Journal of Physical Chemistry B, Vol.106, No.48, 12537-12548, 2002
Adsorption of surfactants at the gas/solution interface of cavitation bubbles: An ultrasound intensity-independent frequency effect in sonochemistry
A major limitation in determining the effects of ultrasound frequency in sonochemistry in relation to cavitation is that no reliable relationship exists between the energy supplied to the system and the energy converted by the cavitation process in producing a sonochemical effect. However, the current study presents a frequency effect that is independent of the energy supplied to the system. Spin-trapping of secondary carbon radicals with 3,5-dibromo-4-nitrosobenzenesulfonic acid-d(2) (DBNBS-d(2)) and electron paramagnetic resonance (EPR) have been used to determine the relative ability of two nonvolatile surfactants [sodium 1-pentanesulfonic acid (SPSo) and sodium dodecyl sulfate (SDS)] to scavenge .H atoms and .OH radicals at the gas/solution interface of cavitation bubbles. The results obtained at 354 and 1057 kHz are compared to those observed previously at 47 kHz (Sostaric, J. Z.; Riesz, P. J. Am. Chem. Soc. 2001, 123, 11010-11019). At particular bulk surfactant concentrations, both surfactants reached a limiting plateau value in radical scavenging ability. At 354 kHz (and 47 kHz), the magnitude of this plateau was greater for SPSo compared to that for SDS. However, at 1057 kHz, no difference in the plateau value was observed between SPSo and SDS. Decreasing the ultrasound intensity at constant frequency during the sonolysis of SPSo and SDS resulted in a decrease in the -(CH)-C-.-radical yield. However, there was no change in the relative plateau yield of -(CH)-C-.- radicals between SPSo and SDS. Thus, at plateau concentrations, the relative ability of these n-alkyl chain surfactants to scavenge radicals at the gas/solution interface of cavitation bubbles depends on the frequency of sonolysis but is independent of ultrasound intensity. The results were interpreted in terms of a decrease in the rate of change of the surface area of "high-energy-stable cavitation bubbles" at higher frequencies. This would affect the relative adsorption and hence radical scavenging efficiencies of SPSo and SDS at the gas/solution interface of these types of cavitation bubbles.