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When should I specify RGB, CMYK and PMS colours?

RGB - For anything on a screen - eg. TV, web, video, presentations.

CMYK - Is a printing specification when printing the process colours (cyan, magenta, yellow and black). This process prints 4 layers of ink dots in various sizes that make up millions of colours - eg. magazines, brochures, newsletters.

PMS - Another printing specification where base inks are mixed in percentages to make a specific colour and printed solid (100%) and or tints of that colour - generally used for stationery, merchandise, plastic bags.