Jishnu Bhattacharya

1st Semester - 2015-16

Lecture -2

Reactants and Products

Combustion, as any other reaction, involves reactants and products.
Typically, a hydrocarbon reacts with air in a combustion process.

C x H y + a(O2 + 3.76 N 2 ) xCO2 + ( y 2 )H 2O + 3.76aN 2

Typical
hydrocarbon

Standard
Air

Nonparticipating
part of air

Air-fuel ratio (A/F)

If we balance the equation to match number of moles of different elements,

C x H y + a(O2 + 3.76 N 2 ) xCO2 + ( y 2 )H 2O + 3.76aN 2

a = x+ y/4
By balancing, we are allowing the exact amount of air that is required to burn
the fuel completely without any constraint on the rate of reaction
Stoichiometric

( A F )stoic

mair
=
m
fuel

4.76a MWair

1 MW fuel
stoic

Air-fuel ratio (A/F)

In a real combustion process, the stoichiometric air-fuel ratio is neither easy
to maintain nor desirable.

Lean

( A F ) > ( A F )stoic

Rich

( A F ) < ( A F )stoic

To quantify the leanness/richness of an air-fuel mixture, Equivalence ratio

() is defined as:

( A F )stoic
=
(A F )

Lean < 1

Rich > 1

Air-fuel ratio (A/F)

Another way of quantifying the richness: percent stoichiometric air and
percent excess air

100%
% Stoichiometric air =

1
% Excess air =
100%

Various Enthalpy terms

Enthalpy of Reaction
Enthalpy of Combustion
Enthalpy of Formation
Heating value
Higher heating value
Lower heating value

Fixing the reference state

During a chemical reaction, composition is no longer fixed. Chemical
bonds are broken and formed. Some material species are destroyed to
form some other material species.
Assumption: No change in overall mass; i.e., no nuclear reaction.
If the change in KE and PE are negligible compared to the change in
chemical energies, the change in energy of a system will be due to change
in state and change in chemical composition.

Esys = Estate + Echem

Fixing the reference state

Now, if the products of a chemical reaction are in the same state as the
reactants,

Estate = 0
OR,

Esys = Echem

The concept is helpful not only when the entry and exit states are actually
same, but also when they are not and we want to isolate the chemical
energy from the energy due to state-change.

Fixing the reference state

In thermodynamics, we are interested in the changes only and hence
the choice of reference state does not alter the analysis.
However, the change in composition in chemical reaction demands that
the choice of reference state for different materials must be consistent.
The common reference state for all substances is chosen to be 25 C and
0.1 Mpa and it is called the standard reference state or standard
temperature and pressure (STP).
Property values at the standard reference state are indicated by the
superscript o such as ho, uo etc

Enthalpy of reaction
Consider a reaction where Carbon and O2 react to form CO2.
Q

1 kmol C
@ STP
1 kmol CO2
@ STP
1 kmol O2
@ STP

Enthalpy of reaction
Q
1 kmol
C@
STP
1 kmol
O2 @
STP

We do a controlled reaction to get

product at the STP as well.
1 kmol
CO2 @
STP

So,

Estate = 0

And

Esys = Echem

Under the assumption of SSSF,

Q = HP HR

This heat is termed enthalpy of reaction (hR) and defined as

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
For a combustion reaction (such as the example reaction), the enthalpy
of reaction is called the enthalpy of combustion(hC).
It represents the amount of heat released during a steady-flow
combustion process when unit amount of fuel is burned completely at a
specified temperature and pressure.
For the example reaction, the value is -393520 kJ/kmol for carbon.
This value for a particular fuel will be different at different T and P

Enthalpy of combustion
Enthalpy of combustion is very useful property for a fuel
However,
o The fuel composition in real-life combustion is so varied, it is not
possible to tabulate this property for all such combinations.
oIt is relevant only in case of complete combustion, which is almost
never a case in a real life combustion.
oWe need some more fundamental property which will be applicable
in analysing a general combustion reaction.

Enthalpy of formation
This quantity can be very simply defined as
The enthalpy of a substance at a specified state due to its chemical
composition
From definition, it looks very vague and philosophical, however, if we
look back at the same example of combustion of carbon,
Q
1 kmol
C@
STP
1 kmol
O2 @
STP

1 kmol
CO2 @
STP

Here, CO2 is being formed from its

basic elemental ingredients.
Instead of focusing on which fuel is
burnt, we are considering the
product from its constituent
elements.

Enthalpy of formation
With additional assumption of zero
Q
1 kmol
C@
STP

enthalpy for the elements at STP,

1 kmol
CO2 @
STP

1 kmol
O2 @
STP

HR = 0
And,

Q = HP

The heat released is property of the

0
f

product and in particular, the heat

h = 393520kJ / kmol
Notations ::

released during its formation. Hence, it

is called the enthalpy of formation.

0: STP; f: formation; h: enthalpy; over bar: per mole