Rate constant of base catalyzed

The Hammett substituent constant o is a measure of the electron-with-drawing capacity of substituents directly conjugated to the reaction center [84], Since the values of this parameter were obtained from the rate constants of base-catalyzed hydrolysis of other aryl esters, it can be concluded from Eqn. 8.5 that the same electronic factors are involved in both cases. 

This property of organophosphate esters may be of environmental importance since phosphoric acid diesters are much more soluble and very little is known concerning the environmental toxicity of these compounds. The available data do not provide sufficient descriptions of the experimental methods to determine if the rates are reliable (Barnard et al. 1961 Ciba-Geigy 1984e, 1986 Howard and Deo 1979 Mayer et al. 1981 Wolfe 1980). The majority of reports provide only a minimum of information and exclude important facts such as the duration of the experiments and the concentration of buffers. Despite the lack of experimental detail, published rate constants for base-catalyzed hydrolysis appear to be reasonably consistent and suggest that the hydrolytic half-life of triphenyl phosphate will vary from... 

Figure C. Rate constants for base-catalyzed hydrolysis of Si(acac)z+...

That the expression (fcHo[HO-] + fcgb[B])[CH] pertains to the rate of carbanion formation is established under conditions of high [Flox] when carbanion formation is rate determining. Under this condition, the rate constant for the flavin oxidation of dimethyl trans-1,2-dihydrophthalate to dimethyl phthalate is identical to the rate constant for base-catalyzed isomerization of the substrate to its 1,4-isomer (Equation 15) (8). This flavin oxidation serves as abiomimetic reaction... 

In principle, extrathermodynamic relationships that deviate from the simple Hammett equation (equation 8) can be treated by equation 14. The major problem is the determination of the different sets of o s, (e.g., set and 0 set) in a way that will indeed reflect their relation to independent properties. An example of such a procedure is the separation of polar and steric effects (10). The need for such a separation arose when a nearly complete lack of correlation was observed between substituent effects represented by the Hammet a constants and the rates for alkaline hydrolysis of aliphatic systems (12). Inspection of the structures indicated that the proximity of the substituents to the reaction site was a common feature. The steric interaction between R and X had to be considered separately from the electronic effects. Polar substituent constants were thus defined as the difference between the rate constants of base and acid catalyzed hydrolysis of esters. From the structural similarity of the transition states for these reactions (equation 15) it was assumed that the difference in their charge reflects only the polar effect of the substituent... 

Photoreactions of [Ru(bipy)3]Cl2 and of [Ru(phen)3]Cl2 in acetonitrile proceed more slowly as pressure increases. The activation volumes increase dramatically with temperature, from +12 and +9 cm mol respectively at 288 K to +22 and +27 at 333 K. These increases are ascribed to a key role for chloride ion pairs in these dissociatively activated reactions. Rate constants for base-catalyzed isomerization of the y to the p form of [Ru(azpy)2Cl2], azpy = (22), are not linear in hydroxide concentration, prompting speculation on the detailed role of hydroxide in this conversion.Rate constants for replacement of coordinated water in cis- and tra 5-[Ru(LL)2X(OH2)]" by acetonitrile span a range of nearly 2 X 10" times. Several factors have to be invoked to explain the observed trend in the effects of ligand X on the ease of replacement of the aqua-ligand. " The... 

Two factors could contribute to the observed regiochemistry of base-promoted halogenation of ketones. One is a kinetic preference for formation of the less substituted enolate. Evidence for this effect can be seen in the rate constants for base-catalyzed iodination of phenyl alkyl ketones with the structure C6H5COCHR1R2, which are found to decrease with increasing alkyl substitution (Table 7.8). ... 

Base-catalyzed hydrolysis in PET is important for fiber manufacture, because both organic and inorganic bases are used for dyeing, subsequent treatment, and during washing. The rate constant for base-catalyzed hydrolysis of dibasic esters is smaller than the acid hydrolysis constant, resulting in a higher stability of PET fibers in alkaline solutions than in acid solutions. 

The question about the relation between the reactivity of reactants and their structure is one of the fundamental problems of chemistry. This problem as one of the main directions of chemical kinetics was formulated in the general form about 100 years ago by N.A. Menshutkin in his works on hydrolysis of esters. One of the most important directions in this area is correlation equations relating the reaction rate constant to thermodynamic and structural parameters of reactants. The first correlation was proposed by Ch. Taylor (1914) who noticed a proportionality between the ionization rate constant of the catalyst and rate constant of the catalyzed reaction. The systematic work on correlations in chemical kinetics started from the works of J. BrSnsted and K. Pedersen who, using the results of their study of the reactions catalyzed by acids ( ha) and bases ( a), proposed the equations relating the rate constants of catalytic reactions to the dissociation constants of acids ituA (1924)... 

Based on the reaction scheme shown below, derive an expression for k /k, the ratio of the rate constants for the catalyzed and uncatalyzed reactions, respectively, in terms of the free energies of activation for the catalyzed (AGe ) and the uncatalyzed (AG ) reactions. 

H/D exchange of H and Hg protons of sulfone 86 and estimated the difference in the free energies of activation for 79a and 79b to be < 1.2 kcal mol , based on the kjk value of 3 0.5. In the base-catalyzed H/D exchange of 87, kjk = 1.6, where k and k are the rate constants of H/D exchange of H, and H, respectively. Based on the small kjk value. Brown and colleagues suggested that if the carbanion is pyramidal, the steric stabilities of 79a and 79b are almost identical. Meanwhile, based on their C-NMR study Chassaing and Marquet proposed that the hybridization of the carbon atom of the sulfonyl carbanion, PhSOjCHj , would be between sp and sp . 

The electrochemical rate constants for hydrogen peroxide reduction have been found to be dependent on the amount of Prussian blue deposited, confirming that H202 penetrates the films, and the inner layers of the polycrystal take part in the catalysis. For 4-6 nmol cm 2 of Prussian blue the electrochemical rate constant exceeds 0.01cm s-1 [12], which corresponds to the bi-molecular rate constant of kcat = 3 X 103 L mol 1s 1 [114], The rate constant of hydrogen peroxide reduction by ferrocyanide catalyzed by enzyme peroxidase was 2 X 104 L mol 1 s 1 [116]. Thus, the activity of the natural enzyme peroxidase is of a similar order of magnitude as the catalytic activity of our Prussian blue-based electrocatalyst. Due to the high catalytic activity and selectivity, which are comparable with biocatalysis, we were able to denote the specially deposited Prussian blue as an artificial peroxidase [114, 117]. 

For those systems where Ri = R2 = H or Ri = H, R2 = CH3, i.e. where the number of alkyl groups at C, is <1, and R3 = H to NO3, the alkoxynitroxyl radicals formed according to Eq. 7 under steady-state-ESR or pulse radiolysis conditions do not give rise to nitrobenzene radical anions. This means that the rate constants for heterolysis of the nitroxyls are < 10 s . This is not only true in weakly acidic (pH 4) or neutral but also in strongly alkaline solution (pH 13-14). The latter observation means that the nitroxyls are not susceptible to base catalyzed heterolysis. From this the rate constant for OH catalyzed decomposition can be estimated to be < 10 M s [19]. This low number for... 

The hydrolysis of pesticides which are sorbed to sterilized natural sediments has been investigated in aqueous systems at acid, neutral and alkaline pH s. The results show that the rate constants of pH independent ("neutral") hydrolyses are the same within experimental uncertainties as the corresponding rate constants for dissolved aqueous phase pesticides. Base-catalyzed rates, on the other hand, are substantially retarded by sorption and acid-catalyzed rates are substantially enhanced. A large body of evidence will be presented which substantiates these conclusions for a variety of pesticide types sorbed to several well-characterized sediments. The significance of our results for the evaluation of the effects of sorption on the degradation of pesticides in waste treatment systems and natural water bodies will also be discussed. 

---