CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES

Dobereiner’s Law of Triads

When elements are arranged in increasing order of their atomic weight, the middle
element of each of the Triads had an atomic weight about half way between the atomic
weights of the other two.

The Newland’s Law of Octaves

When elements are arranged in increasing order of their atomic weights then properties of
every eighth element is similar to the first element (Table). The relationship was just like
every eighth note that resembles the first in octaves of music.

Mendeleev’s periodic law--

The properties of the elements are a periodic function of their atomic weights

He left the gap under aluminium and a gap under silicon, and called these elements Eka-
Aluminium and Eka-Silicon.
Drawbacks of mendeleev’s periodic table—
1. He could not justify the position of isotopes. i.e. different atomic positions but they
have same position in periodic table, 1H1, 1H2 and 1H3
2. He could not justify the position of isobars, i.e. same atomic masses but elements
having different positions in the periodic table, e.g. 20Ca40 and 19K39.
3. There is no position for f-block elements in the main body of periodic table.
MODERN PERIODIC LAW
The physical and chemical properties of the elements are periodic functions of their atomic
numbers.
THE PRESENT FORM OF THE PERIODIC TABLE or ―long form‖ of the Periodic Table--
1. It has 7 horizontal rows are called periods, hence there are altogether seven periods.
2. 18 vertical columns known as groups. Elements having similar outer electronic
configurations in their atoms are arranged in vertical columns, referred to as groups
or families.
3. The period number corresponds to the highest principal quantum number (n) of the
elements in the period. The first period contains 2 elements. The subsequent periods
consists of 8, 8, 18, 18 and 32 elements, respectively. The seventh period is incomplete
and like the sixth period would have a theoretical maximum (on the basis of quantum
numbers) of 32 elements.
4. In this form of the Periodic Table, 14 elements of both sixth and seventh periods
(lanthanoids and actinoids, respectively) are placed in separate panels at the bottom*.

Advantage of modern periodic law over Mendeleev’s periodic law—

1. Position of isotopes and isobars became clear.
2. Position of lanthanides and actinides are justified.
But position of hydrogen is still controversial.

NOMENCLATURE OF ELEMENTS WITH ATOMIC NUMBERS > 100

A systematic nomenclature be derived directly from the atomic number of the element
using the numerical roots for 0 and numbers 1-9. These are shown in Table. The roots are
put together in order of digits which make up the atomic number and ―ium‖ is added at the
end. The IUPAC names for elements with Z above 100 are shown in

.
Classification of the elements into four blocks viz., s-block, p-block, d-block and f-block

The s-Block Elements---Elements in which last electron enter in to the s-sub shell are known
as s-block elements.
The elements of Group 1 (alkali metals) and Group 2 (alkaline earth metals) which have ns1
ns2 outermost electronic configuration belong to the s-Block Elements. Hence general
electronic configuration is ns1 to 2.
Important properties of s-Block Elements are as :
1. They are all very reactive metals with low ionization enthalpies.
2. They lose the outermost electron(s) readily to form 1+ ion (in the case of alkali metals) or
2+ ion (in the case of alkaline earth metals).
3. The metallic character and the reactivity increase as we go down the group.
4. Because of high reactivity they are never found pure in nature.
5. The compounds of the s-block elements, with the exception of those of lithium and
beryllium are predominantly ionic.

Q. ―He belongs to the s-block but its positioning in the p-block along with other group 18
elements.‖ Justify the position of He.
Ans. It is justified because it has a completely filled valence shell (1s2) and as a result,
exhibits properties of other noble gases.
Q. What is the reason ―position of hydrogen in periodic table is controversial‖?
Ans. It has a lone s-electron and hence can be placed in group 1 (alkali metals). It can also
gain an electron to achieve a noble gas arrangement and hence it can behave similar to a
group 17 (halogen family) elements. Because it is a special case, we shall place hydrogen
separately at the top of the Periodic Table

The p-Block Elements---- Elements in which last electron enter in to the p-sub shell are
known as p-block elements.
The elements of Group 13 (aluminium family), Group 14 (Carbon family), Group 15
(Nitrogen family), Group 16 (Chalcogens), Group 17 (Halogens) and Group 18 (Inert Gases)
are p-block elements. General electronic configuration is ns2 np1 to 6
s-Block Elements and p-block elements collectively are calledthe Representative Elements or
Main Group Elements.
Important properties of p-Block Elements are as ---
1. This block has elements in all physical states and maximum elements are non-metals..
2.Noble gas (Gr. 18) element have completely filled valence shell with ns2np6
configuration so they show very low chemical reactivity..
3. Halogens (Group 17) and chalcogens (Group 16) are another important groups of non-
metals. These two groups of elements have high negative electron gain enthalpies and
readily add one or two electrons respectively to attain the stable noble gas configuration.
4. 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.

The d-Block Elements : Elements in which last electron enter in to the (n-1)d-sub shell are
known as d-block elements. They also known as Transition Elements.
The elements of Group 3 to Group 12 in the centre of the Periodic Table belong to transition
elements. Their general electronic configuration is ns1 or 2 (n-1)d1 to 10 .
The elements of Group 3 to Group 11 in the Periodic Table belong to transition elements.
Their general electronic configuration is ns1 or 2 (n-1)d1 to 9
Important properties of d-Block Elements are as ---
1.They are all metals.
2.They mostly form coloured ions, exhibit variable valence (oxidation states),
paramagnetism and oftenly used as catalysts.
Q. What is the reason Zn, Cd and Hg do not show most of the properties of transition
elements‖.
Zn, Cd and Hg which have the electronic configuration, ns2 (n-1)d 10
so due to complete
d-orbitals they do not show most of the properties of transition elements.

The f-Block Elements: Elements in which last electron enter in to the (n-2)f-sub shell are
known as f-block elements. And they also known as Inner-Transition Elements.
---The two rows of elements at the bottom of the Periodic Table, called the Lanthanoids, Ce
(Z = 58) – Lu(Z = 71) and Actinoids, Th (Z = 90) – Lr (Z = 103) are belong to this group. Their
general electronic configuration is or outer electronic configuration is (n-2) f 1-14 (n-1) d 0–1 ns 2.
Important properties of f-Block Elements are as ---
1.They are all metals. Within each series, the properties of the elements are quite similar
because they have same electronic configuration for last two orbits.
2. They show large number of oxidation states.
3. Actinoid elements are radioactive and not available in the nature. They are artificially
prepared, hence their chemistry is not fully studied.
The elements after uranium are called Transuranium Elements.
PERIODIC TRENDS IN PROPERTIES OF ELEMENTS

Trends in Properties ----Physical properties of elements such as melting and boiling points,
heats of fusion and vaporization, energy of atomization, atomic and ionic radii, ionization
enthalpy, electron gain enthalpy and electronegativity. etc. which show periodic variations.
(a) Atomic Radius
Q. It is very difficult to measure the size/radius of an atom, why?
Ans. 1. Because the size of an atom is very small.
2.The electron cloud surrounding the atom does not have a sharp boundary.
―Covalent Radius‖---Half of the distance between the atoms (center to center) in the
combined state of a non-metallic element when their atoms are bound together by a single
bond in a covalent molecule
―Metallic Radius‖--- Half of the inter nuclear distance separating the metal cores in the
metallic crystal.
Atomic Radius word refers to both covalent or metallic radius depending on whether the
element is a non-metal or a metal.
Trend in periodic table--- It is in terms of nuclear charge and energy level.
The atomic size generally decreases across a period, because within the period the outer
electrons are in the same valence shell and the effective nuclear charge increases as the
atomic number increases resulting in the increased attraction of electrons to the nucleus.
Within a family or vertical column of the periodic table or in a group the atomic radius
increases regularly with atomic number because the principal quantum number (n) increases
and the valence electrons are farther from the nucleus. Because the inner energy levels are
filled with electrons, which serve to shield the outer electrons from the pull of the nucleus.
Consequently the size of the atom increases.
Note The atomic radii of noble gases are not considered here. Being monoatomic, their van
der Waals radii (non-bonded radii) values are very large.
Q. When we go left to right across the period atomic radii first decreases and then abruptly
increases for inert gases. Explain well.
Ans. In case of other elements of period we consider metallic and covalent radii i.e. in
bonded form but for inert gases we consider vander wall’s radii i.e. in non-bonded form.
(b) Ionic Radius
The removal of an electron from an atom results in the formation of a cation, whereas gain
of an electron leads to an anion.
The ionic radii is the distances between cations and anions in ionic crystals.
In general, the ionic radii of elements exhibit the same trend as the atomic radii.
A cation is smaller than its parent atom because it has lesser electrons than its atom while
its nuclear charge remains the same.
The size of an anion will be larger than that of the parent atom because it has more
electrons than its atom while its nuclear charge remains the same. The addition of one or
more electrons would result in increased repulsion among the electrons and a decrease in
effective nuclear charge.
Isoelectronic species--Atoms and ions which contain the same number of electrons,
e.g. O2–, F–, Na+ and Mg2+ have the same number of electrons (10).
The cation with the greater positive charge will have a smaller radius because of the greater
attraction of the electrons to the nucleus. Anion with the greater negative charge will have
the larger radius, e.g. O2–> F–> Na+> Mg2+
(c) Ionization Enthalpy [ΔieH]
It is the energy required to remove an electron from an isolated gaseous atom (X) in its
ground state.
First ionization enthalpy is the energy required to remove first electron from an isolated
gaseous atom (X) in its ground state.
For an element X , the first enthalpy change (ΔiH1) can be depicted as--

Units of ionization enthalpy is kJ mol–1.

Second ionization enthalpy is the energy required to remove second electron from an
monovalent cation (X+). in its ground state. the second enthalpy change (ΔiH2) can be
depicted as--

Energy is always required to remove electrons from an atom and hence ionization enthalpies
are always positive.
The second ionization enthalpy will be higher than the first ionization enthalpy because it
is more difficult to remove an electron from a positively charged ion than from a neutral
atom. In the same way the third ionization enthalpy will be higher than the second and so
on.
Ionization Enthalpy is maximum at the noble gases which have closed electron shells and
very stable electron configurations. And minimum occur at the alkali metals and their low
ionization enthalpies can be correlated with their high reactivity.
First ionization enthalpy generally increases as we go across a period and decreases as we
descend in a group.
Anomalous behavior of some elements—
Case-I—Boron (Z = 5) has slightly lesser ionization enthalpy than that of beryllium (Z = 4)
even though the former has a greater nuclear charge,--
-When considered the same principal quantum level, an s-electron is attracted to the
nucleus more than a p-electron. In beryllium, the electron removed during the ionization is
an s-electron whereas the electron removed during ionization of boron is a p-electron. The
penetration of a 2s-electron to the nucleus is more than that of a 2p-electron; hence the
2p electron of boron is more shielded from the nucleus by the inner core of electrons than
the 2s electrons of beryllium. Therefore, it is easier to remove the 2p-electron from boron
compared to the removal of a 2s- electron from beryllium. Thus, boron has a smaller first
ionization enthalpy than beryllium.
Case-II-- Oxygen (Z = 8) has slightly lesser ionization enthalpy than that of Nitrogen (Z = 7)
even though the former has a greater nuclear charge--
---because in the nitrogen atom, three 2p-electrons reside in different atomic orbitals
(Hund’s rule) whereas in the oxygen atom, two of the four 2p-electrons must occupy the
same 2p-orbital resulting in an increased electron-electron repulsion. Consequently, it is
easier to remove the fourth 2p-electron from oxygen than it is, to remove one of the three
2p-electrons from nitrogen i.e. half filled orbitals are most stable (Hund’s rule)

(d) Electron Gain Enthalpy

When an electron is added to a neutral gaseous atom (X) to convert it into a negative ion,
the enthalpy change during this process is known as the Electron Gain Enthalpy (ΔegH)
represented by equation as--
Electron gain enthalpy provides a measure of the ease with which an atom adds an electron
to form anion
X (g) + e-  X- (g)
Depending on the element, the process of adding an electron to the atom can be either
endothermic or exothermic.
--- noble gases have large positive electron gain enthalpies because the electron has to
enter the next higher principal quantum level leading to a very unstable electronic
configuration.

Electron gain enthalpy becomes more negative with increase in the atomic number across a
period because the effective nuclear charge increases from left to right across a period.
Electron gain enthalpy to become less negative as we go down a group because the size
of the atom increases and the added electron would be farther from the nucleus.
Electron gain enthalpy of O or F is less negative than that of the succeeding element S and
Cl.
---This is because when an electron is added to O or F, the added electron goes to the
smaller n = 2 quantum level and suffers significant repulsion from the other electrons
present in this level due to small size of n = 2 orbit than n = 3 orbit.. For the n = 3 quantum
level (S or Cl), the added electron occupies a larger region of space and the electron-
electron repulsion is much less.
(e) Electronegativity
It is the ability of bonded atom in a molecule to attract shared electron pair to itself is
called electronegativity.
It is maximum for F > O > N>Cl .
Electronegativity also increases in a period as the atomic radius, decreases and the nucleus
charge increases and its values decrease with the increase in atomic radii down a group. The
trend is similar to that of ionization enthalpy.

Hence Non-metallic elements have strong tendency to gain electrons. Therefore,

electronegativity is directly related to that non-metallic properties of elements or
electronegativity is inversely related to the metallic properties of elements. Thus, the
increase in electronegativities across a period there is an increase in non-metallic properties
(or decrease in metallic properties) of elements.

Periodic Trends in Chemical Properties

Periodicity - It is repetition of properties after a regular time interval is known as
periodicity.
(a) Periodicity of Valence or Oxidation States
It can be understood in terms of their electronic configurations. The valence of
representative elements is usually (though not necessarily) equal to the number of electrons
in the outermost orbitals and / or equal to eight minus the number of outermost electrons
as shown below.

(b) Anomalous Properties of Second Period Elements

i) Diagonal relationship
it is the similarity in properties between the elements that are present diagonally is known
as diagonal relationship in the periodic properties. e.g. lithium unlike other alkali metals,
and beryllium unlike other alkaline earth metals, form compounds with pronounced
covalent character; the other members of these groups predominantly form ionic
compounds.
The anomalous behaviour is attributed to their small size, large charge/ radius ratio and
high electronegativity of the elements.
Q.What are the reasons for the different chemical behaviour of the first member of a group
of elements in the s- and p-blocks compared to that of the subsequent members in the
same group?
Ans. The anomalous behaviour is due to (a) their small size (b) large charge/radius ratio and
(c) high electronegativity of the (d) The first member of each group has only four valence
orbitals (2s and 2p) available for bonding, whereas the second member of the groups have
nine valence orbitals (3s, 3p, 3d).
(i) This is the reason the maximum covalency (number of pair of electrons around central
atom) of the first member of each group is 4
(e.g., boron can only form BF4-] whereas the other members of the groups can expand their
valence shell to accommodate more than four pairs of electrons e.g., aluminium forms
[AlF63-]
(ii) The first member of p-block elements displays greater ability to form pπ – pπ
bonds to itself (e.g. C = C, C ≡ C, N = N, N ≡ N ) and to other second period elements
(e.g., C = O, C = N, C ≡ N, N = O) compared to subsequent members of the same group.

Elements on two extremes of a period easily combine with oxygen to form oxides. 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 centre 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.