IS THERMODYNAMICS A DEAD SCIENCE?

http://philsci-archive.pitt.edu/archive/00000313/
Jos Uffink: "Before one can claim that acquaintance with the Second Law [of thermodynamics] is as indispensable to a cultural education as Macbeth or Hamlet, it should obviously be clear what this law states. This question is surprisingly difficult. The Second Law made its appearance in physics 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 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 that it continues to attract new efforts at clarification. (...) The historian of science and mathematician Truesdell made a detailed study of the historical development of thermodynamics in the period 1822-1854. He characterises the theory, even in its present state, as 'a dismal swamp of obscurity' and 'a prime example to show that physicists are not exempt from the madness of crowds'. (...) Clausius' verbal statement of the second law makes no sense.... All that remains is a Mosaic prohibition ; a century of philosophers and journalists have acclaimed this commandment ; a century of mathematicians have shuddered and averted their eyes from the unclean..... Seven times in the past thirty years have I tried to follow the argument Clausius offers... and seven times has it blanked and gravelled me.... I cannot explain what I cannot understand."

Perpetual motion machines of the second kind published in prestigious journals and no reaction at all from the scientific community:

http://www.researchgate.net/publicat...2604889353.pdf
Electricity generated from ambient heat across a silicon surface, Guoan Tai, Zihan Xu, and Jinsong Liu, Appl. Phys. Lett. 103, 163902 (2013): "We report generation of electricity from the limitless thermal motion of ions across a two-dimensional (2D) silicon (Si) surface at room temperature. (...) ....limitless ambient heat, which is universally present in the form of kinetic energy from molecular, particle, and ion sources, has not yet been reported to generate electricity. (...) This study provides insights into the development of self-charging technologies to harvest energy from ambient heat, and the power output is comparable to several environmental energy harvesting techniques such as ZnO nanogenerator, liquid and gas flow-induced electricity generation across carbon nanotube thin films and graphene, although this remains a challenge to the second law of thermodynamics..."

http://link.springer.com/article/10....701-014-9781-5
Experimental Test of a Thermodynamic Paradox, D. P. Sheehan et al, Foundations of Physics, March 2014, Volume 44, Issue 3, pp 235-247: "...there arise between the vane faces permanent pressure and temperature differences, either of which can be harnessed to perform work, in apparent conflict with the second law of thermodynamics. Here we report on the first experimental realization of this paradox, involving the dissociation of low-pressure hydrogen gas on high-temperature refractory metals (tungsten and rhenium) under blackbody cavity conditions. The results, corroborated by other laboratory studies and supported by theory, confirm the paradoxical temperature difference and point to physics beyond the traditional understanding of the second law."

There is some small reaction but only the technological effect is discussed, the violation of the second law of thermodynamics not even worth mentioning:

http://sciencequestionswithchris.wor...ricity-source/
"...electronic devices can charge their batteries through various methods without being plugged into a source of electricity. What all the different methods have in common is that they absorb energy that is in some other form (heat, light, vibrations, radio waves, etc.) from the external environment and then convert the energy into electrochemical energy that is stored in the device's batteries. (...) The ambient heat in the natural environment can be captured and converted to electricity. There are many ways to do this, but the basic concept is to funnel the random thermal motion of ions or electrons into a more ordered motion of charge, which constitutes an electrical current. This funneling is often accomplished by layering various materials with different thermal and electrical properties. For instance, the researchers Guoan Tai, Zihan Xu, and Jinsong Liu have recently demonstrated the conversion of heat to electricity using the ion layer that forms between silicon and a copper(II) chloride solution."

Pentcho Valev

Violations of the second law of thermodynamics would be obvious if it were not for misleading education of this kind:

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."

This is simply wrong - the two temperatures are not always necessary. There are heat engines functioning in isothermal conditions - the work-producing force is activated by some chemical agent, not by heating. Here are examples of macroscopic contractile polymers which, on adding acid (H+) to the system, develop a huge work-producing force, contract and light a weight:

http://www.gsjournal.net/old/valev/val3.gif

http://www.google.com/patents/US5520672
"When the pH is lowered (that is, on raising the chemical potential, μ, of the protons present) at the isothermal condition of 37°C, these matrices can exert forces, f, sufficient to lift weights that are a thousand times their dry weight. This is chemomechanical transduction..."

http://www.ncbi.nlm.nih.gov/pmc/arti...00645-0017.pdf
"FIGURE 4: Polyacid gel in sodium hydroxide solution: expanded. Polyacid gel in acid solution: contracted; weight is lifted."

http://pubs.acs.org/doi/abs/10.1021/jp972167t
FIG. 16A on p. 11025 in 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

The following four-step isothermal reversible cycle clearly violates the second law of thermodynamics:

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

Note that adding H+ to the system and then removing it (steps 1 and 3), if performed reversibly, amount to zero work involved (the work gained in step 1 is lost in step 3).

Pentcho Valev

The second law of thermodynamics is almost obviously false for chemical systems. Consider the (valid) argument that, if catalysts can shift chemical equilibrium, the second law would be violated:

https://www.boundless.com/chemistry/...lyst-447-3459/
"In the presence of a catalyst, both the forward and reverse reaction rates will speed up equally, thereby allowing the system to reach equilibrium faster. However, it is very important to keep in mind that the addition of a catalyst has no effect whatsoever on the final equilibrium position of the reaction. It simply gets it there faster. (...) To reiterate, catalysts do not affect the equilibrium state of a reaction. In the presence of a catalyst, the same amounts of reactants and products will be present at equilibrium as there would be in the uncatalyzed reaction. To state this in chemical terms, catalysts affect the kinetics, but not the thermodynamics, of a reaction. If the addition of catalysts could possibly alter the equilibrium state of the reaction, this would violate the second rule of thermodynamics...."

It is almost obvious that, for the dissociation-association reaction

A - B + C,

a catalyst cannot speed up the forward and the reverse reaction rates equally, due to the entirely different forward and reverse catalytic mechanisms. In the forward (dissociation) reaction, the catalyst should just meet and split A. In the reverse (association) reaction, the catalyst should first get together B and C, a step which, if the diffusion factor is predominant, could be highly improbable.

Catalysts do shift chemical equilibrium, in violation of the second law of thermodynamics.

I have started the same discussion (and it has developed in an interesting way) he

https://www.youtube.com/watch?v=aL_iNGh8CNo
Chemical Thermodynamics - Second Law / Entropy Review

Pentcho Valev

A second law-violating device I proposed in 2002:

http://proceedings.aip.org/resource/...cs/643/1/430_1
AIP Conf. Proc. 643, pp. 430-435, Pentcho Valev 2002: "...as two vertical constant-charge capacitor plates partially dip into a pool of a liquid dielectric (e.g. water), the liquid between them rises high above the surface of the rest of the liquid in the pool. Evidently, if one punches a macroscopic hole in one of the plates, nothing could prevent the liquid between the plates from leaking out through the hole and generating an eternal waterfall outside the capacitor. This hypothesis has been discussed on many occasions but so far no serious counter-argument has been raised."

Here are an experimental demonstration of the rise of the liquid between the plates:

http://www.youtube.com/watch?v=T6KAH1JpdPg
"Liquid Dielectric Capacitor"

and a schematic picture of the "eternal waterfall":

http://energythic.com/usercontent/3/...PU_caphole.gif

Why will water leak out through the hole? Because the additional elevation (beyond that due to capillary forces) is caused by an increase in the liquid pressure between the plates:

http://www.amazon.com/Introduction-T.../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://farside.ph.utexas.edu/teachin...es/node44.html
"However, in experiments in which a capacitor is submerged in a dielectric liquid the force per unit area exerted by one plate on another is observed to decrease... (...) This apparent paradox can be explained by taking into account the difference in liquid pressure in the field filled space between the plates and the field free region outside the capacitor."

http://www.amazon.com/Classical-Elec...iglink21401-20
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."

Here is my explanation of the effect:

http://www.gsjournal.net/old/valev/valev2.pdf
Pentcho Valev: Biased Thermal Motion and the Second Law of Thermodynamics

The "floating water bridge" is essentially the same phenomenon - water absorbs heat from the surroundings and use it to "climb out of the beakers":

http://phys.org/news/2007-09-bridge-...h-voltage.html
"When exposed to a high-voltage electric field, water in two beakers climbs out of the beakers and crosses empty space to meet, forming the water bridge. The liquid bridge, hovering in space, appears to the human eye to defy gravity."

https://www.youtube.com/watch?v=FhBn1ozht-E
The Floating Water Bridge

Pentcho Valev