Organic Chemistry Hydrocarbons

The Alkanes

1
 Topics
• Definition: hydrocarbons
• The alkanes
• Common alkanes, nomentclature
• Some physical characteristics of alkanes
• Other families of hydrocarbons
• Structural Isomers
• Alkane chemistry – reactions
• Hydrocarbons and the economy
• Sources of alkanes
• Petroleum and natural gas
• Petroleum and natural gas formation

2
 Topics (Continued)
• Energy flow
• Time scale
• The Hubbert Curve
• Petroleum deposits
• World oil consumption
• From the deposits to the consumer
• Petroleum refining
• Gasoline
• Octane ratings
• Internal Combustion Engine Video
• The Combustion Reaction- Balancing Act

3
 Topics (Continued)
• Heats of Combustion
• Unintended consequences
• Climate Change
• Some Environmental Changes
• An Expanded Example – Tundra
• Petroleum Toxicity
• The Clean-up
• Cleaning Action of a Soap, a Dispersant
• Bio-degradation of Alkanes and Dispersants
• Conclusion

4
 Hydrocarbon Molecules
• Contain only carbon and hydrogen
• Important fuels
• Base stock for the synthesis of many useful
compounds
• Familiar examples: methane, propane,
butane and octane
• There are several families of hydrocarbons
• The major sources are natural gas and
petroleum
• We’ll first focus on the alkanes 5
 The Saturated Hydrocarbons, the Alkanes
• Contain only hydrogen and carbon
• Only single covalent bonds
• Methane’s molecular formula, CH4 (g)

• Octane’s molecular formula, C8H18 (l)

6
 Common Alkanes
• Alkanes all fit this formula scheme:
• CnH2n+2 where n can be any whole number

• Methane, CH4 fuel, major component of natural gas

• Ethane, C2H6 fuel, component of natural gas
• Propane, C3H8 fuel, LPG bottled gas
• Butane, C4H10 fuel, cigarette lighters
• Pentane, C5H12 fuel, component of gasoline
• Hexane, C6H14 fuel, component of gasoline

7
 Common Alkanes
• Heptane, C7H16 fuel, component of gasoline
• Octane, C8H18 fuel, major component of gasoline
• Nonane, C9H20 fuel, component of gasoline
• Decane, C10H22 fuel, component of gasoline

• Hexadecane C16H34 fuel, component of diesel and heating oil

• You’ll see that the prefixes, meth, eth, prop, etc mean
1, 2, 3, carbons etc. These prefixes carry on to other
organic compound names such as ethanol.
• Ethanol has the formula C2H5OH
• How many carbons would be in propanol?
• Answer 3
8
 Common Alkanes in the Home
• Paraffin wax refers to the solids with 20 ≤ n
≤ 40
• White, odorless, tasteless, waxy solid, with a
typical melting point between about 47 °C
and 64 °C ( 117°F to 147°F)
• Uses: Candles, drywall, thermostats

9
 Common Alkanes in the Home

Mineral Oil refers to liquid alkanes in the range

typically - 25.

10
 Common Alkanes in the Home
• Petroleum Jelly: Semi-solid; C range greater
than 25; FDA approved; one of the first
alkane products
• Improper uses
• Fresh Burns
• Nasal congestion
• or dryness
• Sexual Lubricant

11
 Alkanes MP’s and BP’s
Room
Temp

.
B.P.
Gases
Temperature Liquids
Celsius
M.P.
Solids

Number of Carbon Atoms

At room temperature, 25 C, how many alkanes (C1 –C14)

are gases?
At 25 C, how many are liquids? Solids?
12
 Some Other Families of Hydrocarbons

• Cycloalkanes CnH2n

Cyclohexane, C6H12

• Alkenes CnH2n Unsaturated hydrocarbons

Ethene, C2H2

13
 Some Other Families of Hydrocarbons
• Aromatics (arenes) (Only responsible for
benzene)
• Ring compounds with alternating single
• (C-C) and double (C=C) carbon to carbon bonds.

14
 Structural Isomers
• Compounds that have the same molecular
formulas but different structural formulas.

butane
Methylpropane
(isobutane)
B.P. -11.7 C
B.P. -.5 C
15
 Isomers of C5H12

As branching
increases
what happens
To the boiling
points of these
isomers?

16
Number of Isomers

17
 Crude Oil (Petroleum)
• Crude oil is a complex, highly variable
mixture of hydrocarbons.

• Including: alkanes,
• Cycloalkanes,
• Alkenes, and
• Aromatic hydrocarbons

18
 From Simple to Complex
• These compounds vary from very small
molecules to large, complex ones, such as
the arene on the right.

19
 Alkane Reactions
• The most important alkane reaction is
combustion. Otherwise, alkanes are relatively
stable chemically.
• Combustion refers to the burning of a substance.
• Methane + oxygen produces carbon dioxide,
water, and lots of energy (heat and light)
• CH4 +O2  CO2 + H2O + Energy (unbalanced)
This is an exothermic process
• Recall that energy is the ability to do work
• This energy drives our economy
20
 Top Five Global Corps. ($ millions) 2009
• 1 Royal Dutch Shell Revenues Profits
• $ 458,361 $26,277
• 2 Exxon Mobil
• $442,851 $45,220
• 3 Wal-Mart Stores
• $405,607 $13,400
• 4 BP
• $ 367,053 $21,157
• 5 Chevron $263,159 $23,931
21
 Sources of Alkanes

• The major sources are natural gas and

petroleum (coal too, especially methane)
• Other sources are methanogen bacteria
(produce swamp or marsh gas) and cattle
• Biologically produced short chained alkanes
are referred to as “biogas”.
• Petroleum is a complex mixture of alkanes
and other hydrocarbons
• Petroleum deposits vary in their mixtures of
hydrocarbons
22
 Petroleum and Natural Gas
• These are classified as fossil fuels because
the preponderance of evidence suggests that
they were formed from microscopic
phytoplankton and zooplankton in ancient
marine and freshwater environments.

23
 Anoxic Environment
• Petroleum and NG form under anoxic
conditions when dead plankton drift to the
ocean bottom (benthos) and are covered by
sediments. The organic molecules are
deprived of oxygen (anoxic). Over time these
organic compounds are gradually converted
to alkanes. Pressures and temperatures are
high.

24
 Conversion of Sugar to Methane and Carbon
Dioxide
• Example: sugar, under high pressure and
temperature, anoxically decomposes to
carbon dioxide and methane.
• Sugar  carbon dioxide and methane

Energy + C6H12O6  CO2 + CH4

Balanced:
Energy + C6H12O6  3 CO2 + 3 CH4
This is an endothermic process (energy input
required)
25
 The Energy Flow
• Sun  Phytoplankton  sugar  methane  available for work

Photons arrive from the sun (8 minutes)

Photosynthesis converts photon energy

to chemical bond energy (millisecond to
second time scale)

Sugar’s energy
transferred to
Chemical bond energy
Methane over
Stored in sugar molecules
millions of year
26
 Time Scale
• From the former slide, you call see that the
time scales for the energy flow range from
less than a second (photosynthesis) to
millions of years (formation of fossil fuels).
• The preponderance of evidence suggests
that the world’s consumption of petroleum
and natural gas is out pacing it’s natural rate
of production.
In other words we are rapidly running out of
these resources.
27
 Hubbert Curve (1956)
• A model for predicting the explotation of
geological resources.

28
Hubbert Prediction vs. US Data

29
 Petroleum Deposits
• Plankton biomass accumulates constantly on
the bottom of the world’s oceans. However
the distribution is not even, nor are the
physical requirements for the conversion of
this biomass to petroleum always present.

• Rates of
• Photo-
• synthesis
30
 Anticline

Impervious
rock layer

Oil

Petroleum is formed in an “oil window” of favorable temperature

And pressure in the sedimentary rock below the oil deposit.
31
 Petroleum - Complex Mixtures
• Petroleum is a complex mixture of alkanes,
cycloalkanes, unsaturated hydrocarbons, as
well as other carbon compounds. These
deposits will often contain (1) an upper layer
of gases,(2) a middle layer of liquid/solid
materials (mostly organic compounds) with
(3) a lower layer of saline water.
• These mixtures have names such as West
Texas Intermediate (WTI), Tapis, and Brent
Blend
32
 Asphalt Deposits
• Sometimes the cap rock is eroded away
• The lighter (volatile) compounds evaporate
• Leaving behind very heavy semisolid
material - asphalt

Brea Tar Pits

Los Angeles 33
 World Oil Consumption (2007)
•

Oil Consumption > Thousand barrels daily (most recent) by

country
• Rank   Countries  Amount 
• # 1   United States: 20,517 
• # 2   China: 6,684 
• # 3   Japan: 5,288 
• # 4   Germany: 2,625 
• # 5   Russia: 2,574 
• # 6   India: 2,555 
• # 7   Korea, South: 2,280 
• # 8   Canada: 2,206 
• # 9   France: 1,975 
• # 10   Mexico: 1,896 

34
From the Deposit to the Consumer

35
 Petroleum Refining

Oil Refinery, Washington State, USA

36
 Three Approaches to Petroleum Refining
• (1) Fractional distillation: Relies on
differences in boiling points to separate
compounds from the petroleum mixture
• (2) Hydrocarbon Cracking: Using energy and
catalysts, large molecules are broken down
into smaller molecules.
• (3) Organic synthesis: Special products
called petroleum derivatives are produced
using specific chemical processes.

37
 Fractional Distillation

Based on boiling points, molecules are

separated from a complex mixture. 38
 Hydrocarbon Cracking

• “Hydrocarbon cracking is the process of breaking

long chain hydrocarbons into short ones.” Wikipedia
• C6H14g(Hexane) --> C3H8g (Propane)+ C3H6g(Propene)

• A large molecule is “cracked” into two smaller

molecules.

• Depending on the demand, products are provided to the

market by balancing these two processes as well as
others.

39
 Organic Synthesis

• Here’s an example: The hydration (addition

of water) to ethene (C2H4) results in the
production of ethanol (drinking alcohol)
catalyst

• C2H4(g) + HOH(g)  CH3CH2OH(l) ethanol

ethene
40
 Gasoline
• A mixture of alkanes, usually in the range of
C4 to C10
• These molecules can be “straight” chains or “branched”

n-heptane, C7H16 2,2,4 –

Octane rating, zero trimeythlpentane
Octane rating, 100

Two common examples: there are many more possibilities.

41
 Octane Rating
• Octane Rating is a measure of the “auto-
ignition” properties of a fuel in a spark -
ignition internal combustion engine. In other
words, the fuel’s “anti-knock” characteristics.

42
 Octane Ratings
• Fuels are compared to 2,2,4-trimethyl
pentane (iso-octane) 100 octane and n-
heptane zero octane
• What is compared? The anti-knock
characteristics of the fuel

• If a fuel performs as does a mixture of 90%

2,2,4 trimethylpentane (iso-octane) and 10%
n-heptane, then the fuel is rated as 90
octane and so on….
43
 Octane Ratings

• Research Octane Number (RON): most

common number used internationally

• Motor Octane Number (MON): Also known as

the “aviation lean octane rating”
• Trends 8-10 points below the RON for any
given fuel
• (R+M)/2) = the average value and is reported
in the U.S.A as the octane rating
• All the same: Road Octane Number (RdON), Pump Octane Number (PON), or
(R+M)/2.
44
 Internal Combustion Engine Video
• http://www.youtube.com/watch?
v=wRIKJ6Av5zo

45
 The Combustion Reaction
• Combustion of alkanes
• Alkane(g) + Oxygen(g)  Carbon dioxide (g) Water vapor
• CnH2n+2 + O2(g)  CO2(g) + H2O(g) + energy (mostly heat)
• The reaction must be balanced with coefficients.
• Balance carbons first:
• C5H12(g) + O2(g)  5 CO2(g) + H2O(g) + Energy
• Balance hydrogen next:
• C5H12(g) + O2(g)  5 CO2(g) + 6 H2O(g) + Energy
• Now balance the oxygen:
• C5H12(g) + 8 O2(g)  5 CO2(g) + 6 H2O(g) + Energy

46
 Another Example
• Butane + Oxygen  Carbon dioxide + Water + Energy

• C4H10 + O2  4 CO2 + 5 H2O + Energy

• Note that there are 13 atoms of oxygen on the right side, so we’ll use
(13/2) as our coefficient for the oxygen molecule on the left side to
temporarily balance the equation.
• C4H10 + 13/2 O2  4 CO2 + 5 H2O + Energy

• Sometimes you’ll see the equation left as is, but most often it will be
“cleaned up” by multiplying everything by a factor of two. This removes
the fractional coefficient for the oxygen.

• 2 C4H10 + 13 O2  8 CO2 + 10 H2O + Energy

47
 Heats of Combustion
• These combustion reactions are extremely
important.
• “The combustion of carbon compounds,
especially hydrocarbons, has been the most
important source of heat energy for human
civilizations throughout recorded history.”
http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/funcrx1.htm

• Recall that the U.S’s daily consumption of

petroleum is about 21,000 thousand barrels per
day. That’s 21 million barrels per day!!!
48
 Unintended Consequences
• Every gallon of gasoline consumed produces
about 19 pounds of carbon dioxide gas.
• Humans are shifting the carbon balance on a
massive scale from the geologic carbon
“sinks” to the atmosphere.
• Carbon dioxide is a greenhouse gas.
Greenhouse gases absorb infrared light
(heat) and the result is an increase in
atmospheric temperature. This leads to
climate change.
49
Recent Data

50
 Geologic Time Data

http://www.pir.sa.gov.au/__data/assets/image/0009/51102/cc_figure_16.jpg 51
Global Temperature Anolmaly, 1850-2010

52
 Climate Change
• From the EPA:
• “Many elements of human society and the
environment are sensitive to climate
variability and change. Human health,
agriculture, natural ecosystems, coastal
areas, and heating and cooling requirements
are examples of climate-sensitive systems.”

53
 Some Environmental Changes
• “Some observed changes include:
• (1) shrinking of glaciers
• (2) thawing of permafrost
• (3) later freezing and earlier break-up of ice
on rivers and lakes
• (4) lengthening of growing seasons
• (5) shifts in plant and animal ranges
• (6) earlier flowering of trees “
http://www.epa.gov/climatechange/effects/index.html
54
 An Expanded Example
• Thawing of Permafrost
• The Arctic is expected to experience the greatest
rates of warming compared with other world regions
• As permafrost melts, methane and CO2 are released
from the frozen soil.
• Methane is a greenhouse gas (25 times more potent
than CO2)
• The permafrost system seems to be in a positive
feedback mode (higher temperatures increase the
melting and release of more GHG’s  higher
temperatures and so on)
55
 Global Warming Potential (GWP)
• “For example, the GWP for methane over
100 years is 25 and for nitrous oxide 298.
This means that emissions of 1 million metric
tonnes of methane and nitrous oxide
respectively is equivalent to emissions of 25
and 298 million metric tonnes of carbon
dioxide.”
• http://en.wikipedia.org/wiki/Carbon_dioxide_equivalent

56
57
 Petroleum Toxicity
• Alkanes have relatively low toxicity
• Aromatic hydrocarbons (arenes) have relatively
high toxicity
• Aromatics are components of petroleum.
Benzene, C6H6, is an example of an aromatic
hydrocarbon.
• Benzene is one of the
• 20 most widely used
• chemicals in the
• United States.
58
 Benzene Toxicity
• Benzene is classified as a carcinogen by the
National Toxicology Program because it has
been known to cause cancer. Long-term
exposure to high levels of benzene can
cause leukemia. 
• Short-term exposure to high levels of benzene by
breathing or eating affects the central nervous
system, and can cause paralysis, coma,
convulsions, dizziness, sleepiness, rapid heart rate,
tightness of the chest, tremors, and rapid breathing.
• http://toxtown.nlm.nih.gov/text_version/chemicals.php?id=5
59
 Methane Clathrate (Hydrate)

Methane clathrate
clogs containment
dome.
60
 Clean up
• Combustion

• Pick up

61
 The Clean-up
• Dispersants

62
 How do Dispersants Work?
• Soaps are dispersants.
• Soaps are compounds which are made by
heating fats or oils, from animal or vegetable
sources, with lye, a strongly basic compound.
A typical soap molecule has the formula:
• Long alkane – like nonpolar tail
• CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CO2-1 Na+1
 Polar end
Polar tail dissolves in oils and the
polar end dissolves in water
63
 Cleaning Action of a Soap, a Dispersant
• The large oil drops are reduced to micro-
droplets by the action of the
• soap or detergent – dispersed.

64
 Detergents
• A detergent is a similar kind of molecule, that
is made from petroleum products. A typical
formula is:
• Nonpolar alkane-like tail
• CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2OSO3-1 Na+1
• Polar head

• Where do we source detergents? Take a guess- petroleum!

• So we don’t really remove the oil from the water; it’s still
there. So what happens to it and the detergent?

65
 Bio-degradation of Alkanes
• Certain types of bacteria can metabolize
alkanes: they prefer even-numbered carbon
chains as they are easier to degrade than odd-
numbered chains.
• The steps start with the oxidation of one end of
the chain to form an alcohol and then proceed
step-wise to end up with CO2 and H2O plus
metabolic energy.
• Laboratory experiments suggest that microbial
communities can adapt to an alkane diet.
66
 Biodegradation of Dispersants
• “The two dispersants used by BP, Corexit
EC9500A and Corexit EC9527A, are either
comparable or 10 to 20 times more toxic than
12 other dispersants on the EPA’s approved
list. “
• http://www.csmonitor.com/USA/2010/0520/EPA-scolds-BP-in-Gulf-oil-spill-
dispersant-is-too-toxic-change-it/(page)/2

• The two dispersants used are produced by Nalco Holding Company, NYSE,
NLC. Website: http://www.nalco.com

67
 Nalco Response
• Nalco Releases Additional Technical
Information About COREXIT
• COREXIT 9500, the only dispersant Nalco is manufacturing to help
break up the oil spilling into the Gulf of Mexico, is a simple blend of six
well-established, safe ingredients that biodegrade, do not bioaccumulate
and are commonly found in popular household products, the company
said today. The COREXIT products do not contain carcinogens or
reproductive toxins. All the ingredients have been extensively studied for
many years and have been determined safe and effective by the EPA.

Biodegradation
• A March, 1994, report created by France’s Institut National de
L’Enviroenment Industriel et des Risques indicated that COREXIT 9500
largely biodegraded in 28 days. COREXIT oil dispersant was first
applied to the Gulf oil slick on April 23.
68
 Nalco Response
• Bioaccumulation

• Based on modeling using US EPA software (as part of the

EPI Suite v4.0, 2009), none of the COREXIT product
components pose a risk of bioaccumulating.
• • At 840,000 gallons, the amount of dispersant in the region of the 3,850
square-mile slick represents an average concentration of about 30 parts
per billion to the 10 meters of depth the dispersant will go – even without
factoring in that a substantial portion of the product has already
biodegraded.

• By comparison, the EPA allows drinking water to contain non-

biodegradable contaminants -- including carcinogens and reproductive
toxins -- that exceed the level of biodegradable chemicals present in
COREXIT in the Gulf.
• http://www.nalco.com/news-and-events/4279.htm
69
 The Future?
• Uncertain: first time that dispersants have
been used at a wellhead.
• Plumes of hydrocarbons/dispersants present
• In deep water
• Bacteria “eat” some of the hydrocarbons but
reduce the oxygen levels in doing so; this will
likely impact many marine ecosystems
throughout the Gulf.
• Heavier petroleum consonants remain as “tar
balls”
70
 “Even with leak stopped, Gulf's pain may last years”

• Over time tar balls can lose their lighter

materials, become denser and sink below the
surface to resurface after storms.
• "It could show up in Miami next spring," he
said. "It is likely that the heavier oils ... will
continue to wash in for several years.“
• said Tony Wood, director of the National Spill
Control School at Texas A&M-Corpus Christi.
• http://hosted.ap.org/dynamic/stories/U/US_GULF_OIL_SPILL_FOR_HOW_LON
G?SITE=FLTAM

71
 Florida beach visitors soak up sun, ignore
occasional tar ball
• http://www.cnn.com/2010/TRAVEL/06/20/flori
da.tourism.oil.disaster/index.html

• Massive Gulf of Mexico oil spill

• http://postpix.palmbeachpost.com/mycapture
/folder.asp?
event=991197&CategoryID=50973&ListSub
Albums=0

72
 Predictions

Here is a good interactive map…..

http://map.floridadisaster.org/gator/

73
 Some Final Comments
• From the preceding slides, you can begin to
understand the important role of
hydrocarbons in our biosphere.
• From the concept of hydrocarbons, one can
also begin to understand how petroleum is
connected to products, that a first, may seem
totally unrelated. A couple of examples:

74
 Functional Group Substitution
• Alcohols are derivatives of hydrocarbons as
we saw with the synthesis of ethanol from
ethene and water.
• C2H4 + HOH  CH3CH2OH (ethanol)

• Think of the carbon chain (in this case, C-C) as

derived from ethane (C-C chain or backbone). The
only difference in the number and types of atoms is
that a H atom has been substituted with a –OH
functional group (called a hydroxyl group). Note:
Technically the C2H4 reaction with water is called an addition reaction.
75
• Continuing with this concept of substitution,
we have,
• CH2OHCH2OH (a diol, ethane-1,2-diol) recall that di refers
to two. In this case, two hydroxyl groups attached ,one to
each carbon).
• The common name for this compound is ethylene glycol, or
antifreeze, a toxic liquid.

• Precursor to polymers
• “In the plastics industry, ethylene glycol is important precursor to
polyester fibers and resins. Polyethylene terephthalate, used to make
plastic bottles for soft drinks, is prepared from ethylene glycol.”
Wikipedia
76
 A Series of Substitutions
• Ethane - fuel
• Remove H
• and add OH
• Ethanol – drinking alcohol, solvent, fuel
• Remove H
• and add another OH
• ethane-1,2-diol – antifreeze and precursor for
plastics, etc

77
 A Word from The Graduate
• Youtube:

• http://www.youtube.com/watch?
v=PSxihhBzCjk

78
 “Everybody's plastic, but I love plastic. I want to be plastic.“
Andy Warhol
• http://www.whatisplastic.com/?page_id=599
• Plastics is divided into 2 major categories -
thermoplastics and thermosets.

can recycle Can not recycle

Polyethylene (PE)
79
Polyvinyl Chloride (PVC) Vulcanized Rubber
Urea Formaldehyde (UF)
 Glycerol to Triose, a Sugar
• Consider glycerol (glycerine), CH2OHCH2OHCH2OH

C #2 C #3
C #1

Triose is a
biologically

important sugar .

• What changes were

• made to derive C #1
• this triose, D-aldotriose
• (a sugar)? It is a precursor
C #2
• to lactic acid.
• C3H6O3 Answer: remove
• 2H’s from C #1 and double
• bond the oxygen.

C #3
80
 Conclusion
• Hydrocarbons are arguably the most important
source of energy and chemical base stock in
recorded history.
• Hydrocarbons makeup the “backbones” of
biologically important compounds such as alcohols,
sugars, lipids, and amino acids.

• A knowledge of hydrocarbons is absolutely

necessary to help one understand the complexities
of the biosphere, as well as, economics in the 21 st
century.
81