Inorganic Chemistry

Year 1: Organic and Analytical Chemistry

Lecturer:

Dr Consolee Sibosiko
Lectures Part A
Academic year 2023-2024
 Part I: Inorganic Chemistry
• Knowledge and Understanding

• Having successfully completed the module, students should be

able to demonstrate knowledge and understanding of:

• Part 1: Inorganic Chemistry

1. Chemical Bonding and properties;

2. Molecular Geometry: molecular shapes, VSERP model,

and hybrides;

3. Atomic and molecular orbitals;

 Part II: Transition Metals and
Coordination Chemistry

1. Evolution of their physical and chemical properties: Hardness, melting point, Metal-
metal effects, Chelating effect, Acid base theory, Oxidation states

2. d-block elements and their major compounds: Transition elements (3d, 4d and 5d), Types
ligands: monodentante, bidentante, multidentante, Major compounds

3. Formation of Complexes and their nomenclature: Effective atomic number (Octet rule),
Formation of complexes, Coordination Number, Naming of complexes

4. Structure and Isomerism of complexes : Stereoisomer (optical isomers and geometrical

isomers), Structural isomerism (Coordination isomers, linkage isomers, ionisation
isomers and hydrate isomers, coordinate isomers, .......)

5. Crystal field theory: General Introduction, Splitting diagram energy of Tetrahedral,

Square Plan and Octahedral structure, Cristal Field Stabilisation Energy (strong and
weak Field), Series Chemical Spectroscopy, Magnetic properties of complexes,
Influence of ligands on the CFSE
 Part III: Reactions of inorganic
Complexes
1. Reactivity of complexes : Substitution reactions; Addition reactions;
Elimination reactions; Redox reactions.

2. Rate and mechanism of coordination compounds: Labile and inert

coordination compounds, Outer and inner sphere mechanism in
octahedral, Outer and inner sphere mechanism in tetrahedral complexes,
Outer and inner sphere mechanism in square Plan complexes, The
kinetic effect

3. Applications of complex compound: Medicinal applications, Analysis

applications, Catalyst applications, Environmental applications
 General Introduction
Aim
• This unit will allow you to be familiar with the basic concepts of inorganic
chemistry.
This unit will cover the following topics:
• The atomic models.
• The periodic table of elements.
• The evolution of properties in the periodic table.
Learning outcomes
• Chemical bonding and properties;
• Molecular geometry: molecular shapes, VSERP model, and Hybrids;
• Atomic and molecular orbitals;
 Essential ideas
Knowledge of
chemistry is
central to
understanding a
wide range of
scientific
disciplines. This
diagram
shows just some
of the
interrelationships
between
chemistry and
other fields.
 General Introduction
• Definition: Inorganic chemistry is the study of the synthesis,
reactions, structures and properties of compounds of the
elements.
• It also studies the behavior
of inorganic and organometallic compounds.
• This field covers all chemical compounds except the
myriad organic compounds (carbon based compounds,
usually containing C-H bonds).
• Inorganic Chemistry finds many applications such as:
chemical industry, including catalysis, material
science, pigments, coatings, medications, fuels,
and agriculture.
 General Introduction
• Many inorganic compounds are salts, consisting of cations and
anions joined by ionic bonding.
• Examples:
MgCl2, which consists of magnesium cations, Mg2+ and
chloride anions Cl−; Na2O, which consists of sodium cations
Na+ and oxide anions O2−
• In any salt, the proportions of the ions are such that the electric
charges cancel out, so that the bulk compound is electrically
neutral.
• Important classes of inorganic compounds: oxides, carbonates,
sulfates and the halides.
• Many inorganic compounds are characterized by high melting
points.
• Inorganic salts typically are poor conductors in the solid state.
Another important feature is their solubility in water, and
ease of crystallization. Where some salts (e.g. NaCl) are
very soluble in water, others (e.g. SiO2) are not.

The simplest inorganic reaction is double displacement

when in mixing of two compounds the ions are swapped
without a change in oxidation state.
Example: HCl + AgNO3 AgCl + HNO3

In redox reactions one reactant, the oxidant, lowers its

oxidation state and another reactant, the reductant, has its
oxidation state increased.
Example: Na(s) + HCl(aq) NaCl(aq) + H2(g)
In a more general definition, an acid can be any chemical
species capable of binding to electron pairs is called a Lewis
acid; a Lewis base is any molecule that donates an electron pair.

Inorganic compounds are found in nature as minerals.

Inorganic compounds can be used as biomolecules: electrolytes
(sodium chloride), energy storage (ATP) or in construction (the
polyphosphate backbone in DNA).
The first important man-made inorganic compound was
ammonium nitrate for soil fertilization through the Haber
process.

Inorganic compounds are synthesized for use as catalysts such

as vanadium(V) oxide and titanium(III) chloride, or as reagents
in organic chemistry such as. lithium aluminium hydride
Subdivisions of inorganic chemistry are organometallic
chemistry, cluster chemistry and bioinorganic chemistry.

Their classification focuses on:

- the position in the periodic table of the heaviest element
(the element with the highest atomic weight) in the compound.
- grouping compounds by their structural similarities.

Different classifications are:

Coordination compounds
Classical coordination compounds feature metals bond to "lone
pairs" of the ligands such as H2O, NH3, Cl−, and CN−.
In modern coordination compounds almost all organic and
inorganic compounds can be used as ligands.
One of the most important properties of metallic elements is
their ability to act as Lewis acids that form complexes with a
variety of Lewis bases. A metal complex consists of a central
metal atom or ion that is bonded to one or more ligands (from
the Latin ligare, meaning “to bind”), which are ions or
molecules that contain one or more pairs of electrons that can
be shared with the metal. Metal complexes can be neutral, such
as [Co(NH3)3Cl3]; positively charged, such as [Nd(H2O)9]3+; or
negatively charged, such as [UF8]4−. Electrically charged metal
complexes are sometimes called complex ions. A coordination
compound contains one or more metal complexes
Coordination compounds are important for at least three
reasons. First, most of the elements in the periodic table are
metals, and almost all metals form complexes, so metal
complexes are a feature of the chemistry of more than half the
elements. Second, many industrial catalysts are metal
complexes, and such catalysts are steadily becoming more
important as a way to control reactivity. For example, a mixture
of a titanium complex and an organometallic compound of
aluminum is the catalyst used to produce most of the
polyethylene and polypropylene “plastic” items we use every
day. Finally, transition-metal complexes are essential in
biochemistry. Examples include hemoglobin, an iron complex
that transports oxygen in our blood; cytochromes, iron
complexes that transfer electrons in our cells; and complexes of
Fe, Zn, Cu, and Mo that are crucial components of certain
enzymes, the catalysts for all biological reactions.
Transition metal compounds
Compounds containing metals from group 4 to 11 are
considered transition metal compounds.
Compounds with a metal from group 3 or 12 are sometimes
also incorporated into this group, but also often classified as
main group compounds.
Transition metal compounds show a rich coordination
chemistry, varying from tetrahedral for titanium (e.g. TiCl4)
to square planar for some nickel complexes to octahedral
for coordination complexes of cobalt.
A range of transition metals can be found in biologically
important compounds, such as iron in hemoglobin.
Examples: Fe(CO)5 iron pentacarbonyl, TiCl4 titanium
tetrachloride
Organometallic compounds
Organometallic compounds contain the M-C-H group. The
metal (M) in these species can either be a main group element
or a transition metal.
Organometallic compounds are mainly considered a special
category because organic ligands are often not sensitive to
hydrolysis or oxidation.
Organometallic compounds need more specialized preparative
methods than was traditional in Werner-type complexes.

Synthetic methodology, especially the ability to manipulate

complexes in solvents of low coordinating power, enabled the
exploration of very weakly coordinating ligands such as
hydrocarbons, H2, and N2.
Examples: Ferrocene Fe(C5H5)2, Molybdenum hexacarbonyl
Mo(CO)6
Cluster compounds
A cluster compound consists minimally of a triangular
set of atoms that are directly bonded to each other.
A metal-metal bonded dimetallic complexes are highly
relevant to the area. Clusters occur in "pure" inorganic
systems, organometallic chemistry, main group
chemistry, and bioinorganic chemistry.
Examples: Fe3(CO)12, B10H14, [Mo6Cl14]2−, B5H9,
[Re(CO)3(Hbhp)]2 (with (μ-O)2Re2 moiety)
Bioinorganic compounds
These compounds occur in nature, but the subfield includes
anthropogenic species, such as pollutants (e.g.
methylmercury) and drugs (e.g. Cis platin).
The field of biochemistry, includes many kinds of compounds,
e.g. phosphates in DNA, metal complexes containing
ligands that range from biological macromolecules, commonly
peptides, to defined species such as humic acid, and to water
(e.g. coordinated to gadolinium complexes employed for
MRI).
Bioinorganic chemistry focuses on electron- and energy-
transfer in proteins relevant to respiration.
Medicinal inorganic chemistry includes the study of both non-
essential and essential elements with applications to diagnosis
and therapies.
Examples: hemoglobin, methylmercury H3C-Hg+X-,
Solid state compounds
This important area focuses on structure, bonding, and the
physical properties of materials.

In practice, solid state inorganic chemistry uses techniques

such as crystallography to gain an understanding of the
properties that result from collective interactions between the
subunits of the solid.
Solid state compounds are metals and their alloys or
intermetallic derivatives.
Related fields are condensed matter physics, mineralogy, and
materials science.
Examples: YBa2Cu3O7 (Barium copper Yttrium oxide).
 Atom, element and
compound
• Any atom is composed of a little nucleus surrounded
by a "cloud" of electrons. In the nucleus there are
protons and neutrons
• When an atom is defined by the number of protons
contained in its nucleus, chemists refer to it as an
element.
• All elements have a very specific identity that makes
them unique from other elements.
• Compounds are composed of different type of
atoms. More precisely, a compound is a chemical
substance that consists of two or more elements.
 Properties of matter/
Physical properties
• Intensive: A physical property that will be the same regardless of the
amount of matter.
– density: m/v
– color: The pigment or shade
– conductivity: Electricity to flow through the substance
– malleability: if a substance can be flattened
– luster: How shiny the substance looks
• Extensive: A physical property that will change if the amount of matter
changes.
– mass: How much matter in the sample
– volume: How much space the sample takes up
– length: How long the sample is
 Physical changes
• Physical changes are change in which the matter's physical
appearance is altered, but composition remains unchanged.
(Change in state of matter).
• In a physical change, there is a change in the form of a
substance, not in its chemical composition. The substances
(atoms, molecules, or ions) present before or after a change
are the same.
• In a physical change, there is a change in the form of a
substance, not in its chemical composition. The substances
(atoms, molecules, or ions) present before or after a change
are the same. For e.g when water freezes or boils, it changes
its state but remains water; it is still composed of H2O
molecules; melting of a solid
 Chemical properties and
Chemical changes
• Any characteristic that gives a sample of matter the
ability/inability to undergo a change that alters its
composition.
• Chemical change is the change in which one or more kinds of
matter are transformed to new kinds of matter with altered
compositions.
• Is one in which one or more substances (the reactants) are
transformed into one or more different substances (the
products) with different properties and different composition.
Eg: Magnesium + Oxygen --> Magnesium Oxide
or 2 Mg + O2 --> 2 MgO
 Atomic mass
• The modern system of atomic masses is based on carbon 12
as the standard.
• In this system, carbon twelve is assigned a mass of exactly 12
atomic mass units (amu), and the masses of other atoms are
given relative to this standard.
• The average atomic mass is simply called atomic mass for an
element.
• The relative atomic mass of a compound is the sum of the
relative atomic mass of all atoms in the molecule of the
considered compound.
• Ex: H2O: relative molar mass= 2*1+ 16 = 18grams
• Absolute atomic mass of carbon atom
12amu=12*1.66054*10 -24 g
 Mole
• Because samples of matter typically contain many atoms, a
unit of measure called the mole has been established to
counting atoms.
• Mole is defined as the number equal to the number of carbon
atoms in exactly 12 g of pure 12C.
• With the help of mass spectrometer, this number was found
to be 6.02214 x 1023. This number is called Avogadro’s number
to honor his contributions to chemistry.
• One mole of something consists of 6.02214 x 1023 units of that
substance. Just as a dozen eggs is 12 eggs, a mole of eggs is
6.02214 x 1023 eggs.
 Molar mass
• It is the mass in grams of one mole of the compound.
• The molar mass of a compound is obtained by
summing the masses of the component atoms
• Molar mass is used to convert grams of a substance
to moles and is used often in chemistry.
• The molar mass of an element is found on the
periodic table and it is the element's atomic weight
in grams/mole (g/mol). The atomic mass is the mass
of one mole of that element.
• If we know the mass of a substance, we can then
determine how many moles are in the substance.
• Converting the mass, in grams, of a substance to
moles requires a conversion factor of (one mole of
substance/molar mass of substance).
• Using Avogadro's constant, it is also easy to calculate
the number of atoms or molecules present in a
substance. By multiplying the number of moles by
Avogadro's constant, the mol units cancel out, leaving
the number of atoms.
• Examples
1) Calculate the molar mass of potassium dichromate
K2Cr2O7
2) How many atoms are in a 3.0 g sample of
sodium (Na)?
3) Convert to moles and find the total number
of atoms of
a) 5.06 grams of Oxygen; b) 2.14 grams of K
c) 0.134 Kg of Li
4) Convert the following to grams
a) 4.5 mols of C; b) 7.1 mols of Al; c) 2.2 mols
of Mg
 Concentration
• Mass percent = (g of solute/g of solution)*100
• Malarity (M) = (number of mole/L of solution)
• Molality (m) = (number of mole/Kg of solvent)
• Normality(N) = ( equivalent of solute/ L of
solution)
• Mole fractional = number of mole of one
component / total number of moles of all
substances
 Fundamental Chemistry
Laws
• 1) Law of conservation of mass or Lavoisier’s law by Antoine
Lavoisier (1743-1794), a French chemist. ‘Mass is neither
created nor destroyed’.
• The law implies (requires) that during any chemical reaction,
nuclear reaction, in an isolated system, the total mass of the
reactants or starting materials must be equal to the mass of
the products.
• 2) Law of definite proportion or Proust’s law by Joseph
Proust (1754-1826), a Frenchman,.
• “a given compound always contains exactly the same
proportion of elements by mass”.
• 3) Law of multiple proportions by John Dalton (1766-1844),
an English schoolteacher.
• “When two elements form a series of compounds, the ratios
of the masses of the second element that combine with 1g of
the first element can always be reduced to small whole
numbers”.
• E.g. carbon forms two oxides by combining with oxygen in
different proportions. A fixed mass of carbon, say 100 grams,
may react with 133 grams of oxygen to produce one oxide, or
with 266 grams of oxygen to produce the other.
• The ratio of the masses of oxygen that can react with
100 grams of carbon is 266:133 ≈ 2:1, a ratio of small whole
numbers.
• The two oxides have one and two oxygen atoms respectively
for each carbon atom. In modern notation the first is CO
(carbon monoxide) and the second is CO2 (carbon dioxide).
• 4) Avogadro’s law by the Italian chemist in 1811“equal volumes
of gases at the same temperature and pressure contain equal
number of moles or molecules” V& n (T and P constant). V = a n
(A = constant of proportionality).
• It follows that one mole of any gas at a given T and P has the
same fixed volume called the molar gas volume. At standard
temperature and pressure (STP), one mole of any gas occupies a
volume of 22.4 litres.
• 5) Dalton’s law of partial pressures.
• In a mixture of gases, each component gas exerted a pressure as
if it were alone in the container.
• The individual pressure of each gas in the mixture is defined as
its partial pressure.
• By John Dalton in 1807. “the total pressure of a mixture of gases
is equal to the sum of the partial pressures of all the gases
present ” P = P + P + P + …(V and T are constant). P = n RT/V
 Atomic Structure: Historical
background
• Democritus was a Greek philosopher who was
the first person to use the term atom (atomos:
meaning indivisible). 400 BC
• He thought that if you take a piece of matter
and divide it and continue to divide it you will
eventually come to a point where you could
not divide it any more. This fundamental or
basic unit was what Democritus called an
atom
 Atomic Structure: Historical
background
He called this the theory of the universe:
• All matter consists of atoms, which are bits of
matter too small to be seen.
• There is an empty space between atoms
• Atoms are completely solid
• Atoms have no internal structure
• Each atom (of a different substance) is
different in size, weight and shape.
 Scientist: John Dalton (1800’s)
• John Dalton was the first to adapt Democritus’
theory into the first modern atomic model.
JOHN DALTON’S ATOMIC MODEL:
1. All matter consists of tiny particles called
atoms
2.Atoms are indestructible and unchangeable
3.Elements are characterized by the weight of
their atoms
4.When elements react, it is their atoms that
have combined to form new compounds
 Scientist: J.J Thomson
(1890’s)
• J.J Thomson was a physicist who is credited for
discovering the electron. He used his research
on cathode ray tube technology in this
discovery.
• The charge is invisible, so to see where it traveled a
fluorescent screen is placed at back of tube. Where
the beam hits, a dot will appear on the screen. You
could also use a fluorescent gas and the whole tube
will light up.
• This beam will always travel straight if not interfered
with.
• The deflection coils each have a specific charge. One
is positive and the other is negative.
 THOMSON’S ATOMIC MODEL
• Using what he had discovered, Thomson predicted what an
atom should look like. These are the key points to Thomson’s
Atomic Model:
• Because of its design this model is known as the plum pudding
model
• Each atom is a sphere filled with positively charged ‘fluid’. This
resembles the sticky jam part of a pudding.
 Properties Fundamental of
the particle
• Properties
 Scientist: Ernest Rutherford
(1910’s)
• Ernest Rutherford was not convinced about the model of the
atom proposed by Thomson. He thus set up his now famous
Gold Foil Experiment.
– He fired alpha particles (positively charged) at a gold foil.
– He measured the deflection as the particles came out the
other side.
– Most of the particles did not deflect at all. Every now and then
a particle would deflect all the way back.
 RUTHERFORD’S ATOMIC MODEL
(THE PLANETARY MODEL)
• The nucleus of the atom is a dense mass of positively
charged particles.
• The electrons orbit the nucleus
• A problem raised was: Why are the negatively charged
particles not attracted by the positively charged nucleus
• Rutherford stated that the atom was like a mini solar
system and that the electrons orbited the nucleus in a wide
orbit. That is why it is known as the planetary model.
 Scientist: Niels Bohr
(1910’s)
• Niels Bohr agreed with the planetary model of the
atom, but also knew that it had a few flaws. Using his
knowledge of energy and quantum physics he was
able to perfect Rutherford’s model. He was able to
answer why the electrons did not collapse into the
nucleus.

• The energy difference can be calculated as the above

Spectrum emission series
 BOHR’S ATOMIC MODEL
1. Electrons orbit the nucleus in orbits that have a set size and
energy.
2. The lower the energy of the electron, the lower the orbit.
3. This means that as electrons fill up the orbitals, they will fill
the lower energy level first.
4. If that energy level is filled (or at capacity), a new energy level
will begin.
5. Radiation is when an electron moves from one level to
another. Problems with this theory:
Electrons do not travel on a specific orbit or path.
 Scientist: Erwin Schrödinger
(1920’s)
• Erwin Schrödinger was a revolutionary physicist who used
Heisenberg’s uncertainty principle to come up with the
atomic model that we still use today.
SCHRÖDINGER’S ATOMIC MODEL (THE CLOUD MODEL)
1. An electron does not travel in an exact orbit
2. We can predict where it will probably be
3. We cannot say for certain where it is, but only where it ought
to be.
 SUMMARY OF ATOM
• The smallest part of an element is called an atom
• Each atom (of an element) is different in structure
from other atoms (of other elements)
• An atom can be divided in smaller subatomic
particles: Protons, Electrons and Neutrons
Atom 'structure
Electromagnetic radiation
Electromagnetic radiation
Electromagnetic radiation
 Quantum numbers
The shape, size, and energy of each orbital is a function
of 3 quantum numbers which describe the location
of an electron within an atom or ion
n (principal) ---> energy level
l (orbital) ---> shape of orbital
ml (magnetic) ---> designates a particular
suborbital
The fourth quantum number is not derived from the
wave function
s (spin) ---> spin of the electron
(clockwise or counterclockwise: ½ or – ½)
 Quantum numbers
So… if two electrons are in the same place at the
same time, they must be repelling, so at least
the spin quantum number is different!
The Pauli Exclusion Principle says that no two
electrons within an atom (or ion) can have the
same four quantum numbers.
If two electrons are in the same energy level,
the same sublevel, and the same orbital, they
must repel.
Think of the 4 quantum numbers as the address
of an electron… Country > State > City > Street
 Example
• Write n, l, ml and s quantum numbers for the
5 electrons of a boron atom
Answer:
1,0,0,+1/2
1,0,0,-1/2
2,0,0,+1/2
2,0,0,-1/2
2,1,-1,+1/2
This example shows that no two electrons in one atom
will have the same four quantum numbers.
Quantum numbers
 Types of orbitals
• The most probable area to find these
electrons takes on a shape
• So far, we have 4 shapes. They are named s,
p, d, and f.
• No more than 2 e- assigned to an orbital – one
spins clockwise, one spins counterclockwise
P orbitals
d orbitals
The shapes and labels of
the five 3d orbitals
f orbitals
Electronic configuration
Electronic
configuration

Energetic
levels and
sublevels of
polyelectronic
atoms
 Electron configuration
• Orbitals and quantum numbers (Shells and sub shells)

• In atomic physics and quantum chemistry, the electron

configuration is the distribution of electrons of an atom or
molecule in atomic or molecular orbitals.
• Electron configuration was first conceived of under the Bohr
model of the atom
• The electrons occupy a series of electron shells (numbered
shell 1, shell 2 up to 7 or K, L up to Q).
• Each shell consists of one or more subshells (named s, p, d, f
and g). Electrons fill the shells according to the Madelung
rule or energy ordering rule.
An electron shell is the set of allowed states electrons may
occupy which share the same principal quantum number, n

An atom's nth electron shell can accommodate 2n2 electrons,

e.g. the first shell (n=1) can accommodate 2 electrons, the
second shell 8 electrons, and the third shell 18 electrons.

The factor of two arises because the allowed states are doubled
due to electron spin-each atomic orbital admits up to two.

electrons have opposite spin, one with a spin +1/2 (usually noted
by an up-arrow) and one with a spin -1/2 (with a down-arrow).
A subshell is the set of states defined by a common
azimuthal quantum number, l, within a shell. The values l =
0, 1, 2, 3 correspond to the s, p, d, and f labels, respectively.

The maximum number of electrons which can be placed in a

subshell is given by 2(2l + 1).

This gives two electrons in an s subshell, six electrons in a

p subshell, ten electrons in a d subshell and fourteen
electrons in an f subshell

Example: The electronic configuration for neon is

1s2 2s2 2p6.
Orbitals and the periodic table
 Exceptions to the Aufbau
Principle
• Remember d and f orbitals require large
amounts of energy
• If we can’t fill these sublevels, then the next
best thing is to be half full (one electron in
each orbital in the sublevel)
• There are many exceptions, but the most
common ones are
d4 and d9
For the purposes of this class, we are going to
assume that all atoms (or ions) that end in d4
or d9 are exceptions to the rule. This may or
may not be true, it just depends on the atom.
 Exceptions to the Aufbau
Principle
Ok, so this helps the d, but what about the poor
s orbital that loses an electron?
Remember, half full is good… and when an s
loses 1, it too becomes half full!
So… having the s half full and the d half full is
usually lower in energy than having the s full
and the d to have one empty orbital.
 Exceptions to the Aufbau
Principle
d9 is one electron short of being full
Just like d4, one of the closest s electrons will go into
the d, this time making it d10 instead of d9.
For example: Au would be [Xe] 6s2 4f14 5d9, but since
this ends exactly with a d9 it is an exception to the
rule. Thus, Au should be [Xe] 6s1 4f14 5d10.
Procedure: Same as before! Find the closest s orbital.
Steal one electron from it, and add it to the d.
 Exceptions to the Aufbau
Principle
d4 is one electron short of being half full
In order to become more stable (require less energy),
one of the closest s electrons will actually go into the
d, making it d5 instead of d4.
For example: Cr would be [Ar] 4s2 3d4, but since this
ends exactly with a d4 it is an exception to the rule.
Thus, Cr should be [Ar] 4s1 3d5.
Procedure: Find the closest s orbital. Steal one electron
from it, and add it to the d.
Lanthanides elements
 EC of an atom in AO
Eg:Using complete s, p, d, f subshell notation, predict the
electron configurations of the following atoms or ions. (Note:
The atomic number (Z) for S=16, Gd=64, Cs=55, and Cr=24)
• i) S- ii) Gd3+ iii) Cs iv) Cr
Answer:
• i) [Ne] 3s²3p5 or 1s22s22p63s23p5
• ii) [Xe] 4f7 or [Xe] 4f7 5d06s0 or
1s22s22p63s23p63d104s24p64d105s25p64f7
• iii) [Xe] 6s1 or
1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s25p6 6s1
• iv) [Ar] 3d⁵4s¹ or 1s22s22p63s23p63d54s1
Periodic table
 Periodic table variation
• Describe and explain the observed trends in atomic size, ionization energy, and
electron affinity of the elements:
• The elements in groups (vertical columns) of the periodic table exhibit similar
chemical behavior. This similarity occurs because the members of a group have
the same number and distribution of electrons in their valence shells.
• However, there are also other patterns in chemical properties on the periodic
table. For example, as we move down a group, the metallic character of the
atoms increases. Oxygen, at the top of group 16 (6A), is a colorless gas; in the
middle of the group, selenium is a semiconducting solid; and, toward the
bottom, polonium is a silver-grey solid that conducts electricity.
• As we go across a period from left to right, we add a proton to the nucleus and
an electron to the valence shell with each successive element. As we go down
the elements in a group, the number of electrons in the valence shell remains
constant, but the principal quantum number increases by one each time. An
understanding of the electronic structure of the elements allows us to examine
some of the properties that govern their chemical behavior.
 Periodic table variation
• (a) The radius of an atom is defined as one-half the distance between the nuclei in
a molecule consisting of two identical atoms joined by a covalent bond. The atomic
radius for the halogens increases down the group as n increases.
• (b) Covalent radii of the elements are shown to scale. The general trend is that
radii increase down a group and decrease across a period
Within each period, the trend in atomic radius decreases as Z increases; for example,
from K to Kr. Within each group (e.g., the alkali metals shown in purple), the trend is that
atomic radius increases as Z increases.
 Periodic table variation
• As we move across a period from left to right, we generally
find that each element has a smaller covalent radius than the
element preceding it. This might seem counterintuitive
because it implies that atoms with more electrons have a
smaller atomic radius.
• This can be explained with the concept of effective nuclear
charge, Zeff. This is the pull exerted on a specific electron by
the nucleus, taking into account any electron–electron
repulsions. For hydrogen, there is only one electron and so
the nuclear charge (Z) and the effective nuclear charge (Zeff)
are equal.
 Periodic table variation
• For all other atoms, the inner electrons
partially shield the outer electrons from the
pull of the nucleus and thus:
• Zeff = Z − shielding
• Shielding is determined by the probability of
another electron being between the electron
of interest and the nucleus, as well as by the
electron repulsions the electron of interest
encounters.
 Periodic table variation
• Core electrons are adept at shielding, while electrons in the same valence shell do
not block the nuclear attraction experienced by each other as efficiently.
• Thus, each time we move from one element to the next across a period, Z
increases by one, but the shielding increases only slightly. Thus, Zeff increases as
we move from left to right across a period. The stronger pull (higher effective
nuclear charge) experienced by electrons on the right side of the periodic table
draws them closer to the nucleus, making the covalent radii smaller.
• Thus, as we would expect, the outermost or valence electrons are easiest to
remove because they have the highest energies, are shielded more, and are
farthest from the nucleus. As a general rule, when the representative elements
form cations, they do so by the loss of the ns or np electrons that were added last
in the Aufbau process.
• The transition elements, on the other hand, lose the ns electrons before they
begin to lose the (n – 1)d electrons, even though the ns electrons are added first,
according to the Aufbau principle.
 Periodic table variation
• Predict the order of increasing covalent radius for Ge, Fl, Br, Kr.
Solution
• Radius increases as we move down a group, so Ge < Fl (Note: Fl is the symbol for
flerovium, element 114, NOT fluorine). Radius decreases as we move across a
period, so Kr < Br < Ge. Putting the trends together, we obtain Kr < Br < Ge < Fl.
Effective nuclear charge Z*
• The presence of other electrons around a nucleus “screens” an electron from the
full charge of the nucleus.
• We can approximate the energy of the electrons by modifying the Bohr equation
to account for the lower “effective” nuclear charge

 Z *2 
En = − R  2 
n 
 Prediction  and Z*
• Slater’s rules for the prediction of  for an electron:
1. Group electron configuration as follows:
(1s)(2s,2p)(3s,3p)(3d)(4s,4p)(4d)(4f)(5s,5p) etc.
2. Electrons to the right (in higher subshells and shells) of an electron do not
shield it.
3. For ns or np valence electrons:
a) Each other electron in the same group contributes 0.35 (0.30 for
1s)
b) Each electron in an n-1 group contributes 0.85
c) Each electron in an n-2 or lower group contributes 1.00
4. For nd or nf valence electrons:
a) Each other electron in the same group contributes 0.35
b) Each electron in a lower group (to the left) contributes 1.00
 Prediction  and Z*
Example 1 with a valence electron on oxygen: O, Z = 8
Electron configuration: 1s2 2s2 2p4

a) (1s2) (2s2 2p4)

a)  = (2 * 0.85) + (5 * 0.35) = 3.45

1s 2s,2p
Z* = Z - 

Z* = 8 – 3.45 = 4.55

This electron is actually held with about 57% of the force

that one would expect for a +8 nucleus.
 Example
• Prediction  and Z*
For N, O and F and compare their size
 Prediction  and Z*
Example 2 with two electrons for nickel: Ni, Z = 28
Electron configuration: 1s2 2s2 2p6 3s2 3p6 3d8 4s2

(1s2) (2s2 2p6) (3s2 3p6) (3d8) (4s2)

For a 3d electron:
 = (18 * 1.00) + (7 * 0.35) = 20.45
1s,2s,2p,3s,3p 3d

Z* = Z -  Z* = 28 – 20.45 = 7.55

For a 4s electron:
 = (10 * 1.00) + (16 * 0.85) + (1 * 0.35) = 23.95
1s,2s,2p 3s,3p,3d 4s

Z* = Z -  Z* = 28 – 23.95 = 4.05
 Variation in ionization energy
• The amount of energy required to remove the most loosely bound electron from a
gaseous atom in its ground state is called its first ionization energy (IE1). The first
ionization energy for an element, X, is the energy required to form a cation with +1
charge: X(g) ⟶ X+(g) + e− IE1
• The energy required to remove the second most loosely bound electron is called
the second ionization energy (IE2). X+(g) ⟶ X2+ (g) + e− IE2
• The energy required to remove the third electron is the third ionization energy,
and so on. Energy is always required to remove electrons from atoms or ions, so
ionization processes are endothermic and IE values are always positive.
• For larger atoms, the most loosely bound electron is located farther from the
nucleus and so is easier to remove. Thus, as size (atomic radius) increases, the
ionization energy should decrease.
• Relating this logic to what we have just learned about radii, we would expect first
ionization energies to decrease down a group and to increase across a period.
The first ionization energy of the elements in the first five periods
are plotted against their atomic number.
 Variation in electron affinity
• The electron affinity (EA) is the energy change
for the process of adding an electron to a
gaseous atom to form an anion (negative ion).
• X(g) + e− ⟶ X−(g) EA1
• As we might predict, it becomes easier to add
an electron across a series of atoms as the
effective nuclear charge of the atoms
increases.
 Chemical Bonding and
Properties
• Molecules (and extended solids) are built from atoms that
form chemical bonds. Theories of bonding seek to explain why
molecules and solids form, what their structures are, why
some are more stable than others, and how they react.
• Models such as Lewis dot structures and valence shell
electron-pair repulsion (VSEPR) theory. When combined with
a qualitative quantum mechanical description of bonding
through the concepts of orbital hybridization and resonance,
these simple models can help us understand a great deal
about the structures, stabilities, and reactions of inorganic
molecules.
 Chemical Bonding and
Properties
• A chemical bond is a lasting attraction between atoms that
enables the formation of chemical compounds.
• The bond may result from the electrostatic force of attraction
between atoms with opposite charges, or through the sharing
of electrons as in the covalent bonds.
• Example. The element sodium is a silver-colored metal
• The element chlorine is a greenish-colored gas that is so
poisonous that it was used as a weapon in World War I.
• When chemically bonded together, these two dangerous
substances form the compound sodium chloride (NaCl), a
compound so safe that we eat it every day - common table salt.
 Assignment
“There is no topic more fundamental to
Chemistry than the nature of the chemical
bond”
Write an essay project of such statement
 Chemical Bonding and
Properties
• Ionic Bonding
• Covalent Bonding
• Lewis Symbols and Structures
• Formal Charges and Resonance
• Strengths of Ionic and Covalent Bonds
• Molecular Structure and Polarity
 The Formation of Ionic Compounds

• Binary ionic compounds are composed of just

two elements: A metal (which forms the
cations) and a nonmetal (which forms the
anions)
• For example, NaCl is a binary ionic compound.
We can think about the formation of such
compounds in terms of the periodic
properties of the elements.
 The Formation of Ionic Compounds

• Many metallic elements have relatively low

ionization potentials and lose electrons easily. These
elements lie to the left in a period or near the
bottom of a group on the periodic table.
• Nonmetal atoms have relatively high electron
affinities and thus readily gain electrons lost by metal
atoms, thereby filling their valence shells.
• Nonmetallic elements are found in the upper-right
corner of the periodic table.
 The Formation of Ionic Compounds
• As all substances must be electrically neutral, the total
number of positive charges on the cations of an ionic
compound must equal the total number of negative charges
on its anions
• The formula of an ionic compound represents the simplest
ratio of the numbers of ions necessary to give identical
numbers of positive and negative charges.
• For example, the formula for aluminum oxide, Al2O3, indicates
that this ionic compound contains two
• aluminum cations, Al3+, for every three oxide anions, O2−
[thus, (2 × +3) + (3 × –2) = 0].
 The Formation of Ionic Compounds
• The atoms in sodium chloride
(common table salt) are arranged
to (a) maximize opposite charges
• interacting. The smaller spheres
represent sodium ions, the larger
ones represent chloride ions. In
the expanded view
• (b), the geometry can be seen
more clearly. Note that each ion
is “bonded” to all of the
surrounding ions six in this case.
 The Formation of Ionic Compounds

• The strong electrostatic attraction between

Na+ and Cl– ions holds them tightly together in
solid NaCl. It requires 769 kJ of energy to
dissociate one mole of solid NaCl into separate
gaseous Na+ and Cl– ions:
• NaCl(s) ⟶ Na+(g) + Cl-(g) ΔH = 769 kJ
 Electronic Structures of Cations

• When forming a cation, an atom of a main group element

tends to lose all of its valence electrons, thus assuming the
electronic structure of the noble gas that precedes it in the
periodic table.
• For example, calcium is a group 2 element whose neutral
atoms have 20 electrons and a ground state electron
configuration of 1s22s22p63s23p64s2. When a Ca atom loses
both of its valence electrons, the result is a cation with 18
electrons, a 2+ charge, and an electron configuration of
1s22s22p63s23p6. The Ca2+ ion is therefore isoelectronic with
the noble gas Ar.
 Electronic Structures of Cations

• Exceptions to the expected behavior involve

elements toward the bottom of the groups. In
addition to the expected ions Tl3+, Sn4+, Pb4+, and
Bi5+, a partial loss of these atoms’ valence shell
electrons can also lead to the formation of Tl+, Sn2+,
Pb2+, and Bi3+ ions. The formation of these 1+, 2+,
and 3+ cations is ascribed to the inert pair effect,
• which reflects the relatively low energy of the
valence s-electron pair for atoms of the heavy
elements of groups 13, 14, and 15.
 Electronic Structures of Cations

• Transition and inner transition metal elements

behave differently than main group elements.
• Most transition metal cations have 2+ or 3+
charges that result from the loss of their
outermost s electron(s) first, sometimes
followed by the loss of one or two d electrons
from the next to outermost shell.
 Electronic Structures of Cations

• For example, iron (1s22s22p63s23p63d64s2) forms the

ion Fe2+ (1s22s22p63s23p63d6) by the loss of the 4s
electron and the ion Fe3+ (1s22s22p63s23p63d5) by the
loss of the 4s electron and one of the 3d electrons.
• Although the d orbitals of the transition elements are
according to the Aufbau principle the last to fill when building
up electron configurations, the outermost s electrons are the
first to be lost when these atoms ionize. When the inner
transition metals form ions, they usually have a 3+ charge,
resulting from the loss of their outermost s electrons and a d
or f electron.
 Practice
• There are at least 14 elements categorized as
“essential trace elements” for the human body. They
are called
• “essential” because they are required for healthy
bodily functions, “trace” because they are required
only in small amounts, and “elements” in spite of the
fact that they are really ions. Two of these essential
trace elements, chromium and zinc, are required as
Cr3+ and Zn2+. Write the electron configurations of
these cations. Answer: Zn2+: [Ar]3d10
• Cr3+: [Ar]3d3
 Practice
• Selenium and iodine are two essential trace
elements that form anions. Write the electron
configurations of the anions.
Solution
• Se2–: [Ar]3d104s24p6
• I –: [Kr]4d105s25p6
 Ionic Bonding
• Atoms gain or lose electrons to form ions with
particularly stable electron configurations.
• The charges of cations formed by the representative
metals may be determined readily because, with few
exceptions, the electronic structures of these ions
have either a noble gas configuration or a completely
filled electron shell.
• The charges of anions formed by the nonmetals may
also be readily determined because these ions form
when nonmetal atoms gain enough electrons to fill
their valence shells.
 Covalent Bonding
By the end of this section, you will be able to:
• Describe the formation of covalent bonds
• Define electronegativity and assess the polarity of
covalent bonds
• Ionic bonding results from the electrostatic attraction
of oppositely charged ions that are typically
produced by the transfer of electrons between
metallic and nonmetallic atoms.
• A different type of bonding results from the mutual
attraction of atoms for a “shared” pair of electrons.
Such bonds are called covalent bonds.
 Covalent bonds
• Covalent bonds form when electrons are shared
between atoms and are attracted by the nuclei of
both atoms.
• In pure covalent bonds, the electrons are shared
equally. In polar covalent bonds, the electrons are
shared unequally, as one atom exerts a stronger
force of attraction on the electrons than the other.
The ability of an atom to attract a pair of electrons in
a chemical bond is called its electronegativity.
 Covalent bonds
• Covalent bonds are formed between two atoms
when both have similar tendencies to attract
electrons to themselves (i.e., when both atoms have
identical or fairly similar ionization energies and
electron affinities).
• For example, two hydrogen atoms bond covalently to
form an H2 molecule; each hydrogen atom in the H2
molecule has two electrons stabilizing it, giving each
atom the same number of valence electrons as the
noble gas He.
 Covalent bonds
• The difference in electronegativity between two
atoms determines how polar a bond will be.
• In a diatomic molecule with two identical atoms,
there is no difference in electronegativity, so the
bond is nonpolar or pure covalent.
• When the electronegativity difference is very large,
as is the case between metals and nonmetals, the
bonding is characterized as ionic.
 Electronegativity
• Whether a bond is nonpolar or polar covalent is
determined by a property of the bonding atoms
called electronegativity. Electronegativity is a
measure of the tendency of an atom to attract
electrons (or electron density) towards itself. It
determines how the shared electrons are distributed
between the two atoms in a bond.
• The more strongly an atom attracts the electrons in
its bonds, the larger its electronegativity.
 Electronegativity
• Electrons in a polar covalent bond are shifted
toward the more electronegative atom; thus,
the more electronegative atom is the one with
the partial negative charge.
• The greater the difference in electronegativity,
the more polarized the electron distribution
and the larger the partial charges of the
atoms.
 Electronegativity versus Electron
Affinity
• We must be careful not to confuse electronegativity
and electron affinity. The electron affinity of an
element is a measurable physical quantity, namely,
the energy released or absorbed when an isolated
gas-phase atom acquires an electron, measured in
kJ/mol. Electronegativity, on the other hand
describes how tightly an atom attracts electrons in a
bond.
Electronegativity and Bond Type
 Lewis Symbols and
Structures
• Valence electronic structures can be visualized by drawing
Lewis symbols (for atoms and monatomic ions) and
• Lewis structures (for molecules and polyatomic ions). Lone
pairs, unpaired electrons, and single, double, or triple
• bonds are used to indicate where the valence electrons are
located around each atom in a Lewis structure.
• Most structures, especially those containing second row
elements obey the octet rule, in which every atom (except H)
is surrounded by eight electrons. Exceptions to the octet rule
occur for odd-electron molecules (free radicals), electron-
deficient molecules, and hypervalent molecules.
 Lewis Symbols
• We use Lewis symbols to describe valence
electron configurations of atoms and
monatomic ions. A Lewis symbol consists of an
elemental symbol surrounded by one dot for
each of its valence electrons:
Lewis symbols can also be used to illustrate the formation of
cations from atoms, as shown here for sodium and
calcium:
 Lewis Symbols

Cations are formed

when atoms lose
electrons, represented
by fewer Lewis dots,
whereas anions are
formed by atoms
gaining electrons. The
total number of
electrons does not
change.
 Writing Lewis Structures with the
Octet Rule
• For very simple molecules and molecular ions,
we can write the Lewis structures by merely
pairing up the unpaired electrons on the
constituent atoms. See these examples:
 Writing Lewis Structures with the
Octet Rule
• For more complicated molecules and
molecular ions, it is helpful to follow the step-
by-step procedure outlined here:
• 1. Determine the total number of valence
(outer shell) electrons. For cations, subtract
one electron for each positive charge. For
anions, add one electron for each negative
charge.
 Writing Lewis Structures with the
Octet Rule
2) Draw a skeleton structure of the molecule or
ion, arranging the atoms around a central atom.
(Generally, the least electronegative element
should be placed in the center.) Connect each
atom to the central atom with a single bond
(one electron pair).
3) Distribute the remaining electrons as lone
pairs on the terminal atoms (except hydrogen),
completing an octet around each atom.
 Writing Lewis Structures with the
Octet Rule
4) Place all remaining electrons on the central
atom.
5) Rearrange the electrons of the outer atoms to
make multiple bonds with the central atom in
order to obtain octets wherever possible.
 Writing Lewis Structures with the Octet Rule

• Let us determine the Lewis structures of SiH4,

CHO2−, NO+, and OF2 as examples in following
this procedure:
• 1. Determine the total number of valence
(outer shell) electrons in the molecule or ion.
For a molecule, we add the number of valence
electrons on each atom in the molecule:
 Writing Lewis Structures with the
Octet Rule
• For a negative ion, such as CHO2−, we add
the number of valence electrons on the atoms
to the number of negative charges on the ion
(one electron is gained for each single
negative charge):
 Writing Lewis Structures with the Octet
Rule
• For a positive ion, such as NO+, we add the
number of valence electrons on the atoms in
the ion and then subtract the number of
positive charges on the ion (one electron is
lost for each single positive charge) from the
total number of valence electrons:
 Writing Lewis Structures with the
Octet Rule
• Since OF2 is a neutral molecule, we simply add
the number of valence electrons:
 Writing Lewis Structures with the
Octet Rule
• Draw a skeleton structure of the molecule or ion, arranging
the atoms around a central atom and connecting each atom
to the central atom with a single (one electron pair) bond.
(Note that we denote ions with brackets
• around the structure, indicating the charge outside the
brackets:)
 Writing Lewis Structures with the Octet
Rule

• Distribute the remaining electrons as lone

pairs on the terminal atoms (except hydrogen)
to complete their valence shells with an octet
of electrons. There are no remaining electrons
on SiH4, so it is unchanged:
 Practice
• NASA’s Cassini-Huygens mission detected a
large cloud of toxic hydrogen cyanide (HCN)
on Titan, one of Saturn’s moons. Titan also
contains ethane (H3CCH3), acetylene (HCCH),
and ammonia (NH3). What are the Lewis
structures of these molecules?
 Writing Lewis Structures: Octet Rule
Violations

• Xenon is a noble gas, but it forms a number of

stable compounds. We examined XeF4 earlier.
What are the Lewis structures of XeF2 and
XeF6? Answers a)

b)
 Formal Charges and Resonance
• In a Lewis structure, formal charges can be assigned to each
atom by treating each bond as if one-half of the electrons are
assigned to each atom. These hypothetical formal charges are
a guide to determining the most appropriate Lewis structure.
A structure in which the formal charges are as close to zero as
possible is preferred.
• Resonance occurs in cases where two or more Lewis
structures with identical arrangements of atoms but different
distributions of electrons can be written.
• The actual distribution of electrons (the resonance hybrid) is
an average of the distribution indicated by the individual
Lewis structures (the resonance forms).
 Formal Charges and Resonance
Examples
• Eg 1)

• Eg 2)
 Strengths of Ionic and Covalent Bonds
• The strength of a covalent bond is measured by its bond
dissociation energy, that is, the amount of energy required to
break that particular bond in a mole of molecules.
• Multiple bonds are stronger than single bonds between the
same atoms. The enthalpy of a reaction can be estimated
based on the energy input required to break bonds and the
energy released when new bonds are formed.
• For ionic bonds, the lattice energy is the energy required to
separate one mole of a compound into its gas phase ions.
Lattice energy increases for ions with higher charges and
shorter distances between ions. Lattice energies are often
calculated using the Born-Haber cycle, a thermochemical
cycle including all of the energetic steps involved in converting
elements into an ionic compound.
 Molecular Structure and Polarity
• VSEPR theory predicts the three-dimensional
arrangement of atoms in a molecule.
• It states that valence electrons will assume an
electron-pair geometry that minimizes repulsions
between areas of high electron density (bonds and/
or lone pairs).
• Molecular structure, which refers only to the
placement of atoms in a molecule and not the
electrons, is equivalent to electron-pair geometry
only when there are no lone electron pairs around
the central atom.
 Molecular Structure and Polarity
• A dipole moment measures a separation of charge.
For one bond, the bond dipole moment is
determined by the difference in electronegativity
between the two atoms.
• For a molecule, the overall dipole moment is
determined by both the individual bond moments
and how these dipoles are arranged in the molecular
structure.
• Polar molecules (those with an appreciable dipole
moment) interact with electric fields, whereas
nonpolar molecules do not.
 VSEPR Theory
• Valence shell electron-pair repulsion theory (VSEPR
theory) enables us to predict the molecular
structure, including approximate bond angles around
a central atom, of a molecule from an examination of
the number of bonds and lone electron pairs in its
Lewis structure.
• VSEPR theory predicts the arrangement of electron
pairs around each central atom and, usually, the
correct arrangement of atoms in a molecule.
 VSEPR Theory
• As a simple example of VSEPR theory, let us
predict the structure of a gaseous BeF2
molecule.

• Two regions of electron density around a central

atom in a molecule form a linear geometry; three
regions form a trigonal planar geometry; four regions
form a tetrahedral geometry; five regions form a
trigonal bipyramidal geometry; and six regions form
an octahedral geometry.
 VSEPR Theory
• The basic
electron-pair
geometries
predicted by
VSEPR theory
maximize the
space around
any region of
electron density
(bonds or lone
pairs).
 VSEPR Theory
• The molecular structures are
identical to the electron-pair
geometries when there are
no lone pairs present (first
column).
• For a particular number of
electron pairs (row), the
molecular structures for one
or more lone
• pairs are determined based
on modifications of the
corresponding electron-pair
geometry.
 Practice
• Predicting Electron-pair Geometry and
Molecular Structure:
• CO2, BCl3, NH4+
• H2O
 Hydrogen bonding and
Metallic Bonding
• Metallic bonding:
• Metallic bonding is the electromagnetic interaction
between delocalized electrons, called conduction
electrons and gathered in an "electron sea", and the
metallic nuclei within metals.
• Understood as the sharing of "free" electrons among a
lattice of positively charged ions (cations).
• Electrons move freely within the molecular orbitals,
and so each electron becomes detached from its
parent atom (electrons are delocalised.
 • The metal is held together by the strong forces of
attraction between the positive nuclei and the
delocalized electrons.
• Not all metals exhibit metallic bonding: one such
example is the mercurous ion (Hg2+2), which
forms covalent metal-metal bonds.

This is sometimes described as "an array of positive ions in a sea

of electrons".
• A hydrogen bond is the attractive interaction of a hydrogen
atom with an electronegative atom, such as nitrogen, oxygen
or fluorine.

• The hydrogen must be covalently bonded to another

electronegative atom to create the bond.

• These bonds can occur between molecules

(intermolecularly), or within different parts of a single
molecule (intramolecularly).
 Molecular geometry
• Molecular geometry or molecular structure is the three-
dimensional arrangement of the atoms that constitute a
molecule.
• It determines several properties of a substance including its
reactivity, polarity, phase of matter, color, magnetism, and
biological activity.
• The molecular geometry can be determined by various
spectroscopic methods and diffraction methods.
• IR, Microwave and Raman spectroscopy can give information
about the molecule geometry from the details of the vibrational
and rotational absorbances detected by these techniques.
• X-ray crystallography, neutron diffraction and electron
diffraction can give molecular structure for crystalline solids
based on the distance between nuclei and concentration of
Gas electron diffraction can be used for small molecules in
the gas phase.
NMR and FRET methods can be used to determine
complementary information including relative distances,
dihedral angles, angles, and connectivity.

Molecular geometries are best determined at low

temperature because at higher temperatures the molecular
structure is averaged over more accessible geometries.

Larger molecules often exist in multiple stable geometries

(conformational isomerism) that are close in energy on the
potential energy surface.
Geometries can also be computed by quantum chemistry
methods to high accuracy.

The molecular geometry can be different as a solid, in

solution, and as a gas.

The position of each atom is determined by the nature of

the chemical bonds by which it is connected to its
neighboring atoms.

The molecular geometry can be described by the positions

of atoms in space, evoking bond lengths of two joined
atoms, bond angles of three connected atoms, and torsion
angles (dihedral angles) of three consecutive bonds.
Molecular Shapes
There are six basic shape types for molecules
Linear: In a linear model, atoms are connected in a
straight line. The bond angles are set at 180°.

A bond angle is very simply the geometric angle between

two adjacent bonds.
For example, carbon dioxide has a linear molecular shape.

Trigonal planar: the trigonal planar shape are somewhat

triangular and in one plane (meaning a flat surface).
Consequently, the bond angles are set at 120°.
An example of this is boron trifluoride (BF3).
Tetrahedral: Tetra- signifies four, and -hedral relates to a
surface, so tetrahedral almost literally means "four surfaces."
This is when there are four bonds all on one central atom,
with no extra unshared electron pairs.
In accordance with the VSEPR (valence-shell electron pair
repulsion theory), the bond angles between the electron bonds
are across = 109.5°.
An example of a tetrahedral molecule is methane (CH4).

Octahedral: Octa- signifies eight, and -hedral relates to a

surface, so octahedral almost literally means "eight surfaces."
The bond angle is 90 degrees.
An example of an octahedral molecule is sulfur hexafluoride
(SF6).
Pyramidal: Pyramidal-shaped molecules have pyramid-like
shapes.
Unlike the linear and trigonal planar shapes but similar to the
tetrahedral orientation, pyramidal shapes requires three
dimensions in order to fully separate the electrons.

Here, there are only three pairs of bonded electrons, leaving

one unshared lone pair.

Lone pair - bond pair repulsions change the angle from the
tetrahedral angle to a slightly lower value.

An example is NH3 (ammonia).

Bent: The final basic shape of a molecule is the non-linear
shape, also known as bent or angular.

One of the most unquestionably important molecules any

chemist studies is water, or H2O.

A water molecule has a non-linear shape because it has two

pairs of bonded electrons and two unshared lone pairs.
Like in the other arrangements, electrons must be spaced as
far as possible.
Lone pair - bond pair repulsions push the angle from the
tetrahedral angle down to around 106°.
Valence shell electron pair repulsion (VSEPR) theory is a
model in chemistry used to predict the shape of individual
molecules based upon the extent of electron-pair electrostatic
repulsion.
It is also named Gillespie-Nyholm theory after its two main
developers.
The acronym "VSEPR" is sometimes pronounced "vesper" for
ease of pronunciation.
The premise of VSEPR is that the valence electron pairs
surrounding an atom mutually repel each other, and will therefore
adopt an arrangement that minimizes this repulsion, thus
determining the molecular geometry.

The number of electron pairs surrounding an atom, both bonding

and nonbonding, is called its steric number.
The "AXE method" of electron counting is commonly used
when applying the VSEPR theory.
The A represents the central atom and always has an implied
subscript one.

The X represents the number of sigma bonds between the central

atoms and outside atoms. Multiple covalent bonds (double,
triple, etc) count as one X.

The E represents the number of lone electron pairs surrounding

the central atom.
The sum of X and E, known as the steric number, is also
associated with the total number of hybridized orbitals used by
valence bond theory.
Based on the steric number and distribution of X's and E's,
VSEPR theory makes the predictions of the geometry of the
molecules.

Note that the geometries are named according to the atomic

positions only and not the electron arrangement.

example the description of AX2E1 as bent means that AX2 is

a bent molecule without reference to the lone pair, although
the lone pair helps to determine the geometry.
Exceptions
There are groups of compounds where VSEPR fails to
predict the correct geometry.
Many transition metal compounds do not have
geometries explained by VSEPR which can be
ascribed to there being no lone pairs in the valence
shell and the interaction of core d electrons with the
ligands.

The structure of some of these compounds, including

metal hydrides and alkyl complexes such as
hexamethyltungsten, can be predicted correctly using the
VALBOND theory (VBT), which is based on sd hybrid
orbitals and the 3-center-4-electron bonding model.
Crystal field theory is another theory that can often
predict the geometry of coordination complexes.
Exceptions
There are groups of compounds where VSEPR fails to
predict the correct geometry.
Many transition metal compounds do not have
geometries explained by VSEPR which can be
ascribed to there being no lone pairs in the valence
shell and the interaction of core d electrons with the
ligands.

The structure of some of these compounds, including

metal hydrides and alkyl complexes such as
hexamethyltungsten, can be predicted correctly using the
VALBOND theory (VBT), which is based on sd hybrid
orbitals and the 3-center-4-electron bonding model.
Crystal field theory is another theory that can often
predict the geometry of coordination complexes.
VSEPR Table:

The bond angles in the table below are ideal angles from
the simple VSEPR theory, followed by the actual angle for
the example given in the following column where this
differs.

For many cases, such as trigonal pyramidal and bent, the

actual angle for the example differs from the ideal angle,
but all examples differ by different amounts.

For example, the angle in H2S (92°) differs from the

tetrahedral angle by much more than the angle for H2O
(104.5°) does.
Hybridization and Molecular geometry

Hybridization is the combining of two or more orbitals of

nearly equal energy within the same atom into orbitals of equal
energy.

The concept of orbital hybridization focuses on mixing atomic

orbitals to form new hybrid orbitals.

The obtained hybrid orbitals have different energies, shapes,

etc., than the component atomic orbitals.

Hybrid orbitals are very useful in the explanation of molecular

geometry and atomic bonding properties.
 sp3, sp2 and sp hybridization in
carbon
• Carbon ground state configuration
• The carbon atom has six electron, thus it
electronic configuration is 1s22s22p2
• The diagram bellow shows the expected orbital
notation of carbon in its ground state
sp3 hybridization of carbon
(C) in CH4
• Overlapping and bond formation in CH4
Geometry: Tetrahedral

translates into
 sp2 hybridization in carbon
(covalent bonding - double bonds)
Overlapping and bond formation in C2H4
Geometry: Planar
Ex: formation of ethene is CH2=CH2 (C2H4).

In ethene, each carbon atom is sp2-hybridized.

In this way six sp2-orbitals are generated (three for each
carbon). One sp2-orbital of each carbon atom by overlapping
forms a sigma bond between carbon atoms.

Remaining two sp2-orbital of each atom overlap with 1s-

orbital of hydrogen atom to produce four sigma bonds.
pz un-hybrid orbital of each carbon atom by the parallel
overlapping form a pi-bond between two carbon atoms.

Geometry in ethene molecule is trigonal in which bond

angles are120o.
sp2 diagram
 Sp hybrid orbitals
•The total of two orbitals is formed (sp) : 2s mixes with
2p orbital, with two remaining unchanged p-orbitals.
•This is the type of hybridization of carbon in ethyne (
C2H2).
•The chemical bonding in ethyne consists of sp-sp
overlap between the two carbon atoms forming a σ
bond and two additional π bonds formed by p-p
overlap.
•Each carbon also bonds to hydrogen in sigma s-sp
overlap at 1800 angles.
• Overlapping and bond formation in C2H2
Geometry: Linear

0
180
H C C H
0
180
sp diagram
 Discussion: Tetracyanoethylene has the skeleton
shown below

• How many sigma and pi

From its Lewis structure determine
the following:
bonds are in the
molecule?

• How many of the atoms

are sp2 hybridized?

• How many of the atoms

are sp hybridized?
 Lecture 5
Representative metals, metalloids
and nonmetals
 Assignment
• A series of six elements called the metalloids separate
the metals from the nonmetals in the periodic table.
The metalloids are boron, silicon, germanium, arsenic,
antimony, and tellurium. These elements look metallic;
however, they do not conduct electricity as well as
metals so they are semiconductors.
Question: Describe the general preparation, properties,
compounds, toxicity and uses of the mentioned
metalloids.
Note: Do not exceed 10 slides