22.5 is the angle measurement used when cutting crown molding. If you cut a compound mitre at 22.5 degrees (both angle and bevel) and put two of these pieces together, you come up with a 90 degree angle, with beveled edges at 45 degrees. (It's totally counter-intuitive, I know.... but it's true.)
So you normally wouldn't cut crown molding with a radial arm saw (but you might) - but that is a common application for the 22.5 degree mitre. You might build a four-sided box or picture frame where you want the sides to be sloped at 45 degree angles. (Make one and see...)