What would a Pittsburgh topic be without
pitflyer responding?
For a day you've listed a good itinerary there. Go a little bit past downtown to the strip and you can sample many ethnic food delicacies, and also hit the Heinz Regional History Center, which is pretty interesting.
Fallingwater is 1.5-2 hours as chexfan stated. Their hours of operation are pretty limited so check the website or call them if you decide to go. You can pre-book a new special tour they offer -- pretty expensive (around $100, I believe) but if you are a Wright buff than it might be worth it.
Since you are coming in May, probably before Memorial Day, Kennywood and the other area amusement parks will probably not be open. But you can check their websites and see if you are into that sort of thing. Kennywood will have a new extension to their marquee Steel Phantom open this season.
If you just want to kill some time, there are several miniature golf and bowling places around the airport and area -- let me know if you want some directions. There's also a large shopping center not too far from the airport (Century III) and several movie theaters.
Down in Homestead (about 20-30 minutes from the airport) there is a new Dave & Buster's (arcade and other entertainment) along with a brand new (and supposedly very nice) Lowes movie theater. I've wasted many a hours and much much money at that Dave & Buster's perfecting my skills at '18 Wheeler'. Battletech is fun too -- but again darn expensive.
And of course lets not forget PNC Park. While it may not work it in your layover, if you have the opportunity to visit the magnificent new stadium (we won't talk about the team that PLAYS there) you should. The Carnegie Science Center nearby is also neat and undergoing an expansion; tho admittedly it's a bit more for the kiddies.
Finally, if I'm in town I'll be happy to meet you at a McDonalds <grin>