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According to first law of thermodynamics, energy is always conserved. The possibility or impossibility of
putting energy to use is the subject of the second law of thermodynamics. It also describes the directionality
of natural thermodynamic processes. It can be stated in several equivalent forms.
In other words, Heat never flows spontaneously from low temperature to high
temperature.
The Refrigerator statement:
Refrigerator:
It is impossible to make heat flow from a body at a lower temperature to a body at a higher temperature
without doing external work on the working substance. Energy will not flow spontaneously from a low
temperature object to a higher temperature object. This precludes a perfect refrigerator.
No cyclic process can transfer heat from a colder place to a hotter place with no input of mechanical
work.
Second Law of Thermodynamics: Refrigerator Statement
Q
Q
W
1 C 1 C
QH
QH
QH
thermal disorder--refers to the distribution of the available energy among the particles.
dQ dU dW dU PdV
For an ideal gas, we can write dU in terms of the heat capacity, dU C V dT , and we can substitute
dV
V
dQ
dT
dV
CV
nRT
T
T
V
The gas is in a more disordered state after the expansion than before because the molecules are moving in a
larger volume and have more randomness of position. Thus the fractional volume change
dV
is a measure
V
of the increase in disorder, and the above equation shows that it is proportional to the quantity
dQ
. The
T
dT
is a measure of thermal disorder which refers to the distribution of the available energy among the
T
particles.
term
We introduce the symbol S for the entropy of the system, and we define the infinitesimal entropy change dS
during an infinitesimal reversible process at absolute temperature T as
dS
dQ
dT
dV
CV
nR
T
T
V
For simplicity, we will assume that CV is constant. Integrating this equation, we get
T
V
dQ
CV ln 2 nR ln 2
T
T1
V1
The above Equation gives the entropy change of an ideal gas that undergoes a reversible expansion from an
initial state of volume V 1 and temperature T1 to a final state of volume V 2 and temperature T2. When an ideal
gas undergoes an isothermal expansion, T2 = T1 and its entropy change is
V
dQ
nR ln 2
T
V1
If a total amount of heat Q is added during a reversible isothermal process at absolute temperature T, the
total entropy change S S 2 S 1 is given by
S S 2 S 1
Q
T
dQ
for the entire process; that is,
T
dQ
T
1
0.
A
P
B
C
1
V
Consider a closed system undergoing a reversible process from state 1 to state 2 along the path A and from
state 2 to state 1 along the path B. Since it is a reversible cyclic process
dQ
0
T
2A
1B dQ
dQ
0
2
B T
T
1A
. (i)
Now, consider the reversible cycle from state 1 to 2 along the path A from state 2 to state 1 along path C. For
this reversible cyclic process
2A
1C dQ
dQ
0 (ii)
2
C T
T
1A
1B
dQ
T
2B
1C
2C
dQ
T
dQ
has the same value for all the reversible paths from state 2 to state 1. This quantity
T
is independent of path and is a function of the end states only, therefore it is a property. This property is
called entropy and defined by the relation dS
dQ
T
The change in entropy is then the inverse of the temperature integrated over the change in heat transfer.
2
dS
1
dQ
T
2
S 2 S1
dQ
T
1
The quantity S2 S1 represents the change in entropy of the system when it is changed from state 1 to state
2.
Consider a closed system undergoing a reversible process from state 1 to state 2 along the path A and from
state 2 to state 1 along the path B. For a reversible cyclic process
dQ 0 .
2A
1B
dQ
dQ
1A T 2B T 0 .. (i)
Now consider an irreversible path C from state 2 to state 1.
Applying Clausius inequality for the cycle of process A and C
dQ
0
T
2A
1C
dQ
dQ
1 A T 2C T 0 (ii)
So,
1C
dQ
dQ
2 B T 2C T 0
dQ
2 B T
dS
or
S 2 S1
1B
1C
2B
2C
dS
dS
dQ
T
dQ
T
The above equation shows that the effect of irreversibility is always to increase the entropy of a system.
(3) Adiabatic Process: We know that the heat absorbs in a reversible adiabatic process is zero. Hence,
for such a process entropy change is given by
dS
dQ
0
T
S = Constant
That is Entropy of a system remain constant for a reversible adiabatic process.
(4) Isothermal process: If Q amount of heat absorbed during an isothermal process at constant
temperature T, the change of entropy,
dS
dQ Q
T
T
Q1
and the gain of entropy of the sink is
T1
Q2
. The net gain of entropy of the system is
T2
dS = (
Q1 Q 2
).
T1 T2
Q1 Q 2
=
T1 T2
Q1 Q 2
=0
T1 T2
Q1 Q 2
Q1
T1 T2
, working between the same two
T1
temperatures.
Q1 Q 2
T1 T2
<
Q1
T1
Or, 1-
Q2
T2
<1Q1
T1
Or,
Q 2 T2
>
Q1 T1
Or,
Q 2 Q1
>
T2 T1
Or,
Q 2 Q1
>0
T2 T1
Q2
Q1
is the gain in entropy of the sink and
is the loss of entropy of the source. The change of entropy of
T2
T1
the working substance is zero as it returns to the original state at the end of a complete cycle.
Q 2 Q1
= positive.
T2 T1
Clausius-Clapeyron Relation:
The Clausius-Clapeyron relation, in thermodynamics, is a way of characterising the phase transition
between two states of matter, such as solid and liquid. On a pressure-temperature (P-T) diagram, the line
separating the two phases is known as the coexistence curve. The Clausius-Clapeyron relation gives the
slope of this curve
Mathematically,
dP
L
dT TV
where
dP
is the slope of the coexistence curve, L is the latent
dT
Q1 Q 2
T1 T2
or
Q1 Q 2 T1 T2
Q2
T2
Q1 T1
Q 2 T2
dL dT
L
T
Here,
Q1 = L + dL,
Q2 = L,
T1 = T + dT,
T2 = T
Q1 Q2 = L + dL - L = dL
dP (V 2 V1 ) dT
T1 T2 = T + dT T = dT
L
T
dP
L
(1)
dT T (V 2 V1 )
This is called the Clapeyrons latent heat equation.
Applications:
(1)
dP
is a positive quantity.
dT
It means that the rate of change of pressure with respect to temperature is positive. In such cases, the
melting point of the substance will increase with increase in pressure and vice versa.
(ii) If V2 is less than V1, then
dP
is a negative quantity.
dT
It means that the rate of change of pressure with respect to temperature is negative. In such cases, the
melting point of the substance will decrease with increase in pressure and vice versa. In the case of melting
ice, the volume of water formed is less than the volume of ice taken. Hence, V 2 V1.
Therefore, the melting point of the ice decreases with increase in pressure. Hence ice will melt at a
temperature lower than zero degree centigrade at a pressure higher than the normal pressure. Ice melts at 0
o
C only at a pressure of 76 cm of Hg.
(2)
When a liquid is converted into a gaseous state, the volume V 2 of the gas is always greater than the
corresponding volume V1 of the liquid i.e. V2 > V1.
Therefore,
dP
is a positive quantity.
dT
With increase in pressure, the boiling point of a substance increases and vice versa. The liquid will boil at a
lower temperature under reduced pressure. In the case of water, the boiling point increases with increase in
pressure and vice versa. Water boils at 100 oC only at 76 cm of Hg pressure. In the laboratories, while
preparing steam, the boiling point is less than 100 oC because the atmospheric pressure is less than 76 cm
of Hg. In pressure cookers, the liquid boils at a higher temperature because the pressure inside is more than
the atmospheric pressure.
SOLVED PROBLEMS
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Problem No. 1: One kilogram of ice at 00C is melted and converted to water at 0 0C. Compute the change in
entropy, assuming that the melting is done reversibly. The heat of fusion of water is L f = 3.34x105 J/kg.
Solution: The heat needed to melt the ice is Q = mLf = 3.34x105 J
S S 2 S 1
Q 3.34 x10 5 J
1.22 x10 3 J / K .
T
273 K
This increase corresponds to the increase in disorder when the water molecules go from the highly ordered
state of a crystalline solid to the much more disordered state of a liquid.
When we refreeze the water, Q has the opposite sign, and the entropy change of water is
S 1.22 x10 3 J / K .
The water molecules rearrange themselves into a crystal to form ice, so disorder and entropy both decrease.
Problem No. 2: One kilogram of water at 00C is heated to 1000C. Compute its change in entropy.
Solution: We know dQ = mcdT.
So,
2
S S 2 S 1
1
2
T
dQ
dT
373K
mc
mc ln 2 [1.00kg ][4190 J / kg.K ][ln
] 1.31x10 3 J / K
T
T1
273K
1 T
Problem No. 3: Suppose 1.00 kg of water at 100 0C is placed in thermal contact with 1.00 kg of water at 0
0
C. What is the change in entropy? Assume that specific heat capacity of water is constant at 4190 J/kg.K
over this temperature range.
Solution: The final temperature = 50 0C = 323 K.
The entropy change of the hot water =
T2
323 K dT
323 K
dT
[1.00kg][ 4190 J / kg.K ]
[ 4190 J][ln
] 603
373 K
T1 T
373 K T
mc
J/K
The entropy change of the cold water =[4190 J/K][ln(323/273)] = 705 J/K.
Therefore, the total entropy change of the system = -603+705 = 102 J/K
Problem No. 4: Find the entropy change for the isothermal expansion of 0.75 mol of an ideal gas from V 1 =
1.5 L to V2 = 3 L.
Solution: The change in entropy can be calculated from
V
Q
nR ln 2 [0.75mol][8.31 J / mol.K ][ln 2 ] 4.32
T
V1
11
J/K
Problem No. 5: An inventor claims to have constructed an engine that has an efficiency of 75% when
operated between the boiling and freezing points of water. Is it possible?
Solution: The efficiency of a real engine [with its irreversible processes and wasteful energy transfers] must
be less than the efficiency of a Carnot engine operating between the same two temperatures.
The efficiency of a Carnot engine operating between the boiling and freezing points of water is
TL
273
1
0.268 27 %
TH
373
Thus the claimed efficiency of 75% for a real engine operating between the given temperatures is impossible.
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