Classification of Elements and Periodicity in Properties

Q. WHY DO WE NEED TO CLASSIFY ELEMENTS?

With such a large number of elements it is very difficult to study individually the chemistry of all 118 elements and
their innumerable compounds individually. To ease out this problem, scientists searched for a systematic way to
organize their knowledge by classifying the elements.

Mendeleev’s classification

He proposed a periodic law which states that “The properties of elements are the periodic functions of their atomic
weights.” That is, when elements are arranged in the increasing order of their atomic weights, their properties repeat
after a regular interval.

Mendeleev’s periodic table contains horizontal rows called series (periods) and vertical columns called groups.
Elements with similar properties are placed in the same group.

When Mendeleev proposed his periodic table, some of the elements were not discovered. He left some vacant places
(gaps) for them in the periodic table and predicted some of their properties.

For e.g. both Gallium and Germanium were not discovered at that time. He named these elements as Eka-Aluminium
and Eka-Silicon respectively and predicted their properties.

Merits of Mendeleev’s periodic table

1) It was the first comprehensive classification of elements.

2) He corrected the wrong atomic weights of some elements and placed them in correct position in the periodic table.

3) He left vacant places for undiscovered elements and predicted some of their properties.

4) Elements with similar properties are placed in the same group.

Demerits of Mendeleev’s periodic table

1) Elements with dissimilar properties are found in same group.

2) He could not give an exact position for hydrogen.

3) He could not give exact position for Lanthanoids and Actinoids and also for isotopes.

4) Mendeleev’s periodic table did not strictly obey the increasing order of atomic weights.
Modern Periodic table

Henry Moseley modified the Mendeleev’s periodic law as “the physical and chemical properties of elements are the
periodic functions of their atomic numbers”. This is known as Modern Periodic law.

In this periodic table, the elements are arranged in the increasing order of their atomic number. It contains 7
horizontal rows called periods and 18 vertical columns called groups.

PERIODS

There are 7 periods in Modern periodic table. The period number corresponds to the highest principal quantum
number of the elements.

Periods Elements No. of Elements Subshell filled Description

The 14 elements each of sixth and seventh periods are placed in separate rows below the main body of the periodic
table. These are together called inner transition elements. The 14 elements of sixth period [from 57Ce (cerium) to 71Lu
(lutetium)] are called Lanthanides or Lanthanones or Lanthanoids or rare earths. The 14 elements of seventh period
[from 90Th (thorium) to 103Lr (lawrencium)] are called Actinides or Actinones or Actinoids.

GROUPS

Vertical columns in Long form of Modern periodic table are called groups or families. There are 18 groups and these
are numbered from 1 to 18. Due to the similar outer electronic configuration and same valency, the elements present
in the same group have similar properties.
The Blocks in the Modern periodic table

The Modern periodic table is divided into 4 blocks based on the subshell in which the last electron enters. They are s
block, p block, d block and f block.

1. The s-block elements

• These are elements in which the last electron enters in the outer most s sub shell. They include
elements of the groups 1 and 2.
• Their general outer electronic configuration is ns1 or ns2 .
• They are all reactive metals with low ionization enthalpies.
• They lose their outer most electrons readily to form +1 and +2 ions.
• Their metallic character and reactivity increases down the group.
• They mainly form ionic compounds (except Li and Be).
2. The p-block elements
• These are elements in which the last electron enters in the outer most p sub shell. They include
elements of the groups 13 to 18.
• Their general outer electronic configuration is ns2 np1 to 6.
• Their non-metallic character increases from left to right in a period and metallic character increases
from top to bottom in a group.
• The 16th group elements are called chalcogens and that of 17th group are called halogens.
• The 18th group elements are called Noble gases or inert gases.
• They have completely filled orbitals and so they do not undergo chemical reactions at ordinary
conditions.
 • s and p block elements are together called Representative elements, because these are the only
elements which show the general trends in the periodic table and also they contain metals, non-metals
and metalloids.
3. The d-block elements

• These are elements in which the last electron enters in the penultimate d sub shell. They include
elements of the groups 3 to 12.
• They are also called Transition elements (Transition metals), since they show a regular transition
(change) from the most electropositive s block elements to the least electropositive p block elements.
• Their general outer electronic configuration is (n-1)d1 to 10 ns0 to 2 .
Some properties of transition elements are:
a) They are all metals.
b) They form coloured compounds or ions in aqueous solution.
c) They show variable oxidation states and valencies.
d) They are generally paramagnetic.
e) They show catalytic properties.

4. The f-block elements

• These are elements in which the last electron enters in the anti-penultimate f sub shell.
• They include lanthanides of 6th period and actinides of 7th period.
• They are also called Inner transition elements. Their general outer electronic configuration is
(n-2)f 1 to 14(n-1)d0 to 1 ns2 .
• They are all metals.
• Within each series the properties of these elements are similar.
• Actinoid elements are radioactive.
• Elements after Uranium (z=92) in the actinide series are called trans-uranium elements or artificial
elements.

Electronic configuration of an element and its position in the periodic table

From the electronic configuration of an element, we can assign its period, group and block in the periodic
table.
Block: The subshell in which the last electron enters.
Period number = the highest principal quantum number in its electronic configuration.
Group number:
For s block elements = no. of valence s electrons
 For p block elements = no. of valence s electrons + valence p electrons + 10
For d block elements = no. of valence s electrons + no. of penultimate d electrons.

Nomenclature of elements with atomic numbers > 100

For naming elements with atomic number > 100, IUPAC has made some recommendations. A systematic
nomenclature be derived directly from the atomic number of the element using the numerical roots for 0 and
numbers 1-9. The roots are put together in order of digits which make up the atomic number and “ium” is
added at the end.

Periodic properties of Elements

The properties which repeat after a regular interval are called periodic properties. Some of the important
periodic properties of elements are atomic and ionic radii, ionization enthalpy, electron gain enthalpy,
electropositivity, electronegativity etc.
1. Atomic Radius
It is defined as the distance from the centre of the nucleus to the outermost shell having electrons.
Atomic radius of individual atoms cannot be determined. So it is expressed in any of the following methods:
a) Covalent radius: It is half of the inter nuclear distance between two covalently bonded (single bonded)
atoms. It is used to express the atomic radius of non-metal atoms. For e.g. the bond distance of Cl2
molecule is 198 pm. So the covalent radius is 99 pm.
b) Metallic radius: It is half of the inter nuclear distance between two metallic ions in a metal crystal.
c) van der Waal’s radius: It is defined as the half of the inter nuclear distance between two non-bonded
atoms of separate molecules in the solid state.
Atomic radius is commonly expressed in picometre (pm) or angstrom (A0 ) unit.
2. Ionic radius
It is defined as the half of the inter nuclear distance between cations and anions of an ionic crystal.
The variation of ionic radius is same as that of atomic radius.
Generally a cation is smaller than its parent atom (e.g. Na+ is smaller than Na atom). This is because a
cation has fewer electrons, but its nuclear charge remains the same as that of the parent atom.
An anion is larger than its parent atom (e.g. Cl- anion is larger than Cl atom). This is because the addition of
one or more electrons would result in an increased electronic repulsion and a decrease in effective nuclear
charge.
Isoelectronic species

Atoms and ions having the same number of electrons are called isoelectronic species. E.g. O 2- , F- , Ne, Na+
, Mg2+ etc. (All these contain 10 electrons)
Among isoelectronic species, the cation with greater positive charge will have the smaller radius. This is
because of the greater attraction of electrons to the nucleus. The anion with greater negative charge will
have the larger radius. Here the repulsion between electrons is greater than the attraction of the nucleus.
So the ion will expand in size.

3. Ionization enthalpy (∆iH)

It is defined as the energy required to remove an electron from the outer most shell of an isolated gaseous
atom in its ground state. It may be represented as:
X(g) + ∆iH → X+(g) + e–
Its unit is kJ/mol or J/mol.
The energy required to remove the first electron from the outer most shell of a neutral atom is called first
ionization enthalpy (∆iH1).
X(g) + ∆iH1 → X+ (g) + e–
Second Ionization enthalpy (∆iH2) is the amount of energy required to remove an electron from a
unipositive ion.
X +(g) + ∆iH2 → X2+(g) + e–
Energy is always required to remove an electron from an atom or ion. So ∆iH is always positive.
The second ionization enthalpy is always higher than first ionization enthalpy. This is because it is more
difficult to remove an electron from a positive charged ion than from a neutral atom. Similarly third
ionization enthalpy is higher than second ionization enthalpy and so on. i.e. ∆iH1 < ∆iH2 < ∆iH3…………
As the ease of removal of electron increases, the ionization enthalpy decreases.
Factors affecting ionization enthalpy
The important factors which affect ionization enthalpy are:
a) Atomic size: Greater the atomic size (atomic radius), smaller will be the ionization enthalpy.
b) Effective nuclear charge: The value of ionization enthalpy increases with effective nuclear charge.
c) Shielding effect: As the shielding effect increases, the electrons can easily be removed and so the
ionization enthalpy decreases.
d) Presence of half filled or completely filled orbitals increases ionization enthalpy.
Variation of ∆iH along a period and a group
• Along a period, ionization enthalpy increases from left to right. This is because of the decrease in
atomic radius and increase in effective nuclear charge. Thus alkali metals have the least ∆iH and
 noble gases have the most. Down a group, ∆iH decreases due to increase in atomic radius and
shielding effect.
• Thus among alkali metals, lithium has the least ∆iH and francium has the most. In the second period
of modern periodic table, the first ionization enthalpy of Boron is slightly less than that of Beryllium.
This is because of the completely filled orbitals in Be (1s22s2 ).
• Similarly the first ionization enthalpy of N is greater than that of Oxygen. This is because N has half-
filled electronic configuration (1s22s22p3 ), which is more stable and so more energy is required to
remove an electron.

3. Electron gain enthalpy (∆egH)

• It is the enthalpy change when an electron is added to the outermost shell of an isolated gaseous
atom. Its unit is kJ/mol.
• It can be represented as X(g) + e– → X- (g)
• It may be positive or negative depending on the nature of the element.
• For most of the elements, energy is released when electrons are added to their atoms. So ∆egH is
negative.
• Noble gases have large positive electron gain enthalpy because of their completely filled (stable)
electronic configuration.
• Electron gain enthalpy also depends on atomic size, nuclear charge, shielding effect ,etc. As the
atomic size increases ∆egH decreases. When effective nuclear charge increases, electron gain
enthalpy increases and become more negative. Shielding effect decreases ∆egH. Presence of half-
filled or completely filled orbitals makes ∆egH less negative.
Periodic variation of ∆egH
• From left to right across a period, ∆egH become more negative. This is because of decrease in atomic
radius and increase in effective nuclear charge. So the ease of addition of electron increases and
hence the ∆egH.
• Down a group, ∆egH becomes less negative. This is due to an increase in atomic radius and shielding
effect.
• Electron gain enthalpy of fluorine is less negative than chlorine. This is because, when an electron
is added to F, it enters the smaller 2nd shell. Due to the smaller size, the electron suffers more
repulsion from the other electrons. But for Cl, the incoming electron goes to the larger 3rd shell. So
the electronic repulsion is low and hence Cl adds electron more easily than F.
• Due to the same reason, ∆egH of Oxygen is less negative than S.
 • Thus in modern periodic table, alkali metals have the least negative ∆egH and halogens have the
most negative ∆egH.
• Among halogens, the negative ∆egH decreases in the order: Cl> F > Br > I
• The negative electron gain enthalpy is also called electron affinity.

4. Electronegativity
• Electronegativity of an atom in a compound is the ability of the atom to attract shared pair of
electrons to itself.
• It is not a measurable quantity and so it has no unit.
• There are different scales for measuring the Electronegativity of elements.
• The most commonly used is the Pauling Electronegativity scale developed by Linus Pauling.
Electronegativity depends on atomic size and nuclear charge.
• As the atomic radius increases, electronegativity decreases.
• Greater the nuclear charge, greater will be the electronegativity.
• Generally electronegativity increases across a period and decreases along a group.
• So in modern periodic table, F has the maximum electronegativity and Fr has the minimum
electronegativity. In Pauling Scale, electronegativity of F is 4.0
• The electronegativity of an element is not constant. It varies depending on the element to which it
is bound. It is directly related to the non-metallic character of elements.
• An increase in electronegativity across a period indicates an increase in non-metallic character and
decrease in metallic character.
5. Electropositivity
• It is the tendency of an atom to lose the most loosely bound electron (valence electron). It is
directly related to the metallic character of elements. It depends on atomic size and nuclear charge.
As the atomic radius increases, electropositivity increases.
• Along a period, electropositivity decreases from left to right.
• But down a group, it increases. So francium is the most electropositive element and fluorine is the
least electropositive element.
6. Valency
• It is the combining capacity of an element. Or, it is the number of electrons lost or gained by an
atom during a chemical reaction.
• Along a period, valency first increases upto the middle and then decreases (for s and p block
elements only).
• In a group, valency remains constant.
 • Transition elements can show variable valency.
• Valency is numerically equal to oxidation number of the element.
• The difference is that oxidation number has a positive or negative sign but the valency doesn’t.

Anomalous Properties of Second Period Elements

The first element in groups 1 (lithium) and 2 (beryllium) and groups 13 to 17 (boron to fluorine) differs
from the other members of their respective group in their properties.
This is known as anomalous properties. This is due to their small size, large charge to radius ratio, high
electronegativity and absence of vacant d-orbitals.
Some of the anomalous properties are:
• They can form multiple bonds with themselves (e.g. C = C, N ≡ N etc.) and with other elements of the
second period (e.g. C = O, C ≡ N etc.).
• Their maximum covalency is 4, due to the absence of vacant d-orbitals. But other elements of the
respective groups can expand their covalency beyond 4 (due to the presence of vacant d-orbitals).
For this reason, Aluminium forms [AlF6] 3- whereas boron cannot form [BF6] 3- but forms only [BF4] - .
Similarly, Phosphorus forms PCl5 while nitrogen cannot form NCl5.

Diagonal relationship
The similarities in properties shown by the diagonally placed elements of the 2nd and 3rd periods in the
Modern periodic table are called Diagonal relationship. This is due to their similar atomic radii, ionization
enthalpy, electronegativity etc. E.g. Lithium shows similarities with Mg, Be with Al, B with Si ,etc.

• The normal oxide formed by the element on extreme left is the most basic (e.g., Na2O),
whereas that formed by the element on extreme right is the most acidic (e.g., Cl2O7).

• Oxides of elements in the center are amphoteric (e.g., Al2O3, As2O3) or neutral (e.g., CO, NO,
N2O).
• Amphoteric oxides behave as acidic with bases and as basic with acids, whereas neutral
oxides have no acidic or basic properties.