Light-induced nitration pathways of phenols are important processes for the transformation of pesticide-derived secondary pollutants into toxic derivatives in surface waters and for the formation of phytotoxic compounds in the atmosphere. Moreover, phenols can be used as ~·NO2 probes in irradiated aqueous solutions. This paper shows that the nitration of 4-chlorophenol (4CP) into 2-nitro-4-chlorophenol (NCP) in the presence of irradiated nitrate and nitrite in aqueous solution involves the radical ~·NO2. The experimental data allow exclusion of an alternative nitration pathway by ~·OH + ~·NO2. Quantum mechanical calculations suggest that the nitration of both phenol and 4CP involves, as a first pathway, the abstraction of the phenolic hydrogen by~·NO2, which yields HNO2 and the corresponding phenoxy radical. Reaction of phenoxyl with another ~·NO2 follows to finally produce the corresponding nitrated phenol. Such a pathway also correctly predicts that 4CP undergoes nitration more easily than phenol, because the ring C1 atom increases the acidity of the phenolic hydrogen of 4CP. This favours the H-abstraction process to give the corresponding phenoxy radical. In contrast, an alternative nitration pathway that involves~·NO2 addition to the ring followed by H-abstraction by oxygen (or by ~·NO2 or ~·OH) is energetically unfavoured and erroneously predicts faster nitration for phenol than for 4CP.
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