银化学分析方法 第7部分：金、钯量的测定 电感耦合等离子体发射光谱法 征求意见稿

3银化学分析方法第7部分：金和钯量的测定电感耦合等离子体原子发射光谱法警示——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。本文件规定了银中金和钯含量的测定方法。本文件适用于银中金和钯含量的测定。测定范围：金：0.0002%～0.050%，钯:0.0002%~0.050%。2规范性引用文件下列文件中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。GB/T6682分析实验室用水规格和试验方法GB/T8170数值修约规则与极限数值的表示和判定3术语和定义本文件没有需要界定的术语和定义。4方法原理试料用硝酸溶解，过滤分离金，将沉淀置于坩埚中，于马弗炉中灼烧，加入王水沸水浴中溶解。滤液加盐酸沉淀分离基体银，合并两种溶液，在盐酸介质中，于电感耦合等离子体原子发射光谱仪上,分别在242.7nm，340.458nm处测定试液中金和钯的强度。5试剂和材料除非另有说明，在分析中仅使用确认为分析纯及以上的试剂。5.1水，GB/T6682,二级水。5.2盐酸(p=1.19g/mL)5.3硝酸(p=1.42g/mL)5.4盐酸(1+1)5.5盐酸(1+4)5.6盐酸(5+95)5.7硝酸(1+5)5.8硝酸(2+98)5.9混合酸（盐酸：硝酸=3:1）5.10混合酸（盐酸：硝酸：水=3:1:4）5.11金标准贮存溶液:称取纯金0.1000g(质量分数≥99.99%),置于100mL烧杯中,加入20mL王水(5.9),盖上表面皿,低温加热溶解,取下用水洗表皿及杯壁,冷却。移入100mL容量瓶中,用水稀释至刻度,混4匀。此溶液1mL含1000μg金。5.12钯标准贮存溶液:称取0.1000g金属钯(质量分数≥99.99%)于100mL烧杯中,加入20mL混合酸(5.9),低温加热溶解,驱赶氮的氧化物,冷却至室温,移入100mL容量瓶中,用水稀释至刻度,混匀。此溶液1mL含1000μg钯。5.13金和钯混合标准溶液（100μg/mL):分别移取金标准贮存溶液(5.11)钯标准贮存溶液(5.12)各10.0mL于100mL容量瓶中,加入10mL混合酸(5.10)，用水稀释至刻度,混匀,此溶液1mL含有100μg金，100μg钯。6仪器和设备6.1分析天平：分度值0.1mg。6.2瓷坩埚：容积为50mL。6.3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0.010nm；400nm时光学分辨率不大0.020nm；——仪器稳定性:在仪器的最佳工作条件下，用最低浓度的标准溶液（不是“零”浓度标准溶液）测量11次，各元素光强度的相对标准偏差不超过2.5%。——各元素推荐的分析谱线见表1。表1测定元素推荐波长AuPd仪器推荐工作条件参数参见附录A。7样品试料用20mL盐酸（5.5）微沸5分钟，用水清洗至无氯离子后，再用无水乙醇冲洗两次，自然晾干后备用。8分析步骤按表2称取试料，精确至0.0001g。表2称样量及定容体积g55%3118.2空白试验随同试料做空白试验。8.3测定58.3.1按表2称取试料置于250mL烧杯中、按表2加入硝酸(5.7)，盖上表面皿,低温加热溶解,取下,用水冲洗表皿及杯壁加热煮沸。用定量慢速滤纸加少许滤纸浆过滤,用热硝酸(5.8)洗涤烧杯及沉淀共6-7次，洗液用250mL烧杯承接。将沉淀连同滤纸一起放入50mL瓷坩埚中,在电热板上烘干,置于马弗炉中从低温升至700℃,灼烧15min,取出放冷。加入10mL混合酸(5.9),在沸水浴上加热溶解金,至体积约为1mL。8.3.2将7.3.1所得滤液(体积约70mL，如体积过大浓缩至70mL左右)置于电热板上加热煮沸,取下，按表2边搅拌边慢慢滴加盐酸(5.5例如：25mL盐酸溶液滴加时间控制在3~5min,加入速度约0.12mL/s~0.17mL/s），加热并不断搅拌至溶液清亮，于沸水浴保温30min，保温过程中每隔10min用玻璃棒搅拌沉淀。用慢速定量滤纸过滤,先将上清液倒入漏斗过滤完后，沉淀留于原杯中每次加入约10mL热稀盐酸(5.6)于杯中，用玻璃棒搅拌后将洗液倒入漏斗中过滤，沉淀留于原杯中重复上述动作5~6次后，连同沉淀一起倒入漏斗中，热稀盐酸(5.6)洗涤杯壁及沉淀3~4次,滤液收集于400mL烧杯中。8.3.3将7.3.1和7.3.2所得溶液合并，置于低温电热板上蒸至近干,取下冷却后，用适量水吹洗杯壁及表面皿,按表2加入盐酸(5.4),低温溶解盐类，取下冷却。按表2移入相应体积容量瓶中,用水稀释至刻度,混匀。干过滤后，于电感耦合等离子体发射光谱仪上，波长267.59nm、340.458nm处,在选定的仪器工作条件下,测量分析试液及随同试料空白中被测元素的谱线强度，扣除空白值,从工作曲线上确定被测元素的质量浓度。8.4工作曲线的绘制8.4.1系列标准工作溶液配制移取0mL、0.25、0.50mL、1.00mL、200mL、5.00mL、10.00mL金和钯混合标准溶液（5.13），置于一组100mL容量瓶中，加入10mL盐酸（5.4），用水稀释至刻度，混匀。8.4.2工作曲线的绘制在与试液测定相同条件下,以“零”标准溶液调零,测量系列标准工作溶液的光谱强度,以被测元素的浓度为横坐标,谱线强度为纵坐标,由仪器自动绘制工作曲线。9试验数据处理被测元素以质量分数wx计，按公式（1）计算：wx100%…………（1）式中：c0——自工作曲线上查得空白溶液中金、钯的质量浓度，单位为微克每毫升(µg/mLc——自工作曲线上查得试液中金、钯的质量浓度，单位为微克每毫升(µg/mL）；v——测定试液的体积，单位为毫升（mL）;m——试料的质量，单位为克（g）；计算结果表示到小数点后4位；若质量分数小于0.0010%时，计算结果表示到小数点后5位。10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数据采用线性外延法求得。表3重复性限wAu/%wPd/%10.2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，在以下给出的平均值范围内，这两个测试结6果的绝对差不超过再现性限（R），超过再现性限（R）的情况不超过5%，再现性限（R）按表4数据采用线性外延法求得。表4再现性限wAu/%R/%wPd/%R/%11.试验报告本章规定试验报告所包括的内容。至少应给出以下几个方面的内容：——试验对象；——使用的方法；——分析结果及其表示；——与基本分析步骤的差异；——观察到的异常现象；——试验日期。7电感耦合等离子体发射光谱仪，工作参数见表1。表1仪器工作参数雾化器气体流量（L/min）观测高度（mm）辅助气体流量（L/min）泵稳定时间分析泵速（rpm）0.70.58精密度试验原始数据精密度数据是在2023年由18家实验室对金、钯含量的5个不同水平样品进行试验确定的。每个实验室对每个水平的金、钯含量在重复性条件下独立测定7次。测量的原始数据见表A·2、A·3。表A·2金精密度原始数据实验室次数Au-水平j123451、大冶有色设计研究院有限公司（牵头起草）10.000200.001480.003020.01440.052620.000200.001480.003120.01500.049130.000210.001680.002960.01490.051540.000190.001410.002970.01360.052050.000200.00160.002940.01400.051660.000200.001510.003090.01440.055970.000200.001660.003060.01510.0516均值0.000200.001550.003020.014490.05204s0.000010.000100.000070.000560.002022、南京市产品质量监督检查院（参与起草）10.00016*0.001490.003020.014600.03911**20.00015*0.001600.002720.014220.03755**30.00021*0.001470.002660.013990.03812**40.00020*0.001470.00230**0.013650.03779**50.00014*0.001470.002650.014030.03791**60.00015*0.001670.002660.014210.03879**70.00018*0.001700.002680.013710.03764**均值0.000170.001550.002670.014060.03813s0.000030.000100.000210.000320.000603、北京达博有色金属焊料有限责任公司（一验单位）10.000170.0009**0.00260.0126*0.047920.00026**0.0010**0.00270.0118*0.048630.000180.0009**0.00280.01380.046840.000230.0011**0.00260.01350.047050.00015**0.0010**0.00270.01330.0473860.000210.0011**0.00280.0130*0.046970.000170.0011**0.00270.01350.0476均值0.000200.00100.00270.01310.0474s0.000040.000090.000080.000680.000654、中船黄冈贵金属有限公司（一验单位）10.00027**0.001200.00260**0.014500.04720**20.00031**0.001400.00211**0.01290*0.0493030.00030**0.001150.00256**0.014740.04724**40.00024**0.001400.00223**0.013870.0482550.00025**0.001400.00250**0.01322*0.0540660.00024**0.001400.00212**0.01287*0.0508270.00026**0.001500.00234**0.014540.04982均值0.000270.001350.002350.013810.04953s0.000030.000130.000210.000810.002405、江西铜业股份有限公司（一验单位）10.000190.00170.00310.01550.053920.000180.00170.00310.01540.055530.000180.00170.00310.01530.054640.000190.00180.00300.01540.054150.000200.00170.00300.01550.053460.000200.00160.00280.01510.054070.000200.00170.00300.01520.0534均值0.000190.00170.00300.01530.0541s0.000010.000060.000110.000150.000736、紫金矿业集团股份有限公司测试中心（二验单位）10.000170.001690.003030.0160.055220.000170.001680.002950.01540.054130.000160.001610.002910.01540.054140.000170.001630.002950.01530.053750.000170.00160.003010.01510.053560.000180.001550.002810.01510.052770.000180.001570.002860.01510.0523均值0.000170.00160.00290.01530.0537s0.000010.000050.000080.000320.000967、金川集团股份有限公司检测中心（二验单位）10.000220.00160.00310.0150.0520.000230.00170.0030.0140.05230.000230.00170.0030.0150.05240.000210.00170.0030.0150.05150.000230.00160.0030.016*0.05160.000230.00160.00310.0140.052970.000240.00170.00290.016*0.053均值0.000230.00170.00300.0150.052s0.000010.000050.000070.000820.000988、山东招金金银精炼有限公司（二验单位）10.0001930.0014630.002940.01360.049120.0002010.0014920.002940.01400.048830.0002030.0014440.003030.01400.048540.0001960.0014670.003090.01380.049050.0001890.0014830.003020.01320.050260.0001940.0014430.003070.01440.048870.0001970.0014370.002940.01410.0484均值0.000200.001460.003000.01390.0490s0.000000.000020.000060.000380.000589、中国有色桂林矿产地质研究院有限公司（二验单位）10.000180.00160.00280.01480.051620.000170.00160.00290.01470.05230.000180.00150.00290.01460.051940.000180.00160.00280.01460.050850.000180.00160.00280.01480.050660.000180.00160.00290.01460.05170.000190.00160.00280.01450.0507均值0.000180.00160.00280.01470.0512s0.000010.000040.000050.000110.0005910、国标（北京）检验认证有限公司（二验单位）10.00020.00160.00290.0130.04520.000210.00160.00290.0130.04530.00020.00150.0030.0130.04540.000190.00160.00310.0130.04550.00020.00160.00310.0140.04660.00020.00170.00310.0140.04670.00020.00160.00300.0140.046均值0.000200.00160.00300.01340.0454s0.000010.000060.000090.000530.0005311、北京有色金属与稀土应用研究所有限公司理化中心（二验单位）10.000220.00160.00320.01310.0446**20.000170.0012**0.00320.01480.0444**30.000180.00140.00330.0150.0467**40.000190.0012**0.00330.0150.050450.000160.001**0.00340.01480.049160.00020.0012**0.00310.01420.05170.00020.00140.00310.01470.049均值0.000190.00130.00320.01450.0479s0.000020.000200.000110.000680.0026812、云南黄金矿业集团贵金属检测有限公司（二验单位）10.000210.00170.00310.01460.054120.000190.00160.00300.01490.054530.000210.00160.00310.01510.052240.000210.00170.00310.01530.053050.000210.00170.00310.01510.052860.000210.00170.00320.01520.053570.000210.00180.00320.01510.0526均值0.000210.00170.00310.01500.0532s0.000010.000070.000070.000230.0008313、贵研检测科技云南有限公司（二验单位）10.000170.00160.00300.01510.051320.000190.00160.00300.01490.050630.000190.00160.00280.01480.050740.000200.00160.00280.01500.051250.000180.00160.00280.01540.051460.000170.00150.00290.01470.051170.000170.00160.00300.01470.0522均值0.000180.00160.00290.01490.0512s0.000010.000040.000100.000250.0005314、中金岭南有色金属股份有限公司（二验单位）10.000170.001590.002940.01440.049620.000140.001630.0030.01430.04930.000160.001620.002980.01450.049640.000170.001560.00290.01430.049550.000180.001430.002920.01420.0560.000160.001520.002940.01420.049870.000150.001550.002920.01440.0495均值0.000160.001560.002940.01430.0496s0.000010.000070.000040.000110.0003115、铜陵有色金属集团控股有限公司（二验单位）10.000170.00160.00280.0150.04820.000160.00150.00280.0140.04630.000170.00160.00290.0140.04840.000170.00150.00290.0140.04750.000170.00160.00280.0140.04760.000180.00160.0030.0140.04770.000170.00170.0030.0150.046均值0.000170.00160.00290.0140.047s0.000010.000070.000090.000490.0008216、江苏北矿金属循环利用科技有限公司（二验单位）10.000170.001330.002700.013910.0477120.000160.001400.002890.013650.0483830.000140.001620.002650.013630.0474840.000160.001550.002740.013590.0482950.000140.001570.002770.013990.0475360.000150.001470.002650.013560.0486570.000150.001530.002630.013770.04721均值0.000150.00150.00270.01370.0479s0.000010.000100.000090.000170.0005417、山东恒邦冶炼股份有限公司（二验单位）10.000210.00170.00320.016*0.056**20.00020.00160.00310.016*0.055*30.00020.00150.0030.016*0.055*40.000210.00160.00310.0150.054*50.000190.00170.00310.0150.05160.000190.00170.00310.0140.05170.000190.00170.00310.0150.052*均值0.000200.00160.00310.01530.0534s0.000010.000080.000060.000760.0020718、云南铜业股份有限公司（二验单位）10.000180.001560.002930.01280.049720.000190.001630.002850.01460.052030.000210.001580.002960.01380.053340.000200.001610.003110.01380.051750.000190.001650.003080.01330.049060.000170.001570.002830.01410.051270.000200.001570.002850.01370.0505均值0.000190.001600.002940.013730.05106s0.000010.000030.000110.000570.00146表A·3钯精密度原始数据实验室次数Pd-水平j123451、大冶有色设计研究院有限公司（牵头起草）10.0001560.001480.002830.01360.04820.0001490.001530.002930.01380.048530.0001530.001480.002770.01360.048640.0001390.001450.00280.0140.048350.0001380.00150.002830.01440.049960.0001310.001460.002720.01340.050770.0001520.001490.002790.01330.0466均值0.000150.001480.002810.013730.04866s0.000010.000030.000070.000380.001332、南京市产品质量监督检查院（参与起草）10.000037**0.001410.00330**0.012980.0498420.000031**0.001470.00368**0.012720.0476230.000022**0.001480.00362**0.012860.05336**40.000034**0.001490.00354**0.012900.05221**50.000029**0.001560.00333**0.012610.05413**60.000024**0.001490.00325**0.012080.05353**70.000023**0.001380.00328**0.012320.05294**均值0.000030.001470.003430.012640.05195s0.000010.000060.000180.000330.002363、北京达博有色金属焊料有限责任公司（一验单位）10.000110.0010**0.00260.0189**0.047620.000120.0010**0.00270.0185**0.047930.000100.0010**0.00260.0197**0.047440.000120.0010**0.00270.0185**0.046850.000100.0012**0.00270.0193**0.047360.000090.0011**0.00260.0195**0.04870.000100.0012**0.00270.0187**0.0488均值0.000110.00110.00270.01900.0477s0.000010.000100.000050.000490.000634、中船黄冈贵金属有限公司（一验单位）10.00018*0.001700.002800.013700.04588**20.00017*0.001600.002800.013200.04506**30.00018*0.001720.002870.014500.04231**40.00015*0.001770.002640.013500.04151**50.00020*0.001690.002450.014500.04278**60.00016*0.001760.00236**0.01150**0.04476**70.00019*0.001770.00214**0.01270**0.04532**均值0.000180.001720.002580.013370.04395s0.000020.000060.000270.001050.001715、江西铜业股份有限公司（一验单位）10.000160.00170.0030.01470.051420.000170.00160.00310.01450.053130.000170.00170.0030.01460.052140.000180.00170.00310.01460.051550.000170.00170.0030.01470.052660.000150.00170.0030.01460.051570.000170.00170.0030.01450.0518均值0.000170.00170.00300.01460.0520s0.000010.000040.000050.000080.000646、紫金矿业集团股份有限公司测试中心（二验单位）10.000180.001710.003020.01480.051720.000170.001670.002950.01440.05130.000160.001640.002870.01450.050840.000160.001680.003060.01460.051250.000170.001690.003030.01450.049960.000160.001640.002890.01470.051570.000170.001650.002930.01460.0503均值0.000170.001670.002960.01460.0509s0.000010.000030.000070.000130.000647、金川集团股份有限公司检测中心（二验单位）10.00024**0.00160.00280.0140.0520.00027**0.00160.00280.0140.04930.00026**0.00170.00280.0140.04940.00026**0.00160.00280.0150.04850.00024**0.00170.00270.0140.04960.00025**0.00180.00280.0140.04970.00027**0.00180.00290.016*0.050均值0.000260.00170.00280.0140.049s0.000010.000090.000060.000790.000698、山东招金金银精炼有限公司（二验单位）10.000210.001470.003070.01290.046220.000210.001470.002930.01340.047330.000210.001460.003030.01340.046840.000200.001440.003080.01320.048050.000190.001470.003020.01250.049360.000210.001470.002930.01370.047970.000210.001500.002940.01350.0477均值0.000200.001470.003000.01330.0476s0.000010.000020.000060.000400.000979、中国有色桂林矿产地质研究院有限公司（二验单位）10.000160.00150.00280.01370.048620.000170.00150.00290.01390.048830.000160.00160.00280.01360.048940.000160.00170.00280.0140.049750.000150.00170.00290.01410.049560.000170.00170.00280.01360.049670.000160.00160.00280.01380.0488均值0.000160.00160.00280.01380.0491s0.000010.000090.000050.000200.0004510、国标（北京）检验认证有限公司（二验单位）10.000210.00170.0030.0140.04820.000210.00170.00310.0140.04830.000220.00170.0030.0140.04840.000210.00160.00310.0150.04950.000210.00170.00310.0140.04960.000210.00180.00320.0140.04970.000210.00180.0030.0140.049均值0.000210.00170.00310.01410.0486s0.000000.000070.000080.000380.0005311、北京有色金属与稀土应用研究所有限公司理化中心（二验单位）10.000150.00140.00240.01360.0463**20.000140.00150.00260.01340.0473**30.000130.00150.00270.01350.050240.000160.00140.00260.01380.050850.000140.00150.00280.01410.050260.000130.00140.00260.01360.052**70.000140.00150.00270.01360.0513均值0.000140.00150.00260.01370.0497s0.000010.000050.000130.000230.0021212、云南黄金矿业集团贵金属检测有限公司（二验单位）10.000160.00140.0024**0.0131*0.0458*20.000150.0012**0.0024**0.0133*0.0463*30.000170.0013**0.00270.0132*0.0460*40.000140.00160.00300.01460.049250.000170.00160.00300.01480.049860.000150.00150.00270.01430.049570.000150.00150.00270.01400.0500均值0.000160.00140.00270.01390.0481s0.000010.000150.000240.000700.0019413、贵研检测科技云南有限公司（二验单位）10.000200.00170.00300.01460.050020.000210.00170.00280.01450.050030.000180.00160.00280.01460.049840.000170.00160.00280.01450.047350.000180.00160.00280.01440.050260.000190.00160.00290.01410.049870.000200.00160.00280.01400.0509均值0.000190.00160.00280.01440.0497s0.000010.000050.000080.000240.0011314、中金岭南有色金属股份有限公司（二验单位）10.00011**0.001550.002850.01350.047620.000140.001540.002840.01330.047730.00011**0.001530.00291