NO T9y- ¢— Nang— chilt * describe the wg a the 71 Eneais nts SSE 7.1,1 Occurrence Molecular nit nn comprises In the earth's tt occurs as =a and potassium nitrate (indian) proteins in plants and animals roaie |. ‘fer studying thls Unt, you wil be able to appreciate general trends in the chemistry of elements of groups 15,16,17 and 18; dinitrogen and of their Preparation, Properties and uses of dioxygen and ozone and chemistry of some simple oxides; * know allotropic forms of sulphur, chemistry of its important compounds’ and the structures of {its oxoacids; 7 preparation, Propertiea and uses of chlorine ic ‘acid; chemistry ” of interhalogens and structures’ of oxoacids of halogens; * enumerate the uses of noble gases; * appreciate the importance of these elements and their compounds in our day to day life. “block elements miaiifestey Diwersity tn chemistry ts the bfp- elements of s-, d- and f-blocks's, Ttetr ability to react with well as with their own. In Class XI, you have learnt that the p-block clement, are placed in groups 13 to 18 ote periodic table, pd figuration is n at of others are greatly infused ty atomic sizes, ionisation enthalpy, electron’ gain enthalpy and electronegativity. The absence of d. orbitals in second period and presence of d or dandf orbitals in heavier elements (starting from third period onwards) have bare effects on the properties of elements. In dalton, tha he presen of el the three types of elements; metals, metalloids_an ~~ Having ‘learnt the chemistry of elements of Groups 13 and 14 of the p-block of periodic table in Class XI, you will learn the chemistry of the elements of subsequent groups in this Unit. Group 15 includes nitrogen, phosphorus, arsenic, antimony? » bisenuth sxnaecovan] Aa we go down the group, tee aa metallic through metalloidic character, “Nioas. as ds, rus are non-metals, arsenic and antimot metallol Blt terye. KN, — Indt'ew im are typical metals, — lumé)of the atmosphere ate, NaNO, (called Chil) altpetre). Tris | found in the . Phosphorus occurs in mineralsjatomie Humbe [Rn] 5f"6d°7975* availability in very little amount, its Chemis Here, except for moscovium, important atomic ani Properties of other elements of this group along configurations are given in Table 7.1. Table 7.1: Atomic and Physical Properties of Group 15 Elements id physical electro! Pry cats f Melting point/K Bolling point/K “ sngle bond (E = element); *E°; “ B:“ White phosphorus; * Grey a-form at 98.6 atm: / Sublimation temperature; 'At 63 K: “Grey a-form; * Molecular Ny “a = ‘Trends of some of the atomic, physical and chemical properties of the group are discussed below. 1.2 Electronic ‘The valence shell electronic configuration of these elements lendng ‘The s orbital in these elements is completely filled and p orbitals are half-filled, making their electronic configuration extra stable. Ao de 7,8 Atomic and, Covalent and ionic (in a particular state) radii increase in size Tonic Radii ’ down the group. There is @ considerable Increase in covalent radius from N to P. Howéver, from As to BI only a small increase in Covalent radius is observed. is te due to completely filled d and/or f orbitals in heavier members. 7.4lonisation _Jonisation enthalpy decreases down the group due to gradual increase Enthalpy in atomic elze. Because ofthe extra stable half-filled p orbitals electronic configuration and smaller size, the ionisation enthalpy of the group 15 elements is much greater than that of group 14 elements in the corresponding periods. The order of successive ionisation fas expected 18 ble 7-1). onisation enthalptee, The p-Block Elementsa ais - ode ao nar No +eu! f | a “eo. cusiot] { Piet 2 eragattum 7.1.5 — al, decreases down the gativity value, in general, deci vis Hiectronegativity Sasa ciacemees ame 7.1.6 Physical All the elements of up are p f 1s a Glaton) ‘ea rs Dae Sa imereases down ‘and phosphorus are non-1 metals, arsenic and antimony metalioigg, Properties FS att mesmedian os] and bismuth is a metal, Tis is due to decrease in ionisation enthalpy ang aaa uo to +e G2] increase in atomic size. DOWIE bape Rett 7.1.7 Chemical Oxidation states and trends in chemical reactivity Properties The common oxidation states of these elements are -3, +3 and 45, oe the group due to increase in size and metallic character. In fact last member of ‘ bismuth hardly forms any compound in -3 oxidation state. The stability Sra terns down be oo, Ten oe area Bi Gmpona gyn eT eS aaa that of +3 state inci (due down the group. Besides +5 oxidation state, Hitrogen its + 1, + 2, + 4 oxidation states also when it reacts with oxygen. However, it does not form compounds in +5 oxidation state with halogens as nitrogen does noi to-accommiodate electrons from other elements: to, forin- bones, Phosphorus: also shows +1 and +4 oxidai ites in 5 ~ Nitrogen is restricted to am: um covalen rs 4 since only four (one Sand three p) orbitals are Ta aD cy se elements . have vacant d orbitals in the outermost shell which can be used for bonding (covalency) and hence, expand their covalence as in PF;. Anomalous properties of nitrogen Nitrogen differs from the rest of the members of this group due to its small size, high electronegativity, high ionisation enthalpy and non-availability of d orbitals. Nitrogen has unique ability to form px-px multiple bonds with itself and with other elements raving small size and high electronegativity (e.g.. C, O). Heavier elements this group do not form px-pz bonds as their atomic orbitals are $0 farge an fuse that they carmot have effective overlapp! us, nitrogen exists as a diatomic molecule with a triple bon between the two atoms. Consequently, its bond enthalpy is very high. On the contrary, phosphorus, arsenic 4 and_antimom -P,_AS=. =As and SOS WH bismuth forms metallic bon [Link] state. However, 2 Chemistry 9172,- factor which affects the chemistry © gen Is corals of d orbitals in its valence shell. Besides restricting gts . =p as elements can pk nitrogen cannot form ar x bon’ ; reactivity towards Tiydrogess, AIT the elements o ; rm hydrides of the here E = N, P, As, Sb oF Bt. Some of the properties 0 hydrides are shown in Table eae cular gradation in their properties. . ‘whi erved from Consequently, th the Ammonia is only-a mild reducing agent WI g agent amongst all the hydrides. H(S)BiHs. Due to Melting point/K Boiling point/K tif’ Reactivity towards oxygen: All these elements form two types of oxides: E,0, and E;0s, The ; These elements react to form two EX. Nitrogen does not form pentahalide e “a orbitals in its valence shell. "in pentahi far rinalides *3 oxidation state exists. Since elements in ¥5 Ox nents in ¥5 Oxidation a ee The_p-Block Elementsn nature R Towards metals: All these elements yeact With m, to form theln binary compounds exhibiting\-S)oxidation in such as, Ca,N, (calcium nitride). CasP, (calclum phiospp,* it) NayAs (sodium arsenide), ZnsSb, (zinc antimonide) ang Mea (magnesium bismuthide). Though nitrogen exhibits +5 oxidation state, it does not form pentahalide. Give reason, Nitrogen with n = 2, has s and [Link] only. It does not have d Solution orbitals to expand its covalence beyond four. That is why it does not tahalide, form pent PH, has lower boiling point than NH. Why? z Unie NH, PH molecules are not assocated through hydrogen bonding Solution tn liquid state. That is why the bolling point of PH, is lower than NH, eons are pentahalides of P, As, Sb and Bi more covalent than their | NeyOg A> a rao a 7.2 Dinitrogen Preparation ————— 77,2. K) distils out first leaving In the laboratory, dinitrogen is prepared by treating an aqueous solution of ammonium chloride with sodium nitrite. NH,Cl(aq) + NaNO,{aq) > Nz(g) + 2H,O()) + NaCl (a ———_— eet Na i ed (Small amounts of NO and (NH,),Cr,0, —Hs- N, + 4H,0 + Cr,0, ‘an be obtained by the thermal decomposition of. ide,, eee Ba(N3),> Ba + 3N4}6Li + N, Hat OLN ' a +N, —liuty Mg,N, combines with hy at catalyst (Haber's Proceed) oon ana : Ni@ + SH@ —Zt» 2NH,@: : The Main use of dinitrogen is in th and other aining nit Exa “3 Write the reaction of thermal decomposition of sodium azide. Solution ‘Thermal decomposition of sodium azide gives dinitrogen gas. 2NaN, -> 2Na+3N, 3 Ammonia Preparation ‘Ammonia 1s present in’small quantities in air and soil where it is formed by the decay of nitrogenous fer urea, NH,CONH, +2H,0 — (NH,),CO, +* 2NH, +H,0+CO, on ammonia is obtained which decompose when ted with caustic soda or tum hy% ide. 2NH,Cl + Ca(OH), + 2NH, + 2H,0 + CaCl, (NH). SO, + 2NaOH ~ 2NH, + 2H,O + Na,SO, The_p-Block Elementsnu Fig. 7.1 Chemistry 76, a Conastay 760K Ah enh ammonia js manufactured by Haber's Process, Ni@_+ SHalg)-= 2NH(@): AyH® = = 46.1 kJ mot! In accordance with Le Chatelier’s prinet iple, high pressure would favour the formation-of-ammonia. The optimum conditions for, ar a pressure of 200 * 10° of IRS a his Ghd N,—> ympressor 20 MPa at fron 700K | 4,0, (N,+H,+NH) Hauid NER Properties > ‘Ammonia is a colourless gas with Its freezing and boiling points eee an -fand 239. ively. In the solid and yy liquid states, it is associated through hydrogen bonds as in the case © bf water and that accounts for its higher melting and boiling points , than expected on the basis ofits molecular mass. The ammonia molecule r the apex. It has three is trigonal py (dal with the nitrogen atom at th Jone pair aeeeten 's as shown in the structure. boi Ammonia gas is ae soluble in water. Its aqueous solution is weakly basic due to the seantion of OF Tors. NH,(@) + H,0() = NH,’ (aq) + OF” faq) It forms ammonium salts with acids, e.g., [Link], (NH,), SO, ete. AS a weak base, it precipitates ted oxides in case of some metals) of many met solutions. For example. ‘|p, ZnSO, (aq) +2NH,OH (aq) — Zn (0 5 (s) + (NH, ), SO, (29) i ib) / h FeCl, (aq) + NH,OH (aq) — Fe,0y-x H,0(s) + NH,Cl (aq) UiThe presence of atom of a lone pair of electrons on the nitro; jen a ionia molecule makes Tt a Lewis base. It donates the € eer forms Tinkage with meta Tons and the formation of sue ce a ex compouinds finds applications In detection of metal TOT ‘as Cu”, Ag? eo + 4 NH,(aq) # [Cul ne Jaq) AB" (aq)'+ CI (aq) > Agcl(e) (colourless) tetute ppt AgC(s) + 2NH; (aq) — [Ag( NH), ]C1(29) ae (cloutesd Use: ee used to produce various nitrogenous fertilisers (qmmontum nitrate ures, ammonium phosphate ESR ema phate) and in te ae of some inorganic nitrogen compounds, the most important one being nitric acid, Liguid ammonia is also used as a refrigerant. Exar 4 Why does NH; act as a Lewis base ? Solution | Nitrogen atom in NH, has one lone pair of electrons which is available for donation. Therefore, it acts as a Lewis base. Intex Questions . “4 Mention the conditions required to maximise the yield of ammonia. 7 tiow does ammonia react with a solution of Cu"? 7.4 Oxides of Nitrogen forms a number of oxides in different oxidation states. The Ni names, formulas, preparation and physical appearance of these oxides itragen are given in Table 7.3. . Wily NOs, wd Table 7.3: Oxides of Nitrogen Peet moe CLC.y rrr Physical Ares: pests ead Py eee) prey ta) Pron Peterman Dinitrogen oxide N,0+2H,0 colourless _gas, Iitrogen() oxide] neutral Nitrogen monoxide | NO +2 | 2NaNO, +2FeSO, +3H,SO, | colourless gas, INitrogen(il) oxide] | Fe, (SO,),+2NaHSO, | neutral, | +2H,0 +2NO anaes BETH PBlsk ElementsDinitrogen trioxide (Nitrogen(II1) oxide} Nitrogen dioxide INitrogen(tv) oxide] Dinitrogen tetroxide 4HNO s+ POi9 >) 4HPO, +2N,0, Ty POURS N-N-O 113pm 119 pm Linear N-0O 115 pm Chemistry dS,Na Co eins, valence electrons, It behaves as a typical Solution odd Miyen number of ejttrone, {t 1s converted to stable N,O,molecule ‘why does NO, dimerise ? : Intext_ Question. mPa ‘What is the Su e covalence of nitrogen in NsOs pgrQr—? NT bes ps Nile Bei Nitrogen forms oxoacids such nee ihe (nitrous acid) and HNO, (nitric acid). Amongst them °° ems t tan mes ee KAN HNO F Nally cous. & my trvelgigeggy ite ats prepared by NORD HEN is) adcteamaeiso meee [> we) faNO, + H,S0, > NaHSO, + HINO, . dino, = WSDY a On a large scale it is p) mainly method is based uy ol atmospheric . oxygen. ; aN, (¢)+ 50,(€) oma} 4no(g)+6H,0(6) (from air) Nitric oxide thus formed combines with oxygen giving NO. 2NO(g) +02 (g) = 2NO; (8) Nitrogen dioxide so formed, dissolves in water to 3NO, (g) +H,0(1) > 2HNO, (aq)+NO(g) formed is recycled and ‘by distillatic upto\4 y give HNOs. & HNO, exists as H QF oan =N’ )19" the structure 25 jown. PX tn aqueous solution, nitric acid behaves as a strong acid giving ‘Ohydronium and nitrate tons. HNO,(aq) + H.00) > H,O"(aq) + NOs” (aq) Concentrated nitric acid is a strong oxidising agent and attacks most Metals except noble metals such and platinum. TW ‘and platinum. TheGrgr NO ale = ep m0 = ww Cu + 4HNO,(conc,) +Cu(NO,); + ay reacts wld neato ve TO and wth cong, acid give NO,. hay 4Zn + 10HNO,(dilute) -4 Zn (NO,), + 5H,O Zn + 4HNO,(conc.) Zn (NO,), + 2H,O + eNO) Concentrated nitric acid also oxidises non-metals and compounds. Iodine is oxidised to todic acid, carbon to car aut sulphur to H,SO,, and: phosphorus to phosphoric acid, kid ly+ 10HNO, +2HIO, + 10NO, + 44,0 / C + 4HNO, CO, + 2H,0 + 4NO, S, + 48HNO, +8H,SO, + 48NO, + 16H,O Py+ 20HNO, 4H,PO, + 20NO,+-4H,0 Brown Ring Test: The familiar brown Ting test fc K ntfaes) un_the ability of Fe" ia reduce nitrates to nitric ih with Fe™ to form out by adding diful e test Is Usually ease us Sulphate Softtion to an aqueous solnie A brown ring at the inj it etween the softrtion and sulphuric acid layers indict cates the presen, of nitrate ion in solution. ~ eS cates EP NO, + Fe" + 4H? On 3Fe" + 2H,0 [Fe(H,0),)* + NO oy, (H,0), (NO)|*" + H,0 : The major use of nitric acid {s in the manufacture of ammonium nitrate | for fertilisers"and other nitrates foruse in explosives and pyrotechnics. I , trinitro also used for the preparation,a 7.6 Dhosphonss — Phosphorus is’ found ini'mam ly allotropic forms, the important ones AAllotropic ‘being white, red anid black, —_ ‘orms whi oS ODDS P, +3NaOH +3H,0 — PH, +3NaH,PO, iN Chy chumituminescency, \ophosphite)ante Phosphorus is less stable and therefore, more react than seeagtte® sold phases vet normal condilons Deen train in the Py molecu v catches fire WIP 7g ala eT ee pharets As, wu mamestiete z er MoUoS lar 72 Hite phosphorus Black phosphorus has two forms phosphorus and psphorus. 61 p phi 7ig.7.9 Red phospeiis-< - hosphorus_is forme {i 11 Phosphine phy rt =CO9, Phosphine is prepared ZICH phosphide with water or dilute HCl. ‘CasP, + 6H,0 +3Ca(OH), + 2PHs Ca,P, + 6HC] +3CaCl, + 2PH, P, +3NaOH+3H,0 > PH, + SNaH,PO, hypophosphite) PH,1+ KOH» KI+H,0+ Fly, Properties Irs a colourless ges and It spate ae agents Te ANG Ca e tea sifiiy The _p-Block Elements Part hay ;"8 aint > Cala Cagle i J "copper sulphate or mercuric chloride solution, the corresponding phosphides are obtained. — SCuSO, + 2PH, + Cu,P, +3H,S0, oot SHgCl, +2PH, ~ Hg,P, +6HCI Phosphine is voale basic and like ammonia, gives phosphonium compounds with ac eg. PH, + HBr -> PH{Br In what way can it be proved that PH, fs basic in nature? PH, reacts with acids like HI to form PHI which shows that it 1s basic in nature, ee PH, +HI 5 PH, Pet's Ione paron phosphorus atom, Psi acting as aes base inthe above eatin Fler Bond angle in PH,’ is higher than that in ‘PH: Why? * is formed when PH, reacts with an acid? ‘What happens when white Phosphorus is he solution in an inert atmosphere of CO; ? 8 horus _Halides Phosphorus forms two f halides, =F,CL,Br, 28 Phosphorus Halides PR RCL Ba OPCS fhaldes, PX OK = F, Cl Brand 7.8.1 Phosphorus — Preparation . Trichloride It is obtained by passing dry chlorine over heated white phosphorus, P, #6Cl, > 4PCI, It is also obtained by the action’ of thionyl chloride with white phosphorais = = P, +8SOCI, > 4PCI, + 450, Properties () Itis Diowseek FGA and hycrotyses in the presence of moisture. . PO PO, + 3HCI a ‘ ‘Sah Ge Sas cee Gp & CH,COOH, CH,OF. ~ 2 aoa “SCH, COOH PCI, + 8CcH,COCl + H,PO, ‘eated with concentrated NaOH . a 3C,H,OH + PCI, -+ 3C,H,Cl + HPO, | f 7.8.2 Phosphorus It has a pyram{dal shape as shown, in which phosphorus sgt Pentachloride hybridised. emistiPreparation Phosphorus Pentachloride is prepared horus with excess of dry enti. Pit oe the_reaction of white - < Poe “Gag pote ad in moist air, it hydrolyses to 206i anfinaly georcmeret photon Sa PCI, +H,0 ~ POCI, +2HCl_. POCI, +3H,0 — HPO, +3HCL PCI, —Het 5 PCI, +Cly C,H, OH + PCI, — C,H,Cl + POCI, +HC ae CH,COOH+ PCI, 3. CH,COCI+POCIs+HCl 5 s QAg¥PCl, > 2AgC! +PCls sn+2PCl, > SCI, +2PCls synthesis of some organic H,COCl. : 6=cl bonds are equivalent Jonger than equatorial bonds. This is [Link] the cl fhe axial Bond pairs sulier more repulsion as ‘compared tg equatorial bond pairs. — npee_/- Why does PCly fume in moisture ? Solution Pel, hydrolyses in the presence of motsture giving fumes of HCl. PCI, +3H,0 $H,PO, + SHC! molecule equivalent? Justify your answer. trigonal bi fal structure and the three equatorial equivalent, while the two axial bonds are different and ‘equatorial bonds, |pep hp {Gy¥ BOS RDO ‘ Questions wa What happens when PCI, is heated? 0 ‘Write a balanced equation for the reaction of PCI, with water. 7.9 Ovoacids of Phosphorus forms a Phosphorus number of oxoacids. The important oxoacids Phosphorus with their formulas, methods of preparation anq le Presence. of some:characteristic bonds in their structures are ive, in Table 7.5. Table 7.5: Oxoacids of Phosphorus oe Tt ae eee cer rsd Perret ony Crag Perret mse Pea Bree \ophosphoric Sxophosphoric fetaphosphoric’ poz P,0,9¢H1,0 heat phosphoric acid * Exists in_polymeric forms only. Characteristic bonds of (HPOJ, —_—_—== The compositions of the oxoacids are interrelated in terms of loss . or gain of H,0 molecule or O-atom. The structures of some important oxoacids are given next, In oxoacids phosphorus is tetrahedrally surrounded by other atoms. ~All these acids contain at least one P=O bond and one P-OH bond. The oxoacids in which phosphorus has lower oxidation stat (less thian +5) contain, in to P=O and P-O €g., in H,P,0;) These acids in #3 oxidation — of phosphorus tend to dis proportionate to higher and lower oxidation states. For example, orthophophorous acid (or phosphorous acid) on heating disproportionates to give orthophosphoric acid (or Phosphpric acid) and phosphine. 4H,PO, > 3H,PO, +PH, Chemistry w8ay— OO fier Hore +40 —— qt nay + H5h rt fe. ; ertant axbacids of ev ie | botsimetaphosphore ald, HPO), Byfintaphosphore ald (HPO). contairf P-H bond ‘Thus, hypophosphorous actis a good reducing agent as two P-Hbonds. for Ai, AgNO, + 2H,0 + HPO, — 4Ag + 4HNO, + eo ae give H’ and do not play any role in baSteny- ‘ose Fratoms which are attached with oxygen in P-OH form are ionisable and-cause the basicity. Thus, H,PO, and H,PO, are dibasic and tribasic, respectively as the structure of HyPOs has two P-OH bonds and H,PO, three. .Q How do you account for the reducing behaviour of H,PO, on the basis of its structure ? Solution in HjPO,, two H atoms are bonded directly to P atom which imparts reducing character to the acid. 741, What is the basicity-of H,PO.? 72. What happens when H,PO, is heated? 0 Group 16 Oxygen, sulphur selenium, tellurium, polonium and livermorlum ements constitute Group 16 of the periodic table. This 1s sometimes known as Elements, ens. The name is derived from the rand its congeners wil oxygen or sulphur and— points to the association of sy Soper Most copper minerals contain either Frequently the other members of the group. ‘4851 The p-Block Elements| CU eek ele ab curtn, ate ' Th ft Nus— _0:04-0+] 7- Table 7.6: Some Physical Properties of Group 16 Elements posing : nt of all the elements on earth. Oyy, forms about £6.69) a Dry air contains 20, er eke, However, the abundance of suilphuir in the earth's crust jg combined sulphur exists as sulphates auch ‘gypsum CaSO,.2H,0, A Fae PSO an sulphides such as galena PbS, zinc blende re Traces of sulphur occur a Org aterlals euch as eggs, proteins, garlic, onion, mustard, hair and wo, contain sulphur. Selenium and tellurium are also found as metal selenide rides in -sulphid inal ure a8 aa product of andi erals. a Ly, atomic number 116, a smi radigactive element. Its symbol Is atomic Geant ‘electronic eonfiguration (Ral 5f"6d°7s'7p It has bet small amount and has very short hal og action ont). This limits the study of properiles of, Here, except fer-tvermorium, important atomic and physica properties of other elements of Group16 along with thetr-el configurations are given in Table 7.6. Some of the atomic, physical an, chemical properties and their trends are discussed below. 32.06 78.96 (Nel3s’3p* | [arj3d'"as"4p* DXelaf*sa"ectept 104 uz 146 184 230° oo -174 1000 Bensity /g cm” (298 K) Melting point/K Bolling point/K Oxidation states” “Single bond: "Approximate value; ‘At the melting point: “ Rhombic sulphur; ‘Hexagonal grey: ‘Monoclinic form, 673 K. * Omygen shows oxidation states of +2 and +1 in oxygen fluores OF, and OsF; respectively. 7.10.2 Electronic 7.10.3 Atomic and Ionic Radii Chemistry 86: ‘The elements of Group16 have six electrons in the outermost shell and have ns’np* general electronic configuration. Due to increase in the number of shells, atomic and tonic radi incre==* from top to bottom in the group. The ower era ; ip. size of oxygen atom is, howefUumu 4 Ioniéation — Tonisation enthalpy decreases down the group. It fs due to increase In Enthalpy size, However, the elements of this group have lower lonisaton enthalpy values compared to those of Group165 in the corresponding periods. This {s due to the fact that Group 15 elements have extra stable half- filled p orbitals electronic configurations. SG (pecan) lng] HES 5 Electron Gain Enthalpy 6 Next to fluorine, oxygen has the highest electronegativity value amongst ronegativity the clements. Within the group, electronegativity decreases with an increase in atomic number. This implies that the metallic character increases from oxygen to polonium. ee ments of Group 16 generally show lower value of first onisatiot thalpy compared to the corresponding periods of group 15. Why? e to extra stable half-filled p orbitals electronic configurations of Solution oup 15 elements, larger amount of energy is required to remove ctrons compared to Group 16 elements. : 7 Physical Properties Some of the physical erties of Group 16 elements a C a s, ie jonium is radioacti ll these elements éxh ) nese elements exhibiL gio 3Chemical Oxidation states and trends in chemical reactivity Properties ‘The elements of Group 16 exhibit a number of oxidation states (Table ' 7.6). The stability of -2, oxidation state decreases down the group. Polonium hardly shows -2 oxidation state. Since electronegativity of oxygen is very high, it shows only negative oxidation state as ~2 except in the case of OF, where its oxidation state ts + 2. Other elements of the + 4, + 6 oxidation states but *4-ar or iellurium usually shaw ¢ 4 pxidati , I S 1¢ stability o eases down the group and stability of + 4 oxidation state increases Bonding in +4 and +6 oxidation states is primarily covalent. == Anomalous behaviour of oxygen The anomalous behaviour of oxygen, like other members of p-block present in second period is due to its small size and high electronegativity. One typical example of effects of small size and high electronegativity is the presence of strong hydrogen bonding in H,O which is not found in H,S. 48% The p-Block ElementsMp, Ate the ey Cel alency to four The absence of d orbitals in 07 mits {ts cov! and pe in practice Tare Ice, Ga ihe other hand, in case of 3 clements of the group, ihe valence shells can be expanded and covalence exceeds four. ua Reactivity with h All the elements of Group 16 form hydrides of the typ HVE = O, S, Se, Te, Po). Some properties of ter inc; hydrides are given ii Table 7.7. Their, acidic charact eases fas "07% ] amo w He The meee ae nets cancer A Me 6 from H,0 to H,Te, The in ean | | | in terms of decrease in bond enthalpy for the di | Bond down the group. Owing to the decrease in enthalpy for i “dissociation of H-Etond down the soup. tt je th | hydrides also decreases from 1,0 to H e hy ROP | HS to H,Te. 208 232 146 91 -286 73 5 463 276 rake y1sx10" —1.3x107 13x10 * Aqueous solution, 298K, Reactivity with oxygen: All these elements form oxides of the EO, and EO, types where E = S, Se, Te or Po. Ozone (Q,}a sely — gud + Tefy > sedi 3). Both types of oxides a are acidic in nature: eis towards the halogens: Elements of Group 16 form a SHU. eC + 9e large number of halides of the type, EX. EX, and EX, where E is pans decease ic cS Geass i yre. Theyhaye octahedral-siguct These fluorides have sp ior bipyramidal structures in which one of quatorial postions @ Secupied by a lone pair of electrons. This ‘geometry {8 also regard fecena ) geometry. oy 3. These dihalides are formed by “8 hybridisatio: us, have tetrahedra srcture Th wal lnown mnhalde fede nature sam Chemistry GBs ,