p BLOCK ELEMENTS (Group 15)

GROUP 15 ELEMENTS: THE NITROGEN FAMILY

Group 15 includes nitrogen, phosphorus, arsenic, antimony, bismuth and moscovium.

Occurrence
ELEMENT ABUNDANCE SOURCE
N N2 comprises In the earth’s crust,
78% (by Sodium nitrate, NaNO3 (called Chile saltpetre) potassium nitrate
volume) (Indian saltpetre).
of the In the form of proteins in plants and animals.
atmosphere.
P Occurs in minerals of the apatite family,
Ca9(PO4 )6 CaX2 (X = F, Cl or OH) (ex- fluorapatite Ca9(PO4 )6 CaF2 )
which are the main components of phosphate rocks.
Essential constituent of animal and plant matter. It is present in
bones as well as in living cells.
Phosphoproteins are present in milk and eggs.
As, Sb &Bi found mainly as sulphide minerals

Electronic Configuration
Outer electronic configuration is ns2np3.

Element N P As Sb Bi
EC [He]2s22p3 [Ne]3s2 3p3 [Ar]3d104s2 4p3 [Kr]4d105s25p3 [Xe]4f145d106s26p3

NOTE – Moscovium (Mc -115) is a synthetic radioactive element.

Electronic configuration - [Rn] 5f 146d107s27p3

Atomic Radii
Element N P As Sb Bi
Covalent radius(pm) 70 110 121 141 148
Ionic radius (pm) 171(E ) 212(E ) 222(E ) 76 (E ) 103(E3+)
3– 3– 3– 3+

• Order of atomic radius - N < P < As < Sb < Bi

• Order of ionic radius - N < P < As
• Covalent and ionic (in a particular state) radii increase in size down the group.
• N to P - Considerable increase in covalent radius.
As to Bi - Only a small increase in covalent radius is observed.
This is due to the presence of filled d and/or f orbitals in heavier members.
Ionization Enthalpy
Element N P As Sb Bi
-1
Ionization enthalpy (kJmol )1st 1402 1012 947 834 703
2nd 2856 1903 1798 1595 1610
3rd 4577 2910 2736 2443 2466
• First ionisation enthalpy – N > P > As > Sb > Bi
• Second ionisation enthalpy – N > P > As > Bi > Sb
• Third ionisation enthalpy – N > P > As > Bi > Sb
• Decreases down the group due to gradual increase in atomic size.
• Ionisation enthalpy of the group 15 elements is much greater than that of group 14
elements in the corresponding periods due to the extra stable half-filled p orbitals &
smaller size.
• The order of ionisation enthalpies is ∆H1 < ∆H2 < ∆H3
Electronegativity
Element N P As Sb Bi
Electronegativity 3.0 2.1 2.0 1.9 1.9
Order – N > P > As > Sb ≈ Bi

Physical Properties
• All the elements of this group are polyatomic.
Dinitrogen - diatomic gas All others are solids.
• Metallic character increases down the group due to decrease in ionisation enthalpy
and increase in atomic size.
N & P - non-metals As & Sb – metalloid Bi - metal.
• Except nitrogen, all the elements show allotropy.
• Melting point & Boiling point
Boiling point - increase from top to bottom in the group.
Melting point - increases upto arsenic & then decreases upto bismuth.
Element N2 White P As Sb Bi
MP (K) 63 317 1089 (Grey α-form at 38.6 atm) 904 544
BP K) 77.2 554 888 (Sublimation temperature) 1860 1837
Melting point – As > Sb> Bi> P > N Boiling point – Sb > Bi > As > P > N

• Density of the elements increases down the group from N to Bi

Element N P As Sb Bi
Density (at 0.879 (at 63K) 1.823 5.778(Grey α-form) 6.697 9.808
298K)
Order- Bi > Sb > As> P > N

Oxidation state and trends in chemical reactivity

• The common oxidation states of these elements are –3, +3 and +5.
• The tendency to exhibit –3 oxidation state decreases down the group due to increase
in size and metallic character.
 Exception - Bi hardly forms any compound in –3 oxidation state.
• The stability of +5 oxidation state decreases and that of +3 state increases down the
group due to inert pair effect.
The only well characterised Bi (V) compound is BiF5.
Exception - N does not form compounds in +5 oxidation state with halogens as it does
not have d-orbitals to accommodate electrons from other elements to form bonds.

• Nitrogen (besides +5) exhibits + 1, + 2, + 4 oxidation states also when it reacts with
oxygen.
• Phosphorus also shows +1 and +4 oxidation states in some oxoacids.
• In the case of nitrogen, all oxidation states from +1 to +4 tend to disproportionate in
acid solution. For example, 3HNO2 → HNO3 + H2O + 2NO.
• In case of phosphorus nearly all intermediate oxidation states disproportionate into +5
&–3 both in alkali and acid.
• +3 oxidation state in case of arsenic, antimony and bismuth becomes increasingly
stable with respect to disproportionation.

Anomalous properties of nitrogen

Nitrogen differs from the rest of the members of this group
Reason- due to its small size, high electronegativity, high ionisation enthalpy and non-
availability of d orbitals.

• Nitrogen exists as a diatomic molecule with a triple bond (one s and two p) between
the two atoms. Its bond enthalpy (941.4 kJ mol–1) is very high.
Reason - Nitrogen has unique ability to form pπ -pπ multiple bonds with itself and
with other elements having small size and high electronegativity (e.g., C, O).
• Phosphorus, arsenic and antimony form single bonds as P–P, As–As and Sb–Sb while
bismuth forms metallic bonds in elemental state
Reason- Heavier elements of this group do not form pπ-pπ bonds as their atomic
orbitals are so large and diffuse that they cannot have effective overlapping.
• The single N–N bond is weaker than the single P–P bond
Reason – due to small bond length the non-bonding electrons experience high
interelectronic repulsion.
• The catenation tendency is weaker in nitrogen.
Reason - The single N–N bond is weaker than the single P–P bond
• N 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 also with transition metals when their
compounds like P(C2H5)3 and As(C6H5)3 act as ligands
Reason- due to the absence of d orbitals in nitrogen in its valence shell.

• Nitrogen is restricted to a maximum covalency of 4 since only four (one s and three p)
orbitals are available for bonding. The heavier elements have vacant d orbitals in the
outermost shell which can be used for bonding (covalency) and hence, expand their
covalence.
Chemical properties
Reactivity towards hydrogen:
All the elements of Group 15 form hydrides of the type EH3 where E = N, P, As, Sb or Bi

Property NH3 PH3 AsH3 SbH3 BiH3

Melting point(K) 195.2 139.5 156.7 185 -
Boiling point(K) 238.5 185.5 210.6 254.6 290
(E-H) bond distance(pm) 101.7 141.9 151.9 170.7 -
HEH bond angle (°) 107.8 93.6 91.8 91.3
∆f HO/kJ mol–1 –46.1 13.4 66.4 145.1 278
∆diss H0(E–H)/kJ mol–1 389 322 297 255

• Bond length (E-H) - NH3 < PH3 < AsH3 < SbH3
• Bond dissociation energy (E-H) - NH3 > PH3 > AsH3 > SbH3
• Stability of hydrides - NH3 > PH3 > AsH3 > SbH3
Reason – due to decrease in bond dissociation enthalpy down the group.
• Reducing character of the hydrides - NH3 < PH3 < AsH3 < SbH3 < BiH3
Reason – due to decrease in bond dissociation enthalpy down the group
• Basicity - NH3 > PH3 > AsH3 > SbH3 > BiH3 .
Reason –
• B.Pt - BiH3 > SbH3 > NH3 > AsH3> PH3
Due to high electronegativity and small size of nitrogen, NH3 exhibits hydrogen
bonding in solid as well as liquid state. Because of this, it has higher melting and
boiling points than that of PH3 & AsH3
• M.Pt - NH3 > SbH3 > AsH3> PH3
• Bond angle - NH3 > PH3 > AsH3 > SbH3
Reactivity towards oxygen:
• All these elements form two types of oxides: E2O3 and E2O5 .
• Acidic character - E2O3 < E2O5
Reason - The oxide in the higher oxidation state of the element is more acidic than
that of lower oxidation state.
• Acidic character - N2O3 > P2O3 > As2O3 > Sb2O3 > Bi2O3
Reason-
N2O3 & P2O3 - acidic
As2O3 & Sb2O3 - amphoteric
Bi2O3 - predominantly basic
Reactivity towards halogen
• These elements react to form two series of halides: EX3 and EX5.
• Nitrogen does not form pentahalide due to non-availability of the d orbitals in its
valence shell.
• Pentahalides are more covalent than trihalides.
 Reason -This is due to the fact that in pentahalides +5 oxidation state exists while
in the case of trihalides +3 oxidation state exists. Since elements in +5 oxidation
state will have more polarising power than in +3 oxidation state, the covalent
character of bonds is more in pentahalides.
• All the trihalides of these elements except those of nitrogen are stable. In case of
nitrogen, only NF3 is known to be stable.
• Trihalides are predominantly covalent in nature.
Exception - BiF3
Reactivity towards metals
• All these elements react with metals to form their binary compounds exhibiting –3
oxidation state.
Ex- Ca3 N2 (calcium nitride) Ca3 P2 (calcium phosphide)

Na3 As (sodium arsenide) Zn3 Sb2 (zinc antimonide)

Mg3 Bi2 (magnesium bismuthide).