Thermodynamics of aqueous carbon dioxide and sulfur dioxide: heat capacities, volumes, and the temperature dependence of ionization

Abstract

. Can. J. Chem. 61, 2509Chem. 61, (1983. A flow microcalorimeter and vibrating tubc densimeter were used at 25°C to obtain apparcnt molar heat capacitics and volumes of aqueous NaHCO1, KHCO,. NaHSO,, and KHSO, from 0. I to I .O mol kg-'. aqueous CO, from 0.01 to 0.10 mol kg-' and aqueous SO, from 0.045 to 2.0 mol kg-'. The contribution of "chemical relaxation" (changes in cquilibrium state and enthalpy due to change in temperature) to thc experimental heat capacitics of aqucous SO, required special attention, leading to the derivation of a new equation for calculating this cffcct. Standard statc valucs for thc heat capacities and volurnes of aqueous CO,, SOz, HCO,.., and H S O , were obtained from the apparent molar properties by extrapolation to infinite dilution. Combining these rcsults with othcr thcrmodynamic data from the literature gave estimates of log K,", the cquilibrium constant for the first neutralization of CO, and SO?, at high temperatures. The results for CO, reproducc very accuratc literature values to within 0.2 at 200°C. The expression for the reaction SO, t O H S HS0,-, log K l h = 22.771 t 2776.0/T -8.058 log T, is consistent with the sparse and limited experimental data.

Volumes of aqueous solutions of CH4, CO2, H2S and NH3at temperatures from 298.15 K to 705 K and pressures to 35 MPa

“…8 Barbero et al (28) 0.1 33. 9 Moore et al (27) maximum compressibility of water (T=667 K at p=28 MPa, and T=693 K at p=35 MPa); above these temperatures, the uncertainty decreased to about 2·10 −2 ·V f at T=705 K.…”

Correlation and prediction of thermodynamic properties of nonelectrolytes at infinite dilution in water over very wide temperature and pressure ranges (2000K and 10GPa)

“…c An average of values in (Ellis and McFadden, 1972;Murphy and Gaines, 1974;Barbero et al, 1982;Hnědkovský et al, 1996). d An average of values in (Barbero et al, 1983;Sharygin et al, 1997). e An average of values in (Allred and Woolley, 1981;Kaulgud et al, 1982;Hnědkovský et al, 1996).…”

Convective stability analysis of the long-term storage of carbon dioxide in deep saline aquifers

“…Because the dependence between the apparent molar volume and concentration of CO 2 is very weak [12], the density variation is approximated as linear. By using Boussinesq approximation, the fluid density coupled with the concentration of dissolved CO 2 only appears in the buoyancy term in the Darcy equation (1).…”