In the present work a basic numerical-experimental study was carried out, in vertical annular geometry, about the solidification of a salt hydrate, whose change of phase takes place similarly to the binary metallic alloys. It was chosen the NH4CL-H2O binary system, and the solidification process was studied in three cavities of different aspect ratios, utilizing solutions of distinct initial concentrations. In all the experiments, identical initial and boundary conditions were adopted. For that, an experimental apparatus was set up to be allowed not only the visualization of solid structure growth, that attaches the cold wall, but also local measurements of temperature and concentration. The initial concentration values were chosen to provide an experimental data base that depicted sufficiently the system behavior during the solidification process, in which part of them were used in the comparison with numerical predictions. The numerical problem was solved bi-dimensionally, utilizing the finite volume method and, analytically, it was applied the averaging volume technique to the conservation equations. Besides the comparison between numerical and experimental results about temperature and concentration transients, it was also investigated the solidification behavior. Additionally, it was evaluated both the temporal influence of the aspect ratio against the heat transfer to the cold wall of the cavity, and about the solidification front progress. Further, in the experimental part of this study, it was developed a technique for the determination of the concentration in any point of interest, making use of thermocouples attached to optical fiber sensors, that allowed to make several measurements simultaneously, in real time, causing minimal disturbance in the medium.