Periodic Properties

The concept of periodic table is undoubtedly the most important concept of chemistry. It is the
periodic table that provides complete data about the occurrence, nature and properties (both
physical and chemical) of all the elements along with their trends. It is a matter of immense
wonder that the elements are not a cluster of diverse identities but belong to families and
behave accordingly with respect to their family members.

5.1 BASIC CONCEPTS ABOUT PERIODIC TABLE

In the 19th century, only 63 elements were known. Many scientists tried to establish periodic
relation between elements but only a few of them succeeded. Some of their works are
discussed here.

5.1.1 Dobereiner's Law of Triads.

The first initiative was taken by Johann Dobereiner, a German scientist, who first considered
trends among properties of elements and established that certain elements can form a group of
three members, i.e., a triad in which the average of the sum of atomic weights of the first and
last element is approximately equal to the atomic weight of the middle element. For example,
lithium, sodium and potassium form a Dobereiner's triad.

Atomic weight of Na = (Atomic weight of Li + Atomic weight of K)/2 = 7+39/2 = 23,

which is the atomic weight of Na. Similarly, phosphorus, arsenic, antimony and sulphur,
selenium, tellurium are also examples of Döbereiner's triad.

5.1.2 Newland's Law of Octaves

After Dobereiner, another chemist John Alexander Newlands formulated his periodic table
where every eighth element exhibited similar properties of the first element if they are arranged
in order of increasing atomic masses. He established the Law of Octaves for elements up to
calcium.
5.1.3 Mendeleev's Periodic Table
In 1869, a Russian chemist named Dmitri Ivanovich Mendeleev published a periodic table in
which the elements (known at the time) were arranged in order of relative atomic masses. But
there were certain changes that made his table much more useful.
5.1.4 Modern Periodic Table
The modem periodic table is different from the previous periodic tables. It is based on the
modern periodic law. The modern periodic law states that 'properties of elements are a
periodic function of their atomic numbers'.

There are 18 vertical columns which are called groups and 7 horizontal rows called periods. The
modern periodic table contains 118 elements which includes the four newly discovered
elements, namely, Nihonium (Nh)-113, Moscovium (Mc)-115, Tennessine (Ts)- 117 and
Oganesson (Og)-118.

5.1.5 Method of Determining Groups from Atomic Numbers

Let us assume that atomic number of a given element is 20. So, there are 20 electrons.
Thus, its distribution of electrons will be 1s 2s2 2p 3s2 3p 4s2.
The last electron pair occupies 4s orbital. Hence it belongs to 4th period.
Again, elements with an outer s orbital with two electrons are classified as group 2
elements. Hence the element is Ca. The elements of group 2 are also called alkaline earth
metals.
5.2 ELECTRONIC CONFIGURATION ON THE BASIS OF PERIODIC CLASSIFICATION
Electronic configuration is defined as the arrangement of electrons in the different orbitals
present in an atom. The position of an element inside the periodic table can be explained from
the four quantum numbers

5.2.1 Electronic Configuration in a Group

Eighteen groups are present in the periodic table, each with a specific configuration of the
valence shell which is similar for all the members belonging to that particular group. The only
variation is the principal quantum number which changes with successive periods.

Group Electronic Group Electronic Group Electronic Configuration

Configuration Configuration

1 ns1 7 (n-1)d5ns2 13 ns2np1

2 ns2 8 (n-1)d6ns2 14 ns2np2
3 (n-1)d1ns2 9 (n-1)d7ns2 15 ns2np3
4 (n-1)d2ns2 10 (n-1)d8ns2 16 ns2np4
5 (n-1)d3ns2 11 (n-1)d10ns1 17 ns2np5
6 (n-1)d4ns2 12 (n-1)d10ns2 18 ns2np6

5.2.2 Electronic Configuration in a Period

There are seven periods in the modern periodic table, each indicating an increase in the value
of n, i.e., outermost shell or valence shell. The first period starts with filling of lower energy Is-
subshell. This gradually increases with increase in number of electrons in an atom. For
example, the electronic configuration of the alkali metals, with increase in periods, is as follows:

Element Period Electronic Configuration Element Period Electronic Configuration

Li 2 [He] 2s1 Rb 5 [Kr] 5s1
Na 3 [Ne] 3s1 Cs 6 [Xe] 6s1
K 4 [Ar] 4s1 Fr 7 [Rn] 7s1

5.3 TYPES OF ELEMENTS (s-, p-, d-, f-BLOCKS)

The modern periodic table contains four blocks named after four subshells. They are s-block, p-
block, d-block and f-block. The elements are distributed into blocks depending on the subshell in
which its last (valence) electrons are present.
(a) s-Block Elements

The s-block contains those elements for which the last valence electron enters the s-subshell.
There are two groups involved in the s-block, namely, alkali metals (group 1) having one
valence electron and alkaline earth metals (group 2) having two valence electrons.

(b) p-Block Elements

If the last electron in an atom enters the p-subshell, it then belongs to the p-block. This block
involves six groups (13-18). Group 18 elements are called noble gases. Preceding the noble
gases are the halogens and the chalcogens respectively.

c) d-Block Elements
If the last electron in an atom enters the d-sub-shell, it then belongs to the d-block. They
connect the s-block elements (metals with low electronegativity) and the p-block elements (non-
metals with high electronegativity) representing the transition between them and hence are
called transition elements. Here, the valence electron enters the d-subshell. They are all metals
and exhibit variable oxidation states. They form coloured ions and show good catalytic activity.

(d) f-Block Elements

The f block elements consist of the Lanthanides [Ce (58) to Lu (71)] and Actinides [Th (90)
to Lr (103)] and due to their unique position in the periodic table, they are called inner transition
elements. Among the lanthanides, lanthanum, cerium, praseodymium, neodymium, and
europium are very reactive. They react with aerial oxygen to form an oxide coating that
tarnishes the surface. The actinides on the other hand are mostly radioactive and highly
electropositive.
QnA
1. Some transition elements are not considered as d-block elements. Explain.
2. Why are s-block elements more electropositive than d-and f-block elements?
5.4. SOME IMPORTANT PERIODIC PROPERTIES AND PERIODIC TRENDS

5.4.1 Atomic and Ionic Sizes

Atomic size is derived from atomic radius which refers to covalent as well as metallic radii based
on the nature of the concerned element (non-metal or metal). The atomic and ionic sizes cannot
be measured directly. They are diffraction studies. obtained from spectroscopic or X-ray

(a) Covalent radius: The average inter-nuclear distance between the two bonded homo- nuclear
nuclei is called covalent radius.
(b) Metallic radius: The average inter-nuclear distance between the two metal atoms in metallic
lattice is called metallic radius.

(c) Van der Waals radius: The average distance between the closest approach of the two atoms

that are non-bonded and are present in a given element is called Van der Waals radius.

(d) Ionic radius: The average distance between two ions in an ionic lattice is called ionic radius.
(e) Calculation of ionic radii by Pauling's method: In case of crystals like NaF, KCl,
RbBr and Csl, the ionic radii of corresponding ions are calculated from the observed
inter-nuclear distances using Pauling's method. The cations and anions present in
the crystals are isoelectronic with each other. For example, if we consider NaF, here
Na+→ (2,8) & F-→(2,8). Similarly for KCI, K+→(2,8,8) and CI- → (2,8,8). Apart from
this, in order to assign the ionic radii, the following assumptions are made:

(i) It is assumed that the cations and anions present in a crystal lattice are in contact with each
other. As a result, the inter-nuclear distance between them will be equal to the sum of their radii.

Radius (cation) + Radius (anion) = Distance (cation - anion) ….(1)

(ii) The radius of an ion will decrease with increase in effective nuclear charge (Zeff) for a given
inert gas, i.e.,

1
Radius(cation) ∝ …(2)
Effective nuclear cℎarge of cation

1
Radius (anion) ∝ …(3)
Effective nuclear cℎarge of anion

From eqns. (2) and (3), we can write,

Radius (cation) Effective nuclear charge of anion

∝ ……(4)
Radius (anion ) Effective nuclear charge of cation
Hence, eqns. (1) and (4) can be used to calculate the values of radius (cation) + radius (anion) if
the values of distance (cation - anion), and the Zeff of cation and anion are provided.

(f) Periodic trends:

Along a group: Atomic and ionic size increases down the group.
Across a period: Atomic and ionic size decreases across a period from left to right.
Explanation: In the periodic table, moving from top to bottom, the electrons are added to the
new shell with a greater n value. Hence, atomic size increases. On the other hand,moving left to
right, the electrons are added to the same valence shell. Hence, with increase in atomic
number, effective nuclear charge increases, so there is an increased attraction of electrons to
the nucleus resulting in decrease of atomic size.

(g) Factors affecting atomic and ionic size:

(i) Magnitude of positive charge of the nucleus, i.e., number of protons present.
(ii) number of shells present in the atom/ion
(iii) shielding effect

(h) Isoelectronic ions: lons having the same number of electrons are called isoelectronic ions.
Examples: Ca2+, K+, CI- , S²- are isoelectronic (18 electrons each) and Na+ , Mg2+ , F- , O2- , N3-
are isoelectronic (10 electrons each)

5.4.2 Ionization Enthalpy

The amount of energy that, if supplied to an atom in gaseous state in ground state ejects one
electron from the valence shell and results in the formation of a cation, is called ionization
enthalpy. It is expressed in kJ mol-1.

(a) Successive Ionization Enthalpies

The amount of energy which, if supplied, ejects the first electron from an atom is called the 1"
ionization enthalpy (IE1).
M(g) → M+(g) + e-

The amount of energy which, if supplied, ejects the second electron from a uni-positive gaseous
ion is the 2nd ionization enthalpy (IE2).
M+(g) → M2+ (g) + 2e-

Generally, IE2 is greater than IE1 because on removal of the first electron, the atom is converted
to a cation due to which the nuclear pull increases. In order to remove the second electron, one
has to overcome this nuclear pull. Hence, IE2 > IE1.
(b) Periodic Trends:
Along a group: On moving from top to bottom, ionization enthalpy decreases.
Across a period: On moving from left to right, ionization enthalpy increases.
Explanation: In the periodic table, moving top to bottom, atomic size increases resulting in less
attraction between nucleus and corresponding electrons. Hence, removal of electrons becomes
easy. So, IE decreases. On the other hand, moving left to right, atomic size decreases resulting
in increased attraction between nucleus and corresponding electrons. Hence, removal of
electrons requires more energy. So, IE increases.

(c) Factors Affecting lonization Enthalpy

(i) Atomic size
(ii) Shielding/Screening effect
(iii) Penetration effect
(iv) Nuclear charge

5.4.3 Electron Affinity

The amount of energy released on addition of an electron to an atom to form an anion is called
electron affinity. It is expressed in KJ mol-1.
X(g) + e- → X- (g) + energy
(a) Successive Electron Affinities
The 1" electron affinity of almost all atoms is negative (EA1). In case of EA2, the electron is to be
added to a uni-negative ion. So energy is required to overcome the electron - electron repulsion,
making the 2nd electron affinity positive for all atoms.

(b) Periodic Trends

Along a group: On moving from top to bottom, electron affinity decreases.
Across a period: On moving from left to right, electron affinity increases.
Explanation: In the periodic table, moving from top to bottom, electron affinity decreases
because the electrons are added to the higher energy levels far away from the nucleus,resulting
in less attraction of the nucleus for the incoming electrons. On the other hand, moving left to
right, electron affinity increases since with decrease in atomic size,electrons move closer to the
nucleus.

(c) Factors Affecting Electron Affinity

(i) Atomic size
(ii) Nuclear charge

5.4.4 Electronegativity
The ability of an atom to attract the shared pair of electrons to itself is known electronegativity.

(a) Pauling's electronegativity equation: Linus Pauling stated that a covalent ben A-B should
be stronger than that of the average of A-A and B-B bonds. Th electronegativity is the power of
an atom in a molecule to attract the bonded pair electrons towards itself. Pauling scale is for
those elements which are joined by covalent bonds and is based on bond-energy calculations.
The electronegativity difference u exists between two atoms, namely A and B, can be
represented as,
XA - XB= 0.012 √(EAB - (EAA EBB)1/2)
Here, XA, and XB denotes the electro-negativities of atoms A and B respectively, such that XA-
XB. EAA ,EBB and EAB represents the bond energies of A-A, B-B and A-B bonds.

(b) Mulliken's electronegativity equation: According to Mulliken's equation,electronegativity is

simply the average of the first ionization enthalpy and electron affinity.

XM = (IE + EA) / 2

where IE = first ionization enthalpy and EA = electron affinity.

(c) Periodic trends:

Along a group: On moving from top to bottom, electronegativity decreases.
Across a period: On moving from left to right, electronegativity increases.
Explanation: In the periodic table, moving top to electronegativity affinity decreases because the
electrons are added to the higher energy levels far away from the nucleus, resulting in less
attraction of the nucleus for the incoming electrons. On the other hand, moving left to right,
electronegativity increases since with decrease in atomic size; the electrons move closer to the
nucleus.

Factors affecting electronegativity:

(i) Atomic size, (ii) Atomic number, (iii) Electron affinity, (iv) Oxidation state, (v) Hybridization.

5.4.5 Polarizability
The distortion of electron clouds of an atom in presence of an electric field is called polarization
and the ability of an atom to polarize the other resulting in formation of instantaneous dipoles is
called polarizability. The extent of polarization is the measure of the tendency of an atom to
share its electrons and attain covalent character.

(a) Effects of Polarization:

(i) Bromides and iodides are much more stable than expected because of their higher lattice
energies. As a result, instead of an ionic bond, a more stable polar covalent bond is formed.
(ii) In case of polar solvents, solubility of ionic compounds decreases with increase in degree of
polarization.
(iii) The hardness of ionic compounds decreases with increase in degree of polarization.

(b) Periodic Trends:

Along a group: On moving from top to bottom, polarizability increases.
Across a period: On moving from left to right, polarizability decreases.
Explanation: In the periodic table, moving top to bottom, atomic size increases and the electron
clouds distort more easily since they are larger in size. Hence, polarizability increases. On the
other hand, moving left to right, effective nuclear charge (Zeff) increases resulting in more
attraction between nucleus and the electrons. Hence, polarizability decreases.
(c) Factors affecting polarizability:
(i) Atomic number, (ii) Atomic size, (iii) Molecular orientation with respect to an electric field.

(d) Fajan's rules on polarizability:

According to Fajan's rules, polarizibility will increase if-

(i) charge on a cation is high.
(ii) size of the cation is small.
(iii) charge on an anion is high.
(iv) size of the cation is large.

In addition, if two cations are present and if they exhibit same size and charge, then the cation
having a pseudo noble gas configuration with 18 electrons will have more polarizing power
compared to the one with a noble gas configuration.

5.4.6 Oxidation State or Oxidation Number

The number that an element in a molecule attains due to gain or loss of electrons is known as
oxidation number or oxidation state. It arises due to different electronic configurations in the
valence shell of the atoms.

(a) Rules for Calculation of the Oxidation State

(i) Homo-nuclear molecules or free atoms like H2, O2, Cl2, O3, S8, Na, Mg, have their oxidation
state zero.
(ii) Ions with a single atom have the oxidation state equal to the charge on the ion. Thus Na + ion
has an oxidation number of +1, and CI- ion has -1.
(iii) Generally oxidation number of O remains -2 for most of the compounds but there are two
exceptions;
 In case of peroxides, there are two O atoms each with -1 oxidation number. Example-H2O2,
Na2O2 and for superoxides there are two O atoms each with - 1/2, Examples: KO2, RbO2.

 Oxygen has oxidation number of +2 and +1 respectively in oxygen difluoride (OF2) and
dioxygen difluoride (O₂F₂).

(iv) Generally, oxidation number of H remains +1 for most of the compounds but for hydrides it
is -1, for example, in LiH, NaH and CaH2.

(v) Halogens, especially fluorine, have a general oxidation state of -1. Other halogens also show
similar behaviour for their salts.

(vi) Chlorine, bromine and iodine in compounds with oxygen (oxoacids and oxoanions) have
positive oxidation numbers.
Case of Some Simple Compounds

⚫ Calculate the oxidation number of C in H2CO3,

2(+1)+C+ 3(-2) = 0; C = +4

⚫Calculate the oxidation number of C in (HCO3)-

1(+1) + C +3(-2)=-1; C = +4

⚫ Calculate the oxidation number of C in glucose (C6H12O6)

6 x C+12(+1)+6(-2) = 0; C = 0

⚫ Calculate the oxidation number of S in (SO4)2-, H2S:

In (SO4)2- : S+4(-2)= 0; S = +6
In H₂S : 2(+1)+S=0; S= -2

⚫ Calculate the oxidation number of Fe in Fe(s) & Fe(OH)3(s):

In Fe(s): Fe=0
In Fe(OH)3(s): Fe + 3(-2)+3(+1) = 0; Fe = +3

⚫ Calculate the oxidation number of P in NaH2PO4, & H4P₂O7:

In NaH2PO4: 1+2(+1) +P+4(-2)= 0; P= +5

In H4P2O7: 4(+1)+2 P+7(-2)= 0; P= +5

⚫Calculate the oxidation number of S in H₂S₂O7, & NaHSO4:

In H₂S₂O7: 2(+1)+2 x S+ 7(-2) =0 ; S = +6
In NaHSO4: 1+1+S+4(-2) = 0; S = +6

⚫Calculate the oxidation number of Mn in KMnO4, & K2MnO4:

In KMnO4 : 1+ Mn+ 4(-2) = 0; Mn = +7

In K₂MnO4 : 2(+1) + Mn+4(-2)= 0; Mn = +6

⚫ Calculate the oxidation number of B in NaBH, & LIAIH

In NaBH4 : 1 + B + 4(-1) = 0 ; B = +3
In LiAlH4 : 1+Al+4(-1)= 0; Al = +3

⚫ Calculate the oxidation number of Cr in K2CrO, & K₂Cr₂O,:

In K2CrO4 : 2(+1)+ Cr +4(-2)=0; Cr = +6

In K2Cr₂O7: 2(+1)+ 2 x Cr +7(-2)=0; Cr = +6
(b) Nature of Oxides

(i) Element at the left side of the periodic table forms basic oxides (e.g., Na 2O, MgO). Basic
oxides, on reaction with water, form bases.
Na2O+ H2O → 2NaOH
MgO+ H₂O →Mg(OH)2

(ii) Element at the right side of the periodic table forms acidic oxides (e.g., Cl2O7, SO3). Acidic
oxides, on reaction with water, form acids.
Cl₂O7 + H2O → HCIO4
SO3 + H₂O → H₂SO4

(iv) Element at the centre of the periodic table forms either amphoteric oxides (e.g., Al 2O3,
As2O3) or neutral oxides (e.g., CO, NO, N2O).

QnA
3. Electron gain enthalpy of N is positive but for O it is negative, although O has lower IE than N.
Explain.
4. The radius of Na atom is greater than that of Na' cation. Explain.
5. Why are ionization enthalpies of Be and N more than those of B and O
6. Why inert gases have positive electron gain enthalpies?

5.5 EFFECTIVE NUCLEAR CHARGE

It is defined as the net positive charge experienced by valence electrons of an atom. It can also
be stated as the core charge experienced by the electrons of an atom from the nucleus of the
respective atom. It is denoted by Z The inner electrons present in an atom impose a shielding
effect due to which the outer electrons are unable to experience the nuclear pull, on account of
the repulsion between the inner-layer electrons. Effective nuclear charge can be calculated as
follows:
Zeff = Z - S
where Z is the atomic number and S is the number of inner shell (shielding) electrons.
Periodic trends:
Along a group: On moving from top to bottom, Zeff decreases.
Across a period: On moving from left to right, Zeff increases.

Explanation: In the periodic table, moving from top to bottom, although nuclear charge
increases, it is counter balanced by the shielding effect of the inner electrons. On the other
hand, moving left to right, nuclear charge increases but there is no accompanying increase in
shielding effect. Hence, effective nuclear charge (Zeff) increases.

5.6 PENETRATION IN ORBITALS

It refers to the ability of electrons to get closer to the nucleus. Different orbitals have different
nuclear penetration.
(a) Electrons having greater penetration power will experience less shielding. Hence they will
experience more Zeff resulting in shielding to a large extent.
(b) Electrons present in different orbitals will possess different wave functions and hence
different distributions around the nucleus. However, penetration is not the measure of how
effectively the higher electrons can penetrate this shield made by the inner electrons, it is a
measure of to what extent the electrons feel the nucleus.
(c) Since the core electrons do not shield themselves, they penetrate the most and experience
to the most effective nuclear charge.
(d) The s-orbitals have the highest electron probability density in the centre of the orbital or at
the nucleus and hence the electrons residing there exhibit higher electron density compared to
a 2p electron. So it penetrates the nucleus of the atom more than the 2p electrons.
(e) For atoms with multiple electrons, penetration power depends on both the shell and subshell
in an atom. Therefore,

⚫ For a given shell, the penetrating power of an electron follows the order s>p> d>f

⚫ For different # and I values, the penetration power of the electrons is in the following
order: 1s > 2s > 2p > 3s > 3p> 4s > 3d > 4p> 5s > 4d > 5p > 6s>4f..... and so on.

5.7 HARD-SOFT ACIDS AND BASES

R.G. Pearson (1963) classified acids and bases for the first time as hard or soft, depending
on their Kf values.

An acid is said to be hard if it is smaller in size and is highly charged. Examples: H+, Na+ Li+, K+,
Ca2+, Al3+, BF3,, CO2, RCO+, SO3,, (VO2)+, AICI3.

A base is said to be hard if it has a very low polarizability and is highly electronegative in nature.
Examples: F-, OH-, NH3, N2H4, H₂O, (SO4)2-,( PO4)3-

A soft acid contains extremely low charged cations and are readily polarizable in nature.
Examples: Cs+, Cu+, Au+, Pt2+, Hg+, Br2, I2, RO+
Soft bases are those which have low electronegativity and are much less polarizable.
Examples: H-, R- , CO, PR3 , C6H6 , SCN-

Salient Features:
 Hard acids and hard bases react with each other readily compared to soft ones.
 Hard acids and bases are smaller in size and are compact.
 Hard acids react preferentially with hard bases.
 Hard acids generally form bonds in the order: F> Cr> Br>I
 Hard acids generally have a high charge density.
 No unshared pair of electrons is present in the valence shell of hard acids.
 Soft acids and bases are diffused and are larger in size compared to the hard ones.
 Soft acids react preferentially with soft bases. • Soft acids generally form bonds in the order:
I> Br>C> F
 Soft acids generally have low charge density. The elements of 2nd and 3rd row transition
metals with +1 or +2 charge often form soft acids.
 Unshared pair of electrons is present in the valence shell of soft acids.
 Strength of acids or bases is not influenced by hard/soft considerations. An acid or a base
may be hard or soft and also be either weak or strong.
.QnA
7. Effective nuclear charge Zen increases across a period. Explain.
8. Why is the energy of the 2s orbital lower than the energy of a 2p orbital?
9. Comment on the charge densities of hard and soft acids.