Microstructure technologies have attracted interests in chemistry, chemical engineering, and biotechnology. To investigate the mass transfer of ions and crystallization of crystals in microscale and then to explain the formation mechanism of the porous structure materials, a microscale mathematical model for mass transfer processes coupling with local reactions is proposed in which the chemical potential gradient Delta mu is used as the driving force to avoid the discontinuity of the kinetics equations in the micro-channels. Meanwhile, the dissolution kinetics of KCl at 298.15 K is measured to determine the dissolution rate constant k(d) and the average area of crystals Ac. The investigation for the fractional crystallization process of carnallite shows that the calculated mixing time versus channel width agree with the Einstein diffusion equation, which validates that the model can be used to describe the ion diffusion very well. Meanwhile, to have an accurate Delta mu of KCl, in the channel width of or narrower than 2.0 x 10(-6) m, it is enough to consider the diffusion only, while in the channel width of or wider than 2.0 x 10(-5) m, diffusion should be coupled with reaction. The investigation also shows the vital of the consideration of the ionic activity coefficient for the investigated systems in micron scales. Moreover, the new formation mechanism of the porous structures in the inorganic material fabrication will be proposed from the process simulation for the synthesis of porous KCl, which will provide a reference for the porous structure formation in the advanced inorganic material synthesis. (C) 2010 Elsevier Ltd. All rights reserved.