I have noticed that sometimes my various Macintosh's (I have an iMacG3, iMacG5, and PowerBook G4, running 10.2.8, 10.4.6, and 10.3.9) have more space available after rebooting. This might be due to some housekeeping like the kind mentioned by Chuckit which is performed when the Mac starts up. I suspect the process is a bit different with different versions of OS X.
There is another possibility, although probably somewhat unlikely. If your disk's file system needs maintenance, running fsck or Disk Utility or Disk Warrior will sometimes result in more free space being "available."
Probably the most likely is just adding files over time. At work, I get scores of emails every day with attachments, the attachments really eat up space (powerpoint files, for instance). Other disk space eaters include iTunes and iPhoto, as each picture or music file takes up several megabytes. Be aware also that web browsers have caches that fill up and are emptied according to some sort of defined process within the browsers.