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10.VA Group Elements 171-175

10.VA Group Elements 171-175

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 1
10. GROUP 15 ELEMENTS (V A GROUP ELEMENTS)
Synopsis :
 
VA group elements are Nitrogen (N) (7), Phosphorus (P) (15), Arsenic (As) (33), Antimony (Sb)(51), Bismuth (Bi) (83).
 
These elements are called as pnicogens.
 
Their compounds are called pnictides.
 
78% of Atmosphere posses Nitrogen.
 
It is also available in the form of nitrate salts in earth’s crust.Eg : Salt petre KNO
3
, Chile salt petre NaNO
3
etc,.
 
Most abundant element of this group in earths crust is P.
 
The important minerals of phosphorus are phosphate rocks, fluorapatite [3Ca
3
(PO
4
)
2
, CaF
2
],phosphorite [Ca
3
(PO
4
)
2
] etc,.
 
These are p–Block elements with ns
2
np
3
configuration.
 
As the P – orbitals in the outermost shells are half-filled these elements are stable.
 
Nitrogen is a gas, P, As, Sb and Bi are solids.
 
Nitrogen and Phosphorus are non – metals, Arsenic and antimony are metalloids and Bismuth is ametal.
 
Nitrogen exists as triple bonded diatomic gaseous molecule. Bismuth is a metal (monoatomic).
 
P, As and Sb exists as tetratomic, tetrahedral molecules.
 
The existence of Nitrogen as diatomic molecule is due to existence of p
π
- P
π
multiple bonds.
 
The bond dissociation energy of Nitrogen is 945.4kJ. (225 kcal/mole)
 
p
π
- P
π
multiple bonds are not possible in other elements due to repulsion between non – bondedelectrons of the inner core.
 
Phosphorus form layered structures with a co-ordination number of 3.
 
P
4
has a regular tetrahedral structure having one P atom at eachvertex of the tetrahedron. The bond angle
PPP
is 60°.
 
Atomic size increases from Nitrogen to Bismuth, less increase fromAs to Bi is because of less shielding effect of (n-1) d electrons.
 
Due to smaller size of nitrogen it’s electronegative value is high.
 
Electronegativity decreases from nitrogen to Bismuth.
 
B.P. increases from Nitrogen to Bismuth.
 
M.P. increases from Nitrogen to Arsenic and then decreases.
 
Low M.P of nitrogen is due to its diatomic discrete gaseous molecules.
 
Due to large size and metallic character the M.P. of antimony and Bismuth decreases.
 
Nitrogen in solid state exists in cubic crystalline structure (
α
- nitrogen) and hexagonal crystallinestructure (
β
- nitrogen).
 
Phosphorous exists in white, red, scarlet, violet,
α
- black,
β
- black etc. forms.
 
Nitrogen can form a chain of two atoms (NH
2
–NH
2
) and a chain of three atom (N
3(-)
).
 
Less catenation capacity for Nitrogen is due to less dissociation energy of N – N bond.
 
Phosphorus forms (P
2
H
4
).
 
The general oxidation states of these elements are +3 and +5 and –3 (except Bi).
 
Stability of + 3 form increases from nitrogen to bismuth and + 5 decreases due to inert pair effect.
PPPP60°
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V A Group Elements
2
 
Nitrogen show various oxidation states because of small size and high electronegativity. It shows– 3 in Li
3
N, Mg
3
N
2
, Ca
3
N
2
etc.– 2 in N
2
H
4
– 1 in NH
2
OH
31
in N
3
H0 in N
2
 + 1 in N
2
O+ 2 in NO+ 3 in N
2
O
3
 + 4 in NO
2
+ 5 in N
2
O
5
 
 
Phosphorous show – 3 in Zn
3
P
2
, Ca
3
P
2
.
 
Nitrogen can show maximum covalency of 4 (NH
4+
).
 
Remaining elements shows covalency of 5 and a maximum of 6 as in AsF
6(–)
, PCl
6(–)
.
 
Phosphorous is reactive due to the presence of single P – P covalent bonds.
HYDRIDES :
 
These elements form hydrides of the type MH
3
 NH
3
(Ammonia) PH
3
(Phosphine)AsH
3
(Arsine) SbH
3
(Stibine)BiH
3
(Bismuthine)
 
NH
3
to BiH
3
the stability decreases.
 
The size of the central atom increase and there by the metal – hydrogen bond becomes weaker dueto decreased overlap between the large central atom and the small H – atom.
 
Reducing character of these hydrides gradually increases. Stibine and bismuthine are strongreducing agents.
 
All the hydrides can be prepared in similar methods. On hydrolysis of binary compounds of these metalswith water or dilute acids gives these hydrides.Mg
3
N
2
+ 6H
2
O
3Mg (OH)
2
 
+ 2NH
3
 Ca
3
P
2
+ 6HCl
3CaCl
2
+ 2PH
3
 
 
 
NH
3
and PH
3
are volatile , colourless gases.
 
The thermal stability of this hydrides decreases from NH
3
to BiH
3
due to decrease in M – H bondenergy.
 
These hydrides have a pyramidal shape with a lone pair of electron on the central atom.
 
In NH
3
N is sp
3
hybridised in other hydrides central atom uses pure p-orbitals.
 
In NH
3
the bond angle is 107°.
 
In PH
3
the bond angle is 94°.
 
Due to presence of lone pair of electrons on the central atom these hydrides acts as lewis bases.
 
The basic nature decreases as followsNH
3
> PH
3
> AsH
3
> SbH
3
> BiH
3
 Due to decrease in the electron density of the lone pair on the central atom.When Hydrogens are methylated basic nature increases PH
3
< P(CH
3
)
3
.
 
Because of donation of lone pair of electron by NH
3
to H
+
ion NH
4+
ion forms.
 
Phosphonium (PH
4+
) ion is less stable.
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V A Group Elements
3
 
Due to high electronegative difference between Nitrogen and Hydrogen NH
3
is capable of forminghydrogen bonding.
HH|NH........... HH||NH.......HH||NH.......HH||NH
 
 
M–H bond energies NH
3
>PH
3
> AsH
3
> SbH
3
> BiH
3
 From NH
3
to BH
3
:
1) Thermal stability decreases2) Reducing character increases3) Basic nature decreases4) Complex forming ability decreases5) Ease of formation of hydrides decreases
HALIDES :
 
All trihalides of these elements are possible except NBr
3
and NI
3
due to large size difference.
 
Trihalides are covalent and have a tetrahedral structure.
 
Trichlorides act as Lewis acids by utilizing the vacant d- orbitals.
 
On hydrolysis of NCl
3
the products are NH
3
and HOCl.
 
On hydrolysis of PCl
3
the main product is H
3
PO
3
(Phosphorous acid).
 
On hydrolysis of ASCl
3
the main product is H
3
ASO
3
(Arsenious acid).
 
On hydrolysis of SbCl
3
the main product is SbOCl (Antimony chloride).
 
On hydrolysis of BiCl
3
the main product is BiOCl (Bismuthyl chloride).In SbOCl and BiOCl the radicals are SbO
+
and BiO
+
are present.
 
With the increasing metallic character of the elements the halides become more ionic and theirtendency towards hydrolysis decreases.
 
PF
3
and PF
5 
are not hydrolysed because P–F bonds are stronger bonds than P – O bonds.
 
With the increase in the metallic character of the elements the halides become more ionic and theirtendency towards hydrolysis decreases.
 
All these elements except N and Bi doesn’t form pentahalides. N because of non – available vacantd –orbitals and Bi due to inert pair effect.
 
PCI
5
and SbCl
5
exists in triagonal bipyramid structures.
 
But as some bond angles are 90° and some are of 120° they are not stable.PCl
5
 
PCl
3
+ Cl
2
(chlorinating agent)
 
Hydrolysis of PCl
5
gives orthophosphoric acid.PCl
5
+ 4H
2
O
H
3
PO
4
+ 5HCl
 
Solid PCl
5
is ionic compound consisting of [PCl
4
]
+
, [PCl
6(–)
] cation is tetrahedral anion isoctahedral.
 
PBr
5
exists as [PBr
2
] Br
3(–)
.
OXIDES :Oxides of Nitrogen :
 
Oxides of N
2
are endothermic (except N
2
O
5
) and acts as better oxidants.
 
Except N
2
O
5
all are gases.
 
N
2
O (Laughing gas)
: First prepared by priestly.
 
Berthelot prepared it from Ammonium nitrate or ammonium sulphate and sodium nitrate.
OH2ONNONH
22C25034
0
+ ⎯  ⎯  ⎯  ⎯ 
 
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