Thermodynamic and Transport Properties of H2/H2O/NaB(OH)4 Mixtures Using the Delft Force Field (DFF/B(OH)4-)

Sodium borohydride (NaBH4) has a high hydrogen (H2) gravimetric capacity of 10.7 wt %. NaBH4 releases H2 through a hydrolysis reaction in which aqueous NaB(OH) 4 is formed as a byproduct. NaB(OH) 4 strongly influences the thermophysical properties of aqueous solutions (i.e., densities, viscosities, and electrical conductivities) and the hydrolysis reaction kinetics and conversion of NaBH4. Here, molecular dynamics (MD) simulations are performed to compute viscosities, electrical conductivities, and self-diffusivities of H2, Na+, and B(OH) 4- for a temperature and concentration range of 298-353 K and 0-5 mol NaB(OH)4/kg water, respectively. Continuous fractional component Monte Carlo (CFCMC) simulations are used to compute the solubilities of H-2 and activities of water in aqueous NaB(OH) 4 solutions for the same temperature and concentration range. A new force field is developed (Delft force field of B(OH) 4-: DFF/B(OH) 4-) in which B(OH) 4- is modeled as a tetrahedral structure with a scaled charge of -0.85. The OH group in B(OH) 4- is modeled as a single interaction site. This force field is based on TIP4P/2005 water and the Madrid-2019 Na+ force field. The MD simulations can accurately capture the densities and viscosities within 2.5% deviation from available experimental data at 298 K up to a concentration of 5 mol NaB(OH)4/kg water. The computed electrical conductivities deviate by ca. 10% from experimental data at 298 K for the same concentration range. Based on the molecular simulations results, engineering equations are developed for shear viscosities, self-diffusivities of H2, Na+, and B(OH) 4-, and solubilities of H2, which can be used to design and model NaBH4 hydrolysis reactors.