Thermal Physics

Instructor-
Golam Dastegir Al-Quaderi
Professor
Department of Physics, DU

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 Conversion of Work into Heat and
Vice-versa
• Conversion of Work into Heat:
• Consider a thermodynamic system, consisting of an
object (such as a resistor or a piece of stone) immersed
into a medium of large heat capacity, which we call a
reservoir.
• If by mechanical means (by rubbing or friction) or by
electrical means (by passing electricity through it)
some work is done on the object, temperature of the
object tends to rise.
• Any rise of temperature will result in a transfer of
energy, in the form of heat, from the object (system)
to the medium (reservoir) and vice-versa.

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 Conversion of Work into Heat and
Vice-versa
• Conversion of Work into Heat:
• Since the heat capacity of the surrounding
medium (e.g. water) is large, the transfer of heat
to the medium would change the temperature of
the medium only by an infinitesimal amount
(which is negligible).
• Hence, the object would essentially remain at
constant temperature (isothermal work done), so
also the state of the object.
• This may continue for ever (ad infinitum).
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 Conversion of Work into Heat and
Vice-versa
• Conversion of Work into Heat:
• Hence, we may have a process in which work
is continuously converted into heat without
changing the state of the system.
• In general, work of any kind 𝑊, may be done
on a system in contact with a reservoir,
causing heat 𝑄 to leave the system, without
altering the state of the system.
• The system acts merely as an intermediary.
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 Conversion of Work into Heat and
Vice-versa
• Conversion of Work into Heat:
• From the first law, the work is equal to the
heat, 𝑊 = 𝑄; i.e. transformation of work into
heat is accomplished with 100% efficiency.
• Furthermore, this transformation may be
continued indefinitely.
Work → Heat : Efficiency= 100% (possible)
Duration =infinite time (possible)

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 Conversion of Work into Heat and
Vice-versa
• Conversion of Heat into Work:
• For the conversion of heat into work, we need a
series of processes or a cycle, by which the
conversion may continue indefinitely.
• Also, we need the system to return to its original
state after the end of each cycle.
• In general, a cycle that would to convert heat into
work involves:
• A. A heat reservoir at high temperature 𝑇𝐻
• B. A heat reservoir at lower temperature 𝑇𝐿

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 Conversion of Work into Heat and
Vice-versa
• Conversion of Heat into Work: Let,
• 𝑄𝐻 = heat taken from the high temperature
reservoir by the system
• 𝑄𝐿 = heat expelled from the system to the low
temperature reservoir
• 𝑊 = work done in each cycle
• Then the thermal efficiency of the process is
defined as:
Work output |𝑊|
𝜂= =
Heat input |𝑄𝐻 |

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 Conversion of Work into Heat and
Vice-versa
• Conversion of Heat into Work:
• From the first law, since Δ𝑈 = 0, (cyclic process), we have:
𝑄𝐿
𝑄𝐻 − 𝑄𝐿 = 𝑊 ⇒ 𝜂 = 1 −
𝑄𝐻
• Any such cycle (series of processes), where work is
delivered continuously to the surroundings, running the
cycle over and over again, constitutes a heat engine.
• It is a common experience that:
No heat-engine has ever been developed that converts
the heat extracted from a reservoir at a higher
temperature into work without rejecting some heat to
a reservoir at a lower temperature.

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 The Second Law of Thermodynamics
• The negative statement of impossibility, as observed
in our daily life experience, is the second law of
thermodynamics:
• Kelvin: "It is impossible by means of inanimate material
agency to derive mechanical effect from any portion of
matter by cooling it below the temperature of the
coldest of the surrounding objects."
• Max Planck: "It is impossible to construct an engine
which, working in a complete cycle, will produce no
effect other than, the raising of a weight and the
cooling of a heat reservoir."

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 The Second Law of Thermodynamics
• Thus the Kelvin-Planck statement of the
second law of thermodynamics is:
It is impossible to construct an engine that,
operating in a cycle, will produce no effect
other than the extraction of heat from a
reservoir and the performance of an equivalent
amount of work.

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 The Second Law as a New law of
Nature
• Example of Scenarios Violating the Second Law:
• If the second law were not true, it would be possible
to:
• A. Propel a ship across the ocean by extracting heat
from the ocean.
• B. Run a power plant by extracting heat from the
surrounding air.
• Notice that, neither of the “impossibilities” violate the
first law of thermodynamics.
• Both the ocean and the surrounding air contain an
enormous store/amount of internal energy, part of
which we may hope to extract in the form of heat.
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 The Second Law as a New law of
Nature
• The second law, therefore, is not a deduction
from the first law.
• It stands by itself as a separate law of nature.
• Refers to an aspect of nature different from that
described by the first law.
• In addition to the quantity of energy, we must
consider its quality, as indicated by its usefulness.
• The second law refers to the usefulness of
energy.

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 The Second Law and the Usefulness
Quality of Energy
• As we use energy, its quantity remains
constant, but its quality is degraded.
• Energy degradation is called entropy increase.
• The empirical observation that:
There is always net entropy increase in real
processes
is the second law of thermodynamics.
Energy Degradation ≡ Increase of Entropy
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 The Second Law and the Usefulness
Quality of Energy
• The first and second laws of thermodynamics allow us
to analyze the limits on the processes that can occur in
nature.
• The first law allows only those processes that conserve
total energy.
• The second law allows only those processes in which
the quality of energy never increases in the system
and surroundings as a whole.
• The property of energy becoming less useful as we use
it, is purely a characteristic of the macroscopic realm.
• This behaviour emerges from the microscopic
properties for large number of particles.

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 The Second Law and the Direction of
Processes in Real World
• What is the criterion for the direction of real processes?
• What do we mean by a real process?
• Obviously, any process that is not ‘‘real’’ cannot occur, at
least it cannot occur in a finite time.
In any real process, there is net degradation of energy.
• According to the second law, processes that result in net
upgrading of energy are not possible.
• The second law thus gives the direction or arrow of time.
• Any process in real macroscopic world that violates the
second law can not run forward in time:
The Second Law ⇒ Arrow of Time 15
 Lack of Proof of the Second Law of
Thermodynamics
• We have not proved and cannot prove the second
law, just as we did not prove the first law.
• These laws are a generalization of our experience,
and no apparent violation of them has ever
survived close scrutiny.
• We must be content to state it as a crystallization
of our experience.
• Both of these laws are fundamental laws of
nature.
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 The Second Law and the Perpetual
Machine
• Machines that would violate the first law are
called perpetual motion machines of the first
type.
• Machines that violate the second law are called
perpetual motion machines of the second type.
• A perpetual motion machine of the first kind
produces work without the input of energy.
• A perpetual motion machine of the second kind
is a machine which spontaneously converts
thermal energy into mechanical work.
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 The Second Law and Entropy
• We have defined a new thermodynamic function
that measures energy degradation.
• We call this function the entropy and designate it
by the symbol 𝑆.
• In terms of entropy our second law becomes:
In any real process, there is net entropy increase.
• The mathematical form of our second law then
becomes:
Δ𝑆univ = Δ𝑆sys + Δ𝑆sur ≥ 0

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 Entropy as a State Function
• Is entropy a state function?
• There is no reason that the quality of energy
should be less a state function than the quantity
of energy.
• When the system is completely defined, both the
quantity of energy as well as the quality of energy
should be known.
• The state function nature of entropy is critical for
the mathematical definition of this
thermodynamic quantity.
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 Refrigerators and the Second Law of
Thermodynamics
• Imagine the cycle of a heat engine performed in a
sequence of processes opposite to that of an engine.
• Then some heat is absorbed by the system from a heat
reservoir at a low temperature, a larger amount of heat
is rejected to a heat reservoir at a high temperature.
• Also a net amount of work is done on the system by
the surroundings.
• A machine that performs a cycle in this direction is
called a refrigerator.
• The working substance of a refrigerator is called a
refrigerant.
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 Refrigerators and the Second Law of
Thermodynamics
• Let, 𝑄𝐻 = the amount of heat rejected by the
refrigerant to the high-temperature reservoir;
• 𝑄𝐿 = the amount of heat absorbed by the refrigerant
from the low-temperature reservoir; and
• 𝑊 = the net work done on the refrigerant by the
surroundings.
• Since the refrigerant undergoes a cycle, there is no
change in internal energy.
• From the first law:
𝑄𝐻 = 𝑄𝐿 + 𝑊

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 Refrigerators and the Second Law of
Thermodynamics
• The purpose of a refrigerator is to extract as
much heat |𝑄𝐿 | as possible from the low-
temperature reservoir with the expenditure of as
little work |𝑊| as possible.
• Work is always necessary to transfer heat from a
lower-temperature reservoir to a higher-
temperature reservoir.
• Heat does not flow spontaneously
from low temperature body to a
high temperature body.

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 Refrigerators and the Second Law of
Thermodynamics
• The negative statement that heat does not
spontaneously flow from low temperature
body to a high temperature body leads us to
the Clausius statement of the second law:
It is impossible to construct a refrigerator that,
operating in a cycle, will produce no effect
other than the transfer of heat from a lower-
temperature reservoir to a higher-temperature
reservoir.

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 Equivalence of Kelvin-Planck and
Clasius Statements
• Two propositions or statements are said to be
equivalent when:
• The truth of one implies the truth of the second
• And the truth of the second implies the truth of the
first.
𝐾 = truth of the Kelvin-Planck statement;
−𝐾 = falsity of the Kelvin-Planck statement;
𝐶 = truth of the Clausius statement;
−𝐶 = falsity of the Clausius statement.
• Let, ⊃ means “implies” and ≡ means “equivalence”

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 Equivalence of Kelvin-Planck and
Clasius Statements
• We wish to prove, 𝐾 ≡ 𝐶 which means:
𝐾 ⊃ 𝐶 and 𝐶 ⊃ 𝐾
• Alternatively, 𝐾 ≡ 𝐶 means:
−𝐾 ⊃ −𝐶 and −𝐶 ⊃ −𝐾
• To prove that −𝐶 ⊃ −𝐾, consider a refrigerator, shown
in the left side:

.
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 Equivalence of Kelvin-Planck and
Clasius Statements
• It requires no work to transfer |𝑄𝐿 | units of heat from a
low-temperature reservoir to a high-temperature
reservoir.
• Hence it violates the Clasius statement i.e. implies −𝐶.
• Suppose that a heat engine (on the right) also operates
between the same two reservoirs.
• Through it the same heat |𝑄𝐿 | is delivered to the low-
temperature reservoir.
• This second engine does not
violate any law by itself alone.

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 Equivalence of Kelvin-Planck and
Clasius Statements
• But the refrigerator and the second engine
together constitute a self-contained machine,
that:
• Takes a (fraction) of heat 𝑄𝐻 − |𝑄𝐿 | from the
high temperature reservoir and converts all this
heat into work without producing any change in
the low-temperature reservoir.
• Therefore, the refrigerator and engine together
constitute a violation of the Kelvin-Planck
statement i.e. implies −𝐾 .
• Thus, −𝐶 ⊃ −𝐾 i.e. −𝐾 is a consequence of −𝐶.
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 Equivalence of Kelvin-Planck and
Clasius Statements
• To prove that −𝐾 ⊃ −𝐶, consider an engine,
shown on the left side of the figure below:
• It rejects no heat to the low-temperature
reservoir and that, therefore, violates the Kelvin-
Planck statement i.e. implies −𝐾.
• Suppose that a refrigerator
on the right also operates
between the same two
reservoirs and uses up all the
work performed by the engine.

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 Equivalence of Kelvin-Planck and
Clasius Statements
• The refrigerator on the right violates no law.
• But the engine and refrigerator together constitute a
self-contained machine that:
• Transfers heat |𝑄𝐿 | from the low-temperature reservoir
to the high-temperature reservoir without producing
any changes elsewhere.
• Therefore, the engine and the
refrigerator together
constitute a violation of the
Clausius statement i.e. −𝐶 .
• Thus, −𝐾 ⊃ −𝐶

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