CHINESE JOURNAL OF ENERGETIC MATERIALS
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亲水色谱-质谱联用方法分析水中肼、甲基肼和偏二甲肼
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北京航天试验技术研究所, 北京 100074

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Determination of Hydrazine, Monomethylhydrazine, and Unsymmetrical Dimethylhydrazine in Water by Hydrophilic Interaction Chromatography Coupled with Mass Spectrometry
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Beijing Institute of Aerospace Testing Technology, Beijing 100074, China

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    摘要:

    针对现有方法(分光光度法和液相色谱法)在分析水样中肼、甲基肼和偏二甲肼含量中存在的选择性差、分析效率低等问题,开发了一种基于亲水色谱-质谱联用的肼类化合物含量分析方法。分别考察了样品配制条件、流动相组成及质谱分析条件对分离效果、分析时间、检测灵敏度的影响,优化得到了适合于肼类化合物分析的液相色谱-质谱分析条件。该方法使用80%异丙醇-0.1%甲酸溶液作为样品溶剂,进样10 μL进行分析;以70%乙腈-10 mmol·L-1甲酸铵、pH=3.5的混合溶剂作为流动相,用亲水色谱柱进行分离;分别选取质子化肼-乙腈非共价加合物、质子化甲基肼、质子化偏二甲肼作为检测离子,并分别采用50、100、100 eV源后碰撞能对肼、甲基肼和偏二甲肼进行质谱分析。在0.01~2 mg·L-1之间一定的浓度范围内,三种肼类化合物的质谱响应与其浓度呈现出良好的线性关系,可应用于水样中三种肼类化合物的定量分析。三种肼类化合物的方法检出限分别为0.04、0.005、0.025 mg·L-1。对加标水样进行了分析,所得方法回收率介于92%~115%。

    Abstract:

    A method of determination of hydrazine, monomethylhydrazine (MMH), and unsymmetrical dimethylhydrazine (UDMH) in water by hydrophilic interaction chromatography (HILIC) coupled with mass spectrometry (MS) was developed. Sample preparation, composition of mobile phase and parameters of MS detection were investigated for optimization for HILIC-MS analysis of hydrazine compounds. 80% isopropanol-0.1% formic acid was used as sample solvent, and injection volume was 10 μL. Composition of mobile phase was 70% acetonitrile-10 mmol·L-1 ammonium formate, pH=3.5. Hydrophilic interaction chromatographic column was utilized for separation. Protonated non-covalent adduct of hydrazine and acetonitrile, protonated MMH and protonated UDMH were selected as detection ions, and post-source collision energy were 50, 100, 100 eV, respectively. Good linearity between MS response intensity and analyte concentration for quantitative analysis was obtained in certain range of analyte concentration. The limits of detection for hydrazine, MMH and UDMH were 0.04, 0.005, 0.025 mg·L-1, respectively. Recovery of spiked water sample was determined as 92%-115%.

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引用本文

徐林楠,张旭,赵坦,等.亲水色谱-质谱联用方法分析水中肼、甲基肼和偏二甲肼[J].含能材料, 2022, 30(10):1022-1029. DOI:10.11943/CJEM2021220.
XU Lin-nan, ZHANG Xu, ZHAO Tan, et al. Determination of Hydrazine, Monomethylhydrazine, and Unsymmetrical Dimethylhydrazine in Water by Hydrophilic Interaction Chromatography Coupled with Mass Spectrometry[J]. Chinese Journal of Energetic Materials, 2022, 30(10):1022-1029. DOI:10.11943/CJEM2021220.

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历史
  • 收稿日期: 2021-08-17
  • 最后修改日期: 2022-01-18
  • 录用日期: 2022-01-13
  • 在线发布日期: 2022-01-17
  • 出版日期: 2022-10-25