Chapter

15
Chemical Periodicity

Periodic table is an arrangement of elements with similar properties (i) Position of hydrogen : Dual behaviour of hydrogen is explained on the
placed together. The periodic table evolved largely as a result of fact that it has one electron in its outermost orbit. When it loses its electron it
experimental observations. gives H and behaves like alkali metals and when it gains an electron it gives H
+ –

and behaves like halogens. Thus, it resembles with both the alkali metals and the
Earlier attempt to classify elements halogens.
(1) Dobereiner’s law of triads (1829) : It was the classification of (ii) Dissimilar elements placed together : The lengths of periods are
elements into groups of three elements each with similar properties such determined by the arrangement of electrons in different orbits. The period
that the atomic weight of the middle element was the arithmetic mean of ends on the completion of last orbits (last members always being the inert
the other two e.g. Ca, Sr, Ba, Cl, Br, I etc.
gas). Different periods contain 2, 8, 18 or 32 elements. Now out of the two
(2) Telluric screw or Helix (1862): It was proposed by Chancourtois. elements which every long period adds to the group, one resembles the
(3) Newlands law of octaves (1864) : It was an arrangement of typical elements while the other does not. This gives rise to formation of
elements in order of increasing atomic weights in which it was observed subgroups. This explains the inclusion of dissimilar elements in the same
that every eighth element had properties similar to those of the first just group but different subgroups.
like the eighth node of an octave of music.
(iii) Position of rare earth elements : The electronic arrangement of
(4) Mendeleef’s period law (1869) : The first significant classification rare earths can be written as 2, 8, 18, (18 + x), 9, 2 where x varies from 0 to
was given by Mendeleeff in the form of periodic table, commonly known as 13, i.e., from Lanthanum to Lutecium. The number of electrons in valency
Mendeleeff's periodic table. His periodic table was based on periodic law, shell, in case of all the elements remain the same although the atomic
''The physical and chemical properties of elements are periodic functions of
number increases. Since they possess the same number of valency electrons,
their atomic weights.''
the chemical behaviour is also similar. This justifies their positions in the
In Mendeleef’s periodic table elements are arranged in order of their same group and in the same place of the periodic table.
increasing atomic weights in such a way that elements with similar
properties are placed in the same group. It consists of seven horizontal rows (iv) Anomalous pairs of elements : Now the basis of classification is
called periods. These are numbered from 1 to 7. atomic number, therefore, this anomaly disappears as the elements occupy their
normal position in the new periodic table.
Mendeleef’s original table consists of 8 vertical columns called
groups. These are numbered as I, II III….. VIII. However, 9 vertical column
th
(v) Position of isotopes : Since the isotopes of same element possess
called Zero group was added with the discovery of inert gases. Except for same atomic number they should occupy one and the same position in the
group VIII and zero, each group is further divided into two sub-groups periodic table.
designated as A and B. Group VIII consists of 9 elements arranged in three (vi) Position of VIII group elements : In long periods 18 elements are
sets each containing three elements. to be distributed among 8 groups; 1 to 7 groups get 2 elements each and
(5) Modern Periodic Law : The recent work has established that the zero group accommodates inert elements, the rest three elements are placed
fundamental property of an atom is atomic number and not atomic weight. at one place in a new group, known as VIII group. This lack of space
Therefore, atomic number is taken as the basis of the classification of the justifies the induction of VIII group in the periodic table.
elements. The modern periodic law was given by Moseley, it may be stated as : (vii) Transuranic elements : These elements form a series known as
''The properties of elements are periodic functions of their atomic number". actinide series, it begins from actinium and ends at lawrencium (89–103).
This series has been placed outside the periodic table. The electronic
When atomic number is taken as the basis for classification of elements, configuration of these elements can be written as 2, 8, 18, 32, (18 + x), 9, 2,
many anomalies of Mendeleef's table disappear, such as the, where x varies from zero (for actinium) to 14 (for lawrencium). The number
of valency electrons remains the same for all these elements although
atomic number increases. Therefore, their chemical behaviour is similar. (ii) Actinides from Th(90) to Lr(103)
This justifies their position outside the periodic table at one place.
Each series consists of 14 elements i.e. in the lanthanides, 4 f is
Classification of element on the basis of
gradually filled up while in actinides, 5 f is gradually filled up.
electronic configuration
The properties of these elements are similar to transition elements.
According to Bohr the element have been grouped into four types The members of actinide series are radioactive and majority of them are not
(1) Inert gases : These atom have been full fill outer most s and p found in nature. The elements from atomic number of 93 onwards are
subshell and having the configuration ns 2np 6 (Exception helium having called transuranic elements and have been discovered artificial means.
In this classification the element, Zn, Cd and Hg have not been
1s 2 ) due to stable configuration these element do not show chemical
activity under normal condition and thus termed as inert gases. Under included in any of the four groups of elements. The elements Lu and Lr of
special conditions, the higher members do form some compounds with the inner transition group have (n  2) f shell complete consisting 14
other elements and hence, the name has been changed to Noble gases. Six electron hence their inclusion in this group is not justified.
element He, Ne , Ar, Kr, Xe and Rn belongs to this group. Extended or long form of periodic table
(2) Representative or normal elements : Element in which atom have Modern periodic table is also called long form of the periodic table
all shells complete except outermost shell which is incomplete. The number or Bohr’s table. In this table, the elements are arranged in order of their
of electrons in the outermost shell varies from 1 to 7 i.e. the configuration of increasing atomic number. It consists of 4 blocks (s, p, d and f), 18 groups
the outermost shell varies from ns 1 to ns 2np 5 . These consist of some numbered from 1 to 18 and 7 periods numbered from 1 to 7.
metals, all non metals and metalloid. These are the elements which are Blocks : The periodic table is divided into four main blocks (s, p, d
found in nature in abundance and active in nature. On account of this, and f) depending upon the subshell to which the valence electron enters
these elements are called representative elements. All the three types of into.
valencies are observed in the case of these elements. These elements have (1) Elements of group 1 and 2 constitute s-Block.
one of the following configuration in their outermost shell. (2) Elements of group 13, 14, 15, 16, 17, 18 constitute p-Block
ns1 ns 2 ns 2 np 1 ns 2 np 2 ns 2np 3 ns 2 np 4 ns 2 np 5 (3) Elements of group 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 constitute d-Block
1 2 2 4 5 6 7
(4) The f-Block elements comprise two horizontal rows placed at the
The number of electrons present in the outermost shell signify the bottom of the periodic table to avoid its unnecessary expansion.
group to which these element belong.
Elements of s- and p-blocks are called normal or representative
(3) Transition elements : In the atoms of these elements the elements, those of d-block are called transition elements while the f-block
outermost shell and the penultimate shell (Next to the outermost) are elements are called inner transition elements.
incomplete. These elements have the general configuration
Groups : The 18 vertical columns are called groups. The elements
(n  1) d 19 ns 0 or 1 or 2 either in the ground state or in excited state. These belonging to a particular group is known as a family and is usually named
elements are present in IV th , V th , VIth and VIIth period of periodic table after the first number. Apart from this some of the groups are given typical
names as examplified beneath,
and called transition elements. There are four transition series every series
consists 9 elements each. (1) Elements of group 1 are called Alkali-Metals.
(4) Inner transition elements : Atoms of these elements have three (2) Elements of group 2 are called Alkaline Earths.
outermost shell incomplete. The general configuration is (3) Elements of group 3 are called Pnicogens.
(n  2) f 114 (n  1) d 0 or 1ns 2 . There are two series of elements. (4) Elements of group 16 are called Chalcogens.
(5) Elements of group 17 are called Halogens.
(i) Lanthanides or rare earths from Ce (58) to Lu (71) .
(6) Elements of group 18 are called Noble Gases or Aerogens.

Discovery of element 104, 105 and 112 has recently been reported
[(n–2)f1–14(n–1)d0–10ns2]

(4f1–145d0–106s2)

(5f1–146d0–107s2)
 All the other groups are named after the first member of each Due to screening effect the valency electron experiences less
group. attraction towards nucleus. This brings decrease in the nuclear charge (Z)
Periods : The horizontal rows are called periods. There are seven periods actually present on the nucleus. The reduced nuclear charge is termed
in the long form of the periodic table, effective nuclear charge and is represented by Z * . It is related to actual
(1) Ist period  2 He) contains 2 elements. It is the shortest nuclear charge (Z) by the following formula,
1H
period. Z *  (Z   ) where  is screening constant.
(2) 2nd period (3 Li 10 Ne ) and 3rd period (11 Na 18 Ar) It is observed that magnitude of effective nuclear charge increases in
contains 8 elements each. These are short periods. a period when we move from left to right.
(3) 4th period (19 K 36 Kr) and 5th period (37 Rb 54 Xe) In a subgroup of normal elements the magnitude of effective nuclear
contains 18 elements each. These are long periods. charge remains almost the same.
(4) 6th period (55 Cs 86 Ra) consists of 32 elements and is the Covalent, Ionic and Vander waal's radii
longest period.
The radius of an atom is the distance between the centre of its
(5) 7th period starting with 87 Fr is incomplete and consists of 19 nucleus and electrons in the last orbit. However, according to quantum
elements. mechanics, there is no certainty about the exact position of electrons at
any time. Theoretically, an electron, at one time, may be very close to
the nucleus while at other time it may be far away from the nucleus. In
Periodicity in properties spite of these limitations we need to have some operational definition of
''The repetition of similar electronic configuration after a definite period is the term atomic radius. There are three operational concepts of atomic
the cause of periodicity of the properties of elements.'' radius.
It can be explained with the help of electronic arrangement of (1) If the bonding is covalent, the radius is called a covalent radius.
elements. According to the modern views, the valency of an element is
indicated by the number of electrons present in the outermost orbit. The (2) If the bonding is ionic, the radius is called ionic radius.
chemical properties of elements are dependent on valency electrons. (3) If the two atoms are not bonded by a chemical bond (as in noble
Variation in electronic arrangement leads to the variation in properties. gases) the radius is called vander Waal's radius.
After a definite interval, recurrence of similar electronic arrangement takes
(1) Covalent radius : It is half of the distance between the nuclei of
place when the number of valency electrons is the same. Thus, there is a
two like atoms bonded together by a single bond. Thus covalent radius of
regular gradation and repetition in the properties of elements.
carbon in a compound having C – C single bond can be determined by
Periodic properties are directly or indirectly related to their dividing the bond length by 2, i.e.,
electronic configuration and show a regular gradation on moving from left
C C
to right in a period or from top to bottom in a group. Some period or from rc   C  C  2rc or rc  rc
top to bottom in a group. Some important periodic properties are : 2
oxidation number, shielding effect, atomic radii, ionization energy, electron
where, rc is the single bond covalent radii (SBCR) of carbon.
affinity, electro-negativity, valency, density, m.pt. and b.pt.
However, if atoms forming the covalent bond are different i.e., one is more
The screening effect or shielding effect electronegative than the other then the atomic radius is determined by the
relation
A valence-electron in a multi-electron atom is attracted by the nucleus,
and repelled by the electrons of inner-shells. The combined effect of this A  B  rA  rB  0.009 ( A   B )
attractive and repulsive force acting on the valence-electron experiences less
attraction from the nucleus. This is called shielding or screening effect. The where  A and  B are electronegativities of the atoms A and B
magnitude of the screening effect depends upon the number of inner
electrons, i.e., higher the number of inner electrons, greater shall be the respectively. This relation was given by Stevenson in 1941.
value of screening effect. The screening effect constant is represented by the In a given period, atomic radius generally decreases from left to
symbol '  ' is determined by the Slater's rules. right and thus in any period, alkali metal is the largest and halogen is the
The magnitude of screening constant in the case of s- and p- block smallest atom. For example, in second period elements the covalent radii
elements increases in a period as well as in a group as the atomic number
increases. decrease from Li to F.
Li Be B C N O F Ne
Effective nuclear charge 3 4 5 6 7 8 9 10
 1.23 0.89 0.80 0.77 0.74 0.74 0.72 1.6 The covalent radius is always smaller than the corresponding
vander Waal's radius. This is because of the fact that in the formation of a
The decrease in size along a period is due to the effect of successive chemical bond, the two atoms have to come closer to each other. This also
increasing nuclear charge without addition of a new shell, i.e., in each explains why covalent bonds are much stronger than the vander Waal's
element of a given period a new electron is added in the same principal forces. It is important to note that since the noble gases ordinarily do not
quantum number. For example, in the second period the nuclear charge form any covalent bond, in crystals of noble gases, no chemical forces are
increases from + 3 in Li to + 9 in F. The increased nuclear charge attracts operating between the atoms. Hence the vander Waal's forces are the only
the electrons more strongly to the nucleus and thus decreases the size of attractive forces in these cases. In other words, the vander Waal's radii
the atom. In case of noble gases, the atomic radii are only the vander Waal's constitute the atomic radii of noble gases and since vander Waal's radii are
radii which are naturally higher than the covalent radii of other elements. larger than covalent radii, atomic radii of noble gases are largest in their
In a given group, Atomic radius generally increases as one moves from top respective periods (anomaly).
to bottom, e.g., in group 1 atomic size increases steadily from lithium to cesium,
Ionisation potential or ionisation energy
i.e. rCs  rRb  rK  rNa  rLi
The electrons in an atom are attracted by the nucleus. When an
The increase in size on descending a group is due to addition of electron is to be removed then work is done against this nuclear attraction.
extra shell which outweighs the effect of increased nuclear charge. In other words energy is required to remove an electron from an atom. To
Remember that He and Fr are smallest and largest atom respectively. understand the details of chemical behaviour of an element we must have
(2) Ionic radius : It is the effective distance from the nucleus of an an indication of the energy with which an atom binds its electrons. This is
ion upto which it has its influence on its electron cloud. obtained by the measurement of ionisation potential or ionisation energy. It
may be defined as the energy required to remove an electron from the
A cation is always much smaller than the corresponding atom. outermost orbit of an isolated gaseous atom in its ground state. It is
Further, more the number of electrons removed smaller will be the size of expressed in electron volts (eV) or kilo calories per gram atom. In an atom,
the resulting positive ion. For example, rFe  r 2   r 3  . This is the energy required to remove first electron from a gaseous atom is called
Fe Fe
first ionisation energy. The energy required to remove one electron from a
1 .26 0 .76 0 .64
unipositive ion to form a bipositive ion is called second ionisation energy.
due to following two factors Second ionisation energy is higher than the first. The reason is that in
(i) A cation formed by the loss of electrons may result in the unipositive ion left after the removal of one electron from the atom, the
electrons are more firmly bound to the nucleus than in the atom. Hence
complete disappearance of the outer shell and since the remaining inner
more energy is needed to remove the second electron.
shells do not extend so far in space, the cation is much smaller than the
metal atom. For example, A  A   e 1 (First I. E.)
Sodium atom (Na)  Sodium ion (Na ) +

A   A 2  e 1 (Second I. E.)
(2, 8, 1) (2, 8)
(ii) Whenever a cation is formed, the ratio of nuclear charge to the A 2  A 3  e 1 (Third I. E.)
number of electrons (Z/e ratio) is increased with the result the effective
nuclear charge is increased and the electrons are pulled towards the nucleus. Similarly, third ionisation energy is even more than second ionisation
Consequently, the cation becomes smaller. An anion is always larger than the energy.
corresponding atom. For example, Atomic radius of I = 1.23 ; Ionic radii of I –

= 2.16 (1) Variation of ionisation energy in periodic table

(i) Ionisation energy decreases in a group as the atomic number
This is again due to following two factors : (a) Since in the increases. It is based on the fact that as we move down a group, the size of
formation of an anion, one or more electrons are added, the electron cloud atom increases, and the outer electrons become farther away from the
expands and the ionic size increases. (b) In the formation of anion, the nucleus thus reducing the force of attraction and hence ionisation energy
effective nuclear charge decreases with the result the electrons get away decreases.
from the nucleus and thus the anion becomes larger than the corresponding
atom. Li Na K Rb Cs

In any particular group, the ions of elements increase in size on 5.4 eV 1. eV 4.3 eV 4.2 eV 3.9 eV
moving from top to bottom. (ii) Ionisation energy increases along a period with increase in
In case of isoelectronic ions (ions having same number of electrons atomic number. This is due to the size of atom since it decreases along a
but different nuclear charge); the greater the nuclear charge, the greater is period and outer electrons are most strongly attracted by the nucleus and
the attraction for electrons and smaller is ionic radius. Hence size of such hence more energy is required to remove the electron.
ions decreases. Which is as follows Li Be B C N O F Ne
4 3 2 1  2 3 4 5 6 7
C N O F  Ne  Na  Mg  Al  Si P S  Cl 5.4eV 9.3eV 8.3eV 11.3eV 14.6 eV 13.6eV 17.0eV 21.6eV

(iii) The ionisation energies of inert gases are greater than that of their
Size of ions (in decreasing order) immediate neighbour. It is due to their complete octet ns p configuration
2 6

(3) Vander Waal's radius : It is one–half of the distance between which is highly stable. Therefore, it is very difficult to remove an electron from
the outermost orbit of an inert gas.
the nuclei of two adjacent atoms belonging to two neighbouring molecules
of an element in the solid state. (2) Factors affecting the value of ionisation energy
 (i) Size of atom : With an increase in atomic size, the ionisation (iii) The relative values of ionisation potential and electron affinity of
potential is reduced, since the distance of the outermost electron from the two elements are related to the nature of bond formed during their
nucleus increases and hence the force of attraction decreases. combination.
(ii) The charge on the nucleus : With an increase in the nuclear (iv) The ionisation potentials provide an indication about the
charge, there is an increase in force of attraction of nucleus for electrons number of valence electron (s) in an atom; the abnormally high value
making the removal of the electrons more difficult. Thus an increase in indicates that the electron removed is other than the valence electron.
nuclear charge increases the ionisation potential. For example, IE , IE and IE values are 5.39, 75.62 and 122.42 eV.
1 2 3

(iii) The shielding or screening effect of inner shells : The valence Since the values shows sudden jump, it indicates that the number of valence
electrons in a multi–electron atom are pulled by the nucleus but are electron in its atom is one. Similarly, values of IE , IE and IE as 9.32, 18.21
1 2 3

repelled by the electrons of the inner shells. The valence electrons, therefore, and 153.85 eV indicate that the number of valence electrons in its atom is
do not experience the total pull of the nucleus. Instead the total pull of the two.
nucleus is reduced by the electrons in inner shells. This effect of reducing
the force of attraction of nucleus by the inner shells is called screening
effect. This effect is exhibited maximum by s p (the most stable) shell.
2 6
Electron affinity
Therefore, the ionisation energy of K is much less than Cu, however, both Those atoms whose nuclear forces are not completely screened by
have one electron in their fourth shell. electronic shells, offer attraction for electrons. Such atoms capture electrons
if these are available with in their effective fields to neutralise the
K19  1s 2 , 2 s 2 p 6 , 3 s 2 p 6 , 4 s1
electrostatic forces of the nucleus. Energy is always liberated whenever there
is a force of attraction offered by an atom or ion, and this energy is called
Cu 29  1s 2 , 2 s 2 p 6 , 3 s 2 p 6 d 10 , 4 s 1
electron affinity. This may be defined as, ''the energy released when an extra
The ionisation energy of K is 4.33 eV while that of Cu is 7.72 eV. electron is added to a neutral gaseous atom''.
This is due to a large screening effect of s 2 p 6 , penultimate orbit in K while When first electron is added in a neutral atom then some energy is
released that is called first electron affinity but in case of second electron
s 2 p 6 d 10 , penultimate orbit in Cu which exhibit little screening effect. affinity energy will be absorbed due to electronic repulsion. Example as
(iv) Type of electrons involved : Ionisation energy also depends upon (a) O(g)  e   O(g)  E1 (H  ve , Exoenergic)
the type, i.e., s, p, d or f, electrons which are to be removed, s –electrons
are closer to the nucleus and are more tightly held as compared to p, d or f (b) O(g)  e   O 2  E2 (H  ve , Endoenergic)
electrons. Hence, ionisation energy decreases in the order of s > p > d > f
Thus, higher the energy released in the process of taking up an extra
orbitals.
electron, the higher will be the electron affinity. Higher the value of electron
(v) Completely filled or half filled sub-shells : According to Hund's affinity of an atom, the more is its tendency to change into anion. It is very
rule, completely filled or half filled orbitals are more stable. Therefore, it is difficult to determine the electron affinity experimentally. The values have
comparatively difficult to remove the electrons from these shells. The been calculated on the basis of thermodynamic concepts. It is expressed in
ionisation energy of Be (9.3 eV) is more than B (8.3 eV) because Be has 2s 2

electron volts. The values of inert gases are assumed to be zero because
configuration of the outermost orbit which is fully filled. Similarly, nitrogen they have stable ns p configuration and unable to accept any electron. The
2 6

(14.6 eV) has more ionisation energy than oxygen (13.6 eV) because values for alkali metals are between zero and one.
nitrogen has outermost shell configuration as 2s p in which p shell is half
2 3

The electron affinities of Be, Mg and zero since they have complete
filled and is more stable. Similarly, ionisation energy of Mg is more than Al
ns configuration which can not accommodate extra electron. Similarly, the
2

and that of P is more than S.

values for N and P are very low because they also have completely half–
(3) Relative ionisation energies filled p orbitals (ns p ) and are more stable.
2 3

 IE and IE of the 2 period elements

nd (1) Factors affecting the value of electron affinity
1 2

(i) Atomic size : The value of electron affinity decreases with the
IE : Li < B < Be < C < O < N < F < Ne
1
increase in the size of atom since the nuclear attraction decreases down a
IE : Be < C < B < N < F < O < Ne < Li
2 group as the atomic number increases. Its value increases as we move along
 IE and IE of the 3 period elements
rd
a period since the size of atoms decreases along a period. The lower value
of F than Cl is due to the very small size of F in which negative charge is
1 2

IE : Na < Al < Mg < Si < S < P < Cl < Ar

1
highly concentrated and repels the incoming electron thereby reducing the
IE : Mg < Si < Al < P < S < Cl < Ar < Na
2
force of attraction of the nucleus towards the adding electron and hence
decreasing the electron affinity. Thus, chlorine has a highest value of
 IE of elements with very high values
1
electron affinity.
Cl < H < O < Kr < N < Ar < F < Ne < He (ii) Nuclear charge : The value of electron affinity increases with
(4) Importance of ionisation energy increasing nuclear charge. Thus, its value increases with increase in nuclear
charge along a period.
(i) Lower is the ionisation potential of an element, more would be
its reducing power and also reactivity. (iii) Screening or shielding effect : The value of electron affinity
increases with the decrease in shielding effect of inner electrons. Besides,
(ii) It gives rough estimate about the basic character of the
the value of electron affinity also depends to some extent upon the type of
elements.
orbital in which electron is added. The value is greater when electron enters
's' orbital and decreases successively for p, d and f orbitals.
 (2) Importance of electron affinity : Certain properties of the
elements are predicted on the basis of values of electron affinity.
(i) The elements having high value high values of electron affinity
are capable of accepting electron easily. They form anions and electrovalent
compounds. These elements are electronegative in nature. (1) Factors affecting the value of electronegativity
(ii) The elements having high values of electron affinity act as strong (i) The size of the atom.
oxidising agents, for example, F, Cl, Br, O, S , etc. (ii) Electronic configuration. Small atoms attract electrons more than
the larger one and are therefore more electronegative. Secondly, atoms with
On the basis of the general trend of ionisation potential and electron
nearly filled shell of electrons, will tend to have higher electronegativity than
affinity, the following properties can be predicted,
those sparsely occupied ones.
(a) Metallic nature decreases in a period while nonmetallic nature
(2) Variation of electronegativity in the periodic table
increases. Metallic nature increases in a group while non-metallic nature
decreases. The arrow () represents a group and () represents a period. (i) In a period, electronegativity increases from left to right. This is
due to decrease in size and increase in nuclear charge. Thus the alkali
Metallic Non-Metallic metals possess the lowest value, while the halogens have the highest. Inert
gases have zero electronegativity.
Metallic Decreases Non-Metallic Increases
(Electro +Ve) (Electro –Ve)
(ii) In a group, electronegativity decreases from top to bottom. This
is due to increase in atomic size.
Increases Decreases
If an element exhibits various oxidation state, the atom in the higher
(b) Reducing nature decreases in a period while oxidising nature
oxidation state will be more negative due to greater attraction for the
increases. The reducing nature increases in a group while oxidising nature electron, e.g., Sn II (1.30) and Sn IV (1.90).
decreases.
(3) Electronegativity may be expressed on the following three scales
Reducing nature Oxidising nature
(i) Mulliken's scale : Mulliken regarded electronegativity as the
average value of ionization potential and electron affinity of an atom.
Reducing Decreases Oxidising Increases
nature nature Ionizationpotential  Electronaffinity
Electronegativity
Increases Decreases 2
(c) Stability of metal increases while activity of the metal decreases (ii) Allred-Rochow scale : Allred and Rochow defined electronegativity
in a period and in a group stability decreases while activity increases. as the electrostatic force exerted by the nucleus on the valence electrons. Thus
Stability of the metal 0 .359 Z
  0 .744 where Z is the effective nuclear charge and r is the
r2
Stability of Increases covalent radius of the atom in Å.
the metal
(iii) Pauling scale : Pauling scale of electronegativity is the most
Decreases widely used. It is based on excess bond energies. He determined
This trend is observed especially in IA, IIA and IIIA elements. electronegativity difference between the two atoms and then by assigning
(d) The basic nature of the oxides decreases in a period while arbitrary values to few elements (e.g. 4.00 to fluorine, 2.5 to carbon and 2.1
acidic nature increases. In a group, basic nature increases while acidic to hydrogen), he calculated the electronegativity of the other elements.
nature decrases.
 A   B  0.208 E where  A and  B are electronegativities of
the atoms A and B respectively, the factor 0.208 arises from the conversion
Basic nature of oxides Acidic nature of oxides of kcal to electron volt (1 eV = 23.0 kcal/mole),

Basic nature Decreases Acidic nature while E  Actual bond energy  (E A  A  E B  B )

Increases
of oxides of oxides
Pauling and Mulliken values of electronegativities are related as
Increase Decreases
below  (Pauling) = 0.34  (Mulliken) – 0.2
(4) Importance of electronegativity : The following predictions can
Electronegativity be made from value of electronegativity,
The tendency of an atom in a compound to attract a pair of bonded (i) Nature of the bond between two atoms can be predicted from the
electrons towards itself is known as electronegativity of the atom. It is eelctronegativity difference of the two atoms.
important to note that electron affinity and electronegativity both measure
(a) The difference X A  X B  0, i.e., X A  X B the bond is
the electrons attracting power but the former refers to an isolated gaseous
atom while the latter to an atom in a compound. Thus electron affinity is purely covalent.
attraction for a single electron while electronegativity is for a pair of bonded
(b) The difference X A  X B is small, i.e., X A  X B , the bond is
electrons. Further electron affinity is energy while electronegativity is a
tendency. polar covalent.
Activity of the metal

Activity of Decreases
the metal

Increases
 (c) The difference X A  X B is 1.7, the bond is 50% covalent and (3) Melting and boiling points : The melting points of the elements
50% ionic. exhibit some periodicity with rise of atomic number. It is observed that
elements with low values of atomic volumes have high melting points while
(d) The difference X A  X B is very high, the bond is more ionic and elements with high values of atomic volumes have low melting points. In
general, melting points of elements in any periodic at first increase and
less covalent. The molecule will be represented in such case as BA (B  A  ) .
become maximum somewhere in the centre and thereafter begins to
Percentage ionic character may be calculated as, decreases.
Percentage of ionic character  16(X A  X B )  3.5(X A  X B )2 Tungsten has the maximum melting point (3410°C) amongst metals
and carbon has the maximum melting point (3727°C) amongst non-metals.
where X A and X B represents electronegativity of bonded atoms A Helium has the minimum melting point (–270°C). The metals, Cs, Ga and
and B. Hg are known in liquid state at 30°C.
This relation was given by A.L. Allerd (1961). The boiling points of the elements also show similar trends,
(ii) Greater the value of difference (X A  X B ) more stable will be however, the regularities are not so striking as noted in the case of melting
points.
the bond.
(4) Oxidation state (Oxidation number, O.N.) : Oxidation number of an
HF H  Cl H  Br H I element in a compound is the total number of electrons it appears to have
(X A  X B ) 1.9 0.9 0.7 0.4 gained or lost (negative and positive oxidation states respectively) during
the formation of that particular compound.
Stability decreases
Note : For detail see chapter redox reaction.
Stability of compounds in which X A  X B is very small are
unstable in nature, SiH 4 (0.3), NCl 3 (0.0) , PH3 (0), AsH3 (0.1) are
unstable.
(iii) (X O  X A ) difference predicts the nature of the oxides formed
by the element A. X O is the electronegativity of oxygen.

X O  X A is large, the oxide shows basic nature, (e.g., Na 2O ).

X O  X A is small, the oxide shows acidic nature, (e.g., SO 2 ).

(iv) Ionic compounds having percentage ionic character less than
20% were found coloured, e.g.,
AgCl AgBr AgI Ag2 S
22% 18% 11% 8%
White Light yellow Dark yellow Black
Lesser the percentage ionic character, darker will be the colour.
Some other periodic properties
(1) Atomic volume : It is defined as the volume occupied by one
gram atom of an element. Mathematically,
Gram atomic weight
Atomic volume 
Densityin solidstate
Units of atomic volume are c.c./mole. Atomic volume signifies the
volume occupied by one mole (Avogadro number) of atoms of the given
element in solid state. Lower atomic volume generally leads to higher
density, increased hardness and brittleness, higher melting and boiling
points, less malleability and ductility.
(i) While descending a group, the atomic volume generally increases
which is due to increase in the number of shells though the valence
electrons in a given group remains constant.
(ii) While going left to right across a period the atomic volume first
decreases to a minimum and then increases. Francium has the highest atomic
volume and boron has lowest atomic volume.
(2) Density : The density of the elements in solid state varies
periodically with their atomic numbers. At first, the density increases
gradually in a period and becomes maximum somewhere for the central
members and then starts decreasing afterwards gradually.
 (5) Magnetic properties : Magnetic properties of matter depend on (ii) Covalent nature of hydrides increases across a period and
the properties of the individual atoms. A substance (atom, ion or decreases down the group.
compound) capable of being attracted into a magnetic field is known as (iii) Ionic hydride are better reducing agents than covalent hydride
paramagnetic. The paramagnetic substances have a net magnetic moment and reducing nature of hydride decreases across a period and increases
which in turn is due to the presence of unpaired electron(s) in atoms, ions down the group.
or molecules. Since most of the transition metal ions have unpaired d–
electrons, they show paramagnetic behaviour. The exceptions are
(A) (B) (C) LiH NaH MgH2 AlH3 SiH3
Sc 3  , Ti 4  , Zn 2  , Cu  , etc. which do not contain any unpaired electron
covalent
and hence are diamagnetic. NaH (A)
On the other hand, a substance which is repelled by a magnetic field ionic
is known as diamagnetic. Such substances do not have any net magnetic KH (B)
moment because they do not have any unpaired electron. Electrons reducing nature
RbH (C)
determine the magnetic properties of matter in two ways,
 Each electron can be treated as a small sphere of negative charge (Minimum Maximum)
CsH
spinning on its axis. The spinning of charge produces magnetic moment.
 An electron travelling in closed path around a nucleus will also (iv) Covalent and ionic hydrides are classified as follows,
produce magnetic moment just as does electric current travelling in a loop
of wire. Diagonal relationship
The observed magnetic moment is therefore the sum of the two Certain elements of 2 period show similarity with their diagonal
nd

moments: the spin moment and the orbital moment. It is expressed in units elements in the 3 period as shown below :
rd

called Bohr Magnetons (BM). In terms of n (number of unpaired electron),

Group 1 Group 2 Group 13 Group 14
magnetic moment is given by the formula,   n (n  2) 2 perio
nd
Li Be B C
Greater the number of unpaired electrons in a substance, the greater
is the magnetic moment of the substance. The value of magnetic moment 3 period
rd
Na Mg Al Si
has been used to calculate the number of unpaired electrons in an ion. In
some cases, even the structure of the molecule or complex is indicated by Thus, Li resembles Mg, Be resembles Al and B resembles Si. This is
its magnetic moment. called diagonal relationship and is due to the reason that these pairs of
Paramagnetism is generally measured by a simple device known as element have almost identical ionic radii and polarizing power (i.e.
Guoy's balance which involves weighing the species in presence of a charge/size ratio). Element of second period are known as bridge elements.
magnetic field. Anomalous behaviour of the first elements of a group: The first
Ferromagnetism is a special property observed in some substances element of a group differs considerably from its congeners (i.e. the rest of
in the solid state. Such substances are strongly attracted to magnetic field the element of its group). This is due to (i) small size (ii) high
and may retain the magnetic properties for some time even after the electronegativity and (iii) non availability of d-orbitals for bonding.
removal of the field. The most common example is of Fe followed by Co and Anomalous behaviour is observed among the second row elements (i.e. Li to
Ni. F).
(6) Hydration and hydration energy
(i) Hydration energy is the enthalpy change that accompanies the
dissolving of 1 mol of gaseous ions in water.
(ii) Size of ions and its charge determines extent of hydration.
Greater the charge smaller the size of the ion, greater the attraction for the
lone pair of O of H 2 O , hence greater the extent of hydration energy.
(a) Size of the hydration ion increases.
(b) Ionic mobility decreases i.e. heavier (hydrated) ions moves
slower.
(7) Acid-base-character of oxides
(i) On moving across a period, the basic character of the oxides
gradually changes first into amphoteric and finally into acidic character.
(ii) On moving down a group, reverse behaviour is observed i.e.,
from more acidic to more basic.
(iii) Stability of oxides decreases across a period.
(8) Hydrides
(i) Hydrogen combines with a number of other elements including
metals and non-metals to form compounds called hydrides.
  The electron affinity of exactly half-filled configuration is
approximately zero and exactly zero for fully filled configuration.
 The electron affinities of gaseous anions are always negative.
 Some of the polar crystals when heated produce electric current.
This phenomena is termed as piezoelectric effect.
 The IUPAC nomenclature of elements > 100  All the elements of f- block (4f series – Lanthanides and 5f series –
In IUPAC system, the names are derived by using roots for the three Actinides) are placed in 3rd group (IIIB) and form a separate block
digits in the atomic number of the element and adding the ending : ium. at the bottom of the periodic table.
The roots for the numbers are
Number 0 1 2 3 4 5 6 7 8 9
Root nil un bi tri quad pent hex hept oct enn
Atomic
Number Name Symbol
101 un-nil-unium Unu
102 un-nil-bium Unb
103 un-nil-trium Unt
104 un-nil-quadium Unq
105 un-nil-pentium Unp
106 un-nil-hexium Unh
107 un-nil-septium Uns
108 un-nil-octium Uno
109 un-nil-ennium Une
110 un-un-nilium Uun
111 un-un-unium Uuu
112 un-un-bium Uub
113 un-un-trium Uut
114 un-un-quadium Uuq
115 un-un-pentium Uup
116 un-un-hexium Uuh
117 un-un-septium Uus
118 un-un-octium Uuo
119 un-un-ennium Uue
 Elements of second period are known as Bridge elements. Their
properties resemble with the properties of diagonal elements of third
period.
 For isoelectronic ions the size depends on the nuclear charge.
Greater is the nuclear charge smaller is the size.
 The incease in magnitude of radii is more in the beginning of a
group because the difference in energy between energy shells is
more.
 The ionisation potentials provide an indication about the number of
valence electrons (s) in an atom e.g., Na has IE >>> IE (because it
2 1

has one valence electron) while Mg has IE >>> IE > IE because it

3 2 1

has two valence electrons and attains noble gas configuration after
losing 2 electrons.
 The highest I.E. in a period is shown by noble gas.
 The electronegativity of a series of transition metals is almost
similar. The electronegativity of all lanthanide’s are identical (1.1).
 The most electronegative elements is Fluorine (value is 4.0 on the
Pauling scale). The least electronegative elements is Cs and Fr with
a value of 0.700.