Thermodynamics laws, violation

No laws of physics or thermodynamics are violated in such open dissipative systems exhibiting increased COP and energy conservation laws are rigorously obeyed. Classical equilibrium thermodynamics does not apply and is permissibly violated. Instead, the thermodynamics of open systems far from thermodynamic equilibrium with their active environment—in this case the active environment-rigorously applies [2-4]. 

At equilibrium, the affinities vanish (A] = 0,A2 = 0). Therefore, Jrl - Jt3 = 0 and. /r2. Jr3 0 and the thermodynamic equilibrium does not require that all the reaction velocities vanish they all become equal. Under equilibrium conditions, then, the reaction system may circulate indefinitely without producing entropy and without violating any of the thermodynamic laws. However, according to the principle of detailed balance, the individual reaction velocities for every reaction should also vanish, as well as the independent flows (velocities). This concept is closely related to the principle of microscopic reversibility, which states that under equilibrium, any molecular process and the reverse of that process take place, on average, at the same rate. 

Many skeptics of oscillating reactions dismisses these classic examples as aberrations due to contamination. Concerns that oscillating reactions could not exist because of apparent violations of thermodynamic laws have recently been refuted by careful studies that establish that oscillating reactions are in accord with thermodynamic laws. Oscillating chemical reactions are unlike the oscillations of a pendulum. Oscillating chemical re-... 

At first sight it might appear that the second law of thermodynamics is violated for reverse diffusion to occur. This is not so. One process may depart from equilibrium in such a sense as to consume entropy provided it is coupled to another process that produces entropy even faster. This is, of course, the basic principle of any pump, whether it moves water uphill or moves heat towards a higher temperature region. For the second law requirement <7 > 0 to hold it is allowable for to be less than zero, corresponding to reverse diffusion for 1, provided <72 and 0-3, due to species 2 and 3 diffusion, be such that the overall entropy production rate is positive (a + 0-2 + <73 > 0). 

Max Planck thought otherwise. He doubted that atoms existed at all, as did many of his colleagues—the particulate theory of matter was an English invention more than a Continental, and its faintly Britannic odor made it repulsive to the xenophobic German nose—but if atoms did exist he was sure they could not be mechanical It is of paramount importance, he confessed in his Scient c Autobiography, that the outside world is something independent from man, something absolute, and the quest for laws which apply to this absolute appeared to me as the most sublime scientific pursuit in life. Of all the laws of physics, Planck believed that the thermodynamic laws applied most basically to the independent outside world that his need for an absolute required. He saw early that purely mechanical atoms violated the second law of thermodynamics. His choice was clear. 

The probability of the second law violations diminishes in a large system and occurs exponentially rarely. This observation essentially reconciles the effective validity of thermodynamics on the macroscale and states that even for large systems, in principle, such violations must occur in even macroscales. Detailed fluctuation theorems corresponding to... 

If M is less than 2, the second law of thermodynamics is violated. It also can be shown that for stability and convergence of the finite-difference solution M must be 2. 

A number of other mechanisms [53-65] have been suggested for melt fracture. Based on a stick-slip mechanism, it is purported [53] that, above a critical shear stress, die polymer experiences intermittent slipping due to a lack of adhesion between itself and die wall, in order to relieve the excessive deformation energy adsorbed during the flow. The stick-slip mechanism has attracted a lot of attention [53-63], both theoretically and experimentally. The other school of drought [64,65] is based on thermodynamic argument, according to which, melt fracture can initiate anywhere in the flow field when reduction in the fluid entropy due to molecular orientation reaches a critical value beyond which the second law of thermodynamics is violated and flow instability is induced [64]. 

In Section XVII-16C there is mention of S-shaped isotherms being obtained. That is, as pressure increased, the amount adsorbed increased, then decreased, then increased again. If this is equilibrium behavior, explain whether a violation of the second law of thermodynamics is implied. A sketch of such an isotherm is shown for nitrogen adsorbed on a microporous carbon (see Ref. 226). 

This has the advantage that the expressions for the adsotbed-phase concentration ate simple and expHcit, and, as in the Langmuir expression, the effect of competition between sorbates is accounted for. However, the expression does not reduce to Henry s law in the low concentration limit and therefore violates the requirements of thermodynamic consistency. Whereas it may be useful as a basis for the correlation of experimental data, it should be treated with caution and should not be used as a basis for extrapolation beyond the experimental range. 

The inaccuracy seems not to prohibit study of the structural properties of associating fluids, at least at low values of the association energy. However, what is most important is that this difficulty results in the violation of the mass action law, see Refs. 62-64 for detailed discussion. To overcome the problem, one can apply thermodynamical correspondence between a dimerizing fluid and a mixture of free monomers of density p o = P/30 = Po/2 and dimer species [12]. The equation of state of the corresponding mixture... 

The energy released from the breakdown of ATP has been used to drive an unfavorable process. A reaction (the formation of XY) that would not have occurred spontaneously has taken place. Of course, the amount of energy required for the formation of one molecule of XY must be less than the ainount released when one ATP is broken down, otherwise the system would have gained total energy during the coupled reaction, and violated the first law of thermodynamics. 

In summaiy, the first law of thermodynamics. Equations la and lb, states that energy is conserved and the energy associated with heat must be included as a form of energy. No process i f is possible if it violates the first law of thermodynamics energy is always conserved in our world as dictated by Equation lb. If Equation lb is applied to an adiabatic process, then because Q = 0 the first part, Equation la is recovered, but one still needs both parts of the first law to define the quantities. 

This remarkable result shows that the efficiency of a Carnot engine is simply related to the ratio of the two absolute temperatures used in the cycle. In normal applications in a power plant, the cold temperature is around room temperature T = 300 K while the hot temperature in a power plant is around T = fiOO K, and thus has an efficiency of 0.5, or 50 percent. This is approximately the maximum efficiency of a typical power plant. The heated steam in a power plant is used to drive a turbine and some such arrangement is used in most heat engines. A Carnot engine operating between 600 K and 300 K must be inefficient, only approximately 50 percent of the heat being converted to work, or the second law of thermodynamics would be violated. The actual efficiency of heat engines must be lower than the Carnot efficiency because they use different thermodynamic cycles and the processes are not reversible. 

The device will be impossible if it violates either the first or second law of thermodynamics. From Figure 2-34 the inlet and outlet properties are ... 

At first sight, self-organization appears to violate the Second Law of Thermodynamics, which asserts that the entropy S of an isolated system never decreases (or, more formally, > 0) see figure 11.2-a. Since entropy is essentially a measure of the degree of disorder in a system, the Second Law is usually interpreted to mean that an isolated system will become increasingly more disordered with time. How, then, can structure emerge after a system has had a chance to evolve ... 

The earliest hint that physics and information might be more than just casually related actually dates back at least as far as 1871 and the publication of James Clerk Maxwell s Theory of Heat, in which Maxwell introduced what has become known as the paradox of Maxwell s Demon. Maxwell postulated the existence of a hypothetical demon that positions himself by a hole separating two vessels, say A and B. While the vessels start out being at the same temperature, the demon selectively opens the hole only to either pass faster molecules from A to B or to pass slower molecules from B to A. Since this results in a systematic increase in B s temperature and a lowering of A s, it appears as though Maxwell s demon s actions violate the second law of thermodynamics the total entropy of any physical system can only increase, or, for totally reversible processes, remain the same it can never decrease. Maxwell was thus the first to recognize a connection between the thermodynamical properties of a gas (temperature, entropy, etc.) and the statistical properties of its constituent molecules. 

Figure 3.2 compares a series of reversible isothermal expansions for the ideal gas starting at different initial conditions. Note that the isotherms are parallel. They cannot intersect since this would give the gas the same pressure and volume at two different temperatures. Figure 3.3 shows a similar comparison for a series of reversible adiabatic expansions. Like the isotherms, the adiabats cannot intersect. To do so would violate the Caratheodory principle and the Second Law of Thermodynamics, since the gas would have two different entropies at the same temperature, pressure, and volume. 

No, this would be a violation of the 2nd Law of Thermodynamics. The value of A is restricted between -1 and 1 for reactions with AG>0. Thus with reactions with AG>0 the original formulation of Faraday s 1st law is always valid. 

Autocatalysis can cause sustained oscillations in batch systems. This idea originally met with skepticism. Some chemists believed that sustained oscillations would violate the second law of thermodynamics, but this is not true. Oscillating batch systems certainly exist, although they must have some external energy source or else the oscillations will eventually subside. An important example of an oscillating system is the circadian rhythm in animals. A simple model of a chemical oscillator, called the Lotka-Volterra reaction, has the assumed mechanism ... 

We have already stated that some defects are related to the entropy of the solid, and that a perfeet solid would violate the second law of thermodynamics. The 2nd law states that zero entropy is only possible at absolute zero temperature. However, most solids exist at temperatures far above absolute zero. Thus, most of the solids that we eneounter are defeet-solids. The defects are usually "point defeets", which are atomlstie... 

Less obviously, perhaps, the second law of thermodynamics assures us that the intensity, 1(A), is also constant along the beam, for if this were not the case, then it would be possible to focus all the radiation from a hot body onto a part of itself, increasing the radiation flux onto that portion and raising its temperature of that portion without doing work - a violation of the second law. The constancy of beam energy and intensity has other consequences, some of which are familiar to most of us. If we solve equation 29-3 for the product (den da) we get ... 

An essential step in the Caratheodory formulation of the second law of thermodynamics is a proof of the following statement Two adiabatics (such as a and b in Fig. 6.12) cannot intersect. F rove that a and b cannot intersect. (Suggestion Assume a and b do intersect at the temperature Ti, and show that this assumption permits you to violate the Kelvin-Planck statement of the second law.)... 

However, AS = — 90.4 J mol for this system. As the change occurs even though AS is negative, this reaction apparently violates the second law of thermodynamics. How do you explain this anomaly in terms of the second law ... 

These corollaries can be proved by demonstrating that the violation of any one of them results in the violation of the second law of thermodynamics. 

One never should try to make a process violate the Second Law of Thermodynamics, but one should never assume that AGr alone predicts what will happen in a chemical reactor. 

We should be clear as to what a catalyst can and cannot do in a reaction. Most important, no catalyst can alter the equilibrium composition in a reactor because that would violate the Second Law of Thermodynamics, which says that equilibrium in a reaction is uniquely defined for any system However, a catalyst can increase the rate of a reaction or increase the rate of one reaction more than another. One can never use a catalyst to take a reaction from one side of equilibrium to another. The goal in reaction engineering is typically to find a catalyst that will accelerate the rate of a desired reaction so that, for the residence time allowed in the reactor, this reaction approaches equihbrium while other undesired reactions do not. Attempts to violate the laws of thermodynamics always lead to failure, but maity engineeis still try. 

---