Combustion

(ME 301A)

Jishnu Bhattacharya
2022
Combustion & IC engines

Combustion

https://en.wikipedia.org/wiki/Candle

https://flamingoappliance.com/oven-repair/what-to-
do-when-your-gas-cooktop-has-weak-flames/

https://en.wikipedia.org/wiki/Coal-fired_power_station

https://ec.europa.eu/jrc/en/news/more-countries-ever-hit-forest-fires-2018
https://www.somagnews.com/happens-aircraft-engine-fails-flight/

Internal Combustion (IC) engines https://video.nationalgeographic.com/video/science/101-videos/0000016b-dd68-d9ed-a5fb-ddfc68550000

https://en.wikipedia.org/wiki/Marine_LNG_Engine

http://www.crankshift.com/internal-combustion-engine/

https://www.indiamart.com/proddetail/cummins-diesel-generator-set-
20294183597.html

https://24coaches.com/indian-railways-wdm-series/
https://www.carhelpcanada.com/volkswagen-settlement-reached/
Definitions 𝑛𝑖 ≡ number of moles of species 𝑖
𝑚𝑖 ≡ mass of species 𝑖
Species 𝑖 = 1: 𝑁

𝑛𝑡𝑜𝑡𝑎𝑙 = σ 𝑛𝑖 ≡ total number of moles in the gas-mixture

𝑚𝑡𝑜𝑡𝑎𝑙 = σ 𝑚𝑖 ≡ total mass of the gas-mixture
𝑛𝑖 𝑛𝑖
Mole fraction of species 𝑖: 𝑥𝑖 = = Note: ෍ 𝑥𝑖 = 1
σ 𝑛𝑖 𝑛𝑡𝑜𝑡𝑎𝑙

෍ 𝑦𝑖 = 1
𝑚𝑖 𝑚𝑖
Mass fraction of species 𝑖: 𝑦𝑖 = =
σ 𝑚𝑖 𝑚𝑡𝑜𝑡𝑎𝑙

Note:
Molecular weight of the mixture:
Molecular weight of the mixture is the
𝑚𝑡𝑜𝑡𝑎𝑙
𝑀𝑊𝑚𝑖𝑥 = weighted average of the molecular
𝑛𝑡𝑜𝑡𝑎𝑙 weights of all the species in the
mixture.
σ 𝑛𝑖 𝑀𝑊𝑖
= = σ 𝑥𝑖 𝑀𝑊𝑖
𝑛𝑡𝑜𝑡𝑎𝑙
Relation between mole fraction and mass fraction of a particular species:
𝑚𝑖
𝑦𝑖 =
𝑚𝑡𝑜𝑡𝑎𝑙

𝑛𝑖 𝑀𝑊𝑖 𝑥𝑖 𝑛𝑡𝑜𝑡𝑎𝑙 𝑀𝑊𝑖 𝑛𝑡𝑜𝑡𝑎𝑙 1

= = = 𝑥𝑖 𝑀𝑊𝑖 = 𝑥𝑖 𝑀𝑊𝑖
𝑚𝑡𝑜𝑡𝑎𝑙 𝑚𝑡𝑜𝑡𝑎𝑙 𝑚𝑡𝑜𝑡𝑎𝑙 𝑀𝑊𝑚𝑖𝑥

𝑀𝑊𝑖
𝑦𝑖 = 𝑥𝑖
𝑀𝑊𝑚𝑖𝑥

Similarly, one can show that

𝑅𝑢 𝑅𝑢
𝑅𝑚𝑖𝑥 = , just as 𝑅 = for a single gas.
𝑀𝑊𝑚𝑖𝑥 𝑀𝑊
Mixture properties We will use the overbar ( ഥ ) to indicate
molar-specific quantities, and variables
Molar-specific mixture enthalpy ℎത 𝑚𝑖𝑥 = ෍ 𝑥𝑖 ℎത 𝑖 (𝑇) without the overbar to indicate mass-
specific quantities.
Mass-specific mixture enthalpy ℎ𝑚𝑖𝑥 = ෍ 𝑦𝑖 ℎ𝑖 (𝑇)
Note:
and similarly for internal energies: 1. For ideal gases ℎ and 𝑢 are functions of 𝑇
alone.
Molar-specific mixture internal energy 𝑢ത 𝑚𝑖𝑥 = ෍ 𝑥𝑖 𝑢ത 𝑖 (𝑇) 2. Since the components in the gaseous
mixture are assumed to be at the same
temperature, all the enthalpies and internal
Mass-specific mixture internal energy 𝑢𝑚𝑖𝑥 = ෍ 𝑦𝑖 𝑢𝑖 (𝑇)
energies are evaluated at the mixture
temperature 𝑇.
and for entropies:

Molar-specific mixture entropy 𝑠𝑚𝑖𝑥

Mass-specific mixture entropy
ҧ = ෍ 𝑥𝑖 𝑠𝑖 (𝑇, 𝑝𝑖 ) Note:
1. For ideal gases 𝑠 is a function of 𝑇 and 𝑝.
𝑠𝑚𝑖𝑥 = ෍ 𝑦𝑖 𝑠𝑖 (𝑇, 𝑝𝑖 ) 2. The entropy of the gas i depends on its
temperature (which is the same as the
mixture temperature, 𝑇) and its partial
pressure 𝑝𝑖 .
 Review: First Law of Thermodynamics
A) For a system (fixed mass)
𝑄 = ∆𝐸 + 𝑊 In going from state 1 to state 2.

Heat added to the system Work done by the system

Change in
system energy on the surrounding
For a system with mass 𝑚,
1 2 specific internal energy 𝑢, speed
Here, the energy 𝐸 = 𝑚(𝑢 + 𝑐 + 𝑔𝑧) 𝑐 and elevation 𝑧 above a
2
datum. 𝑔 is acceleration due to
gravity.
B) For a control volume
Assumptions:
1. Control volume is fixed w.r.t. the coordinate system.
2. Steady-state steady-flow process

𝑄ሶ + 𝑚𝑒 ሶ 𝑖𝑛 𝑣𝑖𝑛 = 𝑊ሶ + 𝑚𝑒
ሶ 𝑖𝑛 + 𝑚𝑝 ሶ 𝑜𝑢𝑡 + 𝑚𝑝
ሶ 𝑜𝑢𝑡 𝑣𝑜𝑢𝑡
1 2
i.e., ሶ ሶ
𝑄 − 𝑊 = 𝑚ሶ (ℎ𝑜𝑢𝑡 − ℎ𝑖𝑛 ) + 𝑐𝑜𝑢𝑡 − 𝑐𝑖𝑛 2
+ 𝑔(𝑧𝑜𝑢𝑡 − 𝑧𝑖𝑛 )
2
 Stoichiometry

Stoichiometry describes the mass balance in a chemical reaction

For a hydrocarbon fuel CxHy, the oxidation reaction

can be represented as
Note:
CxHy + 𝑎 (O2 + 3.76 N2)  xCO2 + (y/2)H2O + 3.76𝑎 N2 Air contains 21% O2 and 79% N2 by volume.
Since
Equating the number of oxygen atoms on both sides, 𝑝𝑉𝑂2 = 𝑛𝑂2 𝑅𝑢 𝑇 and 𝑝𝑉𝑁2 = 𝑛𝑁2 𝑅𝑢 𝑇
𝑦 𝑦
2𝑎 = 2𝑥 + i.e., 𝑎=𝑥+ We have, 𝑉𝑂2 𝑛𝑂2 21
2 4 = =
𝑉𝑁2 𝑛𝑁2 79
Thus, the complete oxidation of 1 mole of the fuel requires
𝑎 moles of O2 + 3.76𝑎 moles of N2 i.e., 𝑛𝑁2 =3.76 𝑛𝑂2
Thus for each mole of O2, air contains
3.76 moles of N2.
e.g., in case of burning of methane (CH4), 𝑎 = 1 + 1 = 2.
CH4 + 2 (O2 + 3.76 N2)  CO2 + 2H2O + (3.76 × 2) N2
Thus, the complete oxidation of 1 mole of methane requires
2 moles of O2 & 3.76 × 2 = 7.52 moles of N2
 Stoichiometry

Define:
Stoichiometric quantity of oxidizer: minimum amount
needed to completely burn a given quantity of fuel.
 In most cases, atmospheric air is the oxidizer.

CH4 + 2 (O2 + 3.76 N2)  CO2 + 2H2O + (3.76 × 2) N2

The complete oxidation of 1 mole (16 gm) of methane requires:

2 moles (64 gm) of O2 + 7.52 moles (210.56 gm) of N2

Quantity of CH4 Stoichiometric quantity of air

1 mole (16 gm) 64 gm of O2 + 210.56 gm of N2
=274.56 gm of air
2 moles (32 gm) 274.56 x 2 = 549.12 gm of air
 Stoichiometry

Stoichiometric air-fuel ratio: the stoichiometric

quantity of air per unit mass of the fuel is called the Note: The term Stoichiometric
Stoichiometric air-fuel ratio: 𝑚𝑎𝑖𝑟 fuel-air ratio, (𝐹/𝐴)𝑠𝑡𝑜𝑖𝑐 , is
(𝐴/𝐹)𝑠𝑡𝑜𝑖𝑐 = also widely used.
𝑚𝑓𝑢𝑒𝑙
𝑠𝑡𝑜𝑖𝑐

𝑛𝑎𝑖𝑟 𝑀𝑊𝑎𝑖𝑟
=
𝑛𝑓𝑢𝑒𝑙 𝑀𝑊𝑓𝑢𝑒𝑙
𝑠𝑡𝑜𝑖𝑐

𝑎 + 3.76𝑎 𝑀𝑊𝑎𝑖𝑟 Molecular weight of the air

= (neglecting gases other than O2 and
1 𝑀𝑊𝑓𝑢𝑒𝑙
N2) is
𝑀𝑊𝑎𝑖𝑟 = 𝑥𝑂2 𝑀𝑊𝑂2 + 𝑥𝑁2 𝑀𝑊𝑁2
2 + 3.76(2) 28.84 1 3.76
e.g., for methane (CH4), 𝑎 = 2. So (𝐴/𝐹)𝑠𝑡𝑜𝑖𝑐 = × = 17.16 = 𝑀𝑊𝑂2 + 𝑀𝑊𝑁2
1 16 4.76 4.76

i.e., 17.16 g (or kg) of air is required to completely burn 1 g (or kg) of methane. = 28.84

Thus, (𝐴/𝐹)𝑠𝑡𝑜𝑖𝑐 for methane is 17.16.

Stoichiometry

𝐴/𝐹 𝑠𝑡𝑜𝑖𝑐
Equivalence ratio Φ=
(𝐴/𝐹)
For combustion of
methane
Rich mixture
Φ>1 Less than stoichiometric quantity of oxidizer (𝐴/𝐹) < 17.16
(Fuel-rich mixture)
Φ<1 Lean mixture
Greater than stoichiometric quantity of oxidizer (𝐴/𝐹) > 17.16
(Oxidizer-rich mixture)

Φ=1 Stoichiometric
Stoichiometric quantity of oxidizer (𝐴/𝐹) = 17.16
mixture
Off-stoichiometric Combustion
Off-stoichiometric Combustion
Off-stoichiometric Combustion
Analysis of Fuel

Proximate Analysis: How much of different compounds are present -hydrocarbons, coal, hydrogen, sulphur,
moisture, ash etc.

Ultimate Analysis: How much of each elements are present - carbon, hydrogen, oxygen, nitrogen etc.

Both can be done on mass basis or mole basis

Combustion
(ME 301A)

Jishnu Bhattacharya
2022
Standardized enthalpy

Standardized enthalpy
Take into account the chemical energy changes in reactions
Enthalpy of reaction

Chemical energy (𝒖𝒄𝒉𝒆𝒎 ): energy associated with the chemical bonds of a

substance.

Why do we need to consider chemical energy?

Breaking chemical bonds needs energy

E
e.g., dissociation of oxygen: O2 2O

Energy
Interatomic distance
Conversely, formation of new bonds releases energy
 Standardized enthalpy

Why do we need to consider chemical energy in reactions?

A chemical reaction involves both breaking and formation of bonds

e.g., burning of carbon: C + O2  CO2

Breaking of O − O bond Formation of C − O bonds

Energy associated with all the bonds (𝒖𝒄𝒉𝒆𝒎 ) is different 

energy will be absorbed/released in chemical reactions

This chemical energy (𝒖𝒄𝒉𝒆𝒎 ) needs to be accounted for when analysing reacting systems

Non-reacting systems: 𝑄 − 𝑊 = 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝑝𝑉 𝑜𝑢𝑡 − 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝑝𝑉 𝑖𝑛 (First Law for SSSF system)

But in reacting systems, 𝑄 − 𝑊 = 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑜𝑢𝑡 − 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑖𝑛

Standardized enthalpy

𝑄 − 𝑊 = 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑜𝑢𝑡 − 𝑢 + 𝐾𝐸 + 𝑃𝐸 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑖𝑛

Neglecting changes in KE and PE,

𝑄 − 𝑊 = 𝑢 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑜𝑢𝑡 − 𝑢 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 𝑖𝑛

𝑄 − 𝑊 = ℎ𝑜𝑢𝑡 − ℎ𝑖𝑛

where ℎ = 𝑢 + 𝒖𝒄𝒉𝒆𝒎 + 𝑝𝑉 Standardized enthalpy

How to evaluate h? 𝑇,𝑝

ℎ 𝑇, 𝑝 = ℎ 𝑇𝑟𝑒𝑓 , 𝑝𝑟𝑒𝑓 + ∆ℎ 𝑇𝑟𝑒𝑓 ,𝑝𝑟𝑒𝑓

ℎ due to chemical composition (bond energy) Sensible enthalpy change

Enthalpy of formation: ℎ𝑓
Standardized enthalpy
𝑇,𝑝
ℎ 𝑇, 𝑝 = ℎ 𝑇𝑟𝑒𝑓 , 𝑝𝑟𝑒𝑓 + ∆ℎ 𝑇𝑟𝑒𝑓 ,𝑝𝑟𝑒𝑓

ℎ due to chemical composition (bond energy) Sensible enthalpy change

Enthalpy of formation: ℎ𝑓

ഥ 𝒇 ):
Enthalpy of formation (𝒉
∆ℎ associated with the breaking of chemical bonds of elements at the
standard state and forming new bonds to create the compound of
interest at the standard state.
e.g. C + O2  CO2
Standard reference state: 𝑇 = 25 oC,
𝑝 =1 atm (1.01325×105 Pa)
 Standardized enthalpy
ഥ𝒇?
How to calculate 𝒉
Convention:
ഥ 𝒇 for elements in their naturally occurring state
𝒉
(chemically stable form) at reference 𝑇 and 𝑝 is zero, i.e., ഥ𝑓0 𝑇𝑟𝑒𝑓 = 0
𝒉

ഥ𝑓0 𝑇𝑟𝑒𝑓 = 0
𝒉 for N2
but ഥ𝑓0 𝑇𝑟𝑒𝑓 ≠ 0
𝒉 for N

Energy required to break N—N bond:

Bond dissociation energy for N2 at 298K is 945300 kJ/kmol of N2
Both N2 and N at
ഥ𝑓,𝑁
0 945300
Thus, 𝒉 𝑇 = 298 K = = 472650 kJ/kmol of N at 298 K reference conditions !
2
Standardized enthalpy

ഥ𝑓0 > 0
𝒉 Heat is absorbed during the formation of the substance
ഥ𝑓0 < 0 from its stable-state elements
𝒉 Heat is released
Q
N2  N+N ഥ𝑓,𝑁
𝒉 0
>0

Note: In principle, ℎ𝑓 can also be defined at non-reference conditions.

But the conditions for both reactants and products must be the same !

Note: If more than one stable states exist for an element, choose one of
them to have 𝒉 ഥ𝑓0 𝑇𝑟𝑒𝑓 = 0

e.g.: ഥ𝑓0 𝑇𝑟𝑒𝑓 = 0

𝒉 for graphite
but ഥ𝑓0 𝑇𝑟𝑒𝑓 ≠ 0
𝒉 for diamond
 Standardized enthalpy

Standardized enthalpy: ℎ 𝑇 = ℎത𝑓0 𝑇𝑟𝑒𝑓 + ∆ℎ𝑠 (𝑇)

Enthalpy of formation at reference state Sensible enthalpy change

(No chemical energy changes)

N2  N+N

472650 kJ/kmol
Enthalpy of formation table
Standardized enthalpy tables
Standardized enthalpy tables
 Standardized enthalpy

Example: calculating enthalpy of gas mixtures

 Standardized enthalpy

Example: calculating enthalpy of gas mixtures

 Standardized enthalpy

For a steady-state steady flow (SSSF) process/reaction, 𝑄 − 𝑊 = ℎ𝑜𝑢𝑡 − ℎ𝑖𝑛

When work done is negligible 𝑄 = ℎ𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

𝑄 = (ℎ𝑓0 + ∆ℎ)𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 −(ℎ𝑓0 + ∆ℎ)𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

If both reactants and products are at the reference state,

then
∆ℎ𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 = 0 and ∆ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = 0

Thus (ℎ𝑓0 )𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 = 𝑄 + (ℎ𝑓0 )𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

So we can calculate (ℎ𝑓0 )𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 if we measure 𝑄 and we know (ℎ𝑓0 )𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

C + O2  CO2
 Enthalpy of reaction

Consider a SSSF reaction, e.g.: C

CO2
298 K, 1 atm
298 K, 1 atm
O2
𝑊=0
𝑞 = ℎ𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

Define enthalpy of reaction: ∆ℎ𝑅 = 𝑞 = ℎ𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

assuming  The reaction is complete

 Reactants and products are at the same state (𝑇 and 𝑝)
*Not necessarily at the reference 𝑇 and 𝑝.

Note: ∆ℎ𝑅 will be different at different 𝑇 𝑎𝑛𝑑 𝑝 !

∆ℎ𝑅 = ℎ𝐶𝑂2 − (ℎ𝐶 + ℎ𝑂2 )

 Enthalpy of reaction

∆ℎ𝑅 = ℎ𝑝𝑟𝑜𝑑𝑐𝑢𝑡𝑠 − ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

If both reactants and products are at the reference 𝑇 and 𝑝,

=0 =0
∆ℎ𝑅 = (ℎ𝑓0 + ∆ℎ𝑠 )𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 −(ℎ𝑓0 + ∆ℎ𝑠 )𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

∆ℎ𝑅 = (ℎ𝑓0 )𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 −(ℎ𝑓0 )𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

0 0 0
e.g., ∆ℎ𝑅 = ℎ𝑓,𝐶𝑂2 − (ℎ𝑓,𝐶 + ℎ𝑓,𝑂2 )

For combustion reaction, Enthalpy of combustion = ∆ℎ𝑅

∆ℎ𝑅 < 0 For an exothermic reaction (combustion)

∆ℎ𝑅 > 0 For an endothermic reaction

Enthalpy of reaction

∆ℎ𝑅 = ℎ𝑝𝑟𝑜𝑑𝑐𝑢𝑡𝑠 − ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

Heat of combustion
Define heat of combustion OR heating value as ∆ℎ𝐶 = −∆ℎ𝑅

assuming  The reaction (combustion) is complete

 Reactants and products are at the same state

C + O2  CO2
∆ℎ𝐶 = 393,520 kJ/kmol
∆ℎ𝑅 = −393,520 kJ/kmol

Higher and Lower heating values

Higher heating value (HHV): When H2O in products is in the liquid state

When H2O in products is in the vapour state

Lower heating value (LHV):

HHV = LHV + (𝑁ℎത𝑓𝑔 )𝐻2𝑂

𝑁 = Number of moles
ℎത𝑓𝑔 = Molar enthalpy of vaporization at the specified state
Combustion
(ME 301A)

Jishnu Bhattacharya
2022
Heat of combustion
Define heat of combustion OR heating value as ∆ℎ𝐶 = −∆ℎ𝑅

assuming  The reaction (combustion) is complete

 Reactants and products are at the same state

C + O2  CO2
∆ℎ𝐶 = 393,520 kJ/kmol
∆ℎ𝑅 = −393,520 kJ/kmol

Higher and Lower heating values

Higher heating value (HHV): When H2O in products is in the liquid state

When H2O in products is in the vapour state

Lower heating value (LHV):

HHV = LHV + (𝑁ℎത𝑓𝑔 )𝐻2𝑂

𝑁 = Number of moles
ℎത𝑓𝑔 = Molar enthalpy of vaporization at the specified state
Heating values of fuel

Example:
Determine the HHV and LHV of gaseous octane (C8H18) at 298 K and 1 atm.
Solution
Combustion equation (stoichiometric)

C8H18(g) +12.5(O2 +3.76 N2)  8CO2 +9H2O (l or g) +12.5(3.76)N2

HV = −∆ℎ𝑅
= −(ℎ𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 )

= ℎത𝑓0 + ∆ℎത 𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 + 12.5 ℎത𝑓0 + ∆ℎത 𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 +12.5 × 3.76 ℎത𝑓0 + ∆ℎത 𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒
𝐶8𝐻18 𝑂2 𝑁2

−8 ℎത𝑓0 + ∆ℎത 𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 − 9 ℎത𝑓0 + ∆ℎത 𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 −12.5 × 3.76 ℎത𝑓0 + ∆ℎത 𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒
𝐶𝑂2 𝐻2𝑂 𝑁2

Note: ∆ℎത 𝑠𝑒𝑛𝑠𝑖𝑏𝑙𝑒 = 0, (ℎത𝑓0 )𝑂2 = 0, (ℎത𝑓0 )𝑁2 = 0

LHV = ℎത𝑓0 − 8 ℎത𝑓0 − 9 ℎത𝑓0

𝐶8𝐻18 𝐶𝑂2 𝐻2𝑂,(𝑔)
 Heating values of fuel

LHV = ℎത𝑓0 − 8 ℎത𝑓0 − 9 ℎത𝑓0

𝐶8𝐻18 𝐶𝑂2 𝐻2𝑂,(𝑔)

LHV = −208,450 − 8(−393,520) − 9(−241,820)

Table A-26 Table A-26 Table A-26 Property tables

LHV = 5,116,090 kJ/kmol of C8H18

For HHV use ℎത𝑓0 = ℎത𝑓0 − ℎത𝑓𝑔 = -241,820 – 2441.7 x 18 kJ/kmol = 285,771 kJ/kmol
𝐻2𝑂, 𝑙 𝐻2𝑂,(𝑔) 𝐻2𝑂,298K
ℎത𝑓0 = 285,830 kJ/kmol (From table A-26)
𝐻2𝑂, 𝑙
HHV = LHV + 9 ℎത𝑓𝑔
𝐻2𝑂,298K)

= LHV + 9 43950 = 5,511,640 kJ/kmol of C8H18

First-law analysis of combustion system
Steady state steady flow (SSSF) system:
𝑄ሶ − 𝑊ሶ = 𝑚(ℎ
ሶ 𝑜𝑢𝑡 − ℎ𝑖𝑛 ) ℎ is the standardized enthalpy

In terms of the number of moles, say per mole of the fuel:

𝑄 − 𝑊 = ෍ 𝑛𝑝 ℎത 𝑝 − ෍ 𝑛𝑟 ℎത 𝑟
𝑝 𝑟

𝑄 − 𝑊 = ෍ 𝑛𝑝 (ℎത𝑓0 + ∆ℎത 𝑠 )𝑝 − ෍ 𝑛𝑟 (ℎത𝑓0 + ∆ℎത 𝑠 )𝑟

𝑝 𝑟

𝑄 − 𝑊 = ෍ 𝑛𝑝 (ℎത𝑓0 )𝑝 − ෍ 𝑛𝑟 (ℎത𝑓0 )𝑟 + ෍ 𝑛𝑝 ( ∆ℎത 𝑠 )𝑝 − ෍ 𝑛𝑟 ( ∆ℎത 𝑠 )𝑟

𝑝 𝑟 𝑝 𝑟

Enthalpy of reaction
𝑄 − 𝑊 = ∆ℎ𝑅 + ෍ 𝑛𝑝 ( ∆ℎത 𝑠 )𝑝 − ෍ 𝑛𝑟 ( ∆ℎത 𝑠 )𝑟
𝑝 𝑟
First-law analysis of combustion system
Closed system (fixed mass):
𝑄 − 𝑊 = 𝐸𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐸𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 𝐸 is the energy, 𝑈 is the
internal energy
𝑄 − 𝑊 = 𝑈𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝑈𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 ---neglecting KE and PE

Similar to ℎത𝑓0 , we can define the internal energy of formation, say 𝑢ത𝑓0 : 𝑢ത = 𝑢ത𝑓0 + ∆𝑢ത 𝑠

But we note that 𝑢ത = ℎത − 𝑝𝑣ҧ

Thus, 𝑄 − 𝑊 = ෍ 𝑛𝑝 𝑢ത 𝑝 − ෍ 𝑛𝑟 𝑢ത 𝑟
𝑝 𝑟

can be written as 𝑄 − 𝑊 = ෍ 𝑛𝑝 ℎത − 𝑝𝑣ҧ 𝑝

− ෍ 𝑛𝑟
ത − 𝑝𝑣ҧ
ℎ 𝑟
𝑝 𝑟

𝑄 − 𝑊 = ෍ 𝑛𝑝 ℎത𝑓0 + ∆ℎത 𝑠 − 𝑝𝑣ҧ − ෍ 𝑛𝑟 ℎത𝑓0 + ∆ℎത 𝑠 − 𝑝𝑣ҧ

𝑝 𝑟
𝑝 𝑟
𝑄 − 𝑊 = ෍ 𝑛𝑝 ℎത𝑓0 + ∆ℎത 𝑠 − 𝑅𝑢 𝑇 − ෍ 𝑛𝑟 ℎത𝑓0 + ∆ℎത 𝑠 − 𝑅𝑢 𝑇
𝑝 𝑟
𝑝 𝑟
Example SSSF
Example Heat of Reaction
Example Heat of Reaction
Example Heat of Reaction
Example Heat of Reaction
Example Closed System
Combustion
(ME 301A)

Jishnu Bhattacharya
2022
 Adiabatic Flame Temperature (AFT)
AFT important from metallurgical considerations −𝑄
C
CO2
298 K, 1 atm
𝑊=0 600 K, 1 atm
O2

𝑄𝑖𝑛 = −𝑄𝑜𝑢𝑡 = 𝑚(ℎ

ሶ 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 )
𝑄𝑜𝑢𝑡
ℎ𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 = ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 −
𝑚ሶ

ℎ𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 highest when 𝑄𝑜𝑢𝑡 = 0 (adiabatic system)

Assuming the (generally) gaseous products to be ideal gases with ℎ = ℎ(𝑇)

𝑇𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 highest when 𝑄𝑜𝑢𝑡 = 0 Adiabatic Flame Temperature (AFT)

Adiabatic Flame Temperature (AFT): max temperature the combustion

products will reach when the combustion process is adiabatic.
 Adiabatic Flame Temperature (AFT)

AFT

constant-pressure AFT constant-volume AFT 𝑝

For a steady-flow combustion process For a fixed mass of reactants undergoing

at constant pressure, e.g. gas-turbine combustion at constant volume, e.g., in
combustors, furnaces etc. an ideal IC engine Otto cycle 𝑣

Find AFT using Find AFT using

ℎ𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 = ℎ𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 𝑢𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 = 𝑢𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

෍ 𝑛𝑝 ℎത𝑓0 + ∆ℎത 𝑠 = ෍ 𝑛𝑟 ℎത𝑓0 + ∆ℎത 𝑠 ෍ 𝑛𝑝 ℎത𝑓0 + ∆ℎത 𝑠 − 𝑝𝑣ҧ − ෍ 𝑛𝑟 ℎത𝑓0 + ∆ℎത 𝑠 − 𝑝𝑣ҧ
𝑝 𝑟 𝑝 𝑟
𝑝 𝑟 𝑝 𝑟

𝑝𝑓𝑖𝑛𝑎𝑙 𝑉 = fixed 𝑝𝑖𝑛𝑖𝑡𝑖𝑎𝑙

𝑝𝑓𝑖𝑛𝑎𝑙 𝑣ҧ = 𝑅𝑢 (𝑨𝑭𝑻) 𝑉 = fixed

𝑝𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑣ҧ = 𝑅𝑢 𝑇𝑖𝑛𝑖𝑡𝑖𝑎𝑙
Adiabatic Flame Temperature (AFT)

Graphical representation

Constant pressure AFT Constant volume AFT

Adiabatic Flame Temperature (AFT)

AFT example
Adiabatic Flame Temperature (AFT)
Adiabatic Flame Temperature (AFT)

If product composition is known,

a) 𝑐𝑝ҧ = 𝑓 𝑇
𝑇𝑎𝑑
∆ℎത 𝑠 = න 𝑐𝑝ҧ 𝑑𝑇 = 𝑔(𝑇𝑎𝑑 )
298𝐾

b) 𝑐𝑝,𝑎𝑣𝑒𝑟𝑎𝑔𝑒
ҧ

c) Trial and error

• Assume 𝑇𝑎𝑑

• ത 𝑎𝑑 ) for all species

Look up charts for ℎ(𝑇

• Check if 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 is satisfied.

• If not, choose a different 𝑇𝑎𝑑 .

Adiabatic Flame Temperature (AFT)

Points to note

If equations for sensible enthalpy changes are not available, determination of AFT requires an
iterative process in general.

• Assume 𝑇𝑎𝑑
ത 𝑎𝑑 ) for all species
• Look up charts for ℎ(𝑇
• Check if 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 is satisfied.

Maximum temperature attained in a combustion reaction is less than the AFT due to:
− Incomplete combustion
− Heat loss to the surroundings
− Dissociation of combustion products at high temperature

Maximum temperature attained can be adjusted by controlling the amount of excess air which
acts as a coolant.
Adiabatic Flame Temperature (AFT)

AFT depends on

− The state of the reactants

− Degree of completion of the reaction

− AFT depends on composition of the products (e.g. different 𝑐𝑝ҧ ),
1 “For a specified fuel
CO + O2  CO2
2 @specified state burned with
Reaction complete  only CO2 in product air @specified state,
Reaction incomplete  CO, O2 and CO2 in product AFT is max when complete
combustion occurs with Φ =
− Composition of products in turn depends on AFT (e.g. dissociation) 1.”
• So guess AFT  determine product composition  check AFT

− Amount of excess air

− System pressure – higher pressure tends to suppress dissociation
Adiabatic Flame Temperature (AFT)
Dependence of AFT on excess air (or 𝜱):
Composition  𝑄 released
𝑄 decreases, but 𝑐𝑝 of products decreases faster

Methane-air system: Φ~1.05

𝑇𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 600 K
~2350 K

~2200 K 𝑇𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 300 K

𝑇𝑎𝑑 (K)

≠ 600 − 300 K
Due to dissociation
Excess air Incomplete combustion
𝐴/𝐹 𝑠𝑡𝑜𝑖𝑐
Φ= Φ = 1.0
(𝐴/𝐹) Lean Φ Rich