Lecture 5

Second Law of Thermodynamics

According to Clausius: The spontaneous flow of heat from a cold to a hot temperature reservoir
is impossible without the action of an external device. It is a law that says nature constrains us
from getting certain kinds of outcomes without putting a lot of work into it.

Kelvin Plank statement of the 2nd law of thermodynamics is: It is impossible to construct an
engine which operating in a cycle will produce no effect other than extraction of heat from a
reservoir and performance of an equivalent amount of work.

Another way of stating the second law in terms of entropy is: The entropy of an isolated system
increases during any natural process.

Carnot's theorem, also called Carnot's rule is a principle which sets a limit on the maximum
amount of efficiency any possible engine can obtain, which thus solely depends on the difference
between the hot and cold temperature reservoirs. Carnot's theorem states: that all Carnot engines
operating between two given temperatures have the same efficiency, and no cyclic heat engine
operating between two given temperatures is more efficient than a Carnot engine.

Description of the Carnot Cycle

An important reversible cycle is the Carnot cycle. The Carnot cycle is the most efficient existing
cycle capable of converting a given amount of thermal energy into work

The system consists of a working substance such as an ideal gas, starting from a given initial
condition of temperature, pressure and volume is made to undergo two successive expansions
(one isothermal and another adiabatic) and then two successive compression (one isothermal and
another adiabatic) and then brought back finally to its original condition. The working substance
may also be a solid or liquid. This working substance is contained in a cylinder with a heat-
conducting base and non-conducting walls. We also provide, as part of the environment, a heat
reservoir in the form of a body of large heat capacity at a temperature T1, another reservoir at a
lower temperature T2 and two non-conducting stands. The Carnot Cycle is described by the
diagram below.

Four reversible sequence of Carnot cycle is:

1. isothermal expansion at high temperature T1
2. adiabatic expansion
3. isothermal compression at low temperature T2
4. adiabatic compression and back to stage 1

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Stage 1: The gas is in the initial equilibrium state a represented by p1, V1, T1. The first process
performed on the gas is an isothermal expansion. Pressure of the gas is lowered so the volume
increases. To keep temperature constant at T1, the heat source is brought into contact with the
cylinder and Q1 heat is transferred from the source to the gas. The gas goes to point b with p2,V2,
T1.

Stage 2: The second process performed on the gas is an adiabatic expansion. The cylinder is put
on the non conducting stand. The pressure in the gas is lowered further. The temperature
decreases to T2 and the volume increases and the gas goes to p3, V3, T2. During the process from
State 2 to State 3 no heat is transferred.

Stage 3. We put the cylinder on the colder heat reservoir. Compress the gas slowly to p4. So, the
pressure is raised, but the volume decreases. During this process from State 3 to State 4 heat
energy Q2 is transferred from the gas to the reservoir by conduction through the base to maintain
the temperature. The process is an isothermal compression and the system goes to state p4, V4, T2.

Stage 4. In the fourth state we put the cylinder on a non conducting stand and compress the gas
slowly to the initial condition p1, V1, T1. The pressure in the gas is raised. The temperature
increases and the volume is decreased. During the process from State 4 to State 1 no heat is
transferred and is adiabatic because no heat can enter or leave the system.

The net work W done by the system during the cycle is represented by the area enclosed by path
abcd in the Fig. The net amount of heat energy received by the system in the cycle is Q1 – Q2,
where Q1 is the heat absorbed in Step 1 and Q2 is that given up in Step 3. The initial and final
states are the same so that there is no net change in the internal energy U of the system.

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Heat Engine

A device which converts heat into work is called a heat engine. In general, work of any kind can
be converted into heat with 100% efficiency. However, the opposite process, the continual
conversion of heat into work, is never 100% efficient

We shall consider a gas enclosed in a cylinder by a piston. If heat is supplied to the gas, it
expands and pushes back the piston. Thus heat has been converted to work. But the process
stops, as soon as the pressure of the gas becomes equal to the pressure outside the cylinder.
Before there can be any further conversion of heat into work, the gas has to be returned to its
initial (compressed) state. That is, if there is to be a continual conversion of heat into work, the
gas has to undergo a cycle. Furthermore, the gas can be returned to its initial state only if some of
the heat it initially absorbed is given up to a sink which is at a lower temperature than the source.

Thus, in practice we find that all heat engines operate by taking some working substance around
a cycle, and:

(a) take heat at a high temperature,

(b) do work
(c) reject some of the heat at a lower temperature.

The engine has converted some heat to work and the rest is rejected as heat into the cold one.
This is not a violation of the first law of thermodynamics as there is no loss of energy.

Efficiency of a Heat Engine

The efficiency of an engine is the percentage of energy input that the engine can convert to
useful work.

The efficiency η of a heat engine is described by the ratio of the net work done by the engine
during one cycle to the heat taken in from the high temperature source in one cycle.

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Where

W = amount of work

Q1 = amount of heat

Now, W = Q1 – Q2 = amount of heat converted into work, so

Q1  Q2 Q
  1 2
Q1 Q1

Efficiency is expressed in percentage.

To show that the efficiency of a Carnot engine using an ideal gas as the working substance
is η = (T1-T2)/T1.

Along the isothermal path ab, the temperature, and hence the internal energy of an ideal gas,
remains constant. From the first law, the heat Q1 absorbed by the gas in its expansion must be
equal to the work W1 done in this expansion. But Q1 = W1 = µRT1 ln (V2/V1).
Likewise, in the isothermal compression along the path cd, we have
Q2 = -W2 = µRT2 ln (V3/V4). [work done here is negative]

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On dividing the first equation by the second, we obtain

From the equation describing an isothermal process for an ideal gas we obtain for the paths ab
and cd
p1V1 = p2V2 as we know pV = µRT
p3V3 = p4V4
From the equation describing an adiabatic process for an ideal gas we have for paths bc and da

p 2V2  p3V3

p 4V4  p1V1

Multiplying these four equations together and canceling the factor p1p2p3p4 appearing on both
sides, we obtain
V1V2 γ V3V4 γ = V2V3 γV4V1 γ,
From which (V2V4) γ-1 = (V3V1) γ-1
V2V4 = V3V1
=And V2/V1 = V3/V4.
Using this result in our expression for

Q1/Q2, we see that

Q1/Q2 = T1/T2
So that η = 1- Q2/Q1 = 1 – T2/T1

Entropy
Our experiences, tell us that there is a preferred direction to many natural processes. We aren't
surprised when a cup of coffee gradually loses heat to its surroundings as it cools, for example,
or when the ice in a glass of lemonade absorbs heat as it melts. But we would be surprised if a
cup of coffee suddenly grew hotter until it boiled or the water in a glass of lemonade froze on a
hot summer day, even though neither process violates the first law of thermodynamics.

Many chemical and physical processes are reversible and yet tend to proceed in a direction in
which they are said to be spontaneous. This raises an obvious question: What makes a reaction
spontaneous? What drives the reaction in one direction and not the other?

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The second law of thermodynamics describes the relationship between entropy and the
spontaneity of natural processes.

Second Law of Thermodynamics: In an isolated system, natural processes are spontaneous

when they lead to an increase in disorder, or entropy.

Entropy, S, is the degree of randomness or disorganization of the system. Entropy, the measure
of a system’s thermal energy per unit temperature that is unavailable for doing useful work.
Because work is obtained from ordered molecular motion, the amount of entropy is also a
measure of the molecular disorder, or randomness, of a system. The concept of entropy provides
deep insight into the direction of spontaneous change for many everyday phenomena Natural
processes tend to have increases in randomness or entropy. Gases are more random than liquids
which are more random than solids.

If dQ is the quantity of heat absorbed or rejected at the temperature T, the small change of
entropy dS is given by

Now, ds = 0 for adiabatic process and ds ≠ 0 for non-adiabatic process.

Entropy change for a reversible process

(1) Reversible adiabatic process:

By definition, the heat absorbed in a reversible adiabatic process is given by

= S = constant Q is constant here.

That is, the entropy of a system remains constant for a reversible adiabatic process.

(2) Reversible isothermal process:

In a reversible isothermal process the temperature remains constant and for such a process

That is, the change in entropy of a system in a reversible isothermal process is equal to the heat
absorbed or given out by the system, divided by the thermodynamic temperature of the system

If heat flows into the system, Q is positive and the entropy increases. If heat flows out of the
system, Q is negative and the entropy decreases.

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Entropy Change for an irreversible process:

In an irreversible process like conduction or radiation, heat is lost by a body at a higher

temperature T1 and is gained by the body at a lower temperature T2. Here T1 is greater than T2.

Let Q = quantity of heat given out by a hot body at a higher temperature T1. So it loses energy Q
and so its entropy change is ΔSH = - Q/T1.

Q = Heat gained by the body at a temperature T2. Because it absorbs energy its entropy increases
by ΔSC = Q/T2

Consider the hot and cold bodies as one system then

Q
Loss in entropy of the hot body ΔSH = - T1

Q
Gain in entropy of the cold body ΔSC = T2

Q Q

Therefore, the change in entropy of the system is ΔS = ΔSH + ΔSC = T2 T1 --------- (eq 1)

But, here T1 is greater than T2. So (eq 1) is a positive quantity.

Hence the change in entropy is positive. Thus the entropy of the system increases in all
irreversible processes.

State Function: State functions are "variables" that define the state of a system. By states we mean
the system can be described by a set of properties. For example, the state of a system might be that 1
mole of argon in a 10 L container with a temperature of 300 K. Here the state of the system is defined
by the "state functions" of volume and temperature as well as the amount of the gas.

Entropy is a State Function: Like pressure, energy and temperature, entropy is a property of
the state of a system and is independent of how the state is reached.

We can prove that entropy is a state function by the special case in which an ideal gas is taken
through a reversible process.

To make the process reversible, it is done slowly in a series of small steps, with the gas in an
equilibrium state at the end of each step. For each small step, the energy transferred as heat to or
from the gas is dQ, the work done by the gas is dW, and the change in internal energy is dEint .
These are related by the first law of thermodynamics in differential form

dEint = dQ – dW

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But as the steps are reversible, we can put dW = pdV and dEint = μCvdT then

dQ= pdV + nCvdT --------------- (i)

Using the ideal gas law pV = μRT, we get

In equation (i) put this value of p and divide by T

Now let us integrate each term eq (2) between an arbitrary initial state I and final state f we get

But

Therefore

Here change in entropy ΔS depends only on properties of the initial state (Vi and Ti) and
properties of the final state (Vf and Tf) and does not depend on how the gas changes between
the two states.

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Third law of thermodynamics The third law of thermodynamics is a statistical law of nature
regarding entropy and the impossibility of reaching absolute zero of temperature. “As a system
approaches absolute zero, all processes cease and the entropy of the system approaches a
minimum value”.

The Third Law of Thermodynamics can be visualized by thinking about water. Water in gas
form has molecules that can move around very freely. Water vapor has very high entropy
(randomness). As the gas cools, it becomes liquid. The liquid water molecules can still move
around, but not as freely. They have lost some entropy. When the water cools further, it becomes
solid ice. The solid water molecules can no longer move freely, but can only vibrate within the
ice crystals. The entropy is now very low. As the water is cooled more, closer and closer to
absolute zero, the vibration of the molecules diminishes. If the solid water reached absolute zero,
all molecular motion would stop completely. At this point, the water would have no entropy
(randomness) at all which is a contradiction as the entropy cannot be zero.

Probable Questions

1. Define second law of thermodynamics (i) according to Clausius (ii) according to Kelvin
and Planck.
2. Draw the Graph of a Carnot cycle. What are stages of Carnot cycle.
3. Explain the stages of a Carnot cycle.
4. What is Heat engine? Give a description of a heat engine.
5. Explain the efficiency of a heat engine.
6. Show that the efficiency of a Carnot engine using an ideal gas is η = (T1-T2)/T1.
7. Define Entropy and expain the change in entropy in case of a reversible process.
8. Show that entropy increases in all natural processes.
9. Explain third law of thermodynamics.