Chapter 1

Atoms, Molecules &

Chemical Bonding
CPE 435: PROCESS CHEMISTRY
Prepared by:
Rabiatul Adawiyah Abdol Aziz
Atomic Structure
The atom consists of positive, negative, and neutral entities
(protons, electrons, and neutrons).
Protons and neutrons are located in the nucleus of the
atom, which is small. Most of the mass of the atom is due
to the nucleus.
Electrons are located outside of the nucleus. Most of the
volume of the atom is due to electrons.

2
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Atomic Structure (2)
3
Structure of an atom
Positively charged nucleus (very dense, protons and neutrons)
and small (10
-15
m)

Negatively charged electrons are in a cloud (10
-10
m) around
nucleus
Diameter is about 2 10
-10
m (200 picometers (pm))
[the unit angstrom () is 10
-10
m = 100 pm]
Particle Symbol Relative electric
charge
Relative mass
Proton
Neutron
Electron
p
n
E
+1
0
-1
1
1
0.0005
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Atomic Number and Atomic Mass
4
The atomic number (Z) is the number of protons in the
atom's nucleus
The mass number (A) is the number of protons plus
neutrons
All the atoms of a given element have the same atomic
number
Isotopes are atoms of the same element that have
different numbers of neutrons and therefore different mass
numbers
The atomic mass (atomic weight) of an element is the
weighted average mass in atomic mass units (amu) of an
elements naturally occurring isotopes
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Atomic Orbitals
5
Quantum mechanics: describes electron energies and
locations by a wave equation
Wave function solution of wave equation
Each wave function is an orbital;

A plot of
2
describes where electron most likely to occupy

Electron cloud has no specific boundary so we show most
probable area
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Shells & Subshells
Electrons are arranged around the nucleus of an
atom, in shells. These numbers are known as
principal quantum numbers, n.
For example, the first shell is called as quantum
number = 1.
Each shell consists of a number of subshells,
labelled as s, p, d or f.

Shells & Subshells (2)
The number of subshells in each shell equals the
shell number. Hence, the first shell has one
subshell, the second shell has two subshells, etc.

shell number number of subshells
1 1 (1s)
2 2 (2s, 2p)
3 3 (3s, 3p, 3d)

Shells & Subshells (3)
Each subshell contains a number of orbitals, in which the
electrons are placed.
The number of orbitals in each subshell depends on the
type of subshell:
type of subshell number of orbitals
s 1
p 3
d 5
f 7

Shapes of Atomic Orbitals for Electrons
9
s and p orbitals most important in organic and biological
chemistry
s orbitals: spherical, nucleus at center
p orbitals: dumbbell-shaped, nucleus at middle
d orbitals: 4 of 5 (cloverleaf-shaped) & the 5
th
(elongated
dumbbell-shaped), nucleus at center
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Orbitals and Shells
10
Orbitals are grouped in shells of increasing size and
energy
Different shells contain different numbers and kinds of
orbitals
Each orbital can be occupied by two electrons
Orbitals and Shells (2)
11
First shell contains one s orbital, denoted 1s, holds only
two electrons
Second shell contains one s orbital (2s) and three p
orbitals (2p), eight electrons
Third shell contains one s orbital (3s), three p orbitals
(3p), and five d orbitals (3d), 18 electrons
p-Orbitals
12
In each shell there are three perpendicular p
orbitals, p
x
, p
y
, and p
z
, of equal energy

Two lobes of each p orbital are separated by
region of zero electron density; a node
Electron Configurations
13
Ground-state electron configuration (lowest energy
arrangement) of an atom lists orbitals occupied by its
electrons.
Rules:
1. Lowest-energy orbitals fill first: 1s 2s 2p 3s 3p
4s 3d (Aufbau (build-up) principle)
2. Electrons act as if they were spinning around an axis.
Electron spin can have only two orientations, up | and
down +. Only two electrons can occupy an orbital, and
they must be of opposite spin (Pauli exclusion
principle) to have unique wave equations
3. If two or more empty orbitals of equal energy are
available, electrons occupy each with spins parallel until
all orbitals have one electron (Hund's rule).
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Exercises:
1. Write the complete or condensed electronic configuration
for the following elements:
i. Sulphur (S) (z=16);
ii. Magnesium (Mg) (z=12);
iii. Bromine (Br) (z=35);
iv. Chromium (Cr) (z=24)
2. Using the Periodic Table, give the symbol(s) of:
i. an element with the ground state electronic configuration of
[Xe]6s
2
4f
14
5d
10
6p
1
.
ii. an ion with a double positive charge (2+) with an electronic
configuration of [Ar]3d
5
.
iii. two elements with a groundstate configuration of ns
2
np
3
.
Quantum Mechanics
Orbital Each allowed combination of n, l and m
l
values specifies
one of the atoms orbitals to describe the shape, size and the
spatial orientation.
An atomic orbital is specified by 3 quantum numbers:
1. Principal Quantum Number, n, related to the size of
the orbital. As n becomes larger, the atom becomes larger
and the electron is further from the nucleus. The higher the
value of n, the higher the energy level.

Note: the total number of orbitals = n
2
.


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Quantum Mechanics (2)
2. Orbital Angular Momentum (or, Azimuthal) Quantum
Number, l. (related to shape). This quantum number depends on
the value of n. The number of l value= the number of n value. The
values of l begin at 0 and increase to (n - 1). We usually use letters for
l (s, p, d and f for l = 0, 1, 2, and 3, respectively). Usually we refer to
the s, p, d and f-orbitals. The number of orbitals in each subshell is
2l+1 for a given l value. One s orbital (l=0), 3 p orbitals (l=1) and 5 d
orbitals (l=2) and 7 f orbitals (l=3).
3. Magnetic Quantum Number, m
l
related to orientation in
space. This quantum number depends on l. The magnetic quantum
number has integral values between -l and +l. The number of possible
m
l
values equals the number of orbitals, which is 2l+1 for a given l
value.



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Quantum Mechanics (3)
How many orbitals exist for n = 3?
For n = 3, l will have 3 values, i.e., 0, 1 and 2.
For l = 0, m
l
will have 1 value (0)
For l = 1, m
l
will have 3 values (-1, 0 and +1)
For l = 2, m
l
will have 5 values, -2 through 0 to +2.
(i.e., -2, -1, 0 ,+1 and +2).
There are 9 m
l
values which means 9 orbitals. In
other words, n
2
=3
2
=9.

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Orbitals and Quantum Numbers

Molecular Orbitals
Molecular Orbital (MO) Theory - Just as electrons in atoms
are found in atomic orbitals, electrons in molecules are found in
molecular orbitals.
Additive combination (bonding) MO is lower in energy
Subtractive combination (antibonding) MO is higher energy











Sigma (o) bonds - Circular cross-section and are formed by head-on
interaction



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Molecular Orbitals in H
2
& He
2
H
2
has two bonding electrons.
He
2
has two bonding electrons and two antibonding
electrons.

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Molecular Orbitals in Ethylene
The t bonding MO is from combining p orbital lobes
with the same algebraic sign
The t antibonding MO is from combining lobes with
opposite signs
Only bonding MO is occupied








Pi (t) bonds dumbbell shape from sideways interaction of p
orbitals

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Bond Order


Bond order = 1 for single bond.
Bond order = 2 for double bond.
Bond order = 3 for triple bond.
Fractional bond orders are possible.

( ) electrons g antibondin - electrons bonding order Bond
2
1
=
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Bond Order (2)
For H
2


Therefore, H
2
has a single bond.

For He
2


Therefore He
2
is not a stable molecule

( ) 0 2 2 order Bond
2
1
= =
( ) 1 0 2 order Bond
2
1
= =
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Homonuclear diatomic molecules
Molecules composed only one type of element
For examples: Li
2
, Be
2
, B
2
etc.
AOs combine according to the following rules:
The number of MOs = number of AOs;
AOs of similar energy combine;
As overlap increases, the energy of the MO decreases;
Pauli exclusion principle?
Hunds rule?

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Molecular Orbitals for Li
2

Molecular Orbitals for Li
2
(2)
Each 1s orbital combines with another 1s orbital to give
one o
1s
and one o
*
1s
orbital, both of which are occupied
(since Li and Be have 1s
2
electron configurations).
Each 2s orbital combines with another 2s orbital, two give
one o
2s
and one o
*
2s
orbital.
The energies of the 1s and 2s orbitals are sufficiently
different so that there is no cross-mixing of orbitals (i.e.
we do not get 1s + 2s).

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Molecular Orbitals for Li
2
(3)
There are a total of 6 electrons in Li
2
:
2 electrons in o
1s
;
2 electrons in o
*
1s
;
2 electrons in o
2s
; and
0 electrons in o
*
2s
.

Since the 1s AOs are completely filled, the o
1s
and
o*
1s
are filled.
Note: Generally ignore core electrons in MO
diagrams.

( ) 1 2 4 order Bond
2
1
= =
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Molecular Orbitals for Be
2

There are a total of 8 electrons in Be
2
:
2 electrons in o
1s
;
2 electrons in o
*
1s
;
2 electrons in o
2s
; and
2 electrons in o
*
2s
.

Since the bond order is zero, Be
2
does not exist.

( ) 0 4 4 order Bond
2
1
= =
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Molecular Orbitals from 2p Atomic
Orbitals
The six p-orbitals (two sets of 3) must give rise to 6
MOs:
o, o
*
, t, t
*
, t, and t
*
.
Therefore there is a maximum of 2 t bonds that can come from p-
orbitals.
The relative energies of these six orbitals can change.
There are two ways in which two p orbitals overlap:
end-on so that the resulting MO has electron density on the axis
between nuclei (i.e. o type orbital);
sideways so that the resulting MO has electron density above and
below the axis between nuclei (i.e. t type orbital).



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Molecular Orbitals from 2p Atomic Orbitals (2)
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Heteronuclear diatomic molecules
Molecules composed two different elements
For examples: CO
2
, H
2
O, etc.
Pauli exclusion principle?
Hunds rule?


Chemical Bonds

Chemical bond: attractive force holding two or
more atoms together.
Covalent bond results from sharing electrons
between the atoms. Usually found between non-
metals.
Ionic bond results from the transfer of electrons
from a metal to a non-metal.
Metallic bond: attractive force holding pure
metals together.
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The Octet Rule
All noble gases except He has an s
2
p
6
configuration.
Octet rule: atoms tend to gain, lose, or share
electrons until they are surrounded by 8 valence
electrons (4 electron pairs).
Caution: there are many exceptions to the octet
rule.
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Exceptions to the Octet Rule
There are three classes of exceptions to the octet rule:
Molecules with an odd number of electrons;
Molecules in which one atom has less than an octet;
Molecules in which one atom has more than an octet.

Odd Number of Electrons
Few examples. Generally molecules such as ClO
2
, NO,
and NO
2
have an odd number of electrons.

N O N O
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Exceptions to the Octet Rule (2)
Less than an Octet
Relatively rare.
Molecules with less than an octet are typical for compounds of Groups
1A, 2A, and 3A.
Most typical example is BF
3
.
Formal charges indicate that the Lewis structure with an incomplete
octet is more important than the ones with double bonds.

More than an Octet
This is the largest class of exceptions.
Atoms from the 3
rd
period onwards can accommodate more than an
octet.
Beyond the third period, the d-orbitals are low enough in energy to
participate in bonding and accept the extra electron density.
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Ionic Bonding (Definition)
Involves a metal and a nonmetal ion through
electrostatic attraction.
Bond formed by the attraction between two oppositely
charged ions.
The metal donates one or more electrons, forming a
positively charged ion or cation with a stable electron
configuration. These electrons then enter the non metal,
causing it to form a negatively charged ion or anion
which also has a stable electron configuration. The
electrostatic attraction between the oppositely charged
ions causes them to come together and form a bond.
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Ionic Bonding (Example)

Consider the reaction between sodium and chlorine:
Na(s) + Cl
2
(g) NaCl(s) AH
f
= -410.9 kJ
The reaction is violently exothermic.
NaCl is more stable than its constituent elements.
Na has lost an electron to become Na
+
and chlorine
has gained the electron to become Cl

. Note: Na
+

has an Ne electron configuration and Cl

has an Ar
configuration.
That is, both Na
+
and Cl

have an octet of electrons

surrounding the central ion.

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Energetics of Ionic Bond Formation
The formation of Na
+
(g) and Cl
-
(g) from Na(g) and Cl(g) is
endothermic.
Why is the formation of Na(s) exothermic?
The reaction NaCl(s) Na
+
(g) + Cl
-
(g) is endothermic
(AH = +788 kJ/mol).
The formation of a crystal lattice from the ions in the gas
phase is exothermic:
Na
+
(g) + Cl
-
(g) NaCl(s) AH = -788 kJ/mol
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Energetics of Ionic Bond Formation (2)
Lattice energy: the energy required to completely
separate an ionic solid into its gaseous ions.
Lattice energy depends on the charges on the ions and
the sizes of the ions:


k is a constant (8.99 x 10
9
Jm/C
2
), Q
1
and Q
2
are the
charges on the ions, and d is the distance between ions.
Lattice energy increases as
i. The charges on the ions increase
ii. The distance between the ions decreases

d
Q Q
E
l
2 1
k =
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Electron Configurations of Ions of the
Representative Elements
These are derived from the electron configuration of
elements with the required number of electrons added
or removed from the most accessible orbital.
Electron configurations can predict stable ion
formation:
Mg: [Ne]3s
2

Mg
+
: [Ne]3s
1
not stable
Mg
2+
: [Ne] stable
Cl: [Ne]3s
2
3p
5

Cl
-
: [Ne]3s
2
3p
6
= [Ar] stable

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Covalent Bonding
When two similar atoms bond, none of them wants to lose or
gain an electron to form an octet.
When similar atoms bond, they share pairs of electrons to each
obtain an octet.
Each pair of shared electrons constitutes one chemical bond.
Example: H + H H
2
has electrons on a line connecting the two
H nuclei.

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Strengths of Covalent Bonds
The energy required to break a covalent bond is called the
bond dissociation enthalpy, D.
That is, for the Cl
2
molecule, D(Cl-Cl) is given by AH for
the reaction: Cl
2
(g) 2Cl(g).
When more than one bond is broken:
CH
4
(g) C(g) + 4H(g) AH = 1660 kJ
the bond enthalpy is a fraction of AH for the atomization
reaction: D(C-H) = AH = (1660 kJ) = 415 kJ.
Bond enthalpies can either be positive or negative.

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Strengths of Covalent Bonds (2)
Bond Enthalpies and the Enthalpies of Reactions
Bond enthalpies can be to calculate the enthalpy for a
chemical reaction.
Chemical reaction bonds need to be broken and then new
bonds get formed.
The enthalpy of the reaction is given by the sum of bond
enthalpies for bonds broken minus the sum of bond
enthalpies for bonds formed.
For example;
CH
4
(g) + Cl
2
(g) CH
3
Cl(g) + HCl(g) AH
rxn
= ?
Where AH
rxn
= the enthalpy for a reaction
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Strengths of Covalent Bonds (3)
Bond Enthalpies and the Enthalpies of Reactions
In this reaction one C-H bond and one Cl-Cl bond gets
broken while one C-Cl bond and one H-Cl bond gets
formed.


The overall reaction is exothermic which means than the
bonds formed are stronger than the bonds broken.
The above result is consistent with Hesss law.

( ) ( ) | | ( ) ( ) | | { }
kJ 104
Cl - H Cl - C Cl - Cl H - C
=
+ + = A D D D D H
rxn
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Strengths of Covalent Bonds (4)
Bond Enthalpy and Bond Length
Multiple bonds are shorter than single bonds.
Multiple bonds are stronger than single bonds.
As the number of bonds between atoms increases, the
atoms are held closer and more tightly together.

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Bond Polarity and Electronegativity
In a covalent bond, electrons are shared.
Sharing of electrons to form a covalent bond does not
imply equal sharing of those electrons.
There are some covalent bonds in which the electrons
are located closer to one atom than the other.
Unequal sharing of electrons results in polar bonds.
Electronegativity: The ability of one atoms in a
molecule to attract electrons to itself.
Pauling set electronegativities on a scale from 0.7 (Cs)
to 4.0 (F).


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Bond Polarity and Electronegativity (2)
Electronegativity increases
across a period and
down a group.
Difference in electronegativity is a gauge of bond
polarity:
electronegativity differences around 0 result in non-
polar covalent bonds (equal or almost equal sharing of
electrons);
electronegativity differences around 2 result in polar
covalent bonds (unequal sharing of electrons);
electronegativity differences around 3 result in ionic
bonds (transfer of electrons).

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Electronegativity
Bond Polarity and Electronegativity (3)
There is no sharp distinction between bonding types.
The positive end (or pole) in a polar bond is represented o+
and the negative pole o-.

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Bond Polarity and Electronegativity (4)
Dipole Moments
Consider HF:
The difference in electronegativity leads to a polar bond.
There is more electron density on F than on H.
Since there are two different ends of the molecule, we
call HF a dipole.
Dipole moment, m, is the magnitude of the dipole:

where Q is the magnitude of the charges.
Dipole moments are measured in debyes, D.

Qr =
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Metallic Bonding
Important physical properties of pure metals: malleable,
ductile, good conductors, and feel cold.
Most metals are solids with the atoms in a close packed
arrangement.
In Cu, each atom is surrounded by 12 neighbors.
There are not enough electrons for the metal atoms to be
covalently bonded to each other.

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Electron-Sea Model of Metallic Bonding
Delocalized model is used for electrons in a metal.
The metal nuclei are seen to exist in a sea of electrons.
No electrons are localized between any two metal atoms.
Therefore, the electrons can flow freely through the metal.
Without any definite bonds, the metals are easy to deform
(and are malleable and ductile).
Problems with the electron sea model:
As the number of electrons increase, the strength of
bonding should increase and the melting point should
increase.
But: group 6B metals have the highest melting points
(center of the transition metals).

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Chapter 23
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Chapter 23
Molecular-Orbital Model for Metals
Delocalized bonding requires the atomic orbitals on one
atom to interact with atomic orbitals on neighboring
atoms.
Example: graphite electrons are delocalized over a whole
plane, benzene molecules have electrons delocalized over a
ring.
Recall: the number of molecular orbitals is equal to the
number of atomic orbitals.
In metals there is a very large number of orbitals.
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Molecular-Orbital Model for Metals (2)
As the number of orbitals increase, their energy spacing
decreases and they band together.
The number of electrons do not completely fill the band of
orbitals.
Therefore, electrons can be promoted to unoccupied
energy bands.
Since the energy differences between orbitals are small, the
promotion of electrons occurs at low energy costs.

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Molecular-Orbital Model for Metals (3)

Molecular-Orbital Model for Metals (4)
As we move across the transition metal series, the
antibonding band starts becoming filled.
Therefore, the first half of the transition metal series have
only bonding-bonding interactions, the second half has
bonding-antibonding interactions.
We expect the middle of the transition metal series to have
the highest melting points.
The energy gap between bands is called the band gap.

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Ketelaar Triangle
triangles used to show different compounds in varying degrees of ionic,
metallic and covalent bonding.
On the right side (from ionic to covalent) should be compounds
with varying difference in electronegativity, in the covalent corner
compounds with equal electronegativity such as Cl
2
, in the ionic corner
compounds with large electronegativity difference such as NaCl
The bottom side (from metallic to covalent) is metallic bonds
with delocalized bonding and the other are covalent bonds in which the
orbitals overlap in a particular direction.
The left side (from ionic to metallic) is for delocalized bonds with
varying electronegativity difference.

Ketelaar Triangle (2)
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Chapter 6
Intermolecular Forces
The covalent bond holding a molecule together is an
intramolecular forces.
The attraction between molecules is an intermolecular
force (also called Van der Waals forces).
Intermolecular forces are much weaker than
intramolecular forces (e.g. 16 kJ/mol vs. 431 kJ/mol for
HCl).
When a substance melts or boils the intermolecular forces
are broken (not the covalent bonds).
There are several types : ion-dipole, dipole-dipole,
hydrogen bonding and London dispersion forces.
Intermolecular Forces
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Chapter 11
Ion-Dipole Forces
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Chapter 11
Interaction between an ion and a dipole.
For example: ionic compound dissolve in water. The
ions become separeted because the attaractions
between the ions and the oppositely charged poles
of H
2
O molcules overcome the attraction between
the ions themselves.
Strongest forces among all intermolecular forces.
Ion-Dipole Forces (2)

--- ion-depole forces
Dipole-Dipole Forces
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Dipole-dipole forces exist between neutral polar
molecules.
Polar molecules need to be close together.
Weaker than ion-dipole forces.
There is a mix of attractive and repulsive
dipole-dipole forces as the molecules tumble.
If two molecules have about the same mass and size,
then dipole-dipole forces increase with increasing
polarity.
Dipole-Dipole Forces (2)
Hydrogen Bonding
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Special case of dipole-dipole forces.
By experiments: boiling points of compounds with
H-F, H-O, and H-N bonds are abnormally high.
Intermolecular forces are abnormally strong.
H-bonding requires H bonded to an electronegative
element (most important for compounds of F, O,
and N).
Electrons in the H-X (X = electronegative element) lie much closer to X than
H.
H has only one electron, so in the H-X bond, the o+ H presents an almost
bare proton to the o- X.
Therefore, H-bonds are strong.
Hydrogen Bonding
Exercise
Which of the folloing substances exhibits H bonding?
For those that do, draw to molecules of the substance
with the H bond(s) beteen them.
i. C
2
H
6
ii. CH
3
OH
iii. CH
3
C=O
NH
2
London Dispersion Forces
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Chapter 11
Weakest of all intermolecular forces.
Very weak for small particles (like H
2
and He) but stronger
for larger particles (like I
2
and Xe)
It is possible for two adjacent neutral molecules to affect
each other.
The nucleus of one molecule (or atom) attracts the electrons
of the adjacent molecule (or atom).
For an instant, the electron clouds become distorted.
In that instant a dipole is formed (called an instantaneous
dipole).
The forces between instantaneous dipoles are called
London dispersion forces.

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Polarizability is the ease with which an electron cloud can be
deformed.
The larger the molecule (the greater the number of electrons)
the more polarizable - increase as molecular weight increases
London dispersion forces exist between all molecules -
depend on the shape of the molecule.
The strenght of the dispersion force depends on the
polarizability of the particle.
London Dispersion Forces (2)
London Dispersion Forces (3)
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The greater the surface area
available for contact, the greater
the dispersion forces.
London dispersion forces
between spherical molecules are
lower than between sausage-like
molecules.

Increasing the strenght
of dispersion forces
References
1. David P. White (2003) Chemistry - The Central
Science (9
th
edition). Prentice Hall.
2. John McMurry (2008) Organic Chemistry.
Brooks/Cole Cengage Learning.