Periodic Properties of Elements in the Periodic Table

Chapter 38

Periodic Table (Modern Form)

Periodic Law

The properties of elements are a periodic function of their atomic number

P = F(z)

Periodic Law

When elements are arranged in order of atomic number, similar properties recur periodically.

Atomic radii vs. Z K Na Li

Periodic Law
First Ionization Energy Atomic number

Why Periodic Law?
Chemical and Physical properties Type of Bonding and structure

Atomic properties

Atomic number

Ionization Energies
He Variations: 2. Across a period 3. Down the group Ne N H Li Be B C O Na F Mg Al Ar P Si S Cl K Ca

First I.E.

Atomic number

Atomic radius
K Ca Na Li Be H He Ne Ar Mg

Atomic Radius (pm) 1pm=1x10-12m
H 37 Li Be 156 105 Na Mg 186 160 B 91 C 77 N 71 O 60 F 67 He 54 Ne 80 Ar 96

Al Si P S Cl 143 117 111 104 99

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 231 197 161 154 131 125 118 125 125 124 128 133 123 122 116 115 114 99 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 243 215 180 161 147 136 135 132 132 138 144 149 151 140 145 139 138 109 Cs Ba 265 210 Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 154 143 137 138 134 136 139 144 147 189 175 155 167 145

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 187 183 182 181 181 180 199 179 176 175 174 173 173 194 172

Electronegativity
Electronegativity

F Cl H Li He Na K Ca

Ne Ar Atomic number

Electronegativity
Increase in electronegativity H 2.1 Be 1.5 Mg 1.2 He N O F Ne B C 2.0 2.5 3.0 3.5 4.0 P S Cl Al Si Ar 1.5 1.8 2.1 2.5 3.0 -

Decrease Li 1.0 Na 0.9

K Al 0.8 1.0

Melting Points
m.p./oC
4000 3000 2000 1000 0 -1000 0

C

Si Ca He
5

Ne
10 15

Ar
20

Atomic number

Melting Points
Increase H
-259

He
-270

Li
180

Be
1280

B Al

C Si

N P
44.2

O S
119

F Cl
-101

Ne
-249

2300 3730

-210 -218 -220

Na
97.8

Mg
650

Ar
-189

660 1410

K

Ca

63.7 850

Unit: oC

Periodic Variation of Physical Properties

Structure & Bonding

Giant metallic → Giant covalent → Simple molecular

Periodic Variation of Chemical Properties

Formulae of hydrides, oxides, chlorides Hydrolytic behaviours and explanations

Peiodicity in formulae
Moles of Cl atoms per mole of atoms of element 6 4 2

Li Be B C N O F Ne Na Mg Al Si P S Cl Ar

Hydrides
Period 2 Period 3 LiH BeH2 B2H6 CH4 NH3 H2O HF SiH4 PH3 H2S HCl Typically Polar Covalent covalent

NaH MgH2 AlH3 Ionic Covalent with some ionic character

Hydrides
Bonding
Ionic

Hydrolytic behaviour
NaH + H2O → NaOH + H2 (H- + H2O → OH- + H2)

Covalent withBeH2 + 2H2O → Be(OH)2 + 2H2 ionic character MgH2+ 2H2O → Mg(OH)2 + H2 B2H6 + 6H2O → 2H3BO3 + 6H2 AlH3 + 3H2O → Al(OH)3 + 3H2

Be(OH)2, Mg(OH)2, Al(OH)3 are alkaline H3BO3 is acidic

Hydrides
Typically CH4 does not dissolve nor react Covalent SiH4 reacts to give SiO2.2H2O + H2 PH3 very slight soluble H Si H H H :OH2 H H Si H OH + H2 etc

Hydrides
Polar covalent NH3 + H2O → NH4+ + OHH2S + H2O → H3O+ + HSHF + H2O → H3O+ + FHCl + H2O → H3O+ + ClNote: From gp4 to gp7 Acidity increases because polarity of bond increase

Check point 38-3
H-O-H + H2O: + :NH3 H-Cl OH- + NH4+ H3O+ + Cl-

N is more electronegative, hence more basic than Cl. It reacts with water by donating its lone pair electron. CH4 , due to its non-polar covalent bond, it does not dissolve nor react with water.

Oxides
Ionic Ionic with Covalent character Covalent Basic Na2O Al2O3 CO2 SO2 NO2

Amphoteric Acidic

Ionic Oxides
O2- + H2O → 2OHNa2O(s) + H2O(l) → 2NaOH(aq) Li2O(s) + H2O(l) → 2LiOH(aq) MgO(s) + H2O(l) → Mg(OH)2(s)

Amphoteric Oxides
BeO + 2H+ → Be2+ + H2O BeO + 2OH- + H2O → [Be(OH)4]2Al2O3 + 6H+ → 2Al3+ + 3H2O Al2O3 + 2OH- + 3H2O → 2[Al(OH)4]-

Covalent Oxides
Mechanism of the Hydrolytic behaviour of covalent oxides: O=Xδ+ :O-H H

[O-X-OH]- + H+

CO2 + H2O  H2CO3  H+ + HCO3SO2 + H2O  H2SO3  H+ + HSO32NO2 + H2O → HNO3 + HNO2

Covalent Oxides
P4O6 and P4O10 : P4O6(s) + 6H2O(l), cold → 4H3PO3(aq) P4O6(s) + 6H2O(l), hot→ 3H3PO4(aq) + PH3(g) P4O10(s) + 6H2O(l) → 4H3PO4(aq) The actual reactions are complicated. The products formed depend on the amount of water present and the conditions of reaction.

Covalent Oxides
Group VIIA: F2O, Cl2O and Cl2O7 F2O(g) + H2O(l) → 2HF(aq) + O2(g) Cl2O(g) + H2O(l) → 2HOCl(aq) Cl2O7(l) + H2O(l) → 2HClO4(aq) O Cl O O O Cl O O Cl O O Cl2O7(s) + O O Cl O O -

O O Cl2O7(g)/(l)

Check point 38-4
• SiO2 does not react with water. The giant covalent structure has high lattice energy. It is not possible to break it down in aqueous solution.

Chlorides
LiCl BeCl2 BCl3 CCl4 NCl3 OCl2 ClF AlCl3 SiCl4 PCl5 S2Cl2 Cl2 PCl3 SCl2 Covalent

NaCl MgCl2 Ionic

Intermediate with covalent character

Ionic chlorides

Group IA

LiCl, NaCl are not hydrolysed in aqueous solution, neutral solution formed when dissolved. NaCl (s) → Na+(aq) + Cl-(aq), LiCl (s) → Li+(aq) + Cl-(aq) MgCl2 is not hydrolysed. Hydrated crystals undergoes hydrolysis when heated. MgCl2.6H2O → MgCl(OH) + 5H2O + HCl

Group IIA
 

Intermediate chlorides
BeCl2 and AlCl3 : Be2+ and Al3+ High charge/size ratio, strong polarizing power, cation hydrolysis. Be2+ :O H H Be(OH)2 + HCl :OH2

BeCl2 + 2H2O

AlCl3 + 3H2O → Al(OH)3 + 3HCl

Covalent chlorides
Group IIIA BCl3 Cl Cl B
δ+

:OH2 Cl

Due to presence of vacant orbital and the polar B-Cl bond. BCl3 reacts vigorously with water to give boric acid, H3BO3 and HCl. BCl3(l) + 3H2O(l) → H3BO3 (aq) + 3HCl(aq)

Covalent chlorides
Group 4A : CCl4 and SiCl4 Cl C Cl Cl Cl Cl Cl Si Cl Cl

CCl4 does not hydrolyzed by water SiCl4 hydrolyzes. SiCl4(g) + 4H2O(l) → SiO2.2H2O(s) + 4HCl(aq)

Covalent chlorides
Group VA: NCl3 NCl3(l) + 3H2O(l) → NH3(aq) + 3HOCl(aq)
chloric(I) acid

:O

H H

:Nδ-Cl3

N does not have low-lying vacant orbital, it hydrolyses through the donation of lone pair electron of N atom to the H atom of water molecule.

Covalent chlorides
Group VA: PCl3 and PCl5 PCl3(l) + 3H2O(l) → H3PO3(aq) + 3HCl(aq) PCl5(s) + 4H2O(l) → H3PO4(aq) + 5HCl(aq) P is less electronegative than Cl. PCl3 and PCl5 hydrolyze by accepting the electron pair from water molecule.

Covalent chlorides
Group VI: SCl2 , S2Cl2 SCl2(g) + H2O(l) → HSCl(aq) + HOCl(aq) S2Cl2(l) + 2H2O(l) → H2S(g) + SO2(g) + 2HCl(aq) Group VII: FCl, Cl2 FCl(g) + H2O(l) → HF(aq) + HOCl(aq) Cl2(g) + H2O(l) → HCl(aq) + HOCl(aq)

Check point 38-5
Give the equation for the reaction between the following compounds with water: • AlCl3 • Cl2O6

Past paper questions
Periodicity 1999 IIA 3c 2001 IIA 3c

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