Chapter 9

Calorimetry
Definitions

CALORIFIC VALUE
The amount of energy which becomes available when 1kg or 1m3 of fuel is completely
burnt under specified conditions. Other names include specific energy and heating
value.

HIGHER CALORIFIC VALUE

The heating value obtained when water in the combustion products is in the form of a
liquid

LOWER CALORIFIC VALUE

The heating value obtained when water in the combustion products is in the form of
steam (vapor)
Calorific values of Solid or Liquid Fuels

Heat liberated by combustion = heat gained by water + apparatus

where CV = calorific value of fuel (kJ/kg)

mw = equivalent mass of water + apparatus (kg)
Cp = specific heat capacity of water (4.185 kJ/kg.K)
True ΔT = actual temperature rise (oC of K)
Mf = mass of fuel sample (kg)
Example 9.1

A sample of coal of mass 0.864g was burnt in a bomb calorimeter and the following details
were recorded:

Mass of water surrounding bomb 2000g

Mass of water in bomb 10g
Water equivalent of apparatus 350g
Initial temperature of water 16.235oC
Final recorded temperature of water 19.280oC
Cooling correction +0.017oC

Given that the specific heat capacity of water is 4.185kJ/kg.K, determine the calorific value of
the coal.
Lower Calorific Values

The higher and lower calorific values are related by:

LCV = HCV – (mass of water formed x 2440kJ/kg)

In which the mass of water formed is always given by 9 times the mass of hydrogen
(H2) in 1 kg of the fuel.

Example 9.2:
The calorific value of diesel fuel (C12H26) as dertermined by using a bomb calorimeter
was found to be 46 MJ/kg. Determine the LCV of the fuel. The latent heat of
condensed steam may be taken as 2440 KJ/kg.
Dulong’s Formulae

Dulong’s Formula for estimating the HCV of fuels:

The HCV can be estimated by the empirical formula:

in which the symbols C, H2, O2 and S are the masses of carbon, hydrogen, oxygen
and sulphur contained in 1kg of the fuel, and the coefficients represent the higher
calorific values (in MJ/kg) of the respective constituents.

The term gives the amount of hydrogen available for combustion.

Example 9.3

A boiler uses coal having an ultimate analysis of 88,7% carbon, 2,1% hydrogen, 2,4%
oxygen, 0,5% sulphur, and the remainder ash.

Use Dulong’s formula to estimate the HCV of the coal.

Given that the latent heat of the moisture formed by combustion is 2440KJ/kg,
estimate the LCV of the coal.
Calorific Values of Gaseous Fuels

This is generally referred to as the volumetric calorific value and is obtained using a
continuous flow calorimeter.

Heat liberated by combustion = heat gained by water

where CV = calorific value of fuel (KJ/kg)

mw = mass of circulating water (kg)
Cp = specific heat capacity of water (KJ/kg.K)
T = temperature rise of water (oC)
volf = volume of fuel burnt (m3)

NB: the calorific value should be measured as standard temperature and pressure
(0oC and 101.3kPa)
Example 9.4:

The following results were recorded during the determination of the calorific value of a
gaseous fuel using a calorimeter:
Water circulated 2500g
Inlet temperature 14oC
Outlet temperature 28.3oC
Mass of condensed steam 9.6g
Volume of gas condensed 0.01m3
Gas pressure 104.85kPa
Gas temperature 170C

Determine the HCV and LCV of the gas in MJ/m3 measured at STP. Take the specific
heat capacity of water as 4.184KJ/kg.K, and the latent heat of the condensed steam
as 2440KJ/kg.