Ionization Equilibria of Derivatives of Triphenylchloromethane in Liquid Sulfur Dioxide

THE STRUCTURE OF ARYLCARBONIUM IONS1

“…In solvents of lesser solvating power for positive ions, this effect should not be so pronounced. Thus Bartlett and Lichtin (6,7) found in contrast to our results that p-ferf-butyl groups increased the stability of the triphenylcarbonium. ion as measured by the extent of ionization of the carbinyl chlorides in liquid sulfur dioxide and nitromethane.…”

“…A result is that the J0 values from equation 6 can be used to determine the thermodynamic pKR+ values for carbinols from equation 2. In effect the change in activity coefficients that occur in going from water to the sulfuric acid concentration where the measurements are conducted is exactly counterbalanced by the same change in activity coefficients of the indicators used to set up the Ho scale. The values of pKB+ given in the Tables are thus thermodynamic pK values for equation 7 based on water as the standard state.…”

Ionization and dissociation of weak electrolytes. An initial approach to Ki and Kd evaluation

“…From eqs 2.4 and 8 and these calculating procedures, we have obtained the Kd isodielectric values for picric acid in Gliet/ Gliem solvent system in the range 20 < e < 40 (Table V); these values were well fitted by an empirical equation of the type Kd = SeUt (10) which has been chosen from a set of similar relations because (i) it provides the best fit, (ii) it is quite simple, and (iii) it is in good accord with observations mentioned above of Lichtin (8,24,25). This equation has, in its logarithmic form, a linear correlation coefficient r = 0.999, and the trend of Kd vs e is shown in Figure 2.…”

Solvolytic Displacement Reactions At Saturated Carbon Atoms

“…Electrical conductivity measures the amount of dissociated ions (428), whereas spectrophotometric methods measure the total amount of carbonium ion in ion-pairs and dissociated (41, 79). However, the measurements in nitroalkanes are greatly dependent on the purity of the solvent; hence the results should be considered as questionable (42a).…”