In this article, we propose a generalized non-equilibrium chemical kinetics model from ab initio simulation data obtained using accurate potential energy surfaces developed recently for the purpose of studying high-temperature air chemistry. First, we present a simple cross section model for dissociation that captures recent ab initio data accurately. The cross section model is analytically integrated over Boltzmann distributions and general non-Boltzmann distributions to derive a general non-equilibrium dissociation model. The general non-Boltzmann model systematically incorporates key physics such as dependence on translational energy, rotational energy, vibrational energy, internal energy, centrifugal barrier, and non-Boltzmann effects such as overpopulation and depletion of high energy states. The model is shown to reproduce the rates from quasi-classical trajectory calculations for Boltzmann distributions of internal energy states. The reduced rates in a non-equilibrium steady state due to depletion of high internal energy states are also predicted well by the model. Furthermore, the model predicts the enhanced rates as observed due to significant overpopulation of high vibrational states relative to Boltzmann distributions while the gas is in non-equilibrium in the transient phase. The model provides a computationally inexpensive way of incorporating non-equilibrium chemistry without incurring additional cost in the existing computational tools. Further comparisons of the model are carried out in Paper II, where simplifications to the model are proposed based on the results.