Chapter 15

CHEMICAL REACTIONS
Objectives
Give an overview of fuels and combustion.
Apply the conservation of mass to reacting systems to
determine balanced reaction equations.
Define the parameters used in combustion analysis, such
as airfuel ratio, percent theoretical air, and dew-point
temperature.
Apply energy balances to reacting systems for both steady-
flow control volumes and fixed mass systems.
Calculate the enthalpy of reaction, enthalpy of combustion,
and the heating values of fuels.
Determine the adiabatic flame temperature for reacting
mixtures.
Evaluate the entropy change of reacting systems.
Analyze reacting systems from the second-law perspective.
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 FUELS AND COMBUSTION
Fuel: Any material that can be burned to release thermal energy.
Most familiar fuels consist primarily of hydrogen and carbon.
They are called hydrocarbon fuels and are denoted by the general formula
CnHm.
Hydrocarbon fuels exist in all phases, some examples being coal, gasoline
(usually treated as octane C8H18), and natural gas.

Most liquid hydrocarbon fuels

are obtained from crude oil by
distillation. 3
The oxidizer most often used in combustion processes is air. Why?
On a mole or a volume basis, dry air is composed of 20.9% O2, 78.1% N2,
0.9% Ar, and small amounts of CO2, He, Ne, H2.
In the analysis of combustion processes, dry air is approximated as 21% O2
and 79% N2 by mole numbers.

Combustion is a chemical reaction during Each kmol of O2 in air

which a fuel is oxidized and a large quantity is accompanied by 3.76
of energy is released. kmol of N2.
4
The fuel must be brought above its ignition
temperature to start the combustion. The
minimum ignition temperatures in
atmospheric air are approximately 260C for
gasoline, 400C for carbon, 580C for
hydrogen, 610C for carbon monoxide, and
630C for methane.
Proportions of the fuel and air must be in the
proper range for combustion to begin. For
example, natural gas does not burn in air in
concentrations less than 5% or greater than
about 15%.
The mass (and number of atoms)
of each element is conserved
during a chemical reaction.

The total number of

moles is not
conserved during a
chemical reaction.
In a steady-flow combustion process, the components that
enter the reaction chamber are called reactants and the
components that exit are called products.
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 Air-fuel ratio (AF) is usually
expressed on a mass basis and
is defined as the ratio of the m mass
mass of air to the mass of fuel
N number of moles
for a combustion process
M molar mass

Fuelair ratio (FA): The reciprocal of airfuel ratio.

The airfuel ratio (AF) represents the amount of air used

per unit mass of fuel during a combustion process.

6
THEORETICAL AND ACTUAL COMBUSTION
PROCESSES
Complete combustion: If all the carbon in the fuel burns to CO2, all the
hydrogen burns to H2O, and all the sulfur (if any) burns to SO2.
Incomplete combustion: If the combustion products contain any unburned
fuel or components such as C, H2, CO, or OH.
Reasons for incomplete combustion: 1 Insufficient oxygen, 2 insufficient
mixing in the combustion chamber during the limited time that the fuel and the
oxygen are in contact, and 3 dissociation (at high temperatures).
Oxygen has a much
greater tendency to
combine with hydrogen
than it does with carbon.
Therefore, the hydrogen
in the fuel normally
burns to completion,
A combustion process is complete if all the forming H2O.
combustible components of the fuel are burned to
completion.
7
Stoichiometric or theoretical air: The minimum amount of air needed for the
complete combustion of a fuel. Also referred to as the chemically correct
amount of air, or 100% theoretical air.
Stoichiometric or theoretical combustion: The ideal combustion process
during which a fuel is burned completely with theoretical air.
Excess air: The amount of air in excess of the stoichiometric amount. Usually
expressed in terms of the stoichiometric air as percent excess air or percent
theoretical air.
Deficiency of air: Amounts of air less than the stoichiometric amount. Often
expressed as percent deficiency of air.
Equivalence ratio: The ratio of the actual fuelair ratio to the stoichiometric
fuelair ratio.

50% excess air = 150% theoretical air

200% excess air = 300% theoretical air.
90% theoretical air = 10% deficiency of air

The complete combustion process with no free oxygen

in the products is called theoretical combustion.
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Predicting the composition of
the products is relatively
easy when the combustion
process is assumed to be
complete.
With actual combustion
processes, it is impossible to
predict the composition of
the products on the basis of
the mass balance alone.
Then the only alternative we
have is to measure the
amount of each component
in the products directly.
A commonly used device to Determining the mole fraction of the CO2 in
analyze the composition of combustion gases by using the Orsat gas
combustion gases is the analyzer.
Orsat gas analyzer.
The results are reported on
a dry basis.
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ENTHALPY OF FORMATION AND ENTHALPY
OF COMBUSTION
Disregarding any changes in kinetic and potential energies, the energy change
of a system during a chemical reaction is due to a change in state and a change
in chemical composition:

When the existing chemical bonds are

destroyed and new ones are formed
during a combustion process, usually
The microscopic form of energy of a
a large amount of sensible energy is
substance consists of sensible, latent,
absorbed or released.
chemical, and nuclear energies. 10
Enthalpy of reaction hR : The difference between the enthalpy of the products at a
specified state and the enthalpy of the reactants at the same state for a complete
reaction.
Enthalpy of combustion hC : It is the enthalpy of reaction for combustion
processes. It 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 temperature and pressure.
The enthalpy of formation hf : The amount of energy absorbed or released as
the component is formed from its stable elements during a steady-flow process at
a specified state.

To establish a starting
point, we assign the
enthalpy of formation
of all stable elements
(such as O2, N2, H2,
and C) a value of zero
at the standard
reference state of
25C and 1 atm.

11
Heating value: The amount of heat
released when a fuel is burned
completely in a steady-flow process
and the products are returned to
the state of the reactants. The
heating value of a fuel is equal to
the absolute value of the enthalpy
of combustion of the fuel.
Higher heating value (HHV):
When the H2O in the products is in
the liquid form.
Lower heating value (LHV): When
the H2O in the products is in the
vapor form.
The higher heating value of a fuel is equal to the sum of the lower heating
value of the fuel and the latent heat of vaporization of the H2O in the products.
For the fuels with variable
composition (i.e., coal, natural gas,
fuel oil), the heating value may be
determined by burning them
directly in a bomb calorimeter.
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FIRST-LAW ANALYSIS OF
REACTING SYSTEMS
The energy balance (the first-law) relations developed
in Chaps. 4 and 5 are applicable to both reacting and
nonreacting systems. We rewrite the energy balance
relations including the changes in chemical energies.
Steady-Flow Systems

When the changes in kinetic and potential energies are

negligible, the steady-flow energy balance for a
chemically reacting steady-flow system: The enthalpy of a chemical
component at a specified state

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Taking heat transfer to the system and work done by
the system to be positive quantities, the energy balance relation is

If the enthalpy of combustion for a particular reaction is available:

Most steady-flow combustion processes do not involve any work interactions.

Also, combustion chamber normally involves heat output but no heat input:

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Closed Systems
Taking heat transfer to the system and work done
by the system to be positive quantities, the general
closed-system energy balance relation can be
expressed for a stationary chemically reacting An expression for the
closed system as internal energy of a
chemical component
in terms of the
enthalpy.

Utilizing the definition of enthalpy:

The Pv terms are negligible for solids and liquids, and can be
replaced by RuT for gases that behave as an ideal gas.

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ADIABATIC FLAME TEMPERATURE
In the limiting case of no heat loss to the surroundings (Q = 0), the temperature
of the products reaches a maximum, which is called the adiabatic flame or
adiabatic combustion temperature.
since

The determination of the adiabatic flame temperature by hand requires the

use of an iterative technique.

The temperature of a
combustion chamber
becomes maximum when
combustion is complete and
no heat is lost to the
surroundings (Q = 0).

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The adiabatic flame temperature of a fuel depends on
(1) the state of the reactants
(2) the degree of completion of the reaction
(3) the amount of air used
For a specified fuel at a specified state burned with air at a
specified state, the adiabatic flame temperature attains its
maximum value when complete combustion occurs with the
theoretical amount of air.

The maximum temperature encountered in a

combustion chamber is lower than the theoretical
adiabatic flame temperature.
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ENTROPY CHANGE OF REACTING SYSTEMS
entropy balance for any
system (including reacting
systems) undergoing any
process

for a closed or steady-flow

reacting system

for an adiabatic process (Q = 0)

The entropy
change
associated with a
chemical relation.

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 Entropy of a P0 = 1 atm
component Pi partial pressure
yi mole fraction
Pm total pressure of mixture.
When evaluating the entropy of a
component of an ideal-gas mixture, we
should use the temperature and the partial
pressure of the component.
The absolute entropy values are listed in
Tables A18 through A25 for various ideal
gases at the specified temperature and at a
pressure of 1 atm. The absolute entropy
values for various fuels are listed in Table
A26 at the standard reference state of
25C and 1 atm.

At a specified temperature, the absolute

entropy of an ideal gas at pressures other
than P0 = 1 atm can be determined by
subtracting Ru ln (P/P0) from the tabulated
value at 1 atm. 19
SECOND-LAW ANALYSIS OF REACTING SYSTEMS
Exergy destruction

The reversible work for a steady-flow combustion process that involves

heat transfer with only the surroundings at T0

When both the reactants and the

products are at T0
Gibbs
function

The difference between the

exergy of the reactants and of
the products during a chemical
reaction is the reversible work
associated with that reaction. 20
For the very special case of
Treact = Tprod = T0 = 25C

The negative of the Gibbs

function of formation of a
compound at 25C, 1 atm
represents the reversible
work associated with the
formation of that
compound from its stable
elements at 25C, 1 atm
in an environment that is
at 25C, 1 atm.

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 Summary
Fuels and combustion
Theoretical and actual combustion processes
Enthalpy of formation and enthalpy of
combustion
First-law analysis of reacting systems
Steady-flow systems
Closed systems
Adiabatic flame temperature
Entropy change of reacting systems
Second-law analysis of reacting systems

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