FOUNDATION CHEMISTRY I

CHM092
CHAPTER 2
CHM092 2015
ELECTRONIC
STRUCTURE OF
ATOMS AND
PERIODICITY
1
 MAIN TOPICS

2.1 ATOMIC STRUCTURE

2.2 NUCLEAR ATOMIC MODEL

2.3 QUANTUM MECHANICS MODEL

2.4 ATOMIC ORBITALS

2.5 ELECTRONIC CONFIGURATIONS AND ORBITAL DIAGRAMS

2.6 PERIODIC CLASSIFICATION OF THE ELEMENTS

2.7 PERIODIC VARIATIONS IN PHYSICAL PROPERTIES

 2.1 ATOMIC STRUCTURE
• An atom is electrically neutral because the number of
protons are equal to the number of electrons

• Atoms do not lose or gain protons in any chemical

reaction but they do lose or gain electrons to become
ions
 2.2 NUCLEAR ATOMIC MODEL
Theories on nuclear atomic model:
• THOMSON’S MODEL
• RUTHERFORD’S MODEL
• BOHR’S MODEL
• DUAL NATURE OF ELECTRON (De Broglie’s
Postulate and Heisenberg’s Uncertainty Principle)
 THOMSON’S MODEL
• An English scientist, J. J.
Thomson founded electron in
1897 and proposed a model for
the structure of an atom

• Thomson proposed that an

atom could be thought of as a
uniform, positive sphere of
matter in which electrons are
embedded like raisins in cake
(refer figure)

• suggested electrons are

positioned by electrostatic
forces
 RUTHERFORD’S MODEL

• In 1910, Ernest Rutherford

proposed that the atoms
positive charge are all
concentrated in the nucleus

• The positively charged particles

in the nucleus are called proton
(p) and it has opposite (+)
charge of electron (-)
 BOHR’S ATOMIC MODEL
• The nuclear model of the atom does not explain what
structural changes occur when the atom gains or loses
energy

• In 1913, Neils Bohr developed a model of the atom to

explain how the structure of the atom changes when it
undergoes energy transitions

• Bohr’s major idea was that the energy of the atom was
quantized, and that the amount of energy in the atom
was related to the electron’s position in the atom

– quantized means that the atom could only have very specific
amounts of energy

7
Bohr’s atomic model postulates the following:
(a)The electrons in an atom are not randomly distributed but are
arranged in a series of “ORBITS” or “ENERGY LEVEL” which
are situated at various distances from the nucleus.
(b) The energies of electron are quantized
(c) Energy of an electron in one of its orbits is fixed as long as
the electron remains in one of its allowed orbit.
(d) The energy of an electron in a orbit is known as the principal
quantum number ; n can have values from 1 to infinity.
(e) If an electron jumps from higher energy level to a lower
energy level, it release a definite amount of energy.
 Bohr’s Model of the Atom (1913)
• e- can only have specific
(quantized) energy
values
• light is emitted as e-
moves from one energy
level to a lower energy
level

n (principal quantum number) = 1,2,3,…

45
 E = h

E = h

46
 The Bohr Model of Atom

• The single electron moves around the nucleus in orbits or

energy levels

• The orbits are pictured as concentric circles around the

nucleus. Energy levels are arranged in parallel lines.

• The orbits are given letter notations: k, l, m, n

• The energy levels are specified by the quantum number

‘n’ (n = 1, 2, 3 etc.)

11
 DUAL NATURE OF
ELECTRON
De Broglie’s postulate
• In 1924, Louis de Broglie
proposed that if light waves can
behave like a stream of
particles (photons), the
perhaps particles such as
electron can possess wave
properties
• He proposed that light and
matter appears to have dual
natures, that its, wave like as
well as particle-like.
Heisenberg’s uncertainty principle
• In 1927, Werner Heisenberg
showed from quantum
mechanics that it is not
possible to know with
unlimited accuracy both the
momentum (defined as mass
times velocity) and the
position of a particle, for
example, an electron.
• Electron does not orbit the
nucleus in a well-defined path
2.3 QUANTUM-MECHANICAL
MODEL OF ATOM

• ELECTRON TRANSITIONS

• SCHRODINGER WAVE EQUATION

• QUANTUM NUMBER (n,l,ml,ms)

 ELECTRON TRANSITIONS
• For transition to a higher energy state, the electron
must gain the correct amount of energy corresponding to
the difference in energy between the final and initial states.

• When an electron is in the first orbit, the atom is in its

lowest energy state, called the ground state.

• Electrons in high energy states are unstable. They are

in the excited state, and tend to lose energy and fall back to
lower energy states

• Electrons emit radiation when they “jump” from an orbit

with higher energy down to an orbit with lower energy.
– the emitted radiation was a photon of light
– the distance between the orbits determined the energy of the
photon of light produced
Quantum Leaps

15
 THE QUANTUM-MECHANIC
(Schrodinger Wave Equation)
The Schrödinger wave equation is the fundamental
equation for describing quantum mechanical behavior. It is
a partial differential equation that describes how the wave
function of a physical system evolves over time.
The solution of the Schrödinger equation gives not the exact
position of the electron (remember Heisenberg), but the
probability of finding the electron in a specific place
around the nucleus.

This most probable “place” is known as an orbital.

An orbital is a volume space around the nucleus that
contains the electron 90% of the time.
 n, l, ml, ms
• The size, shape, and orientation in space of an orbital are
determined by three integer terms called quantum
numbers n, l and m
l.

• In quantum mechanics, the distribution of electrons in an

atom or an atomic orbital is specified by principal quantum
number (n), the angular momentum quantum number
(l), and the magnetic quantum number (m ).
l

• These quantum numbers will be used to describe atomic

orbitals and to label electrons that reside in them. A fourth
quantum number – the spin quantum number (m ) –
s
describes the spin of a specific electron and completes
the description of electrons in atoms.
 PRINCIPAL QUANTUM NUMBER, n

• The principal quantum number, n, designates the

principal energy level (shell).
• As n increases, the energy of the electron increases and
the electron is farther from the nucleus.
• n = 1, 2, 3, 4, 5 …..
• Orbitals with the same value of n are in the same
principal energy level (or same shell)
• The larger the value of n, the more energy the orbital
has and the larger the orbital.

18
 Principal Quantum Number, n
n = 1, 2, 3, 4, ….
distance of e- from the nucleus

n=1 n=2 n=3

19
 ANGULAR MOMENTUM QUANTUM
NUMBER, l
• Angular momentum quantum number, l defines the
three-dimensional SHAPE of an orbital.

• Each principal quantum number, n has an angular

momentum quantum number, l or subshell.

• For a given value of n, l = 0, 1, 2, 3, … n-1

If n = 1, l = 0
n = 2, l = 0 or 1
n = 3, l = 0, 1, or 2
  Different subshells are usually referred to by letter
rather than by numbers as follows:
Value of l 0 1 2 3…
Subshell s p d f…
notation

 The number of subshells, l in any given shell equals to

the value of n for the shell.
Principal quantum 1 2 3 4
number (n)
Subshells 1s 2s, 2p 3s, 3p, 3d 4s, 4p, 4d, 4f
Number of subshells 1 2 3 4

For example: the shell with n=1 has one subshell (1s) while
the shell with n=2 has two subshells (2s and 2p)
Angular Momentum Quantum Number, l
l = 0 (s orbitals)
Spherical in shape

1 orbital diagram (refer section 2.5)

Angular Momentum Quantum Number, l
l = 1 (p orbitals)
Shaped like two balloons tied at the knots

3 orbital diagram (refer section 2.5)

Angular Momentum Quantum Number, l

l = 2 (d orbitals)
Shape like four balloons tied at the knot

5 orbital diagram (refer section 2.5)

 MAGNETIC QUANTUM NUMBER, ml

• The magnetic quantum number, ml determines the

ORIENTATION IN SPACE of the electron cloud
surrounding the nucleus.

• the direction in space the orbital is aligned relative

to the other orbitals

• Values of ml are integers from −l to +l including

zero
 Magnetic Quantum Number, ml

for a given value of l

ml = -l, …., 0, …. +l

if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

For a given type of orbital with the angular momentum

number l, there are (2l +1) different spatial orientations
in space
If l =1, so 2 (1) +1 =3
Thus, there are three different spatial orientations in space:
ml = -1, 0, or 1
Magnetic Quantum Number, ml

3 orientations in space: ml = -1, 0, or 1

5 orientations is space: ml = -2, -1, 0, 1, or 2
 SPIN QUANTUM NUMBER ms

 An electron can spin on its

own axis either clockwise
or anticlockwise.
 This spin of an electron is
described by the electron
spin quantum number, ms.
 Two possible values:
ms = +½ or -½

ms = +½ ms = -½
CHECKPOINT 1

List the values of n, ℓ, and mℓ for orbitals in the 4d subshell.

 2.4 ATOMIC ORBITALS
•Each set of n, l and ml describes an orbital
•Orbital with the same value of n are in the same principal
energy level
•Orbital with the same value of n and l are said to be in
the same subshell
70
 2.4 ATOMIC ORBITALS
Four types of atomic orbital that need to know:

• s ORBITAL

• p ORBITAL

• d ORBITAL

• f ORBITAL
 2.4 ATOMIC ORBITALS
• Each value of l designates the shape of the orbital
– s orbitals are spherical
– p orbitals are like two balloons tied at the knots
– d orbitals are mainly like four balloons tied at the knot
– f orbitals are mainly like eight balloons tied at the knot

• Within the same value of n, subshells increase in

energy in the order:
s<p<d<f

34
 The Shapes of Atomic Orbitals
l = 0, the s orbital

• Each principal energy level has

one s orbital

• Lowest energy orbital in a principal

energy state

• Spherical

• As n increases, the s-orbitals get

larger.

35
 The Shapes of Atomic Orbitals
l = 1, p orbitals
• Each principal energy state above n = 1 has three p
orbitals

ml = −1, 0, +1

• Each of the three orbitals points along a different axis

px, py, pz

• 2nd lowest energy orbitals in a principal energy state

36
The 2p orbitals
 The Shapes of Atomic Orbitals

l = 2, d orbitals
• Principal energy level where n = 3 or greater has five d
orbitals

– ml = −2, − 1, 0, +1, +2

• Four of the five orbitals are aligned in a different plane

– dxy, dyz, dxz, dx2 – y2

– the fifth is aligned with the z axis, dz2

38
3d orbitals

39
3d orbitals

40
 The Shapes of Atomic Orbitals
l = 3, f orbitals
• Each principal energy state with n = 4 or greater
has seven f orbitals

• ml = −3, −2, −1, 0, +1, +2, +3

• 4th lowest energy orbitals in a principal energy

state

41
The Shapes of Atomic Orbitals
The 4fxyz orbital, one of the seven 4f
orbitals.
CHECKPOINT 2
What is the total number of orbitals associated with the
principal quantum number n = 3?
CHECKPOINT 3

Write the four quantum numbers for an electron in a 3p orbital

2.5 ELECTRONIC CONFIGURATIONS
AND ORBITAL DIAGRAMS

• ELECTRON SPIN

• ORBITAL DIAGRAM

• ELECTRON CONFIGURATION

• PARTIAL ORBITAL DIAGRAMS AND CONDENSED

CONFIGURATIONS

• VALENCE ELECTRONS
 The Property of Electron Spin
• Spin is a fundamental property of all electrons

• The orientation of the electron spin is quantized, it can only

be in one direction (clockwise) or its opposite
(counterclockwise)

• spin up or spin down

• The electron spin adds a fourth quantum number to the

description of electrons in an atom, called the Spin
Quantum Number, ms

46
 Spin Quantum Number, ms, and
Orbital Diagrams
• ms can have values of +½ or −½

• Orbital Diagrams use a square to represent

each orbital and a half-arrow to represent each
electron in the orbital

• By convention, a half-arrow pointing up is

used to represent an electron in an orbital
with spin up

• Spins must cancel in an orbital with 2 electrons

(paired e-)

47
 ORBITAL DIAGRAMS
• We often represent an orbital as a square and
the electrons in that orbital as arrows

• the direction of the arrow represents the spin of the

electron

unoccupied orbital with orbital with

orbital one electron two electrons

48
 ELECTRON CONFIGURATION
Electron configuration is how the electrons are
distributed among the various atomic orbitals in
an atom.
number of electrons
in the orbital or subshell
1s1
principal quantum angular momentum
number n quantum number l

Orbital diagram
H
1s1
CHECKPOINT 4
What is the maximum number of electrons that can be
present in the principal level for which n = 3?
CHECKPOINT 5
An oxygen atom has a total of eight electrons. Write the four
quantum numbers for each of the eight electrons in the ground
state.
 RULES IN ASSIGNING ELECTRON
CONFIGURATION AND ORBITAL
DIAGRAM

 AUFBAU PRINCIPLE

 PAULI’S EXCLUSION PRINCIPLE

 HUND’S RULE
2.5 ELECTRON CONFIGURATIONS AND
ORBITAL DIAGRAM
Splitting of shells into Subshells
 Each energy level is split into subshells of differing
energy.
 Splitting is caused by penetration and its effect on
shielding.
 For a given n value, a lower l value indicates a lower
energy subshell

Increasing order of energy levels

s<p<d<f
 2.5 ELECTRON CONFIGURATIONS AND
ORBITAL DIAGRAM
Penetration and subshell (sublevel) energy

Orbital shape causes

electrons in some
orbitals to “penetrate”
close to the nucleus.

Penetration increases
nuclear attraction and
decreases shielding.
 AUFBAU PRINCIPLE
• According to the Aufbau Principle:

• Electrons occupy orbital in the orderr

of the energy levels of the orbital
starting with 1s as shown by the
diagram

• Arrows are drawn through the

diagonals, looping back to the next
diagonal each time

• The order is :

1s 2s 2p 3s 3p 4s 3d 4p 5s
55
 Order for filling energy
sublevels with electrons.

In general, energies of subshells

increase as n increases (1 < 2 < 3,
etc.)
and as l increases (s < p < d < f).

As n increases, some subshells

overlap.
“Fill up” electrons in lowest energy orbitals first
(Aufbau principle)
Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n

n=3

n=2

n=1
Energy of orbitals in a multi-electron atom

n=3 l = 2

n=3 l = 1
n=3 l = 0

n=2 l = 1
n=2 l = 0

n=1 l = 0
Energy depends on n and l
MAGNETIC PROPERTIES OF A SPECIES
A species that has one or more unpaired electrons
exhibits paramagnetism and it is called paramagnetic.

As example:
Ag (Z = 47) ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
5s 4d 5p

A species with all its electrons paired exhibits

diamagnetism and it is called diamagnetic.
As example:
He (Z = 10)
CHECKPOINT 6
Write the ground-state electron configurations for

(a) sulfur (S)

(b) palladium (Pd), which is diamagnetic.

 PAULI EXCLUSION
PRINCIPLE
• According to pauli exclusion principle, no two electrons
in an atom may have the same set of four quantum
numbers (n, l, ml, ms)
• Therefore the exclusion principle states that each orbital
may contain a maximum of 2 electrons, which must
have opposite spins.
A horizontal orbital
He (Z = 2) 1s2 diagram for the He
ground state.
1s
(a)
1s 1s
(b) (c)

Electrons in (a) and (b) are both

having the same set of quantum
number - not acceptable
Only (c) is acceptable
62
 HUND’S RULE
• Hund’s rule state that when electrons are places in a set of
orbitals with equal energies, the electrons must occupy
singly with parallel spins before they can occupy the
orbitals in pair.

• An atom tends to have as many unpaired electrons as

possible so that the electron arrangements is more stable.

Example: Nitrogen (Z= 7)

Allowed
1s2 2s2 2p3

Not allowed
1s2 2s2 2p3
The most stable arrangement of electrons in subshells is the
one with the greatest number of parallel spins (Hund’s rule).
 CHECKPOINT 7

Write a set of quantum numbers for the third electron and a

set for the eighth electron of the F atom.
PARTIAL ORBITAL DIAGRAMS AND CONDENSED
CONFIGURATIONS

A partial orbital diagram shows only the highest energy sublevels

being filled.

Al (Z = 13) 1s22s22p63s23p1

3s 3p

A condensed electron configuration has the element symbol of the

previous noble gas in square brackets.

Al has the condensed configuration [Ne]3s23p1

 Partial Orbital Diagrams and Electron Configurations* for the
Elements in Period 3.

*Colored type indicates the sublevel to which the last electron is added.
 Partial Orbital Diagrams and Electron Configurations* for the
Elements in Period 4.

*Colored type indicates the sublevel to which the last electron is added.
 Partial Orbital Diagrams and Electron Configurations* for the
Elements in Period 4.

*Colored type indicates the sublevel to which the last electron is added.
Condensed electron configurations
in the first three periods.
 CHECKPOINT 8

Using the periodic table, give the full and condensed electron
configurations, partial orbital diagrams showing valence
electrons only, and number of inner electrons for the following
elements:
 VALENCE ELECTRONS

• The electrons in all the sublevels with the highest

principal energy shell are called the valence
electrons
• Electrons in lower energy shells are called core
electrons
• Chemists have observed that one of the most
important factors in the way an atom behaves, both
chemically and physically, is the number of valence
electrons

72
ELECTRON CONFIGURATION & VALENCE
ELECTRONS
• Kr = 36 electrons

1s22s22p63s23p64s23d104p6

• there are 28 core electrons and 8 valence electrons

• Rb = 37 electrons

1s22s22p63s23p64s23d104p65s1

[Kr]5s1

• For the 5s1 electron in Rb the set of quantum numbers is n

= 5, l = 0, ml = 0, ms = +½
73
 ELECTRON CONFIGURATION AND
GROUP
 Elements in the same group of the periodic table have
the same outer electron configuration.
 Elements in the same group of the periodic table exhibit
similar chemical behavior
 Similar outer electron configurations correlate with
similar chemical behavior.
 ELECTRON CONFIGURATION &
THE PERIODIC TABLE

• The Group number corresponds to the number of valence

electrons

• The length of each “block” is the maximum number of

electrons the sublevel can hold

• The Period number corresponds to the principal energy

level of the valence electrons

76
 Ground State Electron Configurations of the Elements

ns2np6
ns1

ns2np3
ns2np1

ns2np2

ns2np4
ns2np5
ns2

d10
d1

d5

4f
5f
 Orbital filling and the periodic table.

The order in which the orbitals are filled can be obtained directly
from the periodic table.
 ELECTRON CONFIGURATIONS FOR
TRANSITION ELEMENTS
• For the d block metals, the principal energy level is one
less than valence shell

• one less than the Period number

• sometimes an s electron is “promoted” to d sublevel

Zn
Z = 30, Period 4, Group 2B
[Ar]4s23d10 4s 3d

79
 Electron Configuration from
the Periodic Table
1A 8A
1 2A 3A 4A 5A 6A 7A
2
3 3d10 Ar
4 4s2 As
5 4p3
6
7
As = [Ar]4s23d104p3
As has five valence electrons
To calculate the number of electron valence in transition metals:
Sum the number of electron from the highest subshells (sublevels)
 ANOMALOUS ELECTRON
CONFIGURATIONS

• We know that because of sublevel splitting, the 4s sublevel is

lower in energy than the 3d; and therefore the 4s fills before
the 3d

• But the difference in energy is not large

• d subshells that are half-filled of fully filled are

particularly stable.

• Because of this, some of the transition metals have irregular

electron configurations in which the ns only partially fills
before the (n−1)d or doesn’t fill at all.

81
 ANOMALOUS ELECTRON
CONFIGURATIONS
For Example:

• The electron configuration of chromium is Cr =

[Ar]4s13d5 and not Cr = [Ar]4s23d4.

• Instead of adding a second electron into 4s orbital, the

electron is placed in a 3d orbital so that the 3d orbitals
are half-filled.
 ANOMALOUS ELECTRON
CONFIGURATIONS
Other examples of transition metals:

Expected Half-filled or full subshells

• Cu = [Ar]4s23d9 • Cu = [Ar]4s13d10

• Mo = [Kr]5s24d4 • Mo = [Kr]5s14d5

• Pd = [Kr]5s24d8 • Pd = [Kr]5s04d10

83
 The Noble Gas
Electron Configuration

• The alkali metals have one more electron

than the previous noble gas

• In their reactions, the alkali metals tend to

lose one electron, resulting in the same
electron configuration as a noble gas

• forming a cation with a 1+ charge

 The Noble Gas
Electron Configuration

• The electron configurations of the halogens

all have one fewer electron than the next
noble gas

• In their reactions with metals, the halogens

tend to gain an electron and attain the
electron configuration of the next noble gas

• Forming an anion with charge 1−

• In their reactions with nonmetals, they tend

to share electrons with the other nonmetal
so that each attains the electron
configuration of a noble gas
 ELECTRON CONFIGURATION OF IONS

• We have seen that many metals and nonmetals form one

ion, and that the charge on that ion is predictable based on
its position on the Periodic Table

• Group 1A = 1+, Group 2A = 2+, Group 7A = 1−, Group

6A = 2−, etc.

• These atoms form ions that will result in an electron

configuration that is the same as the nearest noble gas

86
 ELECTRON CONFIGURATION OF
ANIONS IN THEIR GROUND STATE
• Anions are formed when nonmetal atoms gain enough
electrons to have eight valence electrons

• filling the s and p sublevels of the valence shell

• The sulfur atom has six valence electrons

S atom = 1s22s22p63s23p4

• To have eight valence electrons, sulfur must gain two more

S2− anion = 1s22s22p63s23p6

87
 ELECTRON CONFIGURATION OF
CATIONS IN THEIR GROUND STATE
• Cations are formed when a metal atom loses all its valence
electrons

• The magnesium atom has two valence electrons

Mg atom = 1s22s22p63s2

• When magnesium forms a cation, it loses its valence

electrons

Mg2+ cation = 1s22s22p6

88
 ELECTRON CONFIGURATIONS OF MAIN GROUP
CATIONS IN THEIR GROUND STATE

• Cations form when the atom loses electrons from the

valence shell
Al atom = 1s22s22p63s23p1
Al3+ ion = 1s22s22p6

89
 Electron Configurations Of Cations And Anions
Of Representative Elements

Na [Ne]3s1 Na+ [Ne]

Atoms lose electrons so that
Ca [Ar]4s2 Ca2+ [Ar] cation has a noble-gas outer
electron configuration.
Al [Ne]3s23p1 Al3+ [Ne]

H 1s1 H- 1s2 or [He]

Atoms gain electrons so
that anion has a noble- F 1s22s22p5 F- 1s22s22p6 or [Ne]
gas outer electron
configuration. O 1s22s22p4 O2- 1s22s22p6 or [Ne]

N 1s22s22p3 N3- 1s22s22p6 or [Ne]

 Cations and Anions Of Representative Elements
+1
+2

+3

-3
-2
-1
 ELECTRON CONFIGURATIONS OF
TRANSITION METAL CATIONS

• When transition metals form cations, the first

electrons removed are the valence electrons, even
though other electrons were added after
• Electrons may also be removed from the sublevel closest
to the valence shell after the valence electrons
• The iron atom has two valence electrons
Fe atom = 1s22s22p63s23p64s23d6
• When iron forms a cation, it first loses its valence
electrons
Fe2+ cation = 1s22s22p63s23p63d6
• It can then lose 3d electrons
Fe3+ cation = 1s22s22p63s23p63d5
92
 Electron Configurations of Cations of
Transition Metals

When a cation is formed from an atom of a

transition metal, electrons are always removed
first from the ns orbital and then from the (n – 1)d
orbitals.

Fe: [Ar]4s23d6 Mn: [Ar]4s23d5

Fe2+: [Ar]4s03d6 or [Ar]3d6 Mn2+: [Ar]4s03d5 or [Ar]3d5
Fe3+: [Ar]4s03d5 or [Ar]3d5
 ISOELECTRONIC

Isoelectronic: Any atoms/ions that have the same

number of electrons, and hence the same ground-state
electron configuration

Na+: [Ne] Al3+: [Ne] F-: 1s22s22p6 or Ne]

O2-: 1s22s22p6 or [Ne] N3-: 1s22s22p6 or [Ne]

Na+, Al3+, F-, O2-, and N3- are all isoelectronic with Ne
 2.6 PERIODIC
CLASSIFICATION OF
ELEMENTS

• CLASSIFICATION OF ELEMENTS

• PERIODIC TABLE
 CLASSIFICATION OF
ELEMENT
• In the periodic table contains a systematic classification
and arrangement of the elements according to
increasing atomic numbers.

• According to the type of subshell being filled, the elements

can be divided into categories - the representative
elements, the noble gases, the transition elements, the
lanthanides, and the actinides.

• Elements are arranged in vertical columns called groups

and horizontal rows called periods.
 PERIODIC TABLE
• Elements in the same group of the periodic table possess
same number of valence electrons, therefore similar
valence shell electron configurations.

• As a result elements in the same group show similar

chemical properties.

• Generally, metal atoms have small numbers of electrons in

their valence shells. Except for hydrogen and helium, all s
block elements (groups I and II) are metals.
• Hydrogen is a group IA element but not an alkali
metal because it does not have any of the chemical
characteristics of a metal. It is a nonmetal.

• All d and f block elements are metals.

• A few of the p block elements like Al, Ga, Pb, Sn, In

and Bi are also metals.

• Metalloids are elements that have the physical

appearance of metals but some nonmetallic
properties. This group of elements separates the
metals from the nonmetals in the periodic table.

• Boron (B), silicon, (Si), germanium (Ge) are some

examples of metalloids.
• Non-metals are all p-block elements (groups IVA to
VIIA).
• Examples:
H2, N2, O2, F2 and Cl2 = diatomic gas
Noble gases = monatomic gas
C, P4, S8, I2 = solids with low melting points
Br2 = liquid.
• The noble gases (the group VIIIA elements) all
have a completely filled p subshell except He. The
electron configurations are 1s2 for He and ns2 np6
for the other noble gases, where n is the principal
quantum number for the outermost shell.
Classification of the Elements
 CHECKPOINT 9

An atom of a certain element has 15 electrons. Without

consulting a periodic table, answer the following questions:

(a)Whatis the ground-state electron configuration of the

element?

(b) How should the element be classified?

(c) Is the element diamagnetic or paramagnetic?

 2.7 PERIODIC VARIATIONS IN
PHYSICAL PROPERTIES
• SHIELDING EFFECT
• EFFECTIVE NUCLEAR CHARGE
• ATOMIC RADII
- TRENDS IN ATOMIC/IONIC SIZE
• IONIZATION ENERGY
-TRENDS IN IE
• ELECTRON AFFINITY
-TRENDS IN EA
• METALLIC CHARACTER
 2.7 PERIODIC VARIATIONS IN
PHYSICAL PROPERTIES

• From left to right across a period, there is a

transition from metals to metalloids to
nonmetals.

• There is also a gradual periodic variation in the

characteristic physical properties of metallic and
nonmetallic elements across a period.
FACTORS AFFECTING THE SIZE OF THE
ATOM OF AN ELEMENT

The atomic radius of an element is

determined by two factors:

(a) Shielding effect (a.k.a screening effect) of

inner shell electrons
(a) Nuclear charge
 Shielding Effect
The shielding effect of the inner shell electrons
makes the atomic radius larger:
a) The shielding effect is due to mutual repulsion
between the inner shell electrons and the outer
shell electrons.
b) Filled inner shells shield the outer electrons from
the nucleus more effectively than do electrons in
the same subshell.
• The presence of shielding electrons reduces the
electrostatic attraction between the positively charged
protons in the nucleus and the outer electrons.

• The shielding effect increases down a group as

quantum number of the valence electron increases.

• All the elements across a period have the same

shielding effect because the number of inner shells
remains the same across a period
 THE EFFECT OF
NUCLEAR CHARGE (ZEFF)
 The nuclear charge pulls
all the electron closer to
the nucleus.
 As nuclear charge increases,
the atomic radius become
smaller.
 The effective nuclear charge, Ze
ff is given by:

Zeff = Z - s

Where Z = actual charge, and

s = shielding constant (number of inner core electrons)
 THE EFFECT OF NUCLEAR
CHARGE (Zeff)

Example:
 Sodium, Na atom with 1 valence electron in 3s sublevel
which is shielded from the positively charged nucleus
by the 1s and 2s electrons.
 Therefore, experience an effective nuclear charge :
Zeff : (+11) – (10) = +1.
 Across a period, the value of Z increases while the
number of inner electrons remains the same.
Other examples:
Zeff  Z – number of inner or core electrons

Z Core Zeff Radius (pm)

Na 11 10 1 186
Decreasing
Mg 12 10 2 160 size of
atom as
Al 13 10 3 143 the Zeff
increases
Si 14 10 4 132
 Effective nuclear charge increases from left to right
of a period in the periodic table.
 The effective nuclear charge remains the same
going down the group of the periodic table.
 The effective nuclear charge calculated for elements
Be, Mg and Ca in group II are the same shown to be
equal to +2.
 The effective nuclear charge for Al, P and Cl increases
as these atoms are arranged from left to right in the
periodic table.
 Effective Nuclear Charge (Zeff)

Increasing Zeff
Same shielding effect
Increasing shielding effect
Same Zeff
 ATOMIC RADII

metallic radius covalent radius

• Atomic radius of an element is one-half the distance between the

two nuclei in two adjacent metal atoms or two like atoms joined into
a particular diatomic molecule.
 ATOMIC RADII
• Atomic radii of the elements decrease from left to right
across the periodic

• This is due to the increase in the effective nuclear

charge across the period which causes the valence
electrons to be held more strongly by the nucleus.

• Atomic radii of the elements increase going down the

group of the periodic table .

• This due to the increase in the principal quantum

number, n, of the valence electrons which causes the
outer electrons to be farther from the nucleus.
 Defining atomic size

A. The metallic radius of aluminum. B. The covalent radius of chlorine.

C. Known covalent radii and distances

between nuclei can be used to find
unknown radii.
 TRENDS IN ATOMIC SIZE
• The trends in atomic size is the same with the trends in
atomic radii.
• Going down the group, atomic size increases as the
principal quantum number n increases.
• As n increases, the probability that the outer electrons
will be further from the nucleus increases.
• From left to right across the periodic, the atomic size
decreases as the effective nuclear charge Zeff
increases.
• As Zeff increases, the outer electrons are pulled closer
to the nucleus.
Trends in Atomic Size
Atomic radii of the main-
group and transition
elements.
Periodicity of atomic radius.
Trends in Atomic Radii
CHECKPOINT 10

Using only the periodic table, rank each set of main-group elements in
order of decreasing atomic size:

(a) Ca, Mg, Sr (b) K, Ga, Ca

(c) Br, Rb, Kr (d) Sr, Ca, Rb

 Ionic Size vs. Atomic Size
• Cations are smaller than their parent atoms while
anions are larger.
• Ionic radius increases down a group as n increases.
• Cation size decreases as charge increases.
• An isoelectronic series is a series of ions that have
the same electron configuration. Within the series, ion
size decreases with increasing nuclear charge.

3- > 2- > 1- > 1+ > 2+ > 3+

Ionic vs. atomic radii.
Comparison of Atomic Radii with Ionic Radii
 TRENDS IN IONIC RADIUS
• Ions in same group have same charge
• Ion size increases down the group and decreases from
left to right across the periodic table.
• Cations smaller than neutral atoms; anions larger
than neutral atoms
• Cations smaller than anions except Rb+ & Cs+ bigger or
same size as F− and O2−
• Larger positive charge = smaller size of cation for
isoelectronic species
• Larger negative charge = larger size of anion for
isoelectronic species
Ionic Radius
 TRENDS IN CATION RADIUS
When atoms form cations, the valence electrons
are removed.
The rest of the electrons will be attracted more
strongly and closer to the nucleus.
Result: cations are smaller than their parent
atoms

• These “new valence electrons” also experience a larger

effective nuclear charge than the “old valence electrons.”
• Traversing to the right across a period increases the
effective nuclear charge for isoelectronic cations, causing
the cations to get smaller. Example: Na+ > Mg2+ > Al3+
Radii of Atom & Their Cations
 TRENDS IN ANION RADIUS

When atoms form anions, electrons are added to the

valence shell, Zeff remains unchanged. Repulsion
between electrons in the valence shell causes the
valence electron to be further from the nucleus.
Results: Anions are larger than their parent atoms

• These “new valence electrons” experience a smaller effective

nuclear charge than the “old valence electrons,” increasing the
size
• Traversing to the right across a period increases the effective
nuclear charge for isoelectronic anions, causing the anions
to get smaller. The more negative charge the anion the
larger the size. Example: N3– > O2– > F –
Radii of Atom & Their Anions
Cation is always smaller than atom from
which it is formed.
Anion is always larger than atom from
which it is formed.
The Radii (in pm) of Ions of Familiar Elements
CHECKPOINT 11
Rank each set of ions in order of decreasing size, and
explain your ranking:
+ 2− −
(a) Ca2+, Sr2+, Mg2+ (b) K , S , Cl (c) Au+, Au3+
CHECKPOINT 12

Referring to a periodic table, arrange the following atoms in

order of increasing atomic radius: P, Si, N.
CHECKPOINT 13
For each of the following pairs, indicate which one of the two species
is larger:
(a)N3− or F-
(b)Mg2+ or Ca2+
(c)Fe2+ or Fe3+
 IONIZATION ENERGY
• IONIZATION ENERGY (IE): The minimum energy
required to remove 1 mole of electron from 1 mole of
gaseous atoms or ions.
• The greater the ionization energy of an atom, the tendency
of the atom to retain the electron is greater.

• The first ionization energy is the minimum energy

required to remove the first valence electron from the
gaseous atom in its ground state.

• The second ionization energy is the energy required to

remove the second electron from the gaseous positive
ion in its ground state.
Example:

I1 + X (g) X+(g) + I1 first ionization energy

e-
I2 + X+(g) X2+(g) + e- I2 second ionization energy

I3 + X2+(g) X3+(g) + I3 third ionization energy

e-

I1 < I2 < I3
 TRENDS IN IONIZATION
ENERGY

• Atoms with a low IE tend to form cations.

• Atoms with a high IE tend to form anions (except
the noble gases).
• Ionization energy tends to decrease down a group
and increase across a period.
 TRENDS IN IONIZATION ENERGY
The first ionization energies generally increase
from left to right across the period.
As the atomic radii decrease from left to right of a
period, the outer electrons are more tightly held to the
nucleus and higher ionization energies have to be
supplied to remove the first electron

The first ionization energies decrease going down a

group in the periodic table.
As the atomic radii of the elements within a group
increase from top to bottom, the average distance
between the valence electrons and the nucleus increase
resulting in weaker nucleus-valence electron attraction.
 General Trends in First Ionization Energies

Increasing First Ionization Energy

Increasing First Ionization Energy
 ANOMALIES IN THE VARIATION OF
THE FIRST IONIZATION ENERGY
ACROSS A PERIOD

• The increase in the 1st ionization energy (I.E.) across a

period is not uniform.
• The anomalies occur in between Periods 2 and 3.
• In Period 2:
(a) From beryllium (Group 2A) to aluminium (Group 3A)
(b) From nitrogen (Group 5A) to oxygen (Group 6A)
• In Period 3:
(a) From Mg (Group 2A) to Al (Group 3A)
(b) From phosphorus (Group 5A) to sulphur (Group 6A)
 Atomic radius decreases across a period.
 So in Period 2, we expect the 1st IE of B to be larger
than Be because B has a smaller atomic radius.
 The reverse occurs, that is the ionization energy of
boron is lower than the ionization energy of
beryllium because Be (1s2 2s2) loses a 2s electron
whereas B ( 1s2 2s2 2p1) loses a 2p electron.
This is due to:
(a)The valence electrons in the filled 2s orbitals of Be are
more stable than the single valence electron in the
partially filled 2p orbitals of B.
(b)The single electron in the 2p orbital is better shielded by
the inner electrons than the electrons in 2s orbitals
(c) More energy is required to remove an electron from the
lower energy 2s orbital in Be than from the 2p orbital in B.
 In period 3, the same goes with Al (group 3A) with
smaller atomic radius are expected to have higher
I.E. than Mg (group 2A), but the reverse occurs.
 The I.E. of Al is lower than that in Mg due to the
valence electrons in the 3s orbitals of Mg are more
stable than the single valence electron in the partially
filled 3p orbital of Al
Electron in partially
filled 3p orbital is
Al: 1s2 2s2 2p6 3s2 3p1 less stable,
thus smaller Ionization
energy

2 2 6 2 Electron in 3s
Mg: 1s 2s 2p 3s orbital is more stable,
thus higher Ionization
energy
 The IE of the group 6A elements are expected to have
higher energy than the group 5A elements but the reverse
occur.
 In period 2, the first ionization energy of oxygen is lower
than nitrogen.
 The electronic structures and orbital diagram of nitrogen
and oxygen are as follows:
N: 1s2 2s2 2p3
O :1s2 2s2 2p4

This is due to:

 Half-filled and filled p orbitals have special stability.
In this case of the oxygen atom, two electrons are in the
same 2p orbital. The two parallel electrons in the same
orbital results in greater repulsion. Thus makes it easier to
remove one of these electrons compared with the
unpaired electron from a half filled 2p orbital.
• The same goes with phosphorus atom and sulphur
atom.
• The valence electrons in the 3p orbitals of phosphorus
are in 3 separate orbitals with minimum repulsion,
whereas, the paired electrons in one of the p orbitals of
and sulphur experience strong repulsion.
• Therefore , it is easier to remove the valence
electron from S than the valence electron of
phosphorus which are more stable with the least
repulsion among the valence electrons.
 Anomalies in the 1 st IE Trends

• First Ionization Energy generally increases from

left to right across a Period
• Except from 2A to 3A, 5A to 6A
  N     
Be
1s 2s 2p 1s 2s 2p

B    O     
1s 2s 2p 1s 2s 2p

Which is easier to remove an electron from, N or O? Why?

Which is easier to remove an electron from B, or Be? Why?
147
 Anomalies in the
First Ionization Energy Trends,
Be and B

   
Be Be+
1s 2s 2p 1s 2s 2p
To ionize Be you must break up a full sublevel, costs extra
energy

B    B +  
1s 2s 2p 1s 2s 2p
When you ionize B you get a full sublevel, costs
less energy

148
 Anomalies in the
First Ionization Energy Trends,
N and O

N      N+    
1s 2s 2p 1s 2s 2p

To ionize N you must break up a half-full sublevel,

costs extra energy

O      O+     
1s 2s 2p 1s 2s 2p
When you ionize O you get a half-full sublevel,
costs less energy

149
Variation of the First Ionization Energy with Atomic Number

Filled n=1 shell

Filled n=2 shell

Filled n=3 shell

Filled n=4 shell
Filled n=5 shell
CHECKPOINT 14
Using the periodic table only, rank the elements in each of the following
sets in order of decreasing IE1:
(a) Kr, He, Ar (b) Sb, Te, Sn
(c) K, Ca, Rb (d) I, Xe, Cs
CHECKPOINT 15

Name the Period 3 element with the following ionization

energies (in kJ/mol) and write its electron configuration:
IE1 IE2 IE3 IE4 IE5 IE6
1012 1903 2910 4956 6278 22,230
Successive Ionization Energies of the Elements
Lithium Through Sodium
 CHECKPOINT 16
(a) Which atom should have a smaller first ionization energy: oxygen or
sulfur?
(b) Which atom should have a higher second ionization energy: lithium
or beryllium?
The first three ionization energies of beryllium.

Beryllium has 2 valence electrons, so

IE3 is much larger than IE2.
 ELECTRON AFFINITY
• The first Electron affinity (EA) of an atom is the energy
released when one mole of atoms or ions in the gaseous
state accept 1 mole of electron to form anions.

• The more energy that is released, the larger the electron affinity.
X (g) + e- → X-(g)

• For example, the first electron affinity of fluorine is the energy

released when one mole of fluorine atoms in the gaseous state is
converted to fluoride ions.

F (g) + e- F-(g) ΔH = -328 kJ/mol EA = +328 kJ/mol

• The first electron affinities of elements are negative.
• If a gaseous atom gains an electron, heat energy is
released.
• However, if an electron is added to an anion, a strong
repulsion is felt, and the energy of the system increases.
Thus, heat is absorbed to overcome the electrostatic
repulsion between electron and negative charge on the
anion.
• Thus, the second electron affinity of any element is
always positive (endothermic).
 ELECTRON AFFINITY
The more negative the electron affinity, the greater the
tendency of the atom to accept an electron.
 TRENDS IN ELECTRON
AFFINITY
 Atoms with a low electron affinity tend to form cations. Atoms with a
high electron affinity tend to form anions.

 The trends in electron affinity are not as regular as those for atomic
size or IE.

 Within a group, electron affinity values of elements become less

negative from top to bottom.

 The increase in atomic radii causes the attractive forces of the nucleus to
decrease and so there is less tendency to accept an electron.

 The atom with the Highest Electron Affinity in any period is

halogen
Trends in Electron Affinity
TRENDS IN ELECTRON AFFINITY
 The electron affinity values become more negative
from left to right across a period.
 As the atomic radius of the element decreases, the
attractive forces of the nucleus increases, hence the
tendency to accept electrons increases.
 The electron affinities of metals (left) are generally
more positive (or less negative) than those of
nonmetals.
 Group 5A generally lower EA than expected because
extra electron must pair.
 Group 2A and 8A generally very low EA because
added electron goes into higher energy level or sublevel
Electron affinities of the main-group elements.
Behavior Patterns for IE and EA
Elements IE and EA Reasons
Reactive Have high IEs These elements attract
nonmetals and highly electrons strongly and
negative EAs. tend to form negative
ions in ionic compounds.

Reactive metals Have low IEs and These elements lose

slightly negative electrons easily and tend
EAs. to form positive ions in
ionic compounds
Noble gases Have very high These elements tend to
IEs and slightly neither lose nor gain
positive EAs electrons.
Variation of Electron Affinity With Atomic Number (H – Ba)
CHECKPOINT 17

Why are the electron affinities of the alkaline earth metals, shown in
Table 8.3, either negative or small positive values?
 ELECTRONEGATIVITY

• Electronegativity (EN) of an element is a value used to

indicate the ability of an atom to attract electrons to
itself when the atom is sharing electrons with atom of
another element
• Trends in electronegativity are similar to those for
electron affinity.
 EN value decreases from top to bottom within a group
 EN value increases from left to right across a period
Electronegativity (EN) Values for Representative Elements

Group 1A 2A 3A 4A 5A 6A 7A

Period
1 H
2.1
2 Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
3 Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
4 K Ca Ga Ge As Se Br
0.8 1.0 1.6 1.8 2.0 2.4 2.8
5 Rb Sr I
0.8 1.0 2.5
6 Cs Ba
0.7 0.9
Electronegativity Scale

170
 METALLIC CHARACTER
• Metallic character is how closely an element’s properties
match the ideal properties of a metal
• typically shiny solids with moderate to high melting points.
• good conductors of heat and electricity, and can easily be
shaped.
• tend to lose electrons and form cations, i.e., they are easily
oxidized.
• generally strong reducing agents.

• In general, metallic character

(a) decreases across a period
(b) increases down a group
Trends in metallic behavior
Trends in metallic behavior
 Metallic behavior in Group 5A(15) and Period 3.
` Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Metallic behavior decreases across the period

Metallic behavior increases down the group

The McGraw-Hill Companies, Inc./Stephen Frisch Photographer

Highest and lowest O.N.s of reactive main-group elements.
Main-group elements whose ions have noble gas electron
configurations.
 MAGNETIC PROPERTIES OF TRANSITION
METAL IONS

A species with one or more unpaired electrons exhibits

paramagnetism – it is attracted by a magnetic field.

Ag (Z = 47) ↑ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
5s 4d 5p

A species with all its electrons paired exhibits

diamagnetism – it is not attracted (and is slightly
repelled) by a magnetic field.
 Measuring the magnetic behavior of a sample.

The apparent mass of a The apparent mass of a

diamagnetic substance is paramagnetic substance increases
unaffected by the magnetic field. as it is attracted by the magnetic
field.
MAGNETIC PROPERTIES OF TRANSITION
METAL IONS
Magnetic behavior can provide evidence for the
electron configuration of a given ion.

Ti (Z = 22) ↑↓ ↑ ↑
4s 3d 4p

Ti2+ ↑ ↑
4s 3d 4p

Ti2+ has 2 unpaired electrons and is paramagnetic,

providing evidence that the 4s electrons are lost
before the 3d electrons.
Exercise 18 Writing Electron Configurations and
Predicting Magnetic Behavior of
Transition Metal Ions

PROBLEM: Use condensed electron configurations to write

the reaction for the formation of each transition
metal ion, and predict whether the ion is
paramagnetic or diamagnetic.

(a) Mn2+(Z = 25) (b) Cr3+(Z = 24) (c) Hg2+(Z = 80)

PLAN: Write the condensed electron configuration for each atom,

recalling the irregularity for Cr. Remove electrons, beginning
with the ns electrons, and determine if there are any unpaired
electrons.
 Sample Problem

SOLUTION:

(a) Mn2+(Z = 25) Mn ([Ar] 4s23d5) → Mn2+ ([Ar] 3d5) + 2e−

Since there are 5 d electrons they are all unpaired. Mn2+ is paramagnetic.

(b) Cr3+(Z = 24) Cr ([Ar] 4s13d5) → Cr3+ ([Ar] 3d3) + 3e−

Since there are 3 d electrons they are all unpaired. Cr3+ is paramagnetic.

(c) Hg2+(Z = 80) Hg ([Xe] 6s24f145d10) → Hg2+ ([Xe] 4f145d10) + 2e−

The 4f and the 5s sublevels are filled, so there are no unpaired
electrons. Hg2+ is diamagnetic.
END OF CHAPTER 2
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