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(1)Journal of the Korean Chemical Society 2001, Vol. 45, No. 6 Printed in the Republic of Korea. vª"«ªCV»j jÏ "Öz>²~ >ª7» ;ïö & . ¿¿ú*Áxd¬Á³â. ;ö&v ¶"& z" (2001. 9. 28 7>) A Study on the Spectrometric Determination of Hydrogen Peroxide Using a Technique of Flow Injection Analysis Hoon Hwang*, Seung-Ki Hong and Ji-Yeon Lee Department of Chemistry, Kangwon National University, Chunchon 200-701, Korea (Received September 28, 2001). º £. ÖWöB H O & HCrO N" >w~ ê Óï~ CrO(O ) ¢ ;W~º >wö vª "«ªCj ê«~ >Ïò 7 H O ~ ·j ;ï > ®º >ª7ªC»j BB~& . ªC» ö ~ H O ~ ;ïº*º 2.00×10 M~0.020 M, G;êº £ 1.5×10 M . 6, ªC»f. B ;Öf ;J 7ö Ò~º "Öz>²~ ³êÖ;öê ÒÏ > ®r C&r . 2. −. 2. 4. 2. 2. 2 2. 2. −6. 2. −6. ABSTRACT. Hydrogen peroxide(H2O2) reacts with HCrO−4 in an acidic condition to produce CrO(O2)2 which exhibits an intense blue color. This reaction is coupled with a technique of Flow Injection Analysis(FIA) for the absorption spectrometry of H2O2 in the aqueous samples. The method could be applied for the determination of H2O2 over the range of 2.00×10−6M¥0.020 M with the limit of detection of ¥1.00×10−6 M. The method was also used to successfully determination of the H2O2 content in the snow and rain samples.. B . 2. æçb¦V OÂB Öz(SO )VÚ& &V 7 ~ w»ç(condensed phase)öB n; ;~ z« b æ~>º ";f j" 7º~ . F 7~ ~¾º ;Ö¾ ;J ~ ÖWzö ~º 'Ë r^. . >w³êö &NB þÖ" " ' >~. ö "~, H O º &V7 b(atmospheric water)öB S(IV)z« S(VI)z« æz>º ";(.: )öB "º ÖzBB~ j >¯ SO SO. º Ò C&r . f ? H O ö ~ Öz> w 7º~² J>º F f r" ? . Ñ, H O ö ~ S(IV)~ Öz>wf ÖW öB ³ê& z ¢æV r^ . V¢B ÖWb æzB ~ãöBê H O ö ~ Öz>wf æ³F > 2. 2. 2(g). 2−. 4. 2. (aq). 1. 2. 2. 2. 2. 2. ® º Ò . ~, H O f þ ÖzB J >º J(O )¾ Ö²(O ) Ò Özî²(NO ). 7öB H O & bö &Ë ¾ V r^ . V¢B H O & &V 7~ Úçö &Ë ô j Ú& ³ »F > ® º Ò . Ö H O ~ ;ï·ëf & V 7öB B~º &æ "; ö & ¢ * j>' ·ë¢ > ® . 6, H O ~ ;ï O»f ê(glucose)¾ .Êr(cholesterol) Ò ºÖ(uric acid)" ? ªç'b 7º bî ~ ;ï·ëö ÒÏ>Vê ~º, Fº b î Î²(enzyme)ö ~ ª>º ãÖ W>º bî 7~ ~¾& : H O V r^ . V¢B Î²ö ~ ª>wf z·'b ¢Ú¾æ WB H O ~ ³ê¢ rjÞ ª>w ¢Ú¾V * >wb~ .V³ê¢ rjâ >& ® . >Ï 7. 2. 3. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 520. 2. 2. 2.

(2) vª"«ªCV»j jÏ "Öz>²~ >ª7» ;ïö & . ö Ò~º H O ~ ³ê¢ rjÚº O» f . ·~² BB>Ú ÒÏ> ®b, ¢>'b ª7 ' O»(spectrophotometric method) ¾ *Vz' O»(electrochemical method) j > ® . . O» ~ G;ê(limit of detection, LOD)º £ 10 M . ;ï»ö j z ¸f 6ê(sensitivity)¢ º~º ªCöBº ;7(fluorescence)¾ zB7 (chemical luminescence)*çö "¢ z B7»(luminescence method) Ï>Vê . þöBº V~ ª7ªC» ö j ã B' *Þ~² >Ï 7 H O ¢ ;ï > ®º >ª7ªC»j BB~¶ ~& . ¢ * r " ?f z>wj ÒÏ~&b, HCrO +2H O +H CrO(O ) +3H O z>wf Cr(VI)~ ;ïö ÒÏ>Úê ' ® . ¯, ÖWöB H O º Cr(VI)" >w~ ê Óï~ CrO(O ) ¢ ;W . >wf ;ï'b ê¯~, WB CrO(O ) º ®n;~ vï~ Cr Nb £² ªB . V¢B ³vª"«ªC V»j ê«~ ç&'b ¸f Ö7ê>¢ &æº ê ï~ CrO(O ) ª>V *ö ·j ; ïb ªC»~ 6êf Ò*Wj Ã&V . 2. 2. 2. 3. −6. 4. 2. − 2. 2. 2. 5. +. 2. 2. 2 2. 2. 2. 2 2. 2 2. 3+. 2 2. þ þöB ÒÏ FIA system~ êÛ ê& Fig. 1ö J® . systemöBº peristaltic pump (PP, Ismatec MV Pump System)f 2B~ channel j ÒÏ~, ' channelj Û Ï~ Ú>j *Bº Tygon pump tubing(Úã: 0.38 mm, Cole-Parmer Instrument FIA system.. 521. j jÏ~& . 6, pumpê~ system Ú~ Î line º Úã 0.38 mm r2& (PTFE tubing)j ÒÏ~& . Sample injection valve (SV, Rheodyne 6-port valve, loop volume: 107 µL)ö ~ "«B H O Fòº pump(PP)~ Ñ ® channelj Û b~ vªj V¢ FIA system~ Ú¦ Ú>B . ò~ vªf mixing teeöB pump~ v ® channelj Û ÖW K Cr O Ï(K Cr O in H SO )~ vª" D ê >wz¢(R)j Û"~B H O f Cr O NÒ~ >w ¢ÚÂ . VB > wz¢f £ 10 cm;ê~ PTFE tubingj ~ ; Rj B· ©b mixing teeöB ö^ ¾Jº v &æ Ï ~ ¢ Dªj Fê" ÿö jº ö V¢Bº v &æ z« Ò~ >w*j ¦ ~¾ >w~ ÏWj ¦~º ê >¯ . H O f Cr O Ò~ ³ z·' >w~ Wb ê ï~ CrO(O )j F~º Ï~ v ªf flow-through cell(¦b: 10 µL) ËOB ¦ÂV (DT, UV/VIS detector, Spectra-Physics)¢ Û"~B CrO(O ) ö ~ 7ê& G;B . £. 10 M~0.1 M ³ê'~ H O &Ï f Na S O ¢ ÒÏ &z';j Û B stock solutionj '.® c& B~& . H O f~ >wö jº Cr O Nj F~º Ï (0.05, 0.07, 0.09, 0.1, 0.2 M)f K Cr O (extra pure, Junsei Chemical)j B>(pure water, Milli Q, Academic, Millipore)ö B~& . VB HCrO N & Cr O Nj F~º Ïj ÒÏ Fº þ öB~ .j. þÖ" HCrO Nj F~º Ïj ÒÏ~º ã Ö baseline~ noise level ² Ã&~ ªC»~ 6 ê& 6² º Ò j &V~&V r^ . «*~. þöBê HCrO N & Cr O Nj F~º Ïj ÒÏ~º ãÖ H O f~ >wWöº jZ æ Ë ìº ©b C&rV r^ . Company). 2. 2. 2. 2. 2. 7. 2. 2. 7. 4. 2−. 2. 2. 2. 7. 2. 2. 2. 7. 2−. 2. 2 2. −6. 2. 2. 2. 2. 3. 2. 2. 2. 2−. 7. 2. 2. 7. −. 2. 2. 2−. 7. −. 4. −. 4. 2. 2. 2−. 7. 2. 5. Ö" 5 V 'ªC2Ë. ¢>' >ª7ªC»ö ~Bº N" H O Ò~ Öz-~ö>wö ~ W >º >Ï 7 CrO(O ) ~ >Ê¿Þ"j áj > ì º, Fº >ÏöBº CrO(O ) ~ n;ê&. Ö Ôj Cr Nb £² ª>V r^ . «*~. Cr2O2− 7 Fig. 1. Schematic diagram of the FIA system for the determination of H2O2 in environmental aqueous samples. PP: peristaltic pump, SV: sample injection valve, R: reaction coil (knotted delay lines), and DT: UV-VIS detector. 2001, Vol. 45, No. 6. 2. 2. 2 2. 2 2. 3+.

(3) ¿ úÁxd¬Á³â. 522. Table 1. The effect of [H2SO4] on the formation of CrO(O2)2. The concentration of the Cr2O72− solution was fixed at 0.1 M and a standard H2O2 solution of 1.00×10−4 M was used to measure the absorbance [H2SO4], M. 0.05. 00.1. 00.2. 00.5. 01.0. Relative peak height 52.6. 52.9. 43.8. 27.3. 16.3. ©b áÚr . 0.2 M" 0.3 M~ K Cr O Ï j ÒÏ~ áÚê Ö"f jv Ö"ö ~~, 0.3 M Ï~ ÒÏb ^~ Vº ² Ã&~&æ ò baseline~ noise level Ã&~ ^Ã&~ Î" & >6Nj " > ®î . ê ³ê(1.00×10 M)~ H O Ïj ÒÏ~º ãÖ &Û 0.1 M;ê& '³êª &G>î . þöBº ;ï»~ 6ê (sensitivity)~ Ãêj * cf ³êöB z ^¢ áj > ®º 0.20 Mj K Cr O Ï~ '³ ê Ö;~& . 'F³. FIA systemöB 0.10 M H SO Ïj Ò Ï~ B 0.20 M K Cr O Ïj ÒÏ çöB *ÚF³j æzÊB CrO(O ) ö ~ 7ê æ z¢ G;~& . Ö" Ï~ F³ ¶Ö ãÖö º >wWb ¦ÂVö ê~º * ^Úöö V¢ CrO(O ) ~ ªö V¢ 7êº ² 6²~& b, >& F³~ ¢æ 7êº Ã&~&æò Ã&f Ò æ p~ . V¢B "Úê * ªC&Ë ò~ >, ²º>º £~ ·, Ò 7 ê j J~ Ö; 'F³f 2.09 mL/min . 'ªCöB~ ¦;F. öB~ þ j Û~ áÚê 'ªC(0.20 M K Cr O in 0.10 M H SO , &>2Ë: 590 nm, *ÚF³: 2.09 mL/min) öB H O &Ï j ÒÏ~ áÚê ¦;Ff Fig. 2f ? . H O &Ï ö ~ áÚæº ^. ~ Ò*Wf ¸~b, ' ³ê'öB~ Ò*W, ¯ JNêº ¦;F çöB ' ³êê B 6 ~ VÚ . ö V 2.00×10 ~2.00×10 M~ 9f ³êº*ö ö >Ï ò 7 H O ~ ;ï &Ëj r > ® .. B ~ãò 7 H O ~ ;ï. öB áÚê ' öB B ~ãò ;Öf ;Jj j÷ ê ³ö FB H O ~ ³ê¢ Ö; Ö"& Table 3 ö J® . ö V 2001j 1ú" 2ú ¾Â æ öB j÷B ;Ö 5 ;Jò 7öº £ 10 M; ê~ H O & F>Ú ®rj r > ® . ;Öf ; M. 2. þöB CrO(O ) ~ &>2Ëö & þ j >¯~&b, Ö" 590 nm CrO(O ) ~ ' ªC2Ëb áÚr . V¢B þöBê 590 nm ¢ & ÒÏ~& . H SO Ï~ '³ê. '~ ÖWj * H SO Ï~ '³ê¢ ~V * FIA system~ * Ú F³j ;~ Cr O Ï~ ³êº 0.10 M ¢ ;~² Fæ çöB 1.0×10 M H O Ïj ÒÏ ~ H SO Ï~ ³êæzö V 7ê æz¢ G ;~& . Ö" VVö ¾æ¾º ^~ V j G;~ Table 1" ?f jvÖ"¢ áî . ö V , H SO Ï~ ³ê& 0.10 M¢ r CrO(O ) ö ~ 7ê& &, H SO Ï~ ³ê& 0.10 M. z êæ(K Cr O Ï~ ÖW jºçb Ã &>º ãÖ) CrO(O ) ö ~ 7êº /Ï® 6² j " > ® . H SO Ï~ ³ê& Ã&ö V¢ CrO (O ) ö ~ 7êº /Ï® 6²~º Fº r" ? º; > ® . K Cr O Ï~ ÖW jºç b Ã&~² >, HCrO N¾ Cr O N ' ' H CrO f HCr O Nb æ~º ï;>w / ê>Ú H O f >w~ CrO(O ) ¢ W~º HCrO N~ ³êº 6²~ ö V¢ CrO(O ) ö ~ 7ê& 6²~º © . þöBº H SO Ï~ '³ê 0.10 Mj F~& . K Cr O Ï~ '³ê. FIA system~ *Ú F³f ;Ê 0.10 M H SO Ïj ÒÏ öB K Cr O Ï~ ³ê¢ æzÊB 7ê¢ G;~ Table 2¢ áî . Ö"ö V H O ~ ³ê& cf(8.00×10 M) ãÖ K Cr O Ï~ '³ê& 0.2 2 2. 2. 2 2. 4. 2. 4. 2−. 2. 7. −4. 2. 2. 2. 4. 2. 4. 2 2. 2. 2. 2. 4. 7. 2 2. 2. 4. 2 2. 2. 2. 7. −. 4. 2. 4. 2. 2. 2−. 2. 7. −. 7. 2. −. 2 2. 4. 2 2. 2. 2. 2. 7. 2. 2. 2. 4. 4. 7. 2. −6. 2. 2. 2. 7. 7. −4. 2. 5. 2. 2. 2. 2. 7. 2. 2. 2. 4. 7. 2 2. 2 2. 2. 2. 2. 7. 4. 2. 2. 2. 2. −6. −2. 2. 2. 2. 2. 2. 2. −5. 2. 2. Table 2. The effect of [K2Cr2O7] on the formation of CrO(O2)2. The concentration of the H2SO4 solution was fixed at 0.1 M and the two standard H2O2 solutions of 1.00×10−4 M and 8.00×10−6 M were used to measure the absorbance [K2Cr2O7], M Relative Peak Height. [H2O2] 1.00×10-4 M [H2O2] 8.00×10-6 M. 110.05. 10.07. 10.08. 10.09. 10.1. 10.2. 104.8 17.8. 106.8 8.4. 109.5 8.7. 110.5 9.1. 107.5 18.7. 104.7 10.1. Journal of the Korean Chemical Society.

(4) vª"«ªCV»j jÏ "Öz>²~ >ª7» ;ïö & . 523. «~ >Ïò 7 H O ~ ·j ;ï > ®º >ª7ªC»j BB~& . V~ ª7' ªC». ~ ãÖ ÞÒ~² « > ìº £ ~ ÒÏj º~¾ ªC"; ² Ç~&b¾ ö j *Ò BBB ;ï»f z ãB' ¶Ú ªC »¢ > ® . 6, H O ~ ;ïº*º 2.00×10 M ~0.020 M j" 9b, G;êº £ 1.5×10 M. . 6, ªC»f B ;Öf ;J 7ö Ò~ º "Öz>²~ ³êÖ;öê ÒÏ > ®r C& r . 2. 2. 2. −6. 2. −6. Ï^ò. Fig. 2. Plot of log (relative peak height) vs. log [H2O2] over the analytical concentration range of [H2O2]=2.00×10−6 M and 2.00×10−2 M. Table 3. The concentration of H2O2 in the snow and rainwater samples collected around the buildings of the College of Natural Sciences at Kangwon National University, Chunchon, Kangwon-Do during the period of Jan. 8 and Feb. 23, 2001 Dates. Jan. 8. Feb. 8. Feb. 23. [H2O2], M 1.06×10−5 1.34×10−5 5.00×10−6 1.00×10−5. Jò¦V áÚê ªCÖ"& B H O ö ~ ©æ¢ {~V * òö ²ï~ MnO (MnO º >Ï 7 H O ~ ª¢ /ê)¢ & ê ò 7 H O ~ ;ïj >¯~& . Ö" j Z 7êê G;>æ p~bæ ;Öf ;Jò ö & H O G;Ö"º Ö > ®º ©b Aj. ¢ > ® . 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. Ö ÖWöB H O & HCrO N" >w~ ê Óï~ CrO(O ) ¢ ;W~º >wö vª"«ªCj ê 2. 2 2. 2001, Vol. 45, No. 6. 2. −. 4. 1. (a) Mader, P. M, J. Am. Chem. Soc. 1958, 80, 2634. (b) Hoffman, P. M.; Edwards, J. O. J. Phy. Chem. 1975, 79, 2096. (c) Martin, L. R.; Damschen, D. E. Atmos. Environ. 1981, 15, 1615. (d) Kunen, S. M.; Laxrus, A. L.; Kok, G.: Heikes, B. J. J, Geophy. Res. 1983, 88, 3671. 2. (a) Frew, J. E.; Jones, P.; Scholes, G. Anal. Chim. Acta 1983, 155, 139. (b) Patterson, B. D.; Macrae, E. A.; Ferguson, I. B. Anal. Biochem. 1984, 139, 487. (c) Gupta, B. L. Mikrochem. J. 1973, 18, 363. (d) Olsson, B.; Ogreen, L. Anal. Chim. Acta 1983, 145, 87. 3. (a) Feldman, F. J.; Bosshart, R. E. Anal. Chem. 1966, 38, 1401. (b) Diez, L. P.; Mender, J. H.; Parra, J. A. Talanta 1981, 28, 951. (c) Brestovoski, J.; Zumen, P. Practical Polarography; Academic Press Inc.: New York, 1968. (d) Cho. T; Toshida, S.; Hirose, S. Bunseiki Kagaku 1983, 32, 6. 4. (a) Pilosof, D.; Nieman, T. A. Anal. Chem. 1982, 54, 1968. (b) Van Zoonen, P.; Gooijer, C.; Velthorst, N. H.; Frei, R. W. Anal. Chim. Acta 1985, 167, 249. (c) Boveris, A.; Martino, E.; Stoppani, A. O. M. Anal. Biochem. 1977, 80, 145. (d) Kelly, J. B.; Christian, G. D. Anal. Chem. 1983, 53, 2110. (e) Guilbaoult, G. G.; Brignac, P.; Juneau, D. T. Anal. Chem. 1968, 40, 1256. (f) Hwang, H.; Dasgupta, P. K. Anal Chem. 1986, 58, 1521. 5. Hwang, H. J. Korean Chem. Soc. 2000, 44, 322..

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