Often times, a fire is not built in a way that provides optimal airflow. So when you blow on a fire you are increasing the amount of air and therefore the amount of oxygen. The more oxygen, the more efficient the oxidation reduction reaction of combustion. The more oxygen, the more complete the conversion, you will get more carbon dioxide instead of carbon monoxide.
A fire requires a steady supply of oxygen to burn continously. Blowing on a fire increases the airflow around the fire, which increases the amount of oxygen around the fire. The reason small fires go out after you blow on them vigorously is because the force of your breath is strong enough to physically remove the fire from its fuel source.
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