Your vomit contains really harsh acid. Your saliva can help to protect your mouth from this by basically forming a layer between your skin and the acid.
As far as how it knows, your stomach has a ton of sensors in it that tell your brain something is wrong. As the brain gets a stronger and stronger signal it starts prepping the body (deep breaths, increased saliva, tensing of the abs, closing of the wind pipe). Eventually the signal crosses a threshold and you vomit.
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