A Stopped-flow Study on the Kinetics and Mechanism of CO2 Uptake by the cis-[Cr(1,10-phenanthroline)2(OH2)2]3+ Complex Ion

Abstract

The kinetics of the reaction between gaseous CO2 and the cis-[Cr(phen)2(OH2)2]3+ ion leading to the formation of the carbonato complex ion, have been studied over the pH and temperature ranges: 3 < pH < 6 and 5 < T < 25 °C, respectively, at a constant ionic strength of 1 m (NaClO4). Investigations were carried out using the stopped-flow spectrophotometry technique in the UV–Vis range: 340–700 nm. The major reactant species in the pH range studied was cis-[Cr(phen)2(OH)(OH2)]2+ ion, which underwent reaction with CO2 to form cis-[Cr(phen)2(OH2)(HCO3)]2+ ion. Subsequently, slower ring closure of the latter species to form the bidentate carbonato chelate was observed. The possible mechanism has been discussed and the activation parameters ΔH† and ΔS† were also determined for the reaction studied.