If there is a seat and you want to take the earlier flight, you have to pay the $25 fee. There is no free standby on open flights. If the flight is booked full and you cannot be confirmed at the counter, then there is no charge.
As for taking a later flight, I actually called our help desk on this one because I wasn't sure. It wasn't very clear to me either. However if you chose to take a later flight you now must requalify for the fare. It's the whole $100 plus any additional collection. There is no standby of any sort for later flights.
You may get lucky and find someone who will just charge the $25 and be done with it, that is actually what I would do. However if you find yourself with a stickler and you missed your earlier flight, have your credit card ready.