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.
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.
Comment on the nature of two S-O bonds formed in S02 molecule. Are the two S-O bonds in this molecule equal ?
Discuss the general characteristics of Group 15 elements with reference to their electronic configuration, oxidation state, atomic size, ionisation enthalpy and electronegativity.
Discuss the general characteristics of Group 15 elements with reference to their electronic configuration, oxidation state, atomic size, ionisation enthalpy and electronegativity.
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).
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.
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).
What are the oxidation states of phosphorus in the following: –
(i) H3PO3 (ii)PCl3
(iii) Ca3P2(iv)Na3PO4
(v) POF3
Write a balanced chemical equation, for the reaction showing catalytic oxidation of NH3 by atmospheric oxygen.
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.
PCl5 reacts with finely divided silver on heating and a white silver salt is obtained, which dissolves on adding excess aqueous NH3 solution. Write the reactions involved to explain what happens.
How is nitrogen prepared in the laboratory? Write the chemical equations of the reactions . involved.
With which neutral molecule is ClO– isoelectronic? Is this molecule Lewis acid or base ? (Pb. Board 2009)
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.
In qualitative analysis when H2S is passed through an aqueous solution of salt acidified with dil. HCl, a black precipitate is obtained. On boiling the precipitate with dil. HNO3, it forms a solution of blue colour. Addition of excess of aqueous solution of ammonia to this solution gives
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 ——-
Which of the following orders are correct as per the properties mentioned against each?