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941.
The reactions of ten main group acidic oxides and oxyanions with molten alkali metal carbonate eutectics have been studied by thermogravimetry. Products have been identified by IR and Raman spectroscopy and stoichiometries suggested for the several reactions as oxide is progressively incorporated. Ultimately the tetrahedral ortho-oxyanion was formed except with the less acidic oxides (As2O3, Sb2O3, SiO2). Sulphite was partially oxidised by the carbon dioxide atmosphere to sulphate. 相似文献
942.
H.G. Wiedemann 《Thermochimica Acta》1973,7(2):131-149
A combination of thermobalance and X-ray camera is described which allows simultaneous thermogravimetric (TG) and X-ray measurements under high vacuum. During these measurements the sample is positioned in the sample holder of the camera in the usual fashion and is X-raved while the temperature is varied. The molecular beam of the gaseous decomposition products flows through a connecting tube which acts as a molecular beam former between camera and thermobalance. The molecular beam is directed towards the empty balance pan. The orifice through which the beam exits as well as the pan have special shapes that allow transfer of the angular momentum of the decomposition beam to the balance. The exerted force is a function of time and corresponds to the first derivative of the TG curve. i.e. to the DTG curve. The integrated curve is directly proportional to the change in mass of the probe. A quantitative evaluation is possible if the molecular composition of the beam is known. The calibration of the molecular beam and the evaluation of the measurements will be discussed. The results show that simultaneous detection of X-ray scattering and indirect TG curves allows a better interpretation of decomposition reactions.An additional investigation shows that thermal synthesis of chemical com- pounds can also be studied by thermogravimetry. Based on the same compound as described in the analysis. the pyrosynthesis is demonstrated. The special instrumentation and the test conditions are discussed. 相似文献
943.
The system POCl3–NaAlCl4 was investigated by measuring the conductivity and the Raman and NMR spectra (27Al, 23Na and 31P) as a function of the mol fraction x of NaAlCl4 in POCl3. Additionally, Raman spectra of POCl3 solutions of NaFeCl4, LiAlCl4, LiFeCl4, and KAlCl4 were recorded. In solutions containing Li+ or Na+ ions a liquid to solid (or jelly) phase transition was observed under certain conditions, dependent on salt concentration and temperature. Observed changes in the Raman spectra of the electrolyte solutions in comparison to the pure solvent POCl3 demonstrate the existence of interactions. Clearly, the POCl3 eigenfrequencies and hence the molecules are pertubed. The formation of [M(POCl3)4]+ complexes (M = Li, Na) can be deduced from the Raman measurements. NMR investigations support this conclusion. For assigning of Raman spectra, (Li+, K+) cation and ([FeCl4]?, [SbCl6]?) anion substitutions were employed. 相似文献
944.
Abstract. Two biological effects of UV radiation upon Smittia eggs are observed, both of which seem to be associated with the formation of pyrimidine dimers in the RNA (largely ribosomal) of the eggs. While irradiation of the anterior pole region causes the formation of an aberrant segment pattern (double abdomen induction), irradiation of entire eggs leads to an arrest of their development (inactiva-tion). Both UV effects are photoreversible with different action spectra of the photoreactivating light. A dose rate dependence of the photoreactivation can be observed after both UV effects. The saturating dose rate is about 6 W/m2 (at 440 nm) after UV induction of double abdomens. Upon UV inactivation, the saturating dose rate level for the photoreactivating light is much higher, and a single light flash causes both a considerable biological reactivation and the disappearance of about 7 × 109 pyrimidine dimers from the total RNA per egg. The results indicate the presence of heterogeneous light-dependent repair activities acting upon UV induced pyrimidine dimers in the RNA of the eggs. 相似文献
945.
Kadhim H. Al-Obaidi Robert D. Gillard Leon A. P. Kane-Maguire Peter A. Williams 《Transition Metal Chemistry》1977,2(1):64-66
Summary Bis-(5-nitro-1,10-phenanthroline)platinum(II) dichloride and diperchlorate have been prepared. The reaction between the parent cation and hydroxide ion has been studied using 1 FI n.m.r. spectroscopy and found to involve attack at the ligand. The bis-(2,2-bipyridyl)platinum(II) ion has been shown to be highly reactive towards methoxide ion. The dissociation of a 2,2-bipyridyl ligand is preceded by attack at the ligand.Part XI: R. D. Gillard, t.. A. P. Kane-Maguire and P. A. Williams,Transition Met. Chem., 2, 47 (1977).On leave from the University of Baghdad, Iraq. 相似文献
946.
H. J. Veith 《Journal of mass spectrometry : JMS》1976,11(6):629-633
The field desorption mass spectra of salts such as quaternary ammonium and carbenium salts with organic cations in addition to high cation intensities show signals for cluster ions composed of the salt cation + salt molecule, i.e. [C + nM]+, n = 1–5, thus allowing determination of the molecular weights of salts. In some cases cluster ions of the type [nM – 1]+ are detected. Conditions for the formation of cluster ions are discussed. 相似文献
947.
R. H. Stokes 《Journal of solution chemistry》1974,3(8):671-681
The calorimeter developed in this laboratory for isothermal enthalpy-of-dilution measurements is adapted for use as an adiabatic calorimeter for freezing-point studies. Results are obtained for ethanol solutions in cyclohexane at mole fractions of ethanol from 0.001 up to 0.08. Activities calculated from the results are used to test association models. 相似文献
948.
949.
Summary AT-x phase diagram of the system sodium stearate (NaSt)-stearic acid (HSt) has been determined by DTA. It shows the existence
of five defined association compounds, three of them (2 NaSt · 3 HSt, NaSt · HSt and 3 NaSt · 2 HSt) with an incongruent melting
point and the others (5 NaSt · 2 HSt and 5 NaSt · HSt) with a congruent melting point. The latter two compounds pass through
various mesomorphic phases before melting.
The components do not form solid solutions and are even non-miscible in the mesomorphic state below 200 °C. Mutual miscibility
is only observed above this temperature in the subneat and neat region, occurring in the HSt composition range from 0 to 15
and from 0 to 5 mole% respectively.
The existence of molecular associations in the liquid state is very probable, particularly in the composition range between
30 and 40 mole% stearic acid. This might result in a liquid structure similar to that present in the melt of anhydrous soaps.
Zusammenfassung EinT-x Zustandsdiagramm des Natriumstearat (NaSt)- Stearins?ure (HSt)-Systems wurde mittels DTA bestimmt. Es weist fünf definierte assoziierte Verbindungen auf, drei (2 NaSt · 3 HSt, NaSt · HSt und 3 NaSt · 2 HSt) mit einem inkongruenten Schmelzpunkt und zwei (5 NaSt · 2 HSt und 5 NaSt · HSt) mit einem kongruenten Schmelzpunkt. Die zwei letzteren Verbindungen durchlaufen verschiedene mesomorphe Phasen, bevor sie schmelzen. Die Komponenten bilden keine festen L?sungen und sind im mesomorphen Zustand unter 200 °C nicht einmal miteinander mischbar. Nur bei h?heren Temperaturen sind sie v?llig mischbar, und zwar in der “subneat” und “neat” Region, die im HSt-Bereich von 0 bis 15 bzw. von 0 bis 5 Mol% reicht. Die Existenz molekularer Assoziate im flüssigen Zustand ist sehr wahrscheinlich, vor allem im Bereich zwischen 30 und 40 Mol% Stearins?ure. Dies k?nnte zur Bildung von Strukturen in der Flüssigkeit führen ?hnlich, wie dies bei der Schmelze wasserfreier Seifen der Fall ist.相似文献
950.
The C-methylation of the potassium salt of 1-t-butyl-2-phenyl-3-(p-phenylbenzoyl)azetidine ( 1a ) with methyl iodide was studied in three solvents, and the stereochemical outcome of the reaction was shown to be dependent upon the solvent used. These results are rationalized in terms of the probable relative rates of the reaction in the various solvents and/or the effect of solvent on the structure of the anionic intermediate. Similar treatment of the potassium salt of 1-t-butyl-2-phenyl-3-benzoylazetidine ( 3a ) in ethyl ether gave a comparable result. The configurations of the epimeric C-methyl products ( 2a and 2b , and 4a ) were assigned on the basis of their spectral properties. With the aid of spectral data for a model compound, l-t-butyl-3-benzoyl-azetidine ( 5 ), several stereostructure-spectra relationships for 3-azetidinyl ketones are presented. 相似文献