On a Galileo with PMG you can definitely switch between gases underwater at any time, back and forth, as many times as you need (as long as the gases are predefined at surface, and enabled). The only "impact" will be that (a) the computer will ask you to switch to the optimal gas at the correct MOD, which you can ignore and it goes away, and (b) that at depth, the total ascent time will assume that you will use the optimal gases. While you ascend and ignore the switches, it will recalculate, but it will give you incorrect information about your total deco obligation during the dive.
The above issues are true for any other multi-gas computer.
What is worse than that is that if you use air and your computer thinks you have EAN32, then it will underestimate your nitrogen intake, and depending on how many minutes it takes you to correct the situation, your total real NDL will be shorter than estimated - so you should not stay in water until it goes to zero, and you cannot tell how sooner you should end your dive in reality - (or your deco will be longer than computed). The reverse (using EAN32 with an air configured computer) is not unsafe, it will just artificially shorten your NDL.