Preface: THREE STEPS toward UNDERSTANDING HEAT and ENERGY

Thermodynamics is the science of heat, one of its fundamental laws is the second law of
thermodynamics. There have been nearly as many formulations of the second law as there have
been discussions of it, observed Percy Bridgman (1941) in The Nature of Thermodynamics. It
remains so today. This state of the subject is akin to that of philosophy, as noted in an op-ed of
NYT, There are as many definitions of philosophy as there are philosophers, (What is a
philosopher? May 16, 2010). This, however, does not make the subject matter necessarily
incomprehensible, as the historian Durant once said, Every science begins as philosophy
Thermodynamics may seem to be a natural philosophy of heat because we inherited from Joule
and Kelvin, two pioneers of the science, their error of mistaking two things that are equivalent
(equal in quantity) to be ones that are convertible (exchangeable because they are equal in value).
This book aims for cleansing that philosophical error transforming the subject into a real science
of heat, finally.
Heat can be transferred, produced, and extracted. A
electric water kettle boils water when it is turned on, for
water is heated with heat produced from electric power
input. We also know that an air conditioner, which is
sometime called a heat pump, can extract heat from a
space and move this heat to be dissipated to another
space. But, most of us do not know that heat engines, in
fact all engines and all power producing devices, are heat
extraction devices as well. I want to talk about this
understanding, which has huge implication in how we
shall use energy resources in the future. This
understanding of heat will be elucidated as a three step
story: the first step of transfer of heat in a one-place
relation, the second step of the production of heat from
mechanical work in a two-place relation, and the third
step of the extraction of heat in a three-place relation.
What is this thing we call heat, which can be
transferred, produced and extracted? At the end of the 18th
century and the beginning of the 19 th century, the
prevailing theory of heat is the caloric theory, considering
heat or caloric as an imponderable weightless fluid
substance. The materiality of caloric was discredited by
Rumford, Mayer and Joule; the theory was supplanted by
the mechanical theory of heat (MTH, which became

hot cup of coffee cools down. An

CATEGORY of relations:
think, and is blue are
examples of one-place relation or
predicate (firstness).
respects is a dyadic or twoplace relation (secondness).
gives to is a triadic or threeplace relation (thirdness).
C. S. Peirce: A language adequate for
scientific or descriptive purposes must
contain relationship terms of all three
kinds, but there are no phenomena
that can only be described in a
language which contains expressions
for four-place relations. That is, an
erstwhile apparent four-place relation
can be reduced to a set of relations of
the three kinds, whereas thirdness is
irreducible.
_____________
Footnote in the above
examples represents a relatum
(plural_relata),
one of the objects between which
a rela-tion is said to hold.

known as thermodynamics) on the basis of the mechanical equivalent of heat (MEH, or the
equivalence principle), and has been viewed as a failed project. But the caloric theory was a
cogent theory in the treatment of heat transfer processes and thermal/chemical processes. Rather
than a discredited or disgraced theory, a case can be made that its place in science was the first
step toward understanding heat phenomena 1 the establishment of one-place relation, heat is
conserved, in thermal/chemical processes.
More than placing the caloric theory as an one-place relation theory, this way of using
category of relations (see sidebar on previous page) to understand theories is important in the
following sense: We all know that emergent from the caloric theory in the early 19 th century was
Carnots theory of heat (R e flexions1824, a memoir predated Mayers and Joules
publications). The overthrow of the caloric theory was a complicated affair and, strictly
speaking, it was Carnots theory that was absorbed into MTH by Kelvin and Clausius, the great
founders of thermodynamics. However, their new emphasis on the definition of heat as a peculiar
motion of the ultimate particles of matter led them to misunderstanding Carnots theory of heat
as a caloric theory and adjudging it deficient because a caloric theory considered heat to be a
peculiar kind of substance. It was the latter-day emphasis on the mechanical definition of heat
that put his memoir in the wrong light (Hirshfeld Am. J. Phys. 23:103-105) misplacing it under
the category of caloric theories, whereas the thesis of this title will argue that the essence of
Carnots theory places it outside that category, and instead, under the category of a three-place
relation theory. That failure of Kelvin and Clausius to correctly characterize the target to which
they applied the force of their critical thinking, ironically, was the root of endless confusions
among students of thermodynamics continuing thereafter up to today.
Difficulty with caloric theory arose when Joule (1843-50) demonstrated that heat can be
obtained with no input of caloric, but only mechanical or electric work. This discovery led to the
acceptance of the two-place (dyadic) relation, i.e., the second step, between heat and work, thus
the understanding, Thermodynamics is mainly concerned with the transformations of heat into
mechanical work and the opposite transformations of mechanical work into heat (Fermi
Thermodynamics [1937]). In these transformations, it is energy rather than heat which is
conserved. Any suggestion in the symmetry of heat-to-work and work-to-heat, however, is
misleading, for the two-place, conservation-relation of work being converted into heatas
suggested by MEHcannot encapsulate the nature of the opposite relation, which should be, as
itll be argued, classified a three-place one. That is, in the second step, we only get the correct

1 Though that understanding failed to disclose the dynamical nature of heat, e.g., the static gas
structure of the caloric theory was completely contradicted by the later discovered kinetic nature
in gaseous molecules (see Fox The Caloric Theory of Gases [Oxford 1971])

understanding of the production of heat, not the extraction of heat for the production of work
(see details below).
Hint of asymmetry between work and heat could be found in the earlier insight reached by
Carnot in 1824. Carnot theorized that work is produced from the transfer of heat, whereas Joule
upheld that work is produced from the consumption of heat: Strictly speaking, only Carnot
framed his investigation as a problem of the production of work from heat and he noted, Heat
alone is not sufficient to give birth to the impelling power: it is necessary that there should also
be cold; without it, the heat would be useless, whereas Joules experimental investigations were
limited to the demonstration of the production of heat from work input; Joules generalization of
MEH from the proven equality of disappeared work and produced heat to the equality of
disappeared (consumed) heat and produced work was a bold postulate rather than a proven
conclusion. That proof came later. The conflict between the two assertions was resolved by
Thomson (later known as Lord Kelvin) in terms of the Carnot-Kelvin formula (obtained by
T1
Q2
T2
Kelvin, 1854), W rev =Q 2 1 T 2 , where
is a high-grade heat at temperature
. The

formula captures the asymmetry nature of the conversion of high-grade heat into work from that
of work into heat,2 and success in engineering application of high-grade heat in industrial and
transportation sectors proves the usefulness of that understanding. Kelvin, thus, was able to
frame thermodynamics in terms of energy andwith his announcing the universal tendency to
the dissipation of mechanical energy 3 (Kelvin [1852])that the two overarching principles of
energy to be its conservation and its availability (availability of energy in an energy system
inevitably decreases). In these works, Kelvin applied MEH with asymmetry understanding.
However, Kelvin was inconsistent. That is not a severe indictment as it might sound applied
to a pioneer of a new science, as Russell noted, A philosophy which is not self-consistent cannot
be wholly true, but a philosophy which is self-consistent can very well be wholly false. Kelvin
did get a lot right and in some instance his idea has become hugely influential as in the case of
aforementioned universal dissipation because people see the idea as self-evident. 4 While Kelvin
2 In the latter case all the mechanical energy is automatically converted into heat.
3 This will be referred to as the energy principle as Kelvins version of the second law of
thermodynamics and the Clausius/Planck version of the second law will be referred to as (for
short) the entropy principle.
4 This is one example of an idea that is self-evident but in fact (happily, one may add) not true,
as itll be demonstrated in the book that high grade energy dissipates spontaneously, but not
universally.

got it right with energys conservation and availability, he also accepted (after his initial
reluctance) Joules interpretation of the equivalence principle as the convertibility principle,
which held heat and work to be exchangeable, i.e., they have a symmetrical relation. In his
authoritative and influential 1851 paper On the dynamical theory of heat, Kelvin opened with
these fateful words, Considering it as thus established, that heat is not a substance, but a
dynamical form of mechanical effect, we perceive that there must be an equivalence between
mechanical work and heat, as between cause and effect. This account interpreting MEH to be
the principle of convertibility has since acquired almost biblical authority in textbooks
concerned with energy (Smith The Science of Energy [Univ. of Chicago 1998]): not only that
MEH asserts the equality of produced work and consumed energy (correctly, of course) but that
there is full equivalence or interconvertibility between work and heat (thermal energy) in the
sense of work causes heat and heat causes work. One of the results is the standard energy
definition todayenergy is the capacity of doing work (Maxwell: see Garver Science
43[No.1112]:567-71 [April 21, 1916]). That is an example of Kelvins legacy of profound
contributions to physics and engineering/industry that have also caused a lasting confusion due
to his inconsistency. The definition is either wrong since clearly energy is conserved while a
systems capacity for doing work is not, or that the definition is evidence of the widely held
energetic interpretation of thermodynamics by upholding the conservation principle while totally
disregarding the availability principle. Only energy matters.
Between 1854 and 1865, Clausius was on parallel track with Kelvin pursuing the

Qi

implication of a quantity
being shown to be zero for reversible cyclic processesand
i Ti
gradually he came to the realization that a new fundamental physical property was required
beyond energy in terms of the energy principleto make sense of the unidirectional nature of the
universe and finally in 1865 he introduced the concept of entropy. Later Planck (1887)
formulated the principle of the increase of entropy (short as the entropy principle), which will be
called the Clausius-Planck version of the second law. It must be recognized that the two versions
of the second law, the Kelvin version and the Clausius-Planck version (see Footnote 3), have not
been synthesized. Planck realized the need for synthesis and in fact emphasized, The real
meaning of the second law has frequently been looked for in a dissipation of energy. This view
[misrepresents the full meaning] of the question. There are irreversible processes in which the
final and initial states show exactly the same form of energyThey occur only for the reason
that they lead to an appreciable increase of the entropy (Planck [1897]; see also Footnote 4 in
which it is noted that this point can be used for refuting the universal dissipation principle).
Unfortunately this insightful point has not been duly appreciated and we still have the bizarre
situation among students of thermodynamics that the entropy law is accepted as the official
second law but the law is understood in terms of Kelvins energy (dissipation) principle. Kelvins

influence, though not being explicitly acknowledged, remains supreme: the general perception
on energy remains one that regards energy as the driver of changerather than energy as a
driver of change.
The real universal driver of change is entropy growth. Whereas entropy growth ensures the
production of heat from work in a dyadic framework, it is necessary to account for the
management of entropy growth to bring about the production of work. This account, however,
is not possible in the framework. Without this possibility, the second step of our journey has
suffered from an endless chain of paradoxes, (Mares et al. Thermochimica Acta 474:16-24
[2008]) a situation that has not escaped the notice of many scientists: E. Mach (1896), Callendar
(1910), Hirshfeld (1955), Truesdell (1980), and Mares et al. (2008).
Synthesis of the two versions of the second law is one principal goal of this book:
Dissipation of energy has served well (with appreciation to Kelvin) as a proxy to entropy growth,
which is the real driving force of change. Had dissipation of energy exhausted (completely
encapsulated) growth of entropy, there would have had no need of an independent concept of
spontaneity (entropy growth). The proxy would have been the real thing; but it is not. It is useful,
therefore, to introduce an independent concept of spontaneity, which is defined by the measure of
the non-equilibrium-ness of a system, resulting in a framework of triad: spontaneity, heat from
reservoir and mechanical work. This is the third step in understanding heat, a three-place
(triadic) relation in the heat phenomena of conversion of heat (thermal energy) into mechanical
work. In the triadic framework, fuel energy with spontaneous tendency (burning of which in a
boiler would produce a large amount of heat to be dissipated to a heat reservoir in a spontaneous
event) can insteadin an event of fuel inputted to an engineextract a part of the heat
converting it into mechanical work. That is, any power producing engine is a heat extraction
device in the triadic framework.
This development suggests what went wrong in the second step taken by Kelvin and
Clausius to be the result of their failure to understand that Carnots theory was not a caloric
theory of one-place framework. In fact by arguing, it is necessary that there should also be cold;
without it, the heat would be useless [in giving birth to power], Carnot laid out a framework of
the triad of heat, cold and poweran imperfect version of spontaneity, heat from reservoir and
power. Their dyadic framework made Kelvin and Clausius to view the advance in the theory of
heat they ushered in to be the rejection of calorics materiality in Carnots theory. But, the real
essence of which is its triadic framework not its conservation of caloric (which turned out to be
corresponding to the conservation of entropy for reversible processes). By unduly emphasizing
the dynamical definition of heat they accepted Joules interpretation of MEH as a principle of
convertibility (an equivalence between mechanical work and heat, as between cause and
effect) extending the equality of consumed (disappeared) heat and produced work to be the

inter-convertibility between heat and work. Whereas mechanical work may automatically results
in heat, the idea that heat can straightforwardly cause mechanical work was an error.
The correct understanding should be: MEH applies in the narrow sense to the one-way
dyadic transformation of work into heat while the other-way transformation may be understood,
instead, to be the entropic (entropy growth) equivalent of useful work (EEW), a triadic operation
of entropy growth potential which enables extraction of reservoir heat converting it into useful
work. Both ways are driven by entropy growth or irreversibility in nature: The former production
of heat results automatically from any dissipating mechanical energy with no human intervention
necessary (irreversibility as the sole mechanism)ending with entropy growth. The latter
production of work, in contrast, requires human (engineers) action (irreversibility as the driving
force but not the mechanism, which is supplied by man); the end result of the process in itself
ends with partial entropy growth; only at the eventual ending when work, or the orders (cities for
example) created by work, is dissipated or are disintegrated, the full entropy growth will be
realized. In all cases the ultimate ending is always the same: all entropy growth potentials turn
into dissipated heat eventually.
The principle of convertibility in failing to account for this fundamental difference in
causality between the two ways should be rejected as well as the idea that only energy matters,
which fails to accord entropy growth its role of universal driver of changes. The mechanical
theory of heat (i.e., standard thermodynamics), which rests on the foundation of convertibility
principle, should be supplanted by the entropic theory of heat (ETH) for self-consistency:
consistency might be a bad thing for philosophy (as noted by Russell) without empirical
grounding, but it surely is a good thing that a science of heat needs.
What ETH teaches is the following: Heat or energy alone can cause no work. Spontaneity
alone too causes little, or only modest amount of, mechanical energy. It is spontaneity (or energy
systems with spontaneity) as controlled by man which can produce significant amount of
mechanical energy. Energy matters but entropy growth matters more.
Another useful insight of ETH is that all reversible-like processes are heat extraction
processes as shown in Chapters 7 and 9. Chapters 9 to 12 represent the engineering application
of ETH. Chapter 10 of the book gives a review of traditional treatment of power cycles driven by
high grade heat: this part of application breaks no new ground other than injecting a perspective
of heat extraction interpretation of the Carnot-Kelvin formula. We did not have such a formula
for the rational handling of low grade heat; in Chapter 11 the idea of generalized heat extraction
is applied to reinventing the management of low grade heat for building conditioning. This
represents a new approach to an important energy consumption sector, which consumes around
40% of primary energy and about 50% of which (i.e., about 20% of total primary energy) is
consumed for building heating and cooling. A case is made that more than 90% saving of this
20% of total primary energy is possible to be derived from this new understanding of heat and

energy eventually resulting in technological change in how buildings will be designed, built and
operated.

The conceptual plot of the essay as it progresses through chapters is given here:
Chapter 1_Temperature (the measurement of the degree of heat)
Chapter 2_The measurement of heat
Chapter 3_The production of heat (the mechanical equivalent of heat [MEH])
Chapter 4_The production of work (the second law of thermodynamics)
Chapter 5_The entropy principle (the second law of thermodynamics)
Chapter 7_The meaning of heat and the definition of energy
Chapter 9_ The necessity of providing mechanisms for harnessing the driving force
and finally,
Chapter 12_Energy matters but entropy growth matters more