[Shadow]

What are some cases and how to recognize the reactions where steady-state and rate-determining step can't be used to derive the overall rate equation? What tool is used then?

[curiouscat]

What are some cases and how to recognize the reactions where steady-state and rate-determining step can't be used to derive the overall rate equation? What tool is used then?

There's no fundamental reason why there ought to be a neat, closed form expression in the first place. You might have to stay content with a full model that you solve numerically.

In most practical kinetics models these days that is exactly what is done.

[Shadow]

I supposse that the computers are needed then.
What are some cases where steady-state and rate-determining step can't be used to derive the overall rate equation?