Surface second harmonic generation (SSHG) has been used to study
the two successive acid/base equilibria
of eosin B at the air/water interface. Surface tension
measurements have shown that the neutral and
anionic forms of eosin B are not surface-active. Nevertheless,
SSHG was able to follow the appearance
and the disappearance, as a function of the aqueous bulk pH, of the
three different species at the interface
despite the low number of molecules per unit surface present there.
The two surface
values were
measured at
= 4.0 and
= 4.2, and both were found to be shifted to larger values as
compared
to the corresponding ones measured by UV−vis spectroscopy in aqueous
bulk solution, at pK
a1 = 2.2 and
pK
a2 = 3.7, respectively. These values
indicate that the neutral and the monoanionic forms of eosin B
are
favored at the interface compared to the monoanionic and the dianionic
forms, respectively. A wavelength
analysis of the SH response of the dianionic form of eosin B at this
interface suggests a lower hydration
of the molecule at the air/water interface compared to the bulk
solution, in agreement with the observed
smaller stabilization of the charged species at the interface. The
interfacial orientation has been measured
for the doubly-charged and neutral forms of eosin B and found at 33°
and 31°, respectively.
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