CHM111

Periodicity
 DR. A. F. ADEYEMI
DEPARTMENT OF CHEMISRY,
UNIVERSITY OF MEDICAL SCIENCES,
ONDO-CITY, NIGERIA

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 Introduction
• In chemistry, periodicity refers to repeating trends in element
properties on the periodic table.
• Basically, what this means is if you drop down a row (period) on
the table and move across it, elements follow the same trend as
other periods.
• Periodicity reflects Periodic Law.
• Periodic Law states that chemical and physical properties of
elements repeat in a predictable way when elements are
arranged by increasing atomic number.

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 Introduction
• In periodic table, elements within a group (column) display
similar characteristics. The rows in the periodic table (the
periods) reflect the filling of electrons shells around the
nucleus, so when a new row begins, the elements stack on
top of each other with similar properties.
• For example, helium and neon are both fairly unreactive
gases that glow when an electric current is passed through
them. Lithium and sodium both have a +1 oxidation state
and are reactive, shiny metals.
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 Periodic Trends
• Periodic trends are specific patterns that are present in the
periodic table that illustrate different aspects of a certain element,
including its size and its electronic properties. Major periodic
trends include: electronegativity, ionization energy, electron
affinity, atomic radius, melting point, and metallic character.
• Periodic trends, arising from the arrangement of the periodic
table, provide an invaluable tool to quickly predict an element's
properties.
• These trends exist because of the similar atomic structure of the
elements within their respective group families or periods, and
because of the periodic nature of the elements.
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 Electronegativity Trends
• Electronegativity describes an atom's ability to attract and bind
with electrons.
• Because electronegativity is a qualitative property, there is
no standardized method for calculating electronegativity. However,
the most common scale for quantifying electronegativity is the
Pauling scale, which assign a value of 4.0 to Fluorine (the most
electronegative element).
• The numbers assigned by the Pauling scale are dimensionless due
to the qualitative nature of electronegativity.
• Electronegativity values for each element can be found on certain
periodic tables. An example is provided below.
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 Electronegativity Trends

Figure 1: Electronegativity values

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 Electronegativity Trends
• Most atoms follow the octet rule (having the valence, or outer, shell
comprise of 8 electrons).
• Because elements on the left side of the periodic table have less than a half-
full valence shell, the energy required to gain electrons is significantly higher
compared with the energy required to lose electrons. As a result, the
elements on the left side of the periodic table generally lose electrons when
forming bonds.
• Conversely, elements on the right side of the periodic table are more energy-
efficient in gaining electrons to create a complete valence shell of 8
electrons.
• The nature of electronegativity is effectively described thus: the more
inclined an atom is to gain electrons, the more likely that atom will pull
electrons toward itself, and the higher the electronegativity.
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 Electronegativity Trends
• From left to right across a period of elements, electronegativity increases. If the valence
shell of an atom is less than half full, it requires less energy to lose an electron than to
gain one. Conversely, if the valence shell is more than half full, it is easier to pull an
electron into the valence shell than to donate one.
• From top to bottom down a group, electronegativity decreases. This is because atomic
shell increases down a group, and thus there is an increased distance between the
valence electrons and nucleus, or a greater atomic radius.
• Important exceptions of the above rules include the noble gases, lanthanides, and
actinides. The noble gases possess a complete valence shell and do not usually attract
electrons. The lanthanides and actinides possess more complicated chemistry that does
not generally follow any trends. Therefore, noble gases, lanthanides, and actinides do not
have electronegativity values.
• As for the d-block transition metals, although they have electronegativity values, there
is little variance among them across the period and up and down a group. This is
because their metallic properties affect their ability to attract electrons as easily as the
other elements.
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 Electronegativity Trends
• According to these two general trends, the most electronegative element
is fluorine, with 4.0 Pauling units.

Figure 2. Periodic Table showing Electronegativity Trend

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 Ionization Energy Trends
• Ionization energy is the energy required to remove an electron from a
neutral atom in its gaseous phase. Conceptually, ionization energy is the
opposite of electronegativity.
• The lower this energy is, the more readily the atom becomes a cation.
Therefore, the higher this energy is, the more unlikely it is the atom becomes
a cation.
• Generally, elements on the right side of the periodic table have a higher
ionization energy because their valence shell is nearly filled. Elements on the
left side of the periodic table have low ionization energies because of their
high willingness to lose electrons and become cations. Thus, ionization
energy increases from left to right on the periodic table.

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 Ionization Energy Trends

Figure 3: Graph showing the Ionization Energy of the Elements from

Hydrogen to Argon
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 Ionization Energy Trends

• In figure 3 above we observe some irregularities such between Be (4)

& B (5); N (7) & O (8); Mg (12) & Al (13); P (15) & S (16).
• These irregularities are due to relative stability of their orbitals
Note: A completely filled orbital is more stable than a half-filled orbital
A half-filled orbital is more stable than a partially filled orbital
The more stable the orbital is, the higher the ionisation energy
• Thus, N: 1s2 2s2 2px1 2py1 2pz1 (half-filled p-orbital) more stable
O: 1s2 2s2 2px2 2py1 2pz1 (partially filled p-orbital)
Hence, the ionisation energy of nitrogen should be higher than that
of oxygen
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 Exercise
• 1. Account for observed variation in the ionisation energies shown in
figure 3 between each of the following pairs of atoms
(i). Be & B
(ii). Mg & Al
(iii). P (15) & S (16).
2. Why helium has the highest ionisation energy?

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 Ionization Energy Trends

• Another factor that affects ionization energy is electron shielding.

• Electron shielding describes the ability of an atom's inner electrons to
shield its positively-charged nucleus from its valence electrons.
• When moving to the right of a period, electrons are being added to the
same shell, causing shrinking and less atomic radius, higher effective
nuclear charge (less shielding) and hence, higher ionization energy.
• Down the group, electrons are added to new shell, the number of
electrons increases and the strength of shielding increases and as a
result, it is easier for valence shell electrons to leave, causing ionization
of the atom. Thus the ionization energy decreases down a group.
• Electron shielding is also known as screening.
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 Ionization Energy Trends

Trends
• The ionization energy of the elements within a period generally
increases from left to right. This is due to increasing valence shell
stability.
• The ionization energy of the elements within a group generally
decreases from top to bottom. This is due to electron shielding.
• The noble gases possess very high ionization energies because of
their full valence shells as indicated in the graph.
• Note that helium has the highest ionization energy of all the elements. Could you
account for this? Hint: smallness and filled K-shell

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 Ionization Energy Trends

• Some elements have several ionization energies; these varying energies are
referred to as the first ionization energy, the second ionization energy, third
ionization energy, etc. The first ionization energy is the energy required to remove
the outermost or highest energy electron. The second ionization energy is the
energy required to remove any subsequent high-energy electron from a
monovalent gaseous cation, etc. Below are the chemical equations describing the
first and second ionization energies:
• First Ionization Energy:
X(g) → X+(g) + e− (1)
• Second Ionization Energy:
X+(g) → X2+(g) + e− (2)
• Generally, any subsequent ionization energies (2nd, 3rd, etc.) follow the same
periodic trend as the first ionization energy.
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 Ionization Energy Trends

Figure 4. Periodic Table Showing Ionization Energy Trend

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 Ionization Energy Trends

• Ionization energies decrease as atomic radii increase. This

observation is affected by n (the principal quantum number) and
effective nuclear charge, Zeff (based on the atomic number and
shows how many protons are seen in the atom) on the ionization
energy (I.E).
• The relationship is given by the following equation:
I.E = RH Z 2eff /n2 (3)
Across a period, Zeff increases and n (principal quantum number) remains
the same, so the ionization energy increases.
Down a group, n increases and Zeff increases slightly; the ionization energy
decreases.
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 Electron Affinity Trends
• As the name suggests, electron affinity is the ability of an atom to
accept an electron.
• Unlike electronegativity, electron affinity is a quantitative
measurement of the energy change that occurs when an electron is
added to a neutral gas atom.
• The more negative the electron affinity value is, the higher an atom's
affinity for electrons.

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 Electron Affinity Trends

Figure 5. Periodic Table showing Electron Affinity Trend

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 Electron Affinity Trends
• Electron affinity generally decreases down a group of elements because
each atom is larger than the atom above it (this is the atomic radius trend,
discussed below). This means that an added electron is further away from the
atom's nucleus compared with its position in the smaller atom. With a larger
distance between the negatively-charged electron and the positively-charged
nucleus, the force of attraction is relatively weaker. Therefore, electron
affinity decreases.
• Moving from left to right across a period, atoms become smaller as the forces
of attraction become stronger (decrease in atomic radius). This causes the
electron to move closer to the nucleus, thus increasing the electron affinity
from left to right across a period.

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 Atomic Radius Trends
• The atomic radius is one-half the distance between the nuclei of two atoms
(just like a radius is half the diameter of a circle).
• However, this idea is complicated by the fact that not all atoms are
normally bound together in the same way. Some are bound by covalent
bonds in molecules, some are attracted to each other in ionic crystals, and
others are held in metallic crystals. Nevertheless, it is possible for a vast
majority of elements to form covalent molecules in which two like atoms
are held together by a single covalent bond. The covalent radii of these
molecules are often referred to as atomic radii.
• This distance is measured in picometers.
• Atomic radius patterns are observed throughout the periodic table.

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 Atomic Radius Trends
• Atomic size gradually decreases from left to right across a period
of elements. This is because, within a period, all electrons are
added to the same shell. However, at the same time, protons are
being added to the nucleus, making it more positively charged.
The effect of increasing proton number is greater than that of the
increasing electron number; therefore, there is a greater nuclear
attraction (greater effective nuclear charge).
• This means that the nucleus attracts the electrons more strongly,
pulling the atom's shell closer to the nucleus. The valence
electrons are held closer towards the nucleus of the atom. As a
result, the atomic radius decreases.
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 Atomic Radius Trends
• Down a group, atomic radius increases. The valence electrons occupy higher
levels due to the increasing quantum number (n). As a result, the valence
electrons are further away from the nucleus as ‘n’ increases.
• Electron shielding prevents these outer electrons from being attracted to the
nucleus; thus, they are loosely held, and the resulting atomic radius is large.
Note
• Atomic radius decreases from left to right within a period. This is caused by the
increase in the number of protons and electrons across a period. One proton has a
greater effect than one electron; thus, electrons are pulled towards the nucleus,
resulting in a smaller radius.
• Atomic radius increases from top to bottom within a group. This is caused by electron
shielding.

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 Atomic Radius Trends

Figure 6: Periodic Table showing Atomic Radius Trend

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 Metallic Character Trends
• The metallic character of an element can be defined as how
readily an atom can lose an electron.
• From right to left across a period, metallic character increases
because the attraction between valence electron and the nucleus
is weaker, enabling an easier loss of electrons.
• Metallic character increases as you move down a group because
the atomic size is increasing. When the atomic size increases, the
outer shells are farther away. The principal quantum number
increases and average electron density moves farther from
nucleus. The electrons of the valence shell have less attraction to
the nucleus and, as a result, can lose electrons more readily.
This causes an increase in metallic character.
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 Metallic Character Trends
Note
• Metallic characteristics decrease from left to right across a period. This is
caused by the decrease in radius (caused by Zeff, as stated above) of the
atom that allows the outer electrons not to ionize more readily from left to
right across a period.
• Metallic characteristics increase down a group. Electron shielding causes
the atomic radius to increase thus the outer electrons ionizes more readily
than electrons in smaller atoms.
• Metallic character relates to the ability to lose electrons, and nonmetallic
character relates to the ability to gain electrons.

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 Metallic Character Trends
• Another easier way to remember the trend of metallic character is that
moving left and down toward the bottom-left corner of the periodic table,
metallic character increases toward Groups 1 and 2, or the alkali and alkaline
earth metal groups.
• Likewise, moving up and to the right to the upper-right corner of the periodic
table, metallic character decreases because you are passing by to the right side
of the staircase, which indicate the nonmetals. These include the Group 8, the
noble gases, and other common gases such as oxygen and nitrogen.
• In other words:
• Move left across period and down the group: increase metallic character (heading
towards alkali and alkaline metals)
• Move right across period and up the group: decrease metallic character (heading
towards nonmetals like noble gases)
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 Metallic Character Trends

Figure 7: Periodic Table of Metallic Character Trend

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 Summary

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Figure 8: Summary of Periodic Trends 31
 Exercise
• Discuss the ionic radius trend of elements in the periodic
table

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