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Can I assume that transition at a specific pH is equivalent to the pKa value of the embedded acid functionalities?

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Can I assume that transition at a specific pH is equivalent to the pKa value of the embedded acid functionalities?

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Your assumption is right for aqueous solutions, but in many cases RP chromatography is performed in a mixture of organic solvent and water. For these mobile phases, the pKa can shift by one or more pH units.

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