CHAPTER 7

THERMODYNAMICS
 LESSON OUTCOMES
At the end of this chapter, students should be able to :

 understand the concept of heat as the transfer of energy

( able to determine heat due to temperature change & phase change )

 define the internal energy

( increases & decreases due to heat lost or gain )

 understand the First Law of Thermodynamics and thermodynamics

processes
( describe & solve the problems related to isobaric, isochoric, isothermal &
adiabatic process)

 understand the Second law of Thermodynamics & working principle of

heat engine

 determine the efficiency of the heat engine

 understand the working principle & determine the COP of refrigerators, air
conditioners and heat pumps
 HEAT & INTERNAL ENERGY
HEAT, Q
 Heat is the transfer of energy between a system and its environment due to
a temperature difference between them.

INTERNAL ENERGY, U
 Internal energy is the total of all the energy of the molecules within the
system.
 The internal energy should increase if heat added to the system,
and it should decrease if heat flows out of the system.

3
For monatomic gas : U nRT
2

diatomic gas : 5
U nRT
2

polyatomic gas :
 SPECIFIC HEAT CAPACITY

Specific heat capacity, c

 The amount of heat required to raise the temperature of 1kg
substance by 1 °C.
SI unit: J/kg °C

Q Q
c  
mT m ( T2  T1 )
 Q  mc ( T2  T1 )
Q  mcT
MOLAR SPECIFIC HEAT FOR GAS
 SPECIFIC HEAT & MOLAR SPECIFIC HEAT
 The specific heat, c, is characteristic of the material. Some values are listed in
the tables below :
 PHASE CHANGE AND HEAT OF TRANSFORMATION

  A phase change is characterized by a change in thermal energy

without a change in temperature.
 The amount of heat energy that causes 1 kg of substance to undergo a
phase change is called the heat of transformation (or latent heat).
 The symbol for heat of transformation is L.
 The heat required for the entire system of mass, m to undergo phase
change is :
(phase change)

 Two specific heats of transformation are the heat of fusion Lf, the

heat of transformation between a solid and a liquid, and the heat

of vaporization Lv, the heat of transformation between a liquid and
a gas.
 PHASE CHANGE AND HEAT OF TRANSFORMATION

  The heat needed for these phase changes is

(melt/freeze)
(boil/condense)
PHASE CHANGE AND HEAT OF TRANSFORMATION
 THERMODYNAMICS

Thermodynamics is the branch of physics that is built upon the

fundamental laws that heat and work obey.

The collection of objects on which attention is being focused is called

the system, while everything else in the environment is called the

surroundings.

Walls that permit heat flow are called diathermal walls, while walls
that do not permit heat flow are called adiabatic walls.

To understand thermodynamics, it is necessary to describe the state

of a system.

10
 CLOSED, OPEN & ISOLATED SYSTEM

 Systems may be considered to be closed or open, depending on

whether a fixed mass or a fixed volume in space is chosen for study.

 A closed system consists of a fixed amount of mass and no mass may

cross the system boundary. The closed system boundary may move.
Energy may flow across the boundary.

Examples of closed systems are sealed tanks

and piston cylinder devices (note the volume
does not have to be fixed). However, energy
in the form of heat and work may cross the
boundaries of a closed system.
 CLOSED, OPEN & ISOLATED SYSTEM

 An open system, or control volume, has mass as well as energy

crossing the boundary, called a control surface. Examples of open
systems are pumps, compressors, turbines, valves, and heat
exchangers.

 An isolated system is a general system of fixed mass where no

heat or work may cross the boundaries.

 An isolated system is a closed system with no energy crossing

the boundaries and is normally a collection of a main system and
its surroundings that are exchanging mass and energy among
themselves and no other system.
 ZEROTH OF THERMODYNAMICS

 The Zeroth Law states that:- “two systems which are equal in
temperature to a third system are equal in temperature to each other”.
 If an object with a higher temperature comes in contact with a lower
temperature object, it will transfer heat to the lower temperature object.
 The objects will approach the same temperature, and in the absence
of loss to other objects, they will maintain a single constant
temperature. Therefore, thermal equilibrium is attained.
 THE FIRST LAW OF THERMODYNAMICS
Definition :
The change in internal energy, ∆U of a closed system is equal to the
energy added to the system by heating minus the work done by the system
to the surrounding.

U  Q  W

Q is positive when the system gains heat and negative when it loses heat.
W is positive when work is done by the system and negative work is done
on the system.

Sign Convention
1) HEAT : Q (+) : when the system GAIN heat
Q (-) : when the system LOSES heat
2) WORK : W (+) : when it is done BY the system
W (-) : when it is done ON the system
Example 1
The figure shows a system and its surroundings.
(a) The system gains 1500 J of heat from its surroundings, and
2200 J of work is done by the system on the surroundings.
Determine the change in the internal energy of the system.

(b) The system also gains 1500 J of heat, but 2200 J of

work is done on the system by surroundings.
Calculate the change in the internal energy of the system.

Solution :

-700 J, 3700 J
 THERMAL PROCESS IN THE FIRST LAW of
THERMODYNAMICS
1) ISOBARIC PROCESS
 Thermodynamics process that occurs at a constant PRESSURE

Pressure (P)

work done : W = P (Vf – Vi)

W = P ΔV
Work done :area under the graph.

Volume (V)

W  Fs , F  PA
 PAs , but the product As is the change in volume
of the material . ( As   V  V f  Vi )
 P (V f  Vi )
Example 2
1.0 g of water is placed in the cylinder and the pressure
is maintained at 2 x 105 Pa. The temperature of the
water is raised by 31oC.
Find the work done and the change in internal
energy if the water is in the liquid phase expand by the
amount of 1 x 10-8 m3.
( cwater = 4186 J/Kg.°C )

Solution :

0.002 J, 129.764 J
2) ISOCHORIC PROCESS or ISOVOLUMETRIC
 Thermodynamics process that that occurs at constant VOLUME
Pressure ( P)

The area under the graph is

zero, indicating that no work
is done ( W= 0 J).

Volume (V)

Since no work is done, the heat in an isochoric process serves only to

change the internal energy:
W  Fs
 PA s , s  0
 P (V f  Vi )
0
 3) ISOTHERMAL PROCESS
 Thermodynamics process that occurs at constant TEMPERATURE
V 
The work done is; W  nRT ln  f 
V  Pressure ( P)
 i 

The work done = area under graph

The internal energy depends entirely

on the temperature of the system.

Volume (V)

 U  nR T f  Ti 
3
2
 
If the temperature remains constant,
the change in internal energy
must be zero.
3) ISOTHERMAL PROCESS

For higher temperature, the constant (nRT) is bigger resulting the curve
being further away from origin of the axes.

Pressure ( P)

Volume (V)
Example 3

Two moles, of the monatomic gas argon expand isothermally at 25 °C, from
0.025 m3 to 0.05 m3. Assuming that argon is an ideal gas, find ;
a) the work done by the gas
b) the change in the internal energy of the gas
c) the heat supplied to the gas.

Solution :

3434.64 J, 0 J,3434.64 J
4) ADIABATIC PROCESS

 Thermodynamics process that occurs without the transfer of heat.

When the system performs work adiabatically, no heat flows into or

out of the system (Q = 0 J)
Pressure ( P)

 U  Q W , Q  0J
3
 W , U  nRT
2
U  U f  Ui   W

 nR T f  Ti 
3
2 Volume (V)

  W , T in K temperatur e
A plot of pressure versus volume yields
the adiabatic curve shown in red, which
intersects the isotherm (blue) at the initial
nR Ti  T f 
3
W  temperature Ti and the final temperature Tf.
2
The work done by the gas is given by the
Example 4

An insulated cylinder contains a gas with initial volume, pressure and temperature ;
3.2 x 10-4 m3, 1.01 x 105 Pa and 47 °C respectively. Assume that there is no heat
lost through the cylinder.
a) Calculate the number of mol of the gas.
b) The gas is compressed until its volume becomes 4.5 x 10-5 m3 and temperature
becomes 750 K. Calculate the final pressure of the gas.
c) The work done on the gas is 120 J. Calculate the increase in the internal
energy of the gas.

Solution :

Ans : 0.012 mol, 1.66 x 106 Pa, 120 J

For processes where the pressure varies, the work done is the area
under the P-V curve.

Isochoric
Example 5

An ideal gas is slowly compressed at a constant pressure of 2.0 atm from 10.0 L
to 2.0 L. This process is represented in figure as the path B to D. Heat is then
added to the gas, holding the volume constant and the pressure and temperature
are allowed to rise (line DA) until the temperature reaches its original value ( TA =
TB ). Calculate :
a) the total work done on the gas in the process BDA.
b) The total heat flow out of the gas

Solution :
Isochoric
Isochoric

-1620.8J, -1620.8 J
Example 6
A vessel contains 2 mol of monatomic gas at temperature, 27 °C. Determine :
a) the quantity of heat transferred in order to raise the temperature of gas to 127 °C
i) at a constant volume ii) at a constant pressure
b) the work done to heat the gas at a constant pressure.
( R = 8.314 Jmol.K , Cv= 3/2 R , Cp= 5/2 R )

P
Solution :

2494.2J, 4157 J, 1662.8 J

 THE SECOND LAW OF THERMODYNAMICS
Definition:

Heat flows spontaneously from a substance at a higher temperature to a

substance at a lower temperature and does not flow spontaneously in the
reverse direction (or it will not flow spontaneously from a cold object to a hot
object.)

HEAT ENGINE
 A heat engine is any device that uses heat to perform work or changes
thermal energy into mechanical work.
• Basic idea is that mechanical energy can be obtained from thermal energy
only when heat is allowed to flow from a high temperature to a lower
temperature.
• In this process, some of the heat can be transformed to mechanical work.
• Useful heat engines run in a repeating cycle: that is, the system returns
repeatedly to its starting point, and thus can run continuously.
• In each cycle ∆U = 0, because it returns to the starting state
The symbols QH, QL and W refer to magnitudes only, without reference to
algebraic signs. Therefore, when these symbols appear in an equation, they do
not have negative values assigned to them.
To be highly efficient, a heat engine must produce a relatively large amount of
work from as a little input heat as possible.

W  QH  QL
Q H  W  QL

The schematic representation of

heat engine shows the input heat
(magnitude = QH) that originates
from the hot reservoir, the work, W
and rejected heat (magnitude = QL)
that the engine rejects to the cold
reservoir.
This is a heat engine; mechanical energy can
be obtained from thermal energy only when
heat can flow from a higher temperature to a
lower temperature.
 HEAT ENGINE

A boiling heat reactor, which is an external heat engine

 HEAT ENGINE

 The Carnot engine was created to examine the efficiency of a heat

engine. It is idealized, as it has no friction.
 Each leg of its cycle is reversible.
 The Carnot cycle consists of:
- Isothermal expansion
- Adiabatic expansion
- Isothermal compression
- Adiabatic compression
CARNOT CYCLE
EFFICIENCY, e
Definition: efficiency of heat engine is defined as the ratio of the work, W done by the
engine to the input heat QH.
work done W
e 
input heat QH

Efficiencies are often quoted as percentages obtained by multiplying the ratio W/QH
by a factor 100.
If there are no other losses in the engine, the engine’s input heat, QH is converted into
work, W and the remainder QL is rejected to the cold reservoir.
W = QH – Q L

Q H = W + QL

For an ideal reversible engine, the efficiency can be written in terms of the
temperature:
Example 7
A automobile engine has an efficiency of 22 % and produces 2510 J of work.
How much heat is rejected by the engine?
Solution :

8899.1 J
Example 8

A Carnot engine has efficiency of 70% and the temperature of its cold
reservoirs is 105 °C.
i) Determine the temperature of its hot reservoir.
ii) If 5230 J of heat is rejected to the cold reservoir, what amount of heat is
put into the engines?

Solution :

Ans : 1260 K, 1.743 x 104 J

 APPLICATIONS
Refrigerators, Air Conditioners, and Heat Pumps
These appliances can be thought of as heat engines operating in
reverse.
Refrigerators, air conditioners, and
heat pumps are devices that make
heat flow from cold to hot. This is
called the refrigeration process.

By doing work, heat is extracted from

the cold reservoir and exhausted to the
hot reservoir.
Basic Refrigeration Cycle
 Refrigerators

Refrigerator performance is measured by the coefficient of

performance (COP):

Substituting:
 Heat Pumps

A heat pump can heat a house in the winter:

Heat Pumps