That is a valid solution, but what IO block size should you use for the best performance? What if you end up reading half a word at the end of a chunk?

Handling that is in my opinion way more complex than letting the kernel figure it out via mmap. The kernel knows way more than you about the underlying block devices, and you can use madvise with MADV_SEQUENTIAL to indicate that you will read the whole file sequentially. (That might free pages prematurely if you keep references into the data rather than copy the first occurance of each word though, so perhaps not ideal in this scenario.)