Chapter 6

Electronic Structure and Periodic Properties of

Elements
Electromagnetic Energy

In the 19th century James Clerk Maxwell developed

his theory of electromagnetic radiation and
showed that light was a visible part of the
spectrum of electromagnetic waves.

It was also determined that light could act as both

a wave or as a particle.
Electromagnetic Waves
A wave is an oscillation or periodic movement that
can transport energy from one point in space to
another.

Characteristics of waves:

1.Wavelength (denoted by λ, lambda)

2.Frequency (denoted by ν, nu)

3.Amplitude--height of the wave

4.Wavelength-- the distance between two

Units of Characteristics

Wavelengths-Electromagnetic waves have

wavelengths that fall within an enormous range-
wavelengths of kilometers (103 m) to picometers
(10−12 m)

Frequency-expressed as cycles per second [s−1], is

the hertz (Hz). Common multiples of this unit are
megahertz, (1 MHz = 1 × 106 Hz) and gigahertz
(1 GHz = 1 × 109 Hz).
Equation

frequency is given as c= 𝞴𝝂, where c is the

The relationship between wavelength and

speed of light, 𝞴 is wavelength and 𝝂, is

frequency.

The value of c is 2.998 × 108m/s.

Check Your Learning

1.One of the frequencies used to transmit and

receive cellular telephone signals in the United
States is 850 MHz. What is the wavelength in
meters of these radio waves?
Photoelectric Effect

States that electrons are ejected from the clean

surface of a metal when light having a frequency
greater than some threshold frequency was
shone on it.

Discovered by Einstein in 1905

In other words, the higher the energy of the light,

the more electrons that are dislodged,

Equation is E = h𝝂, where h is 6.626 x 10-34 J s.

Check Your Learning

2. The microwaves in an oven are of a specific

frequency that will heat the water molecules
contained in food. (This is why most plastics and
glass do not become hot in a microwave oven-they
do not contain water molecules.) This frequency is
about 3 × 109 Hz. What is the energy of one photon
in these microwaves?
Spectra
Continuous spectra show all wavelengths of
visible light, as a rainbow.

Line spectra show narrow lines of light, that are

emitted as electrons fall back to lower levels.
Each element produces its own unique line
spectra.
Bohr Model
States that electrons can only exist at discrete
distances from the nucleus of the atom.

He called the stable, lowest possible energy the

ground state.

When electrons are at higher energy, they are in

the excited state.
Heisenberg Uncertainty
Principle
This states that we can not accurately know both
the position and the speed of an electron.

We can know one or the other (with accuracy).

Quantum Numbers
Quantum numbers help us know the location of
electrons in atoms.

The principle quantum number(n) defines the

location of the energy level (shell) and size.

The angular momentum quantum number (l)

defines the type of sublevel (s=0, p=1, d=2, or
f=3).

The magnetic quantum number (ml) defines the

orbital in the sublevel.
Sublevel shapes

These shapes are predictions about

where the electron is located in the
atom.

High probability of finding the electron

in these regions.

s is spherical

p is dumbbell shaped

d is four-leaf clover shaped

 Quantum Numbers
Summary
Name Symbol Allowed Values Meaning

Principle quantum n 1, 2, 3, 4, ... Shell, the general

number region for the value
of the energy for an
electron on the
orbital

Angular momenttum l 0< l < n-1 subshell

or azimuthal
quantum number

Magnetic quantum ml -l < ml < l Orientation of orbital

number

Spin quantum ms -½, +½ Direction of spin

number
Pauli Exclusion Principle

States that no two electrons can have exactly the

same set of all four quantum numbers.

Therefore, no more than two electrons can occupy

an orbital.
Check Your Learning

3. Identify the subshell in which electrons with the

following quantum numbers are found: (a) n = 3, l
= 1; (b) n = 5, l = 3; (c) n = 2, l = 0.

4. If a shell contains a maximum of 32 electrons,

what is the principle quantum number, n ?

5. How many orbitals have l = 2 and n = 3?

Energy of Orbitals

The energy of orbitals increases as the principle

quantum number increases, n.

The energy of the orbitals increases within a shell

in the order s < p < d < f.

1s orbital fills first because it has lowest energy.

The energy increases as we move up to the 2s

and then 2p , 3s , and 3p orbitals.

Sometimes, the orbitals of an energy level overlap

Electron Configurations

The arrangement of electrons in the orbitals of an

atom is called the electron configuration of the
atom.

Configurations contain three pieces of information:

1.The number of the principal quantum shell, n

,

2.The letter that designates the orbital type

(the subshell, l ), and
Aufbau Principle

When writing an electron configuration, we begin

with hydrogen and add electrons until we get to
our element.

This procedure is called Aufabu principle.

Each added electron occupies the subshell of

lowest energy available, subject to the
limitations imposed by the allowed quantum
numbers according to the Pauli exclusion
principle.
Orbital Diagrams

Orbital diagrams are pictorial representations of

the electron configuration, showing the
individual orbitals and the pairing arrangement
of electrons.

For example, hydrogen would be

Check Your Learning

6. Identify the atoms from the electron

configurations given:
(a) [Ar]4s2 3d5
(b) [Kr]5s2 4d10 5p6

7. Give the full electron configuration for the

following elements.
(a)Calcium
(b)Carbon
(c)Molybdenum
(d)Mercury
Exceptions to Filling Order
Most elements fill according to the rules we have
laid out.

Exceptions occur

For instance, the electron configurations of the

transition metals chromium (Cr) and copper (Cu).

Exceptions involve subshells with very similar

energy, and small effects can lead to changes in
the order of filling.

In the case of Cr and Cu, we find that half-filled

Periodic Table

The periodic table arranges atoms based on

increasing atomic number so that elements with
the same chemical properties recur periodically.

When their electron configurations are added to

the table we see a periodic recurrence of similar
electron configurations in the outer shells of
these elements.

Because they are in the outer shells of an atom,

valence electrons play the most important role
Valence Electrons

Elements in any one group (or column) have the

same number of valence electrons.

The similarity in chemical properties among

elements of the same group occurs because they
have the same number of valence electrons.

It is the loss, gain, or sharing of valence electrons

that defines how elements react.
Categories of Elements

Elements can be categorized based on which

orbitals are counted in the valence shell, or
highest energy level of an atom.

There are three main categories of elements on

the periodic table:

Main group elements (representative elements) enters s or

p

Transition elements (transition metals) enter d

Inner transition elements enter f

Electron Configurations of
Ions
A cation (positively charged ion) forms when one
or more electrons are removed.

For main group elements, the electrons that were added last
are the first electrons removed.

For transition metals and inner transition metals, however,

electrons in the s orbital are easier to remove

An anion (negatively charged ion) forms when one

or more electrons are added.

The added electrons fill in the order predicted by the Aufbau

Check Your Learning

8. Which ion with a +2 charge has the electron

configuration 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d5 ?
Which ion with a +3 charge has this configuration?
Periodic Trends
The elements in groups (vertical columns) of the
periodic table exhibit similar chemical behavior.
This similarity occurs because the members of a
group have the same number and distribution of
electrons in their valence shells.

However, there are also other patterns in chemical

properties on the periodic table.

The trends we will consider are (1) size (radius) of

atoms and ions, (2)ionization energies, and (3)
electron affinities.
Variation in Covalent Radius

The covalent radius, which is defined as one-

half the distance between the nuclei of two
identical atoms when they are joined by a
covalent bond.

The size of the atom (and its covalent radius)

must increase as we increase the distance of the
outermost electrons from the nucleus.

As we travel down a column radius gets larger.

However, as we move across the period, the
Effective Nuclear Charge
(Zeff)
This is the pull exerted on a specific electron by
the nucleus, taking into account any electron–
electron

repulsions. For hydrogen, there is only one electron

and so the nuclear charge (Z ) and the effective
nuclear charge (Zeff ) are equal.

For all other atoms, the inner electrons partially

shield the outer electrons from the pull of the
nucleus,and thus: Zeff = Z − shielding.
 Shielding

Shielding is the blocking of the pull of the nucleus for an electron by

being in between the two.

Electrons that are in the same valence shell do not shield.

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) experienced by

electrons on the right side of the periodic table draws them closer
Check Your Learning

9. Give an example of an atom whose size is

smaller than fluorine.
Ionic Radius: Cations
Ionic radius is the measure used to describe the
size of an ion.

A cation always has fewer electrons and the same

number of protons as the parent atom; it is
smaller than the atom from which it is derived.

As electrons are removed from the outer valence

shell, the remaining core electrons occupying
smaller shells experience a greater effective
nuclear charge Zeff and are drawn even closer to
the nucleus.
Ionic Radius: Anions
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 .
Ionization Energy
The amount of energy required to remove the
most loosely bound electron from a gaseous
atom in its ground state is called its first
ionization energy (IE1 ).

The first ionization energy for an element, X, is the

energy required to form a cation with +1 charge.

Energy is always required to remove electrons

from atoms or ions, so ionization processes are
endothermic and IE values are always positive.

Within a period, the IE1 generally increases with

Exceptions
Note that the ionization energy of boron (atomic
number 5) is less than that of beryllium (atomic
number 4) even though the nuclear charge of
boron is greater by one proton.

This is explained because the energy of the

subshells increases as l increases, due to
penetration and shielding.

Within any one shell, the s electrons are lower in

energy than the p electrons.
Other Exceptions

Another deviation occurs as orbitals become more

than one-half filled. This has to do with stability.

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.

Likewise, removing an electron from a cation with

a higher positive charge is more difficult than
removing an electron from an ion with a lower
Successive Ionization
Energies
It is possible to remove more electrons, after the
first electron has been removed.

However, successive ionization energies for one

element always increase.
Check Your Learning

10. Which has the lowest value for IE1 : O, Po, Pb,
or Ba? Explain.
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).

How much an element loves electrons.

Value can either be positive or negative.