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Chapter 1
Pure Substance
A pure substance is defined as a substance having a constant and uniform chemical composition.
A homogeneous mixture of gases which do not react with one another
Solid Fuels
Solid fuel is a term given to various types of solid materials that provide energy. This energy is
usually released by combustion.
Most liquid fuels are derived from fossil fuels. These can be classified according to their
volatility (the ease with which they evaporate and turn into vapor).
The most volatile fuels are gasoline and kerosene.
Ethanol produced from the fermentation of sugar is a prominent liquid fuel.
Gaseous fuels
These are the fuels in gaseous phase. They are also generally hydrocarbon fuels derived from
petroleum reserves available in nature.
Most common gaseous fuel is natural gas.
Gaseous fuels may also be produced artificially from burning solid fuel (coal) and water.
A mixture of methane (CH4) and ethane (C2H6) is an example of a gaseous fuel.
Some of gaseous fuels produced artificially are coal gas, producer gas etc.
Nuclear Fuels
Fuels such as uranium or thorium that can be used in nuclear reactors as a source of electricity
are called nuclear fuels.
The energy derived during fission or fusion processes is called nuclear energy.
Examples of nuclear fuels are: 235U, 238U, and 239Pu.
Important Terms
Air fuel ratio: It refers to the ratio of amount of air in combustion reaction with the amount of
fuel. Mathematically, it can be given by the ratio of mass of air and mass of fuel.
massofair
AF
massoffuel
Fuel-air ratio: is inverse of Air-fuel ratio. Theoretical air-fuel ratio can be estimated from
stoichiometric combustion analysis for just complete combustion.
Equivalence ratio: It is the ratio of actual fuel-air ratio to the theoretical fuel-air ratio for
complete combustion.
Lean mixture and Rich mixture: Fuel-air mixture will be called lean mixture when
equivalence ratio is less than unity while for equivalence ratio value being greater than unity the
mixture will be rich mixture.
Theoretical air: Theoretical amount of air refers to the minimum amount of air that is required
for providing sufficient oxygen for complete combustion of fuel. This theoretical air is also
called “stoichiometric air”.
Excess air: Any air supplied in excess of “theoretical air” is called excess air. Generally excess
air is 25 to 100% to ensure better and complete combustion.
Flash point: Flash point refers to that temperature at which vapour is given off from liquid fuel
at a sufficient rate to form an inflammable mixture but not at a sufficient rate to support
continuous combustion.
Fire point: refers to that temperature at which vaporization of liquid fuel is sufficient enough to
provide for continuous combustion.
Adiabatic flame temperature: Adiabatic flame temperature refers to the temperature that could
be attained by the products of combustion when the combustion reaction is carried out in limit of
adiabatic operation of combustion chamber.
This is the maximum temperature which can be attained in a combustion chamber and is
very useful parameter for designers.
Wet and dry analysis of combustion: Combustion analysis when carried out considering water
vapour into account is called “wet analysis” while the analysis made on the assumption that
vapour is removed after condensing it, is called “dry analysis”.
Volumetric and gravimetric analysis: Combustion analysis when carried out based upon
percentage by volume of constituent reactants and products is called volumetric analysis.
Combustion analysis carried out based upon percentage by mass of reactants and products is
called gravimetric analysis.
Pour point: It refers to the lowest temperature at which liquid fuel flows under specified
conditions.
Cloud point: When some petroleum fuels are cooled, the oil assumes cloudy appearance. This is
due to paraffin wax or other solid substances separating from solution. The temperature at which
cloudy appearance is first evident is called cloud point.
Composition of air: Atmospheric air is considered to be comprising of nitrogen, oxygen and
other inert gases. For combustion calculations the air is considered to be comprising of nitrogen
and oxygen in the following proportions. Molecular weight of air is taken as 29.
• Composition of air by mass = Oxygen (23.3%) + Nitrogen (76.7%)
• Composition of air by volume = Oxygen (21%) + Nitrogen (79%)
Enthalpy of combustion: Enthalpy of combustion of fuel is defined as the difference between
the enthalpy of the products and enthalpy of reactants when complete combustion occurs at given
temperature and pressure.
It may be given as higher heating value or lower heating value. Higher heating value
(HHV) of fuel is the enthalpy of combustion when all the water (H2O) formed during
combustion is in liquid phase.
Lower heating value (LHV) of fuel refers to the enthalpy of combustion when all the
water (H2O) formed during combustion is in vapour form. The lower heating value will
be less than higher heating value by the amount of heat required for evaporation of water.
HHV = LHV + (Heat required for evaporation of water)
It is also called calorific value of fuel and is defined as the number of heat units liberated
when unit mass of fuel is burnt completely in a calorimeter under given conditions.
Enthalpy of formation: Enthalpy of formation of a compound is the energy released or
absorbed when compound is formed from its elements at standard reference state.
Enthalpy of formation will have positive (+ ve) value if formation is by an endothermic
reaction and negative (– ve) value if formation is by an exothermic reaction.
Standard Reference State: It refers to thermodynamic state at which the enthalpy datum can be
set for study of reacting systems.
At standard reference state, zero value is assigned arbitrarily to the enthalpy of stable
elements. Generally, standard reference state is taken as 25°C and 1 atm, i.e. Tref = 25°C =
298.15 K, pref = 1 atm
Dissociation: It refers to the combustion products getting dissociated and thus absorbing some of
energy.
Such as, the case of carbon dioxide getting formed during combustion and subsequently
getting dissociated can be explained as below,
Combustion: C + O2 → CO2 + Heat
Dissociation: Heat + CO2 → C + O2
Thus generally, dissociation has inherent requirement of high temperature and heat.
GAS CALORIMETER
Gas calorimeter is used for estimating the heating value of gaseous fuels. It has burner with
arrangement to regulate and measure flow rate and pressure of gaseous fuel.
For precise estimation of heating value of gaseous fuels the procedure as specified by ASTM is
to be followed.
COMBUSTION OF FUEL
Combustion of fuel refers to the chemical reaction that occurs between fuel and air to form
combustion products with energy release
Generic forms of combustion equation defined on page 11
HCV & LCV formulas defined on page 13
COMBUSTION ANALYSIS
Based on chemical reactions the mass of oxygen required per kg of element can be estimated
Mass of oxygen required for constituents;
Consider the following for example, how air required for complete burning of a fuel having
85.5% carbon, 12.3% hydrogen and 2.2% ash is calculated;
1 kg of carbon shall require 8/3 kg of oxygen
1 kg of hydrogen shall require 8 kg of oxygen
Ash shall not undergo oxidation
Orsat analyser
It is also called as Orsat apparatus and is used for carrying out volumetric analysis of dry
products of combustion
• It has three flasks containing different chemicals for absorption of CO2, O2 and CO
respectively and graduated eudiometer tube connected to an aspirator bottle filled with
water.
• Flask I is filled with NaOH or KOH solution (about one part of KOH and 2 parts of water
by mass).
• KOH solution absorbs CO2.
• Flask II is filled with alkaline solution of pyrogallic acid and above KOH solution.
• This solution absorbs O2.
• Flask III is filled with a solution of cuprous chloride which absorbs CO