CHEMISTRY II PUC

P-BLOCK ELEMENTS
The elements of the groups like 13 to 18 in the periodic table are called p-block elements.
The differentiating electrons enters in to the p-orbital of the valence shell and hence they are called p-block
elements.
P - block elements includes metals, non metals and metalloids. The general electronic configuration
is [Nobel gas] ns2 np1-6.

GROUP 15 ELEMENTS:
ELEMENT AT.NO E.CONFIGURATION
Nitrogen(N) 7 [He] 2S2 2P3
Phosphorous(P) 15 [Ne] 3S2 3P3
Arsenic(As) 33 [Ar]3d10 4S2 4P3
Anitomy(Sb) 51 [Kr]4d10 5S2 5P3
Bismuth(Bi) 83 [Xe]4f14 5d10 6S2 6P3

Elements like N, P, As, Sb and Bi are belongs to group 15 elements. Among these, Nitrogen and
Phosphorou are non-metals, arsenic and Antimony are metalloids and Bismuth is a typical metal. The
general electronic configuration is [noble gas] ‘ns2 np3’.

OCCURRENCE:
78% of molecular nitrogen present in atmosphere. In the earth crust it occurs as sodium nitrate
NaNO3 (Chile salt petre) and KNO3 (Indian salt petre). Phosphrous occurs in minerals of the apatite family
Ex: Fluoro apaptite Ca9(PO4)6 CaF2 and Ca9CaX2(X-F,Cl or OH).
Arsenic, Anitomy and Bismuth are found mainly as sulphide minerals. P.N are main component in
plants and animals.

GENERAL PROPERTIES:
1. Atomic and ionic radii:
Atomic and ionic radii increases in size down the group. The Atomic and ionic radii
increases from N to P. but As to Bi small increases in covalent radii because of presence of
completely filled d or f orbitals.
2. Ionization enthalpy:
Ionization enthalpy decreases down the group due to gradual increase in atomic size.
Because of the extra stable half filled p-orbitals electronic configuration and smaller size.
3. Electronegativity:
The electronegativity value decreases down the group with increasing atomic size.

PHYSICAL PROPERTIES:
All the elements of this group are poly atomic . Dinitrogen is a atomic gas while all others are solid,
metallic character increases down the group. Nitrogen and phosphorous are non metals, orsenic and
antimony are metalloids and bismuth is a metal.
CHEMICAL PROPERTIES:
1. Oxidation states:
 The common oxidation states of this elements are -3,+3 and +5. The tendency to exhibit -3
oxidation state decreases down the group due to increases in size and metallic character. Rarely
Bismuth shows -3 oxidation state. Stability of +5 oxidation state decreases down the group (Best ex
is BF5) and +3 state increases (due to inert pair effect) down the group. Nitrogen exhibits +1, +2,
+4 when it reacts with oxygen. Phosphorous shows +1,+4 oxidation states in oxoacids.
2. Anomalous properties of Nitrogen:
Nitrogen is the first member of the group 15 element. It shows Anomalous behaviour and
differs from other members of its group due to following reasons.
 Small atomic size.
 High ionization enthalpyz.
 High electronegativity.
 Absence of d-orbitals in its valence shell.

PROPERTIES OF ANOMALOUS BEHAVIOUR OF NITROGEN:

1. Nitrogen has unique ability to form Pπ- Pπ multiple bonds with its own atoms due to small atomic
size and high electronegativity while others donot form Pπ- Pπ multiple bond.
2. Nitrogen exist as diatomic gaseous molecule with a triple bond between two atoms while other
elements forms single bond between the elements.
3. Nitrogen exhibits maximum covalency of four due to the absence of d-orbitals in its valence shell
for bonding where as other members of the group exhibit covalency greater than 4 due to the
presence of d-orbitals in the valence shell.
4. Nitrogen cannot form dπ-Pπ bond where as the heavier elements phosphorous and As forms
compounds of the type R3P=0 and R3P=CH2.
5. Nitrogen in NH3 exhibits intermolecular hydrogen bonding while hydrides of other elements donot
form hydrogen bonds.
3. Reaction with Hydrogen:
All the elements form hydrides of the type EH3. The stability of hydrides decreases from
NH3 to BiH3 and reducing character increases consequently. Therefore NH3 is mild reducing agent
and BiH3 is the strongest reducing agent and basicity in the order of NH3>PH3>AsH3>SbH3≥BiH3
4. Reactivity towards oxygen:
All these elements form two types of oxides E2O3 and E2O5. The oxide in the higher
oxidation state of the element is more acidic than that of lower oxidation state. The acidic character
decreases down the group. The oxides of N and P are purely acidic. As and Sb are amphotoric and
Bismuth is basic.
5. Reactivity towards Halogens:
The elements of this group reacts with halogen to form halides of the type EX 3 and EX5.
Nitrogen doesnot form penthalide due to non availability of the d-orbitals in the valence shell. All
the trihalides of these elements except those of nitrogen are stable, but in case of NF3 is stable.
6. Reaction with metals:
All the elements reacts with metal to form their binary compounds exhibiting -3 oxidation
state.
Ex: Ca3N2(Calcium Nitride), Ca3P2(Calcium Phosphide), Na3As2(Sodium arsenide),
Zn3Sb2(Zinc antimonide) and Mg3Bi2(Magnesium Bismuthide)

NOTE:
1) why are pentahalides more covalent than trihalides?
 higher the oxidation state greater it’s the polarising power and greater is the covalent
character. hence pentahalides are more covalent.
2) Why BiH3 is the strongest reducing agent among all the hydrides of group 15 elements?
Among all the hydrides of group 15 elements, Bi has largest atomic size and Bi-H bond as
the longest and is the weakest bond. It can easily break to liberate hydrogen. Hence it acts as a
strongest reducing agent.

-:DINITROGEN:-

PREPARATION:
1) Commercial preparation:
Nitrogen can be obtained commercially by the liquefaction and fractional distillation of air.
Liquid nitrogen (B.P 77.2 K) distills out first leaving behind liquid O2(B.P-90K).

2) Laboratory method:
a) It is prepared by treating an aqueous solution of NH4Cl with sodium nitrite.
NH4Cl + NaNO2 N2 + 2H2O+NaCl

b) By the thermal decomposition of Ammonium dichromate:

Nitrogen is ibtained by thermal decomposition of Ammonium dichromate.
(NH4)2Cr2O7  N2 + 4H2O + Cr2O3

c) Very pure nitrogen can be obtained by the thermal decomposition of sodium or Barium azide.
Ba(N3)2  Ba + 3N2
PROPERTIES:
PHYSICAL PROPERTIES:
 it is a colourless and non-toxic gas.
 it is sparingly soluble in water.
 it exists in two isotopic forms as 14N and 15N.
 it has low freezing point (63.2k) and boiling point(77.2K)
 it is absorbed on activated carbon.

CHEMICAL PROPERTIES:
a) Reaction with metals:
Nitrogen combines with active metals like lithium, magnesium and calcium and aluminium
on heating to form metalnitrides.
6Li + N2  2Li3N
3mg + N2  Mg3N2
2Al + N2  2AlN
b) Nitrogen combines with Hydrogen at 773K in the presence of a catalyst to form Ammonia.
N2 + 3H2 773k 2NH3
c) Dinitrogen combines with Oxygen only at very high temperature to form Nitric Oxide – NO
N2 + O2 2NO
USES:-
1. It is used in the manufacture of Ammonia.
 2. It is used in the manufacture of Nitrogen containing industrial chemicals.
Ex: Calcium Cyanamide
3. Liquid nitrogen is used as refrigerant to preserve biological material, food material and in
Cryosurgery.
4. It is used for filling in electric bulb.

NOTE:-
 Nitrogen is inert at room temperature. Why?
Nitrogen is more stable due to the presence of triple bond in it & bond dissociation enthalpy of
nitrogen is very high. Hence it is very inert at room temperature.

COMPOUNDS OF NITROGEN:-
1. AMMONIA (NH3) :-
Ammonia is present in small quantities in air & soil. Where it is formed by the decay of
nitrogenous organic matter such as Urea.
NH2CONH2 + 2H20 (NH4)2CO3 2NH3 + H20 +CO2

Preparation:
On a smallscale Ammonia is obtained from ammonium salts which decompose when
treated with caustic soda or lime.
2NH4Cl + Ca(OH)2 2NH3 + 2H2O +CaCl2
(NH4)2SO4 + 2NaOH 2NH3 + 2H2O + Na2SO4

MANUFACTURE BY HABERS PROCESS:

In haber’s process ammonia is manufactured by the direct combination of nitrogen and hydrogen.
N2(g) + 3H2(g) 700 K 2NH3(g) Hf= -46.1 KJmol-1 & H= -92.2KJ
200atm

According to Le-chateliers principle in order to get maximum yield of NH3 the reaction conditions are

* Pressure of 200 atm

* Temperature of ~700K
* Catalyst: Iron Oxide
* Promoters :K2O and Al2O3

PHYSICAL
PROPERTIES:
 1. Ammonia is a colourless gas with a pungent odour.
2. Its freezing and boiling points are 198.4 and 239.7K respectively.
3. In the solid and liquid states it is associated through hydrogen bonds and therefore its melting and
boiling points are higher than expected on the basis of molecular mass.
4. It is readily soluble in water.

STRUCTURE:
The ammonia molecule is trigonal pyramidal with the nitrogen atom at the apex. It has three bond
pairs and one lone pair of electrons as shown in the structure below.

CHEMICAL PROPERTIES:
1. Ammonia gas is highly soluble in water. Its aqueous solution is weakly basic due to the formation
of OH- ion.
+ -

NH3(aq) + H2O  NH4(aq) + OH(aq)

2. Ammonia reacts with acids to forms ammonium salts.
NH3 +HCl NH4Cl
2NH3 +H2SO4 (NH4)2SO4
3. As a weak base, it precipitates the hydroxides of many metals from their salt solutions.
ZnSO4(aq) + 2NH4OH(aq) Zn(OH)2 + (NH4)2SO4(aq)
4. Ammonia is a lewis base due to the presence of a lone pair of electrons on the nitrogen atom. It acts
as legand by donating the electron pair and forms complex compounds with metal ions. These
complexes find applications in detection of metal ions such as Cu2+, Ag+ etc.
Cu2+(aq) + 4NH3(aq) [Cu(NH3)4]2+aq
Blue deepblue
Ag (aq) +Cl (aq)
+ -
AgCl
White PPT

AgCl + 2NH3 → [Ag(NH3)2]Cl(aq)

White PPT Colourless
USES:
1. Ammonia is used in the manufacture of various nitrogenous fertilizers (Ammonium nitrate,
Ammonium Phosphate and Ammonium Sulphate)
2. In the manufacture of some inorganic compounds, such as nitric acid.
3. Liquid NH3 is used as a refrigerant.
NOTE:
Why does NH3 acts as a lewis base?
Nitrogen atom in Ammonia has one lone pair of electron which is available for donation therefore it
acts as a lewis base.
Nitrogen forms a number of oxides in different oxidation states. the names, formulas, and structures
of these oxides are given in the table below.
OXIDES OF NITROGEN:

NOTE:
1. NO2 contains odd numbers of valence electrons. It undergoes dimerization to form stable N 2O4
molecule with even number of electrons.
2. In N2O5 oxidation state of nitrogen is +5 and covalency is 4.

NITRIC ACID
Nitrogen forms oxoacids such as Hyponitrous acid (H 2N2O2), Nitrous acid(HNO2) and Nitric acid
(HNO3). Among them HNO3 is the most important.

Preparation of HNO3:
a) Laboratory method:
Nitric acid is prepared by heating KNO3 or NaNO3 and conc.H2SO4 in a glass retort.
NaNO3 + H2SO4 → NaHSO4 + HNO3
b) Manufacture by ostwalds process:
On large scale HNO3 is prepared by Ostwald’s process. This method involves the following steps
 catalytic oxidation of NH3 by atmospheric oxygen.
4NH3 + 5O2 pt/Rh gauge catalyst 4NO(g) + 6H2O(g)
500k,9bar

 Nitric oxide thus formed combines with oxygen to give nitrogen dioxide.
2NO(g) + O2(g)  2NO2(g)
 The NO2 formed dissolved in water to give HNO3
3NO2 + H2O 2HNO3 + NO
PROPERTIES:
1. Nitric acid is a colourless liquid.
2. Its freezing point is 231.4 and B.P is 355.6 k
3. When the solution contains more than 98% HNO3. It is reffered to as fuming nitric acid.
4. Laboratory grade HNO3 contains 68% of the HNO3 by mass and has specific gravity of 1.504
5. It usually aquires yellow colour due to its decomposition by sunlight in to NO2.
4HNO3 → 4NO2 + 2H2O + O2
6. It is extremely corrosive to skin and causes painful sores.
7. Nitric acid is an monobasic acid and it is supposed to exist in two resonating forms.
8. In the gaseous state,HNO3 exists as a planar molecule with the structure shown below.

CHEMICAL PROPERTIES:
a) Nitric acid reacts with water to give hydronium ion and nitrate ion.
HNO3 + H2O → H3O+ + NO3-.
b) Oxidizing nature:
Nitric acid acts as a strong oxidizing agent as it decomposes to give nascent oxygen easily.
2HNO3 → H2O + 2NO2 + [O]
2HNO3 → H2O + 2NO +3[O]
c) Oxidation of metals:
Conc.HNO3 is a strong oxidizing agent and attacks the most metals except noble metals.
The product of oxidation depend upon the concentration of the acid, temperature and the nature of
the material undergoing oxidation.
 Copper reacts with dilute Nitric acid to give NO and Conc. Nitric acid to give NO2.
3Cu + 8HNO3(dilute) → 3Cu(NO3)2 + 2NO + 4H2O
Cu + 4HNO3(Conc) → Cu(NO3)2 + 2NO2 + 2H2O
 Zinc reacts with dilute nitric acid to give N2O and react with conc.HNO3 to give NO2
4Zn + 10HNO3(dilute) → 4Zn(NO3)2 + 4H2O +N2O
Zn + 4HNO3(Conc.) → Zn(O3)2 + 2H2O + 2NO2
d) Conc.HNO3 also oxideses no metals and their compounds. Iodine is oxidised to iodic acid, carbon
to carbon dioxide, sulphur to sulphuric acid and phosphorous to phosphoric acid.
I2 + 10HNO3 → 2HIO3 + 10NO2 + 4H2O
C + 4HNO3 → CO2 + 2H2O +4NO2
S8 + 48HNO3 → 8H2SO4 + 48NO2 + 16H2O
P4 + 20HNO3 → 4H3PO4 + 20NO2 + 4H2O
Brown Ring Test:
This is confirmation test for nitration. An aqueous solution of salt containing nitrate ion is taken in
a test tube and mixed with equal volume of freshly prepared ferrous sulphate solution. Conc.H 2SO4 is
added from the sides of the test tube. A brown ring is formed at the interface of sulphuric acid and aqueous
layer.
No3- + 3Fe2+ +4H+ → NO + 3Fe3+ + 2H2O
[Fe(H2O)6]2+ + NO → [Fe(H2O)5(NO)]2+ + H2O
USES:
1. In the manufacture of ammonium nitrate for fertilizers and other nitrates for used in explosives.
2. For the preparation of nitroglycerin, trinitro toluene and other organic nitro compounds.
3. As a oxidizer in rocket fuels.
4. In the pickling of stainless steel.

Phosphorous – Allotropic forms:

Phosphorous is found in many allotropic forms, the important ones being white, red and black.

WHITE PHOSPHOROUS:
1. White phosphorous is a translucent white waxy solid.
2. It is poisonous.
3. It is insoluble in water but soluble in carbon disulphide.
4. It glows in dark. The phenomenon is called chemiluminescence.
5. It dissolves in boiling NaOH solution in an inert atmosphere giving PH3.
P4 + 3NaOH + 3H2O → PH3 + 3NaH2PO2
Sodium hypophosphite
6. While phosphorous is less stable and therefore, more reactive than the other solid phases under
normal conditions because of angular strain in P4 molecule where the angles are only 60°.
7. It readily catches fire in air to give dense white flumes of P 4O10. Hence it is always kept under
water.
P4 + 5O2 → P4O10
8. It consists of discrete tetrahedral P4 molecule as shown in figure below.

RED PHOSPHOROUS
Preparation:
It is obtained by heating white phosphorous at 573K in an inert atmosphere for several days red
phosphorous is formed.

Properties:
1. It is a odourless, non-poisonous solid.
2. It is insoluble in water as well as carbon disulphide.
3. It is chemically less reactive than white phosphorous.
4. It doesnot glow in dark condition.
5. It possess iron grey lustre.
6. It is polymeric consisting of chains of P4 tetrahedral linked together in the manner as shown below.
BLACK PHOSPHOROUS:
Black phosphorous has two forms.
1.  – Black Phosphorous
2.  - Black phosphorous

 – Black Phosphorous :
 – Black Phosphorous is formed when red phosphorous is heated in a sealed tube at 803K. it can
be sublimed in air and has opaque monoclinic or Rhombohedral crystals. It doesnot oxidize in air.

 - Black phosphorous:
 - Black phosphorous is prepared by heating white phosphorous at 473 K under high pressure. It
doesnot burn in air upto 673K.

PHOSPHINE – PH3:-
Preparation:
a) Phosphine is prepared by the reaction of calcium phosphide with water or dilute HCl.
Ca3P2 + 6H2O → 3Ca(OH)2 + 2PH3
Ca3P2 + 6HCl → 3CaCl2 + 2PH3
b) Laboratory method:
It is prepared by heating white phosphorous with conc.NaOH solution in an inert
atmosphere of CO2.
P4 + 3NaOH +3H2O → PH3 + 3NaH2PO2
(Sodium Hypo Phosphite)
PROPERTIES:
PHYSICAL PROPERTIES:
 It is a colourless gas with rotten fish smell.
 It is highly poisonous.
 It explodes in contact with HNO3,Cl2,Br2 vapours.

CHEMICAL PROPRTIES:
The solution of PH3 in water decomposes in presence of light giving red phosphorous and H2.

BASIC NATURE:
Phosphorous is a very weak basic and like Ammonia , gives phosphonium compounds with acids.
Ex: PH3 + HBr PH4Br

USES:
1. Spontaneous combution of phosphine is technically used Holme’s signals.
(containers containing calcium carbide and calcium phosphide are pierced and thrown in the sea
when the gases evolved burn and serves as a signal.)
2. It is also used in smoke screens.

Phosphorous Halides:
Two types of phosphorous halides PX3 & PX5.
1. Phosphorous trihalide :PCl3
Preparation: It is prepared by passing dry chlorine over heated white phosphorous.
P4 + 6Cl2 4PCl3
 It is also prepared by action of Thionyl Chloride with white phosphorous
P4 + 8SOCl2 4PCl3 + 4SO2 + 2S2Cl2

Properties:
1. It is a colourless oily liquid.
2. Action of water: Phosphorous trichloride undergo hydrolysis in the presence of moisture.
PCl3 +3H2O H3PO3 + 3HCl
3. It reacts with organic compound containing OH groups.
3C2H5OH + PCl3 3C2H5Cl + H3PO3

2. Phosphorous penta chloride: PCl5

Preparation: it is prepared by the reaction of white phosphorous with excess of dry chlorine.
P4 + 10Cl2 4PCl5
 It is also prepared by action of Sulphuryl Chloride on white phosphorous
P4 + 10SO2Cl2 4PCl5 + 10SO2

Properties:
1. It is a yellowish white powder.
2. Action of water:- it undergo hydrolysis to POCl3 and finally gets converted to phosphoric acid.
PCl5 + H2O POCl3 + 2HCl
POCl3 + 3H2O H3PO4 + 3HCl
3. When it heated strongly, it get decomposes to PCl3.
∆
PCl5 PCl3 + Cl2
4. It reacts with organic compound containing OH groups.
C2H5OH + PCl5 C2H5Cl + POCl3 + HCl
CH3COOH+PCl5 CH3COCl+POCl3+HCl
5. Finely divided metals on heating with PCl5 giving corresponding Chlorides
2Ag+PCl5 2AgCl+PCl3
Sn+2PCl5 SnCl4 +2PCl3
NOTE:
1. Why does PCl3 fume in moisture?
PCl3 hydrolysis in the presence of moisture giving fumes of HCl.
PCl3 + 3H2O H3PO3 + 3HCl

2. Are all the five bonds in PCl5 molecule equivalent? Justify your answer.
PCl5 has a trigonal bipyramidal structure and the three equatorial bond are equivalent.
While the two axial bonds are different and longer than equatorial bonds.

OXO ACIDS OF PHOSPHOROUS:-

Phosphorous forms a number of oxo acids. The important oxo acids of phosphorous with their
structures are given below.
Properties:
REDUCING AGENT:
The acid which contain P-H bond have strong reducing properties. Thus, Hypophosphorous acid is
a good reducing agent as it contains two P-H bonds and reduces. For Ex. AgNO3 to metallic silver.
4AgNO3 + 2H2O + H3PO2 4Ag + 4HNO3 + H3PO4

BASICITY:-
The P-H bonds are not ionisable to give H + and donot play any role in basicity. Only those H atoms
which are attached with oxygen in P-OH form are ionisable and are responsible for cause the basicity.
Thus H3PO3 and H3PO4 are dibasic and tribasic respectively as the structure of H 3PO3 has two P-OH bonds
and H3PO4 three.

NOTE:
How do you account for the reducing behaviour of H3PO2 on the basis of its structure?
In H3PO2 two H atoms are bonded directly to P atom which imparts reducing character to
the acid.