A novel driven‐rod, radiant pyrolysis technique has been used to study steady‐state linear regression of vertically mounted polystyrene rods degrading under high‐flux, nonflaming conditions that simulate those of combustion. With this technique a reliable, reproducible temperature‐depth profile (identical for combustion and radiant pyrolysis) for polystyrene has been obtained and used to successfully calculate the observed mass loss rate. Residues and volatiles have been analyzed. Mechanistic treatment of these results indicates that degradation of polystyrene under these rapid‐heating conditions is similar to that under more conventional slow‐heating conditions in the absence of oxygen. Oxidation is unimportant in the condensed‐phase degradation of polystyrene in this configuration. This radiant pyrolysis technique has also been used to obtain the heat of gasification of polystyrene.
SynopsisPorous glass packing materials have been used for gel permeation chromatography using an aqueous phosphate buffer. Elution volumes were determined for polystyrene sulfonates, dextrans, and small neutral and charged molecules a t three different ionic strengths, viz., 0.01M, O.lM, and 1.OM phosphate, pH 7.0. The pore diameters of the glasses studied were 75,240,700, and 2000 A.Elution volumes of nonionic species were unaffected by changing the solvent ionic strength. Elution volumes of charged species were markedly affected by the ionic strength of the solvent. This was attributed to a combination of decreased polymer dimensions and decreased ionic exclusion with increasing buffer concentration. The use of low ionic strength solvents may be exploited to tailor the separating range for polyelectrolytes with porous glass packings. This is particularly useful in the low molecular weight range where the lowest pore size available is 75 A.
A B S T R A C TAn improved oxygen bomb apparatus has been developed. The increased precision and readability of the continuous pressure recording allows a new method of end-point measurement. It was possible to use smaller test samples than any previously reported. Sample size and oxygen pressure were shown to be relatively unimportant variables. Temperature is the most useful variable for controlling test time. This is preferable over sample dispersion or addition of catalysts in terms of simplifying the procedure. Peroxide formation at the oxygen bomb test end point is three to four times the value at the end point of the Active Oxygen Method.
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