Spin Trapping EPR Method for Simultaneous Monitoring of Hydroxyl Radicals and Hydrogen Atoms in γ-Irradiation Process

Dae Hyun Yoo; Sang Kuk Han; Myun Joo Lee; Joon Wun Kang

Journal of Industrial and Engineering Chemistry, Vol.11, No.2, 215-221, March, 2005

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Spin Trapping EPR Method for Simultaneous Monitoring of Hydroxyl Radicals and Hydrogen Atoms in γ-Irradiation Process

Dae Hyun Yoo, Sang Kuk Han¹, Myun Joo Lee, and Joon Wun Kang^{1, †}

Radioisotope & Radiation Application Team, Korea Atomic Energy Research Institute, Daejeon 305-600, Korea
¹Department of Maritime Environmental Engineering, Mokpo National Maritime University, Mokpo 530-729, Korea

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We have examined the generation of ' OH and ' H under low-dose γ-radiolysis in aqueous solution a through a spin trapping electron paramagnetic resonance (EPR) using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a trapping reagent. Here we discus separately the reaction schemes of DMPO-involved radiolysis for the cases during and after radiolysis. A method based on kinetic calculations has been developed to quantify exactly the concentrations of ' OH and ' H in situ. In the case when a batch monitoring method is employed, the time-resolved instability of DMPO adducts after sampling can be the sources of errors in estimating the in situ concentration of those radical species if it is not corrected with the due instability rates. The main causes of the instability of the DMPO adducts after the cessation of γ-irradaition were the homo-dimerization (adduct/adduct) reaction (DMPO-OH/DMPO-OH or DMPO-H/DMPO-H) and the hetero-(cross)-dimerization of DMPO-adducts (DMPO-OH and DMPO-H). The corresponding instability rate constants for the DMPO-OH/DMPO-OH and DMPO-OH/DMPO-H processes were 80 M-1s-1 and 2.8 × 103 M-1s-1, respectively. The ' OH trap yield in the 0.05 M DMPO solution at 10 GY was low (9.3%), which implies that ' OH might attack radicals might react with the DMPO adducts, causing a slight deviation from linearity for the plot of the DMPO adducts versus the γ-dosage.

Keywords:γ-irradiation;EPR; OH; H;DMPO adducts

[References]

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Han SK, Ichikawa K, Utsumi H, Water Res., 32, 3261 (1998)
Chung HH, Lee MJ, Jung J, Choi SW, J. Ind. Eng. Chem., 8(5), 483 (2002)
Utsumi H, Hakoda M, Shimbara S, Nagaoka H, Chung YS, Hamada A, Water Sci. Technol., 30, 91 (1994)
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Carmichael AJ, Makino K, Riesz P, Radiat. Res., 100, 222 (1984)
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[1] Glaze WH, Kang JW, Chapin DH, Ozone-Sci. Eng., 9, 335 (1987)

[2] Glaze WH, Kang JW, Ind. Eng. Chem. Res., 28, 1573 (1989)

[3] Kang PH, Nho YC, J. Ind. Eng. Chem., 7(4), 199 (2001)

[4] Draganic ZD, Draganic IG, J. Phys. Chem., 77, 2803 (1973)

[5] Bhler RE, Staelin J, Hoign J, J. Phys. Chem., 88, 2560 (1984)

[6] Lee GD, Jung SK, Jeong YJ, Park JH, Suh CS, Ahn BH, Hong SS, J. Ind. Eng. Chem., 8(1), 22 (2002)

[7] Buxton GV, Greenstock CL, Helman WP, Ross AB, J. Phys. Chem. Ref Data, 17, 513 (1988)

[8] Elovitz M, VonGunten U, Ozone-Sci. Eng., 21, 239 (1999)

[9] Janzen EG, Blackburn BJ, J. Am. Chem. Soc., 91, 4481 (1969)

[10] Buettner GR, Oberley LW, Biophys. Res. Commun., 83, 69 (1978)

[11] Bullock AT, Gavin DL, Ingram MD, J. Chem. Soc. Chem. Commun., 329 (1980)

[12] Han SK, Ichikawa K, Utsumi H, Water Res., 32, 3261 (1998)

[13] Chung HH, Lee MJ, Jung J, Choi SW, J. Ind. Eng. Chem., 8(5), 483 (2002)

[14] Utsumi H, Hakoda M, Shimbara S, Nagaoka H, Chung YS, Hamada A, Water Sci. Technol., 30, 91 (1994)

[15] Makino K, Magdi MM, Riesz P, J. Am. Chem. Soc., 104, 3537 (1982)

[16] Kalyanaraman B, Felix CC, Sealy RC, Agric. Biol. Chem., 41, 1787 (1982)

[17] Allen AO, The radiation chemistry of water and aqueous solutions, Van Nostrand-Reinhold, Princeton, N.J. (1961)

[18] Carmichael AJ, Makino K, Riesz P, Radiat. Res., 100, 222 (1984)

[19] Yanagida H, Masubuchi Y, Minagawa K, Ogata T, Takimoto JI, Koyama K, Ultrason. Sonochem., 5, 133 (1999)

[20] Madden KP, Taniguchi H, Free Radic. Biol. Med., 30, 1374 (2001)

[21] Castelhano PR, Perkins MJ, Griller D, Can. J. Chem., 61, 298 (1983)