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A selectivity method for modelling the kinetics of pentene‐2 hydrogenation
Author(s) -
Rao M. S.,
Hudgins R. R.,
Reilly P. M.,
Silveston P. L.
Publication year - 1971
Publication title -
the canadian journal of chemical engineering
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.404
H-Index - 67
eISSN - 1939-019X
pISSN - 0008-4034
DOI - 10.1002/cjce.5450490310
Subject(s) - selectivity , isothermal process , thermodynamics , kinetics , chemistry , hydrogen , kinetic energy , catalysis , mathematics , organic chemistry , physics , quantum mechanics
A maximum likelihood ratio was used as a statistical criterion for discriminating among twenty‐two kinetic models posited to describe the hydrogenation of mixed pentenes (cis‐ and trans‐2‐pentenes) with a Raney nickel catalyst. Selectivity ratio, the ratio of reaction rates of two different species, was used and found to be a suitable extension of conventional techniques for identifying rate controlling steps owing in this case to its reproducibility. Selectivity ratio models were of the Langmuir‐Hinshelwood form. Hydrogenation was performed isothermally at 20°C in benzene at five constant pressures corresponding to partial pressures of hydrogen of 22.5, 42.3, 62.3, 112.3 and 122.1 psia. Discrimination was attempted at each pressure, but found acceptable only at the three intermediate pressures. At each of these pressures, a model of similar functional form was found to represent the selectivity data; however, this model appears to be empirical. The likelihood ratio approach appears to be a powerful one for discriminating among a large number of models even with only a moderate number (˜ 20) of experimental observations.