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Appendix4.MASSSPECTROMETERMASSSPECTROSCOPY
Appendix4aIntroductiontotheMassSpectrometer
Themassspectrometerisaninstrumentbywhichyoucanseparate
ionised/charged(+)particlesofdifferentmassanddeterminethe
amountsofeachparticleinamixture.
Thetechniqueiscalledmassspectroscopyormassspectrometry('mass
spec'and'MS'inshorthand!).
Massspectrometrygivesaccurateinformationontherelativemasses
ofisotopesandtheirrelativeabundance(proportions).
Massspectrometryisanimportantmethodofanalysisinchemistry
andcanbeusedtoidentifyelementsbytheircharacteristicmass
spectrumpatternthetechniqueisusedinplanetaryspaceprobese.g.
massspectrometerinstrumentationisincorporatedintheMars
explorervehicles.
Thesubstancetobeanalysedisintroduced/injectedintoahighvacuum
(extremelylowpressure)tubesystem(atKleftdiagram)wheretheparticles
areionisedbycollidingwithbeamofhighspeedelectrons(atQinleftdiagram).
Note:Ifthesampleisnotalreadyagas,thenaliquidorsolidsubstancemustbe
vapourised,i.e.thematerialmustbeinthegaseousstatetobeanalysedinamass
spectrometer.Thematerialbeinganalysedmustintheformoffreemovinggaseous
atomsormoleculeswhichcanbethenbombardedwithelectronstoproduceequallyfreemovingpositiveions
whichcanrapidlybeacceleratedinapowerfulelectricfield.Itisthemanipulationofthestreamofgaseous
ionsthatformsthebasisofmassspectrometry.Youcannotanalyseanyliquidorsolidmaterialinthisway
unlessitisvapourised.
Theresulting(+)ionsareaccelerateddownatube(from+toplates,Pinleftdiagram)andthenthroughapowerful
magneticfield.
Thechargedorionisedparticlesaredeflectedbythispowerfulmagneticfield(Rinleftdiagram).
Howmuchtheyaredeflecteddependsontheparticlemassandthespeedoftheparticleandthestrengthofa
magneticfieldi.e.lighterparticlesoflowermass(andmomentum)aredeflectedmorethanheavierparticlesofbiggermass
(seerightdiagrambelow)foragivensetofconditions.
Byvaryingthestrengthofthemagneticfield,itispossibletobringintofocusontoaniondetector(Ninleftdiagram)at
theendofthetube(effectivelyanelectricaleventisdetected),everypossiblemassinturnandameasurethestrengthof
theioncurrent,whichisameasureofhowmuchofthationhasbeenformedfromthesampleunderanalysis.
12/12/13 A Level Introduction to Mass Spectrometry - mass spectra, mass spectrum time of flight mass spectrometer, relative peak height, relative abundance of i
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Asimplifieddiagramofamassspectrometertubesystemisshownbelow(left)withfurtherexplanationastowhatis
goingonandanextradiagramtoshowtherelativepathsoflighttoheavyionsforagivenstrengthofmagneticfield.

KEYTODIAGRAMandmoredetailofeachcomponent'sfunction
K=sampleinjectionpoint,itmustbeagas,soaliquid/solidmustbevaporisedattheinjection
point.
IONISATION
Q=highvoltage(high+/p.d.)electrongunwhichfiresabeamofhighspeed/energyelectronsfromaheated'metal
element'intothevaporisedsampleunderanalysisandcausesionizationoftheatoms(ormolecules)formingpositive
ions(mainlymonopositiveincharge).
ThecollisionofhighKEelectronswithatomsormoleculescausesanotherelectrontobeknockedofftheparticleleavinga
negativedeficiti.e.apositivelychargedparticleisformede.g.
M
(g)
+e

==>M
+
(g)
+2e

,usuallywrittenasjust
M
(g)
==>M
+
(g)
+e

(Mmightrepresente.g.ametalatomoramolecule)
Theionsformedshouldbewrittenas[M]
+
,anotationthatishandyifyouaredealingwithionisedmolecule
fragmentswithanoverallsinglepositivechargee.g.[CH
3
]
+
isseeninthemassspectrumofmethanegas,
CH
4
.
Thelowpressure(~vacuum)isneededtopreventtheionsfromcollidingwithairparticleswhichwouldstop
themreachingtheiondetectorsystem.
ACCELERATION
P=arenegativeplateswhichacceleratethepositiveionsdownthetube(therearepositiveplatesatthestartofthe
tube).Amovingbeamofchargedparticlescreatesamagneticfieldarounditself,andthis'ionbeam'magneticfield
interactswiththemagneticfieldatR.
DEFLECTIONSEPARATION
R=themagneticfieldthatcausesdeflectionofions,thisiscanbevariedtochangetheextentofdeflectionforagiven
massandtofocusabeamofionsofparticularmassdownontothedetector.Hence,byprogrammingthemass
spectrometerto'sweep'throughalllikelyparticlemasses,intermsoftherighthanddiagram,youcanincreasethestrength
ofthemagneticfieldtobringintofocusontotheiondetectormonopositiveionsofincreasingmass.
DETECTION
N=aniondetectionsystemwhichessentiallygeneratesatinyelectricalcurrentwhentheionshitit.
Thestrengthsofthe'electronic'signalsfromthevariousionpeaksaresenttoacomputerforanalysis,computationand
display.Theytellyoutheparticlemassespresentandtheirrelativeabundance(seethemassspectrumdiagramforthe
elementstrontiumbelow).
MASSSPECTRUM
Theresultingrecordoftheionpeaksiscalledthemassspectrumormassspectra.Thehighestpeakiscalledthebase
peakandisoftengiventherelativeandarbitraryvalueof100,particularlyinthemassspectraoforganiccompounds.
MASSSPECTRA
Forelementsyougetaseriesofsignalsorionpeaksforeachisotopepresentandtheratioofpeakheightsgivesyouthe
12/12/13 A Level Introduction to Mass Spectrometry - mass spectra, mass spectrum time of flight mass spectrometer, relative peak height, relative abundance of i
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Forelementsyougetaseriesofsignalsorionpeaksforeachisotopepresentandtheratioofpeakheightsgivesyouthe
relativeproportionofeachisotopeintheelementsothatyoucancalculatetherelativeatomicmassofanelement.This
'simple'spectraofmononuclearionslikeSr
+
isonlytruefornonmolecularelementslikemetals(seemassspectrumof
strontiumdiagrambelow)ornoblegases,butformolecularelementslikenitrogenorthehalogensthingsarenotso
simple(seechlorineexamplebelow).
Forlargere.g.organicmolecules,thingscanbeverycomplexindeed,asmoleculesfragmentandmanydifferentionscan
beformedBUTyoucangettherelativemolecularmassofamoleculebyidentifyingwhatiscalledthemolecularion
peak,thatis,whenoneelectronisknockedofthemoleculebutthemoleculeretainsitsfullmolecularstructure.
e.g. benzoicacid(M
r
=122)givesamolecularionpeakofm/e=122,dueto[C
6
H
5
COOH]
+
butyoualsogetfragmentssuchas[C
6
H
5
]
+
withanm/eof77asthemoleculebreaksuponfurtherelectron
impact.
CHLORINEEXAMPLE
Chlorineisagoodexampleofamolecularelementwhosemassspectracanbeabittrickywhen
firstencountered...
Chlorineconsistsoftwoprincipalisotopes,chlorine37(25%is
37
Cl)andchlorine35(75%is
35
Cl).
BUT,chlorineconsistsofCl
2
diatomicmolecules,which,onionisation,cansplitintochlorineatoms.
Theresultisaseriesof5differentmasspeaksfromthevariousisotopicatomicormolecularion
possibilities.
1. [
37
Cl
37
Cl]
+
or[
37
Cl
2
]
+
m/z=74
2. [
37
Cl
35
Cl]
+
m/z=72(notethatyoumustshowthetwoisotopesseparately)
3. [
35
Cl
35
Cl]
+
or[
35
Cl
2
]
+
m/z=70
4. [
37
Cl]
+
m/z=37
5. [
35
Cl]
+
m/z=35
m/zmeanstherelativemassoftheionoveritscharge,whichforourpurposesthechargeistaken+1(little
z)andthemass(littlem)istherelativeatomic/formulamassoftheparticle.m/zsometimesquotedasm/e.
Youshouldwritethestructureoftheioninsquarebracketsandputthechargeontheoutsideoftheminthe
toprightthisisanimportantanduniversallyacceptednotationinmassspectrometry.
Examplesofthecalculationoftherelativeatomicmassofanelementusing%ofisotopesisgiveninPart1
ofGCSEAS(basic)calculations,anexampleofcalculatingrelativeatomicmassfromamassspectrumis
givenbelowforthemetallicelementstrontium.
Themassspectraoforganiccompoundscanbeverycomplexasthemoleculesfragmentunderelectronbombardment,
buttheresultingmassspectracanusedtoidentifycompoundsfromtheir'fingerprint'patternofionpeaksofdifferent
massandparticularproportionsforagivensetofexperimentalconditions.
Thelargestm/zvaluegivesthemolecularmassofamolecule,i.e.theionoflargestmass,priorto
fragmentation,isformedwhentheoriginalwholeandneutralmolecule,losesoneelectrone.g.forethaneit
wouldbeduetotheformationof[C
2
H
6
]
+
,m/z=30andiscalledthemolecularionpeak.
STRONTIUMEXAMPLE
A'simple'elementspectrumtointerpretANDasubsequentrelativeatomicmasscalculation
basedonthemassspectrumoftheelementstrontium
12/12/13 A Level Introduction to Mass Spectrometry - mass spectra, mass spectrum time of flight mass spectrometer, relative peak height, relative abundance of i
www.docbrown.info/page04/4_71atomMSintro.htm 4/7
Therelativeatomicmassofanelement,A
r
,istheweightedaveragemassoftheisotopes
present,comparedto1/12thoftherelativemassofthecarbon12isotope.[
12
Cisgiventherelative
massvalueof12.0000]
Quiteoftenthehighestm/epeakisarbitrarilygiventherelativevalueof100,asinthiscaseandreferredtoasthebase
peak,butthepeaklinesmightwellindicate%abundanceofisotopes.Thediagramofabundancesissometimescalleda
stickdiagram.
Relativepeakheight=relativeabundanceasmeasuredfromtheioncurrentdetectorsignal.
Themassspectrumshowsstrontiumconsistsoffourisotopes,
84
Sr(peakheight=0.68),
86
Sr(peakheight=12.0),
87
Sr
(peakheight=8.47)and
88
Sr(peakheight=100.0)
Thesumoftheheights=0.68+12.0+8.47+100.0=121.15
SowecannowcalculatetheweightedaveragemassofALLtheisotopes.
ThereforeA
r
={(0.68x84)+(12.0x86)+(8.47x87)+(100.0x88)}/121.15=87.7
Thebookvalueis87.62,BUTthiscalculationdoesNOTtakeintoaccounttheveryaccuraterelativeatomicmassesbased
onthecarbon12scale,itmerelyusesthemassnumbers,whicharealwaysinteger.
ISOTOPICMASSESdefinitionanduses
Veryaccurateisotopicmassesareusuallyatinyfractiondifferentfromawholenumberbutprovideinvaluableinformation.
Modernmassspectrometersareexceedinglyaccurateandverysophisticatedinstrumentsandcanmeasuremasstoat
least4decimalplaces.TheycanreadilydistinguishbetweenN
2
,COandC
2
H
4
molecules,allwithanintegerM
r
of28.
Theveryaccuratemolecularionmassesare[N
2
]
+
=28.0061,[CO]
+
=27.9949and[C
2
H
4
]
+
=28.0313
Averyaccuratemassspectrometer(forhighresolutionmassspectroscopy)canevendifferentiatebetweenorganic
moleculesofthesameintegermolecularmass.
e.g.forthemolecularmass103,somepossible,howeverunlikely,molecularformulaecouldtheoreticallybe
C
5
HN
3
=103.0170,C
3
H
5
NO
3
=103.0269,C
2
H
5
N
3
O
2
=103.0382,C
7
H
5
N=103.0427,CH
5
N
5
O=103.0494
Calculationsof%compositionofisotopes
ItispossibletodothereverseofarelativeatomicmasscalculationifyouknowtheA
r
andwhichisotopesarepresent.
Itinvolvesalittlebitofarithmeticalalgebra.
12/12/13 A Level Introduction to Mass Spectrometry - mass spectra, mass spectrum time of flight mass spectrometer, relative peak height, relative abundance of i
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Itinvolvesalittlebitofarithmeticalalgebra.
TheA
r
ofboronis10.81andconsistsofonlytwoisotopes,boron10andboron11
Therelativeatomicmassofboronwasobtainedaccuratelyinthepastandmassspectrometerscansortouttheisotopes
present.
IfyouletX=%ofboron10,then100Xisequalto%ofboron11
ThereforeA
r
(B)=(Xx10)+[(100X)x11)/100=10.81
so,10X11X+1100=100x10.81
X+1100=1081,11001081=X(changesideschangesign!)
thereforeX=19
sonaturallyoccurringboronconsistsof19%
10
Band81%
11
B(thedatabooksquote18.7and81.3)
Itshouldbepointedoutthattherelativeratioofisotopescanbeveryaccuratelydeterminedusingamodernmass
spectrometerANDindividualisotopicmassescanbemeasuredtofourdecimalplaceswhichwereNOTusedintheabove
calculation.
Appendix4bTheTimeofFlightMassSpectrometer(foradvancedlevelstudentsonly!)
Ionmassseparationusingatimeofflightmassspectrometeramoremoderninstrument
Inatimeofflightmassspectrometertheionsareformedinasimilarmannerbyelectronbombardment,andthe
resultingionsacceleratedbetweenelectricallychargedplates.
Again,thesamplemustbeagasorvapourisedandisbombardedwithanelectronbeamorlaserbeamtoknockoff
electronstoproducepositiveions.
However,themethodofseparationduetodifferentm/e(mass/charge)valuesisthendependentonhowlong
ittakestheiontotravelinthedriftregion'i.e.theregionNOTundertheinfluenceofanacceleratingelectricfield.
Theionsareacceleratedinthesamewaybetweenpositivetonegativeplatesinanelectricfieldoffixed
strengthi.e.constantpotentialdifference.
Thesmallerthemassoftheionisedparticle(ionizedatom,fragmentorwholemolecule)theshorterthetime
offlightinthedriftregionwherenoelectricfieldoperates.
12/12/13 A Level Introduction to Mass Spectrometry - mass spectra, mass spectrum time of flight mass spectrometer, relative peak height, relative abundance of i
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offlightinthedriftregionwherenoelectricfieldoperates.
Thisisbecauseforagivenacceleratingpotentialdifference,alighterparticleisacceleratedmoretoahigher
speedthanaheavierion,sothe'timeofflight'downthetubeisshorter.
ThereforetheionsaredistinguishedbydifferentflighttimesNOTbydifferentmassesbeingbroughtintofocus
withamagneticfieldasdescribedinsection4aBUTtheseparationbytimeofflightisstilldeterminedbythem/e
(m/z)valueoftheion.
ThegeneralprinciplesoftheseparationarerequiredknowledgebutthemathematicsisNOTneededbyAlevel
students,butifyouareinterested,asimplifiedsummaryisgivenbelow
t=K
inst
(m/q)
t=timeofflight,m=massofion,q=chargeonion,
K
inst
=aproportionalityconstantbasedontheinstrumentsettingsandcharacteristicse.g.theelectricfield
strength,lengthofanalysingtubeetc.
Thereforetisproportionaltothesquarerootofthemassoftheionforparticlescarryingthesame
chargethebiggerthemassthelongerthe'flighttime'.
Thefirstequationisderivedpartlyfromtheextramathematicsoutlinedbelow.
KE=qV,thekineticenergyimpartedtotheionisgivenbyitschargexthepotentialdifferenceofthe
acceleratingelectricfield.
Theacceleration,forafixedelectricfield,resultsinanionhavingthesamekineticenergy(KE)asanyother
ionofthesamechargeqbutthevelocityvoftheiondependsonthem/e(m/z)value.
v=d/t(ort=d/v),wherev=velocityofacceleratedparticleinthedriftregion,d=lengthoftubeinthedrift
region.(ort=d/v)
KE=
1
/
2
mv
2
,sothebiggerm,thesmallerisvinthedriftregionandhencethebasisofdetectingionsof
differentmassbydifferent'flighttimes'.
Thediagrammakesthemethodlooksimple,butfarfromit,theinstrumentworksinapulsedmanneri.e.
pulsedelectricfield,andsomeprettysophisticatedelectronicsareusedtoanalysethesignalsfromthe
detectorandthesoftwarecalculatesthemassoftheionbasedonthedriftflighttime.
BasicGCSE/IGCSE/ASAtomicStructureNotes
RevisionnotesforGCEAdvancedSubsidiaryLevelASAdvancedLevelA2IBReviseAQAOCREdexcelSaltersCIE
revisingcoursesforpreuniversitystudents(equaltoUSgrade11andgrade12andHonours/honorslevelcourses)
RevisionnotesforGCEAdvancedSubsidiaryLevelASAdvancedLevelA2IBReviseAQAOCREdexcelSaltersCIE
revisingcoursesforpreuniversitystudents(equaltoUSgrade11andgrade12andHonours/honorslevelcourses)

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