Analytical Methods in Rubber Chemistry. (IV) The Determination of Peroxidic Oxygen

Abstract

In the previous publication, of Farmer, Tristram and Bolland, it was stated that methods were required to estimate the various forms in which oxygen occurs united to the rubber molecule, and a method for the estimation of hydroxyl oxygen was discussed. The determination of peroxidic oxygen in oxidized rubber presents two distinct problems. It is necessary to employ a method which, first, is satisfactory in the presence of unsaturation and, secondly, ensures effective contact between the long rubber chains and the analytical reagent. These requirements are both satisfied by the modification described below of the colorimetric method of Young, Vogt and Nieuwland. Before describing the modified technique, some mention must be made of the earlier methods and of the errors which arise when they are applied to the determination of peroxidic oxygen in unsaturated compounds. All the earlier methods for the determination of peroxidic oxygen depend on the oxidation of potassium iodide and titration of the liberated iodine. This method is open to the objection that the liberated iodine immediately attacks the double bonds remaining in the oxidized material. This difficulty was recognized by Stephens, who, using a method in which the peroxidic oxygen was reduced with stannous chloride, succeeded in estimating about 80 per cent of the total peroxide present in cyclohexene peroxide. Yule and Wilson estimated the peroxide in cracked gasoline by shaking with an acid solution of ferrous thiocyanate and back-titrating the resulting ferric salt with titanous chloride. The results were later contested by Young, Vogt and Nieuwland, who described the colorimetric method which has been adopted, with some modification, in the present work.

Evaluation of Ferrous Thiocyanate Colorimetric Method

“…In the light of later studies with the colorimetric method (2) which indicated that values obtained on autoxidized rubber samples were in no case higher than warranted by the amount of oxygen absorbed by the rubber, it seemed more likely that oxygen either catalyzes the reduction reaction or inhibits the ferrous ioncatalyzed decomposition reaction. Failure to obtain quantitative reduction of peroxides of known purity by the Yule-Wilson method even in the presence of oxygen is ascribed to too low a ratio of dissolved oxygen to peroxide, this ratio being of the order of only one hundredth of that obtaining with the ferrous thiocyanate colorimetric method.…”

Kinetic Studies of Petroleum Antioxidants

“…Peroxide analyses were made by the ferrous thiocyanate method of Bolland and coworkers (6). Phenol was extracted from the mineral oil solutions diluted w'ith heptane by using 0.5;V aqueous sodium hydroxide, was then acidified, and w'as analyzed by bromination to the 2,4,6-tribromophenol with iodimetric determination of excess bromine.…”

Trace determination of hydroperoxides by spectrophotometry in organic media

“…The thiocyanate method was originally developed for work in acetone5 or methanoliclO media. Bolland et a1., 3 Smiths and Lea9 used benzenemethanol (7 + 3) and Lebelll reduced the proportion of methanol to 12%. Zeppenfeldl2 reduced the concentration of methanol even more (8%) for the determination of hydroperoxides in PVC.…”