Ionisation of Triphenylmethylbromide in Nitromethane
Dissolving triphenylmethylbromide in nitromethane leads to the formation of HBr which complicates conductivity and spectroscopic measurements of carbenium ion absorption. As a result of addition of bromide ions (as tetraethylammonium bromide = Et4NBr) the triphenylmethylabsorption totally disappeares. It can be concluded that Ph3CBr in nitromethane is partially present in form of free (solvated) ions. The carbenium ion concentration has been determined as a function of gross concentration and temperature.
Ionization and Dissociation of Triphenylmethyl Halides in Methylendichloride
The Winstein scheme is valid for triphenylmethyl halides in methylendichloride. The equilibrium of ionization and dissociaton has been determined by investigation of the ratio between the sum of concentrations of ionic species and the covalent form. Tritylbromide in methylendichloride shows an exothermic ionization but endothermic dissociation. In the case of tritylchloride ionization and dissociation are nearly independent on the temperature.
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