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2.1 Introduction
Structure and bonding lie at the heart of modern inorganic chemistry. We can deduce
from chemical evidence that atoms combine to form larger units and the stability of
these units is due to chemical bonds.
There are about 118 elements, but when the elements combine they can make a huge
number of compounds. Some of them existed when the world began. Some have been
made by men and women, either by accident or design. Bonding is a consequesnce of
interaction of electrons in the outermost shells of atomic or ionic species involved.
In this chapter, we shall encounter methods of explaining and predicting the bonding in
a variety of compounds.
Why do chemical bonds form?
Chemical bonds form if the resulting arrangement of the atoms has lower energy than
the separated atoms i.e., atoms combine to attain a state of lower energy (potential)
than that in the isolated ones, e.g. H2, P4, S8, H2O, C6H12O6 etc.
Various changes in energy that occur when bonds form results from the movement of
the valence electrons (the electrons in the outermost shell) of atoms.
What holds atoms together in chemical compounds?
The forces that hold atoms together are called chemical bonds. A chemical bond is a
manifestation of a force of attraction.
What is the nature of chemical bonds?
Atoms combine in a variety of ways. Mainly, three different types of bonds may be
formed, depending on the electropositive or electronegative character of the atoms
involved.
Ionic bond
It involves the complete transfer of one or more electrons from one atom to another and
is characterized by a large difference in electronegativity. An ionic bond is formed
between an electropositive and an electronegative element.
Covalent bond
It involves the sharing of a pair of electrons between two atoms and is characterized by
a small difference in electronegativity. A covalent bond is formed between two
electronegative elements or could be generated between a less electropositive and an
electronegative element.
Metallic bond
It involves the free movement of valence electrons throughout the crystal and is also
characterized by small difference in electronegativity. A metallic bond is formed between
two electropositive elements.
Classification of chemical bonds based on the types of forces that hold the atoms
together as shown in Fig. 2.1.
NaCl, CaO
Na, Cu, Alloys
(NH3)n (H2O)n, (HF)n
(NF3)n
HF, H2O
H2, Cl2
C (diamond), SiC
octet rule:
Each atom shares electrons with neighbouring atoms to achieve a total of eight
valence electrons.
Lewis
electron-dot diagrams provide a good starting point for analysing the bonding in
molecules.
These diagrams show the number of bonds between specific atoms and the resonance
possibilities. A few examples of Lewis structures are given in Fig. 2.2.
Modern theories
description of bonding must be consistent with experimental data on bond
Any
lengths, bond angles and bond strengths.
Application
The magnitude of the bond energy is a measure of the strength of the bond.
Biographich Sketch
2.3 Ionic Bonding (Electrovalent Bonding)
The first explanation of chemical bonding was suggested by the properties of salts,
substances now known to be ionic. The ionic bond is a consequence of electrostatic
interaction between the oppositely charged ions that result from the transfer of one or
more electrons from a less electronegative atom to a more electronegative atom. The
atom that loses electrons becomes cation (positive ion), the atom that gains electrons
becomes an anion (negative ion). Any given ion tends to attract as many neighbouring
ions of opposite charge as possible. The formation of solid sodium chloride from sodium
atom and chlorine atom is shown in Fig. 2.3.
Figure 2.3: Formation of Na+Cl- solid from sodium atom and chlorine atom
M (g) M+ (g) + eX (g) + e- X- (g)
M+ (g) + X- (g) MX (s)
Ionization enthalpy
Electron gain enthalpy
Lattice enthalpy
Ionic bonds will be formed more easily between elements with comparatively low
ionization enthalpies and elements with comparatively high electron gain enthalpies.
We can represent electron transfer by the following equation
Na ([Ne] 3s1) + Cl ([Ne] 3s2 3p5) Na+ ([Ne]) + Cl- ([Ne] 3s2 3p6)
As a result of the electron transfer, ions are formed, each of which has a noble gas
configuration.
Characteristics of ionic solids
Ionic compounds tend to have very low electrical conductivity as solids but
conduct electricity quite well when molten or dissolved in water. This conductivity
is attributed to the presence of oppositely charged ions, which are free to move
under the influence of an electric field.
Ionic compounds are soluble in polar solvents like water and insoluble in nonpolar
solvents like benzene and carbon tetrachloride.
The most stable arrangement is the one in which the ions are in contact with
each other and arranged in a symmetrical manner (close packed geometry).
Lattice coordination number is the number of immediate neighbouring oppositely
charged ions.
The size factors largely determine the geometry of the structures and
coordination number.
Examples
Uncommon among
ionic solids
Uncommon among
ionic solids
Linear
0 - 0.155
Triangular
0.155 - 0.225
Tetrahedral
0.225 - 0.414
ZnS
Octahedral
0.414 - 0.732
NaCl, TiO2
Cubic
0.732 1.0
CsCl, CaF2
Figure 2.4: Potential Energy Diagram for ionic bond At a certain critical distance between
the atoms (as shown in Fig.2.4) the energy drop is maximum that results in stability. If
the distance between the atoms is decreased further it results in repulsion.
The attraction of oppositely charged ion does not stop with the bonding of pairs of ions.
The maximum attraction of ions of opposite charge with the minimum repulsion of ions
of the same charge is obtained with the formation of crystalline solid. Then even more
energy is released. Clustering of ion pairs to form an ionic solid and progressive release
of energy is shown in Fig 2.5.
Lattice enthalpy of an ionic compound is defined as the energy released when one mole
of the compound is formed in the regular lattice structure from requisite number of ions
(1 mole of positive ions and 1 mole of negative ions) in the gaseous state.
The lattice enthalpy of an ionic solid is also defined as the energy required for seperating
completely. one mole of a solid ionic compound into its gaseous constituent ions.
Lattice enthalpy cannot be measured experimentally. Lattice enthalpies are calculated
from experimental data using the Born-Haber cycle.
The force of attraction, , between two ions carrying unlike charges separated
by a distance, , is given by Coulombs law.Fer
The corresponding potential energy would be obtained by computing the work
done in bringing the charges to this distance from infinity.
Thus,
The negative sign indicates that this amount of energy is released by the system
resulting in lowering of potential energy, which we expect when stable bonding
has occurred.
= -755.2 kJ mol-1
The Born-Lande equation gives a calculated value of lattice enthalpy, U0 = -755.2 kJ
mol-1 for sodium chloride, which is close to the experimental value of -770 kJ mol-1 at
25 C. For more precise work, several other functions have been suggested for repulsion
energy. Other variables like van der Waals forces, zero point energy and correction for
heat capacity are included. The refined value for lattice enthalpy is -757.5 kJ mol-1.
The values of lattice enthalpy calculated by means of the above equation have been
found to be in good agreement with those obtained experimentally as shown for some of
the compounds in the Table 2.2.
Table 2.2 Lattice Enthalpy of Some Compounds
Compound
Theoretical
AgCl
-895
-849
CaF2
-2
The Madelung constant depends on the coordination number of each ion and geometric
arrangement of ions in the crystal lattice. Hence, lattice enthalpy and stability of an
ionic crystal is directly proportional to the Madelung constant. Values of Madelung
constants for different ionic crystals are given in Table 2.3.
.
Table 2.3
Structure
Formula
Coordination number
Sodium chloride
NaCl
1.7475
Cesium chloride
CsCl
1.7627
Zinc blend
ZnS
1.6380
Wurzite
ZnS
Zn2+(4); S2-(4)
1.6413
Fluorite
CaF2
5.0388
Example
Calculate the value of Madelung constant for MgO from the following data.
r0 = 2.10 x 10-10 m
n=7
U0 = -3940 kJ mol-1
Solution:
In case of MgO, the charges on cation and anion are +2 and -2 respectively.
Therefore, A = 1.74.
Factors Influencing the Magnitude of Lattice Enthalpy
The lattice enthalpy is useful in correlating properties of ionic substances because the
formation or destruction of the crystal is frequently more important step in reactions
involving ionic substances.
Some properties of ionic compounds can be explained on the basis of their lattice
enthalpy values.
The higher the charge on cation and anion, the greater would be the magnitude of the
lattice enthalpy.
-1
U0 ( kJ mol )
Na+F 914.2
Mg2+(F -)2
2882.0
<
Mg2+O23895.0
<
Smaller the size of ions, the smaller would be inter-ionic distance, the higher would be
the value of lattice enthalpy.
U0 ( kJ mol-1)
U0 ( kJ mol-1)
LiF
1034
LiF
1034
>
NaF
>
914.2
LiCl >
840.1
>
KF
812.1
LiBr
781
>
Down the group, lattice enthalpy decreases as the size of the cation increases.
U0 ( kJ mol-1)
BeO
4541
>
MgO
3895
>
CaO
3520
>
SrO >
3325
BaO
3108
The greater the lattice enthalpy, the more stable is the ionic compound.
CaCl2
Ionic compounds with high lattice enthalpy require a greater input of thermal energy
to breakdown the crystal lattice. Consequently, the greater the strength of the ionic
solid, higher will be its melting point.
LiF
>
U0 (kJ mol-1)
1034
m.p. (C)
870
The lattice enthalpy affects the solubility of the
LiCl
>
840.1
613
ionic compounds.
LiBr
781
597
>
LiI
718
446
1. For a solid to dissolve in a solvent, the strong forces of attraction between its
ions (U0) must be overcome.
2. The solvation of ions is referred to in terms of solvation energy,which is always
exothermic.
3.
M+(g) + aq M+(aq) + hydration energy
4.
X-(g) + aq X-(aq) + hydration energy
1. These exothermic solvation energies have their origin in the electrostatic
interaction between the polar solvent molecules and the solute ions.
2. Since cations are smaller than anions, the positive field of a cation will be greater
than the negative field of an anion, so that the solvation energies of cations
generally exceed those of anions.
3. An ion with high value of the ionic potential will tend to form the solvated ion
more easily than the ion with a smaller value of ionic potential. Ionic potential is
given by
Ions with small size and high charge get extensively hydrated.
(a)
charge
Na+
(+)
Mg2+
(2+)
Al3+
(3+)
422
1953
4694
(b)
size (pm)
Hhydration(kJ mol-1)
Li+ Na+ K+
Rb+
60 95 133 148
531 422 338 318
Cs+
169
280
Ionic crystals are generally soluble in polar solvents like water and insoluble in non-polar
solvent such as carbon tetrachloride. As a general rule, for a solid to dissolve in a
particular solvent, its solvation energy (Hhydration refers to hydration energy) should be
greater than the lattice energy of that solid.
solvation energy > lattice energy .. salt dissolves in the solvent
solvation energy < lattice energy .. salt does not dissolve in the solvent
Lithium chloride and lithium bromide are soluble in water since the hydration energy is
greater than lattice energy in both the cases.
LiCl
LiBr
Hhydration
883
854
U0 (kJ mol-1)
840
781
Silver chloride and Silver bromide are insoluble in water since the
hydration energy is smaller than lattice energy in both the cases.
AgCl
AgBr
Hhydration
848
815
U0 (kJ mol-1)
895
877
Some ionic compounds like sulphates and phosphates of barium and strontium are
insoluble in water inspite of being ionic. This can be attributed to the high
lattice enthalpies associated with these compounds due to polyvalent nature of
both cation and anion. In these cases, hydration of ions fails to liberate sufficient energy
to offset the lattice enthalpy.
2.3.3 The Born-Haber Cycle
Direct calculation of lattice enthalpy is quite difficult because the required data is often
not available. Therefore, lattice enthalpy is determined indirectly by the use of the Born
Haber cycle. It is based on Hesss law. Hesss law states that the enthalpy of a reaction
is the same, whether it takes place in a single step or in more than one step.
The formation of an ionic compound, MX, shown in Fig 2.7, may occur either by direct
combination of the elements or by a stepwise process involving vaporisation of
elements, conversion of the gaseous atoms into ions and the combination of the gaseous
ions to form the ionic solid.
Biographic Sketch
Biographic Sketch
Example
Calculate the lattice enthalpy of KCl from the following data by the use of Born-Haber
cycle.
Enthalpy of sublimation for
K(s) K(g)
H1 = + 89 kJ mol-1
Hf = -438 kJ mol-1
Solution:
According to Hesss law, we have
fH= H1 + H2 + H3 +H4 + H5
-438 kJ mol-1 = (+89 + 122 + 425 355) kJ mol-1 + H5
Hence, Lattice enthalpy of KCl, H5 is 719 kJ mol-1.
Example
Assuming, hypothetical NaCl2 would crystallize in the fluorite structure (A=2.52),
calculate enthalpy of formation of NaCl2. Comment on the calculated value of fH.
Enthalpy of sublimation of Na (s), H1= + 109 kJ mol-1
Enthalpy of dissociation of Cl2 (g), H2 = + 247 kJ mol-1
First ionization enthalpy of Na (g), H3I= + 494 kJ mol-1
Second ionization enthalpy of Na+ (g), H3II = + 4561 kJ mol-1
Electron gain enthalpy of Cl (g), H4= - 355 kJ mol-1
Lattice enthalpy , H5= -2155 kJ mol-1
Solution:
Figure 2.9: (a) Far apart: no influence on each other (b) Closer together: the negative
ion is
polarized by the positive ion (c) Even closer: the charge cloud
of the negative
ion merges with that of the positive ion; covalence
results
The power of an ion to distort the other ion is known as its polarizing power.
The power of an ion to distort the other ion is known as its polarizing power.
The polarizing power of a cation is proportional to its ionic potential, change/ size
The large negative ion is highly polarizable.
MCO3 MO + CO2
Small size cations show greater tendency to polarize the carbonate anion (CO32-) into an
oxide (O2-) and CO2. Hence, as the size of cation increases polarizing power of the cation
decreases and the thermal stability of metal carbonates increases.
BeCO3 (unstable) < MgCO3 (350C) < CaCO3 (900C) < SrCO3 (1290C) < BaCO3
(1360C).
2.3.5 Ionic Character in Covalent Compounds and Dipole Moment
Covalent bonds having partial ionic character are referred to as polar covalent bonds.
The polarity of a bond, such as that in HF is characterized by a separation of electric
charge (partial charge, ).
+ HF
The degree of polarity in a covalent bond can be expressed in terms of the bond
moment, that is, the product of the charge, q and the internuclear distance, r, since
each bond amounts to a dipole.
=qxr
= (4.8 x 10-10 esu) (10-8 cm)
= 4.8 x 10-18 esu-cm
= 4.8 D
(1D =10-18 esu-cm)
In SI units, unit of charge is Coulombs (C) and that bond length in meters (m),
therefore has units of C m.
= (1.6022 x 10-19 C) (10-10m)
= 1.6022 x 10-29 C m
= 4.8 D
(1 D = 3.336 x 10-30 Cm)
The average polarity of a given species over a period of time is measured by its
permanent dipole moment (), which is designated as a vector, pointing from the
centre of positive charge to the centre of negative charge with a positive charge
at one end.
The permanent dipole moments of polar diatomic molecules are same as their
bond moments. The permanent dipole moments of polyatomic molecules,
however, are determined by both the bond moments and lone pair moments.
A molecule will have a dipole moment if the summation of all of the individual
bond moment vectors is nonzero.We can sometimes relate the presence or
absence of a dipole moment in molecules to its molecular geometry. For
The two bond moments of equal magnitude but opposite direction cancel each other,
giving rise to a net dipole moment of zero for the molecule.
For comparison, consider water molecule. The bond moments point from the hydrogen
atoms towards the more electronegative oxygen.
Here, however, the two bond moments do not points directly towards, or away from
each other. As a result, they add together to give a nonzero dipole moments for the
molecule.
The dipole moment of H2O has been observed to be 1.85 D. If the water molecules were
linear, the dipole moment would be zero. Figs 2.11 and 2.12, and Table 2.4 give the
geometries and dipole moments of some molecules.
Biographic
Table 2.4 Dipole Moments of Some Polar Molecules
Molecule
Geometry
HF
Linear
1.92
HCl
Linear
1.08
HBr
Linear
0.78
HI
Linear
0.38
H 2O
Bent
1.85
NH3
Pyramidal
1.47
SO2
Bent
1.60
Table 2.5 summarizes the relationship between the molecular geometry and dipole
moment for the molecules of type AXn in which all X atoms are identical. The geometries
in which AX bonds are directed symmetrically about the central atom (for example
linear, trigonal planar, and tetrahedral) give molecules of zero dipole moment, that is
the molecules are nonpolar. Those geometries in which the X atoms tend to be on one
side of the molecule (for example bent and trigonal pyramidal) can have nonzero dipole
moments, that is, they can give polar molecules.
The NH3 and NF3 molecules present an interesting case in relation to the resultant dipole
moment. Although fluorine is more electronegative than nitrogen the resultant dipole
moment of NH3 (4.90 x 10-10C m) is greater than that of NF3 (0.80 x 10-30 C m) in both
cases the central nitrogen atom has a lone pair whose bond moment points away from
the nitrogen atom.
Table 2.5 Relationship Between Molecular Geometries and Dipole
Formula
Molecular Geometry
Dipole Moment
AX
Linear
Can be nonzero
AX2
Linear;
Bent
Zero;
Can be nonzero
AX3
Trigonal planar;
Trigonal pyramidal;
T-shape
Zero;
Can be nonzero;
Can be nonzero
AX4
Tetrahedral;
Square planar;
See saw
Zero;
Zero;
Can be nonzero
AX5
Trigonal bi-pyramidal;
Square pyramidal
AX6
Octahedral
Zero
Moment
resulting into a larger net dipole moment. In NF3, the resultant of the
bond
moments (fluorine is the negative end) act in opposition to the lone pair moment, cancel
each other and hence, the net dipole moment of the NF3 molecule is lowered. Figure
2.13 shows the net dipole moments in NH3 and NF3.
Example
Calculate the percentage of ionic character in HCl. The experimental dipole moment of
HCl is 1.03 D and bond distance in HCl is 1.27 x 10-10 m.
Solution:
obs = 1.03 D = (1.03)( 3.34 x 10-30) C m
cal = q x r = (1.6 x 10-19 C) (1.27 x 10-10 m)
Percentage ionic character
Example
The electronegativities of hydrogen and chlorine are 2.1 and 3.0. Calculate percentage
ionic character in HCl.
Solution:
Percentage ionic character = 16 (A B) + 3.5 (A B)2
= 16 (3.0-2.1) + 3.5 (3.0-2.1)2=17.2
Therefore, HCl is 17.2 % ionic.
In general, a bond corresponding to an electronegativity difference of 2.1 is nearly 50%
ionic.
The ionic character of a bond may be estimated in simple cases from its dipole
moment values Percentage ionic character =
There are several different theories, which explain the electronic structures and describe
the shapes of different molecules.
2.4.1 Lewis Theory: The Octet Rule
For many light atoms a stable arrangement is attained when the atom is surrounded by
eight electrons. A formulation of this type indicates only the importance of a shared pair
of an electron but gives no information as to how sharing is effected or as to the nature
of the bond.
Theoretical approaches and interpretations
The characteristics of covalent compounds suggest that an increase in electronic charge
density between bonded atoms occurs. This increase has been rationalized in terms of
two somewhat different theoretical approaches, each of which is the result of
approximate solutions of appropriate wave equations.
Figure 2.14: The potential energy curve for the formation of H2 molecule as a function
of
internuclear distance
Now imagining the process to be reversed, energy must be added to seperate the atoms
in the molecule from their normal bond length to infinite distance. This energy that must
be added is called the bond dissociation energy. Higher the bond dissociation energy,
the stronger would be the bond.]
In the case of hydrogen molecule, the distance between the two hydrogen atoms
corresponding to minimum energy is 74 pm and the decrease in potential energy in the
formation of H2 molecule has been found to be 431.4 kJ mol-1. Therefore, H2 molecule
would be much more stable than hydrogen atoms due to decrease of energy.
Heitler-London
proposed
quantum-mechanical
treatment
of
the
hydrogen
molecule. According to this theory, the calculated bond distance is 74.9 pm and the
decrease in potential energy is 388 kJ mol-1. Introduction of sufficient parameters can
improve the wave function to any desired accuracy, giving rise to the bond distance 74
pm and potential energy 431.4 kJ mol-1.
By making use of the concept of hybridization, VB theory, succeeds in accounting for the
principles of molecular geometry. By introducing the idea of resonance, it rationalizes
the chemical properties of many molecules.
Biographic
Types of Overlapping of Atomic Orbitals and Orbital Diagrams
overlappings-s
s-p overlapping
pz-pz overlapping
px-px overlapping
py-py overlapping
p-d overlapping
d-d overlapping, etc.
A sigma bond () is formed by the overlap of atomic orbitals along the internuclear axis
while a pi bond is formed by the lateral (sideways) overlap of atomic orbitals. Sigma
bond is a stronger bond because the extent of overlap is quite large. Pi bond is a weaker
bond because the extent of overlapping is small.
Hydrogen fluoride molecule forms through s-p overlap. The half filled 2pz orbital of
fluorine overlapps with half filled 1s orbital of hydrogen atom resulting in the formation
of sigma bond. The formation of sigma bond in hydrogen fluoride molecule is shown in
Fig 2.15.
Biographic
Rules of hybridization
The concept of hybridization is described in the following examples. The linear geometry
of BeF2 can be described by assuming Be to be sp hybridized. The two sp hybrid orbitals
overlap with the two 2pz orbitals of fluorine to form two covalent bonds.
The electronic configuration of Be atom in its ground state is 1s22s2. The promotion of 2s
electron to 2p orbital results in an excited state configuration of Be, i.e; 1s22s12pz1. It is
then postulated that the s and p orbitals of Be mixed with each other i.e., hybridised to
give identical orbitals i.e., (orbitals of equivalent energy)(Figure 2.17, 2.18 and 2.19).
Since in the formation of bivalent compounds of beryllium one s and one p orbital is
involved in hybridization, it is called sp hybridization and the resulting orbitals are called
hybrid orbitals. The electronic configuration of fluorine is 2s22px2 py2 pz1. The half filled pz
orbital of each fluorine atom overlaps with each of the two half filled sp hybrid orbitals of
beryllium to form two covalent bonds (Figure 2.20).
Thus, with the help of concept of hybridization, we are successful in describing the
bonding as well as the geometry in BeF2 molecule.
.The quantum mechanical wave functions for s and p atomic orbitals derived from
Schrodinger wave equation can be mathematically combined to form a new set of
equivalent wave functions called hybrid atomic orbitals
sp1 =
N (s +p)
sp2 =
N (s - p)
is the normalizing coefficient and sp1 and sp2 are the new diagonal or sp
hybrid orbitals.
Energetics of Hybridization
As an illustration, we may consider the formation of methane molecule. The outer
electronic configuration of carbon atom in the ground state is 2s2p2. Energy is required
for the promotion of an electron 2s to 2p.
Figure 2.22: Formation of four sp3 hybrid orbitals by overlapping of one s and
three p orbitals
The energy of the resulting hybrids is the weighted average of the participating atomic
orbitals.
Esp3 =
[Es + 3EP]
=
= -1241 kJ mol-1
sp3d Hybridization
Non metal atoms like phosphorus (3s23p33d) can exhibit variable covalency due to
availability of vacant 3d orbitals. The possibility of sp3d hybridization in phosphorus
describes the formation and trigonal bipyramidal (TBP) geometry of PF5 molecule (Fig
2.23) and for PCl5 molecule (Fig 2.24).
Figure 2.23: TBP geometry of PF5 molecule resulting from sp3d hybridization of
valence Shell orbitals of central P atom
sp3d hybrid orbitals are directed towards the corners of a trigonal bipyramid. They form
three coplanar bonds with bond angles of 120 and two bonds at right angles to this
plane, one above and one below.
Number of Hybrid
Orbitals
Shape of
Molecule
Example
sp
Linear
BeCl2
sp2
Triangular planar
BCl3
sp3
Tetrahedral
CH4
dsp2
Square planar
[PtCl4]2-
sp3d
Trigonal
bipyramid
PCl5
sp3d2
Octahedral
SF6
,
,
.
However, the number of bps are 4, 3 and 2 and lone pairs are 0, 1, and 2
respectively.
Electron pairs tend to minimize repulsions. If the central atom is surrounded by
only bond pairs, then the repulsions among bps are equal and the molecule
would have a regular geometry. On the other hand, when the central atom is
surrounded by both bps as well as lps, then the repulsions among them are
unequal, which is of the order: lone pair - lone pair > lone pair - bond pair >
bond pair - bond pair and the molecule would have a distorted or irregular
geometry.
Accordingly, the presence of one or more orbitals with lone pairs of electrons has
the effect of altering the bond angles i.e., the molecules with lps of electrons do
not retain regular geometry.
For the prediction of geometrical shapes of molecules with the help of VSEPR model, it is
convenient to divide molecules into two categories
1. molecules in which the central atom has no lone pairs, i.e., surrounded by only
bond pairs and
2. molecules in which the central atom has one or more lone pairs, i.e., surrounded
by both bond pairs as well as lone pairs.
Tables 2.7 shows the arrangement of electron pairs about a central atom (A) and X
represents the surrounding atom.
Table 2.7
Molecule
Number of electron
pairs
Number of
bond pairs
Regular geometry
Example
AX2
Linear
BeCl2
AX3
Planar Trigonal
BF3
AX4
Tetrahedral
CH4
AX5
Trigonal bipyramidal
PCl5
AX6
Octahedral
SF6
Let us take an example wherein we take different systems containing four electron pairs
with different combinations of lone pairs and bond pairs and observe their shape and
bond angles.
In CH4 molecule, all of the valance-shell electron pairs about the carbon atom are
bonding and because all of the bonds are alike, we expect the CH4 molecule to have an
exact tetrahedral geometry with bond angle 109.50. However, if one or more of the
electron pairs is non bonding or if there are dissimilar bonds, all four valence-shell
electron pairs will not be alike. Then we expect the bond angles to deviate from 109.50
and geometry becomes distorted.
.
Table 2.8
Molecule
CH4
Tetrahedral
109.5
NH3
Trigonal pyramidal
107
OH2
Angular
104.5
Figure
2.29:
Consider the trigonal pyramidal molecule, NH3. The lone pair on the nitrogen atom
requires more space than the bonding pairs. Therefore, the N-H bonds are effectively
pushed away from the lone pair, and the H-N-H bond angles become smaller than the
tetrahedral value of 109.5. Consequently, NH3 molecule has distorted tetrahedral or
trigonal pyramidal geometry with a bond angle 107. Similarly H2O molecule with two
lone pairs has bent geometry with a bond angle 104 (Table 2.8 and Fig 2.29).
Central atom with five or six valence-shell electron pairs
Five electron pairs tend to have a trigonal bi-pyramidal (TBP) arrangement and six
electron pairs tend to have an octahedral arrangement. In trigonal bi-pyramidal
Figure 2.32:Structure (T-shaped) of ClF3 molecule in which two lone pairs (lps)
occupy equatorial positions
As a rule, if lone-pair occurs in a trigonal bi-pyramidal geometry, the lp always occupies
equatorial position to minimize the repulsions. Consequently, the molecule will have
distorted trigonal bi pyramidal geometry.
Similar arguments indicate that ClF3 will have T-shaped geometry (Fig 2.32).
In sulphur hexafluoride, there are six electron pairs (all bonding pairs) around sulphur
atom. Thus, it has an octahedral molecular geometry, with sulphur at the centre of the
vertexes. In iodine pentachloride, IF5 (five bond pairs and one lone pair) the lone pair of
iodine occupies one of the six equivalent positions in the octrahedral arrangement,
giving a square pyramidal geometry. In xenon tertafluoride, XeF4 (four bond pairs, two
lone pairs), the two lone pairs on xenon occupy opposite positions in the tetrahedral
arrangement to minimize their repulsion. The result is a square planar geometry.
Molecular geometries of molecules with a total of five and six electron pairs with
different combination of lone pairs and bond pairs are summarized in Table 2.9.
Table 2.9
IF7
sp d
7
Pentagonal bi- 72 and 90
pyramidal
Table 2.11 Geometry of covalent molecules involving different
types of
hybrid orbitals, lone pairs and bond pairs on
the central atom
Number of Valence Shell
Electron Pairs on a
Hybridization and
Central Atom
Example
Type of
Shape of
Distribution of
Molecule
Molecule
Orbitals
Bond
Lone Pair Total
Pair
AX2
AX2L
2
2
0
1
2
3
sp
sp2
Linear
Trigonal
planar
Linear
Bent (V shaped)
AX2L2
sp3
Tetrahedral
Bent (V shaped)
AX2L3
sp3d
Trigonal bipyramidal
Linear
AX3
sp2
trigonal
planar
triangular
AX3L
sp3
Tetrahedral
Trigonal
pyramidal
AX3L2
sp3d
Trigonal bipyramidal
T - shaped
AX4
sp3
Tetrahedral
Tetrahedral
AX4L
sp3d
Trigonal bipyramidal
See-Saw
AX4L2
sp3d2
Octahedral
Square
planar
AX5
sp3d
Trigonal bipyramidal
Trigonal bipyramidal
Cl-Be-Cl
AX5L
sp3d2
Octahedral
Square
pyramidal
AX6
sp3d2
Octahedral
Octahedral
Figure 2.33: Angular geometry of H2O molecule resulting from sp3 hybridization.
Geometry of molecules involving sp3d hybridization
The molecules involving sp3d hybridization are
1. SF molecule (Figure 2.34)4
2. ClF3 molecule (Figure 2.35)
3. XeF2 molecule (Figure 2.36)
Figure 2.35: Distorted T-shaped geometry of ClF3 molecule involving sp3d hybridization
Figure 2.41: Trigonal planar geometry of nitrate ion involving sp2 hybridization
of the
central atom
Geometry of sulphate ion
The ground state electronic configuration of S atom is 3s23px2py1pz1 and the excited state
electronic configuration is 3s13px1py1pz1dxy1dyz1. One 3s and three 3p orbitals hybridize to
produce four sp3 hybrid orbitals, involving four sigma bonds. The d orbitals are excluded
from hybridization and they involve in the formation of pi bonds.
Figure 2.43: Geometry of ClO3The geometry of ClO3- ion is actually pyramidal. This is due to the fact that a lone pair of
electrons occupies one of the sp3 hybrid orbitals. The repulsions between lone pair-bond
2 22
+ 2 22
ii.
+ 2 22
iii.
>
104.5
103.2
NF3
102
iv.
As the electronegativity of the surrounding atoms increases, the bond pair is
v.
II
The electron pair, which forms a double bond wherever written is not localized in
any one of the two bonds, but rather smeared out over all the bonds.
The various structures of which the ions/molecules is said to be a resonance
hybrid are known as contributing structures or canonical forms or mesomeric
structures. They cannot be isolated, i.e., the canonical forms have no real
existence.
Figure 2.46: Resonance in NO3- ion I , II and III represents the canonical forms.
A straight, double- headed arrow always indicates resonance; it is never used any other
purpose
There are certain rules to write various canonical forms which contribute towards
resonance.
The contributing structures should have the same relative arrangement of atoms.
They should differ only in the positions of electrons.
The contributing structure should have the same number of unpaired electrons.
The contributing structures should be of comparable energy.
The contributing structures should be such that the negative charge resides on an
electronegative element and positive charge resides on an electropositive
element.
In contributing structure, like charges should not reside on atoms close to each
other and unlike charges should not be widely separated.
The larger the total number of covalent bonds, the more important is the
contributing structure.
Misconceptions
Benzene does not contain equal properties of molecules with structures shown in Fig
2.47, nor is there a tautomeric equilibrium nor can it be said that benzene exists for a
certain fraction of time in the form (I) and for another fraction of time as (II).
The molecule itself has a single structure of its own which cannot be described
directly by a conventional bond diagram.
Figure 2.49: Resonance energy for the structures I, II and III of CO2
For example, the enthalpy of formation of benzene fH calculated from its enthalpy of
combustion and the enthalpies of formation of its products is -5535 kJ mol-1, whereas
the value calculated from the summation of bond energies, 6 CH + 3 CC + 3 C=C
bonds, is 5381 kJ mol-1. The benzene molecule is thus more stable by 154 kJ mol-1 due
to resonance. Similarly, for CO2, the resonance energy is 138 kJ mol-1.
E = Resonance Energy
= Eactual Emost stable canonical structure
= Eobserved Ecalculated
= -1602.5 kJ mol-1 - 2[Energy of C=O bond]
= -1602.5 kJ mol-1 + 1464.5 kJ mol-1
= -138.0 kJ mol-1
The dipole moment of a molecular species is less than that predicted in terms of
contributing structures.
The chemical properties of a given species are not those of a specific canonical
form but rather those of a hybrid of all forms.
Bond order =
[Nb - Na]
Figure 2.54: Energy levels of different molecular orbitals for O2, F2 and Ne2
However, this sequence of energy levels does not apply to homonuclear diatomic
molecules of lighter elements, i.e., boron through nitrogen (Figs 2.55 and 2.56).
The difference in the energy of 2s and 2pz atomic orbitals in kJ mol-1 for the lighter
elements is given below
Li
178
Be
262
B
449
C
510
N
570
O
1430
F
1970
Figure 2.56: The change in energies of MOs due to mixing of orbitals of same energy
We may now consider the formation of diatomic molecules from H2 to Ne2. Molecular
orbital theory shall give us information about the nature of homonuclear diatomic
species.
Hydrogen molecule, H2
The hydrogen molecule is formed by the combination of the hydrogen atoms. 1s orbital
of each hydrogen atom form two molecular orbitals, BMO and ABMO. Each hydrogen
atom has one electron in 1s orbital and, therefore, there are two electrons to be
accommodated in MOs. Both these electrons would be accommodated in the (1s) BMO.
The energy level diagram for H2 molecule is shown in Fig 2.57.
Figure 2.58 Energy level diagrams for H2+ molecule ion and H2 molecule
The hypothetical He2 molecule
There are four electrons to be accommodated in He2 molecule. Since each molecular
orbital can accommodate two electrons with opposite spins, only one pair can be
accommodated in (1s) bonding molecular orbital and the other in (*1s) antibonding
molecular orbital.
Thus, the electronic configuration for He2 is [(1s)2 (*1s)2] and the bond order is zero.
In effect, the bonding and antibonding cancel each other and hence the molecule He2
does not exist.
Boron molecule, B2
The electronic configuration of Boron atom is 1s2 2s2 2px1.
There are ten electrons to be accommodated in B2 molecule (Fig .2.59)
Figure 2.61: Molecular orbital energy level diagrams showing electronic configuration
for
Li2, Be2, B2, C2, N2, O2, F2 and Ne2
Table 2.13 The physical properties of homonuclear
diatomic
molecules of the second period
Molecule/
Bonding Anti bonding Bonds r(pm) Bond energy
Molecule Ion electrons
electrons
kJ mol-1
+
H2
1
0
0.5
106
255
H2
2
0
1
74
431.4
He2+
2
1
0.5
108
293
He2
2
2
0
-0
Li2
2
0
1
267
113
Be2
2
2
0
-0
B2
4
2
1
159
288
C2
6
2
2
131
585
N2
8
2
3
110
940
+
N2
7
2
2.5
112
~800
O2
8
4
2
121
493
O 2+
8
3
2.5
112
600
O 28
5
1.5
130
-O228
6
1
148
-F2
8
6
1
144
~150
Ne2
8
8
--0
Magnetic
property
Paramagnetic
Diamagnetic
Paramagnetic
-Diamagnetic
-Paramagnetic
Diamagnetic
Diamagnetic
Paramagnetic
Paramagnetic
Paramagnetic
Paramagnetic
Diamagnetic
Diamagnetic
--
Whatever has been studied so far in connection with molecular orbital theory can be
summarized as follows.
The positive value of bond order with H2+ ion indicates that the bond does get
formed and the molecule is stable. The molecule ion H2+ has been detected
through spectroscope when electric discharge is passed through hydrogen gas
under pressure.
The zero bond order in He2, Be2 and Ne2 molecules indicate their nonexistence. However, He2+ ion has been isolated and its existence was proved in
cosmic rays.
Surprisingly, the bond in Li2 molecule is much longer and weaker than in
H2. This may be attributed to
the 2 orbital of Li is bigger in size than 1 orbital of hydrogen and the overlap
involving orbitals of Li is less effective and diffuse.ss2s-2s
the 1s2 electrons of Li cause repulsion between the atoms and thus do not allow
two Li atoms to come nearer to each other than 2.67.
The observed paramagnetic character of B2 is explained on the basis of the
mixing of molecular orbitals of the same symmetry as discussed earlier. Due to
this mixing, the 2px and 2py molecular orbitals lie at lower energy level than
the 2pz molecular orbital. Since each bonding molecular orbital contains a
single, i.e., an unpaired electron, the molecule B2 is paramagnetic.
The molecule C2 should be stable, since 2p bonding orbitals provide four lots of
stabilization energy giving two bonds. The fact that carbon exists as
macromolecules in graphite and diamond illustrates the point that an even more
stable arrangement is formed in preference, where each atom forms four bonds.
The bond order in N2 molecule is three and thus nitrogen molecule contains a
triple bond. Hence, the nitrogen molecule is highly stable. This is confirmed by its
high bond dissociation energy (940 kJ mol-1).
Since there are two unpaired electrons (one in each) in *2px and *2py the
oxygen molecule is paramagnetic. Bond order in this case is 2 and thus oxygen
molecule contains a double bond.
Example
Of the species O2, O2+, O2-, O22-, which would have the maximum bond strength?
Solution:
The bond orders, bond lengths of the above species are in the order:
i.
ii.
Bond length
O22-> O2-> O2 > O2+
+ - 22 22 2
(1)
Higher bond orders are associated with shorter bond lengths and higher bond strengths.
Since O2+ has the highest bond order, it has the shortest bond length and hence the
maximum bond strength.
Bond order and bond length and bond energy of homonuclear diatomic molecules
are given below. Bond order
B2 (1) < C2 (2) < N2 (3) > O2 (2) > F2 (1)
Bond Length (pm)
B2 (159) > C2 (130) > N2 (100) < O2 (121) < F2 (144)
Bond Energy (kJ mol-1)
B2 (288) < C2 (585) < N2 (940) > O2 (493) > F2 (151)
Hence bond order is directly proportional to bond strength and inversely proportional to
bond length.
Biographic
Table 2. 13
Table 2.13 The physical properties of homonuclear
diatomic
molecules of the second period
Molecule/
Bonding Anti bonding Bonds r(pm) Bond energy
Molecule Ion electrons
electrons
kJ mol-1
H 2+
1
0
0.5
106
255
H2
2
0
1
74
431.4
He2+
2
1
0.5
108
293
He2
2
2
0
-0
Li2
2
0
1
267
113
Be2
2
2
0
-0
B2
4
2
1
159
288
C2
6
2
2
131
585
N2
8
2
3
110
940
N 2+
7
2
2.5
112
~800
O2
8
4
2
121
493
O 2+
8
3
2.5
112
600
O2
8
5
1.5
130
-O228
6
1
148
-F2
8
6
1
144
~150
Ne2
8
8
--0
Magnetic
property
Paramagnetic
Diamagnetic
Paramagnetic
-Diamagnetic
-Paramagnetic
Diamagnetic
Diamagnetic
Paramagnetic
Paramagnetic
Paramagnetic
Paramagnetic
Diamagnetic
Diamagnetic
--
Figure 2.62: Molecular orbitals resulting from mixing of atomic orbitals of different
energy
The MO configurations for heteronuclear diatomic molecules are developed based on
isoelectronic principle, i.e. two molecular species with the same number of atoms and
the same total number of valence electrons are said to be isoelectronic. Isoelectronic
principle states that such molecular species will have similar molecular orbitals and
molecular structures.
Carbon monoxide CO
CO is isoelectronic with N2 molecule.
1s2 2s2 2p2
1s2 2s2 2p4
C
O
Bond order =
Thus CO contains a triple bond. Its bond dissociation energy has been found to be 1067
kJ mol-1 and bond length is equal to 114 pm.
Nitric Oxide, NO
The electronic configuration of N and O atoms are
N
O
Differences
The VBT visualizes the bond formation as localized interaction between two
atomic orbitals belonging to the constituent atoms while the molecular orbital
theory involves delocalized molecular orbitals spread over the whole molecule.
While VBT fails to account for paramagnetic character of oxygen, MOT offers
satisfactory explanation.
While resonance plays an important role in VBT, this concept has no place in
MOT.
VBT is simple to apply, while MOT is difficult to apply, i.e., the calculations
involved in MOT are much more tedious than those involved in VBT.
The MO description, however, provides better descriptions of simple species such
as H2+ and O2 than do the one and three electron bonds that must be involved in
VB approach.
The MO method has the additional advantages of better describing excited states,
multiple bonding and bond weakening via occupancy of antibonding orbitals.
In summary, each approximation has its own specific uses and advantages and it is
often desirable to use the approach that is better suited to the specific situation in
question. In general, molecular orbital theory is more relevant as it considers two
possibilities of bonding, i.e., the electrons can occupy both bonding and antibonding
molecular orbitals whereas in valence bond theory the electrons represent only bonding
state.
Summary of Covalent bonding
Summary
Exercises
1. Why do atoms combine in a definite and not in an arbitrary number to form a
given molecule?
2. (Water is H2O but neither H3O nor HO2).
3. Explain why H2 is a stable molecule formed from two hydrogen atoms while He2 is
unstable?
4. Write Lewis structures for N2, C2, O3, PO43-, SO42- and HClO4.
5. Oxalic acid,
Book References
Inorganic Chemistry,
Principles of Structure and Reactivity
James E. Huheey et al.
Addison-Wesley Publishing Company
Advanced Inorganic Chemistry