30/06/2015

GasChromatographyTheory

updatedSunday,April06,2014
GasChromatography(GCorGLC)isacommonlyusedanalytictechniqueinmanyresearchand
industriallaboratoriesforqualitycontrolaswellasidentificationandquantitationofcompoundsina
mixture.GCisalsoafrequentlyusedtechniqueinmanyenvironmentalandforensiclaboratoriesbecause
itallowsforthedetectionofverysmallquantities.Abroadvarietyofsamplescanbeanalyzedaslongas
thecompoundsaresufficientlythermallystableandvolatile.
Howdoesgaschromatographywork?
Likeforallotherchromatographictechniques,amobileandastationaryphasearerequiredforthis
technique.Themobilephase(=carriergas)iscomprisedofaninertgasi.e.,helium,argon,ornitrogen.
Thestationaryphaseconsistsofapackedcolumnwherethepackingorsolidsupportitselfactsas
stationaryphase,oriscoatedwiththeliquidstationaryphase(=highboilingpolymer).Mostanalytical
gaschromatographsusecapillarycolumns,wherethestationaryphasecoatsthewallsofasmalldiameter
tubedirectly(i.e.,0.25mfilmina0.32mmtube).
Theseparationofcompoundsisbasedonthedifferentstrengthsofinteractionofthecompoundswiththe
stationaryphase(likedissolveslikerule).Thestrongertheinteractionis,thelongerthecompound
interactswiththestationaryphase,andthemoretimeittakestomigratethroughthecolumn(=longer
retentiontime).Intheexampleabove,compoundXinteractsstrongerwiththestationaryphase,and
thereforelacksbehindcompoundOinitsmovementthroughthecolumn.Asaresult,compoundOhasa
muchshorterretentiontimethancompoundX.
Whichfactorsinfluencetheseparationofthecomponents?
1.Boilingpoint
Theboilingpointofacompoundisoftenrelatedtoitspolarity(seealsopolaritychapter).Thelowerthe
boilingpointis,theshorterretentiontimeusuallyisbecausethecompoundwillspentmoretimeinthe
gasphase.Thatisoneofthemainreasonswhylowboilingsolvents(i.e.,diethylether,dichloromethane)
areusedassolventstodissolvethesample.Thetemperatureofthecolumndoesnothavetobeabovethe
boilingpointbecauseeverycompoundhasanonzerovaporpressureatanygiventemperature,even
solids.Thatisthereasonwhywecansmellcompoundslikecamphor(0.065mmHg/25oC),isoborneol
(0.0035mmHg/25oC),naphthalene(0.084mmHg/25oC),etc.However,theirvaporpressuresarefairly
lowcomparedtoliquids(i.e.,water(24mmHg/25oC),ethylacetate(95mmHg/25oC),diethylether
(520mmHg/25oC)).
2.Thepolarityofcomponentsversusthepolarityofstationaryphaseoncolumn
Ifthepolarityofthestationaryphaseandcompoundaresimilar,theretentiontimeincreasesbecausethe
compoundinteractsstrongerwiththestationaryphase.Asaresult,polarcompoundshavelongretention
timesonpolarstationaryphasesandshorterretentiontimesonnonpolarcolumnsusingthesame
temperature.Chiralstationaryphasesthatarebasedonaminoacidderivatives,cyclodextrinsandchiral
silanesarecapableofseparatingenantiomersbecauseoneenantiomerinteractsslightlystrongerthanthe
otheronewiththestationaryphase,oftenduetostericeffectsorotherveryspecificinteractions.For
instance,acyclodextrincolumnisusedinthedeterminationoftheenantiomericexcessinthechiral
epoxidationexperiment(Chem30CL).
3.Columntemperature
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Aexcessivelyhighcolumntemperatureresultsinveryshortretentiontimebutalsoinaverypoor
separationbecauseallcomponentsmainlystayinthegasphase.However,inorderfortheseparationto
occurthecomponentsneedtobeabletointeractwiththestationaryphase.Ifthecompounddoesnot
interactwiththestationaryphase,theretentiontimewilldecrease.Atthesametime,thequalityofthe
separationdeteriorates,becausethedifferencesinretentiontimesarenotaspronouncedanymore.The
bestseparationsareusuallyobservedfortemperaturegradients,becausethedifferencesinpolarityandin
boilingpointsareusedhere(forexamplesseetheendofthechapter)
4.Carriergasflowrate
Ahighflowratereducesretentiontimes,butapoorseparationwouldbeobservedaswell.Likeabove,
thecomponentshaveverylittletimetointeractwiththestationaryphaseandarejustbeingpushed
throughthecolumn.
5.Columnlength
Alongercolumngenerallyimprovestheseparation.Thetradeoffisthattheretentiontimeincreases
proportionallytothecolumnlengthandasignificantpeakbroadeningwillbeobservedaswellbecause
ofincreasedlongitudinaldiffusioninsidethecolumn.Onehastokeepinmindthatthegasmoleculesare
notonlytravelinginonedirectionbutalsosidewaysandbackwards.Thisbroadeningisinversely
proportionaltotheflowrate.Broadeningisalsoobservedbecauseofthefiniterateofmasstransfer
betweenthephasesandbecausethemoleculesaretakingdifferentpathsthroughthecolumn.
6.Amountofmaterialinjected
Ideally,thepeaksinthechromatogramdisplayasymmetricshape(Gaussiancurve).Iftoomuchofthe
sampleisinjected,thepeaksshowasignificanttailing,whichcausesapoorerseparation.Mostdetectors
arerelativelysensitiveanddonotneedalotofmaterialinordertoproduceadetectablesignal.Strictly
speaking,understandardconditionsonly12%ofthecompoundinjectedintotheinjectionportpasses
throughthecolumnbecausemostGCinstrumentsareoperatedinsplitmodetopreventoverloadingof
thecolumnandthedetector.Thesplitlessmodewillonlybeusedifthesampleisextremelylowin
concentrationintermsoftheanalyte.
7.Conclusion
Hightemperaturesandhighflowratesdecreasetheretentiontime,butalsodeterioratethequalityofthe
separation.
Whichdetectorsareused?
1.MassSpectrometer(GC/MS)
ManyGCinstrumentsarecoupledwithamassspectrometer,whichisaverygoodcombination.TheGC
separatesthecompoundsfromeachother,whilethemassspectrometerhelpstoidentifythembasedon
theirfragmentationpattern(seeMassSpectrometrychapter).
2.FlameIonizationDetector(FID)

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Thisdetectorisverysensitivetowardsorganicmolecules(1012g/s=1pg/s,linearrange:106107),but
relativeinsensitiveforafewsmallmoleculesi.e.,N2,NOx,H2S,CO,CO2,H2O.Ifproperamountsof
hydrogen/airaremixed,thecombustiondoesnotaffordanyorveryfewionsresultinginalow
backgroundsignal.Ifothercarboncontainingcomponents,areintroducedtothisstream,cationswillbe
producedintheeffluentstream.Themorecarbonatomsareinthemolecule,themorefragmentsare
formedandthemoresensitivethedetectorisforthiscompound.Unfortunately,thereisnodirect
relationshipbetweenthenumberofcarbonatomsandthesizeofthesignal.Asaresult,theindividual
responsefactorsforeachcompoundhavetobeexperimentallydeterminedforeachinstrument.Dueto
thefactthatthesampleisburnt(pyrolysis),thistechniqueisnotsuitableforpreparativeGC.Inaddition,
severalgasesareusuallyrequiredtooperateaFID:hydrogen,oxygen(orcompressedair),andacarrier
gas.
3.ThermalConductivityDetector(TCD)
ThisdetectorislesssensitivethantheFID(105106g/s,linearrange:103104),butiswellsuitedfor
preparativeapplications,becausethesampleisnotdestroyed.Thedetectionisbasedonthecomparison
oftwogasstreams,onecontainingonlythecarriergas,theotheronecontainingthecarriergasandthe
compound.Naturally,acarriergaswithahighthermalconductivityi.e.,heliumorhydrogenisusedin
ordertomaximizethetemperaturedifference(andthereforethedifferenceinresistance)betweentwo
filaments(=thintungstenwires).Thelargesurfacetomassratiopermitsafastequilibrationtoasteady
state.Thetemperaturedifferencebetweenthereferenceandthesamplecellfilamentsismonitoredbya
Wheatstonebridgecircuit(thestudentlearntaboutthiscircuitryinphysics!).
4.ElectronCaptureDetector(ECD)
Thisdetectorconsistsofacavitythatcontainstwoelectrodesandaradiationsourcethatemitsradiation
(i.e.,63Ni,3H).Thecollisionbetweenelectronsandthecarriergas(methaneplusaninertgas)produces
aplasmacontainingelectronsandpositiveions.Ifacompoundispresentthatcontainselectronegative
atoms,thoseelectronswillbecapturedtoformnegativeionsandtherateofelectroncollectionwill
decrease.Thedetectorisextremelyselectiveforcompoundswithatomsofhighelectronaffinity(1014
g/s),buthasarelativelysmalllinearrange(~102103).Thisdetectorisfrequentlyusedintheanalysisof
chlorinatedcompoundsi.e.,pesticides(herbicides,insecticides),polychlorinatedbiphenyls,etc.for
whichitexhibitsaveryhighsensitivity.
UsefulLinks:

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