CHEMY 101

CHAPTER (6)

Electronic Structure and the Periodic Table

CHAPTER OUTLINE
6.1 Light, Photon, Energies, and Atomic Spectra
6.2 The Hydrogen Atom
6.3 Quantum Numbers
6.4 Atomic Orbitals, Shapes and sizes
6.5 Electron Configurations in Atoms
6.6 Orbital Diagrams of Atoms
6.7 Electron Arrangements in Monatomic ions
6.8 Periodic Trends in the properties of Atoms
6.1 Light, Photon, Energies, and Atomic Spectra
The Wave Nature of Light

Wavelength (l) is the distance

between identical points on
successive waves. measured in
nanometers (1 nm = 10-9 m).
Amplitude is the vertical distance
from the midline of a wave to the peak
or trough.
Frequency (n) Number of successive crests or troughs (wave cycles) that pass a
point in a unit of time. If 108 cycles pass in one second, the frequency is 108/s
or 108Hz

The speed of the wave C = l x n

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 Electromagnetic radiation.

Electromagnetic radiation is the emission and transmission of energy in

the form of electromagnetic waves.

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

All electromagnetic radiation

lxn=c 3
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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?

lxn=c
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

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➢ The Particle Nature of Light; Photon Energies
➢ Before the 20th century, light was explained in terms of waves
only
➢ Experiments from showed that light has properties not explained
by waves Max Planck, blackbody radiation
Albert Einstein, photoelectric effect
Today, we consider light to be a stream of particles called photons,
whose energy, E, is given by

h is Planck’s constant = 6.626  10-34 J  s (or 6.63  10-34 J s)

Energy (light) is emitted or absorbed in discrete units (quantum).

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When copper is bombarded with high-energy electrons, X rays
are emitted. Calculate the energy (in joules) associated with
the photons if the wavelength of the X rays is 0.154 nm.

E=hxn
E=hxc/l
E = 6.63 x 10-34 (J•s) x 3.00 x 10 8 (m/s) / 0.154 x 10-9 (m)
E = 1.29 x 10 -15 J

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Atomic Spectra

In 17th century, Sir Isaac Newton showed that visible (white) light
from the Sun can be broken down into its various color
components by a prism.

The atomic spectrum obtained is continuous; it contains all

wavelengths between 400 and 700 nm.

The situation with high-energy atoms of gaseous elements is quite

different (Figure 6.7). Here the spectrum consists of discrete
lines given off at specific wavelengths. Each element has a
characteristic spectrum that can be used to identify it.

For sodium, there are two strong lines in the yellow region at 589.0
nm and 589.6 nm. These lines account for the yellow color of
sodium vapor lamps used to illuminate highways. 8
The fact that the photons making up atomic spectra have only certain discrete
wavelengths implies that they can have only certain discrete energies, because
E = hn = hc/l

Since these photons are produced when an electron moves from one energy
level to another, the electronic energy levels in an atom must be quantized,
that is, limited to particular values.
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One of the simplest of atomic spectra, and the most important from a
theoretical standpoint, is that of hydrogen. When energized by a high-
voltage discharge, gaseous hydrogen atoms emit radiation at
wavelengths that can be grouped into several different series (Table 6.2).

The first of these to be discovered, the Balmer series, lies partly in the
visible region. It consists of a strong line at 656.28 nm followed by
successively weaker lines, closer and closer together, at lower
wavelengths.

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6-2 The hydrogen Atom
The hydrogen atom, containing a single electron, has played a major role in the
development of models of electronic structure
Bohr Model
The Bohr model assumed that a hydrogen atom consists of a central proton about which
an electron moves in a circular orbit.
He related the electrostatic force of attraction of the proton for the electron to the
centrifugal force due to the circular motion of the electron.

In this way, Bohr was able to express the energy of the atom in terms of the radius of the
electron’s orbit.
To this point, his analysis was purely classical, based on Coulomb’s law of electrostatic
attraction and Newton’s laws of motion. Bohr boldly and arbitrarily assumed, in effect,
that the electron in the hydrogen atom can have only certain definite energies.
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 Bohr’s Model of the Atom
1. e- can only have specific
(quantized) energy values
2. light is emitted as e-
moves from one energy
level to a lower energy
level

1
En = -RH ( )
n2

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

RH (Rydberg constant) = 2.18 x 10-18J
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 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
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6-3 Quantum Numbers

• The Schrödinger equation can be solved exactly

only for the hydrogen atom
• Approximations allow for solutions of the
equation relevant to atoms with two or more
electrons
• The solutions result in orbitals, which have an
energy, a shape and an orientation in space
• The solutions result in three quantum numbers:
• n
• ℓ
• mℓ
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1st Quantum Number (n)
(Principal Quantum Number)

The principal energy level is specified by the first

quantum number, n
n = 1, 2, 3, 4, …
n = 1 is the first principal level
n = 2 is the second principal level, and so on …

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The Second Quantum Number, ℓ
(Angular Momentum Quantum Number), ℓ ;
Sublevels (s, p, d, f)

Each principal energy level (specified by n) has one or

more sublevels
•The sublevel is specified by the quantum number ℓ
•ℓ is derived from n:
•ℓ = 0, 1, 2 … (n-1)
•In the nth principal level, there are n sublevels
•Instead of using numbers, the sublevels are given
letter designations
•For ℓ = 0, 1, 2, 3 we use s, p, d, f
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Combining n and ℓ

n and ℓ are combined to indicate the principal and

subsidiary levels

➢1s means n = 1 and ℓ =0

➢2s means n = 2 and ℓ = 0
➢3p means n = 3 and ℓ = 1

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Relative Energy

❑For atoms with more than one electron, the energy is

dependent on both n and ℓ
ns < np < nd < nf
❑Recall that as n increases, energy increases
2s is higher energy than 1s
❑Combining both
2p is higher energy than 2s

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The Third Quantum Number, mℓ
(Magnetic Quantum Number ), mℓ; Orbitals
➢Each sublevel contains one or more orbitals, which
differ from one another in the value of the third
quantum number, mℓ
➢Just as ℓ depends on n, mℓ depends on ℓ
• mℓ = -ℓ … -1, 0, +1, … +ℓ
• There are 2ℓ + 1 orbitals per sublevel

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Sublevels s through f

➢For an s sublevel, ℓ = 0, so mℓ = 0
➢For a p sublevel, ℓ = 1 so mℓ = -1, 0, or 1
➢For a d sublevel, ℓ = 2 so mℓ = -2, -1, 0, 1, or 2
➢For an f sublevel, ℓ = 3 so mℓ = -3, -2, -1, 0, 1, 2 or 3

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The Fourth Quantum Number, ms
➢ The last quantum number is associated with the
electron spin
➢ Two spins are possible, clockwise and
counterclockwise
➢ There are two values of ms, + ½ and – ½

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❑ The Pauli Exclusion Principle
➢ No two electrons in the same atom may have the
same set of four quantum numbers
➢ Two electrons may occupy an orbital; these will differ
in spin
➢ The spins of two electrons in an orbital will be
opposite to each other

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■ A principal level of quantum number n has a capacity of 2n2.
For example, the total capacity of the fourth principal energy level is 2(4)2 = 32e–
■ A sublevel of quantum number (l) has a capacity of 2(2 l + 1).
For example, a 3d sublevel (l = 2) has a capacity of 2(2  2 + 1) = 10e–.

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6.4 Atomic Orbital Shapes and Sizes
➢ Recall that an orbital is a physical representation of the region in
space where there is a 90% probability of finding an electron
➢ We will consider the shapes of two types of orbitals in this
chapter

➢ s orbitals
are spherical, differing only in size
(they become larger as n increases)
• Each s orbital can hold 2 electrons

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➢ p orbitals
consist of two lobes along an axis
➢ There are three axes – x, y and z
➢ There are three p orbitals – px, py, and pz
➢ Each p orbital can hold 6 electrons

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 d Subshell

• Start at the third principle energy level

• Have a double dumbbell shape
• Each d subshell can hold 10 electrons

f Subshell
• Start at the fourth shell
• Have a complicated shape
• Each f subshell can hold 14 electrons
Summary

No. of Max., no., of Starts at

Subshell orbitals electrons energy level
s 1 2 1

p 3 6 2

d 5 10 3

f 7 14 4
Quantum numbers chart
6.5 Electron Configurations in Atoms
 Rules for Filling Electrons
1. Aufbau Principle:
Lowest energy fill first, then build up.
 7s 7p
Increasing energy

6s 6p 6d
5s 5p 5d 5f
4s 4p 4d 4f

3s 3p 3d

2s 2p Each box is an orbital

(Room for two electrons)
1s
❑ 4s, 5s, and 6s lie in energy lower than 3d, 4d, and
5d. Ex., 4s is filled before 3d Why?

❑ Because, as the size of the shell becomes larger, the

spacing between shells decreased

So, overlapping between higher subshells is occured

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 7p 6d
7s 6p 5f
5d
6s 5p 4f
4d
5s
Increasing energy

4p
4s 3d
3p
3s ►Distribution of 15 e
2p • The first 2 electrons go into
2s the 1s orbital
• Notice the opposite spins
• Only 13 more
1s
 7p 6d
7s 6p 5f
5d
6s 5p 4f
4d
5s
Increasing energy

4p
4s 3d
3p
3s • Distribution of 15 electrons
2p • 3 unpaired electrons
2s • 1s22s22p63s23p3

1s
Methods Representing Electron Configurations

1) Orbital Box Notation

➢ Shows each orbital as a box or line to be filled in.

➢ Follow order of filling.
Ex. Nitrogen, N, (Z=7) 1s 2s 2p

2) Standard or spdf Notation

Number of electrons
1s2 2s2 2p3

Sublevels
3) Shorthand Notation
• Use the last noble gas before the element.
• Write the symbol of the noble gas in brackets.
[He] = 2, then start with 2s
[Ne] = 10, then start with 3s
[Ar] = 18, then start with 4s, 3d

• Write the remaining configuration after the brackets

follows:
Ex: Chlorine, Cl, (Z= 17): [Ne] 3s2 3p5
Ex. Iron,Fe, (Z= 26)

1s 2s 2p 3s 3p 4s 3d

Or 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d6

Or [Ar] 4s2, 3d6

Remark:

Completely filled and half filled orbitals are more

stable than partially filled.
Ex. Chromium, Cr (Z=24)
1s2, 2s2, 2p6, 3s2, 3p6, 4s1, 3d5
NOT 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d4
Ex. Cupper, Cu (Z=29)
1s2, 2s2, 2p6, 3s2, 3p6, 4s1, 3d10
NOT 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d9
➢ For Negative Ions (Anions):
Add 1 electron for each negative charge i.e., (Z + charges)

Ex. Sulphide ion S-2 : for S (Z=16)

no of electrons distributed = (16 + 2) = 18 es
S-2 : 1s2, 2s2, 2p6, 3s2, 3p6

➢ For Positive Ions (Cations):

Remove 1 electron for each positive charge i.e., (Z - charges)

Ex. Magnesium ion (Mg2+): for Mg (Z=12)

no of electrons distributed = (12 - 2) = 10 es
Mg2+: 1s2, 2s2, 2p6
❑ Filling of Sublevels and the Periodic Table

➢ By using the periodic table, it is possible to quickly write an

electron configuration for any element
➢ Consider the Group 1 elements
➢ All have the outer configuration s1
➢ Consider the Group 2 elements
➢ All have the outer configuration s2
➢ Atoms of elements in a group have the same distribution of
electrons in the outermost principal energy level

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❑Notes on The Periodic Table
1. Elements in Group 1 and 2 fill an s sublevel
2. Elements in Groups fill a p sublevel
3. Elements of the transition metals fill a d sublevel
4. The two sets of 14 elements each at the bottom of the
periodic table fill f sublevels with a principal quantum number
two less than the period number
➢ First row: lanthanides
➢ Second row: actinides

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The Periodic Table

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Exceptions
➢ Some elements have electron configurations that
differ from those expected from the application of
the rules we have seen
➢ Cr is actually [Ar]4s13d5
➢ Cu is actually [Ar]4s13d10
These difference arise because
• The energy levels of the orbitals are close to each
other
• There is a gain in stability by producing a half-filled
or a filled shell where possible

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6.6 Orbital Diagrams of Atoms
One step beyond the assignment of electrons to orbitals is the
depiction of electrons in orbitals
Parentheses indicate orbitals (__)
Arrows, up and down, indicate electrons (↑↓)
Recall the ms quantum number
One electron in an atom has ms = ½ and the other has ms = - ½

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Note that:
Hund’s Rule: Maximize unpaired spins where possible
Substances with unpaired electrons are paramagnetic
Substances with all paired electrons are diamagnetic

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6.7 Electron Arrangements in Monatomic Ions

In forming an ion, electrons are removed from (cation) or

added to (anion) sublevels in the highest principal energy
level

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Problems: Give the Electron Configurations of the
following:
Mn :[Ar] 4s2 3d5
Mn2+ :[Ar] 4s0 3d5
Fe :1s22s22p63s23p64s23d6
Fe2+ :1s22s22p63s23p63d6
Fe3+ : 1s22s22p63s23p63d5
Br : [Ar] 4s² 3d¹⁰ 4p⁵
Br 1- : [Ar] 4s² 3d¹⁰ 4p6

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6.8 Periodic Trends in the properties of Atoms
➢ The chemical and physical properties of elements are a
periodic function of atomic number
➢ Recall that the number of electrons is equal to the atomic
number of an element
➢ Properties to be considered
1. Atomic radius or size (and ionic radius)
2. Ionization energy (I.E)
3. Electronegativity (E.N)

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(1) Atomic Size or radius
➢ Atomic size increases from top to down through a group.
Due to the increase in the number of energy levels (shells).
➢ Atomic size decreases from left to right to down through a period.
Due to As atomic number increases, electrons are added in the same energy
level, and the nuclear charge increases. So, attractive force between the
nucleus and the outermost electrons (valence electrons) increases, thus
electrons are pulled closer to the nucleus.
 Ionic Radius Cations are smaller than the atoms from
which they form
Fewer electrons mean increased effective nuclear charge on
those that remain

Anions are larger than the atoms from which they form
More electrons mean that there is more electron-electron
repulsion, so the size of the ion increases relative to that of
the atom.
(2) Ionization Energy (IE)
Ionization energy (IE) is the amount of energy required to
completely remove an electron from a gaseous atom.
IE is inversely proportional with atomic size

❖ Ionization energy decreases down a family from top to

bottom (Group Trends)
Because the electron is further away from the attraction of the
nucleus, and There is more shielding.

❖ Ionization energy increases across a period from left to

right (Period Trends)
Because All the atoms in the same period have the same energy
level, so same shielding. But increasing nuclear charge.
(3) Electronegativity (EN)
Electronegativity : the ability of an atom to attract electrons to itself
when it is chemically combined with another element.
EN is inversely proportional with atomic size
Trends
➢ Electronegativity decreases down a family from top to bottom
(Group Trends)
➢ Electronegativity increases across a period (Period Trends)

➢ Metals are at the left of the table have low electronegativity.

➢ Nonmetals are at the right end of the table have high electronegativity
End of Chapter 6