Jishnu Bhattacharya

1st Semester - 2016-17

Lecture -3

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

Enthalpy of formation

Enthalpy of formation
Two confusing facts:
Negative value: The enthalpy of formation is negative for
CO2. Why?
It only means that the formation reaction is
exothermic.
It also means that the mixture of elements are less
stable than the compound at the particular T and P
Multiple values:
For example, liquid and vapour phases of water. As
both forms are present at 25 C and the effect of
pressure on enthalpy of formation is small, both the
phases are tabulated. The difference between these two
values are approximately hfg of water at 25 C.

Heating Value
It is defined as
Amount of energy released when unit amount of fuel is burnt
under SSSF condition and the products are brought to the state
of reactants
If we look back at the definition of enthalpy of combustion,
heating value is nothing but the absolute value of the enthalpy
of combustion.

HV = hC

Heating Value
As the combustion product often contains water as a product (due to
the presence of H2 in the hydrocarbon fuels), the phase of the water
affects the heating value (so as the enthalpy of combustion).
This leads to two heating values: Lower and higher.
When water is in vapour form, the latent heat of condensation is
not included in the heating value -- That is the lower heating value
(LHV).
When water is in liquid form, enthalpy of condensation is included
in the heating value. Thats why it is higher in magnitude. It is called
higher heating value (HHV).

HHV = LHV + N h fg
H 2O

Heating Value

Absolute enthalpy
Not all reactions occur at STP.
We need to analyse the thermodynamics while away from STP.

o
f

h = h + h
STP T , P

Absolute
Enthalpy

Enthalpy
of
formation

Sensible
Enthalpy