High octane fuel should not smell any different when burning to ordinary unless something like naptha or benziene or some other hydrocarbon or wierd substance is added.
A lot of high octane fuels are "old" , IE have been stored a while under bad conditions and the octane rating actually drops or they absorb water - this might be the case if the motor runs rough with them.
As many other posters have said , using higher octane fuel if a lower one works well is a waste of money and depending whats added to raise the octane level , can actually harm your engine - like benziene attacks anything rubber.
Hesitiation on acceleration would not be due to octane ratings , especially if using a HIGHER octane
Its generally a lean condition that causes hesitation (unless it stumbles and emits black smoke) and that might be due to the mix of the 2 fuels and the "vaporising" properties.
As you floor the throttle , intake vaccum drops radically and the engine doesnt "suck" enough fuel , thats where an acceleration pump adds a "booster" shot to stop this.
Changes in the way the fuel reacts with heat etc will change the fuel delivery pattern , for example if the new mix vaporises more readily with heat , then the engine might be starved relative to a fuel that doent vaporise - IE cos you have no vacuum , the better vaporisation is not a desireable trait , a stream of unvaporised fuel might be better to cure the lean condition.