14-11-2022

Unit-V
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
air–fuel 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 is accompanied by 3.76
quantity of energy is released. kmol of N2.
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The fuel must be brought above its ignition

temperature to start the combustion. The
minimum ignition temperatures in
atmospheric air are approximately 260°C for
gasoline, 400°C for carbon, 580°C for
hydrogen, 610°C for carbon monoxide, and
630°C 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. 5

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

Fuel–air ratio (FA): The reciprocal of air–fuel ratio.

The air–fuel ratio (AF) represents the amount of air used

per unit mass of fuel during a combustion process.

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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, forming
A combustion process is complete if all the combustible H O.
2
components of the fuel are burned to completion.

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 fuel–air ratio to the stoichiometric
fuel–air 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 • Incomplete Combustion

the products is relatively • Dissociation
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
analyze the composition of
combustion gases is the
Orsat gas analyzer.
The results are reported on Determining the mole fraction of the CO2 in
a dry basis. combustion gases by using the Orsat gas
analyzer.
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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,
The microscopic form of energy of a
usually a large amount of sensible
substance consists of sensible, latent,
energy is absorbed or released.
chemical, and nuclear energies. 10

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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
25°C and 1 atm.
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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
earlier 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 use

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. 17

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Liquid octane at 25C, 1 atm enters a well-insulated reactor and reacts with air entering at the
same temperature and pressure. For steady-state operation and negligible effects of kinetic and
potential energy, determine the temperature of the combustion products for complete
combustion with
(a) the theoretical amount of air,
(b) 400% theoretical air.

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(a) For combustion of liquid octane with the theoretical amount of air

Each term on the left side of this equation

depends on the temperature of the products, TP.
This temperature can be determined by an
iterative procedure.

Interpolation between these temperatures gives TP = 2395 K

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(b) For complete combustion of liquid octane with 400% theoretical air

Observe that the right side has the same value as in part (a).
Proceeding iteratively as above, the temperature of the products is TP = 962 K.

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A natural gas has the following molar analysis: CH4, 80.62%; C2H6, 5.41%; C3H8, 1.87%;
C4H10, 1.60%; N2, 10.50%. The gas is burned with dry air, giving products having a molar
analysis on a dry basis: CO2, 7.8%; CO, 0.2%; O2, 7%; N2, 85%.
(a) Determine the air–fuel ratio on a molar basis.
(b) Assuming ideal gas behavior for the fuel mixture, determine the amount of products
in kmol that would be formed from 100 m3 of fuel mixture at 300 K and 1 bar.
(c) Determine the percent of theoretical air.

(a)

(b)
The amount of fuel in kmol

Total amount of products is b + c = 12.931 + 1.93 = 14.861 kmol of products per kmol of fuel
So, the amount of product mixture that would be formed from 100 m3 of fuel mixture is
(14.861)(4.01) = 59.59 kmol of product gas.

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(c) The balanced chemical equation for the complete combustion

The theoretical air–fuel ratio on a molar basis is

The percent of theoretical air

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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 A–18 through A–25 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
A–26 at the standard reference state of
25°C 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. 24

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In case of reacting system, a common datum must be used to assign entropy

values for each substance involved in the reaction. This is accomplished using
the third law of thermodynamics and the absolute entropy concept.
The third law deals with the entropy of substances at the absolute zero of
temperature. Based on empirical evidence, this law states that the entropy of a
pure crystalline substance is zero at the absolute zero of temperature, 0 K.
The entropy relative to this datum is called the absolute entropy.

The change in entropy of a substance between absolute zero and any given state can
be determined from precise measurements of energy transfers and specific heat data
or from procedures based on statistical thermodynamics and observed molecular data.

The entropy of the ith component of an ideal gas mixture

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Entropy Balances for Reacting Systems

CONTROL VOLUMES AT STEADY STATE

where is the molar flow rate of the fuel and the coefficients appearing in the underlined
terms are the same as those for the corresponding substances in the reaction equation.

CLOSED SYSTEMS

When the reactants and products form ideal gas mixtures, the entropy balance can be expressed
on a per mole of fuel (n) basis as

n: moles of each reactant or product per mole of fuel

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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. 27

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For the very special case of

Treact = Tprod = T0 = 25°C

The negative of the Gibbs function of

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

Setting a datum for the Gibbs function resembles that used in defining the enthalpy of
formation: To each stable element at the standard state is assigned a zero value
of the Gibbs function.

The Gibbs function of formation of a compound equals the change in the Gibbs
function for the reaction in which the compound is formed from its elements, the
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compound and the elements all being at Tref and pref

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[Pb] Determine the Gibbs function of formation of methane at the

standard state, 25C and 1 atm, in kJ/kmol

At the standard reference state, the enthalpies and Gibbs functions for carbon and hydrogen
are zero by definition.

Thus,

With enthalpy of formation and absolute entropy data from Table A-25

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Fuel Cells
 A fuel cell is an electrochemical device in which fuel and an oxidizer
(normally oxygen from air) undergo a chemical reaction, providing electrical
current to an external circuit and producing products.
 The fuel and oxidizer react catalytically in stages on separate electrodes:
(anode & cathode). An electrolyte separating the two electrodes allows
passage of ions formed by reaction. Depending on the type of fuel cell, the
ions may be positively or negatively charged.
 The reaction is not a combustion process.
Rates of reaction in fuel cells are limited by the time it takes for diffusion
of chemical species through the electrodes and the electrolyte and by the
speed of the chemical reactions themselves.
 The internal irreversibilities that are inherently less significant than
encountered in power producing devices relying on combustion.
 By avoiding highly irreversible combustion, fuel cells have the potential of
providing more power from a given supply of fuel and oxidizer, while
forming fewer undesirable products, than internal combustion engines and
gas turbines. 31

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Characteristics of Major Fuel Cell Types

Proton
Molten
Exchange Phosphoric Acid Solid Oxide Fuel
Carbonate Fuel
Membrane Fuel Fuel Cell (PAFC) Cell (SOFC)
Cell (MCFC)
Cell (PEMFC)
- vehicle auxiliary
Transportation power
- automotive power - large vehicle power
application - heavy vehicle
propulsion
- on-site - on-site - on-site
- portable power
Other cogeneration cogeneration cogeneration
- small-scale
applications - electric power - electric power - electric power
stationary power
generation generation generation

Electrolyte
Charge carrier

Operating
60–100C 150–220C 600–700C 800–1000C
temperature
Fuel reforming external external internal or external internal or external

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PROTON EXCHANGE MEMBRANE FUEL CELL (PEMFC)

• Operating temperature range 60–100C, which is below the boiling point of water.
Cooling is generally needed to maintain the fuel cell at the operating temperature.
• Due to such relatively low temperature operation, costly platinum catalysts are
required at both the anode and cathode to increase ionization reaction rates.
• Catalytic activity is more important in lower temperature fuel cells because reaction
rates tend to decrease with decreasing temperature.
• Hydrogen is preferred for fuel cell applications because of its exceptional ability to
produce electrons when suitable catalysts are used, with no harmful emissions.
Methanol (CH3OH) and carbon monoxide can be used directly as fuels in some
applications, but often with performance penalties 33

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CHEMICAL EXERGY
• A combined system is formed by an environment and an amount of a
hydrocarbon fuel at T0, p0.
• The object is to evaluate the work obtainable by allowing the fuel to react with
oxygen from the environment to produce the environmental components carbon
dioxide and water, each at its respective state in the environment.
• The chemical exergy is, by definition, the maximum theoretical work that could
be developed by the combined system.
• The sum of the thermomechanical and chemical exergies is the total exergy
associated with a given system at a specified state, relative to a specified exergy
reference environment.
CHEMICAL EXERGY OF A HYDROCARBON: CaHb
Assuming the environment consists of an ideal gas
mixture. The oxygen enters at its condition within the
environment: temperature T0 and partial pressure
where is the mole fraction of the oxygen in the
exergy reference environment.
The fuel and oxygen react completely within the cell
to produce carbon dioxide and water vapor, which
exit in separate streams at their conditions within the
environment: temperature T0 and their partial
pressures. 34

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For steady-state operation, the energy

rate balance for a control volume

An entropy rate balance

Eliminating the heat transfer rate between Eqs.

The maximum theoretical work (Ch Exergy) when no irreversibilities are present

replacing the specific entropy terms

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This can also be expressed in terms of the Gibbs functions of the respective substances

The specific Gibbs functions are

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CHEMICAL EXERGY OF OTHER SUBSTANCES

The method introduced for pure hydrocarbons can also be used in principle for
substances other than hydrocarbons.
The chemical exergy is the maximum theoretical work that could be developed by a
fuel cell into which a substance of interest enters at T0, p0 and reacts completely with
environmental components to produce environmental components. All environmental
components involved enter/exit the cell at their conditions within the environment.
For pure CO:

If CO is not pure, the last term will be changed to:

Pure water at T0, p0

water would enter the cell as a liquid at T0, p0 and exit as a vapor at T0, with no
cell reaction occurring

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No cell reaction would occur

For an ideal gas mixture at T0, p0 consisting only of substances

present as gases in the environment, the chemical exergy is
obtained by summing the contributions of each of the components.
The result, per mole of mixture, is

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Standard Chemical Exergy

• It is based on a standard exergy reference environment exhibiting
standard values of the environmental temperature T0 and pressure p0 such
as 298.15 K and 1 atm, respectively.
• The exergy reference environment also consists of a set of reference
substances with standard concentrations reflecting as closely as possible
the chemical makeup of the natural environment.
• To exclude the possibility of developing work from interactions among
parts of the environment, these reference substances must be in
equilibrium mutually.

STANDARD CHEMICAL EXERGY OF A HYDROCARBON: CaHb

a substance not present in the environment

All substances are assumed to enter and exit at T0, p0 and heat transfer occurs only
at temperature T0. Assuming no irreversibilities, an exergy rate balance is

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From enthalpy &

Entropy balance

From these 2 Eqs

the molar higher heating value (T0, p0)

In terms of molar Gibbs functions

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STANDARD CHEMICAL EXERGY OF OTHER SUBSTANCES

any substance not present in the environment

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CHEMICAL EQUILIBRIUM
Consider a closed system containing five components, A, B, C, D, and E (inert), at
a given temperature and pressure, subject to a single chemical reaction

The stoichiometric coefficients A, B, C, and D do not correspond to the respective
number of moles of the components present.
The amounts of the components present are designated nA, nB, nC, nD, and nE.
However, changes in the amounts of the components present do bear a definite
relationship to the values of the stoichiometric coefficients

The parameter  is sometimes referred to as

the extent of reaction

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at equilibrium, dG=0

equation of reaction equilibrium

In principle, the composition that would be present at equilibrium for a given

temperature and pressure can be determined by solving this equation.

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Equilibrium Constant for Ideal Gas Mixtures

LHS =

From the above 2 Eq

where K is the
thermal equilibrium/dissociation constant
It gives temperature of the fluid (table) for dissociation
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Equilibrium Flame Temperature the effect of incomplete combustion

on the adiabatic flame temperature

the products would exit the reactor at a temperature we have designated the maximum
adiabatic flame temperature. This temperature can be determined by solving a single
equation, the energy equation.
At such an elevated temperature, however, there
would be a tendency for CO2 to dissociate
Since dissociation requires energy (an endothermic reaction), the temperature of the products
would be less than the maximum adiabatic temperature found under the assumption of
complete combustion.

When dissociation takes place, the gaseous products exiting the reactor would not be CO2 and
N2, but a mixture of CO2, CO, O2, and N2.

z is the amount of CO, in kmol, present in the exiting mixture for each kmol of CO entering

There are two unknowns: z and the temperature of the exiting stream- Requires 2 Eqs
(1) an energy equation. (2) the equilibrium constant, If the exiting gas mixture is in equilibrium

The temperature of the products may then be called the equilibrium flame temperature

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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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