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A number of practical applications where dual fuel systems are used, such as in gas fuelled diesel engines, involve the combustion in air of a gaseous fuel, such as methane in the presence of a higher hydrocarbon vapour. There is a need to examine and understand the nature and extent of any chemical interaction that may take place between the gaseous and higher hydrocarbon fuel components and how this interaction influences the combustion processes and hence the performance of dual fuel engines. Detailed chemical kinetics for the oxidation of the typical higher hydrocarbon fuel n-heptane, representing the behaviour of diesel vapours, in the presence of methane, are examined while using a comprehensive kinetic scheme (1966 reaction steps and 380 species) at different conditions relevant to engine applications, including constant temperature, constant pressure and constant volume processes.