The kinetics of the Al+N2O→AlO+N2 reaction has been studied in a high-temperature fast-flow reactor (HTFFR). The expression k(520–1030 K)=4.6×10−12 (T/K)0.5 exp(−778 K/T) cm3 molecule−1 s−1 has been derived from a nonlinear regression analysis of the measured rate coefficients. 2σ precision limits are about ±5% and accuracy limits are estimated to be about ±23%. Combining the data with a 296 K literature measurement yields k(296–1030 K)=5.8×10−15 (T/K)1.37 exp(−90.4 K/T) cm3 molecule−1 s−1, with 2σ estimated accuracy limits of about ±27%. The semiempirical approach used previously to predict activation barriers for s1 and s2 metal atom reactions with N2O has been modified to allow predictions of group 13 atom reactions with N2O. The activation barriers for the B, Ga, In, and Tl atom reactions are calculated from the experimental activation barrier of the Al+N2O reaction.
The kinetics and products of the Cu + HCl reaction have been studied using high-temperature fast-flow reactors (HTFFR). The rate coefficient measurements were made using laser-induced fluorescence (LIF) of Cu atoms and yielded k(680-1500 K) ) 1.2 × 10 -10 exp(-7719 K/T) cm 3 molecule -1 s -1 . Product analysis was achieved by coupling a specially designed HTFFR to a chopped molecular beam quadrupole mass spectrometer. Those observations, which covered the approximately 1150-1500 K temperature range, showed formation of CuCl and the previously unknown species HCuCl. Confirmation of the latter assignment was made using DCl. Increasing pressure and decreasing temperature favor the HCuCl formation. These findings and this molecular structure are supported by ab initio calculations. These also indicate passage through a CuClH f HCuCl transition state as the rate-controlling step for formation of both products, in agreement with the observed pressure independence of the overall, Cu disappearance, rate coefficients.
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