The rate of hydrolysis of the sulphate acid ester in unstabilized cellulose nitrates in acetone/ water solution a t 25' C. has been studied. The rate of hydrolysis in 90% acetone/water was too slo\\l to produce a measurable increase in acidity during 24 hours. In 99% acetone/water solution the initial hydrolysis was \:cry rapid and was followed by slower hydrolysis which was complete after 24 hours. Si~nilar results were obtained with wood cellulose nitrates.In the case of cotton cellulose nitrates, there was an indication that hydrolysis of the sulphate acid ester decreased as the nitrogen content increased. The rate of hydrolysis of the sulphate acid ester in both cotton and wood cellulose nitrates was \-ery similar to that of the sulphate acid ester in cellulose acetate sulphate.
Cetrimidel is a widely used germicidal material, which is composed of a mixture of quaternary ammonium salts of the general type CH,(CH,),N(CH3)3 Br-where n = 11, 13 and 15, the tetradecyl homologue predominating. It is a powerful germicide whose properties arise largely from its considerable surfactant nature. At the same time it is comparatively free from unwanted side-effects when applied to wounds and the skin in general and these properties have led to the widespread use of cetrimide in proprietary pharmaceutical preparations. However, excessively large applications can cause hypersensitivity to cetrimide, and when taken internally it causes nausea and vomiting followed by further deterioration, leading to paralysis of the respiratory muscles and finally asphyxia.The work described in this paper has been carried out for two main purposes: firstly, to establish a convenient analytical procedure, which is specific for cetrimide and which can be used for most, if not all, of the preparations in which it is included, and secondly, to show that pyrolysisgas chromatography can probably be used for the quantitative analysis of many quaternary ammonium salts. Pyrolysisgas chromatography has been used previously for the determination of trace amounts of herbicidal quaternary ammonium salts, viz., paraquat and diquat, in pond and river waters2J but as a technique it has not been widely used other than in the polymer field and only rarely as a quantitative analytical technique. Similarly, little has been published on the analytical chemistry of cetrimide although its composition has been inve~tigated.~ The official assay procedure5 is in no way specific for cetrimide and is only applicable in the absence of other quaternary ammonium salts.
The influence of water concentration upon the hydrolysis of the sulphate acid ester in unstabilized cotton and wood cellulose nitrates in acetone/water solutio~l a t 2 5 " f O.1° C. has been determined. When the water content of these systems was increased, the rate of hydrolysis of the sulphate acid ester in cotton or wood cellulose nitrates decreased. This effect was greatest in the first hour of hydrolysis. The presence of more than about 2% water in t h e acetone/water solution prevented the completion of hydrolysis after 24 hours.
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