Episode 14 of Batman the Animated Series was entitled Heart of Ice. It is one of the most critically acclaimed episode of Batman the Animated Series and obviously one of the most memorable. It has the first appearance of Mr. Freeze in Batman the Animated Series. Interestingly enough, while it was the fourteenth episode to be made, it was the third episode of Batman the Animated Series to air on September 7th 1992. As always, I'm going in order of production as opposed to air date.
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