The Reactivity of the Solvated Electrons with KNO<sub>3</sub> in tert-Butanol/Water Mixtures

Se-Ryugn Hong; Hyun-Kyung Lee; Tae-Bum Kang

Journal of Industrial and Engineering Chemistry, Vol.9, No.6, 704-712, November, 2003

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The Reactivity of the Solvated Electrons with KNO₃ in tert-Butanol/Water Mixtures

Se-Ryugn Hong, Hyun-Kyung Lee¹, and Tae-Bum Kang^†

Department of Chemistry, Sang Myung Universtiy, Seoul 110-743, Korea
¹Department of Industrical Chemistry, Sang Myung University, Seoul 110-743, Korea

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The reactivity of the solvated electrons (e_s^-) with a charged scavenger in tert-butanol/water mixtures is analyzed according to the effective reaction radius (_kR_r) and the effective diffusion radius (R_d). In tert-butanol/water mixtures, the effective reaction radius (_kR_r) for the reaction (e_s^- + NO₃^-) decreases rapidly first, and then tends to increase gradually upon addition of alcohol to water. _kR_r increases as the reaction temperature increases at 0.64 ≤ X_w < 0.90 of the mole fraction of water (X_w), but decreases as the reaction temperature increases at 0.90 < X_w ≤ 1.00. _kR_r is dependent on the probability of the reaction per encounter pair (k). The values of _kR_r for the reaction (e_s^- + NO₃^-) are 0.20 ~ 0.39 nm at 0.64 ≤ X_w ≤ 1.00 and 298.15 ≤ T(K) ≤ 348.15. The effective diffusion radius (R_d) for the reaction (e_s^- + NO₃^-) in tert-butanol/water mixtures increases as the reaction temperature increases, and the minimum value of R_d is shifted from X_w 0.85 to 0.94 as the reaction temperature increases from 298.15 K to 348.15 K. The values of R_d are larger in the alcohol-rich region than in the water-rich region owing to the larger size of the solvent molecules that solvate ions. The values of R_d for the reaction (e_s^- + NO₃^-) are 23.12 ~ 64.12 pm at 0.64 ≤ X_w ≤ 1.00 and 298.15 ≤ T(K) ≤ 348.15.

Keywords:solvated electron scavenger;molar conductivity;effective reaction radius;effective diffusion radius

[References]

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Berntolini D, Cassettori M, Salvetti G, J. Chem. Phys., 78, 365 (1983)
Nakanishi K, Ikari K, Okazaki S, Touhara H, J. Chem. Phys., 80, 1656 (1984)
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Maham Y, Freeman GR, J. Phys. Chem., 92(6), 1506 (1988)
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Afanassiev AM, Okazaki K, Freeman GR, Can. J. Chem., 57, 839 (1979)
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[Referenced By]

[1] Milosavljevic BH, Micic OI, J. Phys. Chem., 82(12), 1359 (1978)

[2] Berntolini D, Cassettori M, Salvetti G, J. Chem. Phys., 78, 365 (1983)

[3] Nakanishi K, Ikari K, Okazaki S, Touhara H, J. Chem. Phys., 80, 1656 (1984)

[4] Senanayake PC, Freeman GR, J. Chem. Phys., 87(12), 7007 (1987)

[5] Maham Y, Greeman GR, Can. J. Chem., 66, 1706 (1988)

[6] Maham Y, Freeman GR, J. Phys. Chem., 89(20), 4347 (1985)

[7] Maham Y, Freeman GR, J. Phys. Chem., 92(6), 1506 (1988)

[8] Chen R, Freeman GR, Can. J. Chem., 71, 1303 (1993)

[9] Afanassiev AM, Okazaki K, Freeman GR, Can. J. Chem., 57, 839 (1979)

[10] Leu AD, Jha KN, Freeman GR, Can. J. Chem., 60, 2342 (1982)

[11] Leu AD, Jha KN, Freeman GR, Can. J. Chem., 61, 1115 (1983)

[12] Tanaka H, Nakanishi K, Touhara H, J. Chem. Phys., 81(9), 4065 (1984)

[13] Bender TM, Pecora RJ, J. Phys. Chem., 90(8), 1700 (1986)

[14] Senanayake PC, Freeman GR, J. Phys. Chem., 91(8), 2123 (1987)

[15] Senanayake PC, Freeman GR, J. Phys. Chem., 92(18), 5142 (1988)

[16] Lai Cc, Freeman GR, J. Phys. Chem., 94(1), 302 (1990)

[17] Zhao Y, Freeman GR, Can. J. Chem., 73, 392 (1995)

[18] Afanassiev AM, Okazaki K, Freeman GR, J. Phys. Chem., 83(10), 1244 (1979)

[19] Jou FY, Freeman GR, Can. J. Chem., 57, 592 (1979)

[20] Kang TB, Freeman GR, Can. J. Chem., 71, 1297 (1993)

[21] Senanayake PC, Ph.D. Thesis, Alberta University, Canada (1987)

[22] Timmermans J, The Physico-Chemical Constants of Binary Systems in Concentrated Solutions, Vol. 4, p. 235, Interscience, New York (1960)

[23] Lide DR, Handbook of Chemistry and Physics, 74th Edn., pp. 5-91, CRC, London (1993)

[24] Barker GC, Fowles P, Sammon DC, Stringer B, Trans. Faraday Soc., 66, 1498 (1970)

[25] Hart EJ, Anbar M, The Hydrated Electron., Wiley-Interscience, New York (1970)