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The primary reason is that Mai and Ty Lee, her two best friends, betrayed her.

She had always been partly crazy. You could see it in her cruelty; her cold, calculating personality, and the way she treated her servants. She managed to keep her composure through most of the series, putting on a very clean and professional demeanor.

However, once Mai (the knife-throwing goth-like girl) and Ty Lee (the happy, chi-blocking acrobatic girl) betrayed her in The Boiling Rock Part 2, she began to slip. She began to banish everyone, believing that everyone, at some point, would betray her. Then when her father, Fire Lord/Phoenix King Ozai, dubbed her the next Fire Lord, all the power went right to her head. She didn't know how to handle it, and it was too much for her.

The Last Agni Kai was the obvious part of her mental breakdown, as she fought Zuko with no mercy as usual. You could see her lightening was also very messy and all over the place as opposed to her usual form.

Finally, upon defeat, she lost it, and we all saw how that ended up.

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Q: Why was azula slipping at the end?
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