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Separation of zirconium by thin-layer chromatography
Short c4mmlmications
409
R&tun&On a d&rmln6 les longueurs d’onde des maximums d’excitation et d’&nission de pho horescen ce, les d&es de vie, les limites de d6tection et les domaines 7 e concentration d’utilite analytique pour 37 antim6tabolites en solution 6thanolique rigide (77°K). Dix sept des m6tabolites produisent une phosphorescence analytiquement utile, tandis que les 20 restant sont d’emploi analytique limit6 ou nul. REFERENCES 1. J. D. Wineforclner, W. J. McCarthy, and P. A. St. John, Phospharimetry as an Analytical Approach in Biochemistry, in Metbo& of Biochemical Analysis, D. Glick, editor, Vol. 15, Interscience. New York, 1967. 2. J. D. Winefordner and H. A. Moye, Anal. Chim. Acta, 1965,32,278. 3. J. D. Winefordner and H. W. Latx, Anal. Cbem., 1963,35,1517. 4. J. D. Winefordner and M. Tin, Anal. Cbim. Acta. 1964,31,239. 5. H. C. Hollitield and J. D. Winefordner, ibid., 1966,36,351. 6. I&m, TaIanta, 1965, 12,860. 7. R. H. Stille and A. Srent-Gyorgyi, Proc. Natl. Acad. Sci. U.S.A., 1957, 43,477. 8. H. A. Move and J. D. Wmefordner. - J. Apr. Food Chem.._ 1965.13,516. . Y
9. Idem, ibid:, 1965, 13,533.
10. J. D. Winefordner, W. J. McCarthy, and P. A. St. John, Anal. Chem., 1967,39,1495.
Tdmta, 1969,Vol. 16,pp. 409to 412. permmonPress. primedin NorthernIdand
Separation of zirconium by thin-layer chromatograplty (Received 20 May 1968. Accepted 29 .Wy 1968) RBWRSD-PHASE thin-layer chromatography has been used for the separation of xirconlum,lJ but normal-phase thin-layer chromatography has scarcely been used. Galiardi and Pokomp separated Zr(IV), Ni(II), Al(m), Ti(IV), Mn(II), Cd(n), V(V), IJO, Fe0 and ZnO by development with acetone-6M hydrochloric acid-dioxan or ethyl methyl ketone on silica 1 layers. Breccia and Spalletti6 separated zirconium-95 and niobium-95 by eluting with methano K” -lOM hydrotbroric acid (25:l) on silica gel layers. Moghissi@separated these radionuclides by eluting with 025M oxalic acid and O-lit4 hydrochloric acid in ethyl methyl ketone, dioxan and water (5:l:l) on Kieselguhr or Kieselgel layers. The present work was, therefore, undertaken to provide more simple and effective TLC systems for the separation involving Zr. SC.Y. Th. U(VI), rare earth and other metal ions. Zirconium remains at the starting point on s&a gel-cellulsoe (5: 1) plates in mesityl oxide-ethanol-nitric acid media, whilst 19 of the other metal ions tested have lamer R, values. extent silver. which tails. This forms the basis of a very selective method for the +ation of zircon&i. ’
EXPERIMENTAL Reagents Test solutions of metal ions, @lM. Appropriate amounts of the nitrates of IJO?), Th, Al, Pb,
Co(B) and Ag were dissolved in 1M nitric acid. Appropriate amounts of the oxides or carbonates of Fe(III), Zn, Cd, Cu(II), Ni, Sc, Y, La, Sm, In, Bi(III), Hg(II), Mg and Ca were converted into the nitrate by treatment with excess of nitric acid, followed by evaporation to dryness. The resulting nitrates were dissolved in 1M nitric acid. Zirconyl chloride was dissolved in dilute nitrrc acid and the solution made ammoniacal. The precipitate of zirconium hydroxide was filtered off and washed free from chloride with demineralized water, and dissolved in nitric acid. The solution was evaporated to dryness and the residue dissolved in 1M nitric acid. Preparation of thin-layer plates. Silica gel (25 g, WAKOGEL B-O, Wako Pure Chemical Industries Co. Ltd., Osaka, Japan) purified according to Seiler’s method,’ and cellulose powder MN-300 (5 g, Machery , Nagel Co., Ltd., Dtlren, Germany) were mixed thoroughly with 87 ml of demineralired water. The slurry was spread 250 p thick on 100 x 100 mm or 200 x 200 mm glass plates. The thin-layer plates were dried first in air for 1 hr and then in an oven at 105-110” for 1 hr and were stored in a desiccator till used.
cc 3
411
Short communications Procedure
About 0.5 & of each test solution was spot&ii with a micro pipette at 25 mm from one end of the plate The spots were air-dried for -30 mm, but drying for up to 45 min did not affect the r~~uci~~ty of R, vahxes. The plates were inserted in the tanks, which had aheady been conditioned with solvent vapour for 10 mmn,and immediately developed (lOO-mm solvent travel) by the ascending technique at room temperature. The developing solvents used are listed in Table I. The plates were then air-dried and the metal ions detected as follaws. Arsenazo III,1 % solution; W(W), Th, Sm, La, Zr, Y and SC were detected as green spots on a pink background. ~~~~~ ~~~, dilute colourless solution; Bi(III), Hg@Q, Pb, Hi, Cu@), Co(H) and Ag formed co~oured snots. ~~~~yqa~jj~e, 1% solution in ethanol, fohowed by exposure to ammonia; &Q, Ca, Al, Fe(HI), Zn, cd and In showed up in UV light, All Rr values are given for the leading and trailing edges of the spots. RESULTS
AND
DISCUSSION
Tabte: f shows Rr vahma for Zr, SC, Y, La, Sm, Th and UfsI in various solvent systems. Zirconium remains stationary in all systems. Tailing is dependent on nitric acid concentration in some systems (esp. 11-3,SC). Khopkar and Dhan? reported that the presence of ammonium and sodium nitrate in the aqueous phase increased the extraction of zirconium with 100% mesityl oxide in the acidity range 2+-4N, but it is clear that the salting-out effect does not affect the developing process in this system. Twenty-one metal ions inchulin those described above were chromatographed in me&y1 oxideethanol-5M nitric acid f5:3:2) an 6, m me&y1 oxids-S&f nitric acid, and the additional results are summarized in Table IL The results show that it should be possible to resolve several 2-4 ion m&urea and this was confirmed e~eu~ly for 29 mixtures. TABLBIL--RI VXLVESFOR Metal ion
MBTAL
KIN&
NOT ~NCLVDEII IN TABLEf
Mesityl oxidtrsMHN0,
Mesityl oxideethanol-5&f HNOs (5:3:2)
030410
0*53-k
0.8~1.00 0*00-0.10 0+0-0~06 0+3&0*03 &03+13 0@0-0~05 0~02-@09 OXWX6 O*WO6 0W-O~03 0+0+05 e-45
0*90-1GO @35-0*51 0*42+65 0~39-060 0*64-0*85 0*45-0*65 0*55-0~71 0.39-0.66 0.42-0.71 0.48-0.75 0.46-0.62 0+0-0*74
Zirconium is separated from niueteen of the ions tested in mesit 1 oxide-ethanoI-5M nitric acid (5: 3 : 2), but not from silver. In order to be use&d this separation o%.mconium and other metal ions should include varying ratios of zirconium and other metal ions. This was verified exp&mentahy for 100: 1 and 1: 100 mixtures of Zr and either Fe, In, Co, Si, La, Th or U.
Me&y1 oxide was found to be gradually decomposed by nitric acid, so that nit+ acid >5.&$was not used. The mixture of silica gel and c&dose formed thim layers that were more stable during handling and brought about better separation more rapidly than the mixture of silica gel and starch which is generally used in inorganic thinlayer chromatography.
412
Short communications
Acknowlec&ement-The author is indebted to Prof. R. Kuroda, University of Chiba, for his helpful discus&on and comment, and to Dr. I?. Aoki and Dr. M. Kojima, tbis f&oratory, for their encoura~ ment througIl the investigation. 6&emmen$ C?le?niiXz~ Ixdl&&r~ &&?ilr& I?lsr&&? Honnruchi, Shibuya-ku, Tokyo, Japan+
KoWriI OauaaA
S--The thin-layer chromate phic se aration of a number of metal ions [!!$c,Y, Zr, La, Sm, m pi”(VI), etc.P with solvent mixtures of me&y1 oxide, ethanol and 5M nitric acid on silica gel-celhrlose (3:l) thin-layer plates is reported. Zircotium remains stationary wldlst the other metal ions move with the solvent, thus allowing a selective separation of zirconium from about 20 metal ions in ratios ranging from 1OO:l to 1:lOO. Mixtures of various metal ions can also be separated, Zusammeafassun8-Die dttschichtchromatograph~sche Tremnmg einer Anxabl von Metallionen [SC,Y, Zr, La, Sm, Th, UM usw.f mit L~~~~i~ von Mesitvioxid. &hart01 und 5&f Salpetersiture >uf ~~ehtp~att~ a& S~~~-~~~o~ (5: I) a wird mitgeteilt, Zirkonium bleibt steben, w&rend die anderen Metallionen mit dem LBsungsmittel waudern. Damit ist eine Abtrennung von Zirkonium van etwa 20 Metallionen in MengenverbaWssen xwischen 100: 1 und X:I00 mbglich. Gemische verschiedener Metallionen kbnnen ebenfalh getreunt werden. R&aa&-Gn rapporte fa s6paration c~~~~ap~e sur coucbe rniuce d’un c-ertam nombre d’zons m6talfiquea [SC,Y, Zr, La, Sm, Th, U(W), etc.1 aver de+ melanges solvants d’oxyde de mesityle, ethaaol et acide nitrique !Wf sur des plaques B couches minces de gel de siiic+ cellulose (5: 1). Le zirconium reste stationnaire tandis que les autres ions metalliques se d6placent avec 1s solvant, permettant ainsi une separation selective du zircouium d’environ 20 ions metalliques dans dea rapports ahant de 10&l 8 l:tOO_ On peut aussi &parer dea m6lange.s de divers ions rn6t~~qu~* REFERENCES 1. U. A. Th. Brinkman, G. de Vries and E. van D&n, J. Chromatog., 1966,25,447. 2. L. S. Bark, G. Duncan and R. J. T. Graham, Analyst, 1967,928 347. 3. D. Markel and F. Hecht. Mikrochim. Acta, 1963,980. 4. E. Gall&i and G. Pokorny, ibid,, 1966,577. 5, A. Breccia and F. Spalletti, Natrrre, 1%3,198,756. 1964,f3,542. 6. A. Mogbissi, J; Chrorrrr 7. H. Se&r, in E, Stahl (a, .), FJzi#-&-+?r C~o~f~~~hy* p. 495, Academia Press, New York, 1965. 8. S. M. Khopkar and S. C. Dhara, Anal. Chem., 1965,37,1158. l Present address: Laboratory for Analytical Chemistry, Faculty of Enfieeriug, University of Chiba, Yayoicbo, Chiba, Japan, ‘l&r&a, 1969s V&. 16,&@ 431to 414. l%irfm~n Prea. Printi in Nixthai Irek+nd
A highly wmsitiveextraction-photometricmethodfor nickel with dithizone and phenanthrolb (Received 3 Septenrber 1968. Accepted 24 September 1968) ALTXW~~~dip~yl~~b~one @W&one) serves as an extractant and hi@zly sensitive colorimetric reagent for many transition and heavy metai ions, it has not been found useful for determining nickeI Ref. (I). Two reasons for this are (a} the spectrum of the nicket chelate is rather complex and does not contain an absorption band of comparable intensity to those of other metal ions and (b) the rate of formation of the nickel complex is SO slow that equilibration may require over an hour of shaking.
409
R&tun&On a d&rmln6 les longueurs d’onde des maximums d’excitation et d’&nission de pho horescen ce, les d&es de vie, les limites de d6tection et les domaines 7 e concentration d’utilite analytique pour 37 antim6tabolites en solution 6thanolique rigide (77°K). Dix sept des m6tabolites produisent une phosphorescence analytiquement utile, tandis que les 20 restant sont d’emploi analytique limit6 ou nul. REFERENCES 1. J. D. Wineforclner, W. J. McCarthy, and P. A. St. John, Phospharimetry as an Analytical Approach in Biochemistry, in Metbo& of Biochemical Analysis, D. Glick, editor, Vol. 15, Interscience. New York, 1967. 2. J. D. Winefordner and H. A. Moye, Anal. Chim. Acta, 1965,32,278. 3. J. D. Winefordner and H. W. Latx, Anal. Cbem., 1963,35,1517. 4. J. D. Winefordner and M. Tin, Anal. Cbim. Acta. 1964,31,239. 5. H. C. Hollitield and J. D. Winefordner, ibid., 1966,36,351. 6. I&m, TaIanta, 1965, 12,860. 7. R. H. Stille and A. Srent-Gyorgyi, Proc. Natl. Acad. Sci. U.S.A., 1957, 43,477. 8. H. A. Move and J. D. Wmefordner. - J. Apr. Food Chem.._ 1965.13,516. . Y
9. Idem, ibid:, 1965, 13,533.
10. J. D. Winefordner, W. J. McCarthy, and P. A. St. John, Anal. Chem., 1967,39,1495.
Tdmta, 1969,Vol. 16,pp. 409to 412. permmonPress. primedin NorthernIdand
Separation of zirconium by thin-layer chromatograplty (Received 20 May 1968. Accepted 29 .Wy 1968) RBWRSD-PHASE thin-layer chromatography has been used for the separation of xirconlum,lJ but normal-phase thin-layer chromatography has scarcely been used. Galiardi and Pokomp separated Zr(IV), Ni(II), Al(m), Ti(IV), Mn(II), Cd(n), V(V), IJO, Fe0 and ZnO by development with acetone-6M hydrochloric acid-dioxan or ethyl methyl ketone on silica 1 layers. Breccia and Spalletti6 separated zirconium-95 and niobium-95 by eluting with methano K” -lOM hydrotbroric acid (25:l) on silica gel layers. Moghissi@separated these radionuclides by eluting with 025M oxalic acid and O-lit4 hydrochloric acid in ethyl methyl ketone, dioxan and water (5:l:l) on Kieselguhr or Kieselgel layers. The present work was, therefore, undertaken to provide more simple and effective TLC systems for the separation involving Zr. SC.Y. Th. U(VI), rare earth and other metal ions. Zirconium remains at the starting point on s&a gel-cellulsoe (5: 1) plates in mesityl oxide-ethanol-nitric acid media, whilst 19 of the other metal ions tested have lamer R, values. extent silver. which tails. This forms the basis of a very selective method for the +ation of zircon&i. ’
EXPERIMENTAL Reagents Test solutions of metal ions, @lM. Appropriate amounts of the nitrates of IJO?), Th, Al, Pb,
Co(B) and Ag were dissolved in 1M nitric acid. Appropriate amounts of the oxides or carbonates of Fe(III), Zn, Cd, Cu(II), Ni, Sc, Y, La, Sm, In, Bi(III), Hg(II), Mg and Ca were converted into the nitrate by treatment with excess of nitric acid, followed by evaporation to dryness. The resulting nitrates were dissolved in 1M nitric acid. Zirconyl chloride was dissolved in dilute nitrrc acid and the solution made ammoniacal. The precipitate of zirconium hydroxide was filtered off and washed free from chloride with demineralized water, and dissolved in nitric acid. The solution was evaporated to dryness and the residue dissolved in 1M nitric acid. Preparation of thin-layer plates. Silica gel (25 g, WAKOGEL B-O, Wako Pure Chemical Industries Co. Ltd., Osaka, Japan) purified according to Seiler’s method,’ and cellulose powder MN-300 (5 g, Machery , Nagel Co., Ltd., Dtlren, Germany) were mixed thoroughly with 87 ml of demineralired water. The slurry was spread 250 p thick on 100 x 100 mm or 200 x 200 mm glass plates. The thin-layer plates were dried first in air for 1 hr and then in an oven at 105-110” for 1 hr and were stored in a desiccator till used.
cc 3
411
Short communications Procedure
About 0.5 & of each test solution was spot&ii with a micro pipette at 25 mm from one end of the plate The spots were air-dried for -30 mm, but drying for up to 45 min did not affect the r~~uci~~ty of R, vahxes. The plates were inserted in the tanks, which had aheady been conditioned with solvent vapour for 10 mmn,and immediately developed (lOO-mm solvent travel) by the ascending technique at room temperature. The developing solvents used are listed in Table I. The plates were then air-dried and the metal ions detected as follaws. Arsenazo III,1 % solution; W(W), Th, Sm, La, Zr, Y and SC were detected as green spots on a pink background. ~~~~~ ~~~, dilute colourless solution; Bi(III), Hg@Q, Pb, Hi, Cu@), Co(H) and Ag formed co~oured snots. ~~~~yqa~jj~e, 1% solution in ethanol, fohowed by exposure to ammonia; &Q, Ca, Al, Fe(HI), Zn, cd and In showed up in UV light, All Rr values are given for the leading and trailing edges of the spots. RESULTS
AND
DISCUSSION
Tabte: f shows Rr vahma for Zr, SC, Y, La, Sm, Th and UfsI in various solvent systems. Zirconium remains stationary in all systems. Tailing is dependent on nitric acid concentration in some systems (esp. 11-3,SC). Khopkar and Dhan? reported that the presence of ammonium and sodium nitrate in the aqueous phase increased the extraction of zirconium with 100% mesityl oxide in the acidity range 2+-4N, but it is clear that the salting-out effect does not affect the developing process in this system. Twenty-one metal ions inchulin those described above were chromatographed in me&y1 oxideethanol-5M nitric acid f5:3:2) an 6, m me&y1 oxids-S&f nitric acid, and the additional results are summarized in Table IL The results show that it should be possible to resolve several 2-4 ion m&urea and this was confirmed e~eu~ly for 29 mixtures. TABLBIL--RI VXLVESFOR Metal ion
MBTAL
KIN&
NOT ~NCLVDEII IN TABLEf
Mesityl oxidtrsMHN0,
Mesityl oxideethanol-5&f HNOs (5:3:2)
030410
0*53-k
0.8~1.00 0*00-0.10 0+0-0~06 0+3&0*03 &03+13 0@0-0~05 0~02-@09 OXWX6 O*WO6 0W-O~03 0+0+05 e-45
0*90-1GO @35-0*51 0*42+65 0~39-060 0*64-0*85 0*45-0*65 0*55-0~71 0.39-0.66 0.42-0.71 0.48-0.75 0.46-0.62 0+0-0*74
Zirconium is separated from niueteen of the ions tested in mesit 1 oxide-ethanoI-5M nitric acid (5: 3 : 2), but not from silver. In order to be use&d this separation o%.mconium and other metal ions should include varying ratios of zirconium and other metal ions. This was verified exp&mentahy for 100: 1 and 1: 100 mixtures of Zr and either Fe, In, Co, Si, La, Th or U.
Me&y1 oxide was found to be gradually decomposed by nitric acid, so that nit+ acid >5.&$was not used. The mixture of silica gel and c&dose formed thim layers that were more stable during handling and brought about better separation more rapidly than the mixture of silica gel and starch which is generally used in inorganic thinlayer chromatography.
412
Short communications
Acknowlec&ement-The author is indebted to Prof. R. Kuroda, University of Chiba, for his helpful discus&on and comment, and to Dr. I?. Aoki and Dr. M. Kojima, tbis f&oratory, for their encoura~ ment througIl the investigation. 6&emmen$ C?le?niiXz~ Ixdl&&r~ &&?ilr& I?lsr&&? Honnruchi, Shibuya-ku, Tokyo, Japan+
KoWriI OauaaA
S--The thin-layer chromate phic se aration of a number of metal ions [!!$c,Y, Zr, La, Sm, m pi”(VI), etc.P with solvent mixtures of me&y1 oxide, ethanol and 5M nitric acid on silica gel-celhrlose (3:l) thin-layer plates is reported. Zircotium remains stationary wldlst the other metal ions move with the solvent, thus allowing a selective separation of zirconium from about 20 metal ions in ratios ranging from 1OO:l to 1:lOO. Mixtures of various metal ions can also be separated, Zusammeafassun8-Die dttschichtchromatograph~sche Tremnmg einer Anxabl von Metallionen [SC,Y, Zr, La, Sm, Th, UM usw.f mit L~~~~i~ von Mesitvioxid. &hart01 und 5&f Salpetersiture >uf ~~ehtp~att~ a& S~~~-~~~o~ (5: I) a wird mitgeteilt, Zirkonium bleibt steben, w&rend die anderen Metallionen mit dem LBsungsmittel waudern. Damit ist eine Abtrennung von Zirkonium van etwa 20 Metallionen in MengenverbaWssen xwischen 100: 1 und X:I00 mbglich. Gemische verschiedener Metallionen kbnnen ebenfalh getreunt werden. R&aa&-Gn rapporte fa s6paration c~~~~ap~e sur coucbe rniuce d’un c-ertam nombre d’zons m6talfiquea [SC,Y, Zr, La, Sm, Th, U(W), etc.1 aver de+ melanges solvants d’oxyde de mesityle, ethaaol et acide nitrique !Wf sur des plaques B couches minces de gel de siiic+ cellulose (5: 1). Le zirconium reste stationnaire tandis que les autres ions metalliques se d6placent avec 1s solvant, permettant ainsi une separation selective du zircouium d’environ 20 ions metalliques dans dea rapports ahant de 10&l 8 l:tOO_ On peut aussi &parer dea m6lange.s de divers ions rn6t~~qu~* REFERENCES 1. U. A. Th. Brinkman, G. de Vries and E. van D&n, J. Chromatog., 1966,25,447. 2. L. S. Bark, G. Duncan and R. J. T. Graham, Analyst, 1967,928 347. 3. D. Markel and F. Hecht. Mikrochim. Acta, 1963,980. 4. E. Gall&i and G. Pokorny, ibid,, 1966,577. 5, A. Breccia and F. Spalletti, Natrrre, 1%3,198,756. 1964,f3,542. 6. A. Mogbissi, J; Chrorrrr 7. H. Se&r, in E, Stahl (a, .), FJzi#-&-+?r C~o~f~~~hy* p. 495, Academia Press, New York, 1965. 8. S. M. Khopkar and S. C. Dhara, Anal. Chem., 1965,37,1158. l Present address: Laboratory for Analytical Chemistry, Faculty of Enfieeriug, University of Chiba, Yayoicbo, Chiba, Japan, ‘l&r&a, 1969s V&. 16,&@ 431to 414. l%irfm~n Prea. Printi in Nixthai Irek+nd
A highly wmsitiveextraction-photometricmethodfor nickel with dithizone and phenanthrolb (Received 3 Septenrber 1968. Accepted 24 September 1968) ALTXW~~~dip~yl~~b~one @W&one) serves as an extractant and hi@zly sensitive colorimetric reagent for many transition and heavy metai ions, it has not been found useful for determining nickeI Ref. (I). Two reasons for this are (a} the spectrum of the nicket chelate is rather complex and does not contain an absorption band of comparable intensity to those of other metal ions and (b) the rate of formation of the nickel complex is SO slow that equilibration may require over an hour of shaking.