GROUPS 15 ELEMENTS - THE NITROGEN FAMILY COLLECTIVELY THESE ARE KNOWN AS PNICOGENS AND THEIR COMPOUNDS AS PNICTIDES. __| Electronic Configuration [Hej2s" 2p" i — = ING ap ees =e ey ____[fan3a™. 4s? 4p" = —_[IKnad™, 5s” 5p: [Xe]4f"", 5d", 68" 6p" CHARACTERISTIC OF NITROGEN FAMILY 24 244 24.2 24.3 241.4. 2.4.5. 24.6. 247. Physical Properti Electronic Configuration All these elements have general configuration of ns* np®. These are also p-block ‘elements since differentiating electron enters in p-block + fl Git Abundance Nitrogen is widely present in nature both in free as well as in the combined state. Phosphorus is an active element and thus, not found free in nature. It occurs as phosphates in the rocks and soil ; as phosphoproteins in all living beings (an essential constituent of bones, teeth, blood and nervous tissues). It is necessary for the growth of plants Non-metallic nature Like group 13 and group 14, there is a transition from non-metallic to metallic nature on moving down the group. N PAS Sb Bi wee Non-metals Semi-metals or metalloid Metal Melting point and boiling point The m.p. of pnicogens increases from nitrogen to arsenic and then decreases from arsenic to bismuth The lower values of Bi and Sb than As are explained on the basis of their more, tendency to show three covalent bonds instead of five covalent bonds due to inert pair effect. This brings in weak forces of attraction between their atoms in solid state leading to lowering in m.p. Morever, Bi being larger in size than antimony and thus, shows relatively weaker attractive forces between their atoms in solid state. The bp. of pnicogens, however, shows a regular trend as given below Element N Pe AS sb Bi bp. (K) 772 554 BBB 1860 1837 Physical state Nitrogen, the first element, is a gas while phosphorus, the second member, a soft waxy solid, however, can pass readily into vapour state. The remaining elements are solids. These all (except N and Bi) exist as discrete, tetraatomic, tetrahedral molecules. N exists as No in gaseous state and Bi as Bi, in solid state, Atomic radii Atomic radii increase with the increase of atomic number. The difference between N and P is comparatively high due to more effective shielding of 2s and 2p-orbitals in phosphorus. lonisation eneray The first ionisation energy decreases regularly on moving down the group. The ionisation energy of nitrogen is very high due to smaller size. The difference in ionisation energy between N and P is more but the difference afterwards between to consecutive members is small due to less shielding effect of d-electrons in As and Sb and of d and f-electrons in Bi2.4.10 Furthermore, it should be noted that first ionisation energies of group 15 members are much higher than those of eoresponding group 14,and group 16 elements, The higher values of IE, {group 14 elements are due to increase in nuclear charge. Extra stable ie haff filed configuration of p-subshell of group 15 elements accounts for the hhigher values of IE, than corresponding group 16 elements. Electronegativity ()—Electronegativity decreases gradually on moving down the group from N to Bi (i) N being most electronegative element of group 15 and shows more affinity to ‘show Non, (i) Bi having lowest electronegative nature and thus, shows ionic compound with most electronegative element, viz. , BiF has ionic lattice Oxidation state and valency ()All'these elements have two paired s-electrons and three unpaired p-electrons. in their valence shell and thus, exhibit three covalence involving sharing of | three electron pairs to attain stable noble gas configuration. (i) Except N, all have got vacant d-orbitals in their valence shell. One of the valence electron of s-orbital is excited to d-orbital to give five unpaired electron ‘and so the state of five covalency (except N which show + 5 oxidation state by co-ordinate bonding). | } ‘ie 7. Ground a ATA State Excited State Day (Except N) (ii) ‘The various oxidation state for each group members are } N=-3,-2,-1,41,42,43,44,45 Pa-3,43,44,45 As=-3,43,+5 Sb=-3,43,+5 =-3,43 (iv) Oxidation state Nitrogen 0 Ne 4 NH,OH (Hydroxylamine) 2 NoHe 3 NHs 4 NO 42 NO +4 ‘ No, +5 NOs (¥)_Allthese elements exhibit -3-oxidation state (covalency) in hydrides. (vi) The tendency to show - 3 ionic nature is not possible due to high-eneray considerations. However, nitrogen being smallest and most electronegative and thus, forms N™ ions in nitrides such as Mgs No, Ca:N:, etc. Rest all show - 3- oxidation state forming covaient compounds (wil) The +3 oxidation states are covalent and ionic both. The + 5 oxidation states are covalent as they cannot form M ions due to large amount of energy | involved therein (vil) The tendency to show M™ ionic state however, increases down the group due to inert effect. Sb and Bi form ionic compounds of + 3 oxidation state as SUF, _ ‘and iF. Most of the other compounds of + 3 oxidation state are covalent. e.g. NF5, PCly are covalent. Catenation It is a self linkage property of an element but itis in lesser extent in group 15 due to repulsion between lone pair HoN-NHz — Hydrazine H-N=N°=N° Hydrazoic acid2.4.14. 24.42. Ny" azide jon PoHy, AssHe Electrical and thermal conductivity Both these properties increase on moving down the group because of the increasing delocalization of electrons from nitrogen (N= N:) with a co-ordination number one to bismuth having metallic crystals with co-ordination number of six. Thus, nitrogen and phosphorus are non-conductors while bismuth is an excellent conductor of electricity Allotropy All these elements (except bismuth) show allotropy. Nitrogen exists in two solid allotropic forms, a-nitrogen (cubic, crystalline structure) and [-nitrogen (hexagonal, crystalline structure). Phosphorus exists in number of allotropic forms such as white fed, scarlet, a-black, p-black and violet. Arsenic exists in three allotropic forms, ie, yellow. black and explosive, Antinomy also exists in three forms, ie., yellow, black and explosive 2.2 Chemical properties : 2. A 2.2.2 Formation of hydrides : () Hydrides formed have YHs formula ~ (NH, PHs, AsH, SbHs, BiH) (i) Except NH, all hydrides are poisonous. (ii) NH neutralises protic acids as well as aprotic acids (Lewis acid), so, ammonia is strong base. ) PHo + Hi—> PH4I Phosphene Phosphonium lodide Phosphene is a weak base as compared to NHs and rest all have amphoteric nature. (v) NH will have high boiling point due to H-bond. (vi) Tendency of H-bonding and 8. P. NHs> PH < AsHs < SbH3 < Bills (vil) NH cannot acts as a reducing agent and BiH, is strongest reducing agent (vil) Stability decreases from NHs to Bits Size increases and so bond strength decreases (>) Hydrazine is used as propellant for rocket fuels, Itundergoes combustion releasing large amount of energy. (*) Ny is called azide ion -—> Has 4 lone pair Ba‘?N3 » Barium Azide (Ba(N; )2]. Formation of halid ()— Trihalides: All possible trihalides of all these elements are known except NCls, NBrs, and Nis Because Low polarity of the N~ X bond. ‘Weakness of N - X bond due to large size difference. Properties NCly +-3H20——> NH3 +3HOC! PCls +3H20——+ HgPO + SHC! SbCIg +H20—» SbOCI + 2HCI - (Stiony! Chloride) BIClz +H20-—> BiOCI + 2HCI (Bismithy! Chloride) When an aq. solution of BiCl; is prepared, after some time a turbidity appears in it which is milky in appearance and finally a white ppt. is formed due to formation of BiOC|, Lewis base order : NF3 PC + Cle DINITROGEN (N:) (i) Nitrogen is most abundant element in air (78% by volume) (ii) Itexists in the form of diatomic molecule, N; and is also called dinitrogen. )__ Dinitrogen can be prepared in the laboratory by the following reactions, NH,Cllaq) + NaNO. (aq) —“*"_yN,(g) + 2H,0(¢) + NaCKaq) (NHe)26r07 "+ Crg05(5) + 4H20(") + No(9) Armen eromate 2NH, + CuO —»2Cu + 3,0 +Np 2NH, + CaOCl; ——»3CaCl, +3H;0 +N; (9) ‘Commercial preparation of dinitrogen is carried out by liquefaction of air and its subsequent frac distillation. Dinitrogen (b.p. 77 K) cistills over first leaving behind liquid dioxygen (bp. 90 K). Dinitrogen| derived from ir does contain some traces of noble gases and dioxygen Properties of dinitrogen (i) Nitrogen is colourless, tasteless, odourless and non toxic gas. (i) Ithas very low solubility in water (23.2 em* per litre of water at 273 K and 1 atm.) (i) Its mop. and bp. are 63.2 K and 77 K respectively. ‘Chemical reactions of dinitrogen () Nitrogen has low chemical reactivity. It is stable because of N = N bond which has high bond: dissociation energy. Some of the chemical reactions are listed below. (ii) Highly electropositive metals react with Noto form respective nitrides 6Li + Np ——>2L.i,N;3Ca-+Nz —»CayN,3Mg + Ny ———>Mg,N, (ii) Non-metals tike H, and O; react at high temperature. BH, +Ny — F225 2H, +Ny 25, 3H on 050 es Cocca Mote (iv) Reaction with compounds like AlOs and calcium carbide (CaC.) 2100K 100K AO +Np+3C—2100K,2AIN +360 Cay +N °K, canon +c cane tre stan ‘unin a qenme Natrol 3.1. Fixation of Nitrogen The process of conversion of atmospheric nitrogen into its useful compounds is called fixation nitrogen. Fixation is brought about in following ways 3.1.1 Natural fixation. A large amount of atmospheric nitrogen is brought to the soil either lightening discharge or by symbiotic bacteria. Lightening discharge converts dinitrogen. and dioxygen of air into oxides of nitrogen which are eventually converted into nitric acid and nitrates in the soi ‘The process of conversion of dinitrogen into its useful compounds by natural or artificial meaning. Lightning Higtemp iscreated ” 2HNO3 + CaCO3——» CalNO3)p +H1z0 + CO eq. N2+O2 > HNO3 (Rainwater) from ran waters Ca(NO3}2 ——»Plant roots 184 _, proteins eed = oe urea+ amino acid —“**"°_, wasteproduct —A™°nfvtg P22", Ammoniumsalt Nitrosifyng bacteria nitrites inpbactera® Fifrates —Semmnyiing bacterle 5. (iroxi 0 “ ca) (iv) w 2 Artificial fixation. Nitrogen can be made to take part in chemical combination under Suitable conditions to form useful compounds (refer to chemical reactions) (Haber's process) () Na + 3Ha qa 2Mo ants 73K, (i) Np + 0p 923% yano(g) 22 sng M2 NOs (i) GLNy 4+ 2Lign unum tie (vy) 2AlsNp—2 DAN i - Aluminium nitride CaG2 +N2 ——»CaNCN + clu rae NIHON) 5 urea —"29 (NH, )2CO3 26 ides N,0 : laughing gas Highly poisonous gas, in very tte amount it will have hysteric effect. N=N-» 0, ithas linear geometry, 1. must be zero but itis more than zero because it has only ‘one polar bond. ‘Only NO and N2O are neutral oxides of N. Itis only N which forms paramagnetic oxide. Stability of oxides decreases with increasing atomic number. Thus, NzOs is stable while Bi,Os is not known. (vi) The acidic character of oxides decreases with decrease in OS. (vip (wi Nitrogen oxides 0 iy @w (w) N,O +1 = Neutral While NO; +4 = Acidic ) _SbaOs and BizOs are insoluble in water but dissolve in alkali Sb205 +6NaOH —-> 2NazSbO, +3H20 (Sodium Antimonate) i205 +6NaOH——> 2NagBiO, + 3H20 (Sodium Bismuthate) i) Types of Oxides: Element Types of Oxides [N PTAs SB, Bi X,0, N,O3 | P:03 | As:O3 | Sb,0; | Bi,05_| Ou N:O4 | P,0, | As;O, | Sb,0s | Bi,0« X,0: NOs | P70; | As,Os | Sb,0: Nitrogen also form NzO, NO, NO> oxides. The oxides show the wide range of oxidation numbers of N, from +1 to + 5. All the oxides are covalent ‘Aare gases at room temperature (except NzOs which is unstable sold at room temperature) The lower oxides are neutral and the higher ones are acidic, Oxides are summarised below, Oxidation | Physical Lewis Formula | Method of preparation Number of N | Appearance = 4 Célouriess gas | :N=N-2 56: | NHyNOs —"" N20 +220 if Pt ANHg +502 Pt ,4NO+6H20 Hs +802 sso0 * +2 Colourlessgas | :N =O In sold and fiquid states, itexists as loose gimer N02 +3. | Biuesota ea NO{g) + NOz(9)—22°S 5 ns05 ree nS[N2O. Dinitrogen +4 Colouriess liquid tetroxide NO; Nitrogen +4 Brown gas. dioxide | O. te ie Nos °. 0 | 4HNOs + P4010» Porcdie +5 Colourless YON 2N205 + 4HPOs ae Bs noephor o ‘o : phorshe 3.3.1. Nitrous oxide (N20) ()— NHyNOs 22°C N04 2450 (rnatten} (i) NHgOH+ HNO2 ——>N20+2+20 Gi) tis stable, relatively unreactive colouriess gas, itis a neutral oxide (iv) It's soluble in water (1 "1 by volume), but solution is neutral and the following equilibrium lies in left hand side N20 +H20 === HyN202 hyponitrous act ‘Therefore, it may be taken as anhydride of HNO: (v) _N,O is also used as an anaesthetic, particularly by dentists. It is also celled laughing gas, because its smell cause euphoria, francs wry at Nan 80 fe OHNO If we] |s v Ra tno] [ee] 3.3.2 Nitric Oxide (NO) (i) NO is an odd-electron molecule ; alternately we can say it is a free-rad Hence itis highly reactive 2NO +02 —>2NOp (brown fumes) 2NO +Cly ——»2NOCI ano 298°C 54,0 4NOz eee (i) Bohborder Is 2.5as described by MO, theory) anil ‘bond length Ws 1.18 which ntegndisabetenen srcoubie Solel and a irole fered bel Biogen snaitdgen ater333 (ii) thean be represented by the following resonance structures 11 valence electrons). itis paramagnetic. In Solid and liquid states it dimerises forming N;0: and paramagnetism disappears O-N-N-O o O-N-O-N (ny I is asymmetrical and is formed as a red solid in the presence of HC (iv) NO readily forms coordination complexes with transition metal ions. These complexes are called nitrosyls, [Fe(H0)sNO}" (brown ring) Net 0 HNO: Fe nrnon oO: Nojabe [Fe(HO)y (i) NOp molecule js angular with an O.N-O angle of 132° and N-1 bond length of 1.20 A (which is intermediate between a single and a double bond between nitrogen and oxygen atoms) (il) N:Oc has planar structure studied by X-ray. ON 184A, N o ° N-N bond lenath (1.64 A) in N:Os is about 20 % larger than the usual N-N single bond. We can think ofthe positive charge formed on the adjacent N atoms which Causes repulsion and thus increases the bond length (i) NOe soliciies at - 11.2°C ands colourless. AAs the temperature increases, proportion of brown NO, increases and the colour of the liquid darkens. At around 140°C, the mixture is almost entirely NOsPD(NOs)s Cu+ HNOs(cone) a = l= Tt J ao Wes ngs Neuse rise NO.F ZnCle Zn(NOsj2 + NOC! 3.3.4 Dinitrogen trioxide(N;0;) @___ itis an intensely blue liquid or @ pale blue solid. It exists only at low temperature and readily dissociates to give NO and NO2, N:O; == NO+NOz (i) The NOs molecule has an O2N - NO structure in the gas phase and at low temperature, with an extremely long (1.86 A) N- N_ bond which is consistent with its easy dissociation. Q 168 9 N72 198A 105" N. 4240 Two interconvertibie structures (in presence of light radiations of a particulat wavelength) are assigned to it ° NN IN == O=N NEO a SS INO + NO; won IE 40 NHANO2 fe N23 SHINO: NaOH an Not H:0 Nallo, 3.3.5 Dinitrogen pentoxide (N:Os) o 2HNO3 208 5 Nos +H20 Tow temp ‘Thus NzOs is the anhydride of HNOs (i) this colourless deliquescent solid and highly reactive (ii) Inthe gaseous phase: Nz05 —* »NO2 +NOs 02 No05 +03 ——>2NO3 +02 (wv) Insolid state: NoOs +H20 N2Os +Na——>NaNOs +NOz >2HNO3N2Os +NaCl--—>NaNO3 + NOC! (¥) With cone, H:S0,,itforms NO} (nitronium ion) which can attack benzene nucleus forming nitrobenzene N25 +3HSO, ——>2NO} : 3HSO4 + H20 Calg +NO} ——>CgHeNO2 +H! (vi) X-ray diffraction shows that solid NzOs is jonic, NO3NO3 (nitronium nitrate), In the solution and gaseous phase, itis covalent with structure: SNe we Each N atom is sp*-hybridised NOs HNOs, NO; + NO +O; Ho POs % Na ¥ NaNO + NO»<———{(in solid phase) |N2Os | (in gaseous phase) Neci NOs+NO; | 604 NaNOs + NO-CI pane : yO) tadean nos -———>(O) > 3.3.6 Nitrogen oxides and air pollution Collectively, nitrogen oxides are often given the symbol NOx. Two of them, NO and NO; are (of special importance in envionment chemistry, causing considerable amount of air pollution. ‘They are given off in automobile exhaust and when fossil fuels are bumt, as wall as being ‘made during thunderstorms. In each case, NO is made and then NO; Nz +02—> 2NO No+ fo2- —NO2 NO; is more unpleasant and gives rise to acid rain and also takes part in photochemical reactions forming smog. The photons making up sunlight can cause the NO2 molecules to decompose, releasing oxygen atoms. No, 5 NO+0 ‘Oxygen atoms are extremely reactive and will attack other molecules, especially those in car exhaust fumes. For examples hydrocarbons that escape combustion, can be ‘changed into aldehydes. The oxygen atoms can also react with Oto form Os NO; is also involved in the production of one of the most unpleasant of all chemicals, present in photochemical smog, Its known as PAN (peroxyacetyl nitrate) 0 chy ¢ ee -O-NOs Its presence in the atmosphere irritates eyes and lungs and generally makes breathing difficult, 4 2NH, + CO, == NH;COONH, == NH,CONH, + H20 arenin carbamate wea34 _Oxyacids of nitrogen = BO Se ere Hyponitrous acid HaN2O2 Nitrous acid HNO; (aa ee EN - HyN202 +H20 +N20 H2Nz Oz gives N2O (anhydride) only on heating but N,O when dissolved in H,0 will not form H> N2O2 3.4.1 NITRIC ACID ‘Chemical properties of nitric acid Decomposition 4HNO, (aq) —"**—»4NO, (g) + ©2(g) + 2H,0(1) Acidic nature. HNO (aq) + H2O(!) -» Hs" (aq) +NO3(aq) Oxidising agent. 2HNO, (conc. )-—»H,0 + 2NO; + [0] ; 2HNO,(dil)-—+H,0 + 2NO + 3{0} Oxidation of non - metals. (i) Carbon is oxidised to carbonic acid (H.CO3). 2HNOs > HO + 2NO> + [0] «2 C+ 2{0] + H,0 > HCO: (C+ 4HNO, -» HzCOs + H,0 + 4NO2 T (ii) Sulphuric is oxidised to sulphuric acid (H,S0.) 2HNOs -» HO + 2NO, + [0] « 24 Sq + 24[0] + 8H,0 > 8H,SO, S. + 48 HNO, —> BH,SO, + 48NO; + 16 HzO (il) lodine is oxidized to iodie acid (HIO,). 2HNOs ~» H;0 + 2NO> + [0] «5 b+ 5 [0] > 05 1,05 + H,0 > 2HIO; I, + 10 HNO; > 2HIO; + 10NO; + 4H;0 (iv) Phosphorus is oxidised to phosphoric acid (HsPO,) 2HNOs -» H,0 + 2NO2 + [0] x 10 Py + 1010] > PsOro P4O1o + GH:0 > 4HsPOs P+ 20HNO3 > 4HsPO, + 20NO; + 4H,0 (v) Arsenic is oxidised to arsenic acid (H AsO.) 2HNO, > H:0 + 2NO; + [0] «5 2As + 5[0] > As,0; ‘As,Os + 3H,0 > 2H 2As + 10 HNO, > 2H,ASO, * 210 + 10 NO, or As +5 HNOs > H,ASO, + H,0 + 5NO; ‘Arion sot Oxidation of compounds. Dilute as well as concentrated nitric acid oxidises a number of compounds. For examp! () Hydrogen sulphide is oxidised to sulphur With nane HNA.With dil. HNO, 2HNO, —>H;0 + 2NO+3{0] _H,S +[0] —>H,0 +S]x3_ 3H,S +2HNO, ——>4H,0+2NO +3S 4 (i) Sulphur dioxide is oxidised to sulphuric acid With conc. HNO; 2HNO; —»H,0+ 2NO, +[O] SOREH,O% 10) sO, SO, +2HNO; ——>H,SO, +2NO, With dil. HNO 2HNO, ——+H,0 + 2NO 4 3[0] SO, +H,0 + [O0]—-+H,S0,]«3 i 380. +2HNO, + 2H,O——>3H,SQ, + 2NO (iii), Ferrous sulphate is oxidised to ferric sulphate 2HNO, —->H,0 + 2NO, +[O] 2FeSO, +H,SO0, +[0]—-»Fe2(SO,). +H;0_ 2FeSO, + 2HNO, +H,S0, — With dil. HNO, 2HNO, —>H,0 + 2NO + 3[0] = + HSO, + [0] —>Fe; (S04) + H,0]x3 6FeSO, +2HNO, + 3H,SO, > 3Fe,(SO,)5 + 4H,0 + 2NO >Feo(SO,), + 2H,0 + 2NO, Action of metal. With the exception of gold and platinum (noble metals), nitric acid attacks all metals forming a variety of products. On the basis of reactivity, metals have been divided into three categories: Reaction with metals which are more electropositive than hydrogen (Na, K, Ca, Mg, Al, Mn, Zn, Cr, Cd, Fe, Co, Ni, Sn, Pb, Sb etc), In this case, nascent hydrogen is liberated which further reduces nitric acid HNO, +H—> Reduction product + HzO HNO; —*4_,NO, —?"_,NO-*#4_,NH, —"N°3_5NH.NO, —*>N,O “H20 “HO “Hg “240 The stage to which the reduction actually occurs, however, depends upon the following factors, (a) nature of the metal, (b) concentration of the acid and (c) temperature. For example, () Very dilute nitric acid. Magnesium and manganese are the only metals which produce hydrogen with very dilute (1 — 2%) nitric acid. Mg + 2HNOs —> Mg (NO3)2 + Hz Mn + 2HNOs > Mn (NO3)z + Hz (i) Cold dilute nitric acid. More active metals like magnesium, zinc, tin and iron react with cold dil. HNO to form ammonium nitrate. Zn+ 2HNO, ——>Zn(NO;), + 2Hx4 HNO, + 8H——->NH, +31 - 4Zn+10HNO, ——>4Zn(NO,), + 3H, +NH,NO3 ‘amen aie Simitarly, 4Sn +10HNO, —»4Sn(NO3 )> + 3H,O +NH,NO,,(iy i) 4Fe + 10HNO; ——+4Fe(NO;)> +3H2O +NH,NO3 Lead, under similar conditions gives nitric oxide instead of ammonium nitrate Pb +2HNO, -—»Pb(NO,), + 2H} 3 eles ea Ee 3Pb + 8HNO, ——->3Pb(NO;)2 + 4H,0 + n2NO,, With hot dilute nitric acid. With hot dilute nitric acid, ammonium nitrate thus formed undergoes decomposition to form nitrous oxide (N20), Zn+2HNO,~-—>Zn(NO3)2 +2H}«4 HNO, | 8H_-->3H,0 +NH, } NH, + HNO, ~—>NH,NO3 NH,NO, ——>N20 1 2H,O | Zn 4 10HNO; —->4Zn(NO3)> +5H;O+ NO trove oxide Similarly, 4Mg + 10HNO, ——>4Mg(NO3)> +5H20 1 N20 With conc. nitric acid. With conc. HNO, metals like zinc, magnesium bismuth, lead etc. from nitrogen dioxide (NO2) Zn+2HNO, ——>Zn(NO,)2 + 2H HNO, +H———+H,0 +NO.]2 Zn + 4HNO, ——>Zn(NOs)p +2H,0+ 2NO, trogen dione Similarly, Mg + 4HNO, ——>Mg(NO,). +2H,O + 2NO, BI+6HNO,— —>Bi(NO3), +3H,0+3NO, Pb + 4HNO; ~-—>Pb(NO, )2 + 2H,0 + 2NO; Reaction with metals which are less electropositive than hydrogen (Cu, Ag, Hg, etc). Metal + HNOs -> Metal oxide + NO; or NO + H2IO Metal oxide + HNO; —> Metal nitrate + HO ‘The metal oxide thus formed reacts further with excess of nitric acid to form the } corresponding metal nitrate and water. For example, : a CO} ‘With conc. HNOs, nitrogen dioxide (NOz) is formed 2HNO, —+H,0 + 2NO, +[0} | Cu+[0}—>cuo CuO + 2HNO, — >Cu(NO,),2H,0 + 2NO; Similarly, Ag + 2HNO, > AgNO, +H,0 + NO». Hg + 4HNO, —>Hg(NO3)2 +2Hz0 + 2NO, With dil HNOs, nitric oxide is evolved 2HNO, — —>H,0 + 2NO + 3{0) Cur[O]—>Cuo 3 PICNDe ANOS SSeS SUNOS) He OlnBe: ‘3Cu(NO, ), + 4H,0 + 2NO 3Gu + 8HNO, Similarly, 3Ag + 4HNO, ——>3AgNO, +2H,O +NO 6Hg + 8HNO, ——->3Hg,(NO,)2 +4H,O +2NO.Reaction with noble metals. Noble metals ike gold and platinium do not react with conc. HNO: However these metals dissolve in aqua regia (3 parts of cone. HCI + 1 part conc. HNO) forming thew respective chiorid HCI first reacts with HNO; to produce nascent chlorine which then reacts with noble ‘metals forming their respective chlorides. SHCI +HNO, ——+NOCI+2H,0+ 2Cl -Au+3Cl—> AuCl, wor, yas agua ga am ‘awe ce Pts 4Cl—+PICl, Pita ‘These chlorides subsequently dissolve in excess of HCI forming their corresponding soluble complexes. Thus, AuCl, +HCI——> HAUCl,] ; PICly+2HCI-—>_H,[PtCle] ‘verstnords —— AuocnonesoPiicenoae ———_Chiosainicant ‘Action of organic compounds (Oxidation, Many organic compounds are oxidised by conc. HNO For example. cae sugar on oxidation ges orale ac ‘COOH CiaHasss + 1810] 6 +5H,O Cane Sugar — from nitric COOH acid Oxalic acid WW) Nitration. A mixture of cone. HNO3 and conc. H,SO, (also called nitrating mixture) is used for introducing one or more -NO3 (nitro) groups, into the benzene ring, This process is called nitration. For example, NOs (OQ) sto, 4 (OF +40 ae tensive Hs om ‘Onn, NO2 4+3HNO, —S% M2804, + 3H,0 (oe) Tousoe a 24s: Tonrtobene TNT) Hy OH CHa —O—NO2 | I GH— on 34N0 SMBH, GH—O—NO2 +3420 I (cone) CHAOH Ct—0 —NOz Giyeerol ‘Trinitrogiycerol 3.5 AMMONIA (NH,) 36.1 Preparation : () Ammonia can be prepared by following methods By heating ammonia salts witn strong alkalies NH,CI+ NaOH -> NaCI+H,O + NH By hydrolysis of metal nitides or calcium cyanamide Mg:Nz + 8H,0-—>3Mg(OH), + 2NH, CaNCN, + 3H,0-——+CaCO; + 2NH, cat yoann35.2 35.3 (i) Inthe laboratory it is prepared by heating a mixture of ammonia chioride and sodium hydroxide. itis collected by downward displacement of air (ii) tis dried by quick lime (Cad). (Ww) Since NHs, reacts with dehydrating agents like CaCl, P20; H:SOx. They ‘cannot be used for drying ammonia (v) It's manufactured by Haber's process in which a mixture of Nz and Hz in the falio 1: 3 is passed over heated Fe/Mo at 750 K and pressure ranging between 200-900 atm. /Mo SHe +Neo—ropK-200-s00 aim? ZN Properties of ammonia () Ammonia is a colourless gas with a characteristic pungent smell. It causes tears in eyes. (i). itis lighter than air (i) Itis extremely soluble in water. One volume of water can dissolve about 1000 volumes of the gas at 273 K. The concentrated solution of ammonia in water called liquor ammonia. (iv) Wliquefies on cooling under pressure to liquid ammonia (bp. 2396 K) and freezes at 202 K. On evaporation, it produces intense cooling ‘Chemical reaction of ammonia (Basic nature NHs + HO == NH,’ + OH NH, + HCI > NH.CI (i) Ammonia is a Lewis bi due to its tendency to donate electron pair. Thus it forms complexes with metal ions such as Ag’, Cu*", Cd’ etc. Ag’ +2NHS=[Ag(NHsh]" Cu" + 4(NHs) <> (CuNHg )4]?" (Goon Be nu) (ii) Oxidation of Ammonia ©} oxidises it to NO and CuO oxidises it to Nz NH3 + Op ene 4NO +6H,0 — 2NH3 + 3Cu0 7, 3cu +N) +3H,0 (iv) Decomposition ‘NH, —Ret heen, + 3H, ‘rete seat (¥) Reaction with Halogens Chlorine Excess of chlorine 8NHs+Cl-+NHCl+Nz NH + 3Cl,-» NCI; + 3HCI Bromine gives similar products and iodine gives harmless explosive, basic ‘ammono nitrogen triodide (NH NIs) which decomposes on applying pressure. 2NH3 + I> 2NHsNIs + 3HI BNH3NIs —*8_5 6NH,I + Sly + 6N> (vl) Heavy metal ions such as Fe™*, Ai”, Cr°* are precipitated as their respective hydroxides Fe""(aq) + NH\OH -» Fe(OH), + 3NH," Al" + NH,OH -> Al(OH), + 3NH," (vil) CO; reacts with ammonia to produce urea CO; + NH; —*22*_ {NH,COONH,]——+(NH;),CO+ HO 220a0n ” Anecmbarae Ses (vil) Active metals like Na, K forms metal amides, 2Na+2NH; "5 52NaNH. +H, 2K +2NH, 575" , 2KNH, + Hy ‘Socarise Potassamae(ix) Nessler's reagent an alkaline solution of KzHal, gives brown precipitate with ‘ammonia or ammonia salt. ‘2K gHalg + NH3 +3KOH-—-+>HpN—Hg—O—Hg—I 7KI + 220 Nessler's Reagent lode of mitions base 3.5.4 Uses of ammonia (Ammonia is used mostly to produce various nitrogenous fertilizers (ammonium nitrate, urea, ammonium phosphate and ammonium sulphate); (i Inthe manufacture of some inorganic nitrogen compounds, the most important cone being nitric acid. (ii) Liquid ammonia is also used as a refrigerant. 3.5.5. Tests of ammoni ()__ Itturns moist turmeric paper brown. (i) Itgives brown precipitate with Nessler's reagent {ii It given dense white flumes with a drop of HCl. (iv) It gives a deep blue solution with solution of copper (II) sulphate due to the formation of [Cu(NHs})SO., (V)__Itgives yellow precipitate with chloroplatinic acid. PHOSPHOROUS Does not occur in free state Occurs as Ca,(PO,); in bones. ‘As mineral phosphorite As phospho protein Catal 44 Minerals: Phosphorite : Ca:(PO,)2 Chlorapatite = 3Cax(PO,), CaCl, Apatite or Flourapatite : 3Ca,(PO,), CaF Preparation. : White P : (from bone ashes) ~ 80% 2Cas(PO,)2 + 6SiI02 __, 6CaSi0s+POre sand Oyo + 106-24 5 4p + 100 White P Red P Tetrahydral P, molecule in solidivapour phase ‘Chains of P. tetrahydral Soft waxy solid, garlic smell, white Dark red, brittle solid without smell Soluble in CS; Insoluble Ignites at 303 K Ignites at 533 k Poisonous ‘Non-poisonous Phosphorescence in air Dorot Dissolve in hot NaOH Does not Cubic Rhombic Less stable Stable sp. gr= 18 sp.gr =24 cout with knife Hard stored under water Not stored under water Red P is used in making of matches due to non-poisonous nature while white phosphorus causes disease to the worker called Phossy Jaw. wnite P —SN®OH_, aNaH2PO. +PHs 7 sodhypo phosphite42 Pas N; Black phosphorus Most inactive form = - ae Metallic or c Black RedP 88d Back P 400°C. = Stable form = Bad conductor => Resemble like graphite => P-P-P bond angle = 99° = P-P distance = 2.18 A° = Good conductor sp.gr.=2.69 Scarlet Phosphorus : Red P —S820¥S4PB_, Scarlet Non Poisnous Sp. gr. 1.88 Scarlet + NaQH —> PH; t More reactive than Red. Reduces CuSO, 530°C) condensation > Violet ‘orcrystallsation Violet phosphorus : White rhombohedral in shape Bad conductor sp. gr. = 2.35 Insoluble in CS Phosphorescence: glow in dark Py + 3S —-» P,S; (Tetraphosphorustrisulphide) (Strike any where Matches) Rat Poison ‘Smoke screens ‘Compounds of phosphorus Phosphorus and the other members of the group can make use of d orbitals in their bonding, and thus + 5 oxidation state is shown beside + 3 which is common in all the compounds, Thus PCls is formed while NCI is not formed. Three electrons unpaired in ee ee 3p, hence PCs is formed. 3s 3p | Exite 3d ¥ Satna ¥ fve electrons unpaired in outa) i 1 shell hus, PClis formed 3s" 3p 3d Three electrons unpaired in 2p, hence NCis is ter — []_— ETE) Stern: since 24 doss not exist hence electrons of oe 2p! { 28 can't be made unpaired, thus NCI is not formed 1 Phosphine (PHs) ()_ Phosphine can be formed by4.22 CazP2 + 3HzO ——>» 2PH3 + 3Ca(OH)2 calcium phosphide Pa +9NaOH + 3H,0-—“2 PH; + 3NaH2PO2 Its necessary to.exclude air from the apparatus because, although pure PHs will not burn unless ignited, itis offen accompanied with PH and H; which are spontaneously flammable. (iy) 2AIP + 3H.S04 + 2PHs + Ale (SO,)3 dil Itis @ colourless, highly reactive and extremely toxic gas, which smells slightly of garlic or bad fish. (iv) Itis better reducing agent than NH Ag’ is reduced to Ag metal GAg" + PH + SH.O —» HPO, + 6Ag! + 6H Cu" is reduced to Cu 4Cu” + PHs + 4H,0 —+ HPO, + 4Cut + BH* () PHs unlike NH3, is not very soluble in water. It aqueous solution is netural. (v)__ Itis more soluble in CS; and other organic convents. (vil) Anhydrous PHs and anhydrous HCI (not in aqueous solution) combine to form PH4CL (vill) Pure PHs is stable in air, but it catches fire when heated to about 150°C. PHs + 20, —+ HsPO. (x) © In liquid NH, phosphine dissolves to give NHjPH3 NH3 + PH3 ——>NHjPH5 base acid Oxides of Phosphorus () Two important oxidies of phosphorus are known : Oxides | Oxyacids Oxidation Number —_| POs HyPO, +3 PsOig | HaP Ox +5. The oxides of phosphorus react vigorously with H20 to give acidic solution - P4Qg+6H20——> — 4H3PO3 ‘-phosphorous acid - P4049 + 6HyO——> 4HgPO4 ‘o-phosphoric acid This takes place in stages: P,Q + 2Hz0 —> 4HPOs 4HPOs + 2H;0 —> 2H,P;07 2H4P;0; + 2H,0 —+ 4HPO. @) —__POro is white flocculent powder that has greater affinity for water hence, is used as ‘dehydrating agent in: = GHNO3 + P,Oy9 > 4HPOS + 2NZO5, ~ 2CHsCONH; + P,Ojo —+ 2CHSCN + 4HPO3 = __ 4CHsCOOH + PxOjo —> 2(CHsCO)20 + 4HPOs 2H2SO4 + PaOi0-—> 2503+ 4HPO3 (ii) 6CaO + PxOo—> 2Ca,(PO.)2 (iv) 100 + PaOro—> 4P + 1007 () _ PaQo reacts with alcohols and ethers forming phosphate estersOH OEt | i P4019 +BEIOH —+20- P-OH+20 = P-OH O&t Okt o8t P4010 + 6€1,0-——>20 =P Ot bet OH (Formation of esters confirms that HsPO, has structure O = p OH) OH 4.2.3 Phosphorus halides Two series of halides are known PXs and PXs, where X = halogen. Among these Pls is highly unstable, whereas iodine forms a stable di-iodide Pala Pq 1 6X2 —>4PXg (in the limited supply of Xz) Py +10X2—— 4PX5, (in excess amount of Xz) All these halides are gases, volatile liquids or low-metting solids. (i) PCI; is a colourless liquid (sp. grav. = 1.6, b.p. = 76°C). PCls is an off-white solid m.p. = 187°C) Itfumes strongly in moist air and reacts strongly with HzO giving phosphorous acid PCl3 +Clp —>PClg PClz +H20—~+H3P03 + 3H,0 (i) $03 +PClg > POCIg + S02 {ii) $03 +PCls —> S0yCly + POC, (iv) $xClz +3PClg ——s. 2PSCly PCs (vy) 3RCOOH+PCls > 3RCOCI+H3P03 (vi) RCOOH+PCls —>RCOCI+POCI, + HCI (vil) 3ROH+PCl, 5 3RCI + H3P05 (vil) ROH+PCls ——> RCI+ POCls + HCI (i) S02(OH)2 +PCls —-> SO2Cly + 2POCIy + 2HCI In all the oxo-acids and hydroxy compounds, -OH group is replaced by Cl HNO3(HO -NO2)+PCis > NO2CI+ POIs +HCI (x) In carbonyl compounds, 0 is replaced by two Cl atoms. RCHO + PCl; ——>RCHCI, + POCIs RCOR +PCl5 ——> RCCIpR + POCIs POCI is the chloroanhydride of phosphoric acid (xi) In the liquid and vapour state, PCls has the trigonal bipyramidal structure, atom being sp'd-hybridised.* eA Te 3a Excit. oie od Nel [FU] 3p" ved i Be ohephorus) = ve ru (phosphorus) Y ° CIESESESCS ¢ 'sp'd hybrid orbitals forming « e-P bonds vith Ct atoms O= ca } Cho(limited) __ Phosphorus | PCly ROC! wo {80 nooo POC! H:PO3 LO [ae HsPo. _ 3CallHzPO4)2 Phosphoricacis ‘Triple Super phosphate greater %age of Phosphorus i.e. 43.50% available P20, which is three times to the super phosphate (16-18%) Rock Phosphate can't be used as fertilizer because it is insoluble in water. .g., Ammonium phosphate 3NH3 + HsPO,—> (NH«)sPO« Potash Fertilizer: Which supply Potassium. increase resistant in plants and counteracts Undesirable effects due to excessive supply of Ns. Helps in formation of sugar, starch etc. ¢.g., Muriate (KCl) KNO>, KSO, 5:3 Mixed Fertiliser: N.P.K. MATCH INDUSTRY Rough material like sand or powdered glass to produce heat by friction. Low kindling substance (P,S,) or Red P to start the fire. Combustible substance Ike sulphur, paraffin wax, antimony sulphide to continue combustion. Oxidising agent - KCI, NaCIO; or red lead to supply air. Binding agent like glue “ SbH > NH3 > ASH, > PH, (18. Bond angle : NHs > PHs > ArH > SbH.(106' SbCl is butter of antimony. Critical temperature of NH3 = 132°C Liquid ammonia is polar solvent (22 = Dielectric const.) INHs autoionizes 2NHy <= HY MM, ‘Ammono acid whichgiveiniiquid NH ‘ammono base Pls: Formation of PHs from P by reaction with NaOH is redox reaction. In which P is oxidised. as well as reduced PH, was discovered by Gengembre in 1783, H:PO, =H! + HPO, Ky = 7.1 x 107 HPO. Hi + HPO¥? Ke = 7.99 x 10° HPO,? H+ PO,? Ky=4x 10 H,PO, and HPO. can act as Lowry Brownsted Acid as well as Base, White PO, act as only Lowery Brownsted Base. HPO; is also called glacial phosphoric of airand collected as snowy powder 18.4, -34.5, -62.4, ~87.5°C. respectively) ' > 94° > 91.8° > 91.3°) id.GROUP 16 ELEMENTS (OXYGEN FAMILY) THE CHALCOGENS GROUP 16 ELEMENTS - THE CHALCOGENS ‘Oxygen Sulphur Selenium Tellurium Potonium The outer shell configuration is ns* np* Le., A lalttt 0 [He} 252 2p* 138 [Ne} 3s 3p* Se [Ar] 3d", 45° 4p! wate [kr] 4d"®, $5? 5p" Po [Xe] 4" 5d"°, 68” 6p* CHARACTERISTICS OF OXYGEN FAMILY 7A iabiitieal Proven A 24.2 24.4 24.5 24.6 Electronic configuration All the elements posses general configuration of ns” np*. These are also called p-biock elements since differentiating electron enters into p-block. Abundance ‘Oxygen is the most abundant element in nature. It is an important constituent of atmosphere, ocean and earth’s crust. It forms about 21 % by volume of air, 89 % by weight of water and 46.6 % of earth's crust. Most of the metals are found in form of oxides, silicates, nitrates, etc. Sulphur is relatively much less abundant and is found in free state as well as in combined state : many metals such as Cu, Ag, Ha are found as sulphide deposits. Sulphur is about 0.052 % of the earth’s crust. The other members of this family ate found very rare, Metallic and non-metallic character () 0, S, Se are non-metals and also known as chalcogens of ore forming elements since many metals occur as oxides or sulphides. (i) Non-metallic character is however strongest in O and S, weaker in Se and Te and some metallic properties begin to develop in them (ii) Po is metal, being radioactive, itis short lived Melting point and boiling points i) The melting points and boiling points show a regular increase down the group. However, Po shows exception (i) The regular increase in m.p. and b.p. down the group is due to increase in molecular size which results in an increase in vander Waals’ forces of attraction. Physical state () Oxygen is gas while others are solids Q ®) (i) Oxygen molecule is diatomic while sulphur, selenium and tellurium exist © KG ‘as staggered 8-atoms rings. However, the tendency to exist in 8-atoms rings 3 is maximum with sulphur and ©) decreases as we go down the group. Se molecule (ii) Oxygen being smallest in size among its family members and is thus, capable of forming px - px bond to show O = O structure, The inter particle forces of attraction among O, molecules are weaker and thus, it exists as diatomic gas The rest all elements being larger in atomic size are not able to form pr-pr bonds and thus, do not exist in diatomic state. On the other hand, they exist as puckered rings or chain polymers in which atoms are linked by covalency and therefore, they exist in solid state, In polyatomic molecule of this family, pr ~ dx bonding is present Atomic radii ‘Atomic radil increase with increase in atomic number247 2.1.8 219 2.4.10 24.41 24.12 lonization energy The ionization energies of elements of gp. 16 are high due to small size and thus, these elements do not form positive ions easily. The ionization energy values decreases from Q to Po and thus, the tendency to form positive ion increases gradually Electronegativity Electronegativity also decreases gradually down the group. Oxygen is second most electronegative element after fluorine Allotropy All these elements show allotropy or polymorphism Oxygen : It has two allotropic forms, €.g., ordinary oxygen and ozone. Sulphur : It has the following allotropic forms, e.g, Rhombic, monoclinic, plastic, colloidal In addition to these forms, unstable small molecules S, (n = 2 to 5) which exist in various concentrations in liquid sulphur at elevated temperatures and in sulphur vapour S2 species predominate at approximately 1000 K and like O:, it is also paramagnetic Selenium : Selenium exists in six allotropic forms , three of them are red monoclinic and non-metallic forms containing Ses rings. The other three are grey monoclinic and metallic forms. The grey hexagonal monoclinic allotrope containing infinite spiral chains is most stable allotropic form of Se. Element selenium is used in xerography, in photoelectric cells and as a rectifier in semiconductor devices. Tellurium : it has two allotropic forms, viz., crystalline and amorphous. Polonium : it has two allotropic forms, viz.. «and fi forms (both are metallic forms) Catenation Oxygen and sulphur show the property of catenation. However, catenation is more Pronounced in sulphur. The poly-sulphides containing 1 to 6 sulphur atoms (S32) Sulphanes (H ~ S, ~ H), polysulphuric acids HOsSS,SO,H and various allotropic forms of the element contains different sized S, rings and chains. The S-S bond is also found in a number of compounds of biological importance such as cysteine, some proteins and enzymes. Multiple bond formation The tendency of this group elements to form multiple bonds with C, N and O decreases as we move down the group. This is evident by the facts that CS; (S = C = S) is fairly stable compound whereas, CSe,(Se = C = Se) decomposes readily whereas, CTez is not known. The multiple bond formation is also noticed in oxides of this group elements Valency and oxidation state ()Allthese elements have six electrons in their valency shell and thus, they can complete their octet. Either by forming bivalent anion gaining two electrons. eg., 0%, S*, Se* and Te® showing electrovalence of 2 ie, Na+S+Na— NaS or ‘or by forming two covalent links involving sharing of two electrons, e.g., HS ‘showing co-valence of 2 (i) The elctronegativities of S, Se and Te are low and hence, their compounds even with most electropositive elements are only 50 % ionic and the formation of S*, Se® and Te” oxidation states are less probables as compared to O*- Furthermore, Po does not show Po” oxidation state. On the contrary Po shows +2 ionic nature. (ii) Oxygen show divalent nature since it has only two unpaired electrons in p- orbitals and have no vacant d-orbitals. (iv) All the rest elements have vacant d-orbitals to which one of the paired s-and p-orbitals electron from valence shell are excited to show the + 4 and + 622 oxidation state, i.e., all these elements except oxygen can extend their co- ordinates number to 4 and 6 ae Gormene CO) [Olt [A sp® hybridization to give tetrahedral pair of electrons or V-shaped. ns Ap nd. S atom excitedstate 1] TTT4] ff ‘spd hybridization to give trigonal pyramid-structure Position with two positions occupied by lone z a ns mp nd atom inturther FF) TATA] [TA excited state spd" hybridization to give octahedral structure Chemical properties Formation of hydrides: 224 0 (ii) (i) (iv) Hydrides have H2Y formula where Y is the 16" group element and has oxidation state of +2 HzO —> Neutral hydrides (liquid state) HS H:Se + Acidic nature (Gaseous) HaTe H,0 undergoes strong intermolecular H-bonding and exist in liquid state The lowest boiling hydride is H;S. It is because of absence of H-bonding and smaller size of S The B Pt. of these hydrides vary as HO > HzS < H,Se < H;Te Properties: o (i) id) (iv) Volatility: a lerirdaae HS decreases HS HeTe So, H¢S is most volatile among these. Thermal stability: HO decreases Hee Acidic character: 1:0 | increases H.Te ‘Since charge density decreases and size increases Reducing character: All hycrides eycant water ere reducing agents jeducing power tite | neveases Only on reaction with F, HzO is reducing agent and releases O2 because F is more electronegative than O.2.22 223 “ (vi) Formation of Halic i) ii, a) Bond angle : Decreases downward due to decrease in electronegativity of central atom. Structure In all these hydrides, the central atom is sp* hydridized. The bond angles are 104.5°, 92.5, 91° and 90° in HO, HS, HzSe and H,Te respectively due to lone pair effect and thus all are V shaped. The decreasing trend in bond angles from H,0 to HzTe is due to decrease in electronegativity down the group which results in decrease in bond pair — bond pair repulsion and bring in a decrease in bond angles. YX: YoXa YXe YXe Oxygen forms halides with F only OF, OF, OSofO 42 4 Shape and structure of O,F; is same as H.O7 Sci Sih SCly SFo. S,Cl, is used in preparation of mustard gas. (ii) Same for Se. (iv) TexCly and Po;Clz are not known . This is due to weaker Te - Te and Po - Po bonds. (v) Thermal stability of halides F > Cl> Br>1 (vi) All elements form hexa fluoride i.e. among halogen only fluorine shows the maximum valency of six due to its small size. (vi) Sulphur hexafluoride is extremely unreactive and is obtained by the combustion of sulphur in a stream of fluorine, Due to low reactivity and high dielectric strength, it is used as a gaseous insulator in high voltage generators and switch gears. (vi) In the hexaflucrides of S, Se and Te (i.e. SF», SeFs and TeF®), the central atom shows sp'd* hybridization and therefore, these exhibit octahedral structure having S ~ F bond length in SF. equal to 155 pm. Note that hexahalides with Cl, Br and | are not formed because of the larger size of these halogens, the coordination number of six is not achieved by central atom, Due to small F atom a maximum covalency of six is noticed in fluorides. (vill) Sulphur tetrafluoride is prepared by fluorinating SClp with NaF. It is very reactive and is readily hydrolyzed by water to give: SO2 and HF. It is used as fiuorinating agent for many inorganic and organic compounds. Sabaeeler: Structure of SF OXIDES ()_ Allthese elements (S, Se, Te; Po) form oxides on burning in air of the type MO di) i) @.g, SO», SeO2, TeO, and POO, ‘The acidic character as well as stability of these oxides decreases down the group. SO2 and SeO, are acidic oxides; TeO, and PoO; are amphoteric as they react with acid and alkalies both. SQz is gas, SeQ: is volatile covalent solid and TeO, and PoO, are white crystalline ionic solid, SQ2 molecule possesses a resonating hybrid structure as shown below. The SO2 molecule has bent structure with bond angle 119° It exists as discrete molecule in gaseous phase as well as in solid phase. However, SeO2 and TeO; are solids with polymeric chain or layer structure.