INORGANIC CHEMISTRY (AS)

 The Periodic table

 Groups 2 , 17 , 15 and 16
 Transition elements

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THE PERIODIC TABLE (AS)

Trends in physical and chemical

properties
Across a period from left to right

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Periodic table
 1869 : proposed by Mendeleev
 63 elements arranged according to
increasing atomic mass
 1913 : modern periodic table proposed
by Moseley
 108/109 elements arranged according
to increasing atomic number

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 Structure of the Table

 Elements are arranged according to their atomic no.

 Period = the horizontal row
 Group = the vertical column
 Divided into sections:
 ‘s-block’ (Groups I and II) : outermost subshell ‘s’
 ‘p-block’ (Groups III to VIII):outermost subshell ‘p’
 ‘d-block’ with transition elements : partially filled d
subshell

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Diagonal relationship
 First element in any group usually
shows unusual behaviour unlike the rest
of the elements in the same group
 More similar to the second element in
the neighbouring group

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 Example :
 Group 1 2 13
 Li Be B

 Na Mg Al

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 Rxn Typical Li Mg
Group 1 (Group 1) (Group 2)
element
Heat No Li2O + CO2 MgO +
carbonate reaction CO2

Heat MNO2 + O2 Li2O + O2 MgO + O2

nitrate + NO2 + NO2

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 Trends in physical properties
( Physical periodicity )
 1. Atomic and ionic radii
 a. Atomic radius :
 i) Size of atoms = atomic (covalent) radii
 = half internuclear distance between 2
atoms of the same element joined by a
single bond
 Eg Cl - Cl Size of Cl = x/2

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x
 Note :atomic radius for other elements
 (1)Metals – metallic radius of the atom
in the metal
 (2)Noble gases -atomic/ VDW radius is
half the average distance between
adjacent non-bonded atoms -unusually
large value

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 ii) Atomic size decreases from left to right
due to increase in nuclear charge
 iii) Decrease in size becomes smaller with
increasing atomic number due to increased
repulsion between electrons
 Eg Li Be B C
Radius 0.123 0.089 0.080 0.077
Decrease 0.034 0.009 0.003

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 Period 2
Atomic Li
radius

Be

Atomic number

11
 Period 3 ( data from Data Booklet )
Unusually
Atomic large value

radius (VDW radius)

Ar Atomic number

12
 b. Ionic radius
 i) Positive ions :
 Atom - electrons  Positive ion
 (p = e) ( p > e)
 In ion , nuclear charge has greater pull on
remaining electrons
 Or sometimes positive ion has one shell less
than atom
 Size of positive ion smaller than neutral atom
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 ii) Negative ions :
 Atom + electrons  Negative ion
 (p = e) ( p  e)
 In ion , nuclear charge has weaker pull on
the electrons
 Also increased repulsion between electrons
 Size of negative ion bigger than neutral atom

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 c. Eg : Period 3
 i) Positive ions Na+ Mg2+ Al3+ Si4+
 Ionic radius 0.095 0.065 0.050 0.041
( nm)
 All ions are isoelectronic (10 e ), [Ne]
 From Na to Si, nuclear charge increases
 Attractive force on outer electrons increases
 Decrease in ionic radii

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 ii)Negative ions P3- S2- Cl-
 Ionic radius/nm 0.212 0.184 0.181
 All ions are isoelectronic ,18 e , [Ar]
 From P to Cl, nuclear charge increases
 Attractive force on outer electrons increases
 Decrease in ionic radii

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 iii)Radii of negative ions are larger than
that of positive ions
 Reasons :
 Extra shell of electrons in negative ions
( 18 e vs 10 e ) (*)
 Increased repulsion between larger no
of electrons
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 iv)Graph

Ionic
radius

Na+ Si4+ P3- Cl- Atomic

number
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 2. Melting* and boiling points :
 Depends on strength of the bonds and
on the structure in the solid state
 Eg Period 3 ( Na to Ar )
 Na Mg Al Si P S Cl Ar

Giant metallic Giant molecular

Simple molecular
structure structure
structure
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 a. Na , Mg , Al :
 Giant metallic structure
 Strong metallic bonds  high m.p
 M.p increases from Na to Al as metallic
bonds becomes stronger

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 Reasons : Increasing no of delocalised
electrons (*)
 Increasing nuclear charge
 Decreasing atomic radius

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 b. Si :
 Giant molecular structure
 Numerous strong covalent bonds
present
 Highest melting point

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 c. P to Ar :
 Simple molecular structure
 Weak VDW forces  low m.p
 Strength of VDW forces  no of electrons
 P4 S8 Cl2 Ar
no of electrons most least
VDW force strongest weakest
m.p / 0C 44 119 -101 -189
highest lowest
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 Note:
 Structure of P4 : tetrahedral

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 Sulphur, S8

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 Q) Why the M.P. of Mg is greater than Na?
Si A) Mg2+ has a higher charge density than Na+ , and more
number of delocalised electron hence stronger metallic
Melting bonds

Q) Why is the difference in M.P. of Al and Mg less than the

Point / 0 C difference of M.P. between Na and Mg?
A) There's a higher difference in strength of metallic bond
between Na and Mg and lesser difference in strength of
Mg Al metallic bond between Mg and Al, because all the valence
electron of Al are not entirely delocalised due to its high
charge density

Na S

P
Cl Ar

Atomic number

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 3. Electrical conductivity :
 In period 3 (from Na to Ar) , elements
change from metal to non metal
 a. Na , Mg , Al :
 Metals with metallic structures consisting of
cations in a sea of delocalised electrons
 Mobile electrons  Good conductors/high
conductivity
 Conductivity increases as no of delocalised
electrons increases from Na to Al

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 b. Si :
 Semi metal , semi conductor / moderate
conductivity
 c. P to Ar :
 Non metals , exists as simple discrete
molecules
 All electrons paired in covalent bonds
 No free electrons or ions  non conductors/
low conductivity
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Electrical Al
conductivity

Na

Si

Atomic number

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 4. Ionisation energy ( first I.E ) :
 a. Generally , the I.E of elements
increase across a period due to
 i) increase in nuclear charge (*)

 ii)slight decrease in atomic radius

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 Note : However there are anomalies :
 (1)between elements in Groups 2 and 13 ,
and
 (2)between elements in Groups 15 and 16

 b. In any period , the elements in Group 18

( inert or noble gases ) being stable have the
highest first I.E

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 Q) Why are 1st ionization
energies of first transition series
First I.E (d-block elements of 4th period,
Sc to Cu, largely similar across
the period?
A) In d-block elements of 4th
period, the d subshell gradually
fills from Sc to Cu, this increases
the shielding effect on the outer
4s electrons, off-setting
Ar (countering) the increase in
P effective nuclear charge.
Cl
Mg S
Si
Na Al

Atomic number

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 5. Electronegativity :
 a. Definition : electronegativity of an
element is a measure of its attraction
for bonding electrons
 b. Electronegativities increases from left
to right across a period due to
 increase in nuclear charge

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 c. Electronegativity decreases down a
group
 due to increase in shielding effect

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 Changes in Physical Properties of
Elements in a Period
Property Na Mg Al Si P S Cl Ar

Proton # 11 12 13 14 15 16 17 18

Ionisation energy 500 740 580 790 1010 1000 1260 1520
(kJ/mol)
Covalent bond 0.15 0.136 0.125 0.117 0.110 0.104 0.099 0.19
radius (nm) 6 2
Electronegativity 1.0 1.25 1.45 1.74 .05 2.45 2.85

Structure Giant Giant Simpl

Metal molec e
-lic -ular Molec
-ular
Density (gcm-3) 0.97 1.74 2.70 2.33 1.82 2.07 gas Gas

Melting pt (oC) 98 651 660 1410 44 119 -101 -189

low high high high low low low low
Boiling pt (oC) 890 1117 2447 2355 280 445 -35 -186
Electrical high high high mode low low low low
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conductivity rate
Trends in chemical properties
(chemical periodicity)

Eg : elements in period 3
( Na to Ar )

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 Reaction with water
 1. 2Na + 2H2O  2NaOH + H2

slow
 2. a. Mg +2H2O Mg(OH)2 +H2 (g)
cold

Al reacts very slowly with
water due to formation of
Al2O3 layer on the surface.
Al + 3H2O --> Al2O3 + 3H2
Obs: very slow bubbling,
white solid form (white
layer forms on the surface
of Aluminium)
b. Mg + H2O  MgO + H2(g)
steam
Silicon, Sulfur and
Phosphorous don't react
with water under normal
conditions
Why?
High 1st I.E. & low
oxidizing ability of Si,S,P
fast
Cl2 + H2O --> HOCl(aq) +
HCl(aq)
No particular observation
as aqueous solutions are
formed. HOCl is a strong
oxidizing agent.
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Reaction with oxygen
( Na to S )
 1. 4Na + O2  2Na2O
 Observation : burns with yellow flame
to form white solid
 2. 2Mg (s) + O2(g)  2MgO (s)
white
The reaction has high EA Does
not happen at rtp. Mg has to be
heated strongly

 Observation : burns with intense white

flame to form white solid
 3. 4Al + 3O2  2Al2O3
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 4. Si + O2  SiO2 burns very slowly

 5. P4 + 5O2  P4O10
 white solid at rtp
 (or 4P + 5O2  P4O10 )
 Observation: burns with white/yellow
flame.
 Another possible compound : P4O6

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 6. S + O2  SO2
 Observation: burns with a blue flame/
choking or pungent gas produced
 Further oxidation: 2SO2 + O2  2SO3

Cl2 does not directly

react with Oxygen
under normal
conditions. Nor does
Ar 40
Reaction with chlorine
( Na to P )
 1. 2Na + Cl2  2NaCl
 white solid
 Observation : burns with yellow flame /
forms white solid /colour of Cl2 disappears
 2. Mg + Cl2  MgCl2
 Observation : burns with intense white
flame / forms white solid

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 1800 C
 3. 2Al + 3Cl2  2AlCl3  Al2Cl6
covalent
simple molecular
ions formed in aq soln
Al3+(aq) or [Al(H2O)6]3+ and Cl-(aq)
Note : Al2O3 is ionic as difference in
electronegativity between Al and O is larger

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 Method :
 Pass dry chlorine gas over heated
aluminium foil in a tube.

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 4. Si + 2Cl2  SiCl4 (l)
slow reaction,
 colorless liquid
formed

 5. P4 + 10Cl2  4PCl5 (s)

 white solid
 ( or 4P + 10Cl2  4PCl5 )
 Observation : burns with white flame / forms
white solid
 Another possible compound : PCl3 , colourless
liquid
2S + Cl2 --> S2Cl2
foul smelling liquid
formed 44
Oxides of elements in Period 3
I) Trend in acidity of oxides :
Na2O MgO Al2O3 SiO2 P4O10 SO3

Ionic oxide Mainly ionic

Covalent oxide
Basic oxide Oxide
Acidic oxide
Amphoteric oxide
Oxides becomes more acidic across the period

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 1. Na2O : basic oxide
 a. dissolves in water  strongly alkaline
solution
 Na2O + H2O  2NaOH (pH=13)
 NaOH + HCl  NaCl + H2O
(alkali)

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 b. able to neutralize acids
 Na2O + 2HCl  2NaCl + H2O

 2. MgO : basic oxide

 a. dissolves slightly in water  weakly
alkaline solution

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 MgO + H2O  Mg(OH)2 Mg2+ + 2OH-
pH = 9
 Mg(OH)2 + 2HCl  MgCl2 + 2H2O
(alkali)

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 b. able to neutralize acids :
 MgO + 2HCl  MgCl2 + H2O

 3. Al2O3 :
 a. stronger ionic bonds not broken by
water
 therefore insoluble in water
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 b. nature of oxide : amphoteric
 i) Al2O3 + 6H+  2Al3+ + 3H2O
 acid
 ii) Al2O3 + 2OH- + 3H2O  2Al(OH)4-
alkali aluminate ion
Example:
Al2O3 + 2NaOH + 3H2O --> 2NaAl(OH)4

Al2O3 + 6HCl --> 2AlCl3 + 3H2O

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 c. nature of hydroxide : amphoteric
 i) Al(OH)3 + 3H+  Al3+ + 3H2O
 ii) Al(OH)3 + OH-  Al(OH)4-
 4. SiO2 :
 a. giant molecular structure with strong
Si – O bonds not broken by water ,
therefore insoluble in water
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 b. nature of oxide : acidic oxide
SiO2 + 2OH-  SiO32- + H2O
hot , conc silicates
Example
Notes : SiO + 2NaOH --> Na SiO + H O
2 2 3 2

(1) no reaction with aqueous alkali

(2) SiO2 + O2-  SiO32-
acidic basic silicates
Example
SiO2 + CaO --> CaSiO3 52
 5. Oxides of P and S: P4O6 / P4O10*, SO2 /SO3
 a. nature of oxide : acidic oxide
 b. hydrolyses in water  acidic solutions
 i) P4O10 + 6H2O  4H3PO4 (phosphoric
Vigorous
reaction acid)*
 ii) P4O6 + 6H2O  4H3PO3 (phosphonic
acid)
 Observation : white solid dissolves Vigorous
reaction

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 iii) SO2 + H2O  H2SO3 (sulfurous
acid)
 iv) SO3 + H2O  H2SO4

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 c. able to neutralize alkali :
 i) P4O10 + 12OH-  4PO43- + 6H2O
phosphate
 ii) SO2 + 2OH-  SO32- + H2O
sulfite
 iii) SO3 + 2OH-  SO42- + H2O
P4O10 + 12NaOH --> 4Na3PO4 + 6H2O
P4O6 + 12NaOH --> 4Na3PO3 + 6H2O

SO2 + 2NaOH --> Na2SO3 + H2O

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SO3 + 2NaOH --> Na2SO4 + H2O
II) Trends in physical
properties of the oxides
Related to structure and bonding
Na2O MgO Al2O3 SiO2 P4O10 SO3

Ionic oxides Covalent oxide Covalent oxide

Giant ionic structure Giant molecular Simple molecular
structure structure

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 1. Na2O , MgO , Al2O3 :
 a. ionic with giant ionic structure
 b. strong ionic bonds , therefore high
m.p
( m.p MgO  Al2O3  Na2O )
 c. presence of mobile ions,
good electrical conductor in aqueous
solution or molten state 57
 2. SiO2 :
 a. covalent with giant molecular
structure
 b. numerous strong covalent bonds
between atoms , therefore relatively
high m.p
( lower than m.p of MgO and Al2O3 ,
but higher than Na2O )
58
 c. molecular , all electrons paired in
covalent bonds
no free electrons or ions  non
conductor

 3. P4O10 , SO3 :
 a. covalent with simple molecular
structure
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 b. exists as discrete molecules held by
weak VDW forces  low m.p
 m.p of P4O10 (more electrons)  SO3
 c. molecular , all electrons paired in
covalent bonds ,
no free electrons or ions ,
therefore non conductor
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m.p of
oxides

Na Mg Al Si P S Atomic no
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Chlorides of elements in
Period 3
 I)Reaction with water
 1. NaCl : dissolve in water without
chemical reaction  neutral solution
NaCl (s)  Na+ (aq) + Cl- (aq)
 2. MgCl2 :
 a. ionic with a little covalent character

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  b. relatively high charge density on
Mg2+ causes polarisation of water
 Undergoes slight hydrolysis in water to
form slightly acidic solution (pH=6.5)
MgCl2 + H2O  Mg(OH)Cl(s) + HCl(aq)
Equation to show
slight hydrolysis of
water by MgCl2 

 However only very slight reaction –

observation : dissolves without reaction
Equation to show dissolution of MgCl2 in water
MgCl2 (s) + aq --> Mg2+(aq) + 2Cl-(aq)
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 3. AlCl3 :
 a.covalent with a little ionic character
 b.high charge density on Al3+ polarises
water
 Undergoes substantial hydrolysis in
water to form acidic solution ( pH=3 )

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 AlCl3 + 6H2O  [Al(H2O)6]3+ + 3Cl-
covalent ionic
 [Al(H2O)6]
3+ + H O  [Al(H O) OH]2+
2 2 5
+ H3O+
( first of 3 equations , polarisation continues )
Overall equation :
AlCl3 + 3H2O  Al(OH)3 + 3HCl (*) gas (white
Burst of HCl

fumes) forms
H=exothermic with limited H O 2

Single Equation to show hydrolysis of water by Aluminium Chloride

AlCl3 + 6H2O --> [Al(H2O)5(OH)]2+ + H+ + 3Cl- 65
 4. SiCl4 ,PCl3/PCl5
 a. covalent chlorides
 b. hydrolysed in water  strongly acidic
solution ( pH = 0 – 3 )
 SiCl4 + 2H2O  SiO2 + 4HCl(g) HCl(g):
Observation
 PCl3 + 3H2O  H3PO3 + 3HCl(g) white fumes
 PCl5 + 4H2O  H3PO4 + 5HCl(g) SiO2 white
solid
66
II)Trends in physical
properties of the chlorides
 Related to structure and bonding

 NaCl MgCl2 AlCl3 SiCl4 PCl5

Covalent Covalent
Ionic
Layered Simple
Giant ionic
structure structure molecular
structure

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 1. NaCl , MgCl2 :
 a. ionic with giant ionic structure
 b. strong ionic bonds therefore high
m.p/b.p
( m.p NaCl  MgCl2 )
 c. presence of free ions : good
conductor when molten or in aqueous
solution
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 2. AlCl3 :
 a. predominantly covalent with layered
structure in the solid state
 b. in each layer , all AlCl3 molecules are
joined by dative bonds and forms a
giant structure
 Layers are held together by weak VDW
forces
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 c. when it melts , the VDW forces and
dative bonds have to be broken
relatively high m.p / b.p but lower than
that of ionic chlorides
 d. molecular , all electrons paired in
covalent bonds
no free electrons or ions
therefore non conductor
70
71
 3. SiCl4 , PCl5 / PCl3 :
 a. covalent with simple molecular
structure
 b. i) exist as discrete molecules held by
weak VDW forces
therefore low m.p / b.p

72
 ii) m.p of PCl5 > m.p of SiCl4
 Reason :
 no of electrons in PCl5 > SiCl4
 stronger VDW forces , higher b.p/m.p
 PCl5 ( white solid ) ,
 SiCl4 ( colourless liquid )

73
 c. molecular , all electrons paired in
covalent bonds
no free electrons or ions
therefore non conductor

74
b.p of
chlorides

Na Mg Al Si P Atomic no
75
Patterns in the formula of
compounds (oxides & chlorides)
 1. Oxidation no of the element = no of
electrons used for bonding
 Eg Compound Oxidation no
SO2 +4
Na2O +1
PCl3 +3

76
 2. Many of the oxidation no corresponds to
loss or gain of enough electrons to obtain
a stable octet in its outermost shell.
 Eg Na - 1e  Na+
 1s22s22p63s1 1s22s22p6

 P + 3e  P3-
 [Ne]3s23p3 [Ne]3s23p6

77
 3. The maximum oxidation no = group no
 = no of valence electrons
 Egs: oxides
 a. S (Group 16) : forms SO2 and SO3
 max oxidation no (in SO3 )= +6

 b. P (Group 15) : forms P4O6 and P4O10

 max oxidation no in P4O10 = + 5

78
 Trend in maximum oxidation:
 Increases across the period
 Na Si Cl
 +1 +4 +7

79