Eine gaskinetische Studie zur Reaktion von HOCl mit F‐, Cl‐ und H‐Atomen bei Raumtemperatur

The reactions of HOCl with F‐, Cl‐ and H‐atoms were investigated at room temperature in a discharge flow system equipped with an OH‐resonance fluorescence cell and a mass spectrometric detector. All kinetic studies were carried out under pseudo first order conditions with HOCl being the minority component. Branching ratios for individual processes were obtained by following simultaneously the rates of HOCl consumption and product formation. The following rate constants (in units cm3 molecule−1 s−1) were determined F + HOCl → Products k(1) = (4.9±0.6)·10−11 (1) → ClF + OH k(1a) = (1.2±0.4)·10−11 (1a) CL + HOCl → Products k(2) = (1.4±0.37)·10−12 (2) → Cl2 + OH k(2a) = (3.4±1.4)·10−13 (2a) H + HOCl → Products k(3) = (3.5±0.7)·10−12 (3) → HCl + OH k(3a) ≤ (6.7±2.1)·10−13 (3a) Calibration for [HOCl] using reaction (1) for gas titration is discussed. The data are evaluated to yield ΔHf (298) = ‐79.7 kJ mol−1 for the heat of HOCl formation.