PHM 106: BASIC PHARMACEUTICAL

CHEMISTRY
PREMPEH AGYEMAN
Department Of Pharmaceutical Chemistry
School of Pharmacy and Pharmaceutical
sciences
University Of Cape Coast
PERIODIC CHEMISTRY

2
THE PERIODIC TABLE
Mendeleev and Meyer organized the elements in order
of atomic weight and then identified groups of elements
with similar properties.
Mendeleev found vacancies in the table and was able to
predict the properties of several elements that had not
yet been discovered gallium, scandium,
germanium and polonium
In the modern periodic table, the horizontal row of
elements is called a period and the vertical column is a
group
(IUPAC) has recommended that the groups be
numbered 1 through 18.
Some sections of the periodic table have traditional
names

3
HENRY MOSELEY
Later, Moseley discovered that the periodic nature of the elements was
dependent on atomic number, not atomic mass
Argon P=18 N= 22 M=40
Potassium P=19 N= 20 M= 39

Image taken from:

http://dewey.library.upenn.edu/sceti/smith/
THE PERIODIC TABLE
THE PERIODIC TABLE

Column = Group or
Family
18 columns on the
Periodic Table

Row = Period
7 rows on the
Periodic Table
7
PERIODS
•Each row is called a “period”
•The elements in same period have
the same number of energy levels

1st Period = 1 E. Level

2nd Period = 2 E. Levels
3rd Period = 3 E. Levels
4th Period = 4 E. Levels
5th Period = 5 E. Levels
6th Period = 6 E. Levels
7th Period = 7 E. Levels
 GROUPS
•Each column is called a “group”
•Elements in same group has the same number of
valence electrons
Group 1 = 1 valence electron He is an
exception,
Group 2 = 2 valence
It has 2
electrons
electrons

Group 8 =
8 valence electrons
10
METALS, NONMETALS, AND SEMI-METALS
SPECIAL ROWS ON THE PT

Lanthanides

Actinide
s
THE GROUPS OF THE PERIODIC TABLE
Group 1: The Alkali Metals H
1

1.008

Most reactive among the metals 3

Li

Rarely found free in nature

6.941

11
Na
Forms a charge of +1
22.990

19

1 valence electron K
39.098

37

-
- Rb
85.468

 Core electrons

-
-

+
++ +
+ ++

55
+

Cs
+

-
-
+
-

132.905
-

87
Fr
-
-

(223)
-
THE GROUPS OF THE PERIODIC
TABLE
Group 2: The Alkaline Earth Metals
 Less reactive compared to group 1, but quite reactive
 Charge of +2
THE GROUPS OF THE PERIODIC TABLE

Groups 3-12: Transition Metals

 Found freely and in compounds in nature
 Charge is usually +2 but can vary
 usually 2 valence electrons

Group 13: Boron Family

 Charge is +3
 3 valence electrons
THE GROUPS OF THE PERIODIC TABLE

Group 14: The Carbon Family

 Contains elements that can form unusual bonds (carbon and silicon)
 Charge is +4 or -4
 contains 4 valence electrons

Group 15: The Nitrogen Family

 Charge is -3
 contains 5 valence electrons
THE GROUPS OF THE PERIODIC TABLE

Group 16: The Oxygen Family

 Also known as the chalcogens
 Charge is -2
 6 valence electrons

Group 17: The Halogens

 Most reactive nonmetals
 charge is -1
 7 valence electrons

Group 18: The Noble Gases (The Inert Gases)

 Nonreactive
 Charge is 0
 2 or 8 valence electrons
ISOELECTRONIC SERIES

18
 The effective nuclear charge: is the nuclear
PERIODIC VARIATION charge felt by an electron when both the actual
IN PHYSICAL nuclear charge (Z) and the repulsive effects
PROPERTIES (shielding) of the other electrons are taken into
account.
effective nuclear charge increases across a
period, and decrease down a group
Atomic Radius: it is one-half the distance between
the two nuclei in two adjacent metal atoms or in a
diatomic molecule.
decrease across a period, and increase
down a group
Ionic radius: is the radius of a cation or an anion
Cations decrease
in size and anions increase in size compare to
neutral atom. Same trend atomic radius on periodic
table.
For isoelectronic cations, we see that the radii of
tripositive ions are smaller than those of dipositive
ions which in turn are smaller than unipositive ions

19
PERIODIC VARIATION IN CHEMICAL PROPERTIES
Ionization Energy: Ionization energy (IE) is the minimum energy (in kJ/mol) required
to remove an electron from a gaseous atom in its ground state.
1st IE, < 2nd IE< 3rd IE, etc
always an endothermic process
first ionization energies of
elements in a period increase across the period
For a given group, ionization energy decreases
down a group metallic
character of the elements within a group increases from top to bottom.
Electron Affinity: the negative of the energy change that occurs when an electron is
accepted by an atom in the gaseous state to form an anion.
increase in the tendency to accept electrons from left to right across a period
The halogens (Group 7A) have the highest electron affinity values.
Diagonal relationships are similarities between pairs of elements in different groups and
periods of the periodic table. The reason for this phenomenon is the closeness of the
charge densities of their cations.

20
DEVELOPMENT OF
CHEMICAL BONDING
THEORY
The alkali metals in group 1A, achieve a noble-gas configuration by
losing the single S electron from their valence shell to form a
cation,
The halogens in group 7A achieve a noble-gas configuration by
gaining a P electron to fill their valence shell and form an anion.
The resultant ions are held together in compounds like NaCl by an
electrostatic attraction that we call an ionic bond.

21
IONIC BOND
Between atoms of metals and nonmetals with very different electronegativity
Bond formed by transfer of electrons
Produce charged ions.
Conductors and have high melting point.
Examples; NaCl, CaCl2, K2O
ENERGETICS OF IONIC BONDING
2Na(s) + Cl2(g) -------> 2NaCl(s)

it takes 495 kJ/mol

to remove 1
electron from
sodium.
495x2 = 990 kJ/2 Na
ENERGETICS OF IONIC
BONDING
We get 349 kJ/mol Cl back by
giving 1 electron to each to 1
mole of Cl2.

-349x2 = -700 kJ/mol Cl2

990 kJ/2Na – 700 kJ/Mol Cl2 =
290kJ
 ENERGETICS OF IONIC
BONDING
There must be a
third factor ….
The electrostatic
attraction
Between Na+ and
Cl-.

The ionic Bond

LATTICE ENERGY
The energy required to completely separate a mole of a
solid ionic compound into its gaseous ions.

The energy associated with electrostatic interactions is

governed by Coulomb’s law:

Q1Q2
Eel = 
d2
LATTICE ENERGY
Q1Q2
Eel = 
d2
LATTICE ENERGY
Lattice energy increases with the charge on
the ions.
• It also increases with decreasing size of ions.
COVALENT BOND
In1858, August Kekulé and Archibald Couper independently
proposed that, in all organic compounds, carbon is tetravalent—it
always forms four bonds when it joins other elements to form
stable compounds.
carbon atoms can bond to one another to form extended chains of
linked atoms. In 1865, Kekulé provided another major advance
when he suggested that carbon chains can double back on
themselves to form rings of atoms.
Jacobus van’t Hoff and Joseph Le Bel added a third dimension to our
ideas about organic compounds when they proposed that the four
bonds of carbon are not oriented randomly but have specific spatial
directions.
Van’t Hoff went even further and suggested that the four atoms to
which carbon is bonded sit at the corners of a regular tetrahedron,
with carbon in the center.
32
 COVALENT
BONDused to show three-
conventions
dimensionality: solid lines represent
bonds in the plane of the page,
The heavy wedged line represents a
bond coming out of the board toward
the viewer.
The dashed line represents a bond
receding back behind the board, away
from the viewer.
Energy flows out of the chemical
system when a bond forms.
Conversely, energy must be put into
the chemical system to break a bond.
Making bonds always releases energy, 33
 COVALENT BOND
The bonding in methane is not ionic because it would take too much energy
for carbon (1s2 2s2 2p2) either to gain or lose four electrons to achieve a
noble-gas configuration.
As a result, carbon bonds to other atoms, not by gaining or losing electrons,
but by sharing them.
Such a shared-electron bond, first proposed in 1916 by G. N. Lewis, is called a
covalent bond.
The neutral collection of atoms held together by covalent bonds is called a
molecule.
A simple way of indicating covalent bonds in molecules is the use of Lewis
structures, or electron-dot structures, where the valence-shell electrons of
atoms are represented as dots.
Thus, hydrogen has one dot representing its 1s electron, carbon has four dots
(2S2 2P2), oxygen has six dots (2S2 2P4), and so on.

34
COVALENT BOND
Another simpler way is the use of Kekulé structures, or linebond
structures, in which a two-electron covalent bond is indicated as a
line drawn between atoms.

35
COVALENT BOND
The number of covalent bonds an atom forms depends on
how many additional valence electrons it needs to reach a
noble-gas configuration.
Hydrogen has one valence electron (1s) and needs one more
to reach the helium configuration (1s2), so it forms one bond.
Carbon has four valence electrons (2S2 2P2) and needs four
more to reach the Neon configuration (2S2 2P6), so it forms
four bonds.
The halogens have seven valence electrons, need one more,
and form one bond.
Nitrogen has …….. valence electrons, needs ………….
Oxygen ?

36
Covalent bonds- Two atoms share one or more pairs of outer-
shell electrons.

Oxygen Atom Oxygen Atom

Oxygen Molecule (O2)

Valence electrons that are not used for bonding are called lone-
pair electrons, or nonbonding electrons. The nitrogen atom in
ammonia, NH3, for instance, shares six valence electrons in three
covalent bonds and has its remaining two valence electrons in a
nonbonding lone pair.
nonbonding electrons are often omitted when drawing line-bond
structures

38
VALENCE BOND THEORY
Two models have been developed to
describe covalent bonding: valence
bond theory and molecular orbital
theory.
According to valence bond theory, a
covalent bond forms when two atoms
approach each other closely and a
singly occupied orbital on one atom
overlaps a singly occupied orbital on
the other atom.
The electrons are now paired in the
overlapping orbitals and are attracted
to the nuclei of both atoms, thus
bonding the atoms together. In the H2
molecule, the H-H bond results from
the overlap of two singly occupied 39
If two nuclei in the H2 molecule are too close, they will repel each
other because both are positively charged, yet if they’re too far
apart, they won’t be able to share the bonding electrons.
Thus, there is an optimum distance between nuclei that leads to
maximum stability. This distance (bond length), is 74 pm in the
H2 molecule.
Every covalent bond has both a characteristic bond strength and
bond length.

40
TRY
How many hydrogen atoms does phosphorus
bond to in forming phosphine?

Draw both electron-dot and line-bond structures

for chloromethane, CH3Cl.

Draw a molecule of chloroform, CHCl3, using

solid, wedged, and dashed lines to show its
tetrahedral geometry.

41
LEWIS ELECTRON-DOT DIAGRAMS
In Lewis diagrams, bonds between two atoms
exist when they share one or more pairs of
electrons. In addition, some molecules have
nonbonding pairs, also called lone pairs of
electrons on atoms.

These electrons contribute to the shape and

reactivity of the molecule but do not directly
bond the atoms together.

Simple molecules such as water follow the octet

42
LEWIS ELECTRON-DOT DIAGRAMS

Shared electrons are considered to contribute to the

electronic requirements of both atoms involved
The electron pairs shared by H and O in the water
molecule are counted toward both the 8-electron
requirement of oxygen and the 2-electron
requirement of hydrogen.

The Lewis model defines double bonds as containing

four electrons and triple bonds as containing six
electrons:
43
It is rare to use Lewis dot
structures for other elements
such as transition metals
They have incomplete d
orbitals, leading to variable
valence electron configurations

One dot = 1 electron

 DIAGRAMS FOR BONDING IN MOLECULES

Lines correspond to 2 electrons in bond

Lewis structures are representations of molecules showing
all valence electrons, bonding and nonbonding.
COVALENT BONDING
There are several
electrostatic interactions
in these bonds:
 Attractions between electrons
and nuclei
 Repulsions between electrons
 Repulsions between nuclei
 POLAR COVALENT
BONDS
electron sharing not always equal.

•Fluorine pulls harder on the shared electrons than

hydrogen does due to its higher Electronegativity
A measure of how much an atom attracts
electrons when
it is in a molecule
•Therefore, the fluorine end has more electron
density than the hydrogen end.
H-F bond is much stronger than H-H or F-F bond
because there is an ionic component making
the H-F bond polar
Water is a polar molecule because oxygen is more
electronegative than hydrogen, and therefore electrons are
pulled closer to oxygen.
POLAR COVALENT BONDS
When two atoms share electrons
unequally, a bond dipole results.
The dipole moment, , produced by
two equal but opposite charges
separated by a distance, r, is
calculated:
 = Qr
It is measured in debyes (D).
It’s a vector, with magnitude and
direction
The greater the difference in
electronegativity, the more polar is the
bond.
 CO-
ORDINATION
A type of covalent bond in which
both electrons are supplies by one
of the bonding atoms. Eg
Amonium ion

In coordination, the donating atom

does not lose the electrons
outright as seen in ionic bonds.
Loosing electrons outright violates
the octet rule

In ionic bonds, loosing electrons

outright satisfies the octet rule.
50
RESONANCE When alternate locations for single bonds
and multiple bonds are possible that all
afford valid Lewis structures, a structure
demonstrating each option should be drawn.
For example, three drawings
(resonance structures) of carbonate are
needed to show the double bond in
each of the three possible C-O
positions.
In fact, experimental evidence shows
that all three C-O bonds are equivalent,
with bond lengths (129 pm) between
typical C-O double-bond and single-
bond distances (116 pm and 143 pm,
respectively)
This is called resonance; there is more than
one possible way in which the valence51
 DISCOVERY OF SUBATOMIC PARTICLES
Discoveries in atomic spectra showed that each element
emits light of specific energies when excited by an electric
discharge or heat.
In addition to emission of visible light, infrared and
ultraviolet emissions were also discovered in the spectrum
of the hydrogen atom.
The origin of this energy was unknown until Niels Bohr’s
quantum theory of the atom
This theory assumed that negatively charged electrons in
atoms move in stable circular orbits around the positively
charged nucleus with no absorption or emission of energy.
Electrons may absorb light of certain specific energies and
be excited to orbits of higher energy; 52
 THE BOHR As the electrons drop from lower to higher
level, energy is released in the form of
ATOM electromagnetic radiation.
Conversely, if radiation of the correct
energy is absorbed by an atom, electrons
are raised from lower to higher level.
An infinite quantum number means that
the nucleus and the electron are separate
entities.
Instead of being able to describe precise
orbits of electrons, as in the Bohr theory,
we can only describe orbitals, regions that
describe the probable location of
electrons.
Quantum numbers and orbital states
53
THE SCHRÖDINGER EQUATION
The Schrödinger equation describes the wave
properties of an electron in terms of its position,
mass, potential energy and total energy.
The equation is based on the wave function,
which describes an electron as a wave in space; (it
describes an atomic orbital).
In its simplest notation, the equation is

54
SUBATOMIC PARTICLES
Atom consists of a dense, positively charged nucleus
surrounded at a relatively large distance by negatively
charged electrons
Nucleus made up of protons, which are positively
charged, and neutrons, which are electrically neutral.
n(Protons) = n(electrons)
The nucleus contains essentially all the mass of the
atom.
Electrons have negligible mass and circulate around the
nucleus
angstrom (Å) is used to express atomic distances, 55
 SUBATOMIC PARTICLES
A specific atom is described by its atomic number (Z),
which gives the number of protons (or electrons) it
contains, and its mass number (A), which gives the total
number of protons and neutrons in its nucleus.
All the atoms of a given element have the same atomic
number but they can have different mass numbers
depending on how many neutrons they contain.
Atoms with the same atomic number but different mass
numbers are called isotopes.
The weighted-average mass in atomic mass units (amu)
of an element’s naturally occurring isotopes is called
atomic mass (or atomic weight)
1.008 amu for hydrogen, 12.011 amu for carbon, 30.974
56
ORBITALS Orbital describes the volume of
space around a nucleus that an
electron is most likely to occupy
There are four different kinds of
orbitals, denoted s, p, d, and f, each
with a different shape.
An s orbital is spherical, with the
nucleus at its center;
A p orbital is dumbbell-shaped;
Four of the five d orbitals are
cloverleaf-shaped
The fifth d orbital is shaped like an
elongated dumbbell with a doughnut
around its middle. 57
F-ORBITALS
 The orbitals in an atom are
organized into different electron
ORBITALS shells, centered around the nucleus
and having successively larger size
and energy.
Different shells contain different
numbers and kinds of orbitals, and
each orbital within a shell can be
occupied by two electrons
The first shell contains only a single
s orbital, denoted 1s, and thus holds
only 2 electrons.
The second shell contains one 2s
orbital and three 2p orbitals and
holds a total of 8 e-. 59
ORBITALS
The three different p orbitals within a given shell
are oriented in space along mutually
perpendicular directions, denoted Px, Py, and Pz.
The two lobes of each p orbital are separated by
a region of zero electron density called a node.

60
ELECTRON
CONFIGURATIONS
The lowest-energy arrangement, or ground-
state electron configuration, of an atom is a
listing of the orbitals occupied by its electrons.
We can predict this arrangement by following
three rules.
Rule 1
The lowest-energy orbitals
fill up first, according to the order 1s 2s 2p 3s
3p 4s 3d.
Note that the 4s orbital lies between the 3p
and 3d orbitals.
This is the Aufbau principle.
All orbitals related to
an energy level are of equal energy.
 Eg. The three 2p orbitals are the same energy
61
 ELECTRON
CONFIGURATI Rule 2
ONS Electrons act in some ways as if they were
ELEMENT ATOMI CONFIGURATIO
C N
spinning around an axis, like how the earth
NUMB spins. This spin can have two orientations,
ER denoted as up ( ) and down ( )
HYDROGEN 1
Only two electrons can occupy an orbital,
and they must be of opposite spin,
CARBON 6 This is the Pauli
exclusion principle.
Rule 3
If two or more empty orbitals
PHOSPHORU 15 of equal energy are available, one electron
S occupies each with spins parallel until all
orbitals are half-full. this
is the Hund’s rule. 3
1s
the2sground-state
2p
2 2
configuration of
Nitrogen is1s22s22p3 1s2 2s2 62
D4 AND D9 RULES OF
ELECTRONIC CONFIGURATION
Eg. Arsenic (As)
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p3
The first number represents the principal quantum
number (n)
The character is the sub-orbital (l)
The superscript is the total number of electrons in the
suborbital
When an electronic configuration ends with 4 or 9
electrons in the d-suborbital the atom is relatively
unstable
Promotion of electrons from the s-suborbital to the d-
TRY

Give the ground-state electron configuration for

each of the following
elements:
(a) Oxygen (b) Nitrogen (c) Sulfur

How many electrons does each of the following

elements have in its outermost electron shell?
(a) Magnesium (b) Cobalt (c) Selenium

64
HYBRID in 193, Linus Pauling showed mathematically how
an s orbital and three p orbitals on an atom can
ORBITALS combine, (hybridize), to form four equivalent
atomic orbitals with tetrahedral orientation.
These tetrahedrally oriented orbitals are called
SP3 hybrid orbitals. The superscript 3 in the
name tells how many of each type of atomic
orbital combine to form the hybrid
When an s orbital hybridizes with three p orbitals,
the resultant sp3 hybrid orbitals are
assymmetrical about the nucleus.
One of the two lobes is larger than the other and
can therefore overlap more effectively with an
orbital from another atom to form a bond.
As a result, sp3 hybrid orbitals form stronger
bonds than do unhybridized s or p orbitals
65
 SP3 HYBRID
The asymmetry of sp3 orbitals arises because
ORBITALS AND the two lobes of a p orbital have different
THE STRUCTURE algebraic signs, 1 and 2, in the wave function.
OF METHANE
Thus, when a p orbital hybridizes with an s
orbital, the positive p lobe adds to the s orbital
but the negative p lobe subtracts from the s
orbital. The resultant hybrid orbital is therefore
asymmetrical about the nucleus and is
strongly oriented in one direction.
When each of the four identical sp3 hybrid
orbitals of a carbon atom overlaps with the 1s
orbital of a hydrogen atom, four identical C-H
bonds are formed and methane results.
Sigma bond
Each C-H bond in methane has a strength of
Sigma bond
439 kJ/mol (105 kcal/mol) and a length of 109
Sigma bond pm.
Sigma bond
Because the four bonds have a specific
geometry, we also can define a property66 called
 SP3 HYBRID ORBITALS
AND THE STRUCTURE OF
The ETHANE
C - H bonds in ethane are
similar to those in methane,
although a bit weaker
421 kJ/mol (101 kcal/mol) for
ethane versus 439 kJ/mol for
methane.
The C-C bond is 154 pm long and
has a strength of 377 kJ/mol (90
kcal/mol).
All the bond angles of ethane are
near the tetra hedral value of
109.5°. 67
SP2 HYBRID ORBITALS The three sp2 orbitals lie in a plane at
AND THE STRUCTURE angles of 120° to one another, with the
OF ETHYLENE remaining p orbital perpendicular to
the sp2 plane,
Note that the electrons in the s bond
occupy the region centered between
nuclei, while the electrons in the p
bond occupy regions above and below
a line drawn between nuclei.
Ethylene thus has a planar structure,
with H-C-H and H-C-C bond angles of
approximately 120°.
(The actual values are 117.4° for the
H-C-H bond angle and 121.3° for the
H-C-C bond angle.)
Each C-H bond has a length of 108.7
pm and a strength of 464 kJ/mol (111
kcal/mol). 68
SP2 HYBRID ORBITALS
AND THE STRUCTURE OF
ETHYLENE
Hybrid orbitals Hybrid orbitals
of two hydrogen of two hydrogen
atoms atoms

Atomic orbital and

hybrid orbitals of
a carbon atom

Pi bond

Sigma bond
SP2 HYBRID ORBITALS AND
THE STRUCTURE OF
ETHYLENE
The carbon–carbon double bond in ethylene is both shorter
and stronger than the single bond in ethane because it has
four electrons bonding the nuclei together rather than two.
Ethylene has a C-C bond length of 134 pm and a strength
of 728 kJ/mol (174 kcal/mol) versus a C-C length of 154 pm
and a strength of 377 kJ/mol for ethane.
C-C double bond is less than twice as strong as a single
bond because the sideways overlap in the pie bond of the
double bond is not as great as the head-on overlap in the
sigma bond.
70
SP HYBRID ORBITALS Two p orbitals remain unchanged. The
AND THE STRUCTURE two sp orbitals are oriented 180°
OF ACETYLENE apart on the x-axis, while the p
orbitals are perpendicular on the y-
axis and the z-axis,
As suggested by sp hybridization,
acetylene is a linear molecule with H-
C-C bond angles of 180°.
The C-H bonds have a length of 106
pm and a strength of 558 kJ/mol (133
kcal/mol).
Has a C-C bond length of 120 pm, and
its strength is about 965 kJ/mol (231
kcal/mol), making it the shortest and
strongest of any carbon–carbon bond.

71
SP HYBRID ORBITALS
AND THE STRUCTURE
OF ACETYLENE
Atomic orbital Atomic orbital
of a hydrogen of a hydrogen
atom atom

Atomic orbitals and

hybrid orbitals of
a carbon atom

Sigma bonds
Pi bond
 HYBRIDIZATION OF
NITROGEN
The nitrogen atom in methylamine (CH NH ), an
3 2
organic derivative of ammonia (NH3) and the
substance responsible for the odor of rotting fish.
The experimentally measured H-N-H bond angle in
methylamine is 107.1°, and the C-N-H bond angle
is 110.3°, both of which are close to the 109.5°
tetrahedral angle found in methane. We therefore
assume that nitrogen forms four sp3-hybridized
orbitals
Note that the unshared lone pair of electrons in
the fourth sp3 hybrid orbital of nitrogen occupies
as much space as an N-H bond does and is very
important to the chemistry of methylamine and
other nitrogen-containing organic molecules. 73
HYBRIDIZATION OF OXYGEN

The oxygen atom in methanol (methyl alcohol) and

many other organic molecules can be described as sp3-
hybridized.
The C-O-H bond angle in methanol is 108.5°, very close
to the 109.5° tetrahedral angle.
Two of the four sp3 hybrid orbitals on oxygen are
occupied by nonbonding electron lone pairs, and two are
used to form bonds.

74
 HYBRIDIZATION OF
PHOSPHORUS,
Because of their positions in the third row, however,
both phosphorus and sulfur can expand their outer-
shell octets and form more than the typical number
of covalent bonds.
Phosphorus, often forms five covalent bonds, and
sulfur often forms four.
Eg. organophosphates, compounds that contain a
phosphorus atom bonded to four oxygens, with one
of the oxygens also bonded to carbon.
Methyl phosphate, CH3OPO3 is the simplest example.
The O-P-O bond angle in such compounds is
typically in the range 110 to 112°, implying an sp3
hybridization in the phosphorus orbitals.
75
 HYBRIDIZATION OF SULFUR
Sulfur is most commonly encountered in
biological molecules either in compounds
called thiols, which have a sulfur atom bonded
to one hydrogen and one carbon,
or in sulfides, which have a sulfur atom
bonded to two carbons.
methanethiol (CH3SH) is the simplest example
of a thiol, and dimethyl sulfide [(CH3)2S] is the
simplest example of a sulfide.
Produced by some bacteria,
Both can be described by approximate sp3
hybridization around sulfur, although both have
significant deviation from the 109.5°
tetrahedral angle.
76
VALENCE SHELL ELECTRON-PAIR REPULSION
Valence shell electron-pair repulsion (VSEPR) is an
approach that provides a method for predicting the shape of
molecules based on the electron-pair electrostatic repulsion
The most common method of determining the actual
structures is X-ray diffraction, although electron diffraction,
neutron diffraction, and many spectroscopic methods are
also used.
Electrons can be accommodated in the same region of space
as bonding pairs or lone pairs, but each pair repels all other
pairs.
According to the VSEPR model, molecules adopt geometries
such that valence electron pairs position themselves as far
from each other as possible to minimize electron–electron
repulsions
77
VALENCE SHELL ELECTRON-PAIR
REPULSION
The steric number is the total number of positions occupied
by atoms or lone pairs around a central atom
Carbon dioxide is a molecule with two atoms attached (SN = 2)
to the central atom via double bonds. The electrons in each
double bond must be between C and O, and the repulsion
between these electron groups forces a linear structure on the
molecule.
Sulfur trioxide has three atoms bound to the sulfur (SN = 3),
with equivalent partial double bond character between sulfur
and each oxygen, a conclusion rendered by analysis of its
resonance forms.
The best positions for the oxygens to minimize electron–
electron repulsions in this molecule are at the corners of an
equilateral triangle, with O-S-O bond angles of 120°.
78
The multiple bonding does not affect the geometry, because all
VALENCE SHELL ELECTRON-PAIR
REPULSION
As a general guideline, the VSEPR model predicts that
electron-pair repulsions involving lone pairs (lp) are stronger
than those involving bonding pairs (bp) in the order lp -lp
repulsions > lp-bp repulsions > bp-bp repulsions

Accounts for the H-N-H angle in ammonia being smaller

than the tetrahedral angle in methane and larger than the
H-O-H angle in water.
The isoelectronic molecules CH4, NH3, and H2O illustrate the
effect of lone pairs on molecular shape. Methane has four
identical bonds between carbon and each of the
hydrogens.
When the four pairs of electrons are arranged as far from
each other as possible, the result is the familiar tetrahedral 79
VALENCE SHELL ELECTRON-PAIR
REPULSION
Ammonia also has four pairs of electrons around the
central atom, but three are bonding pairs between N and H,
and the fourth is a lone pair on the nitrogen.
The nuclei form a trigonal pyramid with the three
bonding pairs; the lone pair occupies the fourth region in
space resulting in a tetrahedral arrangement of the four
electron groups.
Because each of the three bonding pairs is attracted by two
positively charged nuclei (H and N), these pairs are largely
confined to the regions between the H and N atoms.
The lone pair, is attracted solely by the nitrogen nucleus; it
has no second nucleus to confine it to a small region of
space. The lone pair tends to spread out and to occupy
more space around the nitrogen than the bonding pairs.
As a result, the H-N-H angles are 106.6°, nearly 3° smaller 80
VALENCE SHELL
ELECTRON-PAIR
REPULSION
The same principles apply to the water molecule, in which
two lone pairs and two bonding pairs repel each other.
Again, the electron pairs adopt a nearly tetrahedral
arrangement, with the atoms arranged in a V shape/bent.
The angle of largest repulsion, between the two lone pairs,
cannot be measured.
However, the lone pair–bonding pair (lp–bp) repulsion is
greater than the bonding pair bonding pair (bp–bp)
repulsion; as a result, the H-O-H bond angle is only 104.5°,
another 2.1° decrease from the ammonia angles.
The net result is that we can predict approximate molecular
shapes by assigning more space to lone electron pairs; lone
pairs are able to spread out and occupy more space since
they are attracted to one nucleus rather than two. 81
VALENCE SHELL ELECTRON-PAIR REPULSION
The VSEPR model considers double and triple bonds to
have slightly greater repulsive effects than single bonds
because of the repulsive effect of pie electrons that
increase the electron density between the bonded atoms
beyond that present in a sigma bond.

Linear Trigonal planar Bent Pyramidal

Tetrahedral Trigonal Octahedral Square

bipyramidal planar
82
MOLECULAR ORBITAL THEORY
Molecular orbital (MO) theory describes covalent bond
formation as arising from a mathematical combination of
atomic orbitals (wave functions) on different atoms to form
molecular orbitals,
So called because they belong to the entire molecule
rather than to an individual atom.
Just as an atomic orbital, whether unhybridized or
hybridized, describes a region of space around an atom
where an electron is likely to be found,
Molecular orbital describes a region of space in a molecule
where electrons are most likely to be found.

83
MOLECULAR ORBITAL THEORY
Like an atomic orbital, a molecular orbital has
a specific size, shape, and energy.
In the H2 molecule, for example, two singly
occupied 1s atomic orbitals combine to form
two molecular orbitals.
H H
There are two ways for the orbital combination
to occur—an additive way and a subtractive
way.
The additive combination leads to the H H
formation of a molecular orbital that is lower
in energy and roughly egg-shaped,
while the subtractive combination leads to a
molecular orbital that is higher in energy and
has a node between nuclei
84
BONDING AND ANTIBONDING MOLECULAR ORBITAL
Note that the additive combination is a single,
egg-shaped, molecular orbital; it is not the
same as the two overlapping 1s atomic orbitals
of the valence bond description.
Similarly, the subtractive combination is a
single molecular orbital with the shape of an
elongated dumbbell.
The additive combination is lower in energy
than the two hydrogen 1s atomic orbitals and
is called a bonding MO because electrons in
this MO spend most of their time in the region
between the two nuclei, thereby bonding the
atoms together.
The subtractive combination is higher in
energy than the two hydrogen 1s orbitals85and
BONDING AND ANTIBONDING MOLECULAR
ORBITAL
Just as bonding and antibonding s molecular
orbitals result from the headon combination of
two s atomic orbitals in H2, so bonding and
antibonding p molecular orbitals result from
the sideways combination of two p atomic
orbitals in ethylene.
The lower-energy, p bonding MO has no node
between nuclei and results from the
combination of p orbital lobes with the same
algebraic sign.
The higher-energy, p antibonding MO has a
node between nuclei and results from the
combination of lobes with opposite algebraic
signs. Only the bonding MO is occupied;
the higher-energy, antibonding MO is vacant.
86