Chapter 8

Electron configurations and

periodicity
Learning objectives
1. Electronic structure of atoms
- Electron spin and the Pauli exclusion principle
Define electron configuration and orbital diagram.
State the Pauli exclusion principle.
Apply the Pauli exclusion principle.
2. Building-up principle and the periodic table
Define building-up principle.
Define noble-gas core, pseudo-noble-gas core, and valence
electron.
Define main-group element and (d-block and f-block) transition
element.
Learning objectives

3. Writing electron configurations

Determine the configuration of an atom using the building-up
principle.
Determine the configuration of an atom using the period and
group number.
4. Orbital diagrams; Hund's rule
State Hund's rule.
Apply Hund's rule.
Define paramagnetic substance and diamagnetic substance.
Learning objectives
Periodicity of the Elements
5. Mendeleev's predictions from the periodic table
Describe how Mendeleev predicted the properties of
undiscovered elements.
6. Some periodic properties
State the periodic law.
State the general periodic trends in size of atomic radii.
Define effective nuclear charge.
Atomic size
Ionization energy.
Electron affinity.
7. Periodicity in the main-group elements
Define basic oxide, acidic oxide, and amphoteric oxide.
Metallic/nonmetallic character (or reactivities)
Discovery of magnetic properties of atoms
In 1921, Otto Stern and Walther Gerlach first observed electron spin
magnetism. In the diagram below, a beam of hydrogen atoms divides in
two while passing through a magnetic field. This correlates with the two
values of ms: +½ and -½.
Electron configurations
An electron configuration of an atom is a particular distribution of
electrons among available subshells.

An orbital diagram of an atom shows how the orbitals of a subshell

are occupied by electrons. Orbitals are represented with a circle;
electrons are represented with arrows up for ms= +½ or down for ms=
-½.

The Pauli exclusion principle: no two electrons in one atom can have
the same four quantum numbers.
That means that within one orbital, electrons must have opposite
spin and one orbital can hold a maximum of two electrons (with
opposite spin).
Orbital diagrams
Orbital diagrams
The building-up principle (or Aufbau principle): orbitals are filled with
electrons in the increasing order of orbital energy.
Ex: you can’t fill 2s with electrons before 1s is full
Hund’s rule: in the subshells with multiple orbitals (p,d,f) place one
electron with the same spin in each before pairing up.
Ex: the correct order to fill a p orbital is:

Pauli’s exclusion principle: you can’t have 2 electrons with the same spin
in the same orbital
Orbital diagrams
Determine which of the following orbital diagrams or electron
configurations are possible and which are impossible. Provide
explanations.
a. b.
1s 2s 2p 1s 2s
Possible Impossible; there are three
electrons in the 2s orbital.
c.
1s 2s 2p d. 1s32s1
Impossible; there are two electrons Impossible; there are three in a 2p
orbital with the same spin. electrons in 1s.
e. 1s22s12p7 f.1s22s22p63s23p63d84s2
Impossible; there are seven Possible. The 3d subshell can hold as
electrons in 2p many as three electrons.
Electron configuration and periodic table
The lowest-energy configuration of an atom is called its ground state.
Any other allowed configuration represents an excited state.

The order of orbital filling is:

1s 2s 2p 3s 3p 4s 3d 4p 5s 5d …..
Electron configuration and periodic table
Electron configuration and periodic table

The pattern that develops among the ground-state electron

configurations of the atoms, explains the periodic table.
• Noble gases (Group 8A or 18): are relatively unreactive. These
elements have a configuration in which a p subshell has just filled.
Ex: He, Ne, Ar, Kr
• Alkaline earth metals ( Group 2A): are moderately reactive
elements. Contain a noble-gas core - an inner-shell configuration
corresponding to one of the noble gases.
Ex: Mg, Ca
Electron configuration and periodic table
Elements such as boron and aluminum have three noble-gas cores as
well as three electrons with the configuration ns2np1.

The noble-gas core along with the (n – 1)d10 electrons are referred to as
a pseudo-noble-gas-core as these electrons are not involved in chemical
reactions.

The noble gas core is used in shorthand notation of electron

configuration.

A valence electron is an electron in an atom outside the noble-gas or

pseudo-noble-gas core.
Electron configuration and periodic table
There are exceptions to the electron configuration predicted by the
rules.
Ex: the configuration of chromium is [Ar]3d44s2. The actual
configuration is [Ar]3d54s1.

Basically, elements that have d4 or d9, 1 electron from the next s

orbital will move to the d orbital. A d orbital with 5 or 10 electrons
is more stable.
Electron configuration and periodic table
Ex: Write the complete electron configuration of the arsenic atom, As.
Z = 33
1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p3
valence electrons
highest energy level

We can use the position of an element in the periodic table to guide

us in writing electron configurations:
- Period number = highest energy level
- Group number (A) = number of valence electrons
Electron configuration and periodic table
Use the building-up principle to obtain the configuration for the
ground state of the gallium atom (Z = 31). Give the configuration
in complete form and determine the valence-shell
configuration.

Fill the subshells with electrons; remember that there is a total

of 31 electrons. This gives:
1s22s22p63s23p64s23d104p1

Rearranging gives: 1s22s22p63s23p63d104s24p1

The valence shell configuration is 4s24p1

Magnetic properties of atoms
Although an electron behaves like a tiny magnet, two electrons that
are opposite in spin cancel each other. Only atoms with unpaired
electrons exhibit magnetism.

This allows for the classification of atoms based on their behavior in

a magnetic field.

A paramagnetic substance is one that is weakly attracted by a

magnetic field, usually as the result of unpaired electrons.

A diamagnetic substance is not attracted by a magnetic field

generally because it has only paired electrons.
Periodic table
• Antoine Lavosier
• In the late 1790’s, compiled a list of the 23 elements known at
that time.
• J. W. Dobereiner
• In 1829, published a classification system in which he grouped
elements in triads – a set of 3 elements with similar properties.
• By this time, almost 70 elements were known. Unfortunately,
not all known elements could be grouped in triads.
• John Newlands
• In 1864, proposed an organization scheme with elements
arranged by increasing relative atomic mass.
• He observed that properties repeated every eighth element,
calling this relationship the “law of octaves” (an octave is a
group of musical notes that repeats every eighth tone).
Periodic table
Mendeleev's periodic table generally organized elements by
increasing relative atomic weight and with similar properties in
columns. Elements were missing and Mendeleev predicted their
properties based on the position in the periodic table.

When gallium, scandium, and germanium were isolated and

characterized, their properties were almost identical to those
predicted by Mendeleev for eka-aluminum, eka-boron, and eka-
silicon, respectively.

Periodic law states that when the elements are arranged by atomic
number, their physical and chemical properties there is a periodic
repetition of physical and chemical properties of elements..
Factors determining trends

Effective nuclear charge (ENC): how

strong the attraction is between the
nucleus and the electrons. More
protons in the nucleus mean higher
attractive force.

Shielding: the inner electron shells

“mask” the outer electrons from the
attractive force of the nucleus. The
further apart the electron is from the
nucleus, the lower the attractive force.
Atomic radius
It is the maximum in the radial distribution function of the outer shell.

Group (vertical column): the atomic radius increases with the period
number (with each step down you add another energy level)-
increased shielding.

Period (horizontal row): the atomic radius tends to decrease with

increasing atomic number (nuclear charge)- increased ENC
Atomic radius
Atomic radius is plotted against atomic number in the graph below.
Note the regular periodic variation.
Atomic radius
First ionization energy
The minimum energy needed to remove the highest-energy (outermost)
electron from a neutral atom.

Generally, ionization energy increases with atomic number.

Ionization energy is proportional to the effective nuclear charge divided by the

average distance between the electron and the nucleus.

Because the distance between the electron and the nucleus is inversely
proportional to the effective nuclear charge, ionization energy is proportional
to the square of the effective nuclear charge.
First ionization energy
There are small deviations occur between Groups 2A and
3A and between Groups 5A and 6A.
First ionization energy
The size of each sphere indicates the size of the
ionization energy in the figure below.
Ionization energy
Electrons can be successively removed from an atom. Each successive
ionization energy increases, because the electron is removed from a positive
ion of increasing charge.

Ionizations become difficult in some elements. This is because once the

valence electrons are removed a stable noble-gas configuration is obtained.
Electron affinity (E.A.)
It is the energy required to remove an electron from the atom's negative
ion.

It can also be defined as the negative energy obtained when the neutral
atom picks up an electron. When a stable negative ion forms, the
quantity is positive.

Electron affinities in the main-group elements show a periodic variation

when plotted against atomic number, although this variation is
somewhat more complicated than that displayed by ionization energies.

In a given period, the electron affinity rises from the Group 1A element
to the Group 7A element but with sharp drops in the Group 2A and
Group 5A elements.
Electron affinity (E.A.)

All Group 1A elements have moderately positive electron affinities.

Group 2A elements have a lesser electron affinity when compared

to 1A elements.

With the exception of the Group 5A element, the electron affinity

tends to rise from the Group 2A element to the Group 7A element.

No stable negative ions of the Group 8A elements have been

found.
Electron affinity (E.A.)
Metallic character
Elements with low ionization energies tend to be metals. Those with
high ionization energies tend to be nonmetals.

Oxides
A basic oxide reacts with acids. Most metal oxides are basic.

An acidic oxide reacts with bases. Most nonmetal oxides are acidic.

An amphoteric oxide has both acidic and basic properties.

Main groups
Hydrogen (1s1)
Its electron configuration is similar to that of Group 1A, but its
properties are different.
It is a colorless gas composed of H2 molecules.

Group 1A, alkali metals (ns1)

These elements are metals; their reactivity increases down the group.
The basic oxides formed have the general formula R2O.
Main groups
Group 2A, alkaline earth metals (ns2)
They are less chemically reactive when compared to alkali metals.
They form basic oxides with the general formula RO.

Group 3A (ns2np1)
Boron is a metalloid; all other members of Group 3A are metals.
The oxide formula is R2O3.

B2O3 is acidic.
Al2O3 and Ga2O3 are amphoteric
In2O3 and Tl2O3are basic.
Main groups
Group 4A (ns2np2)
Carbon is a nonmetal; silicon and germanium are metalloids; tin
and lead are metals.
All elements form oxides with the general formula RO2
CO2 exists as a gas
SiO2, and GeO2 exist as quartz and white sand.
SnO2 and PbO2 are amphoteric.
 Some oxides of Group IVA
PbO
PbO2
(yellow)
(dark brown)

SnO2 (white)
SiO2
(crystalline solid quartz)
Main groups
Group 5A (ns2np3)
Nitrogen and phosphorus are nonmetals; arsenic and antimony
are metalloids; bismuth is a metal.

The oxide formulas are R2O3 and R2O5, with some molecular
formulas being double these (R4O6 and R4O10).

Nitrogen, phosphorus, and arsenic oxides are acidic.

Antimony oxides are amphoteric.
Bismuth oxide is basic.
Main groups

Group 6A, chalcogens (ns2np4)

Oxygen, sulfur, and selenium are nonmetals; tellurium is a
metalloid; polonium is a metal.

They form oxides with general formulas RO2 and RO3.

Sulfur, selenium, and tellurium oxides are acidic except for TeO2,
which is amphoteric.
PoO2, though amphoteric, is more basic than TeO2.
Main groups
Group 7A, halogens (ns2np5)
These elements are reactive nonmetals, with the general molecular
formula being X2. They include fluorine, chlorine, bromine, and
iodine. All isotopes of astatine are radioactive with short half-lives.
This element might be expected to be a metalloid.

Each halogen forms several acidic oxides that are generally unstable.

Group 8A, noble gases (ns2np6)

These elements are generally unreactive and exist as gaseous atoms.