Exchange enthalpies of aluminum with Na-montmorillonite suspension are determined at 3O3.15K and PH=3, and 4, using titration calorimetry and the exchange reaction mechanism are further studied by combining calorimetric results and exchange isotherm determined by static method. The adsorption of aluminum on Na-montmorillonite is endothermic, and therefore exchange reaction is a process driven by entropy. X-ray diffraction patterns of montmorillonite saturated by Na+ and Al3+ are determined at wet and dry state respectively. The reslllts show Al3+ adsorbed on the clay can dramatically reduce the expansion of montmorillonite because Al3+prevents osmotic swelling.