Thermodynamics

You can observe many physics principles in your kitchen. When

you put a pot of water on a stove, heat is transferred from its
source to the water that eventually boils and converts it from liquid
stream. When you cannot open the metal lid of a jar, you can heat
the lid to loosen it. Likewise, you can cook meat faster using a
pressure cooker.

Careful study of these concepts is essential for a good

understanding of topics in thermodynamics. One of the main goals
of this module will be to formalize the relationship between heat,
work, and energy.
Heat boils water and gives
At the end of the module, students can: warmth.

1. Explain the connection between the Zeroth Law of Thermodynamics, temperature, thermal
equilibrium, and temperature scales
2. Convert temperatures and temperature differences in the following scales: Fahrenheit,
Celsius, Kelvin
3. Define coefficient of thermal expansion and coefficient of volume expansion
4. Calculate volume or length changes of solids due to changes in temperature
5. Solve problems involving temperature, thermal expansion, heat capacity, heat transfer, and
thermal equilibrium in contexts such as, but not limited to, the design of bridges and train
rails using steel, relative severity of steam burns and water burns, thermal insulation, sizes
of stars, and surface temperatures of planets
6. Enumerate the properties of an ideal gas
7. Solve problems involving ideal gas equations in contexts such as, but not limited to, the
design of metal containers for compressed gases
8. Interpret PV diagrams of a thermodynamic process
9. Compute the work done by a gas using dW=PdV
10. State the relationship between changes internal energy, work done, and thermal energy
supplied through the First Law of Thermodynamics
11. Differentiate the following thermodynamic processes and show them on a PV diagram:
isochoric, isobaric, isothermal, adiabatic, and cyclic
12. Calculate the efficiency of a heat engine
13. Describe reversible and irreversible processes
14. Explain how entropy is a measure of disorder
15. State the 2nd Law of Thermodynamics
16. Calculate entropy changes for various processes e.g., isothermal process, free expansion,
constant pressure process, etc
Let’s Check Your Knowledge! : What I Know?
In your own words, give the meaning of the following words.
1. Heat_______________________________________________________________________________________________
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2. Thermal___________________________________________________________________________________________
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3. Temperature______________________________________________________________________________________
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4. Refrigerator_______________________________________________________________________________________
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5. Engine____________________________________________________________________________________________
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INTRODUCTION: Thermodynamic Systems and Their Surroundings

Thermodynamics can be defined as the study of energy, energy
transformations and its relation to matter. 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.

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.

Closed and Open Systems

A system is defined as a quantity of matter or a region in space
chosen for study. The mass or region outside the system is called
the surroundings.

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 Boundary: the real or imaginary surface that separates the system from its surroundings.
The boundaries of a system can be fixed or movable. Mathematically, the boundary has
zero thickness, no mass, and no volume.
 Closed system or control mass: consists of a fixed amount of mass, and no mass can
cross its boundary. But, energy in the form of heat or work, can cross the boundary, and
the volume of a closed system does not have to be fixed.
 Open system or control volume: is a properly selected region in space. It usually encloses
a device that involves mass flow such as a compressor. Both mass and energy can cross the
boundary of a control volume.
Important note: some thermodynamics relations that are applicable to closed and open systems
are different. Thus, it is extremely important to recognize the type of system we have before
start analyzing it.
 Isolated system: A closed system that does not communicate with the surroundings by
any means.
 Rigid system: A closed system that communicates with the surroundings by heat only.
 Adiabatic system: A closed or open system that does not exchange energy with the
surroundings by heat.

State and Equilibrium

At a given state, all the properties of a system have fixed values. Thus, if the value of even one
property changes, the state will change to different one.

In an equilibrium state, there are no unbalanced potentials (or driving forces) within the
system. A system in equilibrium experiences no changes when it is isolated from its
surroundings.
 Thermal equilibrium: when the temperature is the same throughout the entire system.
Mechanical equilibrium: when there is no change in pressure at any point of the system.
However, the pressure may vary within the system due to gravitational effects.
 Phase equilibrium: in a two phase system, when the mass of each phase reaches an
equilibrium level.
 Chemical equilibrium: when the chemical composition of a system does not change with
time, i.e., no chemical reactions occur.

Lesson 13 Zeroth Law of Thermodynamics

 The forgotten Law of Science
 Two systems are said to be in thermal equilibrium if there is no
heat flow between them when they are brought into contact.
 Temperature is the indicator of thermal equilibrium in the
sense that there is no net flow of heat between two systems in thermal
contact that have the same temperature.
 The 0th law makes a thermometer possible. In accordance with
the 0th law, any system that possesses an equation of state that
relates temperature T to other accurately measurable properties can
be used as a thermometer

Two systems individually in thermal equilibrium with a third system

are in thermal equilibrium with each other.

Temperature and Thermometers

• Temperature is usually associated with the hotness or the coldness of an object.
Temperature depends on the kinetic (motion) energy of the molecules of a substance.

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• Temperature is a measure of the
average kinetic energy of the
molecules of a substance.
• Thermometer - an instrument
that utilizes the physical
properties of materials for the
purpose of accurately determining
temperature
• Thermal expansion is the physical
property most commonly used to
measure temperature.
• Expansion/contraction of metal
• Expansion/contraction of
mercury or alcohol
Three common scales of
measurement for temperature:
1. Celsius Scale °C- designed by
Andre Celsius in 1710.
2. Fahrenheit Scale °F- designed by
Gabriel Fahrenheit in 1717
3. Kelvin scale K- designed by Lord Kelvin
Absolute Temperature
The lowest temperature of -273.16
Diff. at which a gas is supposed to
Absolute Ice Steam
Scale (Boil have zero volume and zero
Zero Point Point
– Ice) pressure and at which entire
molecular motion stops is called
°F - 460o 32o 212o 180 absolute zero temperature. A new
scale of temperature starting with -
°C -273o 0o 100o 100
273.16 by Lord Kelvin as zero.
K 0o 273o 373o 100 This is called Kelvin scale or
absolute scale of temperature.

Converting Temperatures is Easy!

Example: The normal human body
• TK = TC + 273 (Celsius to Kelvin) temperature is usually 98.6oF. Convert
• TC = TK – 273 (Kelvin to Celsius) this to Celsius.
• TF = 1.8TC + 32 (Celsius to Fahrenheit) TC = TF – 32 (Fahrenheit to Celsius)
• TC = TF – 32 (Fahrenheit to Celsius) 1.8
o
1.8 TC = 98.6 – 32 = 66.6 = 37.0 C
1.8 1.8
What Have I Learned So Far?
1. At what temperature is the temperature reading in the Celsius scale equal to the
Fahrenheit Scale? Fahrenheit and Kelvin? Support your answer with a computation
showing their respective conversions.
2. Room temperature is often taken to be 680F. What is this on the Celsius and Kelvin scales?

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 Thermal Expansion
What will you do to open a tightly covered metal lid of a glass jar? Perhaps you have seen that
people heat the cover on the stove to “loosen” the lid. When a body (almost all) is heated it
expands. The expansion can take place in the length, area or volume of the body. Depending
upon the expansion in length, area or volume we have three types of expansion.
1. Linear Expansion (one dimension)
- Change in the length of a body due to a temperature change
-
Where change in length, Lo is is initial length, constant is the coefficient of linear
expansion (depending upon the nature of the material) and is change in temperature.
2. Superficial or Areal Expansion (two dimension)
- Change in area of a body due to a temperature change
- A= 2
Where is change in area, A is initial area, constant is the coefficient of areal expansion
(depending upon the nature of the material) and is change in temperature.
3. Cubical or volume expansion (three dimension)
- increase in volume of a substance on heating
- V=
Where is change in volume, V is the initial volume constant is the coefficient of volume
expansion (depending upon the nature of the material) and is change in temperature.
Example: Consider a glass tube with a volume of 200 cm3 that is filled to the brim with
mercury at 20 . How much mercury would overflow if the temperature is raised to 100 ? Note
that the coefficients of the glass and that of mercury are 0.40 x 10-5 K-1 and 18 x 10-5 K-1,
respectively.
Solution:
Solve for the volume expansion of both:
Mercury: Glass:
V= V=
= (18 x 10-5 K-1)( 200 cm3)(80K) = (0.40 x 10-5 K-1)( 200 cm3)(80K)
= 2.88 cm3 = 0.064 cm3

Thus, the amount of mercury that overflows is

This describes how a thermometer
= 2.88 cm3-0.064 cm3 works.
= 2.816 cm3
What Have I Learned So Far?
Consider a C- shaped metal and a doughnut- shaped metal shown here. Will the size of the gap
in the C-shaped metal decrease in size when heated? Explain. What about the diameter of the
hole of the doughnut-shaped metal? Would it increase in size when heated? Explain.
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Science In Action
• A small gap is left between the iron rails of railway tracks.
• Space is left between the girders used for supporting bridges.
• Clock pendulums are made of invar. Invar has extremely small temperature coefficient of
expansion, so the length of invar pendulum does not change with the change of season i.e.
temperature.
• Anomalous Expansion of water
-Almost all liquids expand on heating but water when heated from 0 to 4 its volume
decreases and hence density increase until its temperature reaches 4 as its density
maximum at 4 and on further heating its density decreases. This behavior is called
anomalous behavior of water. This allows aquatic animals to remain alive and move freely
on water.

Internal Heat and Heat

Energy

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In thermodynamics, we deal with change of the total energy only. Thus, the total energy of a
system can be assigned a value of zero at some reference point. Total energy of a system has
two groups: macroscopic and microscopic. Macroscopic forms of energy: forms of energy that a
system posses as a whole with respect to some outside reference frame, such as kinetic and
potential energy. 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.
 Kinetic energy: energy that systems posses as a result of its relative motion relative to some
reference frame, KE
KE= where V is the velocity of the system in (m/s).
 Potential energy: is the energy that a system posses as a result of its elevation in a
gravitational field, PE
PE = mgh kJ  where g is the gravitational acceleration and z is the elevation of the
center of gravity of the system relative to some arbitrary reference plane.
Microscopic forms of energy: are those related to molecular structure of a system. They are
independent of outside reference frames. The sum of microscopic energy is called the internal
energy, U.
The total energy of a system consists of the kinetic, potential, and internal energies:
E = U  KE  PE = U  + mgh
where the contributions of magnetic, electric, nuclear energy are neglected. Internal energy is
related to the molecular structure and the degree of molecular activity and it may be viewed as
the sum of the kinetic and potential energies of molecules.
 The sum of translational, vibrational, and rotational energies of molecules is the kinetic
energy of molecules, and it is also called the sensible energy. At higher temperatures, system
will have higher sensible energy.
 Internal energy associated with the phase of a system is called latent heat. The
intermolecular forces are strongest in solids and weakest in gases.

 The internal energy associated with the atomic bonds in a molecule is called chemical or
bond energy. The tremendous amount of energy associated with the bonds within the
nucleolus of atom itself is called atomic energy.
Energy interactions with a closed system can occur via heat transfer and work.

Example: When you lift a book, does its internal energy increase, decrease or remain the
same?
Answer: Internal energy does not include energies associated with the interaction of the body
with its surroundings. When you lift a book, its gravitational potential energy increases but not
its internal energy. Thus, the internal energy of the book remains the same even if you lift it.

CALORIMETRY
Heat is the energy being transferred between bodies with different temperatures. Heat is energy
in transit; it has the same unit as energy.

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We know that there is spontaneous transfer of heat from a hot body to colder body. If heat
exchange with the surrounding is negligible then the total heat lost by a hot body is always
equal to the heat gained by the cold body, this is the Principle of Calorimetry or, law of
mixture.

Specific Heat Capacity

When we supply heat to a body, its temperature rises. If m is mass, is temperature rise and
Q is the heat supplied, then
Q= mc
where ‘c’ is constant called specific heat which depends upon the nature of material and its
surrounding.

Specific capacity of a material is equal to the heat required to raise the temperature of unit
mass from 14.5 to 15.5 . Its SI unit is either J/kg●K or J/kg●C°.

Table: Specific Capacities of selected substances

Substance Specific Heat Substance Specific Heat
Capacity Capacity
(J/kg●K or J/kg●C°) (J/kg●K or J/kg●C°)
Aluminum 910 Lead 130
Beryllium 1970 Mercury 138
Copper 390 Silver 234
Ice (near 0°C) 2100 Water (liquid) 4190
Example: During daytime at the beach, the sand is hotter than the water in the sea. Why is
this so?
Answer: Consider the same mass of sand and water that receive the same amount of heat from
sunlight. Because sand easily becomes hotter than water, a particular amount of heat raises
the temperature of sand more than water. Hence, water requires more heat to have the same
increase of temperature as sand. This implies that water has a higher specific heat capacity
than sand.

During nighttime at the beach, the sand is colder than the water. Because sand has lower
specific capacity than water, it changes its temperature more easily than water relative to its
cold environment.

Molar Heat Capacity and Heat Capacity

Molar heat capacity of a substance is the amount of heat required to raise the
temperature of one mole of a substance by unit degree.
Sm= n= number of moles
Heat capacity of a substance is the amount of heat required to raise temperature of a
body by unit degree. It is represented by C, its unit is J/°C or cal °C. Heat capacity
depends upon nature of material and it’s mass.

Heat capacity, C= = ms
Water Equivalent and Latent Heat
Water Equivalent of a body is defined as the mass of water which has the same heat capacity
as that of the body. It is represented by W.

Latent Heat or Hidden Heat: When state of a substance changes, change of state takes place
at constant temperature (m.pt. or B. pt.) heat is released or absorbed and is given by Q= mL
where L is latent heat. The S.I. unit of latent heat is J/kg. (can be positive or negative)
Latent heat of fusion or melting (Lf): It is the amount of heat required to change unit mass of
solid into liquid state at its melting point. It is represented by Le. For ice its value is 80 cal g-1.

Latent heat of vaporisation or boiling (Lv): It is the amount of heat required to change unit
mass of liquid into its vapors at its boiling point. It is represented by Lv

For water Lv = 540 cal g-1

Q= mLv
Sublimation: It is the conversion of a solid directly into vapours.
Heat
Solid Vapour

Latent heats of fusion and of vaporization for some substances

Substance Heat of Fusion, Lf, (J/kg) Heat of Vaporization, Lv, (J/kg)
Water 334 x 103 2256 x 103
Lead 24.5 x 10 3 871 x 103
Silver 88.3 x 103 2336 x 103

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 Gold 64.5 x 103 1578 x 103
Copper 134 x 10 3 5069 x 103
Example: Compute the amount of heat needed to convert a 2.0-kg block of ice at -25 into
steam at 125 .

First, we need to find how much heat is needed to convert the temperature of solid ice from -
25 to 0 .
Q= = (20 kg)

Next, we find how much heat is needed to change the phase of the ice into water
Q= mLf = (2.0 kg)(334 x 103 J/kg) = 668 000 J
Then, we need to find how much heat is needed to convert the temperature from 0 to 100
Q= = (20 kg)
Again, we need to find how much heat is needed to change the phase of the 2.0 kg
water to steam,
Q= mLf = (2.0 kg)(2.256 x 106 J/kg) = 4 512 000 J
Finally, how much heat is needed to convert the temperature of steam from 100 to
125
Q= = (20 kg)

Add all of them to get the total heat Q:

QT = + 668 000 J + + 4 512 000 J +
QT = 6.22 x 106 J or 6.22 MJ
What Have I Learned So Far?
Solve. Show your solution.
1. What is the specific heat capacity of a metal X if its mass is 75 g and requires 3.0 x 104 J of
heat for its temperature to increase by 10 ?
2. Consider a 1.30-kg steel kettle that is filled with 1.50 kg of water. Determine the amount of
heat necessary to make the water boil if the system is initially at 15 . Assume the system
is isolated.

Science in Action
 Skating is possible due to regelation. Water layer below the skates is formed due to
the increase of pressure and it acts as a lubricant. Regelation is the phenomenon in
which ice melts when pressure is increased and again freezes when pressure is
removed is called regelation.
 By pressing snow in our hand, we can transform it into a snow-ball.
HEAT TRANSFER
Heat energy can be transferred from a body at higher temperature to a body at lower
temperature by three different ways viz. conduction, convection and radiation.

Conduction
Conduction is the process in which heat is transmitted from one point to the other through the
substance without the actual motion of the particles. When one end of a metal is heated, the

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molecules at the hot end start vibrating with higher amplitudes (kinetic energy) and transmit
this K.E. to the next molecule and so on. However, the molecules still remain in their mean
positions of equilibrium. This process of conduction is prominent in the case of solids.

Heat is transmitted by conduction when it passes from the hotter to the colder parts of the
medium material without any movement of the medium itself and all intermediate parts of the
material being warmed in the process. e.g. Metal rod held at one end in a fire after a period of
time the top end becomes hot and all intermediate parts also are warm.

THERMAL CONDUCTIVITY
It is the measure of ability of the solid to conduct heat through it. Examples: silver, copper, etc.
are good conductors of heat and glass, wood are bad conductors of heat.

The coefficient of thermal conductivity (k) is defined as the amount of heat flowing in unit time
across the opposite faces of a cube of side having unit length maintained at unit temperature
difference.
H= kA
Where H is the thermal conductivity, k is the coefficient of thermal conductivity,
is the temperature difference, A is the cross- sectional area and L is the length.

SI unit of Thermal Conductivity is (W/m◦K)

Thermal Conductivities for Some Substances
Substance k (W/m◦K) Substance k (W/m◦K)
Aluminum 205.0 Concrete 0.8
Brass 109.0 Cork 0.04
Copper 385.0 Fiberglass 0.04
Lead 34.7 Glass 0.08
Example: During summer, the air temperature in Metro Manila can reach as high as 36 .
Consider an air-conditioned house with air temperature of 22 . Calculate the rate of heat flow
through a glass window that is 1.8 m x 1.2 m in area and 3.0 mm thick.
Solution:
Assume that the temperatures at the inner and outer surfaces of the window are the ambient
temperatures 22 and 36 , respectively. Based on the table, the representative value for the
thermal conductivity of glass is 0.08 W/m◦K. Cross- sectional area of the glass window is A =
(i.8 m) (1.2 m) = 2.16 m2. Using the heat equation,
H= kA = H= (0.08 W/m◦K)(2.16 m2) = 8640 W
What Have I Learned So Far?
A metal bar is made up of 3.0 cm of aluminum and 5.0 cm of steel. The free end of the
aluminum bar is placed in contact with steam at 100 . At the other side, the free end of the
steel bar is maintained at 0 by placing it in contact with the ice. Find the temperature at the
point that connects the aluminum and the steel (junction).
Solution:

Convection
Convection is the process in which heat is transmitted from one place to the other by the
actual movement of the vibrating particles. It is prominent in the case of liquids and gases.
Land and sea breezes and trade winds are formed due to convection. Convection plays an
important part in ventilation, gas filled electric lamps and heating of buildings by hot water
circulation. It is the process of transfer of heat in a fluid by the movement of the fluid itself.

In fluids, convective heat transfer takes place through both diffusion – the random Brownian
motion of individual particles in the fluid – and by advection, in which matter or heat is
transported by the larger-scale motion of currents in the fluid.

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Density is defined as mass per unit Volume. As the fluid is heated the Volume increases, the
mass is constant therefore the density decreases.

Hot fluids are less dense than cold fluids and will rise therefore convection currents (circular
currents or movement within a fluid) due to different densities of the hotter and cooler parts
are set up

When heat is transferred by the circulation of fluids due to buoyancy from the density changes
induced by heating itself, then the process is known as free or natural convective heat transfer.
What Have I Learned So Far?
Answer the following questions.
1. In which part of the water tank should a heater be placed to be able to efficiently heat the
water? Explain your answer.
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2. Suppose you will install an air conditioner inside your room. Where should you install the
appliance to attain maximum efficiency? Justify your answer.
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Radiation
Radiation is the process in which heat is transmitted from one place to the other directly
without the necessity of any intervening medium. We get heat radiations directly from the sun
without affecting the intervening medium. Heat radiations can pass through vacuum. Heat
radiations are a part of the electromagnetic spectrum.

Radiation has the following properties

 Radiant energy travels in straight line and when some object is placed in the path; its
shadow is formed at the detector.
 It is reflected and refracted or can be made to interfere. The reflection or refraction are
exactly as in case of light.
 It can travel through vacuum.
 Intensity of radiation follows the law of inverse square
 Thermal radiation can be polarised in the same way as light by transmission through a
nicol prims.
Heat is transmitted by Radiation when it is passed from one place to another without the aid of
a material medium and does not heat the space through which it travels.

All hot bodies radiate the also absorb radiant heat. If Rate of heat absorbed = Rate of heat
radiated, then the body has a constant temperature.

The rate at which a body radiates heat depends on

 Temperature of the body
 Surface area of the body
 Nature of the surface

The Stefan–Boltzmann law, also known as Stefan's law, states that the total energy radiated
per unit surface area of a body in unit time is directly proportional to the fourth power of the
body's temperature in Kelvin T (also called absolute temperature):
H= AT4
Where

= Stefans constant = 5.67x10 W/m2 K4

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H = Rate of energy emitted in Watts

Emissivity of the material
T = Temperature of the surface in Kelvin
A = Surface area in m2

A black body is an object that absorbs all electromagnetic radiation that falls on it.

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The emissivity of a material (usually written ε) is a measure of a material's ability to radiate
absorbed energy. A true black body would have an e = 1 while any real object would have e < 1.
Emissivity is a dimensionless quantity (does not have units).
In general, the duller and blacker a material is, the closer its emissivity is to 1. The more
reflective a material is, the lower its emissivity. Highly polished silver has an emissivity of about
0.02.
Example: To cool your body, you decided to relax in a cool swimming pool with a temperature
of 20 . The total surface area of a human body is approximately 1.50 m2 with emmisively very
close to unity ( , irrespective of skin pigmentation. If the surface temperature of your skin
is 32 , what is the net rate of heat loss from your body when you soak in this pool?
Solution:
H= AT4
H= (1.50 m2 )[(305.15 K)4-(293.15 K)4]
Hnet= 109 W
What Have I Learned So Far?
The silica cylinder of a radiant wall heater is 60 cm long and has a radius of 5 mm. If it is
rated at 1.5 kWatts estimate its temperature when in operation.
Assume and = 5.67 x 10-8 W / m2 K4

Science in Action
 During the winter season, birds often swelt their feathers, this encloses the air
between the body and feathers| and thus stops the flow of heat from its body to the
surroundings.
 Metallic handles of doors during winter season appear colder as it is a good
conductor, heat flows from the body to the handle.

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