Combustion chemistry calculations

FIRE3700 / 7600 lecture 3

David Lange
Concepts
Combustion chemistry

𝐹𝑢𝑒𝑙 + 𝑂𝑥𝑦𝑔𝑒𝑛 → 𝐶𝑂! + 𝐻! 𝑂 + 𝐶𝑂 + 𝑠𝑜𝑜𝑡 + 𝑒𝑛𝑒𝑟𝑔𝑦

Need to know how much fuel

Need to know how much Oxygen

It is the ratios that are important here, not the total quantities
 Gas mixtures and control volumes
A control volume is a useful concept that allows us to do a mass or energy balance based on
Closed boundary

known quantities. If the boundaries are open then the control volume can exchange mass or
energy with the external environment, if they’re closed then mass and energy are not exchanged.
Air
The control volume shown has a known volume, and contains air.

𝐴𝑖𝑟 = 𝑂! + 𝑁! + 𝐴𝑟 + ⋯

Inert – do not react, only exist as heat sinks which absorb energy

We often, but not always, ignore the contribution of Argon and

other inert elements which comprise a small percentage of air to
simplify problems.

We always have to account for nitrogen since it makes up such a

significant amount of air
 Matter quantities
Examples of quantities of interest include: N = the number of species in the
control volume, for air in the
examples given, this is 2 –
Oxygen and Nitrogen

Quantity: Example (using air):

A mole is a 𝑚𝑎𝑠𝑠 𝑚 𝑔 𝑚 #$#%&,() = ∑-

*+, 𝑚* = 𝑚$! + 𝑚-!
convenient unit
that is used to
define the number 𝑀𝑜𝑙𝑒𝑠 𝑛 𝑚𝑜𝑙 𝑛 #$#%&,() = ∑-
*+, 𝑛* = 𝑛$! + 𝑛-!
of atoms /
molecules, etc. of
a particular
substance 𝑉𝑜𝑙𝑢𝑚𝑒 𝑉 𝑚" 𝑉#$#%&,() = ∑-
*+, 𝑉* = 𝑉$! + 𝑉-!

These are the totals of the given quantity in the control volume, e.g the
total mass, the total number of moles, the total volume comprised of
partial volumes.
 Matter quantities The relationship between mass and
Examples of quantities of interest include: moles is given by:
𝑚
𝑛=
𝑀
Where M is the molecular weight of a
Quantity: Example (using air): material. e.g. M of a single atom of
Nitrogen is 14, M of a molecule of N2
𝑚𝑎𝑠𝑠 𝑚 𝑔 𝑚 #$#%&,() = ∑-
*+, 𝑚. = 𝑚$! + 𝑚-!
is 28 (2 x 14)

𝑀𝑜𝑙𝑒𝑠 𝑛 𝑚𝑜𝑙 𝑛 #$#%&,() = ∑-

*+, 𝑛. = 𝑛$! + 𝑛-!
The relationship between mass and
volume is given by the density:
𝑉𝑜𝑙𝑢𝑚𝑒 𝑉 𝑚" 𝑉#$#%&,() = ∑-
*+, 𝑉. = 𝑉$! + 𝑉-!
𝑚
𝜌=
𝑉
Fractions
Fractions allow us to deal with known quantities of mixtures easily. They non-dimensionalise
(this means that they have no units) the physical quantities discussed, mass, moles and volume.

𝑚* e.g. the mass fraction of a particular species is the ratio of

𝑚𝑎𝑠𝑠 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 (𝑌* ) 𝑌* = the mass of that species to the total mass in the control
𝑚 #$#%&,()
volume. The same concept is true for the mole and the
Volume fraction
𝑛*
𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 (𝑋* ) 𝑋* =
𝑛 #$#%&,()

𝑉*
𝑉𝑜𝑙𝑢𝑚𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 (𝑣* ) 𝑣* =
𝑉#$#%&,()
Flammability
We often discuss flammability in terms of an upper flammability limit (UFL) and a lower
flammability limit (LFL). These are defined in percentages of the volume fraction of a species in
a control volume
LFL, e.g. the LFL of ethane in air is 3 %. This corresponds to a
volume fraction of 0.03
FLAMMABILITY
NOTE: the chemical formula for ethane is C2H6
UFL

Compare this concept with the balanced equation for the stoichiometric reaction of ethane with Oxygen:
7
1𝐶! 𝐻/ + 𝑂! → 2𝐶𝑂! + 3𝐻! 𝑂
2

The coefficients tell us how many moles of a substance we have on the left and on the right hand side.

PROBLEM: We describe flammability in volume fractions, but we describe chemical reactions in

terms of moles!
Ideal gas law
An ideal gas is one which is incompressible – it does not change in volume under pressure.
The ideal gas law describes the relationship between pressure, temperature, volume and the number of moles of a
substance, under the assumption that it behaves as an idea gas.

P [N/m2] OR [Pa] 𝑃𝑉! = 𝑛! 𝑅𝑇 For one species

Air
V [m3] 𝑃𝑉"#"$%,'( = 𝑛 "#"$%,'( 𝑅𝑇 For the whole
volume and all
species
T [K]

n [mol] OR m [g]
R is a constant, the ideal gas constant, equal to 8.3
m3⋅Pa⋅K−1⋅mol−1
Consider the control volume
again, we can define these
quantities for a control
volume
Ideal gas law
We can use the ideal gas law to show that the mole fraction is equal to the volume fraction, assuming that the gases are
incompressible:

𝑃𝑉*
𝑛* H𝑛 𝑅𝑇 𝑉*
*
𝑋* = = = = 𝑣*
𝑛 #$#%&,() 𝑃𝑉#$#%&,() 𝑉#$#%&,()
L𝑛
#$#%&,() 𝑅𝑇
Air and fuel mixtures
We can also develop an expression to calculate mass fraction as a function of the mole fraction

𝑚 #$#%&,() = 𝑚%*0 + 𝑚1234

Air+Fuel
???

𝑛 #$#%&,() = 𝑛%*0 + 𝑛1234

𝑚*
𝑛* H𝑀 𝑚* 𝑀#$#%&,() 𝑀#$#%&,()
*
𝑋* = =𝑚 = M = 𝑌*
𝑛 #$#%&,() #$#%&,()
H𝑀 𝑚 #$#%&,() 𝑀* 𝑀*
#$#%&,()
Solution process
 1st step: Conversion of units
The first step to looking at these combustion reactions is to convert from mass to moles if
necessary

𝑚1234

𝑚$!
Need to calculate the mole fractions of these different species in the control volume
Air 𝑚-!
𝑚…
2nd step: Balanced equation
Stoichiometric conditions are defined by the complete reaction of all fuel and oxidizer – there is
no fuel or oxidizer left on the right hand side, e.g. for ethane:

𝐶! 𝐻/ + 3.5 𝑂! + 3.76𝑁! → 2𝐶𝑂! + 3𝐻! 𝑂 + 13.16𝑁! + 𝑒𝑛𝑒𝑟𝑔𝑦

For stoichiometric conditions we can write the balanced equation in a general form:

𝑥 𝑦 𝑧 𝑦 𝑥 𝑦 𝑧
𝐶6 𝐻7 𝑂8 + + − 𝑂! + 3.76𝑁! → 𝑥𝐶𝑂! + 𝐻! 𝑂 + 3.76 + − 𝑁! + 𝑒𝑛𝑒𝑟𝑔𝑦
2 4 2 2 2 4 2
Note: Air = 0.21O2 + 0.79N2 => 4.76 Air = O2+3.76N2
Stoichiometric conditions
We call this ideal condition stoichiometric. Note the number of moles of oxygen and fuel on the
previous slide, remember that we assume that the molar fraction is the same as the volume
fraction:

𝑣9234 1
= This is the stoichiometric ratio of ethane in air
𝑣$! 3.5

This allows us to define the equivalence ratio:

𝑣9234 ∅ > 1 𝑖𝑚𝑝𝑙𝑖𝑒𝑠 𝑅𝐼𝐶𝐻 𝑐𝑜𝑛𝑑𝑖𝑡𝑖𝑜𝑛𝑠, 𝑖. 𝑒. 𝑒𝑥𝑐𝑒𝑠𝑠 𝑓𝑢𝑒𝑙

𝑣$!
:;<2:4
∅= 𝑣
9234
𝑣$! ∅ < 1 𝑖𝑚𝑝𝑙𝑖𝑒𝑠 𝐿𝐸𝐴𝑁 𝑐𝑜𝑛𝑑𝑖𝑡𝑖𝑜𝑛𝑠, 𝑖. 𝑒. 𝑒𝑥𝑐𝑒𝑠𝑠 𝑜𝑥𝑦𝑔𝑒𝑛
=<>*;?*@3<0*;
Equivalence ratios (RICH conditions)
E.g. for ethane again 𝑣9234
𝑣$!
:;<2:4
∅= 𝑣 =2
9234
𝑣$!
=<>*;?*@3<0*;

We can rearrange this to show

𝑣9234 2
=
𝑣$! 3.5
:;<2:4

Which results in the following formula for the reaction

2𝐶! 𝐻/ + 3.5 𝑂! + 3.76𝑁! → 2𝐶𝑂! + 3𝐻! 𝑂 + 13.16𝑁! + 1𝐶! 𝐻/ + 𝑒𝑛𝑒𝑟𝑔𝑦

Equivalence ratios (LEAN conditions)
E.g. for ethane again 𝑣9234
𝑣$!
:;<2:4
∅= 𝑣 = 0.5
9234
𝑣$!
=<>*;?*@3<0*;

We can rearrange this to show

𝑣9234 0.5 1
= = Note: whole numbers of fuel are easier to deal with
𝑣$! 3.5 7
:;<2:4

Which results in the following formula for the reaction

1𝐶! 𝐻/ + 7 𝑂! + 3.76𝑁! → 2𝐶𝑂! + 3𝐻! 𝑂 + 26.32𝑁! + 3.5𝑂! + 𝑒𝑛𝑒𝑟𝑔𝑦

 3rd step: energy balance
The next step is to do an energy balance Adiabatic conditions imply that
and to solve for the adiabatic energy lost equals zero.

flame temperature, Tadi 𝐸A3B30:<3C = 𝐸4>=< + 𝐸=<>03C

𝐸=<>03C = ∆𝐻D0>C2;<=
𝐸A3B30:<3C = 𝑚1234 ∆𝐻;,9234
𝜕ℎ = 𝑐D 𝜕𝑇
NOTE: Be VERY careful of the units throughout. Specific enthalpy
∆𝑯𝒄,𝒇𝒖𝒆𝒍 can be expressed in [MJ/kg] or in [MJ/mol]. ∆𝐻 = 𝑛𝑐D 𝑑𝑇
𝒄𝒑 can be expressed in [J/kgK] or in [J/molK].
##$% 𝑐! is the specific heat capacity of a material.
𝑚1234 ∆𝐻;,9234 = a 𝑚𝑐D 𝑑𝑇 It is the amount of energy required to raise
#" the temperature of one unit mass by one
Kelvin. It typically has units [J/kgK]

𝑐! may or may not be a function of temperature

Intiial temperature, typically ambient (293 K)
3rd step: energy balance
If we assume that 𝑐) is constant with temperature, then we can rewrite this as:
##$%
𝑚1234 ∆𝐻;,9234 = a 𝑚𝑐D 𝑑𝑇
#"

𝑚1234 ∆𝐻;,9234 = b 𝑚* 𝑐D* (𝑇:C* − 𝑇E )

*+,

𝑚1234 ∆𝐻;,9234
𝑇:C* = 𝑇E +
∑-
*+, 𝑚* 𝑐D*
4th step: solution
The easiest way to solve this is to create a table such as the following (using ethane as an
example again, with ∅=1):
𝐶! 𝐻/ + 3.5 𝑂! + 3.76𝑁! → 2𝐶𝑂! + 3𝐻! 𝑂 + 13.16𝑁! + 𝑒𝑛𝑒𝑟𝑔𝑦

number of Molar Mass, m Specific ∆𝐻 𝑚𝑐D

moles, n mass [g] [g] heat, cp
[mol] [J/kgK]
Fuel 𝐶! 𝐻/ 1 𝑀(!F& 𝑚 = 𝑛𝑀 𝑐D,(!F& 𝑚1234 ∆𝐻;,9234
Products 𝐶𝑂! 2 𝑀($! 𝑚 = 𝑛𝑀 𝑐D,($! 𝑚𝑐D,($!
𝐻! 𝑂 3 𝑀F!$ 𝑚 = 𝑛𝑀 𝑐D,F!$ 𝑚𝑐D,F!$
𝑁! 13.16 𝑀-! 𝑚 = 𝑛𝑀 𝑐D,-! 𝑚𝑐D,-!

𝑚1234 ∆𝐻;,9234
𝑇:C* = 𝑇E +
∑-
*+, 𝑚* 𝑐D*