ORGANIC CHEMISTRY

To understand life as we know it, we must first understand a little bit of organic chemistry. Organic
molecules contain both carbon and hydrogen. Though many organic chemicals also contain other
elements, it is the carbon-hydrogen bond that defines them as organic. Organic chemistry defines
life. Just as there are millions of different types of living organisms on this planet, there are millions
of different organic molecules, each with different chemical and physical properties. There are
organic chemicals that make up your hair, your skin, your fingernails, and so on.

Carbon and Its Compounds

Carbon, a non-metal with atomic number 6 and mass number 12, occurs in free as well as in
combined form. Because carbon is in Group IVA of the periodic table, it has four valence electrons.
To fill its octet, it requires four additional electrons, which can be obtained through the formation
of four covalent bonds. Carbon forms single, double, and triple bonds to achieve a filled octet.
Therefore, the possible bonding combinations for carbon are as follows.

A unique feature of carbon is its ability to bond with other carbon atoms to form chains and rings
of various lengths. Several other elements have limited ability to form such chains or rings of like
atoms, but only carbon does this with more than a few atoms. Some petroleum-containing
products, such as asphalt, consist of molecules with 30 or more carbon atoms bonded together; the
molecules that make up polyethylene (plastics) can have chains with thousands of carbon atoms.
The diversity of organic chemicals is due to the versatility of the carbon atom. Why is carbon such
a special element?

Two characteristic properties of carbon are responsible for this. These properties are:

1. Catenation
2. Tetravalency

Catenation
Carbon atoms have a unique ability to form bonds (single, double as well as triple) with other
carbon atoms toform large molecules. These can arrange themselves in straight chain, in branched
chains or in the form of rings.This property of self-linking of carbons atom throughcovalent bonds
to form straight chains or cyclic rings ofcarbon atoms is called catenation. Carbon exhibits the
property of catenation to maximum extent due to large C-C bond energy and hence, forms large
number of compounds. The C-C and C-H bonds in organic compounds are very strong. During
chemical reactions, these bonds generally do not break easily. However other atoms or groups such
as Cl, OH etc., attached to the carbon atom may get replaced easily. For example, aqueous KOH
reacts with halo-alkanes to give the corresponding alcohol. All these features make carbon to form
a more variety of compounds.

Tetravalency
Due to the valence of four, carbon is capable of bonding or pairing with four other carbon atoms
or with the atoms of some other monovalent elements. It also forms compounds with oxygen,
nitrogen, sulphur, hydrogen and many other elements. This gives rise to compounds with specific
properties which depend on the element other than carbon present in the molecule. Bonds which
carbon forms with other elements are very strong thus, making these compounds very stable. The
main reason for such strong bond formation is the small size of carbon. As a result, the shared pair
of electrons is tightly held by the nucleus. The strength of bond decreases with increase in the size
of atoms.
The simplest organic compounds are hydrocarbons, compounds containing only carbonand

hydrogen. All other organic compounds—for example, those containing O, N, andthe halogen

atoms—are classified as being derived from hydrocarbons. At first glance,you might think that the

hydrocarbons represent a very limited set of molecules; however,several hundred thousand

molecules exist that contain only hydrogen and carbon atoms.Hydrocarbons can be separated into
three main groups:

a. Saturated hydrocarbons (alkanes or paraffin) are hydrocarbons that contain

only single bonds between the carbon atoms. Saturated hydrocarbon molecules
can be cyclic or acyclic. Acyclic hydrocarbon is one in which a chain of carbon
atoms has formed a ring.An acyclic hydrocarbon is one that does not contain a
ring of carbon atoms.
 b. Unsaturated hydrocarbons are hydrocarbons that contain double or triple
bonds between carbon atoms.
c. Aromatic hydrocarbons are hydrocarbons that contain benzene rings or
similarfeatures.

The saturated and unsaturated hydrocarbons are often referred to as the aliphatichydrocarbons.

Alkanes and Cycloalkanes

The alkanes are acyclic saturated hydrocarbons, and the cycloalkanes are cyclic
saturatedhydrocarbons. The simplest hydrocarbon, an alkane called methane, consistsof one
carbon atom to which four hydrogen atoms are bonded in a tetrahedral arrangement.You can
represent methane by its molecular formula, CH4, which gives the numberand kind of atoms in the
molecule, or by its structural formula, which shows howthe atoms are bonded to one another.

The Alkane Series

The alkanes, also called paraffins, have the general formula CnH2n+2. For n = 1,methane, the
formula is CH4; for n = 2, C2H6; for n = 3, C3H8; and so on. Note thatthe general formula conveys
no information about how the atoms are connected. Fornow, we will assume that the carbon atoms
are bonded together in a straight chainwith hydrogen atoms completing the four required bonds to
each carbon atom; theseare called straight-chain or normal alkanes. The structural formulas for
the first fourstraight chain alkanes are shown.

Because carbon atoms typically have four bonds, chemists often write the structuresof the parts of
organic compounds using condensed structural formulas, or condensedformulas, where the
bonds around each carbon atom in the compound are not explicitlywritten.Condensed formulas of
the first four alkanes (n = 1 to 4) are:

CH4 CH3CH3 CH3CH2CH3 CH3CH2CH2CH3

Methane Ethane Propane Butane

Note that the condensed formula of an alkane differs from that of the precedingalkane (n=1) by a

—CH2— group. The alkanes constitute a homologous series,which is a series of compounds in

which one compound differs from a preceding oneby a fixed group of atoms. Members of a
homologous series have similar chemicalproperties, and their physical properties change
throughout the series in a regularway. The melting points and boiling pointsgenerally increase in
the series with an increase in the number of carbon atoms inthe chain. This is a result of increasing
intermolecular forces, which increase withmolecular mass.

Constitutional Isomerism and Branched-Chain Alkanes

In addition to the straight-chain alkanes, branched-chain alkanes are possible. Forexample,
isobutane (or 2-methylpropane) has the structure:

Isobutane, C4H10, has the same molecular formula as butane, the straight-chain
hydrocarbon.However, isobutane and butane have different structural formulas and,
therefore,different molecular structures. Butane and isobutane are constitutional (or
structural)isomers, compounds with the same molecular formula but different structural
formulas.Because these isomershave different structures, they have different properties. For
example, isobutane boils at -12°C, whereas butane boils at 0°C. Here the difference in boiling
point can be attributedto the fact that isobutane has a more compact molecular structure than
butane,which results in weaker intermolecular interactions between isobutane molecules.The
number of constitutional isomers rapidly increases with the number of carbons inthe series. For
example, there are three constitutional isomers with the molecular formulaC5H12 (pentanes; five
of C6H14 (hexanes), and 75 of C10H22 (decanes).Branched alkanes are usually written using
condensed structural formulas.
Cycloalkanes
The general formula for cyclic cycloalkanes is CnH2n. The figure below gives the namesand
structural formulas for the first four members of the cycloalkane series. In thecondensed structural
formulas, a carbon atom and its attached hydrogen atoms areassumed to be at each corner.The
smallest possible ring consists of cyclopropane, C3H6.

Fossil fuels (natural gas, petroleum, and coal) are the principal sources of all typesof organic
chemicals. Natural gas is a mixture of low-molecular-mass hydrocarbonsmade up primarily of
methane, CH4, with lesser amounts of ethane, C2H6; propane,C3H8; and butane, C4H10. Petroleum,
or crude oil, is the raw material extracted froma well. It is a mixture of alkanes and cycloalkanes
with small amounts of aromatichydrocarbons. The composition of petroleum is not consistent; it
is dependent on geologiclocation and the organic matter present during oil formation. Because of
this, abarrel of oil from Saudi Arabia contains a much different mixture of organic materialsthan
a barrel of oil from the North Slope of Canada. The Saudi crude oil mightbe made up primarily of
molecules with 5 to 20 carbon atoms, whereas theCanadian crude might consist mainly of
molecules containing 20 to 40carbonatoms. Crude oils that contain a majority of the lower-
molecular-masshydrocarbons are often more desirable because they are easier to transport
andrequire less refining to convert to high-demand products like gasoline.
Reactions of Alkanes with Oxygen
From your experiences with alkanes, it is probably apparent that they are not particularlyreactive
molecules at normal temperatures. But imagine if this were not thecase; you would have to be
extremely careful about how you filled your automobilewith fuel, and you couldn’t safely use
natural gas in your home for heating or cooking.Also, the refining process could not involve the
separation of the crude oil componentsat high temperatures by distillation. However, we do react
alkanes every daythrough combustion with O2; all hydrocarbons burn (combust) in an excess of
O2 atelevated temperatures to produce carbon dioxide, water, and heat. For example, apropane gas
grill uses the reaction

C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l); ΔH= -2220 kJ/mol

The large negative ΔH value for this reaction and all hydrocarbon reactions with
oxygendemonstrates why we rely on these molecules to meet our energy needs.

Substitution Reactions of Alkanes

Under the right conditions, alkanes can react with other molecules. An importantexample is the
reaction of alkanes with the halogens F2, Cl2, and Br2. Reaction withCl2, for example, requires
light (indicated by hv) or heat.

This is an example of a substitution reaction. A substitution reaction is a reaction inwhich a part

of the reacting molecule is substituted for an H atom on a hydrocarbonor hydrocarbon group. All
of the H atoms of an alkane may undergo substitution,leading to a mixture of products.

The CCl4 product can be reacted with HF in the presence of a SbCl5 catalyst to
producetrichlorofluoromethane, CCl3F, also known as CFC-11.
This compound is one of a number of chlorofluorocarbons (CFCs) used for much ofthe twentieth
century as a refrigerant but have been identified as contributing to destruction of the ozone
layer.Recent refrigerants that do not as readily contribute to ozonedestruction include
hydrofluorocarbons (HFCs), such as CF3CH2F, which do not containchlorine atoms. These HFCs
are now used to replace CFCs.

Alkenes and Alkynes

Alkenes and alkynes are unsaturated hydrocarbons. Because they contain carbon–carbon multiple

bonds, they are typically much more reactive than alkanes.Under the proper conditions, molecular
hydrogen can be added to an alkane oralkyne to produce a saturated compound in a process called
catalytic hydrogenation.For example, ethylene adds hydrogen to give ethane.

Catalytic hydrogenation is also used in the food industry to convert (hydrogenate)carbon-carbon

double bonds to carbon–carbon single bonds. For example, margarinecan be manufactured by

hydrogenating some of the double bonds present in corn oilto change it from oil to a solid (fat).