| The gas-phase kinetics of several metal species reactions of interest to combustion and waste incineration has been studied over wide temperature ranges. A high-temperature fast-flow reactor (HTFFR) has been used in combination with laser-induced fluorescence (LIF) or atomic resonance absorption spectrometry (ARAS) to obtain the rate coefficients or upper limits for the Pb + N 2O, Cl2, and HCl, Sb + O2, N2O, and HCl, and CUCl + Cl2 reactions. The following results, in cm 3 molecule-1 s-1, have been obtained: Pb + N2O, k(650--1205 K) = 1.80 x 10-10 exp(-8948 K/T); Pb + Cl2, k(530--1165 K) = 2.28 x 10 -10 exp(-718 K/T); Pb + HCl, k(1090--1320 K) = 8.22 x 10-10 exp(-17233 K/T); Sb + O2, k(1165--1495 K) = 6.25 x 10-11 exp(-9107 K/T); Sb + N2O, k(1131 +/- 8 K) = (9.0 +/- 0.8) x 10-15; Sb + HCl, k(1120 +/- 1660 K) < 3.0 x 10-15; CUCl + Cl 2, k(980 +/- 1150 K) = 3.10 x 10 -11 exp(-4765 K/T). The kinetics of the Pb + O2 reaction, which was found to exhibit complex temperature behavior, could only be interpreted in terms of heterogeneous processes. The results from the Pb + HCl and the Sb + O2 studies also suggest that D0(Pb-Cl) = 318 +/- 31 kJ mol-1 and D0(Sb-O) = 444 +/- 28 kJ mol-1. In the course of this work the experimental technique and procedures have been further improved leading to the decrease in the lower limit to the rate coefficients that can be measured in the HTFFR by an order of magnitude. Exploratory work on the temperature dependence of metal ion-molecule reactions has been performed. For this purpose a different experimental technique, a high-temperature photochemistry (HTP), has been employed and an attempt was made to study the Ca+ + N2O reaction. These efforts were mainly focused on the testing and development of the Ca+ production technique. At this point more work needs to be done to make the technique operational. Preliminary measurements, however, suggest that in the 1000--1100 K temperature range the Ca+ + N2O reaction proceeds at k ≈ 9 x 10-11 cm3 molecule -1 s-1. |
