Exergetic and energetic analysis has been utilized to estimate the effect of process design and conditions on the hydrogen purity and yield, exergetic efficiencies and CO2 avoided. Methane was chosen as a model compound for evaluating single stage separation. Simple steam reforming was considered as the base case system. The other chemical processes that were considered were steam reforming with CO2 capture with and without chemical looping of a reactive carbon dioxide removal agent, and steam gasification with both the Boudouard reaction catalyst and the reactive carbon dioxide removal agent with and without the solids regeneration. The information presented clearly demonstrates the differences in efficiencies between the various chemical looping processes for hydrogen generation. The incremental changes in efficiencies as a function of process parameters such as temperature, steam amount, chemical type and amount were estimated. Energy and exergy losses associated with generation of syngas, separation of hydrogen from CO as well as exergetic loss associated with emissions are presented. The optimal conditions for each process by minimizing these losses are presented. The majority of the exergy destruction occurs due to the high irreversibility of chemical reactions. The results of this investigation demonstrate the utility of exergy analysis. The paper provides a procedure for the comparison of various technologies for the production of hydrogen from carbon based materials based on First and Second Law Analysis. In addition, two figures of merit, namely the comparative advantage factor and the sustainable advantage factor have been proposed to compare the various hydrogen production methods using carbonaceous fuels. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.