Hmm yes it is 1/3, not 1/5
I think your collegue is mistakenly thinking about "what are the changes of picking both purple balls"
But the fact that the first purple ball was picked is a given, that fact has a 100% probability, thus the only chance remaining is the chance of picking the 'other' purple ball from the remaining three balls, which is 1/3.
Here's another riddle for you though.
Assume you're playing the infamous ball-and-cup game, where you have three cups with a ball under one cup.
Now, after the dealer shuffles the cups, you get to choose one cup, but you can't lift it up yet. Now the dealer will lift one of the remaining cups to show wether that one has the ball under it or not. Now he gives you a chance to change your mind and pick another cup if you wish.
Q: should you change your mind and pick another cup? or does it not matter?