Carbon activation energy

The activation energy for ro tation about a typical carbon-carbon double bond IS very high—on the order of 250 kj/mol (about 60 kcal/ mol) This quantity may be taken as a measure of the ir bond contribution to the to tal C=C bond strength of 605 kJ/mol (144 5 kcal/mol) in ethylene and compares closely with the value esti mated by manipulation of thermochemical data on page 191... 

Figure 10 12 shows the interaction between the HOMO of one ethylene molecule and the LUMO of another In particular notice that two of the carbons that are to become ct bonded to each other m the product experience an antibondmg interaction during the cycloaddition process This raises the activation energy for cycloaddition and leads the reaction to be classified as a symmetry forbidden reaction Reaction were it to occur would take place slowly and by a mechanism m which the two new ct bonds are formed m separate steps rather than by way of a concerted process involving a sm gle transition state... 

Decomposition. Acetaldehyde decomposes at temperatures above 400°C, forming principally methane and carbon monoxide [630-08-0]. The activation energy of the pyrolysis reaction is 97.7 kj/mol (408.8 kcal/mol) (27). There have been many investigations of the photolytic and radical-induced decomposition of acetaldehyde and deuterated acetaldehyde (28—30). 

Fig. 8. Variation of activation energy with kinetic molecular diameter for diffusion in 4A 2eohte (A), 5A 2eohte (0)> carbon molecular sieve (MSC-5A) (A). Kinetic diameters are estimated from the van der Waals co-volumes. From ref. 7. To convert kj to kcal divide by 4.184.

The activation energy for burning from a coked zeoHte has been reported as 109 kj/mol (29) and 125 kj/mol (30 kcal/mol) has been found for coke burning from a H-Y FCC catalyst. Activation energies of 167 kJ/mol (40 kcal/mol) (24) and 159 kJ/mol (25) have been reported for the burning of carbon from a coked amorphous siUca-alumina catalyst. 

Fig. 6. The three ideal zones (I—III) representing the rate of change of reaction for a porous carbon with increasing temperature where a and b are intermediate zones, is activation energy, and -E is tme activation energy. The effectiveness factor, Tj, is a ratio of experimental reaction rate to reaction rate which would be found if the gas concentration were equal to the atmospheric gas concentration (80).

Endotliermic Decompositions These decompositions are mostly reversible. The most investigated substances have been hydrates and hydroxides, which give off water, and carbonates, which give off CO9. Dehydration is analogous to evaporation, and its rate depends on the moisture content of the gas. Activation energies are nearly the same as reaction enthalpies. As the reaction proceeds in the particle, the rate of reaction is impeded hy resistance to diffusion of the water through the already formed product. A particular substance may have sever hydrates. Which one is present will depend on the... 

In tire transition-metal monocarbides, such as TiCi j , the metal-rich compound has a large fraction of vacairt octahedral interstitial sites and the diffusion jump for carbon atoms is tlrerefore similar to tlrat for the dilute solution of carbon in the metal. The diffusion coefficient of carbon in the monocarbide shows a relatively constairt activation energy but a decreasing value of the pre-exponential... 

The value of the activation energy approaches 50000 near the stoichiometric composition. This diffusion process therefore approximates to the selfdiffusion of metals at stoichiometty where the vacancy concentration on the carbon sub-lattice is small. 

Kisamori, S., Kuroda, K., Kawano, S., Moehida, 1., Matsumura, Y. and Yoshikawa, M., Oxidative removal of SO2 and recovery of H2SO4 over poly(acrylonitrile)-baacd active carbon fiber. Energy Fuels, 1994, 8(6), 1337 1340. 

NHj at room temperature over calcined active carbon fibers, Energy Fuels, 1995, 9(4), 659 664. 

Cal, M. P., Rood, M. J. and Larson, S. M., Gas phase adsorption of volatile organic compounds and water vapor on activated carbon cloth. Energy Fuels, 1997, 11(2), 311 315. 

A stronger bond between the nucleophilic atom and carbon is reflected in a more stable transition state and therefore a reduced activation energy. Since the 8 2 process is concerted, the strength of the partially formed new bond is reflected in the energy of the transition state. 

Huonne specifically weakens the carbon-carbon bond opposite the carbon atom beanng fluonne by about 4-5 kcal/mol per fluonne atom [ 25] It has been shown expenmentally that isomenzation of cir-l, l-difluoro-2,3-dimethylcyclopropane to the trans isomer has an activation energy )of 49 7 kcal/mol [126], which is about 10 kcal/mol lower than that of the parent hydrocarbon [127] (equation 26)... 

Sketch a potential energy diagram for rotation around a carbon-carbon bond in propane. Clearly identify each potential energy maximum and minimum with a structural formula that shows the conformation of propane at that point. Does your diagram more closely resemble that of ethane or of butane Would you expect the activation energy for bond rotation in propane to be more than or less than that of ethane Of butane ... 

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