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In theory Nitrogen suffocation should be incredibly humane. Nitrogen gas is incredibly dangerous in the workplace exactly because the human body is incapable of noticing it displacing air. It can kill you without you even noticing until you keel over dead.
Problem is when you shove a mask on someone's face and pump nitrogen into it, that's not what you're doing...
That doesn't displace the air the executed was breathing, because the air has nowhere to go, so it just mixes with the Nitrogen gas. The O2 gets used up and CO2 builds up until they die, which is basically normal suffocation (which is incredibly inhumane) with a side of Nitrogen gas.
To do it properly, you'd need to a much bigger chamber so that the air in the executed's lungs would be easily displaced, or a way to filter the CO2 out of the air they're breathing... But who's got time for that, when you can just torture prisoners with something that should be humane and pretend you have no idea why it "doesn't work properly" /s
And you'll likely laugh about it while you're dying!
https://youtu.be/kUfF2MTnqAw