PERIODIC PROPERTIES

Need for classification:

It is very difficult to study individually the chemistry of all the elements and millions of their
compounds,
Hence to simplify and systematize the study of chemistry of the elements and their
compounds, they are classified into groups and periods. Early attempt to classify the
elements:

 Classification of Lavoiser
Elements had been classified into two major groups by Lavoiser
1. Metals 2. Non–metals
This classification was based on the differences in their properties.
 Dobereiner’s law of triads:
It was first attempt towards classification. He arranged similar elements in a group of three
elements called triad and the atomic mass of the middle elements of the triad is
approximately the arithmetic mean of the other two.

 Newland’s law of octaves:

When the lighter elements are arranged in order of their increasing atomic weights, then
every eighth element is similar to the first element in its properties, similarly as the eighth
node of a musical scale is similar to first one. E.g. Na resembles in their properties with Li.
MENDELEEV’SPERIODICLAW

Mendeleev’s Periodic Law - The physical and chemical properties of elements are the
periodic function of their atomic weight

 Characteristics of Mendeleev’s Periodic Table

(a) It is based on atomic weight

(b) 63elements were known, noble gases were not discovered.

(c) 12 Horizontal rows are called periods.

(d) Vertical columns are called groups and there were 8 groups in Mendeleev’s Periodic
table.

(e)Each group up to VIIth is divided into A& B sub groups.

(f) The VIIIth group consists of 9elements in three rows (Transition metals group).

(g) The elements belonging to same group exhibit similar properties.

 Merits of Mendeleev’s periodic table

1. Study of elements - First time all known elements were classified in groups according
to their similar properties. So study of the properties becomes easier
2. Prediction of new elements – It gave encouragement to the discovery of new elements
as some gaps were left in the table. Scandium, Gallium, Germanium, Technetium were
the elements for whom position and properties were defined by Mendeleev even before
their discoveries and he left the blank spaces for them E.g.-Blank space at atomic
weight 72 in silicon group was called Eka silicon (means properties like silicon) and
element discovered later was named Germanium. Similarly, other elements discovered
after Mendeleev periodic table were. Eka aluminium-Gallium (Ga) Eka Boron-
Scandium (Sc)Eka Silicon-Germanium (Ge) Eka Manganese-Technetium (Tc)
3. Correction of doubtful atomic weights - Correction was done in atomic weight of
some elements. Corrections were done in atomic weight of elements are – U, Be, In,
Au, Pt.
 Demerits of Mendeleev’s periodic table

1. Position of hydrogen - Hydrogen resembles both, the alkali metals (IA) and the
halogens (VIIA) in properties so Mendeleev could not decide where to place it.

2. Position of isotopes - As atomic weight of isotopes differs, they should have placed in
differentpositioninMendeleev’[Link]
Mendeleev’s table.

3. Anomalous pairs of elements - There were some pair of elements which did not
follow the increasing order of [Link]. Ar and Co were placed before K and Ni
respectively in the periodic table, but having higher atomic weights.

4. Like elements were placed in different groups - There were some elements like
Platinum (Pt) and Gold (Au) which have similar propertiesbut were placed in different
groups in Mendeleev’s table. Pt– VIII, Au–IB

5. Unlike elements were placed in same group - Like cu and Ag placed together in Ist
group with Na.
MODERN PERIODIC LAW

 Mosley proved that the square root of frequency of the rays, which are obtained from
metal on showering high velocity electrons, is proportional to the nuclear charge of the
atom.
 According, to modern periodic law:”The properties of elements are the periodic
functions of their atomic numbers”.
 Cause of periodicity: It is due to the repetition of similar outer shell electronic
configuration at a certain regular intervals
 Structural features of the long form of the periodic table:
 It consists of 18 vertical columns called groups and 7 horizontal rows called periods.
 Elements of groups 1, 2, 13– 17are called normal or representative elements.

 Elements of groups 3 – 11are called transition elements.

 The14 elements with atomic numbers (Z)=58– 71(occurring after lanthanum La in the
periodic table) are called lanthanides or rare earth elements and are placed at the
bottom of the periodic table.

 The 14 elements with atomic numbers (Z) = 90 – 103(Occurring after actinium Ac in

the periodic table) are called actinides and are placed at the bottom of the periodic
table.
 The Eleven elements with Z = 93 – 103 (93Np –Lr103) which occur in the periodic
table after uranium and have been prepared from it by artificial means are called
Trans uranics. These are all radioactive elements.
 The elements belonging to a particular group are said to constitute a chemical family
which is usually named after the name of the first element. For example, Boron
family (group 13), carbon family (group 14), nitrogen family (group 15), and oxygen
family (group 16). In addition to this, some groups have typical names. For example,
Elements of group 1 are called alkali metals
 Elements of group2 are called alkaline earth
metals
 Elements of group 16 are called chalcogens
 Elements of group 17 are called halogens
 Elements of group18 are called zero group or
noble gases.
 The long form of the periodic table contains
seven periods.
  1st period (1H–He) contains only two elements. This is the shortest period.

 2nd period (3 Li –10Ne) and third period (11Na –Ar) contain 8 elements each and are
called short periods.
 4th period (19K–36Kr) and 5th period (37Rb–54Xe) contain18elements each and are
called long periods.
 6th period (55Cs –86Rn) contains 32 elements and is the longest period.

 7th period (87Li –) is, however, incomplete and contains at present only24 elements.

 In yet another classification,the long form of the periodic table has been divided into
four blocks (i.e. s, p, d and f ), depending upon the subshell to which the last electron
enters.

 s-block elements.

Elements of groups 1 and 2 including He in which the last electron enters the s-orbital of the
valence shell are called s-block elements. There are only 14 s-block elements in the periodic
table.

 p-block elements.

Elements of groups 13–18 in which the last electron enters the p-orbitals of the valence shell
are called p-block elements.
• d-block elements.

There are three complete series and one incomplete series of d-block elements. These are: 1st
or 3d transition series which contains ten elements which atomic numbers 21–30 (Sc- Zn).
2nd or 4d transition series contains ten elements with atomic numbers39–48 (Y-Cd).

3rd or 5d transition series also contains ten elements which atomic numbers 57 and 72–
80(57La, 72Hf –80Hg).
4th or 6d transition series is incomplete at present and contains only nine elements.
Z = 111 has not been discovered so far. Thus, in all there are 39 d-block elements.
• f-Blockelements
They are called inner-transition elements. In these elements, the f-subshell of the anti-
penultimate is being progressively filled up. There are two series of f-block elements each
containing 14 elements. The fourteen elements from 58 (Ce –Lu) in which 4 f-subshell is
being progressively filled up are called lanthanides or rare elements. Similarly, the fourteen
elements from 90Th –103Lr in which 5 f-subshell is being progressively filled up are called
actinides
  Periodic Properties:

Properties which are directly or indirectly related to their electronic configuration and show a

regular gradation when we move from left to right in a period or from top to bottom in a
group are called periodic properties. Some important periodic properties are atomic size,
ionization energy electron affinity, electro negativity, valency, density, atomic volume,
melting and boiling points etc.
 Effective nuclear charge: effective nuclear charge is also abbreviated as ENC. It is
defined as the net positive charge experienced by the valance electron with nucleus. It
can be represented by Zeff
Zeff = Z-S
Zeff= effective nuclear charge
Z= atomic number
S= shielding electron (inner shell electron)
 Shielding effect or screening effect: The repulsive force felt by the valance shell
electron from the electrons present in inner shell is called shielding effect, or screening
effect.
Penetration of electron: the ability of an electron to get close to the nucleus is known as
penetration of electron. The electrons in different orbital have different penetration effect and
even electrons present in same shell differ in the penetration effect of their sub shell. S>p>d>f

1. Atomic size:
• It refers to the distance between the centres of the nucleus of the atom to the outermost
shell containing electrons.
• Covalent radii: it is defined as one half of the distance between the nucleus of two
covalently bonded atoms of some element in a molecule.
• Ionic radii: it is the radius of ions in an ionic crystal. It is defined as the effective
distance from the nucleus of the ion up to which it has an influence in the ionic bond.
• Since absolute value of the atomic size cannot be determined, it is usually expressed in
terms of the following operational definitions.
• Atomic radii decrease as we move from left to right in the periodic table and it
increases as we move down in the periodic table
• As we move down a group, electrons are added to new shells and the effective
nuclear charge felt by each electron decreases. Hence atomic radii increase down
the group.
• As we move across a period from left to right, electrons are added in the same
subshell and the effective nuclear charge felt by each electron would be more.
 Hence atomic radii decrease along a period.
• A cation is always smaller than the parent atom because during its formation effective
nuclear charge increases and sometimes a shell may also decrease. Mg2+< Mg
• An anion is always larger than the parent atom because during its formation effective
nuclear charge decreases. Cl–> Cl
• The size of a cation is smaller in comparison to the size of its corresponding atom. This
is because of the fact that an atom on losing electrons/s forms a cation, which has lesser
number of electrons/s than the number of proton/s. This results in increase in the
effective nuclear charge.
• The size of an anion is greater than the size of its corresponding atom, because the
number of electrons present in the anion gets larger than the number of protons due to
gain of electron/s. This results in decrease in the effective nuclear charge.

 Size of Iso electronic Series

• Iso electronic ions or species are the neutral atoms, cations or anions of different
elements which have the same number of electrons but different nuclear charge
• The size of the isoelectronic species depends upon their nuclear charge. Greater the
nuclear charge, lesser the radii.
• The ionic radii decrease moving from left to right across any period in the periodic table

2. IONISATIONPOTENTIAL
• The energy required to remove the most loosely bound electron from the outermost orbit
of one mole of isolated gaseous atoms of an element, is called ionization potential (IP).

• The energy required to remove one electron from a neutral gaseous atom to convert it to
mono-positive cation, is called first ionization potential.

• The energy required to convert a mono positive cation to a di positive cation is called
second ionization potential

• In the group ionization energy decreases as atomic size increases and effective nuclear
charge also decreases. Hence it is easy to remove an electron from the outermost subshell
of an atom.

• In the period ionization energy increases as atomic size decreases and effective nuclear
charge also increases. Hence it will be difficult to remove an electron from its outermost
shell.

• Factors Affecting Ionization Potential

• Atomic size: When the size of an atom is very large the electron of the outermost orbit
bound to the nucleus by weaker attractive forces. Such an electron will be readily
 removed from the atom. Therefore the value of ionization potential will be low.
• Effective Nuclear Charge: Atomic size decreases with increase in effective nuclear
charge because, higher the effective nuclear charge stronger will be the attraction of the
nucleus towards the electron of the outermost orbit and higher will be the ionization
potential.
• Shielding Effect: The electrons of internal orbits repel the electrons of the outermost
orbit due to which the attraction of the nucleus towards the electron of the outermost
orbit decreases and thus atomic size increases and the value of ionization potential
decreases.
• Stability of half filled and fully filled orbitals: The atoms whose orbitals are half-
filled (p) or fully-filled (s2, p6) have greater stability than the others. Therefore, they
required greater energy for removing out an electron. However stability of fully filled
orbitals is greater than that of the half- filled orbitals.
• Penetration power: In any atom the s orbital is nearer to the nucleus in comparison to
p, d and f orbitals. Therefore, greater energy is required to remove out electron from s
orbital than from p, d and f orbitals.

• EXCEPTIONS

• Ionization energy of beryllium is greater than boron: Although the nuclear charge of
beryllium is greater than boron, yet ionization, energy of beryllium, is greater than boron.
This is due to fact that the electronic configuration of boron is 1s2 2s2 2p1
is less stable than beryllium 1s2 2s2 which has completely filled orbital. Hence ionization
energy of boron is less than that of beryllium.

• When we move from nitrogen to oxygen ionization energy of nitrogen is more than
that of oxygen. Why?

Although the nuclear charge of nitrogen is slightly greater than oxygen, yet, there is
slight decrease in ionization energy from nitrogen to oxygen. This is due to the fact that
electronic configuration of nitrogen (2s22p3) is half filled. In oxygen it is (2s2 2p4) Hence
ionization energy of oxygen is less than that of nitrogen.
• The increasing order of the values of ionization potential of the second
period elements is Li < B <Be<C <O<N<F<Ne

• The increasing order of the values of ionization potential of the third period
elements is Na < Al < Mg < Si < S < P < Cl <Ar

3. ELECTRON AFFINITY:

• The energy released on adding up one mole of electron to one mole of neutral atom
 (A) in its gaseous state to form an anion (A–) is called electron affinity of that atom.
In general, electron affinity is associated with an exothermic process.

• On adding one more electron to the mono-negative anion, there is repulsion between
the negatively charged electron and anion. In order to counteract the repulsive forces,
energy has to be provided to the system. Therefore, the value of the second electron
affinity is positive.

• Electron affinity increases from left to right in a period and decreases from top to
bottom in a group.

• Factors affecting electron affinity

• Effective Nuclear charge: When effective nuclear charge is more, then the atomic
size less. Hence EA increases.
• Atomic Size or Atomic Radius: When the size or radius of an atom increases, the
electron entering the outermost orbit is more weakly attracted by the nucleus and the
value of electron affinity is lower.
• Shielding Effect: Shielding effect is directly proportional to atomic size and atomic
size is inversely proportional to electron affinity.

• Stability of Fully-Filled and Half-Filled Orbitals: The stability of the configuration

having fully-filled orbitals (p6,d10)and half-filled orbital is relatively higher than that of
other configurations.

• Electron affinity of fluorine is less than that of chlorine. Why?

The low value of electron affinity of fluorine is due to very small size of fluorine atom.
As a consequence of small size there is strong inter-electronic repulsion in the relatively
compact 2p sub shell of fluorine and thus the incoming electron does not feel much
attraction. As a result, its electron affinity value is small. On the other hand, the electron
affinity of chlorine atom is larger where electrons are added to a relatively large 3p
orbital which can easily accommodate the additional electron.
• Electron affinity of noble gases as 0 why?
The electron affinity of noble gases as zero because they have stable electronic
configuration and thus they have absolutely no tendency to take additional electron. This
means that incoming electron does not feel any attraction for the nucleus that no energy is
released and their electron affinity is 0.

• Halogens have the highest electron affinity

4. ELECTRONEGATIVITY:
 • Electronegativity is a measure of the tendency of an atom to attract a bonding pair of
electrons.
• The Pauling scale is the most commonly used.
• Fluorine (the most electronegative element) is assigned a value of 4.0, and values
range down to cesium and francium which are the least electronegative at 0.7.
• On moving along a period, the electronegativity increases and on moving down the
group electronegativity decreases.
• Electronegativities generally increase from left to right across a period. This is due to an
increase in nuclear charge. Alkali metals have the lowest electronegativities, while
halogens have the highest.
• Most noble gases do not form compounds, they do not have electronegativities.
• Electronegativities generally decrease from top to bottom within a group, due to the
larger atomic size.
• Of the main group elements, fluorine has the highest electronegativity and cesium the
lowest. This indicates that fluorine has a high tendency to gain electrons from other
elements.

• Factors affecting electronegativity:

• Size of an atom: atom which have small size have a higher value of electronegativity
• Oxidation state: electronegativity of an atom varies from one bonding state to another,
depending on the oxidation state of the atom in the molecule the electronegativity
increases as the positive oxidation state of atom increases. This is because with the
increase in positive oxidation state the tendency to attract the electron will increase.
• Bond order: as the bond order increases, its electronegativity increases.
• Type of hybridization: with the increase in s character, the electronegativity increases
 VALENCY
• It is the number of electrons gained or lost or shared by one atom of an element
during a chemical combination.
• It is the combining capacity of an atom
• It is always a whole number and should be a constant.
 OXIDATION NUMBER
• Residual charge which an atom appears to have when all atoms are removed as ions
• Since it refers to charge it can be positive or negative and can have values as zero,
whole numbers or fractional numbers.
• Elements can exhibit variable oxidation state mainly d block elements.
 METALLIC AND NON METALLIC CHARACTER
• Metallic character refers to the level of reactivity of a metal. Metals tend to lose
electrons in chemical reactions, as indicated by their low ionization energies.
• The most reactive metal is cesium, which is not found in nature as a free element. It
reacts explosively with water and will ignite spontaneously in air.
• The metallic character increases as you go down a group. The atomic
radius increases going down a group, placing the outer electrons further away
from the nucleus making that electron less attracted by the nucleus. Therefore,
the ionization energy decreases going down a group, and hence the ability to lose
electrons increases leading to the increased metallic character.
• Nonmetals tend to gain electrons in chemical reactions and have a high attraction for
electrons within a compound. The most reactive nonmetals reside in the upper right
portion of the periodic table. Since noble gases are a special group because of their
lack of reactivity, the element fluorine is the most reactive nonmetal.

• As we move across the periodic table, there is an increasing tendency to accept

electrons (nonmetallic) and a decrease in the possibility that an atom would give
up one or more electrons.
INERT PAIR EFFECT
• Among the elements of p-block, in groups 13, 14 and 15, there is a general trend that
the higher oxidation states become less stable in going down the group.
• Outer electron configurations of group 13, 14 and 15 elements are ns2 np1, ns2 np2
and ns2 np3, respectively. They are thus expected to show the higher oxidation state of
+3, +4 and +5 respectively.
• The preference of heavier elements of these groups to show +1, +2 and +3 states,
respectively indicate that two electrons do not participate in bonding.
• The reluctance of s-electrons to take part in chemical bonding is known as inert
pair effect.
• The net result is the lesser stability of higher oxidation state with the increasing
atomic number in these groups.
• Thus although boron and aluminium are universally trivalent, gallium, indium and
thallium exhibit +1 state as well. In fact +1 state of thallium is very stable. Similar
situations are noticed in groups 14 and 15. Though carbon is universally tetravalent, it
is possible to prepare divalent germanium, tin and lead compounds. The stable state
of +3 in antimony and bismuth in group 15 is another example.