I agree that experience will develop an intuition for how C statement map to assembly. But experience is no replacement for standards -- no implementation defines the language. In most cases, it's more useful to reason about the guarantees within the language rather than inferring what the compiled assembly will be. Possible? Yes, if as you said development is on homogeneous platforms. Painful? If you need to know how 5 compilers act instead of 1, I suspect so.
The point is not to know the actual assembly. The point is that you'll never run an operation that might take a non-deterministic amount of time to run.
Contrast to, say, Python (as an obviously exaggerated counterexample). Just calling a function in Python means performing a lookup in a hash table.
