MEC551 WANWM

Chapter 5
PROPERTIES OF MIXTURES AND COMBUSTION
In this chapter, study of combustion processes is the main objective. Combustion analysis requires
balancing of chemical equations, where the substances involved are normally in the form of
mixtures. This chapter starts with the fundamental method for measuring strengths and quantities of
a mixture. Then, the theories of combustion are introduced, covering from solving basic combustion
equations, determination of the amount of heat released and estimating the flame temperature of
the combustion process. By the end, students should be able to integrate the theories of
combustion into engineering analysis of heat-producing devices such as boilers and combustion
chambers.

1.0 Properties of Mixtures

In combustion processes, it normally involves mixtures of components, rather than singlecomponent systems. Mixtures are defined as substances that has 2 or more components that forms
it, where the easiest example would be the substance we refer to as air. Air composes primarily of
nitrogen, oxygen, carbon dioxide and other inert gases. All these components have their own
properties in terms of mole and mass fractions, molecular weight, gas constant and other
thermodynamic properties. The overall property of air would be influenced by each individual
component property.
1.1 Mole and mass fraction
Mole fraction, y, is described as
N number of moles
i - individual component
m - mixture

N
yi i
Nm

Mass fraction, mf, is defined as

mf i

m mass
i - individual component
m - mixture

mi
mm

The total number of moles and mass of the mixture is the summation of each individual component.
The molecular weight of a mixture is given by,

N M
i

yi M i

The mixture gas constant would then be,

R

R
M

where R is the universal gas constant, 8.314 kJ/kmol.K

1.2 Ideal-Gas law for Mixtures

The Dalton model is used to determine the total pressure of a mixture,. The total pressure is
basically the sum of the component pressures, termed as partial pressures. For the Dalton model

Gas A
V, T
PA

Gas B
V, T
PB

Mixture A+B
V, T
Pm = P A + P B

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Amagats law is referred to as the law of additive volume, used to measure the volume of a mixture
at constant pressure and temperature.

Gas A
P, T

VA

Gas B
P, T

Mixture A+B
P, T

VB

Vm = V A + V B

For any component of a mixture of ideal gases, the ideal-gas law is

Pi

N i RT
V

For a mixture as a whole,

therefore,

N RT
V

yi

Pi
V
N
i i
Pm Vm N m

so that

Pi
N RT / V
N
i
i
P
N
N RT / V

1.3 Properties of a Mixture of Ideal Gases

The extensive properties of a mixture, such as h, u, s, and c p can be found simply by adding the
contributions of each component.
Example, for specific enthalpy h,

mf h
i

(kJ/kg)

and

y h
i

(kJ/kmol)

2.0 Combustion
2.1 Theory of Combustion
Definition : A chemical reaction during which a fuel is oxidized and a large quantity of energy is
released. Combustion is a microscopic process to convert stored chemical energy into useful heat
energy.
There are 3 main elements for combustion to occur :
Fuel

Oxygen
(air)
Heat

Fuels
1. Any material that releases energy when oxidized.
2. consist primarily of hydrogen and carbon (hydrocarbon fuel, C nHm)
3. exists in al phases; solids, liquid and gas.

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4. Common hydrocarbon fuels : gasoline (C 8H18 octane), diesel (C 12H26 dodecane), methane
(CH4), LPG etc.
Oxygen (air)
1. Air is free and readily available, so concentrated O 2 used only in specialized conditions.
2. Dry air consists of 20.9% O2, 78.1% N2, 0.9% argon and the rest are other gases.
3. For each mole of oxygen entering a combustion process, it is accompanied by 0.79/0.21 =
3.76 mol of N2.
4. At ordinary combustion temperature (less than 1400 oC), nitrogen does not react (inert gas).
At temperatures higher than 1400oC, fraction of N2 reacts with oxygen to form oxides of
nitrogen (NOx).
5. Normal combustion processes requires oxygen in adequate quantity to fully achieve
complete combustion. Insufficient amount of oxygen leads to incomplete combustion where
the amount of heat released would be less than maximum, and products other than CO 2,
H2O and N2 will exist.
6. Most common products of incomplete combustion are CO, CH 4, unburned C (soot and tar),
NOx, OH, H2, and particulates.
7. Air also contains water vapor (moisture). At low temperatures, water vapor can be treated
as ideal gas. At high temperatures, it breaks into H2, O2, H, and OH.
8. Due to attraction of oxygen is stronger to hydrogen than to carbon, usually hydrogen is
assumed to burn to completion, producing H2O.
Heat
1. Required to increase the fuel temperature to ignition temperature (combustion starts).
2. Ignition temperatures of various fuels at atmospheric air :
Ignition T (oC)
260
400
580
610
630

Fuel
Gasoline
Carbon
Hydrogen
Carbon Monoxide
Methane

3. For combustion to begin, the proportions of fuel and air must be in proper range.
2.2 Combustion Equations
In a combustion equation, the left-hand side are the reactants, while the right-hand side are the
products.
REACTANTS + OXYGEN (AIR)

PRODUCTS + heat

The number of atoms and mass of an element must be equal on each side.
BUT, the number of moles of each element on both sides may not be equal.

This is referred to as balancing a combustion (chemical) equation.

reactants

REACTION
CHAMBER

C + O2

products

CO2

For a complete combustion process, the products are already well known ie. CO 2 , H2O and N2 (if
applicable).
C3H8 + 5O2

3CO2 + 4H2O

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Incomplete combustion results in products that contain other substances than those mentioned
above. Therefore, a more complex equation would evolve and requires careful balancing of each
element. The following systematic approach may be applied :
1.
2.
3.
4.
5.
6.
7.

Set the number of moles of fuel equal to 1.

Assume (or fix) the possible substances in the products.
Write down known mole numbers ie. fuel, air, certain products.
Set the unknown mole numbers with letters, ie. a, b, c, x, y etc.
Balance CO2 , CO, and unburned C with the number of C from the fuel.
Balance H2O, OH and H2 with H from the fuel.
Balance O2 from the other components.

It must be remembered that if air is used instead of concentrated oxygen in the reactant, than 1
mole of oxygen in the air will be accompanied by 3.76 mole of nitrogen. For example (refer to above
equation),
C3H8 + 5(O2 +3.76N2)

3CO2 + 4H2O + 18.8N2

In this case, 5 moles of oxygen is required for complete combustion, however, the total number of
moles for air required is 5(1) + 5(3.76) = 23.8 moles.
2.3 Air-Fuel Ratio
AF ratio is a ratio to quantify the amount of air and fuel that exists in the combustion process. It is
expressed in a mass basis.

AF

mair
m fuel

FA

m fuel
mair

where m = N x M
In combustion analysis, an equivalence ratio is applied to measure the amount of air actually
supplied to the combustion process.
Equivalence ratio,

AFactual
AFstoic

Example
Determine the AF ratio for 1 kmol of octane burned with air containing 20 kmol of O 2, assuming
complete combustion and excess oxygen exists in the products.
Ans : 24.2 kg air/kg fuel
2.4 Stoichiometric (Theoretical) air
Definition : the minimum required air for complete combustion to occur.
When a fuel is burned with stoichiometric air, no unburned fuel and free oxygen exists, ie.
CH4 + 2(O2 + 3.76N2)

CO2 + 2H2O + 7.52N2

In actual practice, combustion processes uses more air than stoichiometric to increases the
combustion efficiency as well as a temperature control procedure.
Excess air is the term used when combustion air is supplied greater than stoichiometric air.
0% excess air is equal to 100% stoichiometric air.
50% excess air is equal to 150% stoichiometric air.

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If combustion air is supplied less than stoichiometric, it is termed as air deficiency or starved air.
10% starved air is equal to 90% stoichiometric air.
Air deficiency is mostly practiced in industries where a solid fuel is converted into gaseous fuels,
with minimum heat generation from the chemical process. For example, coal can be utilized as a
solid fuel in steam engines. The process will require supply of excess combustion air to gain
maximum heat by complete combustion. However, coal can also be gasified to form methane. In
this process, the combustion air supplied must be less than stoichiometric so that methane can be
formed.
2.5 Analyzing Combustion Products
Combustion is a complex process due to diverse chemical reactions accruing within the controlled
system. Theoretically, to achieve complete combustion requires the supply of excess air. However,
in actual cases even the supply of excess air fails to ensure complete combustion occurs. It is
almost impossible to predict the exact composition of composition products on the basis of mass
conservation alone.
In practice, products of combustion are analyzed using gas analyzers located downstream from the
main combustion chamber. These gas analyzers operates using Orsat gas analysis, where chemical
compounds are used to absorb certain gas compositions and measures their volumes.

Gas
Sample
inc. CO2
100 kPa
25oC
1 liter

Absorbs CO2

Gas
Sample
w/o CO2
100 kPa
25oC
0.9 liter

Mole fraction of CO2 in gas sample,

yCO 2

Vco 2 0.1

10%
V
1

2.6 Effect of Moisture in Combustion Air

If dry air is used as combustion air, than its chemical composition can be written as
ath (O2 + 3.76N2)
If the moisture content is significant (high humidity), the it should be considered in the combustion
process
ath (O2 + 3.76N2) + Nv,air (H2O)
where the number of moles of moisture can be determined from

N v , air
N total

Pv , air
Ptotal

and

Pv , air
Psat @ Tv

mv , air
mg

(relative humidity)

2.7 Energy Analysis of Combustion Processes

Previous sections involves solving chemical equations for a combustion process only. In
thermodynamics point of view, the amount of heat energy released during a combustion process is
the important aspect for study.
Basically, the heat energy released from a combustion process comes from the chemical energy
contained in the fuel. The energy change of a system during a chemical reaction can be stated as

Esystem Estate Echemical

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If there is no change in the state, ie. state of reactants = state of products, then the energy change
due to change of state would be zero. However, most combustion processes involves a change of
state (temperature change and solid/liquid fuels to gaseous products).
In the analysis of energy for combustion processes, a standard reference state is defined at 25 oC
and 1atm. The property values at the standard reference state is written as
ho , so and uo
The standard reference state is used as a reference to measure the energy release, where it is
assumed that all reactants and products are at thermal equilibrium at this state (the minimum level
where heat energy can be released to the surrounding).
For example, consider nitrogen gas whose enthalpy at the standard reference state is
h

8669 kJ / kmol

Now, we want to measure the maximum amount of energy that can be released by this gas when
the gas temperature is assumed at 500K.
At 500K, the ideal-gas enthalpy for N2

h 500 K 14,581 kJ / kmol

o

Therefore, the max amount of heat released, H max h 500 K h 5912 kJ / kmol
2.7.1

Heat value and the enthalpy of combustion

Heat transfer during a combustion process is written as

Exothermic ve
Endothermic +ve

Q = hc = Hprod - Hreact

H is the heat value and hc is the enthalpy of combustion.

The enthalpy of combustion represents the amount of heat released during a steady-flow
combustion process when 1 kmol (or 1 kg) of fuel is burned completely at a specified pressure and
temperature. It is dependant on state, therefore h c of a fuel will differ at different pressures and
temperatures.
To define heat value, H, another property called the enthalpy of formation, h f is introduced. h f is
the enthalpy of a substance at a specified state due to its chemical composition.
As a rule, h f for all stable elements such as O2, N2, H2, and C at standard reference state is zero.
Then, the heat value of the reactants or products at standard reference states can be related to h f
by
H react

and

h f ,r

H prod

h f ,p

Example, in the reaction between 1 mol of carbon and oxygen to form carbon dioxide
C + O2

CO2

hc

hc H p H r

1 kmol C
25 oC and 1 atm

h f , p N r h f , r
o

Combustion
o
o
NChamber
.h f N .h f

N .h f
1 kmol O2

CO 2
C

25 oC and 1 atm 1 393,520 1 0 1 0

o

O2

CO2
25 oC and 1 atm

393,520 kJ / kmol

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The enthalpy of formation for various substances at different pressures and temperatures can be
referred to the table of properties.
In actual combustion processes, the temperatures of the reactants and products are NOT at
standard reference state. Then, the heat value of the reactants or products at elevated temperature
states can be written by
H react

N (h

o
f

h T h )i

H prod

N (h

o
f

h T h )i

and

and the enthalpy of combustion is still, hc = Hprod - Hreact