Gasoline

Chemistry of Petroleum
• Petroleum is composed of organic
compounds containing Carbon and
Hydrogen
– Hydrocarbon Molecules
• CH4 Methane, the simplest Hydrocarbon

CH4 + 2 O2  2 H20 + CO2 + Energy

 More Hydrocarbons

2 Carbon Atoms 3 Carbon Atoms 4 Carbon Atoms

ETHANE (C2H6) PROPANE (C3H8) BUTANE (C4H10)

And so on.
Five Carbon Atoms give you PENTANE (C5H12)
Six Carbon Atoms give you HEXANE (C6H14)
Seven give you HEPTANE (C7H16).
The World’s Favorite Hydrocarbon
Octane: Eight Carbons (C8H18).

The main ingredient in gasoline

 Hydrocarbons
• Use the formula below to determine the
number of Hydrogen Atoms busing the
number of Carbon atoms (n).

CnH2n+2
 Chemistry of Petroleum
• Temperature and number of carbon atoms
determine the form of petroleum
• At Ordinary surface temperatures:
– Less than 5 Carbon atoms
• Gas
– 5 to 15 Carbon Atoms
• Free-Flowing Liquids.
• CRUDE OIL
– Greater than 15
• Thick viscous liquids to waxy solids.
 Crude Oil
• Liquid petroleum recovered directly from the well
is called crude (unrefined or unprocessed) oil.
• Crude oil is comprised of a mixture of
hydrocarbon molecules
• Light (sweet) Crude
– low S impurities
– Can easily be refined to gasoline
– Produced in Nigeria, U.S. Gulf States, Canada
• Heavy (sour) Crude
– high S impurities
– Difficult to refine to gasoline
– Produced in Saudi Arabia, Mexico, Venezuela, Iraq
 Petroleum Refining
• An oil refinery is an industrial plant where
crude oil is processed and refined into
more useful petroleum products.

Every barrel of
crude oil can be
refined into many
products or
fractions.
 Crude Oil Fractions
• Petroleum gas (1-4 Carbons)
– used for heating, cooking, making plastics
• Naphtha (8 Carbons)
– dry cleaning solution; intermediate that will be
further processed to make gasoline
• Gasoline (8 Carbons)
– motor fuel
• Kerosene (12 Carbons)
– fuel for jet engines and tractors; starting
material for making other products
 Crude Oil Fractions
• Gas Oil or Diesel (16 Carbons)
– used for diesel fuel and heating oil; starting
material for making other
• Lubricating Oil (36 Carbons)
– used for motor oil, grease, other lubricants
• Heavy gas or Fuel oil (44 Carbons)
– used for industrial fuel; starting material for
making other products
• Residuals (80 Carbons)
– coke, asphalt, tar, waxes; starting material for
making other products
Components of a Refinery
 Fractional Distillation
• The hydrocarbons in crude oil have
different boiling points, according to the
number of carbon atoms their molecules
contain and how they are arranged.
• Fractional distillation uses the difference
in boiling point to separate the
hydrocarbons in crude oil.
• The fractionating column is cooler at the
top than the bottom, so the vapors cool
as they rise.
Fractional Distillation
 Fractional Distillation
• Vapors condense onto a tray when they
reach the part of the column which is
cooler than their boiling point.
• As the last gases from the bottom of the
column pass through the holes in a tray,
any lighter hydrocarbons still in the
condensed liquid are boiled off, and rise
through the column.
 Chemical Processing
• Very few of the components come out of
the fractional distillation column ready for
market.
• Many of them must be chemically
processed to make other fractions.
– For example, only 40% of distilled crude oil is
gasoline
• After distillation, one fraction can be
changed into another by two methods of
chemical processing: Cracking and
Unification
 Cracking
• Cracking breaks large
chains into smaller
chains.
• After various
hydrocarbons are
cracked into smaller
hydrocarbons, the
products go through
another fractional
distillation column to
separate them.
 Unification
• Unification combines
smaller hydrocarbons
into larger ones
• A reformer combines
chains to make naphtha
into gasoline.
• A significant by-product
of this reaction is
hydrogen gas, which is
then either used for
hydrocracking or sold.
Refineries and the Environment
• The refining process releases
numerous different chemicals into
the atmosphere; consequently,
there are substantial air pollution
emissions.
• Due to pollution problems there is
strong pressure to prevent the
development of new refineries,
and no major refinery has been
built in the U.S. since 1976.
• However, many existing
refineries have been expanded
during that time.
 Illinois Refineries
• Illinois leads the
Midwest in crude
oil refining
capacity with four
refineries.
• About 5.2% of
U.S. Petroleum is
refined in Illinois
and is mainly
supplied by the
Tar Sands on
Canada.
 Cost of Gasoline
• While it isn't
represented in the
diagram, some of
the actual money
you spend at the
pump does go to
the service station.
• Service stations add
on a few cents per
gallon.
• Gas prices mainly
rise when there are
changes in refining
and the price of
crude oil
 Gasoline (4-Stroke) Engine
• Burns fuel and air in
enclosed space
producing hot gases
• Allows heat to flow
from hot engine to cold
outside air
• Converts some of this
heat into useful work
• Example of a Heat
Engine
 Gasoline (4-Stroke) Engine
• The four strokes of the
cycle are induction,
compression, power,
and exhaust.
• Each corresponds to
one full stroke of the
piston, therefore the
complete cycle
requires two
revolutions of the
crankshaft to complete.
 Induction Stroke

• During the induction

stroke, the piston
moves downward,
drawing a fresh
charge of vaporized
fuel/air mixture.
• The carburetor
mixes the fuel and
air.
 Compression Stroke
• As the piston rises the
poppet valve is forced
shut by the increased
cylinder pressure.
• Flywheel momentum
drives the piston
upward, compressing
the fuel/air mixture.
• Compressed Fuel is
easier to ignite.
 Power Stroke
• At the top of the
compression stroke the
spark plug fires, igniting
the compressed fuel.
• As the fuel burns it
expands, driving the
piston downward.
• Chemical energy
converted to thermal
energy converted to
mechanical energy.
 Exhaust Stroke
• At the bottom of the
power stroke, the
exhaust valve is
opened by the
cam/lifter
mechanism.
• The upward stroke
of the piston drives
the exhausted fuel
out of the cylinder.
 Gasoline (4-Stroke) Engine
• Power stroke: heat in,
work out
• Exhaust stroke: heat
out
• Some of the extra
work out is used
during induction and
compression
• Some heat lost to
conduction and
convection in and
around the engine.
 Gasoline and 4-stroke Engines

• A 4-stroke engine is designed to run on a

refined mixture of hydrocarbons from C7–
Heptane and C8–Octane.
• This mixture is called Gasoline
• C7 and C8 vaporize at temperatures
below the boiling point of water.
– That's why if you spill gasoline on the ground
it evaporates very quickly.
 Octane Rating

• The octane rating of gasoline tells you how much

the fuel can be compressed before it
spontaneously ignites.
• Eighty-seven-octane gasoline is gasoline that
contains 87-percent octane and 13-percent
heptane
• Most gas stations offer three octane grades:
– regular, usually 87 octane
– mid-grade, usually 89 octane
– premium usually 92 or 93.
• The ratings must be posted on bright yellow
stickers on each gasoline pump.
 Knocking
• Knocking occurs when gas
ignites by compression
rather than because of the
spark from the spark plug.
• Problems
– Annoying
– Reduces efficiency
– Damages engine
• Heptane handles
compression very poorly
• Octane handles
compression very well
 Solutions to Knocking
• Increase the octane
rating of the gasoline
• This costs $$$$$
• Requires chemical
processing techniques to
be done numerous times
• Almost impossible to
refine 100% octane.
• Most car engines today
are designed to run
effectively on an octane
rating of 87.
 Gasoline Additives
• During WWI, it was discovered that you
can add a chemical called tetraethyl
lead to gasoline and significantly
improve its octane rating.
• Lower octane grades of gasoline could
be made usable by adding this
chemical.
• This led to the widespread use of "ethyl"
or "leaded" gasoline.
 Tetraethyl Lead (TEL)
• TEL was cheap to
manufacture.
• Most oil companies could
process TEL at their
refineries.
• This increased profits for
the oil company.
• However…….
 Tetraethyl Lead (TEL)
• Due to the
combustion of TEL
in gasoline, the
Earth became
covered in a thin
layer of lead.
• Even glacial ice at
the north pole
recorded an
alarming increase of
lead during the mid
to late 1900s.
 Health Risks of TEL Exposure
Acute Exposure in Low Level Exposure in
Adults Children
• Blindness • Lowered IQ
• Brain Damage • Reading and Learning
• Kidney disease Disablities
• Cancers • Impaired hearing
• Death • Hyperactivity
• Impaired Growth
 Removal of TEL
• In the early 1970s, catalytic converters
were required in vehicles by the Clean Air
Act to reduce smog forming pollutants.
• Lead from gasoline additives clogs a
catalytic converter.
Note: Leaded
Gasoline was not
phased out due to
health concerns
directly from the
lead!
 Removal of TEL
• Leaded gasoline was phased out in the
United States staring in 1973 due to the
Clean Air Act.
• Illegal to sell leaded gasoline for on-road
vehicles as of January 1, 1996.
• Fuel containing lead may continue to be
sold for off-road uses, including aircraft,
racing cars, farm equipment, and marine
engines until 2008
 Lead is Still a Problem

Most of the 7 million tons of lead

burned in the gasoline in the United
States in the twentieth century
remains --- in the soil, air, and water
and in the bodies of living organisms.
 MTBE
• MTBE has been used in U.S. gasoline at
low levels since 1979 to replace TEL to
increase its octane rating and help prevent
engine knocking.
• A hydrocarbon molecule that is created at
a refinery from methanol.
– Big money maker for petrochemical
companies
• Gasoline can contain as much as 10
percent to 15 percent MTBE.
MTBE Use and Releases
 MTBE
• The main problem with MTBE is that it is
thought to be carcinogenic and it mixes
easily with water.
• If gasoline containing MTBE leaks from an
underground tank at a gas station, it can
get into groundwater and contaminate
wells.
• Twenty seven states have passed laws to
ban MTBE in certain areas.