PHY 121: Waves and Oscillations, Optics and Thermal Physics (EEE)

Instructor: Dr. Md. Azizar Rahman (Azizar)

E-mail: [email protected]

Phone: 01714658898

Office Location: OAB, Room 136

Course website: All documents (syllabus, lectures, problems) will be posted at:
google class room.

Google Class code: ujzkbvg

Teaching strategies to be used to develop that knowledge: • Lectures • Assignments, at
home • Discussions in the Class • Reading (books, internet search)
 Mark distribution

Credit hours = 3 (EEE) and 4 (CSE)

Content Percentage of mark Mark (EEE) Mark (CSE)
Attendance 10% 30 40
Class test 20% 60 80
Final examination 70% 210 280

Attendance Mark
Above 90% 10 Class test = Best 3 class test mark from 4 class test
85-89 % 9
80-84% 8 Final exam: Section A = 3 questions out of 4
75-79 % 7 Section B = 3 questions out of 4
70-74% 6 35 marks for each questions
65-69 % 5 Exam time 3 hours
60-64% 4
Below 60% 0
 Course contents
Lecture No. Course Content Remarks
L:1-3 Principle of temperature measurements: Platinum resistance Quiz-1
thermometer, Thermo-electric thermometer, Pyrometer
L: 4-7 Kinetic theory of gases: Maxwell's distribution of molecular speeds,
Mean free path, Specific heats of ideal gases, Equipartition of energy,
equation of state
L: 8-10 Review of the First Law of Thermodynamics and its application, Quiz-2
Reversible and irreversible processes, Second Law of thermodynamics,
Carnot cycle; Efficiency of heat engines, Carnots theorem, Entropy and
disorder
L: 11-14 Thermodynamic functions, Maxwell relations, Clausius-Clapeyron
equation, Third law of thermodynamic
Books Recommended
1.Fundamentals of Engineering Thermodynamics -Moran, M.J & Saprio, H.N
2.Fundamentals of Thermodynamics -Sonntag, R.E, Borgnakke, C & Van Wylen
3. Thermodynamics: An Engineering Approach-Cengel, YA and Boles, M.A
4. Fundamental of Physics by D. Halliday, Resnics and J Walker
 What is physics
The branch of science concerned with the nature and
properties of matter and energy

Most fundamental things in the universe are

Matter
Energy
 Branches of Physics
Classical Physics (Pre 19th century): Classical physics refers to theories of physics that
predate modern, theories (Galileo, Newton, Lagrange, Hamilton, Maxwell)

 Mechanics (motion of object and system under the influence of force)

 Thermodynamics (heat energy)

 Acoustics (sound)

 Electrodynamics (electricity and magnetism)

 Optics (light)
 What went wrong with classical physics?
Classical physics could not explain
• Electron configuration in atoms
• Black body radiation
• Photoelectric effect
• Compton effect

 Classical idea that each

frequency of vibration should
have the same energy must be
wrong.
 Quantum idea , energy comes
in clumps called quantum,
E = hf
 Branches of Physics

Modern Physics (Post 19th century): Modern physics refers

characteristics of matter and energy (Einstein, Heisenberg,, Schrodinger, De
Broglie, Max Born, Lorentz, Roentgen, )

 Quantum Physics
 Atomic Physics
 Molecular physics
 Nuclear Physics
 Solid State Physics
 Plasma Physics
 Cryogenics
 Astronomy
 Geophysics
 Course Objectives
After completing this course, Student should be able to
1. Comprehend the properties of materials used for the measurements of temperature

2. Understand the significance of kinetic molecular theory of gasses

3. Understand the laws of thermodynamics and their applications

4. Calculation of work done from different thermodynamic processes

5. Understand thermodynamic functions & relations and their applications for solving

thermodynamic problems
Why do you study
thermodynamics
 Why do you study thermodynamics
Thermometer is an invention born from zeroth law of thermodynamic
 Why do you study thermodynamics
 1st law of thermodynamics says “Energy is conserved “.
 All the processes which occur in nature and daily life are guided by thermodynamic laws.

Adenosine triphosphate (ATP) is a Energy cannot be created or

complex organic chemical that provides destroyed; it can only change
energy to drive many processes in living cells, forms (the first law)
e.g. muscle contraction, nerve impulse
propagation, and chemical synthesis
 Why do you study thermodynamics
2nd law of thermodynamic:
Heat can’t flow from colder to hotter body
All refrigerators and ACs, works on this law
 Why do you study thermodynamics
2nd law of thermodynamic: Thermodynamic cycles are used in each definite and vast
areas. For ex: Otto cycle for petrol engine, Rankine cycle for
100% efficiency is not possible steam power plant, brayton cycle for gas turbines, Bell
colemen cycle for refrigerator, diesel cycle for diesel engine,
All petrol-, diesel-, jets- engines, power and the famous Carnot cycle as a standard for all the above
cycles.
plants, heat pump, works on this law

Cars Aircrafts

Boats-engine
 Why do you study thermodynamics
 Heat sinks in phones, CPUs, laptops, tablets, etc are designed based on
heat transfer laws.
 Power consumption and performance of your devices (phone, laptop,
tablet, etc).

Heat flows in the

direction of
Boiling water Cooling system of laptop
decreasing temperature
 Heat
Heat is a kind of energy that can transferred from one object to another object.

Result of heat
1. Change of temperature
2. Change of state
3. Change of physical properties
 Temperature
A degree of hotness and coldness

How you measure the temperature?

1. Different types of thermometer

Ref: Channel I online news (30-04-2019)

 Principle of temperature measurement
Measurement of temperature depends on some physics properties of matter which varies
with temperature.

These physical properties are

Change in length, volume or pressure, liquid (mercury or alcohol) ----

examples are liquid thermometer, gas thermometer

Change in electrical energy such as change in resistance---

Examples are thermo-couples thermometer, platinum resistance thermometer

Change of state or color-----

Examples are radiation and optical pyrometers
 Principle of temperature measurement
The essential requirements of a thermometer

Construction (physical properties of a substance)

Calibration:

(i) Need standard fixed points.

(ii) Melting points of ice, boiling point of water are taken as fixed points.

Sensitiveness:
The thermometer will be sensitive if it

(i) measures small change of temperature

(ii) Shows temperature with in short time

(iii) Does not take large heat from the measuring body
Principle of temperature measurement
 Liquid thermometer
Mercury and Alcohol thermometers

Range= -39 to 357 °C

Constant volume gas
Gas Thermometer
thermometer (air, Hydrogen, 𝑃𝑡 −𝑃𝑜
nitrogen, helium) 𝑡= × 100
𝑃100 −𝑃𝑜

ℎ𝑡 −ℎ𝑜
Principle: 𝑡= × 100
change in pressure with increasing ℎ100 − ℎ𝑜
temperature

𝑃𝑜 = 𝐻 + ℎ𝑜
Construction:
As shown in figure 𝑃𝑡 = 𝐻 + ℎ𝑡

Working: 𝑃100 = 𝐻 + ℎ100

At constant volume, the pressure
increases according to the relation

𝑃𝑡 = 𝑃𝑜 (1 + 𝛼𝑡)

𝑃𝑡 −𝑃𝑜 = 𝑃𝑜 𝛼 𝑡 H= Barometric height

Constant-volume air thermometer
𝑃100 −𝑃𝑜 = 𝑅𝑜 𝛼. 100
 Gas Thermometer
Advantages
 With hydrogen gas, the temperature range is -200 to 500 °C for platinum bulb, and 1100 °C for porcelain bulb
[Above 500 °C, hydrogen diffuse into the platinum bulb]
 With nitrogen gas, the range is 1500 °C
 With helium gas, the rage is below -200 °C
 Sensitivity 0.005 °C (in 0-100 °C range) and 0.1 °C (in 100-500 °C range)
 It serves as a standard of reference for other thermometers

Disadvantages
 This is not easily portable and cannot used for ordinary temperature measurements
 It takes time to measure the temperature and is not a quick thermometer.
 Platinum Resistance Thermometer
In 1871 Siemen first design it You can find 𝛼 and 𝛽 considering
improved by Callendar and Griffiths 1. Melting point of ice (0 ℃)
2. Boiling point of water (100 ℃)
Principle: 3. Boiling point of sulfur (444.6 ℃)
Electrical resistance of a metallic wire increases with 𝑅100 = 𝑅𝑜 (1 + 100 𝛼 + 1002 𝛽)
temperature by the following relation 𝑅400 = 𝑅𝑜 (1 + 400 𝛼 + 4002 𝛽)
𝑅𝜃 = 𝑅𝑜 (1 + 𝛼𝜃 + 𝛽𝜃 2 ) Solve for 𝛼 and 𝛽 (home work)
𝛼 = 3.94 × 10−3 and 𝛽 = −5.8 × 10−7 are constant.
Since 𝛽 is very small, by neglecting 𝛽
𝑅𝜃 = 𝑅𝑜 1 + 𝛼𝜃𝑝 ⇒ 𝑅𝜃 −𝑅𝑜 = 𝑅𝑜 𝛼𝜃𝑝
𝑅100 = 𝑅𝑜 (1 + 100𝛼) ⇒ 𝑅100 −𝑅𝑜 = 𝑅𝑜 𝛼. 100

𝑅𝜃 −𝑅𝑜
⇒ 𝜃𝑝 = × 100 … … … … … … … (1)
𝑅100 −𝑅𝑜
Knowing 𝑅𝜃 , 𝑅𝑜 and 𝑅100 , t can be calculated
 Platinum Resistance Thermometer
In 1871 Siemen first design it
improved by Callendar and Griffiths

Principle:
Electrical resistance of a metallic wire increases with temperature

Construction:
 Pure platinum wire doubled on itself to avoid self induction effect
 The wire is wound on a mica frame
 Free ends of the wire connected to thick platinum lead and then connected
to the binding terminal PP
 Compensating leads of same resistance as the lead connected to CC
 Whole arrangement is enclosed in porcelain tube
 Platinum Resistance Thermometer K
B
Q
Working Principle: P
𝑋𝑌 = 2𝑙 = bridge wire C
A G
S= Variable resistance 𝑅𝜃 + 𝑟 S
r = resistance of platinum leads and compensating leads
𝑅𝜃 = resistance of the platinum wire X D O Y
𝑋𝐷 = 𝑙 − 𝑥 and YD = 𝑥 + 𝑙
𝜌 = Resistance per unit length of XY wire
Since Resistance P = Resistance Q
Resistance of the arm AD = Resistance of the arm CD
𝑅𝜃 + 𝑟 + 𝑙 − 𝑥 𝜌 = 𝑆 + 𝑟 + 𝑙 + 𝑥 𝜌
𝑅𝜃 = 𝑆 + 2𝑥𝜌 [For balance point left to O]
𝑅𝜃 = 𝑆 − 2𝑥𝜌 [For balance point right to O]
Callendar and Griffith’s brigde
 Corrections of platinum resistance thermometer
Corrections: 𝑅𝜃 −𝑅𝑜
∴ 𝜃 − 𝜃𝑝 = 𝜃 − × 100
𝑅100 −𝑅𝑜
temperature determined by eq (1) is not accurate due 𝛼𝜃 + 𝛽𝜃 2
⇒ 𝜃 − 𝜃𝑝 = 𝜃 − × 100
to the negligence of 𝛽. The actual temperature 𝜃 can 100 𝛼 + 1002 𝛽
𝛼𝜃 + 100𝛽𝜃 − 𝛼𝜃 − 𝛽𝜃 2
⇒ 𝜃 − 𝜃𝑝 =
be expressed as 𝛼 + 100𝛽
100𝛽𝜃 − 𝛽𝜃 2
⇒ 𝜃 − 𝜃𝑝 =
𝜃
2
𝜃 𝛼 + 100𝛽
2
𝜃 − 𝜃𝑝 = 𝛿 − −1002 𝛽 𝜃 𝜃
100 100 ⇒ 𝜃 − 𝜃𝑝 = −
𝛼 + 100𝛽 100 100
Derivation: 2
𝜃 𝜃
𝑅𝜃 = 𝑅𝑜 (1 + 𝛼𝜃 + 𝛽𝜃 2 ) 𝜃 − 𝜃𝑝 = 𝛿 −
100 100
𝑅100 = 𝑅𝑜 (1 + 100 𝛼 + 1002 𝛽) Where 𝛿 =
−1002 𝛽
= 1.5 for pure platinum.
𝛼+100𝛽
𝑅𝜃 −𝑅𝑜 𝛼𝜃 + 𝛽𝜃 2
=
𝑅100 −𝑅𝑜 100 𝛼 + 1002 𝛽

Range= -200 to 1200 °C

Characteristics of materials used in Resistance Thermometer

Platinum: −270 to +1000°C

Copper: −200 to +260°C

Nickel: −200 to +430°C

Tungsten: −270 to +1100°C

Advantages and disadvantages of platinum resistance thermometer

Advantages: Advantages:
 Need some time to adjust or balance the bridge
 Measured temperature range -200 to 1200 °C
 Take some time to acquire the temperature of
 Sensitivity 0.01°C up to 500 °C and 0.1 °C up to the bath
 Not possible to measure the temperature of a
1200 °C
point body due to its large size
 Able to measure the average temperature of large
 Need highly pure platinum
volume due to its large size.  The formula is not corrected for impure
platinum
 Highly pure platinum is expensive
Problem 1. The value of resistance of a platinum resistance thermometer are 2.585 ohms and 3.51 ohms at 0°C and
100 °C, respectively. When placed in a hot bath, the resistance is found to be 9.098 ohms . Calculate the temperature
of the hot bath on the gas scale. Assume δ=1.5 for platinum.

Solution
𝑅𝑡 = 9.098 𝑜ℎ𝑚𝑠, 𝑅𝑜 = 2.585 𝑜ℎ𝑚𝑠, 𝑅100 = 3.51 𝑜ℎ𝑚𝑠

𝑅𝑡 −𝑅𝑜
𝑡= × 100 = 704°C
𝑅100 −𝑅𝑜

2
𝜃 𝜃
𝜃−𝑡 =𝛿 − = 785°C
100 100
Problem 2. If a platinum temperature, corresponding to 50 °C on the gas scale is 50.25 °C, what will be the
temperature on the platinum scale corresponding to 150 °C on the gas scale?
Solution

2
𝜃 𝜃
𝜃−𝑡 =𝛿 −
100 100
𝜃 = 50°C𝑎𝑛𝑑 𝑡 = 50.25°C

2
50 50
50 − 50.25 = 𝛿 − … … … … … … … . (1)
100 100

𝜃 = 150°C𝑎𝑛𝑑 𝑡 = 𝑥
2
150 150
150 − 𝑥 = 𝛿 − … … … … … … … . (2)
100 100

From equation (1) and (2), 𝑥 = 149.25°C

 THERMO-COUPLE THERMOMETER

Seeback experiment (1821):

If two junctions of dissimilar metals are placed at different
temperature, then an emf will be produced

This experiment is used to construct thermometer called

thermo-coupled (thermoelectric) thermometer

Thermocouple:
A thermocouple is an electrical device consisting of two
dissimilar electrical conductors forming electrical
junctions at differing temperatures.

The generated electromotive force (emf) developed is

known as thermo-electromotive force.

The magnitude and direction of emf depend on the

temperature difference between the two junctions and also
on the metal used
 Metal used in the thermocouples
Antimony (Sb), Fe, Cd, Zn, Ag, Au, Rb, Mo, Cr, Sn, Pb, Hg, Cu, Pt, Co, Ni, Bismuth (Bi)

Points to be remembered

 Current flow from A (antimony) to B (Bismuth) through C (cold junction)

 Metals to the right of Pb are thermoelectrically positive

 Metals to the left of Pb are thermoelectrically negative

 The magnitude of thermo emf depends on the separation of metals in this series.

 Larger the separation between metals, greater is the thermo emf.

 Temperature versus emf graph
Neutral temperature: the temperature at which the emf maximum
This is constant for a pair of metals
Temperature of inversion: the temperature beyond which the emf is
reversed. This is not constant

𝐼𝑓 𝑡𝑒𝑚𝑝. 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑙𝑑 𝑗𝑢𝑛𝑐𝑡𝑖𝑜𝑛 = 𝜃𝑐

𝑁𝑒𝑢𝑡𝑟𝑎𝑙 𝑡𝑒𝑚𝑝. = 𝜃𝑛
𝑇ℎ𝑒𝑛, 𝜃𝑛 − 𝜃𝑐 = 𝜃𝑖 − 𝜃𝑛

𝜃𝑖 + 𝜃𝑐
𝜃𝑛 =
2
For Cu-Fe thermocouple, if 𝜃𝑐 = 0 𝑜 𝐶, 𝜃𝑖 = 440 𝑜 𝐶
if 𝜃𝑐 = 100 𝑜 𝐶, 𝜃𝑖 = 540 𝑜 𝐶
 Thermocouple thermometer- what you need for construction
Elements of thermocouple thermometer:
1. Two dissimilar metals constituting the thermocouple
2. An outer protecting tube for the thermocouple
3. A potentiometer for measuring the thermo e.m.f developed in the thermocouple
4. A sensitive galvanometer

Choice of suitable metals for the thermocouple

 The materials selected should develop relatively large emf
 Neutral temp. of thermocouple should be higher than the temperature range to be measured to avoid
reversal emf
 melting temp. of thermocouple should be higher than the temp. range to be used
 Thermocouple thermometer- construction

Why electrical insulation of the thermocouple wires

1. To avoid contamination
2. To protect from oxidation and corrosion effect

Measurement of emf developed in the circuit

 Need a sensitive potentiometer, which can measure 0.1 µV for 0.25 °C change of temp.

Galvanometer

 Highly resistive and sensitive

 Thermocouple thermometer- Construction
L
Calibration of the thermocouple 𝑇 𝑇
L
 Thermocouple wires are insulated by passing through
capillary tube of hard glass
 Wires are kept in position by passing through several 𝐷 = 𝑀𝑖𝑐𝑎 𝑑𝑖𝑠𝑐
𝐵 = 𝑄𝑢𝑎𝑟𝑡𝑧 𝑡𝑢𝑏𝑒
mica disc D closely fitted in tube B
𝑇ℎ𝑒𝑟𝑚𝑜𝑐𝑜𝑢𝑝𝑙𝑒 𝑤𝑖𝑟𝑒
 The free ends of wires are attached to the terminals TT.
𝐶 = ℎ𝑎𝑟𝑑 𝑔𝑙𝑎𝑠𝑠 𝑡𝑢𝑏𝑒
 these terminals are connected to long flexible wire of
𝐴 = ℎ𝑜𝑡 𝑗𝑢𝑛𝑐𝑡𝑖𝑜𝑛
same metal, which form the cold junction
 Thermocouple thermometer working principle
Working principle:
 Need sensitive potentiometer to read µV
 AB potentiometer wire connected in series with
resistance box R and battery E
 Kept the cold junction at 0 ºC
 Increase the temperature of hot-junction
 The emf developed in the thermocouple can be
calculated from balancing length.
𝑅 = 𝑐𝑜𝑛𝑛𝑒𝑐𝑡𝑒𝑑 𝑠𝑒𝑟𝑖𝑒𝑠 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒
𝑟 = 𝑟𝑒𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑜𝑓 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑜𝑚𝑒𝑡𝑒𝑟 𝑤𝑖𝑟𝑒 𝐴𝐵
AB=1000 cm (say)
𝐸 = 𝑒𝑚𝑓 𝑜𝑓 𝑡ℎ𝑒 𝑏𝑎𝑡𝑡𝑒𝑟𝑦
𝐴𝐶 = 𝑙 = 𝑏𝑎𝑙𝑒𝑛𝑐𝑖𝑛𝑔 𝑙𝑒𝑛𝑔𝑡ℎ
 Thermocouple thermometer working principle

𝑇𝑜𝑡𝑎𝑙 𝑟𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 𝑖𝑛 𝑠𝑒𝑟𝑖𝑒𝑠 = 𝑅 + 𝑟

𝐸
𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑓𝑙𝑜𝑤𝑖𝑛𝑔 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑖𝑟𝑐𝑢𝑖𝑡, 𝑖 =
𝑅+𝑟
𝐸
𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑑𝑟𝑜𝑝 𝑜𝑣𝑒𝑟 𝑡ℎ𝑒 𝑒𝑛𝑡𝑖𝑟𝑒 𝑙𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑡ℎ𝑒 𝑤𝑖𝑟𝑒, 𝑉 = 𝑖𝑟 = ×𝑟
𝑅+𝑟

𝐸 𝑟
𝑃𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑑𝑟𝑜𝑝 𝑝𝑒𝑟 𝑐𝑚 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑜𝑚𝑒𝑡𝑒𝑟 𝑤𝑖𝑟𝑒, 𝑉 = 𝑖𝑟 = ×
𝑅 + 𝑟 1000

𝑒𝑚𝑓 𝑑𝑒𝑣𝑒𝑙𝑜𝑝𝑒𝑑 𝑖𝑛 𝑡ℎ𝑒 𝑡ℎ𝑒𝑟𝑚𝑜𝑐𝑜𝑢𝑝𝑙𝑒 𝑓𝑜𝑟 𝑡ℎ𝑒 𝑏𝑎𝑙𝑒𝑐𝑖𝑛𝑔 𝑙𝑒𝑛𝑔𝑡ℎ 𝑙 𝐴𝐶 𝑜𝑓 𝑡ℎ𝑒 𝑤𝑖𝑟𝑒,
𝐸 𝑟
= × ×𝑙
𝑅 + 𝑟 1000
 Some standard thermocouple and their calibration curves
 Keep the cold junction at 0 and increase the temperature of
hot junction
 Plot emf versus temp. called calibration curve.
 Unknown Temp. can be found from the calibration curve
corresponding to emf at that temp.

Positive Negative
Thermocouple type
Thermoelement Thermoelement
B Pt-30%Rh Pt-6%Rh
R Pt-13%Rh Pt
S Pt-10%Rh Pt
K Ni-10%Cr Ni-5%
N Ni-14%Cr-1.5%Si Ni-4.5%Si-0.1%Mg
E Ni-10%Cr 45%Ni-55%Cu
J Fe 45%Ni-55%Cu
A copper constant thermocouple having a mean thermoelectric power of 40 µV/ºC is used to
measure an unknown temperature. The potentiometer wire is 1000 cms long having a resistance
of 0.01 ohm per cm and is used in series with a cell of emf 2 volts and a resistance of 2000
ohms. The balance point is obtained with a length of 402 cms of the wire between the thermo-
couple terminals. Calculate the value of the unknown temperature. The cold junction is at 0 ºC.
𝐸 𝑟
Potential drop per cm of the wire is × ×𝑙
𝑅 + 𝑟 1000

2 × 10 × 402
The potential drop in 402 cm = = 4 × 103 𝜇𝑉 E= 2 volts
(2000 + 10) × 1000 R = 2000 ohms
r = 1000 * 0.01= 10 ohms
4 × 103 𝜇𝑉
𝑇𝑒𝑚𝑝. 𝑑𝑖𝑓𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑡𝑤𝑜 𝑗𝑢𝑛𝑐𝑡𝑖𝑜𝑛 = = 100 ºC Thermoelectric power
40𝜇𝑉/ºC 𝑑𝑉
𝑆=
𝐻𝑒𝑛𝑐𝑒 𝑡ℎ𝑒 𝑢𝑛𝑘𝑛𝑜𝑤𝑛 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑖𝑠 = 0 + 100 ºC 𝑑𝑇
 Advantage and disadvantages of thermocouple thermometer
Disadvantages
 Cold junction error- if it is not at 0 ºC
 Parasitic emf developed in the ckt due to (i) Peltier effect and (ii) Thomson effect. These are
eliminated by the use of materials free from such effect
 Increased resistance of the thermocouple due to the increase of temperature- this effect can be
avoided by the use of high-resistive galvanometer.
 No satisfactory relation between E and θ

Advantages:
 Can measure the wide range of temp. -200 to 3000 ºC
 Thermocouples are sensitive, cheap and simple
 Suitable for measuring the rapidly varying temp.-due to the low thermal capacity of hot junction
 Pyrometer
Radiation pyrometer:
Instrument used to measure high temp. by the method of radiation

Type of radiation pyrometer

(i) Total radiation pyrometer
(ii) Optical pyrometer

Total radiation pyrometer:

(i) the intensity of total radiation emitted by the body is measured by this pyrometer
(ii) Temperature is deduced by Stefan’s low of radiation

Stefan's Law: the rate of emission of radiant energy per unit area of a blackbody is proportional to the
forth power of absolute temp.

Optical pyrometer
In an optical pyrometer, the intensity of the standard lamp is varied until its intensity is equal to the
intensity of the radiation emitted by the measured body.
 Fery’s total radiation Pyrometer-Construction
M = Concave mirror made of Cu with Ni plated on the front 𝑀
E= eye piece is fitted with the central hole of the mirror C 𝑆 𝑅
𝐸
D= diaphragm is placed at the focus of M and is made of two
𝐷 𝑇 𝑇
semi-circular mirror with a central hole of 1.5 mm to allow
the radiation to pass
S= a blackened metal strip placed behind D
P G
TT= a thermocouple of one junction connected to S and
other junction kept at 0 °C and connected to galvanometer
P= screw for adjusting M
R= a screen to protect the S from direct radiation
 Fery’s total radiation Pyrometer-Working principle
 Radiation from the measured body incident on M
𝑀
 Focus the beam by adjusting M by the screw P 𝑆 𝑅
𝐸
 The focus beam fall on S through D
𝐷 𝑇 𝑇
 A circular focus beam is appeared through E like
figure (a) for in focus and (b) for out of focus P G
𝑇 = 𝑡𝑒𝑚𝑝𝑒𝑟𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑏𝑜𝑑𝑦
𝐸 = 𝑟𝑒𝑎𝑑𝑖𝑛𝑔 𝑜𝑓 𝑔𝑎𝑙𝑣𝑎𝑛𝑜𝑚𝑒𝑡𝑒𝑟
𝐸 ∝ 𝑇4
𝑎 𝑖𝑛 𝑓𝑜𝑐𝑢𝑠 𝑏 𝑜𝑢𝑡 𝑜𝑓 𝑓𝑜𝑐𝑢𝑠
Fery’s total radiation Pyrometer- Calibration

𝐸1 𝑎𝑛𝑑 𝐸2 𝑏𝑒 𝑡ℎ𝑒 𝑟𝑒𝑎𝑑𝑖𝑛𝑔 𝑜𝑓 𝑡ℎ𝑒 𝑔𝑎𝑙𝑣𝑎𝑛𝑜𝑚𝑒𝑡𝑒𝑟

𝑓𝑜𝑟 𝑘𝑛𝑜𝑤𝑛 𝑎𝑛𝑑 𝑢𝑛𝑘𝑛𝑜𝑤𝑛 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝑟𝑒𝑝𝑒𝑐𝑡𝑖𝑣𝑒𝑙𝑦
𝑇ℎ𝑒𝑛 𝐸1 ∝ 𝑇14
𝐸2 ∝ 𝑇24

𝐸1 𝑇14
= 4
𝐸2 𝑇2

1/4
𝐸2
𝑇2 = 𝑇1
𝐸1
 Fery’s total radiation Pyrometer- Calibration

For accurate measurement you need to calibrate the pyrometer

.
 The pyrometer is calibrated by using radiation from a .

log 𝐸
blackbody maintained at different known temperatures.
. .
.
 The galvanometer can be directly calibrated in degree kelvin
log 𝑇 (𝐾)
 Or a calibration curve is obtained by plotting galvanometer 𝐶𝑎𝑙𝑖𝑏𝑟𝑎𝑡𝑖𝑜𝑛 𝑐𝑢𝑟𝑣𝑒
deflection versus temperature
 Fery’s total radiation Pyrometer- For high temperature
 The usual range is 1500 °C,
 For higher temp , need a rotatory device R (a circular disc)
 Cut the disc at angle 𝜃
 R is rotated about the axis of pyrometer 𝜃

 R limit the amount of radiation incident on M

 If 𝑇1 be the temperature with disc, according tot Stefan’s law
𝜃 ∝ 𝑇14
If 𝑇 the actual temp of the hot body 𝐹𝑜𝑟 𝑒𝑥𝑎𝑚𝑝𝑙𝑒 , 𝑖𝑓 𝜃 = 22.5 𝑑𝑒𝑔𝑟𝑒𝑒
𝑇1 = 1500 𝐾, 𝑡ℎ𝑒𝑛
360 ∝ 𝑇 4 𝑇 = 1500 ×
360
= 3000 𝐾
1/4 22.5
360
𝑇 = 𝑇1
𝜃
 Fery’s total radiation Pyrometer- Applications

Used to measure temperature of moving target.

Used to measure temperature of a target where physical contact is impossible.

Used to measure invisible rays from radiations.

Fast response.

Used to measure very high temperature.

 Optical Pyrometer
Pyrometer
A pyrometer is a device that is used for the temperature measurement of an object. The device actually tracks
and measures the amount of heat that is radiated from an object. The thermal heat radiates from the object to
the optical system present inside the pyrometer. The optical system makes the thermal radiation into a better
focus and passes it to the detector. The output of the detector will be related to the input thermal radiation. The
biggest advantage of this device is that, unlike a Resistance Temperature Detector (RTD) and Thermocouple,
there is no direct contact between the pyrometer and the object whose temperature is to be found out.

Basic principle
The object whose temperature is above absolute zero (i.e.273.15 K) emits or generates radiation .The
emission is heat radiation which depends on temperature.Generally the infrared radiation is referred to the
measurement type as majority of radiations lie in the electromagnetic spectrum of infrared domain.This
domain lies in the spectrum of above visible red light.The energy radiated by the object is used to measure
the temperature of the object through the use of detective device which converts the received signal in to
electrical signal. The instruments or systems which is used for measurement purpose is known by common
names such as pyrometer/temperature guns or radiation pyrometers .
 Optical Pyrometer
Optical Pyrometer
In an optical pyrometer, a brightness comparison is made to measure the temperature. As a measure of the reference
temperature, a color change with the growth in temperature is taken. The device compares the brightness produced by the
radiation of the object whose temperature is to be measured, with that of a reference temperature. The reference
temperature is produced by a lamp whose brightness can be adjusted till its intensity becomes equal to the brightness of the
source object. For an object, its light intensity always depends on the temperature of the object, whatever may be its
wavelength. After adjusting the temperature, the current passing through it is measured using a multimeter, as its value will
be proportional to the temperature of the source when calibrated. The working of an optical pyrometer is shown in the figure
below.
 Optical Pyrometer
1. An eye piece (observer) at the left side and an optical lens on the right.
2. A reference lamp, which is powered with the help of a battery.
3. A rheostat to change the current and hence the brightness intensity.
4. So as to increase the temperature range which is to be measured, an
absorption screen is fitted between the optical lens and the reference
bulb.
5. A red filter placed between the eye piece and the reference bulb helps in
narrowing the band of wavelength.
 Optical Pyrometer
Working
The radiation from the source is emitted and the optical objective lens captures it. The lens helps in focusing
the thermal radiation on to the reference bulb. The observer watches the process through the eye piece and
corrects it in such a manner that the reference lamp filament has a sharp focus and the filament is super-
imposed on the temperature source image. The observer starts changing the rheostat values and the
current in the reference lamp changes. This in turn, changes its intensity. This change in current can be
observed in three different ways.
1. The filament is dark. That is, cooler than the temperature source.
2. Filament is bright. That is, hotter than the temperature source.
3. Filament disappears. Thus, there is equal brightness between the filament and temperature source. At
this time, the current that flows in the reference lamp is measured, as its value is a measure of the
temperature of the radiated light in the temperature source, when calibrated.
Optical Pyrometer
 Optical Pyrometer

Advantages
1. Simple assembling of the device enables easy use of it.
2. Provides a very high accuracy with +/-5 degree Celsius.
3. There is no need of any direct body contact between the optical pyrometer and the object. Thus, it can be used
in a wide variety of applications.
4. As long as the size of the object, whose temperature is to measured fits with the size of the optical pyrometer,
the distance between both of them is not at all a problem. Thus, the device can be used for remote sensing.
5. This device can not only be used to measure the temperature, but can also be used to see the heat produced by
the object/source. Thus, optical pyrometers can be used to measure and view wavelengths less than or equal to
0.65 microns. But, a Radiation Pyrometer can be used for high heat applications and can measure wavelengths
between 0.70 microns to 20 microns.
6. Can measure the moving objects.
7. Electrical items temp. can be measured which is very critical if we think of contact type measurement expl HT
panels,transformers.
8. The instruments can be used where physical approach is difficult Small ducts or some object at roof heights.
 Optical Pyrometer

Disadvantages
1. As the measurement is based on the light intensity, the device can be used
only in applications with a minimum temperature of 700 degree Celsius.
2. The device is not useful for obtaining continuous values of temperatures at
small intervals.

Applications
1. Used to measure temperatures of liquid metals or highly heated materials.
2. Can be used to measure furnace temperatures.
 Kinetic theory of gas
The molecules of all bodies are always in a state of random motion
and thus posses kinetic energy.

The kinetic energy increases with increasing temperature.

Kinetic theory of gases explains the macroscopic properties of

gases, such as pressure, temperature, viscosity, thermal

conductivity, and volume, by considering their molecular

composition and motion.

 Kinetic theory of gas-Assumptions
 The molecules are point masses. Their volumes are negligible compared to the volume of the container.

 Molecules motion is completely random in all directions with all possible velocities ranging from zero to infinity.

 Between two collisions, molecules move in a straight line with uniform velocity , i.e. they follow the Newton’s law.

 If no external force, then molecules distributed uniformly throughout a container; on the average the number of molecules

present in a small element of volume remain constant.

 The size of the molecules is infinitely small as compared to the distance travelled by a molecule between any two

consecutive collisions, called its mean free path.

 As molecules are perfectly elastic, the momentum and kinetic energy of the molecules before and after collision remain the

same

 The time during which a collision last is negligible in comparison to the time taken to traverse the mean free path
 Mean velocity:
The average value of all molecular velocities

c1  c2  .........  cn
c
n
Mean Square velocity:
The mean of the square of all the molecular velocities

c12  c22  ......... cn2

c 
2

n
Root means square velocity:
The square root of the mean square velocity

c 2
 c 2
 .........  c 2
c  c2  1 2 n
n

n c 2  c12  c22  .........  cn2 
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 Expression for pressure exerted by a gas:

𝐶 𝐴

𝑣
𝑣𝑦 = 𝑣𝑠𝑖𝑛𝜃
𝜃
𝑂 𝑣𝑥 = 𝑣𝑐𝑜𝑠𝜃 𝐵

𝑂𝐴2 = 𝑂𝐵2 + 𝐵𝐴2

𝑣 2 = 𝑣𝑥 2 + 𝑣𝑦 2

Therefore c u v w
2
1
2
1
2
1
2
1
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1/7/2025 81
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 Kinetic interpretation of temperature

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 Derivation of gas equation:
From kinetic theory of gas, we have
1 1M 2 1
P   c2  c or PV  M c 2 ...............(1)
3 3V 3
Consider one gram molecule of a gas at an absolute temperature T. The mean
energy of the molecules is
1 1 2 1
M c 2  mnc 2  n ( mc2 )...........(2)
3 3 3 2
2 1
Using equations (1) and (2) PV  n ( mc2 )...........(3)
3 2
1 2 3
The mean kinetic energy of a molecule mc  kT..............(4)
2 2
Using equations (3) and (4)
2 3
PV  n ( kT )
3 2
 PV  n kT But , R  nk

 PV  RT

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 Mean free path:

𝑇𝑜𝑡𝑎𝑙 𝑝𝑎𝑡ℎ 𝑡𝑟𝑎𝑣𝑒𝑙𝑙𝑒𝑑 𝑏𝑦 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 𝑖𝑛 𝑜𝑛𝑒 𝑆𝑒𝑐𝑐𝑜𝑛𝑑 𝑑1 + 𝑑2 + 𝑑3 +. . . . . . . . . . . . . +𝑑𝑛

𝑀𝑒𝑎𝑛 𝑓𝑟𝑒𝑒 𝑝𝑎𝑡ℎ = =
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑐𝑜𝑙𝑙𝑖𝑠𝑖𝑜𝑛𝑠 𝑖𝑛 𝑜𝑛𝑒 𝑆𝑒𝑐𝑐𝑜𝑛𝑑 𝑛

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 Mean Free Path
if the molecules have diameter d, then the effective cross-section for collision can be
modeled by

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 The above equation was derived by Clausius. The problem with this expression is that the
average molecular velocity is used and the target molecules are assumed geometrical
points.
But in actual practice, the target molecules also move. The frequency of collisions depends
upon the average relative velocity of the randomly moving molecules.
Maxwell amended the equation of mean free path by considering the relative velocity.

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 The resulting mean free path is

The number of molecules per unit volume can be determined from Avogadro's number
and the ideal gas law, leading to

Problem1: Calculate the mean free path and collision frequency for air molecules
at 0°C and 1 atom pressure. Given that the effective diameter of the air molecules 2
Å, the root means square velocity of air molecules at N.T.P. is about 10 5 cm/sec
and the number of molecules per cc is 3 x1019.

Problem 2: Estimate the size of the helium atoms, assuming its mean free path at N.T.P.
to be 28.5 x 10-6 cm. Given that the density of helium at N.T.P. is 0.178 g/litre and the
mass of the helium atom is 6 x 1024 g.
Problem3: Find the mean free path of a gas molecules of diameter 2 x 10 -8 cm and the
number of molecules per cc is 3 x 1018.
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 Average Relative Velocity
In order to calculate the mean free path for a molecule of a gas, it is necessary to assess the
average relative velocity of the molecules involved rather than just the average velocity of any
given molecule. The relative velocity of any two molecules can be expressed in terms of their
vector velocities.

The magnitude of the relative velocity can be expressed as the square root of the scalar
product of the velocity with itself.

This expression can be expanded as follows

Taking the average of the terms leads to

Since the same average velocity would be associated with each molecule, this becomes

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 Problem1: Calculate the number of molecules per c.c. of a gas if the mean
free path of the molecules is 2.4x10 -6 cm. and the molecular diameter is
equal to 2x10-8 cm.
1

2d 2 n
Problem2: The diameter of a molecule of gas is 3x 10 -10 m and number of
molecules per cm3 is 6X 1020. Calculate the mean free path of the
molecules.

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Degrees of Freedom

The number of degrees of freedom of a dynamical system is defined as the total number of co-ordinates or
independent variables required to describe the position and configuration of the system.

Three type of degree of freedoms

1. Degree of freedom of translational motion, 𝑓𝑡
2. Degree of freedom of rotational motion, 𝑓𝑟
3. Degree of freedom of translational motion, 𝑓𝑣

𝑇𝑜𝑡𝑎𝑙 𝑑𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑓𝑟𝑒𝑒𝑑𝑜𝑚, 𝑓 = 𝑓𝑡 + 𝑓𝑟 + 𝑓𝑣

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 Monoatomic gas (He, Ne, Ar)

1. Translation degree of freedom = 3

2. Rotational degree of freedom = 0
3. Vibrational degree of freedom = 0

 The 3 translational motion is due to movement of

atom along x, y and z axes
 the molecule can also rotate about x, y and z axes.
 For spherical molecule , the moment of inertial of a
2
spherical atom 𝐼 = 𝑚𝑟 2 ~0, since mass of the is
5
negligible and size of molecule is very small. We
know all mass of the atom can thought to be
concentrated in the nucleus and the radius , 𝑟 , of the
nucleus 10−15
 For single atom, there is no bond, so no vibrational
degree of freedom

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Diatomic gas molecules (H2, O2, N2)

1. Translation degree of freedom = 3

2. Rotational degree of freedom = 2
3. Vibrational degree of freedom = 2

 The 3 translational motion is due to movement of

atom along x, y and z axes
 the molecule can also rotate about x, y and z axes.
 For spherical molecule , the moment of inertial of a
2
spherical atom 𝐼 = 𝑚𝑟 2 ~0, since mass of the is
5
negligible and size of molecule is very small. We
know all mass of the atom can thought to be
concentrated in the nucleus and the radius , 𝑟 , of the
nucleus 10−15
 For single atom, there is no bond, so no vibrational
degree of freedom
 𝑇 < 100𝐾, 𝑓 = 3, 𝑛𝑜 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛 𝑏𝑒𝑙𝑜𝑤 100 𝐾
 100𝐾 < 𝑇 < 1000𝐾, 𝑓 = 5, no vibration below 1000K
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 𝑇 > 1000𝐾, 𝑓 = 7 94
 Diatomic gas molecules (H2, O2, N2)

1. Translation degree of freedom = 3

2. Rotational degree of freedom = 2
3. Vibrational degree of freedom = 2

 The 3 translational motion is due to movement of

atom along x, y and z axes
 the molecule can also rotate about x, y and z axes.
 For spherical atom , the rotational energy along the X
axis is negligible due to spinning of atom along the
axis, Only Y and Z axes have the rotational energy, So
the rotational degree of freedom = 2
 For diatomic molecule , there is a bond between two
atoms

 𝑇 < 100𝐾, 𝑓 = 3, 𝑛𝑜 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛 𝑏𝑒𝑙𝑜𝑤 100 𝐾

 100𝐾 < 𝑇 < 1000𝐾, 𝑓 = 5, no vibration below 1000K
 𝑇 > 1000𝐾, 𝑓 = 7
 Triatomic gas molecules (H2, O2, N2)

1. Translation degree of freedom = 3

2. Rotational degree of freedom = 2 (linear atomic arrangement)
3. Vibrational degree of freedom = 4x2=8

 The 3 translational motion is due to movement of

atom along x, y and z axes
 the molecule can also rotate about x, y and z axes.
 For spherical atom , the rotational energy along the X
axis is negligible due to spinning of atom along the
axis, Only Y and Z axes have the rotational energy, So
the rotational degree of freedom = 2
 For diatomic molecule , there is a bond between two
atom

 𝑇 < 100𝐾, 𝑓 = 3, 𝑛𝑜 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛 𝑏𝑒𝑙𝑜𝑤 100 𝐾

 100𝐾 < 𝑇 < 1000𝐾, 𝑓 = 5, no vibration below 1000K
 𝑇 > 1000𝐾, 𝑓 = 7
 Triatomic gas molecules (H2, O2, N2)
1. Translation degree of freedom = 3
2. Rotational degree of freedom = 3 (non linear atomic
arrangement)
3. Vibrational degree of freedom = 3x2=6

 The 3 translational motion is due to movement of

atom along x, y and z axes
 the molecule can also rotate about x, y and z axes.
 For spherical atom , the rotational energy along the X
axis is negligible due to spinning of atom along the
axis, Only Y and Z axes have the rotational energy, So
the rotational degree of freedom = 2
 For diatomic molecule , there is a bond between two
atom
 Translation Rotation Vibration Total
Molecule geometry
ftransftrans frotfrot fvibfvib ff

monatomic 3 0 0 (×2) 3

diatomic 3 2 1 (×2) 7

triatomic
3 3 3 (×2) 12
(non-linear)

triatomic
3 2 4 (×2) 13
(linear)
Maxwell law of equi-partition of energy:
Maxwell showed that if during motion the molecules obey ordinary law of mechanics, the total energy of a system is
1
equally divided among all degrees of freedoms and for each degrees of freedom of a molecule its equals to 𝑘𝑇
2
where k is boltzmann constant.

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 Application of law of equipartition energy in specific heat of a gas

 Meyer’s relation CP − CV = R connects the two specific heats for one mole of an ideal gas.
 Equipartition law of energy is used to calculate the value of CP − CV and the ratio between them γ = CP / CV.
 Here γ is called adiabatic exponent.

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1. Specific heat at a constant volume and
2. Specific heat at a constant pressure

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Relation between pressure (P) and volume (V) of a gas in an adiabatic
change:

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1/7/2025 106
Application of the law of equipartition energy in specific heat of a monoatomic gas
Application of the law of equipartition energy in specific heat of a diatomic gas
Application of the law of equipartition energy in specific heat of a triatomic gases

For linear molecule For non-linear molecule

Neglecting the vibrational energy which is effective only at high temperature (above 1000 K)
Relation between the ratio of specific heats and degree of freedom
Find the adiabatic exponent γ for mixture of μ1 moles of monoatomic gas and
μ2 moles of a diatomic gas at normal temperature.
5.7 Maxwell’s Distribution Curves

112
 At a particular temperature, a gas molecule has a fixed mean kinetic energy
 It does not mean that the molecule is moving with the same speed throughout its movement.
 After each encounter the speed of the molecule changes and due to a large number of collisions, the speed is different
at different instants
 But the root means square velocity (C) remain the same at fixed temperature
 At any instant al the molecules are not moving with the same velocity
 Some are moving with a velocity higher than C and the other with a velocity lower than C
 But the mean kinetic energy of all the molecules remains constant at a given temperature.

 For many physical and chemical problems, it is important to know the speed distribution of the molecules.
 For instnant, we may like to know how many molecules have more than twice the C or how many have speeds in the
interval 0.79C to 0.80C.
 This can be found from Maxwell’s distribution law

 Let the velocity of a molecule denoted by c have the components u, v and w at right angles to each other.
 One of the components of the velocity of a molecule will not depend upon the values of other components
 N be the total number of molecule

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 Equation of state
The equation state of a perfect gas is (obtained by
combining Boyle and Charles law)

𝑃𝑉 = 𝑅𝑇
𝑃= pressure, V= volume, T= absolute temperature
of a gas and R = gas constant

This equation is valid at high temperature and low

pressure

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 Deviation of Boyle law- K. Onnes equation state
A more general form is proposed by K. Onnes
M𝑜𝑟𝑒 𝑃𝑒𝑟𝑓𝑒𝑐𝑡 𝑔𝑎𝑠 (𝐻2 , 𝐻𝑒)
𝑃𝑉 = 𝐴 + 𝐵𝑃 + 𝐶𝑃2 + 𝐷𝑃3
A, B, C, D are constant depending on nature of gases
𝑃𝑒𝑟𝑓𝑒𝑐𝑡 𝑔𝑎𝑠
and temperature ↑
𝐴𝑡 𝑙𝑜𝑤 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒, 𝑃 → 0, 𝑃𝑉 = 𝐴 = RT 𝑃𝑉 L𝑒𝑠𝑠 𝑃𝑒𝑟𝑓𝑒𝑐𝑡 𝑔𝑎𝑠 (𝑂2 , 𝑁2, 𝐶𝑂2, air)
𝑑
𝑃𝑉 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝑃𝑉 = 0
𝑑
𝑑𝑃
𝑃 →
𝐴 + 𝐵𝑃 + 𝐶𝑃2 + 𝐷𝑃3 = 0
𝑑𝑃
𝐵 + 2𝐶𝑃 + 3𝐷𝑃2 = 0
𝐴𝑏𝑜𝑣𝑒 𝐵𝑜𝑦𝑙𝑒 𝑡𝑒𝑚𝑝.
𝐴𝑡 𝑙𝑜𝑤 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒, 𝑃 → 0, 𝐵 = 0
𝐴𝑡 𝐵𝑜𝑦𝑙𝑒 𝑡𝑒𝑚𝑝.
The temp at which B=0 is known as Boyle temp, 𝑇𝐵 .
At low temperature, B is negative and increase to zero
↑
𝑃𝑉 𝐵𝑒𝑙𝑜𝑤 𝐵𝑜𝑦𝑙𝑒 𝑡𝑒𝑚𝑝.
with increase of temperature and become positive with
further increase of temp. 𝑃 →
Andrew’s experiment-on CO2
The point C on the critical isothermal where liquid, vapor and gaseous
states of a substance meet is described as the critical point.

Critical temperature: below this temperature vapor can be liquefied by

the application pressure and above this temperature the gas can not be
liquefied

Critical pressure: The pressure applied to a gas at its critical temperature

Critical volume: the particular volume of gas at critical temperature and
critical pressure.

Scientific difference between vapor and gas may now be understood

Vapor: A substance below its critical temperature is vapor, which can be

converted into liquid by application of pressure.

Gas: A substance above its critical temperature is gas, which can not be
converted into liquid by application of pressure.
 Van der Waals equation state
The perfect gas equation PV = RT
This equation was derived based on the following assumptions
1. The size of the gas molecules is negligible, so volume
occupied by the molecule is negligible compared to the
volume of the container.
2. The force of intermolecular attraction are absent

But in actual practice, At high pressure

1. The size of the gas molecules becomes significant and can
not be neglected compared to the volume of the container
2. The molecules come closer at high pressure and the force of
intermolecular attraction are appreciable
1/7/2025 125
 Van der Waals equation state

1. Pressure correction:
Intermolecular force balance
 At high pressure, the intermolecular distance is decreased, so
B
intermolecular attraction force is no more negligible. A
 For molecule A, the intermolecular force is balanced
Inward pull
 The B molecule B will experience inward pull

Pressure being observed (𝑃 ) on the walls of vessel is a less than ideal

pressure.
𝑃 = 𝑃𝑖 – 𝑝1
Wher 𝑃𝑖 = ideal pressure and 𝑝1= Pressure lessened due to molecular
attraction
1/7/2025 𝑃𝑖 = 𝑃 + 𝑝1 126
 Van der Waals equation state
Pressure correction: Intermolecular force balance
The 𝑝1 is proportional to the square of the density (𝜌) of gas
molecules
B
𝑝1 ∝ 𝜌2 A Inward pull
𝑝1 = 𝐶𝜌2
𝑁𝑚 It is obvious that the magnitude of the pressure p1
𝐶 is a constant depends on nature of gas molecules, 𝜌 = is
𝑉 due to the inward pull will be proportional jointly
where N= total number of molecule in volume V and m = mass to (i) the number of molecules striking unit area of
the wall per second and (ii) the resultant normal
of each molecules component of the cohesive forces. As each of these
two factors is directly proportional to the number of
𝑁2𝑚2 𝑎 molecules present in a given volume, i.e., the
𝑝1 = 𝐶 2 = 2 [Assume, 𝐶𝑁2𝑚2 = 𝑎] density of the gas p1 will be proportional to the
𝑉 𝑉
square of the density.
𝑎
𝑆𝑜, 𝑃𝑖 = 𝑃 + 2
𝑉
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 Van der Waals equation state
Volume correction: S is the volume of the sphere of influence
Consider empty encloser of volume V and imagine a number of N molecules are formed by two molecules (Figure)
introduced one by one. Sphere of
influence
Volume available for the 1st molecules = 𝑉
Volume available for the 2nd molecule = 𝑉 − 𝑆 (Now two molecule inside the encloser) 𝑟 𝑟
Volume available for the 3rd molecule = 𝑉 − 2𝑆
Volume available for the nth molecule = 𝑉 − (𝑛 − 1)𝑆 𝑑
Average volume available for each molecule
4
𝑉 + 𝑉 − 𝑆 + 𝑉 − 2𝑆 + ⋯ … … … + [𝑉 − 𝑛 − 1 𝑆] Volume of each molecule 𝑥 = 𝜋𝑟 3
3
= 4
𝑛 Volume of the sphere of influence, 𝑆 = 𝜋𝑑3
3
4 4
𝑛𝑉 𝑆 𝑛𝑉 𝑆 𝑛 𝑛 − 1 𝑆 = 𝜋(2𝑟)3 = 8 × 𝜋𝑟 3 = 8𝑥
= − × [1 + 2 + ⋯ … … . . + 𝑛 − 1 ] = + × 3 3
𝑛 𝑛 𝑛 𝑛 2

𝑆 𝑛−1 𝑆 𝑛−1
=𝑉− =𝑉−𝑏 𝑤ℎ𝑒𝑟𝑒 𝑏 =
2 2 128
 Van der Waals equation state
Volume correction: S is the volume of the sphere of influence
formed by two molecules (Figure)
𝑆 𝑛−1 4 3 𝑛−1 4 3 Sphere of
𝑏= = 8 × 𝜋𝑟 = 4 × 𝑛 × 𝜋𝑟 influence
2 3 2 3
𝑏 = 4 × 𝑛𝑥 = 4 × 𝑎𝑐𝑡𝑢𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
𝑟 𝑟

So, The Van der Waals equation of state of gas is 𝑑

𝑎
𝑃+ 2 𝑉 − 𝑏 = 𝑅𝑇 4
Volume of each molecule 𝑥 = 𝜋𝑟 3
3
𝑉 Volume of the sphere of influence, 𝑆 = 𝜋𝑑3
3
4

4 4
𝑆 = 𝜋(2𝑟)3 = 8 × 𝜋𝑟 3 = 8𝑥
3 3

129
Critical constant

130
Critical constant

131
Critical constant

132
 Relation between Boyle temperature and critical temperature

𝑣 𝑎
𝑅𝑇𝐵 −1 =
𝑣−𝑏 𝑣

𝑏 𝑎
𝑅𝑇𝐵 =
𝑣−𝑏 𝑣
At Boyle Temperature, T becomes TB; our
perfect gas equation becomes 𝑎(𝑣 − 𝑏)
𝑇𝐵 =
𝑅𝑣𝑏
pν = RTB (2)
𝑎
𝑇𝐵 = {𝑠𝑖𝑛𝑐𝑒 𝑏 𝑖𝑠 𝑠𝑚𝑎𝑙𝑙, 𝑣 − 𝑏 ≈ 𝑣}
From Eqn (1) and (2), we get 𝑅𝑏
8𝑎 8
𝑤𝑒 𝑘𝑛𝑜𝑤, 𝑇𝑐 = = 𝑇
27𝑅𝑏 27 𝐵
27
TB = 𝑇
8 𝑐
 Defect of Van der Waals equation

1. 𝑇ℎ𝑒 𝑐𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒, 𝑉𝑐 = 3𝑏 𝑏𝑢𝑡 𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 𝑜𝑏𝑠𝑒𝑟𝑣𝑎𝑡𝑖𝑜𝑛 ℎ𝑎𝑣𝑒 𝑠ℎ𝑜𝑤𝑛 𝑡ℎ𝑎𝑡 𝑉𝑐 𝑣𝑎𝑟𝑖𝑒𝑠 𝑓𝑟𝑜𝑚 1.4 𝑏 𝑡𝑜 2.8𝑏

𝑅𝑇𝑐
2. Tℎ𝑒 critical coefficient = 2.67 𝑏𝑢𝑡 𝑡ℎ𝑒 𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡 𝑣𝑎𝑙𝑢𝑒 𝑖𝑠 3.7
𝑃𝑐𝑉𝑐

3. The value of a and b slightly changes with temperature and pressure

4. The theoretical P-V curve is not similar to the experiment P-V diagram
Critical constant
Thermodynamic system
A thermodynamic system is defined as a quantity
of matter or a region in space which is selected for
the study.

The mass or region outside the system is called

surroundings.

The real or imaginary surfaces which separates the

system and surroundings is called boundary. The
boundary of a system can be fixed or movable.
Thermodynamic system
 Thermodynamic variable, state and process
The properties of system such as temperature (T), Pressure (P),
volume (V) when changed, the system also changes. These
properties are called state variables.

The state of a system which is expressed by thermodynamic

variables is called thermodynamic state.

The changes which causes the changes of values of

thermodynamic variables is called thermodynamic process.
 Thermodynamic process
Isothermal process → the process takes place at constant temperature
(e.g. freezing of water to ice at –10C)
Isobaric → constant pressure
(e.g. heating of water in open air→ under atmospheric pressure)
Isochoric → constant volume
(e.g. heating of gas in a sealed metal container)
Adiabatic process → (no heat is added/removed to/from the system)
 Thermodynamic equilibrium
The system is said to be in thermodynamic equilibrium if the conditions for following three equilibrium is satisfied:
1) Mechanical equilibrium
2) Chemical equilibrium
3) Thermal equilibrium

1) thermal equilibrium
For a system to be in thermal equilibrium there should be no temperature difference between the parts of the
system or between the system and the surroundings.
2) Chemical equilibrium
For a system to be in chemical equilibrium, the composition of the system should remain fixed and definite
3) Mechanical equilibrium
For a system to be in mechanical equilibrium, there should be no unbalanced force existing between different
parts of the system or between the system and the surroundings.
 Heat and work
Heat vs work

Heat and work are two different ways of transferring energy from
one system to another.

Heat is the transfer of thermal energy between systems, while work is the
transfer of mechanical energy between two systems.

Heat can be transformed into work and vice verse (see mechanical
equivalent of heat), but they aren't the same thing.
 How do we determine the sign of the work done from a PV diagram?
Let's say our gas starts out in the state shown in the PV diagram
below.

If we press the piston downward, the volume of the gas will decrease,
so the state must shift to the left toward smaller volumes (as seen in
the diagram below). Since the gas is being compressed we can also say
for sure that positive work is being done on the gas.

Similarly, if we let the gas expand, pushing the piston upward, the
volume of the gas will increase, so the state must shift to the
right toward larger volumes (as seen in the diagram below). Since the
gas is expanding we can also say for sure that negative work is being
done on the gas.

So if we ever see a state shifting to the left on a PV diagram we can

say for sure that the work done on the gas was positive.

Similarly, if we ever see a state shifting to the right on a PV diagram

we can say for sure that the work done on the gas was negative.
 What are PV diagrams?
Consider a gas in a sealed container with a movable piston
You can do work on the gas by pressing the piston downward Fig. 1
You can heat up the gas by placing the container over flame

When you subject the gas to these thermodynamic processes, the

pressure and volume of the gas can change

PV diagram- a convenient way to visualize these changes in the Fig. 2

pressure and volume. Each point on a PV diagram corresponds to a
different state of gas

PV diagram is obtained by plotting the pressure on the vertical axis

and volume in the horizontal axis (fig. 2).

As a gas goes through a thermodynamics process, the state of the gas

will shift around in the PV diagram, tracing out a path
as it moves (as shown in the diagram below) Fig. 3
 PV diagram in different thermodynamic process
P P

V V
Isobaric: pressure constant Isochoric: volume constant

P P

V
Adiabatic : No heat exchange V
Isothermal : Temperature constant
Summary of Processes
Application of the first law of thermodynamic

Specific heat of a gas

Consider the application of the first law of thermodynamics to unit mass of working
substance. When the system expands by a volume dV against the uniform external
pressure P, we have
𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉 … … (1)

The internal energy of a system is a complex function of temperature, pressure, volume,

etc.
Incase of gas any of the two variables are sufficient to define completely its state.

If V and T are chosen as the independent variables,

𝑈 = 𝑓 𝑉, 𝑇 … … 2
 Application of the first law of thermodynamic
Specific heat of a gas
Differentiating equation (2)

𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉 … … 3
𝜕𝑇 𝑉
𝜕𝑉 𝑇
From equation (1) and (3)
𝜕𝑈 𝜕𝑈
𝑑𝑄 = 𝑑𝑇 + 𝑑𝑉 + 𝑃𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇
Dividing by dT
𝑑𝑄 𝜕𝑈 𝜕𝑈 𝑑𝑉 𝑑𝑉
= + +𝑃 … … … (4)
𝑑𝑇 𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝑑𝑇 𝑑𝑇
If the gas heated at constant volume,

𝜕𝑄 𝑑𝑉
𝐶𝑉 = 𝑎𝑛𝑑 =0
𝜕𝑇 𝑉 𝑑𝑇
𝜕𝑄 𝜕𝑈
𝐶𝑉 = = 𝜕𝑄 = 𝜕𝑈 + 0, 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑣𝑜𝑙𝑢𝑚𝑒
𝜕𝑇 𝑉
𝜕𝑇 𝑉
 Application of the first law of thermodynamic
Specific heat of a gas
If the gas heated at constant pressure,

𝜕𝑄
𝐶𝑃 =
𝜕𝑇 𝑃

𝑑𝑄 𝜕𝑈 𝑑𝑉 𝜕𝑉
= 𝐶𝑉 + +𝑃 … … … (4)
𝑑𝑇 𝜕𝑉 𝑇 𝑑𝑇 𝜕𝑇
At constant pressure equation (4) can be written as
𝜕𝑄 𝜕𝑈 𝜕𝑉
= 𝐶𝑉 + +𝑃
𝜕𝑇 𝑃 𝜕𝑉 𝑇
𝜕𝑇
𝑃

𝜕𝑈 𝜕𝑉
𝐶𝑃 = 𝐶𝑉 + +𝑃 … … … … … . (5)
𝜕𝑉 𝑇
𝜕𝑇
𝑃
 Application of the first law of thermodynamic
Specific heat of a gas
Particular case, from Joules experiment for an ideal gas on opening the stop cork, no work was done and
no heat transfer took place
So, 𝜕𝑄 = 0 = 𝜕𝑈 + 0. therefore 𝜕𝑈 = 0. Even though the volume the volume changed while the
temperature is constant, there is no change in internal energy.
𝜕𝑈
=0
𝜕𝑉 𝑇
From ideal gas equation, 𝑃𝑉 = 𝑅𝑇
𝜕𝑉
𝑃 =𝑅
𝜕𝑇 𝑃
Equation (5) becomes
𝐶𝑃 = 𝐶𝑉 + 𝑅
𝐶𝑃 − 𝐶𝑉 = 𝑅
Work done during expansion or compression of a gas
Work done during isothermal expansion or compression of a gas
Work done during adiabatic expansion or compression of a gas
Work done during adiabatic expansion or compression of a gas
 Slopes of adiabatic and isothermal
𝐼𝑛 𝑖𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑝𝑟𝑜𝑐𝑒𝑠𝑠, 𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Differentiating 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 0

𝑑𝑃 𝑃
= − ……….. 1
𝑑𝑉 𝑉
In adiabatic process, 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃𝛾𝑉 𝛾−1 𝑑𝑉 + 𝑉𝑑𝑃 = 0

𝑑𝑃 𝛾𝑃
= − ……….. 2
𝑑𝑉 𝑉
The slope of an adiabatic is 𝛾 times the slope of the isothermal
The adiabatic curve is steeper than the isothermal curve.
 Second law of thermodynamics

 The first law of thermodynamic deals with the principle of conservation of energy.

 It tells that whenever work is obtained, an equivalent amount of heat is used up and vice versa

 The first law does not tell anything about the limitation and condition in the conversion of heat into work

 Work can not be converted into heat without the help of any machine

 For example two hands rubbed together heat will produce

 To obtain mechanical work from heat, we take the help of a heat engine
 Heat Engines

A device which converts heat into mechanical work is called a heat engine.
All heat engines have:
 Source: a high-temperature reservoir (Th), from which heat engine
takes heat.
 Sink: a low-temperature reservoir (Tc), at which any amount of heat
can be rejected
 Working substance: the substance, which on being supplied with heat,
performs mechanical work, is called the working substance.

Working principle: In a heat engine, the working substance takes in heat

from the source, converts a prat of it into external work, gives out the rest to
the sink and returns to its initial states.
 Reversible process
A reversible process is one which can be retraced in opposite direction so that all changes occurring in direct
process are reversed exactly with corresponding parts in the reverse process

No wastage of energy at all in the reversible process.

Condition of reversibility:
 the pressure and temperature of the working substance must not differ applicably from those of the
surrounding at any stage of the cyclic operation.
 the substance undergoing a reversible change must not lose heat. Hence for reversibility complete absence
of dissipative effects is a must.
 All reversible processes must take place slowly.
 The working part of the engine must be free from friction. These conditions are never strictly realized in
practice because no mechanical process is frictionless, and no insulator or conductor is perfect.
 There should not be any loss of energy due to conduction or radiation during the cycle of operation.

Thus reversibility is an ideal conception only while irreversibility is the rule.

Examples:

1. All isothermal and adiabatic processes when performed very slowly may be considered as reversible.
2. Exactly slow concentration or extension of a spring also may be considered as reversible process.
 Irreversible process
Those processes which can not be retraced in the opposite order by reversing the controlling factors are
known as irreversible process.

All natural process are irreversible.

Example:

1. Exchange of heat between bodies at different temperatures by conduction or radiation

2. Frictional processes
3. Heat generated by the transfer of electricity through a resistor
4. Diffusion of gasses and liquids
5. Sudden unbalanced expansion of gas
 Carnot’s heat engine
In 1824, Sadi Carnot discovered a method that the most
efficient engine is none in which all the operations are
made in a reversible manner.

He suggested an ideal theoretical engine free from all the

imperfectness of actual engines.. This imaginary engine
is taken as a standard against which the performance of
actual engines is judge.

Description of the Carnot’s engine:

Source: A body of high heat capacity maintained at a constant high temperature serving as the source of heat
Cylinder: A cylinder with perfectly non-conducting walls but perfectly conducting base containing working substance. The
cylinder is fitted with a perfectly insulating and frictionless piston. The cylinder may be placed on any of the three bodies
(source, stand and sink) and my be moved without friction.
Stand: A perfectly non-conducting stand is also provided so that the working substance can undergo adiabatic operation.
Sink: A cold body of high heat capacity maintained at a constant low temperature serving as sink.
 Carnot’s cycle
A cycle in which the working substance starting a certain
temperature, pressure and volume is made to undergo
two successive expansions (one isothermal and the other
adiabatic) and ten two successive compressions ( one
isothermal and the other adiabatic), and then brought
back finally to its initial state is called Carnot’s cycle.

Step 1. a → b. An isothermal expansion of the

gas at temperature T1 .

Step 2. b → c. An adiabatic expansion of the

gas until the temperature drops to T2 .

Step 3. c → d. An isothermal compression of

the gas at temperature T2 .

Step 4. d → a. An adiabatic compression of the

gas until its temperature reaches T1.
 Calculation of work done in each Carnot’s cycle
Operation I (Isothermal Expansion, Curve AB): The cylinder is placed on the source and the piston be moved forward
slowly. The cylinder containing ideal gas as working substance allowed to expand slowly at this constant temperature T₁.

Work done = Heat absorbed by the system

 Work done is equal to the area under the curve-why
The work done during a thermodynamic process is equal to the area under the curve as seen in the diagram
below.

The reason why work is equal to the area under the curve is that,
𝑊 = 𝐹Δ𝑥 = (𝑃𝐴)Δ𝑥 = 𝑃(𝐴Δ𝑥) = 𝑃Δ𝑉
 Calculation of work done in each Carnot’s cycle
Operation II (Adiabatic Expansion, Curve BC): The cylinder is then placed
on the non – conducting stand and the gas is allowed to expand adiabatically
till the temperature falls from T₁ to T₂.

𝑉3

𝑊2 = න 𝑃𝑑𝑉 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝑘
𝑉2
𝑉3

𝑊2 = 𝑘 න 𝑉 −𝛾 𝑑𝑉
𝑉2
𝑉 −𝛾+1 −𝛾+1
𝑉 −𝛾+1 3 𝑘𝑉 − 𝑘𝑉2 𝛾 𝛾
=𝑘 = 3 𝑃2 𝑉2 = 𝑃3 𝑉3 = 𝑘
−𝛾 + 1 𝑉2
−𝛾 + 1
𝛾 −𝛾+1 𝛾 −𝛾+1
𝑃3 𝑉3 𝑉3 − 𝑃2 𝑉2 𝑉2 𝑃3 𝑉3 − 𝑃2 𝑉2
= = 𝑃2 𝑉2 = 𝑅𝑇2 𝑎𝑛𝑑 𝑃3 𝑉3 = 𝑅𝑇3
1−𝛾 1−𝛾
𝑅 𝑇2 − 𝑇1
= = 𝐴𝑟𝑒𝑎 𝐵𝐶𝐻𝐺
1−𝛾
 Calculation of work done in each Carnot’s cycle
Operation 3 (Isothermal Compression, Curve CD): The
cylinder is placed on the sink and the gas is compressed at
constant temperature T₂.

Work done = Heat released by the system

Operation 4 (Adiabatic Compression, Curve DA): Finally, the cylinder

is again on non – conducting stand and the compression is continued so
that gas returns to its initial stage.
𝑉1
𝑅 𝑇1 − 𝑇2
𝑊4 = − න 𝑃𝑑𝑉 = − = 𝐴𝑟𝑒𝑎 𝐴𝐷𝐹𝐸
1−𝛾
𝑉4

𝑇ℎ𝑒 𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 = 𝑊1 + 𝑊2 + 𝑊3 + 𝑊4 = 𝑊1 − 𝑊4 = Q1 − Q2

 Efficiency of Carnot’s engine
The efficiency of the engine is given by
ℎ𝑒𝑎𝑡 𝑐𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑 𝑖𝑛𝑡𝑜 𝑤𝑜𝑟𝑘
𝜂=
ℎ𝑒𝑎𝑡 𝑑𝑟𝑎𝑤𝑛 𝑓𝑟𝑜𝑚 𝑠𝑜𝑢𝑟𝑐𝑒
Q1 − Q2 Q2
𝜂= =1−
Q1 Q1
𝑉2 𝑉2
𝑄1 𝑊1 𝑅𝑇 1 𝑙𝑜𝑔 𝑇1 𝑙𝑜𝑔
𝑉1 𝑉1
= = = … … . . (1)
𝑄2 𝑊3 𝑅𝑇 𝑙𝑜𝑔 𝑉3 𝑇 𝑙𝑜𝑔 𝑉3
2 𝑉4 2 𝑉4
Since the point B and C lie on the same adiabatic process, we
have
𝛾−1
𝛾−1 𝛾−1 𝑇1 𝑉3
𝑇1 𝑉2 = 𝑇2 𝑉3 ⇒ = … … … (2)
𝑇2 𝑉2
Similarly the point D and A lie on the same adiabatic
𝑇1 𝑉4
𝛾−1 Q2 𝑇2
𝑇1 𝑉1
𝛾−1
= 𝑇2 𝑉4
𝛾−1
⇒ = ……… 3 𝜂 =1− =1−
𝑇2 𝑉1 Q 1 𝑇1
This relation shows that the efficiency depends
From equation (2) and (4)
𝑉3 𝑉2 only upon the temperature of the source and sink.
= ……… 4
𝑉4 𝑉1
From equation (1) and (4)
𝑄1 𝑇1
=
𝑄2 𝑇2
An ideal gas in a sealed container is taken through the process shown in
the PV diagram-1. The initial volume of the gas is 𝑉𝑖 = 0.25 𝑚3 and final
volume of the gas is 𝑉𝑓 = 0.75 𝑚3. the initial pressure of the gas is 𝑃𝑖 =
70000 Pa and the final pressure of the gas 𝑃𝑓 = 160 000 𝑃𝑎. What is
the work done on the gas during the process shown?
Diagram-1
 Entropy
Entropy is a measure of the degree of randomness of
energy in a system.

The lower the entropy the more the order and less
randomness

Physical significance of entropy:

 Entropy of a substance is the physical quantity which remain constant when the substance undergoes a reversible
adiabatic process.
 Natural process take place in such a direction along which the entropy increases
 Entropy is a state function-change in entropy depends only on the two state and does not depends on the path along
which it reaches to the final state.
 General notation of Entropy
A1
A2
Consider a series of isothermal at temperature T1, T2,
P Q1
T3 on a PV diagram. A1 and A2 adiabatic cutting the a
isothermals at a, b and c, d and f,e. T1
b
Abcd represent the carnot’s reversible cycle
𝑄1 𝑄2 Q2
= d
𝑇1 𝑇2 T2
Similarly considering dcef cycle c
𝑄2 𝑄3 Q3
= f T
𝑇2 𝑇3
𝑄1 𝑄2 𝑄3 e
= =
𝑇1 𝑇2 𝑇3
𝑄 V
The quantity is constant known as entropy (S).
𝑇 The entropy for adiabatic A1 and A2 be S1 and S2 , then the
change in entropy
If the adiabatic are very close , and the heat absorbed 𝑆2 𝑏
or rejected at a temperature T, then 𝑑𝑄
𝑑𝑄 න 𝑑𝑆 = 𝑆2 − 𝑆1 = න
𝑑𝑆 = 𝑇
𝑆1 𝑎
𝑇
Change in entropy in reversible process
A1
A2
Abcd a complete reversible cycle
P Q1
In ab isothermal expansion, the working substance a T1
absorb Q1 heat at a constant temp T1. b
Here Q1 positive entropy change is positive. Q2
Hence the gain in entropy of the working substance d
𝑄 T2
from a to b = 1 c
𝑇1
𝑄1
The decrease of entropy by the source is =
𝑇1
During adiabatic process bc, no change in entropy T3
During isothermal compression from c to d, the
working substance gives out a quantity of heat Q2 at a
constant temp T2. The loss of entropy by the working
V
𝑄
substance from c to d is = 2 For a Carnot’s cycle
𝑄1
=
𝑄2
𝑇2 𝑇1 𝑇2
𝑄2 𝑄1 𝑄2
Increase in entropy by the sink = Thus the change in entropy in reversible process is − =0
𝑇2 𝑇1 𝑇2

Thus the net gain in entropy of the working substance

𝑄 𝑄
is 1 − 2
𝑇1 𝑇2
Entropy is a state-function
Entropy is a state-function
 Entropy of a perfect gas
Consider one gram of a perfect gas at a temperature
T1, Volume V1 and pressure P1. Let this gas be heated
𝑆2 𝑇2 𝑉2
in general manner to a final temperature T2, volume 𝑑𝑇 𝑑𝑉
V2 and pressure P2. න 𝑑𝑆 = 𝐶𝑣 න +𝑅 න
𝑇 𝑉
From first law 𝑆1 𝑇1 𝑉1
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 𝑇2 𝑉2
𝑆1 − 𝑆2 = 𝐶𝑣 log 𝑒 + 𝑅 log 𝑒 … … … … … (3)
𝐵𝑢𝑡 , 𝑑𝑈 = 𝐶𝑣 𝑑𝑇 𝑎𝑛𝑑 𝑑𝑊 = 𝑃𝑑𝑉 𝑇1 𝑉1
𝑑𝑄 = 𝐶𝑣 𝑑𝑇 + 𝑃𝑑𝑉 … … … … … . . (1) This equation express the relation between temperature ,
For an ideal gas volume and entropy.
𝑃𝑉 = 𝑅𝑇 By putting𝐶𝑃 − 𝐶𝑣 = 𝑅 in equation (3) and using the
𝑃 𝑉 𝑃 𝑉
𝑅𝑇 relation 1 1 = 2 2, we get two more relations
𝑃= … … … … … … … … … … (2) 𝑇1 𝑇2
𝑉 𝑃2 𝑉2
From equation (1) and (2) 𝑆1 − 𝑆2 = 𝐶𝑣 log 𝑒 + 𝐶𝑃 log 𝑒 … … … … … (4)
𝑅𝑇 𝑃1 𝑉1
𝑑𝑄 = 𝐶𝑣 𝑑𝑇 + 𝑑𝑉 𝑇2 𝑃2
𝑉 𝑆1 − 𝑆2 = 𝐶𝑃 log 𝑒 − 𝑅 log 𝑒 … … … … … (5)
So the change in entropy 𝑇1 𝑃1
𝑑𝑄 𝑑𝑇 dV
𝑑𝑆 = = 𝐶𝑣 +𝑅
𝑇 𝑇 𝑉
If the gas changes from a state of temperature T1,
volume V1 to a state of temperature T2 and volume V2
then the change in entropy
 What are the thermodynamic functions
 The state of a system may be specified by means of certain selected variables such as P, V, or S. They are related to each
other.
 The two laws of thermodynamics provides two more relations 𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊 𝑎𝑛𝑑 𝑑𝑄 = 𝑇𝑑𝑆
 For a complete knowledge of the system some other relations, such as equation state of fluid, will be necessary.
 But in general when such an equation of state is not available certain functions of these variables may be introduced for
the purpose of simplifying the mathematical operations connected with a change in the condition of the system. These
functions called thermodynamic function

There are four thermodynamic functions

1. Internal energy
2. Helmholtz free energy
3. Gibb’s function (thermodynamic potential)
4. Enthalpy (total heat).
 Internal energy
From the first law of thermodynamic
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 … … … . . (1)

Internal energy is therefore a function of entropy and volume

𝑈 = 𝑈 𝑆, 𝑉
𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑆 + 𝑑𝑉 … … … … … … 2
𝜕𝑆 𝑉 𝜕𝑉 𝑆
Equating the coefficient of 𝑑𝑆 and 𝑑𝑉

𝜕𝑈
𝑇=
𝜕𝑆 𝑉
𝜕𝑈
−𝑃 =
𝜕𝑉 𝑆
 Helmholtz free energy function
From the first law of thermodynamic
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 … … … . . (1)

For isothermal system, there is no change in entry

𝑇𝑑𝑆 = 𝑑(𝑇𝑆)
𝑑𝑄 = 𝑇𝑑𝑆 = 𝑑 𝑇𝑆 … … … … 2
Equating the coefficient of 𝑑𝑆 and 𝑑𝑉

dU = d TS − dW
𝑑𝑈 − 𝑑 𝑇𝑆 = −dW
𝑑(𝑈 − TS) = −dW
𝑑F = −dW
Here F = 𝑈 − TS is Helmholtz free energy function.
F = 𝑈 − TS
 Helmholtz free energy function
F = 𝑈 − TS
Differentiating

From the first law of thermodynamic

𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
Putting 𝑑𝑈 from equation (4) to equation (3)
dF = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 − TdS − SdT
dF = −𝑃𝑑𝑉 − SdT … … … . (5)
Therefore HelmholtZ free energy is a function of volume and temperature
F = F(V, T)
𝜕𝐹 𝜕𝐹
𝑑𝐹 = 𝑑𝑇 + 𝑑𝑉 … … … … … . (6)
𝜕𝑇 𝑉 𝜕𝑉 𝑇
Equating the coefficient of 𝑑𝑇 and 𝑑𝑉
𝜕𝐹
−𝑃 =
𝜕𝑇 𝑉
𝜕𝐹
−S =
𝜕𝑉 𝑇
 Enthalpy
H = 𝑈 + PV
Differentiating

From the first law of thermodynamic

𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉
Putting 𝑑𝑈 from equation (4) to equation (3)
dH = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + PdV + VdP
dH = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 … … … . (5)
Therefore enthalpy is a function of Entropy and pressure
H = H(S, T)
𝜕𝐻 𝜕𝐻
𝑑𝐻 = 𝑑𝑆 + 𝑑𝑃 … … … … … . (6)
𝜕𝑆 𝑃 𝜕𝑃 𝑆
Equating the coefficient of 𝑑𝑇 and 𝑑𝑉
𝜕𝐻
𝑇=
𝜕𝑆 𝑉
𝜕𝐻
V=
𝜕𝑇 𝑆
Change in enthalpy Gibb’s free energy
dH = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 … … … (1)
For isothermal system 𝑇𝑑𝑆 = 𝑑(𝑇𝑆) and if temperature is not change then
pressure is not change 𝑑𝑃 = 0

d H − TS = 0
d G =0
Where G = H − TS is Gibb′ s free enegy function
G = H − TS
Differentiating
𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 … … … (2)
From equation (1) and (2)
𝑑𝐺 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

dG = VdP − SdT … … … . (5)

Change in enthalpy Therefore Gibb’s free energy is a function of pressure and temperature
G = G(P, T)
𝜕𝐺 𝜕𝐺
𝑑𝐺 = 𝑑𝑃 + 𝑑𝑇 … … … … … . (6)
𝜕𝑃 𝑇 𝜕𝑇 𝑃
Equating the coefficient of 𝑑𝑇 and 𝑑𝑉
𝜕𝐺 𝜕𝐻
−𝑆 = and V =
𝜕𝑃 𝑇 𝜕𝑇 𝑃
Exact differential equation
 Maxwell’s relations
Internal energy
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 For exact differentials
𝐻𝑒𝑟𝑒 𝑀 = 𝑇, 𝑁 = 𝑃, 𝑥 = 𝑆, 𝑦=𝑉 𝑑𝑍 = 𝑀𝑑𝑥 + 𝑁𝑑𝑦
𝜕𝑇 𝜕𝑃 𝐻𝑒𝑟𝑒 𝑍, 𝑀, 𝑁 𝑎𝑟𝑒 𝑎𝑙𝑙 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛𝑠 𝑜𝑓 𝑥 𝑎𝑛𝑑 𝑦
=− 𝜕𝑀 𝜕𝑁
𝜕𝑉 𝑆 𝜕𝑆 𝑉 =
𝜕𝑦 𝑥 𝜕𝑥 𝑦
Enthalpy
dH = 𝑇𝑑𝑆 + 𝑉𝑑𝑃

𝐻𝑒𝑟𝑒 𝑀 = 𝑇, 𝑁 = 𝑉, 𝑥 = 𝑆, 𝑦=𝑃
𝜕𝑇
=−
𝜕𝑉 Gibb’s free energy
𝜕𝑃 𝑆 𝜕𝑆 𝑃 dG = VdP − SdT
𝐻𝑒𝑟𝑒 𝑀 = 𝑆, 𝑁 = 𝑉, 𝑥 = 𝑇, 𝑦=𝑃
Helmholtz free energy 𝜕𝑆 𝜕𝑉
=−
dF = −𝑃𝑑𝑉 − SdT 𝜕𝑃 𝑇 𝜕𝑇 𝑃
𝐻𝑒𝑟𝑒 𝑀 = 𝑆, 𝑁 = 𝑃, 𝑥 = 𝑇, 𝑦=𝑉
𝜕𝑆 𝜕𝑃
=−
𝜕𝑉 𝑇 𝜕𝑇 𝑉
Maxwell’s relations: table

191
 Application Maxwell's relation
Derivation of the following relations from Maxwell's equations from the book ( Physics for engineering-part I)
and the application of these equations
𝜕𝑃 𝐿
(i) 𝜕𝑇 𝑉
=
𝑇(𝑉𝑣𝑎𝑝 −𝑉𝑙𝑖𝑞 )
𝜕𝑄
(ii) 𝜕𝑃 𝑇
= −𝑇𝑉𝛼

192
Thermodynamics is the study of the movement of heat. It covers everything from how heat transfers during
melting and boiling, to what temperature means, to whether and how heat flows between cold and hot places.
Thermodynamics has various laws, and today we're going to talk specifically about the third law of
thermodynamics.
The third law of thermodynamics says that the entropy of a perfect crystal at absolute zero is exactly equal to
zero.
But hold on a minute. What exactly is entropy? Well, entropy is a measure of disorder in the universe. An object
or substance with high entropy is highly disordered. When you put things in order, such as, putting your child's
toys away in a box, you're decreasing entropy. Or when you look at the result of a farmer's market at the end of
the day, that's a lot of entropy. Unfortunately, you're also producing entropy through the heat in your muscles. In
fact, entropy in the universe can only increase. It can never decrease. A solid is more orderly than a liquid,
because a solid contains molecules in nice, neat rows.
Going back to the third law: it says that entropy at absolute zero is zero. Or in other words, things are most
orderly when they're really cold. Absolute zero is the temperature at which molecules stop moving or vibrating at
all. Sounds pretty orderly to me! So the third law of thermodynamics makes a lot of sense. This complete stop in
molecular motion happens at -273 Celsius, which is defined as 0 kelvin, or absolute zero.

193
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.

Most of the direct use of the Third Law of Thermodynamics occurs in ultra-low temperature chemistry and physics.
The applications of this law have been used to predict the response of various materials to temperature changes.
These relationships have become core to many science disciplines, even though the Third Law of Thermodynamics is
not used directly nearly as much as the other two.

The third law of thermodynamics has very few practical applications in day-to-day life, as opposed to the first and the
second laws. The third law essentially tells us that it is impossible, by any procedure, to reach the absolute zero of
temperature in a finite number of steps.

Most of the direct use of the third law of thermodynamics occurs in very low temperature applications, to predict the
response of various materials to temperature changes.

Another useful application of the third law is the computation of absolute entropies of pure substances at temperatures
other than 0 K from their heat capacities and heats of transition.

194