REVIEWER IN GENERAL CHEMISTRY 1

The Bohr model was a one-dimensional model that used one quantum number to describe the distribution of
electrons in the atom. The only information that was important was the size of the orbit, which was described by
the n quantum number. Schrodinger's model allowed the electron to occupy three-dimensional space. It
therefore required three coordinates, or three quantum numbers, to describe the orbitals in which electrons can
be found.

The three coordinates that come from Schrodinger's wave equations are the principal (n), angular (l), and
magnetic (m) quantum numbers. These quantum numbers describe the size, shape, and orientation in space of
the orbitals on an atom.

The principal quantum number (n) describes the size of the orbital. Orbitals for which n = 2 are larger than
those for which n = 1, for example. Because they have opposite electrical charges, electrons are attracted to the
nucleus of the atom. Energy must therefore be absorbed to excite an electron from an orbital in which the
electron is close to the nucleus (n = 1) into an orbital in which it is further from the nucleus (n = 2). The
principal quantum number therefore indirectly describes the energy of an orbital.

The angular quantum number (l) describes the shape of the orbital. Orbitals have shapes that are best
described as spherical (l = 0), polar (l = 1), or cloverleaf (l = 2). They can even take on more complex shapes as
the value of the angular quantum number becomes larger.

There is only one way in which a sphere (l = 0) can be oriented in space. Orbitals that have polar (l = 1) or
cloverleaf (l = 2) shapes, however, can point in different directions. We therefore need a third quantum number,
known as the magnetic quantum number (m), to describe the orientation in space of a particular orbital. (It is
called the magnetic quantum number because the effect of different orientations of orbitals was first observed in
the presence of a magnetic field.)

Rules Governing the Allowed Combinations of Quantum Numbers

The three quantum numbers (n, l, and m) that describe an orbital are integers: 0, 1, 2, 3, and so on.

The principal quantum number (n) cannot be zero. The allowed values of n are therefore 1, 2, 3, 4, and so on.

The angular quantum number (l) can be any integer between 0 and n - 1. If n = 3, for example, l can be either 0,
1, or 2.

The magnetic quantum number (m) can be any integer between -l and +l. If l = 2, m can be either -2, -1, 0, +1,
or +2.

Magnetic Properties

Substances whose atoms, molecules, or ions contain unpaired electrons (which must be in different orbitals) are
weakly attracted into a magnetic field, a property known as paramagnetism. This is because the Spin Quantum
Number for the substance will not be zero since each electron will not have a partner to cancel. Paramagnetism
is typically 0.1% as strong as the familiar "ferromagnetism" of common magnets.

Most substances have all their electrons paired. This means that each electron's spin number will be canceled by
another electron (although they're usually in the same orbital, they need not be). The net spin will be zero for the
substance, and it will not be attracted into a magnetic field, but actually repelled slightly. The repulsion is
typically 0.1% as great as paramagnetic attraction. This property is known as diamagnetism.

Paramagnetic vs Diamagnetic Example

Which of the following elements would be expected to be paramagnetic? Diamagnetic?

He, Be, Li, N

All of the electrons are spin-paired in diamagnetic elements so their subshells are completed, causing them to be
unaffected by magnetic fields. Paramagnetic elements are strongly affected by magnetic fields because their
subshells are not completely filled with electrons.

To determine whether the elements are paramagnetic or diamagnetic, write out the electron configuration for
each element.

• He: 1s2 subshell is filled

• Be: 1s22s2 subshell is filled

• Li: 1s22s1 subshell is not filled

• N: 1s22s22p3 subshell is not filled

Answer

Li and N are paramagnetic.

He and Be are diamagnetic.

Lewis Dot Structure

Lewis symbols (also known as Lewis dot diagrams or electron dot diagrams) are diagrams that represent the
valence electrons of an atom. Lewis structures (also known as Lewis dot structures or electron dot structures)
are diagrams that represent the valence electrons of atoms within a molecule. These Lewis symbols and Lewis
structures help visualize the valence electrons of atoms and molecules, whether they exist as lone pairs or within
bonds.

Octet of Valence Electrons

Atoms gain, lose, or share electrons in their valence level in order to achieve greater stability, or a lower energy
state. From this perspective, bonds between atoms form so that the bonded atoms are in a lower energy state
compared to when they were by themselves. Atoms can achieve this more stable state by having a valence level
which contains as many electrons as it can hold. For the first principal energy level, having two electrons in it is
the most stable arrangement, while for all other levels outside of the first, eight electrons are necessary to
achieve the most stable state.

Lewis Symbols

In the Lewis symbol for an atom, the chemical symbol of the element (as found on the
periodic table) is written, and the valence electrons are represented as dots surrounding it.
Only the electrons in the valence level are shown using this notation. For example, the
Lewis symbol of carbon depicts a “C’ surrounded by 4 valence electrons because carbon
has an electron configuration of 1s22s22p2.

Procedure for Drawing Simple Lewis Structures

We have looked at how to determine Lewis structures

for simple molecules. The procedure is as follows:

1. Write a structural diagram of the molecule to

clearly show which atom is connected to which
(although many possibilities exist, we usually
pick the element with the most number of
Alternate view of lewis dot structure of water: This arrangement of shared
possible bonds to be the central atom). electrons between O and H results in the oxygen atom having an octet of
electrons, and each H atom having two valence electrons.
 2. Draw Lewis symbols of the individual atoms in the molecule.
3. Bring the atoms together in a way that places eight electrons around each atom (or two electrons for H,
hydrogen) wherever possible.
4. Each pair of shared electrons is a covalent bond which can be represented by a dash.

VSEPR Rules

1. Draw the Lewis structure for the molecule or ion.

2. Count the total number of regions of high electron density (bonding and unshared electron pairs)
around the central atom.

o Double and triple bonds count as ONE REGION OF HIGH ELECTRON DENSITY.

o An unpaired electron counts as ONE REGION OF HIGH ELECTRON DENSITY.

o For molecules or ions that have resonance structures, you may use any one of the resonance
structures.

3. Identify the most stable arrangement of the regions of high electron density as ONE of the following:

o linear
o trigonal planar
o tetrahedral
o trigonal bipyramidal
o octahedral
4. Determine the positions of the atoms based on the types of electron pairs present (i.e., bonding pairs vs.
unshared pairs). For trigonal bipyramidal and octahedral arrangements, there can sometimes be more
than one possible arrangement of the bonding and unshared pairs:

Trigonal bipyramidal - place any unshared pairs in the plane of the triangle.

Octahedral - if you have two unshared pairs, place them on opposite sides of the central atom.

5. Identify the molecular structure based on the positions of the ATOMS (NOT on the regions of high electron
density).
Molecular Polarity

To determine if a molecule is polar or nonpolar, it is frequently useful to look at Lewis structures. Nonpolar
compounds will be symmetric, meaning all of the sides around the central atom are identical - bonded to the
same element with no unshared pairs of electrons. Notice that a tetrahedral molecule such as CCl4CCl4 is
nonpolar Figure (4.12.14.12.1. Another non polar molecule shown below is boron trifluoride, BF 3. BF3 is a
trigonal planar molecule and all three peripheral atoms are the same.

Polar molecules are asymmetric, either containing lone pairs of electrons on a central atom or having atoms
with different electronegativities bonded. This works pretty well - as long as you can visualize the molecular
geometry. That's the hard part. To know how the bonds are oriented in space, you have to have a strong grasp of
Lewis structures and VSEPR theory. Assuming you do, you can look at the structure of each one and decide if it
is polar or not - whether or not you know the individual atom electronegativity. This is because you know that
all bonds between dissimilar elements are polar, and in these particular examples, it doesn't matter which
direction the dipole moment vectors are pointing (out or in).

A polar molecule is a molecule in which one end of the molecule is slightly positive, while the other end is
slightly negative. A diatomic molecule that consists of a polar covalent bond, such as HFHF, is a polar
molecule.

Steps to Identify Polar Molecules

1. Draw the Lewis structure

2. Figure out the geometry (using VSEPR theory)
3. Visualize or draw the geometry
4. Find the net dipole moment (you don't have to actually do calculations if you can visualize it)
5. If the net dipole moment is zero, it is non-polar. Otherwise, it is polar.

All About Functional Groups

• Functional groups are specific groupings of atoms within molecules that have their own characteristic
properties, regardless of the other atoms present in a molecule.

• Common examples of functional groups are alcohols, alkenes, alkynes, amines, carboxylic acids,
aldehydes, ketones, esters, and ethers, among others.

1. Functional Groups

A functional group is what we call specific groupings of certain atoms within molecules that have their own
characteristic properties.

Here are some of the most commonly encountered functional groups. Note that “R” is a placeholder for a
generic carbon substituent.
A second group of slightly less commonly encountered functional groups are here. This is by no means an
exhaustive list, but it’s at least a good start.

Do these names sound familiar?

Propane. Tylenol. Ibuprophen. Testosterone. Dopamine.

Learning functional groups will be a matter of connecting those names to general structures.

Another good way to get to know functional groups is to think about the relative electronegativities of the
elements in each group. That will help you understand their properties and help you think about how they
behave in chemical reactions

2. Alkanes, Alkenes, Alkynes, and Aromatic Rings

The hydrocarbon functional groups are very non-polar and tend to be extremely weak acids.

In hydrocarbons, the only types of intermolecular interactions are London dispersion forces and their boiling
points tend to be quite low, relative to molecules containing more polar functional groups.

2. Alkanes, Alkenes, Alkynes, and Aromatic Rings

The hydrocarbon functional groups are very non-polar and tend to be extremely weak acids.

In hydrocarbons, the only types of intermolecular interactions are London dispersion forces and their boiling
points tend to be quite low, relative to molecules containing more polar functional groups.

Alkanes are hydrocarbons containing no multiple bonds. Alkane substituents are called alkyl groups, which
refers to alkanes lacking a C-H bond such as methyl, ethyl, or propyl.

• Common examples of alkanes are methane, ethane, propane, butane, and octane.

• The C-H bond is highly covalent and alkanes are very non-polar. They do not mix with water.

• Alkyl carbons are sp3 hybridized and have tetrahedral geometry about the carbon.

• You can often think of alkyl groups as the “spectator” functional groups of organic chemistry,
abbreviated as R-. With the exceptions of free-radical substitution and, of course, combustion, alkanes
 don’t undergo a huge number of different reactions. They tend to provide the backbone of most organic
molecules.

Alkenes are hydrocarbons with one or more carbon-carbon double bonds.

• Common examples are ethene, propene, and butene.

• Alkene substituents are called alkenyl groups; vinyl is often used to refer to -CH=CH2 .

• Alkenyl carbons are sp2 hybridized, with a trigonal planar geometry.

Alkynes contain a carbon-carbon triple bond.

• Ethyne (acetylene) is the simplest alkyne; alkynes are sometimes called acetylenes.

• Alkyne substituents are called alkynyl groups.

• Terminal alkynes have a C-H. Internal alkynes have C-C bonds at each end.

• Alkynyl carbons are sp hybridized with a linear geometry.

Benzene rings are six-membered rings containing 3 double bonds. Benzene rings are common in nature due to a
property called aromaticity (nothing to do with its smell) that make them unusually stable. Can also be drawn as
a hexagon with a circle.

• Benzene, methylbenzene (toluene) is responsible for the smell of model airplane glue.

• Benzene substituents C6H5– are called phenyl groups.

• The carbons in benzene are sp2 hybridized with trigonal planar geometry.

3. Alcohols, Ethers, Amines, Thiols, Alkyl Halides

These functional groups is considerably more polar due to the greater difference in electronegativities between
the bonding atoms.

Stronger intermolecular forces are present in these functional groups due to the dipole-dipole interactions.
Additionally, alcohols and amines are capable of hydrogen bonding, which further increase boiling points.
Alcohols R-OH contain carbon bonded to the hydroxyl group -OH.

• Common examples include methanol, methanol, isopropanol.

• The O-H bond is highly polarized and participates in hydrogen bonding.

• Hydroxyl groups also increase water solubility.

• Alcohols are weak acids and can also act as Lewis bases.

• Hydroxyl groups bonded to C=O are considered to be carboxylic acids, a separate functional group (see
below)

Ethers R-O-R are oxygen atoms flanked by two bonds to carbon.

• Diethyl ether, tetrahydrofuran, and dioxane are ethers that are commonly used as lab solvents.

• Ethers cannot serve as hydrogen-bond donors, so their boiling points are lower than those of alcohols
of equivalent molecular weight, but higher than those of hydrocarbons due to greater dipole-dipole
forces.

Alkyl halides have functional group R-F, R-Cl, R-Br, R-I where R is an alkyl group.

• Bromobutane, methyl bromide, and chloroform are all examples of alkyl halides.

• Dipole-dipole interactions lead to higher boiling points than those found in alkanes.

• If R is alkene, they are alkenyl halides.

• Very important functional groups for substitution and elimination reactions.

Amines contain the functional group -NH2, -NHR, or NR2 where R is a hydrocarbon.

• Morphine, codeine, and cocaine are just three of many prominent molecules that contain amines.

• Amine substituents are known as amino groups.

• Amines with N-H bonds are capable of hydrogen bonding, which leads to higher boiling points and
water solubility.

• The lone pair on the nitrogen can act as a base.

Thiols (mercaptans) R-SH are the sulfur-containing cousins of alcohols.

• The sulfur atom is not nearly as electronegative as oxygen, so the S-H bond is considerably less
polarized.

• Thiols can act as weak acids; stronger acids than alcohols.

• Thiols are most notorious for their strong stench; ethanethiol is added to natural gas to give it its
characteristic smell.

4. Aldehydes, Ketones, Carboxylic Acids, Esters

The C=O group is referred to as the carbonyl group. The C=O bond is strongly polarized towards oxygen and
the carbon bears a partial positive charge.

Carbonyls are found in aldehydes, ketones, esters, and carboxylic acids.

Aldehydes RCHO have C=O bonded to carbon and to C-H

• Formaldehyde, acetaldehyde, and benzaldehyde are common examples.

• They have polar covalent bonding but are not hydrogen bond donors

Ketones RC(O)R have C=O bonded to two carbons.

• Acetone (2-propanone) is nail polish remover.

Carboxylic Acids RCOOH have a carbonyl bonded to -OH. They are distinct functional groups from alcohols.

• Acetic acid (vinegar) and formic acid are the simplest carboxylic acids. Other short-chain acids like
butanoic and pentanoic acids are notorious for their locker-room smells (or worse).

• The hydroxyl group participates in hydrogen bonding and carboxylic acids have higher boiling points
as a result.

• Despite the name, carboxylic acids tend to be relatively weak acids, not undergoing full dissociation in
water (as compared to strong acids such as HCl and H2SO4).

Esters RCOOR are similar to carboxylic acids, except the O-H bond is replaced with an O-C bond.

• Esters are notable for their sweet smells

• Contain polar bonds, but do not participate in hydrogen bonding.

5. Amides, Acid Halides, Anhydrides, Nitriles

There are actually quite a few important functional groups containing carbonyls. These functional groups are all
considered to be derived from carboxylic acids, as they can be obtained through replacement of OH with various
groups. (Nitriles might not appear to be related to carboxylic acids at first glance, but they can actually be
converted into amides through dehydration.)
Amides contain a carbonyl carbon attached to an amino group.

• Amino acids linked together through formation of an amide are known as peptides.

• Amides containing N-H bonds can participate in hydrogen bonding.

Acid Halides have -OH replaced with F, Cl, Br, or I.

Anhydrides contain an oxygen flanked by two carbonyls. Distinct from esters.

• Anhydrides can be formed from two equivalents of a carboxylic acid with accompanying loss of H2O,
hence the name.

Nitriles don’t look like carboxylic acid derivatives at first, but they can be formed via the dehydration of
amides.

• Acetonitrile is a common solvent.

• “Nitrile gloves” are made from nitrile rubber, a co-polymer of butadiene and acrylonitrile.

• The -CN substituent is sometimes referred to as a cyanide.

• HCN, hydrogen cyanide, is a highly toxic gas. The cyanide ion (-)CN, is often encountered in
introductory courses (on paper, not in the lab!) and undergoes reactions with alkyl halides.

6. Miscellaneous: Epoxides, Thioethers, Nitro, Imine, Azide

No common thread here; just a few more prominent functional groups worth knowing.

Technically, Epoxides are ethers, but since they participate in a number of reactions that ethers generally
don’t , they deserve their own category.
 Thioethers (sulfides) are the sulfur equivalents of ethers. Dimethyl sulfide is the most commonly
encountered example.

Nitro groups are strongly electron-withdrawing. Nitromethane, a solvent, is the simplest example of a
nitroalkane.

Imines are the nitrogen-containing equivalents of aldehydes and ketones.

Azides pop up from time to time. The “A” in the anti-HIV drug AZT stands for azido.

Naming Alkanes

From the sheet, here are the 7 core steps for naming alkanes and derivatives.
A. Determine the priority of functional groups (not covered here since we’re dealing with alkanes
only)
B. Find the longest linear chain of your molecule. This is the “Chain length rule” which defines both
the “main chain” and also the suffix.
-tiebreaker: where more than one “path” along the molecule leads to the longest chain, the main chain
is the one that contains the most substituents.
C. Identify the substituents along your main chain. Substituents are classified according to length of
carbon chain and the suffix “yl” is attached.
D. Number your chain from one of the ends. The Lowest Locator Rule determines which end is chosen as
carbon #1: “Number the chain such as to provide the lowest possible locators for the chain.”
-tiebreaker for lowest-locator rule: alphabetization
E. Multiple instances of substituents are given the prefixes di, tri, tetra, etc.
-note: must have locator for all substituents. Example: 1,1-dimethyl is correct. 1-dimethyl is incorrect.
1,1-methyl is incorrect. These are common mistakes.
F. Branched substituents are numbered and named seperately from the main chain, and put in
brackets.
G. The FINAL name is assembled such as to arrange the substituents in alphabetical order.
-“di”, “tri”, “tetra” are ignored for alphabetization purposes.
-prefixes like “n”, “tert”, “i” and “sec” are ignored for alphabetization purposes.
THE EXCEPTION is “isopropyl” and “isobutyl”. For some reason the “i” counts for alphabetization here.
– This is also the point where stereochemistry prefixes such as “cis”, “trans”, (E), (Z), (R), (S) and so on are
added.
In organic chemistry, isomers are molecules with the same molecular formula (i.e. the same number of
atoms of each element), but different structural or spatial arrangements of the atoms within the
molecule. The reason there are such a colossal number of organic compounds – more than 10 million – is in
part down to isomerism. This graphic looks at the 5 main types of isomerism in organic molecules, with a
more detailed explanation of each given below, as well as the reason why isomerism is important in our
day-to-day lives.

STRUCTURAL ISOMERISM

Isomers can be split into two broad groups – structural (or constitutional) isomers, and stereoisomers. We’ll
consider structural isomers first, which can be split again into three main subgroups: chain isomers, position
isomers, and functional group isomers. Structural isomerism can quickly get quite out of hand in terms of
the number of possible isomers; butane (four carbons) has two possible isomers, decane (ten carbons) has
seventy-five, and a simple hydrocarbon containing 40 carbon atoms has an estimated 62,000,000,000
structural isomers.

Chain Isomers

Chain isomers are molecules with the same molecular formula, but different arrangements of the carbon
‘skeleton’. Organic molecules are based on chains of carbon atoms, and for many molecules this chain can
be arranged differently: either as one, continuous chain, or as a chain with multiple side groups of carbons
branching off. The name of the molecule can be changed to reflect this, but we’ll save the naming of
molecules for another post. Obviously, there’s often more than one way of branching off groups of carbons
from the main chain, which leads to the large numbers of possible isomers as the number of carbons in the
molecule increases.

Position Isomers
Position isomers are based on the movement of a ‘functional group’ in the molecule. A functional group in
organic chemistry is the part of a molecule that gives it its reactivity. There are a range of different
functional groups, the more common of which were summarized in a previous post here. Nothing else about
the molecule changes, simply where the functional group in it is, and the name simply alters slightly to
indicate whereabouts in the molecule it is located.

Functional Isomers

Also referred to as functional group isomers, these are isomers where the molecular formula remains the
same, but the type of functional group in the atom is changed. This is possible by rearranging the atoms
within the molecule so that they’re bonded together in different ways. As an example, a standard straight-
chain alkane (containing only carbon and hydrogen atoms) can have a functional group isomer that is a
cycloalkane, which is simply the carbons bonded together in such a way that they form a ring. Different
functional group isomers are possible for different functional groups.

STEREOISOMERISM

There are two main types of stereoisomerism – geometric isomerism, and optical isomerism. These, as the
difference in name suggests, aren’t to do with any large-scale rearrangements of the structure of molecules;
instead, they involve different arrangements of parts of the molecule in space. They’re a little more
complicated to think about than the structural isomers, so let’s have a look at each of them in turn.

Geometric Isomers

Geometric isomerism is actually a term that is ‘strongly discouraged’ by IUPAC (the International Union of
Pure & Applied Chemistry), who prefer ‘cis-trans’, or ‘E-Z’ in the specific case of alkenes. However,
‘geometric isomerism’ is still consistently used in many A Level courses to refer to both, so for that reason
I’ve used that name here.

This type of isomerism most frequently involves carbon carbon double bonds (shown by two lines joining
each carbon instead of one). Rotation of these bonds is restricted, compared to single bonds, which can
rotate freely. This means that, if there are two different atoms, or groups of atoms, attached to each carbon
of the carbon carbon double bond, they can be arranged in different ways to give different molecules. These
atoms or groups can be given ‘priorities’, with atoms with higher atomic numbers given higher priorities. If
the highest priority groups for each carbon are on the same side of the molecule, that molecule is denoted as
the ‘cis’ or ‘Z’ isomer. If they’re on opposite sites, it’s denoted as the ‘trans’ or ‘E’ isomer.

The two different nomenclatures are a little confusing – cis/trans is now less commonly used, with E/Z
instead being favoured. E stands for ‘entgegen’ (‘opposite’ in german) whilst Z stands for ‘zusammen’
(‘together’ in german). The letter is simply added in brackets at the start of the molecule’s name in order to
indicate which isomer it is.

Optical Isomers

Optical isomers are so named due to their effect on plane-polarised light, about which you can read more
here, and come in pairs. They usually (although not always) contain a chiral centre – this is a carbon atom,
with four different atoms (or groups of atoms) attached to it. These atoms or groups can be arranged
differently around the central carbon, in such a way that the molecule can’t be rotated to make the two
arrangements align. Since one arrangement can’t line up to look exactly like the other, we refer to them as
‘non-superimposable mirror images’ – one of the isomers is the mirror image of the other. Think of it like
your hands – you can’t exactly superimpose one hand on top of the other, because your thumbs will stick
out in opposite directions.

These can be allocated an identifying letter, in much the same way as with geometric isomerism. The
groups around the carbon are given priorities, then the lowest priority group is oriented pointing away.
Looking at the remaining groups, if they decrease in priority going in an anti-clockwise direction, it’s the S
isomer (from the Latin ‘sinister’, meaning ‘left’). If they decrease in priority going in a clockwise direction,
it’s the R isomer (from the Latin ‘rectus’, meaning ‘right’). Again, this letter is simply added in front of the
isomer’s name in order to indicate which one it is.

There are other ways in which optical isomerism can be exhibited, but this is the simplest.

The Importance of Isomerism

As previously mentioned, isomers of the same molecule have the potential to have different physical or
chemical properties. These differences can have some important implications.

Let’s look particularly at the case of optical isomerism. The two possible isomers can also be referred to as
‘enantiomers’ of each other. A prime, and well cited example of enantiomers with differing properties is
that of the compound ‘carvone’. In its (R) form, it is found in mint leaves, and is the principle contributor to
the aroma. However, in its S form, it is found in caraway seeds, and has a very different smell.

There can also be less benign differences. By far the most well known example here is that of thalidomide.
This drug was prescribed in the 1950s and 60s to treat morning sickness in pregnant women; however,
unknown then was that the (S) enantiomer could be transformed in the body into compounds that caused
deformities in embryos. The two enantiomers also interconvert in the body, meaning that even if just the
(R) enantiomer could be isolated, it would still produce the same effects. This emphasized the importance
of testing all of the optical isomers of drugs for effects, and is part of the reason why present-day
pharmaceuticals have to go through years of rigorous tests, to ensure that they are safe.

The two enantiomers of thalidomide (Fuse809, Wikimedia Commons)

Introduction to Polymers

Polymers are substances containing a large number of structural units joined by the same type of linkage.
These substances often form into a chain-like structure. Polymers in the natural world have been around
since the beginning of time. Starch, cellulose, and rubber all possess polymeric properties. Man-made
polymers have been studied since 1832. Today, the polymer industry has grown to be larger than the
aluminum, copper and steel industries combined.

Prior to the early 1920's, chemists doubted the existence of molecules having molecular weights greater
than a few thousand. This limiting view was challenged by Hermann Staudinger, a German chemist with
experience in studying natural compounds such as rubber and cellulose. In contrast to the prevailing
rationalization of these substances as aggregates of small molecules, Staudinger proposed they were made
up of macromolecules composed of 10,000 or more atoms. He formulated a polymeric structure for rubber,
based on a repeating isoprene unit (referred to as a monomer). For his contributions to chemistry,
Staudinger received the 1953 Nobel Prize. The terms polymer and monomer were derived from the Greek
roots poly (many), mono (one) and meros (part).

Recognition that polymeric macromolecules make up many important natural materials was followed by the
creation of synthetic analogs having a variety of properties. Indeed, applications of these materials as fibers,
flexible films, adhesives, resistant paints and tough but light solids have transformed modern society. Some
important examples of these substances are discussed in the following sections.

There are two general types of polymerization reactions: addition polymerization and condensation
polymerization. In addition polymerization, the monomers add to one another in such a way that the
polymer contains all the atoms of the starting monomers. Ethylene molecules are joined together in long
chains.

Chain-Reaction (Addition) Polymerization

The polymerization can be represented by the reaction of a few monomer units:

The bond lines extending at the ends in the formula of the product indicate that the structure extends for
many units in each direction. Notice that all the atoms—two carbon atoms and four hydrogen atoms—of
each monomer molecule are incorporated into the polymer structure. Because displays such as the one
above are cumbersome, the polymerization is often abbreviated as follows:

nCH2=CH2 → [ CH2CH2 ] n

During the polymeriation of ethene, thousands of ethene molecules join together to make poly(ethene) -
commonly called polythene. The reaction is done at high pressures in the presence of a trace of oxygen as
an initiator.
Regio and Stereo isomerization in Macromolecules

Symmetrical monomers such as ethylene and tetrafluoroethylene can join together in only one way.
Monosubstituted monomers, on the other hand, may join together in two organized ways, described in the
following diagram, or in a third random manner. Most monomers of this kind, including propylene, vinyl
chloride, styrene, acrylonitrile and acrylic esters, prefer to join in a head-to-tail fashion, with some
randomness occurring from time to time. The reasons for this regioselectivity will be discussed in the
synthetic methods section.

If the polymer chain is drawn in a zig-zag fashion, as shown above, each of the substituent groups (Z) will
necessarily be located above or below the plane defined by the carbon chain. Consequently we can identify
three configurational isomers of such polymers. If all the substituents lie on one side of the chain the
configuration is called isotactic. If the substituents alternate from one side to another in a regular manner
the configuration is termed syndiotactic. Finally, a random arrangement of substituent groups is referred to
as atactic. Examples of these configurations are shown here.

Many common and useful polymers, such as polystyrene, polyacrylonitrile and poly(vinyl chloride) are
atactic as normally prepared. Customized catalysts that effect stereoregular polymerization of
polypropylene and some other monomers have been developed, and the improved properties associated
with the increased crystallinity of these products has made this an important field of investigation. The
following values of Tg have been reported.

Polymer Tg atactic Tg isotactic Tg syndiotactic

PP –20 ºC 0 ºC –8 ºC

PMMA 100 ºC 130 ºC 120 ºC

The properties of a given polymer will vary considerably with its tacticity. Thus, atactic polypropylene is
useless as a solid construction material, and is employed mainly as a component of adhesives or as a soft
matrix for composite materials. In contrast, isotactic polypropylene is a high-melting solid (ca. 170 ºC)
which can be molded or machined into structural components.

What are Biomolecules?

Biomolecules are the most essential organic molecules, which are involved in the maintenance and
metabolic processes of living organisms. These non-living molecules are the actual foot-soldiers of the
battle of sustenance of life. They range from small molecules such as primary and secondary metabolites
and hormones to large macromolecules like proteins, nucleic acids, carbohydrates, lipids etc.
There are four major classes of Biomolecules – Carbohydrates, Proteins, Nucleic acids and Lipids. Each of
them is discussed below.

Carbohydrates

Carbohydrates are chemically defined as polyhydroxy aldehydes or ketones or compounds which produce
them on hydrolysis. In layman’s terms, we acknowledge carbohydrates as sugars or substances that taste
sweet. They are collectively called as saccharides (Greek: sakcharon = sugar). Depending on the number of
constituting sugar units obtained upon hydrolysis, they are classified as monosaccharides (1 unit),
oligosaccharides (2-10 units) and polysaccharides (more than 10 units). They have multiple functions’ viz.
they’re the most abundant dietary source of energy; they are structurally very important for many living
organisms as they form a major structural component, e.g. cellulose is an important structural fibre for
plants.

Proteins

Proteins are another class of indispensable biomolecules, which make up around 50per cent of the cellular
dry weight. Proteins are polymers of amino acids arranged in the form of polypeptide chains. The structure
of proteins is classified as primary, secondary, tertiary and quaternary in some cases. These structures are
based on the level of complexity of the folding of a polypeptide chain. Proteins play both structural and
dynamic roles. Myosin is the protein that allows movement by contraction of muscles. Most enzymes are
proteinaceous in nature.

Nucleic Acids

Nucleic acids refer to the genetic material found in the cell that carries all the hereditary information from
parents to progeny. There are two types of nucleic acids namely, deoxyribonucleic acid (DNA) and
ribonucleic acid (RNA). The main function of nucleic acid is the transfer of genetic information and
synthesis of proteins by processes known as translation and transcription. The monomeric unit of nucleic
acids is known as nucleotide and is composed of a nitrogenous base, pentose sugar, and phosphate. The
nucleotides are linked by a 3’ and 5’ phosphodiester bond. The nitrogen base attached to the pentose sugar
makes the nucleotide distinct. There are 4 major nitrogenous bases found in DNA: adenine, guanine,
cytosine, and thymine. In RNA, thymine is replaced by uracil. The DNA structure is described as a double-
helix or double-helical structure which is formed by hydrogen bonding between the bases of two
antiparallel polynucleotide chains. Overall, the DNA structure looks similar to a twisted ladder.

Lipids

Lipids are organic substances that are insoluble in water, soluble in organic solvents, are related to fatty
acids and are utilized by the living cell. They include fats, waxes, sterols, fat-soluble vitamins, mono-, di- or
triglycerides, phospholipids, etc. Unlike carbohydrates, proteins, and nucleic acids, lipids are not polymeric
molecules. Lipids play a great role in the cellular structure and are the chief source of energy.