It's a different kind. Say, some reaction should run 1.23x faster theoretically. But the theory is approximate (in order to be tractable at all), and so are its predictions. This particular element is special in its own way, diverging from the theory a bit, even though its neighbors fit well. That particular bond requires a bit less energy to break than the theory predicts, due to a complex interplay of bonds nearby, understood only qualitatively. Etc, etc.
A general theory of everything might describe all of it from first principles, without magic coefficients. But likely computing it would take a decade with current methods.
Oh alright fair enough, measured vs. expected basically?