Chapter 2

Electron configuration and chemical

periodicity
2.1. Electron configuration
2.1.1. Orbital energy levels in a many- electron atom
✓The Schrodinger equation is much more
complicated for many-electron atoms
✓ The Schrodinger does not give the exact solutions
for many-electron atoms
✓To solve this equation for we must use symplying
approximations
✓The solutions of the Schrodinger are wave functions
and the corresponding energies
* The orbitals resemble the atomic orbitals of
hydrogen. Each electron also is described by the same
combinations of four quantum numbers (n, l, ml, ms)
* Energies of the orbitals are different from that in
hydrogen. The energy is dependent on two quantum
numbers: n and l (no phenomena is so-called
degeneration in energy)
• The energy of the orbitals increases with
increasing value of n.
• For a given value of n, energy increases with
increasing value of l
That means, within a main shell, the s subshell is
lowest in energy, the p subshell is the next lowest
then the d, f and so on
Within a given value of n, sublevels increase in
energy in the order:
Ens< Enp < End< Enf
Fig. 5. Orbital energy levels in a many-electron atom

The energies of orbitals

are closer together at
higher energies

The largest energy gap is

between 1s and 2s
2.1.2. The shielding effect in many electron atoms
✓ In many electron atoms, each electron not only
attracts to the nuclear, but also repel other electrons
✓ This repulsion counteracts the nuclear attraction
somewhat, making each electron easier to remove
✓ Each electron shields the other electrons
somewhat from the nuclear
✓ Shielding reduces the full nuclear charge to an
effective nuclear charge (Zeff )
✓ Much greater shielding is provided by inner
electrons. Since they spend nearly all their time
between the outer electrons and the nucleus. Inner
electrons shield outer electrons very effectively
2.1.2. The shielding effect in many electron atoms
+ An outer electron can spend time existing nearly the
nucleus. The phenomenon is called penetrating.
+ The penetrating decreases as the principle quantum
number n increases. The electron with the large value
of n will have less penetrating as compared to the
electron with small n and will be more shielded
+ For the same principle quantum number n, the
penetrating effect decreases and the shielding effect
increases as l increases by the order: ns> np > nd > nf
2.1.3. The general rules for arranging electrons in
atomic orbitals
✓ We must know electron configuration for many-
electron atoms (how the electrons are distributed
among the various atomic orbitals)
✓ The arrangement of electrons in an atom will obey
three following rules:
- The pauli exclusion principle
- The stable principle
- Hund’s rule
2.1.3.1. The Pauli exclusion principle
Statement:
No two electrons in an atom may have the same set
of four quantum numbers.
➢In other words, given values of the quantum
numbers n, l, ml, ms can characterize only one electron.
➢It follows directly from Pauli’s principle that two
electrons can be presented in one orbital with ms=+1/2
and ms=-1/2
s subshell (1 orbital) 2e
p subshell (3 orbitals) 6e
d subshell (5 orbitals) 10e
f subshell (7 orbitals) 14 e
2.1.3.2. The stable principle
In a multi-electron atom, electrons are first filled with orbitals
in the lowest energy level by the order as follows:
1s < 2s < 2p < 3s < 3p < 4s  3d < 4p < 5s  4d < 5p < 6s 4f 
5d < 6p < 7s, ….
There are two general rules help to predict electron
configuration:
+ Electrons are assigned to orbitals in order of increasing
value of (n+l)
+ For subshells with the same value of (n+l), electrons are
assigned first to the subshell with lower n.
Due to the early saturation,1e in 4f will shift to 5d
therefore the configuration of the element (Z=57)
6s2 5d1 instead of 6s24f1 : Lanthane
Z=58: 6s2 4f2
due to E(4f) E(5d), so 1e in 4f will promote to 5d, so the
configuration of the element (Z=58) will be:
6s24f15d1
2.1.3.3. Hund’s rule
Statement
The most stable arrangement of electrons in
subshells is the one with the greatest number of
parallel spins

Note: the Hund rule is applied for the incomplete

subshell
np3
3/2

-3/2
2.1.4. Write the electron configuration of an atom
Remember two principles and one rule:
1. The Pauli exclusion principle
2. The stable principle
3. The Hund’s rule
To write electron configurations have to know:
- The total number of electrons in the atom (the
atomic number Z)
- Place electrons in orbitals according to the stable
principle (the energy order of orbitals)
- Know the maximum number of electrons in a
subshell: 2e -s subshell, 6e- p subshell; 10e –d; 14e- f
To write orbital diagram, you should:
- Firstly, write electron configuration
- Write orbital diagram and for an outer unfilled
subshell electron will be placed based on the Hund’s
rule
* For example:
N (Z=7): 1s22s22p3

Note: When electrons are placed to orbitals obeying

the principles and Hund’s rule, the atom in its ground
state with the lowest energy.
2.2. Periodic table
2.2.1. The recurrence in electron structure of atoms in
periodic table
- 1869, Dmitri Mendeleev (Russian 1834-1907)
introduced a periodic table based on recurence of the
element properties.
- He discovered the period law and arranged 63
elements into a periodic table (by increasing atomic
masses).
Some examples of grouping by properties:
- Li, Na, K were originally grouped together, because
they are all soft, malleable, reactive metals
- He, Ne, Ar were grouped together because of their
inertness
+ Some glaring inconsistencies:
The a.m of Ar (39.95 amu) is greater than that of K
(39.1amu), if the elements were arranged according
to a. m, Ar would appear in the position occupied by
K in modern periodic table.
But no chemist would place Ar, an inert gas in the
same group with Li and Na (two very active metals)
+ This suggested that some fundamental propety
other than atomic mass must be the basic of
periodicity
✓ In a modern periodic table: the elements were
arranged with the increasing atomic numbers Z
✓ When arranging elements by increasing of atomic
numbers and write electron configuration, it was
found that a new shell of electrons will be filled
after a row of elements
Row 1:
Z = 1: H 1s1
Z = 2: He 1s2 - complete the 1st shell
containing an orbital 1s. The elements were placed in
1st row (1st period )
Row 2:
Z = 3: Li 1s22s1 ([He] 2s1) - the appearance
of a new shell
Z = 4: Be 1s22s2 ([He] 2s2)
Z = 5: B 1s22s22p1 ([He] 2s22p1)
Z = 6: C 1s22s22p2 ([He] 2s22p2)
Z = 7: N 1s22s22p3 ([He] 2s22p3)
Z = 8: O 1s22s22p4 ([He] 2s22p4)
Z = 9: F 1s22s22p5 ([He] 2s22p5)
Z = 10: Ne 1s22s22p6 ([He] 2s22p6)- complete the
second shell
8 elements complete the second shell and were placed in the
second period.
Row 3:
Z = 11: Na [Ne] 3s1 - the appearance of a new
shell
Z = 12: Mg [Ne] 3s2
…….
…….
Z = 18: Ar [Ne]3s23p6 - complete the third
shell
After Ar, the next electrons start to fill the lowest
sublevel of the 4th level (4s) instead of the highest
sublevel of the third level (3d).
Row 4:
Z = 19: K [Ar] 4s1 - the appearance of a new
shell (new period)
Z = 20: Ca [Ar]4s2
In the 4th period, 10 elements will be appeared since the
next 10e will be filled 3d sublevel of the inner shell.
Z = 21: Sc [Ar] 4s23d1
Z = 22: Ti [Ar] 4s23d2
Z = 23: V [Ar] 4s23d3
Z = 24: Cr [Ar] 4s23d4 → 4s13d5 (experimental
evidence showed that 4s13d5 is more favourable than
4s23d4)
Z=25: Mn [Ar] 4s23d5
Z = 29: Cu [Ar] 4s23d9 → 4s13d10
Z = 30: Zn [Ar] 4s23d10
Z = 31: Ga [Ar] 4s23d104p1
Z = 32: Ge [Ar] 4s23d104p2
.
.
Z = 36: Kr [Ar] 4s23d104p6 - complete the 4th
shell
Row 5:
Firstly, 5s orbital, then five 4d orbitals and three 5p
orbitals will fill to take us to xenon
There are all 18 elements in the 4th and 5th periods
Remarks:
* The atomic number Z increased continuously, but the
electron configuration of atoms periodically repeated after a
row of elements
* The formation of the period: Period is a row of chemical
elements, starting with the element having the outermost
orbital ns1 and finishing by the element having the outermost
orbital ns2np6 (except for the 1st period)
* The number of a period = the number of the electron shells
= the principle quantum number n of the outermost shell
* The periodic property in electronic structure of the
elements exhibit clear development.
+ 1st period: there are only two elements (fill the 1s
subshell)
+ 2nd, 3rd period: there are 8 elements in every period (fill
the subshells: 2s, 2p, 3s, 3p)
+ 4th and 5th period: there are 18 elements in every period
+ 6th period: there are 32 elements (fill 6s, 4f, 5d, 6p)
+ 7th period: not complete (fill 7s, 5f, 6d, 7p)
➢Since 2016, the periodic table has 118 confirmed elements, from element
1 (hydrogen) to 118 (oganesson). Elements 113, 115, 117 and 118, the most
recent discoveries, were officially confirmed by the International Union of
Pure and Applied Chemistry (IUPAC) in December 2015.
2.2.2. The periodic table
Two principles to build the periodic table:
1. In the periodic table, elements are arranged by
increasing the atomic numbers, therefore the periods
were formed. Each period includes one or two rows.
2. In the periodic table, elements with the same
electron configuration of the outermost shell are
placed in one column, called a group
The periodic table includes 18 columns, but has only
16 groups: 8A groups (main groups) and 8B groups
(secondary groups).