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Odds are, if you've got inventive players, you've had a character create these in game. My question is, how good should they be?
A bit of context: A player wanted to load a lit oil flask into a sling (they're a halfling, so they wanted the bonus). The player was envisioning the bottles as small and round, so aerodynamically at least it should work. I was skeptical, though, about whether flasks of oil would actually be shaped that way and be small enough to load into a sling. We agreed to get an answer on the forums later.
So, can you sling molotovs?

Kobold Catgirl |

But I have no skill points. And no way to get artisan's tools. :(
It's not so much the bonuses I mind, I'm just looking for ways to avoid the -10 range penalties I've been dealing with so often. In the next encounter we got brutalized partially because I literally couldn't hit the broad side of a (flammable) wall. Four times in a row.
I also thought it'd look cool. Considering I have to give up a full-round action beforehand for a 50% chance of setting someone on fire, it seemed balanced to me.

Kobold Catgirl |

This is the rule I am using:
Oil: A pint of oil burns for 6 hours in a lantern or lamp. You can also use a flask of oil as a splash weapon. Use the rules for alchemist's fire (see Special Substances and Items on Table: Goods and Services), except that it takes a full-round action to prepare a flask with a fuse. Once it is thrown, there is a 50% chance of the flask igniting successfully.

gustavo iglesias |

Range penalties.
As for creating the molotov itself, the concept of molotovs is fairly established in the Pathfinder system. It's a pain in the ass, but it's not obscure knowledge. :P
Scrolls of fireball are also well stablished, but you need scribe scroll to write them :)
The oil rules are ok. If you want to use aeridinamic incendiary bullets for the sling, I'd ask for some craft, or engineering, por something like that

Kayerloth |
Enchant the sling you'll be using to help deal with range penalties. But yes Alchemist Fire is basically the flammable part of a Molotov. And as others have suggested various craft skills to create the aerodynamic 'missile' intended portion.
Edit: And if both enchanting and craft skills are out the window make sure you are correctly employing the rules ... I'm assuming some of the "couldn't hit the wall issue" was exaggeration due to annoyance over the problem. If not then rereading those rules should help, again assuming it wasn't a streak of auto missing 1's getting rolled (which no amount of crafting, enchanting or other fixes is going to take care of).

Claxon |

The rules for improvised flammable weapons made from oil have been quoted. They're crappy alchemist's fire.
In regards to using a sling with them...sorry but no. Not unless you buy specially made flasks for it, they're probably too big to fit.
You could alternatively also buy a launching crossbow, which is intended do exactly this sort of thing.

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This is a limited supply of oil flasks that KC has been using pretty sparingly. This is actually in the context of an isolated adventure location that is very difficult to escape - there aren't any shops, getting the raw materials for crafting is going to take something like a Survival check.
KC's linked me to google images of pretty spherical-looking flasks, so I'm willing to believe that they'd be aerodynamic now. But how do scales compare, between a flask and a sling pouch? This is sort of related to Claxon's point.

Kobold Catgirl |

It looks like sling stones could get to be around the size of a tennis ball. Example. This would make the flask significantly larger.

Claxon |

Is there a reason you can't get closer to the targets?
As a GM, I might be kind and let you improvise a special sling cup to accommodate something the size of an alchemist's fire flask with double the normal range increment (20ft). I would probably administer a -2 penalty for "awkwardness". So, a slight improvement of your overall situation depending on range.