Stomach acid is pretty nasty – as the name suggests, it is an acid, and its main purpose is to break down food.
When it is in your stomach and lower digestive system, this is fine – your stomach is designed to cope with the acid.
Your mouth and esophagus however are not designed to cope with this level of acidity, only the much more neutral foods your will be eating. This means that when you are sick, the acids you vomit up can damage the throat and mouth on the way out.
By salivating lots when you are going to be sick, your body is attempting to coat itself in saliva to provide some protection against the acidic vomit.
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