Chapter - 7
Anomalous behaviour of first member of p-Block Elements
VSA QUESTIONS (1 - MARK QUESTIONS)
1. In group 15 elements, there is considerable increase in covalent
radius from N to P but small increase from As to Bi. Why?
The covalent radius in group 15 elements increases considerably from N to
P due to the addition of a new electron shell. However, from As to Bi, the
increase is smaller because the filled d and/or f orbitals in heavier elements
cause a shielding effect, reducing the effective nuclear charge experienced
by the outer electrons.
2. The tendency to exhibit – 3 oxidation state, decreases down the group
in group 15 elements. Explain.
The tendency to exhibit a -3 oxidation state in Group 15 elements
decreases as you move down the group due to increasing atomic size and
metallic character. This means that elements like nitrogen and phosphorus
readily form -3 compounds, while bismuth, at the bottom of the group,
rarely does
3. Maximum covalence of Nitrogen is ‘4’ but the heavier elements of
group 15 show covalence greater than ‘4’. Why?
Nitrogen's maximum covalency is 4 because it lacks vacant d-orbitals in its
valence shell, limiting it to forming a maximum of four bonds (one s and
three p orbitals). Heavier elements in group 15, like phosphorus, arsenic,
etc., have vacant d-orbitals in their valence shells, allowing them to expand
their octets and exhibit covalencies greater than four.
4. Nitrogen exists as a diatomic molecule with a triple bond between the
two atoms, whereas the heavier elements of the group do not exist as
E2 at room temperature. Assign a reason.
Nitrogen forms a stable diatomic molecule (N₂) with a triple bond due to its
small size and high electronegativity, allowing for effective pπ-pπ
bonding. Heavier elements in the group, like phosphorus, lack this ability
due to their larger size and lower electronegativity, preferring to form single
bonds in structures like P₄
5. The ionization enthalpies of group 15 elements are higher than those
of corresponding members of group 14 and 16 elements. Assign the
reason.
The higher ionization enthalpies of Group 15 elements compared to Group
14 and 16 elements in the same period are primarily due to the extra
stability of their half-filled p-orbitals. Group 15 elements have a valence
electron configuration of ns²np³, where the p-orbitals are exactly half-
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filled. This half-filled configuration provides additional stability, making it
more difficult to remove an electron and thus requiring more energy.
6. The boiling point of PH3 is lesser than NH3. Why?
The boiling point of PH3 is lower than that of NH3 because NH3 molecules
are capable of forming intermolecular hydrogen bonds, while PH3
molecules are not. Hydrogen bonds are strong intermolecular forces that
require more energy to overcome, leading to a higher boiling point.
7. NO2 dimerises to form N2O4. Why?
Nitrogen dioxide (NO2) dimerizes to form dinitrogen tetroxide
(N2O4) because NO2 is a molecule with an odd number of valence
electrons (17), making it unstable and reactive. To achieve a more stable
configuration, two NO2 molecules combine to form N2O4, which has an
even number of valence electrons (32) and a stable structure with all
electrons paired
8. Draw the structure of N2O5 molecule.
9. How does ammonia solution react with Ag + (aq)? Write the balanced
chemical equation.
Ammonia solution reacts with Ag+ (aq) to form a soluble complex ion called
diamminesilver(I) ion, [Ag(NH3)2]+. Initially, a brown precipitate of silver
oxide (Ag2O) may form, but it dissolves in excess ammonia to produce the
complex. The balanced chemical equation for the overall reaction is:
2Ag+(aq) + 4NH3(aq) -> 2[Ag(NH3)2]+(aq)
10. Why does NH3 forms intermolecular hydrogen bonds whereas PH 3
does not?
NH3 (ammonia) forms intermolecular hydrogen bonds due to the high
electronegativity of nitrogen, which creates a strong dipole moment in the
N-H bonds. This allows for attractive forces between the slightly positive
hydrogen atoms and the lone pair of electrons on the nitrogen atom of
another NH3 molecule. In contrast, PH3 (phosphine) does not form
hydrogen bonds because the electronegativity difference between
phosphorus and hydrogen is much smaller, resulting in a weak or non-polar
P-H bond, and therefore, weaker intermolecular forces
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11. Write disproportionation reaction of H3PO3?
The disproportionation reaction of H3PO3 (phosphorous acid) is: 4H3PO3
→ 3H3PO4 + PH3. In this reaction, the phosphorus atom in H3PO3, which
has an oxidation state of +3, is both oxidized to +5 in H3PO4 and reduced
to -3 in PH3
12. How does NH3 acts as a complexing agent?
NH3 acts as a complexing agent due to the presence of a lone pair of
electrons on the nitrogen atom, which allows it to donate electrons to metal
ions and form coordinate covalent bonds, thus creating a stable
complex. This behavior classifies ammonia as a Lewis base, capable of
donating electron pairs.
13. Why HF is the weakest acid and HI is the strongest.
HF is the weakest acid among the hydrohalic acids (HF, HCl, HBr, HI)
because the H-F bond is exceptionally strong due to the small size and
high electronegativity of fluorine, making it difficult to break and release a
hydrogen ion. Conversely, HI is the strongest acid because the H-I bond is
the weakest due to the large size of iodine, which leads to a longer bond
length and lower bond dissociation energy, making it easier to break and
release a hydrogen ion
14. Explain why halogens are strong oxidising agents.
Halogens are strong oxidizing agents due to their high electronegativity,
large negative electron gain enthalpies, and tendency to readily gain an
electron to achieve a stable noble gas configuration. This means they
easily attract and accept electrons from other substances, causing those
substances to be oxidized
15. Why is Bi(V) a stronger oxidant than Sb(V)?
Bi(V) is a stronger oxidizing agent than Sb(V) primarily due to the inert pair
effect and the resulting stability differences of the +3 and +5 oxidation
states. As you move down Group 15, the +3 oxidation state becomes more
stable compared to the +5 state. This means Bi(V) readily accepts
electrons to form the more stable Bi(III) state, making it a stronger oxidizing
agent than Sb(V) which has a more stable +5 oxidation state.
SF
16. Why SF4 is easily hydrolysed, whereas 6 is resistant to hydrolysis?
SF₄ is readily hydrolyzed because its central sulfur atom is not sterically
shielded by fluorine atoms, allowing water molecules to easily attack and react
with it. In contrast, SF₆ is highly resistant to hydrolysis due to the six fluorine
atoms surrounding the sulfur atom, which create a steric barrier that prevents
water molecules from reaching and reacting with the sulfur
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17. Bond dissociation enthalpy of F2 is less than that of Cl2. Why?
The bond dissociation enthalpy of F₂ is less than that of Cl₂ because
of greater interelectronic repulsions between the lone pairs of electrons in
F₂. These repulsions weaken the F-F bond, making it easier to break
compared to the Cl-Cl bond
18. Write the reaction of PCl5 with heavy water.
PCl5 + D2O POCl3 + 2DCl
19. How many P – O – P bonds are there in cyclotrimetaphosphoric acid?
3 bonds
20. In group 16, the stability of +6 oxidation state decreases and that of +4
oxidation state increases down the group. Why?
In Group 16, the +6 oxidation state becomes less stable, and the +4
oxidation state becomes more stable down the group due to the inert pair
effect. This effect describes the reluctance of the valence s-electrons (ns²)
to participate in bonding as you move down the group. This reluctance
increases as you go down because the increasing atomic number leads to
a greater attraction between the nucleus and the s-electrons, making them
more difficult to remove or share
21. Why we can not prepare HBr by heating KBr with sulphuric acid.
Concentrated sulfuric acid cannot be used to prepare HBr from KBr
because it acts as an oxidizing agent and oxidizes the HBr produced back
into bromine (Br2). This means that instead of obtaining HBr gas, you'll
primarily get bromine, sulphur dioxide, and water
24. Fluorine exhibits only –1 oxidation state whereas other halogens
exhibit +ve oxidation states also. Explain.
Fluorine, unlike other halogens, only exhibits a -1 oxidation state because it
is the most electronegative element and lacks d-orbitals in its valence shell,
preventing it from forming positive oxidation states
25. Arrange the following oxoacids of chlorine in increasing order of
acidic strength.
HOCl, HOClO, HOClO3, HOClO3
*26. Most known noble gas compounds are those of Xenon. Why?
Xenon forms the most known noble gas compounds primarily because it has the
lowest ionization enthalpy among the noble gases, making it easier to oxidize and
form compounds with strong oxidizing agents like fluorine and oxygen. While
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noble gases are generally unreactive due to their stable electron configurations,
xenon's larger atomic size and consequently weaker attraction between its
nucleus and outer electrons allows it to participate in chemical reactions under
suitable conditions
*27. “Hypophosphorus acid is a good reducing agent.” Justify with an
example.
[Hint : 4AgNO3 + H3PO2 + 2H2O 4Ag + HNO3 + H3PO4.
*28. Draw the structure of H4P2O7 and find out its basicity?
[Hint : Tetrabasic]
*29. Arrange the following triatomic species in the order of increasing
bond angle.
NO2, NO2+, NO2– [Hint :
NO2 has one non-bonding electron, NO 2– has two non-bonding
electrons,+ NO2+ has no non-bonding electron on N atom. Bond angle
of NO 2 is maximum that of NO2– minimum].
30. With what neutral molecule ClO– is isoelectronic?
31. Draw the structure of H2S2O8 and find the number of S–S bond if any.
32. What is cause of bleaching action of chlorine water? Explain it with
chemical equation?
[Hint : Formation of nascent oxygen]
*33. Electron gain enthalpy of fluorine is more negative than that of chlorine.
[Hint. : Due to small size of F atom, there are strong interelectronic
repulsions in the relatively smaller 2p orbitals of fluorine. So the
incoming electron does experience less attraction than in Cl]
*34. Which one of the following is not oxidised by O 3. State the reason. Kl,
FeSO4, K2MnO4, KMnO4
[Hint. : KMnO4 since Mn is showing maximum oxidation state of +7.]
SA (I) TYPE QUESTIONS (2 - MARK QUESTIONS)
2. Why is red phosphorus denser and less chemically reactive than
white phosphorus?
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3. Give chemical reaction in support of the statement that all the bonds
in PCl5 molecule are not equivalent.
[Hint : PCl5 + H2O POCl3 + 2HCl
4. Account for the following :
(a) XeF2 has linear structure and not a bent structure. (b)
Phosphorus show marked tendency for Catenation.
5. Draw the structures of BrF3, XeOF4, XeO3 using VSEPR theory.
6. Write the conditions that favour the formation of ammonia gas along
with the reactions involved in Haber’s Process.
7. Write the chemical equations of the following reactions (a)
Glucose in heated with conc. H2SO4.
(b) Sodium nitrate is heated with conc. H2SO4.
Complete the following reactions :
8. (i) (NH4)2 Cr2O7 →heat
(ii) N4H Cl (aq) + NaNO2 (aq) →
9. (i) NH2CONH2 + H2O →
(ii) FeCl3 (aq) + NH4OH →
10. (i) Ca3 P2 + H2 O (l) →
(ii) I2 + HNO3 (conc.) →
11. (i) Ba(N3)2 →heat
(ii) 4H3PO3 →heat
12. (i) PH4I + KOH →
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(ii) HgCl2 + PH3 →
13. (i) PCl3 + 3H2O →
(ii) S + H2SO4 (conc.) →
14. (i) Al2O3(s) + NaOH (aq) + H2O(l) →
CuCl
(ii) HCl + O2 →2
15. (i) Ca(OH)2 + Cl2 →
(ii) XeF4 + H2O →
16. (i) Na2SO3 + Cl2 + H2O →
(ii) NaHCO3 + HCl →
17. (i) XeF6 + H2O →hydrolysisComplete
(ii) XeF6 + H2O →hydrolysisPartial
18. (i) NO3– + Fe2+ + H+ →
(ii) Zn + HNO3 (dil) →
19. (i) Zn + HNO3 (conc) → (ii) P4 + HNO3 (conc) →
20. (i) NH3 + O2 →Pt/Rh
(ii) P4 + NaOH + H2O →
21. (i) P4 + SOCl2 →
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(ii) P4 + SO2Cl2 →
22. (i) PbS + O3 →
(ii) KI + H2O + O3 →
23. (i) MnO4– + SO2 + H2O →
(ii) Zn + HNO3 →
(dil)
24. (i) NH3 (Excess) + Cl2 →
(ii) NH3 + Cl2 (Excess) →
25. (i) Cl2 + NaOH (cold and dil) →
(ii) Cl2 + NaOH (hot & conc) →
26. (i) Fe + HCl →
(ii) Cl2 + F2 (Excess) →
27. (i) U + ClF3 →
(ii) FeSO4 + H2SO4 + Cl2 →
28. (i) What is the covalency of N in N2O5?
(ii) Explain why phosphorus forms pentachloride whereas nitrogen
and bismuth do not?
29. (i) The acidic character of hydrides of group 15 increases from H 2O to
H2Te. Why?
(ii) Dioxygen is a gas while sulphur (S8) is a solid. Why?
30. (i) Interhalogen compounds are more reactive than halogens except
F2. Why?
(ii) Give one important use of ClF3.
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31. (i) Write the composition of bleaching powder.
(ii) What happens when NaCl is heated with conc. H 2SO4 in the
presence of MnO2. Write the chemical equation.
32. Arrange the following in the decreasing order of their basicity. Assign
the reason :
PH3, NH3, SbH3, AsH3, BiH3.
*33. A colourless and a pungent smelling gas which easily liquifies to a
colourless liquid and freezes to a white crystalline solid, gives dense
white fumes with ammonia. Identify the gas and write the chemical
equation for its laboratory
preparation. [Hint : HCl]
*34. Complete following disproportionation reactions.
(a) P4 + NaOH + H2O →
(b) HNO2 →H+
35. Arrange the following trichlorides in decreasing order of bond angle
NCl3 PCl3, AsCl3, SbCl3
36. Suggest reason why only known binary compounds of noble gases
are fluorides and oxides of Krypton, Xenon.
[Hint : F and O are most electronegative elements. Kr and Xe both
have low lonisation enthalpies.]
37. Which fluorinating agent are oftenly used instead of F 2? Write two
chemical equations showing their use as fluorinating agents.
[Hint : BrF5 + 3H2O HBrO3 + 5HF
2IF7 + SiO2 2IOF5 + SiF4]
38. (a) Hydrolysis of XeF6 is not regarded as a redox reaction. Why?
(b) Write a chemical equation to represent the oxidising nature of XeF 4.
[Hint : (b) XeF4 + 2H2 Xe + 4HF)]
39. Write Chemical equation :
(a) XeF2 is hydrolysed
(b) PtF6 and Xenon are mixed together.
SA (II) TYPE QUESTIONS (3 - MARK QUESTIONS)
1. (i) How is HNO3 prepared commercially?
(ii) Write chemical equations of the reactions involved.
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(iii) What concentration by mass of HNO3 is obtained?
2. (i) How does O3 react with lead sulphide? Write chemical equation.
(ii) What happens when SO2 is passed in acidified KMnO4 solution?
(iii) SO2 behaves with lime water similar to CO2.
3. Assign reason for the following :
(i) Sulphur in vapour state exhibits paramagnetism.
(ii) F2 is strongest oxidising agent among halogens.
(iii) In spite of having same electronegativity, oxygen forms
hydrogen bond while chlorine does not.
4. Give appropriate reason for each of the following :
(i) Metal fluorides are more ionic than metal chlorides.
(ii) Perchloric acid is stronger than sulphuric acid.
(iii) Addition of chlorine to KI solution gives it a brown colour but
excess of Cl2 makes it colourless.
[Hint :
(i) According to Fajan’s Rule, bigger ions more are polarised than
the smaller ion by a particular cation.
(ii) ClO4– is more resonance stabilised than SO42– since dispersal of
negative charnge is more effective in ClO4– as compared with SO42–
(iii) 2KI + Cl2 2KCl + I2
I H HIO
Excess 5Cl2 + 2 + 6 2O 2 3 + 10 HCl (Colourless).
5. Explain why :
(i) No chemical compound of helium is known.
(ii) Bond dissociation energy of fluorine is less than that of
chlorine.
(iii) Two S–O bonds in SO2 are identical.
6. Out of the following hydrides of group 16 elements, which will have :
(i) H2S (ii) H2O (iii) H2Te
(a) lowest boiling point
(b) highest bond angle
(c) highest electropositive hydrogen.
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7. (i) How is XeO3 prepared from XeF6? Write the chemical equation for
the reaction.
(ii) Draw the structure of XeF4.
8. (i) Thermal stability of hydrides of group 16 elements decreases down
the group. Why?
(ii) Compare the oxidising powers of F 2 and Cl2 on the basis of bond
dissociation enthalpy, electron gain ethalpy of hologens and
hydration enthalpy of halide ions.
(iii) Write the chemical equation for the reaction of copper metal with
conc. HNO3.
*9. An unknown salt X reacts with hot conc. H 2SO4 to produce a brown
coloured gas which intensifies on addition on copper turnings. On
adding dilute ferrous sulphate solution to an aqueous solution of X
and then carefully adding conc. H 2SO4 along the sides of the test tube,
a brown complex Y is formed at the interface between the solution
and H2SO4. Identify X and
Y and write the chemical equation involved in the reaction.
[Hint : X is NO3– salt].
10. Assign reason to the following :
(i) Noble gases have large positive values of electron gain enthalpy.
(ii) Helium is used by scuba divers.
11. Arrange the following in the order of the property indicated for each
set–
(a) F2, Cl2, Br2, I2 (Increasing bond dissociation energy).
(b) HF, HCl, HBr, HI (decreasing acid strength).
(c) NH3, PH3, ASH3, SbH3, BiH3 (decreasing base strength).
[Hint :
(a) F2 has exceptionally low bond dissociation enthalpy. Lone pairs
in F2 molecule are much closer to each other than in Cl 2
molecule. Larger electron–electron repulsions among the lone
pairs in F2 molecule make its bond dissociation enthalpy
exceptionally low.
(b) Depends upon H–X bond dissociation enthalpy as the size of
atom increases, bond dissociation enthalpy of H–X decreases.
(c) Electron availability on the central atom ‘E’ in EH 3 decreases
down the group.
*12. A transluscent while waxy solid (A) on heating in an inert atmosphere is
converted to its allotropic form (B), Allotrope (A) on reaction with very
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dilute aqueous NaOH liberates a highly poisonous gas (C) having a
rotten fish smell, with excess of chlorine forms D which hydrolyses to
form compound (E). Identify the compounds (A) to (E).
A : White phosphorus, B : Red phosphorus, C : PH 3, D : PCl3, E : H3PO4
13. Write balanced equation for the following reactions :
(a) Zn is treated with dilute HNO3.
(b) NaCl is heated with H2SO4 in the presence of MnO2.
(c) Iodine is treated with conc. HNO3.
14. X2 is a greenish yellow gas with pungent offensive smell used in
purification of water. It partially dissolves in H 2O to give a solution
which turns blue litmus red. When X 2 is passed through NaBr
Solution, Br2 is obtained.
(a) Identify X2, name the group to which it belongs.
(b) What are the products obtained when X 2 reacts with H2O? Write
chemical equation.
(c) What happens when X2 reacts with hot and conc. NaOH? Give
equation.
16. Assign the appropriate reason for the following:
(a) Nitrogen exists as diatomic molecule and phorphorous as P 4,
Why? (b) Why does R3P = 0 exist but R3N = 0 does not ? (R = an alkyl
group).
(c) Explain why fluorine forms only one oxoacid, HOF.
[Hint :
(a) Due to its small size and high electronegativity N forms p – p
multiple bond (N ≡ N). whereas P does not form p – p bonds
but forms P – P single bond.
(b) Due to the absence of d-orbitals, N cannot expand its covalence
beyond four.
In R3N = 0, N should have a covalence of 5 so the compound R 3N
= 0 does not exist since maximum covalence shown by N
cannot exceed 4.
(c) F does not form oxoacids in which the oxidation state of F would
be +3, +5, +7, it forms one oxoacid, because of unavailability of d
orbitals in its valence shell.
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LONG ANSWER TYPE QUESTIONS (5 - MARK QUESTIONS)
1. How is PH3 prepared in the laboratory? How is it purified? How does
the solution of PH3 in water react on irradiation with light and on
absorption in CuSO4? How can you prove that PH3 is basic in nature?
Write the chemical equations for all the reactions involved.
2. Assign a possible reason for the following :
(a) Stability of +5 oxidation state decreases and that of +3 oxidation
state increases down the group 15 elements.
(b) H2O is less acidic than H2S.
(c) SF6 is inert while SF4 is highly reactive towards hydrolysis.
(d) H3PO2 and H3PO3 act as good reducing agents while H 3PO4 does
not.
(e) Noble gases have comparatively large size in their respective
periods.
3. (a) How is XeF6 prepared from the XeF4? Write the chemical equation
for the reaction.
(b) Deduce the structure of XeF6 using VSEPR theory.
(c) How does XeF2 reacts with PF5?
(d) Give one use each of helium and neon.
(e) Write the chemical equation for the hydrolysis of XeF 4.
4. (a) Why does nitrogen show anomalous behaviour? Discuss the trend
of chemical reactivity of group 15 elements with.
(a) oxygen (b) halogens (c) metals
(b) H3PO3 is a dibasic acid. Why?
5. (a) Arrange the following in the order of their increasing acid
strength.
(a) Cl2O7, SO2, P4O10
(b) How is N2O gas prepared? And draw its structure.
(c) Give one chemical reaction to show O3 is an oxidising agent.
*6. Identify A, B, C, D and E in the following sequence of reactions
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Complete the reactions of the above mentioned sequence.
[Hint : A is P4].
*7. A white waxy, translucent solid, M, insoluble in water but soluble in CS 2,
glows in dark. M dissolves in NaOH in an inert atmosphere giving a
poisonous gas (N). Also M catches fire to give dense white fumes of Q
:
(a) Identify M, N and Q and write the chemical equations of the
reactions involved.
(b) M exists in the form of discrete tetrahedral molecules. Draw its
structure.
(c) M on heating at 573 K is changed into other less reactive form,
Q, which is non-poisonous, insoluble in water as well as in CS 2
and does not glow in dark, Identify Q and draw its structure.
8. Write the structure of A, B, C, D and E in the following sequence of
reactions :
Complete reactions of the above mentioned sequence and name the
process by which ‘C’ is obtained.
[Hint. : A is NO and Ostwald process for the manufacture of HNO 3].
9. Give reason for each of the following :
(a) NH3 is more basic than PH3.
(b) Ammonia is a good complexing agent.
(c) Bleaching by SO2 is temporary.
(d) PCl5 is ionic in solid state.
(e) Sulphur in vapour state exhibits paramagnetism.
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10. Knowing the electrons gain enthalpy value for O O– and O– O2– as
–141 and 720 kJ mol–1 respectively, how can you account for the
formation of large number of oxides having O 2– species and not O–?
[Hint : Latlice enthalpy of formation of oxides having O 2– more than
compensates the second egH of oxygen.
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