The Energy of Activation

Hawkins J M, Nambu M and Meyer A 1994 Resolution and configurational stability of the chiral fullerenes C-g, C g, and Cg. A limit for the activation energy of the Stone-Wales transformation J. Am. Chem. Soc. 116 7642-5... 

The rupture force measured in AFM experiments is given, therefore, by the average slope of the energy profile minus a correction related to the effects of thermal fluctuations. Equation (11) demonstrates that the rupture force measured in AFM experiments grows linearly with the activation energy of the system (Chilcotti et ah, 1995). A comparison of (10) and (11) shows that the unbinding induced by stiff springs in SMD simulations, and that induced by AFM differ drastically, and that the forces measured by both techniques cannot be readily related. 

The first term, the apparent activation energy of the encounter reaction, was evaluated from the temperature coefficient of the viscosity of sulphuric acid. 

It IS important to note that although methyl and primary alcohols react with hydro gen halides by a mechanism that involves fewer steps than the corresponding reactions of secondary and tertiary alcohols fewer steps do not translate to faster reaction rates Remember the order of reactivity of alcohols with hydrogen halides is tertiary > sec ondary > primary > methyl Reaction rate is governed by the activation energy of the slowest step regardless of how many steps there are... 

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). 

Oxidation. AH inorganic siUcon hydrides are readily oxidized. Silane and disilane are pyrophoric in air and form siUcon dioxide and water as combustion products thus, the soot from these materials is white. The activation energies of the reaction of silane with molecular and atomic oxygen have been reported (20,21). The oxidation reaction of dichlorosilane under low pressure has been used for the vapor deposition of siUcon dioxide (22). 

An estimate of the enthalpy change which conesponds to the activation energy of the collision theory analysis of 167kJmoP may be made by assuming that the formation of tire dimer from two molecules of the monomer is energetically equivalent to tire dipole-dipole and dispersion interactions of two HI molecules. These exothermic sources of interaction are counterbalanced... 

Enzymes increase the rate of chemical reactions by decreasing the activation energy of the reactions. This is achieved primarily by the enzyme preferentially binding to the transition state of the substrate. Catalytic groups of the enzyme are required to achieve a specific reaction path for the conversion of substrate to product. 

This mechanism can reduce the overall activation energy of the reaction in at least two ways. The partial transfer of a proton to the carbonyl oxygen increases the electrophilicity of the carbonyl. Likewise, partial deprotonation of the amino group increases its nucleophilicity. 

Lu and Pizzi [83] showed that lignocellulosic substrates have a distinct influence on the hardening behavior of PF-resins, whereby the activation energy of the hardening process is much lower than for the resin alone [84]. The reason is a catalytic activation of the PF-condensation by carbohydrates like crystalline and amorphous cellulose and hemicellulose. Covalent bonding between the PF-resin and the wood, especially lignin, does not play any role [84]. 

These results predict that the hydroxycarbene to formaldehyde reaction will proceed significantly more easily than the fonvard reaction. However, for this problem, electron correlation is needed for good quantitative values. For example, the MP4/6-31G(d,p) level predicts a value of 86.6 kcal mol" for the activation energy of the forward reaction. 

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. 

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