General chemistry

lecture 3
Quantum numbers
 Principal Quantum number(n)

• This quantum number is the one on which the energy of an electron in an

atom principally depends; it can have any positive value: 1, 2, 3, and so
on.
• The energy of an electron in an atom depends principally on n. The
smaller n is, the lower the energy.
• The size of an orbital also depends on n. The larger the value of n is, the
larger the orbital. Orbitals of the same quantum state n are said to belong
to the same shell. Shells are sometimes designated by the following
letters:
 Angular Momentum Quantum Number (l )
(Also Called Azimuthal Quantum Number)
• This quantum number distinguishes orbitals of given n having different shapes; it can
have any integer value from 0 to n 1. Within each shell of quantum number n, there
are n different kinds of orbitals, each with a distinctive shape denoted by an l quantum
number. For example, if an electron has a principal quantum number of 3, the possible
values for l are 0, 1, and 2. Thus, within the M shell (n=3), there are three kinds of
orbitals, each having a different shape.
• Although the energy of an orbital is principally determined by the n quantum number,
the energy also depends somewhat on the l quantum number (except for the H atom).
For a given n, the energy of an orbital increases with l. Orbitals of the same n but
different l are said to belong to different subshells of a given shell. The different
subshells are usually denoted by letters as follows:
 Magnetic Quantum Number (ml)

• This quantum number distinguishes orbitals of given n and l—that is, of given energy
and shape but having a different orientation in space; the allowed values are the
integers from l to l.
• For l=0 (s subshell), the allowed ml quantum number is 0 only; there is only one
orbital in the s subshell. For l =1 ( p subshell), ml 1, 0, and 1; there are three different
orbitals in the p subshell.
• The orbitals have the same shape but different orientations in space. all orbitals of a
given subshell have the same energy. Note that there are 2l 1 orbitals in each subshell
of quantum number l.
 Shapes of different
orbitals
The orbital does not abruptly end at some particular
distance from the nucleus. An atom, therefore, has an
indefinite extension, or “size.” We can gauge the
“size” of the orbital by means of the 99% contour. The
electron has a 99% probability of being found within
the space of the 99% contour (the sphere indicated by
the dashed line in the diagram).
 Spin Quantum Number (ms)
• This quantum number refers to the two possible orientations of the
spin axis of an electron; possible values are -1/2 and +1/2. An
electron acts as though it were spinning on its axis like the earth.
Such an electron spin would give rise to a circulating electric
charge that would generate a magnetic field. In this way, an
electron behaves like a small bar magnet, with a north and a south
pole.
• Otto Stern and Walther Gerlach first observed electron spin
magnetism in 1921.
Overview of quantum numbers
Difference between orbit and orbital
Orbits Orbitals

Orbits are fundamental to the Bohr model, a predecessor of the

quantum mechanics model; it describes the orbit as a circular An orbital is a space around that the nucleus of an atom that
path followed by an electron. Orbits are concentric circular has a high probability of finding an electron.
paths of electrons.

Orbits originated from the Bohr-Rutherford atomic model. The notion of orbitals was derived from the quantum model of
an atom.

Orbitals come in multiple shapes and their shapes become

Orbits are always concentric circular paths. In the modified Bohr incomprehensible as we move toward higher orbitals. The
model, orbits have an elliptical shape.
simplest of them is the s orbital, which has a spherical shape.

The orbit is a two-dimensional figure. Orbitals are in three dimensions.

They are non-directional. They are directional except s orbitals.

Because orbits have a definite path, we can predict its position We cannot estimate the exact position of an electron in an
and momentum. This contradicts the Heisenberg uncertainty orbital. We can only find the probability of an electron; the
principle. uncertainty always remains.

Orbits are not real; they do not exist, and electrons do not
revolve around the nucleus in a definite path. Orbitals are realistic.
 Electron Configuration
• An electron configuration of an atom is a particular distribution of electrons among
available subshells.
• The notation for a configuration gives the number of electrons in each subshell, but we
use a diagram to show how the orbitals of a subshell are occupied by electrons. It is
called an orbital diagram. An orbital is represented by a circle. Each group of orbitals
in a subshell is labeled by its subshell notation. An electron in an orbital is shown by
an arrow; the arrow points up when ms + 1/2 and down when ms - 1/2. The orbital
diagram
 Pauli Exclusion Principle
• Not all of the conceivable arrangements of electrons among the orbitals of an atom are
physically possible.
• The Pauli exclusion principle, which summarizes experimental observations, states
that no two electrons in an atom can have the same four quantum numbers. If one
electron in an atom has the quantum numbers n =1, l = 0, ml= 0, and ms = +1/2 no
other electron can have these same quantum numbers.
 Building-Up Principle (Aufbau Principle)
• building-up principle (or Aufbau principle), a
scheme used to reproduce the electron
configurations of the ground states of atoms by
successively filling subshells with electrons in a
specific order (the building-up order).
• Electrons will fill orbitals by the sum of the
quantum numbers n and l. Orbitals with equal
values of (n+l) will fill with the lower n values first.
Exception Building-Up Principle (Aufbau Principle)

• electronic configuration of chromium is [Ar]4s13d5 and not [Ar]4s23d4

(as the Aufbau principle suggests). This exception is attributed due to
several factors such as the increased stability provided by half-filled
subshells and the relatively small energy gap between the 3d and 4s
subshells.Half-filled subshells have lower electron-electron repulsions
in the orbitals, increasing stability. Similarly, subshells also increase
the stability of the atom. Therefore, the electron configurations of
certain atoms disobey the Aufbau rule. Copper is another exception
to this principle with an electronic configuration corresponding to
[Ar]4s13d10. This can be stability provided by a fully filled 3D subshell.
 Hund’s Law
• There may be several different ways of arranging electrons in a particular configuration. Consider the carbon atom (Z 6)
with the ground-state configuration 1s22s22p2. Three possible arrangements are given in the following orbital diagrams.

• Hund’s rule states that the lowest-energy arrangement of electrons in a subshell is obtained by putting electrons into
separate orbitals of the subshell with the same spin before pairing electrons.
• Let us see how this would apply to the carbon atom, whose ground-state configuration is 1s22s22p2.The first four
electrons go into the 1s and 2s orbitals.

• The next two electrons go into separate 2p orbitals, with both electrons having the same spin, following Hund’s rule.
 Magnetism and electron configuration
• The magnetic properties of a substance can reveal certain information about the arrangement of
electrons in an atom (or molecule). Although an electron in an atom behaves like a small magnet,
the magnetic attractions from two electrons that are opposite in spin cancel each other. As a result,
an atom that has only doubly occupied orbitals has no net spin magnetism. However, an atom with
unpaired electrons—that is, with an excess of one kind of spin—does exhibit a net magnetism.

• A paramagnetic substance is a substance that is weakly attracted by a magnetic field, and this
attraction is generally the result of unpaired electrons. < For example, sodium vapor has been
found experimentally to be paramagnetic. The configuration is [Ne]3s1.

• diamagnetic substance is a substance that is not attracted by a magnetic field or is very slightly
repelled by such a field. This property generally means that the substance has only paired
electrons. Mercury vapor is found experimentally to be diamagnetic. The explanation is that
mercury vapor consists of mercury atoms, with the electron configuration [Xe]4f 145d106s2, which
has only paired electrons.
 Electron configuration and periodic table

a noble-gas core, that is, an inner-shell configuration corresponding to one of

the noble gases,

The noble-gas core together with (n -1)d10 electrons is often referred to as a

pseudo-noble-gas core

An electron in an atom outside the noble-gas or pseudo-noble-gas core is called a valence electron. Such electrons are
primarily involved in chemical reactions, and similarities among the configurations of valence electrons (the valence-
shell configurations)account for similarities of the chemical properties among groups of elements.

The main-group (or representative) elements all have valence-shell configurations nsanpb, with some choice of a and b.
(b could be equal to 0.) In other words, the outer s or p subshell is being filled. Similarly, in the d-block transition
elements (often called simply transition elements or transition metals), a d subshell is being filled. In the f-block
transition elements (or inner transition elements), an f subshell is being filled.
Periodic table