UNIT 2 CHEMICAL BONDING

Introduction:
A chemical bond represents a strong force of attraction between two atoms. According to
the Lewis’s octet rule, atoms of all elements have a tendency to acquire an electronic
configuration similar to that of inert gases because it represents the most stable electronic
configuration. All atoms having an unstable or incomplete outer shell have a propensity to
gain or lose electrons so as to acquire an electronic configuration of the nearest inert gas in
the periodic table. It is this tendency of atoms to complete and hence stabilize their
outermost orbit of electrons which is mainly responsible for chemical combination between
the atoms.
The requirement of electron pairing are mainly accomplished by the following modes:
1. By complete transfer of one or more electrons from one atom to another this results
in the formation of ions and hence is called ionic bonding.
2. By sharing of electrons between the two combining atoms, which results in the
formation of a covalent bond.
3. A special type of covalent linkage in which both the shared electrons are contributed
by one atom only and not one by each atom as in the case of proper covalent
linkage.

Ionic or electrovalent bond:

This type of bond is formed by the transference of electrons from one atom to another.
Essentially an atom that losses one or more of its electron, and a one that can accept
them is required. The metals in group I and group II in the periodic table has the greatest
tendency to lose electrons and turn into positive ions. The non-metals of group VI and
VII the greatest affinity for electrons and readily change into negative ions. The atom
which losses electrons acquires positive charge and contracts while the atoms which
gains electrons acquires negative charge and increases in size. The cation and anion thus
produced are held together by electrostatic lines of force and hence the linkage is called
electrovalent bond and the compound so produced is called electrovalent compounds.
These are also called polar compounds since their molecule acquires polarity due to the
formation of ions by electron transfer.
Characteristics of ionic compounds:
1. They consist of oppositely charged ions held together by electrostatic forces of
attraction.
2. They are generally soluble in water and insoluble in organic solvents.
3. Due to the powerful electrostatic force between the ions in the crystals,
considerable amount of energy is required to separate the molecules from each
other. Hence they have high melting and boiling points.
4. When dissolved in water or in the molten state, they conduct electricity because
then the binding forces in the crystal lattice are weakened.
5. They are crystalline compound.

Covalent bond:
This type of bond is formed by sharing of one or more electron pairs between the atoms
and thus achieve the stability by attaining their octet or duplet in their outermost shell.
The electrons for pair formation are contributed equally by the two participating atoms
and become their common property. The covalent linkage can connect similar atoms
when both of them are short of a few electrons to achieve their nearest inert gas
configuration. Since there is no transference of electrons and ions are not formed, the
covalent linkage is also called non-ionised linkage.
Polar and non-polar character:
Depending upon whether the electron pairs are shared equally or unequally between the
bonding atoms a covalent bond may be non-polar or polar. In homodiatomic molecules
like H2 and Cl2, the sharing of electron pair is equal between the two atoms and such a
bond is called as a non-polar covalent bond. But in hetero atomic molecules like HF or
HCl the sharing of electron pair is unequal because, one of the two atoms is likely to
attract the electrons more strongly than the other. The atom that attracts the electrons
more strongly develops some negative charge; and the other atom develops some
positive charge. These fractional charges are designated as δ + and δ-. In HCl, Cl atom is
more electron attracting than H atom and hence HCl can be depicted as H δ+ ---- Cl δ-. Such
covalent bonds are said to be polar and the bond is said to have partial ionic character.
Characteristics of covalent compounds:
1. The atoms in a covalent molecule are firmly held together by the shared pair of
electrons and hence covalent compounds do not dissociate or conduct electricity
when put in water or melted.
2. Covalent compounds are generally insoluble in water and soluble in organic solvents.
3. A covalent molecule is non polar and hence do not have external field of force. Due to
this they have low melting and boiling points.
4. Normal covalent compounds are liquids or gases at room temperature. However,
covalent compounds with high molecular weights exist as solids.
5. Covalent compounds in solution react slowly as compared to ionic compounds.
 Co-ordinate or dative bond
This is a special type of covalent bond. The atom which donates the electron pair is
called as donor and the other atom which does not contribute an electron towards
the shared electron pair is called acceptor. The pair of the valency electrons
possessed by the donor is called the lone pair. The bond formed as above is called the
co-ordinate or co-ordinate covalent or dative bond. Further, since such a bond always
renders the molecule polar, it is also called semi polar bond. Compounds containing
one or more of such co-ordinate bonds in their molecules are termed co-ordination
compounds. A co-ordinate bond is usually represented by an arrow pointing from the
donor to the acceptor atom.

Characteristics of co-ordinate compounds:

1. The co-ordinate bond is rigid and directional and hence provides opportunity for
exhibiting stereoisomerism of molecules.
2. These compounds are generally insoluble in water and soluble in organic solvents.
3. These compounds have relatively higher melting and boiling points than those of
covalent compounds and lower than those of electrovalent compounds.
4. The co-ordinate linkage being partly covalent in nature, the atoms are firmly held by
electrons and hence these compounds do not dissociate when placed in water or
melted.
5. The co-ordinate compounds are stable like covalent compounds.
Vander Waals interactions:
 Vander Waals force is a general term used to define attraction of intermolecular
forces between the molecules. These forces are distance dependent between the
atoms or molecules. It is important to remember that van der Waals' forces are
forces that exist between molecules of the same substance. They are quite different
from the forces that make up the molecule. For example, a water molecule is made
up of hydrogen and oxygen, which are bonded together by covalent bond. The van
der Waals' forces are the forces that exist between the millions of separate water
molecules, and not between the hydrogen and oxygen atoms in the case of water. 

There are three types of Vander Waals forces

1. Weak- London dispersion forces
2. Dipole-dipole forces
3. Strong- hydrogen bonding forces

London dispersion forces:

London Dispersion forces are type of van der Waals' forces. They exist between nonpolar
molecules. For example, chlorine gas is made up of two chlorine atoms. In this bond, the
electrons are equally shared and are not dominant on one side of the molecule as is the
case in HCl. The atom looks like this Cl - Cl , no overall charge on either side but, within a
bond, electrons are constantly MOVING. They zoom around the atoms really quickly. As a
result, there may be a tiny instant in time where the electrons happen to be dominant on
one side, creating a situation like, Cl+ - Cl-
However, this temporary charge disappears as quickly as it appeared because the
electrons are moving fast. These temporary dipoles allow the temporarily negative side
of one molecule to attract the temporarily positive side of another molecule, which is the
intermolecular force. 
Cl+- Cl- ….. Cl+- Cl-….. Cl+- Cl-

Strong- Dipole-dipole forces:

Dipole Dipole forces occur in polar molecules, that is, molecules that have an unequal
sharing of electrons. For example, HCl comprising of Hydrogen and Chlorine is polar
molecule. The Chlorine atom has an extra electron, donated by the hydrogen atom.
 Because of this, the chlorine part of the molecule is negatively charged, and the hydrogen
side of the molecule is positively charged. H+ - Cl-
Hence in an aqueous HCl, there are thousands of these molecules around that are slightly
charged on each side, the molecules naturally orient themselves as shown in the figure
H+ :Cl- ….. H+ :Cl-….. H+ :Cl-
The positive part of one molecule will move until it is next to the negative part of a
neighbouring molecule. These forces between molecules tend to make them 'stick'
together. 

Hydrogen bonding forces:

A hydrogen bond is a dipole dipole interaction that occurs between any molecule with a
bond between a hydrogen atom and any of oxygen/fluorine/nitrogen. So, Hydrogen
Fluoride (HF), Water (H2O), ammonia (NH3) and any other molecule that has a hydrogen
bonded to either an oxygen, fluorine or nitrogen atom, exhibits hydrogen bonding.

The hydrogen bond is just the dipole dipole force but it is extremely strong compared to
other dipole dipole forces like in HCl. It is extremely strong because F, N and O are highly
electronegative and H is highly electropositive. So basically, the bond is EXTREMELY a one-
sided affair, resulting in an extreme dipole situation, thus named, a hydrogen bond. The
extremely positive side of the molecule will orient itself with the extremely negative side of
another molecule. 

Types of Hydrogen bonding

There are two types of H-bonds, and it is classified as the following:
1. Intermolecular hydrogen bonding – This type of bond formation occurs between the
different molecules of same or different compounds. For example- p-nitro phenol.
2. Intramolecular hydrogen bonding – This type of bond formation occurs when the
hydrogen atom lies in between the two electronegative elements present in the same
molecule. For example- o-nitro phenol

o-nitrophenol shows less intermolecular hydrogen bonding than in p-nitrophenol, as

a consequence, the boiling point of o-nitrophenol is less than that of p-nitrophenol
(different molecules of the same substance are bound together by hydrogen bonds
and hence these bond breakings is difficult).

Introduction to co-ordination chemistry

A simple ion is a single species and exists as a free ion. If an ion is composed of two
or more species, the resultant ion is called complex ion and the corresponding
compound is called complex compound. A complex is a species comprising of several
parts, each of which has an independent existence in solution. It usually consists of a
positive metal ion and a number of electron rich ligands which can be anions or
neutral molecules, for example K4 [Fe(CN)6] where, [Fe(CN)6]4- is anionic complex ion
denoted by square bracket and K4 [Fe(CN)6] is a complex compound. Fe+2 is the
central metal cation and 6 CN - are ligands. Number of ligands attached to the central
metal ion is called as co-ordination number i.e 6 is the co-ordination number of Fe +2
metal ion in the complex compound K4 [Fe(CN)6].
The species that binds directly to the central metal ion is called a co-ordinating group
or ligand. The central metal cation is a lewis acid and the ligand is a lewis base. Any
species with a pair of nonbonding electrons can be a ligand.
Ligands may be bound at only one position to the central ion or they may be linked
at two, three, or even upto six positions. Ligands that can bind at more than one
position i.e. polydentate are also called as chelates. The ligands may be anions such
as, F-, Cl-, CN-, OH-, I- and neutral molecules with lone pair of electrons such as, H 2:O:,
:NH3. Some typical examples of complex compositions are given below:

Lewis acids Lewis bases Complexes

Co3+ + 6NH3 Co(NH3)63+
neutral ligand

Fe2+ + 6CN- Fe(CN)64-

anionic ligand

Pt4+ + 2NH3 + 4Cl- Pt(NH3)2Cl40

mixed ligands

The complex may have a positive, negative or zero charge. The charge is always the
sum of the charges on the individual components.
The structures of some of the complexes are shown below:
 To explain the complex ion, Alfred Werner introduced the concept of secondary
valency. Transition d-block elements form ionic or covalent bonds to fulfil their octet,
this is primary valency of metals. In addition to that, d-block elements have
incomplete inner d-orbital and empty shells. These factors are responsible to attract
surrounding anions and neutral molecules having lone pair of electrons to form co-
ordinate bonds, which is the secondary valency.
The important postulates of Werner’s theory are:
1. The central metal or the metal atoms in coordination compounds show two types of
valency. They are the primary and the secondary valency.
2. The primary valency relates to the oxidation state or ionisable valency
The secondary valency or nonionizable valency relates to the coordinate number.
3. The number of secondary valences is fixed for every metal atom. It means that the
coordination number is fixed.
4. The metal atom works towards satisfying both its primary and secondary valences. A
negative ion satisfies the primary valency. On the other hand, a negative ion or
neutral molecules satisfy secondary valences.

5. The secondary valences point towards a fixed position in space. This is the reason
behind the definite geometry of the coordinate compound.

Limitations of Werner’s Theory:

 1. It could not explain the inability of all elements to form coordination compounds.
2. The Werner’s theory could not explain the directional properties of bonds in various
coordination compounds.
3. It does not explain the colour, the magnetic and optical properties shown by
coordination compounds.

Sidgwick proposed the following postulates to explain the limitation of Werner’s theory:
1. Co-ordinating groups also called as ligands, donate their pair of electrons to central
metal cation to form inner co-ordination sphere. So each and every ligand must have
atleast one pair of electron.
2. Co-ordination number will be such that central metal cation achieves the electronic
configuration of next inert gas. In a complex ion total number of electrons possessed
by central metal cation is called effective atomic number (EAN) of that metal. This is
known as EAN rule of Sidgwick. EAN = metal atom's electrons + the bonding
electrons from the surrounding electron-donating ligands.

Example: When Co3+ ions react with ammonia, the Co3+ ion accepts pairs of nonbonding
electrons from six NH3 ligands as shown in the figure below.

The Co3+ ion is an electron-pair acceptor, or Lewis acid, because it has empty orbitals that
can be used to hold pairs of electrons. The configuration of the Co3+ ion as follows.
Co: [Ar] 3d7 4s2 4p0
Co3+: [Ar] 3d6 4s0 4p0
There is place in the empty shells of this ion for 12 more electrons. Thus six NH 3 ligands can
contribute 12 electrons and combine with Co3+.
In the formation of the co-ordination sphere, the number of ligands surrounding the
central metal ion are such that, the ion releases most energy and becomes most
energetically stable.
 Classification of Ligands:
On the basis of co-ordinate bonds ligands can be divided in to different categories:
1. Monodentate ligands: Any ligand donating one pair of electron is called
monodentate ligands, examples, :NH3, H2:O:, C:N-
2. Bidentate ligands: Any ligand donating two pairs of electron is called bidentate
ligands, examples,
Ethylene diamine

Oxalate ion

3. Tridentate ligands: Any ligand donating three pairs of electron is called tridentate
ligands, examples

Bisethylene triamine

4. Polydentate ligands: Any ligand donating more than three pairs of electron is called
bidentate ligands, examples

Ethylene diamine tetra

acetic acid (EDTA)
The donor atoms in EDTA4- are
the two N atoms, and the four,
negatively charged O atoms.

Application of EDTA in hard water analysis:

Hardness of water is that characteristic which prevents the lathering of soap. The hardness
is imparted due to the presence of certain salts of multivalent cations like Ca2+, Mg2+, Fe2+,
Mn2+ and Al3+ (heavy metals) dissolved in water especially bivalent cations like Ca2+, Mg2+
present abundantly in nature. Temporary hardness (Carbonate/Alkaline Hardness) is
caused by the soluble bicarbonates of Ca and Mg. Temporary hardness is removed by mere
boiling and filtering off the precipitates formed.
Permanent hardness (Non-carbonate/Non-alkaline Hardness) is due to the more soluble
chlorides, sulfates, nitrates of Ca, Mg, Fe, and other heavy metals.

Units of Hardness:
(1) CaCO3 equivalent
Calculation of calcium carbonate equivalent hardness:
Equivalent of CaCO3 for any substance =
Weight of the substance (mg/L) x Chemical equivalent of CaCO3 (Eq.wt of CaCO3)
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Chemical equivalent of the substance (Eq.wt of substance)

Equivalent weight = Molecular weight/n,

where n is either the positive or negative charge present on the salt.
For example, in CaCl 2 where n = 2, Ca ion bears 2+ charge and two chloride ions bear
total two
negative charges.

(2) mg/Litre
It is the number of milligrams of CaCO3 equivalent hardness present in 1 litre of water
1 L water = 1 kg = 1000 g (103 g) = 106 mg water
mg/L is the same as ppm (parts per million)

(3) Other units

1 ppm = 1 mg/L = 0.1° French (Fr) = 0.07° Clarke (Cl)
1° Russian = 1 part of Ca/106 parts of water
1° German = 1 part CaO/105 parts of water
= 10 ppm as CaO or 17.9 ppm CaCO3
Determination of Hardness of water by complexometric titration using EDTA (disodium salt
of EDTA) method:
EDTA can bind at more than one position (hexadentate ligand) to the metal ions and called
as a chelating agent. One molecule of EDTA forms a soluble octahedral complex with one
bivalent metal ion (1:1).

EDTA is used as titrant and the hard water is titrated against the EDTA using an
indicator dye (Eriochrome Black-T) to mark the endpoint of titration, i.e. the complete
complex formation between bivalent metal ions and EDTA.
An initial unstable complex between the Ca2+ & Mg2+ ions and EBT indicator gives a
wine red coloration, but at the end point of the titration, a more stable [Ca-EDTA]/ [Mg-
EDTA] complex is formed which releases the free EBT and the color changes from wine red
(or purple) to a persistent blue or bluish green color of free indicator i.e . EBT

Since hardness of water is expressed in terms of calcium carbonate equivalent, after

performing titration hardness is calculated by below mentioned relation and its unit is parts
per million (ppm):

1000 mL 1N EDTA = 1 equivalent of CaCO3