VERSIONS OF THE SECOND LAW OF THERMODYNAMICS

The "entropy always increases" version of the second law of
thermodynamics was a conclusion deduced by Clausius from two false
premises. Clausius eventually abandoned it but the enchanted
scientific world did not:

http://philsci-archive.pitt.edu/archive/00000313/
Jos Uffink, "Bluff your Way in the Second Law of Thermodynamics", pp.
39-40: "On many occasions Clausius was criticised by his
contemporaries. I do not know if, in his own time, he was criticised
in particular for his famous formulation of the second law as the
increase of the entropy of the universe. However, Kuhn (1978, pp.
13-15, p. 260) has pointed out the remarkable fact that in the book
(Clausius 1876) he eventually composed from his collected articles,
every reference to the entropy of the universe and even to the idea
that entropy never decreases in irreversible processes in
adiabatically isolated systems is deleted!"

Let us assume that Kelvin's version of the second law can be violated,
that is, in some cases, heat can be converted into work cyclically and
isothermally. Would there be respective violations of the "entropy
always increases" version? Only if Clausius' deduction of the latter
version is valid and based on true premises. If not, a scenario is
conceivable in which violations of the second law do occur in nature
but our entropic glasses prevent us from seeing them. In this scenario
the "entropy always increases" version automatically becomes the red
herring suggested by Ehrenfest-Afanassjewa and Uffink:

http://philsci-archive.pitt.edu/archive/00000313/
Jos Uffink, "Bluff your Way in the Second Law of Thermodynamics", p.
94: "This summary leads to the question whether it is fruitful to see
irreversibility or time-asymmetry as the essence of the second law. Is
it not more straightforward, in view of the unargued statements of
Kelvin, the bold claims of Clausius and the strained attempts of
Planck, to give up this idea? I believe that Ehrenfest-Afanassjewa was
right in her verdict that the discussion about the arrow of time as
expressed in the second law of the thermodynamics is actually a RED
HERRING."

Pentcho Valev

Take a suspended and stretched spring. It can lift a weight as it
contracts, that is, we GAIN work. However, in order to restore the
initial stretched state of the spring, we must SPEND work so there is
no net gain. If both contraction and stretching are carried out in a
reversible fashion, the net work gained at the end of the cycle is
zero.

Consider again a suspended and stretched spring but this time it is
"chemical", that is, we have one of the macroscopic contractile
polymers described by Dan Urry in:

http://pubs.acs.org/doi/abs/10.1021/jp972167t
J. Phys. Chem. B, 1997, 101 (51), pp 11007 - 11028
Dan W. Urry, "Physical Chemistry of Biological Free Energy
Transduction As Demonstrated by Elastic Protein-Based Polymers"

If, before contraction, we add acid (H+) to the system, the force of
contraction and, respectively, the work gained as the polymer
reversibly contracts increase. Then, just before stretching, we remove
the added H+ from the system: the force of contraction and,
respectively, the work spent as we reversibly stretch the polymer
decrease. At the end of the cycle, THE NET WORK GAINED FROM
CONTRACTION AND STRETCHING IS POSITIVE.

So far things go against the second law of thermodynamics but the
complete account requires that the net work gained from adding H+ to
and removing H+ from the system be evaluated. If it is positive or
zero, the second law is definitively violated. If it is negative, the
second law is saved for the moment.

In the absence of the polymer, adding H+ to and removing the same
amount of H+ from the system, in a reversible fashion, would amount to
zero net work gained. The polymers designed by Urry, however, release H
+ as they contract, and absorb H+ as we stretch them. It is easy (for
people experienced in electrochemistry at least) to see that this
makes the net work gained from reversibly adding H+ to and then
removing the same amount of H+ from the system POSITIVE.

Conclusion: The reversible cycle:

1. The polymer is stretched. We add H+ to the system.
2. The polymers contracts and lifts a weight.
3. We remove the same amount of H+ from the system.
4. We stretch the polymer and restore the initial state of the
system.

violates the second law of thermodynamics.

Pentcho Valev

If a constant-charge parallel-plate capacitor is totally immersed in
water, the force of attraction between the plates is 80 times weaker
than the force of attraction in vacuum. However, if we thrust some
solid dielectric between the plates (not necessarily occupying the
whole distance between them - it could be rather thin), the force of
attraction becomes even greater than in vacuum. Accordingly, the
following four-step cycle (carried out very slowly) violates the
second law of thermodynamics:

1. Plates are immersed and fixed. We thrust the solid dielectric.
2. Plates get closer. We GAIN work.
3. We withdraw the solid dielectric.
4. Plates get apart; initial state restored. We SPEND work.

When the plates are immersed in a liquid dielectric (water), some
additional pressure between them emerges, pushes them apart and so
counteracts their electrostatic attraction (W. Panofsky, M. Phillips,
Classical Electricity and Magnetism, Addison-Wesley, Reading,
Massachusetts (1962), pp. 111-116). If the plates are vertical and
only partially immersed, the same pressure forces the liquid between
the plates to rise above the surface of the water pool (see fig. 6-7
on p. 112 in Panofsky's book). What if one punches a small hole in one
of the plates, just above the surface of the pool? Will the lifted
water leak through the hole and fall? If lifting is due to an
additional pressure generated within the bulk, as assumed by Panofsky
and Phillips, then water WILL leak through the hole and the second law
will be violated. No matter how weak the waterfall is, in principle it
can rotate a waterwheel...

The perpetuum mobile of the second kind described above will never
become a money-spinner and will not solve the energy problems of
humankind. However Nature may occasionally have used such (inefficient
from an anthropocentric point of view) mecanisms and the knowledge of
them could make us unexpectedly rich in some unconventional sense.

Pentcho Valev

Panofsky's mysterious pressure produces a water bridge "defying"
gravity:

http://www.fmf.uni-lj.si/~podgornik/...ad/clanek2.pdf
J. Phys. D: Appl. Phys. 40 (2007) 6112-6114
The Floating Water Bridge, Elmar C. Fuchs et al.
"When high voltage is applied to distilled water filled into two glass
beakers which are in contact, a stable water connection forms
spontaneously, giving the impression of a floating water bridge."

Relevant quotations:

http://www.amazon.com/Introduction-E.../dp/0763738271
Introduction to Electromagnetic Theory: A Modern Perspective, Tai
Chow
p. 267: "Calculations of the forces between charged conductors
immersed in a liquid dielectric always show that the force is reduced
by the factor K. There is a tendency to think of this as representing
a reduction in the electrical forces between the charges on the
conductors, as though Coulomb's law for the interaction of two charges
should have the dielectric constant included in its denominator. This
is incorrect, however. The strictly electric forces between charges on
the conductors are not influenced by the presence of the dielectric
medium. The medium is polarized, however, and the interaction of the
electric field with the polarized medium results in an INCREASED FLUID
PRESSURE ON THE CONDUCTORS that reduces the net forces acting on
them."

http://www.amazon.com/Classical-Elec.../dp/0486439240
Classical Electricity and Magnetism: Second Edition (Dover Books on
Physics)
Wolfgang K. H. Panofsky, Melba Phillips
p. 114: "This means that if a system maintained at constant charge is
totally surrounded by a dielectric liquid all mechanical forces will
drop in the ratio 1/k. A factor 1/k is frequently included in the
expression for Coulomb's law to indicate this decrease in force. The
physical significance of this reduction of force, which is required by
energy considerations, is often somewhat mysterious. It is difficult
to see on the basis of a field theory why the interaction between two
charges should be dependent upon the nature or condition of the
intervening material, and therefore the inclusion of an extra factor 1/
k in Coulomb's law lacks a physical explanation"
p.115: "Therefore the decrease in force... cannot be explained by
electrical forces alone."
pp.115-116: "Thus the decrease in force that is experienced between
two charges when they are immersed in a dielectric liquid can be
understood only by considering the effect of the pressure of the
liquid on the charges themselves. In accordance with the philosophy of
the action-at-a-distance theory, no change in the purely electrical
interaction between the charges takes place."

Pentcho Valev

Carnot dealt with two reversible heat engines which DID NOT INTERACT.
In 1850 Clausius used NON-INTERACTING heat engines again:

http://www.mdpi.org/lin/clausius/clausius.htm
"Ueber die bewegende Kraft der Wärme", 1850, Rudolf Clausius: "Carnot
assumed, as has already been mentioned, that the equivalent of the
work done by heat is found in the mere transfer of heat from a hotter
to a colder body, while the quantity of heat remains undiminished. The
latter part of this assumption--namely, that the quantity of heat
remains undiminished--contradicts our former principle, and must
therefore be rejected... (...) It is this maximum of work which must
be compared with the heat transferred. When this is done it appears
that there is in fact ground for asserting, with Carnot, that it
depends only on the quantity of the heat transferred and on the
temperatures t and tau of the two bodies A and B, but not on the
nature of the substance by means of which the work is done. (...) If
we now suppose that there are two substances of which the one can
produce more work than the other by the transfer of a given amount of
heat, or, what comes to the same thing, needs to transfer less heat
from A to B to produce a given quantity of work, we may use these two
substances alternately by producing work with one of them in the above
process. At the end of the operations both bodies are in their
original condition; further, the work produced will have exactly
counterbalanced the work done, and therefore, by our former principle,
the quantity of heat can have neither increased nor diminished. The
only change will occur in the distribution of the heat, since more
heat will be transferred from B to A than from A to B, and so on the
whole heat will be transferred from B to A. By repeating these two
processes alternately it would be possible, without any expenditure of
force or any other change, to transfer as much heat as we please from
a cold to a hot body, and this is not in accord with the other
relations of heat, since it always shows a tendency to equalize
temperature differences and therefore to pass from hotter to colder
bodies."

NON-INTERACTION means that the work-producing force generated by the
first engine, F1, is independent of the displacement, X2, in the
second engine, and vice versa:

F1 = F1(X1, X2); F2 = F2(X1, X2)

dF1/dX2 = dF2/dX1 = 0

where "d" is the partial derivative symbol. It can be shown that, if
the two reversible heat engines DO INTERACT and the conditions are
isothermal, the equation:

dF1/dX2 = dF2/dX1

is a consequence of the second law of thermodynamics (Kelvin's
version). Accordingly, if the partial derivatives dF1/dX2 and dF2/dX1
are not equal, heat from a single reservoir CAN, cyclically, be
converted into work, in violation to the second law of thermodynamics.
Consider, for instance, INTERACTING "chemical springs". There are two
types of macroscopic contractile polymers which on acidification
(decreasing the pH of the system) contract and can lift a weight:

http://pubs.acs.org/doi/abs/10.1021/jp972167t
J. Phys. Chem. B, 1997, 101 (51), pp 11007 - 11028
Dan W. Urry, "Physical Chemistry of Biological Free Energy
Transduction As Demonstrated by Elastic Protein-Based Polymers"

Polymers designed by Urry (U) absorb protons on stretching (as their
length, Lu, increases), whereas polymers designed by Katchalsky (K)
release protons on stretching (as their length, Lk, increases). (See
discussion on p. 11020 in Urry's paper).

Let us assume that two macroscopic polymers, one of each type (U and
K) are suspended in the same system. At constant temperature, if the
second law is true, we must have

(dFu / dLk)_Lu = (dFk / dLu)_Lk

where Fu0 and Fk0 are work-producing forces of contraction. The
values of the partial derivatives (dFu/dLk)_Lu and (dFk/dLu)_Lk can be
assessed from experimental results reported on p. 11020 in Urry's
paper. As K is being stretched (Lk increases), it releases protons,
the pH decreases and, accordingly, Fu must increase. Therefore, (dFu/
dLk)_Lu is positive. In contrast, as U is being stretched (Lu
increases), it absorbs protons, the pH increases and Fk must decrease.
Therefore, (dFk/dLu)_Lk is negative. One partial derivative is
positive, the other negative: this proves that the second law of
thermodynamics is false.

Pentcho Valev

On Nov 8, 12:02*am, Pentcho Valev wrote:
Carnot dealt with two reversible heat engines which DID NOT INTERACT.
In 1850 Clausius used NON-INTERACTING heat engines again:

http://www.mdpi.org/lin/clausius/clausius.htm
"Ueber die bewegende Kraft der Wärme", 1850, Rudolf Clausius: "Carnot
assumed, as has already been mentioned, that the equivalent of the
work done by heat is found in the mere transfer of heat from a hotter
to a colder body, while the quantity of heat remains undiminished. The
latter part of this assumption--namely, that the quantity of heat
remains undiminished--contradicts our former principle, and must
therefore be rejected... (...) It is this maximum of work which must
be compared with the heat transferred. When this is done it appears
that there is in fact ground for asserting, with Carnot, that it
depends only on the quantity of the heat transferred and on the
temperatures t and tau of the two bodies A and B, but not on the
nature of the substance by means of which the work is done. (...) If
we now suppose that there are two substances of which the one can
produce more work than the other by the transfer of a given amount of
heat, or, what comes to the same thing, needs to transfer less heat
from A to B to produce a given quantity of work, we may use these two
substances alternately by producing work with one of them in the above
process. At the end of the operations both bodies are in their
original condition; further, the work produced will have exactly
counterbalanced the work done, and therefore, by our former principle,
the quantity of heat can have neither increased nor diminished. The
only change will occur in the distribution of the heat, since more
heat will be transferred from B to A than from A to B, and so on the
whole heat will be transferred from B to A. By repeating these two
processes alternately it would be possible, without any expenditure of
force or any other change, to transfer as much heat as we please from
a cold to a hot body, and this is not in accord with the other
relations of heat, since it always shows a tendency to equalize
temperature differences and therefore to pass from hotter to colder
bodies."

NON-INTERACTION means that the work-producing force generated by the
first engine, F1, is independent of the displacement, X2, in the
second engine, and vice versa:

F1 = F1(X1, X2); F2 = F2(X1, X2)

dF1/dX2 = dF2/dX1 = 0

where "d" is the partial derivative symbol. It can be shown that, if
the two reversible heat engines DO INTERACT and the conditions are
isothermal, the equation:

dF1/dX2 = dF2/dX1

is a consequence of the second law of thermodynamics (Kelvin's
version). Accordingly, if the partial derivatives dF1/dX2 and dF2/dX1
are not equal, heat from a single reservoir CAN, cyclically, be
converted into work, in violation to the second law of thermodynamics.
Consider, for instance, INTERACTING "chemical springs". There are two
types of macroscopic contractile polymers which on acidification
(decreasing the pH of the system) contract and can lift a weight:

http://pubs.acs.org/doi/abs/10.1021/jp972167t
J. Phys. Chem. B, 1997, 101 (51), pp 11007 - 11028
Dan W. Urry, "Physical Chemistry of Biological Free Energy
Transduction As Demonstrated by Elastic Protein-Based Polymers"

Polymers designed by Urry (U) absorb protons on stretching (as their
length, Lu, increases), whereas polymers designed by Katchalsky (K)
release protons on stretching (as their length, Lk, increases). (See
discussion on p. 11020 in Urry's paper).

Let us assume that two macroscopic polymers, one of each type (U and
K) are suspended in the same system. At constant temperature, if the
second law is true, we must have

(dFu / dLk)_Lu = (dFk / dLu)_Lk

where Fu0 and Fk0 are work-producing forces of contraction. The
values of the partial derivatives (dFu/dLk)_Lu and (dFk/dLu)_Lk can be
assessed from experimental results reported on p. 11020 in Urry's
paper. As K is being stretched (Lk increases), it releases protons,
the pH decreases and, accordingly, Fu must increase. Therefore, (dFu/
dLk)_Lu is positive. In contrast, as U is being stretched (Lu
increases), it absorbs protons, the pH increases and Fk must decrease.
Therefore, (dFk/dLu)_Lk is negative. One partial derivative is
positive, the other negative: this proves that the second law of
thermodynamics is false.

Pentcho Valev


The examples wherein heat is not converted into some other form of
energy in a cyclic process, do not come under the purview of second
law of thermodynamics. For example the polymer contraction - extension
reversible cycle, or the Capacitor between whose plates a dielectric
is introduced and withdrawn in a reversible cyclic process do not
concern with the second law; they concern with the first law only.
Since the aim is to show that second law of thermodynamics is false,
those examples do not serve the intended purpose.

I must mention, however, that the second law of thermodynamics suffers
from inconsistencies: The standard statements of the law due to
Caratheodory and Kelvin are not equivalent. See http://arxiv.org/abs/1102.4235.

Similarly, Clausius and Kelvin statements of the second law are not
equivalent.

On Nov 5, 3:22*am, Pentcho Valev wrote:
If a constant-charge parallel-plate capacitor is totally immersed in
water, the force of attraction between the plates is 80 times weaker
than the force of attraction in vacuum. However, if we thrust some
solid dielectric between the plates (not necessarily occupying the
whole distance between them - it could be rather thin), the force of
attraction becomes even greater than in vacuum. Accordingly, the
following four-step cycle (carried out very slowly) violates the
second law of thermodynamics:

1. Plates are immersed and fixed. We thrust the solid dielectric.
2. Plates get closer. We GAIN work.
3. We withdraw the solid dielectric.
4. Plates get apart; initial state restored. We SPEND work.

When the plates are immersed in a liquid dielectric (water), some
additional pressure between them emerges, pushes them apart and so
counteracts their electrostatic attraction (W. Panofsky, M. Phillips,
Classical Electricity and Magnetism, Addison-Wesley, Reading,
Massachusetts (1962), pp. 111-116). If the plates are vertical and
only partially immersed, the same pressure forces the liquid between
the plates to rise above the surface of the water pool (see fig. 6-7
on p. 112 in Panofsky's book). What if one punches a small hole in one
of the plates, just above the surface of the pool? Will the lifted
water leak through the hole and fall? If lifting is due to an
additional pressure generated within the bulk, as assumed by Panofsky
and Phillips, then water WILL leak through the hole and the second law
will be violated. No matter how weak the waterfall is, in principle it
can rotate a waterwheel...

The perpetuum mobile of the second kind described above will never
become a money-spinner and will not solve the energy problems of
humankind. However Nature may occasionally have used such (inefficient
from an anthropocentric point of view) mecanisms and the knowledge of
them could make us unexpectedly rich in some unconventional sense.

Pentcho Valev


I believe that you may have overlooked the work done on the dielectric
itself. The change in capacitance is also left out of your analysis.
It's a bit muddled, but good for you for going after thermodynamics
and a bit of electricity too. I'm used to your relativity criticism
and read some of it.

Please consider this in your thermodynamic analysis:
The interpretation of heat as vibrating atoms is compromised in the
solid state, where heat propagation remains remarkably slow. In say a
crystalline lattice we witness atoms in contact with each other to the
point that sound propagates readily through the lattice, which is a
vibration of the atoms at quite a faster rate of propagationa. Where
is the additional room for the heat mode and how can it be so slow?
Where is this discussion in the literature? For the lack of discussion
I would say that the modern interpretation of heat as vibrating atoms
is flawed. This is an interesting crux to focus on, for it is geometry
which has been offended. It is such a plain and simple problem that I
find it difficult to understand how we all were hoodwinked.

I suppose you can take this analysis back to the same era as your
relativity criticisms. During the late 1800's tremendous energy was
spent on electromagnetic phenomena, and Maxwell always attempted to
integrate heat into his electromagnetic analysis. Could it be that
people just got worn out after fifty or so years of struggling and
threw in the towel? The rest of us are caught, for if we fail to mimic
the status quo then we are viewed as inadequate for our inability to
mimic. Then too, it is not quite enough to simply criticize the status
quo. What we really want is a clean(er) replacement. Still, it is by
such criticisms that the leads can be found.

I do respect your criticism of entropy and I find it difficult to
accept. But this is somewhat like the conservation of energy; an even
more difficult law to challenge, yet since energy lays all about us
then who are we to claim that it is zero? No, we can't very well
challenge all of thermodynamics since heat flow is a fairly well
behaved and understood phenomenon. But have they really got a clean
theory? Nah. There are so many odd-ball details that have only curve
fitters equations that we cannot call this theory. It seems we need
more dynamics within the basis.

- Tim http://bandtech.com/polysigned

On Nov 10, 2:40*pm, "Tim Golden BandTech.com"
wrote:
On Nov 5, 3:22*am, Pentcho Valev wrote:





If a constant-charge parallel-plate capacitor is totally immersed in
water, the force of attraction between the plates is 80 times weaker
than the force of attraction in vacuum. However, if we thrust some
solid dielectric between the plates (not necessarily occupying the
whole distance between them - it could be rather thin), the force of
attraction becomes even greater than in vacuum. Accordingly, the
following four-step cycle (carried out very slowly) violates the
second law of thermodynamics:

1. Plates are immersed and fixed. We thrust the solid dielectric.
2. Plates get closer. We GAIN work.
3. We withdraw the solid dielectric.
4. Plates get apart; initial state restored. We SPEND work.

When the plates are immersed in a liquid dielectric (water), some
additional pressure between them emerges, pushes them apart and so
counteracts their electrostatic attraction (W. Panofsky, M. Phillips,
Classical Electricity and Magnetism, Addison-Wesley, Reading,
Massachusetts (1962), pp. 111-116). If the plates are vertical and
only partially immersed, the same pressure forces the liquid between
the plates to rise above the surface of the water pool (see fig. 6-7
on p. 112 in Panofsky's book). What if one punches a small hole in one
of the plates, just above the surface of the pool? Will the lifted
water leak through the hole and fall? If lifting is due to an
additional pressure generated within the bulk, as assumed by Panofsky
and Phillips, then water WILL leak through the hole and the second law
will be violated. No matter how weak the waterfall is, in principle it
can rotate a waterwheel...

The perpetuum mobile of the second kind described above will never
become a money-spinner and will not solve the energy problems of
humankind. However Nature may occasionally have used such (inefficient
from an anthropocentric point of view) mecanisms and the knowledge of
them could make us unexpectedly rich in some unconventional sense.

Pentcho Valev


I believe that you may have overlooked the work done on the dielectric
itself. The change in capacitance is also left out of your analysis.
It's a bit muddled, but good for you for going after thermodynamics
and a bit of electricity too. I'm used to your relativity criticism
and read some of it.

Please consider this in your thermodynamic analysis:
* *The interpretation of heat as vibrating atoms is compromised in the
solid state, where heat propagation remains remarkably slow. In say a
crystalline lattice we witness atoms in contact with each other to the
point that sound propagates readily through the lattice, which is a
vibration of the atoms at quite a faster rate of propagationa. Where
is the additional room for the heat mode and how can it be so slow?
Where is this discussion in the literature? For the lack of discussion
I would say that the modern interpretation of heat as vibrating atoms
is flawed. This is an interesting crux to focus on, for it is geometry
which has been offended. It is such a plain and simple problem that I
find it difficult to understand how we all were hoodwinked.

I suppose you can take this analysis back to the same era as your
relativity criticisms. During the late 1800's tremendous energy was
spent on electromagnetic phenomena, and Maxwell always attempted to
integrate heat into his electromagnetic analysis. Could it be that
people just got worn out after fifty or so years of struggling and
threw in the towel? The rest of us are caught, for if we fail to mimic
the status quo then we are viewed as inadequate for our inability to
mimic. Then too, it is not quite enough to simply criticize the status
quo. What we really want is a clean(er) replacement. Still, it is by
such criticisms that the leads can be found.

I do respect your criticism of entropy and I find it difficult to
accept. But this is somewhat like the conservation of energy; an even
more difficult law to challenge, yet since energy lays all about us
then who are we to claim that it is zero? No, we can't very well
challenge all of thermodynamics since heat flow is a fairly well
behaved and understood phenomenon. But have they really got a clean
theory? Nah. There are so many odd-ball details that have only curve
fitters equations that we cannot call this theory. It seems we need
more dynamics within the basis.

*- Timhttp://bandtech.com/polysigned



Hi.

It's just a confusion of terms.
Inner energy leads to temperature. Work leads to warmth.

KON