COMPARATIVE STUDY ON GROUP 15 ELEMENTS

The properties of Group 15 elements may be conveniently discussed in a

comprehensive manner based on the following points together with the present members,
electronic structures, oxidation states, coordination numbers etc.

Elements Electronic Configuration Oxidation State Coordination Number

Nitrogen (N) [He]2s22p3 −III, −II, −I, 0, I, *(1), (2), 3, 4
II, III, IV, V
Phosphorus (P) [Ne]3s23p3 III, V 3, 4, 5, 6
Arsenic (As) [Ar]3d104s24p3 III, V 3, 4, (5), 6
10 2 3
Antimony (Sb) [Kr]4d 5s 5p III, V 3, 4, (5), 6
Bismuth (Bi) [Xe]4f145d106s26p3 III, V 3, 6
*Values within parentheses indicate less-favorable coordination number

The variation of ionization energy, electron affinity, electronegativity and

catenation property for Group 15 elements may be best explained on the basis of the
following graphical representations:

Figure 1(a) Figure 1(b)

Dr. Jishnunil Chakraborty - Assistant Professor - St. Paul’s C. M. College, Kolkata 1

 Figure 1(c) Figure 1(d)

Element I.E. (kJ mol−1) E.A. (kJ mol−1) E.N. (Pauling Scale)
Nitrogen 1403 −6.72 3.0
Phosphorus 1012 +71.94 2.1
Arsenic 947 +77.28 2.0
Antimony 834 +101.64 1.9
Bismuth 703 +105 1.9

Ionization energy: There is a drop in ionization energy from N→P (Figure 1(a)) with
the increase in atomic volume. From P→As the drop in I.E. is lower due to greater
effective nuclear charge (3d10) for As. Again, from As→Sb→Bi there is a gradual drop in
I.E. as normally expected.
Electron affinity: The electron affinity of N (Figure 1(b)) is unusually low due to strong
interelectronic repulsion in ‘2p’ sublevel. The sudden increase in E.A. in P is a result of
relaxation of this repulsion, which gradually diminishes with the increase in atomic
volume explaining the gradual increase in E.A. on descending the group.

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Electronegativity: Electronegativity (Figure 1(c)) is maximum at N due to its smallest
volume in the group and then decreases gradually on descending the group. From As
(3d10) to Bi(4f14), the decrease in E.N. values become smaller due to the increase in
effective nuclear charge.
Catenation property: Catenation property (Figure 1(d)) follows more or less the same
trend for bond energy− the resultant of (i) constructive contribution of overlap integral
and (ii) disruptive interaction due to lp-lp repulsion. For nitrogen B.E. is very low as it
suffers from severe lp-lp repulsion which is relaxed in P−P linkage, attaining maximum
value. Again from ‘As−As’, ‘Sb−Sb’ etc., the drop in B.E. is due to increasing
insufficient overlap with increasing atomic volume.
Comparison of the Hydrides of Group 15 Elements
1. With respect to preparation.
2. Boiling point trend: NH3 > PH3 < AsH3 < SbH3. The high boiling point of NH3 is due
to its association through hydrogen bonding which is more or less absent from PH3, but
boiling point increase gradually with the increase in molecular weight.
3. Reducing property: follows the trend NH3 < PH3 < AsH3 < SbH3.
Explanation: (i) As we move from N→P→As→Sb, the stability E−III decreases with
decrease in electronegativity, and (ii) ‘E−H’ bond energy decreases with decrease in
overlap integral.
4. Thermal stability: follows the trend NH3 > PH3 >AsH3 >SbH3 − a sequence of
decreasing bond energy.
5. Basic property: NH3 > PH3 >AsH3 >SbH3. this is more or less the similar trend of
‘E−H’ bond formations after the acceptance of proton.
6. Structure: This has been discussed latter.
7. pKa values: NH3 (39) < PH3 (37) < AsH3 (−15) < SbH3 (−19) − similar trend of
decreasing bond energy, thus favoring acidity.
Electronic Structures and Oxidation State
All the elements belonging to this group contain five electrons in their outer-shell.
They exhibit a maximum oxidation state of five towards oxygen by using all the five
outer electrons in forming bonds. The tendency of the s-electron pair to remain inert (i.e.

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inert pair effect) increases with the increase in atomic number and becomes most
pronounced in bismuth. Thus only the p-electrons are used in bonding and trivalency
results. The valency of three and five are shown with sulfur and halogens and the
hydrides are trivalent. A very wide range of oxidation states are exhibited by nitrogen
from −3 to +5 in the following compounds:
NH3(−3), N2H4(−2), NH2OH(−1), N2(0), N2O(+1), NO(+2), N2O3(+3), NO2(+4),
N2O5(+5), etc.
The negative oxidation states for nitrogen arise as it has a considerably large
electronegativity of 3.0 in Pauling’s scale. In the intermediate oxidation state (+3) e.g., in
HNO2, the central nitrogen atom exhibits both oxidizing and reducing properties as it
may pass on to the lower oxidation states by capturing electrons and also to the higher
oxidation states by ejecting electrons. On the other hand nitrogen when present in the
highest possible oxidation state i.e., (+5) e.g., in HNO3 it acts exclusively as an oxidant as
it has the ability to accept electrons.
Bi(V) e.g., Bi2O5 and NaBiO3 are potentially very strong oxidizing agents due to
the inert pair effect which is operative in Bi for its +5 oxidation state. The next stronger
oxidizing agent is NO3−, As(V) and Sb(V) are mild oxidizing agents. Higher oxidizing
strength for N(V) is due to smaller atomic volume with higher electronegativity and the
stability of N(IV), N(III) and N(II)− oxides enjoying π-bonding in 2p-sublevel. So the
order of oxidizing strengths for the Group 15 elements in their +5 oxidation state is:
Bi(V) >> N(V) As(V) > Sb(V) > P(V)
Molecular Structures of the Elements
The first element in each group differs from the rest and thus nitrogen is gaseous
and diatomic involving triply bonded nitrogen. N≡N having high bond dissociation
energy (~946 kJ mol−1) and is relatively inert. The other members are solid and have
allotropic forms.
Phosphorus exists as tetrahedral P4 molecules in gaseous and liquid states, and
also as solid called white phosphorus. If white phosphorus is heated above 250 °C for
some time, the less reactive red phosphorus is formed and heating white phosphorus
under high pressure results in black phosphorus which is inert and has a giant structure.

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Red phosphorus has intriguing double-layer structure consisting of mutually
perpendicular, connected, pentagonal tubes (Figure 2a).

Figure 2(a). Red phosphorus

The higher reactivity of white phosphorus over other allotropes is due to the
following tetrahedral structure suffering from considerable strain having P−P−P bond
angle 60° differing widely from the ideal angle 109°28′:

Figure 2(b). White phosphorus

Arsenic and antimony each have allotropic forms− a reactive tetrahedral
form As4 and Sb4 which resemble white phosphorus and much less reactive metallic
forms with layered structure. The following calculation reveals that:
EN≡N = 946 kJ mol−1
EN−N = 159 kJ mol−1
EN≡N − 3EN−N = (946−477) = 469 kJ mol−1

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The reason for the existence of nitrogen as N2 rather than N4 (e.g., P4, As4, Sb4, etc.) may
be explained based on bond energy calculation shown above. Incase of nitrogen, EN≡N >
3EN−N, but EP≡P < 3EP−P for phosphorus and other elements of the group:
EP≡P = 523 kJ mol−1
EP−P = 209 kJ mol−1
3EP−P = 3 × 209 = 627 kJ mol−1
3EP−P > EP≡P
Besides, after the formation of N−N σ-bond there is strong π-bond formation by
the overlap of small and localized p-orbitals of nitrogen while in case of phosphorus and
other elements of the group, π-bonding occurs in a less efficient way by the overlap of
the larger and diffused p-orbitals with long interatomic distance. This accounts for the
formation of N≡N and forbids the formation of P≡P, As≡As, etc.
Difference of Nitrogen from the Rest of the Group Elements
The small size, higher electronegativity, strong pπ− pπ interaction in 2p-sublevel
and absence of vacant d-orbital of suitable energy to expand its covalency beyond four
makes nitrogen different from the rest of the group. Thus phosphorus forms PCl5 through
sp3d hybridization while nitrogen fails to form NCl5 as it is devoid of low-lying vacant d-
orbitals.
Nitrogen differs from the rest of the group via the formation of strong pπ−pπ
multiple bonds and so form a number of compounds, a class of itself, and have no
counterparts in the other elements e.g., NO3−, NO2−, N3− (azide), N≡N, N2O, NO, NO2,
C≡N, etc. because nitrogen forms multiple bonds, the oxides N2O3, N2O5 are monomeric,
whilst the tri- and pentoxides of other elements are dimeric. For many similar compounds
of the second and third period may be noted as follows: BCl3/(AlCl3)2(g); CO2/(SiO2)n;
HNO3/(HPO3)n; N2O3/(P2O3)2; N2O5(g)/(P2O5)2(g).
The reason for the dimerization in the compounds of phosphorus stems from the
fact that very weak π-bonding occurs due to the wide difference in orbital sizes of
diffused p-orbitals of phosphorus and that of oxygen. As such charge neutralization is not
possible here and this is met up via coordination of electron pair from the other

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negatively charged oxygens to the electron deficient central element favoring
polymerization in the compounds:

δ+ δ−
P O

Figure 3
Electronegativity and Metallic and Nonmetallic Character
Metallic character increases within the group with increase in atomic number.
Nitrogen and phosphorus are nonmetals, arsenic and antimony are metalloids and
bismuth is a true metal. This is evidenced by the increase in basic nature of the oxides
with the increase in atomic number and increased tendency to form positively charged
ions. Thus the normal oxides of N and P are strongly acidic, whilst that for As and Sb are
amphoteric and Bi is largely basic.
Compounds of Group 15 Elements and Bond type
The ionization energy required to produce M5+ ion is so immense that it never
occurs. The sum of the first three ionization energies for Sb and Bi are just low enough
for them to form M3+ ions.
Fluorine is the only element which gives a large enough electronegativity
difference to permit ionic bonds and thus SbF3 and BiF3 exist as ionic solids. The M3+
ions are rapidly hydrolyzed in water to produce SbO+ and BiO+, but this change is
reversed by the addition of 5(M) HCl:
H 2O
Bi
3+
BiO+
HCl
It is possible to attain inert gas configuration ns2np6 e.g., N3− by the acceptance of
three electrons only by the reaction of nitrogen with highly electropositive metals to give
ionic nitrides e.g., Li3N, Be3N2, Mg3N2, Ca3N2 etc. In majority of the cases the bonds are
predominantly covalent.
Hydrides: All the elements form volatile hydrides. The ease of formation, stability,
ability to use the lone pair of electrons for coordination (and hence the basic strength)
decrease on descending the group.
NH3 is prepared in the laboratory by heating ammonium salts with a strong base
e.g., NaOH: NH4Cl + NaOH = NaCl + NH3 + H2O

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While AsH3 and SbH3 are formed in Marsh’s test by the reduction of trivalent arsenic and
antimony with zinc and acid.
In all the hydrides MH3, the central element is in the sp3 state of hybridization
leading to pyramidal geometry with one position occupied by a lone-pair of electrons.
The bond-angle in the hydrides decreases from NH3 to SbH3 e.g.,

NH3 ∠H−N−H 106° 45′

lp-bp repulsion PH3 ∠H−P−H 94°
M
AsH3 ∠H−As−H 91° 48′
SbH3 ∠H−Sb−H ∼91°
H H
H
Figure 4
The contraction of bond-angle in NH3 from the ideal tetrahedral value (109° 28′) results
from the greater lp-bp repulsion over bp-bp repulsion where the former is responsible for
squeezing the bond-angle from the ideal value as mentioned above.
The prime factor for hybridization is the equalization in energy of the orbitals
undergoing such a process. In the ground state the ns and np levels differ to some extent
in energy and is compensated by the bond energy via the formation of strong N−H bond
(where the sizes of the orbitals of N and H does not differ too much i.e., S = ∫Ψsp3(N)Ψ1s
(H) is high). Thus NH3 is properly sp3 hybridized where the lone-pair of electrons will be
in sp3 hybrid orbital having only 25% s-character. In case of PH3 and other hydrides of
the following elements, weak ‘M−H’ bonds are formed by the overlap of the more
diffused orbitals of the central elements (P, As, Sb, etc.) and that of hydrogen where
orbital sizes differ widely. Thus the low bond-energy is not sufficient to compensate
completely the excitation energy necessary for energy equalization and hence in such
cases sp3 hybridization practically does not occur. The ‘M−H’ bonds are formed in such
cases via the overlap of pure p-orbitals of the central element with the s-orbital of
hydrogen. The bond-angles in such cases e.g., ∠H−P−H, ∠H−As−H etc. are close to 90°
rather than the ideal tetrahedral angle. Therefore the lone-pair of electrons in PH3, AsH3,
SbH3 etc. remains in an orbital having almost 100% s-character ad hence has lower donor

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ability or basic strength. NH3 is thus a stronger base than PH3, AsH3 etc. and readily
forms NH4+ salts using the lone-pair while PH3 forms salts preferably with strong acids
e.g., HI only under anhydrous condition. NH3 also forms coordination complexes with the
ions of Co, Ni, Cu, Zn, etc. NH3 is a weak base and remains hydrogen bonded. PH3 is a
very much weaker base and like AsH3, SbH3 and BiH3 does not form H-bond and reserve
reducing capacity.
The formation of penta-hydrides of type MH5 requiring sp3d hybridization is not
possible as the electronegativity of H is not sufficiently large to create electron deficiency
on the central element e.g., P, As, Sb (and not N) to cause d-orbital contraction and hence
the equalization in energy of the ns, np and nd orbitals as demanded as an essential
criterion for hybridization is not met.
Hydrides of type M2H4: The bond energy value for ‘N−N’ single bond is 159 kJ mol−1
while that for ‘P−P’ bond is 209 kJ mol−1 and this ordering of bond-energy in the lighter
and heavier atoms is maintained in the remaining groups of the representative elements.
This may be attributed to the greater lp-lp repulsion of the neighboring atoms (having
smaller and localized orbitals) than those in the heavier members. Hydrazine, N2H4, the
simplest catenated ‘N−N’ compound is unstable with respect to its elements and the
higher homologs become increasingly unstable. This is due to the fact that N−N single
bond energy is only about one sixth of the N≡N triple bond energy (946 kJ mol−1).
The simplest pernitride hydrazine or diamide is prepared by the oxidation of NH3
(excess) with NaOCl in presence of glue or gelatin. The latter acts as a negative catalyst
for the side reaction.
NH3 + NaOCl = NH2Cl + NaOH (fast)
2NH3 + NH2Cl = N2H4 + NH4Cl (slow)
The structure of hydrazine is similar to that of H2O2 where both the N atoms are sp3
hybridized with a lone-pair (in sp3 hybrid orbital) of electrons on each of the nitrogen
atoms and hence it is basic.
H H H

N N N N
H H H H H
Structure-I: staggered Structure-II: gauche
Figure 5
Dr. Jishnunil Chakraborty - Assistant Professor - St. Paul’s C. M. College, Kolkata 9
Figure 5 shows that the lp-lp repulsion is smaller in Structure-I and hence seems to be
more stable. The high dipole moment value of N2H4 can of course be explained only by
assuming the gauche form (Structure-II).
It forms two series of salts:
N2H4 + HX = N2H5+ + X−
N2H4 + 2HX = N2H62+ + 2X−
Hydrazine is a powerful reducing agent in alkaline solution but a mild one in acidic or
neutral solution:
N2H4 + 2I2 = 4HI + N2
N2H4 + O2 = 2H2O2 + N2
Phosphorus has greater catenated compounds (P−P, B.E.= 209 kJ mol−1) than nitrogen
e.g., P2H4, P3H6, P4H6 etc.) which are unstable.
Halides: Unlike heavier members nitrogen forms a series of halides derived from HN3,
for example FN3, ClN3, BrN3 and IN3 resembling covalent azides in extreme instability
and explosive nature.
Trihalides: All the possible trihalides of N, P, As, Sb and Bi are known; with the
nitrogen compounds are least stable. NF3 is stable but NCl3 is explosive and NBr3 and
NI3 are known only as their unstable ammoniates e.g., NBr3.6NH3 and NI3.6NH3. The
trend for stability: NF3 >> NCl3 > NBr3 > NI3. The greater stability of NF3 over the other
analogs is due to the higher N−F bond strength (arising out of the overlap of less diffused
orbitals having similar sizes with no steric congestion) and absence of vacant d-orbital of
suitable energy.
The instability and explosive nature of NCl3, NBr3 and NI3 may be attributed to
the lower bond-strength of N−X (X = Cl, Br, I) arising out of the overlap of orbitals
having wide differences in sizes and greater steric congestion.
All the trihalides are sp3 hybridized leading to a pyramidal geometry with one
position occupied by a lone-pair of electrons.
The trihalides all hydrolyze readily with water, but the products vary depending
upon the central element.
NCl3 + 3H2O = NH3 + 3HOCl

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 Cl H Cl
SN2
N Cl N + HOCl
Mechanism
Cl Cl
H O Repeating in two steps

H NH3
Figure 6
PCl3 + 3H2O = Cl H3PO3 + 3HCl
Cl Cl
SN 2 P
P Cl
sp3d hybridized
Cl Cl TBP structute
O
H O
H H
H

OH Cl
Repeating in two steps
P OH P Cl
OH OH

O H O
P OH Tautomerization P
OH HO OH
H
Phosphorous acid
Figure 7

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 PCl3 + 3H2O = H3PO3 + 3HCl
AsCl3 + 3H2O = H3AsO3 + 3HCl
H 2O + - +
SbCl3 + H2O SbO + 3Cl + 2H
5 (M) HCl
H 2O + - +
BiCl3 + H2O BiO + 3Cl + 2H
5 (M) HCl
NF3 is not hydrolyzed under ordinary conditions as both the constituent elements
have no vacant d-orbitals of suitable energy to accept electrons from water molecules.
Pentahalides: Nitrogen is unable to form pentahalides owing to the absence of vacant d-
orbitals of suitable energy (requiring sp3d hybridization). The subsequent elements can do
so and PF5, PCl5, PBr5, AsF5, SbF5 and SbCl5 are known. These molecules have TBP
geometry in the gaseous state arising out of sp3d hybridization of the central elements. In
contrast to the high volatility of PF5 (B.P. −85 °C) and AsF5 (B.P. −53 °C), SbF5 is a
highly viscous liquid and nBiF5(s) has melting point of 154 °C.
The TBP geometry is not strictly regular as some of the
bond angles are 120° while the rest are 90° and hence
the molecule is unstable in the solid state. PCl5
undergoes Lewis acid-base reaction yielding PCl6−
(sp3d2) and PCl4+ (sp3).

Figure 8
PCl5 + Cl PCl4 PCl4+ PCl6-
Acid Base

Complete hydrolysis of pentahalides yield acids, e.g.,

PCl5 + 4H2O = H3PO4 + 5HCl
Despite the existence of pentahalides, no hydrides MH5 are known. To attain the
pentavalent state, d-orbitals must be used and hydrogen is not electronegative enough to
contract the d-orbitals sufficiently, though PHF4 and PH2F3 have been isolated.
One nitrogen oxyhalide seems to stand out as being related to the phosphorus
oxyhalide, trifluoroamine oxide, F3NO which is kinetically stable and is not easily
hydrolyzed. The stability of F3NO towards nucleophilic attack may be assigned to the
fact that steric shielding occurs at the central atom (nitrogen) site by the fluorine and

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oxygen atoms. Also, the terminal oxygen of F3NO, possessing lone-pairs of electrons,
fails to undergo lp−lp repulsive interaction with nitrogen as the latter lacks a lone-pair.
The unusual stability of F3NO is partially attributed to an important contribution from the
N=O resonance structure:
_
F F
+
N O
F
Figure 9
NF5 is unknown but the N(V) species, [NF4]+ is known for the compound: [NF4+][SbF6−].
Oxides: The oxides and oxyacids of nitrogen all exhibit pπ−pπ multiple bonding between
nitrogen and oxygen atoms. This does not occur with the heavier elements in the group
and consequently nitrogen forms a number of compounds which have no P, As, Sb or Bi
analog. Nitrogen forms a wide range of oxides N2O, NO, NO2, N2O3, N2O5 etc. of which
the lower ones being neutral, and higher ones are acidic. Because N forms strong multiple
bonds, the oxides N2O3 and N2O5 are monomeric while tri-and pentoxides of other
elements are dimeric e.g., (P2O3)2, (P2O5)2, etc. The structures of (P2O3)2 and (P2O5)2 are
based on insertion of oxygen atoms into P−P bonds of tetrahedral P4 unit:

Figure 10. The structures of P4O6 and P4O10

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Nitrous oxide: It is linear and molecular spectroscopic study shows that the nuclei are
arranged in N−N−O fashion rather than in a N−O−N fashion as evidenced from the bond
length measurement ‘N−N’ = 1.13 Å and ‘N−O’ = 1.19 Å. A valence bond description of
the molecule is a combination of the following structures:
+
N N O (I)
+
N N O (II)
Here the central nitrogen atom is in sp state of hybridization with one localized π-orbital
between the two nitrogen atoms and a delocalized π-orbital orbital extending over all the
three atoms.
Nitric oxide: It is a colorless diatomic π* radical which tends to dimerize weakly (∆H ≈
17 kJ mol−1) in liquid (B.P. = −152 °C) and solid (M.P. = −164 °C) states to (NO)2 and is
readily oxidized to nitrosyl cation (NO+). The structure of the colorless dimer is planar
and cyclic with long (220 pm) and weak bonds between the nitrogen atoms. In the
dimerization the weak ‘N−N’ bond-energy and the planar structure are easily understood
to arise from the half-occupied HOMO of NO. The constructive overlap of both the
nitrogen p and oxygen p atomic orbital components of the π* HOMO introduces both
N−N and to a lesser extent O−O bonding and ∠O−N−N of ~ 100°:

N + + N N
220 pm
N

+ O O + O
262 pm
O

Figure 11
The notable reluctance of NO to dimerize can be related both to the geometrical
distribution of the unpaired electrons over the entire molecule and to the fact that the
dimerization to O=N−N=O leaves the total bond-order unchanged (2 × 2.5 = 5). When
NO condenses to a liquid, partial dimerization occurs and the cis form is more stable than
the trans form.
The valence bond description of NO as a hybrid of (I) and (II) is less efficient and
gives a three electron bond between the nitrogen and oxygen atoms:
N O (I)

N O (II)
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Nitrogen dioxide: It is a sigma radical and not a pi radical with a slight tendency to
dimerize to N2O4 and tends to lose its brown color. The N−N bond distance in this
compound is 175 pm and is weak (B.E. = 63 kJ mol−1). The most stable structure of the
dimer is planar.
O O

N N

O O

Figure 12
The planarity of N2O4, according to a full MO study arises from the fact that the
HOMO of NO2 has appreciable ‘O’ character affording some long range bonding
between the syn oxygen atoms in the N2O4 M.O. otherwise characterizing the N−N bond.
According to valence bond theory, in NO2 the central nitrogen atom is in the state
of sp2 hybridization (angular) with one position occupied by an odd electron.

N
O O
1340
Figure 13
Nitrogen sesquioxide: Spectroscopic studies show that N2O3 has a nitronitroso structure
with one nitrogen atom planar (sp2) and other angular:

O O
N N
N N O O O
Unstable
O Stable
Figure 14
In the vapor or liquid state it dissociates as:
N 2O 3 NO + NO2

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Dinitrogen pentoxide: It is prepared by dehydrating HNO3 with P2O5. X-ray diffraction
shows that solid N2O5 is ionic NO2+ NO3−: it should in reality be called nitronium nitrate.
It is covalent in solution and in the gas phase, and probably has the dinitro etherial
structure:

O sp2 O
O
sp3 sp2
N N

O O
Figure 15
Oxyacids of Group 15 Elements
Oxyacids of nitrogen: The two most commonly known oxyacids of nitrogen are nitrous
(HNO2) and nitric (HNO3) acid. Nitric acid may be regarded as the contribution of H+
and NO3− and also an adduct of OH− and NO2+ according to the following dissociation:
_ + _
OH + NO2 HNO3 H+ + NO3
In presence of strong acid In neutral solution
e.g., H2SO4 or
in basic medium

H2SO4 apparently dehydrates HNO3 to form NO2+ according to the following equation:

H2SO4 _
HNO3 NO2+ + HSO4 + H2O (solvated)

The structure of HNO3 is represented as follows:

0

O 116 sp2 sp3

0
130 N O
O H
0 0
114 102
Figure 16
The nitrate ion is a sp2 hybrid and has a planar structure having the following canonical
forms:

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 O O O O O O

N N N N N N
O O O O O O O O O O O O

HNO2: It is considerably less stable than nitric acid in the sense that the acid solution
tends to disproportionate to NO and HNO3. It may be noted that there is no change in the
number of OH bonds, and an increase in N−O π-bonding and an associated loss of
effective lpN−lpO repulsion is achieved in the disproportionation reaction:
π∗
O
H
3 O N 2 N O + HO N + H2O
O O

3πNO → 4πNO; 3 lp/lp → 0 lp/lp

Thus HNO2 is unstable due to the lpN−lpO repulsion (which tends to cleave the
bond) which is absent in HNO3 as the lone-pair on nitrogen is engaged in the formation
of a σ-bond with oxygen.
HNIIIO2 posses both the oxidizing and reducing capacity as it is present in an
intermediate oxidation state and may pass on to the lower and higher oxidation state
respectively. HNVO3 on the other hand acts exclusively acts as an oxidant as the nitrogen
atom is present in the topmost oxidation state of +5 and has only the ability to accepts
electrons to pass on to the lower oxidation state.
Oxyacids of phosphorus: Phosphorus forms two series of oxyacids− the phosphoric and
the phosphorous series. In phosphoric acid series the oxidation state of phosphorus is +5
and the compounds have oxidizing properties, whilst in the phosphorous acid series the
oxidation state of Phosphorus is +3 and they are reducing agents. In all these cases the
central P atom is tetrahedrally sp3 hybridized with P−O back-bonding by the overlap of
the filled p-orbital of oxygen and vacant d-orbital of phosphorus.
Phosphoric acid: It is prepared according to the following reaction:
P4O10 + 6H2O = 4H3PO4
PCl5 + 4H2O = H3PO4 + 3HCl

Dr. Jishnunil Chakraborty - Assistant Professor - St. Paul’s C. M. College, Kolkata 17

 Orthophosphoric acid has the following structure:
o

HO OH OH
Figure 17
A large number of phosphoric acids and their salts, phosphates arise by sharing oxygen
atoms at one or two corners of the P4 tetrahedron:

O O O O
O

P P P P P
O OH O O OH
HO HO O O
O O O H
H H H H
H4P2O7 H5P3O10
Pyrophosphoric acid Tripolyphosphoric acid
Figure 18
Metaphosphoric acid, (HPO3)n is prepared by heating Orthophosphoric acid. The
metaphosphate ions have the following structures: O
O
O O O P
O O
P P O O

O P P
O O
O O O
Di-metaphosphate ion
O O Tri-metaphosphate ion

O P O P O

Tetra- metaphosphate ion O O

O P O P O

O O
Figure 19

Dr. Jishnunil Chakraborty - Assistant Professor - St. Paul’s C. M. College, Kolkata 18

Phosphorous acid: The phosphorous acids are less well-known of which
hypophosphorous, orthophosphorous and pyrophosphorous acids are important.

Cl OH
P Cl + 3H2O = P OH + 3HCl
Cl OH

OH
O P H
OH
sp3
Orthophosphorous acid
From the hydrolysis of PCl3, orthophosphorous acid seems to have the trihydroxy
structure. It is readily tautomerized to the P=O oxo form by the overlap of the filled p-
orbital of oxygen and the vacant d-orbital (which is contracted as it is linked with oxygen
atom of high electronegativity) of P. The dibasicity of H3PO3 and its reducing character
supports its structure.
Hypophosphorous acid, which is a dibasic one, is prepared by the following
reaction:
P4 + 3NaOH + 3H2O = PH3 + 3NaH2PO2

H+

H H OH
Hypophophorous acid
Dr. Jishnunil Chakraborty - Assistant Professor - St. Paul’s C. M. College, Kolkata 19
 Pyrophosphorous acid is formed by the hydrolysis of P4O6 and has the following
structure:
H H

HO P O P OH

O O
Pyrophosphorous acid
Figure 20
Of the oxyacids of phosphorus, e.g., H3PVO4 (pKa1 = 2.16), H3PIIIO3 (pKa1 =
2.00), and H3PIO2 (pKa1 = 1.00), H3PO4 is the weakest and H3PO2 is the strongest one,
which is the reverse trend as expected from the oxidation state of the central element.
This may be explained from the stand-point of acid weakening due to salvation effect
where H3PO4 has the maximum number of OH groups for this purpose (Figure 21).
H

H
O

OH H
O P OH O
OH H
O

H
H

Figure 21

Dr. Jishnunil Chakraborty - Assistant Professor - St. Paul’s C. M. College, Kolkata 20