Molecular Orbital Theory

Molecular orbital Theory for Cyclic

Molecules
• Generator Orbitals
Simple cyclic Hn molecules
Conjugated cyclic polyenes CnHnz
(aromatic hydrocarbons) – Pz atoms overlap to form ring structure.
- Dnh point group – where x and y directions are indistinguishable.

- This in distinguishability results in many of the MOs falling in doubly

degenerate pairs of equal energy.
• Increasing vertical nodal planes
A quick way of generating the MOs of cyclic (and other compact) molecules is known
as the Generator Orbital (GO) approach. In this approach, it is recognized that the
vertical nodal planes of the MOs of a molecule, which must pass through the center
of the molecule, match the vertical nodal planes of appropriate atomic orbitals of a
real or imaginary atom situated at the center of the molecule.
For a two dimensional ring of n atoms, there will be n Mos.
Successive MOs, and the GOs used to generate them, will have
increasing numbers of vertical nodal planes: 0, 1, 1, 2, 2,

An xz nodal plane generated by a Py generator orbital is doubly

degenerate with a corresponding nodal plane in the second dimension,
the yz plane generated by the Px GO.

Example : Cyclo H3 molecule - 0, 1 and 1 nodal

planes – s, Px, Py
Therefore the three  molecular orbitals of cyclo- C3H3 have the same number of vertical nodal
planes as those of cyclo-H3, but also have one horizontal nodal plane
each.
Draw and label the MOs and the energy level diagram of the conjugated cyclic
polyene, C4H4, cyclobutadiene. Predict its number of unpaired electrons.

Generator orbitals, MOs, symmetry labels, and energy level diagram for the  electrons of
cyclo- C4H4. The drawings of the MOs show tiny generator orbitals at the centers, but do
not show the lobes of opposite sign for each MO, which fall below the plane of the paper.
 Orbital Symmetry Rules for Concerted Reactions
• In organic chemistry, we use Push arrows to show a smooth
flow of electron pairs around a series of bonds as species
react.
• Concerted reactions occur in single step.
• The frontier orbital concept has been extended to allow us
to predict whether such a concerted reaction between two
molecules or polyatomic ions can occur readily, or whether
it will have a high activation energy.
• If the activation energy is high an alternate mechanism may
apply, which involves several steps and intermediates and
perhaps free radicals instead of acids and bases.
 Orbital Symmetry Rules for Concerted Reactions

1. As the reactants approach each other, electron

density must flow from the HOMO of the donor
to the LUMO of the acceptor.

2. The HOMO of the donor and the LUMO of the

acceptor must approach each other so that they
have a net positive overlap, and they must be
relatively close in energy (within  6 eV).
3. The net effect of HOMO → LUMO electron
transfer must be to make the bonds to be the
formed and weaken the bonds to be broken.
Molecular Orbitals for Dnh Complexes
• Polygonal Molecules.
• Central generator atom is the real atom.
• Outer atoms around the polygon use their
valence orbitals to bond, not to each other,
but to the real central atom.
• Generation of MOs of BH3 from cyclo-H3
• The MOs of cyclo–H3 – TASOs
• Bond is formed only if both belong to the
same irreducible representation.
Molecular Orbitals for Dnh Complexes
B2S – TASO H1S B2Px – TASO H1S B2Py – TASO H1S

B2Pz – NB

BH3 - Electronic Configuration – (a’1)2 (e’)4

Molecular Orbitals for Dnh Complexes
B2S – TASO F2Px B2Py – TASO F2Px
B2Px – TASO F2Px

Other 2 TASO F2Pz - NB

B2Pz – TASO F2Pz

BF3 - Electronic Configuration – (a’1)2 (e’)4 (a2”)2

 Molecular Orbitals for Dnh Complexes
P3S – TASO F2Px P3Py – TASO F2Px
P3Px – TASO F2Px

Other 2 TASO F2Pz - NB

P3Pz – TASO F2Pz

PF5 - Electronic Configuration – (a’1)2 (e’)4 (a2”)2 (a1nb)2

 Triiodide Ion (I3-)
I (53) – 5S2 5Px2 5Py2 5Pz1
It is 3C – 2e Molecule
Each I atom has 4 valence orbitals (5s, 5px, 5py, 5pz), making a total of 12 frontier
orbitals, and the I3- anion has 22 electrons.
We can simplify the problem by recalling two periodic trends:
The s-p orbital splitting is large, relative to the bond energy, after the second row
of the periodic table. Thus, the 5s orbital is low in energy and too contracted to
make bonds with its neighbors.
π-overlap of 5p orbitals is very weak, so the 5px and 5py orbitals will also be non-
bonding.
This leaves only the three 5pz orbitals to make
bonding/nonbonding/antibonding combinations. Again, the problem is entirely
analogous to ozone or H3-.
 Triiodide Ion (I3-)

Counting orbitals we obtain 9 lone pairs from the nonbonding 5s, 5px, and
5py orbitals, as well as one bond and one lone pair from the 5pz orbital
combinations above.
The total of 10 nonbonding pairs and one bond accounts for the 22 electrons in the
ion.
The non-bonding 5pz pair is localized on the terminal I atoms, giving each a -1/2
formal charge.
 316 all the
three molecules are

shell. Thus O-N-0 bonda

number of electrons)
in their
respective
angular
has
(V-shaped)
structure.
ngle inN
(ood molecules = 118°.
molecules. Each of th se
molecule
in CI0, is odd-electro.
o - C H O angle
an
tron
molecule
molecules
and each of the
molecule 132° molecular orbital theory,
=

3-electron
According to bonds and
one
0
2-clectron of the
Since it
contains three
bond order of each
Thus the due to the N132
bond (See Fig. 10.25). order of 0.5 is
3.5. Bond of
molecules is equal to due to the presence
3-electron bond. It is molecules
presence of one that these
in 3-electron bond molecule the
one unpaired
electron
In case of NO2
(a) (b) (A=ClBn
show paramagnetic
character localised
bond is more
Ig. 10.25: Angular
structr.
in 3-electron s of
unpaired electron present
molecules
when two NO, NO2 molecule [shown at (a)], Co
N-atom and hence
on the central
E link- and BrO2 molecules [shown
with each other, they comoin The
arebrought in contact or N,O4.
and form nitrogen tetroxide,
O,N NO2 -

N- N o-bond, Th
two
of
molecules in N204
NO%
moleçule takes place through NO
ing to dimerise to
form N2O4 molecule.)
molecule has a tendency and reactive, and has marked enl
molecule is also paramagnétic
But, Like
unlikeNO
NO>, CIO2 hacCIO,
molecule, no tendency to dimerise to form Cl%O4. This is perhaps due to the
the
molecule is less localised
present in 3-electron bond in CIO,
that the unpaired electron shorter C C - 0 bond lengths(
3-electron bond accounts for the
central Cl-atom. The presence of
- 0 bond length = 1.49)
molecules. Like NO2, CI0, and Bro
(iü) Tetratomic molecules: Structure of CIO, and Clh0, electrons (=7+6
contains odd number of
CI03 molecule is also odd-electron molecule, since it
an
which is localisedou
CI0, molecule has one unpaired electron
x 3 25) in its valence-shell(Thus shows paran
on Cl-atom,
electron ClO,
the central Cl-atom. Due to the presence of one unpaired
molecules come in contact with each other they combine
agnetic character and when two ClO3 or Cl,0g which can be represented as O0,C-CIO,
together to form dimeric molecule, (CIO3)2 the sharing of two unpaired electrons ontwo
Thus ClCI bond in Cl,0, molecule is formed by
C-atoms of two Cl0, molecules. Thus we find thatin
Cl,O molecule all the electrons become paired andhence
this molecule is diamagnetic) The above discussionshows
O=C1 :0-CI-Ç=0: that the structures of ClO3 and Clh0 molecules cane
shown as depicted in Fig. 10.26.
:0: :0:
Properties of odd electron bonds/molecules or ions
a) (b) ) One-and three-clectron bonds are weaker than
Fig. 10.26: Structure of CIO3 [shown at normal covalent bond (two-electron bond) and hence n
(a)] and Cl0s [shown at (6)] molecules. bond length of one-electron bond is greater than thal o
wo-electron bond, e.g. H-H bond length in H, molecule [H Hor H-H] is 0.74A while
bond length in H ion, H-HJ* which contains one-clectron bond is 1.06A. The bond lenguof
three-electron bond is intermediate between that of a doublebond and a triple bond.
almos
(i) Odd electron bond is generally formed between the atoms which have similar or
ffereoce
similar electronegativity. Odd electron bonds are not stable, if the electronegativiy
between the atoms involved is large.
(ii) Molecules having odd electron bonds are paramagnetic, coloured and very r a a
NO is paramagnetic, brown in colour and so reactive that it dimerises to form N,O, e
agnetic character of such molecules is because of the presence of one (e.g. NO, N , ; °?
NO, CI0,) or two (eg. NO", O,Junpaired electron in three-electron bond(s).
Hydrogen Bond
What is hydrogen bond?
twee

Hydrogen bond or hydrogen bonding is defined as the electrostatic force of

attracu
 Chemical Bonds
2erent ypes of 317
(which is already covalently bonded
-a and highly electronegative atom to a highly electrone gative atom like N, 0 or F in a
a
olec le of different substance or present in a molecule of the same
substance or present
present within
eeen molecules ot the same substance
the the same molecule. Thus H-bond is
formed
substances
ifferent substa (see Fig. 10.28) or between
(see Fig. 10.27) between the molecules of
or
10.29). H-bond is represent by a dotted line. two atoms present in the same molecule (see F1g.

H-N-H-NH-N H -H -H
H H H
H H

(a) (b

1.5 A 107A

o=¢
A .

2.55A H 146 H H-c121A

F
2.70A
c) (d)
HO-
N=0-OH -N=0OH N=0

(e)
F10.27: H-bonding taking place between two or more molecules of the same substance
(a) between
several molecules of NH3 : Formation of (NH3)x cluster
(b) between several molecules of H20
Formation of (H20)x cluster (c) between several molecules of HF: Formation of
between two molecules of formic acid (HCOOH), (HF)x cluster (d)
leading to the formation of a dimer,
(HCOOH)2. (e) between several molecules of p-nitrophenol.
CH
Q-HO= CI CH
R
H CH CI--H0=C OH Cl-H-0
H-O Cl CH
(a)
(d)

b)

CH,
H-c=C-H-0 HO N=0H-0HO =o-
CH
(e) substances (a) between water (H20)
Hbonding taking place between the molecules of different
and water (H20) (c) between chloro-
(CH3CO.CH3) (b) between pyridine (CsHsN)
acetone between HCI and dimethyl ether (HC.O.CH).
(d)
(CHCl] and fatty acid (RCOOH)acetone
om (CH3.CO.CH3) ) between p-nitrophenol (OH
e) between acetylene(HC = C-H) and
-CsH4. NO2) and water (H20).
 Advancea
Vol
318
H
C C 0-H

H
(c) (d)
(b) (a) betwecn Hat
(a) between the atoms
within the same molecule
between Cl-atom and of O
Fle. 10.29: olace
Hhnding taking place belwe nin C-hydroxy
o-hydroxy
benzaldehyde (b)
f OH grou NO
and O-atom of Om
grup
andO-atom ofCHO group
(c) between H-atom
of OH group O2 group in
0-atom of COOH group in
CO
OH group in ochloruphenol
onitrophenol ()
between H-atom of
OH group and ohydroxy
benzoic acid.

Types of hydrogen bonding Intcr moleculer Hbo

H-bonding
ater-moleculer
(Association or polymerisation).
substance or between
bonding
between scveral molecules of the same Severa
is that which takes place er-mere molecules of the
molecules of different substances. In
this type of H-bonding, to same
or associated and form a large cluster. Th
substance or different substances get polymerised
Examples given in Fig. 10.27 are h
fomation of a cluster is called association or polymerisation.
between the molecules of the same substan
examples of inter-molecular H-bonding taking place
of inter-molecular H-bonding taking place he.
while those given in Fig. 10.28 are the examples
twoen the molecules of different substances.
2. Intra-molecular or internal H-bonding (chelation). Intra-moleculer H-bonding is tha
which takes place between two atoms prescnt in the same molecule. In this type of H-bonding, a
planar 5-membered or 6-membered chclate ring is obtained. Examples given in Fig. 10.29 are the
examples of intra-molecular H-bonding. In this type of H-bonding, the interacting atoms should be
placed in such a way that there is minimum strain during the closure of the ring. Thus the anti form
of pyridine-2-carboxaldoxime () contains intra-molecular H-bonding while the syn form (1) can
not have intra-molecular H-bonding, since the lone pair of electrons on N-atom in the pyridine ring
is not oriented towards he OH group of the oxime. (See Fig. 10.30).

H
-H

( (1)
Flg10.30: Anti form of pyridine -
2- carboxald oxime has
is not possible in syn. form.
intra-molecular H-bonding while this bondung
Nature of bhydrogen bond: How is
As
hydrogen
bond formed?
an
example, let
explain us the
formation of H-bonding in several
luonde (HIF). know that, due to high molecules of ny n
We electronegativity
which is represented as and
molecule is a polar covaent bond small size of F-atom, H-To
dipole. Now when several such dipoles come H** F. Thus HF molecule -

H)in oneH*-P dipole is auracted towards to cach other, H-atom carrying posiuve
nearer bena
P dipole and gets attached with F-atom carrying H
it (ie., with
hydrogen bond. The ultimate result of H-bonding Fatom)
is that abynumber negative charge
of HF force
molecules (i.e.
get ass hisiscald
clectrostatic of attractiuon
and form alarge
cluster of molecules which can be wiuog
get associated
gesther

between several HF molecules [ie., the formation represented as (HF), Thus the fomauon (H-bonds

(HF), cluster] can be shown as:

&+
&+8 8+

H-H-H:H-
 Chemical Bonds
types of
Diferent
above discussion we can say that hydrogen bonding is simply dipole-dipolc
Onthe basis of the
attractions.
attraction. This dipole-dipole attraction is stronger than other dipole-di
anditions for the formation of hydrogen bonds
Following conditions must be satisfied for the formation of H-bonds in compounds.
atom. The nolecule having H-bonds should
have a
) Presence of highly electronegative
N, O or F directly linked to H-atom by a covalent bond.
ohiv clectronegative atom like
with small size. The highly electronegative atom should be of smal
) Presence of the atom interaction
eize so that B-H bond (B N, O
= or F) may be highly polar (B*-H)
and a strong
almost
occur. This explains that, although O and CI both have
several such dipoles may
wcen
betw
3.5, Cl = 3.0), O-atom, due to its smal size (0= 0.73A, CI
=

the same electronegativity (O =

lines of argument, it can be

a99A) fonns H-bonds while C-atom does not do so. On the same so. Their electronegativity values
explained that O and N can form H-bonds but S and P cannot do
and covalent radii are as N 3.0, 0.76A; P 2.1, 1.06Å; O =3.5, 0.73Å andS 2.5, 1.02A.
= = =

Strength of H-bond
attraction and not a chemical
H-bond is a weak bond, since it is merely electrostatic force of
increase of the electronegativity of the atom
bond. The strength of a H-bond increases with the
0 and F-H F. Now since the
attached with H-atom by a covalent bond inN-H N, O-H
in N-H. N («g.
electronegativity of N, O and F is in the order N<0 <F, the strength of H-bond
is also in
inNH molecules), O-H.. O (eg. in H,O molecules) and FH F (eg. HF molecules)
in

thesame order, i.e. N-H N(=8.37KJ/mole) <0-H. O0 29.29 kJ/mole)<R-H.F(=41.85

but weaker than a covalent bond and an
KJmole). H-bond is much stronger than van der Waals forces covalent bond <
van der Waals forces < H-bond <
ionic bond. The order of strength is, therefore, as
ionic bond.
of the compounds containing hydrogen bonds
Efect of hydrogen bonding on the physical properties
number of physical properties of hydrogen
Although H-bond is a weak bond, it affects largebelow:
a
are given
bonded componds. Some of these properties of
1. Variation in the boiling points of the binary hydrogen compounds of the elements
of binary hydrogen com-
groups VA, VIA and
VIIA. Molecular weights and boiling points (°C)
VIA and VILA are given in Table 10.6.
pounds of the elements of groups VA,
hydrogen compounds of
Table 10.6: Variation of the boiling points (°C) of binaryVII A.
the elements of groups VA, VIA and

Group VI A Group VIllA

Group V A
Mol. Wt. B.P. (C) Hydride Mol. Wt B.P. (C)
Hydride Mol. Wt. B.P. (C) Hydride
+100.0 HF 20 +19.4
18
NH 17 34.5 H,O 36.5 -85.0
33 - 60.7 HCI
PH 34 87.5 H4S - 67.1
41.5 HBr 81
81
AsH 78 - 62.4
H,Se 128 - 35.0
130 - 1.8 HI
SbH 125 - 18.4
HTe
in each group, the
the increase in the molecular weight of the hydrides
We know that with same direction (ie., down-
Waals forces of attraction also increases in the
magnitude of van der of the
the magnitude of van der Waals forces the boiling points
Wards). Due to the increase in ie., the boiling points should be in the
order 1st member
downwards,
nydrides should also increase
member. But we see from the
table that as we move from the
Znd member < 3rd member < 4th decreases and then the
S the boiling point, instead of increasing,
member to the 2nd member, member.
St increasing trend on moving from 2nd to 4th
001ling points show the expected of the Ist member is higher
than that of 2nd member in
Explanation. Why the boiling point have much more
the basis of the fact that since N, O and F
ach group can be explained and the electronegativity values of other elements are close to that of
on

ectronegativity than H atom

 2.3,
2.5, Se
.1,F40,
=

O3.5, S =

1.9, inter-molecu
320 2.0, Sb
=

H-atom (H=2.1,N=
3.0,
and I
2.5), NHg,=
H,O
P= 2.1;
As =

and HF

ofhydrogen
molecules

bonding is
formed.
undergo
absent in other
In order to
hu
H-b
hydrogea
hyo
molecules. It in
and oonda
= 28
Cl 3.0, Br of this type clusters are
is require
and (HF),
hence
o c c u r e n c e

while the (H,O), more

heat energy r e s p e c t i n d
bonding that (NH),, their
clusters
and HCl
m o l e c u l e s in H2S
H-bonding
because of PH3,
HF
H,O andm o l e c u l e s are higher than
those of heat of vaporisation of.
holding NH, fusion and YdroP
points of these heat of H - a t o m of
hydrogen
boiling
points, boiling
points, derivatives.
When
derivatives. The
Com
2. Melting and their methyl we get
methyl
or
groups, extent of H-bond
bonded
compounds
by one, by CH, decrease in the
he
are replaced,
one
derivatives.
With the for methyl derivos
pounds methyl vaporisation
decreases in and heat of o
H-bonding heat of fusion the melting pointe
points, is evident from
boiling This fact
melting points,
compounds) also decrease.
or H--OH,
CHGOH and (CH,).O. CH,0 given as
hydrogen-bonded of H,0
of fusion and
heat of vaporisation boiling points ( H
points, heat -97.8, (CH3),0 =-138.3; CH.OH 20
CH,OH
=0.0, -23.7;
=

(K mol): H20
6.0, =

Metring points (°C): H,O heat of fusiom

(CH),0 CH3OH 35.6, (CH,)0=21
=

100.0, CH,OH 64.7,

=
mo); H,0 40.6, = 1.5.
=

vaporisation (KJ donot boil but decom

(CHy,O=49; heat ofcompounds namely H,SO4, H,PO, and HgBO, ompose a
Hydrogen-bonded On the other hand the methyl dederiva
respectively with the loss of water.
and (CH3)3BO; which are non hvdroo
185°C
340, 213°C and (CH,),PO,
tives of these compounds viz (CH3)»SO4, and 65°C respectively T
boil at lower temperatures which are 188°C, 193°C
bonded compounds similar trend in their boiling points (HE
and HNg-CH,Ng also show the
pairs namely HF-CHF
19.5°C, CHF=-78°C; HNg=37°c, CHJN 20°C).
=

3. Comparison between the boiling points of CH, NH3, H,O

and HlE The boiling points of
< AF = (=+19.4°C
thesehydrides are in the order of: CH, (= -161°C) < NH, (=-34.5°C)
H,0 (=+100°C).
Explanation. Due to very low electronegativity of C-atom (=2.5), there is no possibility of the
formation of (CH), cluster. In fact, in CH, several molecules are linked together by van der Wals
forces which are very weak, weaker even than H-bonds. It is due to the presence of weak van der
Wals forces in methane molecules that methane has the lowest boiling point. Now, due to the high
tronegativiy and small size N, and F atoms, all the three molecules viz. NH, H,O and HF
have H-bonding. The way in which H-bonds are formed in these molecules as
shown in Fig. 10.27,
suggests that, due to the presence of one lone pair of electrons on N-atom and three H-atoms
attached covalently with N-atom, each
NH molecule can form four H-bonds with other four NH
molecules. Similarly, due to the presence of the lone
attached covalently with O-atom, each pairs of electrons on O-atom and two H-atoms
with other four H,O molecules. HO molecule, like NH molecule, can form four H-bonas
But, since F-atom, in HF
and one H-atom attached with
it, each HF molecule can form
molecule, has three lone pairs of elecro
molecules. Thus the
strength of H-bonding, which is only two H-bonds with two other
bondsformed, in NH3, H,0 and HF molecules should directly be
proportional to the number o
since N-atom has the lowest value of in the order of NH,> H0>
HE
=
4.0), the strength of
H-bonding in
electronegativity
of all the three
atoms (N 3.0, O3
Now since the NH,
of two H-bonds in molecule becomes minimum of all the three
3.
strength
the order of the HF molecule is mo
strength of
boiling points of these hydrides H-bonding NH3, HO and HFless than that of four H-bonds in ngn
in
assaid aboe, the order of are also in
this order. Now molecules is NH, < HF < H
HF <HO. the boiling points of all the four since CH has the lowest bol
4.
Solubility of hydrides is in the order :CH*** NH
e formation
of organic compounds. The
HO but alkanes H-bondsare not:
between H,O moleculessolubility of organic
and
is due to
compounds H2Oli
in
foming H-bonds with This is because of the reasonorganic
alcohol molecules can H,O molecules and hence are
compounds. Alcohols
that alkane
soluble

aableo
form H-bonds with not molecules are no
h
H,0 moleculesmiscible
and
with HO. On
heh other
hence are miscibie H
HO
 321
types of Chemical Bonds
Diferent
leohols having alkyl groups with three carbon atoms are freely soluble in H,O. With the increase
he number of C-atoms, the solubility decreases, i.e., it is only lower alcohols (e.g. CH,OH
H.OH.C,H,OH etc.)which are freely soluble in H,0. (CH),O forms H-bonds with H,O (H-O-
CH
) and hence is completely miscible with
HO CH, H,O whereas (CH,)hS which is not
eanable of forming H-bonds with H,O is partially miscible. Benzene (C,H,) is partially miscible in
H.O while pyridine (CsHgN) is miscible in all proportions due to strong H-bond formation through
the lone pair of electrons residing on N-atonm in C<HN molecule
The solubility of some compounds in non-aqueous solvents like CHCl, HCI, (CH,),CO etc.
ean also be explained on the basis of H-bonding. For example (a) organic fatty acids (RCOOH)
disolve in chloroform (CHCI3) due to the formation of H-bonds between polar H-atom of C - H
H
R
bond in chloroform and O-atom of coOH group. Cl-CH 0=CKOH (b) HCI

CH
dissolves in (CB3)2 due to Cl-H. o bond formation. (c) acetylene (H-C = C-H)
CH
=C-H 0<
CH bond formation. Here it
dissolves in acetone (CH,.CO.CH,) due to H-C
CH
in HO molecules are
should be noted that acetylene is not soluble in HO, since H-bonds present
H-atoms of acetylene molecule and O-atoms of H,O molecule.
stronger than those formed between and hence is 'squeezed
Thus acetylene is not able to break the H-bonds present in H,O molecule
out, i.e., acetylene does not dissolve in H,0
the attraction between molecules of
5. Viscosity of liquids. Due to inter-molecular H-bonding,
increase in the attraction decreases the tendency of the
hydrogen-bonded liquids is increased. This
since glycerol (CH,OH-CHOH-CH,OH) has three OH
liquids to flow smoothly. For example
glycerol forms more number of H-bonds, i.e., more
groups and C2H,OH has only one OH group, inter-molecular H-bonding and hence its viscosity is
glycerol molecules are associated together by CH,OH-CHOH-CHOH 10 mil-
=
5.97 millipoise,
greater than that of C,HOH(CH;OH
=

lipoise). is that of
than
On similar grounds it can be explained why the viscosity of H,O greater is
the viscosity of CH2OH-CHOH-CHOH greater
GgH,OH (H,0 10.05 millipoise). SimilarlyIt is due to intermoleculer H-bondig between several
=

than that of (CH,)0 ( = 2.33 millipoise). and is highly viscous. Its highly viscous nature makes
HSO, molecules that the acid has high b.pt
the acid a syrupy liquid. VIA and VIIA. First
of the hydrides of the elements of groups VA,
6. Physical state while the remaining hydrides are
of each of these is a liquid at ordinary temperature
nydride groups
since the central atom of each
of the first hydride has high
said that,
ases. We have already these molecules unite together through
inter-molecular H-bonding
ectronegativity and small size, formation of the cluster that these
molecule. It is due to the
form a cluster or an associated central atom of the
and temperature. On the other hand, since the
ydrides exist as liquids at ordinary and bigger size, they are
not capable of uniting
have low electronegativity
maining hydrides exist as gases under normal
conditions.
Eether to form the cluster i.e., these hydrides combination of
This ion is formed by the
Formation ofhydrogen difluoride ion, HF,
ion and HF molecule.
F +HF HF2
 e l e c t r o n e g a t i v i t y ,
gets attached ith H-alor
322
because of itshigh ion can be show as
HF,ion, F
ion, formation
ofHF,
Int th e formation of bond.
Thus the

of HF (H-P
molecule
+H-
by hydrogen HËorHIF
these ions cannot
jons, mbina
ions arewinotth
Br and and H and
Due to smaller
electronegativity of C,
H-bond and
hence HC, HBr, Hi
by KF (This
of HCI, HBr
and HI
molecules

HF can
combine with
is salt F
non-formation of in
-alom
ion that
of HF; due to the non-formation
It is due to the existence other hand,
Tomed. the
salt (acid salt). On with KCI, KBr and
combine
donor) and form K°[HFJ molecules
cannot
HBr and HI by the combination
HBr, and HI ions,
HCI,
The formation of K.HF2J ion of HF
respectively.
K[HCh], K[HBr,] and K[HI,]
and KF can be shown as

KF K + :
H- H-orHE,
On adding we get:
KF HF K'[HF
in which the individual
Structure of molecular crystals. There are many molecular crystals
8. chain
The formation of H-bonding gives
molecules are connected together through H-bonding.
structure (e.g. linear chains in HCN, zig-zag chains in HF, CH,OH, formic acid etc.), sheet stnuc.

ture (e.g. -oxalic acid) or

three-dimensional net work (e.g. 0-H H-Oo oH-O
KH,PO,) to the. crystals. In
some cases the crystals contain
units consisting of dimeric or
o-H-0 0-HO

trimeric H-bonded species. Zig-

zag structure of solid HF has al- H-0 H-0
ready been shown at (c) of Fig.
10.27 and the sheet structure of Fig. 10.31 : Shect structure of a-Oxalic acid
a-Oxalic acid is shown in Fig. 10.31.
9. Comparison between the structures of the crystals of NH F , NH C, NH,Br and NH.
The crystals of NH,CI, NH,Br and NH,I have CsCI
structure below 184.3°C, 137.8°C and
-17.6°C respectively, but above these
structure. The radius ratio value of
temperatures the crystals of these halides have Na
should have CsCl structure. Instead,
NH,F (= 0.92) suggests that the crystals of this mole
NH,F crystals have wurtzite structure (zinc sulp
structure) in which each NH ion is
tetrahedrally surrounded by F ions and H-bOn are
formed between the F ions and H-atom
of NH; ions. H-bonds thus formed lock NH,
position. Thus we see that the difference
in structure of of other
halides is due to the formation NHF as compared to thar
in other halides, since F of H-bonds
in NH,F. H-bonds
has the are
highest electronegativity formed only in NHr
and smallest size.
10.
Comparison between the properties of o, m and
Since the two
p-isomers of an aromac
c o m p o u n d

groups in m-and
other, these isomers show p-isomers of a given aromatic e a c h

inter-molecular H-bonding, i.e., compoundare far away

polymerised or associated
severals molecules of
to form a
cluster. The
several molecules of thes
isome

inter-molecular H-bonding taking

etween

in o-isomer p-nitrophenol has

the two alreadybeen shown in pl b
i.e., internal) H-bonding groups are nearer to
each other and Fig. 10.27 (e). On t
which does not lead to hence this eo
the formation of isomer shows i"nuf
any cluster as in
 Bonds
Chemical 323
npes
ermt

-molecular H-bonding taking place in o-nitrophenol has already been shown in

The intra-molecula

. e the formation of a cluster in m-and

O29(). hoiling points than the o-isomer. Due top-isomers,
boi
these isomers have higher
lower volatility than the o-isomer. Due tohigher boiling noint of m-and p-iso
and
pounis
Reting have
greater volatility of o-isomer than
ly be separated from the latter by steam distillation.
former can casily
R N I , (he former

and p-iso
mers
are more soluble in water, since the molecules of these isomers can
molecular
olecules by inter-mo associate
u hH , Om H-bonding. The formation of inter-molecular H-bonding
nitrophenol and water molecules has
already been shown in
tion of intra-moleculer H-bonding in o-isomer prevents the Fig.
10.28 (). On the other
n
a n d thef o r m e t
formation of inter-moleculer
and HO molecules and this results in the
Honding between. decrease in the solubility of
factsihave been shown for o-, m- and
All the above p-nitrophenols in Table 10.7.
Table 10.7: Physical properties of o, m- and p-nitrophenols.

Compound
m.pt. (C) b.pt (°C) Volatility Solubility in H,O
rOphenol 45 217 highly volatile less soluble

aropbenol 96 290 less volatile more soluble

I p b e n o l 114 245 non-volatile more soluble

Other compounds in which intra-molecular H-bonding affects their melting points, boiling points,
waity and solubility as in o-nitro-phenol are o-chlorophenol and o-hydroxy benzoic acid.
1. Monomeric or polymeric nature of HE, HCI, HBr and HI molecules. In case of HC1,
HBr and Hl, H-bonding does not take place and hence these molecules are not able to form
associated molecules, (HX), where X = Cl, Br or I, ie., these molecules exist as monomeric

molecules
HF vapour is monomeric above 353 K (1 atom). However, at higher pressures and
lower

temperatures liquid as well as gaseous HF molecule,

due to H-bonding, exists as a polymerric
has shown that, due to H-bond-
associated) molecule, (HF), (n = 2 to 6). X-ray diffraction study
HIF a ug-zag chain structure in
which H-F= 1.00A, H- -F= 1.55Å and HFH -

ng, solid possesses

shown by dotted lines. HCI, HBr and HI are
angle = 140°. [See Fig. 10.27 (c)]. H-bonds have been
not able to form zig-zag chains.
The anhydrous acid is probably a mixture of H,F2, HF3, HF4 and HgFs

van der Waals Forces

(Inter-molecular Forces) moleues of po d
aS wein

a t t a c t o n betweem me Waals or lel.

uction f r r tej oL
are ca
ubsian(e
lied vam des
dnom-Polar between the molecules of
known with certainty that there exist forces of attraction
now of these forces is maximum in case of solids
as non-polar substances. The magnitude
well forces are called inter-molecular
we move form solid liquid - gas. These
eases as
was first recognised
forces. The existence ofthese forces
in
by
te
van der
Waals ane hence
gases
inter-molecular

The crystals whose

constituent
forces are also
x)
Dartielvan der Waals forces. van der Waals
forces are
alare held together in position by
Called molecular crystas.
ngin of van der Waals forces.
molecules of polar
van der the
ad non-polar Waals
forces existing between presence
the
of different
Substances are due to
es of interactions discussed below:
which are
tractions are present
1. Dipole-dipole interactions. These
HCI etc. are the
polar molecules. The gases like NH3, SO2,
HF Fig. 10.32: Dipole-dipole inter
action between polar molecules.
 Advanced Inorganic Chemistn
324
they haveDes
-Vo.
molecules. Althongh
poiamolecules-are-neutrat,
der Waals forces existine
permaRe
examples of polar behaves as a dipole.
van

mOPRentse, a polar
molecule
interactions end
between the positive oe
polar
electrostatic
molecules are due to the der Waals forces between the
.nedi
dipale
Thus van
the other dipole. The magnitude of d
and the negative end of
interactions (see Fig.
10.32). mole
cules are due to dipole-dipole molecule concerned. Greater i ip
moment of the
interaction depends on the dipole he n
interaction. It is due to the

moment, greater is the magnitude

dipole-dipole
of
the gases can be liquified.
presence
dipole-dipole interactions that interactions: London forces. These inter
2. Instantaneous dipole-induced dipole molecules like He, Ne A
molecules. Cl2, l, Oz, N2
and mono-atomic
present in non-polar
molecules. Non-polar
molecules have noO permanent dipole mo
the examples of non-polar forces existing between non-polar ma
of van der Waals
1930, Fritz London explained the origin mehanics. We know that the l
of quantum (wave)
in the solid and liquid state with the help
non-polar molecule is symmetrically distributed
surrounding the nucleus in the atom of each are in continuous and rapid motion with resnet
nucleus. According to London, these
electrons tothe
nucleus and hence it is possible that at any instant the electron density (negative charge) dthe
and the nucleus (positive charge) may concentratedin
be
nucleus may be concentrated in one region
other region of the same molecule. This results
in an unsymmetrical distribution
of the electron densih
molecule becomes an instantaneous or temperary dini
round the nucleus and hence the non-polar
another non-polar molecule, the other non-polar mole
When this instantaneous dipole comes closer to
instaneous dipole and induced dipole are
cule developes an induced dipole in it. The two dipoles viz,
forces which are called London forces (see Fia
then attracted towards each other by electrostatic
forces because the phenomenon of dispersion
10.33). These forces are called dispersive or dispersion
of light is also connected with these dipoles.

Continuous and rapid

motion of electron round
the nucleus +
Instanta-
9 Induced
neous dipole dipole
Oringinal
dipole
Fig. 10.33 : Instantaneous dipole-induced dipole interactions between non-polar molecules: London forces
For a pair of adjacent molecules, London forces vary inversely as (= distance betweenthe
pair of molecules). Thus the magnitude of these forces is very smalI. The above discription shows
that the van der Waals forces between non-polar molecules is exclusively due to Londonlorc
Characteristics of van der Waals forces
These forces are only short range forces. In the simplest molecules they areimporan
upto 10 cm mole

(ii) These forces are much weaker than covalent and hydrogen bonds. The energies pe 1040
cule involed in covalent bond, hydrogen bond and van der Waals attraction are 200-3400
and 2-20 KJ respectively.
Applications rises
and

Since van der Waals forces are easily overcome, the condensed gas readily vapors
molecular crystals are soft and have low melting points.
Factors affecting the magnitide of van der Waals forces
Waals forct
1. Number of electrons present in a molecule. The of van der
der
magnitude Woa
increases as the number of electrons in the molecules increase. With the increase in
forces the boiling points of the molecules also increase. For example:
Vu
(a) Noble gases He Ne Ar Kr Xe Rn
No. of electrons 2 10 18 36 54 86
Boiling points (K) 4.1 27 67.2 121 165 211.2
 325
Chemical Bonds
Diferent types of
(b) Molecules
CH SiH GeH
No. of electrons 10 18 36
Boiling points(R) 112 161 183
2. Molecular size or molar mass. Larger is the molecular size or roughly larger is the molar
mass, the stronger is the van der Waals force and hence boiling point also increases. Thus boiling
noint of ethane, CH, is higher than that of methane, CH, (C,H, = 18SK, CH, = 112K). Similarly
the boiling point of CF, is higher than that of CF, (CF, = 195K, CF = 145K).

Metallic Bond
See "Metallic Crystals" discussed in the chapter on "Structure ofSolids"
Universtiy Questions
ic bond and electrovalency
LWhat is an ionic bond? What are the factors favouring an ionic bond formation? (Meerut 94)
Write a note on "Elecctovalency and variable electrovalency". Exaplain your answer with exam-
ples (Agra 92, Kanpur, 92)
Under what conditons does ionic valency pass into co-valency? How are the properties of ionic com-
pounds affected by lattice energy? (Allahabad 1991)
Explain the following
(lonic compounds are normally solids and soluble in polar solvents, having high dielectric
constant. (Manipur 81)
() NaCI is electrolyte but CCl4 is not? (Utkal 81, Punjabi 82)
(iü ) lonie compounds, like solid NaCl, does not conduct electricity, whereas molten (fused) NaCl
does. (Venkateswara, 81; Agra 88)
(iv) Electrovalent compounds are mostly solids and have higher m.pts. than covalent com-
pounds. (Manipur, 81; Kanpur 85)
(v) lonic compounds melt at a higher temperature as compared to covalent compounds.
Inert pair effect
5. What is inert pair effect?. Discuss this effect with special reference to VA group elements
(ECC Allahabad 94, Meerut 90, 93, Agra 92)
6. (a) What is inert pair effect and how is the variable valency of Pb and Tl explained on this basis?
(Lucknow 95, Avadh 93)
How does inert pair effect affect the chemical nature of some of the elements? Give examples.
b)
(Lucknow 95, Meerut 96)
Explain the follwing:
(i) Thallous compounds are more stable than thallic compounds
(ii) Boron forms no compound in the unipositive state while T compounds quite stable.
are
(M.D. Rohtak 1984)
(il ) The lower oxidation states become more stable progressively as we descend down in group IIIA
and IVA of the periodic table. (Delhi 91)
(iv) Boron forms BCla and not BCI. (Raj. 86)
() TI(+1) compounds are more stable as compared to TI(+3) compounds. (Meerut 94)
(vi) Tin forms divalent compounds more easily than silicon.
(vii ) On descending the group IVA the stability of +IV oxidation state decreases and that of +II
oxidation state increases. (Delhi B.Sc. Hons, 1986, Punjab 86, Pune 86)
(Agra 85, Raj. 85)
(vii) PbO2 is an oxiding agent while SnO2 is not.

Sn" is stable than Sn*" whereas Pb" is more stable than Pb*
(ix) not more

(x) Ge(II) is a strong reducing agent and Ge (IV) is not. Pb(IV) is an oxidising agent and Pb(lI) is not
(Delhi Hons., 1980)
(xi) PbCh is morestable than PbCl4 (Delhi 1976)
xii ) Compounds of Bi(+lll) are more stable than Bi(+V). doutful existence? (Meerut 96)
stable and has
(tii ) Which of the following halides is least
(a) Cl (b) Gel^ (c) Snl (d) Pbl (IT 96)
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