Chemical Bonding - by WWW - Learnengineering.in
Chemical Bonding - by WWW - Learnengineering.in
Chemical Bonding - by WWW - Learnengineering.in
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CHEMICAL BONDING
I NT RO DU CT IO N
(a) It is well known fact that except for inert gases, no other element exists as independent atoms under
ordinary condition.
(b) Most of the elements exist as molecules which are cluster of atoms. How do atoms combine to form
molecules and why do atoms form bonds? Such doubts will be discussed in this chapter.
(c) A molecule will only be formed if it is more stable and has a lower energy, than the individual atoms.
Chemical Bond :
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(a) A force that acts between two or more atoms to hold them together as a stable molecule.
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(c) This process accompanied by decrease in energy.
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(e) Therefore molecules are more stable than atoms.
(b) Two nuclei and electron of both the atoms repells each other.
Potential Energy diagram
(c) If net result is attraction, the total energy of the system (molecule) decreases and a chemical bond forms.
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2. Octet rule
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Atoms Combines to complete an octet of electrons in their outer most orbit. Complete orbital represents to get most
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stable state. Hence all atoms have a tendency to acquire octet (s2p6) configuration in their outermost orbit.
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Be F2 B
——
F
— 3
Al Cl3 B
—— —
Cl3 F
×
|
..
(4e) (6e) (6e) (6e)
B
. ×F (6 Electrons)
|
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|
×
4. Expansion of Octet (due to empty d-orbitals) F
F
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PCl 5 SF 6 ClF3 ICI5 IF7 F
F S F
(10e) (12e) (10e) (12e) (14e)
5. Odd electron species
e F (12e) F
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Ex. NO, NO2, ClO2 etc.
O
N ,
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N O
O
6. Compounds of Noble gases
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Noble gases which have already completed their octets (or douplet in case of He.) should not form compounds.
However, their compouinds like XeF2, XeF6 & KrF2 etc., have been actually prepared.
CL ASSIFICATION OF BONDS
A T T R A C T IV E F O R C E S
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×
×
× O= O
×× N N
× ×
× ×
H2 molecule O O N N
(b) The shared pair of electrons should have opposite spins, and are localised between two atoms
concerned.
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H
N N Triple bond. (not three single bond) O = O (Double bond) H – O – H (Two single bonds.)
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CO-ORDINATE BOND
(a) It is a covalent bond in which the shared electron pair come from one atom is called coordinate bond.
(b) Necessary conditions for the formation of co-ordinate bond are -
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(i) Octet of donor atom should be complete and should have atleast one lone pair of electron.
(ii) Acceptor atom should have a defficiency of at least one pair of electron.
(c)
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Atom which provide electron pair for shairing is called donor.
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(d) Other atom which accepts electron pair is called acceptor. That is why it is called donor-acceptor or
dative bond.
H F
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H–N: + B–F NH3 BF3
H F
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H3N NH
3
+
H
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(Lowry-Bronsted acid) H
(e– acceptor)
H H
+
H3O ; O + H +
O H+
H H
Note : Compounds in which Ionic, covalent and co-ordinate bonds are present, are as follows -
NH4Cl, CuSO4.5H2O, K4[Fe(CN)6], KNC, KNO3, etc.
(a) One orbital can accomodate at the most 2 electrons with opposite spins
(b) Half filled orbital or unpaired electron orbital accepts one electron from another atom, to complete its orbital.
(c) Tendency to complete orbital or to pair the electron is an condition of covalent bond.
Completion of octet is not the essential condition of covalent bond.
(d) If the outermost orbit has empty orbitals then covalent bonds are formed in excited state.
Variable valenc y i n covalent bonds :
(i) Variable valencies are shown by those elements which have empty orbitals in outermost shell.
(ii) Lone pair electrons get excited in the subshell of the same shell to form the maximum number of
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unpaired electrons. Maximum covalency is shown in excited state.
(iii) The energy required for excitation of electrons is called promotion energy.
(iv) Promotion rule – Excitation of electrons in the same orbit.
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Ex.
(I) Phosphorus Ground state
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Covalency 3 (PCl3)
3s 3p
Phosphorus Excited state
e
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Covalency – 5 (PCl5)
3s 3p 3d
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3s 3p 3d Covalency - 2 (SF2)
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3s 3p 3d
(Ground state)
5s 5p 5d
So it shows three excited states – Maximum number of unpaired electrons = 7
Variable Valencies are 1, 3, 5, 7
To explain the formation of covalent bond two theories based on quantum mechanics have been proposed.
Valence bond theory (VBT) Molecular orbital theory (MOT)
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(i) Nature of orbitals – p, d and f are directional orbitals more overlapping
s-orbital non directional – less overlapping
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(ii) Nature of overlapping –
Co-axial overlapping - extent of overlapping more.
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Collateral overlapping - extent of overlapping less
Order of strength of Co - axial overlapping – p - p > s - p > s - s
• • e • • • •
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p-p p–s s–s
1s - 2p > 2s - 2p > 3s - 3p
(i) Electron which is already paired in valency shell can enter into bond formation, if they can be unpaired
first and shifted to vacant orbitals of slightly higher energy of the same energy shell.
(j) This point can explain the trivalency of boron, tetravalency of carbon, pentavalency of phosphorus etc.
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s - s, s - p, p - p (axial), sp3 – s, sp2 – s, sp3 – sp3, sp3 – sp2 & sp – sp atomic orbitals.
Sigma bond
+
S – S overlapping
-bond
2. Pi () bond : When two p-orbitals along the lateral axis (side way), -bond is formed.
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+
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Sigma-bond Pi-bond
e
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1. A -bond is formed by the axial overlapping A -bond is formed by the side ways overlapping
of atomic orbitals. of orbitals.
2. -bond formation involves overlapping of s-s, It involves overlapping of p-p orbitals.
s-p and p-p orbitals.
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3. -bond is stronger because of larger extent of -bond is relatively weaker because of smaller
overlapping extent of overlapping.
4. The molecular orbital is symmetrical about The molecular orbital is discontinuous and consists
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internuclear axis and electron cloud is present on two electron clouds below and above the internuclear
this axis axis
5. Free rotation exists around a -bond. Free rotation does not exist around -bonds.
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6 A sigma bond may exist either alone or A -bond is always present along with a sigma-bond
or along with -bonds.
7. Hybridised orbitals or unhybridised orbitals are Hybridised orbitals are never involved in -bond.
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involved in -bond.
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3. Dalta()-bond: It is special type of lateral overlapping in which all four lobs of d-orbital are overlap laterally
with other smilar d-orbital produce delta()-bond.
–
+
–
+ +
–
+ z
–
dx2–y2 dx2–y2
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orbitals. and the phenomenon is called hybridisation.
Now after considering s–p hybridisation in BeCl2
p–sp sp–p
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Cl ——— Be ———— Cl
bond strength of both the bonds will be equal.
Characteristic of Hybridisation :
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(a) Hybridisation is a mixing of orbitals and not electrons. Therefore in hybridisation full filled, half filled and
empty orbitals may take part.
(b) Number of the hybrid orbitals formed is always be equivalent to number of atomic orbital which have
taken part in the process of hybridisation.
e
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(c) Each hybrid orbital having two lobes, one is larger and other is smaller. Bond will be formed from large lobe.
(d) The number of hybrid orbitals on central atom of a molecule or ion = number of bonds + lone pair of
electron.
(e) One element can represent many hybridisation state depending on experimental conditions
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stronger sigma bond. The directional property of different hybrid orbitals will be in following order.
sp < sp2 < sp3 < sp3d < sp3d2 < sp3d3
(h) Hybridize orbitals show oxial overlapping & form bond
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TYPES OF HYBRIDISATION :
1. sp hybridisation :
(a) In this hybridisation one s– & one p– orbital of an atom are mixed to give two new hybrid orbitals which
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2s 2p
Be (excited state)
sp hybridisation
F F
B (ground state)
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B (excited state)
sp2 hybrid orbitals
2 2 2
sp sp sp
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B atom share 3 electrons
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3. sp 3 Hybridisation :
(a) In this hybridisation one s orbital & three p orbitals of an atom of a molecule or ion, are mixed to give four
new hybrid orbitals called as sp3 hybrid orbitals.
(b)
e
The angle between these four hybrid orbitals will be 109° 28'
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2s 2p
C (ground state)
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C (excited state)
sp3 hybridisation
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4 hydrogen atoms
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(c) The shape obtained from these hybrid orbitals would be tetrahedron.
4. sp 3 d Hybridisation :
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(a) In this hybridisation one s orbital, three p orbitals and one d orbital are mixed to give five new hybrid
orbitals which are equivalent in shape and energy called as sp3d hybrid orbitals.
(b) Out of these five hybrid orbitals, three hybrid orbitals are at 120° angle and two hybrid orbitals are
perpendicular to the plane of three hybrid orbitals that is trigonal planar, the shape of molecule becomes is
trigonal bipyramidal.
For example, PCl5 showing sp3d hybridisation
3s 3p 3d
P (ground state)
3s 3p 3d Cl
P* (excited state)
Cl P Cl
sp3d hybridisation
3 3 3 3 3
Cl
sp dsp dsp dsp dsp d
P atom share five e with Cl
Cl Cl Cl Cl Cl Cl
Structure of PCl5
(c) In this hybridisation dz2 orbital is hybridised with s and p orbitals.
In this way five sp3d hybrid orbitals form five sigma bond with five Cl atoms and give a molecule of PCl5,
shape of this molecule is trigonal bipyramidal.
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Axial two P–Cl bonds are longer than equatorial three P–Cl bond due to repulsion
between 3 equitorial b.p. of e– and 2 axial b.p. of e–
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5. sp 3 d 2 Hybridisation :
(a) In this hybridisation, one s-orbital, three p-orbitals & two d-orbitals are mixed to give six new hybrid
orbitals known as sp3d2 hybrid orbitals.
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(b) The shape of molecule obtained from above six hybrid orbitals will be symmetrical octahedral.
(c) The angle between all hybrid orbitals will be 90°.
Ex. SF6, AlF6–3, PF6–, ICl5, XeF4, XeOF4, ICl4–,
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(d) Two 'd' orbital participates in the hybridisation are dx2–y2 and dz2.
3s 3p 3d
SF6 S (ground state)
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3s 3p 3d
S (IInd excited state)
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sp3d2 hybridisation
3 2 3 2
sp3d2 sp3d2 sp3d2 sp3d2 sp d sp d
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6. sp 3 d 3 Hybridisation :
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(a) In this hybridisation, one s-orbital, three p-orbitals & three d-orbitals are mixed to give seven new hybrid
orbitals known as sp3d3 hybrid orbitals.
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F F
I
F F
F
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(iii) The electronic repulsion between two pairs of electrons will be minimum if they are as far apart as possible.
(iv) The actual shape of the molecules containing lone pairs is a little distorted from the basic shape as in the
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NH 3 and H 2O molecules, the bond angles are not 109º28' but 107º and 104.5º respectively due to
presence of one lone pair in NH3 and two lone pairs in H2O.
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Number of Molecule Electronic Bonding Non-bonding Molecular Example
electron pairs type geometry pair pair (E) geometry
2 AB 2
2e 0 B A B BeF 2,BeCl 2
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Linear Linear
O C O etc
B
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F
A
3 AB 3 3 0 B B B
Trigonal planar Trigonal planar
F
F
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N
AB2 Trigonal planar 2 1
B B O O ,SO2, O3
Bent
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B
H
A
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4 AB 4
4 0 B B C
B H H
H
Tetrahedral Tetrahedral
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A
N
B B H H
AB 3 E Tetrahedral 3 1 B
H
Trigonal pyramidal
A
O
B
AB 2 E 2 Tetrahedral 2 2 H
B
H
Bent
B
B
A B
B
5 AB5 5 0 PCl5
B
Trigonal bipyramidal
Trigonal bipyramidal
B
A B
AB4E Trigonal bipyramidal 4 1 B SF4
B
See saw
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B
A B
AB3E2 Trigonal bipyramidal 3 2 ClF 3
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B
T-shaped
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A
e B
Linear
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B
B B
A
B B
6 AB 6 6 0 SF 6
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B
Octahedral
Octahedral
B
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B B
A
AB 5 E Octahedral 5 1 B B BrF 5
Square pyramidal
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B B
A
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B B
AB 4 E 2 Octahedral 4 2
XeF 4
Square planar
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1
No. of hybrid orbital = [Total number of valence e– in the central atom + total number of
2
monovalent atoms – charge on cation + charge on anion]
1
Ex. NH 4 2
[ 5+ 4 – 1] = 4 sp3 hybridisation.
1
SF4 [6 + 4] = 5 sp3d hybridisation.
2
1
SO 2 sp3 hybridisation.
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4
[ 6 + 2] = 4
2
( 'O' is divalent so add only charge on anion)
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1
NO 3 [5 + 1] = 3 sp2 hybridisation.
2
If such type of e– pairs are –
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two – sp hybridisation
three – sp 2 hybridisation
four – sp 3 hybridisation
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five – sp 3 d hybridisation
six – sp 3 d 2 hybridisation
seven – sp 3 d 3 hybridisation
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BOND LENGTH
(i) The internuclear distance between the two single covalently bonded atoms is called bond length or bond
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distance.
(ii) If the electronegativities of both the atoms are equal, then the bond length is equal to the sum of the
covalent radii of two bonded atoms. dA – A = rA + rA
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(ii) If the electronegativities of two bonded atoms differ, then the bond length is smaller than the sum of their
covalent radii. dA – B < rA + rB
Factors affecting bond length
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Ex. CH 4 NH 3 H2 O
Hybridisation sp 3 sp 3 sp 3
Lone pair e–
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zero one two
Bond angle 109º28' 107º 105º
The different in bond angle is explained on the basis of following repulaion sequence
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The repulsion between
lone pair-lone pair > lone pair - bonded pair > bonded pair - bonded pair
(iii)
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Electronegativity: When compounds having same hybridisation state of central atom and some number
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of lone pair of electrons, then bond angle depends on electronegativity.
Bond angle electronegativity
Ex. H2O > H2S
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(iv) Size of terminal atoms: When size of terminal stoms increases, bond angle increases.
Ex. OF2 < Cl2O < Br2O
PF3 < PCl3 < PBr3
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BOND ENERGY
(i) The amount of energy required to break one mole of the bond and separate the bonded atoms in the
gaseous state is known as the bond energy of that particular bond.
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(a) Electronegativity difference of the bonded atoms : As the EN difference of the bonded atoms
increases the bond energy increases because the ionic nature of the bond increases.
Ex. Bond strength of hydrogen halides decreases in the order
H – F > H – Cl > H – Br > H – I
(b) Bond Order Bond energy Bond order, therefore the increasing order of bond energy is
C–C<C=C<CC
(c) Hybridisation state of the bonded atoms : Bond energy s-character
Ex. –C – H < –C = H < – C H
sp3 sp2 sp
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Ex. the bond energies of the following single bonds having zero, one, two and three lone pair of electrons
are in the order.
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C – C > N– N> O– O > F – F
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(a) The degree of polarity of covalent bond is given by the dipole moment (µ), which is the product of either
charge (e) and the distance (d) between them. µ = d × e. 'e' is the order of magnitude of the electronic
e
charge, i.e., about 10–10 esu and d is the distance between the atomic centres, i.e., about 10–8 cm.
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(b) Hence dipole moments may be expected to have value around 10 –10 × 10 –8 = 10 –18 esu-cm. It is
however, general particle to express dipole moments in Debye units (D), 1 D = 10–18 esu-cm.
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–
A B
Electronegativity of A < Electronegativity of B
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If the charge is in SI units (Coulumbs) and d in metre, µ will be coulumb-metre (cm) unit.
1D = 3.336 × 10–30 cm
(c) Any covalent bond which has a certain degree of polarity will have a coresponding dipole moment,
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though it does not follow that compound containing such bonds will have dipole moment,for the polarity
of the molecule as a hole is the vector sum of the individual bond moment.
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(i) For example, CO2 is a linear molecule, O = C = O, so that the dipole moments of the two C = O bonds
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cancel out.
(ii) The C Cl bond has a definite polarity and a definite dipole moment but carbon tetrachloride has zero
dipole moment becaue it is a tetrahedral molecule, and the resultant of the 4C – Cl bond moments is
zero.
(iii) On the contrary CH3Cl, CH2Cl2 and CHCl3 have definite dipole moments.
(Order of dipole moment CH3Cl > CHCl3 > CH2Cl2 > CCl4 = CH4)
Application of Dipole Moment Measurements
Dipole mement is a measure of the electrical dissymmetry (polarity) in the molecule and so its measurement
provides valuable information concerning the shape of molecules. Conversely, when the symmetry of the molecules
is known, dipole moment could be estimated fairly.
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2
and symmetrical (triangular) structure; other example are BF3, BBr3, CO 3 , and NO 3
Cl
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µ= 0
B
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Cl Cl
(e) PCl3, AsCl3, NH3, PH3, AsH3, H3O+ have apreciable dipole moment. They possess trigonal pyramidal structure.
P
e
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Cl Cl Cl
2. Organic substances
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(a) Mathane and CCl4 have zero dipole moment. So thay posess symmetrical tetrahedral structures with C
atom at the centre of the tetrahedron.
H
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C
H H
H
Methane
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(b) Benzene has zero dipole moment. All the 6C and 6H atoms are assumed to be in the same plane
(symmetrical hexagonal structure).
H
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H H
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H H
H
(c) Measurement of dipole moments will enable us to detect cis-and trans isomers of organic compounds (you
will learn about cis-trans or geometrical isomerism later in the organic chemistry).
The trans-isomer, which is symmetrical, has zero dipole moment while the cis-isomer has a definite dipole moment.
H H H Br
C C C C
Br Br Br H
cis-dibromoethylene (µ = 1.4D) trans-dibromoethylene (µ = 0)
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Y
Ortho Meta Para
In those cases where X = Y, the para isomer becomes symmetrical and have zero dipole moment. In
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order to find their dipole moment, we need to know about the nature of the groups linked to the benzene
ring. In nitro phenols, one group (OH) is electron pushing and the other (NO2) is electron withdrawing
while in aminophenols, both the groups (OH and NH2) attached are electron pushing. So, depending on
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the nature of the groups attached, the isomers have different dipole moment. Then calculation of dipole
moment follows as:
Case (i) : When X and Y both are electron pushing or electron withdrawing.
e
Let the bond dipole of C–X bond is represented by µ1 and that of C–Y bond by µ2. Now let us assume that
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the electgron pushing groups have +ve bond moment and the electron withdrawing groups have –ve
bond moment. The net dipole moment is the resultant of two bond dipoles at different orientations.
1
µortho = µ12 µ22 2µ1 µ2 cos 60 o = µ12 µ22 2µ1 µ2 ·
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µo = µ12 µ22 µ1 µ2
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µm = µ12 µ22 µ1 µ2
µp = µ1 – µ2
From the above expressions of µo, µm and µp, it is clear that when both X and Y are of the same nature
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i.e., both are electron withdrawing or both are electron pushing the para product has the least dipole
moment and ortho product has the highest dipole moment. When X = Y, µ1 = µ2, thus µp would be zero.
Case (ii) : When X is electron pushing and Y is electron withdrawing or vice versa.
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Let the bond moment of C–X dipole is µ1 and that of C–Y dipole is µ2.
= (µ1 µ2 ) 2 3µ1 µ2
= (µ1 µ2 ) 2 µ1 µ2
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(a) The chemical bond formed between two or more atoms as a result of the complete transfer of one or
more electons from one atom to another is called Ionic or electrovalent bond.
(b) Electro possitive atom loses electron (group IA to IIIA)
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(c) Electro negative atom gains electron (group VA to VIIA)
(d) Electrostatic force of attraction between cation and anion is called ionic bond or electrovalent bond.
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(e) Total number of electron lose or gained is called electrovalency.
Ex.
(i) Mg + O
e
Mg+2 + O–2
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2, 8, 2 2, 6
2e–
electrovalency of Mg = 2
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electrovalency of O = 2
+2 –
(ii) Ca Cl Ca + 2Cl
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+
2,8,8,2 2,8,7
One e–
Cl
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2,8,7
One e–
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electrovalency of Ca = 2
electrovalency of Cl = 1
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–2
(iii) Ca + O Ca+2 + O
2e–
electrovalency of Ca = 2
electrovalency of O = 2
(f) The force of attraction is equal in all direction so ionic bond is non-directional.
(g) A definite three dimensional structure is formed called crystal lattice.
(h) Ionic compound do not have molecular formula. It has only empirical formula.
Ex. NaCl is empirical formula of sodium chloride
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(c) A whole series of energy changes is involved when one starts from the elements and finishes with an ionic
crystal. These changes are shown in the Born-Haber cycle.
Formation of NaCl (s) involves
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1 Hf
Na(s) + Cl NaCl(s)
2 2(g)
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S D
2
Na(g) Cl(g) –U
I.P. –e– + e–
Na+(g)
– EGE
e
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Cl–(g)
D
thus S + I.P. + – EGE – U = Hf
2
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Higher lattice energy Greater will be the stability or strength of ionic compound.
Factors affecting lattice energy :
(i) Magnitude of charge U z+ z– (Ionic charge)
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Lattice energy Magnitude of charge
NaCl MaCl 2 AlCl 3
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Na+ Mg +2 Al +3
– Lattice energy increases
– Size of cation decreases.
1 e
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(ii) Size of Cation :- Lattice energy
r r
(a) Physical state – Ionic compounds are hard, crystalline and brittle due to strong electrostatic force of attraction.
Brittleness {Same charged ions comes nearer. So they repell each other}
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+ + + + + +
+ + + +
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+ + +
+ + +
+ +
+ +
Attraction Repulsion
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(b) Isomorphism : Different ionic compounds, having same configuration/geometry of ions are isomorphs
of each other and phenomenon is known as isomorphism
Ex. NaF, MgO, ZnSO4 · 7H2O, FeSO4 · 7H2O. All alums M2'SO · M2"(SO4)3 · 24H2O.
(c) Boiling point and melting point –
Ionic compounds have high boiling point and melting point due to strong electrostatic force of attraction
among oppositely charged ions.
(d) Conductivity – It depends on ionic mobility.
(i) In solid state - No free ions - Bad conductor of electricity.
(ii) In fused state or aqueous solution Due to free ions - Good conductor of electricity.
Conductivity order Solid state < fused state < Aqueous solution
(e) Solubility – Highly soluble in water (Polar solvents) Ex. NaCl in water
(i) The Na+ ions get associates with - vely charged 'O' of water
(ii) And Cl– ions associates with +vely charged 'H' of water.
+
H
– –
Na+ = O +
Cl–
H
(iii) Thus charge on Na+ and Cl– decreases and electrostatic force of attraction also decreases which leads
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to produce free ion.
(iv) The energy released due to interaction between solvent and solute is called solvation energy. If water is
used as solvent it is called hydration energy.
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(v) For an ionic compound to be soluble in water – Hydration energy > Lattice energy
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1
Lattice energy
So lub ility
e
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1 1
Hydration energy (H) { r+ & r– are radius of cation and anion}
r r
1 1
(vi) Hydration energy mainly depends on the cation radius because the value of is negligible in comparision to
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r r
(vii) Down the group both the lattice energy & hydration energy decreases, if decrease in lattice energy is
greater than hydration energy, solubility increases down the group and vice versa.
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represented by
(i) Water has maximum dielectric constant ( = 80)
(CH3OH = 35) , (Acetone = 21)
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H2O > CH3OH > CH3CH2OH > CH3COCH3 > CH3OCH3 > C6H6
(ii) Ionic compounds are more soluble in the solvents, having high dielectric constant.
(iii) H2SO4 and H2O2 have high dielectric constant but these are not a good solvent due to oxidising nature.
(b) Size of ion :
(i) Keeping size of cation constant, the lattice energy decreases with the increase of anionic radius.
Hence order of solubility of LiX in water is LiF < LiCl < LiBr < LiI
1
As solubility
lattice energy
(iii) Keeping size of anion constant, the hydration energy decreases with the increase of cationic radius.
Hence order of solubility of MSO4 will be – BeSO4 > MgSO4 > CaSO4 > SrSO4 > BaSO4 ( Exception of
Fajan's rule)
(iv) If size of cation and anion is very large, solubility decreases from top to bottom.
(v) Solubility decreases in a period (as ionic nature decreases and covalent nature increases)
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(a) Just as a covalent bond may have partial ionic character an ionic bond may also show a certain degree of
covalent character. When two oppositely charged ions aproach each other closely, the cation would
attract the electrons in the outer shell of the anion and simultaneously repel its nucles. This produces
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distortion or polarization of the anion, which is accompanied by some sharing of electrons between the
ions, i.e., the bond acquires a certain covalent character. The formation of a covalent bond between two
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ions may be illustrated with reference to formation of Agl.
The greater the charge on the cation, the more strongly will it attract the electrons of the anion. For
example, Al 3+ can distort Cl – ion more than Na + ion. So aluminium chloride is a covalent compound
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For a small cation, the electrostatic force with which its nucleus will attract the anion will be more.
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Moreover a large anion cannot hold the electrons in its outermost shell, especially when they are attracted
by a neighbouring cation. Hence there will be increased covalent charcter with a small cation and a large
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anion, as in AgI.
A cation with a 18 electron in outermost shell such as Ag+ ([Kr] 4d10) polarizes anions more strongly than
a cation with a 8 electron arrangement as in K+. The 'd' electrons in Ag+ do not screen the nuclear charge
as effectively as the 's' and 'p' electron shell in K+. Thus AgI is more covalent than KI, although Ag+ and
K+ ions are nearly of the same size. Cuprous and mercurous salts are covalent.
The above statements regarding the factors, which influence covalent character, are called Fajans' rules.
It can thus be seen easily that there is nothing like a purely ionic compound or a purely covalent compound.
Covalent character
Ionic character
From left (larger size) to right (smaller size) in a period increases so covalent character increases.
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- charge increases
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- Covalent character increases with particular anion
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Li +
K+ e
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- decreases
Cs +
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Neutral oxides doesn't react with acid & base eg. H2O, CO etc.
– decreases
– Basic character increases
Smaller the cation, more will be the tendency of forming complex compounds.
s-block metals (larger size) doesn't have the tendency to form complex compounds.
d-block metals have the tendency to form complex compounds (small in size, high charge).
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1
(e) To determine thermal stability of metal carbonates : stability (Covalent nature)
–––––––––––
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O
–
M+2 O— C MO + CO2
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O–
e
More smaller the size of metal cation, its polarisation capacity increases - strength of M—O bond increases
gin
and C—O bond decreases. So thermal stability of carbonates decreases.
CO3–2
O–2 + CO2
From top to bottom thermal stability of carbonates increases (as size of cation increases)
En
SnO 2 SnS 2
(White) (Yellow)
Since the value of for Be2+ is almost of the same order as that of diagonally situated Al3+. Hence have
many similar properties. Similarly value of for Li+ is equal to Mg+2 , so have diagonal relationship.
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(d) Energy of BMO < Energy of ABMO.
(e) Order of energy in molecular orbitals of di-atomic molecules.
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(i) From H2 to N2:
1s < *1s < 2s < *2s < 2pz = 2py < 2px < *2pz = *2py < *2px
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For N 2 molecule
^
e pz
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2p 2p
Increasing energy in N 2 molecule
pz
arn
px py
2s
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2s 2s
w.
2s
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1s
1s 1s
1s
pz
^
Bond order = ½ (8–4) = 2
p x p y
2p 2p
* Having two unpaired
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electrons so paramagnetic p x py
pz
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Increasing energy
2s
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2s 2s
e
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2s
1s
En
1s 1s
arn
1s
Nb Na
w.
Bond order =
2
Nb Na 2 0
Bond order = = = 1, Hence H – H (dimagnetic)
2 2
H2 2 ( s)2 1 Diamagnetic
H2+ 1 ( 1s)1 0.5 Paramagnetic
H2 3 ( 1s)2, ( * 1s)1 0.5 Paramagnetic
He 2 4 ( 1s)2, ( * 1s)2 0 Diamagnetic
N2 14 KK ( 2s)2, ( * 2s)2 , 3 Diamagnetic
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( 2py)2=( 2pz)2, ( 2px)2
O2 16 KK ( 2s)2, ( * 2s)2 ( 2px)2, 2 Diamagnetic
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( 2py)2=( 2pz)2 ( * 2py)1 ( * 2pz)1
O2+ 15 Remove one electron from 2.5 Paramagnetic
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* 2pz from O2
O 2 2+ 14 Same as that of N2 3 Diamagnetic
O2 17 KK ( 2s)2, ( * 2s)2 ( 2px)2, 1.5 Paramagnetic
( 2py)2,( 2pz)2
e
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( *2py)2,( *2pz)1
O22– 18 KK ( 2s)2, ( * 2s)2 ( 2px)2 1 Diamagnetic
( 2py )2,( 2pz)2
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NO – 16 Same as in O2 2 Paramagnetic
CN 13 Same as in NO2+ 2.5 Paramagnetic
ww
–
CN 14 Same as in N2 3 Diamagnetic
HYDROGEN BOND
(a) An atom of hydrogen linked covalently to a strongly electronegative atom can estabilish an extra weak
attachment to another electronegative atom in the same or different molecules. This attachment is called
a hydrogen bond.
(b) To distinguish from a normal covalent bond, a hydrogen bond is represented by a broken line,
e.g. X – H ... Y where X and Y are two electronegative atoms. The strength of hydrogen bond is quite low
about 2-10 kcalmol–1 or 8.4-42 kJmol–1.
H H H H
H H H H
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+ – + – + – + – + –
H — O ····· H — O ····· H — O, H — F ····· H — F
+ + +
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H H H
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H .............. F bond dissociation energy = 41.8 kJ mol–1
H .............. O bond dissociation energy = 29.3 kJ mol–1
bond dissociation energy = 12.6 kJ mol–1
H .............. N
e
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(e) Effect of H-bond
(i) It causes the association of many molecules.
(ii) Due to hydrogen bond molecules are associated and show high moleculer weight.
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solvents.
Examples : Alcohol & Ammonia are water soluble.
Type of H-bonding :
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(i) This type of H-bonding takes place between two moleules. Ex. ROH, H2O, R - OH & H2O
R R H H R H R
ww
| | | | | | |
O – H ... O – H, O – H ... O – H, O – H ... O – H ... O – H
(ii) In such compounds molecular wt., M.P, & B.P. are high.
(iii) Extent of H-bonding viscosity & density .
(b) Intramolecular Bond:
(i) It is the H-bonding in the same molecule of a compound. The bonding also known as chelation.
(ii) Solubility in water, M.P. & B.P. of these compounds decreases.
(iii) The value of acid strength of acid depends on the relative stability of the acid and its canjugated base
if the interamolecular H-bonding stablises the conjugate base then, the acid strength increase and if
the conjugate acid is stabilised in this way then the acid strength decreased.
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H2O > R-OH > R-OH Exceptional
H2S < R-SH < R-S-R Normal
H-bond increases
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H2O > R-OH > R-O-R
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B.P. increases
R-O-R no H-bond
H2O H-bonds
R-OH H-bond. e
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(iv) Alcohol and water are miscible in any proportion due to formation of H-bonds.
(v) Ammonia is excessively soluble in water whereas other gases are partially soluble. This is due to the
tremendous capacity of NH3 molecule to generate 4-H-bonds.
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– + – –
[ F ... H – F ] [Cl ... H – Cl]
exist does not exist
w.
o-nitro phenol, intra molecular H-bond exists which reduces the capacity of the molecule to produce
intermolecular H-bonds with other molecules like water. This brings interamolecular forces among the o-
nitrophenol molecules resulting into high volatility.
(ix) Acetic acid has a molecular weight of 60 in benzene and it shows a very high boiling points. This is due to
dimerization of molecule.
O – H ... O
CH3 – C C CH3
O ... H O
(x) Salicylic acid has very high acidity due to chelation of salicylate ion through the H-bond
–
O ··· H
C O
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C
H— C O–
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H— C OH
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O
(xiii) Normally when 2 hydroxyl groups are present on the same carbon atom i.e. gem diols are unstable, but
"chloralhydrate" is a stable molecule due to formation of H-bond.
e
Cl ..... H — O
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Cl C— C— H
En
Cl ..... H — O
O O
(xiv)
CH3 – C – CH2 – C – CH3
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In the above compound, (acetyl acetone) enol form is stable because of the intramolecular H-bond.
H
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O O
C C
w.
CH3 CH3
CH
ww
H
+
Na ······ O
H
(e) Dipole-dipole attraction : The force of attraction between the oppositely charged poles of two polar
molecules (for example : H2O, H–F, NH3 etc.) is called dipole-dipole attraction. This type of attraction is
weaker than the ion-dipole attraction.
O
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H–Cl
··
·· ·· H H
···
O
ng
···
O
H H
H H
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(f) Ion-induced dipole attraction : When non polar molecules come in contact with ions, its electron cloud
gets polarised and the oppositely charged end of it is attracted by the ion. For example attraction
between Na + and Cl 2 molecule.
– +
e
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Na+ + Cl – Cl Na+ ........ Cl – Cl
(g) Dipole-induced dipole attraction : This type of cohesive forces occurs in a mixture of polar and non
polar molecules. The former induce polarity in non polar molecules by disturbing their electron system.
for example force of attraction between Cl2 and H2O.
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O H
+ Cl – Cl O ........ + –
Cl – Cl
arn
H H H
(h) Induced-Induced dipole : The weak intermolecular forces operating in similar non polar gaseous
molecules are called London forces. These forces are very weak in nature and exists only at low
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temperature. For example weak intermolecular forces in F2, Cl2, N2, molecules and in nobal gasses.
w.
+ +
ww
– –
+ +