Hmm... no chemist on the list, odd.
With the octane ratings, you can "blend" the fuel. A neat trick, YEARS AGO, was to mix leaded and unleaded. OK, most folks haven't seen leaded for 15 years... but the early unleaded fuel, when added to leaded, would give it a nice kick. So when "regular" was 91 octane, and "unleaded regular" was 91 octane... a blend of 70/30 gave a 96 octane! Way too cool for high compression carb'd engines back then.
Odd thing about fuel... same base is used. Fuel flame fronts will travel at the same speed for regular or premium. It is the additive package that changes the knock index.
The thing that still blows my mind is a perfect 14.7:1 a:f ratio (remember that stoic only applies to regular gasolene, alcohol, and other fuels have a different ratio)... the flame front is in the order of meter per second. So if you had a ROOM full of A:F in the proper mixture, and ignited it 30 ft away... you would have 10 SECONDS to leave the room (if you were at the far end by the exit door!). So if that is true, and I have a piston of 75mm bore... doesn't that mean it takes a long time for the mixture to burn? YES, catch is TURBULENCE. The more turbulence, the faster the mixture burns. Turbulence also will affect any "knock" issues to the motor.
Had some friends up in Ann Arbor who could mix up stuff and test it on the octane test engine. Pretty cool, but lots of the fuel boosters were plain ol' industrial toluene (janitor supply stuff for stripping floors). VERY NASTY chemical, but we could buy it in 5 gallon buckets cheap. Wouldn't mess with it these days.
With the modern EFI systems, there is a knock sensor -- or way of detecting knock via misfire (crank angle speed), so the timing is backed way off when that occurs. Stock engine doesn't blow up or melt down, just you can feel the power back off. Thankfully most of us keep our foot of the throttle when we feel that. Now if you are running 20 psi boost, horrible gas, things might go really bad in that short 1/4 run!
EuroSx -- I hear you! Lived in Germany, and paid about $4/gallon for my VW Golf Bistro (1600cc 8V, GTi interior & suspension). Loved living there... but blowing $50 to fill up once a week was a pain! :pface
Too much coffee this morning!
Tom