Migration of translationally excited fluorine atoms in solid argon and their reactions with small guest molecules
作者:Eugenii Ya. Misochko、Alexander V. Akimov、Charles A. Wight
DOI:10.1016/s0009-2614(97)00626-x
日期:1997.8
Solid state reactions of photogenerated F atoms with CO and O2 molecules were studied in dilute mixtures of F2 + CO and F2 + O2 in solidargon by infrared spectroscopy. UV laser photolysis of F2 at 16 K produces high yields of stabilized FCO and FO2 radicals. Spectral and kinetic analysis reveals that formation of radicals occurs by reaction of translationallyexcited F atoms with isolated CO or O2
Spectrokinetic studies of the gas-phase equilibrium F+O2⇌FO2 between 295 and 359 K
作者:Palle Pagsberg、Emil Ratajczak、Alfred Sillesen、Jerzy T. Jodkowski
DOI:10.1016/0009-2614(87)80097-0
日期:1987.10
Spectrokineticstudies of the gas-phaseequilibriumF+O2⇌FO2 have been undertaken at six temperatures between295 and 359K. F atoms were produced by pulse radiolysis of Ar/F2/O2 mixtures. The yield of FO2 radicals and the rates of formation and decay were studied as a function of the oxygen concentration, and the temperature dependences of both the forward and reverse rate constants, k1 and k−1, were
气相平衡的Spectrokinetic研究F +Ò 2 ⇌FO 2具有六个温度K. F原子295和359之间通过的Ar / F的脉冲辐解产生的已进行2 / O 2混合物。研究了FO 2自由基的产率以及形成和衰变的速率与氧浓度的关系,得出了正向和反向速率常数k 1和k -1的温度依赖性。平衡常数K p = k 1 / k -1 RT被证明是与压力无关的。ΔS 298 0 = -24.917 cal / mol K的计算值,与其他计算出的热力学变量和测得的平衡常数结合使用时,得出ΔH 298 0 = -12.62±0.50 kcal / mol,ΔH f,298 0(FO 2)= 6.24±0.50千卡/摩尔,特性FO 2粘结强度Δ ħ 0 0 = 11.68±0.50千卡/摩尔。
Laser flash photolysis of O2 and F2 mixtures: The O2F ν1 band at 6.7 μm
作者:K.C. Kim、G.M. Campbell
DOI:10.1016/0009-2614(85)80160-3
日期:1985.5
We report the first experimental observation of the ν1band (OO stretching) of the O2F radical in the gas phase and its equilibrium existence with O2F2. The radical was formed by laserflashphotolysis of O2 and F2mixtures in a very long pathlength cell and the detection was done by a Fourier transform infrared spectrometer.
Novel method for the measurement of gas-phase peroxy radical absorption spectra
作者:Timothy J. Wallington、M. Matti Maricq、Thomas Ellermann、Ole J. Nielsen
DOI:10.1021/j100181a080
日期:1992.1
The pulse radiolysis method has been used to generate methyl peroxy radicals in the presence of high concentrations of NO. The CH3O2 radicals are then rapidly converted to CH3ONO by reaction with NO. Methyl nitrite absorbs strongly in the UV. Hence the initial absorption attributable to CH3O2 is rapidly replaced by absorption by CH3ONO. By varying the monitoring wavelength one can readily determine the isosbestic point, where sigma(CH3O2) = sigma(CH3ONO) + sigma(NO2). For methyl peroxy radicals the isosbestic point was determined to lie in the wavelength range 228-230 nm, and hence sigma(CH3O2) = (3.9 +/- 0.4) x 10(-18) cm2 molecule-1. Quoted errors are the sum of statistical (2-sigma) and our estimate of potential systematic errors (5%). As part of the present work rate constants for reactions 11 and 14 at 298 K and 600 mbar total pressure of SF6 were determined to beCH3 + NO + M --> CH3NO + M (11) F + O2 + M --> FO2 + M (14) k11 = (1.07 +/- 0.03) x 10(-11) cm3 molecule-1 s-1 and k14 = (2.35 +/- 0.20) x 10(-13) cm3 molecule-1 s-1 at 298 K. Results are discussed with respect to previous literature data.
Matrix photochemistry of hypofluorous acid, HOF: oxygen atom transfer and other reactions
作者:Evan H. Appelman、Anthony J. Downs、Christopher J. Gardner