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A zero-dimensional, thermodynamic model with detailed chemical kinetics and cylinder wall heat transfer correlations has been used to study the detailed oxidation mechanism of natural gas in homogeneous charge compression ignition (HCCI) engine. A short mechanism made up of 241 reversible elementary reactions among 47species has been assembled from a previously extended detailed mechanism. The mechanism was numerically investigated at different operating and geometry conditions of HCCI engine during the time period in which both intake and exhaust valves are closed. The study is performed to elucidate the mechanisms of extinction and combustion behaviors of natural gas fuel with the effect of hydrogen addition to overcome the control of autoignition timing over a wide range of speeds and loads, limiting the heat released rate at high load operation, and meeting emission standards.