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Periodic Table: Development O F Peri O Dic Ta B L E
Periodic Table: Development O F Peri O Dic Ta B L E
INTRODUCTION : Periodic table helps us to undergo a systematic study of the various elements found in
nature, Without which it would have been impossible for us to study all the elements. By classifying the elements
into various groups and periods a comparative study of the elements and their compounds can be done. It also
help us to analyze the periodic trend in various properties such as ionization potential, electron affinity, electronegativity etc.
He simply assumed that all the elements are made up of hydrogen, so we can say that
Drawback or Limitation :
(b) The atomic weights of all elements were not found as whole numbers.
Ex. Chlorine (atomic weight 35.5) and Strontium (atomic weight 87.5)
2. DOBEREINER TRIAD RULE
J.W. Dorbereiner pointed out that within a group of three elements having similar chemical and physical properties,
the atomic weight of the middle element is the mean of the other two. Some examples of such triads are given
below. He also pointed out the triad - iron, cobalt and nickel in which the atomic weights of the elements are
almost the same.
Some representative triads of Dobereiner
Triad Li Na K Ca Sr Ba S Se Te Cl Br I
Elements
Though it was the first successful attempt to rationalise the problem, it could not be generalised or extended.
Drawback or Limitation : All the known elements could not be arranged as triads.
John Alexander Reina newland in England made the first attempt to correlate the chamical properties of the
elements with their atomic weight. According to him -
(a) If the elements are arranged in order to their increasing atomic weights, every eighth element had similar
properties to first one like the first and eighth note in music. For example
Sa Re Ga Ma Pa Dha Ni Sa
Li Be B C N O F Na
Na Mg Al Si P S Cl K
(b) Inert gases were not discovered till then.
(a) He plotted a curve between atomic weight and atomic volume of different elements.
(b) The following observation can be made from the curve –
(i) Most electropositive elements i.e. alkali metals (Li, Na, K, Rb, Cs etc.) occupy the peak positions on
the curve.
(ii) Less electropositive i.e. alkali earth metal (Be, Mg, Ca, Sr, Ba) occupy the descending position on the
curve.
(iii) Metalloids (B, Si, As, Te, At etc.) and transition metals occupy bottom part of the curve.
(iv) Most electronegative i.e. halogens (F, Cl, Br, I) occupy the ascending position on the curve.
Note : Elements having similar properties occupy similar position on the curve.
Conclusion : On the basis of this curve Lother Meyer proposed that the physical properties of the elements are
periodic function of their atomic wt. and this become the base of Mendeleef's periodic table.
(vi) Each group upto VIIth is divided into A & B subgroups.'A' sub groups element are called normal elements
and 'B' sub groups elements are called transition elements.
(vii) The VIIIth group was consists of 9 elements in three rows (Transitional metals group).
(i) Study of elements : First time all known elements were classified in groups according to their similar
properties. So study of the properties of elements become easier .
(ii) Prediction of new elements : It gave encouragement to the discovery of new elements as some gaps
were left in it.
These were the elements for whom position and properties were well defined by Mendeleev even before
their discoveries and he left the blank spaces for them in his table.
Ex. Blank space at atomic weight 72 in silicon group was called Eka silicon (means properties like
silicon) and element discovered later was named Germanium .
(iii) Correction of doubtful atomic weights : Correction were done in atomic weight of some elements.
Initially, it was found that equivalent weight of Be is 4.5 and it is trivalent (V = 3), so the weight of Be was
13.5 and there is no space in Mendeleev's table for this element. So, after correction, it was found that
Be is actually divalent (V = 2). So, the weight of Be became 2 × 4.5 = 9 and there was a space between
Li and B for this element in Mendeleev's table.
– Corrections were done in atomic weight of elements are – U, Be, In, Au, Pt.
(i) Position of hydrogen is uncertain. It has been placed in lA and VII A groups because of its resemblance
with both the groups.
(iii) It is not clear whether the lanthanides and actinides are related to IIA or IIB group.
(iv) Although there is no resemblance except valency of subgroups A and B, they have been put in the same
group.
(v) Order of increasing atomic weights is not strictly followed in the arrangement of elements in the periodic
table. For e.g. – Co (At. wt. 58.9) is placed before I (127) and Ar (39.9) before K (39).
7. MODERN PERIODIC TA BLE (MODIFIED MENDELEEF PERIODIC TA BLE) :
(c) Moseley did an experiment in which he bombarded high speed electron on different metal surfaces and
obtained X-rays.
(d) Modern periodic law : The physical & chemical properties of elements are the periodic function of
their atomic number.
(It is also called as 'Bohr, Bury & Rang, Werner Periodic Table)
(a) It is based on the Bohr-Bury electronic configuration concept and atomic number.
(e) Elements belonging to same group having same number of electrons in the outermost shell so their
properties are similar.
(f) Elements belonging to same group having same no. of electrons in the outermost shell so their properties
are similar.
Description of periods
1. 1 1s 2 1
H, 2He Shortest
2. 2 2s, 2p 8 3
Li – 10Ne Short
3. 3 3s, 3p 8 11
Na – 18Ar Short
4. 4 4s, 3d, 4p 18 19
K – 36Kr Long
5. 5 5s, 4d, 5p 18 37
Rb – 58Xe Long
6. 6 6s, 4f, 5d, 6p 32 55
Cs – 86Rn Longest
7. 7 7s, 5f, 6d, 26 87
Fr – 112Uub Incomplete
Important Points :
(a) 2nd period elements (Li, Be, B) Shows diagonal relationship with 3rd period elements (Mg, Al, Si) so (Li,
Be, B) are called Bridge elements. Because of same ionic potential value they shows similarity in properties.
Li Be B
Na Mg Al Si
rd
(b) 3 period elements (Na, Mg, Al, Si, P, S, Cl) are called typical elements because they represent the
properties of other element of their respective group.
(c) Atomic number of last inert gas element is 86.
(d) Number of Gaseous elements – 11 (H, N, O, F, Cl + Noble gases)
Number of Liquid elements – 6 (Cs, Fr, Ga, Hg, Br, Uub)
Bromine is the only non-metal which exists in liquid form.
Number of Solid elements – 95 (if discovered elements are 112)
(e) 2nd period contains maximum number of gaseous elements. They are 4 (N, O, F, Ne)
Nomenclature of elements
(a) IUPAC gave names to elements above atomic number 100 as follows –
0 1 2 3 4 5 6 7 8 9
nil un bi tri quad pent hex sept oct enn
Atomic No. IUPAC Name Symbol IUPAC Official Name IUPAC Symbol
101 Un nil unium Unu Mendelevium Md
102 Un nil bium Unb Nobelium No
103 Un nil trium Unt Lawrencium Lr
104 Un nil quadium Unq Rutherfordium Rf
105 Un nil pentium Unp Dubnium Db
106 Un nil hexium Unh Seaborgium Sg
107 Un nil septium Uns Bohrium Bh
108 Un nil octium Uno Hassnium Hs
109 Un nil ennium Une Meitnerium Mt
110 Un un nilium Uun Darmstadtium Ds
CL ASSIFICATION OF ELEMENTS
s-BLOCK ELEMENTS
(a) The elements of the periodic table in which the last electron enters in s-orbital, are called s-block elements.
(c) Their general formulae are ns1 and ns2 respectively, where n = (1 to 7)
(d) IA group elements are known as alkali metals because they react with water to form alkali. II A group
elements are known as alkaline earth metals because their oxides react with water to form alkali and
these are found in the soil or earth.
(f) Fr57 and Ra88 are radioactive elements while H and He are gaseous elements.
p-BLOCK ELEMENTS
(a) The elements of the periodic table in which the last electron gets filled up in the p-orbital, called p-block
elements.
(b) p-orbital can accommodate a maximum of six electrons. Therefore, p-block elements are divided into six
groups which are III A, IV A, V A, VI A, VII A and zero group.
(d) The zero group elements having general formula ns 2p6 are inert, because their energy levels are fully
filled.
(e) The total number of p-block elements in the periodic table is 30 (excluding He).
(f) There are nine gaseous elements (Ne, Ar, Kr, Xe, Rn, F2, Cl2, O2 and N2) belonging to p-block. Gallium
(Ga) and bromine (Br) are liquids.
(g) The step-like thick lines drawn in the periodic table in the p-block divides elements into metals, nonmetals
and metalloids.
d-BLOCK ELEMENTS
(a) The elements of the periodic table in which the last electron gets filled up in the d-orbital, called d-block
elements.
(b) The d-block elements are placed in the groups named III, IV B, V B, VI B, VII B, VIII, I B and II B.
(c) In d-block elements the electron gets filled up in the d-orbital of the penultimate shell.
(e) The general formula of these elements is (n–1)s2, p6, d1-10 ns1-2 where n = 4 to 7.
(g) Out of all the d-block elements, mercury is the only liquid element.
f-BLOCK ELEMENTS
(a) The element of the periodic table in which the last electron gets filled up in the f-orbital, called f-block
elements.
(b) The f-block elements are from atomic number 58 to 71 and from 90 to 103.
(c) The lanthanides occur in nature in low abundance and therefore, these are called rare earth elements.
(e) The elements from atomic number 58 to 71 are called lanthanides because they come after lanthanum
(57). The elements from 90 to 103 are called actinides because they come after actinium (89).
(g) All the elements after atomic number 92 (i.e. U92) are transuranic elements.
(h) The general formula of these elements is (n–2) s2 p6 d10 f(1-14) (n–1) s2 p6 d0-1 ns2 where n = 6 & 7.
TYPE OF ELEMENTS
Using electronic configuration as the criteria, we generally recognize four general type of elements; the inert
gas elements, the representative elements, the transition elements, and the inner transition elements. The
classification of the elements into these groups is dependent on the extent to which the s, p, d and f orbitals are
filled.
Inert Gases
(a) s and p orbitals of the outer most shell of these elements are completely filled. The outermost electronic
configuration is ns2np6.
(b) Helium is also inert gas but its electronic configuration is 1s2
(a) Outermost shell of these elements is incomplete. The number of electrons in the outermost shell is less
than eight.
(c) s-and p-block elements except inert gases are called normal or representative elements.
(a) Last two shells of these elements namely outermost and penultimate shells are incomplete.
(b) The last shell contains one or two electrons and the penultimate shell may contain more than eight or up
to eighteen electrons.
(c) Their outermost electronic configuration is similar to d-block elements i.e. (n–1) d 1-10 ns 1-2.
(d) According to definition of transition elements, those elements which have partly filled d-orbitals in neutral
state or in any stable oxidation state are called transition elements. According to this definition Zn, Cd and
Hg (IIB group) are d-block elements but not transition elements because these elements have d 10
configuration in neutral as well as in stable +2 oxidation state.
(e) Because of the extra stability which is associated with empty, half-filled, and fully filled subshells, there
are some apparent anomalies in electronic arrangements in the transition series. This empirical rule is
illustrated by the chromium and copper configuration in the first d series of elements:
Sc Ti V Cr Mn Fe Co Ni Cu Zn
3d 1 2 3 5 5 6 7 8 10 10
4s 2 2 2 1 2 2 2 2 1 2
Inner Tra nsit ion Element s
(a) In these elements last three shells i.e. last, penultimate and prepenultimate shells are incomplete.
(c) The last shell contains two electrons. Penultimate shell may contain eight or nine electrons and pre-
penultimate shell contains more than 18, up to 32 electrons.
(d) Their outemost electronic configuration is similar to f-block element i.e. (n-2)f1-14 (n-1)s2 (n-1)p6 (n-1)d0-1ns 2
Magic Numbers
(a) Knowing the atomic number of the first member of a group, we can write the atomic number of the
subsequent elements by adding given magic number
I + 2 – 8
II+ 8 8 8 8
III+ 8 8 18 18
PERIOD
IV + 18 18 18 18 18 18
V+ 18 18 18 32 32 32
VI + 32 32 32 32 – –
VII
(b) In group IA – Atomic number of H is 1 and atomic number of other element will be as follows –
H1 1 2 3
Li 3 8 11 Na 11 8 19 K 19 18 37 Rb 37 18 55 Cs
Magic number
2 8 8 18 18
(a) Period number: The period no. of the element can be predicted from the principal quantum no. (n) of
the valence shell.
(b) Block number: Last electron enter in which orbital is knows as block no. .
(c) Group number: It is predicted from the number of electrons in the valence shell and penultimate shell.
Example :
S.No. Electronic Period Block Prediction Group
Configuration number number of Group number
1. [Ar]4s 2 3d 104p 6, 5s 1 5 s No. of ns e– 1
PERIODICITY
(a) The regular gradation in properties from top to bottom in a group and from left to right in a period is
called periodicity in properties.
(b) In a period, the ultimate orbit remain same, but the number of e– gradually increases.
(c) In a group, the number of e– in the ultimate orbit remains same, but the values of n increases.
Causes of periodicity
(a) The cause of periodicity in properties is due to the same outermost shell electronic configuration coming
at regular intervals.
(b) In the periodic table, elements with similar properties occur at intervals of 2, 8, 8, 18, 18 and 32. These
numbers are called as magic numbers.
Periodic Properties
Valency : It is defined as the combining capacity of the elements. The word valency is derived from an Italian
word "Valentia" which means combining capacity.
Old concept : Given by : Frankland
Valency with respect to Hydrogen : Valency of H = 1
It is defined as the number of hydrogen atoms attached with a particular element.
IA IIA IIIA IVA VA VIA VIIA
Na H MgH 2 AlH 3 SiH 4 PH 3 H 2S H–Cl
Valency 1 2 3 4 3 2 1
Note : Valency w.r.t. H across the period increases upto 4 and then again decreases to 1.
Valency with respect to oxygen : Valency of 'O' = 2
It is defined as twice the number of oxygen atoms attached with a particular atom.
IA IIA IIIA IVA VA VIA VIIA
Na 2 O MgO Al 2O 3 SiO 2 P 2O 5 SO 3 Cl 2O 7
Valency 1 2 3 4 5 6 7
Note : Valency with respect to oxygen increases from 1 to 7 across the period. Valency w.r.t. 'O' is equal to the
group number.
New concept : This concept is based on the electronic configuration. According to this concept valency for IA
to IVA group elements is equal to number of valence shell e– and from VA to zero group, it is –
[8– (number of valence e–)].
Valency = No. of valence e– Valency = (8– no. of valence e–)
(a) Valence shell e– suffer force of attraction due to nucleus and force of repulsion due to inner shell electrons.
(b) The decrease in force of attraction on valence e – due to inner shell e – is called screening effect or
shielding effect.(i.e. total repulsive force is called shielding effect.)
(c) Due to screening effect. valence shell e– experiences less force of attraction exerted by nucleus.(i.e. total
attraction force experienced by valence e– is called Zeff.)
(d) There is a reduction in nuclear charge due to screening effect. Reduced nuclear charge is called effective
nuclear charge.
(e) If nuclear charge = Z, then effective nuclear charge = Z – (Where (Sigma)= Screening constant)
So, Zeff = (Z – )
3
Li 1s2 2s 1 3 – 0.85× 2=1.70 1.70 1.30
4
Be 1s2, 2s 2 4 1× 0.35=0.35 0.85× 2=1.70 2.05 1.95
5
B 1s 2,2s 2,2p 1 5 2× 0.35=0.70 0.85× 2=1.70 2.40 2.60
6
C 1s 2,2s 2,2p 1 6 3× 0.35=1.05 0.85× 2=1.70 2.75 3.25
7
N 1s 2,2s 2,2p 3 7 4× 0.35=1.40 0.85× 2=1.70 3.10 3.90
8
O 1s 2,2s 2,2p 4 8 5× 0.35=1.75 0.85× 2=1.70 3.45 4.55
9
F 1s 2,2s 2,2p 5 9 6× 0.35=2.10 0.85× 2=1.70 3.80 5.20
Periodic variation
(a) From left to right in a period Zeff increases
(i) That is why in a period Zeff increases by 0.65 and hence atomic size decreases considerably.
(ii) In transition series Z increase by + 1 but screening effect increases by 0.85 So Zeff is 0.15
(1– 0.85 = 0.15) [Because e– enters in (n – 1) orbit which has value of = 0.85]
In transition series Zeff increases very less amount, by 0.15 from left to right and hence atomic size
remains almost constant.
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Zeff 3.00 3.15 3.30 3.45 3.60 3.75 3.90 4.05 3.70 4.35
Element Li Na K Rb Cs Fr
ATOMIC RADIUS
The average distance of valence shell e– from nucleus is called atomic radius. It is very difficult to measure the
atomic radius because –
(i) The isolation of single atom is very difficult.
(ii) There is no well defined boundary for the atom. (The probability of finding the e– is 0 only at infinity).
So, the more accurate definition of atomic radius is –
Half the inter-nuclear distance(d) between two atoms in a homoatomic molecule is known as atomic
radius.
This inter-nuclear distance is also known as bond length.Inter-nuclear distance depends upon the type of
bond by which two atoms combine.
Based on the chemical bonds, atomic radius is divided into four categories –
1. Covalent radius 2. Ionic radius 3. Metallic radius 4. Vander waal radius
1. Covalent radius
One half of the distance between the nuclei (internuclear distance) of two covalently bonded atoms in homodiatomic
molecule is called the covalent radius of that atom. The covalent bond must be single covalent bond. The
covalent radius (rA) of atom A in a molecule A2 may be given as:
d A A
rA =
2
i.e. the distance between nuclei of two single covalently bonded atoms in a homodiatomic molecule is equal to
the sum of covalent radii of both the atoms
dA–A = r A + r A
In a heterodiatomic molecule AB where the electronegativity of atoms A and B are different, the experimental
values of internuclear distance dA-B is less than the theoretical values (r A + r B).
DA-B = rA + rB – 0.09 x
According to Pauling – If the electronegativities of the two atoms A and B are xA and xB respectively then
2. Metallic Radius
Metal atoms are assumed to be closely packed spheres in the metallic crystal. These metal atom spheres are
considered to touch one another in the crystal. One half of the internuclear distance between the two closest
metal atoms in the metallic crystal is called metallic radius.
For example – Metallic radius and covalent radius of potassium are 2.3 Å and 2.03 Å respectively.
The molecules of non metal atoms are generally gases. On cooling, the gaseous state changes to solid state.
In the solid state, the non metallic elements usually exist as aggregations of molecules are held together by van
der wall forces. One half of the distance between the nuclei of two adjacent atoms belonging to two
neighbouring molecules of a compound in the solid state is called van der walls radius.
It may also be defined as half of the inter nuclear distance of two non bonded neighbouring atoms of two
adjacent molecules.
2 × vander waal's radius
1
van der Wall's radius = × Internuclear distance between two successive nuclei of two covalent molecules (d)
2
Van der wall's radius > Metallic radius > Covalent radius
The vander walls radius and covalent radius of chlorine atom are 1.80 Å and 0.99 Å respectively
4. Ionic Radius
A neutral atom changes to a cation by the loss of one or more electrons and to an anion by the gain of one or
more electrons. The magnitude of charge on cation and anion is equal to the number of electrons lost or gained
respectively. The ionic radii of the ions present in an ionic crystal may be calculated from the inter molecular
distance between the two ions.
Reasons
Reasons
(i) The effective nuclear charge decrease in the formation of anion. Thus the electrostatic force of attraction
between the nucleus and the outer electrons decreases as the size of the anion increases.
1
(a) Atomic radius (b) Atomic radius number of shells
Effective nuclear charge (Zeff)
Li > Be > B > C > N > O > F Li < Na < K < Rb < Cs
(c) Atomic radius Screening effect (d) Atomic size Magnitude of –ve charge
O < O– < O–2
1 1
(e) Atomic radius (f) Atomic radius
Magnitude of + ve charge Bond order
(b) In a group : It increases from top to bottom in a group as number of shell increases
Exceptions
(a) Tra nsit ion element s
Sc Ti V Cr Mn Fe Co Ni
Z eff Screening effect Z eff Screening effect
(b) Lanthanide Contraction
(iii) Mutual screening effect of e– is very less, because of complicated structure of f-orbital
(iv) Nuclear charge increases by one (+1) in lanthanides and actinides so atomic size of these elements slightly
decreases. It is known as lanthanide contraction. Its effect is also observe in 5d transition series.
(v) In Ist, 2nd and 3rd transition series,Radii– 3d < 4d 5d (except III rd B)
IIIB IVB
increases Y Zr
La Hf
} Equal due to lanthanide contraction
IIIA B<Al Ga Note : While atomic size should increases down the group.
(vi) Increase in nuclear charge is only 0.15 so atomic size remains almost constant.
A series of atoms, ions and molecules in which each species contains same number of electrons but different
nuclear charge is called isoelectronic series.
Na+ Mg2+
–
N3– O2– F Ne
Number of e– 10 10 10 10 10 10
Number of p 7 8 9 10 11 12
Minimum energy required to remove most loosly held outer most shell e – in ground state from an isolated
gaseous atom is known as ionisation potential.
(Isolated Without any bonding with other atom)
1. Successive Ionisation Energy
(a) For an atom M, successive ionisation energies are as follows -
st
M + E1 M+ + e– E1 = I Ionisation Potential
1
Ionisation Potential
Atomic size
(b) Effective nuclear charge ( Z eff ) : Ionisation potential increases with the increase in nuclear charge
between outermost electrons and nucleus.
1
Ionisation Potential
Screening effect
After loosing one e–, B attains electronic configuration of Be, so II nd ionisation potential of B is more than
Be. II nd Ionisation Potential of B > Be
(e) Stability of half filled and fully filled orbitals :
(i) Half filled p3,d5, f7 or fully filled s2, p6, d10, f14 are more stable than others so it requires more energy.
Ex. N O
1
Ionisation Potential
Metallic property
1
Re ducing character
Ionisation Potential
(i) IA group has minimum ionisation potential so they are strong reducing agents in gaseous state
( Li < Na < K < Rb < Cs)
(iii) VIIA group has maximum ionisation potential so they are strong oxidising agents (F > Cl > Br > I)
(i) If the difference between two successive ionisation potential > 16eV then lower oxidation state is stable.
(ii) If the difference between two successive ionisation potential < 11 then higher oxidation state is stable.
Al Al+
+ +2
} 12.8 eV So Al+ is more stable
Al Al
} 6.0 eV So Al+3 is more stable
Al+2 Al+3
419 590 631 656 650 652 717 762 758 736 745 906 579 760 947 941 1142 1351
403 549 616 674 664 685 703 711 720 804 731 876 558 708 834 869 1191 1170
376 503 541 760 760 770 759 840 900 870 889 1007 589 715 703 813 912 1037
ELECTRON AFFINITY
(a) The amount of energy released when an electron is added to the outermost shell of one mole of an
isolated gaseous atom in its lower energy state.
(b) The positive value of the electron affinity indicates that the process, i.e. X(g) + e– X (–g ) , is exothermic
and the negative value indicates the process to be an endothermic one. Thus the convention accepted in
defining the electron affinity apparently contradicts the established convention in the thermodynamics.
Thus, F(g) + e– F ( –g ) , H = – 328 kJ mol–1, and EA = 328 kJ mol–1 and
Li Be B C N O F Ne
59.8 –60 27 122 –31 141 328 –90
Na Mg Al Si P S Cl Ar
53 –60 44 134 72 200 349 0
Ga Ge As Se Br
29 120 77 195 324
(b) In a group : For the representative elements, in moving down in a group generally the electron affinity
falls down with the increases of atomic number because the effective nuclear charge Zeff at periphery
per electron remain almost same but the size gradually increases due to addition of new shell.
Exceptions
(a) Electron affinity values of nitrogen and phosphorous (VA) are lesser than the electron affinity values of
carbon and silicon respectively. It is due to the comparatively stable half filled configuration (np 3) of
nitrogen and phosphorus and the tendency to acquire the stable np3 configuration by the gain of one
electron in carbon and silicon (np2).
(b) The theoretical value of the electron affinity of zero group i.e. inert gas elements is zero due to stable s2p6 configuration.
(c) F < Cl, O < S, N < P, B < Al. Here it is interesting to note that the electron affinity sequence is in the
opposite order as is expected from the size sequence. To explai n the observed
sequence of electron affinity, we are to consider the other factors. Though the electrostatic attractive pull
towards the nucleus favours the 2nd period elements more compared to the corresponding 3rd period
elements, the added electron creates an unfavourable effect, i.e. electron-electron repulsion, which is
more for the 2nd period elements because of their smaller sizes. This repulsive force is not so large in the
3rd period elements because of their larger size.
ELECTRONEGATIVITY (EN)
(a) The tendency of an atom to attract shared electrons towards itself is called electronegativity.
(b) Electronegativity and Electron affinity both have tendency to attract electrons but electron affinity is for
isolated atoms. Where as electronegativity is for bonded atoms.
(c) A polar covalent or ionic bond of A – B may be broken as
(i) A – B A– : + B+ (Electronegativity A > Electronegativity B)
or (ii) A – B A+ + :B– (Electronegativity A < Electronegativity B)
(e) Electronegativity is property of a bonded atom not an isolated gaseous atom so no energy will be liberated
or absorbed.
Difference between electronegavity and Electron Affinity
Note : Small atoms are normally having more electronegativity than larger atoms.
Pauling's Scale
Pauling related the resonance energy (AB) of a molecule AB with the electronegativities of the atoms A and B.
If xA and xB are the electronegativities of atoms A and B respectively then
0.208 AB = xA – xB if xA > xB
E AB(theoritical) = (E A A E B B )
In a purely covalent molecule, AB, the experimental and theoritical values of bond energy A–B are equal,
So AB = 0
or xA = xB
Pauling assumed the electronegativity value of fluorine 4 and calculated the electronegativity values of other
elements from this value.
According to Mulliken, the electronegativity of an element is the average value of its ionisation potential and
electron affinity.
1
Electronegativity Electronegativity Zeff
Atomic size
(b) In a group : In the representative elements, in moving down in a group, the size increase while Zeff per
electron at the periphery remains almost constant. This is why, the electronegativity generally falls in a
group with the increase of atomic number.
Exceptions
(a) In '0' group – Electronegativity is always zero, because inert gas do not form molecule.
(b) Electronegativity of Cs and Fr are equal, it is because from 55
Cs to 87
Fr only one shell increases but
nuclear charge (No. of proton) increases by +32.
Note: So effect of nuclear charge balanced the effect of increase in number of shell.
Electronegativity of F > Cl but Electron affinity of Cl > F
(c) In group of IIB elements (Zn, Cd, Hg) value of electronegativity increases down the group, because of
lanthanide contraction
(d) In IIIA group, value of electronegativity increases down the group, because of transition contraction
Electronegativity of Ga > Electronegativity of Al
Application of electronegativity
(a) Metallic and non metallic nature
Metallic character increases down the group but decreases along a period.
1
EN Here EN = difference in electronegativities of bonded atoms
Bond length
Note : HF has minimum bond length as expected because of much difference in the electronegativities of H and F.
(c) Acidic strength of hydrides
NH3 < H2O < HF
In a perticular period acidic strength of hydride is depends on electronegativity of M in M – H bond.
Higher the electronegativity of M greater the acidic strength of hydride.
(d) Nature of bonds :
(i) According to Hanny & Smith formula
Ionic % = 16 (XA – XB) + 3.5 (XA – XB)2
Here X A = Electronegativity of A
XB = Electronegativity of B
If XA – XB > 2.1 Ionic % > 50% i.e. Ionic bond
If XA – XB < 2.1 Ionic % < 50% i.e. covalent bond
(ii) According to Gallis
XA – XB > 1.7 Ionic
XA – XB < 1.7 Covalent
If XA = XB ; then A – B will be non polar.
Ex. H—H, F—F
If XA > XB and difference of electronegativities is small then
A —— B bond will be polar covalent
(e) Nature of hydroxides
(i) As per Gallis, In AOH if electronegativity of A is more than 1.7 (Non metal) then it is acidic in nature.
(ii) If electronegativity of 'A' is less than 1.7 (metal) then AOH will be basic in nature
Ex. NaOH ClOH
XA 0.9 3.0
Nature Basic Acidic
(iii) If XA – X0 > X0 – XH then AO bond will be more polar and will break up as
A —— OH A +
+ OH –
It shows basic nature
(iv) If XA – XO < XO – XH
A — O ——H H+ + AO– It shows Acidic nature
Ex. In NaOH
XO – XNa (2.6) > XO – XH (1.4) So hydroxide is basic
In ClOH
XO – XCl (0.5) < XO – XH (1.4) So hydroxide is acidic
B 2O 3 CO 2 N 2O 5
EN increase, acidic nature increasse.
Acidic properties increases with increasing oxidation state of an element when centrel atom is same. Ex.
(i) Sb2O5 > Sb2O3 (ii) HClO4 > HClO3 > HClO2 > HClO
(iii) HNO 3 > HNO 2 (iv) SO 3 > SO 2
Cl
H OH
B Cl + H OH 3HCl + B(OH)3
Cl H OH
DENSITY
(a) In a group volume of an atom increases along with atomic weight but atomic weight increases more than
atomic volume, So density increases in a group.
(i) Inner shell configuration (ii) Atomic weight (iii) Packing capacity (iv) Chemical bond
Periodic variation
(a) In period density first increases till maximum and then decreases. (s-block to d-block increases, d-block
to p-block decreases)
Exceptions
(a) The density of sodium and magnesium is greater than K and Ca respectively. This can be explained by
inner shell configuration.
In K, 3d0 orbital is vacant, 3rd orbit has the capacity to hold 18e– but it has only 8e–. Due to empty orbitals
atomic volumes increases and so density decreases
(c) Highest density of solid metal Ir (22.63 gm/cc) and Os (22.6 gm/cc) and liquid metal Hg(13.6 gm/cc)
Order of density of elements
Li < K < Na < Rb < Cs Sc < Y < La Hg < Au < Os < Ir Cr < Fe < Cu
Ca < Mg < Be < Sr < Ba Ti < Zr << Hf Sc < Zn < Fe < Hg Fe < Cu < Pb
He < Ar < Kr < Rn Zn < Cd < Hg Fe < Hg < Au
(c) Structure of solid made up of (i) atomic solid (ii) molecular solid (iii) metallic solid.
Order of decreasing melting point is : Atomic solid > Metallic solid > Molecular solid
(e) Bond energy – Covalent solids like diamond, SiO2 etc have only covalent bonds between atoms so their
bond energy is higher than molecular or metallic solids.
Periodic variation
In period from left to right boiling point and melting point first increases then decreases.
Alkali metals – Crystal structure BCC (low boiling point & melting point)
Transition metals – ............"..... FCC (High boiling point & melting point)
Inert gases ............. Lowest boiling point & melting point (Vander waal force)
Transition elements .......... Highest melting point
(a) In s-block elements boiling point & melting point decreases down the group.
(b) In d-block elements boiling point & melting point increases down the group (due to lanthanide
contraction, zeff increases and hence bond energy increases)
(i) From IIIA – IVA group boiling point & melting point decreases down the group and from VA to '0' group,
boiling point & melting point increases down the group. (Atomic or molecular weigh vander waal force)
(ii) boiling point and melting point of monoatomic molecules are lesser than diatomic molecules.
'0' group < Halogens
(iii) Atomic solid non metals like B, C and Si has higher boiling point and melting point due to strong covalent
bond.
(iv) Boiling point & melting point of molecular solids are less because of weaker vander waal force among
molecules Ex. I 2.