Indicators salt effects

Turning the argument around reactions that do not involve proton transfer steps will only experience a significant effect of the Lewis acids if a direct interaction exists between catalyst and reactant. The conventional Diels-Alder reaction is a representative of this class of reactions. As long as monodentate reactants are used, the effects of Lewis acids on this reaction do not exceed the magnitude expected for simple salt effects, i.e. there are no indications for a direct interaction between Lewis-acid and substrate. 

The indicator method is especially convenient when the pH of a weU-buffered colorless solution must be measured at room temperature with an accuracy no greater than 0.5 pH unit. Under optimum conditions an accuracy of 0.2 pH unit is obtainable. A Hst of representative acid—base indicators is given in Table 2 with the corresponding transformation ranges. A more complete listing, including the theory of the indicator color change and of the salt effect, is also available (1). 

The existence of the primary and secondary salt effects indicates the importance of maintaining control over ionic strength in kinetics studies. One may choose to keep the ionic strength low so as to minimize its effects, or one may make a series of measurements at various ionic strengths in order to permit extrapolation to the limit of infinitely dilute solution. Another useful alternative is to maintain the ionic strength constant at a value that is suffi-... 

Salt effects in kinetics are usually classified as primary or secondary, but there is much more to the subject than these special effects. The theoretical treatment of the primary salt effect leans heavily upon the transition state theory and the Debye-Hii ckel limiting law for activity coefficients. For a thermodynamic equilibrium constant one should strictly use activities a instead of concentrations (indicated by brackets). 

Surface-active crown ethers are distinctly differ from usual type of nonionics in salt effect on the aqueous properties, due to the selective complexing ability with cations depending on the ring size of the crown. As shown in Figure 3 (22), the cloud point of the crowns is selectively raised by the added salts. This indicates that the degree of cloud point increase is a measure of the crown-complex stability in water (23). 

Available information on DEHPA indicates an effect of salt concentration similar to that shown for the carboxylic acids [17]. Figure 7.11 indicates a significant difference between sodium and ammonium salts and solutions containing sodium and ammonium hydroxides. Moreover, below about 5 wt% salt concentration, the solubility becomes uneconomic. However, all the data given in Fig. 7.11 are for alkaline systems. For acid systems... 

Data have been presented for five salts in methanol-water solutions, which indicate clearly the influence of salt concentration on the observed salt effects and the Wilson parameters. 

An examination of Figures 1-6 indicates that Equation 1 is valid under conditions of constant x for potassium, ammonium, and tetramethylammonium bromides in ethanol-water mixtures. All three salts show an ability to salt out ethanol from these mixtures (i.e., increase its concentration in the equilibrium vapor) which is verified by their k values shown in Table XVIII. Also, the results for tetra-n-propylammonium bromide and tetra-n-butylammonium bromide in ethanol-water mixtures reveal that Equation 1 can be used to predict the salt effects of these systems however, these two salts demonstrate a propensity to salt in ethanol (i.e., decrease its vapor concentration) in ethanol-water mixtures. On the other hand, Figures 7-9 and the data in Table XVIII reveal that Equation 1 cannot be used to correlate the salt effects of tetraethylammonium bromide in ethanol-water. For this system, a linear dependence of log aja vs. z is observed initially however, a gradual levelling off occurs at higher concentrations. 

A long series on the kinetics and mechanism of the unimolecular heterolysis of commercial haloorganic compounds has continued in a study of the effect of bromide salts and lithium perchlorate on the ionization rate of benzhydryl bromide in y-butyrolactone and acetone.122 The verdazyl indicator method was applied. The nature of special and normal salt effects has also been discussed.123... 

Positive kinetic salt effects indicate that these reactions proceed by mechanism SE2(open). Product analyses indicate that these reactions proceed by mechanism SE2(open). 

The equilibrium constants for the formation in water of the sulphite adducts of a number of nitro-compounds are given in Table 6. Where NMR studies have been carried out these indicate the formation of 1 1 and 1 2 adducts, addition occurring in each case at an unsubstituted ring position. The formation of the higher complexes is subject to a large salt effect and the values given for Kz are those extrapolated to zero ionic strength. 

---