Investigation of the gas-phase kinetics of the reaction potassium + sulfur dioxide + argon

Abstract

The recombination of atomic potassium, K(42S), with SO2 has been investigated at about 863 K, in a bath of Ar at pressures from 20 to 690 mbar. K was generated by flash photolysis of KI vapor and monitored by time-resolved resonance absorption of a D-line at 766 nm under pseudo-first-order conditions. The measured pseudo-second-order rate constants lie in the low-pressure and falloff regions and were fitted with an empirical RRKM expression to yield ko = 5.9 X cm6 s-l and k, = 6.2 X 1O-l0 cm3 s-l. Error limits are discussed in the text. The KSOz adduct was characterized by ab initio methods. An RRKM analysis of ko, together with a lower limit to the equilibrium constant, yielded a K S 0 2 bond strength of 190 f 10 kJ mol-'. k, was shown to be consistent with a simple harpoon model for electron transfer.

The vibrational spectra of molecular ions isolated in solid neon. XI. NO+2, NO−2, and NO−3

“…Ramondo and Bencivenni 9 later reported the results of unrestricted Hartree-Fock calculations for SO 2 Ϫ and NaSO 2 , which were consistent with that assignment. A recent gas-phase kinetic study 10 of the KϩSO 2 reaction also yielded evidence for the formation of a long-lived KSO 2 complex, and the associated Hartree-Fock calculations suggested that the structure of KSO 2 , like that of NaSO 2 , is planar, with C 2v symmetry. Recent photoionization/Penning ionization studies in this laboratory have led to stabilization in a neon matrix of sufficient concentrations of a wide variety of molecular cations and anions for infrared spectroscopic detection.…”

Experimental and computational studies of the kinetics of the reaction of hydrogen atoms with carbon disulfide

“…This means H atoms are being regenerated and a plausible reaction scheme involves decomposition of the stabilized adduct back to H + CS 2 : H → diffusion loss rate constant k diff (10) C S 2 H → loss without H regeneration rate constant k 11 (11) The integrated biexponential rate law is [22]…”

“…Details of our apparatus for laser flash photolysis experiments with time-resolved resonance fluorescence detection of atomic hydrogen, including with other sulfur-containing species, have been provided previously [10][11][12][13][14] and so the method is outlined here. Inside a heated stainless steel reaction cell, H atoms are created by pulsed photolysis of a precursor at 193 nm, ammonia (NH 3 ) in this case, and then react with a large excess of CS 2 which is therefore effectively at constant concentration.…”

On-line spectroscopic and spectrometric methods for the determination of metal species in industrial processes☆

“…For example, the fine-structure splitting (Dl) of Li is only 0.015 nm or 10 GHz, whereas in K, it is 3.4 nm and in Rb, 14.7 nm [227]. The hyperfine splitting broadens the Doppler absorption profile of K from a halfwidth at full maximum (HWFM) of 0.39 GHze0.45 GHz at 298 K. However for Rb, the splitting distorts even the pressurebroadened absorption lines at 1 bar, as shown by comparing measured Rb(D2) absorption profiles in a combustor at 1273 K and in a low-pressure (<1 mbar), room-temperature cell; in the latter case, the four hyperfine lines of 87 Rb and 85 Rb were clearly resolved.…”

“…The reactions of sodium atoms with oxygen and nitrous oxide have been the most frequently studied [73e83], but reactions with SO 2 have also been investigated [84,85]. Kinetic studies of alkali species in flames are reported in Refs.…”