GENERAL I ARTICLE

Sadi Carnot and the Second

Law of Thermodynamics

J Srinivasan

T h e second law of t h e r m o d y n a m i c s is one of the enigmatic

1
1 .
I laws of physics. Sadi Carnot, a F r e n c h engineer played an
I
I
I
important role in its discovery in the 19th century. We
recount here how he proposed the basic postulates of this
~ i~' ~ ' law although he did not fully understand the first law of
thermodynamics.
J Srinivasan is a Professor
both at Centre for
Introduction
Atmospheric and Oceanic
Sciences and D e p a r t m e n t
A major revolution in physics in the 19th century was the
of Mechanical Engineer-
ing st Indian Institute of discovery of the two laws of thermodynamics. Thermodynamics
Science, Bangalore. His is a subject concerned with the interaction of energy with
research interests include matter. The first law of thermodynamics states that energy can
thermal science,
neither be created nor destroyed. The first law established the
atmospheric science and
solar energy. equivalence of heat and work interactions. The second law of
thermodynamics states that it is not possible to convert all heat
(or thermal energy) to work in a continuous process. The second
law of thermodynamics, as stated above, has never been violated
so far although the first law of thermodynamics has to be
modified if there is a nuclear reaction. Most of you may be
surprised to learn that the basic ideas related to the second law of
thermodynamics were discovered earlier and the first law of
thermodynamics was discovered much later! Sadi Carnot, who
discovered the basic ideas that lead to the discovery of second
law of thermodynamics, was a brilliant French military engi-
neer. This genius lived for just 36 years and wrote only one
important paper but this paper laid the foundation for one of the
most enigmatic laws of physics. The second law of thermody-
namics is both enigmatic and profound because it indicates the
arrow of time.

Sadi Carnot, the eldest son of Lazare Carnot was born on 1st

42 RESONANCE I November 2001

 GENERAL I ARTICLE

June 1796 in Paris. Lazare Carnot named his son Sadi

:~]~ : ~: = . = : ,
after the famous Persian poet and philosopher Sadi of
Shiraz. Sadi Carnot grew up during a time when French
politics and science were going through tumultuous
times. Sadi Carnot's father was a famous general and
was a minister of war under Napoleon Bonaparte.
Lazare Carnot was known for his work in engineering
mechanics. In 1807, he withdrew from politics and
concentrated on teaching mathematics, science, lan-
guages and music to his son. Sadi Carnot went to Ecole
Polytechnique at the age of 16. He studied under
eminent faculty such as Gay-Lussac, Poisson and Am-
pere. His contemporaries were eminent scientists such
as Navier and Coriolis. After spending some years in
~ ))~,ii ~ A P
the army, he concentrated his efforts on study and
research.

Sadi Carnot was fascinated by the steam engine be-

cause it had a profound impact on the industrial revolution in Figure 1.
England. He wanted to popularize the use of steam engines in
France. In" 1824, he wrote a monograph entitled 'Reflections on
the motive power of fire and on machines fitted to develop that
power'. This monograph was concerned with the theoretical as
well practical issues related to the conversion of thermal energy
to mechanical energy. This monograph begins with the follow-
ing statement:

"Every one knows that heat can produce motion. That it possesses vast
motive power no one can doubt, in these days when the steam engine is
everywhere so well known. The study of these engines is of great
interest, their importance enormous, their use is continually increasing,
and they seem destined to produce a great revolution in the civilized
world".

Caloric Theory

In 1824, the law of conservation of energy (i.e., the first law of

thermodynamics) was not known. Most scientists assumed that
heat can neither be created nor destroyed. Heat was considered

RESONANCE I November 2001 43

 GENERAL I ARTICLE

To overthrow the to be an invisible fluid without mass that moved from one body
caloric theory that to another when heat was transferred. This fluid was called
was accepted by 'caloric' by the famous French chemist Lavoisier. The caloric
most physicists theory of heat reigned supreme for hundreds of years. It was
and chemists at assumed that caloric was neither created nor destroyed. Hence
that time required the amount of caloric in the universe was finite. The major
a good experiment limitation of the caloric theory was the assumption that me-
that would quantify chanical energy cannot be converted to heat. In 1798, Count
the relationship Rumford had demonstrated categorically that mechanical en-
between ergy was converted to heat during the boring of a cannon. His
mechanical energy experiments did not convince the believers in the caloric theory
and heat. because he was not able to quantify the relationship between
mechanical and thermal energy. Later, Robert Mayer, a medical
doctor, proposed that thermal and mechanical energy were
different forms of the same energy but his ideas were not
accepted. Robert Mayer had obtained a rough estimate of the
relationship between work (measured as force times distance)
and heat measured in calories. This remarkable result was not
understood for a long time because Mayer, being a doctor,
adopted a line of reasoning that was alien to the physicists and
chemists of those times. To overthrow the caloric theory that
was accepted by most physicists and chemists at that time
required a good experiment that would quantify the relation-
ship between mechanical energy and heat. James Prescott Joule
and Lord Kelvin (formerly William Thompson) performed a
series of elegant experiments between 1850 and 1860 to obtain a
quantitative relationship between mechanical and thermal en-
ergy. This led to the demise of the caloric theory by the close of
the 19th century.

Second Law

Sadi Carnot had, however, formulated the basic ideas relevant to

the second law of thermodynamics at a time when the caloric
theory of heat was reigning supreme. Sadi Carnot somehow
managed to formulate the second law of thermodynamics cor-
rectly although he did not understand the first law of thermody-
namics. He arrived at the basic postulates of the second law of

44 RESONANCE I November 2001

 GENERAL I ARTICLE

thermodynamics through his knowledge of hydraulic turbines.

His father, Lazare Carnot was well versed with the design of
water wheels to extract kinetic energy from the potential energy
of falling water. Sadi Carnot proposed that the simplest heat
engine would be one between two thermal reservoirs. A heat
engine is a device that works in a cycle and converts thermal heat
to work. A water wheel receives water from a hydraulic reservoir
at a higher level and discharges water to a hydraulic reservoir at
a lower level. Hence it converts a part of the potential energy of
the falling water to kinetic energy of the water wheel. In the
water wheel the potential energy available in the water can be
extracted as kinetic energy without any loss of water. Sadi
Carnot argued that, like the water wheel, a heat engine receives
heat from a thermal reservoir at a higher temperature and
conducts heat to a thermal reservoir at a lower temperature
(Figure 2). Since he believed in the caloric theory of heat he
assumed that heat is not lost in the process.
Figure 2. Hydraulic analogy
In his own words, "The production of motive power is then due in of a heat engine according
steam engines not on actual consumption of the caloric but to its to Carnot.

w ter .... ........... I[High

Te p - ,e /
.................
i
" HeatIn

. H~f~ghetnce.\ , , ~ Difference ~ ~:~ Work

9 owg - '
. . . . . . . . . . . . . . ~"~'-- ~ ..... TRee~Per~)ir
Water
Out
Water Wheel Heat 'Engine

RESONANCE I November 2001 45

 GENERAL I ARTICLE

Although transportation fiom a warm body to a cold body". We now know that
mechanical energy this is not true from the first law of thermodynamics. Although
can be converted Sadi Carnot did not apply the first law correctly, he postulated
to heat easily the that a heat engine cannot convert all heat to work in a cyclic
reverse is not so process. Carnot, like many geniuses, was able to arrive at the
easy! Sadi Carnot correct postulate for the second law of thermodynamics because
tried to find out he was guided by his intuition. It is truly remarkable that Carnot
what fraction of was able to discover the second law of thermodynamics without
heat (or thermal understanding the first law of thermodynamics!
energy) can be
Today many students find it much easier to understand the first
converted to
law of thermodynamics than the second law of thermodynamics.
mechanical energy
This is not surprising! The law of conservation of mechanical
in a cyclic process.
energy is well-known and easy to understand. The first law
merely extends this notion to the conservation of mechanical
and thermal energy. The great scientists of the 18th and 19th
centuries were however wedded to the concept of heat as a
material fluid and hence were unable to see the fact that me-
chanical energy can be easily converted to heat through friction.
Although mechanical energy can be converted to heat easily the
reverse is not so easy! Sadi Carnot tried to find out what fraction
of heat (or thermal energy) can be converted to mechanical
energy in a cyclic process. The concept of cyclic processes is
central to the various postulates of Sadi Carnot. This is natural
since Sadi Carnot's primary concern was with the devices such
as steam engines that work in a cycle and convert heat to work.
The thermal efficiency of steam engines (i.e., the ratio of work
done to heat added) was less than 5% during the 18th century.
Hence there was a strong incentive to find ways to increase the
efficiency of these steam engines. Sadi Carnot postulated the
existence of an ideal heat engine whose efficiency was indepen-
dent of the working fluid used and dependent upon the tempera-
ture of the hot and cold thermal reservoirs. This postulate was
truly the creation of an inspired genius. In his own words:

"The motive power of a waterfall depends on its height and on the

quantity of the liquid; the motive power of heat depends also on the
quantity of caloric used and on what may be termed the height of its fall,

46 RESONANCE J November 2001

 GENERAL I ARTICLE

that is to say, the difference of temperature of bodies between which the Rudolf Clausius
exchange of caloric is made. In the waterfall the motive power is developed the
exactly proportional to the difference in level between the high and low second law of
reservoirs. In the fall of the caloric the motive power undoubtedly thermodynamics
increases with difference in temperature between the warm and cold without appealing
bodies". to the caloric
theory of heat. He
The basic postulates proposed by Sadi Carnot form the basis of
defined an
the derivation of the second law of thermodynamics in all
important property
modern books on engineering thermodynamics. The mono-
called entropy that
graph published by Sadi Carnot in 1824 was not really under-
emerges directly
stood and appreciated during his lifetime. This was partly on
from the basic
account of the fact that his ideas were well ahead of his time and
postulates of Sadi
also because the caloric theory that he had adopted was attacked
Camot.
by many scientists. Emil Clapeyron recognized the importance
of Carnot's monograph and extended his ideas further by dis-
playing the ideal heat engine in thermodynamic diagrams. Kelvin
completed this task by showing that an ideal heat engine can be
used to define an absolute temperature scale. Rudolf Clausius,
who was professor of physics at Berlin, developed the second law
of thermodynamics without appealing to the caloric theory of
heat. He defined an important property called entropy that
emerges directly from the basic postulates of Sadi Carnot.

After the publication of his monograph in 1824, Sadi Carnot

examined the caloric theory further and began to entertain
doubts about the caloric theory. He died on 24th August, 1832 in
Paris in a cholera epidemic. Many of his unpublished papers
were buried with him. Hence we will never know whether Sadi
Carnot had reformulated the second law without using tl~e
concepts from caloric theory. On account of the premature
death of Sadi Carnot, the correct formulation of the first and
second law of thermodynamics was not achieved till 1865. In
1865, Clausius stated the first and second laws of thermodynam-
ics in an elegant way.

1. The energy of the universe remains a constant.

2. The entropy of the universe tends to a maximum.

RESONANCE I November 2001 47

 GENERAL I ARTICLE

Can we say that Sadi Carnot discovered the second law of

thermodynamics? Most scientists will consider entropy to be
the cornerstone of the second law of thermodynamics and hence
Sadi Carnot will not be considered as the discoverer of the
second law of thermodynamics. The monograph that he pub-
lished in 1824 represents the first attempt to address the issues
related to the efficiency of conversion of heat to work in a cyclic
process. Without Sadi Carnot's original and revolutionary ideas
the discovery of the second law of thermodynamics may have
taken much longer.

Address for Correspondence Suggested Reading

J Srinivasan
Chairman, Centre for Atmo- [I] TheSecondLa~ ofZTwrmodymzmics,Ed.J Kestin, Dowden,Hutchinson
spheric & Oceanic Sciences and Ross Inc., 1976.
Indian institute of Science [2] D S L Cardwell, From Watt to Clausius, Comell Univeristy Press,
8angalore 560 0]2, India. Ithaca, NY, 1971.
Email: ]ayes@caos.iisc.ernet.in [3] C C Gillispie, Lazare Carnot Savant, Princeton University Press,
Princeton, NJ, 1971.

A n A n c i e n t I n d i a n P r o o f o f t h e R i e m a n n H y p o t h e s i s ?!
~+ ~ . -.'. : .' .

9 I t has come to/~ht,l~ the lo,m o ~ R i e m m m hy~ .j~hesis

which isthought to, be as
yet unsolved, was actually already solved by and known to the arw.ient Indians in
their monumental work "Ramayana : The name ~Riemann zeta function "is actuaUy
9 9 . , , .

a corrupted version of the 'Roman Sita function: The reason the name "Sita' became "Zeia'on
reaching Germany is clear as the German prrmounciation of the letter '$' is similar to the English
pronunciation of the letter 'Z'. What the western world calla the ~ritical line' is already known to
the ancient Indians as the 7 . ~ h m a n Reltha: Having been drawn by Lakshmana, a half-brother
of Roman, the critical line is atso known at times by the name of%all-line: Sita vanished precisely
when she stepped on the critical llne.
- ~ . - .

It is not clear whether this proof did rcack t ~ western world although there are reports that the
name of Vashishta did reachGerm~my.. Unfortunately, they could make nothing of it and forgot
the whole thing after merely quipping ']~as ist?'

Hanuman 's character came to be known tO:the wes~rn world where it came to be identified as one
with super powers who often flew over mountains and ot~ans in a cape rescuing damsels in
distress. Of course, gradually, "Hanuman' became 'Hanu Man' and following that it became
'Simian Man' which finally ended up as a big "S'. (Another version has it that due to his attribute
of scattering largesse to the multitude, he himself became a large "S"
B Sury, ISI, Bangalore

48 RESONANCE I November 2001