Measurement of absolute rate data for the reaction of atomic potassium, K(4 2S1/2), with CF3Cl, CF2Cl2, CFCl3, CF3Br and SF6 as a function of temperature by time-resolved atomic resonance absorption spectroscopy at λ = 404 nm [k(5 2PJ) ← K(4 2S1/2)]

David Husain, Yook Heng Lee

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Abstract

We present a kinetic study of the reactions of atomic potassium in its electronic ground state, K(42S1/2), with the molecules CF3Cl, CF2Cl2, CFCl3, CF3Br and SF6. Atomic potassium was generated by pulsed irradiation of potassium halide vapour at elevated temperatures and monitored in the 'single-shot mode' by time-resolved atomic resonance absorption using the Rydberg doublet at λ = 404 nm [K(5 2PJ) ← K(4 2S1/2)]. Absolute rate constants for reaction with these molecules were determined as a function of temperature yielding the following Arrhenius parameters (errors 1σ): A/10-10 cm3 molecules-1 s-1 E/kJ mol-1 CF3Cl 1.1±0.5 13.8±2.5 CF2Cl2 2.1±0.6 5.5±0.5 CFCl3 ca. 1 ca. 0 CF3Br 3.9±0.4 12.3±0.6 SF6 8.4±1.33 12.3±0.9 CF4 exhibited anomalous kinetic behaviour. These results represent the first kinetic measurements, relative or absolute, for these fundamental reactions of atomic potassium. This new set of absolute rate data are compared with analogous results reported hitherto for atomic sodium, Na(3 2S1/2), both alkali-metal atoms exhibiting rapid reactions characterised by small energy barriers and being highly exothermic in character.

Original languageEnglish
Pages (from-to)2325-2337
Number of pages13
JournalJournal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics
Volume83
Issue number12
DOIs
Publication statusPublished - 1987
Externally publishedYes

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Absorption spectroscopy
potassium
Potassium
absorption spectroscopy
Molecules
Kinetics
kinetics
Alkali Metals
molecules
Temperature
temperature
Energy barriers
alkali metals
Ground state
shot
halides
Rate constants
Sodium
Vapors
sodium

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

Cite this

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title = "Measurement of absolute rate data for the reaction of atomic potassium, K(4 2S1/2), with CF3Cl, CF2Cl2, CFCl3, CF3Br and SF6 as a function of temperature by time-resolved atomic resonance absorption spectroscopy at λ = 404 nm [k(5 2PJ) ← K(4 2S1/2)]",
abstract = "We present a kinetic study of the reactions of atomic potassium in its electronic ground state, K(42S1/2), with the molecules CF3Cl, CF2Cl2, CFCl3, CF3Br and SF6. Atomic potassium was generated by pulsed irradiation of potassium halide vapour at elevated temperatures and monitored in the 'single-shot mode' by time-resolved atomic resonance absorption using the Rydberg doublet at λ = 404 nm [K(5 2PJ) ← K(4 2S1/2)]. Absolute rate constants for reaction with these molecules were determined as a function of temperature yielding the following Arrhenius parameters (errors 1σ): A/10-10 cm3 molecules-1 s-1 E/kJ mol-1 CF3Cl 1.1±0.5 13.8±2.5 CF2Cl2 2.1±0.6 5.5±0.5 CFCl3 ca. 1 ca. 0 CF3Br 3.9±0.4 12.3±0.6 SF6 8.4±1.33 12.3±0.9 CF4 exhibited anomalous kinetic behaviour. These results represent the first kinetic measurements, relative or absolute, for these fundamental reactions of atomic potassium. This new set of absolute rate data are compared with analogous results reported hitherto for atomic sodium, Na(3 2S1/2), both alkali-metal atoms exhibiting rapid reactions characterised by small energy barriers and being highly exothermic in character.",
author = "David Husain and Lee, {Yook Heng}",
year = "1987",
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TY - JOUR

T1 - Measurement of absolute rate data for the reaction of atomic potassium, K(4 2S1/2), with CF3Cl, CF2Cl2, CFCl3, CF3Br and SF6 as a function of temperature by time-resolved atomic resonance absorption spectroscopy at λ = 404 nm [k(5 2PJ) ← K(4 2S1/2)]

AU - Husain, David

AU - Lee, Yook Heng

PY - 1987

Y1 - 1987

N2 - We present a kinetic study of the reactions of atomic potassium in its electronic ground state, K(42S1/2), with the molecules CF3Cl, CF2Cl2, CFCl3, CF3Br and SF6. Atomic potassium was generated by pulsed irradiation of potassium halide vapour at elevated temperatures and monitored in the 'single-shot mode' by time-resolved atomic resonance absorption using the Rydberg doublet at λ = 404 nm [K(5 2PJ) ← K(4 2S1/2)]. Absolute rate constants for reaction with these molecules were determined as a function of temperature yielding the following Arrhenius parameters (errors 1σ): A/10-10 cm3 molecules-1 s-1 E/kJ mol-1 CF3Cl 1.1±0.5 13.8±2.5 CF2Cl2 2.1±0.6 5.5±0.5 CFCl3 ca. 1 ca. 0 CF3Br 3.9±0.4 12.3±0.6 SF6 8.4±1.33 12.3±0.9 CF4 exhibited anomalous kinetic behaviour. These results represent the first kinetic measurements, relative or absolute, for these fundamental reactions of atomic potassium. This new set of absolute rate data are compared with analogous results reported hitherto for atomic sodium, Na(3 2S1/2), both alkali-metal atoms exhibiting rapid reactions characterised by small energy barriers and being highly exothermic in character.

AB - We present a kinetic study of the reactions of atomic potassium in its electronic ground state, K(42S1/2), with the molecules CF3Cl, CF2Cl2, CFCl3, CF3Br and SF6. Atomic potassium was generated by pulsed irradiation of potassium halide vapour at elevated temperatures and monitored in the 'single-shot mode' by time-resolved atomic resonance absorption using the Rydberg doublet at λ = 404 nm [K(5 2PJ) ← K(4 2S1/2)]. Absolute rate constants for reaction with these molecules were determined as a function of temperature yielding the following Arrhenius parameters (errors 1σ): A/10-10 cm3 molecules-1 s-1 E/kJ mol-1 CF3Cl 1.1±0.5 13.8±2.5 CF2Cl2 2.1±0.6 5.5±0.5 CFCl3 ca. 1 ca. 0 CF3Br 3.9±0.4 12.3±0.6 SF6 8.4±1.33 12.3±0.9 CF4 exhibited anomalous kinetic behaviour. These results represent the first kinetic measurements, relative or absolute, for these fundamental reactions of atomic potassium. This new set of absolute rate data are compared with analogous results reported hitherto for atomic sodium, Na(3 2S1/2), both alkali-metal atoms exhibiting rapid reactions characterised by small energy barriers and being highly exothermic in character.

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