A study of the hydrogen absorption and desorption processes using LaNi(5) metal hydride is presented for investigation on the influences of expansion volume and heat convection. The hydrogen storage canister comprises a cylindrical metal bed and a void of expansion volume atop the metal. The expansion volume is considered as a domain of pure hydrogen gas. The gas motion in the metal hydride bed is treated as porous medium flow. Concepts of mass and energy conservation are incorporated in the model to depict the thermally coupled hydrogen absorption and desorption reactions. Simulation results show the expansion volume reduces the reaction rates by increasing thermal resistance to the heat transfer from the outside cooling/heating bath. The assumption usually adopted in simulating heat transfer in a metal hydride tank that heat convection in the reaction bed may be ignored is not valid when expansion volume is used because heat convection dominates the heat transfer through the expansion volume as well as the metal bed. The details of the thermal flow pattern are demonstrated. It is found that, due to the action of thermal buoyancy, circulations are likely to happen in the expansion volume. The hydrogen gas accordingly, instead of going directly between the inlet/outlet and the metal bed, tends to move with the circulation along the boundary of the expansion volume. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.