Le Chatelier-Braun Research Articles

Local Concentration Deviations in a Glycolytic Model of Nonequilibrium Thermodynamics: Emergence of Bistability from Thermodynamic Theories due to Violation of the Lyapunov Stability Theory.

The thermodynamics of nonequilibrium states in the reversible Sel'kov model, a mathematical model of glycolytic oscillations, is reported in terms of the Lyapunov properties of the second differential of its local equilibrium entropy ( S) and that of its entropy production (e.p.) function (σ) per unit volume. This theory interprets the appropriate limit of validity of the generalized Le Chatelier-Braun (LCB) principle for stable nonequilibrium and equilibrium steady states obeying the Lyapunov stability postulate and its implications in terms of the local concentration deviations of the reacting intermediate species S(ATP) and P(ADP) in response to external excitations. The local concentration deviations of the reacting intermediates are reported to be asymmetric for stable steady states in this model system obeying the Lyapunov stability postulate out of equilibrium (both linear and nonlinear domains), whereas symmetrical local concentration deviations prevail at the state of thermodynamic equilibrium, which however never exists in a living cell. In the unstable steady states in this model reaction, as for example, along a limit cycle trajectory not obeying any Lyapunov stability postulate, the two bistable e.p. branches characterized by two forms of deviation product function δ sδ p may be identified separated by a large δ p > 0 value ( p being scaled concentration of the species P) for dσ > 0 and dσ < 0, respectively, which may be generalized as LCB principle for bistability/hysteresis in this model reaction. The method outlined here may be applied safely to other well-known two-variable models of chemistry/biology. For an appropriate three-variable model with one variable in a pseudo-steady-state approximation, this method may be applicable, albeit with some constraints.

A Homeopathy Model in the Light of Hahnemann’s Pristine Idea

The well-known definition of disease, which Samuel Hahnemann presented while making a challenge to provide a tentative theory for his new science and art of healing, is used as a starting point for the model. The biochemical equilibrium is used for a demonstration of the Le Chatelier-Braun principle and/or the Guldberg–Waage Law in order to clarify the principles and to explain the well-known “Law of Similar”. It is shown that a high dilution accompanied by succession is required to release the remedies to their constituent molecular species in order to increase their “vital energy” when taking part in the overall complex biochemical equilibrium that is essential for healing. In addition, it is revealed that, in principle, a single remedy constituent molecular species, when it is in excess, as well as satisfying the dynamic equilibrium, can shift this biochemical equilibrium and trigger the healing process.

The phase space interpretation of the Le Chatelier-Braun principle and its generalization as a principle of natural philosophy

The phase space interpretation of the Le Chatelier-Braun principle and its generalization as a principle of natural philosophy

Applying the expanded Le Chatelier-Braun principle to carbon oxidation in converter baths. 1. Stochastic structure of the harmonic series in the fluctuation of the variable oxidation component

In converter baths, the arrhythmic behavior in the oxidation of carbon and the probability of surges may be assessed from the dispersion of the fluctuation in the variable component of carbon’s oxidation rate ΔVC during intense oxidation. In such conditions, ΔVC may be regarded as a weakly ergodic random process. That approach permits investigation of the frequency series in the fluctuation of the random component ΔVC. It is represented by a practically continuous frequency sequence corresponding to the structural components of the converter process.

Le Chatelier-Braun principle

Le Chatelier-Braun principle was modified for calculating the rate of free energy production [RFEP] in the flow of poly vinyl chloride (PVC) plastisol. At low-to-intermediate shear rate, viscosity decreases with increasing shear rate and reaches a minimum. The behavior was explained by the dominance of the rheological effect at the lower shear rates and that of the thermodynamic effect at the higher shear rates. In the former, viscous resistance was reduced by stress-induced phase separation into an immobilized layer and a mobile phase. In the latter the RFEP increases, reaching a maximum at the minimum viscosity. In the pseudo-plastic flow region, the flow is stable and the RFEP is negative. At shear rates higher than those at minimum viscosity, the immobilized layer dilates and then fractures when the stress becomes higher than the strength of the layer. Both dilatation and fracture are manifestations of flow instability and RFEP is positive, indicating insufficient resistance against failure of the immobilized layer. At super high shear rates, a plug flow takes place with a very thin layer of plasticizer lubricating at the capillary wall. Pseudo-plastic behavior may be explained by two different mechanisms. One is that a very small amount of particles are present in the lubricating layer. The particles are expelled from the layer with the increase in shear rate. The other possibility is that even though the lubricating layer consists of pure plasticizer, the layer increases in thickness in order to avoid excessive secondary flow such as eddy formation.

Backward jump continuous-time random walk: An application to market trading

The backward jump modification of the continuous-time random walk model or the version of the model driven by the negative feedback was herein derived for spatiotemporal continuum in the context of a share price evolution on a stock exchange. In the frame of the model, we described stochastic evolution of a typical share price on a stock exchange with a moderate liquidity within a high-frequency time scale. The model was validated by satisfactory agreement of the theoretical velocity autocorrelation function with its empirical counterpart obtained for the continuous quotation. This agreement is mainly a result of a sharp backward correlation found and considered in this article. This correlation is a reminiscence of such a bid-ask bounce phenomenon where backward price jump has the same or almost the same length as preceding jump. We suggested that this correlation dominated the dynamics of the stock market with moderate liquidity. Although assumptions of the model were inspired by the market high-frequency empirical data, its potential applications extend beyond the financial market, for instance, to the field covered by the Le Chatelier-Braun principle of contrariness.

Non-Diversifiable Risk and Quantity Discounts in Taiwanese Urban Land Markets

Land assembly and subdivision costs are negligible in residential land markets in certain land readjustment districts of Taichung City, Taiwan. Our empirical investigation finds evidence for significant quantity discounts in the case of land sales in these post-consolidated markets. This finding contradicts the prediction of the Le Chatelier-Braun Principle put forward in the work of Lin and Evans (2000). Moreover, the discounts are larger for land sales zoned in R-2 districts than those zoned in R-1 districts. These results are consistent with Brownstone and De Vany's (1991) non-diversifiable risk hypothesis.

New physical interpretation of thermoelectric cooling in semiconductor structures

Nontraditional approach to explain the thermoelectric cooling is suggested . It is based on the Le Chatelier-Braun thermodynamic principle. New effect of cooling and heating of junction of two materials (barrierless thermoelectric cooling) is theoretically predicted, and this effect is different from the Peltier effect (barrier thermoelectric cooling). The suggested thermoelectric effect must be displayed always at the finite values of the junction surface heat conductivity eta. Barrierless thermoelectric effect occurs even in the case when the conducting materials are identical with the same Peltier coefficients. It is shown that both barrier and barrierless thermoelectric cooling effects always exist simultaneously in the general case. The reasons proving reversibility of the thermoelectric cooling process are resulted.

Two characterizations of inverse-positive matrices: the Hawkins-Simon condition and the Le Chatelier-Braun principle

It is shown that (a weak version of) the Hawkins-Simon condition is satisfied by any real square matrix which is inverse-positive after a suitable permutation of columns or rows. One more characterization of inverse-positive matrices is given converning the Le Chatelier-Braun principle. The proofs are all simple and elementary.&nbsp;

Some special features of the le chatelier-braun principle

The relaxation reaction of a system that follows from the Le Chatelier-Braun principle and weakens the result of an external influence turns out to be more intense under a complex action. A method for quantitative determination of the weakening effect for simple and complex actions is suggested.

A Generalized Evolution Criterion in Nonequilibrium Convective Systems

A general evolution criterion, applicable to transport processes such as the conduction of heat and mass diffusion, is obtained as a direct version of the Le Chatelier-Braun principle for stationary states. The present theory is not based on any radical departure from the conventional one. The generalized theory is made determinate by proposing the balance equations for extensive thermodynamic variables which will reflect the character of convective systems under the assumption of local equilibrium. As a consequence of the introduction of source terms in the balance equations, there appear additional terms in the expression of the local entropy production, which are bilinear in terms of the intensive variables and the sources. In the present paper, we show that we can construct a dissipation function for such general cases, in which the premises of the Glansdorff-Prigogine theory are accumulated. The new dissipation function permits us to formulate a generalized evolution criterion for convective systems.

Coordination complexes and equilibrium

The results of this demonstration are explained in terms of equilibrium, Le Chatelier-Braun's principle, and coordination complex formation.

On the unorthodox versions of the Le Chatelier-Braun principle

The different formulations of the unorthodox version of the L e C h at e l i e r-B r a u n principle, as presented by E h r e n f e s t, P l a n c k, Mmes E h r e n f e s t-A f a n a s j e w a and de H a a s-L o r e n t z, and E p s t e i n are discussed. It. is shown that they cover a narrow field only, whereas the orthodox formulation, as explained in some previous work of the author, applies to all possible systems in equilibrium.

The application of the van't Hoff‐ le Chatelier‐Braun principle to chemical equilibria. II

Recueil des Travaux Chimiques des Pays-BasVolume 53, Issue 4 p. 308-311 Articles The application of the van't Hoff- le Chatelier-Braun principle to chemical equilibria. II K. Posthumus, K. Posthumus Bandoeng (Java), Dutch East IndiesSearch for more papers by this author K. Posthumus, K. Posthumus Bandoeng (Java), Dutch East IndiesSearch for more papers by this author First published: 1934 https://doi.org/10.1002/recl.19340530403Citations: 7AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Citing Literature Volume53, Issue41934Pages 308-311 RelatedInformation