PERIODICITY 1

CHAPTER-1

PERIODICITY

Basics of Periodic Table:

Periodic table represents the arrangement of all of the known elements according to their properties so that
similar elements fall within the same vertical column and dissimilar elements are arranged in horizontal rows with
slow gradation in properties.
“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, 18 and 32
elements in 1st, 2nd , 3rd and 4th period respectively. The numbers 2, 8, 18 and 32 are also referred as magic
numbers.
The periodicity is repetition of elements with similar properties after certain regular intervals when the
elements are arranged in order of increasing atomic numbers.
The periodic repetition of properties is due to the recurrence of similar valence shell electronic configu-
rations after regular intervals.

1.1 Mendeleev’s Periodic Law : According to Mendeleev’s periodic law

“The physical and chemical properties of the elements are a periodic function of their atomic weight.”
He arranged the elements in increasing order of atomic weights into groups and periods.

Drawbacks of Mendeleev’s Periodic Table :

Anomaly was found in three pairs of elements -
(i) Tellurium (Te) and Iodine (I)
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(ii) Argon (Ar) and Potassium (K)
(iii) Nickel(Ni) and Cobalt (Co)
which were not in accordance of their chemical behaviours.

1.2 Moseley’s Law: Long form (modern) Periodic Table:

On the basis of X-ray diffraction, Mosely proposed that
“The physical and chemical properties of elements are a periodic function of their atomic number or
their electronic configuration”.

Characteristic features of Long form of Periodic Table :

(1) The modern periodic table is divided into two main categories known as -
(a) Vertical Column- groups (18)
(b) Horizontal rows - periods (7)
(2) Elements of the same group have same valence shell configurations.
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(3) Elements of group IA to VII A (1,2,13,14,15,16,17) are known as representative elements (main group
elements) and of group IB to VIII B (3.................12) are known as transition elements.
(4) Elements of group-18 (also known as zero group) are noble gases.
(5) In periods , the number of valence shell remains the same, however the number of electrons increases from left
to right.

IA p-block
Zero
IIA IIIA IVA VA VIA VIIA

d-block
VIII
IIIB IVB VB VIB VIIB IB IIB

s-block

1.3. Classification of elements based on electronic configuration: All the electrons in an atom into specific
shells or orbitals (s, p, d, f) is known as the element’s electronic configuration. The elements can be arranged
in the long form of the periodic table based on the electronic configuration and classified as s, p, d and f
block elements. The s-block and p-block elements are called representative elements. The d-block elements
are called transition elements and f-block elements are called inner transition elements.
1. s-block elements: If the last electron enters into s-orbital, the elements are called as s-block elements.
 The general valence (outermost) shell electronic configuration is ns1–2 (where n represents the outermost
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shell). It contains elements of group 1 and 2. 1 are called alkali metals and 2 are called alkaline earth
metals.
 They are all reactive elements
 Except Beryllium, all other compounds of this block are predominantly ionic.
2. p-block elements: If the last electron enters into the p-orbital, the elements are called p-block
elements.
 Electronic configuration is ns2 np1–6.
 They are placed in group number IIIA to VIII A (13 to 18).
 He (ns2) is excluded from p-block in terms of electronic configuration and it is better to consider it as
s-block element. But according to its chemical behaviour it is justified to place it in the group 0, that
is group 18.
 Most of these, elements are non-metals, some are metalloids and a few other are heavy elements which
exhibit metallic character.
 The non-metallic character increases as we move from left to right across a period and metallic
character increases as we go down the group.
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3. d-block elements (Transition elements): If the last electron enters into d-orbital, the elements are
called as d-block elements (except Thorium)
 Electronic configuration is ns0–2 (n–1)d1–10
or, ns1–2 (n–1)d1–10 (except for palladium)
 d-block contains three complete, row of ten elements in each. The fourth row is incomplete the three
rows are called first, second and third transition element series. They involve the filling of 3d, 4d and
5d orbitals respectively.
 The d-block contains elements of group 3 to 12 of the periodic table.
4. f-block elements: (Inner transition elements): If the last electron of the elements enters into f-
orbital, they are considered as f-block elements.
 Electronic configuration is ns2 (n–1)d0–1 (n–2)f1–14
 They consist of two series of elements placed at the bottom of the periodic table. The elements of first
series follow lanthanum (La) and are called Lanthanoids. The elements of second series follow actinium
(Ac) and are called actinoids.

1.4 Periodic trends in properties of elements

(i) Metallic and Non-Metallic Character :

• The tendency of an element to lose electrons and form the ions is called electropositive character or
metallic character.
e.g. alkali metal are the most electropositive elements
• The tendency of an element to accept electrons to form an anion is called electronegative character or non-
metallic character.
e.g. chlorine, oxygen, nitrogen etc.

Groups
Metallic Character decreases on moving across the period
i.e non-metallic character increases

Periods
Metallic character increases down the group.
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i.e. non-metallic character decreases

Problem-1: Arrange the following elements in the increasing order of their metallic character.
Si, Be, Mg, Na, P
Soln. P  Si  Be  Mg  Na
Note
Metals are usually solids at room temperature having high melting point and boiling point mercury is an
exception (liquid metal) and Ga and Fr also have very low melting points (303K and 302K respectively).

(ii) Metalloids / semi-metals :

There are no sharp line dividing metals from non-metals. A zig-zag line separates metals from non-metals as
shown in figure. The borderline elements such as silicon, germanium, arsenic, antimony and tellurium exhibit
characteristic properties of metals as well as non-metals. These elements are called semimetals or metalloids.
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e.g. Si, As, Sb, Ge, Te

Metals have the tendency to form cations by loss of electrons and this property make the elements as electro
positive elements or metals.
 M  (g)  e 
M  g  
• The tendency of an element to lose electron is closely connected to the (IE) of the element.
• Smaller the (IE) of an element, the greater will be its tendency to lose electrons and thus greater will be
its metallic character.
• Greater the metallic character, greater the reducing nature.
* (IE) increases moving along a period left to right and decreases down the group, hence metallic and
reducing nature decrease along the period and increase down the group.

increases left to right in period

Nuclear charge 
increases left to right in period
Shielding 
But the nuclear charge wins so :
decreases left to right in period
Tendencey to form the ions  
decreases left to right in period
Reducing power  
Metallic nature www.careerendeavour.com
  decreases left to right in period

Problem-2: Tendency to lose electrons shows reducing property of the element. Arrange the following in
order of reducing property.
(a) Na,K,Rb (b) Na, Mg, Al (c) F , Cl , Br  , I (d) Mg, Ca, Sr

Soln. (a) Na  K  Rb (b) Na  Mg  Al

(c) F  Cl  Br   I  (d) Mg < Ca < Sr
(iii) Size of atoms and ions
(a) Atomic Radii :
The distance from centre of the nucleus to the outermost shell is called radius of an atom, it depends on
following factors:
(i) Principal Quantum number (n)
(ii) Effective Nuclear Charge A B
1
AB  covalent radius
2
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Effective nuclear charge (ENC) or Z*:

• The effective nuclear charge is the positive charge that an electron experience from the nucleus.
• It is the nuclear attractive force experienced by the electron when it is shielded by innerlying electrons.
• It is the nuclear charge reduced by shielding or screening from any intervening electrons.
• 2p electron is shielded more than or 2s electron as it penetrates the 1s orbital less than 2s orbital.
• As a result we have the energy sequence.
2s < 2p
3s < 3p < 3d
4s < 4p < 4d < 4f
As we move to atoms of elements of higher atomic number, the energy difference between orbitals of same
value of n decreases.
Screening Effect:

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The decrease in the nuclear force of attraction on the valence electrons or outermost electrons due to repulsive
forces of inner lying electrons is called screening effect.
The electrons of inner shell repel the electrons of outermost shells. The electrons of outermost shell are
thus shielded or screened from the nucleus by inner electrons.
As a result of screening effect the outermost electrons do not experience the complete nuclear charge.
The radial distribution of electron densities indicates that 2s and 2p orbitals of H-atom have substantial values
at the distance of 1s orbital also, the 2s and 2p orbitals penetrate the 1s orbtial.

2s 2p
A.O.
2
4rdr



r
Figure: Probability distribution of electron density
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• Accurate calculations indicate the penetration effect of 2s orbital is greater than 2p orbital.
• Penetration of 2s > 2p.
• So, when an electron is filled in 2s or 2p atomic orbital it experiences
(a) the attractive nuclear charge
(b) the repulsive forces due to innerlying electrons.
• Electrons of ns, np group contribute nearly 35% each to screening constant.
• (n–1) electrons contribute 85%
• (n–2) electrons contribute 100% to screening.
Empirical Rules for estimating ENC – “Slater Rules”:
The actual nuclear charge experienced by the electrons in different orbitals is estimated by Slater Rules. These
rules are based upon experimental data for electron promotion energies and ionization energies. The ENC (Z*)
acting on a given electron is obtained by substracting the screening or shielding constant ‘S’, ‘S’ is estimated as
follows
(1) Write the E.C. in the following order and groupings
(1s), (2s, 2p), (3s, 3p) (3d), (4s 4p), (4d) (4f), (5s, 5p) etc.
(2) Electron in any group higher in this sequence than the electron under consideration contributes nothing to
‘s’.
(3) Then for an electron in an ‘ns’ or ‘np’ orbital.
(a) All other electrons in the (ns, np) group contribute s = 0.35 each.
(b) All electrons in the (n–1) shell contribute s = 0.85 each.
(c) All electrons in (n–2) or lower shells contribute s = 1.00 each.
(4) For an electron in an ‘nd’ or ‘nf’ orbital, all electrons in the same group contribute s = 0.35 each.
Those in groups lying lower in the sequence than (nd) or (nf) contributes s = 1.00 each.
e.g. ‘K’ = (1s2) (2s2p6) (3s2p6) (4s1)
The ENC experienced by ‘4s’ electron is Z* = Z – S = 19 – (0.85 × 8) + (1.00×10) = 2.20

 
2 2 6 2 6 1
  
If we consider the E.C. of K as 1s 1s p 3s p 3d then Z* would be Z* = 19 – (1.00 × 18) = 1.00
Thus the electron in the 4s orbital is under the influence of the greater effective nuclear charge and hence in the
ground state this orbital is occupied.

Atomic size decreases from left to right in a period L  R  Atomic Size  

Atomic size increases from top to down in a group.
T
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Li Be B C N O F Ne
Na decreases
K
increases
Rb
Cs

Fr
B