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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
degradation of energy
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
Maximum degradation occurs when the
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
2-3 : Reversible adiabatic
compression
3-4 : Reversible isothermal
heat rejection
4-1 : Reversible adiabatic
compresssion

Nicolas Sadi Carnot

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

Efficiency of Carnot engine


Q1 Q2
Q1

T1 T2
T1

Entropy change for phase change


operation
SV

HV
T

Processes involving ideal gases


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

Gibbs Paradox
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.
This is called Gibbs paradox.

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