ATOMIC ABSORPTION SPECTROPHOTOMETRY

COOKBOOK
Section 1

Basic Conditions of Analysis of Atomic

Absorption Spectrophotometry

Atomic Absorption Spectrophotometry Cookbook

Section 1

CONTENTS
1.

Principal of Atomic Absorption Spectrophotometry

1.1 Why atoms absorb light

1.2

Relation between light absorption rate and atomic density

1.3

Sample atomization method

2.

1
2

a)

Flameatomicabsorption....................................................................................

b)

Electrothermalatomicabsorption.....................................................................

Basic Condition for Analysis

2.1

Conditions of equipment

9
9

a)

Analysisline.......................................................................................................

b)

Slitwidth............................................................................................................. 13

c)

Lampcurrentvalue............................................................................................. 14

2.2

Analysis conditions of flame atomic absorption

15

a)

Flameselection................................................................................................... 15

b)

Mixingratioofoxidantandfuelgas.................................................................. 17

c)

Beampositioninflame....................................................................................... 17

2.3

Analysis conditions of electro-thermal atomic absorption

18

a)

Dryingcondition................................................................................................. 18

b)

Ashingcondition................................................................................................. 19

c)

Atomizingcondition........................................................................................... 21

d)

Sampleinjectionquantity................................................................................... 23

1.
1.1

Principal of Atomic Absorption Spectrophotometry

Why atoms absorb light
Theatomicabsorptionspectrometryusesabsorptionoflightofintrinsicwavelengths
byatoms.
All atoms are classified into those having low energies and those having high
energies.Thestatehavinglowenergiesiscalledthegroundstateandthestatehaving
highenergiesiscalledtheexcitedstate.
Theatominthegroundstateabsorbsexternalenergiesandisputintheexcitedstate.
Forexample,sodiumismainlyintwoexcitedstates,havinghigherenergiesby2.2eV
and3.6eVrespectivelythaninthegroundstate,asshowninFig.1.1.(eVisaunitto
measureenergiesandiscalledanelectronvolt.)When2.2eVenergyisgiventothe
sodiumatominthegroundstate,itmovesuptotheexcitedstatein(I)andwhen3.6eV
energyisgiven,itmovesuptotheexcitedstatein(II).
Energyisgivenaslight,and2.2eVand3.6eVrespectivelycorrespondtoenergyof
lightat589.9nmand330.3nmwavelength.
In the case of sodium in the ground state, only light of these wavelengths are
absorbedandnootherwavelengthlightisabsorbedatall.

Fig. 1.1 Sodium energy states

Thedifferencebetweenenergiesinthegroundstate,andintheexcitedstateisfixed
bytheelementandwavelengthoflighttobeabsorbed.Atomicabsorptionspectrometry
usesthehollowcathodelamp(HCL).
TheHCLgivesofflightcharacteristictotheelementalwavelengthbeingmeasured.
Thus,thelightabsorbedmeasurestheatomicdensity.
3

1.2

Relation between light absorption rate and atomic density

Whenlightofacertainintensityisgiventomanyatomsinthegroundstate,partof
thislightisabsorbedbyatoms.
Theabsorptionrateisdeterminedbytheatomicdensity.

Fig. 1.2 Principle of atomic absorption

WhenlightofIointensityisgiventodensityC,atomsspeedinlength1asshownin
Fig.1.2.ThelightisabsorbedanditsintensityisweakenedtoI.
ThefollowingformulaisformedbetweenIandIo.
I=Ioeklc
or log

(k:Proportionalconstant)

I =klc
Io

ThisiscalledtheLambertBeer'sLaw,andlogIvalueisabsorbance.
Io
Theaboveformulaindicatesthatabsorbanceisproportionaltoatomicdensity.
Whenabsorbanceismeasuredonsamplesof1,2and3ppmforexampleandplotted,
a straight line is obtained as shown in Fig. 1.3. Absorbance and concentration
representedgraphicallyiscalledthecalibrationcurve.
Whentheabsorbanceofanunknownsampleisobtained,theconcentrationcanbe
determinedfromthegraphasshown.

Concentration of unknown
sample

Concentration (ppm)

Fig. 1.3 Calibration curve

1.3

Sample atomization method

Theprinciplementionedabovecanbeappliedtolightabsorptionoffreeatoms.A
freeatommeansanatomnotcombinedwithotheratoms.However,elementsinthe
sampletobeanalyzedarenotinthefreestate,andarecombinedwithotherelements
invariably tomake a socalled molecule. Forexample, sodiumin seawater mainly
combineswithchlorinetoformaNaCl(Sodiumchloride)molecule.Absorptioncannot
bedoneonsamplesinthemoleculestate,becausemoleculesdonotabsorblight.
Thecombinationmustbecutoffbysomemeanstofreetheatoms.Thisiscalled

atomization.Themostpopularmethodofatomizationisdissociationbyheatsamples

areheatedtoahightemperaturesothatmoleculesareconvertedintofreeatoms.This
methodisclassifiedintotheflamemethod,inwhichachemicalflameisusedasthe
heatsource;andaflamelessmethod,inwhichaverysmallelectricfurnaceisused.
a)

Flameatomicabsorption
Theflameisproducedbyaburnerforatomizationandthisisthemostpopular
method.Itisstandardinalmostallatomicabsorptiondevicesavailableonthemarket
atpresent.

Fig. 1.4 Flame atomic absorption

AtypicaldiagramoftheburnerisshowninFig.1.4.
Thisfigureexplainsmeasurementofcalciumcontainedinthesampleliquidas
calciumchloride.Thesampleisatomizedbyanebulizeratfirst.Then,bigwater
dropsaredischargedtothedrain,andonlyafinemistismixedwithfuel,andoxidant
intheatomizerchamberandsenttotheflame.
Whentheygetintheflame,themistevaporatesinstantaneouslyandfineparticles
ofcalciumchloridemoleculesareproduced.Whentheseparticlesfurtheradvancein
theflame,calciumchlorideisdissolvedbyheatandfreecalciumatomsandchloride
atomsareproduced.
Ifabeamoflightatwavelength422.7nm(Ca)isintroducedthroughthispartof
theflame,atomicabsorptioncanbemeasured.Intheupperpartoftheflame,some
ofcalciumatomsarecombinedwithoxygentobecomecalciumoxideandsomeare
further ionized. Therefore, atomic absorption does notshow sufficient sensitivity
eveniflightisgiventosuchaposition.
Many combinations of various gases have been tested as the flame for
atomization.Inconsiderationofanalysissensitivity,safety,easyuse,costandother
points;therearefourstandardflamesused:airacetylene, nitrousoxideacetylene,
airhydrogenandargonhydrogen.Theseflamesareusedforeachelementdepending
onthetemperatureandgascharacteristics.
b)

Electrothermalatomicabsorption
The atomization method using a flame is still popularly used as the standard
atomizationmethodduetogoodreproducibilityofmeasuredvaluesandeasyuse.
6

However, a major defect of the flame method is the atomization rate out of all
samplequantityusedisabout1/10andtheremaining9/10isdischargedtothedrain.
Therefore,ithasbeenpointedoutthatatomizationefficiencyislowandanalysis
sensitivityisnotsohigh.
Electrothermal atomic absorption (flameless method), using a graphite tube,
improves theabovedefects toelevate sensitivity 10to200times asmuch.This
methodwasoriginatedbyDr.L'vovofRussia.

Fig. 1.5 Flameless atomizer

Intheelectrothermalatomicabsorptionmethod,thesampleisinjected inthe
formedgraphitetubeandanelectriccurrentof300ampere(maximum)isappliedto
thetube.Thegraphiteisheatedtoahightemperatureandtheelementsinthesample
areatomized.
Iflightfromthelightsourceissentthroughthetube,lightisabsorbedwhenthey
areatomized.
Inanactualmeasurement,afterthesampleisinjectedinthetube,heatingisdone
inthreestagesasshowninFig.1.6.Thatis,inthedryingstage,thetubeisheatedto
about100oCandwaterinthesampleevaporatescompletely.Then,intheashing
stage,thetubeisheatedto400oCto1000oCandorganicmatterandothercoexistent
matterdissolveandevaporate.Lastly,intheatomizingstage,itisheatedto1400 oC
to3000oCandmetallicsaltsleftinthetubeareatomized.Heatingisusuallydoneby
changingthetemperatureinstepsshownbythesolidlineinFig.1.6(stepheating).
Dependingonthesample,whenthedecompositiontemperatureofcoexistentmatter
is close to its atomization temperature, heating is done by changing temperature
continuously(rampmodeheating).
7

Heating must be done under the conditions (temperature, heating time, and
temperatureraisingmethod),whichsuitthetypeofelementandcompositionofthe
sampletobemeasured.
Ifheatingisstartedaftertheoptimum conditions aresetontheequipment in
advance,thetubeisautomaticallyheatedaccordingtothesettemperatureprogram.

Fig. 1.6 Heating program and absorption curve according to

electro-thermal atomic absorption
c)

Otheratomicabsorptionmethods
Methodshavinghighersensitivitythannormalflameatomicabsorptionorelectro
thermal atomic absorption are often used for special elements including arsenic,
seleniumandmercury.Theyusechemicalreactionsintheprocessofatomizationto
vaporizeintheformofanatomorsimplemolecule.

Hydridevaporgenerationtechnique
Thehydridevaporgenerationtechniqueisusedtomakethesamplereacton

sodiumborohydride.
ItisacidifiedwithHCltoreducetheobjectmetal,andcombineitwiththe
hydrogeninordertoproduceagaseousmetalhydride.Thisgasissenttothehigh
temperatureatomizationunitformeasurement.
As,Se,Sb,Sn,Te,Bi,Hgandothermetalsproduceametalhydridebythis
method.
8

Fig.1.7showstheblockdiagramofthehydridegeneratingequipment.The
peristalsisticpumpisusedtosendthesample,5Mhydrochloricacidand0.5%
sodiumborohydridesolutiontothereactioncoil.Themetalhydrideisgenerated
inthereactioncoilandthegasliquidseparatorisusedtoseparatethegasphase
andliquidphase.Argongasisusedasthecarriergas.Thegasphaseissenttothe
absorption cell, which is heated by the airacetylene flame, and the metallic
elementisatomized.

Peristaltic
pump

Fig. 1.7 Block diagram of hydraulic generating equipment

Reductionvaporatomization
Mercuryinsolutionisapositiveion.Whenitisreducedtoaneutralion,it

vaporizesasafreeatomofmercury,atroomtemperature.Tin(II)chlorideisused
as a reducing agent and mercury atoms are sent to the atomic absorption
equipmentwithairasthecarriergas.
Fig.1.8showstheblockdiagramofthemercuryanalysisequipment.200mlof
thesampleisputinthereactionvessel,andtin(II)chlorideisaddedforreduction.
Whenairissenttothegasflowcellthroughthedryingtube,atomicabsorptionby
mercuryismeasured.

Fig. 1.8 Block diagram of mercury analysis equipment

10

2.

Basic Condition for Analysis

The equipment must be set at the optimum analysis conditions to obtain the best

measurementresults.
Optimumconditionsgenerallyvarywiththeelementandwiththecompositionofthe
sample,evenifthesameelementsarecontained.Therefore,itisnecessarytofullystudy
themeasuringconditionsinactualanalysis.
2.1

Conditions of equipment
a)

Analysisline
Lightfromthehollowcathodelampshowsanumberofprimaryandsecondary
spectrumsofcathodeelementsandfillergas.Theyarecomplicatedparticularlywith
4,5,6,7and8familiesinthemiddleoftheperiodictable,showingseveralthousand
spectrums.
Parts of many spectral lines contribute to atomic absorption. The atomic
absorption analysis selects and uses the spectral line of the biggest atomic
absorbance.
Thespectrallinehavingabsorptionsensitivitysuitablefortheanalysismaybe
used.Thisdependsontheconcentrationrangewheretheelementsinthesampleare
measured.
Anelementmayhavetwoormorespectrallinesshowingatomicabsorptionasin
Table2.1.Itisdesirabletocheckabsorptionsensitivityandemissionintensityof
thesespectrallines.Alsostudytheconcentrationrangeinwhicheachwavelengthis
measuredinordertoavoidthedilutionerrorwhentheconcentrationishighasinthe
maincomponentanalysis.

11

Table 2.1 Analysis lines and absorption sensitivities

(Characteristicsofhollowcathodelampandhandlingmethod
HamamatsuPhotonics)
Ele
ment

Analysisline
wavelength(nm)

Ag

328.07

10

338.29

5.3

309.27

10

396.15

8.6

237.13

237.30

2.0

193.70

10

197.20

6.2

189.00

5.0

242.80

10

267.59

5.5

249.68
249.77
208.89

10

553.55

10

350.11

0.01

Be

234.86

10

N2OC2H2

Bi

223.06

10

AirC2H2

222.83

3.0

306.77

2.5

422.67

10

239.86

0.05

228.80

10

326.11

0.02

240.73

10

251.98

4.4

243.58

1.3

346.58

0.5

357.87

10

425.44

4.4

427.88

2.7

428.97

1.0

Al

As

Au
B

Ba

Ca
Cd
Co

Cr

Absorption
sensitivity

Flametype
AirC2H2

Ele
ment

Analysisline
wavelength(nm)

Cs

852.11

10

AirC2H2

Cu

324.75

10

AirC2H2

327.40

4.7

217.89

1.2

218.17

1.0

222.57

0.6

404.59

10

421.17

8.9

418.68

8.0

400.79

10

415.11

5.9

386.28

5.5

459.40

10

462.72

8.7

466.19

248.33

10

271.90

2.7

371.99

0.9

385.99

0.6

294.36

10

287.42

8.2

403.30

4.2

407.89

10

422.59

10

378.31

10

265.16

10

270.96

4.8

269.13

3.0

286.64

10

307.29

9.3

289.83

5.0

253.65

10

N2OC2H2

ArH2

Dy

AirC2H2

Er

N2OC2H2
Eu

8.2
N2OC2H2

AirC2H2
AirC2H2

Fe

Ga

Gd

AirC2H2
Ge

AirC2H2

Hf

Hg

12

Absorption
sensitivity

Flametype

N2OC2H2

N2OC2H2

N2OC2H2

AirC2H2

AirC2H2

N2OC2H2

N2OC2H2

N2OC2H2

Reduction
vaporization

Ele
ment

Analysisline
wavelength(nm)

Ho

410.38

10

416.30

5.8

303.94

10

325.61

9.4

410.48

4.0

208.88

10

266.47

2.6

284.97

1.5

766.49

10

769.90

In

Ir

La

Li
Lu
Mg
Mn

Mo

Na

Nb

Absorption
sensitivity

Flametype

Ele
ment

Analysisline
wavelength(nm)

N2OC2H2

Nd

492.45

10

463.42

0.8

232.00

10

341.48

5.1

352.45

5.0

231.10

2.0

351.50

0.9

290.90

10

305.86

4.5

2.5

263.71

4.0

404.41

0.03

330.16

2.0

550.13

10

217.00

10

403.72

2.3

283.33

3.9

357.44

0.8

261.41

0.2

364.95

0.5

202.20

0.1

670.78

10

244.79

10

323.26

0.06

247.64

6.8

331.21

10

276.31

2.2

328.17

7.1

340.46

1.5

285.21

10

495.13

10

202.58

0.9

513.34

6.9

279.48

10

504.55

2.5

280.11

4.7

265.95

10

403.08

1.1

292.98

2.0

313.26

10

780.02

10

794.76

4.6

346.05

10

346.47

5.3

345.19

3.5

343.49

10

339.69

2.8

328.09

0.2

349.89

10

319.40

4.7

320.88

0.8

589.00

10

589.59

4.8

330.23

330.30

0.02

334.91

10

405.89

AirC2H2

Ni

AirC2H2
Os
AirC2H2

N2OC2H2

AirC2H2

Pb

Pd

N2OC2H2
AirC2H2

Pr

AirC2H2
Pt
AirC2H2

Rb
Re

AirC2H2
Rh
N2OC2H2
Ru

13

Absorption
sensitivity

Flametype
N2OC2H2
AirC2H2

N2OC2H2

AirC2H2

AirC2H2

N2OC2H2

AirC2H2
AirC2H2
N2OC2H2

AirC2H2

AirC2H2

Ele
ment

Analysisline
wavelength(nm)

Sb

217.58

10

206.83

7.0

231.15

3.6

212.74

1.0

391.18

10

390.74

7.6

402.37

7.0

402.04

5.0

326.99

3.0

196.03

10

203.99

2.0

251.61

10

250.69

3.0

251.43

3.0

252.41

2.5

288.16

0.7

429.67

10

484.17

8.2

224.61

10

286.33

6.2

233.48

6.0

460.73

10

407.77

0.6

Sc

Se
Si

Sm
Sn

Sr

Absorption
sensitivity

Flametype
AirC2H2

ElementAnalysislinewavelength(nm)AbsorptionsensitivityFlame
typeTe214.27
225.9010
1.0AirC2H2Ti364.27
365.35
398.9810

N2OC2H2

9.0
4.0N2OC2H2Tl276.78
377.5710
4.2AirC2H2Tm371.79
410.58

ArH2

374.4110

N2OC2H2

6.5
6N2OC2H2V318.40
306.64
305.6310
3.8
3.0N2OC2H2W255.14

N2OC2H2
AirC2H2

400.87
407.4410
3.6
0.1N2OC2H2Y410.23

AirC2H2

412.83
407.7410
8.5

Ta

8N2OC2H2Yb398.79

271.47

10

N2OC2H2

Tb

264.75

5.9

246.4510

275.83

2.6

3.2

346.43

2.0N2OC2H2Zn213.86
307.5910
0.002AirC2H2Zr360.1210N2OC2H2

14

432.6410N2OC2H2

b)

Slitwidth

Concerningspectrallinesemittedfromthehollowcathodelamp,theirwavelength
isanindependentlineorcomplicatednearbylinedependingontheelement.
Calciumandmagnesiumhavenootherspectrallinesneartheobjectanalysisline
asshowninFig.2.1.
In case of such analysis lines, slit width is set considerably greater to obtain
sufficientenergy.

Fig. 2.1 Lamp spectrums

Nickelhasmanyspectrallinesneartheobjectanalysislineof232.0nm(2320A).
Becauselightofthesenearbywavelengthsishardlyabsorbedwithnickelatoms,the
resolvingpowerspectroscopemustbeincreased(slitwidthisnarrowed)toseparate
only232.0nmlight.
Ifmeasurementismadeinthelowresolvingpowercondition,themeasurement
sensitivity grows worse and at the same time, linearity of the calibration curve
becomesdeteriorated.(Fig.2.2)
Cobalt (Co), iron (Fe), manganese (Mn) and silicon (Si) show complicated
spectrumslikenickel.
Theresolvingpowerofthespectroscope mustbebelow2A tomeasure these
elementsaccurately.

15

Ni Concentration

Fig. 2.2 Slit width and calibration curve

c)

Lampcurrentvalue
Ifthehollowcathodelampoperatingconditionsarenotproper,thespectralline
causes a Doppler broadening or broadening due to selfabsorption, to affect the
measured value. Doppler broadening is caused bythe temperature of the hollow
cathodelamp space, which does notcontribute tolampemission. Asthehollow
cathodelampcurrentincreases,luminanceincreases;thusthespectrallinesbroaden
causingabsorptionsensitivitytodropasshowninFig.2.3.
Thelifeofthehollowcathodelampisgenerallyindicatedbyamperehour(A.Hr).
Therefore,thelifeisshortenedifthecurrentvalueisincreased.
Suchbeingthecase,alowcathodelamplightingcurrentvalueisdesirablebut
luminancedropsifitistoolow. Detectorsensitivitymustbeincreased,butnoise
resultsfromit.
Thelampcurrentvalueisdeterminedbythreefactors:luminance(noise)ofthe
abovelamp,absorptionsensitivity,andlamplife.

16

Fig. 2.3 Sensitivity by changing the hollow cathode lamp current value
2.2

Analysis conditions of flame atomic absorption

a)

Flameselection
Airacetylene,airhydrogen,argonhydrogen,andnitrousoxideacetylenearethe
standardtypesofflamesusedinatomicabsorptionanalysis.
Theseflamesvaryintemperature,reducibilityandtransmissioncharacteristics.
Theoptimumflamemustbeselectedaccordingtotheelementbeinganalyzed,and
propertiesofthesample.
Airacetyleneflame(AIRC2H2)
Thisflameismostpopularlyusedandabout30elementscanbeanalyzedby
this.
Nitrousoxideacetyleneflame(N2OC2H2)
This flame has the highest temperature among flames used for atomic
absorption.Aluminum,vanadium,titanium,etc.combinestronglywithoxygenin
theairacetyleneflameandotherrelativelylowtemperatureflames.Freeatoms
decreaseandmakemeasurementdifficult.However,suchelementsarehardto
combine with oxygen due to high temperature in the nitrous oxideacetylene
flamemakingsatisfactorymeasurementpossible.
The nitrous oxideacetylene flame can also be substituted for the elements
analyzedbytheairacetyleneflame.Thehightemperatureofthenitrousoxide
acetyleneflamehasverysmallinterferences.
17

Airhydrogenflame(AirH2)andargonhydrogenflame(ArH2)
Thehydrogenflameabsorbsverylittlelightfromthecathodelamp,onlyinthe
shortwavelengthregion.(RefertoFig.2.4).
Therefore,measurementcanbedonewithasmallerbackgroundnoise,inthis
short wavelength region, than with the airacetylene flame. Those wavelength
elementsareAs,Se,Zn,Pb,Cd,Sn,etc.
Since the argonhydrogen flame absorbs the smallest amount of light from
200nmandbelow,itistypicallyused.
Thedisadvantageofusingahydrogentypeflameisthatitissusceptibleto
interferencesduetoitslowtemperature.

Fig. 2.4 Light absorbance of various flames

Table2.2showsthemaximumtemperatureofeachflame.
Table2.3showselementsandtypesofflamesused.
Table 2.2 Flame temperature
Maximum
temperature

Flametype
Argonhydrogen

1577oC

Airhydrogen

2045oC

Airacetylene

2300oC

Nitrousoxideacetylene

2955oC

18

Table 2.3 Elements and flames used for measurement

b)

Mixingratioofoxidantandfuelgas
Themixingratioofoxidantandfuelgasisoneofthemostimportantitemsamong
measurement conditions of atomic absorption analysis. The mixing ratio affects
flametemperatureandenvironment,anddeterminesgeneratingconditionsofground
stateatoms.
Therefore,theflametypeaswellasthebeampositionintheflamedescribedin
thenextparagraph,control80to90percentofabsorptionsensitivityand stability
(reproducibility). Cu, Ca, Mg, etc. increase sensitivity in the oxidizing flame
containingmoreoxidant(fuelleanflame)andSn,Cr,Mo,etc.increasesensitivityin
thereducingflamecontainingmorefuelgas(fuelrichflame).
Becauseextremelyfuelleanorfuelrichmaycauseinstability,itmustbesetatthe
optimumvaluedependingonthetargetobject.Absorptionvaluesbychangingthe
acetyleneflowaremeasuredwithconstantairflowandtheconditionshowingthe
maximumabsorptionvalueisobtained.Becausetheabovestudyisconcernedwith
theburnerpositiondescribedinthenextparagraph,acetyleneflowandburnerheight
areadjustedtodecidetheoptimummixingratio.

c)

Beampositioninflame
Distribution of ground state atoms generated in the flame are not uniform
dependingontheelement,butvariesdependingontheflamemixingratio.Fig.2.5
showsdistributionofgroundstateatomswhenthegasmixingratioischangedinthe
measurementofchromium.Itindicates thatatomdistributionanddensitychange
19

whenthemixingratioischanged.Becauseabsorptionsensitivitychangeswiththe
beampositionintheflame,theburnerpositionissetsothatthebeampassesthe
optimumposition.

Fig. 2.5 Distribution of chromium atoms in air-acetylene flame

(Atomicabsorptionspectroscopy,W,salvin)
2.3

Analysis conditions of electro-thermal (flameless) atomic absorption

Electrothermal(flameless)atomicabsorptionconductsheatinginthreebasicstages
forsampleatomization.
ThefirststepistheDryingStage,whichevaporatesthesolvent.
ThesecondstepistheAshingStage;todissolveorganicmatterinthesampleand
evaporatethesalts.
ThethirdstepistheAtomizationStage.Ifneeded,aCleaningStagecanbeset.The
followingdescribeseachconditionsetting.
a)

Dryingcondition
Thisstageistoevaporatethesolvent.Theheatingtemperatureandtimeareset
dependingonthetypeandquantityofthesolventusedformeasurement.
Thestandardheatingtemperatureforevaporatingthesolventis60 oCto150oCfor
watertypesamples,or50oCto100oCfororganictypesamples.
The heating time is based on 1 second per 1l of the sample. The heating
temperature andtime aresetsothatthesolvent is evaporated completely. Ifthe
dryingconditionisnotperfect,afizzle(bumping)isheardorsmokeblowsthrough
thegraphitetubeholewhenthenextstageisentered.Toclearlyexamine,setthe
measurementmodetothedeuteriumlampmode,andcheckiftheabsorptionpeakis
exactlyzero.Theaboveisthejudgmentcriteria.
20

Therearetwoheatingmethods: StepandRampmodes.Inthestepmode,the
furnaceisdirectlyheatedtothetargettemperature,atthebeginningofthestage,and
maintainedataconstanttemperatureuntiltheendofthestage.Intherampmode,
heatingisperformedataconstantratesothatthetargettemperatureisreachedbythe
endofthestage.Thesampleinjectedinthegraphitetubediffuses(spreads)inthe
tube.Iftoomuchsampleisinjectedorsampleviscosityishigh,thesamplemaystay
onthesurfaceofthegraphitetube.
If sharp heating is done, the sample bubbles or bumps. When bubbling or
bumpingoccurs,thesamplefliesofffromthefillerportanddiffusesatrandominthe
tube,makingreproducibilityworse.
Insuchacase,itiseffectivetomakeheatingbystepmodeataslightlylower
temperaturethanthesolventevaporatingtemperature.However,rampmodeheating
iseasiertosetthecondition.Rampmodeheatingandstepmodeheatingmaybe
combinedtoincreasethedryingefficiency.
Thepyrolyticgraphitetubehassmallfiltrationduetoitsfinesurface.Therefore,
specialcareisnecessary.Spreadingconditionsof thesampleintothetubevaries
withthegraphitetubetemperatureandsampleinjectiontoworsenreproducibility.
So,itisdesirabletoinjectthesampleundertheconstanttemperatureof10to15 oC
higherthanroomtemperature.
b)

Ashingcondition
Iforganicmatter,orsalts,existintheatomizationstage,backgroundabsorption
(chemicalinterference)occursgivinganerrorintheanalysisvalue.
Therefore, organic matter and salts are evaporated in the ashing stage where
possible.
Itisdesirabletoincreasetheashingtemperatureashighaspossibletoremove
organicmatterandsalts.
However,iftheashingtemperatureisincreased,evaporationofthetargetmetal
happensanderrorsintheanalysisvaluesoccur.Therefore,itmusthavealimit.The
volatilization(evaporation)temperatureofthetargetmetalischeckedinadvanceto
decidetheashingtemperature.
Fig. 2.6 shows the relation between the ashing temperature and absorption
sensitivityofaleadsolutionwithnitricacid.Theashingtemperatureandabsorption
sensitivityevery100oCsuggestthatvolatilizationoccursfrom500oCinthecaseof
lead.
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Theconditionisstudiedonleadnitrate,butthevolatilizingtemperaturemustbe
checkedonthesamechemicalspeciesasthesampletobemeasured.Thatisbecause
the volatilizing temperature varies with the chemical species of the target metal
generatedintheashingstage.

Fig. 2.6 Relation between lead ashing temperature and sensitivity

Backgroundabsorptiondecreasesastheashingtemperaturerises.Fig.2.7shows
backgroundabsorptionattheleadwavelengthof1/10dilutedwholebloodsolution,
asoneexample,toshowbackgroundtendency.
Astheashingtemperaturerisesto300,400and500 oC,backgroundabsorption
decreases but is not lost completely. Therefore, a higher ashing temperature is
desirable.Itisassumedthatleadstartsvoltilizationattheashingtemperature500 oC
as showninFig.2.6andtheashingtemperature ofleadcannotberaisedabove
500oC.

22

Fig. 2.7 Relation between ashing temperature and background absorption

One means to decrease background absorption is to dilute the sample, but it
cannotbeappliedwhendensityofthetargetmetalisverylow.Amatrixmodifieris
usedinsuchacase.Palladium(II)nitrateandnickelnitrateareusedasthematrix
modifier.Theyhavetheeffectofincreasingthevolatilizingtemperatureofthetarget
metalasmentionedin5.3.Thatis,becausetheashingtemperaturecanberaised,
backgroundabsorptioncanbedecreasedandabsorptionsensitivitycanbeincreased.
Stepmodeheatingandrampmodeheatingareavailableastheheatingmethodin
thesamewayasdrying.Instepmodeheating,saltsinthegraphitetubemayblow
outfromthesamplefillerportaftercompletionofdrying.Generally,themethod
combinedwithrampmodeheating andstepmodeheating; rampheatingisdone
fromdryingtemperaturetoashingtemperature,taking10to20secondsandthenthe
ashingtemperatureiskeptforthespecifiedtime.
Heatingtimeintheashingstagevarieswiththequantityofsalt,ororganicmatter
containedinthesample,andisgenerally30to60seconds.Whetherashingisperfect
ornotforthisheatingtimecanbecheckedbymagnitudeofbackgroundabsorption.
Thedeuteriumlampmodeissetasthemeasuringmodeandabsorptionpeakinthe
atomizingstageismeasured.Thetimewhenabsorptionmagnitudedoesnotchange,
eveniftheashingtimeisextended,isthesettingtime.
c)

Atomizingcondition
Thisstepistoatomizethetargetmetal.Heatingmaybemadeforabout5seconds
ataslightlyhighertemperaturethantheatomizingtemperatureofthetargetmetal.
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Absorptionsensitivity,whentheatomizingtemperatureischanged,ischeckedto
decide the atomizing temperature. Fig. 12.8 shows the relation between the
atomizingtemperatureandabsorptionsensitivity.Itindicatesthatheatingmaybe
doneat2500oCorabove.

Fig. 2.8 Relation between aluminum atomizing temperature and sensitivity

If the atomizing temperature is set too high for metals of low melting points
includingcadmiumandlead,theatomstayingtimeinthetubebecomesextremely
shortandsensitivitymaydrop.Metalsincludingboron,molybdenumandcalcium
are easily maintained in the graphite tube. Therefore, atomization is done at a
temperatureashighaspossibleorpyrolyticgraphitetubeisused.
About1l/minofargonisrunthroughthegraphitetubeinthedryingandashing
stages.Ifargongasisrunintheatomizingstage,sensitivitydropssharply.
Therefore,argonisstopped.Sensitivitycanbeadjustedfivetimesasmuchby
changingargonflowfrom0to1.5l/mintoadjustabsorptionsensitivity.
Stepheatingisgenerallyused.Whenbackgroundabsorptionattheatomization
stageisbig,atomicabsorption,backgroundabsorption,andmeasurementshouldbe
madebyrampheating.
Theheatingtimeissetsothattheatomicabsorptionpeakreturnsto0levelwithin
theheatingtime.However,whenthemetaliseasytostayinthegraphitetubeor
backgroundabsorptionisbiganddoesnotreturnto0level,thetimewhenthepeak
returnstothespecifiedlevelissetasheatingtime,andcleaningisdonethereafter.

24

Cleaningisdonetoevaporatemetalandsalt,whichremainsinthegraphitetube,
attheendoftheatomizingstage.Heatingcanbedonesufficientlyfor2to3seconds
atthemaximumtemperatureof3000oCbutlowertemperatureisdesirablewhere
possible.
The standard cleaning temperature is the atomization temperature plus 200oC.
Cleaningisdoneatabout2500oCforcadmiumandlead,whichhavelowatomization
temperatures.
d)

Sampleinjectionquantity
Proportionalrelationsdonotworkbetweenthesamplequantityinjectedinthe
graphitetubeandabsorptionsensitivity.Thisisbecausethediffusionareainthetube
andfiltrationdepthvarywithsampleinjectionquantity.Therefore,thecalibration
linecanbepreparedbychangingtheinjectionquantityofthestandardsolutionfrom
thespecifieddensity.
Solutionsofdifferentdensitiesareinjectedinthespecifiedquantityatonetime.
Theinjectionquantityofthestandardsampleisnaturallythesameasthat
ofthesample.
Themaximumsampleinjectionquantityis50lbutdiffusionandfilteringdepth
varywithadifferenceinphysicalpropertiesofthesample.Itspreadstothelow
temperaturepart,oroverflowstothefillerportoftendroppinganalysisaccuracy.
Therefore,10to20lisideal.

8.5
6.0
431.88
390.14

25