re: What tipped off The Godfather that it was Barzini

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This is a pretty good detailed explanation of how he knew

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At the start of the Five Families Meeting (FFM), Vito Corleone opens with “How did things ever get so far?” That’s Vito’s way of telling the Five Families that if they wanted his help they should have set up an FFM before this all started. Instead, Barzini calls the meeting and that’s the first tip off to Vito that Barzini is the strategist and Tattaglia is the hot-headed malleable front man.

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No. Vito calls the meeting after Sonny is killed. "I'm going to call a meeting between the heads of the five families. This war must end."

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At the meeting he wants to learn who the real mastermind behind all this is. He sees Barzini taking center-stage, comporting himself as a leader and he has his answer

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Pretty much exactly what I said.