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Yup, basically if you would EQ out the S sounds the normal way (with an equalizer) you permanently affect the sound (it'll sound muffled).
With a deesser, if it's set up correctly, it won't change anything to the sound, until a sybilant sound comes up.
Nowadays, you can find "premade" de-essers, but originally, it's nothing but a compressor with an EQ'ed sidechain.
Example : vocal goes into compressor, but is also splitted to the sidechain (the controlling circuit of the compressor). The splitted version is EQ as to remove low frequencies, and boost the sybilant frequencies (that's your job, you'll try to focus the boost at the place where it's most annoying, and that depends on the voice, and also if it's a male or female, in general between 7 and 9 kHz). In practice that will result in the compressor only reacting to the annoying S sounds.
Of course, when miking vocals, it's always prefered to solve the sybilance problems at the source, by positioning the mic differently (or sometimes using the pencil trick works also).
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