Mmm, I've only played the original (Exxtra), a while ago but plenty of times.
So if you are referring to Excape and I'm assuming there is no change in rules, I confused by the roll of 14 as the dice are combined to make the highest number possible. So 14 would be 41.
Anyway to answer your question yes you can place the dice anywhere on an empty space, though many can occupy the 0 spot (according to Exxtra rules), but say that you rolled a 7 and a 4 making 74, if you placed the pair BELOW the 71, that "71" dice is returned immediately with no movement.
Thanks, you are right, it should 41!
I guess it's fine to put a 41 above a higher number (like a 71) because if the 71 player out theirs at 1, than it's hard for others to put on something anymore.