Treatise with Reasoning Proof of the Second Law of Energy Degradation:

The Carnot Cycle Proof, and Entropy Transfer and Generation

Milivoje M. Kostic
Northern Illinois University
www.kostic.niu.edu ; Email: Kostic@niu.edu
© 2006-2008 by M. Kostic (Manuscript, Version 1a, April 6, 2006; Version 3, May 2008))
Updated/Printed: 5/13/2008 9:44 AM
Outline See updates at: http://www.kostic.niu.edu/2ndLaw/
and an article at: http://goo.gl/l93HK
I. Introduction
also: http://proceedings.aip.org/resource/2/apcpcs/1411/1/327_1?isAuthorized=no
II. Criticality of Language, Terminology andzation:
Understanding and Defining Concepts and Phenomena
III. Work and Heat Transfer, Reversibility and Irreversibility:
Energy Transfer, Redistribution and Disorganization, and Entropy Transfer and
Generation
IV. Physical Explanation and Reasoning Proof of the Carnot Efficiency: Thermal and
Mechanical Net-Expansion -- Reversible Conservation of Energy and Entropy
V. Physical Explanation and Reasoning Proof of the Second Law of Energy Degradation:
Lost of Work Potential, and Generation and Increase of Entropy
VI. Concluding Remarks: Energy is Conserved, Redistributed (Dissipated) and Degraded

Section IV below, other sections are being prepared. Some introductory comments follow:
(*) History of thermodynamics: http://en.wikipedia.org/wiki/History_of_thermodynamics
“It is crystal-clear (to me) that all confusions related to the far-reaching fundamental Laws of
Thermodynamics, and especially the Second Law, are due to the lack of their genuine and subtle
comprehension.” (Kostic, 2006).
There is a cultural abyss between the literary-arts and the exact-sciences intellectuals, and
even between their subgroups. “The Second Law of Thermodynamics” is a vivid illustration:
some of the literary arts intellectuals are “proud” of not knowing it, while expect that all
intellectuals be familiar with “Work of Shakespeare.” The exact science is, in its own right, a vital
part of civilization, and should be valued far beyond its technological applications, especially the
fundamental laws of nature. Namely, the phenomenological Laws of Thermodynamics have much wider,
including philosophical significance and implication, than their simple expressions based on the
experimental observations.
The Second Law made its appearance around 1850, but a half century later it was already surrounded
by so much confusion that the British Association for the Advancement of Science decided to appoint a
special committee with the task of providing clarity about the meaning of this law. However, its final
report (Bryan, 1891) did not settle the issue. Half a century later, the physicist/philosopher Bridgman
(1941) still complained that “there are almost as many formulations of the Second Law as there have been
discussions of it.” And even today, the Second Law remains so obscure, due to the lack of its comprehension,
that it continues to attract new efforts at clarification, including this one.
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The theory of classical thermodynamics was originally based on thermal and mechanical energy
transformations, and is characterized by an empirical, often called “phenomenological” approach,
formulated on empirical, but universal principles that deny the possibility of various kinds of perpetual
motions, while at the same time avoids speculative assumptions about the microscopic constitution and
complex dynamics of the considered material systems. The physical systems are regarded as “black
boxes” and all specific thermodynamic quantities and their general properties are derived by means of
these principal laws. This is the approach to the theory taken by the pioneers: Carnot, Clausius, Kelvin,
and Planck, and with some exceptions by Gibbs.
The classical, phenomenological thermodynamics today has unjustifiably a dubious status. Many
modern physicists regard classical thermodynamics as an obsolete relic. Often, mostly due to lack of
dubious comprehension, the thermodynamics is considered as an engineering subject and thus not as
the most fundamental science of energy and nature. However, a number of prominent modern physicists
have acknowledged fundamental importance of thermodynamics. Einstein, whose early writings were
related to the Second Law, remained convinced throughout his life that “thermodynamics is the only
universal physical theory that will never be refuted.” Many other renowned physicists have been
impressed by the universal and indisputable validity of thermodynamics principles. Apart from the view
that Thermodynamics is obsolete, there is a widespread belief among scientists in Thermodynamics
absolute authority.
Maxwell (1877) regarded the thermodynamics theory as “a science with secure foundations, clear
definitions and distinct boundaries.” But there are also others who dispute its clarity and rigor. Arnold
(1990) stated that “Every mathematician knows it is impossible to understand an elementary course in
thermodynamics.” Von Neumann once remarked that “whoever uses the term “entropy” in a discussion
always wins since no one knows what entropy really is, so in a debate one always has the advantage.”
The historian of science and mathematician Truesdell (1966) explains in his essay of Method
and taste in natural philosophy: “Heads have split for a century trying to define entropy in terms of
other things. Entropy, like force, is an undefined object, and if you try to define it, you will suffer the
same fate as the force-definers of the seventeenth and eighteenth centuries: Either you will get
something too special or you will run around in a circle.”
Existing language terminology defines known concepts, phenomena and experiences, thus it cannot
explain precisely new concepts without “misuse and abuse” of existing terminology until new one is
established. Due to “misuse of language” and individual perception of reality the scientific history has
witnessed many useless and on occasion harsh debates including lost friendships. Trying to understand,
reason and explain fundamental concepts is a daunting endeavor, and different from understanding other
concepts derived from the fundamental ones. However, there is factual reality that we should be always
aware of and guided by. The fundamental interactions and their inter-relations along with subtle reasoning
may help to resolve ambiguities and close the needed loops. “Going in circle” does not mean we are not
going anywhere as long as we succeed in comprehension of the “circular” subtle interactions, including
interrelated causes and effects. A barrier between our understanding and reasoning explanation is a
language ambiguity, which could be partially offset by more objective and more primitive mathematics,
but a price paid is the discrepancy between reality and mathematical idealizations and simplicity, but
sometimes unnecessary complexity. Another critical tool for resolution of reasoning ambiguities is
experimental ingenuity with observation and quantification of reality, and again the price paid is the
discrepancy between reality and experimental limitations, including inevitable and unconscious errors and
uncertainties. We must bear in mind that new ideas and concepts (a way one perceive reality) are not only
difficult for a reader to grasp but equally difficult and excruciating for an author to express, as it is
experienced here. There is a need of using synonyms, redundant and imaginative explanations, quotation
marks for words that are not quoted, and similar, since new or creative ideas, concepts and explanations
are to be expressed with existing word terminology [5].
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IV. The Physical Explanation and Proof of the Carnot Efficiency: Thermal and Mechanical
Net-Expansion -- Reversible Conservation of Energy and Entropy

Carnot’s “Reflections on the Motive Power of Fire (Heat)”

Carnot reasoning of reversible cycles is in many ways equal if not more significant than the
Einstein’s relativity theory in modern times.

Sadi Carnot (then at age 28) published in 1824, now famous “Réflexions sur la puissance
motrice du feu (Reflections on the Motive Power of Fire [1]).” At that time, when the energy
conservation law was not known and heat was considered as indestructible caloric, when heat
engines were in initial stage of development with efficiency of less than 5%, the confusion and
speculations flourished. Can the efficiency be improved by different temperatures or pressures, a
different working substance than water; or some different mode of operation than pistons and
cylinders? With ingenious and far-reaching reasoning, Carnot answered all of those questions
and proved that maximum, limiting efficiency of heat engine does not depend on medium used in
the engine but only depends on (and increases with) the temperature difference between the heat
source and cooling medium or heat sink, not directly as, but similarly to the water wheel
efficiency dependence on the waterfall height difference (see Fig. 1, formulas are developed after
Carnot followers’ work). In addition Carnot introduced the reversible processes and cycles and
proved that maximum heat engine efficiency is achieved by any reversible cycle (thus all must
have the same efficiency), i.e.:

“The motive power of heat is independent of the agents employed to realize it; its quantity is
fired solely by the temperatures of the bodies between which is effected, finally, the transfer of
the caloric.” [1] .

WnetOUT
WC = WnetOUT = QIN ⋅ f c (TH , TL ); ηC = = f c (TH , TL ) (1)
QIN 1424 3
Max Qualitative function Rev.

Carnot cycle consists of four reversible processes, see Fig. 2: isothermal heating and expansion
at constant high-temperature TH (process 1-2); adiabatic expansion to archive low-temperature TL
(process 2-3); isothermal cooling and contraction at constant low-temperature TL (process 3-4);
and adiabatic compression to archive high-temperature TH and complete the cycle (process 4-1).
All processes are reversible, thus the cycle could be reversed along the same path and with the
same quantities of all heat and work in opposite directions (in-to-out and vice versa), see Fig. 3,
i.e.:

{QH , QL ,WC } ⇔
{ {− QH ,−QL ,−WC } (2)
IF REVERESED

The consequence of the cycle reversibility is far-reaching, see Fig. 4 (see also next Section). Let
us consider three heat-engine (HE) cycles on Fig. 4: two reversible, HER1 and HER2, and third
irreversible, HEIrr. The cycles are taking place between the same temperature reservoirs (one at
TH and other at TL<TH) and consuming the same quantity of heat QH, but have different
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efficiencies (η R1 < η R 2 < η Irr , where η = WnetOUT / QH ). If we reverse the HER1 with the smallest
efficiency and couple it with either HER2 or HEIrr then the net-effect will be production of net-
work ( WIrr − WR1 > WR 2 − WR1 > 0 ) while consuming heat ( QL , R 2 Irr − QL , R1 ) from one thermal
reservoir only; or alternatively, if the three heat-engines produce the same amount of work WR1,
then the higher efficiency engines will require less heat consumption ( QH , Irr < QH , R 2 < QH ), and
then the net-effect will be transferring heat ( QL , R 2 Irr − QL , R1 ) from low-to-high temperature
reservoirs only (from TL to TH), thus violating the Second Law of Thermodynamics (perpetual
motion machine of the second kind), see Fig. 4. At the time, Carnot was under impression that
the above scenario will be producing work without spending any caloric and thus violating the
impossibility of the perpetual motion machine (of the first kind; note that neither
Thermodynamics not its Laws were known at that time) [2,3]. The above analysis proves that a
reversible cycle cannot have smaller efficiency than any other cycle, thus all reversible cycles
(we could have reversed either HER1 or HER2 but not HEIrr irreversible one) must have the same
maximum possible efficiency for the given temperature of the two thermal reservoirs,
independently from anything else, including the nature of heat-engine agent undergoing the
cyclic process. Since the irreversible cycles could not be reversed they may have lower than
maximum reversible efficiency up to zero (no net-work produced) or even negative (external
work input required to run an engine), i.e.:

η Irr < η Rev = η max = f C (TH , TL ) (3)

Carnot did not provide quantitative, but qualitative relation for the ideal heat engine efficiency,
and specified conditions that must be satisfied to achieve the maximum efficiency: the need for
“re-establishing temperature equilibrium for caloric transfer,” i.e. reversible cycles, where heat
transfer has to be achieved at negligibly small (in limit zero) temperature difference at both
temperature levels, TH , high temperature for heat source (heating), and TL , low temperature for
heat sink (cooling of heat-engine medium), see Fig. 3.

Carnot ingenious reasoning (1824), at the time when little was known about heat and work
interactions, much before establishment of the “mechanical equivalent of heat” (Joule, 1843),
helped his followers to extend his work and to define absolute thermodynamic temperature
(Kelvin, 1848) and entropy, a new thermodynamic material property (Clausius, 1850, Boltzman,
1880), as well as the Gibbs free energy (Gibbs 1878), one of the most important thermodynamic
functions for the characterization of electro-chemical systems and processes, like the voltage
outcomes of an electrochemical cell, and the equilibrium constant for a reversible chemical
reaction. The Carnot work, almost unnoticed at his time and not enough recognized even now,
has have unprecedented and far-reaching consequences, and was crucial for development of new
science of Thermodynamics. Carnot answered many questions related to the equivalency of
“motive power” and “heat” through his ingenious reasoning of reversible cycles. His reasoning
opened the way to generalization of reversibility and energy process equivalency (conserving
non-equilibrium during reversible processes), and formulation of the far-reaching Second Law of
Thermodynamics:

Carnot reasoning of reversible cycles is in many ways equal if not more significant than the
Einstein’s relativity theory in modern times.
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Carnot reasoned that mechanical expansion and compression are needed to decrease and increase
the temperature of the engine medium to match the temperature of the high- and low-temperature
thermal reservoirs, respectively, and thus provide for the reversible heat transfer (see also [4]).
Carnot then reasoned that in limiting case a reversible cycle could be reversed using the obtained
work and transfer back the heat from low- to high-temperature thermal reservoirs (refrigeration
cycles are reversed heat engine cycles), see Fig. 3 and Eq. (2).

Actually, Carnot (1824) established the fundamentals for the second Law of thermodynamics
(Clausius 1850, and finalized by Thomson in 1874), before the First Law was even known
(Meyer, 1841; Joule, 1843, and finalized by Helmholtz, 1847).

Kelvin Absolute Temperature

Carnot analyzed critical concepts and qualitative relations related to the “motive-power
equivalent of heat” through his ingenious reasoning of reversible cycles, before the Joule’s
“mechanical equivalent of heat” was even known. Only after the latter was established it was
possible (actually easy) to quantify Carnot engine efficiency, i.e.:

WnetOUT QH − QL Q
ηC = = =1− L (4)
QIN QH QH

The above Eq. (4) is valid for both, real and ideal, reversible heat engine cycles. However, for
reversible Carnot cycles the efficiency depends only on the temperature values of the two heat
reservoirs (Eq. 1). Furthermore, more specific relation for the Carnot efficiency could be inferred
by considering the three related Carnot cycles on Fig. 5. For a given TH, for arbitrary high-
temperature reservoir and given arbitrary low TRef, for reference-temperature reservoir, the
combined Carnot efficiency of the two heat engines, HEHT and HETR, cascaded at an arbitrary
intermediate temperature level T, must be the same as the corresponding Carnot efficiency of a
third heat engine HEHR, running between the two temperature reservoirs with the same heat input
QH, and thus releasing the same heat QRef, at a given reference temperature TRef, see Fig. 5. Thus
for everything, but intermediate temperature T, given as fixed quantities, the heat Q(T)
transferred from HEHT to HETR engine must be directly proportional to QRef (efficiency is an
intensive HE property) and an increasing function of T only, i.e.:

Q(T ) = QRef ⋅ f (T , TRef ) T = given

= QRef ⋅ f (T ) (5)
Ref

Then, the above could be applied for any temperature level, say T=T1 or T=T2 or T= TH, and
very important correlation deduced:

Q(T1 ) QRef ⋅ f (T1 ) f (T1 ) T1 Q1

= = = = (6)
Q(T2 ) QRef ⋅ f (T2 ) f (T2 ) f ( T ) =θ = T
T2 Q2

The above function f(T) could be any arbitrary, but non-negative and increasing function of
temperature, thus defining a new absolute temperature scale, say θ = T .
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The above function, the Carnot ratio equality (Eq. 6), is much more important than what it
appears at first. Actually it is probably the most important equation in Thermodynamics and
among the most important equations in natural sciences.

Not only that Eq. (6) defines the Thermodynamic absolute temperature scale, which is
independent of the substance of a thermometer, but it will define a fundamental property of
matter, the entropy S, the related process-equilibrium functions and correlations, and quantify
irreversibility (loss of work potential), and the far-reaching Second Law of Thermodynamics.

In some references the Carnot ratio equality of heat and related absolute temperature function
ratios is deduced from the following reasoning, see Fig. 5 again:

⎛ QRef ⎞ ⎛Q ⎞ ⎛ QRef ⎞
⎜⎜ ⎟⎟ = 1 − f C (TH , TRef ) = ⎜⎜ T ⎟⎟ ⋅ ⎜⎜ ⎟⎟ = f C1 (TH , TT ) ⋅ f C1 (TT , TRef )
⎝ QH ⎠ 1Not 442443 ⎝ QH ⎠ ⎝ QT ⎠ 14 44424444 3
function of T Dependance of T must cancel must be (7)
⎛ f (TT ) ⎞ ⎛ f (TRef ) ⎞ ⎛ f (TRef ) ⎞ ⎛ QRef ⎞
= ⎜⎜ ⎟⎟ ⋅ ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟
⎝ f (TH ) ⎠ ⎝ f (TT ) ⎠ ⎝ f (TH ) ⎠ ⎝ QH ⎠

Now, it is easy to write the correlation to define the absolute temperature scale for a given
arbitrary reference temperature and unit increment, say TRef= 273.15 K and unit of absolute
temperature 1 K = 1 0C (Kelvin, 1848), i.e.:

T Q(T ) Q(T ) Q(T ) Q(T )

= = or T = TRef = TRef (8)
TRef Q(TRef ) QRef Q(TRef ) QRef

Where, Q and QRef , are heat transferred in any reversible Carnot cycle working between an
arbitrary temperature T and the reference temperature TRef.

Clausius Equality (Entropy) and Inequality

Another important consequence of the Carnot ratio correlation, Eq. (6), for a Carnot cycle
working between the two constant temperature thermal-reservoirs, T=TH or T=TL, is:

QH , IN QL ,OUT Q(TH ) Q(TL )

− = + = 0; where Q (T ) = QIN = −QOUT > 0 (9)
TH TL TH TL

Or in general, for a variable temperature, reversible Carnot Cycle working between the variable
temperature thermal-reservoirs, see Fig. 6, and after integration of Eq. (9) for infinitely many
Carnot cycles of infinitesimally small heat transfer δQ at virtually constant temperature T , we
have:
B
⎛ δQH , IN δQL ,OUT ⎞ ⎛ δQ(TH ) δQ(TL ) ⎞ δQ(T )
∫ ⎜⎜⎝
A
TH
−
TL
⎟⎟ = ∫ ⎜⎜
⎠ ⎝ TH
+
TL ⎠
⎟⎟ = ∫
T
=0 (10)
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This is well-known Clausius equality (more about Clausius inequality later), which defines new
fundamental property entropy, since it is independent on process path Q(T), namely (compare
with Eq. 10):

δQ B
δQ (TH = Tany ) A
δQ (TL , as given ) B
δQ (TH = Tany ) B
δQ (TL , as given )
∫ T
=∫
TH
+∫
TH
=∫
TH
−∫
TH
=0
Cycle A Re v B Re v A Re v A Re v
14442 444
3 144
42 444
3 14442 444
3 144
42 444
3
Any Rev. Path Fixed Pat Any Rev. Path Fixed Pat
(11)
δQ (TH = Tany ) δQ (TL , as given )
= const (independent of path Q (T = Tany )
B B
S A − SB = ∫ =∫
T TH 144444 42444444 3
1
A
442H443 A
144
42 Re v
444
3 Thus System Property
Any Rev. Path Re v Fixed Path

For real, irreversible cycles, the heat engine efficiency is smaller than for reversible cycles, i.e.,
for everything else being the same WIrr<WRev. Then we can reason the proof of the famous
Clausius inequality as follow:

(W = ∫ δQ ) < (∫ δQ
Irr Irr Rev = WRev ) (12)

δQ ⎛ δQ ⎞ δQ
∫T < ⎜⎜ ∫ = 0 ⎟⎟ or ∫T ≤0 (13)
⎝14 3⎠
T Re v
Irr
4244
Eq . (10 )

Physical Explanation and Reasoning Proof of the Carnot Work Equivalency of Heat

Joule’s experiments have proved the equivalency of fully irreversible conversion of mechanical
work to heat or more accurately via generated heat into the internal thermal energy (of a single
thermal reservoir). However, the Joule’s “mechanical equivalent of heat” does not work for
thermal energy (or heat) conversion to mechanical energy, since it is not possible to reverse
original, fully-irreversible Joule’s process and convert heat (thermal energy) from a single
reservoir to work without any other impact with the surroundings. Here the Carnot principle
provides the missing “heat equivalent of work” or “Carnot motive-power equivalent of heat” via
reversible heat-engine conversion of thermal energy into mechanical work. In order to extract
work from a heat reservoir, it is necessary to employ a heat engine running a power cycle, while
transferring part of the heat from a high-temperature reservoir to a low-temperature reservoir,
that is, it is necessary to have, in addition to high-temperature reservoir for heating, also a low-
temperature reservoir to cool a part of the heat-engine cycle. Without the low-temperature
reservoir to provide thermal compression by cooling (cycle heat removal) all obtained expansion
work (or even more in non-ideal cycle) will be needed to compress the cycle medium to the
original temperature and all absorbed heat (or even more in non-ideal cycle) has to be removed
out from the cyclic medium in order to complete the cycle, see Fig. 7 (right).

Heat transfer is manifested as internal-thermal energy transfer due to temperature difference,

both the internal-thermal energy as an extensive quantity and the temperature as an intensive,
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particulate quantity are related (in its own right) to random motion of molecular or other
substructure of a material system [5]. The entropy is a measure of a system internal-thermal
energy randomization in space per absolute temperature level (from the Clausius equality).
During the heat transfer (across a stationary boundary, thus no work transfer), the randomized
energy along with entropy is transferred, while during the organized energy transfer in form of
work (no random but directional boundary displacement) no entropy will be transferred,
therefore all mechanical reversible processes are isentropic. It means that any reversible
mechanical (adiabatic) cyclic process will be isentropic with zero net-work (up-down only on the
T-S diagram). Furthermore, any thermal cyclic process with reversible heat transfers at
infinitesimally small temperature difference with a constant-temperature reservoir only, will
close the cycle with zero net-heat (right-left only on the T-S diagram). Therefore, any thermo-
mechanical reversible cycle working with a constant-temperature reservoir only, see Fig. 7-right
and Fig. 8-top, regardless of complexity and including internal regenerative reversible heat
transfer (processes 7-8-9 and 15-16-17 on Fig. 8-top, for example), may be composed of
arbitrary many adiabatic expansion-compression and equal amount of overall thermal heating-
cooling, resulting in net-zero work and net-zero heat for any cycle (limiting zero Carnot
efficiency when TH=TL). Since a reversible cycle is the most efficient one, it follows that no
positive net-work out could be obtained from a single constant-temperature heat reservoir. Any
irreversible cycle with a single constant-temperature heat reservoir will result in negative net-
work-out or will require net-work-in, i.e., will be irreversibly converting mechanical energy via
heat into the thermal energy of the single heat reservoir, and with such irreversible process we
will confirm the Joule’s “mechanical equivalent of heat.” Therefore, the above reasoning proves
the following [similar to the Clausius inequality, Eq. (13)]:

⎧= 0, for a reversible cycle ⎫

WnetOUT = ∫ δQ(T ) ⎨ ⎬ ≤0 (14)
T =const < 0, for an irreversible cycle
⎩ ⎭ T =const

Furthermore, see Fig. 8-bottom, it is obvious that any combination of thermo-mechanical

reversible processes, including arbitrary regenerative reversible-heating and cooling (must be
overall net-zero regeneration, processes 7-8-9=7 and 17-18 & 19-20), must satisfy the Carnot
ratio equality for two constant-temperature reservoirs (see Eq. 15), or Clausius integral equality
for variable temperature heat reservoirs (Eq. 10):

∑ Q(T H )
+∑
Q(TL ) QH , netIN QL , netOUT
= − = 0; where Q(T ) = QIN = −QOUT > 0 (15)
TH TL TH TL

Then the net-work out and the reversible cycle efficiency for an arbitrary reversible cycle
between the two constant-temperature reservoirs (see Fig. 8-bottom) will be:

QH ,netIN
WnetOUT = QnetIN = QH ,netIN − QL ,netOUT = (ΔT )
TH
(16)
Q
= L ,netOUT (ΔT ) ; where ΔT = TH − TL
TL
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WnetOUT ΔT TH − TL T
ηC = = = = 1− L (17)
QH ,netIN TH TH TH

TABLE 1: Carnot cycle with ideal gas as working medium, see Fig. 2.
Process Condition QnetIN = ΔU + WnetOUT WnetOUT = QnetIN − ΔU

V2 V2
1-2 TH=const 0 + R g T H ln = Q H , IN RgTH ln − 0 = WH ,OUT
V1 V1
TL V
2-3 SE=const CV ln + Rg ln 3 = 0 0 − Cv (TL − TH ) = WE ,OUT
TH V2
V4 V4
3-4 TL=const 0 + R g T L ln = − Q L ,OUT RgTL ln − 0 = −WL ,IN
V3 V3
T V
CV ln H + Rg ln 1 = 0 0 − Cv (TH − TL ) = −WC ,IN = −WE ,OUT
4-1 SC=const
TL V4
WnetOUT = QnetIN
QnetIN = Rg (TH − TL )ln
V2
Cycle
= Rg (TH − TL )ln
1-2-3-4-1 V1 V2
V1
WnetOUT = QnetIN
= Rg (TH − TL )ln 2
(1-2) All V
QnetIN
= Rg (TH − TL )ln
+(3-4) Thermal
V2
V1
V1
(2-3) All
+(4-1) Adiabatic
Q ad netIN = 0 W ad netOUT = 0

R T ln(V4 / V3 ) TL
NOTE: From Q2 −3 = Q4 −1 = 0 it follows that V3 = V4 or V2 = V3 . Then, QL = g L = , confirms
V2 V1 V1 V4 QH Rg TH ln(V2 / V1 ) TH
equality of ideal gas and Thermodynamic absolute temperature scales. Overall adiabatic processes do not
contribute to any net-energy conversion, but only adjust temperature for reversible heat transfer.

Or for a variable-temperature heat reservoirs, see Fig. 6, we have:

S B = S Max

W
∫ [T
S A = S Min
H ( S ) − TL ( S )]dS
∫ T (S )dS
η C = netOUT = S B = S Max
= (18)
QH ,netIN QH ,netIN
∫T
H
S A = S Min
( S )dS

The physical analysis and proof given above could be confirmed using ideal gas with constant
specific heat, see Fig. 2 and Table 1. However, for real engine medium with more complex
TREATISE WITH REASONING PROOF OF THE SECOND LAW OF ENERGY DEGRADATION - M. KOSTIC, APRIL 6, 2006 PAGE 10 of 16

medium properties, including change of phase, the thermo-mechanical effects are coupled,
however the above reasoning proof is generally valid, since it is not dependent on the nature of
the engine medium.

As expected, all the reasoning proofs discussed above are confirmed with the related results for
an ideal gas in Table 1, since the Carnot cycle relations do not depend on nature of the working
medium.

Thermal and mechanical energy and their energy-potentials, temperature and pressure, are
interrelated (coupled). Reversible addition of work (mechanical compression) or heat (heating
via thermal energy transfer), or irreversible heating (via loss of work or work potential) will
increase simultaneously pressure (mechanical elastic energy potential) and temperature (thermal
energy potential), and vice versa. The reversible Carnot cycle is the “gauge tool” to uncouple the
mechanical energy from thermal energy. If we heat a gas in a piston its internal energy will
increase, and mechanical work potential with regard to other reference thermal reservoir is
expressed with Carnot efficiency (only if non-equilibrium exist, otherwise no work potential).
The cyclic process is ideal method to decouple and measure the mechanical power-equivalent of
the thermal energy. It is accomplished by an intermediary system, which after making the whole
reversible cycle (or integer number of cycles; very important) it will not make any trace (i.e.
change of volume or any other) by itself to the environment, since reversible processes do not
generate entropy, and it will come to the same final state as initial (same temperature, pressure,
volume, entropy, energy, etc.). There will be thermal and mechanical expansions and
compressions. The net work is due to the net-thermal expansion-compression, since the net-
mechanical expansion-compression is zero for any reversible adiabatic (isentropic) cycle
exposed to thermal reservoirs only (see ideal gas Carnot cycle, Table 1). However the
mechanical expansion-and-compression are needed to adjust temperature for reversible heat
transfer at virtually zero temperature difference. Such reversible cycle, in limit, will run
spontaneously when transferring heat from high to low temperature reservoirs and extract
maximum work possible. If the cycle is reversed by using the obtained work, it will transfer the
same heat in reverse, from low to high temperature, thus performing a reversible refrigeration (or
heat pump) cycle, to be elaborated elsewhere.

For given heat reservoirs’ temperatures, no other heat engine could be more efficient than a (or
any) reversible cycle, since otherwise such reversible cycle could be reversed and coupled with
that higher efficiency cycle to produce work permanently (create non-equilibrium) from a single
low-temperature reservoir in equilibrium (with no net-heat-transfer to the high-temperature
reservoir). This implies that all reversible cycles, regardless of the cycle medium, must have the
same efficiency which is also the maximum possible, and that irreversible cycles may and do
have smaller, down to zero (no net-work) or even negative efficiency (consuming work, thus no
longer power cycle). Carnot reasoning opened the way to generalization of reversibility and
energy process equivalency, definition of absolute thermodynamic temperature and a new
thermodynamic material property “entropy,” as well as the Gibbs free energy, one of the most
important thermodynamic functions for the characterization of electro-chemical systems and
their equilibriums, thus resulting in formulation of the universal and far-reaching Second Law of
Thermodynamics. It is reasoned and proven here that the net-cycle-work is due to the net-
thermal expansion-compression, thus necessity for the thermal cooling and compression,
TREATISE WITH REASONING PROOF OF THE SECOND LAW OF ENERGY DEGRADATION - M. KOSTIC, APRIL 6, 2006 PAGE 11 of 16

since the net-mechanical expansion-compression is zero for any reversible cycle exposed to a
single thermal reservoir only.

In conclusion, it is only possible to produce work during energy exchange between systems in
non-equilibrium. Actually, the work potential is measure of the systems’ non-equilibrium, thus
the work potential could be conserved only in processes if the non-equilibrium is preserved
(conserved, i.e. rearranged), and such ideal processes could be reversed, and thus named
reversible processes. When the systems come to the equilibrium there is no potential for any
process to produce (extract) work. Therefore, it is impossible to produce work from a single
thermal reservoir in equilibrium (then non-equilibrium will be spontaneously created leading to a
“black-hole-like energy singularity,” instead to the equilibrium with randomized equi-partition of
energy at particulate level). It is only possible to produce work from thermal energy in a process
between two thermal reservoirs in non-equilibrium (with different temperatures). Maximum
work for a given heat transfer from high to low temperature thermal reservoir will be produced
during ideal, reversible cyclic process, in order to prevent any other impact to the surrounding,
(like net-volume expansion, etc.; net-cyclic change is zero). All real natural processes between
systems in non-equilibrium have tendency towards common equilibrium and thus loss of the
original work potential, by converting other energy forms into the thermal energy accompanied
with increase of entropy (randomized equi-partition of energy per absolute temperature level).
Due to loss of work potential in a real process, the resulting reduced work cannot reverse back
the process to the original non-equilibrium, as is possible with ideal reversible processes. Since
non-equilibrium cannot be created or increased spontaneously (by itself and without interaction
with the rest of the surroundings) then all reversible processes must be the most and equally
efficient (will equally conserve work potential, otherwise will create non-equilibrium by
coupling with differently efficient reversible processes). The irreversible processes will loose
work potential to thermal energy with increase of entropy, thus will be less efficient than
corresponding reversible processes … this will be further elaborated and generalized in other
Sections of this “Treatise with Reasoning Proof of the Second Law of Energy Degradation,” --
the work is in progress to be finished soon.

References:

1. Sadi Carnot, Reflections on the Motive Power of Heat, English translation by R.H. Thurston
(1824) http://www.thermohistory.com/carnot.pdf or
http://www.history.rochester.edu/steam/carnot/1943/

2. J. Uffink, Bluff your way in the second law of thermodynamics, Studies in History and Philosophy
of Modern Physics, 32(3), 305-394 (2001) http://philsci-archive.pitt.edu/archive/00000313/

3. E.T. Jaynes, The evolution of Carnot's principle, in G. J. Erickson and C. R. Smith (eds.)
Maximum-Entropy and Bayesian Methods in Science and Engineering vol. 1, p. 267 (1988).
http://bayes.wustl.edu/etj/articles/ccarnot.pdf

4. Kostic, M., Irreversibility and Reversible Heat Transfer: The Quest and Nature of Energy and
Entropy, IMECE2004, ASME Proceedings, ASME, New York, 2004.
http://www.kostic.niu.edu/Kostic-Energy-Entropy-Irreversibility.pdf
TREATISE WITH REASONING PROOF OF THE SECOND LAW OF ENERGY DEGRADATION - M. KOSTIC, APRIL 6, 2006 PAGE 12 of 16

5. Kostic, M., Treatise with Reasoning Proof of the First Law of Energy Conservation, Manuscript,
Northern Illinois University, 2006, 2007.
http://www.kostic.niu.edu/1st-law-proof1-ALL.pdf

6. Kostic, M., Physics of Energy (Abstract), In Encyclopedia of Energy Engineering and

Technology (B. L. Capehart, Editor), ISBN: 978-0849336539, Taylor & Francis/CRC Press,
2007.
http://www.kostic.niu.edu/Energy_Physics-Kostic.pdf
TREATISE WITH REASONING PROOF OF THE SECOND LAW OF ENERGY DEGRADATION - M. KOSTIC, APRIL 6, 2006 PAGE 13 of 16

TH TH ZH
QH V
S=QH/TH
Z = ρgz
W= WW
W= W=
HE HE
=S(TH-TL) =V(ZH-ZL)
=(QH-QL)
S =QL/TL V
QL
TL ZL

Fig. 1: Similarity between a heat engine (HE) and a water

wheel (WW).

1 1 TH
P 2
T
QH , WH
QH WH
WC WE
TH
2 QL , WL
WE
4 3
WC TL
4
TL QH Q
W= (TH − TL ) = L (TH − TL )
QL TH TL
3
W T
WL ηCt = = 1− L
V QH TH

S
W W + WE − WL + WC Q H − QL T
ηC = = H = =1− L
QH QH QH TH

Fig. 2: Heat-engine ideal Carnot cycle: note thermal and mechanical expansions
and compressions (the former is needed for net-work out, while the latter is needed
to provide reversible heat transfer).
 TREATISE WITH REASONING PROOF OF THE SECOND LAW OF ENERGY DEGRADATION - M. KOSTIC, APRIL 6, 2006 PAGE 14 of 16
TH+
- TH
T TH
QH

WC|T WT|C

QL
TL+
- TL
TL
W = (W netOUT = WT |C − WC |T )
= (Q H , IN − Q L ,OUT = Q netIN ) = Q
Q H , IN Q L ,OUT
= (TH − TL ) = (TH − TL )
TH TL

S
Fig. 3: Reversible Heat-engine (solid lines)
and Refrigeration (dashed lines, reversed
directions) Carnot cycle.
TH
QH or QH
TH TH

QH QH (or QH,R2) QH (or QH,Irr) HEHT

? or WHT
WR1 WR2 WIrr
HER1 Q(T) WHR
or REF HER2 HEIrr
(or WR1) (or WR1) T HEHR
Q(T)
QL,R1 QL,R2 QL,I
WTR
TL HETR
⎛ W ⎞ ⎛ W W ⎞ ⎛ W ⎞
If(?) ⎜⎜η R1 = R1 ⎟⎟ < ⎜⎜η R2 = R2 = R1 ⎟⎟ < ⎜⎜η Irr = Irr ⎟⎟
⎝ QH ⎠ ⎝ QH QH ,R2 ⎠ ⎝ QH ⎠
QRef QRef
and QH = constant, then: WR1 < WR2 < WIrr
TRef
and QL,R > QL,R2 > QL,I (or QH ,R2|I < QH )
Q(T) =QRef ⋅ f (T) for given TRef
Fig. 4: If a reversible heat engine (HER1) has a
smaller efficiency than other reversible HER2 or
Fig. 5: For a fixed TH, TRref, QH, and QRef, the
irreversible HEIrr , then if HER1 is reversed
Q(T) is proportional to QRef (efficiency is
(Refrigeration REF cycle) and combined with other
intensive property) and an increasing function
HE, it will result in impossible net-work from a single
of T for a given TRef.
reservoir (WR2|I –WR1), or heat transfer from low to
high temperature (QH-QH,R2|Irr).
TREATISE WITH REASONING PROOF OF THE SECOND LAW OF ENERGY DEGRADATION - M. KOSTIC, APRIL 6, 2006 PAGE 15 of 16

δW = δQH − δQL = [TH ( S ) − TL ( S )]dS

T

TH(S)
B
A
TH(S)
δQL

W = ∫δW = ∫δQ = ∫ [TH (S) −TL (S)]dS

SB

SA

= ∫T(S)dS
dS S
Fig. 6: Variable temperature reservoirs
require multi-stage Carnot cycles

1 TH TL=TH 4H
2 1
T T
QH 2
QH
-QH
WC WT WT

QL WC
4 3 4L 3
TL TL
W WT − WC W − WC 0
ηC = = ηC =
W
= T =
QH QH QH QH QH
Q H − QL T QH − QL
= = 1− L > 0 =
T
= 1− L = 0
QH TH QH TH
S S

Fig. 7: Heat engine ideal Carnot cycle between two different temperature heat-reservoirs
(TH>TL and W>0) (left), and with a single temperature heat-reservoirs (TH=TL and W=0,
ideal reversible cycle) (right). Low-temperature thermal compression is needed (critical),
not the mechanical (isentropic) compression, to realize work potential between the two
different temperature heat-reservoirs, due to internal thermal energy transfer via heat
(W=QH-QL>0). The isentropic expansion and compression are needed to provide
temperature for reversible heat transfer, while net thermal expansion-compression
provides for the net-work out of the cycle.
TREATISE WITH REASONING PROOF OF THE SECOND LAW OF ENERGY DEGRADATION - M. KOSTIC, APRIL 6, 2006 PAGE 16 of 16
16
Zero (N0) area within the cycle path.
T
3
19
17
2 4 18 15 5
1 11
21 14 12 10
20 9
7
8
61
13
Reversible Cycle: 1-21-1
Reversible heat regeneration:
7-8-9 and 15-16-17
QnetIN = WnetOUT = 0 S

Reversible Cycle: 1-20-1

T Reversible heat regeneration: 7-8-9 and
17-18 & 19-20 3
2 4 5
TH 1 20 11
16
17
QB QA 12 9
10
TL 18 7
19 15 8
14 13 6
Q netIN = W netIN
Q L , netOUT
= QA + QB = ΔT > 0
TL
S
Fig. 8: Arbitrary reversible thermo-mechanical
cycle with a single constant-temperature reservoir
(including reversible regeneration heat transfer):
upon completion of the cycle the net heat and work
transfer are zero (top).
Arbitrary reversible thermo-mechanical cycle
between two constant-temperature reservoirs
(TH>TL) and including reversible regeneration heat
transfer: upon completion of the cycle the net heat
and work transfer are equal and positive (bottom).
Low-temperature thermal compression is needed
(critical), not the mechanical (isentropic)
compression, to realize work potential between the
two different temperature heat-reservoirs. The
isentropic expansion and compression are needed to
provide temperature for reversible heat transfer,
while net thermal expansion-compression provides
for the net-work out of the cycle.