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Effects of octane rating
Higher octane ratings correlate to higher activation energies. Activation energy is the amount of energy necessary to start a chemical reaction. Since higher octane fuels have higher activation energies, it is less likely that a given compression will cause knocking. (Note that it is the absolute pressure (compression) in the combustion chamber which is important - not the compression ratio. The compression ratio only governs the maximum compression that can be achieved).
Octane rating has no direct impact on the deflagration (burn) of the air/fuel mixture in the combustion chamber. Other properties of gasoline and engine design account for the manner at which deflagration takes place. In other words, the flame speed of a normally ignited mixture is not directly connected to octane rating. Deflagration is the type of combustion that constitues the normal burn. Detonation is a different type of combustion and this is to be avoided in spark ignited gasoline engines. Octane rating is a measure of detonation resistance, not deflagration characteristics.
It might seem odd that fuels with higher octane ratings explode less easily, yet are popularly thought of as more powerful. The misunderstanding is caused by confusing the ability of the fuel to resist compression detonation as opposed to the ability of the fuel to burn (combustion). However, premium grades of petrol often contain more energy per litre due to the composition of the fuel as well as increased octane.
A simple explanation is that carbon-carbon bonds contain more energy than carbon-hydrogen bonds. Hence a fuel with a greater number of carbon bonds will carry more energy regardless of the octane rating. A premium motor fuel will often be formulated to have both higher octane as well as more energy. A counter example to this rule is that ethanol blend fuels have a higher octane rating, but carry a lower energy content on a volume basis (per litre or per gallon). The reason for this is that ethanol is a partially oxidized hydrocarbon which can be seen by noting the presence of oxygen in the chemical formula: C2H5OH. Note the substitution of the OH hydroxyl radical for a H hydrogen which transforms the gas ethane (C2H6) into ethanol. Note that to a certain extent a fuel with a higher carbon ratio will be more dense than a fuel with a lower carbon ratio. Thus it is possible to formulate high octane fuels that carry less energy per liter than lower octane fuels. This is certainly true of ethanol blend fuels (gasohol), however fuels with no ethanol and indeed no oxygen are also possible.
In the case of alcohol fuels, like Methanol and Ethanol, since they are partially oxidized fuels they need to be run at much richer mixtures than gasoline. As a consequence the total volume of fuel burned per cycle counter balances the lower energy per unit volume, and the net energy released per cycle is higher. If gasoline is run at its preferred max power air fuel mixture of 12.5:1, it will release approximately 19,000 BTU (about 20 MJ) of energy, where ethanol run at its preferred max power mixture of 6.5:1 will liberate approximately 24,400 BTU (25.7 MJ), and Methanol at a 4.5:1 AFR liberates about 27,650 BTU (29.1 MJ).
To account for these differences, a measure called the fuel's specific energy is sometimes used. It is defined as the energy released per air fuel ratio. For the case of gasoline compared to the alcohol fuels the specific energys are as follows:
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