The optimal dose of oxidants in UV-based advanced oxidation processes with respect to primary radical concentrations

Misconceptions about the chemistry of aqueous chlorine atoms and HClOH˙(aq), and a revised mechanism for the photochemical peroxydisulfate/chloride reaction

“…11 Here we report an additional 37 publications that have mechanisms including this loop. 51,64,65,[67][68][69][70][71][81][82][83]85,[87][88][89][90][92][93][94][95]97,[99][100][101][102][103][104][105][106][108][109][110][111][112][113]118,119 In our previous report we showed that correcting Loop ''D'' by supplying the requisite value for the reverse rate constant in the first step had no effect on the simulations of the overall mechanism in one of the publications. This outcome was traced to the fact that the first step could be eliminated entirely without affecting the results of the simulation.…”

“…Two examples of published illegal loops involving HClOH˙ are discussed below. A total of 18 such illegal loops have been published, 10,18,20,21,23,26,27,30–33,35,39,40,46–118 and these are described in the ESI †…”

“…In addition to the 24 publications previously identified as having illegal Loop 7 (“E”), it also appears in 26 newly identified publications. 23,30,32,35,40,68,70,81,82,85,89,90,92,96,99–104,108–113,117,119 The rate constants in Xiang et al 2022 require a value of 5.7 × 10 11 M −1 s −1 for the reverse of the first step. 117 Simulations of Loop 7 (“E”) at pH 3 with 1 mM Cl − and 1 μM show that the steady-state concentration of HClOH˙ changes from 9.8 × 10 −14 M to 2.6 × 10 −10 M when the reverse rate constant of the first step is increased from zero to its required value.…”