GROUP VA (N, P, As, Sb, Bi

NITROGEN
• Occurs in nature as Di-nitrogen (N2).
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• Isotopes 7 N and 157 N

N2 (g) = 2N(g)  HDISS = 944.7 kJ/mol-1

HDISS extremely large due to the strength of the NN triple bonds.
NN has TWO  bonds and ONE σ bond
eg. E(NN) ~ 6E(N-N) E(C  C) ~ 2.5E(C-C)
NOTE:
Being one of the most electronegative elements, it enters extensively into
hydrogen-bond formation in its hydrogen compounds.
N-----H-X or N-H-----X
proton acceptor Proton donor.

EXPANSION OF OCTET
Normally no expansion of octet is permissible (inaccessibility of d
orbitals) EC = Is2 2s2 2p3
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EC = Is22s22p3
Nitrogen can complete its valence shell by:
1) Electron gain to form the nitride ion, N-3
Found only in salt-like nitrides of the most electropositive metals.
2) Formation of electron pair bonds
(a) single bonds as in NH3
(b) multiple bonds as in :NN:,
-N=N-
3) Formation of electron pair bonds with electron gain as in
NH2- or NH2-
(amide) (imide)
4) Formation of electron pair bond with electron loss as in the
tetrahedral ammonium and substituted ammonium ions:
eg R4N+ ,NH4+
ie. H3N: + H+  NH4+
R3N: + RX  R4N+ + X-

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 NOTE: There are some few stable species in which formally
the nitrogen valence shell is incomplete.
eg. NO, NO2 and nitro-oxides R2N=O
All these have one unpaired electron and are
paramagnetic
Formal oxidation number

Classically, formal oxidation number from –3 eg. NH 3 to +5

eg. HNO3 have been assigned to N2.

THREE COVALENT NITROGEN

In molecules eg. NR3 the bonding is considered as
involving sp3 hybrid orbitals and the lone pair
occupies the fourth position
SEE STRUCTURE OF NR1R2R3
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NOTE:
 As a result of a non-bonding electron pair, all NR3 compds
behave as LEWIS BASES.
 The bond angles depend on the groups attached to the N-atom.

SINGLE BOND ENERGIES

H3C-CH3 H2N-NH2 HO-OH F-F

356 160 140 150

So the N-N single bond is weak.

• This is due to the effects of repulsion between non-
bonding lone pairs. The result is that N 2 has a little
tendency to catenate.

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Catenation in Nitrogen.
• Nitrogen forms compounds containing a maximum of
eight nitrogen atoms in a chain.

• Many of these compounds incorporate multiple

bonded systems such as –N=N- which carry
hydrogen or organic substituents.

• E.g., R2N-N=NR2; R2N-N=N-NR2; RN=N-NR-NR2;

RN=N-NR-N=N-NR-N=NR; RN=N-NR-N=NR, etc.
where R represents an organic radical (some R’s
may be H, but known compounds contain only a few
H’s)

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 MULTIPLE BONDS
N2- Readily forms multiple p–p bonds like C, and in this
respect differ from P, As Sb and Bi.

 N forms many compounds for which there are no

analogues among the heavier elements.

 P, As and Sb do not exist as diatomic molecules. They form

tetrahedral molecules P4, As4, Sb4.

 N2 also forms triple bonds with other atoms.

eg. CH3C  N, F3S  N.

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Note: In compounds in which N forms one
single and one double bond:
X-N=Y
This grouping is NON- LINEAR.

N2 uses a set of sp2 hybrid orbitals, two of

which form  bonds to X and Y, whilst the
third houses the lone pair. A  bond to Y is
then formed using the Nitrogen’s pz orbital.

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 NITROGEN COMPDS
1) NITRIDES
Nitrides of the electropositive metals can be regarded as ionic eg.
Li3N, Ca3N2.
Some covalent nitrides are known eg. BN, S4N4, P3N5 etc.
NOTE:
Transition metals form nitrides analogous to transition borides, and
carbides in their constitution and properties.

2) HYDRIDES
(a) NH3: In the lab, can be formed by the reaction:
NH4X + OH-  NH3 + H2O + X-
• Industrially by the HABER PROCESS
N2(g) + 3H2(g) = 2NH3 (g) H= -46 kJ/mol
Cat + 400-550oC K25 = 103 Atm-2
102-103Atm
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 NOTE:
 Liquid ammonia is similar to water, although its auto dissociation is
less.
(BP of NH3 = - 33.35oC FP = -77.7oC)
2NH3 = NH4+ + NH2- K-50oC = 10-30
2H2O = H3O+ + OH- K25oC=10-14.
 Ammonia forms complexes with some metals.
eg. AgI +4NH3[Ag(NH3)4]+ + I-

Result: AgI is insoluble in H2O but soluble in NH3.

Some reactions of NH3

750  900oC
In the presence of Pt or Pt-Rh catalyst: 4NH3 + 5O2 Pt  Rh 4NO + 6H2O
Also 2NO + O2  2NO2.
The sequence in the industrial utilization of atmospheric N 2 is:
N2  NH3  NO  HNO3 (aq)
Haber Ostwald O2 + H 2O
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Process Process
3. OXIDES:
N2O, NO, N2O3, NO2, N2O4, N2O5, NO3, N2O6.
- NO+ = Nitrosonium ion
- NO2+ = nitronium ion.
 READ ON THE OXIDES OF NITROGEN

N 2O - Structure N-N-O (linear) Nitrous oxide

Obtained by thermal decomposition of molten NH4NO3 at 250-260oC:
NO as a contaminant is removed by passage through a FeSO 4 soln
and 1-2% of nitrogen.
Properties:
 Relatively not reactive. At RT it is inert to halogens and alkali metals.
 On heating decomposes to N2 and O2 and also reacts with alkali
metals and many organic compds.

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NO: (Nitric Oxide) N O
(Nitrogen monoxide, solid)
N O
 Paramagnetic. Formed in reactions involving reduction of HNO 3 and
solns of nitrates and nitrites.
8HNO3 + 3Cu  3Cu(NO3)2 + 4H2O + 2NO.
 Reacts instantly with O2
2NO + O2  2NO2.
 Can lose an electron to form the Nitrosonium ion (NO+) which forms
many salts.

NO2 and N2O4 (Nitrogen dioxide and Dinitrogen tetroxide).

 These two oxides exist in a strongly temperature dependent equilibrium,
both in solution and in the gas phase.
2NO2  N 2O4
Brown Colourless
(paramagnetic) (diamagnetic)
 In the solid state the oxide is wholly N2O4
 In the liquid, partial dissociation occurs:
eg. At 21.5oC it is 15% NO2. Dissociation is complete at 140oC.
The gases are highly toxic. 11
Nitrogen halides

 NX3, X = F, Cl, Br have been prepared.

 NF3 is the most stable (like CF4) and is unaffected by

water, dilute acid or alkali at RT.
 NCl3 = highly explosive liquid (mp -40oC) , rapidly
hydrolyzed by moisture.
NCl3 + 3H2O  NH3 + 3HOCl (bleach)
1. N-F bond much stronger than N-Cl bond.
2. Presence of d-orbitals in chlorine, diffuses the electron
cloud and thus makes N-Cl bond weak hence more
reactive.

 NBr3 = volatile solid

 NI3 = Not yet prepared.
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 Phosphorus(P), Arsernic (As), Antimony (Sb),
Bismuth(Bi)
P- Essentially covalent.
P P3- 1450 kJ/mol. Ionic compounds such as Na3P are very few.
As, Sb, Bi – Show an increasing trend to metallic character.
eg. BiF3 & Sb2(SO4)3 are ionic.
Differences between the chemistry of N & P

N P

1) Very strong p- p bonds 1) Unstable p-p bonds

2) p- d bonding is rare 2) Weak to moderate but
important p-d and d-d
3) No valence expansion bonding
3) There is valence
expansion. PF5, PF6-
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 Phosphorus:
Allotropes: White, Black and Red.

(i) White P:
 In the liquid and solid forms it consists of tetrahedral P4
molecules. P atoms are at the corners of a tetrahedron.
 In the vapour phase above 800oC appreciable dissociation
to P2 occurs.
 HAS HIGH ANGLE STRAIN (60o)

(ii) Black P:
- obtained by heating white P either under very high
pressure or at 220-370oC for 8 days in the presence
of Hg as a catalyst (with a seed of Black P).
- Has a complex polymeric structure.
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 (iii) Red P:
 Made by heating P4 at 270-300oC for several hours.
 A polymer with less strained bonds than white P.
 Much less reactive.

Reactivity:
 White P is the most volatile, reactive and least stable whereas
Black P is the least reactive.
White P – Inflames in air (stored under H 2O in which it is
insoluble)
 Red & Black P are stable in Air.
 White P is soluble in organic solvents e.g. CS 2, C6H6, PCl3,
liquid SO2 and NH3.
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• Bond Energy E (N-N) < E (P-P)
• Bond energies:
• N-N = 167 kJmol-1, P-P = 207 kJmol-1, As-As = 180
kJmol-1, Sb = Sb = 142 kJmol-1

• E(PP) = 490 kJ mol-1

– The repulsion between lone pairs on N lengthens and

weakens the bond between N-N atoms.
 COMPOUNDS OF GROUP V

1. HYDRIDES MH3.
BE: N-H = 391 kJ/mol, P-H = 322, As-H = 297, Sb-H =
255
N-H is stronger than the rest because N & H sizes are
comparable.

• Thermal stability of the gases fall rapidly down the

group and SbH3 and BiH3 are very unstable
thermally.

• MH3 compds, M = P, As or Sb are

exceedingly poisonous. AsH3 & SbH3 are unstable.
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 2. HALIDES: MX3 & MX5 : X = F, Cl, Br, I
M = P  Bi.
 MX3 (except PF3) compds are obtained by direct halogenation, keeping
the element in excess. An excess of the halogen gives MX5.

 MX3 compds – rapidly hydrolysed by water and are volatile. (PF 3

hydrolysed only slowly by water).

 PF3 is highly poisonous, due to formation of hemoglobin complex like

CO.

READ ON REACTIONS OF PCl3

THESE REACTIONS ARE TYPICAL FOR OTHER MCL3 COMPDS.

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Some properties of MX3 halides:
Hydrolysis reaction:
NCl3 + 3H2O → NH3 + 3HOCl
PCl3 + 3H2O → H3PO3 + 3HCl
SbCl3 + H2O → SbOCl + 2HCl
BiCl3 + H2O → BiOCl + 2HCl
Attack of water molecule on nitrogen is impossible because of non
availability of d-orbitals.

Lewis acid character:

 The trihalides, except NX3, act as Lewis acids, i.e. electron
pair acceptors, forming haloanions, SbCl4-, BiCl4-, etc.

 The trihalides (except NX3) can be oxidized to the

pentahalides.

• The lighter tri-halides of the group are predominantly covalent

in nature whilst the heavier ones e.g. BiF3 are ionic in nature.

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 Penta-halides, MX5

 Nitrogen does not form any pentahalides (MX 5) [due to

unavailability of d-orbitals].

 The stability of the pentahalides of the Group decreases in

the order P>Sb>As>Bi and in the order F>Cl>Br for the
halogens.

 Almost all the penta-halides can accept an electron pair

and act as Lewis acids, to form e.g. PF 6, PF5L, etc.

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OXIDES

Like the oxides of all the GROUPS:

(i) stability of higher oxidation state DECREASES with
increasing atomic number.
(ii) in a given oxidation state, the basicity of the oxides
INCREASES with increasing atomic number.
• THEREFORE: PIII & AsIII Oxides are
acidic
• SbIII oxide is amphoteric
• BiIII oxide is strictly
basic.

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 GROUP V OXIDES:

P4O6 As4O6 Sb4O6 Bi2O3

P4O7

P4O8 As2O4? Sb2O4

P4O9

P4O10 As2O5 Sb2O5 Bi2O5

4. SULPHIDES
 P & S combine directly above 100oC to give several sulphides: P4S3,
P4S5, P4S7, P4S10.
- P4S3 is used in safety matches.
 Asernic forms As4S3, As4S4, As2S3 and As2S5 by direct interaction.
 Sb2S3 and Bi2S3 are also known.
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