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Natural gas represents today maybe the most valid alternative to conventional fuels for road vehicles propulsion. The main constituent of natural gas, methane, is characterized by a high autoignition temperature, which makes the fuel highly resistant to knocking: this allows a considerable downsizing of the engine by means of supercharging even under high compression ratio. Starting from these considerations, the authors realized a thermodynamic model of a 4-cilynder s.i. engine for the prevision of in-cylinder pressure, employing a two-zone approach for the combustion and adding sub-models to account for gas properties change and knocking occurrence. An extensive experimental campaign has been carried out on the test bed, equipped with a naturally aspirated bi-fuel s.i. engine (i.e. an engine which can run either with gasoline or with compressed natural gas), so as to set the model constants to the best matching values.