It has to be mixed with water or it'll be too harsh. You can experiment with the dilution rate but I usually use 1 tablespoon of vinegar to every 2 cups of water.
You can choose whether to use it as a final rinse or to rinse it out after you're done. Some people said that the smell of vinegar goes away after the hair dries but I've found that it always lingers. Also, some people complained that the smell reappears Shen they get caught in the rain. So I choose to rinse again with water after the vinegar rinse.
The acidic nature of the rinse is supposed to balance your scalp's pH level and it's also supposed to make hair more shiny by making hair cuticles lie flatter I think
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