Reactivity of Solvated Electrons with NH<sub>4</sub>NO<sub>3</sub> in 1-Propanol/Water Mixtures

Hyun-Kyung Lee; Tae-Beom Kang

Journal of Industrial and Engineering Chemistry, Vol.10, No.6, 899-905, November, 2004

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Reactivity of Solvated Electrons with NH₄NO₃ in 1-Propanol/Water Mixtures

Hyun-Kyung Lee, and Tae-Beom Kang^{1, †}

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

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The reaction rate constants of the solvated electrons (e_s) with ammonium nitrate in 1-pro-panol/water mixtures are related to the transport properties, such as the electrical conductance of the salt. The values of the molar conductivity (Λ_o) of NH₄NO₃ are (20-150)X 10^-4 S m² mol^-1 at 298.15 K. The molar conductivity (Λ_o) increases gradually as the mole fraction of water (X_w) goes from 0.00 to 0.70 and increases rapidly as X_w reaches the pure water solvent region. The values of the activation energy of conductance (E_Λ) have a maximum at X_w reaches the pure water solvent region. The values of the activation energy of conductance (E_Λ) have a maximum at X_w 0.70 in the range 298.15 ~ 358.15 K. The maximum value of E_Λ corresponds to the maximum value of viscosity. The values of the effective reaction radius (_KR_r) for the reaction [e_s^-+ (NH₄⁺)_s] are 0.09 ~ 0.74 nm at 0.00 ≤ X_w 0.50, and those for the reaction [e_s^-+(NO₃^-)_s] are 0.20 ~ 0.30 nm at 0.70 ≤ X_w ≤ 1.00 and 278.15 ≤ T(K) ≤ 338.15. This finding indicates that the reactivity of the reaction [e_s^- + ammonium nitrate] increases as the composition of 1-propanol increases in the alcohol-rich region (0.00 ≤ X_w ≤ 0.50). The values of the effective diffusion radius (R_d) for the reaction [e_s^-+ ammonium nitrate] are 28 ~ 178 pm at 0.00 ≤ X_w ≤ 1.00 and 278.15 ≤ T(K) ≤ 338.15. The decrease of R_d upon initial addition of alcohol to water (0.97 ≤ X_w ≤ 1.00) is attributed to the dynamic viscosity (η) of the mixed solvent, and the increase of R_d upon further addition of alcohol to water (0.00 ≤ X_w≤0.97) is attributed to the larger dependence on Λ_o than η

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

[References]

Lai CC, Freeman GR, J. Phys. Chem., 94, 4891 (1990)
Duplatre G, Jonah CD, J. Phys. Chem., 95, 897 (1991)
Maham Y, Freeman GR, J. Phys. Chem., 89, 4347 (1985)
Berntolini D, Cassettori M, Salvetti G, J. Chem. Phys., 78, 365 (1983)
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Chen R, Freeman GR, Can. J. Chem., 71, 1303 (1993)
Hong SR, Lee HK, Kang TB, J. Ind. Eng. Chem., 9(6), 704 (2003)
Zhao Y, Freeman GR, Can. J. Chem., 73, 392 (1995)
Kang TB, Freeman GR, Can. J. Chem., 71, 1297 (1993)
Sedigallage AP, Freeman GR, Can. J. Phys., 68, 940 (1990)
Jou FY, Freeman GR, Can. J. Chem., 57, 592 (1979)
Lide DR, Handbook of Chemistry and Physics, 74th Edn., pp. 5-91, CRC, London (1993-1994)
Barker GC, Fowles P, Sammon DC, Stringer B, Trans. Faraday Soc., 66, 1498 (1970)
Senanayake PC, Freeman GR, J. Chem. Phys., 87, 7007 (1987)
Kim SW, Nam JD, J. Ind. Eng. Chem., 8(3), 212 (2002)
Timmermans J, The Physico-chemical Constants of Binary Systems in Concentrated Solutions, Vol. 4, p. 217, Interscience, New York (1960)

[Referenced By]

[1] Lai CC, Freeman GR, J. Phys. Chem., 94, 4891 (1990)

[2] Duplatre G, Jonah CD, J. Phys. Chem., 95, 897 (1991)

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

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

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

[6] Zhao Y, Freeman GR, Can. J. Chem., 74, 300 (1996)

[7] Zhao Y, Freeman GR, Can. J. Chem., 76, 407 (1998)

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

[9] Hong SR, Lee HK, Kang TB, J. Ind. Eng. Chem., 9(6), 704 (2003)

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

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

[12] Sedigallage AP, Freeman GR, Can. J. Phys., 68, 940 (1990)

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

[14] Lide DR, Handbook of Chemistry and Physics, 74th Edn., pp. 5-91, CRC, London (1993-1994)

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

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

[17] Kim SW, Nam JD, J. Ind. Eng. Chem., 8(3), 212 (2002)

[18] Timmermans J, The Physico-chemical Constants of Binary Systems in Concentrated Solutions, Vol. 4, p. 217, Interscience, New York (1960)