When Orochimaru approaches his old squad-mate, he asks her to repair his arms, but when she asks how they were damaged, she is appalled to learn that they were damaged while killing their former teacher, The Third Hokage. This news causes Shizune, Tsunade's aid, to attack Orochimaru, but his aid Kabuto steps in and intercepts the attack. Before the battle can get too heated, Tsunade calls off Shizune (much to her surprise); could it be that she is actually considering helping Orochimaru? What kind of potential Hokage has Jiraiya chosen? Thankfully, before Tsunade can make any rash decisions, Orochimaru decides to give her a week to think about it.
Meanwhile, Naruto has mastered the first two steps of using the Rasengan; he can use his chakra to spin the water in a rubber ball so fast that it bursts the ball. But the last step is even harder. Jiraiya explains that Naruto must now focus all that power into such a tight sphere that it doesn't destroy the ball. So just as much power, but far more control. Needless to say, it will take a lot of work before Naruto can pull this move off.
When these two meet up with Tsunade, Jiraiya realizes that she has already been approached by Orochimaru. When Naruto finally meets up with Tsunade, he doesn't see her, a person with a reputation for drinking and gambling, as worthy of the title of Hokage, needless to say, his hot-headedness causes him to challenge her to a duel. During their brief fight, Tsunade is reminded greatly of two people who were important in her life and are now dead, her lover and her younger brother. Both had dreams of becoming Hokage, and Naruto's typical declaration of eventually holding that title shocks her into realizing how much her former village needs her.
When she sees Naruto attempt to use the Rasengan, she can't believe Jiraiya would teach a kid such a high-level move. But when the knuckleheaded ninja claims that he will master it in three days, Tsunade bets Naruto's skills against a necklace that has been in her family for a long time, and was previously worn by her brother (after all, it took The Fourth Hokage years to be able to use this attack). Before Tsunade fully commits to becoming Hokage, she sneaks off and looks for Orochimaru, but at this point, her decision is still unclear.
Like I said at the beginning, Volume 23 is all about character development between the three Sannin, but mostly for Tsunade. We learn a lot about her complex path, both with her as a ninja and with her family. While quite a few important events happen in these four episodes, it feels fairly drawn out. If you aren't much for character development, then you can probably skip this disc, but if you've got all of the other ones, you might as well get this one at some point.