Catalysts Violate the Second Law of Thermodynamics

https://www.scientificexploration.org/edgescience/24
Daniel P. Sheehan, Beyond the Second Law of Thermodynamics: "These culminated in 2012-13 with a series of laboratory experiments that showed true second law breakdown. The demonstration was straightforward. A small, closed, high- temperature cavity contained two metal catalysts (rhenium and tungsten), which were known to dissociate molecular hydro- gen (H2) to different degrees (Figure 1). (Rhenium dissociates hydrogen molecules into atoms better than tungsten does; conversely, tungsten recombines hydrogen atoms back into hydrogen molecules better than rhenium.) Because the dissociation reaction (H2 - 2H) is endothermic (absorbs heat), and the recombination reaction (2H - H2) is exothermic (liberates heat), when hydrogen was introduced into the cavity, the rhenium surfaces cooled (up to more than 125 K) relative to the tungsten (Figure 2). Because the hydrogen-metal reactions were ongoing in the sealed cavity, the rhenium stayed cooler than the tungsten indefinitely. This permanent temperature difference--this steady-state nonequilibrium--is expressly forbidden by the second law, not just because the system won't settle down to a single-temperature equilibrium, but because this steady-state temperature difference can, in principle, be used to drive a heat engine (or produce electricity) solely by converting heat back into work, which is a violation of one of the most fundamental statements of the second law (Kelvin- Planck formulation)."

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 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) he

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

Pentcho Valev

A perpetual motion machine of the second kind published in a prestigious journal and no reaction at all from the scientific community:

http://scitation.aip.org/content/aip...1063/1.4825269
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..."

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

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

Another perpetual motion machine of the second kind:

http://arxiv.org/abs/1203.0161
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..."

No reaction from the scientific community, except that UCLA researchers present the discovery as their own:

http://beforeitsnews.com/self-suffic...s-2486966.html
"...scientists in Hong Kong built a graphene battery that turns ambient heat into electric current. This technology was picked up by UCLA researchers who claimed this same discovery as their own, seen in the video below:

https://www.youtube.com/watch?v=RVUf7-tTLXo
The Super Supercapacitor"

Pentcho Valev

http://gas2.org/2015/08/24/graphene-...t-electricity/
"Graphene Converts Heat Into Electricity. The team--led by Prof Ian Kinloch, Prof Robert Freer, and Yue Lin--added a small amount of graphene to strontium titanium oxide. The resulting composite was able to convert heat that would otherwise be wasted into an electric current over a broad temperature range, beginning at room temperature."

"Beginning at room temperature"? And no cold body to provide the temperature gradient? Then this is a violation of the second law of thermodynamics par excellence. The implication is that any writing based on the concept of entropy is not even wrong. Einstein's 1905 paper on the photoelectric effect is an example.

Pentcho Valev

https://www.sciencenews.org/article/...thermodynamics
"Over the last few decades, physicists have gradually explored heat flow at the quantum level, intrigued by the possibility of finding violations of thermodynamics' second law. So far, the second law has held strong."

It hasn't. There are violations even at the macroscopic level, some published in prestigious journals. See my comment on the paper.

Pentcho Valev