Boundary phase stability and critical phenomena in higher order solid solution systems II

The thermodynamic treatment of double-pseudobinary solutions of the type (A _xB_y) _{r o}(M _uN_v) _{s o} presented in a preceding publication was extended to include the conditions defining the critical points for the asymmetric case (r _os _o) and approximations for the spinodal and binodal surface near the critical solution point.Closed solutions for the coordinates of the critical points were obtained only for systems with ideal mixing behavior, and the isothermal binodal and spinodal near the critical solution point in such systems are adequately approximated by circles and ellipses, respectively. An axes ratio of is nearly independent of the relative sublattice abundance and the major effect of changes in the ratios _o/r _o is a rotation of the binodal by an angle tg .The principal features of nonideal regular systems for temperatures close to the critical solution point are described by expressions derived from small term expansions of the conditional equations, but generalizations are not possible to the same extent as for the case with ideal boundary systems. The results are discussed and the application of the equations demonstrated on model examples.Mit 6 Abbildungen     

Interactions intramoléculaires en série cyclohexanique: Partie II. Spectres photoélectroniques de chloro-2 cyclohexanones

The photoelectronic spectra of cis-2-chloro, 4-tert-butylcyclohexanone and cis-2-methyl-2-chlorocyclohexanone have been analysed. These analyses have been used in an investigation into the nature of the orbital interactions in these molecules, and into the dependence of these interactions on the axial or equatorial position of the halogen atom. The preferential conformations of 2-chlorocyclohexanone and 4,4-dimethyl-2-chlorocyclo-hexanone have thus been obtained.     

Benzo[b] thiophene derivatives. XVIII. The sulfur isosteres of harmaline,harmine and related isomers

The sulfur analogs of harmaline, 7-methoxy-3,4-dihydro-1-methyl[1]benzothieno[2,3-c]-pyridine (Ib), harmine, 7-methoxy-1-methyl[1]benzothieno[2,3- c ]pyridine (IIb), and corresponding 6-methoxy isomers (Ic and IIc) have been synthesized for pharmacological evaluation as monoamine oxidase inhibitors.     

Reactions of tetrahydro-as-triazine-3(2H)-thiories with α, β-difunctional compounds

The results of allowing tetrahydro-as-triazine-3(2H)-thiones to react with various α,β-diiunctional compounds, such as, α-bromoethyl p-toluenesulfonate, chloroacetaldehyde, α-bromophenylacet-uldehyde, phenaeyl bromide, chloroacetonitrile, α-bromophenylaeelonitrile, and α-cyanobenzyl p-toluenesulfonate are discussed. These condensations give either a 5H-thiazolo[3,2-b]-as-triazine or a 2H-thiazolo[2,3-c]-as-triazine.     

Bulk and localized oxygen concentration measurements of steam-oxidized zircaloy-4 using nuclear analysis techniques

Quantitative measurement of both bulk and localized oxygen concentrations is of importance in the study of oxidation kinetics. We describe the combined application of two nuclear techniques, fast neutron activation analysis and (d, p) nuclear microprobe, to the determination of oxygen concentrations and surface profiles for steam-oxidized Zircaloy-4 cladding specimens. Results of measurements using these techniques are presented. Work partially supported by Electric Power Research Institute Contract T.S.A. No. 20.     

Vibrational emission of NO2 from the reaction of NO with O3

Vibrational chemiluminescence in the Δν₁ = Δν₃ = ?1 band of NO₂ is observed both in the O + NO and O₃ + NO reactions and shown to be emitted by molecules with up to 11 000 cm^?1 of vibrational energy. Quenching rate constants of NO₂³ are estimated ranging from about 6 × 10^?14 for Ar to about 3 × 10^?12 cm³ s^?1 for NO₂. The ratio of vibrational to electronic emission is 0.06 ± 0.03 for O + NO and 5.3 ± 1.0 for O₃ + NO. It is suggested that vibrationally excited NO₂ is a major product of that channel of the O₃ + NO reaction which forms ground-state NO₂(²A₁) directly.     

Conformational energies of cyclenes

An universal function for non-bonded interactions, which takes into account the relative orientation of the bonds is considered in calculating the conformational energies of cycloalkenes and cycloalkadienes. A comparison is made with previous results obtained by using usual 6-exp functions for non-bonded interactions.     

Template synthesis in the nickel(II)–thiocarbohydrazide–propanone triple system

The complexing process proceeding in the Ni^II–thiocarbohydrazide (H₂N–H–NC(=S)–NH–NH₂)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of Ni^II with (N,N,S,S)-donor tetradentate ligands having NiL¹, NiL² and NiL³compositions where L¹ is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L² is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L³ is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur.     

Reaction of mercury(II) and xylenol orange-I Effect of the buffering media

The influence of the buffering medium on the reaction of Hg(II) with Xylenol Orange has been studied. Amine-type compounds are complexed by Hg(II)/Xylenol Orange with a sharp hyperchromic effect on the reagent itself, at 590 nm, but complex formation of Hg(II)/Xylenol Orange in non-amine-type buffer, such as citric acid-phosphate, gives a hypochromic effect on Xylenol Orange at 580 nm. Hg(II) is determined at pH 7.5 in two ranges of concentration, 2-9 ppm in citrate buffer, measured at 580 nm ( = 2.50 x 10(4)), and 6-11 ppm in hexamine buffer, at 590 nm ( = 4.18 x 10(4)).     

Synthesen von Heterocyclen, 111. Mitt.: Zur Umsetzung von Benzoylaceton und seinen Derivaten mit Malonylchlorid

Zusammenfassung Der Vorgang der thermischen Umlagerung des 4-Hydroxy-5-acetyl-6-phenyl-pyrons-(2) (1) zum 4-Hydroxy-5-benzoyl-6-methyl-pyron-(2) (4) wird an Hand weiterer Beispiele studiert und ferner der Einfluß der Substituenten am C-5 bzw. C-6 des Lactonringes untersucht.

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An investigation of more examples of the thermal rearrangement of 5-acetyl-4-hydroxy-6-phenyl-pyrone-(2) to 5-benzoyl-4-hydroxy-6-methyl-pyrone-(2) was carried out, it showed the influence of substituents at C-5 and C-6 of the lactone ring.