• [deleted]

Maybe the Hutterites are on to something ...

5 days later
  • [deleted]

Congratulations Raissa. This sounds wonderful! Please let us know when the stock market is about to transition and in which direction. Seriously though, climate change might be a good field for this kind of analysis. Cheers, Allan & Sonia

  • [deleted]

Really interesting talk, lots to think about. The fleeting comments on exponential population growth and of wild fluctuations near the end is the really important bit, never mind people getting bored with their Facebook information overload. Vast impending problems. Seems it is in part the uniformity that permits connection that is also a vulnerability. Like agricultural monocultures that have lost the resilience to disease afforded by natural variation.

    8 days later

    "So we're at the point where we can begin to analyze systems of systems," says D'Souza, each evolving on its own timescale, with feedbacks between these systems."

    Exactly so. And I think we're finding further -- as Raissa's research suggests -- that assuring the independence of systems within systems is becoming increasingly important to avoid the kind of out of control degradation of an interdependent system that Battiston's group identified.

    It's long been presumed that " ... bounded rationality -- i.e., individual human (or, abstractly, individual node)limitations to acquire sufficient information for central control decisions might be solved or mitigated by information technology integrated vertically into the system (hierarchical up and down, rather than lateral, communication ).

    "Bar-Yam reveals that distributed control -- lateral information -- increases variety. Increased variety increases the coordination strength of the network; i.e., 'In considering the requirements of multi-scale variety more generally, we can state that for a system to be effective, it must be able to coordinate the right number of components to serve each task, while allowing the independence of other sets of components to perform their respective tasks without binding the actions of one such set to another.' * [Ray, T. NECSI ICCS 2007, "Time, Change and Self Organization] * Bar-Yam, Y. "Multiscale Variety in Complex Systems." Complexity vol 9, no 4, pp 37-45

    Thanks, Grace, Raissa and FQXi for another great informative article on the leading edge of research.

    Tom

    4 days later
    • [deleted]

    I like the association of time with the growth of the complexity of the systems.

    It seems to me there is that kind of time associated with any kind or growth or senescence and decay, or dismantling. It is a very different kind of time to the time dimension of space-time though. As it does not have the same association with space that forms the 'fabric of space-time'. It could be imagined as a time line where the structures (or systems) are arranged in increasing or decreasing complexity, giving the historical sequence of arrangements. However only the youngest arrangement still exists. (Though it may incorporate an 'older' arrangement as part of its structure.) That historical time line is an imaginary thing and not something melded with space.

    Which means there are two importantly different kinds of time that are parts of different aspects, or types, of reality and should not be muddled. There are not two different geometric time dimensions. There is only one. That one is associated with the potential sensory data in the environment from which space-time manifestations can be produced. There is continual change associated with the material aspect of the Universe, giving passage of time and the effect of a one way arrow of time (which are missing from the space-time continuum).

    • [deleted]

    Cambridge University is to launch a centre for the study of existential risks to the human race Quote: "But new hazards are emerging that could be so catastrophic that even a tiny probability is disquieting. For instance, global society depends on elaborate networks - electricity grids, air traffic control, international finance, just-in-time delivery and so forth. Unless these systems are highly resilient, their manifest benefits could be outweighed by catastrophic (albeit rare) breakdowns cascading through the system." The Guardian

    a year later
    • [deleted]

    SO-MISCALLED "COMPLEXITY" IS UTTER-SIMPLICITY!!! (VERSUS COMPLICATEDNESS)

    UNIVERSALLY OBSERVED IN SO-MISCALLED "COMPLEXITY" ARE 1/f-"NOISE" ~(FLUCTUATION-DISSIPATION THEOREM) ~ GENERALIZED-SUSCEPTIBILITY POWER-SPECTRUM AND SCALE-INVARIANCE.

    PARAPHRASING(SEE FIRST ATTACHMENT!!!) SIEGEL'S 1993 DEFINITION OF SO-MISCALLED "COMPLEXITY" AS UTTER-SIMPLICITY!!!:

    (d/dx)log x = 1/x

    HENCE

    (d/dw)log w = 1/w

    BUT THE LOGARITHM-FUNCTION IS BY DEFINITION SCALE-INVARIANCE. SO

    (d/dw)[SCALE-INVARIANCE SYMMETRY-RESTORING](w) = 1/w

    HENCE BY NOETHER'S-THEOREM RELATING CONTINUOUS-SYMMETRIES TO CONSERVATION-LAWS

    (d/dw)[EINSTEIN SUMMATION CONVENTION{d[sub-mu]J[super-mu;sub-SCALE](w)}] = 1/w

    THUS SO-MISCALLED "COMPLEXITY" IS THE 1/f POWER-SPECTRUM INSURANCE THAT SCALE-INVARIANCE IS CONSERVED; FROM MICRO VIA MESO TO MACRO AND FROM MACRO VIA MESO TO MICRO. UTTER-SIMPLICITY!!!

    ANYTHING ELSE SUCH AS ONE'S MOTHER-IN-LAW AND 1/f POWER-SPECTRUM AND SCALE-INVARIANCE IS COMPLICATEDNESS!!!Attachment #1: 1_FULL_PAPER_on_so_MIScalled_COMPLEXITY_IS_UTTER-SIMPLICITY_vs._COMPLICATEDNESS.pdfAttachment #2: FULL_PAPER_on_NEWTONS-LAW_INVERSE-TRANSFORM_IN_1-OVER-f_NOISE.pdf

    a month later

    Emergence of Macroscopic Directed Motion in Water Systems

    "A team of researchers from several facilities in France has devised a means for modeling coordinated swarming behavior in a controlled environment. (...) To get the balls moving the researchers applied a small electric charge. Doing so caused chaotic movement at first, but as time passed, the researchers observed that the balls formed a swarm that moved around the track as a single entity."

    Emergence of macroscopic directed motion in populations of motile colloids, Antoine Bricard, Jean-Baptiste Caussin, Nicolas Desreumaux, Olivier Dauchot, Denis Bartolo, Nature 503, 9598 (07 November 2013)

    I suggest that the microscopic mechanism triggering the swarm moving "around the track as a single entity" may be similar to that triggering the "waterfall" described in an old paper of mine:

    August 12, 2004, Biased Thermal Motion and the Second Law of Thermodynamics, Pentcho Valev: "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, thereby dissipating its potential energy as heat? If this happens, one will have a perpetual macroscopic cycle capable of producing work. Needless to say, such a cycle contradicts the second law of thermodynamics. No matter how weak the waterfall is, theoretically it can rotate a waterwheel..."

    The "floating water bridge" is based on the same molecular mechanism:

    Floating Water Bridge - Elmar Fuchs (SETI Talks)

    Pentcho Valev

      Emergence of Macroscopic Directed Motion in Water Systems II

      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."

      Experimental demonstration:

      "Liquid Dielectric Capacitor"

      More arguments:

      "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."

      The pressure difference will constantly pump water through a small hole punched in one of the plates, in violation of the second law of thermodynamics. In FIG. 1 below the water rises to a height h - the hole could be drilled at h/2. Will water leak out through the hole? If the pressure inside the capacitor is indeed greater, the answer is YES:

      Can. J . Phys., 60. 449 (1982), Fluids in electric and magnetic fields: Pressure variation and stability, I. BREVIK: "FIG. 1. Two charged condenser plates partly immersed in a dielectric liquid. (...) FIG. 2. The hydrostatic pressure variation from point 1 to point 5 in Fig. 1."

      Pentcho Valev

      There is a problem in physics that acts like the face of Medusa the Gorgon - on seeing it, physicists get petrified and remain so until the problem is completely forgotten. If a constant-charge parallel-plate capacitor is totally immersed in a liquid dielectric, e.g. water, the force of attraction between the plates SHARPLY DECREASES - for water, it becomes 80 times weaker. However, if instead of liquid dielectric one thrusts some solid dielectric between the plates, the force of attraction the plates exert on one another (slightly) INCREASES. In both cases the dielectric between the plates - liquid or solid - polarizes and the picture of polarization is quite standard; yet when the dielectric is liquid (water) the force of attraction between the plates decreases by a factor of 80 while in the case of solid dielectric the force of attraction increases. Where does the drastic difference come from?

      Two things are sure: 1. The sharp decrease of the force of attraction in the case of liquid dielectric "cannot be explained by electrical forces alone". 2. In the case of liquid dielectric, a "mysterious" pressure emerges between the plates that pushes them apart and so counteracts the original electric force of attraction between them:

      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."

      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."

      "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."

      Pentcho Valev

      5 days later

      An Easily Refutable Version of the Second Law of Thermodynamics

      For a closed system (exchanges energy but not matter with the surroundings) the first law of thermodynamics defines the internal energy change, dU, to be:

      dU = dQ - dW = dQ - FdX /1/

      where dQ is the heat absorbed, dW is the work done by the system on the surroundings, F>0 is the work-producing force and dX is the respective displacement.

      Let us consider a system with two work-producing forces, F1 and F2 - here is an illustration. We assume that the system does work UNDER ISOTHERMAL CONDITIONS (that is, the system converts heat absorbed from the surroundings into work but operates so slowly, virtually reversibly, that the temperature of both the system and the surroundings remains unchanged). The work done by this system on the surroundings is:

      dW = dW1 dW2 = F1dX1 F2dX2 /2/

      Is W a function of X1 and X2? If yes, the second law of thermodynamics (Kelvin's version) is obeyed - at the end of the (isothermal) cycle W returns to its initial value and no net work is done on the surroundings.

      The following theorem is relevant:

      Theorem: W is a function of X1 and X2 if and only if the mixed partial derivatives are equal:

      "Mixed Partial Derivatives"

      Since F1 and F2 are in fact the first partial derivatives, the theorem can be expressed in the following way:

      Theorem: W is a function of X1 and X2, that is, the second law is obeyed, if and only if:

      dF1/dX2 = dF2/dX1 /3/

      where "d" should be the partial derivative symbol - when X2 varies, X1 is fixed and vice versa.

      In terms of the system with two work-producing forces which does work under isothermal conditions, the second law now states:

      SECOND LAW OF THERMODYNAMICS (KELVIN'S VERSION): The partial derivatives dF1/dX2 and dF2/dX1 are EQUAL.

      That is, if experiments show that the two sides of /3/ are equal, the second law is confirmed. If, however, experiments unambiguously show that the two sides of /3/ are not equal - e.g. dF1/dX2 is positive and dF2/dX1 negative - the second law of thermodynamics is false and will have to be abandoned.

      Consider, for instance, the so-called "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:

      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 = dFk / dLu

      where Fu>0 and Fk>0 are work-producing forces of contraction. The values of the partial derivatives dFu/dLk and dFk/dLu 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 is positive. In contrast, as U is being stretched (Lu increases), it absorbs protons, the pH increases and Fk must decrease. Therefore, dFk/dLu is negative. One partial derivative is positive, the other negative: this shows that the second law of thermodynamics is false.

      Pentcho Valev

        An Easily Refutable Version of the Second Law of Thermodynamics II

        In 1824 Sadi Carnot deduced the second law of thermodynamics from a postulate that went against the future law of conservation of energy (the first law of thermodynamics). Here is an oversimplified but consonant with the quotations below presentation of (part of) Carnot's 1824 argument:

        Postulate: Heat is an indestructible substance (caloric) that cannot be converted into work by the heat engine.

        Consequence: A cold body accepting ALL THE HEAT taken from the warm body is ABSOLUTELY NECESSARY.

        Unpublished notes written in the period 1824-1832 reveal that, after discovering the first law of thermodynamics (much earlier than the official discovery), Carnot started to doubt the necessity for a cold body:

        REFLECTIONS ON THE MOTIVE POWER OF HEAT, Sadi Carnot: p. 225: "Heat is simply motive power, or rather motion which has changed form. It is a movement among the particles of bodies. Wherever there is destruction of motive power there is, at the same time, production of heat in quantity exactly proportional to the quantity of motive power destroyed. Reciprocally, wherever there is destruction of heat, there is production of motive power." p. 222: "Could a motion (that of radiating heat) produce matter (caloric)? No, undoubtedly; it can only produce a motion. Heat is then the result of a motion. Then it is plain that it could be produced by the consumption of motive power, and that it could produce this power. All the other phenomena - composition and decomposition of bodies, passage to the gaseous state, specific heat, equilibrium of heat, its more or less easy transmission, its constancy in experiments with the calorimeter - could be explained by this hypothesis. But it would be DIFFICULT TO EXPLAIN WHY, IN THE DEVELOPMENT OF MOTIVE POWER BY HEAT, A COLD BODY IS NECESSARY; why, in consuming the heat of a warm body, motion cannot be produced."

        It seems that, almost 200 years later, Carnot's question is still relevant:

        Carnot's question (asked after discovering the first law of thermodynamics): WHY, IN THE DEVELOPMENT OF MOTIVE POWER BY HEAT, A COLD BODY IS NECESSARY?

        Pentcho Valev

        2 months later

        Perpetuum Mobile of the Second Kind ?

        Consider FIG. 1 and FIG. 2 in:

        Can. J . Phys., 60. 449 (1982), Fluids in electric and magnetic fields: Pressure variation and stability, I. BREVIK: "FIG. 1. Two charged condenser plates partly immersed in a dielectric liquid. (...) FIG. 2. The hydrostatic pressure variation from point 1 to point 5 in Fig. 1."

        FIG. 2 shows that the hydrostatic pressure between the plates of the capacitor is much greater than that in the rest of the liquid. Therefore, if we punch a small hole in one of the plates, somewhere between "3" and "2" in FIG. 1, water will constantly flow through the hole, pushed by the pressure between the plates. The resulting waterfall outside the capacitor can, in principle, rotate a wheel...

          a month later

          Perpetuum mobile of the second kind published in a respectable journal:

          Electricity generated from ambient heat across a silicon surface, Guoan Tai, Zihan Xu and Jinsong Liu, Appl. Phys. Lett. 103, 163902 (2013). ABSTRACT: "We report generation of electricity from the limitless thermal motion of ions across a two-dimensional (2D) silicon (Si) surface at room temperature. (...) This finding provides a self-charging technology for energy harvesting from ambient heat."

          An earlier version of the paper:

          "However, this finding does not agree with the second law of thermodynamics, which limits the utilization of the random thermal motion of ions to be spontaneously collected to produce electricity. We cannot explain why either this experiment or the previous experiment of graphene did not agree with the traditional theory. More research will be required to fully understand this phenomenon."

          Pentcho Valev

          18 days later

          Is Thermodynamics Dead?

          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..."

          A perpetual motion machine of the second kind described in Appl. Phys. Lett. and no reaction at all from the scientific community? Similarly, in 2001 Jos Uffink's alarming paper alarmed nobody:

          Jos Uffink: "Snow stands up for the view that exact science is, in its own right, an essential part of civilisation, and should not merely be valued for its technological applications. Anyone who does not know the Second Law of Thermodynamics, and is proud of it too, exposes oneself as a Philistine. Snow's plea will strike a chord with every physicist who has ever attended a birthday party. But his call for cultural recognition creates obligations too. Before one can claim that acquaintance with the Second Law 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."

          Thermodynamics must have been dead for a long time.

          Pentcho Valev

          The second law of thermodynamics is no longer valid but... who cares?

          "...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."

          Needless to say, professors in universities will continue to teach the false second law - the truth may be valuable but money is more valuable.

          Pentcho Valev

          6 months later

          Sadi Carnot : Why Is a Cold Body Necessary ?

          If a heat engine converts heat into work under isothermal conditions (no cold reservoir, only a hot one), the second law of thermodynamics is violated. Unpublished notes written in the period 1824-1832 reveal that, at the end of his (short) life, Carnot discovered the first law of thermodynamics and immediately started doubting the second:

          Sadi Carnot: (p. 225) "Heat is simply motive power, or rather motion which has changed form. It is a movement among the particles of bodies. Wherever there is destruction of motive power there is, at the same time, production of heat in quantity exactly proportional to the quantity of motive power destroyed. Reciprocally, wherever there is destruction of heat, there is production of motive power." (p. 222) "Could a motion (that of radiating heat) produce matter (caloric)? No, undoubtedly; it can only produce a motion. Heat is then the result of a motion. Then it is plain that it could be produced by the consumption of motive power, and that it could produce this power. All the other phenomena - composition and decomposition of bodies, passage to the gaseous state, specific heat, equilibrium of heat, its more or less easy transmission, its constancy in experiments with the calorimeter - could be explained by this hypothesis. But it would be DIFFICULT TO EXPLAIN WHY, IN THE DEVELOPMENT OF MOTIVE POWER BY HEAT, A COLD BODY IS NECESSARY; why, in consuming the heat of a warm body, motion cannot be produced."

          I think that, almost 200 years later, Carnot's question is still relevant. Isothermal heat engines are possible in principle (that is, the second law is wrong) but they are so slow and powerless that experimental demonstrations (perpetuum mobile of the second kind) are virtually impossible.

          I started the same discussion here:

          Doc Physics - A Heat Engine Can Use Heat to do Work. But It Can't Be Perfectly Efficient!

          Pentcho Valev

            Perpetual motion machines of the second kind published in prestigious journals and no reaction at all from the scientific community (science is dead?):

            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..."

            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."

            Pentcho Valev

            2 months later

            Again: Published descriptions of perpetual motion machines of the second kind (no reaction at all in the scientific community):

            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..."

            Self-Charged Graphene Battery Harvests Electricity from Thermal Energy of the Environment, Zihan Xu et al: "Moreover, the thermal velocity of ions can be maintained by the external environment, which means it is unlimited. However, little study has been reported on converting the ionic thermal energy into electricity. Here we present a graphene device with asymmetric electrodes configuration to capture such ionic thermal energy and convert it into electricity. (...) To exclude the possibility of chemical reaction, we performed control experiments... (...) In conclusion, we could not find any evidences that support the opinion that the induced voltage came from chemical reaction. The mechanism for electricity generation by graphene in solution is a pure physical process..."

            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."

            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:

            "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 evident that, for the dissociation-association reaction

            A B C,

            a catalyst cannot speed up both the forward and 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, 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) here:

            Chemical Thermodynamics - Second Law / Entropy Review

            Pentcho Valev