Water is an exceptionally good coolant – it takes a *ton* of energy to raise the temperature of water. When you add water to a burning material, the energy produced by the fire is being absorbed by the water rather than doing things that sustain the fire, like volatilising small molecules from the fuel (since combustion is primarily a vapour phase process).
Think about lighting a wood fire – you need to supply a fair bit of energy to the wood before it will start burning. This is because what needs to happen is for the large molecules in the wood to break down into small volatile ones that can actually react with oxygen. This still need to happen when the fire has started, but the energy comes from fire itself. Take that energy away from the fuel, fire goes out.
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