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3. CLASSIFICATION OF ELEMENTS AND

PERIODICITY IN PROPERTIES
Earlier classifications
1) Dobereiner’s classification:
Johann Dobereiner classified elements into small groups each containing three elements. These
small groups were called triads.
E.g. for triads are: i) 7Li 23Na 39K

ii) 40Ca 88Sr 137Ba

In triads, the atomic mass of the middle element is approximately the average of the other two
elements. This is known as Law of Triads. This classification was rejected, since the law of triad is
applicable only to a very few elements.
2) Newlands classification:
Newland arranged elements in the increasing order of their atomic masses. He noted that the
properties of every eighth element, starting from a given element, are similar to that of the first
element. The relationship is just like the resemblance of first and eighth musical notes. He named this as
law of octaves.
But his classification was rejected since the law of octaves was applicable to elements upto calcium.
A.E.B. de Chancourtois arranged elements in increasing order of atomic weights and made a
cylindrical table of elements to display the regular repetition of properties.
3) Lothar Meyer’s classification: Lothar Meyer plotted the physical properties of elements like
atomic volume, melting point and boiling point against atomic weight and obtained a periodically
repeated pattern. Based on this, he developed a periodic table similar to that of Mendeleev’s.
4) Mendeleev’s classification:
Dmitri Mendeleev (a Russian chemist) classified the elements in the increasing order of their atomic
weights. He found that the properties of elements repeat after a regular interval. Based on this
observation, 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. He
mainly depends on the similarities in the empirical formulae and the properties of the
compounds formed by the elements. So he did not strictly obey the increasing order of
atomic weights. Also he corrected the wrong atomic masses of some elements.
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. These elements were
discovered later and found that Mendeleev’s predictions were correct.
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.

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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’s work on the X-ray spectra of elements proved that atomic number is a more
fundamental property than atomic mass. Based on this observation, he 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.
Based on the modern periodic law, numerous forms of periodic tables have been proposed. The
most commonly used is the long form of periodic table.
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 or families.
In the long form of modern periodic table, hydrogen has given a particular position at the top centre.
PERIODS
There are 7 periods in Modern periodic table. The period number corresponds to the highest
principal quantum number of the elements.
Period No. Elements No. of Elements Subshells filled Description
I 1H & 2He 2 1s Very short period
II 3 Li to 10Ne 8 2s & 2p
Short periods
III 11 Na to 18Ar 8 3s & 3p
IV 19K to 36Kr 18 4s, 3d & 4p
Long periods
V 37Rb to 54Xe 18 5s, 4d & 5p
VI 55Cs to 86Rn 32 6s, 4f, 5d & 6p
Longest periods
VII 87 Fr to 118 Og 32 7s, 5f, 6d & 7p
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.
Group General outer
Elements Family name
No. Electronic configuration
1 Li, Na, K, Rb, Cs & Fr ns1 Alkali metals
2 Be, Mg, Ca, Sr , Ba & Ra ns2 Alkaline earth metals
3 to 12 4 rows of elements (n-1)d1 to 10 ns 0 to 2 Transition elements
13 B, Al, Ga, In, Tl & Nh ns2 np1 Boron Family
14 C, Si, Ge, Sn, Pb & Fl ns2 np2 Carbon Family
15 N, P, As, Sb, Bi & Mc ns2 np3 Nitrogen Family
16 O, S, Se, Te, Po & Lv ns2 np4 Oxygen Family
17 F, Cl, Br, I, At, Ts ns2 np5 Halogen Family
18 He, Ne, Ar, Kr, Xe, Rn, Og ns2 np6 Noble gases

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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 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)f1 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 trans-uranic elements or artificial elements. [Neptunium
(93Np) and Plutonium (94Pu) are also found naturally in Pitch blende, an ore of Uranium].
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.

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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.
Digit 0 1 2 3 4 5 6 7 8 9
Root name nil un bi tri quad pent hex sept oct enn
Abbreviation n u b t q p h s o e
The roots are put together in order of digits which make up the atomic number and “ium” is added at
the end.
Atomic Number Name according to Symbol IUPAC Official Name
IUPAC nomenclature and Symbol
101 Unnilunium Unu Mendelevium (Md)
102 Unnilbium Unb Nobelium (No)
103 Unniltrium Unt Lawrencium (Lr)
104 Unnilquadium Unq Rutherfordium (Rf)
105 Unnilpentium Unp Dubnium (Db)
106 Unnilhexium Unh Seaborgium (Sg)
107 Unnilseptium Uns Bohrium (Bh)
108 Unniloctium Uno Hassium (Hs)
109 Unnilennium Une Meitnerium (Mt)
110 Ununnilium Uun Darmstadtium (Ds)
111 Unununium Uuu Rontgenium (Rg)
112 Ununbium Uub Copernicium (Cp)
113 Ununtrium Uut Nihonium (Nh)
114 Ununquadium Uuq Flerovium (Fl)
115 Ununpentium Uup Moscovium (Mc)
116 Ununhexium Uuh Livermorium (Lv)
117 Ununseptium Uus Tennessine (Ts)
118 Ununoctium Uuo Oganesson (Og)
119 Ununennium Uue
120 Unbinilium Ubn

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.

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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 the 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. [1 pm = 10-12m and
1 A = 10-10 m]. It is measured by x-ray diffraction method or by spectroscopic method.
0

Variation of atomic radius along a group and a period

The atomic size decreases from left to right in a period. This is because in a period,
the electrons are added to the same valence shell. Thus the number of shells remains the
same, but the effective nuclear charge increases. So the atomic radius decreases. In a given
period, alkali metals (group 1) have the maximum size and halogens (group 17) have the minimum size.
In a group, the atomic radius increases from top to bottom. This is because of the
increase in no. of shells and shielding effect. (In atoms with higher atomic number, the inner
electrons partially shield the attractive force of the nucleus. So the outer electrons do not experience
the full attraction of the nucleus and this is known as shielding effect or screening effect).

Variation of atomic radii along 2nd period Variation of atomic radii along 1st and 17th groups.

Atomic radius of noble gases is larger than that of halogens. This is because noble
gases are monoatomic. So van der Waal’s radius is used to express their atomic radius
which is greater than covalent radius or metallic radius.
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.

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An anion is larger than its parent atom (e.g. Cl- 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:
Species (atoms and ions) having the same number of electrons are called isoelectronic
species. E.g. N3-, O2-, F-, Ne, Na+, Mg2+, Al3+ 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.
Thus among the isoelectronic species N3-, O2-, F-, Ne, Na+, Mg2+and Al3+, the largest ion is N3- and
the smallest ion is Al3+.
3. Ionisation 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. Or, it is the energy required to convert a gaseous
neutral atom to a gaseous unipositive ion. 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 ionisation enthalpy (∆iH1).
X(g) + ∆iH1 → X+(g) + e–
Second Ionisation 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 ionisation enthalpy is always higher than first ionization enthalpy. This is
because it is more difficult to remove an electron from a positively charged ion than from
a neutral atom.
Similarly third ionisation enthalpy is higher than second ionisation enthalpy and so on.
i.e. ∆iH1 < ∆iH2 < ∆iH3…………
As the ease of removal of electron increases, the ionisation enthalpy decreases.
Factors affecting ionisation enthalpy
The important factors which affect ionisation enthalpy are:
a) Atomic size: Greater the atomic size (atomic radius), smaller will be the ionisation enthalpy.
b) Nuclear charge: The value of ionisation enthalpy increases with nuclear charge.
c) Shielding effect: As the shielding effect increases, the electrons can easily be removed and so the
ionisation enthalpy decreases.
d) Presence of half-filled or completely filled orbitals increases ionisation enthalpy.
[As the ease of removal of electron increases, ionisation enthalpy decresaes].
Variation of ∆iH along a period and a group
Along a period, ionisation enthalpy increases from left to right. This is because of the
decrease in atomic radius and increase in nuclear charge. Thus alkali metals have the least
∆iH and noble gases have the most.

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Down a group, ∆iH decreases due to increase in atomic radius and shielding effect.
Thus among alkali metals, lithium has the highest ∆iH and francium has the lowest.

Variation of ionisation enthalpy along 2nd period Variation of ionisation enthalpy along 1st group

In the second period of modern periodic table, the first ionisation enthalpy of Boron
is slightly less than that of Beryllium. This is because after the removal of one electron
from boron, it gets the stable configuration (1s22s2). So B loses one electron faster.
Similarly the first ionisation enthalpy of nitrogen 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.
4. Electron gain enthalpy (∆egH)
It is the heat change (enthalpy change) when an electron is added to the outer most
shell of an isolated gaseous atom. It can be represented as X(g) + e– → X-(g)
Its unit is kJ/mol. It may be positive or negative depending on the nature of the element. For
most of the elements, energy is released when electron is added to their atoms. So ∆ egH is negative.
Noble gases have large positive electron gain enthalpy because of their stable
completely filled electronic configuration.
Electron gain enthalpy also depends on atomic size, nuclear charge, shielding effect etc. As the
atomic size increases, ∆egH becomes less negative. When nuclear charge increases, electron gain
enthalpy becomes more negative. As shielding effect increases, ∆egH becomes less negative. Presence of
half-filled or completely filled orbitals make ∆egH less negative.
[As the ease of addition of electron increases, electron gain enthalpy becomes more 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 nuclear charge. So the ease of addition of electron increases.
Down a group, ∆egH becomes less negative. This is due to 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 into 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. [OR, Due to the compactness of the 2p subshell of F, electronic
repulsion is greater in F and hence it does not easily add electron]. Due to the same reason ∆egH of
oxygen is less negative than sulphur.
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Thus in modern periodic table, alkali metals have the least negative ∆egH and halogens have the
most negative ∆egH. Among halogens, ∆egH becomes less negative in the order: Cl> F > Br > I
[The negative electron gain enthalpy is also called electron affinity].
5. Electronegativity
Electronegativity of an atom in a compound is the ability of the atom to attract
shared pair of electron of electrons. 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 one is the
Pauling Electronegativity scale developed by Linus Pauling. The other electronegativity scales are
Mulliken-Jaffe scale, Allred-Rochow scale etc.
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, Fluorine is the most electronegative element and Francium is the least electronegative
element. Since francium is radioactive, caesium is the least electronegative stable element. In Pauling
Scale, electronegativity of Fluorine is 4.0 and that of Oxygen is 3.5.
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.
6. 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.
7. 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 co-valency 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.

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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, ionisation enthalpy, electronegativity etc.
E.g. Lithium shows similarities with Mg, Be with Al, B with Si etc.

Periodic Trends and Chemical Reactivity

The periodicity in properties of elements is related to electronic configuration. That is, elements
having similar outer electronic configuration show similarities in chemical and physical properties.
The atomic and ionic radii, generally decrease in a period from left to right. As a consequence,
the ionization enthalpies generally increase and electron gain enthalpies become more negative across a
period. This results into high chemical reactivity at the two extremes and the lowest in the centre. Thus,
the maximum chemical reactivity at the extreme left (among alkali metals) is exhibited by the loss of an
electron leading to the formation of a cation and at the extreme right (among halogens) shown by the
gain of an electron forming an anion. This property can be related with the reducing and oxidizing
behaviour of the elements. i.e. Elements at the extreme left (alkali metals) of the periodic table are good
reducing agents and those at the extreme right (halogens) are good oxidising agents.
The chemical reactivity of an element can be explained by its reactions with oxygen. Elements on
two extremes of a period (1st and 17th groups) easily combine with oxygen to form oxides. The normal
oxide formed by the element on extreme left (1st group) is the most basic (e.g. Na2O), whereas that
formed by the element on extreme right (17th group) is the most acidic (e.g. Cl2O7). Oxides of elements
in the centre are amphoteric (e.g. Al2O3, As2O3) or neutral (e.g. CO, NO, N2O). Amphoteric oxides behave
both as acidic (with bases) and basic (with acids), while neutral oxides have no acidic or basic properties.

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