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Preheat oven to 375°F. Grease and flour twenty-four 3-inch madeleine molds; set aside. In a small bowl stir together flour, baking powder, baking soda, and salt; set aside.
In a medium mixing bowl beat egg yolks and sugar with an electric mixer on medium to high speed about 30 seconds or until combined. Add melted butter, orange peel, orange liqueur, and vanilla. Beat on low speed until combined.
Sprinkle about one-fourth of the flour mixture over egg yolk mixture; fold in gently. Repeat, folding in the remaining flour mixture by fourths. Gently stir in egg whites. Spoon batter into the prepared madeleine molds, filling each about half full.
Bake for 10 to 12 minutes or until edges are golden and tops spring back when lightly touched. Cool in molds for 1 minute. Using the point of a knife, loosen each madeleine from mold; invert onto a wire rack. Cool completely.