THERMODYNAMI

CS
  Thermodynamics is the branch of
physics that deals with the
relationships between heat and other
forms of energy.

WHAT IS
 Thermal energy is the energy a
THERMODYN substance or system has due to its
AMICS? temperature, i.e., the energy of moving
or vibrating molecules, Units of Heat.

 Thermodynamics involves measuring

this energy.
Thermal conductivity (k) is the rate at which heat passes through
a specified material, expressed as the amount of heat that flows
per unit time through a unit area with a temperature gradient of
one degree per unit distance.

The unit for k is watts (W) per meter (m) per kelvin (K). Values
of k for metals such as copper and silver are relatively high at
401 and 428 W/m·K, respectively.

THERMAL
Other materials are useful because they are extremely poor CONDUCTIVITY
conductors of heat; this property is referred to as thermal
resistance, or R-value, which describes the rate at which heat is
transmitted through the material.

R-value is given in units of square feet times degrees Fahrenheit

times hours per British thermal unit (ft2·°F·h/Btu) for a 1-inch-
thick slab.
NEWTON'S LAW OF COOLING
 In 1701, Sir Isaac Newton first stated his Law of
Cooling in a short article titled ‘Scala graduum
Caloris’ (‘A Scale of the Degrees of Heat’) in the
Philosophical Transactions of the Royal Society.
Newton's statement of the law translates from the
original Latin as, ‘the excess of the degrees of the
heat ... were in geometrical progression when the
times are in an arithmetical progression.’
Worcester Polytechnic Institute gives a more
modern version of the law as ‘the rate of change of
temperature is proportional to the difference
between the temperature of the object and that of
the surrounding environment.’
THE CARNOT
CYCLE
 In 1824, Nicolas Léonard Sadi Carnot
proposed a model for a heat engine based
on what has come to be known as the
Carnot cycle. The cycle exploits the
relationships among pressure, volume
and temperature of gasses and how an
input of energy can change form and do
work outside the system.
ENTROPY
 All thermodynamic systems generate
waste heat. This waste results in an
increase in entropy, which for a closed
system is a quantitative measure of the
amount of thermal energy not available to
do work.
 Entropy is also defined as a measure of
the disorder or randomness in a closed
system, which also inexorably increases.
THERMODYNAMIC
TERMS
 Thermodynamic system: A thermodynamic system refers to a
definite quantity of matter, which is considered unique and
separated from everything else, which can influence it. Every system
is enclosed by an arbitrary surface, which is called its boundary.
 (a) Open System: It is a system, which can exchange mass and
energy with the surroundings. A water heater is an open system.
 (b) Closed system: It is a system, which can exchange energy but not
mass with the surroundings. A gas enclosed in a cylinder fitted with
a piston is a closed system.
 (c) Isolated system: It is a system, which can exchange neither mass
nor energy with the surrounding. A filled thermos flank is an ideal
example of an isolated system.
THERMODYNA
MIC TERMS
 Thermodynamic Variables or Coordinates: To
describe a thermodynamic system, we use its physical
properties such on temperature (T), pressure (P), and
volume (V). These are called thermodynamic
variables.
 Indicator diagram: To study a thermodynamic system,
we use a pressure-volume graph. This graph indicates
how pressure (P) of a system varies with its volume (V)
during a thermodynamic process and is known as an
indicator diagram.
ΔW = P ΔV
= Area of a shaded strip ABCD
If within the system, there are variations in pressure
or elastic stress, then parts of the system may
undergo some changes. However, these changes
cease ultimately, and no unbalanced force will act on
the system. Then we say that it is in mechanical
equilibrium.
THERMODYNAMIC
EQUILIBRIUM
If a system has components which react chemically,
after some time, all possible chemical reactions will
cease to occur. Then the system is said to be in chemical
equilibrium. A system, which exhibits thermal,
mechanical and chemical equilibrium, is said to be in
thermodynamic equilibrium. The macroscopic
properties of a system in this state do not change with
time.
THERMODYNAMIC PROCESSES
 Thermodynamic Processes –

 (i) Reversible process: If a process is executed so that all intermediate stages between the initial and
final states are equilibrium states and the process can be executed back along the same equilibrium
states from its final state to its initial state, it is called reversible process. A reversible process is
executed very slowly and in a controlled manner.
 (ii) Irreversible process: A process, which cannot be retraced along the same equilibrium state from
final to the initial state, is called irreversible process.
 All natural processes are irreversible

 (iii) Isothermal process: A thermodynamic process that occurs at constant temperature is an

isothermal process. The expansion and compression of a perfect gas in a cylinder made of perfectly
conducting walls are isothermal processes. The change in pressure or volume is carried out very slowly
so that any heat developed is transferred into the surroundings and the temperature of the system
remains constant. The thermal equilibrium is always maintained. In such a process, ΔQ, ΔU and ΔW are
finite.
 (iv) Adiabatic process: A thermodynamic process in which no exchange of thermal energy occurs is an
adiabatic process. For example, the expansion and compression of a perfect gas in a cylinder made of
perfect insulating walls. The system is isolated from the surroundings. Any amount of heat neither
leaves the system nor enters it from the surroundings. In this process, therefore ΔQ = 0 and ΔU = –ΔW.
 (v) Isobaric process: A thermodynamic process that occurs at constant pressure is an isobaric process.
Heating of water under atmospheric pressure is an isobaric process.
 (vi) Isochoric process: A thermodynamic process that occurs at constant volume is an isochoric
process. For example, heating of a gas in a vessel of constant volume is an isochoric process. In this
process, volume of the gas remains constant so that no work is done, i.e.,
 ΔW = 0

 We therefore get ΔQ = ΔU.

THERMODYNAMIC
PROCESSES
 Cyclical processes: There are processes in which, after certain
interchanges of heat and work, the system is restored to its initial
state. In that case, no intrinsic property of the system—including its
internal energy—can possibly change.
 Putting, ΔEint = 0 in the first law yields

 ∴ ΔQ = ΔW (cyclical process)

 Constant-volume processes: If the volume of a system (such as a

gas) is held constant, that system can do no work. Putting W = 0 in
the first law yields
 ΔEint = Q (constant-volume process)

 Free expansions: These are adiabatic processes in which no transfer

of heat occurs between the system and its environment and no work
is done on or by the system. Thus, Q = W = 0, and the first law
requires that
 ΔEint = 0 (free expansion)
THE FOUR LAWS OF
THERMODYNAMICS
The Zeroth Law states that if two bodies are in thermal equilibrium with some third body, then
they are also in equilibrium with each other. This establishes temperature as a fundamental and
measurable property of matter.

The First Law states that the total increase in the energy of a system is equal to the increase in
thermal energy plus the work done on the system. This states that heat is a form of energy and is
therefore subject to the principle of conservation.

The Second Law states that heat energy cannot be transferred from a body at a lower temperature
to a body at a higher temperature without the addition of energy. This is why it costs money to run
an air conditioner.

The Third Law states that the entropy of a pure crystal at absolute zero is zero. As explained above, entropy is sometimes called ‘waste
energy,’ i.e., energy that is unable to do work, and since there is no heat energy whatsoever at absolute zero, there can be no waste energy.
Entropy is also a measure of the disorder in a system, and while a perfect crystal is by definition perfectly ordered, any positive value of
temperature means there is motion within the crystal, which causes disorder. For these reasons, there can be no physical system with lower
entropy, so entropy always has a positive value.
ZEROTH LAW OF THERMODYNAMICS
 If bodies A and B are each in thermal equilibrium with a third body C, then A and B are in thermal
equilibrium with each other.

FIRST LAW OF THERMODYNAMICS

 ΔEint = Eint,f – Eint,i = Q – W

 dEint = dQ – dW

 Rules: The work done on a system is always the negative of the work done by the system, so if we
rewrite
 ΔEint = Eint,f – Eint,i = Q – W

 in terms of the work Won done on the system, we have

 ΔEint = Q + Won
SECOND LAW OF THERMODYNAMICS
 The Kelvin-Planck’s statement is based on the experience about the
performance of heat engines. (Heat engine is discussed in next
section.) In a heat engine, the working substance extracts heat from
the source (hot body), converts a part of it into work and rejects the
rest of heat to the sink (environment). There is no engine, which
converts the whole heat into work, without rejecting some heat to
the sink. These observations led Kelvin and Planck to state the
second law of thermodynamics as it is impossible for any system to
absorb heat from a reservoir at a fixed temperature and convert
whole of it into work.
 Clausius statement of second law of thermodynamics is based on
the performance of a refrigerator. A refrigerator is a heat engine
working in the opposite direction. It transfers heat from a colder
body to a hotter body when external work is done on it. Here
concept of external work done on the system is important. To do this
external work, supply of energy from some external source is
necessary. These observations led Clausius to state the second law of
thermodynamics in the following form.
 It is impossible for any process to have as its sole result to transfer
heat from a colder body to a hotter body without any external
work.
THIRD LAW OF
THERMODYNAMICS
 The third law of thermodynamics just says that you
cannot reach absolute zero through any process that uses
a finite number of steps. Which is to say, you cannot get
down to absolute zero at all. Each step in the process of
lowering an object’s temperature to absolute zero can get
the temperature a little closer, but you can’t get all the
way there, unless you use an infinite number of steps,
which isn’t possible.
 The Third Law of Thermodynamics is concerned with the
limiting behaviour of systems as the temperature
approaches absolute zero.
 Most thermodynamics calculations use only entropy
differences, so the zero point of the entropy scale is often
not important.
THIRD LAW OF
THERMODYNAMICS
 The Third Law states, the entropy of a perfect crystal is zero
when the temperature of the crystal is equal to absolute zero
(0 K). The crystal must be perfect, or else there will be some
inherent disorder. It also must be at 0 K; otherwise, there will
be thermal motion within the crystal, which leads to disorder.
 The Third Law of Thermodynamics was first formulated by
German chemist and physicist Walther Nernst. In his book, ‘A
Survey of Thermodynamics’ (American Institute of Physics,
1994), Martin Bailyn quotes Nernst’s statement of the Third
Law as, ‘It is impossible for any procedure to lead to the
isotherm T = 0 in a finite number of steps’. This essentially
establishes a temperature absolute zero as being
unattainable in somewhat the same way as the speed of light
c. Theory states and experiments have shown that no matter
how fast something is moving, it can always be made to go
faster, but it can never reach the speed of light. Similarly, no
matter how cold a system is, it can always be made colder,
but it can never reach absolute zero.
IMPLICATIONS OF THE THIRD LAW

There is a field of ultra-low-temperature

research, and every time you turn around there’s While a temperature of absolute zero does not exist
in nature, and we cannot achieve it in the laboratory,
a new record low. These days, nanokelvin (nK = the concept of absolute zero is critical for
10−9 K) temperatures are reasonably easy to calculations involving temperature and entropy.
achieve, and everyone is now working on Many measurements imply a relationship to some
picokelvins (pK =, 10−12 K). The record-low starting point. When we state a distance, we have to
temperature was achieved 1999 by the YKI- ask, distance from what? When we state a time, we
group of the Low Temperature Laboratory at have to ask, time since when? Defining the zero
Aalto University in Finland. They cooled a value on the temperature scale gives meaning to
positive values on that scale. When a temperature is
piece of rhodium metal to 100 pK, or 100 stated as 100 K, it means that the temperature is 100
trillionths of a degree Celsius above absolute K above absolute zero, which is twice as far above
zero besting the previous record of 280 pK set absolute zero as 50 K and half as far as 200 K.
by them in 1993.
THANK YOU FOR
WATCHING.