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The autoignition resistance of a practical gasoline is best characterized by the Octane Index, OI, defined as RON-KS, where RON and MON are respectively, Research and Motor Octane Numbers, S is the sensitivity (RON-MON) and K is a constant depending on the pressure and temperature history of the fuel/air mixture in an engine. Experiments in knocking SI engines, HCCI engines and in premixed compression ignition (PCI) engines have shown that if two fuels of different composition have the same OI and experience the same pressure/temperature history, they will have the same autoignition phasing. A practical gasoline is a complex mixture of hydrocarbons and a simple surrogate is needed to describe its autoignition chemistry. A mixture of toluene and PRF (iso-octane + n-heptane), TPRF, can have the same RON and S as a target gasoline and so will have the same OI at any given K value and will be a very good surrogate for the gasoline.

As SI engines strive for higher efficiency they are more likely to encounter knock and fuel anti-knock quality, which is currently measured by RON and MON, becomes more important. However, the RON and MON scales are based on primary reference fuels (PRF) - mixtures of iso-octane and n-heptane - whose autoignition chemistry is significantly different from that of practical fuels. Hence RON or MON alone can truly characterize a gasoline for its knock behavior only at their respective test conditions. The same gasoline will match different PRF fuels at different operating conditions. The true anti-knock quality of a fuel is given by the octane index, OI = RON −KS where S = RON − MON, is the sensitivity. K depends on the pressure and temperature evolution in the unburned gas during the engine cycle and hence is different at different operating conditions and is negative in modern engines.

Extensive tests have been carried out in a single-cylinder Direct Injection Spark Ignition (DISI) engine using up to fifteen different fuels at inlet pressure of up to 3.4 bar abs. to study fuel effects as well as inlet pressure effects on knock. In addition fuel effects on particulate emissions at part-throttle were measured. Fuel anti-knock quality does not correlate with MON and is best described by the Octane Index, OI = RON-KS where S = RON -MON is the sensitivity of the fuel and K is a constant depending on the engine pressure/temperature regime. The RON of the fuels considered was in the range between 95 and 105 and the sensitivity between 8 and 13. K is negative at all the conditions tested, i.e., for a given RON, a higher sensitivity fuel has better anti-knock quality. K decreases with increasing intake pressure and more generally, decreases as Tcomp₁₅, the temperature of the unburned gas at a pressure of 15 bar decreases.

Detailed combustion studies have historically been conducted in simplified reacting systems, such as shock-tubes and rapid compression machines. The reciprocating internal combustion engine presents many challenges when used to isolate the effects of fuel chemistry from thermodynamics. On the other hand, the conditions in such engines are the most representative in terms of pressure and temperature histories. This paper describes the use of a single-cylinder research engine as an advanced reactor to better determine fuel effects experimentally. In particular, a single-cylinder engine was operated in a manner that allowed the effects of changes in charge composition and temperatures to be isolated from changes in equivalence ratio. An example study is presented where the relative effects of low-temperature and high-temperature chemistry, and their effects on combustion phasing, are isolated and examined.