Influence of Ultrasonic Frequency on Swan Band Sono luminescence and Sonochemical Activity in Aqueous tert-Butyl Alcohol Solutions

The multibubble sonoluminescence (MBSL) spectra of t-BuOH aqueous solutions submitted to power ultrasound at 20, 204, 362, and 613 kHz show emissions for the Delta upsilon = -1 to Delta upsilon = +2 vibrational sequences of C-2* Swan system (d(3)pi g -> a(3)pi u). The Delta upsilon=+2 emission overlaps with the CH(AX) emission band. The maximal Swan band emission is observed when the MBSL of water itself is almost completely quenched. In general, MBSL is more intense at high-frequency compared to 20 kHz ultrasound. However, in the presence of Xe, the MBSL of C2* at 20 kHz is so bright that it can be seen by the unaided eye as a blue glow in the close vicinity of the ultrasonic tip. The intensity of the C2* band emission exhibits a maximum vs t-BuOH concentration: 0.1-0.2 M at 20 kHz and (18) x 10 (3) M at high-frequency ultrasound. Such a huge difference is attributed to a much smaller bubble size at high ultrasonic frequency or, in other words, to a much higher bubble surface/volume ratio providing more efficient saturation of the bubble interior with t-BuOH vapors and to the fact that high frequency bubbles remain active for many more cycles than 20 kHz ones, thus accumulating more hydrocarbon decomposition products. Simulation of the emission spectra using Specair software demonstrated the absence of thermal equilibrium for C-2* radicals (Tv > Tr), where Tv and Tr are the vibrational and the rotational temperature, respectively. In Ar, T-v decreases with increasing t-BuOH concentration reaching a steady value in the concentration domain that corresponds to C2* emission maximum intensity. In the presence of Xe an extremely high T-v is obtained, which is explained by the relatively low ionization potential of Xe providing a higher electron temperature of nonequilibrium plasma generated during bubble collapse. Analysis of the gaseous products of t-BuOH sonolysis reveals a significant sonochemical activity even at high t-BuOH concentration when MBSL is totally quenched, indicating that drastic conditions could be produced also within nonsonoluminescing cavitation bubbles.