01208331 Internal Combustion Engines

Chapter 3
Thermochemistry
of Fuel-Air Mixture

Asst.Prof.Dr. Tanet Aroonsrisopon

Department of Mechanical Engineering
Faculty of Engineering
Kasetsart University

Update: Jan 2016 Sec 451

 (Readings: Section 3.1)

Overview
 Combustion of the fuel-air mixture inside the engine cylinder is one of the
processes that controls engine power, efficiency, and emissions.
 This chapter reviews the thermochemistry of combustion:
 Composition of air and fuels
 Combustion stoichiometry
 1st-Law of Thermodynamics and combustion
 Chemical equilibrium
 Although actual combustion processes (e.g. in SI engines and CI engines)
are sophisticated and involve with various features, the study of
combustion theory help provide firm background and concepts necessary
for analysis of engine combustion processes.

01208331: Chapter 3 2
Overview (cont.)
Topics to be discussed include
Section in
Heywood
 Composition of air and fuels (3.2, 3.3)
 Combustion stoichiometry (3.4)
 The first law of thermodynamics for combustion (3.5)
 Chemical equilibrium: an analysis derived from second law (3.7)

01208331: Chapter 3 3
 (Readings: Sections 3.2, 3.3, Appendix B)

Composition of Air and Fuels

• Review of ideal gas model
• Composition of the air
• Classifications of hydrocarbon fuels

01208331: Chapter 3 4
 (3.2 Ideal Gas Model)

Ideal Gas Model

 In the analysis of engine processes, we usually treat the working

fluids as the ideal gases. (more details in Appendix B)

~
R ~
pV = mRT = m T = nR T (3.1)
MW
p = Absolute pressure [kPa]
V = Volume [m3]
m = Mass of gas [kg]
~
R = Gas constant [kJ/kg-K] = R MW
~
R = Universal gas constant = 8.314 kJ/kmole-K
MW = Molecular weight [kg/kmole]
n = Number of moles [kmole]
01208331: Chapter 3 5
 (Appendix B Ideal Gas Relationships)

Ideal Gas Mixture

 Consider a species i in the ideal gas mixture
Mole fraction of species i in the mixture:
n V p
~
xi = i = i = i
ntot Vtot p
where ∑i
~
xi = 1

Mass fraction of species i in the mixture:

m
xi = i
mtot
where ∑i
xi = 1

Rearrange, we have
~x MWi x MWmix
xi = i or ~
xi = i
MWmix MWi
 Molar mass (or Molecular weight) of the mixture
1
MWmix = = ∑~xi MWi
∑( xi MWi )

01208331: Chapter 3 6
 (3.3 Composition of Air and Fuels)

Air

 In the study of the real mixture, we treat: Air = Dry Air + Water

Erratum in the Heywood’s International edition.

 To facilitate the analysis, we assume that Air = O2 + atm N2 where

1 mole of Air = 0.2095 mole of O2 + 0.7905 mole of atm N2
01208331: Chapter 3 7
 Air (cont.)
Air = O2 + atm N2

 Molar mass to be used in calculations [Heywood 1988]:

28.962 − (0.2095 × 31.998)
MWO2 = 31.998 kg/kmole MWaN 2 =
1 − 0.2095
MWair = 28.962 kg/kmole = 28.16 kg/kmole

 Density of the dry air at the standard reference condition (1 atm, 25°C):
p = ρRT
p 101.325 kPa
ρ= ~ =
   8.314 kg/kmole − K  ⋅ 298.15 K
 R MW  ⋅ T  
 air   28. 962 kg/kmole 
∴ ρ = 1.184 kg/m 3

01208331: Chapter 3 8
Fuels

Definition:
“Fuels can be classified as substances that liberate
heat when reacted chemically with an oxidizer.”
 Most fuels currently used in combustion systems are derived
from non-renewable fossil sources.
 “Fossil fuels” - fuels formed by natural processes such as
anaerobic decomposition of buried dead organisms.
 Fuels most commonly used in IC engines are blends of many
different hydrocarbon compounds obtained by refining
petroleum or crude oil.

01208331: Chapter 3 9
 Hydrocarbons
Basic hydrocarbon families
Family name Other designations Molecular Carbon-Carbon Primary
Formula Bonding Molecular Structure

Alkanes Paraffins CnH2n+2 Single bonds only Straight or branched

open chains

Alkenes Olefins CnH2n One double bond, Straight or branched

remainder single open chains

Alkynes Acetylenes CnH2n-2 One triple bond, Straight or branched

remainder single open chains

Cyclanes Cycloalkanes, CnH2n or (CH2)n Single bongs only Closed rings

Cycloparaffins,
Naphthenes
Aromatics Benzene family CnH2n-6 Resonance Closed rings
hybrid bonds
(Aromatic bonds)
Source: Turns, S.R., An Introduction to Combustion: Concepts and Applications, 3rd-Int’l Edition, 2012.
01208331: Chapter 3 10
Selected Hydrocarbon Families

Examples of hydrocarbon species in each family

1. Alkanes (Paraffins): all single bonds with a formula CnH2n+2
such as Methane (CH4), Propane (C3H8), n-Heptane (C7H16), n-Octane (C8H18),
iso-Octane (C8H18), n-Dodecane (C12H26).

H H H

H C H Methane (CH4) H C H H C H

H H H
H
H C C C C C H
H H H H H H H H
H H H H
H C C C C C C C C H
H C H

H H H H H H H H H

n-Octane (C8H18) iso-Octane (C8H18)†

† IUPAC name = 2,2,4-Trimethylpentane

01208331: Chapter 3 11
 Selected Hydrocarbon Families (cont.)

2. Alkenes (Olefins): 1 double bond 3. Alkynes: 1 triple bond with a

with a formula CnH2n such as formula CnH2n-2 such as
Ethene (C2H4), Propene (C3H6). Acetylene (C2H2).

H H

C C Ethene (C2H4) H C C H Acetylene (C2H2)

H H

H H
H

C C C H Propene (C3H6)
H
H

01208331: Chapter 3 12
 Selected Hydrocarbon Families (cont.)

4. Aromatics: at least 1 benzene ring. 5. Cyclanes (Cycloparaffins or

A formula for the structure with Napthenes): Single-bonded ring
1 benzene ring is CnH2n-6. structure with a formula CnH2n
H
H H
H C H
C C
Benzene H C C H Cyclopropane
C C (C6H6) C (C3H6)
H C H
H H
H

H H H H
H
H C C
C C H C C H
H Toluene Cyclobutane
C C (C6H5CH3 or C7H8) H C C H (C4H8)
H C H
H H
H

01208331: Chapter 3 13
Alcohols

 In these organic compounds, one hydroxyl (–OH) group is

substituted for one hydrogen atom in an alkane molecule.
 Formula: CnH2n+1OH

H C OH Methanol
(CH3OH)
H

H H

H C C OH Ethanol
(C2H5OH)
H H

01208331: Chapter 3 14
Conventional Fuels
Conventional fuels used IC engines, composed of various types of
hydrocarbons, are from crude oil refinery and petrochemical processes:
 Gasoline (or petrol) Typical gasoline composition [Stone 1999]:
Alkanes 20–30%
 Diesel fuels Alkenes 30–45%
 LPG Aromatics 30–45%
 Natural gas Cycloalkanes 5%

Composition of commercial gasoline fuels

Composition of a commercial
diesel fuel

01208331: Chapter 3 15
 (Readings: Section 3.4)

Combustion Stoichiometry
• Air-fuel mixture
• Combustion equation

01208331: Chapter 3 16
 (3.4 Combustion Stoichiometry)

Combustion Stoichiometry
“Stoichiometric combustion” means fuel and oxidizer (air or
pure O2) combust in exact proportions.

Ex 3.1 Write the overall chemical equation for the complete

combustion of 1 mole of propane (C3H8) and oxygen (O2):
C3H8 + a O2 = b CO2 + c H2O
Carbon balance: 3=b ∴ b=3
Hydrogen balance: 8 = 2c ∴ c=4
Oxygen balance: 2a = 2b + c ∴ a=5
Thus, C3H8 + 5O2 = 3CO2 + 4H2O

01208331: Chapter 3 17
Overall Complete Combustion Equation
A hydrocarbon fuel with a formula of CaHb reacts with
stoichiometric air: Fuel + Oxidizer → Products
 b b  b
C a H b +  a + (O 2 + 3.773N 2 ) → aC O 2 + H 2 O + 3.773  a +  N 2
 4 2  4
b
Define y= “Fuel Molar H/C Ratio” (3.5)
a
 y y  y
CH y + 1 + (O 2 + 3.773N 2 ) → C O 2 + H 2 O + 3.773 1 +  N 2
 4 2  4
The stoichiometric A/F ratio† is defined as
 A F  (1 + y 4 )(31.999 + 3.773 × 28.16 )
−1

  =  =
 F s  A s 12.011 + 1.008 y
34.56(4 + y )
= (3.6)
12.011 + 1.008 y
01208331: Chapter 3
† Also called “Theoretical A/F ratio” 18
Fig. 3-3 (Stoichiometric A/F Ratio)
This plot is valid for hydrocarbons with a formula CaHb only!

According to Eq.(3.6), we can

determine (A/F)s from the known
H/C ratio (parameter y).
For example,
CH4 has the H/C ratio of 4.
From the plot, (A/F)s ≈ 17.2
With Eq.(3.6), (A/F)s of CH4 = 17.234

01208331: Chapter 3 19
Generalized Combustion Equation

For any fuel composed of C, H, O, N, we can write a

general equation for stoichiometric combustion as
 b c
C a H b O c N d +  a + − (O 2 + 3.773N 2 )
 4 2
b d  b c 
→ aCO 2 + H 2 O +  + 3.773 a + −  N 2
2 2  4 2 
Where the stoichiometric A/F ratio:
 A (a + b 4 − c 2 )(31.999 + 3.773 × 28.16 )
  =
 F  s 12.011a + 1.008b + 15.999c + 14.006d

01208331: Chapter 3 20
A/F Mixture: Exhaust Composition
A change in the A/F ratio changes the exhaust composition. In a simplified
analysis at the moment, we consider the product mixture as follows:
 Stoichiometric mixture: neither O2 nor incomplete combustion products
(e.g. CO, free C, HC and etc.) exist in the exhaust gases.
 Fuel-lean mixture: more air than (A/F)s. The excess air results in O2
remained in the exhaust gases.
 Fuel-rich mixture: less air than (A/F)s. As a result, the exhaust gases contain
some incomplete combustion products (e.g. free C, CO, HC and etc.).

To quantitatively compare between the actual (A/F) and the (A/F)s, we define

φ=
(F / A)act = ( A / F )s “Fuel-air equivalence ratio”
(F / A)s ( A / F )act
λ=
( A / F )act = 1 “Relative A/F ratio”
( A / F )s φ
01208331: Chapter 3 21
A/F Mixture: Summary
Summary
1) Lean mixture: φ < 1, λ > 1
2) Stoichiometric mixture: φ = 1, λ = 1
3) Rich mixture: φ > 1, λ < 1

Values of (A/F)s and (F/A)s for selected fuels (from Table D.4, page 915)
Molecular Weight
Fuels Chemical Formula (A/F)s (F/A)s
[g/mole]
Methane CH4 16.04 17.23 0.0580
Propane C3H8 44.10 15.67 0.0638
Isooctane C8H18 114.23 15.13 0.0661
Ethanol C2H6O 46.07 9.00 0.111
Gasoline CnH1.87n ~110 14.6 0.0685
Light diesels CnH1.8n ~170 14.5 0.0690

01208331: Chapter 3 22
 Table D.4 (Heywood p. 915)

01208331: Chapter 3 23
 Example 3.2
[Heywood, Example 3.1]
Ex 3.2 A hydrocarbon fuel of composition 84.1 percent by mass C and 15.9 percent
by mass H has a molecular weight of 114.15. Determine the number of
moles of air required for stoichiometric combustion and the number of
moles of products produced per mole of fuel. Calculate (A/F)s, (F/A)s, and
the molecular weights of the reactants and the products.
1) The fuel is a hydrocarbon composed of C and H: Ca Hb

Molar mass: a ⋅ MWC + b ⋅ MWH = MWfuel

a ⋅ (12.011) + b ⋅ (1.008) = 114.15 (1)

b mH MWH 15.9 1.008

H/C molar ratio: = = = 2.25 (2)
a mC MWC 84.1 12.011

From Eq.(1) and (2), we rearrange to solve for a and b, which gives us a
chemical formula of this fuel as C8H18.
01208331: Chapter 3 24
Example 3.2 (cont.)
2) Combustion stoichiometry
C8H18 + 12.5(O2 + 3.773N2) = 8CO2 + 9H2O + 47.16N2

fuel air products

Per mole of fuel:

1 + 12.5(1 + 3.773) ≠ 8 + 9 + 47.16
1 + 59.66 ≠ 64.16
Thus, nR = 60.66 moles and nP = 64.16 moles Ans

Per mass of fuel:

114.15 + 59.66(28.96) = 8(44.01) + 9(18.02) + 47.16(28.16)
114.15 + 1727.8 = 1842.3
1 + 15.14 = 16.14
Thus, (A/F)s = 15.14 and (F/A)s = 1/15.14 = 0.0661 Ans
01208331: Chapter 3 25
Example 3.2 (cont.)
3) Molecular weights of reactants and products
The molar mass of an ideal gas mixture can be determined from
MWmix = ∑ ~
xi MWi where ~
xi = mole fraction of species i
i

Reactant mixture:

MWR =
1
∑ ni MWi =
1
[(1)(114.15) + (59.66)(28.96)]
nR i 60.66
Thus, MWR = 30.36 g mole Ans

Product mixture:

MWP =
1
∑ ni MWi =
1
[(8)(44.01) + (9)(18.02) + (47.16)(28.16)]
nP i 64.16
Thus, MWP = 28.71 g mole Ans

01208331: Chapter 3 26
 Excess Air
Sometimes the excess air is used, for example “25% excess air”. This is equal
to 1.25 times of the air used in the stoichiometric mixture.
Now, consider C8 H18 as the fuel. We can write the combustion equation for
25% excess air as
C8 H18 + 1.25(12.5)(O 2 + 3.773N 2 ) = 8 C O 2 + 9 H 2 O + 3.13 O 2 + 58.95 N 2

Or in a general expression, we can write

b
(a + )
C aH b + 4 (O + 3.773N ) = c C O + d H O + e O + f N + ...
φ
2 2 2 2 2 2

1 1 4
where λ = 1 .25 = φ = = = 0.8
φ 1.25 5
Note: 25% Excess air = 125% Theoretical air

01208331: Chapter 3 27
 (Readings: Section 3.5)

The First Law of Thermodynamics

and Combustion
• Review of 1st-Law
• Enthalpy of Formation
• Heating Values
• Adiabatic Combustion Temperatures
• Combustion Efficiency

01208331: Chapter 3 28
 (3.5 The First Law of Thermodynamics and Combustion)

1st-Law for Combustion

Consider a system of mass m

QR-P

System System System

WR-P
Initial state Combustion process Final state
Reactants Heat and work transfer Products
TR , pR , VR , U R interactions TP , pP , VP , U P

We can write the energy balance equation (1st-Law eqn.):

QR − P − WR − P = U P − U R (3.13)

01208331: Chapter 3 29
 Section 3.5.1

1st-Law for Combustion (cont.)

Const. volume
Consider two different combustion processes
Const. pressure
1) Constant-volume process (∆V = 0)
Given Initial temperature = Final temperature = T ′
0
QR − P − WR − P = U P′ − U R′ = (∆U )V ,T ′ (3.14)

The values of QR − P and (∆U )V ,T ′ are negative as the combustion is

an “exothermic” process.
The magnitude of the above parameter, which is − (∆U )V ,T ′ , is
called the heat of reaction at constant volume at temperature T ′.

Note: U R′ > U P′ internal energy of the system decreases.

01208331: Chapter 3 30
1st-Law for Combustion (cont.)

2) Constant-pressure process (∆p = 0)

Given Initial temperature = Final temperature = T ′
QR − P − p(VP′ − VR′ ) = U P′ − U R′
QR − P = H P′ − H R′ = (∆H ) p ,T ′ (3.16)

The values of QR − P and (∆H ) p ,T ′ are negative as the combustion is

an “exothermic” process.
The magnitude of the above parameter, which is − (∆H ) p ,T ′ , is
called the heat of reaction at constant pressure at temperature T ′.

Note: H R′ > H P′ enthalpy of the system decreases.

01208331: Chapter 3 31
1st-Law for Combustion (cont.)

Heat of reaction at T’

Heat of reaction at To

01208331: Chapter 3 32
 1st-Law for Combustion (cont.)
The difference between the two heats of reaction at T ′ is
(∆H ) p ,T ′ − (∆U )V ,T ′ = p(VP − VR ) (3.17)

For reactant species and product species being ideal gases, we have
~ ~
pVR = nR′ R T ′ and pVP = nP′ R T ′
Sub. in (3.17), (∆H ) p ,T ′ − (∆U )V ,T ′ = R (nP′ − nR′ )T ′
~
(3.18)
Note: any inert gases do not contribute to (nP′ − nR′ ).

In the combustion of hydrocarbon fuels, the product mixture composes

of H2O, which can be either in the gaseous and liquid phases. (see Fig.3-6a)
(∆U )V ,T ′,H O liq − (∆U )V ,T ′,H O vap
2 2
= mH 2Ou ′fg H 2O (3.19)

(∆H ) p ,T ′,H O liq − (∆H ) p ,T ′,H O vap

2 2
= mH 2O h′fg H 2O (3.20)
Note: u ′fg H 2O = internal energy of vaporization of water, h′fg H 2O = enthalpy of vaporization of water
01208331: Chapter 3 33
 H2O in products Fuel as liquid or vapor

01208331: Chapter 3 34
Standardized Enthalpy
 Enthalpy is a thermodynamic potential that is a measure of total
energy of a thermodynamic system.
 The change of enthalpy can be linked with energy associated with
the combustion processes.
 We define an enthalpy of species i in terms of the standardized
enthalpy:
~ ~o ~
hi (T ) = h f ,i (Tref ) + ∆hs ,i (T )
Standardized enthalpy Enthalpy of formation Sensible enthalpy change
at temperature T at standard reference in going from
state (Tref, po) temperature Tref to T

Associated with Associated only with

chemical bonds temperature

01208331: Chapter 3 35
 Section 3.5.2

Enthalpies of Formation
~
Enthalpy of formation ( h fo ) of a
chemical compound is defined as:
“The enthalpy increase associated with the
reaction of forming one mole of the given
compound from its elements, with each
substance in its thermodynamic standard
state at the given temperature.”

See Table 3.2

01208331: Chapter 3 36
Standard Reference State
 Define the standard reference state (Tref , p o )
Tref = 25°C + 273.15 = 298.15 K
p o = 1 atm = 1.01325 bar = 101.325 kPa = 1.01325 ×105 Pa
 At the standard reference state, the enthalpies of formation are zero for
the elements in their naturally occurring state. These include O2, N2, H2,
and C (graphite).
 For compounds (e.g. reactants and products), the enthalpies at standard
reference state are given by
~o ~o
H Ro = ∑ i f ,i
n h
reactants
and H = ∑ ni h f ,i
o
P (3.21)
products

 The enthalpy increase, as reactants change to products, is given by

(∆H ) p ,To = ( H Po − H Ro )
and we can use Eq. (3.17) to determine (∆U )V ,To.
01208331: Chapter 3 37
 Example 3.3
[Heywood, Example 3.2]
Ex 3.3 Calculate the enthalpy of the products and reactants, and the enthalpy
increase and internal energy increase of the reaction, of a stoichiometric
mixture of methane and oxygen at 298.15 K
The stoichiometric reaction is CH 4 + 2O 2 = C O 2 + 2 H 2 O
~o ~o 0
Reactants, H = (1)(h f ,CH 4 ) + (2)(h f ,O 2 ) = −74.87 MJ kmol CH 4
o
R Ans

Products, consider the two cases when H2O is gaseous and liquid
~ ~
For H2O gas: H Po = (1)(h fo,CO 2 ) + (2)(h fo,H 2O gas )
= −393.52 + 2(−241.83) = −877.18 MJ kmol CH 4 Ans
~ ~
For H2O liquid: H Po = (1)(h fo,CO 2 ) + (2)(h fo,H 2O liquid )
= −393.52 + 2(−285.84) = −965.20 MJ kmol CH 4 Ans
01208331: Chapter 3 38
 Example 3.3 (cont.)
Enthalpy increase of the reaction: for H2O gas
(∆H )op = H Po − H Ro
= −877.18 − (−74.87) = −802.31 MJ kmol CH 4 Ans
Enthalpy increase of the reaction: for H2O liquid
(∆H )op = H Po − H Ro
= −965.20 − (−74.87) = −890.33 MJ kmol CH 4 Ans
Find (∆U )V from Eq. (3.18),
o

For H2O gas: nP = nR = 3 kmol

Thus, (∆U )Vo = (∆H )op = −802.3 MJ kmol CH 4 Ans

For H2O liquid: nP − nR = 1 − 3 = −2 kmol

Thus, (∆U )Vo = (∆H )op − R~(nP − nR )T0 = −890.33 − (8.3143 ×10−3 )(1 − 3)(298.15)
= −885.4 MJ kmol CH 4 Ans
01208331: Chapter 3 39
Observations from Example 3.3

 Changes in the internal energy and the enthalpy per unit mass of
fuel can be determined if we know a composition of the fuel.
 For this example, the fuel is methane. We know the molar mass
of CH4: MWCH 4 = 16.04 kg kmol

 The presence of N2 in the mixture or O2 in the excess air does not

change any of these calculations.
(∆H )op stoich
= (∆H ) p lean
o

(∆U )Vo stoich

= (∆U )V lean
o

 Use of excess air will only change the fractions of O2 and N2 in

the mixture.

01208331: Chapter 3 40
 Section 3.5.3

Heating Values

 The heating value (also called calorific value) of fuel is the amount of energy
released associated with the complete combustion of unit mass of fuel.
 There are two types of heating values, defined by either the magnitude of
heat of reaction at constant pressure or at constant volume at a standard
temperature (25°C):
QHVp = −(∆H ) p ,T0 (3.22a)

QHVV = −(∆U )V ,T0 (3.22b)

SI Unit: J/kg or kJ/kg or MJ/kg (or in EE unit, BTU/lbm)
 For fuels containing hydrogen, H2O will be present in the products which
affects the heating values
For liquid H2O: higher heating value (or gross heating value)
For vapor H2O: lower heating value (or net heating value)

01208331: Chapter 3 41
Heating Values (cont.)
For a constant pressure process, the higher and lower heating values are
related by
 mH 2O 
QHHVp = QLHVp + h fg ,H O (3.23)
 m  2
 f 
For H2O at 25°C, h fg ,H 2O = 2442 kJ kg

Note that it is necessary to know the composition of the fuels in order to

calculate the heating values by using data of enthalpies of formation.
 For fuels with unknown composition, we can obtain the heating values
from measurement by using:
 Continuous-flow atmosphere pressure calorimeter for gaseous fuels

 Bomb calorimeter for liquid fuels and solid fuels

01208331: Chapter 3 42
 Gas Calorimeter
For gaseous fuels

Wet-test meter

Calorimeter

01208331: Chapter 3 43
Oxygen Bomb Calorimeter
For liquid and solid fuels

Bomb
01208331: Chapter 3 44
 Example 3.4
Ex 3.4 Given the standard enthalpy of formation for propane of -103.85 MJ/kg (see
Table 3.2). Calculate the lower and higher heating values.
Write the combustion equation
C3 H 8 + 5(O 2 + 3.773N 2 ) = 3C O 2 + 4H 2 O + 18.865 N 2
~o ~o 0 ~o 0
Reactants, H R = (1)(h f ,C3H8 ) + (5)(h f ,O 2 + 3.773 h f , N 2 )
o

= −103.85 MJ kmol C3 H 8
~o
Products with vapor H2O (use h f from Table 3.2),
~o ~o ~o 0
H P = (3)(h f ,CO 2 ) + (4)(h f ,H 2O gas ) + (18.865)(h f , N 2 )
o

= (3)(−393.52) + (4)(−241.83) = −2147.88 MJ kmol C3 H 8

H Ro − H Po (−103.85) − (−2147.88)
Thus, QLHV = = = 46.35 MJ kg Ans
MWC3H8 44.097
01208331: Chapter 3 45
 Example 3.4 (cont.)
~
Products with liquid H2O (use h fo from Table 3.2),
~o ~o ~o 0
H = (3)(h f ,CO 2 ) + (4)(h f ,H 2O liq ) + (18.865)(h f , N 2 )
o
P

= (3)(−393.52) + (4)(−285.84) = −2323.92 MJ kmol C3 H 8

H Ro − H Po (−103.85) − (−2323.92)
Thus, QHHV = = = 50.35 MJ kg Ans
MWC3H8 44.097

Note:
 To calculate the heating values, we consider the amount of oxidizer to obtain
complete combustion.
 For your own exercise, determine the heat of vaporization of H2O from data in
this example.

01208331: Chapter 3 46
 Section 3.5.4

Adiabatic Combustion Processes

System System

Initial state Final state WR-P

Reactants Products
TR , pR , VR , U R TP , pP , VP , U P

 Adiabatic = no heat transfer

 In engine analysis, we now use the relationships developed in the
previous section, for the two special combustion processes:
1) Constant-pressure combustion
2) Constant-volume combustion
 Oxidizer can be the air or pure O2.

01208331: Chapter 3 47
Adiabatic Constant-pressure Combustion
From 1st-Law,
0
1 Q2 − 1W2 = U 2 − U1
p (V2 − V1 ) = U 2 − U1 TR TP

H R (TR , p ) = H P (TP , p )
hR = hP

where
 ~ o TR 
~
[ ~
( ~
)]
H R (TR , p ) ≡ H R (TR ) = ∑ ni h fo,i + h (TR ) − h (T0 ) i = ∑ ni h f ,i + ∫ c p ,i dT 
~
R R  T0 
 ~ o TP 
~o
[ ~
( ~
)]
H P (TP , p ) ≡ H P (TP ) = ∑ ni h f ,i + h (TP ) − h (T0 ) i = ∑ ni h f ,i + ∫ c p ,i dT 
~
P P  T0 
01208331: Chapter 3 48
Adiabatic Constant-volume Combustion
0 0
1 Q2 − 1W2 = U 2 − U1
U R (TR , pR ) = U P (TP , pP )
H R − H P − V ( pR − pP ) = 0
Consider the ideal-gas mixture
~ ~ ~ ~
pRV = ∑ ni R TR = nR R TR and pPV = ∑ ni R TP = nP R TP
R P
~
Thus, H R − H P − R (nRTR − nPTP ) = 0
The expression in the per-mass-of-mixture can be written as
~ TR TP 
hR − hP − R  −  = 0
 MWR MWP 

01208331: Chapter 3 49
Specific Heat (Cp) for Ideal Gasses
 For most ideal gases,
c p ≡ c p (T )
 For ease of calculation,
we can use Tavg and use
the approximation for the
integral term:
T

∫ c dT ≈ c
T0
p p , avg (T − T0 )

@Tavg (between T0 and T)

 Adiabatic const-pressure
combustion temperatures
of a stoich. A/F mixture
for most hydrocarbon
fuels are in a range of
2100 K to 2300 K.

01208331: Chapter 3 50
 Specific Heat (Cp)
Source:
Sonntag, R.E., and Borgnakke, C., Fundamental
of Classical Thermodynamics, John Wiley & Sons,
7th Edition, 2009.

Some useful formulas:

c~p ,i ~
R
c p ,i = Ri =
MWi MWi
~
c p ,i − cv ,i = Ri , c~p ,i − c~v ,i = R

c p ,i c~p ,i
γ= =~
cv ,i c v ,i

where c p ,mix = ∑ xi c p ,i
c~p ,mix = ∑ ~
xi c~p ,i
01208331: Chapter 3 51
Oxidizer Effect: O2 Vs. Air

O2 N2

01208331: Chapter 3 52
 (Readings: Section 3.7)

Chemical Equilibrium:
An Analysis Derived from Second Law
• Review of Entropy
• Chemical Reactions
• Chemical Equilibrium

01208331: Chapter 3 53
 Section 3.6.1

Review of Entropy
 Entropy of ideal gas species i:
T
p dT p
si = si (T , pref ) − Ri ln i = si (Tref , pref ) + ∫ c p ,i − Ri ln i
pref Tref
T pref

sTo = Standard entropy at pref (which is a function of T )

where pref = 1 atm = 101.325 kPa , Tref = 25°C = 298.15 K

 App. B presents how to calculate the entropy of ideal gas mixture
(known composition). Calculation of H and U of the reactants and
products are also presented.
 Standard entropy at a certain temperature ( sTo ) of selected species
are given in the JANAF tables (At 0 K, sTo = 0)

01208331: Chapter 3 54
 (3.7 Chemically Reacting Gas Mixtures)

Chemically Reacting Gas Mixtures

The working fluids in engines are mixtures of gases. Depending on the
problem under consideration and the portion of the engine cycle, the
chemical reactions associated with the working fluids can be classified
as follows:
1) Chemical reactions being so slow that they have a negligible effect
on the mixture composition (i.e. “frozen” composition).
2) Chemical reactions being so rapid that the mixture state changes
and the composition remains in chemical equilibrium (i.e.
“equilibrium” composition).
3) At least one of the chemical reactions that determines the mixture
composition changes with time and is not rapid enough to reach
chemical equilibrium.

01208331: Chapter 3 55
 Section 3.7.1

Chemical Equilibrium

So far, we treat the combustion reaction by assuming a complete

conversion from reactants to products. The analysis is based only on
the 1st-Law of thermodynamics.

Fuel + Oxidizer → Products

 In practice, at the end of combustion process, there are some

reactant species remaining in the product mixture. This is because
some of the chemical reactions do not go to completion, but reach
chemical equilibrium.
 Chemical equilibrium calculations consider both 1st-Law and 2nd-
Law of Thermodynamics.

01208331: Chapter 3 56
Species Dissociation
1
Consider the combustion reaction: CO + O 2 
→ CO 2 (R1)
2
 If the final temperature is high enough, CO2 will dissociate.
 Assuming the final products to consist only of CO2, CO, and O2, with all
being in chemical equilibrium, the rate of CO2 dissociation (i.e. forming CO
and O2) will be equal to the rate of recombination of CO and O2 (i.e.
forming CO2).
 Let the degree of CO2 dissociation be α , using (R1) we can also write
1 α
CO + O 2 → (1 − α ) ⋅ CO 2 + α ⋅ CO +
 ⋅ O2 (R2)
2 2
Initial state Final state (equilibrium)

Note: the fraction of CO2 remained at equilibrium is (1 − α ) .

01208331: Chapter 3 57
Illustration of Chemical Equilibrium for a Fixed-mass Isolated System

01208331: Chapter 3 58
Observation
 For this system, the maximum entropy occurs near (1 − α ) ≈ 0.5. This can
be described by the 2nd-Law of thermodynamics.

01208331: Chapter 3 59
Reaction in Equilibrium

 For any reaction being at chemical equilibrium

aA + bB cC + dD

 Define the equilibrium constant based on partial pressure

νi
 pi 
Kp = ∏i  p  (Eq.11)
 o
c d
 pC  p 
   D 
= 
po   po 
or Kp a b
 pA   pB 
  
 
 po   po 

01208331: Chapter 3 60
Reaction in Equilibrium (cont.)

 Mole fraction of species i in the ideal gas mixture

n V p ~
~
xi = i = i = i where piV = ni R T
ntot V p

 Sub in Eq.(11),
c d
 xC p   xD p 
~ ~
    c + d − a −b
x x  p
~ c~d
=  o  a o  b = ~Ca ~Db  
p p
Kp
~ xA p   ~ xB p  x A x B  po 
   
 po   po 
∑ν i
 p
∏ i
~ νi
or =   (Eq.12)
i
Kp x
 po  i

01208331: Chapter 3 61
Reaction in Equilibrium (cont.)

 To facilitate the calculation, the equilibrium constants are provided

in a form of the followings
(1) K p for a species as a function of temperature
(2) K p for a reaction as a function of temperature
Both are related by
log10 (K p )reaction = ∑ν i log10 (K p )i (Eq.13)
i

 Data of K p presented in JANAF tables are of species (see Ex 3.5).

01208331: Chapter 3 62
Reaction in Equilibrium (cont.)

 Besides the equilibrium constant based on partial pressure ( K p ),

we also have the equilibrium constant based on concentration (K c )

Kc = (
∏ i
C )ν i
(Eq.14)
i
ni
where the concentration of species i is Ci =
V
 K p and K c are related by
~ ∑ν i
K p = K c RT i ( ) (Eq.15)

With po = 1 atm (always) and if the number of reactant moles

equals the number of product moles (i.e. ∑ν i = 0 ), we yield K p = K c
i

01208331: Chapter 3 63
 Example 3.5
[Heywood, Example 3.4]
Ex 3.5 A stoichiometric mixture of CO and O2 in a closed vessel, initially at 1 atm, 300
K, is exploded. Calculate the composition of the products of combustion at
2500 K and the gas pressure.

01208331: Chapter 3 Assoc. Prof. Sompong Pichetpinyo 64

01208331: Chapter 3 Assoc. Prof. Sompong Pichetpinyo 65
01208331: Chapter 3 Assoc. Prof. Sompong Pichetpinyo 66
01208331: Chapter 3 Assoc. Prof. Sompong Pichetpinyo 67
Example 3.5 (cont.)

01208331: Chapter 3 Assoc. Prof. Sompong Pichetpinyo 68

Example 3.5 (cont.)

01208331: Chapter 3 Assoc. Prof. Sompong Pichetpinyo 69

 Example 3.6
[Heywood, Example 3.5]
Ex 3.6 In fuel-rich combustion product mixtures, equilibrium between the species
CO2, H2O, CO, and H2 is often assumed to determine the burned gas
composition. For φ = 1.2, for C8H18-air combustion products, determine the
mole fraction of the product species at 1700 K.

01208331: Chapter 3 Assoc. Prof. Sompong Pichetpinyo 70

Example 3.6 (cont.)

01208331: Chapter 3 Assoc. Prof. Sompong Pichetpinyo 71

Example 3.6 (cont.)

01208331: Chapter 3 Assoc. Prof. Sompong Pichetpinyo 72

Fig. 3-10: Mole Fractions of Equilibrium Products

Note: see changes in species such as NO and CO

01208331: Chapter 3 73
Adiabatic Combustion Temperatures

01208331: Chapter 3 74
Fig. 11-2 (pp. 571)

01208331: Chapter 3 75
Problems
1. [Heywood 3.1] Isooctane is supplied to a four-cylinder spark-ignition engine at 2 g/s. Calculate the air
flow rate for stoichiometric combustion. If the engine is operating at 1500 rev/min, estimate the mass
of fuel and air entering each cylinder per cycle. The engine displaced volume is 2.4 liters. What is the
volumetric efficiency?
2. [Heywood 3.2] Calculate the exhaust gas composition of a butane-fueled spark-ignition engine
operating with equivalence ratio of 0.9. Assume the fuel is fully burned within the cylinder.
Butane is C4H10.
3. The measured dry exhaust gas composition of a research engine is given as follows:
CO2 = 12.0% CO = 3.6% O2 = 1.2% H2 = 1.0% C3H6 = 0.2%
The molar mass of the fuel is 100 kg/kmole. Assume that the fuel is a typical hydrocarbon, CaHb,
determine
(3.1) Molar H/C molar of the fuel (y = b/a)
(3.2) Chemical formula of the fuel molecule
(3.3) Stoichiometric air-fuel ratio
(3.4) Equivalence ratio
(3.5) Based on the given information above, what kind of engine would it be (e.g. SI, CI, or not
enough information to evaluate)? Explain.

01208331: Chapter 3 76
Problems (cont.)
4. Liquid petroleum gas (LPG) is used to fuel spark-ignition engines. Let the fuel consist of 40% by volume
of propane (C3H8) and 60% by volume of n-butane (C4H10). Determine
(4.1) Overall combustion reaction for stoichiometric combustion of 1 kmole of LPG
(4.2) Stoichiometric air-fuel ratio
(4.3) Lower heating value of LPG (in MJ/kg)
5. Estimate the adiabatic combustion temperatures for the stoichiometric propane-air mixture under the
following ideal combustion processes:
(a) Adiabatic constant-pressure process (b) Adiabatic constant-volume process
Assume that the initial condition of the reactant mixture is at 1 atm, 25°C and the final products consist
only of CO2, H2O, and N2.
6. Based on Problem #5, what would be the adiabatic combustion temperature under constant pressure if
the oxidizer is pure oxygen, instead of the air.
7. Consider the reaction H 2 + (1 2)O 2 ⇔ H 2 O in a closed vessel which is initially at 3 bar, 300 K. After
ignition, the system reaches a uniform state and the final temperature is 3000 K.
Given: at 3000 K, log10 (K p )H 2 = 0 , log10 (K p )O 2 = 0, and log10 (K p )H O = 1.346 . Determine
2

(7.1) Degree of dissociation of H2O at the final state.

(7.2) Mole fraction and mass fraction of each species at the final state.
(7.3) Adiabatic combustion temperature and why is it not 3000 K?

01208331: Chapter 3 77