The Evolving Second Law

Howard W. Butler
3A Quartz Drive, Westerly, RI 02891
Abstract. A brief historical review of the evolution of the Second Law from Sadi Carnot (1824)
to present times is presented. The complex nature of irreversibility is used to identify three interrelated domains of thermodynamics, each having a different mathematical form and different types
of application. In addition, a proposal is made to bring the nomenclature of the Second Law into
parallel alignment with that of the First Law. Some of this material is excerpted from a paper by the
author published in the July, 2007 issue of the Mechanical Engineering Magazine.

The Second Law developed in phases over some 125 years and is one of the most
abstract laws of physical science. It has been the bane of students and others seeking to
understand its complexities since its formulation.
The rst phase in the evolution of the Second Law is due to Sadi Carnot who was a
graduate of the famous Ecole Polytechnique in Paris. He joined the French Army Corps
of Engineers, where he became fascinated with the development of the steam engine.
He was impressed with the idea that such useful machines could be developed in the
total absence of guiding principles or analysis, but on empirical reasoning alone. His
technical background led him to try to remedy this situation, but he soon discovered that
a major obstacle was the inability to give mathematical precision to the many irreversible
effects, This led to his two most signicant discoveries.
The rst was the observation that all irreversible processes have associated with them
an ideal process that is the limiting case when the irreversibility is progressively reduced
to zero. This ideal case is amenable to mathematical analysis using the appropriate
available principles. The other discovery was the idea of combining several of these
ideal processes into a cycle, so that the last one ended where the rst one began. This
was quite novel, since no steam engine operated on such a cycle. By combining these
two ideas, Carnot was able to analyze a number of cycles in which caloric owed in
and out of the cycle while producing useful work. His most famous cycle has the caloric
added at a constant high temperature and leaving at a constant lower temperature. For
this cycle he demonstrated that the maximum possible efciency depended only on the
two temperatures, and was independent of the nature of the thermodynamic medium.
His work was published in the book,Reections on the Motive Power of Fire in 1824.
The second phase in the evolution of the Second Law took place in 1849, when
William Thomson (later Lord Kelvin) studied Carnots work, corrected the caloric heat
error, and discovered the absolute temperature scale. This led to his nding that the heat
discharged to the low temperature reservoir was only a fraction of that added by the
high temperature reservoir, and that the difference was work done by the cycle. He then
showed that the efciency of the Carnot cycle took the form = 1 To /T , where To is
lower than T .
CP1033, Meeting the Entropy Challenge, An International Thermodynamics Symposium
edited by G. P. Beretta, A. F. Ghoniem, G. N. Hatsopoulos
2008 American Institute of Physics 978-0-7354-0557-8/08/$23.00

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The third phase in the evolution of the Second Law was carried out by Rudolf
Clausius, who became aware of the work of Carnot, Joule and Kelvin in 1850. He
extended Kelvins modication of Carnots analysis by recognizing that the cycle might
have more than two heating and cooling processes, and that a more general form of
Kelvins modication could be expressed in the calculus form,
%

Q
=0
T

(1)

where T is the temperature at the surface across which the small quantities of heat ow.
During the next 15 years, Clausius studied the logic that Carnot used in his analysis, to
see if a more general expression than Equation (1) might obtain if an unspecied type
and amount of irreversibility occurred during the cycle. This effort was rewarded by the
discovery of his famous inequality,
%

Q
0
T

(2)

where the equality holds for reversible cycles, and the inequality for irreversible cycles.
Clausius recognized that when the cyclic integral of any quantity is equal to zero, the
integral of that quantity between different states is independent of the nature of the
process, and depends only on the end states, and hence on the change of a property.
Using the ideal form of Equation (1), he obtained the form of the Second Law,
Q
= dS
T

(3)

where S is the property that he named entropy. From 1865 until quite recently this was
the only form of the Second Law that was used in mathematical analysis. Occasional
recognition of the inequality in Equation (2) was given by indicating that an irreversible
process could go in one direction but not in another. In 1878, Willard Gibbs published
his famous treatise On the Equilibrium of Heterogeneous Substances, and established
the domain of classical thermodynamics which most textbooks followed.
Clausiuss inequality of Equation (2) can be rigorously converted to an equality by
recognizing that the magnitude of the negativeness of the cyclic integral is monotonically
related to the intensity of the irreversibility. As the intensity of the irreversibility is
reduced, this magnitude is correspondingly reduced. If it is reduced to zero,Equation
(2) becomes Equation (1). Thus Equation (2) may be written as,
%

Q
= , with 0
T

(4)

where is always positive for irreversible cycles. Moreover, this total magnitude for
the cycle accumulates bit-by-bit during the cycle wherever irreversibility occurs and is
simply the sum of all such bits. It is often called the entropy production, i.e.,
=

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(5)

Equation (4) becomes,

%

( Q/T + ) = 0, with 0

This is now in the proper form to be converted to a single process as,

D
# 2/
Q
+ = S2 S1
T
1

(6)

(7)

which is a general form of the Second Law for closed systems and where each term must
be expressed in the same units. For an open system, the right side must be supplemented
by the entropy of the convected mass. This is the form of the Second Law that should
be taught to all engineering students at an early stage in a rst course following the development of the First Law. Since it is not specic for a particular type of irreversibility,
the magnitude of is found by difference. This domain might be called engineering
thermodynamics.
Many interesting processes can be solved using Equation (7). For simple, steady
heat conduction it becomes Q1 /T1 Q2 /T2 + = 0, with Q1 = Q2 = Q12 , giving
= Q12 (T1 T2 )/T1 T2 showing that heat will only ow from point 1 to point 2 if
T1 exceeds T2 . For the adiabatic ow of an ideal gas through a throttling valve, =
S2 S1 = mR ln p2 /p1 showing that the ow must be from a high pressure to a
lower pressure region. Equation (7) may be used to solve more complex systems, often
suggesting ways to modify the processes so as to minimize the entropy production.
A third domain of thermodynamics was developed by Ilya Prigogine in 1945. As
a doctoral student in the Free University of Brussels he became interested in nonequilibrium thermodynamics, where the principle of local equilibrium is invoked. This
principle states that the derived intensive properties of a substance, v, u and s, retain the
same dependence on the state-determining properties, P and T when they vary in space
and time, as they do when there are no space-time variations. The applicability of this
principle is clearly dependent on the intensity of the space-time gradients. Fortunately, a
large number of important types of irreversible phenomena satisfy this condition over a
wide range of intensities, and terms in both the First and Second Laws must be expressed
as time rates. This requires the use of more advanced mathematics and instruction at the
graduate level.
The unique feature of this domain of thermodynamics is that particular types of
irreversibility may be included in the Laws, and the expression for the rate of production
of entropy contains positive terms for each type considered. Each term consists of
a product of a cause and an effect, leading to the derivation of a phenomenological
relationship between them. For example, in the case of heat conduction, a general form
of Fouriers law is found that applies to anisotropic substances such as crystals or
laminated materials where the conductivity is different in different directions. Similar
results are obtained for viscous stresses, diffusion and chemical reactions. When two or
more of such phenomena are acting simultaneously, they may have interrelated effects,
such as thermal diffusion or viscous heating.
There are several interesting corollaries to the Second Law. A non-equilibrium system
that is suddenly isolated from any energy transfer from its environment, will undergo
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internal changes that ultimately reduce the rate of entropy production to zero, with all
thermodynamic properties homogeneously distributed. A non-equilibrium system that
has all properties at the surface suddenly frozen it time, will undergo internal changes
that ultimately produce a stationary state where the rate of production of entropy is the
minimum consistent with the surface conditions. Such statements are usually simple to
verify for particular cases, but often more difcult to prove in general.
We have come to an understanding that thermodynamic irreversibility may take on
several forms and that each form may produce entropy over a range of monotonic
intensities. Moreover, when these intensities are extrapolated to zero. they all produce
zero entropy, and if two or more are acting simultaneously, their effect is cumulative and
the total is the sum of the individual effects. This would seem to cover all aspects of the
subject, but that is not the case. It turns out that certain substances and processes have
a natural ability to tolerate increasing intensities of irreversibility with commensurate
increases in entropy production only up to a certain point. When this point is reached, the
system nds alternate modes of behavior that make it possible to tolerate the increases.
Laminar boundary layer ow may proceed from a low to a higher shear rate then
suddenly collapse into a chaotic turbulence at higher rates. Continuous changes in
temperature gradients cause orderly increases in entropy production up to a point, then
without warning, a phase change may occur that disrupts this continuity. A particularly
interesting case is that of a viscous uid conned in the annulus between two cylinders,
the inner one being caused to rotate at an adjustable rate. For low rotational speeds, the
uid moves in circular paths in the annulus with varying shear rates across the annulus.
This results in a dissipation of work into internal energy causing a temperature rise
in the uid. The temperature gradients cause heat to ow from the inner to the outer
cylinder. For specied conditions, the velocity and temperature distributions may be
easily determined. However, and without warning, when the speed of the inner cylinder
is raised to a certain point, this simple ow pattern transforms itself into a complex
series of Taylor vortices that look like right and left hand springs wrapped around the
annulus. It might be concluded that this transition takes place because the new mode
produces entropy at a lesser rate than if the original mode continued, To my knowledge,
this has never been proved. Similar changes occur in chemical systems where one
stoichiometric relation holds for a certain range of chemical potentials then at some
point a new stoichiometry results in a new arrangement of the same atoms. If this idea is
generalized, it might be assumed that the monotonic relationship between the intensity
and the entropy produced holds from zero to some upper limit, then shifts to a new
monotony to take advantage of the lower entropy production. To the extent that this is
true, the idea represents a thermodynamic extension of the principle of least action in
applied mechanics.
In conclusion, it is important to note that an important aspect of the Second Law has
been neglected until recently. In every textbook, the First Law is clearly shown to be
all about the concept of energy, relationships between different forms of energy, with
each having universally recognized names and symbols, heat, Q, work, W , and internal
energy, U. By international agreement, the units for all energy forms are designated in
joules, in honor of the contributions of James Prescott Joule. In the case of the Second
Law, only one term has such a universally recognized name and symbol, the property
entropy, S. The following proposals are suggested to remedy this long neglect. First, that
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it be recognized that the Second Law is all about the the concept of entropy, relationships
between different forms of entropy, with each having universally recognized names and
symbols. With the name entropy generalized to a broad concept like energy, the property
should be re-named the internal entropy by analogy with internal energy. The term
containing Q/T has a special Second Law signicance beyond its First Law elements,
and might be called the entropy transfer, since like heat transfer, it only exists at the
surface. The (sigma) term is what makes the Second Law the most unique of all the
laws of science. Its positive-denite character has led to its being called the entropy
production, generation or creation. Finally, it is proposed that all forms of entropy be
designated in carnots, in honor of the man who struck the rst Second Law spark. If these
proposals, or equivalent alternatives could be widely adopted, much of the confusion
about entropy would be eliminated.

REFERENCES
1.

H.W. Butler, Tracing the Second Law, Mechanical Engineering Magazine, ASME, July 2007.

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