Atomistic Molecular Dynamics Simulations of CO2 Diffusivity in H2O for a Wide Range of Temperatures and Pressures

摘要

Molecular dynamics simulations were employed for the calculation of diffusion coefficients of CO2 in H2O. Various combinations of existing force fields for H2O (SPC, SPC/E, and TIP4P/2005) and CO2 (EPM2 and TraPPE) were tested over a wide range of temperatures (283-15 K < T< 623.15 K) and pressures (0.1 MPa < P < 100.0 MPa). All force-field combinations qualitatively reproduce the trends of the experimental data; however, two specific combinations were found to be more accurate. In particular, at atmospheric pressure, the TIP4P/2005—EPM2 combination was found to perform better for temperatures lower than 323.15 K, while the SPC/E—TraPPE combination was found to perform better at higher temperatures. The pressure dependence of the diffusion coefficient of CO2 in H2O at constant temperature is shown to be negligible at temperatures lower than 473.15 K, in good agreement with experiments. As temperature increases, the pressure effect becomes substantial. The phenomenon is driven primarily by the higher compressibility of liquid H2O at near-critical conditions. Finally, a simple power-law-type phenomenological equation is proposed to correlate the simulation values; the proposed correlation should be useful for engineering calculations.