If you're talking about using gel electrophoresis to separate proteins by their pI. The set up is so that the "pool" is composed of gradient of pH buffers. Proteins are then loaded at one end, and they will keep traveling toward the opposite end until their pI=pH of the buffer. pH of the buffer does not increase as current is applied, but as current is applied, proteins start moving toward the opposite end. For example, if they're loaded at pH=0 end, all proteins will be + charged, so when current is applied, they will go toward - end (cathode, where cations go) When proteins are at the pI, the charge is 0, so current applied can't move the proteins, that's where they stop and we use that to separate proteins.