I remember my chemistry book depicted a testing apparatus for determining caloric content of food. The short answer is they burn it in an essentially oxygen-rich, closed environment that’s surrounded by a known quantity of water. The experiment measures the temperature change of the water, after the dried food sample is burned. The definition of a Calorie gives us a hint: “a unit of energy, often used to express the nutritional value of foods, equivalent to the heat energy needed to raise the temperature of 1 kilogram of water by 1 °C, and equal to one thousand small calories” from the Oxford English Dictionary.
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