SALLOTROPIC FORMS OF PHOSPHORUS ~The important altropie fons of phosphorus are who ve 1 pions whi ad ad © of discrete eaheral Py molecule (Beit is poisonous, insokbe in water tut “ use in ES, and glows in (@) Icesot +g (Te reaciy catches rein acto give danse white fumes of PaDry 2. Red phosphorus: ec PIs heaasundntigh uss, srs of phases of black Pi formed Wei on olsonBlack phosphorus “ (2) [thas two forms : ablack and B-black phosphorus. |, () a-black phosphorus is formed when red phosphorus is heated in a sealed tube at 803 K. It can sublime in air and has opaque monoclinic or rhombohedral crystals. nite phosphorus at 473 K under high pressure. It does - @ () B-black phosphorus is prepared by heating not burn in air upto 673 KPHOSPHINE, Preparation ofa posi wih wal or. P+ 6 —> scan, +@R) * Lab preparation : By heating white P with conc. NaOH in an inert atmosphere of CO>. NaOH + 3H,0 oe ‘3NaH;PO, 9 Soda tpophcepite)Properties 5 gas with rotten fish smell and is highly poisonous. i contact with traces of oxidising agent like HNO3, Cl, and Br vapours. ly soluble in water, solution of PH, in water decomposes in presence of light giving red Pi ISO, or HaCly, phesphides are obtained. — Cur) + sH,s0, Prs ——> (HasP2) + HCI 1nd like NHs, give phosphonium compounds with acids, Use of PH 1. Used in Holmes sans ce fo spontanecusconbuston of phosphine. Containers containing Cal Case per ad town nse when gases evolve bum and serve as signal Abo sed in smoke sugeasPHOSPHORUS HALIDE ors forme halides of type phosphorus Trichloride, PCI, Preparation : Propertios : + Colouress oy quid and hyerlys in the presence of moist, PGR + HO — HPO) + aH! + treacts with organs CHCPhosphorus pentachloride, PC! ly and finally for : cid. osphoric a 2¢i, and finally forms phosplI reacts with organic compound containing ~OH gtOUP. CHAGH + Po, —>(CoHsCDY POCk| cane Be PKceO ea Cre on meres te CH.COGH + Pc, —+(CH,COC)} |POCK) + HC! my Finely cided metals on heating wih Pol, give coesponcing chloe 7 2g + PC, —> 2aq0! + CCR Race Nm as Sn + 2Cl; —+ snc, +Gecy) ‘+ [tis used in the synthesis of some organic compounds @.g., C,HsCl, CH;COCL. Structure + In gaseous and fad phases, iss hybsed and has tgonal bgyramdal saci, The two axial ands dre longer than Tree equatorial ponds. This is due to fact that axial bond pair suffer more repulsion as compared to equatorial bond pas. in golid state, it exists as an fone solid (PCI ]* [PERT TIPCI,|* Is tetrahedral and {POT 1s octahedralOxides of Phosphorus : It forms two oxides P,O, and P,O49. A P,O,: P4+302 Tice P40ILis white solid with garlic odour. It dissolves in cold and het water to form phosphorus acid and phos a ectively,Its a white solid with snow like appearance and sublimes on heating. it readily dissolves in both cold and hot water. P,Oy9 + 2H,0 —> 4HPO, (Meta phosphoric acid) (col), P,0;, + 6H,0 —> 4H,PO, (Phosphoric acid) (bat tis a powerful dehydrating agent.“hem "7+ Radioactive metal (half-life 13.8 days) ins ore forming elements such as oxides and sulphides.by mass of earths crust. Dry air conta oxygen n earth It forms about 46 Sulphur In earth curst only 0.03-0.19% Selenium and Tellurium : Found as metal selenides and tollurides in sulphide ores, Polonium : Occurs as decaAtomic and lonic Radii the group atom exceptionally smal lonization Enthalpy zation enthalpy to Group $5 ri tronic ae ompact ha again become less negative upt Negative electron gal 4. Electronegativity fluorine‘Anomalous behaviour of oxygen in Group 16 This is and high electronegativily. o absence of d orbital in oxygen, limits its covaleney to four and in pr sh lency more than four. 11 is very high, it shows only n late deoreases down the group. Polonium hardly shows 72 #4, #6, where +4 and +6 are more common. S, Se, Te th fluorine. Bonding in +4 and +6 are primarily covalent. ‘and that of +4 increases due to inert pair effect He)Thermal stability ~ Reducing character ing po P=HOV— > H-Bond Boiling point : HS < H,Se = Hp) 6 —* Melting point : HzS < HzSe < HeTe s| =Reactivity with oxygen : All elements form oxides of type EQ, and EO, (E = S, Se, Te, or Po). Oz and SOz are gases, but SeO2 ig solid. From SO, to TeO, reducing property decreases. TeO, is an oxidising agent. Sulphur, selenium and tellurium also form EO; type oxide. Both type of oxides are acidic in nature. Tendency to form EO, decreases down the group due to inert pair effect. aio en his of Ye Ex, Xa = Grup 18 emer (= Hen (ecRcecae oe mar, et a a F418 sod. They have gga hyncsed contra (Al elements excat soln form dcrides and amen. They aco sp hybried and have tetshoura svesure. Manhole ln 8°80 Ship Soyo ant Segkey Ne ores aeas tag, ——s Bete + teeDIOXYGEN Preparation In lab 0, can be obtained by +. By heating oxygen containing salt as chlorates. nitrates and permananates. 2KCI0g a —> HCI + G02 2. By thermal decompositinn of oxides of metals, 2Ag,0(s) ——+ 4Ag(s) + (O29) 2HgO(s) ——> 2Hall) + O2(9) 2Pb;0,(s) ——> 6PbO(s) + O2(9) 2PbO, ——> 2Pb0(s) + O2(9) 3, By decomposition of HO, 24,0 (2a) sre sed nt 24,00 { 0)Solubility in water is approx. n 100 cm? water at 293 K, sufficient for marine and aquatic ie} It liquefies at 90 K and freezes at 55 K. It has three stable isotopes : O'8, O°7 and OF® 0» is paramagnatic and this can be explained on bass of uo theon) 4s and non-metals (except Au, Pt and some noble gas Dioxygen directly reacts with nearly all metals ond dissociaty reactions are exothermic, however to initiate reaction, some extemal heating is required jenthalpy of O=O is high (493.4 kJ/mol).Some reactions are 2Ca + O27 ———» 2Ca0 4Al + 30) ———> 2Al,0, Py + 502 ——> P4019 Cc + 0, —— CO, 2znS + 302 —— 2Zn0 + 2802 GH) + 20. ——> C02 + %h0 + O» __¥205__, 2803 CuCl _, (2Cl) + 2H,0an important gas for normal res O2 is used in oxyacetylene welding, ration and combustion For manufacturing of many metals and steel 02 cylinders are used in hospitals, high altitude flying and in mountaineering Combustion of fuels, ¢.9., hydrazines in liquid oxygen provides thrust in rockets.SIMPLE OXIDES: Binary compound of oxygen with other elements. Oxides vary widely in nature and properties. Simple oxides can be classified as () Acidic Oxide : Non metal oxides are acidic but oxides of some metals in higher oxidation state also show acidic character. They combine with water to give acid e.9., NOx, Mnz07, CrO5, VoOs rela oride For example, SO. 60, Basic Oxige xides are basic. These oxides give base with water e.g. -ombines with water to given Ca(OH)>, a base. 9) + Garon»,(iy Amphoteric Oxide amphoteric O° ides show cur ofboth acid as well as alkali 92, ALO; ) + 94,01) ——> ZAKHOg)* (aq) + 6Cr (aa) ) ——= 2Na,[AKOH)g] (aq) “oo v) Mixed oxides v aha ala with different oxidation states are called mixed oxides. g N‘OZONE itis allotepic form of 20 km, its formed fe Preparation Properties |. gen. Bs 0 0 eave carnal rama amoaphee ee evel AION a atmospheric oxygen in the presence of sunight. Ozone layer prevents earths surg through silent electrical discharge, so as to prevent decomposition of O,, (aHeoax = +1424 mol) * _Qyis pale blue gas, dark blue liquid and vjolet black sold [thas characteristic smell and in small concentration iLis haumless. But in concentration above 100 FP breathing becomes uncomfortable resulting in headache and nausea.0, 2s stg oxidising agent, (05 > 29, POsis) + @Oo) —> Prsoui6) + 40,6) 2 (aq) + HzO + O3(9) ——+ 20H-(aq) + bs) + 0,19) Quantitative estimation of 0; On reaction of O. with excess of Ki buffered with borate butler (pH 9.2), lis liberated which can be titrated. against standard sodium thiosulphate, nani ~ 2Ki(aq) + HO(l) + O,(g) —> 2KOH(aq) + |2(8) + Op(9) Nitrogen oxides (especially NO) emitted from exhaust systems of supersonic Jet aeroplanes might slowly deplete the concentration of O, in upper atmosphere ~ P NO(g) + O3(9) > NOzig) + O2(9) Use of freons (in aerosol sprays and as refrigerants) can also damage ozone layer.‘The various allotropes of sulphur are Saas S=CRS Non Clos 1 Rhombic sulphur (q-gulphur) Its yellow in colour, melting point $85.8 K and specific gravity 2.06. It is stable form of sulphur at temperature porating the solution of roll sulphur in CS. It Is insoluble in water, readily solub + Rotor Solera, Itis formed on o1 and dissolves in benzene, alcohol and ether. its meting pc fic gravity 1.98. + Itis prepared by melting rhombic sulphur in a dish and cooling, til crust is formed. Two hok made in crust and remaining liquid is poured out. On removing crust, colourless neediest f B ormed, iio suphur is stable above 969 K and bolow 269 K a-suiphur is stable. At 969 K both and this temperature is called transition temperature. oth rhombic and monoclinic suohurs have S, molecules, these are packed to give diferent structure and has qfowp shape.paramagnetic ike O,SULPHUR DIOXIDE C806" ulphur is burt. » $O2(9) aq) + 2H* (aq) ——— 1,0 (I) + $O,(9) industrially : oy-pioduct of roasting of sulphide ores.et ee ey I + OO a) re gas after drying Is liquefied under pressure and stored in stot cylinders propatios + SO, is colourless gas with pungent smell and is highly soluble in wale It liquefies st room temperature under pressure of two atmosphere and bolls at 263 K. SO, when passed through water, forms guishuraus cis S0;(9) + H20() H,S0,(¢q) ‘readily reacts with sodium hydroxide, 2NaoH +"’SO, ——+ NaySO + 1,0 NaSO3 + HjO + SQ; ——> 2NaHSO; it reacts with Cl in the presence of charooal which acts 2s catalyst 20510) + Ce ed es Itis converted into SO, by the action of Op in the presence of Vz0s 0s, 280; (9) 2803 (9) + O2(9) + Moist $0, acts as reducing agent ©. ® . sot + a 7® + so, + 240 —— FH + aH nif‘Some more reactions of SO, SO, acting as oxidizing atStructure of SO, It is angular and is resonance hybrid of the following two canonical forms Use of SO, : 1. In refining petroleum and sugar. In bleaching wool and sik. in ant lor, disinfectant and preservative. In preperation of H=SO,, NaHSO,, CaHSOs, Liquid SO, used as solvent to dissolve organic and inorganic compounds.‘SULPHURIC Manufacturing moving impure Sn as arsenic compound. en in the presence 5 (catalyst). 196.6 kul 720 K and jolume. Therefore, | 2 bar pressure AS04544 D™ 128,04 Awe of desired conggntration. H, 10, obtained is 96-9Water spray ‘ Soong Star ‘Uys (gelatinous hycrated “eqicosse Sy ig. : Flow diagram for the manufacturing of sulphuric acidphysical Properties: erirced vine ROO Goren, 0 and a boiling point of 611K. The high ntrated sulphuric acid has a specific gravity of ling point and high ig point of SI boling point and high v indicate that sulphuric acid has associated structure due to hydrogen bonding as shown bel . pf Hydrogen bond oH 7 JN 0” °. uble in water and the dissolution proasss S| ‘thermic. So acid is} nd not by adding water to acid. This is done because to spurt out of the container. (ii) The concentrated.acid is by adding acid to the wa ¢, lot of heat is produ ter slowly which causes the acidChemical Pro} 4, Decomposition. Sulphuric acid is quite stable but o Acidic nature. ~ () Itis a typical acid and it turns blue litmus (i) It ionises in water asxides and carbonates etc. as:is an oxidising agent 2s & HO, \rex os) ov s. Sulphuric acid decomposes the salts ike nitrates and chlord heating. NaHSO, ate NaCl +H, » NaHSO, +sulphuric acid. (i) Aromatic compounds react with conc. H,SO, to form sulphonic acids. H)+ H,0 Benzene sulp acidUses of sulphuric acid itis an important industrial chemical and is used in many industries. Its major uses (i) For preparation of fertilizers like ammonium sulphate, super—phosphate of lime etc (il) For (iii) In storage _batteri 1d lead_accumulators ad metal surfaces before electroplating)