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PERIODIC PROPERTIES

PERIODIC TABLE PERIODIC TABLE

GROUPS PERIODS Ionisation Electron Electro Radii Lanthanide Metallic


energy affinity negativity Contraction Character

Old convention IA IIA IIIB IVB VB VIB VIIB VIII IB IIB IIIA IVA VA VIA VIIA 0
New convention 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

S– Block p - Block

1 H He

2 Li Be B C N O F Ne
d - Block
3 Na Mg Al Si P S Cl Ar

4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

6 Cs Ba La *
Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

7 Fr Ra Ac **

f-Block

 Helium belongs to s-block because last entered electron goes in s-block.

 Iridium is the most dense element followed by Osmium.

 NOTE : (1) Last entered electron (According to Aufbau’s Principle) decides the block of the element.
(2). The valence shell determines the period number.

GENERAL PROPERTIES OF PERIODIC TABLE

(1) There are Seventeen non-metals (including hydrogen) in periodic table.


(2) Five non - metals are solid C, P, S, Se, I.
(3) One non - metal is liquid i.e. Br.
(4) Eleven non-metals are gaseous.

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(5) Six gases are monoatomic (noble gases) i.e. He, Ne, Ar, Kr, Xe, Rn.
(6) Five gases are diatomic, they are H, F, N, O, Cl
(7) There are eight metalloids in periodic table like, B, Si, Ge, As, Sb, Te, Po, At.
(8) Five elements are liquid at room temperature namely Cs, Fr, Ga, Hg, and Br,
(9) s - Block and p - Block together are called Representative elements.
(10) Five elements are radioactive amongst representative elements. They are Po, At, Rn, Fr and Ra
(11) There are seven periods in long - form of periodic table.

1.DEVELOPEMENT OF MODERN PERIODIC TABLE

Dobereiner's Triads :
He arranged similar elements in the groups of three elements called as triads, in which the atomic mass
of the central element was merely the arithmatic mean of atomic masses of other two elements or all
the three elements possessed nearly the same atomic masses
Li Na K
7 23 39 7 + 39/2 = 23
Fe Co Ni
55.85 58.93 58.71 nearly same atomic masses
It was restricted to few elements, therefore, discarded

NEWLAND'S LAW OF OCTAVES :


He was the first to correlate the chemical properties of the elements with their atomic masses.
According to him if the elements are arranged in the order of their increasing atomic masses the eighth
element starting from given one is similar in properties to the first one.
This arrangement of elements is called as Newland's law of Octave.
Li Be B C N O F
Ns Mg Al Si P S Cl
K Ca
This classification worked quite well for the ligher elements but it failed in case of heavier elements
and, therefore, discarded

LOTHER MEYER'S CLASSIFICATION


He determined the atomic volumes by dividing atomic mass with its density in solid states.
He ploted a graph between atomic masses against their respective atomic volumes for a number of
elements. He found the following observations.
(i) Elements with similar properties occupied similar positions on the curve.
(ii) Alkali metals having larger atomic volumes occupied the crests.
(iii) Transitions elements occupied the troughs.
(iv) The halogens occupied the ascending portions of the curve before the inert gases.
(v) Alkaline earth metals occupied the positions at about the mid points of the descending portions of
the curve.
On the basis of these observations he concluded that the atomic volumes (a physical property) of the
elements are a periodic function of their atomic masses.
It was discarded as it lacks practical utility.

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(d) Mendeleev's Periodic Table :


Mendeleev's Periodic's Law
According to him the physical and chemical properties ofthe elements are a periodic function oftheir
atomic masses. He arranged then known elements in order of their increasing atomic masses considering
the facts that elements with similar properties should fall in the same vertical columns and leaving out
blank spaces where necessary.
Merits of Mendeleev's Periodic table :
(i) It has simplified and systematised the study of \3lements and their compounds
(ii) It has helped in predicting the discovery of new elements on the basis of the blank spaces given in its
periodic table.
Mendeleevs predicted the properties of those missing elements from the known properties of the other
elements in the same group. Eka - Aluminium and Eka-silicon names were given for gallium and germanium
(not discovered at the time of mendeleevs). Properties predicted by Mendeleevs for these elements
and those found experimentally were almost similar.

(iii) Atomic weights of elements were corrected. Atomic weight of Be was calculated to be 3 × 4.5 = 13.5
by considering its valency 3, was correctly calculated considering its valency 2 (2 × 4.5 = 9)
Demerits In Mendeleev's Periodic Table:
(i) Position of hydrogen is uncertain .It has been placed in lAand VilA groups because of its resemblance
with both the groups.
(ii) No separate positions were given to isotopes.
(iii) Anomalous position of lanthanides and actinides in periodic table.
(iv) Order of increaseing atomic weights is not strictly followed in the arrangment of elements in the
periodic table. For e.g.-Ar(At.wt.39.94) is placed before K(39.08) and Te (127.6) is placed before I
(126.9)
(v) Similar elements were placed in differents groups(CuIB and Hg IIB) and the elements with different
properties were placed in same groups(alkali metals IA and coinage metals IB)
(vi) It didn't explained the cause of periodicity.

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LONG FORM OF THE PERIODIC TABLE OR MOSELEY'S PERIODIC TABLE


He studied (1909) the frequency of the X-ray produecd by the bombardment of a strong beam of
electrons on 'metal target. He found that the square root of the frequency of X-rays ( v ) is directly
proportional to number of effective nuclear charge (z) of metal i.e. to atomic number and not to atomic
mass of the atom of that metal.(as nuclear charge of metal atom is equal to atomic number)
i.e. ( v ) = a (z - b)
Where 'a' is the proportionality constant and 'b' is a constant for all the lines in a given series of X-rays.
Therefore, he, concluded that atomic number was a better fundamental property of an element than
its atomic weight He suggested that the atomic number (z) instead of atomic weight should be basis of
the classification of the elements.
Modern Periodic Law (Moseley's Periodic Law)
Physical and chemical properties of elements are the periodic functions of their atomic number.lf the
elements are arranged in order of their increasing atomic numper, after a regular interval ,element with
similar properties are repeated.
Periodicity
The repetition of the properties of elements after regular intervals when the elements are arranged in
the order of increasing atomic number is called periodicity.

Cause of Perlodlcty:
The periodic repetition of the properties of the elements is due to the recurrence of similar valence
shell electronic configuration after certain regular intervals. For example, alkail metals have same
electronic configuration ns1, therefore, have similar properties.
The long form of periodic table is the contribution of Range, Werner, Bohr and Bury
This table is also referred to as Bohr's table since it follows Bohr's scheme of the arrangements of
elements into four types based on electronic configuration of elements
The modern periodic table consits of horizontal rows (periods) and vertical column (groups)
Periods:
There are seven periods numbered as 1, 2,3,4,5,6 and 7.
(i) Each period consists of a series of elements haVing same valence shell.
(ii) Each period corresponds to a particular principal quantum number of the valence shell present in it.
(iii) Each period starts with an alkali metal having outermost electronic configuration ns1.
(iv) Each period ends with a noble gas with outermost electronic configuration ns2np6 except helium having
outermost electronic configuration 1s2.
(v) Each period starts with the filling of new energy level.
(vi) The number of elements in each period is twice the number of atomic orbitals available in energy level
that is being filled. To illustrate
1st period shortest period having only two elements. Filling of electron takes place in the first energy
shell, for which,
n = 1, . = 0 (s-subshell) and m = O.
Only one orbital (1s) is available and thus it contains only two elements.
3rd period short period having only eight elements. Filling of electrons takes place in the third energy
level. For which,
n = 3, . = 0, 1,2 and no. of orbitals m = 0, 3, 5
no. of orbitals 1 3 5
(3s) (3p) (3d)
________________________
Total no. of orbitals 9
________________________

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But the energy of 3d orbitals are higher than 4s orbitals. Therefore, four orbitals (one 3s and three 3p
orbitals) corresponding to n = 3 are filled before filling in 4s orbital (next energy elevel). Hence 3rd
period contains eight elements not eighteen elements.
Groups:
There are eighteen groups numbered as 1,2,3,4,5, ................ 13, 14, 15, 16, 17, 18.
Group consists of a series of elements having similar valence shell electronic configuration.

2. CLASSIFICATION OF THE ELEMENTS :

It is based on the type of orbitals which receives the differentiating electron (i.e., last electron).

s-block elements

When shells upto (n - 1) are completely filled and the last electron enters the s-orbital of the
outermost (nth) shell, the elements of this class are called s-block elements.
• Group 1 & 2 elements constitute the s-block.
• General electronic configuration is [inert gas] ns1-2
• s-block elements lie on the extreme left of the periodic table.
• This block includes metals.
GROUP – IA OR 1 ALKALI METALS :

Li
Solids Na
K Metals ¼y huk d h jc l sQ fj;kn½
Rb
Cs
Liquids + Radiactive
Fr

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 GROUP – II A OR 2 , ALKALINE EARTH METALS :

Be
Solids Mg
Ca ¼csVk ekaxsd U;k l qUnj cki jkt h½
Metals
Sr
Ba
Radioactive
Ra

p-block elements
When shells upto (n -1) are completely filled and differentiating electron entres the p-orbital of the nth
orbit, elements of this class are called p-block elements.
• Group 13 to 18 elements constitute the p-block.
• General electronic configuration is [inert gas] ns2np1-6
• p-block elements lie on the extreme right of the periodic table.
• This block includes some metals, all non-metals and metalloids.
• s-block and p-block elements are collectively called normal or representative elements.
 GROUP – III A OR 13 , BORON FAMILY :

B Metalloids + Highest/Maximum Catenation property in group.


Al
Solids Ga Metals ¼cky xaxk/kj bafM;u fry d ½
In
Liquid TI

 GROUP – IV A OR 14 , CARBON FAMILY :

C } Non-metal+Maximum Catenation property in its group.


Si
Solids Ge Metalloids
¼d gksfl ;k t h l wuksizHkq½
Sn
Liquid Metals
Pb

 GROUP – V A OR 15 , NITROGEN FAMILY :

Gas N
P Maximum Catenation property in its group
As
Solids Metalloids
Sb ¼U;wt hy S.M] ikfd Lrku vkLVªsfy ;k l c fHk[kkjh½
Bi Metals

 GROUP – VI A OR 16 , OXYGEN FAMILY :

Maximum Catenation property in its group


Gas O
S
Non-metals
Se
Solids
Te ¼O style l sVhiks½
Po Metalloids
Radiactive

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d-Block elements

When outermost (nth) and penultimate shells (n - 1)th shells are incompletely filled and differentiating
electon enters the (n -1) d orbitals (i.e., d-orbital of penultimate shell) then elements of this class are
called d-block elements.
• Group 3 to 12 elements constitute the d-block.
• General electronic configuration is [inert gas] (n – 1)d1–10 ns0–2
• d-block elements are classified into four series
Series Elements (n–1)d being filled
3d Sc –30Zn
21
3d
4d Y–
39 48
Cd 4d
5d La,
57 72
Hf–80Hg 5d
6d Ac,
89 104
Rf – Uub
112
6d (incomplete series)
• Those elements which have paratially filled d-orbits in neutral state or in any stable oxidation state are
called stransition elements.

f-Block elements

When n, (n–1) and (n –2) shells are incompletely filled and last electron enters into f-orbital of
antepenultimate i.e., (n–2)th shell, elements of this class are called f-block elements., General electronic
configuration is (n – 2)f1–14 (n – 1)d0–1 ns2
• All f-block elements belong to 3rd group.
• They are metals
• Within each series, the properties of the elements are quite similar.
• They are also called as inner-transition elements as they contain three outer most shell incomplete
and were also referred to as rare earth elements since their oxides were rare in earlier days.
The elements of f-block have been classfied into two series.
• The actinides and lanthanides have been placed at the bottom of the periodic table to avoid
the undue expansion of the periodic table.
1. Ist inner transition or 4 f-series, contains 14 elements Ce to
58 70
Lu. Filling of electrons takes place in 4f
subshell.
2. IInd inner transition or 5 f-series, contains 14 elements Th to
90
Lr. Filling of electrons takes placed in
103
5f subshell.

3.NOMENCLATURE OF THE ELEMENTS WITH ATOMIC NUMBER > 100 (IUPAC)

According to IUPAC, elements with atomic number > 100 are represented by three latter symbols.
• These symbols are based on first letter of numbers from 0 to 9. The names of these number are derived
from Greek and latin languages.
• The latin words for various digits of the atomic number are written together in the order of which
makes the atomic number and suffix 'ium' is added at the end. In case of bi and tri one 'i' is omitted.

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NOTATION FOR IUPAC NOMENCLATURE OF ELEMENTS

Digit Name Abbreviation


0 nil n
1 un u
2 bi b
3 tri t
4 quad q
5 pent p
6 hex h
7 sept s
8 Oct o
9 enn e

• Official IUPAC name yet to be announced + Elements yet to be discovered

•• IUPAC recommended this nomenclature to be followed until their names are officially recognised

4.PREDICTION OF PERIOD, GROUP AND BLOCK

The block of an element corresponds to the type of subshell which receives the last electron

The group is predicted from the number of electrons in the valence shell or/and penultimate shell as
follows.

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(a) For s-block elements

Group number = the no. of valence electrons

(b) For p-block elements

Group number = 10+ no. of valence electrons

(c) For d-block elements

Group number = no. of electrons in (n - 1) d sub shell + no. of electrons in valence shell.

5.METALS AND NON-METALS

• The metals are characterised by their nature of readily giving up the electron and from shinning
lusture. Metals comprises more than 75% of all known elements and appear on the left hand side of the
periodic table. Metals are usually solids at room temperature (except mercury). They have high melting
and boiling points and are good conductors of heat and electricity. Oxides of metals are basic in
nature. (Some metals in their higher oxidation state form acid oxides e.g. CrO3)

• Non-metals do not lose electrons but take up electrons to form corresponding anions. Non-metals are
located at the top right hand side of the periodic table. Non-metals are usually solids or gases at room
temperature with low melting and boiling points. They are poor conductors of heat and electricity.
Oxides of non-metals are acidic in nature.

6. METALLOIDS (SEMI METALS)

• It is very much clear from the periodic table that non-metallic character increases as we move from
left to right across a row. It has been found that some elements lying at the border of metallic and
non-metallic behaviour, possess the properties that are characteristic of both metals and non-metals.
These elements are called semi metals or metalloids.

• The metalloids comprise of the elements B, Si, Ge, As, Sb and Te.

• Oxides of metalloids are enerall am hoteric in nature.

7.TYPICAL ELEMENTS :

• Third period elements are called as typical elements. These include Na, Mg, AI, Si, P, S, CI.

• The properties of all the elements belonging to a particular group resemble the properties of the
corresponding typical element of that group. For example, the general properties of alkali metals (IA)
can be predicted from the properties of Na, not Li, the first member of the group.

• The properties of the elements of second period differ in the many respect belonging to the same
group due to the smaller atomic size and absence of vacant d-orbitals.

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8. 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.

Diagonal relationship arises because of


(i) similar size of atom and ions
(Li = 1.23 Å & Mg = 1.36 Å; Li+ = 0.60 Å & Mg2+ = 0.65 Å
(ii) similar electropositive characters
(iii) similar polarising powers (charge to radius ratio)
(iv) similarity in electronegativity values
(Li = 1.0 & Mg = 1.2; Be = 1.5 &AI = 1.5)
• Similarities between properties of Li and Mg are as follows.
(a) Li and Mg both reacts directly with nitrogen to form lithium nitride (Li3N) and magnesium nitride (Mg3N2)
whereas other alkali metals of IA group does not form nitride.
(b) Fluoride, carbonate and phosphate of Li and Mg are insoluble in water whereas these compounds of
other alkali metals are soluble.
(c) Li and Mg both are hard metals, whereas other metals of IA group are soft.
(d) LiOH and Mg(OH)2 both are weak bases, whereas hydroxides of other elements of IA group are strong
base.
(f) Metallic bond in Li and Mg both are strong compare to other alkali metals.
(g) Their melting and boiling points are high.
(h) By thermal disintegration of LiNO3 and Mg (NO3)2 ; Li2O and MgO is obtained respectively.
(I) Thermal stability of Li2CO3 and Mg CO3 is very less compare to other alkali metals and they liberates CO2
gas easily.
• Similarly Be shows similarity to AI of IIIA group compare to other elements of IIA group which are as
follows.
(a) These both elements do not provide colour to Bunsen bumer.
(b) They both are comparatively stable in air.
(c) Both are insoluble in NH3 therefore do not form blue coloured solution.
(d) There is no tendency of making peroxide and superoxide in them.
(e) Reducing power is very less due to low value of standard electrode potential in the form of oxidation
potential.
(f) Be and AI both forms halogen bridge halides.

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9. THE PERIODICITY OF ATOMIC PROPERTIES:


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 valenece 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.

ATOMIC RADIUS:

Probability of finding the electron is never zero even at large distance from the nucleus. Based on
probability concept, an atom does not have well defined boundary. Hence exact value of the atomic
radius can't be evaluated. Atomic radius is taken as the effective size which is the distance of the
closet approach of one atom to another atom in a given bonding state.
Atomic radius can be
(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 -


(a) For Homoatomic moleucles dA–A = rA + rA or 2rA

dA – A
rA 
2
• (b) For hetrodiatomic molecules in which electro negativity remains approximately same.
dA–B = rA + r B
• For heteronuclear diatomic molecule, A – B, where difference between the electronegativity values of
atom A and atom B is relativity larger,
dA–B = rA + rB – 0.09 (XA – XB)
where XA and XB electronegativity values of high electronegative element A and less electronegative
element B, respectively. This formula is given by Stevenson & Schomaker.

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Ex.2 Calculate the bond length of C – X bond, if C – C bond length is 1.54 Å, X – X bond length is 1.00
Å and electronegativity values of C and X are 2.0 and 3.0 respectively
Sol. (1) C – C bond length = 1.54 Å
154
.
rC = = 0.77 Å
2
100
.
rX = = 0.50 Å
2
(2) C – X bond length
dC–X = rC + rX – 0.09 (Xx – XC)
= 0.77 + 0.50 – 0.09 (3 – 2)
= 0.77 + 0.50 – 0.09 × 1
= 1.27 – 0.09 = 1.18 Å
Thus C – X bond length is 1.18 Å

(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 Waa's radius does not apply to metal. its magnitude depends upon the packing of the atoms
when the element is in the solid state.
• Comparision of convalent 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 overlaping 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,

(C) Metallic radius (crystal radius) :

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It is one -half of the distance between thenuclei 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 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 pm
• rcovalent < rcrystal < rvander Walls

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.
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 nucleus 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 successive addition of d-electrons screen the outer electrons (4s) from the
inward pull of the nucleus. As a result of this, the size of the atom does not change much in moving
from Cr to Cu.

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Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radius (A) 1.44 1.32 1.22 1.18 1.17 1.17 1.16 1.15 1.17 1.25
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 peroid) and Ta (6th period) are
almost same due to poor shielding of f-orbitals electrons.

IONIC RADIUS:
The effective distance from the centre of nucleus of the ion up to which it has an influence in the ionic
bond is called ionic radius.

For example : Na Na+


Number of Electrons 11 10
Number of Protons 11 11
2 2 6 1
Electronic Configuration 1s 2s 2p 3s 1s2 2s2 2p6
Cl Cl–
Number of Electrons 17 18
Number of Proton 17 17
• The sizes of ions increases as we go down a group (cosidering the ions of same charge)
For example
Li+ < Na+ < K+ < Rb+
Be2+ < Mg2+ < Ca2+ < Sr2+
F– < Cl– < Br– < I–
• The d and f orbitals do not shield the nuclear charge very effectively. Therefore there is significant
reduction in the size of the ions, just after d or f orbitals have been filled completely. This is called a
lanthanide contraction. Atomic radii of Zr and Hf are almost identical due to lanthanide contraction.
• 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– N2–

Ionic radii increase

As effective nuclear charge decrease.

1
• Pauling's empirical formula : Ionic radius 
nuclear ch arg e
• Following are the examples of isoelectronic series
(i) S2- Cl- K+ Ca+2 Sc+3 (ii) SO2, NO3–, CO32- (iii) N2, CO, CN– (iv) NH3, H3O–

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IONISATION ENTHALPY
lonisation enthalpy/energy (IE) , sometimes also called ionisation potential (IP) , of an element is
defined as the amount of energy required to remove an electron from an isolated gaseous atom of that
element resulting in the formation of positive ion.
(E )
M(g)  
1
 M (g)  e –

M   IE2  M2   e –

M2   IE3  M 3  e –
IE2 & IE3 are the IInd & IIlrd ionization energies to remove electron from monovalent and divalent
cations respectively.
In general: (IE)1 < (IE)2 < (IE)3 < ............. because, as the number of electrons decreases, the
attraction between the nucleus'and the remaining electrons increases considerably and hence sUbsequent
1.E.(s) increase.
• Units of ionisation energy: KJ mol-1 ,K Cal mol-1, eV (electron volt)
• Factors Influencing lonisation enthalpy
(IE) variation in a period and group may or may not be regular and can be influenced by:

(A) Size of the Atom :


lonisation energy decreases with increase in atomic size. As the distance between the outermost
electrons and the nucleus increases, the force of attraction between the valence shell electrons and
the nucleus decreases. As a result, outer most electrons are held less firmly and lesser amount of
energy is required to knock them out.
For example, ionisation energy decreases in a group from top to bottom with increase in atomic size.

(B) Nuclear Charge:


The ionisation energy increases with increase in the nuclear charge. This is due to the fact that with
increase in the nuclear charge, the electrons of the outer most shell are more firmly held by the
nucleus and thus greater amount of energy is required to pull out an electron from the atom. For
example, ionisation energy increases as we move from left to right along a period due to increase in
nuclear charge.

(C) Shielding effect:


The electrons in the inner shells act as a screen or shield between the nucleus and the electrons in the
outermost shell. This is called shielding effect. The larger the number of electrons in the inner shells,
greater is the screenin effect and smaller the force of attraction and thus (IE) decreases.

(D) Penetration Effect of the Electron :


The ionisation energy increases as the penentration effect of the electrons increases.
It is a well known fact that the electrons of the s-orbital has the maximum probability of being found
near the nucleus and this probability goes on decreasing in case of p, d and f orbitals of the same
energy level. Within the same energy level, the penetration effect decreases in the order
s>p>d>f
Greater the penetration effect of electron more firmly the electron will be held by the nucleus and thus
higher will be the ionisation energy of the atom.

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For example, ionisation energy of aluminium is comparatively less than magnesium as outer most
electron is to be removed from p-orbital (having less penetration effect) in aluminium where as in
magnesium it will be removed from s-orbital (having large penetration effect) of same energy level.

(E) Electronic Configuration :


If an atom has exactly half-filled or completely filled orbitals, then such an arrangement has extrastability.
The removal of an electron from such an atom requires more energy than expected. For example,

As noble gases have completely filled electronic configuration, they have highest ionisation energies in
their respective periods.

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Metallic or electropositive character of elements increases as the value of ionisation energy decreases.
The relative reactivity of the metals increases with the decrease in ionisation energy.
The reducing power of elements increases as the value of ionisation energy decreases (Li is exception
in Alkali metals group which has highest reducing power)

Ex.3 First and second ionisation energies of Mg(g) are 740 and 1450 kJ mor–1. Calculate percentage
of Mg+(g) and Mg2+(g), if 1 g of Mg(g) absorbs 50 kJ of energy.

1
Sol. Number of moles of 1g of Mg = = 0.0417
24
Energy required to convert Mg(g) to Mg+(g)
= 0.0417 x 740 = 30.83 kJ
Remaining energy = 50 – 30.83 = 19.17 kJ

19.17
Number of moles of Mg2+ formed = = 0.0132
1450
Thus, remaining Mg+ will be = 0.0417 – 0.0132 = 0.0285

0.0285
% Mg+ = × 100 = 68.35%
0.0417
% Mg+ = 100 – 68.35 = 31.65%

ELECTRON GAIN ENTHALPY (ELECTRON AFFINITY) :

When an electron is added to a neutral gaseous atom (X) to convert it into a negative ion, the
enthalpy change accompanying the process is defined as the electron gain enthalpy.
Electron gain enthalpy provides a measure of the ease with which an atom adds an electron to form
anion.

X( g)  e –  X – ( g); H  Heq ...(i)


The negative of the enthalpy change for the process depicted in equation (i) is defined as the electron
affinity (EA) of the atom undergoing the change for the formation of.an anion.
Depending on the elements, the process of adding an electron to the atom can be either endothermic
or exothermic. When an electron is added to the atom and the energy is released, the electron gain
enthalpy is negative and when energy is needed to add an electron to the atom, the electron gain
enthalpy is positive. The addition of second electron to an anion is opposed by electrostatic repulsion
and hence the energy has to be supplied for the addition of second electron.

O(g)  e –  O – (g) + Energy EA (i)

O – ( g)  e –  energy  O 2 – (g) EA(ii)


EA (i) is exothermic whereas EA(ii) is endothermic.

Group 17 elements (halogens) have very high negative electron gain enthalpies because they can
attain stable noble gas electronic configuration by picking up an electron.
Noble gases have large positive electron gain enthalpies because the electron has to enter the next
higher energy level leading to a very unstable electronic configuration.
Electron gain enthalpy of O or F is less than S or CI. This is due to the fact that when an electron is
added to O or F, the added electron goes to the smaller n = 2 energy level and experiences significant
repulsion from the other electrons present in this level. In S or CI, the electron goes to the larger
n = 3 energy level and consequently occupies a larger region of space leading to much less electron-
electron repulsion.

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Electron gain enthalpies of alkaline earth metals are very less or positive because the extra electron is
to be added to completely filled s-orbitals in their valence shells.
Across a period, with increase in atomic number, electron gain enthalpy becomes more negative
because left to right across a period effective nuclear charge increases and consequently it will be
easier to add an electron to a small atom.
As we move in a group from top to bottom, electron gain entalpy becomes less negative because the
size of the atom increases and the added electron would be at larger distance from the nucleus.
1
(i) Electron affinity  (ii) Electron affinity  Effective nuclear charge (zeff)
Atomic size
1
(iii) Electron affinity  (iv) Stability of half filled and completely filled orbitals of a subshell
screening effect
is comparatively more and the addition of an extra electron to such an system is difficult and hence
the electron affinity value decreases.

Ex.4 How many CI atoms can you ionise in the process Cl  Cl   e the energy liberated for the

process Cl  e  Cl – for one Avogadro number of atoms. Given IP = 13.0 eVand EA= 3.60 eV
Sol. Let n atoms be ionised.
6.02 × 1023 × EA = n × IP

6.02  10 23  3.60
n = 1.667 × 1023
13

Ex.5 The first ionisation potential of Li is 5.4 eV and the electron affinity of CI is 3.6 eV Calculate H in
kcal mol–1 for the reaction.

Li(g)  Cl(g)  Li   Cl –


Carried out at such low pressures that resulting ions do not combine with each other.
Sol. The overall reaction is written into two partial equations

Li(g)  Li   e E1 = 5.4 eV

Cl(g)  e  Cl – E2 = –3.6 eV


H = E1 – E2 = 5.4 – 3.6 = 1.8 eV
= 1.8 × 23.06 kcal mol–1
= 41.508 kcal mol–1

Ex.6 For the gaseous reaction,

K (g)  F( g)  K   F – ,H was calculated to be 19 kcal under conditions where the cations and
anions were prevented by electrosatic separation from combining with each other. The ionisation
potential of K is 4.3 eV. What is the electron effinity of F ?
Sol. K  K   e E1 = 4.3 eV

F  e  F – E2 = – E eV

19.0
 E1 – E2  4.3 – E
23.06
0.82 = 4.3 – E  E = 3.48

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Ex.7 The electron affinity of chlorine is 3.7 eV. How much energy in kcal is released when 2 g of
chlorine is completely converted to CI– ion in a gaseous state?
(1 eV = 23.06 kcal mol-1)
Sol. C  e  Cl –  3.7eV
35.5 3.7 × 23.06 kcal
.'. Energy released for conversion of 2 g gaseous chlorine into CI– ions

3.7  23.06
 × 2 = 4.8 kcal
35.5

ELECTRO-NEGATIVITY
Electronegativity is a measure of the tendency of an element to attract electrons towards itself in a
covalently bonded molecules .

X(g) + e–  X–(g)


The magnitude of electronegativity of an element depends upon its ionisation potential & electron
affinity. Higher ionisation potential & electron affinity values indicate higher electronegativity value.
With increase in atomic size the distance between nucleus and valence shell electrons incerases,
therefore, the force of attraction between the nucleus and the valence shell electrons decreases and
hence the electronegativity values also decrease.
With increase in nuclear charge force of attraction between nucleus and the valence shell electrons
increases and, therefore, electronegativity value increases
In higher oxidation state, the element has higher magnitude of positive charge. Thus, due to more
positive charge on element, it has higher polarising power. Thus, with increase in the oxidation state of
element, its electronegativity also increases.
Charge on cation  electronegativity of the atom

There is no direct method to measure the value of electronegativity, however, there are some scales
to measure its value .
(a) Pauling's Scale:
Linus Pauling developed a method for calcUlating relative electronegativities of most elements. According
to Pauling

 A – B  0.208  where    A –B –  A – A  B –B

where 'S refer to bond enthalpies (K Cal mol-1). By assigning F  4.0 ,  values of other atoms can be
computed.

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(b) Mulliken's scale


Electronegativity (EN) can be regarded as the average ofthe ionisation energy (IE) and the electron
affinity (EA) of an atom.

IE  EA
(EN) 
2
If both (EA) and (IE) are determined in eV units then paulings's electronegativity (EN)p is related to
Mulliken's electronegativity. Mulliken's values were about 2.8 times larger than the Pauling's values.

(c) Allred-Rochow's Electronegatlvlty


Allred and Rochow defined electronegativity as the force exerted by the nucleus of an atom on its
valence electrons:

0.359 Z effective
(EN) AR   0.744
r2
where Zelleclive is the effective nuclear charge and r the covalent radius (in Å ).

The electron negativity of Cs (55) is less than Fr (87). This is due to the increase of + 32 units in
nuclear charge of Fr which makes the effective nuclear charge comparatively high.
The electroneativity of inert gas elements of zero group is zero. Inert gases exist as monoatomic
molecules and the electronegativity is the property of bonded atoms.

Ex.8 lonisation potential and electron affinity of fluorine are 17.42 and 3.45 eV respectively. Calculate
the electronegativity of fluorine.
Sol. According to Mulliken equation

IP  EA
X when both IP and EAare taken in eV..
5.6

17.42  3.45
XF   3.726
5.6
APPLICATIONS OF ELECTRONEGATIVITY :
(I) Nomenclature:
Compounds formed from two nonmetals are called binary compounds. Name of more electronegative
element is written at the end and 'ide' is suffixed to it. The name of less electronegative element is
written before the name of more electronegative element of the formula.

Ex.9 Write the correct formula and name of the following


(a) ICI or CIl (b) FCI or CIF (c) BrCI or CIBr (d) BrI or IBr
(e)OF2 or F2O (f)Cl2O or OCI2
Sol. Correct formula Name
(a) I+ Cl– Iodine chloride
(b) CI+ F– Chlorine fluoride
+ –
(c) Br CI Bromine chloride
(d) IBr Iodine bromide
(e) OF2 Oxygen difluoride
(f) Cl2O Dichlorine oxide

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(II) Nature of Bond:


If difference of electronegativities of the two elements is 1.7 or more, then ionic bond is formed
between them whereas if it is less than 1.7, then covalent bond is formed. (HF is exception in which
bond is covalent although difference of electronegativity is 1.9)

(iii) Metallic and Nonmetallic Nature :


Generally values of electronegativity of metallic elements are low, whereas electronegativity values of
nonnmetals are high.

(iv) Partial Ionic Character in Covalent bonds


Partial ionic characters are generated in covalent compounds by the difference of electronegativities.
Hanny and smith calculated percentage of ionic character from the difference of electronegativity.
Percentage of ionic character = 16(XA – XB) + 3.5 (XA – XB)2
= 16 + 3.52
= (0.16 + 0.035 2) × 100
XA is electronegativity of element A
XB is electronegativity of element B
 = XA – XB

(v) Bond length


When difference of electronegativities of atoms present in a molecule is increased, then bond length
decreases. Shoemaker and stephensen determined.
Bond length dA – B = rA + rB – 0.09 |XA – XB|

1
or dA = (DA – A + DB – B) – 0.09 |XA – XB|
–B
2

(vi) Bond Strength & Stability


Bond strength and stability of A – B increases on increase in difference of electronegativities of atoms
A and B bonded A – B. Therefore H – F > H – Cl > H – Br > H – I

Ex.10 Electronegativity of which of the following is high ?


(1) –CH3(sp3) (2) H2C = CH2(sp2) (3) CH  CH(sp) (4) Equal in all
Ans. (3)

Ex.11 CF3NH2 is not a base, whereas CH3NH2 is a base. What is the reason ?
Sol. Due to high electronegativity of F tendency of donating the lone pair of electrons present on N will be
less

Ex.12 OF2 is called oxygen difluoride, whereas Cl2O is called dichlorine monoxide. Why ?
Sol. Electronegativity of O in OF2 is less than F. Therefore, there will be positive charge on oxygen and
negative charge on fluorine. Whereas in Cl and O, electronegativity of Cl is less than that of O
therefore there will be positive charge on Cl and negative charge on O. Positive charge is written first
followed by negative charge.

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Ex.13 Calculate the electronegativity of fluorine from the following data :


EH – H = 104.2 kcal mol–1, EF–F = 36.6 kcal mol–1
EH–F = 134.6 kcal mol–1, XH = 2.1
Sol. Let the electronegativity of fluorine be XF.
Applying Pauling's equation.

X F – X H  0.208[EH–F – (EF –F  EH–H )1/ 2 ]1/ 2


In this equation, dissociation energies are taken in kcal mol–1.
XF – 2.1 = 0.208 [134.6 – (104.2 × 36.6)1/2]1/2
XF = 3.87

Ex.14 The electron affinity of chlorine is 3.7 eV. How much energy in kcal is released when 2 g of
chlorine is completely converted to Cl– ion in a gaseous state ?
(1 eV = 23.06 kcal mol–1)

Sol. Cl + e  Cl– + 3.7 eV


35.5 3.7 × 23.06 kcal
 Energy released for conversion of 2 g gaseous chlorine into Cl– ions

3.7  23.06
 × 2 = 4.8 kcal
35.5

Ex.15 Calculate the electronegativity of fluorine from following data :


EH–H = 104.2 kcal mol–1
EF–F = 36.6 kcal mol–1
EH–F = 134.6 kcal mol–1
Electronegativity of H is 2.05.
Sol. On Paulling scale :

xF – xH = 0.182  H – F

(using B.E. in kcal mol–1)

H–F = EH–F – EH– H  EF –F = 13.45 – 104.2  36.6 = 72.84 kcal


From (i)

xF – xH = 0.182 72.84 = 1.5534


xF = xH + 1.4434 = 2.05 + 1.5534 = 3.6034

UNSOLVED EXERCISE :

1. The standard enthalpies of formation of gaseous XeF2, XeF4 & XeF5 are –108, –216 & –294 kJ mol–1
respectively and the bond energy in F2 is 159 kJ mol–1. Calculate the average Xe–F bond energy in each
of these compounds and use of the value for XeF2 to obtain a value for the electronegativity of xenon
on the Pauling scale assuming the electronegativity of fluorine to be 4.
2. Calculate the electronegativity value of chlorine on Mulliken's scale, given that IP = 13.0 eV and EA =
4.0 eV.

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(VII) METALLIC PROPERTY


Metals have the tendency to form cations by loss of electrons and this property makes the elements
as electropositive elements or metals.

M(g)  M  ( g)  e –

(IX) OXIDES
Oxygen react with all elements except noble gases, Au, Pd and Pt to form oxides. In general, metallic
oxides (O2–), peroxides (O22–) and super oxides (O2–1) are ionic solids.
The tendency of group IA metals (alkali metals) to form oxygen rich compounds increases from top to
bottom i.e. with increasing cation radii and decreasing charge density on the metal ion.
IIA metals also show the similar trend. Except Be, the IIA metals react with oxygen at normal conditions
to form normal ionic oxides and at high pressure of O2, they form peroxides (CaO2, SrO2, BaO2). Oxides
of metals are called as basic anhydries as most of them combine with water forming hydroxides with no
change in oxidation state of metals.
Oxides of IA and IIA dissolve in water forming basic solution where as other oxides do not dissolve in
water.

Na 2 O  H2 O  2NaOH
Oxygen combines with many non-metals to form covalent oxides such as CO, CO2, SO2, P4O10, Cl2O7 etc.
Non-metals with limited supply of oxygen usually form oxides in which non-metals are present in lower
oxidation states where as with excess of oxygen, oxides with higher oxidatin state are formed. Oxides of
non-metals are called as acid anhydrides as most of them dissolve in water forming acids of oxy-acids.
P4O10 + 6H2O  4H3 PO4 ; SO3 + H2O  H2SO4 : Cl2O7 + H2O  2HClO4

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In a group, basic nature of oxides increases or acidic nature decreases. Oxides of the metals are
generally basic and oxides of the non-metals are acidic. The oxides of the matalloids are amphotetric in
nature. The oxides of Al, Zn, Sn, As and Sb are amphoteric.
In a period the nature of the oxides varies from basic to acidic.
Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7
Strongly basic Basic amphoteric Weakly acidic Acidic Acidic Strongly acidic
CO, N2O, NO and H2O are neutral oxides.

GRAPHS OF PERIODIC PROPERTIES

ALKALI METALS

LANTHANIDES

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IMPORTANT POINTS TO REMEMBER

1. The basis of Mendeeleev's periodic table was his periodic law. According to it the physical and chemical
properties of the elements are a periodic function of their atomic masses.

2. According to Moseley, that a plot of v (where v is frequency of X-Rays emitted) against atomic
number (Z) gave a straight line and not the plot of ~ vs atomic mass. Therefore, he concluded that
atomic number (Z) instead of atomic mass was a better fundamental property of an element and
atomic number instead of atomic mass should be basis of the classification of the elements.

3. Long form of periodic table contains seven periods (horizontal rows) and eighteen groups (vertical
columns).

4. In the modern periodic table, the period indicates the value of principle quantum number.

5. The number of elements in each period is twice the number of atomic orbitals available in the energy
level that is being filled.

6. Group consists of a series of elements having similar valence shell electronic configuration.

7. In modern periodic table each block (s, - p, - d - and f -) contains a number of columns equal to the
numbers of electrons that can occupy that sub-shell.

8. The 4f - (i.e., actinides) and 5f - (i.e., lanthanides) inner transition series of element are placed
separately in the periodic table to maintain its structure and to preserve the principle of classification.

9. Metals comprise more than 78% of all known elements and appear on the left side of the periodic table.
Silicon, germanium, arsenic, antimony, selenium and tellurium all are semi - metals or metalloids.

10. The combined effect of attractive force due to nucleus and repulsive force due to intervening electrons,
acting on the valence electrons is that the valence - electron experiences less attraction from the
nucleus. This is called shielding or screening effect.

11. Covalent radius < metallic or crystal radius < Van der Waal's radius.

12. Species having same number of electrons but different in the magnitude of their nuclear charges are
called as isoelectronic species and their size is inversely proportional to their effective nuclear charge.

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13. The smaller the ionisation energy, the easier it is for the neutarl atom to change in to a positive ions in
gaseous state.IE1 < IE2 < IE3 .........•

14. The greatest increase in ionization enthalpy is experienced on removal of electrons from core noble gas
configuration. End of valence electrons is marked by a big jump in ionization enthalpy.

15. Electron gain enthalpy provides a measure of the ease with which an atom adds an electron to form
anion:

x(g)  e –  X – (g); H   egH

16. The negative value of electron gain enthalpy of C > F (similarly S > 0) because there is weak electron-
electron repulsion in the bigger 3p subshell of C as compared to compact 2p - subshell of F.

17. Noble gases have larger positive electron gain enthalpies because the electron has to enter the next
higher energy level.

18. Addition of 2nd electron to an anion is opposed due to electrostatic repulsion and thus requires the
absorption of energy e.g in case of the formation of S2–, O2– etc.

19. The relative reactivity of metals increases with the decrease in their ionisation energies. Similarly the
relative reactivity of non-metals increases with increases in the negative value of electron gain
enthalpy.

20. According to Pauling, the electronegativity difference between two atoms is equal to 0.208  where
L\ is the extra bond energies in K cal mol-1. The acidic character of oxides increases when electronegativity
difference decreases between element and oxygen (E - O).

21.

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