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In-cylinder ion sensing through sparkplug electrodes can be used to determine in-cylinder A/F ratio by using a modified production coil-on-plug ignition system having ion sensing capability. The in-cylinder ionization can be characterized by the height of the peak, location of the peak from ignition command and area under the ionization signal curve. The effects of A/F ratio on the in-cylinder ionization can be isolated from other affecting factors by conducting tests on a constant volume combustion device in which the initial pressure and temperature can be well controlled. This results in a parabolic correlation of the ionization characteristics with the mixture equivalence ratio. Additionally the ionization characteristics show strong dependence on engine load and speed. Equivalence ratio characteristics during engine cranking and warm up are investigated, and a method for on-line calibration of ionization detection is discussed.