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No. The molecules MAY (and probably are if you are presented with this situation in school/college lab courses) be identical but just the Rf values is not enough information to determine, you must conduct additional tests. Two different molecules can have the same Rf value.

Compound A will always have an Rf of X in solvent M. Compound B will always have and Rf of Y in solvent M. But, Rf X can be equivalent to Rf Y without compounds A and B being identical.

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