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I believe the officer in charge of the firing squad has a pistol that they'll use to finish you off, but that's still not my definition of quick or painless.
For the record, I'm like 99% against the death penalty (I could be convinced if the crime was bad enough, the perpetrator was completely unrepentant and there was absolutely zero doubt of guilt, but that last one is a very high bar to clear), but can someone explain why instead of nitrogen, they don't use carbon dioxide? Doesn't that have a very similar "you fall asleep and never wake up" effect?
I think you're thinking of carbon monoxide. Carbon dioxide buildup in your lungs would be most unpleasant.
I guess that could work too though but it's a dangerous gas where nitrogen isn't.
Sure, our body has excess CO2 detectors. The feeling of not getting enough air usually has very little to do with not enough oxygen, because there is a lot of oxygen in the air, much more than we need. It's usually the excess CO2 detectors going off. This is also the reason we pant after holding our breath, the quick deep breaths help quickly lower the CO2 level.
For other gasses you are right. CO (Carbon monoxide) doesn't trigger our CO2 detectors, which is why you can die so easily due to a faulty heater or something like that. Killing yourself by running a car in the garage also kills using CO, the body does not notice, you fall asleep and die.
A lot of other gasses also displace oxygen, without our bodies knowing. For example argon or even natural gas (methane). This is where the putting your head in the oven thing comes from. Back in the day there was pure gas in the pipes, so gassing yourself this way was easy. These days they mix in a lot of other stuff so it doesn't work anymore.
The reason nitrogen is used is because it is cheap, easily available and non toxic. Regular air is almost all nitrogen, so the nitrogen itself isn't the dangerous part, the dangerous part is the lack of oxygen. Since CO2 is still exhaled, the detectors don't trigger and you die peacefully.