Chemistry: The Molecular Science

Moore, Stanitski and Jurs

Chapter 12: Fuels, Organic Chemicals and

Polymers

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 Petroleum
Petroleum is a complex mixture of:
• alkanes
• cycloalkanes
• alkenes
• aromatic hydrocarbons
Its composition and color vary with origin.

Crude oil is extracted from the earth and must be

refined (separated into different fractions).

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 Petroleum Refining
• Petroleum components range from gases to liquids
to solids
• Separated by fractional distillation according to
their boiling points
• gasoline = fraction with boiling range of 20-200 °C
 composed of C5-C12 hydrocarbons

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 Fractional Distillation
Separation of cyclohexane (bp = 80.7 °C) and
toluene (bp = 110.6 °C).

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 Petroleum Refining
Fractional distillation of petroleum

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 Octane Number
Hydrocarbons will autoignite
• Burn without a spark when T ≥ Tautoignition
• As P increases, Tautoignition falls.

Gasoline is compressed in an engine before spark

ignition.
• If gasoline ignites before the spark, the engine “knocks”.

Octane number rates a fuel’s ability to burn smoothly.

• Assigned in comparison to 2 fuels
 n-heptane (poor fuel, low Tautoignition) = 0
 i-octane (good fuel, high Tautoignition) = 100

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 Petroleum: Octane Number
Name* Octane
Regular gasoline (87 octane) could n-octane -20
be 87% isooctane + 13% n-heptane n-heptane 0
n-hexane 25
n-pentane 62
(or a mix of many others…) 1-pentene
i-octane
91
100
benzene 106
methanol 107
ethanol 108
t-butyl alcohol 113
toluene 118
*n = normal = straight chain
In general: i = iso t = tertiary.
straight-chain < branched  aromatic.

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 Catalytic Cracking
Larger hydrocarbons can be “cracked”:

Catalyst
C16H34 pressure & heat C8H16 + C8H18
alkane alkene alkane

• Changes kerosene fraction into gasolines

• Alkenes have high octane numbers
• Alkenes are polymer starting materials

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 Catalytic Reforming
Converts small straight-chains into branched or
aromatic hydrocarbons.
CH3
|
catalyst
CH3CH2CH2CH2CH3 CH3CHCH2CH3
n-pentane (62 octane) 2-methylbutane (94 octane)
C5H12 C5H12

This produces better fuels.

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 Catalytic Reforming

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 Chemical Raw Materials from Petroleum

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 Octane Enhancers
Octane enhancers (“antiknock” agents) are added to
increase octane numbers.

Tetraethyl lead, Pb(C2H5)4

• Used before catalytic converters were added to automobile
exhausts
• Health hazard

Current octane enhancers

• toluene,
• t-butyl alcohol
• methanol
• ethanol.
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 Oxygenated & Reformulated Gasolines
High-CO areas must use oxygenated gasolines.
• Contain > 2.7% O (by mass).
• Extra O promotes complete combustion.

High-O3 areas must use reformulated gasolines.

• Less volatile (atmospheric hydrocarbons promote
O3 formation).
• Oxygenated gas.

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 Oxygenated & Reformulated Gasolines

Car exhausts are much cleaner, but…

…the number of cars keeps growing
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 Natural Gas and Coal
Natural gas = mix of low-mass hydrocarbons.

N. American natural gas

• CH4 (60 – 90%)
• C2H6 (5 – 9%)
• C3H8 (3 – 18%)
• C4H10 (1 – 2%)
• other gases (CO2, N2, H2S, He).

Europe = CH4 (~100%). Comparison of natural gas

and gasoline powered
vehicles.
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 Natural Gas and Coal
Coal
Irregular array of partially-hydrogenated 6-membered
rings; also contains S, N and O atoms.
• Most coal is used to produce
electricity.
• >300 million tons/yr burned.
• S compounds yield SO2 and
SO3 on combustion.

US sources of energy
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 Energy Conversions

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 Tertiary Structure of a Protein
A globular protein (chymotrypsin):

α-helix (blue)
β-sheet (green)

random coils (copper)

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