Ok, thanks. I do know about subnets, at least enough to choose masks properly to set up a 10.x.x.x network, with different kinds of devices on the different subnets (we had four at a broadcast facility I worked at). I thought perhaps Pfsense might had some sort of exception handling mechanism to treat specific requests differently.
The purpose of this project is to duplicate a manufacturing system we have (for testing purposes), with many unusual sensors and process controllers on one subnet, and the office LAN on the other. It's been proving to have some difficult lessons for me.