Kinetics of thermal depolymerization of trimethylsiloxy end-blocked polydimethylsiloxane and polydimethylsiloxane-N-phenylsilazane copolymer

The thermal degradation of Me₃SiO end-blocked polydimethylsiloxane (eb-PDMS) and polydimethylsiloxane-N-phenylsilazane (eb-PDMS–NPhSz) copolymer was studied. For both polymers relative degree of polymerization (DP /DP ₀) as a function of conversion (1 – W/W₀) data were obtained. For eb-PDMS the results were consistent with a mechanism involving a rate determining random siloxane bond cleavage initiation step followed by a rapid and complete depropagation of the active fragments evolving volatile cyclic oligomers. Rate constants (k) for initiation were obtained at four temperatures from plots of DP ^?1 vs. time. An Arrhenius activation energy of approximately 80 kcal/mol was determined and is consistent with a SiOSi scission transition state. The degradation of eb-PDMS–NPhSz appears to follow the same depolymerization process evolving cyclic oligomers. Although DP /DP ₀ vs. C data suggest a random cleavage–complete depolymerization mechanism, an Arrhenius plot suggests a more complex degradation mechanism. The role of impurities as degradation catalysts is discussed.     

Volatile phase profiling of mainstream smoke by glass capillary gas-chromatographic techniques

A heated injection system for a microprocessor-controlled GC has been developed for the (GC)² analysis of the volatile phase of whole smoke of a cigarette. Effects of injection port temperature and the presence of a Cambridge filter pad are demonstrated. Chromatograms are shown for smoke samples with and without a Cambridge Filter with the sample valve oven at 25°, 165° and 205°C. The use of a flame ionization and a nitrogen-phosphorous detector is illustrated.     

Determination of cadmium in mixtures with metal ions

A method for the determination of cadmium microamounts in mixtures with metallic ions withE _1/2 near toE _1/2 of cadmium is discussed. For higher selectivity cadmium was extracted in the form of the pyridin-thiocyanate complexes prior to polarography.

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Bestimmung von Cadmium(II) neben anderen Metallionen

Zusammenfassung Es wird eine polarographische Methode zur Bestimmung von Cd(II) neben anderen Metallionen mitE _1/2 naheE _1/2(Cd) diskutiert. Zur Erhöhung der Selektivität und Genauigkeit wird eine Pyridin-Thiocyanat-Extraktion vorgeschalten.

     

Detection of the pesticide compound 1080 (sodium monofluoroacetate) using fluorine-19 nuclear magnetic resonance spectroscopy

Fluorine-19 nuclear magnetic resonance (19F NMR) spectroscopic measurements were used to determine the chemical nature and amounts of organofluorine in dosed meat baits. Earlier work implied that sodium monofluoroacetate (compound 1080) in meat baits was broken down into other organofluorine compounds such as fluorocitrate. No chemical evidence was found for such compounds. Only monofluoroacetate was detected in the prepared 1080 bait samples. Once the baits have aged, aqueous extraction fails to recover all the added 1080. Analysis using 19F NMR confirmed that the 1080 present in the aqueous extracts of the bait is recovered by Kramer's liquid chromatography method. It was shown here that the aqueous extracts do not recover all the 1080 in the meat bait.     

On [Na(POCl3)4]+ Complex Ion Formation: Conductivity,Raman, and NMR studies in the system phosphoryl chloride–sodium tetrachloro aluminate and related compounds

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.     

Studies on thermal decomposition of 3-chlorobenzoates of rare earth elements in air atmosphere

The conditions of thermal decomposition of the 3-chlorobenzoates of Y, La and the lanthanides from Ce(III) to Lu have been studied. The complexes of La, Pr(III), Sm, Eu, Gd, Tb(III) and Dy were prepared as heptahydrates, those of Ce(III) and Y as pentahydrates, that of Nd as the tetrahydrate, that of Ho as the dihydrate and those of Er, Tm, Yb and Lu as anhydrous salts. On heating, these complexes decompose in three or two stages. They first lose some water molecules and then decompose to oxides through the intermediate formation of LnOCl. Cerium(III) 3-chlorobenzoate loses its crystallization water in two stages and yields the anhydrous salt, which is then transformed directly into CeO₂. All these complexes melt before decomposition in the temperature range 441–513 K.     

A statistical thermodynamic supermolecule-continuum study of ion hydration: Cell and shell methods

A theoretical study of ion hydration using the statistical thermodynamic supermolecule-continuum method is described. The cell and shell methods are used for configurational averaging. Enthalpies, free energies and entropies are calculated for Li⁺, Na⁺, K⁺, F^– and Cl^– each four coordinated with water. The results are in reasonable accord with experiment. A comparison of the site method, cell method and shell method results is presented. The supermolecule-continuum approach to solvent effects seems to be capable of accommodating essential features for the calculation of solvation energy and solvent effects on structure and properties.     

The oxidative cyclization of n-phenyl-3-methylthiopropylamines to form N-phenyl-s-methylisothiazolidinium salts

A series of N-phenyl-3-methylthiopropylamine hydrochlorides were prepared by reacting a series of anilines with methional and sodium cyanoborohydride. These were cyclized upon oxidation by N-chloro-succinimide to the corresponding N-phenyl-S-methylisothiazolidinium derivatives which were isolated as the tetraphenylborate salts. Compounds successfully prepared included the m-methyl, p-methyl, m-methoxy, and p-methoxyphenyl derivatives.     

Germacreme derivatives from diverse marine soft-corals (octocorallia)

Examinations of the extracts of 8 taxonomically-diverse marine soft-corals (Orders Gorgonaceae, Alcyonaceae and Stolonifera, Subclass Octocorallia, Phylum Cnidaria), have resulted in the isolation of 4 new sesquiterpenoids (1–4) of the germacrene type. Three previously known germacrene derivatives (5–7), and the elemane 8, have also been isolated, and complete ¹H and ¹³C NMR assignments for these compounds are reported.     

Synthesis of substituted 3-amino[6,5-b]triazinoindoles

4-[(9-Methyl-as-triazino[6,5-b]indol-3-yl)amino]-2-methyl-2-butanol ( 13 ) and the corresponding 2-methyl-3-imino derivative 12 were synthesized and tested in vitro against Rhino 2 virus. The two compounds were more active than the known triazino[5,6-b]indole 4 . 2,9-Dimethyl-3-methoxy-9H-as-triazino[6,5-b]indolium tosylate ( 21 ) and the related 3-methylthio compound 9 were prepared. Quaternary 21 formed a pseudo base, 22a , whereas quaternary 9 did not form a pseudo base.