CHM012

CHEMISTRY FOR
ENGINEERS
TOPIC 1
Atomic Structure and Periodicity

MARIA DISTRESSA GENITA-BILLACURA, RCh, PhD

MSU-ILIGAN INSTITUTE OF TECHNOLOGY
CHEMISTRY DEPARTMENT 9/4/23 1
 Electromagnetic Radiation
Electromagnetic radiation (EMR) – is one of the ways that energy
travel through space. The visible light is one type of EMR.

Classification of electromagnetic spectrum.

BILLACURA, M.D.
 Electromagnetic Radiation

Characteristics of Electromagnetic
radiation (EMR)

Relationship of
wavelength and frequency:

BILLACURA, M.D.
 Example 1
The brilliant red colors seen in fireworks are due to the emission of light
with wavelengths around 650 nm when strontium salts such as Sr(NO3)2
and SrCO3 are heated. Calculate the frequency of red light of
wavelength 6.50 x 102 nm.

𝑐 = 𝜆𝜈
𝑐 2.9979 𝑥 10! 𝑚/𝑠
𝜈= = = 4.61 𝑥 10$% 𝑠 &$
𝜆 1𝑚
6.50 𝑥 10" 𝑛𝑚 𝑥
1.0 𝑥 10# 𝑛𝑚

Practice Exercise 1
The laser in an audio CD player uses light with a wavelength of 7.80x102 nm.
Calculate the frequency of this light. Ans. 3.84 x 1014 s-1

BILLACURA, M.D.
 Nature of Matter

Max Planck found that energy can be gained or

lost only in whole-number multiples of hv.

Energy was found to be quantized, wherein a where h is called

system can transfer energy in whole quanta or Planck’s constant,
“packets”. Thus energy has a particle-like 6.626x10-34 Js
properties.

Einstein suggested that electromagnetic

radiation can be viewed as a stream of
“particles” called Photons. Where the energy of
a photon is:

BILLACURA, M.D.
 Example 2

The blue color in fireworks is often achieved by heating copper (I)

chloride (CuCl) to about 1200oC. Then the compound emits blue light
having a wavelength of 450 nm. What is the increment of energy (the
quantum) that is emitted at 4.50x102 nm by CuCl?

Practice Exercise 2
Microwave radiation has a wavelength on the order of 1.0 cm. Calculate the
frequency and the energy of a single photon of this radiation. Ans. 3 x 108 s-1 , 1.99
x 10-23 J

BILLACURA, M.D.
 Atomic Spectrum of Hydrogen

Continuous spectrum (results when

white light is passed through a prism) –
contains all the wavelengths of visible
light
Line spectrum – each line corresponds
to a discrete wavelength:

Significance

Only certain energies are allowed for

the electron in the hydrogen atom.
Energy of the electron in the hydrogen
atom is quantized.
Emission and absorption spectrum of hydrogen

BILLACURA, M.D.
 The Bohr Model
Assumptions

Electrons in an atom can only

occupy certain orbits
(corresponding to certain
energies).
Electrons in permitted orbits have
specific “allowed” energies; these
energies will not be radiated from
the atom.
Energy is only absorbed or emitted
in such a way as to move an Electronic Transitions in the Bohr Model for the
electron from one “allowed” energy Hydrogen Atom
state to another; the energy a) An Energy-Level Diagram for Electronic
Transitions
defined by: E = hv. b) An Orbit-Transition Diagram, Which Accounts
for the Experimental Spectrum

BILLACURA, M.D.
 The Bohr Model
The energy absorbed or emitted from a single electron transition
from one energy level to another:

ΔE = change in energy of the atom (energy of the emitted photon)

nfinal = integer; final distance from the nucleus
ninitial = integer; initial distance from the nucleus

Limitations of Bohr’s model

It only works for hydrogen!
Classical physics would result in an electron falling into the positively charged
nucleus. Bohr simply assumed it would not!
Circular motion is not wave-like in nature.

Important ideas of Bohr’s model

Electrons exist only in certain discrete energy levels.
Energy is involved in the transition of an electron from one level to another.

BILLACURA, M.D.
 Example 3
Calculate the energy required to excite the hydrogen electron from level n=1 to level n=2. Also
calculate the wavelength of light that must be absorbed by a hydrogen atom in its ground state
to reach this excited state.

Solution:

Practice Exercise 3:
Calculate the energy required to remove the electron from a hydrogen atom in its ground state. (Ans. 2.178x10-18 J)

BILLACURA, M.D.
 Quantum Numbers
❖Solving the wave equation gives a set of wave functions, or orbitals, and their
corresponding energies.
❖Each orbital describes a spatial distribution of electron density.
❖An orbital is described by a set of three quantum numbers.

Principal Quantum Number (n)

The principal quantum number, n, describes the energy level on which the orbital resides.
The values of n are integers ≥ 1.
These correspond to the values in the Bohr model.

Angular Momentum Quantum Number (l)

This quantum number defines the shape of the orbital.

Allowed values of l are integers ranging from 0 to n − 1.
We use letter designations to communicate the different
values of l and, therefore, the shapes and types of
orbitals.

BILLACURA, M.D.
 s Orbital

The value of l for s orbitals is 0.

They are spherical in shape.
The radius of the sphere increases with the
value of n.
For an ns orbital, the number of peaks is n.
For an ns orbital, the number of nodes
(where there is zero probability of finding an
electron) is n – 1.
As n increases, the electron density is more
spread out and there is a greater probability
of finding an electron further from the
nucleus.

BILLACURA, M.D.
 p Orbital
The value of l for p orbitals is 1.
They have two lobes with a node between them.

BILLACURA, M.D.
 d Orbital
The value of l for a d orbital is 2.
Four of the five d orbitals have four lobes; the other resembles a p orbital
with a doughnut around the center.

BILLACURA, M.D.
 f Orbital

Very complicated shapes.

Seven equivalent orbitals
in a sublevel, l = 3

BILLACURA, M.D.
 Orbital Energy – Hydrogen Atom

For a one-electron hydrogen atom,

orbitals on the same energy level have
the same energy.
Chemists call them degenerate orbitals.

BILLACURA, M.D.
 Orbital Energy – Many-electron Atom

As the number of electrons

increases, so does the repulsion
between them.
Therefore, in atoms with more than
one electron, not all orbitals on the
same energy level are degenerate.
Orbital sets in the same sublevel
are still degenerate.
Energy levels start to overlap in
energy (e.g., 4s is lower in energy
than 3d.)

BILLACURA, M.D.
 Quantum Numbers
Magnetic Quantum Number (ml)

The magnetic quantum number describes the

three-dimensional orientation of the orbital.
Allowed values of ml are integers ranging from
−l to l: −l ≤ ml ≤ l

Therefore, on any given energy level, there

can be up to 1 s-orbital, 3 p-orbitals, 5 d-
orbitals, 7 f-orbitals, and so forth.

❖ Orbitals with the same value of n form an

electron shell.
❖ Different orbital types within a shell are
subshells.

BILLACURA, M.D.
 Example
1. For principal quantum level n = 5, determine the number of allowed
subshells (different values of l), and give the designation of each.

For n = 5, the allowed values of l run from 0 to 4 (n – 1 = 5 – 1).

Thus the subshells and their designations are:

l=0 l=1 l=2 l=3 l=4

5s 5p 5d 5f 5g

2. For l = 2, determine the magnetic quantum numbers (ml) and the number
of orbitals.

magnetic quantum numbers = –2, – 1, 0, 1, 2

number of orbitals = 5

BILLACURA, M.D.
 Quantum Numbers
Spin Quantum Number (ms)

In the 1920s, it was discovered that two

electrons in the same orbital do not have
exactly the same energy.
The “spin” of an electron describes its
magnetic field, which affects its energy.
This led to the spin quantum number, ms.
The spin quantum number has only two
allowed values, +½ and –½.

BILLACURA, M.D.
 Pauli Exclusion Principle

No two electrons in the same atom can have exactly the same
energy.
Therefore, no two electrons in the same atom can have
identical sets of quantum numbers.
This means that every electron in an atom must differ by at
least one of the four quantum number values: n, l, ml, and ms.

BILLACURA, M.D.
 Electron Configuration

The way electrons are distributed in an atom is

called its electron configuration.

4p 5
The most stable organization is the lowest possible
energy, called the ground state.
Each component consists of
❖a number denoting the energy level;
❖a letter denoting the type of orbital;
❖a superscript denoting the number of electrons in
those orbitals.

BILLACURA, M.D.
 Orbital Diagrams

Each box in the diagram represents one orbital.

Half-arrows represent the electrons.
The direction of the arrow represents the relative
spin of the electron.

Example
The orbital diagram of oxygen:

Total no. of electrons: 8

Electron configuration, O: 1s22s22p4

BILLACURA, M.D.
 Hund's Rule
“For degenerate orbitals, the
lowest energy is attained when
the number of electrons with
the same spin is maximized.”

This means that, for a set of

orbitals in the same sublevel,
there must be one electron in
each orbital before pairing and
the electrons have the same
spin, as much as possible.

BILLACURA, M.D.
 Condensed Electron Configuration

Elements in the same group of the periodic table have the

same number of electrons in the outer most shell. These are
the valence electrons.
The filled inner shell electrons are called core electrons.
These include completely filled d or f sublevels.
We write a shortened version of an electron configuration
using brackets around a noble gas symbol and listing only
valence electrons.

BILLACURA, M.D.
 Filling of Orbitals in the Periodic Table
We fill orbitals in increasing order of energy.
Different blocks on the periodic table correspond to different types of
orbitals: s = blue, p = pink (s and p are representative elements); d =
orange (transition elements); f = tan (lanthanides and actinides, or inner
transition elements)

BILLACURA, M.D.
BILLACURA, M.D.
 Electron Configuration Anomalies
Some irregularities occur when there
are enough electrons to half-fill s and d
orbitals on a given row.

❖For instance, the electron configuration

for chromium is
[Ar] 4s1 3d5
rather than the expected
[Ar] 4s2 3d4.
❖This occurs because the 4s and 3d
orbitals are very close in energy.
❖These anomalies occur in f-block atoms
with f and d orbitals, as well.

BILLACURA, M.D.
 Example
Give the electron configurations for sulfur (S) and cadmium (Cd)
Solution:
Sulfur is element 16 and resides in Period 3, where the 3p orbitals are being
filled. Since, sulfur is the fourth among the “3p elements,” it must have four 3p
electrons. Its configuration is:

S: 1s22s22p63s23p4 or [Ne]3s23p4

Cadmium is element 48 and is located in Period 5 at the end of the 4d transition

metals. It is the tenth element in the series and thus has 10 electrons in the 4d
orbitals, in addition to the 2 electrons in the 5s orbital. The configuration is:

Cd: 1s22s22p63s23p64s23d104p65s24d10 or [Kr]5s24d10

BILLACURA, M.D.
 Periodicity

Periodicity is the repetitive pattern of a property for elements based on

atomic number.
The following properties are discussed in this chapter:
• Sizes of atoms and ions
• Ionization energy
• Electron affinity
First, we will discuss a fundamental property that leads to may of the
trends, effective
nuclear charge.

BILLACURA, M.D.
 Effective Nuclear Charge

Many properties depend on attractions between

valence electrons and the nucleus.
Electrons are both attracted to the nucleus and repelled
by other electrons.
The forces an electron experiences depend on both
factors.
The effective nuclear charge, Zeff, is found this way:
Zeff = Z − S
where Z is the atomic number and S is a screening
constant, usually close to the number of inner electrons.

Effective nuclear charge is a periodic property:

❖ It increases across a period.
❖ It decreases down a group.

BILLACURA, M.D.
 Atomic Radius

The bonding atomic

radius is half the
internuclear distance
when atoms are bonded.
The bonding atomic
radius tends to
— decrease from left to
right across a period
(Zeff ↑).
— increase from top to
bottom of a group (n ↑).

BILLACURA, M.D.
 Ionic Radius

Determined by interatomic distances in ionic

compounds
Ionic size depends on
• the nuclear charge.
• the number of electrons.
• the orbitals in which electrons reside.
Cations are smaller than their parent atoms:
• The outermost electron is removed and
repulsions between electrons are reduced.
Anions are larger than their parent atoms:
• Electrons are added and repulsions between
electrons are increased.

BILLACURA, M.D.
 Ionic Radius – Isoelectronic Series

In an isoelectronic series, ions have the same number of electrons.

Ionic size decreases with an increasing nuclear charge.

An Isoelectronic Series (10 electrons)

• Note increasing nuclear charge with decreasing ionic radius as atomic
number increases

O2– F– Na+ Mg2+ Al3+

1.26 Å 1.19 Å 1.16 Å 0.86 Å 0.68 Å

BILLACURA, M.D.
 Electron Configuration of Ions
Cations: The electrons are lost from the highest energy level (n value).

Example:
Li+ is 1s2 (losing a 2s electron).
Fe2+ is 1s22s22p63s23p63d6 (losing two 4s electrons).

Anions: The electron configurations are filled to ns2np6.

Example:
F– is 1s22s22p6 (gaining one electron in 2p).

BILLACURA, M.D.
 Example
Predict the trend in radius for the following ions:
Be2+, Mg2+, Ca2+, and Sr2+

Solution:
• All of these ions are formed by removing two electrons from an atom of a Group 2A
element
• In going from beryllium to strontium, we are going down the group, so the sizes
increase:

BILLACURA, M.D.
 Ionization Energy, I
The ionization energy is the minimum energy required to remove an electron from the ground state of
a gaseous atom or ion.
The first ionization energy is that energy required to remove the first electron.
The second ionization energy is that energy required to remove the second electron, etc.
Note: the higher the ionization energy, the more difficult it is to remove an electron!

It requires more
energy to remove
each successive
electron.
When all valence
electrons have been
removed, it takes a
great deal more
energy to remove the
next electron.

BILLACURA, M.D.
 Ionization Energy - Trends
1. I1 generally increases across a period.
2. I1 generally decreases down a group.
3. The s- and p-block elements show a larger range of values for I1. (The d-
block generally increases slowly across the period; the f-block elements
show only small variations.)

Factors that Influences

Ionization Energy
Smaller atoms have higher I
values.
I values depend on effective
nuclear charge and average
distance of the electron from
the nucleus.

BILLACURA, M.D.
 Ionization Energy – Irregularities

The trend is not followed when the

added valence electron in the next
element
• enters a new sublevel (higher
energy sublevel);
• is the first electron to pair in one
orbital of the sublevel (electron
repulsions lower energy).

BILLACURA, M.D.
 Example
Consider atoms with the following electron configurations:
1s22s22p6 ; 1s22s22p63s1 ; 1s22s22p63s2
Which atom has the largest first ionization energy, and which one has the smallest second ionization
energy? Explain your choices.
Solution:
• The atom with the largest value of l1 is the one with the configuration 1s22s22p6 (this is the
neon atom), because this element is found at the right end of Period 2
• Since the 2p electrons do not shield each other very effectively, l1 will be relatively large
• The other configurations given include 3s electrons, which are effectively shielded by the core
electrons and are farther from the nucleus than the 2p electrons in neon
• Thus l1 for these atoms will be smaller than for neon
• The atom with the smallest value of l2 is the one with the configuration 1s22s22p63s2 (the
magnesium atom)
• For magnesium, both l1 and l2 involve valence electrons
• For the atom with the configuration 1s22s22p63s1 (sodium), the second electron lost
(corresponding to l2) is a core electron (from a 2p orbital)
BILLACURA, M.D.
 Electron Affinity
Electron affinity is the energy change accompanying
the addition of an electron to a gaseous atom:

Cl + e− ⎯⎯→ Cl−

It is typically exothermic, so, for most elements, it is

negative!
Not much change in a group.
Across a period, it generally increases. Three notable
exceptions include the following:
1) Group 2A: s sublevel is full
2) Group 5A: p sublevel is half-full
3) Group 8A: p sublevel is full

Note: For Group 8A the electron affinity for many of

these elements is positive (X– is unstable).

BILLACURA, M.D.
SUMMARY

BILLACURA, M.D.