Organic Chemistry

History:
Vital Force Theory: organic molecules can only be created by living organisms.
In 1828, Professor Wöhler was finishing up his post-doctoral work as a student. While working the
laboratory he succeeded in synthesizing an organic compound, urea, previously observed only in
living tissue. Wöhler, pictured below, made this organic compound from a non-living chemical
substance, Ammonium Cyanate. He evaporated a solution of Ammonium Cyanate to produce Urea.
Organic Chemistry has undergone a substantial change since then. There are well over a million
synthetic organic compounds. Organic Chemistry is defined as the Chemistry of Carbon and its
compounds.
Carbon is a Lego like element. These
atoms tend to form bonds with
themselves creating different shapes.
Like the two below, octane on the left
and a steroid precursor on the right.

The shapes are created by the chemical property of carbon to form 4 bonds.

Hybridization:
The 4 bonds carbon forms is explained by Linus Pauling’s theory of hybridization. Carbon atoms
have an electron configuration of 1s 2 2s2 2p2 This configuration corresponds to the following energy
level diagram.

2p
2s

1s
From the looks of this diagram, carbon might form 3 bonds as appears to be nowhere for a 4 th bond
to form. Linus theorized that the two sublevels, s and p, in the second energy level formed a hybrid
sublevel.

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This new energy level diagram is draw below

2sp

1s
This shows four open orbitals, allowing for the formation of four bonds. Linus won a noble prize for
this theory.
Depending upon the number and types of bonds will dictate the hybridization of a carbon atom. A
carbon atom with four single bonds is designated as sp3, with two single bonds and one double bond
sp2 and with one single and one triple or with two double bonds is designated as sp.
When carbon atoms are bonded using all single bonds, sp 3, a molecular shape is formed (draw the
Lewis structure for CH4 to confirm this to yourself). In this instance the carbon atom forms bonds
with 4 other atoms, resulting in a tetrahedral shape, the blue sections of the below picture. This
shape is formed by the repulsion of the electrons which surround all atoms. So, if four objects are
connected to a central object the farthest these objects can be from each other forms a tetrahedral
shape. The angle between these bonds is 109.5.

When carbon atoms are bonded using one double bond and two single bonds, sp 2, a molecular shape
is formed (draw the Lewis structure for H2CO (H only bonds to C) . In this instance the carbon atom
forms bonds with 3 objects, resulting in a triangular shape (the blue sections of the below picture).
This shape is formed by the repulsion of the electrons which surround all atoms.
The angles
between these bonds are 120. The clear bubbles are showing a pi-bond, a hybrid p orbital which will
be used to create the double bond.

When carbon atoms are bonded using one single bond and one triple bond or two double bonds, sp,
a molecular shape is formed (draw the Lewis structure for CO 2 or HCCH (as written) to confirm this to
yourself) . In this instance the carbon atom forms bonds with 2 objects, resulting in a linear shape,
the blue sections of the below picture. This shape is formed by the repulsion of the electrons which
surround all atoms. So, if two objects are connected to a central object the farthest these objects

2

can be from each other forms a linear shape. The angle across this bond is 180. The clear bubbles
are showing pi bonds, hybrid p orbitals which will be used to create the double or triple bonds.

The shapes around a given carbon atom will have the following shapes based on their hybridization,
sp3, sp2, sp respectively.

General Properties of Organic Molecules:
1. Flammable
2. High Vapor Pressure
3. Odorous
4. Covalently Bonded
5. Non-Polar – functional groups can change these from non-polar to polar or cause the molecule to
be bi-polar.
6. Low Solubility in Water – due to being non-polar as water is polar
7. Rate of Chemical Reaction is Normally Slow
8. Normally Found as Gases and Liquids at Room Temp
9. Non-Conductive of Electrical Current
Alkanes:
The first classification for organic molecules is the most simple, the alkane. The most simple alkane
consists of only carbon and hydrogen atoms connected by single bonds.
Alkanes are common and for the most part chemically unreactive, the chemical reaction combustion
being the major exception.
Alkanes can be found in many common substances; natural gas, gasoline, plastics…
The chemical formula can be generalized as:
CnH2n+2
Where n represents the number of carbons and 2n+2 equals the number of hydrogen’s.
Nomenclature:
Nomenclature is the scientific term for naming compounds. The governing body is “The International
Union of Pure and Applied Chemistry”, or IUPAC for short. The following statement is from their web
site:
“The International Union of Pure and Applied Chemistry (IUPAC) serves to advance the worldwide
aspects of the chemical sciences and to contribute to the application of chemistry in the service of
Mankind. As a scientific, international, non-governmental and objective body, IUPAC can address
many global issues involving the chemical sciences.”

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IUPAC was formed in 1919 by chemists from industry and academia. One of there main functions is
to objectively create rules for naming compounds in the most simplified manner possible. This is
equivalent to creating a new language, just like English grammar, there are

rules.

Even with the advent and acceptance of the IUPAC system some common names still persist, when
discussing a substance the IUPAC name should be used but the common name will be accepted by
most chemical organizations.
Alkane Nomenclature:
Naming of organic structures, unlike biological classification, follows a rigid set of rules. The
International Union of Pure and Applied Chemistry, abbreviated IUPAC, came up with a set of rules
that follows the same standards worldwide, and is accepted among all chemists. However, common
names of compounds, or names that have historical roots, are still used today for many compounds.
The suffix for the alkane family is –ane.

prefix – root – suffix

prefix – where the substitutions, or other interesting things (anything but hydrogen
is interesting to organic chemists!) is/are located. The number associated with the
interesting “thing” or side group will always receive the lowest number possible in
the alkane chain.
root – how many carbons are in the longest chain in the molecule (the longest chain
might twist and turn. Longest chain represents carbon atoms that are bonded to
each other.
suffix – family – type of functional group (alkane, alkene, alcohol, ester, etc...)
Root words are named for its number of carbons:
# of
root
carbons
1
meth2
eth3
prop4
but5
pent6
hex7
hept8
oct9
non10
decExample:
an alkane with 3 carbons is named propane
prop – for the 3 carbons
ane – for the family alkane (meaning all single bonds)

Formula Types:
A variety of methods are used to describe a chemical compounds composition. Sometimes you will
find the chemical formula sufficient. Other times you need to see the structure drawn out, this is
referred to as the structural formula. This is a larger drawing which will show the atoms are
connected. Another is the condensed structural formula, this shows the connections in around about
manner. Lastly, a more lazy form is the line structure. This simplified drawing assumes you know

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that carbon atoms make 4 bonds and that if you do not see a bond drawn assume a hydrogen is
occupying the undesignated bond. Also all ends and turns in the line signify carbon atoms.
Examples:
Chemical Formula:
C4H10

Condensed Structural Formula:
CH3CH2CH2CH3

Structural Formula:

Line Structure:

H H H H
H C

C C

C

H

H H H H

Rules:
1. Find the longest chain of carbons, and use this number as the base/root/parent name
2. Number the chain with the end nearest the first substituent carbon #1.
3. Give the location of the alkyl substituent by the number of the main-chain carbon that it is
attached to.
4. Put the Substituents in alphabetical order (i.e. ethyl before methyl)
5. Substitution Syntax:
a. between numbers and words add a dash
b. between numbers add commas
Examples:

4-ethyl-octane
Correct

5-ethyl-octane
Incorrect

4-ethyl-2-methylheptane
Correct

4-ethyl-6-methylheptane
Incorrect

2-methyl-4-ethylheptane
Incorrect

Isomers:
Structural Isomers – have the same molecular formula, but different structure (are connected/bonded
differently). This is important as it causes different chemical and/or physical properties for the
molecule. The number of possible isomers increases rapidly as the length of the chain increases.
These molecules are isomers of the same chemical formula.

Examples:

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Each of the following molecules has a chemical formula of C 4H10 but they are different molecules
having different properties.

butane

2-methyl propane (isobutane)

More Examples:

hexane

2-methyl pentane

3-methyl pentane

2,3-dimethyl butane

2,2-dimethyl butane (not 3,3-dimethyl butane)

Cyclic Alkanes:
Alkanes can form compounds with themselves. By this I mean they commonly form rings.

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Shown below is cyclohexane. It is a hexane molecule that has come around back onto itself. The
below you will find the chemical formula, structural formula and the line diagram.

H

C6H12

H

H
C

H

C H
H C
H C
C H
C
H
H HH

Sources of Alkanes:
Crude oil is the main supplier. Crude oil is gently heated in a tower, this heating produces vapors,
the lighter compounds to rise higher in the tower, while the heavier compounds rise very little.
Collection equipment is stationed at various levels ready to remove hydrocarbons of various masses.
Alkanes tend to be light and very non-polar, thus they travel to the top of the tower. Natural gas is
the name given to the lightest of the alkanes, this gas is a combination of methane, ethane and
propane. Natural gas pockets are found above large deposits of crude oil. (see picture of refinement
tower below).
Alkanes can also be made these synthetically in a lab, like Professor Wöhler, in 1828 made urea. But
his process is time consuming and expensive. Verify this yourself by pricing synthetic motor oil verse
regular motor oil. Synthetic can easily be 15 times more expensive

Modifications of Straight Chained Alkanes:
Cracking
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Hydrocarbons are indeed flammable, but as it turns out this is not enough to make a fuel a “good”
fuel. An important characteristic for fuels made up of different chemicals, like the mixture named
gasoline, is that all the fuels ignite at the same time. If some fuel ignites before it is designed to
ignite undesirable result occur. This phenomenon in your conventional internal combustion engine is
called “Engine Knock.” The effects of engine knocking vary, some symptoms include; unpleasant
sounds, poor fuel economy, poor engine performance or even engine damage.
The timing of ignition is very important. Many processes are occurring in concert with each other to
deliver smooth power to the cars wheels. Pistons are rising then being forced down by the explosion
of these hydrocarbon vapors mixed with oxygen gas from the atmosphere. The idea is to detonate
this mixture, with a spark plug in gasoline engines, when the piston has reached the top of the
chamber, as the fuel explodes the piston is forced down, this downward motion is mechanically
converted to rotating motion and transferred to the wheels.
The knock occurs when some of the fuel enters the cylinder and ignites before the spark plug has
fired. This causes the piston to apply force to the parts in the motor at that are not designed to
accept this force, at this time. The reason for the premature ignition is due to the varied flammability
of the different hydrocarbons found in gasoline. Some hydrocarbons fire simply because they find
themselves in a hot cylinder, and ignite before the spark plug sparks.
You have no doubt seen the different ‘flavors’ of gasoline available at any gas station. Normally
“octane numbers” 87, 89 and 92 are available. The higher the number the less chance of knocking.
The alkane heptanes is considered the worst and is assigned an octane number of 0. 2,2,4trimethylpentane, common name isooctane, earns an octane number of 100.

2,2,4-trimethylpentane
So, the more isooctane the higher the octane number and the less likely you will have a knock occur.
The more branching the better the fuel. Catalytic cracking, breaks apart straight chained alkanes,
then catalytic reforming “reforms” the bonds, as branched hydrocarbons. The above isooctane could
have been octane cracked and reformed as isooctane. The branching gives the molecule increase
stability. Is allows it to withstand higher temperatures as it waits to be ignited by the firing spark
plug. Aromatics, compound containing benzene rings, are also desirable hydrocarbons due to their
high stability.
Alkenes: the presence of a double bond.
Alkenes are very similar to alkanes. In fact, all organic functional groups that we will be dealing with
will be based off the alkane (simple carbon) structure. An organic molecule is determined to be an
alkene if there are carbons that are doubly bonded to one another. The naming system is VERY
similar to the alkane – so be careful.

prefix – root – ene
You will need to find the longest carbon chain that CONTAINS the double bond functional group. You
will then number your carbon chain beginning at the end nearer to the double bond. IF the double
bond is equidistant from either end, check to see if other functional groups or branch points are
present. Make sure that the numbers assigned to those other branch points are as low as possible.
Multiple double bonds are indicated by additional prefixes such as dienes, trienes, etc. (di for a
species that contains 2 double bonds, and tri for a species that contains 3 double bonds).
Consider the following structure below:

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CH3CH=CHCH3

compared to

CH2=CHCH2CH3

Both compounds contain 4 carbons and 8 hydrogens. What is different about them? Right! The
location of the double bond. So this is something that the name of the compound will help us in
differentiating between the two compounds. These two species are not the same, they will not
behave the same chemically and therefore they will not and can not have the same name
Concept Test:
CH3CH=CHCH3
compared to
CH2=CHCH2CH3
What is the root for a species that has 4 carbon?
Since there is a double bond present, what will the suffix be?
Number the carbons on the structure on the left. What carbon does the
double bond begin on?
Number the carbons on the structure on the right. What carbon does the
double bond begin on?
Therefore the name of the species on the left is
The name of the species on the right is

These species have the same molecular formula. But they are different.
chemical species like this – what was it? Right – an isomer.

We had a name for

When more than one double bond is present in a compound the location of EACH double bond must
be identified by a number (the lowest numbering system is still used!) and then since more than one
double bond is present, the name will be a diene or a triene, etc.
Concept Test
Name the following:
CH3CH=CHCH=CHCH2CH2CH3
CH2=CHCH2CH2CH=C=CH2

Alkynes: presence of a triple bond
Again the naming system will follow the base alkane naming system. You will need to find the
longest carbon chain that contains the triple bond moiety. The carbons will be numbered at the end
nearest to the triple bond. Multiple triple bonds are named as diynes or triynes.
Example: HCCCH2CH2CH3 is named as 1-pentyne

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Organic Functional Groups:
Organic molecules can be very complex, not only for their ability to branch off but also for specialized
groupings of atoms each of which give molecules special properties. Most any of these groupings,
named organic functional groups, can attach themselves to any organic molecule in most any
location. One molecule may have more than one of these groups giving the molecule different
properties. In our studies of “Organic Chemistry” the reactivity of these functional groups will a main
focus.

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Alcohols, and Phenols
This set of notes discusses another set of related organic functional groups. The groups can be found
attached to normal straight chain alkanes as well as unsaturated organics: alkenes, alkynes and
aromatics. Alcohols and phenols deal with oxygen groups
Here are the general formulas and examples of each.
alcohol
general
structure

phenol

OH

R OH

H H
example
structure

OH

H C C OH
H H
ethanol
or
ethyl alcohol

example
name

Br
o-bromo phenol
or
2-bromo phenol

Nomenclature of Alcohols:
1. Select the longest chain containing the alcohol, -OH.
2. Number the chain with the –OH group getting the lowest possible number.
3. Replace the –e at the end of the suffix with –ol.
4. If there are more than one –OH group do not remove the –e from the suffix, but add a di- or triprefix to the –ol suffix.
5. Add a prefix number to indicate which carbon the –OH group is bonded to. This is not always
necessary.
Examples:
ethanol

H H
H C C OH
H H

2-propanol
or
isopropyl alcohol
(rubbing alcohol)

2,4-pentanediol

cyclopentanol

H OH H
H C

C

C

H

OH

H H H

OH

OH

For the first example there is no prefix number to indicate the location of the –OH group. The
reason is that no matter which carbon the –OH group is attached to that carbon is carbon number
one. The name 1-ethanol would be redundant.
For the last example there is no prefix number to indicate the location of the –OH group. The
reason is that no matter which carbon the –OH group is attached to that carbon is carbon number
one. The name 1-cyclopentanol would be redundant .

Alcohols are often classified based on the classification of the carbon they are attached to.

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primary carbon is bonded to one other carbon:
o both of these carbons

H H
H C

C

H

H H

secondary carbon is bonded to two other carbons:
o the center red carbon only

H H H
H C

C

C

H

H H H

tertiary carbon is bonded to three other carbons:
o the center red carbon only

H
H C

H

H

H

H C

C

C

H

H H H
Following the format of the above diagrams, if we replace one hydrogen with a –OH group we get the
following classifications of alcohols:

1, primary alcohol has –OH group bonded to a carbon which is bonded to one other carbon:

H H
H C

C

OH

H H

2, secondary alcohol has –OH group bonded to a carbon which is bonded to two other carbon:

H OH H
H C

C

C

H

H H H

3, tertiary alcohol has –OH group bonded to a carbon which is bonded to three other carbon:

H
H C

H

H

H

H C

C

C

H

H OH H
The classification dictates what types of reactions the alcohol will undergo. Simple test can be
performed to determine which classification of alcohol is present.

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Ethers
An ether functional group is indicated by the presence of an oxygen atom sandwiched in-between
two carbons. The generic formula description of an ether is C-O-C. Ethers are named as each C
group on either side of the oxygen are alkyl groups followed with the word ether. The alkyl groups
are alphabetized but in the grand scheme of things, ethyl methyl either is the same compound as
methyl ethyl ether.
CH3CH2-O-CH2CH2CH3
A 2 carbon alkyl group is an ethyl group (eth for 2 and yl for alkyl group)
A 3 carbon alkyl group is a propyl group (prop for 3 and yl for alkyl group)
Therefore the name is ethyl propyl ether
If both groups are the same on either side of oxygen then the alkyl group is named as a dialkyl group.
For example:
CH3CH2-O-CH2CH3
A 2 carbon alkyl group is an ethyl group, there are two ethyl groups therefore
Diethyl ether is the name for this species

Aldehydes and Ketones
Aldehydes and ketones are compounds that are very similar to one another and oftentimes confused
with one another when you are first starting out. Examine the two structures below and notice a
subtle difference between the aldehyde moiety and the ketone moiety.

O

O

CH3CCH3

CH3CH2CH

Aldehydes are always TERMINAL or on the end of the carbon chain
Ketones are always INTERNAL, they can never be on the end of the carbon chain.
Aldehydes are named the same as the parent alkane, but the e on the alkane name is dropped and al
is added.
The longest carbon chain must contain the aldehyde functional group.
Ketones are named the same as the parent alkane, but the e is dropped on the alkane and one is
added. Since the carbonyl group is internal, and may vary in location, the exact location must be
identified using the same numbering system that we have been talking about.

Concept Test

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Name the following:

O
CH 3CH 2CH 2CH 2CH 2CH

O
CH3CH2CH2CH2CH2CH2CH2CH
O
CH3CH2CH

O
CH3CH2CH2CCH2CH3
O
CH3CH2CH2CH2CCH3
O
CH3CH2CCH2CH2CH3

O
CH3CCH3
O
CH3CH2CH2CH2CCH2CH2CH3

O
CH3CCH2CH2CH2CH2CH2CH3

Carboxylic Acids
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Carboxylic acids and esters are like aldehydes and ketones in that they contain the carbonyl
functional group.

O
C
carbonyl

O

-OH

O

C OH

hydroxyl

carboxylic acid

R'

C O C R
ester

Carboxylic acids are the acids found in organic molecules, the carbon based compounds necessary
for life. The term “carboxylic” is derived from carbonyl and “hydroxyl”, the two structures which
make an organic acid.
None of the these carboxylic acids are classified as strong acids. Remember a strong acid is an acid
which fully dissociates in an aqueous environment. This is not to say an organic acid is not able to
cause harm.
Small concentrations of hydrogen ion given off by organic acids are potent enough to kill most
microscopic organisms and cause tissue irritation and/or damage to larger organisms. Acetic acid is
the acid found in vinegar, a pickle stored in its brine may not spoil and be edible for years partly
because of the organic acid from the vinegar kills the bacteria which will cause spoilage.

Nomenclature:
carboxylic acids:

1. count number of carbons in the longest carbon chain containing the –COOH group
2. replace the –e with the suffix –oic acid
3. compound containing multiple -COOH groups do not drop the –e but add a di- or tri- to the
ending – carboxylic acid or add a di- or tri- to the suffix –oic acid.

Examples:
Structural Formula
Condensed
Structural Formula
IUPAC
Common Name

O
CH3

O

C OH

CH3

CH2

C OH

O
HO C CH2

C OH

CH3COOH

CH3CH2COOH

HOOCCH2COOH

ethanoic acid
acetic acid

propanoic acid
-

propandioic acid
malonic acid

Esters:


1.
2.
3.

O

to create an ester an alcohol is reacted with a carboxylic acid
an ester is named for its starting materials, the acid and the alcohol
the first part names the alcohol, use the side chain abbreviation, i.e. methyl, ethyl…
the second part names the carboxylic acid
to end the second part change the –ic of the carboxylic acid to -ate

Examples:
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O

Structural
Formula

CH3

Condensed
Structural
Formula
IUPAC
Common
Name

O

O

C O CH3

CH3

CH2

CH3

C O CH2 CH3

C O

CH3COOCH3

CH3CH2COOCH2CH3

CH3COOC6H5

methyl ethanoate

ethyl propanoate

phenyl ethanoate

methyl acetate

ethyl propyrate

phenyl acetate

Salts of Carboxylic Acids:
 to create a salt of a carboxylic acid, neutralize an organic acid with a strong base
1. change the name of the carboxylic acid suffix from –ic acid to –ate, just as you did with the ester
2. the first word will by the name with the cation, probably a metal
Examples:
Structural Formula
Condensed
Structural Formula
IUPAC
Common Name

CH3

C O Na

O

O

O
CH3

CH2

C O

C O

K

CH3COONa

CH3CH2COOK

C6H5COONa

sodium ethanoate
sodium acetate

potassium propanoate
-

sodium benzoate
phenyl acetate

Na

Preparation:
Carboxylic Acids:
The oxidation of a primary alcohol will lead through an aldehyde to a carboxylic
acid.
H H
H O
H O
[O]
[O]
H C C OH
H C C H
H C C OH
H H
H H
H H
primary alcohol

carboxylic acid

aldehyde

Esters (esterification):
To create an ester an alcohol combines with a carboxylic acid in a dehydration reaction, which
produces the ester and a water molecule.

carboxylic acid

alcohol

O

H H

CH3

C OH

acetic acid

ester

HO C C H

CH3

H H
ethanol

O

H H

C O

C C H

H H
ethyl ethanoate

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H2O

Extra Information
Reactions:
Ionization:

The first definition of an acid is a proton donator. A carboxylic acid donates the hydrogen attached to
the oxygen fulfilling the definition of an acid.

O

O
CH3

CH3

C O H

H+

C O

This reaction has a double arrow. The reason is that organic acids are weak acids and form an
equilibrium in a solution. Only a small percentage of the acids give up their hydrogen. Once the
equilibrium has been reached the concentration of acid, hydrogen ion and anion remain constant. In
the above case we have acetic acid, acetate anion and hydrogen ion.

Acid/Base:
Just as you can neutralize an inorganic acid, organic acid can be neutralized. They same product is
formed, a salt and water. If sodium hydroxide is used to neutralize acetic acid the following reaction
occurs.

O

O
CH3

NaOH

C O H

ethanoic acid

CH3

H
O

C O Na

sodium ethanoate

sodium hydroxide

H

water

Acid Anhydrides:
Two carboxylic acids can be combined to form an acid anhydrides. The term anhydride combines anand -hydride. The prefix an- means anti, in this form it is describing a loss. The loss is of water,
which is where the hydride portion comes to play. So, two carboxylic acids are

O
CH3

C O H

O
CH3

H O C CH3

O

O

C O

C CH3

H2O

Common Sources:
Carboxylic Acids:
The carboxylic acid function group can be found in all facets of nature. A few of the more common
acids follow, formic acid, a chemical defense for some ants, acetic acid, found in vinegar, propanoic
acid, found in cheese, butanoic acid, from spoiled butter, citric acid, from citric fruits, lactic acid, from
dairy products, palmitic acid, found in palm oil and stearic acid, from beef fat.

Esters:
The most utilized ester is that found in soap. Soap pre-dates history. The production is simple, boil a
fat in wood ash. The fat is actually the carboxylic acid, hence the name fatty acid. A fat like stearic
acid, beef fat, would work very well for producing soap. A component of wood ash is potassium
hydroxide, which is a strong base. So, your average caveman could easily produce soap by boiling
some beef fat combined with ash from the campfire.
Other uses include dry cleaner fluids, pharmaceutical drugs, flavorings an scents. Methyl salicylate
can be found in wintergreen flavored mints.

Polymers
Polymers are an extremely important material in our world. Plastics are the most commonly used
polymer, and they are all around us, intertwined in our daily lives. How many of you brushed your
teeth this morning? Well, that was not horsehair on your toothbrush! (I hope!) How many of you put
on clothes? Hopefully all of you. Ever paid attention to that material label inside your shirt or pants?

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Anyone wearing Nylon or Dacron or polyester today? Because of their abundance in our society, as
chemists, we should study the properties as well as structures of polymer materials.
Polymers are extremely large molecules with molar masses exceeding 1.0 x 10 6 grams/mole. A
polymer is a material composed of many repeating units called monomers. Monomers are molecules
which have the structural ability to react and form a repeating sequence. The chemical structure of a
monomer affects both the type of polymer that it can form as well as the way in which the polymer
forms in a chemical reaction. The main classes of polymer materials are: addition polymers and
condensation polymers.
An addition polymer is formed from a compound that contains a multiple bond. An initiator is used to
open the first monomer's multiple bond, but once the reaction starts, the open monomer reacts with
other monomers in order to form a polymer.

This reaction requires an initiator, like benzoyl peroxide or t-butyl benzoyl peroxide. Initiators are
unstable molecules that split apart into free radicals. Free radicals are highly reactive! They cause
the first monomer’s double bond to open and allow the polymerization process to begin. Often heat
or ultraviolet light are needed before the initiator will form free radicals; however, initiators
(especially, peroxide initiators) should be handled with care because they can explode if dropped
with sufficient force.
Polymers all share some similar properties. These include: 1) the flexibility and structure 2)
strength (try ripping apart your nylon coat!) 3) the presence of crosslinks (usually covalent bonds)
between polymer chains
Crosslinking can occur if there is a double bond or other reactive group present on a side chain.
These reactive areas can be used to create new bonding regions which will make a stronger, more
rigid material. Crosslinking restricts the ability of the individual polymer chains to slide past one
another. Crosslinking can be thought of as a three-dimensional network structure. Depending on the
degree of crosslinking that occurs, different properties result. Low levels of crosslinking, such as
elastomers (e.g. rubber bands) are elastic and deformable. Highly crosslinked materials, such as
Bakelite (billiard balls) are obviously rigid and brittle.
Because we use so much plastic, recycling is an excellent way to conserve resources. A code for
plastics was established based on the most frequently used plastics (see chart below).

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Methyl Methacrylate:
Poly(methyl methacrylate), which lazy scientists call PMMA, is a clear plastic, used as a shatterproof
replacement for glass. The barrier at the ice rink which keeps hockey pucks from flying in the faces of
fans is made of PMMA. The chemical company Rohm and Haas makes windows out of it and calls it
Plexiglas. Ineos Acrylics also makes it and calls it Lucite. Lucite is used to make the surfaces of hot
tubs, sinks, and the ever popular one piece bathtub and shower units, among other things. PMMA is
a member of a family of polymers which chemists call acrylates, but the rest of the world calls
acrylics. Another polymer used as an unbreakable glass substitute is polycarbonate, but PMMA is
cheaper!
When it comes to making windows, PMMA has another advantage over glass. PMMA is more
transparent than glass. When glass windows are made too thick, they become difficult to see
through. But PMMA windows can be made as much as 13 inches (33 cm) thick, and they're still
perfectly transparent. This makes PMMA a wonderful material for making large aquariums, whose
windows must be thick in order to contain the high pressure millions of gallons of water. In fact, the
largest single window in the world, an observation window at California's Monterrey Bay Aquarium, is
made of one big piece of PMMA which is 54 feet long, 18 feet high, and 13 inches thick (16.6 m long,
5.5 m high, and 33 cm thick).
PMMA is also found in paint. The painting on your right, Acrylic
Elf was painted by Pete Halverson with acrylic paints. Acrylic
"latex" paints often contain PMMA suspended in water. PMMA
doesn't dissolve in water, so dispersing PMMA in water requires
we use another polymer to make water and PMMA compatible
with each other.
But PMMA is more than just plastic and paint. Often lubricating
oils and hydraulic fluids tend to get really viscous and even
gummy when they get really cold. This is a real pain if you trying
to operate heavy equipment in really cold weather. When a small amount of PMMA is dissolved in
these oils and fluids, they do not get viscous in the cold, and machines can be operated down to -100
o
C! (the question is, can the human operating the machine take that weather!!) PMMA is made by
free radical vinyl polymerization from the monomer methyl methacrylate.

As you can see from the picture, the structure of methyl methacrylate kind of looks like
Massachusetts. But Massachusetts does not polymerize, because there is only one.
NYLON 6,6:
Nylons are some of the most important fibers produced commercially. If you have ever slept in a tent
or used a toothbrush, you have used nylon fibers. But nylon can be more than just fibers. It is also
used for self-lubricating gears and bearings. Nylon-clay composites are used to make under-hood
automobile parts.
The two most important kinds of nylon are nylon 6,6 and nylon 6. These two nylons have almost
identical properties. Both were invented in the late 1930s. Nylon 6,6 was discovered first. It was

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invented in the United States by Wallace Carothers who was working for DuPont. Not long after that
Nylon 6 was invented in Germany by Paul Schlack who was working for I.G. Farben.
Physical Properties
You may ask yourself, "Why does nylon act as it does?" You may ask yourself, "Why does nylon make
such good fibers?" The answer to both is pretty simple: intermolecular forces. When you are talking
about nylons, the most important intermolecular force is hydrogen bonding. The nitrogen-bonded
hydrogens of one nylon chain will hydrogen bond very strongly with the carbonyl oxygens of another
nylon chain. These hydrogen bonds make crystals of nylon very strong, because they hold the nylon
chains together very tightly. Of course, these strong crystals make strong fibers.
Unless it has been drawn into fibers, only about 20-30% of the nylon in a given sample is crystalline
when in solid form. The rest is in the amorphous phase. But even though it's non-crystalline, the
chains are still bound strongly to each other by hydrogen bonds. This combination of crystalline and
strongly associated amorphous phases is what makes nylon thermoplastics so tough. (This only
applies to nylons used as thermoplastics, mind you. When drawn into fibers nylons become almost
entirely crystalline).

We all know that a lot of the nylon produced ends up as clothing. But it also ends up as other
everyday things like rope, tents, and toothbrush bristles. Sometimes nylon is used to make the belts
that reinforce tires. Most passenger car tires have steel belts, but tires for aircraft, trucks and offroad vehicles are often made of nylon. Under the hood of your car you'll find nylon fibers reinforcing
rubber belts, too.
Theory
Step-growth Polymerizations and Chain-growth Polymerizations
All polymerizations fall into two categories: step-growth polymerizations and chain-growth
polymerizations. Both step-growth polymerizations and chain-growth polymerizations are used to
make nylons. Making nylon from a diacid and a diamine is a step-growth polymerization.
So what is the difference between the two types of polymerization?
differences you should know about for this experiment...

There are some practical

In a step-growth system, we start off with monomers. The monomers combine and grow into dimers,
trimers, tetramers, and so forth. The molecules get bigger and bigger, but only when you done
(when the polymerization reaches high conversion) do you have high molecular weight polymers.

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But in a chain growth system, again you start off with monomers, but the monomers quickly form
high molecular weight polymers. There are high molecular weight polymers present in your test tube
just after you start the polymerization. There are no dimers, trimers, and other oligomers (many
units) hanging around. A growing polymer chain grows so fast that it reaches high molecular weight
quickly, and it does not spend any real length of time as an oligomer.
Polycondensations
There is another way to describe polymerizations other than the step-growth/chain-growth system.
There is also the condensation/addition system. The most important thing you need to know about
this system is that it classifies all polymerizations as polycondensations or polyadditions.
Polycondensations are polymerizations in which a small molecule by-product is produced. The byproduct is usually something like water, HCl, or once in awhile NaCl. Polyadditions on the other hand
are polymerizations in which no by-product is produced.
Polycondensation can be used to make nylons. The simplest polycondensation for making nylons is
the polymerization of a diacid and a diamine. This reaction might not normally go to high
conversions (make a lot of nylon as the product), but by removing the water by-product, we can force
this reaction go to higher conversions.

Removing water makes the reaction go to high conversion thanks to LeChatlier's Principle.
Our preparation of nylon uses the diacid, and is a condensation polymer. It is produced when a
diamine and a diacid chloride react. The small molecule produced is hydrochloric acid.

Today in lab, you will react 1,6-hexanediamine and adipoyl chloride to form nylon-6,6 and HCl. The
structures for the monomers and polymer are shown below.

The Silly Polymer:

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Silly Putty is a dilatant compound, a silicone based polymer that is highly elastic, exhibits high
bounce, can be easily molded, yet can hold it shape while at rest. It is non-toxic and non-irritating to
the skin.
The history of silly putty is quite amusing. In 1943 James Wright, an engineer, was attempting to
create a synthetic rubber. He was unable to achieve the properties he was looking for and put his
creation (later to be called silly putty) on the shelf as a failure. A few years later, a salesman for the
Dow Corning Corporation was using the putty to entertain some customers. One of his customers
became intrigued with the putty and saw that it had potential as a new toy. In 1957, after being
endorsed on the "Howdy Doody Show", silly putty became a toy fad. Recently new uses such as a
grip strengthener and as an art medium have been developed. Silly putt even went into space on
the Apollo 8 mission.
The polymers in silly putty have covalent bonds within the molecules, but hydrogen bonds between
the molecules. The hydrogen bonds are easily broken. When small amounts of stress are slowly
applied to the putty, only a few bonds are broken and the putty "flows". When larger amounts of
stress are applied quickly, there are many hydrogen bonds that break, causing the putty to break or
tear.
If a substance springs back to its original shape after being twisted, pulled, or compressed, it is most
likely a type of polymer called an elastomer. The elastomer has elastic properties (i.e., it will recover
its original size and shape after being deformed). An example of an elastomer is a rubber band or a
car tire.
The liquid latex (Elmer's glue) which you use contains small globules of hydrocarbons suspended in
water. The silly putty is formed by joining the globules using sodium borate (a cross-linker). The silly
putty is held together by very weak intermolecular bonds that provide flexibility around the bond and
rotation about the chain of the cross-linked polymer. If the cross-linked bonds in a polymer are
permanent, it is a thermosetting plastic. If the bonds are non-permanent, it can be considered either
thermoplastic or an elastomer.
The covalent bonds along the chain are strong, but the bonds between chains are normally weak.
However, additives such as borax allow the formation of strong "cross-links" between chains, such as
C-B-C. As the number of cross-links increases, the material becomes more rigid and strong.

Borax crosslinking in a polymer
I’m Melting . . .
Polystyrene is an inexpensive and hard plastic, and probably only polyethylene is more common in
your everyday life. The outside housing of the computer you are using now is probably made of
polystyrene. Model cars and airplanes are made from polystyrene, and it also is made in the form of
foam packaging and insulation. Clear plastic drinking cups are made of polystyrene, so are a lot of

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the molded parts on the inside of your car, like the radio knobs. Polystyrene is also used in toys, and
the housings of things like hairdryers, computers, and kitchen appliances. What we commonly call
styrofoam, is actually the most recognizable form of foam polystyrene packaging. Styrofoam ® is a
Dow Chemical Co. trademarked form of polystyrene foam insulation, introduced in the U.S. in 1954.
Styrofoam® is a trademarked name, the real name of the product is foamed polystyrene.
Polystyrene is a vinyl polymer. Structurally, it is a long hydrocarbon chain, with a phenyl group
attached to every other carbon atom. Polystyrene is produced by free radical vinyl polymerization,
from the monomer styrene.

Polystyrene is a polymer which is cross-linked to provide extra stability in keeping its shape. Air (or
other common gas) can be blown into molten polystyrene (plastic) to create a light and foamy
material called styrofoam. This air-filled product is good for packing and insulation. Water tends to
dissolve molecules that contain OH groups (hydrophilic), but styrofoam does not have OH groups
associated with them which makes styrofoam cups good to drink out of! However, styrofoam cups
cannot hold all types of liquid.

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