I created this for the watercolor class I teach. It shows which direction the warm and cool of each primary leans. For example, a warm red leads orange/yellow while a cool leans blue/purple. When mixing a secondary, if both primaries lean toward that secondary color, it will be vibrant. If one leans towards and the other leans away, it will be slightly dulled. If they both lean away, then the color is more neutralized and can look gray or brown. For a vibrant orange, you need warm red and warm yellow. For a vibrant green, you need cool yellow and cool blue. However, for a vibrant purple, you need cool red and warm blue.
As far as determining which specific colors or pigments are warm or cool, if I can't determine it visually I will typically look it up on the brand's web page. I downloaded a PDF from Daniel Smith that lists all of their colors and whether they are warm or cool.
Cool to me would be a color with blue in it, I think of the sky, the water. Hot, warm tones , I think of the sun, yellows, oranges. A cool red ( alizarin crimson, has blue in it. ) A warm red has yellow in it, more orange. (Cadmium red light. Cadmium orange )
Take a look on this site, lots of good in depth info, http://handprint.com/HP/WCL/water.html
If you have questions like this I find the www.handprint.com site is great for such information. Bruce Macevoy spent years researching watercolour pigments and their behaviour. He has info on a primary palette secondary palette etc. Pity he stopped quite a few years ago, so some brands and extra colours have appeared since then but it’s still my go to guide!
Easiest way to explain warm and cool colours...All colours in nature go blue grey in the distance and they go cooler...Warmer colors are closer to the viewer.... eg ..cool yellow will have a greenish tinge where a warm yellow will have a orange tinge...green brown is cool ..a red brown is warm.
Mix burnt sienna with Ultramarine Blue for natural, non-muddy shadows.
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