There may be several episodes in which Starfire drinks mustard, but the first one that I know of was 'The Sum of his Parts', which was Season 1's episode 5, the second and last being 'Mother Mae Eye', which was Season 4's episode 10.
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Original series episode 3
Brian: Portrait of a Dog
"8 Simple Rules For Dating My Teenage Daughter"
She made $11,000 an episode at the height of the show's popularity and all the free drinks she could drink.
BOSTON