The One With Rachel's Inadvertent Kiss - S5-E17
Revealing mistake: When Ross is doing his "Watching TV" bit, there is a brief shot of the blank screen that he is sitting on the sofa pretending to watch. In the screen's reflection, it is clear that the sofa is empty. (00:03:55)
Answer: The statements that she's contradicting (that it is common, it happens to every guy, and it's not a big deal), are the things that a woman commonly says to a man who is suffering from erectile difficulty, typically to assuage his bruised ego. However, most men do not believe that these statements are true, as evidenced by Chandler's outburst. He's so caught up in the proof that women are lying about it that he gives himself away.
Rooster of Doom