Rhodium promotion of iron-chromium oxide (Fe-Cr) catalysts for the water-gas shift (WGS) reaction was investigated through measurement of the rates of individual reduction and reoxidation steps. The temperature-programmed reduction of the starting Fe2O3 form by H-2 is accelerated by rhodium, with the extent of oxygen removal at 450 degrees C corresponding to Fe3O4 formation. The corresponding reduction by CO proceeds further, in agreement with bulk thermodynamic expectations. However, rhodium has no effect oil the oxygen removal rate. although it leads to substantially increased carbon deposition. The behavior with respect to reoxidation of reduced catalysts is somewhat similar. Rhodium greatly enhances H-2 release during reoxidation by water, presumably by recombining hydrogen atoms transferred from oxide to metal by reverse spillover. The rate of H-2 evolution from the Rh/Fe-Cr system at 280 degrees C is greater than that from Fe-Cr at 380 degrees C. Reoxidation by CO2 is not promoted by Rh and is much slower than that by H2O for the Rh-contaming catalyst. Likewise, reoxidation by H2O/CO2 mixtures results in a much higher yield of H-2 relative to CO for the promoted catalyst compared with the Unpromoted one. The extent to which catalysts previously equilibrated in WGS feeds at 350 degrees C can then be reduced in pulses of CO or H-2 depends oil the composition of the WGS feed. Fe-Cr catalysts do not reduce in H-2 after exposure to H2O/CO (2:1) or it reformate (H2O/CO/H-2/CO2) feed. Hydrogen reduction is possible with Rh/Fe-Cr after exposure to H2O/CO but not after exposure to reformate, for which thermodynamic considerations suggest that the working oxidation state may be lower. The greater reducing power of CO leads to continuing reduction after treatment with both prior feeds. Overall. it is concluded that of the two steps that may restrict the rate of the WGS reaction over iron-chromium oxide catalysts (reduction by CO and H-2 generation through reoxiclation by water), rhodium acts primarily by accelerating the second. (c) 2006 Elsevier Inc. All rights reserved.