I've actually always used the freezing method to put my fish to sleep. My mother would think I was nuts running around to 10 different stores trying to find an oil to euthanize my fish with. I've never done it slowly though because I think thats cruel. :/ I take a bowl, fill it with cold water (From my fridge since it's colder than tap water) and then fill it with ice cube. I make it as fast and easy as possible on me and the fish. I let the bowl of water and ice sit in the freezer for 5-10 minutes and then I remove the fish and drop it in. Longest time to die I've ever witnessed was 3 seconds and I've put down more fish than I can count. (I had a strain of Guppies who threw out severly deformed fry. It didn't ever show until they got bigger which I always found weird.)
Not sure how a cold water method would work for Goldfish though since they're cold water fish and can live in partially frozen ponds. I'd say boiling would probably be best (If you can't handle hitting it with something, cutting it's head off, can't find clove oil, ect) since it'd work in the same way as the freezing water, the temperature change is so dramatic in change the fish goes into shock and dies.
Keep in mind I've never used a freezing method for anything larger than a 3in Guppy (I mainly have only had to do Guppies but I've also had to put down a beloved Betta like this too.

) so I have no idea how long it'd take to kill a larger fish.
I wouldn't ever slowly kill a fish by putting it in a bowl of water and then letting it sit in the freezer to die though.

My brother killed all but 4 of my tropical fish (I had over 100. Cherry Barbs, Platies, Plecos, an Oscar, a Corydoras and Pluppies which are Platy/Guppy hybrids.) after he left the garage door cracked on a really cold night. (Dropped to like 20 degrees F) Needless to say I first discovered my Oscar who was laying on his side at the bottom, the Pleco who was with him was by some Java Moss laying as if he just froze where he was. My little fish were huddled together for the most part, some laying on the bottom as if they were sleeping. I have described my findings as the scene from Titantic where they're going through the ocean trying to find survivors but everyones frozen over. I managed to find 5 Platys and one lucky Pleco alive. One of the Platys died the next morning though. (Pleco and the other 3 Platys are doing great.

My Goldfish survived the night as well. I've always been against slowly killing a fish but after that (Rather tramatizing experience because it gives me the creeps to go in the garage now. I even took out my Goldfish just because I didn't want to feed them in there much less do anything like water changes that they needed. So I got them out so I'd feel better.) experience I'd never in a million years consider it. I do like using the freezing water method but never making it slow.