Solvation of CO₂ in Water: Effect of RuBP on CO₂ Concentration in Bundle Sheath of C₄ Plants

Abstract

An understanding of the temperature-dependence of solubility of carbon dioxide (CO₂) in water is important for many industrial processes. Voluminous work has been done by both quantum chemical methods and molecular dynamics (MD) simulations on the interaction between CO₂ and water, but a quantitative evaluation of solubility remains elusive. In this work, we have approached the problem by considering quantum chemically calculated total energies and thermal energies, and incorporating the effects of mixing, hydrogen bonding, and phonon modes. An overall equation relating the calculated free energy and entropy of mixing with the gas-solution equilibrium constant has been derived. This equation has been iteratively solved to obtain the solubility as functions of temperature and dielectric constant. The calculated solubility versus temperature plot excellently matches the observed plot. Solubility has been shown to increase with dielectric constant, for example, by addition of electrolytes. We have also found that at the experimentally reported concentration of enzyme RuBP in bundle sheath cells of chloroplast in C₄ green plants, the concentration of CO₂ can effectively increase by as much as a factor of 7.1–38.5. This stands in agreement with the observed effective rise in concentration by as much as 10 times