pH,Definition and measurement at high temperatures

In this review paper, the NBS scale and its limitations are briefly discussed. The magnitude of liquid junction potentials and some calculated values are presented. The use of a molality scale for hydrogen electrode concentration cells at high temperatures is described, and results from measurements on ionization equilibria are summarized. Use of this scale is also recommended for certain circumstances with cells without liquid junction. As an alternative activity scale, use of the Pitzer ion-interaction treatment for ions is recommended for special cases. Finally, reference data are presented for _±HCl in HCl(aq) to 350°C and (HCl+NaCl)(aq) to 200°C that were derived by use of the Pitzer ion-interaction treatment.Presented at the Second International Symposium on Chemistry in High Temperature Water, Provo, UT, August 1991.     

Thermogravimetric analysis of polycarbonates and polythiocarbonates with chlorinated aromatic side-rings

The thermal stability and kinetics parameters of polycarbonates and polythiocarbonates derived from diphenols with chlorinated aromatic side-rings were studied. The polycarbonates exhibited a higher thermal stability than the polythiocarbonates, except for polythiocarbonate Ib, which displayed similar behaviour to that of the analogous polycarbonate. The kinetic parameters of the thermal decomposition were determined by using the Arrhenius relationship and a computer program. In the considered temperature range, all the polymers degraded in a single stage with first-order kinetics.

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Zusammenfassung Es wurde die thermische Stabilität und die kinetischen Parameter von aus Diphenolen mit chlorierten aromatischen Nebenringen abgeleiteten Polycarbonate und Polythiocarbonate untersucht. Polycarbonate zeigen eine höhere thermische Stabilität als Polythiocarbonate. Eine Ausnahme bildet das Polythiocarbonat Ib, das in seinem Verhalten den Polycarbonaten gleicht. Mittels der Arrheniusschen Gleichung und einem Rechnerprogramm wurden die kinetischen Parameter der thermischen Zersetzung ermittelt. Im untersuchten Temperaturbereich zersetzen sich alle Polymere in einer einstufigen Reaktion erster Ordnung.

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The authors acknowledge financial support from the Dirección de Investigación of the Pontificia Universidad Católica de Chile.     

Radical copolymerization of 2-acryloyl thioxanthone with methyl methacrylate

A novel monomer, 2-acryloyl thioxanthone (TXA), was prepared by reaction of 2-hydroxy thioxanthone with acryloyl chloride. Copolymerization of TXA with methyl methacrylate (MMA) in DMF at 80°C was studied in order to evaluate relative reactivities of these monomers. Values of 1.36 and 0.5 were found for the respective reactivity ratios of MMA and TXA, respectively. The resonance stabilization and polar properties were determined and discussed in terms of spectroscopic data.     

1-Arylsulfonylamino-1,2,3-triazole derivatives from functionalyzed 1,2-cyclohexanediones

The heterocyclization reaction of arylsulfonylhydrazones from alkyl substituted 1,2-cyclohexanediones is sensitive to the steric requirements of the alkyl groups. A mechanism for the cyclization in acidic medium is also reported.     

Identification of low molecular vaporizable components in silicone resins using gas chromatography/mass spectrometry

An experimental set-up for the detection of elemental chlorine in chlorinated hydrocarbons (CHCs) is described based on a miniaturized system, which could be used for on-line monitoring of chlorinated compounds. With an optimized time-resolved detection chlorine from CHCs like CCl₄ can be determined by Laser-Induced-Breakdown-Spectroscopy (LIBS) with g/g-detection limits in the gas phase. The application of a miniaturized Nd : YAG laser resulted only in a minor loss in performance, hence it could be used for designing a rugged and small on-line sensor. In addition, preliminary results for the detection of chlorine via the formation of CuCl in the plasma formed by focussing the laser on a copper surface are reported. Utilizing the luminescence of the CuCl D-system at 440 nm, a tenfold improvement in the detection limits was obtained. It appears that the formation of ad hoc selected, small molecules in a laser plasma could be a promising alternative for the selective and sensitive analysis of gaseous chlorinated and other species.