B. Tech.

- 2nd Semester
CHEMISTRY-I
Unit-5

Periodic Properties

18-06-2022 1
Effective Nuclear Charge
For an atom or an ion with only a single electron, we can calculate the potential energy by
considering only the electrostatic attraction between the positively charged nucleus and the
negatively charged electron.

But when more than one electron is present, the total energy of the atom or the ion depends not
only on attractive electron-nucleus interactions but also on repulsive electron-electron interactions.

When there are two or more electrons, the repulsive interactions depend on the positions
of both electrons at a given instant, but because we cannot specify the exact positions of the
electrons, it is impossible to exactly calculate the repulsive interactions. Therefore we need
approximate methods to derive the influence of electron-electron repulsion.
If an electron is far from the nucleus (i.e., the distance r between the nucleus and the electron is large), then at
any given moment, many of the other electrons will be between that electron and the nucleus (Check Fig
below).

Hence the electrons will cancel a portion of the positive charge of the nucleus and thereby decrease the
attractive interaction between it and the electron farther away. As a result, the electron farther away
experiences an effective nuclear charge ( Zeff ) that is less than the actual nuclear charge Z . This effect is called
electron shielding.
As the distance between an electron and the nucleus (r) approaches infinity, Zeff approaches a value of 1
because all the other ( Z−1 ) electrons in the neutral atom are, on the average, between that electron and the
nucleus.

On the other hand, if an electron is very close to the nucleus, then at any given moment most of the other
electrons are farther from the nucleus and do not shield the nuclear charge.
At r ≈ 0 , the positive charge experienced by an electron is approximately the full nuclear charge, or Zeff ≈ Z .
At intermediate values of r , the effective nuclear charge is somewhere between 1 and Z . Thus;

1 ≤ Zeff ≤ Z
And for Hydrogen Zeff = Z

Thus, Shielding refers to the core electrons repelling the outer electrons, which lowers the effective charge of the
nucleus on the outer electrons. Hence, the nucleus has "less grip" on the outer electrons insofar as it is shielded
from them
 Effective Nuclear Charge, Zeff can be calculated by subtracting the magnitude of shielding from the total nuclear
charge and the effective nuclear charge of an atom is given by the equation below;

Zeff = Z − S

where Z is the atomic number (number of protons in nucleus) and S is the shielding constant and is approximated
by number of electrons between the nucleus and the electron in question (the number of nonvalence electrons). The
value of Zeff will provide information on how much of a charge an electron actually experiences.

Shielding Constant S is affected by the penetration of the orbitals which in turn affects the Effective nuclear Charge.
Electron Penetration/ Penetration of Orbitals

The actual Zeff experienced by an electron in a given orbital depends not only on the spatial distribution of the
electron in that particular orbital but also on the distribution of all the other electrons present.

This gives rise to large differences in Zeff for different elements, as shown in Figure below (this figure only
represents the elements of the first three rows of the periodic table)
Penetration describes the proximity to which an electron can approach to the nucleus. In a multi-electron system,
electron penetration is defined by an electron's relative electron density or probability density near the nucleus of
an atom (as shown in below Figure).
Electrons in different orbitals have different electron densities around the nucleus. In other words, penetration
depends on the shell ( n ) and subshell ( l ).
For example, a 1s electron (purple curve below) has greater electron density near the nucleus than a 2p electron
(red curve below) and has a greater penetration. This related to the shielding constants since the 1s electrons are
closer to the nucleus than a 2p electron, hence the 1s screens a 2p electron almost perfectly ( S=1 . However, the 2s
electron has a lower shielding constant ( S<1 because it can penetrate close to the nucleus in the small area of
electron density within the first spherical node (green curve below). In this way the 2s electron can "avoid" some of
the shielding effect of the inner 1s electron.
 For the same shell value ( n ) the penetrating power of an electron follows this trend in subshells

s>p>d≈f

for different values of shell (n) and subshell (l), penetrating power of an electron follows this trend

1s>2s>2p>3s>3p>4s>3d>4p>5s>4d>5p>6s>4f
Basically, penetration describes the proximity of electrons in an orbital to the nucleus. Electrons that have
greater penetration can get closer to the nucleus and effectively block out the charge from electrons that have
less proximity
Table : Effective Nuclear Charges for Selected Atoms
Atom Sublevel Z Zeff
H 1s 1 1
He 1s 2 1.69
Li 1s, 2s 3 2.69, 1.28
Be 1s, 2s 4 3.68, 1.91
B 1s, 2s, 2p 5 4.68, 2.58, 2.42
F 1s, 2s, 2p 9 8.65, 5.13, 5.10
Na 1s, 2s, 2p, 3s 11 10.63, 6.57, 6.80, 2.51
 Electronic Configuration and Periodicity

The Electronic configuration of elements in the periodic table is a fundamental property of an element. Electronic
configurations can vary based on the number of electrons and protons within an atom, which determines how
many shells there are.

The Electronic configuration relate it to periodic trends such as atomic radius, ionization energy, electron affinity,
electronegativity and boiling point.

These different properties come into play when considering electronic configurations because they determine
what type of chemical bonds formed between atoms with different Electronic configurations – for example
whether or not covalent bonds can form at all!
Electrons in an atom are distributed according to the electrons’ stability. Usually, atoms will have one or two unpaired
electrons. The distribution of these unpaired electrons is called electron configuration and each type of arrangement has
a name:

The most stable arrangement for atomic orbitals is “a bonding orbital” where there’s not any net negative charge; this is
when the number of electrons in bonding orbitals equals the number of protons.

The next stable configuration for electron distribution would be a “nonbonding orbital” where there’s not any net
positive charge, then an antibonding orbital that has more electrons than protons and finally a lone pair with one
unpaired electron on either end.

The electrons in an atom are considered more stable when they’re “bonding orbitals” because this is where there’s no
net charge and the electron distribution is symmetrical; if you had to choose between bonding or antibonding, it would
always be better for the electrons to be in a bonding orbital.

This doesn’t mean that the electrons will be in a “bonding orbital” the entire time. Electrons can jump between orbitals
by absorbing energy from outside sources that’s either transmitted (photon) or absorbed, then released into an orbital of
lower potential.
Shells
The maximum number of electrons that can be accommodated in a shell is based on the principal quantum
number (n). This formula 2n2, where ‘n’ is the shell level. The shells and values for n have been tabulated
below:

Shell and ‘n’ value Max. Electrons in the Electron

Configuration
K shell, n=1 2*12 = 2

L shell, n=2 2*22 = 8

M shell, n=3 2*32 = 18
N shell, n=4 2*42 = 32
Subshells
Electrons are distributed into subshells depending on their azimuthal quantum number (denoted by ‘l’). This quantum
number is dependent upon the value of the principal quantum, n. When n has a value of 4, four different subshells can
exist with electrons occupying l=0, 1 , 2 and 3 respectively. The s-subshell accommodates up to 2 electrons; p-subshell:
6; d-subshell contains 10 while f does not have any restrictions in this regard accommodating 14 total or two less than
its maximum occupancy capacity as given by the formula max =2*(2l+1) .
All the possible subshells for values of n up to 4 are tabulated below

Principle Quantum Value of Azimuthal Resulting Subshell in the

Number Value Quantum Number Electron Configuration
n=1 l=0 1s
n=2 l=0 2s
l=1 2p
n=3 l=0 3s
l=1 3p
l=2 3d
n=4 l=0 4s
l=1 4p
l=2 4d
l=3 4f
Aufbau principle and filling of atomic orbitals
The Aufbau principle, is the idea that electrons occupy orbitals of lower energy before occupying higher-energy
orbitals. Electrons are filled in order from 1s to 7p and an illustration can be seen below
Pauli Exclusion Principle and filling of atomic orbitals
In 1931, Wolfgang Pauli postulated an important principle to limit the number of electrons in a single orbital. He
found that only two can occupy this space at any given time and they must be oppositely spin for it not to create
instability in atoms with more than one electron.
This is also known as his “Principle of No More Than Two Electrons”. The idea behind this was what if there were
too many? It would cause extreme chaos and lack stability which could lead to chemical reactions depending on
how strong their magnetic fields are (since all electrons have slight magnets).

Hund’s Rule and filling of atomic orbitals

Hund’s rule is a quantum mechanical rule that determines the order in which electrons are filled. It states that
every orbital in a given subshell must be singly occupied by an electron before another one enters, and it explains
how to maximize total spin of all these electrons.
Electronic configuration chart

*Students must refer to the chart upto 30 (Z = 30) elements which is available in text books and on websites
In the Modern Periodic Table, the elements are arranged in the ascending order of their atomic
number. Elements are placed in groups and periods on the basis of similar properties and
systematic variation of properties.

The following periodic properties in the modern periodic table show the trends or periodicity and
shall be discussed.

• Atomic radius
• Ionic radius
• Ionization energy or ionization potential
• Electron affinity
• Metallic and nonmetallic character
• Melting and boiling point
• Oxidation State
• Electrical conductivity
Atomic radius trends
The average distance between the nucleus of the atom and its outermost shell provided that the atom is assumed
to be spherical is called the atomic radius

Atomic radii vary systematically in the periodic table

Atomic radii vary systematically in the periodic table

Due to increasing nuclear charge, the outermost orbital comes closer to the nucleus and atomic radii are
decreased.
• The number of shells remain the same
• The shielding effect remains the same

Atomic radii increase in a group from upper to downward direction

Number of shells increases down the group due to which the distance between outermost shell and nucleus is
also increased. Therefore radius is increase in a group.

Shielding effect increases down the group

Ionic radius trends in the periodic table

The distance from the center of charged atom to the periphery of the active sphere is called ionic radius

Cations:
When electrons are removed from the atoms positively charged ions are produced. The radii of positively
charged ions are smaller than the neutral atoms, which is known ad Ionic Radii

Anions:
When the electron is provided to the atom negatively charged ion is produced, which is bigger in size than
the neutral atom. The ionic radii of some negatively charged ions are given as follow
Ionic radii vary systematically in groups and periods in the periodic table
ionic radius trends in periods
As we move from left to right in a period, the ionic radii of the isoelectronic positive ions go on decreasing. Anyhow,
the values of ionic radii of the negatively charged ions go on increasing from left to right.

ionic radius trends in a group

The value of the positive charge remains the same in a group from top to the bottom. The ionic sizes of the positively
charged ion go on increasing from top to bottom.
Similarly, the values of ionic radii of negatively charged ions go on increasing down the group.
Ionization energy trend in the periodic table
It is the minimum amount of energy which is required to remove the most loosely bounded electron from
outermost orbital in its isolated state.
It is also known as ionization potential. It is abbreviated as I.E or I.P.

Explanation of ionization energy

Electrons are bounded to the nucleus in an atom, The electrons in the inner levels ( closer to nucleus) have greater
force of attraction than the outermost electrons.
The outermost electrons are valance electrons which require less energy to be removed.

Examples of Ionization energy

First ionization energy
The energy required to remove the first outermost electron is called first ionization energy. This happens in case of
group II-A and II-A elements.
The removal of electrons from the outermost orbital of the hydrogen atom, sodium, magnesium, and aluminum
along with required energies are as follows
Second ionization energy
When second electron is removed from the outermost orbital of the unipositive ions, then the higher amount of
energy is required. This is called second ionization energy of that element.
For example.
Mg——Mg+ + 1e–

Factors affecting the ionization energy values

The ionization energy of an atom depends upon the following factors.

Atomic size
Greater the atomic size of the atom, smaller the ionization energy value and vice versa.

Nuclear charge
Greater the nuclear charge of the atom greater the ionization energy value

Shielding effect
Shielding effect is decreasing force of attraction between the nucleus and outermost electron due to inner
electrons. Greater the shielding effect left the ionization energy of the atom.
 Variation of ionization energy values in the periodic table
Ionization energy values vary systematically in periods and Groups.
ionization energy trend in the period
As we go from left to right in a period ionization energy value increases. This is due to the sizes and increasing in
nuclear charges of atoms. Further the shielding effect also remains the same in a period.
ionization energy trend in a group
Ionization energy value decreases down the group. This is due to the increasing size of atom and increasing shielding
effect.
Graphical explanation of ionization energy
Groups
When a graph is plotted between atomic number on x axis and ionization energy values on y axis, then following
curve is obtained for alkali metals.
Periods
Rising curves obtained for the first, second, and third periods. Anyhow there are certain abnormalities are
which have their own reasons.
Alkali metals like Lithium Sodium and potassium have lowest ionization energy values in respective periods.
Electron affinity trend in periodic table

The minimum amount of energy that is released the observed when an electron is added to an isolated
neutral gaseous atom in its lowest energy state. It produces an anion is called electron affinity.

Explanation of electron affinity

Electron affinity is a quantitative measurement of the tendency of an atom of an element to accommodate
the electron in its outermost orbital.
If the atom has a tendency to accept the electron then it will release the energy and electron affinity is
represented by a negative sign. If the energy required by the electron then the electron affinity is positive.
Units of electron affinity
Electron affinity can be expressed in following units
I) KJ / mole
Ii) Kcal / mol
Second electron affinity
When an electron is added to an anion the process is endothermic due to its repulsion. And energy is supplied
to form a dinegative ion. This energy is given positive sign and it is called second electron affinity. The reason
is that energy is observed and a positive sign is given to the endothermic process.

Examples of electron affinity

Chlorine accepts the electron leases the 337 KJ / mole of energy. This is the first electron affinity.

Oxygen atom accepts one electron to form O negative anion and related 141 kilo joule per mole of energy. This
is first electron affinity.

O-1 can accept one more electron to make over -2. It absorbs 880 KJ / mol of energy. This is called second
electron affinity
Factors affecting the electron affinity
There are three factors which control the electron affinity values.

Atomic sizes
Greater the atomic size of an atom smaller the electron affinity

Nuclear charge
Greater the number of protons in the nucleus greater the electron affinity

Shielding effect
Greater the shielding effect of inner levels lesser electron affinity.

Electron affinity trend in a period

Electron affinity is increased from left to right in a period. This is due to the decreasing atomic sizes and
encouraging the Nobel charges. What’s the reason alkali metals have the lowest and halogen have the highest
value of electron affinity.

Electron affinity trend in group

Electron affinity decreases from upper to downward direction in a group. This is due to the increasing number
of shells increasing shielding effect.
Electronegativity is generally the ability of an atom to attract pair of bonding electrons toward
itself. It is dimensionless property because it is just an ability or capability of an atom to attract
pair of electrons.
As per definition;
The ability of an atom to get pair of electrons toward itself is known as electronegativity.
Periodicity of Electronegativity
The trend in the periodic table refers to the periodicity. Here we are going to discuss the
periodicity of the electronegativity along the groups and periods.

Electronegativity trend in periods

The trend in periods of electronegativity is given as the period’s electronegativity increases.

Explanation:
we go from left to right along period there is a decrease in size of atoms. Know why size
decreases as we move along periods. The reason is an electron and proton number increases
over the period. But shell no remains the same. Due to the increase in nuclear charge more
attraction is faced by the outermost shell and due to this reason shell size shrink along the
period and electronegativity increases.
Electronegativity trend in groups
The trend in groups of electronegativity is
given as the group’s electronegativity
decreases.

Explanation:
we go from top to bottom along with
group there is an increase in the size of an
atom. Know why size increases as we
move along the group. The reason is an
electron and proton number increases
along with groups. And also shell no
increases. As shell no increase size of
atoms also increases and shielding e also
increases and reduce the tendency to
attract shared pair of electron.
Factors which govern the electronegativity :
Some factors govern the electronegativity, how and in which manner detail is given below.

•Atomic size
•Nuclear charge
•Substitution effect

Atomic Size and electronegativity :

Electronegativity and atomic size are inversely proportional to each other. As the size of the atom
increases shielding effect also increases that reduces the ability of the atom to attract shared pair of
electrons toward itself. Similarly when the size of atom decreases then more attractive forces attract a
shared pair of electrons toward itself. So as a result increase in size causes a reduction in
electronegativity and a decrease in size causes an increase in electronegativity.

Nuclear charge and electronegativity :

Electronegativity and nuclear charge both are directly proportional to each other. With the increase in
nuclear pull when the size does not increase then electronegativity also increases. And with the
decrease in nuclear pull causes a decrease in electronegativity.