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p-BLOCK ELEMENTS - NITROGEN FAMILY

GENERAL CHARACTERISTICS

The group 15 of the periodic table consists of nitrogen, phosphorous, arsenic, antimony and bismuth. These elements are known as pnicogens and their compounds as pnicomides.

ELECTRONIC CONFIGURATION

Element
At. No.
Electronic configuration
Valence shell
Nitrogen
7
[He] 2s2 2p3
2s2 2p3
Phosphorous
15
[Ne] 3s2, 3p3
3s2 3p3
Arsenic
33
[Ar] 3d10, 4s2 4p3
4s2 4p3
Antimony
51
[Kr] 4d10, 5s2 5p3
5s2 5p3
Bismuth
83
[Xe] 4f14, 5d10 6s2 6p3
6s2 6p3

METALLIC CHARACTER

N, P(non metals), As, Sb(metalloids), Bi(metal)

PHYSICAL STATE

Nitrogen is first element after hydrogen to be a diatomic gas in normal form. All other elements in the group are normally solids.

ATOMICITY

N2 is diatomic while others are tetra-atomic M4

MELTING AND BOILING POINTS

The melting point increases from nitrogen to arsenic. The boiling points increase regularly on moving down the group.

DENSITY

Density increases down the group.

ATOMIC RADII

Atomic radii increases with increase in atomic number.

COVALENT RADII

Covalent radii increases in a regular fashion down the group.

ALLOTROPY

All the elements (except bismuth) show allotropy.
Nitrogen - a-nitrogen, b-nitrogen
Phosphorus - white, Red, scarlet, violet, a-black, b-black
Arsenic - Grey, Yellow, Black
Antimony - Metallic, Yellow, Explosive

OXIDATION STATE

N
P
As
Sb
Bi
–3 to +5  
–3, +3, +4, +5
+3, +5
+3, +5
+3, +5

Nitrogen has a wide range of oxidation states
Oxidation state
Example
+5
N2O5, HNO3,
+4
NO2, N2O4
+3
HNO2, , NF3
+2
NO
0
N2
–1
NH2OH, NH2F
–2
N2H4
–3
NH3, ,

NEGATIVE OXIDATION STATES

–3 oxidation state is exhibited by other elements also. Ca3P2, Na3As, Zn3Sb2

INERT PAIR EFFECT

Inert pair effect increases down the group and due to this effect, the stability of +3 oxidation state increases and stability of +5 oxidation state decreases on moving down the group.

IONISATION ENERGY

Ionisation energy of nitrogen is very high due to small atomic radius. The ionisation energy decreases down the group.

ELECTRONEGATIVITY

The electronegativity decreases from nitrogen to bismuth.

CATENATION

They exhibit the property of catenation but due to weak M–M bond to less extent than 14 group elements.
Bond C–C N–N P–P As–As
kJ/mol 353.3 163.7 201.6 147.4

REACTIVITY

Elemental nitrogen is highly unreactive largely because of its strong triple bond. (almost as inert as noble gases).
While phosphorus is extremely reactive and kept in water. It is inflammable and can be ignited at 45ºC. It shows green luminescence or glow in dark on account of its slow oxidation. This glow phenomenon is known as phosphorescence.

MULTIPLE BOND FORMATION

Only nitrogen has a tendency to form pp—pp multiple bonds. Others forms dp–pp multiple bonds easily.

COMPOUNDS OF GROUP 15 ELEMENTS

HYDRIDES

All the elements of this group form hydrides of the type MH3 which are covalent and pyramidal in shape.
Some properties follow the order which are
NH3 >    PH3 >          AsH3 >    SbH3 >  BiH3
Ammonia    Phosphine   Arsine Stabene   Bismuthene
  • Ease of formation
  • Stability
  • Basic character
  • Solubility
  • Bond angle (NH3 107.5º ; PH3 92º, AsH3 91, SbH3 90º)
  • Strength of M – H bond
  • Dipole moment
  • Decomposition temperature

Some properties follow the order
NH3 < PH3 < AsH3 < SbH3 < BiH3
  • Reducing character
  • Covalent character
  • Poisonous character
  • Rate of combustion

Boiling points : BiH3 > SbH3 > NH3 > AsH3 > PH3

PREPARATION OF HYDRIDES
Some hydrides  can be prepared as follows :
  1. Ammonia
    1. Any ammonium salt + metal oxide or hydroxide NH3
eg.
or (NH4)3PO4, NH4NO3, (NH4)2SO4,
(NH4)2SO3, (NH4)2S or (NH4)2 (C2O4)
  1. Phosphine
  1. Other hydrides
, M = As, Sb, Bi

HALIDES

All the elements of this group form trihalides of the type MX3 and except nitrogen all form pentahalides of the type MX5
MX3    M = N, P, As, Sb, Bi and X = F, Cl, Br or I
MX5    when X = F, M can be P, As, Sb and Bi
when X = Cl, M can be P, As and Sb
when X = Br, M can be P
NF3 is a colourless, odourless gas and the most stable of this series. It has low reactivity.
NCl3 is a yellow oily liquid that reacts with water to form ammonia and hypochlorous acid.
NI3 is shock sensitive and decomposes explosively when touched.

HYDROLYSIS
  • Ease of hydrolysis BiCl3 > SbCl3 > AsCl3 > PCl3 > NCl3
  • Trihalides except BiF3 are covalent in nature
  • Trihalides have pyramidal structure.

PENTAHALIDES

As nitrogen does not contain-vacant d-orbitals in the second shell and cannot expand its outer shell hence it does not form pentahalides.
  • The hybridisation in pentahalides is sp3d (trigonal bipyramidal)
  • Thermally less stable than trihalides
  • Act as Lewis acids   
  • On complete hydrolysis they produce acids   

OXIDES

All the elements of this group form oxides of the type M2O3 and M2O5. either by direct combination with O2 or indirectly.  
Oxides of N  
Oxides of P
Oxides of As   
Oxides of Sb     
Oxides of Bi    

N2O (DINITROGEN OXIDE OR NITROUS OXIDE) known as laughing gas
Preparation :
  • Priestley’s method :
  • Bertholet’s (common method) :

Properties :
Colourless, fairly unreactive, pleasing odour, sweet taste, supports combustion. It is neutral.
Structure : Linear  

Uses : Mixed with oxygen it is used as anaesthetic

NO (NITROGEN OXIDE OR NITRIC OXIDE)
Preparation :
  • (common method)
  •  (commercial)
  •  (Lab method)
  •  (Ostwald’s process)

Properties : Colourless, paramagnetic, slightly toxic gas, blue in liquid state. It is combustible and supports combustion. It is neutral.
     
It is reducing as well as oxidising in nature.

Uses :
i) For manufacturing of nitric acid
ii) For detection of Oxygen
iii) For manufacturing of sulphuric acid as catalyst (Lead chamber process)
Structure :

NO2 (NITROGEN DIOXIDE)
Preparation :
  • (Common method)

Properties :
Highly toxic, paramagnetic, reddish brown gas with choking odour, acidic

Reactions :
  • (Hence it is mixed anhydride of HNO2 and HNO3)
  • It is combustible and supports the combustion of burning P, Mg or charcoal. Burning S or candle is extinguished.
  • It is oxidising and reducing in nature

Uses :
  • For Manufacturing of HNO3
  • As Catalyst in lead chamber process for Sulphuric acid

Structure :
N2O3 (DINITROGEN TRIOXIDE) NITROGEN SESQUIOXIDE
Preparation :  
  • (common method)

Properties : It is blue solid, acidic
Hence it is anhydride of HNO2
Absorbed by sulphuric acid

Structure : Shape and structure is not definitely known
                          

N2O5 (DINITROGEN PENTOXIDE)
Preparation :
  • (common method)

Properties : Colourless crystalline solid and sublimes
It is anhydride of nitric acid

Uses : It is powerful oxidising agent

Structure :
It’s ionic structure (by X-ray) is . It is also called nitronium nitrate.
P2O3 or P4O6 (PHOSPHORUS TRIOXIDE)
Preparation :

Properties : white solid like wax, garlic odour, highly poisonous.
Structure :
P2O5 or P4O10 (PHOSPHORUS PENTOXIDE) FLOWER OF PHOSPHOROUS
Preparation :

Properties : White crystalline solid smells like garlic, sublimes

Uses : Powerful dehydrating agent
Structure :

OXYACIDS OF N AND P

Both form a number of oxy acids which are as follows:


Oxidation number
Basicity
Hyponitrous acid
H2N2O2
+1

Nitroxylic acid
H4N2O4
+2

Nitrous acid
HNO2
+3

Nitric acid
HNO3
+5

Peroxynitric acid
HNO4
+5

Hydronitrous acid
H2NO2
+2

Hypophosphorus acid
H3PO2
+1
1
Phosphorus acid
H3PO3
+3
2
Orthophosphoric acid
H3PO4
+5
3
Pyrophosphoric acid
H4P2O7
+5
4
Meta phosphoric acid
HPO3
+5
1
Hypophosphoric acid
H4P2O6
+4
4

NITROGEN

Discovered by Daniel Rutherford. Abundance in air is 78.15% by volume. It occurs in combined state as saltpetre (KNO3) and Chile Saltpetre (NaNO3). It is also known as Azote (without life)

PREPARATION

  • . It is violent reaction with flashes of light (volcano experiment)
  • Preparation of very pure N2 : By heating Sodium azide

MANUFACTURING

LINDE’S OR CLAUDE’S PROCESS
Atmospheric air is compressed and then released into a bigger area when liquid air is obtained (Joule Thomson effect) which is mainly mixture of N2 and O2. They are separated by fractional distillation.

PROPERTIES

  • It is colourless, odourless, tasteless, slightly lighter than air, slightly soluble in water, non poisonous gas.
  • It is incombustible and non supporter of combustion.
  • It combines with metals and non metals to form number of compounds.

USES

To decrease concentration of oxygen in air and make combustion less rapid. To create inert atmosphere and in the preparation of NH3, HNO3, CaCN2, etc.

AMMONIA (NH3)

PREPARATION

(lab method)

MANUFACTURING

  • Haber’s process :
Other catalysts employed are
(i) finely divided Os or U
(ii) Finely divided Ni deposited over pumice stone
(iii) Fe(OH)3 with traces of SiO2 and K2O
  • Cyanamide process :
Mixture of Calcium Cyanamide and graphite under the name of nitrolim is used as fertilizer.
  • Serpeck's process : As by product during hydrolysis of AlN

PROPERTIES

  • Colourless gas, characteristic pungent odour, brings tears into eyes, collected by downward displacement of air.
  • Extremely soluble in water due to H-bonding. It is a strong lewis base.
  • Ammonia is dried over any metal oxide but CaO is cheaper.
  • When passed through alkaline solution of Nessler's reagent a brown coloured complex known as Millon’s base is formed.
         

NITRIC ACID (HNO3)

also known as aqua fortis

PREPARATION

(lab method)

MANUFACTURING

  • Birkeland - Eyde process : Air is passed through an electric arc (3000ºC) when N2 combines with O2 to form NO. It is cooled and allowed to combine with O2 to form NO2. The latter is passed in water in presence of excess of air to give HNO3.
  • Ostwald’s Process : From ammonia

PHYSICAL PROPERTIES

Syrupy, colourless, pungent liquid usually available as 68% and 15.7 M. Aqueous solution is often yellow due to small concentrations of NO2
Fuming nitric acid (HNO3 + NO2)

CHEMICAL PROPERTIES

  • As an acid
It is a strong acid and in aqueous solution the ionisation is virtually complete.
Thus it reacts with basic oxides, hydroxides, carbonates etc.
  • As oxidising agent
       
or  (concentrated HNO3)
 (dil. HNO3)

OXIDATION OF NON METALS -IC ACIDS ARE FORMED
(Sulphuric acid)
(Carbonic acid)
(Phosphoric acid)
(Iodic acid)
(Arsenic acid)
(Metastannic acid)
(Selenious acid)
(Tellurous acid)

OXIDATION OF COMPOUNDS

ACTION OF NITRIC ACID ON METALS

ARMSTRONG’S THEORY
The metal first displaces nascent hydrogen from acid which further reacts with acid to give secondary reactions.

Factors affecting the secondary reactions
  • Nature of the metal
  • Concentration of the acid
  • Temperature
  • Presence of impurities

ACTION OF NITRIC ACID ON ZINC UNDER DIFFERENT CONDITIONS
  • Cold and very dil. acid evolves ammonia which reacts with HNO3 forming ammonium nitrate
  • Cold and dil HNO3
  • Cold and moderately conc.
  • Cold and concentrated

ACTION OF NITRIC ACID ON COPPER UNDER DIFFERENT CONDITIONS
  • Cold and dil.
  • Cold and moderately concentrated
  • Cold and concentrated
  • Hot and conc.
  

Metals like Mg and Mn give hydrogen with dil. HNO3

PASSIVITY
Metals like, Fe, Cr, Ni, Al or Co become inactive or passive due to stable oxide layers.
Noble Metals like Pt, Pd, Os, Ir and Au do not react with nitric acid. They react with aqua regia (1 vol. Conc. HNO3 + 3 vol. Conc. HCl).
Similarly platinum forms

STRUCTURE OF NITRIC ACID

USES

In the manufacture of fertilizers ii) For purification of silver and gold iii) In the manufacture of explosives iv) oxidising reagent v) As nitrating reagent

NITROUS ACID (HNO2)

PREPARATION

PROPERTIES

It has slight bluish colour in solution may be due to anhydride N2O3. It is very unstable.
  • Decomposition
 (auto oxidation)
  • Action of heat
  • Oxidising nature
 (electron acceptor)
  • Reducing nature
(electron donor)
  • Reaction with ammonia
  • Formation of diazonium compounds

USES

In the manufacture of azo dyes.

STRUCTURE

It is a tautomeric mixture of the following forms

PHOSPHOROUS

Discovered by Brand

OCCURRENCE

It occurs in combination only as phosphates
  • Phosphorite Ca3(PO4)2
  • Chlorapatite CaCl2.3Ca3(PO4)2
  • Fluorapatite CaF2.3Ca3(PO4)2
In phosphoproteins of brain, bones, teeth, milk, egg, nervous tissues of animal and plants.

MANUFACTURING

By reduction of calcium phosphate with carbon in presence of SiO2 in an electric furnace
Purification : By melting under acidified solution of K2Cr2O7. The impurities are oxidised and redistilled.

PROPERTIES

Freshly prepared phosphorus is colourless. On standing acquires pale lemon colour due to formation of red phosphorus on the surface. It is therefore called yellow phosphorus. Due to its poisonous nature the jaw bones decay and disease is known as “Phossy jaw

ALLOTROPIC FORMS OF PHOSPHORUS AND THEIR PREPARATION
  • Red phosphorous
    By carefully heating yellow phosphorus in an inert atmosphere for about 8 days
  • Violet phosphorus
    By crystallisation of white phosphorous from molten lead
  • Scarlet
By exposing the solution of red P in PBr3 to light or by boiling
By heating PBr3 with Hg at 513K
  • Black
    By heating white P to 473K under 1000kg/sq. cm.
    It is the most stable form, good conductor of electricity.

CHEMICAL PROPERTIES

  • With non metals
    • ,
    • ,
  • With metals
    •          
  • With compounds

USES

In matches, explosives, as rat poison and in fertilizers and alloys.
Match box
Side contains : Red P or P2S3 + Sand + Glue
On tip : Red P + Oxidising agent like KClO3 or KNO3 or Pb3O4 + glass powder or chalk for friction + glue

PHOSPHINE (PH3)

PREPARATION

  • Any phosphide + H2O PH3
  • Decomposition of H3PO3 :
  • Lab. method :
  • Pure PH3  :

PROPERTIES

  • Physical Properties : Colourless, highly poisonous, with rotten fish odour gas, slightly soluble in water
  • Basic nature :
  • Decomposition :
  • Combustibility :
Pure PH3 is not spontaneously inflammable. Ordinary PH3 is spontaneously inflammable due to the presence of P2H4
  • With metallic salts :
  • With chlorine :

USES

  • Holme’s signals : A mixture of CaC2 and Ca3P2 when treated with water, phosphine is liberated which catches fire and lights up acetylene. Burning gases serve the purpose of a signal. They are used in ships.
  • Smoke screen : Ca3P2 is used smoke screen. PH3 obtained from it catches fire to give the needed smoke.
  • Celphos : It is trade name of AlP, aluminium phosphide and used as fumigant. In presence of moisture it gives PH3 which kills insects and pests
  • Rat poison : Zinc phosphide Zn3P2 is a rat poison, which gives PH3

ORTHOPHOSPHORIC ACID (H3PO4)

PREPARATION

PROPERTIES

  • Physical Properties - Colourless syrupy liquid
  • Action of heat
      
  • It is tribasic and ionises in three steps
 (Readily)
 (Weakly)
(very weak ionisation)

USES

  • For preparation of HBr, HI in laboratory
  • For preparing metaphosphoric acid
  • Stabiliser for H2O2

ORTHOPHOSPHORUS ACID (H3PO3)

PREPARATION

PROPERTIES

  • Physical Properties - It crystallises as deliquescent white solid
  • Acidic nature :
  • Decomposition : . This reaction is disproportionation
  • Reducing nature :
(colour of I2 discharged)
                                                          

USES

As reducing agent

FERTILIZERS

Fertilizers are the chemical substances which are added to soil in order to make up the deficiency of nutrients required by plants. Nutrients are classified as-
  • Primary nutrients : which are consumed in large quantities eg. Nitrogen, Phosphorus and Potassium
  • Secondary nutrients : Calcium and Magnesium
  • Micro nutrients : which are required in minute quantities eg. Copper, Zinc, Manganese, Boron, Molybdenum, chlorine and Iron

TYPES OF FERTILIZERS

NITROGENOUS FERTILIZERS
These provide nitrogen to the plants.
  • Urea
It contains about 47% N2
  • Ammonium sulphate (Sindri fertilizer)
  • Basic Calcium nitrate
    (nitrate of lime or Norwegian saltpetre)
  • Calcium cyanamide
or   

PHOSPHATIC FERTILIZERS
These provide phosphorus to plants
  • Super phosphate of lime
available phosphorus 16 - 18% P2O5
  • Phosphatic slag or Thomas slag
It is by product of steel industry, available phosphorus 14-18% P2O5
  • Triple super phosphate
  • Nitrophos

POTASH FERTILIZERS
These provide potassium to plants. eg. KCl, KNO3, K2SO4

MIXED FERTILIZERS
  • Ammoniated superphosphate
    It is prepared by spraying ammoniation solution (NH4NO3 = 65.0%, NH3 = 21.7% and H2O = 13.27%) on superphosphate

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p-Block Elements - Nitrogen Family | Chemistry Notes for IITJEE/NEET
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