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.

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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.

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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.

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

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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.     

Complexation of Cu(II) with <Emphasis Type="SmallCaps">L</Emphasis>- and <Emphasis Type="SmallCaps">DL</Emphasis>-threonine: An ESR study

Complexation of Cu(II) ions with L- and DL-threonine in aqueous solution was studied. Treatment of the ESR spectra of solutions containing Cu(II) and threonine in various ratios and having various pH, involving total line shape analysis, revealed formation of geometric isomers of the complex ions [Cu(thrH_–1)₂]^2– differing in the mutual arrangement of the N and O atoms in the equatorial plane; the complexation and isomerization equilibrium constants were determined.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1388–1391.Original Russian Text Copyright © 2004 by Statsenko, Bolotin, Panyushkin.This revised version was published online in April 2005 with a corrected cover date.     

Oxidation of alcohols by transition metal complexes—iv : The rhodium catalysed synthesis of esters from aldehydes and alcohols

Both RhH(CO)PPh₃)₃ and a catalyst made in _situ from RhCl₃·3H₂O, PPh₃ and Na₂CO₃ catalyse the reaction of a range of aldehydes with simple primary alcohols to give esters together with alcohols formed by reduction of the aldehydes. The proportion of ester can be increased by adding an efficient hydrogen acceptor. The reaction can also be used to produce 5- and 7-membered lactones from aromatic dialdehydes. Propan-2-ol and the _{in situ} catalyst reduce some aromatic aldehydes to the corresponding alcohols without concomitant ester formation.     

Crystal and molecular structure of 5-ethyl-5,10-dihydrido-10,10-diphenylphenazasiline

The structure of 5-ethyl-5,10-dihydro-10,10-diphenylphenazasiline has been determined from three-dimensional X-ray data collected by counter methods. The compound in the monoclinic space group P2₁/b with a 10.782(5), b 22.642(9), c 8.830(4) Å and γ 74°41′(2). The observed and calculated densities (Z = 4) are 1.22 and 1.21 g cm^-3, respectively. Anisotropic(Si, N, C)-isotropic block-diagonal least squares refinement gave a conventional R factor of 3.9% for 1871 reflections with I>2σ(I). The central six-membered ring of the tricyclic system adopts a boat conformation; the dihedral angle between the benzo-group planes is 157.3°. The CSiC angle in the heterocycle is 101.1(1)°; the mean SiC bond length is 1.850(2) Å (in the cycle) and 1.862(2) Å (with Ph group). The nitrogen atom is displaced 0.05 Å from the plane of the adjacent carbon atoms; the sum of the angle about N is 359.7°.     

A comparison of SCF-Xα and extended Hückel methods for metal clusters

A comparison of some results from Xα-scattered wave (Xα-SW) and extended Hückel (EH) calculations for metal clusters is given. It is found that small clusters of atoms (≈ 13 atoms) using the Xα-SW method reproduce many of the features of the electronic structure of the bulk metals, whereas this is not the case for the same clusters using the EH method. A more systematic approach to EH parametrizations is suggested in order to make this method a more viable approach to treating metal clusters.     

Enhanced capacity of chitosan for transition-metal ions in sulphate-sulphuric acid solutions

Batch measurements have shown that the collection yields of chitosan for chromium(III), iron(III), nickel, copper(II), zinc and mercury(II) from sulphuric acid solutions are higher when the solutions contain ammonium sulphate, or when chitosan conditioned in ammonium sulphate is used, particularly at pH 3.0 and 5.0. The contrary is verified for the oxy-anions vanadate, chromate and molybdate. Manganese is never collected. At pH 1.0 no collection occurs. A procedure for recycling chromatographic columns includes fixation of Cu or Ni from a sulphate solution at pH 3-5 on sulphate-conditioned chitosan, and elution with 0.1M sulphuric acid/0.1M ammonium sulphate at pH 1.0; the presence of sulphate in the eluent obviates the detrimental effect of sulphuric acid on the next cycle. Sulphate is the favoured counter-ion of the chelated cations and its action produces shorter chromatographic bands. The interaction of sulphate with chitosan is discussed in terms of crystallinity and steric distribution of the protonated amino-groups in the polymer. Data on the new diethylaminohydroxypropylcellulose are included.     

Zum Mechanismus der Hydrogenolyse aromatisch gebundenen Halogens

The selective chlorination of a m/p-xylene mixture, followed by distillation of the unreacted p-xylene, leaves a residue containing up to 90% of monochlorinated m-xylenes. m-Xylene is recovered from the latter by heterogeneous catalytic hydrogenolysis in the gas-phase. It was found that the hydrogenolysis on certain noble metal catalysts proceeds according to an ionic reaction mechanism at temperatures below a definite temperature range. At temperatures above this range hydrogenolysis follows a radical reaction mechanism.     

Use of spectroscopy of gamma-radiation from the inelastic scattering of reactor fast neutrons for elemental analysis

Gamma-spectra of stainless-steel and soil samples have been measured to study the potentialities of using spectroscopy of γ-radiation from the inelastic scattering of reactor fast neutrons for element analysis of various materials. Contents of iron, chromium, nickel, manganese, silicon and titanium in stainless steel, and those of silicon, iron, aluminium, magnesium, calcium, sodium, titanium, carbon and oxygen in soil have been determined by comparing the spectra of the samples with those of specially prepared mixtures of elements. The distinguishing features, advantages, and limitations of this method are discussed.     

lα-hydroxy previtamin D3, and its selective formation from 1-keto previtamin D3

An efficient method for the preparation of crystalline α-hydroxy previtamin D₃ is described. Also the stereoselective reduction of 1-keto previtamin $\text{9}$ is discussed; it was observed that with aluminum hydride $\text{7}$ is the most abundant product. This stands in contrast with previously reported LiAlH₄ and NaBH₄ mediated reductions.     

Determination of mono-, di- and polyamines in foods using a single-column amino acid auto-analyzer

A fully automated, rapid and sensitive method was developed to analyze fourteen different biogenic amines in food. Using a Technicon C4 ion-exchange resin column (20 m X 0.5 cm), adapted to an automatic Technicon TSM amino acid analyzer, the following amines were separated and quantified: adrenaline, noradrenaline, 1,3-diaminopropane, putrescine, cadaverine, histamine, spermidine, dopamine, spermine, agmatine, tyramine, serotonin, phenethylamine and tryptamine. Five buffers were required to elute the amines using a gradient of pH from 5.6 to 12.7; the column temperature was maintained at 65 degrees C. The method was also assayed on ground beef, cheese and wine samples. Amines from cheese and ground beef samples were extracted with 0.6 M perchloric acid. No extraction of wine samples was necessary.