Ions in water: the microscopic structure of a concentrated HCl solution

A neutron diffraction experiment with isotopic H/D substitution on a concentrated HCl/H2O solution is presented. The full set of partial structure factors is extracted, by combining the diffraction data with a Monte Carlo simulation. This allows us to investigate both the changes of the water structure in the presence of ions and their solvation shell, overcoming the limitations of standard diffraction experiments. It is found that the interaction with the solutes affects the tetrahedral network of hydrogen bonded water molecules, in a manner similar to the application of an external pressure to pure water, although HCl seems less effective than other solutes, such as NaOH, at the same concentration. Consistent with experimental and theoretical data, the number of water molecules in the solution is not sufficient to completely dissociate the acid molecule. As a consequence, both dissociated H+ and Cl- ions and undissociated HCl molecules coexist in the sample, and this mixture is correctly reproduced in the simulation box. In particular, the hydrated H+ ions, forming a H3O+ complex, participate in three strong and short hydrogen bonds, while a well-defined hydration shell is found around the chlorine ion. These results are not consistent with the findings of early diffraction experiments on the same system and could only be obtained by combining high quality experimental data with a proper computer simulation.