There are differing views, but the latest I've heard of is a paper published earlier this year in "The Herptile" (journal of the International Herpetological Society). This states that freezing is inhumane as it is now known that reptiles' nervous systems behave very differently than those of mammals. Essentially, snakes can remain conscious under extreme conditions and current thinking is that they are conscious throughout the freezing process with all the pain and distress that this entails (rupturing blood vessels, eyes etc. as the ice crystals form). The article was written by fully qualified vets, so it was enough to give me pause for thought.
There was further input on a UK forum from a reptile rescue expert, who put forward her view that even decapitation does not cause instant death, because a reptile's brain can survive for much longer than a mammal's without oxygen. The severed head may continue to react to its surroundings for some time and death is therefore not instantaneous. This person's view was that the only true way of ensuring an instant and painless death for a suffering reptile, was a blow to the head forceful enough to destroy the brain.
Lethal injection was also discussed, but it was said that a reptile will need a much larger dose than a vet would use for a mammal (due to the fact that their nervous systems behave in a different way than a mammal's). Therefore, unless a vet can be persuaded to increase the dose to three times what they would expect to use per bodyweight for a mammal, it's possible for a snake that has been lethally injected, to still be conscious when the body is disposed of.
Please PM me if you'd like links to these discussions and I'll try to dig them out.