Determination of Fe(II) ion and Fe(III) ion by Chemiluminescence Method Fe(II) Fe(III)

전체 글

(1)Journal of the Korean Chemical Society 2002, Vol. 46, No. 6 Printed in the Republic of Korea. Fe(II) Fe(III)

(2) *. (2002. 8. 6 ) Determination of Fe(II) ion and Fe(III) ion by Chemiluminescence Method Sang Hak Lee* and Myeong Sik Nam Department of Chemistry, Kyungpook National University, Taegu 702-701, Korea (Received Augsut 6, 2002). .

(3) Fe(II) Fe(III)

(4) !" #$ %&'. #( lucegenin H O )*$ Fe(III) + ,-& . /0- 1-" 2 03 &'. KOH, H O 4 Fe(II) - 56 7 citric acid 89 :; <=>9- /0 $ ?@" AB CD&'. EF G

(5) ! H %7 [H O ], [KOH] 4 >9 IJCK( LL 4.0 M, 2.0 M 4 3.5 mL/min MN, O7 IJCK $P Q( R

(6) ST$P UTV VW" XH" 1.0×10 M$ P 1.0×10 M MN, YZ[ " 0.996, R\7[" 1.0×10 MM'. Fe(III) +

(7) ! H %7 [H O ], [KOH], [citric acid] 4 >9 IJCK( LL 4.0 M, 2.0 M, 0.01 M 4 3.5 mL/min MN, O7 IJC K $P Q( R

(8) ST$P UTV VW" XH" 1.0×10 M$P 1.0×10 M MN, YZ[ " 0.997, R \7[" 5.0×10 MM'. : , Fe(II)

(9) !, Fe(III)

(10) ! 2. 2. 2. 2. 2. 2. −6. −4. −7. 2. −6. 2. −4. −7. ABSTRACT. A method to determin Fe(II) and Fe(III) ion in aqueous solution by chemiluminescence method using a stopped flow system has been studied. The method is based on the increased chemiluminescence intensity with the addition of Fe(III) ion to a solution of lucigenin and hydrogen peroxide. The effects of KOH concentration, flow rate of reagents, H2O2 concentration and citric acid concentration used for the masking of Fe(II) ion on the chemiluminescence intensity have been investigated. The calibration curve for total Fe was linear over the range from 1.0×10−6 M to 1.0×10−4 M, coefficient of correlation was 0.996 and the detection limit was 1.0×10−7 M under the optimal experimental conditions of 4.0 M, 2.0 M, 3.5 mL/min for the concentration of H2O2, KOH and flow rate of reagents, respectively. The calibration curve for Fe(III) was linear over the range from 1.0×10−6 M to 1.0×10−4 M, the coefficient of correlation was 0.997 and the detection limit was 5.0×10−7 M under the optimal experimental conditions. Keywords: Chemiluminescence, Determination of Fe(II), Determination of Fe(III). G( ]F ^$P _`ab 4 EEc

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(21) !" #$ CD &'. Fe(II) + $ 0.01 M _ `k , - Fe(II) + Fe(III) + _ :Á Â$ ]V Fe(III) + 89$ Ãº /01-"

(22) 9k Ä

(23) EF G

(24) !&N, Fe(III) +

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(27) Fe(III) +

(28) !&'. :;$ <=q" KOH 89, _ ` 89 4 À <=z@$P <=q " :Æg >9- $ ?@" AB C D&'. O7 IJCK$P Fe(II) + Fe(III) +

(29) ! ¾ . R

(30) ST QMj R\7[k %&'.. . :Æ". 1.0×10−4 M Bis-N-. methylacridium nitrate(lucigenin, guaranteed reagent,. Çz 6C7 Â$ ÈÉP D &'. b «hÊ . pHk CË0 H KOH(Duksan Pure Chemical Co. Ltd) D &'. - 56" citric acid(first grade. Shinyo Pure Chemicals Co., Ltd.)k, _ 6" H O (guaranteed reagent, Junsei Chemical Co., Ltd., Japan)k D& N, Fe(II) Çz( FeSO (NH ) SOÌ6H O(first grade, Wako Pure Chemical Industries Ltd., Japan) D 6C&j, Fe(III)Çz( Fe (SO ) (NH ) SO Ì Aldrich, USA). 2. 4. 4 2. 4. 2. 2. 4 3. 2. 4 2. 4. 24H2O(special grade, Wako Pure Chemical Industries. D 6C&'. ¿ ÍÎ$P D 7 'º :Æg( ¯Ï:Æ

(31) 6 rN Ð D &'. ÑÒ 6C" MilliporeD(Bedford, MA, USA) Mill1-Q water system Q( Ó+ k D &j, ÔÕ( ÍÎ UE$ JÖ7 89 È ÉP D&'. . ¿ ÍÎ$P D7 z@ À z@ ×Ø9k Fig. 1$ ^M'. ¿ ÍÎ$P D7 Ù × ÀÚÛ <= Ltd., Japan). 26. Fig. 1. Schematic diagram of the flow system for chemiluminescence: (a) personal computer, (b) PMT, (c) power supply, (d) monochromator, (e) fiber optic bundle, (f) cell compartment, (g) and (h) peristaltic pump. Journal of the Korean Chemical Society.

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(33) Fe(II) Fe(III) . ÀÚÛ(Ismatec, Model 404, Switzerland)" H O , KOH 4 lucegenin 4 :;k Ü$ À ab" $ &N, Ý\ ÀÚÛ(MS-4 Reglo/6-100, Switzerland)" Ü$P Ä

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(36) 7 Ys$P #\q" å'(Oriel, Model 77800, USA) µ dæ z@k ¥@9ç & j, /0 Ä

(37) 0 H photomultiplier tube(PMT, Hamamatsu, Model R928, USA)k D &'. PMT Eè( 800 V N

(38) &'. Ä

(39) é n :; Ä

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(41) ! ¾ ë$" )* 6C7 ê: Fe(II) + Fe (III) + _ :ì'. Fe(III) +

(42) !" ë$" )* 6C¾ .$ citric acidk ,-& '. 6.0 M H O KOH ( ÍÎ UE$ Ó + 6C&N, JÖ! á ÍÎ UE$ KOH-H O )* Ó+ JË° È í Â$ )* D&'. Ü$ ÀÚÛk 22 rpm >9 H O -KOH )* 4 1.0×10 M lucigenin 9=N, :; «

(43) :w w î L 3ïà <=&'. Ü$P ]q" ( 473 nm N

(44) dæ z@k µ:Á Â Ä

(45) &'. R\7[k %¾ . · £¸©" 3 &'. 2. 2. 2. 2. 2. 2. 2. 2. 511. Fig. 2. Chemiluminescence spectrum of lucigenin solution containing hydrogen peroxide in aqueous solution: [Lucigenin]: 1.0×10−5 M, [H2O2]: 4.0 M, flow rate: 3.5 mL/min.. lucigenin [>J <=nP Ä

(46) &'. Fig. $P ÷ iø lucigenin #\/0" 473 nm$ P -z ù'. ðz( Montano úN 7 475 nm ¥ «@7'. ÃP Â ÍÎ$ P" #\ðz 473 nm N

(47) :û ÍÎ&'. H O . Fe(III)+

(48) !$P H O <=q" 89$ Ãº /0$ ?@" AB üú0 H Ü$ <=q" >9k 3.5 mL/min N, 1.0×10 M lucigenin, 1.0×10 M Fe(III) + ÔÕ 4 KOH-H O )*$P KOH 89" 2.0 M N

(49) N, H O 89k ñ :¬ nP /0k Ä

(50) &N, Ð k Fig. 3 $ ^M'. Fig. 3$P ÷ iø _ 6 89- 1-¾ 2. 2. 2. 2. −5. 2. −5. 2. 2. 2. 2. −5.

(51)

(52) . Ä

(53) ðz ñ :¬nP 1.0× 4.0 M _ `$ 7 /0k Ä

(54) 7 k Fig. 2$ ^M'. òóô õ ö0 .$ _ `. 10−5 M lucigenin. 2002, Vol. 46, No. 6. Fig. 3. Effects of [H2O2] on chemiluminescence intensity: [Fe(III)]: 1.0×10−5 M, [Lucigenin]: 1.0×10−5 M, [KOH]: 2.0 M, flow rate: 3.5 mL/min..

(55) . 512. ç /0" 1-'- 4.0 M$P I /0k úN, Ð Y 89$T /0- `p ü i'. 4.0 Mý /0 - [> 1-" " lucigenin _ q" þ 1 -0 .N, Ð Â ã$P" _ 6 þ ! tu qh :Æ 89- Èh 0 .$ /0- `&'N ]L'. ÃP, 1.0×10 M lucigenin$ <=q" H O IJ 89" 4.0 M ÑÒ ÍÎ ÿ&'. KOH . Fe(III)

(56) !$P <=q" KOH 89- /0$ ?@" AB üú 0 H Ü$ <=q" :Æ >9k 3.5 mL/min N

(57) N 1.0×10 M lucigenin, 1×10 M Fe(III) + ÔÕ 4 KOH-H O )*$P H O 89" 4.0 M N

(58) N, KOH 89k ñ :¬ nP /0k Ä

(59) &N, Ð k Fig. 4 $ ^M'. Fig. 4$P ÷ iø KOH 89- 1-p$ Ã /0- 1-'- 2.0 M$P -z / 0k ^MN, Ð Â$" /0- `&'. Ã P Â ÍÎ$P KOH 89k 2.0 M N

(60) ÍÎ&'. Citric acid . Fe(III) + Fe(II)+ )*qh i" :; $P Fe(III) + T J

(61) !0 H Ü$ <=q" :Æ > 9k 3.5 mL/min N

(62) N 1.0×10 M lucigenin, −5. 2. −5. 2. −5. 2. 2. 2. 2. −5. Fig. 4. Effects of KOH concentration on chemiluminescence intensity: [Fe(III)]: 1.0×10−5 M, [Lucigenin]: 1.0×10−5 M, [H2O2]: 4.0 M, flow rate: 3.5 mL/min.. Fig. 5. Effects of citric acid concentration on chemiluminescence intensity: (a) [Fe(III)]: 1.0×10−5 M, [Lucigenin]: 1.0×10−5 M, [H2O2]: 4.0 M, [KOH]: 2.0 M, flow rate: 3.5 mL/min, (b) [Fe(II)]: 1.0×10−5 M, [Lucigenin]: 1.0×10−5 M, [H2O2]: 4.0 M, [KOH]: 2.0 M, flow rate: 3.5 mL/min.. KOH-H O )* 4 Fe(III) + citric acid )* $P" Fe(III) + 89k 1.0×10 M N

(63) N, citric acid 89k ñ :¬nP /0 k Ä

(64) &N, Ð k Fig. 5(a)$ ^M'. 7 Ü$ <=q" :Æ >9k 3.5 mL/min N

(65) N 1.0×10 M lucigenin, KOH-H O )* 4 Fe(II) + citric acid )*$P" Fe(II) + 89k 1.0×10 M N

(66) N, citric acid 89k ñ :¬nP /0k Ä

(67) &N, Ð k Fig. 5(b)$ ^M'. Fig. 5(a)$P ÷ iø citric acid 89- 1¾ ç /0- 1-&N, 0.01 M « . I /0k ú&'. ÃP citric acid" Fe(III) ¼½¹$ 7 $P 16 ¾ 7'" 2 ü'. Fig. 5(b)$P ÷ iø citric acid 89- 1-n Fe(II) + opqh i" $ 7 /0" Ïî° `N, citric acid 89- 0.01 M « . /0" /0 Å'. ÃP, Fe(III) + Fe(II) + )*$P Fe(III) + T J

(68) !$ citric acid 89k 0.01 M N

(69) &'. . :Æ <= >9- $ ?@" AB CD0 H lucigenin 89k 1.0×10 M, KOH 89k 2.0 M, H O 8 2. 2. −5. −5. 2. 2. −5. −5. 2. 2. Journal of the Korean Chemical Society.

(70)

(71) Fe(II) Fe(III) . Fig. 6. Effects of flow rate on chemiluminescence intensity: (a) [Fe(III)]: 1.0×10−5 M, [Lucigenin]: 1.0×10−5 M, [H2O2]: 4.0 M, [KOH]: 2.0 M, (b) [Fe(III)]: 1.0×10−5 M: [Fe(II)]: 1.0×10−5 M, [citric acid]: 0.01 M, [Lucigenin]: 1.0×10−5 M, [H2O2]: 4.0 M, [KOH]: 2.0 M.. 9k 4.0 M 4 Fe(III) + 89k 1.0×10 M À ÚÛ >9k 1.0 mL/min5.5 mL/min ñ : ¬nP /0k Ä

(72) &N, Ð k Fig. 6(a)$ ^MN, lucigenin 89k 1.0×10 M, KOH 89k 2.0 M, H O 89k 4.0 M, Fe(III) + Fe(II) + 4 citric acid 89- LL 1.0×10 M, 1.0×10 M, 0.01 Mv )* ÀÚÛ > 9k 1.0 mL/min5.5 mL/min ñ :¬nP <= /0k Ä

(73) &N, Ð k Fig. 6(b) $ ^M'. Fig. 6$P ÷ iø, 3.5 mL/miný " > 9- 1-¾ ç /0" 1-p ü i'. ÃP Â ÍÎ$P lucigenin _ ` >9k 3.5 mL/min N

(74) ÍÎ&'. . /0 u~V CD0 H KOH89k 2.0 M CËN, lucigenin, H O , 4 Fe(III) 89k LL 1.0×10 M, 4.0 M, 1.0×10 M N

(75) :¬N, #\ðz 473 nm$P /0 k Ä

(76) , Ð k Fig. 7$ ^M'. Fig. 7$P ÷ iø /0- YJ ä hª" ( b ÿqnP ^" 89- `0 .N, Y J Ïî hª" ( Ü /ß H7 ½ 9= .'. 10ï Ä

(77) 7 /0 Y ÔÕ " 1.5% M'.. 513. Fig. 7. Reproducibility of chemiluminescence signals obtained using a stopped flow system: [Lucigenin]: 1.0×10−5 M, [Fe(III)]: 1.0×10−5 M, [H2O2]: 4.0 M, [KOH]: 2.0 M, flow rate: 3.5 mL/min.. −5. −5. 2. 2. −5. −5. 2. −5. 2002, Vol. 46, No. 6. 2. −5. Fig. 8. Calibration curve for total Fe obtained by chemiluminescence method using a stopped flow system: [Lucigenin]: 1.0×10−5 M, [H2O2]: 4.0 M, [KOH]: 2.0 M, flow rate: 3.5 mL/min.. !" Fe(III) #$%&. EF G

(78) ! H Ü$ <=q" :Æ >9k 3.5 mL/ min N, lucigenin 89k 1.0×10 M, KOH 8 9k 2.0 M, H O 89k 4.0 M, Fe(II)+ 89 k 1.0×10 M N

(79) N, Fe(III) + 89- ñ " )*g <= R

(80) ST QMN, Ð k Fig. 8$ ^M'. R

(81) ST UTV VW" XH" 1.0×10 M$ P 1.0×10 M M'. 89XH$P YZ[ " 0.996MN, R\7[" 1.0×10 MM'. Fe(III)+ T J

(82) ! H Ü$ <=q " :Æ >9k 3.5 mL/min N 1.0×10 M −5. 2. 2. −5. −6. −4. −7. −5.

(83) . 514. . Fig. 9. Calibration curve for Fe(III) ion obtained by chemiluminescence method using a stopped flow system: [Lucigenin]: 1.0×10−5 M, [H2O2]: 4.0 M, [KOH]: 2.0 M, [citric acid]: 0.01 M, [Fe(II)]: 1.0×10−5 M, flow rate: 3.5 mL/min.. 2.0 M KOH 4.0 M H O 4 citric acid 89k 0.01 M N

(84) N, Fe(III) + Fe(II)+ )*$P Fe(II) + 89k 1.0×10 M N

(85) N, Fe(III) + 89k ñ :¬nP R

(86) ST QMN, Ð k Fig. 9$ ^M'. R

(87) ST UTV VW" XH" 1.0×10 M$ P 1.0×10 M M'. 89XH$P YZ[ " 0.997MN, R\7[" 5.0×10 MM'. lucigenin. 2. 2. −5. −6. −4. −7.

(88) À lucigenin _ `$ 7 Fe(II) Fe(III)

(89) !" #$ %&'. Fe(III) + Fe(II)+

(90) !$ IJ H O 89, KOH 89 4 >9" LL 4.0 M, 2.0 M, 3.5 mL/min M'. Fe(III) + T J

(91) ! H Fe(II) + 0 H D7 citric acid IJ 89" 0.01 M M'. O7 IJ CK $P Q( EF G R

(92) ST$P UTV VW" XH" 1.0×10 M$P 1.0×10 M M'. 89XH$P YZ[ " 0.996 MN, R\7[" 1.0×10 MM'. Fe(III) + R

(93) ST( UTV VW" XH" 1.0×10 M$P 1.0×10 M M'. 89XH$P YZ[ " 0.997 MN, R\7[" 5.0×10 MM'. 2. 2. −6. −4. −7. −6. −4. −7. 1. In Encyclopedia of Analytical Science; Townshend, A., Ed.; Academic Press: New York, U. S. A., 1995, 4, 2369. 2. Patruta, S. I.; Edlinger, R.; Sunder-Plassmann, G.; Horl, W. H. J. Am. Soc. Nephrol. 1998, 9, 655. 3. Uchida, T. Int. J. Hematol. 1995, 62, 193. 4. Mulero, V.; Brock, J. H. Blood 1999, 94, 2383. 5. Shears, G. E.; Neale, R. J.; Ledward, D. A. Br. J. Nutr. 1989, 61, 573. 6. Kochana, J.; Parczewski, A. Chem. Anal. 1997, 42, 411. 7. Kosse, J. S.; Yeung, A. C.; Gil, A. I.; Miller, D. D. Food Chem. 2001, 75, 371. 8. Damkroger, G. Fresenius J. Anal. Chem. 1997, 357, 817. 9. Fernandez, P. L.; Pablos, F.; Martin, M. J.; Gonzalez, A. G. Food Chem. 2002, 76, 483. 10. Budic, B. Fresenius J. Anal. Chem. 2000, 368, 371. 11. Budic, B.; Klemenc, S. Spectrochim. Acta 2000, 55B, 11. 12. Watanabe, M.; Narukawa, A. Analyst 2000, 125, 1189. 13. Ueoka, S.; Furukawa, J.; Nakanishi, T. M. J. Radioanal. Nucl. Chem. 2001, 249, 475. 14. Favaro, D. I. T.; Maihara, V. A.; Mafra, D.; Souza, S. A.; Vasconcellos, M. B. A.; Cordeiro, M. B. C.; Cozzolino, S. M. F. J. Radioanal. Nucl. Chem. 2000, 244, 241. 15. Dutta, R. K.; Acharya, R. N.; Chakravortty, V.; Nair, A. G. C.; Reddy, A. V. R.; Chintalapudi, S. N.; Manohar, S. B. J. Radioanal. Nucl. Chem. 1998, 237, 91. 16. Duan, T.; Chen, H.; Zeng, X. J. Anal. At. Spectrom. 2002, 17, 410. 17.Chen, H. H.; Beauchemin, D. J. Anal. At. Spectrom. 2001, 16, 1356. 18. Harrington, C. F.; Elahi, S.; Merson, S. A.; Ponnampalavanar, P. Anal. Chem. 2001, 73, 4422. 19. Martino, F. A. R.; Sanchez, M. L. F.; Sanz-Medel, A. Anal. Chim. Acta 2001, 442, 191. 20. Rose, A. L.; Waite, T. D. Anal. Chem. 2001, 73, 5909. 21. Alapont A. G.; Zamora, L. L.; Calatayud, J. M. J. Pharm. Biomed. Anal. 1999, 21, 311. 22. Bowie, A. R.; Achterberg, E. P.; Mantoura, R. F. C.; Worsfold, P. J. Anal. Chim. Acta 1998, 361, 189. 23. In Encyclopedia of Analytical Science; Townshend, A., Ed.; Academic Press: New York, U. S. A., 1995, 1, 608. 24. Weber, A. J.; Grayeski, M. L. Anal. Chem. 1987, 59, 1452. 25. Robarrds, K.; Worsfold, P. J. Anal. Chim. Acta 1992, 266, 173. 26. Luminescence Biotechnology: Instrumentation and Applications; Dyke, K. V.; Dyke, C. V.; Woodfork, K., Ed.; CRC Press: New York, U. S. A., 2002. Journal of the Korean Chemical Society.

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Determination of Fe(II) ion and Fe(III) ion by Chemiluminescence Method Fe(II) Fe(III)   

Determination of Fe(II) ion and Fe(III) ion by Chemiluminescence Method Fe(II) Fe(III)