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Thermodynamics is a branch of science that deals with energy in all its forms and the
laws governing the transformation of energy from one form to another. The form of energy
are mechanical, thermal or heat, chemical, electrical etc.
Thermodynamics deals with the behavior of gases and vapours i.e., the working
substances when subjected to variation of temperature and pressure and the relationship
between heat energy and mechanical energy commonly referred to as work.
Energy transformation takes place when a substance undergoes a change from one
condition to another in a process. The processes are heating or cooling and expansion or
compression in the cylinder or passages with or without production or supply of mechanical
work. The laws of thermodynamics based on the experimental results obtained from the study
of gases and vapours are useful in the design of boilers, steam engines, steam turbines, I.C
engines, gas turbines, refrigerating machines and air compressors.
Working substances or thermodynamic medium is one which has the ability to
receive, store and reject energy as required by the particular process. The medium may be in
any one of the four physical states namely solid, liquid vapour and gaseous. The vapours and
gaseous substances are sometimes termed together as gases.
Matter may be defined as that which has mass and occupies space. It is made up of a
large number of particles known as molecules or atoms. Matter may exist as solid, liquid or
gas. When enough energy is added then solid may be converted into liquid phase and again if
sufficient energy is added to the liquid phase to overcome the binding force between the
molecules, the molecules breakaway from each other and the vapour and gaseous phase
results. Thus energy has to be defined more appropriately as that which causes some effects
on matter rather than the capacity to do work. In most of the work producing and work
absorbing devices the working substance is a gas or vapour and sometimes vapour and liquid
in equilibrium. Example: Steam in steam engine, Freon or Ammonia in refrigerator, Air-fuel
mixture in I.C engine.
Engineering thermodynamics:
It deals with the laws that govern the conversion of one form of energy into another.
The scope is restricted to the study of heat and work and the conversion of one into the other.
Thermodynamic laws are applied to the work producing and work absorbing devices in order
to understand their functioning and improve their performance. In these days of fuel shortage
and energy crisis the importance of such a study is well appreciated. Also there is need to
study new work producing devices using nonconventional energy sources like solar energy.
Efficient practical apparatus have to be designed and developed using such energy sources.
This will be possible only with a basic understanding of thermodynamics.
The low pressure steam leaving the turbine now enters into a condenser, where it is
cooled and condensed back to water. The condensate is then raised to the boiler pressure by a
boiler feed pump and sent back to the boiler as feed water. Steam power plant is also
provided with an air pre heater to supply hot air to the combustion chamber. Air pre heater
makes use of heat of flue gases to heat the air.
2. I.C Engines:-
Air is used as working substance in case of I.C Engines.
3. Gas turbines:-
In case of gas turbines the combustion of the fuel is carried out with compressed air in
a separate combustion chamber. The products of the combustion enter the turbine and impart
their momentum to the turbine blades before being exhausted. Gas turbine units are used in
very small aircrafts for propulsion through a propeller. These are also used in stationary gas
turbine power plants for power generation.
Thermodynamic system:
In the analysis of energy interaction, it becomes convenient to define and restrict
study to a region. Such a specified region where transfer of energy and/or mass is to be
studied is known as system.
a) Isolated system: These systems cannot have either energy or mass transfer with the
surroundings. This system is of purely theoretical interest to study and analyse
thermodynamic principle and laws.
b) Control mass or closed system: Across the boundary of a closed system the transfer of
energy (Work and/or heat) takes place but transfer of mass does not takes place. E.g.: Piston
and cylinder.
Figure shows a gas confined between a cylinder and piston. The gas is considered as
the system. The enveloping broken line is the system boundary. When the gas is heated, it
will expand and the piston will rise. Then the boundary of the system moves. It is seen that
heat energy flows into the system and as the piston rises mechanical work is done by the
system. The reverse will happen, if instead, the gas is cooled. The system has the following
characteristics:
i) It has fixed mass, also called control mass.
ii) Energy both in the form of heat and work can cross the boundary.
iii) The boundary can move.
c) Control volume or open system: In this system mass and energy both may be transferred
between the system and the surroundings. E.g.: Gas turbine, Steam turbine, Compressor,
Boiler etc.
Fig. An Open System with one inlet and one exit
Figure shows a turbine as the open system. Here the mass of the system is not fixed.
In this case we specify the system in the form of a control volume that encloses the
equipment. The boundary that remains fixed in space, enveloping the control volume is called
the control surface. The control volume may be either stationery or moving in space. The
system has the following characteristics:
i) The system has fixed volume called control volume and a fixed control surface.
ii) Both heat and work can flow across the control surface.
iii) Mass can also enter and leave the control surface.
Thermodynamic properties:
The variables which determine state or exact condition of a substance or system is
called as its properties. The various properties of thermodynamic system are pressure,
temperature, specific volume, internal energy, enthalpy, entropy, etc.
a) Pressure: Pressure may be defined as normal force per unit area. In S.I system the unit of
pressure is pascal (Pa).
b) Volume: The space occupied by the substance is called volume. It is measured in m3.
1litre = 1000cc = 10-3m3
c) Specific volume: Specific volume of a substance is its volume per unit mass. Its unit is
m3/kg.
Density of a substance is its mass per unit volume. Unit - kg /m3.
Specific volume
e) Energy: Energy may be defined as the capacity a body possesses for doing work. All
forms of energy are mainly classified as i) Stored energy ii) Transient energy or energy in
transition or transient energy.
Stored energy is the energy possessed by a system within its boundaries. E.g., K.E,
P.E, and I.E.
Transit energy is the energy possessed by a system which is capable of crossing its
boundaries. E.g. Heat and Work.
f) Heat: Heat is defined as the energy transferred without transfer of mass across the
boundary of a system due temperature difference between the system and the surroundings.
The energy in transition is called heat. Heat energy cannot be stored in a system. Unit for heat
and any other form of energy is joule (J).
Heat flow into a system is positive and heat flow out of a system is negative.
g) Work: Work is defined as the energy transferred without transfer of mass across the
boundary of a system because of intensive property difference other than temperature that
exists between the system and the surroundings. Work also cannot be stored in a system. Unit
of work done is N-m or joule.
Work done by the system is positive and work done upon the system is negative.
h) Internal energy: It is the energy possessed by a body or system due to its molecular
arrangement and motion of the molecules. It is the sum of internal K.E and internal P.E of the
molecules. It is a function of temperature and can be increased or decreased by adding or
subtracting heat to or from the substance. Absolute value of the I.E cannot be measured but
change in I.E can be measured when a substance undergoes a change of state from 1 to 2. It
can be expressed in general way as;
du = u2 – u1
i) Enthalpy: Enthalpy is nothing but total heat and heat content. Enthalpy or total heat =
Internal energy + Product of absolute pressure and volume.
h = u + pv
Absolute value of enthalpy cannot be measured, only change in enthalpy can be
measured.
1.Extensive property: The properties of the system, whose value for the entire system is
equal to the sum of their values for the individual parts of the system, are called extensive
properties. These properties depend on the mass of the system. E.g. K.E, P.E, I.E, Total
volume, Total mass, Enthalpy, etc.
2. Intensive properties: It is the property of the system whose value for the entire system is
not equal to the sum of their values for the individual parts of the system. This property does
not depend on the mass. E.g., temperature, Pressure, Density, Specific volume, etc.
Thermodynamic process:
When one or more of the thermodynamic properties of a system change, we say that
there is a change of state of the system. This change of state of a system is referred to as
thermodynamic process.
Since the state of a system can be defined only when it is in equilibrium, we say that a
process is any transformation of a system from one equilibrium state to another. A process
occurs as a result of heat and work interaction between system and surroundings.
In the Fig above 1 is a state and 2 is another state. 1-2 is a process. The curve or line
connecting two states is the path. The change of state from1 to 2 can be attained by different
processes which can be shown by different paths.
It can be seen that state 2 may be reached from state 1 by following many different
paths such as A or B or C. The state 2 irrespective of the path will have same values of
properties p2 and V2. Thus the values of properties of system in a given state are, therefore
independent of the path followed to reach the state and are called point functions.
The converse of the above is also true viz, any quantity whose change is
independent of the path is a point function and hence is a property. Thermodynamic
properties are point functions, since for a given state; there is a definite value for each
property. The differentials of point functions are exact or perfect differentials and the
integration is simply
2 2
∫1 𝑑𝑝 = 𝑝2 – 𝑝1 And ∫1 𝑑𝑣 = 𝑉2 – 𝑉1
The process is a path. The quantity, the value of which depends on the path followed
during a change of state is a path function. In the illustration above, the area under 1-A-2 or
1-B-2 or 1-C-2 are different and therefore the quantity which depends on path is also
different for different paths. Work and heat are path functions. For a path function, we can
write,
2 2
∫1 𝑑𝑊 = 1W2 or W1-2 And ∫1 𝑑𝑄 = 1𝑄2 or Q1-2
Here dW and dQ are inexact or imperfect differential.
NOTE: Area under P-V diagram is WORK and area under T-s diagram is HEAT.
Quasi-static process:
Properties describe the state of a system only when it is in thermodynamic
equilibrium. A process takes place when the equilibrium is disturbed. The intermediate states
of a system along the path of a process are explained by quasi-static process.
Thermodynamic cycle:
When a number of processes in sequence bring the system back to its initial state, then
the system is said to have undergone a thermodynamic cycle.
In Fig 1-2-3-4-1 is cycle consisting of four processes. The change in value of any
property is zero for a cyclic process.
∮ 𝑑𝑝 = 0, ∮ 𝑑𝑉 = 0,
Thermodynamic equilibrium:
A system is in thermodynamic equilibrium if it is not capable of a finite spontaneous
change to another state. According to this definition all thermodynamic properties have the
same value at all points of the system in equilibrium. Complete thermodynamic equilibrium
implies the following:
i) Thermal equilibrium
ii) Mechanical equilibrium
iii) Chemical equilibrium
When a system is in contact with its surroundings across a diathermal wall and if
there is no spontaneous change in any of the properties of the system, the system is said to
exist in thermal equilibrium with its surroundings. For thermal equilibrium to exist between
two systems or between a system and the surroundings, the temperature must be same.
A system is said to be in mechanical equilibrium, when there is no unbalanced force
acting on any part of the system or the system as a whole. For mechanical equilibrium to exist
between a system and the surroundings the pressure must be same.
A system is said to be in chemical equilibrium, when there is no chemical reaction
within the system and also there is no movement of any chemical constituent from one part of
Temperature scales:
We know that temperature is a function of resistance R, emf E, pressure P, volume V
and radiation intensity I in case of electric resistance thermometer, thermocouple, constant
volume thermometer, constant pressure thermometer and radiation thermometer respectively.
In establishing a temperature scale we need a relationship between the temperature and the
thermometric property. For the purpose the function ‘f’ can be expressed in the following
different mathematical forms:
Direct proportionality : t = Ax
Linear relation : t = ax + b
Quadratic relation : t = αx + βx + ϒ
2
Similarly the absolute temperature in Fahrenheit scale is called degree Rankine (R),