Chapter 5 The Atom: Electronic

Structure

The electron configuration of an atom is the representation of the

arrangement of electrons distributed among the orbital shells and
subshells. Commonly, the electron configuration is used to describe
the orbitals of an atom in its ground state, but it can also be used to
represent an atom that has ionized into a cation or anion by
compensating with the loss of or gain of electrons in their
subsequent orbitals. Many of the physical and chemical properties of
elements can be correlated to their unique electron configurations.
The valence electrons, electrons in the outermost shell, are the
determining factor for the unique chemistry of the element.
Purpose of Electron Configurations
• When atoms come into contact with one another, it is the
outermost electrons of these atoms, or valence shell, that
will interact first. An atom is least stable (and therefore
most reactive) when its valence shell is not full. The valence
electrons are largely responsible for an element's chemical
behavior. Elements that have the same number of valence
electrons often have similar chemical properties.
• Electron configurations can also predict stability. An atom is
most stable (and therefore unreactive) when all its orbitals
are full. The most stable configurations are the ones that
have full energy levels. These configurations occur in the
noble gases. The noble gases are very stable elements that
do not react easily with any other elements. Electron
configurations can assist in making predictions about the
ways in which certain elements will react, and the chemical
compounds or molecules that different elements will form.
The Aufbau section discussed how that
electrons fill the lowest energy orbitals first, and
then move up to higher energy orbitals only
after the lower energy orbitals are full. However,
there a problem with this rule. Certainly, 1s
orbitals should be filled before 2s orbitals,
because the 1s orbitals have a lower value of n,
and thus a lower energy. What about the three
different 2p orbitals? In what order should they
be filled? The answer to this question involves
Hund's rule.
• Hund's rule states that:
1. Every orbital in a sublevel is singly occupied before any
orbital is doubly occupied.
2. All of the electrons in singly occupied orbitals have the
same spin (to maximize total spin).
When assigning electrons to orbitals, an electron first seeks to
fill all the orbitals with similar energy (also referred to as
degenerate orbitals) before pairing with another electron in a
half-filled orbital. Atoms at ground states tend to have as
many unpaired electrons as possible. In visualizing this
process, consider how electrons exhibit the same behavior as
the same poles on a magnet would if they came into contact;
as the negatively charged electrons fill orbitals, they first try to
get as far as possible from each other before having to pair
up.
• Consider the correct electron configuration of
the nitrogen (Z = 7) atom: 1s2 2s2 2p3
The p orbitals are half-filled; there are three
electrons and three p orbitals. This is because the
three electrons in the 2p subshell will fill all the
empty orbitals first before pairing with electrons in
them.
Keep in mind that elemental nitrogen is found in
nature typically as dinitrogen, N2, which
requires molecular orbitals instead of atomic orbitals
as demonstrated above.
Next, consider oxygen (Z = 8) atom, the element after nitrogen in the same period; its
electron configuration is: 1s2 2s2 2p4

Oxygen has one more electron than nitrogen; as

the orbitals are all half-filled, the new electron
must pair up. Keep in mind that elemental oxygen
is found in nature typically as dioxygen, O2O2,
which has molecular orbitals instead of atomic
orbitals as demonstrated above.
• Hund's Rule Explained
According to the first rule, electrons always enter an
empty orbital before they pair up.
Electrons are negatively charged and, as a result,
they repel each other.
Electrons tend to minimize repulsion by occupying
their own orbitals, rather than sharing an orbital
with another electron.
Furthermore, quantum-mechanical calculations
have shown that the electrons in singly occupied
orbitals are less effectively screened or shielded
from the nucleus.
Electron shielding is further discussed in the next
section.
For the second rule, unpaired electrons in singly
occupied orbitals have the same spins.
Technically speaking, the first electron in a
sublevel could be either "spin-up" or "spin-
down.“
Once the spin of the first electron in a sublevel
is chosen, however, the spins of all of the other
electrons in that sublevel depend on that first
spin.
To avoid confusion, scientists typically draw the
first electron, and any other unpaired electron,
in an orbital as "spin-up."
• Consider the electron configuration for carbon
atoms: 1s22s22p2: The two 2s electrons will
occupy the same orbital, whereas the two 2p
electrons will be in different orbital (and aligned
the same direction) in accordance with Hund's
rule.
• Consider also the electron configuration of
oxygen. Oxygen has 8 electrons. The electron
configuration can be written as 1s22s22p4. To
draw the orbital diagram, begin with the
following observations: the first two electrons
will pair up in the 1s orbital; the next two
electrons will pair up in the 2s orbital. That leaves
4 electrons, which must be placed in the 2p
orbitals.
• According to Hund’s rule, all orbitals will be
singly occupied before any is doubly occupied.
Therefore, two p orbital get one electron and
one will have two electrons. Hund's rule also
stipulates that all of the unpaired electrons
must have the same spin. In keeping with
convention, the unpaired electrons are drawn
as "spin-up", which gives
• The Pauli Exclusion Principle states that, in an
atom or molecule, no two electrons can have
the same four electronic quantum numbers.
As an orbital can contain a maximum of only
two electrons, the two electrons must have
opposing spins. This means if one is assigned
an up-spin ( +1/2), the other must be down-
spin (-1/2).
• Electrons in the same orbital have the same
first three quantum numbers,
e.g., n=1n=1, l=0l=0, ml=0ml=0 for the
1s subshell. Only two electrons can have these
numbers, so that their spin moments must be
either ms=−1/2ms=−1/2 or ms=+1/2ms=+1/2.
If the 1s orbital contains only one electron, we
have one msms value and the electron
configuration is written as 1s1 (corresponding
to hydrogen). If it is fully occupied, we have
two msms values, and the electron
configuration is 1s2(corresponding to helium).
Visually these two cases can be represented as
As you can see, the 1s and 2s subshells for beryllium
atoms can hold only two electrons and when filled, the
electrons must have opposite spins. Otherwise they will
have teh same four quantum numbers, in violation of
the Pauli Exclusion Principle.
• Electron configuration of an atom represents
that how the electrons are distributed in its
atom among the orbits (shells) and sub shells.
• The electron configuration of an atom is very
important as it helps to predict the chemical,
electrical and magnetic behavior of substance.
Based on electron configuration of atom, we
can predict that whether two substances will
chemically react or not and if they react, we
can also predict what kind of reaction is likely
to be happen and how strong it will be.
• The electron configuration of an atom, describes the
arrangement of electrons in space around the nucleus.
The electrons are distributed over different energy
level. These energy levels are called the shell or orbits.
Basically the distribution of electrons over various
shells (energy levels) is such that, the overall energy of
all electrons of an atom remains minimum for stability
of the atom.
The electron distribution over various energy level is
governed by the following rules –
• The maximum number of electrons in any main energy
level (shell) is given by, ‘2n2’, where, n is an integer and
representing the “principal quantum number”. For
different main energy levels the value of ‘n’ and
maximum number of electrons are given in table
below-
 Principal
Energy level or Orbit Maximum Number of
Sl. No. quantum
(shell) electrons (2n2)
number ‘n’

1 K 1 2×12 = 2

2 L 2 2×22 = 8

3 M 3 2×32 = 18

4 N 4 2×42 = 32
The each main shell (energy level) is subdivided
into sub shells. These sub shell are called
orbitals. These sub shells /orbitals are
designated by s, p, d, f etc. with corresponding
orbital quantum number, l = 0, 1, 2, 3, 4,…..(n-1)
etc. The number of sub shells in any main shell is
equal to “principal quantum number” ‘n’.
The maximum electron capacity of sub shells is governed formula of 2(2l + 1). The
capacity of sub shells are given in table below-

Quantum Electron capacity of sub shell

Sl. 2(2l+1)
Subshell number
No.
(l)

1 s 1 2(2 × 0+1) = 2

2 p 2 2(2 × 1+1) = 6

3 d 3 2(2 × 2+1) = 10

4 f 4 2(2 × 3+1) = 14
 Chemical Atomic Distribution of electrons over orbits Electron configuration of
Element
Symbol No. (shells), 2n2 atom

K(n=1) L(n=2) M(n=3) N(n=4)

Hydrogen H 1 1 0 0 0 1s1

Helium He 2 2 0 0 0 1s2

Lithium Li 3 2 1 0 0 1s2 2s1

Beryllium Be 4 2 2 0 0 1s2 2s2

Boron B 5 2 3 0 0 1s2 2s2 2p1

Carbon C 6 2 4 0 0 1s2 2s2 2p2

Nitrogen N 7 2 5 0 0 1s2 2s2 2p3

Oxygen O 8 2 6 0 0 1s2 2s2 2p4

Fluorine F 9 2 7 0 0 1s2 2s2 2p5

Neon N 10 2 8 0 0 1s2 2s2 2p6

Sodium Na 11 2 8 1 0 1s2 2s2 2p6 3s1

Magnesium Mg 12 2 8 2 0 1s2 2s2 2p6 3s2

Aluminum Al 13 2 8 3 0 1s2 2s2 2p6 3s23p1

Silicon Si 14 2 8 4 0 1s2 2s2 2p6 3s23p2

Phosphorus P 15 2 8 5 0 1s2 2s2 2p6 3s23p3

Sulphur S 16 2 8 6 0 1s2 2s2 2p6 3s23p4

Chlorine Cl 17 2 8 7 0 1s2 2s2 2p6 3s23p5

Argon Ar 18 2 8 8 0 1s2 2s2 2p6 3s23p6

1s2 2s2 2p6 3s23p6 4s1

Potassium K 19 2 8 8 1 Or
[Ar]4s1

1s2 2s2 2p6 3s23p6 4s2

Calcium Ca 20 2 8 8 2
Or
• Aufbau Principle
“Aufbau” is a German word whose meaning is
“building up”. Therefore, “Aufbau Principle” is
also called “building up principle”. According
to this principle, the electrons occupy the
orbitals in the order of increasing energy. The
increasing energy order of various orbitals and
order of occupation is as below –
1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s<4f<
5d<6p<7s<5f<6d<7p To simplify the
understanding of order of increasing energy,
“Madelung’s rule” is used, which is given
below-
• Based on above rules, the electron
configuration of atom of some elements is
shown in table below-
• Where, [Ar] = 1s2 2s2 2p6 3s2 3p6 represents
the electron configuration of Argon which is
having completely filled 3-shells. It is used to
simplify the electron configuration of
elements of higher atomic number.