These reactions are catalyzed by HN03 and H20 through heterogeneous reaction paths having negative temperature dependences. The active reaction sites in these heterogeneous paths appear to be HN03 dimers and polymers which are hydrated in the presence of H20. Only the first reaction with an equilibrium constant of 645 ± 79 (atm units) at 25 °C has an appreciable homogeneous rate that is second order in N02 and first order in HCI. The experimental rate equations for these reactions, their temperature dependences, and reaction mechanisms are presented.
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