15th Group Elements

JEE-MAIN-SR-CHEM-VOL-II 15th GROUP ELEMENTS
15th GROUP ELEMENTS

Basics at a glance Oxides of Nitrogen:
Minerals of elements Ø Nitrous Oxide (or)
Mineral sources of nitrogen Laughing gas (or) : N2O
Salt petre (or) Bengal salt petre : KNO3 Nitrogen monoxide (or)
Di nitrogen monoxide
Chile salt petre : NaNO3 Ø Nitric Oxide : NO
Ø Minerals of Phosphorous Ø Nitrogen dioxide : NO2
Fluorapatite : {3Ca ( PO ) .CaF } ;
3 4 2 2 Di Nitrogen Tetroxide : N 2O4
Chlorapatite : {3Ca 3 ( PO 4 )2 .CaCl 2 } ; Ø Dinitrogen trioxide (or) Sesquioxide: N 2 O3
Hydroxyapatite : {3Ca (PO ) .Ca (OH ) } ;

3 4 2 2
Ø Di Nitrogen Pentoxide : N 2 O5
Oxides of Phosphorous:
Phosphorite rock : {Ca ( PO ) } .
3 4 2
Phosphorus trioxide : P2 O3 or P4 O 6
Ø Minerals of As, Sb and Bi
As: Phosphorus pentoxide : P2 O5 or P4 O10
Realgar : {( As4 S4 )}{red − orange colour} Oxy acids of phosphorous
Orpiment: {( As2 S3 )}{ yellowcolour}

Hypophosphorous acid : H 3 PO2
Sb: Stibinite : {( Sb2 S3 )} and in flue dust as Sb2O3

Orthophosphorous acid : H 3 PO3
Bi: Bismuth glance : {( Bi S )}
2 3
or Bismuthinite Orthophosphoric acid : H 3 PO4

Bismuth ochre or Bismite: {( Bi2O3 )} Peroxy phosphoric acid : H 3PO5
Bismuthite : {( BiO )2 CO3 } Pyrophosphorus acid : H 4 P2O5
Ø Allotropes of Nitrogen Hypophosphoric acid : H 4 P2O6
α -Nitrogen (Solid State)
β - Nitrogen (Solid State) Pyrophosphoric acid : H 4 P2O7
Ø Allotropes of Phosphorous Metaphosphoric acid : ( HPO3 )n
White or yellow phosphorous
Super Phosphate of Lime:
Red phosphrous
α -Black phosphorous Ca ( H2PO4 )2 CaSO4.2H2O
β -Black phosphorous Ø Nitrolim : CaNCN + C (Calcium cyanamide
Violet phosphorous + graphite)
Scarlet phosphorous
Ø Allotropes of Arsenic Ø Triple Phosphate of Lime: 3Ca ( H 2 PO4 )2
Metallic or grey Ø Drying agent for ammonia is quick lime, CaO
Non-Metallic or yellow, black arsenic Ø Acidic oxides : N2O3 and N2O5
Ø Allotropes of Antimony P4O6 and P4O10
Crystalline Ø Amphoteric oxides : As4O6 and Sb4O6
Non-metallic or Yellow Ø Basic oxide : Bi2O3
α -antimony Ø Neutral oxides : N2O, NO
Explosive antimony
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15th GROUP ELEMENTS SR-MAIN-CHEM-VOL-II
JEE-MAIN-SR-CHEM-VOL-II
Ø Phosphoproteins are present in milk and eggs.
SYNOPSIS Ø Important sources of “P” are phosphate rocks
Introduction like
Ø Fluorapatite - 3Ca3(PO4)2. CaF2
Ø Nitrogen, Phosphorous, Arsenic, Antimony and
ØChlorapatite - 3Ca3 (PO4)2. CaCl2
Bismuth belong to VA group or 15th group of
Ø Hydroxy apatite [3Ca3(PO4)2Ca(OH)2]
the periodic table.
Ø Phosphorite rock [Ca3(PO4)2]
Ø The atomic numbers of N, P, As, Sb, and Bi are
Ø As, Sb and Bi are mostly available as their
7, 15, 33, 51 and 83 respectively.
sulphide minerals
Ø Elements of Nitrogen family are called
Ø In the flue dust antimony is available as Sb2O3
pnicogens and their compounds are called
Ø In air occurance of VA group elements decreases
pnictides as these elements forms pungent
from N to Bi
smelling compounds.
Electronic configuration: The general
valency shell electronic configuration of these
elements is ns2 np3.
Ø The penultimate shell of nitrogen contains two
electrons, phosphorous contains eight electrons
while As, Sb and Bi contains eighteen electrons.
Ø These elements are extra stable due to
completely filled s-subshell and half filled p-
sub shell.
General properties: Nitrogen is a diatomic
gas while the other elements are solids.
Ø P, As and Sb are tetra atomic. Bi is mono atomic.
Bonding: Nitrogen is a diatomic gaseous
molecule where as phosphorus is a tetraatomic
Ø Occurrence: The percentage of relative solid.
abundance of elements in the earth crust is This is because nitrogen atoms are small in size
P>N>As>Sb>Bi and can approach very close to one another so
Ø Except ‘P’ all other elements occur in free state. lateral overlap of p-orbitals can takes place to
Ø In air N2 occurs to the extent of 78% by volume form π -bonds.
or 80% by mass. N2 is an essential constituent Phosphorus atoms are larger in size hence lateral
of proteins and amino acids. overlapping is not possible. So P4 molecules are
Ø In the earth crust nitrogen is available as nitrates formed by single bonds between P atoms.
Ø Nitrogen is chemically inert at room temperature
Ø Phosphorus is the 11th most abundant element because N ≡ N energy is very high (941.4 K.J. /
in the earth’s crust. mole).
Ø Phosphorus occurs in minerals of the apatite
Ø In Nitrogen molecule 1σ and 2π bonds are
family,
present.
Ca 9 ( PO4 )6 .CaX 2 ( X = F, Cl or OH )
Atomic Radius:Atomic radius of the
(e.g. fluorapatite Ca 9 ( PO 4 )6 .CaF2 ) which are elements gradually increase from nitrogen to
the main components of phosphate rocks. bismuth
Ø Phosphorus is an essential constituent of animal Ø The increase in the radius is less predominat
and plant matter. It is present in bones as well beyond phosphorus due to shielding effect by
as in living cells. inner d - orbitals .
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Metallic character: Nitrogen and Ø In P4 molecule, the four P atoms are present at
Phosphorus are non metals. Arsenic and the corners of a tetrahedron and bond angle is
Antimony are metalloids and Bismuth is a metal. 600.
Ø Atomic radius, metallic character, Density and Ø White phosphorus molecule has 6 P-P bonds. It
B.P. gradually increase from N to Bi. has a regular tetrahedral structure.
Ø Most reactive form of phosphorous is white due
Conductivity: The Nitrogen and Phosphorus to high bond angle strain.
are non conductors of heat and electricity. Ø It is a translucent white waxy solid. It is
Arsenic is a poor conductor Antimony and poisonous.
Bismuth are the good conductors of heat and Ø Insoluble in water but soluble in carbon
electricity. disulphide and glows in dark
Ionisation Potential: The IP of the elements ( chemiluminescence).
is relatively high compared Ø It dissolves in boiling NaOH solution in an inert
to the corresponding elements of the adjacent atmosphere giving PH 3
groups.This is due to the stable electronic P4 + 3NaOH + 3H2O → PH3 + 3NaH2PO2
configuration of ns 2 np 3 in their valency shell Ø It readily catches fire in air to give dense white
Ø Ionisation potential, electronegativity, fumes of P4 O10 .
electron affinity gradually decrease from N to
Bi. Red Phosphorous: Phosphorous tetrahedron
Ø The order of electron affinity is polymerises to form more inactive “Red -
N < P > As > Sb > Bi phosphorous.”
Ø M.P. increases upto As (grey α − form) and then
decreases.
Allotropic forms: Allotropy may observed
in all the 3 states of matter i.e solids, liquids,
gases
Ø Except bismuth all the elements of this group
exhibit allotropy.
Ø Nitrogen has two allotropes in the solid state. Ø It is obtained by heating white phosphorous at
They are α - Nitrogen (cubic crystalline) and 573K in an inert atmosphere for several days.
β -Nitrogen (hexagonal crystalline). When red phosphorous is heated under high
pressure, a series of layers of black phosphorous
Ø Phosphorus exists in a variety of forms. The
are formed which are similar to graphite.
most important forms of phosphorus are white
Ø Red phosphorous possesses iron grey lustre. It
or yellow, red, α - Black, β - Black, scarlet, is odourless, non poisonous and insoluble in
violet. water as well as in carbon disulphide.
Ø White Phosphorous:White phosphorous is Ø Less reactive than white phosphorous.It does not
stored under water. glow in the dark.
Ø White phosphorous contains discrete P 4 Black phosphorous: It has two forms α -black
molecules.
phosphorous and β -black phosphorous.
Ø α - black is formed when red phosphorous is
heated in a sealed tube at 803K.
Ø β -black is prepared by heating white
phosphorous at 473K under high pressure.
Ø Allotropes of As & Sb
As : Metallic or grey arsenic
Non-metallic or yellow arsenic
Black Arsenic
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Ø Most of the scientists believe that “yellow Ø Similarly, in case of phosphorus nearly all
antimony” is nothing but a solid solution of intermediate oxidation states disproportionate
antimony trichloride (SbCl3) in yellow antimony. into +5 and -3 both in alkali and acid medium.
Ø The allotropes of Antimony are yellow, metallic However +3 oxidation state in case of arsenic,
form and explosive forms. antimony and bismuth becomes increasingly
stable with respect to disproportionation.
Catenation: The catenation capacity depends
on bond energy Greater the bond energy value, GRADATION IN THE PHYSICAL
higher the “catenation capacity” CONSTANTS OF GROUP VA ELEMENTS
Ø Nitrogen has more bond energy than
phosphorus.
Ø Nitrogen forms upto eight atoms chains that are
known at room temperature, but only
N2H4 - hydrazine
HN3- Hydrazoic acid are stable
Ø Tetrazenes (H2N - N = N - NH2) having organic
substituents give chains longer than 2 -
tetrazenes
Ø Phosphines containing more than 2
‘Phosphorous atoms in linear as well as cyclic
forms are also identified
Ex:P4H6 tetraphosphine
Catenation capacity decreases from N - Bi
Oxidation states: “P” similar to nitrogen
exhibits all possible oxidation states between +
III and +V in its hydrides, oxides
Ø VA group elements exhibit -3, +3 and + 5
oxidation numbers.
Ø Nitrogen exhibits all the oxidation states from -
3 to +5 and -1/3 in N 3 H
Stable oxidation number of Bi is +3 due to inert
pair effect. Anomalous properties of Nitrogen
Ø The stability of -3 oxidation state decrease from Ø Nitrogen differs from the rest of the members
N to Bi due to decrease of non-metallic nature. of this group due to its.
Ø Nitrogen forms tri negative ion N 3− easily. Ø Small size • high EN • high IE
Ø Non-availability of vacant d-orbitals.
Phosphorus forms P 3− ions with difficulty.
Ø Nitrogen exhibts unique ability to form
Ø The stability of +5 oxidation state decreases Pπ - Pπ multiple bonds with itself and other
and +3 oxidation state increases down the
elements having small size and high EN like
group from N to Bi due to inertpair effect.
C, O.
Ø As, Sb and Bi cannot form trinegative ions. Ø Due to absence of vacant d-orbitals nitrogen
Ø In the case of nitrogen, all oxidation states from covalency is restricted to four and cannot form
+1 to +4 tend to disproportionate in acid
dπ − Pπ similar to the heavier elements
solution. For example,
Eg : R3 P = 0(or ) R3 P = CH 2
3HNO 2 → HNO3 + H 2 O + 2NO
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W.E-1: Red phosphorous is less reactive than Ø Ammonia is only a mild reducing agent while
white phosphorous .why ? BiH3 is the strongest reducing agent amongst
Sol. Red phosphorous is stable due to its chain like all the hydrides.
polymeric structure, therefore red phosphorous Ø The tendency to form co-ordinate covalent
is less reactive .Moreover, white phosphorous bonds gradually decreases from NH3 to BiH3 .
is very reactive due to its discrete P4 structure Ø Except NH3 other hydrides have little or no
tendency to form coordinate covalent bonds (to
and P - P - P bond angle strain at 600
donate e − pair)
W.E-2: Nitrogen exhibits a maximum covalency Ø From NH3 to BiH3 ionic nature increases.
of four .Explain Ø MH3 type hydrides are trigonal pyramidal in
shape.
Sol. Nitrogen has no vacant ‘d’ orbital (ie. 1s 2 2s 2 2 p 3 ).
Ø In NH 3 molecule central atom will make use of
Excitation of 2s electron into 3s is not possible.
Therefore it can form only 4 bonds ie, three sp3 hybrid orbitals.
single covalent bonds and one dative bond due Ø In MH3 type hydrides, the bond angle decreases
to the lone pair of electrons in 2s. from NH3 to BiH3 due to increase in the size of
atom M and decrease in the E.N.
Chemical Properties: Ø As pure ‘p’ orbitals of As and Sb are involved,
Hydrides: Hydrides of Nitrogen are NH 3 the HMH bond angle in AsH3 and SbH3 are
(Ammonia), N2H4 (Hydrazine), N3H (Hydrazoic expected to be 90 0. But due to repulsions
Acid) between M-H bonds, the angle is likely greater
Ø Hydrazoic acid is a mono basic acid. than 900
Hydrides of phosphorus are PH3 (Phosphine), Ø PH3 is quite stable in air. But, PH3 frequently
P2H4 (Diphosphine) contains P2H4 (diphosphine) in traces as impurity
P2H4 is the least stable hydride. so when heated to 1500C P2H4 catches fire.
As, Sb and Bi forms only AsH3 (Arsine), SbH3 Ø PH3 can also act as an electron pair donor and
(Stibine) and BiH3 (Bismuthine). forms complex. Ex: [Cl3Al ← PH3 ]
Ø All the hydrides of the type MH3. (M = VA group Reaction of NH 3,PH 3 and AsH 3 with HI is
element) are prepared by the action of water or similar
dilute acids on their metal compounds like NH 3 + HI → NH 4 I − Ammonium iodide
Mg3N2, Ca3P2, Zn3As2, Mg3Sb2 and Mg3Bi2.
PH3 + HI → PH 4 I − Phosphonium iodide
Ø BiH3 is very difficult to prepare because, it
Ø Hydrogen atoms of NH3 may be substituted
dissociate even at 250 C
by groups like Cl2 alkyl groups such as CH 3 .
Ø The ease of formation of hydrides decreases
from NH3 to BiH3. Similar substitutions are less common in PH 3 .
Ø Except NH 3 , the remaining hydrides are Ø P(CH3)3 is more basic than PH3 due to + I effect
poisonous gases. of −CH3 groups
Ø MH3 type hydrides are colourless and volatile Note:
gases. Ø VA group elements cannot form MH5 type of
Ø From N to Bi, E.N decreases and so that polarity hydrides due to small size of hydrogen atom.
of M-H bond decreases hence their solubility Ø Though ‘N’ has greater EN ammonia is the
also decreases. strongest electron pair donor of all the hydrides
Ø The ability to donate lone pair (Lewis basic of VA group elements. This is
nature), stability and basic strength of the • Because the small size of the “nitrogen atom”
hydrides decrease from NH3 to BiH3. (because of small size e − density is more on sp3
Ø Reducing power of the hydrides increases from hybrid orbital compared to ‘p’ and other
NH3 to BiH3 due to decrease in bond enthalpy elements.)
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• In other hydrides greater M-H bond length leads Ø Trioxides and pentoxides of P, As and Sb are
to weakening of the covalent bond. dimers.
• The lone pair of e– is spread over a larger atom. Ø From N2O3 to Bi2O3 acidic nature decreases and
As a result of this e– density on the atom and e– basic nature increases.
donating nature (basic nature) decreases.
Ø The most acidic trioxide is N 2 O3 and most basic
Ø NH3 forms hydrogen bonds with water
trioxide is Bi 2 O3 the acidic and basic nature of
Trends in some properties of hydrides an oxide depends on the size and charge on the
of VA group elements: VA group element.
• M.P PH3 < AsH3 < SbH3 < NH3 Ex: N is small and having +III oxidation state
• B.P PH3 < AsH3 < NH3 < SbH3
hence N2O3 is acidic.
• B.L NH3 < PH3 < AsH3 < SbH3
• B.E NH3 > PH3 > SbH3 > AsH3 Ø Except Bi other elements form pentoxides.
• B.A NH3 > PH3 > AsH3 > SbH3 Ø Acidic nature decreases or basic nature increases
• Reducing power NH3<PH3<AsH3<SbH3 <BiH3 from N2O5 to Sb4O10
• Basic Nature: NH3>PH3>AsH3>SbH3>BiH3 Ø N2O5 is the most acidic oxide in VA group
• Stability: NH3>>PH3>AsH3>SbH3>>BiH3 elements.
Ø Trioxides dissolve in water giving - Ous acids.
W.E-3: PH 3 has lower boiling point than
P4O6 + 6 H 2O → 4 H3PO3
NH 3 .Why?
(Orthophosphorus acid )
Sol. Unlike NH 3 , PH 3 molecules are not associated
Ø Pentoxides dissolve in water giving - ic acids.
through hydrogen bonding in liquid state. That P4O10 + 6H 2O → 4H 3PO 4 (Ortho phosphoric
is why the boiling point of PH 3 is lower acid)
than NH 3 . P4O10 + 2H2O → 4HPO3 (Meta phosphoric acid)
Ø From top to bottom Oxidising nature of trioxides
W.E-4: The Lewis basic strength of PH 3 is less decreases.
Ø Trioxides are more stable than pentoxides
than that of NH 3 .Explain . (Because in pentoxides elements are in excited
Sol. The electron pair density on the smaller ‘N’ state)
atom is more than the larger ‘P’ atom .Electron Ø The stability of pentoxides decreases from N2O5
donation is more for ‘N’ of NH 3 compared to to Bi2O5.
‘P’of PH 3 . Therefore PH 3 is a weaker Lewis Halides: VA group elements form trihalides
of the type MX3 and pentahalides of the type
base than NH 3 .
MX5.
Oxides: These elements form two series of Ø Trihalides are prepared by the reaction of VA
oxides - Trioxides (M 2O3) and Pentoxides group element or its compound with halogen.
(M2O5). Ø NF3 does not undergo hydrolysis.
Ø Nitrogen forms number of oxides due to Ø NCl3 on hydrolysis gives NH3 and Hypochlorous
Pπ − Pπ multiple bonding between N and acid.
oxygen atoms. NCl3 + 3H2O → NH3 + 3HOCl
Ø As oxidation number of the element increases, Aqueous solution of NCl3 acts as a bleaching
acidic nature of its oxides increases. agent due to formation of HOCl.
Ø As the atomic number increases acidic nature
Ø PF3 is weakly reactive with water
of oxides decreases.
Ø Acidic nature of pentoxides is more than that of Ø The extent of hydrolysis decreases from NX3 to
trioxides. BiX3.
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Ø PCl3 on hydrolysis gives HCl and H3PO3. Ø Very pure nitrogen can be obtained by the
PCl3 + 3H2O → H3PO3 + 3HCl thermal decomposition of sodium or barium
PCl3 is a covalent but the aqueous solution of azide.
PCl3 is good conductor due to the formation of
Ba ( N3 )2 → Ba + 3N 2
HCl.
Ø Trihalides except BiF3 are predominantly 2NaN 3 → 2Na + 3N 2
covalent in nature.
Properties: Dinitrogen is a colourless,
Ø Trihalides use Sp3 hybridised orbitals of the
odourless, tasteless and non-toxic gas.
central atom.
Ø Trihalides have trigonal pyramid structure. Ø Nitrogen atom has two stable isotopes: 14 N and
Ø Penta halides use the sp3d hybridised orbitals of 15
N.
the central atom. Ø Nitrogen has a very low solubility in water
Ø Pentahalides have trigonal bipyramidal
( 23.2cm3 per litre of water at 273K and 1 bar
structure.
Ø In the formation of PCl5 the central phosphorous pressure) and low freezing and boiling points
will make use of Sp3d hybrid orbitals. Ø Dinitrogen is rather inert at room temperature
Ø Nitrogen cannot form NCl5 because it has no d- because of the high bond enthalpy of N ≡ N
orbitals in the valency shell. bond. Reactivity, however, increases rapidly
Ø PCl5 is obtained by passing Cl2 into liquid PCl3. with rise in temperature.
Ø PCl5 undergoes a two step hydrolysis. Ø At higher temperatures, it directly combines
PCl5 + H2O → POCl3 + 2HCl with some metals to form predominantly ionic
POCl3 + 3H2O → H3PO4 + 3HCl nitrides, and with non-metals, Covalent nitrides.
Ø Bi cannot form stable penta halides due to inert A few typical reactions are
pair effect. 6 Li + N 2 
Heat
→ 2 Li3 N
Ø Pentahalides are more covalent than trihalides.
Ø All the trihalides of these elements except those 3Mg + N 2 
Heat
→ Mg 3 N 2
of nitrogen are stable.( NF3 is stable). Ø It combines with hydrogen at about 773K in the
persence of a catalyst (Haber’s Process) to form
Dinitrogen preparation: Dinitrogen is ammonia:
produced commercially by the liquefication and
N 2 ( g ) + 3H 2 ( g )
2 NH 3 ( g ) ;

773 K
fractional distillation of air.
Ø Liquid dinitrogen (b.p. 77.2K) distils out first
∆ f H Θ = −46.1 Kjmol −1
leaving behind liquid oxygen (b.p.90K).
Ø In the laboratory, dinitrogen is prepared by Ø Dinitrogen combines with dioxygen only at very
treating an aqueous solution of ammonium high temperature
chloride with sodium nitrite. N 2 + O2 ( g )
2 NO ( g )

Heat
NH 4 Cl (aq ) + NaNO2 (aq ) → (at about 2000 K)

N 2 (g ) + 2H 2O (l ) + NaCl (aq ) Ø The main use of dinitrogen is in the manufacture
of ammonia and other industrial chemicals
Small amounts of NO and HNO3 are also containing nitrogen (e.g.,calcium cyanamide).
formed in this reaction which are removed by Ø It also finds use where an inert atmoshpere is
passing the gas through aqueous sulphuric acid required (e.g., in iron and steel industry, inert
containing potassium dichromate. It can also diluent for reactive chemicals).
be obtained by the thermal decomposition of Ø Liquid dinitrogen is used as a refrigerant to
ammonium dichromate. preserve biological materials, food items and in
( NH4 )2 Cr2O7 
Heat
→ N2 + 4H2O + Cr2O3 cryosurgery.
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W.E-5: What are the products obtained by the Ø Now a days ammonia is manufactured from coal
thermal decomposition of sodium azide. Coal on destructive distillation gives
A. The thermal decomposition of sodium azide Ø Coal gas
gives dinitrogen gas Ø Ammonical liquor and Coaltar
Ø Pitch
2 NaN 3 → 2 Na + 3 N 2
Ø The ammonical liquor is treated with “milk of
lime” and steam is blown through the solution.
W.E-6: When compared to CN − , NO + and Ø The mixture of steam and NH3 gas produced is
CO, N 2 is chemically inert. Explain . absorbed in H2SO4. (NH4)2SO4 is formed in the
A. Nitrogen is inert because of non-polar bond solution.(The salt is seperated by crystalisation)
nature and high bond dissociation energy on the other hand if the mixuture of steam and
NH3 is passed through water under pressure
( N ≡ N ) .The rest all are polar molecules Conc. Solution of NH3 is obtained.
which can easily dissociate to participate in Ø Ammonia forms ammonium salts with acids,
chemical reactions.
e.g., NH 4 Cl, ( NH 4 )2 SO4 , etc. As a weak base,
Ammonia: In modern times ammonia is it precipitates the hydroxides (hydrated oxides
manufactured by following process. in case of some metals) of many metals from
• By Cyanamide process their salt solutions. For example,
• From coal • By Haber’s process
Ø Ammonium salt on heating with an alkali gives ZnSO4 (aq ) + 2NH 4 OH (aq ) →
ammonia gas.
NH4Cl + NaOH → NaCl + NH3 + H2O Zn ( OH )2 (S ) + ( NH 4 )2 SO 4 ( aq )
2NH4Cl + Ca(OH)2 → CaCl2 + 2NH3 + 2H2O ( White ppt )
Haber’s process: On large scale, ammonia
FeCl3 (aq ) + NH 4 OH (aq ) →
is prepared by Haber’s process.
Ø In Haber’s process ammonia is synthesised Fe 2 O3 .xH 2 O (s ) + NH 4 Cl (aq )
directly from elements.
Ø The nitrogen and hydrogen used in the Haber’s ( brown ppt )
process must be very pure Due to Lewis basic nature it forms complex
N2 + 3H2 ⇔ 2NH3 : ∆H = −93.63 KJ
compounds with metals like Cu 2+ , Ag +
Ø Conditions
2+
Ø Temperature : 725 to 775 K Cu 2 + (aq ) + 4NH 3 (aq )  Cu ( NH 3 )4  (aq )
Ø Pressure : 200- 300atm
Ø Catalyst : Finely divided iron
( blue ) (deep blue )
Ø Promotor: Molybdenum or Oxides of Ø Ag + ( aq ) + Cl − ( aq ) → AgCl ( s )
Potassium and Aluminium
Ø The nitrogen required for the process is colourless white ppt
obtained from air by liquefication, followed AgCl ( s ) + 2 NH 3 ( aq ) →  Ag ( NH 3 )2  Cl
by liquid air, Hydrogen is produced by the
white ppt colourless
electrolysis of water,
Ø Ammonia is formed to extent of about 10% in Uses of Ammonia
the reaction Ø as a refrigerant
Ø Nitrogen and Hydrogen are mixed in the ratio Ø as a solvent
1:3 Ø in the manufacture of Ammonium sulphate,
Ø Dehydrating agents like P2O5, Con. H2SO4, Urea and other fertilizers.
anhydrous CaCl2 are not used for drying NH3, Ø in the manufacture of HNO 3 by Ostwald’s
because they react with ammonia. process.
Ammonia is dried over CaO (Quick lime).
8
Tests for ammonia : Ammonia gives brown Ø It is a blue liquid at low temperature.
precipitate with Nessler’s reagent K2[HgI4]. The Ø It is an acidic oxide.
formula of the precipitate formed in the above, Ø It is anhydride of Nitrous acid.
i.e. Hg2O. NH2I (Iodide of millon’s base). The following two structures are proposed.
Ø Nessler’s reagent is a mixture of KI, HgCl2 and
NaOH.
Ø It gives dense white fumes when exposed to a
glass rod dipped in HCl solution.
Oxides of Nitrogent
Nitrous oxide (or) Nitrogen monoxide
(N2O): It is also known as laughing gas.
Ø It is prepared by heating ammonium nitrate.
NH 4 NO 3  Heat
→ N 2 O + 2H 2 O
Ø It is a colourless neutral oxide. Ø
Ø It is a linear molecule.
The structure of N 2O is
•• •• Nitrogen dioxide (or) Dinitrogen tetroxide
:N ≡ N →O:↔:N = N = O: (NO2 (or) N2O4) :
•• ••
N N O (lin ea r) Ø It is obtained by heating Lead Nitrate.

11 3p m 11 9p m 2Pb (NO3)2  ∆
→ 2PbO + 4NO2 + O2
Ø Usually N2O is administered to patients to Ø It is a reddish brown poisonous gas soluble in
induce sleep. Hence used as local anaesthetic. water.
Nitric Oxide (NO): It is formed as an Ø It becomes a colourless solid on cooling due to
intermediate in the manufacture of HNO3 by the formation of dimer N2O4.
catalytic oxidation of NH3 in presence of Pt. Ø It dissolves in water giving HNO2 and HNO3.
So it is called mixed anhydride.
4NH3 + 5O 2  ∆ → 4NO + 6H2O
Pt
Ø NO2 is an odd electron molecule and exhibits
Ø NO formed during lightening stage paramagnetic property.
Ø It is a colourless, neutral gas. Ø In dimeric state (N2O4 ) it is colourless and
Ø It is paramagnetic due to the presence of diamagnetic in nature
unpaired electron .
Ø It gives reddish brown gas in air by oxidation.
Ø It readily reacts with O2 as
2NO + O2 → 2NO2 (Reddish brown gas)
••
Its structure is : N = O••g ↔ : N = O :
. ••
N−O
Ø
115pm
Nitrogen trioxide (N2O3): It is also known

as Nitrogen sesqui oxide. Dinitrogen pentoxide (N2O5)
Ø It is formed by cooling an equimolar mixture of Ø It is obtained by dehydrating HNO3 with P2O5.
NO and NO2. 4HNO3 + P4 O10 → 4HPO3 + 2N 2 O5
−20º C Ø
NO + NO2 
→ N 2O3 It is the anhydride of Nitric acid.
9
Ø It is a powerful oxidising agent. Oxyacids of Nitrogen
Ø It is a colourless solid. Hypo nitrous acid: HNO (or) H2N2O2
Ø It disolves in water to give nitric acid. Ø The molecular formula of Hypo nitrous acid is
N 2 O5 + H 2 O → 2HNO3 H 2 N 2O2 , its basicity = 2.
Ø It has planar structure and is represented as Nitrous acid (HNO2):
Ø Nitrous acid is unstable except in dilute solutions
Ø In the laboratory it is prepared by the addition
of ice cold dilute acid to Barium nitrite
’ Ba ( NO 2 )2 + H 2SO 4 → BaSO 4 + 2HNO 2
(ice cold )
Ø It is obtained by dissolving N2O3 in water.
Ø Its solution is slightly bluish in colour due to
the presence N2O3.
Ø HNO2 is a weak acid and its salts are known as
nitrites
Ø Ex : Sodium Nitrite NaNO2
Ø It is an unstable.
Ø On long standing it undergoes
disproportionation in acidic solution
Note: In solid state it exists as NO2+, NO3- ions.
(Nitrosonium Nitrate) 3HNO 2 → HNO3 + 2NO + H 2 O
In this reaction
W.E-7: Explain why NO is colourless and NO2 In HNO2 → HNO3 O.S of ‘N’ changes from +3
is coloured even if both contain odd number to +5
of electron . In HNO2 → NO O.S of N changes from +3 to +2
Sol. In NO molecule , the odd electron is involved i.e “HNO2” as oxidant changes to ‘NO’ and as
in bonding between two bonded atoms, and reductant changes to “HNO3” so it acts as an
the excitation of it is difficult (possible only in oxidising and reducing agent.
Ø With oxidising agents stronger than HNO2 like
uv region) In NO2 the unpaired electron can be
excited easily by absorption of vissible light. KMnO4, K2Cr2O7, Br2 + H 2 O or H2O2 solutions
HNO2 functions as reductant.
Thus NO is colourless and NO2 is coloured.
Ø Where as with weaker oxidants i.e reducing
agents like H2S, SO2 ‘or’ Sn+2 solutions HNO2
W.E-8:Why does NO2 dimerise? functions as oxidant
Sol. NO2 contains odd number of valence Ø At low temperatures HNO2 reacts with aromatic
electrons .It behaves as a typical odd molecule. primary amines and gives “diazonium
On dimerisation , it is converted to a stable compounds”
Diazonium compounds can be converted into
N 2O4 molecule, with even number of different substituted aromatic compounds
electrons. Structure of (HNO2)
Ø Its structure is HO - N = O
W.E-9: NO2 and N 2O4 exhibit different magnetic HNO2 exists in two tautomeric forms i.e in two
properties . Explain . structural isomers.
Sol. NO2 is paramagnetic and is reactive due to
the presence of unpaired electron . N 2O4 is
the dimer of NO2 which has no unpaired
electron . It is diamagnetic .
10
Thus the product formed is recycled and the
W.E-10: N 2O3 , N 2O4 and N 2O5 are anhydrides
of which oxyacids . aqueous HNO3 can be concentrated by
distillation upto : 68% by mass. Further
Ans. N 2O3 is an anhydride of nitrous acid
concentration to 98% can be achieved by
N 2O3 + H 2O → 2 HNO2 dehydration with cencentrated H 2 SO4 .
N 2O5 is an anhydride of nitric acid Concentration of HNO3 : The crude HNO3
N 2O5 + H 2O → 2 HNO3 is concentrated in three stages.
Stage-1: 61% HNO3 is distilled until 68% HNO3
N 2O4 is a mixed anhydride of nitrous acid is obtained
and nitric acid Stage-2: 68% HNO3 is mixed with Conc H2SO4
N 2O4 + H 2O → HNO2 + HNO3 and subjected to azeotropic distillation, where
98% acid is obtained.
Preparation and uses of Nitric acid Stage-3: 98% HNO3 is cooled in a freezing
(HNO3) mixture then crystals of pure HNO3 seperates
Ø Nitric Acid is also called aqua fortis (strong out.
water)
Structure of Nitric acid
Ø HNO3 is the most important oxy acid of +
+
Nitrogen HO− N =O HO − N → O −
↓ ||
Ø HNO3 is prepared on large scale by O− O
1) Birkland-Eyde process (Arc process)
2) Ostwald’s process (from ammonia)
Ø Birk land-Eyde process is used at places
where electric power is cheap.
Principle : In air N2 and O2 are converted to
Nitric oxide at an electric arc.
N 2 + O2 
Electric arc
→ 2 NO; ∆H = +180.7 kJ Uses of HNO3: In the manufacture of fertilisers
Ø NO is oxidised to NO2 by atmospheric oxygen. like basic calcium nitrate [CaO.Ca(NO3)2]
2 NO + O2 → 2 NO2 Ø In the preparation of explosives like TNT,
Ø NO2 is made to react further with air and water nitroglycerine etc.
to form HNO3 Ø as nitration mixture along with H2SO4
Ø In the preparation of perfumes, dyes and
4 NO2 + O2 + 2 H 2O → 4 HNO3 medicines
Ostwald’s process (from ammonia):NH3 Ø HNO3 is a very strong oxidising agent used in
mixed with air in 1 : 7 or 1 : 8 when passed over the oxidation of cyclohexanol or Cyclohexanone
a hot platinum gauze or rhodium catalyst is to adipic acid.
oxidised (95%) to NO Ø p-xylene to terepthalic acid
Ø In the preparation of artificial silk i.e “cellulose
4NH3+5O2  1155 K

pt gauze
→ 4NO+6H 2
O+1275 K.J nitrate”
Nitric oxide thus formed combines with oxygen Ø In laboratory it is prepared by the action of conc
giving NO2 . H2SO4 on KNO3 or NH4NO3
KNO3 + H2SO4 → KHSO4 + HNO3
2 NO + O2 ( g ) 2 NO2 ( g ) Ø A mixture of 1 : 1 Conc HNO3 and Conc H2SO4
Ø Nitrogen dioxide so formed, dissolves in water is known as nitration mixture
It is used in nitration reaction of organic
to give HNO3 .
compounds like Benzene, Toluene and phenol
3NO2 ( g ) + H 2O (l ) → 2 HNO3 ( aq ) + NO ( g ) C6H6 + HNO3  H 2SO 4
→ C6H5NO2 + H2O
11
Properties: It is a colourless liquid (f.p.231.4K between the solution and sulphuric acid layers
and b.p 355.6K). indicates the presence of nitrate ion in solution
Ø It is a very strong oxidising agent. It oxidises NO3− + 3Fe 2 + + 4 H + → NO + 3Fe3+ + 2 H 2O
non-metals to their corresponding oxides or
2+
oxoacids  F e ( H 2 O )6  + NO →
Ø i) It oxidises iodine to iodic acid
2+
I 2 + 10HNO3 → 2HIO3 + 10NO 2 + 4H 2 O  F e ( H 2 O )5 ( N O ) + H 2O
ii) Carbon to carbon dioxide, In brown ring, Fe exhibits +1 oxidation state.
C + 4HNO3 → CO 2 + 2H 2 O + 4NO 2 Phosphine
iii) Sulphur to H 2SO4 Ø Preparation: Phosphine is prepared by the
S8 + 48HNO3 → 8H 2SO 4 + 48NO 2 + 16H 2 O reaction of calcium phosphide with water or
dilute HCl.
iv) Phosphorus to phosphoric acid
Ca 3P2 + 6H 2 O → 3Ca (OH )2 + 2PH3
P4 + 20HNO3 → 4H 3PO 4 + 20NO 2 + 4H 2 O
Ø Concentrated nitric acid is a strong oxidising Ca 3P2 + 6HCl → 3CaCl2 + 2PH 3
agent and attacks most metals except noble Ø In the laboratory, it is prepared by heating white
metals such as gold and platinum. phosphorus with concentrated NaOH solution
Ø 3Cu + 8 HNO3 ( dilute ) → in an inert atmosphere of CO2
3Cu ( NO3 )2 + 2 NO + 4 H 2O P4 + 3NaOH + 3H 2 O → PH 3 + 3NaH 2 PO 2

Ø Properties: It is a colourless gas with rotten
Ø Cu + 4 HNO3 (conc.) → fish smell and is highly poisonous.
Ø It explodes in contact with traces of oxidising
Cu ( NO3 )2 + 2 NO2 + 2 H 2O
agents like HNO3, Cl2 and Br2vapours
Ø Zinc reacts with dilute nitric acid to give N 2 O Ø It is slightly souble in water. The solution of PH 3
and with concentrated acid to give NO 2 in water decomposes in presence of light giving
Ø 4Zn + 10HNO3 ( dilute ) → red phosphorus and H 2 .
Ø When absorbed in copper sulphate or mercuric
4Zn ( NO 3 )2 + 5H 2 O + N 2 O chloride solution, the corresponding
phosphides are obtained.
Ø Zn + 4HNO3 (conc.) →
3CuSO 4 + 2PH3 → Cu 3 P2 + 3H 2SO 4
Zn ( NO3 )2 + 2H 2O + 2NO2
3HgCl2 + 2 PH 3 → Hg3 P2 + 6 HC l
Ø Some metals (e.g., Cr,Al) do not dissolve in Ø Phosphine is weakly basic and like ammonia,
concentrated nitric acid because of the formation gives phosphonium compounds with acids e.g.,
of a passive film of oxide on the surface.
PH 3 + HBr → PH +4 Br −
Brown ring test: The familiar brown ring Ø When pure it is non inflammable but becomes
test for nitrates depends on the ability of Fe 2+
inflammable owing to the presence of P2 H 4 or
to reduce nitrates to nitric oxide, which reacts
with Fe 2+ to form a brown coloured complex. P4 vapours.
The test is usually carried out by adding dilute Ø To purify it from the impurities, it is absorbed
ferrous sulphate solution to an aqueous solution in HI to form phosphonium iodide ( PH 4 I )
containing nitrate ion, and then carefully adding which on treating with KOH gives phosphine.
concentrated sulphuric acid along the sides of
the test tube. A brown ring at the interface PH 4 I + KOH → KI + H 2 O + PH 3
12
Ø Uses: The spontaneous combustion of Ø Finely divided metals on heating with PCl 5 give
phosphine is technically used in Holme’s
corresponding chlorides.
signals. (Mixture of calcium carbide and
calcium phosphide). 2Ag + PCl 5 → 2AgCl + PCl 3
It is also used in smoke screens.
Sn + 2PCl 5 → SnCl 4 + 2PCl 3
Halides of phosphorous
Ø In the solid state it exists as an ionic solid.
Phosphorous Trichloride
[PCl 4 ] [PCl 6 ] in which the cation, [PCl 4 ]
+ − +
Ø Preparation: It is obtained by passing dry
chlorine over heated white phosphrous.
P4 + 6Cl 2 → 4PCl 3
is tetrahedral ( sp ) and the anion. [PCl ]
3
6
−
Ø It is also obtained by the action of thionyl octahedral ( sp d ) .3 2
chloride with white phosphorous

P4 + 8SOCl 2 → 4PCl 3 + 4SO 2 + 2S2 Cl 2 Ø In solid state PBr5 exists as monomeric ionic
Ø Properties: It is a colourless oily liquid and solid - [ PBr4 ] Br −
+
hydrolysis in the presence of moisture.

PCl 3 + 3H 2 O → H 3 PO3 + 3HCl
W.E-11: PCl3 is an electrical conductor in its
Ø It reacts with organic compounds containing-
aqueous solution. Explain .
OH group such as CH 3COOH, C2 H 5OH .
Sol. PCl3 hydrolysis in moisture (in water) giving
3CH 3COOH + PCl 3 → 3CH 3COCl + H 3 PO3
the fumes of HCl .
3C2 H 5OH + PCl 3 → 3C2 H 5Cl + H 3 PO3
PCl3 + H 2O → H 3 PO3 + 3HCl
Phosphorous Pentachloride: It is
prepared by the reaction of white phosphorous In aqueous solutions , HCl ionises and it
with excess of dry chlorine. therefore act as an electrical conductor .
P4 + 10Cl 2 → 4PCl 5
W.E-12: ‘P’ forms pentahalides and not
Ø It can also be prepared by the action of SO2Cl2 pentahydrides .Explain.
on phosphorous. Sol. ‘P’ can exhibit pentavalency in its excited
P4 + 10SO 2 Cl 2 → 4PCl 5 + 10SO 2 state. The electro negativity of F, Cl and Br
Properties: can easily influence the excitation in ‘P’ to
Ø PCl 5 is yellowish white powder. form PX 5 . However ,, hydrogen is not much
Ø It hydrolysis to POCl 3 and finally gets conveted electronegative to influence the excitation in
to phosphoric acid ‘P’ PH 5 cannot be formed .
PCl 5 + H 2 O → POCl 3 + 2HCl
POCl 3 + 3H 2 O → H 3PO 4 + 3HCl W.E-13: All five bonds of PCl5 are not
Ø When heated it sublimes but decomposes on equivalent and PCl5 is less stable. Explain .
stronger heating
Ans. PCl5 has a trigonal bipyramidal structure and
PCl 5 Heat
→ PCl 3 + Cl 2
Ø It reacts with organic compounds containing - the three equatroial P - Cl bonds are
OH group converting them to chloro derivaties. equivalent, while the two axial bonds suffer
more repulsions as compared to the equatorial
C 2 H 5OH + PCl 5 → C 2 H 5Cl + POCl 3 + HCl
bonds. Hence , PCl5 is less stable.
CH 3COOH + PCl 5 → CH 3COCl + POCl 3 + HCl
13
Oxides of Phosphorous
Phosphorous trioxide (P4O6 ): It is obtained
by burning phosphorous in limited supply of air.
∆
P4 + 3O2 
→ P4O6
Ø It is the anhydride of phosphorous acid.
Ø It dissolves in cold water to form phosphorous
acid.
Ø In P4O6 each phosphorous is surrounded by three
oxygen atoms.
Ø It is an acidic oxide.
Ø Number of P-O-P bonds are six
Ø It has four lone pairs on phosphorous and 12
covalent bonds. Oxyacids of Phosphorous: The
phosphorous series of acids contains P-Hbonds
Ø P-H bonds are responsible for reducing property
of ous acids
Ø O-H bonds are responsible for acidic properties.
Hypo Phosphorous acid (H3PO 2): It is
prepared by the heating yellow or white ‘p’ with
dilute Ba(OH)2
6H 2O + 2P 4 + 3Ba(OH) 2 → 3Ba(H 2PO 2) 2 +
2PH3 ↑
from Ba(H 2 PO 2) 2 , H 3 PO 2 is obtained by
hydrolysis.
Ø H3PO2 in monobasic acid and a very strong
reducing agent is basic solutions and it is
oxidised to H3PO3
Meta phosphorous acid(HPO2): It is mono
Phosphorous pentoxide (P4O10) basic acid normally exist as a cyclic compound
Ø It is obtained by burning phosphorous in excess due to polymerisation.
of air or oxygen. Ortho phosphorous acid (H3PO3): It is
∆ prepared by disolving P4O6 in cold H2O
P4 + 5O2 
→ P4O10 P4O6 + 6H2O → 4H3PO3 or P(OH)3
Ø It is the anhydride of phosphoric acid. Ø It forms two types of salts
Ø It dissolves in water to form H3PO4. Ø Primary phosphites H 2 PO 3 – (dihydrogen
phosphite) (acidic salt)
Ø In P4O10 each phosphorous is surrounded by four Ø Secondary phosphites HPO3–2 (monohydrogen
oxygen atoms. phosphites) (normal salts)
Ø Number of P-O-P bonds are six Ø Phosphorous acid and phosphites are very strong
Ø It is a strong dehydrating agent. reducing agents in basic solutions.
Ø It has 16 covalent bonds. Ex : Hg+2, Ag+, Cu+2 salts are reduced to Hg, Ag
and Cu
Ø As 4 O10 and Sb4O10 are produced by oxidation of H3PO3 + 2AgNO3 + H2O → H3PO4 + 2Ag +
2HNO3
As 4 or Sb 4 with conc HNO3
here H3PO3 is oxidised to H3PO4
14
Ortho Phosphoric acid (H3PO4): It is the
simplest of ‘ic’ acid series
(PO ) . But tri and tetra meta phosphate are well
−
3 2
Ø It is prepared by dissolving P4O10 in water known. They form a family of ring compounds.
P4O10 + 6H2O → 4H3PO4
Ø It is a weak tribasic acid and has oxidising
properties.
Ø Solid H 3 PO 4 absorbs water and forms a
colourless syrupy liquid (syrupy phosphoric
acid)
Ø Ortho phosphoric acid is prepared in the lab by
the action of HNO3 on phosphorus. Cyclic trimetaphosphoric acid
Ø H3PO4 is manufactured by heating bone ash or Ø Hypo phosphoric acid (H4P2O6) is obtained
phosphorite rock with dil. H2SO4. by the oxidation of phosphorous and dissolving
Ø H3PO4 is a tribasic acid and forms three types in water gives H4P2O6 . It is a tetra basic acid.
of salts. Pyrophosphoric acid (H 4P2O7): It is
Ø Primary phosphates : H 2 PO 4 − (acidic salt) prepared by heating an equimolar mixture of the
ortho and meta phosphoric acids at 373 K
Ø Secondary phosphates : HPO 4 2 − (acidic salt)
H 3 PO 4 + HPO3 
373K
→ H 4 P2 O 7
3−
Ø Tertiary phosphates : PO 4 (Normal salt) Ø Pyrophosphates also give molybdate test. i.e
In H3PO4 phosphorous atom is sp3 hybridised. they give ammonium phospho molybdate
Ø In qualitative analysis orthophosphates are
identified by ammonium phospho molybdate
( NH 4 )3 PO4 .12 ( MoO3 )
formation (Molybdate test)
Ø The canary yellow ammonium
phosphomolybdate is(NH4)3PO4.12(MoO3)
Ø Sodium dihydrogen orthophosphate (NaH2PO4)
on heating first changes to pyrophosphate on
further heating it changes to meta phosphate or
trimeta phosphate
− H2O > 240°
2NaH 2 PO4 
>160°
→ Na 2 H 2 P2O7  →
( NaPO3 )3 or Na P O3 3 9
sod.trimeta phosphate
Meta Phosphoric acid (HPO 3 ): Meta

phosphoric acid:It is formed by heating
pyrophosphoric acid or orthophosphoric acid to
870 k
H3PO4 
520k
− H2O
→ H4 P2O7 
870k
− H2O
→ HPO3
Ø It is a transparent glassy solid. Hence also known
as glacial phosphoric acid.
Ø HPO3 is a monobasic acid and its salts are called
meta phosphates. There is no evidence for the
existence of true monometaphosphate
(PO ) Ions or of the dimeta phosphate (P O ) or
−
3 2
−2
6
15
PREPARATION OF OXOACIDS Additional Synopsis
Cyanamide process: Calcium carbide
reacts with N 2 gas at 1273-1378K to form
calcium cynamide and graphite mixture
1273−1378 K
CaC2 + N 2 
→ CaCN 2 + C( graphite )
finely powdered anhydrous CaCl2 or CaF2 it acts
as a catalyst.
Ø Nitrolim is a mixture of calcium cyanamide and
graphite (CaCN 2 + C). Nitrolim is used as
fetilizer.
Ø Calcium cyanamide on hydrolysis gives
ammonia gas.
CaCN2 + 3H2O → CaCO3 + 2NH3
Calcium super phosphate (or) super
phosphate of lime
Ø Super phosphate of lime is also known as
Important features about oxyacids of calcium super phosphate.
phosphorous: In all these oxyacids, Ø This is one of the few soluble phosphates
phosphorous is tetra hedrally surrounded by Ø Calcium super phosphate is a mixture of calcium
atoms. dihydrogen phosphate (Ca(H 2 PO 4 ) 2 ) and
Ø In all these oxyacids, at least one OH group is gypsum. ( CaSO4 . 2H2O)
linked to the phosphorous atoms. The hydrogen Ø Calcium super phosphate is manufactured by the
atoms in OH groups are ionisable, and are action of conc. H2SO4 (chamber acid 60% acid)
responsible for the acidic nature. on powdered bone ash or calcium phosphate.
Ø P-H bonds are responsible for reducing Ca3 ( PO4 )2 + 2 H 2 SO4 + 4 H 2O →
properties of the acids phosphoric series of
Ca ( H 2 PO4 )2 + 2 (CaSO4 2 H 2O ) + heat
acids do not have P-H bonds.
Ø All oxoacids contain at least one P=O and one The composition of super phosphate of lime may
P-OH bond. be variable.
Ø The reaction mixture is allowed to take place
W.E-14:How is the reduction ability of H 3 PO2 for 24-36 hours, In this period the temperature
and H 3 PO3 accounted on the basis of rises to about 373-383 K.
Ø The impurties in phosphate rock i.e carbonates
structures of molecules
liberated as CO2 and fluoride liberated as HF
Sol. H 3 PO2 have two ‘H’ atoms linked directly
gases
to ‘P’ imparting reducing character to the Ø The final product is a hard mass (due to the
acid . Similarly in H 3 PO3 only one ’H’ is linked presence of gypsum)
directly to ‘P’ imparting reducing character . Ø It is a phosphatic fertilizer. It is soluble in water.
Ø The CaSO4 in super phosphate of lime is an
W.E-15: Aqua - regia can dissolve noble metals.
Explain insoluble waste product.
To avoid this waste product, the super phos
Sol. 1 : 3 mixture of conc. HNO3 and conc. HCl is phate is converted into “Triple phosphate” by
Aquaregia . The mixture produces nascent treating with "H 3 PO 4 ” which completely
chlorine, which reacts with noble metals to
dissolves in water.
dissolve them
Ca 3 ( PO4 )2 + 4H3 PO4 → 3Ca ( H 2 PO4 )2
HNO3 + 3HCl → 2 H 2O + 2(Cl ) + NOCl
Ø Superphosphate of lime is converted into triple
Au + 3(Cl ) → AuCl3 ; AuCl3 + HCl → (chloroauric
HAuCl4
acid) phosphate.
16
C.U.Q OXIDATION STATES

12. In the compound NCl3 , negative oxidation
GENERAL CHARACTERISTICS state is exhibited by
1. The outer electronic configuration of group 1) Nitrogen 2) Chlorine
VA elements is 3) Nitrogen & Chlorine
1) ns2 np2 2) ns2 np3 3) ns2 np4 4) ns2 np5 4) Neither nitrogen nor chlorine
2. VA group elements are known as 13. The oxidation state that is not exhibited by
1) Halogens 2) Normal elements VA group elements
3) Chalcogens 4) Pnicogens 1) +1 2) +3 3) -3 4) +6
3. The most abundant element in the earth’s
crust among the following is DINITROGEN
1) P 2) As 3) Sb 4) Bi 14. The bond energy of N ≡ N in KJ per mole is
4. Which one of the following has the lowest 1) 180 2) 941.4 3) 350 4) 120
melting point? 15. Anamolous behaviour of Nitrogen is due to
1) N 2) P 3) As 4) Sb 1) Small size and high electronegativity
5. The molecular formula of Phosphorous is 2) Non availability of d-orbitals in valency shell
1) P 2) P4 3) P2 4) P5 3) Ease of multiple bond formation
4) All are correct
6. The elements present in Flourapatite are
1) Ca, N & O only 2) Ca & P only HYDRIDES
3) Ca, N, O, F 4) Ca, P, F,O 16. The trend in the hydrides from Bi to N is
7. List-I List-II 1) Bond length increases
A) Phosphorite 1) KNO3 2) Bond length decreases
3) Acidic nature increases
B) Bengal salt petre 2) Ba ( NO3 )2 4) Bond energy decreases
C) Fluoroapatite 3) NaNO3 17. Which of the following hydrides has the
lowest melting point
D) Chile salt petre 4) 3Ca3 ( PO4 )2 .CaF2 1) NH3 2) PH3 3) AsH3 4) SbH3
18. The largest bond angle is in
5) Ca3 ( PO4 )2
1) AsH3 2) NH3 3) H2O 4) PH3
The correct match is 19. Among the following which one is more
A B C D A B C D stable?
1) 1 2 3 5 2) 2 4 3 1 1) PH3 2) NH3 3) AsH3 4) SbH3
3) 4 3 5 2 4) 5 1 4 3 20. The formula of the Hydride of nitrogen that
ALLOTROPIC FORMS is acidic in nature is
8. The most thermodynamically stable 1) NH3 2) HN3 3) N2H4 4) NH2OH
allotropic form of phosphorus is 21. The element which forms acidic hydride is
1. Red P 2. Yellow P 1) Nitrogen 2) Phosphorus
3. Black P 4. All are stable 3) Arsenic 4) Antimony
9. The element of 15 th group which cannot 22. Which of the following is correct about V
exhibit allotropy group Hydrides (from ammonia to
1) N 2) As 3) Sb 4) Bi Bismuthine)
10. Nitrogen shows allotropy in -------- state 1) Their thermal stability gradually increase
1) gaseous 2) liquid 2) Their ease of preparation gradually increase
3) solid 4) Liquid and Solid 3) The electron pair donating Nature gradually
11. The VA group element having more decrease
number of allotropes is 4) The bond energies gradually increase
1) N 2) P 3) Bi 4) Sb
17
23. Which of the following is a Hydride of HALIDES
Nitrogen 39. Nitrogen cannot form penta halide because
1) NH3 2) N2H4 3) HN3 4) All 1) Nitrogen atom is very small
24. The oxidation state of nitrogen is a fractional 2) Nitrogen atom has no vacant orbitals in
value in valency shell
1) Hydroxyl amine 2) Hydrazoic acid 3) Electronegativity of nitrogen is very high.
3) Nitrate ion 4) Hydrazine
4) Nitrogen molecule contains a very strong
25 Thermally more stable hydride is
triple bond
1) NH 3 2) PH 3 3) AsH 3 4) BiH 3 40. Which of the following trihalides is not
hydrolysed
OXIDES
1) NF3 2) PCl3 3) AsCl3 4) SbCl3
26. Which of the follwing is both neutral and
paramagnetic 41. Which one of the following exceeds octet
rule?
1) N 2O 2) NO 3) NO2 4) N 2O4
1) NCl3 2) PCl3 3) PCl5 4) NH3
27. Oxide of nitrogen formed in the atmosphere 42. The hybrid orbitals used by Phosphorus in
during the lightening is the formation of PCl5 are
1) NO 2) N2O 3) NO2 4) None 1) sp3 2) sp2 3) dsp2 4) sp3d
28. A colourless paramagnetic gas among the
43. PCl3 on hydrolysis gives
following is
1) H3PO4 2) H3PO3 3) POCl3 4) H3PO2
1) Nitric Oxide 2) Nitrous Oxide
44. Which of the following is explosive
3) Nitrogen dioxide 4) Dinitrogen trioxide
29. A blue liquid among the following is 1) NCl3 2) NF3 3) NH3 4) N2O5
1) N2O3 2) N2O 3) N2O4 4) NO2 45. Which of the following undergoes hydrolysis
30. The oxide of Nitrogen which has three- very easily
electron bond in its structure is 1) NCl3 2) PCl3 3) AsCl3 4) BiCl3
1) N2O 2) NO 3) N2O3 4) N2O5 46. PCl3 is prepared by the action of Cl2 on
31. The laughing gas is 1) P2O3 2) P2O5 3) White P 4) H3PO3
1. Nitrous oxide 2. Nitric oxide 47. Which of the following pentahalides of Bi
3. Nitrogen oxide 4. Nitrogen pentoxide exists
32. FeSO4 forms brown ring with 1) BiCl5 2) BiBr5 3) BiI5 4) BiF5
1) NO3 2) NO 3) NO2 4) N2O3 48. Which chloride is not appreciably hydrolysed
33. Ammonium nitrate crystals on heating at by water
250-2600 C gives 1) NCl3 2) PCl3 3) AsCl3 4) SbCl3
1) N2 2) NO2 3) N2O 4) NO
34. Number of oxygen atoms attached to 49. The shape and hybridisation of PCl3 molecule
phosphorus atom in P4O6 molecule are
1) Tetrahedral and sp 3 2) Pyramidal and sp 3
1) 6 2) 4 3) 3 4) 2
35. Which of the following is paramagnetic 3) Angular and sp 3 4) Planar trigonal and sp 3
1) NO 2) NO2 3) ClO2 4) All
36. Acidic para magnetic oxide of nitrogen
OXYACIDS
1) NO 2) N2O3 3) NO2 4) N2O5 50. In hyponitrous acid the number of Hydroxyl
37. Regarding N2O, the wrong statement is groups present are
1) It is called laughing gas 1) 1 2) 2 3) 3 4) 4
2) It is called nitrous oxide 51. Oxidation state of phosphorus is + 3 in
3) It is a linear molecule 1) Orthophosphorus acid
4) It is a more reactive oxide 2) Orthophosphoric acid
38. Which of the following exist as dimer 3) Pyrophosphoric acid
1) NO 2) NO2 3) P2O3 4)All 4) Metaphosphoric acid
18
52. A tribasic acid with peroxy bond is 66. NH3 on burning in oxygen gives
1) H3PO2 2) H3PO3 3) H3PO4 4) H3PO5 1) NO and H2O 2) NO2and H2O
53. The salts of phosphorous acid are called 3) N2and H2O 4) N2O and H2
1) Phosphates 2) Phosphites 67. An aqueous solution of ammonia contains
3) Hypophosphites 4) Phosphides 1) Ammonium ions 2) Hydroxy ions
54. Which contains O-O linkage? 3) both of them 4) H+ ions
1) H3PO3 2) H4P2O7 3) H4P2O6 4) H 3 PO5 68. Nitrolim is
55. The formula of meta phosphoric acid is 1) CaC2 + N2 2) CaCN2 + Graphite
1) H2PO3 2) H3PO3 3) HPO3 4) H4P2O7 3) Ca NCN 4) Ca(CN)2 + C
56. Oxidation state of +1 for phosphorous is
69. In the preparation of HNO3 by Ostwald
found in
process ammonia is
1) H 3 PO3 2) H 3 PO4 3) H 3 PO2 4) H 4 P2O7
1) reduced 2) oxidised
57. Number of hydroxy groups present in
3) reduced and oxidised 4) hydrolysed
Phosphoric acid
1) 1 2) 2 3) 3 4) 4 70. NH 4Cl on heating with NaOH liberates
58. Which of the following is an acid 1) NaCl 2) NH 3 3) HCl 4) NaOCl
1) Ca(OH)2 2) P(OH)3 3) NH4OH 4) NaOH
59. The oxyacid of phosphorous which has more 71. Ammonia gas is dried over
non-ionisable hydrogens 1) Quick lime 2) Conc. H 2 SO4
1) H3PO2 2) H3PO3 3) H4P2O7 4) H4P2O6
3) P2O5 4) CaCl2
PREPARATION AND USES OF NITRIC ACID 72. Which of the following compound is not used
60. Mixture of conc. HNO3 and conc. H2SO4 is as fertilizer
known as 1) Ammonium sulphate 2) Urea
1) Sulphonating mixture 2) Nitration mixture 3) Calcium super phosphate 4) Ca3 ( PO4 )2
3) Explosion mixture 4) Fusion mixture
73. Which of the following can serve as a
61. Iron is rendered passive in
solvent for both ionic and covalent
1) aquaregia 2) conc. H2SO4
compunds?
3) conc. HNO3 4) conc. HCl
62. The industrial preparation of nitric acid by 1) Liquid ammonia 2) H 2O
ostwald’s process involves 3) Benzene 4) CCl4
1) reduction of NH3 2) oxidation of NH3
3) hydrogenation of NH3 4) hydrolysis of NH3 ADDITIONAL SYNOPSIS BITS
63. Catalyst in the Ostwald’s process is SUPER PHOSPHATE OF LIME
1) Pt 2) Fe 3) V2O5 4) Ni 74. Teeth and bones are made of mainly
1) Calcium silicate
AMMONIA 2) Calcium phosphate
64. In Haber’s process for the manufacture of 3) Calcium silicon phosphate
ammonia, the catalyst used is 4) Calcium hydrogen phosphate
1) finely divided Nickel 75. Superphosphate of lime is a good fertilizer
2) finely divided molybdenum because it is
3) finely divided iron
1) Calcium containing substance
4) finely divided Platinum
2) Soluble in water
65. The catalytic promoter used in Haber’s
process is 3) Containing gypsum
1) Mo 2) Ni 3) Pt 4) V O 4) None of these
2 5
19
C.U.Q - KEY 30. NO ( nitric oxide) has three electron bond.
1) 2 2) 4 3) 1 4) 1 5) 2 6) 4 7) 4 32. FeSO4 forms brown ring with NO
∆
8) 3 9) 4 10) 3 11)2 12) 1 13) 4 14) 2 33. NH 4 NO3 → N 2O + 2 H 2O
15) 4 16) 2 17) 2 18) 2 19) 2 20) 2 21) 1 34. In P4O6 molecule number of oxygen atoms
22) 3 23) 4 24) 2 25)1 26) 2 27) 1 28) 1 attached to phosphorous is ‘3’.
29) 1 30) 2 31) 1 32) 2 33) 3 34) 3 35) 4 35. NO = 5+6 = 11, ClO2 = 7 + 2 × 6 = 19 ,
36) 3 37) 4 38) 4 39) 2 40) 1 41) 3 42) 4
NO2 = 5 + 2 × 6 = 17 all are paramagnetic
43) 2 44) 1 45) 1 46) 3 47) 4 48) 4 49)2
50) 2 51) 1 52) 4 53) 2 54) 4 55) 3 56) 3 36. NO2 is acidic paramagnetic oxide
57) 3 58) 2 59) 1 60) 2 61) 3 62) 2 63)1 37. N 2O is relatively unreactive
64) 3 65) 1 66) 1 67) 3 68) 2 69)2 70)2
38. NO, NO2 , P2O3 all exists as dimers.
71)1 72)4 73)1 74) 2 75) 2
39. Nitrogen cannot form pentahalides due to
C.U.Q - HINTS absence of d orbitals.
6. 3s 2 3 p 3 3d 0 40. Because NF3 is a stable halide.
9. ‘Bi’ is metal 41. In the valency shell of PCl 5 10 electrons
10. Nitrogen exhibits allotropy in solid state are present
12. Nitrogen has greater effective nuclear charge
42. In PCl5 P undergoes SP3d hydridisation due to
than chlorine
15. Due to 1) Small size absence of d-orbitals
2) Absence of ‘d’ orbitals 45. NCl 3 undergoes hydrolysis easily
3) Ease of multiple bond formation
46. P4 + 6C l 2 → 4 PC l 3
16. From Bi to N bond length decreases
17. PH 3 having lowest melting point 48. SbCl 3 is not easily hydrolysed.
18. As electronegativity decreases down the group 55. HPO3
the electron density on central atom of hydride 61. Fe, Cr , Al forms a protective passive layer.
decreases and thus repulsion between bond pair
64. Powderd Iron
and lone pair of electrons decreases which
ultimately decreases H − M − H bond angle. 65. Mo (or) K 2O + Al 2O3
67. A mixture of Ca.cyanamide and graphite
Therefore NH 3 having highest bond angle.
19. due to inter molecular H-bond CaC 2 + N 2 → CaCN + C!
"""" 2""""
.
Nitro lim
21. Nitrogen forms acidic hydride
22. From NH 3 to BiH 3 the electron pair donating 68. 4 NH 3 + 5O2 → 4 NO + 6 H 2O
nature gradually decreases 72. Ca3 ( PO4 )2
23. Hydrides of nitrogen NH 3 , N 2 H 4 , HN 3 etc more soluble fertilizer.
24. Hydrazoic acid NH 3 3x + 1 = 0
LEVEL-I (C.W)
−1
3x = −1 ; x=
3 GENERAL CHARACTERISTICS
electric 1. A metalloid of nitrogen family is
27. N 2 + O2 → 2 NO 1) N 2) As 3) P 4) Bi
arc
28. NO = 5 + 6 = 11 paramagnetic, colourless oxide 2. The element having the higher boiling point
is
29. N 2O3 is a blue coloured liquid 1) P 2) As 3) Sb 4) Bi
20
3. Phosphide ion has electronic structure similar HYDRIDES
to that of 12. Non combustible hydride is
1) Nitride ion 2) Chloride ion 1) PH3 2) SbH3 3) NH3 4) AsH3
3) Fluoride ion 4) Sodium ion 13. The substance that is neutral to litmus
1) N2O3 2) NH3 3) P4O10 4) PH3
ALLOTROPIC FORMS
14. Which of the following is least stable
4. The most reactive form of phosphorus is
1) NH4+ 2) SbH4+ 3) PH4+ 4) AsH4+
1) White P 2) Red P
15. Which statement is false
3) Black P 4) Scarlet P 1) NH3 is a Lewis base
5. Which is oxidised in air 2) NH3 molecule is triangular planar
1) White P 2) CH 4 3) H 2O 4) SO2 3) NH3 does not act as reducing agent
6. Which of the following exist in mono-atomic 4) NH3 (liquid) is used as a solvent
state 16. Which is used to produce smoke screens?
1) Phosphorus 2) Nitrogen 1) Zinc sulphide 2) Calcium phosphide
3) Antimony 4) Bismuth 3) Zinc phosphate 4) Sodium carbonate
7. Which property of white phosphorus is 17. Which one of the following statements is
common to red P correct with respect to basic character ?
1. It burns when heated in air 1) PH 3 > P (CH 3 )3 2) PH 3 = NH 3
2. It reacts with hot caustic soda solution to give
phosphine 3) PH 3 > NH 3 4) P(CH 3 )3 > PH 3
3. It shows chemiluminescence 18. Which is in the decreasing order of boiling
4. it is soluble in carbon disulphide points of hydrides ?
OXIDATION STATES 1) NH 3 > PH 3 > AsH 3 > SbH 3
8. Oxidation state of +3 for phosphorous is 2) SbH 3 > AsH 3 > PH 3 > NH 3
found in
1) H3PO3 2) H3PO4 3) H3PO2 4) H4P2O7 3) PH 3 > NH 3 > AsH 3 > SbH 3
9. List - I List - II 4) SbH 3 > NH 3 > AsH 3 > PH 3
A) HNO3 1) -3, +5 oxidation state
B) NH4NO3 2) -1/3 oxidation state OXIDES
C) N3 H 3) +5 oxidation state 19. Amphoteric oxide among the following is
D) H3PO3 4) +3 oxidation state 1) N2O5 2) As2O3 3) Bi2O3 4) N2O
5) + 1/3 oxidation state 20. Which of the following exists as monomer
The correct match is molecules only
A B C D A B C D 1) Nitrogen (III) Oxide 2) Phosphorus (V) Oxide
1) 3 1 2 4 2) 5 2 3 4 3) Arsenic (III) Oxide 4) Antimony(V) Oxide
3) 1 2 3 4 4) 4 3 2 5 21. Nitrogen (I) oxide is produced by
10. The stable oxidation state of Bismuth is 1) Thermal decomposition of Ammonium
1) +1 2) +5 3) -3 4) +3 Nitrate
2) Decomposition of NO2
DINITROGEN 3) By the decomposition NaNO2
11. Fixation of nitrogen means 4) By the interaction of Hydroxyl amine and
1. reaction of nitrogen with oxygen Nitrous acid
2. conversion of free atmospheric nitrogen into 22. In P O the number of the oxygen atoms
4 10
nitrogen compounds bonded to each phosphorous atom is
3. the action of denitrifying bacteria on nitrogen 1) 2 2) 3 3) 4 4) 5
compounds 23. Which of the following oxide is brown
4. decomposition of nitrogenous compounds to coloured gas
yield free nitrogen. 1. NO2 2. NO 3. N 2O 4. N 2O5
21
24. The gas not having oxidizing as well as 36. Among the following an acidic salt is
bleaching properties is 1) NaH 2 PO2 2) NaH 2 PO3
1) Chlorine 2) Ozone 3) SO2 4) N2O
3) Na2 HPO3 4) Na3 PO4
25. P4O10 is the anhydride of the following
PREPARATION AND USES OF NITRIC ACID
1) H 3 PO2 2) H 3 PO3 3) H 3 PO4 4) H 3 PO5
37. Ammonia and air are the starting materials
HALIDES for the manufacture of Nitric acid in
26. Which of the following trihalides give unique 1) Birkland - Eyde process 2) Ostwald’s process
products on hydrolysis. 3) Haber’s process 4) Hasen Clever method
38. Moles of oxygen that can oxidise one mole
1) NCl3 2) PCl3 3) ASCl3 4) SbCl3
of NH 3 to NO
27. The element which gives explosive halides is
1) Phosphorus 2) Nitrogen 1) 1 2) 1.25 3) 2.5 4) 5
3) Arsenic 4) Bismuth 39. Percentage of nitric acid obtained in
28. Which of the following is most stable Ostwald’s process is
1) NI3 2) NF3 3) NBr3 4) NCl3 1) 61% 2) 68% 3) 74% 4) 82%
29. Among NCl 3 , PF 5 and NF 5 why NF 5 is AMMONIA
impossible? 40. Which does not give ammonia with water
1) N has high electronegativity 1) Mg3N2 2) AlN 3) CaCN2 4) Ca(CN)2
2) N has high ionisation energy 41. When a mixture of NH3 and air is passed over
3) N has lowest atomic size heated platinum gauze at 8000 C, it produces
4) N has no vacant d-orbital 1) NO 2) NO2 3) POCl3 4) HOCl
30. Which of the following is not correct ? 42. Aqueous NaOH reacts with white
1) Hydrolysis of NCl3 gives NH 3 and HOCl Phosphorous to form Phosphine and
2) NH 3 is less stable than PH 3 1) NaH 2 PO2 2) P2O5 3) Na3 PO3 4) P2O3
3) NH 3 isa weak reducing agent compared to ADDITIONAL SYNOPSIS BITS

PH 3
SUPER PHOSPHATE OF LIME
43. Superphosphate is a mixture of
4) Nitric oxide in solid state exhibits 1) Ca(H2PO4)2 H2O + CaCl2 2H2O
diamagnetic property 2) Ca(H2PO4)2 + 2(CaSO4. 2H2O)
OXYACIDS 3) Ca3(PO4)2 H2O + 2CaSO4 2H2O
31. An element X belongs I, II, III or V groups. 4) Ca3(PO4)2 H2O + CaCl2 2H2O
Its oxide reacts with water to produce highly 44. Superphosphate of lime is obtained by
acidic solution the element X belongs to treating
1) I groups 2) II group 3) III group 4) V group 1) Calcium phosphate with HCl
32. The anhydride of orthophosphoric acid is 2) Calcium phosphide with HCl
1) P4O6 2) P2O4 3) P4O10 4) H2P2O6 3) Calcium phosphate with H2SO4
33. The oxyacid of phosphorous which exists as 4) Calcium phosphate with NaOH
a dimer in vapour phase is
1) Hydrophosphorous acid
LEVEL-I (C.W) - KEY
2) Pyrophosphoric acid 1) 2 2) 4 3) 2 4) 1 5) 1 6) 4 7) 1
3) Peroxy phosphoric acid 8) 1 9) 1 10) 4 11) 2 12) 3 13) 4 14) 2
4) Metaphosphoric acid 15) 2 16) 2 17) 4 18) 4 19) 2 20) 1 21) 1
34. Salt of the following is used as a water
22) 3 23) 1 24) 4 25) 3 26) 1 27) 2 28) 2
softner
29) 4 30) 2 31) 4 32) 3 33) 4 34) 3 35) 2
1) H 4 P2O6 2) H 4 P2O7 3) HPO3 4) HPO2
36) 2 37) 2 38) 2 39) 1 40) 4 41) 1 42) 1
35. Basicity of orthophosphoric acid is
1) 2 2) 3 3) 4 4) 5 43) 2 44) 3
22
LEVEL-I (C.W) - HINTS 5. Red phosphorous is less soluble and less
volatile than white phosphorous because its
12. NH 3 is non combustable hydride
structure is
13. PH 3 is neutral to litmus 1) polymerised chains 2) hexagonal rings
3) tetrahedral 4) Planar sheets
14. SbH 4+ is least stable
OXIDATION STATES
15. NH 3 - pyramidal 6. In Ba(H 2PO 2) 2 the oxidation number of
19. As2 O3 is Amphoteric oxide phosphorous is
1) + 5 2) + 1 3) + 3 4) + 4
20. Nitrogen ( III ) oxide forms monomer molecules 7. The oxidation state of nitrogen in
only hydrazine is
21. NH 4 NO3 → N 2O + 2 H 2O 1) -1 2) -2 3) +1 4) +2
8. Substance Oxidation state of N
(nitrogen in N 2O has +1 oxidation state) A) HNO3 1) -3 , +5
23. presence of unpaired e − B) NH 4 NO3 2) -1/3
24. N 2O is not having oxidising and bleaching C) N 3 H 3) +5
properties
D) H 3 PO3 4) +3
27. Nitrogen forms NCl 3 which is explosive 5) +1/3
29. excitation is not possible The correct match is
31. from left to right acidic nature increases A B C D A B C D
1) 3 1 2 4 2) 5 2 3 4
38. 4 NH 3 + 5O2  
Pt gauze
→ 4 NO + 6 H 2O 3) 1 2 3 4 4) 4 3 2 5
39. A.C to Ostwald process DINITROGEN
40. CaNCN on hydrolysis gives NH3
9. Nitrogen forms N 2 but phosphorus forms
43. Ca.dihydrogen phosphate and Gypsum
P4 due to
44. Ca3 ( PO4 )2 + 2 H 2 SO4 + 4 H 2O →
1. Triple bond is present between phosphorus
Ca ( H 2 PO 4 ) + 2 (CaSO4 .2 H 2O ) atoms
2 2. Pπ − Pπ bonding is weak.
3. Pπ − Pπ bonding is strong
LEVEL-I (H.W) 4. Multiple bond is formed easily
HYDRIDES
GENERAL CHARACTERISTICS
10. Which of the following is least stable
1. Atomicity of white phosphorus is
1) NH3 2) N3H 3) H2NNH2 4) N2H2
1) 4 2) 3 3) 2 4) 8
11. The bond angle decreases from NH3 to BiH3
2. Which of the following is able to form ionic due to
compounds 1) The decrease in basic strength
1) Bi 2) As 3) Sb 4) P 2) The decrease in bond dissociation energy
3. The percentage of P-character in the orbitals 3) The decrease in electronegativity of the cental
forming P − P bonds in P4 is atom
1) 25 2) 33 3) 50 4) 75 4) All of these
12. Which one of the following can more readily
ALLOTROPIC FORMS donate the lone pair?
4. Which of the following exists in more number 1) NH3 2) PH3 3) AsH3 4) BiH3
of allotropic forms 13. The most polar compound among the
1) Nitrogen 2) Bismuth following is
3) Arsenic 4) Phosphorus 1) NH3 2) PH3 3) AsH3 4) BiH3
23
14. Acidic hydride of nitrogen is 26. PCl5 on hydrolysis gives
1) NH 3 2) N 2 H 4 3) N 2 H 2 4) N 3 H
1) H 3 PO3 2) H 3 PO4 3) H 3 PO2 4) H 3 PO5
15. The correct order of reducing abilities of
VA group hybrides is OXYACIDS
1) NH 3 < PH 3 < AsH 3 < SbH 3 < BiH 3 27. H3PO2 is the molecular formula of an acid of
phosphorous. It’s name and basicity
2) NH 3 > PH 3 > AsH 3 > SbH 3 > BiH 3 respectively are
3) NH 3 < PH 3 > AsH 3 > SbH 3 > BiH 3 1) Metaphosphorous acid and one
2) Hypophosphorous acid and one
4) SbH 3 > BiH 3 > AsH 3 > NH 3 > PH 3 3) Metaphosphoric acid and two
4) Hypophosphoric acid and two
OXIDES
28. Which of the following is a normal salt
16. Which of the following is most acidic
1) Na2HPO4 2) NaH2PO3
1) As2O3 2) P2O3 3) Sb2O3 4) Bi2O3
3) NaH2PO4 4) Na3PO4
17. Which of the following is a mixed acid
29. Which of the folowing is tetrabasic acid
anhydride
1.Orthophosphoric acid
1) Nitrogen (III) Oxide 2) Nitrogen (II) Oxide
2.Orthophosphorous acid
3) Nitrogen (V) Oxide 4) Nitrogen (IV) Oxide
3. Metaphosphoric acid
18. Which of the following oxides of nitrogen is
4. Pyrophosphoric acid
anhydride of nitric acid ?
30 Covalency of phosphorous in peroxy
1) N2O3 2) N2O4 3) N2O5 4) N2O
phosphoric acid is
19. Which one of the following elements does not
1) 6 2) 5 3) 4 4) 3
form the compound, M 4O10 (M = element)? 31 The starting material used for the
1) P 2)Sb 3) As 4) Bi manufactured of HNO3 by Ostwalds process
20. Nitrous oxide is
is
1. Soluble in cold water
2. Soluble in hot water without decomposition 1) Ammonia and N 2O
3. Acidic in nature 4. Basic in nature 2) Ammonia
21. NO2 can not be obtained by heating 3) Air only
1) KNO3 2) Pb(NO3)2 4) Ammonia and nitrogen
3) Cu(NO3)2 4) Hg(NO3)2 PREPARATION AND USES OF NITRIC ACID
22. P4O6 is the anhydride of the following 32. Which of the following is rendered passive
by con. HNO3 is
1) H 3 PO2 2) H 3 PO3 3) H 3 PO4 4) H 3 PO5 1) Al 2) Au 3) Zn 4) Sn
33. Which of the following is used in
HALIDES pyrotechniques
23. The V A group clement that doesn’t directly
1) NH 3 2) HNO3 3) PH 3 4) H 3 PO4
react with chlorine
1) N 2) As 3) Sb 4) Bi AMMONIA
24. Which of the following gives an alkaline gas 34. Which one of the following gas is most soluble
on hydrolysis in water?
1) PCl3 2) BiCl3 3) NCl3 4) PBr3 1) CO 2) N2O 3) NO 4) NH3
25. Which of the following halide does not 35. Calcium cyanamide on treatment with steam
contain a lone pair of electrons on the central under pressure gives ammonia and
atom 1) Calcium carbonate 2) Calcium hydroxide
1) PCl3 2) NCl3 3) AsCl3 4) PCl5 3) Calcium oxide 4) Calcium bicarbonate
24
36. Which of the following reactions yield 24. NC l + 3H O → NH ↑ +3HOC l
3 2 3
elementary gases like N 2 , H 2 , O2 as the 32. Al rendered passive on treatement with
byproducts ? Con HNO3
I) CuO + NH 3 → 34. due to H-bond
II) 2 NH 3 + 2 Na  Fe
300 − 4000 C
→ 35. CaNCN + 3H 2O → CaCO3 + 2 NH 3
III) ( NH4 )2 Cr2O7 
∆
→
LEVEL-II (C.W)
IV) 2Pb ( NO3 )2 
∆
→
1) I and II only 2) II , III and IV only GENERAL CHARACTERISTICS
3) I, II and III only 4) all of these 1. The number of covalent bonds made by
phosphorus atom never exceeds
LEVEL-I (H.W) - KEY 1) 3 2) 6 3) 2 4) 12.
1) 1 2) 1 3) 4 4) 4 5) 1 6) 2 7) 2 2. Ionic radius ( in A o ) of As3+ ,Sb3+ and Bi3+
8) 1 9) 2 10) 4 11) 3 12) 1 13) 1 14) 4 follow the order ...
15) 1 16) 2 17) 4 18) 3 19) 4 20) 1 21) 1 1) As3+ >Sb 3+ >Bi 3+ 2) Sb3+ >Bi3+ >As 3+
22) 2 23) 1 24) 3 25) 4 26) 2 27) 2 28) 4 3) Bi3+ >As 3+ >Sb3+ 4) Bi3+ >Sb 3+ >As 3+
3. The shape and bond angle of white
29) 4 30) 2 31) 2 32) 1 33) 2 34) 4 35) 1
Phosphorous molecule is \
36) 4 1) Linear and 1800
2) Trigonal planar and 1200
LEVEL-I (H.W) - HINTS
3) Tetrahedral and 1090 281
2. ‘N’ is able to form ionic compounds
3. In P4 molecule phosphorus is SP 3 hybridised 4) Tetrahedral and 600
DINITROGEN
6. ( +2 ) + 4 ( +1) + 2 p + 4 ( −2 ) = 0 4. Nitrogen liberated by the thermal
2 p = +2 decomposition of only
p = +1 1. NH 4 NO2 2. NaN3
9. N 2 O4 is used an oxidant with liquid propellants. 3. ( NH 4 )2 Cr2O7 4.all the three
10. N 2 H 2 is least stable 5. The CN − ion and N 2 are isoelectronic. But
11. The bond angle decreases from NH 3 to BiH 3 in contrast to CN − , N 2 is chemically inert
due to the decrease in electronegativity of the because of
central atom 1) low bond energy
12. NH 3 is the strongest electron pair donor due to 2) absence of bond polarity
its small size as the electron density of the 3) unsymmetrical electron distribution
electron pair is concentrated over a small region 4) presence of more number of electrons in
bonding orbitals
13. In VA group hydrides most polar compound is HYDRIDES
NH 3 6. Which of the following has maximum
complex forming ability with a given metal
16. P2O3 is most acidic ion
17. N 2O4 + H 2O → HNO2 + HNO3 1) PH3 2) BiH3 3) NH3 4) SbH3
7. The oxidation number of N in N3H is
21. KNO3 on heating doesnot gives NO2 1) + 1/3 2) 0 3) - 1/3 4) 1
25
8. The bond energies (in KJ mole −1 ) of HALIDES
P -H , As-H and N-H respectively ? 18. The trihalide which forms oxocations on
1) 247 , 318 and 389 2) 247 , 389 and 318 hydrolysis is
3) 318 , 389 and 247 4) 318 , 247 and 389 1) NCl3 2) PCl3 3) SbCl3 4) AsCl3
9. What is the order of basic nature of hy- 19. Bismuth forms the only pentahalide with the
drides of VA group elements ? halogen
1) AsH 3 > SbH 3 > PH 3 > NH 3 1) Bromine 2) Fluorine 3) Chlorine 4) Iodine
2) NH 3 > SbH 3 > PH 3 > AsH 3 OXYACIDS
20. Acid having peroxide linkage in its structure
3) NH 3 > PH 3 > AsH 3 > SbH 3
is
4) PH 3 > NH 3 > SbH 3 > AsH 3 1) HNO3 2) H3PO4 3) H4P2O7 4) HNO4
10. White phosphorous reacts with caustic soda 21. Two oxides of Nitrogen, NO and NO2 react
to give phosphine and sodium hypophosphite. together at 253 K and form a compound
In this reaction phosphorous undergoes Nitrogen X. X reacts with water to yield
1) Oxidation 2) Reduction another compound of Nitrogen Y. The shape
3) Both 4) None of these of the anion of Y molecule is
OXIDES 1) Tetrahedral 2) Triangular planar
11. The hybridization of phosphorous atom in 3) Square planar 4) Pyramidal
P4O6 and P4O10 is 22. Oxidation state of +1 for phosphorous is
1) sp 2) sp2 3) sp3 4) sp3d found in
12. The bonds present in P4O10 are 1) H 3 PO3 2) H 3 PO4 3) H 3 PO2 4) H 4 P2O7
1) Ionic and covalent 2) Ionic and dative
3) Covalent and dative 4) Only covalent bonds 23. The number of hydroxyl groups in
13. Which of the following oxides of nitrogen pyrophosphoric acid is
is the anhydride of nitrous acid ? 1) 3 2) 4 3) 5 4) 7
1) NO 2) N 2O3 3) N 2O4 4) N 2O5 24. H 3 PO2 is the formula for one of the
14. The number of oxygen atoms bonded to one phosphorous acids. Its name and basicity
are respectively
phosphorous atom in P4O10 is
1) Phosphorous acid and two
1) 4 2) 3 3) 6 4) 5 2) Hypophosphorous acid and two
15. The arrangement of oxygen atoms around 3) Hypophosphorous acid and one
each phosphorous in P4O10 4) Hypophosphoric acid and two
1) Pyramidal 2) Octahedral 25. The acid that forms primary, secondary and
3) Tetrahedral 4) Square planar tertiary phosphates is
16. When NH 4 NO3 is gently heated, an oxide of 1) H 3 PO2 2) H 3 PO3 3) HPO3 4) H 3 PO4
Nitrogen is formed. What is the oxidation 26. Which of the following is not an acidic
state of Nitrogen in this oxide ? salt?
1) + 4 2) + 2 3) + 3 4) + 1
1) NaH 2 PO2 2) NaH 2 PO3
17. The following are some statements about
oxides of VA group elements 3) NaH 2 PO4 4) Na2 HPO4
I) N 2O molecule is linear 27. The reducing strength of oxyacid of the
II) NO2 molecule is angular Phosphorous depends on
1) The number of H-atoms directly attached to P
III) N 2O5 molecule is angular 2) The number of H-atom attached to oxygen
The correct combination is atom
1) All are correct 2) I & III are correct 3) The number of O-atoms attached to P-atoms
3) II & III are correct 4) I & II are correct 4) The number of P-atoms
26
28. Regarding H 3 PO5 the wrong statement is 36. 4Zn + 10 HNO3 → 4Zn ( NO3 )2 + NH 4 NO3 + 3H 2O .
1) It’s basicity is three In this reaction one mole of HNO3 is reduced
2) Oxidation state P in it is +5
by
3) It contains O - O linkage
1) 32g Zn 2) 64g Zn 3) 128g Zn 4) 256g Zn
4) It can form a dimer
29. The following are some statements about 37. CaO.Ca ( NO3 )2  is the chemical composition
HNO2 of the substance, commonly used as
I) Its undissociated forms are tautomers 1) Fertiliser 2) Explosive
II) Its undissociated forms are resonance 3) Perfume 4) Medicine
structures 38. Which of the following is not correct ?
III) Its anhydride in pure state exists as 1) Ammonia is used as refrigerant
pale blue solid and that melts to deep blue 2)A mixture of Ca (CN )2 and C is known nitrolim
liquid
The correct combination is 3) A mixture of Ca ( H 2 PO4 )2 and
1) All are correct 2) I , III are correct CaSO4 .2 H 2O is known as superphosphate of
3) II , III are correct 4) I,II are correct lime
30. The statements regarding oxyacids of
phosphorous are 4) Hydrolysis of NCl3 gives NH 3 and HOCl
I) HPO3 molecule is monobasic acid Note:
1) Both (A) and (R) are true and (R) is the correct
II) H 4 P2O6 molecule has P - P bond explanation of (A)
III) H 4 P2O7 molecule has P-O-P linkage 2) Both (A) and (R) are true and (R) is not the
correct explanation of (A)
The correct combination is
3) (A) is true and (R) is false
1) All are correct 2) Only II is correct
4) (A) is false but (R) is true
3) II&III are correct 4) I&II are correct
39. Assertion (A): P4 is more reactive than N2
31. Which pair of oxyacids of phosphorous
Reason(R) : P - P bonds are relatively weaker
contain ‘P-H’ bonds ?
than N ≡ N
1) H 3 PO4 , H 3 PO3 2) H 3 PO5 , H 4 P2O7 40. Assertion (A): Bismuth compounds are stable
3) H 3 PO3 , H 3 PO2 4) H 3 PO2 , HPO3 in +V oxidation state than in +III oxidation
state.
AMMONIA AND NITRIC ACID Reason (R): Inert pair effect is observed in
32. A & B are two gases. ‘A’ is identified with Bismuth compounds.
the glass rod dipped in NH 3 and ‘B’ is 41. Assertion (A): The hydrides of VA group
identified with the glass rod dipped in HCl. elements are good reducing Agents.
Then A, B are Reason (R): NH3 is a weak reducing Agent
1) HCl, NO2 2) HCl, NH3 among the hydrides of VA group.
3) NH3, HCl 4) NH3, SO2 42. Assertion (A): P2O3 is more basic than N2O3
33. Nesslers reagent is used to detect trace Reason (R): Metallic nature of the central
amounts of ammonia. Its formula is atom increases down the group
1) KHgI4 2) K2HgI2 3) K2HgI4 4) KHgI3 43. Assertion (A): Ortho phosphoric acid is
34. Cyanamide process is used to prepare tribasic acid
1) Cyanide 2) Isocyanide Reason (R): Orthophosphoric acid forms
3) Ammonia 4) Nitric acid three series of salts.
35. Conc. HNO3 is treated with iron. The metal 44. Assertion (A): In the synthesis of Ammonia
is passive because by Habers process, mixture of potassium and
1) It is a transition metal aluminum oxides can be used as promotor.
2) It forms protective oxide film Reason (R): Promotor enhances the activity
3) It is reduced 4) It liberates laughing gas of catalyst
27
45. Assertion (A): Anhydrous Calcium chloride 21. NO + NO2 → N 2O3
is used as catalyst in cyanamide process
Reason (R): Catalyst increases the rate of N 2O3 + H 2O → 2 HNO2
reaction. HNO2 → H + + NO2−
46. Assertion (A): The basic nature of VA group
hydrides decreases from ammonia to 32. White densy fumes of NH 4Cl
bismuthine. 33. with NH 3 gives reddish brown ppt
Reason (R): Availability of lone pair on the
central atom in hydrides decreases down the LEVEL-II (H.W)
group.
47. Assertion (A): Stability of NH3 is greater than
GENERAL CHARACTERISTICS
PH3
Reason (R): M - H bond energy increases 1. How do we get pure N 2 gas
down the group in the hydrides of pnicogens. 1. NH 3 + NaNO2 2. NH 4Cl + NaNO2
48. Assertion (A): PH3 is more basic than NH3
Reason(R) : EN of N is more than that of P 3. N 2O + Cu 4. Ba ( N3 )2
49. Assertion (A): NH3 is liquid while the other 2. One mole of calcium phosphide on reaction
hydrides of V-A group elements are gases at with excess of water gives
room temp. 1) 1 mole of phosphine
Reason(R) : NH3 possess inter molecular H - 2) two moles of phosphoric acid
bonds in liquid state 3) two moles of phosphine
4) one mole of phosphourous pentoxide
LEVEL-II (C.W) - KEY 3. The p - p bond energy is x’ KJ/mole. Then
1) 2 2) 4 3) 4 4) 4 5) 2 6)3 7) 3 the energy needed for the dissociation of
124g of white phosphorous is
8) 4 9) 3 10) 3 11) 3 12)3 13) 2 14)2
1) x KJ 2) 4x KJ 3) 6x KJ 4) 8x KJ
15)3 16) 4 17) 4 18) 3 19) 2 20) 4 21) 2 4. The following are some statements
22) 3 23) 2 24) 3 25) 4 26) 1 27) 1 28) 4 about VA group elements
29) 2 30) 1 31) 3 32) 2 33) 3 34) 3 35) 2 I) All elements exhibits allotropy
36) 4 37) 1 38) 2 39) 1 40) 4 41) 2 42) 1 II) Boiling points decrease down the group
III) They contain five electrons in their
43) 2 44) 1 45) 1 46) 1 47) 3 48) 4 49) 4
valency shell
The correct combination is
LEVEL-II (C.W) - HINTS 1) All are correct 2) Only III is correct
1. ‘P’ atom never exceeds ‘5’ covalent bonds. 3) I & II are correct 4) II & III are correct
‘P’ belongs to VA group 5. With reference to protonic acids, which of
2. In down the group ionic radius gradually the following statements is correct ?
increases
1) PH 3 is more basic than NH 3
6. NH 3 having maximum complex forming
ability 2) PH 3 is less basic than NH 3
1 3) PH 3 is equally basic as NH 3
7. N3 H = −
3 4) PH 3 is amphoteric while NH 3 is basic
11. In P4O6 and P4O10 phosphrous has SP 3
DINITROGEN
hybradisation.
6. A diatomic gas will be obtained in
12. In P4O10 covalent and dative bonds both are
1) Cu + dil.HNO3 → 2) ( NH 4 )2 Cr2O7 
Heat
→
present.
3) Both 1 & 2 V→
4) NH 4 NO3 
18. S b C l 3 + H 2O → S b o C l + 2 H C l
o x o c a tio n
28
7. For NH 4 Cl + NaNO3  ∆
→ IV) Ease of formation of hydrides decreases
→ ( A ) 
Cu
→ ( B ) + ( X )gas , from NH 3 to BiH 3
which of the following is correct? The correct statements are
1) I , II , III , IV 2) I , III and IV
1) ( B ) is an amphoteric oxide 3) I , II and IV 4) I and IV
2) ( X ) is a colourless, diamagnetic gas which OXIDES
combines with Al on heating 13. The number of Oxygen atoms surroundings
3) ( X ) can be produced by action of each Nitrogen atom in N2O5 is
1) 2 2) 3 3) 4 4) 5
( Zn + NaOH ) on NaNO2 14. Oxide of nitrogen used as one of the
4) ( X ) is a coloured, paramagnetic gas which constituents in making anesthetics is
1) Nitric Oxide 2) Nitrogen dioxide
combines with Al on heating
3) Nitrous Oxide 4) Dinitrogen Pentoxide
8. The statements regarding N 2 15. The number of bridge oxygen atoms present
molecule are in both P4O6 and P4O10 are respectively
I) The Bond energy is 945.4 KJ/mole
II) It has triple bond 1) 4 , 6 2) 4 , 4 3) 6 , 4 4) 6 , 6
III) It contains 2σ and 1π bond 16. The number of P-O bonds and lone pair of
The correct combination is electrons present in P4O6 molecule .
1) Only II is correct 2) I & II are correct 1) 12 , 16 2) 12 , 12 3) 8 , 8 4) 12 , 4
3) II and III are correct 4) All are correct
17. LIST - 1 LIST - 2
HYDRIDES A) NO 1) Colourless and paramagnetic
9. Which of the following is not correct B) NO2 2) Greenish yellow gas
1) Hydrolysis of NCl3 gives NH3 and HOCl
2) NH3 is less stable than PH3 C) N 2O3 3) Reddish brown and
3) NH3 is weak reducing agent compared to PH3 paramagnetic
4) Nitric Oxide in solid state exhibits
diamagnetic property. D) N 2O5 4) Anhydride of Nitric acid
10. Silver chloride dissolves in excess of NH 4OH . 5) Anhydride of Nitrous acid
The cation present in solution is The correct match is
+ A B C D A B C D
1) Ag + 2)  Ag ( NH 3 )4  1) 2 4 5 1 2) 1 3 5 4
+ + 3) 3 2 1 5 4) 1 4 4 3
3)  Ag ( NH 3 )2  4)  Ag ( NH 3 )6 
18. LIST - 1 LIST - 2
11. The oxyacid of phosphorous which has more
non-ionisbale hyderogens A) NCl3 + H 2O → 1) HOCl
1) H 3 PO2 2) H 3 PO3 3) H 3 PO4 4) H 3 PO5 B) PCl3 + H 2O → 2) H 3 PO3
12. The following are some statements related
to VA group hydrides C) PCl5 + H 2O → 3) H 3 PO4
I) Reducing property increases from D) PF3 + H 2O → 4) H 3 PO2
NH 3 to BiH 3 5) No Hydrolysis
II) Tendency to donate lone pair decreases The correct match is
from NH 3 to BiH 3 A B C D A B C D
III) Ease of replacing H with Cl decreases 1) 1 2 3 5 2) 2 4 2 5
3) 3 2 2 4 4) 5 3 2 1
from NH 3 to BiH 3
29
19. When orthophosphoric acid is strongly 25. In solid state PCl exists as ionic solid i.e.,
5
heated the product formed is
[ X ] [Y ] , shapes of X + and Y − are respectively
+ −
1) Phosphine , PH 3
1) Tetrahedral, Pyramidal
2) Phosphorous trioxide , P2O3 2) Tetrahedral, Octahedral
3) Phosphorous acid , H 3 PO3 3) Octahedral , Linear
4) Octahedral , Trigonal bipyramidal
4) Metaphosphoric acid, HPO3
AMMONIA AND NITRIC ACID
HALIDES 26. Atomicity ot dimeric phosphorous pentoxide is
20. N 2 forms NCl3 whereas P can form both ‘x’ and the number of shared electron pair is
PCl3 and PCl5 . Why? ‘y’. Then
a) y-x=6, b)2x=y+8 c)10x-7y=0
1) P has d-orbitals which can be used for bonding 1) only ‘a’ is correct 2) only ‘b’ is correct
but N 2 does not have 3) only ‘c’ is correct
2) N atom is larger than P in size 4) all the above are correct
3) P is more reactive towards Cl than N 27. The number of P-P bonds in cyclotrimeta
4) None of the above phosphoric acid is
1) 3 2) 9 3) 6 4) zero
OXYACIDS 28. A mixture of potassium nitrite and
21. Thomas Slag is ammonium chloride on heating liberates the
1. Ca3 PO4 2 + CaSiO3 2. MnSiO3 gas
3. CrSiO3 4. FeSiO3 1) O2 2) N 2O 3) NH 3 4) N 2
22. The following some statements about HNO2 29. Which of the following can acts as
are both oxidant and redutant
i)It acts as both oxidising and reducing agent.
1) H 2 N 2O2 2) HNO2 3) HNO3 4) HNO4
ii) It is a strong acid.
iii) Its Anhydride in pure state exists as pale blue 30. Concentrated nitric acid oxidises
liquid phosphorous and iodine, respectively to
The correct combination is 1) H 3 PO3 , HI 2) H 3 PO3 , HIO4
1) All are correct 2) i, iii are correct
3) H 3 PO4 , HIO3 4) H 3 PO4 , HIO4
3) ii, iii are correct 4) i, ii are correct
Note:
23. In H 3 PO3 molecule
1) Both (A) and (R) are true and (R) is the correct
1) P-atom is surrounded by three - OH groups explanation of (A)
2) P-atom is tetrahedrally surrounded by two 2) Both (A) and (R) are true and (R) is not the
-OH groups, one oxygen atom and one correct explanation of (A)
hydrogen atom 3) (A) is true and (R) is false
3) P-atom is surounded by four -OH groups 4) (A) is false but (R) is true
4) P - atom is surrounded by two -H atoms 31. Assertion (A): NH4NO3 on gently heating
24. The following are some statements about gives N2O
oxyacids of VA group elements Reason(R) : N2O is acidic in nature
−
I) The salt of nitric acid contains NO3 ion 32. Assertion (A): HNO 3 stronger acid than
II) The salt of phosphoric acid contains PO43− ion HNO2
Reason(R) : Both are monobasic acids
III) Salts of meta phosphoric acid contains
33. Assertion (A): HPO3 is monobasic acid
HPO32− ion Reason(R) : The salts of HPO3 are called meta
The correct combination is phosphates
1) All are correct 2) I , III are correct 34. Assertion (A): N3- is isostructural with I3-
3) II , III are correct 4) I , II are correct Reason(R) : The E.N of N is greater than I
30
35. Assertion (A): A mixture of CaCN 2 and Zn + NaOH → ( H 2 ) . The evolved H 2 reduces
graphite is known as nitration mixture
Reason(R) : NH3 is collected by downward NaNO2 to form NH 3 gas
displacement of air
9. NH 3 is more stable. due to H-bond
36. Assertion (A): Nitrogen is inactive in normal
chemical reactions. 10. AgCl + 2 NH 4OH
Reason (R): The bond dissociation energy is
→  Ag ( NH 3 )2  Cl + 2 H 2O
directly proportional to reactivity.
37. Assertion (A): White phosphorous is less Diammine silver ( I ) chloride
reactive than red phosphorous. 13. Three oxygen atoms surrounds each nitrogen atom
Reason (R): white phosphorous has more 14. N2O is used as anesthetic.
bond angle strain than red phosphorous
+C
38. Assertion (A): Nitric oxide is neutral oxide 26. CaNCN
14243
Nitro lim
Reason (R): Nitric oxide is paramagnetic, as
it possess an odd electron. PREVIOUS EAMCET QUESTIONS
39. Assertion (A): NO2 is paramagnetic molecule, 1. The gases evolved in the decomposition of
where as N2O4 is diamagnetic lead nitrate are:
Reason (R): Molecules with unpaired 1. N 2O3 , NO 2. NO2 , O2 3. N 2O3 , O2 4. N 2O3 , O2
electrons are Diamagnetic. 2. The total number of σ and π bonds in
40. Assertion(A):The basicity of pyrophosphoric acid are respectively:
orthophosphorous acid is two 1. 8,2 2. 10,2 3. 12,2 4. 8,4
Reason (R): In orthophosphorous acids, two 3. An oxide of nitrogen (X) is formed when Z is
replaceable hydrogen atoms are present
41. Assertion (A): Nitrogen cannot form reacted with P2O5 , X is soluble in water and
pentahalides. gives Z. Which one of the following is Z?
Reason (R): Nitrogen cannot expand its octet 1. HNO3 2. H 2 N 2O2 3. HNO2 4. HN3
configuration. 4. Which one of the oxides of nitrogen dimerises
into colourless solids/liquid on cooling?
LEVEL-II (H.W) - KEY
1. N 2O 2. NO 3. N 2O3 4. NO2
1) 4 2) 3 3) 3 4) 2 5) 2 6) 3 7) 2
5. Which one of the acids is a dibasic acid?
8) 2 9) 2 10) 3 11) 1 12) 1 13) 2 14) 3
1. H 3 PO3 2. H 3 PO2 3. HPO3 4. H 3 PO4
15) 4 16) 1 17) 2 18) 1 19) 4 20) 1 21) 1
6. Amongst the trihalides of nitrogen, which one
22) 2 23) 2 24) 4 25) 2 26) 4 27) 4 28) 4 is least basic
29) 2 30) 3 31) 3 32) 2 33) 2 34) 2 35) 4 1. NF3 2. NCl3 3. NBr3 4. NI 3
36) 3 37) 4 38) 2 39) 3 40) 1 41) 1
PREVIOUS EAMCET - KEY
LEVEL-II (H.W) - HINTS 1) 2 2) 3 3) 1 4) 4 5) 1 6) 1
6. 3Cu + 8 HNO3
LEVEL-III
→ 3Cu ( NO3 )2 + 2 NO + 4 H 2O
( NH 4 )2 Cr2O7 → N 2 + Cr2O3 + 4 H 2O GENERAL CHARACTERISTICS
1. Which of the following statements is not true
7. NH 4OH .HCl + NaNO2 1) Nitrogen differs markedly from the other
members of its family
→ N 2O 
Cu
→ CuO + N2
(B) (x) 2) Nitrogen has five valency electrons
(Colourless, dia magnetic)
( Basic Oxide ) 3) Nitrogen show covalency greater than four
4) Nitrogen shows great stability as a free
2 Al + N 2 → 2 AlN element
31
2. The correct statement is 8. In Nitrogen family the H-M-H angle in the
1) High reactivity of white phosphorus is due hydrides MH 3 gradually becomes closer to
to small bond angle (600) in P4 molecule which
causes large strain 900 on going from N to Sb. This shows that
2) Low reactivity of red phosphorus is due to gradually
polymeric structure 1) The basic strength of the hydrides increases
3) Black phosphorus conducts electricity due 2) Due to the increase in the size of central atom
to presence of delocalised π electrons M and increase in its electronegativity
4) All the above 3) The bond energies of M-H increase
3. Which of the following statement is wrong? 4) The bond pairs of electrons become closer to
1) The stability of hydride increases from NH 3 each other.
9. Gas obtained by heating a mixture of
to BiH 3 in group 15 of the periodic table
ammonium chloride and slaked lime is
2) nitrogen cannot form d π − pπ bonds 1) NH3 2) N2 3) N2O 4) NO2
3) single N − N bond is weaker than the single 10. Ammonia is not a product in the
P − P bond 1) Hydrolysis of nitrolim
4) N 2O4 has two resosnance structures 2) Hydrolysis of Aluminium nitride
3) Decomposition of Ammonium nitrite
DINITROGEN 4) Hydrolysis of urea
4. Nitrogen can be purified from the impurities 11. Which fo the following statements is correct
of oxides of nitrogen and ammonia by passing 1. All the hydrides of VA group elements are
through
pyramidal in shape
1. Conc. HCl
2.Alkaline solution of pyrogallol 2. The bond angle decreases from NH3 to BiH3
3. A solution of K 2 Cr2 O7 acidified with H 2SO4 down the group because of bond pair-bond pair
4. A solution of KOH repulsion
5. Animals die in nitrogen because 3. The basic strength decreases from NH3 to
1. It destroys haemoglobin
BiH3 , because of decreases in the availability
2. Of the want of oxygen
3. It is heavier than air 4. It is poisonous of lone pair of electrons
−
4. All are correct
6. PCl5 + Cl − → PCl6 . The wrong statement
12. Some of the reasons of reaction of NH3 with
regarding the above equation is
hydrogen chloride are given below. Pick up
1) Hybridisation of P changes from sp 3 d to the incorrect are
3 2
sp d 1. The nitrogen atom of NH3 gains electrons
2) Oxidation number of P changes from +5 to
2. NH3 can give a pair of electrons
+6
3) Covalency of P changes from 5 to 6 3. A proton in HCl can accept an electron pair
4) Here PCl is a Lewis acid from NH3
5
4. The Cl −ion has a stable configuration of 8
HYDRIDES
electrons.
7. Sodium dissolved in Ammonia has Blue
colour due to 13. Phosphine is not obtained by the reaction
1) Solvated Sodium 2) Amide Ion 1. White P is heated with NaOH
3) Solvated electron 2. Red P is heated with NaOH
4) Lone pair of electrons on Nitrogen in NH3 3. Ca 3P2 is heated with water
molecule 4. Phosphorus trioxide is boiled with water
32
14. The bottles of liquid ammonia are opened 23. In nitroprusside ion, the iron and ‘NO’ exist
after cooling them in ice for sometime. It is as Fe+2 and NO + rather than Fe+3 and NO.
because liquid ammonia
These forms can be differentiated by
1. Has high vapour pressure at room temperature
1. Estimating the concentration of iron
2. Is corrosive liquid
3. is an explosive 4. Brings tears in eyes 2. Measuring the concentration of CN −
15. The dipole moment of NF3 is less than NH3 3. Measuring the solid state magnetic moment
4. Thermally decomposing the compound
because
24. The correct order of bond angle of
1. NH3 forms associated molecules
NO2+ , NO2 and NO2− is
2. F is more reactive than H
3. The resultant of bond polarity is less 1) NO2+ < NO2 < NO2− 2) NO2+ = NO2− < NO2
4. The resultant of individual polarities is 3) NO2+ > NO2 > NO2− 4) NO2+ > NO2 < NO2−
opposed by the polarity of lone pair
16. Ammonia will be obtained in 25. A tetra-atomic molecule ( A) on reaction with
1) CaCN 2 + H 2O → 2) NH 4 H 2 PO4  → nitrogen ( I ) oxide, produces two substances
Heat
V→ V→
3) NH 4 NO2  4) Ca (CN )2 + H 2O 
(B) and (C ) . ( B ) is a dehydrating agent
17. The compound ( SiH 3 )3 N is expected to be
while substance (C ) is a diatomic gas which
1) pyramidal and more basic than (CH 3 )3 N shows almost inert behaviour. The substances
2) planar and less basic than (CH 3 )3 N ( A) , ( B ) and (C ) are
3) pyramidal and less basic than (CH 3 )3 N 1) P4 , P4O10 , N 2 2) P4 , N 2O5 , N 2
4) planar and more basic than (CH 3 )3 N 3) P4 P2O3 , Ar 4) P4 , P2O3 , O2
OXIDES HALIDES
18. The number of P-O-P bonds present in P4O6 26. Bottle of PCl is kept stoppered because it
3
and P4O10 are respectively 1) explodes 2) gets oxidized
1) 4 and 5 2) 4 and 6 3) 6 and 6 4) 3 and 6 3) is volatalised 4) reacts with moisture
19. One of the acids listed below is formed from 27. What may be expected to happen when
P2O3 and the rest are formed from P2O5. The phosphine gas is mixed with chlorine gas?
acid formed from P2O3 is
1) HPO3 2) H4P2O7 3) H3PO4 4) H3PO3 1. PCl 3 and HCl are formed and the mixture
20. Group 15 of the periodic table consists of the warm up
elements N, P, As, Sb and Bi. On passing from 2. PCl 3 and HCl are formed and the mixture
N to Bi, the oxides of the elements of general
cools down
formula M 2O3 becomes.
3. PH 3 , Cl 2 is formed with warming up
1. Strong reducing agents 2. More ionic
4. The mixture only Cools down
3. More basic 4. More volatile
28. Which of the following halides is most acidic?
21. The number of bonds in P4 O10 is
1) PCl3 2) SbCl3 3) BiCl3 4) CCl4
1. 6 2. 16 3. 20 4.7
22. The nitrate which when heated gives off a gas 29. In the compound of the type POX 3 , P atom
(or) a mixture of gases which cannot relight show multiple bonding of the type
a glowing splinter is 1) pπ − pπ 2) dπ − dπ
1. Sodium nitrate 2. Ammonium nitrate
3) pπ − d π 4) no multiple bonding
3. Lead nitrate 4. Potassium nitrate
33
30. The BCl3 is a planar molecule whereas, NCl3 38. Which of the following is a cyclic oxoacid
is pyramidal because 1. H 4 P2 O7 2. H 4 P2 O6 3. H 3 P3O 9 4. H5P5O15
1) N − Cl bond is more covalent than B − Cl 39. When rain is accompained by a thunderstorm,
bond the collected rain water will have a PH value,
2) B − Cl bond is more polar than N − Cl bond 1. Slightly higher than that when the thunder
3) nitrogen atom is smaller than boron storm
2. unifluenced by occurrence of thunder storm
4) BCl3 has no lone pair but NCl3 has a lone 3. which depends on the amount of dust in air
pair of electron 4. slightly lower than that of rain water without
OXYACIDS thunderstorm
31. The correct statement in respect of structure 40. The following are some statements about
of hypo phosphorous acid is oxyacids of VAgroup elements
1) 2-OH groups, 2-H atoms are attached directly i) The salt of Nitric acid contains NO3- ion
to P ii) The salt of phosphoric acid contains PO43- ion
2) One OH group and 2-H atoms are directly iii) Salts of meta phosphoric acid contains
attached to P H2PO3- & HPO32- ions
3) One OH group and 3 - H atoms are directly The correct combination is
attached to P 1) i and ii are correct 2) ii and iii are correct
4) Three OH groups are attached directly to P 3) all are correct 4) only ii is correct
41. Which of the following metals, Fe, Zn, Pb,
32. In NO 3− ion, the number of bond pair and Ag and Pt do not give metal nitrate on
lone pair of electrons on nitrogen atom are treatment with concentrated HNO3 ?
1. 2,2 2. 3,1 3. 1,3 4. 4,0
1) Fe and Zn 2) Fe and Pt
33. List - I List - II
3) Pb, Ag and Pt 4) Fe, Ag and Pt
A) N2O 1) Sp2 and planar triangle
B) HNO2 2) Nitrite and Nitro form 42. Among the following ions, pπ − d π overlap
C) NO3 -- 3
3) Sp and Tetrahedron is present in
D) HNO4 4) Laughing gas 1) NO3− 2) PO43− 3) CO32 − 4) NO2−
5) Peroxy bond
The correct match is 43. Phosphate + conc.HNO3 + ( NH 4 )2 MoO4
A B C D A B C D so ln . → Yellow precipitate .
1) 1 2 3 4 2) 3 2 4 1 The composition of yellow precipitate is
3) 2 5 3 4 4) 4 2 1 5
34. By the reduction of HNO3 to NO2 the number 1) ( NH 4 )3 PO4 .MoO3 2) ( NH 4 )3 PO4 .12MoO3
of moles of electrons involved per mole of 3) ( NH 4 )2 PO4 .12MoO3 4) NH 4 PO4 .MoO3
HNO3 is 44. Concentrated nitric acid reacts with iodine
1) 8 2) 6 3) 3 4) 1 to give
35. Sodium hexametaphosphate is known as
1) HI 2) HOI 3) HOIO2 4) HOIO3
1. Calgon 2. Permutit 3. Natalite 4.Nitrolim
36. Poly phosphates are used as water softening 45. Three reactions involving H 2 PO4− are given
agents because they below
1. Form soluble complexes with anionic species
(i) H 3 PO2 + H 2O → H 3O ( − ) + H 2 PO4(−)
2. Precipitate anionic species
3. Form soluble complexes with cationic species (ii) H 2 PO4(−) + H 2O → H 3O(+ ) + HPO42−
4. Precipitate cationic species
37. In the reaction (iii) H 2 PO4− + OH (−) → O 2− + H 3 PO4
4HNO3 + P4 O10 → 4HPO3 + X the product In which of the following does H 2 PO4− act as
X is an acid [AIEEE-2010]
1) (i) only 2) (ii) only
1. N 2 O5 2. N 2 O3 3. NO 2 4. H 2 O 3) (iii) only 4) (i) and (ii) only
34
LEVEL - III - KEY PREVIOUS MAINS QUESTIONS

1) 3 2) 4 3) 1 4) 3 5) 2 6) 2 7) 3 1. Which one of the following pairs is obtained
on heating ammonium dichromate?
8) 4 9) 1 10) 3 11) 4 12) 1 13) 2 14) 1
1) N 2 and H 2O 2) N 2O and H 2O
15) 4 16) 1 17) 3 18) 3 19) 4 20) 3 21) 2
22) 2 23) 3 24) 3 25) 1 26) 4 27) 1 28) 1 3) NO2 and H 2O 4) NO and NO2
29) 3 30) 4 31) 2 32) 4 33) 4 34) 4 35) 1 2. The hybridization of atomic orbitals of
36) 3 37) 1 38) 3 39) 4 40) 1 41) 2 42) 2 nitrogen in NO2+ , NO3− and NH 4+ are:
43) 2 44) 3 45) 2 1) sp, sp 3 and sp 2 respectively
LEVEL-III - HINTS 2) sp, sp 2 and sp 3 respectively
1. Nitrogen belongs to VA group
2. Due to polymerized structure 3) sp 2 , sp and sp 3 respectively
6. 2 KNO3 + 10 K → 6 K 2O + N 2 ; 4) sp 2 , sp 3 and sp respectively
NH 4 NO3 → N 2O + 2 H 2O 3. A metal X on heating in nitrogen gas gives Y.
16. CaCN 2 + 3H 2O → CaCO3 + 2 NH 3 ; Y on treatment with H 2O gives a colourless

gas which when passed through CuSO4
NH 4 H 2 PO4 → NH 3 + HPO3 + H 2O
solution gives a blue colour.Y is :
17. ( SiH 3 )3 N is planar and less basic than
1) Mg ( NO3 )2 2) Mg3 N 2
(CH 3 )3 N because lone pair of N atom is used
3) NH 3 4) MgO
to form d π − pπ back bonding with Si-atom
4. Extra pure nitrogen can be obtained by
∆
22. NH 4 NO3 → N 2 O + 2H 2 O.N 2 O is non heating :
combustable. 1) NH 3 with CuO 2) NH 4 NO3
2−
23. The nitroprusside ion is  Fe (CN )6 NO  . The+
3) ( NH 4 )2 Cr2O7 4) Ba ( N3 )2
magnetic moment measurement reveal the
presence of 4 unpaired electrons in Fe which 5. The reaction of white phosphours with
aqueous NaOH gives phosphine and another
must be then in Fe ++ (3d 6 ) and not Fe +++ (3d 5 ) phosphorus containing compound. The
24. NO2+ − 1800 ; NO2− − 1150 ; NO2 − 1320 reaction type, the oxidation states of
phosphorus in phosphine and other products
25. P4 + 10 N 2O → P4O10 + 10 N 2 are respectively:
28. In CCl4 , carbon atom does not have d-orbitals 1) redox reaction, −3 and − 5
to accommodate a lone pair of electrons and 2) redox reaction, +3 and + 5
hence is not a Lewis acid. In PCl3 , SbCl3 and 3) disproportionation reaction −3 and + 1
BiCl3 central atom has empty d-orbitals in each 4) disproportionation reaction −3 and + 3
case but electronegativity of P is maximum, 6. The molecule having smallest bond angle is:
hence PCl3 is strongest acid. 1) AsCl3 2) SbCl3 3) PCl3 4) NCl3
3
29. Hybridisation of P is Sp d
42. Phosphorus has vacant d-orbitals PREVIOUS MAINS - KEY
43. Ammonium phosphomolybdute test 1) 1 2) 2 3) 2 4) 4 5) 3 6) 2
35
9. Which of the following hydrides is Thermally
LEVEL-IV stable
1. White phosphorus ( P4 ) has 1) PH 3 2) AsH 3 3) NH 3 4) BiH 3
1. Six P-P single bonds 10. Which of the following is more basic hyrides
2. Four lone pairs of electrons 1) NH 3 2) BiH 3 3) PH 3 4) AsH 3
3. P-P-P angle of 60 4) All the above
0
11. The strong reducing agent is
2. A lightning flash through air may result in 1) NH 3 2) BiH 3 3) PH 3 4) AsH 3
the formation of
1. NO 2. HNO2 3. HNO3 4. NH 3 (P-2)Regarding H 3 PO2 , its structure is as follows
3. Pyrophosphorous acid, H 4 P2 O5 O
1. It is dibasic acid ||
2. It is strongly reducing in nature HO − P −H

|
3. It contains one P-O-P bond H
4. ‘P’ is sp3 hybridised
Its basicity is one. Its salts are known as
4. Nitrogen can combine directly at higher
hyphophosphites
temperature to give nitrides with
12. In the above structure the no. of
1. Mg 2. Al 3. 1 & 2 4. Fe
5. White phosphorus can be removed from red Pπ − d π bonds
phosphorus by 1) 1 2) 2 3)zero 4) 3
1. sublimation 13. In the above oxyanion the hybridisation of P
2. heating with alkali solution atoms is
3. distillation 4. both 1 & 2 1) Sp 2) Sp 2 3) Sp 3 4) Sp 3d
6. The molecules having pyramidal shape are
14. In the above structure the number
1. PH 3 2. NH3 3. NCl 3 4. PCl5 replaceable H- atoms
7. Which of the following are correct statements 1) 1 2) 2 3) 3 4) zero
1. Solid PCl 5 exists as tetrahedral [PCl 4 ] and 15. The above acid is
+
1) Reducing agent 2) Dehydrating agent

octahedral [PCl 6 ] ions
−
3) Drying agent 4) Pickling agent
2. Solid PBr5 exists as [PBr4 ] Br −

+
Matrix Matching
16. List-1 List-II
3. Solid N 2 O5 exists as NO +2 NO3−
A) Anhydride of HNO2 P) N 2O3
4. All the above
8. The nitrogen oxide(s) that contains N − N B) Anhydride of HNO3 Q) NO
bond(s) is (are)
C) Neutral oxides R) N 2O5
1) N 2O 2) N 2O3 3) N 2O4 4) All
D) Paramagnetic S) T) N 2O
COMPREHENSION TYPE QUESTIONS
(P-1)Vth A group hydrides
The hydrides of V th A group elements are
LEVEL-IV - KEY
good reducing agents, their reducing ability 1) 1,3,4 2)1,2,3 3)2,3,4, 4)1,2,3
increases from NH 3 to BiH 3 and basic nature 5) 1,2,4 6) 1,2,3 7) 1,2,3,4 8) 1,2,3,4
decreases from NH 3 to BiH 3 , thermal 9) 3 10) 1 11) 2 12) 1 13) 3 14) 1 15) 4
stability and bond angles decreases from
16) A-P; B-R; C-Q,T; D-Q,S
NH 3 to BiH 3
36

15th Group Elements

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15th Group Elements

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JEE-MAIN-SR-CHEM-VOL-II 15th GROUP ELEMENTS

15th GROUP ELEMENTS

Hydroxyapatite : {3Ca (PO ) .Ca (OH ) } ;

Orpiment: {( As2 S3 )}{ yellowcolour}

Sb: Stibinite : {( Sb2 S3 )} and in flue dust as Sb2O3

or Bismuthinite Orthophosphoric acid : H 3 PO4

NH 4 Cl (aq ) + NaNO2 (aq ) → (at about 2000 K)

N N O (lin ea r) Ø It is obtained by heating Lead Nitrate.

Nitrogen trioxide (N2O3): It is also known

3Cu ( NO3 )2 + 2 NO + 4 H 2O P4 + 3NaOH + 3H 2 O → PH 3 + 3NaH 2 PO 2

Ø It is also obtained by the action of thionyl octahedral ( sp d ) .3 2

chloride with white phosphorous

hydrolysis in the presence of moisture.

Meta Phosphoric acid (HPO 3 ): Meta

C.U.Q OXIDATION STATES

3) NH 3 isa weak reducing agent compared to ADDITIONAL SYNOPSIS BITS

LEVEL - III - KEY PREVIOUS MAINS QUESTIONS

16. CaCN 2 + 3H 2O → CaCO3 + 2 NH 3 ; Y on treatment with H 2O gives a colourless

2. It is strongly reducing in nature HO − P −H

1) Reducing agent 2) Dehydrating agent

2. Solid PBr5 exists as [PBr4 ] Br −

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