The second law of thermodynamics and

entropy

The second law of thermodynamics

In any cyclic process the entropy will either increase or
remain the same.
Entropy
A state variable whose change is defined for a reversible
process at T where Q is the heat absorbed.
A measure of the amount of energy which is unavailable
to do work.
In thermodynamics, entropy is a measure of the number
of specific ways in which a thermodynamic system may
be arranged, commonly understood as a measure of
disorder.
 dQrev
The entropy is defined as: dS , (unit: J/K)
T
B
dQrev
So that S B S A
A
T
,

where S is a function of state.

For an adiabatic process, dQrev 0

Thus an adiabatic process involves no change in entropy. This process is also

called isentropic.
T-S diagram

Area under the T-S curve represents the

heat flow during the process

b b

a TdS a dQ Q

Carnot cycle
Entropy changes in irreversible processes:
Entropy, S is defined in terms of reversible changes of heat.
Since S is a state function, then the integral of S around a closed
loop is zero, dQ
T
rev
0

The Clausius inequality implies that, integrating

around this loop,
dQ
T
0

p B dQ A dQ

B A T

B T
rev
0
B dQ B dQ

A T

A T
rev

This is true however close A and N get to each

other, the change in entropy,
A dQrev dQ
V dS
T T
Consider a thermally isolated system. In such a system dQ = 0 for any
process, so that the above inequality becomes

dS 0

This shows that any change for this thermally isolated system
always results in the entropy either staying the same (for a
reversible change) or increasing (for an irreversible change).
Another statement of second law of thermodynamics the entropy
of an isolated system tends to a maximum
Application to the Universe
Assuming that the Universe can be treated as an isolated system, the first
law of thermodynamics become:
(a) UUniverse = constant,
(b) SUniverse can only increase.
 Example 1:
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.
After a sufficiently long time, thermal
equilibrium is established at temperature
T2.
This overall process is irreversible.
From the small system, its temperature is
changed from T1 to T2,

T
If the process is isobaric, the change in entropy is: Sb CP ln 2
T1

Or, if the process is isochoric, the change in entropy is: Sb CV ln T2

T1
 Q
For the reservoir, S r
T2

If P is not changed, dQ CP dT
Q CP T2 T1

CP T2 T1
S r
T2

Total entropy change: S Sb S r

T2 CP T2 T1
CP ln
1 T T2
always positive

The entropy of a system will increase after a irreversible process

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

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

b b dQ Q2
a dS a T
Sb S a
T
 (c) Reversible isochoric process

dT Tb
Sb Sa V CV CV ln
T Ta
(d) Reversible isobaric process

dT Tb
Sb S a P CP CP ln
T a
T

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 system) is not change for reversible
process.
Summary:
dQ
dS (=for reversible, for irreversible)
T
dQ 2 dQ
Sb S a
1 T
T
0 reversible
2 dQ dQ
Sb S a
1 T
T
0 irreversible

dQ
Adiabatic & reversible: dQ 0 , dS , so dS 0 ,
T
dQ
Adiabatic & irreversible: dQ 0 , dS , so dS 0 ,
T
dQ
Isentropic & reversible: dS 0 , dS , so dQ 0 ,
T
dQ
Isentropic & irreversible: dS 0 , dS , so dQ 0 ,
T
Combined the first and second laws of
thermodynamics
The first law
dU dQ dW for all processes
The second law
dQ TdS
and for reversible processes
dW pdV

Combined
dU TdS pdV

The first combined First and Second Laws of Thermodynamics for P-V-T system
 For an irreversible change, dQ TdS and also dW -pdV, but
dQ being smaller than for the reversible process and dW
being larger than for the reversible process so that dU is the
same whether the change is reversible or irreversible.

dU TdS pdV

S and V are called natural variables (extensive; they scale

with the size of the system).
p and T are both intensive (they do not scale with the size of
the system).
Combined
dU TdS pdV

write dU as
U U
dU dS dV ,
S V V S

so U
T and
S V
U
p
V S
The ratio of p and T can also be written in terms of the variables U,
S and V, as follows:
p U S p S
U
T V S U V T V
Example 2:
Consider two systems, with pressure p1 and p2 and
temperatures T1 and T2. If internal energy U is transferred
from system 1 to system 2, and volume V is transferred from
system 1 to system 2 (Figure below), find the change of entropy.
Show that equilibrium results when T1=T2 and p1=p2.

T1 U, V T2
p1 p2

Two systems, 1 and 2, which are able to

exchange volume and internal energy
 dU TdS pdV
1 p
dS dU dV
T T

The change in entropy:

1 1 p1 p2
S U V
T1 T2 T1 T2

The entropy always increases in any physical process. Thus, when

equilibrium is achieved, the entropy will have achieved a
maximum, so that S = 0. This means that the joint system cannot
increase its entropy by further exchanging volume or internal
energy between system 1 and system 2. S = 0 can only be
achieved when T1 = T2 and p1 = p2.
The Joule expansion
Example of irreversible process; Joule expansion. One mole
of ideal gas (pressure pi, temperature Ti) is confined to the
left side of a thermally isolated container and occupies as a
volume V0. The right side of the container (volume V0) is
evacuated. The tap between the two parts of the container
is then suddenly opened and the gas fills the entire
container of volume 2V0 (new temperature Tf and pressure
pf). Both container are assumed to be thermally isolated
from their surroundings.
For the initial state, the ideal gas law implies that:
piV0 RTi
and for the final state,
p f 2V0 RT f
Since the system is thermally isolated from its surroundings,
U = 0. Also, since U is only a function of T for an ideal gas,
T = 0 and hence Ti = Tf. This implies that piV0 = pf(2V0), so
that the pressure,
pi
pf
2
 It is difficult to calculate directly the change of entropy
of a gas in Joule expansion along the route that it takes
from its initial state to the final state.
The pressure and volume of the system are undefined
during the process immediately after the partition is
removed since the gas is in a non-equilibrium state.
Entropy is a function of state therefore the changes of
functions state are independent if the route taken.
The change in entropy for a reversible isothermal
expansion of the gas can calculated.

Since the internal energy is constant in the isothermal expansion

of an ideal gas, dU = 0, and hence, dU TdS pdV TdS pdV

So,
f 2V0 pdV 2V0 R
S i dS V
0 T
V
0 V
dV Rln2

Since S is a function of state, this increase in entropy Rln2 is also the change of
entropy for the Joule expansion.
Question 1:
What is the change of entropy in the gas, surroudings, and
Universe during a Joule expansion?