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OXIDATION OF CYCLOHEXANE IN SUPERCRITICAL CARBON-DIOXIDE MEDIUM

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Title OXIDATION OF CYCLOHEXANE IN SUPERCRITICAL CARBON-DIOXIDE MEDIUM
 
Creator SRINIVAS, P
MUKHOPADHYAY, M
 
Subject water
fluid
mixtures
kinetics
solvent
catalysis
cumene
pyrolysis
methanol
behavior
 
Description Cyclohexane oxidation has been studied in supercritical carbon dioxide medium for homogenizing the initial reaction mixture to produce cyclohexanone and cyclohexanol as the chief reaction products. The kinetic experiments have been performed at three temperatures 410, 423, and 433 K and two pressure's 170 and 205 bar. The results have been interpreted in the light of transition state theory and cage effects. Conversions obtained are low compared to the liquid phase oxidation because of dilute concentrations of the reactants. Cyclohexanone is more selectively formed and favored by both pressure and temperature. A 20% increase in pressure results in (i) reduction of the induction period by 50%, (ii) a change in activation energy from 13.0 kcal/mol at 170 bar to 22.6 kcal/mol at 205 bar, (iii) an increase in the preexponential factor by 5 orders of magnitude, and (iv) an increase in the first-order rate constant at 433 K by about 70%. The variation in the observed activation volume from 36 cm(3)/mol at 410 K and 170 bar to -775 cm(3)/mol at 433 K and 205 bar suggests that the reaction in supercritical CO2 medium can be greatly manipulated.
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-14T14:58:40Z
2011-12-26T12:48:27Z
2011-12-27T05:39:06Z
2011-07-14T14:58:40Z
2011-12-26T12:48:27Z
2011-12-27T05:39:06Z
1994
 
Type Article
 
Identifier INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 33(12), 3118-3124
0888-5885
http://dx.doi.org/10.1021/ie00036a029
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3990
http://hdl.handle.net/10054/3990
 
Language en