I don't remember where I read it, but in castle defence, slings where used for their large harassing range, to disrupt camp life and make attacker's lives more uncomfortable. I also believe they were used to target oxen pulling the heavy siege weapons.

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I actually found it on a "www.omglolfunnypics.com" sort of website. Just google llamapillar though, it's one of those 'memes'.

You could use a flaming projectile from a castle wall, however, most castle walls had wooden structures on the walls.  Most illistrations that I have seen have the attackers using flame to burn out the defenders.  There goes the loot, incedently, so it was probably a last resort.  When throwing at a formation, your splatter is pretty small, small container, and also the liquid is going to be fairly thick.  Think vegtable oil to honey thick.  It will spread, but it won't splatter over a wide area.  It would suck to get hit with it and when your buddies got in, they would make examples of every slinger they catch.  In the next battle, you may have a hard time getting slingers to throw a flaming weapon.  Bill