Kwame Nkrumah University of

Science & Technology, Kumasi, Ghana

KNUST PHY 255

Thermodynamics

February, 2023
OUTLINE Kwame Nkrumah University of
Science & Technology, Kumasi, Ghana

❖ Revision
❖ Reversible & Irreversible Processes
❖ Heat Engine
❖ Heat Pump
❖ Carnot Engine (Cycle)
❖ Entropy & 2nd Law
❖ Next Lecture Topics
❖ Assignment for the Week
 Reversible & Irreversible
Processes
❖ A reversible process is one in which every point along some path
is an equilibrium state.

❖ A reversible process is defined as a process in which the system

and surroundings can be returned to the original conditions from
the final state without producing any changes in the
thermodynamics properties of the universe, if the process is
reversed.

❖ Reversible processes actually do not occur in nature. It is an

idealized process but its used to approximate systems with very
slow changes.

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 Reversible & Irreversible
Processes
❖ Irreversible processes: system does not return to its original state
and there is usually some work done on it by the surroundings.
❖ Eg: Friction, temperature difference and others

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 Heat Engine
❖ A heat engine is a device that takes in energy by heat, operates
in a cyclic process and expels a fraction of that energy by means
of work.
❖ More precisely the device converts internal energy to mechanical
energy.
• Denis Papin (1647-1712): first to condense water and built a
digester to cook food.
• James Watt (1712) improved on Thomas Newcomen's steam
engine as he improved Thomas Sarvey's.

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 Heat Engine
❖ Thermal efficiency: the ratio of the
net work done by the engine during
one cycle to the energy input at the
higher temperature.

𝑊𝑒𝑛𝑔 𝑄ℎ − 𝑄𝑐 𝑄𝑐
𝜂= = =1− … . (2)
𝑄ℎ 𝑄ℎ 𝑄ℎ
Qh=Heat energy from hot reservoir.
Qc=Heat energy into cold reservoir.

❖ In practice, all heat engines expel

only a fraction of the input energy by
mechanical work.
❖ Why is 𝜂 always less than 1 or
100%???
❖ How can we obtain 𝜂 = 1 𝑜𝑟 100%?
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 Heat Pump
❖ Heat pumps runs in reverse form of heat
engines. Work is done on the system to
enable the transfer of heat from low to
high.
❖ E.g. refrigerator and an air conditioner.
❖ Unlike the heat engine, effectiveness of a
heat pump is described by a number called
the coefficient of performance (COP).

𝑄ℎ
𝐶𝑂𝑃 = … . (3)
𝑊
Qh= energy transferred at high temp.
W = done by pump
❖ In practice, all heat engines expel only a
fraction of the input energy by mechanical
work.
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 Carnot Engine (Cycle)
❖ Sadi Carnot wondered how to achieve/attain the best improved
efficient steam engine.
❖ A heat engine operating in an ideal, reversible cycle two
reservoirs.

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 Carnot Engine (Cycle)
❖ Carnot showed that the efficiency
of the engine depends on the
temperatures of the reservoirs.

𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑇𝐿
𝜂= = 1 − … . (4)
𝐻𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑇ℎ

❖ What are the Conclusions you think

Carnot made from his eqn 4???

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 Carnot's Theorem
❖ No real heat engine operating between two energy reservoirs
can be more efficient than a Carnot engine operating between
the same two reservoirs.
• All real engines are less efficient than a Carnot engine because
they do not operate through a reversible cycle.
• The efficiency of a real engine is further reduced by friction,
energy losses through conduction and others.

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 Entropy & 2nd Law

❖ Nicolas Leonard Sadi Carnot: transformation of heat in a cycle.

❖ Lord Kelvin (1851): 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.

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 Entropy & 2nd Law

What is an Entropy?

❖ Rudolf Clausius quest to move away from

(1) Carnot cycles
(2) Cycles of whatever type
(3) Infinitesimal Carnot cycles
(4) Reversible processes
(5) Ideal gases

❖ Rudolf Clausius (1865): "Heat cannot pass by itself from a colder

to a warmer body"

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 Entropy & 2nd Law

𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑄ℎ − 𝑄𝐿 𝑄𝐿
𝜂= = =1− …. 5
𝐻𝑒𝑎𝑡 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑄ℎ 𝑄ℎ

But knowing from Carnot:

𝑄ℎ 𝑄𝐿
= …. 6
𝑇ℎ 𝑇𝐿

❖ Clausius noticed two types of transformations going on in the

heat engine:
(1) Conversion of heat into work
(2) Passage of heat from high temperature to low temperature

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 𝑄
Entropy, 𝑆 = , meaning transformation or change.
𝑇

Assumptions:

Consider an arbitrary cycle with infinitesimal isothermal

steps open reversible process not a cycle "=" and irreversibility,
">“.
𝑓
𝛿𝑄
𝑑𝑆 ≥ න … . (7)
𝑇
𝑖
S is entropy, Q is amount of energy transferred by heat, T is
absolute temperature.

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❖ Constantin Caratheodory, Principle of Caratheodory (1909): "In
every neighborhood of any state, S, of an adiabatically enclosed
system there exist inaccessible states".

𝛿𝑄 = 𝑇𝑑𝑆 … . (8)

❖ Max Planck, Planck's principle (1926): "The internal energy of a

closed system is increased by an adiabatic process, throughout
the duration of which, the volume of the system remains
constant". S(n, V, U)

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❖ Entropy is a measure of disorderliness.
❖ The entropy of the Universe increases in all real processes.
❖ Rudolf Clausius "If the entropy of the Universe reach a maximum
value, the Universe will be in a state of uniform temperature and
density - Heat Death of the Universe.

• The state of perfect disorder implies that no energy is available

for doing work.
• All physical, chemical, and biological processes will cease.

❖ Kinetic theory in the late 1800s burst out probabilistic principle

of further understanding of entropy from the microscopic view
point [Boltzmann's equation from statistical mechanics]:
𝑆 = 𝑘𝐵 𝑙𝑛Ω … . (9)
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 Next Lecture Topics

Potential and its derivatives

❖ Enthalpy
❖ Helmholtz and Gibbs free energies.
❖ Caratheodory formulation
❖ Legendre transformations of the thermodynamic potentials.
❖ The Maxwell relations.
❖ Clausius-Clapeyron equation
❖ Joule-Thompson Coefficient
❖ Physical significance of the potentials.

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 Assignment 3
(1) Given a thermodynamic function ℎ = ℎ(𝑠, 𝑃) show how to
Evaluate 𝑇, 𝑉, 𝑈, 𝐴 𝑜𝑟 𝐹 𝑎𝑛𝑑 𝐺.
𝑉𝑇𝛽 2
(2) Show 𝐶𝑝 − 𝐶𝑉 = , and make all conclusions possible.
𝛼
(3) The volume expansivity of water at 20𝑜 𝐶 is 𝛽 = 0.207 × 10−6 𝐾 −1
Treating this value as a constant, determine the change in
volume of 1 m3 of water as it is heated from 10𝑜 𝐶 to 30𝑜 𝐶 at
constant pressure.
(4) Can the variation of specific heat Cp with pressure at a given
temperature be determined from a knowledge of P,V,T data
alone? Explain your answer by any mathematical expression
possible.
(5) What does the Joule-Thomson coefficient represent?

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 Assignment 3
(6) State an example of a process that occurs in nature that is as
close to reversible as can be.
(7) Find the efficiency of a heat engine that absorbs 2000J of energy
from a hot reservoir and exhausts 1500 J to a cold reservoir.

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Kwame Nkrumah University of
Science & Technology, Kumasi, Ghana

20