Vaporisation et dissociation thermique des sulfures de phosphore P4S3, P4S7 et P4S10 a l'etat gazeux

Résumé Nous avons montré par spectrométrie Raman à chaud et mesure des tensions de vapeur que P₄S₃ se vaporise de façon congruente tandis que P₄S₇ et P₄S₁₀ se dissocient dès le début de leur vaporisation. P₄S₇ donne réversiblement P₄S₃ et soufre. P₄S₁₀ se dissocie irréversiblement en P₄S₇ et soufre. A l'état de vapeur non saturante, P₄S₃ se dissocie au-dessus de 600° avec formation de phosphore, de soufre et d'autres espèces non identifiées.Nous avons mesuré expérimentalement la capacité calorifique de P₄S₃ liquide, calculé celle de P₄S₃ gazeux et son entropie standard. Nous avons aussi estimé l'enthalpie standard de vaporisation de P₄S₃ à l'aide des mesures des tensions de vapeur saturante. Nous en avons déduit l'entropie standard de P₄S₃ liquide et son point d'ébullition.

---

It is shown by Raman spectroscopy at high temperature and by vapor tensimetric measurements that the vaporisation of P₄S₃ is congruent, whereas P₄S₇ and P₄S₁₀ dissociate at the beginning of vaporisation. P₄S₇ gives P₄S₃ and sulfur reversibly. The dissociation of P₄S₁₀ into P₄S₇ and sulfur is irreversible. Above 600°, in non-saturated vapour the dissociation of P₄S₃ gives phosphorus, sulfur and some unidentified gaseous species. The heat capacity of liquid P₄S₃ has been measured. That of gaseous P₄S₃ and its standard entropy have been calculated. The vaporisation standard enthalpy of P₄S₃ has been estimated from the experimental results on the saturated vapour pressures. The standard entropy of liquid P₄S₃ and its boiling point have been derived from these data.

---

Zusammenfassung Mittels Raman-Spektrometrie bei erhöhter Temperatur und durch Messung der Dampfdrucke wurde festgestellt, daß sich P₄S₃ verflüchtigt, während P₄S₇ und P₄S₁₀ mit Beginn der Verflüchtigung dissoziieren. P₄S₇ ergibt reversibel P₄S₃ und Schwefel. Im Zustand ungesättigten Dampfes dissoziiert P₄S₃ oberhalb von 600° unter Bildung von Phosphor, Schwefel und anderer nicht identifizierter Substanzen.Die Wärmekapazität von flüssigem P₄S₃ wurde gemessen, während die vom gasförmigem P₄S₃ sowie seine Standard-Entropie berechnet wurden. Die Standard-Enthalpie der Verflüchtigung des P₄S₃ wurde durch Messungen der Sättigungs-Dampfdrucke ermittelt. Daraus wurden die Standard-Entropie des flüssigen P₄S₃ sowie sein Siedepunkt berechnet.

---

- - , P₄S₃ , P₄S₇ P₄S₁₀ . P₄S₇ P₄S₃ , P₄S₁₀ P₄S₇ . 600° P₄S₃ , . P₄S₃, P₄S₃ . P₄S₃. P₄S₃ .

---

---

Nous remercions Monsieur Letoffe du laboratoire du Professeur J. Bousquet, INSA de Lyon, 20 Avenue Albert Einstein 401, 69621 Villeurbanne, qui a r6alis6 pour nous les déterminations expérimentales des capacités calorifiques de P₄S₈ liquide.     

Molecular adjustment of the electronic properties of nanoporous electrodes in dye-sensitized solar cells

Molecular modification of dye-sensitized, mesoporous TiO2 electrodes changes their electronic properties. We show that the open-circuit voltage (V(oc)) of dye-sensitized solar cells varies linearly with the dipole moment of coadsorbed phosphonic, benzoic, and dicarboxylic acid derivatives. A similar dependence is observed for the short-circuit current density (I(sc)). Photovoltage spectroscopy measurements show a shift of the signal onset as a function of dipole moment. We explain the dipole dependence of the V(oc) in terms of a TiO2 conduction band shift with respect to the redox potential of the electrolyte, which is partially followed by the energy level of the dye. The I(sc) shift is explained by a dipole-dependent driving force for the electron current and a dipole-dependent recombination current.     

Simulation of immiscible multiphase flow in porous media: A focus on the capillary fringe of oil-contaminated aquifers

This paper deals with the analysis of some aspects of the vertical and lateral migration of oil spills in the unsaturated and the capillary zone of a phreatic aquifer. Our motivation stems from the fact that such contamination represents a severe danger for ground-water resources all over the world and from the present acute problem of jet-fuel contamination in some location of Israel. In the present study, we shall focus our efforts on the analysis of the upper layers of the aquifer which are often subjected to the most significant oil contamination. Neglecting coupled processes effects such as dilution, adsorption and volatilization, also adopting Richard's assumption, a three-phase flow model is introduced with capillary heads of the water and the oil as variables. The resulting model which is coupled and strongly non-linear is solved using a vertical two-dimensional Finite-Element procedure together with a quasi-Newton optimization algorithm. Applying that scheme, various scenarios of oil migration in the unsaturated and the capillary zone were simulated. Some migration characteristics prediced by the numerical simulations are discussed. In particular, the dynamics of the water and oil phases during the migration process is discussed.     

Dimensionality of algebras of symmetry classes of tensors

In this paper we give necessary and sufficient conditions for Algebras of Symmetry Classes of Tensors to be finite dimensional.     

Mixed convexity and optimization results for an (S ? 1, S) inventory model under a time limit on backorders

Das (Oper Res 25(5):835–850, 1977) considered the optimization of a cost function associated with an (S ? 1, S) inventory model assuming the parameters to be the initial number of items in the stock and the service rate. A similar optimization problem associated with an M/E _k /1 queueing system with parameters being the number of servers and the service rate was considered by Kumin (Manag Sci 20:126–129, 1973). Both carried out case-dependent computations and indicated the difficulty of finding general convexity and optimization results for functions with both integer and real variables. In this paper, generalized mixed convexity and computational optimization results for the cost function associated with the (S ? 1, S) inventory system suggested by Das are provided. The generalized convexity results determine the convexity region of the cost function, and therefore the region of possible minimal values of the cost function in the domain. In addition, algorithms to determine the generalized convexity and computational optimization results for the cost function are given.     

Inequalities for cohomology classes of Kaehler manifolds

A set of inequalities for deRham cohomology classes of Kaehler manifolds is proved. As an application, an inequality for Chern numbers of a Kaehler manifold is obtained.     

On locally symmetric vector fields on Riemannian manifolds

It is shown that if ann-dimensional (n≧3) Riemannian manifold admitsr≧2 locally symmetric vector fields (LSVF's), then it is aV(k)-space. In particular, ifr=n−1 then the manifold is a space of constant curvature. In the case of a 3-dimensional Riemannian manifold a close connection between LSVF's and eigenvectors of the Ricci tensor is found.