Differential thermal analysis study of various oxalates in oxygen and nitrogen

Differential thermal analysis (DTA) of some 25 oxalates are reported in atmospheres of oxygen and nitrogen. It is shown that in some cases in nitrogen the metal is formed, in other cases the oxide of lowest valency state is produced, while a third group give the same oxide product in nitrogen and oxygen. The production in oxygen of the oxide for the first group, and of a higher oxide in the second group is a phenomenon which in the first case involves a further reaction of the metal with the oxygen atmosphere. Another group of oxalates produce characteristic DTA curves due to the formation of carbonate as the initial decomposition product. The dehydrations of these oxalates are marked by endothermic peaks.

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Zusammenfassung Es wurden 25 verschiedene Oxalate durch DTA in Stickstoff- und Sauerstoffatmosphäre untersucht. In einigen Fällen wurde in Stickstoff das Metall gebildet, in anderen das Oxyd von niedrigster Wertigkeit. Es kommt auch vor, daß das gleiche Produkt in beiden Gasen entsteht. Beide erwähnten Produkte werden in Sauerstoff entsprechend oxydiert. Bei einigen Oxalaten erhielt man charakteristische Spitzen, die zeigten, daß das erste Zersetzungsprodukt Karbonat war. Die Dehydration dieser Oxalate zeigte sich durch endothermische Spitzen.

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Résumé On communique les résultats de l'étude de 25 oxalates par analyse thermique différentielle, dans l'oxygène et dans l'azote. On montre que pour certains d'entre eux, dans l'azote, le métal se forme, et que pour d'autres l'oxyde correspondant à la valence la plus faible apparaît; d'autres encore donnent le même oxyde dans l'azote et dans l'oxygène. Dans l'oxygène, et pour le premier groupe, il se forme l'oxyde, tandis que l'oxyde supérieur apparaît pour le second groupe; dans le premier cas, une réaction ultérieure du métal avec l'oxygène de l'atmosphère est mise en jeu. Un autre groupe d'oxalates donne des enregistrements d'ATD caractéristiques en raison de la formation de carbonate comme produit de décomposition initial. Ces oxalates se déshydratent en donnant des pics endothermiques.

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Perovskite Phases in the Systems AIIO–UVIO3. II. On The System ABIIUVIO6, with AII,BII = Ba,Sr, Ca

Studies on the system AB^IIU^VIO₆ with A^II, B^II = Ba, Sr, Ca or combinations of these have shown that the alkaline earth ions cannot substitute each other in all proportions. The perovskites were studied by X-ray diffraction and vibrational spectroscopic methods. The lattice vibration region of the far infrared spectra proved to be of particular value in providing information on the occupancy of the A and B sites. Analysis of the spectra shows that, in the majority of cases, contary to the geometrical predictions some of the larger alkaline earth ions occupy the six-coordinated B sites and some smaller ions the A positions. The number of ions that take in this A ? B site-exchange can amount to 20%, but in normally smaller.     

Microwave spectrum and rotational isomerism in isopropyl mercaptan

A microwave investigation of isopropyl mercaptan has established the existence of both trans and gauche conformers, the trans being more stable by 57 cal mole^?1. Stark effect measurements give the dipole moments as 1.61 ± 0.2 D for the trans and 1.53 ± 0.2 D for the gauche species. The spectra of the isotopic species (CH₃)₂CH³²SD, (CH₃)₂CH³⁴SH, and (CH₃)₂CH³⁴SD of the trans form have also been analyzed, providing a limited amount of structural data.The rotational spectrum of the gauche isomer is noticeably influenced by inversion. Interactions between energy levels in the two lowest inversion states have been satisfactorily accounted for in terms of rotational constants, coupling parameters (G_a and G_c), and ΔE₀, the inversion level splitting. ΔE₀ is found to be 562.4 MHz for the ground state of (CH₃)₂CHSH and 10.0 MHz for (CH₃)₂CHSD. A value of 1.98 kcal mole^?1 has been calculated for the barrier to internal rotation of the -SH group in terms of a V₃ potential.     

Subjective effects of traffic noise exposure: reliability and seasonal effects

Repeated interview surveys were made in suburban residential areas of London. At six selected sites, four sets of interviews were conducted at different times of year and at a further two sites two sets of interviews were conducted during summer months. At all sites traffic noise levels were measured over 24 hours at each interview phase with a microphone 1 m from the dwelling facade at first floor level. Seasonal weather data were also collected. In the course of the repeated interviews the initial sample of 364 respondents was reduced to 222. The questionnaire included two types of noise nuisance scale, questions bearing on the typicality of road traffic conditions, and on the opening and closing of windows. The results confirm others already reported but in addition, show that if annoyance scores are averaged over repeated occasions a highly significant increase in reliability is obtained, and the proportion of score variance accounted for by noise increases significantly. No evidence was found of seasonal changes in traffic noise levels and annoyance scores did not vary significantly despite significant differences in the proportion of windows open at different times of the year.     

Structure–chain length correlations in poly(N-vinylcarbazole)

Narrow molecular weight distribution samples of PVK have been prepared over the molecular weight (M_n) range of 3.7 × 10³ to 2.7 × 10⁶. No evidence of influence of the synthetic procedure on polymer tacticity has been observed. The glass-transition temperature T_g was linearly dependent on 1/M_n (T_g^∞ = 227°C) as predicted by the Fox-Flory chain-end free-volume model but no measurable change in free volume was detected. Crystallizability decreased with M_n and was zero in fractions below M_n = 46,000. This behavior coincides with that predicted by the nucleation theory outlined by Hoffman.²¹ This indicates that the chain-end free energy controls the stability of PVK folded-chain nuclei. The critical molecular weight for nucleation at 305°C was found to be some where in the range M_n = 1 ± 0.5 × 10⁵. No change in the structure of the folded-chain lamellae with M_n was observed but evidence was obtained to support adjacent reentry of chains and a resulting localized crystal distortion.     

A class of bivariate Poisson processes

Tyan and Thomas (J. Multivariate Anal.5 (1975), 227–235), have given a characterization of a class of bivariate distributions which yields, as a special case, a characterization of a class of bivariate Poisson distributions. In this paper we develop an analogous characterization of a class of bivariate Poisson processes and give some properties and examples of such processes.     

Some physical properties of neutrino-gravitational fields

A new solution of the Einstein-neutrino field equations is given. This solution is of Plebanski class [4n]₃ and describes a beam of neutrinos propagating along straight geodesies but possessing an inherent angular momentum density. Another previously known solution is also examined, and using some calculations given by Bonnor it is concluded that a uniform beam of neutrinos is gravitationally stable and that two such beams radiating in the same sense do not interact.     

Influence of composition on the superconducting transition temperature of alloys with the A-15 structure

Superconducting transition temperatures are presented for a wide range of compositions within the A-15 phase of the NbAl system. The maximum T_c of 19.0 K clearly occurs for a composition greater than that of stoichiometric Nb₃Al. This observation, together with a modern calculation by Shen, suggests that the important controlling factor for the maximum T_c in the A-15 class of materials is the approach to the “$\text{λ ? 2}$ limit” rather than structural instabilities or the stoichiometric composition.     

Newer methods of determining electrolytic conductivity

This paper describes, in outline, the theory, construction and use of a three-terminal transformer ratio-arm bridge. The effect of strong impedance and capacitance are minimized without the use of a Wagner earth. By using special cells the use of contacting metal electrodes can be eliminated. The use of the bridge for measuring dielectric constants is also described.