Solubility of NaCl under anisotropic stress state.

Salt solubility is generally determined under isotropic stress conditions. Yet, in the context of salt weathering of porous media, mechanical constraints on the in-pore growth of salt crystals are likely to be orientation-dependent, resulting in an anisotropic stress state on the crystal. In this paper, we determine by molecular simulation the solubility of NaCl in water when the crystal is subjected to anisotropic stress. Such anisotropy causes the chemical potential of the crystal to be orientation-dependent, and proper thermodynamic formulation requires describing the chemical potential as a tensor. The solute and crystal chemical potentials are computed from free energy calculations using Hamiltonian thermodynamic integration, and the usual condition of solubility is reformulated to account for the tensorial nature of the crystal chemical potential. We investigate in detail how the uniaxial compression of the crystal affects its solubility. The molecular simulation results led to revisiting the Correns law under anisotropic stress. Regarding the solute, the non-ideal behavior of the liquid phase is captured using Pitzer's ion interaction approach up to high concentrations of interest for in-pore crystallization and beyond the concentrations addressed in the existing literature. Regarding NaCl crystals, the validity of the generalized Gibbs-Duhem equation for a tensorial chemical potential is carefully verified, and it is found that crystallization progresses almost orthogonally to the crystal surface even under high shear stresses. Comparing uniaxial and isotropic compression highlights the major differences in solubility caused by stress anisotropy, and the revisited Correns law offers an appropriate framework to capture this phenomenon.