Prediction of Dipole Moments of Small Molecules

Qualitative Prediction of dipole moments using VSEPR shapes

When a bond is formed between two different atoms of a diatomic molecule, it acquires a polarity because of the difference in
electronegativities of the two atoms. The atom which is more electronegative gets a fractional negative charge and the other atom gets
a fractional positive charge. Such a molecule is called a dipole and the degree of polarity in such molecule is given by dipole moment
(

), which is defined as the product of charge and distance between two dipoles.
=e

d(

= dipole moment, e = electronic charge, d = distance)

is measured in debye (D)

1D = 1 10-18 e.s.u cm = 3.336 10-30 cm
In a molecule of the type ABmEn each of the bonds will have a bond dipole moment or bond moment depending on the polarity of the
A-B bonds which is directed towards the atom with the -charge.
In such molecules we also have a dipole moment due to the lone pairs (called lone pair moment) and is directed towards the lone pair
and away from the atom.
Note:
Dipole moment is a vector quantity and has both magnitude and direction. In physics the standard convention gives the direction of
dipole moment from positive charge towards negative charge. In chemistry since we give importance to the electron, the convention is
the opposite, i.e. the direction is from positive to negative or from electron poor atom to electron rich atom.
VSEPR theory gives us the shapes of molecules and thus the angles between the bond moment and lone pair moment vectors. We
can therefore predict qualitatively the relative values of dipole moments of molecules by considering the vector sum of the
contributing bond and lone pair moments.
Predicting dipole moments
Once we write down the VSEPR formula for a molecule we may easily find out whether it will have a net dipole moment or whether
the dipole moment will become zero.
Rule 1.
All molecules of the type ABm will have zero dipole moment.
Examples: CO2 (AB2), BF3 (AB3) CF4 (AB4), PCl5 (AB5), SF6 (AB6), IF7 (AB7) and all examples of the respective classes will have a
zero net dipole moment since the individual bond moments will cancel each other.
Note:
In this and in the following rules we are only considering cases where all the 'B' atoms are identical. If they are different, then in some
cases we might have a non-zero dipole moment. e.g.
has zero dipole moment, but,
will have a finite dipole moment.
Rule 2.
AB2E3 and AB4E2 types of molecules will also have zero dipole moment, since in each case the resultant of bond moments and the
resultant of the pair moments individually cancel each other.
Example 1. XeF2 (AB2E3)

The structure is linear

The two Xe-F bond moments are equal and opposite which implies that the resultant bond moment in zero. The three lone pair
moment are directed away form Xe and make 120o with each other on the same plane which implies that resultant lone pair moment in
zero.
Example 2. XeF4 (AB4E2)

The structure is square planar

Here too resultant of bond moments is equal to zero which is equal to resultant of lone pair moments which implies that net dipole
moment is zero.
Rule 3. All other ABmEn type of molecules will have a net dipole moment.

Example 3:
Which of the following molecules will have resultant dipole moments?

(a) F2 (b) XeFCl (c) CH2F2 (d) ClF3 (e)

(f) BF3 (g) XeO3 (h)

Solution:
(a)

=0

(b) Lewis structure

(c) CH2F2

VSEPR formula ABB'E3

VSEPR formula

(d)

(e)

(f)

(g)

(h)

(Note: All the N - O bonds are equivalent because of resonance)

Valence Bond Theory, Hybridization and Shapes

Applying valence bond theory to bonding involving pure orbitals
Valence bond theory is an extension of the Lewis approach. In brief, the valence bond theory is the description of bond formation in terms of
the merging of the atomic orbitals in the valence shell of neighboring atoms and of the pairing of the spins of the electrons that occupy these
orbitals. This merging can take place in two different ways.

1. The sigma ( ) bonds

A bond consists of two electrons in an orbit that has cylindrical symmetry about the inter-nuclear axis.
A bond can be formed by the
1. overlap of two s orbitals
2. end on overlap of a s orbital with a p orbital
3. end on overlap of two p orbitals.
Conventionally the bonding or the inter-nuclear axis is taken as the z-axis. The resultant orbital must have z-axis as an axis of symmetry if it
has to be a bond. Hence the p orbitals involved in - bonding are pz orbitals. The figures (a) - (c) depict the formation of - bonds
corresponding to cases (1) - (3) respectively.

Figure (a) - (c) The formation of

bonds.

Note:
1. We will see later that the orbitals involved in bonding need not always be pure orbitals of constituent atoms. They may also be mixed or
hybrid orbitals.
2. -bonds are strong.
3. There cannot be more than one -bond between two atoms.
2.

- bonds

A -bond consists of two electrons that occupy an orbital that has two lobes, one on each side of the inter nuclear axis which lies on a nodal
plane. The -bond has a plane of symmetry which is perpendicular to the nodal plane.
A - bond is formed by the sidewise overlap of (usually) two p orbitals which must be parallel to each other. Since the inter-nuclear axis or
the z-axis must lie on a nodal plane, there are two ways in which a - bond may be formed.

1.

overlapping orbitals

nodal plane

plane of symmetry

py + py

xz plane

yz place

2.

px + px

Fig: The formation of

yz plane

-bonds involving p-orbitals (

xz plane

bond)

Note:
1. -bonds are always formed between pure orbitals.
2. -bonds are weaker than -bonds since the overlap is less
3. Since -bonds are weak, we rarely observe a -bond as the only bond between two atoms. It can be there only if a -bond is also there.
Also the longer the -bond, the weaker is the -bond.
4. Unlike -bonds, more than one -bonds may be there between two atoms.
5. In case of multiple bonds, one of them must be a - bond while the others must be -bonds. Thus in a double bond we have 1 - bond +
1 - bond and in a triple bond we have 1 - bond + 2 - bonds.
6. A -bond cannot be formed with an s orbital.
7.

-bonds may also form between p and d orbitals

or between two d orbitals

as shown below.

Fig. The formation of

and

bonds involving p and d orbitals.

3. Bonding and structure in simple molecules

The structure of the bonds can be identified by using orbitals box diagrams of the electronic configuration of atoms for molecules more
complicated than the cases of H2, HF or F2. (as shown in the figure below)
1. Bonding in H2O

2. Bonding in BeF2

Half filled orbitals for overlap with

orbitals F

4. Shapes of molecules using VB theory. Need for hybridized orbitals

The description shown above cannot explain the shapes as predicted by the VSEPR theory and which are consistent with experimental
observation.
1. Bond angle in H2O
VSEPR prediction 109o28' (actually slightly less due to LP - LP repulsion)

Experimental value 104.5o

Prediction based on above scheme. 90o (angle between the two p-orbitals)
We may explain the angle greater than 90o in terms of repulsion between the H atom of water which carry
how can the angle between two 'p' orbitals be > 90o?

charges. But the problem is,

(Note: This scheme nicely explains the bond angles in H2S (92o) or H2Te (90o) meaning that the additional effect of hydrogen - hydrogen
repulsion is not operative in these cases to any great extent)
2. Bond angle in BeF2
VSEPR prediction
experimental value = 180o.
Since the s orbitals has no directionality associated with it, the above scheme is incapable of predicting the shape of BeF2.
Hybridization of orbitals and VSEPR shapes.
The problems highlighted above can be solved using the concept of hybridization.
1. Hybridization
The concept of hybridization involves mixing of dissimilar atomic orbitals followed by redistribution of energies to form new hybrid orbitals
of same energy.
The number of hybrid orbitals produced is equal to the number of orbitals taking part in hybridization. These hybrid orbitals are distributed in
space symmetrically so as to have minimum electron pair - electron pair repulsion. These hybrid orbitals have shapes in between the
constituent atomic orbitals and they still follow Pauli's exclusion principle and Hund's rule. The bonds formed by hybrid orbitals are generally
stronger due to greater overlapping.
The important characteristics of some of the hybridization are given below.

Steric
Hybridization
number of
central
atom

Number of
hybrid
orbitals
formed

Distribution in
space

Angle

180o

's'
character

Example and shape

BeCl2, Cl - Be - Cl

two

sp

Two

Planar, linear

three

sp2

Three

Planar, Trigonal 120o

four

sp3

Four

Non planar,
Tetrahedral

109.5o

CH4

five

sp3d

Five

Non planar,
Trigonal
bipyramid

1200
(planar)90o
(180o)

PCl5

six

sp3d2

Six

Non planar,
Octahedral

90o

SF6

seven

sp3d3

Seven

Non planar
Pentagonal
bipyramid

720 (Planar)
90o (180o)

Note:
1. The relation between VSEPR shapes and shapes predicted due to hybridization is quite obvious. This is because hybridized orbitals
also take care of - bonds and lone pairs (and not -bonds) and are also distributed in space according to electron pair electron pair repulsion.
2. The determination of hybridization of an atom is very simple since number of hybridized orbital is equal to the number of
valence shell electron pairs which is equal to steric number.
Steric number

Hybridization

sp

sp2

sp3

sp3d or dsp3

sp3d2 or d2sp3

sp3d3

3. In some cases, specially in metal complexes, we may also have a square planar dsp2 hybridization corresponding to a steric number
of 4.
e.g. [Ni (CN) 4]2-, [Pt (NH3)2Cl2], etc.

How the combinations of the different wave functions (orbitals) give rise to the hybridized orbitals of the given shapes?
The 2s and 2p orbitals mix and redistribute to form two new equivalent hybrid orbitals each having 50% s and 50% p character. This
type of hybridization is called sp hybridization as it involves only one s orbital and one p orbital. Since the p orbital is directed along
one axis and the s orbital is spherical, both the sp hybrid orbitals must lie along the same axis as that of the p-orbitals used, and the
angle between them must be 180o. Thus BeF2 molecule should be linear and have zero dipole moment both of which are also
observed.

In the formation of BF3 or BCl3, B the central atom, has 1s2 2s2, 2px1 electronic configuration. In order to form three equivalent bonds
first we promote one 2s electron to the vacant 2py orbitals and then hybridize 2s 2px and 2py orbitals to get three new equivalent sp2
hybrid orbitals lying in xy plane and having an angle of 1200 to each other. These hybrid orbitals will have one third s and two third pcharacter and the type of hybridization is sp2 or trigonal hybridization. Thus BF3 molecule should be planar and being symmetrical
should have zero dipole moment as is actually observed.

In CH4 or CCl4 the central atom C has the electronic configuration 1s2, 2s2, 2px1 (Hund's rule). In order to form four equivalent bonds

we promote one 2s electron to vacant 2pz orbital and then hybridize 2s, 2py and 2pz orbitals to get four new equivalent sp3 hybrid
orbitals distributed in 3 dimensions and having an angle of 109o 28' to each other. This type of hybridization is sp3 or tetrahedral
hybridization as it results in distribution of hybrid orbitals towards the corners of a regular tetrahedron. Thus CCl4 molecule will be
non-planar and still being symmetrical should have zero dipole moment. This is also observed experimentally.

We can in a similar way see how the symmetry of the participating orbitals is related to the symmetry of the distribution of hybridized
orbitals even in other cases.
Contributing pure atomic orbitals

Hybridization
type

Geometry

dsp2

square planar (xy plane)

dsp3 or sp3d2

trigonal bipyramid (three on xy plane two

along z axis)

d2sp3 or sp3d2

octahedral (four on xy plane two along z axis)

sp3d3

pentagonal bipyramid (five on xy plane two

along z axis)

2. Bond angles different from standard hybridization angles

Experimentally observed bond angles are often different from the standard angles between hybridized orbitals. We may explain there
variations based on.
1. lone pair repulsion,
2. size of the central atom,
3. electronegativity of the central atom and hence the polarity of bonds involved.
How does the angle between hybridized orbitals and the 'size' (or length) of hybridized orbitals depend on the type of
hybridization?
If you look at the table given above, you will find that with each type of hybridization we have given the value of 's' character. The
assignment is based on the fact that if 'n' orbitals are hybridized and one of them is ans orbital, then each of the hybridized orbitals

's' character.
will have
You will also notice that as thes character of the hybridized orbitals decrease, the angle between the constituent orbitals also
decrease. Since the angle between hybridized orbitals in also the bond angle (if the orbitals are of bonding electrons) we can say that,
bond angles increases with increasing 's' character of hybridized orbitals e.g.
F - Be - F angle (180o) > F - B - F angle (120o)
Be in BeF2 is sp hybridized
B in BF3 is sp2 hybridized

50% 's' character

33.33 % 's' character.

Another related factor is the 'size' of hybridized orbitals. Thes orbitals are spherical and shorter than the lobe shaped 'p' or 'd' orbitals.
Hence,
The size of orbitals decrease with increasing 's' character of hybridized orbitals
If the size of a hybridized orbital participating in bonding in smaller (than another) then, it would give rise to
1. Smaller bond length
2. Higher bond energy and

3. Higher electronegativity.
Example 1.
Consider the compounds C2H6 and C2H4

(C - H)1 is longer than (C - H)2 (sp3 orbital longer than sp2)

(C- H)2 is stronger than (C - H)1 (shorter bond has higher energy)
Carbon in C2H4 has higher electronegativity than the carbon in C2H6 (shorter orbital implies higher electronegativity)
The bond angles are in the order of H2O > H2S > H2Te. Since the angles of all are less than 109o28', the bonding orbitals have less 's'
character (that means the non bonding orbitals will have greater s - character). The variation in bond angles is because of the variation
in amount of 's' character in the bonding orbitals. In H2Te the bonding orbitals are almost pure p-orbitals and hence the angle is 90o.

Multiple Bonds and Multicentre Bonds

Bonding in molecules having more than one central atoms - valence bond description of multiple bonds.
In such molecules, the hybridization of the different atoms have a profound effect on the structures, shapes and dipole moments. This is
because there is now the additional possibility of the formation of multiple bonds.
(a) Applying valence bond theory to multiple bonds
Let us consider the bonding in N2F2 using the valence bond theory.
The Lewis structure is

The steric number of N is 3 in each case. This implies N atoms are sp2 hybridized. Two of the three sp2 hybridized orbitals will
correspond to -bonding electrons and the third will correspond to a lone pair.
The unhybridized 2p orbitals of the two nitrogen atoms may now form the -bond. The valence bond scheme is shown below:

(b) Shapes of molecules involving multiple bonds

Groups connected by

bonds may rotate with respect to each other, but a

The orbital diagrams and shapes of C2H4 and C2H2

-bond 'locks' or restricts such rotation.

The bonding in C2H4 may be analyzed in the same way as that in the case of N2F2. The result may then be represented in the form of
orbital overlap diagrams as shown in figure.
Figure 1(a) shows the overlaps of the - frame work
Figure 1(b) and 1(c) shows how the sp2 hybridized planar CH2 units may rotate with respect to each other.
Figure 1(c) shows how the - bond formation takes place only when the two 2p orbitals on the two carbon atoms are parallel to each
other. When the - bond forms, the two CH2 groups become co-planar and the molecule takes a rigid planar shape.

Fig. 1. (a) - (c) orbital overlap diagram of ethylene showing

and

bonds separately.

If we analyze the C2H2 molecule we will find that the molecule is completely linear. The orbital overlap diagrams of C2H4 and C2H2 are
given in figure 2.

Fig. 2. Orbital overlaps diagrams of (a) ethylene and (b) acetylene.

(c) Multiple bonds, conjugation and planarity
Conjugation of bonding electrons mean that the constituent p-orbitals must be parallel to each other. Only then can we have
alternative schemes of bond formation. We had seen earlier that H2C = C = CH2 (allene) shows no resonance since there is no
conjugation between the two -bonds. We may understand the reason from the orbital diagram shown in figure3.

Fig. 3.

-orbital diagram in CH2 = C = CH2.

The molecule is not planar and the two CH2 groups are perpendicular to each other. The two
are not conjugated.

-bonds are on perpendicular planes and

The figure 4 shows the -orbital diagrams in (a) butadiene and (b) benzene showing that the p-orbitals involved in
parallel and conjugation is possible.

Fig 4. The

-bonding are all

orbital diagram in (a) CH2 = CH - CH = CH2 and (b) C6H6 where all p-orbitals are parallel and conjugation is possible.

Electron deficient molecules and multi-centre bonding

Elements of groups 13 have only 3 valence electrons and hence cannot complete their octets by forming covalent bonds. Such molecules
are called electron deficient compounds . There are a number of ways in which electron deficient compounds try to attain stabilisation.
One of them is formation of multicentre bond formation. In this rection we will do a comparative study of all the different methods.
BF3 stabilizes by the p -p 'back donation' of electrons from F to B by resonance.

when we go to AlCl3, both Al as well as Cl belong to a higher period than B and F respectively. The Al-Cl -bond is much longer than
the B-F -bond. The p -p back bonding in AlCl3 will be far too weak to lead to stabilisation. AlCl3 solves this problem by forming
a dimer involving the coordinate bond formation by bridging chlorine atoms as shown below:

There are four electrons which bind the bridging chlorine atoms to the two aluminum atoms. This may also be 'imagined' as a three
centre four electron bonds.
Three centre two electron bonds is observed in boron hydride. Unlike F, hydrogen does not have any lone pairs for back bonding.
Hence BH3 cannot be stabilized either in the BF3 manner or in the AlCl3 manner. The bonding is explained using the concept of
hyperconjugation as follows:

3centre - 2electron bond

Another electron deficient molecule which stabilizes in a manner similar to that of AlCl3 is BeCl2. BeCl2 forms a polymer instead of a
dimer as in the case of AlCl3.

Bond Length and Bond Energy

Bond Length
Bond length is the average distance between the centers of two atoms joined by covalent linkage. It is generally expressed in
Angstrom,
or picometre, pm (1 pm = 10-10 cm = 10-12 m). Generally, the bond length is the sum of
atomic or covalent radii of two atoms bonded together. Bond length therefore depends on:
(1) Covalent radii of constituent atoms: For example, HI > HBr > HCl > HF.
(2) Presence of bonds: A double bond is shorter than a single bond and a triple bond is shorter than a double bond. For
and in C C, the bond length is 1.2
.
instance, the bond length in C-C is 1.5 , in C = C it is 1.33
(3) Type of Hybridization: Bond length decreases with an increase in the s character of a hybrid orbital. Thus,
Bond type (C-H)

Bond length

(4) Inductive Effect: Greater the inductive effect shorter will be the bond length between similar atoms having same hybridization.

(5) Resonance Effect: In molecules exhibiting resonance, the single bond lengths decrease while the double bond length increases.
Thus, in
1,3-butadiene C1-C2 and C3-C4 bond length is 1.35

, which is greater than the bond length of an isolated double bond, which

measures 1.33
. The C2 - C3 bond length is 1.47
, which is less than that of a C-C single bond, which is 1.54
.
In case the resonance is between identical contributing structures, all bond lengths become identical. In benzene, for example, all C-C
bond lengths are 1.39
, which is somewhere in between the lengths of single and double bonds. Similarly, in nitro compounds, both
N-O bonds have identical bond lengths, which is between the length of a single and double bond. In carboxylate anion also, both C-O
bond lengths are identical and lie between those of single and double bonds.
Example 12
Assign proper bond lengths to the following bonds (a to h) by selecting values from the

Solution
We have:
(i) C-H bonds a, e and h
(ii) C-C bonds b, c and f
(iii) C = C bond d
C bond g.
(iv) C
Thus, we have four groups of bond lengths. In the pool we have four groups corresponding to C-H, C-C, C=C and C
respectively.
(a) 1.06, 1.08, 1.10
(b) 1.46, 1.50, 1.53
(c) 1.34
(d) 1.21
This is based on the following factors:
(i) C-H bonds are the smallest.
(ii) Among carbon-carbon bonds C-C > C=C > C C.
Within group (i),

Hence a = 1.10 , e = 1.08

Within group (ii),

and h = 1.06

Hence b = 1.53
, c = 1.50
We are left with,

and f = 1.46

d = 1.34

and g = 1.21

C,

Bond Energy
In the formation of a covalent bond, energy is released. The same energy will be required to break the bond and is referred to as bond
energy. It is a measure of bond strength. The same bond in a different structural environment will generally have different bond energy
values. Therefore, we use an average of these values obtained from the study of a large number of compounds having the same bond.

In diatomic molecules the bond energy may be directly obtained, as the energy required to break bonds in one mole of the molecule.
But in polyatomic molecules, for example H2O, the actual bond energies for the same type of bonds are different for first and second OH bonds. Therefore the bond energy of -OH bond is taken as an average of the two values. Similarly, in NH3 the actual N-H bond
energies are different and again, an average is taken to determine the bond energy of N-H. Similarly, in CH4, the four C-H bonds have
different values for bond dissociation energy and an average of these is used as the bond energy of CH bond. Thus, bond energy values
are an average of the various values of bond dissociation energies of the same type of bonds present in the molecule.
Generally, the bond energies depend on:
bond is more than that of bond.
(1) Bond energy for sigma
(2) Amongst the various sigma bonds formed by hybrid orbitals, the bond energy increases with increase in the s-character of the
hybrid orbital. Thus, the bond energy of a sigma bond formed by sp-sp overlap is greater than that of a bond formed by sp2-sp2 overlap
which in turn is greater than that of a sp3-sp3 sigma bond. Similarly, the bond energies of sigma bond are in the following order:
sp-sp > sp-sp2 > sp-sp3 or
s-sp > s-sp2 > s-sp3
(3) Multiple bonding increases the bond energy i.e. bond energy C-C< C C < C C and N-N < N = N < N N.
This is due to the presence of additional bonds along with a
bond.
(4) Generally, the bond energy values decrease as the size of the atom increases.
Thus, H-H > Li-Li >Na-Na > K-K
and HF > HCl >HBr > HI.
Similarly, C-C > Si-Si > Ge-Ge > Sn-Sn.
But in the series of the group 15, 16 and 17 of the periodic table, the bond energies are in the following order:
Group 15: N-N < P-P > As-As > Sb-Sb
Group 16: O-O < S-S > Se-Se > Te-Te
Group 17: F-F < Cl-Cl > Br-Br > I-I
The first member should have the highest bond energy but the bond energies of these single bonds decrease due to the presence of 1,2
and 3 lone pairs of the electrons, respectively. But in P-P, S-S and Cl-Cl vacant d-orbitals are available which can interact with the
lone pair on another atom to form
p -d bonds. This is called back bonding and it increases the strength of the bond.
This is, in fact, responsible for a large number of related interesting facts. The very low bond energy of F2 is responsible for its high
reactivity. The low energy of N-N or O-O single bonds is the reason why N does not exist as N4 (analogous to P4) and is not a solid, or
why O does not exist as O8 (analogous to S8).
Similarly, the strength of single C-O is less than Si-O because of the interaction of the lone pair of oxygen with empty d-orbitals of Si
which is not possible in C. This explains why multiple bonding C-O makes CO2 gas, while the strength of Si-O bond results in a large
polymeric network of silica which solidifies.
The strength of bonds is in the order Al-Cl> Al-Br> Al-I, again because of the interaction of the lone pair of halogen with the vacant p
orbital of Al. This results in the strength of aluminum halides such as Lewis acids to be in the order AlCl3 < AlBr3< AlI3.
Given below is the table of average bond energies:
Single bond

kJ mol-1

Single Bond

kJ mol-1

Multiple Bond

kJ mol-1

H-H

436

C-F

489

C=C

614

H-C

413

C-Cl

339

H-N

391

C-Br

285

C=O

H-O

463

C-I

218

H-S

367

N-N

163

C=N

H-F

567

N-F

278

H-Cl

431

N-CI

192

H-Br

366

O-O

146

O=O

H-I

298

O-F

193

C-C

348

O-CI

208

C-N

305

S-S

255

C-O

358

F-F

159

C-S

272

CI-CI

242

Br-Br

193

I-I

151

839
745
891
615
418

945
498