If you put the radiators away from the windows then the people sitting near the windows would complain about the cold temperatures and crank up the heaters. In order to make them comfortable you would end up heating the rest of the room a lot higher then necessary. And it would still use just as much energy to keep the room at that temperature but now part of it is too hot while part of it is just comfortable.
By heating up the coldest part of the room, under the windows, you end up with a lot more even temperature in the entire room. This means you can make the room more comfortable with the same amount of energy.
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