Chapter CHEMICAL BONDING·AND

MOLECULAR STRUCTURE
,.-.1. IONIC BONDING
- A chemical bond fom1ed between two atoms by complete transfer of one or more electrons from
one atom to another is known as ionic bond and the phenomena is known as ionic bonding. The atom
which loses electron fonns cation ( +ve charge) and the atom which gains electron forms anion (-ve
charge). Between cation and anion, there are electrostatic forces of attraction, therefore, this type of
t,ond is also known as electrovalent bond.
for example, reaction between sodium (Na) and chlorine (Cl2) results in formation of ionic bond
be(Wt"ll two typeS of atoms. Sodium loses electron and form cation whereas chlorine atom gains

eleCtfOll to fonn anion.

e-
~ +
Na + CI2 ~ Na Cl
2
Electt0nic configuration 2, 8, 1 2, 8, 7 2, 8, 2, 8, 8

Similarly in CaC1 (Calcium chloride) ionic bonding takes place because of transfer of two electron
2
from calcium atom to two chlorine atoms. ., /

e-
~l ci
l Ca + Cl ~ Ca2 + Cl (CaClJ
~ 2,8,8
e- 2,8,8
2, 8, 8, 2 2, 8, 7
I
.aJ. GENERAL CHARACTERISTICS OF IONIC BONDING
1. Ionic bonding talces place between a highly electropositive element and .a. big,hl_y ele~tronegative
element. -
2. The electropositive element loses electron(s) to fortn cation and the highly electronegative atom
gains electrons to form anion.
3. Between cation and anion, there is electrostatic force of attraction.
4. Substance having ionic bonding in them are ·usually solids and have high melting and boiling
~m~. t
5. Substance having ionic bonds are bard and rigid because of presence of strong electrostatic force
of attraction between cations and anions.
. 6. Substance having ionic bonds in them are soluble in water and other polar solvents having high
dielectric constant. '
t 1· Ionic solids donot conduct electricity in solid state but they do so in molten form and solution
1~. ~
J

29
31 l)fJftSff Ateti!k Slrtdtrt1 ~ I.St. Sem. I (Cffltu Umv. ~t J
2..3. ENERGY CONSIDERATION IN IONIC BONDING (Lattice Energy)

2..3.1. lattice NEnergy {U)

b 6 defined 35 l:he ~....in of energJ released when one mole of an ioni~ c.om~nd is formed
it! ~dJilldl ~ f i gate.
Fmmanoo of ODe n»!e of an tOOJC compound from its constituent gaseous state may be represented

~t;' ~ 1
__.,. MX + Lattice energy(- U) ; tiH = -U
fo:"SaOii.eam ,te
Xa Cg) ~ er- (g) --> NaCl l1H = - 778 kJ mo1- 1 (Lattice energy)
Il:.e _ ? ~ loss of energy °: ~lease of ~gy wb~ o~positely charged ions comb" ~
~ .. 1le llai::e: energy of an ionic solid 1s meas~ _of its stabihty_,.e., ~eater the value of Latt1ct
eae:,:gy p • 15 ns sw,illi}. Lattice energy of some tome compounds JS as gwen below :
T.a.le 1.1 : 1sUin- magy or some common ionic compounds.
~l;-TJpe Solids AXrType Solids

Campom2d I attire energy Compound Lattice energy

kl mo1-1 kJmo1-1

LiF -1033 CaF2 -2581

NaC1 -733 MgF2 - 2882
l.iI - 140 MnC12 -2525
AgCI -895 CaCl2 - 2254
Agl -795
M,o -3932
lfgS -3254

~"" Energy Change In Formation of Ionic Substance

8cJm.Baber lJ919J proposed medJod ro relate the lattice energy of ionic crystals (solids) with other
_..lyiumic' daa .. This is Born-Haber cycle.
Acco.nlina to BonJ..Haber cycle. the formation of ionic compound from its constiment elements
oceed' in JJl#Dber lJl ttq,s, For example, the formation of one mole of sodium chloride from sodium
daJorine atmm may be represented as follows ;
Na(J) SIIJJiroauon ) Na( ) lonisauon +
s g l > Na(g)
J ~ EJectrou -
2 Clz(g) l D ~ Cl2(g) affinity E > Cl(g)
2

N~J + Cl(g) Cry&taJ formation NaCJ(s)

u
__.e I • ~ energy of sodium
S • Sublimation energy of sodhnn metal
 1
AHt==S+ 2 D+I+E+U
1
-U == S + D + I + E - .MI1
2
Putting the different values (given) on right hand side, we get :
l
-U == 108'·8 + l X 242·7 + 498·3 - 380·7 + 410·9
U = -758·65 Id mot- 1
~--'· SOLVATION ENERGY AND._ITS IMPORTANCE IN CONTEXT TO STABIIJ'P/ AND
~LUBILITY OF IONIC COMPOUNDS ·
Solvatian Eaergy. : It
..... is defined
,, ~ .,. . ~ mole of an ionic ac,,tid
as the amount of energy released
dissolves ~ l y ID ~~s ~fa SQIV~~puom-~.,,-
The value of solvation..eaergy for a solid ~ uoon na~ of the solveot used, If •urn ad is

- -
water. then salvation enefl}' is known a~ Jlydiiiiion Me.tgy :-
Solvatioa eoel1D' or Hydration-energy is produced becauso of attractive foa:es aI j :t.~Ioped
between ions of. tie solid and opposimly charged poles of the polar selvents. Wfllil a ilfmc solid is
 o DINESH Atomic Structure, Bondlng.f, .. B.Sc. Sem. I (Cluster Univ of J
J • GffllJta)
dassohcd in O sohenl. the solvent molecules surround the ion~ uf the solid by using its OPP<> •
• nm_f uni_ons 1s partly ~eutral~sed and the solveo
ch rgcd {mini' ends. As a •~suit, the cI1~~g~ t~n cnllt!ns I Sllcly
molecules net as on insula11ng sphere. 1lus msulut111g effect is known as dielectric effect. Thus t
dipole intcruction due to which there is u loose comhination between the ion and solvent molccul~ ~
called sohation nnd the energy rclcnscd in this process is called solvation energy. If 01e solvent is wa~ts
dk:n these tenns arc called hydration nnd hydration energy. For example r,

M" '1 (g) t aq - ➔ M(~q) + Hydration energy

As the hydration energ) increases, the solubility of ionic solid increases. The ions with smaJJ siz
and high charge are heavily hydrated and are having maximum hydration energy. Therefore, the orde~
of h}dration energy of Li +. Na + and K+ is Li+ > Na+ > K+.
Thus. it can be concluded that
Solubility ex: solvation energy
Again from the concept of Lattice energy and solvation energy, it can be concluded that the
dissolution of ionic .solids in water depends upon their lattice energy and hydration energy (solvation
energy). These two tenns are related with the enthalpy of solution (L\H), as :
Mi = Hydration energy - Lattice Energy
1n general, the solubility of ionic compounds decrease with the increase in lattice energy i.e. the
stability of ionic compounds. This is due to the fact if the energy needed to break up the ions, i.e. the
ener;gy oost is greater than the energy released, then solvation does not take place and compound will
most likely to be insoluble.
For example, compounds like BaSO4, PbSO4, AgCI etc. are ionic in nature but are sparingly
.soluble in water as they have high value of lattice energy and low value of solvation energy.
It is interesting to note that the solubilities of silver halides are lower than alkali metal halides while
their lattice energies are of same order as that of alkali metal halides. The outer electronic configuration
1
of u+, Na• or K+ is ns , while that of Ag+ ion is 4d10 5s2. It has been suggested that the d~Iectrons
screen the nuclear charge from the outer electrons less effectively than s- and p-electrons. The Ag+ ion,
therefore, behaves as if it has a greater charge than Li+, Na+ or K + ions. Hence silver salts undergo
appreciable polarisation and therefore, appreciable change from ionic to convaJent character. This
accounts for their lower solubility in water.
Dependence of Solubility on solvation energy. Solubility and solvation energy are directly related
to each other i.e., More the solvation energy more will be the solubility of the compound.
Solubility ex: Solvation energy
Depen~ence of Solubility on Lattice energy. Solubility and Lattice energy are inversely related ro
each other 1.e., more the lattice energy, lesser will be solubility of the compound.

1
Solubility ex
Lattice energy n1 .
N0 t_e. Compounds hke
·
BaS04, PbS04 , AgCl etc, are ionic in nature but _they are O Y spanng1}
Jvation energy.
~Jubie m water because they have high value of lattice energy and low ,'Slue of so
2.5. BORN-HABER CYCLE AND ITS APPLICATIONS
 DINESH Atomic Structure, Bonding ..... B.Sc. Sem. I (Cluster Univ. of Jamlltt)

Perio.Uc Trends
On mo"ing along the row. since the size or the atom decreases due to increased effective nuclcat
charge and thus the polarisation decreases and hence the covalent charnctcr incrca5es in their compou_nd\
On moving do\\ n the group, the size of cntion increases un<l hence ionic ctrnractcr increases.
2.8. IONIC CHARACTER IN COVALENT COMPOUNDS
~·
A covalent bond is formed between the two atoms by mutual sharing of the electrons. ~f the two
atoms fonning tbe bond are same, then the bond is ~a id to he non-polur covalent hond. But if the two
atoms forming the covalent bond are dissimilar nnd arc of different clectronegativitics; then the bond is
said to be polar covalent bond. In such bond, the etc, iron density between atoms is shared i_n such a W:!J
that it is displaced more towards the more electronegative atom and this results in fonnauon of pa~,~
negatt\'e charge on more electronegative atom and the partial positive charge on _less electrone~a~1ve
atom. Thus, in heteroatomic molecules having the two atoms differing considerably m electronegativl!y,
the two electric poles develop i.e. bond shows ionic character.
For example, the dipole in hydrogen chloride can be represented as
+J - r5
H - Cl
1berefore, it can be concluded that a covalent bond between two same atoms is a 100% covalent
bond whereas a covalent bond between different atoms always have same ionic character in it.
Ujonic = 4·77 X 10- lO e.s.u. X 92 X 10- IO cm
= 438·84 x 10-20 e.s.u cm
= 4·3884 D [·: 1D = 10- 10 esu cm]
Obse~ed dipole moment of HF = 1·98 D. The degree of ionic character is given by the ratio of
observed dipole moment to the dipole moment of 100 % ionic character.
Hence,
. . h 1·98
~rcentage of 1omc c aracter of HF = -4·3884
- x 100
L =45•12
} : BOND MOMENT AND DIPOLE MOMENT
Bond mome~t :_ Whenever a covalent bond is present between different atoms (say A & B) th
•.u d donot remam ID the centre. as it shifts slightly towards atom of higher electronegativity
, ..,,..""hifting Th~
s of bond towards atom of higher electronegativity is known as Bond moment. ·
_ B Bond moment c5+ ' 6-
A A- B
Atom with
higher electronegativity
1:1e bond moment results in polarity of bond and dipole moment(µ),
Dipole moment (µ) : In a polar covalent bond (covalent bo d 6' ·
remains shifted towards atom of higher electronegativit as a re n 1 e~een different atoms), the bond
negative charge (o-) and the other atom acquires partialypositive c::g~f(i:;ch an atom acquires partial
o+ b'-
e.g., H -CI
Such a bond is said to possess dipole moment which may be defined as :
The product of partial charge (q) and distance between centres of •
bond is known as dipole moment. two atoms (d) m a polar covalent
Mathematically, µ =q x d
µ = dipole moment
 I

(ltellkal Bonding and Molcculor Structµt~

partial charge <8 I· or 6 wilhour sign)
t1 = distance ol scr,cratiou hctwccn the centres of two at
"q·· is ?f 1hc order 1~-10 c.•.u and "ti" is ol the order 10 8 cm, thcrelo,e, µ(<lipole momen,';7~';,f
the order 10 18 e.s.u x 10 rR cm = 10-18 c.s.u. cm.
Units of dipole moment arc Debyc or D.
11) = 10· 18 c.s.u. cm,
Greater the value of dipole moment , greater is the polarity of bond and vice versa.
2.10. PERCENTAGE IONIC CHARACTER (FROM DIPOLE MOMENT AND
ELECTRONEGATIVITY DIFFERENCE)
- A covalent bond between two different atoms is never 100% covalent in nature, it always has some
percentage of ionic character in it. It is because of t11c fact thal out of two different atoms, one will have
bigher electroncgativity than the other. Hence, highly electronegative atom acquires partial - ve charge
while the other atom (lower electronegativity) will acquire partial +ve charge, As a result of it, bond
acquires some percentage of ionic character in it.
The percentage ionic character of a covalent bond can be calculated as shown below :
1. From dipole moment (µ). Consider a polar covalent bond between two different ato~ i.e.,

~ _i . The actual dipole moment of this molecule can be found experimentally by multiplying charge
(o+ or b- ) with distance between two atoms. This value of dipole moment is also known as experimental
va}ue of dipole moment. Now the dipole moment of same molecule can be found by considering it as
purely ionic compound i.e., A+ B-. It is theoretical value of dipole moment. The percentage ionic
cl}aracter would then be given by
. . Actual dipole of bond ~ ~M
Percentage 10mc character= Dipole moment of pure ionic bond ,)>-x,; u ~
2. From electronegativity. Pauling proposed following equation for the detewination of percentage
ionic character of a covalent bond.
4
Percentage ionic character = 18 [XA - x8 J1"
where XA and x are electronegativities of atoms A and B respectively. He established following
8
rules for directly calculating percentage ionic character.
Table 2.2 : Electronegativity difference and % age ionic character.

1·0 1·4 1·7 2·0 2·4 3·0

XA - X8 Values 0·6
22 39 50 63 76 89
% age ionic character 9

Example : The C-O bond has 22 % ionic character and 78 % covalent character because
electronegativity difference between two is 1·0 (C = 2·5 & 0 = 3·5).
Hamnay & Smith proposed another equation to calculate percentage ionic character of covalent
bond. According to them
2
Percentage ionic character == 16 (xA - x8 ) + 3·5 (x,A - x,8 )
Both the equations give only approximate value of ionic character.
Problem:
1. Calculate percentage ionic character of HF molecule (given actual dipole moment is l ·98 D
and dipole moment of same molecule when it ts considered purely ionic bond is 4·42 D.)
198
Solution. Percentage ionic character of HF = ' x 100 = 44·8.
4·42
 41
- - ' • • • 11 dM• c l S1r ct rr
1 Stre~ of a u"'81cn1 hond is directly prop<)rtional to cx1ent of overlapping betWeen the ntomi
10
"~tlllflll nnpatred electrons. c
(b) 01-erlaffl)lflll ocA:1111! only t,etwcn those orbilJlls which are involved in bonding and not between
cntntals of coJflbining atoms.
(ti ov.rlapping o~ Mnd fonnelion is posslbl belwcen 1hose orbilJlls which are of nearly same

,ene®
(tfland same ~tab,hty.
A i:pberically symmcirical ort,ital i.e .. s-orbital donol cxhibil any _directional preference. while
dll'l'Cli(tnal ort)ital i.e., p or d tends 10 fonn a bond in 1he direclion of maximum electron density within
u,c orbtUlL i.e.• along their axis,
2.13. SHAPES OF SIMPLE INORGANIC MOLECULES AND IONS ON THE BASES OF
y5£PR MODEL & HYBRIDIZATION WITH SUITABLE EXAMPLES OF LINEAR,
ffllGONAL PLANAR, SQUARE PLANAR, TETRAHEDRAL, TRIGONAL BIPYRAMIDAL
~ND OCTAHEDRAL ARRANGEMENT
;,11. Valence Shell Electron pair repulsion theory (VSEPR theo~ & Shapes of
moJeeUleS and ions. ~~
JM i; -
This lheOIY was proposed by Sidgwick and Powell (1940) and developed by Gillespie and Nyholm
(1957l- According to this theocy, the geometry or shape of a given species (molecule or ion) depends
flJ'OI' number and nature of electron pairs surrounding the central atom of the molecule or ion.
Toe VSEPR theory may be discuss~d as under :
(a) The electrons present in the val~nce shell of the central atom occupy localised orbitals wlli_ch ~
jjjJeCIOO in space in such a manner that they kee"Ji:.aJJ;!!I froni e3ch~othtir in ordefto ei]Jilrien<:ie fuinimmn
t1ccUosmfic repulsiori between tbeill. Thus such a siwi;tion imparlsminimum energy and heiice maximtJID
stability to molecule or ion. It can be further explained as below.
(I) If the sum of bonding electron pairs (bps) and non-bonding or Jone pairs o.f electrons (lps)
,aaounding +
!he centtal atotDlion is 1\VO re:: (bps 1ps =_1Lthen the sbaiie ofsuch a moJeculeiioo
!llJll)d be linear in order ,to have ioinimmn electrostatic repulsion between the bonds having the bond
,..
q1e equal to 180°. c
(ii) If central atomlioilis surrounded by three electron pairs (bps + Jps = 31 then electron pairs are
4jm:l!!!! at the comers of a triangle. Shape of such molecule is Jrigooal plannar with bond angles equal

.,~
(iii/ If central atotDlion is surrounded b t<far electron pairs (Jps + Ips = 4), then electron pairs are
~ wwards the comer ofJ reguJa, tel atiedro . Thus molecule/ion will fiiive tetrahedral sliape wilh
bond angle JW 2J., /
. (Iv) If ceo1ral arotDlion is surrounded five electron pairs (bps + Jps =jJ. then electron pairs are
direaed towards comer o~ a ocaihedron. Thus molecule/ion will have trigonal bipvt!!!Jidal_strucrure.
The angle between equatorial electron pairs are of 120°. The angle between equatorial and axial electron
,pain is 90° and angle between two axial bond is oris0°.
. (f) fr"centriil aromlion is surrounded by Six electron pairs (bps + Jps = jl.. then electron pairs are
directed towards the comer of a regular octahedron, Bond angles between any tw0 electron pairs is 90°
0
and bond angle between two axial electron pairs 1slso •
('.i) If oeDIIII a!o!"/ion is surrounded by seven electron pairs (bps + lps =:J).. then electron pairs
are duected plllrd~ the comers of a pentaS9nal hipyramid· The geometry of moleculer or ion is
pemagOIIII b~dal- !11• bond ao~I~ between equatorial electron pair is W, The bond angle
llelweM eci~ria! ..., axial electron pair 1s •• and between two axial etectr0n"'palr is 180°.
 ;,. I s, Ser.L I '011if r Unfv. of J
DINESH AfQtnic Sfrv(fure, S r.n! 9-· . ,.. '
42
, , .. .....
\

,,
/\\
/ \.\,
.I
I
\~ ..
,,, ,,, ·-..:- ~-
~
I
• 0 • '' ,,,,,
I

1)Unear
4) Trigonal 6) Pentagona
5) octahedral
2) Trigonal planar 3) Tetrclledral blpyramidaJ . bipyrarmdal

Ffg. 2.3. Shapes of MoJeadcs

(b Regular & irregular geometry of species (molecules/ions). The el~ctron pairs surro~nd
centra/ atom/ion may be lone pair (Ip) & bond pair (bp) or only bond pairs (bp). If at?mhon ts
surrounded by bond pairs only. then the molecule or ion wiJI have regular shapes_ (as_ already dtscuSsedJ.
However. presence of lone pair makes the geometry of molecule/ion irregular. It JS d1~ssed as below._
The repulc.ion between bond pairs (bp-bp) is lesser than repulsion betw~n lone parr. and bond P_au
(lp-bp) which in tum is lesser than repulsion between Jone patr & Jone pair (Ip - Ip). ,.e.• Repulsne
forces Juve following order : Ip - Ip > Ip - bp > bp - bp
1f central atom or ion has no lone pairs, all the_repulsty~fQrces between bond £airs wiJl have same
magnitude, hence molecule will be symmetrical in shape as in case of'fkF2, BF3, CH4, CC4 etc.
H
F

~ / k·:·
1so·
F~F F-B

""F H\H
Fig. 2.4. Regular geometries of some molecules
.. + .. - ..
If cemral atom has one or more lone pairs as in case of NH3 , H3O:, SF4 , :9F3, ICI2 , Hi~ etc,
then repulsion brings the bond pairs closer and hence shape of the molecule becomes irregolar, because
greater repulsion by Ione pair changes the value of bond angles. e.g., required value of bond angle in
:r--11 is109°·28' but acrual value is 107°. Similarly bond angle in water molecule should also be
3
109°·28' but presence of two Ione pairs causes distortion and actual bond angle value becomes 104°·5'.
~

2.13.2. Shapes of Simple Molecules and Ion Based upon VSEPR Theory
I . ~ In ammonia (~ 3 ) molecule, ~ybridisation of nitrogen is sp3, hence the h2_nd angle .should
be equal to W2°. 28'. But 1t ts not so, as mtrogen atom contains three bond pairs and OBMOne ~ on
it. 1be lode pair causes-i&ronger repulsion to bond pairs and hence bond angle -decreases to 1l>7°. The
shape of N"3 gets distorted to pyramidal, as given below :

or

Fl1. l.!. Shape of NH1

t. a,o+. The formation of H30 + involves a co-ordinate covalent boµ.4. In hydroniwn ion, the
Jt11X,rllliliilJ"- -.i ii sp1 hybridised. Out of four hybrid orbitaJs, two unpaired orbitals form bond pairs with
 h-Onds, fhe rornnitt ng two t: , or 11c n 01 1.
ot• ordh111to bonds.
5uSr • • ........... 5o2 s1,1 Sd Ground 5tate electronic

{1~ D]1IJ .I I :I(hybrid

I] J configuration
orbitals)

sQSr
(llxcned stntc)
lil l1I1JIJ [ I
. 5s· . S 1 6I I 1
Sd
p sp-' d2 hybridisation
Two co~ordinate bonds

~m
ti Cl Cf CJ
fI;;~:;) 71l
CJ

: Sn : I
; / At " ' - :
Cl········l·,····-·C1
Cl 2
_
Fig. 2.23. Shape of SnCl6

~PPROACH MOLECULAR ORBITAL APPROACH THEOAY)

·- ........:... :t.oncept was given by Hunds & Mulliken, hen~e is aJ~o knQJ!n it: Hund-Mulliken th~·_ This
11:!tlW} ctt,iains the formatio~ of £.._OValt;nt tiond ~ in a b~tter and .JDOre !filIOnal paarn:r. 1b.e _lll!POrtam
1111,nv,uons of""dlis theory are : .
1. A molecule is different from the a_!om, from ~hich _it is_obtain~. ~l the electr~ns ~lon_gmg to
atnm !eaves the atomic orbitals and in the molecule they are __!!llder the influern:e o.f all the !lllCleL.Of the
oombming atoms. · - - - - ·
2. Aromic orbitals combine together to form a new ~et of _orbitals which are known as molecular
ortntals (MOs). The no. of molecular orbitals fo·rmed is equal to number of atomic orbitals combined.
). Half of the atomic orbitals have energy lesser than combining atomic orbitals and are known as
boncJing molecular 011bitals (BMOs). The remaining half of molecular orbitals are of higher energy than
the 1-X)mbining atomic orbitals and they are known as Anti-bonding molecular orbitals. M :o lecular
orbiptls are named as a1s, a*1s, a2s, a*2s, cr2pz, 1t2px ::::: 1t2py etc.
4. The various electrons in molecule occupy the new molecular orbitals and each electron is
belitved w be .associated with aJl the nuclei.
~. 1he molecular orbitals like atomic orbital are filled in increasing order of energy and each
orbiq¼J can have a maximum of two electrons.
\ . The shape of mo.Jecufar orbitals depends upon .the shape of the co.mbining atoms.
~.1 RULES FOR LINEAR COMBINATION OF ATOMIC ORBITALS (LCAO)
Linear Combinadon of Atomfo Orbitals (LCAO) Method
!13e formation of bond~ng and antibondlng mo!ecij~ar orbitals ca~ be~x_plained b_x worki:n~ wave
funcnon for moJ~tar _orb1taJs. The method apphed ts known as hnear combination of atomic·ortlMs
(L.C.A.O.) approxmiauon. .,/
TI1e linear combination of :fwo_ atomic orbitals take place either by addition or subtraction of two
wave functions of atoms A & B. This can be expressed as;
'P = ~A :f 'Jle I 1
.. , (~