PERIODIC PROPERTIES

DIAGONAL RELATIONSHIP:
Some elements of certain groups of 2nd period resemble much in properties with the elements of third period of
next group i.e. elements of second and third period are diagonally related in properties. This phenomenon is known
as diagonal relationship.
2nd period Li Be B C

3rd period Na Mg Al Si
Diagonal relationship arises because of
(i) similar size of atom and ions
(Li = 1.23 Å & Mg = 1.36 Å ; Li+ = 0.76 Å & Mg2+ = 0.72 Å)
(ii) similar polarising powers (charge to radius ratio)
(iii) similarity in electronegativity values
(Li = 1.0 & Mg = 1.2 ; Be = 1.5 & Al = 1.5)

THE PERIODICITY OF ATOMIC PROPERTIES:

(I) EFFECTIVE NUCLEAR CHARGE:
Between the outer most valence electrons and the nucleus of an atom, there exists finite number of shells
containing electrons. Due to the presence of these intervening electrons, the valence electrons are unable to
experience the attractive pull of the actual number of protons in the nucleus. These intervening electrons act as
shield between the valence electrons and protons in the nucleus. Thus, the presence of intervening (shielding)
electrons reduces the electrostatic attraction between the protons in the nucleus and the valence electrons
because intervening electrons repel the valence electrons. The concept of effective nuclear charge allows us to
account for the effects of shielding on periodic properties.
The effective nuclear charge (Zeff) is the charge felt by the valence electron. Zeff is given by Zeff = Z – . Where Z is
the actual nuclear charge (atomic number of the element) and  is the shielding (screening) constant.
There are some simple rules for determining the degree to which electrons in the various types of orbitals shield
other electrons from the nucleus & hence for determining the Zeff experienced by other electrons.
Write the full electronic configuration.
If the electron in question resides in an s or p orbital,
1. All electrons in principal shells higher than the electron in question contribute zero to .
2. Each electron (other than in the question) in the same principal shell contributes 0.35 to .
3. Electrons in the (n – 1) shell each contribute 0.85 to .
4. Electrons in deeper shells each contribute 1.00 to .

If the electron in question resides in a d or f orbital,

1. All electrons in principal shells higher than electron in question contribute zero to .
2. Each electron (other than in the question) in the same principal shell contributes 0.35 to .
3. All inner-shell electrons [i.e., (n – 1) and lower] uniformly contribute 1.00 to .

Sum the shielding constants from steps 1–4 for s or p orbital or from steps 1–3 for d or f orbital and subtract them
from the actual nuclear charge (Z) of the atom in question to obtain the Zeff felt by the electron in question.
The relative extent to which the various orbital penetrates the electron clouds of of other orbitals is s > p > d > f.
Thus, for any given principal quantum number n, an electron will experience the greatest effective nuclear charge
when in s-orbital than p-orbital and so on.

Ques: What is the effective nuclear charge at the periphery of nitrogen atom when a extra electron is added during the
formation of an anion. Compare the value of Zeff when the atom is ionized.
Sol. Ground state electron configuration of N (Z = 7) = 1s2 2s2 2p3
Electron configuration of N– = (1s2) (2s2 2p4)
Shielding constant for the last 2p electron,
 = [(5 × 0.35) + (2 × 0.85)] = 3.45
 Zeff = Z – 
Zeff for last p electron on N– = 7 – 3.45 = 3.55
Electron configuration of N+ = (1s2) (2s2 2p2)
Shielding constant for the last 2p electron,
 = [(3 × 0.35) + (2 × 0.85)] = 2.75
Zeff for last electron on N+ = 7 – 2.75 = 4.25
2. ATOMIC RADIUS:
(A) Covalent radius:
It is one-half of the distance between the centres of two nuclei (of like atoms)
bonded by a single covalent bond. Covalent radius is generally used for non-
metals.

Single Bond Covalent Radius, SBCR (bond length) -

d
(a) For homodiatomic molecules dA–A = rA + rA or 2rA so, rA = A-A

(b) For heterodiatomic molecules in which electronegativity remains approximately same.

dA – B = rA + rB

For heteronuclear diatomic molecule, A–B, where difference between the electronegativity values of atom A and
atom B is relatively larger,
dA – B = rA + rB – 9.0 
Electronegativity values are given in Pauling units and radius in picometers.
 = XA – XB where XA and XB are electronegativity values of high electronegative element A and less
electronegative element B. This formula is given by Stevenson & Schomaker.

(B) Van der Waals radius (Collision radius):

It is one-half of the internuclear distance between two adjacent atoms
in two nearest neighbouring molecules of the substance in solid state.
 Van der Waal’s radius does not apply to metals. Its magnitude
depends upon the packing of the atoms when the element is in the
solid state.

Comparison of covalent radius and van der Waal’s radius

(i) The van der Waal’s force of attractions are weak, therefore, their internuclear distances in case of atoms held by
van der Waal’s forces are much larger than those of between covalently bonded atoms. Therefore, van der Waal’s
radii are always larger than covalent radii.
(ii) A covalent bond is formed by the overlapping of two half-filled atomic orbitals, a part of the orbital becomes
common. Therefore, covalent radii are always smaller than the van der Waals radii. For example,

Elements H O F S Br

Covalent radius (Å) 0.37 0.66 0.64 1.04 1.11

van der Waal's radius (Å) 1.20 1.40 1.35 1.85 1.95

(C) Metallic radius (Crystal radius) :

It is one-half of the distance between the nuclei of two adjacent metal atoms in the
metallic crystal lattice.
 Metallic radius of an element is always greater than its covalent radius. It is due to the
fact that metallic bond (electrical attraction between positive charge of an atom and
mobile electrons) is weaker than covalent bond and hence the internuclear distance
between the two adjacent atoms in a metallic crystal is longer than the internuclear
distance between the covalently bonded atom.
For example: Metallic radius Covalent radius
K 231 pm 203 pm
Na 186 pm 154

rcovalent < rmettalic < rvander Waals

Variation in a period: On moving left to right due to increased nuclear charge the size decreases.
Variation in a group: On moving top to bottom due extra addition of a shell the size increases.
Some Irregularities
(a) The atomic radius of inert gas (zero group) is given largest in a period because it is represented as van der Waals’s
radius which is generally larger than the covalent radius. The van der Waal’s radius of inert gases also increases
from top to bottom in a group.
(b) In the transition series (e.g. in first transition series), the covalent radii of the elements decrease from left to right
across a row until near the end when the size increases slightly. On moving from left to right, extra protons are
placed in the nucleus and the extra electron are added. The orbital electrons shield the nuclear charge
incompletely. Thus the nuclear charge attracts all the electrons more strongly, hence a contraction in size occurs.
The radii of the elements from Cr to Cu, are very close to one another because the extra electron being added
increases the repulsion between the electrons and counter balances the increased nuclear charge on the outer
electrons (4s). As a result of this, the size of the atom does not change much in moving from Cr to Cu and for
zinc this repulsion even dominates the nuclear charge so size slightly increases.
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radius (Å) 1.44 1.32 1.22 1.18 1.17 1.17 1.16 1.15 1.17 1.25

(c) rAl  rGa

because of d orbital contraction.
(d) 4d 5d (Zr – Hf)
(lanthanide contraction)
The lanthanide contraction counter balances almost exactly the normal size increase on descending a group of
transition elements. Thus, covalent and ionic radii of Nb (5th period) and Ta (6th period) are almost same due to
poor shielding of f-orbitals electrons.

IONIC RADIUS :

 The sizes of ions increases as we go down a group (considering the ions of same charge). For example:
Li+ < Na+ < K+ < Rb+
Be2+ < Mg2+ < Ca2+ < Sr2+
F– < Cl– < Br – < –
 Cation is smaller than parent atom but anion is bigger than parent atom.

 The species containing the same number of electrons but differ in the magnitude of their nuclear charges are
called as isoelectronic species. For example, N3– , O2–, F–, Ne, Na+ , Mg2+ and Al3+ are all isoelectronic species with
same number of electrons (i.e. 10) but different nuclear charges of +7, +8, +9, +10, +11, +12 and +13 respectively.

Within a series of isoelectronic species as the nuclear charge increases, the force of attraction by the nucleus on
the electrons also increases. As a result, the ionic radii of isoelectronic species decrease with increases in the
magnitude of nuclear charges. For example,
Al3+ Mg2+ Na+ F– O2– N3–

Ionic radii increase

As effective nuclear charge decreases.

 Zero group elements should not be considered while comparing the size or ionic radii as their atomic radii are
expressed as van der Wall’s radii.

Ionisation Energy ( Ionisation potential)

Min amount of energy required to remove an electron from an isolated gaseous atom / species.

(I.E.)1 M(g)  M+(g) + e– H = +ve

(I.E.)2 M+(g)  M2+ (g) + e–

(I.E.)3 > (I.E)2 > (I.E.)1 – Difficult to remove an electron from a positively charged ion than from a neutral atom

Factors affecting I.E.

(a) Size Size   I.E. 

(b) Zeff Z
eff   I.E.  but   (i.e. Zeff  )  E 
(c) Electronic configuration – For a stable electronic configuration i.e. half-filled or fully filled configurations (stable
because of symmetry) I.E. will be larger
(d) The relative extent to which the various orbital penetrates the electron clouds of other orbitals is s > p > d > f. Thus,
for any given principal quantum number n, an electron will experience the greatest effective nuclear charge when in
s-orbital than p-orbital and so on. Hence the order of I.E. is as follows: s > p > d > f

Periodicity

L–R I.E.  (Zeff  )

T–B I.E.  (Size  )

Irregularities
(a) In  period (also in  period )

Be > B, N > O, Ne >> F

(b) .E.Ga> .E.Al
size same extra nuclear charge 
(c) 5d > 3d > 4d (lanthanide contraction)
Note: I.E. can be correlated with the reactivity e.g., (a) Noble gases are inert towards chemical reactivity.
(b) low I.E. of alkali metals correlate with their high reactivity.

# Ionisation energies of some elements

Electron Affinity (E.A)

The energy released when an electron is added to an isolated gaseous atom to produce a monovalent anion is
known as E.A. and enthalpy change of this process is known as electron gain enthalpy
Heg  ve energy released
M(g) + e–  M–(g) E.A.  ve
Heg  ve
energy released
E.A.  ve
(Heg)2 is always +ve – because of electrostatic repulsion between anion and electron (having same charge).

M–(g) + e–  M2–(g) Heg2 = + ve

Factors affecting E.A.

(a) Size Size   E.A. 

(b) Zeff Zeff   E.A.     E.A. 

(c) E.C. Stable E.C. will have smaller or –ve E.A

Periodicity

LR Zeff   E.A. 

TB Size   E.A.  (Except 3rd period elements)

Irregularities
(a) nd period

(b) E.A. 3P > 2P

E.A (low) B C N O F
(added electron goes to the smaller n = 2 and suffer significant repulsion from the other electrons present in this
level.)

E.A. (high) Al Si P S Cl
(added electron goes to the bigger n = 3 i.e. occupies larger region of space and the electron-electron repulsion is
much less.)

(c) Noble gases have large positive electron gain enthalpies because the electron has to enter the next higher
principal quantum level leading to a very unstable electronic configuration.
e.g.H in kJ / mol of groups 16th and 17th
S Se Te Po O
–200 –195 –190 –174 –141

Cl F Br I At
–349 –328 –325 –295 –270

Electronegativity.
A qualitative measure of the ability of an atom in a chemical compound to attract shared electrons to itself iscalled
electronegativity not a measurable quantity. A number of numerical scales of electronegativity have been
proposed.
Differences in E.A. & E.N.

(a) E.A. is defined in isolated gaseous state while E.N. is defined in bonded state
(b) E.A. is a absolute term, it has proper units while E.N. is a relative concept has no units

Different Scales of Measurement of Electronegativity.

(a) Pauling’s scale: Linus Pauling developed a method for calculating relative electronegativities of most elements.
According to Pauling

(b) Mullikan’s scale : Electronegativity  (chi) can be regarded as the average of the ionisation energy (IE) and the
electron affinity (EA) of an atom (both expressed in electron volts).

M =
IE  EA
2

Factors affecting Electronegativity.

(a) Size Size   EN 

(b) Zeff Zeff   EN     EN 

(c) Charge on cationic species
A3+ > A2+ > A+1 (for the same element)
Greater the charge on cation, greater E.N value
 (d) Charge on anionic species 
A3– < A2– < A– 
(e) State of hybridization
Greater the %s character  greater the attraction on the shared pair  Greater will be E.N sp > sp2 > sp3

Electronegativity of some elements according to Pauling scale

Elements H Li Be B C N O F Na P S Cl Br I

Electronegativity 2.1 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0.9 2.1 2.5 3.0 2.8 2.5

Periodicity
L – R  Zeff  E.N  T – P  Size  E.N 



Applications

Prediction of nature of bond

(a) XA = XB  pure covalent bond (b) XA  XB  partly ionic + covalent

Acc. to Pauling, if
XA – XB = 1.7 50% ionic
 < 1.7 more covalent less ionic  > 1.7 more ionic less covalent
Henny smith formula % ionic character = 16 + 3.5 2   = | XA – XB|
Bond to be 50% ionic  = 2.1

Ques: Calculate % ionic character of bond formed between the most electropositive element Cs (x = .7) and most
electronegative element F (x = 4.0).
Ans:
According to Henny Smith formula % ionic character
= 16(3.3) + 3.5 (3.3)2 = 52.8 + 38 .115 = 91.915 %

Inert pair effect:

The outer shell ‘s’ electrons (ns2) penetrate to (n – 1) d electrons and thus become closer to nucleus and are more
effectively pulled towards the nucleus. This results in less availability of ns2 electron pair for bonding of ns2 electron
pair becomes inert. The inert pair effect begins after n  4 and increases with increases value of n.

(i) Dominance of lower oxidation state on moving down the group in boron, carbon & nitrogen family may also be
explained by the inert pair effect.
(ii) The inert pair effect is not the explanation of monovalency, bivalency and trivalency in group 13, 14 & 15. It
merely describes what happens, i.e. two electrons do not participate in bonding. The reason that they do not take
part in bonding in energy.

Order of stability of oxidation state according to Inert pair effect :

Tl   Tl 3
Pb 2
 Pb 4 Ga   In   Tl  Sn2  Pb2 Sb3  Bi3
Bi 3  Bi 5
Ga 3  In 3  Tl 3 Sn4  Pb4 Sb5  Bi5
Types of Oxides and acidic / basic nature of oxyacid and hydra acid:

(c) Amphoteric oxides

Can react with an acid as well as with a base.
Ex Generally, metalloids or elements close to metalloids can form amphoteric oxides.

BeO  BeO + 2HCl BeCl2 + H2O, BeO + 2NaOHNaAlO2 (Sodiuni meta aluminate)
ZnO  ZnO + HCl  ZnCl2 , ZnO + NaOH Na2ZnO2 (sodium zincate)
SnO  (stannous oxide)

SnO + HCl SuCl2, SnO + NaOH  Na2SnO2 (sodium stanite)

SnO2  (stannic oxide)
SnO2 + 4HCl  SnCl4 SnO2 + NaOH  Na2SnO3 (sodium stanate)
(d) Neutral oxides: will not react with acids or bases CO, N2O, NO, OF2
(e) Amphiprotic oxide: which can accept and release H+ ions
Ex. H2O

Periodicity in nature of oxides

For oxy acids

(a) On moving L  R non-metallic character  acidic strength 

H3BO3 < H2CO3 < HNO3 H2SiO3 < H3PO4 < H2SO4 < HClO4

(b) On moving T  B, non – metallic character  acidic strength 

HNO3 > H3PO4 > H3AsO4 HClO4 > HBrO4 > HO4
(c) If same element is forming oxyacids in different oxidation states then, Greater the oxidation no. of the element
greater will be the acidic strength
HNO3 > HNO2 > H2N2O2 HClO4 > HClO3 > HClO2 > HClO

***