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Third Report of the Committee on Photochemistry Reprint and Circular Series of the National Research Council (1938) / Chapter Skim
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Secondary Processes in the Photochlorination of Carbon Monoxide and Hydrogen
Pages 91-96

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From page 91...
... is occupied with the publication of the definitive conclusions of this long series of investigations and is attempting to incorporate within the framework of those conclusions, or reject for reasons ascertained, the auxiliary data that have accumulated from the investigations of other workers, notably Rollefson (15, 19, 20, 21) , Ritchie (17, 18)
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From page 92...
... [C121 tCO] The reaction constants ~c' and K2 are related by the following equations to the several constants of the individual reaction steps: k4 K1 = - ; 5 KCOC1 k4 K2 = k5,Kcoc1 By reason of the additional investigations of Bodenstein, Brenschede, and Schumacher (4, 5)
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From page 93...
... By trial, the equation obtained was log KCOCI = _ 5676 + 1.770 For reactions 4 and 5 the data are given in the form of equations E4.571T + log Zen + 1/2 log T—log f where E is the activation energy, Z.. the collision yield for T = 1°K., end f is the steric factor.
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From page 94...
... II. THE HYDROGEN—CHLORINE PHOTOREACTION The reaction sequence in the hydrogen-chlorine combination is, it is quite generally agreed, the Nernst chain mechanism, with the chains normally terminated by interaction of atomic hydrogen with oxygen impurities.
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From page 95...
... , with experiments in which both water and hydrogen chloride were formed, log k3—log k4 = 0.41 and hence log k3 = 9.01. The steric factor corresponding is then log fa = - 0.78.
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From page 96...
... Faraday Soc.
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Key Terms

  • numerical data
  • reaction constants
  • hence log
  • following equations
  • atomic hydrogen

  • steric factor
  • reaction sequence
  • normally terminated
  • definitive conclusions
  • individual reactions

  • third report
  • five reactions
  • additional investigations
  • chains normally
  • final revision

  • schemes assumed
  • practical equilibrium
  • equilibrium constant
  • definitive form
  • steadily consumed

  • factor corresponding
  • experimental results
  • accurate data
  • low concentration
  • perature coefficient

  • scheme pertaining
  • recently completed
  • chain mechanism
  • collision yield
  • auxiliary data


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