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This paper presents a combined experimental and numerical study of a modified Cooperative Fuel Research (CFR) engine that allows both the Research and Motor octane numbers (RON and MON) of any arbitrary Liquefied Petroleum Gas (LPG) mixture to be determined. The design of the modified engine incorporates modern hardware that enables accurate metering of different LPG mixtures, together with measurement of the in-cylinder pressure, the air-fuel ratio and the engine-out emissions. The modified CFR engine is first used to measure the octane numbers of different LPG mixtures. The measured octane numbers are shown to be similar to the limited data acquired using the now withdrawn Motor (LP) test method (ASTM D2623). The volumetric efficiency, engine-out emissions and combustion efficiency for twelve alternative LPG mixtures are then compared with equivalent data acquired with the standard CFR engine operating on a liquid fuel. Finally, the modified CFR engine is modelled using GT-Power.