I studied the schematic a bit more: on the PB 100, the 85C80's SERIALA goes to the modem, all signals (except) are buffered via a 244, SERIALB just goes to the line transceiver (the schematic does not say what it is, I will open my unit later for curiosity) and then out to the port. So I think that unless there is a software limitation (scc's portb is hardcoded?) probably using a patched driver that shows the modem port could work.
Edit it is an LTC902CS, but I could not find a datasheet, in any case it does not make any difference since I would use the other port.