CHM 102

PROF. O.F. ADEKUNLE

 COURSE OUTLINE
 HYBRIDIZATION AND SHAPES OF SIMPLE
MOLECULES
EXTRACTION OF METALS
COMPARATIVE CHEMISTRY OF GROUP IA, IIA
AND IVA ELEMENTS
 OBJECTIVES
 To understand hybridization and the different
types that exist
To determine the geometries/shapes of
simple molecules
Understanding the methods of extraction of
metals
Identify similarities and differences in Groups
IA, IIA and IVA elements
 HYBRIDIZATION
 Definition: The phenomenon of mixingup of atomic orbitals of similar
energies and formation of equivalent number of entirely new orbitals of
identical shape and energy is known as "hybridization" and the new orbitals
so formed are called " hybrid orbitals".

 The hybridization of atomic orbitals takes place either by reshuffling of all

or some of the atomic orbitals in the excited state.
 The hybrid orbitals have same shape, size and energy i.e they are
equivalent to each other.
 The number of hybrid orbitals is equal to the number of reshuffled pure
atomic orbitals.
 The shape, size, orientation and energy content of the hybrid orbitals are
different from the pure atomic orbitals.
 The labels given to hybrid orbitals reflect the contributing atomic orbitals.
For example, an sp hybrid orbital possess equal amounts of s and p orbital
character.
TYPES OF HYBRIDIZATION
HYBRIDIZATION
HYBRIDIZATION
HYBRIDIZATION
HYBRIDIZATION
HYBRIDIZATION
 HYBRIDIZATION
(4) sp3d- hybridization: The combination of one s,
three p and ond d- orbitals to form five hybrid
orbitals of equal energy is known as sp3d -
hybridization.
Example: PCl5 molecule.
3s 3p 3d
15P (Ground state) =
HYBRIDIZATION
 HYBRIDIZATION
(5) sp3d2 - hybridization : The combination of
one s, and three p and two d-orbitals to form
six hybrid orbitals of equal energy is as sp3d2 -
hybridization.
Example: SF6 molecule.
 HYBRIDIZATION
16S (Excited state)

Note: the longer arrow is from F.

 VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR)
THEORY

Definition: The valence Shell Electron Pair

Repulsion Theory (VSEPR), proposes that the
stereochemistry of an atom in a molecule is
determined primarily by the repulsive
interactions among all the electron pairs in its
valence shell.
The main postulates of this theory are:
 VSEPR THEORY

 The shape of the molecule is determined by repulsion

between all of the electron pairs present in the valence
shell.
 A lone pair of electrons takes up more space round the
central atom than a bond pair, this is due to the fact that
lone pair is attracted to one nucleus while the bond pair is
shared by two nuclei. It follows that repulsion between two
lone pairs is greater than the repulsion between a lone pair
and a bond pair , which in turn is greater than the repulsion
between two bond pairs. The repulsive interactions
decrease in the order: LP - LP > LP - BP > BP - BP
 The magnitude of repulsion between bonding pairs of
electrons, depends on the electronegativity difference
between the central metal and the other atoms
 VSEPR THEORY
 Double bonds cause more repulsion than
single bonds and triple bonds cause more
repulsion than a double bond. Repulsive
forces decrease sharply with increasing bond
angle between the electron pairs.
VSEPR THEORY
VSEPR THEORY
VSEPR THEORY
VSEPR THEORY
VSEPR THEORY
 VSEPR THEORY
Important points on hybridization:
The hybridization of C, O or N atom can be
determined by the number of pi bonds it
forms. If it forms no pi bonds, it is sp3
hybridized; if it forms one pi bond, it is sp2
hybridized and; if it forms two pi bonds, it is sp
hybridized.
The hybridization of C, O or N is sp (2 number
of pi bonds)
VSEPR THEORY
VSEPR THEORY
 CHM 102

DR TUNMISE EUGENE-OSOIKHIA
 COURSE OUTLINES

* ELECTRONIC CONFIGURATION

* PERODICITY

* BUILDING UP OF THE PERIODIC TABLE

 OBJECTIVES

At the end of the course the following objectives

must be realised
Students should be able to describe atomic structure
Students should be able to write electronic
configurations of elements in the periodic table
Students should know history of the periodic table
Properties and relationship of elements in the
periodic table
 Refresher on Atom

Matter is anything that takes up

space and has mass.

All matter is made of atoms.

Atoms are the building blocks of

matter, sort of how bricks are the
building blocks of houses
An Atom
 Dalton’s Atomic Theory (1808)
*1. Each element is made of tiny indivisible particles called atoms
that cannot be created nor destroyed (law of conservation of matter).

*2. Atoms of an element cannot be converted to atoms of another

element. In chemical reactions, atoms re-combine to form different
substances (change the way they are bound to each other).

*3. The atoms of a given element are identical, and different from
those of any other element.

*4. Atoms of one element can combine with atoms of other elements
to form compounds. A given compound always has the same relative
numbers and types of atoms.
Earnest Rutherford conclusion about atom (1911-1919)
• An atom is mostly empty space that is occupied by electrons.

• Atom has a tiny, dense center of positive charge:nucleus.

• The nucleus contains particles called protons, which have

charge of same magnitude as electrons but are positive.

• Most nuclei also contain a neutral particle: neutron. (with

Chadwick, 1932)
An atom has three parts:
Proton = positive
Neutron = no charge
Electron = negative

The proton & neutron are found in the

center of the atom, a place called the
nucleus.

The electrons orbit the nucleus.

Elements are made of atoms. While the

atoms may have different weights and electron
organization, they are all built in the
same way.
Particles Symbol Mass Charge Discovered By
–1e or β 9.1096 × 10–31 kg –1.602 × 10–19
Electron 0 J.J. Thompson
0.000548 amu Coulombs Stoney Lorentz
–4.803 × 10–10 1887
esu
Proton 1H1 1.6726 × 10–27 kg +1.602 × 10–19 Goldstein
1.00757 amu Coulombs Rutherford 1907
+ 4.803 × 10–10
esu
Neutron 0n
1 1.6749 × 10–27 kg Neutral James Chadwick
1.00893 amu 0 1932
1 amu ≈ 1.66 ×
10–27 kg

Mass Symbols for Atoms (Isotope Symbols)

Z
number
A X Element Symbol
Z = No of (protons +neutrons)
Atomic
number A= No of protons
 Where are Electrons?

•Electrons exist in different energy levels or

shells

The farther away an energy level is from the

nucleus, the more energy the sublevel has.
 Where are Electrons?

*Orbitals are areas within shells where the electrons are located
–These orbitals may have different shapes orbitals(represented
by the letters s, p, d, and f)

–There may be different numbers of orbitals within a shell

* A number can be placed in front of the orbital letter to

represent the energy level that an orbital belongs to
 Orbitals, con’td

Different shaped orbitals can hold different numbers

of electrons:

s orbital can hold up to 2electrons (1 pair)

p orbital can hold up to 6electrons (3 pairs)

d orbitals can hold up to 10electrons (5 pairs)

f orbitals can hold up to 14electrons

 s Orbitals

• Spherical in shape.
• Radius of sphere increases
with increasing value of n.
 p Orbitals

Note: always 3 p orbitals for a given n

 d Orbitals

• Four of the five orbitals have 4 lobes; the other resembles a p orbital
with a doughnut around the center.
 f orbitals

f has seven suborbitals

Where are the electrons? Every electrons has a home.

Sublevels No of orbitals No of electrons

S 1 2

P 3 6

D 5 10

F 7 14
 Orbital Energies

Another way to look at it….

The boxes represent the different orbitals. As

the number of the level increases, the energy
increases. Each individual box can hold
2electrons at a time.
 ORBITAL ENERGIES
The energy of atomic orbitals increases as the principal
quantum number, n, increases. The closer to the nucleus,
the lower the energy
For a given energy level
(n):
• s<p<d<f
• s lowest energy, where
electrons go first
• Next p
• Then d
Why?
For a one-electron hydrogen atom,
orbitals on the same energy level have
the same energy. • That is, they are
degenerate.
Orbital Energies
• As the number of electrons increases,
though, so does the repulsion between them.
• Therefore, in many electron atoms, orbitals
on the same energy level are no longer
degenerate.

Making sense of the order

 Orbital Energies

Filling order of electron subshells

1s2, 2s2,2p6, 3s2, 3p6,4s2,3d10, 4p6,5s2,4d10, 5p6, 6s2,4f14,5d10,

6p6,7s2,5f14,6d10, 7p6
 Rules for constructing orbital diagrams
The orbital diagram or orbital notation simply represents the
arrangement of electrons in different orbitals of an atom.

In an orbital diagram, an electron is represented by an arrow,

while a box represents an atomic orbital.
 Filling of electrons in orbitals
There are three different rules used for constructing an atomic orbital
diagram.
The Aufbau Principle: The electrons fill the available orbitals from lowest energy
to highest energy. In the ground state all the electrons are
in the lowest possible energy level.
That is electrons occupy
atomic orbitals in an
ascending energy order
 Filling of electrons in orbitals
Hunds rule of maximum multiplicity:
The electrons must be placed into the orbitals in such a way that
no pairs are put together unless absolutely necessary. That is,
single electrons must be placed into boxes first and then paired
up if necessary

“For degenerate orbitals, the

lowest energy is attained when
the number of electrons with
the same spin is maximized.”
Filling of electrons in orbitals
Pauli’s Exclusion Principle
It states that no two electrons have identical sets of
the four quantum numbers (n, l, m and s) in an atom.

*No two electrons in the same atom can have exactly the
same energy.

• For example, no two

electrons in the same atom
can have identical sets of
quantum numbers.
 Filling of electrons in orbitals
Example 1: Draw the orbital
Example 2: Draw the orbital diagram for nitrogen
diagram for chlorine
Solution
 Filling of electrons in orbitals

Exercise
Give the orbital diagrams of the following: Be, K, Ti and Fe(II)
 Electronic Configuration
In the atom, electrons and the nucleus interact to make the most stable
arrangement possible.
The ways that electrons are arranged around the nucleus of an atom is
called the electron configuration
The electron configuration is similar to an “address” for each electron in an
atom.

Example 1, the electron configuration for Helium is:

1s2
1 = the energy level
s = the sublevel
2 = the number of electrons
Electronic Configuration
 Electronic Configuration
Example 2: Write the electron configuration for Oxygen
Solution: 1s2,2s2, 2p4
When you write electron configurations for elements in the D sublevel
section, the energy level is one number less than the period the
element is in.
Example 3: Write the electron configuration for Iron (Fe)
Solution: 1s2,2s2, 2p6,3s2,3p6,4s2, 3d6
Exercise
Write the electronic configurations of the following elements:
Neon, Scadium, Fluorine,

Which element has the following configuration: [Xe] 6s2

 Electron Configurations and Valence Electrons
The outermost shell of electrons in an atom is the valence shell and it
contains the valence electrons.
The outermost shell contains the electrons that can interact most with the rest
of the world.
A full valence shell contains 8 electrons (2 from an s orbital and 6 from a p
orbital), unless you’re hydrogen or helium(only want 2 to fill their outermost s
shell to become stable).
More Practice
How many valence electrons in….
Oxygen -1s2,2s2, 2p4
Sulfur -1s2,2s2, 2p6,3s2,3p4
Thallium, Xenon and Rubidium
 Periodicity/ Building up of the Periodic Table
During the 1800s, when most of the elements were being discovered, many
chemists tried to classify the elements according to their similarities.

In 1829, Johann Dobringer noted chemical

similarities in several groups of three elements
and placed these elements into what he called
triads

Johann groupings included the triads of (1)

chlorine, bromine, and iodine; (2) sulfur,
selenium, and tellurium; (3) calcium, strontium,
and barium; and (4) lithium, sodium, and
potassium.
 Periodicity/ Building up of the Periodic Table
In 1864, John Newlands saw a connection between the chemical
properties of elements and their atomic masses.

He stated that if the known elements, beginning with lithium,

are arranged in order of increasing mass, the eighth element
will have properties similar to the first element, the ninth
similar to the second, the tenth similar to the third,and so on.
Newlands called his relationship the law of octaves,

Newland compared the

elements to the notes in a
musical scale
Newlands tried to force all the known elements
to fit into his octaves, but many of the heavier
elements, did not fit into his patterns.
 Periodicity/ Building up of the Periodic Table
In 1869, Dmitri Mendeleev, unaware of Newlands’s work, also
developed a table of the elements that showed a relationship
between the chemical properties of elements and their atomic
masses.
Mendeleev avoided Newlands’s mistake of trying to force
elements into groups where their chemistry did not match.
Instead, he left empty spaces in his table for where no known
element fit the properties and atomic mass for that space.
He assumed that elements discovered in the future would fit in
those spots.
Dmitri Mendeleev
Mendeleev’s table listed the elements in order of increasing atomic
mass and grouped elements with similar chemical behavior together.
 Periodicity/ Building up of the Periodic Table
Mendeleev
–Grouped elements (66) according to properties
–Predicted properties for elements not yet discovered
–Though a good model, Mendeleev could not explain inconsistencies,
for instance, all elements were not in order according to atomic mass
The periodic table in its present form was organized by
Dmitri Mendeleev. The basis was the chemical behavior
of the elements.
In 1913 -Henry Moseley explained the discrepancy

–Discovered correlation between number of protons

(atomic number) and frequency of X rays generated

–Today, elements are arranged in order of increasing

atomic number
Henry Moseley
Modern day Periodic Table
 Modern day Periodic Table
Classification of elements
* When Mendeleev created his periodic table, he did not know why certain
elements had similar chemistry.

*Mendeleev placed the elements in their positions because they exhibited similar
chemical behaviors
*Thus, vertical columns in Mendeleev’s table were composed of elements with
similar chemistry.
*These vertical columns are
called GROUPS, OR
FAMILIES.
 Modern day Periodic Table
Classification of elements
Elements in the same groups are Example 1 Example 2- Halogen
related to each other by their
electronic configurations

On the periodic table, a number written above each group (column). These
numbers serve as a labels.
Groups are often referred to by their labels.
 Modern day Periodic Table
Classification of elements
*Two different numbering sysetms referring to families/ groups can be seen
on the periodic table

*In the older system, the numbers 1 – 8 and the letters A and B were used to
label the groups. The newer convention label each group from 1 – 18 in
sequential order.

*The older labeling scheme helps to provide more insight into the electronic
configurations of each group.

–Main group elements -“representative elements” Group 1A-7A

–Noble gases -Group 8A all have ns2np6 (except He)
–Transition elements -1B, 3B -8B “d-block”
–Lanthanides/actinides -“f-block”
 Modern day Periodic Table

Lanthanides
Actinides
 Modern day Periodic Table
Classification of elements

Group 1A are:
Lithium = 1s22s1 or [He]2s1
Sodium = 1s22s22p63s1 or [Ne]3s1
Potassium = 1s22s22p63s23p64s1 or [Ar]4s1
Rubidium = 1s22s22p63s23p64s23d104p65s1 or [Kr]5s1
Cesium =1s22s22p63s23p64s23d104p65s24d105p66s1 or [Xe]6s1
Francium =1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p67s1 or [Rn]7s1
Properties:
Group 1A are also called ALKALI METALS *Low Ionization Energy
Group 1A metals •Never found in nature in
have similar electron All of the Group1A elemental state
configurations which elements have one •React with oxygen to form
causes them to have valence electron metal oxides
similar chemistry •Peroxides and
superoxides with some
LiNa
 Modern day Periodic Table
Classification of elements
Group 2A/ THE ALIKALI EARTH METALS
Beryllium = [He],2s2 Properties
Magnesium = [Ne],3s2 •Less reactive than 1A
Calcium = [Ar],4s2 •Some react with water to
Strontium = [Kr],5s2 produce H2
Barium = [Xe],6s2 •Some react with acid to
Radium = [Rn] 7s2 produce H2
All of the elements in this family have two valence electrons and have very
similar chemistry. This group of metals is called the alkali earth metals
As with the 1A family, the elements in this family also increase in reactivity as
the elements become larger and the valence electrons are held more loosely.
 Modern day Periodic Table
Classification of elements
Group 3A
Boron = [He]2s22p1 All the members of
this family have three
Aluminum = [Ne]3s23p1
2 10 1
valence electrons
Gallium = [Ar]4s 3d 4p
Indium = [Kr]5s24d105p1
Thallium =[Xe]6s2 4f145d106p1
The chemical behaviors of the elements in this family are similar to each other,
but they are not as consistent from element to element as they are for other
families of elements Properties
*Metalloid (Boron) and metals (all others)
•Al forms Al2O3with oxygen
•Al forms +3 ions in acid
•Other metals form +1 and +3
B
 Modern day Periodic Table
Classification of elements

Group 4A
Carbon = [He]2s22p2
Silicon = [Ne]3s23p2
Germanium = [Ar]4s23d104p2
Tin = [Kr]5s24d105p2
Lead = [Xe]6s24f145d106p2
Group 4A (also known as Group 14)
members have four valence electrons.
Properties
Show considerable variation among Nonmetal (C) metalloids (Si, Ge)
properties from metallic to non-metallic and other metals
•Form +2 and +4 oxidation states
•Sn, Pb react with acid to produce
H2
 Modern day Periodic Table
Classification of elements
Group 5A
Group 5A (also known as Group 15) members have
five valence electrons.
Properties
Non-metal (N2, P) metalloid
(As,Sb) and metal (Bi)
•Nitrogen, N2 forms variety of oxides
•Phosphorus, P4
•As, Sb, Bi (crystalline)
•HNO3and H3PO4 important industrially
N2

Show considerable variation among properties from metallic to non-metallic

 Modern day Periodic Table
Classification of elements
Group 6A/ Oxygen family
Group 6A (also known
as Group 16)
members have six Se
valence electrons.
Properties
•Nonmetals (O, S, Se)
•Metalloids (Te, Se)), metal (Po)
•Oxygen, O2
•Sulfur,S8
•Selenium, Se8
•Te, Po (crystalline)
S •SO2, SO3, H2S, H2SO4
SeS
 Modern day Periodic Table
Classification of elements
Group 7A/ Halogen family
Group 7A (also
known as Group 17)
members have seven
valence electrons.

Properties
*They are non -metals
*All diatomic
•Do not exist in elemental form in nature
•Form ionic “salts”
•Form molecular compounds with each
other eg I2 , Br2
 Modern day Periodic Table
Classification of elements
Group 8A/ Inert or noble family

Group 8A (also known

as Group 18)
members have eight
valence electrons.

Properties
•All monatomic
•Filled valence shells
They are inert and •Considered “inert” until 1963
thus chemically when Xe and Kr were used to
stable form compounds
•No major commercial use
 Modern day Periodic Table
Classification of elements
Group 1B, 2B-8B/ Transition metals (d- block elements

Transition elements have their d orbitals

being fiiled
Transition metals exhibit variable oxidation
states

Transition metals form coloured

compounds
 Modern day Periodic Table
Classification of elements
Group F/ Lanthanides and Actinides

The Lanthanides elements have their 4f

orbitals being fiiled while the Actinides
have their 5f orbitals being filled

Lanthanides
Actinides
 Periodic Variations in Element Properties
Trends across the periodic table
The Periodicity of Atomic radius:

Atomic radius: distance between nucleus of

an atom and its valence shell
•Metallic radius: half the distance between
nuclei of two adjacent, identical metal atoms

Covalent radius: half

the distance between
adjacent, identical nuclei
in a molecule that are
joined together by
covalent bond
Covalent radius
 Periodic Variations in Element Properties
Trends across the periodic table
The Periodicity of Atomic radius:

*The metallic radius in a metal is half the distance between nuclei of two
atoms in contact in a crystalline solid metal.

*An ionic radius is derived from the distance between nuclei of a cation and
anion pair in an ionic bond.

Values of Atomic radii are obtained from measurements of distances

between the nuclei of atoms in the chemical bonds of molecular substances.

distance between nuclei is determined experimentally by X-ray

crystallography
Periodic Variations in Element Properties
Trends across the periodic table
The Periodicity of Atomic radius:
Examples
Periodic Variations in Element Properties
Trends across the periodic table
The Periodicity of Atomic radii:
Across a period, the effect of shielding decreases
which allows the valence electron to be held tighter.

Thus, atomic radius of atoms decreases going from

left-to right across a period.

Atomic radius increases down a group. Each step

down involves adding a new shell, which increases
size
 Periodic Variations in Element Properties
Variation in Covalent Radius
*As we move down a group, the principal quantum number, n, increases
by one for each element.

*The electrons are being added to a region of space that is increasingly

distant from the nucleus. Consequently, the size of the atom (and its covalent
radius) must increase as the distance of the outermost electrons from the
nucleus increases.
Thus, covalent radius increases down the group and also decreases across the
period as atomic radius
 Periodic Variations in Element Properties
Variation in Covalent Radius/Atomic radius
-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.
-It
implies that atoms with more electrons across the period have a smaller atomic
radius/covalent radius. This is due to the effective nuclear charge, Zeff.
Effective nuclear charge, Zeff 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. For all other atoms, the inner
electrons partially shield the outer electrons from the pull of the nucleus.
Periodic Variations in Element Properties
Effective nuclear charge

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–electron repulsions the electron of
interest encounters

Shielding reduces the charge Z that the

valence electrons feel to Zeff, which is called
the effective nuclear charge
 Periodic Variations in Element Properties
Effective nuclear charge
The innermost electrons (core) screen or “shield” the nucleus from the view of
the outer (valence) electrons.
Electrons in the same valence shell do not block the nuclear attraction experienced
by each other as efficiently
As 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 (Z) experienced by electrons
on the right side of the periodic table draws the electrons closer to the nucleus,
making the Atomic/covalent radii smaller.
 Periodic Variations in Element Properties
Effective nuclear charge

Note: The valence electrons are easiest to remove because they have the
highest energies, are shielded more, and are farthest from the nucleus
The valence electrons in effect see a
charge (Zeff) that is less that the actual
charge on the nucleus, Z.

The interaction of the electrons reduces the

attractive forces between the nucleus and
the electrons. The extent of this effect is a
function of the screening ability of the core
electrons:
 Periodic Variations in Element Properties
Effective nuclear charge
The trend is:
s-electrons > d-electrons > p-electrons This indicates that Zeff
increases from left-to-right
Increasing Screening ability across a period.

Zeff increases As one moves

down a group,
Zeff decreases as
Zeff decreases screening
increases
 Periodic Variations in Element Properties
Effective nuclear charge
This explains the trend in atomic radius/covalent radius: Across, as Zeff
gets larger, the valence electrons are held more tightly. Down a group, the
reverse is seen.

Sorting Atomic Radii

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.
 Periodic Variations in Element Properties
Variation in ionic radius
The radii of cations are smaller than radii of the corresponding neutral
atoms. (same Z, less electrons)
The radii of anions are larger than radii of the corresponding neutral
atoms. (same Z, more electrons)
Ionic radius is the measure
used to describe the size of an
ion
 Periodic Variations in Element Properties
Variation in ionic radius

As electrons are removed from the outer valence shell, the remaining core
electrons occupying smaller shells experience a greater effective nuclear
charge Zeff are drawn even closer to the nucleus.

Example

Cations with larger charges are smaller than cations with smaller
charges (e.g., V2+ has an ionic radius of 79 pm, while
that of V3+ is 64 pm).
 Periodic Variations in Element Properties
Variation in ionic radius

An anion (negative ion) is formed by the addition of one or more electrons to

the valence shell of an atom. This results in a greater repulsion among the
electrons and a decrease in Zeff per electron. Both effects (the increased
number of electrons and the decreased Zeff) cause the radius of an anion to be
larger than that of the parent atom
Atoms and ions that have the same electron configuration are said to be
isoelectronic.

Examples of isoelectronic species are N3–, O2–, F–, Ne, Na+, Mg2+, and Al3+
(1s22s22p6). Another isoelectronic series is P3–, S2–, Cl–, Ar, K+, Ca2+, and Sc3+
([Ne]3s23p6). For atoms or ions that are isoelectronic, the number of protons
determines the size. The greater the nuclear charge, the smaller the radius
in a series of isoelectronic ions and atoms.
 Periodic Variations in Element Properties
Variation in ionic radius
Rank the following ions in order of decreasing size?
Na+, N3-, Mg2+, F- and O2-
Ion No of protons #No of electrons ne/np
Na+ 11 10 0.909
N3- 7 10 1.43
Mg2+ 12 10 0.833
F- 9 10 1.11
O2- 8 10 1.25
· Notice that they all have 10 electrons: They are isoelectronic
(same electron configuration) as Ne.
· Since N3- has the highest ratio of electrons to protons, it must be
the largest.
· Mg2+ must then be the smallest.
N3- > O2- > F- > Na+ > Mg2+
 Periodic Variations in Element Properties
Variation in ionization energies

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:

The energy required to remove the second most loosely bound electron is
called the second ionization energy (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
 Periodic Variations in Element Properties
Variation in ionization energies

For larger atoms, the most loosely bound electron is located farther from the
nucleus and so is easier to remove.

Within a period, the IE1 generally increases with increasing Z. Down a group,
the IE1 value generally decreases with increasing Z.

Within any one shell, the s electrons are lower in energy than the p electrons.
This means that an s electron is harder to remove from an atom than a p
electron in the same shell. The electron removed during the ionization of
beryllium ([He]2s2) is an s electron, whereas the electron removed during the
ionization of boron ([He]2s22p1) is a p electron; this results in a lower first
ionization energy for boron, even though its nuclear charge is greater by one
proton.
 Periodic Variations in Element Properties
Variation in ionization energies

IE1 increases from left to right across a period due to increasing

Zeff
IE1decreases down a column of the periodic table because the distance
of the electron from the nucleus increases as n increases
 Periodic Variations in Element Properties
Variation in ionization energies

What do you notice about the

1st IE between 2A and 3A?
Why? (hint: draw the electron
configuration)

What do you notice about the 1st

IE between 5A and 6A? Why?
(hint: draw the electron
configuration

Grp 5A: Have- filled Grp 6A: Disruption of

stable p configuration configuration by extra one
electron
 Periodic Variations in Element Properties
Variation in ionization energies
Multiple Ionizations: it takes more energy to remove the
2nd, 3rd, 4th, etc. electron and much more energy to remove
core electrons.

•Why?
–Core electrons are closer to nucleus
–Core electrons experience greater Zeff

Removing an electron from a cation is more difficult than removing an

electron from a neutral atom because of the greater electrostatic attraction
to the cation
Periodic Variations in Element Properties
Variation in ionization energies
Periodic Variations in Element Properties
Variation in ionization energies
 Periodic Variations in Element Properties
Variation in ionization energies
What do you notice about the 1st IE (Ionization Energy) across a period?
Why? (hint: Zeff)
Solution : IE1 increases from left to right across a period due to increasing
Zeff.

What do you notice about the 1st IE down a column? Why? (hint: n)

Solution: IE1 decreases down a column of the periodic table because

the distance of the electron from the nucleus increases as n increases
 Periodic Variations in Element Properties
Variation in ionization energies

Ranking Ionization Energies

Predict the order of increasing energy for the following processes: IE1 for
Al, IE1 for Tl, IE2 for Na, IE3 for Al.
Solution
Removing the 6p1 electron from Tl is easier than removing the 3p1
electron from Al because the higher n orbital is farther from the nucleus,
so IE1(Tl) < IE1(Al). Ionizing the third electron from
Al (Al2+ ⟶ Al3+ + e−) requires more energy because the cation Al2+
exerts a stronger pull on the electron than the neutral Al atom, so IE1(Al)
< IE3(Al). The second ionization energy for sodium removes a core
electron, which is a much higher energy process than removing valence
electrons. Putting this all together, we obtain: IE1(Tl) < IE1(Al) < IE3(Al) <
IE2(Na).
 Periodic Variations in Element Properties
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)
OR energy released when an atom in the gas phase accepts an
electron
Representation:
Cl(g) + e- Cl-(g)
This process can be either EA for this equation =
endothermic or exothermic, depending 349.0 kJ/mol energy
on the element released (∆H= negative

Elements that have negative values of EA, which means that

energy is released when the gaseous atom accepts an electron.

For some elements, energy is required for the atom

to become negatively charged and the value of their EA is
positive
Periodic Variations in Element Properties
Variation in Electron Affinity
 Periodic Variations in Element Properties
Variation in Electron Affinity
Just as with ionization energy, subsequent EA values are associated with
forming ions with more charge. The second EA is the energy associated
with adding an electron to an anion to form a –2 ion, and so on.

It becomes easier to add an electron across a series of atoms as the

effective nuclear charge of the atoms increases. As we go from left to right
across a period, EAs tend to become more negative

Trends in Electron
Affinity
 Periodic Variations in Element Properties
Variation in Electron Affinity
Periodic Interruptions in EA

As we go from left to right across a period, EAs tend to become more negative.
exceptions is found in elements of group (2A), group (5A), and group (8A)

Group 2 (2A) has a filled

ns subshell, and so the
next electron added goes
into the higher energy np,
so, the observed EA value
is not as the trend would
predict.
Periodic Variations in Element Properties
Variation in Electron Affinity
Periodic Interruptions in EA

Group 15 (5A) has a half-filled np

subshell and the next electron
must be paired with an existing np
electron.
 Periodic Variations in Element Properties
Variation in Electron Affinity
Periodic Interruptions in EA
The noble gases, group 18 (8A), have a completely filled shell and the
incoming electron must be added to a higher n level, which is more difficult
to do.

In all of these cases, the initial relative stability of the electron configuration
disrupts the trend in EA.
 Periodic Variations in Element Properties
Variation in Electron Affinity
Trends in EA down the group

It is expected that the atom at the top of each group should have the largest
EA because their first ionization potentials suggest that these atoms have the
largest effective nuclear charges
As we move down a group, the second element in the group most often has
the greatest EA. The reduction of the EA of the first member can be attributed
to the small size of the n = 2 shell and the resulting large electron–electron
repulsions
The EA of fluorine is –322 kJ/mol. When we
add an electron to a fluorine atom to form a
fluoride anion (F–), we add an electron to
the n = 2 shell. The electron is attracted to
the nucleus, but there is also significant
repulsion from the other electrons already
present in this small valence shell.
 Periodic Variations in Element Properties
Variation in Electron Affinity
Trends in EA down the group
Also, chlorine, with an EA value of –348 kJ/mol, has the highest value of any
element in the periodic table.

Chlorine atom has the same electron configuration in the valence shell, but
because the entering electron is going into the n = 3 shell, it occupies a
considerably larger region of space and the electron–electron repulsions are
reduced. The entering electron does not experience as much repulsion and the
chlorine atom accepts an additional electron more readily
Fluorine has an energetically favorable EA and a large energy barrier to
ionization (IE), it is much easier to form fluorine anions than cations
Read and Practise

Thank you for listening

COMPARATIVE CHEMISTRY OF GROUP IA,
IIA AND IVA ELEMENTS
PERIODIC TABLE OF ELEMENTS
 Concepts

Periodic table, Reactivity, Ionization

energy
Groups IA, IIA, and IVA in the periodic
table show different trends in reactivity
and ionization energy due to their
distinct electronic configurations.
 Group IA

Group IA (Alkali Metals): the elements in this

group comprises of Lithium
(Li), sodium (Na), Potassium (K), Rubidium (Rb),
Caesium (Cs) and Francium (Fr) . These elements
have one electron in their outermost shell (ns1).
They are highly reactive, especially with water,
and their reactivity increases down the group.
The ionization energy is low because it is easy to
remove the single outer electron.
 ELECTRONIC CONFIGURATION
Na - 1s22s22p63s1(2, 8, 1)
K - 1s22s22p63s23p64s1(2, 8, 8, 1)
Rb – [Kr] 5s1(2, 8, 18, 8, 1)
Cs– [Xe] 6s1(2, 8, 18, 18, 8, 1)
Fr – [Rn] 7s1(2, 8, 18, 32, 18, 8, 1)
 PROPERTIES

 Group IA elements react with non-metals such as oxygen,

halogens, nitrogen, hydrogen and sulphur to give oxides
(regular oxides, peroxides and superoxides), halides,
nitrides, hydrides, and sulphide respectively. However there
is an exception with nitrogen, lithium alone in the group
react directly with nitrogen to form trilithium nitrides
(Li3N), others do not react with nitrogen at all.
Due to their highly reactive nature, they are stored in an
airtight container, under liquid paraffin, inert liquid or an
inert gas to prevent contact with the atmosphere because
they rapidly tarnish in air.
 Group IIA
 Group IIA (Alkaline Earth Metals): Elements in this group
include
Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium
(Sr), Barium (Ba) and Radium (Ra) are known as alkaline
earth metals (with the exception of beryllium) because their
oxides react with water to form alkalis. Beryllium is not
considered an alkaline earth metal because its oxide and
hydroxide show amphoteric behavior.
 These elements have two electrons in their outermost shell.
They are less reactive than Group IA elements but still react
with water and acids. Their reactivity also increases down
the group. The ionization energy is higher than Group IA
but still relatively low, making it easier to lose the two outer
electrons.
 Group IIA
Beryllium and Magnesium can be stored in dry
air due to a thin passivating oxide layer, but
the more reactive Calcium, Strontium, and
Barium must be stored under mineral oil, in an
inert atmosphere, or sealed in airtight
containers to prevent reaction with oxygen
and moisture. Storage under an inert gas, such
as argon, is also an effective method for
preventing oxidation.
 ELECTRONIC CONFIGURATION
Beryllium (Be): [He]2s²
Magnesium (Mg): [Ne]3s²
Calcium (Ca): [Ar]4s²
Strontium (Sr): [Kr]5s²
Barium (Ba): [Xe]6s²
Radium (Ra): [Rn]7s²
 Group IVA
 Group IVA (Carbon Group): The elements in this group
comprises carbon (C), silicon (Si), germanium (Ge), tin
(Sn), lead (Pb) and flerovium (Fl) which is a radioactive
element (little is known about their chemical
reactivity)
 These elements have four electrons in their outermost
shell. They show varied reactivity; carbon and silicon
are less reactive, while tin and lead are more reactive.
The ionization energy is higher compared to Groups IA
and IIA because more energy is required to remove
electrons from a more stable half-filled p-orbital.
 ELECTRONIC CONFIGURATION
C: [He] 2s2p2
Si: [Ne] 3s2p2

Ge: [Ar] 3d10,4s2p2

Sn: [Kr] 4d10, 5s2p2

Pb: [Xe] 4f14, 5d10 6s2p2
Fl: [Rn] 5f¹⁴, 6d¹⁰ 7s²7p2
 Comparison
 Group IA elements are the most reactive and
have the lowest ionization energies. Group IIA
elements are less reactive than Group IA but
more reactive than Group IVA, with moderate
ionization energies. Group IVA elements have
the highest ionization energies and show the
least reactivity among the three groups.
 Comparison
Group IA elements are highly reactive with low
ionization energies. Group IIA elements are
moderately reactive with higher ionization
energies than Group IA. Group IVA elements have
the highest ionization energies and show varied
reactivity, generally less than Groups IA and IIA.
Groups IA, IIA, and IVA in the periodic table show
different trends in reactivity and ionization
energy due to their distinct electronic
configurations.
3d

Lanthanides
Actinides
5
 EXTRACTION OF METALS
The process of extracting metal ores buried deep
underground is called mining. The metal ores are
found in the earth’s crust in varying abundance.
The extraction of metals from ores is what allows
us to use the minerals in the ground. The ores are
very different from the finished metals that we
see in buildings and bridges. Ores consist of the
desired metal compound and the impurities and
earthly substances called gangue. The extraction
of metals and their isolation occurs over a few
major steps:

1
 EXTRACTION OF METALS
Extraction of metals and the reactivity series:
The most reactive metals are at the top of the
series
The tendency to become oxidised is thus linked to
how reactive a metal is and therefore
its position on the reactivity series
Metals higher up are therefore less resistant to
oxidation than the metals placed lower down
which are more resistant to oxidation
The position of the metal on the reactivity series
determines the method of extraction
2
REACTIVITY SERIES OF METALS

3
 EXTRACTION OF METALS
Concentration of Ore – the ore is
separated from earthy impurities.
Isolation of metal from concentrated
Ore – Here the ore is converted to its
oxide form and then reduced. The
steps involved are either calcination
or roasting and then heating with a
reducing agent. 4
Metals extraction method table
Metal Extraction method

Most reactive

Potassium

Sodium

Lithium Extracted by electrolysis of the molten chloride or oxide

Large amounts of electricity are required, which makes this an expensive
Calcium process

Magnesium

Aluminium

Zinc
Extracted by heating with a reducing agent such as carbon or carbon
Iron monoxide in a blast furnace
A cheap process as carbon is cheap and can also be a source of heat
Copper

Silver
Found as pure elements
Gold

Least reactive 5
EXTRACTION FLOW CHAT

6
7
 The extraction method depends on
the position of a metal in the
reactivity series
Higher placed metals (above carbon)
have to be extracted
using electrolysis as they are too
reactive and cannot be reduced by
carbon
Lower placed metals can be extracted
by heating with carbon
which reduces them
8
 Steps in the extraction of metals from their
ores.

Concentration of Ores
The very first step, which is the
concentration of ore, involves the
removal of gangue particles that can
be achieved using gravity separation,
froth floatation, magnetic
separation, and leaching processes.
9
 EXTRACTION OF METALS
The gravity separation method is used when
gangue particles are lighter than the ore. This
method is generally used for the
concentration of oxides and carbonate ores.
The method involves the passing of crushed
ore particles through a stream of water during
which the lighter gangue particles are washed
away.

10
Steps in the extraction of metals from
their ores.
The froth floatation method is used to remove
gangue particles from sulfide ores. In this
method, the crushed ore and water are added
to a tank in which a frother, such as pine oil, is
added and then air is blown under pressure to
create the froth. The gangue particles will be
wetted by water and the metal comes up with
the froth.

11
Steps in the extraction of metals from
their ores.
The magnetic separation method is used when
either metal or gangue particles have magnetic
properties. In this method, the crushed ore is
passed over conveyor belts with magnetic rollers.
The leaching method is used to concentrate ores
of aluminium, silver, and gold, etc. In this
method, the crushed ore is treated with a solvent
that dissolves the ore leaving behind the
impurities.

12
 Metal Extraction Processes

Roasting and Calcination

Roasting is the heating of concentrated metal ore
in presence of air. It is mainly done for metal
sulfide ores to convert them into their respective
oxides. For example, cinnabar is a sulfide ore of
mercury with the chemical formula of HgS. When
the ore is heated in presence of air, it is first
converted into mercuric oxide and then upon
further heating, liquid mercury is formed:

13
 Metal Extraction Processes
Δ
2HgS(s) + 3O2(g) ⟶ 2HgO(s) + 2SO2(g)
Δ
2HgO(s) ⟶ 2Hg(l) + O2(g)
When zinc blende undergoes roasting, zinc sulfide
present in the ore is converted into zinc oxide:
Δ
2ZnS(s) + 3O2(g) ⟶ 2ZnO(s) + 2SO2(g)

14
 Metal Extraction Processes
• Calcination is the process in which ore is
heated in the absence or in a limited supply of
air. This method is commonly used to convert
metal carbonates and metal hydroxides into
their respective oxides.
• Zinc oxide and carbon dioxide gas are formed
when smithsonite, the carbonate ore of zinc,
is heated in absence of air:

15
 Metal Extraction Processes

Δ
ZnCO3(s) ⟶ ZnO(s) + CO2(g)
Similarly, calcium oxide and carbon dioxide gas
are formed when limestone, the carbonate ore of
calcium, is heated in a limited supply of air:
Δ
 CaCO3(s) ⟶ CaO(s) + CO2(g)

16
 Metal Extraction Processes
Reduction and Electrolytic Reduction
The metal oxides produced in the roasting and
the calcination processes further undergo
reduction to produce impure metal. Reduction
can be done using an appropriate reducing
agent such as carbon or hydrogen. When zinc
oxide is reduced with carbon, impure zinc
metal and carbon monoxide gas is produced:

17
 Metal Extraction Processes
ZnO(s) + C(s) → Zn(s) + CO(g)
When copper oxide is heated in presence of
hydrogen, copper oxide is reduced to copper:
Δ
CuO(s) + H2(g) ⟶ Cu(s) + H2O(g)
The reduction of metal oxide can also be
achieved by using a displacement reaction in
which a more reactive metal replaces the less
reactive one. Since aluminium is a more reactive
metal than copper, when copper oxide is heated
with aluminium metal,
18
 Metal Extraction Processes
 copper and aluminium oxide are produced. This is
known as the thermite reaction in which aluminium
metal is oxidized by some other metal:
 3CuO(s) + 2Al(s) → 3Cu(l) + Al2O3(s)

 A thermite reaction is used to join railway tracks. When

iron oxide is heated with aluminium, iron and
aluminium oxide are produced along with a large
amount of heat that keeps the metal in a molten state
which is helpful for joining the railway tracks.
 Fe2O3(s) + 2Al(s) → 2Fe(s) + Al2O3(s)
19
 Metal Extraction Processes
The highly reactive metals such as sodium and
magnesium, etc., cannot be obtained by the
reduction of their respective metal oxides
because these metals have a high affinity for
oxygen. Therefore, these metals can
be isolated by the electrolytic reduction of
their molten salts.
The electrolytic cell consists of an anode and a
cathode made of graphite and an

20
 Metal Extraction Processes
electrolyte which is the molten metal salt. The
molten salts contain their respective ions. For
example, molten sodium chloride contains
sodium ions and chloride ions. When an
electric current is passed through the cell, the
sodium

21
 Metal Extraction Processes
ions present in the electrolyte get reduced at
the cathode and converted into pure sodium
metal while the chloride ions are oxidized at
the anode and released as chlorine gas.
At the cathode:
Na+ + e− → Na

22
 Metal Extraction Processes
At the anode:
2Cl− → Cl2 + 2e−
The overall reaction:
2NaCl(s) → 2Na(s) + Cl2(g)

23
 Refining of Metals

The impure metal produced in the

reduction process needs to be
refined in order to obtain pure metal.
One of the refining methods
is electrolytic refining in which a strip

24
 Refining of Metals
of impure metal is made at the anode
while pure metal is made at the
cathode. The metal salt solution is
used as the electrolyte in this
process.

25
 Refining of Metals
When an electric current is passed
through the cell, the pure metal from
the anode goes into the electrolyte
and the same amount of pure metal
then is deposited at the cathode.
During this process, the insoluble
impurities settled below the anode
as anode mud.
26
 Refining of Metals

Impure copper can be purified by the

electrolytic refining method. An
impure copper strip acts as
the anode, pure copper strip as the
cathode, and the aqueous solution of
copper sulfate as the electrolyte.

27
 Refining of Metals
When an electric current is passed
through the cell, copper at the
anode will be oxidized into copper
ions and go into the electrolyte
solution. The copper ions in the
electrolyte are reduced and get
deposited at the cathode.
28
 EXTRACTION OF IRON
Extraction of iron from hematite
Iron is extracted in a large container called a
blast furnace from its ore, hematite
Modern blast furnaces produce approximately
10,000 tonnes of iron per day
This is a continuous process with new raw
materials added and products removed all the
time due to the time and cost associated with
getting the furnace up to temperature
29
The blast furnace

30
 EXTRACTION OF IRON
The raw materials: iron ore
(hematite), coke (an impure form of
carbon), and limestone are added
into the top of the blast furnace
Hot air is blown into the bottom

31
 EXTRACTION OF IRON

Raw material Formula Use

Iron ore (hematite) Fe2O3 Source of iron

Coke C To provide carbon

Limestone CaCO3 To neutralise acidic impurities

32
 EXTRACTION OF IRON
Zone 1
Coke burns in the hot air forming carbon
dioxide
The reaction is exothermic so it gives off
heat, heating the furnace
carbon + oxygen → carbon dioxide
C (s) + O2 (g) → CO2 (g)

33
 EXTRACTION OF IRON
Zone 2
At the high temperatures in the furnace, more
coke reacts with carbon dioxide forming
carbon monoxide
Carbon dioxide has been reduced to carbon
monoxide
carbon + carbon dioxide → carbon monoxide
CO2 (g) + C (s) → 2CO (g)
34
 EXTRACTION OF IRON
Zone 3
Carbon monoxide reduces the iron(III) oxide in
the iron ore to form iron
This will melt and collect at the bottom of the
furnace, where it is tapped off:
iron(III) oxide + carbon monoxide → iron +
carbon dioxide
Fe2O3 (s) + 3CO (g) → 2Fe (I) + 3CO2 (g)
35
 EXTRACTION OF IRON
 Removal of impurities
Limestone (calcium carbonate) is added to the furnace to remove
acidic impurities in the ore
– The calcium carbonate in the limestone thermally decomposes to form
calcium oxide
calcium carbonate → calcium oxide + carbon dioxide
CaCO3 (s) → CaO (s) + CO2 (g)
The calcium oxide formed reacts with the silicon dioxide, which is an
impurity in the iron ore, to form calcium silicate by neutralisation
calcium oxide + silicon dioxide → calcium silicate
CaO (s) + SiO2 (s) → CaSiO3 (l)
This melts and collects as a molten slag floating on top of the molten
iron, which is tapped off separately

36
 EXTRACTION OF ALUMINIUM
Extraction of aluminium
Aluminium is a reactive metal, above carbon in
the reactivity series
Its main ore, is bauxite, which contains aluminium
oxide
Aluminium is higher in the reactivity series than
carbon, so it cannot be extracted by reduction
using carbon
Instead, aluminium is extracted by electrolysis

37
 EXTRACTION OF ALUMINIUM
The electrolytic cell for extraction of aluminium

38
 EXTRACTION OF ALUMINUM
Bauxite is first purified to produce aluminium
oxide, Al2O3
Aluminium oxide is then dissolved in molten
cryolite ( a rare white to colourless sodium
aluminium fluoride mineral)
– This is because aluminium oxide has a melting
point of over 2000°C which would use a lot of
energy and be very expensive
– The resulting mixture has a lower melting point
without interfering with the reaction
39
 EXTRACTION OF ALUMINIUM
The mixture is placed in an electrolysis cell, made
from steel, lined with graphite
The graphite lining acts as the negative electrode,
with several large graphite blocks as the positive
electrodes
At the cathode (negative electrode):
– Aluminium ions gain electrons (reduction)
– Molten aluminium forms at the bottom of the cell
– The molten aluminium is siphoned off from time to
time and fresh aluminium oxide is added to the cell
Al3+ + 3e– → Al
40
 EXTRACTION OF ALUMINIUM
 At the anode (positive electrode):
– Oxide ions lose electrons (oxidation)
– Oxygen is produced at the anode:
2O2– → O2 + 4e–
The carbon in the graphite anodes reacts with the oxygen
produced to produce CO2
C (s) + O2 (g) → CO2 (g)
As a result the anode wears away and has to be replaced
regularly
A lot of electricity is required for this process of extraction,
this is a major expense

41
 CHM 102/CHE 126

INTRODUCTION TO TRANSITION METAL

CHEMISTRY
 TRANSITION METALS
 Elements in the middle of the periodic table (d-
block)

 They serve as a bridge, or transition, between the

metallic elements (Groups I and II) and the
elements of Groups III  VIII

 And since they are all metals,

Hence, are called “transition metals”

2
 TRANSITION METALS
Abridged Periodic Table

3
 TRANSITION ELEMENTS
 The transition metals are found in the d-
block) while the lanthanides and
actinides are called ‘f-block metals’

 The lanthanides and the actinides are

sometimes known as rare ear th
elements.

 Also called the inner transition metals

 because they have atomic numbers that fall
between the last two periods on the Periodic 4
3d

Lanthanide
s Actinide
s
5
General characteristics of Transition Metals

 Exhibit variable oxidation states, except a few

 Hav e incompletely f il led d orbital i n any o f t he i r
commonly occurring oxidation states

 Their ions and compounds are usually coloured

 Many are paramagnetic

 They form a wide range of complexes with ligands

 Alloy formation

6
 ELECTRON CONFIGURATION

• Sc [Ar] 3d14s2 • Fe [Ar] 3d64s2

• Ti [Ar] 3d24s2 • Co [Ar] 3d74s2
• V [Ar] 3d34s2 • Ni [Ar] 3d84s2
• Cr [Ar] 3d54s1 • Cu [Ar] 3d104s1
• Mn [Ar] 3d54s2 • Zn [Ar] 3d104s2

 Additional stability associated with half- or fully-

filled orbitals as seen in 24Cr & 29Cu
7
 OXIDATION STATES
 Oxidation states of TMs are variable
 You need to f ind the specif ic oxidation state of the
TM in a given complex!
 This can be determined by calculation:

Examples:
1. [Pt(CN)4]2– x + (-1x4) = -2, x = +2…..Pt(II)
2. [Fe(CO)5] x + (0x5) = 0, x = 0……Fe(0)

3. [Co(NH3)6]Cl3 x + (0x6) + (-1x3) = 0,

x = 3….Co(III)
8
 TMs AND COLOUR
 Most TMs and their compounds are coloured,
arising from two phenomena

1. d d transition: due to their incompletely f il led d

orbitals, electron(s) can be promoted from the lower
energy d orbital to a higher energy d orbital.
The energy absorbed is related to colour (this can
be directly predicted for complexes containing
only one d electron)

Those with no electrons or full electrons in the d

orbital are usually pale or colourless e.g.
Ti (d ) – purple;
3+ 1 Cr (d ); Cu (d ) – blue; 2+ 4 2+ 9

V (d ); Fe (d ); Ni (d ) – green
3+ 3 2+ 6 2+ 8

Sc (d ); Cu (d ), Zn (d ) – colourless (or white)

3+ 0 + 10 2+ 10

Mn (d ) – pale pink;
2+ 5

9
 TMs AND COLOUR
d d transition:
 There are 5 d orbitals of equal energy

 In an octahedral field, splitting of the 5 d orbitals occurs

due to differences in their shapes and relative orientation of
the ligands

 eg
Orbitals

t2g
Orbitals
10
 TMs AND COLOUR
 t2g & eg orbitals are separated by an energy gap, Δo
 t2g orbitals are lower in energy, hence electrons are
arranged there first
 t2g orbitals are said to occupy the Ground state while the
eg orbitals are in the Excited state

11
TMs AND COLOUR

eg

Δo

t2g

12
 TMs AND COLOUR
 Absorption of light causes transition of electrons
from the t orbitals (ground state) to e orbitals
2g g

(excited state)

 T he whi te l i g ht ab so rb e d ( ROYGBI V ) i s o f a
particular wavelength

 Wavelength of light absorbed is related to Energy ( ~

Δ in some cases)
o

 Colour seen = light not absorbed, complementary

Absorption of ORANGE light, complex appears
BLUE
13
Colour Wheel for UV Absorption

14
Wavelength (nm) Absorbed
Complementary

360-420 Violet Green

420-450 Indigo Yellow
450-490 Blue Orange
490-520 Blue-green Red
520-580 Green Violet
580-590 Yellow Indigo
590-630 Orange Blue
630-720 Red Blue-green

15
Approximate Colours for Some Common TM
Complex Ions

16
 TMs AND COLOUR
2. The second phenomenon ascribed to colour in
TMs is the charge transfer transition which
could be

 Ligand to metal (L→ M) or

 Metal to ligand (M → L) charge transfer

transition

e.g. in KMnO4, Mn7+ with d0, the purple colour is

due to L →M charge transfer transition.
17
 Naming of TM Complexes and Ions
1. [Fe(CO)5] pentacarbonyliron(0)
2. [Pt(CN)4]2– tetracyanoplatinate(II) ion
3. [Co(NH3)6]Cl3 hexaamminecobalt(III) chloride [Co(NH3 ) 6 ]3+
3Cl–
4. K3[Co(CN)6] 5. [Ni(H2O)6]2+

 Name as a single-word all entity within the coordination

sphere (cs), starting with the ligand first
 Name the ligand appropriately
 End the name of TM with –ate in an anionic complex
 Write the oxidation state of TM in parenthesis
 End the name with ion if containing positive/negative
charges
18
 Leave a space for counter ions before or after the coord
 TMs AND MAGNETISM
 M ag net ic p rop er t ies of T M s are relat ed to t he
presence or absence of unpaired (lone) d electrons
o Diamagnetism  All electrons are paired (repelled
by the magnetic field).
o Clockwise & anticlockwise spins cancel

o Paramagnetism  Unpaired electrons (attracted

to the poles of the magnet)
 Paramagnetism gives rise to magnetic moments
o Electron spinning on its axis  spin magnetic
moment
o Electron orbiting round the nucleus  orbital
magnetic moment 19
 PARAMAGNETISM
•

20
 PARAMAGNETISM
•

21
 I–– < Br–– < Cl–– < F–– < OH–– < H2O < EDTA < NH3 < CN–– < CO

Weak field Increasing ligand field strength Strong

field

High spin Low spin

22
d6 High d6 Low spin
spin eg
eg

Δo Δo

t2g
t2g

Weak field Strong field

Smaller Δo Larger Δo
More n Fewer n
High spin Low spin
complex complex
23
CALCULATION OF MAGNETIC MOMENTS

24
FORMATION OF COMPLEXES OR COMPLEX
IONS
 Not all transition-metal compounds are complexes

 Transition metal (or ion) + LIGAND = Complex (or

complex ion)

 The molecules or ions surrounding the central metal

ion are called ligands e.g. water, ammonia and
chloride ions

 Ligands are Lewis bases capable of donating

electron (pairs) to the metal ion;
 can be neutral or negatively charged
 T hey b ind t o t he m e t al io n t hro ug h d at iv e
bonding (coordinate bonding)
25
 Examples of ligands

Water Ammonia Choride

Aqua Ammine Chloro

H2O NH3 Cl–

26
Complexes – “Coordination Compounds”
• Most transition metals have vacant d-orbitals to
accept electron pairs
– Forming coordinate covalent bonds in complexes
or coordination compounds
– The complexes formed could be:

Cationic: [Cr(H2O)6]3+, [Co(NH3)6]3+, [Ag(NH3)2]+

Neutral: [Fe(CO)5] , [PtCl2(NH3)2]

Anionic: [Ni(CN)4]2–, [Cr(OH)6]3 –, [CuCl4]2–

27
COMPLEXES – Coordination Compounds
 Ligands are Lewis bases electron donors
 TM ions are Lewis acids electron acceptors

 Ligands attach (coordinate) to Lewis acid by “lone pair”

of electrons

 Atom directly attached (through its lone pair of electron)

is called the ‘donor atom’
H2O NH3 Cl–

 Coordination Number – Number of donor atoms directly

attached

28
COMPLEXES – Coordination Compounds
OH 2+
2
H2 OH
O Fe 2
Examples
H2 OH [Fe(H2O)6]2+
O 2
OH CN?
[Co(NH3)6]2+
2

NH3 3+ [Cr(OH)6]3-

H3 NH
[CuCl4]2-
N Co 3

H3 NH
N 3 CN?
NH3 29
 ALLOY FORMATION
 An alloy is a mixture of elements, including at least a
metal

 P ure m e t a l s d o no t usua l l y hav e a l l t he d e si re d

properties

 Alloys are created to get the desired and enhanced

properties of the combined elements such as corrosion
resistance, mechanical strength, tensile strength, etc.

 TMs form alloys with one another and/or other elements

due to their
 similar atomic sizes, one metal can replace the other
metal in its lattice
 miscibility in the molten state 30
 ALLOY FORMATION
Examples
 Brass – Copper 80% and zinc 20%. Other components can
be added in smaller amounts.
 Brass is more corrosion-resistant, and is harder than
c o ppe r, i nc re asi ng the Zn c o nte nt i nc re ase s i ts
hardness

 Bronze – Copper 90% and tin 10%. Very small amounts of

zinc, Al, Si, P, nickel, or manganese may be added.
 Bronze is harder, stronger, more durable, has better
corrosion resistance, its lower mpt makes it easier to
cast into shapes

 Duralumin – Cu and Al,

 known for its strength and hardness, making it suitable
for various applications, especially in the aviation and
31
 ALLOY FORMATION
 Steel – Iron 90% and carbon 1%, small amounts of Mn, Si,
P, S, O.
 Steel is stronger, yet, lightweight enough for various
applications,
 more corrosion-resistant and durable than pure iron,
 has higher tensile strength,
 tougher and can handle stress without breaking,
though might be deformed

 Stainless steel – Iron, chromium 16-18% and nickel 5%,

 resistant to corrosion and staining, etc.

32
 CATALYTIC PROPERTIES
 A catalyst alters the rate of a reaction without itself
being consumed, by providing an alternative reaction
route with a lower activation energy.

 TMs and their compounds are being used as catalysts in

many chemical reactions
 with variable oxidation states, they form unstable
intermediate compounds and provide a new path with
lower activation energy for the reaction, thereby
increasing the reaction rate

 In some cases the f in ely divided metals or their

c o m po u n d s pr o v i d e a l a r ge s u r f a c e a r e a f o r
adsorption and the adsorbed reactants react faster
due to the closer contact
33
 CATALYTIC PROPERTIES
Examples

 TiCl3 – Ziegler-Natta catalyst in production of polythene

 V2O5 – Contact process for H2SO4, converts SO2 to SO3

 MnO2 – Catalyst to decompose KClO3 to give O2

 Fe – Haber-Bosch process for making NH3

 Ni – Raney nickel, reduction processes

34
INTRODUCTION TO NUCLEAR CHEMISTRY
The Atom

Protons Neutrons Electrons

Charge +1 0 –1
Mass (amu) 1 1 0
Location Nucleus Nucleus Orbital

1
INTRODUCTION TO NUCLEAR CHEMISTRY
The Nucleus

Is composed of protons +
neutrons

Nucleons

Is denoted by two numbers….A & Z

A A = Atomic mass number = Number of nucleons

X
2
Z
 INTRODUCTION TO NUCLEAR
CHEMISTRY
Electrons determine the physical and
chemical properties of atoms, ion,
molecules etc.

Nucleus/Nucleons do not determine these

properties of the atom but are rearranged
to form different nuclei

Nuclear chemistry involves the

phenomena in the nuclei of atoms
Atoms are not conserved but nucleons are,
Main difference between a chemical
reaction and a nuclear reaction. 3
 The Mass Defect of a nuclide
(Δm)
Difference between the sum of the
masses of its constituent nucleons
and the actual mass of an atom’s
nucleus
Mass defect = mass of nucleons – mass of
nucleus

It is mass of the energy binding

the nucleus
Evidence – Sum of the masses of
4
 Nuclear Binding Energy
Energy required to split a nucleus of
an atom into its component nucleons

Measure of the stability of the nucleus

Strength of the nuclear bond depends

on the number of nucleons (n + p)

5
 Nuclear Binding Energy
Einstein equation describes the equivalence
and interconvertibilty of mass and energy
Law of conservation of mass-energy
“the total of the mass and energy of the
universe is a constant”
Every energy change must be accompanied
by change in mass
ΔE = Δmc2
Nuclear binding energy is calculated by
converting mass defect to energy
Mass defect ꭀ nuclear binding energy
o energies in nuclear processes
6
 Nuclear Binding Energy (Units)
E = Δmc2
Unit of E = Joules, when m = kg, c = m s–1
Other units are Joules/nucleon, Joules/mole, MeV

To convert to Joules/mole, Joules x Avogadro’s number

To convert to Joules per nucleon, Joules / nucleons
To convert to MeV, Joules x 6.2415064799632 x 1012
MeV
1 Mev = 1.6021892 x 10-13 J

Unit of mass = kg,

mass (kg) = atomic mass unit (u) x 1.66053886 x
10–27 kg
7
8 –1
 Calculation Examples
(i) Calculate the average binding energy per
mole of a U-235 isotope. Show your answer in kJ/
mole and in J/nucleon. (U-235 has 92 protons, 143
neutrons, and has an observed mass of 235.04393
u).

Solution
Mass defect = 235.04393 u – (1.007825 x 92 + 1.008665 x
143) = 1.915065 u
Convert to kg: 1.915065 u x 1.66053886 x 10–27 kg =
3.18004 x 10–27 kg
Calculate the energy: E = Δmc2
E = 3.18004 x 10-27 kg x (3 x 108 )2 = 2.862 x 10-10 J
= 2.862 x 10-13 kJ = 2.862 x 10-13 x 6.02 x 1023 kJ/mole 8
 Calculation Examples
Atomic mass of 3919K is 38.96371u.
(i) Calculate the binding energy for this nuclide
(n = 1.008665 u, p = 1.007825 u, c = 3 x 108 m s-1,
1 u = 1.6605655 x 10-27 kg).
(ii) Calculate the total binding energy of one mole
of 3919K atoms.

Solution
39
19K has 19 protons, 20 neutrons
(i) Mass of nucleons = (19 x 1.007825) + (20 x
1.008665)
= 19.148675 u +20.1733 u = 39.32197 u
Mass defect = mass of nucleons – mass of nucleus
= 39.32197 – 38.96371 = 0.35826 u 9
 Calculation Examples
Mass defect in kg = 0.35826 x 1.6605655 x 10-27
= 5.9493 x 10-28 kg
Energy equivalent of this mass = mc2
= (5.9493 x 10-28) x ( 2.9979 x 108)2 = 5.3469 x 10-11
J

(ii) For 1 mole, total binding energy is this

energy x Avogadro number
= 5.3469 x 10-11 x 6.022 x 1023 = 3.2199 x 1013 J/mol

In MeV/nucleon; E = (0.35826 u x 931.5 MeV/c2)c2

/39
= 8.56 MeV/nucleon

Note: 1 u = 931.5 MeV/c2 10

Binding energy per nucleon
Average energy required to remove an individual
nucleon from a nucleus

Binding energy per nucleon = nuclear binding

energy / number of nucleons in nucleus
– Values are estimated from nuclear scattering
experiments
– Is useful for comparing one nucleus with another
– Is a measure of the stability of nuclei, large
energy = stability
– Analogous to IE of an electron in an atom
• Values ≈ 6–10 MeV to remove a nucleon from a
nucleus
• cf. 13.6 eV needed to ionize an electron in the
ground state of hydrogen 11
Binding energy per nucleon
Increases rapidly for lighter elements

The plot of the variation of binding energy

per nucleon with increase in atomic number
is shown below

Maximum occurs around atomic mass 56,

here nucleons are most strongly bound
together
• Suggests nuclei with mass numbers in the
region of 56, e.g. nickel, iron are the most
stable
• This is why nuclear fusion in the cores of
stars ends with Fe 12
 Binding energy per nucleon
The shape of the graph has to do with
competing forces in the nucleus

As number of nucleons increases, the nucleons

are held together more strongly

At low atomic masses, attractive nuclear forces

(between nucleons and outer electrons)
dominate over the repulsive electrostatic
forces between protons

At high atomic masses, repulsive electrostatic

forces between forces begin to dominate, and
these forces tend to break apart the nucleus
rather than hold it together 14
 Nuclear Reactions
The four main types of nuclear reactions:

Fission – of unstable heavy nuclei

Fusion - of light nuclei

o occurs naturally only in the sun
and other stars
Decay – spontaneous decay of
radioactive nuclides

Transmutation – Nuclear reaction

induced by bombardment reactions
15
 Nuclear Fission
The nucleus of a large atom is split into smaller and
lighter nuclei
o when bombarded with particles such as neutrons
o releasing a large amount of energy
o plus neutrons and photons (in form of γ
radiations)

Mass of original nucleus is slightly higher than the

masses of its individual nuclei
o This difference is the mass defect

The final products are more stable

16
 Nuclear Fission
Most important is uranium-235 fission:
235 1 89 144 1
92 U + 0 n → 36 Kr + 56 Ba + 3 0n

For every neutron consumed, three neutrons

are produced
Hence, used in nuclear power plants
o to provide electricity to an entire city
E.g., 1 kg of uranium can release sufficient
energy for combusting 4 billion kg of coal.
Used to produce steam to generate electricity

Used in nuclear bombs - to destroy an entire

17
city
Nuclear Fusion

18
 Nuclear Fusion
Two pairs of protons fuse, forming two deuterons. 4 1H →
2 2D
Each deuteron fuses with an additional proton to form
helium-3;
2
D + 1H → 3He
1
3
He + 3He → 6Be → 2 H + 4He + 2 v + 2 e+ + γ
Since the helium-4 atom has less energy or resting mass
than the 4 protons which initially came together, energy
is radiated outside the core and across the solar system

Sun uses up about 600 million tons of hydrogen nuclei per

second
converting it to helium and releasing 384.6 trillion
trillion Joules of energy per second 19
 Radioactivity
Spontaneous decomposition of one nuclide to form
a different nuclide
by unstable nuclide
with the emission of high-energy particles or
electromagnetic radiation or both, to gain
stability

226 4 222
88 Ra 2 He + 86 Rn

Parent nuclide Daughter nuclide

Natural or artificial
Approx. 33% of the elements has natural
radionuclides, which are called radioisotopes
or radioactive nuclides
All known isotopes of elements heavier than 20
 Radioactive Emissions
α-particle now known as helium nucleus 42He
Emission of α- particle by radionuclide
A A-4 4
Z X → Z-2 X + 2He + γ
238 234
92U → 90Th + 42He + γ

Net effect – reduction of the mass number by

4, and the atomic number by 2

α-particle emission leaves nuclide in an

excited state, then γ-radiation is emitted to
reach the stable (or ground) state.
Total energy of emitted α-particle + γ-
radiation is equal to the reaction energy.
21
 Radioactive Emissions
α-particle
Heavy nuclides with low neutron/proton
ratio and
those with Z > 83 undergo α-decay
185 181 4
79Au 77Ir+ 2He

185
Au with 106n & 79p (106/79 = 1.34)
79
lies below stability band and
the daughter nuclide with 104n & 77p is
closer to the band and hence more stable
(104/77 = 1.35).
22
 Radioactive Emissions
β-particle - Electron emission
No change in mass number but increases
atomic no. by 1
A A 0
z X Z+1 Y + –1e
14 14 0
6 C 7 N + –1e

Net effect - conversion of neutron to proton

( 10n 1
1p +
0
–1e)
n/p ratio decreases

Most common mode of decay for radioactive

nuclides since they lie above stability band
(too many neutrons)
24
 Radioactive Emissions
γ-Radiation
Gamma radiation is an high-energy photon of light
with short wavelength; it has no charge or mass

Radioactive decay sometimes leaves nucleus at

unstable excited nuclear energy level, emission of γ-
rays leads to ground state nuclear energy level
γ-ray is the excess energy of the electromagnetic
radiations
γ-ray often accompanies different types of
nuclear decays, though it is not usually shown in
nuclear reactions
A * A 0
Z X Z X + 0γ
238 234 4 0
92 U 90 Th + 2 He + 2 0γ 25
 Radioactive Emissions
Positron emission (β+ or 01e )

Positron is equal to electron in mass but

opposite charge (+1 instead of –1)

Net effect - conversion of proton to neutron

1 1 0
1 p 0 n + +1e
Atomic no decreases by 1, no change in
mass number 116C 11
5 B + 0
1e

increases n/p ratio, isotopes with too many

protons (below stability band) decay by this
process 26
 Radioactive Emissions
Electron capture
Capture of an inner-shell electron by an
unstable nucleus (proton) to produce a neutron

Net effect - conversion of proton to neutron

(11p + 0–1e 1
0n)
201 0 201 0
80Hg + –1 e 79Au + 0γ

As electrons rearrange themselves to

compensate for the electron pulled into the
nucleus, x-rays are emitted
50 0 50
23V + -1 e 22Ti + x-rays 27
 Nuclear Transmutation
This change from one isotope to another is
called transmutation
through radioactive decay

by bombarding the atoms of an isotope

with high energy particles
alpha particles from natural alpha
emitters
neutrons from atomic reactors
protons made by the removal of
electrons from hydrogen
28
 Nuclear Transmutation
Beta particles (electrons) are strongly repelled by
the orbital electrons
hence unable to get through in most cases & are not
used to cause transmutations

The first transmutation to occur under laboratory

conditions was by Rutherford research group (1925)
4 14 18 17 1
2 He + 7 N → 9 F** → 8 O + 1p

(** = high energy ; 178O is a rare but stable isotope)

Over 3000 radionuclides have been made by

transmutations and many are isotopes that do not
occur in nature
29
 Nuclear Transmutation
ALL trans-uranium elements with Z > 92 are
radioactive were made artificially
using high energy bombardment techniques in
nuclear reactors and accelerators
or by bombarding one atom type with another
E.g. Element Z = 111 was made by bombardment of
bismuth with nickel for several days

The synthetic elements 93–103 complete the

actinide series of the periodic table
Elements 104, 105, 106, 107 & 109 have been made
but are surrounded by controversies which have
complicated naming them
30
 Formation and decay of unstable
compound nuclei
With capture of bombarding particle,
compound nucleus is formed which has all of
the energy of the bombarding particle & is
therefore unstable

Its additional energy is soon distributed among

all of its nuclear particles but eventually the
nucleus has to get rid of the excess energy
o by ejecting a high-energy particle such as
o a neutron
o a proton
o an electron
o by emitting gamma radiation

The overall effect is a transmutation

31
 Nuclear Transmutation
The first experimentally induced
transmutation was the conversion of
Li-7 to He-4
Li-7 captured a proton to give a
compound beryllium nucleus, which
promptly breaks into two alpha particles:-

1 7 8
1p + 3Li → 4 Be** → 2
4
2He

32
 Nuclear Transmutation
Decay pattern depends on the amount of
energy, not on the bombarding particle used
in producing it e.g.
high-energy Al-27 compound nucleus
could be made
using alpha particles, protons or
deuterons:
4 23 27
2 He + 11 Na → 13Al**

1
1 p + 2612Mg → 2713Al**

2 25 27
1 D + 12 Mg → 13Al** 33
 Nuclear Transmutation
Once formed, the high-energy compound
nucleus has the following decay modes,
depending on the amount of energy it has

27 27 0
13 Al** → 13 Al + 0γ
27 26 1
13Al** → 12Mg + 1p
27 26 1
13 Al** → 13 Al + 0n
27 25 1 1
13 Al** → 12 Mg + 0 n + 1p
27 23 4
13 Al** → 11 Na + 2He.

All isotopes are stable except Aluminium-26

with a half-life of 7.4 x 105 y
34
 Radionuclides above number 83
Many of the other possible isotopes above 83
may well have existed at one time in nature,
but had half-lives too short in relation to the
age of the planet to have survived into the
20th century
For example, neptunium – 237, with a half life of
over 2 million years, undoubtedly existed
naturally at one time

Estimated age of the earth is over 4 billion

years, long enough for all the neptunium to
have decayed
35
 Radionuclides above number 83
To make heavier elements, bombarding
particles that are larger than neutrons have
been used
alpha particles
highly accelerated cations from isotopes
like carbon-12
nitrogen-15
Oxygen-18 &
neon-22

36
 Radionuclides above number 83
From the standpoint of practical
applications, most useful transmutations
produced radionuclides with sufficiently
long half-lives for use in research, medicine
& technology

37
 Band of Stability (Neutron/Proton
Ratio)
Why are some nuclides radioactive and
others are not?
A plot of the number of neutrons versus the
number of protons in stable nuclei will
provide an answer

The plot shows nuclei with an equal number

of n and p fall along the ‘broken’ line, n/p
= 1:1
Isotopes of lighter elements up to 4020Ca
fall on or quite close to the n = p line
(stable isotopes)
38
while in heavier elements n increases
Band of Stability (Neutron/Proton Ratio)
The additional neutrons provide the
additional nuclear force necessary to hold
larger no of protons close together within
the nucleus
Once Atomic No. reaches 83, even extra
neutrons cannot maintain stability
Hence, all known nuclides of Z > 83 are
unstable and radioactive
For each nuclear charge, only isotopes with
a neutron/proton ratio within a specific
range (band of stability) are stable and not
radioactive
40
Band of Stability (Neutron/Proton Ratio)
Essentially, radioactivity is the spontaneous
transformation of unstable nuclei to nuclei
with more favorable n/p ratios

Nuclides with too many protons fall below the

stability band and decay so that there is a
decrease in the number of protons relative to
the number of neutrons (greater n/p ratio)

Nuclides with too many neutrons are above the

stability band and decay so that there is a
decrease in the number of neutrons relative to
the number of protons (smaller n/p ratio)

42
Band of Stability (Neutron/Proton Ratio)
Thus, the elements are β-emitters, since beta
decay has the overall effect of losing a
neutron and gaining a proton:
1 1 0
0 n → 1 p + -1e

E.g., 209F → 20
10Ne + 0
-1e

β decay of F-20 reduces the n/p ratio from

11/9 to 10/10 thereby moving the
surviving nucleus (Neon-20) closer to the
center of the stability band.

43
Band of Stability (Neutron/Proton Ratio)
However, positron emission has the opposite effect
(increasing n/p ratio) e.g. F-17 improves its stability
by emitting a positron:
17 17 0
9 F → 8 O + +1 e

(n/p = 8/9 to 9/8)

Positron decay by Mg-23 to Na-23 produces a similar

favorable shift

The heavy nuclei above atomic number 83 are α-

emitters, because their nuclei have too many
protons for stability.
The loss of an alpha particle is the quickest way
to get rid of protons 44