If you’re talking about true cough suppressant (q.v. dextromethorphan), it doesn’t. It actually interferes with your brains ability to detect tiny foreign objects and irritation in your throat. Expectorants (q.v. guaifensen) increase the amount of moisture secreted in your throat and lungs, thereby making it easier to cough up the resulting mucous.
When your airway is constricted it tends to rub on itself becoming further inflamed/irritated. The airway will create mucous as a lubricant to help ease this irritation.
Suppressants help relax (dialate) your airway so the mucous can drain easier they can also act by blocking the signal to your brain that the airway is irritated so you wont cough and further irritate the airway.
Expectorants will make the mucous more clumpy and easier to cough up.
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