Enroll

Ahmad
No: 124/14
Ali Mir
Ahmadmir96@gmail.com
Roll No: 35
Semester: 3rd
Branch: Mechanical

2ND LAW OF
THERMODYNAM
ICS
With 5
Numerical

2nd Law of Thermodynamics

Statement: - The Second Law of Thermodynamics states that the state
of entropy of the entire universe, as an isolated system, will always
increase over time.
The second law also states that the changes in the entropy in the universe
can never be negative.

Introduction:Why is it that when you leave an ice cube at room temperature, it begins
to melt? Why do we get older and never younger? And, why is it
whenever rooms are cleaned, they become messy again in the future?
Certain things happen in one direction and not the other, this is called the
"arrow of time" and it encompasses every area of science.
The thermodynamic arrow of time (entropy) is the measurement of
disorder within a system. Denoted as S, the change of entropy suggests
that time itself is asymmetric with respect to order of an isolated system,
meaning: a system will become more disordered, as time increases.

Major players in developing the Second

Law:

Nicolas Lonard Sadi Carnot was a French Physicist, who is

considered to be the "Father of Thermodynamics," he is responsible for
the origins of the Second Law of Thermodynamics, as well as various
other concepts. The current form of the Second Law uses Entropy rather
than Caloric, which is what Sadi Carnot used to describe the law. Caloric
relates to heat and Sadi Carnot came to realize that some caloric is
always lost in the motion cycle. Thus, the thermodynamic reversibility
concept was proven wrong, proving that irreversibility is the result of
every system involving work.

Rudolf Clausius was a German Physicist, and he developed the

Clausius statement, which says
"Heat generally cannot flow spontaneously from a material at a lower
temperature to a material at a higher temperature."

William Thompson, also known as Lord Kelvin, formulated the

Kelvin statement, which states
"It is impossible to convert heat completely in a cyclic process." This
means that there is no way for one to convert all the energy of a system
into work, without losing energy.

Constantin Carathodory, a Greek Mathematician, created his own

statement of the Second Law arguing that
"In the neighborhood of any initial state, there are states
which cannot be approached arbitrarily close through adiabatic changes
of state."

Probabilities:If a given state can be accomplished in more ways, then it is more

probable than the state that can only be accomplished in a fewer/one
way.
Assume a box filled with jigsaw pieces were jumbled in its box, the
probability that a jigsaw piece will land randomly, away from where it
fits perfectly, is very high. Almost every jigsaw piece will land
somewhere away from its ideal position. The probability of a jigsaw
piece landing correctly in its position, is very low, as it can only
happened one way. Thus, the misplaced jigsaw pieces have a much
higher multiplicity than the correctly placed jigsaw piece, and we can
correctly assume the misplaced jigsaw pieces represent a higher entropy.

Derivation and Explanation:To understand why entropy increases and decreases, it is important to
recognize that two changes in entropy have to be considered at all times,
i.e. the entropy change of the surroundings and the entropy change of the
system itself.
Given the entropy change of the universe is equivalent to the sums of the
changes in entropy of the system and surroundings:
Suniv = S sys + S surr =

qsys q surr
+
(1)
T
T

In an isothermal reversible expansion, the heat q absorbed by the system

from the surroundings is

q rev=nRTln

V2
(2)
V1

Since the heat absorbed by the system is the amount lost by the
surroundings, q sys=q surr . Therefore, for a truly reversible process, the
entropy change is
V2
V
nRTln 2
V1
V1
+
=0(3)
T
T

nRTln
Suniv =

If the process is irreversible however, the entropy change is

nRTln
Suniv =

V2
V1

>0( 4)

If we put the two equations for Suniv together for both types of
processes, we are left with the second law of thermodynamics,
S univ= S sys + S surr 0 (5)
Where Suniv equals zero for a truly reversible process and is greater
than zero for an irreversible process. In reality, however, truly reversible
processes never happen (or will take an infinitely long time to happen),
so it is safe to say all thermodynamic processes we encounter everyday
are irreversible in the direction they occur.

Note:The second law of thermodynamics can also be stated as

"All Spontaneous processes produce an Increase in the entropy of the
Universe".

Gibbs Free Energy:Given another equation:

Stotal=Suniv=Ssurr + Ssys(6)

The formula for the entropy change in the surroundings is

Ssurr= Hsys /T

. If this equation is replaced in the previous formula,

and the equation is then multiplied by T and by -1 it results in the
following formula.
TSuniv= HsysTSsys(7)

If the left side of the equation is replaced by G, which is known as Gibbs

energy or free energy, the equation becomes
G=H TS(8)

Now it is much simpler to conclude whether a system is spontaneous,

non-spontaneous, or at equilibrium.

H refers to the heat change for a reaction.

A positive H means that heat is taken from the environment
(endothermic).
A negative H means that heat is emitted or given the
environment (exothermic).

G is a measure for the change of a system's free energy in which

a reaction takes place at constant pressure (P) and temperature (T).

According to the equation, when the entropy decreases and enthalpy

increases the free energy change, G, is positive and not spontaneous,
and it does not matter what the temperature of the system is.
Temperature comes into play when the entropy and enthalpy both
increase or both decrease. The reaction is not spontaneous when both
entropy and enthalpy are positive and at low temperatures, and the
reaction is spontaneous when both entropy and enthalpy are positive and
at high temperatures. The reactions are spontaneous when the entropy
and enthalpy are negative at low temperatures, and the reaction is not
spontaneous when the entropy and enthalpy are negative at high
temperatures. Because all spontaneous reactions increase entropy, one
can determine if the entropy changes according to the spontaneous
nature of the reaction (Equation 8).
Table 1: Matrix of Condition Dictating Spontaneity
Case

Answer

high temperature

Spontaneous

low temperature

Spontaneous

high temperature

Nonspontaneous

low temperature

Spontaneous

high temperature

Spontaneous

low temperature

Nonspontaneous

high temperature

Nonspontaneous

low temperature

Nonspontaneous

Application of the Second Law:The second law occurs all around us all of the time, existing as the
biggest, most powerful, general idea in all of science.

Explanation of Earth's Age:When scientists were trying to determine the age of the Earth during
1800s they failed to even come close to the value accepted today. They
also were incapable of understanding how the earth transformed. Lord
Kelvin, who was mentioned earlier, first hypothesized that the earth's
surface was extremely hot, similar to the surface of the sun. He believed
that the earth was cooling at a slow pace. Using this information, Kelvin
used thermodynamics to come to the conclusion that the earth was at
least twenty million years, for it would take about that long for the earth
to cool to its current state. Twenty million years was not even close to
the actual age of the Earth, but this is because scientists during Kelvin's
time were not aware of radioactivity. Even though Kelvin was incorrect
about the age of the planet, his use of the second law allowed him to
predict a more accurate value than the other scientists at the time.

Evolution and the Second Law:Some critics claim that evolution violates the Second Law of
Thermodynamics, because organization and complexity increases in

evolution. However, this law is referring to isolated systems only, and

the earth is not an isolated system or closed system. This is evident for
constant energy increases on earth due to the heat coming from the sun.
So, order may be becoming more organized, the universe as a whole
becomes more disorganized for the sun releases energy and becomes
disordered.

Numerical:Example 1:Propose ideal reversible processes to reverse the

processes listed below. Hence show that the original
processes are irreversible.
(i) A block of metal at 120 C is placed in thermal contact
with a heat reservoir at 30 C until their temperatures are
equal.
(ii) A well-insulated cylindrical vessel is divided into two
compartments with a light insulating piston. Initially a
fixed mass of air at 80 C and
1 bar pressure is
trapped in one section while the other section is
evacuated. The piston is held in position by a pin. The pin
is removed and the air expands to fill the whole vessel.
(iii) A well-insulated piston-cylinder apparatus contains
wet steam at a temperature of 105 C and quality of 0.3.
The external pressure on the piston due to the weight of
the piston and the surrounding air pressure is constant.
Located inside the cylinder is an electrical-resistance
heater. The heater is switched on and the steam
evaporates until the quality is 0.4.

Solution:(i) In the final equilibrium state the metal block will have
the same temperature of 30 C as the reservoir. We
operate a reversible or Carnot heat pump to transfer heat
from the reservoir to the block to raise its temperature to
120 C thus completing the cycle executed by the
composite system consisting of the block and heat pump.
The net work interaction of this cycle which exchanges
heat with a single reservoir at 30 C is negative because
of the work input to the heat pump. Therefore the cycle is
irreversible according to

Eq.

Wi 0 .

cycle

Since the second process introduced by us is reversible,

the original process has to be irreversible.
(ii) When the pin is removed, the light piston will be
pushed out and the air will expand to fill the vessel. For
this process the work done is zero because of the free
expansion and the heat interaction is zero due the
insulation. Therefore according to the first law the internal
energy is unchanged. Treating the air as an ideal gas we
conclude that the temperature of the air at the final state
is also 80 C . In order to reverse the process we compress
the air in a quasi-static isothermal process to the original
volume maintaining thermal contact with a reservoir at
80 C . The net work interaction of the cycle is negative
because of the work of compression and therefore the
cycle is irreversible according to Eq.

W i 0 . Since the

cycle

compression process is reversible, the original freeexpansion process has to be irreversible.

(iii) The process can be reversed by removing some of the

insulation and placing a reservoir at 105 C in thermal
contact with the steam. An infinitesimal temperature
difference between the steam and the reservoir will
initiate condensation. The condensation process at
constant pressure and temperature is continued until the
quality of the steam is 0.3 thereby returning the steam to
its original state. The work done by the piston during the
expansion is equal in magnitude and opposite in direction
to the compression work during condensation. However,
the electrical energy input during original evaporation
process is a negative work interaction which makes the
net work interaction of the cycle negative. Therefore the
cycle is irreversible according to Eq.

W i 0 . The

cycle

condensation process is reversible and therefore the

original heating process is irreversible.

Example 2:A fixed mass of air is trapped in a cylinder behind a

2
frictionless piston of area 0.035 m . The mass of the
piston is 12 kg and the external pressure on the piston is
zero. Initially, the conditions of the air are:
P1=1.5 , V 1=104 m 3 ,T 1=30 . The piston is held in position by a
pin. The air, the piston and the cylinder are in thermal
equilibrium with the surroundings which may be regarded
as a thermal reservoir at 30 C . The pin is now removed
and the piston moves up until a final equilibrium state is
attained.

Calculate
(i) The final, temperature, pressure and volume of the air
and
(ii) The heat and work interaction between the system
and the surroundings. Describe a reversible process to
return the air to its initial state. Hence show that the
original expansion process is irreversible.
Solution:Since the air is in thermal equilibrium with the
surroundings, the final temperature is T 2 =30 C . The force
balance of the piston in the final state gives
A P2=0. 035 P 2=12 g

Where the acceleration due to gravity,

Hence

g=81.9 m s2

P2=3.363 103 N m2 .

Applying the ideal gas equation to states 1 and 2 we have

mR=P1 V 1 /T 1=P2 V 2 /T 2

Substituting numerical values in the above equation

4

V 2=150 10 /3.363=44.6 10 m

The change in elevation of the piston is given by

H=(V 2V 1 )/ A=(44.61)104 /0.035=0.1246 m

The work done by the air is equal to the potential energy

gained by the piston. Hence
W 12=M g H =12 9.91 0.1246=14.67 J

The change in internal energy of the air is

U 2U 1 =mC v ( T 2T 1 )=0 J

Applying the first law we have

Q12=U 2U 1 +W 12=14.67 J

To reverse the state of the air we use a reversible

isothermal compression process while the air exchanges
heat with a reservoir at 30 C . The work input for this
isothermal process is given
W 23=mR T 2 ln ( V 2 /V 3 ) =P 2 V 2 ln(V 2 /V 1)

Substituting numerical values in the above equation we

have
W 23=3.363 103 44.6 104 ln ( 44.6 /1.0 ) =56.96 J

The net work output of the cycle consisting of the original

process 1-2 and the isothermal compression process is
W net =14.6756.96=42.3 J

The system interacts only with a single reservoir at

and the net work output of the cycle is negative.
Therefore the cycle is irreversible according to Eq.

30

W i 0 .The isothermal compression process is reversible

cycle

and therefore the original process 1-2 has to be

irreversible.

Example 3:A fixed mass of an ideal gas undergoes a cycle 1-2-3

consisting of three processes. In the first constant volume

process 1-2 it receives heat from a reservoir at 600 K.

During the next adiabatic process 2-3 it delivers a work
output of 88 kJ to the surroundings. The gas rejects heat
to a reservoir at 280 K during the isothermal process 3-1
while it receives a work input of 64.5 kJ. Show that the
cycle is irreversible.
Solution:From the given information we draw the following
conclusions concerning the heat and work interactions of
the three processes. For the constant volume process,
W 12=0
. For the adiabatic process Q23=0 . The change in
internal energy of the ideal gas during the isothermal
process is zero.
Hence
Q31=W 31=64.5 J

Applying the first law to the cycle

Q12+Q23 +Q31=W 12 +W 23 +W 31

Substituting the numerical values in the above equation

we have
Q12+ 064.5=0+8864.5

Therefore
Q12=88 kJ
2

i
0 to the cycle
Applying the condition given by Eq.
i=1 T i

operating with two heat reservoirs we have

Q12 /600Q31 /280=88 /60064.5/280=0.084 <0

Therefore the cycle is reversible.

Example 4:An inventor claims that he has designed a heat engine
that operates in a cycle receiving heat at the rate of 120
kW from a waste-heat source at 320 . The engine
delivers work at the rate of 65 kW and rejects heat to the
atmosphere at 30 . Is the claim of the inventor valid?
Solution:We shall treat the engine as a cyclic device operating
between two heat reservoirs. The hot and cold reservoir
temperatures are respectively,
T h=320+273=593 K

&

T c =30+273=303 K

The heat transfer rate between the cycle device and the
hot reservoirs is
Qh=120 kW

Applying the first law to the cyclic device, the heat

rejection rate is
Qc =QhW =12065=55 kW
2

i
0
Apply the condition given by Eq.
T
i=1
i

to the cycle

operating with two reservoirs,

Qh /593Qc / 303=120/59355/303=0.0208>0

The cycle violates the second law according to Eq.

2

T i 0 Therefore the claim of the inventor is not valid.

i=1
i

Example 5:A Carnot heat engine operates between hot and cold heat
reservoirs of temperature T h and T c respectively.
Determine which of the following changes to the reservoir
temperatures will be more effective in increasing the
thermal efficiency of the engine:
(i) Increase

Th

(ii) Decrease

to
Tc

T h+ T

to

keeping

T c T

Tc

keeping

constant, or
Th

constant.

Solution:The efficiency of the Carnot heat engine is given by

=1T c /T h(1)

Substituting the proposed changes (i) and (ii) to the

reservoir temperatures in above equation (1) we obtain
the following expressions for the efficiency under the new
conditions.
h T c + T
T
( h+ T )(2)
T /
h=1T c / ( T h + T )=

T
T hT c + T /T h(3)
T h=
( cT )/
c =1

Dividing Eq (3) by Eq (2), we have

c
=(T h + T )/T h >1
h

From the above equation it follows that decreasing the

cold reservoir temperature leads to a larger increase in
the cycle efficiency.