Clove oil, when used properly, is a sedative. I've used it on both fish and crabs. Added very slowly to the container, it causes zero visible distress; they slow down, become less and less wary, and eventually pass out. Never had either of them show any signs of irritation; no head-shaking, no flashing. Heck, it's used as an anesthetic for surgeries on fish sometimes. It'd definitely be an irritant if you poured in a ton at once, so, don't do that.
Unless you've got a reputable source that says clove oil is inhumane when properly used, you might need to do some more reading.
Sometimes, yes.
Decapitation is NOT humane on cold-blooded animals, as it can take a long time for the brain to die. Pithing or otherwise destroying the brain entirely is humane, but gruesome, and can be difficult to do properly. Clove oil is probably the best bet for the hobbyist; it's hard to mess up, the opposite of gruesome, and easily available at health food stores and the like.
Freezing is highly debated but likely inhumane.