GENERAL CHEMISTRY

Lecture 4

Module: Chemistry/Biochemistry

Academic Year : 2022-2023

www.um6ss.ma

Prof. Tarik OUCHBANI 1

 9. Atomic Orbitals

95% of the time (or any other percentage you choose), the electron will be
found within a fairly easily defined region of space quite close to the
nucleus. Such a region of space is called an orbital. You can think of an
orbital as being the region of space in which the electron lives.

The orbital occupied by the hydrogen electron is called a 1s

orbital. The "1" represents the fact that the orbital is in the energy level
closest to the nucleus. The "s" tells you about the shape of the orbital.
s orbitals are spherically symmetric around the nucleus .
 9. Atomic Orbitals

The 2s orbital is similar to a 1s orbital except that the region where there
is the greatest chance of finding the electron is further from the nucleus -
this is an orbital at the second energy level.

2s (and 3s, 4s, etc) electrons spend some of their time closer to the nucleus
than you might expect. The effect of this is to slightly reduce the energy of
electrons in s orbitals. The nearer the nucleus the electrons get, the lower
their energy.

3s, 4s (etc) orbitals get progressively further from the nucleus.

 9. Atomic Orbitals

« P » orbitals:

Not all electrons inhabit s orbitals (in fact, very few electrons live in s
orbitals). At the first energy level, the only orbital available to electrons is
the 1s orbital, but at the second level, as well as a 2s orbital, there are
also orbitals called 2p orbitals.
the “p” orbital shows where there is a 95% chance of finding a particular
electron.
At any one energy level it is possible to have three absolutely equivalent
“p” orbitals pointing mutually at right angles to each other. These are
arbitrarily given the symbols px, py and pz. This is simply for convenience
- what you might think of as the x, y or z direction changes constantly as
the atom tumbles in space.
 9. Atomic Orbitals
p orbitals:
The p orbitals at the second energy level are called 2px, 2py and 2pz. There
are similar orbitals at subsequent levels - 3px, 3py, 3pz, 4px, 4py, 4pz and so
on.
 9. Atomic Orbitals
d and f orbitals:

In addition to s and p orbitals, there are two other sets of orbitals which
become available for electrons to inhabit at higher energy levels. At the third
level, there is a set of five d orbitals (with complicated shapes and names) as
well as the 3s and 3p orbitals (3px, 3py, 3pz). At the third level there are a
total of nine orbitals altogether.

At the fourth level, as well the 4s and 4p and 4d orbitals there are an
additional seven f orbitals - 16 orbitals in all. s, p, d and f orbitals are then
available at all higher energy levels as well.

For the moment, you need to be aware that there are sets of five d orbitals at
levels from the third level upwards, but you probably won't be expected to
draw them or name them. Apart from a passing reference, you won't come
across f orbitals at all.
 9. Atomic Orbitals
d and f orbitals:
 10. Electronic structure of atoms
The electron configuration of an element describes how electrons are
distributed in its atomic orbitals. Electron configurations of atoms follow a
standard notation in which all electron-containing atomic subshells (with the
number of electrons they hold written
in superscript) are placed
in a sequence.
For example, the electron configuration
of sodium is 1s22s22p63s1.
 10. Electronic structure of atoms
Fitting electrons into orbitals
You can think of an atom as a very bizarre house (like an inverted pyramid!)
- with the nucleus living on the ground floor, and then various rooms
(orbitals) on the higher floors occupied by the electrons. On the first floor
there is only 1 room (the 1s orbital); on the second floor there are 4 rooms
(the 2s, 2px, 2py and 2pz orbitals); on the third floor there are 9 rooms (one
3s orbital, three 3p orbitals and five 3d orbitals); and so on. But the rooms
aren't very big . . . Each orbital can only hold 2 electrons.
A convenient way of showing the orbitals that the electrons live in is to draw
"electrons-in-boxes".

"Electrons-in-boxes"
Orbitals can be represented as boxes with the electrons in them shown as
arrows. Often an up-arrow and a down-arrow are used to show that the
electrons are in some way different.
 10. Electronic structure of atoms
A 1s orbital holding 2 electrons would be drawn as shown on the right,
but it can be written even more quickly as 1s2. This is read as "one s
two" - not as "one s squared".

You mustn't confuse the two numbers in this notation:

 10. Electronic structure of atoms

Electron Configurations are useful for:

•Determining the valency of an element.

•Predicting the properties of a group of elements (elements with similar
electron configurations tend to exhibit similar properties).
•Interpreting atomic spectra.

This notation for the distribution of electrons in the atomic orbitals of atoms
came into practice shortly after the Bohr model of the atom was presented
by Ernest Rutherford and Niels Bohr in the year 1913.
 10. Electronic structure of atoms

Writing Electron Configurations

Shells
The maximum number of electrons that can be accommodated in a shell
is based on the principal quantum number (n). It is represented by the
formula 2n2, where ‘n’ is the shell number. The shells, values of n, and the
total number of electrons that can be accommodated are tabulated below.
 10. Electronic structure of atoms

Writing Electron Configurations

Subshells

•The subshells into which electrons are distributed are based on the
azimuthal quantum number (denoted by ‘l’).
•This quantum number is dependent on the value of the principal quantum
number, n. Therefore, when n has a value of 4, four different subshells are
possible.
•When n=4. The subshells correspond to l=0, l=1, l=2, and l=3 and are
named the s, p, d, and f subshells, respectively.
•The maximum number of electrons that can be accommodated by a
subshell is given by the formula 2*(2l + 1).
•Therefore, the s, p, d, and f subshells can accommodate a maximum of 2,
6, 10, and 14 electrons, respectively.
All the possible subshells for values of n up to 4 are tabulated below.
 10. Electronic structure of atoms

Writing Electron Configurations

Subshells
 10. Electronic structure of atoms
Writing Electron Configurations
Notation:
•The electron configuration of an atom is written with the help of subshell
labels.
•These labels contain the shell number (given by the principal quantum
number), the subshell name (given by the azimuthal quantum number) and the
total number of electrons in the subshell in superscript.
•For example, if two electrons are filled in the ‘s’ subshell of the first shell, the
resulting notation is ‘1s2’.
•With the help of these subshell labels, the electron configuration of
magnesium (atomic number 12)
• can be written as 1s2 2s2 2p6 3s2.
 10. Electronic structure of atoms
Filling of Atomic Orbitals

Aufbau Principle:

•This principle is named after the German word ‘Aufbeen’ which means
‘build up’.
•The Aufbau principle dictates that electrons will occupy the orbitals having
lower energies before occupying higher energy orbitals.
•The energy of an orbital is calculated by the sum of the principal and the
azimuthal quantum numbers.
•According to this principle, electrons are filled in the following order: 1s, 2s,
2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p…
The order in which electrons are filled in atomic orbitals as per the Aufbau
principle is illustrated below.
 10. Electronic structure of atoms
Filling of Atomic Orbitals
 10. Electronic structure of atoms
Filling of Atomic Orbitals

It is important to note that there exist many exceptions to the Aufbau principle such
as chromium and copper. These exceptions can sometimes be explained by the
stability provided by half-filled or completely filled subshells.
 10. Electronic structure of atoms
Filling of Atomic Orbitals

Pauli Exclusion Principle

•The Pauli exclusion principle states that a maximum of two electrons,
each having opposite spins, can fit in an orbital.
•This principle can also be stated as “no two electrons in the same atom
have the same values for all four quantum numbers”.
•Therefore, if the principal, azimuthal, and magnetic numbers are the
same for two electrons, they must have opposite spins.
Hund’s Rule
•This rule describes the order in which electrons are filled in all the orbitals
belonging to a subshell.
•It states that every orbital in a given subshell is singly occupied by
electrons before a second electron is filled in an orbital.
•In order to maximize the total spin, the electrons in the orbitals that only
contain one electron all have the same spin (or the same values of the
spin quantum number).
 10. Electronic structure of atoms
Filling of Atomic Orbitals

An illustration detailing the manner in which electrons are filled in

compliance with Hund’s rule of maximum multiplicity is provided above.
 10. Electronic structure of atoms
Filling of Atomic Orbitals
Example: Electronic configuration (or electronic structure) of nitrogen N
and of oxygen O