Optimization technique based on learning automata

Optimization techniques are finding increasingly numerous applications in process design, in parallel to the increase of computer sophistication. The process synthesis problem can be stated as a largescale constrained optimization problem involving numerous local optima and presenting a nonlinear and nonconvex character. To solve this kind of problem, the classical optimization methods can lead to analytical and numerical difficulties. This paper describes the feasibility of an optimization technique based on learning systems which can take into consideration all the prior information concerning the process to be optimized and improve their behavior with time. This information generally occurs in a very complex analytical, empirical, or know-how form. Computer simulations related to chemical engineering problems (benzene chlorination, distillation sequence) and numerical examples are presented. The results illustrate both the performance and the implementation simplicity of this method.Nomenclature c _i penalty probability - cp precision parameter on constraints - D variation domain of the variablex - f(·) objective function - g(·) constraints - i,j indexes - k iteration number - N number of actions - P probability distribution vector - p _i ith component of the vectorP as iterationk - r number of reactors in the flowsheet - u(k) discrete value or action chosen by the algorithm at iterationk - u _i discrete value of the optimization variable in [u _min,u _max] - u _min lowest value of the optimization variable - u _max largest value of the optimization variable - Z random number - x variable for the criterion function - xp precision parameter on criterion function - W(k) performance index unit output at iterationk - ₀, ₁ reinforcement scheme parameters - _p sum of the probability distribution vector components     

Sur une conjecture de M. Kac

Summary We consider the following heat conduction problem. Let K be a compact set in Euclidean space ³. Suppose that K is held at the temperature 1, while the surrounding medium is at the temperature 0 at time 0. Following Spitzer we investigate the asymptotic behaviour of the integral E _K (t) which represents the total energy flow in time t from the set K to the surrounding medium ³–K. An asymptotic expansion is given for E _K (t) which refines a theorem due to Spitzer. This expansion also verifies and improves a formal calculation of Kac. Similar results are proved in higher dimensions. Up to the constant m(K), the quantity E _K (t) can be interpreted as the expected value of the volume of the Wiener sausage associated with K and a d-dimensional Brownian motion. This point of view both plays a major role in the proofs and leads to a probabilistic interpretation of the different terms of the expansion.     

LiCoO2中锂离子固相扩散系数随循环次数的变化

The solid diffusion coefficient of lithium-ion in LiCoO₂ cathode material has been investigated by the capacity intermittent titration technique (CITT) at different voltages and at different charge/discharge cycles. By SEM, XRD and FTIR techniques, the structure of LiCoO₂ was studied before and after charge-discharge cycles, and the relationship between solid diffusion coefficient and crystal structure was further discussed. CITT results show that the value of Li⁺ solid diffusion coefficient of LiCoO₂ is about 10^-12 cm²·s^-1. During the whole charge-discharge cycles, the Li⁺ solid diffusion coefficient decreased within the voltage of 4.0～4.3 V, which is attributed to the change of the structure of LiCoO₂.     

Nouveaux thiochlorures de molybdène(II): Mo6Cl10Y (Y = S,Se, Te): Structure et propriétés magnétiques et électriques

The thiochlorides Mo₆Cl₁₀Y (Y = S, Se, Te) have been prepared; they are isostructural with Nb₆I₁₁, space group Pccn, and have four formula units per unit cell. The X-ray structure of Mo₆Cl₁₀Se has been determined from three-dimensional single-crystal counter data and refined to a final R value of 0.053 for 3350 independent reflections. The most important result concerning this structure is a statistical distribution of the Se atom on the unit (Mo₆X′₈) with $\text{X′ ?}\text{7}\text{8}\text{Cl}\text{+}\text{1}\text{8}\text{Se}$: so the compound Mo₆Cl₁₀Se must be formulated $\text{(Mo}{}_6\text{Cl}{}_7\text{Se)Cl}{}_{\mathrm{<mtext>4</mtext><mtext>2</mtext>}}\text{Cl}{}_{\mathrm{<mtext>2</mtext><mtext>2</mtext>}}$. The diamagnetic and dielectric behavior of these new thiochlorides is discussed.     

Synthesis of oxychelerythrine using lithiated toluamide-benzonitrile cycloaddition

Oxychelerythrine, benzo[c]phenanthridine alkaloid, was synthesized from easily available starting toluamide 5 and benzonitrile 6 using toluamide-benzonitrile cycloaddition reaction in 6 steps.     

Study of the State of Water and Oil in Frozen Emulsions Using Time Domain NMR

Here T(1) and T(2)(*) relaxation time measurements by low-field NMR have been used to quantify the state of oil and water in frozen emulsions. Water-in-oil and oil-in-water emulsions have been studied. A discrete method (NLREG program) and a continuous method (CONTIN program) have been used to analyze the FID and inversion-recovery relaxation curves. The FID signal (T(2)(*)) analysis allowed us to calculate the global solid-intermediate-liquid ratio, and the state of the solid and liquid phases was determined by the T(1) values. Thus we have been able to show that the major part of water ( approximately 99%) is in a solid state in such emulsions (average droplet diameter of about 1.5 &mgr;m). This result was confirmed by the study of a solid paraffin-Span 80-water emulsion and a heavy water-caseinate-triolein emulsion. These first results have shown the interest of this new method for the study of the state of water and oil in frozen emulsions. Copyright 2000 Academic Press.     

The "invisible" 13C NMR chemical shift of the central carbon atom in [(Ph3PAu)6C]2+: a theoretical investigation

The experimental 13C NMR chemical shift of the central carbon atom in the octahedral [(Ph3PAu)6C]2+ cluster was investigated on the basis of relativistic density functional calculations. In order to arrive at independent model conclusions regarding the value of the chemical shift, a systematic study of the dependence of the cluster structure on the phosphine ligands, the chosen density functionals, and the basis set size was conducted. The best structures obtained were then used in the NMR calculations. Because of the cage-like cluster structure a pronounced deshielding of the central carbon nucleus could have been expected. However, upon comparison with the 13C NMR properties of the related complex [C{Au[P(C6H5)2(p-C6H4NMe2)]}6]2+, Schmidbaur et al. have assigned a signal at delta=135.2 ppm to the interstitial carbon atom. Our calculations confirm this value in the region of the aromatic carbon atoms of the triphenylphosphine ligands. The close-lying signals of the 108 phenyl carbon atoms can explain the difficulties of assigning them experimentally.