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# II Law of Thermodynamics

## Limitations of the first law of

thermodynamics
Unable to deal with the direction of change
and the extent of change
Cannot tell whether the proposed change
would actually occur or not
Fails to recognize the qualitative difference
between the various forms of energy

## Second law deals with

Direction of change
Puts restrictions on useful conversion of heat
to work
Provides set of principles for
Determining the direction of spontaneous change
Determining the equilibrium state of the system

## Kelvin Planck Statement for II law

It is impossible to create a cyclically operating
device which produces no other effect than
the extraction of energy a heat from a single
thermal reservoir and delivers and equivalent
amount of work

## Clausius Statement for II law

It is impossible to construct a self-acting
device which when working cyclically will
produce no other effect than transfer of
energy as heat from a low temperature body
to a high temperature body

## Equivalence between both the

statements
Violation of one of the statements leads to the
violation of the other.

Entropy
Entropy = Transformability

## Introduced by Clausius in 1851

Entropy
Gives the quantitative significance of the II law
It is the measure of the spontaneous
behaviour of processes
It is the measure of unavailability or
It is a state function
It is an intrinsic property.. Not affected by
motion or external position of the body

Entropy
It is affected by the
nature of matter under consideration and
state in which it exists

## Entropy is increased by addition of heat

Increase in entropy is proportional to the heat
exchanged but not equal to it
Amount of increase depends on
Amount of heat added to the system
Temperature of the system to which heat is added

Entropy
For measuring entropy, nature of the process
should be known reversible or irreversible
process is reversible

Entropy
Entropy change

dS

dQR
dT

## Entropy change requires

Amount of heat transferred
Temperature level at which heat transfers
Nature of process reversible or irreversible

Carnot cycle
1-2: Reversible isothermal
heat absorption
compression
3-4 : Reversible isothermal
heat rejection
compresssion

## Propositions of Carnot cycle

No heat engine operating in a cycle between
two constant temperature reservoirs can be
more efficient than a reversible engine
operating between the same two reservoirs

## Propositions of Carnot cycle

All reversible engines working between two
constant temperature reservoirs have the
same efficiency, irrespective of the working
substance and the efficiency is dependent on
temperature only

## Thermodynamic temperature scale

II proposition helps to define a universal
temperature scale irrespective of the
properties of fluid.. Proposed by Lord Kelvin
Q1
Q2

T1
T2

Q1 Q2
Q1

T1 T2
T1

operation
SV

HV
T

S

T2
CV ln
T1

V2
R ln
V1

T2
C P ln
T1

P2
R ln
P1

## Constant volume and constant

pressure processes
For constant volume process

T2
CV ln
T1

## For constant pressure process

T2
C P ln
T1

Isothermal process
S

V2
R ln
V1

P1
R ln
P2

## Isothermal mixing of gases

S

xi ln xi

When two intermingling gases are
mixed for equimolar mixture, the
entropy change is
S = R ln 2
This is true as long as the gases are
different. If the gases are same, then
the entropy change on mixing is zero.

J. W. Gibbs

## Entropy change accompanying a

chemical reaction

S = S Products S Reactants

Lost work
Wlost = T0 ( S)Total
where ,
T0 is the temperature of the surrounding

## Third Law of thermodynamics

The absolute entropy is zero for a perfect
crystalline substance at absolute zero of
temperature.

Significance
To calculate the absolute entropy of
substances
Tf

C Ps dT
T
0

HF
Tf

Tb

C PL dT
T
Tf

HV
Tf

C PG dT
T
Tb

Refrigerator

## Ranque Hilsch Vortex tube

(Pg.90, Ex.4.5 , Kyle)

## The Ranque-Hilsch vortex tube, is a heat pump

with no moving parts.
Pressurized gas is injected into a specially
designed chamber. The chamber's internal
shape, combined with the pressure,
accelerates the gas to a high rate of rotation
(over 1,000,000 rpm).
The gas is split into two streams, one giving
kinetic energy to the other, and resulting in
separate flows of hot and cold gases.
It was invented in 1930 by French physicist
Georges J. Ranque. German physicist Rudolf
Hilsch improved the design and published a
widely read paper in 1945 on the device