+Unit III

Periodic table: Modern periodic table, periodicity in properties of elements, atomic radii,
ionic and covalent radii, ionization energies, electron affinity, electro-negativity.

Modern periodic table

“The properties of elements are periodic functions of their atomic numbers”. If elements are
arranged in increasing order of their atomic numbers, there is repetition of properties after 2,
8, 8, 18 and 32 elements. 2, 8, 18 and 32 numbers are also referred as magic numbers.
Repetition of properties after these numbers is due to repetition of electronic configurations of
the outermost orbit.
H1 1s1
Li3 1s2, 2s1
Na11 1s2, 2s2, 2p6, 3s1
K19 1s2, 2s2, 2p6, 3s2, 3p6, 4s1
Rb37 [Kr] 5s1
Cs55 [Xe] 6s1
Fr87 [Rn] 7s1 [H to Fr have been placed together in group IA due to outer most ns 1 configuration]

Long form (Modern form) of Periodic table:

 It can explain why certain elements resemble one another and also why they differ
from other elements in their properties.
 This table also explain the cause of periodicity of properties and the reason why
similar properties recur at certain regular intervals.
 The horizontal rows constitute periods while the vertical rows constitute groups or
families.
 4th, 5th, 6th, and 7th periods also include transition elements.
 6th, and 7th periods also include inner transition elements (rare-earth) and grouped at
the bottom of the main periodic table.
 Element (58-71) are called lanthanides while elements (90-103) are called actinides.
Each has 14 elements and grouped in III B.
The arrangement of the long periodic table may be explained from the distribution of
electrons in various quantum levels. Electrons in various subshells have been filled based on
Aufbau Principle. It follows (n + l) rule. According to this electron enter in that subshell
which has minimum value of n + l and for equal value of n + l, electron goes in that subshell
which has less vlue of n.

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s- and p- block elements are called representative elements, those to the d-block are called
transition elements and f-block are termed the inner-transition elements.

IUPAC Nomenclature of Elements with atomic number above 100

Digit Name Abbreviation

0 Nil n
1 Un u
2 Bi b
3 Tri t
4 Quad q
5 Pent p
6 Hex h
7 Sept s
8 Oct o
9 enn e

Ex: 101- Unu, 102- Unb, 110- Uun, 117- Uus

Periodicity
When elements are arranged in increasing order of atomic number, the recurrence of similar
properties of elements after certain regular intervals is called periodicity.
 Periodicity is due to recurrence of similar outer electronic configurations of their
atoms at certain regular intervals.
 Recurrance of properties is after 2, 8, 8, 18 and 32 elements.

Size of an atom and ion

Atomic radius is taken as the distance from the centre of the nucleus to the outermost shell.
Atomic radius is taken as the effective size which is the distance of the closest one atom to
another atom in a given bonding situation. Atomic radius can be:
 Covalent radius
 Vander Waals radius
 Ionic radius
Covalent Radius: It is one half of the distance between the centres of two nuclei bonded by a
single covalent bond.
In a heteronuclear, diatomic molecule of AB type, bond length rA-B is equal to the sum of
covalent radii of A and B i.e.,

rA-B = rA + rB
If there is difference in the electronegativities of the bonded atoms, it causes shortening of the
bonds. Schoemaker and Stevenson gave following relation:

rA-B = rA + rB – 0.07 (XA- XB )2

where, rA and rB are radius of atom A and B respectively. XA and XB are electronegavity of
atom A and B respectively.
The radii decrease from left to right along a period with increase in nuclear charge. The radii
increase downward along group with increasing principal quantum number of the outermost
shell.

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Vander Waals radius: It is one-half of the internuclear distance between two adjacent atoms
in two nearest neighbouring molecules of the substance in solid state.

Ionic radius: The effective distance from the nucleus of the ion upto which it has an
influence in the ionic bond is called ionic radius.
 Metal ions (positive ions) are smaller than the atoms from which they were formed.
This is because the number of positive charges on the nucleus exceeds the number of
orbital electrons. Eg. Order of size as follows-
Na > Na+
As positive charge increases on atom, its size decreases. Eg. Order of size as follows-
Mg > Mg+ > Mg2+
 The negative ion is always larger than that of the corresponding atom. This is because
by gaining of electrons number of electrons increases but magnitude of nuclear charge
remains the same. Nuclear charge is thus reduced and the electron cloud is held less
tightly by the nucleus resulting in the expansion of outer-shell. Thus size of negative
ion is increased as follows:
O2- > O- > O
 Iso-electronic species (containing equal number of electrons) will have different size
due to different value of atomic number (Z). (F-, Na+, Mg2+, Al3+, Si4+).
Size of isoelectronic species is inversely proportional to effective nuclear charge
(e/Z).
 In the main group, radii increases on descending the group because extra shell is
added.
Li+ < Na+ < K+
 The ionic radii decrease moving from left to right across any period in the periodic
table.
Na+ > Mg2+ > Al3+
 The d and f- orbital do not shield nuclear charge very effectively. Thus there is
significant reduction in the size of the ions just after d and f-orbitals have been filled
completely. This is called lanthanide [Link] d block elements have equal
size due to lanthanide contraction.
Eg: Zr (160 pm) and Hf (159 pm)

Ionization Energy (IE):

Ionization energy (IE) is also called ionization potential (IP). It is defined as the amount of
energy required to remove an electron from an isolated gaseous atom of that element resulting
in the formation of positive ion.
𝐼𝐸1
M (g) → M+ (g) + e−
𝐼𝐸2
M+ (g) → M2+(g) + e−
𝐼𝐸3
M2+ (g) → M3+ (g) + e−

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  The smaller the ionization energy, the easier it is for the neutral atom to change in to a
positive ion.
 (IE) 1, (IE) 2, (IE) 3….. are respectively first, second, third….ionization energies
required to remove first, second, third… electron from the isolated gaseous atoms. It
is difficult to remove electron from positively charged atom thus-
(IE) 1 < (IE) 2 < (IE) 3
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(1 eV = 1.6 x 10 J )

Factors influencing Ionization Energy

IE variation in a period and group may or may not be regular and can be influenced by:
1. Size of the Atom: With increase in the atomic radius, the attraction between the
nucleus and the outermost electron decreases. Due to this, the outermost electron is
loosely held. Due to this, less energy is required to remove the electron. Hence, with
increase in the atomic radii, the ionization potential decreases.
2. Effective nuclear charge: With increase in the effective nuclear charge, the attraction
between the nucleus and the outermost electron increases. Due to this, the outermost
electron is tightly held, so more energy is required to remove the electron. Hence, IE
increases with increase in nuclear charge.
3. Shielding effect: The electrons in the inner-shell act as a screen or shield between the
nucleus and the electron in the outermost-shell. This is called shielding or screening
effect. The larger the number of electrons in the inner-shells, greater is the screening
effect and smaller the force of attraction and thus IE decreases.
4. Penetrating effect: The IE also depends on the type of electron which is removed. s,
p, d and f-electrons have orbitals with different shape. An s-electron penetrates nearer
to the nucleus and and is therefore more tightly held than a p-electron. Thus order of
penetration effect of orbitals as follows:
s>p>d>f
With increase in the penetrating effect, the ionization energy increases.
5. Stability of half-filled and completely filled orbitals: Half-filled and completely
filled orbitals have extra stability. This extra stability increases the ionization energy.
Eg: IE1 of Be is greater than B and IE of nitrogen (N) is greater than oxygen (O).
Be (4)- 1s2, 2s2 & B (5) - 1s2, 2s2, 2p1

N (7)- 1s2, 2s2, 2p3 & O (8)- 1s2, 2s2, 2p4

Note: When an electron is removed from an atom, energy is needed. When an

electron is added to an atom, energy is released. Usually, alkali metals and alkaline
earth metals have very low first and second ionization energies respectively.
Electron Affinity (EA):
Electron affinity (EA) is the amount of energy which is released with the gain of electron by
the gaseous atom. It is also called first electron affinity.

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 Cl (g) + e− → Cl− (g), ∆H = - x kJ mol-1
EA = x kJ mol-1
Electron affinity is also called electron gain enthalpy.
 The greater the energy released in the process of taking up electron, the greater is the
electron affinity.
 The electron affinity of an atom measures the tightness with which it binds an
additional electron to itself.
 When addition of electron experience repulsion, energy will be required to add an
electron.
Ex. In noble gases extra electron goes in to (n +1) s orbital of higher energy.

Ne (10): 1s2, 2s2, 2p6 + e− → Ne− : 1s2, 2s2, 2p6, 3s1 ∆H = 29 KJmol-1
EA = -29 KJmol-1

Ex. The group II A elements with filled s subshell (ns2), also have negative or almost
zero EA.
Ex. When second electron is added to negatively charged atom, it feels repulsion due
to same charge (negative). Energy of system increases.
O− + e− → O 2− ∆H = 702 kJ mol-1
EA = -702 kJ mol-1
Note: First electron affinity is positive while enthalpy (∆H) is negative quantity. Second
electron affinity is negative while enthalpy (∆H) is positive quantity.
Variation of EA in a Period
 On moving across a period, the atomic size decreases and the force of attraction
exerted by the nucleus on the electron increases. Consequently the atom has greater
tendency to attract additional electron, i.e. electron affinity increases.
 EA value of metals is low while those of non-metals are high.
 Halogens have high electron affinity.
Variation of EA in a Group
 On moving down a group, the atomic size increases and the force of attraction exerted
by the nucleus on the electron decreases thus electron affinity decreases.

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  Note: Fluorine has less electron affinity than chlorine. This is due to small size of
fluorine atom where greater effectiveness of 2p- electrons repel the additional electron
entering the atom than to 3p- electrons in the larger Cl atom.
Electronegativity (EN)
It is tendency of atom to attract electrons to itself.
X (g) + e − → X− (g)
In a molecule, tendency of atom to attract shared electron pair towards itself is called
electronegativity of that atom. If in AB molecule EN of B atom is more than EN of A atom
then B pulls shared electron pair towards itself and bond becomes polar.

A ∗. B → 𝐴𝛿+ − 𝐵𝛿−

The absolute magnitude of electronegativity value of an element is not fixed. Different values
may be assigned to the same atom. Ex. Electronegativity tends to increase with higher
positive charge in cation because the remaining electrons are held more tightly to the nucleus.
Therefore, Fe3+, having a higher charge, is more electronegative than Fe2+.
Variation of EN in a Group
 On moving down the group atomic number (Z), number of shells (n) and atomic
radius (r) increases but effective nuclear charge (Z*) remains constant.
 So force of attraction between added electron and nucleus decreases. Therefore EN
decreases moving down the group.
Ex. In VII group F has highest EN and I has lowest EN.
Variation of EN in a Period
 While moving across a period left to right Z, Z* increases, r decreases and n remains
constant.
 So force of attraction between added electron and nucleus increases. Therefore EN
increases along a period.
Ex. Along II period Li has lowest EN and F has highest EN
Note:
 Fluorine is the most electronegative element, second is oxygen and third is nitrogen.
 Noble gases have zero value of electronegativity.
 The group I A meals have their nuclei quite strongly shielded. Hence they show little
tendency to gain new electron. The EN of transition metals do not change greatly
from one another.

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  The EN increases as we go from Li to Be but it decreases as we move from Be to Mg.
Li and Mg have close value of electronegativity. Because of this, Li and Mg show
similarity in properties- a diagonal relationship. Like this elements of II period show
diagonal relationship with III period elements. Elements pair showing this
relationship are:
Li−Mg, Be−Al, B−Si
 Hybrid orbitals with greater s-character should be more electronegative than hybrid
orbitals with less s-character. As s-character increases acidic character increases. sp-
hybridises nitrogen is more electronegative than fluorine.
If two atoms have similar electronegativity, the bond between H and X will be
covalent. Atoms with large difference in electronegativity lead to a bond with ionic
character. If A and B atom has χA and χB electronegativity respectively then:
χA –χB = 1.7 50 % ionic

χA –χB > 1.7 predominantly ionic

χA –χB < 1.7 predominantly covalent

Pauling,s Electronegativity Scale

If A and B atom has χA and χB electronegativity respectively then electronegativity difference:
χA –χB = 0.208 √∆A-B
Where, ∆A-B is
∆A-B = EA-B − √EA − A x EB − B
EA-B, EA-A, and EB-B represent bond energy of A-B, A-A and B-B respectively.

Mulliken,s Electronegativity Scale

Electronegativity (EN) can be regarded as the average of the ionisation energy (IE) and the
electron affinity (EA) of an atom.
𝐼𝐸+𝐸𝐴
EN =
2
Relation between Pauling,s and Mulliken,s Electronegativity

𝑀𝑢𝑙𝑙𝑖𝑘𝑒𝑛′ 𝑠 𝐸𝑁
Pauling’s EN =
2.8

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