The p-Block Elements

p-Block Elements (Group 13 to 18 )

s-Block Elements (group 1 and 2 )

s and p- block
Representative Elements or Main Group
Elements.

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 The p-Block Elements

Outermost electronic configuration varies from

ns2np1 to ns2np6

• Group 13 elements--- ns2np1

• Group 14 elements--- ns2np2

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 The p-Block Main points (properties)
Elements
 Most of p-Block elements are non-metals.
 They have variable oxidation states.
 They form acidic oxides
 They impart no characteristic colour to the
flame
 Generally they form covalent compounds.
Halogens form salts with alkali metals

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 The p-Block Elements
Main points (properties) cont…d

• They have high ionization potentials.

• They have very large electron gain

enthalpies.

• They are solids/liquids/gases at room

temperature (Br is liquid)

• The aqueous solutions their oxides are

acidic in nature.
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 THE p -BLOCK ELEMENTS
• why p-block elements consist of
only six groups?
• The number of p orbitals is three therefore,
the maximum number of electrons that can
be accommodated in a set of p orbitals is six.
• Therefore, there are six groups of p–block
elements in the periodic table numbering
from 13 to 18.
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• Boron, carbon, nitrogen, oxygen, fluorine and
helium head the groups.

• Their valence shell electronic configuration is

ns2np1-6(except for He).

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 The important oxidation states
exhibited by p-block elements are shown in Table

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PROPERTY N P AS SB BI
Atomic
number 7 15 33 51 83

Atomic mass/g mol-1 14.01 30.97 74.92 121.75 208.98

Electronic
configuration [He]2S22p3 [Ne]3S22p3 [Ar]3d104s24p3 [Kr]4d105s25p3 [Xe]4f145d106s26p3

Ionisation I 1402 1012 947 834 703

enthalpy II 2856 1903 1798 1595 1610
(ΔiH/(kj III mol-1) 4577 2910 2736 1610 2466

Electronegetivity 3.0 2.1 2.0 1.9 1.9

Covalent radius/pma 70 110 121 141 148

Ionic radius/pm 171b 212b 222b 76c 103c

Melting point/K 63* 317d 1089e 904 544

Boiling point/K 77.2* 554d 888f 1860 1837

Density/[g cm-3(298
K)] 0.879g 1.823 5.778h 6.697 9.808
Table 7.1: Atomic and Physical Properties of Group 15 Elements

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 Group 15 elements
Electronic Configuration
• The valence shell electronic configuration
ns2np3.
• The s orbital is completely filled and p orbitals
are half-filled, making their electronic
configuration extra stable.
• +3 and +5 oxidation state .

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 7.1.3 Atomic and Ionic Radii
• Covalent and ionic (in a particular state) radii
increase in size down the group.
• There is a considerable increase in covalent
radius from N to P.
• As to Bi only a small increase in covalent
radius is observed due to the presence of
completely filled d orbitals and/or f orbitals in
heavier members.

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 7.1.4 Ionisation Enthalpy
• Ionisation enthalpy : decreases down the group
due to gradual increase in atomic size.

• Ionisation enthalpy of group 15 elements greater

than group 14 elements:Because of the extra
stable half-filled p orbitals electronic
configuration and smaller size of group 15
elements .
• Increase in magnitude of effective nuclear charge.

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 7.1.5 Electronegativity
• The electronegativity value, in general,
decreases down the group with increasing
atomic size.

• However, amongst the heavier elements, the

difference is not that much pronounced.

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 7.1.6 Physical Properties
• Polyatomic nature : Dinitrogen diatomic gas while all
others are solids (Polyatomic P4 ).
• Metallic character : increases down the group.
Nitrogen and phosphorus are non-metals,
arsenic and antimony metalloids
bismuth is a metal.
This is due to decrease in ionisation enthalpy and increase
in atomic size.
• The boiling points, increase from top to bottom in
the group .
• The melting point increases upto arsenic and then
decreases upto bismuth.
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 Anomalous properties of nitrogen
Anamalous property is due to
1) its small size
2) High electronegativity
3) High ionisation enthalpy
4) Non-availability of d orbitals.

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 Anomalous property
• Nitrogen form p π -p π multiple bonds .
• Bond enthalpy (941.4 kJ mol–1 ) is very high.
• Heavier elements do not form p π -pπ bonds as
their atomic orbitals are so large and diffuse that
they cannot have effective overlapping.
• phosphorus (P–P), arsenic(As–As) and
antimony (Sb–Sb)form single bonds and bismuth
forms metallic bonds in elemental state.
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 Anamalous property
• N-N single bond is weaker than P-P single bond .
Because
• Bond length is short in N-N .
• High interelectronic repulsion of the non-bonding
electrons.
• Therefore catenation is weak in nitrogen .

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• Nitrogen cannot form bond with transition
elements :
• Absence of d orbitals in its valence shell.
• Nitrogen cannot form dπ –pπ bond as the heavier
elements can e.g., R3P = O or R3P = CH2 (R = alkyl
group).
• Phosphorus and arsenic can form dπ –dπ bond
with transition metals when their compounds like
P(C2H5)3 and As(C6H5)3 act as ligands.

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 (i) Reactivity towards hydrogen
• Hydride formation : Group 15 form EH3
( E = N, P, As, Sb or Bi )
• The hydrides show regular gradation in their
properties.
• Stability : decreases from NH3 to BiH3 due to increase
in atomic size , decrease in bond dissociation enthalpy.
• Reducing character :Increases ,due to small bond
dissociation enthalpy ,covalent character decreases.
• Basicity :decreases NH3 > PH3 > AsH3 > SbH3 > BiH3.
• NH3 Is strong base :Small size and high electron
density, has lone pair .
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 (ii) Reactivity towards oxygen
• Form two types of oxides: E2O3 and E2O5.
• The oxide in higher oxidation state is more acidic.
Their acidic character decreases down the group.
• Nitrogen atom has small atomic size ,strong pull of
electron pair between O-H bond ,releases the H+
ion .
• Effect decreases as atomic size increases .
• The oxides of type E2O3 of nitrogen and
phosphorus are purely acidic, arsenic and antimony
amphoteric ,bismuth predominantly basic.
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 (iii) Reactivity towards halogens
• Halides formation: MX3 and MX5.
• Nitrogen does not form pentahalide due to non-
availability of the d orbitals in its valence shell,
contains only 1 - s and 3- p orbitals .
• Pentahalides are more covalent than trihalides.
• All the trihalides (covalent nature) of these
elements except those of nitrogen are stable.
• In case of nitrogen, only NF3 is known to be
stable. Trihalides except BiF3 are predominantly
covalent in nature.
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• Though nitrogen exhibits +5 oxidation state, it does
not form pentahalide. Give reason.
• Solution
Nitrogen with n = 2, has s and p orbitals only. It does
not have d orbitals to expand its covalence beyond
four. That is why it does not form pentahalide.

• PH3 has lower boiling point than NH3. Why?

• Solution
Unlike NH3, PH3 molecules are not associated through
hydrogen bonding in liquid state. That is why the
boiling point of PH3 is lower than NH3.
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 7.2 Dinitrogen
Preparation :( NH4CI, NaNO2 / (NH4)2Cr2O7 / Ba(N3)2 )
Laboratory : dinitrogen is prepared by treating an aqueous solution
of ammonium chloride with sodium nitrite.

NH4CI(aq) + NaNO2(aq) → N2(g) + 2H2O(l) + NaCl (aq)


It can also be obtained by the thermal decomposition of
ammonium dichromate.

 Very pure nitrogen :thermal decomposition of sodium or

barium azide.

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Ba(N3)2 → Ba + 3N2
Vijaykumar Nazare 25
 Properties
• Dinitrogen : colourless, odourless, tasteless and non-toxic gas.
• Two stable isotopes: 14N and 15N.
• Low Solubility in water , low freezing and boiling points
• Inert at room temperature because of the high bond enthalpy
of N ≡N bond. Reactivity increases rapidly with rise in
temperature.
• At higher temperatures, form ionic nitrides and with non-
metals, covalent nitrides.

• Reaction with hydrogen to form ammonia:

• Reaction with dioxygen (at about 2000 K) form nitric oxide,

NO.
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 Uses:

• Manufacture of ammonia and industrial

chemicals containing nitrogen, (e.g., calcium
cyanamide).
• Finds use where an inert atmosphere is
required (e.g., in iron and steel industry, inert
diluent for reactive chemicals).
• Refrigerant to preserve biological materials,
food items and in cryosurgery etc.

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 Oxides of Nitrogen

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Sr. White Phosphorus Red Phosphorus Black phosphorus
no
1 Transparent , waxy solid Odourless ,non-poisonous Red P4 + 803 K → α-black P4
,poisonous . white P4 + 573 K → Red P4 white P4 + 4373 K → β-black P4
iron grey lustre Two forms α and β

2 insoluble in water but insoluble in water and CS2 Sublime,opaque,monoclinic

soluble in CS2

3 Glows in dark Does not Glow in dark Does not glow in dark

4 Burns in air β-black P4 Does not burn in air

P4 + 5O2 → P4O10
5 Less stable ,reactive due Less reactive Less reactive
to angular strain
6 tetrahedral P4 molecule polymeric, chains of P4
tetrahedra linked together .

Layered structure
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 Phosphine PH3

• Preparation : Reaction of calcium phosphide with water or

dilute HCl.
Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3
Ca3P2 + 6HCl → 3CaCl2 + 2PH3

• Laboratory : Heating white phosphorus with concentrated

NaOH solution in an inert atmosphere of CO2.
P4 + 3NaOH + 3H2O → PH3 + 3NaH2 PO2
(sodium hypophosphite)
When pure, it is non inflammable but becomes
inflammable owing to the presence of P2H4 or P4 vapours.
• To purify
PH4I + KOH → KI + H2O + PH3
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 Properties
• Colourless gas with rotten fish smell and highly
poisonous.
• It explodes in contact with oxidising agents like HNO3,
Cl2 and Br2 vapours.
• Slightly soluble in water. The solution of PH3 in water
decomposes in presence of light giving red phosphorus
and H2.
• When absorbed in copper sulphate or mercuric
chloride solution, phosphides are obtained.
3CuSO4 + 2PH3 → Cu3 P2 + 3H2SO4
3HgCl2 + 2PH3 → Hg3P2 + 6HCl
• Phosphine is weakly basic and like ammonia, gives
phosphonium compounds with acids e.g.,
PH3 + HBr → PH4 Br
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 Uses:
• The spontaneous combustion of phosphine is
technically used in Holme’s signals.
• Containers containing calcium carbide and
calcium phosphide are pierced and thrown in
the sea when the gases evolved burn and
serve as a signal.
• It is also used in smoke screens.

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 Phosphorus Halides
Two types of halides, PX3 (X = F, Cl, Br, I) and PX5 (X = F, Cl, Br).

• Phosphorus Trichloride • Phosphorus Pentachloride

• Preparation : • Preparation :
• The reaction of white phosphorus • The reaction of white
with excess of dry chlorine. phosphorus with excess of dry
P4 + 6Cl2 → 4PCl3 chlorine.
P4 + 10Cl2 → 4PCl5
• Action of thionyl chloride with • Action of SO2Cl2 on
white phosphorus. phosphorus.
P + 8SOCl → 4PCl + 4SO + 2S Cl P4 + 10SO2Cl2 → 4PCl5 + 10SO2
4 2 3 2 2 2

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 Properties
• Phosphorus Trichloride Phosphorus Pentachloride
1. Colourless oily liquid 1. Yellowish white powder
2. hydrolysed in presence of 2. Hydrolyses in presence of
moisture. moisture.
PCl3 + 3H2O →H3PO3 + 3HCl PCl5 + H2O → POCl3 + 2HCl
POCl3 + 3H2O → H3PO4 +
3. Reacts with organic compounds 3HCl
containing –OH group. 3. Reacts with organic
3CH3COOH + PCl3 → 3CH3COCl compounds containing –OH
+H3PO3 group .
3C2H5OH + PCl3 → 3C2H5Cl + H3PO3 C2H5OH + PCl5 → C2H5Cl + POCl3 + HCl
4. It has a pyramidal shape sp3 . CH3COOH + PCl5 → CH3COCl + POCl3
+HCl
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5. Trigonal bipyramidal sp3d44
Vijaykumar Nazare
• Metals on heating with PCl5 .
2Ag + PCl5 → 2AgCl + PCl3
Sn + 2PCl5 → SnCl4 + 2PCl3
• Trigonal bipyramidal structure .Two axial bonds
are longer than equatorial bonds. This is due to
the fact that the axial bond pairs suffer more
repulsion as compared to equatorial bond pairs.
• [PCl4]+ is tetrahedral and the anion, [PCl6]-
octahedral
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 CHARACTERISTIC

OXIDATION STATE OF S BONDS AND

NAME FORMULA PHOSPHORUS THEIR NUMBER PREPARATION

One P – OH
Hypophosphorus Two P – OH
(phosphinic) H3PO2 +1 One P = O white P4 + alkali
Two P – OH
Orthophosphorous One P – OH
(phosphonic) H3PO3 +3 One P = O P2O3
Two P – OH
two P – OH
Pyrophosphorous H4P2O5 +3 Two P = O PCl3 + H3PO3
Four P – OH
two P – OH
Hypophosphoric H4P2O6 +4 One P = O red P4 + alkali
Three P – OH
Orthophosphoric H3PO4 +5 One P – OH P4O10+H2O
Two P – OH
Two P – OH
Pyrophosphoric H4P2O7 +5 One P-O-P heat phosphoric acid
Three P – OH phosphorus acid +
Three P – OH Br2, heat in a sealed
Metaphosphoric
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Table 7.5: Oxoacids of Phosphorus
 Oxoacids of Phosphorus

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• Acids having P–H bond have strong reducing
properties. Thus, hypophosphorous acid H3PO2 is a
good reducing agent as it contains two P–H bonds
and reduces.
4 AgNO3 + 2H2O + H3PO2 → 4Ag + 4HNO3 + H3PO4
• These P–H bonds are not ionisable to give H+ and
do not play any role in basicity.
• H atoms which attached with oxygen in P–OH
form are ionisable and cause the basicity. Thus,
H3PO3 and H3PO4 are dibasic and tribasic,
respectively as the structure of H3PO3 has two P–
OH bonds and H3PO4 three.
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