Lecture 7

PHY 305
 Petroleum
Petroleum, complex mixture of hydrocarbons that occur in Earth in liquid, gaseous, or solid
form. The term is often restricted to the liquid form, commonly called crude oil, but, as a
technical term, petroleum also includes natural gas and the viscous or solid form known as
bitumen, which is found in tar sands. The liquid and gaseous phases of petroleum constitute
the most important of the primary fossil fuels.

Liquid and gaseous hydrocarbons are so intimately associated in nature that it has become
customary to shorten the expression “petroleum and natural gas” to “petroleum” when
referring to both. The word petroleum (literally “rock oil” from the Latin petra, “rock” or “stone,”
and oleum, “oil”) was first used in 1556 in a treatise published by the German mineralogist
Georg Bauer, known as Georgius Agricola.
PHY 305
 Oil

PHY 305
Crude oil is a fossil fuel
(like coal and natural
gas).
Oil was formed from the
remains of ancient
marine organisms.

Over millions of years of

intense heat and
pressure, these organic
remains (fossils)
transformed into carbon-
rich substances we rely
on as raw materials for
fuel and a wide variety of
products
The geological conditions that would eventually create petroleum
formed millions of years ago, when marine plants, algae, and
plankton drifted in oceans and shallow seas. These organisms
sank to the seafloor at the end of their life cycle. Over time, they
were buried and crushed under millions of tons of sediment and
even more layers of plant debris.

Deep under the basin floor, the organic material was compressed
between Earth’s mantle, with very high temperatures, and millions
of tons of rock and sediment above. Oxygen was almost
completely absent in these conditions, and the organic matter
began to transform into a waxy substance called kerogen.

With more heat, time, and pressure, the kerogen underwent a

process called catagenesis, and transformed into hydrocarbons.
Hydrocarbons are simply chemicals made up of hydrogen and
carbon. Different combinations of heat and pressure can create
different forms of hydrocarbons. Some other examples are coal,
peat, and natural gas.
 Crude oil is usually black or
dark brown, but can also be
yellowish, reddish, tan, or
even greenish. Variations in
color indicate the distinct
chemical compositions of
different supplies of crude oil.
Petroleum that has few metals
or sulfur, for instance, tends to
be lighter (sometimes nearly
clear).

 Petroleum is used to make

gasoline, an important product
in our everyday lives. It is also
processed and part of
thousands of different items,
including tires, refrigerators,
life jackets, and anesthetics.
Chemistry A hydrocarbon is an organic compound consisting
 Crude oil is composed of hydrocarbons, which are mainly entirely of hydrogen and carbon.
hydrogen (about 13% by weight) and carbon (about 85%).
Other elements such as nitrogen (about 0.5%), sulfur
(0.5%), oxygen (1%), and metals such as iron, nickel, and
copper (less than 0.1%) can also be present in with the
hydrocarbons in small amounts.

 The way molecules are organized in the hydrocarbon is a

result of the original composition of the algae, plants, or
plankton from millions of years ago. The amount of heat
and pressure the plants were exposed to also contributes
to variations that are found in hydrocarbons and crude oil.
Octane, a hydrocarbon found in petroleum. Lines
represent single bonds; black spheres represent carbon;
white spheres represent hydrogen.

 Due to this variation, crude oil that is pumped from the

ground can consist of hundreds of different petroleum
compounds. Light oils can contain up to 97%
hydrocarbons, while heavier oils and bitumens might
contain only 50% hydrocarbons and larger quantities of
other elements. It is almost always necessary to refine
crude oil in order to make useful products.
 Under surface pressure and temperature conditions, lighter hydrocarbons methane, ethane, propane and butane exist as
gases, while pentane and heavier hydrocarbons are in the form of liquids or solids. However, in an underground oil
reservoir the proportions of gas, liquid, and solid depend on subsurface conditions and on the phase diagram of the
petroleum mixture

 An oil well produces predominantly

crude oil, with some natural gas
dissolved in it. Because the pressure is
lower at the surface than underground,
some of the gas will come out of solution
and be recovered (or burned/flared) as
associated gas or solution gas.

 A gas well produces predominantly

natural gas. However, because the
underground temperature is higher than
at the surface, the gas may contain
heavier hydrocarbons such as pentane,
hexane, and heptane in the gaseous
state. At surface conditions these will
condense out of the gas to form
"natural-gas condensate", often
shortened to condensate.
An LPG tank (propane
tank) or LPG storage
tanks is made from
welded steel and is
designed for the
required pressures and
heat expansion of the
stored hydrocarbon
gases, including
propane and butane.
Four different types of hydrocarbon molecules appear in crude oil: Paraffins, Naphtalenes, Aromatics, and
Asphaltics. The relative percentage of each varies from oil to oil, determining the properties of each oil.
 Paraffins (alkanes) are the most common hydrocarbons in
crude oil; certain liquid paraffins are the major constituents of
gasoline (petrol) and are therefore highly valued.

An alkane consists of hydrogen and carbon atoms arranged

in a tree structure in which all the carbon–carbon bonds are
single. Alkanes have the general chemical formula C nH2n+2.

 Naphthenes (cycloalkanes) (not to be confused with

naphthalene) is a term specific to the petroleum industry that
refers to the saturated cyclic hydrocarbons (cycloalkanes).
Naphthenes are an important part of all liquid refinery
products, but they also form some of the heavy asphalt like
residues of refinery processes.

Cycloalkanes are organic compounds in which a sequence

of carbon atoms, rather than being connected in a chain,
closes to form a ring. Saturated hydrocarbons that contain
one ring are referred to as cycloalkanes. With a general
formula of CnH2n (n is an integer greater than 2), they have
two fewer hydrogen atoms than an alkane with the same
number of carbon atoms.
 Aromatics generally constitute only a small percentage of most crudes. The most common aromatic in
crude oil is benzene, a popular building block in the petrochemical industry.

Aromatics, is a cyclic (ring-shaped), planar (flat) compound with pi bonds in resonance (those
containing delocalized electrons) that gives increased stability compared to other geometric or
connective arrangements with the same set of atoms.

 Asphaltenes in the form of asphalt or bitumen products from oil refineries are used as paving materials
on roads, shingles for roofs, and waterproof coatings on building foundations.

 Oils containing primarily paraffin hydrocarbons are called paraffin-based

or paraffinic

 Naphthenic-based crudes contain a large percentage of cycloparaffins in

the heavy components.

 Highly aromatic crudes are less common but are still found around the
world.
 Classification

Oil is classified according to three main categories:

- The geographic location where it was drilled

- Sulfur content

- API gravity (a measure of density).

Classification: Sulfur Content Classification: API Gravity
The American Petroleum Institute (API) is
Sulfur is considered an “impurity” in
a trade association for businesses in the
petroleum. Sulfur in crude oil can corrode
oil and natural gas industries. The API
metal in the refining process and contribute to
has established accepted systems of
air pollution. Petroleum with more than 0.5%
standards for a variety of oil- and gas-
sulfur is called “sour,” while petroleum with
related products.
less than 0.5% sulfur is “sweet.”
API gravity is a measure of the density of
Sweet oil is usually much more valuable than
petroleum liquid compared to water. If a
sour because it does not require as much
petroleum liquid’s API gravity is greater
refining and is less harmful to the
than 10, it is “light,” and floats on top of
environment.
water. If the API gravity is less than 10, it
is “heavy,” and sinks in water.

Light oils are preferred because they

have a higher yield of hydrocarbons.
Heavier oils have greater concentrations
of metals and sulfur and require more
refining.
 Classification: Geography

A benchmark crude or marker crude is a crude oil that

serves as a reference price for buyers and sellers of crude
oil.

There is always a spread between WTI, Brent and other

blends due to the relative volatility (high API gravity is
more valuable), sweetness/sourness (low sulfur is more
valuable) and transportation cost. This is the price that
controls world oil market price.

Oil is drilled all over the world. However, there are three
primary sources of crude oil that set reference points for
ranking and pricing other oil supplies: Brent Crude, West
Texas Intermediate, and Dubai/Oman.
 West Texas Intermediate (WTI) is a lighter oil that is
produced mostly in the U.S. state of Texas. It is “sweet”
and “light”—considered very high quality. WTI supplies
much of North America with oil. West Texas Intermediate is
ideal for producing products like low-sulfur gasoline and
low-sulfur diesel.

 Brent Crude is a mixture that comes from 15 different oil

fields between Scotland and Norway in the North Sea.
These fields supply oil to most of Europe. Brent Crude is
produced near the sea, so transportation costs are
significantly lower than WTI, which is produced in
landlocked areas..

 Dubai crude, also known as Fateh or Dubai-Oman crude,

is a light, sour oil that is produced in Dubai, part of the
United Arab Emirates. The nearby country of Oman has
recently begun producing oil. Dubai and Oman crudes are
used as a reference point for pricing Persian Gulf oils that Prior to 2011, Brent Crude tended to be cheaper than West Texas
are mostly exported to Asia.
Crude. Since 2011, and due to advancements in oil drilling and
 The OPEC Reference Basket is another important oil fracking, of West Texas Intermediate becoming cheaper than
source. OPEC is the Organization of Petroleum Exporting Brent Crude oil.
Countries. The OPEC Reference Basket is the average
price of petroleum from OPEC’s 12 member countries:
Algeria, Angola, Ecuador, Iran, Iraq, Kuwait, Libya, Nigeria, This has been dubbed the American shale revolution, and the
Qatar, Saudi Arabia, the United Arab Emirates, and increased production led oil prices to fall from above $100 to
Venezuela. The OPEC basket is slightly heavier and more below $50 from 2014 to 2015
sour than Brent.
OPEC
The Organization of the Petroleum Exporting
Countries (OPEC) is an intergovernmental
organization or cartel of 13 countries. Founded
on 14 September 1960 in Baghdad by the first
five members (Iran, Iraq, Kuwait, Saudi Arabia,
and Venezuela), it has since 1965 been
headquartered in Vienna, Austria, although
Austria is not an OPEC member state. As of
September 2018, the 13 member countries
accounted for an estimated 44 percent of
global oil production and 81.5 percent of the
world's "proven" oil reserves.
Note that this measures oil
production, not consumption.
Many countries consume
energy from oil in their energy
supply. But not all countries
have oil reserves to produce
this themselves. This therefore
measures oil production before
trade between countries.
Oil production is an important
indicator to follow – it helps us
understand where it’s being
extracted, who the main oil producers
are, and how this related to oil
reserves. But we also care about
where that oil is being consumed –
that tells us what role it’s playing in
the energy system of each country.
Oil is the world’s largest energy
source today. It is the dominant
source of energy for the transport
sector in particular.
Oil is the world’s largest energy
source today. It is the dominant
source of energy for the transport
sector in particular.

This interactive map shows the share

of primary energy that comes from oil
across the world.
 Gasoline

PHY 305
Crude oil itself is not extremely useful, so it is refined to
produce a variety of useful products.

Petroleum products are products that can be obtained

by refining and comprise ethane, liquefied petroleum gas
LPG, naphtha, gasoline, aviation fuel, marine fuel,
kerosene, diesel fuel, distillate fuel oil, residual fuel oil,
gas oil, lubricants, white oil, grease, wax, asphalt, as
well as coke.

The main refining process used for crude oil involves

fractional distillation. In this process, crude oil is heated
and vaporized and rises up through a vertical column, with
different fractions condensing at different heights due to
their different condensing temperatures.
 Gasoline or petrol is a derivative product of crude oil/petroleum. ... In the US and Latin countries, term gasoline
is used, but in Europe and Asian countries it's called petrol. In many languages, the name of the product is
derived from benzene, such as Benzin in Arabic/Persian‫ بنزین‬,Turkish and German, benzina in Italian, or bensin
in Indonesian; but in Argentina, Uruguay, and Paraguay, the colloquial name nafta is derived from that of the
chemical naphtha
 Gasoline consists mostly of organic
compounds obtained by the fractional
distillation of petroleum, enhanced with
a variety of additives.

 On average, a 160-liter (42-U.S.-gallon)

barrel of crude oil can yield up to about
72 liters (19 U.S. gallons) of gasoline
after processing in an oil refinery.
The exact chemical composition of gasoline varies Gasoline Energy Density ( 32 MJ/L)
depending on its grade or octane rating, but generally
speaking it is a mixture of combustible hydrocarbons.

This higher quality of the fuel ensures that the ignition of

the fuel happens on time as a result of a spark from the
spark plug and not early as a result of compression from
the piston.

Additionally, the specific composition of gasoline results

in a high energy density. This high energy density is what
makes gasoline such a valuable fuel, as a relatively small
volume of fuel can provide a large amount of useful
energy.
Octane ratings are not indicators of the energy content
of fuels. They are only a measure of the fuel's tendency
to burn in a controlled manner, rather than exploding in
an uncontrolled manner. It is a standard measure of a
fuel's ability to withstand compression in an internal
combustion engine without detonating. The higher the
octane number, the more compression the fuel can
withstand before detonating
The octane rating of a specific gasoline mixture is
based off the ratios of two compounds in the
gasoline—iso-octane, a compound with the same
chemical formula as octane but with slightly different
structure and properties (they are chemical isomers),
and normal heptane. These two compounds outline
the two extremes of the scale, with pure iso-octane
having a rating of 100 and n-heptane having a rating
of zero. Thus, a blend of 90% iso-octane and 10% n-
heptane would have an octane rating of 90

The higher the octane number, the more

compression from the piston the gasoline can
withstand before igniting in the engine. The ability for
gasoline to withstand being compressed is most
important for vehicles that run on traditional
gasoline. In contrast, diesel engines do not
compress fuel but rather air and then inject fuel.
These engines rely on different ratings, known as
cetane numbers
 Measurement methods
Research Octane Number (RON) A US gas station pump
The most common type of octane rating worldwide offering five different
is the Research Octane Number (RON). RON is (R+M)/2 octane ratings
determined by running the fuel in a test engine
with a variable compression ratio under controlled
conditions and comparing the results with those for
mixtures of iso-octane and n-heptane.

Motor Octane Number (MON)

Another type of octane rating, called Motor Octane
Number (MON), is determined at 900 rpm engine
speed instead of the 600 rpm for RON. MON testing
uses a similar test engine to that used in RON
testing, but with a preheated fuel mixture, higher
engine speed, and variable ignition timing to
further stress the fuel's knock resistance.
Depending on the composition of the fuel, the
MON of a modern pump gasoline will be about 8 to
12 octane lower than the RON.
In Europe, the octane rating on the pump is simply the RON
figure. America, by contrast, uses the average of the RON
and the MON figures, called the AKI (anti-knock index). Thus,
97 octane “super unleaded” in Britain is roughly equivalent to
91 octane premium in the United States.
Lebanon: 95 RON and 98 RON are widely available.
  A toxic breakthrough
In 1921, researchers at General Motors discovered that
adding a compound called tetraethyl lead to gasoline
could improve engine performance.
(Not-so-fun fact: Thomas Midgley Jr., a scientist who
played a key role in what proved to be a calamitous
discovery, also developed chlorofluorocarbons, a class
of refrigerants that went on to damage the ozone layer.)

 The final holdout, Algeria, used up the last of its

stockpile of leaded gasoline in July, 2021. That's
according to the U.N. Environment Programme,
which has spent 19 years trying to eliminate leaded
gasoline around the globe.

 "The successful enforcement of the ban on leaded

petrol is a huge milestone for global health and our
environment," Inger Andersen, UNEP's executive
director
Leaded gasoline for cars and trucks has been phased
out worldwide, but leaded fuels are still used in
aviation, motor sports and other off-road uses.

https://www.npr.org/2021/08/30/1031429212/the-world-has-finally-stopped-using-leaded-gasoli
ne-algeria-used-the-last-stockp
 There were other additives that could serve the
same purpose — today, ethanol is widely used
as a far safer alternative.

 There are a few countries around the globe

that are using Ethanol in their fuels. One of
them is Brazil, where by law all fuels need to
have at least 20% Ethanol. This usually does
not have an impact on power, but it does bring
slightly higher fuel consumption. As long as the
fuel type gets a 95RON or 98RON rating, it is
suitable for use in the car.
 Oil Spill

PHY 305
Deepwater Horizon, 2016 movie, trailer: https://www.youtube.com/watch?v=8yASbM8M2vg
https://youtu.be/UPAqfTNiais