THERMODYNAMICS

Thermodynamics is derived from Greek word

thermo meaning heat and dynamos
meaning work or power.
Thermodynamics is a science that deals
with heat and work, and the properties of the
substance that are connected with heat and
work.
Thermodynamic systems,
Boundary and Surrounding
A thermodynamic system is prescribed region
in the space or a finite quantity of matter upon
which the attention is focussed for study.
An imaginary envelope enclosing a system is
boundary.
Everything external to system is surrounding.
System and surrounding both comprises the
universe.
Systems
There are mainly three types of system. They
are
Open system
System which permits the passage of both
energy and mass across the boundary is called
an open system. For instance, take hot cup of
tea.
Closed system
System which permits the passage of only
energy is called a closed system. For instance,
take a closed refrigerator.
Isolated system
A system which doesnt permit the passage of
both energy and mass across the boundary is
known as isolated system. For example, take a
thermos flask.
Consider an open system,
An imaginary envelope enclosing an open
system is called as control surface; and the
volume enclosed in the control surface is
called control volume.
Property and State of a System
A property is an observable or measurable
characteristic of a system. For instance,
pressure, volume, temperature. State is the
condition of the system described by the
property.
There are two type of property, namely
Intrinsic property
Properties which are Independent of the mass
are called intrinsic properties. E.g. temp,
density, viscosity
Extrinsic property
Properties that are dependent on mass are
extrinsic properties. E.g. weight, volume,
enthalpy
Point function and Point Path
The property which depends only upon the
thermodynamic state and not on the process
by which the state is reached is called point
function.
1 2
1 2
V V V
P P P
= c
= c

The curve can take any path to reach the
value.
The property which depends upon the process
by which the process has reached is called
point path. E.g. Heat, Work. It depends upon
the path taken by the curve.
Thermodynamic Equilibrium
When the system is under mechanical,
chemical and thermal equilibrium, the system
is said to be in thermodynamic equilibrium.
Process
When a system changes its state from one
state to another state, it is said to have
undergone a process.
Quasi-Static Process
It is process by which the system is in the
equilibrium. Quasi-Static process is very slow
process and is often called reversible
process. All the processes that occur in nature
are irreversible process.
Cycle
When the processes are performed on the
system such that the system starting from a
certain state and reaches back to its original
state, then the system is said to have
undergone a cycle.
Zeroth Law of Thermodynamics
When the body A is in thermal equilibrium
with body B, and body B is in thermal
equilibrium with body C, then body A and C are
in thermal equilibrium with each other.
Work and Heat
Work is the energy transferred because of the
property difference that exists between the
system and the surrounding.
Heat is the energy transferred across the
boundaries of the system due to temperature
difference between the system and the
surrounding.
First Law of Thermodynamics
For a system operating in a cycle, the net work
done is equal to net heat transfer.
Cycle:
} }
= dW dQ
Process:
V P dU dQ
dW dU dQ
A + =
+ =

Enthalpy
The sum of internal energy and flow work is
called as Enthalpy.
V P U H A + =
Specific Heat
At constant volume,
V
C
V P dU dQ A + =
Here, 0 , 0 = A A V V P
dU dQ=
dU dT mC
V
=
V
V
dT
dU
C
|
.
|

\
|
=
It is the ratio of increase in internal energy to
corresponding increase in the temperature
difference at constant volume.
At constant pressure,
P
C
V P dU dQ A + =

) (
1 2 1 2
V V P U U dQ + =
) ( ) (
1 1 2 2
PV U PV U dQ + + + =
1 2
H H dQ =
dH dT mC
P
=
P
P
dT
dH
C
|
.
|

\
|
=
It is the ratio of increase in the enthalpy to the
corresponding increase in the temperature at
constant pressure.
Perpetual Motion Machine of
First Kind (PMMI)
} }
= dW dQ

If
}
= 0 dQ
Then
}
= 0 dW
It is the machine which gives continuous
output of work from a system working in the
cycle with zero input of energy. It is impossible
to have such a machine.
Limitations of First Law