林一民(1965—), 女, 主任技师, 主要从事医学检验研究, (E-mail)
用过量的糠醛衍生转化肼,用质谱对肼的糠醛衍生晶体进行结构定性,对肼糠醛衍生物的晶体、溶剂及肼糠醛衍生物的提取液进行毛细管气相色谱对比分析,获得可靠的定性定量分析信息,优化衍生、萃取和色谱分析等条件,用标准曲线、精密度和准确度试验进行方法评价。实验表明,在糠醛过量的条件下,肼完全转化为2-糠醛嗪,保留时间为6.20 min,方法检出下限为0.007 8 mg/L,相对标准偏差2.5%,加标回收率98%~100%。方法的色谱峰形对称、准确、灵敏度高、选择性好,为不同实验室仪器及色谱柱条件下分析检测肼提供了一种快速、准确的条件探索程序。
Hydrazine is derived with excessive furfural. The crystal of hydrazine derivative conversion is characterized by mass spectrometry. The comparative analyses are made between the hydrazine-derived furfural crystal, solvent, as well as extraction solution of furfural derivatives of hydrazine by the method of capillary gas chromatography. Reliable qualitative and quantitative analytical information is obtained, and the conditions of derivation, extraction and chromatographic analysis are optimized. The method is evaluated by standard curve, precision and accuracy tests. Experiments show that in the case of excessive furfural, hydrazine is completely converted to 2-furaldehyde azine, whose retention time is 6.20 min. The detection limit of the method is 0.007 8 mg/L, the relative standard deviation is 2.5%, and the recovery is in the range of 98% to 100%. The method has the advantages of symmetrical peak shape, high accuracy, high sensitivity and good selectivity. It provides a rapid and accurate procedure for the analysis and determination of hydrazine under different laboratory instruments and chromatographic column conditions.
肼又称联氨,具有强还原性[
肼的测定方法主要有化学分析法、电化学分析法、荧光光谱法、分光光度法和气相色谱法等[
笔者拟用过量糠醛与肼反应合成肼糠醛衍生物,经质谱定性结构,再用已定性结构的纯净糠醛衍生产物晶体与溶剂、衍生试剂糠醛等对比分析,获得可靠的定性定量分析信息,探索分析检测最佳条件,建立适于不同实验室仪器与色谱柱条件下气相色谱快速、准确分析肼的方法及条件探索程序。
所用的主要仪器包括质谱仪(PerkinElmer Clarus SQ8T)、气相色谱仪配FID检测器(PerkinElmer Clarus 680)、毛细管柱(PerkinElmer,Elite-WAX-ETR,30 m×0.25 mm×0.25
肼标准溶液:在100.0 mL容量瓶中加入一定量0.2 mol/L的硫酸(分析纯,成都艾科达化学试剂有限公司)溶液,准确称量后,加入烘干的硫酸肼(分析纯,成都艾科达化学试剂有限公司),再准确称量,得硫酸肼的质量为0.203 1 g,加0.2 mol/L硫酸溶液至刻度,得到浓度为500.0 mg/L的标准贮备液,临用前,取1.0 mL于100.0 mL的容量瓶中,用0.2 mol/L硫酸溶液稀释定容,得到5.00 mg/L的肼标准应用液。衍生剂:临用前,用0.5 mol/L乙酸钠(优级纯,成都科龙试剂有限公司)溶液稀释4.0 mL经重新蒸馏的糠醛(优级纯,成都西亚试剂有限公司)至100.0 mL。乙酸乙酯(色谱纯,成都科龙试剂有限公司),实验用水均为超纯水。
称取0.80 g烘干的硫酸肼溶于50.0 mL的0.2 mol/L硫酸溶液中,另取1.2 mL经过重新蒸馏过的糠醛,用0.5 mol/L乙酸钠溶液稀释至50.0 mL,将上述两种溶液混合均匀,室温反应静置得淡黄色结晶,过滤后先后用少量超纯水和乙酸乙酯洗涤晶体,风干备用。
用0.5 mol/L乙酸钠溶液稀释0.2 mL新蒸的糠醛成20.0 mL糠醛溶液。称取糠醛衍生物晶体0.100 0 g,用乙酸乙酯溶解成100.0 mL溶液。在汽化室温度300 ℃、柱温210 ℃、离子源温度230 ℃、EM电压1 888 V、溶剂延迟时间6 min条件下,在m/35~300范围内分别对上述两种样品进行全扫描,对比定性分析糠醛和糠醛衍生物。
肼标准溶液或样品溶液用0.2 mol/L的硫酸溶液稀释定容到2.0 mL,加入2.0 mL衍生剂,振摇后静置反应1 h,用0.5 mL乙酸乙酯萃取1 min。在汽化室温度300 ℃、柱温210 ℃、氢火焰检测器温度350 ℃、载气流速2.0 mL/min、分流比10:1等色谱条件下,取2.0
线性范围实验:准确配制浓度为0.25,0.50,0.75,1.00,1.25 mg/L肼系列标准溶液2.0 mL,加入2.0 mL衍生剂,后续处理同步骤1.2.3,以峰面积为纵坐标、质量浓度为横坐标绘制标准曲线。
检出限测定:配制0.10 mg/L的肼标准溶液,加入2.0 mL衍生剂,后续处理同步骤1.2.3,平行测定11次。
精密度实验:分别配制浓度为0.25,0.50,1.00 mg/L的肼标准溶液,衍生化等后续操作同步骤1.2.3,各平行测定6次。
准确性(回收率)实验:用5.00 mg/L的肼标准应用液分别配制2.0 mL浓度分别为0.50 mg/L和1.25 mg/L的肼质控样,衍生化、萃取及后续操作同步骤1.2.3,进行空白加标回收实验。
肼的糠醛衍生可能按式(1)与肼进行单分子糠醛衍生,也可能按式(2)与两分子糠醛形成衍生产物。
实验采用过量的衍生剂,充分反应后得到衍生产物的结晶,对结晶产物进行质谱分析,结果见
质谱图对比分析:(a)肼的糠醛衍生物,(b)2-糠醛嗪
Mass spectrometric analysis for (a) furfural derivatives of hydrazine, and (b) 2-furaldehyde azine
肼糠醛衍生物乙酸乙酯溶液的气相色谱分析结果如
肼糠醛衍生物乙酸乙酯溶液的气相色谱分析
Result of gas chromatographic analysis for furfural derivatives of hydrazine
乙酸乙酯的气相色谱分析
Gas chromatographic analysis for ethyl acetate
上述分析表明,肼的糠醛衍生按式(2)进行,得到淡黄色结晶,该结晶是单一的纯净衍生物2-糠醛嗪。但肼的糠醛衍生也可能按式(1)进行,停留在单分子糠醛衍生阶段,按式(1)生成的衍生产物在硫酸溶液中能形成可溶性的盐而不结晶。鉴于此,将糠醛过量的肼衍生溶液不经过晶体过滤和洗涤,直接用乙酸乙酯充分振摇萃取,将该萃取液与糠醛的乙酸乙酯溶液在相同条件下进行气相色谱对比分析,结果分别见
肼的糠醛衍生物乙酸乙酯萃取液的气相色谱分析
Gas chromatographic analysis for ethyl acetate extraction solution of furfural derivatives of hydrazine
糠醛乙酸乙酯溶液的气相色谱分析
Gas chromatographic analysis for ethyl acetate solution of furfural
上述实验结果表明,肼在过量糠醛存在时完全衍生转化为2-糠醛嗪,同时用乙酸乙酯可以有效地萃取糠醛衍生产物,在汽化室温度300 ℃、柱温210 ℃、氢火焰检测器温度350 ℃、载气流速2 mL/min、分流比10:1的色谱条件下可以得到定性定量分析肼(肼对应的糠醛衍生物)的对称色谱峰。
肼的糠醛衍生可以用气相色谱方法进行定性和定量,依据职业卫生标准制定指南,该方法用于肼的分析检测还需进一步从标准曲线的线性范围、检出限、标准偏差、精密度和准确性(回收率)等方面进行方法评价。
浓度为0.25,0.50,0.75,1.00,1.25 mg/L肼系列标准溶液经过衍生化、萃取后,在选定的最优分析条件下进行气相色谱分析,以峰面积为纵坐标
标准曲线
Standard curve
对0.10 mg/L低浓度的肼标准溶液,按照前述色谱分析的方法和条件平行测定11次,其标准偏差SD为0.002 5 mg/L,计算得到方法的检出限DL为0.007 8 mg/L,说明方法的灵敏度较高。
对方法线性范围内的浓度为0.25,0.50,1.00 mg/L的肼标准溶液进行衍生化、萃取及气相色谱分析,平行测定6次的平均值及相对标准偏差如
精密度实验结果
Test results of precision
标准液浓度/(mg·L-1) | 测定平均值/(mg·L-1) | 相对标准偏差/% |
0.25 | 0.253 422 | 1.90 |
0.50 | 0.509 590 | 0.70 |
1.00 | 1.001 933 | 0.29 |
用新配制的0.50 mg/L和1.25 mg/L肼质控样溶液各2.0 mL,进行空白加标回收实验,结果见
加标回收实验结果
Test results of recoveries
标准浓度/(mg·L-1) | 实测浓度/(mg·L-1) | 峰面积 | 回收率/% |
0.50 | 0.49 | 40 552.98 | 98.0 |
1.25 | 1.25 | 101 929.99 | 100.0 |
上述结果表明,肼经过糠醛衍生在选定的色谱分析最优条件下,具有较宽的测定范围,方法的灵敏度、精密度和准确性较好,具有较高的精确度,是测定肼的较理想方法。
肼需要衍生转化后测定,但分析测定时定性定量依据来源于衍生转化产物2-糠醛嗪,而不是给定标准物质肼的直接色谱信息。先利用衍生转化原理,分析可能的转化途径,合成衍生转化的目标产物,用质谱定性结构,获得可靠的定性定量信息来源;再利用已定性结构的衍生产物与溶剂、衍生试剂等进行对比分析,确定理想的气相色谱分析条件;最后通过标准曲线法、平行测定法、加标回收法证明方法准确、灵敏度高、选择性好且色谱峰形对称。本研究不仅为不同实验室仪器及色谱柱条件下分析检测肼提供了一种快速、准确的条件探索程序,也为分析检测其它需衍生转化后测定的物质提供了可借鉴的方法。
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