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What's Octane???
Copyright 2004 by Dan Nguyenphuc This paper may be freely distributed,
provided it is distributed in its entirety
Last revised: May 13, 2004

Background
There's always a lot of confusion regarding octane,
octane-boosters and how they work. Typical
misconceptions are evident in blank-statements
like:
"Higher octane fuels burn slower, thus their higher
octane number"
"Higher octane fuels burn hotter, therefore more
power is generated"
Higher octane fuels explodes with more force, thus their higher power"
Both of which are untrue and are coincidental in effect, rather than causal.
In actual practice, an engine has to be tuned specifically for high-octane
fuels to generate extra power. If you have an engine fully-tuned and
optimized for 91-octane pump gas, adding 100-octane race-gas into it will
yield little if any increase. However, if you were to take that engine and
increase the compression, advance the knock and/or increase the boost,
then you can take advantage of the higher-octane fuel. But this precludes
going back to the previous lower-octane fuels.

Three Kinds of Octane Boosters - 1.

ORGANO-METALLICS
There are three primary octane-boosting additives
mixed
in
with
gasoline:
organo-metallics,
ethers/alcohols and aromatics. Each one has
distinct chemical properties and results (along with
side-effects) on octane-boosting. Some people get
these families of compounds and their effects
mixed up.
First, let's look at organo-metallics which is used in
the little bottles of over-the-counter octane boosters, what makes them
work and how they compare. By far and large, these work on the same
principle as TEL-Tetra Ethyl Lead which is the principle octane-boosting
component of AvGas. For automotive OTC use, a slightly less carcinogenic
MMT compound is used (methylcyclopentadienyl manganese tricarbonyl); it
has pretty much the same structure as TEL, but with manganese
substituted for lead. These compounds have a non-linear octane-boosting
curve. The initial amounts give the most boost and adding more gives
decreasing benefits. Typically you get 3-4 'points' increase with these types
of additives; going from 91-octane to 91.4 octane max. I've uploaded a
comparison article of these types of additives: 951 RacerX: Octane Booster
Comparison
As you can imagine from the metallic
content, these boosters create nasty
deposits in your engine. That's why they
typically include a solvent such as mineral
spirits to try and dissolve the deposits.
Then a lubricant such as ATF or Marvel
Mystery Oil is typically added to the
cocktail to help your rings slide over the
deposits easier and minimize the damage.
If
you
dyno-test
a
car
using
organo-metallics (with straight-through

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exhaust), you can actually collect metallic pellets coming out your tailpipe.
Not a good thing to be putting into your combustion chambers no less...

2.

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OXYGENATES

The next group of octane-boosting compounds are oxygenates: ethers &

alcohols which also serves an emissions purpose by bundling their own
oxygen along with the fuel. The best compound here is ethanol
(CH3CH2OH) with a 115-octane (R+M)/2 rating and containing 34.73%
oxygen by weight. However, its high volatility with a RVP of 18 makes it
unsuitable for use in warm climates for emissions control. In which case,
MTBE
(CH3OC(CH3)3),
ETBE
(CH3CH2OC(CH3)3)__
and
TAME
((CH)3CCH2OCH3) are used which has more favorable RVPs of 1.5-8.0. But
they also have correspondingly lower octane of 105-110 along with lower
oxygen content of 15.66-18.15 by weight.
Ethers & alcohols are basically hydrocarbons fuels with an
extra hydroxyl -OH group added to one end. These
fuel-additives reduce your gas-mileage due to the
displacement of hydrogen and carbon atoms by the larger
oxygen molecules. The increased molecular-mass of the
compounds with the attahced -OH is what gives the
octane-boosting effect. The -OH group also makes the
compound polar, water-soluble and highly reactive
chemically. They will dissolve rubber and plastic fuel lines
and thus their concentration in fuels is fairly limited. Thus
their octane-boosting power is also reduced. Ethers and
alcohols are starting to be banned in a lot of areas because their
water-solubility makes tank leaks and dispersion by ground-water a big
problem

3.

AROMATICS

The final group of octane-boosting compounds, aromatics show the most

promise. Due to their stable benzene-ring structures, the compounds are
non-polar and chemically stable (non-reactive). In fact, they are less
volatile and less reactive than most other hydrocarbons in gasoline. This
stability is what gives aromatics their octane-boosting powers. Normal
gasoline typically contain around 25-30% aromatics, primarily toulene and
xylene. Adding more will simply increase the octane rating and bring their
concentrations up to what you find in higher-octane European gas (40-45%
aromatics): Gasoline composition.

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So by using aromatic toluene and xylene as

octane-boosters, you get none of the bad
side-effects of using organo-metallics (cancer
and engine-deposits) or ethers & alcohols (low
gas-mileage and rotting fuel-lines). By using
just two gallons of xylene in a 15-gal tank of
91-octane pump gas, you've brought the
octane-rating up to 94.5 and have roughly the
same aromatic content as German or French
gasoline. You may also notice in the Octane
Booster Comparison article above, that the
best octane-boosting solution was to use unleaded race-gas; the primary
octane-boosting components used are toluene and xylene.

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"Doesn't higher octane fuel have higher

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Well, it's not so simple. Really depends upon what you mean by 'higher' and
'energy content'. 'Octane' does not directly relate to 'energy content' or
'power' in anyway. There are many, many components and properties of
gasoline that is custom-tailored by the refinery, such as specific-gravity,
octane, oxygenates (ethers & alcohols), RVP-reid vapor pressure (volatility),
D86-distillation curve, combustion-temperature, sensitivity, flame-front
speed, VL-vapor/liquid ratio, etc. Just about each and every one of these
properties can be tailored and are sometimes dependent, and sometimes
independent upon each other.

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One of the basic measures of energy-content is BTU/gallon or

Calories/gal. The amount of heat released by any given volume of fuel is
directly related to the number of Hydrogen and Carbon atoms in that gallon.
Oxygenated fuels that use MTBE or alcohols to have extra Oxygen onboard
deliver much less energy per gallon because the oxygen atoms are simply
HUGE compared to a hydrogen or carbon. Such fuels tend to deliver less
mileage per gallon than non-oxygenated fuels. BUT, they do not deliver less
power, because that's more of a function of air-mass ingested into the
engine per 4-stroke cycle than fuel (air is tough to cram in, fuel is simple to
inject).
Compared to gasoline's specfic-gravity of 0.751-g/cc, toluene is 0.881-g/cc
and xylene (most likely a mixture of m-xylene; o-xylene; p-xylene) is
around 0.871-g/cc. This means they have more hydrogens and carbons to
combust per gallon with the O2 in the air that's being pumped through the
engine. The results of using large-percentage mixtures of these aromatics in
your fuel is a richer mixture than before with just pure pump gas (without
re-jetting). This will be safer than using the other common additive, 100LL
AvGas which is lighter than gasoline and will result in lean mixtures and
melted catalytics and O2-sensors. (LowLead AvGas is still contains several
times more organometallics than leaded auto gasoline). I've known of
several people that have destroyed some very expensive engines because
they ran a large amount AvGas without re-tuning their air-fuel ratios.
Besides, 100LL AvGas is only about 98-MON anyway, so it's not as effective
as toluene or xylene.

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Octane Doesn't Predict...

Another factor that octane doesn't predict is combustion temperature
which may or may not relate to the power produced. It's possible to blend
two mixtures of branched-chain paraffins along with aromatics to create two
concoctions both of which have higher octane than pump gas, and one of
them will have higher combustion temps than pump-gas, and yet the other
will have lower combustion temps.
A lot of people also confuse octane with flame-front propagation speed
which is yet another independent factor. Take the old-days measurement of
octane-ratings with iso-octane (2,2,4-trimethylpentane) with a octane-100
rating and n-heptane with a 0-octane rating. They both have the exact
same flame-front speed, yet one of them has a fairly high anti-knock index.
The other, n-heptane, has such low knock-resistance that you can just tap
the beaker and the stuff would explode!

Octane Does Predict...

In the end, all that octane predicts is AKI-Anti Knock Index as measured
on a knock engine. These are variable-compression single-cylinder engines
that can vary their compression between about 7.0:1 to 15.0:1. There's a
highly-sensitive and accurate knock-sensor and computer hooked up to this
engine that gives a readout of knock. The engine is run with the mystery
fuel and starts at a low-compression. Then the compression is increased
gradually while knock is monitored. Various levels of compression-ratios are
used and the corresponding knock measured. This is looked-up on
standardized tables and the MON-octane rating of the fuel is then
determined. In the end, that's ALL that the octane predicts, is how much
resistance the fuel has to knock.
So what's the point of all this? Just use the xylene to increase your fuel's
octane-level!!! Two to three gallons in a 15-gal tank won't change the
specific gravity by so much that it'll mess up your AF-ratios. By itself, the
resultant 96-octane mix won't automatically give you any more or less
power. But will allow you to TUNE your car for higher power by increasing
ignition advance, increasing compression or turning up the boost!
I've accumulated a couple of good posts on octane-blending on my RacerX
website under the Fuel-FAQ section. There's the obligatory 4-part
Gasoline-FAQ, and the F1-Rocket Fuel and DIY Octane Boosters FAQ.
Also the toxicity of xylene and toluene is actually lower than gasoline (due
to their stable ring-structures):

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Toxicity Profile: Toluene

Toxicity Profile: Xylene
REFERENCES:

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The Chemistry of Hydrocarbon Fuels - Harold H. Schobert_

-_ Butterworth-Heinemann Ltd.
Automotive Fuels Reference Book - Keith Owen, Trevor
Coley - SAE#R151
Mixture Formation in Spark-Ignition Engines - H.P. Lenz Springer-Verlag
Fuel Injection - Jeff Hartman - Motorbooks International
Lean Combustion in Spark-Ignited Internal Combustion
Engines - Germane, Wood, Hess - SAE#831694
An Introduction to Thermal Fluid Engineering - Z. Warhaft
- Cambridge University Press

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