CHM012

Chemistry for TOPIC 1

Engineers
Atomic
Structure and
Periodicity
MA. KARLA BARELA-CARMONA, M.Sc., R.Ch.
Department of Chemistry, CSM, MSU-IIT
 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.

 Electromagnetic Radiation
Characteristics of Electromagnetic
radiation (EMR)

Relationship of
wavelength and frequency:
 Example
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.

Practice Exercise
The laser in an audio CD player uses light with a wavelength of 7.80x102 nm.
Calculate the frequency of this light.
 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:
 Example
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
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.
 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
 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 Electronic Transitions in the Bohr Model for the
in such a way as to move an Hydrogen Atom
a) An Energy-Level Diagram for Electronic
electron from one “allowed” energy Transitions
state to another; the energy b) An Orbit-Transition Diagram, Which Accounts
defined by: E = hv. for the Experimental Spectrum
 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.
 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.
Topic 1: Atomic Structure and Periodicity
 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.
 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.
 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
 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.

Topic 1: Atomic Structure and Periodicity

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

Topic 1: Atomic Structure and Periodicity

 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.

Topic 1: Atomic Structure and Periodicity

 f Orbital
✔ Very complicated shapes.
✔ Seven equivalent orbitals
in a sublevel, l = 3

Topic 1: Atomic Structure and Periodicity

 Assignment #1
1. What color of light is emitted when an excited electron in the hydrogen atom
falls from:
a. n = 5 to n = 2
b. n = 4 to n = 2
c. n = 3 to n = 2
Which transition results in the longest wavelength of light?

❖ Reading Assignment: Quantum mechanical model of an atom, (pp 69)

2. (a). Why does the Bohr model of hydrogen atom violate the uncertainty
principle?
(b). In what way is the description of the electron using the wave function
consistent with de Broglie’s hypothesis?
(c). What is meant by the term probability density?
Topic 1: Atomic Structure and Periodicity
 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.
✔ When the electron occupies the lowest-
energy orbital (1s ), the hydrogen atom
is said to be in its ground state.
✔ When the electron occupies any other
orbital, the atom is in an excited state.

Topic 1: Atomic Structure and Periodicity

 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.)
✔ For a given value of n, the energy of
an orbital increases with increasing
value
Topic of l Structure and Periodicity
1: Atomic
 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.

Topic 1: Atomic Structure and Periodicity

 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.
✔ we conclude that an orbital can hold a maximum of two electrons and
they must have opposite spins.

Topic 1: Atomic Structure and Periodicity

 Electron Configuration
✔ The way electrons are distributed in an atom is
called its electron configuration.
✔ The most stable organization is the lowest possible
energy, called the ground state.
✔ the orbitals are filled in order of increasing energy,
4p 5
with no more than two electrons per orbital;
✔ 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.
Topic 1: Atomic Structure and Periodicity
 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.
✔ This representation is called orbital diagram

Example
The orbital diagram of oxygen:

Total no. of electrons: 8

Electron configuration, O: 1s22s22p4

Topic 1: Atomic Structure and Periodicity

 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.

Topic 1: Atomic Structure and Periodicity

 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.

Topic 1: Atomic Structure and Periodicity 30

 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)

Topic 1: Atomic Structure and Periodicity

 Filling of Orbitals in the Periodic Table
✓ 2A elements have an 𝑛𝑠 2 outer configuration,
and all 3A elements have an 𝑛𝑠 2 𝑛𝑝1 outer
configuration, with the value of n increasing as
we move down each column.

Topic 1: Atomic Structure and Periodicity

 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
with1:fAtomic
Topic and dStructure
orbitals, as well.
and Periodicity
 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

Topic 1: Atomic Structure and Periodicity
 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.

Topic 1: Atomic Structure and Periodicity

 Effective Nuclear Charge
✔ Many properties depend on attractions between valence
electrons and the nucleus.
✔ Electronsare 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.
❖ 1:ItAtomic
Topic decreases
Structuredown a group.
and Periodicity
 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 ↑).

Topic 1: Atomic Structure and Periodicity

 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.
Topic 1: Atomic Structure and Periodicity
 Ionic Radius – Isoelectronic Series
✔ Inan 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

Topic 1: Atomic Structure and Periodicity

 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).

Topic 1: Atomic Structure and Periodicity

 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:

Topic 1: Atomic Structure and Periodicity

 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
next1:electron.
Topic Atomic Structure and Periodicity
 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
the1:nucleus.
Topic Atomic Structure and Periodicity
 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).

Topic 1: Atomic Structure and Periodicity

 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
Topic elements
1: Atomic Structureisand
positive (X– is unstable).
Periodicity
 Electron Affinity
✔ This trend of lower electron affinities for metals is
described by the Group 1 metals:

✔ Notice that electron affinity decreases down the

group.

Topic 1: Atomic Structure and Periodicity

 Assignment #2
1. Which of the following would require more energy to remove an electron? Why?
Sodium vs. Chlorine
Lithium vs. Cesium

2. Which element has the larger second ionization energy? Why?

Lithium vs. Beryllium

3. Which of the following should be the larger atom? Why?

Sodium vs. Chlorine
Lithium vs. Cesium
4. Which is larger? Why?
The hydrogen 1s orbital
The lithium 1s orbital
5. Which is lower in energy? Why?
The hydrogen 1s orbital
Topic 1: The lithium
Atomic 1sand
Structure orbital
Periodicity