No what I saying is that is how you could flag traffic in windows. Then you should be able to route that traffic with whatever specific marker you put.
There is no other way I know of to tag or mark traffic coming from a specific application other than with dcsp.
You can route traffic in pfsense really easy based upon source IP, source port, Dest port, dest IP, etc. And then you can tag that traffic for other rules to process, etc. But that is not what you asked - you asked per application how to mark the traffic.
So for example you could part traffic that is coming from your browser with af11, and traffic coming from say application XYZ with af12.. Then you could tag traffic coming from IP of your box with af11 as browser, and traffic with af12 as application and then route it based on those tags i pfsense rules.
This way even if going to the same dest IP, you could could tell what is browser traffic and what is application traffic.