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Annamay Pierse of Canada, who set the world record of 2:20.12 in Rome, finished eighth.
In the men's 50 free semifinals, Brazilians Bruno Fratus and Cesar Cielo went 1-2, with American Nathan Adrian third. French standout Alain Bernard just made the final in eighth.
"It's going to be better to have my Brazilian teammate by my side," Cielo said. "I think he's hands down the favorite for the gold tomorrow."
Cielo swept both the 50 and 100 free at the last worlds and is also the Olympic champion in the 50. He was cleared of doping by the Court of Arbitration for Sport last week.
Phelps led the 100 butterfly semifinals in 51.47, then hurried out of the pool to prepare himself for the leadoff leg in the 4x200. Milorad Cavic, the Serb who challenged Phelps in Beijing and Rome, failed to qualify in morning heats as he recovers from back surgery.
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