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Which is the most appropriate word to describe the state of a system which is ready to work: operative or operational?

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Operational. But did you try dictionaries first? If so, what leaves you unsure? – Jon Hanna Feb 6 at 20:57
I endorse Jon's comment. "Operational" can mean "able to function" while "operative" has its own applications in reference to a secret agent or a private detective. And you might be intesested in our new site for English language learners link – Carlo_R. Feb 6 at 21:13

closed as general reference by Jon Hanna, Carlo_R., MετάEd, RegDwighт♦ Feb 6 at 21:39

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