Most people agree that this is the reason:
The song that is heard begins with the words, "Tell me, where is fancy bred?" In fact, the [first two lines of] the song end [with] a word that rhymes with "lead."
Tell me where is fancy bred,
Or in the heart, or in the head?
Perhaps, Portia is subconsciously trying to help Bassanio in his choice, since she cannot openly help him. It would break her oath to her father. In truth, Bassanio, with his noble nature, needs no help in making the right decision.
Bassanio rejects the gold casket, for he sees gold as deceitful and
superficial; he rejects the silver casket for being symbolic of money. His preference for the lead casket shows that he knows that true worth is often found beneath false appearances.
http://www.pinkmonkey.com/booknotes/mon ... hant25.asp
http://www.web-books.com/Classics/Shake ... ant3_2.htm