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Dosing. You can order crystalline caffeine, but you have to take micrograms. If you overdose you could have a heart attack.
Availability, coffee is a social and calmly accepted drink wherever you go. Even if you can't get coffee you can get tea. Finding pills is more troublesome.
Because liquid is consumed slowly because it's hot, it's easier to dose to the level of excitement you want. If you ingest a pill there's a delay effect, so it's easy to take too many pills before the impact hits you. Sipping hot coffee, you can get to the point where you're just the right level of jittery and then stop
Caffeine is definitely dosed in milligrams not micrograms.
Typical doses of caffeine are in the high tens to low hundreds of milligrams, which is much easier to measure than micrograms. A potentially lethal dose for a healthy adult is around 10 grams, about a hundred times as much as one would typically take.
There have been incidents of people dying from caffeine powder overdoses; a tablespoon or so is dangerous, but it's easy for anyone who understands what a typical dose looks like to not do that. If it would fit in a pill capsule, it won't kill a healthy, non-hypersensitive adult.
You can buy a whole bag of caffeine pills that will last months.
Dosing on pills is more exacting than coffee which has variability per batch, so you can get the exact amount you want. You have an interesting point about stopping drinking though. You could also take a half pill. I wonder how that would play out with experienced people, if you know how much caffeine you want you can get that exact amount with pills, but you have to know already of time.
There's also the ritual and social aspects.
Nothing stopping people from taking coffee pills. They're pretty cheap. They just don't
I do this all the time. I've gotten used to judging how I feel in the morning, and determining from that how much to take.
You really can't decide by how much difference you feel right after taking a caffeine pill. If someone is going to keep taking one every 10 minutes until it kicks in, that would be deadly.
There's a short lived placebo effect, then half an hour to 45 minutes later, after I've forgotten whether I took one or not, my energy suddenly ramps up. If I've taken more than I need for the day, it's a bit of a ride that I just have to hang on for, it's not going away until the chemicals are done doing chemistry with my brain.
There are also slow-release caffeine pills. It's a slower, smoother ride up and down the energy boost, and more analogous to sipping a caffeinated drink through the day. But without needing to pee 2 or 3 quarts of water that would come with sipping enough drinks to reliably get 100-200mg of caffeine out of it.
I tracked down pills because I can't stand the taste of coffee, so the whole ritual thing is ruined because I hate the stuff. Tea seems more variable in dosage, and energy drinks or Mtn Dew are too expensive both upfront and in long term health expenses.