To me it’s very clear where a friendship and an emotional affair differ.
If he wouldn’t be comfortable with you being there and hearing what they talk about, seeing how they interact or reading his messages to her then he’s crossing a line.
Not that you should have to, but it’s more of a self regulation deal. He needs to ask himself if what he’s doing and saying would bother you. And he’ll know the answer to that already.
From your perspective, if you feel the attention, time or investment he’s making in her is disproportionate to the time and affection he has for you, it’s an issue.
The tone of his conversations about her would also indicate to me whether it’s something to be worried about. My new BF has a female best friend who he sees several times a week. They’ve been friends forever, and he’s also friends with her husband. They all go out together (and I’m sure at some point I’ll join them!) and the way he talks about her is much like a sister or a male friend, a bit of piss taking, general (hate the word!) banter, but certainly nothing about her looks, the way she makes him “feel” or how amazing she is!
I don’t know how you can quantify it as you’ll never be party to the whole relationship he has with her but if it’s making you uncomfortable he needs to address it one way or the other.