Dn. Rassokhin et al., TEMPERATURE EFFECT ON THE SONOLYSIS OF METHANOL-WATER MIXTURES, Journal of the American Chemical Society, 117(1), 1995, pp. 344-347
Methanol/water mixtures with various concentrations of methanol (from
pure water to pure methanol) were exposed to ultrasonic irradiation (7
24 kHz, 50 W) under an argon atmosphere at various bulk temperatures l
ying in a range from -30 to +58 degrees C. It was shown that changing
the bulk temperature dramatically influenced the rate of the sonolytic
formation of molecular hydrogen. With increasing temperature, the rat
e initially grows, reaches a maximum, then falls. Increasing the conce
ntration of methanol in the mixture decreases the temperature at which
the maximal H-2 formation rate is reached. The observed effect is exp
lained in terms of two opposing factors, and relative contributions of
those factors change with the alteration of the bulk temperature: it
is suggested that saturating the cavitational bubbles with methanol va
pors as the temperature of the mixture being sonicated increases (1) o
n one hand, accelerates the methanol vapor thermolysis in the cavitati
onal hot spots during the collapse of the bubbles because methanol is
a reactant, but (2) on the other hand, decreases the local temperature
of the cavitational hot spots that, in turn, disfavor the thermolysis
. The effect of the bulk solution temperature on a constant methanol c
oncentration is compared with that of the concentration of methanol in
the mixture when a constant bulk solution temperature is kept.