BONDING

Atoms can share pairs

of electrons to make
covalent bonds

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If the electronegativity
difference is large - greater
than 1.7 or so - they can
transfer electrons to form
ionic bonds

Molecular Shape

Directional bonds with fixed lengths lead to the idea of molecular shape. Can
the shapes be predicted ?

YES. Prediction - which works - is based on the simple principle that electrons
(and therefore bonds!) repel each other:-

THE SHAPE OF ANY MOLECULE IS THAT WHICH MINIMIZES

THE REPULSIONS BETWEEN THE VALENCE SHELL
ELECTRON PAIRS ON THE ATOMS IN THE MOLECULE

VALENCE SHELL electron pairs means electrons in bonds and non-bonding

electrons (lone pairs)
This simple principle leads to a (relatively) simple procedure : the Valence
Shell Electron Pair Repulsion (VSEPR) method
aka Nyholm-Gillespie method after the guys most people think invented it
& as Sidgwick-Powell method after the guys who really invented it

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Molecular Shape : VSEPR Method

Procedure : Working atom by atom:(1) Find total number of electrons around atom. This is :
The number of valence electrons (s & p only for p-block elements)
PLUS one for each normal covalent bond (2 for double bonds etc)
PLUS 2 for each dative bond TO the atom.
(2) Count total number of bonds (B : all bonds - single, double or triple add 1
to B) and lone pairs (L) round atom under consideration BL(L is half
no. of electrons not in bonds)
(3) Arrange BLbonds and lone pairs in 3D to be mutually as far apart as
possible.
This gives the BASIC GEOMETRY of the molecule. (Possibilities for
molecules of formula AB n are on the next slide)
(4) The molecular shape is then that defined by the resulting relative
positions of the atoms alone.

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VSEPR : Basic Geometries

B + L = 2;
linear
B + L = 3;
planar triangle
= 120o.
B + L = 4;
tetrahedron
= 109.5o.
B + L = 5;
trigonal
bipyramid
= 90o ; =
120o.

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B + L = 6;
octahedron
all angles 90o.

B + L = 7;
pentagonal bipyramid
axial angles 90o;
equatorial angles 72o

VSEPR examples (1) : CH4, NH3, H2O

H

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H
H

NH3 : Pyramidal
HNH = 107.3o.

H
H

In each case, 8 electrons = 4 pairs

around central atom (C, N or O)
CH4 : B = 4; L = 0
NH3 : B = 3; L = 1
H2O : B = 2; L = 2
Therefore Basic Geometry is
tetrahedral.
See : H atoms are squeezed
together by lone pairs, which
require more room
Can predict distortions if single
bond (S), double bond (D), and
lone pairs (L) present, as
repulsions vary as :
D-D > D-L > L-L D-S > L-S > S-S

CH4 : Tetrahedral
o
HCH
=
109.5
.
H

H2O : Bent
HOH = 105.8o.

VSEPR examples (2)

Ethyne (C2H2)
One triple bond and one single bond
about each C B = 2; L = 0;
linear :H-CC-H, with 180 bond angles.

PF5
Around P : 5 P valence electrons, + 1
from each F = 10 electrons in five
bond pairs; B = 5; L = 0;
trigonal bipyramid :F

BF3
Six electrons around B (3 from B; 1
from each F); all in bond pairs - 3
single bonds. B = 3; L = 0planar
triangular :F
with 120
bond angles.
B
F
F

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F
P
F

VSEPR examples (3) : Slightly more difficult!

XeF4

SF4

Xe : 8 valence electrons + 1 from each

F = 12; 4 bond pairs & two lone
pairs: B = 4; L = 2; octahedral
F
but two posibilities :

S : 6 valence electrons + 1 from each

F = 10; 4 bond pairs & a lone pair:
B = 4; L = 1; trigonal bipyramid,
but again two posibilities :
F
F
F
F

OR

F
F

F
F

OR

F
F

keeps lone pairs

further apart, so this
correct and geometry
is SQUARE PLANAR

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reduces L-S repulsions (2 at

90 + 2 at 120 vs. 3 at 90)
therefore geometry is seesaw shape

VSEPR examples (4)

XeOF4
Xe : 8 valence electrons + 2 from O + 1 from each F : total 14 electrons.
4 in double bond (D) to O; 8 in 4 single bonds (to F); 2 in lone pair
i.e. B = 5; L = 1 and basic geometry is octahedral :
Largest repulsion is D-L; therefore O opposite
lone pair (in axial positions, with F all in one equatorial - plane

O
F

F
Xe
F

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Remember : D-S repulsion > L-S and S-S, so

Xe=O bond pushes Xe-F bonds down ;
RESULT : - OXeF > 90 (slightly) and molecule
is SQUARE PYRAMIDAL

VSEPR - two further details

The same method can be applied to the ionic species formed by some of the
p-block elements e.g.
AsF4+ & AsF4- : In each case, As has 5 valence electrons + 1 from each F = 9;
in first case less 1 for +ve charge = 8 in (B = 4, L = 0); Tetrahedral
in 2nd. case plus 1 for -ve charge = 10 in (B = 4, L = 1); same shape as SF4

HYBRIDIZATION - for those who have heard of it - is essentially a scheme

for deciding which atomic orbitals are involved in bond formation. This is
decided by molecular geometry (in particular, symmetry) so that, for
example :

C in methane is sp3 hybridized BECAUSE methane is

tetrahedral
and not vice versa

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Polar Bonds

Where a covalent bond joins two atoms (or groups) of different electronegativity
then the more electronegative atom will have a greater attraction for the
electrons - which means, effectively, that atom acquires a partial negative
charge, - (and the other, a partial charge, +). Hence :
(1) there is a dipole moment, B = L, where L is the bond length associated
with the bond
(2) the bond has a partial ionic character - ionic bonds are an extreme case of
polar covalent bonding!
Some examples of polar bonds are :
H-Cl O-H in H2O
C-C in CH3CF3

Note : B is directional; i.e. is a VECTOR quantity

The more electronegative element almost always has the partial negative charge
- the only important exception is carbon monoxide (CO) where the C is - rather
than the O
Dipoles are measured in Debye (D) - 4.8D is the dipole arising from charges of
+e and -e separated by 0.1 nm (1 A)

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Molecular Dipole Moments ()

A polar molecule is one with a non-zero dipole moment () - arising from the
polarity of the bonds in the molecule AND the presence of directional lone
pairs
Dipole moments are important as the ability of a solvent to dissolve ionic/polar
solutes depends on its molecular dipole moment; so do the dielectric constant
and refractive index of a material.
The molecular dipole moment is the vector sum of the bond dipoles and the
dipoles resulting from lone pairs on non-terminal atoms

= LONE PAIRS)

(Contribution from lone pairs is normally MUCH bigger than from bonds)
ALL heteronuclear diatomics (CO, HCl etc) have dipole moments.
Homonuclear diatomics (H2, O2 etc) all have zero dipole moment

Not all molecules with polar bonds have dipole moments (e.g. CO2)

THERE IS NO SUCH THING AS A PURELY IONIC BOND

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Molecular Dipole Moments ()

Consider the three di-chloro benzene molecules :

Cl

Cl

Cl
Cl

Cl
A : 1,2 dichlorobenzene

B : 1,3 dichlorobenzene

Cl
C : 1,4 dichlorobenzene

A & B have permanent dipole moments; C has = 0. Since dipole moment is

the vector sum of the bond dipoles, (A) > (B)
Some other molecules with permanent dipole moments are :
H2O SF4
BrF3
O3

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Bond Energy

Given that bond formation lowers energy, breaking bonds requires energy the bond energy
There are three meanings to bond energy :
(1) BOND DISSOCIATION ENERGY is the energy required to break a
specific bond
e.g. the O-H bond dissociation energy in H2O is the energy change for H2O
OH + H and is 498 kJ mole-1.
(2) BOND ENERGY in a compound (e.g. the O-H bond energy in H2O) is
the average of the energy required to break ALL the identical bonds
in the molecule
e.g. the O-H bond energy in H2O is half the energy change for
H2O O + 2H and is 463 kJ mole-1.
(3) MEAN BOND ENERGY (as presented in tables of Bond Energy) is the
mean value of (2) over a large number of compounds.
For O-H bonds it happens to be 463 kJ mole-1.
Such tables NORMALLY present values of BOND ENTHALPY.

In diatomics, there can be no confusion (as (1) & (2) are the same)

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Bond Energies (II) : Reaction enthalpy

For any chemical reaction :H (all bond energies in reagents) - (all bond energies in products)
e.g. :
Estimate the standard enthalpy of the reaction :
CH4 + 2 F2 = CH2F2 + 2 HF

In the reagents : there are 4 C-H single bonds and 2 F-F single bonds
(mean enthalpies : 412 & 158 kJ mol -1 respectively - see tables such
as Atkins & Jones pp 317,318)
In products there are 2 C-H bonds, 2 C-F bonds and 2 H-F bonds
(enthalpies : 412, 484 & 565 kJ mol-1 respectively)
therefore H = (4x412 + 2x158) - (2x412 + 2x484 + 2x565) kJ mol -1
= -958 kJ mol-1
Since the tabulated values are averages this gives an ESTIMATE of
the true value for reaction enthalpy

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