SIMPLE VIOLATION OF THE SECOND LAW OF THERMODYNAMICS

Misleading education:

http://physics.bu.edu/~duffy/py105/Heatengines.html
"A necessary component of a heat engine, then, is that two
temperatures are involved. At one stage the system is heated, at
another it is cooled. In a full cycle of a heat engine, three things
happen: 1. Heat is added. This is at a relatively high temperature, so
the heat can be called QH. 2. Some of the energy from that input heat
is used to perform work (W). 3. The rest of the heat is removed at a
relatively cold temperature (QC)."

The two temperatures are by no means "necessary". Consider the
macroscopic contractile polymers designed by Dan Urry which, on adding
acid (H+) to the system, contract and 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"

It is easy to show that the four-step isothermal reversible cycle:

1. The polymer is initially 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

Urry's polymers are chemical "springs" allowing one to manipulate the
force of contraction, thereby shifting the work production in favour
of the violation of the second law. You acidify the system (increase
the concentration of H+, the hydrogen ion) and the force of
contraction increases - the "spring" vigorously contracts and lifts a
relatively heavy weight, that is, does a lot of work for you:

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, p. 11025, fig. 16A

Then you decrease the H+ concentration, the force of contraction
decreases and the work you spend to stretch the "spring" and restore
its initial (stretched) state is less than the work gained previously.
So the net work gained from contraction and subsequent stretching is
positive.

Of course, the above balance does not take into account the work
involved in acidifying and then basifying the system. Note that you
GAIN work as you acidify the polymer-containing system by transfering H
+ to it, isothermally and reversibly, from a reservoir at higher H+
concentration, but then LOSE work as you move the same amount of H+
back to the reservoir. The behaviour of Urry's polymers - they absorb H
+ as they stretch and release H+ as they contract - is such that the
net work gained from acidifying and subsequently basifying the polymer-
containing system is positive again.

Pentcho Valev wrote:

Misleading education:

http://physics.bu.edu/~duffy/py105/Heatengines.html
"A necessary component of a heat engine, then, is that two
temperatures are involved. At one stage the system is heated, at
another it is cooled. In a full cycle of a heat engine, three things
happen: 1. Heat is added. This is at a relatively high temperature, so
the heat can be called QH. 2. Some of the energy from that input heat
is used to perform work (W). 3. The rest of the heat is removed at a
relatively cold temperature (QC)."

The two temperatures are by no means "necessary". Consider the
macroscopic contractile polymers designed by Dan Urry which, on adding
acid (H+) to the system, contract and 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"

It is easy to show that the four-step isothermal reversible cycle:

1. The polymer is initially 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

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: "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."

Below I will try to show that, by replacing NON-INTERACTION with
INTERACTION, one reaches the conclusion that the second law of
thermodynamics is an absurdity, not a Law of Nature.

NON-INTERACTION means that the work-producing force generated by the
first engine ("substance"), F1, is independent of the displacement,
X2, in the second engine ("substance"), and vice versa. F1 is
presented as a function of X1 and X2 and the independency condition is
expressed as the partial derivative dF1/dX2 being equal to zero
("partial" because X1 is kept constant):

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 CAN, cyclically and isothermally, 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 as their length, Lu,
increases, whereas polymers designed by Katchalsky (K) release protons
as their length, Lk, increases. (See discussion on p. 11020 in Urry's
paper: "stretching causes an uptake of protons", for Urry's polymers,
and "stretching causes the release of protons", for Katchalsky's
polymers).

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 Feb 6, 12:08*pm, 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: "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."

Below I will try to show that, by replacing NON-INTERACTION with
INTERACTION, one reaches the conclusion that the second law of
thermodynamics is an absurdity, not a Law of Nature.

NON-INTERACTION means that the work-producing force generated by the
first engine ("substance"), F1, is independent of the displacement,
X2, in the second engine ("substance"), and vice versa. F1 is
presented as a function of X1 and X2 and the independency condition is
expressed as the partial derivative dF1/dX2 being equal to zero
("partial" because X1 is kept constant):

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 CAN, cyclically and isothermally, 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 as their length, Lu,
increases, whereas polymers designed by Katchalsky (K) release protons
as their length, Lk, increases. (See discussion on p. 11020 in Urry's
paper: "stretching causes an uptake of protons", for Urry's polymers,
and "stretching causes the release of protons", for Katchalsky's
polymers).

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



Idiot

Consider the "somewhat mysterious" pressure emerging between and
PUSHING APART the plates of a constant-charge capacitor immersed in
water:

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."

Common sense forces one to conclude that, if the mysterious pressure
pushes the plates apart, then it will constantly pump water through a
small hole punched in one of the plates. But the constant flow through
the hole can in principle be harnessed to do work and so the second
law of thermodynamis is violated. Could common sense be misleading in
this case?

Pentcho Valev