White is an equal mixture of all three channels. As is a neutral grey and also pure black. When sampling colours in Photoshop the value of each of the three channels will range from 0 to 255 (if working in 8 bit). Values of 0,0,0 will be black, and 255,255,255 will be white. Various shades of grey will be somewhere between.
That's what makes using a grey card so useful. By comparing the amount of red green and blue present, it's possible to see if there is too much/not enough of any of the three colours, and to make adjustments so that all three colours are equal, giving a neutral image with no colour cast, irrespective of the light source being used.