高純度試薬中の微量不純物分析 - tosoh.co.jp

1 25.. 1. Determination of Trace Impurities in Highly Purified Reagent Tomoaki TAKATA. The determination of trace impurities in a highly purified reagent. Ultra pure water, hydrochloric acid and hydrofluoric acid the sample was evaporated to dryness on a heater. The residue was dissolved by nitric acid. The trace elements (Al, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, Pb and Zn) of pg mL -1 level were determined by inductively coupled plasma mass spectrometry (ICP-MS). The recovery of each element was greater than about 80 . Aqueous sodium hydroxide the removal of major element (Na) could be carried out by chelating resin which has an iminodiacetic acid group.

2 After conditioning, the chelating resin was run through with sample and an ammonium acetate buffer and water to remove the major element, such as Na, and was then eluted with 3M nitric acid. Cr( ) was determined by the anion-exchange method. Cr( ) was adsorbed on an anion-exchange resin disk. The anion-exchange resin was washed with ultra pure water to remove the major element, and was then eluted with 20 nitric acid. The trace elements (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) of ng g-1 level were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) or ICP-MS. The recovery of each element was greater than about 80 , and Na concentration was decreased to g g-1 level in the final solution.

3 ICP MS . 1 .. Si P . ng g 1 pg g 1 .. ICP MS . ICP MS . Cl . SO 42 .. 1 . 26 TOSOH Research Technology Review 2010 . ICP MS ELAN DRC . ICP AES . Optima5300DV . Table pH . Twin pH . KR 12A . ICP MS 2 .. PURELAB Ultra . cm 20 . 38 TAMAPURE AA 10. 10ppt . Na 60 11 . Ultrapur 10M .. SPEX . XSTC 13 31 10mg L 1 Cr . 11 .. 12 13 . 1000ppm . PTFE 3M . Empore 10mm . 14 16 . SDB . GL SPE . C r 3 M . Empore Anion SR 47mm 4 . 1. pg mL SDB . 3 .. 1. Na ng g .. 2 .. 1 .. Table Operating conditions for ICP MS and ICP AES. ICP MS Perkin Elmer ELAN DRC ICP AES Perkin Elmer Optima5300DV. Plasma conditions Plasma conditions . RF power 1500W RF power 1300W.

4 Plasma gas flow rate min 1 Ar Plasma gas flow rate min 1 Ar Auxiliary gas flow rate min 1 Ar Auxiliary gas flow rate min 1 Ar Nebuliser gas flow rate min 1 Ar Carrier gas flow rate min 1 Ar Data acquisition Data acquisition . Dwell time 50ms Integration 1 5s Number of readings 20points Repetition 3times Repetition 3times 54 2010 27. 50mL . 20mL 100mL Na 20 . 20mL Cr . PFA 10mL Cr ICP . PFA AES ICP MS .. 3 . 17 19 . 3 1 . pg PFA 1 .. 4 1000 . 4 1 100 . 1000 100mL PFA 1cf cubic feet .. 1mL . Empore Chelating Disk Sample min 1 ICP MS 15 Cartridge 24mL . 100mL 3M HNO3 5mL. 100pg Zn 500pg H2O 12mL. CH3 COONH4 6mL. 4 2 Sample Loading 100 20mL CH3 COONH4 30mL.

5 H2O 6mL. 4 1 . Elute 3M HNO3 2. 200pg . 4 1 Constant volume 5mL . 4 3 . Ultrapur 11 25g . Analysis ICP AES or ICP MS.. 10M pH Fig. Separation procedure for the impurities in aqueous sodium hydroxide 50mL pH.. Empore . Empore Disk Anion SR Sample Fig. 20mL . 3 M 5mL 12mL 20 HNO3 10mL. 6mL H2O 50mL. 24mL Sample Loading 30mL 6mL H2O 100mL. Na 3M 2 . Elute 20 HNO3 20mL. 5mL . Na ICP MS Evaporation ICP AES Constant volume 10mL .. Analysis ICP AES or ICP MS. C r . Anion SR Fig. Fig. Separation procedure for Cr . in aqueous sodium hydroxide 20 10mL . 28 TOSOH Research Technology Review 2010 . 5 5 3. 1. m 5counts cf 80 . 1.

6 M 40counts cf . 3 . 71mm PFA 50g . 20 38 . 1 Table . 5 2 3 . mL 1 . Table 50pg 1pg mL 1 . T a b l e Zn . 2 mL 1 .. 20 38 Teble Recovery of the impurities in hydrochloric acid a Table 3 Added Foundb Recovery Element pg mL 1 pg mL 1 . Al 10 102. Ca 10 105. Teble Amounts of analytical element Cd 10 96. in clean draft or room Cr 10 108. Clean draft Clean room Cu 10 95. Element Fe 10 113. pg pg . Al 50 50 K 10 103. Ca 50 50 Mg 10 96. Cr 50 50 Mn 10 100. Cu 50 50 Na 10 102. Fe 50 50 Ni 10 102. K 50 50 Pb 10 99. Mg 50 50 Zn 10 93. Na 50 50 a Sample volume 20mL. b Values are the mean of four measurements standard deviation.

7 Teble Recovery of the impurities in ultra pure water a Added Foundb Recovery Teble Recovery of the impurities in Element pg mL 1 pg mL 1 hydrofluoric acid a Al 93 Added Foundb Recovery Element Ca 100 pg mL 1 pg mL 1 . Cd 97 Al 107. Co 94 Ca 10 102. Cr 90 Cd 10 101. Cu 83 Cr 10 93. Fe 108 Cu 10 91. K 92 Fe 96. Li 97 K 10 107. Mg 112 Mg 98. Mn 93 Mn 10 102. Na 103 Na 10 99. Ni 92 Ni 10 104. Pb 94 Pb 10 99. Zn 90 Zn 10 98. a Sample volume 100mL a Sample volume 20mL. b Values are the mean of three measurements b Values are the mean of three measurements standard deviation. standard deviation. 54 2010 29. 3 2 . Zn Fig. 3 2 1.

8 Zn . Zn 1 . 1. mL Zn . 3M . Ca Mg 3mL 4 . 1. Fe 10pg mL ICP AES Fig.. Al Ca Cu Fe Mg Zn 3M 12mL . Al 10ng . Fe 3M .. 38 2 pH . Table Al Ca Fe pH. 1. pg mL Fig. Cr . Teble Determination of the impurities in highly purified reagents Ultra pure watera Hydrochloric acidb Hydrofluoric acidb Element c 1 c 1. Found pg mL Found pg mL Foundc pg mL 1 . Al 1 Ca 1. Cd 1 1. Co 1 1. Cr 1 1. Cu 1 1. Fe K 1 1. Li 1 1. Mg 1. Mn 1 1. Na 1 1. Ni 1 1. Pb 1 1. Zn 1 1. a Sample volume 100mL. b Sample volume 20mL. c Values are the mean of five measurements standard deviation. Teble Determination of the impurities in a 25 hydrofluoric acid 20 Found pg mL 1.

9 Element Lot. 1 Lot. 2 Lot. 3 Lot. 4 Lot. 5. Zn pg . 15. Al 2 1 1 1 3. 10 Ca 2 1 1 1 6. Cr 1 1 1 1 1. 5. Cu 1 1 1 1 1. 0 Fe 1 1 3 1 3. 0 10 20 30 K 1 1 1 1 1. Volume of sample mL Li 1 1 1 1 1. Mg 1 1 1 1 1. Fig. Amount of Zn in ultra pure water Na 1 1 1 1 1. a Sample volume 20mL n 2. 30 TOSOH Research Technology Review 2010 . 10000. 100 a . Eluted amount ng . Al Ca 1000 Cu Fe Mg Zn 80. Recovery . 100 60. 10 40. Al Cd Co Cu 1 20 Fe Mn Ni Pb 0 3 6 9 12 Zn 0. 3M HNO3 mL . 2 3 4 5 6 7. pH. Fig. Amount of eluted elements from chelating resin by 3M nitric acid 100 b . Recovery . 80. pH5 80 . 60. Cr pH8 80 . Cr 3 40. Cr Cr pH8 20.

10 Cr OH 3 pH8 . 0. 2 3 4 5 6 7 8 9 10. 3+ pH. Cr NH3 6 . Cr Fig. The effect of pH on recovery of a . 9 elements and b Cr with Empore chelating resin disk 10 pretreatment Cr Cr3+ Cr OH 2+ . Cr CrO 42 HCrO 4 Cr2O72 .. Na concentration g g 1 . 1000. 20 25 . 100.. Cr 10. Cr pH8 . 1. pH5 6 . 3 0 10 20 30. Volume of solution mL . 3M Fig. Washing volumes dependencies for ICP AES Na concentration of Na Na 100 g g 1 . Na pH 24mL . 10M . 5mL 6 Al 11ng g 1 Fe . Na Fig. 12ng g 1 10M . 25mL Na 1 . 1. 1 g g Al Fe . 26 27 . 30mL g 1 . 1 . Ca Mg . 5 . 4 11 .. 54 2010 31. 28 . Table pH4 6 . 80 pH Cr . Table HCrO 4 . 3 Al g 1 Cr g 1 29 31.