5.

Entropy and the second law of thermodynamics

5.1

Entropy
We note that for the Carnot cycle,
processes b c and d a are reversible adiabatic,

T2Vb 1 = T1Vc 1

and

Vb Vc
=
Va Vd

V
n b
V a

T2Va 1 = T1Vd 1

V
= n c

V d

The magnitudes of heat flow during the reversible isothermal processes are
a b:

V
Q2 = nRT2n b
Va

c d:

V
Q1 = nRT1n c
Vd

V
nRT2 n b
Q2
Va = T2
=
Q1
V T1
nRT1n c
Vd

We see that

if

T2 > T1 ,

This seems to imply that

Q
T

|Q2| > |Q1|

is a constant within a cyclic process such as the Carnot cycle

Taking into account of the direction of heat low,

Q2
T
= 2
Q1
T1

or

Q1 Q2
+
=0
T1 T2

Q1 = +ve , Q2 = -ve

Generally for any reversible cyclic process, if it is divided into small processes, the sum of the
Q
Q
quantities
for all the isothermal processes,
= 0.
T
T

dQ
T =0

For sufficiently small processes,

dQ
= dS
T

Define quantity

dS = 0

S is called the entropy of the system (unit : J/K)

s=

S
m

or

S
n

is the specific entropy

T-S diagram
T
b

Area = TdS = dQ = Q
a

Sa

Sb

Area under the T-S curve represents the heat flow during the process
For a Carnot cycle,

5.2

Entropy changes in reversible processes

All reversible processes can be represented by a curve in the T-S diagram
(a) Reversible adiabatic process (b-c or d-a in the Carnot cycle)
dQ = 0

dS = 0

means that the entropy does not change during this process.
(b) Reversible isothermal process (a-b or c-d in the Carnot cycle)
b

dQ
a T

dS =
a

Sb Sa =

(c) Reversible isochoric process

( Sb Sa )v = C v

T
dT
= C v n b
T
Ta

Q2
T

(d) Reversible isobaric process

( Sb Sa ) P = C P

T
dT
= C P n b
T
Ta

For every reversible process, if the entropy of the system increases, the entropy of the
environment will decrease by the same amount
This means that the total entropy of the system and the environment (or any isolated closed
system) is not change for reversible process.
5.3

Entropy changes in irreversible processes

Although we define the change in entropy for reversible process, the entropy of a system S is
actually a property of a system determined by the state of the system.
This means that the change in entropy between two states of a system is the same for reversible
as well as irreversible processes

Consider a system at temperature T2 acting as reservoir (its temperature will NOT change)
Take a second small system at temperature T1 and combine it with the reservoir.
T1

T2

After a sufficiently long time, thermal equilibrium is established at temperature T2

This overall process is irreversible
For the small system, its temperature is changed from T1 to T2 ,

T
If the process is isobaric, the change in entropy is Sb = C P n 2
T1
T
Or, if the process is isochoric, the change in entropy is Sb = C v n 2
T1

Q
T2

For the reservoir,

S r =

If P is not changed,

dQ = C P dT

(Isothermal)

Q = C P (T2 T1 )

S r =

C P (T2 T1 )
T2

Total entropy change :

S = S b + S r
T T T1
= C P n 2 2

T2
T1

always positive

The entropy of a system will increase after a irreversible process

Example :

Air conditioner
Outside Q1
W
Q2
room
W : Work done to the system
Q1 : heat flow out of the system to the environment
Q2 : heat flow into the system from the room

Q2 T2
=
Q1 T1

Carnot cycle

We need to get Q2 < Q1 so that T2 < T1

Hence,

S =

Q1 Q2

0
T1 T2

5.4

The second law of thermodynamics

For any closed and isolated system (example: object + reservoir),
Change of entropy after any process

S 0

S = 0

reversible process

S > 0

irreversible process

S object

S reservoir

but the overall S or

The second law of thermodynamics states that :

After a process, the entropy of a closed system either increases or remains constant.
or,

The entropy of a closed system cannot be destroyed but can be created.

The Clausius Statement

No process is possible whose sole result is a heat flow out of one system at a given
temperature and a heat flow of the same magnitude into a second system at a higher
temperature.

Kelvin-Planck Statement
No process is possible whose sole result is a heat flow Q out of a reservoir at a single
temperature, and the performance of work W equal in magnitude to Q.