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1510s, from Latin alternatus "one after the other," past participle of alternare "to do first one thing then the other; exchange parts," from alternus "one after the other, alternate, in turns, reciprocal," from alter "the other" (see alter). Alternate means "by turns;" alternative means "offering a choice." Both imply two kinds or things.
1718, "that which alternates (with anything else)," from alternate (adj.). Meaning "a substitute" is first attested 1848.