Coupling Solvation Thermodynamics and Chemical Speciation

Abstract

We present a simulation-based framework to characterize the solvation and aqueous-phase reactivity of nitric oxide (NO) and nitrogen dioxide (NO2) in water. Using Continuous Fractional Component Monte Carlo (CFCMC) simulations, we compute Henry coefficients and chemical potentials of NO and NO2, while molecular dynamics (MD) simulations provide diffusion coefficients for NO. The results for NO are quantitatively in agreement with the experimental data when using the Saji force field. For NO2, we model the chemical equilibrium involving hydrolysis and acid-base reactions that generate HNO2, HNO3, NO2-, NO3-, and H3O+. By combining the chemical potentials obtained via CFCMC with a thermodynamic equilibrium model, we resolve the temperature- and pressure-dependent speciation and pH of the system. The model captures a transition from nitrous to nitric species with increasing temperature and predicts ionic distributions and pH shifts under varying NOx gas fluxes. This work provides a transferable methodology to connect molecular simulations with chemical speciation in reactive aqueous systems.