Reaction rates trapping

Regarding photocatalytic reaction rates, trapping is obviously favorable if (1) it helps charge separation (which is not always the case) (2) it permits storage of charges and (3) the trap sites are close to sites enabling transfer to adsorbates. 

Obviously, if the step in which T reacts is rate-controlling, then the overall reaction rate depends in some way upon the concentration and identity of T. This dependence may take the form of a direct proportionality to [T], but more complex forms have been given in the preceding paragraphs. If the reaction of an intermediate with a trap is faster than the step generating the intermediate, on the other hand, then the rate may not depend on either the concentration or the identity of the trap. If, for example, an organometal (RM) undergoes a slow, homolytic decomposition,... 

The effect of antioxidants such as hindered phenohcs, secondary amine, and thioester on the radiation cross-linking efficiency of LDPE has been reported [260]. Amount of cross-linking at a given dose decreases with aU the antioxidants, the thioester being the most effective. IR absorption spectroscopy has been used to demonstrate dose-rate dependence of trani -vinylene unsaturation in irradiated Marlex 50 PE [261]. When the irradiated polymer is stored in vacuum a decrease is observed in trani-vinylene absorbance over a period of several weeks. After high dose-rate irradiation the decay is preceded by an initial increase. These phenomena have been ascribed to the reaction of trapped radicals. 

In addition, the results of adsorption experiment in Fig. 4 revealed that H2O2 promotes the adsorption of 4-NP on the Cr-Ti-MCM-41 surface. From considering above results, it can be said that H2O2 increases the reaction rate by the promotion of adsorption of reactant and the removing of surface-trapped electrons. 

Other salts of formic acid have been used with good results. For example, sodium and preferably potassium formate salts have been used in a water/organic biphasic system [36, 52], or with the water-soluble catalysts discussed above. The aqueous system makes the pH much easier to control minimal COz is generated during the reaction as it is trapped as bicarbonate, and often better reaction rates are observed. The use of hydrazinium monoformate salts as hydrogen donors with heterogeneous catalysts has also been reported [53]. 

A big problem in asymmetric hydroformylation is that the chiral aldehyde products may be unstable and may undergo racemization during the reaction. This problem is even more serious for the Pt catalyst systems, which are usually plagued by slow reaction rates. Stille et al.121 tackled this problem by using triethyl orthoformate to trap the aldehyde products as their diethyl acetals and consequently increased the product ee values significantly. 

Several possible complications in the kinetic analysis were pondered and ruled out by the authors. For instance, they demonstrated that the direct reaction of the peroxide with P did not occur because a change of concentration of this radical trap did not affect the reaction rate. 

The ethylene bromonium and 1-bromoethyl cations and their neutral and anionic counterparts have been the subject of a tandem mass spectrometric study of dissociation and gas-phase redox reactions. IR and Raman studies of the bioactive bromonium cation (19), as its hydrogensulfate salt, agree with the results of an X-ray structure determination, and theoretical calculations are also in agreement, except for the details of the NO2 groups. The azaallenium ion (22) is an intermediate in the photolysis of (20) (21) and (22) could both be seen. Flash photolysis of (23) leads to (24), (25), and (26), all of which could be trapped by nucleophiles (27) was not an intermediate. NMR lineshape analysis of the spectmm of (28) leads to reaction rate constants of formation for both the intimate ion pair (29) and the solvent-separated ion pair (30). ... 

Micellar catalytic methods were used to operate a choice between these two mechanisms. When an ion-radical has a charge opposite to that of the micelle surface, it is trapped by the micelle (Okamoto et al. 2001). In the presence of a surface-active compound, the aromatic substrate is nitrated in the very depth of a micelle, and the reaction rate depends on the local concentration of the nitrating agent on phase boundaries between the micelle and solution. A positively charged... 

A kinetic study has been carried out in order to elucidate the mechanism by which the cr-complex becomes dehydrogenated to the alkyl heteroaromatic derivative for the alkylation of quinoline by decanoyl peroxide in acetic acid. The decomposition rates in the presence of increasing amounts of quinoline were determined. At low quinoline concentrations the kinetic course is shown in Fig. 1. The first-order rate constants were calculated from the initial slopes of the graphs and refer to reaction with a quinoline molecule still possessing free 2- and 4-positions. At high quinoline concentration a great increase of reaction rate occurs and both the kinetic course and the composition of the products are simplified. The decomposition rate is first order in peroxide and the nonyl radicals are almost completely trapped by quinoline. The proportion of the nonyl radicals which dimerize to octadecane falls rapidly with increase in quinoline concentration. The decomposition rate in nonprotonated quinoline is much lower than that observed in quinoline in acetic acid. 

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