Kinetics and mechanism of para-chlorophenol photoconversion with the presence of nitrite in ice.

The photochemistry of para-chlorophenol (4-CP) under UV irradiation by using a 125-W high-pressure mercury lamp as light source with the presence of nitrite in a solid water ice matrix had been studied. The experiments were carried out in a photochemical cold chamber reactor at −14 to −12°C. Each influence factor of the 4-CP photoconversion kinetics in the water ice was inspected. The results show that the 4-CP photoconversion obeys the first-order kinetics model and the initial concentration of 4-CP, the initial concentration of nitrite, pH value, light intensity, inorganic ions and the water quality all have significant influence on the photoconversion rate. In addition, nine intermediate products were characterized by GC–MS, HPLC–ESI-MS and HPLC techniques and the possible photoconversion mechanism was proposed accordingly. It is concluded that the mechanism and photoproducts of 4-CP photolysis in ice are changed due to the presence of NO2−.