The man in front knew he was wearing a black hat because he knew the first man did not see two white hats and he knew that the second man did not see one white hat because if he saw a white hat, the second man would have known that his hat was black from hearing the first man's statement.
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The solution is a bit confusing, but ask me in person (or via personal message) if you don't understand it.

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A Riddle a Day -- 78 Logical and Mathematical Puzzles
RandomSome riddles and brainteasers to give you a little something to think about each day!