The definition of a calorie is the amount of energy needed to raise 1 gram of water 1°C.
The way they measure this is by putting food into a tool called a bomb calorimeter. Like how you can use natural gas to boil water on a stove, they burn the food as a fuel source and see how much it heats the water.
That’s a lot of work to do for every single thing on grocery store shelves so they can just estimate it and add the ingredients used.
They can also back into it if they know what’s in it by approximating it. Fat is about 9 calories, while protein and and carbohydrates are 4 calories.
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