CHEM F211 : Physical Chemistry-I

The second law of thermodynamics (continued)

(Lecture 05)
- Prashant Uday Manohar
In the last class, we learned
●
The second law statements
●
Carnot’s principle
●
Carnot cycle

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Objectives
●
Entropy
●
Entropy change
●
Reversibility
●
Thermodynamic temperature scale

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The second law: Historical developments
Pictures on this slide have been downloaded from Wikimedia commons
Sadi Carnot (1824), a French engineer, in
a book “Reflections on the Motive Power
of Fire”, pointed out that a heat engine
must exchange heat with two bodies at
different temperatures in order to
produce continuous mechanical work.
His work was based on the then known
(but later, discarded) caloric theory of
heat and had some limitations. Carnot
died of cholera in 1832. Sadi Carnot Rudolph Clausius William Thomson
(Lord Kelvin)
In 1850, Rudolph Clausius and William Thomson (Lord Kelvin) corrected Carnot’s work to
conform with the first law of thermodynamics.
The Second law of thermodynamics
The Kelvin-Planck statement: It is impossible for a system to undergo a cyclic process whose
sole effects are the flow of heat into the system from a heat reservoir and the performance of
an equivalent amount of work by the system on the surrounding.
The Clausius statement: It is impossible for a system to undergo a cyclic process whose sole
effects are the flow of heat into the system from a cold reservoir and the flow of an equal
amount of heat out of the system into a hot reservoir.

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Carnot’s principle

Since the magnitude of the heat exchange of each engine with

the hot reservoir is same and since, the super-engine is more
efficient than the reversible engine, the work output of the
super-engine is greater than the work input required by the
reversed reversible heat engine. Thus, there will be surplus
work output available from the super-engine.

By first law, this surplus work output must be consequence of

some energy input.

Since there is no net absorption/emission of energy from/to the hot reservoir, the energy input
must be from the cold reservoir. However, this violates the second law of thermodynamics, and
is only due to our initial assumption that the efficiency of the super-engine is greater than that
of the reversible heat engine, which must be wrong.
Thus, we have:
e any engine ≤erev
Now imagine, if we replace the super-engine in the figure by another reversible engine. Then, it
is trivial to prove that both the engines will have identical efficiencies as long as they operate
between same set of temperatures. In other words, the efficiency of a heat engine would be a
function of the working temperatures only.
e rev =f ( τ H , τ C )
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Efficiency of reversible heat engine
We have seen that the efficiency of a heat engine is the function of the temperatures of the hot
and the cold reservoirs only. e =f ( τ , τ )
rev H C
Thus, one can choose any set of reversible processes between
these temperatures, such that the overall process is cyclic. We
will find the function f, for the ideal-gas temperature scale by
taking τ=T.
τ=T We consider four reversible processes in the
following sequence as shown in the figure:
● Isothermal expansion at TH (1→2)
● Adiabatic expansion from TH to TC (2→3)
● Isothermal compression at TC (3→4)
● Adiabatic compression from TC to TH (4→1)

This reversible cycle is called Carnot cycle. The working substance in Carnot cycle need not be
a perfect gas. However, we will use the cycle with perfect gas as our working substance,
because, the calculation of various thermodynamic quantities is very simple for perfect gas. For
perfect gas, we have: P=nRT/V and dU=CV(T)dT.(T)dT By first law, we thus have:
dV dT δ q rev dV
C V (T )dT =δ q rev −nRT ; C V (T )
= −nR
V T T V
δq
∮ C V (T ) dT
T
=∮ rev −nR ∮
T
dV
V

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Efficiency of reversible heat engine

dV dT δ q rev dV
C V (T )dT =δ q rev −nRT ; = C V (T )
−nR
V T T V
δ q rev
∮ V T ∮ T −nR ∮ dV
C (T )
dT
=
V

Consider:
TC TH

∮ C V (T ) dT
T
=0+∫ C V (T )
dT
T
dT
+0+∫ C V (T ) =0 ;
T
T H T C

Similarly, we see that:

V2 V3 V4 V1
dV dV dV dV dV
nR ∮ =nR ∫ +nR ∫ +nR ∫ +nR ∫ =0 ;
V V V 1 V V V2
V V V 3 4

It thus, follows:
δ q rev
∮ T =0
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Efficiency of reversible heat engine

We have obtained: δ q rev

∮ T =0=dS

Now, let us expand the above cyclic integral. The processes

2→3 and 4→1 being adiabatic, the δqrev is zero and the integrals
in the corresponding intervals is zero. We thus have:

δ q rev 2 δ q rev 4 δ q rev 1 2 1

4
qH qC
0=∮ =∫ +∫ = ∫ δ q rev + ∫ δ q rev = +
T 1 T 3 T TH 1 TC 3 T H TC

It thus, follows: qH q qC T
=− C ; =− C
TH TC qH TH

The efficiency of the reversible heat engine (or Carnot heat engine) will thus be:
T C T H −T C
e rev =1− =
TH TH

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Entropy
Figure taken from I.N. Levine, Physical Chemistry,
Consider a reversible cyclic process as shown in the adjacent PV diagram. We 6th Ed. (McGraw Hill Education)

draw the reversible adiabats (dashed curves) so as to divide the cycle into
adjacent strips. Consider the strip between the adiabats: a-c and b-d.
b-d The strip
is bound by a-b on the top and c-d on the bottom.
Now we draw reversible isotherm m-n at some temperature, say, Tab such that
the area under the zig-zag curve a-m-n-b equals to the area under the smooth
curve a-b.
a-b

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Entropy
Figure taken from I.N. Levine, Physical Chemistry,
Consider a reversible cyclic process as shown in the adjacent PV diagram. We 6th Ed. (McGraw Hill Education)

draw the reversible adiabats (dashed curves) so as to divide the cycle into
adjacent strips. Consider the strip between the adiabats: a-c and b-d.
b-d The strip
is bound by a-b on the top and c-d on the bottom.
Now we draw reversible isotherm m-n at some temperature, say, Tab such that
the area under the zig-zag curve a-m-n-b equals to the area under the smooth
curve a-b.
a-b
Since this area corresponds to negative to the work done on the system during
the given process, we have: wa-m-n-b= wa-b.

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Entropy
Figure taken from I.N. Levine, Physical Chemistry,
Consider a reversible cyclic process as shown in the adjacent PV diagram. We 6th Ed. (McGraw Hill Education)

draw the reversible adiabats (dashed curves) so as to divide the cycle into
adjacent strips. Consider the strip between the adiabats: a-c and b-d.
b-d The strip
is bound by a-b on the top and c-d on the bottom.
Now we draw reversible isotherm m-n at some temperature, say, Tab such that
the area under the zig-zag curve a-m-n-b equals to the area under the smooth
curve a-b.
a-b
Since this area corresponds to negative to the work done on the system during
the given process, we have: wa-m-n-b= wa-b.

Since the both the processes start at same initial state and end at same final state, the internal energy change
in both the processes is identical. By first law, thus, we have: qm-n= qa-b.

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Entropy
Figure taken from I.N. Levine, Physical Chemistry,
Consider a reversible cyclic process as shown in the adjacent PV diagram. We 6th Ed. (McGraw Hill Education)

draw the reversible adiabats (dashed curves) so as to divide the cycle into
adjacent strips. Consider the strip between the adiabats: a-c and b-d.
b-d The strip
is bound by a-b on the top and c-d on the bottom.
Now we draw reversible isotherm m-n at some temperature, say, Tab such that
the area under the zig-zag curve a-m-n-b equals to the area under the smooth
curve a-b.
a-b
Since this area corresponds to negative to the work done on the system during
the given process, we have: wa-m-n-b= wa-b.

Since the both the processes start at same initial state and end at same final state, the internal energy change
in both the processes is identical. By first law, thus, we have: qm-n= qa-b.
Analogously, one can imagine an isotherm r-s at temperature, say, Tcd, such that the area under the zig-zag
curve c-r-s-d equals to that under the smooth curve c-d,c-d so that wc-r-s-d= wc-d; and from the first law, it
follows: qr-s= qc-d.

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Entropy
Figure taken from I.N. Levine, Physical Chemistry,
Consider a reversible cyclic process as shown in the adjacent PV diagram. We 6th Ed. (McGraw Hill Education)

draw the reversible adiabats (dashed curves) so as to divide the cycle into
adjacent strips. Consider the strip between the adiabats: a-c and b-d.
b-d The strip
is bound by a-b on the top and c-d on the bottom.
Now we draw reversible isotherm m-n at some temperature, say, Tab such that
the area under the zig-zag curve a-m-n-b equals to the area under the smooth
curve a-b.
a-b
Since this area corresponds to negative to the work done on the system during
the given process, we have: wa-m-n-b= wa-b.

Since the both the processes start at same initial state and end at same final state, the internal energy change
in both the processes is identical. By first law, thus, we have: qm-n= qa-b.
Analogously, one can imagine an isotherm r-s at temperature, say, Tcd, such that the area under the zig-zag
curve c-r-s-d equals to that under the smooth curve c-d,c-d so that wc-r-s-d= wc-d; and from the first law, it
follows: qr-s= qc-d.
Now, it is obvious that the work and heat transfer in a Carnot cycle m-n-s-r-m is same as in the process a-b-
d-c-a around the strip, and consequently, qc-d /Tcd= qa-b/Tab. Continuing like this for all the strips, we see that
∮ δ q rev / T =0 for the arbitrary reversible cyclic process.

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Entropy
Figure taken from I.N. Levine, Physical Chemistry,
Consider a reversible cyclic process as shown in the adjacent PV diagram. We 6th Ed. (McGraw Hill Education)

draw the reversible adiabats (dashed curves) so as to divide the cycle into
adjacent strips. Consider the strip between the adiabats: a-c and b-d.
b-d The strip
is bound by a-b on the top and c-d on the bottom.
Now we draw reversible isotherm m-n at some temperature, say, Tab such that
the area under the zig-zag curve a-m-n-b equals to the area under the smooth
curve a-b.
a-b
Since this area corresponds to negative to the work done on the system during
the given process, we have: wa-m-n-b= wa-b.

Since the both the processes start at same initial state and end at same final state, the internal energy change
in both the processes is identical. By first law, thus, we have: qm-n= qa-b.
Analogously, one can imagine an isotherm r-s at temperature, say, Tcd, such that the area under the zig-zag
curve c-r-s-d equals to that under the smooth curve c-d,c-d so that wc-r-s-d= wc-d; and from the first law, it
follows: qr-s= qc-d.
Now, it is obvious that the work and heat transfer in a Carnot cycle m-n-s-r-m is same as in the process a-b-
d-c-a around the strip, and consequently, qc-d /Tcd= qa-b/Tab. Continuing like this for all the strips, we see that
∮ δ q rev / T =0 for the arbitrary reversible cyclic process.
Thus, δqrev /T is an exact differential. The corresponding thermodynamic property is referred to as entropy,
S. δ q rev
The entropy change of the system in an infinitesimal process is given by: dS=
T

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Entropy changes in various processes
δ q rev
The entropy change in an infinitesimal process is given by: dS=
T 2
δ q rev
Integrating this, one obtains entropy change for a finite process: Δ S=S 2 −S 1=∫
1 T
The entropy being state function, remains unchanged when a system undergoes a cyclic
process.
Since there is no heat transfer in an adiabatic process, the entropy change in a reversible
adiabatic process is zero.
2 2
δ q rev 1 q rev Δ H tr
Phase change at constant T and P: Δ S= ∫ T T ∫ rev T = T
= δ q =
1 1
2
CP
Constant pressure heating with no phase change: Δ S=∫ T dT
1
2
CV
Constant volume heating with no phase change: Δ S=∫ dT
1 T
q rev
Reversible isothermal process: Δ S=
T 2
CV V2
Reversible change of state of a perfect gas: Δ S=∫T dT +nR ln
1 V1
V V
Mixing of two inert perfect gases: Δ S=Δ S a +Δ S b =n a R ln +n b R ln
Va Vb
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Entropy, reversibility and irreversibility

We have so far discussed entropy change of system in various processes.

We will now consider the entropy change of universe. We have,
Δ S universe =Δ S system +Δ S surrounding

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Entropy, reversibility and irreversibility

We have so far discussed entropy change of system in various processes.

We will now consider the entropy change of universe. We have,
Δ S universe =Δ S system +Δ S surrounding

Reversible process:
In a reversible process, the heat transfer between the system and the surrounding takes place
very very slowly, so that there is no finite temperature difference between the system and
the surrounding. The infinitesimal heat transfer, δqrev, for system and surrounding are
negatives of each other and the temperature of the system is same as that of the surrounding.

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Entropy, reversibility and irreversibility

We have so far discussed entropy change of system in various processes.

We will now consider the entropy change of universe. We have,
Δ S universe =Δ S system +Δ S surrounding

Reversible process:
In a reversible process, the heat transfer between the system and the surrounding takes place
very very slowly, so that there is no finite temperature difference between the system and
the surrounding. The infinitesimal heat transfer, δqrev, for system and surrounding are
negatives of each other and the temperature of the system is same as that of the surrounding.
Thus,

δ q rev , syst δ q rev , surr δ q rev δ qrev

Δ S universe =Δ S system +Δ S surrounding = + = − =0 ; (reversible process)
T syst T surr T T

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Entropy, reversibility and irreversibility
Figure taken from I.N. Levine, Physical Chemistry,
6th Ed. (McGraw Hill Education)

Irreversible process:
In an irreversible process, the heat transfer the changes in the state of
the system are not smooth.

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Entropy, reversibility and irreversibility
Figure taken from I.N. Levine, Physical Chemistry,
6th Ed. (McGraw Hill Education)

Irreversible process:
In an irreversible process, the heat transfer the changes in the state of
the system are not smooth. Consider, for example, an irreversible
adiabatic process, 1-2 as shown by the dotted line in the adjacent
figure. The processes, 2-3,
2-3 3-4,
3-4 and 4-1 are reversible in nature.

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Entropy, reversibility and irreversibility
Figure taken from I.N. Levine, Physical Chemistry,
6th Ed. (McGraw Hill Education)

Irreversible process:
In an irreversible process, the heat transfer the changes in the state of
the system are not smooth. Consider, for example, an irreversible
adiabatic process, 1-2 as shown by the dotted line in the adjacent
figure. The processes, 2-3,
2-3 3-4,
3-4 and 4-1 are reversible in nature.
The entropy change of the system during the process, 1-2,
1-2 is dependent only on the initial and
final states, and should thus be same as the entropy change in a reversible process:1-4-3-2.

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Entropy, reversibility and irreversibility
Figure taken from I.N. Levine, Physical Chemistry,
6th Ed. (McGraw Hill Education)

Irreversible process:
In an irreversible process, the heat transfer the changes in the state of
the system are not smooth. Consider, for example, an irreversible
adiabatic process, 1-2 as shown by the dotted line in the adjacent
figure. The processes, 2-3,
2-3 3-4,
3-4 and 4-1 are reversible in nature.
The entropy change of the system during the process, 1-2, 1-2 is dependent only on the initial and
final states, and should thus be same as the entropy change in a reversible process:1-4-3-2.
The processes 1-4 and 3-2 being reversible adiabatic, the net entropy change in the process,
3
1-4-3-2, equals to that in the process, 4-3. Thus,
Δ S system ,1→ 2 =∫ δ q rev / T hr =−q3 → 4 /T hr
4

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Entropy, reversibility and irreversibility
Figure taken from I.N. Levine, Physical Chemistry,
6th Ed. (McGraw Hill Education)

Irreversible process:
In an irreversible process, the heat transfer the changes in the state of
the system are not smooth. Consider, for example, an irreversible
adiabatic process, 1-2 as shown by the dotted line in the adjacent
figure. The processes, 2-3,
2-3 3-4,
3-4 and 4-1 are reversible in nature.
The entropy change of the system during the process, 1-2, 1-2 is dependent only on the initial and
final states, and should thus be same as the entropy change in a reversible process:1-4-3-2.
The processes 1-4 and 3-2 being reversible adiabatic, the net entropy change in the process,
3
1-4-3-2, equals to that in the process, 4-3. Thus,
Δ S system ,1→ 2 =∫ δ q rev / T hr =−q3 → 4 /T hr
4
Now, consider the cyclic process, 1-2-3-4-1.
1-2-3-4-1 Except the process, 4-3, the other three processes
are adiabatic. Thus the heat transfer during the cyclic process is q3→4. The internal energy
change is zero in the cyclic process.

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Entropy, reversibility and irreversibility
Figure taken from I.N. Levine, Physical Chemistry,
6th Ed. (McGraw Hill Education)

Irreversible process:
In an irreversible process, the heat transfer the changes in the state of
the system are not smooth. Consider, for example, an irreversible
adiabatic process, 1-2 as shown by the dotted line in the adjacent
figure. The processes, 2-3,
2-3 3-4,
3-4 and 4-1 are reversible in nature.
The entropy change of the system during the process, 1-2, 1-2 is dependent only on the initial and
final states, and should thus be same as the entropy change in a reversible process:1-4-3-2.
The processes 1-4 and 3-2 being reversible adiabatic, the net entropy change in the process,
3
1-4-3-2, equals to that in the process, 4-3. Thus,
Δ S system ,1→ 2 =∫ δ q rev / T hr =−q3 → 4 /T hr
4
Now, consider the cyclic process, 1-2-3-4-1.
1-2-3-4-1 Except the process, 4-3, the other three processes
are adiabatic. Thus the heat transfer during the cyclic process is q3→4. The internal energy
change is zero in the cyclic process. Thus, the work done on the system equals to negative of
the heat transfer. In other words, the work done by the system on the surrounding equals to heat
transfer to the system: w=-q3→4.

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Entropy, reversibility and irreversibility
Figure taken from I.N. Levine, Physical Chemistry,
6th Ed. (McGraw Hill Education)

Irreversible process:
In an irreversible process, the heat transfer the changes in the state of
the system are not smooth. Consider, for example, an irreversible
adiabatic process, 1-2 as shown by the dotted line in the adjacent
figure. The processes, 2-3,
2-3 3-4,
3-4 and 4-1 are reversible in nature.
The entropy change of the system during the process, 1-2, 1-2 is dependent only on the initial and
final states, and should thus be same as the entropy change in a reversible process:1-4-3-2.
The processes 1-4 and 3-2 being reversible adiabatic, the net entropy change in the process,
3
1-4-3-2, equals to that in the process, 4-3. Thus,
Δ S system ,1→ 2 =∫ δ q rev / T hr =−q3 → 4 /T hr
4
Now, consider the cyclic process, 1-2-3-4-1.
1-2-3-4-1 Except the process, 4-3, the other three processes
are adiabatic. Thus the heat transfer during the cyclic process is q3→4. The internal energy
change is zero in the cyclic process. Thus, the work done on the system equals to negative of
the heat transfer. In other words, the work done by the system on the surrounding equals to heat
transfer to the system: w=-q3→4. Thus, if q3→4 is positive, the cyclic process would generate
positive work output by just drawing the heat, q3→4 from the hot reservoir, which is against the
second law. Therefore, we must have: q3→4≤0; and hence, Δ S system , 1→ 2 =−q 3→ 4 /T hr ≥0

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Entropy, reversibility and irreversibility
Figure taken from I.N. Levine, Physical Chemistry,
6th Ed. (McGraw Hill Education)

Irreversible process:
In an irreversible process, the heat transfer the changes in the state of
the system are not smooth. Consider, for example, an irreversible
adiabatic process, 1-2 as shown by the dotted line in the adjacent
figure. The processes, 2-3,
2-3 3-4,
3-4 and 4-1 are reversible in nature.
The entropy change of the system during the process, 1-2, 1-2 is dependent only on the initial and
final states, and should thus be same as the entropy change in a reversible process:1-4-3-2.
The processes 1-4 and 3-2 being reversible adiabatic, the net entropy change in the process,
3
1-4-3-2, equals to that in the process, 4-3. Thus,
Δ S system ,1→ 2 =∫ δ q rev / T hr =−q3 → 4 /T hr
4
Now, consider the cyclic process, 1-2-3-4-1.
1-2-3-4-1 Except the process, 4-3, the other three processes
are adiabatic. Thus the heat transfer during the cyclic process is q3→4. The internal energy
change is zero in the cyclic process. Thus, the work done on the system equals to negative of
the heat transfer. In other words, the work done by the system on the surrounding equals to heat
transfer to the system: w=-q3→4. Thus, if q3→4 is positive, the cyclic process would generate
positive work output by just drawing the heat, q3→4 from the hot reservoir, which is against the
second law. Therefore, we must have: q3→4≤0; and hence, Δ S system , 1→ 2 =−q 3→ 4 /T hr ≥0
The possibility of ∆Ssystem,1→2 =0 is discarded as it requires q3→4=0; =0 and hence, w=0, =0 which
means that in the cyclic process the system and surrounding restore their original states, which
means that the process is reversible. Thus, Δ S syst ,irrev >0 ; Δ S univ ,irrev >0
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Entropy, spontaneity

Thus, in general, for a given process, one can write:

Δ S univ ≥0

For reversible processes, Δ S univ =0

whereas,
for irreversible processes, Δ S univ >0

Spontaneous processes are irreversible in nature and thus, for spontaneity of a process the
∆Suniverse > 0 condition must be obeyed.

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Thermodynamic temperature scale

We have seen that the efficiency of a reversible heat engine is e rev =f ( τ H , τ C )

qC
Using e rev =1+ ; it follows: -qC/qH = 1 – f(τH,τC) ≡ g(τH,τC).
qH
By operating two Carnot engines with one of the reservoirs common, one can show that the
g(τH,τC) needs to obey: g(τH,τC)=φ(τC)/φ(τH).

Thus, we have: -qC/qH =φ(τC)/φ(τH) .

The simplest choice for φ(τ) is just the first power of τ; and results in the thermodynamic scale
for temperature measurement. The scale is further calibrated by fixing the triple point of water
to be 273.16 units in the thermodynamic temperature scale. It then coincides with the ideal gas
temperature scale or the absolute temperature scale.

|q C|
T =273.16 L
|q H|

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