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Q7 Nitrogen exists as diatomic molecule and phosphorus as P4. Why?

P Block elements ANS- Nitrogen has a tendency to form pp multiple bonds with itself.
Nitrogen thus forms a very stable diatomic molecule, N 2.
Q8 Why does nitrogen show catenation properties less than
phosphorus?
ANS- This is because of the relative weakness of the NN single bond as
Q1 Why does the reactivity of nitrogen differ from phosphorus? compared to the PP single bond. NN single bond is weaker because there
ANS- the two nitrogen atoms form a strong triple bond. This triple bond is greater repulsion of lone pairs of two nitrogen atoms,
has very high bond enthalpy and strength,
Q9 Can PCl5 act as an oxidising as well as a reducing agent? Justify.
Q2 Why does NH3 form hydrogen bond but PH3 does not? ANS- PCl5 can only act as an oxidizing agent not a reducing agent . The
ANS- ANS Nitrogen is highly electronegative as compared to phosphorus.. highest oxidation state that P can show is +5. In PCl5, phosphorus is in its
highest oxidation state (+5). now, it can only decrease its oxidation state and
Q3The HNH angle value is higher than HPH, HAsH and HSbH angles. act as an oxidizing agent.
Why?
ANS- Hydride NH3 PH3 AsH3 SbH3 Q10 Bond angle in is higher than that in PH3. Why?
the electronegativity of the central atom is highest in NH 3due to which bond ANS- In PH3, . Three bond pair and one lone pair. As lone pair-bond pair
pairs are closer to cetre N and repel more that leads to more separartion of repulsion is stronger than bond pair-bond pair repulsion, shape is changed to
bond pairs . pyramidal.
Due to the absence of lone pair in PH4+, there is no lone pair-bond pair
repulsion. Hence, the bond angle in is higher than the bond angle in PH3.
[structure must ]

Q 4 Some metals (e.g., Cr, Al) do not dissolve in concentrated nitric Acid
ANS- because of the formation of a passive film of oxide on the surface.the
single
Q11:Why are pentahalides more covalent than trihalides?
Q5:Why does R3P=O exist but R3N=O does not (R = alkyl group)? ANS In pentahalides, the oxidation state is +5 and in trihalides, the oxidation
ANS- N (unlike P) lacks the d-orbital. This restricts nitrogen to make 5 state is +3. Since the ion with a high charge has more polarizing power,
bond . Hence, R3N=O does not exist.
Q6 Explain why NH3 is basic while BiH3 is only feebly basic. Q12: Why is BiH3 the strongest reducing agent amongst all the hydrides
. ANS- Nitrogen valence shell has a small size due to which the lone pair of of Group 15 elements?
electrons is concentrated in a small region. This means that the charge ANS- because Bi-H bond is weakest and is most un stable hydride in
density is high. group 15 from NH3[most stable] to BiH3.[least stable ]

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Q13 Why is N2 less reactive at room temperature? three equatorial P-Cl bonds are equivalent, while the two axial bonds are
ANS- the two nitrogen atoms form a strong triple bond. This triple bond longer and weaker because of under more repulsions than equatorial bonds.
has very high bond strength,
Q21How do you account for the reducing behavior of H3PO2 on the basis
Q14 PH3 has lower boiling point than NH3. Why? of its structure ?
ANS- Unlike NH3, PH3 molecules are not associated through hydrogen ANS- In H3PO2, two H atoms are bonded directly to P atom which imparts
bonding reducing character to the acid

Q15 Though nitrogen exhibits +5 oxidation state, it does not form Q22. Give reasons for the following:
pentahalide. Give reason. (a) CN ion is known but CP ion is not known.
ANS- It does not has vacant d orbitals to expand its covalence beyond four. (b) NO2 dimers to form N2O4
ANS (a) Nitrogen being smaller is size forms p- p multiple bonding with
Q16Why does NH3 act as a Lewis base ? carbon, So ion is known, but phosphorus does not form p- p bond as it is
ANS- Nitrogen atom in NH3 has one lone pair of electrons which larger in size.
is available for donation. (b) NO2 is an odd electron molecule and there fore gets dimerised to stable
N2O4.
Q17 Why does NO2 dimerise ? Q23. (a) What is the covalence of nitrogen in N2O5?
ANS- NO2 contains odd number of valence electrons which make it (b) Explain why both N and Bi do not form pentahalides while
unstable . On dimerisation, it is converted to stable N 2O4 molecule with even phosphorus does.
number of electrons. ANS- (a) 4
(b) unlike P, N has no vacant d-orbitals in its valence shell.
Q`18In what way can it be proved that PH3 is basic in nature? Bi prefers +3 oxidation state is more stable because of inert pair effect.
ANS- PH3 has alone pair and reacts with acids like HI to form PH 4I which
shows that it is basic in nature. Q24 In which one of the two structures, NO2+and NO2-, the bond angle
has a higher value and why ?
Q19Why does PCl3 fume in moisture ? ANS- The bond angle in NO2+ is greater than that in. NO2- As in NO2+ there
PCl3 hydrolyses in the presence of moisture giving fumes of HCl. are two bond pairs at nitrogen which make it linear where as in NO 2-
there are two bond pairs and one lone pair which make it bent shape
Q 25 Assign a reason for each of the following statements:Ammonia is a
Q20Are all the five bonds in PCl5 molecule equivalent? Justify your stronger base than phosphine.

(i) In the structure of HNO3 molecule, the N O bond (121 pm) is


shorter than the N OH bond (140 pm).

(ii) Why is Bi (V) a stronger oxidant than Sb (V)?

(iii) H3PO2 and H3PO3 act as as good reducing agents while H3PO4
ANS-. does not

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ANS- (i)Nitrogen has a small size due to which the lone pair of electrons is (iii) On moving down the elements of group 15, the stability of +5 oxidation
concentrated in a small region. This means that the charge density is high. state decreases. This is because of inert pair effect. It is the reluctance of s-
electrons of the valence shell towards bonding
(ii) The structure of nitric acid is
(iv) PCl5 is covalent in the vapour state but in the crystalline state, it exists as
[PCl4]+ [PCl6]. These ions have tetrahedral and octahedral geometry. Thus,
solid phosphorous pentachloride behaves as ionic compounds.
The N O bond has a double-bond
character. On the other hand, N OH bond is a
Q27 State reasons for each of the following:
single bond. Since a double bond is shorter than a
(i) The N O bond inNO2-is shorter than the N O bond in NO3-
single bond, the N O bond (121 pm) is shorter
(ii) All the P-Cl bonds in PCl5 molecule are not equivalent.
than the N OH bond (140 pm
(iii) Why white phosphorous is kept in water ?
(iv) Why NF3 is not hydrolysed ?
(iii) +5 oxidation state for Bi is unstable because of the inert pair effect.
Thus, Bi (V) converts easily into , Bi (III) and become stronger oxidant than (v) Why PF3 and PF5 are not hydrolysed ?
Sb (V). ANS- (i) The shorter N O bond inNO2-is due to the existence of resonance
inNO2. The resonating structures can be drawn as follows.
(iv) Both H3PO2 and H3PO3 have P- H bonds, so they act as reducing agents,
but H3PO4, has no P-H bond but has O-H bonds, so it cannot act as a
reducing agent.

Due to resonance in NO2, the two bonds are equivalent. This leads to
Q26 How would you account for the following? a decrease in bend length. Thus, the N O bond length in NO2resembles a
(i) The value of electron gain enthalpy with negative sign for double bond Now, the resonating structures for NO3 can be drawn as:
phosphorous is higher than that for nitrogen
(ii) NF3 is an exothermic compound but NCl3 is endothermic compound.
(iii) The stability of + 5 oxidation state decreases down the group in
group 15 of the periodic table.
(iv) Solid phosphorus pentachloride behaves as an ionic compound.
(v) Tendency to form pentahalides decreases down the group in group 15 As seen from the above resonating structures of NO 3, the three oxygen
of the periodic table atoms are sharing two single bonds and one double bond. So, the real
ANS- (i) . Because of the electron-electron repulsions in 2p sub-shell are N O bond length resembles a single bond closely. This explains the
quite high. Hence, the incoming electron is not accepted as easily in nitrogen existence of shorter bond length of the N O bond in
as it is in phosphorous . Hence, the negative electron gain enthalpy for NO2 than in NO3.
phosphorous is higher than that of nitrogen .
(ii) In gaseous and liquid state, PCl5 has a trigonal bipyramidal structure. In
(ii) The instability of NCl3 is due to the weak NCl bond. This is due to. On this structure, the two axial P Cl bonds are longer and less stable than the
the other hand, N-F bond is stronger as size are similar three equatorial P Cl bonds. This is because of the greater bond pair bond

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pair repulsion in the axial bonds. Hence, all the bonds in PCl 5 are not as compared to equatorial bond pairs
equivalent. [ii]Because in PCl3 water attacks vacant d orbital of P but in NCl3 vacant d
orbital are present on Cl only to be attacked
.(ii) The tendency to form pentahalides decreases down the group
15 due to inert pair effect i.e., in Bi the s-electrons remain inert TRENDS
and do not take part in bonding
(iii) Highly reactive, burning into flames when exposed to air. 34 Arrange the following in correct order of property given
(iv)N has no d-orbital thus it can't accept H2O as a ligand for
hydrolysis.
(v) Due to higher strength of P -F bond

Q28Why Nitrogen is restricted to a maximum covalency of 4 since only


four (one s and three p) orbitals are available for bonding.
ANS- Nitrogen is restricted to a maximum covalency of 4 since only four
(one s and three p) orbitals are available for bonding

Q29 The heavier elements, expand their covalence as in PF6


ANS-The heavier elements have vacant d orbitals in the outermost shell
which can be used for bonding (covalency) and hence, expand their
covalence
Q30 why Nitrogen differs from the rest of the members of this group
ANS- [bond angle]
due toits smaller size, high electronegativity, high ionisation enthalpy and
non-availability of d orbitals. Nitrogen has unique ability to form
p -p multiple bonds with itself and with other elements having
small size and high electronegativity
Q 31 Heavier elements of 15 group do not form p -p bonds
ANS-
as their atomic orbitals are so large and diffuse that they cannot have
effective overlapping.

Q 32 Why NN bond is weaker than the single PP bond


ANS-because of high interelectronic repulsion of the non-bonding electrons,
owing to the small bond length.

Q 33[i]Why PCl5 has two types of bond length for P-Cl bond
[ii] Why PCl3 on hydrolysis forms H3PO3 but NCl3 does not give H3NO3 NO2- < NO2< NO2+

ANS-This is due to the fact that the axial bond pairs suffer more repulsion 35 A translucent white waxy solid (A) on heating in an inert atmosphere
is converted to its allotropic form (B).Allotrope (A) on reaction with

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very dilute aqueous KOH liberates a highly poisonous gas (C) having gas ceases after sometime. Upon addition of Zn dust to the same solution the
rotten fish smell. With excess of chlorine forms (D) which hydrolyses to gas evolution restarts. Identify the colourless salt J and write the equations of
compound (E). Identify compounds (A) to (E). reactions involved.
ANS- ANS-
(A) : white phosphorus [Hint. : Salt J forms brown complex with acidic FeSO4, therefore it is nitrate
(B) : red phosphorus salt. Salt produces
(C) : phosphine or (PH3) non-inflammable gas with NaOH when evolution of this gas stops and when
(D) : phosphorus pentachloride or (PCl5) Zn dust is added
(E) : phosphoric acid or (H3PO4) to the solution after evolution of gas stops, the evolution of same gas occurs.
This shows that
36 When conc. H2SO4 was added into an unknown salt present in a test tube, NH3 gas is produced by the reaction of NO3 ions of solution with Zn dust.
a brown gas (A) was evolved. This gasintensified when copper turnings were The same gas is
also added into this test-tube. On cooling, the gas (A) changed into a
colourless gas (B).
(a) Identify the gases A and B.
(b) Write the equations for the reactions involved. produced by the reaction of colour salt J solution. Hence salt J is NH 4NO3
ANS-
39 Complete the following chemical equations:
(i) Ca3P2(s) + H2O(l) ..

ANS-

37. A colourless inorganic salt (A) decomposes completely at about 250 C to


give only two products, (B) and (C), leaving no residue. The oxide (C) is a
liquid at room temperature and neutral to moist litmus paper while the gas
(B) is a neutral oxide.
White phosphorus burns in excess of (B) to produce a strong white
dehydrating agent. Write balanced equations for the reactions involved in the 40 Complete the following chemical reaction equations:
above process. Gradual addition of KI to Bi(NO 3)3 solution initially produces
a dark brown precipitate (i)
which dissolves in excess of KI to give a clear yellow solution. Write
chemical equations for the a
(ii)
38 A solution of colourless salt J forms brown complex with FeSO4
solution acidified with H2SO4. The solution of salt J on boiling with ANS-
NaOH, produces a non-inflammable gas. The evolution of

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(i) 42 What do you mean by disproportination give an example of each N
and P compound
(ii) ANS-Self redox reaction is called disproportination

41 Write chemical equations for the following processes:


(i) to prepare vert pure form of N2 43 Complete the following reactions
(ii) to prepare N2 from sodium nitrite
(iii) to prepare PH3 from P4
(iv) to prepare PH3 from Ca3P2
ANS-

What happenes when:-


(i) Ammonia react with FeCl3 ANS-
(ii) Ammonia react with white ppt of AgCl
(iii) Silver nitrate is reacted with hypophosphorous acid
(iv) Orthophosphorous acid is heated
(v) PCl5 is kept in moisture
(vi) White phosphorous is kept in air

ANS-

(i)

44
Complete the reaction
(ii)

(iii) ANS-

(iv)
(v) catches fire in air to give dense white fumes of P4O10.
45 Draw the structures of white phosphorus and red phosphorus. Which
one of these two types of phosphorus is more reactive and why?

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ANS-

White phosphorus is more reactive than red phosphorus.


The various P4 molecules of white phosphorus are held together by weak
Vander Waals force of attraction, which makes it very reactive. On the other
hand, molecules of red phosphorus are joined by covalent bonds to give a
polymeric structure, which makes it very stable and less reactive.

46 Which oxo-acid of Phosphorus contains P-P linkage?


ANS-Hypophosphoric H4P2O6

47 Name the acidic hydride of nitrogen ?


ANS-HN3 [H-N=N+=N-]
Q 54 Name the following oxoacids of phosphorous acids
50 State the difference between the nature of Pi bonds in H3PO3 and (i) a tribasic acid
HNO3 molecules? (ii) acid with One P O P linkage
HNO3contain P-P where as H3PO3 d-P (iii) acid with Two P OH ,Two P H, Two P = O
(iv) acid with Three P O P
51 (SiH3)3 N is a weaker base than (CH3)3 N. Give reason. ANS-
ANS-Lone pair is delocalized in to vacant d-orbital of silicon (v) a tribasic acid - ortho phosphoric acid
(vi) acid with One P O P linkage Pyrophosphoric
52 Calculate the amount of 0.1 M NaOH solution required to neutralize (vii) acid with Two P OH ,Two P H, Two P = O
the solution produced by dissolving 1.1 g of P4O6 in water. aPyrophosphorous
[HINT :-P4O6 will react with water to form H3PO3 which is dibasic acid][do (viii) acid with Three P O P : Tri cycloMetaphosphoric
your self ]
53 Draw the structure of Q 55 Elements of Group 16 generally show lower value of first
ANS- ionisation
(i) Hypophosphorous enthalpy compared to the corresponding periods of group 15.
(ii) (Phosphinic)Orthophosphorous (Phosphonic) Why?
(iii) Pyrophosphorous ANS- Due to extra stable half-filled p orbitals electronic configurations of
(iv) Hypophosphoric Group 15 elements, larger amount of energy is required to remove electrons
(v) Orthophosphoric compared to Group 16 elements
(vi) Pyrophosphoric
Q 56.[a] Why is dioxygen a gas but sulphur a solid?

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ANS- [a] it can effectively form pp bonds and form O2 (O==O)
molecule. Also, the intermolecular forces in oxygen are weak van der Walls, [h] H2S is less acidic than H2Te. Why?
which cause it to exist as gas. On the other hand, sulphur does not form M 2 , ANS-Due to the decrease in bond (EH) dissociation enthalpy down the group, acidic
it form S8 which is a solid. character increases.

Q57 Complete the following reactions:


[b]Why is for H2SO4 in water? (i) C2H4 + O2 (ii) 4Al + 3 O2

ANS- [b] ANS- (i)

It can be noticed that This is because common ion effect of H+ from


first dissociation on second dissociation . (ii)

[c]Why does O3 act as a powerful oxidising agent? Q 58Which form of sulphur shows paramagnetic behaviour ?
ANS- [c]Ozone is unstable and decomposes readily to give a nascent ANS- In vapour state sulphur partly exists as S2 molecule which has two
oxygen. Nascent oxygen, being a free radical, is very reactive. unpaired electrons in the antibonding * orbitals like O2 and, hence,
exhibits paramagnetism.

Q 59Knowing 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?
[d]Why is H2O a liquid and H2S a gas?
ANS-Stability of an ionic compound depends on its lattice energy. More the
ANS- [d] there is strong and extensive hydrogen bonding in H 2O, which is
lattice energy of a compound, more stable it will be.
absent in H2S. Molecules of H2S are held only by weak van der Waals
Lattice energy is directly proportional to the charge carried by an ion. When
forces of attraction.
a metal combines with oxygen, the lattice energy of the oxide involving O 2
ion is much more than the oxide involving O ion. Hence, the oxide having
[e] SF4 is easily hydrolysed whereas SF6 is not easily hydrolysed. O2 ions are more stable than oxides having O. Hence, we can say that
formation of O2 is energetically more favourable than formation of O .
ANS- [e] This is due to the S of SF6 is stearically protected by six fluorine
atoms. Q 60 Which aerosols deplete ozone?
[f] Sulphur has a greater tendency for catenation than oxygen. ANS-Freons or chlorofluorocarbons (CFCs) are aerosols that accelerate the
depletion of ozone. In the presence of ultraviolet radiations, molecules of
[f] ANS-The tendency for catenation depends upon the bond energy. the CFCs break down to form chlorine-free radicals that combine with ozone to
sulphur sulphur bond strength is higher, and as a result, the tendency of form oxygen.
catenation is also higher.
Q 61Describe the manufacture of H2SO4 by contact process?
[g] Sulphur in vapour state exhibits a paramagnetic behaviour ANS-Sulphuric acid is manufactured by the contact process. It involves the
[g] ANS- (ii) In vapour state, sulphur exists as S2 molecule. S2 molecule, like following steps:
O2 molecule, has two unpaired electrons in the anti-bonding * orbitals.
Hence, like O2, it exhibits paramagnetism.

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Step (i):Sulphur or sulphide ores are burnt in air to form SO 2. (e) disappearance of yellow powder along with evolution of colourless
gas.
Step (ii):By a reaction with oxygen, SO2 is converted into SO3 in the
presence of V2O5 as a catalyst.

Step (iii):SO3 produced is absorbed on H2SO4 to give H2S2O7 (oleum).

ANS-
This oleum is then diluted to obtain H2SO4 of
the desired concentration..

Q 62 How is SO2 an air pollutant?


ANS-Sulphur dioxide causes harm to the environment in many ways:

1. It combines with water vapour present in the atmosphere to form sulphuric


acid. This causes acid rain. Acid rain damages soil, plants, and buildings,
especially those made of marble.

2. Even in very low concentrations, SO2 causes irritation in the respiratory


tract. It causes throat and eye irritation and can also affect the larynx to cause
breathlessness. Q 64 An element A exists as a yellow solid in standard state. It forms a
volatile hydride B which is a foul smelling gas
and is extensively used in qualitative analysis of salts. When treated with
3. It is extremely harmful to plants. Plants exposed to sulphur dioxide for a
oxygen, B forms an oxide C which is
long time lose colour from their leaves. This condition is known as chlorosis.
a colourless, pungent smelling gas. This gas when passed through
This happens because the formation of chlorophyll is affected by the
acidified KMnO4 solution, decolourises it. C
presence of sulphur dioxide.
gets oxidized to another oxide D in the presence of a heterogeneous
catalyst. Identify A,B,C,D, and also give the
Q 63 Concentrated sulphuric acid is added followed by heating to each
chemical equation of reaction of C with acidified KMnO 4 solution and
of the following test tubes labelled (i) to (v)
for conversion of C to D.
Identify in which of the above test tube the following change will be
ANS-
observed. Support your ANS- with the help
of a chemical equation.
A = Sulphur ()
(a) formation of black substance
B = H2S gas ()
(b) evolution of brown gas
C = SO2 gas ()
(c) evolution of colour less gas
D = SO3 gas (
(d) formation of brown substance which on dilution becomes blue.

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Q 68 :Comment on the nature of two SO bonds formed in SO2
molecule. Are the two SO bonds in this molecule equal?
Q 65 Which of the following does not react with oxygen directly?
ANS-The electronic configuration of S is 1s2 2s2 2p6 3s2 3p4.During the
Zn, Ti, Pt, Fe formation of SO2, one electron from 3p orbital goes to the 3d orbital and S
undergoes sp2 hybridization. Two of these orbitals form sigma bonds with
ANS-Pt is a noble metal and does not react very easily. All other elements, two oxygen atoms and the third contains a lone pair. p-orbital and d-orbital
Zn, Ti, Fe, are quite reactive. Hence, oxygen does not react with platinum contain an unpaired electron each. One of these electrons forms p- p
(Pt) directly. bond with one oxygen atom and the other forms p- d bond with the
other molecule. This is the reason SO2 has a bent structure. Also, it is a
Q 66 [i]How is O3 estimated quantitatively? resonance hybrid of structures I and II.
[ii] How is the presence of SO2 detected?
ANS- [i]Quantitatively, ozone can be estimated with the help of potassium
iodide. When ozone is made to react with potassium iodide solution buffered
with a borate buffer (pH 9.2), iodine is liberated. This liberated iodine can be
titrated against a standard solution of sodium thiosulphate using starch as an Both SO bonds are equal in length (143 pm) and have a multiple bond
indicator. The reactions involved in the process are given below. character.

Q 69

[ii]SO2 is a colourless and pungent smelling gas.It can be detected with the
help of potassium permanganate solution. When SO2 is passed through an
acidified potassium permanganate solution, it decolonizes the solution as it
reduces

Q 67 What happens when sulphur dioxide is passed through an


aqueous solution of Fe(III) salt? ANS-
ANS-SO2 acts as a reducing agent when passed through an aqueous solution
containing Fe(III) salt. It reduces Fe(III) to Fe(II) i.e., ferric ions to ferrous
ions.

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obtain the maximum amount of SO3 gas, temperature should be low and
pressure should be high.

Q 72 List the important sources of sulphur.


ANS- Sulphur mainly exists in combined form in the earths crust primarily
as sulphates [gypsum (CaSO4.2H2O), Epsom salt (MgSO4.7H2O), baryte
(BaSO4)] and sulphides [(galena (PbS), zinc blends (ZnS), copper pyrites
(CuFeS2)].

Q 73 Write the order of thermal stability of the hydrides of Group 16


elements.
ANS-The thermal stability of hydrides decreases on moving down the group.
This is due to a decrease in the bond dissociation enthalpy (HE) of hydrides
on moving down the group.Therefore,
Q 70 Mention three areas in which H2SO4 plays an important role.
ANS-Sulphuric acid is an important industrial chemical and is used for a lot
of purposes. Some important uses of sulphuric acid are given below.

(i) It is used in fertilizer industry. It is used to make various fertilizers such as


ammonium sulphate and calcium super phosphate.

(ii) It is used in the manufacture of pigments, paints, and detergents.


74 Draw the structure of the following molecules:
(iii) It is used in the manufacture of storage batteries. (i) SF4 (ii) H2S2O8
ANS-
Q 71 Write the conditions to maximize the yield of H2SO4 by Contact
process. (i)
ANS- Manufacture of sulphuric acid by Contact process involves three steps.
1. Burning of ores to form SO2
2. Conversion of SO2 to SO3 by the reaction of the former with O2

(V2O5 is used in this process as a catalyst.)

3. Absorption of SO3 in H2SO4 to give oleum (H2S2O7)


75 Halogens have maximum negative electron gain enthalpy in the
The key step in this process is the second step. In this step, two moles of respective periods of the periodic table. Why?
gaseous reactants combine to give one mole of gaseous product. Also, this ANS-
reaction is exothermic. Thus, in accordance with Le Chateliers principle, to Halogens have the smallest size in their respective periods and therefore

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high effective nuclear charge. As a consequence, they readily accept one electron to (a) Chlorine water produces nascent oxygen which is responsible for
acquire noble gas electronic configuration. bleaching action and oxidation:
76Although electron gain enthalpy of fluorine is less negative as compared
to chlorine, fluorine is a stronger oxidising agent than chlorine. Why? (b) Ozone gas acts as a strong oxidising agent, so it oxidises iodide ions to
It is due to Iodine
ANS- I2 Vapours evolved have violet colour
(i) low enthalpy of dissociation of F-F bond (Table 7.8).
(ii) high hydration enthalpy of F (Table 7.8).
.
77 Fluorine exhibits only 1 oxidation state whereas other halogens
exhibit + 1, + 3, + 5 and + 7 oxidation states also. Explain. 82. (a) Why does chlorine water lose its yellow colour on standing?
ANS- (b) What happens when Cl2 reacts with cold dilute solution of sodium
Fluorine is the most electronegative element and cannot exhibit any positive hydroxide?
oxidation state. Other halogens have d orbitals and therefore, can expand ANS-
their octets and show + 1, + 3, + 5 and + 7 oxidation states also. Write equation only.
(a) Chlorine water looses its
78Write the balanced chemical equation for the reaction of Cl2 with hot yellow colour on standing due
and concentrated NaOH. Is this reaction a disproportionation to the formation of HCl and
reaction? Justify. HClO.
ANS- 83 Deduce the molecular shape of BrF3 on the basis of VSEPR theory.
3Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O ANS-
Yes, chlorine from zero oxidation state is changed to 1 and +5 The central atom Br has seven electrons
oxidation states. in the valence shell. Three of these will form electronpair
bonds with three fluorine atoms leaving behind four electrons.
79When HCl reacts with finely powdered iron, it forms ferrous chloride Thus, there are three bond pairs and two lone pairs. According
and not ferric chloride. Why? to VSEPR theory, these
ANS- will occupy the corners of a trigonal bipyramid. The
Its reaction with iron produces H2. two lone pairs will occupy the equatorial positions
Fe+2HClFeCl 2+H2 to minimise lone pair-lone pair and the bond pairlone
Liberation of hydrogen prevents the formation of ferric chloride.
pair repulsions which are greater than the bond pair-bond pair repulsions. In addition,
80 Account for the following observations the axial fluorine atoms will be bent towards the equatorial
HOCl < HOClO < HOClO2 < HOClO3 fluorine in order to minimise the lone-pair-lone pair repulsions. The shape would be
ANS- that of a slightly bent T.
(iii) Higher the oxidation state of chlorine in oxo acid, more resonance 84Write balanced equations for the following:
stabilization in conjugate base which makes acid to be stronger the acid. (i) NaCl is heated with sulphuric acid in the presence of MnO 2.
(ii) Chlorine gas is passed into a solution of NaI in water.
81. Account for the following: (iii)U is heated with ClF3
(a) Chlorine water has both oxidizing and bleaching properties. (iv) BrF3 is hydrolysed
(b) On addition of ozone gas to KI solution, violet vapours are obtained ANS-
ANS-

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iodine as sodium iodide. Thus, sea is the greatest source of halogens.
(i)
(ii) 88Give the reason for bleaching action of Cl2.
ANS- When chlorine reacts with water, it produces nascent oxygen. This
(iii)
nascent oxygen then combines with the coloured substances present in the
organic matter to oxide them into colourless substances.
(iv) BrF5 + 3H2O HBrO3+5HF [lareger halogen forms oxo-acid in same
O.N. ] Coloured substances + [O] Oxidized
colourless substance
85Considering the parameters such as bond dissociation enthalpy,
electron gain enthalpy and hydration enthalpy, compare the oxidising 89 Name two poisonous gases which can be prepared from chlorine
power of F2 and Cl2. gas.
ANS- Fluorine is a much stronger oxidizing agent than chlorine. The ANS- Two poisonous gases that can be prepared from chlorine gas are(i)
oxidizing power depends on three factors. Phosgene (COCl2) (ii) Mustard gas (ClCH2CH2SCH2CH2Cl)

1. Bond dissociation energy 90 Why is ICl more reactive than I2?


ANS- ICl is more reactive than I2 because ICl bond in ICl is weaker than
2. Electron gain enthalpy II bond in I2.
91 How are xenon fluorides XeF2, XeF4 and XeF6 obtained?
3. Hydration enthalpy ANS- XeF2, XeF4, and XeF6 are obtained by a direct reaction between Xe and
because of its small size, the hydration energy of fluorine is much higher F2. The condition under which the reaction is carried out determines the
than that of chlorine. Therefore, the latter two factors more than compensate product.
for the less negative electron gain enthalpy of fluorine. Thus, fluorine is a
much stronger oxidizing agent than chlorine.

86Give two examples to show the anomalous behaviour of fluorine.


ANS-Anomalous behaviour of fluorine

(i) It forms only one oxoacid as compared to other halogens that form a
number of oxoacids. 92 With what neutral molecule is ClO isoelectronic? Is that
(ii) Ionisation enthalpy, electronegativity, and electrode potential of fluorine molecule a Lewis base?
are much higher than expected. ClO is isoelectronic to ClF. Also, both species contain 26 electrons in all as
shown.
87 Sea is the greatest source of some halogens. Comment.
ANS- Sea water contains chlorides, bromides, and iodides of Na, K, Mg, and Total electrons ClO = 17 + 8 + 1 = 26 In ClF = 17 + 9 = 26
Ca. However, it primarily contains NaCl. The deposits of dried up sea beds
contain sodium chloride and carnallite, KCl.MgCl2.6H2O. Marine life also ClF acts like a Lewis base as it accepts electrons from F to form ClF 3.
contains iodine in their systems. For example, sea weeds contain upto 0.5%

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93 ClF3 molecule has a T-shaped structure and not a trigonal 97 Arrange the following in the order of property indicated for each
planar one. set:(i) F2, Cl2, Br2, I2 - increasing bond dissociation enthalpy.
-ClF3 molecule involves a sp3d hybridization of the central atom Cl (ii) HF, HCl, HBr, HI - increasing acid strength.
ANS- (i) Bond dissociation energy usually decreases on moving down a
group as the atomic size increases. However, the bond dissociation energy of
F2 is lower than that of Cl2 and Br2. This is due to the small atomic size of
Electronic structure of Cl fluorine. Thus, the increasing order for bond dissociation energy among
(ground state) halogens is as follows:
(i) I2 < F2 < Br2 < Cl2
(ii) HF < HCl < HBr < HI

Electronic structure of Cl The bond dissociation energy of H-X molecules where X = F, Cl, Br, I,
(excited state) decreases with an increase in the atomic size. Since H-I bond is the weakest,
HI is the strongest acid.

98 Which one of the following does not exist?


Thus, ClF3 have trigonal bipyramidal geometries with two positions occupied (i) XeOF4 (ii) NeF2 (iii) XeF2 (iv) XeF6
by 2 lone pairs. Hence it is T-shaped. NeF2 does not exist.

94 99 Give the formula and describe the structure of a noble gas


(a) Account for the following: species which is isostructural with:
(ii) F2 is most reactive of all the four common halogens.
(ii) The acidic strength decreases in the order HCl > H2S > PH3
ANS- (i) Due to the small size of F atom, the three lone pair of electrons on (i) (ii) (iii)
each F atom in F F molecule repels the bond pair. As a result, F F is most
reactive of all the four common halogens
(i) XeF4 is isoelectronic with and has square planar geometry.
(ii) In a period, the electro negativity decreases in the order Cl > S
> P. As a result, the loss of H+ ions decreases.
Thus, the acidic strength of the hydrides decreases in the
following order. HCl > H2S > PH3
96 How are XeO3 and XeOF4 prepared?
ANS- (i) XeO3 can be prepared in two ways as shown.

(ii) XeOF4 can be prepared using XeF6. (ii)XeF2 is isoelectronic to and has a linear structure.

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ANS-Noble gases being monoatomic have no interatomic forces except weak
dispersion forces and therefore, they are liquefied at very low
temperatures. Hence, they have low boiling points.

104 Does the hydrolysis of XeF6 lead to a redox reaction?


ANS-No, the products of hydrolysis are XeOF4 and XeO2F2 where the oxidationstates
of all the elements remain the same as it was in the reacting state.

(iii) XeO3 is isostructural to and has a pyramidal molecular structure. 105 Write down the equations for hydrolysis of X F4 and XeF6. Which
of these two reactions is a Redoxreaction?
ANS-

Hydrolysis of XeF4 is a Redox reaction. Here Xe4+ is changing into Xe and


100Why do noble gases have comparatively large atomic sizes? Xe6+.
ANS-Noble gases do not form molecules. In case of noble gases, the atomic
radii corresponds to van der Waals radii. On the other hand, the atomic radii 106 Write chemical equations for the following processes PtF6 and
of other elements correspond to their covalent radii. By definition, van der xenon are mixed together
Waals radii are larger than covalent radii. It is for this reason that noble
gases are very large in size as compared to other atoms belonging to the same ANS-
period. 107 Draw the structures of the following molecules:
101 List the uses of Neon and argon gases. (i) XeF4(ii) BrF3 (iii) XeF6 (iv)XeOF4
ANS-Uses of neon gas:(i) It is mixed with helium to protect electrical ANS-
equipments from high voltage.
(ii) It is filled in discharge tubes with characteristic colours.
(iii) It is used in beacon lights.Uses of Argon gas: (i) Argon along with
nitrogen is used in gas-filled electric lamps. This is because Ar is more inert
than N. (ii) It is usually used to provide an inert temperature in a high
metallurgical process.(iii) It is also used in laboratories to handle air-sensitive
substances.
108 Complete the following chemical reaction equations:
102 Why are the elements of Group 18 known as noble gases ? (i)
ANS-The elements present in Group 18 have their valence shell orbitalscompletely
filled and, therefore, react with a few elements only undercertain conditions.
Therefore, they are now known as noble gases.
ANS- (i)

103 Noble gases have very low boiling points. Why?


109 Explain the following situations:
(i) XeF2 has a straight linear structure and not a bent angular structure.

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(ii) The majority of known noble gas compounds are those of Xenon.
ANS- (i)

According to VSEPR theory, XeF2 has trigonal


bipyramidal geometry with sp3d hybridisation. It has two
bond pairs and three lone pairs of electrons. The bond
pairs occupy axial positions and the lone pairs occupy the
equatorial positions. This is the most favourable arrangement as far as
stability is concerned. The two fluorine atoms if placed at the equatorial
positions will face minimum repulsion, and this would consequently increase
the stability. Hence, the structure is linear.

(ii) All noble gases have full s and p outer electron shells, so they do not form
chemical compounds easily. However, in heavier members like Xe, the
outermost electrons experience a shielding effect from the inner electrons, so
they are comparatively easily ionised. Hence, the first ionisation energy is
roughly equivalent to that of molecular oxygen. Xe reacts with
electronegative elements like fluorine and oxygen to form stable compounds.

110Why is helium used in diving apparatus?


ANS- Air contains a large amount of nitrogen and the solubility of gases in
liquids increases with increase in pressure. When sea divers dive deep into
the sea, large amount of nitrogen dissolves in their blood. When they come
back to the surface, solubility of nitrogen decreases and it separates from the
blood and forms small air bubbles. This leads to a dangerous medical
condition called bends. Therefore, air in oxygen cylinders used for diving is
diluted with helium gas. This is done as He is sparingly less soluble in blood.
111Balance the following equation: XeF6 + H2O XeO2F2 + HF
ANS-Balanced equation XeF6 + 2 H2O XeO2F2 + 4 HF

111 Why has it been difficult to study the chemistry of radon? xix O2 F2, O F2, Cl2O Br2O [thermal stability]
ANS-It is difficult to study the chemistry of radon because it is a radioactive xx Cl2O, ClO2, Cl2O6, Cl2O7 [thermal stability]
substance having a half-life of only 3.82 days. Also, compounds of radon - ANS-
such as RnF2 have not been isolated. They have only been identified.

Arrange the following in increasing order of property given

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xix O2 F2< O F2<Cl2O< Br2O
xx Cl2O, <ClO2< Cl2O6<Cl2O7

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