15TH Group elements
1. The atomic radii increases considerably from N to P but very little increase is observed from A to B. why? There is a considerable increase in size from N to P as expected but due to the presence of completely filled d- orbitals which have very poor shielding effects , the increases in size is very little from As to Bi. 2. Give reason for the following- the first ionization enthalpy of 15th group elements is higher than 16th group elements ? Due to extra stability of half filled configuration, the first Ionisation enthalpy of 15th group elements is higher than 16th group configuration ns2np4) 3. How does metallic character vary down the 15 group & why? The metallic character increases down the group due to decrease in ionization enthalpy and increase in size of atom. 4. What are the common oxidation states of this group? The common oxidation states of the group are- -3 , +3 & +5. 5. What is the maximum covalence shown by N? Nitrogen shows a maximum covalence of +4 because only four orbitals, one S and three P orbital are available for bonding in Nitrogen. And absence of d-orbitals 6. Bi (v) is a stronger oxidizing agent than Bi. Why? Bi is more stable in +3 oxidation state in comparison to +5 due to inert pair effect therefore Bi (v) has a strong tendency to act as oxidizing agent. 7. Give reasons for the following? (a) Nitrogen does not show catenation. Nitrogen being small in size has high electron density . Due to strong inter electronic repulsions, N-N single bond is weak & nitrogen does not undergo catenation. (b) Pcl5 exists but NCl5 does not.
Due to absence of d-orbitals, nitrogen cannot expand its oxidation state to +5 and Ncl5 does not exist whereas in P due to presence of empty 3d orbital +5 oxidation state is attained.
(c) The stability of Hydrides follows the orderAs we move down the group 15, atomic radil increases making the bond(E-H) of element with Hydrogen Weaker this decreases the stability of hydrides of heavier elements. Therefore the order of stability is .
13. Ammonia is a Lewis base. it can donate electron pair and acts as a lewis base. How does ammonia react with a solution of Cu2+? NH3 acts as a Lewis base. N2 is less reactive at room temperature. The bond dissociation energy of this bond is very high.
Molecular nitrogen (N2) is inert because N≡ N bond energy is very high due to small size of N. 9. Since the stability of hydrides decreases on moving from NH3 to BiH3. Ammonia has higher boiling and melting points than expected . As a result. 14. Why? Due to the presence of lone pairs or nitrogen atom of ammonia. pentahalides are more covalent than trihalides. There fore ammonia has higher boiling and melting points 10.(d) PH3 is a weaker base than NH3. It donates its electron pair and forms a linkage with metal ion.
8.atom and present of multiple bond.atom.
As Phosphorous atom is larger than N.Why? In solid and liquid states.
11. Since the metal ion with a high charge has more polarizing power. the oxidation state is +3. Why are pentahalides more covalent than trihalides?
In pentahalides. the cone pain of electrons is distributed over a large surface area of P-atom than N-atom than N. Therefore the tendency of P to donate the cone pair of electrons is less.
. which reacts with Fe2+ to form a brown coloured complex.
(e) Molecular nitrogen is chemically inert. The yield of ammonia can be maximized under the following conditions: (i) High pressure (∼ 200 atm) (ii) A temperature of ∼700 K(iii) Use of a catalyst such as iron oxide mixed with small amounts of K2O and Al2O3 15. Why is BiH3 the strongest reducing agent amongst all the hydrides of Group 15 elements?
As we move down a group. the oxidation state is +5 and in trihalides. Mention the conditions required to maximise the yield of ammonia. Explain the chemistry behind brown ring test for detection of nitrate ions. the atomic size increases and the stability of the hydrides of group 15 elements decreases AS E-H Bond strength decreases . Ammonia is prepared using the Haber’s process.atom. The brown ring test for nitrate ions depends on the ability of Fe2+ to reduce nitrates to nitric oxide. Why is N2 less reactive at room temperature? The two N atoms in N2 are bonded to each other by very strong triple covalent bonds. the reducing character of the hydrides increases on moving from NH3 to BiH3. ammonia molecules are associated by intermolecular hydrogen bonding.
18. Bond angle in
is higher than that in PH3. it is evident that the covalence of nitrogen is 4. What is the basicity of H3PO4?
Since there are three OH groups present in H3PO4. there is no lone pair-bond pair repulsion. Therefore. its basicity is three i. What is the covalence of nitrogen in N2O5?
From the structure of N2O5. P is sp3 hybridized. 19. the
is higher than the bond angle in PH3. PH3 combines with a proton to form to the absence of lone pair in bond angle in in which the lone pair is absent. It has three equatorial and two axial bonds. Hence.
17. it can decrease its oxidation state and act as an oxidizing agent. Why?
In PH3. it decomposes to form PCl3. Due
. it is a tribasic acid.
20. Three orbitals are involved in bonding with three hydrogen atoms and the fourth one contains a lone pair.. In PCl5. the tetrahedral shape associated with sp3 bonding is changed to pyramidal. What happens when PCl5 is heated? All the bonds that are present in PCl5 are not similar.
. phosphorus is in its highest oxidation state (+5).e. As lone pair-bond pair repulsion is stronger than bond pair-bond pair repulsion. when PCl5 is heated strongly. PCl5 can only act as an oxidizing agent. The highest oxidation state that P can show is +5. Can PCl5 act as an oxidising as well as a reducing agent? Justify. However.16. The equatorial bonds are stronger than the axial ones.
24. the two nitrogen atoms form a triple bond. N2. PH3. An aqueous solution of ammonium chloride is treated with sodium nitrite. Why does the reactivity of nitrogen differ from phosphorus? Nitrogen is chemically less reactive. the reaction is a disproportionation reaction. The products of oxidation depend on the concentration of the acid. This triple bond has very high bond strength. It is because of nitrogen’s small size that it is able to form pπ−pπ bonds with itself. undergoes disproportionation reaction to form PH3 and H3PO4. 23. phosphorus is more reactive than nitrogen.
25. How is nitrogen prepared in the laboratory? Write the chemical equations of the reactions
involved. containing potassium dichromate. and also on the material undergoing oxidation. which is very difficult to break. Illustrate how copper metal can give different products on reaction with HNO3. on heating. What happens when H3PO3 is heated?
H3PO3. This is because of the high stability of its molecule. Give the resonating structures of NO2 and N2O5. Thus. and H3PO4 are +3.21.
. These are impurities that can be removed on passing nitrogen gas through aqueous sulphuric acid.
Concentrated nitric acid is a strong oxidizing agent. In N2. As the oxidation number of the same element is decreasing and increasing during a particular reaction. It is used for oxidizing most metals. temperature. This property is not exhibited by atoms such as phosphorus. . and +5 respectively. The oxidation numbers of P in H3PO3. −3.
NO and HNO3 are produced in small amounts.
Nitrogen thus forms a very stable diatomic molecule. resulting in maximum bond angle.
29. Explain why NH3 is basic while BiH3 is only feebly basic. Since nitrogen is highly electronegative. We know that electronegativity decreases on moving down a group. Consequently.
. thereby decreasing the H−M−H bond angle. Nitrogen exists as diatomic molecule and phosphorus as P4. Write main differences between the properties of white phosphorus and red phosphorus. This restricts nitrogen to expand its coordination number beyond four.
30. phosphorus (like other heavier metals) exists in the P4 state.
27. Why? [Hint: Can be explained on the basis of sp3 hybridisation in NH3 and only s−p bonding between hydrogen and other elements of the group]. This causes greater repulsion between the electron pairs around nitrogen. HAsH and HSbH angles. The HNH angle value is higher than HPH. there is high electron density around nitrogen. the size of the central atom increases and the charge gets distributed over a large area decreasing the electron density.
NH3 is distinctly basic while BiH3 is feebly basic. R3N=O does not exist. Therefore. Hence.26. Nitrogen has a small size due to which the lone pair of electrons is concentrated in a small region. This means that the charge density per unit volume is high. the tendency to form pπ−pπ bonds decreases (because of the large size of heavier elements).
White phosphorus It is a soft and waxy solid. the repulsive interactions between the electron pairs decrease. Red Phosphorus It is a hard and crystalline solid. the electron donating capacity of group 15 element hydrides decreases on moving down the group.
28. It possesses a garlic smell. On moving down a group. without any smell. Why does R3P=O exist but R3N=O does not (R = alkyl group)?
N (unlike P) lacks the d-orbital. N2. On moving down a group. Hydride NH3 PH3 AsH3 SbH3 H−M−H angle 107° 92° 91° 90° The above trend in the H−M−H bond angle can be explained on the basis of the electronegativity of the central atom. Hence. Why?
Nitrogen owing to its small size has a tendency to form pπ−pπ multiple bonds with itself.
Explain the chemistry behind brown ring test for detection of nitrate ions. which reacts with Fe2+ to form a brown coloured complex. there is greater repulsion of electron density of two nitrogen atoms. It undergoes spontaneous combustion in air. When heated . Give an equation in support of this statement.
All five bonds in PCl5 are not equal .
It is non-poisonous. On heating. The brown ring test for nitrate ions depends on the ability of Fe2+ to reduce nitrates to nitric oxide.
Give the disproportionation reaction of H3PO3. orthophosphorus acid (H3PO3) disproportionates to give orthophosphoric acid (H3PO4) and phosphine (PH3).
33. This is because of the relative weakness of the N−N single bond as compared to the P−P single bond. Since nitrogen atom is smaller. thereby weakening the N−N single bond.It is poisonous. PCl5 loses a chlorine molecule this shows that two P.
It is relatively less reactive.
It exists as a chain of tetrahedral P4 units. It is insoluble in both water and carbon disulphide.CL bonds are weaker and hence longer than other PCl5 a→ PCl3 + Cl2 t
. it exists as a P4 molecule. It is insoluble in water but soluble in carbon disulphide. Why does nitrogen show catenation properties less than phosphorus?
Catenation is much more common in phosphorous compounds than in nitrogen compounds. In both solid and vapour states. The oxidation states of P in various species involved in the reaction are mentioned below.
Complete and balance –
Complete and balance-3Mg + N →
What happens when white phosphorus is heated with concentrated NaOH solution in an inert atmosphere of CO2? White phosphorous dissolves in boiling NaOH solution (in a CO2 atmosphere) to give phosphine. when calcium phosphide is hydrolised?
COMPLETE write a chemical reaction .
Complete and Balance
41. Draw the structure of following :(i) NO (ii) N2O4 (iii) HNO3 (iv) PCl5 (v) (H3PO3)3 (vi) H3 PO2 (vii) H3PO3