Chemical Bonding

Chemical Bonding & Molecular Structure

Chemical bonding is a force, which binds two or  Transfer of one or more electrons from
more atom into a single entity electropositive to electro negative element.
 Electrovalency – No of e– lost or gain.
Cause of Chemical Bonding
 To attain the nearest inert gas configuration Factors Favoring Ionic Bond
 To loss P.E and become stable Born Haber cycle
Eg. NaCl
Factor Favoring Bonding
 Fattr > Frep
 (-)ve free energy (G)

 High EA and U
 Low SE, IE and BDE
 Size of cation – large
 Size of anion – small
 Hf must be negative i.e. (SE + IE + ½ BDE) <
(– EA – U)
N.B. If size of cation is small and size of anion is
large then ionic character gets converted to
covalent character called polarization.
Classification Of Chemical Bond
Lattice Energy
Chemical Bonding
 Energy released when one mole of ionic crystal
is formed

Inter Atomic Inter Molecular

(Primary Bond) (Secondary Bond)
(Strong Bond) (Weak Bond)

Ionic Bond Hydrogen

(M + NM) Bond
(EP + EN)
Vander
Covalent Bond Waals
(NM + NM) Force  U  Stability
(EN + EN)  U  mp
Metallic Bond  U  ( r = inter ionic distance)
(M + M)
(EP + EP)  U
 U  Charge on cation
Ionic Bond
e.g. NaCl < MgCl2 < AlCl3 < SiCl4
 Proposed Kossel and Lewis.  Lattice energy of – bi-bi valent ions > bi-uni >
 Also called polar or electrovalent bond. uni – uni. E.g MgO > MgCl2 > NaCl

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 Chemical Bonding
Characteristic of Ionic Compound  Solubility 
 Solids with high density and stability. eg:- NaCl > MgCl2 > AlCl3
 M.P. & B.P. are high
 Size of cation 
 Hard + Brittle
 Good conductor when fused or dissolved in eg:- LiNO3 > NaNO3 > KNO3
solvent of high dielectric constant
 Non directional, hence does not exhibit space N.B.
isomerism. Water is a polar solvent of high dielectric constant
 Soluble in polar solvent (like dissolves like) (81) it means that water decreases the force of
 Under goes ionic reaction and rate of reaction attraction between the ions by 81 times
is fast.
 Compound having same electronic structure Covalent Bond
are isomorphous to each other  Proposed by Lewis.
Eg:- NaF or MgO  Bond formed by mutual sharing of electrons
Na+ F- Mg2+ O2- between two electronegative atoms
(2,8) (2,8) (2,8) (2,8)  Electron pair becomes common property of two
N.B. atoms.
Hardness  Electrostatic force of attraction
 Charge on ion Factors Favoring Covalent Bond
  The atom must be E.N
BP/MP  Electrostatic force of attraction  Difference in E.N (x) < 1.7 (x > 1.7 ionic
compound.
Volatile nature 

Characteristics of Covalent Compound

Solvation Energy
 Solid liquid or gas (solid in case of high mol.
 Energy released when 1 mole of solute is wt.)
dissolved in a solvent.  Covalent solid are of 3-types:
 If solvent is water it is called hydration energy (a) Very soft – consist of separate lattice layers
 HE  eg:- (graphite)
e.g. Li+ > Na+ > K+ > Rb+ > Cs+ (b) Soft in which molecules are hold by Vander
 HE  charge of cation Waal’s force eg:- (Organic compounds, S, I, P2O5)
e.g Na+ > Mg2+ > Al3+ (c) Very hard:- due to bonding with other atoms
 HE  charge of anion forming giant molecules
eg:- Diamond, carborandum (SiC), Silicon (SiO2)
E.g. N –3 > O –2 > F –
 Size of hydrated ion is smaller than ion in etc
gaseous phase. e.g.  Low bp except diamond, SiC, SiO2 etc.
Li+ (g) < Na+ (g) while Li+ (aq) > Na+ (aq)  Insoluble in polar solvent and generally bad
 More hydrated ion has less mobility. conductor of electricity (except graphite).
 Compound having polar character like HCl can
e.g. Li+ < Na+ < K+ < Rb+ < Cs+ (order of
mobility) conduct electricity in aqueous solution.
 Covalent bond is rigid and directional, hence
Solubility of Ionic Compound in Polar
exhibit stereo isomers.
Solvent  Undergoes molecular reaction and rate of
 Solvation energy > Lattice energy reaction is slow
 F= q1q2/(rA+ + rB-)2  Covalency – No. of e – which an atom shares.
( )
 Covalency = 8 – valence e – (except H)
 Solubility  Dielectric constant (K)
e.g. C = 8 – 4 = 4, N = 8 – 5 = 3, S = 8 – 6 = 2
 Solubility  Interionic distance ( )
eg LiF < LiCl < LiBr < LiI
 Solubility  Ionic character

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Variable Covalency Characteristics of Coordinate Compounds
2 2 6 2 4 0
16S= 1s 2s 2p 3s 3p 3d  Solid, liquid, gas.
3s 3p 3d  M.p., b.p, higher than covalent lower than
ionic
   
 Bad conductor of electricity
Covalency - 2  More polar than covalent but less than ionic
 Dielectric constant high.
    
 Soluble in organic solvent is it sparingly
Covalency - 4 soluble in polar solvent.
 Shows molecular rxn.
     
 Bond is rigid and directional hence exhibit
Covalency - 6 space isomers.

 Found in those cases where d-orbital is vacant. Octet rule

 This explains why compounds like OF6, NCl5
does not exit but SF6, PCl5 exist.
 Compounds in which central atom possess
maximum covalency are highly inert
Coordinate Bond
 Also known as dative or semi polar bond.
 Proposed by Sedgwick.
 Special kind of covalent bond.
 The shared e- pair is donated by one atom and
shared by both atom.
 Represented by Donor Acceptor
Lewis base
 Proposed by Lewis and Kossel
 It states that each atom tries to obtain the octet
state.
Failure of Octet Rule
 e– deficient molecule – central atom less than
the 8e–. e.g H2, BeX2, BX3, AlX3, BH3, NO etc.
 e– efficient molecule/Super Octet Molecule –
central molecule has more than 8e–. e.g PCl5, SF6,
IF7, OsF8, XeF2, XeF4, XeF6 etc.
Electron Deficient Molecule
Lewis Acid
 It is of two types:-
a) True e– deficient  molecule which cannot
complete its octet eg:- H2, BeCl2, BH3 etc
b) Pseudo e– deficient  molecule which cannot
complete its octet either by back bonding, banana
bonding, Resonance, dimerisation or Lewis adduct
formation or odd e– bond
eg:- BF3, AlCl3, CO, B2H6, NO etc

Back Bonding

 The shared e- always remain in the orbital of

donor.

Dimerisation
Factors Favoring Coordinate Bond
 One atom should be electron rich and other is e-
deficient.
 Co-ordinate bond is formed after saturation of
normal covalency.
Lewis Adduct

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 Chemical Bonding
Back Bonding octet rule but it follow its max covalency.
 After formation of sigma bond, one atom can  Covalency of element depends on their period
donate lone pair of electrons and another atom
should vacant orbital to accept the lone pair, the Period Max.covalency No. of e in outer most
bond formed is called back bonding . orbit
 Two type 1 2 4
(a) pπ-pπ back bonding 2 4 8
(b) pπ-dπ back bonding. 3 6 12
4 6 12
5 8 16
6 8 16

Formal Charge
 Specific charge which appears in the covalent
molecule having co-ordinate bond.
F.C = 0 (covalent)
F.C = + (co-ordinate donor)
F.C = – (co-ordinate acceptor)
FC = TVE – ½ SE – USE

Polar Covalent Bond

 Bonds formed between two different atoms and
bonded atom acquired partial –ve and +ve charge.
Banana Bonding/H-bridge Bond/3- eg:- Cl ÷ Cl H – Cl
centre 2-electron bond/ 3c-2e Bond Equal sharing of e- unequal sharing of e-
Notation:- + – 
 Bond formed like bridge with the help of two
H – F or H – Cl
electrons and 3- orbitals

 Banana bond is found in B2H6, B4H10, B5H9,

B5H11, B6H10 and B10H14.

Odd electron Bond/ 2-Centre 3-Electron

Bond
 Unequal sharing of one electron of one atom
and e- pair of other atom.
 Odd e– molecules are unstable reactive,
paramagnetic, colures and can under go
dimersation and disproportionation reaction.
 E.g. NO
 Bond polarity (ionic character)  difference in
E.N (xA – xB) x
 Ionic character
(i) Pauling = [1 – e – 0.25 x2] x 100 (x < 1.7)
(ii) Hannay + Smith = (16 x + 3.5 x2) (x < 2.1)
(iii) obs/cal x 100

Theory of Maximum Covalency

 Concept given by Sidgwick
 It is not necessary that all molecule follow

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 Chemical Bonding
Polarisation N.B
 Change of ionic to covalent character  Presence of polar medium keeps away the
cation and anion from each other and thereby,
prevent polarization of anion. Therefore,
AlCl3, a covalent molecule behaves as ionic in
water.
 Polarization decrease down a group while
increase along a period.
 Polarizability of anion increase down group
while decrease along a period.
 Polarization explains following facts:-
a) Sulphids are less soluble in water than oxides of
same metal. MgO > MgS
b) Lithium salts are soluble in organic solvent
c) Beryllium compound are less soluble
d) Solubility AlX3 decreases from AlF3 to AlI3

 This inclination of outer most e- cloud

Dipole Moment
decrease overall charge density of ionic bond and
increases in covalent character of ionic bond called  Defined as product of magnitude of charge
polarization (electronic charge) distance between to charges and
bond length
 Polarization  covalent character
 Polarization decreases solubility of ionic
compound in polar solvent

Factors Affecting Polarisation (Fajans

Rule)
 μ = Charge (e) x bond length (l)
 Size of cation  1/polarization  C = 4.8 x 10 – 10 esu = 1.6 x 0 – 19 C
E.g. LiCl > NaCl > KCl  Unit of  =
 Size of anion  polarization
Eg:- CaF2 < CalCl2 < CaBr2 < CaI2 C-m (SI)
 Charge on cation  polarization esu-cm (CGS)
Eg:- NaCl < CaCl2 < AlCl3 Debye (Practical)
N.B:- If a metal forms more than one halide, the
metal having higher charge on cation (O.N) is    x
usually more covalent in nature in comparisation   no of lone pair
with cation having low (O.N). This Explain why  μ is a vector quantity
PbCl2, SnCl2 are ionic while PbCl4, SnCl4 are 1
covalent
 If a cation contains Pseudo inert configuration it q
R
shows more polarization than cation with inert gas
configuration.
CuCl > NaCl 2
2,8,18 2,8  R = 1 +
2
22 +212Cosθ
Summary of Fajan’s Rule  if θ = 0o R = 1 + 2
Ionic Covalent  if θ = 180o R = 1 - 2
Low positive charge High positive charge  if 1 = 2. R = 2 Cosθ/2
Large cation Small cation
 R 
Small anion Large anion

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 Chemical Bonding
Application oF Dipole Moment
 Decides polarity of molecule
 = 0 Non-polar
 > 0 Polar
 Determine geometry of molecules
 = 0 (Regular)
 > 0 (Distorted)
 Determine % of ionic character
%= x 100 = 100
Example:
For HI, calculate the % of ionic character given a  In some cases, trans form may have more
bond length = 161 pm and an observed dipole dipole moment than cis form.
moment 0.44 D.
Solution:
Bond length (l) = 161 pm = 161 x 10–10 cm
Charge of electron (e) = 4.8 x 10–10 esu
Calculated dipole moment:
 l x e = 161 x 10–10 x 4.8 x 10–10 esu-cm Trans-1-chloropeopene has higher dipole moment
= 7.728 x 10–18 esu-cm than cis-1-chloropeopene
Observed dipole moment: 0.44 x 10–18 esu-cm  In ortho position experimental value of  is
different than the theoretical value due to dipole –
%= x 100 = = 5.7 %
dipole interaction
 In general  of trans isomers are zero or lower CH3 Cl
than cis isomer Cl
CH3

 exp =  obs  exp <  obs

(No interaction) (Repulsion)
 Determines orientation of benzene ring
Cl Cl Cl OH CH2CH2CH3
Cl F CH3

Cl
Cl  exp <  obs  exp <  obs
(due to H–bonding) (Repulsion )
60o
120o 180o
 For para derivatives   0 if two unlike atoms
at para positions.
o > m > p Cl

N.B.
 It is not necessary for all trans form to have
their dipole moment zero.

Br
0
 It is not necessary that two like group of at

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 Chemical Bonding
para position will always have  = 0.  Due to overlapping two type of bond is formed
OH a) sigma (σ)
NO2 OCH3
b) pi (π)

Sigma Bond
NO2 OCH3 OH  Formed by linear or axial or end to end or head
on overlapping (along the bonding axis)
=0 0 0
 Formed between s–s, s–pz, pz–pz, pz-dz2, dz2-dz2,
dx2–y2–dx2–y2, AO–HO, HO–HO
N.B.
CH3Cl (1.87D) >CH2Cl2 (1.54D)> CHCl3 (1.02 D)
> CCl4, CH4 (0 D)

Covalent Bond In The Light of Quantum

Mechanics
 Lewis concept of covalent bond could not
explain
AO - HO HO - HO
a) Nature of force between atoms forming covalent AO - HO

bond  σ – bond – has independent existence.

b) Cause of covalent bond formation  Due to linear overlapping e– cloud is
c) Bond length and bond energy symmetrical hence stronger bond.
d) Geometry and shape of molecule  e– are not mobile i.e., localized e–
e) Stability of molecule  free rotation is possible around a sigma bond
 To explain the above limitation, two theories which result confirmation of many alkanes
based on quantum mechanics have been proposed  It determines the direction and extent of
A – Valence bond theory (VBT) internuclear distance.
B – Molecular orbital theory (MOT)  The molecular sigma orbital consists of a single
electron cloud symmetrically around the
Valence Bond Theory internuclear axis.
 No. of sigma bond = n – 1 n = no. of atoms
 Proposed by Heitler and London.
 No. of sigma bond = n – 1 + r r = no. of ring
 Covalent bond is formed by overlapping of
 C2H2 = 4 – 1 = 3
atomic orbitals.
 Half-filled atomic orbital (unpaired e) can enter
into overlapping.
 Two e- in bond orbital must have opposite spin.
 As a result of overlapping there is maximum e-
12 – 1 + 1 = 12
density somewhere between atoms, a large part of
bonding energy come into existence and
electrostatic attraction b/w nucleus and
Pi Bond
accumulated e- cloud between them.  Formed by lateral or parallel or sidewise over
 Extended by Pauling and Slater lapping (above and below bonding axis)
 Greater the overlapping greater strength of  Formed between px–px, py–py, py–dxy, pz–dxz,
bond. dyz–dyz, and dxz–dzx, orbitals
 Paired e– can enter bond formation if they can
unpaired first and shifted to vacant orbitals of same
orbit.
 Between two orbital of same stability, one with
more directionally concentrated would formed
stronger bond
S–S<S–P<P–P

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 Chemical Bonding
+ of minimum energy and maximum stability of the
py dxy py-dxy
overlapping
 Existence of  depends on sigma,
 e– cloud is unsymmetrical hence weaker bond.
 Free rotation is not possible around  - bond
  e– are mobile i.e, delocalized e–
 It has no primary effect on the direction of bond
but shortens the internuclear distance.
 The molecular pi-orbital consists of two
electron clouds, one above and one below the plane
of the bonded atoms.
N.B.
The strength of a bond depends upon the extent of
overlapping of half-filled atomic orbitals. The
extent of overlapping between two atoms is always
greater when there is end to end overlapping of
orbitals than when there is lateral overlapping of
orbitals. Hence a σ - bond is stronger than a π -
bond.
VSEPR Theory
(Valence Shell Electron pair Repulsion)
 Proposed by Gelespi & Nyholm
 This theory provides a simple method to predict
the shapes of covalent molecules.
 The theory is primarily based upon the fact that
in a polyatomic molecule, the direction of bonds
around the central atom depends upon the total
number of electron pairs (bonding as well as non-
bonding) in its valence shell.
 The electron pairs place themselves as far apart
as possible in space so as to have minimum
Cool Chemistry 9051122547/9339228404
repulsive interactions between them.
 The minimum repulsion corresponds to the state
molecule.
 A multiple bond is treated as if it is a single
electron pair and the two or three electron pairs of a
multiple bond are treated as a single super pair.
 Where two or more resonance structures can
represent a molecule, the VSEPR model is
applicable to any such structure.
 The repulsive interactions between two lone
pairs (lp) are different from those between two
bond pairs (bp) or those between a lone pair and a
bond pair. The repulsive interactions between
various electron pairs decreases in the order as: lp –
lp > lp – bp > bp – bp.
 Geometry of molecule
lp = 0 (regular or symmetrical)
lp > 0 (Irregular or distorted)
 Effect of lp on bond angle
BA  bp  1/Lp
 Eg:-
Molecule lp bp B.A
CH4 0 4 109.5o
NH3 1 3 107
H2O 2 2 105
Hybridisation
 Mixing of two more atomic orbital of nearly
same energy to produce a new set of orbital i.e,
H.O (hybridized orbital)
 No. of HO = No. of A.O taking part in
hybridization
 All H.O has equivalent energy.
 H.O of a molecule are identical in shape, size
may very
 Orbitals of central atom of a compound
participates in the hybridization
 H.O always formed sigma bond
 H.O formed stronger bond than A.O
 P.E of H.O is lower than A.O
 Different types of hybridization  sp, sp2, sp3,
dsp2, sp3d, dsp3, sp3d2, d2sp3, sp3d3.
Note - P.E = sp3 > sp2 > sp
8
 Chemical Bonding
 B.A  S-character  1/P character
Bond Length
Character sp sp2 sp3 sp3d sp3d2  Distance between two nuclei of two atoms
s 50 33.33 25 20 16.67 bonded together
p 50 66.67 75 40 50  BL  size of atom
d 0 0 0 20 33.33
 BL 

 E.N  s – character C – C(1.54 Å) > C=C(1.34 Å) > CC(1.20Å)

Eg: C2H6 < C2H4 < C2H2  BL 
 E.N  C(sp3)–H (1.09Å) > C(sp2)–H (1.08Å) > C(sp)–
H (1.06Å)
 Size of hybrid orbital  p character

Bond Energy Molecular Orbital Theory

 Energy required to beak bond
 B.E   orbitals called molecular orbitals.
 B.E  Bond multiplicity (CC > C=C > C–C)
 BE 
 BE  s-character 
C(sp) – C(sp) [103.6 kcal / mol.]
C(sp2) – C(sp2) [91.58 kcal / mol.]
C(sp3) – C(sp3) [82.78 kcal/mol.]
 BE of homolytic < BE of heterolytic
 BE of  bond >  bond
N.B.
 Most of the covalent bond have energy
between 50 to 100 kcal mol.–1
 Homoloytic Bond Fission
C2H5Br  C2H5 + Br; 67.2 kcal mol.–1
 Heterolytic Bond Fission
C2H5Br  +C2H5 + –Br; 183 kcal mol.–1
 Proposed by Hund and Mulliken
 In molecules, electrons are present in new
 Molecular orbitals are formed by combination
of atomic orbitals of nearly same energies.
 Molecular orbitals are not associated with a
particular atom but belong to nuclei of all the atoms
constituting the molecule. Nuclei of different atoms
in the molecule behave as polycentric nucleus.
 No. of AO = No. of MO.
  = wave function (waves)
 2 = probability of finding e- (orbital)
 Linear Combination of Atomic Orbital (LCAO)
(a) Overlapping of wave in same phase or
constructive interference (addition) – Bond
Molecular Orbital (BMO) or Highly Occupied MO
(HOMO)

Bond Angle
 Angle between two adjacent bond
 BA  s-character
 BA  BP 
 BA  EN A = Orbital atom of A
 BA  B = Orbital atom of B
B.M.O = b
 BA  Bond multiplicity ( CC > C=C > C–C)
b = A + B
 Size of central atom 
b2 = A2 + B2 + 2 A B
Eg:- H2O > H2S > H2Se > H2Te  Overlapping of wave is opposite phase or
NH3 > PH3 > AsH3 > SbH3 destructive interference (subtraction) – ABMO or
 Size of terminal atom  BA (due to steric LOMO
hindrance)
Eg:- OF2 < OCl2 < OBr2 < OI2
NH3 > NF3 (exception)

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 Chemical Bonding
 BMO =  , ,  etc
 ABMO = *, *, * etc
  <  <  < n < * < * < *
n = non-bonding orbital

Molecular Orbital Configuration

A = Orbital atom of A
B = Orbital atom of B
A.B.M.O = a
a = A - B
A2 = A2 + B2 + 2 A B
 Follows Pauli exclusion principle, Aufbau and
Hund’s rule
 Configuration up to 14 e- (N2)
 1s < * 1s <  2s < * 2s < 2px =  2py < 
2pz < * 2px = * 2py < * 2pz
e.g. N2:- 1s2 *1s2 2s2 *2s2 2px2 2py2 2pz2

Formation of BMO & ABMO

AO BMO ABMO
1s + 1s  1s * 1s Considering
2s + 2s  2s * 2s z as nuclear
2px + 2px  2px * 2px axis
2py + 2py 2py * 2py
2pz + 2pz  2pz * 2pz

(a) Combination of S –S Orbital

 Configuration more than 14 e- (O2 and above)

1s < *1s < 2s < *2s < 2pz < 2px = 2py
< *2px = *2py < *2pz
e.g. O2 :- 1s2 *1s2 2s2 *2s2 2pz2 *2px2
*2py2 2px1 2py1

(b) Axial combination of p – orbital

N.B
Energy of BMO < ABMO

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 Chemical Bonding
N.B + - + +
 2px & 2py, *2px & *2py are degenerate H – F ……. H – F (dipole –dipole)
orbitals - +
 *1s, *2s, *2pz, 2px and 2py has one F – H …….. F – (ion – dipole)
nodal plane Condition of H.B
 *2px + *2py has two nodal plane Z – Should be small
EN. Of Z – high
 1s, 2s and 2pz do not have any nodal
Z = N,O,F
plane.
 H.B.E  EN ( H – N -- H) < H – O -- H) < (H
 UPE = 0 (Diamagnetic + colourless)
 UPE = 0 (Paramagnetic + colour) – F – H)
 UPE  Paramagnetic  H.B.E  No. of H.B formed
 H.B.E = 2 to 10 Kcal
 Magnetic moment () = n(n + 2) BM
 F−H----F (161.5 kJ/mol or 38.6 kcal/mol)
 O−H----N (29 kJ/mol or 6.9 kcal/mol)
Bond Order
 O−H----O (21 kJ/mol or 5.0 kcal/mol)
 No. of covalent bond between two atoms  N−H----N (13 kJ/mol or 3.1 kcal/mol)
 BO =  N−H----O (8 kJ/mol or 1.9 kcal/mol)
 B.O can be 0, (-), (+), or fraction etc. Hydrogen Bonding
 0, (-) molecule does not exit
 (+), fraction  molecule exit
Inter Molecular
 B.E  Stability  B.O  Inter Molecular Hydrogen
Hydrogen Bonding Bonding Chelation within
 B.L   Na formed between two the molecule
same different molecule
eg:- H2+, H2 , H2-
+

H2 =  1s2 = B.O = 2 – 0/2 = 1

Example of Inter M.H.B
H2+ =  1s1 = B.O = 1 – 0/2 = 0.5
H2- =  1s2, * 1s1, B.O = 2 –1 /2 = 0.5
B.E = H2- < H2+ < H2
B.L = H2 < H2+ < H2-

N.B Example of Intra M.H.B

 Isoelectronic species have same bond order
 CO32-, NO3- (1.33)
 CO, CN–, NO+, N2 (3)
 CN, CO+, N2+ (2.5)

Exceptional BO of CO+
MO configuration of CO N.B
1s2 *1s2 2s2 2px2 2py2 2pz2 *2s2  (HF)n + (H2O)n shows zig – zag structure
BO = = =3  Intra M.H.B is weaker than inter M.H.B
 for intra M.H.B formation
MO configuration of CO+
a) Distance between atom must be closer
1s2 *1s2 2s2 2px2 2py2 2pz2 *2s1
b) Ring should be formed with minimum strength
BO = = = 3.5 and maximum stability

Hydrogen Bond Effect of Hydrogen Bonding

 Proposed by Latimer and Rodebush  Inter M.H.B increases mp, bp, solubility,
H ………Z (E.N element) viscosity, surface tension, intermolecular attraction,
 Due to dipole – dipole interaction or ion – polarity, refractive index
dipole interaction  Intra M.H.B decreases the above properties.

Cool Chemistry 9051122547/9339228404 11

 Chemical Bonding
 Order of BP of hydride of group 16 becomes HCOOH form dimer.
H2O > H2Fe > H2Se > H2S (because O can form
HB)
 BP of NH3 (–33.4oC) is more than that of PH3
(–87.4oC) (because N can form HB)
 Compounds with inter MHB may be liquid in
state  One mole of H2O is surround by 4 mole of
e.g. H2O is liquid while H2S is gas water by inter MHB.
e.g. HF is liquid at 19.5oC while HCl, HBr and
HI are gas)
 Compounds with inter MHB shows association
of molecules (Dimer, Polymer)
Eg:- (HF)n, (H2O)n, (RCOOH)2

 Intra MHB increases strength of organic acid

while inter M.H.B decreases the strength of organic
acid
 Vol = H2O (l) < H2O (s) < H2O (g)
e.g. Ortho hydroxy benzoic acid is stronger
 D = H2O (g) < H2O(s) < H2O (l)
than para because o-hydroxy benzoic acid attains
 M.P anf B.P of p-nitro phenol is more than o-
additional stability through Intra MHB.
nitro phenol.[o-nitro phenol form Intra MHB while
p-nitro phenol form Inter MHB]

 Strands of DNA are held together by H.B.

 CuSO4 5H2O Contains ionic, covalent, co-
ordinate and H.B

 p-nitro phenol is more soluble in water than o-

 B.P of ethyl alcohol (78.5oC) is more than that
nitro phenol.[o-nitro phenol form Intra MHB hence
of dimethyl ether (–24.9oC).[In ethylalcohol H
in capable to form HB with water]
atom is directly attached with O atom hence can
 Ethyl alcohol is highly soluble while dimethyl
form HB but in ether H atom is attached with C, so
ether is sparingly soluble in water. [ethyl alcohol
HB is not formed]
can form HB with water but ether cannot]
 B.P of trimethylamine (CH3)3N (3oC) is less
 Alcohols having lower MW are soluble in
than that of propyl amine CH3CH2CH2NH2(49oC)
water but those with higher MW are insoluble.
[In tertiary amine there is no hydrogen attached
[Bulky alkyl groups does not allow to form HB]
with N, hence HB is not formed]
 NH4Cl is more soluble in water than NaCl.
 B.p of C2H5OH (78.5oC) is less than formic acid
 In spite of being organic compound, glucose
(HCOOH) (100.5oC) though their mol wt is same

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 Chemical Bonding
and sucrose are soluble in water [it contains –OH Vander Waal’s Force
group which can make HB with water].  Force between any two particles
 Boric acid H3BO3 or B(OH)3 contains –OH  5 – types
groups, yet it is sparingly in water.[it forms cyclic 1) Dipole – dipole interaction or keesom force:-
2D associated giant molecules through Inter MHB, interaction between permanent polar molecule
hence cannot form HB with water.]
+ - + -
Permanent Permanent
Dipole Dipole

2) Ion- dipole interaction:- interaction b/w ion

and permanent polar molecule
 H3PO4 is more viscous than H2SO4[number of
–OH group in H3PO4 is more than H2SO4] - + -
 Glycerol is more viscous than glycol. Permanent Anion
 HF is a monobasic acid but it forms KHF2 salt Dipole
because F– ion forms highly stable bifluoride ion
+ - +
(HF2–) by producing HB with HF molecule.
H2F2  H+ + [F---H–F]– Permanent Cation
H2F2 + KOH  KHF2 + H2O Dipole
 KHF2 of HF2– exists due to HB but formation
of HCl2– is not possible.
 On heating crystal of blue vitriol or cupric
sulpahte pentahydrate (CuSO4.5H2O), four
molecules of water of crystallization are easily
removed. But the removal of the last molecule of
water crystallization requires high thermal energy
because the fifth water molecule is hydrogen
bonded with sulphate ion.

 Maleic acid is stronger than Fumaric acid 3) Ion induced dipole interaction:-
Ion attracts neutral molecule and causes temporary
polarity in them resulting interaction between ion
and dipole

- + -
Temporary Anion
Dipole
+ - +
Temporary Cation
Dipole

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 Chemical Bonding

4) Dipole induced dipole

Attraction between permanent and temporary
dipole.

+ - + -
Permanent Temporary
Dipole Dipole

5) London force and dispersal force

Attraction between non-polar molecules

N.B.
H.B is a special kind of dipole –dipole interaction

Order of Strength
(a) ion dipole > ion induced dipole > H.B > dipole
– dipole > dipole induced dipole > London.
(b) ionic > Co-ordinate > covalent > H.B > vander
waal’s

Cool Chemistry 9051122547/9339228404 14