CHAPTER FOUR

4.0: Second law of thermodynamics

It is stated as “in an isolated system, a spontaneous process is always accompanied by an increase

in entropy”

4.1: Third law of thermodynamics

It states that the entropy of a pure and perfectly crystalline solid tends to zero as temperature tends
to absolute zero

The condition of absolute zero of temperature needs to be specified as to all other higher
temperatures, the atoms or molecules in the solid would not be completely at rest and therefore a
certain amount of disorder would be introduced. Perfectly crystalline substances are those in which
all the atoms, ions or molecules are arranged in a flawless lattice. Such ideal materials are very
rare and imperfect crystals, glasses and super cooled liquids all have residual entropies at zero.

4.2: Applications of third law of thermodynamics

The third of thermodynamics enables us to measure absolute entropies. Since a positive heat
energy changes invariably increases the entropy of a given system. It is possible to show that if a
quantity of heat qrev is exchanged between a system and its surroundings in a reversible manner
(thermodynamically) at a temperature T then the corresponding change in disorderness of the
system is given by
𝑄𝑟𝑒𝑣
∆𝑠 = 𝑠2 − 𝑠1 =
𝑇
4.3: Order and disorder in nature
It has been observed that all processes which occur spontaneously in nature are accompanied by
an increase in disorder. We observe that when gases mix although there is little (if any) enthalpy
change during the process, they do so spontaneously and in so doing create greater disorder in the
system.

Page 1|6
4.4: Entropy change during the change of state
Entropy is the degree of disorder or randomness of a system. For quantity of heat 𝑄𝑟𝑒𝑣 being
exchanged between the system and the surroundings in a thermodynamically reversible manner at
a temperature T, then the changes in entropy of the system is given by
𝑄𝑟𝑒𝑣
∆𝑠 = 𝑠2 − 𝑠1 =
𝑇
If the entropy occurs at a constant pressure p and temperature T, then the molar latent heat of
transformation being ΔH, assuming that the change occurs in a thermodynamically reversible
manner then 𝑄𝑟𝑒𝑣 = 𝛥𝐻
∆𝐻
∆𝑆 =
𝑇
4.5: Entropy change when temperature is changing
Consider a change dT in temperature occurring reversibly at a constant pressure P then
𝑐𝑝 𝑑𝑇 = 𝑑𝑄𝑝 , where 𝑐𝑝 is the heat capacity dividing through by T, we get
𝑐𝑝𝑑𝑇 𝑑𝑄𝑝
=
𝑇 𝑇
𝑑 𝑄𝑝
But = ΔS
𝑇
𝑑 𝑄𝑝 𝑐𝑝𝑑𝑇
ΔS = =
𝑇 𝑇

Integrating from T1 to T2 we get

𝑇 𝑐𝑝𝑑𝑇 𝑇 𝑑𝑇 𝑇 𝑇
∆𝑆 = ∫𝑇 2 = 𝐶𝑃 ∫𝑇 2 = 𝐶𝑃 ln[𝑇] 𝑇21 =𝐶𝑃 = (ln 𝑇2 − 𝑇2 ) =𝐶𝑃 = 𝑙𝑛 (𝑇2 )
1 𝑇 1 𝑇 1

4.6: The Carnot cycle

What is a Carnot Engine?

Carnot engine is a theoretical thermodynamic cycle proposed by Leonard Carnot. It gives the
estimate of the maximum possible efficiency that a heat engine during the conversion process of

Page 2|6
heat into work and conversely, working between two reservoirs, can possess. In this section, we
will learn about the Carnot cycle and Carnot Theorem in detail.

Carnot devised a cycle to represent the operation of an idealized engine in which heat is transferred
from a hot reservoir at a temperature TH partly converted into work and partly discarded to a colder
reservoir at a temperature TC

A heat engine is a device that transforms heat energy into work. A heat engine becomes a Carnot
cycle under reversible adiabatic or isothermal conditions.

The essential features of a Carnot cycle or heat engine

Page 3|6
Carnot Theorem:
According to Carnot Theorem:

Any system working between two given temperatures TH (hot reservoir) and TC (cold
reservoir), can never have an efficiency more than the Carnot engine working between the
same reservoirs, respectively.

Also, the efficiency of this type of engine is independent of the nature of the working substance
and is only dependent on the temperature of the hot and cold reservoirs

Carnot Cycle:
A Carnot cycle is defined as an ideal reversible closed thermodynamic cycle in which there are
four successive operations involved, which are isothermal expansion, adiabatic expansion,
isothermal compression and adiabatic compression. During these operations, the expansion and
compression of substance can be done up to the desired point and back to the initial state.

Operation of a Carnot cycle

Page 4|6
 Figure 4.1 illustrating the operation of a Carnot cycle
1. Reversible isothermal expansion from A to B at a temperature TH where heat |𝑄𝐻 | is absorbed
𝑄
from a hot reservoir. The entropy change is ( 𝑇 𝐻) where |𝑄𝐻 | is the heat supplied to the system
𝐻

from the hot reservoir and the work done on the systems surrounded by –W1. The volume
changes from V1 to V3
2. Reversible adiabatic expansion from B to C where temperature of the system is cooled from
TH to that of the cold reservoir at a temperature TC. No heat leaves the system, so the change
in entropy is zero. The volume changes from V3 to V4 and the work done is –W2.
3. Reversible isothermal compression from C to D where heat |𝑄𝐶 | is rejected or released to the
𝑄
cold reservoir at a temperature TC. The change in entropy is |𝑇 𝐶 | and the volume of the system
𝐶

changes from V3 to V2 and the work done on the system is W3.

4. Reversible adiabatic compression from D to A where temperature is raised from Tc to TH of
the hot reservoir. No heat enters the system; so the change in entropy is zero. The volume
changes from V2 to V1 and the work done is W4

Page 5|6
Page 6|6