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Nitrogen
Nitrogen
Contents
Topic
Page No.
Theory
01 - 26
Exercise - 1
27 - 39
Exercise - 2
39 - 44
Exercise - 3
45 - 47
Exercise - 4
48 - 49
Answer Key
50 - 57
Syllabus
As
Sb
Bi
Atomic Number
15
33
51
83
Atomic Mass
14.01
30.97
74.92
121.76
208.98
Electronic configuration
[He] 2s 2p
Covalent Radius / pm
Ionic Radius / pm
a = M3, b = M+3
70
Ionization enthalpy
/ (kJ mol1)
171
[Ne] 3s 3p
[Ar] 3d
10
4s 4p
110
120
222
212
10
[Kr] 4d
5s 5p
[Xe] 4f
14
10
5d
140
150
76
103
1402
1012
947
834
703
2856
1903
1798
1595
1610
4577
2910
2736
2443
2466
3.0
2.1
2.0
1.9
1.9
Electronegativity
6s 6p
CHEMICAL PROPERTIES :
Oxidation States and trends in a chemical reactivity :
The common oxidation states of these elements are 3, +3 and +5. The tendency to exhibit 3 oxidation
state decreases down the group , bismuth hardly forms any compound in 3 oxidation state. The stability of
+5 oxidation state decreases down the group. The only well characterised Bi (V) compound is BiF5 .The
stability of +5 oxidation state decreases and that of +3 state increases (due to inert pair effect) down the
group.
Bi3+ > Sb3+ > As3+ ; Bi5+ < Sb5+ < As5+
Nitrogen exhibits +1, +2, +4 oxidation states also when it reacts with oxygen. Phosphorus also shows +1
and +4 oxidation states in some oxoacids.
In the case of nitrogen, all oxidation states from +1 to +4 tend to disproportionate in acid solution.
For example,
3 HNO2 HNO3 + H2O + 2 NO
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Similarly, in case of phosphorus nearly all intermediate oxidation states disproportionate into +5 and 3 both
in alkali and acid. However +3 oxidation state in case of arsenic , antimony and bismuth become increasingly
stable with respect to disproportionation.
Nitrogen is restricted to a maximum covalency of 4 since only four (one s and three p) orbitals are available
for bonding. The heavier elements have vacant d orbitals in the outermost shell which can be used for bonding
(covalency) and hence , expand their covalence as in PF6 .
ANOMALOUS PROPERTIES OF NITROGEN :
Nitrogen differs from the rest of the members of this group due to its smaller size , high electronegativity, high
ionisation enthalpy and nonavailability of d orbitals. Nitrogen has unique ability to form pp multiple bonds
with itself and with other elements having small size and high electronegativity (e.g., C, O). Heavier elements
of this group do not form pp bonds as their atomic orbitals are so large and diffuse that they cannot have
effective overlapping. Thus, nitrogen exists as a diatomic molecule with a triple bond (one s and two p)
between the two atoms. Consequently , its bond enthalpy (941.1 kJ mol1) is very high. On the contrary,
phosphorus, arsenic and antimony form metallic bonds in elemental state. However, the single
NN bond is weaker than the single PP bond because of high interelectronic repulsion of the nonbonding
electrons, owing to the small bond length. As a result the catenation tendency is weaker in nitrogen. Another
factor which affects the chemistry of nitrogen is the absence of d orbitals in its valence shell. Besides
restricting its covalency to four , nitrogen cannot form dp bonds as the heavier elements can e.g., R3P=O
or R3P=CH2 (R = alkyl group). Phosphorus and arsenic can form dp bond also with transition metals when
their compounds like P(C2H5)3 and As(C6H5)3 act as ligands.
Hydrides :
All the elements of Group 15 form hydrides of the type EH3 where E=N, P, As, Sb or Bi. Some of the
properties of these hydrides are shown in Table. The hydrides show regular gradation in their properties. The
stability of hydrides decreases from NH3 to BiH3 which can be observed from their bond dissociation enthalpy.
Consequently , the reducing character of the hydrides increases. Ammonia is only a mild reducing agent
while BiH3 is the strongest reducing agent amongst all the hydrides. Basicity also decreases in the order
NH3 > PH3 > AsH3 > SbH3 BiH3 .
PROPERTIES OF HYDRIDES OF GROUP 15 ELEMENTS
Property
NH3
PH3
AsH3
SbH3
BiH3
Melting point / K
195.2
139.5
156.7
185
Boiling point / K
238.5
185.5
210.6
254.6
290
(E H) Distance / pm
101.7
141.9
151.9
170.7
107.8
93.6
91.8
91.3
46.1
13.4
66.4
145.1
278
389
322
297
255
HEH angle ( )
fH / kJ mol
dissH (E H) / kJ mol
Oxides :
All these elements form two types of oxides : E2O3 and E2O5 . The oxide in the higher oxidation state of the
element is more acidic than that of lower oxidation state. Their acidic character decreases down the group.
The oxides of the type E2O3 of nitrogen and phosphorus are purely acidic , that of arsenic and antimony
amphoteric and those of bismuth is predominantly basic.
OXIDES OF 15TH GROUP ELEMENTS
Element
Types of Oxides
As
Sb
Bi
X2O3
N2O3
P2O3
As2O3
Sb2O3
Bi2O3
X2O4
N2O4
P2O4
As2O4
Sb2O4
Bi2O4
X2O5
N2O5
P2O5
As2O5
Sb2O5
Halides :
These elements react to form two series of halides : EX3 and EX5 . Nitrogen does not form pentahalide due
to non availability of the d-orbitals in its valence shell. Pentahalides are more covalent than trihalides. All
the trihalides of these elements except those of nitrogen are stable. In case of nitrogen, only NF3 is known to
be stable. Trihalides except BiF3 are predominantly covalent in nature. Halides are hydrolysed in water
forming oxyacids or oxychlorides.
PCl3 + H2O H3PO3 + HCl
SbCl3 + H2O SbOCl (orange) + 2HCl
BiCl3 + H2O BiOCl (white) + 2HCl
NITROGEN (N) :
Dinitrogen comprises 78% of the earth atmosphere but it is not a very abundant element in the earths crust.
Nitrates are all very soluble in water so they are not wide spread in the earths crust. NaNO3 is found together
with small amounts of KNO3, CaSO4 and NaIO3 along the coast of southern Chile under a thin layer of sand
or soil. Nitrates are difficult to reduce under the laboratory conditions but microbes do it easily. Ammonia
forms large number of complexes with transition metal ions. Nitrogen is an important and essential constituent
of proteins and amino acids. Nitrates and other nitrogen compounds are extensively used in fertilizers and
explosive.
Preparation :
(i)
NH4Cl + NaNO2
NH4NO2 + NaCl ;
NH4NO2
N2 + 2H2O.
(ii)
(iii)
By oxidation of ammonia :
(A) At lower temperature
(a)
8NH3 () + 3Cl2 (g) 6NH4Cl + N2
If excess of Cl2 is used in this reaction, nitrogen trichloride is formed as per the following
reaction,
NH3 + 3Cl2 NCl3 + 3HCl
Nitrogen trichloride is an explosive substance.
(b)
By reaction of ammonia with calcium hypochlorite or Br2
4NH3 + 3Ca(OCI)2 3CaCl2 + N2 + H2O
(B) At higher temperature
By passing ammonia over heated cupric oxide or PbO :
2NH3 + 3CuO N2 + 3Cu + 3H2O
(iv)
300C
2NaN3
3N2 + 2Na
(i)
(ii)
(i)
(ii)
It is absorbed by heated Mg and Al. The nitrides formed thus react with water to form NH3.
3Mg + N2 Mg3N2 ;
Mg3N2 + 6H2O 3Mg(OH)3 + 2NH3
2Al + N2 2AlN
;
2AlN + 6H2O 2Al(OH)3 + 2NH3
(iii)
Reaction with H2 : At 200 atm and 500oC, and in the presence of iron catalyst and molybdenum promoter, N2
combines with H2 reversibly to form ammonia. The process is called Habers Process and is the industrial
method of manufacturing ammonia. The reaction is exothermic.
N2 + 3H2 2NH3
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(iv)
Reaction with oxygen: When air free from CO2 and moisture is passed over an electric arc at about 2000 K,
nitric oxide is formed. This reaction is endothermic.
N2 + O2 2NO
(v)
Reaction with CaC2 and BaC2: At 1100oC, these carbides react with N2 forming CaCN2 and Ba(CN)2 respectively.
CaC2 + N2
CaCN2 + C (nitrolim, a fertilizer) ;
BaC2 + N2
Ba(CN)2
CaCN2 reacts with H2O in the soil to produce NH3 gas. NH3 gas is converted into nitrates by the nitrating
bacteria present in soil. (The nitrates are readily absorbed by the plants and meet their requirement of the
element nitrogen.)
COMPOUNDS OF NITROGEN :
AMMONIA :
Preparation :
(i)
NH4NO3 + NaOH
NH3 + NaNO3 + H2O ; (NH4)2SO4 + CaO
2NH3 + CaSO4 + H2O
This is a general method and is used as a test for ammonium salts.
(ii)
(iii)
From nitrates and nitrites: When a metal nitrate or nitrite is heated with zinc powder and concentrated NaOH
solution ammonia is obtained. The reactions are
NaNO3 + 7NaOH + 4Zn 4Na2ZnO2 + NH3 + 2H2O
NaNO2 + 3Zn + 5NaOH 3Na2ZnO2 + H2O + NH3
Thus a nitrite or a nitrate can be identified by this reaction but this test cannot make distinction between
them.
The ammonia evolved is passed through quick lime to dry it and collected by the downward
displacement of air. Ammonia cannot be dried using CaCl2, P2O5 or concentrated H2SO4 because
NH3 reacts with all of these.
CaCl2 + 8NH3 CaCl28NH3 ;
P2O5 + 6NH3 + 3H2O 2(NH4)3PO4
H2SO4 +2NH3
(NH4)2SO4 ;
CaO + H2O Ca(OH)2
INDUSTRIAL METHODS OF PREPARATION :
(i)
Principle : Haber process is the most important industrial method of preparing ammonia. This method
was discovered by a German chemist Fritz Haber. The method involves the direct combination of
nitrogen and hydrogen according to the following reaction.
N2 + 3H2
2NH3 + 24.0 kcal
The reaction is reversible, exothermic and formation of NH3 is followed by a decreased in
volume. According to Le Chatelier's principle, the optimum conditions for the greater yield of
ammonia are :
(a) High pressure : Usually a pressure of 200 atmospheres is applied.
(b) Low temperature : The working temperature of 450550C is maintained.
(c) Catalyst : At low temperature, although the yield of ammonia is more yet the reaction is very slow.
In order to speed up the reaction, a catalyst is used. The following catalysts have been proposed
for this purpose.
(i) Finely divided iron with some molybdenum as a promotor.
(ii) Finely divided nickel and sodalime deposited over pumice stone.
(ii)
Cyanamide process :
2000 C
(i)
Chemical properties :
It forms ammonium salts with acids, e.g., NH4Cl, (NH4)2 SO4 etc. As a weak base, it precipitates the hydroxides
of many metals from their salt solutions. For example ,
2 FeCl3 (aq) + 3 NH4OH (aq) Fe2O3 . xH2O (s) + 3 NH4Cl (aq)
(brown ppt)
(ii)
The presence of lone pair of electrons on the nitrogen atoms of the ammonia molecule makes it a Lewis
base. It donates the electrons pair and forms linkage with metal ions and the formation of such complex
compounds finds applications in detection of metal ions such as Cu2+ , Ag+ ; Cd2+ :
Cu2+ (aq) + 4 NH3 (aq)
[Cu(NH3)4]2+ (aq)
(blue)
(deep blue)
AgCl (s)
(colourless)
(white ppt)
(colourless)
Pt , 550 C
(iii)
(iv)
(v)
high pressure
Ammonium salts decompose quite readily on heating. If the anion is not particularly oxidising
(e.g. Cl CO32 or SO42) then ammonia is evolved.
NH4Cl
NH3 + HCl ;
(NH4)2SO4
2NH3 + H2SO4
If the anion is more oxidising (e.g. NO2, NO3 , ClO4 , Cr2O72) then NH4 is oxidised to N2 or N2O.
NH4NO2
N2 + 2H2O ;
2NH3 + 2KMnO4
Neutral
medium
NH4NO3
N2O + 2H2O
A small quantity or all the product may be destroyed by the side reaction given below.
N2H4 + 2NH2Cl
Chloramine
N2 + 2NH4Cl
This reaction is catalysed by heavy metal ions present in solution. For this distilled water is used (rather than
tap water) and glue or gelatin is added to mask (i.e. complex with) the remaining metal ions. The use of
excess of ammonia reduces the incidence of chloramine reacting with hydrazine. The use of a dilute solution
of the reactant is necessary to minimize another side reaction.
3NH2Cl + 2NH3 N2 + 3NH4Cl
OXIDES OF NITROGEN :
Nitrogen forms a number of oxides, N2O, NO, N2O3, NO2 or N2O4 and N2O5, and also very unstable NO3 and
N2O6. All these oxides of nitrogen exhibit p-p multiple bonding between nitrogen and oxygen.
N2O :
Properties :
It is poisonous and when inhaled in small quantities if causes hysterical laughing.
NO :
2NH3 + 2H2O
N2O5 : (a)
(b)
It is anhydride of HNO3
2N2O5
2N2O4 + O2
(c)
(d)
(e)
(f)
(i)
Properties:
It is an unstable, weak acid which is known only in aqueous solution.
(ii)
(iii)
Nitrous acid and nitrites are good oxidizing agents and convert iodides to iodine, ferrous salts to ferric,
stannous to stannic and sulphites to sulphates eg.
2KI + 2HNO2 + 2HCl 2H2O + 2NO + 2KCl + I2
(iv)
With strong oxidizing agents like KMnO4 nitrous acid and nitrites function as reducing agents and get
oxidized to NO3 ions:
2KMnO4 + 5KNO2 + 6HCl 2MnCl2 + 5KNO3 + 3H2O + 2KCl
NITRIC ACID (HNO3) :
Commonly called as Aqua Fortis. This indicates that strong water, when it falls on skin it causes mild
burning.
Preparation :
(i)
(ii)
Ostwald Process :
In the laboratory, nitric acid is prepared by heating KNO3 or NaNO3 and concentrated H2SO4 in a glass retort.
NaNO3 + H2SO4 NaHSO4 + HNO3
On a large scale it is prepared mainly by Ostwalds process.
This method is based upon catalytic oxidation of NH3 by atmospheric oxygen.
4 NH3 (g) + 5 O2 (g) (from air)
(i)
Concentrated nitric acid is a strong oxidising agent and attacks most metals except noble metals such as
gold and platinum. The products of oxidation depend upon the concentration of the acid , temperature and
the nature of the material undergoing oxidation.
Some metals (e.g., Cr , Al) do not dissolve in concentrated nitric acid because of the formation of a passive
film of oxide on the surface.
Nature of HNO3
Changes to
Reactions
M(NO3)2
NH4NO3
N2 O
NO2
M + 2HNO3 M(NO3)2 + H2
4Zn+10HNO3 4Zn(NO3)2 + NH4NO3 + 3H2O
4Zn + 10HNO3 4Zn(NO3)2 + N2O + 5H2O
Zn + 4HNO3 Zn(NO3)2 + 2NO2 + 2H2O
(a) dilute
(b) concentrated
NH4NO3
NO2
4. Pb
(a) dilute
(b) concentrated
NO
NO2
(a) dilute
NO
(b) concentrated
NO2
concentrated
NO2
Sb + 5HNO3 H3SbO4
(C) Metalloids
Sb, As
+ 5NO2 + H2O
antimonic acid
(ii)
Concentrated nitric acid also oxidises nonmetals and their compounds. Iodine is oxidised to iodic acid ,
carbon to carbon dioxide , sulphur to H2SO4 and phosphorus to phosphoric acid.
I2 + 10 HNO3 2 HIO3 + 10 NO2 + 4 H2O
C + 4 HNO3 CO2 + 2 H2O + 4 NO2
S8 + 48 HNO3 (concentrated) 8 H2SO4 + 48 NO2 + 16 H2O
P4 + 20 HNO3 (concentrated) 4 H3PO4 + 20 NO2 + 4 H2O
PHOSPHORUS :
It occurs in nature in the form of stable phosphates. (Animal bones also contain calcium phosphate (58 %)).
The important minerals are:
(i) Phosphorite, Ca3(PO4)2
(ii) Chloraptite, Ca3(PO4)2CaCl2
(iii) Fluoraptite, Ca3(PO4)2CaF2
(iv) Vivianite, Fe3(PO4)28H2O
(v) Redonda phosphate, AlPO4
ALLOTROPIC FORMS OF PHOSPHORUS :
(i)
2Ca3(PO4)2 (from bone-ash) + 10C + 6SiO2 6CaSiO3 + 10CO + P4(s) (electric furnace method)
Properties :
It is white-to-transparent and soft waxy solid. It is soluble in CS2 but insoluble in water. It glows in dark due
to slow oxidation producing yellowish-green light. This phenomenon is called phosphorescence
P4 + 5O2 P4O10
White phosphorus is poisonous. It undergoes oxidation in the presence of air which slowly raises its temperature
and due to its low ignition temperature (~ 30C) after a few moments it catches fire spontaneously. Due to
this reason, it is stored under water.
It exist as tetrahedral P4 molecule and tetrahedral structure remains in the liquid and gaseous states.
P
P
2.21
60
C
(ii)
Red phosphorus:
Preparation :
When white phosphorus is heated in the atmosphere of CO2 or coal gas at 573 K red phosphorus is produced.
This red phosphorus may still contain some white phosphorus which is removed by boiling the mixture with
NaOH where white phosphorus is converted into PH3 gas but red phosphorus remains inert.
P4 + 3NaOH + 3H2O PH3(g) + 3NaH2PO2
It is also prepared by heating white phosphorus with a few crystals of iodine catalyst at 250oC for a few hours
in a closed iron vessel fitted with a safety valve.
Properties :
It is a reddish-violet crystalline solid. It is stable in air and does not
ignite unless it is heated to 400C. It is less reactive than white
phosphorus and does not dissolve in liquid CS2. This is a polymeric
substance forming linear chains like this.
(iii)
Black phosphorus has two forms -black phosphorus and -black phosphorous, -black phosphorus is
formed when red phosphorus is heated in a sealed tube at 803 K. It can be sublimed in air and has opaque
monoclinic or rhombohedral crystal. It does not oxidise in air, -black phosphorus is prepared by heating
white phosphorus at 473 K under high pressure. It does not burn in air upto 673 K.
-black phosphorus is a good conductor of electricity whereas -black phosphorous is non-conductor. -black
phosphorus has layered structure like graphite. The distance between the two layers is found to be 3.68 .
P
P
P
P
P
P
P
P
P
P
P
P
P
P
Density : White phosphorus= 1.83 ; Red phosphorus = 2.20 ; Black phosphorus = 2.70 gm/cc ;
As polymerisation increases compactness increases and therefore, density increases.
Chemical properties of phosphorus :
Reactivity of the various allotropic forms of phosphorus towards other substances decreases in the order:
white > red > black, the last one being almost inert i.e. most stable.
Apart from their reactivity difference, all the forms are chemically similar.
(i)
(ii)
When white phosphorus is heated with CaO and water phosphine gas is evolved.
3CaO + 8P + 9H2O 3Ca(H2PO2)2 + 2PH3
(iii)
2P + 5H2SO4
2H3PO4 + 5SO2 + 2H2O
COMPOUNDS OF PHOSPHORUS :
PHOSPHINE :
Preparation :
(i)
(ii)
In the laboratory, it is prepared by heating white phosphorus with concentrated NaOH solution in an inert
atmosphere of CO2.
P4 + 3 NaOH + 3 H2O PH3 + 3 NaH2PO2
(sodium hypophosphite)
When pure, it is non inflammable but becomes inflammable owing to the presence of P2H4 or P4 vapours. To
purify it from the impurities , it is absorbed in HI to form phosphonium iodide (PH4I) which on treating with
KOH gives off phosphine.
PH4I + KOH KI + H2O + PH3
(iii)
(i)
(ii)
It is slightly soluble in water but soluble in CS2 and other organic solvents. The solution of PH3 in water
decomposes in presence of light giving red phosphorus and H2.
(iii)
When absorbed in copper sulphate or mercuric chloride, the corresponding phosphides are obtained.
3CuSO4 + 2PH3 Cu3P2 + 3H2SO4
3HgCl2 + 2 PH3 Hg3P2 (brownish black) + 6 HCl
(iv)
Properties :
It is colourless crystalline solid having melting point 23.8oC and boiling point 178oC.
(ii)
It dissolves in cold water to form phosphorus acid. It is thus the anhydride of phosphorus acid.
P4O6 + 6H2O 4H3PO3
(iii)
(iv)
(v)
It burns in Cl2 gas forming phosphorus oxytrichloride (POCl3) and phosphoryl chloride (PO2Cl)
P4O6 + 4Cl2 2POCl3 + 2PO2Cl
PHOSPHORUS PENTAOXIDE (P4O10) :
It is dimeric and has the formula P4O10.
Preparation :
It is obtained by burning phosphorus in excess air.
P4 + 5O2 P4O10
Properties:
(i)
(ii)
(iii)
It dissolves in water with hissing sound forming metaphosphoric acid and finally orthophosphoric acid.
P4O10 + 2H2O 4HPO3 ;
4HPO3 + 2H2O 2H4P2O7 ;
2H4P2O7 + 2H2O 4H3PO4
(iv)
It dehydrates concentrated H2SO4 and concentrated HNO3 to SO3 and N2O5 respectively.
distillation
distillation
4HNO3 + P4O10
4HPO3 + 2SO3
(i)
(ii)
The solution containing H3PO3 and HCl is heated to 180oC and HCl gas is driven out. The resulting solution
on crystallization gives white crystals of H3PO3.
Properties :
(i)
It is a white crystalline solid, soluble in water and having melting point of 74oC.
(ii)
When neutralized with bases or alkalies, it forms neutral salts called phosphites which are unstable.
H3PO3 + NaOH NaH2PO3 + H2O
NaH2PO3 + NaOH Na2HPO3 + H2O
(iii)
4H3PO3
3H3PO4 + PH3 (disproportionation)
(iv)
(b)
Mercury (II) chloride on warming with excess of the phosphite solution gives grey metallic mercury.
HPO32 + 2HgCl2 + H2O Hg2Cl2 (white) + 2Cl + H3PO4
Hg2Cl2 (white) + HPO32 + H2O 2Hg (grey) + 2Cl + H3PO4
(ii)
By hydrolysis of PCl5 :
(iii)
(i)
Pure orthophosphoric acid is a white crystalline solid highly soluble in water having melting point of 42oC. It
is a weak acid. It forms two acid salts and one normal salt.
(ii)
(iii)
H2 O
H2 O
phosphate)
(iv)
Action of heat :
220 C
316 C
H3PO4
NaH2PO4
NaPO3 + H2O
2Na2HPO4
Na4P2O7 + H2O
Na(NH4)HPO4
NaPO3 + NH3 + H2O
Oxoacids of Phosphorus
The chemical compositions of the various oxoacids are interrelated in terms of loss or gain of H2O molecule
or O-atom. The structures of some important oxoacids are given below:
PHOSPHORUS HALIDES :
Phosphorus can form two types of halides, PX3 (X = F, Cl, Br, I) and PX5 (X = F, Cl, Br).
PHOSPHORUS TRICHLORIDE :
Preparation :
(i) It is obtained by passing dry chlorine over heated white phosphorus.
P4 + 6Cl2 4PCl3
(ii) It is also obtained by the action of thionyl chloride with white phosphorus.
P4 + 8SOCl2 4PCl3 + 4SO2 + 2S2 Cl2
Properties :
(i) It is a colourless oily liquid and hydrolyses in the presence of moisture.
PCl3 + 3H2O H3PO3 + 3HCl
(ii) It reacts with organic compounds containing OH group such as
CH3COOH, C2H5OH.
3CH3COOH + PCl3 3CH3 COCl + H3PO3
3C2H5OH + PCl3 3C2H5Cl + H3PO3
PHOSPHORUS PENTACHLORIDE :
Preparation :
(i) Phosphorus pentachloride is prepared by the reaction of white phosphorus with excess of dry chlorine.
P4 +10Cl2 4PCl5
(ii) It can also be prepared by the action of SO2Cl2 on phosphorus.
P4 +10SO2 Cl2 4PCl5 +10SO2
Properties :
(i) PCl5 is a yellowish white powder and in moist air, it hydrolyses to POCl3 and finally gets converted to
phosphoric acid.
PCl5 + H2O POCl3 + 2HCl
POCl3 + 3H2O H3PO4 + 3HCl
(ii) When heated, it sublimes but decomposes on stronger heating.
Heat
PCl5
PCl3 +Cl2
(iii) It reacts with organic compounds containing OH group converting them to chloro derivatives.
C2H5OH + PCl5 C2H5Cl + POCl3 + HCl
CH3 COOH + PCl5 CH3 COCl + POCl3 +HCl
(iv)Finely divided metals on heating with PCl5 give corresponding chlorides.
2Ag + PCl5 2AgCl + PCl3
Sn + 2PCl5 SnCl4 + 2PCl3
(v) It is used in the synthesis of some organic compounds, e.g., C2H5Cl, CH3COCl.
FERTILIZER :
PHOSPHATE FERTILIZERS :
(a) These are phosphorus containing direct fertilizers.
(b) Important function of Phosphourus :
(1) It stimulates root formation.
(2) It stimulates rapid growth.
(c) Types of phosphateFertilizers :
(i)
3 Ca(H2PO 4 )2 7CaSO 4
+ 2HF
[3(Ca3(PO4)2CaF2) + 7H2SO4
(ii)
[3(Ca3(PO4)2CaF2) + 14H3PO4
Super phosphate
10 Ca(H2PO 4 )2
+ 2HF
H3PO4 is used to avoid the formation of the insoluble CaSO4 (waste product).
GROUP 16 ELEMENTS : THE OXYGEN FAMILY :
Oxygen, sulphur, selenium, tellurium and polonium constitute group 16 of the periodic table. This is sometimes
known as group of chalcogens the ore forming elements because a large number of metals ores are oxides
or sulphides.
State and Nature :
(a) Only O2 in gaseous state and rest all are solid.
Only form p p bond.
(b) O and S both non metal
(c) Se and Te are metalloids.
(d) Po is metallic.
Occurrence:
Oxygen is the most abundant of all the elements on the earth. Oxygen forms about 46.6% by mass of
earths crust . Dry air contains 20.946% oxygen by volume.
However, the abundance of sulphur in the earths crust is only 0.03-0.1%. Combined sulphur exists primarily
as sulphates such as gypsum CaSO4.2H2O, epsom salt MgSO4 .7H2O, baryta BaSO4 and sulphides such
as galena PbS, zinc blende ZnS, copper pyrites CuFeS2 . Traces of sulphur occur as hydrogen sulphide in
volcanoes.
Selenium and tellurium are also found as metal selenides and tellurides in sulphide ores. Polonium occurs
in nature as a decay product of thorium and uranium minerals.
Electronic Configuration :
The elements of group 16 have six electrons in the outermost shell and have ns2 np4 general valence shell
electronic configuration.
Atomic and Ionic Radii :
Due to increase in the number of shells , atomic and ionic radii increase from top to bottom in the group.
The size of oxygen atoms is however, exceptionally small.
Ionisation Enthalpy :
Ionisation enthalpy decreases down the group. It is due to increase in size. However, the element of this
group have lower ionisation enthalpy values compared to those of group 15 in the corresponding periods. This
is due to the fact that group 15 elements have extra stable half-filled p orbitals electronic configurations.
Electron Gain Enthalpy :
Because of the compact nature of oxygen atom, it has less negative electron gain enthalpy than sulphur.
However from sulphur onwards the value again becomes less negative upto polonium.
Electronegativity :
Next to fluorine, oxygen has the highest electronegativity value amongst the elements. Within the group,
electronegativity decrease with an increase in atomic number. This indicates that the metallic character
increases from oxygen to polonium.
Melting Point and Boiling Point :
From oxygen to tellurium melting and boiling points go on increasing. The M.P. of polonium is less than
tellurium.
Allotropy and Allotropic Forms :
Oxygen has two allotropes O2 and O3. The type of allotropy is called as monotropy. Sulphur has number of
allotropic forms. The most common are Rhombic sulphur, monolinic sulphur, plastic sulphur, colloidal sulphur
etc.
Physical Properties :
Oxygen and sulphur are non-metal, selenium and tellurium metalloids, whereas polonium is a metal. Polonium
is radioactive and is short lived (Half-life 13.8 days). The melting and boiling points increase with an increase
in atomic number down the group. The larger difference between the melting and boiling points of oxygen and
sulphur may be explained on the basis of their atomicity; oxygen exist as diatomic molecules (O2) whereas
sulphur exists as polyatomic molecule (S8).
Catenation :
Tendency for catenation decreases down the group. This property is prominently displayed by sulphur (S8).
The SS bond is important in biological system and is found in some proteins and enzymes such as
cysteine.
Selenium has unique property of photo conductivity and is used in photocopying machines and also a
decolouriser of glass.
ATOMIC AND PHYSICAL PROPERTIES
Ele m e nt
Se
Te
Atom ic Num be r
16
34
52
Atom ic Ma ss
16
32.06
78.96
127.6
[He] 2s 2 2p 4
[Ne] 3s 2 3p 4
[Ar] 3d10 4s 2 4p 4
Cova le nt Ra dius / pm
74
103
119
142
Ionic Ra dius X
140
184
198
221
1314
1000
941
869
II
3388
2251
2045
1790
/ pm
3.5
2.44
2.48
2.01
1.32
2.06
4.19
6.25
Me lting point / K
54
393
490
725
Boiling point / K
90
718
958
1260
(293 K)]
Chemical Properties :
Oxidation states and trends in chemical reactivity :
The elements of group 16 exhibit a number of oxidation states. The stability of -2 oxidation state decreases
down the group. Polonium hardly shows -2 oxidation states. Since electronegativity of oxygen is very high,
it shows only negative oxidation states as -2 except in the case of OF2 where its oxidation states is + 2.
Other elements of the group exhibit + 2, + 4, + 6 oxidation states but + 4 and + 6 are more common. Sulphur,
selenium and tellurium usually show + 4 oxidation in their compounds with oxygen and +6 oxidations state
with fluorine. The stability of +6 oxidation state decreases down the group and stability of + 4 oxidation state
increases (inert pair effect). Bonding in + 4 and + 6 oxidation states are primarily covalent.
ETOOS ACADEMY Pvt. Ltd
F-106, Road No.2 Indraprastha Industrial Area, End of Evergreen Motor,
BSNL Lane, Jhalawar Road, Kota, Rajasthan (324005) Tel. : +91-744-242-5022, 92-14-233303
HNO3 oxidises sulphur to H2SO4 (S + VI) but only oxidises selenium to H2SeO3 (Se + IV) as the atoms are
smaller and there is poor shielding of 3d electrons as a result the electrons are held more tightly with
nucleus.
Polonium shows metallic properties since it dissolves in H2SO4, HF, HCl and HNO3 forming pink solution of
PoII. However PoII is strongly radio active and the -emission decomposes the water and the PoII is quickly
oxidised to yellow solution of PoIV.
Anomalous behaviour of oxygen :
The anomalous behaviour of oxygen, like other member of p-block present in second period is due to its
small size and high electronegativity. One typical example of effects of small size and high electronegativity
is the presence of strong hydrogen bonding in H2O which is not found in H2S.
The absence of d orbitals in oxygen limits its covalency to four and in practice, rarely increases beyond two.
On the other hand, in case of other elements of the group, the valence shell can be expanded and covalence
exceeds four.
(i)
Reactivity with hydrogen : All the elements of group 16 form hydrides of the type H2E (E = S, Se, Te, Po).
Some properties of hydrides are given in Table. Their acidic character increases from H2O to H2Te. The
increase in acidic character can be understood in terms of decrease in bond (H-E) dissociation enthalpy
down the group. Owing to the decrease in bond (H-E) dissociation enthalpy down the group , the thermal
stability of hydrides also decreases from H2O to H2Po. All the hydrides except water possess reducing
property and this property increases from H2S to H2Te.
PROPERTIES OF HYDRIDES OF GROUP 16 ELEMENTS
Property
H2O
H2 S
H2Se
H2Te
m.p./K
273
188
208
222
b.p./K
373
213
232
269
H-E distance/pm
96
134
146
169
HEH angle ()
104
92
91
90
-286
-20
73
100
463
347
276
238
-1
fH/kJ mol
-1
Dissociation constant
1.8 10
-16
1.3 10
-7
1.3 10
-4
2.3 10
-3
(ii)
Reactivity with oxygen : All these elements form oxides of the EO2 and EO3 types where E = S, Se, Te or
Po. Ozone (O3) and sulphur dioxide (SO2) are gases while selenium dioxide (SeO2) is solid. Reducing
property of dioxide decreases from SO2 to TeO2 ; SO2 is reducing while TeO2 is an oxidising agent. Besides
EO2 type sulphur, selenium and tellurium also form EO3 type oxides (SO3, SeO3, TeO3). Both types of oxides
are acidic in nature.
(iii)
Reactivity toward the halogens : Elements of group 16 form a larger number of halides of the type EX6,
EX4 and EX2 where E is an element of the group 16 and X is an halogen. The stabilities of the halides
decrease in the order F > Cl > Br > l. Amongst hexahalides, hexafluorides are the only stable halides. All
hexafluorides are gaseous in nature. They have octahedral structure. Sulphur hexafluoride SF6 is exceptionally
stable for steric reasons.
Amongst tetrafluorides, SF4 is a gas , SeF4 liquid and TeF4 a solid These fluorides have sp3d hybridisation
and thus, have trigonal bipyramidal structure in which one of the equatorial position is occupied by a lone pair
of electrons. This geometry is also regarded as see - saw geometry.
All elements except selenium form dichlorides and dibromides. These dihalides are formed by sp3 hybridisation
and thus have tetrahedral structure. The well known monohalides are dimeric in nature, Examples are
S2F2, S2Cl2, S2Br2, Se2Cl2 and Se2Br2. These dimeric halides undergo disproportionation as given below :
2Se2Cl2 SeCl4 + 3Se.
DIOXYGEN (O2) :
It differs from the remaining elements of the VIth group because of the following properties.
(A) small size
(B) high electronegativity and
(C) non-availability of d-orbitals.
Preparation :
(i)
450 C
2 HgO
2 Hg + O2 ;
(ii)
350 0 C
4 Ag + O2
2 Ag2O
KClO3
2 KCl + 3O2 (laboratory method) ; 4 K2Cr2O7
4 K2CrO4 + 2 Cr2O3 + 3O2
(iii)
(iv)
(vi)
2 HOCl 2HCl + O2
(vii)
500 C
800 C
2 BaO + O2(air)
2BaO2 ; 2 BaO2
2 BaO + O2
Properties :
Colourless , odourless and tasteless gas. It is paramagnetic and exhibits allotropy. Three isotopes of oxygen
are
16
17
8O , 8O
and
18
8O .
OXIDES :
(i)
Acidic oxides :
The covalent oxides of non-metal are usually acidic; dissolves in water to produce solutions of acids
e.g., CO2, SO2 , SO3, N2O5 , N2O3 , P4O6 , P4O10, Cl2O7, CrO3 , Mn2O7 etc. They are termed as acid anhydride.
Cl2O7 + H2O 2 HClO4 ; Mn2O7 + H2O 2 HMnO4
(ii)
Basic oxides :
Metallic oxides are generally basic oxides. They either dissolve in water to form alkalies or combine with
acids to form salts and water or combine with acidic oxides to form salts; e.g., Na2O, CaO. CuO, FeO, BaO
etc.
Na2O + H2O 2 NaOH ; CaO + H2O Ca(OH)2 ; CuO + H2SO4 CuSO4 + H2O
The metallic oxides with lowest oxidation sate is the most ionic and the most basic but with increasing
oxidation sate the acidic character increases e.g., CrO is basic, Cr2O3 amphoteric and CrO3 acidic.
(iii)
Neutral Oxides :
They neither combine with acids nor with the bases to form salts e.g., CO, N2O, NO etc.
(iv)
Amphoteric Oxides :
Many metals yield oxides which combine with both strong acid as well as strong bases e.g., ZnO, Al2O3,
BeO, Sb2O3, Cr2O3, PbO, SnO, SnO2, GaO etc.
PbO + 2 NaOH Na2 PbO2 + H2O ; PbO + H2SO4 PbSO4 + H2O
Cr2O3 + 2 NaOH Na2Cr2O4 + H2O; Cr2O3 + 3 H2SO4 Cr2(SO4)3 + 3 H2O
(v)
Mixed Oxides :
They behave as mixture of two simple oxides.
e.g.,
Pb3O4 (2PbO + PbO2) ; Fe3O4 (FeO + Fe2O3) ; Mn3O4 (2 MnO + MnO2)
(vi)
Peroxides :
They react with dilute acids and form H2O2, e.g., Na2O2, K2O2, BaO2 etc. They contain O22 ions.
Na2O2 + H2SO4 Na2SO4 + H2O2
They also react with water forming O2 .
Na2O2 + H2O 2NaOH + 1/2O2
(vii)
Super Oxides :
They contain O2 ion, e.g., KO2 , RbO2 and CsO2 . These oxides react with water forming H2O2 and O2
2 KO2 + 2 H2O 2 KOH + H2O2 + O2.
OZONE (O3) :
Preparation :
It is prepared by passing silent electric discharge through pure and dry oxygen.
energy
O + O
O2
O2 + O O3 ; H = 2845 kJ mol-1
3O2
2O3
Mixture obtained contains 5-10% ozone by volume and this mixture is called ozonised oxygen.
Properties:
(i)
Dark blue gas which forms a blue liquid on cooling and on solidification forms violet black crystals. The colour
is due to intense absorption of red light. It also absorbs strongly in the UV region. Thus it protects the people
on the earth from the harmful UV radiation from the sun. It has sharp smell often associated with sparking
electrical equipment. It is toxic and is slightly soluble in water but more in turpentine oil, glacial acetic acid
or CCl4. O3 molecule is diamagnetic but O3 is paramagnetic.
(ii)
Oxidising agent :
(b)
(c)
It oxidises H2S to S.
H2S + O3 H2O + S (yellow)
(iii)
I4O9 yellow solid has the composition I+3 (IO3)3. Formation of this compound is a direct evidence in favour of
basic nature of I2 (i.e. its tendency to form cations).
(iv)
(v)
Bleaching Action :
O3 also bleaches coloured substances through oxidation.
(vi)
Ozonolysis :
Alkenes, alkynes react with ozone forming ozonides.
O
CH2 CH2
CH2 = CH2 + O3
(vii)
Zn H2O
2HCHO
ZnO
Tailing of mercury
Pure mercury is a mobile liquid but when brought in contact with O3 its mobility decreases and it starts
sticking to glass surface forming a type of tail due to the dissolution of Hg2O (mercury sub-oxide) in Hg.
2 Hg + O3 Hg2O + O2
Uses :
1. As a germicide and disinfectant for sterilising water and improving the atmosphere of crowded places.
2. For detecting the position of double bond in the unsaturated organic compounds.
3. In mfg. of artificial silk, synthetic camphor, KMnO4 etc.
4. It is also used for bleaching oil, ivory, flour starch etc.
HYDROGEN PEROXIDE (H2O2) :
Preparation :
(i)
Laboratory method:
BaO2 . 8H2O + H2SO4 (cold) BaSO4 (white) + H2O2 + 8H2O
BaSO4 is filtered to get aqueous hydrogen peroxide.
(ii)
Since H2SO4 can decompose H2O2 at a higher temperature, therefore, the reaction should be carried
out at low temperature or H3PO4 can be used in place of H2SO4
H +
at cathode : H+ + e
1
H
2 2
80 90 C
(iii)
OH
O
C2H5
O2 (air)
(Oxidation)
C2H5
+ H2O2
H2 (Ni)
(Reduction)
OH
2- Ethyl anthraquinol
O
2-Ehtylanthraquinone
(i)
Properties :
Colourless viscous liquid which appears blue in the larger quantity and is soluble in water (due to H- bonding)
in all proportions and form a hydrate H2O2.H2O (melting point 221 K).
(ii)
Its boiling point 423 K is more than water but freezing point (4C ) is less than water. Density and dielectric
constant are also higher than H2O
(iii)
Its aqueous solution is more stable than the anhydrous liquid where it decomposes into water and O2 slowly
on exposure to light.
2H2O2 2H2O + O2
H2O2 is not kept in glass containers because traces of alkali metal ions from the glass can catalyse
the explosive decomposition of H2O2 Therefore, aqueous solution is stored in plastic or wax-lined glass
containers and some urea or phosphoric acid or glycerol is added to that solution because these compounds
have been found to behave as negative catalyst for the decomposition of H2O2
(iv)
(v)
Oxidising Agent :
2e + 2H+ + H2O2 2H2O ; SRP = + 1.77 v
2e + H2O2 2OH- ; SRP = + 0.87 v
On the basis of the above potentials, we can say that H2O2 is strong oxidising agent in acidic
medium but kinetically it is found that reactions are faster in basic medium.
(A)
In acidic medium :
(a)
It oxidises PbS to PbSO4.
H2O2 H2O + [O] 4
PbS + 4[O] PbSO4
(B)
(vi)
(b)
Potassium iodide and starch produces deeper blue colour with acidified H2O2.
H2O2 + 2H+ 2I I3 + 2H2O
In alkaline medium :
(a)
(b)
2NaBO2 + 2H2O2 + 6H2O Na2 [(OH)2 B(O-O)2 B(OH)2 ] 6H2O (sodium per oxoborate)
(b)
It reduces O3 to O2..
H2O2 + O3 H2O + 2O2
(c)
amyl alcohol
CrO5 bright blue coloured compound soluble in diethyl ether, amyl alcohol and amyl acetate.
CrO5 + H2SO4 2Cr2 (SO4)3 + 6H2O + 7O2
OH
(ii)
2 HCOOH + H2
2 HCHO + H2O2
pyrogallol
When this reaction is carried out in dark, it is accompanied by emission of light (yellow coloured). It is an
example of chemiluminescence.
(iii)
An acidified solution of titanium salt gives yellow or orange colour with H2O2.
Ti+4 + H2O2 + 2H2O H2TiO4 (yellow/orange red) + 4H+
Orange red coloured in slightly acid solution and yellow colour with very dilute solution.
Uses :
1.
2.
3.
4.
SULPHUR (S) :
ALLOTROPIC FORMS OF SULPHUR :
Sulphur forms numerous allotropes of which the yellow rhombic ( - sulphur) and monoclinic ( - sulphur)
forms are the most important. The stable forms at room temperature is rhombic sulphur, which transforms to
monoclinic sulphur when heated above 369 K.
RHOMBIC SULPHUR (- SULPHUR) :
This allotrope is yellow in colour , melting point 385.8 K and specific gravity 2.06. Rhombic sulphur crystals
are formed on evaporating the solution of roll sulphur in CS2. It is insoluble in water but dissolved to some
extent in benzene, alcohol and ether. It is readily soluble in CS2 .
MONOCLINIC SULPHUR ( - SULPHUR) :
Its melting point is 393 K and specific gravity 1.98. It is soluble in CS2. This form of sulphur is prepared by
melting rhombic sulphur in a dish and cooling till crust is formed. Two holes are made in the crust and the
remaining liquid poured out. On removing the crust, colourless needle shaped crystals of - sulphur are
formed. It is stable above 369 K and transforms into - sulphur below it . Conversely, - sulphur is stable
below 369 K and transforms into - sulphur above this. At 369 K both the forms are stable. This temperature
is called transition temperature.
Both rhombic and monoclinic sulphur have S8 molecules these S8 molecules are packed to give different
crystal structures. The S8 ring in both the forms is puckered and has a crown shape. The molecular dimensions
are given in figure.
S
S
20
4
pm
S
107 o
102.2o
S
S
205.7 pm
S
S
S
(b)
(a)
Sulphur melts to form a mobile liquid. As the temperature is raised the colour darkens. At 160C C8 rings
break, and the diradicals so formed polymerize, forming long chains of up to a million atoms. The viscosity
increases sharply, and continues to rise up to 200C. At higher temperatures chains break, and shorter
chains and rings are formed, which makes the viscosity decrease upto 444C, the boiling point. The vapour
at 200C consists mostly of S8 rings, but contains 1-2% of S2 molecules. At elevated temperature (~1000 K),
S2 is the dominant species and is paramagnetic like O2, and presumably has similar bonding. S2 gas is
stable upto 2200C.
The sulphur is mined using a process called as Frasch process.
From hydrocarbons contaminated with H2S or a stream of gas containing H2S. It involves two steps :
catalyst converter
Burn
3S(g + 2H2O(g)
(i) H2S + O2
SO2 + H2S(ii) H2S + SO2
200 to 300 C
(i)
(ii)
(i)
(ii)
(iii)
COMPOUNDS OF SULPHUR :
HYDROGEN SULPHIDE (H2S) :
Preparation :
FeS + H2SO4 FeSO4 + H2S
It is prepared in kipps apparatus
Preparation of pure H2S gas
Sb2S3 (pure) + 6 HCl (pure) 2 SbCl3 + 3 H2S
Properties :
Colourless gas with rotten egg smell .
Moderately soluble in water but solubility decreases with increasing temperature.
Reducing Agent :
Acts as a strong reducing agent as it decomposes evolving hydrogen.
(a)
H2S + X2 2 HX + S;
(b)
(c)
moisture
H2S + SO2
H2O + S;
H2O + S
2H2O + NO2 + S
SULPHUR DIOXIDE :
Preparation :
(i)
(ii)
Burn
S + O2 or air
SO2
By heating Cu or Ag with concentrated H2SO4
Cu + H2SO4 CuSO4 + 2H2O + SO2
(iii)
(iv)
(i)
(ii)
Properties :
Colourless gas with burning sulphur smell.
It is heavier than air and is highly soluble in water. SO2 in solution is almost completely present as
SO2.6H2O and only traces of H2SO3.
(iii)
Neither burns nor helps in burning but burning magnesium and potassium continue to burn in its atmosphere.
3Mg + SO2 2 MgO + MgS ; 4K + 3SO2 K2SO3 + K2S2O3
(iv)
Acidic Nature : Acidic oxide and thus dissolve in water forming sulphurous acid.
SO2 + H2O H2SO3
(v)
Addition Reaction :
Sun light
SO2 + Cl2
SO2Cl2 (sulphuryl chloride)
SO2 + O2
(vi)
Reducing Nature :
It is a more powerful reducing agent in alkaline medium than in acidic medium.
H2O + SO2 H2SO3 ; H2SO3 + H2O H2SO4 + 2H
(a)
(b)
(vii)
(viii)
Bleaching Action :
SO2 + 2H2O H2SO4 + 2H
This is due to the reducing nature of SO2
Coloured matter + H
colourless matter..
Air oxidation
(ii)
(i)
Fe2(SO4)3
Fe2O3 + 3SO3
Properties :
Acidic Nature :
Dissolves in water forming sulphuric acid
SO3 + H2O H2SO4
(ii)
(iii)
Oxidising Nature :
1000 C
3SO2
(a)
2SO3 + S
(c)
SO3 + PCl5 POCl3 + SO2 + Cl2
(b)
(d)
OXYACIDS OF SULPHUR :
Sulphur forms a number of oxoacid such as H2SO3, H2S2O4, H2S2O5, H2S2O6 (x = 2 to 5,) H2SO4, H2S2O7,
H2SO8. Some of these acids are unstable and cannot be isolated. They are known in aqueous solution or in
the forms of their salts. Structures of some important oxoacids are shown in figure.
(a)
(b)
Properties :
Sulphuric acid is a colourless, dense, oily liquid with a specific gravity of 1.84 at 298 K. The acid freezes at
283 K and boils at 611 K. It dissolves in water with the evolution of a larger quantity of heat.
The chemical reaction of sulphuric acid are as a result of the following characteristics : (a) low volatility (b)
strong acidic character (c) strong affinity for water and (d) ability to act as an oxidising agent in aqueous
solution,
(i)
(ii)
CO + CO
(iii)
Hot concentrated sulphuric acid is moderately strong oxidising agent. In this respect it is intermediate
between phosphoric and nitric acids. Both metals and non-metals are oxidised by concentrated sulphuric
acid, which is reduced to SO2.
Cu + 2H2SO4 (concentrated) CuSO4 + 2H2O
3S + 2H2SO4 (concentrated) 3SO2 + 2H2O
C + 2H2SO4 (concentrated) CO2 + 2SO2 + 2H2O
(iv)
(v)
Uses :
Sulphuric acid is a very important industrial chemical. A nations industrial strength can be judged by the
quantity of sulphuric acid it produces and consumes .It is needed for the manufacture of hundreds of other
compounds also in many industrial processes .The bulk of sulphuric acid produced is used in the manufacture
of fertilisers (e.g., ammonium sulphate, superphosphate). Other uses are in : (a) petroleum refining (b)
manufacture of pigment, paints and dyestuff intermediates (c) detergent industry (d) metallurgical applications
(e.g., cleansing metal before enameling, electroplating and galvanising) (e) storage batteries (f) in the
manufacture of nitrocellulose products and (g) as a laboratory reagent.
SODIUM THIOSULPHATE (Na2S2O3 .5H2O) :
Preparation :
(i)
Na2SO3 + S
Na2S2O3
(ii)
Na2CO3 + 2SO2 + H2O 2NaHSO3 + CO2 ; 2NaHSO3 + Na2CO3 2Na2SO3 + H2O + CO2
Na2SO3 + S
Na2S2O3
(iii)
(iv)
6NaOH + 4S
Na2S2O3 + 2Na2S + H2O
(i)
Properties :
It is a colourless crystalline substance soluble in water which loses water of crystallisation on strong heating
(ii)
As antichlor :
It removes the chlorine from the surface of fibres (while dyeing) according to following reaction.
Na2S2O3 + 4Cl2 + 5H2O 2NaHSO4 + 8HCl
Therefore , it is known as antichlor.
(iii)
(iv)
(c)
(d)
(v)
4Na2S2O3
3Na2SO4 + Na2S5
(vi)
H2O ( All)
(vii)
2.
In photography as fixer.
3.
2.
Which out of the following gases is obtained when ammonium dichromate is heated (A) Oxygen
(B) Ammonia
(C) Nitrogen
(D) Nitrous oxide
3.
Among the trihalides of nitrogen which one is most basic (A) NF3
(B) NCl3
(C) NI3
(D) NBr3
4.
The correct sequence of decrease in the bond angle of the following hydrides is - :
(A) NH3> PH3 > AsH3> SbH3
(B) NH3> AsH3 > PH3> SbH3
(C) SbH3> AsH3 > PH3> NH3
(D) PH3> NH3 > AsH3> SbH3
5.
6.
(C) both
(D) none
7.
8.
9.
Which one of the following does not undergo hydrolysis (A) AsCl3
(B) SbCl3
(C) PCl3
(D) NF3
10.
Which one of the following properties of white phosphorous are shared by red phosphorous (A) It dissolves in CS2
(B) It burns when heated in air
(C) It reacts with NaOH to give PH3
(D) It phosphorescences in air
11.
12.
13.
14.
15.
16.
(D) Bi2O3
(D) none
(D) BiF5
17.
The dimerisation of NO2 as the temperature is lowered is accompanied by (A) An increase in pressure
(B) A darkening in colour
(C) A decrease in paramagnetism
(D) The formation of a colloid
18.
Which of the following reagents can separate nitric oxide from nitrous oxide (A) Sodium nitroprusside solution
(B) Ferrous sulphate solution
(C) Nessler's reagent
(D) Tollen's reagent
19.
Phosphine is not obtained by the reaction when (A) White P is heated with NaOH
(C) Ca3P2 reacts with water
20.
In P4O6 the number of oxygen atoms bonded to each phosphorus atom is (A) 1.5
(B) 2
(C) 3
(D) 4
21.
22.
NH4Cl (s) is heated in test tube. Vapours are brought in contact with red litmus paper, which changes to
blue and then to red. It is because of :
(A) formation of NH4OH and HCl
(B) formation of NH3 and HCl
(C) greater diffusion of NH3 than HCl
(D) greater diffusion of HCl than NH3
23.
Which of the following will combine with Fe(II) ion to form a brown complex compound ?
(A) N2O
(B) NO
(C) N2O3
(D) NO2
24.
(C) Pb(NO3)2
(C) CO
25.
26.
(D) KNO3
(D) NO2
27.
Which of the following statements are not correct about the hydrides of group 15 elements (A) The hydrides of the elements of group 15 are ionic and have planar triangular shape
(B) The thermal stability of the hydrides decreases down the group
(C) the basic character of the hydrides decreases down the group
(D) The reducing nature of the hydrides increases down the group
28.
(C) H3AsO3
(D) H3SbO3
29.
30.
31.
32.
33.
(C) NH2OH
PCl5 exists but NCl5 does not because (A) Nitrogen has no vacant d-orbitals
(C) Nitrogen atom is much smaller
(C) N2O4
(D) NH3
(D) N2O5
(D) N2O5
(D) BaSO4 + N2 + O2
34.
35.
36.
37.
(D) H3PO4
(D) Hg
38.
39.
The compound which has molecular nature in gas phase but ionic in solid state is :
(A) PCl5
(B) POCl3
(C) P4O10
(D) PCl3
40.
(D) H4P2O7
(D) N2O
41.
42.
43.
44.
When white pnosphorous is heated with caustic soda, the compounds formed are (A) PH3 + NaH2PO3
(B) PH3 + NaH2PO2
(C) PH3 + Na2HPO3 (D) PH3 + NaH2PO4
45.
46.
Phosphine produces smoky rings when it comes in contact with air because (A) It reacts with water vapour
(B) It reacts with nitrogen
(C) It burns in air
(D) It contains impurities of P2H4
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47.
48.
(D) As4O10
49.
Which of the following oxy acids of Phosphorus is a reducing agent and monobasic (A) H3PO2
(B) H3PO3
(C) H3PO4
(D) H4P2O6
50.
(D) NO2
51.
52.
53.
54.
55.
(D) N2O3
Least acidic and most acidic oxides of nitrogen are (A) N2O, N2O5
(B) N2O, N2O4
(C) N2O, NO
56.
The number of molecules of water needed to convert one molecule of P2O5 into orthophosphoric acid
is
(A) 2
(B) 3
(C) 4
(D) 5
57.
(D) nitrogen
58.
59.
60.
61.
62.
(D) H4P2O7
Group 16th
1.
Which of the following hydrides of the oxygen family shows the lowest boiling point?
(A) H2O
(B) H2S
(C) H2Se
(D) H2Te
2.
3.*
(D) CaCO3
4.
(A) 2
(B) O3
(C) O4
(D) 2O5
5.
(C) I2O4
6.
7.
(D) I4O9
(D) All in equal amounts
8.
Hydrogen sulphide reacts with lead acetate forming a black compound which reacts with H2O2 to form
another compound. The colour of the compound is (A) Black
(B) Yellow
(C) White
(D) Pink
9.
Oxygen is gas but sulphur is solid because (A) Oxygen is composed of discrete molecules while sulphur is polymeric
(B) Molecular weight of sulphur is much higher than that of oxygen
(C) Oxygen is a stronger oxidising agent than sulphur
(D) Boiling point of sulphur is much higher than that of oxygen
10.
One gas bleaches the colour of the flowers by reduction while the other by oxidation. The gases are(A) CO and CO2
(B) H2S and Br2
(C) SO2 and Cl2
(D) NH3 and SO3
11.
12.
13.
(D) H2S2O3
Which one of the following gives mixture of SO2 and SO3 on heating ?
(A) ZnSO4
(B) CuSO4
(C) Fe2 (SO4)3
(D) FeSO4
14.
15.*
16.*
(D) HSO4
(D) IO3 to I2
17.
Which of the following product is formed by the reaction of sulphur dioxide with chlorine in presence of
charcoal ?
(A) SO2Cl
(B) SO2Cl2
(C) SOCl2
(D) SO3Cl
18.
19.
When H2S is passed through acidified K2Cr2O7 solution, the solution turns :
(A) yellow
(B) blue
(C) green
(D) white
20.
The following catalyst is used in the manufacturing of sulphuric acid by lead chamber process.
(A) NO
(B) NO2
(C) Pt
(D) V2O5
21.
22.
23.
24.
25.
The term 'thio' is used in the names of all of the following compounds except :
(A) Na2S2O3
(B) Na2S2O6
(C) NaSCN
(D) Na2SO3
26.
The reaction between ferric salt and aqueous sodium thiosulphate produces pink colour which soon
diminishes. The pink colour is due to the formation of :
(A) [Fe(S2O3)3]4
(B) [Fe(S2O3)2]
(C) Fe2 (S4O6)3
(D) none of these
27.
The decreasing order of catenation of group 16 elements is (A) O > S > Se > Te (B) S > O > Se > Te (C) S > Se > O > Te (D) O > S > Te > Se
28.
The correct increasing order of dipole moments of the following is (A) H2O < H2S < H2Se < H2Te
(B) H2Te < H2Se < H2S < H2O
(C) H2Se < H2Te < H2O < H2S
(D) H2S < H2O < H2Se < H2Te
29.
30.
Oxygen is more electronegative than sulphur, yet H2S is acidic while H2O is neutral. This is because(A) Water is a highly associated compound
(B) H S bond is weaker than H O bond
(C) H2S is a gas while H2O is a liquid
(D) The molecular weight of H2S is more than that of H2O
31.
The acidic character of dioxides of members of oxygen family decreases in the order (A) SeO2 > SO2 > TeO2 > PoO2
(B) SO2 > SeO2 >Te O2 > PoO2
(C) PoO2 > TeO2 > SeO2 > SO2
(D) TeO2 > PoO2 > SeO2 > SO2
32.
A solution of SO2 in water reacts with H2S precipitating sulphur. Here SO2 acts as (A) An oxidising agent (B) A reducing agent
(C) An acid
(D) A catalyst
33.
(D) Sb2O5
34.
35.
The oxidation number of sulphur in S8, S2F2 and H2S respectively are :
(A) 0, + 1 and 2
(B) + 2, + 1 and 2
(C) 0, + 1 and + 2
(D) 2, + 1 and 2
(C) Se Se
(D) Te Te
(C) H2SO3
(D) H2SO5
36.
37.
38.
(B) H2S2O8
39.
Concentrated H2SO4 is not used to prepare HBr from KBr because it (A) Oxidizes HBr
(B) Reduces HBr
(C) Causes disproportionation of HBr
(D) Reacts too slowly with KBr
40.
Vegetable colouring matter in presence of moisture is bleached by SO2 due to (A) Oxidation
(B) Reduction
(C) Sulphonation
(D) Unsaturation
41.
When water is added in conc. H2SO4 the reaction is exothermic because (A) H2SO4 is viscous
(B) Hydrates of H2SO4 are formed
(C) H2SO4 is corrosive
(D) None of these
42.
43.
(A) NO 3
(C) BO 33
(D) CO23
44.
The decreasing tendency to exist in puckered 8-membered ring structure is (A) S > Se > Te > Po
(B) Se > S > Te > Po
(C) S > Te > Se > Po
(D) Te > Se > S > Po
45.
The increasing thermal stability of the hydrides of group 16 follows sequence (A) H2O < H2S < H2Se < H2Te
(B) H2Te < H2Se < H2S < H2O
(C) H2S < H2O < H2Se < H2Te
(D) H2Se < H2O < H2S < H2Te
46.
47.
(B) sp3d-Hybridized
(C) d2sp3-Hybridized
(D) sp3-Hybridized
The correct order of decreasing stability of hexafluorides of group 16 members is (A) SF6 > SeF6 > TeF6
(B) TeF6 > SeF6 > SF6
(C) SF6 > TeF6 > SeF6
(D) TeF6 >SF6 > SeF6
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Column I
Column II
(a)
(b)
Laughing gas
(c)
Nitrolim
(d)
Brown ring
(iv) Ammonia
(e)
(f)
2.
Column I
Column II
(a)
H3PO3 (Unbalanced)
(i) N2O
(b)
(c)
Pb(NO3)2 (Unbalanced)
(iii) PH3
(d)
NH4NO3 (Unbalanced)
(iv) NaH2PO2
(e)
(v) NO
(vi) H3PO4
3.
Column I
(A) PCl5
Column II
Moist
(P) Hydrolysis
Air
(C) H3PO3
(R) Disproportionation
CO 2
Group 16th
4.
Column I
Column II
(ii) Sulphur
(iv) Ozone
5.
6.
Column I
Column II
(c) Ozone
(h) Sulphur
Column I
Column II
Distillation
(A) (NH4)2S2O8 + H2O
(P) Hydrolysis
OH
fusion
(C) Na2SO3
temperatur e
(R) Disproportionation.
(S) In one of the products the central atom has sp3 hybridisation.
ASSERTION / REASONING
DIRECTIONS :
The following questions consist of two statements one labelled ASSERTION (A) and the another
labelled REASON (R). Select the correct answers to these questions from the codes given below :
(A) Both Assertion and Reason are true and Reason is the correct explanation of Assertion.
(B) Both Assertion and Reason are true but Reason is not correct explanation of Assertion
(C) Assertion is true but Reason is false
(D) Assertion is false but Reason is true
Group 15th
7.
8.
9.
10.
Assertion : PCl5 is covalent in gaseous and liquid state but ionic in solid state.
Reason : PCl5 in solid state consists of tetrahedral PCl4+ cation and octahedral PCl6 anion.
11.
Assertion : Among nitrogen halides NX 3, the dipole moment is highest for N3 and lowest for NF3.
Reason : Nitrogen halides NX 3 , have trigonal pyramidal structure.
12.
13.
14.
Assertion : Both H3PO3 and H3PO4 have the same number of hydrogen atoms but H3PO4 is a tribasic acid
and H3PO3 is a diabasic acid.
Reason : 1 mol of H3PO3 is neutralised by 2 mol of NaOH while 1 mol of H3PO4 is neutralised by 3 mol of
NaOH.
Group 16th
15.
16.
Assertion : At room temperature oxygen exists as a diatomic gas, where as sulphur exists as solid.
Reason : The catenated - O - O - O - changes are less stable as compared to O = O molecule.
17.
18.
19.
Assertion : Sulphuric acid is less viscous than water due to intramolecular hydrogen bonding.
Reason : Concentrated sulphuric acid has a great affinity for water.
20.
21.
22.
Assertion : A pink coloured solution of potassium permangnate turns green on passing O3 through it.
Reason : K2MnO4 is oxidised by O3 to KMnO4
23.
24.
Assertion : Reaction of SO2 and H2S in the presence of Fe2O3 catalyst gives elemental sulphur.
Reason : SO2 acts as a reducing agent.
25.
26.
TRUE / FALSE
Group 15th
27.
Conc. HNO3 renders iron passive probably because of the formation of an oxide film.
28.
29.
30.
31.
Red phosphorus is less volatile than white phosphorus because the former has a tetrahedral structure.
32.
33.
34.
35.
36.
37.
38.
39.
40.
Group 16th
41.
SO2 does not help in combustion but burning magnesium continues burning in its atmosphere.
42.
Concentrated sulphuric acid must be slowly added to water with constant stirring for dilution.
43.
44.
High boiling point and high viscocity of sulphuric acid is due to intra molecular hydrogen bonding
45.
46.
47.
48.
49.
In the solid state, SO3 exists in several modifications having a cyclic trimeric or a linear polymeric chain
structure.
50.
52.
53.
54.
55.
56.
A mixture of conc. HNO3 and __________ is used for the nitration of organic compounds.
57.
58.
In P4O10, the number of oxygen atoms bonded to each phosphorus atom is _________ .
59.
60.
Among PCl3 , CH3+ , NH2 and NF3 ____________ is least reactive towards water.
61.
62.
The formula of hydrazine is ___________ the oxidation state of nitrogen in hydrazine is _________.
63.
64.
There are ___________ single bonds and __________ double bonds in P4O10 molecule.
65.
The molecules of PCl5 in solid state are _________ in nature consisting tetrahedral __________
cations and ___________ [PCl6] ions.
66.
Red phosphorus is __________ reactive than white phosphorus as red phosphorus is __________
and conists _________ of P4 units.
67.
68.
69.
70.
71.
Group 16th
72.
The lead chamber process involves the oxidation of ....................... by atmospheric oxygen under the
influence of ................ as catalysts.
73.
74.
75.
An oxide,.................. liberates chlorine with HCl and oxygen with conc. H2SO4.
76.
77.
Aqueous solution of sodium chlorate reacts with sulphur dioxide to form................. acid and sodium chloride.
78.
Fluorine reacts with water at very low temp. when mixture of .................is formed
79.
When .................. gas is passed through dry KOH a deep orange coloured compound ................. is formed.
80.
81.
The HM--H bond angle in the hydrides of group 15 elements follows the order
(A) NH3 > PH3 > AsH3 > SbH3
(B) NH3 < PH3 < AsH3 < SbH3
(C) NH3 < PH3 = AsH3 = SbH3
(D) PH3 > NH3 > AsH3 > SbH3
2.
(D) NO2
(D) N2O5
3.
4.
16TH Group
5.
6.
7.
8.
(D) Na2 O
In the reaction
O3 + 2 + H2O (X) + O2
The compound (X) is
(A) HO3
(B) H
(C) HO4
(D) 2O5
Group 15th
9.
As, Sb and Bi show little or no tendency to form negative ions of the type M3. This is because
(A) these elements are less electronegative
(B) their atoms have larger size
(C) they are unable to hold the added electrons due to inert pair effect
(D) they do not posses half filled np subshells
10.
11.
12.
Group 16th
13.
Which of the following statement (s) is/are true for sodium thiosulphate ?
(A) it acts as an antichlor
(B) it is used as an reducing agent in iodometric titration.
(C) it reacts with hydrochloric acid to form SO2 and sulphur.
(D) it is used in photography as hypo to dissolves excess of AgBr as soluble complex.
14.
(D) H2S2O8
15.
16.
17.
18.
2.
Nitrogen cannot be stored as liquid in sealed containers but ammonia can be, why ?
3.
4.
Anhydrous CaCl2, P4O10 or conc. H2SO4 can not be used as drying agent for ammonia. why ?
5.
Red phosphorus is denser, less volatile and chemically less reactive than yellow phosphorus. Explain ?
6.
7.
What happens when molten mixture of KNO3 and KNO2 reacts with Cr2O3 ?
8.
9.
10.
(taken in equimolar)
(f) Ca3 (PO4)2 + SiO2 + C
11.
What products are formed when H3PO2 is heated at 415 K and at 435 K respectively.
12.
13.
14.
Write the chemical reactions of P4O6 with cold and hot water.
15.
16.
17.
Why is BiH3 the strongest reducing agent among all the hydrides of group 15 elements ?
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
State the conditions under which NH3 is manufactured from N2 and H2.
29.
30.
Commercial nitrogen is passed through copper chips kept in ammonia solution for removing oxygen. Explain.
31.
Nitric acid acts only as an oxidising agent while nitrous acid can act both as an oxidising and reducing
agent.
32.
33.
A waxy crystalline solid (A) with a garlic odour is obtained by buring white P in a stream of air. (A) reacts
vigorously with hot water forming a gas (B) and an acid (C). Gas (B) has unplesant odour of rotten fish and
is neutral towards litmus. When passed through CuSO4 solution gas (B) produced a black ppt. (D) What
are (A) to (D) ? Give chemical equations of the reactions.
34.
Why does H3PO3 act as a reducing agent but H3PO4 does not ?
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Group 16th
35.
36.
Explain why the liquid oxygen stickes to the magnet pole but liquid nitrogen does not ?
37.
Write the names of substances which have higher oxidation potential than ozone.
38.
39.
Why sulphur is able to show oxidation state of +4 and +6 with fluorine and oxygen ?
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
Which of the following do not react with oxygen directly ? Zn, Fe, Au,Kr.
50.
51.
52.
Out of following forms of sulphur which one is paramagnetic in nature and why ? S8 ,S6 and S2
53.
54.
55.
56.
57.
What happens when one mole (partial hydrolysis) and excess of water (complete hydrolysis) reacts with
one mole of per oxodisulphuric acid ?
58.
58.
59.
60.
Oxygen almost invariably exhibits an oxidation state of -2 but other members of the family exhibit negative
as well as positive oxidation state of +2, +4 and +6.
61.
62.
Among the hydrides, H2O, H2S, H2Se which has highest bond angle.
63.
64.
65.
An inorganic halide (A) reacts with water to form two acids (B) and (C). Also aqueous solution of (A) reacts
with KOH to form two salts (D) and (E) Which are soluble in water. The solution gives white precipitates
with both AgNO3 and BaCl2 solutions respectively. Identify (A) to (E) and write the chemical reactions
involved.
66.
From the reactions given below, identify (A), (B), (C) and (D) and write their formulae.
(A) + dil. H2SO4 + K2Cr2O7 (B) Green Solution
(A) + dil. H2SO4 + (C) MnSO4
H2 O
(A) + O2
(D)
(D) + BaCl2 White ppt.
67.
68.
On heating rhombic sulpur it melts but viscosity of liquid increases upto 2000C and beyond that it decreases
why ?
69.
70.
For drying H2S gas conc. H2SO4 can not be used why ?
71.
72.
73.
(iii)
(iv)
(v)
(vi)
Group 15th
1.
2.
3.
(B) two
(C) three
(C) CaO
4.
Give Statement-2(s) why elemental nitrogen exists as diatomic molecule whereas elemental phosphorus
is a tetra-atomic molecule.
[JEE 2000 (M), 2/100]
5.
6.
7.
8.
9.
10.
12.
13.
White phosphorus on reaction with NaOH gives PH3 as one of the products. This is a :
[JEE 2008 (P-I), 4/82]
(A) dimerization reaction
(B) disproportionation reaction
(C) condensation reaction
(D) precipitation reaction
14.
15.
Match each of the reactions given in column I with the corresponding products (s) given in column II.
[JEE 2009 (P-II), 8/80]
Column I
Column II
(A)
Cu + dil HNO3
(p)
NO
16.
17.
(B)
Cu + conc HNO3
(q)
NO2
(C)
Zn + dil HNO3
(r)
N2 O
(D)
Zn + conc HNO3
(s)
Cu(NO3)2
(t)
Zn(NO3)2
(C) (NH4)2Cr2O7
Among the following the number of compounds than can react with PCl5 to give POCl3 is
O2, CO2, SO2, H2O, H2SO4, P4O10
[JEE 2011 (P-II), 4/80]
Group 16th
18.
Amongest H2O, H2S, H2Se and H2Te the one with highest boiling point is :
[JEE 2000 (S), 3/35]
(A) H2O because of H-bonding.
(B) H2Te because of higher molecular weight.
(C) H2S because of H-bonding.
(D) H2Se because of lower molecular weight.
18.
19.
20.
(C) K2 MnO4
21.
22.
23.
The difference in the oxidation numbers of the two types of sulphur atoms in Na2S4O6 is.
[JEE 2009 (P-I), 4/80]
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In case of nitrogen, NCl3 is possible but no NCl5 while in case of phosphorus, PCl3 as well as PCl5 are
possible. It is due to :
[AIEEE 2002]
(1) availability of vacant d-orbital in P but not in N.
(2) lower electronegativity of P then N.
(3) lower tendency of H bond formation in P than N.
(4) occurrence of P in solid while N in gaseous state at room temperature.
2.
3.
What would happen when a solution of potassium chromate is treated with an excess of dilute nitric
acid ?
[AIEEE 2003]
(1) Cr3+ and Cr2O72 are formed
(2) Cr2O72 and H2O are formed
(3) CrO42 is reduced to + 3 state of Cr
(4) CrO42 is oxidized to + 7 state of Cr
4.
The number of hydrogen atom (s) attached to phosphorus atom in hypophosphorus acid is :
[AIEEE 2005]
(1) zero
(2) two
(3) one
(4) three
5.
Which of the following chemical reactions depicts the oxidizing behaviour of H2SO4? [AIEEE 2006]
(1) 2HI + H2SO4 I2 + SO2 + 2H2O
(2) Ca(OH)2 + H2SO4 CaSO4 + 2H2O
(3) NaCl + H2SO4 NaHSO4 + HCl
(4) 2PCl5 + H2SO4 2POCl3 + 2HCl + SO2Cl2
6.
7.
Regular use of which of the following fertilizers increases the acidity of soil?
(1) Superphosphate of lime
(2) Ammonium sulphate
(3) Potassium nitrate
(4) Urea
8.
In context with the industrial preparation of hydrogen from water gas (CO + H2), which of the following is
the correct statement ?
[AIEEE 2008, 3/105]
(1) CO is removed by absorption in aqueous Cu2Cl2 Solution.
(2) H2 is removed through occlusion with Pd.
(3) CO is oxidized to CO2 with steam in the presence of a catalyst followed by absorption of CO2 in alkali.
(4) CO and H2 are fractionally separated using differences in their densities.
9.
10.
[AIEEE 2011]
11.*
[JEE Mains2013]
[AIEEE 2003]
(4) NH3 + HOCl
[AIEEE 2006]
(2) In aqueous medium HF is a stronger acid than HCl
(4) HNO3 is a stronger acid than HNO2
Discuss the general characteristics of Group 15 elements with reference to their electronic configuration,
oxidation state, atomic size, ionisation enthalpy and electronegativity.
2.
3.
4.
Why does NH3 form hydrogen bond but PH3 does not?
5.
How is nitrogen prepared in the laboratory? Write the chemical equations of the reactions involved.
6.
7.
Illustrate how copper metal can give different products on reaction with HNO3.
8.
9.
The HNH angle value is higher than HPH, HAsH and HSbH angles. Why?
[Hint : Can be explained on the basis of sp3 hybridisation in NH3 and only sp bonding between hydrogen
and other elements of the group].
10.
Why does R3P = O exist but R3N = O does not (R = alkyl group)?
11.
12.
13.
Write main differences between the properties of white phosphorus and red phosphorus.
14.
15.
16.
17.
Justify the placement of O, S, Se, Te and Po in the same group of the periodic table in terms of electronic
configuration, oxidation state and hydride formation.
18.
19.
Knowing the electron gain enthalpy values for O O and O O2 as 141 and 702 kJ mol1 respectively,
how can you account for the formation of a large number of oxides having O2 species and not O?
(Hint: Consider lattice energy factor in the formation of compounds).
20.
21.
22.
23.
(v) POF3?
24.
25.
Arrange the following in the order of property indicated for each set:
NH3, PH3, AsH3, SbH3, BiH3 increasing base strength.
Pt
NH3 + O2
(A)
(A) + O2 (B) (brown fumes).
(B) + H2O (C) (nitrogen in lower oxidation state) + (D) (nitrogen in higher oxidation state)
(C) and (D) both are oxoacids of nitrogen.
(C) + I (E) (violets vapours).
Identify (A), (B), (C), (D) and (E).
2.
3.
What happens ?
(a) When phosphine is heated at 150C. (b) When phosphine is dissolved in water in presence of light.
4.
warm
P4 + NaOH Products.
Explain the reducing character of one of the products obtained by taking the example of copper sulphate.
5.
Starting with phosphorite, Ca3(PO4)2 , show how you would prepare phosphoric acid.
6.
Give the names and formulae of the compounds in which sulphur exhibits an oxidation state of :
(A) 2
7.
(B) + 4
(C) + 6
8.
9.
SO2 and Cl2 both are used as bleaching agent. What factors cause bleaching ?
10.
Colourless salt (A) decolourises I2 solution and gives white precipitate (changing to black) with AgNO3
solution. (A) also produces pink colour with FeCl3 solution. Identify (A) and explain reactions.
11.
Arrange the following in the increasing order of the properties stated against them.
(a) (i) NH3, (ii) PH3, (iii) AsH3, (iv) SbH3 - boiling point.
(b) (i) Bi3+, (ii) Sb3+, (iii) As3+ - stability of +3 oxidation state.
(c) (i) NH3, (ii) PH3, (iii) AsH3, (iv) SbH3, (v) BiH3 - reducing character.
12.
13.
Warm
(C) + Zn (dust)
gas (B) ;
(A)
both triatomic
Gas (B) gives white fumes with HCl. Identify (A) to (E) and write the chemical reactions involved.
14.
Titanium (IV) ions give an orange-red colouration in slightly acidic solution with hydrogen peroxide because
of the formation of :
(A) peroxo disulphatotitanium (IV) ions
(B) peroxo disulphatotitanium (II) ions
(C) titanium (IV) sulphate
(D) none of these
15.
Aqueous solution of Na2S2O3 gives white precipitate with Ag+ ions; the precipitate dissolves in excess of
Na2S2O3 solution. If the precipitate is boiled with water it changes to black and the supernatant liquid then
gives a white precipitate with a solution containing Ba2+ ions. Explain by writing the chemical equations
involved.
16.
HNO3 can not be used for the preparation of H2S from metal sulphides. Why ?
17.
How will you obtain sodium thiosulphate from aqueous solution of Na2CO3 using SO2 gas and sulphur ?
(only in three steps)
ETOOS ACADEMY Pvt. Ltd
F-106, Road No.2 Indraprastha Industrial Area, End of Evergreen Motor,
BSNL Lane, Jhalawar Road, Kota, Rajasthan (324005) Tel. : +91-744-242-5022, 92-14-233303
EXERCISE # 1
PART - I
Group
15h
1.
8.
15.
(D)
(D)
(A)
2.
9.
16.
(C)
(D)
(D)
3.
10.
17.
(C)
(B)
(C)
4.
11.
18.
(D)
(A)
(B)
5.
12.
19.
(B)
(D)
(B)
6.
13.
20.
(B)
(C)
(C)
7.
14.
21.
(A)
(D)
(B)
22.
29.
36.
43.
50.
57.
(C)
(B)
(B)
(A)
(C)
(D)
23.
30.
37.
44.
51.
58.
(B)
(A)
(D)
(B)
(D)
(C)
24.
31.
38.
45.
52.
59.
(C)
(D)
(C)
(C)
(D)
(D)
25.
32.
39.
46.
53.
60.
(C)
(D)
(A)
(D)
(D)
(D)
26.
33.
40.
47.
54.
61.
(D)
(A)
(B)
(C)
(A)
(C)
27.
34.
41.
48.
55.
62.
(A)
(B)
(B)
(C)
(A)
(C)
28.
35.
42.
49.
56.
(B)
(A)
(B)
(A)
(B)
2.
9.
16.*
23.
30.
37.
44.
(D)
3.*
(A)
10.
(ABCD) 17.
(D)
24.
(B)
31.
(D)
38.
(A)
45.
(ABC)
(C)
(B)
(C)
(B)
(A)
(B)
4.
11.
18.
25.
32.
39.
46.
(A)
(B)
(B)
(D)
(A)
(A)
(B)
5.
12.
19.
26.
33.
40.
47.
(D)
(B)
(C)
(B)
(A)
(B)
(A)
6.
13.
20.
27.
34.
41.
(D)
(B)
(A)
(C)
(C)
(B)
7.
14.
21.
28.
35.
42.
(A)
(D)
(D)
(B)
(A)
(A)
Group 16th
1.
8.
15.*
22.
29.
36.
43.
(B)
(C)
(AC)
(B)
(A)
(B)
(B)
PART - II
15th
Group
1.
(a vi), (b i), (c iv, v), (d ii) (e iii) (f iv)
3.
2.
Group 16th
4.
(a - iv) , (b - vii), (c - v), (d - ii, vi), (e - i) , (f - ii) , (g - iii)
5.
(a - vi), (b - vii), (c - i), (d - ii), (e - iii), (f - iv), (g - ix), (h - v), (i - viii)
6.
(A) P,Q,S ; (B) P,Q,S ; (C) R,S ; (D) Q, S
Group 15th
7.
(D)
14.
(B).
Group 16th
15.
(B)
22.
(D)
8.
(A)
9.
(A)
10.
(B)
11.
(B)
12.
(A)
13.
(D)
16.
23.
(B)
(A)
17.
24.
(B)
(B)
18.
25.
(A)
(C)
19.
26.
(D)
(A)
20.
(A)
21.
(A)
28.
35.
T
T
29.
36.
F
T
30.
37.
F
F
31.
38.
F
T
32.
39.
T
F
33.
40.
T
T
42.
49.
T
T
43.
50.
F
T
44.
45.
46.
47.
oxZ15th
27.
T
34.
T
Group 16th
41.
T
48.
T
N2O or NO.
52.
CaCN2 53.
Conc. H2SO4 57.
Two
58.
High heat of vaporisation.
62.
12, 4
65.
Ionic, [PCl4]+ ,
67.
+5
68.
N2
69.
White 54.
Four 59.
NH2NH2 , -2
Octahedral
Three 70.
71.
nitrous, nitric
NITROGEN & OXYGEN FAMILY
ADVANCED # 50
Group 16th
72.
SO2, oxides of nitrogen
73.
75.
MnO2
76.
Na2SO3 77.
79.
ozone, KO3
80.
basic, neutral
cross linking
74.
sulphuric acid
78.
81.
reduction, temporary
95.60 C
ozonised oxygen
EXERCISE # 2
PART - I
Group 15th
1.
(A)
16TH Group
5.
(C)
Group 15th
2.
(A)
3.
(C)
4.
(D)
6.
(A)
7.
(B)
8.
(A)
10.
(BD)
11.
(ACD) 12.
(BD)
(ABCD) 14.
(BD)
15.
(BCD) 16.
(ABD) 17.
9.
(AB)
Group 16th
13.
(ABD) 18.
(ABD)
PART - II
Group 15th
1.
NO2 being acidic in nature is absorbed by alkali.
2.
Critical tempt of nitrogen is very low where as the critical tempt. of ammonia is higer than the ordinary
tempt. So NH3 is easily liquified.
3.
Sun light
4HNO 3
4NO 2 2H2O O 2
NH3 being basic reacts with P4O10 or H2SO4. CaCl2 forms addition compound with NH3.
5.
Red phosphorus exists as polymeric chains of P4 tetrahedron linked together, whereas in yellow phosphorus
individual P4 molecules are held together by weak van der Walls force (has angle strain).
6.
P4O6 = 12 ; P4O10 = 16
7.
8.
NO colourless, turns brown in air ; N2O5 is volatile solid which forms HNO3 with water ;
NO2 is brown gas which condenses to yellow liquid N2O4 at 20C
9.
10.
H4P2O7
(f) 2Ca3 (PO4)2 + 6SiO2 6CaSiO3 + P4O10
P4O10 + 10C P4 + 10 CO
11.
12.
13.
Undergoes dehydration.
525 K
2H3PO 4
H4P2O 7 H2O
875 K
H3PO 4
HPO 3 H2O
14.
3H3PO4 + PH3
15.
2800 2900 C
(B) CaO 3C CaC 2 CO
500 600 C
CaC2 N2
CaCN2 C
6 8 atm
Nitrolim
NO2 being odd molecule, on dimerisation is converted to stable N2O4 molecule with even number of electrons.
17.
Lowest bond dissociation energy (i.e., least stable) , so breaking of B H bond is easier.
18.
PH3
(Lewis base)
19.
HI
PH4I
(acid)
(salt)
20.
Lone pair of electrons is present in more concentrated sorbital and due to decrease in bond (E H)
dissociation enthalpy down the group acts as acid rather then a base.
22.
Nitrogen has unique ability to form pp multiple bond. Phosphorus does not form p p bonds as their
atomic orbitals are so large and diffuse that they cannot have effective overlapping.
23.
24.
(i) + 3
(ii) 3
(iii) + 5
(iv) + 5
25.
(d) Pb(NO 3 )2
N2 O 4
NO 2 (Brown)
26.
27.
Refer text.
28.
Refer text.
29.
Refer text.
30.
31.
HNO3 es
aN v f/kd re
32.
N2O4()
34.
H3PO3 contains one PH bond and hence acts as a reducing agent but H3PO4 does not contain a PH
bond.
Group 16th
35.
Rhombic Slphur
36.
37.
38.
39.
40.
500 C
800 C
2BaO + O2
2BaO2 ; 2BaO2
2BaO + O2
41.
(a)
4K2Cr2O7
4K2CrO4 + 2Cr2O3 + 3O2
(c)
(d)
(e)
(b)
3O2
2O3
+ H2O2
(f)
(g)
moisture
2H2S + SO2
2H2O + 3S
(h)
(i)
(j)
42.
Due to resonance
43.
44.
As hydrogen catches fire due to heat liberated when water is absorbed by acid.
45.
H-S bond length is bigger than H-O thus H+ is more easily released.
46.
47.
Dioxygen exists as diatomic molecules (weak van der Waals force) where as sulphur as polyatomic
molecules (strong van der Waals forces.).
48.
Due to the decrease in bond (E H) dissociation enthalpy down the group acidic character increases.
49.
Au and Kr.
50.
First ionisation to H3O+ and HSO4 is larger whereas ionisation of HSO4 to H3O+ and SO42 is very small.
51.
2 I (aq) + H2O () + O3 (g) 2OH (aq) + I2 (s) + O2 (g) .It is buffered with a borate buffer (PH 9.2) Iodine
liberated is titrated against a standard solution of sodium thiosulphate.
52.
Sulphur exist as S2 in vapour state which has two unpaired electrons in the anti-bonding * orbitals like O2
53.
54.
55.
Freons .
56.
S8 (melt)
S8 ring break and diradical so formed polymerises to forms long chain polymer and
o
At 444 C
At 200 C
viscosity shorter chains
Viscosity further
viscocity starts to increase
boiling po int
o
At 600
and rings are formed
in vapour state exist as S2 molecules (paramagnetic like O2).
57.
58.
58.
2NaHSO3
H2SO3 + Na2SO3
air
2 Na S O + 2 S
2 Na2S3 + 3 O2
2 2 3
Group 16th
60.
Oxygen has no d-orbitals while other have d-orbitals. Therefore, the paired electrons can be made unpaired
by exciting electrons to d-orbitals.
61.
SO2 + 2OH-
SO2 + 2H2O
direction.
62.
64.
Mercury is a mobile liquid but in presence of ozone it loses its mobility due to the formation of mercury
suboxide and starts sticking to the glass. This is called as tailing of mercury. 2Hg + O3 Hg2O + O2 .
65.
(A) SO2Cl2 ;
66.
(A) Na2SO3 ;
67.
(a) H2O < SiO2 < CO2 < N2O5 < SO3
68.
On heating, S8 rings are broken and long chain polymers are formed up to 2000C. Thus due to polymerisation,
liquid becomes viscous but beyond 2000C long chains are broken into short chains and ultimately S2
molecules are formed in the vapour phase, so viscosity of liquid decreases.
(C) HCl ;
(B) Cr2(SO4)3 ;
(D) K2SO4
(C) KMnO4 ;
(E) KCl
(D) Na2SO4
69.
70.
(B) H2SO4 ;
63.
H2SO4 acts as strong oxidising agent and, therefore, following reaction takes place.
H2S + H2SO4 SO2 + S + 2H2O
S
71.
(a)
(b)
(c)
(d) H O S O H
O
72.
73.
(i)
(ii)
(iii)
(iv)
(v)
(vi)
EXERCISE # 3
PART - I
Group
1.
4.
15th
(C)
2.
(A)
3.
(C)
In the form of elemental nitrogen it exists as a diatomic molecule (N2). This is due to the fact that nitrogen
can form p-p multiple bond (NN) because of small size of nitrogen atom. Heavier elements of this group
do not able to form p-p bonds as their atomic orbitals are so large and diffuse that they cannot have
effective overlapping. Further P P single bond is stronger than N N single bond. Hence phosphorus as
tendency to under go catenation.
N N (N2)
(P4)
5.
(C)
6.
(A)
7.
(A)
10.
(a)
1008 g.
11.
15.
(C)
12.
(C)
13.
A p, s ; B q, s ; C r, t ;
8.
(B)
(b)
Structure of P4O10 .
9.
(C)
(B)
14.
D q, t
(B)
16.
(D)
17.
(B)
21.
(B)
22.
(B)
23.
(1)
6.
(4)
7.
(2)
Group 16th
18.
(A)
18.
(D)
19.
(D)
20.
1.
8.
(1)
(3)
2.
9.
(1)
(1)
3.
10.
(2)
(4)
4.
11.*
PART - II
(2)
5.
(1234)
EXERCISE # 4
PART-I
1.
Higher the positive oxidation state of central atom, more will be its polarising power which, in turn, increases the covalent character of bond formed between the central atom and the other atom.
2.
Because BiH3 is the least stable among the hydrides of Group 15.
3.
6.
7.
Both are sp3 hybridised. In PH4+ all the four orbitals are bonded whereas in PH3 there is a lone pair of
electrons on P, which is responsible for lone pair-bond pair repulsion in PH3 reducing the bond angle to less
than 109 28.
10.
11.
Three POH groups are present in the molecule of H3PO4. Therefore, its basicity is three.
15.
Because of small size and high electronegativity of oxygen, molecules of water are highly associated
through hydrogen bonding resulting in its liquid state.
21.
Both the SO bonds are covalent and have equal strength due to resonating structures.
23.
In general, interhalogen compounds are more reactive than halogens due to weaker XX1 bonding than
XX bond. Thus, ICl is more reactive than I2.
PART-II
1.
Pt
4NH3 + 5O2
4NO + 6H2O.
2.
The high reactivity of white phosphorus is due to an unusual bonding that produces considerable strain in
the P4 molecule. The P4 molecule exists as a discrete molecule whereas the red phosphorus is a polymeric
substance in which the tetrahedral, P4 units are held by covalent bonds as shown in the following structure.
3.
4.
6.
(A) H2S2
7.
8.
(A) As a germicide and disinfectant for sterilising water and improving the atmosphere of crowded places.
(B) S4+O2
(C) S+6O3
(B) For detecting the position of double bond in the unsaturated organic compounds.
(C) In mfg. of artificial silk, synthetic camphor, KMnO4 etc. It is also used for bleaching oil, ivory, flour starch
etc.
9.
10.
2S2O32 + I2 S4O62 + 2I
S2O32 + 2Ag+ Ag2S2O3 (white)
Ag2S2O3 + H2O Ag2S (Black) + H2SO4
Fe3+ + 2S2O32 [Fe(S2O3)2] (Pink or violet)
11.
(a) ) PH3 < AsH3 < NH3 < SbH3 - boiling point.
NH3 has higher boiling point due to H-bonding. In rest of the hydrides the boiling point increases down the
group with increasing atomic number on account of the increasing magnitude of van der Waals attraction.
van der Waal attraction molecular weight.
(b) Bi3+ < Sb3+ < As3+ - stability of +3 oxidation state decreases down the group due to inert pair effect.
(c) NH3 < PH3 < AsH3 < SbH3 < BiH3 - reducing character increases down the group as bond dissociation
energy decreases.
12.
NH4NO3
N2O+ 2H2O ; (NH4)2Cr2O7 N2 + Cr2O3 + 4H2O
13.
NH4NO3 + NaOH
NH3 + NaNO3 + H2O ; NH3 + HCl NH4Cl (white fumes)
NH4NO3
N2O + 2H2O
So, (A) = NH4NO3, (B) = NH3, (C) = NaNO3, (D) = N2O and (E) = H2O.
14.
15.
16.
17.
Na2SO3 + S Na2S2O3