TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

8764333388 ,9414304777

PERIODIC TABLE

Syllabus

1. Introduction
2. Developement of Periodic Table
3. Modern Periodic Table
4. Classification of Elements
5. Classification on the basis of subshell in which last electron enters
6. Periodicity
7. Periodic Properties
8. Atomic Size
9. Ionisation Potential or lonisation energy or Ionisation Enthalpy
10. Electron Affinity/Electron gain Enthalpy

11. Electron Negativity

185-A D-BLOCK , [Link] TEMPLE , SURYA NAGAR, TARON KI KOONT, TONK ROAD, JAIPUR PERIODIC TABLE 3
2
Extended or Long Form of the Periodic Table
s-Block Elements p-Block Elements

Metals Noble gases 0

IA
Group (18)
(1)
1
Non metals 2
Period
H IIIA IVA VA VIA VIIA He
1 1.0079 IIA 4.0026
Hydrogen Metalloids (13) (14) (15) (16) (17) Helium
(2)
3 4 5 6 7 8 9 10

2 Li Be b C N O F Ne
6.940 9.0122 d-Block Elements 10.811 12.011 14.007 15.999 18.998 20.180
Lithium Beryllium Boron Carbon Nitrogen Nitrogen Fluorine Neon

11 12 13 14 15 16 17 18
VIII
3 Na Mg IIIB IVB VB VIB VIIB IB IIB Al Si P S Cl Ar
22.990 24.305 6.982 28.086 30.974 32.066 35.453 39.948
Sodium Magnesium (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) Aluminium Silicon Phosporus Sulphur Chlorine ARgon

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.098 40.078 44.956 47.867 50.941 51.996 54.938 55.847 58.933 58.693 63.9546 65.39 62.723 72.61 74.922 78.96 79.904 83.80
Potassium Calcium Scandium Titanium Vanadium Chrominum Magnanese Iron Cobolt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd ln Sn Sb Te I Xe
85.468 87.62 88.936 91.224 92.906 95.94 98 101.07 102.91 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon

55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Ti Pb Bi Po At Rn
132.91 137.33 138..91 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.59 207.2 208.98 210 210 222
Cesium Barium Lanthanum Hafnium Tantaium Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Rdon

87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118

7 Fr Ra Ac** Unq Unp Unh Uns Uno Une Uun Uuu Uub Uut Uuq Uup Uuh Uus Uuo
223 226 227 263 268 266 272 277 276 281 280 285 283 289 288 292 294 295
Francium Radium Actinium Unnilquadium Unnilpentium Unnilhexium Unnilseptium Unniloctium Unnilennium Ununnilium Unununium Ununbium Ununtrium Ununquadium Ununpentium Ununhexium Ununseptium Ununoctium
TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

f-Block Elements
58 59 60 61 62 63 64 65 66 67 68 69 70 71
6 *Lanthanide Series Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.12 140.91 144.24 145 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 17.07 174.97
Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium

90 91 92 93 94 95 96 97 98 99 100 101 102 103

**Actinide Series Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
7 232.04 231.04 238.03 237 244 243 247 247 251 252 257 258 529 262
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Califonium Einsteinium Fermium Mendelevium Nobelium Lawrencium

IUPAC designations of groups of elements are given in brackets

3
GENERAL TREND OF DIFFERENT PROPERTIES IN THE PERIOD AND
GROUPS

PERIODS
Atomic radius Decreases
Ionisation potential Increases
Electronegativity Increases
Electron affinity Increases
Covalent character of halides Increases
G Increases
Metallic character Decreases
Decreases
Decreases Oxidising nature Increases
R Decreases Reducing nature Decreases
Decreases Screening effect Increases
O Increases Effective nuclear charge (Zef) Increases
Decreases Valency w.r.t. Oxygen Increases
U Increases
Incerases Basic character of hydroxides Decreases
Constant Basic character of hydrides Decreases
P Constant
Basic character of Oxides Decreases
(Metals) Increases
Strength of oxy acids Increases
S (Non metal) Decreases (Metals) Increases
Thermal stability of sulphate Decreases
Increases
Thermal stability of carbonates Decreases
TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

Decreases
Thermal stability of nitrate Decreases
Increases
Increases Thermal stability of hydroxide Decreases
Increases Density First increases then decreases
Increases Electro positively Decrease
Increases
Increases
TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

IMPORTANT FACTS TO REMEMBER

1. Lowest electronegativity : Cs
2. Highest electronegativity : F
3. Highest ionisation potential : He
4. Lowest ionisation potential : Cs
5. Lowest electron affinity : Noble gases
6. Highest electron affinity : Chlorine
7. Least electropositive element : F
8. Lowest m. pt. metal : Hg
9. Highest m. pt. and b. pt. metal : W (Tungsten)
10. Lowest m. pt. and b. pt. non metal : He
11. Notorious element : Hydrogen
12. Lightest element : Hydrogen
13. Smallest atomic size : H
14. Largest atomic size : Cs
15. Largest anionic size : I–
16. Smallest cation : H+
17. Most electropositive element : Cs
18. Element with electronegativity
next to Fluorine : Oxygen
19. Group containing maximum no.
of gaseous elements in periodic table : Zero group
20. Total number of gaseous elements
in periodic table : 11 (H, N, O, F, Cl, He, Ne, Ar, Kr, Xe, Rn)
21. Total number of liquid elements in
periodic table : 6 (Ga, Br, Cs, Hg, Fr, Uub)
22. Smallest anion : H–
23. Liquid element of radioactive nature : Fr
24. Total number of radioactive elements in
periodic table : 25
25. Volatile d-block elements : Zn, Cd, Hg, Uub
26. Element containing no neutron : H
27. Most aboundant element on earth : Oxygen
28. Rarest element on earth : At (astatine)
29. Most aboundant metal on earth : Al
30. Element having maximum tendency
for catenation : Carbon
31. Non metal having highest m. pt., b. pt. : Carbon (diamond)
32. Metals showing highest oxidation number : Os (+8)
33. Most electrovalent compound : CsF

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

34. Most stable carbonate : Cs2CO3

35. Strongest alkali : CsOH
36. Strongest basic oxide : Cs2O
37. Best electricity conductor among metals : Ag
38. Best electricity conductor among non metals : graphite
39. Most poisonous element : Pu (Plutonium)
40. Liquid non metals : Br
41. Element kept in water : Phosphorous
42. Elements kept in kerosene : IA group element (except Li)
43. Elements sublime on heating : I2
44. Noble metals : Au, Pt. etc.
45. Amphoteric metal : Be, Zn, Al, Sn, Pb
46. Amphoteric non metal : Si
47. Metalloids elements : B, Si, As, Te, At, Ge, Sb
48. Non metals having metallic lusture : Graphite, Iodine
49. Heaviest naturally occuring element : Uranium
50. Poorest conductor of electricity : Diamond
51. Hardest naturally occuring element : Diamond
52. Lightest solid metal : Li
53. Amphoteric oxides : BeO, Al2O3, ZnO, PbO, PbO2, SnO, SnO2,
Sb2O3, As3O3 etc.
54. Neutral oxides of non metals : NO, CO, H2O, N2O
55. Dry bleacher : H2O2
56. Dry ice : Solid CO2
57. First man made element : Tc43 (Technicium)
58. Smallest period : Ist (2 elements)
59. Largest period in periodic table : 6th (32 elements)
60. Largest group in periodic table : IIIB (32 elements)
61. Most abundant d-block metal : Fe
62. Most abundant s-block metal : Ca
63. Highest density (Metals) : Os, Ir
64. Highest density (Non Metals) : Boron
65. Most abundant gas in atmosphere : Nitrogen
66. Most abundant element in the universe : Hydrogen

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

PERIODIC TABLE

1. Introduction

The arrangement of all the known elements according to their properties in such a way that the elements of similar
properties are grouped together in a tabular form is called periodic table.

2. Development of Periodic Table


2.1 DOBEREINER TRIAD RULE [1817]
(i) He made groups of three elements having similar chemical properties called TRIAD.
(ii) In Dobereiner triad, at. wt. of middle element is equal to the average atomic weight of first and third element.
e.g.
Cl Br I
35.5 127
35.5 80.0 127 = 8.12
2
Ca Sr Ba
40 137
40 87.5 137 = 88.5
2
Li Na K
7 39
7 23 39 At. wt of Na = = 23
2
(iii) Other examples – (K, Rb, Cs), (P, As, Sb), (S, Se, Te), (H, F, Cl), (Sc, Y, La)

Examples
based on Dobereiner's Law of Triads

Ex.1 The law of triads is applicable to -

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

(A) C, N, O (B) H, O, N (C) Na, K, Rb (D) Cl, Br, I

Sol. (D)

Ex.2 The law of triads is not applicable on -

(A) Cl, Br, I (B) Na, K, Rb (C) S, Se, Te (D) Ca, Sr, Ba
Sol. (B)

2.2 NEWLAND OCTAVE RULE [1865]

(i) He arranged the elements in the increasing order of their atomic mass and observe that properties of every 8 th
element was similar to the 1st one. like in the case of musical vowels notation.
Sa Re Ga Ma Pa Dha Ne Sa
1 2 3 4 5 6 7 8
(ii) At that time inert gases were not known.
H
Li Be B C N O F
Na Mg Al Si P S Cl
K Ca
(iii) The properties of Li are similar to 8th element i.e. Na, Be are similar to Mg and so on.
Drawback or Limitation :
(a) This rule is valid only upto Ca. because after Ca due to presence of d-block element there is difference of 18
elements instead of 8 element.
(b) After the discovery of Inert gas and included in the periodic table it becomes the 8 th element from Alkali metal
so this law had to be dropped out.
(c) He failed in the case of heavier metals as Fe has been placed atoms with O and S.

2.3 LOTHER MEYER’S CURVE [1869]

(i) He plotted a curve between atomic wt. and atomic volume of different elements.
(ii) The following observation can be made from the curve -
(a) Most electropositive elements i.e. alkali metals (Li, Na, K, Rb, Cs etc.) occupy the peak positions on the
curve.
(b) Less electropositive i.e. alkaline earth metal (Be, Mg, Ca, Sr, Ba) occupy the descending position of the curve.
(c) Metalloids (B, Se, As, Te, At etc.) and transition metals occupy bottom part of 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 become the base of Mendelef‘s periodic table.

Cs
Rb
K
Br
Atomic Volume

Na Ca
Li
Cl Sr I
F Ba
Be Mg

Metalloid and transition metals

Atomic Weight

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

2.4 MENDELEEV’S PERIODIC TABLE [1869]

(i) Mendeleev’s Periodic Law - The physical and chemical properties of elements are the periodic function of their
atomic wt.

(ii) Characteristic of Mendeleev’s Periodic Table -

(a) It is based on atomic wt.
(b) 63 elements were known, noble gases were not discovered.
(c) He was the first scientist to classify the elements in a systamatic manner i.e. in horizontal rows and in vertical
columns.
(d) Horizontal rows are called periods and there were 7 periods in mendeleev‘s Periodic table.
(e) Vertical columns are called groups and there were 8 groups in mendeleev‘s Periodic table.
(f) 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.
(g) The VIIIth group was consists of 9 elements in three rows (Transitional metals group).
(h) The elements belonging to same group exhibit similar properties.

(iii) Merits or advantages of Mendeleev’s periodic table -

(a) Study of elements - First time all known elements were classified in groups according to their similar
properties.
So study of the properties become easier of elements.
(b) Prediction of new elements - It gave encouragement to the discovery of new elements as some gaps were left
in it.

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

Sc (Scandium), Ga (Gallium), Ge (Germanium), Tc(Technetium)

were the elements for whom position and properties were defined by Mendeleev even before their discoverties
and he left the blank spaces for them in his table.
e.g.- Blank space at atomic wt. 72 in silicon group was called Eka silicon (means properties like silicon) and element
discovetred later was named Germanium.
Similarly other elements discovered after
mendeleev periodic table were.
Eka aluminium - Gallium (Ga)
Eka Boron - Scandium (Sc)
Eka Silicon - Germanium (Ge)
Eka Mangense - Technetium (Tc)

(c) Correction of doubtful atomic weights - Correction were

done in atomic wt. of some elements.
At. Wt. = Valency × Equivalent weight.
Initially, it was found that equivalent wt. 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 at. wt. of elements are – U, Be, ln, Au, Pt.

(iv) Demerits of Mendeleev’s periodic table -

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

(b) Position of isotopes - As atomic wt. of isotopes differs, they should have placed in different position in
Mendeleev‘s periodic table. But there were no such places for isotopes in Mendeleev‘s table.

(c) Anomalous pairs of elements - There were some pair of elements which did not follow the increasing order
of atomic wts.
eg. Ar and Co were placed before K and Ni respectively in the periodic table, but having higher atomid weights.
Te I Te I
127.5 127 127.5 127

Co Ni Th Pa
58.9 58.6 232 231

(d) Like elements were placed in different groups.

There were some elements like Platinum (Pt) and Gold (Au) which have similar properties but were placed in
different groups in mendeleev‘s table.
Pt Au
VIII IB

(e) Unlike elements were placed in same group.

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

Ist group

IA IB
Li
Na
More reactive K Cu Less reactive
Alkali metal Rb Ag Coin metal
Normal elements Cs Au Transition element
Fr

– Cu, Ag and Au placed in Ist group along with Na, K etc. While they differe in their properties (Only similar
in having ns1 electronic configuration)

3. Modern Periodic Table (Modified Mendeleev Periodic Table)


(i) it was proposed by Moseley.
(ii) Modern periodic table is based on atomic number.
(iii) Moseley did an experiment in which he bombarded high Speed electron on different metal surfaces and obtained
X-rays.

He found out that Z where = frequency of X-rays

from this experiement, Moseley concluded that the physical and chemical properties of the elements are periodic
function of their atomic numbr. It means that when the elements are arranged in the increasing order of their
atomic number elements having similar properties gets repeated after a regular interval. This is also known as
‘Modern Periodic Law’.
(iv) Modern Periodic Law - The physical & chemical propeties of elements are a periodic function of the atomic
nubmer.
(v) Characteristics of Modern Periodic Table -
(a) 9 vertical columns called groups.
(b) Ith to VIII group +0 group of inert gases.
(c) Inert gases were introduced in periodic table by Ramsay.
(d) 7 horizontal series called periods.
3.1 LONG FORM/PRESENT FORM OF MODERN PERIODIC TABLE
(i) It consist of 7 horizontal periods and 18 vertical columns (groups)
(ii) According to I.U.P.A.C. 18 vertical columns are named as I st to 18th group.
(iii) The co-relation between the groups in long form of periodic table and in modern form of periodic table are given
below.

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

(iv) Elements belonging to same group having same no. of electrons in the outermost shell so their properties are
similar.

Description of periods:

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

Period n Subshell No. of elements Element Name of Period

1- 1 1s 2 1H, 2He Shortest
2- 2 2s, 2p 8 3Li – 10Ne Short
3- 3 3s, 3p 8 11Na – 18Ar Short
4- 4 4s, 3d, 4p 18 19K – 36Kr Long
5- 5 5s, 4d, 5p 18 37Rb – 58Xe Long
6- 6 6s, 4f, 5d, 6p 32 55Cs – 86Rn Longest
7- 7 7s, 5f, 6d 26 87Fr – 112Uub Incomplete
DESCRIPTION OF GROUPS –

1st/IA/Alkali metals :
H = 1s1
Li = 1s2, 2s1
Na = 1s2, 2s2, 2p6, 3s1
K = 1s2, 2s2, 2p6, 3s2, 3p6, 4s1
General electronic configuration = ns1(n = Number of shell)
Number of valence shell e– = 1

2nd/IIA/Alkali earth metals :

Be = 1s2, 2s2
Mg = 1s2, 2s2, 2p6, 3s2
Ca = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2
General electronic configuration = ns2
Number of valence shell e– = 2

13th/IIIA/Boron Family :
B = 1s2, 2s2, 2p1
Al = 1s2, 2s2, 2p6, 3s2, 3p1
Ga = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p1
General electronic configuration = ns2 np1
Number of valence shell e– = 3

14th/IVA/Carbon Family :
C = 1s2, 2s2, 2p2
Si = 1s2, 2s2, 2p6, 3s2, 3p2
Ge = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p2
General electronic configuration = ns2 np2
Number of valence shell e– = 4

15th/VA/Nitrogen family/Pnicogen : (Used in fertilizer as urea)

N = 1s2, 2s2, 2p3

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

P = 1s2, 2s2, 2p6, 3s2, 3p3

As = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p3
General electronic configuration = ns2 np3
Number of valence shell e– = 5

16th/VIA/Oxygen family/Chalcogen : (Ore forming)

O = 1s2, 2s2, 2p4
S = 1s2, 2s2, 2p6, 3s2, 3p4
Se = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p4
General electronic configuration = ns2 np4
Number of valence shell e– = 6

17th/VIIA/Halogen family/Halogens : (Salt forming)

F = 1s2, 2s2, 2p5
Cl = 1s2, 2s2, 2p6, 3s2, 3p5
Br = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p5
General electronic configuration = ns2 np5
Number of valence shell e– = 7

18th/Zero group/Inert gases/Noble gases :

Ne = 1s2, 2s2, 2p6
Ar = 1s2, 2s2, 2p6, 3s2, 3p6
Kr = 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d10, 4p6
General electronic configuration = ns2 np6 (except. He)
Number of valence shell e– = 8

(v) 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 (Ionic potential = Charge/Radius) 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 becuase they represent the properties
of other element of their respective group.
(c) In 6th period all types of elements are included (s, p, d & f)
(d) No inert gas in 7th period.
(e) Normal elements present in all periods.
(f) Atomic No. of last inert gas element is 86.
(g) Long form of modern periodic table can be divided into four portions.
1. Left portion – IA & IIA – s-block.
2. Right portion – IIIA to VIIA + O group – p-block.
3. Middle portion – IIIB to VIIB + VIII + IB IIB – d-block.
4. Bottom portion – IIIB – f-block elements
(h) The group containing most electro positive elements – IA GROUP
(i) The group containing most electro negative elements – VIIA GROUP
(j) The group containing maximum number of gaseous elements – ZERO (18th) GROUP

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

(k) The group in which elements have generally ZERO valency – (18th) GROUP ZERO
(l) In the periodic table –
Number of Gaseous elements - 11 (H, N, O, F, Cl + Noble gases) GALIUM

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 - 89 (if discovered elements are 105)
- 95 (if discovered elements are 112)
st th
(m) No p-block elements in 1 and 7 periods.
(n) Ist period has all the elements in gaseous form (H, He)
(o) 0/18 group have all the elements in gaseous form.
(p) 2nd period contains maximum number of gaseous elements. They are 4 : N, O, F, Ne
(q) IIIB/3rd group is called longest group having 32 elements including 14 Lanthanides and 14 Actinides
Sc
Y
La ............... Lanthanides (14)
Ac ............... Actinides (14)

(vi) Nomenclature of elements :

(a) IUPAC gave names to elements above atomic No. 100 as follows -
0 1 2 3 4 5 6 7 8 9
nil un bi tri quad pent hex sept oct enn

(b) In all the elements suffix is - ium

e.g.

Atomic No. IUPAC Name Symbol

101 Un nil Unium Unu
102 Un nil bium Unb
103 Un nil trium Unt
104 Un nil quadium Unq
105 Un nil pentium Unp
106 Un nil hexium Unh
107 Un nil septium Uns
108 Un nil octium Uno
109 Un nil ennium Une
110 Un un nilium Uun

(vii) Merits of long form of periodic table -

(a) Position of isotopes - Atomic No. of isotopes are similar, so different isotopes can be placed at same place in
periodic table.
(b) (Ar - K) (Co - Ni) (Te - I) are now in increasing order of atomic number.

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

(c) Lanthanides and actinides are in IIIB group.

(d) In modern periodic table diagonal line separates out metals, metalloids and non metals.
(e) Elements of same group have same general formula of electronic configuration of outer most shell.

(viii) Demerits of long form of periodic table -

(a) Position of hydrogen is still controversial.
(b) ‗He‘ is a inert gas but it has different electronic configuration than other inert gas elements.
(c) Lanthanides and actinides are still not placed in main frame.
(d) Isotopes have different physical properties but have same place in periodic table.

4. Classification of Elements

(A) Bohr classification - Elements can be divided in four parts on the basis of electronic configuration.

(i) Inert gas elements -

(a) The elements in which ultimate orbit is completly filled up are called inert gas elements.
(b) General electronic configuration is ns2p6 (Except He = 1s2)
(c) Because of most stable configuration, they are very less reactive. Hence known as noble gas or inert gas.
(d) These elements are present in ‗0‘ group or 18 th group and 1 to 6th period of periodic table.
(e) Number of inert gas elements are 6(One in each period upto 6 th) He, Ne, Ar, Kr, Xe, Rn

(ii) Normal or Representative elements -

(a) The elements in which ultimate orbit is incomplete, while penultimate orbits are complete are called normal
elements.
(b) Their general electronic configuration is :
IA IIA IIIA IVA VA VIA VIIA
ns1 ns2 ns1np1 ns2np2 ns2np3 ns2np4 ns2np5

ns1–2 ns2 np1–5

(c) These elements lies in group IA to VIIA and period Ist to 7th
nd
(d) Elements of 2 period known as bridge elements.
(e) Elements of 3rd period (Na, Mg, Al, Si, P, S and Cl) are called typical elements. These are 7 in numbers.

(iii) Transition elements -

The elements in which both ultimate (n) as well as penultimate shells (n – 1) are incomplete either in atomic state
or in some oxidation state are called transition elements.
Note: According to this concept, Zn, Cd, Hg and Uub are not transition elements because they do not have
incomplete penultimate shell either in atomic state or in some oxidation state.
Zn = [Ar] 3d10 4s2
Zn+2 = [Ar] 3d10
(a) group – IIIB to VIIB + VIII + IB
Periods – 4th to 7th
(b) Electronic configuration (n – 1)d1–10 ns1 or 2
(c) Total number of d-block elements = 40
Total number of transition elements = 36 (Except Zn, Cd, Hg and Uub)
Note : All transition elements are d-block elements but all d-block elements are not transition elments.

(iv) Inner transition elements -

(a) The elements in which all the three shells that is ultimate (n) penultimate (n – 1) and pre or antipenultimate
(n – 2) shell are incomplete are called inner transition elements.

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

58C = [Xe] 6s2, 5d1, 4f1

(b) Electronic configuration -
(n – 2)f1 – 14 (n – 1)d0 or 1 ns2
(c) These are 28 in number.
(d) Group – IIIB
(e) Period – 6th & 7th
(f) Inner transition elements are divided into two series.
(A) Lanthanide series/Rare earth elements/Lanthenones (Ce58 – Lu71 14 elements)
The first element of this series is Cerium & not Lanthanum.
In these elements, last electron enters into 4f subshell.
They are present in IIIB group and 6th period of the periodic table.
Promethium (61Pm) is the only lanthanide which is synthetic and radioactive in nature.

(B) Actinide series/Man made elements/Actinones (Th90 – Lw103 14 elements)

The first element of this series is Thorium & not Actinium.
In these elements, last electron enters into 5f subshell.
they are present in IIIB group and 7th period of the periodic table.
All the actinides are radioactive in nature.
First three elements (Th, Pa, U) are found in nature while others are synthetic in nature.
After U92 i.e. from 93Np onwards elements are called transuranic elements because :
They are heavier than uranium.
They are derived from uranium by nuclear reactions.

5. Classification on the basis of subshell in which last electron enters


(i) s-block elements -
(a) In these elements last electron enters in s-subshell.
(b) Groups – IA, IIA + O group (He only)
(c) Period – 1 to 7th|
(d) Electronic configuration – ns1 – 2
IA group n = 1 to 7
IIA group n = 2 to 7
(e) Total s-block elements are (14) including H and He)
(f) Total s-block metals are (12) (excluding H), H is non-metal
General characteristics of s-block elements :
(a) s-block elements are soft metal, that is why these elements have low melting and boiling point.
(b) Their oxides and hydroxides are basic in nature.
(c) They act as reducing agent.
(d) They have very low ionisation energy and highly electropositive so, they form ionic compound.
(e) Flame of these elecments have the property of showing different colour.
(ii) p-block elements -
(a) Last e– enters in p-sub shell
(b) Group – IIIA (13) to VIIA(17) + 0 group (18) (except He)
(c) Period – 2nd to 6th
(d) Electronic configuration – ns2 np1 – 6
(e) Total p-block elements – (30)

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

Characteristic of p-block elements :

(a) p-block possesses all three kind to elements i.e. metals, non-metals and metalloids.
(b) Oxides of non-metals are acidic in nature.
(c) they form covalent compounds mostly.
(d) They are oxiding in nature.
(iii) d-block elements -
(a) Last e– enters in (n – 1)d subshell
(b) Group – IIIB – VIIB, VIII, IB, IIB or group 3 to 12 (IUPAC)
(c) Period – 4th to 7th
(d) Electronic configuration – (n – 1)d1 – 10 ns1 or 2
(e) Total d-block elements – (40)
Total transition elements – (36). If 112 elements are included in periodic table.
(f) IIB elements (Zn, Cd, Hg, Uub) are d-block elements but not transition elements.
General characteristics of d-block elemnets –
(a) They all are metals, which are very hard having high melting and boiling point.
(b) Elements of this block situated in between ‗s‘ and p-block elements. So the character of this block elements
lie between s and p-block elements
(c) They show variable oxidation - state, eg. Mn = Mn+2, Mn+3, Mn+4, Mn+5, Mn+6, Mn+7
(d) They form ionic and covalent bond both.
(e) They are good conductor of heat and electricity and form complex compounds.
(f) Metals, which have unpaired electrons show paramagnetism.
(g) They form alloys and most of the elements act as catalyst.

(iv) f-block elements -

(a) Differentiating e– enters in (n – 2)f subshell.
(b) Group – IIIB
(c) Period – 6th and 7th
(d) From at. no. 58 - 71, 6th period ; Lanthanide series 4f1 – 14 5d0 or 1 6s2
90 - 103 7th period; Actinide series 5f1 – 14 6d0 or 1 7s2
(e) Total number of f-block elements – (28)
(f) All the actinides are radioactive elements.
(g) Transuranic actinides are man made elements (Np93 – Lw103)
(h) Lanthanides are found rarely on earth so these are called rare earth metals.
General characteristics of f-block elements -
(a) All the f-block elements are heavy metals.
(b) It shows high melting and boiling point.
(c) The most common oxidation state of these elements is +3.
(d) The elements of 5f series are radioactive in nature.

Determination of period, block and group of an element -

(i) Period No. - The period no. of the element can be predicted from the principal quantum no. (n) of the valence
shell.
e.g. electronic configuration of iodine is :

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

1s22s22p6, 3s23p63d10, 4s24p64d10, 5s25p5. Therefore the period number of iodine is 5 as the valence shell
configuration is 5s25p5.
(ii) Block No. - The type of orbital which receives the last electron known as block no.
e.g. An element ‗X‘ has its electronic configuration is 1s22s22p63s23p64s23d8. As the last electron enters in the
d-orbital, therefore it is a d-block element.
(iii) Group No. - It is predicted from the number of electrons in the valence shell and penultimate shell as follows.
(a) For s-block elements, group number is equal to the number of electrons in the valence shell after the noble gas
core.
e.g. An element ‗Y‘ having electronic configuration 1s22s22p63s23p64s2 or [Ar] 4s2 has two electron in valence shell
and it is a s-block element. Therefore it belongs to group 2.
(b) For p-block element, the group number is equal to 10 + number of electrons in valence shell.
e.g. An element ‗Z‘ with electronic configuration as 1s22s22p63s23p63p104s24p3 has five electrons in its valence shell
and belongs to p-block.
Therefore its group number is 10 + 5 = 15. It belongs to group VA of the Mendeleev‘s periodic table.
(c) For d-block elements group number is equal to the number of elecrons in (n – 1)d sub-shell and valence
shell.
e.g. An elements ‗A‘ having electronic configuration as.
1s22s22p63s23p63p104s1. So its group number will be 10 + 1 = 11.

Predicting atomic no. of the successive member in a group or family –

(i) Magic Numbers –
Knowing the at. no. of the first member of a group, we can write that at. no. of the subsequent elements by adding
given magic no. For example

Group 1 2 3 4, 5, 6, 7, 8, 9, 10, 11, 12 13, 14, 15, 16, 17 18

IA IIA IIIB IIA IV V VI VII ‗0‘gp
I+ 2 – 8
PERIOD

II+ 8 8 8 8
III+ 8 8 18 18
VI+ 18 18 18 18 18 18
V+ 18 18 18 32 32 32
VI+ 32 32 32 32 – –
VII

(ii) In group IA – Atomic no. of H is 1 at. no. of other element will be as follows –
Magic no. H1 1 2 3 Li 3 8 11 Na 11 8 19 K 19 18 37 Rb 37 18 55
        
2 8 8 18 18

6. Periodicity

(i) 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.
(a) In a period, the ultimate orbit remain same, but the no. of e – gradually increases.

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

(b) In a group, the no. of e– in the ultimate orbit remains same, but the values of n increases.
(ii) Causes of periodicity -
(a) The cause of periodicity in properties is due to the same outermost shell electronic configuration conming at
regular intervals.
(b) In the periodic table, elements with similar peoperties occur at intervals of 2, 8, 8, 18, 18 and 32. These
numbers are called as magnic numbers.

7. Periodic Properties

7.1 VALENCY :
It is defined as the combining capacity of the elements. The word valency is derived from an Italian word
―Valentia‖ which menas combining capacity.
Old concept : Given by : Grankland
Valency with respect to Hydrogen and Chlorine : Valency of H 1
It is defined as the number of hydrogen or Chlorine atoms attached wtih a particular element.
IA IIA IIIA IVA VA VIA VIIA
NaH MgH2 AlH3 SiH4 PH3 H2S H-Cl
NaCl MgCl2 AlCl3 PCl3 SiCl3 PCl3 Cl-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
Na2O MgO Al2O3 SiO2 P2O5 SO3 Cl2O7
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 configurtion. 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–)

IA IIA IIIA IVA VA VIA VII 0

ns1 ns2 ns2np1 ns2np2 ns1np3 ns2np4 ns2np5 ns2np2
Valence shell e– 1 2 3 4 5 6 7 8
Valence 1 2 3 4 1 2 1 0
(8 – 5) = 3 (8 – 8) = 0
Note: All the elements of a group have same valencies because they have same number of valence shell electrons.

7.2 DENSITY:
(a) In a group volume of an atom increases along with atomic weight but atomic weight increases more than
atomic volue, So density increases in a group.
Mass M
Density (D) = =
Volume V

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

(b) In period - Density first increases till maximum and then decreases. (s-block to d-block increases, d-block to
p-block decreases)
(c) In group - From top to bottom in a group density increases regularly
e.g. In VIIA gp - F and Cl are gases (Low density)
Br is liquid (density 3.19 gm/cm–3)
I is solid (density 4.94 gm/cm–3)
(d) From s-block to p-block packing capacity and strength of bond increases.
(e) Exceptions - The density of Na and Mg is greater than K and Ca respectively. This can be explained by inner
shell configuration :
IA IIA
Li Be
Na Mg Na 1s22s22p63s1
K Ca K 1s22s22p63s23p63d04s1
In K, 3d10 orbital is vacant, 3rd orbit has the capacity to hold 18e– but it has only 8e–. Due to empty orbital
atomic volumes increases and so density devreases
Mg > Ca > Na > K
(f) Li is the lightest metal known.
(g) Highest density of solid metal Ir 922.63 gm/cc) and Os (22.6 gm/cc) and liquid metal Hg(13.6 gm/cc)
(h) Order of density of elements
Li < K < Na < Rb < Cs {In K and Ca density is less due to empty d-orbitals in inner shells}
Ca < Mg < Be < Sr
Sc < Y < La
Ti < Zr << Hf
Zn < Cd < Hg

7.3 BOILING POINTS AND MELTING POINTS :

(a) It is a property of aggregate of atoms and not of a single atom.
i.e. why it is a molecular property.
(b) In period - Along the period from left to right B.P. and M.P. first increases then decreases.
Alkali metals – Crystal structure BCC (low B.P. & M.P.)
Transition metals – ........ ― ........ FCC (High B.P. & M.P.)
Inert gases ................Lowest B.P. & M.P. (Vander wall force )
Transition elements................Highest M.P.

W(Tungston)Max. M.P. (3410º C)

Metals
Hg (Mercury )Lowest M.P. ( 38º C)

Carbon (In tha form of diamond)Highest M.P. (3727º C)

Non Metals
Helium Lowest M.P. ( 270º )
(iii) In group -
(a) In s-block elements B.P. & M.P. decreases down the group.
Li, Na (solid) Cs, Fr (liquid)
It is due to more repulsion of non-bonding electrons which weakens the metallic bond.
(b) In d-block elements B.P. & M.P. increases down the group (due to lanthanide contraction, zeff increases and
hence bond energy increases)

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

(c) In p-block elements

i- From IIIA – IVA group B.P. & M.P. decreases down the grou and from VA to ‗0‘ group, B.P. & M.P.
increases down the group. (Atomic or molecular wt vander wall force).
ii- B.P. and M.P. of monoatomic molecules are lesser than diatomic molecules. ‗0‘ group < Halogens.
iii- Atomic solid non metals like B, C and Si has higher B.P. and M.P. due to strong covalent bond.
iv- B.P. & M.P. of molecular solids are less because of weaker vander wall force among molecules eg. I 2.

8. Atomic Size

Atomic radius :
(a) It is distance between outermost e– and nucleus.
(b) Half of the nuclear distance between two atoms is defined as atomic radius.
(c) X-ray diffraction, e– diffraction method and nuclear magnetic resonance (NMR) spectrum methods are used to
determine internuclear distance or bond length.
Inter nuclear distance
Atomic radius =
2
(d) Atomic radius depends on the type of chemical bond between atoms in a molecule. These are :
i) Covalent radius ii) Ionic radius iii) metallic radius iv) Vander waal‘s radius

(i) Covalent radius : (SBCR = Single Bonded Covalent Radius)

(a) Covalent bonds are formed by overlapping of atomic orbitals.
(b) Internuclear distance is minimum in this case.
(c) Covalent radius is the half of the internuclear distance between two singly bonded homo atoms e.g.
internuclear distance of A–A(A2) molecule is (dA – A) and covalent radius is rA then
d A – A = r A + rA or 2rA
dA A
rA =
2
1.98
e.g. – In Cl2 molecule, internuclear distance is 1.98 Å so rCl = = 0.99 Å
2
(d) SBCR of O, N and C etc. elements can be determined by taking H 2O2, N2H4, C2H6 respectively.
Case I - For Heteroatomic molecule with no. E.N. difference.
For A – B molecule Electronegativities of A & B are approximately equal e.g. C – I
E.N. of C & I are approx equal (2.5) internuclear distance of C – I is 2.13Å
dC–1 = rC + r1 (rC is 0.77Å)
r1 = 2.13 – 0.77 = 1.36Å
Case II - Heteroatomic molecule with E.N. difference more :
Schemaker and Stevensos law :
If in a diatomic molecule electronegativities of A – B have more difference. Then actual bond length will be
reduced.
As per schoemaker & Stevenson – The reduction in bond length depends on the difference in
electronegativities of atoms by following manner -
d A – B = rA + rB – 0.09 (XA – XB)
Here XA is E.N. of A & XB is E.N. of B
e.g. - If bond length of F2 = 1.44Å, Bond length of H2 = 0.74Å.
Find out the bond length of H – F ? (EN of F is 4.0, EN of H is 2.1)
Solution - d H – F = rF + rH – 0.09 (XF – XH)

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

 dF–F = 1.44/2 = 0.77Å, dH–H = 0.72/2 = 0.37Å

dH–F = 0.77 + 0.37 – 0.09 (4.0 – 2.1)
= 1.09 – (0.09 × 1.9) = 1.09 – 0.171 = 0.919Å

Examples
based on Covalent Radius

Ex.3 A given compound A2 whose total dA – A is 1.4 Å . The atomic (covalent) radius of an atom A is -
(A) 0.7 Å (B) 0.5 Å (C) 0.2 Å (D) 0.1 Å Ans. (A)
d A–A
Sol. rA = 1.4/2 = 0.7 Å
2

Ex.4 A compound AB whose electronegativity difference is 1.9 . Atomic radius of A and B are 4 and 2 Å. The distance
between A & B means dA – B is –
(A) 6.72 Å (B) 5.82 Å (C) 6.9 Å (D) 7.5 Å Ans. (B)

Sol. Given rA = 4 Å
rB = 2Å
x = 1.9
By the formula dA – B = rA + rB – .09 ( x)
= 4 + 2 – .09 × 1.9
= 6 – 0.171
= 5.82 Å

(ii) Ionic Radius :

(A) Cationic radius :
(a) When an neutral atom loses e– it converts into cation (+ve charged ion)
Atomic radius > Cationic radius
because after loosing e– no. of e– reduces, but no. of protons remains same, due to its Zeff increases, hence
electrons pulls towards nucleus and atomic radius decreases, moreover after loosing all the elecrons from the
outer most shell, penultimate shell becomes ultimate shell which is nearer to nucleus so size dreases.
1
(b) Size of cation
Magnitude of the ch arg e or Zeff
e.g. Fe > Fe+2 > Fe+3
Pb+2 > Pb+4
Mn > Mn+2 > Mn+3 > Mn+4 > Mn+5 > Mn+6 > Mn+7
(B) Anionic radius :
(a) When neutral atom gains e– it converts into anion
Anionic radius > Atomic radius
(b) In an anion e– are more than protons so effective nuclear charge reduces, and inter electronic repulsion
increases, which also increases screening effect. So distance between e – and nucleus increases and size of
anion also increases.
e.g. Z of flourine is 9
F F–
Proton 9 9
–
e 9 10

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

Z 9 9
so = =1 = 0.9 As Zeff of F– is less than F so size of F– > F
e 9 10
(c) Size of iso electronic species :
– Those species having same no. of e– but different nuclear charge forms isoelectronic series.
– for isoelectronic species the atomic radius increases with decrease in nuclear charge
K+ Ca+2 Ar S–2 Cl–
Z 19 20 18 16 17
e 18 18 18 18 18
z 19 20 18 16 17
e 18 18 18 18 18
Order of radius: (S > Cl > Ar > K > Ca ), (N > O2– > F– > Ne > Na+2 > Mg+2 > Al+3)
–2 – + +2 3–

(iii) Metallic radius :

(a) Half of the nuclear distance between two adjacent metallic atoms in crystalline lattice structure.
(b) There is no overlapping of atomic orbitals
(c) so metallic radius > Covalent radius
1
(d) Metallic radius
Metallic bond strength
(e) More metallic radius loose crystal packing less bond strength
(body centred packing)
(f) Less metallic radius Tight crystal packing FCC High bond strength
(Hexagonal close packing)
(iv) Vander Waal’s radius :
(a) Those atoms (like noble gases) which are not bonded with each other, experiences a weak attractive force to
come nearer.
(b) the half of the distance between the nuclei of adjacently placed atoms in solid state of a noble gas is Vander
Waal‘s radius.
(c) Vander Waal radius > Covalent radius.
(d) Inert gas have only Vander Waal radius.
(e) In molecules of nonmetals both covalent and Vander Waal radius exists.
Cl2

Cl2

Cl2 momecules
Covalent radius = 0.99Å
Covalent radius
Vader Waal radius = 1.80Å
Vander Waal distance

Vander Waal radius 2 covalent radius

(f) VWR > Metallic R > Covalent R
(g) Vander Waal force of attraction Molecular wt. or atomic weight (in inert gases)
(h) In a period from left to right VWR decreses.
(i) In a group from top to bottom its values increases.
(v) Factors affecting atomic size are :
1
(a) Atomic radius Li > Be > B > C > N > O > F
Effective nuclear charg e

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

(b) Atomic radius No. of shells Li < Na < K < Rb < Cs

(c) Atomic radius Screening effect

1
(d) Atomic size Mn > Mn+2 > Mn+3 > Mn+4
Magnitude of ve charg e

Atomic size Magnitude of ve charge O < O– < O–2

1
(e) Atomic radius >N–N<>–N=N–>N N
Bond order
(vi) Periodic variation of atomic size :
i- Across a period – It decreases from left to right in a period as nuclear charge increases
e.g. Li > Be > B > C > N > O > F < Ne
ii- In a group – It increases from top to bottom in a group as number of shell increases
e.g. Li < Na < K < Rb < Cs
Exceptions : Transition elements
(a) From Sc21 to Zn30 in first transition series Zeff continuously increases, but atomic size does not decreases
continuously.
(b) From Sc21 to Mn25 size decreases
(c) From Fe26 to Ni28 size almost constant
Nuclear charge Screening effect
(d) From Cu29 to Zn30 size increases. s nuclear charge is less effective than screening effect.
(vii) Lanthanide Contraction :
(a) Outermost electronic configuration of inner transition elements is
(n – 2)f1 – 14, (n – 1)s2p6d0–1, ns2 n = 6 to 7)
(b) e– enters in (n – 2) f orbitals
(c) Mutual screening effect of e– is very less, because of complicated structure of f-orbital
(d) Nuclear charge increases by one (+1) in lanthanides and actinides so atomic size of these elements slightly
decreases. it is known as lanthanide contraction.
Here Nuclear charge > Screening effect.
(e) In transiton series Ist 2nd and 3rd
IIIB IVB
size Sc Ti size increases

Increases Y Zr
La Hf Equal due to lanthanide contraction
Radii 3d < 4d 5d except IIIrd B.
(viii) Orders of atomic and ionic radii -
H+ < H < H –
I+ < I < I –
Ti < Zr Hf
Sc < Y < La
Na+ < Ne < F–
Be < Li < Na
Ni < Cu < Zn
Sc > Ti > V > Cr

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

Ar > Na > Cl
Cu < Au < Ag

9. Ionisation Potential or Ionisation energy or Ionisation Enthalpy


(i) 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.
(ii) Successive I.E.
(a) For an atom M, successive ionisation energies are as follows -
M + E1 M+ + e– E1 = IP1
M+ + E 2 M+2 + e– E2 = IP2
M+2 + E3 M+3 + e– E3 = IP3
IP3 > IP2 > IP1
(b) e– can not be removed from solid state of an atom, it has to convert in gaseous form, Energy required for
conversion from solid state to gaseous state is called Sublimation energy.
(c) IP is always an endothermic process ( H = +ve)
(d) It is measured in eV/atom (electron volt/atom) or [Link]/mole or KJ/mole
(iii) Factors affecting ionisation potential :
(A) Atomic size : Larger the atomic size, smaller is the I.P. It is due to that the size of atom increases the
outermost electrons e– farther away fromt he nucleus and nucleus loses the attraction on that electrons and
hence can be easily removed.
1
IP
Atomic size
(B) Effective nuclear charge (Zeff) : I.P. increases with the increase in nuclear charge between outermost
electrons and nucleus.
(C) Screening effect : Higher is the screening effect on the outer most electrons causes less attraction from the
nucleus and can be easily removed, which is leading to the lower value of I.P.
1
IP
Screening effect
(D) Penetration power of sub shells :
(a) Order of attraction of subshell towards nucleus. (Penetration power) is - s > p > d > f
(b) As s-subshell is more closer to nucleus so more energy will be required to remove e– in comparision to p, d & f.
(c) Order of decreasing IP is s > p > d > f
Example IP1 of Be > IP12 of B
(1s22s2) (1s22s22p1)
–
After loosing one e , B attains electronic configuration of Be, so 2 nd IP of B is more than Be.
IP2 of B > Be
(E) Stability of half filled and fully filled orbitals :
(a) Half filled p3, d5, f7 or fully filled s2, p6, d10, f14 are more stable than others so it requires more energy.
e.g. In C, N, O, F
IP1 order is C < O < N < F
(b) Because of half filled p-orbitals in N, its ionisation energy (stability) is higher than O.
– IP1 order Na < Al < Mg
(c) Because s-orbital in Mg is completely filled and its penetration power is also hgiher than p-orbital (Al).
IP2 order Mg+ < Al+ < Na+
(2, 8, 1) (2, 8, 2) (2, 8)

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

(F) Oxidation state :

I.P. oxidation state of an atom. Ion with high oxidation state will have ionisation potential e.g.
Fe+3 > Fe+2 > Fe
(iv) IP & Periodic table :
In a group : Size increase so IE decrease.
Li Na K Rb Cs
Size increases
IE decreases
Exception :
– IP of Al = I.P. of Ga (While I.P. decreases down the group it is due to Transition contraction)
IP of Hf IP of Zr
(While I.P. should decreases down the group)
5d 4d
– It is due to lanthanide contraction
In a period : In a period atomic size decreases and zeff increases so removal of electron become difficult and
IE increases.
Li Be B C N O F Ne
atomic size decreases ,
zeff increases
IE increases .
IE = Ne > F > N > O > C > Be > B > Li
(v) Application of ionisation potential :
(A) Metallic and non metallic character :
Metallic P. Low (Na, K, Rb etc.)
non metallic I.P. High (F, Cl, Br etc.)
1
I.P.
Ionisation property
(B) Reactivity :
1
Reducing character
Ionisation character
(a) IA group has minimum I.P. so they are strong reducing agents in gaseous state
(Li < Na < K < Rb < Cs)
(b) VIIA group has maximum I.P. so they are strong oxidising agents (F > Cl > Br > I)
(D) Stability of oxidation states -
(a) If the difference between two successive I.P. 16eV then lower oxidation state is stable.

Na Na IP1
e.g. 42.7 eV
2
Na Na IP2
So Na+ is stable.
(b) If the difference between two successive I.P. 11 higher oxidation state is stable.

Mg Mg IP1
e.g. 7.4 eV
2
Mg Mg IP2
So Mg+2 is stable.

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

Al Al+
12.8 eV So Al+is stable
Al+ Al+2
6.0 eV So Al+3is stable
Al+2 Al+3
Al+ is stable only in gaseous state
Al+3 is stable in liquid and solid state
(E) Basic nature – It is property of elements with loosely held electrones
1
I.P.
Basic Pr operty
M2O > MO, Na2O > MgO, NaOH > Mg(OH)2, Cs2O > Rb2O > K2O > Na2O > Li2O

Examples
based on Ionisation Energy

Ex.5 I.E. of one H atom is 2.18 × 10–18J. The I.E. of H atom in kJ mole–1 is -
(A) 1505 kJ mole–1 (B) 1310 kJ mole–1
(C) 1608 kJ mole–1 (D) None Ans. (B)
18 23
2.18 10 J 6.02 10 atom
Sol. I.E. = × = 1.31 × 106 J mole–1 = 1310 kJ mole–1.
1atom mole

Ex.6 Which of the following order is correct of reducing strength -

(A) Cs > Rb > K > Na > Li (B) Li > Na > K > Rb > Cs
(C) Li > Cs > Rb > K > Na (D) None of these Ans. (C)
+
Sol. Li is the best reductant in IA group because oxidation potential of it is very high and Li (aq.) is most stable, since
Li+ is small cation. They have greater hydration energy . Hence the above process occurs easily.

10. Electron affinity/Electron gain enthalpy


(i) The amount of energy released or absored when electron is added to the valence shell of an isolated gaseous atom.
X + e– X– + E.A.
known as Electron affinity.
(ii) Mostly energy is released in the process of first E.A.
X + e– X– + EA1

(iii) If EA1 is exothermic then ( eg H (electron gain enthalpy) = – ve)

– EA1 is mostly positive
(iv) EA of neutral atom is equal to I.P. of its anion.
{Energy evolved in E.A. to convert neutral atom to anion} = {Energy absorbed to remove e – from anion}
EA –
i.e. X + e– X + Energy
IP
On adding 2nd electron in anion X–
X– + e – X–2 – EA2
or X– + e– + EA2 X–2
(v) egis endothermic process, i.e. energy has to given to introduce 2 nd electron in an anion, because repulsion
between negative charge on anion (X–) and 2nd electron.

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

(vi) Factors affecting electron affinity :

1
(a) Atomic size – EA
Atomic size
1
(b) Screening effect – EA
Screening effect
(c) Effect nuclear charge (Zeff) –
EA Zeff
(d) Stability of completely filled or half filled orbitals -
Electron affinity of filled or half filled orbital is very less or zero or energy is fiven to introduce any electron.
It is because of its stability.
(vii) In period
(a) Electron affinity increases along the period due to increase in Zeff and decrease in atomic size.
(b) Halogens posess maximum electron affinity due to small size and maximum z eff and after gaining one
electron. They attain a stable inert gas configuration.
(c) Electron affinity of IIA and noble gases is zero.
(d) In IInd period from 6C to 7N value of electron affinity decreases, because of half filled orbitals present in 7N
which is more stable.
(e) In IIIrd period value of electron affinity of Si is higher than P, because of half filled orbitals present in P.
(f) The value of electron affinity of inert gases is zero due to fully p-orbitals.
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
Zero Less zero
F > O > C > B > N > Be > Ne
Cl > S > Si > Al > P > Mg > Ar
(viii) In Group –
(a) Electron affinity decreases down the group. As the size increase and attraction on additional electron is less.
(b) Electron affinity of 3rd period element is greater than electron affinity of 2 nd period elements of the respective
group.
F 2s22p5
Cl 3s23p5
Due to small size of fluorine, electron density around the nucleus increses. The incoming electron suffers more
repulsion. In case of chlorine electron density decreases due to large size, decreasing order of electron affinity of
halogen. Cl > F > Br > I
S>O>P>N
Si > C > P > N
N & P have low electron affinity due to stable half filled configuration.
(ix) Application of Electron affnity -
(a) Electron affinity Oxidising nature
But F has more oxidising power than Cl because F has more standard reduction potential.
(b) Electron affinity Reactivity
– They form anions by gaining electron
– Their bond nature is ionic

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

(c) Electron affinity electronegativity

(d) Elements of high electron affinity form oxide and hydroxides, which are acidic in nature
(x) Difference between EN and EA
Electronegativity Electron Affinity
– Tendency of an atom in a molecule – Energy released when an electron is added to
to attract the bonded electrons neutral isolated gaseous atom
– Relative value of an atom – Absolute value of an atom
– It regularly changed in a period – It does not changes regularly
or group
– It has no unit – It is measured in eV/atom or KJ mol–1
or [Link] mole–1

11. Electronegativity (EN)


(i) The tendency of an atom to attract shared electrons towards itself is called electronegativity.
(ii) EN and EA both have tendency to attract electrons but electron affinity is for isolated atoms. Where as
electronegativity is for bonded atoms.
(iii) A polar covalent or ionic bond of A – B may be broken
as (a) A – B A– : + B+ (EN A > EN B)
+ –
or (b) A – B A + :B (EN A < EN B)
depending on their tendency to attract bonded electron.
(iv) There is no unit of electronegativity as EN is tendency of a bonded atom not an energy
(v) Pauling explained it first time.
(vi) In Pauling‘s scale, elements having almost same electronegativity are –
N = Cl = 3.0
C = S = I = 2.5
P = H = 2.1
Cs = Fr = 0.7
Be = Al = 1.5
(vii) EN of some other elements are as follows –
H
2.1
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Br
0 .8 2 .8
Rb I
0 .8 2 .5

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

Cs
0 .7
Fr
0 .7

– Small atoms are normally having more EN than larger atoms.

(viii) Factors Affecting electronegativity :
(a) Atomic size -
1
electronegativity
Atomic size
(b) Effective nuclear charge (Zeff) -
Electronegativity Zeff
(c) Hybridisation state of an atom -
Electronegativity % of s character in hybridised atom
sp > sp2 > sp3
s character 50% 33% 25%
Electronegativity 3.25 2.75 2.5
Because s-orbital is nearer to nucleus so by increasing s-character in hybridisation state, EN also in creases.
(d) Oxidation state -
Electronegativity oxidation state
+2 +4
Mn < Mn < Mn+7
O– < O < O +
Fe < Fe+2 < Fe+3
– As atomic radius decreases by increasing oxidation state of cation species, EN increases.
– In anionic species, the order of electronegativity is O –2 < O– < O
(e) Electronegativity does not depends on filled or half filled orbitals, because it is a tendency to attract bonded
electron, not to gain electron from out side.
(ix) Periodic table & Electronegativity :
(a) Electronegativity decreases down the group.
(b) In period on moving from left to right EN increases.

Exceptions -
– ‘O’ group – Electronegativity of ‗0‘ group is always zero, because inert gas do not form molecule.
(c) Electronegativity of Cs and Fr is 6th and 7th period (IA) are equal, it is because from 55Cs to 87Fr only one shell
increases but nuclear charge (No. of proton) increases by +32.
(d) So effect of nuclear charge balanced the effect of increase in number of shell.
Electronegativity of F > Cl but electron affinity of Cl > F
So Fluorine is called Black sheep element.
(e) In group of IIB elements (Zn, Cd, Hg) value of electronegativity increases down the group, because of
lanthanide contraction
(f) In IIIA group, value of electronegativity increases down the group, because of transition contraction
(+ 18 charge)
EN of Ga > EN of Al

(x) Application of electronegativity :

(A) Metallic and non metallic nature -

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

Low electronegativity Metals

High electronegativity Non metals
Metallic character increases down the group but decreases along a period.
(B) Bond length -
1
EN
Bond length
Here EN = difference in electronegativities of bonded atoms
HF < HCl < HBr < HI
– HF has minimum bond length because of much difference in the electronegativities of H and F.
(C) Bond energy - By increasing EN bond length decreases and hence bond energy increases.
Bond energy Electronegativity difference
HF > HCl > HBr > HI
(D) Acidic strength of hydrides -
Bond energy (Strength) stability of molecule.
– Order of stability of hydrohalides is
HF > HCl > HBr > HI and so order of their acidic strength will be -
HF < HCl < HBr < HI
– In VA group -
NH3 *Thermal stability decreases
PH3 *Basic character decreases
AsH3 *Acidic character increases

In PH3 and AsH3 there is less difference in the electronegativites of X A and XB, so their bond energy decreases and
hence acidic character (losing H+ ion) increases.
(E) Reactivity -
1
Bond energy Stability
Re activity
As bond energy difference of electronegativities
1
So, Electronegativity Stability
Re activity
HF HCl HBr HI
Reactivity
– HI is most reactive hydrohalides or strongest acid among all hydrohalides.
(F) Nature of bonds -
(a) It can be determined by Hanny & Smith formula -
Ionic % = 16(XA – XB) + 3.5 (XA – XB)2
Here XA = 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
(b) Gallis experimental values are -
XA – XB 1.7 Ionic
XA – XB 1.7 Covalent
– If XA = XB; then A – B will be non polar, e.g. H – H, F – F
If XA > XB and difference of EN is small then

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].
– +
A —— B bond will be polar covalent
–
e.g. H2O (H —— O —— H +)
+

– If XA >> XB and XA – XB EN is high then, A– B+ bond will be polar or ionic

e.g. Na+Cl–
– In HF, XA – XB = 1.9, which is more than 1.7, even then it is covalent compound.
(G) Nature of hydroxides -
(a) As per Gallis, In AOH if electronegativity of A is more than 1.7 (Non metal) then it is acidic in nature.
(b) If electronegavity of ‗A‘ is less than 1.7 (metal) then AOH will be basic in nature
e.g. NaOH ClOH
XA 0.9 3.0
Nature Basic Acidic
(c) If XA – XO X O – XH
then AO bond will be more polar and will break up as

A OH A+ + OH–
It show basic nature
(d) If XA – XO X O – XH

A O H H+ + AO–
It show acidic nature
e.g. 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
(H) Nature of oxides - Consider an oxide AO
If XA – XO > 2.3 Basic oxide
If XA – XO = 2.3 Amphoteric oxide
If XA – XO < 2.3 Acidic oxide
(a) Along a period acidic nature increases.
(b) Down the group basic nature increases
Li Be B C N O F
Na Mg Al Si P S Cl
XA – XO > 2.3 XA – XO < 2.3
Basic XA – XO = 2.3 Acidic
Amphoteric
i.e. when in periodic table the distance between the element and oxygen increases, basic character increases.
NO2 > ZnO > K2O

acidic character decreases

– BeO, Al2O3, ZnO, SnO, PbO, SnO2, PbO2, Sb2O3 etc. are amphoteric oxides.

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

– CO, H2O, NO, N2O are neutral oxides.

Acidic strength of oxide and oxyacid EN
B2O3 CO2 N2O5
EN increase, acidic nature increase

H3BO3 < H2CO3 < HNO3

SO3 H2SO4 EN
SeO3 H2SeO4 Acidic
TeO3 H2TeO4
H3PO4 > H3AsO4 > H3SbO4
H2SO3 > H2SeO3 > H2TeSO3
HOF > HOCl > HOBr > HOI
HClO4 > HBrO4 > HIO4
N2O5 > P2O5 > As2O5
N2O3 > P2O3 > As2O3 > Sb2O3

Acidic nature oxidation state

Acidic properties increases with increasing oxidation state of an element

HClO4 > HClO3 > HClO2 > HClO
HNO3 > HNO2
H2SO4 > H2SO3
SO3 > N2O3
Sb2O3 < Sb2O5 < N2O < NO < NO2 < N2O5
(I) Hydrolysis of AX - Where A = Other element
and X = Halogen
(a) If electronegativity of X > Electronegativity of A then on hydrolysis product will be HX.
– In example (BCl3), EN of Cl > EN of B
–
Cl H+ OH–
–
B +
Cl + H+ OH– 3HCl + B(OH)3
–
Cl H+ OH–
PCl3 + 3HOH 3HCl + H3PO3
PCl3. Cl2 + H2O 2HCl + POCl3
POCl3 + 3HOH 3HCl + H3PO4
(b) If electronegativity of X < electronegativity of A then on hydrolysis product will be HOX (hypohalous acid)
e.g. Cl2O
+
Cl
O– Here electronegativity of O > Cl
+
Cl
So On hydrolysis –

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TARUN KUMAR ASIWAL [Link]. CHEMISTRY , SLET , CSIR-NET , LL.B. , [Link].

–
Cl HO– H+
– –
O Cl + 2HOCl + H2O
–
Cl HO– H+

Examples
based on Electronegativity

Ex.7 Give the correct order of electronegativity of central atom in following compounds -
CH3 – CH3 , CH2 = CH2 , CH CH
(a) (b) (c)
The correct order is -
(A) a > b > c (B) c > a > b (C) c > b > a (D) b > c > a Ans (C)
Sol. % -S- character
in CH3– CH3 = sp3= 25 %
in CH2= CH2 = sp2= 33.33 %
in CH CH = sp = 50 %
So, the electronegativity order is :
CH CH > CH2 = CH2 > CH3 – CH3

Ex.8 Which of the following compound has highest value of bond length -
(A) CsF (B) CsBr (C) CsI (D) CsCl (Ans. C)

Sol. The E.N. of CsI is minimum.

Ex.9 The electronegativities of F and H are 4.0 and 2.1 respectively. The percent ionic character in H and F bond is -
(A) 43 (B) 34 (C) 94 (D) 39 Ans (A)
Sol. % Ionic character = 16 (4.0 – 2.1) + 3.5 (4.0 – 2.1)2 = 43

Ex.10 Which of the following order is correct for acidic property -

(A) SiH4 > PH3 > H2S (B) SiH4 = PH3 = H2S
(C) SiH4 < PH3 > H2S (D) SiH4 < PH3 < H2S Ans. (D)

Sol. The acidic character of hydrides increase in a period for non-metals.

33