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.
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.
Assertion (A): HNO3 makes from passive.
Reason (R): HNO3 forms a protective layer of ferric nitrate on the surface of iron.
How is nitrogen prepared in the laboratory? Write the chemical equations of the reactions . involved.
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.
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.
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 ?
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?
(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.
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.
Nitric acid forms an oxide of nitrogen on reaction with P4O10. Write the reaction involved. Also write the resonating structures of the oxide of nitrogen formed.
An amorphous solid "A"bums in air to form a gas "B"which turns lime water milky. The gas is also produced as a by-product during roasting of sulphide ore. This gas decolourises acidified aqueous KMnO4 solution and reduces Fe3+ to Fe+2. Identify the solid "A"and the gas "B"and write the reactions involved.
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).
Why does nitrogen show catenation properties less than phosphorus ? (C.B.S.E. Foreign 2009)
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.
Give the formula and describe the structure of a noble gas species which is isostructural with: (i) ICI4– (ii) IBr2– (iii) Br03–
What happens when white phosphorus is heated with concentrated NaOH solution in an inert atmosphere of CO2 ?
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–?
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.
