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A new catalyst for steam reforming of methane based on nickel/calcium aluminate is prepared. The new catalyst has shown stability and high activity at low steam to methane ratios. In this paper the intrinsic rate equations are derived and parameters estimation made. The rate equations show non‐monotonic dependence on steam partial pressure. The rate equations also show that the primary product is CO₂ while CO is formed via the reverse water‐gas shift reaction. The mechanism proposed and the rate equations obtained indicate that it may be essential to propose specific rate models for any given catalyst rather than generalized mechanism and rate models.