화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.14, No.4, 526-532, July, 2008
DOI10.1016/j.jiec.2008.03.002  Export Citation
Solvent effects on reactivity of solvated electrons with ammonium nitrate in 2-propanol/water mixed solvents
Hyun-Kyung Lee†, and Tae-Beom Kang1
  • Department of Industrial Chemistry, Sang Myung University, Seoul 110-743, Republic of Korea
  • 1Department of Chemistry, Sang Myung University, Seoul 110-743, Republic of Korea
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The solvent effects on reactivity of solvated electrons (e(s)-) with ammonium nitrate were studied in 2-propanol/water mixed solvents as a function of solvent composition and temperature. The kinematic viscosities and densities of these mixed solvents were measured as a function of solvent composition and temperature, and the electrical conductances of ammonium nitrate in the mixed solvents were also measured. The measured rate constants of the nearly diffusion controlled reaction were examined according to the Smoluchowski-type models. These models are useful in evaluating the effects of bulk solvents on reactivity of solvated electrons with charged solutes. In the region of 80.100 mol% water, the rate constants for the reaction [e(s)- + (NO3-)(s)] increase with the decrease of viscosity. This indicates that the reaction rates in these solvents correspond well to the Smoluchowski.Stokes model. However in the region of 0.20 mol% water, the rate constant for the reaction [e(s)- +(NH4+)(s)] increases with the increase of viscosity. This phenomenon is attributed to the high values of the effective reaction radius (kRr) for the reaction [e(s)- +(NH4+)(s)] in these solvents. The values of kRr (10^(-10) m) in the region of 0.20 mol% water are 4.8.5.7, whereas 2.3.2.6 in the region of 80. 100 mol% water at 298 K. With the exception of the region from 100 to 93 mol% water, the effective diffusion radius (Rd) decreases with the increase of water content. The activation energies of reaction (E2) display having higher values than those of viscosity (Eη) and conductance (EΛο ) in the 2-propanol-rich region, while they become lower than both of Eη and EΛο in the water-rich region, and converge to similar values in almost pure water.
Keywords:Solvated electron;Kinematic viscosity;Electrical conductance;Effective reaction radius;Effective diffusion radius
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