화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.113, No.1, 141-145, 2009
Determination of Arrhenius and Thermodynamic Parameters for the Aqueous Reaction of the Hydroxyl Radical with Lactic Acid
Lactic acid is a major component of the TALSPEAK process planned for use in the separation of trivalent lanthanide and actinide elements. This acid acts both as a buffer and to protect the actinide complexant from radiolytic damage. However, there is little kinetic information on the reaction of water radiolysis species with lactic acid, particularly under the anticipated process conditions of aerated aqueous solution at PH similar to 3, where oxidizing reactions are expected to dominate. Here we have determined temperature-dependent reaction rate constants for the reactions of the hydroxyl radical with lactic acid and the lactate ion. For lactic acid this rate constant is given by the following equation: In k(1) = (23.85 +/- 0.19) - (1120 +/- 54)/T, corresponding to an activation energy of 9.31 +/- 0.45 kJ mol(-1) and a room temperature reaction rate constant of (5.24 +/- 0.35) x 10(8) M-1 s(-1) (24.0 degrees C). For the lactate ion, the temperature-dependent rate constant is given by 1n k(2) = (24.83 +/- 0.14) - (1295 +/- 42)/T, for an activation energy of 10.76 +/- 0.35 kJ mol(-1) and a room temperature value of (7.77 +/- 0.50) x 10(8) M-1 s(-1) (22.2 degrees C). These kinetic data have been combined with autotitration measurements to determine the temperature-dependent behavior of the lactic acid pK(a) value, allowing thermodynamic parameters for the acid dissociation to be calculated as Delta H degrees = -10.75 +/- 1.77 kJ mol(-1), Delta S degrees = -103.9 +/- 6.0 J K-1 mol(-1) and Delta G degrees = 20.24 +/- 2.52 kJ mol(-1) at low ionic strength.