Effect of gas diluents on assessment of kinetics in pressure response cells

The pressure response cell (PRC) allows direct physical measurements to be used to deduce chemical rate parameters for gas—liquid reactions. The Rice—Benoit approximation allowed both reaction order and rate constant to be found directly, provided only that a single-component gas phase existed. We e...

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Bibliographic Details
Published in:Chemical engineering science 1994, Vol.49 (6), p.845-849
Main Authors: Rice, R.G., Burns, L.F., Miao, R.S.
Format: Article
Language:English
Subjects:
Applied sciences
Chemical engineering
Exact sciences and technology
Reactors
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Summary:The pressure response cell (PRC) allows direct physical measurements to be used to deduce chemical rate parameters for gas—liquid reactions. The Rice—Benoit approximation allowed both reaction order and rate constant to be found directly, provided only that a single-component gas phase existed. We examined the dynamics of PRC for the case when high concentrations of inert diluents are present in the gas phase, so that a damping effect is introduced as a consequence of gas film resistance. The resulting nonlinear problem was solved approximately to allow parameter estimation under damped conditions. The results were used to estimate parameters for PRC experiments on the cobalt catalyzed oxidation of sulfite solutions by oxygen in the presence of varying amounts of nitrogen. The experimental results suggest that the order with respect to oxygen is unity when oxygen partial pressure is greater than 1 atm, and nearly second order when pressure is less than 1 atm.
ISSN:0009-2509
1873-4405
DOI:10.1016/0009-2509(94)80021-9