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Nearly every program, or at least the executable binary, gets installed to /usr/bin/. At least that's how most package managers work. If you compile it yourself though, it might default to /usr/local/bin/ instead (this is configurable at compilation time). The most common problem in this case comes when /usr/local/bin isn't described in your PATH variable, so the system doesn't automatically detect it. Update the PATH and it should work.
Sometimes the file placed in /usr/bin are really just symlinks to the actual files elsewhere, especially if the actual program is big and complicated with many subfiles. But ffmpeg isn't a very big program, and I believe the file in /usr/bin/ is all there is, outside of the documentation files and such.
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