NITROGEN FAMILY

IIT-JEE Syllabus : Nitrogen Family

Isolation/preparation & properties of the Nitrogen family.

As you have gone through the theory part that consists of given fundamental principles,
definitions, concepts involved. After going through theory part it becomes necessary to solve
the unsolved problems based on the concepts given. To solve this purpose we are providing
solved problems and exercise part that comprises of various exercises based on the theory. By
solving various kinds of problems you can check your grasp on the topic and can determine
whether you have been able to find optimum depth in relevant topic or not.
 SOLVED EXAMPLES
Ex.1 Among the following species, identify the Sol.[C] Each P in P4O6 has 3P–O bonds
isostructural pairs. O–P–O
| |
NF3, NO3– , BF3, H3 O+, HN3 P–O–P
|O |
(A) [NF3, NO3– ] and [BF3, H3O+] O–P–O
(B) [NF3 , HN3] and [ NO3– , BF3] Ex. 3 Arrange the group 15 hydrides in the increasing
order of H – N – H bonds angle–
(C) [NF3 , H3O+] and [ NO3– , BF3]
(A) SbH3 < AsH3 < PH3 < NH3
(D) [NF3 , H3O+] and [HN3 BF3]
(B) NH3 < PH3 < AsH3 < SbH3
Sol.[C] Isostructural pairs are the species that have the
(C) NH3 < SbH3 < AsH3 < PH3
same electron-pair geometry and same shape–
(D) NH3 < PH3 < SbH3 < AsH3

Species Lewis Electron-pair Shape of Sol.[A] In all these hydrides, the central atom ‘M’ is
structure geometry the sp3 - hybridized forming four sp3 - hybrid
species orbitals. Three sigma () bonds with three

: F  N
  F : hydrogen atoms; whereas the fourth hybrid
NF3 ·· | ·· Tetrahedral Trigonal orbital contains a lone pair. As a result, these
pyramidal hydrides have trigonal pyramidal geometry.
:F:
··
   H Tetrahedral Trigonal
H3O+ HO M
| pyramidal
H H
H
H H
|
BF3 FBF Trigonal planar Trigonal
The H-M-H bond angle decreases from NH3 to

planar SbH3. Now, as we go down the group from


  :
:O  nitrogen to bismuth, the size of central atom
 |  goes on increasing and its electronegativity goes
: O
  N  O :
NO3–  ·· ··  Trigonal planar Trigonal on decreasing. Consequently, the position of
  planar bond pairs of electrons shifts more and more
 
away from the central atom on moving from
NH3 to BiH3. For example, the bond pair in N –
H Tetrahedral Bent H bond is more closer to nitrogen than the bond
HN3 +
N=N=N pair in P–H bond . As result, the force of
around N of repulsion between the bonded pair of electrons
N–H bond in NH3 is more than that in PH3 . In general, the
force of repulsion between bonded pairs of
Ex. 2 In P4O6 the number of oxygen atoms bonded to electrons decreases as we move from NH3 to
each P atom is– BiH3 and, therefore, the bond angle also
(A) 1.5 (B) 2
decreases in the same order.
(C) 3 (D) 4
Ex. 4 Orthophosphoric acid is ionised in . . . . steps– Ex. 6 Substance used in Holme’s signal is–
(A) 1 (B) 2 (A) NH3 (B) PH3
(C) 3 (D) 4 (C) PH5 (D) P2O5
Sol.[C] H3PO4 H+ + H 2 PO 4– Sol.[B] The spontaneous inflammability of phosphine
with smoky rings (vortex rings) at the time of
H 2 PO 4– HPO 24 – + H+
preparation is due to the presence of highly
HPO 24 – H+ + PO34– inflammable P2H4. This property is used in
Holme’s signal.
Ex. 5 Which trihalides is not hydrolysed by water -
(A) NF3 (B) NCl3 Ex. 7 Pick out incorrect statement–
(A) NF3 molecule has trigonal pyramidal structure
(C) PCl3 (D) AsCl3
(B) It is practically insoluble in water and is
Sol.[A] In the first stage of hydrolysis, an extra bond is
only hydrolysed, when an electric spark is
formed by water molecule. While chlorine and
passed through a mixture with water vapour
the group 15 elements (except nitrogen) can (C) Dipole moment of NF3 is more than that of
expand their octet by using vacant d-orbitals of NH3
the valence shell, F and N cannot. As a result, (D) Nitrogen (III) oxide (N2O) is an acidic
NF3 is extremely stable. oxide.
Trihalides of P, As, Sb, and Bi hydrolyse Sol.[C] Dipole moment of NH3 (0.49 x 10-29 C.m.) is
readily. more than that of NF3 (0.07 x 10-29 C.m.) This
NF3 + H2O (l) 
 No hydrolysis is due to the fact that the directions of the dipole
NCl3 + 3H2O (l) 
 NH3 + 3HOCl moments of the bonding N–H and non-bonding
electron pair coincide in NH3 and, therefore,
PCl3 + 3H2O (l) 
 H3PO3 + 3HCl vector addition of all dipole moments of N–F
2AsCl3 + 3H2O 
 6HCl + As2O3 bonds and of the non-bonding electron pair are
in opposite directions, so that they are partially
Notes -
compensated when summated.
(a) SbCl3 and BiCl3 also hydrolyse to form basic
oxochlorides.
BiCl3 + H2O BiOCl + 2HCl N N
(b) Hydrolysis of NCl3 is thought to proceed by
H H F F
stepwise replacement of chlorine, the lone pair
on N – atom bonding to a hydrogen atom of a H F
water molecule. (A) From the above figure, it is clear that NF3
Cl H has a trigonal pyramidal structure.
| | (B) 2NF3 + 3H2O (vapour)  N2O3 + 6HF
Cl – N× + H – O  
×

| ( D) N2O3 (l) + H2O (l)  2HNO2 (l)

Cl
(Acid)
Cl H Cl
| | | Ex. 8 A hydride of nitrogen having lowest oxidation
Cl – N×× – – – –H – O  Cl – ×N× – H + HClO number of N.
| (A) H3N (B) N3H
Cl
(C) H4N2 (D) H2N2
NHCl2 + H2O 
 NH2Cl + HClO
Sol.[A] N in NH3 has -3 oxidation number, the lowest
NH2Cl + H2O 
 NH3 + HClO value of oxidation number of N.
Ex. 9 Derivatives of nitrogen (III) act as– accommodate five electron pairs in trigonal
(A) Oxidizing agent only bipyramidal orientation, P atom is sp3d-
(B) Reducing agent only hybridized. Since all the five sp3 d-hybrid
orbitals have bond pairs, therefore, the geometry
(C) Both Oxidizing and Reducing agent of PCl5 is also trigonal bipyramidal.
(D) Nitrating agent
(B) PCl5 + 4H2O  H3PO4 + 5 HCl
Sol. Deriatives of nitrogen (III) have both oxidizing
and reducing properties. (C) It is because the central ‘P’ atom can easily
3 accept the halide ion (a Lewis base), due to the
2Na N O 2 + 2KI + 2H2SO4 
 
presence of vacant d-orbital in its valence shell.
  (Oxidant)
2  PCl 6–
PCl5 + Cl¯ 
   I2 + 2 N O + 2K2SO4 + Na2SO4 + 2H2O
5 (Lewis acid) (Lewis base)
2KMnO4 + 5Na NO2 + 3H2SO4 
 
Ex. 12 Complete and balance the following reactions–
 (Reductant)
5 (a) Copper reacts with HNO3 to give NO and NO2
2MnSO4 + 5Na N O 3 + K2SO4 + 3H2O
in molar ratio of 2 : 1
Ex. 10 In the compound of type POX3, P atoms show
(b) Ammonium sulphate is heated with a mixture of
multiple bonding of the type–
nitric oxide and nitrogen dioxide.
(A) p-d (B)d-d
  (C) p-p (D)No multiple bonding (c) The preparation of ammonium sulphate from
Sol.[A] POX3 has sp3- hybridised P having vacant gypsum, ammonia and carbon dioxide.
d-orbitals. p-of O atom and d- of P undergoes (d) Aqueous solution of sodium nitrate is heated
p-d bonding. with zinc dust and caustic soda.
Ex. 11 Pick out the incorrect statement -
(e) The preparation of phosphine from CaO and
Cl
Cl white phosphorus.
Sol.[a]
P 0.204pm
Cl Cl
2HNO3  2NO + H2O + 3O
0.219 pm
Cl 3Cu + 3O + 6HNO3  3Cu(NO3)2 + 3H2O

(A) In PCl5, P atom is sp3d-hybridized and has

3Cu + 8HNO3 
trigonal bipyramidal geometry.
3Cu(NO3)2 + 2NO + 4H2O . . . (a)
(B) PCl5 on hydrolysis forms Lewis-acids
(C) PCl5 acts as Lewis acid 2HNO3  2NO2 + H2O + O
(D) In PCl5 the axial chlorine atoms are closer to Cu + O + 2HNO3  Cu(NO3)2 + H2O
central ‘P’ atom than equatorial chlorine atoms.
Sol.[D] This is clear from structure of PCl5 given Cu + 4HNO3 

below– Cu(NO3)2 + 2NO2 + 2H2O . . . (b)

(A) Lewis structure of PCl5 has five electron pairs.
According to VSEPR theory, the orientation of
five electron pairs is trigonal bipyramidal to
 To get NO and NO2 in the ratio of 2 : 1, the Ex.14 Give the names and formulae of the compounds.
Eqn. (a) be multiplied by two and added in Eqn. described below–
(a) A chromium compound which on heating
(ii)
gives nitrogen and an oxide of chromium.
7Cu + 20HNO3  (b) A compound of N, H and O which is used
7Cu(NO3)2 + 2NO2 + 4NO + 10H2O as a freezing agent and decomposes on
heating giving a neutral oxide of nitrogen.
(b) NO + NO2  N2O3 Sol. (a) Chromium compound is ammonium dichromate,
(NH4)2SO4  2NH3 + H2SO4 (NH4)2Cr2O7
(NH4)2Cr2O7  N2 + Cr2O3 + 4H2O
(NH4)2SO4 + NO + NO2  (b) The compound is ammonium nitrate, NH4NO3
2N2 + H2SO4 + 3H2O NH4NO3  N2O + 2H2O
Neutral oxide
(c) 2NH3 + H2O + CO2  (NH4)2CO3
Ex.15 Write an equation for the reaction of burning
CaSO4 + (NH4)2CO3  (NH4)2SO4 + CaCO3
Mg with NO2.
(d) [Zn + 2NaOH  N2ZnO2 + 2H] x 4 Sol. 4Mg + 2NO2  4MgO + N2
NaNO3 + 8H  NaOH + NH3 + 2H2O
Ex.16 Complete and balance the following reactions–
4Zn + 7NaOH + NaNO3  (a) Ag(NH3)2Cl + HNO3  . . . . .
NH3 + 4Na2ZnO2 + 2H2O (b) Ca3(PO4)2 + SiO2 + C

(e) [CaO + H2O  [Ca(OH)2] x 3 heat

 CaSiO3 + CO + . . . . .
(c) CaCN2 + H2O(steam)  CaCO3 + . . . .
8P + 3Ca(OH)2+ 6H2O 
(d) Ca3(PO4)2 + H3PO4  . . . . .
3Ca(H2PO2)2 + 2PH3
(e) NH3 + NaOCl  . . . . . + NaCl + H2O
8P + 3CaO + 9H2O  3Ca(H2PO2)2 + 2PH3 (f) P4O10 + PCl5  . . . . .
Ex. 13 P4 exists but N4 does not; N2 exists but P2 does Sol. (a) Ag(NH3)2Cl + 2HNO3  AgCl + 2NH4NO3
not; Explain– (b) 2Ca3(PO4)2 + 6SiO2  6CaSiO3 + P4O10
P4O10 + 10C  10CO + P4
P
2Ca3(PO4)2 + 6SiO2 + 10C  6CaSiO3 +
60°
Sol. P P (White phosphorous ; P4) 10CO + P4
(c) CaCN2 + 2H2O  CaCO3 + 2NH3
P
(d) 2Ca3(PO4)2 + 4H3PO4  3Ca(H2PO4)2
NN 946 kJ mol-1
(e) 2NH3 + 3NaOCl  N2 + 3NaCl + 3H2O
PP 481 kJ mol-1
or NH3 + NaOCl  NH2Cl + NaOH
Glue

N–N 216 kJ mol-1

NaOH + HCl  NaCl + H2O
P–P 215 kJ mol-1
Greater the B.E., greater the stability [compare 2NH3 + NaOCl  NH2.NH2 + NaCl + H2O
B.E.of NN and PP and N–N (f) P4O10 + 6PCl5  10 POCl3
(in N4) and P–P (in P4)]
Ex. 17 Colourless salt (A) + NaOH   gas (B) Ex. 21 Complete and balance the following reactions–
giving white fumes with HCl + alkaline (a) KNO3 + FeSO4(conc.)  . . . . .
solution(C)
(C) + Zn  gas (B) (b) Cu + HNO3 NO + . . . . + . . . .

(A)  gas (D) + liquid (E) (c) Pb(NO3)2 

 PbO + . . . . + . . . .
heat

(d) CuSO4 + NH4OH(excess) - - - - - -

Both triatomic
(e) NH3(excess) + Cl2  . . . . .
Identify (A, B, C, D) and (E)
Sol. (A) : NH4NO3 (f) NH3 + Cl2 (excess)  . . . . .
(B) : NH3 (g) AgCl + NH4OH  . . . . .
(C) : (NaNO3 + NaOH) (D) : N2O
(E) H2O Sol. (a) 2KNO3 + H2SO4  2HNO3 + K2SO4
Ex. 18 Fe2+ as well as HNO2 can be used to estimate 2HNO3  2NO + H2O + K2SO4
MnO4– in acidic medium. If 100 ml of 1M Fe2+ [2FeSO4 + H2SO4 O 
can be oxidised by V ml of 1 M MnO4– / H+ Fe2(SO4)3 + H2O] x 3
solution, calculate volume of 1 M HNO2 that
[FeSO4 + NO  FeSO4 .NO] x 2
can be oxidised by V ml of 1 M MnO4– / H+
solution.
2KNO3 + 8FeSO4 + 4H2SO4 
Sol. MnO4–+ 8H+ + 5e¯  Mn2+ + 4H2O
2Fe2(SO4)3 + 2FeSO4. NO+K2SO4 +4H\O
Fe2+ 
 Fe3+ + e¯
Brown ring
HNO2 + H2O  NO3– + 3H+ + 2e¯
(b) 2HNO3 H2O + 2NO + 3O
V mL of 1 MnO4–  100 mL of 1N Fe2+
3Cu + 3O + 6HNO3  3Cu(NO3)2 + 3H2O
or V mL of 1N MnO  100 mL of
3Cu + 8HNO3  3Cu(NO3)2 + 2NO + 4H2O
1N Fe2+ - - - - - Ist
(c) 2Pb(NO3)2  2PbO + 4NO2 + O2
Also V mL of 1M MnO 4–  V´mL of 1M HNO2
(d) CuSO4 + 2NH4OH  Cu(OH2) + (NH4)2SO4
V mL of 5N MnO 4– V´mL of 2N HNO2 - - - - IInd
Cu(OH2) + (NH4)2SO4 + 2NH4OH 
Thus, from Ist and IInd V’ = 50 ml
     Cu(NH3)2SO4 + 4H\O
Ex. 19 NF3 is stable while NCl3 and NI3 are explosive–
Sol. In NF3 the electronegativity difference (N=3.0; (e) 2NH3 + 3Cl2  N2 + 6HCl
F=4.0) permits strong p - p bonding and the 6NH3 + 6HCl  6NH4Cl
molecule is stable. But in NCl3 and NI3, the 8NH3 + 3Cl2  6NH4Cl + N2
electronegativity difference is nil or small and (Excess)
the molecules are unstable with p - pbonding
weak. Hence NF3 is a stable gas, NCl3 an (f) NH3 + 3Cl2  NCl3 + 3HCl
explosive liquid and NI3 and explosive solid (Excess)
(g) AgCl + NH4OH  AgOH + NH4Cl
Ex. 20 With the help of NH3, O2, Pt and H2O , write AgOH + NH4Cl + NH4OH 
equations for preparation of N2O from these Ag(NH3)2Cl + 2H2O
substances.
Sol. 4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)
Pt. AgCl + 2NH4OH  Ag(NH3)2Cl + 2H2O
2NO(g) + O2(g)  2NO2(g)
3NO2(g) + H2O(l)  2HNO3(aq.) + NO(g)
HNO3(g) + NH3(aq.) NH4NO3(aq.)

NH4NO3(aq.)  NH4NO3(s)

NH4NO3(s)  N2O(g) + 2H2O (g)
 EXERCISE # 1
Questions General Physical Properties of Nitrogen
based on Family
Q.9 Nitrogen combines with metals to form -
(A) Nitrites (B) Nitrates
Q.1 Which of the following is the most abundant in (C) Nitrosyl chlorides (D) Nitrides
the earth’s crust -
(A) Arsenic (B) Nitrogen
Q.10 White phosphorus contains -
(C) Phosphorus (D) Antimony
(A) P2 molecules (B) P6 molecules
Q.2 The electronic configuration of outermost shell (C) P4 molecules (D) P5 molecules
of group 15 elements is -
(A) ns2np4 (B) ns2np3 Q.11 In modern process phosphorus is manufactured
2 2
(C) ns np (D) ns2np1 by -
(A) Heating a mixture of phosphorite mineral
Q.3 Which of the following does not show with sand and coke in electric furnace.
allotropy - (B) Heating calcium phosphate with coke
(A) Nitrogen (B) Phosphorus (C) Heating bone ash with coke
(C) Arsenic (D) Antimony
(D) Heating the phosphate mineral with sand

Q.4 The correct order of thermal stability of
hydrides of group 15 is -
(A) NH3 > PH3 > AsH3 > BiH3 > SbH3
(B) NH3 > PH3 > AsH3 > SbH3 > BiH3
(C) NH3 < PH3 < SbH3 > AsH3 > BiH3
(D) BiH3 > SbH3 > AsH3 > PH3 > NH3
Q.12 Red phosphorus is chemically unreactive
because -
(A) It does not contain P — P bonds
(B) It does not contain tetrahedral P4 molecules
(C) It does not catch fire in air even upto 400º C
(D) It has a polymeric structure.

Q.5 Arrange the hydrides of group 15 in the order of Q.13 Phosphorus vapours consists of -
increasing boiling points - (A) P molecule (B) P2 molecule
(A) PH3 < AsH3 < SbH3 < BiH3 < NH3
(C) P3 molecule (D) P4 molecule
(B) PH3 < AsH3 < SbH3 < NH3 < BiH3
(C) PH3 < AsH3 < NH3 < SbH3 < BiH3
Q.14 Labour's working with phosphorus suffer from a
(D) NH3 < PH3 < AsH3 < SbH3 < BiH3
disease in which bones decay. It is known as -
(A) Arthritis (B) Phossy jaw
Q.6 Arrange the group 15 hydrides in the increasing (C) Rickets (D) Cancer
order of H–M–H bond angle.
(A) SbH3 < AsH3 < PH3 < NH3
Questions The
oxides of the Nitrogen and
(B) NH3 < PH3 < AsH3 < SbH3 based on
Phosphorus
(C) NH3 < SbH3 < AsH3 < PH3
(D) NH3 < PH3 < SbH3 < AsH3 Q.15 Nitrogen(I) oxide is produced by -
(A) Thermal decomposition of ammonium
Questions nitrate
based on Preparation of Nitrogen family
(B) Disproportionation of N2O4
Q.7 The percentage of N2 in air is - (C) Thermal decomposition of ammonium
(A) 75% by weight (B) 78.7% by volume nitrite
(C) Both A & B (D) None of these (D) Interaction of hydroxylamine and nitrous
acid
Q.8 The most unstable hydride among the following
is - Q.16 Nitrogen dioxide can not be obtained by heating -
(A) NH3 (B) PH3 (A) KNO3 (B) Pb(NO3)2
(C) AsH3 (D) BiH3 (C) Cu(NO3)2 (D) AgNO3
Q.17 The arrangement of oxygen atoms around Q.26 When conc. HNO3 is added to conc. H2SO4, the
phosphorus atoms in P4O10 is - ions produced are
(A) Pyramidal (B) Octahedral (A) NO 2 , NO3 (B) NO  , NO 2
(C) Square planar (D) Tetrahedral (C) NO  , NO3 (D) N 2 , NO3

Q.18 Phosphorus compound used as drying agent and Q.27 Ammonium nitrate is formed in
desicating agent is - (A) Zn + very dil. HNO3
(B) Fe + very dil. HNO3
(A) PCl3 (B) PCl5
(C) Sn + dil. HNO3
(C) P4O10 (D) P4O6 (D) All of these

Questions Q.28 The correct order of bond angle is

Compounds of nitrogen and phosphorus
based on
(A) NO2  NO2  NO2
Q.19 By the action of conc. H2SO4, phosphorus (B) NO2  NO2  NO2
changes to
(C) NO2  NO2  NO2
(A) H3PO3 (B) HPO3
(C) H3PO4 (D)H4P2O7 (D) NO2  NO2  NO2

Q.20 PH3 produces smoky rings when it comes in

contact with air. This is because TRUE OR FALSE TYPE QUESTIONS
(A) it is inflamable
Q.29 Urea is better nitrogeneous fertilizer than
(B) it combines with water vapour
ammonium sulphate
(C) it combines with nitrogen
(D) it contains impurity of P2H4 Q.30 The H bond present in the aqueous solution of
NH3 is–
Q.21 Which one of the following statement is wrong ?
H
(A) Ammonia is more poisonous than phosphine |
(B) Ammonia is more basic than phosphine
H — N····· H·····OH
(C) Ammonia is more stable than phosphine |
(D) Ammonia is more soluble in water than H
phosphine
Q.31 (CF3)3N is weaker base than (CH3)3N
Q.22 A white ppt is obtained on hydrolysis of
(A) PCl5 (B) NCl3 Q.32 NO is paramagnetic in gaseous state but
(C) BiCl3 (D) AsCl3 diamagnetic in liquid or solid state.

Q.23 Holme's signal is produced by Q.33 The geometry of PBr5 in solid state is
(A) CaC2 (B)Ca3P2 tetrahedral–
(C) Both (D) None of these
FILL IN THE BLANKS
Q.24 Cr2+ + H+ + NO  (X) + Cr3+ ; X is
(A) N2H4 (B) NH2OH Q.34 [Ag(NH3)2]Cl + HNO3(dil) 
 .....(white ppt.)
(C)N2 (D) N2O
Q.35 NH3 (excess) + Cl2 
 ....... + ........
Q.25 MnO 4 + NO + H+  (X) + (Y); (X) and (Y) are
(A) X = Mn3+ , Y = NO3 Q.36 Na2HPO4+ MgSO4 + NH4OH 
 ...... (white ppt)
2+
(B) X = Mn , Y = NO3 
Q.37 Ca3(PO4)2 + H3PO4(conc.)  ..........
(C) X = MnO2 , Y = NO2
(D) X = Mn2+ , Y = NO2 Q.38 I2 + HNO3 
 ....... + ....... + H2O
 EXERCISE # 2
PART–A (ONLY SINGLE CORRECT ANSWER Q.9 Solid PCl5 exists as–
TYPE QUESTIONS) (A) PCl5 (B) PCl4+ & PCl6¯
Q.1 Nitrogen is inert because of– (C) PCl 6 (D) PCl 4
(A) Low atomic size
(B) Presence in gaseous state Q.10 The final product of hydrolysis of P 4O6 is -
(C) More electronegativity (A) H3PO3 (B) (HPO3)n
(D) Presence of triple bond (C) H4P2O7 (D) H3P4O13
Q.2 Pure nitrogen is obtained from– Q. 11 Arrange the hydrides of group 15 in the correct
(A) NH3 + NaNO3 (B) NH4Cl + NaNO2 order of reducing nature–
(C) N2O + Cu (D) (NH4)2Cr2O7 (A) NH3 < PH3 < AsH3 < SbH3 < BiH3
(B) NH3 > PH3 > AsH3 > SbH3 > BiH3
Q.3 Large-scale manufacture of nitric acid by
(C) PH3 < AsH3 < SbH3 < BiH3 < NH3
Ostwald process utilizes the reaction–
(A) 2NaNO3 + H2SO4  Na2SO4 + 2HNO3 (D) PH3 > AsH3 > SbH3 > BiH3 > NH3

(B) 4NH3 + 5O2  4NO + 6H2O Q. 12 Light blue colour of nitrous acid is due to
(C) NO2+ + NO3– + H2O  2HNO3 dissolved–
(A) O2 (B) N2
(D) 2NO + O2 + H2O  HNO3 + HNO2
(C) N2O (D) N2O3
Q.4 Which reaction can be used to prepare
Q.13 Pick out the incorrect statement–
phosphorus acid–
(A) Red phosphorus consists of a complex chain
(A) P2O3 + H2O 
20 º C
structure and black phosphorus has a layer
structure
(B) P2O3 + H2O 
80 º C
(B) Nitrogen shows a little tendency for
(C) P2O3 + H2O 
125ºC
catenation, because N - N single bond is
very strong.
(D) P + conc. HNO3 
(C) The maximum number of covalent bonds
Q.5 PCl5 reacts with compounds containing .... formed by nitrogen is four, since it has no
d-orbitals in its valence shell.
group–
(A) –SO3 (B) –OH (D) The group 15 elements do not form M5+
ions, but +5 oxidation state is realized only
(C) –NO3 (D) –NO through covalent bonding

Q.6 Which of the following sulphides is used in the Q.14 Which of following trihalides of nitrogen
manufacture of “Strike anywhere” matches– behaves as the weakest base–
(A) P2S2 (B) P2S3 (A) NF3 (B) NCl3
(C) P4S3 (D) None (C) NBr3 (D) NI3
Q.15 Arrange the oxides of group 15 elements in
Q.7 The strongest acid is–
decreasing order of their acidity–
(A) H3PO2 (B) H3PO3
(A) N2O5 > P2O5 > As2O5 > Sb2O5 > Bi2O5
(C) HPO3 (D) H3PO4
(B) Bi2O5 > Sb2O5 > As2O5 > P2O5 > N2O5
(C) P2O5 > N2O5 > As2O5 > Sb2O5 > Bi2O5
Q.8 In P4O6 the number of oxygen atoms bonded to
(D) N2O5 > Bi2O5 > P2O5 > As2O5 > Sb2O5
each P atom is–
(A) 1.5 (B) 2 Q.16 Which of the following is least acidic–
(C) 3 (D)4 (A) P4O6 (B) P4O10
(C) As4O6 (D) As4O10
Q.17 Which of the following oxyacids acts as most Q.25 Which of the following is/are paramagnetic–
reducing agent– NO2, NO, N2O4, N2O2, N2O5
(A) H3PO3 (B) H3PO4 (A) Only NO2
(C) H4P2O6 (D) H4P2O7 (B) NO2, NO(C) NO, N O2, N2O5
Q.18 A substance which gives a yellow precipitate (D) All are paramagnetic
when boiled with an excess of HNO3 and
Q.26 A colourless gas X forms a brown coloured gas
ammonium molybdate and a red precipitate when mixed with air. The gas X is–
with silver nitrate is–
(A) NH3 (B) NO
(A) Orthophosphate (B) Pyrophosphate
(C) Metaphosphate (D) Arsenate (C) N2O (D) NO2

Q.19 Pick out the incorrect statement– Q.27 Which of the following can be used as
dehydrating agents–
(A) PH4+ ion is tetrahedral like the NH4+ion and
(A) Conc. H2SO4 (B) POCl3
is obtained when PH3 is bonded to proton
(C) P2O5 (D) All
(B) PH4I is one of the most stable salts
containing the phosphonium ion. It is also Q.28 Arsenic is detected by–
more stable than ammonium salts.
(A) Ring test (B) Lucas test
(C) PH4I is decomposed by water to form PH3
(C) Lake test (D) Marsh test
(D) PH3 converts silver salts in solution to silver
phosphide, which subsequently reacts to
give free metal PART- B (ONE OR MORE THAN ONE CORRECT
ANSWER TYPE QUESTIONS)
Q.20 Oxyacid of phosphorus that can reduce AgNO3
to silver is– Q.29 On rubbing I2 flackes with liquor NH3 dark
(A) H3PO4 (B) H4P2O7 brown residue (X) is obtained. (X) on heating
(C) H3PO3 (D) HPO3 gives.
(A) NH4I (B) N2
Q.21 P4O10 has short and long P–O bonds. The (C) I2 (D) NI2–NH3
number of short P–O bonds in this compounds
is– Q.30 N2 can be obtained from by heating–
(A) 1 (B) 2 (A) NH4I (B) NH4NO3
(C) 3 (D) 4 (C) (NH4)2Cr2O7 (D) NH4Cl + NaNO2

Q.22 A monobasic acid of phosphorus, which reduces Q.31 Which of the following oxyacids of phosphorus
HgCl2 to black Hg is– disproportionate to PH3 on heating ?
(A) Hypophosphorus acid (A) H3PO3 (B) H3PO2
(B) Phosphoric acid
(C) H3PO4 (D) HPO3
(C) Metaphosphoric acid
(D) Pyrophosphoric acid
Q.32 Which of the following is /are correct for NH3
Q.23 In phosphorus estimation, the compound Mg and PH3 ?
NH4PO4 is converted on ignition to– (A) Both are reducing agent.
(A) Mg2P2O7 (B) Mg3(PO4)2 (B) Both form complex compound
(C) Mg3(PO4)2 (D) Mg(PO3)2 (C) PH3 is weaker base than NH3
(D) PH3 is softer lewis base than NH3
Q.24 Write the missing product in the following
reaction–
Q.33 Which of following are not known–
4HNO3 + P4O10 . . . . 4HPO3 (A) PH5 (B) PI5
(A) 2N2O5 (B) 2N2O3 (C) NCl5 (D) NF5
(C) 2NO2 (D) 2N2O
Q.34 Which of the given gaseous substance are very
poisonous ? Q.40 Assertion : The boiling point of hydrides of N-
family shows the order :
(A) CO (B) CO2
NH3 > BiH3 > SbH3 > AsH3 > PH3
(C) PF3 (D) NI3
Reason : The abnormality in b. pt of NH3 in
hydrides of N-family is due to H-bonding.
Q.35 Which of the following gas/gases can not be
dried by NaOH solution ? Q.41 Assertion : The basic nature of trihalides of
nitrogen decreases from NF3 to NI3.
(A) NO (B) N2O5
Reason : The halogens develop + ve charge on
(C) N2O3 (D) NO2 N atom and thus more +ve charge is developed
in NF3 and therefore tendency to lose electron
Q.36 P4O10 on reacting with water form :
pair decreases.
(A) Tetra metaphosphoric acid
Q.42 Assertion : PCl5 molecules has two bond angles
(B) Phosphorus acid
of Cl–P–Cl as 90º and 120º as well as two P–Cl
(C) orthophosthoric acid
bonds are weaker then rest three P–Cl bonds.
(D) Pyrophosphoric acid Reason : P in PCl5 shows sp3 d hybridisation
Q.37 Which of the following exist as tetra atomic leading to trigonal bi-pyramid geometry. Also
molecule ? two P–Cl bonds at axial positions give less
(A) N (B) P (C) As (D) Sb stable bonds.
Q.43 Assertion : NH3 and PH3 differ from each other
Q.38 Which of the following conclusions are correct?
in their reaction with CuSO4 or AgNO3.
(A) The enthalpy of formation of NF3 is
Reason : PH3 acts as oxidising agent in these
exothermic whereas enthalpy of formation
reaction but NH3 not.
of NCl3 is endothermic
(B) The enthalpy of formation of NF3 and NCl3
PART-D (COLUMN MATCHING)
both are exothermic
(C) N–N bond distance in N2O4 is greater than
Q.44 Column A Column B
the N–N usual single bond distance (A) Paramagnetic (i) N2O3
(D) N–N bond distance in N2O4 is smaller than
(B) Dark blue liquid (ii) N2O
the N–N usual single bond distance
in liquid or solid
state
PART-C (ASSERTION & REASONING TYPE
QUESTIONS) (C) Unstable gas due to (iii) NO
auto decomposition.
The following questions 39 to 43 consists of
two statements each, printed as Assertion (D) Brown gas (iv) N2O5
and Reason. While answering these questions (E) Neutral gas and (v) NO2
you are to choose any one of the following unreactive
four responses.
(A) If both Assertion and Reason are true and the Q.45 Column A Column B
Reason is correct explanation of the Assertion. (A) Trivalent phosphorus (i) Ca5(PO4)F
(B) If both Assertion and Reason are true but
Reason is not correct explanation of the (B) Fluoraphatile (ii)Black phosphorus
Assertion. (C) Thermodynamically (iii) Red phosphorus
(C) If Assertion is true but the Reason is false. stable allotrope of
(D) If Assertion is false but Reason is true. phosphorus
(E) If Assertion & Reason are false.
(D) Fuming halides of (iv) PF5
Q.39 Assertion : The bond angles of hydrides of N- phosphorus
family decreases down the group.
(E) Trigonal bipyramidal (v) PCl5
Reason : The electronegativity of central atom
decreases down the group which shows a geometry both in
decrease in lone electron pair and bond pair gaseous and solid
electron repulsion. state
 EXERCISE # 3
PART-A(SUBJECTIVE TYPE QUESTIONS) Q.15 Red phosphorus is denser and chemically less
reactive than white phosphorus.
Explain why (Q.1 to 23)
Q.16 Nitric acid acts as oxidising agent while nitrous
Q.1 N2, CO and CN¯ are isoelectronic but the acid can act as an oxidising and a reducing
former is chemically inert and later two are very agent.
reactive.
Q.17 Ortho phosphoric acid is syrupy liquid.
Q.2 Nitric oxide becomes brown when released into
air. Q.18 Phosphine is prepared in an inert atmosphere of
carbon dioxide or hydrogen.
Q.3 PF5 is known but NF5 is not.
Q.19 Red phosphorus is used for making matches.
Q.4 NF3 is stable but NCl3 and NI3 are explosives.
Q.20 Calcium cyanamide is used as a fertilizer.

Q.5 The experimentally determined N – F bond

length in NF3 is greater than the sum of single Q.21 [PBr6]¯ anion is not formed but [PCl6]¯ anion
bond covalent radii of N and F. exist.
Q.22 Aqua-regia dissolves gold.
Q.6 NF3 is not hydrolysed but NCl3 is readily
hydrolysed. Q.23 Phosphorus pentoxide is used in the preparation
of N2O5

Q.7 Concentrated HNO3 turns yellow in sun light. Q.24 Complete and balance the following reaction–
(a) Red phosphorus is reacted with iodine in
Q.8 Nitrate and nitrite cannot be distinguished by presence of water.
the action of conc. H2SO4. (b) White phosphorus is boiled with a strong
Q.9 Although HNO3 is stronger than HNO2, the solution of sodium hydroxide in an inert
atmosphere.
H3PO3, H3PO4 and are of approximately same
(c) Nitrogen is obtained by the reaction of
strength. ammonia with KMnO4.
(d) Phosphorus reacts with conc. HNO3 to give
Q.10 Copper dissolves in HNO3 but not in HCl.
phosphoric acid.
(e) Sodium nitrite is produced by absorbing
Q.11 On heating Pb(NO3)2 produces a pale yellow oxides of nitrogen in aqueous solution of
gas which on strong heating produces a brown sodium carbonate.
gas.
Q.25 What happens when PH3 reacts with–
Q.12 Burning of magnesium continues to burn in (a) aq. Ag+ (b) aq. Cu2+ (c) O2
nitric oxide, while burning of sulphur is
extinguished. Q.26 Give the name and formulae of a compound of
N, H, C and O which is used as a fertilizer.
Q.13 Commercial nitrogen is passed through copper
chips kept in ammonia solution for reaming Q.27 There are two colourless solutions (A) and (B)
oxygen. both give white ppt. with AgNO3; ppt. dissolves
Q.14 N2 is diatomic while phosphorus molecule is in aq. NH3. Also (A) on reaction with H2O
tetra atomic. gives orange turbidity while (B) gives white
turbidity. Identify (A) and (B). Suggest the
reagent that can dissolve turbidity.
Q.28 Identify (A,B,C,) and (D) in the following– Q.34 Which of the following properties should not be

Al + N2  (A) 
 (B) H 2O associated with the fertilizer–
 (A) Insolubility in water
(
C)
 brown ppt.
(B) It should not change the pH.
(D)
(C) It should be nontoxic to the nitrifying
Q.29 Complete the following in acidic medium -
bacteria.
(A) Fe2+ + NO3– 
(D) It should be suitable in the soil
(B) SO32– + NO3– 
 (C) SO32– + NO2–  Q.35 Which of the following represent the
Q.30 One of the oxoacid salts on heating with conc. preparation of superphosphate of lime from
HNO3 and ammonium molybdate gives yellow fluoroapatite –
ppt., What is this ion ? Give chemical reactions. (A) Ca3 (PO4)2 CaF2 + 6H3PO4 
Q.31 How will you obtained. 4Ca(H2PO4)2 + 2HF 
(a) N2 from a mixture of N2 and CO (B) Ca3 (PO4)2 CaF2 + 4H2 SO4
(b) NH4Cl from a mixture of NH4Cl and KCl 4CaSO4 + 2H3PO4 + 2HF
(c) Nitrogen from a mixture of N2 and O2 (C) 3 [Ca3 (PO4)2 CaF2] + 7H2 SO4 
(d) NH3 from a mixture of N2 and NH3   3Ca(H2 PO4)2 + 7CaSO4 + 2HF
(e) PH3 from a mixture of PH3 and NH3 (D) Ca3(PO4)2 + 3H3PO4 
(f) N2 from a mixture of N2 and CO2 3Ca(HPO4)2
Q.32 NO often acts as a three electron donor in
Q.36 Triple super phosphate of lime approximately
contrast to most ligands which donate two
electrons. What happens when NO replaces contain (X) % available P2O5. Thus (X) is -
three CO in [Fe(CO)5] and six CO in [Cr(CO)6]. (A) (X)  32 % (B) (X)  90 %
(C) (X)  96 % (D) (X)  48 %
NH3 + O2  (A)
Pt.
Q.33
(A) + O2  (B) (Brown fumes) Q.37 What happens when urea is slowly
(B) + H2O  (C) + (D) (Both oxy acid) hydrolyses in soil–
(C) + l–  (E) (violet vapours) (A) CO(NH 2 ) 2  NH 4 CNO
Identify (A,B,C,D and E) (B) CO(NH 2 ) 2  CO  + NH 3 
(C) CO(NH 2 ) 2  CH 4  + N 2 O 
PART-B(PASSAGE BASED QUESTION) (D) CO(NH 2 ) 2 + 2H 2 O  (NH 4 ) 2 CO 3

Passage - I (Q. 34 to 38)

Q.38
An important phosphate fertilizer it super
phosphate of lime by the action of 60–70% of
H2SO4 on the apatite (Ca3(PO4)2) and
fluoroapatite. The mixture of monocalcium
phosphate and CaSO4 constitute super
phosphate of lime. Super phosphate of lime
contains 16–18 % available P2O5. Triple super
phosphate of lime is prepared by digersting
apatite with conc. H3PO4.
What is the disadvantages of using
(NH 4 ) 2 SO 4 as a fertilizer –
(A) (NH 4 ) 2 SO 4 is water soluble
(B) (NH 4 ) 2 SO 4 decomposes slowly to
NH 3 and NH 4 HSO 4 in the soil.
(C) (NH 4 ) 2 SO 4 increases the pH of the
soil.
(D) (NH 4 ) 2 SO 4 decreases the pH of the
soil.
Passage - II (Q. 39 to 41) Passage - III (Q. 42 to 46)
Compared to the oxyacids of nitrogen, phosphorus (V); a linear polymer
presents a much more complicated picture
particularly due to the formation of condensed + PCl5, heat
phosphates. Phosphorus forms oxyacids in the 180-200ºC
oxidation numbers, +1, +3, +4 and +5. The oxyacids excess alkali Higher press
NH4Cl NH3 (P); a
with oxidation number +3 and +5 occur in metal, Heat

slow hydrolysis
pyro and ortho-forms. The three oxyacids, H3PO2,
fertilizer
H3PO3 and H3PO4 are based on sp3 hybridized CO2

phosphorus and may be conceived to be formed heat KNO3 Heated with fused
from hypophosphorus acid by stepwise replacement Na at 200ºC
of H by OH.
(S) (T) (Q)
Q.39 H3PO2 + CuSO4  (X); a red ppt (X) is –
(A) Cu (B) Cu2O
(C) CuO    (D) Cu2H2 Suspension
of gypsum
heat (R); another fertilizer
Q.40 P4(white) + P (an alkaline solution) 
Q (reducing gas) + R (U)
R + dil H2SO4  As per the above passage answer the following
T (ppt) + S (oxyacid of P) question.
T gives apple green colour in the flame.
Thus, P, Q, R, S and T respectively are– Q.42 What is the structure of linear polymer (V) -
(A) Ba(OH)2; PH3 ; Ba (H2PO2)2; H3PO2; Cl Cl Cl
| | |
BaSO4 Cl–P=N–P=N–P–.......
(A)
(B) Ca(OH)2; P2H4; Ca (H2PO2)2;H3PO2; | | |
CaSO4 Cl Cl Cl
(C) Ba(OH)2; PH3; Ba(H2PO3)3 ; H3PO3; —P—N—
| |
BaSO4  (B)
Cl Cl
(D) Ba(OH)2; P2H4; Ba(H2PO2)2; H3PO3;
n
BaSO4
H Cl H Cl H
| | | | |
Q.41 Which of the following represent the (C) —N—P—N—P—N—
isopolyacid of phosphorus– | |
O Cl Cl n
O
|| || (D) All of the above
(A)H—P—O—P—O—H
| |
O–H O–H Q.43 The fertilizer (P) and (R) are respectively–
O O (A) CO(NH2)2 and (NH4)2 CO3
|| || (B) CO(NH2)2 and (NH4)2 SO4
(B) H—P—P—OH (C) CO(NH2)2 and CaCO3
| |
(D) CO(NH2)2 and CaCN2
HO OH
O O Q.44 (S), (T) and (U) are–
|| ||
(C) H—P—O—P—H (A) (S)  N2O (T)  NaNH2 & (U)  N3H
| |  (B) (S)  NO (T)  NaNH2 & (U)  NaN3
OH H
O O (C) (S)  N2O (T)  NaNH2 & (U)  NaN3
|| || (D) (S)  N2O (T)  Na in liquid NH3 &
(D) H—O—P—O—P—OH
| | (U)  NaN3
OH OH
Q.45 Which of the following conclusion is correct Q.47 PH5 is not known Because
regarding (U)–
(A) Bond order equal to 2.5 (A) P5+ is reduced by the H–
(B) PH5 so produced decomposed to PH3&H2.
(B) Bond order are 1.5 and 2 respectively
(C) H form 3 centre 2 electron bond between
(C) Bond orders are 2 and 2.5 respectively
the two PH3 molecules
(D) Bond order equal to 2
(D) To attain the five valent state, d orbital must
Q.46 An orange coloured gas (X) be used and hydrogen is not sufficiently
+ AgNO3 Solution AgCl ppt electronegative to make d orbitals contract
(X)
sufficiently.
KNO3; heat
Q.48 On heating Pb(NO3)2 produces a pale yellow
gas which on strong heating produces–
a dark brown gas(Y) (A) N2O4, brown gas
(A) (X)  NOCl, (Y)  NO (B) N2, colourless gas
(B) (X)  NO2Cl, (Y)  NO2 (C) NO2, brown gas
(C) (X)  N2O, (Y)  NO2 (D) N2O3 , pale blue gas
(D) (X)  NOCl, (Y)  NO2
Q.49 When PH3 is passed through acidified AgNO3
Passage – IV (Q.47 to 49)
solution at first an yellow substance (X) is
Phosphorus, forms two hydrides, phosphine and produced. (X) on further hydrolysis yields (Y).
diphosphine, P2H4, being analogous to NH3 and Therefore (X) and (Y) are–
N2H4. Elementary phosphorus reacts with H2 at 300°  (A) (X)  Ag3P, 3AgNO3
C to form PH3. The hydrolysis of metal phosphides (Y)  Ag2O
is a convenient route of prepration of PH3. White (B) (X)  Ag2O
phosphorus also reacts with hot water to produce (Y)  Ag
phosphine and hypophosphorus acid.
(C) (X)  Ag3P
Hydrazine, N2H4, may be viewed as an oxidation
(Y)  Ag
product of NH3 ,and may linked to H2O2 which may
(D) (X)  Ag3P, 3 AgNO3
be viewed as an oxidation product of H2O. It is
(Y)  Ag
obtained by oxidising aqueous ammonia by
hypochlorite under boiling in the presence of glue or
gelatin.
NH3 + NaOCl  NH2Cl + NaOH
NH2Cl + NH3  N2H4 + HCl
 EXERCISE # 4
Q. 7 Ammonia can be dried by – [IIT - 2000]
OLD IIT JEE OBJECTIVE QUESTIONS (A) Conc. H2SO4 (B) P4O10
(C) CaO (D) Anhydrous CaCl2
Q. 1 STATEMENT EXPLANATION
Although PF5, PCl5 and Phosphorus has Q. 8 The number of P–O–P bonds in cyclic
PBr5 are known, the lower metaphosphoric acid is– [IIT - 2000]
pentahalides of nitrogen electronegativity (A) Zero (B) Two
have not been observed than nitrogen. (C) Three (D) Four
electronegativity [IIT -1994]
Code : Q.9 H3PO4 and H3PO3 – [IIT - 2003]
(A) Both S and E are true, and E is the correct (A) H3PO3 is reducing agent and dibasic acid
explanation of S (B) H3PO4 is reducing agent and dibasic acid
(B) Both S and E are true, but E is ;not the (C) H3PO4 is both reducing agent and tribasic
correct explanation of S acid
(C) S is true but E is false (D) H3PO3 is not reducing agent and dibasic
acid
(D) S is false but E is true
Q.10 Which phosphorus is thermodynamically most
Q. 2 Phosphorus on reaction with hot concentrated
stable ? [IIT - 2005]
HNO3 gives – [REE - 1994] (A) White (B) Red
(A) Orthophosphoric acid (C) Black (D) Yellow
(B) Metaphosphric acid
(C) Phophosphoric acid Q.11 When two gases are mixed at 30ºC the blue
(D) Hypophosphorous acid coloured gas is formed [IIT - 2005]
(A) N2O3 (B) N2
Q.3 NO2 is obtained by heating – [REE -1994] (C) NO2 (D) N2O5
(A) AgNO3 (B) KNO3
(C) LiNO3 (D) NaNO3 Q.12 PbO2 + HNO3 (conc.)  [IIT - 2005]
(A) N2O (B) NO2
Q. 4 STATEMENT EXPLANATION (C) N2 (D) O2
HNO3 is a stronger In HNO3 there are two
acid than HNO2 nitrogen to oxygen bond Q.13 STATEMENT -1 : Alkali metals dissolve in
whereas in HNO2 liquid ammonia to give blue solutions.
there is only one. because
STATEMENT -2 : Alkali metals in liquid
[IIT -1998]
ammonia give solvated species of the type
Code :
[M(NH3)n]+ (M = alkali metals). [IIT - 2007]
(A) Both S and E are true, and E is the correct
(A) Statement-1 is True, Statement-2 is True;
explanation of S Statement-2 is a correct explanation for
(B) Both S and E are true, but E is not the Statement-1.
correct explanation of S (B) Statement-1 is True, Statement-2 is True;
(C) S is true but E is false Statement-2 is N O T a correct explanation
(D) S is false but E is true. for Statement-1
(C) Statement-1 is True, Statement-2 is False
Q. 5 White phosphorus (P4) has– [IIT -1998] (D) Statement-1 is False, Statement-2 is True
(A) Six P–P single bonds
(B) Four P–P single bonds Q.14 The reaction of white phosphorus with aqueous
(C) Four lone pairs of electrons NaOH gives phosphine along with another
(D) PPP angle of 60º phosphorus containing compound. The reaction
type ; the oxidation states of phosphorus
Q. 6 Ammonia, on reaction with hypochlorite anion, phosphine and the other product are respectively
can form– [IIT -1999] (A) redox reaction ; –3 and –5 [IIT - 2012]
(A) NO (B) NH4Cl (B) redox reaction ; +3 and +5
(C) N2H4 (D) HNO2 (C) disproportionation reaction ; –3 and +5
(D) disproportionation reaction ; –3 and +3
 EXERCISE # 5
Passage (Q.12 to Q.14)
OLD IIT JEE SUBJECTIVE QUESTIONS There are some deposits of nitrates and
phosphates in earth’s crust. Nitrates are more
Q. 1 In P4O10 the number of oxygen atoms bonded to soluble in water. Nitrates are difficult to reduce
each phosphorus atom is ...... [IIT -1992] under the laboratory conditions but microbes do
it easily. Ammonia forms large number of
Q. 2 Red phosphorus is reacted with iodine in complexes with transition metal ions.
presence of water - [IIT -1992] Hybridization easily explains the ease of sigma
donation capability of NH3 and PH3. Phosphine
P + I2 + H2O  . . . . . +. . . . . . is a flammable gas and is prepared from white
phosphorous. [IIT-2008]
Q. 3 White phosphorous (P4) is boiled with a strong
Q.12 Among the following, the correct statement is-
solution of sodium hydroxide in an inert (A) Phosphates have no biological significance
atmosphere. [IIT-1987, 93] in humans
(B) Between nitrates and phosphates,
Q. 4 NH3 + NaOCl  . . . . . +. . . . . .+ . . . .
phosphates are less abundant in earth’s
[IIT -1993] crust
(C) Between nitrates and phosphates, nitrates
Q. 5 Ammonia is a good complexing agent. Explain are less abundant in earth’s crust
(D) Oxidation of nitrates is possible in soil
[IIT -1996]
Q. 6 Elemental phosphorous reacts with conc. HNO3 Q.13 Among the following, the correct statement is-
to give phosphoric acid. How ? [IIT-1991, 97] (A) Between NH3 and PH3, NH3 is a better
electron donor because the lone pair of
electrons occupies spherical ‘s’ orbital and
Q. 7 Manufacture of phosphoric acid from is less directional
(B)Between NH3 and PH3, PH3 is a better
phosphorus [IIT -1997] electron donor because the lone pair of
electrons occupies sp3 orbital and is more
Q. 8 Reaction of phosphoric acid with Ca 5 (PO4)3 F directional
yields a fertilizer “ triple superphosphate”. (C)Between NH3 and PH3, NH3 is a better
Represent the same through balanced chemical electron donor because the lone pair of
electrons occupies sp3’ orbital and is more
equation. [IIT -1998] directional
(D) Between NH3 and PH3, PH3 is a better
electron donor because the lone pair of
Q. 9 In the following reaction– [IIT -1999] electrons occupies spherical ‘s’ orbital and
A + 2B + H2O C + 2D is less directional
(A=HNO2,B=H2SO3, C= NH2OH)IdentifyD. Q.14 White phosphorus on reaction with NaOH gives
PH3 as one of the products. This is a-
Q. 10 P4O10 + PCl5  (A) dimerization reaction
(B) disproportionation reaction
Au + HCl + HNO3  . . . . . + H2O
(C) condensation reaction
[IIT -1998 , REE-1999]
(D) precipitation reaction

Q.11 (a) What is the weight of calcium oxide when

852 gms of P4O10 reacts with it.
(b) Draw the structure of P4O10. [IIT - 2005]
 ANSWER KEY

EXERCISE # 1
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Ans. C B A B C A C D D C A D D B
Qus. 15 16 17 18 19 20 21 22 23 24 25 26 27 28
Ans. A A D C C D A C C B B A D C

29. True 30. False 31. True 32. True

33. True 34. AgCl 35. NH4Cl and N2 36. (NH4)PO4, 6H2O

37. Ca(H2PO4)2 38. HO3 and NO2

EXERCISE # 2

PART-A
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans. D D B A B C C C B A A D B A A
Qus. 16 17 18 19 20 21 22 23 24 25 26 27 28
Ans. C A D B C D A A A B B D D

PART-B
Qus. 29 30 31 32 33 34 35 36 37 38
Ans. A,B,C C,D A,B A,B,C,D A,B,C,D A,C B,C,D A,C,D B,C,D A,C

PART-C
Qus. 39 40 41 42 43
Ans. A D D A C

PART-D
44. (A)- iii, v, (B)-i (C)-i, iv, (D)-v, (E)-ii,

45. (A) - ii, iii, (B)-i, (C)-ii, (D)-v, (E)-iv

 EXERCISE # 3
(PART-A)
25. (a) PH3 + 6Ag+ + 3H2O  H3PO3 + 6Ag + 6H+ (b) PH3 + 4Cu2++ 4H2O  H3PO4 + 6Cu + 8H+
(c) 4PH3 + 8O2  P4O10 + 6H2O

26. The compound is urea, NH2CONH2

27. (A) : SbCl3 (B) : BiCl3

SbCl3 or BiCl3 + AgNO3  AgCl - (due to Cl¯ )
AgCl + 2NH3 aq.  [Ag(NH3)2]Cl
SbCl3 + H2O  SbOCl + 2HCl
orange
SbOCl + 2HCl  2BCl3 + H2O
BiCl3 + H2O  BiOCl + 2HCl
BiOCl + 2HCl  BiCl3 + H2O

28. (A) : AlN

(B) : NH3
(C) : K2HgI4 / OH¯ (Nessler’s reagent)
(D) : H2N — Hg — O —Hg — I (Iodide of million’s base)

29. (A) 3Fe2+ + 4H+ + NO3–  3Fe3+ + 2H2O+ NO

(B) SO32–+ 2NO3– + 2H+  SO42– + 2NO2 + H2O
(C) SO32–+ 2NO2– + 2H+  SO42– + 2NO + H2O

30. It is PO4 3– (phosphate) ion –

H3PO4 + 21HNO3 + 12(NH4)2MoO4  (NH4)3PO4 .12MoO3 + 21NH4NO3 + 12H2O

31. (a) By bubbling through ammoniacal cuprous chloride in which CO is absorbed but not N 2.
(b) By sublimation, NH4Cl sublimes leaving KCl as residue.
(c) By bubbling through alkaline solution of pyrogallol in which oxygen is absorbed but not N 2.
(d) By bubbling through H2SO4 when NH3 is absorbed but not N2. Ammonia is recovered by heating the solution of
(NH4)2SO4 with excess of NaOH.
(e) By bubbling through water in which NH3 dissolves but not PH3 .
(f) By bubbling through water under high pressure of through NaOH solution in which CO 2 dissolves but not N2 .

32. Fe(CO)5 + 2NO  [Fe(CO)2](NO)2+ 3CO

33. (A) : NO
(B) : NO2
(C) : HNO2
(D) : HNO3
(E) : I2
(PART-B)

Qus. 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49
Ans. A C D D D D A D A B C D D D C D
 EXERCISE # 4
Q. No. 1 2 3 4 5 6 7 8
Ans. B A A,C C A,C,D B,C C C
Q. No. 9 10 11 12 13 14
Ans. A C A D B C

EXERCISE # 5
1. 4

4. 2NH3 + NaOCl  NH2.NH2 + NaCl + H2O

8. Ca5(PO4)3F + 7H3PO4 + 5H2O  5Ca (H2PO4)2.H2O + HF

9. D is H2SO4

10. P4O10 + 6PCl5  10POCl3

2Au + 3HNO3 + 11HCl  2HAuCl4 + 3NOCl + 6H2O
O
P

O O O
O
11. (a) 1008 gms (b) O P P O
O P O

O
12. (C)

13. (C)
In PH3 p-character is mostly used for bonding while lone pair is in predominantly s-character orbital which is
diffused & less reactive..

14. (B)