PH 1205: THERMAL PHYSICS

Course instructor: Dr Stanley F. Mwanga

Time table: Lect. 2 hours and Tutorial 1 hour per week
TIME
CNMS: Tuesday → 10:00 – 12:00; Friday→ 14:00 – 17:00
COED: Thursday → 09:30 – 11:30; Friday → 17:00 − 20:00;
Tutorial: Every chapter
Assessment: 2 tests (40%) [8th and 12th week]
Final Exam: 60%

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 PH 1205: THERMAL PHYSICS
Credit Rating: 7.5 Credits

Course Aim
▪ This course is intended to explore about ideal and real
gases, thermodynamic laws, and kinetic theory of gases

Expected Learning Outcome

At the end of the course you should be able to:
▪ Explain the equation of state of real gas and Joule-Thomson
effect
▪ Describe the various thermodynamic laws
▪ Explain basic postulates of kinetic theory of gases
▪ Explain Maxwell-Boltzmann statistics

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Reading List
1. Halliday D, Resnick R, Krane K.S., Physics Vol II, John Wiley and
Sons (1992).
2. Ashley H Carter, Classical and Statistical Thermodynamics,
Prentice Hall (2001).
3. David S Betts and Roy E Turner, Introductory Statistical
Mechanics, Addison-Wesley (1993).
4. Schroeder D.V., An Introduction to Thermal Physics, Addison-
Wesley (2000).
5. Baierlein R, Thermal Physics Cambridge University Press (1999)
6. Serway and Jewett, Physics for Scientists and Engineers, 6th
Edition (2004).
7. Young and Freedman, University Physics with Modern Physics,
13th Edition, Pearson Addison-Wesley (2007).
8. Gouglas C. Giancoli, Physics: Principles with Applications, 7th
Edition (6th Edition), Pearson Education Inc. (2005)
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 IDEAL AND REAL GASES

At the end of this chapter the following aspects

should be grasped:
▪ Introduction
▪ Thermal Equilibrium
▪ Temperature Scales And Thermometers
▪ Thermodynamic System
▪ Thermodynamic Variables
▪ Ideal Gas Equation
▪ Van Der Waal’s Equation
▪ Joule – Thomson Effect

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 Introduction

o Thermodynamics can be defined as the study of energy, energy

transformations and their relation to matter.
o The analysis of thermal systems is achieved through the
application of the governing conservation equations, namely
Conservation of Mass, Conservation of Energy (1st law of
thermodynamics), the 2nd law of thermodynamics and the
property relations.
o Energy can be viewed as the ability to cause changes.

Whenever there is an interaction between energy and matter,

thermodynamics is involved. Some examples include heating and
air‐conditioning systems, refrigerators, water heaters, etc.

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o In thermodynamics, we deal with changes in total energy only.
Thus, the total energy of a system can be assigned a value of
zero at some reference point.
o Total energy of a system has two groups: macroscopic and
microscopic.
o Macroscopic forms of energy: forms of energy that a system
possesses as a whole with respect to some outside reference
frame, such as kinetic and potential energy.
o The macroscopic energy of a system is related to motion and
the influence of some external effects such as gravity,
magnetism, electricity, and surface tension.

o Microscopic forms of energy: are those related to the molecular

structure of a system. They are independent of outside reference
frames.
o The sum of microscopic energy is called the internal energy, U.
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 Heat Energy
▪ Heat energy, or thermal energy, is the energy of a substance or
system in terms of the motion or vibration of its molecules.
▪ The faster the molecules in a substance move, the more heat
energy they have.

▪ Heat (internal kinetic energy): always flows from the hotter

region (object) to the cooler region (object) for two
regions/objects in direct contact (sensible heat exchange).

▪ Heat: Is the (sum) total internal kinetic energy of all the

molecules in a given system of interest.

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 TEMPERATURE
Temperature is the degree of hotness or coldness of an object.
Thus, our senses provide us with a qualitative indication of
temperature.

In thermodynamic context, temperature is the average kinetic

energy of the molecules in a substance.
➢ For instance, large and small glass of water might have the
same temperature, even though the large glass of water
contains more overall heat energy.
Therefore, temperature is a measure of the average kinetic energy
of the individual particles in an object.

Why large glass of water have more heat energy than

small one, even if they are at same temperature?
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 THERMAL EQUILIBRIUM
▪ When we put two objects “in contact”, the atoms in those objects
can exchange energy
▪ Some macroscopic (measurable) properties of the objects can
change
▪ After a certain time, all the properties will be constant, and we
say that the objects are in thermal equilibrium with one another.

Zeroth law of thermodynamics:

Figure 1.1: A and C are in thermal
equilibrium with B, therefore A and
C are at the same temperature
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
If two systems are in thermal
equilibrium with a third system, then
they are in thermal equilibrium with
each other. 9
 TEMPERATURE SCALES AND THERMOMETERS
▪ Assigning values of temperature to different bodies is quite
arbitrary (i.e. the very important aspect is to ensure that the
bodies in thermal equilibrium have the same value and those not
in thermal equilibrium have unequal values of temperature)

The three most

common temperature
scales are Fahrenheit,
Celsius, and Kelvin.

Figure 1.2: The three most common temperature scales 10

Figure 1.3: Temperatures scales conversion

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To convert between
Fahrenheit and Kelvin,
convert to Celsius as
an intermediate step.

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Examples:

1. If your doctor tells you that your temperature is 310 kelvins

above absolute zero, should you worry? Explain your answer.

2. (a) In 1964, the temperature in the Siberian village of Oymyakon

reached a value of −71 C. What temperature is this on the
Fahrenheit scale? (b) The highest officially recorded
temperature in the continental United Sates was 13 F in Death
Valley, California. What temperature is this on the Celsius scale?

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▪ Thermometers are devices that are used to define and measure
temperatures

▪ All thermometers are based on the principle that some physical

property of a system changes as the system’s temperature
changes

▪ Some physical properties that change with temperature are:

1. the volume of a liquid
2. the length of a solid
3. the pressure of a gas at constant volume
4. the volume of a gas at constant pressure
5. the electric resistance of a conductor, and
6. the colour of an object

▪ For a given substance and a given temperature range, a

temperature scale can be established on the basis of any one of
these physical properties 14
1. For example in the Celsius scale, temperature scales are
constructed by choosing two fixed points: one to fix the origin
of the scale and the other to fix the size of the unit of the scale.
The two fixed points are assigned the numbers 0 C and 100 C
2. Suppose we choose electrical resistance as the thermometric
property. Then, measure the resistance Ro and R100 of the
resistance at the two fixed points of the Celsius scale. Put the
resistance thermometer in contact with the body whose
temperature is to be measured, and find its resistance Rt.
Assumption is that thermometric property (resistance) change
linearly with temperature. The temperature tR of the body is
then given by the linear relation:
𝑡𝑅 𝑅𝑡 − 𝑅0
= (1.1)
100 𝑅100 − 𝑅0

A similar procedure can be followed for a thermometer that

employs another thermometric property 15
 The Constant-Volume Gas Thermometer and the Absolute
Temperature Scale

Figure 1.5: A typical graph of pressure

Figure 1.4: A constant-volume gas
thermometer measures the pressure of the gas
contained in the flask immersed in the bath.
The volume of gas in the flask is kept constant
by raising or lowering reservoir B to keep the
mercury level in column A constant
versus temperature taken with a constant-
volume gas thermometer. The two dots
represent known reference temperatures
(the ice and steam points of water).
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▪ Suppose that temperatures are measured with gas thermometers
containing different gases at different initial pressures
▪ Experiments show that the thermometer readings are nearly
independent of the type of gas used, as long as the gas pressure is
low and the temperature is well above the point at which the gas
liquefies (Fig. 5).
▪ The agreement among thermometers using various gases improves
as the pressure is reduced.

Figure 1.6: Pressure versus temperature

for three dilute gases. Note that, for all
gases, the pressure extrapolates to zero at
the temperature − 273.15°C.

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▪ The temperature at zero pressure is −273.15°C, this
temperature is used as the basis for the absolute temperature
scale

▪ This temperature is often referred to as absolute zero

▪ The size of a degree on the absolute temperature scale is

identical to the size of a degree on the Celsius scale

▪ Thus, the conversion between these temperatures is

𝑇𝑐 = 𝑇 − 273.15 (1.2)

where TC is the Celsius temperature and T is the absolute

temperature
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 THERMODYNAMIC SYSTEM

• A system is the portion of the physical world being studied.

• The system plus surroundings comprise a universe.
• The boundary between a system and its surroundings is the
system wall.
• If heat cannot pass through the system wall, it is termed an
adiabatic wall, and the system is said to be thermally isolated or
thermally insulated.
• If heat can pass through the wall, it is termed a diathermal wall.
• Two systems connected by a diathermal wall are said to be in
thermal contact.

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 System v/s Surrounding
➢ System is the part of the world chosen for study, while everything
else is part of the surroundings.

➢ The state of a system is defined by specifying a number of

thermodynamic variables for the system under study. In principle,
these could be any or all of the measurable physical properties of
a system.

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 In Summary
• Thermodynamic system, or simply a system, is defined as a
quantity of matter or a region in space chosen for study
(e.g: A container of gas, a piece of metal, or magnet)

• The mass or region outside the system is called the

surroundings

• The real or imaginary surface that separates the system from

its surrounding is called the boundary

• The boundary of a system can be fixed or movable

• The system together with surrounding is called universe

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 THREE TYPES OF SYSTEM

Figure 1.7: Thermodynamic Systems

1. Isolated system → Physically and thermally isolated, i.e.
Neither mass nor energy can enter or leave the system
2. Closed system → Physically isolated, i.e. fixed amount of
mass, no mass can cross its boundary.
3. An open system (or a control volume), is a region in space in
which, both mass and energy can cross the boundary
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 Isolated, Closed and Open Systems

Isolated Closed Open

System System System
Neither energy nor
Energy, but not mass Both energy and mass
mass can be
can be exchanged. can be exchanged.
exchanged.

Figure 1.8: Thermodynamic Systems 23

 Interactions of thermodynamic systems
Type of
Mass flow Work Heat
System

Open v v v

Closed x v v

Isolated x x x

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 Thermodynamic Variables
• Thermodynamic variables are the observable macroscopic variables
of a system, such as P, V and T.
If the are used to describe an equilibrium state of the system, they are
known as state variables. State Variables are determined by current
condition and they are independent of path.
Types of variables:
• Extensive variables depend on the size of the system; e.g. mass,
volume, entropy, magnetic moment.
• Intensive variables do not depend on size; have a value at each
point in a system. May vary from point to point. e.g.
pressure, temperature, magnetic field.
• An extensive variable may be changed to an intensive variable, known as a
specific value, by dividing it by a suitable extensive variable, such as mass,
number of moles, or number of molecules.
Example: the specific heat capacity is normally (heat capacity)/(mass).
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 Summary of extensive and Intensive Variables
▪ Quantities used to describe the macroscopic behaviour are
called properties (or variables), eg: volume, pressure,
temperature , etc

▪ These properties are also classified as extensive or intensive

variables

▪ Extensive property is proportional to the mass. For instance, if

the mass is doubled, then the volume is doubled

▪ Intensive property is independent of the mass. Eg: density is

intensive property, its value is not affected by a change of mass,
others are Pressure and temperature

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 IDEAL GAS EQUATION

▪ Macroscopic description of an ideal gas examine the properties

of a gas of mass m confined to a container of volume V at a
pressure P and a temperature T. The equation that interrelates
these quantities is called the equation of state.
▪ Usually this equation is obtained when the gas is kept at very low
pressure (or low density) or can simply found experimentally.
▪ Such a low-density gas is commonly referred to as an ideal gas.

The amount of gas in a given volume is usually expressed in terms of

the number of moles n.
One mole (mol) of a substance is that amount of the substance that
contains as many particles (atoms, molecules, or other particles) as
there are atoms in 12 g of the carbon-12 isotope

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Experiments have shown that this number, known as Avogadro’s
number, NA, is NA = 6.022 137  1023 particles/mol . Since, there
are 6.022 137  1023 particles in 1 mol of any element, the mass
per atom for a given element is:

𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
𝑚𝑎𝑡𝑜𝑚 = (1.3)
𝑁𝐴

The number of moles n of a substance is related to its mass m

through the expression
𝑚 (𝑔)
𝑛(𝑚𝑜𝑙) = 𝑔 (1.4)
𝑀( )
𝑚𝑜𝑙
where M is the molar mass of the substance

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 𝑓 𝑃, 𝑉, 𝑇 = 0

The equation of state connects the three fundamental state

variable. It is an expression of the results of experiments. Every
system has its own equation of state.

𝑃𝑉 𝛼 𝑇 𝑃𝑉 = 𝑛𝑅 𝑇 (1.5)

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The ideal gas law is often expressed in terms of the total
number of molecules N. Because the total number of molecules
equals the product of the number of moles n and Avogadro’s
number NA

𝑁
𝑃𝑉 = 𝑛𝑅 𝑇 = 𝑅𝑇 = 𝑁𝑘𝛽 𝑇 (1.6)
𝑁𝐴

where kB is Boltzmann’s constant

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Figure 1.9: Diagrams for an ideal gas. In ( a ) the isotherms are
equilateral hyperbolae: in (b) the isochores are straight lines: and
in (c) the isobars are also straight lines.

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 Van der Waal Equation of State

The characteristics equation of an ideal gas represents the

behaviour of real gases fairly well for high temperatures and
low pressures. However, when the temperature and pressure
are such that the gas is near condensation, important deviations
from the ideal gas law are observed.
Van der Waals is among the equation introduced to represent
the behaviour of real gases, because it can describe behaviour of
many substances over a wide range of temperature and
pressure.
𝑎
𝑃 + 2 𝑣 − 𝑏 = 𝑅𝑇 (1.7)
𝑣
Where a and b are characteristic constants for a given 32
substance. For 𝑎 = 𝑏 = 0, equation (1.7) reduces to the
equation of state for an ideal gas equation (1.7)
o The term 𝑎Τ𝑣 2 arises from the intermolecular forces due to
the overlap of the electron clouds.
o the constant b takes into account the finite volume occupied
by the molecules, its effect is to subtract from the volume
term.

Multiplying eq. (1.7) by 𝑣 2 , yields the equation

𝑃𝑣 3 − 𝑃𝑏 + 𝑅𝑇 𝑣 2 + 𝑎𝑣 − 𝑎𝑏 = 0. (1.8)

The result is a cubic equation in 𝑣 with three roots, only one of

which needs to be real. In Figure 1.20, are some isotherms
calculated from the van der Waals equation have been drawn.
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 • As T increases, the curves approach 𝑃𝑣 =
𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡. The correction terms in the van
der Waals equation become less
important.
• For 𝑇 < 𝑇𝑐 , there is a local maximum
and minimum value of P. The transition
between the two types of curves is a
curve having an inflection point CP, the so
called critical curve, 𝑇 = 𝑇𝐶 .
• Suppose the volume decrease along an
isotherm for which 𝑇 < 𝑇𝑐 , after reaching
a maximum of the curve, the pressure
Figure 1.20: Isotherms for begins to fall. This is an unstable region
van der Waal gas since the pressure no longer increases as
the volume diminishing.
Which curve represent the roots of
• At this portion of the isotherm is not
van der Waals equation in Fig. 1.20
really traversed at all because the gas34
undergoes a change of phase.
NB: Inflection point is found where the graph (or image) of a function changes
concavity.
Comparison between Ideal and Real gas Equations

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 Joule – Thomson effect
William Thomson, 1824

❖ Joule-Thomson effect describes the change in temperature of a real gas or liquid

when it is forced to pass through porous plug or valve while it is kept insulated so
that exchange of heat with the environment is not possible.

❖ At ordinary temperatures and pressures, all real gases except hydrogen and
helium cool upon such expansion; this phenomenon often is utilized in liquefying
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gases. Why this?
 ▪ James Prescott Joule and William Thomson (both British
physicists) worked in collaboration, conducting experiments
designed to analyze and advance thermodynamics.
▪ In 1852, these researchers made a particularly notable
discovery. They found that a temperature change can occur in a
gas as a result of a sudden pressure change over a valve, This
discovery is known as Joule-Thomson effect (or sometimes the
Thomson-Joule effect).
▪ The Joule-Thomson (JT) effect is a thermodynamic process that occurs
when a fluid expands from high pressure to low pressure at constant
enthalpy.
▪ Such a process can be approximated in the real world by expanding a
fluid from high pressure to low pressure across a valve.
▪ Under the right conditions, this can cause cooling of the fluid.

Thus Joule-Thomson effect can be defined as the phenomenon of temperature

change produced when a gas is allowed to expand adiabatically from a region
of high pressure to a region of extremely low pressure 37
 Joule-Thomson (JT)

Figure 1.9: Joules – Thomson (JT) experiment

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 Joule-Thomson (JT)

Figure 1.10: Signs changes of Joules – Thomson (JT) experiment

Why enthalpy of the fluid remains approximately constant?

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 𝜕𝑇
𝜇𝐽𝑇 = (1.8)
𝜕𝑃 𝐻

μJT = Joule Thomson Coefficient expressed in °C/bar or K/Pa

∂T = Change in temperature
∂P = Change in Pressure.
H = Constant Enthalpy

All real gases have an inversion point at which the μJT changes
sign. The temperature of this point the Joule-Thomson
inversion temperature depends on the pressure of the gas
before expansion. This bringing about two cases:

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 First case:
In a gas expansion the pressure decreases below the inversion
temperature – the sign ∂P is negative by definition.
With that in mind, if the gas temperature is below the inversion
temperature then μJT is positive since ∂P always negative thus ∂T
must be negative.
So the gas cools; → μJT > 0, then temperature decreases, gas cools.
Second case:
In a gas expansion the pressure decrease and the gas
temperature is above the inversion temperature then μJT is
negative, ∂P always negative thus ∂T must be positive.
So the gas warms; → μJT < 0, then temperature increase, gas
warms.
The Joule–Thomson coefficient will be zero at a point called
inversion point
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Figure 1.11: Joule–Thomson coefficients for various gases at
atmospheric pressure.

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Applications of Joule-Thomson Effect

o The cooling produced in the Joule-Thomson expansion has

made it a very valuable tool in refrigeration.
o The effect is applied in the Linde technique in the
petrochemical industry, where the cooling effect is used to
liquefy gases.
o It is also used in many cryogenic applications. For example for
the production of liquid nitrogen, oxygen, and argon.
o The effect can also be used to liquefy even helium
o Also the effect that is responsible for a tire valve getting cold
when you let out the air from a bicycle tire.

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End of Chapter one: Homework & Tutorils

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