Thermodynamics

Therme is a Greek word which means heat and dynamic which is force. The word
thermodynamics originates from these two words. This is the classical history of thermodynamics
Thermodynamics can be defined as the study of heat, energy, energy and heat transformations and
its relation to matter. The analysis of thermal systems is achieved through the application of the
governing conservation equations, namely Conservation of Mass, Conservation of Energy (1st law
of thermodynamics), the 2nd law of thermodynamics and the property relations. Energy can be
viewed as the ability to cause changes.
Thermodynamic properties describe measurable characteristics of a substance. A knowledge of
these properties is essential to the understanding of thermodynamics.
The thermodynamic state of a system is defined by specifying a set of measurable properties
sufficient so that all remaining properties are determined. Examples of properties: pressure,
temperature, density, internal energy, enthalpy, and entropy.
One of the important fields of thermodynamics is heat transfer, which relates to transfer of heat
between two media. The concept of heat transfer is used in wide range of devices like heat
exchangers, evaporators, condensers, radiators, coolers, heaters, etc.

Thermodynamic Property
A measurable quantity that defines the condition of a system
e.g. temperature T, pressure P, mass m, volume V, density

Heat is the exchange of energy between the system and the surroundings that cannot be identified
as work.

Modes of heat transfer

Conduction: diffusion of heat due to temperature gradients. A measure of the amount of
conduction for a given gradient is the heat conductivity.
Convection: when heat is carried away by moving fluid. The flow can either be caused by
external influences, forced convection; or by buoyancy forces, natural convection. Convective heat
transfer is tightly coupled to the fluid flow solution.
Radiation: transfer of energy by electromagnetic waves between surfaces with different
temperatures, separated by a medium that is at least partially transparent to the (infrared) radiation.
Radiation is especially important at high temperatures, e.g. during combustion processes, but can
also have a measurable effect at room temperatures.
Temperature is a measure of the molecular activity of a substance. The greater the movement of
molecules, the higher the temperature. It is a relative measure of how "hot" or "cold" a substance
is and can be used to predict the direction of heat transfer. It is that property of a system that
determines whether or not a system is in thermal equilibrium with other systems. Heat flows form
hotter to colder object, until temperatures are equal and faster if better thermal contact.
The mass (m) of a body is the measure of the amount of material present in that body. The weight
(wt) of a body is the force exerted by that body when its mass is accelerated in a gravitational field.
Mass and weight are related as shown in Equation.
wt = mg/ gc
where:
wt = weight
m = mass
g = acceleration of gravity
gc = gravitational constant

The weight of a body is a force produced when the mass of the body is accelerated by a
gravitational acceleration. The mass of a certain body will remain constant even if the gravitational
acceleration acting upon that body changes.
The specific volume () of a substance is defined as the volume per unit mass, and is given the
symbol v.

The density of a substance () is defined as the mass per unit volume, and is therefore the
reciprocal of the specific volume.

Pressure is defined as the normal component of force per unit area.

Energy
Energy is the capacity for doing work. One of the very important concepts in a study of
thermodynamics is the concept of energy. Energy is a fundamental concept, such as mass or force
and, as is often the case with such concepts, is very difficult to define. Energy is defined as the
capability to produce an effect. It is important to note that energy can be stored within a system
and can be transferred (as heat, for example) from one system to another.

The energy of a system consists of internal, kinetic, and potential energies. Internal energy consists
of thermal (sensible and latent), chemical, and nuclear energies. Unless there is a chemical or
nuclear reaction the internal change of a system is due to thermal energy change. In the absence of
electric, magnetic, and surface tension effects, among others, the total energy change of a system
is expressed as

E = E2 - E1 = U + KE + PE
Internal Energy
Internal energy (U) represents the total of all the microscopic modes of energy associated with the
random motion and the internal structure of molecules. It includes the kinematic and potential
energy of all the atoms.

These different microscopic modes of energies are strongly related to macroscopic properties such
as the temperature T, pressure P, volume V, electrical charge, magnetic dipole-moment, surface
tension, etc. Internal energy U, which represents the total of all the microscopic modes of energy
in a system, can therefore be taken as a function of all the macroscopic properties, and can be
expressed as

U = U (P, T, V, electrical charge, magnetic dipole-moment, etc.)

Internal energy takes the unit of energy which, in SI units, is the joule, abbreviated J. Internal
energy per unit mass is known as specific internal energy, and it is usually given the unit J/kg.
Internal energy content of a substance divided by the amount of substance is known as molar
internal energy, and it is usually given the unit J/mol.

Note that, internal energy is an extensive property, whereas specific and molar internal energies
are intensive properties

The internal energy, U of the system, which may change, when

Heat passes into or out of the system,
Work is done on or by the system,
Matter enters or leaves the system

Closed and Open Systems

A system is defined as a quantity of matter or a region in space chosen for study. The mass or
region outside the system is called the surroundings.

The universe = The system + The surroundings

Boundary: the real or imaginary surface that separates the system from its surroundings. The
boundaries of a system can be fixed or movable. Mathematically, the boundary has zero thickness,
no mass, and no volume.

Fig. System, surroundings, and boundary

Closed system or control mass: consists of a fixed amount of mass, and no mass can cross its
boundary. But, energy in the form of heat or work, can cross the boundary, and the volume of a
closed system does not have to be fixed.
e.g. piston cylinder.

Open system or control volume: is a properly selected region in space. It usually encloses a
device that involves mass flow such as a compressor. Both mass and energy can cross the boundary
of a control volume.
e.g. water heater, car radiator, turbine,nozzle.

Isolated system: A closed system that does not communicate with the surroundings by any means.

Rigid system: A closed system that communicates with the surroundings by heat only.

Thermodynamic system
A thermodynamic system is defined as a quantity of matter of fixed mass and identity on which
attention is focused for study. Everything external to the system is the surroundings, and the system
is separated from the surroundings by the system boundaries. These boundaries may be either
movable or fixed.

Example:
In Fig.2.1 the gas in the cylinder is considered to be the system. When the cylinder is heated from
below, the temperature of the gas will increase and the piston will rise. As the piston rises, the
boundary of the system moves. Heat and work cross the boundary of the system during this
thermodynamic process, but the matter that comprises the system can always be identified.
The state of a thermodynamic system is described by its measurable or macroscopic (bulk)
properties. We can describe the state of a gas by quoting its pressure (p), volume (V), temperature
(T ), amount (n) etc. Variables like p, V, T are called state variables or state functions because their
values depend only on the state of the system and not on how it is reached

Properties of a System
Any characteristic of a system is called a property.
An intensive property is a property of a system or of a material itself. It is independent of how
much of the material is present. e.g. density, temperature, pressure, specific heat capacity
An extensive property is proportional to the amount of material. e.g. mass, energy, volume, heat
capacity
Generally, uppercase letters are used to denote extensive properties (except mass m), and lower
case letters are used for intensive properties (except pressure P, temperature T). Extensive
properties per unit mass are called specific properties, e.g. specific volume (v=V/m).

The pure substance

A pure substance is one that has a homogeneous and invariable chemical composition. It may exist
in more than one phase, but the chemical composition is the same in all phases. Thus, liquid water,
a mixture of liquid water and water vapour (steam), and a mixture of ice and liquid water are all
pure substances; every phase has the same chemical composition.

If a substance exists as vapour at the saturation temperature it is called Saturated Vapour. When
the vapour is at a temperature greater than the saturation temperature, it is said to exist as
superheated vapour. The pressure and temperature of Superheated Vapour are independent
properties, since the temperature may increase while the pressure remains constant.
 Constant-pressure change from liquid to vapour change

Work is defined as a force F acting through a displacement x, the displacement being in the
direction of the force. Thermodynamics defines work as follows: work is done by a system if the
sole effect on the surroundings (everything external to the system) could be the raising of a weight.
Work done by a system is considered positive and work done to a system is considered negative.

The unit for work in SI units is called the joule (J).

1J = 1 Nm

Heat is defined as the form of energy that is transferred across the boundary of a system at a given
temperature to another system (or the surroundings) at a lower temperature by virtue of the
temperature difference between the two systems. Another aspect of this definition of heat is that a
body never contains heat. Rather, heat can be identified only as it crosses the boundary. Thus, heat
is a transient phenomenon.

Heat transferred to a system is considered positive, and heat transferred from a system is negative.
The symbol Q represents heat.

Heat, like work, is a form of energy transfer to or from a system. Therefore, the units for heat are
the same as the units for work. In the International System the unit for heat (energy) is the joule.
Heat engines and thermal efficiencies

A Heat Engine may be defined as a device that operates in a thermodynamics cycle and does a
certain amount of net positive work through the transfer of heat from a high-temperature and to a
low-temperature body. A heat engine is a device designed to convert disordered energy into
ordered energy. A simple steam power plant is an example of a heat engine (Fig. 6.1).
Processes and Cycles
Any change a system undergoes from one equilibrium state to another is called a process, and the
series of states through which a system passes during a process is called a path. A system is said
to have undergone a cycle if it returns to its initial state at the end of the process.

Figure: To specify a process, initial and final states and path must be specified

A reversible process is defined as a process that can be reversed without leaving any trace on the
surroundings. That is, both the system and the surroundings are returned to their initial states at
the end of the reverse process. This is possible only if the net heat and network exchanged between
the system and the surroundings is zero for the combined (original and reverse) process. Processes
that are not reversible are called irreversible processes.

Reversible processes actually do not occur in nature. They are merely idealizations of actual
processes. Reversible processes can be approximated by actual devices, but they can never be
achieved. That is, all the processes occurring in nature are irreversible.
A process is called internally reversible if no irreversibilities occur within the boundaries of the
system during the process. During an internally reversible process, a system proceeds through a
series of equilibrium states, and when the process is reversed, the system passes through exactly
the same equilibrium states while returning to its initial state.

A process is called externally reversible if no irreversibilities occur outside the system boundaries
during the process. Heat transfer between a reservoir and a system is an externally reversible
process if the surface of contact between the system and the reservoir is at the temperature of the
reservoir.

Quasiequilibrium process: can be viewed as a sufficiently slow process that allows the system
to adjust itself internally and remains infinitesimally close to an equilibrium state at all times.
Quasiequilibrium process is an idealized process and is not a true representation of the actual
process. They serve as standards to which actual processes can be compared.

Advantage: the state of a system that participates in a quasi-equilibrium process can be described
with the same (small) number of macro parameters as for a system in equilibrium (e.g., for an ideal
gas in quasi equilibrium processes, this could be T and P). By contrast, for non-equilibrium
processes (e.g. turbulent flow of gas), we need a huge number of macro parameters.

Examples of quasi equilibrium processes:

Isometric: is process during which the specific volume remains constant.
Isochoric: V = const
Isobaric: is a process during which the pressure remains constant
Isobaric: P = const
Isothermal: is a process during which the temperature remains constant
Isothermal: T = const

Adiabatic: Q = 0

(Prefix iso is used to designate a process for which a particular property is constan).

The zeroth law of thermodynamics

If each of two systems is in thermal equilibrium with a third system they are in thermal equilibrium
with each other.
Zeroth law: in equilibrium with is a transitive property
That is: If system A is in equilibrium with system B and system B is in equilibrium with system C
then system A is in equilibrium with system C.

First law of thermodynamics: one of the most fundamental laws of nature is the conservation of
energy principle. It simply states that during an interaction, energy can change from one form to
another but the total amount of energy remains constant.
Energy can be changed from one form to another (including heat and work), but it is never
created or destroyed: Conservation of Energy
Let us consider the general case in which a change of state is brought about both by doing work
and by transfer of heat.
We write change in internal energy for this case as: U = q + w
For a given change in state, q and w can vary depending on how the change is carried out. However,
q +w = U will depend only on initial and final state. It will be independent of the way the change
is carried out. If there is no transfer of energy as heat or as work (isolated system) i.e., if w = 0 and
q = 0, then U = 0
U = q + w
Is mathematical statement of the first law of thermodynamics, which states that The energy of
an isolated system is constant.
The change in a systems internal energy is related to the heat and the work
U= Uf Ui = Q W
Where:
Uf = internal energy of system at end
Ui = internal energy of system at start
Q = net thermal energy flowing into system during process (Positive when system
gains heat, Negative when system loses heat)
W = net work done by the system

Second law of thermodynamics:

The second law leads to the definition of a new property called entropy

Entropy is a measure of disorder; Entropy of an isolated system Increases in any spontaneous

process. This law also predicts that the entropy of an isolated system always increases with time.

Energy has quality as well as quantity, and actual processes occur in the direction of decreasing
quality of energy. Whenever there is an interaction between energy and matter, thermodynamics
is involved. Some examples include heating and airconditioning systems, refrigerators, water
heaters, etc

It is impossible to construct a device which operating in a cycle operating in a cycle will

produce no effect other than raising of a weight and exchange of heat with a single reservoir

A reservoir that supplies energy in the form of heat is called a source, and one that absorbs energy
in the form of heat is called a sink. Thermal energy reservoirs are often referred to as heat
reservoirs since they supply or absorb energy in the form of heat.

Work can be converted to heat directly and completely, but converting heat to work requires the
use of some special devices. These devices are called heat engines
Clausius Statement: It is impossible to construct a device that operates in a cycle and produces
no effect other than the transfer of heat from a lowertemperature body to highertemperature body.
(Heat never flows spontaneously from a colder body to a hotter body).

Figure. Heat transfer from a hot container to the cold surroundings is possible; however, the reveres
process (although satisfying the first law) is impossible

KelvinPlanck Statement: It is impossible for any device that operates on a cycle to receive heat
from a single reservoir and produce a net amount of work. In other words, no heat engine can have
a thermal efficiency of 100 %.

KelvinPlanck and Clausius statements of the second law are negative statements, and a negative
statement cannot be proved. So, the second law, like the first law, is based on experimental
observations. The two statements of the second law are equivalent. In other words, any device
violates the KelvinPlanck statement also violates the Clausius statement and vice versa.

Third Law of thermodynamics:

It is impossible to reduce the temperature of a material body to the absolute zero of temperature in a finite
number of operations.

The Nernst formulation of the Third Law:

All reactions in a liquid or solid in thermal equilibrium take place with no change of entropy in
the neighborhood of absolute zero

Planck formulation
When temperature falls to absolute zero, the entropy of any pure crystalline substance tends to a
universal constant (which can be taken to be zero)
S 0 as T 0

The entropy of a perfect crystal approaches zero as temperature approaches absolute zero. (It is
impossible to cool a system to absolute zero)
Enthalpy (H, also known as heat content):
The amount of heat released or absorbed by a chemical reaction at constant pressure (as one would
do in a laboratory) is called the enthalpy or heat or reaction. Is a state function and at constant
pressure.
Enthalpy is defined as,
H = U + PV

U= Internal energy of the system

P = pressure of the system
V = volume of the system

At constant pressure (where only PV work is allowed) the change in enthalpy (H) of the system
is equal to the energy flow as heat.

H = U + PV and H = q

For reactions studied at constant pressure The terms heat of reaction and change in enthalpy are
used interchangeably. At constant pressure, the change in enthalpy is equal to the heat released or
absorbed by the system

H is negative for exothermic reactions which evolve heat during the reaction and H is positive
for endothermic reactions which absorb heat from the surroundings
Then, Exothermic: H < 0
Endothermic: H > 0

Difference between enthalpy and enthalpy change

Enthalpy (H) is the total amount of thermal energy in a substance
Enthalpy Change (H) is the energy released to or absorbed from the surroundings during a
chemical or physical change

The unit of enthalpy is the same as that of internal energy, which in general is the joules.

Entropy
Entropy is a measure of the energy associated with the random arrangement and thermal motion
of the atoms and that is therefore unavailable for external work.

The dispersal of energy and matter is described by the thermodynamic state function entropy, (S).
The greater the dispersal of energy or matter in a system, the higher is its entropy. The greater the
disorder (dispersal of energy and matter, both in space and in variety) the higher the entropy.
Adding heat to a material increases the disorder.

Entropy per unit mass is designated by s (kJ/kg.K).

If an amount of heat Q flows into a system at constant temperature, then the change in entropy is
S = Q/ T
The entropy change of a system is zero if the state of the system does not change during the process.
For example: entropy change of steady flow devices such as nozzles, compressors, turbines,
pumps, and heat exchangers is zero during steady operation.

Entropy depends on temperature and increasing temperature, will increase entropy due to increase
in molecular motion. Entropy can be transferred to or from a system in two forms: heat transfer
and mass flow

Gibbs free energy,

G is defined by G = H - TS
where H is the enthalpy, T is the temperature (in Kelvin), and S is the entropy.

Thermal efficiency: The fraction of the heat input that is converted to network output is a measure
of the performance of a heat engine and is called the thermal efficiency. (Efficiency = benefit /
cost). The thermal efficiencies of workproducing devices are low. Ordinary sparkignition
automobile engines have a thermal efficiency of about 20%, diesel engines about 30%, and power
plants in the order of 40%.

Performance or efficiency, in general, can be expressed in terms of the desired output and the
required input as Performance = desired output / required input
 FUELS
Fuel is a carbonaceous combustible substance, which on combustion liberates a large amount of
energy in the form of heat. The fossil fuels consist chiefly of carbon and hydrogen, with small
amounts of oxygen, nitrogen, sulphur, mineral matter and moisture. The composition of fuels vary
widely depending upon the type and source of the fuels. Majority of fossil fuels are being used in
transportation, industries heating and generation of electricity.

Classification
On the basis of occurrence, fuels are classified as primary and secondary fuels; Primary
fuels occur in nature and are used without processing (solid-eg Coal, wood; liquid-eg
crude oil; gaseous- eg natural gas). Secondary fuels are obtained by chemical processing
of primary fuels (solid- eg charcoal, coke; liquid-eg petrol, diesel; gaseous- eg coal and
water gas).
On the basis of physical state, fuels are classified as solid, liquid and gaseous fuels
All conventional fossil fuels, whether, solid, liquid or gaseous, contain basically carbon and
hydrogen which invariably react with the oxygen in the air forming carbon dioxide, carbon
monoxide or water vapor. The heat energy released as a result of combustion can be utilized for
heating purposes or for generation of high pressure steam in a boiler or as power from an engine
or a gas turbine.
Fossils fuels
Fossils fuels (oil, coal, natural gas) are energy rich substances that have formed from the remains
of organisms that lived 200 to 500 million years ago. During the stage of the Earths evolution,
large amount of dead organic matter had collected. Over million of years, this matter was buried
under layers of sediment and converted by heat and pressure into coal, oil and natural gas.
Chemically, fossil fuels largely consist of hydrocarbons, which are compounds of hydrogen and
carbon. Some fossils fuel also contains smaller quantities of other compounds. After the
accumulating sediments exerted increasing heat and pressure for millions of years on the ancient
organisms hydrocarbons were formed. Most common among them are petroleum, coal and natural
gas. However Geologists have identified other types of hydrocarbon rich deposits, which can serve
as fuels. Such deposits are: oil shale, tar sands and gas hydrates. However, they are not widely
used due to the fact that they are very costly to extract and refine.
Majority of fossil fuels are being used in transportation, industries heating and generation of
electricity. Crude petroleum is refined into gasoline; diesel and jet fuel that power the worlds
transportation system. Coal is mostly used in the generation of electricity (thermal power). Natural
gas is used for commercial and domestic purposes like heating, air conditioning and as fuels for
stoves and for other heating appliances.
Environmental effects of Using Fossil Fuels:
Acid rain: When fossil fuels are buried, Sulphur, Nitrogen and Carbon combine with
oxygen to form compounds known as oxide. These oxides when released into the
atmosphere, they react with water form and result in the formation of Sulhuric acid, Nitric
acid and Carbonic acid. These acids can harm biological quality of forests, soils, lakes and
streams.
Ash particles: Ash particles are the unburnt fuel particles. However with strict imposition
of Government regulations, paraben are provided to trap these particles. Petro and natural
gas generate less ash particles than coal, diesel or gasoline.
Global warming: Carbon dioxide is a major byproduct of fossil combustion and this gas is
known as green hour gas. Green hour gas absorbs solar heat reflected off the earths surface
and retains this heat, keeping the Earth warm and habitat for living organisms. Rapid
industrialization between 19th and 20th centuries, however has resulted in increasing
fossils fuel emissions, raining the percentage of carbon dioxide by about 28%. This drastic
increase has led to global warming that could cause environmental problems, including
disrupted weather patterns and polar ice cap melting.

Solid Fuels

Physical properties
Heating or calorific value
Moisture content
Volatile matter
Ash

Calorific Value
The quality of a fuel is determined by the amount of energy released per unit mass or
volume referred to as calorific value.

Moisture content
% of moisture in fuel (0.5 10%)
Reduces heating value of fuel
Weight loss from heated and then cooled powdered raw coal
Volatile matter
Methane, hydrocarbons, hydrogen, CO, other
Typically 25-35%
Easy ignition with high volatile matter
Weight loss from heated then cooled crushed coal
Ash
Impurity that will not burn (5-40%)
Important for design of furnace
Ash = residue after combustion
Chemical properties
Chemical constituents: carbon, hydrogen, oxygen, sulphur
Storage, Handling & Preparation
Storage to minimize carpet loss and loss due to spontaneous combustion
Reduce carpet loss: a) a hard surface b) standard concrete/brick storage bays
Coal preparation before use is important for good combustion

Coal
Coal was known since ancient times, but only used when available on site; most often, a charcoal,
a similar stuff obtained from wood, was used (charcoal leaves less ashes, but yields less heat also).
Coal is a compact black or dark-brown sedimentary rock (a mixture, not a mineral) formed some
300 million years ago, by high pressure and temperature anaerobic decomposition of dead plants
(mainly ferns), but the degree of metamorphosis varies a lot and several types of coal can be found
today;: from more to less cooking: anthracite, bituminous coal, lignite, and peat. Almost 27350
billion metric tones of known coal deposits occur on our planet. Out of which about 56% are
located in Russia, 28% in USA and Canada. India has about 5% of worlds coal reserve and that
too not of very good quality in term of heat capacity. West Bengal, Jharkhand, Orissa, Andhra
Pradesh, Madhya Pradesh and Maharastra are the major coal producing states of India.

Physical properties of coal include the heating value, moisture content, volatile matter and ash.
The chemical properties of coal refer to the various elemental chemical constituents such as
carbon, hydrogen, oxygen, and sulphur.

Types Coals are classified in a maturity rank according to age and fixed carbon content:
Anthracite is the hardest, purest, more brittle and scarce coal; too precious for a fuel (it is
used for chemicals). It is a dense black solid, with brilliant lustre and very low moisture.
Bituminous coal is a dense black solid that frequently contains bright bands with a brilliant
lustre. It has some 2-10% of trapped water. Volatile matter range is 10-30%, and the typical
heating value is 30 MJ/kg.
Lignite, or brown coal, is the most abundant form of coal. It has some 40-60% of trapped
water. Sometimes, the remaining texture of the original vegetation can be discerned.
Volatiles may reach up to 30% in some lignite, and the typical heating value is 15 MJ/kg.
Peat has some 70-90% of trapped water, and it is not used as commercial fuel (it must be
dried to at least 30% in water to be burned, and was used in open fires). Plant
decomposition has progressed only partially, and it is possible sometimes to identify the
remains of individual leaves in peat, cellulose being still the main component.
Lignite is the youngest coal from geological perspective. It is a soft coal composed mainly of
volatile matter and moisture content with low fixed carbon. Fixed carbon refers to carbon in its
free state, not combined with other elements. Volatile matter refers to those combustible
constituents of coal that vaporize when coal is heated.
Since coal consumption in its raw solid form is cumbersome, several fluidification processes have
been developed:
Pulverisation by mechanical grinding.
Gasification by pyrolysis.
Distillation by pyrolysis.
Two types of coal analysis are commonly used:
Proximate analysis, specifying: fixed coal + volatile coal + ash + water.
Ultimate analysis, specifying: water + percentage of C, H, O, N, and S.

Wood
Wood is the hard, porous, fibrous substance found beneath the bark of trees and shrubs. Wood is
used for timber (construction), for paper making, and as a fuel (up to 30% of wood production in
industrialised countries, mostly the debris, but up to 90% in developing countries). Hard wood
(resistant to sawing) comes from deciduous broad-leafed trees: oak, elm and fruit trees. Soft woods
come from pine, cedar, fir. Paper is made from chemically and mechanically processed wood fibres
(typically 30 mm in diameter and 2 mm long) which are self-binding when dried from a wet state.
Composition Wood is a natural composite material consisting of hollow polymer fibres in a
polymer matrix. The hollow fibres are tubular cells (most of them dead), with cellulosic walls
(70% cellulose and 30% lignin) holding aqueous solutions in the inside space (water content varies
a lot, from 60%wt in freshly cut trees, to 5%wt in artificially-dried furniture-wood); the matrix is
made of hemicellulose and lignin. Trees are cut in winter to minimise initial water content.

Analysis of Coal
There are two methods: ultimate analysis and proximate analysis.
The ultimate analysis determines all coal component elements, solid or gaseous and the proximate
analysis determines only the fixed carbon, volatile matter, moisture and ash percentages. The
ultimate analysis is determined in a properly equipped laboratory by a skilled chemist, while
proximate analysis can be determined with a simple apparatus.

Proximate and Ultimate Analysis of Coal

Proximate analysis indicates the percentage by weight of the Fixed Carbon, Volatiles, Ash, and
Moisture Content in coal. The proximate analysis of coal is an empirical procedure for analysis of
coal in order to list the composition in terms of the following items, all expressed as percentages
by weight of coal The different items are Moisture, Volatile matter, Ash and Fixed carbon.
Moisture: The loss of weight when coal is heated in an oven at 105 degree C.
Volatile matter: The loss in weight when coal sample is heated in a covered crucible for about
seven minutes at 950 centigrade minus the weight of the moisture.
Ash: The weight of residue obtained when the sample of coal is subjected to complete combustion
in a muffle furnace at 700-750 degree centigrade.
Fixed carbon: Calculated as 100-the sum of moisture, Volatile matter and ash already obtained.
FC= 100-(M+VCM +A)
(FC -Fixed carbon M-Moisture VCM-Volatile combustible matter A-Ash)

Ultimate Analysis of Coal

The ultimate analysis of coal gives the composition as the percentage by weight of the various
elements such as C, H, N, O, S, etc. and the ash. The ultimate analysis provides the necessary data
required for material balance in the combustion of coal. The analysis is carried out by elaborate
and standard chemical techniques. The carbon dioxide, water and sulphur dioxide formed by
burning coal in a sufficient supply of oxygen determine respectively the amounts of carbon,
hydrogen and sulphur in coal.

Calorific Value
The quality of a fuel is determined by the amount of energy released per unit mass or volume
referred to as calorific value.
Calorific value of a fuel is the amount of heat liberated when a unit mass or a unit volume
of the fuel is burnt completely in air or oxygen.
Fuels generally contain hydrogen in addition to carbon. During combustion, the hydrogen
is converted to steam.
In the determination of calorific value of the fuel if the products of combustion are cooled
to ambient temperature (room temperature), the latent heat of steam is also included. This
is referred to as gross calorific value (GCV) or higher calorific value.
In practice, the products of combustion are allowed to escape and the amount of heat
realized is lesser than the GCV (since the latent heat of vaporization is not released). This
is net calorific value (NCV) or lower calorific value.

Gross Calorific value is the amount of heat liberated when a unit mass or a unit volume of the
fuel is burnt completely in air or oxygen and the products of combustion are cooled to ambient
temperature.
Net Calorific value is the amount of heat liberated when a unit mass or a unit volume of the fuel
is burnt completely in air or oxygen and the products combustion are allowed to escape.

Liquid fuels
Crude oil
Crude petroleum is refined into gasoline; diesel and jet fuel that power the worlds transportation
system. Today, fossil fuels are considered to be non-renewable for the reason that their
consumption rate is far in excess of the rate of their formation.

Crude oil, also called petroleum, is a thick liquid found in underground rock formations. The
petroleum industry extracts crude oil out of the ground and then refines it into products such as
gasoline. Crude oil contains a complex mixture of compounds made of carbon chains with
hydrogen molecules attached to each link in the chain. Extracted crude oil also contains small
amounts of sulfur, oxygen, and nitrogen compounds mixed with the hydrocarbons. The principle
of oil refining is to remove crude oils impurities, that is, anything that is not a hydrocarbon. The
following nations hold the largest oil reserves, in order: Saudi Arabia, Canada, Iran, Iraq, United
Arab Emirates, Kuwait, Venezuela, Russia, Libya, and Nigeria. Crude oil is not used directly as a
fuel but as a feedstuff for the petrochemical factories to produce commercial fuels, synthetic
rubbers, plastics, and additional chemicals.

Petroleum
Convenience of petroleum or mineral oil and its greater energy content as compared to coal on
weight basis has made it the lifeline of global economy. Petroleum is cleaner fuel when compared
to wood or coal as it burns completely and leaves no residue. Petroleum is unevenly distributed
like any other mineral. There are 13 countries in the world having 67% of the petroleum reserves
which together form the OPEC (Organization of Petroleum Exporting Countries). Six regions in
the world are rich in petroleum USA, Mexico, Russia and West Asian countries. Saudi Arabia
has one fourth of the world oil reserves. The oil bearing potential of India is estimated to be above
one million square kilometers is about one third of the total geographic area. Northern plains in
the Ganga-Brahmaputra valley, the coastal strips together with their off-shore continental shelf
(Bombay High), the plains of Gujarat, the Thar Desert and the area around Andaman and Nicobar
Islands are the places where oil reserves exist.

Diesel
Diesel fuel is any liquid fuel used in diesel engines, originally obtained from crude-oil distillation
(petro diesel), but alternatives are increasingly being developed for partial or total substitution of
petro diesel, such as biodiesel (from vegetal oils), and synthetic diesel (usually from a gas fuel
coming from coal reforming or biomass, also named gas to liquid fuels, Gas to liquid (GTL)). In
all cases, diesel nowadays must be free of sulfur.
Kerosene
Kerosene is a crude-oil distillate similar to petro diesel but with a wider-fraction distillation. Jet
fuel is kerosene-based, with special additives. Jet fuel is used for commercial (Jet A-1, Jet A, and
Jet B) and military (JP-4, JP-5, JP-8) jet propulsion; aviation gasoline (avgas) is used to power
piston-engine aircraft. Jet A-1 comprises hydrocarbon chains with 9 to 15 carbon atoms. Jet B
(also named JP-4, with composition distribution from 5 to 15 carbon chains), is used in very cold
weather, and in military aircraft.

Properties of Liquid Fuels

Liquid fuels like furnace oil are predominantly used in industrial application. The various
properties of liquid fuels are given below.

Density: This is defined as the ratio of the mass of the fuel to the volume of the fuel at a reference
temperature of 15C. Density is measured by an instrument called hydrometer. The knowledge of
density is useful for quantity calculations and assessing ignition quality. The unit of density is
kg/m3.

Specific gravity: This is defined as the ratio of the weight of a given volume of oil to the weight
of the same volume of water at a given temperature. The density of fuel, relative to water, is called
specific gravity. The specific gravity of water is defined as 1. Since specific gravity is a ratio, it
has no units.

Viscosity: The viscosity of a fluid is a measure of its internal resistance to flow. Viscosity depends
on temperature and decreases as the temperature increases. Any numerical value for viscosity has
no meaning unless the temperature is also specified. Viscosity is measured in Stokes / Centistokes.
Sometimes viscosity is also quoted in Engler, Saybolt or Redwood. Each type of oil has its own
temperature - viscosity relationship. The measurement of viscosity is made with an instrument
called Viscometer.

Flash Point: The flash point of a fuel is the lowest temperature at which the fuel can be heated so
that the vapour gives off flashes momentarily when an open flame is passed over it. Flash point
for furnace oil is 66o C.

Pour Point: The pour point of a fuel is the lowest temperature at which it will pour or flow when
cooled under prescribed conditions. It is a very rough indication of the lowest temperature at which
fuel oil is readily pumpable.

Specific Heat: Specific heat is the amount of kcals needed to raise the temperature of 1 kg of oil
by 1o C. The unit of specific heat is kcal/kgo C. It varies from 0.22 to 0.28 depending on the oil
specific gravity. The specific heat determines how much steam or electrical energy it takes to heat
oil to a desired temperature. Light oils have a low specific heat, whereas heavier oils have a higher
specific heat.
Ash Content
The ash value is related to the inorganic material in the fuel oil. The ash levels of distillate fuels
are negligible. Residual fuels have more of the ash-forming constituents. These salts may be
compounds of sodium, vanadium, calcium, magnesium, silicon, iron, aluminum, nickel, etc.

Carbon Residue
Carbon residue indicates the tendency of oil to deposit a carbonaceous solid residue on a hot
surface, such as a burner or injection nozzle, when its vaporisable constituents evaporate. Residual
oil contains carbon residue ranging from 1 percent or more.

Gaseous Fuels
Gas fuels are the most convenient because they require the least amount of handling and are used
in the simplest and most maintenance-free burner systems.Fuel should be compared based on the
net calorific value. This is especially true for natural gas, since increased hydrogen content results
in high water formation during combustion.

Classification of gaseous fuels

(a) Fuels naturally found in nature
- Natural gas
- Methane from coal mines
(b) Fuel gases made from solid fuel
- Gases derived from coal
- Gases derived from waste and biomass
- From other industrial processes
(c) Gases made from petroleum
- Liquefied Petroleum gas (LPG)
- Refinery gases
- Gases from oil gasification
(d) Gases from some fermentation

Advantages of gaseous fuels

Least amount of handling
Simplest burners systems
Burner systems require least maintenance
Environmental benefits and other emissions

Natural gas
Methane is the main constituent of Natural gas and accounting for about 95% of the total volume.
Other components are: Ethane, Propane, Butane, Pentane, Nitrogen, Carbon Dioxide, and traces
of other gases. Very small amounts of sulphur compounds are also present.
Natural gas mainly consists of Methane (CH4) along with other inflammable gases like Ethane and
propane. Natural gas is least polluting due to its low Sulphur content and hence is cleanest source
of energy. It is used both for domestic and industrial purposes. Natural gas is used as a fuel in
thermal plants for generating electricity, as a source of hydrogen gas in fertilizer industry and as a
source of carbon in tyre industry. The total natural gas reserves of the world is about 600 000
billion m3 , out of this Russia has 34%, Middle East 18%, North America 17%, Africa and Europe
9% each and Asia 6%. Annual production of natural gas is about 1250 billion m3 and hence it is
expected to last for about 50-100 years. In India gas reserves are found in Tripura, Jaisalmer, off
shore areas of Bombay and Krishna-Godavari Delta.
Natural gas is a high calorific value fuel requiring no storage facilities. It mixes with air readily
and does not produce smoke or soot. It has no sulphur content. It is lighter than air and disperses
into air easily in case of leak.
LPG
LPG may be defined as those hydrocarbons, which are gaseous at normal atmospheric pressure,
but may be condensed to the liquid state at normal temperature, by the application of moderate
pressures. Although they are normally used as gases, they are stored and transported as liquids
under pressure for convenience and ease of handling. Liquid LPG evaporates to produce about 250
times volume of gas. LPG is a predominant mixture of propane and Butane with a small percentage
of unsaturates (Propylene and Butylene) and some lighter C2 as well as heavier C5 fractions.
Included in the LPG range are propane (C3H8), Propylene(C3H6), normal and iso-butane (C4H10)
and Butylene(C4H8)

Liquid Bio-Fuels
They are obtained by subjecting organic materials to one of the various chemical or physical
processes to produce a usable, combustible liquid fuel. Bio fuels such as vegetable oils or ethanol
are often processed from industrial or commercial residues such as biogas or from energy crops
grown specially for this purposes.
Biogas is obtained by an aerobically (without air) digesting organic material to produce a
combustible gas known as methane. Animal waste and municipal waste are two common feed
stocks for an aerobic digestion. At present biogas technology provides an alternative source of
energy in rural India for cooking. It is particularly useful for village households that have their
own cattle. Through a simple process cattle dung is used to provide the gas. The residual dung is
used as manure. The charge from the biogas generation consists of dung and waste in the form of
slurry. The fermentation is carried out between 35 to 500C. The average composition of biogas is
methane 55%. Hydrogen 7.4%, Carbon dioxide 39%, Nitrogen 2.6%, Waster- traces. The average
gross calorific value of the gas is 5300 kilocals /cubic meters

Biodiesel
Biodiesel is a biomass-derived fuel, safer, cleaner, renewable, non-toxic and biodegradable direct
substitute of petroleum diesel in compression-ignition engines, but more expensive. Biodiesel is a
mono-alkyl-ester mixture obtained from natural oils, currently produced by a process called
transesterification, where a new or used oil (sunflower, colza, soybean, or even animal fat) is first
filtered, then pre-processed with alkali to remove free fatty acids, then mixed with an alcohol
(usually methanol) and a catalyst (usually sodium or potassium hydroxide); the oil's triglycerides
react to form esters and glycerol, which are then separated from each other and purified.

Biomass
The traditional biomass through the ages has been wood. Besides the biofuel production here
discussed, biomass is also used as a fertiliser (compost), paper industry and other chemical stuff,
building (e.g. straw in adobe and roofs, timber), etc. Biomass is synonymous of vegetable matter
used as fuel (biofuel), either grown for that purpose, or recovered from other industries waste
(forestry, farming, food industry); urban and animal waste might be included too, but its
importance is marginal.

Combustion
Principle of Combustion
Combustion refers to the rapid oxidation of fuel accompanied by the production of heat, or heat
and light. Complete combustion of a fuel is possible only in the presence of an adequate supply of
oxygen. Oxygen (O2) is one of the most common elements on earth making up 20.9% of our air.
Rapid fuel oxidation results in large amounts of heat. Solid or liquid fuels must be changed to a
gas before they will burn. Usually heat is required to change liquids or solids into gases. Fuel gases
will burn in their normal state if enough air is present. Most of the 79% of air (that is not oxygen)
is nitrogen, with traces of other elements. Nitrogen is considered to be a temperature reducing
dilutant that must be present to obtain the oxygen required for combustion. Nitrogen reduces
combustion efficiency by absorbing heat from the combustion of fuels and diluting the flue gases.
Nitrogen reduces the combustion efficiency and forms NOx at high temperatures. Carbon forms
CO2 and CO resulting in less heat production.

The objective of good combustion is to release all of the heat in the fuel. This is accomplished by
controlling the "three T's" of combustion which are
(1) Temperature high enough to ignite and maintain ignition of the fuel,
(2) Turbulence or intimate mixing of the fuel and oxygen
(3) Time sufficient for complete combustion.

Water vapor is a by-product of burning fuel that contains hydrogen and this robs heat from the flue
gases.

All conventional fossil fuels, whether, solid, liquid or gaseous, contain basically carbon and
hydrogen which invariably react with the oxygen in the air forming carbon dioxide, carbon
monoxide or water vapour. The heat energy released as a result of combustion can be utilized for
heating purposes or for generation of high pressure steam in a boiler or as power from an engine
or a gas turbine.
The solid fuels are burned in beds or in pulversied from suspended in the air stream. The liquid
fuels are burned either by vaporising and mixing with air before ignition, when they behave like a
gaseous fuel. The gaseous fuels are either burned in burners when the fuel and air are premixed or
the fuel and air flow separately in to a burner or a furnace and simultaneously mix together as
combustion proceeds.
The Kg-mole or gram-mole is widely used in combustion calculations as a unit of weight. The
molecular weight of any substance in kg represents one kilogram mole or 1K mole. 1Kmol of
hydrogen has a mass of 2.016Kg and 1Kmol of carbon has a mass of 12Kg

Internal Energy of Combustion

It is defined as the difference between the internal energy of the products and the internal energy
of the reactants when complete combustion occurs at a given temperature and pressure.
Combustion efficiency
It is defined as the ratio of ideal fuel-air to the actual fuel-air ratio

Enthalpy of reaction
Enthalpy of a reaction is 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. For
combustion process, the enthalpy of a reaction is usually referred to as the enthalpy of
combustion it is obviously a very useful property for analyzing the combustion processes of
fuels. However there are so many different fuels and fuel mixtures that is not practical to list
enthalpy of combustion values for all possible cases. Besides, the enthalpy of combustion is not of
much use when the combustion is incomplete. Therefore a more practical approach would be have
a more fundamentally property to represent the chemical energy of an element or compound at
some reference state. This property is the enthalpy of formation which can be viewed as the
enthalpy of a substance at a specified state due to its chemical composition.
Every chemical species has a certain amount of "heat content," or enthalpy, H, which cannot be
measured. However, differences in enthalpy can be measured. The net energy change for a reaction
performed at constant pressure is the enthalpy change for the reaction. This enthalpy change, H,
has units kJ/mol
If energy is given off during a reaction, such as in the burning of a fuel, the products have less heat
content than the reactants and H will have a negative value; the reaction is said to be exothermic.
If energy is consumed during a reaction, H will have a positive value; the reaction is said to be
endothermic.

Stoichiometric equation
A balanced chemical equation for complete Combustion of the reactions with no excess air in the
product is known as a stiochiometric equation. A stiochiometric mixture of the reactants is one in
which the molar proportions of the reactants are exactly as given by the stiochiometric coefficients,
so that no excess of any constituent is present.
In general a chemical reaction may be written as
aA + bB - cC + dD
Where the reactants A and B react to form the products C and D. The small letters a, b, c and d are
known as the stiochiometric coefficients.
The minimum amount of air required for the complete combustion of a fuel is known as theoretical
air. However in practice it is difficult to achieve complete combustion with theoretical air.
Therefore fuel requires some excess air for different application and may vary from 5% ~ 20% and
in gas turbine it may go up to 400% of theoretical quantity.