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There was a recent thread about this on wetcanvas. As a result, I bought Richard Schmid's book, in which he highly recommends (Pleads) that all artists make charts for their entire palette. One chart shows how each pigment looks mixed with varying amounts of white, then the others show each color mixed with every other color on the palette. You'd have say, a cad red chart in which each column contains cad red mixed with one other color on the palette. Then the resulting color is mixed with white, to make a full range of values.
You might think that this results in a lot of duplication (ie. cad red and yellow ochre would look the same on the cad red chart, and the yellow ochre chart), but not so. The colors are mixed so that the main color for each chart dominates, if only by a small degree.
Schmid says that everyone should invest the time to do this, and not just as an exercise, but keep the charts handy as a reference to refer to while painting. From looking at the charts in his book I'd imagine nearly any color you want can be made with only two colors plus white. Mixing five or six pigments to get the right color seems like guesswork compared to his method.
I just got the book this week, and haven't had much time to spend with it, but I will definitely be making those charts, and I'll probably hang them on the wall of my studio.
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