Calorie is just a word we use to describe a unit of energy. A device called a calorimeter can be used to measure the heat of chemical reactions, physical changes or heat capacity. Basically, a calorimeter is made up of a thermometer attached to a metal container full of water which is positioned above a chamber. A sample of the food product would be put into the chamber and combusted. The temperature change that occurs is used to work out the specific heat capacity of the food product and also the energy involved in the combustion (burning) reaction. Some maths is then used to work out the calorie content!
They work it out by burning the food. The amount of energy (or calories) contained in that food can be measured by the amount the burning of the food increases 1ooml of water. A calorie is the amount of energy required to raise the temperature of one gram of water (one ml) by one degree Celsius.
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