GB-T 11066.12-2024 金化学分析方法 第12 部分：银、铜、铁、铅、铋、锑、镁、镍、锰、钯、铬、铂、铑、钛、锌、砷、锡、硅、钴、钙、钾、锂、钠、碲、钒

ICS77.040.30CCSH15中华人民共和国国家标准金化学分析方法电感耦合等离子体原子发射光谱法Methodsforchemicalanalysisofgold—Part12:Determinationofsilver,copper,iron,lead,bismuth,antimony,titanium,zinc,arsenic,tin,silicon,cobalt,calcium,potassium,lithium,国家市场监督管理总局国家标准化管理委员会Ⅰ前言 Ⅲ引言 Ⅳ1范围 12规范性引用文件 13术语和定义 24原理 25试剂或材料 26仪器设备 57样品 57.1试样 57.2试料 58试验步骤 58.1空白试验 58.2测定次数 58.3测定 58.4工作曲线的绘制 69试验数据处理 610精密度 710.1重复性 710.2再现性 1011试验报告 13附录A(资料性)推荐的电感耦合等离子体原子发射光谱仪工作条件参数 14附录B(资料性)电感耦合等离子体原子发射光谱法中多谱线拟合法使用示例 15附录C(资料性)精密度试验原始数据 16Ⅲ本文件按照GB/T1.1—2020《标准化工作导则第1部分:标准化文件的结构和起草规则》的规定起草。本文件是GB/T11066《金化学分析方法》的第12部分。GB/T11066已经发布了以下部分:—金量的测定—银量的测定—铁量的测定火试金法;火焰原子吸收光谱法;火焰原子吸收光谱法;—铜、铅和铋量的测定火焰原子吸收光谱法;—镁、镍、锰和钯量的测定火焰原子吸收光谱法;乙酸乙酯萃取-电感耦合等离子体原子发射光谱法;—砷和锡量的测定氢化物发生-原子荧光光谱法;—硅量的测定钼蓝分光光度法;谱法;请注意本文件的某些内容可能涉及专利。本文件的发布机构不承担识别专利的责任。本文件由中国有色金属工业协会提出。本文件由全国有色金属标准化技术委员会(SAC/TC243)归口。本文件起草单位:紫金矿业集团股份有限公司、福建紫金矿冶测试技术有限公司厦门分公司、北矿检测技术股份有限公司、大冶有色设计研究院有限公司、深圳市中金岭南有色金属股份有限公司、有色金属技术经济研究院有限责任公司、山东恒邦冶炼股份有限公司、华津国检(深圳)金银珠宝检验中心有限公司、紫金铜业有限公司、东北大学、浙江遂昌汇金有色金属有限公司。Ⅳ引言锡、硅等杂质元素的检测。但随着黄金精炼厂、原料提供商、消费者、第三方仲裁机构及中间贸易商对黄金质量把控日益严格,金锭要求检测的杂质元素种类越来越多,检测时效要求越来越高;因此,高效、准确检测金的化学成分显得尤为重要。GB/T11066根据检测对象和检测手段的不同,由12个部分构成。—第1部分:金量的测定火试金法。目的在于规定金中金含量的火试金法及适用的测定范围。—第2部分:银量的测定火焰原子吸收光谱法。目的在于规定金中银含量的火焰原子吸收光谱法及适用的测定范围。—第3部分:铁量的测定火焰原子吸收光谱法。目的在于规定金中铁含量的火焰原子吸收光谱法及适用的测定范围。—第4部分:铜、铅和铋量的测定火焰原子吸收光谱法。目的在于规定金中铜、铅和铋含量的火焰原子吸收光谱法及适用的测定范围。铅、锑和铋含量的原子发射光谱法及适用的测定范围。—第6部分:镁、镍、锰和钯量的测定火焰原子吸收光谱法。目的在于规定金中镁、镍、锰和钯含量的火焰原子吸收光谱法及适用的测定范围。、锰和铬含量的火花原子发射光谱法及适用的测定范围。酯萃取-电感耦合等离子体原子发射光谱法及适用的测定范围。—第9部分:砷和锡量的测定氢化物发生-原子荧光光谱法。目的在于规定金中砷和锡含量的氢化物发生-原子荧光光谱法及适用的测定范围。—第10部分:硅量的测定钼蓝分光光度法。目的在于规定金中硅含量的钼蓝分光光度法及适用的测定范围。谱法及适用的测定范围。匹配-标准曲线法及多谱线拟合法等校正方法,使用电感耦合等离子体原子发射光谱仪测定金质量。1金化学分析方法电感耦合等离子体原子发射光谱法警告—使用本文件的人员应有正规实验室工作的实践经验。本文件并未指出所有可能的安全问题。使用者有责任采取适当的安全和健康措施,并保证符合国家有关法规规定的条件。1范围表1测定范围元素测定范围(质量分数)%元素测定范围(质量分数)%元素测定范围(质量分数)%Ag0.0003~0.0500Cr0.0002~0.0500K0.0002~0.0500Cu0.0004~0.0500Pt0.0003~0.0500Li0.0002~0.0500Fe0.0003~0.0500Rh0.0004~0.0500Na0.0002~0.0500Pb0.0004~0.0500Ti0.0002~0.0500Te0.0003~0.0500Bi0.0005~0.0500Zn0.0003~0.0500V0.0002~0.0500Sb0.0005~0.0500As0.0005~0.0500Zr0.0002~0.0500Mg0.0002~0.0500Sn0.0005~0.0500Cd0.0002~0.0500Ni0.0003~0.0500Si0.0004~0.0500Mo0.0002~0.0500Mn0.0002~0.0500Co0.0002~0.0500Re0.0002~0.0500Pd0.0003~0.0500Ca0.0002~0.0500Al0.0002~0.05002规范性引用文件下列文件中的内容通过文中的规范性引用而构成本文件必不可少的条款。其中,注日期的引用文件,仅该日期对应的版本适用于本文件;不注日期的引用文件,其最新版本(包括所有的修改单)适用于本文件。2GB/T6682分析实验室用水规格和试验方法GB/T17433—2014冶金产品化学分析基础术语3术语和定义GB/T17433—2014界定的术语和定义适用于本文件。4原理试料以盐酸、硝酸混合酸分解,在稀盐酸介质中,采用基体匹配-标准曲线法及多谱线拟合法等校正5试剂或材料除非另有说明,在分析中应仅使用确认为优级纯的试剂。5.1水:符合GB/T6682规定的二级水。5.230%过氧化氢。5.4硝酸(ρ=1.42g/mL)。5.35.4硝酸(ρ=1.42g/mL)。5.55.5盐酸(1+1)。5.6盐酸(1+9)。5.7硝酸(1+1)。5.8混合酸:以1体积硝酸(5.4)、3体积盐酸(5.3)和4体积的水混合均匀。5.9乙醇(1+1)。5.10金(wAu≥99.999%,单个杂质元素含量不大于0.0002%,杂质总和不大于0.0010%)。5.11银标准贮存溶液:称取0.1000g金属银(wAg≥99.99%),置于100mL聚四氟乙烯烧杯中,加入10mL硝酸(5.7),低温加热溶解,驱尽氮的氧化物,冷却至室温,转移至预先加入50mL盐酸(5.3)的100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg银。5.12铜标准贮存溶液:称取0.1000g金属铜(wCu≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg铜。5.13铁标准贮存溶液:称取0.1000g金属铁(wFe≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg铁。5.14铅标准贮存溶液:称取0.1000g金属铅(wPb≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg铅。5.15铋标准贮存溶液:称取0.1000g金属铋(wBi≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg铋。5.16镁标准贮存溶液:称取0.1000g金属镁(wMg≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释3至刻度。混匀。此溶液1mL含1mg镁。5.17镍标准贮存溶液:称取0.1000g金属镍(wNi≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg镍。5.18锰标准贮存溶液:称取0.1000g金属锰(wMn≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg锰。5.19铬标准贮存溶液:称取0.1000g金属铬(wCr≥99.99%),置于100mL聚四氟乙烯烧杯中,加入5mL盐酸(5.5),1mL硝酸(5.7),盖上聚四氟乙烯杯盖,低温加热溶解完全,移入100mL塑料容量瓶中,加入10mL盐酸(5.5),用水稀释至刻度,混匀。此溶液1mL含1mg铬。5.20锌标准贮存溶液:称取0.1000g金属锌(wZn≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg锌。5.21砷标准贮存溶液:称取0.1000g金属砷(wAs≥99.99%),置于100mL聚四氟乙烯烧杯中,加入6mL硝酸(5.4),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg砷。5.22钠标准贮存溶液:称取0.2542g氯化钠(wNaCl≥99.99%),置于100mL聚四氟乙烯烧杯中,用水溶解,溶解完全后,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg钠。5.23钴标准贮存溶液:称取0.1000g金属钴(wCo≥99.99%),置于100mL聚四氟乙烯烧杯中,加10mL水,20mL硝酸(5.7),低温加热溶解,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg钴。5.24钙标准贮存溶液:称取0.2497g碳酸钙(基准试剂,预先在105℃烘2h,置于干燥器中冷却至室温),置于100mL聚四氟乙烯烧杯中,加入10mL水,盖上聚四氟乙烯杯盖,从杯嘴慢慢加入5mL盐酸(5.3),低温加热溶解,煮沸驱尽二氧化碳,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg钙。5.25钾标准贮存溶液:称取0.1907g于500℃~600℃烘至恒重的氯化钾,置于100mL聚四氟乙烯烧杯中,加入50mL水,低温加热溶解,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg钾。5.26锂标准贮存溶液:称取0.5323g碳酸锂(wLi2CO3≥99.99%),置于100mL聚四氟乙烯烧杯中,加入50mL水,盖上聚四氟乙烯杯盖,缓慢加入5mL盐酸(5.3),加热煮沸驱尽二氧化碳,冷却至室温,用水洗去杯盖,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg锂。5.27钒标准贮存溶液:称取0.1000g金属钒(wV≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg钒。5.28镉标准贮存溶液:称取0.1000g金属镉(wCd≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温加热溶解,挥发驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg镉。5.29铼标准贮存溶液:称取0.1000g金属铼(wRe≥99.99%),置于100mL聚四氟乙烯烧杯中,加入3mL盐酸(5.3),1mL硝酸(5.4),低温加热溶解完全,移入100mL塑料容量瓶中,加入10mL盐酸(5.3),用水稀释至刻度,混匀。此溶液1mL含1mg铼。5.30铝标准贮存溶液:称取0.1000g金属铝(wAl≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL盐酸(5.5),低温加热溶解,冷却至室温,用盐酸(5.5)移入100mL塑料容量瓶中并稀释至刻度,混匀。此溶液1mL含1mg铝。45.31锑标准贮存溶液:称取0.1000g金属锑(wSb≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL混合酸(5.8),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg锑。5.32钯标准贮存溶液:称取0.1000g金属钯(wPd≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL混合酸(5.8),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg钯。5.33铂标准贮存溶液:称取0.1000g金属铂(wPt≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL混合酸(5.8),低温加热溶解,驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg铂。5.34铑标准贮存溶液:称取0.1000g金属铑(wRh≥99.99%),置于聚四氟乙烯溶样罐中,加入20mL盐酸(5.3)和4mL30%过氧化氢(5.2),于160℃~180℃烘箱中溶解48h以上至溶解完全。取出溶样罐,冷却至室温。开罐,将溶液转入200mL聚四氟乙烯烧杯中,盖上聚四氟乙烯盖,置于电热板上加热至沸。取下,稍冷,将溶液转入100mL塑料容量瓶中,冷至室温。用水稀释至刻度,混匀。此溶液1mL含1mg铑。5.35钛标准贮存溶液:称取0.1000g金属钛(wTi≥99.99%),置于100mL聚四氟乙烯烧杯中,加入10mL盐酸(5.5)加热溶解,冷却后,用盐酸(5.6)移入100mL塑料容量瓶中,稀释至刻度,混匀。此溶液1mL含1mg钛。5.36锡标准贮存溶液:称取0.1000g金属锡(wSn≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL混合酸(5.8),低温加热溶解,冷却至室温,用盐酸(5.5)移入100mL塑料容量瓶中并稀释至刻度,混匀。此溶液1mL含1mg锡。5.37硅标准贮存溶液:称取0.1000g金属硅(wSi≥99.99%),置于聚四氟乙烯烧杯中,加少量水润湿,加入约0.5g氢氧化钠加热溶解(分多次加入),溶解完全后,冷却至室温,移入100mL塑料容量瓶中并稀释至刻度,混匀。此溶液1mL含1mg硅。5.38碲标准贮存溶液:称取0.1000g金属碲(wTe≥99.99%),置于100mL聚四氟乙烯烧杯中,加入20mL硝酸(5.7),低温溶解,加热驱尽氮的氧化物,冷却至室温,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg碲。5.39锆标准贮存溶液:称取0.1000g金属锆(wZr≥99.99%),置于100mL聚四氟乙烯烧杯中,加入5mL氢氟酸溶液(1+1),再滴加硝酸(5.4)加热,溶解完全后,冷却至室温,移入100mL塑料容量瓶中,补加6mL硝酸(5.4),用纯水稀释至刻度,混匀。此溶液1mL含1mg锆。5.40钼标准贮存溶液:称取0.1500g三氧化钼(wMoO3≥99.95%),置于100mL聚四氟乙烯烧杯中,加少量氢氧化钠,加入水使其溶解,移入100mL塑料容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1mg钼。5.41混合标准溶液A1:在500mL塑料容量瓶中加入80mL盐酸(5.3)后,分别移取5.00mL标准贮5.42混合标准溶液B1:在500mL塑料容量瓶中加入80mL盐酸(5.3)后,分别移取5.00mL标准贮5.43混合标准溶液A2:在500mL塑料容量瓶中加入80mL盐酸(5.3)后,分别移取15.00mL标准贮5.44混合标准溶液B2:在500mL塑料容量瓶中加入80mL盐酸(5.3)后,分别移取15.00mL标准贮55.45金基体标准溶液:称取金(5.10)50.000g,精确至0.0001g,置于250mL聚四氟乙烯烧杯中,加入100mL混合酸(5.8),低温加热至溶液清亮,用水转入500mL塑料容量瓶中,补加100mL混合酸(5.8),用水稀释至刻度,混匀。此溶液1mL含100mg金。5.46氩气(体积分数≥99.99%)。6仪器设备6.1电感耦合等离子体原子发射光谱仪,在仪器最佳工作条件下,凡能达到下列指标者均可使用:—分辨率:200nm时光学分辨率不大于0.008nm;400nm时光学分辨率不大于0.020nm。—仪器稳定性:用1.00μg/mL的铜标准溶液测量11次,其发射强度的相对标准偏差不超过2.0%。推荐的电感耦合等离子体原子发射光谱仪工作条件参数见附录A。6.2分析天平:感量0.1mg。6.3电热板。7样品7.1试样将样品碾成1mm厚的薄片,用不锈钢剪刀剪成小碎片,放入聚四氟乙烯烧杯中,加入20mL乙醇(5.9),于电热板上加热煮沸5min后取下,将乙醇倾去,再用水洗涤试样3次。加入20mL盐酸(5.5),加热煮沸5min,倾去盐酸,再用水洗涤试样3次。将试样用无尘纸包裹,于105℃烘干后取出冷却。7.2试料称取1.000g试样(7.1),精确到0.0001g。8试验步骤8.1空白试验随同试料做基体匹配空白试验。8.2测定次数应独立进行不少于2次的测定,结果取其平均值。8.3测定8.3.1将试料(7.2)置于100mL聚四氟乙烯烧杯中,加入20mL混合酸(5.8),盖上聚四氟乙烯杯盖,低温加热溶解试料,浓缩至约5mL时取下冷却至室温。用盐酸(5.6)冲洗杯盖和杯壁,移入50mL塑料容量瓶中,用盐酸(5.6)稀释至刻度,混匀,得到测试试液。8.3.2于电感耦合等离子体原子发射光谱仪上,在选定的仪器工作条件下,测量试液及随同试料空白中被测元素的谱线强度,采用多谱线拟合法等多种校正方法处理出现的谱线干扰(多谱拟合法使用示例见附录B),扣除空白值,从工作曲线(见8.4)上确定被测元素的质量浓度。68.4工作曲线的绘制8.4.1系列标准溶液的配制铝系列标准溶液的配制分别于8个100mL塑料容量瓶中,加入2.5mL混合酸(5.8),20.00mL金基体标准溶液(5.45),再分别加入混合标准溶液A1(5.41)0mL、1.00mL、2.00mL、5.00mL、10.00mL、25.00mL,混合标准溶液A2(5.43)25.00mL、50.00mL,以盐酸(5.6)稀释至刻度,混匀。系列标准溶液质量浓度见表2。分别于8个100mL塑料容量瓶中,加入2.5mL混合酸(5.8),20.00mL金基体标准溶液(5.45),再分别加入混合标准溶液B1(5.42)0mL、1.00mL、2.00mL、5.00mL、10.00mL、25.00mL,混合标准溶液B2(5.44)25.00mL、50.00mL,以盐酸(5.6)稀释至刻度,混匀。系列标准溶液质量浓度见表2。注:可使用市售有证标准溶液。表2系列标准溶液浓度单位为微克每毫升序号元素STD-1STD-2STD-3STD-4STD-5STD-6STD-7STD-8A组00.100.200.501.002.507.5015.00B组00.100.200.501.002.507.5015.008.4.2工作曲线绘制与测试试液测定相同条件下,测量系列标准溶液中各元素的强度,以被测元素的浓度为横坐标、信号强度为纵坐标,绘制工作曲线。9试验数据处理按式(1)计算被测元素的质量分数wx,数值以%表示:wx=×100…………(1)式中:x—被测元素;ρX—试料溶液中被测元素的浓度,单位为微克每毫升(μg/mL);ρ0—空白溶液中被测元素的浓度,单位为微克每毫升(μg/mL);V—试料溶液的体积,单位为毫升(mL);m—试料质量,单位为克(g);计算结果保留至小数点后四位。710精密度在重复性条件下获得的两次独立测试结果的测定值,在以下给出的平均值范围内,这两个测试结果的绝对值不超过重复性限(r),超过重复性限(r)的情况不超过5%,重复性限(r)按表3数据采用线性内插法求得。精密度试验原始数据见附录C。表3重复性限元素质量分数%重复性限(r)%Ag0.00100.00020.00940.00130.05040.0041Cu0.00110.00020.00960.00100.06160.0030Fe0.00170.00030.01630.00160.06380.0032Pb0.00090.00020.00910.00110.05430.0027Bi0.00080.00020.00810.00110.05140.0038Sb0.00070.00020.00720.00100.05360.0029Mg0.00020.00010.00990.00060.04740.0029Ni0.00090.00020.00940.00070.04990.0022Mn0.00090.00020.00920.00060.05370.00228表3重复性限(续)元素质量分数%重复性限(r)%Pd0.00080.00020.00830.00080.05370.0032Cr0.00030.00020.00940.00050.05670.0029Pt0.00080.00020.00820.00080.06170.0023Rh0.00080.00010.00830.00080.0430.0032Ti0.00030.00010.00980.00080.04860.002Zn0.00090.00020.00850.00050.05450.0038As0.00060.00020.00990.00120.04990.0023Sn0.00080.00020.00730.00090.05380.0031Si0.00030.00010.00910.00080.04810.0028Co0.00080.00010.00820.00060.05410.0025Ca0.00030.00010.01040.00140.04850.00429表3重复性限(续)元素质量分数%重复性限(r)%K0.00030.00010.01010.00140.04940.004Li0.00080.00010.01020.00110.04940.0021Na0.00030.00010.01030.00140.0530.0035Te0.00070.00010.00770.00050.04840.0035V0.00020.00010.01020.0010.05020.0026Zr0.00030.00010.00990.00070.04870.0021Cd0.00070.00010.0080.00050.0630.0024Mo0.00030.00010.010.00070.04290.0029Re0.00020.00010.01040.00080.04920.0025Al0.00030.00010.010.00110.05020.00341010.2再现性在再现性条件下获得的两次独立测试结果的测定值,在表4给出的平均值范围内,这两个测试结果的绝对值不超过再现性限(R),超过再现性限(R)的情况不超过5%,再现性限(R)按表4数据采用线性内插法求得。精密度试验原始数据见附录C。表4再现性限元素质量分数%再现性限(R)%Ag0.0010.00030.00940.0020.05040.005Cu0.00110.00030.00960.00130.06160.0052Fe0.00170.00040.01630.00280.06380.0041Pb0.00090.00020.00910.00130.05430.0042Bi0.00080.00040.00810.00170.05140.0041Sb0.00070.00030.00720.00150.05360.0031Mg0.00020.00010.00990.00150.04740.0056Ni0.00090.00020.00940.00150.04990.0027Mn0.00090.00030.00920.00150.05370.004311表4再现性限(续)元素质量分数%再现性限(R)%Pd0.00080.00030.00830.0010.05370.005Cr0.00030.00030.00940.00180.05670.0044Pt0.00080.00030.00820.0010.06170.0036Rh0.00080.00010.00830.00120.0430.0047Ti0.00030.00010.00980.00120.04860.0036Zn0.00090.00020.00850.00130.05450.004As0.00060.00030.00990.00150.04990.0048Sn0.00080.00020.00730.00140.05380.0037Si0.00030.00020.00910.00180.04810.004Co0.00080.00020.00820.00120.05410.0035Ca0.00030.00020.01040.00150.04850.004412表4再现性限(续)元素质量分数%再现性限(R)%K0.00030.00030.01010.00260.04940.0049Li0.00080.00030.01020.00130.04940.0035Na0.00030.00020.01030.00160.0530.0052Te0.00070.00030.00770.00110.04840.0044V0.00020.00010.01020.00130.05020.0034Zr0.00030.00010.00990.00090.04870.0031Cd0.00070.00020.0080.00180.0630.0047Mo0.00030.00020.010.00140.04290.0037Re0.00020.00020.01040.0010.04920.0032Al0.00030.00020.010.00170.05020.00351311试验报告试验报告至少应给出以下内容:—试样;—本文件编号;—分析结果及其表示;—与基本试验步骤的差异;—试验中观察到的异常现象;—试验日期。14附录A(资料性)推荐的电感耦合等离子体原子发射光谱仪工作条件参数推荐的电感耦合等离子体原子发射光谱仪工作条件参数见表A.1,分析谱线推荐表及干扰元素见表A.2。适宜时,可使用其他波长,注意光学干扰。表A.1电感耦合等离子体原子发射光谱仪工作条件参数推荐表功率W雾化室气流L/min观测高度泵流量L/min等离子体流量L/min辅助体流量L/min时间s观测方式15000.70150.70150.25轴向表A.2电感耦合等离子体原子发射光谱仪分析谱线推荐表及干扰元素元素波长nm干扰元素元素波长nm干扰元素元素波长nm干扰元素AgCrKCuPtVLiFeRhNaPbTiTeBiZnVSbAsPdZrMgCoCdNiCaMoPtMnSnRePdZrSiZrAl注:表格空白指该谱线在试验条件下(或设备本身)未发现干扰元素。15附录B(资料性)电感耦合等离子体原子发射光谱法中多谱线拟合法使用示例以某一型号电感耦合等离子体原子发射光谱仪采用多谱线拟合法消除Pd对As188.979nm的干扰为例。a)谱线选择:选择188.979nm作为As分析谱线,按标准曲线法建立分析方法。b)待测溶液:空白溶液(kb)、As标准溶液(a)20mg/L、Pd标准溶液(i)10mg/L,均含2%金基体。根据多谱线拟合原理,分析元素和干扰元素浓度能采集到干扰峰即可,但从实际出发,所用溶液浓度宜接近实际样品的浓度。c)检测:在与样品检测相同的仪器条件下,将空白溶液(kb)、As标准溶液(a)、Pd标准溶液(i)作为待测试样检测。d)建立多谱线拟合(MSF)模型:在结果数据(Results)的检查光谱窗口(ExamineSpectra),将“检查”(Examine)调整为“检查多谱线拟合”(ExamineMSF)。在数据选择窗口(SelectData)将空白溶液(kb)设为“空白b”(Blank)、As标准溶液(a)设为“分析物a”(Analyte)、Pd标准溶液(i)设为“干扰物i”(Interference),保存该模型。e)在方法中带入多谱拟合(MSF)模型:选择相应的方法,在程序窗口(Process)将“峰值处理”(PeakProcessing)中“峰值算法”(PeakAlgorithm)由“峰面积”(PeakArea)调整为“多谱线拟合法”(MSF)。在“光谱校正”(SpectralCorrections)的“多谱线拟合法模型”(MSFmodel)中选择步骤d)所建立的模型,更新并保存方法。f)采用带入多谱线拟合(MSF)模型的方法处理数据或检测样品。16附录C(资料性)精密度试验原始数据、铝元素不同水平的金样品进行共同试验确、铝含量在重复性条件下独立测定7次。测定的原始数据见表C.1~表C.30。表C.1银的精密度试验原始数据元素实验室水平数wAg/%1234567Ag110.00100.00100.00100.00100.00100.00100.001120.00930.00950.00980.00940.00940.00980.009530.04920.04840.05230.05060.05300.05330.0521210.00100.00110.00100.00110.000980.00100.001020.01040.00950.00990.01000.00970.01020.008530.05280.05340.05120.04940.05190.05240.0485310.00100.00100.00110.00120.000950.00110.001120.00950.00840.00950.00980.00810.00840.008730.05270.05180.04700.04980.05120.04950.0522410.00110.00110.00100.000970.000980.000990.001120.00880.00890.00890.00890.00900.00880.008930.04830.04840.04870.04860.04960.04980.0483510.00110.00100.000910.00110.00110.00110.0009720.01100.00980.01010.01190.00990.00990.009930.05300.04860.04990.04980.05000.05050.0498610.000920.00110.000930.000910.000930.000980.001020.00900.00880.00860.00890.00890.00860.008630.05100.04900.04910.04790.05130.05050.0497710.000990.00100.000990.00100.00100.00100.0009820.00950.00950.00940.00940.00960.00960.009530.05040.05150.05120.05120.05000.05080.050617表C.2铜的精密度试验原始数据元素实验室水平数wCu/%1234567Cu110.00110.00110.00110.00110.00110.00110.001120.00990.00940.01020.01010.00990.01010.010030.06410.06200.06130.06440.06430.06270.0616210.00110.00100.00130.00120.00120.00130.001220.00920.00990.00940.00980.01020.01050.010330.06280.06420.06370.06490.06020.06070.0632310.00110.00120.00120.00110.000980.00100.001120.00970.00930.00860.00880.00970.00970.009930.06370.06120.06120.06270.06090.06060.0616410.000970.000940.000960.000950.000970.000920.0009420.00930.00900.00920.00930.00940.00930.009430.05900.05920.05890.05950.05860.05910.0589510.00120.00120.00110.00120.00120.00120.001220.00880.00940.00930.00900.00940.00950.009530.06030.06090.06050.06070.06070.06010.0599610.000920.00120.00100.00100.00100.00110.001120.00910.00960.00890.00980.00920.00850.009530.06200.06130.05910.06160.05990.06170.0599710.00110.00110.00110.00110.00110.00110.001120.00990.00980.00980.00980.01020.00990.009930.06290.06350.06300.06330.06300.06310.064118表C.3铁的精密度试验原始数据元素实验室水平数wFe/%1234567Fe110.00170.00160.00150.00190.00170.00200.001720.01580.01690.01700.01590.01640.01650.017230.06090.06390.06290.06010.06490.06300.0619210.00180.00160.00150.00150.00160.00150.001720.01560.01670.01730.01690.01650.01700.015930.06150.06420.06180.06200.06430.06390.0631310.00180.00190.00170.00180.00180.00180.001720.01740.01590.01650.01630.01500.01600.017730.06540.06430.06620.06730.06300.06600.0648410.00170.00160.00160.00170.00160.00150.001820.01640.01620.01540.01680.01700.01580.016630.06430.06260.06380.06630.06540.06380.0649510.00190.00180.00170.00180.00180.00180.001820.01590.01490.01520.01580.01490.01500.015130.06450.06330.06510.06510.06450.06460.0640610.00140.00180.00150.00170.00160.00160.001720.01570.01540.01570.01450.01460.01570.015230.06470.06360.06210.06380.06490.06350.0636710.00180.00180.00180.00180.00180.00180.001820.01770.01760.01760.01760.01780.01750.017830.06350.06350.06300.06300.06320.06300.063019表C.4铅的精密度试验原始数据元素实验室水平数wPb/%1234567Pb110.000950.000930.000990.000970.000930.000930.0009120.00880.00900.00880.00920.00920.00900.009130.05490.05490.05630.05540.05560.05610.0553210.000800.000920.00110.000970.000900.000930.0008020.00910.00870.00890.00910.00860.00880.008930.05370.05470.05530.05690.05580.05720.0536310.000850.000870.000960.000950.000970.00100.0008420.00920.00870.00840.00820.00890.00890.008430.05670.05660.05500.05480.05310.05520.0524410.000890.000820.000760.000850.000830.000940.0009320.00960.00980.00930.00950.00960.00950.009530.05250.05270.05350.05260.05280.05300.0528510.000810.000830.000980.000920.00100.00110.001120.00830.00840.00820.00830.00830.00840.008830.05330.05340.05320.05340.05250.05290.0520610.000820.000910.000860.000820.000900.000930.0008820.00890.00890.00910.00880.00880.00870.009330.05340.05270.05320.05300.05330.05370.0537710.00100.000910.000900.000900.000910.00100.0009020.01030.01040.01040.01050.01040.01040.010430.05580.05500.05530.05680.05350.05470.055720表C.5铋的精密度试验原始数据元素实验室水平数wBi/%1234567Bi110.00100.000940.000830.000830.000880.000870.0009320.00800.00820.00840.00800.00780.00840.008530.05110.04750.05150.05300.04960.05000.0534210.000800.000900.000840.00100.000940.000820.001020.00820.00770.00790.00870.00740.00860.007630.05360.05270.04950.04890.05160.05240.0494310.000820.000810.000870.000800.000700.000710.0007720.00880.00870.00760.00740.00740.00810.008030.05110.05110.05280.05340.05240.05110.0514410.000750.000770.000790.000770.000810.000840.0007420.00750.00750.00730.00750.00730.00780.007630.05250.05130.05220.05180.05140.05080.0519510.000820.000640.000510.000570.000580.000600.0005220.00750.00780.00770.00760.00760.00760.007630.05250.04940.05230.05260.05260.05270.0520610.000920.000980.000720.000980.000830.000970.0009120.00720.00900.00800.00780.00900.00760.008530.04900.05000.05040.05240.05300.05150.0524710.000910.000900.000910.000910.000920.000900.0008920.00890.00900.00900.00890.00900.00900.009130.05200.05110.05190.05150.05040.05060.050621表C.6锑的精密度试验原始数据元素实验室水平数wSb/%1234567Sb110.000630.000660.000620.000640.000690.000730.0007920.00740.00750.00750.00700.00710.00720.007330.05290.05300.05490.05290.05170.05430.0539210.000700.000800.000880.000700.000800.000700.0008520.00670.00750.00720.00730.00660.00700.007330.05320.05510.05460.05390.05270.05370.0530310.000720.000610.000670.000690.000700.000620.0006320.00710.00680.00710.00630.00710.00650.007130.05100.05250.05560.05280.05320.05530.0547410.000610.000570.000550.000580.000620.000630.0005720.00760.00770.00710.00740.00750.00760.007630.05330.05460.05550.05520.05460.05340.0543510.000710.000740.000770.000740.000690.000700.0006820.00740.00750.00750.00760.00690.00720.006930.05080.05210.05390.05390.05320.05260.0529610.000660.000710.000620.000640.000610.000760.0006420.00770.00770.00780.00740.00730.00720.007530.05470.05400.05420.05250.05380.05280.0547710.000670.000890.000750.000710.000750.000740.0007520.00690.00730.00720.00710.00720.00710.007130.05400.05340.05330.05340.05410.05410.054022表C.7镁的精密度试验原始数据元素实验室水平数wMg/%1234567Mg110.000210.000210.000180.000190.000240.000230.0001820.00990.00990.00990.00990.00950.01050.009730.04420.04700.04620.04500.04680.04770.0480210.000300.000200.000300.000200.000300.000300.0003020.00990.01020.01040.00990.00990.01010.009930.04510.04550.04600.04710.04690.04590.0466310.000220.000180.000210.000160.000260.000200.0002120.00970.00990.01000.00970.01000.00970.009330.04700.04890.05070.05020.04800.04920.0503410.000280.000240.000250.000290.000280.000290.0002620.01010.01020.00980.01040.01010.01030.010330.05010.05090.05020.05000.05020.05030.0501510.000190.000200.000190.000180.000180.000180.0001820.01070.01060.01080.01070.01080.01080.010630.04570.04500.04630.04690.04560.04620.0462610.000310.000220.000230.000210.000220.000230.0003420.00990.00980.00930.00920.00950.01000.009930.04740.04610.04700.04350.04530.04750.0455710.000230.000250.000240.000250.000230.000220.0002420.00920.00910.00910.00920.00930.00920.009230.04800.04700.04720.04770.04710.04730.048523表C.8镍的精密度试验原始数据元素实验室水平数wNi/%1234567Ni110.00100.00100.000930.00100.00100.000940.001020.00950.00990.00930.00940.00950.00970.009930.04920.05080.04960.05090.05190.05100.0509210.000940.000980.00100.00110.000930.000960.0009620.00880.00940.00950.00960.00900.00930.009930.05170.05130.05140.04980.05040.04930.0506310.00110.00100.000930.000920.000890.000960.0009820.00990.00940.01000.00980.00900.00910.009130.05120.05070.05140.04960.04800.04990.0487410.000910.000970.000920.000880.000900.000940.0009120.00880.00900.00900.00890.00930.00910.009130.04860.04910.04880.04960.04990.05010.0486510.00100.000950.000900.000910.000920.000920.0009220.00860.00850.00860.00840.00850.00860.008630.04890.04960.04910.04940.04940.04950.0488610.000920.000910.000780.000810.000920.000910.0009220.00940.00940.00970.00950.00970.00930.009430.04830.04980.04940.04980.04920.04900.0493710.000930.000960.000910.000930.000900.000910.0009020.01020.01010.01000.01010.01020.01010.010230.05060.05020.05040.05030.05010.05080.050424表C.9锰的精密度试验原始数据元素实验室水平数wMn/%1234567Mn110.00110.00110.00100.00100.00110.00100.001020.00960.00970.00980.00960.00960.00950.009030.05550.05530.05410.05440.05420.05520.0541210.00100.00100.000960.00110.00110.00100.0009720.00920.00940.01000.00970.00960.00970.009230.05350.05450.05610.05520.05360.05500.0538310.00110.00100.000940.000980.00100.00100.0009920.00900.00950.00920.00950.00920.00930.009130.05690.05540.05380.05280.05520.05480.0552410.000930.000870.000890.000940.000910.000970.0009120.00860.00860.00840.00870.00860.00910.008630.05150.05150.05130.05140.05210.05190.0521510.000780.000920.000880.000870.000870.000870.0008720.00860.00840.00840.00840.00840.00850.008530.05260.05310.05330.05350.05270.05270.0532610.000820.000810.000830.000810.000910.000900.0008920.00900.00920.00900.00950.00910.00910.009230.05290.05140.05320.05140.05230.05380.0523710.000810.000840.000810.000800.000830.000800.0008020.00980.00970.00970.00970.00990.00990.009930.05480.05530.05450.05520.05460.05530.055025表C.10钯的精密度试验原始数据元素实验室水平数wPd/%1234567Pd110.000840.000900.000820.000880.000830.000920.0008320.00830.00840.00780.00810.00820.00830.008530.05310.05180.05600.05370.05090.05490.0538210.000900.000870.000860.000850.000910.000940.0009220.00840.00890.00930.00870.00840.00850.008730.05260.04990.05330.05380.05510.05490.0531310.000780.000810.000780.000780.000810.000770.0007220.00830.00820.00820.00810.00840.00810.008130.05490.05510.05460.05350.05350.05270.0534410.000920.000950.000860.000910.000860.000880.0008920.00860.00850.00860.00880.00860.00850.008530.05510.05570.05480.05380.05520.05420.0535510.000900.000860.000910.000890.000860.000850.0008420.00840.00810.00850.00860.00810.00820.008030.05270.05480.05440.05560.05500.05530.0546610.000860.000810.000840.000820.000810.000910.0008320.00840.00810.00790.00840.00810.00820.007930.05330.05290.05270.05190.05370.05350.0536710.000810.000770.000670.000760.000690.000700.0007120.00820.00820.00800.00810.00820.00810.008230.05300.05290.05290.05350.05290.05320.052726表C.11铬的精密度试验原始数据元素实验室水平数wCr/%1234567Cr110.000230.000260.000230.000260.000210.000280.0002220.00950.00940.00950.00960.00900.00930.009430.05700.05900.05750.05690.05690.05600.0580210.000380.000350.000360.000390.000410.000430.0004020.00980.00950.00960.00970.00980.00970.009730.05430.05730.05610.05650.05860.05780.0591310.000220.000260.000280.000290.000250.000240.0002920.00930.00910.00870.00860.00930.00920.009030.05730.05900.05870.05820.05810.05770.0573410.000330.000350.000310.000290.000340.000330.0003320.00890.00880.00870.00910.00870.00890.008730.05600.05660.05580.05540.05620.05580.0558510.000310.000310.000310.000330.000320.000330.0003220.00890.00870.00900.00890.00880.00890.008930.05890.05490.05730.05720.05590.05610.0555610.000220.000230.000240.000170.000180.000190.0002920.00940.00940.00920.00930.00940.00970.009630.05460.05530.05490.05510.05300.05460.0526710.000410.000410.000520.000510.000500.000450.0004220.01060.01050.01040.01050.01070.01050.010730.05760.05720.05770.05750.05750.05800.057227表C.12铂的精密度试验原始数据元素实验室水平数wPt/%1234567Pt110.000920.000920.000920.000930.000870.000930.0009120.00850.00860.00860.00840.00820.00800.007930.06160.06170.06250.06270.06380.06000.0638210.000900.00100.00100.000900.000900.00110.0009020.00860.00910.00790.00860.00850.00810.008730.06340.06290.06220.06410.06130.06270.0623310.00100.000980.000700.000780.000790.000800.0007820.00870.00850.00790.00830.00760.00770.007930.06390.06370.06180.06140.06210.06360.0639410.000700.000680.000720.000730.000710.000720.0007120.00770.00760.00770.00800.00790.00790.007930.06150.06160.06120.06110.06130.06160.0613510.000810.000830.000910.000800.000840.000790.0007020.00840.00860.00850.00870.00800.00830.008030.05980.06000.06040.05970.06010.05960.0600610.000710.000720.000740.000840.000710.000810.0007820.00780.00800.00790.00820.00830.00800.008230.06210.06140.06000.06120.06110.06080.0608710.000890.00100.00110.000920.000890.000890.0008920.00840.00860.00830.00820.00810.00830.008330.06140.06190.06320.06090.06160.06180.061728表C.13铑的精密度试验原始数据元素实验室水平数wRh/%1234567Rh110.000840.000880.000820.000830.000810.000800.0007920.00820.00830.00830.00790.00790.00830.008030.04250.04340.04400.04270.04350.04380.0448210.000850.000870.000880.000840.000890.000840.0008620.00880.00890.00890.00900.00900.00890.008930.04360.04220.04320.04370.04480.04190.0439310.000940.000810.000800.000800.000820.000840.0007920.00880.00850.00770.00750.00850.00820.007430.04110.04270.04540.04540.04150.04170.0411410.000930.000910.000860.000880.000890.000870.0008620.00830.00850.00830.00850.00820.00850.008330.04050.04020.03970.04030.04080.04040.0407510.000850.000800.000770.000830.000830.000790.0007620.00810.00810.00800.00820.00770.00790.007630.04230.04320.04230.04210.04200.04200.0453610.000820.000810.000840.000820.000770.000820.0008120.00890.00830.00870.00800.00800.00810.008730.04460.04480.04500.04290.04270.04200.0456710.000810.000800.000810.000810.000810.000800.0008320.00840.00850.00840.00850.00850.00840.008530.04430.04400.04470.04470.04490.04450.044229表C.14钛的精密度试验原始数据元素实验室水平数wTi/%1234567Ti110.000240.000240.000250.000260.000220.000200.0002420.00980.00990.01040.00930.00980.00990.009630.04720.04890.04790.04950.04900.05030.0486210.000200.000200.000290.000290.000200.000200.0003020.01090.01040.00960.00990.00990.01010.009730.04880.04790.04750.04910.04890.04920.0478310.000270.000250.000300.000320.000300.000310.0003120.00990.01040.00990.00980.01020.