Discuss the trends in chemical reactivity of group 15 elements.
Hydrides: All elements of group 15 form gaseous hydrides of the type MH3.
In all the hydrides the central atom is sp3 hybridized and their shape is pyramidal due to presence of lone pair of electrons.
(a)The basic strength of the hydrides decreases as we move down the group.
Thus, NH3 is the strongest base.
NH3 > PH3 > AsH3 > SbH3
(b)The thermal stability of the hydrides decreases as the atomic size increases, i.e., the M – H bond strength decreases which means reducing character increases.
(c)In the liquid state, the molecules of NH3are associated due to hydrogen bonding. The molecules of other hydrides are not associated.
(d)NH3 is soluble in water whereas other hydrides are insoluble.
(e)All the hydrides, except NH3, are strong reducing agents and react with metal ions (Ag+, Cu2+, etc.) to form phosphides, arsenides or antimonides.
Halides: The elements of group 15 form two series of halides MX3 and MX5.
(a)All the elements of the group form trihalides. The ionic character of trihalides increases as we move down the group. Except NCl3 all the trihalides are hydrolysed by water. This is due to the absence of d-orbitals in nitrogen.
(b)PF3 is not hydrolysed because fluorine being more electronegative than oxygen forms more stable bonds with phosphorus than P – O bonds.
(c)N cannot form NX5 because of non-availability of rforbitals. Bi cannot form BiX3 because of reluctance of 6s electrons of Bi to participate in bond formation.
(d)The hybridisation of M in MX3 is sp3 and shape is pyramidal. M in MX5 is sp3 as hybridised and shape is trigonal pyramidal. The axial bonds in MX5 are weaker and longer, So MX5 are less stable and decompose on heating eg:
Oxides:
(a)Nitrogen forms a number of oxides. The rest of the members (P, As, Sb and Bi) of the group form two types of oxides : E203 and E2O5.
(b)The reluctance of P, As, Sb and Bi to enter into pπ -pπ multiple bonding leads to cage structures of their oxides and they exist as dimers, E4O6 and E5O10.
(c)The basic nature of die oxides increases with increase in atomic number of the element. Thus, the oxides of nitrogen (except N20 and NO), P (III) and As (III) are acidic, Sb (III) oxide is amphoteric and Bi (III) oxide is basic.
Why is BiH3 the strongest reducing agent amongst all the hydrides of group 15 elements? (C.B.S.E. 2013)
Justify the placement of O, S, Se, Te and Po in the same group’of the periodic table in terms of electronic configuration, oxidation state and hydride formation.
Which of the following statements are correct?
(a) Among halogens, radius ratio between iodine and fluorine is maximum.
(b) Leaving F – F bond, all halogens have weaker X – X bond than X – X’ bond in interhalogens.
(c) Among interhalogen compounds maximum number of atoms ate present in iodine fluoride.
(d) Interhalogen compounds are more reactive than halogen compounds.
Which of the following statements are correct for SO2 gas?
(a) It acts as a bleaching agent in moist conditions.
(b) Its molecule has a linear geometry.
(c) Its dilute solution is used as disinfectant.
(d) It can be prepared by the reaction of dilute H2SO4 with metal sulphide.
Name three oxoacids of nitrogen. Write the disproportionation reaction of that oxoacid of nitrogen in which nitrogen is in +3 oxidation state.
Discuss the general characteristics of Group 15 elements with reference to their electronic configuration, oxidation state, atomic size, ionisation enthalpy and electronegativity.
Explain why does the stability of oxoacids of chlorine increase in the order given below:
HClO < HClO2 < HClO3 < HClO4
Assertion (A): HNO3 makes from passive.
Reason (R): HNO3 forms a protective layer of ferric nitrate on the surface of iron.
On heating compound (A) gives a gas (B) which is a constituent of air. This gas when treated with 3 mol of hydrogen (H2 ) in the presence of a catalyst gives another gas (C) which is basic in nature. Gas C on further oxidation in moist condition gives a compound (D) which is a part of acid rain. Identify compounds (A) to (D) and also give necessary equations of all the steps involved. –
How is nitrogen prepared in the laboratory? Write the chemical equations of the reactions . involved.
Justify the placement of O, S, Se, Te and Po in the same group'of the periodic table in terms of electronic configuration, oxidation state and hydride formation.
White phosphorus reacts with chlorine and the product hydrolysis in the presence of water. Calculate the mass of HCl obtained by the hydrolysis of the product formed by the reaction of 62 g of white phosphorus with chlorine in the presence of water.
Phosphorus forms a number of oxoacids. Out of these oxoacids phosphinic acid has strong reducing property. Write its structure and also write a reaction showing its reducing behaviour.
Assertion (A): HI cannot be prepared by the reaction of KI with concentrated H2SO4.
Reason (R): HI has lowest H – X bond strength among halogen acids.
What happens when white phosphorus is heated with concentrated NaOH solution in an inert atmosphere of CO2?
Comment on the nature of two S-O bonds formed in S02 molecule. Are the two S-O bonds in this molecule equal ?
Write balanced equations for the following:
(i) NaCl is heated witlrsulphuric acid in the presence of MnO2
(ii) Chlorine gas is passed into a solution of Nal in water.
If chlorine gas is passed through hot NaOH solution, two changes are observed in the oxidation number of chlorine during the reaction. These are —— and ——-
What happens when sulp’hur dioxide is passed through an aqueous solution of Fe(III) salt?
The HNH angle value is higher than HPH, H AsH and HSbH angles. 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).
Reduction potentials of some ions are given below. Arrange them in decreasing order of oxidizing power.
Which of the following orders are correct as per the properties mentioned against each?
On reaction with Cl2, phosphorus forms two types of halides ‘A' and ‘B'. Halide A is yellowish-white powder but halide B' is colourless oily liquid. Identify A and B and write the formulas of their hydrolysis products.
In the ring test of NO3 ion.Fe2+ion reduces nitrate ion to nitric oxide, which combines with Fe2+ (aq.) ion to form brown complex. Write the reactions involved in the formation of brown ring.
Arrange the following in the order of property indicated for each set: –
(i) F2 , Cl2 , Br2 , I2 – increasing bond dissociation enthalpy.
(ii) HF, HCI, HBr, HI – increasing acid . strength.
(iii) NH3, PH3, AsH3, SbH3, BiH3 – increasing Sol. base strength.
