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 does nitrogen show catenation properties less than phosphorus ? (C.B.S.E. Foreign 2009)
Knowing the electron gain enthalpy values of O—>O– and O—>O2- as -141 and 702 kJ mol-1 respectively, how can you account for [he formation of a large number of oxides having O2- species and not O–?
Explain why inspite of nearly the same electronegativity, nitrogen forms hydrogen bonding while chlorine does not.
Which of the following statements are correct?
(a) All three N – O bond lengths in HNO3 are equal.
(b) All P – Cl bond lengths in PCl5 molecule in gaseous state are equal.
(c) P4 molecule in white phosphorus have angular strain therefore white phosphorus is very reactive.
(d) PCl5 is ionic in solid state in which cation is tetrahedral and anion is octahedral.
On heating with concentrated NaOH solution in an inert atmosphere of CO2, white phosphorus gives a gas. Which of the following statement is incorrect about the gas?
(a) It is highly poisonous and has smell like rotten fish.
(b) Its solution in water decomposes in the presence of light.
(c) It is more basic than NH3
(d) It is less basic than NH3
Which of the following options are not in accordance with the properly mentioned against them?
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.
Why is nitric oxide paramagnetic in gaseous state but the solid obtained on cooling is diamagnetic?
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.
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.
What happens when sulp’hur dioxide is passed through an aqueous solution of Fe(III) salt?
Comment on the nature of two S-O bonds formed in S02 molecule. Are the two S-O bonds in this molecule equal ?
How is nitrogen prepared in the laboratory? Write the chemical equations of the reactions . involved.
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.
On addition of cone. H2SO4 to a chloride salt, colourless fumes are evolved but in case of iodide salt, violet fumes come out. This is because
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
Which of the following acid forms three series of salts?
(a) H2PO2 (b) H3BO3 (C)H3PO4(d)H3PO3
Which of the following is correct for P4 molecule of white phosphorus?
(a) It has 6 lone pairs of electrons (b) It has six P – P single bonds
(c) It has three P – P single bonds (d) It has four lone pairs of electrons,
