POLAR COVALENT BONDS

Electrons are not always shared equally between two bonding atoms: one atom might exert
more of a force on the electron cloud than the other. This "pull" is termed electronegativity
and measures the attraction for electrons a particular atom has. The unequal sharing of
electrons within a bond leads to the formation of an electric dipole: a separation of positive
and negative electric charge. Fractional charges are denoted as δ+ (delta plus) and δ− (delta
minus).

• When two atoms of different EN form a covalent bond, the electrons are not
shared equally between them.
• The chlorine atom pulls the bonding electrons closer to it and becomes

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somewhat electron rich ⇒ bears a partial negative charge (δ–).

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• The hydrogen atom becomes somewhat electron deficient ⇒ bears a partial
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positive charge (δ+).
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The direction of polarity of a polar bond is symbolized by a vector quantity

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•
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POLAR
AND
NONPOLAR
MOLECULES

A molecule is composed of one or more chemical bonds (covalent bonds) between
molecular orbitals of different atoms. A molecule may be polar either as a result of
polar bonds due to differences in electronegativity as described above, or as a result of
an asymmetric arrangement of non-polar covalent bonds and non-bonding pairs of
electrons known as a full molecular orbital. While the molecules can be described as
"polar covalent", "non-polar covalent", or "ionic", it must be noted that this is often a
relative term, with one molecule simply being more polar or more non-polar than
another.
The polarity (dipole moment) of a molecule is the vector sum of the dipole moment of
each individual polar bond.




 
 


 
 Fig.
1.1

 
 
 
 
 
 Fig.
1.2



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Fig 1.1 is showing the charge distribution in carbon tetrachloride and the Fig 1.2
is showing that 4 equal bond moments in tetrahedral orientation are producing
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zero net moment by cancelling each other.
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Table 1.1 Dipole moments of some molecules

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Unshared pairs (lone pairs) of electrons make large contributions to the dipole
moment. (The O–H and N–H moments are also appreciable.)
 

Fig. 1.3 Bond moments and resulting dipole moments of water and ammonia




INTERMOLECULAR
BONDING



Intermolecular bonding is the bonding interaction which takes place between
different molecules. This can take the form of ionic bonding, hydrogen bonding,
dipole–dipole interactions or van der Waals interactions. These bonding forces

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are weaker than the covalent bonds, but they have an important influence on the

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physical and biological properties of a compound.
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Ionic bonding Ionic bonding takes place between molecules having opposite
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charges and involves an electrostatic interaction between the two

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opposite charges. The functional groups, which most easily ionize,

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are amines and carboxylic acids.

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Fig. 1.4 Ionization of an amine (left) and ionization of a carboxylic acid (right)

Ionic bonding is possible between a molecule containing an

ammonium ion and a molecule containing a carboxylate ion. Some
important naturally occurring molecules contain both groups – the
amino acids. Both these functional groups are ionized to form a
structure known as a zwitterion (a neutral molecule bearing both a
positive and a negative charge) and intermolecular ionic bonding
 can take place.

Fig. 1.5

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Fig. 1.6 Intermolecular ionic bonding of amino acids.

Hydrogen bonding .o
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The strong dipole-dipole attractions between hydrogen atoms
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bonded to small, strongly electronegative atoms (O, N, or F) and

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nonbonding electron pairs on other electronegative atoms.

Hydrogen bonding can take place when molecules have a hydrogen
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atom attached to a heteroatom such as nitrogen or oxygen. The

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common functional groups, which can participate in hydrogen

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bonding, are alcohols, phenols, carboxylic acids, amides, and

amines. Hydrogen bonding is possible due to the polar nature of the
N–H or O–H bond. Nitrogen and oxygen are more electronegative
than hydrogen. As a result, the heteroatom gains a slightly negative
charge and the hydrogen gains a slightly positive charge. Hydrogen
bonding involves the partially charged hydrogen of one molecule
(the H bond donor) interacting with the partially charged heteroatom
of another molecule (the H bond acceptor).
1) Bond dissociation energy of about 4-38 KJ mol–1 (0.96-9.08 Kcal mol–1).

2) H-bond is weaker than an ordinary covalent bond; much stronger than the
dipole-dipole interactions.

Fig. 1.7

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Fig. 1.8
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Hydrogen bonding accounts for the much higher boiling point

(78.5 °C) of ethanol than that of dimethyl ether (–24.9 °C)
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Dipole–dipole
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Interactions Dipole–dipole interactions are possible between polarized bonds

other than N–H or O–H bonds. The most likely functional groups
that can interact in this way are those containing a carbonyl group
(C=O). The electrons in the carbonyl bond are polarized towards the
more electronegative oxygen such that the oxygen gains a slight
negative charge and the carbon gains a slight positive charge. This
results in a dipole moment, which can be represented by the arrow
shown in Fig. 1.9. Molecules containing dipole moments can align
themselves with each other such that the dipole moments are
pointing in opposite directions.
Fig. 1.9

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Hydrogen bonding is a special case of dipole-dipole interaction.
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Van der Waals (also called London forces or dispersion forces)

Interactions Van der Waals interactions are the weakest of the
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intermolecular bonding forces and involve the transient

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existence of partial charges in a molecule. Electrons are

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continually moving in an unpredictable fashion around any

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molecule. At any moment of time, there is a slight excess of

electrons in one part of the molecule and a slight deficit in
another part. Although the charges are very weak and
fluctuate around the molecule, they are sufficiently strong to
allow a weak interaction between molecules, where regions of
opposite charge in different molecules attract each other.
Alkane molecules can interact in this way and the strength of the
interaction increases with the size of the alkane molecule. Van der
Waals interactions are also important for alkenes, alkynes and
aromatic rings. The types of molecules involved in this form of
intermolecular bonding are ‘fatty’ molecules, which do not dissolve
 easily in water, and such molecules are termed hydrophobic
(water hating). Hydrophobic molecules can dissolve in nonpolar,
hydrophobic solvents due to van der Waals interactions and so this
form of intermolecular bonding is sometimes referred to as a
hydrophobic interaction.

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Fig. 1.10
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Fig. 1.11 Temporary dipoles and induced dipoles in nonpolar molecules

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resulting from a non-uniform distribution of electrons at a given

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instant.
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This temporary dipole in one molecule can induce opposite (attractive)

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dipoles in surrounding molecules. These temporary dipoles change

constantly, but the net result of their existence is to produce attractive
forces between nonpolar molecules.
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SOLUBILITIES

1. Solubility

1) The energy required overcoming lattice energies and an intermolecular or inter ionic
attraction for the dissolution of a solid in a liquid comes from the formation of new
attractions between solute and solvent.
2) The dissolution of an ionic substance: hydrating or solvating the ions.
3) Water molecules, by virtue of their great polarity and their very small, compact
shape, can very effectively surround the individual ions as they freed from the
crystal surface.
4) Because water is highly polar and is capable of forming strong H-bonds, the dipole-
ion attractive forces are also large.

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2. “Like dissolves like”

1) Polar and ionic compounds tend to dissolve in polar solvents.

2) Polar liquids are generally miscible with each other.
3) Nonpolar solids are usually soluble in nonpolar solvents.
4) Nonpolar solids are insoluble in polar solvents.
5) Nonpolar liquids are usually mutually miscible.
6) Nonpolar liquids and polar liquids do not mix.
3. Methanol (ethanol, and propanol) and water are miscible in all proportions.

1) Alcohol with long carbon chain is much less soluble in water.

2) The long carbon chain of decyl alcohol is hydrophobic (hydro, water; phobic,
fearing or avoiding –– “water avoiding”.
3) The OH group is hydrophilic (philic, loving or seeking –– “water seeking”.

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