title: Determination of the nitrogen content of nitrocellulose from smokeless gunpowders and collodions by alkaline hydrolysis and ion chromatography.
abstract: In this work, a method to determine the nitrogen content of nitrocellulose from gunpowders and collodions is proposed. A basic hydrolysis of nitrocellulose with 1.0% (m/v) NaOH at 150°C during 30 min was carried out for nitrocellulose from gunpowders (after its previous isolation by a protocol optimized by our research group) and from collodion samples. The concentration of nitrate and nitrite ions in the hydrolysate was determined by ion chromatography with suppression and conductimetric detection. The nitrogen content of nitrocellulose was calculated from the values of the concentration of both ions. The quantitative method was evaluated in terms of selectivity, sensitivity, robustness, limits of detection and quantification, and precision, measured as repeatability and intermediate precision. These parameters were good enough to demonstrate the validity of the method and its applicability to the determination of the nitrogen content of nitrocellulose contained in different types of gunpowders (single- and double-base gunpowders, manufactured from 1944 to 1997) and in commercial collodion samples. For gunpowders, the nitrogen content determined with the optimized method was compared with the values reported by the official label of the ammunition (obtained by a digestion/titration method) and errors, by defect, ranging from 1% to 15.2% (m/m) were calculated. The highest errors were obtained for the oldest gunpowders and could be attributed to the loss of nitro groups in the nitrocellulose molecule during aging. For collodion samples, errors could not be calculated since the real nitrogen content for these samples was not given in the label. In addition, the analysis time (2h for nitrocellulose isolation, 1.5h for nitrocellulose hydrolysis, and 0.2h for chromatographic separation) was about 10 times lower than in the digestion/titration method nowadays used for gunpowder samples.
authors.affiliation: Universitary Institute of Research in Police Sciences, Planta Piloto de Química Fina, University of Alcalá, Ctra. Madrid-Barcelona Km. 33.600, 28871 Alcalá de Henares, Madrid, Spain.
authors.forename: María
authors.initials: M
authors.lastname: López-López
authors.forename: Jose María Ramiro
authors.initials: JM
authors.lastname: Alegre
authors.forename: Carmen
authors.initials: C
authors.lastname: García-Ruiz
authors.forename: Mercedes
authors.initials: M
authors.lastname: Torre