[AT] unleaded gas
charlie hill
chill8 at cox.net
Thu Aug 3 07:47:58 PDT 2006
Walt, since you forgot to site your source I'll do it for you:
http://en.wikipedia.org/wiki/Tetra-ethyl_lead
I wouldn't want you to be accused of copyright infringement.
Charlie
----- Original Message -----
From: <DAVIESW739 at aol.com>
To: <at at lists.antique-tractor.com>
Sent: Thursday, August 03, 2006 9:50 AM
Subject: Re: [AT] unleaded gas
TEL is produced by reacting ethyl chloride with a sodium-lead alloy.
Pb + 4 Na + 4 CH3CH2Cl → (CH3CH2)4Pb + 4 NaCl
The product, TEL, is a viscous colorless liquid. Because TEL is charge
neutral (vs. a salt) and contains an exterior of alkyl groups, it is highly
lipophilic and soluble in petrol.
The most noteworthy feature of TEL is the weakness of its four C-Pb bonds.
At the temperatures found in internal combustion engines (CH3CH2)4Pb
decomposes, first into (CH3CH2)3Pb and an ethyl radicals. These radicals
help to
propagating the combustion, which itself is a radical reaction. When
(CH3CH2)4Pb
burns, it produces, not only carbon dioxide and water, but also lead:
(CH3CH2)4Pb + 13 O2 → 8 CO2 + 10 H2O + Pb
This lead can oxidize further to give species such as lead oxide)
Pb + 0.5 O2 → PbO
The Pb and PbO would quickly accumulate and destroy an engine. For this
reason, lead scavengers such as ethylene dibromide and 1,2-dichloroethane
are
used in conjunction with TEL - these agents form volatile lead(II) bromide
and
lead(II) chloride, respectively, which are exhausted from the engine (and
into
the air).
[edit]Uses of TEL as an antiknock agent
TEL was once used extensively as an additive in gasoline (petrol) for its
ability to increase the fuel's octane rating (that is, to prevent its
premature
detonation ("knocking") in the engine) thus allowing the use of higher
compression ratios for greater efficiency and power. In addition some of
the lead
was deposited on the valve seats and helped protect them against wear.
The use of TEL in gasoline was mostly dominant in the US while in Europe
alcohol was used instead. However the dominance of the US oil companies
eventually led to a switch to leaded fuel. When used as an antiknock agent
alcohol
would make the fuel hydroscopic (it would absorb water from the air) over
time
fuel humidity could lead to rusting and corrosion, as well as issues of
biological contamination.
In most Western countries this additive went out of use in the late 20th
century, chiefly because of the realization that most of its lead—which is
toxic
to humans and other organisms—ended up in the exhaust fumes and became a
major health and environmental problem. The need for that additive was also
lessened by the introduction of harder metals for valves and valve-seats, a
general reduction in engine compression ratios and the introduction of
other
anti-knocking additives. The deployment of the catalytic converter (which
lead
oxides from TEL would foul) further reduced TEL use. TEL remains an
ingredient
of aviation gasoline and is also still available from a limited number of
outlets as a fuel additive, mostly for owners of classic and vintage cars
and
motorcycles. In addition, TEL is still in use as an ingredient in the fuels
used
by NASCAR in its top three racing series. A more environmental friendly
additive is composed of 10 ppm potassium (sometimes sodium), solvents and
75%
diesel, and is added to unleaded fuel to boost the octane rating by 2-3
points.
In earlier times many vehicles produced before TEL's phase-out required
modification to a greater or lesser extent to run successfully on unleaded
gasoline. The installation of new hardened valve seats can be done by a
competent
automotive machine shop. A major engine rebuild, generally by the use of
dished pistons, is required to reduce the compression ratio of some older
high-performance engines (which required 100-octane fuel) to a ratio that
is
compatible with currently available gasoline ratings and this reform
necessarily
entails a decrease in engine power. However by the 21st century additives
were
available to allow continued use of even these sensitive engines, more or
less
to their normal function. TEL is still in use today as a component of 100
octane aviation fuel, as a suitable replacement for it in the aviation
industry
has not yet been found.
Walt Davies
Cooper Hollow Farm
Monmouth, OR 97361
503 623-0460
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