When we execute people, we measure how humane the execution is by how much pain the executed appears to be experiencing. That's a flawed methodology. If they appear to be experiencing a lot of pain, how do we know they're not faking it just to make their last moments more dramatic?
The way I see it, if you want to make executions more humane, use methodologies that kill the person instantly or as close to an instantly as possible. Firing squads kill people pretty quickly, and they could be even quicker by having the shooters aim for the head instead of the chest. Electric chairs have gotten a bad rap for taking too long to kill people, but I think they could work faster if they were better engineered. Maybe the next time we execute someone in an electric chair, that someone should stick their feet in cold water, in addition to having a wet sponge on their head. That might speed things up a bit.