GENERAL CHEMISTRY

CHM 131

CHAPTER 3
ELECTRONIC STRUCTURE OF
ATOM & PERIODICITY

Puan Siti Norhayati Binti Mohamad Tarmizi

Email: [email protected] @ [email protected]
Phone Number: 017 6162305 / 05-4067422
1
 Lesson Outcomes
• Understand the general regions of the electromagnetic
spectrum
• Understand how Bohr’s theory explained the line spectra of H
atom
• Find the energy change and wavelength of the photon
absorbed or emitted when H atom’s electron changes energy
level
• Determine quantum numbers and sublevel designations
• Draw the shapes of s, p and d orbitals
• Describe the arrangement of electrons in an atom based on
Aufbau Principle, Pauli Exclusion Principle and Hund’s Rule
• Write full and condensed electron configuration of an element
• Understand the periodic trends of elements
2
 3.1 Definition &
Calculation of e-, proton,
neutron, atomic number
etc (refer chapter 2)

3
 Atomic number & Mass number
Atomic number (Z)
= number of protons in nucleus

Mass number (A)

= number of protons + number of neutrons
= atomic number (Z) + number of neutrons

Number of electron:
+ve charge = loss of electron (deduct)
-ve charge = gain electron (add)

Mass Number A
ZX
Element Symbol
Atomic Number
4
 Electromagnetic Spectrum
 EM spectrum include gamma rays, X-rays, UV light,
visible light, Infra Red (IR), microwaves and radio
waves.
 Light: Mean only visible light (EM spectrum detected
by human eye) and sometimes entire EM spectrum.
 Definition of light: A wave motion because it can be
refracted (dibiaskan) by a prism and diffracted
(merebak) by grating.
 This phenomena can only be explained by light
possessing wave properties

5
 Electromagnetic Radiation
•Electromagnetic radiation is the emission and transmission of
energy in the form of electromagnetic wave

6
 Properties of wave

• Wavelength, λ (lambda)
- the distance between identical points on successive waves
• Amplitude
- the vertical distance from the midline of a wave to the peak &
trough
• Frequency, ν (nu)
- the number of waves that pass through a particular point in 1
second (Hz = 1 cycle/s)
The speed of the wave = λ x ν 7
 Planck’s Quantum Theory
• Max Planck (1900) proposed the Quantum Theory
• Quantum theory states that energy in the form of
electromagnetic radiation can be emitted or absorbed in
discrete amount called quanta (singular: quantum)
• Quantum – the smallest quantity of energy that can be
emitted (or absorbed) in the form of electromagnetic radiation
• Planck’s equation:
E = hν
Where h = Planck’s constant = 6.63×10-34 J s

ν=c/λ

Therefore, E = hc / λ

8
•Light has a particle nature – described as a stream of particles
called photons.
•The Energy of photons (E) is related to the frequency of waves

E= hv

•Where h is constant known as Planck’s constant = 6.63 x 10-34 J.s

•The frequency of any wave is inversely proportional to its wavelength, l

Speed of light (c) in vacuum = 3.00 x 108 m/s (that value

is equal to 186,000 miles per second)

All electromagnetic radiation

lxn=c

9
Example:
The energy of photon is 2.00 x 10-13 J. Calculate the frequency
and the wavelength of light .

Ans:
l
E= hv

2.00 x 10-13 J = (6.63 x 10-34 J.s) n n

n = 3.017 x 1020/s = 3.02 x 1020/s

l = c/v = (3.00 x 108 m/s)(3.017 x 1020/s)

l = 9.94 x 10-13 m
l = 9.94 x 10-4 nm
This photon is in gamma-ray portion of
spectrum
10
Example:
A photon has a frequency of 6.0 x 104 Hz. Convert this frequency
into wavelength (nm). Does this frequency fall in the visible
region?

l
Ans:
lxn=c n

l = c/n
l = 3.00 x 108 m/s / 6.0 x 104 Hz
l = 5.0 x 103 m
l = 5.0 x 1012 nm

11
 Example:
Calculate the energy (in joules) of (a) a photon with a wavelength of
5.00×104 nm (IR region) & (b) a photon with a wavelength of 5.00×10-
2 nm (X-ray region).

Ans:
E = hc / λ
= (6.63×10-34 Js)(3.00×108 m/s)
(5.00×104 nm) 1×10-9 m
1 nm
= 3.98×10-21 J
= 3.98×10-15 J

12
 3.2 Introduction to
Hydrogen Emission
Spectrum, Bohr’s Theory

13
• When gaseous atoms of a given element are
heated, they emit light of only specific
energies.
• When gaseous atoms of that same element
absorbed light, they absorb those same
energies.
• Bohr Theory: Electrons in atoms have
discrete energy levels, that is electrons may
be found only in orbits with specific energies.

14
BOHR’S THEORY
“A theory of atomic structure in which the hydrogen atom is assume to
consist of a proton as nucleus, with a single electron moving in distinct
circular orbits around it, each orbit corresponding to a specific
quantized energy state: the theory was extended to other atoms.”

15
 4 PRINCIPLES OF BOHR’S MODEL
1. Electrons assume only certain orbits around the nucleus. These orbits are
stable and called stationary orbits.
2. Each orbit has an energy associated with it. For example, the orbit closest
to the nucleus has an energy of E1, the next closest E2 and so on.
3. Light is emitted when an electron jumps from a higher orbit to a lower
orbit and absorbed when it jumps from a lower to higher orbit.
4. The energy and frequency of light emitted or absorbed is given by the
difference between the two orbit energies, E (light) = Ef – Ei, where f and
i represent final and initial orbits.

16
 Bohr’s Model of Atom (1913)

1 n (principal quantum number) = 1,2,3,…

En = -RH ( )
n2 RH (Rydberg constant) = 2.18 x 10-18J

17
• When an atoms absorb energy, an electron is
“promoted” to a higher energy level.
• Each orbit has a discrete energy level, so the difference
in energy between the orbits is also definite.
• After an electron has been promoted to a higher energy
level, it falls back to a lower energy level.
• When it falls back, light of energy equal to the difference
in energy between the orbits is emitted from the atom.

18
 The Line Spectrum of Hydrogen

• When electricity is passed through a discharge tube filled with

hydrogen gas at low pressure, a pink light is emitted
• When the light passes through a prism, a line spectrum is
obtained

19
 The line spectrum
• When atoms are excited they emit light of certain
wavelengths which correspond to different colors.
excited state

ENERGY IN PHOTON OUT

ground state

20
• The energy supplied is absorbed by the electrons of hydrogen
atoms and causes them to be promoted from the ground
states to higher energy levels
• Transitions of electron between two energy levels produce
lines in the hydrogen spectrum
• The emission series obtained are classified according to
which level the electrons drop to

Level which Name of series Spectrum

electron drops region
n=1 Lymann Ultraviolet
n=2 Balmer Visible
n=3 Paschen Infrared
n=4 Brackett Infrared
n=5 Pfund Infrared

21
 Ephoton = DE = Ef - Ei
ni = 3 ni = 3 1
Ef = -RH ( 2 )
nf
ni = 2 1
Ei = -RH ( 2 )
nf = 2 ni
1 1
DE = RH( 2 )
ni n2f

nnf f==11

22
Example:
Calculate;
a) The energy an electron has when it occupies a level
equivalent to the quantum number of n = 3 and n = 4
b) The energy of the photon emitted when one mole of electron
drops from the fourth energy level to the third energy level
c) The frequency and wavelength of this photon

Ans:
a) At n=3, E3= -RH = -2.18x10-18 J = -2.42x10-19 J
32 32
At n=4, E4= -RH = -2.18x10-18 J = -1.36x10-19 J
42 42

23
b) ΔE = E3 – E4,
= (-2.42x10-19 J) – (-1.36x10-19)
= -1.06x10-19 J
p/s: Note that the –ve sign indicates that energy is released
when an electron falls.
To calculate the amount of energy released by one
mole of electrons, multiply with NA

ΔE = -1.06x10-19 J x - 6.022x1023
= -63.83 kJ/mol
c) Frequency and wavelength

Frequency, ν= E= -1.06x10-19J = 1.60x1014 s-1

h 6.63x10-34 Js-1
p/s: Ignore –ve sign, frequency value always +ve

Wavelength, λ = c = 3.00x108ms-1 = 1875 nm

24
ν 1.60x1014 s-1
 QUANTUM NUMBERS &
ATOMIC ORBITAL SHAPES 3.2 & 3.3
25
QUANTUM NUMBERS
Atomic orbital – the wave function that is characterized by
values of 4 quantum numbers
Quantum Numbers, Y = (n, l, ml , ms)

1. Principle Quantum Number (n)

2. Angular Momentum Quantum Number (l)
3. Magnetic Quantum Number (ml)
4. Spin Quantum Number (ms)

26
1. PRINCIPAL QUANTUM NUMBER (N)
n = 1, 2, 3, 4, ….
• distance of e- from the nucleus
• the larger n value, the greater average distance of an e- in the
orbital from the nucleus, and the larger the orbital

27
2. ANGULAR MOMENTUM QUANTUM
NUMBER (ℓ)
• determines the shape of the orbitals
for a given value of n,
ℓ = 0, 1, 2, 3, … n-1

n = 1, l = 0 l=0 s orbital
n = 2, l = 0 or 1 l=1 p orbital
n = 3, l = 0, 1, or 2 l = 2 d orbital
l=3 f orbital

28
l = 0 (s orbitals)

l = 1 (p orbitals)

l = 2 (d orbitals)

29
3. Magnetic Quantum Number (mℓ)
• determines the orientation of the orbital in space
for a given value of l
mℓ = -l, …., 0, …. +l

if l = 1 (p orbital), mℓ = -1, 0, or 1
if l = 2 (d orbital), mℓ = -2, -1, 0, 1, or 2
* Each subshell of quantum number (ℓ) contains
(2ℓ+ 1) orbitals.

30
 ml = -1, 0, or 1

3 orientations is space

31
ml = -2, -1, 0, 1, or 2 5 orientations is space

32
Spin Quantum Number (ms)

ms = +½ or -½

ms = +½ ms = -½ 33
34
 Quantum Numbers: (n, l, ml, ms)

Shell – electrons with the same value of n

Subshell – electrons with the same values of n and l

Orbital – electrons with the same values of n, l, and ml

How many electrons can an orbital hold?

If n, l, and ml are fixed, then ms = ½ or - ½

y = (n, l, ml, ½) or y = (n, l, ml, -½)

An orbital can hold 2 electrons
35
Examples:
How many 2p orbitals are there in an atom?
n=2
If l = 1, then ml = -1, 0, or +1
2p
3 orbitals
l=1

How many electrons can be placed in the 3d subshell?

n=3 If l = 2, then ml = -2, -1, 0, +1, or +2
3d 5 orbitals which can hold a total of 10 e-

l=2 36
3.4 Arrangement of
Electrons

37
 Schrodinger Wave Equation

quantum numbers: (n, l, ml, ms)

Existence (and energy) of electron in atom is described

by its unique wave function y.

38
Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n

n=3

n=2

1
En = -RH ( )
n2

n=1

39
Energy of orbitals in a multi-electron atom
Energy depends on n and l

n=3 l = 2

n=3 l = 1
n=3 l = 0

n=2 l = 1
n=2 l = 0

n=1 l = 0
40
 Aufbau principle
“Fill up” electrons in lowest energy

??

Li 3 electrons B 5 electrons
Li 1s22s1 B 1s22s22p1
Be 4 electrons
Be 1s22s2

He 2 electrons
H 1 electron He 1s2
H 1s1
41
Order of orbitals (filling) in multi-electron
atom

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s42
 Pauli’s Exclusion Principle

•An orbital can accommodate a maximum of two

electrons only.
•Both the electrons must have opposite spin

Li (3 electrons) n=2, l=0, ml=0, ms=+1/2

1s 2s

n=2, l=0, ml=0, ms =+1/2 n=2, l=0, ml=0, ms =-1/2

43
 Hund’s rule
The most stable arrangement of electrons in subshells is
the one with the greatest number of parallel spins

F 9 electrons
F 1s22s22p5

O 8 electrons
O 1s22s22p4

C 6 electrons
C 1s22s22p2

Ne 10 electrons N 7 electrons
Ne 1s22s22p6 N 1s22s22p3
44
3.4 Arrangement of
Electrons

45
Electron configuration is how the electrons are distributed
among the various atomic orbitals in an atom.

number of electrons
in the orbital or subshell
1s1
principal quantum angular momentum
number n quantum number l

Orbital diagram

H
1s1
46
Electronic Configurations of Some Second
Row Elements

47
Example:
What is the electron configuration of Mg?

Mg 12 electrons
1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s2 2 + 2 + 6 + 2 = 12 electrons

Abbreviated as [Ne]3s2 [Ne] 1s22s22p6

What are the possible quantum numbers for the last

(outermost) electron in Cl?

Cl 17 electrons 1s < 2s < 2p < 3s < 3p < 4s

1s22s22p63s23p5 2 + 2 + 6 + 2 + 5 = 17 electrons
Last electron added to 3p orbital

n=3 l=1 ml = -1, 0, or +1 ms = ½ or -½ 48

Outermost subshell being filled with
electrons

49
50
 Paramagnetic Diamagnetic
unpaired electrons all electrons paired

2p 2p
51
Example:

How many electrons in 12Mg can have the

following quantum numbers?

a) s=+1/2
b) n=4
c) n = 1,s = -1/2
d) l =1
• Electron configuration:
1s2 2s2 2p6 3s2
• Orbital diagram:

1s2 2s2 2p6 3s2

52
Answer:

a) 6 electrons
b) 0 electron
c) 1 electron
d) 6 electrons

53
 Importance of Atomic Number

• The atomic number uniquely identifies a chemical

element
• Elements in the periodic table are presented in order
of increasing atomic number
• When atom is neutral, the atomic number will equal
the number of electron
• Atomic number determines the properties of the
element

54
3.5 Periodic Trends of
Elements

55
 Lesson Outcomes
• Indicate period, group and block s, p, d, f
• Specifies the position of metals, metalloids and non-
metals in the periodic table
• Describe the metallic behavior and acid-base
• Explain the variation in atomic , ionic and isoelectronic
radii
• Define the first and second ionization energies and
explain the variations in the first ionization energy across
period and down the group
• Define electron affinity and electronegativity
• Explain the variation in electronegativity of elements

56
Element

• Scientists have identified

90 naturally occurring
elements, and created
about 28 others
• The elements, alone or in
combinations, make up
our bodies, our world, our
sun, and in fact, the entire
universe.

57
The most abundant element in the earth’s
crust is oxygen

58
When the Elements Were Discovered

59
The Modern Periodic Table

60
 61

Noble Gas
Halogen
Classification of the Elements

Group
Period
Alkali Earth Metal
Alkali Metal
 Important Group Names

Group(s) Group Name

1 Alkali Metals
(Very Reactive)

Alkaline Earth Metals

2
(Very Reactive)

3-11 Transition Metals

17 Halogens
(Very Reactive)

18 Noble Gases
(Not Reactive)*Stable
62
 Electronic Configurations
Generally the periodic table can be divided into 4 major
regions which called blocks; s-block, p-block, d-block and f-
block, based on their electronic configurations

1.The s-block:
•The s-block is occupied by elements with a half-filled or a
completely-filled outermost s orbital. Having configuration of
ns1 at the Group 1. These elements are metals (except H), also
known as alkali metal.
•The next group in s-block is Group 2, comprised of
elements with a completely-filled outermost s orbital (ns2), also
known as alkaline earth metals

63
2. The p-block:
The p-block elements are elements that have electrons in the
outermost p orbital. The valence electronic configuration
varies from ns2 np1 (Group 13) to ns2 np6 (Group 18).
Consists of metals, metalloids and non-metals. Group 17
known as halogens and group 18 known as noble gas
3. The d-block:
The d-block elements are called the transition elements
which have partially-filled or completely filled d orbitals (d1 to
d10)
4. The f-block:
The f-block is known as the inner transition elements. The
first row elements are called lanthanides and second row is
called actinides. These elements also known as rare
earth elements

64
 ns1

4f
5f
ns2

d1

d5

d10

ns2np1
ns2np2
ns2np3
ns2np4
ns2np5
65

ns2np6
 Exercise 1

Determine the period, block and group for each element with
the following configuration:
1.A: 1s2 2s2 2p3 - Period 2, block p, group 15

2.B: 1s2 2s2 2p6 3s2 3p6 - Period 3, block p, group 18

3.C: 1s2 2s2 2p6 3s2 - Period 3, block s, group 2

66
 Atomic and Ionic Radii
• There are 2 major factors affecting the size of atoms:

1. The effective nuclear charge (Zeff)

- the residual nett charge felt by the velence electrons
2. The shielding effect
- also known as screening effect
- caused by mutual repulsion of electron for each other

67
Effective nuclear charge (Zeff) is is the "positive c harge" felt by
an electron

Zeff = Z - s 0 < s < Z (s = shielding constant)

Zeff  Z – number of inner or core

electrons
Z Core Zeff Radius (pm)

Na 11 10 1 186
Mg 12 10 2 160

Al 13 10 3 143

Si 14 10 4 132

68
Effective Nuclear Charge (Zeff)

69
 Size of Atom
• Across a period, from left to right of the periodic table, a
gradual decrease in size of atom is observed:

• The increase in proton number leads to the increase in zeff

• The valence electrons experience a greater attraction & being
pilled closer to the nucleus
• Results in decrease in size of atoms

70
• Down within a group, the increase in size of atoms is
observed

• Down the group, the additional electrons of each of element

go to bigger (larger value of n)
• The additional inner orbitals leads to an increase in the
shielding effect, hence the size of atom increases

71
72
 A look at one period

Li - 1s22s1 Be - 1s22s2
Be has a smaller
radius than Li
because there is one
1s 1s
3P+ 4P+ more electron and
the attraction
between them is
stronger. The
“shells” get pulled in
tighter around the
nucleus.

73
 A look at one group

• Moving down any group, 4s

another shell is added. 3s
2s
• Example: H, Li, Na, K
• Each new shell is further 1s
from the nucleus so an
atomic size increases
from top to bottom.

74
 The size of Ions
• The size of positive ions (cation)
- formed when atom loses electron
- always smaller than its neutral atom
- The atoms lose the valence electrons, leaving electrons of the
inner shells which tend to attract the nucleus more, thus
decreasing size
- E.g. Na+ ion < Na atom

75
• The size of negative ions (anion)
- formed when atom gains electrons
- always larger than its neutral atom
- electrons are added into the same shell and tend to
repel each other and so increase size
E.g. Cl- ion > Cl atom

76
The Radii (in pm) of Ions of Familiar
Elements

77
Comparison of Atomic Radii with Ionic
Radii

78
 Electron Configurations of Cations and
Anions of Representative Elements

Na: [Ne]3s1 Na+ [Ne] Atoms lose electrons so that

Ca: [Ar]4s2 Ca2+ [Ar] cation has a noble-gas outer
electron configuration.
Al: [Ne]3s23p1 Al3+ [Ne]

H: 1s1 H- 1s2 or [He]

Atoms gain electrons so
that anion has a noble- F: 1s22s22p5 F- 1s22s22p6 or [Ne]
gas outer electron
configuration. O: 1s22s22p4 O2- 1s22s22p6 or [Ne]

N: 1s22s22p3 N3- 1s22s22p6 or [Ne]

79
 Cations and Anions of Representative
Elements

+3
+2
+1

-2
-3

-1
80
 Isoelectronic: have the same number of electrons, and hence the
same ground-state electron configuration

Na+: [Ne] Al3+: [Ne] F-: 1s22s22p6 or [Ne]

O2-: 1s22s22p6 or [Ne] N3-: 1s22s22p6 or [Ne]

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

What neutral atom is isoelectronic with H- ?

H- : 1s2 same electron configuration as He

81
 Electronegativity

•The ability of an atom to attract electrons (or electron density)

towards itself in a covalent bond
•Across a period of elements, electronegativity increases. If
valence shell of an atom is less than half full, it requires less
energy to lose an electron than gain one and thus, it is easier to
lose an electron & vice versa
•Down a group, electronegativity decreases. This is because
the atomic number increases down a group and thus there is an
increased distance between the valence electrons and nucleus,
or a greater atomic radius

82
 electronegativity increase
electronegativity decrease

83
 1st Ionization Energy

•1st ionization energy is the amount of energy required to

remove an electron from an isolated neutral gaseous atom in its
round state

•This process is endothermic as energy must be supplied to

remove electron which is attracted to the positive charge of the
nucleus

84
• Ionization energy across a period:
- From left to right of periodic table, the atomic size decreases,
the outer e- are more closely attracted to the nucleus and thus
are more difficult to be removed
- The ionization energy increases across the period

• Ionization energy down a group:

- Down within a group, the ionization energy decreases
- The atomic radius increases as we go down the group
- The atomic size expands as more e- are added to the
successive energy level (shielding effect increases)
- The outer e- is far from nucleus and less attraction towards
nucleus

85
 General Trends in Electron Affinity

Increasing First Ionization Energy

Increasing First Ionization Energy

86
 Electron Affinity
• Electron affinity is the negative of the energy
change that occurs when an electron is accepted by an
atom in the gaseous state to form an anion
• Electron affinity generally increases across a period
in the periodic table and decreases down a group,
caused by the filling of the valence shell of the atom
• A Group-17 atom releases more energy than a Group-1
atom upon gaining an electron because it obtains a
filled valence shell and therefore is more stable
• Electron affinity follows the trend of electronegativity:
fluorine (F) has a higher electron affinity than oxygen,
and so on

87
General Trends in Electron Affinity

Electron affinity increase

88
89
Summary

90