BASIC CONCEPTS AND DEFINITIONS

DEFINITION OF THERMODYNAMICS
Thermodynamics may be defined as follows :
Thermodynamics is an axiomatic science which deals with the relations among heat,
work and properties of system which are in equilibrium. It describes state and changes in state of
physical systems.
Or
Thermodynamics is the science of the regularities governing processes of energy conversion.
Or
Thermodynamics is the science that deals with the interaction between energy and material
systems.
FOUR LAWS OF THERMODYNAMICS

Thermodynamics, basically entails four laws or axioms known as Zeroth, First, Second and
Third law of thermodynamics.

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The First law law of conservation of energy, quantity of energy, concept of internal energy.
The Zeroth law -- deals with thermal equilibrium and establishes a concept of temperature.

The Second law indicates the limit of converting heat into work and introduces the principle of
increase of entropy. (quantity and quality of energy).
The Third law defines the absolute zero of entropy.
These laws are based on experimental observations and have no mathematical proof. Like all
physical laws, these laws are based on logical reasoning.
MACROSCOPIC AND MICROSCOPIC POINTS OF VIEW
Thermodynamic studies are undertaken by the following two different approaches.
1. Macroscopic approach(Macro mean big or total)
2. Microscopic approach(Micro means small)

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THERMODYNAMIC SYSTEMS
A Thermodynamic system is defined as a quantity of matter or a region in space whose
behaviour is being investigated.
Surroundings
Everything external to the system is defined as surroundings. In its usual context the term
surroundings is restricted to the regions in the immediate vicinity , which has a detectable
influence on the system.
Boundary
Boundary is the surface which separates the system from its surroundings. It may be fixed or
moving and real or imaginary.
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TYPES OF THERMODYNAMIC SYSTEMS

There are three types of thermodynamic systems based on mass and energy transfer
a) Closed System
b) Open System and
c) Isolated System

a) Closed System
In closed system (also known as a control mass) attention is focused on a fixed mass.

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Energy in the form of heat and work can cross the boundary of the system. But there is no mass
flow across the boundary. Hence, the possibility of change in volume is always there in the

closed systems.

Examples: A piston with a cylinder arrangement, a cup of coffee

b) Open System
In open system, or a control volume, both matter and energy can cross the boundary. Here, the
behaviour of a fixed region in space called control volume is investigated and hence, there is no
change in volume. The surface of the control volume is known as control surface.

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Examples: compressor, turbine, nozzle and Water heater

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The boundaries of a control volume are called a control surface, and they can be real or
imaginary

c) Isolated System
An isolated system is that system which exchanges neither energy nor matter with any other
system or with environment.
Examples: Universe,Thermoflask

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Adiabatic System
An adiabatic system is one which is thermally insulated from its surroundings. It can,however,

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exchange work with its surroundings. If it does not, it becomes an isolated system.

TYPES OF SYSTEM BASED ON PHASE CHANGE

Phase.

A phase is a quantity of matter which is homogeneous throughout in chemical composition and

physical structure.
Homogeneous System
A system which consists of a single phase is termed as homogeneous system.
Examples : Mixture of air and water vapour, water plus nitric acid and octane plus heptane.
Heterogeneous System
A system which consists of two or more phases is called a heterogeneous system.
Examples :Water plus steam, ice plus water and water plus oil.
THERMODYNAMIC EQUILIBRIUM
A system is in thermodynamic equilibrium , if the temperature and pressure at all points
are same ; there should be no velocity gradient ; the chemical equilibrium is also necessary.
Systems under temperature and pressure equilibrium but not under chemical equilibrium are
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sometimes said to be in metastable equilibrium conditions. It is only under thermodynamic

equilibrium conditions that the properties of a system can be fixed. Thus for attaining a state of
thermodynamic equilibrium the following three types of equilibrium states must be achieved :
1. Thermal equilibrium. The temperature of the system does not change with time and
has same value at all points of the system.

2. Mechanical equilibrium. There are no unbalanced forces within the system or between

the surroundings. The pressure in the system is same at all points and does not change with

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respect to time.

3. Chemical equilibrium. No chemical reaction takes place in the system and the chemical
composition which is same throughout the system does not vary with time.
PROPERTIES OF SYSTEMS
A property of a system is a characteristic of the system which depends upon its state, but
not upon how the state is reached. There are two sorts of property:
1. Intensive properties. These properties do not depend on the mass of the system.
Examples : Temperature and pressure.

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2. Extensive properties. These properties depend on the mass of the system. Example :
Volume.

Extensive properties are often divided by mass associated with them to obtain the intensive
properties. For example, if the volume of a system of mass m is V, then the specific volume of

STATE

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matter within the system is V/m = v which is an intensive property.

State is the condition of the system at an instant of time as described or measured by its

PROCESS

properties. Or each unique condition of a system is called a state.

A process occurs when the system undergoes a change in a state or an energy transfer at a
steady state.

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NON-FLOW PROCESS
A process may be non-flow in which a fixed mass within the defined boundary is undergoing a
change of state.
Example : A substance which is being heated in a closed cylinder undergoes a non-flow process
.FLOW PROCESS
A process may be a flow process in which mass is entering and leaving through the boundary of
an open system.
QUASI-STATIC PROCESS.
Quasi means almost. A quasi-static process is also called a reversible process. This process is

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a succession of equilibrium states and infinite slowness is its characteristic feature.

Let us consider a system of gas contained in a cylinder (Fig. 1.7). The system initially is in
equilibrium state, represented by the properties p1, v1, t1. The weight on the piston just balances
the upward force exerted by the gas. If the weight is removed, there will be an unbalanced force
between the system and the surroundings, and under gas pressure, the piston will move up till it
hits the stops.
The system again comes to an equilibrium state being described by the properties p2,v2,t2 but
the intermediate state passed through by the system are non-equilibrium state which cannot be
described by thermodynamics coordinates. Figure 1.8 shows points 1 and 2 as the initial and
final equilibrium states joined by a dotted line which has got no meaning otherwise. Now if the
single weight on the piston is made up of many very small pieces of weights and these weights
are removed one by one very slowly from the top of the piston at any instant of the upward travel
of the piston if the gas system is isolated the departure of the state of the system from the
thermodynamic equilibrium state will be infinitesimally small .so every state passed through by
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the system will be an equilibrium state ,such a process which is but a locus of all the equilibrium
points passed through by the system is known as a quasi-static process. Quasi meaning almost
infinite slowness is the characteristic feature of a quasic static process. A quasi static process is
thus a succession of equilibrium states .A quasi static process is also called as reversible process

CYCLE

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Any process or series of processes whose end states are identical is termed a cycle. The
processes through which the system has passed can be shown on a state diagram, but a complete

the system.
POINT FUNCTION

section of the path requires in addition a statement of the heat and work crossing the boundary of

When two properties locate a point on the graph (co-ordinate axes) then those properties are
called as point function.

Examples. Pressure, temperature, volume etc.

PATH FUNCTION
There are certain quantities which cannot be located on a graph by a point but are given by the
area or so, on that graph. In that case, the area on the graph, pertaining to the particular process,
is a function of the path of the process. Such quantities are called path functions.

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Examples. Heat, work etc. Heat and work are inexact differentials.

Their change cannot be written as difference between their end states.

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TEMPERATURE

The temperature is a thermal state of a body which distinguishes a hot body from a cold body.
The temperature of a body is proportional to the stored molecular energy. .i.e., the average

molecular kinetic energy of the molecules in a system. (A particular molecule does not have a
temperature, it has energy. The gas as a system has temperature).
Instruments for measuring ordinary temperatures are known as thermometers and
those for measuring high temperatures are known as pyrometers.
It has been found that a gas will not occupy any volume at a certain temperature. This
temperature is known as absolute zero temperature. The temperatures measured with absolute
zero as basis are called absolute temperatures. Absolute temperature is stated in degrees
centigrade. The point of absolute temperature is found to occur at 273.15C , below the freezing
point of water.
Then , Absolute temperature = Thermometer reading in C + 273.15.
Absolute temperature is degree centigrade is known as degrees kelvin, denoted by K (SI unit).
TEMPERATURE SCALES
The various types as temperature scales in use are :
a) Celsius scale
b) Fahrenheit scale
c) Kelvin scale
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d) Rankine scale
Until 1954, the temperature scales were based on two fixed points : (i) the steam point (boiling
point of water at standard atmospheric pressure), and (ii) the ice point (freezing point of water).

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The fixed points for these temperature scales are :

The relation between a particular value C on Celsius scale and F on Fahrenheit scale is
found to be as mentioned below :

ZEROTH LAW OF THERMODYNAMICS

Zeroth law of thermodynamics states that if two systems are each equal in temperature
to a third, they are equal in temperature to each other.
Example. Refer Fig. 2.7. System 1 may consist of a mass of gas enclosed in a rigid vessel
fitted with a pressure gauge. If there is no change of pressure when this system is brought into
contact with system 2 a block of iron, then the two systems are equal in temperature (assuming
that the systems 1 and 2 do not react each other chemically or electrically). Experiment reveals
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that if system 1 is brought into contact with a third system 3 again with no change of
properties then systems 2 and 3 will show no change in their properties when brought into
contact provided they do not react with each other chemically or electrically. Therefore, 2 and
3 must be in equilibrium.

C
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This law was enunciated by R.H. Fowler in the year 1931.

However, since the first and second laws already existed at that time, it was designated as zeroth

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law so that it precedes the first and second laws to form a logical sequence.
THE THERMOMETER AND THERMOMETRIC PROPERTY
Introduction

The zeroth law of thermodynamics provides the basis for the measurement of
temperature.It enables us to compare temperatures of two bodies 1 and 2 with the help of a
third body 3 and say that the temperature of 1 is the same as the temperature of 2without
actually bringing 1 and 2 in thermal contact. In practice, body 3 in the zeroth law is called
the thermometer. It is brought into thermal equilibrium with a set of standard temperature of a
body 2, and is thus calibrated. Later, when any other body 1 is brought in thermal
communication with the thermometer, we say that the body 1 has attained equality of
temperature with the thermometer, and hence with body 2.This way, the body 1 has the
temperature of body 2 given for example by, say the height of mercury column in the
thermometer 3.The height of mercury column in a thermometer, therefore, becomes a
thermometric property.
PRESSURE
Definition of Pressure
Pressure is defined as a force per unit area. Pressures are exerted by gases, vapours and liquids.
The instruments that we generally use, however, record pressure as the difference between two
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pressures. Thus, it is the difference between the pressure exerted by a fluid of interest and the
ambient atmospheric pressure.
Such devices indicate the pressure either above or below that of the atmosphere. When
it is above the atmospheric pressure,it is termed gauge pressure and is positive. When it is
below atmospheric, it is negative and is known as vacuum pressure. Vacuum readings are given
in mm of Hg or mm of water below the atmosphere. It is necessary to establish an absolute
pressure scale which is independent of the changes in atmospheric pressure. A pressure of
absolute zero can exist only in complete vacuum. Any pressure measured above the absolute
zero of pressure is termed an absolute pressure. A schematic diagram showing the gauge
pressure, vacuum pressure and the absolute pressure.
Absolute pressure = Atmospheric pressure + Gauge pressure

(ii)

Vacuum pressure = Atmospheric pressure Absolute pressure.

(i)

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Pabs = Patm- Pvacc

Vacuum is defined as the absence of pressure. A perfect vacuum is obtained when absolute

pressure is zero, at this instant molecular momentum is zero.

Atmospheric pressure is measured with the help of barometer.

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Unit for Pressure

The fundamental SI unit of pressure is N/m2.

(sometimes called pascal, Pa) or bar.

Standard atmospheric pressure = 1.01325 bar = 0.76 m (or 760 mm) Hg.
Low pressures are often expressed in terms of mm of water or mm of Hg. This is an abbreviated
way of saying that the pressure is such that which will support a liquid column of
stated height.

PURE SUBSTANCE

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A substance that has a fixed chemical composition throughout is called a pure substance.
Examples

Water, nitrogen, helium, and carbon dioxide, are all pure substances.
A pure substance does not have to be of a single chemical element or compound, however. A

mixture of various chemical elements or compounds also qualifies as a pure substance as long as
the mixture is homogeneous.
Air, for example, is a mixture of several gases, but it is often considered to be a pure
substance because it has a uniform chemical composition

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P-T (PRESSURE-TEMPERATURE) DIAGRAM FOR A PURE SUBSTANCE

If the vapour pressure of a solid is measured at various temperatures until the triple point
is reached and then that of the liquid is measured until the critical point is reached, the result
when plotted on a p-T diagram . If the substance at the triple point is compressed until there is
no vapour left and the pressure on the resulting mixture of liquid and solid is increased, the
temperature will have to be changed for equilibrium to exist between the solid and the liquid.
Measurements of these pressures and temperatures give rise to a third curve on the p-T

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diagram, starting at the triple point and continuing indefinitely.

The points representing the coexistence of

(i) solid and vapour lie on the sublimation curve,
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(ii) liquid and vapour lie on the vapourisation curve,

(iii) liquid and solid lie on the fusion curve.
In the particular case of water, the sublimation curve is called the frost line, the
vapourisation curve is called the steam line, and the fusion curve is called the ice line. The slopes
of sublimation and the vapourisation curves for all substances are positive. The slope of the
fusion curve, however may be positive or negative. The fusion curve of most substances have a
positive slope. Water is one of the important exceptions.

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P-V (PRESSURE-VOLUME) DIAGRAM

T-S (TEMPERATUTE-ENTROPY) DIAGRAM

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TRIPLE POINT

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T-V (TEMPERATUTE-VOLUME) DIAGRAM

The triple point is merely the point of intersection of sublimation and vapourisation and fusion
curves.

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UNIT-II FIRST LAW OF THERMODYNAMICS

UNITS OF WORK AND POWER
In the international system (SI), the unit of force is Newton (N) and that of distance is metre (m).
Hence the unit of work is Nm, which is also given a special name Joule. In most of the
applications large quantity of work is involved. Therefore kJ is commonly used.
POWER
Rate of doing work is known as power.
Hence its unit is Nm/S or J/S which is again given a special name Watts(W).
SIGN CONVENTION OF WORK AND HEAT
Work done by the system on the surroundings is considered as positive work.

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Work done on the system by the surroundings is taken as negative work.

Heat gained or absorbed by the system is taken as +ve

Heat liberated or lost by the system is taken as -ve
P- dV WORK OR DISPLACEMENT WORK
Consider a piston cylinder arrangement as given in the Figure. If the pressure of the fluid is
greater than that of the surroundings, there will be an unbalanced force on the face of the piston.
Hence, the piston will move towards right.

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This work is known as displacement work or p dV work corresponding to the elemental

displacement dl. To obtain the total work done in a process, this elemental work must be added
from the initial state to the final state. Mathematically,
Force acting on the piston = Pressure Area = p x A
Work done = Force distance
= pA dl
= p dV

INTERNAL ENERGY
If during heating of the gas the temperature increases its internal energy will also increase.
Joules law of internal energy states that internal energy of a perfect gas is a function of

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temperature only

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