Determination of nitrocellulose by capillary electrophoresis with laser-induced fluorescence detection

The industrial application of nitrocellulose depends on its nitrogen content. When nitrocellulose presents high nitrogen content is used in the manufacture of explosives whereas nitrocellulose with low nitrogen content is used to make a wide range of daily and non-explosive products (e.g. cigarettes, paints, lacquers). This fact makes really important to develop a method for the determination and discrimination of nitrocellulose samples. This work reports, for the first time, the qualitative determination of nitrocellulose previously derivatized with 8-aminopyrene-1,3,6-trisulfonic acid (APTS) by capillary electrophoresis (CE-LIF) with laser-induced fluorescence detection (CE-LIF). APTS-labeled nitrocellulose was determined in lowly and highly nitrated nitrocellulose samples present in collodions and smokeless gunpowders, respectively, after their pulverization in liquid nitrogen. The method described enables the visual discrimination of different nitrocelluloses on the basis of the different electrophoretic profiles obtained, and provides a useful tool to determine nitrocellulose. Additionally, the use of field-amplified sample injection (FASI) enabled enhanced sample detection, which made it possible to determine nitrocellulose contained in ∼15 μg of gunpowder.     

A reproducible method for determination of nitrocellulose in soil

A reproducible analytical method for determination of nitrocellulose in soil is described. The new method provides the precision and accuracy needed for quantitation of nitrocellulose in soils to enable worker safety on contaminated sites. The method utilizes water and ethanol washes to remove co-contaminants, acetone extraction of nitrocellulose, and base hydrolysis of the extract to reduce nitrate groups. The hydrolysate is then neutralized and analyzed by ion chromatography for determination of free nitrate and nitrite. A variety of bases for hydrolysis and acids for neutralization were evaluated, with 5N sodium hydroxide and carbon dioxide giving the most complete hydrolysis and interference-free neutralization, respectively. The concentration of nitrocellulose in the soil is calculated from the concentrations of nitrate and nitrite and the weight percentage of nitrogen content in nitrocellulose. The laboratory detection limit for the analysis is 10mg/kg. The method acceptance range for recovery of nitrocellulose from control samples is 78-105%.     

Hydrogen Bonding in Nitrocellulose and Its Implications on Deterring of Small Arms Propellant

The hydrogen bonding characteristics of well-characterized nitrocellulose samples were studied by means of IR spectroscopy. Results obtained for nitrocellulose samples of varying nitrogen content showed that the strength of the hydrogen bond increases with decreasing nitrogen content. In addition, atmospheric moisture was found to hydrogen bond with nitrocellulose hydroxyl groups. The implications of these findings on the deterring phase of the small arms propellant manufactruring process are discussed.     

High-performance ion chromatography assessment of inorganic and organic nitrogen fractions in potatoes

A new high-performance ion chromatography assay for organic and inorganic nitrogen analysis has been proposed and examined. In the devised protocol, inorganic sample constituents were measured after ultrasonically assisted water extraction. The amine and amide nitrogen content was assessed after modified Kjeldahl digestion and determined as NH₄⁺, and the total nitrogen content was quantified as NO₃⁻ after microwave-facilitated digestion. Finally, the nitro, azo, azoxy nitrogen was calculated by comparison of the total nitrogen content and all measured nitrogen species. The detection limits of the measured ions were 2.0, 0.82 and 0.17 mg L⁻¹ for nitrate, nitrite and ammonium, respectively. For samples of potatoes, the average shares of the nitrogen species found in the total nitrogen content were: 0.83% of nitrate nitrogen, <0.03% of nitrite nitrogen, 2.1% of ammonium nitrogen, 71% of nitro, azo, azoxy nitrogen, and 26% of amine, amide nitrogen. We expect the method to be applicable to different vegetable samples. The quality of the results obtained was verified by analyzing certified reference material and comparing to another analytical method.     

Flow-injection determination of ammonia in kjeldahl digests by gas diffusion and conductometry

A flow injection/conductometric method is proposed for determing ammonia in solutions obtained from Kjeldahl digestion. The method is based on diffusion of ammonia through a PTFE membrane from an alkaline (NaOH/EDTA) medium to a deionized water stream. The change in conductance of the deionized water stream is proportional to the ammonia concentration present in the digest. The effects of flow parameters, temperature and potential interferences are reported. Approximately 100 samples can be injected per hour; the precision is about 1%. Results for total nitrogen in vegetable tissues, animal feeds and fertilizers are in good agreement with those obtained by the usual distillation/titration method.     

Fabrication of Tubular Structure Agglomerates of Calcium Carbonate by Using Collodion Film

A novel and simple method for preparing tubular structure agglomerates of calcium carbonate (CC-tube) is described. Calcium chloride and sodium carbonate aqueous solutions were used as reactants separated by a collodion film (a nitrocellulose material) in aqueous solution. The effects of the concentrations of calcium chloride and sodium carbonate aqueous solutions on the morphology and phase structure of the as-obtained samples were investigated. The CC-tube growth was prevented with the increase of reactant concentration from 0.5 to 1.0 mol•L－1. Compared with Na2CO3 aqueous solution, it is favourable to grow calcite crystals in CaCl2 aqueous solution. The products were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron- microscopy.     

硫酸铵中氮含量的电位滴定检测

建立一种酸碱电位滴定法直接测定硫酸铵中氮含量的方法。样品溶解后,可直接用氢氧化钠标准滴定溶液进行滴定。为了保证检测的准确度,分别使用硫酸铵高纯试剂和邻苯二甲酸氢钾基准试剂对氢氧化钠标准滴定溶液进行标定,并对标定结果进行比较,两种方法基本无差异。同时,通过适量硫酸的加入避免了样品中游离硫酸对检测结果的影响。该方法检测速度快、检测精度高、绿色环保、易于控制,非常适合于硫酸铵中氮含量的检测。将本方法与蒸馏后滴定法(仲裁法)检测结果进行比较,两种方法无显著性差异。采用本方法测得氮含量的加标回收率为99.9 %-100.3 %,相对标准偏差(RSD,n=5)为0.03 %-0.05 %。分别使用实验方法和蒸馏后滴定法测定不同样品的氮含量,结果相吻合。     

配位滴定法测定锌含量的合适酸度条件

调节待测体系的pH值是配位滴定中一种重要的选择性滴定手段。采用CTE1.0程序计算了不同酸度条件下的终点误差,同时用配位滴定法测定了模拟样品和市售药品中的锌含量。计算结果和实测结果均表明,在不含钙离子的待测体系中,测定锌离子含量的合适酸度条件为pH=6;在钙、锌混合离子溶液中,测定锌含量的合适酸度条件为pH=5。平行测定实验的相对标准误差为1.63%,加标回收率为99.1%-101.8%。     

Comparative analysis of smokeless gunpowders by Fourier transform infrared and Raman spectroscopy

Fourier Transform Infrared (FTIR) and Raman spectroscopic techniques were used to perform a comparative study of the spectral profiles of single-base, double-base and triple-base smokeless gunpowders. Preliminary results based on visual comparison of the spectra point out that spectra obtained by both vibrational techniques were useful for a rapid identification of gunpowders containing dinitrotoluene as one of the major components and triple-base gunpowders. Additionally, the Raman spectra of gunpowders with diphenylamine in its primary composition showed a characteristic band, assigned to 2-nitro-diphenylamine, allowing the identification of this type of gunpowders.     

Adsorption of nucleic acids on collodion films

Adsorption of nucleic acids on collodion films from solutions of different ionic strengths was studied, and the adsorption equilibrium constants were determined. The primary adsorption of DNA samples on collodion films was examined depending on various factors. A comparative analysis of different techniques (vacuum drying, UV irradiation) employed for immobilization of DNA samples on collodion films was carried out.     

微机模拟计算各种类型酸的滴定曲线以及滴定误差

本文对三元酸滴定曲线的精确计算公式加以改进,设计出适合各种类型酸的滴定曲线和滴定误差的模拟计算程序,通过在Rainbow-100机上运行,计算结果与文献报道相符。此法简单、快速,对选择滴定条件,优化实验方法具有很重要的应用价值。     

Stability Indicating HPLC Analysis of Dibromodulcitol in Aqueous Solutions

Abstract

A stability-indicating HPLC analytical method for the anticancer agent dibromodulcitol (DBD, Mitolactol, NSC-104800) has been developed that will completely resolve the compound from its degradation products. A 5 μm octadecylsilane analytical column was used in conjunction with a refractive index detector, with a mobile phase of 98:2 water/methanol. The limit of DBD detection was determined to be 250 ng (5 μg/ml) with a signal to noise ratio of 2:1. Intraday variation of the method, as percent relative standard deviation, was 4.37% (12.5 μg/ml) and 0.973% (250 μg/ml), and interday variation was 3.93% (250 μg/ml). Comparison with potentiometric titration of bromide after digestion of DBD with NaOH indicated that the method was more sensitive and specific than titration. The method has been used in tablet content analysis, as well as degradation studies of DBD in solution.     

电感耦合等离子体原子发射光谱法(ICP-AES)测定5XXX系铝合金中的高镁含量

采用电感耦合等离子体原子发射光谱法测定5XXX系铝合金中的高镁含量,选择20mL稀王水溶液溶解试样,以消除合金中的基体元素及其它共存元素的干扰为目标,选择测定镁含量的分析谱线为280.270nm。分别称取与分析试样基体近似的三种铝合金标准物质0.100 0g,按试样相同的溶解方法处理并定容至100mL,选择仪器工作条件,制作分析曲线,进行曲线校准,按照同样的方法对4个样品各测定6次,测定值的相对标准偏差均不大于0.59%,用标准加入法测得加标回收率在94.0%~104.0%,测定值和环己二胺四乙酸分离络合滴定法测定的5XXX系铝合金中的镁量结果一致。     

A high-precision titration of 4-aminopyridine A value for the faraday

A specimen of 4-aminopyridine purified by repeated sublimation in an atmosphere of nitrogen has been titrated coulometrically in two ways: (1) directly, using the hydrazine-platinum anode, and (2) with perchloric acid, the titration being completed coulometrically and the perchloric acid being standardized coulometrically. The values for the faraday calculated from these titrations are 96,486.40 (1.53) and 96,486.78 (0.57), 1972 NBS coulombs per mole, respectively, the average being 96,486.69 (0.81) and the numbers in the parentheses the standard deviations. The maximum error obtained by combining the estimated maximum errors in the various measurements was 8.4 ppm.     

The determination of nitrogen in nitrocellulose

A method for the determination of nitrogen in nitrocellulose has been developed. The sample is dissolved in concentrated sulphuric acid and a salicylic acid solution is added. The nitrosalicylic acid formed is reduced at room temperature with an excess of titanous chloride solution and the excess is estimated by titration with ferric alum. Statistically designed experiments were used to establish the conditions necessary for accurate results. The procedure is more rapid than the usual nitrometer method and gives results of high precision; e.g. on a mean result of about 13.8% nitrogen, the standard deviation is 0.014.     

Analytical applications of condensed phosphoric acid-I Determination of ferrous and total iron in iron ores after decomposition with condensed phosphoric acid

A simple method is described for the determination of ferrous and total iron in iron ores. Iron ores are dissolved by condensed phosphoric acid (CPA) very rapidly without any tedious and time-consuming manipulations such as elimination of silica and filtration. Under the proposed conditions (amount of sample 100 mg, amount of CPA added 10 g, heating temperature 290 degrees , heating time 30 min), magnetite, limonite and hematite are completely dissolved. The iron content can be determined in the presence of condensed phosphoric acid by titration with dichromate solution, if a slight modification is made. The total iron in iron ores, determined by the present method, is in agreement with that found by the JIS method. The ferrous iron in iron ores can be determined by dissolving the samples with CPA in a nitrogen atmosphere and titrating with dichromate solution. Chelatometric titration of iron after solvent extraction with MIBK from solutions prepared by use of CPA is found to be accurate for samples such as pyrite cinder. The ability of CPA to dissolve various materials has been investigated.     

Infrared macro and semimicro determination of nitrogen in raw nitrocellulose and nitrocellulose contained in propellants

The infrared procedure for the determination of nitrogen in raw nitrocellulose has been improved. In the original method 0.31-0.32 g of sample was dissolved in 45 ml of tetrahydrofuran, the solution was weighed, and the infrared peak at 6.0 microm was measured. The calibration curve was prepared by plotting absorbance against mg of nitrogen per g of solution. The method has the disadvantage that the height of the peak is affected by the sample weight. In the improved method the error due to the sample weight is eliminated by using 0.3000 g of sample and diluting to 50 ml in a volumetric flask. The calibration curve is prepared by plotting absorbance against % nitrogen. The method was extended to the semimicro scale by using a 30.0-mg sample and diluting to 5 ml in a volumetric flask. The method has been applied on the macro and semimicro scales to the direct determination of nitrogen in nitrocellulose after a methylene chloride extraction. The amounts of graphite and inorganic salts found in nitrocellulose-base propellants do not interfere, but a correction must be made to refer the results to 0.3000 g of nitrocellulose for the macro method or 30.0 mg of nitrocellulose for the semimicro method. The same calibration curve is used for all procedures.     

电解重量法测定混合铜矿中自由氧化铜

建立了用于混合铜矿石中自由氧化铜测定的方法。试样用含亚硫酸钠(6g/L)的硫酸(10%)溶液浸取2h,选择性溶解铜氧化物,过滤并煮沸滤液,用去离子水稀释后电解。溶液中的铜离子电积至阴极铂网上。用火焰原子吸收光谱法检测残余于电解后液中的铜离子;同时用硝酸(1+1)溶解铂网上的铜,并用火焰原子吸收光谱法检测与阴极铜共电积的杂质元素含量,用铂阴极差重加上电积后液残余铜含量并减去共电积的杂质元素含量可计算出氧化铜矿中酸溶铜含量。与碘量法相比,不用肉眼观察颜色变化确定终点,人为误差小,结果稳定、准确。通过对加拿大氧化铜矿标准物质AMIS0050进行测定(n=12),方法准确度可靠。并选取15批次的氧化铜矿检测,与经典碘量法比对,结果令人满意。     

A numerical method of finding potentiometric titration end-points by use of approximative spline functions

A new numerical method of determining potentiometric titration end-points is presented. It consists in calculating the coefficients of approximative spline functions describing the experimental data (e.m.f., volume of titrant added). The end-point (the inflection point of the curve) is determined by calculating zero points of the second derivative of the approximative spline function. This spline function, unlike rational spline functions, is free from oscillations and its course is largely independent of random errors in e.m.f. measurements. The proposed method is useful for direct analysis of titration data and especially as a basis for construction of microcomputer-controlled automatic titrators.     

微波消解-原子吸收光谱法测定橡胶及其制品中镉

建立了橡胶及其制品中镉含量的快速测定方法. 样品采用微波消解, 消解溶液中的镉用火焰原子吸收光谱法测定. 方法的检出限为2.5 mg/kg, 多种代表性橡胶及其制品的镉元素回收率在101.6%～104.4%之间. 对某含镉橡胶样品的10个实验室3次平行测定的结果表明实验室内和实验室间的相对标准偏差分别1.8%和8.2%. 方法适用于各种橡胶材料中镉的快速分析.