Season 2- Episode 4

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Katherine tells Stefan that she will kill Elena unless he ends his relationship with her, and as a result, Elena realizes that Caroline is working for Katherine.

 Elena and Katherine finally meet, but Katherine ignores Elena's questions.

 Damon stabs Mason with a silver knife, but Mason says it is only a myth that silver hurts werewolves. 

They are now enemies. Katherine remembers how in 1864, after Stefan and Damon were shot in an attempt to save her, she had kissed Stefan, declaring her love and saying they would be together again one day. 

Stefan and Elena stage a fake break-up to prevent Katherine from hurting anybody.

:)

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