32 2 2013 6 GLOBAL GEOLOGY Vol. 32 No. 2 Jun. 2013 1004-5589 2013 02-0412-10 T Pt Rh Ru 130026 : 合成并研究了铬黑 T 形成树脂分离富集地质标准样品中的钌 铂 铑, 获得了最佳实验条件 结果表明 : ph = 2. 00 的盐酸溶液作为介质 温度为 293 K 流速 v 1. 0 ml min - 1 柱高 h 10. 0 cm, 铂 铑 钌吸附率均在 95% 以上 ; 在 293 K, 使用 40 ml 的 ph 2. 00 盐酸 - 3% 硫脲溶液静态洗脱或以 1. 0 ml min - 1 的流速进行动态洗脱, 洗脱率均在 95% 以上树脂对铂 铑 钌的吸附过程符合拟二级动力学模型实验条件下的标准回收实验, 回收率均 > 95% 对地质标准样品进行了分析测定, 相对误差均 < 7% 铂 铑 钌的相对标准偏差分别是铂: 0. 852 0% 和 0. 325 0% ; 铑 : 4. 20% 和 4. 89% ; 钌 : 1. 24% 和 1. 79% 铂 铑 钌的检出限分别为 3. 55 10-6 μg ml - 1 6. 23 10-7 μg ml - 1 1. 92 10-5 μg ml - 1 该方法的准确度和精密度较高 : 铬黑 T; 形成树脂 ; 分离富集 ; 示波极谱法 ; 贵金属 : P599; P618. 5 : A doi: 10. 3969 /j. issn. 1004-5589. 2013. 02. 028 Determination of Pt Rh and Ru in geological samples with oscillolarography after separation and enrichment by EBT forming resin GE Xiao-yan SHE Zhen-bao ZHANG Min LIU Jing College of Chemistry Jilin University Changchun 130026 China Abstract The resin modified with EBT was synthesized and the optimum experiment parameter was identified. The Pt Rh and Ru in geological standard samples were separated and enriched by EBT forming resin. When the ph HCl in 2. 00 the temperature is 293 K. The flow rates of sample solution is lower than or equal to 1. 0 ml / min. Column is longer than 10. 0 cm. The adsorption rates of Pt Rh and Ru are greater than 95%. When the temperature is 293 K elution with ph 2. 00 hydrochloric acid - 3% thiourea 40 ml by batch method or elution with the velocity of fiow at 1. 0 ml per minute by dynamic method the elution rates of Pt Rh and Ru are greater than 95%. The adsorption kinetics follow a pseudo-second - order model for the adsorption of Pt Rh and Ru by EBT forming resin. In the standard recovery experiment the recoveries of Pt Rh and Ru are greater than 95%. Being determined by oscillolarography relative errors are less than 7%. The relative standard deviations are 0. 852 0% and 0. 325 0% for Pt 4. 20 % and 4. 89 % for Rh and 1. 24% and 1. 79% for Ru. The detection limits Pt 3. 55 10-6 μg ml - 1 Rh 6. 23 10-7 μg ml - 1 Ru 1. 92 10-5 μg ml - 1. It is proved that this method is higher in accuracy and precision. 2012-10-08 2013-03-12 1955-. E-mail shezb@ jlu. edu. cn
2 T Pt Rh Ru 413 Key words EBT forming resin separation and enrichment oscillolarography noble metal ph = 2. 00 1 1. 4 1. 000 0 g 450 30 min 600 1 h 2-4 5 5 Na 2 O 2 400 760 15 ~ 20 min 250 ml 6 T -11 HCl T ph 2. 00 HCl Ru Pt Rh T 1. 5 1. 5. 1 静态吸附 100 ml 1 mol /L 48 h φ HCl = 50% 48 h 1. 5. 2 动态吸附 T 1. 3 T ph T 1. 3 30 cm 0. 5 cm 10 ml ± 2% 1. 1 JP -303 1 2 FA2004 PHS-3C Q = C 0 - C e V 1 000 m 30 cm 0. 5 cm D 290 12 E = C 0 - C e 100% C T EBT 0 1 2 10 mg /ml C 0 μg / ml Q mg /g C e 1. 2 T μg /ml V D 290 4 ml m g E % = 2. 00 1. 6 0. 2 ml /min T ph 2. 00 T
414 32 CH 2 6 N 4-1. 2% NH 4 Cl 0. 01% B - 2. 5 mol /L 1. 7 HCl 1. 7. 1 静态脱附 1. 8. 2 测定 3 钟贵金属元素的标准曲线 0. 100 0 g 1. 5. 1 5 5% 2 ml 4 mol /L 100 ml E 0 = - 780 mv 5% Ep = - 1 035 mv E 0 = - 780 mv Ep = - 1 230 mv E 0 = - 750 mv Ep = - 1 050 mv 5% 4 mol /L I P0 2 mol /L I P - 2 1. 7. 2 动态脱附 T 2. 1 100 ml 1. 7. 1 1 2. 2 1. 8 1. 8. 1 测试体系 0. 75 mol /L H 2 SO 4-0. 003% N 2 H 4 H 2 SO 4-1. 25 10-3 mol /L Table 1 1 Regress equations correlation coefficients and linearity ranges of elements r /μg ml - 1 Pt Y = 1 654. 974 97 + 4. 537 8 10 6 X 0. 998 77 0. 000 1 ~ 0. 008 0 Rh Y = - 6 345. 489 25 + 3. 007 10 7 X 0. 998 47 0. 000 5 ~ 0. 002 5 Ru Y = 482. 843 12 + 1. 043 94 10 5 X 0. 998 74 0. 002 ~ 0. 100 2. 2. 1 最佳吸附酸度的选择 6 50 μg 20 μg 20 μg Table 2 5 5% 2 ml 4 mol /L 10 ml 1. 0 mol /L ph = 1. 00 2. 00 3. 00 4. 00 5. 00 0. 100 0 g T 2 ph = 2. 00 96% ph = 2. 00 2 Effect of acidic conditions to resin adsorption rate 1. 0 mol /L HCl 79. 7 80. 7 83. 5 ph = 1. 00 96. 4 96. 6 93. 8 ph = 2. 00 98. 3 97. 8 96. 2 ph = 3. 00 96. 6 94. 8 96. 1 ph = 4. 00 91. 9 89. 3 95. 2 ph = 5. 00 83. 9 86. 8 93. 8
2 T Pt Rh Ru 415 2. 2. 2 最佳吸附温度的选择 4 2. 2. 1 3 20 Table 3 3 Effect of temperature conditions to resin adsorption rate / 20 97. 9 96. 7 96. 7 30 96. 4 94. 6 93. 8 40 92. 3 89. 8 91. 2 50 83. 6 80. 8 86. 1 2. 2. 3 最佳吸附时间的选择 ph = 2. 00 T 95% 1. 0 ml min - 1 ph = 2. 00 30 ml 20 Q t t 1 2 1 2 T Table 4 150 min 120 min 110 min Q Pt = 15. 898 mg /g Q Rh = 3. 501 mg /g Q Ru = 2. 394 mg /g 2 Fig. 2 - Q t - t curves of Rh and Ru 2. 2. 4 最佳过柱流速的选择 6 50 μg 20 μg 20 μg ph = 2. 00 T 2. 0 mg Pt 0. 5 mg Rh 0. 5 mg Ru 4 4 1. 0 3 100 ml 0. 100 0 g ml min - 1 4 Effect of over column velocity to resin adsorption rate /ml min - 1 0. 1 98. 9 97. 8 98. 1 0. 5 97. 9 98. 0 98. 3 1. 0 95. 8 96. 9 97. 5 1. 5 90. 3 91. 6 93. 6 2. 0 83. 7 85. 6 90. 6 2. 5 78. 2 70. 2 75. 6 1 Fig. 1 - Q t - t curve of Pt 2. 2. 5 最佳柱高的选择 ph = 2. 00 T 5 5 10 cm 96% 10 cm
416 32 Table 5 5 Effect of column height to resin adsorption rate 7 Table 7 Choice of eluant consumption /cm /ml 4. 0 73. 2 78. 9 76. 6 6. 0 89. 9 90. 4 92. 1 8. 0 93. 2 95. 1 95. 5 10. 0 97. 2 97. 9 96. 9 12. 0 96. 9 98. 1 98. 0 10. 0 63. 6 52. 7 70. 4 20. 0 78. 5 80. 1 82. 9 30. 0 92. 3 89. 1 93. 5 40. 0 95. 6 97. 6 96. 2 50. 0 97. 6 98. 2 97. 9 15. 0 98. 8 98. 6 97. 9 100 ml 2. 3 40. 0 ml ph = 2. 00-3% 2. 3. 1 洗脱剂的选择 4 T R 100 ml t 3 3 40. 0 ml 3% NH 3 H 2 O 1 1 ph 2. 00-3% 1. 0 mol /L - 1 4 95% 310 min 6 ph = 2. 00-3% 95% 2. 3. 3 洗脱时间的选择 200 min 210 min 310 min 6 Table 6 Choice of eluants 3% 89. 9 78. 7 93. 7 NH 3 H 2 O 1 1 50. 2 54. 9 46. 6 ph 2. 00-3% 95. 9 97. 1 96. 3 1. 0 mol /L - 1 4 68. 4 71. 9 53. 7 3 Fig. 3 - R - t curves of Pt Rh and Ru 2. 3. 2 洗脱剂的用量 5 T ph = 2. 00 100 ml 10. 0 20. 0 30. 0 40. 0 2. 3. 4 洗脱温度的选择 20 30 40 50 8 50. 0 ml ph = 2. 00-3% 20 30 95% 20 7 ph = 2. 00-3% 2. 3. 5 洗脱剂流速的选择 40. 0 ml 6 95% 40. 0 ml 40. 0 ml ph = 2. 00-3%
2 T Pt Rh Ru 417 Table 8 8 Effect of temperature conditions on the elution rate / 20 96. 8 95. 9 96. 7 30 95. 4 96. 3 95. 9 40 96. 2 93. 2 93. 5 50 94. 8 91. 9 95. 6 Table 11 11 /μg Standard recovery under dynamic conditions 5. 0 98. 2 98. 3 95. 6 5. 0 97. 4 97. 6 95. 5 10. 0 98. 6 95. 2 97. 3 10. 0 97. 6 96. 9 98. 1 9 9 1. 0 ml min - 1 95% 2. 5 T 1. 0 ml min - 1 Table 9 9 T Effect of the eluent flow rate on the elution rate /ml min - 1 0. 2 97. 2 98. 6 98. 8 0. 4 98. 6 97. 6 97. 9 0. 6 96. 5 97. 8 96. 6 1. 0 96. 1 96. 6 95. 3 1. 2 92. 5 95. 1 93. 8 1. 5 889 90. 2 86. 6 log q e - q t t q e 2. 4 k 1 T 4 10 11 10 11 95% 50. 0 96. 7 97. 4 98. 6 50. 0 95. 4 96. 2 96. 9 log q e - q t = logq e - k ( 1 2. 303) t 3 q e mg /g q t mg /g t k 1 min - 1 t min 10 Table 10 Standard recovery under static conditions /μg 5. 0 97. 6 98. 1 95. 8 5. 0 96. 4 97. 9 96. 7 10. 0 95. 2 96. 9 97. 5 10. 0 95. 6 97. 2 98. 4 50. 0 95. 9 96. 9 95. 3 50. 0 96. 8 95. 1 96. 0 Fig. 4 4 Pseudo - first order kinetic model for the adsorption of Pt Rh and Ru
418 32 t = 1 q t k 2 q 2 e + ( ) 1 q e t 4 t min q t mg /g t k 2 g mg - 1 min - 1 q e mg /g t /q t t q e k 2 h k 2 q e h = k 2 q 2 e T 5 Fig. 6 6 Intraparticle diffusion model for the adsorption of Pt Fig. 5 5 Pseudo - second order kinetic model for the adsorption of Pt Rh and Ru Fig. 7 lnq t = lnk id + 0. 5lnt 5 7 Intraparticle diffusion model for the adsorption of Rh and Ru t min q t mg /g 12 t k id mg g - 1 R 2 > min - 1 /2 lnq t lnt 0. 99 T 6 7 R 2 q e Table 12 12 Kinetic parameters for adsorption of Pt Rh and Ru k 1 /min - 1 q e /mg g - 1 R 2 k 2 /g mg - 1 min - 1 q e /mg g - 1 R 2 K id /mg g - 1 min - 1 /2 R 2 Pt 0. 021 4. 730 0. 872 0. 016 15. 362 0. 994 8. 639 2. 156 0. 934 Rh 0. 025 7. 138 0. 960 0. 049 3. 551 0. 990 2. 033 0. 709 0. 878 Ru 0. 053 0. 104 0. 924 1. 304 2. 401 0. 999 2. 240 0. 806 0. 921
2 T Pt Rh Ru 419 2 d - T T 13 ph 1. 00 ~ 9. 00 2. 6 T 2. 6. 2 铬黑 T 形成树脂的重复利用 2. 6. 1 铬黑 T 形成树脂稳定性测试 T 8 1. 000 0 g T ph = 1. 00 ~ 3. 00 Table 13 13 T Stability experiment of EBT forming resin in different medium 2. 0 mol /L 1. 0 mol /L ph = 1. 00 ph = 3. 00 ph = 9. 00 0. 2 mol /L 0. 2 mol /L 0. 5 mol /L 0. 68 0. 20 0 0 0 0. 08 0 0 10 15 μg 4 > 95% Table 15 Measurement of Rh 2. 7 2. 7. 1 样品分析 1. 000 0 g 72 - Pt - 02 T 14 15 16 /μg 14 Table 14 Measurement of Pt 1 0. 011 0 0. 011 7 6. 36 2 0. 011 0 0. 011 1 0. 91 /μg 3 0. 011 0 0. 010 6-3. 64 4. 89 1 0. 350 0 0. 345 4-1. 314 2 4 0. 011 0 0. 010 6-3. 64 2 0. 350 0 0. 347 1-0. 828 6 3 0. 350 0 0. 353 1 0. 8857 0. 852 0 5 0. 011 0 0. 011 6 5. 55 4 0. 350 0 0. 350 2 0. 057 1 5 0. 350 0 0. 349 8-0. 0571 /μg 1 0. 350 0 0. 350 9 0. 257 1 2 0. 350 0 0. 350 8 0. 228 6 3 0. 350 0 0. 351 7 0. 485 7 0. 325 0 4 0. 350 0 0. 351 1 0. 314 3 5 0. 350 0 0. 348 7-0. 371 4 /μg 1 0. 011 0 0. 010 6-3. 64 2 0. 011 0 0. 011 3 2. 73 3 0. 011 0 0. 011 5 4. 55 4. 20 4 0. 011 0 0. 010 5-4. 55 5 0. 011 0 0. 010 7-2. 73 2. 7. 2 方法检验 t t < T T 0. 05 4 = 2. 78 3 Pt Rh Ru 3. 55 10-6 μg ml - 1 6. 23 10-7 μg ml - 1 1. 92 10-5 μg ml - 1
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