Abstract
IN a recent communication on the recombination of chlorine atoms Linnett and Booth1 reported a value of 3 × 1014 cm6 moles−2 sec−1 for the third-order rate constant defined by: 
The method used by these workers determines only the relative atom concentration along a tube. It is hence suitable for rate constant determinations when the process is first order in atom concentration. In this case, however, since the process is second order in Cl-atoms the absolute concentration must be known. Linnett and Booth could only ‘assume’ arbitrary values for the absolute concentrations. It is our belief that these assumed values were wrong by an order of magnitude.
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References
Linnett, J. W., and Booth, M. H., Nature, 199, 1181 (1963).
Ogryzlo, E. A., Canad. J. Chem., 39, 2556 (1961).
Bunker, D. L., and Davidson, N., J. Amer. Chem. Soc., 80, 5085 (1958).
Martens, J. W., Disc. Farad. Soc., 33, 297 (1963)
Hiracka, H., and Hardwick, R., J. Chem. Phys., 36, 1715 (1962).
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BADER, L., OGRYZLO, E. Recombinations of Chlorine Atoms. Nature 201, 491–492 (1964). https://doi.org/10.1038/201491a0
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DOI: https://doi.org/10.1038/201491a0
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