Depending upon the ultimate design, the use of porous media in thermal and chemical systems can provide significant operational advantages, including helping to maintain a uniform temperature distribution, increasing the heat transfer rate, controlling reaction rates, and improving heat flux absorption. For this reason, numerous experimental and numerical investigations have been performed on thermal and chemical systems that utilize various types of porous materials. Recently, previous thermal analyses of porous materials embedded in channels or cavities have been re-evaluated using a local thermal non equilibrium (LTNE) modelling technique. Consequently, the second law analyses of these systems using the LTNE method have been a point of focus in a number of more recent investigations. This has resulted in a series of investigations in various porous systems, and comparisons of the results obtained from traditional local thermal equilibrium (LTE) and the more recent LTNE modelling approach. Moreover, the rapid development and deployment of micro-manufacturing techniques have resulted in an increase in manufacturing flexibility that has made the use of these materials much easier for many micro thermal and chemical system applications, including emerging energy-related fields such as micro reactors, micro-combustors, solar thermal collectors and many others. The result is a renewed interest in the thermal performance and the exergetic analysis of these porous thermochemical systems. This current investigation reviews the recent developments of the second law investigations and analyses in thermal and chemical problems in porous media. The effects of various parameters on the entropy generation in these systems are discussed, with particular attention given to the influence of local thermodynamic equilibrium and non-equilibrium upon the second law performance of these systems. This discussion is then followed by a review of the mathematical methods that have been used for simulations. Finally, conclusions and recommendations regarding the unexplored systems and the areas in the greatest need of further investigations are summarized. (C) 2017 Elsevier Ltd. All rights reserved.