If I use a library, I also need to start using threads and need to invent some core synchronization mechanism. I essentially are reinventing a small scheduler, when I already get this from the OS for free. Also know any crash in the third-party code will crash the whole program, the third-party code has access to the whole address space. With invoking a process you also have a standardized API implemented by the OS.
I can recall just one program that's intentionally not implemented as a library, but I think people have since built a library on top of it:
https://dechifro.org/dcraw/#:~:text=Why%20don%27t%20you%20im...