Fundamentals of Combustion

Lec 3: Chemical Thermodynamics

Dr. Zayed Al-Hamamre

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Content

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 Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Process Heat Transfer 1-3
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Process Heat Transfer 1-4
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 Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
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Theoretical and Excess Air

 Combustion reactions are usually run with more air than is
needed to supply oxygen in stoichiometric proportion to the
fuel.
 This has the effect of increasing the conversion of the
valuable reactant at the expense of the cost of the excess
reactant and additional pumping costs.

 Theoretical Oxygen:
The moles (batch) or molar flow rate (continuous) of O2 needed
for complete combustion of all the fuel fed to the reactor,
assuming that all carbon in the fuel is oxidized to CO2 and all the
hydrogen is oxidized to H2O

 Theoretical Air: The quantity of air that contains the theoretical

oxygen.

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  Excess Air:
The amount by which the air fed to the reactor exceeds the
theoretical air

If 50% excess air is supplied

Example
One hundred mol/h of butane (C4H10 ) and 5000 mol/h of
air are fed into a combustion reactor. Calculate the
percent excess air.

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The stoichiometric equation for complete combustion of butane:

The theoretical air from the feed rate of fuel and the
stoichiometric equation

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 Example
Ethane is burned with 50% excess air. The percentage
conversion of the ethane is 90%; of the ethane burned. 25%
reacts to form CO and the balance reacts to form CO2.
Calculate the molar composition of the stack gas on a dry basis
and the mole ratio of water to dry stack gas.

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Basis: 100 mol C2H6 Fed

Assumption: nitrogen is inert-that is, Thus, neglect the trace

amounts of Nox that might form

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Degree-of-Freedom
Analysis

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 Another
approach:
25% Conversion to 75% Conversion to
CO CO2
0.75 CO2 CO2

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Atomic Hydrogen
Balance:

Atomic Oxygen
Balance:

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The analysis of the stack gas is now
complete

Quiz:
Find the
composition in wet
base

The mole ratio of

water to dry stack
gas is

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Example
A hydrocarbon gas is burned with air. The dry-basis product gas
composition is 1.5 mole% CO, 6.0% CO2, 8.2% O2, and 84.3% N2.
There is no atomic oxygen in the fuel. Calculate the ratio of
hydrogen
to carbon in the fuel gas and speculate on what the fuel might
be. Then calculate the percent excess air fed to the reactor.

Basis: 100 mol Product Gas

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Degree-of-Freedom
Analysis

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 The fuel composition described by the formula

To find the Percent Excess Air

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Process Heat Transfer 1-20
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Process Heat Transfer 1-21
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Process Heat Transfer 1-22
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 Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Process Heat Transfer 1-23
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Process Heat Transfer 1-24
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 Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Process Heat Transfer 1-25
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Process Heat Transfer 1-26
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 Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
Process Heat Transfer 1-27
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Process Heat Transfer 1-28
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 Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
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Process Heat Transfer 1-30
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Summary and Examples

25 oC and 1 atm

Example

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Example Cont.

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Example Cont.

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Example Cont.

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Heat of reaction
If there are no gaseous reactants or products, then

Example

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Formation reaction and heat of formation

The standard heat of formation of an elemental species (e.g., O2) is zero.
If νA is the stoichiometric coefficient of the i th species participating in a reaction (+ for
products, - for reactants) and is the standard heat of formation of this species,
then the standard heat of the reaction is

Example

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Heat of combustion
The standard heat of combustion of a substance, , is the heat of the combustion
of that substance with oxygen to yield specified products [e.g., CO2(g) and H2O(l)],
with both reactants and products at 25oC and 1 atm (the arbitrary but conventional
reference state).
standard heats of combustion for a substances are tabulated.
The given values are based on the following assumptions:
(a) All carbon in the fuel forms CO2(g),
(b) All hydrogen forms H2O(l),
(c) All sulfur forms SO2(g), and
(d) All nitrogen forms N2(g).
Standard heats of reactions that involve only combustible substances and combustion
products can be calculated from tabulated standard heats of combustion.
For CO2, H2O and SO2, the standard heats of combustion is equal to zero.

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Heat of combustion
For combustion reaction,

Example

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Energy balance on reactive processes
Example

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Example Cont.

1. Use the heat of reaction method for the energy balance.

2. Choosing as references the reactant and product species in the states for which the
heat of reaction is given

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Example Cont.

Or one step or heat the liquid water from 25°C to l00°C, vaporize it, heat the vapor
from l00°C to 300°C,

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Example Cont.

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Example Cont.

Thus, 19,700 kW of heat must be transferred from the reactor to maintain the product
temperature at 300°C.
If less heat were transferred, more of the heat of reaction would go into the reaction
mixture and the outlet temperature would increase.
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Example

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Example Cont.
Two or multiple reactions system or
Single reaction with unknown ΔΗr

material balance is not required

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Example Cont.

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Example Cont.

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Example Cont.

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Example Cont.

to calculate then ΔΗ

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Processes with Unknown Outlet Conditions: Adiabatic Reactors

Example

Quiz: Find the composition of the output stream

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Example Cont.

Use either the Heat of Reaction Method or Heat of Formation Method

As references for enthalpy

calculations

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Example Cont.

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Example Cont.

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Example Cont.

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Example Cont.

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Example

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Example cont.
Quiz

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Example cont.

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Example cont.

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Example cont.

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Fuels and Their Properties
The heating value
The heating value of a combustible material is the negative of the standard heat of
combustion.
The higher heating value (or total heating value or gross heating value) is
With H2O(l) as a combustion product,.
The lower heating value (or net heating value) is the value based on H2O (v) as a
product.
Since is always negative, the heating value is positive.
To calculate a lower heating value of a fuel from a higher heating value or vice versa,
you must determine the moles of water produced when one mole of the fuel is
burned.
o If this quantity is designated n, then

Where the heat of vaporization of water at 25oC is

If a fuel contains a mixture of combustible substances, its heating value (lower or

higher) is Chemical Engineering Department | University of Jordan | Amman 11942, Jordan
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Fuels and Their Properties

xi is the mass fractions of the fuel components if the heating values are expressed
in units of (energy)/(mass), or
xi mole fractions if the dimensions of the heating values are (energy)/(mole).

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Example Cont.
Example

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Example Cont.

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Adiabatic Flame Temperature
When a fuel is burned,
o A considerable amount of energy is released.
o Some of this energy is transferred as heat through the reactor walls,
o The remainder raises the temperature of the reaction products;
o The less heat transferred, the higher the product temperature.
o The highest achievable temperature is reached if the reactor is adiabatic and all
of the energy released by the combustion goes to raise the temperature of the
combustion products (adiabatic flame temperature, Tad).

In adiabatic reactor ,

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Adiabatic flame temperature

depends on air/fuel ratio

Tad: Increases for preheated air, or for O2

instead of air.

Tad: decreases, if cooled exhaust gas is

mixed with reactants (recycling)

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Adiabatic Flame Temperature

Example

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Example Cont.

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Example Cont.

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Example Cont.

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Example Cont.

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