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THERMODYNAMICS
EPHYSICS LECTURE
 2

PRESENTERS OF GROUP 2
BSEE 1-H

OCAÑA, MICHAEL PAUNIL, ARCHIEVAL

JOHANN A M.
 Thermodynamics 3

INTRODUCTION
Definition of Thermodynamics
• Thermodynamics is a science of the relationship
between heat, work, temperature, and energy.
• Thermodynamics deals with the transfer of energy
from one place to another and from one form to
another.
• Thermodynamics is not concerned about how and at
what rate these energy transformations are carried out.
It is based on the initial and final states undergoing the
change.
• Thermodynamics is a macroscopic science.
4
 Thermodynamics 5

INTRODUCTION
Distinction between Thermodynamics and
Mechanics
• In mechanics, we solely concentrate on the motion of
particles or bodies under the action of forces and torques.
• Thermodynamics only concerned with the internal
macroscopic state of the body.
 Thermodynamics 6

INTRODUCTION
Fundamental Concept
• The application of thermodynamic principles begins by
defining a system that is in some sense distinct from its
surroundings.
• In general, systems are free to exchange heat, work, and
other forms of energy with their surroundings.
 Thermodynamics 7

FUNDAMENTAL CONCEPT
Thermodynamics State
• A system’s condition at any given time is called
thermodynamic state.
• temperature, pressure, and volume, these properties are
characteristic parameters.
• Any change in value of a property depends only on the
initial and final states of the system, not on the path
followed by the system from one state to another. Such
properties are called state functions.
• The work done as the piston moves and the gas expands
and the heat the gas absorbs from its surroundings depend
on the detailed way in which the expansion occurs.
 Thermodynamics 8

FUNDAMENTAL CONCEPT
Thermodynamic Equilibrium
• in which there is no tendency for the state of a system to
change spontaneously.
• The system can then be made to change to a new state
only by an externally imposed change in one of the state
functions, such as the temperature by adding heat or the
volume by moving the piston.
• A sequence of one or more such steps connecting different
states of the system is called a process. In general, a
system is not in equilibrium as it adjusts to an abrupt
change in its environment.
Thermodynamics 9

FUNDAMENTAL CONCEPT
Thermodynamic Equilibrium
• Example
For example, when a balloon bursts, the compressed gas inside is
suddenly far from equilibrium, and it rapidly expands until it reaches
a new equilibrium state. However, the same final state could be
achieved by placing the same compressed gas in a cylinder with a
movable piston and applying a sequence of many small increments in
volume (and temperature), with the system being given time to come
to equilibrium after each small increment. Such a process is said to be
reversible because the system is at (or near) equilibrium at each step
along its path, and the direction of change could be reversed at any
point.
 Thermodynamics 10

FUNDAMENTAL CONCEPT
Thermodynamic Equilibrium
• At a given state, all properties of a system have fixed
values.
 When the temperature is the same throughout the entire system,
we consider the system to be in thermal equilibrium.
 When there is no change in pressure at any point of the system,
we consider the system to be in mechanical equilibrium.
 When the chemical composition of a system does not vary with
time, we consider the system to be in chemical equilibrium.
 Phase equilibrium in a two-phase system is when the mass of
each phase reaches an equilibrium level.
 Thermodynamics 11

FUNDAMENTAL CONCEPT
Temperature
• The concept of temperature is fundamental to any
discussion of thermodynamics, but its precise definition is
not a simple matter.
• When two objects are brought into thermal contact, heat
will flow between them until they come into equilibrium
with each other. When the flow of heat stops, they are said
to be at the same temperature.
 Thermodynamics 12

FUNDAMENTAL CONCEPT
Work and Energy
• Energy has a precise meaning in physics that does not
always correspond to everyday language, and yet a
precise definition is somewhat elusive. The word is
derived from the Greek word ergon, meaning work, but
the term work itself acquired a technical meaning with the
advent of Newtonian mechanics.
Thermodynamics 13

FUNDAMENTAL CONCEPT
Work and Energy
 Examples
• For example, a man pushing on a car may feel that he is doing a
lot of work, but no work is done unless the car moves. The work
done is then the product of the force applied by the man
multiplied by the distance through which the car moves. If there is
no friction and the surface is level, then the car, once set in
motion, will continue rolling indefinitely with constant speed. The
rolling car has something that a stationary car does not have, it has
kinetic energy of motion equal to the work required to achieve
that state of motion. The introduction of the concept of energy in
this way is of great value in mechanics because, in the absence of
friction, energy is never lost from the system, although it can be
converted from one form to another.
Thermodynamics 14

FUNDAMENTAL CONCEPT
Work and Energy
 Examples
• For example, if a coasting car comes to a hill, it will roll some
distance up the hill before coming to a temporary stop. At that
moment, its kinetic energy of motion has been converted into its
potential energy of position, which is equal to the work required
to lift the car through the same vertical distance. After coming to a
stop, the car will then begin rolling back down the hill until it has
completely recovered its kinetic energy of motion at the bottom.
In the absence of friction, such systems are said to be conservative
because at any given moment the total amount of energy (kinetic
plus potential) remains equal to the initial work done to set the
system in motion.
 Thermodynamics 15

FUNDAMENTAL CONCEPT
Work and Energy
• As the science of physics expanded to cover an ever-
wider range of phenomena, it became necessary to include
additional forms of energy in order to keep the total
amount of energy constant for all closed systems (or to
account for changes in total energy for open systems).
 Thermodynamics 16

FUNDAMENTAL CONCEPT
Total Energy
• Although classical thermodynamics deals exclusively
with the macroscopic properties of materials such as
temperature, pressure, and volume thermal energy from
the addition of heat can be understood at the microscopic
level as an increase in the kinetic energy of motion of the
molecules making up a substance.
Thermodynamics 17

FUNDAMENTAL CONCEPT
Total Energy
• Example
For example, gas molecules have translational kinetic energy that is
proportional to the temperature of the gas: the molecules can rotate
about their center of mass, and the constituent atoms can vibrate with
respect to each other (like masses connected by springs).
Additionally, chemical energy is stored in the bonds holding the
molecules together, and weaker long-range interactions between the
molecules involve yet more energy. The sum total of all these forms
of energy constitutes the total internal energy of the substance in each
thermodynamic state. The total energy of a system includes its
internal energy plus any other forms of energy, such as kinetic energy
due to motion of the system as a whole and gravitational potential
energy due to its elevation.
THERMODYNAMIC
SYSTEMS
 Thermodynamics 19

SYSTEM
A thermodynamic system is a specific portion of matter
with a definite boundary on which our attention is
focused. The system boundary may be real or
imaginary, fixed or deformable.
 Thermodynamics 20

SYSTEM
There are three types of systems:
Isolated System – An isolated system cannot exchange energy
and mass with its surroundings. The universe is considered an
isolated system.
Closed System – Across the boundary of the closed system, the
transfer of energy takes place, but the transfer of mass doesn’t
take place. Refrigerator, compression of gas in the piston-cylinder
assembly are examples of closed systems.
Open System – In an open system, the mass and energy both
may be transferred between the system and surroundings. A
steam turbine is an example of an open system.
Surrounding - everything outside the system that has a direct
influence on the behavior of the system is known as a
surrounding.
SYSTEMS
 Thermodynamics 22

THERMODYNAMIC
PROCESS
A system undergoes a thermodynamic process when
there is some energetic change within the system that
is associated with changes in pressure, volume and
internal energy.
 Thermodynamics 23

THERMODYNAMIC
PROCESS
There are four types of thermodynamic processes that
have their unique properties, and they are:
• Adiabatic Process – A process where no heat transfer into or
out of the system occurs.
• Isochoric Process – A process where no change in volume
occurs and the system does no work.
• Isobaric Process – A process in which no change in pressure
occurs.
• Isothermal Process – A process in which no change in
temperature occurs.
 Thermodynamics 24

THERMODYNAMIC
PROCESS
Thermodynamic properties are defined as
characteristic features of a system, capable of
specifying the system’s state. Thermodynamic
properties may be extensive or intensive.
• Intensive properties are properties that do not depend on the
quantity of matter. Pressure and temperature are intensive
properties.
• In the case of extensive properties, their values depends on the
mass of the system. Volume, energy, and enthalpy are
extensive properties.
 Thermodynamics 25

WHAT IS ENTHALPY?
Enthalpy is the measurement of energy in a
thermodynamic system. The quantity of enthalpy
equals the total heat content of a system, equivalent to
the system’s internal energy plus the product of volume
and pressure.
Thermodynamics 26

MATHEMATICALLY, THE ENTHALPY, H, EQUALS THE

SUM OF THE INTERNAL ENERGY, E, AND THE
PRODUCT OF THE PRESSURE, P, AND VOLUME, V,
OF THE SYSTEM.

H = E + PV
Thermodynamics 27

LAWS OF THERMODYNAMICS
Thermodynamics laws define the fundamental physical
quantities like energy, temperature and entropy that
characterize thermodynamic systems at thermal
equilibrium. These thermodynamics laws represent how
these quantities behave under various circumstances. There
are 4 laws of thermodynamics Zeroth law of
thermodynamics, First law of thermodynamics, Second law
of thermodynamics, Third law of thermodynamics.
Thermodynamics 28

LAWS OF THERMODYNAMICS
I. Zeroth Law of Thermodynamics
The Zeroth law of thermodynamics states that if
two bodies are individually in equilibrium with a
separate third body, then the first two bodies are
also in thermal equilibrium with each other. This
means that if system A is in thermal equilibrium
with system C and system B is also in equilibrium
with system C, then system A and B are also in
thermal equilibrium.
 Thermodynamics
29

ZEROTH LAW OF THERMODYNAMICS

Consider two cups A and B, with boiling water. When a thermometer is placed in cup A, it gets warmed up by
the water until it reads 100 °C. When it reads 100 °C, we say that the thermometer is in equilibrium with cup
A. When we move the thermometer to cup B to read the temperature, it continues to read 100 °C. The
thermometer is also in equilibrium with cup B. By keeping in mind, the zeroth law of thermodynamics, we can
conclude that cup A and cup B are in equilibrium with each other.
The zeroth law of thermodynamics enables us to use thermometers to compare the temperature of any two
objects that we like.
Thermodynamics 30

LAWS OF THERMODYNAMICS
II. First Law of Thermodynamics
- What does the first law of thermodynamics state?
The first law of thermodynamics states that energy can
neither be created nor destroyed. It merely transforms from
one form to another. The law states that heat is a form of
energy, and thermodynamic processes are therefore subject
to the principle of conservation of energy. This means that
heat energy cannot be created or destroyed. It can,
however, be transferred from one location to another and
converted to and from other forms of energy.
 Thermodynamics
31

FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics relates to heat, internal energy, and work.
According to this law, some heat given to the system is used to change the internal energy while
the rest is used in doing work by the system.
It can be represented mathematically as △Q = △U + W
Where, △Q is the heat given or lost, △U is the change in internal energy, W is the work done
△U = △Q – W
Thermodynamics 32

FIRST LAW OF THERMODYNAMICS

So, we can infer from the last page equation that the quantity (ΔQ – W) is independent of the
path taken to change the state. Further, we can say that internal energy increases when the
heat is given to the system and vice versa.
Sign Conventions
The table below shows the appropriate sign conventions for all three quantities under
different conditions:

△U (change in internal energy) Q (heat) W (work done on the gas)

Is “+” if temperature increases Is “+” if heat enters gas Is “+” if gas is compressed
Is “-” if temperature decreases Is “-” if heat exits gas Is “-” if gas expands
Is “0” if temperature is constant Is “0” if no heat is exchange Is “0” if volume is constant
Thermodynamics 33

Who stated the first law of thermodynamics?

- Rudolf Clausius and William Thomson stated the first law of thermodynamics.
Can the first law of thermodynamics be violated?
- A machine called a Perpetual Motion Machine of the first kind violates the first law by creating
energy.
Why is the first law of thermodynamics important to the environment?
- The first law states that energy can neither be created nor destroyed it can only e transformed
from one form to another. Sun is the only source of energy for all living organisms on Earth. This
solar energy is converted into chemical energy by plants through the process of photosynthesis.
These energies obtained by the plants do not go back into the solar system. Rather, it is passed
on to herbivores that feed on green plants. Some part of the energy obtained by the herbivores is
utilized by carnivores or transferred to the decomposers when the herbivores die.
What are the limitations of the first law of thermodynamics?
- The first law of thermodynamics does not quantify the energy transfer that takes place, failing to
explain the feasibility of the thermal process.
Thermodynamics 34

LAWS OF THERMODYNAMICS
III. Second Law of Thermodynamics
The second law of thermodynamics put restrictions
upon the direction of heat transfer and achievable
efficiencies of heat engines. The first law of
thermodynamics states that the energy of the
universe remains constant, though energy can be
exchanged between system and surroundings, it
can’t be created or destroyed.
Thermodynamics 35

LAWS OF THERMODYNAMICS
III. Second Law of Thermodynamics
- What is the Second Law of Thermodynamics?
• The second law of thermodynamics states that
any spontaneously occurring process will
always lead to an escalation in the entropy (S)
of the universe. In simple words, the law
explains that an isolated system’s entropy will
never decrease over time.
• The second law is also known as the Law of
Increased Entropy.
Thermodynamics 36

LAWS OF THERMODYNAMICS
III. Second Law of Thermodynamics
• Different Statements of The Law
There are two statements on the second law of
thermodynamics which are;
 Kelvin - Plank Statement
 Clausius Statement
Thermodynamics 37

LAWS OF THERMODYNAMICS
III. Second Law of Thermodynamics
• Different Statements of The Law
 Kelvin - Plank Statement
It is impossible for a heat engine to produce a network in a
complete cycle if it exchanges heat only with bodies at a
single fixed temperature.
Exceptions:
If Q2 =0 (i.e., Wnet = Q1, or efficiency=1.00), the heat
engine produces work in a complete cycle by exchanging
heat with only one reservoir, thus violating the Kelvin-
Planck statement.
Thermodynamics 38

LAWS OF THERMODYNAMICS
III. Second Law of Thermodynamics
• Different Statements of The Law
 Clausius Statement
 It is impossible to construct a device operating in a cycle
that can transfer heat from a colder body to a warmer one
without consuming any work.
 Energy transfer can take place from a cold object to a hot object
by transfer of energetic particles or electromagnetic radiation.
 Thermodynamics
39

SECOND LAW OF THERMODYNAMICS

Both Clausius’s and Kelvin’s statements are equivalent, example if a device

violated Clausius’s statement will also violate Kelvin’s statement and vice versa.
Thermodynamics 40

In addition to these
statements, a French
physicist named Nicolas
Léonard Sadi Carnot also
known as the “father of
thermodynamics,” basically
introduced the Second Law of
Thermodynamics. However,
as per his statement, he
emphasized the use of caloric
theory for the description of
the law. Caloric (self repellent
fluid) relates to heat and
Carnot observed that some
caloric was lost in the motion
cycle.
Thermodynamics 41

LAWS OF THERMODYNAMICS
IV. Second Law of Thermodynamics
- What is the Third Law of Thermodynamics?
• The third law of thermodynamics states that
the entropy of a perfect crystal at a
temperature of zero Kelvin (absolute zero) is
equal to zero.
Thermodynamics 42

LAWS OF THERMODYNAMICS
IV. Second Law of Thermodynamics
- What is the Third Law of Thermodynamics?
• At a temperature of zero Kelvin, the following
phenomena can be observed in a closed
system:
 The system does not contain any heat.
 All the atoms and molecules in the system
are at their lowest energy points.
 Thermodynamics
43

SECOND LAW OF THERMODYNAMICS

This law was developed by the German chemist Walther Nernst between the
years 1906 and 1912.
Thermodynamics 44

Alternate Statements of the 3rd Law of Thermodynamics

The Nernst statement of the third law of thermodynamics implies that it is not possible for a
process to bring the entropy of a given system to zero in a finite number of operations.
The American physical chemists Merle Randall and Gilbert Lewis stated this law differently:
when the entropy of each element (in their perfectly crystalline states) is taken as 0 at
absolute zero temperature, the entropy of every substance must have a positive, finite value.
However, the entropy at absolute zero can be equal to zero, as is the case when a perfect
crystal is considered.
The Nernst-Simon statement of the 3rd law of thermodynamics can be written as: for a
condensed system undergoing an isothermal process that is reversible in nature, the
associated entropy change approaches zero as the associated temperature approaches
zero.
Another implication of the third law of thermodynamics is: the exchange of energy between
two thermodynamic systems (whose composite constitutes an isolated system) is bounded .
Thermodynamics 45

Mathematical Explanation of the Third Law

As per statistical mechanics, the entropy of a system can be expressed via the following equation:
S – S0 = 𝑘B ln𝛀
Where, S is the entropy of the system.
S0 is the initial entropy.
𝑘B denotes the Boltzmann constant.
𝛀 refers to the total number of microstates that are consistent with the system’s macroscopic
configuration.
Now, for a perfect crystal that has exactly one unique ground state, 𝛀 = 1. Therefore, the equation can
be rewritten as follows:
S – S0 = 𝑘B ln(1) = 0 [because ln(1) = 0]
When the initial entropy of the system is selected as zero, the following value of ‘S’ can be obtained:
S–0=0⇒S=0
Thus, the entropy of a perfect crystal at absolute zero is zero.
Thermodynamics 46

Applications of the Third Law of Thermodynamics

An important application of the third law of thermodynamics is that it helps in the calculation of the
absolute entropy of a substance at any temperature ‘T’. These determinations are based on the heat
capacity measurements of the substance. For any solid, let S0 be the entropy at 0 K and S be the
entropy at T K, then
ΔS = S – S0
According to the third law of thermodynamics, S0= 0 at 0 K,
The value of this integral can be obtained by plotting the graph of Cp/ T versus T and then finding the
area of this curve from 0 to T. The simplified expression for the absolute entropy of a solid at
temperature T is as follows:
= Cp ln T = 2.303 Cp log T
Here Cp is the heat capacity of the substance at constant pressure and this value is assumed to be
constant in the range of 0 to T K.
Thermodynamics 47

FAQS ABOUT THERMODYNAMICS

What is the importance of the laws of thermodynamics?
- The laws of thermodynamics define physical quantities i.e. temperature, energy & entropy that characterize
thermodynamic systems at thermal equilibrium.
What is an example of negative work?
- When you’re pushing an object along the floor, the work done by Kinetic Friction is negative.
Can energy be destroyed or lost?
Energy can neither be created nor be destroyed, it can only be transferred from one form to another.
Fans convert electrical energy into mechanical energy – this is explained by which law?
This is explained by the First law of thermodynamics.
Does the human body obey the laws of thermodynamics?
Yes, the human body obeys the law of thermodynamics. When you are in a crowded room with other people, you
start to feel warm, and you start to sweat. This is the body’s way to cool itself. The heat from the body is transferred
to the sweat. As the sweat absorbs more heat, it evaporates from your body, becoming more disordered and
transferring heat to the air, which heats the room’s air temperature. Many sweating people in a crowded room,
“closed system,” will quickly heat the place. This is both the first and second laws of thermodynamics in action. No
heat is lost; it is merely transferred and approaches equilibrium with maximum entropy.
“Nothing in life is certain except
death, taxes and the second law of
thermodynamics.”
- Seth Lloyd

THANK YOU!!