Uhm Galio has already a hextech skin and Urgot won't get a skin until his rework.
And then there's the fact that it makes sense to give the hextech skin to a champion with a low Ip-price,as the skin will most likely come alongside the champ for free and making it so that the skin is for an easily accessible champion will make the hextech boxes probably a lot more desireable.
Also for such a system it would make sense to pick one of the more iconic champions of the game,like annie.
Last but not least you have to keep in mind that it would really suck for these champs to finally get a new skin....only for it to turn out to be an hextech exclusive one that can only be gained with a lot of luck or a lot of RP during the time where premium boxes are avaliable.