Rate constants of chlorine atom reactions with organic molecules in aqueous solutions, an overview

Rate constants of chlorine atom (Cl^•) reactions (k_Cl•) determined using a large variation of experimental methods, including transient measurements, steady-state and computation techniques, were collected from the literature and were discussed together with the reaction mechanisms. The k_Cl• values are generally in the 10⁸-10⁹ mol^-1 dm³ s^-1 range when the basic reaction between the Cl^• and the target molecule is H-atom abstraction. When Cl^• addition to double bonds dominates the interaction, the k_Cl• values are in the 1 × 10⁹-2 × 10¹⁰ mol^-1 dm³ s^-1 range. In the k_Cl• = 1 × 10¹⁰-4 × 10¹⁰ mol^-1 dm³ s^-1 range, single-electron-transfer reactions may also contribute to the mechanism. The Cl^• reactions with organic molecules in many respects are similar to those of ^•OH, albeit Cl^• seems to be less selective as ^•OH. However, there is an important difference, as opposed to Cl^• in the case of ^•OH single-electron-transfer reactions have minor importance. The uncertainty of Cl^• rate constant determinations is much higher than those of ^•OH. Since Cl^• reactions play very important role in the emerging UV/chlorine water purification technology, some standardization of the rate constant measuring techniques and more k_Cl• measurements are recommended.