Determination of Antimony in Antimony Ores by Inductively Coupled Plasma-Optical Emission Spectrometry with Microwave Digestion
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摘要: 采用王水溶解锑矿石常出现溶矿不彻底、提取过程中锑水解的问题，导致测定结果偏低；虽然原子荧光光谱法广泛应用于锑的测定，但是该方法由于仪器线性范围窄，对于高含量锑（>5%）的测定容易引入较大稀释误差。本文对样品采用氢氟酸-硝酸-盐酸混合酸溶后，在提取过程中加入酒石酸与锑络合，充分抑制了锑的水解。实验结果表明：采用氢氟酸、硝酸、盐酸混合酸体系的溶矿方式，能够有效分解矿石中的硅酸盐组分，使溶解更加彻底，锑的测定结果优于王水溶矿，且检出限更低（1.10μg/g）；通过酒石酸与锑的络合及盐酸对锑水解的抑制，锑的测定结果优于王水介质及盐酸介质的结果，且方法精密度（RSD，n=6）为0.11%~1.11%，较其他介质更稳定。在ICP-OES分析中通过对锑元素分析谱线的优选，可以获得更宽的线性范围，从而实现了对较高含量锑的准确测定。本方法能快速、有效溶解锑矿石并避免锑元素水解，经国家一级标物验证，所得结果与认定值相符，适用于分析锑矿石中含量范围在0.7%~40%的锑。
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关键词:
- 锑矿石 /
- 锑 /
- 氢氟酸-硝酸-盐酸酸溶 /
- 常压密闭微波消解 /
- 酒石酸-盐酸提取 /
- 电感耦合等离子体发射光谱法
Abstract:BACKGROUNDThe dissolution of antimony ore by aqua regia is often incomplete and antimony is easy to hydrolyze in the process of extraction, which leads to inaccurate results. Although atomic fluorescence spectrometry has been widely used in the determination of antimony, it is easy to introduce large dilution error for the determination of high-content antimony (>5%) due to the narrow linear range of the instrument. OBJECTIVESTo solve the problem of incomplete dissolution of antimony ores and hydrolysis of antimony in the extraction process, and establish a new method with wider linear range for determination of antimony in antimony ores. METHODSBased on inductively coupled plasma-optical emission spectrometry (ICP-OES), the antimony ore was fully dissolved by hydrofluoric acid, nitric acid and hydrochloric acid, and the hydrolysis of antimony was fully inhibited by the complexation of tartaric acid and antimony. RESULTSThe results showed that the solution of the mixed hydrofluoric acid, nitric acid and hydrochloric acid can effectively decompose the silicate components in antimony ores, which can make antimony ores dissolve more completely. The determination resultof antimony was better than that of aqua regia, and the detection limit was lower (1.10μg/g). The determination result of antimony obtained by the mixed extraction method of tartaric acid and hydrochloric acid was better than that of aqua regia. The precision of the method was 0.11%-1.11%, which was more stable than that of hydrochloric acid or aqua regia. By using an inductively coupled plasma emission spectrometer, a wider linear range can be obtained by optimizing the spectrum of antimony element analysis, therefore realizing the accurate determination of high-content antimony. CONCLUSIONSThis method can dissolve antimony ore quickly and effectively, and avoid the hydrolysis of antimony. The method is confirmed by national first grade standard materials, and the result is in agreement with the certified values. This method is suitable for the analysis of 0.7%-40% antimony in antimony ores. -
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表 1 微波消解升温程序
Table 1. Program of microwave digestion
步骤 升温时间(min) 目标温度(℃) 保持时间(min) 功率(W) 1 5 100 0 1200 2 5 120 3 1200 3 5 130 25 1200 
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表 2 不同提取介质的测定结果
Table 2. Analytical results of Sb in sample pretreated with different volumetric methods
标准物质编号 Sb认定值(%) 定容方式1 (5%酒石酸与5%盐酸混合溶液) 定容方式2 (15%王水定容) 定容方式3 (20%盐酸定容) 4次测定值(%) 平均值(%) 4次测定值(%) 平均值(%) 4次测定值(%) 平均值(%) GBW07175 18.97 19.01 18.99
19.04 19.0019.01 16.24 16.31
16.13 16.2016.22 18.64 18.57
18.69 18.6218.63 GBW07176 39.7 39.74 39.81
39.77 39.7339.76 33.57 33.49
33.26 33.3833.43 39.36 39.31
39.24 39.3839.32 GBW07279 6.26 6.28 6.31
6.27 6.296.29 5.31 5.46
5.37 5.345.37 5.97 5.89
5.91 5.845.90 GBW07280 1.81 1.83 1.84
1.80 1.821.82 1.44 1.51
1.55 1.531.51 1.64 1.59
1.61 1.631.62
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表 3 不同消解方式下锑的测定结果对比
Table 3. Comparison of the analytical results of Sb pretreated with different digestion methods
溶样方式 用酸量(mL) 溶样温度(℃) 溶样时间(h) Sb测定值(%) 敞口酸溶 26 160 4 18.93 常压密闭微波消解 8 130 1.5 18.96 高压密闭消解 6 180 6 18.94
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表 4 方法准确度和精密度
Table 4. Accuracy and precision tests of the method
标准物质编号 Sb含量(%) 相对误差(%) RSD(%) 分次测定值 平均值 认定值 GBW07175 19.01 19.04 18.98
19.00 18.99 19.0219.01 18.97 0.21 0.11 GBW07176 39.81 39.74 39.74
39.82 39.77 39.8039.79 39.7 0.23 0.11 GBW07279 6.31 6.29 6.24
6.28 6.30 6.346.29 6.26 0.48 0.53 GBW07280 1.77 1.73 1.76
1.74 1.72 1.731.74 1.81 0.13 1.11
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表 5 方法加标回收率
Table 5. Spiked recovery of the method
项目 Sb测定值(%) 样品1 样品2 样品3 称样量(g) 0.1000 0.1000 0.1000 溶液体积(mL) 100 100 100 加标前样品溶液测定浓度(μg/mL) 8.74 15.31 32.60 加标前样品溶液锑含量(μg) 874 1531 3260 锑标准溶液浓度(μg/mL) 100 100 100 加标体积(mL) 10 20 40 加标量(μg) 1000 2000 4000 加标后样品溶液测定浓度(μg/mL) 18.91 35.22 72.89 加标后样品溶液锑含量(μg) 1891 3522 7289 加标回收率(%) 102.0 99.6 101.0
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