Thermodynamics predict that you'd be better off drinking gasoline (12kcal/gr > fat's 9kcal/gr), and just as well eating wood chips (a carbohydrage) -- even though you get zero energy from either.
"But we're not using calorimeter data, we're using atwater factors"; Well, those actually DO vary from person to person, IIRC as much as 50%; and other things also matter (e.g., adding activated carbon to your food will result in less energy extracted in general; using Ally would result in less energy extracted from fat).
And that's just for the "calories in" part; metabolic rate can also vary as much as 80% along time and between people, depending on muscle volume, or other random, less understood factors - so without a proper measurement chamber you don't know the "calories out" either.
The food labels and general activity tables serve as a good general approximation that describes probably 80% of the public quite well. But invoking thermodynamics (except as an upper bound for calories in) is not justified by our current understanding of metabolism.