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I don't know much about asphyxiation but it does not sound comfortable. Concerning lethal injection, it's not certain how much pain the paralyzed body feels as the heart is being stopped – have there been EEG studies?
I would prefer execution by firing squad.
The human body can only detect a buildup of carbon dioxide in the lungs, not a lack of oxygen. This is why it's uncomfortable to hold your breath for a long time. If you inhale pure nitrogen while being able to exhale, there is no build up of CO2 and therefore little to no discomfort.
Wikipedia cites a USAF text, saying: "Some individuals experience headache, dizziness, fatigue, nausea and euphoria, and some become unconscious without warning."
If you want to try it at home, try inhaling the air inside a soda bottle
Better yet, try inhaling Nitrous oxide from whipped creme propellant.