Bonding,

Molecular Shape & Structure

By
Dr. Fawaz Aldabbagh

http://www.nuigalway.ie/chem/Fawaz/fawaz.htm
The Periodic Table
 Lewis Symbols
Represent the number of valence electrons as dots
Valence number is the same as the Periodic Table Group Number
n=1

H He
n=2
Li Be B C N O F Ne
Groups 1 2 3 4 5 6 7 8

For example,

Na; Is2, 2s2, 2p6, 3s1 = [Ne] 3s1

Lewis Structure = Na
 Elements want to achieve the stable electron configuration
of the nearest noble gas

n=2
n=3

Ne

Atoms tend to gain, lose or share electrons

until they are surrounded by 8 electrons
Octet Rule
 Nobel Gas Has a Stable Electron Configuration

Ne; 1s2, 2s2, 2p6

Ar; [Ne] 3s2, 3p6

Ar
Example of Ionic Bonding
+
_
Na + F Na + [ F ]
11 9 10

Electronic configuration of Neon achieved in both cases

 There are two types of bonding;

Ionic Bonding refers to electrostatic forces between ions, usually a

metal cation and a non-metal anion

Covalent Bonding results from the sharing of two electrons between

two atoms (usually non-metals) resulting in molecules

Octet Rule applies

H + H H H
number of electrons around each atom = He

Cl + Cl Cl Cl
number of electrons around each atom = Ar

Triple bond
N + N N N
number of electrons around each atom = Ne

Each Covalent Bond contains two electrons

 Carbon has 4 valence electrons

H H
H C H H C H Ne
H H Neon
methane
H C

Stable Octet required

Covalent Bonding Atoms Share Electrons

Hydrogen molecule, H2

Concentration of negative charge between two

nuclei occurs in a covalent bond

7A elements (e.g. F) have one valence electron for covalent bonding,

so to achieve octet
6A elements (e.g. O) use two valence electrons for covalent bonding,
so to achieve octet
5A elements (e.g. N) use three valence electrons for covalent bonding,
so to achieve octet
4A elements (e.g. C) use four valence electrons for covalent bonding,
so to achieve octet
Carbon dioxide, CO2 Total Number of valence electrons = 4 + (2 x 6) = 16

O + C + O O C O = O C O
Double bonds
Rules for Drawing Lewis Structures
First sum the number of valence electrons from each atom
The central atom is usually written first in the formula
Complete the octets of atoms bonded to the central atom
(remember that H can only have two electrons)
Place any left over electrons on the central atom, even if doing so it
results in more than an octet
If there are not enough electrons to give the central atom an octet ,
try multiple bonds

E.g. 1. PCl3 Total Number of valence electrons = 5 + (3 x 7) = 26

Cl P Cl Cl P Cl Cl P Cl
Cl Cl
Cl
 E.g. 2; CHBr3
Total Number of valence electrons = 4 + 1 + (3 x 7) = 26

Br
Br C H
Br

Exceptions to the Octet Rule in Covalent Bonding

1. Molecules with an odd number of electrons

2. Other Natural Radicals, which do not obey Lewis Structures
(e.g. O2)
2. Molecules in which an atom has less than an octet
3. Molecules in which an atom has more than an octet
 1. Odd Number of Electrons
NO Number of valence electrons = 11

N O N O Resonace Arrows

Resonance occurs when more than one valid Lewis structure can be
written for a particular molecule (i.e. rearrange electrons)

NO2
Number of valence electrons = 17

O N O O N O O N O
Molecules and atoms which are neutral (contain no formal charge) and with an
unpaired electron are called Radicals

O2 O O O O
Oxygen is a ground state
"diradical"
 2. Less than an Octet

Includes Lewis acids such as halides of B, Al and compounds of Be

BCl3 Cl
Group 3A atom only has six electrons around it
B
Cl Cl
However, Lewis acids accept a pair of electrons readily from
Lewis bases to establish a stable octet

Cl H Cl H
_ +
Cl Al + N H Cl Al N H
Cl H Cl H
Lewis acid Lewis base salt
 AlX3

Aluminium chloride is an ionic solid in which Al 3+ is surrounded by six Cl-.

However, it sublimes at 192 C to vapour Al2Cl6 molecules

Cl Cl Cl
Al Al
Cl Cl Cl
B2H6
A Lewis structure cannot be written for diborane.
This is explained by a three-centre bond single electron is
delocalized over a B-H-B

H H H
B B
H H H
Octet Rule Always Applies to the Second
Period = n2 ; number of orbitals
2s, 2px, 2py, 2pz ---orbitals cannot hold more than two electrons
Ne [He]; 2s2, 2px2, 2py2, 2pz2

n=2
n=3
 Third Period ; n2 = 32 = 9 orbitals
Ar [Ne]; 3s2, 3px2, 3py2, 3pz2 3d0 3d0 3d0 3d0 3d0

n=3
 3. More than an Octet
Elements from the third Period and beyond, have ns, np and unfilled
nd orbitals which can be used in bonding

PCl5 P : (Ne) 3s2 3p3 3d0

Number of valence electrons = 5 + (5 x 7) = 40 Cl
10 electrons around the phosphorus
Cl
Cl P
Cl
SF4 Cl
S : (Ne) 3s2 3p4 3d0
Number of valence electrons = 6 + (4 x 7) = 34
F F
S
The Larger the central atom, the more atoms you F F
can bond to it usually small atoms such as F, Cl
and O allow central atoms such as P and S to
expand their valency.
Electronegativity is defined as the ability of an atom
in a molecule to attract electrons to itself
Electronegativity is a function of two properties of
isolated atoms;
The atoms ionization energy (how strongly an atom
holds onto its own electrons)
The atoms electron affinity (how strongly the atom
attracts other electrons)

For example, an element which has:

A large (negative) electron affinity
A high ionization (always endothermic, or Prof. Linus Pauling
positive for neutral atoms) Nobel Prize for Chemistry 1954
Nobel Prize for Peace 1962

Will: Attract electrons from other atoms and Resist having electrons attracted
away
Such atoms will be highly electronegative
Pauling scale of electronegativity;

Fluorine is the most electronegative element followed by O and N, Cl are

equal third. Cs is least.
Electronegativity increases from left to right along the Periodic Table.
For the representative elements (s & p block), the electronegativity
decreases as you go down a group.
No trend in the transition metals.
Electronegativity is dictated by
The number of protons in the nucleus
across a period you are increasing the number of protons, but filling electrons in the same Bohr
quantized energy level. You are only filling sub-shells, so electronegativity increases from left
to right

The distance from the nucleus

down groups, you are placing electrons into new quantized energy levels, so moving further away
from the attractive power of the nucleus. Outer shell becomes further away from the nucleus.

The amount of screening by the inner electrons

level of screening upon bonding electrons increases down groups, and adds to the reduction in
electronegativity. Screening is caused by repulsion of electrons for each other.

In hydrogen atom, energy of orbital

depends on the principle quantum
number, n.
But in many electron atoms, electron-
repulsions cause different sub-shells
to have different energies,
Sub-shell energy increases (with
increasing l)
s<p<d
The three major types of intramolecular bond can be described by
the electronegativity difference:
Non-Polar Covalent Bonds which occur between atoms with
little or no electronegativity difference (less than 0.5).
Polar Covalent Bonds which occur between atoms with a
definite electronegativity difference (between 0.5 and 2.0).
Ionic Bonds which occur between atoms with a large
electronegativity difference (2.0 or greater), where electron transfer
can occur.
E.g. F-F (4.0 4.0 = 0) is non-polar covalent
H-F (4.0 2.1 = 1.9) is polar covalent
LiF (4.0 1.0 = 3.0) is ionic

+ -
H F
 Dipole Moment occurs in any polar covalent bond,
because of an unequal sharing of the electron pair
between two atoms

E.g. Which of the following bonds is most polar: S-Cl,

S-Br, Se-Cl or Se-Br?
S-Cl (3.0 2.5) = 0.5
S-Br (2.8-2.5) = 0.3
Se-Cl (3.0-2.4) = 0.6
Se-Br (2.8-2.4) = 0.4
Therefore, Se-Cl is the most polar!

We should be able to reach the same conclusion using the Periodic

Table,
Cl is furthest to the right and to the top of the Periodic Table, so is the
most electronegative. Se is furthest to the left (metallic like) and
towards the bottom. Therefore, difference in electronegativity should
be the greatest!
 Compound Bond Length Electronegativity Dipole
() Difference Moment (D)
H-F 0.92 1.9 1.82
H-Cl 1.27 0.9 1.08
H-Br 1.41 0.7 0.82
H-I 1.61 0.4 0.44

Electronegativity difference decreases as bond length increases

Dipole Moment: = Qr

Prof. Peter Debye

Dipole moment is defined as the magnitude of charge (Q) Noble Prize 1936
multiplied by the distance between the charges;
units are D (Debye) = 3.36 x 1030 C.m
When proton & electron 100 pm apart, the dipole moment is 4.80 D

4.8 D is a key reference value! It represents a pure

charge of +1 and -1, which are 100 pm (100pm = 1)
apart. The bond is said to be 100% ionic!

H-F; = 1.82 D (measured) bond length = 0.92

If 100% ionic,
= 92/100 (4.8 D) = 4.42 D
% ionic = 1.82/4.42 x 100 = 41 % ionic

H-Cl; = 1.08 D (measured) bond length = 1.27

If 100% ionic,
= 127/100 (4.8 D) = 6.10 D
% ionic = 1.08/6.10 x 100 = 18 % ionic

H-Br; = 0.82 D (measured) bond length = 1.41

If 100% ionic,
= 141/100 (4.8 D) = 6.77 D
% ionic = 0.82/6.77 x 100 = 12 % ionic
Polar Molecules = Molecules with permanent dipole
moments

HCl has only one covalent bond (which is polar).

Therefore, its dipole moment = H-Cl bond dipole

In a molecule with two or more polar bonds, each bond

has a dipole moment contribution = bond dipole

Net dipole moment = vector sum of its bond dipoles

Linear Molecules: CO2 is Non-polar O C O

Net dipole = 0

Because CO2 dipoles are orientated in opposite directions.

The dipoles have equal magnitudes; they cancel
Symmetrical molecules (e.g. CCl4, CH4) are non-polar. The four dipoles
are of equal magnitude and neutralize one another at the center of a
tetrahedron

Non-symmetrical molecules (e.g. CHCl3, CO(CH3)2, H2O) are Polar.

The dipoles are not all equal or in opposite directions (partial charges and
bond lengths are all different in C-Cl, C-H, C=O, C-H)

(H2O is a bent molecule not linear, see later notes)

Formal Charges: the number of valence electrons in the isolated atom
minus the number of electrons assigned to the atom in the Lewis structure. These
are not real charges, but help with keeping count of electrons in Lewis structures.

E.g. CN- _ Number of valence electrons = 9 + 1 =10

C N

5 - 4 = -1 5 - 5 = 0

Question: Draw the Lewis structures of NO+ and determine the formal
charges of the atoms. Which Lewis structure is the preferred one?
Number of valence electrons = 11 - 1 = 10
+ + + +
N O N O N O N O
1

0 +1 +1 0 +2 +1
-1 0
Structure 1 is preferred because the positive charge is on the least
electronegative atom.
Lewis structures of Charged Molecules: Predict the most likely structure!

- Number of valence electrons = 15 + 1 =16

E.g. NCS
_ _
N C S N C S N C S

1
0 +1 0 0 0
-2 -1 0 -1
Structure 1 is preferred because the negative charge is on the most
electronegative atom with the lowest formal charge.
Tutorial Questions:
1. Use the electronegativities of C (2.5) and Cl (3.0) to describe the
character of the C-Cl bond in CCl4, and explain why CCl4 is a non-
polar molecule.
2. CHCl3 has a C-Cl bond of 178 pm, and measurements reveal 1.87 D.
Calculate the percentage ionic character. Is this a polar molecule?
3. Draw the most plausible Lewis Structure for NO2+, H2SO4 and SO42-
4. Describe the molecule (ClO2)- using three possible Lewis structures,
which is the most important?
 Shapes of Molecules
We use Lewis structures to account for formula of covalent compounds.
Lewis structures also account for the number of covalent bonds.
Lewis structures however do not account for the shapes of molecules.

Molecules of ABn have shapes dependent on the value of n

AB2 must be either linear or bent: Examples of Linear molecules

Linear - No non-bonding electrons

Linear Molecules have a bond angle = 180
Bent molecules have a bond angle 180 A bent

B B
AB3 most common shapes place the B atoms
at the corners of an equilateral triangle:
Trigonal Planar

The A atom lies in

the same plane as
the B atoms (Flat)

Bond angle = 120

No non-bonding electrons
 Trigonal Pyramidal

The A atom lies above the plane of the B atom.

Pyramid with an equilateral triangle as the base.
 The ideal tetrahedron has a bond angle = 109.5

VSEPR model explains

distortions of
molecules

The lone electron pair exerts a little extra repulsion on the three
bonding hydrogen atoms to create a slight compression to a 107 bond
angle.
Less repulsion is exerted by a bonding pair of electrons because
they feel attraction from two nuclei, while a non-bonding pair feels
attraction from only one nucleus.
Non-bonding pairs spread out more!
 AB4 is Tetrahedral

H
C H
H
H

The carbon has 4 valence electrons and thus needs 4 more

electrons from four hydrogen atoms to complete its octet. The
hydrogen atoms are as far apart as possible at 109 bond angle.
This is tetrahedral geometry. The molecule is three dimensional.
 Valence-Shell Electron-Pair Repulsion Theory (VSEPR)
In molecules there are 2 types of electron
1. Bonding Pairs
2. Non-bonding or lone pairs

The combinations of these determine the shape of the molecule

Single bonds have a big impact on shape, double bonds have little effect

The outer pairs of electrons around a covalently bonded atom

minimize repulsions between them by moving as far apart as
possible
Water is a bent molecule with bond angles of 104.5
Notice the bond angle decreases as the number of non-
bonding pairs increases

H2O

AB2 - classification
 Ozone
O3 ; number of valence electrons = 18 electrons

O O O O O O Resonance structures

AB3 - classification
 Valence Shell Electron-Pair Repulsion Theory
(VSEPR)
Procedure
1. Sum the total Number of Valence Electrons
Drawing the Lewis Structure
2. The atom usually written first in the chemical formula is the Central atom in the Lewis
structure
3. Complete the octet bonded to the Central atom. However, elements in the third row have
empty d-orbitals which can be used for bonding.
4. If there are not enough electrons to give the central atom an octet try multiple bonds.
Predicting the Shape of the Molecule
5. Sum the Number of Electron Domains around the Central Atom in the Lewis Structure;
Single = Double = Triple Bonds = Non-Bonding Lone Pair of Electrons = One Electron
Domain
6. From the Total Number of Electron Domains, Predict the Geometry and Bond Angle(s); 2
(Linear = 180); 3 (Trigonal Planar = 120); 4 (Tetrahedral = 109.5); 5 (Trigonal Bipyramidal
= 120 and 90); 6 (Octahedral = 90)
7. Lone Pair Electron Domains exert a greater repulsive force than Bonding Domains.
Electron Domains of Multiple Bonds exert a greater repulsive force than Single Bonds.
Thus they tend to compress the bond angle.
 Further Examples:

Tutorial Questions :
Draw Lewis structures and the molecular geometry of the following
molecules:
H3O+, NH4+, CS2, SCl2
Shape Bonding- Non- Bond angle Examples
pairs bonding /
pairs

Linear 2 0 180 BeCl2, CO2, HCN,

C2H2
Trigonal 3 0 120 BF3, SO3, NO3-,
planar CO32-, C2H4

Tetrahedral 4 0 109.5 NH4+, SO42-, PO43-,

Ni(CO)4, CH4
Trigonal 3 1 107 PH3, SO32-, NH3
pyramidal

Non-linear 2 2 105 H2S, SO2, H2O

(Crooked)
Molecules with Expanded Valence Shells
When the central atom of a molecule is from the third period of the
Periodic Table and beyond, that atom may have more than four pairs
of electrons around it
Five pairs of electrons around the central atom are based on the
Trigonal Bipyramidal structure.
AB5: e.g. PCl5
Three pairs define an Equatorial Triangle
(Equatorial electrons)
Two pairs lie above and below the triangle plane
(Axial electrons)

The repulsion between pairs located 90 apart

are much greater than for those 120 apart:
Because repulsion is greater for non-bonding than for bonding electron
pairs, then non-bonding pairs occupy equatorial positions on the Trigonal
Bipyramidal structure
116 and 186
SF4 :

The non-bonding pair occupies an equatorial position. The axial and

equatorial S-F bonds are slightly bent back because of the larger
repulsive effect of the lone pair.

BrF3 : T-shaped
90
 Third Period ; n2 = 32 = 9 orbitals
Ar [Ne]; 3s2, 3px2, 3py2, 3pz2 3d0 3d0 3d0 3d0 3d0

n=3
Six pairs of electrons around the central atom are based on the
Octahedron structure.

AB6 : e.g. SF6

The central atom can be visualized as being at the

centre of an octahedron, with the six electrons
pointing to the six vertices all bond angles are 90

E.g. BrF5 E.g. XeF4

Octahedral Square Pyramidal Square Planar

90 Should be less than 90
Intermolecular Forces: are generally much weaker than covalent
or ionic bonds. Less energy is thus required to vaporize a liquid or melt a
solid. Boiling points can be used to reflect the strengths of
intermolecular forces (the higher the Bpt, the stronger the forces)

Hydrogen Bonding : the attractive force between hydrogen in a

polar bond (particularly H-F, H-O, H-N bond) and an unshared
electron pair on a nearby small electronegative atom or ion

Very polar bond in H-F.

The other hydrogen halides dont form
hydrogen bonds, since H-X bond is less
polar. As well as that, their lone pairs are
at higher energy levels. That makes the
lone pairs bigger, and so they don't carry
such an intensely concentrated negative
charge for the hydrogens to be attracted
to.
Hydrogen Bonding & Water
One of the most remarkable consequences of H-bonding is found in the lower
density of ice in comparison to liquid water, so ice floats on water. In most
substances the molecules in the solid are more densely packed than in the
liquid. A given mass of ice occupies a greater volume than that of liquid water.
This is because of an ordered open H-bonding arrangement in the solid (ice) in
comparison to continual forming & breaking H-bonds as a liquid.
 Weaker Intermolecular Forces

Ion-Dipole Forces
An ion-dipole force is an attractive
force that results from the
electrostatic attraction between an
ion and a neutral molecule that has a
dipole.
Most commonly found in solutions.
Especially important for solutions of
ionic compounds in polar liquids.
A positive ion (cation) attracts the
partially negative end of a neutral
polar molecule.
A negative ion (anion) attracts the
partially positive end of a neutral
polar molecule.
Ion-dipole attractions become stronger as either the charge on the ion
increases, or as the magnitude of the dipole of the polar molecule
increases.
 Dipole-dipole Attractive Forces

A dipole-dipole force exists between neutral polar molecules

Polar molecules attract one another when the partial positive charge on one
molecule is near the partial negative charge on the other molecule
The polar molecules must be in close proximity for the dipole-dipole forces to
be significant
Dipole-dipole forces are characteristically weaker than ion-dipole forces
Dipole-dipole forces increase with an increase in the polarity of the molecule
Boiling points increase for polar molecules of similar mass, but increasing
dipole:

Molecular Mass Dipole moment, Boiling Point

Substance (amu) u (D) (K)

Propane 44 0.1 231

Dimethyl ether 46 1.3 248

Methyl chloride 50 2.0 249

Acetaldehyde 44 2.7 294

Acetonitrile 41 3.9 355

 London Dispersion Forces
significant only when molecules are close to each other

Due to electron repulsion, a temporary dipole on one atom

can induce a similar dipole on a neighboring atom

Prof. Fritz London

The ease with which an external electric field can induce a dipole
(alter the electron distribution) with a molecule is referred to as the
"polarizability" of that molecule
The greater the polarizability of a molecule the easier it is to induce a
momentary dipole and the stronger the dispersion forces
Larger molecules tend to have greater polarizability
Their electrons are further away from the nucleus (any
asymmetric distribution produces a larger dipole due to larger
charge separation)
The number of electrons is greater (higher probability of
asymmetric distribution)
thus, dispersion forces tend to increase with increasing molecular
mass
Dispersion forces are also present between polar/non-polar and
polar/polar molecules (i.e. between all molecules)
Van der Waals forces are made of dipole-dipole and London dispersion forces

Group 4A hydrides

Groups 4, 5, 6A hydrides