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Lomac 04-16-2009 11:49 PM

Fuel, Octane & Ignition Information
 
Article originally written by B.Hamilton@irl.cri.nz (Bruce Hamilton) and has been reduced for brevity.

Why do we need Octane Ratings?

To obtain the maximum energy from the gasoline, the compressed fuel-air mixture inside the combustion chamber needs to burn evenly, propagating out from the spark plug until all the fuel is consumed. This would deliver an optimum power stroke. In real life, a series of pre-flame reactions will occur in the unburnt "end gases" in the combustion chamber before the flame front arrives. If these reactions form molecules or species that can autoignite before the flame front arrives, knock will occur.

Simply put, the octane rating of the fuel reflects the ability of the unburnt end gases to resist spontaneous autoignition under the engine test conditions used. If autoignition occurs, it results in an extremely rapid pressure rise, as both the desired spark-initiated flame front, and the undesired autoignited end gas flames are expanding. The combined pressure peak arrives slightly ahead of the normal operating pressure peak, leading to a loss of power and eventual overheating. The end gas pressure waves are superimposed on the main pressure wave, leading to a sawtooth pattern of pressure oscillations that create the "knocking" sound.

The combination of intense pressure waves and overheating can induce piston failure in a few minutes. Knock and preignition are both favored by high temperatures, so one may lead to the other. Under high-speed conditions knock can lead to preignition, which then accelerates engine destruction


What fuel property does the Octane Rating measure?

The fuel property the octane ratings measure is the ability of the unburnt end gases to spontaneously ignite under the specified test conditions.
Within the chemical structure of the fuel is the ability to withstand pre-flame conditions without decomposing into species that will autoignite before the flame-front arrives. Different reaction mechanisms, occurring at various stages of the pre-flame compression stroke, are responsible for the undesirable, easily-autoignitable, end gases.

During the oxidation of a hydrocarbon fuel, the hydrogen atoms are removed one at a time from the molecule by reactions with small radical species(such as OH and HO2), and O and H atoms. The strength of carbon-hydrogen bonds depends on what the carbon is connected to. Straight chain HCs such as normal heptane have secondary C-H bonds that are significantly weaker than the primary C-H bonds present in branched chain HCs like iso-octane.

The octane rating of hydrocarbons is determined by the structure of the molecule, with long, straight hydrocarbon chains producing large amounts of easily-autoignitable pre-flame decomposition species, while branched and aromatic hydrocarbons are more resistant. This also explains why the octane ratings of paraffins consistently decrease with carbon number. In real life, the unburnt "end gases" ahead of the flame front encounter temperatures up to about 700C due to compression and radiant and conductive heating, and commence a series of pre-flame reactions. These reactions occur at different thermal stages, with the initial stage (below 400C ) commencing with the addition of molecular oxygen to alkyl radicals, followed by the internal transfer of hydrogen atoms within the new radical to form an unsaturated, oxygen-containing species. These new species are susceptible to chain branching involving the HO2 radical during the intermediate temperature stage (400-600C), mainly through the production of OH radicals. Above 600C, the most important reaction that produces chain branching is the reaction of one hydrogen atom radical with molecular oxygen to form O and OH radicals.

The addition of additives such as alkyl lead and oxygenates can significantly affect the pre-flame reaction pathways. Antiknock additives work by interfering at different points in the pre-flame reactions, with the oxygenates retarding undesirable low temperature reactions, and the alkyl lead compounds react in the intermediate temperature region to deactivate the major undesirable chain branching sequence.

The antiknock ability is related to the "autoignition temperature" of the hydrocarbons. Antiknock ability is _not_ substantially related to:
• The energy content of fuel, this should be obvious, as oxygenates have lower energy contents, but high octanes.
• The flame speed of the conventionally ignited mixture, this should be evident from the similarities of the two reference hydrocarbons. Although flame speed does play a minor part, there are many other factors that are far more important. ( such as compression ratio, stoichiometry, combustion chamber shape, chemical structure of the fuel, presence of antiknock additives, number and position of spark plugs, turbulence etc.) Flame speed does not correlate with octane.


What does the Motor Octane rating measure?

The conditions of the Motor method represent severe, sustained high speed, high load driving. For most hydrocarbon fuels, including those with either lead or oxygenates, the motor octane number (MON) will be lower than the research octane number (RON).

Test Engine conditions Motor Octane
Test Method ASTM D2700-92 [104]
Engine Cooperative Fuels Research (
Intake air temperature 38 C
Intake air humidity 3.56 - 7.12 g H2O / kg dry air
Intake mixture temperature 149 C
Coolant temperature 100 C
Oil Temperature 57 C
Ignition Advance - variable Varies with compression ratio
(e.g. 14 - 26 degrees BTDC)
Carburetor Venturi 14.3 mm


How is the Octane rating determined?

To rate a fuel, the engine is set to an appropriate compression ratio that will produce a knock of about 50 on the knock meter for the sample when the air-fuel ratio is adjusted on the carburetor bowl to obtain maximum knock. Normal heptane and iso-octane are known as primary reference fuels. Two blends of these are made, one that is one octane number above the expected rating, and another that is one octane number below the expected rating. These are placed in different bowls, and are also rated with each air-fuel ratio being adjusted for maximum knock. The higher octane reference fuel should produce a reading around 30-40, and the lower reference fuel should produce a reading of 60-70. The sample is again tested, and if it does not fit between the reference fuels, further reference fuels are prepared, and the engine readjusted to obtain the required knock. The actual fuel rating is interpolated from the knock meter readings.


Can higher octane fuels give me more power?

On modern engines with sophisticated engine management systems, the engine can operate efficiently on fuels of a wider range of octane rating, but there remains an optimum octane for the engine under specific driving conditions. Older cars without such systems are more restricted in their choice of fuel, as the engine cannot automatically adjust to accommodate lower octane fuel. Because knock is so destructive, owners of older cars must use fuel that will not knock under the most demanding conditions they encounter, and must continue to use that fuel, even if they only occasionally require the octane.

If you are already using the proper octane fuel, you will not obtain more power from higher octane fuels. The engine will be already operating at optimum settings, and a higher octane should have no effect on the management system. Your drivability and fuel economy will remain the same. The higher octane fuel costs more, so you are just throwing money away. If you are already using a fuel with an octane rating slightly below the optimum, then using a higher octane fuel will cause the engine management system to move to the optimum settings, possibly resulting in both increased power and improved fuel economy. You may be able to change octanes between seasons (reduce octane in winter) to obtain the most cost-effective fuel without loss of drivability.

Once you have identified the fuel that keeps the engine at optimum settings, there is no advantage in moving to an even higher octane fuel. The manufacturer's recommendation is conservative, so you may be able to carefully reduce the fuel octane. The penalty for getting it badly wrong, and not realizing that you have, could be expensive engine damage.


Does low octane fuel increase engine wear?

Not if you are meeting the octane requirement of the engine. If you are not meeting the octane requirement, the engine will rapidly suffer major damage due to knock. You must not use fuels that produce sustained audible knock, as engine damage will occur. If the octane is just sufficient, the engine management system will move settings to a less optimal position, and the only major penalty will be increased costs due to poor fuel economy. Whenever possible, engines should be operated at the optimum position for long-term reliability. Engine wear is mainly related to design, manufacturing, maintenance, and lubrication factors. Once the octane and run-on requirements of the engine are satisfied, increased octane will have no beneficial effect on the engine. Run-on is the tendency of an engine to continue running after the ignition has been switched off, and is discussed in more detail in Section 8.2. The quality of gasoline, and the additive package used, would be more likely to affect the rate of engine wear, rather than the octane rating.


Can I mix different octane fuel grades?

Yes, however attempts to blend in your fuel tank should be carefully planned. You should not allow the tank to become empty, and then add 50% of lower octane, followed by 50% of higher octane. The fuels may not completely mix immediately, especially if there is a density difference. You may get a slug of low octane that causes severe knock. You should refill when your tank is half full. In general the octane response will be linear for most hydrocarbon and oxygenated fuels e.g. 50:50 of 87 and 91 will give 89.

Attempts to mix leaded high octane to unleaded high octane to obtain higher octane are useless for most commercial gasolines. The lead response of the unleaded fuel does not overcome the dilution effect, thus 50:50 of 96 leaded and 91 unleaded will give 94. Some blends of oxygenated fuels with ordinary gasoline can result in undesirable increases in volatility due to volatile azeotropes, and some oxygenates can have negative lead responses. The octane requirement of some engines is determined by the need to avoid run-on, not to avoid knock.


What happens if I use the wrong octane fuel?

If you use a fuel with an octane rating below the requirement of the engine, the management system may move the engine settings into an area of less efficient combustion, resulting in reduced power and reduced fuel economy. You will be losing both money and drivability. If you use a fuel with an octane rating higher than what the engine can use, you are just wasting money by paying for octane that you cannot utilize. The additive packages are matched to the engines using the fuel, for example intake valve deposit control additive concentrations may be increased in the premium octane grade. If your vehicle does not have a knock sensor, then using a fuel with an octane rating significantly below the octane requirement of the engine means that the little men with hammers will gleefully pummel your engine to pieces.

You should initially be guided by the vehicle manufacturer's recommendations, however you can experiment, as the variations in vehicle tolerances can mean that Octane Number Requirement for a given vehicle model can range over 6 Octane Numbers. Caution should be used, and remember to compensate if the conditions change, such as carrying more people or driving in different ambient conditions. You can often reduce the octane of the fuel you use in winter because the temperature decrease and possible humidity changes may significantly reduce the octane requirement of the engine.

Use the octane that provides cost-effective drivability and performance, using anything more is waste of money, and anything less could result in an unscheduled, expensive visit to your mechanic.

Can I tune the engine to use another octane fuel?

In general, modern engine management systems will compensate for fuel octane, and once you have satisfied the optimum octane requirement, you are at the optimum overall performance area of the engine map. Tuning changes to obtain more power will probably adversely affect both fuel economy and emissions. Unless you have access to good diagnostic equipment that can ensure regulatory limits are complied with, it is likely that adjustments may be regarded as illegal tampering by your local regulation enforcers. If you are skilled, you will be able to legally wring slightly more performance from your engine by using a dynamometer in conjunction with engine and exhaust gas analyzers and a well-designed, retrofitted, performance engine management chip.

How can I increase the fuel octane?

Not simply, you can purchase additives, however these are not cost-effective and a survey in 1989 showed the cost of increasing the octane rating of one US gallon by one unit ranged from 10 cents (methanol), 50 cents (MMT), $1.00 (TEL), to $3.25 (xylenes). Refer to section 6.20 for a discussion on naphthalene (mothballs). It is preferable to purchase a higher octane fuel such as racing fuel, aviation gasolines, or methanol. Sadly, the price of chemical grade methanol has almost doubled during 1994. If you plan to use alcohol blends, ensure your fuel handling system is compatible, and that you only use dry gasoline by filling up early in the morning when the storage tanks are cool. Also ensure that the service station storage tank has not been refilled recently. Retailers are supposed to wait several hours before bringing a refilled tank online, to allow suspended undissolved water to settle out, but they do not always wait the full period.

Are aviation gasoline octane numbers comparable?

Aviation gasolines were all highly leaded and graded using two numbers, with common grades being 80/87, 100/130, and 115/145 [109,110]. The first number is the Aviation rating (a.k.a. Lean Mixture rating), and the second number is the Supercharge rating (a.k.a. Rich Mixture rating). In the 1970s a new grade, 100LL (low lead = 0.53mlTEL/L instead of 1.06mlTEL/L) was introduced to replace the 80/87 and 100/130. Soon after the introduction, there was a spate of plug fouling, and high cylinder head temperatures resulting in cracked cylinder heads [110]. The old 80/87 grade was reintroduced on a limited scale. The Aviation Rating is determined using the automotive Motor Octane test procedure, and then converted to an Aviation Number using a table in the method. Aviation Numbers below 100 are Octane numbers, while numbers above 100 are Performance numbers. There is usually only 1 - 2 Octane units different to the Motor value up to 100, but Performance numbers vary significantly above that e.g. 110 MON = 128 Performance number.

The second Avgas number is the Rich Mixture method Performance Number (PN - they are not commonly called octane numbers when they are above 100), and is determined on a supercharged version of the CFR engine that has a fixed compression ratio. The method determines the dependence of the highest permissible power (in terms of indicated mean effective pressure) on mixture strength and boost for a specific light knocking setting. The Performance Number indicates the maximum knock-free power obtainable from a fuel compared to iso-octane = 100. Thus, a PN = 150 indicates that an engine designed to utilize the fuel can obtain 150% of the knock-limited power of iso-octane at the same mixture ratio. This is an arbitrary scale based on iso-octane + varying amounts of TEL, derived from a survey of engines performed decades ago. Aviation gasoline PNs are rated using variations of mixture strength to obtain the maximum knock-limited power in a supercharged engine. This can be extended to provide mixture response curves that define the maximum boost (rich - about 11:1 stoichiometry) and minimum boost (weak about 16:1 stoichiometry) before knock.

The 115/145 grade is being phased out, but even the 100LL has more octane than any automotive gasoline.


Can mothballs increase octane?

The legend of mothballs as an octane enhancer arose well before WWII when naphthalene was used as the active ingredient. Today, the majority of mothballs use para-dichlorobenzene in place of naphthalene, so choose carefully if you wish to experiment :-). There have been some concerns about the toxicity of para-dichlorobenzene, and naphthalene mothballs have again become popular. In the 1920s, typical gasoline octane ratings were 40-60, and during the 1930s and 40s, the ratings increased by approximately 20 units as alkyl leads and improved refining processes became widespread.

Naphthalene has a blending motor octane number of 90, so the addition of a significant amount of mothballs could increase the octane, and they were soluble in gasoline. The amount usually required to appreciably increase the octane also had some adverse effects. The most obvious was due to the high melting point, (80C), when the fuel evaporated the naphthalene would precipitate out, blocking jets and filters. With modern gasolines, naphthalene is more likely to reduce the octane rating, and the amount required for low octane fuels will also create operational and emissions problems.


What is the effect of Compression ratio?

Most people know that an increase in Compression Ratio will require an increase in fuel octane for the same engine design. Increasing the compression ratio increases the theoretical thermodynamic efficiency of an engine according to the standard equation;

• Efficiency = 1 - (1/compression ratio)^gamma-1

,where gamma = ratio of specific heats at constant pressure and constant volume of the working fluid (for most purposes air is the working fluid, and is treated as an ideal gas). There are indications that thermal efficiency reaches a maximum at a compression ratio of about 17:1 for gasoline fuels in an SI engine.

The efficiency gains are best when the engine is at incipient knock, that's why knock sensors (actually vibration sensors) are used. Low compression ratio engines are less efficient because they cannot deliver as much of the ideal combustion power to the flywheel. For a typical carbureted engine, without engine management:

Compression Octane Number Brake Thermal Efficiency
Ratio Requirement (Full Throttle)
5:1 72 -
6:1 81 25 %
7:1 87 28 %
8:1 92 30 %
9:1 96 32 %
10:1 100 33 %
11:1 104 34 %
12:1 108 35 %

Modern engines have improved significantly on this, and the changing fuel specifications and engine design should see more improvements, but significant gains may have to await improved engine materials and fuels.


What is the effect of changing the air-fuel ratio?

Traditionally, the greatest tendency to knock was near 13.5:1 air-fuel ratio, but was very engine specific. Modern engines, with engine management systems, now have their maximum octane requirement near to 14.5:1. For a given engine using gasoline, the relationship between thermal efficiency, air-fuel ratio, and power is complex. Stoichiometric combustion (air-fuel
ratio = 14.7:1 for a typical non-oxygenated gasoline) is neither maximum power - which occurs around air-fuel 12-13:1 (Rich), nor maximum thermal efficiency - which occurs around air-fuel 16-18:1 (Lean). The air-fuel ratio is controlled at part throttle by a closed loop system using the oxygen sensor in the exhaust. Conventionally, enrichment for maximum power air-fuel ratio is used during full throttle operation to reduce knocking while providing better drivability [38]. An average increase of 2 (R+M)/2 ON is required for each 1.0 increase (leaning) of the air-fuel ratio [111]. If the mixture is weakened, the flame speed is reduced, consequently less heat is converted to mechanical energy, leaving heat in the cylinder walls and head, potentially inducing knock. It is possible to weaken the mixture sufficiently that the flame is still present when the inlet valve opens again, resulting in backfiring.


What is the effect of changing the ignition timing?

The tendency to knock increases as spark advance is increased. For an engine with recommended 6 degrees BTDC (Before Top Dead Center) timing and 93 octane fuel, retarding the spark 4 degrees lowers the octane requirement to 91, whereas advancing it 8 degrees requires 96 octane fuel [27]. It should be noted this requirement depends on engine design. If you advance the spark, the flame front starts earlier, and the end gases start forming earlier in the cycle, providing more time for the autoigniting species to form before the piston reaches the optimum position for power delivery, as determined by the normal flame front propagation. It becomes a race between the flame front and decomposition of the increasingly squashed end gases. High octane fuels produce end gases that take longer to autoignite, so the good flame front reaches and consumes them properly.

The ignition advance map is partly determined by the fuel the engine is intended to use. The timing of the spark is advanced sufficiently to ensure that the fuel-air mixture burns in such a way that maximum pressure of the burning charge is about 15-20 degree after TDC. Knock will occur before this point, usually in the late compression - early power stroke period.
The engine management system uses ignition timing as one of the major variables that is adjusted if knock is detected. If very low octane fuels are used (several octane numbers below the vehicle's requirement at optimal settings), both performance and fuel economy will decrease.

The actual Octane Number Requirement depends on the engine design, but for some 1978 vehicles using standard fuels, the following (R+M)/2 Octane Requirements were measured. "Standard" is the recommended ignition timing for the engine, probably a few degrees BTDC [38].

Basic Ignition Timing
Vehicle Retarded 5 degrees Standard Advanced 5 degrees
A 88 91 93
B 86 90.5 94.5
C 85.5 88 90
D 84 87.5 91
E 82.5 87 90

The actual ignition timing to achieve the maximum pressure from normal combustion of gasoline will depend mainly on the speed of the engine and the flame propagation rates in the engine. Knock increases the rate of the pressure rise, thus superimposing additional pressure on the normal combustion pressure rise. The knock actually rapidly resonates around the chamber, creating a series of abnormal sharp spikes on the pressure diagram. The normal flame speed is fairly consistent for most gasoline HCs, regardless of octane rating, but the flame speed is affected by stoichiometry. Note that the flame speeds in this FAQ are not the actual engine flame speeds. A 12:1 CR gasoline engine at 1500 rpm would have a flame speed of about 16.5 m/s, and a similar hydrogen engine yields 48.3 m/s, but such engine flame speeds are also very dependent on stoichiometry.

ne14t? 01-12-2010 03:42 PM

Very good information! And a decent little read.

I would just like to state my opinion that water injection is probably the easiest way to increase your octane rating if you remember to keep your tank full. No your dont have to buy special boost juice or anything all you need is -40* winter antifreeze as its about a 60% meth rating just and about $4 for a jug and can increase 94 octance gas upto 108 or so and is probably the easiest way to get race quality gas off the pump.

Second thing I want to point out is E85 more and more people are starting to tune with this stuff and its apparently really nuts. Its not as easy to come by especially here in Canada but apparently the stuff is like 110 octane gas right off the pump. Any car can be converted to run E85 but I have read rumors all over the web of it gumming up injectors and stuff like that, but you cant believe everything on the interweb.

sahan0011 08-21-2013 05:02 AM

Thank you for your valuable information. I have Toyota Corolla II. But unfortunately each and every time I put my car into smoke test, it fails. The results show the fuel consumption is very bad and exhaust air contains more CO and CO2. I had enough of this. Each and every time I caught by police for speeding, they will trace my smoke records also. Can you imaging how many times I have payed tickets due to this. I might get a separate credit card or bank account to pay alabama traffic ticket and get some sleep. So desperate.


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