CHM 122

ELEMENTS OF GROUP VA
BY
DR. A.A ADEBISI
Representative Elements: Groups 5A-
8A

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 ELEMENTS OF GROUP VA
• Elements in this group include: nitrogen
(N), phosphorus (P), arsenic (As),
antimony (Sb) and bismuth (Bi).
• They are collectively called pnicogen.
• Nitrogen and phosphorus are distinctly
non-metallic, arsenic and antimony are
metalloids, while in bismuth, metallic
characteristics, predominate.
 Abundance and Occurrence
• Nitrogen is highly abundant making up 78%
by volume in air as dinitrogen (N 2).
• Phosphorus is highly abundant in crustal
rocks, mostly as orthophosphate of the apatite
group, Ca5(PO4)3X.
• Arsenic, antimony and bismuth are
comparatively less abundant in the earthcrust.
They mostly occur as sulphides
 Extraction
Laboratory preparation of Nitrogen
• Decomposition of sodium azide, NaN 3
2NaN3 → 2Na + 3N2
• Decomposition of ammonium nitrite
NH4NO2→ N2 + 2H2O
Industrially, large amount of nitrogen are
obtained as by-product during isolation of
oxygen by fractional distillation of liquid air.
 Extraction
• Phosphorus is obtained by reducing phosphate
rock with coke in the presence of sand at 1400 -
1500℃ in an electric furnace; phosphorus vapour
distils out and is condensed under water to yield
white phosphorus.
2Ca3(PO4)2 + 6SiO2 + 10C → 6CaSiO3 + 10CO + P4
• Arsenic, antimony and bismuth can be obtained
from their sulphide ores. The ore is roasted in air
to convert the sulphide to the oxide which is then
reduced by heating with coke.
 Uses
• Nitrogen is widely used to provide inert atmosphere both
industrially and in laboratories.
• Liquid nitrogen is a useful refrigerant.
• Besides the use of elemental nitrogen, compounds of
nitrogen have extensive applications in various fields.
Ammonia is used in various forms as a fertiliser, e.g., as
NH4NO3, (NH4)2SO4, (NH4)2HPO4, etc. Its applications also
include refrigeration, as a pH controller in food and beverage
industry, pharmaceuticals and in water purification. Nitric
acid is another important compound of nitrogen. Its major
uses include manufacture of NH4NO3, explosives like
nitroglycerine, nitrocellulose and trinitrotoluene (TNT).
 Uses
• The most important application of phosphorus is
in the production of phosphate fertilizers.
• Phosphorus is also used to make very pure
phosphoric acid.
• Some P is converted to P4S10 (used in making
organo-phosphorus) and P4S3 (used to make safety
matches and in the generation of fireworks).
• Phosphorus is also important in steel manufacture
and production of phosphor bronze.
 Uses
• Elemental arsenic, antimony and bismuth are use
in the production of various alloys.
• Arsenic compounds find extensive use in
agriculture as herbicides for weed and pest
control and as a wood preservative.
• Antimony compound, antimonial lead, is used in
storage batteries. Compounds of antimony with
aluminium, gallium and indium find its
applications in infrared devices and in diodes.
Table 1.1: Some Physical Properties of Group 5A
 Physical Properties
• Nitrogen is gaseous in nature and exists as a
diatomic molecule N2. The dinitrogen molecule
has a triple bond N≡N of unusual stability.
• The stability of this bond is responsible for the
low reactivity of this molecule thus making it
suitable as an inert environment for many
chemical studies of reactions that are either
oxygen or moisture sensitive.
• It has no allotropes.
 Physical Properties
• Phosphorus is solid at room temperature.
• Solid phosphorus has several allotropic forms with
the most common of these been white phosphorus.
Other allotropes include red phosphorus and black
phosphorus which is the least reactive allotrope but
most thermodynamically stable.
• Phosphorus exists as tetrahedral P 4 molecules in the
liquid and gas phases. At very high temperature, P 4
molecules dissociate into P2 molecules.
Figure 14.16 allotropes of phosphorous.

White phosphorous (P4) Strained bonds in P4

Red phosphorous
 Physical Properties
• Arsenic, antimony and bismuth also exhibit a
variety of allotropes. The most stable allotrope
of arsenic is the grey (α) form which is similar
to the rhombohedral form of phosphorus
(black phosphorus).
• Generally, the metallic allotropes become
more stable with increasing atomic number.
 Physical Properties
Catenation
• The catenation tendency of Group 15 elements is less than that of
carbon. This is because of the lower M-M bond energies of the
Group 15 elements as compared to that of carbon.
Bond energy (kJ/mol)
C – C (353) N – N (164) P – P (202) As – As(147)
• Nitrogen and phosphorus show catenation tendencies to form the
following compounds.
Nitrogen(N) : H2N – NH2 (hydrazine),H – N = N≡ N (hydrazoicacid)
Phosphorus (P) : H2P –PH2
• Phosphorus shows a distinct tendency for catenation by forming
both cyclic and open chain compounds. Nitrogen shows little
tendency for catenation due to lower N-N bond energy.
• Other elements do not show any tendency towards catenation.
 Properties and Periodic Trends
• The change from non-metallic to metallic
character with increase in the atomic number is
well illustrated in this group.
• The electronegativity of these elements decreases
gradually on moving down the group.
• The density, melting and boiling points of the
elements increase with increase in atomic number.
• Atomic radii increase with increase in atomic
number and as a consequence, ionization energies
decrease on descending the group.
 Anomalous Properties of Nitrogen
• High value of electronegativity of N atom and high
ionization energy.
• Absence of d-orbitals in the valency shell.
• Nitrogen is gas while others members are solids.
• Nitrogen molecule is diatomic while other elements
form tetratomic molecules such as P4, As4 and Sb4.
• Nitrogen exhibits a large number of oxidation
states from -3 to +5. Other elements do not exhibit
such a variety of oxidation states.
 Chemical Properties
• Nitrogen is quite inert at room temperature
because of the great strength of the N≡N bond.
• White phosphorus is very reactive while red and
black allotropes are not.
• Arsenic, antimony and bismuth are fairly reactive.
• With oxygen, nitrogen combines only at very high
temperatures to yield nitric oxide; white
phosphorus combines so readily giving trioxide
and pentoxide that is stored under water.
 Chemical Properties
• Arsenic, antimony and bismuth on heating in air
form the trioxides As2O3, Sb2O3 and Bi2O3,
respectively. All except nitrogen react with halogens
to form halides EX3 and EX5; bismuth yields only
BiX3.
• All react with sulphur, except nitrogen, to form the
sulphides.
• Only nitrogen reacts with hydrogen under suitable
conditions to form ammonia.
• All the elements of Group 5 react with metals;
nitrogen forming nitrides, phosphorus and arsenic
giving phosphides and arsenides whereas antimony
and bismuth form alloys.
 Ammonia
• It is the most important industrial chemical of all the
nitrogen compounds; it is produced in the largest
quantities.
• Ammonia can be obtained in the laboratory by heating
ammonium salts with an alkali:
2NH4Cl + Ca(OH)2 → CaCl2 + 2NH3 + 2H2O
• Ammonia is manufactured industrially by Haber
process.
N2 + 3H2 → 2NH3, ΔHo = - 92.0 kJmol-1, Temp
800K, Pressure 250atm, Iron catalyst
 Ammonia
Ammonia has a strong characteristic pungent
smell.
It is a colourless gas at room temperature and
can be easily liquefied by either increasing the
pressure or decreasing the temperature.
It is highly soluble in water.
NH3 molecule has a pyramidal structure, having
a lone pair of electrons at the apex.
 Oxides of nitrogen
Formula Name Colour Remarks
N2O Nitrous oxide Colourless Unreactive
NO Nitric oxide Colourless Moderately reactive
N2O3 Dinitrogen Dark blue Extensively
trioxide dissociated as gas
NO2 Nitrogen dioxide Brown Moderately reactive
N2O4 Dinitrogen tetroxide Colourless Extensively
dissociated to NO2 as
gas and partly as
liquid
N2O5 Dinitrogen pentoxide Colourless Unstable as gas; ionic
solid
NO3,N2O6 Nitrogen trioxide, Not well characterised
dinitrogen hexoxide and quite unstable
 Oxide of nitrogen
• Nitrogen oxides are oxidizing agent.
• N2O and NO are neutral oxides, while the other
oxides are acidic.
• Some are acid anhydrides (a compound that
forms an oxoacid when it reacts with water) e.g
N 2O 5
• In atmospheric chemistry where the oxides play
an important two edged role in both
maintaining and polluting the atmosphere they
are referred to collectively as NOx
 Oxides of Phosphorus, Arsenic, Antimony
and Bismuth
• P, As and Sb form oxides in both +3 and +5
oxidation states.
• Only one oxide of bismuth, Bi 2O3 is known as we
know that the stability of higher oxidation states
decreases on going down the group.
• Except for Bi2O3, others exist in dimeric form.
• The basic character of oxides increases on
descending the group. The oxides of P and As are
acidic, those of Sb are amphoteric and of Bi are
wholly basic.
 Oxoacids of nitrogen
• The two better known oxoacids of nitrogen are nitrous acid
and nitric acid.
• Nitrous acid HNO2 is an unstable, weak acid which is
known only in aqueous solution.
• Nitric acid HNO3 is a strong acid as well as a strong
oxidizing agent
• It is made in the three-step Ostwald process
• STEP 1: Oxidation of ammonia
4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(g)
• STEP 2: Oxidation of nitrogen oxide
2NO(g) + O2(g) → 2NO2(g)
• STEP 3: Disproportionation of NO2 in water;
3NO2(g) + H2O(l) → 2HNO3(aq) + NO(g)
 Oxoacid of Phosphorus
• The simplest phosphoric acid is H3PO4 called
orthophosphoric acid.
• H3PO4 can also be made from phosphate rock
by treating it with H2SO4.
Ca3(PO4)2 + 3H2SO4 → 2H3PO4 + 3CaSO4
• Used primarily for the production of fertilizer,
food additives, and detergent.
Nitrogen cycle