Rate constants counterion

Further evidence for an increased efficiency of complexation in the presence of micellar aggregates with bivalent metal counterions is presented in Table 5.4. The apparent rate constants of the reaction of 5.1c with 5.2 in the presence of micelles of Co(DS)2, Ni(DS)2, Cu(DS)2 and Zn(DS)2 are compared to the rate constants for the corresponding bivalent metal ion - dienophile complexes in the absence of micelles. The latter data are not dependent on the efficiency of the formation of the catalyst - dienophile complex whereas possible incomplete binding will certainly be reflected in the former. The good correlations between 1 and and the absence of a correlation between and... 

Calculations usirig this value afford a partition coefficient for 5.2 of 96 and a micellar second-order rate constant of 0.21 M" s" . This partition coefficient is higher than the corresponding values for SDS micelles and CTAB micelles given in Table 5.2. This trend is in agreement with literature data, that indicate that Cu(DS)2 micelles are able to solubilize 1.5 times as much benzene as SDS micelles . Most likely this enhanced solubilisation is a result of the higher counterion binding of Cu(DS)2... 

Here AX is the acetyl compound (acetyl chloride or acetic anhydride), N is N-methylimidazole, I is the intermediate (presumably A -acetyl-A -methylimidazo-lium ion), X is the counterion (chloride or acetate), and ROH is the acetyl acceptor (alcohol or water). A general treatment of Scheme XXIII requires specification of the detailed nature of and k[ and is probably too complicated to be of practical use. However, several important special cases may arise from the operation of the ratio kxlk x, the behavior of apparent rate constants k /. and k, the relative magnitudes of k / and k, the relative concentrations of the reactants, the method of observation, and the nature of ROH. These cases are outlined in Scheme XXIV. 

Fig. 2. Arrhenius plots of the rate constants of the anionic polymerization of methyl methacrylate in THF as the solvent and with Na+ orCs+ as the counterion. (R. Kraft, A. H. E. Muller, V. Warzelhan, H. Hocker, G. V. Schulz, Ref.35>)...

Other investigations include the effect of solvent, counterion, temperature, lig-and/catalyst ratio, and the presence of monomer and copper(II) complexes on the activation rate constant [133,134,135,136,137,138,139],... 

The situation is different for reactions of very hydrophilic ions, e.g. hydroxide and fluoride, because here overall rate constants increase with increasing concentration of the reactive anion even though the substrate is fully micellar bound (Bunton et al., 1979, 1980b, 1981a). The behavior is similar for equilibria involving OH" (Cipiciani et al., 1983a, 1985 Gan, 1985). In these systems the micellar surface does not appear to be saturated with counterions. The kinetic data can be treated on the assumption that the distribution between water and micelles of reactive anion, e.g. Y, follows a mass-action equation (9) (Bunton et al., 1981a). 

The question then becomes that of the significance of the ion-exchange and mass-law equations which successfully account for the dependence of micellar rate constants upon the concentrations of surfactant and reactive and inert counterions. It seems reasonable to continue to use these descriptions at the present time, despite uncertainties as to the location of hydrophilic counterions at the micellar surface. 

Despite all these uncertainties the picture is reasonably self-consistent, in that calculated second-order rate constants in micelles are generally similar over wide ranges of surfactant and reagent concentration and are often little affected by changes in the micellar counterion. Examples are given in Tables 2-5. 

Fig. 20 A plot of the observed pseudo-first-order rate constants (kobs) for the methanolysis of HPNPP (4 x 10 5moldm ) as a function of [35 2Zn(II)] in the presence of 1 equivalent of added CH30 per complex giving jpH = 9.5, T = 25 + 0.1 °C. Dotted line is presented as a visual aid directed through all actual data collected at 280 nm ( ) or 320 nm (O) which are the wavelengths for disappearance of HPNPP and appearance of /j-nitrophenol solid line is a linear fit of the data corrected for inhibition by triflate counterions at 280 nm ( ) or 320 nm ( ). Reproduced with permission from ref. 95.

Table II. Rate Constants of the of the Adsorpt Counterion ion/Desorption...

The rate constants for the reaction of a pyridinium Ion with cyanide have been measured in both a cationic and nonlonic oil in water microemulsion as a function of water content. There is no effect of added salt on the reaction rate in the cationic system, but a substantial effect of ionic strength on the rate as observed in the nonionic system. Estimates of the ionic strength in the "Stern layer" of the cationic microemulsion have been employed to correct the rate constants in the nonlonic system and calculate effective surface potentials. The ion-exchange (IE) model, which assumes that reaction occurs in the Stern layer and that the nucleophile concentration is determined by an ion-exchange equilibrium with the surfactant counterion, has been applied to the data. The results, although not definitive because of the ionic strength dependence, indicate that the IE model may not provide the best description of this reaction system. 

The propagation rate constant and the polymerization rate for anionic polymerization are dramatically affected by the nature of both the solvent and the counterion. Thus the data in Table 5-10 show the pronounced effect of solvent in the polymerization of styrene by sodium naphthalene (3 x 1CT3 M) at 25°C. The apparent propagation rate constant is increased by 2 and 3 orders of magnitude in tetrahydrofuran and 1,2-dimethoxyethane, respectively, compared to the rate constants in benzene and dioxane. The polymerization is much faster in the more polar solvents. That the dielectric constant is not a quantitative measure of solvating power is shown by the higher rate in 1,2-dimethoxyethane (DME) compared to tetrahydrofuran (THF). The faster rate in DME may be due to a specific solvation effect arising from the presence of two ether functions in the same molecule. 

For any specific type of initiation (i.e., radical, cationic, or anionic) the monomer reactivity ratios and therefore the copolymer composition equation are independent of many reaction parameters. Since termination and initiation rate constants are not involved, the copolymer composition is independent of differences in the rates of initiation and termination or of the absence or presence of inhibitors or chain-transfer agents. Under a wide range of conditions the copolymer composition is independent of the degree of polymerization. The only limitation on this generalization is that the copolymer be a high polymer. Further, the particular initiation system used in a radical copolymerization has no effect on copolymer composition. The same copolymer composition is obtained irrespective of whether initiation occurs by the thermal homolysis of initiators such as AIBN or peroxides, redox, photolysis, or radiolysis. Solvent effects on copolymer composition are found in some radical copolymerizations (Sec. 6-3a). Ionic copolymerizations usually show significant effects of solvent as well as counterion on copolymer composition (Sec. 6-4). 

Despite the sometimes impressive reaction rate enhancements, second-order rate constants for most bimolecular reactions involving counterions actually decrease,with just a few remaining virtually constant or increas-ing. As discussed (vide supra), micellar rate constants for (pseudo) unimole-cular reactions are frequently lower than rate constants in water. Many of the... 

As the reasons for rate retardations have been discussed for pseudounimolecular probe reactions already, we focus on the reported increased bimolecular rate constants. Two main reasons for increases in bimolecular rate constants come to the fore (1) dehydration of the reactive counterions and (2) charge delocalization during the activation process leading to the transition state. An intriguing third reason (although, admittedly, not strictly equating to an increased bimolecular rate constant) is (3) the increase in local counterion concentration as a result of comoving counterions. We will discuss these three effects in order. 

Fig. 10 Concentration dependence of the pseudo first-order rate constants in a 100 mM phosphate buffer at pH 7.5 and 37 °C for a niunber of surface active betaine esters with hydrophobic tails of different sizes. For comparison, the rate constant for a non-siuface active compound (ethyl betainate) is included, (o) Oleyl betainate, ( ) tetradecyl be-tainate, ( ) dodecyl betainate, ( ) decyl betainate, (0) ethyl betainate. All compounds have chloride counterions...

Kinetic measurements were performed at several concentrations [C] of living ends for a given counterion, at a fixed temperature. The values of the apparent propagation rate constant ... 

Figure I. Linear dependence of the apparent bimolecular rate constant of living polypropylene sulfide propagation on the fraction of free ions a with Na + [222] as counterion at -30°C in THF ( ) in THP (V) with fBNa + [222] in...

Rate Constants of Formation and of Propagation of T)x in Toluene at Room Temperature, with Li+ + [211] as Counterion... 

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