Influence of carbon dioxide and carbon monoxide on the kinetics of propylene polymerization

1978 ◽  
Vol 9 (1) ◽  
pp. 99-103 ◽  
Author(s):  
M. Lesná ◽  
J. Mejzlík
AIChE Journal ◽  
2010 ◽  
pp. NA-NA ◽  
Author(s):  
C. D. Bohn ◽  
J. P. Cleeton ◽  
C. R. Müller ◽  
J. F. Davidson ◽  
A. N. Hayhurst ◽  
...  

The kinetics of the various individual reactions which may occur in the steam-carbon system have been studied. The pressures of the separate gases have been varied in the range 10-760 mm. Essentially similar results have been obtained with coconut shell charcoal at 700° C and coal charcoal at 800° C. The steam-carbon reaction, the primary product of which is carbon monoxide, is of fractional order with respect to steam and strongly retarded by hydrogen. The carbon dioxide-carbon reaction is of fractional order with respect to carbon dioxide and strongly retarded by carbon monoxide. The rates of both these reactions can be represented closely by an expression of the form rate = k 1 p 1 /1 + k 2 p 2 + k 3 p 1 where p 1 and p 2 are respectively the pressures of steam and hydrogen for the steam reaction, and of carbon dioxide and carbon monoxide for the carbon dioxide reaction. This kinetic scheme provides a consistent interpretation of the apparently conflicting results of previous work under a variety of conditions with many different types of carbon. Further experimental work, however, is necessary to elucidate without ambiguity the mechanisms of these reactions. The water-gas reaction, CO + H 2 O = CO 2 + H 2 , takes place predominantly on the charcoal surface, and the approach to equilibrium has been studied from both sides. The forward reaction is of nearly the first order with respect to carbon monoxide and of fractional order with respect to steam; it is retarded by hydrogen and to a lesser extent by carbon dioxide. The reverse reaction is of fractional order with respect to both carbon dioxide and hydrogen, retarded by steam and unaffected by carbon monoxide. The kinetic expressions for the forward and reverse components of this heterogeneous reversible reaction combine to give the thermodynamically correct form of the equilibrium constant.


1984 ◽  
Vol 17 (6) ◽  
pp. 602-610 ◽  
Author(s):  
HAKUAI INOUE ◽  
MASAKI FUNAKOSHI

1960 ◽  
Vol 38 (8) ◽  
pp. 1261-1270 ◽  
Author(s):  
Margaret H. Back ◽  
A. H. Sehon

The thermal decomposition of phenylacetic acid was investigated by the toluene-carrier technique over the temperature range 587 to 722 °C. The products of the pyrolysis were carbon dioxide, carbon monoxide, hydrogen, methane, dibenzyl, and phenylketene. From the kinetics of the decomposition it was concluded that the reaction[Formula: see text]was a homogeneous, first-order process and that the rate constant of this dissociation step was represented by the expression k = 8 × 1012.e−55,000/RT sec−1. The activation energy of this reaction may be identified with D(C6H5CH2—COOH). The possible reactions of carboxyl radicals are discussed.


Gaseous oxidation phenomena show a great variety, since actions may take place both on the vessel wall and homogeneously, and reaction chains which may thus be set up are broken either in the gas phase or at the wall according to circumstances. With the object of extending the picture of these reactions, we have studied the oxidation of cyanogen, which, in several respects, exhibits a kind of behaviour quite different from that met with in the oxdiation of hydrogen, phosphine and various hydrocarbons. There is evidence of the formation on the vessel wall of activated carbon monoxide molecules, some of which are oxidised immediately to carbon dioxide, and the remainder of which are deactivated. The further oxidation of normal carbon monoxide is inhibited in a remarkable way by cyanogen. An explosion limit exists, but appears to be of a rather special kind, unlike the limits found in the oxidation of hydrogen, and phosphine, and depending on certain particular adsorption relationships.


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