Ionic equilibria associated with acidic protons present in HCl:ImCl (I
m+=-1-ethyl-3-methyl-H-1-imidazolium)ionic liquids (0.38 < HCI mole fr
action, X(HCl) < 0.67) have been investigated by H-1-NMR spectroscopy
(200 MHz, 297 K). We conclude that proton speciation in these liquids
is governed largely by the reaction H2Cl3- + Cl- half arrow right over
half arrow left 2HCl2-, for which the stoichiometric equilibrium cons
tant has been evaluated as 218 +/- 25; the concentration of molecular
HCl is small or negligible relative to that of the anionic species. Vi
rtually identical behavior was observed in an AlCl3:ImCl (AlCl3 mole f
raction = 0.35) ionic liquid. As in the case of the HCl:ImCl system, i
t was found that, maximally, 2 equiv of HCl (relative to available chl
oride ion) could be introduced into the AlCl3:ImCl liquid under ambien
t conditions. On the basis of these observations, and those of other w
orkers, we have constructed an approximate phase diagram for the terna
ry system HCl:ImCl:AlCl3 near ambient temperature and with HCI pressur
e less than 1 atm. Depending on the activity of Al2Cl7-, the behavior
of protic species in this system may range from that of a weak Lewis a
cid to that of a Bronsted superacid.