At the end when Ritsu was talking to Mio on the phone, I thought Mio was upset because Ritsu didn't tell her that she was hanging out with Mugi... the MUGI mind you! And Mio likes Mugi very much and it's a rare occasion for Mugi to be out like that, SOOOO I figured Mio was like "Mugi was there with you???? What the hell Ritsu you should of called me dammit! Then all 3 of US could of have FUN together!".
I believe in Mio's mind, when Mugi joins the party, things get interesting in a "Mugi" kind of way, so knowing that, just Mio hanging out with Ritsu is predictable, with Mugi in the mix it's not. That's why Mio didn't want to screw her studies and go out with only Ritsu, she's done it MANY times before. Overall, Mio and Mugi have this special connection as you see throughout the series and she just wanted to hangout with not only her childhood bestie but also someone she gets along with very well, is laid-back (unlike Ritsu) and have a serious, mature conversation with... hence why she was upset. She missed the opportunity to hang with Mugi dammit! The MUGI!
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