SPECIES AND INDEPENDENT REACTIONS

Independent reactions:
Chemical reactions are independent if the stoichiometric
equation of any one of them cannot be obtained by adding or
subtracting multiples of the stoichiometric equations of the
others.
Example: Rxn 1: 𝐴𝐴 → 2𝐵𝐵 (1)
Rxn 2: 𝐵𝐵 → 𝐶𝐶 (2)
Rxn 3: 𝐴𝐴 → 2𝐶𝐶 (3)

These 3 reactions are not independent since (3) = (1) + 2x(2)

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MOLECULAR SPECIES BALANCES
If molecular species balances are used to determine unknown
stream variables for a reactive process, the balances must
contain generation and consumption terms

Degree of freedom analysis is as follows:

No. unknown labelled variables
+ No. independent chemical reactions
- No. independent molecular species balances
- No. other equations relating unknown variables
= No. degree of freedom 𝑛𝑛𝑑𝑑𝑑𝑑

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 MOLECULAR SPECIES BALANCES
𝐶𝐶2 𝐻𝐻6 → 𝐶𝐶2 𝐻𝐻4 + 𝐻𝐻2
Balances for the flowchart
100kmol 𝐶𝐶2 𝐻𝐻6 /min 40kmol 𝐻𝐻2 /min
𝑛𝑛̇ 1 kmol 𝐶𝐶2 𝐻𝐻6 /min
𝑛𝑛̇ 2 kmol 𝐶𝐶2 𝐻𝐻4 /min
Degree of freedom analysis: Molecular Species Balance:
2 unknown variables (𝑛𝑛̇ 1 , 𝑛𝑛̇ 2 ) Input + Generation
+ 1 independent chemical rxn = Output + Consumption
- 3 independent molecular species balance 𝑪𝑪𝟐𝟐 𝑯𝑯𝟔𝟔 : 100 + 0 = 𝑛𝑛̇ 1 + Cons𝐶𝐶2𝐻𝐻6
- 0 other equations relating unknown variables 𝑪𝑪𝟐𝟐 𝑯𝑯𝟒𝟒 : 0 + Gen𝐶𝐶2𝐻𝐻4 = 𝑛𝑛̇ 2 + 0
= 0 degrees of freedom 𝑯𝑯𝟐𝟐 : 0 + Gen𝐻𝐻2 = 40 + 0
Based on Stoichiometry:
1𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 𝐶𝐶2 𝐻𝐻4 generated / 1𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 𝐶𝐶2 𝐻𝐻6 consumed
1𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 𝐻𝐻2 generated / 1𝑘𝑘𝑘𝑘𝑘𝑘𝑘𝑘 𝐶𝐶2 𝐻𝐻6 consumed

Balance using molecular species  𝑛𝑛̇ 1 = 60kmol and 𝑛𝑛̇ 2 = 40kmol

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ATOMIC SPECIES BALANCE
The number of degrees of freedom is determined
directly by subtracting equations from labelled
unknowns. No additional degrees of freedom are
contributed by the reactions

Degree of freedom analysis is as follows:

No. unknown labelled variables
- No. independent atomic species balances
- No. other equations relating unknown variables
= No. degree of freedom 𝑛𝑛𝑑𝑑𝑑𝑑

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ATOMIC SPECIES BALANCES
𝐶𝐶2 𝐻𝐻6 → 𝐶𝐶2 𝐻𝐻4 + 𝐻𝐻2
Balances for the flowchart
100kmol 𝐶𝐶2 𝐻𝐻6 /min 40kmol 𝐻𝐻2 /min
𝑛𝑛̇ 1 kmol 𝐶𝐶2 𝐻𝐻6 /min
𝑛𝑛̇ 2 kmol 𝐶𝐶2 𝐻𝐻4 /min
Degree of freedom analysis:
2 unknown variables (𝑛𝑛̇ 1 , 𝑛𝑛̇ 2 )
- 2 independent atomic species balance
- 0 other equations relating unknown variables
= 0 degrees of freedom

Atomic Species Balance:

Input = Output
𝑪𝑪 : 2x100 = 2𝑛𝑛̇ 1 +2𝑛𝑛̇ 2
𝑯𝑯: 6 x 100 = 2 x 40 + 6𝑛𝑛̇ 1 +4𝑛𝑛̇ 2

Balance using atomic species  𝑛𝑛̇ 1 = 60kmol and 𝑛𝑛̇ 2 = 40kmol

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EXTENT OF REACTION
Another way is to write expressions for each product
species molar amount or flowrate in terms of extent of
reaction

Degree of freedom analysis is as follows:

No. unknown labelled variables
+ No. independent chemical reactions (1 unknown extent of rxn each)
- No. independent reactive species (1 eqn for each species in terms of
extent of rxn)
- No. independent non-reactive species (1 balance eqn each)
= No. degree of freedom 𝑛𝑛𝑑𝑑𝑑𝑑

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EXTENT OF REACTION
𝐶𝐶2 𝐻𝐻6 → 𝐶𝐶2 𝐻𝐻4 + 𝐻𝐻2
Balances for the flowchart
100kmol 𝐶𝐶2 𝐻𝐻6 /min 40kmol 𝐻𝐻2 /min
Degree of freedom analysis: 𝑛𝑛̇ 1 kmol 𝐶𝐶2 𝐻𝐻6 /min
2 unknown variables (𝑛𝑛̇ 1 , 𝑛𝑛̇ 2 ) 𝑛𝑛̇ 2 kmol 𝐶𝐶2 𝐻𝐻4 /min
+ 1 independent rxn
- 3 independent reactive species balance
- 0 other equations relating unknown variables 𝒏𝒏̇ 𝒊𝒊 = 𝒏𝒏̇ 𝒊𝒊𝒊𝒊 + 𝝊𝝊𝝃𝝃
̇
= 0 degrees of freedom
Reactive species
𝑯𝑯𝟐𝟐 : 40 = 0 + (1) (𝝃𝝃)  𝝃𝝃 = 40
𝑪𝑪𝟐𝟐 𝑯𝑯𝟔𝟔 : 𝑛𝑛̇ 1 = 100 + (-1) (𝝃𝝃)  𝑛𝑛̇ 1 = 60 kmol
𝑪𝑪𝟐𝟐 𝑯𝑯𝟒𝟒 : 𝑛𝑛̇ 2 = 0 + (1) (𝝃𝝃)  𝑛𝑛̇ 2 = 40 kmol

Balance using atomic species  𝑛𝑛̇ 1 = 60kmol and 𝑛𝑛̇ 2 = 40kmol

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PRODUCT SEPARATION AND
RECYCLE

2 definitions of reactant conversion:

Overall Conversion
reactant input to process − reactant output from process
=
reactant input to process

Single − pass Conversion

reactant input to reactor − reactant output from reactor
=
reactant input to reactor

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 EXAMPLE:
100mol G/min 25mol G/min 75mol F/min
75mol G/min Product
Reactor 75mol F/min Separation
Unit
25mol G/min

𝐎𝐎𝐎𝐎𝐎𝐎𝐎𝐎𝐎𝐎𝐎𝐎𝐎𝐎 𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂 % Achieved only due

reactant input to process − reactant output from process
= × 100% to assuming
reactant input to process
𝐺𝐺 𝐺𝐺 perfect
75 𝑚𝑚𝑚𝑚𝑚𝑚 − 0 𝑚𝑚𝑚𝑚𝑚𝑚 separation. If
𝑚𝑚𝑚𝑚𝑚𝑚 𝑚𝑚𝑚𝑚𝑚𝑚
= × 100% = 100%
𝐺𝐺 separation is less
75 𝑚𝑚𝑚𝑚𝑚𝑚
𝑚𝑚𝑚𝑚𝑚𝑚 than 100%,
overall conversion
𝐒𝐒𝐒𝐒𝐒𝐒𝐒𝐒𝐒𝐒𝐒𝐒 − 𝐩𝐩𝐩𝐩𝐩𝐩𝐩𝐩 𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐂𝐧𝐧 % will be less than
reactant input to reactor − reactant output from reactor
= × 100% 100% but always
reactant input to reactor
greater than
100 𝑚𝑚𝑚𝑚𝑚𝑚
𝐺𝐺
𝑚𝑚𝑚𝑚𝑚𝑚
− 25 𝑚𝑚𝑚𝑚𝑚𝑚
𝐺𝐺
𝑚𝑚𝑚𝑚𝑚𝑚
single-pass
= 𝐺𝐺 × 100% = 75% conversion
100 𝑚𝑚𝑚𝑚𝑚𝑚
𝑚𝑚𝑚𝑚𝑚𝑚

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PURGING
• One problem in recycling in process is that materials
entering with the fresh feed or that is produced in a
reaction may remain entirely in a recycle stream,
rather that being carried out in a process product
• Accumulation of the substance can occur, making the
steady state operation impossible
• To prevent such build-up, a portion of the recycle
stream must be withdrawn as a purge stream

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 EXAMPLE
Production of ethylene oxide from ethylene
2𝐶𝐶2 𝐻𝐻4 + 𝑂𝑂2 → 2𝐶𝐶2 𝐻𝐻4 𝑂𝑂
Recycle Purge

40 mol 𝐶𝐶2 𝐻𝐻4 /s 10 mol 𝐶𝐶2 𝐻𝐻4 /s

20 mol 𝑂𝑂2 /s 5 mol 𝑂𝑂2 /s
452 mol 𝑁𝑁2 /s 113 mol 𝑁𝑁2 /s
50 mol 𝐶𝐶2 𝐻𝐻4 /s
25 mol 𝑂𝑂2 /s
565 mol 𝑁𝑁2 /s
Solvent
Fresh Feed
Reactor Absorber
60 mol 𝐶𝐶2 𝐻𝐻4 /s 100 mol 𝐶𝐶2 𝐻𝐻4 /s 50 mol 𝐶𝐶2 𝐻𝐻4 /s
30 mol 𝑂𝑂2 /s 50 mol 𝑂𝑂2 /s 25 mol 𝑂𝑂2 /s
113 mol 𝑁𝑁2 /s 565 mol 𝑁𝑁2 /s 565 mol 𝑁𝑁2 /s
50 mol 𝐶𝐶2 𝐻𝐻4 𝑂𝑂 /s Product
50 mol 𝐶𝐶2 𝐻𝐻4 𝑂𝑂 /s
Solvent

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1.9 COMBUSTION REACTIONS
Combustion is the rapid reaction of a substance with
oxygen.

Oxidation reactions release significant amounts of energy as

heat
• Carbon (C) to CO and CO2
• Hydrogen (H) to H2O
• Sulphur (S) to SO2
• Nitrogen (N) to NO and NO2

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COMBUSTION CHEMISTRY

Common Fuel
– Coal (mainly carbon)
– Fuel oil (high MW hydrocarbons)
– Gaseous fuel (natural gas, etc.)
– Liquified petroleum gas (LPG) (usually propane /
butane)

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COMBUSTION CHEMISTRY
• When fuel is burned, carbon in the fuel reacts to form either
CO or CO2, hydrogen forms H2O and sulfur forms SO2
• At temperatures > 1800 oC, some of the nitrogen in the air
reacts to form NO (nitric oxide)
• Incomplete combustion or partial combustion produced CO
(CO2 may also be produced)

Examples:
𝐶𝐶 + 𝑂𝑂2 → 𝐶𝐶𝑂𝑂2 Complete combustion of carbon
𝐶𝐶3 𝐻𝐻8 + 5𝑂𝑂2 → 3𝐶𝐶𝑂𝑂2 + 4𝐻𝐻2 𝑂𝑂 Complete combustion of propane
7
𝐶𝐶3 𝐻𝐻8 + 𝑂𝑂2 → 3𝐶𝐶𝐶𝐶 + 4𝐻𝐻2 𝑂𝑂 Partial combustion of propane
2
𝐶𝐶𝑆𝑆2 + 3𝑂𝑂2 → 𝐶𝐶𝑂𝑂2 + 2𝑆𝑆𝑂𝑂2 Complete combustion of carbon disulfide

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OXYGEN FOR COMBUSTION

• Air is the source of oxygen for most combustion

reactors
• Average molar composition of air (dry basis)
𝑁𝑁2 78.03% Typically simplified as
𝑂𝑂2 20.99% 79% 𝑁𝑁2 , 21% 𝑂𝑂2
𝐴𝐴𝐴𝐴 0.94%
Average molecular weight = 29.0
𝐶𝐶𝐶𝐶2 0.03%
𝐻𝐻2 , 𝐻𝐻𝐻𝐻, 𝑁𝑁𝑁𝑁, 𝐾𝐾𝐾𝐾, 𝑋𝑋𝑋𝑋 0.01%
100%

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COMPOSITION OF AIR

• Air contains moisture (water vapor)

– Composition on a wet basis denote the
component mole fraction of gas that contains
water
– Composition on a dry basis denote the
component mole fraction of the same gas without
water

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EXAMPLE
A stack gas (or flue gas, i.e. product gas leaving a
combustion furnace) contains 60.0mole% N2,
15.0mole% CO2, 10.0mole% O2, and the balance H2O
Calculate the molar composition of the gas on a dry
basis?

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THEORETICAL AND EXCESS
OXYGEN AND AIR

If 2 reactants participate in a reaction and one is

considerably more expensive than the other, it will be
logical to feed the less expensive reactant in excess of
the valuable one.

In combustion reaction, air is an inexpensive reactant

(technically it is free!)

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THEORETICAL AND EXCESS
OXYGEN AND AIR
Theoretical Oxygen:
The moles (batch) or molar flow rate (continuous) of O2 required
for complete combustion of all fuel fed to reactor, based on all
carbon oxidized to CO2, all hydrogen oxidized to H2O and all
sulfur converted to SO2

Theoretical Air:
The quantity of air that contains the theoretical oxygen

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THEORETICAL AND EXCESS
OXYGEN AND AIR
Excess Air:
The amount by which the air fed to the reactor exceeds the
theoretical air.

Percent Excess Air:

(𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑎𝑎𝑎𝑎𝑎𝑎)𝑓𝑓𝑓𝑓𝑓𝑓 −(𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑎𝑎𝑎𝑎𝑎𝑎)𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡
× 100%
(𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 𝑎𝑎𝑎𝑎𝑎𝑎)𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡

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EXAMPLE
100 mol/h of butane and 5000 mol/h air are fed to a
continuous reactor. Calculate the percent excess of air.

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THEORETICAL AND EXCESS
OXYGEN AND AIR
2 points to note:
1. Theoretical air does NOT depends on how much is actually
burned. The fuel may not react completely or may react to
form both CO and CO2, but the theoretical air is still
calculated based on the required for ALL fuel to combust to
form CO2 only
2. Value of percent excess air depends ONLY on the theoretical
air and air feed rate and not how much O2 is actually
consumed in the reactor, or whether combustion is
complete or partial

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MATERIAL BALANCES ON
COMBUSTION REACTORS
1. When drawing the flowchart, ensure outlet stream (stack gas) includes
(a) Unreacted fuel (unless specified that all is consumed)
(b) Unreacted oxygen and nitrogen (if burned with air)
(c) Water and Carbon dioxide (product) and/or Carbon monoxide if incomplete
combustion specified
2. Calculate oxygen feed rate from specified excess oxygen or excess air
(a) First calculate theoretical oxygen from fuel feed rate and reaction stoichiometry
for complete combustion
(b) Calculate the oxygen feed rate by multiplying the theoretical oxygen by
(1+fractional excess oxygen)
3. If several reactions occur simultaneously (e.g. partial and complete
combustion)
(a) Atomic species balances and extent of reaction will be useful for calculations

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WORKED EXAMPLE 1.9
A hydrocarbon gas is burned with air. The dry-basis product gas
composition is 1.5mole% CO, 6.0%CO2, 8.2% O2 and 84.3% N2.
There is no atomic oxygen in the fuel. Calculate the ratio of
hydrogen to carbon in the fuel gas and speculate on what the
fuel might be. Then calculate the percent excess air fed in the
reactor.

REF. FELDER, R.M. AND ROUSSEAU, R.W., “ELEMENTARY PRINCIPLES OF CHEMICAL

PROCESSES” 4TH EDITION, JOHN WILEY & SONS, 2015 (OR GLOBAL EDITION, 2017)
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WORKED EXAMPLE 1.9

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 End of Lecture 3

Dr Cindy Lee (Senior Lecturer)

Department of Chemical and Biomolecular Engineering

National University of Singapore
NUS Faculty of Engineering, Block E4, Unit #05-12
+65 6601 3877 (Tel) [email protected]
https://blog.nus.edu.sg/chellyc

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