In the previous unit you have learnt that the element 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. This unit incorporates some basic principles and techniques of analysis required for understanding the formation and properties of organic compounds.
GENERAL INTRODUCTION :
Organic compounds are vital for sustaining life on earth and include complex molecules like genetic information bearing deoxyribonucleic acid (DNA) and proteins that constitute essential compounds of our blood, muscles and
skin. Organic chemicals appear in materials like clothing, fuels, polymers, dyes and medicines. These are some of the important areas of application of these compounds.
Science of organic chemistry is about two hundred years old. 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.
The pioneering 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.
The development of electronic theory of covalent bonding ushered organic chemistry into its modern shape.
TETRAVALENCE OF CARBON: SHAPES OF ORGANIC COMPOUNDS :
The Shapes of Carbon Compounds :
The knowledge of fundamental concepts of molecular structure helps in understanding and predicting the properties of organic compounds. You have already learnt theories of valency and molecular structure in Unit 4. Also, you already know that tetravalence of carbon and the formation of covalent bonds
by it are explained in terms of its electronic configuration and the hybridisation of s and p orbitals. It may be recalled that 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
Hybridisation influences the bond length and bond enthalpy (strength) in organic
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 change in hybridisation affects the electronegativity of carbon. 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 ismore electronegative than that possessing sp2
or sp3 hybridised orbitals. This relative electronegativity is reflected in several
physical and chemical properties of the molecules concerned, about which you will learn in later units.
Some Characteristic Features of pi 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 :
Structures of organic compounds are represented in several ways. The Lewis
structure or dot structure, dash structure, condensed structure and bond line structural formulas are some of the specific types. The Lewis structures, however, can be simplified by representing the two-electron covalent bond by a dash (–). Such a structural formula focuses on the electrons involved in bond
formation. A single dash represents a single bond, double dash is used for double bond and a triple dash represents triple bond. Lonepairs of electrons on heteroatoms (e.g., oxygen, nitrogen, sulphur, halogens etc.) may or may not be shown. Thus, ethane (C2H6), ethene (C2H4), ethyne (C2H2) and methanol
(CH3OH) can be represented by the following structural formulas. Such structural representations are called complete structural formulas.
These structural formulas can be further abbreviated by omitting some or all of the dashes representing covalent bonds and by indicating the number of identical groups attached to an atom by a subscript. The resulting expression of the compound is called a condensed structural formula. Thus, ethane, ethene, ethyne and methanol can be written as:
CH3CH3 = ethane
H2C=CH2 = ethene
Similarly, CH3CH2CH2CH2CH2CH2CH2CH3 can be further condensed to CH3(CH2) 6CH3. For further simplification, organic chemists use another way of representing the structures, in which only lines are used. In this bond-line structural representation of organic compounds, carbon and hydrogen
atoms are not shown and the lines representing carbon-carbon bonds are drawn
in a zig-zag fashion. The only atoms specifically written are oxygen, chlorine,
nitrogen etc. The terminals denote methyl(–CH3) groups (unless indicated otherwise by a functional group), while the line junctions denote carbon atoms bonded to appropriate number of hydrogens required to satisfy the
valency of the carbon atoms.
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, the 3-D image of a molecule from a two-dimensional picture can be perceived. 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 (—).
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 balland-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 form molecular modelling.