Effect of ionic dissociation of organic compounds on their rate of reaction with hydrogen atoms

1972 ◽  
Vol 76 (19) ◽  
pp. 2673-2679 ◽  
Author(s):  
P. Neta ◽  
Robert H. Schuler

Kinetic and analytical studies of the gaseous oxidation of aluminium trimethyl at ambient temperatures and at pressures well below those required for spontaneous ignition have shown that, in contrast to the oxidations of less electron-deficient metal alkyls, no peroxides can be detected and no volatile oxygenated organic compounds are formed. Methane, traces of hydrogen and a solid methoxymethyl compound of aluminium are the only products. The initial rate of reaction is approximately proportional to the first power of the alkyl pressure and to the square of the oxygen pressure; it is little influenced by temperature or by inert gases but is lowered by an increase in surface. The observed kinetic and analytical results can be accounted for in terms of a free radical chain mechanism in which termination takes place predominantly at the walls.


Author(s):  
James Wei

After searching the literature and making predictions based on theory without getting sufficient satisfactory results, the next move would be to make estimates. We need the property y of substances pi from a population P that has not been investigated and reported in the literature. Fortunately, there exists a subset S of P that has been investigated, and we have the values for the property y. For instance, we may want the boiling points of all the hydrocarbons, but we have only the boiling points of the normal paraffins from 1 to 20 carbon atoms. Can we use this piece of information on normal paraffins to estimate the boiling points for the rest of the hydrocarbon population? How much effort would be involved and how accurate would the results be? The number of isomers of paraffin is very large; see table 5.1. We see that the iso-paraffins are not as well investigated as the normal paraffins. We have the boiling points of all three isomers of pentane, but not the 75 isomers of decane. It is inevitable that we have to resort to estimations. When we have obtained a good correlation for normal paraffins, we would naturally want to know if we can extend this to the branched paraffins, and onward to the population of all the saturated hydrocarbons (by including the cyclic paraffins), and onward to the population of all hydrocarbons (by including olefins, acetylenes, and aromatic compounds), and then onward to the population of all organic compounds (by including compounds with heteroatoms, such as O, N, Cl). A correlation that applies accurately to a larger domain is more useful than one that works only for a smaller domain. Another example is polychlorinated biphenyls (PCBs), which have 10 hydrogen atoms that can be substituted by chlorine atoms. There are three types of site: the four α sites near the bridge between the two phenyl fragments, the four β sites farther away from the bridge, and the two γ sites that are the farthest away from the bridge. The number of isomers is shown in table 5.2.


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