High activation energy

The simplest of all Diels-Alder reactions cycloaddition of ethylene to 1 3 butadi ene does not proceed readily It has a high activation energy and a low reaction rate Substituents such as C=0 or C=N however when directly attached to the double bond of the dienophile increase its reactivity and compounds of this type give high yields of Diels-Alder adducts at modest temperatures... 

This situation seems highly probable for step-growth polymerization because of the high activation energy of many condensation reactions. The constants for the diffusion-dependent steps, which might be functions of molecular size or the extent of the reaction, cancel out. 

The detailed mechanism of battery electrode reactions often involves a series of chemical and electrochemical or charge-transfer steps. Electrode reaction sequences can also include diffusion steps on the electrode surface. Because of the high activation energy required to transfer two electrons at one time, the charge-transfer reactions are beheved to occur by a series of one electron-transfer steps illustrated by the reactions of the 2inc electrode in strongly alkaline medium (41). 

The solutions are most stable above pH 11 where the decomposition rate is nearly independent of pH. In this region, the decomposition rate has a second-order dependence on the concentration of hypochlorite. It also increases with increa sing ionic strength. Thus concentrated solutions decompose much faster than dilute solutions. Because of an unusually high activation energy, the decomposition rate increases greatiy with temperature. Nevertheless, solutions with less than about 6% available chlorine and a pH above 11 have acceptable long-term stabiUty below about 30°C. 

This particular reaction has quite a high activation energy, which suggests that a nonconcerted mechanism might be involved. An alternative explanation for the observed stereochemistry has been advanced. 

The relatively low rate and high activation energy noted for entry 32 also reflect a stereoelectronic effect. The preference for delocalization at the radical center requires... 

No proton transfers were observed in linear oligomers (catemers) of pyrazoles 8 in the solid, a fact which was understandable because such rearrangements would require a very high activation energy [97JCS(P2)101]. A possible exception to this rule is a catemer 8f, for which slow proton transfer was observed in the solid state [97JCS(P2)1867]. 

Considering the irreversibility of the reactions discussed above and the relatively harsh reaction conditions required (and hence the high activation energies of the processes), these transformations cannot be considered tautomeric processes. 

Compared with uncatalyzed reactions, catalysts introduce alternative pathways that, in nearly all cases, involve two nr more consecutive reaction steps. Each of these steps has a lower activation energy than does the uncatalyzed reaction. We can nse as an example the gas phase reaction of ozone and oxygen atoms. In the homogeneons uncatalyzed case, the reaction is represented to occur in a single irreversible step that has a high activation energy ... 

Film formation In a few instances the temperature dependence of /p, the passive current, has been observed and high activation energies (46 to —84kJ/mol) have been obtained, indicating a large increase in rate as the temperature increases (see Table2.5). 

Yet the reaction is quite slow, even at high temperatures. Evidently the rate is controlled by a high activation energy. In fact, the practical use of reaction (19) depends upon the presence of a catalyst to provide a reaction path with a lower activation energy. The two important commercial methods for manufacture of H2S04 differ principally in the choice of catalyst for this step. 

We now understand why some spontaneous reactions do not take place at a measurable rate they have very high activation energies. A mixture of hydrogen and oxygen can survive for years the activation energy for the production of radicals is very high, and no radicals are formed until a spark or flame is brought into contact with the mixture. The dependence of the rate constant on temperature, its... 

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