On the Rate Expressions for “Reversible” Gas–Solid Reactions

It is argued that the term with the negative sign in the rate expression for an equilibrium-limited gas–solid reaction can be viewed as representing a lowering of the concentration driving force for the forward reaction due to equilibrium limitation. While the gas composition favors the forward reaction, the negative term may represent the local rate of the reverse reaction. When the gas composition changes significantly to the opposite side of equilibrium, however, this term as written for the forward reaction does not represent the rate of the reverse reaction. Even the reaction order with respect to the same gaseous species may become different for the reverse reaction.