Intext Questions p-Block Elements

 

p-Block Elements

7.1 Why are pentahalides of P, As, Sb and Bi more covalent than their trihalides?

 

Ans: In pentahalides, the oxidation state is +5 which is more than the oxidation state of trihalides (+3). According to Fazan’s rule, the cations with higher positive charge have larger polarizing power and can polarise the halide ion to a greater extent. Since larger polarization, larger is the covalent character, therefore, pentahalides are more covalent than trihalides.

 

 

7.2 Why is BiH3 the strongest reducing agent amongst all the hydrides of Group 15 elements ?

 

Ans: Among the hydrides of group 15, BiH3 is the least stable molecule because Bi has largest size in the group and has least tendency to form covalent bond with small hydrogen atom. Therefore, it can readily lost H atom has strongest tendency to act as reducing agent.

 

 

7.3 Why is N2 less reactive at room temperature?

 

Ans: N2 has triple bond (NN) between two nitrogen atoms and it is non polar in character. Due to the presence of triple bond, it has very high bond dissociation energy (941.4 kJ/mol) and therefore, it does not reacts with other elements under normal conditions and is very unreactive.

 

 

7.4 Mention the conditions required to maximise the yield of ammonia.

 

Ans: The conditions to maximise the yield of ammonia are:

        i.            Low temperature of about 700 K

      ii.            High pressure of 200 x 105 Pa (about 200 atm)

    iii.            Presence of catalyst such as iron oxide with small amount of K2O and Al2O3.

 

 

7.5 How does ammonia react with a solution of Cu2+ ?

 

Ans: Ammonia reacts with a solution of Cu2+ to form deep blue coloured complex, tetraamminecopper (ii) ion:

Cu2+ (aq) + 4 NH3 (aq) [Cu(NH3)4]2+ (aq)

 

 

7.6 What is the covalence of nitrogen in N2O5 ?

 

Ans: N2O5 has the structure



The covalence of N in N2O5 is four because it has four shared pair of electrons.

 

 

7.7 (a) Bond angle in PH4+ is higher than that in PH3. Why?

 

Ans: Both PH4+ and PH3 involve sp3 hybridisation of P atom. In PH4+ all the four orbitals are bonded, whereas in PH3 there is a lone pair of electrons on P. In PH4+, the HPH bond angle is tetrahedral angle of 109.5O. But in PH3, lone pair-bond pair repulsion is more than bond pair-bond-pair repulsion so that bond angles become less than normal tetrahedral angle of 109.5O. The bond angle in PH3 has been found to be about 93.6O.

 

(b) What is formed when PH3 reacts with an acid?

 

Ans: Phosphine is weakly basic and like ammonia, gives phosphonium compounds with acids e.g., PH3 + HBr ® PH4Br

 

 

7.8 What happens when white phosphorus is heated with concentrated NaOH solution in an inert atmosphere of CO2 ?

 

Ans: When white phosphorus is heated with concentrated NaOH solution in an inert atmosphere of CO2  phosphine is formed.

 


 

7.9 What happens when PCl5 is heated?

 

Ans: On heating, PCl5 decomposes into PCl3 and Cl2

 


 


7.10 Write a balanced equation for the reaction of PCl5 with water.

 

Ans:



 

 

7.11 What is the basicity of H3PO4?

 

Ans: H3PO4 contains three P-OH bonds and therefore, its basicity is three.


 

 

7.12 What happens when H3PO3 is heated?

 

Ans: On heating, H3PO3 disproportionate to give orthophosphoric acid and phosphine.


 

           

 7.13 List the important sources of sulphur.

 

Ans: Sulphur occurs in the combined form as sulphide ores and sulphate ores. The common sulphide ores in which sulphur occurs are galena (PbS), zinc blend (ZnS), copper pyrites (CuFeS2) and sulphate ores are gypsum (CaSO4.2H2O), Epsom salt (MgSO4.7H2O) and barite (BaSO4). Traces of sulphur occurs as hydrogen sulphide in volcano. Organic material such as eggs, proteins, onion, garlic, mustard, hair and wool also contain sulphur.

 

 

7.14 Write the order of thermal stability of the hydrides of Group 16 elements.

 

Ans: The thermal stability of the hydrides of group 16 elements decreases from H2O to H2Te as:

 

H2O > H2S > H2Se > H2Te.

 

 

7.15 Why is H2O a liquid and H2S a gas ?

 

Ans: Due to high electronegativity and small size of oxygen, there are strong intermolecular hydrogen bonding between water molecules. As a result the water molecules are associated and in liquid at room temperature. Whereas in H2S, molecules do not form hydrogen bonding therefore, these molecules are gas at room temperature.

 

 

7.16 Which of the following does not react with oxygen directly?

Zn, Ti, Pt, Fe

 

Ans: Pt, because Pt is a noble metal.

 

 

7.17 Complete the following reactions:

(i) C2H4 + O2 ®

(ii) 4Al + 3 O2 ®

 

Ans: (i) C2H4 + 3 O2 ® 2 CO2 + 2 H2O

        (ii) 4Al + 3 O2 ® 2 Al2O3.

 

 

7.18 Why does O3 act as a powerful oxidising agent?

 

Ans: Ozone acts as a powerful oxidising agent because it decomposes readily to give atomic oxygen as:

O3 ® O2 + O

Therefore, ozone can oxidise a number of non-metals and other compounds. For example:

PbS (s) + 4 O3 (g) ® PbSO4 (S) + 4 O2 (g)

2 I- (aq) + H2O (l) + O3 (g) ® 2 OH- (aq) + I2 (s) + O2 (g)

                                                  

 

7.19 How is O3 estimated quantitatively?

 

Ans: When ozone reacts with an excess of potassium iodide solution buffered with a borate buffer (pH 9.2), iodine is liberated which can be titrated against a standard solution of sodium thiosulphate.

PbS(s) + 4O3(g) ® PbSO4(s) + 4O2(g)

2I(aq) + H2O(l) + O3(g) ® 2OH(aq) + I2(s) + O2(g)

 

 

7.20 What happens when sulphur dioxide is passed through an aqueous solution of Fe(III) salt?

 

Ans: Sulphur dioxide converts iron(III) ions to iron(II) ions.

2 Fe3+ + SO2 + 2 H2O ® 2 Fe2+ + SO42- + 4 H+.

 

 

7.21 Comment on the nature of two S–O bonds formed in SO2 molecule. Are the two S–O bonds in this molecule equal ?

 

Ans: Sulphur in SO2 involves sp2 hybridisation. Two of these sp2 hybrid orbitals form σ bonds with oxygen atoms. The remaining two unhybridised orbitals of S form pπ-pπ and pπ-dπ double bonds with oxygen atoms.

 

Though the two S-O bonds appear different because of pπ-pπ and pπ-dπ double bonds. However, both the S-O bonds are equal (bond length 143 pm) because of resonance between two structures.

 


 


 

7.22 How is the presence of SO2 detected ?

 

Ans: SO2 can be detected by the following tests:

a)   It decolourises acidified potassium permanganate solution.

b)   It turns acidified potassium dichromate solution green.

c)   It turns blue litmus red.

 

 

7.23 Mention three areas in which H2SO4 plays an important role.

 

Ans:

     i.        Manufacture of fertilisers (e.g., ammonium sulphate, superphosphate).

    ii.        Metallurgical applications (e.g. cleansing metals before enameling, electroplating and galvanising).

   iii.        Petroleum refining

 

 

7.24 Write the conditions to maximise the yield of H2SO4 by Contact process.

 

Ans:

     i.        Low temperature (optimum temperature 720 K)

    ii.        High pressure (optimum pressure 2 bar)

   iii.        Presence of catalyst (V2O5)

 

 

7.25 Why is Ka2 << Ka1 for H2SO4 in water ?

 

Ans: H2SO4 is a strong acid in water because of its first ionisation to H3O+ and HSO4-.

H2SO4 + H2O H3O+ + HSO4-.

It is almost completely ionised so that its Ka1 is very large (Ka1 > 10). However, dissociation of HSO4- in water to H3O+ and SO42- is very small (Ka2 = 1.2 x 10-2). That is why its Ka2 << Ka1.

HSO4-+ H2O H3O+ + SO42-.

 

 

7.26 Considering the parameters such as bond dissociation enthalpy, electron gain enthalpy and hydration enthalpy, compare the oxidising power of F2 and Cl2.

 

Ans: The oxidising powers of both the members of halogen family are expressed in terms of their electron accepting tendency and can be compared as their standard reduction potential values.
F2 + 2e → 2F; E° = 2.87 V,

Cl2 + 2e → 2Cl ; E° = 1.36 V
Since the E° of fluorine is more than that of chlorine, it is a stronger oxidising agent.
Explanation : Three factors contribute towards the oxidation potentials of both the halogens. These are :
(i) Bond dissociation enthalpy: Bond dissociation enthalpy of F2 (158 kJ mol-1) is less compared to that of Cl2 (242·6 kJ mol-1).
(ii) Electron gain enthalpy: The negative electron gain enthalpy of F (- 332·6 kJ mol-1) is slightly less than of Cl (-348·5 kJ mol-1).
(iii) Hydration enthalpy: The hydration enthalpy of F- ion (515 kJ mol-1) is much higher than that of Cl- ion (381 kJ mol-1) due to its smaller size.
From the available data, we may conclude that lesser bond dissociation enthalpy and higher hydration enthalpy compensate lower negative electron gain enthalpy of fluorine as compared to chlorine. Consequently, F2 is a more powerful oxidising agent than Cl2.

 

 

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

 

Ans:

1.       Fluorine is the most electronegative element and it does not show any positive oxidation        state except in HOF.

2.   Ionisation enthalpy, electro-negativity and electrode potential are higher for fluorine than the expected trends of other halogen.

 

7.28 Sea is the greatest source of some halogens. Comment.

 

Ans: Sea water contains chlorides, bromides and iodides of sodium, potassium, magnesium and calcium but sodium chloride being the maximum makes sea water saline. Various sea weeds contain upto 0.5% iodine. The deposits of dried up sea contains sodium chloride, carnallite (KCl, MgCl2.6H2O).

 

 

7.29 Give the reason for bleaching action of Cl2.

 

Ans: Bleaching action of chlorine is due to its oxidation. In the presence of moisture, chlorine gives nascent oxygen. This nascent oxygen bleaches colouring substances to colourless substances.

Cl2 + H2O 2 HCl + O

Colouring substance + O → Colourless substance.

 

 

7.30 Name two poisonous gases which can be prepared from chlorine gas.

 

Ans:

1.   Phosgene (COCl2)

2.   Tear gas (CCl3.NO2)

 

 

7.31 Why is ICl more reactive than I2?

 

Ans: Interhalogen compounds are more reactive than halogens (except fluorine). This is because X–X¢ bond in interhalogens is weaker than X–X bond in halogens except F–F bond. I-Cl is weaker than Cl-Cl and I-I and therefore, ICl is more reactive than I2.

 

 

7.32 Why is helium used in diving apparatus?

 

Ans: Helium along with oxygen is used in the diving apparatus by the sea divers. Since it is very less soluble in blood, it reduces decompression and causes less discomfort to the diver in breathing. A mixture of helium and oxygen does not cause pain due to very low solubility of helium in blood as compared to nitrogen.

 

 

7.33 Balance the following equation: XeF6 + H2O ® XeO2F2 + HF

 

Ans: XeF6 + 2 H2O ® XeO2F2 + 4 HF

 

 

7.34 Why has it been difficult to study the chemistry of radon?

 

Ans: Radon is a radioactive element and has very short half-life period. Therefore, it is difficult to study the chemistry of radon.

 

 

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