CHM012

Chemistry for Topic 1:

Engineers Atomic Structure and
Periodicity
Marybeth Hope T. Banda, R.Ch., M.Sc., Sep 2021
Department of Chemistry
College of Science and Mathematics
MSU-Iligan Institute of Technology

[email protected] | Page
 Review

Sep 2021
Topic 1: Atomic Structure and Periodicity | Page 2
Introduction: Matter, Energy, and Measurement Banda, Sep 2021 Page 3
Introduction: Matter, Energy, and Measurement Banda, Sep 2021 Page 4
 What we’ll learn in this topic
✔ Overview of the development of the modern (quantum) atomic theory

✔ Describe quantum mechanical structure of an atom and its properties

✔ Write the sets of quantum numbers of different atoms

✔ Describe shapes of different atomic orbitals

✔ Predict atomic and chemical properties using periodic trends

Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 5

 How this discussion is structured
✔ Topic 1 Part 1
• Experiments and concepts that led to the development of the quantum mechanical structure of
the atom

✔ Topic 1 Part 2
• Development of the quantum mechanical structure of an atom and its properties
• Quantum numbers

✔ Topic 1 Part 3
• Periodic trends

Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 6

 Electromagnetic Radiation
Electromagnetic radiation (EMR) – is one of the ways that energy travel through space.
The visible light is one type of EMR.

Figure 1. Classification of electromagnetic spectrum.

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 Electromagnetic Radiation
Characteristics of Electromagnetic radiation (EMR)

Relationship of wavelength and

frequency:
 

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 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(NO 3)2 and SrCO3 are
heated. Calculate the frequency of red light of wavelength 6.50 x 10 2 nm.

Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 9

 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(NO 3)2 and SrCO3 are
heated. Calculate the frequency of red light of wavelength 6.50 x 10 2 nm.
Solution:
 
 
 

Practice Exercise 1:
The laser in an audio CD player uses light with a wavelength of 7.80x10 2 nm. Calculate the frequency of this
light. (Ans. 3.84x1014 s-1)
Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 10
 Nature of Matter

✔ Max Planck found that energy can be gained or lost only in

whole-number multiples of hv.

 
where h is called Planck’s constant, 6.626x10-34 Js

britannica.com ✔ Energy was found to be quantized, wherein a system can

Max Planck transfer energy in whole quanta or “packets”. Thus energy has
(1858–1947) a particle-like properties.

Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 11

 Nature of Matter
✔ Einstein suggested that electromagnetic radiation can be
viewed as a stream of “particles” called Photons. Where the
energy of a photon is:
 

❖ Reading Assignment: Photoelectric Effect, (pp 57)

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 Example 2
The blue color in fireworks is often achieved by heating copper (I) chloride (CuCl) to about 1200 oC.
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?

Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 13

 Example 2
The blue color in fireworks is often achieved by heating copper (I) chloride (CuCl) to about 1200 oC.
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?
Solution:
 

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. 3x108 s-1, 1.99x10-23 J)
Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 14
 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.
Figure 2. Emission and absorption spectrum of
❖ Reading Assignment: Atomic Spectrum of Hydrogen, (pp 61) hydrogen
Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 15
 The Bohr Model of the Atom
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
nobelprize.org

atom.
✔ Energy is only absorbed or emitted in such a way as to
move an electron from one “allowed” energy state to
Niels Bohr another; the energy defined by: E = hv.
(1885-1962)
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 The Bohr Model of the Atom
Figure 3. Electronic Transitions in the Bohr
Model for the Hydrogen Atom

An Orbit-Transition Diagram, Which

Accounts for the Experimental Spectrum

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 The Bohr Model of the Atom
✔ Energy levels available to the electron in the hydrogen atom

✔ 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

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 The Bohr Model of the Atom
 

✔ The wavelength of the emitted photon can be calculated from the equation

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 The Bohr Model
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.
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 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.

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

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 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)
Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 22
 End of Part 1 of Topic 1

Sep 2021
Topic 1: Atomic Structure and Periodicity | Page 23
 Quantum Mechanical Model of the Atom
nobelprize.org

Werner Karl Prince Louis-Victor Erwin Schrödinger

Heisenberg Pierre Raymond de
Broglie
Sep 2021
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 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.
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 Quantum Numbers
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.
✔ sharp, principal, diffuse, and fundamental

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 Quantum Numbers
 

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 Example 4
1. For principal quantum level n = 5, determine the number of allowed subshells (different values of l), and
give the designation of each.

Solution:
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.

Solution:
magnetic quantum numbers = –2, – 1, 0, 1, 2
number of orbitals = 5

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 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.

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

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 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.

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

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 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.

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 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.)
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 Quantum Numbers
Spin Quantum Number (ms)
en.wikipedia.org

Samuel George
Goudsmit Uhlenbeck

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 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.

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 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.

Wolfgang Ernst Pauli

❖ Reading Assignment: Polyelectronic Atoms, (pp 77) and History of Periodic Table, (pp 79)
❖ Watch the video on the History of Periodic Table (link https://youtu.be/Xbv5QxOZhqo )
Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 37
 Electron Configuration
✔ The way electrons are distributed in an atom is called its
5 electron configuration.

4p ✔ The most stable organization is the lowest possible energy,

called the ground state.
✔ Each component consists of
• a number denoting the energy level;

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 Electron Configuration
✔ The way electrons are distributed in an atom is called its
5 electron configuration.

4p ✔ 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;

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 Electron Configuration
✔ The way electrons are distributed in an atom is called its
5 electron configuration.

4p ✔ 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.

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 Electron
Configuration

Sep 2021
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 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 5
The orbital diagram of oxygen:

Total no. of electrons: 8

Electron configuration, O: 1s22s22p4

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 Orbital Diagrams
Example 5

The orbital diagram of oxygen:

Total no. of electrons: 8
Electron configuration, O: 1s2 2s2 2p4

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 Hund's Rule of Multiplicity
“For degenerate orbitals, the
lowest energy is attained when the
number of electrons with the same
spin is maximized.”
en.wikipedia.org

Friedrich Hermann Hund

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 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.

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 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.

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 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)

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 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.

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 Example 6
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

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 Example 6
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 Sep 2021 | Page 50
 End of Topic 1 Part 2

Sep 2021
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 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.

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 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.

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 Effective Nuclear Charge
✔ 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 increases down a group.

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 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 ↑).

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 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.

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 Ionic Radius
✔ 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.

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 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

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 Example 7
Predict the trend in radius for the following ions: Be2+, Mg2+, Ca2+, and Sr2+

Topic 1: Atomic Structure and Periodicity Sep 2021 | Page 59

 Example 7
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:

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 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!

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 Ionization Energy, I
✔ 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.

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 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.)

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 Ionization Energy - Trends
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.

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 Ionization
Energy

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 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).

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 Example 8
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.

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 Example 8
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)
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 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).

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 Periodic Properties: Summary
Zeff, IE, EA
increases

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 End of Topic 1 of Module 1

Sep 2021
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