EKC222 Chem. Eng. Thermo.

Semester 2, 2018/19
Lecture #1 – History of Thermodynamics

Origin of Thermodynamics
The origin of thermodynamics, in different from most
of the other disciplines in chemical engineering, started
from the urge of human being to improve the
performance of steam engine driven by motive power.
Even though the creation of steam engine can be trace
back to 1650 with the first design of vacuum pump by
Otto von Guericke, the recognition of thermodynamics
as a modern science was not started until Sadi Carnot
published his seminal paper on Reflection on the Motive
Power of Fire in 1824 [1]. Carnot defined "motive
power" to be the expression of the useful effect that a A steam engine that revolutionalized
motor is capable of producing. Herein, Carnot the process of generating mechanical
introduced to us the first modern day definition of work which will be used to sustain
"work": weight lifted through a height. The desire to the development of human
understand, via formulation, this useful effect in relation civilization.
to "work" is at the core of classical thermodynamics
[2]. Graphic from: www.portlandfiremuseum.com

Thermodynamics based upon phenomenological observations

(a) Robert Boyle, (b) Robert
Hooke, (c) Jacques Charles, and
(d) Emile Clapeyron.
Portraits obtained from [3]
The fundamental principles that govern the amount of
works which can be obtained from a given amount of
heat by a steam engine often involved the need to
understand the correlation between pressure, volume
and temperature (PVT relationship). Although the
understand of heat is still quite primitive before
Carnot’s time (as implied by famous Robert Hooke
statement ~ “Heat being nothing else but a very brisk
and vehement agitation of the parts of a body”) but
phenomenological understanding of PVT relation is
made possible through experience. By observing the
continuous operation of an air pump (together with
Hooke), Robert Boyle noticed that PVT properties
could be related through a simple equation where PV =
constant (published as Boyle’s Law in 1662). Later,
the major mathematical effort to related these 3
properties together is attributed to French scientist
Jacques Charles, in which he proposed that V1T2 =
V2T1. In 1834, Emile Clapeyron combined Charles’s
law with Boyle’s law to produce a single statement
which becomes known as ideal gas law [3]. This is the
period where the foundation for classical
thermodynamics was established.

By JitKang Lim @ Universiti Sains Malaysia 1

EKC222 Chem. Eng. Thermo. Semester 2, 2018/19
Lecture #1 – History of Thermodynamics

Invention of a Steam Engine

Otto von Guericke from Magdeburg (1602 – 1686) is the
first one who designed a device to evacuate an air-filled
container (probably around 1650). He constructed his air
or vacuum pump based on the principles of the fire
extinguisher, he only changed direction of the
pumping/suction actions [4].

In 1663, before the Emperor Ferdinand III (Imperial Diet)

at Regensburg, he attained the famous demonstration of
the Magdeburg hemispheres. These consisted of two
bronze bowls fitted together forming a vacuous sphere and
a pump, which remove the air from the hemisphere. After
the air was expulsed out of the sphere the bowls were
unable to disjoin. In addition, he attempted this
experiment by using horses to try to pull the bowls apart, A vacuum pump of the 2nd
but did not succeed. This was even though these two generation, constructed in 1664,
bowls were held together only by the air around them. was installed in Guericke’s
Hence, the tremendous force that air pressure exerts was private house and it ranged from
first ascertained [5]. the cellar up to his office.

Graphic from: http://www.mk-technology.com/

The first commercial steam-powered device was a water pump, developed in 1698 by Thomas
Savery. It used a vacuum to raise water from below, then used steam pressure to raise it higher.
Small engines were effective though larger models were problematic. They proved only to have
a limited lift height and were prone to boiler explosions. It received some use in mines, pumping
stations and for supplying water wheels used to power textile machinery [3].

(Left) Savery Pump (http://www.egr.msu.edu/~lira/supp/steam/savery.htm), and (Right)

Thomas Savery (Portrait obtained from [3]).

By JitKang Lim @ Universiti Sains Malaysia 2

EKC222 Chem. Eng. Thermo. Semester 2, 2018/19
Lecture #1 – History of Thermodynamics
The later steam pump designs by Thomas Newcomen and James Watt used only atmospheric
pressure steam to avoid pressurized steam. Also, they used liquid pumps that were compact and
could be driven by steam. The compact pumps could be placed more easily in a well or mine
within 25 feet of the water.

Thomas Newcomen (1663-1729), a blacksmith, experimented for 10 years to develop the first
truly successful steam engine to drive a pump to remove water from mines. His ability to sell the
engine was hampered by Savery's broad patent. He was forced to establish a firm with Savery,
despite the improved performance of his engine, the significant mechanical differences, the
elimination of the need for steam pressure, and the use of vacuum in a very different manner. A
schematic of a Newcomen engine is shown in Figure below. The engine is called an
"atmospheric" engine because the greatest steam pressure used is near atmospheric pressure.

Illustration of the Newcomen

atmospheric engine for
pumping water. The
operational procedure of this
steam engine is directly crtl-C
and ctrl-V from [6] as
described below.

Please click on the following

link
http://www.animatedengines.c
om/newcomen.html for
animated version of
Newcomen Engine

Step 1 - upward stroke of steam piston (upward on left side).

Valves A, D, E, are open, and valve B, C, F-J are closed. Weight of the pump side pulls beam
down on the right lowering the pistons in the main and auxilary pumps. (On some engines extra
weight is added to the pump side of the beam to assure it is heavier than the steam side). This
action pulls up the steam piston, and pulls steam into the cylinder. Note that the steam piston is
attached by a chain - it can't push up the beam! The boiler operates at nearly atmospheric
pressure. During this upward motion, steam piston condensate is pulled into the condensate
pump and lifted to the water reservoir. The valves F-J in the main and auxilary pumps are closed
during this step.

Step 2 - downward stroke of steam piston (downward on left side).

Valve A, D, E are closed, valves B, C, F-J are opened. Water is sprayed into the cylinder below
the piston to condense the steam, creating a vacuum inside. The atmospheric pressure on the
outside pushes the piston downwards. This action pulls down the beam and fills the main water
pump and auxiliary pumps and lifts the water above the pistons. The top of the steam cylinder is

By JitKang Lim @ Universiti Sains Malaysia 3

EKC222 Chem. Eng. Thermo. Semester 2, 2018/19
Lecture #1 – History of Thermodynamics
open and the steam piston is visible from the top. Water is sprayed onto the top of the piston via
valve C to maintain a good seal. Even though Newcomen was a blacksmith, he couldn't make
perfectly round cylinders in those days. The cylinders were typically cast and slightly out of
round, as well as the pistons! The seal was made by a packing of oakum (hemp fibers soaked in
tar) that was jammed in a channel between the piston and cylinder and held in place by weights.
Newcomen found it necessary to keep the seal wet in order to maintain the vacuum.

Early Newcomen engines simply drained the condensate water from the steam piston. In the
engine illustrated here, a condensate pump is provided that sits in a well that would have been
filled with water, presumably pumped from the mine by the main pump. This particular
Newcomen engine also has an auxiliary pump to provide condensing water.

(a) Newcomen’s and (b) Watt’s Steam

engine which are currently exhibited at
Herny Ford Musseum in Dearborn, MI.
The person in the photo (a) gives you some
idea of the scale. (c) Illustration of the
Watt atmospheric engine for pumping
water. The main pump is not shown.

All figure are adapted from [6]

Dates in the history of steam engines and James Watt (summarized by Carl T. Lira of Michigan
State University). Please visit Lira’s website [6] for a lot more interesting discussions about
steam engine.

1698 Thomas Savery patent

1712 Thomas Newcomen patent
1736 Watt born
1755 Watt trained in London
1763 Watt discovers problem with Newcomen engine
1765 Watt discovers external condenser
1769 Roebuck and Watt patent the engine
1774 Boulton acquires Roebuck's patent rights. Watt moves
to Birmingham
1776 The first Boulton and Watt engine is commercially applied
1781-2 Patents for sun and planet gears, and the double-acting
engine
1800 Engine patent runs out. Watt retires at 64, healthy, happy, James Watt (1736-1819)
and famous www.bbc.co.uk

1819 James Watt dies, age 83

By JitKang Lim @ Universiti Sains Malaysia 4

EKC222 Chem. Eng. Thermo. Semester 2, 2018/19
Lecture #1 – History of Thermodynamics

Classical Thermodynamics
At the end of 18th century, steam engines had achieved widely recognized economic and
industrial importance, but there had been no real scientific study of them. Although there existed
some intuitive understanding of the workings of engines, scientific theory for their operation was
almost nonexistent. In 1824 the principle of conservation of energy was still poorly developed
and controversial, and an exact formulation of the first law of thermodynamics was still more
than a decade away; the mechanical equivalence of heat would not be formulated for another two
decades. The prevalent theory of heat was the caloric theory, which regarded heat as a sort of
weightless and invisible fluid that flowed when out of equilibrium [3].

Carnot sought to answer two questions about the operation of heat

engines: (1) "Is work available from a heat source potentially
unbounded?" and (2) "Can heat engines in principle be improved by
replacing the steam with some other working fluid or gas?" He
attempted to answer these in a memoir, published as a popular work
in 1824 when he was only 28 years old. It was entitled Réflexions
sur la Puissance Motrice du Feu ("Reflections on the Motive
Power of Fire"). Perhaps the most important contribution Carnot
made to thermodynamics was his abstraction of the essential features
of the steam engine, as they were known in his day, into a more
general and idealized heat engine. In Carnot's idealized model, the
Sadi Carnot caloric heat converted into work could be recovered by reversing the
(1796 - 1832) motion of the cycle, a concept subsequently known as
From Wikipedia
thermodynamic reversibility. (All discussion from [3])

Helmholtz’s important scientific achievement, an 1847 physics

treatise on the conservation of energy was written in the
context of his medical studies and philosophical background. He
discovered the principle of conservation of energy while
studying muscle metabolism. He tried to demonstrate that no
energy is lost in muscle movement, motivated by the
implication that there were no vital forces necessary to move a
muscle. Drawing on the earlier work of Carnot, Clapeyron and
Joule, he postulated a relationship between mechanics, heat,
light, electricity and magnetism by treating them all as
manifestations of a single force (Energy). He published his
Hermann von
theories in his book Über die Erhaltung der Kraft (On the
Helmholtz
Conservation of Force, 1847). (All discussion from [3])
(1821 - 1894)
From Wikipedia

By JitKang Lim @ Universiti Sains Malaysia 5

EKC222 Chem. Eng. Thermo. Semester 2, 2018/19
Lecture #1 – History of Thermodynamics
Thomson was convinced that all forms of energy were interrelated –
heat, light, electrical, magnetic, mechanical – and he believed that
the various theories dealing with matter and energy were converging
towards a grand unified theory. James Prescott Joule established the
conversion relationship that applies when mechanical motion is
converted into heat. This spurred Thomson to great effort
culminating in a major mathematical volume On the dynamical
theory of Heat (1852) in which he outlined his version of the second
law of thermodynamics [7]. Thomson is also widely known for
determining the correct value of absolute zero as approximately -
William Thomson 273.15 Celsius and be the first one who coined the term
(Lord Kelvin) thermodynamics [3].
(1824 - 1907)
From Wikipedia

James Prescott Joule

(1818-1889)
From Wikipedia

By JitKang Lim @ Universiti Sains Malaysia 6

EKC222 Chem. Eng. Thermo. Semester 2, 2018/19
Lecture #1 – History of Thermodynamics

By his restatement of Carnot's principle, Clausius put the theory

of heat on a truer and sounder basis, and he deserves the credit
of having made thermodynamics a science; he enunciated the
second law, in a paper contributed to the Berlin Academy in On
the mechanical theory of heat 1850, in the well-known form,
"Heat cannot of itself pass from a colder to a hotter body."
His results has been applied to an exhaustive development of the
theory of the steam engine [8], laying stress in particular on the
conception of dQ/T (Clausius’s theorem) and later coined the
Rudolf Clausius term entropy.
(1822 - 1888)
From Wikipedia

Statistical Mechanics S = kBlnΩ

The thermodynamic description is limited in scope - it gives only macroscopic information about
the system but this does not come at the price of precision. Once we have defined entropy and
know a few of its properties, what can we do with it? The subject of thermodynamics asks what
can be discovered about substance by just knowing that entropy exists, without knowing a
formula for it. It is one of the most fascinating fields in all of science, because it produces a large
number of dramatic and unexpected results based on this single modest assumption [9]. From
physics, statistical mechanics provides such a bridge by teaching us how to conceive of a
thermodynamic system as an assembly of units. More specifically, it demonstrates how the
thermodynamic parameters of a system, such as temperature and pressure, are interpretable in
terms of the parameters descriptive of such constituent atoms and molecules [3].

Bernoulli pointed out for the first time that the frequent
desirability of resolving a compound motion into motions of
translation and motions of rotation. His chief work is his
Hydrodynamique (Hydrodynamica), published in 1738; it
resembles Joseph Louis Lagrange's Méchanique Analytique in
being arranged so that all the results are consequences of a
single principle, namely, conservation of energy. He speculated
that gases consist of great number of molecules moving in all
directions and heat is simply the kinetic energy of their motion
Daniel Bernoulli [3].
(1700 - 1782)
From Wikipedia

By JitKang Lim @ Universiti Sains Malaysia 7

EKC222 Chem. Eng. Thermo. Semester 2, 2018/19
Lecture #1 – History of Thermodynamics
With Clausius, Maxwell developed the kinetic theory of gases. In
"Illustrations of the Dynamical Theory of Gases" (1860), he
showed the velocity distribution of molecules followed Maxwell
distribution. His studies of kinetic theory led him to propose the
Maxwell's demon paradox in a 1867 letter to Peter Tait. Maxwell's
demon (termed a "finite being" by Maxwell) is a tiny hypothetical
creature that can see individual molecules. He can make heat flow
from a cold body to a hot one by opening a door whenever a
molecule with above average kinetic energy approaches from the
James Clerk cold body, or below average kinetic energy approaches from the hot
Maxwell body, then quickly closing it. This process appears to violate the
(1831 - 1879) second law of thermodynamics, but was used by Maxwell to show
From Wikipedia that the second law of thermodynamics is a statistical law
describing the properties of a large number of particles. Maxwell
also observed in private correspondence that the time reversal of all
events was consistent with the laws of dynamics, but inconsistent
with the Second Law of Thermodynamics. Maxwell published his
views on the limitations of the Second Law in Theory of Heat
(1871) (All discussion from [10]).

Boltzmann's most important scientific contributions were in

kinetic theory, including the Maxwell–Boltzmann distribution
for molecular speeds in a gas. In addition, Maxwell–Boltzmann
statistics and the Boltzmann distribution over energies remain
the foundations of statistical mechanics. They are applicable to
the many phenomena that do not require quantum statistics and
provide a remarkable insight into the meaning of temperature.
To quote Planck, "The logarithmic connection between entropy
and probability was first stated by L. Boltzmann in his kinetic
theory of gases". The idea that the second law of Ludwig Boltzmann
thermodynamics or "entropy law" is a law of disorder (or that (1844 - 1906)
From Wikipedia
dynamically ordered states are "infinitely improbable") is due to
Boltzmann's view of the second law. Following Maxwell,
Boltzmann modeled gas molecules as colliding billiard balls in a
box, noting that with each collision nonequilibrium velocity
distributions (groups of molecules moving at the same speed
and in the same direction) would become increasingly
disordered leading to a final state of macroscopic uniformity and
maximum microscopic disorder or the state of maximum
entropy (where the macroscopic uniformity corresponds to the
obliteration of all field potentials or gradients). (All discussion
from [3]).
Boltzmann's grave
in the Vienna,
with entropy formula.
From Wikipedia

By JitKang Lim @ Universiti Sains Malaysia 8

EKC222 Chem. Eng. Thermo. Semester 2, 2018/19
Lecture #1 – History of Thermodynamics

Gibbs is recognized as the first American who received

doctorate degree in engineering (from Yale in 1863). Together
with Maxwell and Boltzmann, he created statistical mechanics
(a term that he coined), explaining the laws of thermodynamics
as consequences of the statistical properties of large ensembles
of particles. Gibbs's papers from the 1870s On the Equilibrium
of Heterogeneous Substances introduced the idea of expressing
the internal energy U of a system in terms of the entropy S, in
addition to the usual state-variables of volume V, pressure p, and
temperature T. He also introduced the concept of the chemical
Josiah Willard potential of a given chemical species, defined to be the rate of
Gibbs the increase in U associated with the increase in the number N of
(1839 - 1903) molecules of that species (at constant entropy and volume).
From Wikipedia Thus, it was Gibbs who first combined the first and second
laws of thermodynamics by expressing the infinitesimal
change in the energy of a system. He is also the one who defined
the concepts of enthalpy and "free energy", including what is
now known as the "Gibbs free energy" (a thermodynamic
potential which is especially useful to chemists since it
determines whether a reaction will proceed spontaneously at a
fixed temperature and pressure). In a similar way, he also
obtained what later came to be known as the "Gibbs–Duhem
equation".

Much development continued in the twentieth century, with pioneering work by Nobel laureates
[11]:

• Jacobus Henricus van’t Hoff (1901),

John Fenn (Nobel prize in
• Johannes van der Waals (1910),
chemistry 2002) – PhD
• Heike Kamerlingh Onnes (1913), dissertation:“The Thermodynamics
of Hydrochloric Acid in Methanol-
• Max Planck (1918),
Water Mixtures 1940”
• Walther Nernst (1920),
• Albert Einstein (1921),
• Erwin Schrodinger (1933),
• Enrico Fermi (1938),
• Percy Bridgman (1946),
• Lars Onsager (1968),
• Ilya Prigogine (1977), and
• Kenneth Wilson (1982).

By JitKang Lim @ Universiti Sains Malaysia 9

EKC222 Chem. Eng. Thermo. Semester 2, 2018/19
Lecture #1 – History of Thermodynamics

References
1. Sadi Carnot, “Reflections on the Motive Power of Fire: And Other Papers on the Second
Law of Thermodynamics”, 2005, Dover.
2. Josiah Willard Gibbs, “The History of a Great Mind”, 1998, Ox Bow Pr.
3. Wikipedia
4. http://www.mk-technology.com/otto_v_guericke.html?L=2
5. http://library.thinkquest.org/C006011/english/sites/guericke_bio.php3?f=2&b=50&j=1&
v=0
6. J.R. Elliot and C.T. Lira, “Introductory Chemical Engineering Thermodynamics”, 1999,
Prentice Hall. Online supplementary information can be found at
http://www.egr.msu.edu/~lira/supp/steam/index.htm
7. Understanding science http://understandingscience.ucc.ie/pages/sci_kelvin.htm
8. http://www.nndb.com/people/951/000100651/
9. D.F. Styer, “Insight Into Entropy”, Am. J. Phys. 68, 2000, 1090 – 1096.
10. Wolfram research http://scienceworld.wolfram.com/biography/Maxwell.html
11. J.M. Power, “Lecture Notes on Thermodynamics”, 2013, Dept. of Aerospace and
Mechanical Engineering, Uni. Of Notre Dame.

By JitKang Lim @ Universiti Sains Malaysia 10