Resonance-enhanced multiphoton ionization
time-of-flight mass spectrometry
(REMPI-TOFMS) was used to study the characteristic signal behaviors
obtained from two types of emulsions: water-in-oil (W/O) and oil-in-water
(O/W). All emulsions were prepared using phase inversion emulsification,
i.e., a solution for an aqueous phase was added dropwise to an oil
phase with constant stirring to obtain an emulsion. Toluene served
as a detection component. When using REMPI-TOFMS to measure an emulsion,
a time profile for the target component can be constructed by plotting
peak areas for the corresponding component on a series of mass spectra.
In the case of a W/O emulsion at a water volume fraction (f
w) of 0.005, the concentration of toluene was
instantaneously decreased due to the existence of water droplets,
and therefore, several negative spikes were detected on the time profile
while establishing a baseline. In the case of a W/O emulsion at f
w = 0.3, negative peaks consisting of several
plots appeared on the time profile because of the formation of aggregates
of water droplets while the emulsion was flowed through a capillary
column for sample introduction. An O/W emulsion at f
w = 0.995 was analyzed following phase inversion, and
positive peaks were detected due to the aggregates of many oil droplets.
In this manner, the direct mass analysis of emulsions before and after
phase inversion was achieved, and the resultant signal inversion was
confirmed via REMPI-TOFMS.
In this study, we used a quantitative analytical method
to indicate
creaming behavior in an emulsion. An oil-in-water emulsion was directly
measured by resonance-enhanced multiphoton ionization time-of-flight
mass spectrometry, and the time profiles of the peak areas of an oil
component, styrene, were obtained at heights of 1, 2, and 3 cm from
the bottom of a sample that had a height of 4 cm. All time profiles
roughly indicated that the signal intensity increased once, then decreased,
and finally settled. Moreover, we proposed a fitting equation for
the time profiles by subtracting two sigmoid functions, whereby the
degree of the signal increases at the initial stage, the degree of
the signal decreases after the increase, and the times for continuing
the higher signal intensities were all longer as the monitoring positions
were raised. This method would surely provide useful information about
emulsions that undergo creaming behavior.
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