Chapter-07: The P-Block Elements

 The p-Block elements:

Elements belonging to groups 13 to 18 of the periodic table are called p-block elements.
 General electronic configuration of p-block elements:
The p-block elements are characterized by the ns2np1-6 valence shell electronic
configuration.
 Representative elements:
Elements belonging to the s and p-blocks in the periodic table are called the
representative elements or main group elements.
 Inert pair effect:
The tendency of ns2 electron pair to participate in bond formation decreases with the
increase in atomic size. Within a group the higher oxidation state becomes less stable
with respect to the lower oxidation state as the atomic number increases. This trend is
called ‘inert pair effect’. In other words, the energy required to unpair the electrons is
more than energy released in the formation of two additional bonds.
GROUP 15 ELEMENTS
 Nitrogen family:
The elements of group 15 – nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb)
and bismuth (Bi) belong to configuration is ns2np3.
 Atomic and ionic radii:
a) Covalent and ionic radii increase down the group.
b) There is appreciable increase in covalent radii from N to P.
c) There is small increase from As to Bi due to presence of completely filled d or f
orbitals in heavy elements.
 Ionisation energy:
a) It goes on decreasing down the group due to increase in atomic size.
b) Group 15 elements have higher ionisation energy than group 14 elements due to
smaller size of group 15 elements.
c) Group 15 elements have higher ionization energy than group 16 elements
because they have stable electronic configuration i.e., half-filled p-orbitals.
 Allotropy:
All elements of Group 15 except nitrogen show allotropy.
 Catenation:
a) Nitrogen shows catenation to some extent due to triple bond but phosphorus
shows catenation to maximum extent.
b) The tendency to show catenation decreases down the group.
 Oxidation states:
a) The common oxidation states are +3, +5 and –3.
 b) The tendency to show –3 oxidation state decreases down the group because of
decrease in electronegativity by the increase in atomic size.
c) The stability of +5 oxidation state decreases whereas stability of +3 oxidation
state increases due to inert pair effect.
d) Nitrogen shows oxidation states from –3 to +5.
e) Nitrogen and phosphorus with oxidation states from +1 to +4 undergo oxidation
as well as reduction in acidic medium. This process is called disproportionation.
3HNO2  HNO3  H2O  2NO
 Reactivity towards hydrogen:
a) All group 15 elements from trihydrides, MH3.
b) It belongs to sp3hybridisation.
c) The stability of hydrides decreases down the group due to decrease in bond
dissociation energy down the group.
NH3 > PH3 > AsH3 > SbH3 > BiH3
 Boiling point:
PH3 < AsH3 < NH3 < SbH3 < BiH3
a) Boiling point increases with increase in size due to increase in van der Waals
forces.
b) Boiling point of NH3 is more because of hydrogen bonding.
 Bond angle:
NH3 (107.8°) > PH3 (99.5°) > AsH3 (91.8°) ≈ SbH3 (91.3°) > BiH3 (90°)
a) Electronegativity of N is highest. Therefore, the lone pairs will be towards
nitrogen and hence more repulsion between bond pairs. Therefore bond angle is
the highest. After nitrogen, the electronegativity decreases down the group.
d) Basicity decreases as NH3 > PH3 > AsH3 > SbH3 < BiH3. This is because the lone
pair of electrons are concentrated more on nitrogen and hence the basicity will be
maximum in the case of NH3. It will decrease down the group as the
electronegativity decreases down the group. The reducing power of hydrides
increases down the group due to decrease in bond dissociation energy down the
group.
 Reactivity towards oxygen:
a) All group 15 elements from trioxides (M2O3) and pentoxides (M2O5).
b) Acidic character of oxides decreases and basicity increases down the group. This
is because the size of nitrogen is very small.
c) It has a strong positive field in a very small area. Therefore, it attracts the
electrons of water O-H bond to itself and release H+ ions easily.
d) As we move down the group, the atomic size increases and so, the acidic
character of oxide decreases and basicity increases down the group.
 Reactivity towards halogen:
Group 15 elements form trihalides and pentahalides.
a) Trihalides
 These are covalent compounds and become ionic down the group with sp 3
hybridisation, pyramidal shape.
b) Pentahalides
i) They are lewis acids because of the presence of vacant d – orbitals.
ii) They possess sp3d hybridisation and hence possess trigonal birpyamidal
shape.
PCl5 Cl   [PCl6]
iii) PCl5 is ionic in solid state and exist as[PCl4 ][PCl6 ] .
iv) In PCl5, there are three equatorial bonds and two axial bonds. The axial bonds
are longer than equatorial bonds because of greater repulsion from equatorial
bonds.
v) Nitrogen does not form pentahalides due to absence of d- orbitals.
 Reactivity towards metals:
All elements react with metals to form binary compounds in –3 oxidation state.
 Anomalous behaviour of nitrogen:
The behaviour of nitrogen differs from rest of the elements.
Reasons:
i. It has a small size.
ii. It does not have d – orbitals
iii. It has high electronegativity
iv. It has high ionization enthalpy
 Dinitrogen:
a) Preparation:
NH Cl(aq)  NaNO (aq) H 
eat
 N (g )  2H O(l)  NaCl(aq)
4 2 2 2

(NH ) Cr O H 
eat
 N  4H O  Cr O
4 2 2 7 2 2 2 3

Ba(N 3 ) 2   
 Ba  3N2
Heat

b) Physical Properties:
i) It is a colourless, odourless, tasteless and non – toxic gas.
ii) It is chemically un-reactive at ordinary temperature due to triple bond in N ≡
N which has high bond dissociation energy.
 Ammonia:
a) Ammonia molecule is trigonal pyramidal with nitrogen atom at the apex.
b) It has 3 bond pairs and 1 lone pair.
c) N is sp3 hybridised.
d) Preparation:
Haber’s process:
0 1
N2 (g)  3H 2 (g)  2NH3 (g)  fH  46.1kJ mol
Pressure 200x10 Pa Temperature 773 K Catalyst is FeO with small amounts of K 2O
and Al2O3
  Nitric Acid:
Ostwald Process:
The NO thus formed is recycled and the aqueous HNO 3 can be concentrated by
distillation upto ~ 68% by mass. Further concentration to 98% can be achieved by
dehydration with concentrated H2SO4. Nitric acid is strong oxidizing agent in the
concentrated as well as in the dilute state.

4NH  5O  P      4NO  6H

t / Rh gauge 500k, 9 bar

2NO  O2  2NO2
3NO2 (g)  H2O(l)  2HNO3 (aq)  NO(g)
 Phosphorus:
a) It shows the property of catenation to maximum extent due to most stable P – P
bond.
b) It has many allotropes, the important ones are:
i. White phosphorus
ii. Red phosphorus
iii. Black phosphorus
 White phosphorus:
a) Discrete tetrahedral P4 molecules
b) Very reactive
c) Glows in dark
d) Translucent waxy solid
e) Soluble in CS2 but insoluble in water
f) It has low ignition temperature, therefore, kept under water
 Red phosphorus
a) Polymeric structure consisting of chains of P4 units linked together
b) Less reactive than white phosphorus
c) Does not glow in dark
d) Has an iron grey lustre
e) Insoluble in water as well as CS2
 Black phosphorus
a) Exists in two forms -  black phosphorus and  black phosphorus
b) Very less reactive
c) Has an opaque monoclinic or rhombohedral crystals
White phosphorus 5          Red phosphorus
73k in an inert atmosphere for several days

White phosphorus H  

igh pressure,473K
 Black phosphorus
Red phosphorus I     Black phosphorus
n a sealed tube,803K

 Phosphine
a) It is highly poisonous, colourless gas and has a smell of rotten fish.
b) Preparation
 Ca 3 P2  6 H 2 O  3Ca (OH ) 2  2 PH 3
Calcium Water Calcium Phosphine
Phosphide Hydroxide

C a 3 P2  6 H C l  3 C a C l 2  2 P H 3
P h o s p h in e

P4  3 N a O H  3 H 2 O  3 N a H 2 P O 2  P H 3
Sodium P h osphine
H ypophosphite

 Chlorides of Phosphorous:
a) Phosphorus Trichloride
i) It is a colourless oily liquid.
ii) Preparation
P4  6Cl2  4PCl3
P4  8SOCl2  4PCl3  4SO2  2S2Cl2
iii) With water,
It gets hydrolysed in the presence of moisture.
PCl3  3H2O  H3 PO3  3HCl
iv) Pyramidal shape, sp3 hybridisation
v) With acetic acid
3CH3COOH  PCl3  CH3COCl  H3 PO3
vi) With alcohol
3C2 H5OH  PCl3  3C2 H5Cl  H3 PO3
b) Phosphorus pentachloride
i) Yellowish white powder.
ii) Trigonal bipyramidal shape, sp3d hybridisation .
iii) Preparation
P4 10Cl2  4PCl5
P4 10SO2Cl2  4PCl5 10SO2
iv) With water
PCl5  H2O  POCl3  2HCl
POCl3  3H2O  H3 PO4  3HCl
v) With acetic acid
3CH3COOH  PCl5  CH3COCl  POCl3  HCl
vi) With alcohol
C2 H5OH  PCl5  C2 H5Cl  POCl3  HCl
vii) With metals
2 Ag  PCl5  2 AgCl  PCl3
Sn  2PCl5  SnCl4  2PCl3
GROUP 16 ELEMENTS
 Oxidation states:
a) They show -2, +2, +4, +6 oxidation states.
b) Oxygen does not show +6 oxidation state due to absence of d – orbitals.
c) Po does not show +6 oxidation state due to inert pair effect.
d) The stability of -2 oxidation state decreases down the group due to increase in
atomic size and decrease in electronegativity.
e) Oxygen shows -2 oxidation state in general except in OF2 and O2F2
f) Thus, the stability of +6 oxidation state decreases and +4 oxidation state increases
due to inert pair effect.
 Ionisation enthalpy:
a) Ionisation enthalpy of elements of group 16 is lower than group 15 due to half-filled
p-orbitals in group 15 which is more stable.
b) However, ionization enthalpy decreases down the group.
 Electron gain enthalpy:
a) Oxygen has less negative electron gain enthalpy than S because of small size of O.
b) From S to Po electron gain enthalpy becomes less negative to Po because of
increase in atomic size.
 Melting and boiling point:
a) It increases with increase in atomic number.
b) Oxygen has much lower melting and boiling points than sulphur because oxygen
is diatomic (O2) and sulphur is octatomic (S8).
 Reactivity with hydrogen:
a) All group 16 elements form hydrides.
b) They possess bent shape.
c) Bond angle: H2O [373K] > H2S [213K] < H2Se [232K] < H2Te [269K]
 Acidic nature:
H2O < H2S < H2Se < H2Te
This is because the H-E bond length increases down the group. Therefore, the bond
dissociation enthalpy decreases down the group.
 Thermal stability:
H2O < H2S < H2Se < H2Te < H2Po
This is because the H-E bond length increases down the group. Therefore, the bond
dissociation enthalpy decreases down the group.
 Reducing character:
H2O < H2S < H2Se < H2Te < H2Po
This is because the H-E bond length increases down the group. Therefore, the bond
dissociation enthalpy decreases down the group.
 Reactivity with oxygen: EO2 and EO3
 a) Reducing character of dioxides decreases down the group because oxygen has a
strong positive field which attracts the hydroxyl group and removal of H+ becomes
easy.
b) Acidity also decreases down the group.
c) SO2 is a gas whereas SeO2 is solid. This is because SeO2 has a chain polymeric
structure whereas SO2 forms discrete units.
 Reactivity with halogens: EX2, EX4 and EX6
a) The stability of halides decreases in the order F- > Cl- > Br- > I-.
b) This is because E-X bond length increases with increase in size.
c) Among hexa halides, fluorides are the most stable because of steric reasons.
d) Dihalides are sp3 hybridised and so, are tetrahedral in shape.
e) Hexafluorides are only stable halides which are gaseous and have sp3d2 hybridisation
and octahedral structure.
f) H2O is a liquid while H2S is a gas. This is because strong hydrogen bonding is present
in water. This is due to small size and high electronegativity of O.
 Oxygen:
a) Preparation:

2KClO H   2KCl  3O

eat / MnO2
3 2

2H 2O2 (aq)       2H O(l) 2 O(g)

Finely divided metals
2

2 Ag 2O(s) H 
eat
 4 Ag (s)  O2 (g )
2HgO(s) 
 2Hg (l)  O2 (g)
2Pb3O4 (s) 
 6PbO(s)  O2 (g)
Re d lead

2PbO2 (s) 

 2PbO(s)  O2 (g )
 Oxides:
The compounds of oxygen and other elements are called oxides.
 Types of oxides:
a) Acidic oxides: Non- metallic oxides are usually acidic in nature.
SO2  H2O  H2 SO3 (Sulphurous acid)
b) Basic oxides: Metallic oxides are mostly basic in nature. Basic oxides dissolve in
water forming bases e.g.,
Na2O  H2O  2NaOH
K2O  H2O  2KOH
CaO  H2O  Ca(OH )2
c) Amphoteric oxides: They show characteristics of both acidic as well as basic oxides.
Al2O3  6HCl(aq)  2 AlCl3 (aq)  3H2O
Al2O3  6NaOH (aq)  3H2O(l)  2Na3[ Al(OH )6 ](aq)
d) Neutral oxides: These oxides are neither acidic nor basic. Example: Co, NO and N2O
  Ozone:
a) Preparation:
It is prepared by passing silent electric discharge through pure and dry oxygen 10 –
15 % oxygen is converted to ozone.
3O2 (g )  2O3 (g ); H  142kJ mol1
b) Structure of Ozone:
Ozone has angular structure. Both O = O bonds are of equal bond length due to
resonance.
 Sulphur:
a) Sulphur exhibits allotropy:
i. Yellow Rhombic ( - sulphur)
ii. Monoclinic (  - sulphur)
b)   sulphur 3 69 K
   sulphur
c) At 369 K both forms are stable. It is called transition temperature.
d) Both of them have S8 molecules.
e) The ring is puckered and has a crown shape.
f) Another allotrope of sulphur – cyclo S6 ring adopts a chair form.
g) S2 is formed at high temperature ( ∼ 1000 K).
h) It is paramagnetic because of 2 unpaired electrons present in anti bonding  *
orbitals like O2.
 Sulphuric acid:
a) Preparation:
By contact process
1
S  O  SO
8 8 2 2

2SO2 (g)  O2 (g) V    2SO

2 O5 /2bar 720k
3 (g)

H   196.6kJ mol1

b) Exothermic reaction and therefore low temperature and high pressure are
favourable.
SO3 (g)  H2 SO4  H2 S2O7 (oleum)
H2 S2O7  H2O  2H2 SO4
(9698%)

c) It is dibasic acid or diprotic acid.

d) It is a strong dehydrating agent.
e) It is a moderately strong oxidizing agent.
GROUP 17 ELEMENTS
 Atomic and ionic radii:
Halogens have the smallest atomic radii in their respective periods because of maximum
effective nuclear charge.
 Ionisation enthalpy:
They have very high ionization enthalpy because of small size as compared to other
groups.
 Electron gain enthalpy:
a) Halogens have maximum negative electron gain enthalpy because these elements
have only one electron less than stable noble gas configuration.
b) Electron gain enthalpy becomes less negative down the group because atomic size
increases down the group.
 Electronegativity:
a) These elements are highly electronegative and electronegativity decreases down the
group.
b) They have high effective nuclear charge.
 Bond dissociation enthalpy:
a) Bond dissociation enthalpy follows the order: Cl2 > Br2 > F2 > I2
b) This is because as the size increases bond length increases.
c) Bond dissociation enthalpy of Cl2 is more than F2 because there are large electronic
repulsions of lone pairs present in F2.
 Colour:
All halogens are coloured because of absorption of radiations in visible region which
results in the excitation of outer electrons to higher energy levels.
 Oxidising power:
a) All halogens are strong oxidising agents because they have a strong tendency to
accept electrons.
b) Order of oxidizing power is: F2 > Cl2 > Br2 > I2
 Reactivity with Hydrogen:
a) Acidic strength: HF < HCl < HBr < HI
b) Stability: HF > HCl > HBr > HI. This is because of decrease in bond dissociation
enthalpy.
c) Boiling point: HCl < HBr < HI < HF. HF has strong intermolecular H bonding. As the
size increases van der Waals forces increases and hence boiling point increases.
d) % Ionic character: HF > HCl > HBr > HI Dipole moment: HF > HCl > HBr > HI.
Electronegativity decreases down the group.
e) Reducing power: HF < HCl < HBr < HI
 Reactivity with metals:
a) Halogens react with metals to form halides.
b) Ionic character: MF > MCl > MBr > MI. The halides in higher oxidation state will be
more covalent than the one in the lower oxidation state.
 Interhalogen compounds:
Reactivity of halogens towards other halogens:
a) Binary compounds of two different halogen atoms of general formula X X n' are called
interhalogen compounds where n = 1, 3, 5, or 7. All these are covalent compounds.
 b) Interhalogen compounds are more reactive than halogens because X-X’ is a more
polar bond than X-X bond.
c) All are diamagnetic.
d) Their melting point is little higher than halogens.
e) XX’ (CIF, BrF, BrCl, ICl, IBr, IF) (Linear shape) XX’3 (CIF3, BrF3, IF3, ICl3) (Bent T-
shape) XX’5 – CIF5, BrF5, IF5, (square pyramidal shape) XX’7 – IF7 (Pentagonal
bipyramidal shape)
 Oxoacids of halogens:
a) Fluorine forms only one oxoacid HOF (Fluoric (I) acid or hypofluorous acid) due to
high electronegativity.
b) Acid strength: HOCl < HClO2 < HClO3 < HClO4
c) Reason:
HClO  H   ClOMost Stable
4 4

d) Acid strength: HOF > HOCl > HOBr > HOI. This is because Fluorine is most
electronegative.
GROUP 18 ELEMENTS:
 Ionisation enthalpy:
a) They have very high ionization enthalpy because of completely filled orbitals.
b) Ionisation enthalpy decreases down the group because of increase in size.
 Atomic radii:
Increases down the group because the number of shells increases down the group.
 Electron gain enthalpy: They have large electron gain enthalpy because of stable
electronic configuration.
 Melting and boiling point:
It has low melting and boiling point due to the presence of only weak dispersion forces.
 Shapes:
XeF2 is linear, XeF4 is square planar and XeF6 is distorted octahedral. KrF2 is known but
no true compound of He Ne and Ar are known.
 Compounds of Xe and F:
Xe  F 6 
73k ,1bar
 XeF
2 2
Xe  2F 8 
73k / 7bar
 XeF 4
2
Xe  3F 5    XeF
73k /60 70bar
2 6

XeF4  O2 F2  XeF6  O2
XeF2, XeF4 and XeF6 are powerful fluorinating agents.
 Compounds of Xe and O:
6 XeF4 12H2O  4 Xe  2 XeO3  24HF  3O2
XeF6  3H2O  XeO3  6HF