A time-resolved laser photolysis broadband diode array experiment has been used to measure the absorption spectrum of the chlorine atom in aqueous solution formed after excimer laser photolysis of chloroacetone and hypochlorous acid at λ = 248 nm. Laser photolysis-long path laser absorption at λ = 325 nm (He/Cd) was then applied to determine the rate coefficients for the reactions of the chlorine atom at T = 298 K with methanol, k₁ = (1.0 ± 0.1)·10⁹ M⁻¹ s⁻¹; ethanol, k₂ = (2.2 ± 0.3)·10⁹ M⁻¹ s⁻¹; 1-propanol, k₃ = (2.2 ± 0.4)·10⁹ M⁻¹ s⁻¹; 2-propanol, k₄ = (3.2 ± 0.7)·10⁹ M⁻¹ s⁻¹; tert-butanol, k₅ = (1.5 ± 0.1)·10⁹ M⁻¹ s⁻¹; diethyl ether, k₆ = (1.3 ± 0.1)·10⁹ M⁻¹ s⁻¹; methyl-tert-butyl ether, k₇ = (1.3 ± 0.1)·10⁹ M⁻¹ s⁻¹; tetrahydrofuran, k₈ = (2.6 ± 0.4)·10⁹ M⁻¹ s⁻¹; acetone, k₉ = (7.8 ± 0.7)·10⁷ M⁻¹ s⁻¹; formic acid, k₁₀ = (2.8 ± 0.3)·10⁹ M⁻¹ s⁻¹; acetic acid, k₁₁ = (1.0 ± 0.2)·10⁸ M⁻¹ s⁻¹; 2-butanol, k₁₂ = (5.0 ± 0.6)·10⁹ M⁻¹ s⁻¹; 2-butanone, k₁₃ = (2.4 ± 0.3)·10⁸ M⁻¹ s⁻¹; hydrated formaldehyde, k₁₄ = (1.4 ± 0.3)·10⁹ M⁻¹ s⁻¹; propionic acid, k₁₅ = (1.2 ± 0.3)·10⁹ M⁻¹ s⁻¹; isobutyric acid, k₁₆ = (1.7 ± 0.3)·10⁹ M⁻¹ s⁻¹; trichloromethane, k₁₇ = (2.3 ± 0.5)·10⁸ M⁻¹ s⁻¹ and dichloromethane, k₁₈ = (9.3 ± 0.3)·10⁶ M⁻¹ s⁻¹. A correlation between the rate constants at T = 298 K for all oxygenated hydrocarbons and the bond dissociation energy of the weakest C–H bond oflog k_H/l mol⁻¹ s⁻¹ = (29 ± 9) − (5 ± 2)·10⁻² BDE/kJ mol⁻¹(n = 18, r = 0.88) is derived. From temperature dependent measurements (temperature range from 288 to 328 K) the following Arrhenius expressions were derived:k₁ (Cl + CH₃OH) = (7.9 ± 0.3)·10¹⁴ exp[−(4.1 ± 0.7)·10³ K/T] l mol⁻¹ s⁻¹E_a = 34 ± 6 kJ mol⁻¹k₂ (Cl + CH₃CH₂OH) = (4.6 ± 0.4)·10¹² exp[−(2.7 ± 0.9)·10³ K/T] l mol⁻¹ s⁻¹E_a = 19 ± 7 kJ mol⁻¹k₃ (Cl + CH₃CH₂CH₂OH) = (5.0 ± 0.4)·10¹² exp[−(2.3 ± 0.8)·10³ K/T] l mol⁻¹ s⁻¹E_a = 19 ± 7 kJ mol⁻¹k₄ (Cl + CH₃CH(OH) CH₃) = (2.8 ± 0.3)·10¹³ exp[−(3.3 ± 1.2)·10³ K/T] l mol⁻¹ s⁻¹E_a = 23 ± 8 kJ mol⁻¹k₁₀ (Cl + HCOOH) = (8.9 ± 1.4)·10¹² exp[−(2.8 ± 1.1)·10³ K/T] l mol⁻¹ s⁻¹E_a = 20 ± 6 kJ mol⁻¹k₁₁ (Cl + CH₃COOH) = (1.3 ± 0.1)·10¹⁵ exp[−(4.9 ± 1.4)·10³ K/T] l mol⁻¹ s⁻¹E_a = 41 ± 11 kJ mol⁻¹k₁₄ (Cl + HCHO) = (4.7 ± 0.3)·10¹³ exp[−(3.9 ± 0.9)·10³ K/T] l mol⁻¹ s⁻¹E_a = 26 ± 6 kJ mol⁻¹k₁₅ (Cl + CH₃CH₂COOH) = (6.4 ± 0.6)·10¹⁶ exp[−(9.8 ± 2.2)·10³ K/T] l mol⁻¹ s⁻¹E_a = 44 ± 10 kJ mol⁻¹k₁₆ (Cl + CH₃CH(CH₃) COOH) = (5.7 ± 0.3)·10¹³ exp[−(3.8 ± 0.6)·10³ K/T] l mol⁻¹ s⁻¹E_a = 26 ± 4 kJ mol⁻¹A regression for the measured activation energies as a function of the bond dissociation energies (BDE) of the weakest C–H bond yields E_a = (0.8 ± 0.3) BDE/kJ mol⁻¹ − (300 ± 100). The effects of ionic strength (I_eff) on the reactions of chlorine atom with methanol and hydrated formaldehyde were also investigated. A decrease of the rate constant with increasing I_eff was found. All the errors stated throughout this work are statistical errors for a confidence interval of 95%.