Supplementary Data

Figure S-1 shows compositions of CO2-CO-H2O-H2 gas flow rates for the (reverse) water gas
shift reaction within three different support tubes without a nickel catalyst. For the water gas
shift reaction, flow rates of (CO/H2O) gas mixtures were 10/30 and 6/34 ml min-1, while for
the reverse water gas shift reaction, (CO2/H2) flow rates were 30/10 and 34/6 ml min-1. Within
experimental error, no variations were detected for CO or CO2 flow rates. Some minor
variation for the H2 signal was detected, as a result of signal instability due to accumulation of
hydrogen (related to zero blast problems at low masses).

According to thermodynamic predictions of equilibrium compositions, changes in flow rates

should have been easily detectable and of the order of 5.0-7.5 ml min-1. However, kinetic
correlations for the reverse water gas shift reactions predict three orders of magnitude slower
(initial) reaction rates (for homogenous (reverse) water gas shift reaction in the absence of a
nickel catalyst) than necessary to reach thermodynamic equilibrium [32], so that no changes
would be detected within the present experimental system.

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Figure S-1: Compositions of CO2-CO-H2O-H2 gas flow rates for the homogeneous (reverse)
water gas shift reaction at 822 C without a nickel catalyst in support tubes of: (A) alumina,
(B) quartz and (C) 10.5 yttria-stabilized zirconia (YSZ).