P Block Elements
P Block Elements
P Block Elements
p-BLOCK ELEMENTS
Consequences :
1. The rst element in p-block element has four valence orbitals i.e., one 2s and
three 2p. Hence maximum covalency of the rst element is limited to four.
The other elements of the p-block have vacant d-orbitals in their valence shell,
e.g., three 3p and ve three 3d orbitals. Hence, these elements show maximum
covalence greater than four. Following questions can be answered :
(i) Nitrogen (N) does not form pentahalide while P forms PCl5, PF5 and
PF6. Why ?
(ii) Sulphur (S) forms SF6 but oxygen does not form OF6. Why ?
(iii) Though nitrogen forms pentoxide but it does not form pentachloride. Why ?
(iv) Fluorine forms only one oxoacid while other halogens form a number of
oxoacids. Why ?
2. The rst member of p-block elements displays greater ability to form p-p
bond(s) with itself, (e.g., C=C, CC, N=N, N N) and with the other elements
of second period, for example, C =O, C N, N=O compared to the subsequent
members of the group.
This is because p-orbitals of the heavier members are so large and diffuse that
they cannot have effective sideways overlapping. Heavier members can form p
-d bonds with oxygen.
In case of HNO3, two nitrogen-oxygen bonds are identical and smaller than
the third nitrogen-oxygen bond. This is because the third N – OH bond is not
involved in resonance.
Now the following questions can be explained on the basis of this concept :
(i) In SO2, the two sulphur-oxygen bonds are identical. Explain why ?
(ii) In NO3 ion, all the three N– O bonds are identical. Why ?
Bond angle : In regular structures (where no lone pairs are present in the
valence shell of the central atom in a molecule/ion), the bond angle does not depend
upon the size/electronegativity of the central or terminal atoms.
In presence of lone pair(s) on the central tom, the geometry is distorted and the
bond angle is changed.
Comparison of HNH and HPH bond angles
Since N is more electronegative than P, the bonding electron pair of N– H bond
will shift more towards N atom than the bonding electron pair of P – H bond would shift
towards P atom. This results in more bond pair-bond pair repulsion in NH3 molecule
than PH3 molecule. Because of more Ip-bp repulsion, the N– H bonds are pushed closer
to a lesser extent than in PH3. Consequently, HNH bond angle is greater than HPH
angle.
Now, the following questions can be explained using the above mentioned concept :
(i) Bond angle in PH4+ ion is higher than in PH3. Why ?
(ii) H– O – H bond in H2O is greater than H– S– H angle in H2S. Why ?
Boiling and melting points of hydrides depends upon the molar mass (or surface
area) of molecules. More the molar mass, the higher is the m.p. and b.p. Hydrides
forming intermolecular hydrogen bonds have exceptionally high m.p. and b.p. since
intermolecular hydrogen bonds are stronger than the van der Waals forces.
Increasing order of melting point and boiling point of hydrides is as given below :
PH3 < AsH3 < SbH3 < NH3 Melting point
PH3 < AsH3 < NH3 < SbH3 Boiling point
H2S < H2Se < H2Te < H2O Melting point and boiling point
HCl < HBr < HI < HF Boiling point
HCl < HBr < HF < HI Melting point
(i) NH3 has higher boiling point than PH3.
(ii) H2O is liquid and H2S is gas or H2S is more volatile than H2O.
Thermal stability, reducing power and acid strength of hydrides depend upon
bond dissociation enthalpy of E – H bond (E = group 15, group 16, and group 17
element). Due to the increase in size down the group, bond dissociation enthalpy of E –
H bond decreases. Consequently, thermal stability, reducing power and acid strength of
hydrides increases down the group.
The following questions can be explained using the above concepts.
Explain why :
(i) HF is weaker acid than HCl.
(ii) Among hydrogen halides, HI is the strongest reducing agent.
(iii) H2Te is more acidic than H2S.
(iv) NH3 is mild reducing agent while BiH3 is the strongest reducing agent among
the group-15 hydrides.
(v) H2S is weaker reducing agent than H2Te.
Basic nature of hydrides EH3 of group 15 elements
All the hydrides EH3 of group 15 elements has one lone pair of electrons. In ammonia,
the lone pair of electrons is present in sp3 hybrid orbital of the N-atom. The sp3 hybrid
orbital is directional and further N is more electronegative than H, the bond pair of N
– H is shifted towards N atom which further increases the electron density on N atom.
In PH3, the lone pair of electrons is present in large and more diffuse 3s orbital which
is non-directional. As a result, PH3 is less basic than NH3 and basic character decreases
down the group. NH3 donates electron pair more readily than PH3. (SiH3)3N has less
Lewis basic nature than that of (CH3)3N because lone pair of electrons in p-orbital of N
atom in (SiH3)3N is transferred to the vacant d-orbital of Si atom forming d-p bond.
The more negative the value of rH = ½ diss H – eg H – hyd H the higher will be
oxidizing property of the halogen and more positive will be standard reduction potential
Ered of the halogen.
Following questions can be explained on the basis of parameters, like diss H, eg H
and hyd H.
(i) Why does F2 have exceptionally low bond dissociation enthalpy ?
(ii) Although electron gain enthalpy of uorine (F) is less negative as compared to
chlorine (Cl), Fluorine gas (F2) is a stronger oxidizing agent than Cl2 gas. Why ?
Some Important Reactions
1.
5.
6. 4HNO3 + P4O10 4HPO3 + 2N2O5
7. 3Cu + 8HNO3 (dil.) 3Cu(NO3)2 + 2NO + 4H2O
8. Cu + 4HNO3 (conc.) Cu(NO3)2 + 2NO2 + 2H2O
9. 4Zn + 10HNO3 (dil.) 4Zn(NO3)2 + N2O + 5H2O
10. Zn + 4HNO3 (conc.) Zn(NO3)2 + 2NO2 + 2H2O
11. I2 +10HNO3 (conc.) 2HIO3 + 10NO2 +4H2O
12. S8 + 48HNO3 (conc.) 8H2SO4 + 48NO2 + 16H2O
13. P4 + 20HNO3 (conc.) 4H3PO4 + 20NO2 + 4H2O
14. Chemistry of ring test :
NO3 + 3Fe2+ + 4H+ NO + 3Fe3+ + 2H2O
[Fe(H2O)6]2+ + NO [Fe(H2O)5NO]2+ + H2O
15. P4 + 3NaOH + 3H2O PH3 + 3NaH2PO2
16. P4 + 8SOCl2 4PCl3 + 4SO2 + 2S2Cl2
17. P4 + 10SO2Cl2 4PCl5 + 10SO2
18. PCl3 + 3H2O H3PO3 + 3HCl
19. PCl5 + 4H2O H3PO4 + 3HCl
NaHSO4 + HCl
32. XeF2 + PF5 [XeF]+[PF6]
33. XeF6 + MF M+[XeF7] (M = Na, K, Rb or Cs)
34. 6XeF4 + 12H2O 4Xe + 2XeO3 + 24HF + 3O2
35. XeF6 + 3H2O XeO3 + 6HF
36. XeF6 + H2O XeOF4 + 2HF
37. XeF6 + 2H2O XeO2F2 + 4HF
–
VERY SHORT ANSWER TYPE QUESTIONS (1 Mark)
Q. 1. In group 15 elements, there is considerable increase in covalent radius
from N to P but small increase from As to Bi. Why ?
[Hint : Due to completely lled d- and/or f-orbitals in As, Sb and Bi.]
Q. 2. The tendency to exhibit – 3 oxidation state, decreased down the group in
group 15 elements. Explain.
[Hint : Due to increase in size and decrease in electronegativity down the
groups.]
Q. 3. Maximum covalence of nitrogen is ‘4’ but the heavier elements of group 15
show covalence greater than ‘4’. Why ?
[Hint : Nitrogen is not having vacant d- orbitals in its octet, hence cannot expand
its octet, while heavier members have vacant d-orbitals to expand their octet.]
Q. 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 E 2 at room
temperature. Assign a reason.
[Hint : p-p multiple bonds are formed by N due to its small size.]
Q. 5. The ionization enthalpies of group 15 elements are higher than those of
corresponding members of group 14 and 16 elements. Assign the reason.
[Hint : Due to their stable electronic con guration (ns2np3).]
Q. 6. The boiling point of PH3 is lesser than NH3. Why ?
[Hint : NH3 molecules are stabilized by intermolecular H-bonding, while PH3
by weak van der Waals’s forces.]
Q. 7. NO2 dimerises to form N2O4. Why ?
[Hint : Due to presence of odd electron on N.]
Q. 8. Draw the structure of N2O5 molecule.
Ans.
Q. 9. How does ammonia solution react with Ag+ (aq) ? Write the balanced
chemical equation.
[Hint : Ag+ (aq) + 2NH3 (aq) [Ag(NH3)2]+ (aq)]
Q. 10. Why does NH3 forms intermolecular hydrogen bonds whereas PH3 does
not ?
[Hint : Due to strong electronegativity, small size of nitrogen atom and presence
of lone pair of electrons on N atom.]
Q. 11. Write disproportionation reaction of H3PO3 ?
[Hint : 4H3PO3 3H3PO4 + PH3]
Q. 12. How does NH3 acts as a complexing agent ?
[Hint : Metal hydroxides are dissolved in excess of NH4OH. Ammonia acts as
a Lewis base. It can donate electron pair to central metal atom or ion.]
Q. 13. Write the reaction of PCl5 with heavy water.
[Hint : PCl5 + D2O POCl3 + 2DCl]
Q. 14. What is laughing gas ? How is it prepared ?
[Hint : N2O, NH4NO3 N2O + 2H2O]
Q. 15. Why is white phosphorus kept under water ?
[Hint : Due to high angular strain, it is highly reactive and catches re in air,
hence kept under water.]
Q. 16. “Hydrophosphorus acid is a good reducing agent.” Justify with an example.
[Hint : 4AgNO3 + H3PO2 + 2H2O 4Ag + 4HNO3 + H3PO4]
Q. 17. Draw the structure of H4P2O7 and nd out its basicity.
[Hint :
Q. 23. In the structure of HNO3 molecule, the N – O bond (121 pm) is shorter than
N – OH bond (140 pm).
[Hint : Due to resonance N – O bond is having partial double bond character
hence shorter than N – OH bond which is pure single bond character.]
Q. 17. Give chemical reaction in support of the statement that all the bonds in
PCl5 molecule are not equivalent.
GROUP 17 ELEMENTS
VERY SHORT ANSWER TYPE QUESTIONS (1 Mark)
Q. 1. Explain why uorine forms only one oxoacid, HOF.
[Hint : Because of unavailability of d-orbitals in its valence shell.]
Q. 2. Why HF is the weakest acid and HI is the strongest ?
[Hint : Ka (HF) = 7 104 Ka (HI) = 7 1011
Intermolecular H-bonds in H – F and high bond dissociation enthalpy of H – F
makes it weakest and weak bond in H – I makes it strongest.]
Q. 3. Explain why halogens are strong oxidizing agents.
[Hint : High electronegativity and more negative electron gain enthalpies of
halogens.]
Q. 4. I2 is more soluble in KI than in water. Why ?
[Hint : KI + I2 KI3]
Q. 5. What is cause of bleaching action of chlorine water ? Explain it with
chemical equation.
[Hint : Formation of nascent oxygen.]
Q. 6. Electron gain enthalpy of uorine (F) is less negative than that of chlorine
(Cl). Why ?
[Hint : Due to small size of F atom and compact 2p orbitals there are strong
interelectronic repulsions in the relatively smaller 2p orbitals of uorine. So the
incoming electron does experience more repulsion in F than in Cl.]
Q. 7. Why can’t we prepare HBr by heating KBr with sulphuric acid ?
[Hint : As HBr readily reduces H2SO4 forming Br2.]
Q. 8. Explain why : ICl is more reactive than I2 ?
[Hint : Because I – Cl bond is weaker than I – I bond.]
Q. 9. Which oxide of iodine is used for the estimation of carbon mono oxide ?
[Hint : I2O5]
Q. 10. Arrange the following oxoacids of chlorine in increasing order of acid
strength :
HOCl, HOClO, HOClO2, HOClO3
[Hint : HOCl < HOClO < HOClO2 < HOClO3]
Q. 11. Why does uorine not play the role of a central atom in interhalogen
compounds ?
[Hint : Due to smallest size of F.]
Q. 12. Fluorine exhibit only – 1 oxidation state whereas other halogens exhibit
+ve oxidation states also. Explain why ?
[Hint : Due to absence of vacant d-orbitals in the octet of F.]
Q. 13. ClF3 exists but FCl3 does not. Why ?
[Hint : Because F does not show oxidation state other than – 1.]
Q. 14. Despite lower value of its electron enthalpy with negative sign, uorine is a
stronger oxidizing agent than chlorine. Explain.
[Hint : Due to its low bond dissociation enthalpy (F –F bond) and high hydration
enthalpy of F.]
Q. 15. ClF3 molecule has a bent T-shaped structure and not a trigonal planar
structure. Explain.
[Hint : Due to presence of 2LP and 3BP.]
Q. 16. What happens when NaCl is heated with H2SO4 in the presence of MnO2 ?
[Hint : 4NaCl + MnO2 + 4H2SO4 MnCl2 + 4NaHSO4 + 2H2O + Cl2]
Q. 17. With what neutral molecule ClO is isoelectronic ?
[Hint : ClF or OF2.]
Q. 18. Why HF acid is stored in wax coated glass bottle ?
[Hint : HF is corrosive, hence HF attacks glass surface.]
Q. 19. Bond dissociation enthalpy of F2 is less than that of Cl 2. Explain why ?
[Hint : F2 is having higher electron-electron repulsion due to its smaller size, as
compared to Cl2.]
Hint :
Linear Linear
[I – I I ]
[Cl – I Cl]
SHORT ANSWER-II TYPE QUESTIONS (3 Marks)
Q. 1. Give appropriate reason for each of the following :
(i) Metal uorides 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 are more polarized than the
smaller ions by a particular cation.
(ii) ClO4 is more resonance stabilized than SO42 since dispersal of negative
charge is more effective in ClO4 as compared with SO42.
(iii) 2KI + Cl2 2KCl + I2
5Cl2 (excess) + I2 + 6H2O 2HIO3 + 10HCl
(colourless)
Q. 2. X2 is a greenish yellow gas with pungent offensive smell used in puri cation
of water. It partially dissolves in H2O to give a solution which turns blue
litmus red. When X2 is passed through NaBr solution, Br2 is obtained.
(i) Identify X2, name the group to which it belongs.
(ii) What are the products obtained when X2 reacts with H2O ? Write
chemical equation.
(iii) What happens when X2 reacts with hot and conc. NaOH ? Give
equation.
[Hint : (i) Cl2, 17 group.
(ii) Cl2 (g) + 2H2O (l) HCl (aq) + HOCl (aq)
(iii) 3Cl2 + 6NaOH 5NaCl + NaClO3 + 3H2O]
Q. 3. Arrange the following in the order of the property indicated for each set :
(i) F2, Cl2, Br2, I2 (Increasing bond dissocation energy)
(ii) HF, HCl, HBr, HI (decreasing acid strength)
(iii) NH3, PH3, AsH3, SbH3, BiH3 (Decreasing base strength)
[Hint : (i) F2 has exceptionally low bond dissociation enthalpy. Lone pairs
in F2 molecule are much closer to each other than in Cl2 molecule. Stronger
electron-electron repulsions among the lone pairs in F2 molecule make its bond
dissociation enthalpy exceptionally low.
(ii) Acid strength depends upon H – X bond dissociation enthalpy. As the size
of ‘X’ atom increases, bond dissociation enthalpy of H – X decreases.
(iii) Electron availability on the central atom ‘E’ in EH3 decreases down the
group.]
Q. 4. Draw the structure of :
(i) Hypochlorous acid
(ii) Chlorous acid
(iii) Perchloric acid
Hint :
GROUP 18 ELEMENTS
(ii)
(b)
Red phosphorus
(R)
ANSWERS
1. (A) (1) (B) (3) (C) (4) (D) (2)
2. (A) (4) (B) (1) (C) (2) (D) (3)
3. (A) (4) (B) (3) (C) (1) (D) (2)
4. (A) (3) (B) (2) (C) (1) (D) (4)
5. (A) (2) (B) (3) (C) (2) (D) (4)