Chapter 22

Heat Engine, Entropy and the

second law of thermodynamic
Heat Engine and The
Second Thermodynamic law
Heat Pumps & Refrigerators
The carnot Engine
Gasoline & Diesel Engine
Entropy
Entropy Changes in
Irreversible Process
Entropy on a Microscopic
Scale

22.1 Heat Engine and The

second law of thermodynamic

Description Of Heat Engine

A heat Engine is a device that takes in energy
by heat and operating in a cyclic process,
expels a fraction of that energy by means of
work.

 A cyclic process of heat

engine

When the engine absorb a quantity of energy(Qh)

from the hot reservoir and then gives up a quantity
of energy (QC) from cold reservoir
Through a cycle Eint = 0
From the firts law of thermodynamic
EInt = Q + w = Q-Weng
The net Weng done by a heat engine is equal to the
net energy Qnet transferred to it.
Qnet = Qh - Qc ,therefore,

Weng=Qh - Qc

The Thermal Effeciency

The Form of second law of

thermodynamics
Kelvin-Plank : its impossible to construct a heat
engine that, operating in a cycle, produce no
effect other than the input of energy by heat from
a reservoir and performance of an equal amount
of work.
Clausius : does not transfer energy doees not
transferr spontaneously by heat from a cold object
to a hot object

Quick quizz

Answer

22.1 (c). Equation 22.2 gives this result

directly.
22.2 (b). The work represents one third of
the input energy. The remainder, two thirds,
must be expelled to the cold reservoir

Heat Pumps and

Refrigerators
Heat Pumps and Refrigerators is a device that
transfer energy from cold reservoir to hot
reservoir.
In a refrigerator or heat pump, the engine
tahes in energy Qc from a cold reservoir and
expels energy Qh from a hot reservoir.

Coefficient of Performance

Quick Quiz

answer
(d). The COP of 4.00 for the heat pump
means that you are receiving four times as
much energy as the energy entering by
electrical transmission. With four times as
much energy per unit of energy from
electricity, you need only one fourth as much
electricity.

Reversible and Irreversible Processes

In the next section we discuss a theoretical heat engine that is

the most efficient possible. To understand its nature, we must
first examine the meaning of reversible and irreversible
processes. In a reversible process, the system undergoing the
process can be returned to its initial conditions along the same
path on a PV diagram, and every point along this path is an
equilibrium state. A process that does not satisfy these
requirements is irreversible.

Although all real processes are irreversible, some are almost

reversible. If a real process occurs very slowly such that the system is
always very nearly in an equilibrium state, then the process can be
approximated as being reversible. Suppose that a gas is compressed
isothermally in a pistoncylinder arrangement in which the gas is in
thermal contact with an energy reservoir, and we continuously transfer
just enough energy from the gas to the reservoir during the process to
keep the temperature constant. For example, imagine that the gas is
compressed very slowly by dropping grains of sand onto a frictionless
piston, as shown in Figure 22.9. As each grain lands on the piston and
compresses the gas a bit, the system deviates from an equilibrium
state, but is so close to one that it achieves a new equilibrium state in a
relatively short time interval. Each grain added represents a change to
a new equilibrium state but the differences between states are so
small that we can approximate the entire process as occurring through
continuous equilibrium states. We can reverse the process by slowly
removing grains from the piston.

A general characteristic of
a reversible process is that
no dissipative effects (such
as turbulence or friction)
that convert mechanical
energy to internal energy
can be present. Such
effects can be impossible
to eliminate completely.
Hence, it is not surprising
that real processes in
nature are irreversible.

The Carnot Engine

In 1824 a French engineer named Sadi Carnot described a theoretical
engine, now called a Carnot engine, which is of great importance from
both practical and theoretical viewpoints. He showed that a heat
engine operating in an ideal, reversible cyclecalled a Carnot cycle
between two energy reservoirs is the most efficient engine possible.
Such an ideal engine establishes an upper limit on the efficiencies of
all other engines. That is, the net work done by a working substance
taken through the Carnot cycle is the greatest amount of work
possible for a given amount of energy supplied to the substance at
the higher temperature. Carnots theorem can be stated as follows

The net work done in this reversible, cyclic process because the
change in internal energy is zero, the net work W engine done by the
gas in one cycle equals the net energy transferred into the system, |
Qh|-|Qc|. The thermal efficiency of the engine is given by Equation
22.2:

In Example 22.3, we show that for a Carnot cycle

Hence, the thermal efficiency of a Carnot engine is

Entropy Changes in
Irreversible Processes

 If the process is irreversible, then the total

entropy of an isolated system always
increases. In a reversible process, the total
entropy of an isolated system remains
constant.
The change in entropy of the Universe
must be greater than zero for an
irreversible process and equal to zero for a
reversible process.

Entropy Change in Thermal

Conduction
The energy transfer to or from each object is
reversible, and we may set Q = Qr .
Because the cold reservoir absorbs energy Q, its
entropy increases by Q/ Tc . At the same time, the
hot reservoir loses energy Q, and so its entropy
change is -Q/Th. Because Th > Tc , the increase in
entropy of the cold reservoir is greater than the
decrease in entropy of the hot reservoir.
Therefore, the change in entropy of the system
(and of the Universe) is greater than zero:

Entropy Change in a Free

Expansion

Formula of the entropy change for the

gas is

The isothermal, reversible expansion is only a

replacement process that we use to calculate the
entropy change for the gas; it is not the actual
process.
The free expansion has no effect on the
surroundings, and the entropy change of the
surroundings is zero. Thus, the entropy change
for the Universe is positive; this is consistent with
the second law.

Entropy Change in
Calorimetric Processes
Formula
:

Gasoline and Diesel Engines

(Otto cycle)

Entropy

22.8 Entropy on a
Microscopic Scale

In the kinetic theory of

gases, gas molecules are
represented as particles
moving randomly.
Let us suppose that the
gas is initially confined to a
volume Vi , as shown in
Figure 22.17a. When the
partition separating Vi
from a larger container is
removed, the molecules
eventually are distributed
throughout the greater
volume Vf (Fig.22.17b).
For a given uniform
distribution of gas in the
volume, there are a large
number of equivalent
microstates, and we can
relate the entropy of the
gas to the number of
microstates corresponding
to a given macrostate. The
instant after the partition
is removed (and before the
molecules have had a
chance to rush into the
other half of the

The ratio of the number of ways of placing the

molecules in the volume for the initial and final
configurations is

If we now take the natural logarithm of this

equation and multiply by Boltzmanns constant,
we find that

where we have used the equality N = nNA , that

NAkB is
the universal gas constant R; thus, we can write
this equation as

when n mol of a gas undergoes a free

expansion
from Vi to Vf , the change in entropy is

we make the following important connection

between entropy and the number of
microstates for a given macrostate