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The oxygen sensor is positioned in the exhaust pipe and can detect rich and lean mixtures. The mechanism in most sensors involves a chemical reaction that generates a voltage (see the patents below for details). The engine's computer looks at the voltage to determine if the mixture is rich or lean, and adjusts the amount of fuel entering the engine accordingly.
The reason why the engine needs the oxygen sensor is because the amount of oxygen that the engine can pull in depends on all sorts of things, such as the altitude, the temperature of the air, the temperature of the engine, the barometric pressure, the load on the engine, etc.
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