과산화수소가 옥살산의 광분해에 미치는 영향

김응호; 김영환; 정동용; 유재형; 최청송

HWAHAK KONGHAK, Vol.35, No.3, 440-444, June, 1997

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과산화수소가 옥살산의 광분해에 미치는 영향

Effect of H₂O₂ in Photodestruction of Oxalic Acid

김응호, 김영환, 정동용, 유재형, 최청송

초록

질산이 첨가되었을 경우와 첨가되지 않았을 때의 과산화수소와 옥살산 혼합물의 광분해 연구와 아울러 과산화수소 단독의 광분해 연구가 수행되었다. UV 조사시 과산화수소 분해반응은 과산화수소가 고농도일 경우에는 1차 반응, 저농도에서는 0차 반응으로 나타났다. 옥살산 자체는 UV 조사에 의해서 분해되지 않지만, 과산화수소가 존재할 때 UV 조사에 의해 급격히 분해되었다. 그러나 질산 매질에서 과산화수소는 더 이상 옥살산 분해에 영향을 미치지 않았다. 이것은 과산화수소의 광분해에 의해 발생되는 수산화 라디칼이 옥살산과의 반응으로는 소모되지 못하고, NO₃^-의 광분해 생성물인 NO₂^-과의 반응으로 소모됨을 알 수 있었다.

Photodestruction of hydrogen peroxide alone as mixture of hydrogen peroxide and oxalic acid with and without nitric acid were carried out in this study. Decomposition reaction of H₂O₂ under UV radiation showed that rate equation was first order with respect to [H2O2] for high concentration of H₂O₂ and zero order for low concentration of H₂O₂. Oxalic acid itself was not decomposed by UV radiation, whereas in the presence of H₂O₂ decomposed rapidly under UV radiation. But, the presence of H₂O₂ in the nitric acid media affected no longer on decomposition of oxalic acid. This was attributed that OH radical generated by photolysis of H₂O₂ was not consumed by reaction with oxalic acid, but by reaction with NO₂^- ion to be photolysis product of NO₃^-.

Keywords:Photodestruction;Oxalic Acid;Hydrogen Peroxide;UV Radiation;Decomposition

[References]

Choppin G, Rydberg J, Liljenzin JO, "Radiochemistry and Nuclear Chemistry," Butterworth-Heinemann Ltd. (1995)
Rankin T, Burney GA, Smith PK, Sisson RD, Ceram. Bull., 56, 478 (1977)
IAEA Technical Reports Series No. 214: "Evaluation of Actinide Partitioning and Transmutation," IAEA, Vienna (1982)
Yoo JH, "Development of Long-lived Radionuclide Partitioning Technology," KAERI/RR-1632/95, Most (1996)
Kobayashi T, Morita Y, Kubota M, "Development of Partitioning Method; Method of Precipitating Trasuranium Elements with Oxalic Acid," JAERI-M88-026 (1988)
Forberg CW, Nucl. Technol., 49, 2431 (1980)
Kim EH, Shin YJ, Kim WH, Chung DY, Kim SS, Yoo JH, Choi CS, Korean J. Chem. Eng., 12(5), 557 (1995)
Mimura H, Akiba K, Igarashi H, J. Nucl. Sci. Technol., 31(2), 136 (1994)
Kim EH, Kim YH, Chung DY, Lee EH, Yoo JH, HWAHAK KONGHAK, to be published (1997)
Bakore GV, Jain CL, J. Inorg. Nucl. Chem., 3, 2527 (1969)
Barek S, Berka A, Civisora O, Coll. Czechoslovak Chem. Commun., 49, 954 (1984)
Malcom JM, Noyes RM, J. Am. Chem. Soc., 7, 2769 (1952)
Mailen SC, Tallent OK, Arweed PC, "Destruction of Oxalate by Reaction with Hydrogen Peroxide," ORNL/TM-7474 (1980)
Chung DY, Kim EH, Shin YJ, Yoo JH, Choi CS, Kim JD, J. Radioanal. Nucl. Chem. Lett., 201(6), 495 (1995)
Glaze WH, Peyton GR, Lin S, Huang RY, Burleson JL, Environ. Sci. Technol., 16, 454 (1982)
Wang F, Cassidy K, Lum B, "Incineration Alternatives for Combustible Waste Ultraviolet/Hydrogen Peroxide Process," UCRL-ID-112284 (1992)
Carter AH, Weiss J, Proc. Roy. Soc. A, 174, 351 (1940)
Volman DH, Seed JR, J. Am. Chem. Soc., 86, 5095 (1964)
Wang F, Lum BY, "Photolytic Destructionof Oxalate in Aqueous Mixed Waste," UCRL-JC-119739 (1995)
Benedict M, Pigford TH, Levi HW, "Nuclear Chemical Engineering," McGraw-Hill Book Co. (1981)
Kolthoff IM, Sandell EB, Meehan EJ, Bruckenstein S, "Qualitative Chemical Analysis," Fourth ed., Macmillan Co., London (1971)
Patai S, "The Chemistry of Peroxides," John Wiley and Sons, Ltd. (1983)
Volman DH, Chen JC, J. Am. Chem. Soc., 81, 4141 (1959)
Lunak S, Sedlak P, J. Photochem. Photobiol. A-Chem., 68, 1 (1992)
Forbes GS, Heidt LJ, J. Am. Chem. Soc., 56, 2363 (1934)
Daniels M, Meyers RV, Belardo EV, J. Phys. Chem., 72(2), 389 (1968)

[Referenced By]

[1] Choppin G, Rydberg J, Liljenzin JO, "Radiochemistry and Nuclear Chemistry," Butterworth-Heinemann Ltd. (1995)

[2] Rankin T, Burney GA, Smith PK, Sisson RD, Ceram. Bull., 56, 478 (1977)

[3] IAEA Technical Reports Series No. 214: "Evaluation of Actinide Partitioning and Transmutation," IAEA, Vienna (1982)

[4] Yoo JH, "Development of Long-lived Radionuclide Partitioning Technology," KAERI/RR-1632/95, Most (1996)

[5] Kobayashi T, Morita Y, Kubota M, "Development of Partitioning Method; Method of Precipitating Trasuranium Elements with Oxalic Acid," JAERI-M88-026 (1988)

[6] Forberg CW, Nucl. Technol., 49, 2431 (1980)

[7] Kim EH, Shin YJ, Kim WH, Chung DY, Kim SS, Yoo JH, Choi CS, Korean J. Chem. Eng., 12(5), 557 (1995)

[8] Mimura H, Akiba K, Igarashi H, J. Nucl. Sci. Technol., 31(2), 136 (1994)

[9] Kim EH, Kim YH, Chung DY, Lee EH, Yoo JH, HWAHAK KONGHAK, to be published (1997)

[10] Bakore GV, Jain CL, J. Inorg. Nucl. Chem., 3, 2527 (1969)

[11] Barek S, Berka A, Civisora O, Coll. Czechoslovak Chem. Commun., 49, 954 (1984)

[12] Malcom JM, Noyes RM, J. Am. Chem. Soc., 7, 2769 (1952)

[13] Mailen SC, Tallent OK, Arweed PC, "Destruction of Oxalate by Reaction with Hydrogen Peroxide," ORNL/TM-7474 (1980)

[14] Chung DY, Kim EH, Shin YJ, Yoo JH, Choi CS, Kim JD, J. Radioanal. Nucl. Chem. Lett., 201(6), 495 (1995)

[15] Glaze WH, Peyton GR, Lin S, Huang RY, Burleson JL, Environ. Sci. Technol., 16, 454 (1982)

[16] Wang F, Cassidy K, Lum B, "Incineration Alternatives for Combustible Waste Ultraviolet/Hydrogen Peroxide Process," UCRL-ID-112284 (1992)

[17] Carter AH, Weiss J, Proc. Roy. Soc. A, 174, 351 (1940)

[18] Volman DH, Seed JR, J. Am. Chem. Soc., 86, 5095 (1964)

[19] Wang F, Lum BY, "Photolytic Destructionof Oxalate in Aqueous Mixed Waste," UCRL-JC-119739 (1995)

[20] Benedict M, Pigford TH, Levi HW, "Nuclear Chemical Engineering," McGraw-Hill Book Co. (1981)

[21] Kolthoff IM, Sandell EB, Meehan EJ, Bruckenstein S, "Qualitative Chemical Analysis," Fourth ed., Macmillan Co., London (1971)

[22] Patai S, "The Chemistry of Peroxides," John Wiley and Sons, Ltd. (1983)

[23] Volman DH, Chen JC, J. Am. Chem. Soc., 81, 4141 (1959)

[24] Lunak S, Sedlak P, J. Photochem. Photobiol. A-Chem., 68, 1 (1992)

[25] Forbes GS, Heidt LJ, J. Am. Chem. Soc., 56, 2363 (1934)

[26] Daniels M, Meyers RV, Belardo EV, J. Phys. Chem., 72(2), 389 (1968)