@zitqhile... or, to put it differently and much more wordily, the chapter numbers are arbitrarily set by the author (though they usually don't bother to change the default Chapter 1, Chapter 2 etc.), but the URLs MUST be unique, and are assigned by the system, usually consecutively. In particular this means that if there is an Introduction or Prologue, that will (usually) be /1, with chapter 1, 2 etc being /2, /3 etc (or /3, /4... if there are both an intro and prologue). There are a few stories here internally split up into separate books where the chapter numbering restarts at 1 for each, so they have multiple chapters named Chapter 2 for instance, but these similarly-named chapters will have different trailing numbers after the / in the URL.
There is a wrinkle I've only just noticed which also causes a chapter/URL mismatch: some of the URL file numbers don't exist (or at least, are not accessible). For instance I was reading Deja Vu Ascendancy (again) and was near chapter 380 when I saw this thread; on checking, chapter 380 (the first of part 17) has file number 400, but the preceding chapter 379 (last of part 16) has file number /398; in the [More Info] page, listed between those two chapters, is the separator showing Part 17 ..., which presumably corresponds to the missing file number /399. Interesting.