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PRIMARY COLORS are: RED, BLUE, YELLOW.
How Do I Know What Colors My Primaries Will Produce?
Red and yellow always make some kind of orange, yellow and blue a green, and blue and red a purple. The actual color you get depends on which primary you're using and the proportions in which you mix the two primaries. Paint a color chart where you record which two colors you mixed and the (approximate) proportions of each. This will provide you with a ready reference until you get to the stage when you instinctively know what you'll get.
How Much of Each Primary Color Do I Use?
The proportions in which you mix the two primaries is important. If you add more of one than the other, the secondary color will reflect this. For example, if you add more red than yellow, you end up with a strong, reddish orange; if you add more yellow than red, you produce a yellowish orange. Experiment with all the colors you have - and keep a record of what you've done.
Why Do My Colors Keep Turning Out Muddy?
If you mix too many colors together, you'll get mud. If your gray or brown isn't coming out the way you want it to, rather start again than add more color in the hope it'll work.
While it may seem logical that to lighten a color you add white to it and that to darken it you add black, this is an oversimplification. White reduces brightness so although it makes a color lighter, it removes its vibrancy. Black doesn't so much add darkness as create murkiness. Black tends to dirty colors rather than simply darken them.
Browns and grays contain all three primary colors. They're created by mixing either all three primary colors or a primary and secondary color (secondary colors of course being made from two primaries). By varying the proportions of the colors you're mixing, you create the different tertiary colors.
What's the Easiest Way to Mix a Brown?
Mix a primary color with its complementary color. So add orange to blue, purple to yellow, or green to red. Each of these makes a different brown, so once again make up a color chart to give you a quick reference to refer to.
What's the Easiest Way to Mix a Gray?
Mix some orange (or yellow and red) with a blue then add some white. You'll always want more blue than orange, but experiment with the amount of white you use. You can also mix blue with an earth color, such as raw umber or burnt sienna.
The complementary color of a primary color (red, blue, or yellow) is the color you get by mixing the other two primary colors. So the complementary color of red is green, of blue is orange, and of yellow is purple.
What About Secondary Colors?
The complementary of a secondary color is the primary color that wasn't used to make it. So the complementary color of green is red, of orange is blue, and of purple is yellow.