Determination of Trace Impurity Elements in High Purity Silver Nitrate by Inductively Coupled Plasma-Mass Spectrometry with Precipitation Treatment
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摘要: 高纯硝酸银中痕量杂质元素的存在会影响其性能和质量，为提高现代测试技术分析痕量杂质元素的准确度，需要解决的首要问题是通过加入沉淀剂或还原剂将银除去，克服基体元素的基体效应。本文提出采用10 mL 10 g/L柠檬酸-5 g/L乙醇酸作络合保护剂，12 mL 100 g/L氯化铵作沉淀剂，建立了沉淀基体分离-电感耦合等离子体质谱同时测定高纯硝酸银中15种痕量杂质元素的分析方法。探讨了络合剂和沉淀剂浓度及用量、质谱干扰及同位素选择、非质谱干扰及内标选择、实验空白值等因素对测定结果的影响。在最佳的实验条件下，Cu、Pb、Ni、Mn、Au、Pd、Pt、Rh、Ru、Ir元素在0~100 ng/mL，Fe、Hg、Bi、Cr、Sn元素在0~250 ng/mL浓度范围内呈良好的线性关系。方法检出限(3σ)为0.005~0.062 ng/g，方法精密度(RSD，n=11)为0.6%~2.6%，加标回收率为94.1%~103.1%。与现行的分析方法相比，本方法采用的络合剂和沉淀剂能将基体元素与杂质元素完全分离而不影响测定结果；实验流程简单快速，检出限低，准确度和精密度均满足了实际样品的分析要求。Abstract: Trace impurity elements in high purity silver nitrate affect performance and quality. In order to improve the accuracy of analysis of modern testing technology for trace impurity elements, removing the silver by precipitant or deoxidizer to reduce matrix effect is the primary problem. A method has been developed for the simultaneous determination of 15 trace impurity elements in high purity sliver nitrate by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) with precipitation treatment. 10 mL 10 g/L citric acid and 5 g/L glycolic acid were used as complexing protectant to protect trace impurity elements during sample pretreatment. 12 mL 100 g/L ammonia chloride was used as precipitant to separate the matrix silver. The factors affecting the analytical results such as the concentration of complexing protectant and precipitant, the selection of isotope to avoid mass spectra interference, the matrix interference and the experimental blank values were comprehensively investigated and optimized. Under the optimized conditions, good linear relationships were obtained when the content ranges of Cu, Pb, Ni, Mn, Au, Pd, Pt, Rh, Ru and Ir were 0-100 ng/mL and Fe, Hg, Bi, Cr and Sn were 0-250 ng/mL. The detection limits of the method are 0.005-0.062 ng/g, the recovery rates are 94.1%-103.1% with precision of 0.6%-2.6% RSD (n=11). Compared with the existing analytical technique, the impurity elements and complex matrix could be separated completely using complexing protectant and precipitant. This new method is simple and practical with lower detection limits. Precision and accuracy meet the requirements of the simultaneous separation and determination of trace impurity elements in high purity silver nitrate samples.
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表 1 仪器工作参数
Table 1. Optimized measurement parameters of ICP-MS system
工作参数 设定条件 工作参数 设定条件 RF功率 1300 W 观测点 3峰 冷却气流量 15.0 L/min 扫描次数 5次 辅助气流量 1.0 L/min 重复测定次数 3次 雾化气流量 0.9 L/min 积分时间 100 ms 样品提升率 1.0 mL/min 采样深度 7.5 mm 分辨率(峰高) 0.8 amu 四极杆区真空度 6.7×10-2 Pa 测量方式 跳峰 检测器区真空度 6.7×10-4 Pa 
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表 2 分析元素同位素选择
Table 2. The selection of measured isotopes
元素 同位素
质量数天然丰度/% 元素 同位素
质量数天然丰度/% Cu 65 30.91 Rh 103 100 Fe 57 2.19 Ir 193 62.6 Pb 208 52.4 Ni 60 26.2 Bi 209 100 Mn 55 100 Au 197 100 Cd 111 12.9 Hg 202 29.8 Cr 52 83.8 Pd 106 27.33 Sn 118 24.0 Pt 195 33.7
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表 3 样品回收试验结果、方法检出限、回收率和精密度
Table 3. The experiment results,detection limits,recovery and precision of the method
元素 w/(μg·g-1) 回收率/% RSD/%
(n=11)检出限/
(μg·g-1)测定值 加标量 测定总量 Cu 0.39 5.00 5.121 95.0 1.3 0.023 Fe 0.47 3.00 3.529 101.7 2.4 0.045 Pb 0.21 1.00 1.139 94.1 0.8 0.031 Bi 0.009 8.00 8.023 100.2 1.2 0.049 Au 0.011 5.00 5.027 100.3 2.6 0.023 Hg 0.049 10.00 9.879 98.3 0.7 0.012 Pd 0.005 2.00 2.022 100.8 1.3 0.008 Pt 0.020 2.00 1.973 97.7 1.4 0.025 Rh 0.009 2.00 1.949 97.0 2.0 0.005 Ir 0.013 2.00 1.982 98.5 0.6 0.034 Ni 0.19 5.00 5.35 103.1 0.9 0.062 Mn 0.035 5.00 5.036 100.0 2.0 0.042 Cd 0.014 4.00 3.907 97.3 1.5 0.013 Cr 0.003 2.00 1.975 98.6 1.0 0.009 Sn 0.009 5.00 4.951 98.8 0.6 0.037
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表 4 实际高纯硝酸银样品分析
Table 4. Analytical results of elements in real samples
元素 第1种样品 第2种样品 5次测定平均值
w/(μg·g-1)RSD/%
(n=5)5次测定平均值
w/(μg·g-1)RSD/%
(n=5)Cu 0.35 1.1 0.32 1.4 Fe 0.50 2.2 0.45 2.7 Pb 0.27 2.0 0.14 2.2 Bi 0.016 1.2 0.009 1.4 Au 0.008 0.9 0.010 0.6 Hg 0.044 4.0 0.007 5.1 Pd 0.006 2.8 0.005 4.3 Pt 0.017 1.9 0.009 1.8 Rh 0.011 0.9 0.007 1.0 Ir 0.009 1.9 0.006 1.7 Ni 0.25 1.3 0.17 1.4 Mn 0.042 1.0 0.038 1.2 Cd 0.028 2.5 0.019 1.0 Cr 0.039 1.0 0.027 1.0 Sn 0.003 1.3 0.002 1.2
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