PERIODIC TABLE AND PERIODIC PROPERTIES

DOBEREINER’S TRIADS-

Dobereiner noted a similarity among the physical and chemical properties of several
groups of three elements (Triads). In each case, he noticed that the middle element of
each of the Triads had an atomic weight about half way between the atomic weights of
the other two.Also the properties of the middle element were in between those of the
other two members. Dobereiner’s relationship, referred to as the Law of Triads, works
only for a few elements.

NEWLAND’S LAW OF OCTAVES -He arranged the elements in increasing order of their
atomic weights and noted that every eighth element had properties similar to the first
element. The relationship was just like every eighth note that resembles the first in
octaves of music. Newlands’s Law of Octaves seemed to be true only for elements up
to calcium.

MENDELEEV’S PERIODIC TABLE -On arranging elements in the increasing order of

their atomic weights, similarities appear in physical and chemical properties at regular
intervals.

Mendeleev periodic law- The properties of the elements are a periodic function of their
atomic weights.

Mendeleev arranged elements in horizontal rows and vertical columns of a table in

order of their increasing atomic weights in such a way that the elements with similar

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properties occupied the same vertical column or group.He fully recognized the
significance of periodicity and used broader range of physical and chemical properties
to classify the elements. In particular, Mendeleev relied on the similarities in the
empirical formulas and properties of the compounds formed by the elements. He
realized that some of the elements did not fit in with his scheme of classification if the
order of atomic weight was strictly followed. He ignored the order of atomic weights and
placed the elements with similar properties together.For example, iodine with lower
atomic weight than that of tellurium (Group VI) was placed in Group VII along with
fluorine, chlorine, bromine because of similarities in properties. At the same time,
keeping his primary aim of arranging the elements of similar properties in the same
group, he proposed that some of the elements were still undiscovered and, therefore,
left several gaps in the table. For example, both gallium and germanium were unknown
at the time Mendeleev published his Periodic Table. He left the gap under aluminium
and a gap under silicon, and called these elements Eka-Aluminium and Eka-Silicon.
Mendeleev predicted not only the existence of gallium and germanium, but also
described some of their general physical properties. These elements were discovered
later.

Modern Periodic Law -Henry Moseley observed regularities in the characteristic X-ray
spectra of the elements. A plot of (where is frequency of X-rays emitted)
against atomic number (Z ) gave a straight line and not the plot of vs atomic mass.
He thereby showed that the atomic number is a more fundamental property of an
element than its atomic mass. Mendeleev’s Periodic Law was, therefore, accordingly
modified. This is known as the Modern Periodic Law and can be stated as: The physical
and chemical properties of the elements are periodic function of their atomic numbers.
Periodic Law is essentially the consequence of the periodic variation in electronic
configurations, which determine the physical and chemical properties of elements and
their compounds.

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The most commonly known periodic table is the Long form of the periodic table.

There are 7 periods and 18 groups in the long form of periodic table.

Each and every period starts with electrons entering into a new orbit (Thus first element
of each period will have different value of principal quantum no.‘n’).According to Bohr
Bury scheme the maximum no. of electrons in any orbit is given by 2n2.

The first period (n = 1) ) is called as the ‘shortest’ period and starts with the filling of the
lowest level (1s) and therefore has two elements — hydrogen (ls1) and helium (ls2) when
the first shell is completed.

The second period (n = 2) ) is called as ‘short’ period starts with lithium and the third
electron enters the 2s orbital. The next element, beryllium has four electrons and has
the electronic configuration 1s22s2. Starting from the next element boron, the 2p orbitals
are filled with electrons when the second shell is completed at neon (2s22p6). Thus there
are 8 elements in the second period.

The 3rd period is supposed to have 18 elements. Actually there are only 8 elements in
the 3rd period. ).The orbitals available for filling in the 3rd orbit are 3s, 3p, and

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3d.However according to Aufbau principle the 3d subshell can be filled only after the 4s
subshell is filled. Thus, in the 3rd orbit available subshells are only 3s and 3p and hence
there will be only 8 elements in this period. The third period (n = 3) called as ‘short’
period like the second period begins at sodium, and the added electron enters a 3s
orbital. Successive filling of 3s and 3p orbitals gives rise to the third period of 8
elements from sodium to argon .

Similarly 4th period has only 18 elements though it was expected to have 32elements.
(4s,3d and 4p) The fourth period (n = 4) ) is called as a ‘long’ period starts at potassium,
and the added electrons fill up the 4s orbital. Before the 4p orbital is filled, filling up of 3d
orbitals takes place and we get the so called 3d transition series of elements. This starts
from scandium (Z = 21) which has the electronic configuration 3d14s2. The 3d orbitals
are filled at zinc (Z=30) with electronic configuration3d104s2. The fourth period ends at
Krypton with the filling up of the 4p orbitals (Z=36).

The fifth period (n = 5) beginning with rubidium is ) is also called as a long’ period and is
similar to the fourth period in that it contains a total of 18 elements and contains the 4d
transition series starting at yttrium (Z = 39). This period ends at xenon with the filling up
of the 5p orbitals.

The sixth period (n = 6) ) is called as the ‘longest’ period and contains 32 elements with
successive electrons entering in the order -6s, 4f, 5d and 6p orbitals.Filling up of the 4f
orbitals begins with cerium (Z = 58) and ends at lutetium (Z = 71) to give the 4f-inner
transition series which is called the lanthanoid series.

The seventh period (n = 7) is called as incomplete period and is similar to the sixth
period with the successive filling up of the 7s,5f, 6d and 7p orbitals and includes most of
the man-made radioactive elements. This period ends at the element with atomic
number 118 which would belong to the noble gas family. Filling up of the 5f orbitals after
actinium (Z = 89) gives the 5f-inner transition series known as the actinoid series.

The 4f known as lanthanoids and 5f-inner transition series of elements known as

actinoids are placed separately in the Periodic Table to maintain its structure and to
preserve the principle of classification by keeping elements with similar properties in a
single column.

Each and every group in the periodic table has similar outer electronic configuration.
There are 18 groups in the periodic table.

Alkali metals belong to group 1 have general electronic configuration of ns1.

Alkaline earth metals →ns2 (group 2)
Boron family →ns2 np1 (group 13)

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Carbon family →ns2 np2 (group 14)
Nitrogen family ns2np3 (group 15)

Oxygen family (Chalcogens) ns2np4 (group16).

Halogens ns2np5 (group 17)

Noble gases ns2np6 (group 18)

Elements can be classified into four blocks viz., s-block, p-block, d-block and f-block
depending on the type of atomic orbitals that are being filled with the last electron. If the
last electron of an element enters a‘s’ subshell it will be classified as a ‘s’ block element.
Similarly If the last electron of an element enters a ‘p’ subshell it will be classified as a
‘p’ block element and so on. There are two exceptions to this categorisation. Strictly,
helium belongs to the s-block but its positioning in the p-block along with other group 18
elements is justified because it has a completely filled valence shell (1s2 ) and as a
result, exhibits properties characteristic of other noble gases. The other exception is
hydrogen. It has only one 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.

Elements of s and p block are collectively called as main group elements or

representative elements

Elements of d block (groups 3-12) are called as transition elements

Elements of f block are called as inner transition elements.

An element of 2nd period always shows exceptional behavior as compared to other

elements of the same group. (Thus elements of 2nd period are never considered for
study of that group. Rather elements of 3rd period are considered for study of that group.
Hence elements of 3rd period are called as typical elements).

Elements of 2nd period show diagonal relationships with many elements of 3rd period.
Hence elements of 2nd period are called bridge elements. Diagonal relationship is due to
similarities in size.E.g. Li& Mg, Be & Al, B & Si.

Zn, Cd, Hg are soft metals.

Cu, Ag, Au are called coinage metals.

Fe, Co, Ni are Ferromagnetic materials.

Elements from atomic no.92 onwards (after Uranium) are called transuranic elements
(radioactive).

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Characteristics of ‘s’ block elements

General electronic configuration is ns1-2It consists of only metals. The elements of Group
1 (alkali metals) and Group 2 (alkaline earth metals) which have ns1and ns2 outermost
electronic configuration belong to the s-Block elements. They are all reactive metals
with low ionization enthalpies. Majority of these metals are highly reactive in nature and
hence ‘s’block elements are not found in free state. They are highly electropositive and
are good reducing agents. 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). The metallic
character and the reactivity increase as we go down the group. With the exception of Li
and Be majority of the compounds formed by these elements are ionic in nature.

Characteristics of ‘p’ block elements.

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The p-Block elements comprise those belonging to Group 13 to 18.They consists of
metals, non-metals and metalloids. 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. General electronic configuration is ns2 np1-6.. Group 16 elements are called as
chalcogens and group 17 elements are called halogens. These two groups of elements
have highly negative electron gain enthalpies and readily add one or two electrons
respectively to attain the stable noble gas configuration. At the end of each period is a
noble gas element with a closed valence shell ns2np6 configuration .All the orbitals in the
valence shell of the noble gases are completely filled by electrons and it is very difficult
to alter this stable arrangement by the addition or removal of electrons. The noble gases
thus exhibit very low chemical reactivity. Some ‘p’ block elements show variable
oxidation states and they can form ionic as well as covalent compounds.
Characteristics of ‘d’ block elements.

These are the elements of Group 3 to 12 in the centre of the Periodic Table. These are
characterised by the filling of inner d orbitals by electrons and are therefore referred to
as d-block elements. These elements have the general outer electronic configuration
(n-1)d 1-10ns0-2 .They are all metals. They are called as transition elements because their
properties are intermediate between that of s and p block elements. However, Zn, Cd
and Hg which have the electronic configuration,(n-1) d 10ns2 do not show most of the
properties of transition elements. Their general characteristics are:-
They are hard high melting metals.
They show variable oxidation states.
Transition element form large no. of alloys.
They form large no. of complexes due to small size and high nuclear charge.
They form ionic as well as covalent compounds.
They act as good catalysts.
Characteristics of f-block elements

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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 characterised by
the outer electronic configuration (n-2)f1-14 (n-1)d 0–1ns2. The last electron added to
each element is filled in f- orbital. These two series of elements are hence called the
InnerTransition Elements (f-Block Elements). They are all high melting metals , show
variable oxidation states and have ability to form complexes Within each series, the
properties of the elements are quite similar. Most of the elements of actinoid series are
radioactive. The elements after uranium are called Transuranium elements..

Metals, Non-metals and Metalloids-The elements can be divided into Metals and Non-
Metals. Metals comprise more than 78% of all known elements and appear on the left
side of the Periodic Table. Metals are usually solids at room temperature [mercury is an
exception; gallium and caesium also have very low melting points (303K and 302K,
respectively)]. Metals usually have high melting and boiling points. They are good
conductors of heat and electricity. They are malleable (can be flattened into thin sheets
by hammering) and ductile (can be drawn into wires). In contrast, non-metals are
located at the top right hand side of the Periodic Table. Across a period, the property of
elements change from metallic on the left to non-metallic on the right. Non-metals are
usually solids or gases at room temperature with low melting and boiling points (boron
and carbon are exceptions). They are poor conductors of heat and electricity. Most
nonmetallic solids are brittle and are neither malleable nor ductile. The elements
become more metallic as we go down a group; the nonmetallic character increases as
one goes from left to right across the Periodic Table. s’ block and ‘d’ block are entirely
metals whereas ‘p’ block has metals,non-metals and metalloids. The change from
metallic to non-metallic character is not abrupt. The elements (e.g., silicon, germanium,
arsenic, antimony and tellurium) running diagonally across the Periodic Table show
properties that are characteristic of both metals and nonmetals. These elements are
called Semi-metals or Metalloids.

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NOMENCLATURE OF ELEMENTS WITH ATOMIC NUMBERS >100
0 nil n
1 un u
2 bi b
3 tri t
4 quad q
5 pent p
6 hex h
7 sept s
8 oct o
9 enn e

PERIODIC TRENDS IN PROPERTIES OF ELEMENTS

The periodic repetition of elements with similar properties after certain regular intervals
when the elements are arranged in order of increasing atomic number is called
periodicity. It is due to the recurrence of similar valence shell configurations (outer
electronic configuration) after certain regular intervals.

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There are many observable patterns in the physical and chemical properties of
elements as we descend in a group or move across a period in the Periodic Table. For
example, within a period, chemical reactivity tends to be high in Group 1 metals, lower
in elements towards the middle of the table, and increases to a maximum in the Group
17 non-metals. Likewise within a group of representative metals (e.g.alkali metals)
reactivity increases on moving down the group, whereas within a group of non-metals
(e.g. halogens), reactivity decreases down the group. Similarly there are numerous
physical properties of elements such as melting and boiling points, heats of fusion and
vaporization, energy of atomization, etc. which show periodic variations.
ATOMIC RADIUS is defined as the distance from the centre of the nucleus to the region
where the nucleus exerts its influence. It is a theoretical concept and cannot be
determined accurately due to the following reasons.
1. To determine atomic radius, an isolated atom is required which is not possible to get.
2. Where the electron cloud of the atom ends cannot be determined accurately.
3. Shape of electron cloud is influenced by neighbouring atoms and molecules.
4. Shape of electron cloud is also influenced by the type of bonding the atom
undertakes.

1. COVALENT RADII is one half of the distance between two atoms held together by a
single covalent bond. (This definition is applicable exactly only for homo-nuclear
molecules. In the case of hetero-nuclear molecules, the electron cloud shifts towards
the more electro-negative atom, hence calculations won’t be accurate).
2. VANDER-WALLS RADII - The force of attraction between nucleus and electron is
electrostatic in nature and hence non-directional. Thus the nucleus of an atom besides
attracting electrons of the same atom also develops slight attraction for electrons of
neighbouring atoms. These weak forces of attraction which develop between atoms of
neighbouring molecules are called as Vander-walls forces of attraction.
Vander-Walls radius is defined as one half of the distance between two atoms of
neighbouring molecules in solid state. Because Vander- walls forces of attractions are
weak,Vander walls radius in general is larger than covalent radius.
Both covalent and Vander-Walls radius increases down a group and decreases along a
period.

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Size increases down a group due to the addition of new orbits or shells (which
compensates for increased nuclear charge). This happens 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. Exceptions generally arise
due to poor shielding of ‘d’ and ‘f’ electrons preceding ‘p’ electrons.e.g.in the 13 th group,
Gallium is smaller than Aluminum due to poor shielding of ‘d’ electrons preceding outer
‘p’ electron leading to increased nuclear charge on the outer ‘p’ electron and
consequently smaller size.

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Size decreases along a period due to increased nuclear charge (As no. of electrons
increase in the orbit, no of protons in nucleus also increases correspondingly).In a
period electrons enter into the same shell and do not screen each other from the
nucleus. Thus the increase in nuclear charge is not neutralized by the extra valence
electron and consequently electrons are pulled more closely by nucleus leading to
smaller size. However the variation is not uniform and there are exceptions.e.g. In the
second period nitrogen is smaller than oxygen. This is because in oxygen there are two
electrons in one of the ‘p’ orbital leading to greater inter-electronic repulsion, expansion
of electron cloud and larger size. (Nitrogen on the other hand has no paired electron in
its outer ‘p’ orbital).Fluorine in spite of having more inter-electronic repulsion than
oxygen has smaller size than oxygen because in its case increased nuclear charge
outweighs increased inter-electronic repulsion.
In any period the alkali metals have the largest size and halogens the smallest size.
Noble gases have large values of radii as the only forces of attraction in them are the
Vander- walls forces of attraction and hence they possess only Vander walls radius
which in general is large. Along a period size decreases because the expected increase
in size due to increase inter-electronic repulsion is compensated by increased nuclear
charge. This goes on from alkali metal to halogen. From halogen to noble gas inter-
electronic repulsion predominates over increased nuclear charge and hence size
increases.

3. METALLIC RADII is one half of the inter-nuclear distance between the two which is
taken as half the internuclear distance separating the metal cores in the metallic crystal.
4. IONIC RADIUS is the effective distance from the nucleus of the ion up to which it has
an influence in the ionic bond.
A cation is always smaller than the atom from which it is formed and an anion is always
larger than the atom from which it is formed.
Cations are smaller than the atom from which it is formed because of the following
reasons:-

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1. In many cases one or more orbits are removed during formation of cation leading to
decrease in size.
2. Due to loss of electron, nuclear charge increases and the remaining electrons are
held more tightly and hence size decreases.
3. Due to removal of an electron, the inter-electronic repulsion decreases, leading to
decrease in size.
In the case of anions, size is always larger than the atom from which it is formed due to
the following reasons.
1. Due to the addition of an electron, nuclear charge decreases leading to increase in
size.
2. Due to addition of an electron, the inter- electronic repulsion increases, expansion of
the electron cloud happens leading to increase in size.
3. In certain cases, new orbits are added when anion is formed leading to larger size.
All cations are smaller than even the smallest anion F-except for Rb+ and Cs+ which are
bigger than F- but smaller than all other anions.
Cations < F-< Rb + <Cs + < anions.
In the case of iso-electronic species, higher the positive charge, smaller would be the
size of the ion and higher the negative charge, larger would be the size of the ion.
Higher negative charge →lower nuclear charge, larger size.
Higher positive charge →Higher nuclear charge, smaller size.
N3 - >02- > F - > Na+ > Mg2+ > Al 3+
IONIZATION ENERGY OR IONIZATION POTENTIAL OR IONIZATION ENTHALPY
Ionization energy or enthalpy is defined as the energy required to remove the most
loosely bound electron from its isolated gaseous atom in the ground state.
A(g) A+(g) + e-
The energy required to remove the first electron is called first ionization energy (IE 1 or
∆iH1).
A(g) A+(g) + e- (IE1 or ∆iH1).
The energy required to remove the second electron is called second ionization energy
(IE2 or ∆iH2).
A+(g) A2+(g) + e- (IE2 or ∆iH2).
The energy required to remove the third electron is called third ionization energy (IE 3 or
∆iH3).
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A 2+g) A3+(g) + e- (IE3 or ∆iH3).
Successive ionization energy values are always higher because if one or more
electrons are removed, the remaining electrons are held more tightly by the nucleus
(nuclear charge increases).
IE3 > IE2 >IE1 or ∆iH3> ∆iH2 > ∆iH1
Ionization energy in general decreases down the group due to increased size. As we go
down a group size increases and thus IE decreases as the outermost electron will be far
away from the nucleus and hence can be pulled out easily. Moreover due to increase in
the number of inner electrons, shielding effect increases and consequently I.E.
decreases. (Though the nuclear charge also increases down a group, its effect is
cancelled by increase in atomic size and increased shielding effect).

I.E. increases along the period due to increased nuclear charge. Along a period nuclear
charge increases because electrons are added to the same orbit. Thus the distance of
the outermost electron from the orbit remains the same. Due to this electrons are held
more tightly by the higher positively charged nucleus and hence ionization energy
increases. In any period, alkali metals have the lowest and noble gases the highest
values of I.E.

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Besides size and nuclear charge, ionization energy depends on other factors also. Thus
the variation of ionization energy in a period is not uniform.E.g. In the second period
Boron has lower ionization energy than Beryllium and Oxygen has lower I.E. than
Nitrogen.
One of the factors which affect ionization energy is electronic configuration .More stable
the electronic configuration, greater is the ionization enthalpy.i.e.Substances with stable
half filled and fully filled electronic configuration tends to have higher ionization
energy.This explains why noble gases have very large values of ionization energy
(highest amongst all elements in a period). Noble gases have stable ns2np6
configuration and resists loosing it. Thus large amounts of energy will be required to
remove an electron from this stable arrangement. Similarly Nitrogen due to its stable
half-filled electronic configuration has a comparatively higher value of ionization energy
which is higher than Oxygen itself. (Nitrogen doesn’t want to lose an electron and
become unstable).Another reason is that removal of an electron from oxygen gives it a
stable half filled configuration than that obtainable by nitrogen. Phosphorus has higher
ionization energy than sulphur for the same reason.
Alkali metals have lower first ionization energy (IE1)than the alkaline earth metal in a
particular period whereas the reverse is true for second ionization energy (IE2). First
ionization energy of alkaline earth metals are higher than alkali metals because of
higher nuclear charge and smaller size. On the other hand, after removal of an electron,
the alkali metal cation acquires a stable noble gas configuration making removal of
second electron highly difficult and consequently high second ionization energy.In the
case of alkaline earth metal noble gas configuration is attained only after the removal of
the second electron,hence its second ionization energy is comparatively low.
The penetration effect of subshells is another factor which influences ionization
energy.The nucleus always exerts its influence on the subshells in the following order
s>p >d >f.( in multi-electron atoms, electrons in ‘s’ orbital have maximum probability of
being found near the nucleus and this probability goes on decreasing in case of p,d,f
orbitals). Thus it is always more difficult to pull out an electron from ‘s’ subshell as
compared to ‘p’ as compared to d, as compared to ‘f’ subshell. In the case of Beryllium

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and Boron, Beryllium has higher ionization energy because in the first place Beryllium
has a somewhat stable outer electronic configuration of 2s2.Moreover in the case of
Beryllium, the outer electron has to be removed from an ‘s’- sub shell which is always
more difficult as compared to an element like Boron where the outer electron is
removed from a ‘p’ subshell (outer electronic configuration 2s2 2p1).Similarly first
ionization enthalpy of aluminium is less than that of magnesium. Another factor is the
poor shielding of ‘p’ electron as compared to an ‘s’ electron.
Screening effect or shielding effect is another factor influencing ionization energy .In
multi-electron atoms, the inner electrons shield the outer electrons from the effect of the
nucleus.i.e.the electrons present in the outermost shell do not experience the complete
nuclear charge because of repulsive interaction of the intervening electrons. This is
known as shielding or screening effect. If the number of electrons in the inner shells is
large, screening effect will be large and consequently ionization energy will be low. E.g.
Gallium has higher ionization enthalpy than aluminium because the ‘d’ electrons present
before the outermost ‘p’ electron of gallium do not shield properly. Hence the outermost
’p’ electron experiences greater effective nuclear charge and consequently higher
ionization energy .Similarly the unexpectedly high ionization energy value of Thallium
over Indium and that of Lead over Tin is due to the poor shielding of ‘f’ electrons
preceeding their outermost ‘p’ electron.
ELECTRON GAIN ENTHALPY (∆egH)
Electron gain enthalpy of an element is defined as the enthalpy or energy change taking
place when an electron is added to an isolated gaseous atom to form an anion.
X(g) + e- X-(g) ∆H=∆egH
Greater the amount of energy released,higher is the electron gain enthalpy of the
element.Magnitude of electron gain enthalpy measures the tightness with which atom
can hold the additional electron. Thus magnitude of electron gain enthalpy gives an idea
about the electron affinity of an element. Large negative values of electron gain
enthalpy reflects greater tendency of an atom to accept the electron.
Depending on the element, process of addition of electron may be exothermic or
endothermic.
Enthalpy change when first electron is added is called as first electron gain enthalpy.
∆egH1.For majority of the elements it is negative (exothermic).For noble gases it is
however positive as it involves placing an electron into a new shell producing highly
unstable configuration.
From second electron gain enthalpy onwards, values will be positive as it involves
adding an electron to a negatively charged ion and energy must be supplied to
overcome the repulsive force which the incoming electron experiences from the
anion.e.g
O(g) + e- O- (g) ∆egH1= -ve

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O- + e - O2-(g) ∆egH2= +ve.
Thus successive electron gain enthalpies will become more and more positive.
Electron gain enthalpy becomes more negative as we move along the period as
nuclear charge increases and thus the incoming electron will be held more tightly by the
nucleus. Halogens (group 17) have large negative values since addition of an electron
results in stable electronic configuration. Noble gases (group 18) on the other hand
have positive values of electron gain enthalpy as they resist change in their stable
electronic configuration. Group 2 and group 15 elements also show irregularities in their
values due to filled ns and half filled np subshells respectively.
Electron gain enthalpy generally becomes less negative on going down a group. This is
because size increases and consequently the new incoming electron will be far away
from the nucleus and will experience less attraction. Halogens in general have the most
negative values of electron gain enthalpies. This is because they have an electronic
configuration of ns2np5 and gain of an electron gives them stable noble gas
configuration. Since electron gain enthalpy generally becomes less negative on going
down a group, Fluorine was expected to be the element with most negative value of
electron gain enthalpy (highest electron affinity). In practice however it is chlorine which
has the most negative value of electron gain enthalpy. This is because of the small size
and compact nature of the second orbit to which the electron goes in the case of
fluorine due to which it experiences greater inter-electronic repulsion. In chlorine
however it enters into the larger third orbit and experiences less inter electronic
repulsion. Thus chlorine has greater tendency to accommodate an incoming electron
than fluorine and hence has more negative value of electron gain enthalpy (higher
electron affinity). Similar trends are observed between oxygen and sulphur and between
nitrogen and phosphorous.
For noble gases electron gain enthalpy is positive as it involves placing an electron into
a new shell producing highly unstable configuration. Electron gain enthalpy of nitrogen
is slightly positive as it has stable half filled configuration and hence has no tendency to
accept an electron.

ELECTRO NEGATIVITY is defined as the tendency of an atom to attract bonded pairs

of electrons towards itself. It decreases down the group (size increases and bonding
electrons would be far away from the nucleus) and increases along a period (due to
decrease in size and increased nuclear charge). Electronegativity is inversely related to
the metallic properties of elements. Thus, the increase in electronegativities across a
period is accompanied by an increase in non-metallic properties (or decrease in metallic
properties) of elements. Similarly, the decrease in electronegativity down a group is
accompanied by a decrease in non-metallic properties (or increase in metallic
properties) of elements.. Fluorine is the most electronegative element followed by
Oxygen. Cesium is the least electronegative or the most electropositive element. All non
metals except Boron are more electronegative than Hydrogen whereas metals in
general are less electronegative than Hydrogen. As electro negativity of an element

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increases non- metallic character increases. In general as an approximation, elements
with electro negativity 2 or greater (on Pauling’s scale of electro negativity) are non-
metals while those with electro negativity less than 2 are metals. The electronegativity
of an element is not constant bud depends on factors like hybridization
(sp>sp2>sp3),oxidation state(higher the oxidation state,higher is the
electronegativity),nature of substituents attached to the atom ( C in CF3I> C in
CH3I)etc.

Pauling’s scale of electronegativity extends from cesium to fluorine with hydrogen at the
centre. Numerical values are assigned to each element.(e.g. cesium-0.7, fluorine-4.0,
hydrogen-2.1, oxygen-3.5 etc).

∆E = 0, 100% covalent (∆E=difference in electronegativity).

∆E = 1.9, 50% ionic, 50 % covalent

∆E > 1.9 ionic

∆E , if it is between 0 and 1.9 ,the bond is predominantly covalent with some ionic
character. It is called as a polar covalent bond and molecules which possess polar
covalent bonds are called as dipoles.

As difference in electro negativity increases oxide becomes more and more basic
As difference in electro negativity decreases oxide becomes more and more acidic.

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VALENCE
The valence of an element may be defined as the combining capacity of element.
Electrons present in the outermost shell are called as valence electrons and determine
the valence of the atom. In representative elements, valence is equal to either the
number of valence electrons or eight minus the number of valence electrons. Transition
elements exhibit variable oxidation states. In a period valence increases from 1 to 4 and
then decreases from 4 to zero. In a group valence remains the same due to same
number of valence electrons.
The oxidation state of an element in a particular compound can be defined as the
charge acquired by its atom on the basis of electronegative consideration from other
atoms in the molecule. There are many elements which exhibit variable valence. This is
particularly characteristic of transition elements and actinoids.

ANOMALOUS PROPERTIES OF SECOND PERIOD ELEMENTS

The first element of each of the groups 1 (lithium) and 2 (beryllium) and groups 13-17
(boron to fluorine) differs in many respects from the other members of their respective
group. For example, lithium unlike other alkali metals, and beryllium unlike other alkaline
earth metals, form compounds with pronounced covalent character whereas the other
members of these groups predominantly form ionic compounds. The anomalous
behavior is attributed to their small size, large charge/radius ratio and high
electronegativity of the elements. The first member of 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). As a consequence of this, the maximum
covalency of the first member of each group is 4 (e.g., boron can only form [BF 4]-
whereas the other members of the groups can expand their valence shell to
accommodate more than four pairs of electrons e.g.aluminium forms [AlF6]3-.Moreover
the first member of p-block elements displays greater ability to form pπ – pπ multiple
bonds to itself (e.g., C =C, C ≡ C, N = N, N ≡ Ν) 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 of 2nd period show diagonal relationships with many elements of 3rd period.
E.g.The behaviour of lithium and beryllium is more similar with the second element of
the following group i.e., magnesium and aluminium, respectively. This sort of similarity is
commonly referred to as diagonal relationship in the periodic properties. Diagonal
relationship is due to similarities in size .E.g.Li& Mg, Be & Al, B & Si.

Periodic Trends and Chemical Reactivity

The atomic and ionic radii generally decrease in a period from left to right. As a
consequence, the ionization enthalpies generally increases (with some exceptions) and
electron gain enthalpies become more negative across a period. Thus, the ionization
enthalpy of the extreme left element in a period is the least and the electron gain

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enthalpy of the element on the extreme right is the highest negative (noble gases
having completely filled shells have rather positive electron gain enthalpy values). This
results in 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.
Thus elements on the left will be good reducing agents and those on the right good
oxidizing agents. It can also be directly related to the metallic and non-metallic character
of elements. Thus, the metallic character of an element, which is highest at the extreme
left decreases and the non-metallic character increases while moving from, left to right
across the period. The chemical reactivity of an element is best shown by its reactions
with oxygen and halogens. 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, N2 O). Amphoteric oxides behave as acidic
with bases and as basic with acids, whereas neutral oxides have no acidic or basic
properties. Among transition metals (3d series), the change in atomic radii is much
smaller as compared to those of representative elements across the period. The change
in atomic radii is still smaller among inner-transition metals (4f series). The ionization
enthalpies are intermediate between those of s- and p-blocks. Thus they are less
electropositive than group 1 and 2 metals. In a group, the increase in atomic and ionic
radii with increase in atomic number generally results in a gradual decrease in ionization
enthalpies and a regular decrease (with exception in some third period elements as
shown) in electron gain enthalpies in the case of main group elements.

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 EXERCISES
1. What is the basic theme of organisation in the periodic table? [NCERT]
2. Which important property did Mendeleev use to classify the elements in his periodic
table and did he stick to that? [NCERT]
3. What is the basic difference in approach between the Mendeleev’s Periodic Law and
the Modern Periodic Law? [NCERT]
4. Why do elements in the same group have similar physical and chemical properties?
[NCERT]
5. How would you justify the presence of 18 elements in the 5th period of the Periodic
Table? [NCERT]
6. On the basis of quantum numbers, justify that the sixth period of the periodic table
should have 32 elements. [NCERT]
7. In the modern periodic table, the period indicates the value of :(a) atomic number(b)
atomic mass(c) principal quantum number(d) azimuthal quantum number. [NCERT]
8. Write the atomic number of the element present in the third period and seventeenth
group of the periodic table. [NCERT]
9. In terms of period and group where would you locate the element with Z =114?
[NCERT]
10. The elements Z = 117 and 120 have not yet been discovered. In which family /
group would you place these elements and also give the electronic configuration in each
case. [NCERT]
11. Assign the position of the element having outer electronic configuration (i) ns 2np4 for
n=3 (ii) (n-1)d2ns2 for n=4, and (iii) (n-2) f 7 (n-1)d1ns2 for n=6, in periodic table. [NCERT]

12. What would be the IUPAC name and symbol for the element with atomic number
120? [NCERT]
13. Which element do you think would have been named by(i) Lawrence Berkeley
Laboratory(ii) Seaborg’s group? [NCERT]
14. Write the general outer electronic configuration of s-, p-, d- and f- block elements.
[NCERT]
15. What are the major differences between metals and non-metals? [NCERT]
16. Considering the atomic number and position in the periodic table, arrange the
following elements in the increasing order of metallic character : Si, Be, Mg, Na, P.
[NCERT]

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17. Using the Periodic Table, predict the formulas of compounds which might be formed
by the following pairs of elements; (a) silicon and bromine (b) aluminium and sulphur.
[NCERT]
18. Predict the formulas of the stable binary compounds that would be formed by the
combination of the following pairs of elements. (a) Lithium and oxygen (b) Magnesium
and nitrogen (c) Aluminium and iodine (d) Silicon and oxygen (e) Phosphorus and
fluorine (f) Element 71 and fluorine. [NCERT]
19. Anything that influences the valence electrons will affect the chemistry of the
element. Which one of the following factors does not affect the valence shell? (a)
Valence principal quantum number (n) (b) Nuclear charge (Z) (c) Nuclear mass (d)
Number of core electrons. [NCERT]
20. Which of the following statements related to the modern periodic table is incorrect?
(a) The p-block has 6 columns, because a maximum of 6 electrons can occupy all the
orbitals in a p-shell. (b) The d-block has 8 columns, because a maximum of 8 electrons
can occupy all the orbitals in a d-subshell. (c) Each block contains a number of columns
equal to the number of electrons that can occupy that subshell. (d) The block indicates
value of azimuthal quantum number (l) for the last subshell that received electrons in
building up the electronic configuration. [NCERT]
21. Use the periodic table to answer the following questions. (a) Identify an element with
five electrons in the outer subshell. (b) Identify an element that would tend to lose two
electrons. (c) Identify an element that would tend to gain two electrons. (d) Identify the
group having metal, non-metal, liquid as well as gas at the room temperature. [NCERT]
22. Considering the elements B, Al, Mg, and K, the correct order of their metallic
character is : (a) B > Al > Mg > K (b) Al > Mg > B > K (c) Mg > Al > K > B (d) K > Mg >
Al > B. [NCERT]
23. Considering the elements B, C, N, F, and Si, the correct order of their non-metallic
character is : (a) B > C > Si > N > F (b) Si > C > B > N > F (c) F > N > C > B > Si (d) F >
N > C > Si > B. [NCERT]
24. What does atomic radius and ionic radius really mean to you? [NCERT]
25. How does atomic radius vary in a period and in a group? How do you explain the
variation? [NCERT]
26. Explain why cations are smaller and anions larger in radii than their parent atoms?
[NCERT]
27. Describe the theory associated with the radius of an atom as it (a) gains an electron
(b) loses an electron[NCERT]
28. What do you understand by isoelectronic species? Name a species that will be
isoelectronic with each of the following atoms or ions.(i) F– (ii) Ar (iii) Mg2+ (iv) Rb+
[NCERT]

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29. Consider the following species: N3–, O2–, F–, Na+, Mg2+ and Al3+.(a) What is common
in them?(b) Arrange them in the order of increasing ionic radii. [NCERT]
30. Which of the following species will have the largest and the smallest size? i) Mg,
Mg2+, ii) Al, Al 3+.[NCERT]

31. What is the significance of the terms — ‘isolated gaseous atom’ and ‘ground
state’while defining the ionization enthalpy and electron gain enthalpy? [NCERT]
32. Energy of an electron in the ground state of the hydrogen atom is –2.18×10 –18J.
Calculate the ionization enthalpy of atomic hydrogen in terms of J /mol. [NCERT]
33. Would you expect the first ionization enthalpies for two isotopes of the same
element to be the same or different? Justify your answer. [NCERT]
34. What are the various factors due to which the ionization enthalpy of the main group
elements tends to decrease down a group? [NCERT]
35. Which one of the following statements is incorrect in relation to ionization enthalpy?
(a) Ionization enthalpy increases for each successive electron. (b) The greatest
increase in ionization enthalpy is experienced on removal of electron from core noble
gas configuration. (c) End of valence electrons is marked by a big jump in ionization
enthalpy. (d) Removal of electron from orbitals bearing lower n value is easier than from
orbital having higher n value. [NCERT]
36. Among the second period elements the actual ionization enthalpies are in the order
Li < B < Be < C < O < N < F < Ne. Explain why (i) Be has higher Δi H than B (ii) O has
lower Δi H than N and F? [NCERT]
37. The first ionization enthalpy (Δi H ) values of the third period elements, Na, Mg and
Si are respectively 496, 737 and 786 KJ mol–1. Predict whether the first Δi H value for Al
will be more close to 575 or 760 kJ mol–1 ? Justify your answer. [NCERT]
38. How would you explain the fact that the first ionization enthalpy of sodium is lower
than that of magnesium but its second ionization enthalpy is higher than that of
magnesium? [NCERT]
39.The first ionization enthalpy values (in kJ mol–1) of group 13 elements are :
B Al Ga In Tl
801 577 579 558 589
How would you explain this deviation from the general trend? [NCERT]
40.

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Which of the above elements is likely to be: (a) the least reactive element.(b) the most
reactive metal.(c) the most reactive non-metal.(d) the least reactive non-metal. (e) the
metal which can form a stable binary halide of the formula MX2 (X=halogen). (f) the
metal which can form a predominantly stable covalent halide of the formula MX
(X=halogen)? [NCERT]
41. Which of the following will have the most negative electron gain enthalpy and which
the least negative? P, S, Cl, F.Explain your answer. [NCERT]
42. Would you expect the second electron gain enthalpy of O as positive, more negative
or less negative than the first? Justify your answer. [NCERT]
43. Which of the following pairs of elements would have a more negative electron gain
enthalpy? (i) O or F (ii) F or Cl. [NCERT]
44. What is the basic difference between the terms electron gain enthalpy and
electronegativity? [NCERT]
45. How would you react to the statement that the electronegativity of N on Pauling
scale is 3.0 in all the nitrogen compounds? [NCERT]
46. Are the oxidation state and covalency of Al in [AlCl(H2O)5]2+ same ? [NCERT]
47. Show by a chemical reaction with water that Na2O is a basic oxide and Cl2O7 is an
acidic oxide The increasing order of reactivity among group 1 elements is Li < Na < K <
Rb <Cs whereas that among group 17 elements is F > CI > Br > I. Explain. [NCERT]
48. Considering the elements F, Cl, O and N, the correct order of their chemical
reactivity in terms of oxidizing property is : (a) F > Cl > O > N (b) F > O > Cl > N (c) Cl >
F > O > N (d) O > F > N > Cl. [NCERT]

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