화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.102, No.35, 6927-6934, 1998
Chemical bubble dynamics and quantitative sonochemistry
We model the collapse of a bubble by taking into account all the energy forms involved (i.e., mechanical, thermal, chemical, and radiative) and compare the calculated radical yields with sonochemical data in H2O. Water decomposition plays a critical role in the energy balance, but trails equilibrium even in bubbles collapsing at subsonic speeds. Integration of the equation of bubble motion coupled with a full chemical mechanism reveals that (1) terminal gas temperatures and Mach numbers M-L increase in cooler water, (2) Gamma(OH), the number of OH-radicals produced per unit applied work at maximum M-L-when bubbles become unstable and disperse into the liquid-decreases at small and very large sound intensities. We show that available data on the sonochemical decomposition of volatile solutes-such as CCl4, which is pyrolyzed within collapsing bubbles-are compatible with the efficient conversion of ultrasonic energy into transient cavitation. On this basis we calculate Gamma(OH) = (1 +/- 0.5) x 10(17) molecules/J for R-0 = 2 mu m bubbles optimally sonicated at 300 kHz and 2.3 W/cm(2) by assuming mass and energy accommodation coefficients of alpha less than or equal to 7 x 10(-3) and epsilon less than or equal to 0.04, respectively, in gas-liquid collisions, and values about 3-fold smaller after averaging over the nuclei size distribution. Since there is negligible radical recombination during dispersal, these Gamma(OH) values represent available oxidant yields, that agree with experimental data on iodide sonochemical oxidation. Bubbles emit little radiation, suggesting that only radial shock waves may heat small regions to the 10(4)-10(5) K range required by some sonoluminescence experiments. The contribution of this sonoluminescent core to sonochemical action is, however, insignificant. We show that much larger accommodation coefficients would lead to higher temperatures, but also to O atoms rather than OH radicals and ultimately to excess O-2, at variance with experimental evidence.