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When the reactants are heated, the average kinetic energy of the molecules increases. This means that more molecules are moving faster and hitting each other with more energy. If more molecules hit each other with enough energy to react, then the rate of the reaction increases.
The simple answer is that heat is energy. Heat travels in waves like other forms of energy, and can change the matter it touches. It can heat it up-which starts molecules moving or it can cause chemical reactions like burning to occur. Heat can be released through a chemical reaction (such as the nuclear reactions that make the Sun burn) or can be trapped for a limited time by insulators. It is often released along with other kinds of energy such as light, radio waves, or sound waves. A burning candle releases light and heat waves; an explosion releases light, heat, and sound waves. The Sun releases all kinds of energy waves.