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03 Classification of elements and periodicity in properties

Classification of elements
● Classification of elements helps in:
(i) Systematic study of the properties of elements.
(ii) Easy to understand and remember the properties of elements.
● The earlier attempt to classify elements involves dividing them into metals and
nonmetals.
● The classification was done by Antoine Laurent Lavoisier (Father of chemistry).
● This method failed because most of the elements were metals and a very few
were non metals.
● Some elements resembled metals and nonmetals and hence they could not be
classified.

Dobereiner's triads

● In the year 1817, Johann Wolfgang Dobereiner, a German chemist classified

elements having similar properties into groups called triads.
● When the elements were arranged in groups of 3, in the increasing order of
atomic masses, the middle element has the atomic mass and properties roughly
the average of the other two elements.

Newlands law of Octaves - John Newland

When elements are arranged in the increasing order of their atomic masses (from H to
Th), the properties of the 8th element resembled with the properties of the first element.
This was compared to the octaves found in music. Hence called Newlands law of
octaves.

Mendeleev’s Periodic Law - Dmitri Ivanovich Mendeleev

When Mendeleev started his work , 63 elements were known. He examined the
relationship between the atomic masses of the elements and their physical and
chemical properties.

“ The properties of elements are a periodic function of their atomic masses”

Modern Periodic Law

Henry Moseley showed that atomic number is a more fundamental property than atomic
mass.

“ Properties of elements are periodic function of their atomic number”

General features of long form periodic table
● The elements are arranged in the increasing order of atomic number.
● There are 7 horizontal rows called ​periods​.
● There are 18 vertical columns called ​groups​.
● Elements having similar valence electrons are placed in the same group.
● Each period starts with the filling of a new shell.
● The 14 elements after Lanthanum are called ​lanthanoids​.
● The 14 elements after Actinium are called ​actinoids
● To limit the size of the periodic table and to keep the elements with similar
properties together, Lanthanoids and Actinoids are placed at the bottom of the
periodic table.
● The elements of ​group1, 2 and 13-17 ​(s-block and p-block) are called
representative elements​ or main group elements. They have completely filled
inner shells but incomplete valence shell.
● The elements of ​group 3-12​(d-block) are called ​transition elements​. They have
incomplete outer shells and penultimate shells.
● The elements placed at the bottom of the periodic table (f-block) are called inner
transition elements. They are also called ​rare earth metals​ because they occur
rarely in the earth's crust.
● Group 18​ elements are called ​noble gases​ or inert gases. Their outer orbits are
completely filled and are unreactive.
● A zig-zag line separates metals from nonmetals by some elements called
metalloids ​or semimetals (B, Si, Ge, As, Sb, Te and Po)
● Metals are found on the left side of the periodic table and nonmetals on the right
side.

Important points to note

● Elements in any group have same number of valence electrons.

● Size of the atom decreases across a period and increases down a group.
● Each period starts with a new shell.
● Maximum number of electrons in each shell is given by the formula ​2n​2​, where n
is the number of the given shell. (K=1, L=2, M=3, ….)

Periodicity
The periodic repetition of elements with similar properties after certain regular intervals
when the elements are arranged in the order of increasing atomic number.

● 1st period consists of 2 elements (1s)

 ● 2nd period consists of 8 elements (2s,2p)
● 3rd period consists of 8 elements (3s,3p)
● 4th period consists of 18 elements (4s,3d,4p)
● 5th period consists of 18 elements (5s,4d,5p)
● 6th period consists of 32 elements (6s,4f,5d,6p)
● 7th period consists of 32 elements (7s,5f,6d,7p)

Groups

● Group I and 2 - s- block elements

● Group 3 to 12 - Transition elements ( d-block elements)
● Groups 13 to 18 - p-block elements
● Lanthanides and actinides (Placed below - f - block elements)
● Those elements in which the filling of electrons takes place in 4f orbital is called
lanthanoid series.
● Those in which 5f orbitals are filled are called actinoid series.

Different blocks of elements

S-block elements​ ( ns​1-2​ )

● ns​1​ - Alkali metals and ns​2​ - Alkaline earth metals.

1. They are all metals

2. Possess low ionisation energy since they have 1 or 2 electrons in their valence
shell.
3. They form ionic compounds.
4. Metallic character increases down the group.

p - block elements​ ( ns​2​ np​1-6​)

● p block elements consists of groups 13 to 18 together with the s block elements

are called representative elements or main group elements.

1. Group 16 - ns​2​ np​4 ​- Chalcogens(Most of them are found as oxide or sulphide)

2. Group 17 - ns​2​ np​5 ​- Halogens
3. Group 18 - ns​2​ np​6 ​- Noble gases or inert gases
d - block elements​ Transition elements ( (n-1)d​1-10​ ns​1-2​)

● They are called d block elements since they are characterised by the filling of
inner d orbitals.

1. They are all metals

2. They form coloured ions
3. Exhibit variable valency
4. They form complex compounds (Co(NH​3​)​6​)Cl​3

Zn, Cd and Hg do not show the properties of transition elements since they have
completely filled d-orbitals.

f - block elements​ Inner transition elements ( (n-2)f​1-14​ (n-1)d​0-1 ​ns​2​)

1. They are metals
2. Most of the actinoids are radioactive.
3. The elements coming after Uranium are called trans-uranium elements.
4. Elements are also classified as metals, nonmetals and metalloids or semi metals.
5. Semi metals are those that show the properties characteristic of both metal and
nonmetals.

New elements added in the periodic table

113 - Nh -Nihonium - Japan

115 - Mc - Moscovium - Moscow region
117 - Ts - Tennessine - Tennessee
118 - Og - Oganesson - Yuri Oganessian

Periodic Trends in properties

1. Size:
● Atomic radius​ - It is defined as the radius of the sphere or the distance between
the centre of the nucleus and the outermost shell of electrons.
● Covalent radius​ - It is the half the distance between two atoms when they are
joined by a single bond in a covalent molecule.
● Metallic radius​ - It is taken as the half of the internuclear distance separating the
metal ions in the metallic crystal.

Variation

● From left to right ​- Size decreases due to the increase in nuclear charge. So the
 electrons are pulled more closer to the nucleus. Group one elements (Alkali
metals) are the largest in size.
● Top to bottom ​- Size increases as new shells are added up. Thereby attraction
decreases.
● Size of the cations​ : Cations are formed by the loss of electrons. Cations are
smaller than the neutral atom because when the electrons are lost the ion has
greater number of protons. So there are more protons acting on lesser number of
electrons and hence attraction increases.
● Size of the Anions​ : Anions are formed by the gain of electrons. Size of the
anion is greater than the neutral atom because there are more electrons in
anions than the number of protons. Hence attraction decreases.
● Iso electronic ions: Isoelectronic ions are those atoms or ions which contains the
same number of electrons.

Eg: O​2-​ , F​- ​ , Na​+​ , and Mg​2+​. Cation with greater positive charge will have smaller size
due to greater attractive forces.

Size is Mg​2+ ​< Na​+​ < F​-​ < O​2-

2. ​Ionisation enthalpy
● It is the energy required to remove the most loosely bound electron from a
gaseous neutral atom in the ground state.

Factors affecting Ionisation energy

a. Size of the atom: Smaller the size greater is the attractive force and hence higher
IE
b. Effective nuclear energy: Greater the charge greater the attractive forces and
higher the IE values.
c. Shielding of the inner orbitals : The reduction in the force of attraction by the
electrons present between the nucleus and the valence electrons is called
screening or shielding effect. Weaker the shielding effect greater is the attractive
force and higher is the IE.
d. Ionisation energy increases with the increase in atomic number across a period,
due to the increase in nuclear charge and decrease in atomic size.
e. Ionisation energy decreases down a group due to the increase in atomic size and
increase in the shielding effect.
f. Noble gases have high IE due to stable octet configuration.
g. Second IE is always greater than the first, after removing one electron nuclear
 charge increases.
h. IE of N and P is high due to the stable half filled electronic configuration resulting
from symmetrical distribution of electrons and high exchange energy.
i. IE of Be is high due to the completely filled s subshell.
j. IE of alkali metals is low , since they have one electron in their valence shell and
easily loses it to attain octet configuration.

Anomalies

● The first ionisation enthalpy of boron (Z=5) is slightly less than Be(Z=4) even
though B has greater nuclear charge.
(s - electron is more attracted towards the nucleus than p-electrons)
● The first ionisation enthalpy of oxygen (Z=8) is less than Nitrogen (Z=7).
3. ​Electron gain enthalpy​ ​(Electron affinity)

● It is the energy released when an electron is added to a gaseous neutral atom to

produce a negative ion.

X​(g) ​ + e​-​ X​-​(g)​ + Energy

● When energy is released electron gain enthalpy is negative.

● Electron gain enthalpy generally increases across a period due to the decrease
in the atomic size and increase in nuclear charge.( Across a period it becomes
more negative)
● It decreases down a group due to the increase in size of the atom. (Down a
group it becomes less negative)

3. The elements of group 2, 15 and 18 has relatively very low values of electron affinity,
due to stable electronic configuration (Completely filled and half filled outer shells).

● Chlorine has higher electron affinity than fluorine. Why?

In fluorine, the electron is added to the second shell which has 7 electrons. The added
electron will suffer high repulsion from electrons already present in the small shell. But
in chlorine, an electron is added to the third shell which is much bigger than the second
shell and hence the repulsion is less.

(Electron gain enthalpy of O is less than that of S)

 ● Chloride ion is more stable than bromide ion. Why?

The stability of a negative ion depends on the electron affinity. Higher the electron
affinity more stable the negative ion.

4. ​Valency

Valency - It is the combining capacity of an element. It denotes the number of electrons

lost or gained during a chemical reaction.

● On moving from left to right in a period, valency of the elements first increases
from 1 to 4 and then decreases to zero.
● All the elements in a group has same valency, as they have same number of
valence shell electrons.

5. ​Electronegativity​ ​- Linus Pauling

It is the tendency of the bonded molecules to attract the shared pair of electrons more
towards itself.

● Electronegativity increases across a period due to the increase in nuclear charge

and decrease in size with the increase in atomic number in a period.
● Electronegativity decreases down a group due to the increase in size of the
atoms.
● Among the stable elements, Caesium has the lowest electronegativity and
fluorine has the highest electronegativity.

6. ​Metallic character:

● Metals are found on the left hand side of the table and nonmetals on the right
 hand side.
● Metals has a tendency to lose electrons - electropositive.
● Nonmetals has a tendency to gain electrons - electronegative.
● On moving from left to right in a period, the electropositive character decreases
and electro negative character increases.
● On moving from left to right in a period, the tendency of atoms to lose electrons
decreases and tendency of atoms to gain electron increases.
● On moving down a group the metallic character of the elements increases or the
electropositive character of the element increases.
● As we go down in group 17, the electronegative character (nonmetallic character)
of elements decreases.
● Fluorine is the most electronegative element.

7. ​Nature of oxides.

● On moving from left to right in a period the basic nature of oxides decreases and
the acidic nature of oxides increases.
● On moving down a group there is no change in the nature of oxides of elements
● All elements of group 1 form basic oxides
● All the elements of group 17 form acidic oxides
● Elements in the centre form amphoteric oxide

Acidic oxides Cl​2​O​7 ,​ SO​2 ,​ P​2​O​5

Basic Oxides Na​2​O, CaO, MgO

Amphoteric oxides Al​2​O​3 ,​ ZnO

Neutral oxides CO, NO, N​2​O

Anomalous properties
● The first element in each group differs from the rest due to
➔ Small size, high charge to size ratio, high electronegativity of element and non
availability of d-orbitals.
Diagonal relationship

● The similarity in properties of an element with another element lying diagonally

opposite to it in second period is referred as diagonal relationship.
● This is due to similar charge to size ratio. Thus Li resembles Mg, Be resembles
Al.