电感耦合等离子体原子发射光谱法测定锰铁合金、锰硅合金和金属锰中8种微量元素
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摘要
锰铁合金、锰硅合金、金属锰中铅、砷、钛、铜、镍、钙、镁、铝的含量决定了产品质量,以往常采用化学法或原子吸收光谱法进行测定,但存在准确度较差或测定速度不能满足要求等问题。为了实现上述元素的准确、快速测定,建立了采用电感耦合等离子体原子发射光谱法(ICP-AES)测定锰铁合金、锰硅合金和金属锰中微量铅、砷、钛、铜、镍、钙、镁、铝的方法。实验以硝酸、盐酸、氢氟酸、高氯酸分解样品,并使硅与氢氟酸反应生成四氟化硅挥发除去,试液中剩余共存元素主要有铁、锰等。实验结果表明,铁不干扰测定,通过在标准溶液系列中进行锰基体匹配消除锰基体效应的影响。以2mL高氯酸和6mL盐酸混合酸(8%)作为分析介质,可以达到最佳分析效果。在各元素校准曲线线性范围内,线性相关系数在0.999 2～0.999 9之间;方法中各元素的检出限在0.000 1～0.004 0μg/mL。实验方法用于测定锰铁合金、锰硅合金、金属锰中铅、砷、钛、铜、镍、钙、镁、铝,结果的相对标准偏差(RSD,n=11)在2.2%～9.4%;回收率在95%～105%;选择7个实验室进行了验证试验,各实验室间结果基本一致;按照实验方法测定了4个标准样品(材字-32、YSB C 28618、YSB C 26605)中铅、砷、钛、铜、镍、钙、镁、铝,结果与认定值相吻合。
The content of lead,arsenic,titanium,copper,nickel,calcium,magnesium and aluminum in ferromanganese alloy,manganese-silicon alloy and manganese metal determined the quality of products.In the past,their contents were usually measured using chemical method or atomic absorption method,which had some problems such as poor accuracy or slow measurement speed that could not meet the requirements.In order to realize the accurate and rapid determination of above elements,the inductively coupled plasma atomic emission spectrometry(ICP-AES)was employed to measure the contents of trace lead,arsenic,titanium,copper,nickel,calcium,magnesium and aluminum in ferromanganese alloy,manganesesilicon alloy and manganese metal.The samples were decomposed with nitric acid,hydrochloric acid,hydrofluoric acid and perchloric acid.The silicon in sample reacted with hydrofluoric acid to form SiF4 and then be removed by volatilization.The residual coexisting elements in sample solution mainly included iron and manganese.The experimental results showed that the iron had no interference with the determination.The matrix effect of manganese was eliminated by matrix matching in the standard solution series.The mixed acid(8%)of 2 mL perchloric acid and 6 mL hydrochloric acid was used as medium to achieve the best analysis results.Within linear range of calibration curves of elements,the correlation coefficients ranged from 0.999 2 to 0.999 9.The detection limit of elements in this method was 0.000 1-0.004 0μg/mL.The proposed method was applied for the determination of lead,arsenic,titanium,copper,nickel,calcium,magnesium and aluminum in ferromanganese alloy,manganese-silicon alloy and manganese metal.The relative standard deviations(RSD,n=11)were in the range of 2.2%-9.4%,and the recoveries were between 95%and 105%.Seven laboratories were selected for the verification test,and the results were basically the same.The contents of lead,arsenic,titanium,copper,nickel,calcium,magnesium and aluminum in four certified reference materials(Caizi-32,YSB C 28618,YSB C 26605)were determined according to the experimental method,and the found results were consistent with the certified values.
The content of lead,arsenic,titanium,copper,nickel,calcium,magnesium and aluminum in ferromanganese alloy,manganese-silicon alloy and manganese metal determined the quality of products.In the past,their contents were usually measured using chemical method or atomic absorption method,which had some problems such as poor accuracy or slow measurement speed that could not meet the requirements.In order to realize the accurate and rapid determination of above elements,the inductively coupled plasma atomic emission spectrometry(ICP-AES)was employed to measure the contents of trace lead,arsenic,titanium,copper,nickel,calcium,magnesium and aluminum in ferromanganese alloy,manganesesilicon alloy and manganese metal.The samples were decomposed with nitric acid,hydrochloric acid,hydrofluoric acid and perchloric acid.The silicon in sample reacted with hydrofluoric acid to form SiF4 and then be removed by volatilization.The residual coexisting elements in sample solution mainly included iron and manganese.The experimental results showed that the iron had no interference with the determination.The matrix effect of manganese was eliminated by matrix matching in the standard solution series.The mixed acid(8%)of 2 mL perchloric acid and 6 mL hydrochloric acid was used as medium to achieve the best analysis results.Within linear range of calibration curves of elements,the correlation coefficients ranged from 0.999 2 to 0.999 9.The detection limit of elements in this method was 0.000 1-0.004 0μg/mL.The proposed method was applied for the determination of lead,arsenic,titanium,copper,nickel,calcium,magnesium and aluminum in ferromanganese alloy,manganese-silicon alloy and manganese metal.The relative standard deviations(RSD,n=11)were in the range of 2.2%-9.4%,and the recoveries were between 95%and 105%.Seven laboratories were selected for the verification test,and the results were basically the same.The contents of lead,arsenic,titanium,copper,nickel,calcium,magnesium and aluminum in four certified reference materials(Caizi-32,YSB C 28618,YSB C 26605)were determined according to the experimental method,and the found results were consistent with the certified values.
引文
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[12]Coedo A G,Dorado M T,Padilla I.Evaluation of a desolvating microconcentric nebulizer in inductively coupled plasma mass spectrometry to improve the determination of arsenic in steels[J].Appl.Spectrosc.,1999,53(8):974-978.
[13]王立平,冯海涛,董亚萍,等.标准加入ICP-AES法测定铬酸钠中杂质元素[J].光谱学与光谱分析,2015,35(2):523-526.WANG Li-ping,FENG Hai-tao,DONG Ya-ping,et al.Standard addition determination of impurities in Na2CrO4by ICP-AES[J].Spectroscopy and Spectral Analysis,2015,35(2):523-526.
[14]龚琦.对电感耦合等离子体发射光谱法中一些问题的认识[J].冶金分析,2018,38(9):26-30.GONG Qi.Understanding of some issues about inductively coupled plasma optical emission spectrometry[J].Metallurgical Analysis,2018,38(9):26-30.
[15]陶锐,高舸.电感耦合等离子体光发射光谱分析中无机酸基体效应研究(I)无机酸基体效应及其机理[J].理化检验:化学分册,2005,41(1):67-71.TAO Rui,GAO Ge.Matrix effect of inorganic acids in icp-oes analysis(I)matrix effect of inorganic acids and its mechanism[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2005,41(1):67-71.
[16]庞晋山,黄刚,邓爱华,等.电感耦合等离子体原子发射光谱分析中易电离元素的基体干扰及其抑制的研究[J].理化检验:化学分册,2012,48(6):671-673,677.PANG Jin-shan,HUANG Gang,DENG Ai-hua,et al.Study on matrix interference and its inhibition of easily ionized elements in inductively coupled plasma atomic emission spectroscopy analysis[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2012,48(6):671-673,677.
[2]黄仁彬.硅铝钡合金中硅、钙、铝的测定[J].冶金分析,2004,24(6):80-81.HUANG Ren-bin.Determination of silicon calcium aluminum in Si-Al-Ba alloy[J].Metallurgical Analysis,2004,24(6):80-81.
[3]Ramachandraiah C,Kumar Rajesh J,Reddy Janardhan K.Development of a highly sensitive extractive spectrophotometrie method for the determination of nickel(II)from environmental matrices using N-ethyl-3-carbazolecarboxaldehyde-3-thiosemicarbazone[J].Journal of Environmental Management,2008,88(4):729-736.
[4]Niazi Ali,Yazdanipour Ateesa.Simultaneous spectrophotometric determination of cobalt,copper and nickel using1-(2-thiazolylazo)-2-naphtholby chemometrics methods[J].Chinese Chemical Letters,2008,19(7):860-864.
[5]邓冬莉,李芬,向敏婕,等.火焰原子吸收光谱法测定航空煤油中铅锰镁锌铜[J].冶金分析,2016,36(12):26-31.DENG Dong-li,LI Fen,XIANG Min-jie,et al.Determination of lead,manganese,magnesium,zinc and copper in aviation kerosene by flame atomic absorption spectrometry[J].Metallurgical Analysis,2016,36(12):26-31.
[6]孙宝莲,董岐,周恺,等.火焰原子吸收光谱法测定铜磁铁矿中铜[J].冶金分析,2017,37(3):44-47.SUN Bao-lian,DONG Qi,ZHOU Kai,et al.Determination of copper in copper magnetite by flame atomic absorption spectrometry[J].Metallurgical Analysis,2017,37(3):44-47.
[7]朱国忠,徐艳燕,庞燕,等.连续光源火焰原子吸收光谱法同时测定氢氧化钴中镍铜锰铁钙镁钠镉[J].湿法冶金,2017,36(4):346-349.ZHU Guo-zhong,XU Yan-yan,PANG Yan,et al.Simultaneous determination of nickel,copper,manganese,iron,calcium,magnesium,sodium and cadmium in cobalt hydroxide by continuous light souce flame atomic absorption spectrometry[J].Hydrometallurgy of China,2017,36(4):346-349.
[8]Roldana Paulo S,Ialcantara lton L,Padilha Cilene C F.Determination of copper,iron,nickel and zinc in gasoline by FAAS after sorption and preconcentration on silica modified with 2-aminotiazole groups[J].Fuel,2005,84(2):305-309.
[9]周西林,王娇娜,刘迪,等.电感耦合等离子体原子发射光谱法在金属材料分析应用技术方面的进展[J].冶金分析,2017,37(1):39-46.ZHOU Xi-lin,WANG Jiao-na,LIU Di,et al.Inductively coupled plasma atomic emission spectrometry metal material application technology progress[J].Metallurgical Analysis,2017,37(1):39-46.
[10]杨玲,张孟星,赵丽.电感耦合等离子体发射光谱标准基体匹配直接测定纯金中杂质元素[J].现代科学仪器,2011(1):117-122.YANG Ling,ZHANG Meng-xing,ZHAO Li.The standard matrix matching directly determine of impurity element in pure gold directly by ICP-AES[J].Modern Scientific Instrument,2011(1):117-122.
[11]杨新能,冯宗平,羊绍松.电感耦合等离子体原子发射光谱法测定钒铁合金中杂质元素[J].冶金分析,2014,34(11):37-41.YANG Xin-neng,FENG Zong-ping,YANG Shao-song.Determination of impurity elements in ferrovanadium ally by inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2014,34(11):37-41.
[12]Coedo A G,Dorado M T,Padilla I.Evaluation of a desolvating microconcentric nebulizer in inductively coupled plasma mass spectrometry to improve the determination of arsenic in steels[J].Appl.Spectrosc.,1999,53(8):974-978.
[13]王立平,冯海涛,董亚萍,等.标准加入ICP-AES法测定铬酸钠中杂质元素[J].光谱学与光谱分析,2015,35(2):523-526.WANG Li-ping,FENG Hai-tao,DONG Ya-ping,et al.Standard addition determination of impurities in Na2CrO4by ICP-AES[J].Spectroscopy and Spectral Analysis,2015,35(2):523-526.
[14]龚琦.对电感耦合等离子体发射光谱法中一些问题的认识[J].冶金分析,2018,38(9):26-30.GONG Qi.Understanding of some issues about inductively coupled plasma optical emission spectrometry[J].Metallurgical Analysis,2018,38(9):26-30.
[15]陶锐,高舸.电感耦合等离子体光发射光谱分析中无机酸基体效应研究(I)无机酸基体效应及其机理[J].理化检验:化学分册,2005,41(1):67-71.TAO Rui,GAO Ge.Matrix effect of inorganic acids in icp-oes analysis(I)matrix effect of inorganic acids and its mechanism[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2005,41(1):67-71.
[16]庞晋山,黄刚,邓爱华,等.电感耦合等离子体原子发射光谱分析中易电离元素的基体干扰及其抑制的研究[J].理化检验:化学分册,2012,48(6):671-673,677.PANG Jin-shan,HUANG Gang,DENG Ai-hua,et al.Study on matrix interference and its inhibition of easily ionized elements in inductively coupled plasma atomic emission spectroscopy analysis[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2012,48(6):671-673,677.