Laws of Thermodynamics

Classical thermodynamics is the only physical theory of

“

universal content which … will never be overthrown.”

Albert Einstein

1
FIRST LAW OF THERMODYNAMICS
By the end of this subtopic, you will learn:
 Heat and Internal Energy
 Heat Capacity and Specific Heat Capacity
 Latent Heat
 Signs for Heat and Work in Thermodynamics
 Work done during Volume Changes
 Paths between Thermodynamics States
 Heat added in Thermodynamic Process
 First Law of Thermodynamics
 Some Applications of the first law of Thermodynamics
 Cyclic Processes and Isolate Systems
 Infinitesimal Changes of States
 Heat Capacities of Ideal Gas
 Relationship between Cp and CV of an ideal Gas
 The ratios of heat capacities
2
Introduction
When two objects at different temperatures are put in contact,
heat spontaneously flows from the hotter to colder objects. When
the temperatures between the two objects become equal, no
further heat flow, the two objects are said to be in thermal
equilibrium.

Thus, two systems are in thermal equilibrium if and only if they

have the same temperature

Zeroth law of thermodynamics:

If objects A and C are separately in thermal equilibrium with a
third object B, then objects A and C are in thermal equilibrium with
each other
3
HEAT AND INTERNAL ENERGY
At the outset, it is very important to make a clear distinction
between temperature, internal energy and heat:
 Temperature (in kelvins) is a measure of the average kinetic
energy of individual molecules
 Internal energy refers to the total energy of all the molecules
in the object
 Heat refers to a transfer of energy from one object to another
due to temperature difference

In other word

Internal energy is all the energy of a system that is associated with

its microscopic components—atoms and molecules—when
viewed from a reference frame at rest with respect to the object.
4
Internal energy includes kinetic energy of translation, rotation,
and vibration of molecules, potential energy within molecules,
and potential energy between molecules.

Heat is defined as the transfer of energy across the boundary of a

system due to a temperature difference between the system and
its surroundings.

 Heating substance transfer energy from one system to another,

however, internal energy of a system can be changed even if no
energy is transferred by heat.
 For example, when a gas is compressed by a piston, the gas is warmed and
its internal energy increases, but no transfer of energy by heat from the
surroundings to the gas has occurred. If the gas then expands rapidly, it cools
and its internal energy decreases, but no transfer of energy by heat from it to
the surroundings has taken place.
5
HEAT CAPACITY AND SPECIFIC HEAT
 If heat flows into an object, the temperature rises. But how
much does the temperature rise? That depends!
 Experiments show that the amount of heat Q required to
change the temperature of a given material is proportional
to the mass m of the material present and to the
temperature change T
𝑄 𝛼 𝑚∆𝑇 → 𝑄 = 𝑚 𝑐 ∆𝑇 (2.1)
Where c is a quantity characteristic of the material called its
specific heat .
𝑄 𝐽
𝑐 = (2.2)
𝑚∆𝑇 𝑘𝑔𝐶 °
 The heat capacity of a particular sample of a substance is defined as the
amount of energy needed to raise the temperature of that sample by 1°C.
 The specific heat c of a substance is the heat capacity per unit mass.
6
From eq. (2.1), if we assume that the specific heat does not vary
with temperature over the interval, ∆𝑇 = 𝑇𝑓 − 𝑇𝑖 . In general, if c
varies with temperature over the interval, then the correct
expression for Q is:

𝑇𝑓

𝑄=𝑚 𝑐 𝑑𝑇 (2.3)
𝑇𝑖

7
LATENT HEAT

 A substance often undergoes a change in temperature when

energy is transferred between it and its surroundings. There are
situations, however, in which the transfer of energy does not
result in a change in temperature. This is the case whenever the
physical characteristics of the substance change from one form
to another; such a change is commonly referred to as a phase
change

𝑄 = 𝑚𝐿 (2.4)

8
Figure 2.1: A plot of temperature versus energy added when
1.00 g of ice initially at 30.0°C is converted to steam at
120.0°C.
9
SIGNS FOR HEAT AND WORK IN THERMODYNAMICS

Figure 2.2: A thermodynamic

system may exchange
energy with its
surroundings (environment)
by means of heat, work, or
both.
Note the sign conventions
for Q and W

10
WORK DONE DURING VOLUME CHANGES
A common example of a thermodynamic system is a quantity of gas
enclosed in a cylinder with a movable piston. Internal-combustion
engines, steam engines, and compressors in refrigerators and air
conditioners all use some version of such a system.

Figure 2.3: A molecule

striking a piston (a) does
positive work if the piston
is moving away from the
molecule and (b) does
negative work if the piston
is moving toward the
molecule, hence the gas
expanded and compressed
respectively

11
Consider system whose volume can change (a gas, liquid, or solid)
in a cylinder with a movable piston. Suppose that the cylinder has
cross-sectional area A and that the pressure exerted by the system
at the piston face is p. The total force F exerted by the system on
the piston is 𝐹 = 𝑝𝐴

Figure 2.4: The infinitesimal

work done by the system
during the small expansion
dx

When the piston moves out an infinitesimal distance dx, the

word done by this force is:
𝑑𝑊 = 𝐹 𝑑𝑥 = 𝑝𝐴𝑑𝑥 = 𝑝𝑑𝑉
Where dV is the infinitesimal change of volume of the system 12
In a finite change of volume from 𝑉1 𝑡𝑜 𝑉2 ,

𝑉2
𝑊= 𝑝𝑑𝑉 (2.5)
𝑉1

 In general, the pressure of the system may vary during the

volume change. For instance in the case where the cylinders of
an automobile engine the pistons move back and forth.
 To evaluate the integral in Eq. (2.5), we have to know how the
pressure varies as a function of volume. We can represent this
relationship as a graph of p as a function of volume (pV –
diagram)

13
Figure 2.5: The work done equals the area under the curve on a
pV - diagram
If the pressure p remains constant while the volume changes
from 𝑉1 𝑡𝑜 𝑉2 , (Fig. 2.5 c) the work done by the system is:
𝑊 = 𝑝 𝑉2 − 𝑉1 (2.5)
(𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑖𝑛 𝑎 𝑣𝑜𝑙𝑢𝑚𝑒 𝑐ℎ𝑎𝑛𝑔𝑒 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
14
Examples:
An ideal gas undergoes an isothermal (constant-temperature)
expansion at temperature T, during which its volume changes from
𝑉1 𝑡𝑜 𝑉2 . How much work does the gas do?

SOLUTION:
IDENTITY: The ideal-gas law tells us that if the temperature of an
ideal gas remain constant, the quantity 𝑝𝑉 = 𝑛𝑅𝑇 also remains
constant. If the volume V changes, the pressure p must change as
well. Hence this problem asks for the work done by a gas that
changes volume with varying pressure.

Using eq. (2.5), and making the pressure as the function

of volume, solution can be obtained:
𝑉2
𝑛𝑅𝑇
𝑊= 𝑝𝑑𝑉 & →𝑝 =
𝑉1 𝑉
15
16
17
Exercise:
A quantity of ideal gas undergoes an expansion that increases its
volume from 𝑉1 𝑡𝑜 𝑉2 = 2𝑉1 . The final pressure of the gas is 𝑝2 . Does
the gas do more work on its surroundings if the expansion is at
constant pressure or at constant temperature? (i) constant pressure;
(ii) constant temperature; (iii) the same amount of work is done in
both cases; (iv) not enough information is given to decide.

18
PATHS BETWEEN THERMODYNAMIC STATES

 Thermodynamic process involves a change in volume, the

work is done and either is positive or negative on its
surroundings.
 Similarly, heat flows into or out of the system during the
process if there is a temperature difference between the
system and its surroundings.

 When a thermodynamic system changes from initial state

to a final state, it passes through a series of intermediate
states. These series of states are called Path. There are
always infinitely many different possibilities for these
intermediate states. When they are all equilibrium states,
the path can be plotted on a pV-diagram (Figure 2.6 (a)).

19
Figure 2. 6: The work done by a system during a transition between two
states depends on the path chosen, i.e., work done is path dependent. 20
Therefore, the work done by a system depends on the initial and
final states and on the path followed by the system between these
states.

 For a cyclic (closed loop) process such as 1  3  2  4 

1, the final state is the same as the initial state but the total
work done by the system is not zero.
 It is presented on the graph by the area enclosed by the
loop(Figure 2.6) Prove this?

21
HEAT ADDED IN A THERMODYNAMIC PROCESS
The energy transfer by heat Q into or out of a system also depends
on the process. Consider the situations depicted in Figure 2.7

Figure 2.7: (a) A gas at temperature Ti expands slowly while absorbing energy
from a reservoir in order to maintain a constant temperature. (b) A gas
expands rapidly into an evacuated region after a membrane is broken.
22
 Fig. 2.7 (a), the piston is held at its initial position by an
external agent  a hand, for instance. When the force with
which the piston is held is reduced slightly, the piston rises
very slowly to its final position. Because the piston is moving
upward, the gas is doing work on the piston.
 During this expansion to the final volume 𝑉𝑓 , just enough
energy is transferred by heat from the reservoir to the gas to
maintain a constant temperature 𝑇𝑖 .
 Now consider the completely thermally insulated system
shown in Fig. 2.7 (b). When the membrane is broken, the gas
expands rapidly into the vacuum until it occupies a volume 𝑉𝑓
and is at a pressure 𝑝𝑓 . This uncontrolled expansion of a gas
into vacuum is called a free expansion.
 In this case, the gas does no work because there is no movable
piston on which the gas applies a force. Furthermore, no
energy is transferred by heat through the insulating wall.
23
The initial and final states of the ideal gas in Fig. 2.7 (a & b) are
identical to the initial and final states, but the paths are different.

Therefore, we conclude that energy transfer by heat, like work

done, depends on the initial, final, and intermediate states of the
system. In other words, because heat and work depend on the
path, neither quantity is determined solely by the end points of a
thermodynamic process.

24
THE FIRST LAW OF THERMODYNAMICS
First law of thermodynamic can be deduced from Work – Energy
Principle:
 The change in internal energy of a closed system, ∆𝑈, will be
equal to the energy added to the system by heating minus the
work done by the system on the surroundings. In equation
form we write:

∆𝑈 = 𝑄 − 𝑊 (2.6)
FIRST LAW OF THERMODYNAMICS

Where Q is the net heat added to the system and W is the net work
done by the system. Sign conventions for Q & W should be
observed:
- Since, W is the work done by the system, then if work is done on the
system, W will be negative and U will increase,
- similarly, Q is positive for heat added to the system, so if heat leave the
25
system, Q is negative.
Figure 2.8: In a thermodynamic process, the internal
energy U of a system may (a) increase ∆𝑈 > 0 , (b)
decrease ∆𝑈 < 0 , or (c) remain the same ∆𝑈 = 0 26
SOME APPLICATIONS OF THE FIRST LAW OF THERMODYNAMICS

 An adiabatic process is one during which no energy enters or

leaves the system by heat—that is, 𝑄 = 0
 An adiabatic process can be achieved either by thermally
insulating the system from its surroundings (as shown in Fig.
2.7b) or by performing the process rapidly, so that there is
little time for energy to transfer by heat

∆𝑈 = −𝑊 (adiabatic process) (2.7)

 From this result, we see that if a gas expands adiabatically

such that W is positive, then ∆𝑈 is negative and the
temperature of the gas decreases.[ Why temp decreases?]
 Conversely, the temperature of a gas increases when the gas
is compressed adiabatically
27
 A process that occurs at constant pressure is called an
isobaric process. In such a process, the values of the heat
and the work are both usually nonzero. The work done by
the gas is simply

𝑊 = 𝑝 𝑉𝑓 − 𝑉𝑖 (isobaric process) (2.8)

 A process that takes place at constant volume is called an

isovolumetric process. In such a process, the value of the work
done is clearly zero because the volume does not change

∆𝑈 = −Q (isovolumetric process) (2.7)

This expression specifies that if energy is added by heat to a system

kept at constant volume, then all of the transferred energy remains in
the system as an increase of the internal energy of the system
28
Processes
• An isobaric process is one in which the
pressure is constant p = const.
• An isochoric process is one in which the volume
is constant, V = const.
• An isothermal process is one in which the
temperature is constant, T = const.
• An adiabatic process is one in which no heat
enters or leaves the system; i.e. Q = 0.
• An isentropic process is one in which the
entropy is constant, S = const.
29
Three Types of Process

Isothermal process Adiabatic process

P
System Adiabat

Isotherm

Heat bath or reservoir V

Adiabatic free expansion

P

●1
End points

●2
30
V
CYCLIC PROCESSES AND ISOLATED SYSTEMS

There are two special cases of the first law of thermodynamics:

1) Cyclic Process  A process that returns a system to its initial

state, i.e. the final state is the same as the initial state and so
the total internal energy change must be zero.

𝑈2 = 𝑈1 𝑎𝑛𝑑 𝑄 = 𝑊 (2. 8)

If a net quantity of work W is done by the system during this

process, an equal amount of energy have flowed into the
systems as heat Q.

31
2) Isolated system  is the one that does no work on its
surroundings and has no heat to or from its surroundings.
For any process taking place in an isolated system,

𝑄 =𝑊=0
𝑈2 = 𝑈1 = ∆𝑈 = 0 (2. 9)

In other words, the internal energy of an isolated system is

constant.

32
INFINITESIMAL CHANGES OF STATE

Infinitesimal change of state is a small changes of state. Lets

consider a small amount of heat 𝑑𝑄 added to the system, the
system does a small amount of work 𝑑𝑊, and its internal
energy changes by an amount 𝑑𝑈. For such a process we state
the first law in differential forms as:

𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 2.10
(first law of thermodynamics infinitesimal process)

The work done is also given as d𝑊 = 𝑝𝑑𝑉, so we can also state

the first law as:

𝑑𝑈 = 𝑑𝑄 − 𝑝𝑑𝑉 2.11
33
HEAT CAPACITIES OF AN IDEAL GAS

Heat capacity is defined as

1 ∆𝑄 𝐽
𝑐 =
𝑚 ∆𝑇 𝑘𝑔𝐶 °
 It is usually easiest to measure the heat capacity of a gas in a
closed container under a constant volume condition.

 The corresponding heat capacity is the molar heat capacity at

constant volume (𝐶𝑉 ).

 Heat capacity measurements for solids and liquids are usually

carried out in the atmosphere under constant atmospheric
pressure, the corresponding heat capacity is called molar heat
capacity at constant pressure (𝐶𝑝 ).
34
RELATING 𝑪𝒑 AND 𝑪𝑽 FOR AN IDEAL GAS
To derive a relationship between 𝐶𝑝 and 𝐶𝑉 , we first consider the
constant-volume process. Assume n moles of an ideal gas are at
temperature T in a constant-volume container. Then we place it in
thermal contact with a hotter body, an infinitesimal quantity of
heat 𝑑𝑄 flows into the gas, and its temperature increases by an
infinitesimal amount 𝑑𝑇. By the definition of 𝐶𝑉 , the molar heat
capacity at constant volume,

𝑑𝑄 = 𝑛𝐶𝑉 𝑑𝑇 2.12

The pressure increases during this process, but the gas does no
work (𝑑𝑊 = 0) because the volume is constant . Using eq. (2.10),
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊, since 𝑑𝑊 = 0 → 𝑑𝑄 = 𝑑𝑈 thus, eq. (2.12) can
also be written as:

𝑑𝑈 = 𝑛𝐶𝑉 𝑑𝑇 2.13 35
Now consider a constant-pressure process with the same
temperature change 𝑑𝑇. We can place the same gas in a cylinder
with a piston that we can allow to move just enough to maintain
constant pressure and bring the system into contact with a hotter
body. As heat flows into the gas, it expands at constant pressure
and does work. By the definition of 𝐶𝑝 , the molar heat capacity at
constant pressure, the amount of heat 𝑑𝑄 entering the gas is:

𝑑𝑄 = 𝑛𝐶𝑝 𝑑𝑇 2.14

The work 𝑑𝑊 done by the gas in this constant-pressure process is:

d𝑊=𝑝𝑑𝑉
36
We can also express d𝑊 in terms of the temperature change dT by
using the ideal-gas equation of state, p𝑉 = 𝑛𝑅𝑇. Because p is
constant, the change in V is proportional to the change in T:

𝑑𝑊 = 𝑝𝑑𝑉 = 𝑛𝑅𝑑𝑇 2.15

Substitute Eqs. (2.15), (2.14) and (2.15) into 𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊,

we obtain:

𝐶𝑝 = 𝐶𝑉 + 𝑅 2.16

Why should these two molar heat capacities be different?

37
THE RATIO OF HEAT CAPACITIES

 It is the value obtained from the ratio of heat capacities,

𝐶𝑝
γ=
𝐶𝑉
 For gases, 𝐶𝑝 is always greater than 𝐶𝑉 and is always
greater than unity

38
THE SECOND LAW OF THERMODYNAMICS

By the end of this subtopic, you will learn:

 What determines whether a thermodynamic process is

reversible or reversible,
 What a heat engine is, and how to calculate its
efficiency,
 How refrigerators and heat engines are related, and how
to analyse the performance of a refrigerator,
 How to do calculations involving the idealized Carnot
cycle for engines and refrigerators.

39
The second law of thermodynamics tells us about the direction of heat flow!
T40
 The first law of thermodynamic states that energy is conserved.
There are, however, many processes we can imagine that
conserve energy but are not observed to occur in nature.
For examples:
 when a hot object is placed in contact with a cold object, heat flows from
hotter one to the colder one, never spontaneously the reverse. If heat were to
leave the colder object and pass to the hotter one, energy could still be
conserved. Yet it doesn’t happen spontaneously,
 coffee cups and glasses break spontaneously if you drop them. But they don’t
go back together spontaneously.

Figure 2.9: Have you ever observed this process, a broken cup
spontaneously reassembling and rising up onto a table? 41
 Spontaneously, mean by itself without input of work of some
sort. (A refrigerator does move heat from a cold environment to
a warmer one, but only by doing work)
 The first law of thermodynamics (conservation of energy) would
not be violated if any of these processes could occur in reserve.
 To explain this lack of reversibility, second law of
thermodynamics was inverted.

 The second law of thermodynamics is a statement about which

processes occur in nature and which do not. It can be stated in a
variety of ways, all of which are equivalent:

 Statement by R.J.E Clausius (1822-1888) state that heat can flow

spontaneously from a hot object to clod object; heat will not
flow spontaneously from a cold object to a hot object.
42
 The statement applies to one particular process, it is not
obvious how it applies to other processes. A more general
statement is needed that will include other processes in a
more general.
 The development of a general statement of the second law of
thermodynamics was based partly on the study of heat
engines.
 A heat engine is any device that changes thermal energy into
mechanical work, such as steam engines and automobile
engines.

43
HEAT ENGINE

 Any device that transforms heat partly into work or mechanical

energy is called a heat engine. A quantity of matter inside the
engine undergoes inflow and outflow of heat, expansion and
compression, and sometimes changes of phase is called working
substance.
 In internal-combustion engines, such as those used in
automobiles, the working substance is a mixture of air and fuel;
in a steam turbine it is water.

 For this heat engine to work properly, the working substance

undergoes a cyclic process.

44
HOT AND COLD RESERVOIRS

 All heat engines work under two relatively high temperatures;

they absorb heat from a source at high temperature, perform
some mechanical work, and discard or reject some heat at a
lower temperature
 When a system is carried through a cyclic process, its initial
and final internal energies are equal. Thus, for cyclic process,
the first law of thermodynamic requires that:

𝑈2 − 𝑈1 = 0 = 𝑄 − 𝑊 𝑠𝑜 𝑄 = 𝑊

That is, the net heat flowing into the engine in a cyclic process
equals the net work done by the engine

45
That is, when working with heat engine, we can imagine the
working substance interact with two bodies:
1) Hot reservoir, that represents the heat source; it can give
the working substance large amounts of heat at a constant
temperature 𝑇𝐻 without appreciably changing its own
temperature,
2) Cold reservoir, can absorb large amounts of discarded
heat from the engine at a constant lower temperature 𝑇𝐶 .

The quantities of heat transferred from the hot and cold

reservoirs are denoted as 𝑄𝐻 and 𝑄𝐶 respectively. A quantity
of heat Q is positive when heat is transferred into the working
substance and is negative when heat leaves the working
substance. Thus in a heat engine, 𝑄𝐻 is positive but 𝑄𝐶 is
negative.
46
Energy-Flow Diagrams and Efficiency

Figure 2.10: Schematic energy-flow diagram for a heat engine

47
 When an engine repeats the same cycle over and over, 𝑄𝐻 and
𝑄𝐶 represent the quantities of heat absorbed and rejected by the
engine during one cycle; 𝑄𝐻 is positive, and 𝑄𝐶 is negative. These
quantities are usually expressed in terms of the absolute values
of Q’s and W’s because the absolute values are always positive.
 The net heat absorbed per cycle is:
𝑄 = 𝑄𝐻 + 𝑄𝐶 = 𝑄𝐻 − 𝑄𝐶 (2.17)

The useful output of the engine is the net work W done by the
working substance. From the first law:

𝑊 = 𝑄 = 𝑄𝐻 + 𝑄𝐶 = 𝑄𝐻 − 𝑄𝐶 (2.18)

Ideally, we would like to convert all the heat 𝑄𝐻 into work; in that
case we would have 𝑄𝐻 = 𝑊, and 𝑄𝐶 = 0. Experience shows that
this is impossible; there is always some heat wasted, and 𝑄𝐶 is
never zero. 48
Thermal efficiency () of an engine is defined as:

𝑊
η= (2.19)
𝑄𝐻

The thermal efficiency  represents the fraction of 𝑄𝐻 that is

converted to work

Substitute Eq. (2.18) for into eq. (2.19)

𝑊 𝑄𝐶 𝑄𝐶
η= =1 + =1 − (2.20)
𝑄𝐻 𝑄𝐻 𝑄𝐻

Thermal efficiency of heat engine

49
REFRIGERATORS

 Refrigerator is a heat engine operating in reverse way. Heat

engine takes heat from a hot place and gives off heat to a colder
place.

 Refrigerator does the opposite; it takes heat from a cold place

(the inside of the refrigerator) and gives it off to a warmer place
(usually the air in the room where the refrigerator is located).

 Heat engine has a net output of mechanical work, the

refrigerator requires a net input of mechanical work. Using the
sign conventions, for a refrigerator 𝑄𝐶 is positive but both W and
𝑄𝐻 are negative; hence 𝑊 = −𝑊 𝑎𝑛𝑑 𝑄𝐻 = −𝑄𝐻 , as
demonstrated in Figure 2.11
50
Figure 2.11: Schematic energy-
flow diagram of refrigerator

Figure 2.12: (a) Principle

of the mechanical
refrigeration cycle. (b)
How the key elements
are arranged in a
practical refrigerator

51
From the first law for a cyclic process:

𝑄𝐻 + 𝑄𝐶 − 𝑊 = 0 𝑜𝑟 −𝑄𝐻 = 𝑄𝐶 − 𝑊

or, because both 𝑄𝐻 and 𝑊 are negative,

𝑄𝐻 = 𝑄𝐶 + 𝑊 (2.20)

As shown in Fig. 2.11 , the heat 𝑄𝐻 leaving the working substance

and given to the hot reservoir is always greater than the heat 𝑄𝐶
taken from the cold reservoir. The absolute-value relationship is
valid for both heat engines and refrigerators.

𝑄𝐻 = 𝑄𝐶 + 𝑊 (2.21)
52
 From an economic point view, the best refrigeration cycle is
one that removes the greatest amount of heat 𝑄𝐶 from the
inside of the refrigerator for the least expenditure of
mechanical work 𝑊 . The relevant ratio is therefore
𝑄𝐶 𝑊 . The larger this ratio, the better the refrigerator. It
is called the coefficient of performance () of a refrigerator.

𝑄𝐶 𝑄𝐶
 = = (2.22)
𝑊 𝑄𝐻 − 𝑄𝐶

53
PRACTICAL REFRIGERATORS
The principles of the common refrigeration cycle are shown schematically in Fig.
2.12 a. The fluid “circuit” contains a refrigerant fluid (the working substance). The
left side of the circuit (including the cooling coils inside the refrigerator) is at low
temperature and low pressure; the right side (including the condenser coils outside
the refrigerator) is at high temperature and pressure. Ordinarily, both sides contain
liquid and vapour in phase equilibrium.
The compressor takes in fluid, compresses it adiabatically, and delivers it to the
condenser coil at high pressure. The fluid temperature is then higher than that of
the air surrounding the condenser, so the refrigerant gives off heat 𝑄𝐻 and
partially condenses to liquid. The fluid then expands adiabatically into the
evaporator at rate controlled by the expansion valve. As the fluid expands, it cools
considerably, enough that the fluid in the evaporator coil is colder than its
surroundings. It absorbs heat 𝑄𝐶 from its surroundings, cooling them and partially
vaporizing. The fluid then enters the compressor to begin another cycle.
The compressor, usually driven by an electric motor (Fig. 2.12 b), requires energy input and
does work 𝑊 on the working substance during each cycle.
An air conditioner operates on exactly the same principle. In this case the refrigerator box
becomes a room or an entire building. The evaporator coils are inside, the condenser is
outside, and fans circulate air through these. 54
 Experimental evidence suggests strongly that it is impossible
to build a heat engine that converts heat completely to work,
that is an engine with 100% thermal efficiency
 This impossibility is the basis of one statement of the second
law of thermodynamics, as follows:

It is impossible for any system to undergo a process in which it

absorbs heat from a reservoir at a single temperature and
converts the heat completely into mechanical work, with the
system ending in the same state in which it began.

This is called the “engine” statement of the second law. It is also

known as Kelvin-Planck statement.

55
The analysis of refrigerator, form another alternative statement of
the second law of thermodynamics. Heat flows spontaneously
from hotter to colder bodies, never the reverse. A refrigerator
does take heat from a colder to a hotter body, but its operation
requires an input of mechanical energy or work. This gives another
statement of second law of thermodynamics as:

It is impossible for any process to have as its sole result the transfer
of heat from a cooler to a hotter body.

This is called “refrigerator” statement of the second law. It is

also known as Clausius statement.

56
Figure 2.13: Energy-flow diagrams showing that the two forms
of the second law are equivalent
57
Figure 2.13: Energy-flow diagrams showing that the two forms
of the second law are equivalent
Exercise: Would a 100% -efficient engine (Fig. 2.13 a) violate first law of
thermodynamics? What about a workless refrigerator (Fig. 2.13 b)
58
REVERSIBLE AND IRREVERSIBLE PROCESSES

(a)

(b)
Figure 2.14: Reversible and Irreversible Processes
59
In a reversible process, the system undergoing the process can be
returned to its initial conditions along the same path shown on
a PV diagram, and every point along this path is an equilibrium state.

A reversible process, or reversible cycle: if the process is cyclic, is a

process that can be "reversed" by means of infinitesimal changes in
some property of the system without entropy production or dissipation
of energy.

A process that does not satisfy these requirements is irreversible.

Irreversible Process:
The process is said to be an irreversible process if it cannot return
the system and the surroundings to their original conditions when
the process is reversed. The irreversible process is not at equilibrium
throughout the process.
 All natural processes are known to be irreversible 60
Reversible Processes for an Ideal Gas

Adiabatic Isothermal Isobaric Isochoric

process process process process

PVγ = constant T = constant p = constant V = constant

γ = CP/CV
W = – [1/(γ –1)] W = nRT ln(V2 /V1) W = PV W=0
.[P2V2 – P1V1]
ΔU = CV ΔT ΔU = 0 ΔU = CV ΔT ΔU = CV ΔT

PV = nRT, U = ncVT, cP – cV = R, γ = cP/cV.

Monatomic ideal gas cV = (3/2)R, γ = 5/3.

61
THE CARNOT CYCLE

 According to the second law, no heat

engine can have 100% efficiency.

 How great an efficiency can engine have,

given two heat reservoirs at temperatures
𝑇𝐻 𝑎𝑛𝑑 𝑇𝐶 ?

 This question was answered in 1824 by

the French engineer Sadi Carnot who
developed a hypothetical, idealized heat
engine that has the maximum possible
efficiency consistent with the second law.
The cycle of this engine is called the Carnot
cycle.
62
Reversible Engine: the Carnot Cycle
The Carnot cycle consists of two
Reversible isothermal and two
reversible adiabatic processes (Fig.
2.15)
• Stage 1 Isothermal expansion at
temperature T2 (ab), absorbing
heat Q2.
• Stage 2 adiabatic expansion and
temperature drops from T2 to T1.
(bc)
• Stage 3 Isothermal compression at
temperature T1, rejecting heat Q1
Figure 2.15: The Carnot cycle for (cd).
an ideal gas • Stage 4 adiabatic compression and
𝑄1 𝑇1
Since, = , (2.23) back to its initial state, temperature
𝑄2 𝑇2
𝑇1 rises from T1 to T2 (da).
 = 𝑟 = 1 −
𝑇2 63
Heat Engines, The Carnot Cycle

The Carnot heat engine is a

hypothetical, ideal engine
that operates on the
reversible Carnot cycle. It is
used as a reference cycle
although ironically, no real
Carnot Engines are known
to have been made. It is a
closed cycle using the
external application of
heat.
Figure 2.16: The Carnot cycle for
an ideal gas
64
 This simple result says that the efficiency of a Carnot engine
depends only on the temperatures of the two heat reservoirs.

 The efficiency is large when the temperature difference is large,

and it is very small when the temperatures are nearly equal.

 The efficiency can never be exactly unity unless, TC = 0; this is

impossible.

 Caution: Use Kelvin temperature in Carnot calculations

65
Example:

Solution

SET UP: Figure 2.17 shows the energy-

flow diagram for this problem. For this
Carnot engine we are given 𝑄𝐻 =
2000 𝐽, the amount of heat absorbed,
and the temperatures 𝑇𝐻 = 500 𝐾 and
𝑇𝐶 = 350 𝐾 of the hot and cold
reservoirs, respectively. Using eq. (2.23)
Figure 2.17: Set up of the
problem 66
The thermal efficiency is
350 𝐾
 = 𝑟 = 1 − = 30%
500 𝐾

67
From eq. (2.22)

Substitute 

(2.24)

68
Figure 2. 18: Proving that the Carnot engine has the highest
possible efficiency. A “superefficient” engine (more
efficient than a Carnot engine) combined with Carnot
refrigerator could convert heat completely into work with
no net heat transfer to the cold reservoir. This would
violate the second law of thermodynamics 69
THE KELVIN TEMPERATURE SCALE

The thermal efficiency of a Carnot engine operating between two

heat reservoirs at temperatures 𝑇𝐻 𝑎𝑛𝑑 𝑇𝐶 is independent of the
nature of the working substance and depends only on the
temperatures. Thus, it can be used to define a temperature scale that
doesn’t depend on the properties of any particular material.

 Therefore, the ratio 𝑄𝐶 𝑄𝐻 is the same for all Carnot engines

operating between two given temperatures 𝑇𝐻 𝑎𝑛𝑑 𝑇𝐶 .
 Kelvin proposed that we define the ratio of the temperatures,
𝑇𝐶 𝑇𝐻 , to be equal to the magnitude of the ratio 𝑄𝐶 𝑄𝐻 of the
quantities of heat absorbed and rejected.
𝑇𝐶 𝑄𝐶 𝑄𝐶
= =− (2.25)
𝑇𝐻 𝑄𝐻 𝑄𝐻

70
ENTROPY AND THE SECOND LAW OF THERMODYNAMICS

By the end of this section, you will be able to:

 Define entropy.
 Calculate the increase of entropy in a system with
reversible and irreversible processes.
 Explain the expected fate of the universe in entropic
terms.
 Calculate the increasing disorder of a system.

https://courses.lumenlearning.com/physics/chapter/15-6-entropy-and-the-second-
law-of-thermodynamics-disorder-and-the-unavailability-of-energy/

71
 The zeroth law of thermodynamics involves the concept of
temperature, and the first law involves the concept of internal
energy.
 First law of thermodynamics tells us about conservation of energy
 Second law is saying about impossibility, no equation or a
quantitative relationship rather a statement.

o To be more precise, entropy is used (introduce by Clausius in

1860s), which is a state function, similarly to temperature and
internal energy to derive the relationship that explain
quantitatively the second law of thermodynamic.
o State functions — are variables that can be used to describe other
thermodynamic state of a system.

72
What does a change in entropy mean, and why should we be
interested in it? One reason is that entropy is directly related to the
fact that not all heat transfer can be converted into work.

o Entropy is related not only to the unavailability of energy to do

work—it is also a measure of disorder.
o This notion was initially postulated by Ludwig Boltzmann in the
1800s. For example, melting a block of ice means taking a highly
structured and orderly system of water molecules and converting it
into a disorderly liquid in which molecules have no fixed positions

73
ORDER TO DISORDER

The entropy of a system can be considered as a measure of the

disorder of the system. Thus, second law of thermodynamics can
be stated simply as:
 Therefore, all natural processes tend to move toward a state of
greater disorder.

 To derive the quantitative relation, consider an infinitesimal

isothermal expansion of an ideal gas. Add heat dQ and let the
gas expand just enough to keep the temperature constant.
Because the internal energy of an ideal gas depends only on its
temperature, the internal energy is also constant; thus from the
first law, the work dW done by the gas is equal to the heat dQ
added, and is given as:

74
 The gas is in a more disordered state after the expansion, because
the molecules are moving in a large volume and have more
randomness of position.
 Thus the fractional volume change 𝑑𝑉 𝑉 is a measure of the
increase in disorder; and from the above equation shows that it is
proportional to the quantity 𝑑𝑄 𝑇.
𝑑𝑉 𝑑𝑄
𝛼
𝑉 𝑇
 If S denote the entropy of the system, then, we define the
infinitesimal entropy change 𝑑𝑆 during an infinitesimal reversible
process at absolute temperature T as:
𝑑𝑄
𝑑𝑆 = (2.26)
𝑇
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If a total amount of heat Q is added during a reversible isothermal
process at absolute temperature T, the total entropy change ∆𝑆 =
𝑆2 − 𝑆1 is given by:

𝑄
∆𝑆 = 𝑆2 − 𝑆1 = (2.27)
𝑇

 It can be see that the quotient 𝑄 𝑇 is related to the increase

in disorder or randomness when heat flows into a system.

 Higher temperature means greater randomness of motion. If

the substance is initially cold, with little molecular motion,
adding heat Q causes a substantial fractional increase in
molecular motion and randomness.

76
(2.28)

77
Examples:
1) An ice cube of mass 56 g is taken from a storage
compartment at 0 C and placed in a paper cup. After a few
minutes, exactly half of the mass of the ice cube has melted,
becoming water at 0 C. Find the change in entropy of the
ice/water.

Using Eq. (2.27)

78
Examples:
2) A sample of 50 kg of water at 20 C is mixed with 50 kg of water
at 24 C. Estimate the change in entropy.

Approach: The final temperature of the mixture will be 22 C,

since we started with equal amounts of water. We use the
specific heat of water and the methods of calorimetry to
determine the heat transferred. Then we use the average
temperature of each sample of water to estimate the entropy
change (∆𝑄/𝑇).

79
80
 From example 2, we can observe that although the entropy of
one part of the system decreased, the entropy of the other part
increased by a greater amount; the net change in entropy of the
whole system was positive. Thus, the total entropy of an
isolated system is found to increase in all natural processes.

 The second law of thermodynamics can be stated in terms of

entropy as follows: The entropy of an isolated system never
decreases. It can only stay the same or increase

 Entropy can remain the same only for an idealized (reversible)

process. For any real process, the change in entropy ∆𝑆 is
greater than zero.

81
∆𝑆 > 0 (2.29)
If the system is not isolated, then the change in entropy of the
system, ∆ 𝑆𝑆 , plus the change in entropy of the environment,
∆ 𝑆𝑒𝑛𝑣 , must be greater than or equal to zero:

∆ 𝑆 = ∆ 𝑆𝑆 + ∆ 𝑆𝑒𝑛𝑣 ≫ 0 (2.30)
Only idealized processes have ∆ 𝑆 = 0. Real processes have ∆ 𝑆 >
0. This, then, is the general statement of the second law of
thermodynamics:
The total entropy of any system plus that of its environment
increases as a results of any natural process.

Although the entropy of one part of the universe may decrease in

any process, the entropy of some other part of the universe always
increases by a greater amount, so the total entropy always
increase. 82
ENTROPY IN CYCLIC PROCESSES
The total entropy change for a cycle of a particular Carnot engine,
which uses an ideal gas as its working substance, is zero.

(2.31)

𝑄𝐻
The quotient equals ∆𝑆𝐻 , the entropy change of the engine that
𝑇𝐻
𝑄𝐶
occurs at 𝑇 = 𝑇𝐻 . Likewise, equals ∆𝑆𝐶 , the (negative) entropy
𝑇𝐶
change of the engine that occurs at T = 𝑇𝐶 . Hence, Eq. (2.31) says
that ∆𝑆𝐻 + ∆𝑆𝐶 = 0; that is, there is zero net entropy change in one
cycle.
Therefore, we conclude that the total entropy change in once cycle
of any Carnot engine is zero.

(2.32) 83
QUASI-STATIC, REVERSIBLE PROCESS FOR AN IDEAL GAS
Suppose that an ideal gas undergoes a quasi-static, reversible
process from an initial state having temperature Ti and volume Vi
to a final state described by Tf and Vf. Let us calculate the
change in entropy of the gas for this process.

Using first law of thermodynamics:

𝑑𝑄𝑟 = 𝑑𝑈 + 𝑑𝑊 = 𝑑𝑈 + 𝑝𝑑𝑉, 𝑎𝑛𝑑 𝑓𝑟𝑜𝑚 𝑡ℎ𝑒 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠

𝑠𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑒, 𝑝 = 𝑛𝑅𝑇/𝑉

𝑑𝑉
𝑑𝑄𝑟 = 𝑑𝑈 + 𝑝𝑑𝑉 = 𝑛𝐶𝑉 𝑑𝑇 + 𝑛𝑅𝑇
𝑉

Rearranging the terms, then we get:

84
𝑑𝑄𝑟 𝑑𝑇 𝑑𝑉
= 𝑛𝐶𝑉 + 𝑛𝑅 (2.33)
𝑇 𝑇 𝑉
Assuming that 𝐶𝑉 is constant over the interval in question, and
integrating eq. (2.33) we obtain:
𝑓 𝑇𝑓 𝑉𝑓
𝑑𝑄𝑟
∆𝑆 = = 𝑛𝐶𝑉 𝑙𝑛 + 𝑛𝑅𝑙𝑛 (2.34)
𝑖 𝑇 𝑇𝑖 𝑉𝑖
 Therefore, ∆𝑆 depends only on the initial and final states and
is independent of the path between the states.
 Also, note in Eq. (2.34) that ∆𝑆 can be positive or negative ,
depending on the values of the initial and final volumes and
temperatures.
 Finally, for a cyclic process 𝑇𝑖 = 𝑇𝑓 𝑎𝑛𝑑 𝑉𝑖 = 𝑉𝑓 we see
from Eq. (2.34) that ∆𝑆 = 0.
 This is evidence that entropy is a state function.
85
End of Chapter two

86