Thermal decomposition of phosgene

CH3 + Cl = CH3Cl: RRKM/master equation modeling

“…The values of the high-pressure limit for the combination reaction are in essential agreement with Parker et al [15]. These numbers are about a factor of 2 higher than those calculated from Lennard-Jones collisions modified by electronic degeneracy, as proposed by Lim and Michael [12]. Since the data are close to the lowpressure limit and not very sensitive to k ∞ , use of these lower values for the high-pressure limit, while keeping all other parameters constant, lowers the calculated values at 300 K by about 15% at the highest experimental pressure (see Fig.…”

“…Lim and Michael [12] studied the reaction at three different loading pressures of Ar corresponding to pressures of approximately 300, 450, and 600 Torr. They concluded that the difference in rate constants was small enough that the entire data set could be represented by the first-order rate constant, k 1 (s −1 ) = 1.21 × 10 10 exp(−27838/T ).…”

Thermal Decomposition Studies of Halogenated Organic Compounds

“…[ls], CH3Cl [10,11], C3H3Cl [19], CFC13 [16,20], CF2C12 [16,21], CF3Cl [16,22], CF2HCl [13], CF3I [12], CH3I [23], C2H5I [24], C6H5I [25], and CC120 [26]. The methods used are nearly identical in all cases, and for the purposes of discussion, we will illustrate the method with CH3I data -ln(IdIo) (It and Io refer to transmitted and incident I-atom resonance light intensities, respectively), is measured as CH3I decomposes.…”

Thermal decomposition of CF3Br using Br-atom absorption

“…The Br-atom resonance lamp configuration (2.2 torr flow of 0.1% Br 2 in UHP He, at 50 W microwave power) is similar to the Cl-atom lamp detailed elsewhere [17,18]. The Br lamp was derived from that used in flash photolysis-resonance fluorescence work [19].…”

“…Since the path length is 9.94 cm, the Br atom absorption cross-section is . Hence, Br atom analysis Ϫ14 2 ϭ 1.419 ϫ 10 cm is more sensitive than that for Cl atoms [17,18] and is less sensitive than that for I-atoms [3]. At higher concentrations the curve becomes increasingly nonlinear due no doubt to resonance lamp self-reversal.…”