The Bluff Called Second Law of Thermodynamics

Jos Uffink, Bluff your way in the Second Law of Thermodynamics: "I therefore argue for the view that the second law has nothing to do with the arrow of time. [...] 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." http://philsci-archive.pitt.edu/313/1/engtot.pdf

Jos Uffink is arguably the best expert on the foundations of thermodynamics, but even if he wasn't, we can take his statements as hypothesis and try to draw conclusions. So our premises a

1. It is not clear what the second law of thermodynamics states, 167 years after its appearance.

2. The second law has nothing to do with the arrow of time.

The only reasonable conclusion is:

The second law of thermodynamics is a bluff. The countless confusing formulations and the arrow-of-time diversion camouflage some important fact.

The important fact, in terms of the explanation below, is:

A cold body is NOT necessary.

Here is the explanation. The simplest and most precise formulation of the second law was given by Sadi Carnot himself:

"A cold body is necessary"

That is, heat cannot be cyclically converted into work unless there is some temperature gradient (a hot body, source of heat, and a cold body, receiver of heat, must be available). The problem is that in 1824 Carnot deduced "A cold body is necessary" from a postulate that eventually turned out to be false:

Carnot's (false) postulate: Heat is an indestructible substance (caloric) that cannot be converted into work by the heat engine.

Unpublished notes written in the period 1824-1832 reveal that, after realizing that his postulate was false, Carnot found "A cold body is necessary" implausible:

http://www.nd.edu/~powers/ame.20231/carnot1897.pdf
Sadi Carnot, REFLECTIONS ON THE MOTIVE POWER OF HEAT, 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."

Generally, a cold body is not necessary, that is, the second law of thermodynamics is false. The cold body is only TECHNOLOGICALLY necessary as it makes heat engines fast-working. Heat engines working under isothermal conditions (in the absence of a cold body) are commonplace but are too slow and impuissant to be of any technological importance. Yet they do violate the second law of thermodynamics.

Actually, unless the working substance is ideal gas-like, all isothermal heat engines are essentially perpetual-motion machines of the second kind. For instance, there are macroscopic contractile polymers which, on adding acid (H+) to the system, develop a huge work-producing force, contract and lift 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."

See Figure 4 he

http://www.ncbi.nlm.nih.gov/pmc/arti...00645-0017.pdf
A. KATCHALSKY, POLYELECTROLYTES AND THEIR BIOLOGICAL INTERACTIONS, p. 15, Figure 4: "Polyacid gel in sodium hydroxide solution: expanded. Polyacid gel in acid solution: contracted; weight is lifted."

Mineral acid (hydrogen ions, H+) is added to the system and "the polymolecule contracts and lifts the attached weight through a distance ΔL". Then the acid can be removed and the macromolecule resumes its initial stretched state, ready to lift another weight. The work involved in adding and removing (electrochemically) hydrogen ions, if performed very slowly, almost reversibly, is virtually zero, while the net work extracted from contracting and stretching is obviously positive - the system is cyclically lifting weights at the expense of heat absorbed from the surroundings, in violation of the second law of thermodynamics.

There are also macroscopic polymers which contract and lift a weight as H+ is removed, not added:

https://www.youtube.com/watch?v=JGn2a21FvLM
"Here we see a pH-responsive polyacrylic acid hydrogel contained within an unbound carbon fibre braid. The artificial muscle (McKibben style) actuates when placed in a solution with high pH..."

Pentcho Valev

The Clausius statement of the second law of thermodynamics:

"Heat can never pass from a colder to a warmer body without some other change connected therewith, occurring at the same time."

This version of the second law is very popular because, like "Entropy always increases", it is not even wrong (scientists love not-even-wrong statements because they are invincible - criticisms "collapse in deepest humiliation"):

http://link.springer.com/book/10.100...-1-4613-9444-0
Clifford Truesdell, The Tragicomical History of Thermodynamics, 1822-1854, p. 333: "Clausius' verbal statement of the "Second Law" makes no sense, for "some other change connected therewith" introduces two new and unexplained concepts: "other change" and "connection" of changes. Neither of these finds any place in Clausius' formal structure. 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."

http://web.mit.edu/keenansymposium/o...und/index.html
Arthur Eddington: "The law that entropy always increases, holds, I think, the supreme position among the laws of Nature. If someone points out to you that your pet theory of the universe is in disagreement with Maxwell's equations - then so much the worse for Maxwell's equations. If it is found to be contradicted by observation - well, these experimentalists do bungle things sometimes. But if your theory is found to be against the second law of thermodynamics, I can give you no hope; there is nothing for it but to collapse in deepest humiliation."

Pentcho Valev