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Assuming we're not throwing ions into the flame and the color is due strictly to temperature, the blue flame is hotter.

The problem is that flames can be different colors for reasons other than temperature. Specifically, they may contain ionized materials with strong emission lines that color the flame. Probably the easiest example to observe using ordinary household materials is sodium which gives an orangish yellow color (easily seen by dropping a few crystals of table salt into the flame of a gas stove).

The reason that hotter flames are blue is that blue light is more energetic than red light. A hotter flame has more energy, and therefore generates more energetic light.

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