Mechanistic investigations on the heterogeneous solid-state reaction of magnesium amides and lithium hydrides

J Phys Chem B. 2006 Jul 27;110(29):14221-5. doi: 10.1021/jp061496v.

Abstract

Isothermal and non-isothermal kinetic measurements on the chemical reaction between Mg(NH2)(2) and LiH, as well as the thermal decomposition of Mg(NH(2))(2), give apparent activation energies of 88.1 and 130 kJ/mol, respectively, which reveal that the thermal decomposition of Mg(NH2)(2) is unlikely to be an elementary step in the chemical reaction of Mg(NH2)(2) and 2LiH. The H-D exchange between H(delta+) in Mg(NH2)(2) and D(delta-) in LiD gives evidence for the coordinated interaction between amide and hydride. The observed linear and nonlinear kinetic growth in the reaction of Mg(NH2)(2)-2LiH indicates that the reaction rate is controlled by the interface reaction in the early stage of the reaction and by mass transport through the imide layer in the later stage. Both particle size and degree of mixing of the reacting species affect the overall kinetics of the reactions.