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p ‐ tert ‐Butylcalix[6]arene reactant: p ‐ tert ‐Butylphenol from Aldrich Chemical Company, Inc. product: p ‐ tert ‐Butylcalix[6]arene

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Rate constants were determined for the reactions of CH(X2Π,ν=0) with H2 and D2 and for the relaxation of CH(X2Π,ν=1) by H2 and D2. The method, employing pulsed laser photolysis to generate CH radicals and laser-induced fluorescence to observe their rate of removal, was implemented between 744 and 86 K in heated and cryogenically cooled cells and from 295 to 13 K in a Cinétique de Réaction en Ecoulement Supersonique Uniforme (CRESU) apparatus. The rate constants for the reaction of CH(ν=0) with D2 were determined from 13 to 584 K and those for the removal of CH(ν=1) by H2 and D2 from 23 to 584 K. These rate constants show no dependence on total pressure and a mild negative temperature dependence, and they are clearly related closely to the rate of capture to form a strongly bound CH3* or CHD2* energized collision complex. The rate constants for the reaction of CH(ν=0) with H2 were measured from 53 to 744 K. By contrast, their values depend in a complex fashion on temperature and total pressure, the latter effect having been studied from 4 to 400 Torr in heated and cooled cells and from 0.28 to 4.5 Torr at 53 K in the CRESU apparatus. It is clear that reaction proceeds via a CH3* complex which, favored by high temperatures and low total pressures, can dissociate to give CH2+H, CH(X2Π)+H2→CH2+H; ΔrH2980=+(12.0±5.2) kJ mol−1 or, especially at low temperatures and high total pressures, may be stabilized by collisions to yield CH3 radicals CH(X2Π)+H2+M→CH3+M; ΔrH2980 =−(450.7±2.0) kJ mol−1. Careful analysis of the pressure-dependent fall-off behavior yields the following expressions for the rate constants (in the case of the association reaction, in the limit of low pressure): k(1a)=(3.1±0.7)×10−10 exp(−(1650±100)/T) cm−3 molecule−1s−1, k(1b)0[Ar]=(5.2±1.5)×10−30(T/298)−1.6±0.22[Ar] cm3 molecule−1 s−1. Comparison of the rate data obtained for the reaction of CH(ν=0) with D2 and for the removal of CH(ν=1) by H2 and D2 is consistent with all three processes occurring through the formation of a CH3* (CHD2*) complex whose rate of formation is independent of the vibrational state of the CH. Consequently the rate constant for the reaction in the limit of high pressure can be estimated from that for the removal of CH(ν=1) by H2 yielding: k(1b)∞=(1.60±0.11)×10−10(T/298)−0.08±0.05 cm3 molecule−1 s−1.

Time-resolved vibrational chemiluminescence from HF has been recorded following the production of F atoms by the pulsed laser photolysis (A = 266 nm) of F2 in the presence of HCI, CHI, and CF3H. In the first two cases, experiments have been conducted by observing emission from HF(v = 3) at four temperatures from 295 to 139 K. Rate constants have been determined over this range of temperature for the reactions of F atoms with HC1 and CH4 and of CH3 radicals with F2, and for the relaxation of HF(v = 3) by HC1 and CH4. The reaction of F atoms with CF3H is slower than those with HCl and CH4 and measurements on the emission from HF(v = 2) have been used to infer rate constants for reaction and relaxation only a t 295 K.