Chapter- Organic Chemistry – Some Basic Principles and Techniques

➢ Carbon has the unique property called catenation due to which it forms covalent
bonds with other carbon atoms.

➢ It also forms covalent bonds with atoms of other elements like hydrogen, oxygen,
nitrogen, sulphur, phosphorus and halogens.

➢ The resulting compounds are studied under a separate branch of chemistry called
organic chemistry.

GENERAL INTRODUCTION

➢ Around the year 1780, chemists began to distinguish between organic compounds
obtained from plants and animals and inorganic compounds prepared from mineral
sources.

➢ Berzilius, a Swedish chemist proposed that a ‘vital force’ was responsible for the
formation of organic compounds. However, this notion was rejected in 1828 when
F. Wohler synthesised an organic compound, urea from an inorganic compound,
ammonium cyanate.

➢ synthesis of acetic acid by Kolbe (1845) and that of methane by Berthelot (1856)
showed conclusively that organic compounds could be synthesised from inorganic
sources in a laboratory.

TETRAVALENCE OF CARBON: SHAPES OF ORGANIC COMPOUNDS

➢ The Shapes of Carbon Compounds

➢ formation and the shapes of molecules like methane (CH4), ethene (C2H4), ethyne
(C2H2) are explained in terms of the use of sp3, sp2 and sp hybrid orbitals by
carbon atoms in the respective molecules.

➢ Hybridisation influences the bond length and bond enthalpy (strength) in

compounds.

➢ The sp hybrid orbital contains more s character and hence it is closer to its nucleus
and forms shorter and stronger bonds than the sp3 hybrid orbital.

➢ The sp2 hybrid orbital is intermediate in s character between sp and sp3 and, hence,
the length and enthalpy of the bonds it forms, are also intermediate between them.
➢ The greater the s character of the hybrid orbitals, the greater is the
electronegativity. Thus, a carbon atom having an sp hybrid orbital with 50%
s character is more electronegative than that possessing sp2 or sp3 hybridised
orbitals.

➢ Some Characteristic Features of π Bonds

➢ In a π (pi) bond formation, parallel orientation of the two p orbitals on adjacent

atoms is necessary for a proper sideways overlap. Thus, in H2C=CH2 molecule all
the atoms must be in the same plane. The p orbitals are mutually parallel and both
the p orbitals are perpendicular to the plane of the molecule

➢ Rotation of one CH2 fragment with respect to other interferes with maximum
overlap of p orbitals and, therefore, such rotation about carbon-carbon double bond
(C=C) is restricted.

➢ The electron charge cloud of the π bond is located above and below the plane of
bonding atoms. This results in the electrons being easily available to the attacking
reagents. In general, π bonds provide the most reactive centres in the molecules
containing multiple bonds.

STRUCTURAL REPRESENTATIONS OF ORGANIC COMPOUNDS

➢ Complete, Condensed and Bond-line Structural Formulas

➢ complete structural formulas.

or
Methanol

➢ condensed structural formula.

➢ bond-line structural representation

(i) 3-Methyloctane can be represented in various

forms as:
(a) (b)

(c)

(ii) Various ways of representing 2-bromo butane are:

➢ In cyclic compounds, the bond-line formulas may be given as follows:

 THREE-DIMENSIONAL REPRESENTATION OF ORGANIC MOLECULES

➢ The three-dimensional (3-D) structure of organic molecules can be represented on

paper by using certain conventions. For example, by using solid and
dashed wedge formula.

➢ In these formulas the solid-wedge is used to indicate a bond projecting out of the
plane of paper, towards the observer.

➢ The dashed-wedge is used to depict the bond projecting out of the plane of the
paper and away from the observer.

➢ Wedges are shown in such a way that the broad end of the wedge is towards the
observer.

➢ The bonds lying in plane of the paper are depicted by using a normal line (—).

(Wedge-and-dash representation of CH4)

➢ Molecular Models

➢ Molecular models are physical devices that are used for a better visualisation and
perception of three-dimensional shapes of organic molecules.

➢ These are made of wood, plastic or metal and are commercially available.

➢ Commonly three types of molecular models are used: (1) Framework model, (2)
Ball-and-stick model, and (3) Space filling model.

➢ In the framework model only the bonds connecting the atoms of a molecule and
not the atoms themselves are shown. This model emphasizes the pattern of bonds
of a molecule while ignoring the size of atoms.

➢ In the ball-and-stick model, both the atoms and the bonds are shown. Balls
represent atoms and the stick denotes a bond.
➢ Compounds containing C=C (e.g., ethene) can best be represented by using springs
in place of sticks. These models are referred to as ball-and-spring model.

➢ The space-filling model emphasises the relative size of each atom based on its van
der Waals radius. Bonds are not shown in this model. It conveys the volume
occupied by each atom in the molecule. In addition to these models, computer
graphics can also be used for molecular modelling.

(Framework model) (Ball and stick model) (Space filling model)

CLASSIFICATION OF ORGANIC COMPOUNDS

➢ Acyclic or open chain compounds

➢ These compounds are also called as aliphatic compounds and consist of straight or
branched chain compounds, for example:

Ethane Isobutane Acetaldehyde Acetic acid

➢ Cyclic or closed chain or ring compounds

(a) alicyclic compounds

➢ Alicyclic (aliphatic cyclic) compounds contain carbon atoms joined in the form of
a ring (homocyclic).

➢ Sometimes atoms other than carbon are also present in the ring (heterocylic).
Tetrahydrofuran given below is an example of this type of compound:

Tetrahydrofuran
➢ These exhibit some of the properties similar to those of aliphatic compounds.

(b) aromatic compounds

➢ These include benzene and other related ring compounds (benzenoid).

➢ Like alicyclic compounds, aromatic compounds may also have hetero atom in the
ring. Such compounds are called hetrocyclic aromatic compounds.
➢ Benzenoid aromatic compounds

Benzene Aniline Naphthalene

➢ Non-benzenoid compound

Tropone

➢ Heterocyclic aromatic compounds

Furan Thiophene Pyridine

➢ Functional group

➢ The functional group is an atom or a group of atoms joined to the carbon chain
which is responsible for the characteristic chemical properties of the organic
compounds.

➢ The examples are hydroxyl group (–OH), aldehyde group (–CHO) and carboxylic
acid group (COOH) etc.

➢ Homologous series

➢ A group or a series of organic compounds each containing a characteristic

functional group forms a homologous series and the members of the series are
called homologues.
➢ The members of a homologous series can be represented by general molecular
formula.

➢ The successive members differ from each other in molecular formula by a –CH2
unit.

➢ There are a number of homologous series of organic compounds. Some of these

are alkanes, alkenes, alkynes, haloalkanes, alkanols, alkanals, alkanones, alkanoic
acids, amines etc.

➢ It is also possible that a compound contains two or more identical or different

functional groups. This gives rise to polyfunctional compounds.

Nomenclature Of Organic Compounds

➢ IUPAC (international union of pure and applied Chemistry) system of

nomenclature

➢ Before the IUPAC system of nomenclature, however, organic compounds were

assigned names based on their origin or certain properties. For instance, citric acid
is named so because it is found in citrus fruits and the acid found in red ant is
named formic acid since the Latin word for ant is formica. These names are
traditional and are considered as trivial or common names.

➢ Some common names are followed even today. For example,

Buckminsterfullerene is a common name given to the newly discovered C60
cluster (a form of carbon).

➢ Common names are useful and in many cases indispensable, particularly when the
alternative systematic names are lengthy and complicated.