Without Spectroscopy at the Beginning, Catalysis R

1WITHOUTSPECTROSCOPYATTHEBEGINNING,CATALYSISRESEARCHPROCEEDEDINTHEWRONGDIRECTIONFORMORETHAN100YEARSRalphA.Gardner-Chavis1JohnT.Reye2,TheodoreB.Selover,Jr.3,HuixiongZhang41.ChemistryDepartment,ClevelandStateUniversity2.SchoolofChemicalandBiomolecularEngineering,GeorgiaInstituteofTechnology3.CuyahogaCommunityCollege4.Diapedia,LLC,StateCollege,PennsylvaniaKEY:gaseousintermediates,catalystprediction,electricfields,resonance,AtomicEnergyLeveltablesABSTRACTOnehundredsixtyyearsagowithoutthebenefitoftheappropriateinstrument,researchersincatalysiscametotheonlypossiblelogicalconclusionatthattime.Namely,thatthereactants,intermediates,andproductsareattachedtothecatalyst.Thestepsofthestandardexperimentalprocedurebecame:1.preparethecatalyst,2.exposeittoagasforsomeperiodoftime,3.thoroughlyevacuatethesystemtoremoveanyvestigeofphysisorption,4.studythechemisorbedspeciesbyweighingwithamicro-balanceorothermethod.Aftersome80yearsofthisprocedure,wheninfraredspectroscopy,theinstrumentthatcouldidentifymoleculesonsurfacesbecameavailable,itwassoautomaticto“evacuatebeforeinvestigate”apparentlynooneexaminedthephysisorptionregionoftheexperimentalprocedureuntilthispresentauthorin1954.Then,thefirstexperimentsdemonstratedthatwhenthesurfaceisacatalyst,carbonmonoxideproducedseveralsurfacespeciesatfrequenciesdeviatingmorethan200cm-1fromthegasfrequency.Whilethesesurfacespeciesareinagas-likestate,theydesorbedonlyasnormalcarbonmonoxidegas.Thiswasthefirstmajordiscoveryfromthisstudy.Itisbecausetheseintermediatesofcatalysisexistonlyonthesurfacesofcatalystsandarereadilyremovedbyevacuationthattheywerenotdetectedpriortothisstudyin1954.Thefieldofcatalysismustacceptandincorporatethisinformationintoitsprocedurestoaccelerateitsadvances.Newreactionsandcatalystsmaybediscoveredserendipitouslybypresenttechniquesbecausereactantsattachedtothecatalystmaydetachunobtrusivelyandproceedtoproductsasdescribedinthefollowing.Gardner-Chavis,usingtheinfraredtechniquepioneeredbyR.P.Eischens,observedthatthesephysisorbedsurfacespeciesoncatalystshavefrequenciesintermediatetothefrequenciesofionsandneutralmolecules.Thusthesefrequenciescorrespondtonon-integralnumbers,thefractionofwhichisuniqueforeachcatalyst.TheAtomicEnergyLeveltablesfromNISTlistavailableenergystatesforelectronsexcitedoutfromthegroundstateofatomsandpositiveionsofalmostalloftheelementsForexample,thefirststateabovethegroundstateforthechromiumatomisat7,593.16;thefirststateforthepositiveionisat11,961.81;thefirststatesforthedoublepositiveionareat62.22,183.16,356.55,and576.08cm-1.Excitedstatesthisclosetothegroundstatewillbe2occupiedforsomefractionoftimethuscreatinganelectricfieldwithafractionalcharge.Eachpositiveionthatmayfunctionasacatalysthasadifferentsetoftheselow-lyinglevels.Thuseachionpresentsadifferentfractionalfieldtopreparethechemicalreactantsforthecatalyticevent.Electricfieldswithafractionalchargewerethesecondmajordiscoveryofthisstudy.The.catalyticsiteforareactionofthetypeA+B
Ciscomposedoftwoidenticalions,oneforeachreactant.Whilethesetwoionsmustnotbeconnectedbyachemicalbondtheymustbecloseenoughthattheirfieldscreatearegionofoverlap.Thecatalystwhichisappropriateforaparticularreactionhaselectricfieldswiththefractionalchargethatwhenthischargeisimpartedtothetworeactantschangesthefrequencyoftheelectricfieldsofthereactantsatthesitesofreactionsothattheynowmatchharmonically.Thatis,theratioofthefrequencyofonetotheotherequalsapoweroftwo.Asthereactantspassthroughtheoverlapregion,becausetheirfrequenciesnowmatch,resonanceoccurs.Itisduringresonancethatelectronsareshared,pairedandexchangedandbondsarebrokenandmadetosatisfytheFreeEnergyconstraint.Thatthecatalystistheelectricfieldsexplainstheunusualobservationthatthecatalystisnotconsumedbyuse.TheconceptofelectricfieldsoperatinginconcerttocontrolmechanicalandchemicalreactionsisthethirdandmostextraordinarydiscoveryofthisstudyApplicationstoandexplanationsofmanyphenomenainmechanicsandbiologyaswellaschemistrymayresultfromthisdiscovery.Quantitativemathematicalanalysesofreactionsarepresentedforoxidation,chlorination,carbonicanhydrasehomologues,andtheeliminationofnitricoxidefromautoexhaust.DISCUSSIONItisdifficulttointroduceacompletelynewanddifferentparadigmintoafield,suchascatalysis,thathasbeenestablishedfor160years.Thusitwillbenecessarytopresentinthispapernotonlypreviouslypublishedexamplesofquantitativeapplicationsofthenewrelationstocatalysisbutalsooneormoreapplicationstootherrelatedareasofchemistry.Firstsomemisconceptionsmustbeclearedup.Justforamoment,dividecatalystsintototwogroups,inorganiccatalystsandorganiccatalysts.Inorganiccatalystsaremetalsandmetalliccompounds.Somearefoundnaturally,butmostarecompoundedforindustrialapplications.Asinglepieceofcatalyticmaterialmaycontainhundredstomillionsofactivecatalyticsites.Thesecatalystsmayfunctionassolidsorinsolutionandaresimplycalled“catalysts”.Theorganiccatalystsarecalled”enzymes”andarethecatalystsinlivingorganisms.Enzymesgenerallyareasinglesitecomposedoftwoidenticalions.Someandpossiblyallenzymeshaveproteinsassociatedwiththem.Theproteinsfa