Toward the understanding of chemical absorption processes for post-combustion capture of carbon dioxide: electronic and steric considerations from the kinetics of reactions of CO2(aq) with sterically hindered amines.

The present study reports (a) the determination of both the kinetic rate constants and equilibrium constants for the reaction of CO(2)(aq) with sterically hindered amines and (b) an attempt to elucidate a fundamental chemical understanding of the relationship between the amine structure and chemical properties of the amine that are relevant for postcombustion capture of CO(2) (PCC) applications. The reactions of CO(2)(aq) with a series of linear and methyl substituted primary amines and alkanolamines have been investigated using stopped-flow spectrophotometry and (1)H NMR measurements at 25.0 °C. The specific mechanism of absorption for each of the amines, that is CO(2) hydration and/or carbamate formation, is examined and, based on the mechanism, the kinetic and equilibrium constants for the formation of carbamic acid/carbamates, including protonation constants of the carbamate, are reported for amines that follow this pathway. A Brønsted correlation relating the kinetic rate constants and equilibrium constants for the formation of carbamic acid/carbamates with the protonation constant of the amine is reported. Such a relationship facilitates an understanding of the effects of steric and electronic properties of the amine toward its reactivity with CO(2). Further, such relationships can be used to guide the design of new amines with improved properties relevant to PCC applications.

Reactions of CO2 with aqueous piperazine solutions: formation and decomposition of mono- and dicarbamic acids/carbamates of piperazine at 25.0 °C.

Piperazine (PZ) is widely recognized as a promising solvent for postcombustion capture (PCC) of carbon dioxide (CO(2)). In view of the highly conflicting data describing the kinetic reactions of CO(2)(aq) in piperazine solutions, the present study focuses on the identification of the chemical mechanism, specifically the kinetic pathways for CO(2)(aq) in piperazine solutions that form the mono- and dicarbamates, using the analysis of stopped-flow spectrophotometric kinetic measurements and (1)H NMR spectroscopic data at 25.0 °C. The complete set of rate and equilibrium constants for the kinetic pathways, including estimations for the protonation constants of the suite of piperazine carbamates/carbamic acids, is reported here using an extended kinetic model which incorporates all possible reactions for CO(2)(aq) in piperazine solutions. From the kinetic data determined in the present study, the reaction of CO(2)(aq) with free PZ was found to be the dominant reactive pathway. The superior reactivity of piperazine is confirmed in the kinetic rate constant determined for the formation of piperazine monocarbamic acid (k(7) = 2.43(3) × 10(4) M(-1) s(-1)), which is within the wide range of published values, making it one of the faster reacting amines. The corresponding equilibrium constant for the formation of the monocarbamic acid, K(7), markedly exceeds that of other monoamines. Kinetic and equilibrium constants for the remaining pathways indicate a minor contribution to the overall kinetics at high pH; however, these pathways may become more significant at higher CO(2) loadings and lower pH values where the concentrations of the reactive species are correspondingly higher.

Toward rational design of amine solutions for PCC applications: the kinetics of the reaction of CO2(aq) with cyclic and secondary amines in aqueous solution.

The kinetics of the fast reversible carbamate formation reaction of CO(2)(aq) with a series of substituted cyclic secondary amines as well as the noncyclic secondary amine diethanolamine (DEA) has been investigated using the stopped-flow spectrophotometric technique at 25.0 °C. The kinetics of the slow parallel reversible reaction between HCO(3)(-) and amine has also been determined for a number of the amines by (1)H NMR spectroscopy at 25.0 °C. The rate of the reversible reactions and the equilibrium constants for the formation of carbamic acid/carbamate from the reactions of CO(2) and HCO(3)(-) with the amines are reported. In terms of the forward reaction of CO(2)(aq) with amine, the order with increasing rate constants is as follows: diethanolamine (DEA) < morpholine (MORP) ~ thiomorpholine (TMORP) < N-methylpiperazine (N-MPIPZ) < 4-piperidinemethanol (4-PIPDM) ~ piperidine (PIPD) < pyrrolidine (PYR). Both 2-piperidinemethanol (2-PIPDM) and 2-piperidineethanol (2-PIPDE) do not form carbamates. For the carbamate forming amines a Brønsted correlation relating the protonation constant of the amine to the carbamic acid formation rate and equilibrium constants at 25.0 °C has been established. The overall suitability of an amine for PCC in terms of kinetics and energy is discussed.

Kinetics of the reversible reaction of CO2(aq) with ammonia in aqueous solution.

The kinetics of the interactions of aqueous ammonia with aqueous carbon dioxide/carbonate species has been investigated using stopped-flow techniques by monitoring the pH changes via indicators. The reactions include the reversible formation of ammonium carbamate/carbamic acid. A complete reaction mechanism has been established, and the temperature dependence of all rate and equilibrium constants including the protonation constant of the amine between 15 and 45 °C are reported and analyzed in terms of Arrhenius, Eyring, and van't Hoff relationships.

Comprehensive kinetic and thermodynamic study of the reactions of CO2(aq) and HCO3(-) with monoethanolamine (MEA) in aqueous solution.

The temperature dependence of the reversible reaction between CO(2)(aq) and monoethanolamine (MEA) has been investigated using stopped-flow spectrophotometry by following the pH changes during the reactions with colored acid-base indicators. Multivariate global analysis of both the forward and backward kinetic measurements for the reaction of CO(2)(aq) with MEA yielded the rate and equilibrium constants, including the protonation constant of MEA carbamate, for the temperature range of 15-45 °C. Analysis of the rate and equilibrium constants in terms of the Arrhenius, Eyring, and van't Hoff relationships gave the relevant thermodynamic parameters. In addition, the rate and equilibrium constants for the slow, reversible reaction of bicarbonate with MEA are reported at 25.0 °C. At high pH, reactions of the amine with CO(2) and with bicarbonate are significant.