Fundamental Concepts

and Definitions
THERMODYNAMICS:

�It is the science of the relations

between heat, Work and the
properties of the systems.
�How to adopt these
interactions to our benefit?
Thermodynamics enables us to
answer this question.

Analogy
All currencies are not equal
Eg: US$ or A$ or UK£etc. Have a better
purchasing power
than Indian Rupee or Thai Baht or Bangladesh
Taka
similarly,all forms of energy are not the same.
Human civilization has always endeavoured to
obtain
Electrical Energy
�Shaft worky
�Potential energy to make life easier

ExamplesIf we like to�Rise the

temperature of water in kettle�Burn
some fuel in the combustion chamber
of an aeroengine to propel an
aircraft.�Cool our room on a hot
humid day.�Heat up our room on a
cold winter night.�Have our beer
cool.What is the smallest amount of
electricity/fuel wecan get away with?

Examples (Contd…)
On the other hand we burn,
�Some coal/gas in a power plant to
generate electricity.
�Petr
ol in a
car
engine.
What is the largest energy we can get out of
these efforts?
Thermodynamics allows us to answer
some of these questions

Definitions�In our study of

thermodynamics, we will choose a
small part of the universeto which we
will apply the laws of
thermodynamics.We call this subset a
SYSTEM.�The thermodynamic system
is analogous to the free bodydiagram
to which we apply the laws of
mechanics, (i.e.Newton’s Laws of
Motion).�The system is a
macroscopically identifiable collection
of matteron which we focus our
attention(eg: the water kettle or the
aircraft engine).

�The rest of the universe outside the system

close enough

to the system to have some perceptible effect on

the
system is called the surroundings.

�The surfaces which separates the system from

the

surroundings are called the boundariesas shown

in fig
below(eg: walls of the kettle, the housing of the
engine).

Types of System
�Closed system-in which no mass is permitted
to cross the system boundary i.e. we would
always consider a system of constant mass.We
dopermit heat and work to enter or leave but not
mass.
No mass entry or exit

�Open system-in which we permit mass to

cross the system boundary in either direction
(from the system to surroundings or vice
versa).In analysing open systems, we typically
look at a specified region of space, and observe
what happens at the boundaries of that region.

Most of the engineering devices are open

system.
�Isolated System-in which there is no interaction
between system and the surroundings. It is of
fixed mass and energy, and hence there is no
mass and energy transfer across the system
boundary.
 Choice of the System and
Boundaries Are at Our
Convenience

�We must choose the system for each

and every problem we work on, so as to
obtain best possible information on how it
behaves.
�In some cases the choice of the system
will be obvious and in some cases not so
obvious.
�Important: you must be clear in defining what
constitutes your system and make that choice
explicit to anyone else who may be reviewing
your work. (eg: In the exam paper or to your
supervisor in the work place later)

�The boundaries may be real physical surfaces

or they may be imaginary for the convenience of
analysis.
eg: If the air in this room is the system,the
floor,ceiling and walls constitutes real
boundaries.the plane at the open doorway
constitutes an imaginary boundary.

�The boundaries may be at rest or in motion.

eg: If we choose a systemthat has a certain

defined quantity of mass (such as gas contained
in a piston cylinder device) the boundariesmust
move in such way that they always enclose that
particular quantity of mass if it changes shape or
moves from one place to another.
 Macroscopic and Microscopic
Approaches
Behavior of matter can be studied by these two
approaches.

�In macroscopic approach, certain

quantity of matter is
considered,without a concern on the
events occurring at the molecular
level. These effects can be perceived
by human senses or measured by
instruments.
�eg: pressure, temperature

Microscopic Approach
�In microscopic approach, the effect of
molecular motion is Considered.

eg: At microscopic level the pressure of a gas is

not constant, the temperature of a gas is a
function of the velocity of molecules.
Most microscopic properties cannot be
measured with common instruments nor can be
perceived by human senses

Property

�
It is some characteristic of the system to
which some physicallymeaningful numbers
can be assigned without knowing the history
behind it.
�These are
macroscopic
in nature.
�Invariably the properties must enable us
to identify the system.
�eg: Anand weighs 72 kg and is 1.75 m tall.
We are not concerned how he got to that stage.
We are not interested what he ate!!.
We must choose the most appropriate set of
properties.

�For example: Anand weighing 72 kg

and being 1.75 m tall may be a useful
way of identification for police
purposes.
�If he has to work in a company you
would say Anand graduated from IIT,
Chennai in 1985 in mechanical
engineering.
�Anand hails from Mangalore. He has a sister
and his father is a poet. He is singer. ---If you
are looking at him as a bridegroom!!

�
All of them are properties of
Anand. But you pick and choose a
set of his traits which describe him
best for a given situation.
�Similarly, among various properties by which
a definition of a thermodynamic system is
possible, a situation might warrant giving the
smallest number of properties which describe
the system best.

Categories of Properties

�Extensive property:
whose value depends on the size or extent of the
system (upper case letters as the symbols).
eg: Volume, Mass (V,M).
If mass is increased, the value of extensive
property also
increases.

�Intensive property:
whose value is independentof the size or extent
of the system.
eg: pressure, temperature (p, T).
Specific property:
�It is the value of an extensive property per unit
mass of system. (lower case letters as symbols)
eg: specific volume, density (v, , ρρ).).
�It is a special case of an intensive property.
�Most widely referred properties in
thermodynamics:
�Pressure; Volume; Temperature; Entropy;
Enthalpy; Internal
Energy
� State:It is the condition of a system as defined
by the values of all its properties.It gives a
complete description of the system.Any
operation in which one or more properties of a
system change is called a change of
state.�Phase:It is a quantity of mass that is
homogeneous throughout in chemical
composition and physical structure.e.g. solid,
liquid, vapour, gas.Phase consisting of more
than one phase is known as heterogenous
system .

Path And Process

The succession of states passed through during a
change of state is called the path of the system.A
system is said to go through a process if it goes
through a series of changes in state.
Consequently:

�A system may undergo changes in some

or all of its properties.
�A process can be construed to be the
locus of changes of state
Processes in thermodynamics are like streets in
a city
eg: we have north to south; east to west;
roundabouts; crescents

Types of Processes�As a matter of

rule we allow one of the properties to remain a
constant during a process.�Construe as many
processes as we can (with a different property
kept constant during each of them)�Complete
the cycle by regaining the initial state
•Isothermal (T)
•Isobaric (p)
•Isochoric (v)
•Isentropic (s)
•Isenthalpic (h)
•Isosteric (concentration)
•Adiabatic (no heat addition or removal

Quasi-static Processes
The processes can be restrained or unrestrained
We need restrained processes in practice.

A quasi-static process is one in which

�The deviation from thermodynamic

equilibrium is

infinitesimal.

�All states of the system passes through are

equilibrium

states.
�If we remove the weights slowly
one by one the pressure of the gas
will displace the piston gradually. It
is quasistatic.
�On the other hand if we remove all
the weights at once the piston will be
kicked up by the gas pressure.(This is
unrestrained expansion) but we don’t
consider that the work is done
-because it is not in a sustained
manner
�In both cases the systemshave
undergone a change of state.
�Another eg: if a person climbs down a ladder
from roof to ground, it is a quasistatic process.
On the other hand if he jumps then it is not a
quasistatic process.

Equilibrium State

�A system is said to be in an equilibrium

state if its propertieswill not change
without some perceivable effect in the
surroundings.
�Equilibrium generally requires all
properties to be uniform throughout the
system.
�There are mechanical, thermal, phase, and
chemical equilibria
Nature has a preferred way of directing changes.
eg:

�water flows from a

higher to a lower level
�Electricity flows from a higher
potential to a lower one
�Heat flows from a body at higher
temperature to the one at a lower
temperature
�Momentum transfer occurs from a point
of higher pressure to a lower one.
�Mass transfer occurs from higher
concentration to a lower one
Types of EquilibriumBetween the
system and surroundings, if there is no
difference in�PressureMechanical
equilibrium�PotentialElectrical
equilibrium�Concentration of species Species
equilibrium�TemperatureThermal
equilibriumNo interactions between them occur.
They are said to be in
equilibrium.Thermodynamic equilibrium
implies all those together.A system in
thermodynamic equilibrium does not deliver
anything.

Definition Of Temperature and

Zeroth Law Of
Thermodynamics

�Temperature is a property of a system

which determines the degree of hotness.
�Obvious
ly, it is a
relative
term.
eg: A hot cup of coffee is at a higher
temperature than a block of ice. On the other
hand, ice is hotter than liquid hydrogen.
Thermodynamic temperature scale is under
evolution. What we have now in empirical
scale.
 Zeroth Law Of
Thermodynamics (Contd…)

�Two systems are said to be equal in

temperature, when there is no change in their
respective observable properties when they are
brought together. In other words, “when two
systems are at the same temperature they are in
thermal equilibrium”(They will not exchange
heat).

Note:They need not be in thermodynamic

equilibrium.
 Zeroth Law

�If two systems (say A and B) are in thermal

equilibrium with a third system (say C)
separately (that is A and C are in thermal
equilibrium; B and C are in thermal
equilibrium) then they are in thermal
equilibrium themselves (that is A and B will be
in thermal equilibrium

Explanation of Zeroth Law

�Let us say TA,TBand TCare the temperatures

of A,B and C

respectively.
�A and c are in thermal equilibrium. Ta=tc
�B and C are in thermal equilibrium. Tb=tc
Consequence of of ‘0’th law

�A and B will also be in thermal

equilibrium TA=TB

Looks very logical

�

�All temperature measurements are based on

this LAW.