As Zombie said, ball pythons don't need a day/night cycle. I would just use the night bulb and leave it on 24 hours if that's something you're interested in. Depending on the height of the cage, a 25watt may be too little (on the flipside, the 100watt is way too much). You really only need a 50watt on a shorter cage (I have a 50 watt red bulb on a cornsnake 20L cage) or a 75watt bulb on a taller cage.

That bulb will eliminate any humidity you have in there. You'll need to make sure to use a substrate that holds humidity well (cypress mulch, eco earth, coconut husks, etc) and do daily (or twice daily) mistings. You might also consider covering the lid with plexiglass, foil, a damp towel, etc.

If you really want to use both bulbs, that's fine...just make sure to use the appropriate wattage. Also, you may want to get a lamp dimmer for each light. I got one at home depot and it costs about $10. You can manually control how much heat the lamps give off by "dimming" them. This will help you better control the heat.