Halogens Family - Lecture Note

17th group (halogens family )IG.E.C ms2mp5 F, C1, Br, I, At, Ts (Tennessine)membersoxi. stateNature-1 cl, to+7 Br, I (N.metal) At (metalloid).elements F, don't show allotropy. catenationThese These elements don't show liquid I2 solid.F2, C12gases Br2 ;colour F2yellow Cb Greenishyellowdark violetBr2 pale Reddish brownliquid C17 I2 FI > Brtcovalent I onic radii t :-F7 c17 Br>IIonisation EnergyElectron gain enthalpyC17 F7 Bry IF7 CIT Brt IElectronegativity Sm.pt :- I2 Br? CI>EBpt I27 Br,> Cl2>F2Distance (x-x):- F2> cb2 Br2>Iz F2B.D.E :- C12 Br27 F2>I2density :- I27 Br27 cl2>oxi. stateBr, I -1,+1, +3, +5,+7.F = -1oxidiseis strongest C1, oxi. solution agent. or and even it holide in solidother F2 halide In general ions in NO. a haloger oxidisephase of oxi. higher Nature atomic F27 cl27 Br2 7 = I2+ X2 ( x (1,Br,I) Br,I)F2+ 2x+2F + X2 C +=C12+ 2x'2CI 2Br++ X2 (x= I)Br2+ 2x+ active r halogen displaces soln) weak activeC halogen most from its saltLayer's test t (Test for Brt,It)C12cclyallBr-Br2ccl4 (N.polar)Br+actReddish brownlayh No Bry + C12 Nacl + Br2 (Reddish brown)+ NaclCase-2 Cl2+ NaI - I2 (violet layer)[ I2 & Br2 are n. polar !. readily dissolves react in with cclu]reactiveTheymetal All halogens & N. metal are very to decreases form holides down the The It group. reactivityorder of halogens energy :- F+ C1-' > Brt >hydration Fluorine oxidises water to 02.HF + O2toF2+ H2O and Bromine hydroacid. reacts with H2Oform chlorine hyponalous and HBroHBr +Br2 + H2°Rxn cl2 of Iodine is spontaneous with water case. in nature+ H2OHcl + HC10 is nor spontaneous. CReverse similar oxn to jluorine I2 + 21420RxnReaction with hydrogent Et H2 HBr> -H+ + It + O2HEHI1. HF > HCI> HCI> HFT.S order HI> HBr> HBr7 HIorderHFA.N B.N Reducing order 1- HI> HIZ HF> HF> HCL> HBr? HBr> HCI? HCIHFHCIHBrHImpt b.pt t HF > HI> HBr7 HCIReaction with oxygent halogens oxides forms differentin different oxi state.E20, C2203, E205, E2O7finantine E+O2 forms only two oxides OF2 & O2F2 Puis unstable and used in removingas O2F2 puFG 0,F2 from + Pu spent PuF6 nuclear 021 fuel.+Br and I forms different oxides to +7) inoxi state, ranging from (+' orderof oxides are in theI Brleast stable due to middle rowanamalytendency toC1-0form multiplebond.Br-oI-OHigh A E.N difference1.B.E portant pointsw3C102 is used as B. agent in paper pulp.,textile treatment and also in watertreatmentBO2O, Bro2, Bro3 exists insoluble.at v.low tempand act as S. oxi agent exists in solid formI204, I2°5, I207and decompose onneatingquantitative analysis cont (I2015) I2 (violet)co + I205Na2S2°3 (dryposoln)Eq. of O.A = Eq. of R.Aw, = w2I' + Suoga E2(cotourlers)with halogensttoformaRxn combines with compounds. themselves xx', xx3 xxs,xx7'.HalogennterhalogennoofClz+ F2 CIFC12+ F2 CIF3I2+Clz Icl3Br2+ F2 BrF3Br2+ F2 BrF3thanInterhologen C12+ I2 I CI cpds fluorine) are more due reactive to bond polarityhalogen and less (except B.D.E. are used for the U235 production ofCIF3 UF6 in & BrF3 the enrichment (e) of UF6(g) + 3c1F(g)U (S) + 3CIF3compounds of 17th group(univertas)M.O.P:- Ch2 greenish yellow gasmncl2+ cl2+ H2O\mno2+ concHuNaH + H2O + C12+ mnsoNacl+ H2SOU+ mno22Mncl2 + KCI + Cl2+ H2O3kmnoy+ HCIElectrolysis of aq Nacl or molten Nacl.4Na+ at H+ or-C12anode 5Pbo2+ HCIpbcl2 + Ch2 + H2O6Deaconts processHCL + O2cucl2H2O + cl2Properties greenish yellow gas with pungent air or . suffocatingiIt is 2-5 times yellow liquid at 239Kodour heavier than23liquified into greenish It reacts with4metal It is I soluble Nimetal in to water form chloricles Fecl3Fe+c'2Na+Cl2Naclpcl3P+ C2Alt -> AICl3C12chemical pro perties5Rxn with hydrogenHb+ "2HCIHCI + Sthis + C126Rxn with NH3 fNH3N2+ NHuclNH3 + C'2N2+ HCIC12NCl3 + HCI(excess)N2+HctNH3 + C12(excess)Rxn with alkalil1)Nacl + Naclo + H2OC1++ Naoly(cold s dil)Nacl + Nacio, + H2ONaoHCl2+ acidi (not si cation & conc) disproportionated th2 producton give back ebst H+C12 + H2O+ (105'+same ci case withBrt It)slaked limesRxnwithC2ca(ocl)2+ cacl2 + H2OCaloti'spowderBleachingCa(ocl)2 Cacl2 2420 Rxn with Brt, I-15Cb++ BrtBr2+ citC12+ ItJ2+ a-l10oxidising property & bleaching actionsHCI + HC10C12+ H2OHCI + [0]This nascent (0] defines its oxidisingand bleaching actionC12/H2OSH2SsoulSO2NO3-NO2Fe+2Fe+3so,2soulIt,BrBr2,I2HIO3I2Hclbleaching actions2HCI + (o](i) C12 + H2colourlesscoloured matter + (07permanent bleachingH2SOU + [H](ii) sort H2 ocoloured matter + (H] colourless. 0 Temporary colourless + bleach. O2 mair coloured matter11Rxn with hydrocarbonUXCH3 cl + HC/CHut Cl2Addition Rxnj12502+ C12SO2C'2 ( sulphwey chloride)NOCI (Nitrosyl chloride)NO + C'2co + C12cocl2 (carbony chloride)(phosgene) uses) for bleaching wood pulprbleaching cotton $ fabrierproporation of poisonous gaseslike phosgene (cocl2),tear gas C (ccl3NO2)mustard gas CccC1-CH2CH2-C1CH2 +of+SHC-s-11 S-SCH2CH2(mustardgas)Bromine (Br2)tconc + mnoz(i) NaBr + (goodH2SOUagent)oxiNaH sout mm sout Br2+H2O(iiifrom sea water)c12+ Brtci- + Br2(vapours)NaBr+ NaBro3 + CO2BO2+ Na2C33(gas) NaBr+ NaBro3 + 12504 HBr+ HBrO3 + No2sonBo2+ H2OA HBr + HBro3properties Reddish brown liquid fairly solublein water.Iodine (I2) tNaHSou+ mnsout(i) NaI + H2SOU + (good Mno2 H2OI2 +agent)'ii) from sea weeds)NaI + mno2+ ConcH2SO4Narson + mnsout I2 + th2 from chile salt peters7main source of of Is is NaIO3 foundingnature with NaNO3 (chile saet peter). NaJO3is present in small amount After in ocystallisa mothertion of NaNo3, NaIO3 is presentliquer Now we add NaHSO3I03+ + HS03I'+ soul + HtI-' + H+ + I03+I2 + H2Owater(i) Properties dark soluble violet in solid, KI least due to soluble formation in of KI3.butI'+ I2I3+(N:(polar)I2 is soluble polars in org. solvents like ccly, CHCL3to get violet soin-4 + Itsuot'ii) S2032 + I2tetra thionate ion.Fluorine F25m.o.psprocess(as)moissamHF + Ca2SO4firstly CaF2+ conc H2SO4 HF carhydrousHF CasdistillNow anhydrous HF ation is only slightly sod so ionised a mixture &poor conductor and HF is of used electricity. to increase the conductivityofKFof soln.K[HF2]KE+ HFHF + K[HF2] Electro th+ F2lysis Halogen Acids (HI, HBr, HCI) :-preparations direction combination of elementalpt,(i) By 2HCI : H2+ Br2th 2HBr; H2+I2 450 HIMs+ C12.heating halide 150°C with conc NaHSou+ H2sou.HCIiii) (a) By Nacl + H2SO4 550°C Na2Sou' HCI+ H2SO4Nacl is dried by .0 conc it reacts 12504 with It is Hcl. not bydriedcao Hct P205 cacl2 H2Oor+cao HC!Pocl3 + HPO3Pu 01 HCI(b) H2SO4 & oxidises HI can't Brt,It be prepared HBr + by NaHSO4 above methodBr2,J2HBr:Na Br + H2SO4Br, + SO2 + H2OH2SO4KI:. itis prepared HBrt H3PO4 by treating KBr 3HBr/HI orwith coreK3FOUKBr/Kert (conc) H3P04'iii) By reaction of Pu (white P) PBr31PI3 (insitu)Pu+ Br2/J2H3PO3+ HBr/HIpBral+ thoPI3Properties are Colourless pungent tastes. smelling gases1These with (pungent) combustible acidic nor the supporter presence of of combustin moisture23It neither act ag. as medium an acid In in dry state it don't turnsblue It or is litmus quite red. soluble in water4HCI+ H2OH30+ + cit kq=10t 9Aqua regia when smokes HCI mixted is withHNO3 ; aqua regia formedNOC + H2O & (c1]Hclt HNO3Aut [c1]Aucl3 + HCI H (Aucly]p++ (a)ptcly + HCIH2[ptcl6]6Reducing property:-mno2+ HCImncl2+ c12+pbo + C12 of H2OHCIpbo2+ HCImncl2 C12 + kcl + H2Okmnout HCIsame rxn as above, In addition itHBrreduces H2SO4 to SO2 SO2+ H2O + Br2(i) HBr+ H2SO4Br2+ H2O(ii) HBr(as)+ O2same rxn (air) as HCL rxns. In addition itHI :-shows following I2+ SO2+162HI + H2SO4I2+ S + H2O(i)HI + H2 SOUHI + th s ouI2+ H2S F H2OI2+ NO2+ H2O(ii) HNO3 + HI.I2+ NO + H2O'iii) HNO2+ HI(inst HIO3+ HII2+ H2OVFecl3 + HIFect2 I2+ HCI(Ni) HI (ag) + 02I2+ H2O(air)(i) Lab method heating of KHF2Hydrogluoric acid C HF or H2F2)KF + HFKHF2 'ii) Industrial methods heating juscurspar (CaF2)withcone H2SOCaF2+ conctis So, souCa + 2HFreacts with glass So it is stored intoHF wax rxn lined of bottles, glass with HF is as followsTheNa SiO3 + HFNa2SiFG + H2OsiF6 + H2Oca sioz HF casioz+ HF siFy+ H2OsiFu+ HF H2SiF6H2SIF6 + design NaoH on Na2 glass SIE6 by ething of glassuseProperties colourless, corrosive b.pt liquid due with to H purgent BondingIsmell with high metal under ordinary watsHF don't attack K); but in liberation presence of of2conditions Dry reacts (except with metal with to strongHhydrogen it It is a it weak gas form dibasic two series acid H2O (due of sart3bonding)KHF2 +H2F2 + KOH2KF + H2OKHF2 + KOHsome imp order t1Audic strength(i) HI? HBr7HC17 HBr07 HIO [ A.S 2 [ A.S L OXI G.N of C.A]state)'ii) HC10) HC1047 HC1037 HC1O27 HC10'iii)2oxidising powder'iv (i) Brow > C middle row anamoly)3'igp) order of disproportionation [Iots Bro+>c10+]xotx'+ x03'order of stabilityHC107 HBro > HIO4 interhalogen Compounds11when two different halogens react with each otherinter halogens cpd are formed.General compositions xx', XX3, xxs, xx7'ratio between radii X and x increases;As atoms per unit molecule increases moleculeeg. noof IF7 have max no of maximum atoms perI & F isThere . ratio is no of more than 2 halogens in atomolecule. covalent and b.p increases x' C°: due ionicincrease Bonds are in AG.N between res] X $ duechrocter & AX7 is are b.pt form largely by Br 8 than Ito AXS their larger size. are more reactive differ or polarityX2Interhalogen F2) due epds to high AE.N(except bond or Low B.P.E.ofPreprationI2+C12Icl3CIFcl2+ F2F2IFSI2+CIF3C12+ F2I2+ F2IF7BrtsgasThese Br2+ Brt 2 epds F2 F2 inter can BrF3 be halogen gases, opa liquid of are F or is solid colour coloweless, ( CIF mass )but Generally cpds of heavier Tes halogens with nature. The in molecolour All are intensity diamagnetic in in E.N differencestability with CIF) ICI> IBr7 BrclAll IF theses 7 BrF> undergoes from hydrolysis smaller giving halogerhalide ion derived holite, halate halogen & perholateand anion hyponality derived from HX'+ larger Hox!xx' + H2OHX'+ HXO2thoxxs XX3+ th2Hx'+ HXO3++ H2OHx'+ HYOU usesNor aqueou solvents.use for production of UF6 in enrichmentof U235UCS) + CIF3UF6 + CIF (g)( e e(g)Pseudohalogens These are univalent ions in consisting whichatleast one is N, that have property similarof 2 or more atomsto that of halide ions,salts are insoluble in water butegIsilver Sodium Salts are insoluble in HX. waterH- compounds are acids like2some anions can be oxidised to give molecules3X2.AcidsDimerAnionsCN'HCN(CN)2SCNTHSCN(SCN)2(thiocyonicacid)-1HOCNO-CN(cyanic acid)N3HN3chydrazoic acid)CN+ shows maximum similarity with CTBrt and It.1forms HCN.2 forms (CN)23Ag CN4 are insoluble inthoNa CN is soluble in H2O4AgeN is soluble inNH3'3(curcer)u]&[cuci]]3complex tendency.5 yholides f13eg:- KI+ + I2RI3+ICI+ KCIK(III)JIcl3+ KCIIF5+ CSFCs(IF)KEICBB]ICI + KBrHeating effects Product lattice on heating energy depends of holide productThe lattice energy highest of alkaliuponhalide with smaller halogen is ILLRbcl +eg:- Rb(Ic)2]High L.E.RbI + Cl2II']structure of-2Is', If+, IfItd I-II-I[I.I.I.I.I.I.II-I[I-I,ion dipole interactioninducedStability order :-I3 > Br; Cb > F3C depends upon donating abilityof x-1)