INORGANIC AND ANALYTICAL

CHEMISTRY

FALL 2023
LECTURE 7
 QUIZ 1
MONDAY SEPTEMBER 4, 2023
DURING CLASSTIME
LECTURES 1, 2, 3, 4, 5, 6, 7
TUTORIALS 1, 2, 3
 Quantum Numbers

Quantum numbers are required to describe the distribution of

electron density in an atom.

There are three quantum numbers necessary to describe an atomic

orbital.

➢ The principal quantum number (n) – designates size

➢ The angular moment quantum number (l) – describes shape

➢ The magnetic quantum number (ml) – specifies orientation

 Quantum Numbers

The principal quantum number (n) designates the size of the

orbital.

Larger values of n correspond to larger orbitals.

The allowed values of n are integral numbers: 1, 2, 3 and so forth.

The value of n corresponds to the value of n in Bohr’s model of the

hydrogen atom.

A collection of orbitals with the same value of n is frequently

called a shell.
 Quantum Numbers

The angular moment quantum number (l) describes the shape of

the orbital.

The values of l are integers that depend on the value of the

principal quantum number

The allowed values of l range from 0 to n – 1.

➢ Example: If n = 2, l can be 0 or 1.

l 0 1 2 3
Orbital s p d f
designation
A collection of orbitals with the same value of l is referred to as a
subshell.
 Quantum Numbers

The magnetic quantum number (ml) describes the orientation of

the orbital in space.
The values of ml are integers that depend on the value of the
angular moment quantum number:
–l,…0,…+l

What do all these refer to ?

Sub-shells
 Quantum Numbers

Quantum numbers designate shells, subshells, and orbitals.

s subshell accommodates 2 electrons

p subshell accommodates 6 electrons
d subshell accommodates 10 electrons
f subshell accommodates 14 electrons
g subshell accommodates ?
What are the possible values for the magnetic quantum number (m l) when the
principal quantum number (n) is 3 and the angular quantum number (l) is 1?

Strategy: Recall that the possible values of ml depend on the value of l, not on
the value of n.

Setup: The possible values of ml are –l,…0,…+l.

Solution: The possible values of ml are –1, 0, and +1.

 Quantum Numbers

The electron spin quantum number (ms ) is used to specify an

electron’s spin.
There are two possible directions of spin. Allowed values of ms are
+½ and −½.

A beam of atoms is split by a magnetic field.

Statistically, half of the electrons spin clockwise, the other half spin
counterclockwise.
 Quantum Numbers

To summarize quantum numbers:

principal (n) – size
Required to describe an atomic orbital
angular (l) – shape
magnetic (ml) – orientation

principal (n = 2)

2px related to the magnetic

quantum number (ml )

angular momentum (l = 1)

electron spin (ms) direction of spin Required to describe an

electron in an atomic
orbital
 Atomic Orbitals

All s orbitals are spherical in shape but differ in size:

1s < 2s < 3s

principal quantum
number (n = 2)

2s
angular momentum quantum
number (l = 0)

ml = 0; only 1 orientation
possible
 Atomic Orbitals

The p orbitals:

Three orientations:
l = 1 (as required for a p orbital)
ml = –1, 0, +1
 Atomic Orbitals

The d orbitals:

Five orientations:
l = 2 (as required for a d orbital)
ml = –2, –1, 0, +1, +2
 Orbital Energies

The energies of orbitals in the hydrogen atom depend only on the principal quantum
number. BUT THIS IS NOT THE CASE FOR MULTIELECTRON ATOMS

3rd shell(n
3s subshell 3pl =
(n==3;
3) 0)
subshell l = 1) (n = 3; l = 2)
(n =3d3;subshell

shell (n = 2) 2p subshell (n = 2; l = 1)
2s2ndsubshell
(n = 2; l = 0)
List theThink
valuesAbout
of n, l,ItandConsult the following
ml for each figureintoaverify
of the orbitals your
4d subshell.
answers.
Strategy Consider the significance of the number and the letter in the 4d
designation and determine the values of n and l. There are multiple values for ml,
which will have to be deduced from the value of l.
Setup The integer at the beginning of the orbital designation is the principal
quantum number (n). The letter in an orbital designation gives the value of the
angular momentum quantum number (l). The magnetic quantum number (ml) can
have integral values of – l,…0,…+l.
Solution 4d

principal quantum angular momentum

number, n = 4 quantum number, l = 2

Possible ml are -2, -1, 0, +1, +2.

 Electron Configuration

The electron configuration describes how the electrons are

distributed in the various atomic orbitals.
In a ground state hydrogen atom, the electron is found in the 1s
orbital.
Ground state electron
configuration of hydrogen
principal (n = 1) number of electrons in the
1s 1 orbital or subshell
Energy

2s 2p 2p 2p
angular momentum (l = 0)

The use of an up arrow indicates an electron with

ms = + ½
1s
 Electron Configurations

If hydrogen’s electron is found in a higher energy orbital, the atom

is in an excited state.

A possible excited state electron

configuration of hydrogen

2s1
Energy

2s 2p 2p 2p

1s
 Electron Configurations

In multi-electron atoms, the energies of the atomic orbitals are split.

Splitting of energy levels refers to the

splitting of a shell (n=3) into subshells
of different energies (3s, 3p, 3d)
 Electron Configurations

According to the Pauli exclusion principle, no two electrons in an

atom can have the same four quantum numbers.
The ground state electron
configuration of helium

2p 2p 2p
1s2
Energy

2s

Quantum number

Principal (n) 1 1
1s describes the 1s orbital Angular moment (l) 0 0
Magnetic (ml) 0 0
describes the electrons in the 1s orbital Electron spin (ms) +½ ‒½
 Electron Configurations

The Aufbau principle states that electrons are added to the lowest
energy orbitals first before moving to higher energy orbitals.

Li has a total of 3 electrons

The ground state electron

configuration of Li

2p 2p 2p 1s22s1
Energy

2s The third electron must go in the next

available orbital with the lowest
1s possible energy.

The 1s orbital can only accommodate 2 electrons

(following Pauli exclusion principle)
 Electron Configurations

The Aufbau principle states that electrons are added to the lowest
energy orbitals first before moving to higher energy orbitals.

Be has a total of 4 electrons

The ground state electron

configuration of Be

2p 2p 2p 1s22s2
Energy

2s

1s
 Electron Configurations

The Aufbau principle states that electrons are added to the lowest
energy orbitals first before moving to higher energy orbitals.

B has a total of 5 electrons

The ground state electron

configuration of B

2p 2p 2p
1s22s22p1
Energy

2s

1s
Complete the set of quantum numbers for each electron in
the element boron:

Electron ↑ ↓ ↑ ↓ ↑
(half
arrows)
n 1 1 2 2 2

l 0 0 0 0 1

ml 0 0 0 0 -1

ms +1/2 -1/2 +1/2 -1/2 +1/2

 Electron Configurations

According to Hund’s rule, the most stable arrangement of

electrons is the one in which the number of electrons with the same
spin is maximized.

C has a total of 6 electrons The ground state electron

configuration of C

1s 2s 2p
2 2 2
2p 2p 2p
Energy

2s The 2p orbitals are of equal energy, or degenerate.

1s Put 1 electron in each before pairing (Hund’s rule).

 Electron Configurations

According to Hund’s rule, the most stable arrangement of

electrons is the one in which the number of electrons with the same
spin is maximized.

N has a total of 7 electrons The ground state electron

configuration of N

1s 2s 2p
2 2 3
2p 2p 2p
Energy

2s The 2p orbitals are of equal energy, or degenerate.

1s Put 1 electron in each before pairing (Hund’s rule).

 Electron Configurations

According to Hund’s rule, the most stable arrangement of

electrons is the one in which the number of electrons with the same
spin is maximized.

O has a total of 8 electrons The ground state electron

configuration of O

1s 2s 2p
2 2 4
2p 2p 2p
Energy

2s
Once all the 2p orbitals are singly occupied, additional
electrons will have to pair with those already in the orbitals.
1s
 Electron Configurations

According to Hund’s rule, the most stable arrangement of

electrons is the one in which the number of electrons with the same
spin is maximized.

F has a total of 9 electrons The ground state electron

configuration of F

1s 2s 2p
2 2 5
2p 2p 2p
Energy

2s
When there are one or more unpaired electrons, as
1s in the case of oxygen and fluorine, the atom is
called paramagnetic.
 Electron Configurations

According to Hund’s rule, the most stable arrangement of

electrons is the one in which the number of electrons with the same
spin is maximized.

Ne has a total of 10 electrons The ground state electron

configuration of Ne

1s 2s 2p
2 2 6
2p 2p 2p
Energy

2s
When all of the electrons in an atom are paired, as
1s in neon, it is called diamagnetic.
 Electron Configurations
General rules for writing electron
configurations:

1) Electrons will reside in the available

orbitals of the lowest possible energy.

2) Each orbital can accommodate a

maximum of two electrons.

3) Electrons will not pair in degenerate

orbitals if an empty orbital is available.

4) Orbitals will fill in the order indicated

in the figure.
Write the electron configuration and give the orbital diagram of a calcium (Ca)
atom (Z = 20).
Setup Because Z = 20, Ca has 20 electrons. They will fill
in according to the diagram at right. Each s subshell can
contain a maximum of two electrons, whereas each p
subshell can contain a maximum of six electrons.

Solution

Ca 1s22s22p63s23p64s2

1s2 2s2 2p6 3s2 3p6 4s2

Think About It Look at the figure again to make sure you have filled the
orbitals in the right order and that the sum of electrons is 20. Remember
that the 4s orbital fills before the 3d orbitals.
 Electron Configurations

The electron configurations of all elements except hydrogen and

helium can be represented using a noble gas core.

The electron configuration of potassium (Z = 19) is

1s22s22p63s23p64s1.

Because 1s22s22p63s23p6 is the electron configuration of argon, we

can simplify potassium’s to [Ar]4s1.
The ground state electron configuration of K:

1s22s22p63s23p64s1

[Ar] [Ar]4s1
 Electron Configurations

There are several notable exceptions to the order of electron filling

for some of the transition metals.

➢ Chromium (Z = 24) is [Ar]4s13d5 and not [Ar]4s23d4 as

expected.
➢ Copper (Z = 29) is [Ar]4s13d10 and not [Ar]4s23d9 as expected.

The reason for these anomalies is the slightly greater stability of d

subshells that are either half-filled (d5) or completely filled (d10).

Cr [Ar]
4s 3d 3d 3d 3d 3d

Greater stability with half-filled

3d subshell
 Electron Configurations
There are several notable exceptions to the order of electron filling
for some of the transition metals.

➢ Chromium (Z = 24) is [Ar]4s13d5 and not [Ar]4s23d4 as

expected.
➢ Copper (Z = 29) is [Ar]4s13d10 and not [Ar]4s23d9 as expected.

The reason for these anomalies is the slightly greater stability of d

subshells that are either half-filled (d5) or completely filled (d10).

Cu [Ar]
4s 3d 3d 3d 3d 3d

Greater stability with filled 3d

subshell
Write the electron configuration for an arsenic atom (Z = 33) in the ground state.

2
Setup The noble gas core for As is [Ar], where Z = 18 for
Ar. 2 6

The order of filling beyond the noble gas core is 4s, 3d, 2 6 10
and 4p. Fifteen electrons go into these subshells because 2 3
there are 33 – 18 = 15 electrons in As beyond its noble gas
core.

Solution

As [Ar]4s23d104p3

Think About It Arsenic is a p-block element; therefore, we should

expect its outermost electrons to reside in a p subshell.
 The p-block elements are unified by
The p-block elements are found on the the fact that their valence electrons
right side of the periodic table. They include (outermost electrons) are in
the boron, carbon, nitrogen, oxygen and the p orbital
flourine families in addition to the noble
gases. The noble gases have full p-orbital's
and are nonreactive.
 Electron Configurations of Ions

O (8 electrons): 1s2 2s2 2p4

ANION
O (10 electrons): 1s 2s 2p
2– 2 2 6

Mg (12 electrons): 1s2 2s2 2p6 3s2

Mg2+ (10 electrons): 1s2 2s2 2p6 CATION

Ni (28 electrons): 1s2 2s2 2p6 3s2 3p6 4s2 3d8

[Ar] 4s2 3d8

Ni2+ (26 electrons): 1s2 2s2 2p6 3s2 3p6 3d8

For transition metals,
8 remove 4s e–’s first
[Ar] 3d
 Electron Configurations of Transition Metals

Elements up to Ar: Standard orbital energy level diagram is

fine
K and Ca: Standard orbital energy level diagram is fine, 4s
electrons are still lower in energy than the 3d orbitals

d-Block Elements (Transition metals): 3d are slightly

lower in energy than 4s… so why fill the 4s first?

4s
3d

Let’s look at scandium and its ions…

Sc: [Ne] 3s2 3p6 3d1 4s2

 Electron Configurations of Scandium and its Ions
Scandium has 21 protons

4s x eV
y eV 3d
Sc3+: [Ne] 3s2 3p6
Sc2+: [Ne] 3s2 3p6 3d1
Sc+: [Ne] 3s2 3p6 3d1 4s1 NOT: [Ne] 3s2 3p6 3d2
• 3d orbitals are quite compact: repulsion (y eV) associated with having two
electrons in 3d orbitals
• 4s orbitals are higher in energy, but energy gap between 3d and 4s (x
eV) is smaller than repulsion between 3d2 (y eV)

More energetically favorable to occupy the 3d1 4s1 rather than

3d2 configuration

Sc: [Ne] 3s2 3p6 3d1 4s2 3d  4s gap + 4s2 repulsion < 3d2 repulsion
 Molecular Orbital (MO) Theory

• Two atomic orbitals combine to form

– a bonding molecular orbital (σ or π)
– an anti-bonding molecular orbital (σ* or π*)
• e– in bonding MO’s => stability
• e– in anti-bonding MO’s => instability
• # atomic orbitals combined equals # of
molecular orbitals formed
Addition and Subtraction of Waves

Amplitudes of wave Amplitudes of wave functions are

functions are added subtracted.

BONDING ORBITAL ANTI-BONDING ORBITAL