Abstract：Copper in ferromanganese, silico-manganese and manganese metal was a harmful element in most steel smelting processes. It could reduce the mechanical properties of steel and cause oxidation of steel surface in heating. Therefore, a determination method of copper in ferromanganese, silico-manganese and manganese metal by bisoxaldihydrazone spectrophotometry was established. The sample was decomposed with nitric acid and hydrofluoric acid. The perchloric acid smoking was adopted to provide the effect of high temperature and strong oxidation. Under this condition, silicon reacted with hydrofluoric acid to form silicon tetrafluoride and then was removed by volatilization. Carbon was oxidized or decomposed to tiny carbon particles to completely release copper. In hydrochloric acid medium, the pH of solution was controlled at 8.9-9.5 with ammonium chloride-ammonium hydroxide buffer solution (pH 9.2). Copper could react with bisoxaldihydrazone to form stable chelate within 1min. The experimental results showed that the matrix effect of manganese and iron could be eliminated under following conditions: the matrix matching of manganese and iron was conducted in the standard solution series; the citric acid was added into standard solution and sample solution as a masking agent; the special reference solution was prepared for the coloring solutions containing different contents of manganese and iron. In the linear range of calibration curve for copper, the linear correlation coefficient was 0.9991. The detection limit of copper was 0.0066μg/mL. The proposed method was applied for the determination of copper in the samples of ferromanganese, silico-manganese and manganese metal. The relative standard deviations (RSDs, n=11) of the results were between 5.4% and 9.5%, and the recoveries were between 97% and 105%. The content of copper in three certified reference materials of ferromanganese and one certified reference material of silico-manganese was determined. The results were consistent with the certified values. Six laboratories were selected for the verification test, and the results were basically the same.
吕茜茜,张钊,王晋平.电解重量法测定阳极铜中铜[J].冶金分析,2017,37(5):30-33.LÜ Qian-qian,ZHANG Zhao,WANG Jin-ping.Determination of copper in anode copper by electrolytic gravimetry[J].Metallurgical Analysis,2017,37(5):30-33.
[2]
胡建春,赵琎,张瑞霖.电解重量法和电感耦合等离子体原子发射光谱法在测定氧化镍中镍钴铜锌铁锰中的应用[J].冶金分析,2015,35(11):28-33.HU Jian-chun,ZHAO Jin,ZHANG Rui-lin.Application of electrolytic gravimetry and inductively coupled plasma atomic emission spectrometry in the determination of nickel,cobalt,copper,zinc,iron and manganese in nickel oxide[J].Metallurgical Analysis,2015,35(11):28-33.
[3]
佡云.碘量法与电解重量法测定氧化铜矿中酸溶铜的方法比较[J].中国无机分析化学,2013,3(2):43-45.NAO Yun.Comparison of electro-gravimetric method and iodometric method for measuring acid soluble copper in oxide copper ore[J].Chinese Journal of Inorganic Analytical Chemistry,2013,3(2):43-45.
郑晓蓉,陈岩,方振华.聚乙二醇-新铜试剂-硫酸铵萃取光度法测定铜[J].冶金分析,1998,15(4):26-27.ZHENG Xiao-rong,CHEN Yan,FANG Zhen-hua.Study on the extraction spectrophotometry by using polyethylene Glycol-BCO-ammonium sulfate[J].Metallurgical Analysis,1998,15(4):26-27.
[7]
Ali Niazi,Ateesa Yazdanipour.Simultaneous spectrophotometric determination of cobalt, copper and nickel using 1-(2-thiazolylazo)-2-naphthol by chemometrics methods[J].Spectrochimica Acta:Chinese Chemical Letters,2008,19(7):860-864.
[8]
Li Yuan,Shu Hui Huo,Xiao Na Ren,et al.A novel spectrophotometric determination of copper(II) with bromosulphonazo III[J].Spectrochimica Acta:Chinese Chemical Letters,2008,19(1):92-94.
[9]
闻向东,周郑,夏念平,等.双环己酮草酰二腙分光光度法测定铁矿石中铜[J].广州化工,2016,44(2):112-114.WEN Xiang-dong,ZHOU Zheng,XIA Nian-ping,et al.Application of bis(cyclohexanone) oxaldihydrazone spectrophotometry in the determination of copper in iron ores[J].Guangzhou Chemical Industry,2016,44(2):112-114.
[10]
刘宪彬,刘康,郑津津,等.双环己酮草酰二腙分光光度法测定火法冶炼镍基体料中铜[J].冶金分析,2013,33(2):60-64.LIU Xian-bin,LIU Kang,ZHENG Jin-jin,et al.Spectrophotometric determination of copper in fire smelting nickel substrate materials with bisoxaldihydrazone[J].Metallurgical Analysis,2013,33(2):60-64.
[11]
安身景,刘虹,刘小东,等.双环己酮草酰二腙光度法测定合金中高含量铜[J].冶金分析,2013,33(1):50-53.AN Shen-jing,LIU Hong,LIU Xiao-dong,et al.Determination of high content copper in alloys by bis-cyclohexanone oxaldihydrazone spectrophotometric method[J].Metallurgical Analysis,2013,33(1):50-53.
[12]
刘月成,王尚芝,李海,等.火焰原子吸收光谱法测定云冈石窟风化岩石中钙铜铁锰[J].冶金分析,2010,30(2):38-41.LIU Yue-cheng,WANG Shang-zhi,LI Hai,et al.Determination of calcium,copper,iron and manganese in weathering rock of Yungang Grottoes by flame atomic absorption spectrometry[J].Metallurgical Analysis,2010,30(2):38-41.
[13]
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.
[14]
胡净宇,王海舟.激光剥蚀-电感耦合等离子体质谱内标定量法测定高温合金中痕量元素[J].冶金分析,2008,28(1):1-5.HU Jing-yu,WANG Hai-zhou.Trace analysis of superalloy by laser ablation inductively coupled plasma mass spectrometry with internal standard[J].Metallurgical Analysis,2008,28(1):1-5.
[15]
Hu J Y,Wang H Z.Determination of trace elements in superalloy by ICP-MS[J].Mikrochimica Acta,2001,137(3-4):149-155.
[16]
刘伟,曹吉祥,张瑜.熔融制样-X射线荧光光谱法测定钨铁合金中硅锰磷铜钨[J].冶金分析,2019,39(2):46-50.LIU Wei,CAO Ji-xiang,ZHANG Yu.Determination of silicon,manganese,phosphorus,copper,tungsten in ferrotungsten alloy by X-ray fluorescence spectrometry with fusion sample preparation[J].Metallurgical Analysis,2019,39(2):46-50.
