Journal of Supercritical Fluids, Vol.72, 22-27, 2012
In situ Raman spectroscopic study of hydrolysis of carbon tetrachloride in hot compressed water in a fused silica capillary reactor
The uncatalyzed hydrolysis of carbon tetrachloride (CCl4) in hot compressed water (HCW) in a fused silica capillary reactor (FSCR) was investigated with in situ Raman spectroscopy at reaction temperatures up to 300 degrees C. The phase behavior of CCl4 in water during heating at 34.1-260.0 degrees C was observed by a microscope, and images were recorded with a digital camera. The phase phenomena showed that the CCl4 gasified between 231.3 and 260.0 degrees C during the heating process. The hydrolysis was monitored by tracking the in situ vapor-phase Raman signals for CCl4 and product CO2. Increases in the CO2 Raman peak area over time were correlated to the hydrolysis yield. The quenched liquid products were analyzed by gas chromatography-mass spectrometry and ion chromatography, and the results indicated that the only hydrolysis products were HCl and CO2. The effect of the gasified CCl4 initial concentration (0.076-0.145 g/cm(3)), CCl4(1):H2O(1) volume ratio (1:2, 1:6, 1:10), and reaction temperature (240-300 degrees C) on the hydrolysis rate was investigated. The CC1.4 hydrolysis in the FSCR was found to be mainly a vapor phase reaction. Temperature was the prime determining factor for the hydrolysis rate. The CCl4 hydrolysis rate was also dependent on the initial concentration of vapor-phase CCl4 and the initial CCl4(1):H2O(1) volume ratio. The kinetics of CO2 formation was analyzed, and the result showed that it followed the first order with an activation energy of 95.06 +/- 6.71 kJ mol(-1). (c) 2012 Elsevier B.V. All rights reserved.