Name:MohitN.

Mulani Sectioninstructor:BrianKasper LuminolandChemiluminescence

ExperimentDueDate:2/20/14 Section:231

1)In3nitrophthalicacid,thecarboxylicwhichismoreacidicisatthe2positionwithpKa=2. Inthisconjugatedringsystem,thenitrogroupactsasapowerfulelectronwithdrawinggroup (deactivatingagent)whichservestoremove/pullawayelectrondensityfromthecarboxylicacidgroups andmakethemmoreelectrophilicwhichstabilizestheconjugatebase(anion)andmakesiteasierforit tolosetheH+.Thiseffectofthenitrogroupisfeltmuchmorestronglybythecarboxylicgroupcloserto itontheorthoposition(w.r.tit)thantheotheroneinthemetapositionmakingitmoreacidic. 2)TocalculatetheKeq,weneedthepKavaluesoftheacidandtheconjugateacid.Wehaveoneof these(for3nitrophthalicacid:2)andtofindtheother,wecanusethepKbvalueofHydrazinewhichis 5.77.AsthesumofthepKbandpKavaluesforaconjugatepairis14,wecancalculateittobe8.23. Makingdissociationequationsfortheacidsanddividingthemtogettheoriginalreaction,weseethat pKeqis28.23=6.23.Keqthereforeis106.23or1.7x106. 3)Thereactionof3nitrophthalicacidandHydrazinecouldgobothwaysbutonlytheonewhich involvesthereplacementoftheOHgroupwithaminegroup(NH)andthentheintramolecular replacementoftheotherOHgroupof3nitrophthalicacidwiththeotheraminegroupisfavoured.This reactionismorelikelytohappenbecauseasitisintramolecular,itisfasterthantheminoronewhich involves2moleculesofhydrazineattackingtheseparateOHgroups.Wevealsoestablishedthat becauseofitspositionrelativetothenitrogrouponeofthecarboxylicgroupsismoreacidicwhich makesitmorelikelytobetheonewhichisattackedfirstfollowedbyanintramolecularreaction. 4)ThepKbvalueforethant1,3diamineishigherthanthatofhydrazine(itisaweakerbase)which

meansthesubsequentpKaoftheconjugateacidwillbesmallermakingitsKeqhigher.Thislowersthe Keqoftheoriginalreaction(whichiscalculatedastheratioofacidKeqandconjugateacidKeqimplying thattherateofforwardreactionhasbeenlowered.Theproductformedasaresultofreactingtheacid withethane1,3diaminewillbeamuchlargerringastheamidegroupnowattacksthecarboxylicacid forminganeightmemberedring.Eightmemberedringsascomparedtosixmemberedrings(nostrainin chairconformation)orfivememberedrings(onlytorsionalstrain)havebothtorsionalstrainandsteric strain.Thismakesitmoreunstable. 5)Thisoccursbecauseamidesarelessbasicthanaminesonaccountofresonancestabilization.The resonanceoccursduetothepresenceofalonepaironNitrogenwhichisdelocalizedbetweenitandthe electronegativeoxygenofthecarbonylgroup. 6)485nm.TheluminolontreatmentwithK3Fe(CN)6/H2O2emitslightwhichhasabrightblue(almost cyan)colourwhichcorrespondstothehighendofthebluewavelength(450500nm),edgingtowards greenratherthanviolet.Thislightwouldbeamixtureofseveralwavelengthsaroundthehigherendof thisrangesoIselected485nm. 7)Itwouldbeaterriblelightsourcebecauseoftheshorttimeitsglowlasts(onlyafewseconds).This wouldmeanconstantreactionsofluminolwithoxidisingagentswhichiscostlyanddifficultifthesignis torun24hoursaday. 8)A)Luminol:Exactmass177.05g Massoftwomostabundantisotopes:177.05g,178.06g. Luciferin:Exactmass280.00g Massoftwomostabundantisotopes:280.00g,281.00g. B)Luminolwouldhaveauniquesignalataround3000cm1associatedwiththeNHgroupand

Luciferinwouldalsohavearecognizablesignalduetothepresenceofsulphursinglebondedtocarbon initsheterocyclicsystem. C)Luminolhas7signals(with2uniquecarbonsatthecentreofthebicyclicsystemhavingthesame energywithashiftdifferenceofabout1ppm)andLuciferinhas11signalswithdifferentchemicalshifts. D)Luminolhas5signalsandLuciferinhas8signals.