Special considerations

  • E. S. Swinbourne
Part of the Studies in Modern Chemistry book series (SMC)


With certain kinetic systems it may be reasonably assumed that the concentrations of some or all of the participating species do not change appreciably with time. This assumption of time-invariance may be applied, for example, to all species for a volume element in a fixed position within a flow system, or to particular species, such as reactive intermediates in a static system. In such cases, the concentrations of these species are maintained in a dynamic balance of steady state by the interaction of opposing processes which may be either physical or chemical in origin: bulk flow of material, diffusion, and precipitation constitute typical physical processes, while chemical processes may originate from thermal, photochemical, or electrochemical sources. In this chapter two important types of steady-state systems are discussed. These are the flow system, in which the physical process of flow is opposed by the chemical process of reaction, and the radical-chain system in which the opposing acts of formation and removal of reactive intermediates occur by chemical processes.


Rate Coefficient Plug Flow Tubular Reactor Arrhenius Parameter Relaxation Kinetic 
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References to flow systems

  1. 1.
    Denbigh, K. Chemical Reactor Theory. An Introduction. Cambridge University Press, London, 1965.Google Scholar
  2. 2.
    Hougen, O. A., and K. M. Watson. Chemical Process Principles. Part 3: Kinetics and Catalysis. John Wiley, New York, 1947.Google Scholar
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    Aris, R. Introduction to the Analysis of Chemical Reactors. Prentice-Hall, Englewood Cliffs, N.J., 1965.Google Scholar
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    Penner, S. S. Chemical Reactions in Flow Systems. Butterworths, London, 1955.Google Scholar
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    Herndon, W. C. Kinetics in gas-phase stirred-flow reactors. J. Chem. Ed., 1964, 41, 425.CrossRefGoogle Scholar
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    Denbigh, K. G. Trans. Faraday Soc., 1944, 40, 352, and 1947, 43, 648;Google Scholar
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References to chain reactions

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    Dainton, F. S. Chain Reactions. An Introduction. Methuen, London, 2nd ed., 1966.Google Scholar
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    Frost, A. A., and R. G. Pearson. Kinetics and Mechanism. John Wiley, New York, 2nd ed., 1961. Chapter 10.Google Scholar
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    See also the series, Advances in Free Radicals,Academic Press, New York, vol. 1 (1967) and subsequent volumes.Google Scholar

References to relaxation kinetics and related topics

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    Caldin, E. F. Fast Reactions in Solution. John Wiley, New York, 1964.Google Scholar
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    Eigen, M., and L. De Maeyer. Chapter 18 in Investigation of Rates and Mechanisms of Reactions (see reference 9, above). This volume gives a comprehensive coverage by a number of other contributors to the study of very rapid reactions.Google Scholar
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    Eigen, M. Disc. Faraday Soc., 1954, 17, 194, and subsequent papers. See also M. Eigen and J. S. Johnson, Ann. Rev. Phys. Chem., 1960, 11, 307.Google Scholar
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    Swinehart, J. H. Relaxation kinetics. J. Chem. Ed., 1967, 44, 524.CrossRefGoogle Scholar
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    Finholt, J. E. The temperature-jump method for the study of fast reactions. J. Chem. Ed., 1968, 45, 394.CrossRefGoogle Scholar

Copyright information

© E. S. Swinbourne 1971

Authors and Affiliations

  • E. S. Swinbourne
    • 1
  1. 1.New South Wales Institute of TechnologyAustralia

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