General Chemistry

Chem110

Chapter 7
Quantum Theory
and
the Electronic Structure of Atoms
Objectives

• Understand the transition from classical physics to quantum theory

• Define the properties of waves and electromagnetic radiation
• Know Bohr’s theory of the hydrogen Atom and find the electron energy
• Identify the four quantum numbers to describe the electron
• Know the characteristic of atomic Orbitals
• Write and draw electron Configurations
• Apply the Building-Up Principle

2
Outline
7.1 From Classical Physics to Quantum Theory
7.3 Bohr’s Theory of the Hydrogen Atom
7.6 Quantum Numbers
7.7 Atomic Orbital’s
7.8 Electron Configurations
7.9 The Building-Up Principle

3
7.1 From Classical Physics to Quantum Theory
In 19th century : understanding atoms and molecules was unsuccessful.
Classical Physics: successful in understanding Macroscopic Phenomena, e.g.
pressure of the gas
 Quantum Mechanics: successful in understanding microscopic phenomena, e.g.
atoms & molecules
 It was assumed that energy is continuous, and any amount of energy could be
released or absorbed in a radiation process.
Max Planks in 1900: discovered that atoms and molecules emit energy only in
certain discrete quantities (called quanta) → Quantum Theory

4
Properties of Waves
Wavelength (𝛌): is the distance between identical
points on successive waves.

Frequency (𝝂): is the number of waves that pass

through a particular point in 1 second (Hz = 1 cycle/s).

Amplitude: is the vertical distance from the midline

of a wave to the peak or trough.

The speed (u) of the wave = 𝜆 𝑥 𝜈

5
Electromagnatic Radiation

Waves are of different kinds, e.g. water waves, sound waves, and light waves.
In 1873 James Maxwell proposed that visible light consists of electromagnetic
waves or it is an electromagnetic radiation.
Electromagnetic waves has two perpendicular components:
• Electric field component
• Magnetic field components

6
Electromagnetic Radiation

Electromagnetic radiation: is the emission and transmission of energy

in the form of electromagnetic waves.
All electromagnetic radiation travels at the same velocity in specific
medium (speed of light)
Speed of light (c) in vacuum = 3.00 x 108 m/s

𝑐 =𝜆𝑥𝜈

7
Type of Electromagnetic Radaition

8
Example 7.2
The wavelength of the green light from a traffic signal is centered at 522nm . What
is the frequency of this radiation?
Given: 𝜆 = 522 nm; c (known)
∵𝑐=𝜆𝑥𝜈
𝑐 3 𝑥 108 𝑚/𝑠
∴𝜈= = = 5.57 x 1014 Hz
𝜆 522 𝑥 10−9 𝑚

What is the 𝜆 in meter (m) of an electromagnetic wave whose frequency is 3.64 x107
Hz?
Given: 𝜈 = 3.64 x107 Hz; c (known)
∵𝑐=𝜆𝑥𝜈
𝑐 3 𝑥 108 𝑚/𝑠
∴𝜆= = = 8.24 m
𝜈 3.64 𝑥 107 /𝑠
9
Plank’s Quantum Theory

 When solids are heated, they emit an electromagnetic radiation

 FACT: the amount of radiant energy emitted by an object at a certain
temperature depends on the wavelength
 Classical physics failed in explaining why this happens!!!
because classical physics assumed that atoms or molecules could emit
(or absorb) any amount of energy!!!
Plank explained this: Energy (light) is emitted or absorbed in
discrete units (quantum).

10
Plank’s Quantum Theory
Quantum: is the smallest quantity of energy that can be emitted (or absorbed) in the
form of electromagnetic radiation.
 Quantum is given by:
𝑬=𝒉𝒙𝝂
𝒄
𝑬 = 𝒉 𝒙𝝀
where:
𝐸: is the energy
ℎ: Plank’s constant, ℎ = 6.63 𝑥 10−34 J.s
𝜈: frequency of radiation
 According to quantum theory: energy is always emitted in integrals multiples of ℎ𝜈
e.g. ℎ𝜈, 2ℎ𝜈, 3ℎ𝜈, ……………
11
Example 7.3

Calculate the energy (in J) of a photon with a wavelength of 5.00 x 104 nm

(IR region).

𝜆 = 5.0 𝑥 104 nm
→ 5.0 𝑥 104 𝑥 10−9 = 5.0 𝑥 10−5 m

ℎ𝑐
𝐸=
𝜆
6.63 𝑥 10−34 𝐽.𝑠 𝑥 3.0 𝑥 108 𝑚/𝑠
= = 3.98 𝑥 10−21 J
5.0𝑥 10−5 𝑚

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7.3 Bohr’s Theory of the Hydrogen Atom
Emission Spectrum of the Hydrogen Atom
Neil Bohr: study the emission spectrum of the Hydrogen Atom
 Bohr postulates that the electron is occupied ONLY certain orbits of specific
energies → The energies of the electron are quantized
 THUS: the emission spectrum of the H atom results from: the hydrogen atom is
energized → electron excited to higher energy orbit → drop to a lower-energy
orbit emits a quantum of energy (light)
Emission Spectra of atoms are bright lines (spectral lines) in the visible spectrum
 Emission spectrum of any atom is a fingerprint (lines appeared at specific
wavelengths)

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Emission Spectrum of the Hydrogen Atom

Line Emission Spectrum of Hydrogen Atoms

14
Emission Spectrum of the Hydrogen Atom

15
Emission Spectrum of the Hydrogen Atom
Bohr’s Model of the Atom:
• Electron (e-)can only have specific energy values (quantized)
• light is emitted as e- moves from one energy level to a lower energy level

𝟏
𝑬𝒏 = −𝑹𝑯 𝒏𝟐
Where:
𝑛 (principal quantum number) = 1,2,3,…
𝑅𝐻 (Rydberg constant) = 2.18 x 10−18 J

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Emission Spectrum of the Hydrogen Atom

E  E f  Ei
1
E f   RH ( 2 )
nf
1
Ei   RH ( 2
)
ni
  RH    RH 
 E   2    2 
 n 
 f   ni 
 1 1 

E  RH 2  2
n n 
 i f 

17
Emission Spectrum of the Hydrogen Atom
1 1
∆𝐸 = 𝑅𝐻 2− 2
𝑛𝑖 𝑛𝑓
ℎ𝑐
∆𝐸 = ℎ𝜈 =
𝜆

Energy can be absorbed/emitted:

• If 𝑛𝑓 > 𝑛𝑖 → ΔE (+ve) → Energy is absorbed

(Energy is gained from the surrounding)
• If 𝑛𝑖 > 𝑛𝑓 → ΔE (-ve) → Energy is emitted
(Energy is lost to the surrounding)

18
Emission Spectrum of the Hydrogen Atom

19
Example 7.4:

What is the wavelength of a photon (in nm) emitted during a transition from the
𝑛𝑖 = 5 state to the 𝑛𝑓 = 2 state in the hydrogen atom?
1 1
∆𝐸 = 𝑅𝐻 2 − 2
𝑛𝑖 𝑛𝑓
−18 1 1
= 2.18 𝑥 10 52
− 22
= −4.58 𝑥 10−19 J

ℎ𝑐
∆𝐸 = ⇒
𝜆
ℎ𝑐 6.63 𝑥 10−34 𝐽.𝑠 𝑥 3.0 𝑥 108 𝑚/𝑠
𝜆= = = 4.34 𝑥 10−7 m = 434 nm
∆𝐸 4.58𝑥 10−19 𝐽

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7.6 Quantum Numbers (n, ℓ, mℓ, ms)

In quantum mechanics, three quantum numbers are required to

describe the distribution of electrons in hydrogen and other atoms (n,
ℓ, mℓ) . These numbers are derived from the mathematical solution of
the SchrÖdinger equation for hydrogen atom.
 The fourth quantum is the spin quantum number (ms) describes the
behavior of a specific electron and completes the description of the
electron in the atoms.

 Electrons in multi-electron atoms can be classified into a series of:

shells (n) → subshells (ℓ )→ orbitals (mℓ)
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The Principal Quantum Number (n)

 Values: n = 1, 2 , 3, 4 ………
 Meaning: determines the energy of an orbital → determines the
distance of the electron from the nucleus → Size.
Bigger n → larger energy → farther from the nucleus → larger size
The maximum number of orbitals in (𝒏) = 𝒏𝟐
The maximum number of electrons in (𝒏) = 𝟐𝒏𝟐

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The Angular Momentum Quantum Number (ℓ)
Values: ℓ = from 0 to n−1.
Meaning: determines the shape of the orbital
The value of ℓ is designated by letters:

value of 𝑙 0 1 2 3 4 5
Name of orbital s p d f g h

value of 𝑛 values of 𝑙 orbitals

1 0 1s
2 0, 1 2s, 2p
3 0, 1 ,2 3s, 3p, 3d
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The Magnetic Quantum Number (mℓ)

Values: depend on the value of ℓ →

values of mℓ = -ℓ to +ℓ
(what are the mℓ values for each ℓ value?)
Meaning: determines the orientation of the orbital
 The number of orbitals in each subshell ℓ = number of mℓ =2 ℓ +1
(how many mℓ -orbitals- should be obtained for each ℓ value?)
Therefore, for any given energy level, there can be up to 1 s orbital, 3
p orbitals, 5 d orbitals, 7 f orbitals.

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The Electron Spin Quantum Number (ms)
Meaning: determines the electron spin
The spin quantum number has only two allowed values:
ms = +½ and −½ .

Experiments on the emission spectrum of Hydrogen atom indicated that

lines in the emission spectrum cloud be split by the application of an
external magnetic field.

This only explained by assuming that the electron is acting as a tiny

magnet.

The “spin” of an electron describes its magnetic field, which affects its
energy.

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Example

Which of the following is impossible to be a quantum number set?

a) 4, 3, -2, -½
b) 4, 2, -1, -½
c) 4, 5, 0, +½
d) 4, 1, -2, +½

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Example 7.6

List the values of n, ℓ and mℓ for orbitals in 4d subshell.

n=4
ℓ = 0 to (n-1) = 0 to (4-1) = 0, 1, 2, 3 Note: If it is a multiple
BUT d means ℓ = 2 choices question?
mℓ = - ℓ to + ℓ → mℓ = -2, -1, 0, +1, +2 a) 4, 2, -2
b) 4, 2, -1
c) 4, 2, 0
d) 4, 2, +1
e) 4, 2, +2

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 Example 7.7:

What is the total number of orbitals associated with the principal quantum number n = 3 ?

Total Number of Orbitals = n2 = 32 = 9

(OR(
ℓ = 0 to (n-1) = 0 to (3-1) = 0, 1, 2
ℓ = 0 → mℓ = - ℓ to + ℓ → mℓ = 0 → One orbital
ℓ = 1 → mℓ = - ℓ to + ℓ → mℓ = -1, 0, +1 → Three Orbitals
ℓ = 2 → mℓ = - ℓ to ℓ → mℓ = -2, -1, 0, +1, +2 → Five Orbitals
Total Number of Orbitals: 9 Orbitals

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Example 7.9:

Write the four quantum numbers for an electron in a 3p orbital.

1 1
3, 1, −1, + 3, 1, −1, −
2 2
1 1
3, 1, 0, + 3, 1, 0, −
2 2
1 1
3, 1, +1, + 3, 1, +1, −
2 2

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 7.7 Atomic Orbitals
S Orbitals
 value of ℓ= 0.

 Shape: spherical in shape.

 Radius of sphere increases with increasing value of n.

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7.7 Atomic Orbitals
p Orbitals
 Value of ℓ = 1.
 Shape: Two lobes with a node between them.
 Number of mℓ =2 ℓ +1 = 2×1+1 = 3
 Values of mℓ = 1, 0, -1 (px, pz, py)
 Three 2p orbitals are identical in shape and energy, but their orientations are
different; three orientations in space.
 p orbital increase in size from 2p to 3p to 4p and so on.

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7.7 Atomic Orbitals
d Orbitals
 Value of ℓ is 2.
 Number of mℓ =2 ℓ +1 = 2×2+1 = 5
 Values of mℓ = 2, 1, 0, -1, -2 𝑑𝑥𝑦 , 𝑑𝑦𝑧 , 𝑑𝑥𝑧 , 𝑑𝑧 2 , 𝑑𝑥2 −𝑦2
 Shape: four of the five orbitals have 4 lobes, the other resembles a p orbital
with a doughnut around the center; five orientations in space.

32
 The Energies of Orbitals

 For a one-electron hydrogen atom, orbitals on the

same energy level have the same energy.

 That is, they are degenerate.

The energies of H orbitals increase as follows:

1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f < …..

33
The Energies of Orbitals
 For many-electron atoms, the energy of an electron depends on its
angular momentum quantum number as well its principal quantum
number.
 However , the total energy depends on the sum of the orbital
energies and the energy of repulsion between the electron in these
orbitals
 And as the number of electrons increases, the repulsion between
them increases as well.
 As the 3d energy level is very close to the 4s energy level, and the
total energy of an atom is lower when the 4s subshell is filled before
the 3d subshell , thus 4s orbital is lower in energy than the 3d orbital.

 Therefore, in many-electron atoms, orbitals on the same energy level

are no longer degenerate.
 The energies of multi-electrons atoms as follows:

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
34
Order of orbitals (filling) in multi-electron atoms

Method of filling:
1. Start with the 1s orbital and move
downward.
2. Following the direction of the arrows.
3. Thus: the order goes as follows:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s <
4d < 5p < 6s

35
7.8 Electron configuration
Electron configuration: is how the electrons
are distributed among the various atomic
orbitals in an atom.

 The four quantum numbers n, ℓ, m ℓ and ms

enable us to label completely an electron in
any orbital in any atom.
The value of ms has no effect on the energy,
size, shape, or orientation of an orbital, but it
determines , how electrons are arranged in an
orbital.

36
7.8 Electron configuration
Orbital Diagram
 Each box represents one orbital.

 Half-arrows represent the electrons.

 The direction of the arrow represents the spin of the electron.

37
The Pauli Exclusion Principal
 NO two electrons in an atom can have the same set of four quantum numbers
 Only two electrons may occupy the same atomic orbital ( same n, l, ml), and these
two electrons must have opposite spins (ms)
Consider the He atom:

(a) and (b) are ruled out by Pauli Exclusion Principal, (c) is acceptable. WHY?
Thus: the He atom has the following electron configuration:

38
Hund’s Rule
 The most stable arrangement of electrons in subshells is the one with the
greatest number of parallel spins.
 The electron configuration of Carbon (Z = 6) is: 1s2 2S2 2p2.
 Three different ways of distributing two electrons among three p orbitals:

 (a)/(b)/(c) did not violet the Pauli Exclusion principal, Which one/ones of
greatest spins (Hund’s rule)?
The orbital diagram of C is
39
Hund’s Rule:
More examples

40
 Diamagnetism and Paramagnetism
Paramagnetic substance: is the
substance that contains net unpaired
electrons in the outermost subshell. Thus
it will be attracted by a magnet.
Diamagnetic substance: is the substance
that does not contain net unpaired
electrons (all electrons are paired) in the
outermost subshell. Thus it will be
slightly repelled by a magnet. Paramagnatic Diamagnatic
 The Li atom contains one unpaired
electron and → Li metal is paramagnetic.

41
The Shielding Effect in Many Electron Atoms
Electrons in the smaller orbitals (lower energy) are closer to nucleus (e.g., 1s) than
electrons in larger orbitals (e.g., 2p, 3s).
Thus the farther electrons are "shielded" by the closer electron from the attractive
forces of the nucleus.
This causes a slight increase in energy of the more distant electrons.
In fact, for the same principle quantum number n, the attractive forces decrease as
the angular momentum quantum number l increase
s > p > d > f….
In another way, less energy is required to remove 2p electron than 2s electron.

42
Example 7.10:
An Oxygen atom has a total of eight electrons. Write the four quantum numbers for
each of the eight electrons in the ground state.
Electron 𝑛 𝑙 𝑚𝑙 𝑚𝑠 orbital
1
1 1 0 0 + 1s
2
1
2 1 0 0 − 1s
2
1
3 2 0 0 + 2s
2
1
4 2 0 0 − 2s
2
1
5 2 1 -1 + 2py, 2px, 2pz
2
1
6 2 1 0 + 2py, 2px, 2pz
2
1
7 2 1 1 + 2py, 2px, 2pz
2
1
8 2 1 1 − 2py, 2px, 2pz 43
2
7.9 Building-Up Principle
Aufbau Principle (“Fill up” electrons):
The electrons are added one by one to the atomic orbitals in lowest energy orbitals

The Pauli Exclusion Principal:

NO two electrons in an atom can have the same set of four quantum numbers

Hund’s Rule:
The most stable arrangement of electrons in subshells is the one with the greatest
number of parallel spins

44
7.9 Building-Up Principle
• “Fill up” electrons in lowest energy orbitals (Aufbau principle)

? ?

Li
Be
B 6534electrons
C electrons
electrons

BBe 21s
Li1s1s2s222s
22s12 1
2p

He
H 21 electrons
electron

He 1s12
H 1s

45
7.9 Building-Up Principle
• The most stable arrangement of electrons in subshells is the one with the greatest
number of parallel spins (Hund’s rule).

C 967810
N
O
F
Ne electrons
electrons
electrons
Ne
N
C
O 1s222s
F 1s 22s
222p
22p52346

46
Short Notation (abbreviation)
In the short notation: the electron configuration of any element except Hydrogen
and Helium are represented by a noble gas core, which shows in brackets the noble
gas element that most nearly precedes the element being considered, followed by the
symbol for the highest filled subshells in the outermost shells.

Examples: Electron configuration of some elements of group 1A:

Without short notation With short notation
3Li:1s2 2s1 3Li:[He] 2s1
11Na: 1s2 2s2 2p6 3s1 11Na: [Ne] 3s1

19K: 1s2 2s2 2p6 3s2 3p6 4s1 19K: [Ar] 4s1

47
Example:

Write the ground-state electron configuration for Mg? is it paramagnetic or

diamagnetic?
Mg atom has 12 electrons (from: Periodic table (Z = atomic number))
Electron Configuration: 1s22s22p63s2
Short notation: [Ne] 3s2; where: [Ne] = 1s22s22p6

Orbital Diagram:

1s2 2s2 2p6 3s2

So, it is diamagnatic

48
7.9 Building-Up Principle
Exceptions:

Extra Stability of half-filled

and filled d subshells : Some
transition metals.
Reason: Half-filled and filled
subshells have special stability,
leading to some unexpected
electron configurations.

49
7.9 Building-Up Principle
Exceptions:
Half filled d orbital stability
The expected: 24Cr: [Ar] 4s2 3d4 The actual: 24Cr: [Ar] 4s1 3d5
The expected: 42Mo: [Kr] 5s2 4d4 The actual: 42Mo: [Kr] 5s1 4d5

Filled d orbital stability

The expected: 29Cu [Ar] 4s2 3d9 The actual: 29Cu : [Ar] 4s1 3d10
The expected: 47Ag [Kr] 5s2 4d9 The actual: 47Ag: [Kr] 5s1 4d10
The expected: 79Au: [Xe] 6s2 4f14 5d9 The actual: 79Au: [Xe] 6s1 4f14 5d10

50
 7.9 The Building-Up Principle
Aufbau Principle (“Fill up” electrons): the electrons are added one by one to the
atomic orbitals in lowest energy orbitals
Alkali metals and alkaline earth metals fill the s orbitals last.
Main group elements fill the p orbitals last.
Transition metals fill the d orbitals last.
Lanthanides and actinides fill the (4f) and the (5f) orbitals last, respectively.
Elements in same group have same valence shell electron configurations and have
similar chemical properties

51
 Ground State Electron Configuration of Valence Electrons of Elements

ns2np6
ns1

ns2np1
ns2np2
ns2np3
ns2np4
ns2np5
ns2
Within a Period number of electrons increase
Within a group (n) increase

d10
d1

d5

4f
5f 52
Classification of Elements According to the Type of Subshells Being Filled
s block
v.e.=ns
p block
v.e.=ns np
Transition Elements
d block
v.e.=ns (n-1)d

f block
v.e.=ns (n-2)f
53
Examples:
What are the valence electrons of aluminum Al? 13Al: [Ne] 3s2 3p1
a) 3s2
b) 3s2 3d10
c) 3s2 3d10 3p1
d) 3p1
e) 3s2 3p1

What are the valence electrons of gallium Ga? 31Ga: [Ar] 4s2 3d10 4p1
a) 4s2
b) 4p1 Valence electrons are in the highest n
Ga is in p-block (VE = ns np)
c) 4s23d10
Thus: The valence electrons are
d) 4s23d104p1 4s2 4p1
e) 4s24p1

54
Find Period and Group

The highest n gives the period of the element

 The valence electrons give the position of the element within the group
ns1 → group 1A n = 1 → period 1
ns2 → group 2A n = 2 → period 2
ns2 np1 → group 3A n = 3 → period 3
ns2 np2 → group 4A n = 4 → period 4
ns2 np3 → group 5A n = 5 → period 5
ns2 np4 → group 6A n = 6 → period 6
ns2 np5 → group 7A n = 7 → period 7
ns2 np6 → group 8A

55
Example 8.1
An atom of a certain element has 15 electrons. Without consulting a periodic
table, answer the following questions:
(a) What is the ground-state electron configuration of this element?
Electron configuration: 1s2 2s2 2p6 3s2 3p3
Short notation: [Ne] 3s2 3p3
(b) How should the element be classified?
Period 3, group 5A; the element is a representative element.
(c) Is the element diamagnetic or paramagnetic
paramagnetic
3s2 3p3 56
57
Electron Configurations of Cations and Anions of
Representative Elements
Atoms lose electrons so that cation Atoms gain electrons so that anion has a noble-
has a noble-gas outer electron gas outer electron configuration.
configuration. H: 1s1 H- 1s2 or [He]
Na: [Ne] 3s1 Na+ [Ne] F: 1s22s22p5 F- 1s22s22p6 or [Ne]
Ca: [Ar] 4s2 Ca2+ [Ar] O: 1s22s22p4 O2- 1s22s22p6 or [Ne]
Al: [Ne] 3s23p1 Al3+ [Ne] N: 1s22s22p3 N3- 1s22s22p6 or [Ne]

58
Cations and Anions of Representative Elements

+1

+2

+3

-3

-2

-1
59
Electron Configurations of Cations of Transition Metals

When a cation is formed from an atom of a transition metal, electrons are

always removed first from the ns orbital and then from the (n –1) d orbitals.

Fe: [Ar]4s23d6 Mn: [Ar]4s23d5

Fe2+: [Ar]4s03d6 or [Ar]3d6 Mn2+: [Ar]4s03d5 or [Ar]3d5

Fe3+: [Ar]4s03d5 or [Ar]3d5

 Keep in mind that most transition metals can form more than one cation
and frequently the cations are not isoelectronic with the preceding noble
gases.
60
Isoelectronic Species
Isoelectronic: Species with the same number of electrons/the same
electronic configuration.

Na+: [Ne] Al3+: [Ne]

F-: 1s22s22p6 or [Ne] O2-: 1s22s22p6 or [Ne]

N3-: 1s22s22p6 or [Ne]

Thus: Na+, Al3+, F-, O2-, and N3- are all isoelectronic with Ne.

Similarly: H- and He are isoelectronic.

61
 Examples:
Which of the following is paramagnetic ? How many unpaired electrons are in Mn ?
• Mg • 2
• Ar • 5
• He • 4
• N • 3
Which of the following is diamagnetic ? How many unpaired electrons are in Fe2+ ?
• Mg • 2
• Na • 4
• N • 5
• Li • 3
How many unpaired electrons are in Mn2+ ? How many unpaired electrons are in Fe3+ ?
• 2 • 2
• 5 • 5
• 4 • 4
• 3 • 3

62