First Direct Observation of Equilibrium Involving Cl Atoms: Cl + C2H4 ⇔ ClCH2CH2 by VUV Monitoring
Mark A. Blitz, Thomas Henry Speak, Paul W. Seakins
TL;DR
This study directly observes the equilibrium between chlorine atoms and ethylene using VUV monitoring, revealing new insights into reaction kinetics and thermodynamics.
Contribution
First direct observation of equilibrium involving Cl atoms and ethylene using VUV laser-induced fluorescence.
Findings
Equilibrium behavior of Cl + C2H4 was observed between 393 and 490 K.
The enthalpy of reaction was determined as −74.1 ± 0.6 kJ mol–1.
Ab initio calculations were found to be accurate to within ∼4 kJ mol–1 compared to experimental results.
Abstract
The kinetics between Cl and ethylene, R1, have been determined between 298 and 822 K in time-resolved experiments, where the Cl atoms were monitored for the first time via laser-induced fluorescence at 118.877 nm. A key advantage of this method of Cl detection is that there is limited absorption of 118 nm radiation by oxygen, and we report the first Cl reactivity measurements. The kinetics of Cl + C2H4 at room temperature are simple association, k 1a([M]), and have been used in a master equation analysis (via the MESMER application) to show consistency with most of the literature. Between 393 and 490 K, the kinetics exhibited equilibrium behavior: Cl + C2H4 ⇔ Cl–C2H4 (k 1a([M]),k –1a([M])). These forward and reverse rate coefficients have been used in van’t Hoff and reaction rate theory (MESMER) analysis to determine the enthalpy of reaction, Δr H R1a o . This analysis yields a Δr H…
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Taxonomy
TopicsAdvanced Chemical Physics Studies · Quantum, superfluid, helium dynamics · Atmospheric Ozone and Climate