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In one scene, in their makeshift mobile meth lab out in the Arizona desert, Walt is being threatened by two gangsters. He improvises a method to gas them by throwing red phosphorus into hot water. Walt manages to run out, locking the gangsters in. He later explains to Jesse that this reaction produced poisonous phosphine gas. Red phosphorus can react with hydrogen to produce phosphine - but not with hot water. White phosphorus can react with sodium hydroxide (a chemical he would have had) but you can see he throws in a red powder, rather than a white substance. Nor is that what he describes to Jesse. I don't think this trick would work.
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