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What Is Combustion Process and Explain Enthalpy of Formation. Combustion Process
What Is Combustion Process and Explain Enthalpy of Formation. Combustion Process
Combustion process:
Combustion is an exothermic chemical reaction between a fuel and oxygen which proceeds at a fast
rate with the release of energy in the form of heat.
The main combustion elements in a fuel are carbon (c) and hydrogen (h2) with other elements
appearing in small quantities.
The amount of heat liberated when one Kmol of carbon is burnt/oxidized at 25® C equal to 393,522kJ
The enthalpy equation for the combustion of hydrogen to form liquid water.
The standard heat / enthalpy in a combustion reaction is called the standard heat / enthalpy of
combustion. This is always based on 1 mole of the substances burnt/oxidized.
Atmospheric air contains 21% oxygen, 78% nitrogen and 1% argon by volume. In combustion
calculation, the argon is usually neglected and air is assumed to consist of 21% oxygen and 79% nitrogen by
volume. On mass basis, air contains 23% oxygen and 77% nitrogen.
Enthalpy of formation:
Let us consider the steady state steady flow combustion of carbon and oxygen to form Co 2 as shown
in figure.
C.V
C 25°c, 1atm
O2
Let the carbon and oxygen enter the control volume at 25°c and 1 atm, pressure and the heat
transfer be such that the product CO2 leaves at 25°c, 1atm pressure
The measure value of heat transfer is -393,522 KJ per kg of CO2 formed
If HR and HP refer to the total enthalpy of the reactants and products respectively.
HR + Qc.v = Hp
Generally all the reactants and products in a reaction , the equation may be written as
+ Qc.v =
The enthalpy of all the elements at the standard reference state of 25°c ,1 atm is assigned the
value of zero
In carbon- oxygen reaction, HR = 0
It is also denoted by f°
f° = -393522 KJ/Kgmol
But in most cases, the reactants and products are not at 25°c, 1 atm. Therefore, the change in
enthalpy between 25°c, 1 atm and the given state must be known.
T,p = f° + Δ
Where Δ referents the difference in enthalpy between any given state and the enthalpy at 298.15K,
1atm.
n1 n3
Reactants Products
n2 n4
QC.V W C.V
The significance of the enthalpy of formation is that it is most convenient in performing a first-law
analysis, of a reaction system, for the enthalpies of different substances can be added or subtracted.
The first law for a steady-state, steady flow process in the form (SSSF)
Qc.v + HR = Wc.v+ Hp
OR
Qc.v + = Wc.v +
Where R and P refer to the reactants and products respectively.
Where = [ f° + Δ ]i
=[ f° + Δ ]e
When the states of reactants and products are not in the standard reference state (298k,1atm)
Then
Qc.v = HR- Hp
= p - p0 ) +Δ Rp - R - R0 )
= p- p0) +Δ Rp - R - R0)
R
R0
H
P
Δh Rp
P0
298k T
Consider a given combustion process that takes place adiabatically and with no work or changes in
K.E or potential energy involved. The temperature of the products is referred to as the adiabatic Flame
temperature.
With the assumption of no work and no changes in kinetic or potential energy, this is the maximum
temperature that can be achieved for the given reactants because any heat transfer from the reacting
substances and any incomplete combustion would tend to lower the temperature of the products.
For a given fuel and given pressure and temp of reactants, the maximum adiabatic flame temperature
that can be achieved is with a stoichiometric mixture. The Adiabatic flame temperature can be controlled by
the amount of excess air that is used.
HR=Hp
Or
[ f° + Δ ]i = [ f° + Δ ]e
For example:
The enthalpy of combustion is defined as the difference between the enthalpy of the products and the
enthalpy of reactants when complete combustion occurs at a given temperature and pressure
RP = Hp - HR
Or
RP = [ f° + Δ ]e - [ f° + Δ ]i
RP= Up - UR
= [ f° + Δ ]e - [ f° + Δ ]i
If all the gaseous constituent are considered ideal gases and the volume of liquid and solid
considered is assume to be negligible compared to gaseous volume.
RP = RP - T ( η gaseous products - η gaseous Reactants)
In the case of a constant pressure or steady flow process, the negative of the enthalpy of
combustion is frequently called the heating value at constant pressure, which represents the heat
transferred from the chamber during combustion at const. pressure.
Similarly, the negative of the internal energy of combustion is called as the heating value at
constant volume in the case of combustion, because it represents the amount of heat transfer in
the const volume process.
The higher heating value (HHV) or higher calorific value (HCV) is the heat transferred when
H2O in the products is in the liquid phase.
The lower heating value (LHV) or lower calorific value (LCV) is the heat transferred when H2O
in the products is in the vapour phase.
The concepts of first and second laws of thermodynamics are involved in reversible work
irreversibility and availability (energy)
To determining the maximum work (Availability) that can be done through a combustion process and
with examining the irreversibility’s associate with such process.
The reversible work for a steady-state process in which there is no heat transfer with reservoirs other
than the surroundings, and also absence of changes in kinetic and potential energy is
To apply the equation to a steady state process. That involves a chemical reaction
Eq (1) becomes
Wrev = [ f°+Δ -To ]i - [ f°+Δ -To ]e (2)
I = Wrev – W
= To e - To i - QC.V (3)
The availability , Ψ for a steady- flow process in the absence of kinetic and poteneial energy changes
is given by
If a steady- state chemical reaction takes places in such a manner that both the reactants and products
are in temperature equilibrium with the surroundings the Gibbs function (g= h- Ts )
The reversible work is given be Eq (2) becomes
Wrev = i- e
= -ΔG (5)
In which ΔG = ΔH - TΔs
Where a system is at the dead state, it is in thermal and mechanical equilibrium with the
environment, and the value of its energy is zero is thermo mechanical contribution to energy is zero.
However, the content of contents of a system at the dead state may undergo chemical reaction with
environmental components and produce additional work.
Here a combined system formed by an environment and a system having a certain amount of fuel at
To,Po The cork obtainable by allowing the fuel to react with oxygen from the environment to produce the
environment components of CO2 and H2O is evaluated.
The chemical energy is thus defined as the maximum theoretical work that could be developed by the
combined system.
Work
Po,To
Ca Hb
CO2 at To
XCO2 Po
O2 at To
XO2/ Po
H2O at To , XH2O Po
+ = +
= + H R - HP
Where is the rate of fuel flow in moles, and KE and PE are neglected.
Where T0 ,po is the absolute entropy and xi is the mole fraction of component i in the environment .
R To ln (7)
In terms of Gibbs functions
= (u-uo)+po(v-vo)-To(s-so) + + gz +ach