P. 1



# OAR Box 1827 Prepped by Charmelle Mathews



### Document

Number: 

# 139 ) ll-A- 9

Docket Number: 

# A-90-0 7

Printed 11/19/2008 12:40:48 PM Sheet 139 of 147P, 2
\ '- 

### A-90-0 7

Researc h Protoco l Metho d fo r Analysi s o f Detaile d Hydrocarbon s emitte d fro m Automobile s b yGa s Chromatograph y

Prepare d b

y Joh n E
. Sigsb

yJr
. U.S

. Environmenta l Protectio n Agenc y Researc h Triangl e Park , Nort h Carolin a 2771 1

an d

Willia mCrew s an

d Paul a Siudak Mantec h Environmenta l In c
Prepare d fo r

U.S

. Environmenta l Protectio n Agenc y Mobil e Sourc e Emissio n Researc h Branc h Chemica l Processe s an d Characterizatio n Divisio n Atmospheri c Researc h an d Exposur e Assessmen t Laboratory Originall yPrepare d Jun e 198 9 Revise d Jun e 199 1P. 3

AREAL-CPCD-MSER B RPM-00 1 Revisio n No
. 3 Date : Jun e 28 , 1991 , Page : 2

Disclaime r

Th e Researc h Protocol/Metho d (RPM ) describe d herei n shoul d no t b e interprete d a s a generall yaccepte d standar d o r equivalen t metho d o r procedure

. Thi s RP M wa s develope d fo r us e withi n th e Mobil e Sourc e Emissio n Researc h Branc h an d ma yno t b e applicabl e t o th e need s o f othe r organi2ations

.P. 4

AREAL-CPCD-MSER B RPM-00 1 Revisio n No
. 3 Date : Jun e 28 , 1991 , Page : 3

REVISION S Revisio n 1 Origina l writ e up , cleare d Jun e 30 , 198 9 Revisio n 2
Fron t en

d o n SystemAchange d t o provid e propan e propylen e split

. Revisio n 3 Perki n Elme r 870 0 o n lin e wit h dua l FID's
.P. 5

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : Jun

e 28 , 1991 , Page : 4 1. 0 Scop

e an d Applicatio

n Thi s recommende

d metho di s intende

d fo r th e analysi s of detaile d hydrocarbon s (HC ) i nth e emission s fro

m Mobil e Sources . Th e method(s ) minimu

m quantificatio

nan ddetectio

nlimi t ar e determine

d b y th e tota l volum

e o f sampl e taken . The leve l o f quantificatio

ni s 3 time s the limi t o f detection . Typica l value s fo r th e limi t o f detectio nar e aroun

d 0.0 1 pp

m wit ha tenc c sample . Thi s metho

d i s intende

d t o provide a genera l assessmen t of th e natur e o f the emission s an dno t t o b

e a nabsolut e definitio

no f them . I f the emissio nleve l o f a specifi c component i s o f overridin

g interest , a separat e analysi s fo r tha t compoun

d shoul d be made . Se e als o Interferences , Sectio n4.0 . 2. 0 Summar

y o f Metho

d Ther e ar e tw

o separat e analytica l system s i nus e withi nth

e Branch . The

y bothus e th

e sam e basi c methodolog

y but wit h different specifi c parameter s due t o the differenc e i nth e instrumentatio

nutilized . One syste m utilize s Perki nElme r (P&E ) Ga s Chromatographs , SYSTE M A , whil e th

e othe r i s base

d o nth e us e of Hewlet t Packar

d Mode l 588 0 Ga s Chromatograph s (HP),SYSTE M B . Bothsystem

s transfe r th

e ra w dat a t o a PC-A

T o r compatibl e wher e th

e dat a i s verified an dfina l editin

g take s place . Th

e dat a i s the

ntransferre

d t o a centra l P C fo r fina l calculation s an d mergin

g int o th

e laborator

y dat a bas e fo

r fina l reporting . Sample s u

p t o about 15 0 pp

m carbo nar e analyze

do nthes e systems . Sample s containin g highe r concentration s ar e dilute d into thi s range . Eac hsyste m take s a know

nan dprecisel y

measuredvolum

e o f sampl e an

d measure s a wide variety o f hydrocarbon s usin g flam e ionizatio

ndetection . Separat e sample s ar e take nfo r methane . Th

e tw o throug

hthre e carbo

nhydrocarbon s ca

neithe r b

e analyze

d b y a seperat e sampl e or wit hth e tw o throug

heleve ncarbo n hydrocarbons . Eac hsyste m record s the output o f th e flam e ionizatio

n detector (FID ) throug ha nintegrall y

configure

dintegratio

nan d recordin

g syste m tha t record s th

e dat a alon

g withappropriat e retentio

ntime s whichallow s fo r futur e re-editin

g o f th e dat a a s wel l a s deliverin

g "identified " chromatographi c peaks . The signa l i s als o recorde

d o na stri p char t recorde r a s i t i s bein g created . 4. 0 Interference s An y compoun

d tha t co-elute s witha nidentifie

dhydrocarbo

nP. 6

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : June 28 , 1991 , Page : 5
ma y b e terme d a ninterferant . Thes e ma y b e hydrocarbons , i

nwhic h cas e th e respons e facto

r (i npp m Carbon/area ) wil l b e similar t o tha t o f th

e compoun

d identified , o

r i t ma y b e o f a differen t organi c clas s wit ha correspondingl y differen t FI D response . I n th e latter cas e th

e quantificatio

nwil l b

e adversel y

effecte

d an d invalidate

d t o th

e extent o f th

e respons e differences . I nth e cas e o f a co-elutin g hydrocarbon , th

e quantitativ

e mas s calculatio

nwil l no t b

e grossl y

affecte

do na carbo

nbasi s but an y subsequen t interpretatio nof th e result s ma

y b e i nerror du

e t o the misidentification , particularl y i f the tw

o hydrocarbon s are o f differen t classes , fo r exampl e paraffin s an dolefins . 5. 0 Personne l Requirement s The researche r utilizin g thi s procedur e i s expected t o b e familiar wit hga s chromatography , it s practice , an d it s applicatio

nt o hydrocarbo

nanalysis . Inaddition , the operator i s expecte d t o b e familiar withgoo danalytica l practice . The operator wil l be expecte d t o optimiz e th

e ga s chromatograp

han d operat e it . The instrument manua l ma y b e a naide inthi s activity . The procedure s utilize dare th

e resul t o f man

y year s of researchan

d involv

e considerabl e modificatio no f the purchased instrumentation . Norma l operatin g procedure s include : star t up , bothdail y

an d afte r shut down ; sensitivit y determination ; maintenanc e schedules ; sampl e preparation ; an d the regula r reportin

g o f analytica l results , bothroutin e an dthos e tha t ar e at varianc e wit hexpectation . 6. 0 Facilitie s Requirement s
N o specia l laborator y facilitie s are required . 7. 0 Safet

y Requirement s Calibratio

nstandards , samples , an d mos t laborator

y reagent s use d inthi s metho

d pos e n

o unusua l hazar

dt o the researcher , i f norma l laborator

y safet y practice s are followed . Ey e an dhan d protectio

ni s require

d whenusin

g cryogens . Compresse dgase s mus t b e store d an d handle

d properly . Electrica l connection s ca npos e a hazar d i f improperl y

made o r lef t exposed . Th e America

nChemica l Societ

y ( AC S ) guideline s regardin g th e handlin

g o f chemical s use

di nthes e method s shoul db e followed . 7. 3 Heate

d Surface s The G C injectio

nports , column , colum noven , an

ddetector s ma y b e maintained at temperature s hig henoug ht o caus e burns . Th e researche r shoul d exercis e cautio nan davoi d contac t wit hthes eP. 7

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : June 28 , 1991 , Page : 6 surfaces . 7. 5 Compresse

d Gase s Se e page s F1 4 throug hF1 8 of th

e EPA/RT P Safety

manua l (referenc e 2 ) fo

r safet y precautions . 7.5. 2 Cryogeni c Liquids , (Liquid Nitrogen )
Se e page s F1 8 throug hF2 0 o f th

e EPA/RT P Safety

Manua l (referenc e 2 ) for precautions . WARNIN G- Cryogeni c flui d. Ma y caus e sever e frostbite . Wear han d an d ey e protection . Us e withadequat e roo m ventilation . Kee

p contac t wit hai r t o th e minimu

m t o avoi dbuil du

p o f liqui d oxygen . 8.0 . Apparatu s an

d Equipment Thi s sectio

ndefine s th

e specifi c instrumenta l requirement s of thi s method . 8. 1 Ga s Chromatograp h The ga s chromatograph s use di nthi s metho

d ar e equippe

dfo r sub-ambient temperatur e programing , hav e a flam

e ionizatio

n detector (FID ) an

d a nelectroni c integrator . The instrument s use d are : Syste m Al : Perki nElmer Sigm a 200 0 an

d integrator Syste m A2 : Perki nElmer 870 0 an d integrator Syste m B : Hewlet t Packar

d5880A Ga s chromatograph . Eac hsyste m i s described separately , wher e appropriate . 8.1. 1 Ga s Chromatograp hColum n
U p t o thre e differen t column s ar e use di nthi s analysis . Colum nI : Highe r molecula r weight hydrocarbon s throug hCll . Type : Fuse

d Silic a Capillar

y colum n Diameter : 0.3 2 Length : 6 0 meter s X2 = 12 0 meter sP. 8

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3
Date : June 28 , 1991 , Page : 7 Liqui d Phase : DB-1 , Methy l Silicon e bonde dliqui dphas e Liqui d Phas e Thickness : 1. 0 u m Colum nII : Methane - Syste m A & B Type : Packe

d soli d adsorben t Diameter : 1/ 8 thinc hOD Stainles s Stee l Length : 6 fee t Packin g Material : 6 0 - 8 0 mesh , 13XMolecula r siev e Colum nIII : Tw

o an d Thre e Carbo

nHydrocarbon s Type : Packe

d soli d adsorbent Diameter : 1/ 8 inc

hO D Stainles s Stee l

t Length : 6 fee t Packin g Material : 4 0 -6 0 mesh , Typ e 5 8 Silic a Ge l

8.1.2 B Inle t Syste

m A 2 & B Th e inle t syste

m i s illustrate

d i nFigure s 1B 1 an

d 1B2 .
8.1.2. 1 Connectio

no f inle t syste

m t o colum

n Th e capillar

y colum ni s connecte

ddirectl y

t o th e samplin

g valv e usin g a Swagelo

k capillar

y colum nconnector an

dgraphit e ferrules . The packed column s are connecte dusin g standar

d1/8 - i nt o 1/16-inSwagelo k reducin

g union s an

d31 6 stainles s stee l ferrules . 8.1. 3 Sampl e Loop Th e sampl e loo

p i s constructe

do f clean , chromatographi c grad e 1/8-inOD stainles s stee l tubing . A 4-f t i nlength , which i s coile

d t o fi t insid

e th e sampler housin

g o r ga s chromatograph . Th e loo p i s flushe

d wit hmethylene chlorid e an ddrie dwithzer

o grad e ai r prio r t o use . 8.1.3. 1 Sampl e Tra

p Th e sampl e tra

p i s constructedof clean , chromatographi c grad eP. 9

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : Jun

e 28 , 1991 , Page : 8 l/9-i nO D stainles s stee l tubing . A 6-inc hi nlengt hi s firmly packe d wit h10. 2 c

m o f glas s wool . A

temperature controller maintain s concentratio nan d desorptio

ntemperatures . Th e controller i s se t t o -17 0 degree s C (temperature maintaine db y usin g liqui d nitrogen ) fo r trappin

g tw o throug

heleve ncarbo n hydrocarbon s an

d rampe d t o +20 0 degree s C fo r desorption . Th

e tra p i s wrapped wit hinsulatio ntape t o prevent col d an dho t spots . 8. 5 Tubin

g an d Connector s Al l tubin

g i s chromatographi c grade stainles s steel . Al l connection s ar e mad e wit hstainles s stea l compressio ntub e fittings . (Swagelo

k or equivalent) . 8.6- Regulator s fo

r Compresse

d Gase s Carrier gas , hydrogen , an d ai r deliver

y pressure s ar e controlle

d b y tw o stage regulator s mounte d a t th e tank . Caution : Due t o th e possibility

o f contaminatio

nb y organi c materials , onl y

regulator s withstainles s stee l diaphragm

s shoul db

e used . 9. 0 Reagents/Material s Al l gase s use

d t o operat e th

e G C syste m shoul d b

e th e highes t grade reasonable . Detaile dspecification s ma y var y betwee nmanufacturer s but shoul db e restriciv

e enoug hs o a s not t o caus e an

y decreas e ininstrument performance . Propan e calibratio

ngase s ar e obtained fro m NIS T (NBS ) an

dare SRM's . Othe r calibratio

nmaterial s are fabricate db y usin g th e highes t obtainabl e grade o f hydrocarbo nan d dilutin

g i nknow nvolume s of zer o grad e or bette r air . 9. 1 Gase s an

d Cryogen s Th e followin

g ar e recommende

dfo r us e withthi s method . 9.1. 1 Heliu

m Carrie r Ga s Hig hPurity , minimu

m purity o f 99.99 5 percent helium , Burea u of Mine s 9.1. 2 Detector Ai r Zer o Grade , wit htota l hydrocarbo nles s tha

n1 pp m carbon , containin

g 2 0 +/ - 0. 5 % oxyge n 9.1. 3 Detector HydrogenP.1 0

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : June 28 , 1991 , Page : 9 Pre-purified grade , 99.9 9 percent hydrogenor bette r 9.1. 5 Liqui d Nitrogen( fo r G C ove ncooling ) Commercia l grade i s acceptabl e 9.1. 8 Propane inAir , Benzene i nAir , tw

o throug

htwelv e carbo n hydrocarbo

nmixtur e i

nAi r ( fo

r calibration) . Eithe r o r al l ma

y b e availabl e NIS T (NBS ) SR

M 1665 , 3 pp

m compoun

dinai r (nominal )
NIS T SR

M 1666 , 1 0 pp

m compoun

d inai r NATIONA L SPECILIT

YGAS (NIS T TRACEABLE ) 2 5 ppm C (C 2 - Cll , se e als o sectio

n11.3.2 )
SCOT T SR

M CA L 6495 , 0.25 4 pp m i nai r 9.1. 9 Instrumen t Ai r Vacuu m The si xpor t Seiscor ga s samplin g valve s requir e clean , filtere d ai r a t 35 0 kp

a (3 5 psig ) an

d a clea

nvacuu m o f approximatel y

2 0 inH

g fo r prope r operation . 11. 3 Ga s Chromatograp hCalibratio

n Calibratio

no f thes e instrument s i nth e part s pe r millio

n carbo nrang e (pp

m C ) i s performe

dusin g th e followin

g procedure . 11.3. 1 Instrumen t Optimizatio n
A propane inai r sampl e shoul dfirs t b e analyzedan

d adjustment s mad e t o th e carrier ga s linea r velocity

suc htha t th

e propane peak elute s at approximatel y 14. 5 minute s followin g injection . The hydrocarbo ncompound s shoul d elut e inth e order of retentio

ntime s a s show

ni nTabl e 1 whenusin g the capillar

y colum nan d othe r column s a s specifie d i nthi s document . Th e elutio ntime s shoul d b

e determine

db y preparin

g an d analyzin

g know nsample s o f eac

hcompoun

dand/or know

nmixture s o f th

e compound s expected , suc ha s th e gasolin

e use d inthe experiment o r o f know

ncalibratio

nmixtures . Th

e mor e comple

xth e mixtur e th e greate r i s the suret y tha t th

e retentio

norde r ha s bee

n maintained . The precis e retentio ntime s depen

d uponcolum

n length , carrie r flo w rate , effectiv

e colum ntemperature , etc . Th e flame-ionizatio

ndetector hydroge

nan d ai r flo

w rate s are controlle

d b y critica l orifice s installe db y th e manufacturer . Prope r hea dpressure s are specifie d fo r optimu

mP.1 1

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : June 28 , 1991 , Page : 1 0 signa l t o nois e ratio . Syste m Al : Pressure s fo

r the Perki nElmer 200 0 ar e se t wit hthe ai r pressur e a t 4 0 psi g an dthe hydrogenat 2 0 psi g o

ndetecto r an

d heliu m carrier at 6 5 psig . Syste m A2 : Pressure s fo

r th e Perki nElmer 870 0 ar e se t wit hthe ai r pressur e at 2 2 psi g an

d hydrogenpressur e at 22'psi g at the detector , an d th e heliu m carrie r at 6 0 an

d 6 7 psig . Syste

m B : Pressure s fo

r th e HP 588 0 ar e specifie da s Ai r at 4 0 psig , Hydrogena t 4 0 psig , an d heliu m a t 6 8 psig . The carrier ga s flo w o neachsyste

m i s adjuste d t o provide optimu m separation . 11.3. 2 Calibration The respons e o f th

e FI D i s assume

d t o b e linear wit hrespec t t o th e numbe r o f carbo

natom s present i

nth e detectedcompound . Thus , i t i s convenien t t o measur e compoun d peak concentratio nin term s o f part s pe r millio ncarbo n(pp m C ) where : Concentratio

npp m C = (numbe

r o f carbo

natom s i nthe compound ) x (concentratio

npp m Molar ) For a fixe

d sampl e volume , th e concentratio

ni s proportiona l t o th e area unde r th

e chromatographi c peak . Th e are a unde r th

e peak i s converted t o pp m C concentration s i nth e compute r b

y th e followin

g calculation :

Cone , pp

m C = (k)(Area )
Are a i s giveni

nintegrator count s and * k i s a

n experimentall y

determined calibratio nconstant (pp

m C/count) . Multipl e value s o f k are use ddependin

g o ncompoun

dretentio

n tim e an d class , a fifthorder polynomia l fi t i s usedt o appl y th e respons e factor s for th e tw o throug

heleve ncarbo nhydrocarbons . A calibrationmixtur e o f about 1 4 compound s i s usedfor instrument calibratio nan ddail y spa nchecks . The cylinder s are fro m Nationa l Welder s Specialt y Gase s an

dare certifiedb

y them . A typica l Certificat e i s show na s Figure 2 . A

typica l mixtur e might include ; propane , isobutane , n-butane , isopentane , 2 - methylpentane , benzene , cyclohexane , n-heptane , toluene , n octane , para-&-met a xylene , , ortho-xylene , n-nonane , an d n decane . A

separat e cylinde r containin g methane i s use

dfo r tha t analysis . A

minimu m o f si xinjection s are performedo na quarterl y

basi s an

d th e instrument respons e recorded . A contro l char t i s generated fro m thi s dat a an

dkept o

nth e instrumen t PC . Print out s ma

y b e kep t i

nloos e lea f notebook s fo r reference . I f th e su m o f the area count s o r an y of th e individua l area count s fall s outside the 95 % confidenc e interva l o f th e mean(+/ - 1.9 6 standar d deviation s fro

m th e mean) , th

e operator s wil l perfor m standar d troubleshootin

g procedure s t o determin e th e cause . Th

e entire calibratio

nwil l the

nb e repeate

dan d ne w value s entere

dAREAL-CPCD-MSER B RPM-00 1 Revisio nNo . 3 Date : Jun

e 28 , 1991 , Page : 1 1 into th e contro l chart . O na dail y

basis , th

e dilut e calibratio n mi xi s injecte

d int o th

e instrument an

dth e respons e noted . I f th e dail y spa ncheck s indicat e tha t an y of th e individua l response s o

r th e su m o f th e area count s fal l outsid e the 95 % confidenc e interva l o f th e mea no f th e daily calibration s (+/ - 1.9 6 standar

d deviation s fro

m th e mea nof th e dail y calibrations) , a secon d injectio

ni s performed . I f th e secon d injectio

nals o fall s outside th e 95 % confidenc e interva l o f th e mea nof th e dail y calibrations , standar dtroubleshootin

g procedure s ar e performedt o determine th e caus e an

danothe r injectio

ni s performed . A

typica l Contro l Char t i s show nin Figure 3 . Syste

m A an d Syste m B use s th

e lates t fift

y run s t o determin

e the averag e use

d inth e contro l char t an

dthi s averag e i s update

d daily . The contro l chart s are visuall y inspecte

d dail y (o nth e PC ) wit hthe result s store do nth e P C associate

d withth e dat a reductio

nfor eac

hunit . Selecte

dtypica l result s are output quarterl y for inclusio

ninth e quarterl y

report s for th e project s covered . 11.3. 3 Calibratio

nQuality

Contro l Problem s leadin

g t o a failure o f th e syste m t o mee t the qualit y assuranc e requirement s show ni nth e abov e contro l chart s roust b e correcte

d befor e proceedin

g withth

e analysis . Large variation s ma

y be due t o equipment failure . I t i s assume

d tha t th

e respons e of th

e FI D i s linea

r wit h carbo nnumber an

d clas s (i.e . r > 0.95) . Thi s assumptio nha s bee npreviousl y

verifiedfo

r severa l hydrocarbons . Th e intercept shoul d no t b

e significantl y

different fo

r zer o at th e 0.0 5 confidenc e level . A positiv

e intercept ma

y impl y contamination . Th e slop e o f the calibratio ncurv e shal l b

e withi n5 percen t o f th e previousl y

determined value . 11.3.3. 1 Establishmen t o f Initia l Warnin g an dContro l Limit s Initia l Warnin

g an dContro l limit s are determine da s 1.9 6 an d Thre e standar

d deviation s of th e previousl y

determine

d averages . (Sectio

n11.3.2 ) 11. 4 Standardizatio n Informatio

nt o b e supplie

d at a late

r date . Bot

hdetaile

d hydrocarbo

nlaboratorie s ar e undergoin g modification s inorde r t o standardiz e the G

C an d dat a processin

g systems . 12. 0 Analysi s Procedure s Th e analysi s procedur e i s th e sam e fo r eac hga s chromatograp

hbu t the preparatio nstage s differ slightly .P.1 3

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : Jun

e 28 , 1991 , Page : 1 2
12. 1 Preparatio

nstage steps : 12.1.1. A

Perki nElmer Sigm a 2000 , Syste

m Al , Evaporativ

e Emissions , C 4 throug hCl l
A . Adjustmen t o f instrument ga s flo w rate s (excep

t carrier gas ) whichshoul db e correcte

d o r adjuste

dbefor e hand . 1 . Se t th

e detecto r ai r pressur e t o 14 0 KP a (2 0 psig) . 2 . Se t th

e detector hydrogenpressur e t o 14 0 kP a (2 0 psig) . B . Adjustmen t o f Carrie r Ga s Flo w Rat e Verif y tha t th

e carrie r ga s pressur e i s a t th e optimu

m pressur e fo

r th e separatio

nrequired . C . Se t u

p detecto r

Hol d the detector igniter a t th e chimne

y o f FI D number 2 an d slowly

increas e th

e detector ai r pressur e t o 28 0 kPa (4 0 psig) . A

poppin g soun d shoul db

e heard , indicatin

g th e detector lit . Thi s ca nb e verified b

y holdin g a mirro r o

r piec e o f glas s u

p t o th e chimne

y an d lookin

g fo r condensation . D . Colum

nan d Valv e Temperature s Detector • 275°C . Initia l OvenTemperatur e = -100°C . Ther e i s a

ninitia l hol d o f 6. 5 minutes . OvenTemperatur e Programmin g Rat e 1 = 20°C/min . OvenTemperatur e 1 = -45°C . Hol d fo r 4 minutes . Ove nTemperatur e Programmin g Rat e 2 = 2°C/min . Ove nTemperatur e 2 = -15°C . Ove nTemperatur e Programmin g Rat e 4 = 6°C/min . Fina l Ove

nTemperatur e = 175°C .P.1 4

AREAL-CPCD-MSER B RPM-00 1 Revisio n No
. 3 Date : Jun e 28 , 1991 , Page : 1 3

Si x Por t Valv e Temperatur e = 90°C

. 12.1.I. B Fron t En

d Analysi s Isotherma l a t ambien t temperatur e Analytica l carrie r flow3 5 ml/mi n Backflus h flo w3 5 ml/mi n
Detecto r temperatur e 27 5 ° AC

. 12.1.2. ASystem

A2 , Perki n Elme r 8700 , C 2 throug h Cl l
A
. Adjustmen t o f instrumen t ga s flo wrate s (excep t carrie r gas ) whic h shoul d b e correcte d o r adjuste d befor e hand

. 1

. Se t th e detecto r ai r pressur e t o 2 0 psig

. 2

. Se t th e detecto r hydroge n pressur e t o 2 0 psig

. B
. Adjustmen t o f Carrie r Ga s Flo wRat e Verif ytha t th e carrie r ga s pressur e i s a t 8 0 psi g a t th e heliu

mcylinder

. Adjus t th e carrie r ga s pressur e regulato r o n th e 870 0 t o th e pressur e indicate d i n th e metho d an

d displaye d o n th e screen . Refe r t o Sectio n 1.11. 1 fo r fin e tuning o f th e carrie r ga s flo wrate
. C

. Se t up detecto r Ope n th e hydroge n toggl e valv e o n th e bac k o f th e 870 0 t o allo wth e hydroge n t o purg e th e lines

. Afte r approximatel ytw o minutes , clos e th e hydroge n toggl e valv e an

d hol d th e FI D ignite r agains t th e chimne yo f th e FID
. Ope n th e hydroge n toggl e valv e an d th e ignite r shoul d glo wbrightl yan d a sligh t poppin g soun d ma yb e heard , indicating ignition

. Thi s ca n b e verifie d b

yholding a mirro r o r piec e o f glas s u p t o th e chimne yan

d looking fo r condensation

. D
. Colum

n an d Valv e Temperatur e Th e ove n temperatur e adjustment , R47 , o n th e analo g boar d wa s adjuste d 1 0 - 1 1 turn s CC W t o obtai n a

temperatur e colde r tha n tha t allowe d b yth e method s software

. Th e actua l ove n temperatur e i s 15° C colde r tha n th e scree n indicate s whe n th e metho d i s se t t o -80° C an d 25° C coole r whe n th eP.1 5

AREAL-CPCD-MSER B RPM-00 1 Revisio n No
. 3 Date : Jun e 28 , 1991 , Page : 1 4

metho d i s se t fo r 200°C

. Thi s adjustmen t allow s th e initia l ove n temperatur e t o attai n -95° C whil e th e metho d i s se t fo r -80°C

. Th e followin g temperatur e listing wil l b e thos e se t i n th e metho d an

d no t th e actua l ove n temperatures
. Th e programmin g rate s ar e unaffected

. Detecto r = 275°C

. Initia l Ove n Temperatur e = -80°C

. Ove n Temperatur e Programming Rat e 1 • = 20°C/min

. Ove n Temperatur e l = -40°C

. Ove n Temperatur e Programming Rat e 2 = 2°C/min

. Ove n Temperatur e 2 = -15°C

. Ove n Temperatur e Programming Rat e 3 = 6°C/min

. Ove n Temperatur e 3 = i20°C

. Ove n Temperatur e Programming Rat e 4 = 8°C/min

. Fina l Ove n Temperatur e = 220°C

. Si x Por t Valv e Temperatur e = 90°C

. 12.1.I. B Hewlet t Packar d 5880A

. A
. Adjustmen t o f instrumen t ga s flowrate s (excep t carrie r gas ) whic h shoul d b e correcte d o r adjuste d befor e hand

. 1

. Se t th e detecto r ai r pressur e t o 27 5 KP a (4 0 psig)

. 2

. Se t th e detecto r hydroge n pressur e t o 27 5 kP a (4 0 psig)

. B
. Adjustmen t o f Carrie r Ga s FlowRat e Verif ytha t th e carrie r ga s pressur e i s a t th e optimu m pressur e fo r th e separatio n required

. C

. Se t up detecto r

Hol d th e AChanne l detecto r ignite r switc h t o manual

. Apoppin g soun

d shoul d b e heard , indicatin g th e detecto r lit

. Thi s can b e verifie d b yholdin g a mirro rP.1 6

AREAL-CPCD-MSER B RPM-00 1 Revisio n No
. 3 Date : Jun e 28 , 1991 , Page : 1 5

o r piec e o f glas s u p t o th e chimneyan d looking fo r condensation

. D
. Colum

n an d Valv e Temperature s Detecto r = 275°C

. Initia l Ove n Temperatur e = -60°C

. Ther e i s a n initia l hol d o f 9 minutes

. Ove n Temperatur e Programming Rat e 1 = 20°C/min

. Ove n Temperatur e 1 = -25°C

. Ove n Temperatur e Programming Rat e 2 = 3°C/min

. Ove n Temperatur e 2 = 25°C

. Ove n Temperatur e Programming Rat e 4 = 8°C/min

. Fina l Ove n Temperatur e = 190°C

. Ther e i s a n fina l hol d o f 1 0 minutes

. Si x Por t Valv e Temperatur e = 90°C

. 12.2. AAnalysi s Stag e Step s Filling th e sampl e loop an d injecting th e sampl e ar e carrie d ou t a s follows :
Tur n o n th e sampl e pum p fo r on e minut e whic h insure s tha t a t leas t 1 0 sampl e volume s hav e flowe d through th e loop

. Afte r on e minut e o f sampl e loop fil l time , clos e valv e V 2 whic h pick s up th e 5-c c sampl e an

d divert s i t t o V 3 fo r methan e analysis

. Afte r methan e elute s V 2 i s returne d t o ope n positio n an d V I an d V 3 ar e close d whic h bac k flushe s th e molecula r siev e porapa k systeman d bring s th e Silic a Ge l colum n o n lin e fo r th e C 2 -C 3 analysis

. A secon d sampl e i s pulle d an d injecte d following th e same procedur e use d fo r methane

. Afte r acetylen e elute s (1 5 minutes) , VI , V2 , an d V 3 ar e returne d t o thei r normall yope n position s whic h no w backflushe s th e silic a ge l column

. Not e tha t propan e an d propylen e ar e als o analyze d during thi s analysis

. Th e rawdat a i s calculate d an

d entere d i n th e IB M PC/A T whe n editing

. 13. 0 Calculation s Using th e calibratio n constan t (k ) determine d i n sectio n 11.3.2 , calculat e th e concentratio n o f eac h compoun d (peak ) a sP.1 7

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : Jun

e 28 , 1991 , Page : 1 6 follows : Concentration , pp m C = (k)(Area ) wher e th

e area i s integrator counts . Mos t integrator s ma y b e programme

d t o perfor

m thi s calculatio

nan dpresent th

e result s directly

i nunit s o f concentration . Th e appropriat e formul a t o calculat e th e limit s o f predictio

nar e giveni

nsectio

n11.3.3.1 . 14. 0 Dat a Reportin

g Th e concentratio

no f eac

hhydrocarbo

nfoun dshoul db

e reporte d t o the compute r sectio ninth e forma t proscribed . The integrato

r outpu t an

d stri pchar t recor d fo r al l samples , calibrations , an

d dail y standard s are identifie duniquel y

an d saved . Electroni c storage i s made o f eac ho f thes e run s fo

r archivin

g an d latter editin

g an dtransfe r t o th

e mai ncompute r group . Eac

hsampl e i s logge

dina,sampl e lo

g a s run . The lo

g boo k ha s th e followin

g format : Date , AM

E ru nnumber , Fil e name , Remark s (descriptio no f run , instrument # o nwhichi t wa s run , dilutio no f liqui d samples , tota l hydrocarbo nconcentration , an d an y other informatio

npertinen t t o th

e current project.) . Th e fil e nam

e i s 8 character s i nlengt han duse s the followin

g convention :
X9999 9 XX

Progra m I D AM E RU N # Ru

nType
A - Z 9999 9 A - Z
CAS E PROGRA

M OF (1S T Letter ) Sampl e Positio n
A - Z

• f
• g
• h

" j ' O R 1 O R

• O R
' O R

• O R

• O R

• O R
' O R A 1 : B ' : C : F 1 : G' : H« : J 1 : '0' : G_CPR0 G G_CPR0 G G_CPRO G G_CPRO G G_CPR0 G G_CPR0 G G_CPR0 G GCPRO G FF

V CN G ALTFUE L SHEDR L FF V CN G ALTFUE L SHEDR L

CAS E CYCLE O

F (2N

D Letter )P.1 8

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : June 28 , 1991 , Page : 1 7

•a ' O R'A' : G_CCY

C = FTP •b ' O R'B• : G_CCY

C = HWFE T •d • O R•D• : G_CCY

C = NYCC •f • O R•F• : G_CCY

C = CU

E •h ' O R'H' : G_CCY

C = LIQFC I F G_CPRO

G= SHEDR

L THE N •n ' O R'N« : G_CCY

C = EVA

P ELS E : G_CCY

C = N/ A •o ' O R*0' : G_CCY

C » MFT P
CAS E BAGPO S OF (3R D Letter )
'a ' O R'A' : BAGPO S • BA GI , HWFET , NYCC , CUE , HOTSOA KSTAR T •b ' O R'B' : BAGPO S = BAGII , HOTSOA KFINA L •c* O R'C 1 : BAGPO S - BAGIII , DIURNA L START •d 1 O R'D' : BAGPO S - BKG , DIURNA L FINA L
NOTE : The detail s o f th e abov e tabl e ar e modifiedand/or expande d t o includ

e ne w project s a s the

y occur . Thi s number , th

e date , an

d th e AM E ru nnumbe r ar e recorde d wit hal l electronicall y

store d dat a fo

r eac hchromatographi c ru nt o provid

e unique identification . The accurac y o f dat a transfe r i s checke d b y th e dat a processin

g sectio

nb y checkin

g th e su m o f the transmitte

d dat a value s agains t the su m o f thes e value s whichi s calculate d at th e poin t of editin

g an d transmitte

d at th e en do f th e dat a file . I f ther e i s a discrepanc

y the caus e i s ascertaine d an d the fil e resubmitted , there ar e severa l othe r check s tha t are preforme d prio r t o dat a entr y into "Archive

d Mobil e Sourc e Emissions " (AME ) suc ha s reasonablenes s of th e ru nnumber , individua l compound s numbers , etc . Agai ni f a discrepanc y a t an y poin t i s see

ni t i s corrected . 15. 0 Correctiv

e Actio n Correctiv

e actio nwil l b

e take nwheneve r abnormalitie s are observe d o r dail y check s fal l outsid e contro l points . Specifi c check s include : Contro l chart s
respons e factor s Relativ e retentio

ntime s Variatio

nsee ni neditin

g proces s o f referenc e peak s Physica l malfunction s The natur e an

d typ e of correctiv

e actio nrequire

di nan y situatio

n i s determine

d an d documente

d b y th e operator . Thi s require sP.1 9

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : June 28 , 1991 , Page : 1 8 chromatographi c experienc e an d i s par t of th

e basi c qualification s required . 16. 0 Metho

d Precisio

n Precisio

no f repetitiv

e analysi s of dail y standard s o f th

e methods are bein

g updated . The

y wil l b e include

dwhencompleted . Typica l RS D o f th e calibratio

nmi xi s les s tha

nsixpercent . Precisio

ni s maintainedan

ddemonstrate

d i nth e contro l charts . Precisio

no f othe r measured compound s shoul d b e simila r t o tha t of compound s whic har e clos e inretentio ntime . Thi s statemen t applie s onl y t o hydrocarbons . Oxygenated material s behav e differentl y

an d ca neffec t th e precisio

no f thos e compound s near b y an dwil l hav

e a separat e bu

t undetermined precisio no f thei r own . 18. 0 Quality

Contro l Thi s sectio

nspecifie s th

e regular QC progra m an ddiscusse s responsibilitie s fo r evaluatio

no f th e QC data . Calibratio nQC wa s discussed i nsectio n11.3 . Thes e procedure s requir e real-tim e revie w o f analytica l performanc e b y th e analyst , an

d QC revie

w directl y

after input int o the mai ndat a base . 18. 1 QC Check s an

d Frequenc

y

* O na quarterl y

basi s th

e calibratio

nmi xi s analyze

dconsecutively si xtimes . For thes e si xanalyse s th e mea nan d standar

d deviatio

no f th e area count s ar e calculate dfo r eac ho f th e compounds . Th

e averag

e area s ar e thensummed , th e summation s the

nfor m th e basi s fo

r th e instrument respons e factor s (k) . Th e respons e factor s ar e update d fo r an y trend s tha t appea r ininstrument respons e or i f th e instrument reache s a

nou t o f contro l state . A dilut e calibratio

nmi xi s ra

ndaily t o assur e instrument stability . Correctiv e actio ni s take

ni f unacceptabl e trend s are note d o r i f th e instrumen t reache s a nou t o f contro l state . Dail y check s ar

e compare d t o the contro l char t t o ensure tha t th e instrument i s operatin g withi nthe contro l limit s o nan y give nday . I f th

e dail y spa nchec k is ou t o f contro l thena secon dspa ncheck i s preformed . Correctiv e actio n i s take ni f the secon

d check i s als o ou

t of control . The firs t ou t o f contro l chec k wil l b e treate

da s a nanomaly

i f th e secon d chec k i s withi nthe contro l limits . O na quarterl y

basi s sample s are exchange d betweeninstrument systems . Thes e ar e t o b e either "real " sample s collecte d durin g a n ongoin g progra

m or "simulated " sample s prepare d b y th e vaporizatio

no f a ful l range gasoline . Sample s ma y b e prepare

d b y eithe r o

r bot hgroup s an d the nru no nal l systems . Result s fro m eac hanalysi s wil l b

e co-pare

d o na compoun

d b y compoun

dbasi s a s wel l a s b y carbo nnumber an

d clas s total s an

d overal l total . Thi s compariso ni s examine

db y th e QCP.2 0

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : June 28 , 1991 , Page : 1 9 coordinator or hi s designe e t o assur e tha t th e instrument s bein

g use d agree o nth e compoun

d identificatio

nan dquantification . Limit s are currently

bein g investigated . 18.1. 3 Contro l Chart s See als o Sectio

n11.3. 2 Calibratio

ncontro l chart s wil l b e maintaine

do nth e respons e factor s observed whe nrunnin g th e dail y calibratio

nmix . At leas t fift y runs wil l b

e use d a s the dat a backgroun dt o provide average s an d varianc e statistics . If , du e t o syste m change s fift

y point s ar e not availabl e th

e larges t numbe r possibl e wil l b e used . Thes e averag e an d varianc e statistic s ar e t o be update da s previousl y

described . Whe

n value s are foun

d inth e warnin

g area (greate

r tha n+/ - 2 sigma ) th

e projec t office r an

d th e Q C office r wil l b e notified . I f th

e exceedanc e continue s or i f the value exceed s th e actio nlimi t ( 3 sigma ) immediat e step s t o ascertai nthe caus e wil l b e instituted . Appropriat e correctiv e actio nfo r th e situatio

nwil l b

e determine

db y th e analys t i n cooperatio

nwit hthe Q C Office r an dth e projec t Officer . Al l exceedance s an d correctiv

e action s wil l b

e recorde

di nth e appropriat e laborator y notebook . The contro l char t wil l b e distribute

dquarterl y

a s par t of th

e norma l reportin

g procedure . Copie s wil l b e give nt o the QC office r a s wel l a s include

d inth e quarterl y

repor t t o th

e projec t officer . Trend s wil l als o b

e monitored an

d reporte

dwhe nsignificant . I t i s recognized tha t majo r instrument repai r ma y caus e a ste

p change i

naverage values . I f suc ha change occur s an dth e instrumentatio

ni s otherwis e operatin g properly

th e chang e wil l b

e accommodated . I t wil l b e assume

d tha t th

e previou s statistic s ar e stil l soun d althoug

hthe meanha s bee ndisplaced . Thi s accommodatio nwil l continu e unti l eithe r fifty day s calibration s hav e bee ncomplete

d a t whic hpoint the ne

w dat a statisti c wil l replac e th e previousl y

use d ones . I f at an

y time , the ne

w statistic s significantl y excee d th e old a n explanatio

nwil l be immediatel y b e sough t an dappropriat e correctiv e actio nagree d uponinconjunctio nwithth

e QC Officer . 18. 2 Performanc e Evaluation s Participatio

ni nperformanc e evaluatio nstudie s i s recommende d an d encourage

d fo r thi s method . The sample s use dfo r thes e audit s shoul d b e withi nth

e norma l concentratio nrange an

db e of th e sam e specie s typ

e as normally

seen . The true value s o f thes e audit s shoul dremai nunknow nt o th e analys t unti l afte r the stud y i s complet e t o preven t operator bias . Al l suc hstudie s shal l be reporte dt o th e QC office r a s wel l a s th e appropriat e projec t office r an di nth e quarterly

reports . 18. 3 System

s Audit s Thi s sectio

ncontain s th

e recommende

dprocedur e fo

r performin

g aP.2 1

AREAL-CPCD-MSER B RPM-00 1 Revisio n No
. 3 Date : Jun e 28 , 1991 , Page : 2 0 syste maudi t fo r thi s method

. Th e nee d an d scheduling o f system s audit s wil l b e determine d b yth e projec t office r i n conjunctio n wit h th e q c officer

. Th e basi c scop e o f th e systemaudi t wil l be : 1

. T o verif yth e adherenc e t o thi s researc h protocol/method ; an d
2

. T o verif yth e dat a flo wan d archiving proces s use d fo r th e computerize d dat a base

. Organization s performin g system s audit s shoul d revie wth e followin g an d th e audi t questionnair e (Appendi x A)

. I t i s recommende d tha t th e independen t audi t pla n b e compare d t o thi s documen t an d difference s noted

. I n al l cases , method s fo r assessing th e dat a qualit yfo r thi s metho d mus t b e approve d b yth e organizatio n being audite d prio r t o th e initiatio n o f th e audit

. 18.3. 1 Audi t Pla n 1

. Mee t wit h organizationa l personnel , identif yke ypersonnel , identif yth e purpos e o f th e audit , an d revie wth e audi t pla n an d questionnaire

. 2

. Collec t al l Q C documentatio n (i.e. , Q C Charts,forms , notebooks,etc

. ) an d dat a bas e prin t outs
. 3

. Performaudi t o f sampl e analysis

. 4

. Performaudi t o f sampl e dat a processing activities

. 5

. Performaudi t o f dat a validation

. 6

. Preformaudi t o f dat a base

. 7

. Complet e audi t questionnaire

. 8

. Hol d audi t revie wmeetin g an d critiqu e audi t findings

. Mak e correction s t o audi t finding s o r questionnair e i f required

. I t i s suggeste d tha t dat a qualit ymigh t b e assigne d on e o f thre e level s according t o th e following guidelines : 1

. Unknow

n Qualit y- a vita l piec e o f Q C dat a i s missin g o r can no t b e verified

. 2

. Questionabl e Qualit y- generall yal l dat a an d document s ar e i n goo d order , bu t a secondaryite mneede d t o completel y characteriz e th e dat a i s missing , e.g. , a contro l char t t o demonstrat e tha t th e metho d wa s i n contro l ove r a give n tim eP.2 2

AREAL-CPCD-MSER

B RPM-00 1 Revisio nNo . 3 Date : June 28 , 1991 , Page : 2 1 interval . 3 . Know

nQuality

- al l documentatio ni s inorder , with dat a traceabl e fro

m th e fina l repor t t o th e dat e an

dtim

e of th e analysis . 18.3. 2 Document s Th e followin

g document s wil l b

e reviewe

dat th e tim e of th e audit : 1 . Laborator

y notebook s or form

s use dwit hth

e method . 2 . Q C chart s 3 . Al l Instrumenta l calibratio ndocumentatio

n 4 . Instructio

nmanual s an

drelate

dSOP' s or RPM's . 5 . Document s relate dt o quality

o f th e material s used . 6 . Al l documentatio nfo r G C computer , dat a validation , dat a transfer , an

d dat a archivin

g an dreporting .P.2 3

AREAL-CPCD-MSER B RPM-00 1 Revisio n No
. 3 Date : Jun e 28 , 1991 , Page : 2 2

APPENDI X A

DETAILE D HYDROCARBON S

B Y GA S CHROMATOGRAPHY
AUDI T QUESTIONNAIR EP.2 4

AREAL-CPCD-MSER B RPM-00 1 Revisio n No
. 3 Date : Jun e 28 , 1991 , Page : 2 3

1 ) Doe s th e technicia n hav e a curren t cop yo f th e RP M availabl e a t o r nea r hi s statio n 2 ) Ar e al l referenc e compound s o f maximu mpurit y available , AC S Reagen t grad e o r simila r 3 ) Ar e calibratio n result s within ; a ) 5 % o f th e mea n b ) r 2 >/ = 0.9 5
4 ) Hav e an youtlyin g standard s bee n rejecte d

I f s o ha s th e rejectio n bee n satisfactoril y explained , documente d an d reviewe d
5 ) Ha s th e calibratio n mi x bee n ru n fo r precisio n a t th e beginnin g o f eac h wee k i n whic h testin g occurre d
6 ) Wer e thes e run s fo r precisio n properl yinclude d i n th e instrumen t dat a bas e 7 ) Hav e th e statistica l contro l chart s bee n update d a t th e prescribe d interval s 8 ) Hav e th e dail ystandard s bee n ru n eac h da ytha t testin g occurre d
9 ) Hav e problem s apparen t fro mdail ystandard s bee n resolve d befor e testin g commence d
10 ) Hav e al l appropriat e statistic s bee n kep t current

_ 11 ) Hav e al l trend s bee n note d an d reporte d
12 ) Ha s appropriat e actio n bee n take n t o resolv e problem s note d fro mtrend s an d statistic s 13 ) Hav e contro l chart s bee n reporte d a t specifie d interval s t o projec t office r an d t o Q AOffice r 14 ) Hav e exchang e sample s bee n ru n i n timel yfashio n 15 ) Hav e result s fro mexchang e sample s bee n reported , YE S N OP.2 5

AREAL-CPCD-MSER B RPM-00 1 Revisio nNo . 3 Date : Jun e 28 , 1991 , Page : 2 4
recorde d i nnotebook s properl y

16 ) Hav e al l problem s uncovere d b y exchang e sample s o r audi t sample s bee nadequatel y resolved , explained , correcte d and reporte d t o al l concerned

_ 17 ) Hav e NIS T (NBS ) sample s bee nruna t appropriat e interval s 18 ) Ar e al l result s fro m thes e sample s properl y recorde d and withi nspecification s 19 ) I s preventativ e maintenanc e preforme d a s scheduled

_ 20 ) Ar e file s i nth e P C properl y maintaine d
21 ) Ar e laborator y an d instrumen t notebook s properl y maintaine d and al l necessary.informatio nrecorde d
22 ) Ar e correctiv e action s take nwhenneede d an d properl y

recorde d and reporte d
23 ) Ar e dat a transfer s properl y recorde d an

d checke d
24 ) Ar e Q C report s file d i na timel y manne r 25 ) Hav e an

y o f th e followin g audit s bee npreforme d onth e laborator y a ) System

Audi t b ) Performanc e audi t

# valv e 2

1 0 c c stimpl o loo p

Colum n

- Flus h
> - Von l

L-

. 1 CC 

### .-rumpl e loo p

J"ainp ! 

### Colum n Flus h

> Ven t


## LJ Cryogeni c Tra p 

# valv e 1 valv e 3
( Methane ) 1'olccula

r Slcv o 13 XColum

n

Colum n Flus h 

# valv e -

1

(C ; C n) 2 " ^ 3 Silic a Go l Colum n

Ven t


# r V t j A 

### v 

### Colum

n Fluu h
Vent 

# u

0.10; i Picri c Aci d Colum n (1,3-Uutadtcnc )
FI D 

# Offi^^X



# C l C 4 An a1ytica l Syste m

llr.ur c V"•^4}^:^.-,^iit**wrf-> v •-*.-* • - . P.2 7

v.i'. ! C-' > Ci
- "

• . i 0* S Vts t^1
.

I:..V

. 

# 3~ |

/':
. . \

• l:v.".: S 

### L J 

# ^

C- C :.s err,
. v.
. V.

. ;- ; v.
. Srscs r i*.::".- : *0>»<?

s •• i :- e :• ' rr&:c v 7. Z. •.-'•9-»av"r.ee c e va..es : 9

. * 0 ;- 3 i V :-.vo-*.i

v ••»: • va..cs : cc-~ n A

. s...caze~Z2Zr.ec cciun-n ; ccumn 3

. co : or yP.2 8



# National Specialty $ases

63 0 UNITE D DRIV E DURHAM , NC2771 3 (919)544-377 2

TOi Nationa l We i de n Raleigh , N.C . DAT E REPORTED i 3-27-9 0 REFERENCE l 8 8 788 7

••* &

MATERIA

L SUBMITTED i Cyl#CC&374 6 Certifie d +/ - 57 .

INFORMATIO

N REQUESTED i Rati o analysi s

METHO D O F ANALYSIS ! Ga s chromatograph

RESUL T O F INVESTIGATION ! Traceabl e Certificat e numbe r 1323 0 Traceabl e t o NB S throug hNB S repor t numbe r 731/24269 7

itF'zi'*; .•'••-•'•)• ..' A'.tl ?

;•;•»
. .'*v<.

.

*t*'i^.«»*'--'-v. . -•iiW.'..,

- .-"
.

^•V"."^:

- •••*' • Hf»>--*»>••.••••

. •:'-.

_ ••g-:~ftcy\--- sJTi-A'-Jipfr'.': —
*;^ « .:?•:••••-• • »«]£• • v *•'*'

- '':

- CONCENTRATION COMPONEN T
•'..- • Benzen e /"Butadien e
• N-Butan e

' • Cyclopentan e .•:'- / N-He;:an e

" • Methan e '• • Propan e N-Heptan e

. Iso-octan e 'Toluen e

. ' 1,2, 4 Trimethylbenzen e • P-Xylen e Nitroge n

AUTHORIZE D SIGNATURE !
"THI S REPOR T STATE S ACCURATEL YTH E RESULT S O F TH E INVESTIGATIO

N MAD E UPO N

THE ' MATERIAL S SUBMITTE D T O TH E ANALYTICA

L LABORATORY . EVERYEFFOR T HA S BEEN MAD E T O DETERMINE OBJECTIVELY , TH E INFORMATIO N REQUESTED i HOWEVER , I N CONNECTION

WIT H IT S RENDERIN GOF THI S REPORT , NATIONA L SPECIALT YGASE S SHAL L HAVE N O LIABILIT YI

N EXCES S O F IT S ESTABLISHE D CHARG E FO RTH E SERVICE . AN YUS E O F THI S REPOR T O RTH E INFORMATION

CONTAINE D HEREI N SHAL L B E AT TH E SOL E RIS K O F TH E USER . M 3-'-^K... . -....: • ••; / -*•*..

_;.' 4

. 6. 6

. 4

. 8

.

N! > a y t y t

T * ? o

*T 0
5

^ T h 1 ii 8 1 PP M PP M PP M PP M PP M PP M PP M PP M PP M PP M PP M PP M Ba l anc eP.29

Figur e 3 

### CONTRO L CH. '

o a t l a. •M..'W.'M'.M.'.W.Ul.l.'.Mi'.l 3 ••• » I.LIJ.IJ.I.U.I.IA'. ' n^A'J.pqc :

>.^>-.t^.V.w^vv^>-> > V^T^-yjl>l|i>» , ,ij^yi«-»iVi^V»->>i^^-.,-.v-aA>- ^

- n J (=•*»• * 

# ri-wi i r 

# \

./i t/H i

/ V
. . I f

r\ n*ift^lfti>-ft >

A i 7 .«

. W

iir^ »

I I M j H 

# ft 17 0 - I I I I jl l M l II I T l M M Mil l 

# A l 1 1 rrv i M i n i n i I ''11 1 M l HIT*

. I I II I M l llTllri l M l II I M lil t I I l«

. I I • 

# 1

Sy"'rifinr'i^'i'nnr^x i )TC"TC ^ •-•^^^«-^-^~-^~^"*-^^-7'"^^.^"-^'"^*'"»~'-"^^'"-»-'"^ ^

, . I ; ; I : I , i1 1 1 1 111 1 1111 1 1 1 1111, 1 11 1 11 1 n I 1 1 11111 1 11 1 1 1 11 1 11 1 II I 1 1 I I I I I I I. I I

. 5 ' 0 1 5 2 0 2 5 3 0 3 5 * 0 « 5 5 0 5 5 -.' O '. 5 "" : ~ r:

".•;..U A• -

Tast e 1

kE' « 30 6 'lt.<LCOX P TA5L E

K:re : Titl e i< ;

CA L «

8 9 1 0 1 1 1 2 1 3 1 4 1 5 1 6 1 7 1 3 1 9

• 2 0 2 1 2 2 2 3 2 4 2 5 >l 6
i

. J 2 3 2 9 3 3 T I 2 2 3 3 I » 3 5 3 6 3 7 3 3 i r 4 0 4 1

- 2

• 7 l i

- "j
, ^

. 4 7

„ 5

- f

- - sooc i fi e f

M W

16.0 4 28.05 4 30.0 7 26.03 S 44.09 7 42.06 1 40.0 6 4 0

. C 6 53.12 4 53.12 4 56.1C 3 56.10 3 54.09 2 53.12 4 53.12 4 56.1C 3 5 2 5 2 55.10 3 5 2 5 0 70.13 5 72.11 5 72.11 5 5 2 70.13 5 6 3 6 6 73.13 5 72.15 1 65.11 9 70.13 5 63.11 9 70.13 5 7:.13 5 I£.1 3 66. 1 16.:7c. i4.'1 9 6 3 iz

. a

. 9 £4.H 2
7 •

. " )

~ ~ " 3 3 - "

- • ? r

• - . - J --.. :~z

_- . " • - 2

-

_• ^ 2

- - -i

. - . y.'~

- d / 1

o rc

_

C #

c
A 6 ; 5 ^ 0 « . : ^ 7/39 )

rren t

S C

1 0 2 0 1 1 4 0 1 1 2 0 2 2 4 0 1 2 0 2 0 2 0 2 2 1 1 0 2 1 4 0 0 2 1 4 0 4 0 2 3 1 2 0 4 0 2 0 2 2 4 0 2 3 1 1 2 2 2 1 2 2 2 1 2 1 2 3 2 3 1 3 2 2 2 2 2 2 2 2 2 2

• i

->• > ' - 3

' 3 C i ', ' i

. ' Ta b e 1

instrumen t condition s an d i s

C L

1 2 1 4 1 2 2 4 1 5 2 2 2 1 5 2 4 5 2 4 4 2 1 5 4 2 2 4 2 1 2 2 2 2 2 2 2
*t

• 2 2 2 2 2
t

w • C ' 2 : i H

4 4 6 2 8 6 4 4 1 0 1 0 8 8 6 1 0 1 0 8 4 4 8 4 2 1 0 1 2 1 2 4 1 0 8 6 1 0 1 2 8 1 0 8 1 0 1 0 8 6 1 4 2 8 6 Q
D

. 3

• ?

• i

• o

• -

• -

~ DENSIT Y

18.832 9 16.513 1 17.699 8 1S.326 4 17.304 2 16.513 1 16.116 4 15.696 5 17.1C6 4 17.106 4 16.513 1 16.513 1 15.919 8 17.106 4 17.106 4 16.513 1 15.304 1 15.3C4 1 16.513 1 14.715 5 15.3C4 1 16.513 1 16.979 3 16.979 3 15.334 1 16.513 1 16.01C 4 15.539 5 16.513 1 16.937 8 16.033 4 16.513 1 16.035 4 16.513 1 16.513 1 16.041 0 15.563 1 16.933 7 16.C33 4 16.010 4 16.010 4 16.C1C 4 16.C10 4 16.513 1 '5.513 1 16.3'3 1 1S.S13 1 '.;.>:2 7

' :. ' . ' ! l ':. : 13 1
' - '. n " ':..'• 1' H/ C

4.00 0 2.00 0 3.00 0 1.00 0 2.66 7 2.00 0 1.33 3 1.33 3 2.50 0 2.50 0 2.00 0 2.00 0 1.50 0 2.50 0 2.50 0 2.00 0 1.00 0

' 1.03 0 2.00 0 1.00 0 0.50 0 2.03 0 2.40 0 2.40 0 1.0C 0 2.CC 0 1.6C 0 1.23 0 2.00 0 2.40 0 1.60 0 2.00 0 1.63 0 2.CC 0 2.CO O 1.60 0 1.60 0 2.33 3 1.60 3 1.60 0 1.60 0 1.60 3 1.60 3 2.00 3 2.00 3

- I* r - \ 2.00 0 2.33 3 o . o; o 0.00 3 1.33 3 :.;. j

- • ^

change d i f th e ehromatoarsc'ii c

NAM E

METHAN E ETHYLEN E ETHAN E ACETYLEN E PROPAN E PROPYLEN E PROPAOIEN E METHYLACETYLEN E ISO-BUTAN E

• • • UNKNOW N •• • 1-BUTEN E ISO-BUTYLEN E 1,3-BUTADlEN E N-BUTAN E • * • UNKNOW N •* * TRANS-2-6UTEN E 1-BUTEN-3-Y N

• • • UNKNOW N •• * CIS-2-BUTEK E C4H 4 1 , 3 BUTAOYN E 3-HtTHYL-1-BLITcN c ISO-PENTAN E

• • • UNKNOW N ** * 2 6UTTN E 1-PENTEN E C5K 8 CSH 6 2-HETHYL-1-BUTEN E N-PENTAN E ISOPREN E TRANS-2-PENTEN E C5H 3 CIS-2-PENTEN E 2-HETHYL-2-BUTcK i CYCLCPENTEN E CYCLCPENTAOIEN E 2,2-OIHcTHYLBUTAi. E 1-CIS- 3 FcNTADltS E C5H 3 C5K 3 C5H 3 C5H 3 3-"?THYL-1- D E>iT£s ; C6H1 2 CTCLC^SIAK E " • * US«.KC- N •• * :.3-DIM£THYLSUTAS E 0:iil 2 C i i 1 2 3 - M STn-LC;STAS c :i*\ i ' • ' '.MkNO'- N ** • scoera t ic n

FCSHJLA S

CTr 4 C2^

. C2h 6 C2H 2 C3H 8 C3H 6 C3H 4 C3H 4 C4H1 0 C4H1 C C4K 8 C4n 8 C4H 6 C4K1 C C4K1 3 C4K 3 C4K 4 C4K 4 C4r. 3 C4h 4 C4k 2 C5rtl 0 C5H1 2 C5H1 2 C4H 4 C5«1 0 C5« S C5r 6 C5.H1 0 C5n1 2 C5H 3 C5S1 3 C5-- S C5r<1 0 C5M C C5r S C5- 6 C6»l

- "5- 5 05- 5 C:- 5 0 5 - 5 0 C - c

::•• ; C:- '

. 1 0 : -'.. '

- c

. • • 0 ; - ,' • - ." : -'

. .":.- ' C

:.--• -

. : •^

'P.3 1

T s b l e 1

5 4

5 5 5 6 5 7 5 3 5 9 6 0 6 1 6 2 6 3 6 4 6 5 6 6 6 7 6 8 6 9 7 0 7 1 7 2 7 3 7 4 7 5 7 6 7 7 7 3 7 9 £ 3 3 1 £ 2 £ 3 C * £ 5 e 6 6 7 c c £ 9 9 0 9 1 9 2 9 3 C i < o 9 6 9 7 9 3 9 9 10 3 10 1 10 2 10 3

« • r\ t 1 w" » 10 5 * * * 10 7

. - o 10 9

1 * ** t V I

' :2

• • T
* * -

• - e 64.16 2 84.16 2 £ 3 102.13 0 86.17 8 64.16 2 64.16 2 84.16 2 84.16 2 86.17 8 84.16 2 84.16 2 84.16 2 84.16 2 82.14 6 84.16 2 82.14 6 100.20 5 84.16 2 84.16 2 84.16 2 84.16 2 100.20 5 100.20 5 30.1 3 80.1 3 9 6 £2.14 6 7E.11 4 93.15 9 1C3.20 5 93.18 9 84.16 2 9S.1£ 9 9S.1E 9 93.13 9 £ 2 9 5 1C3.20 5 1C3.23 5 93.13 9 £2.14 6 1C3.20 5 93.13 ? 93.13 9 93.13 9 93.is ; 93.13 ? 114.23 2 93.13 9 96.16 1 1 CO.23 5 93.13 ? 93.13 ? 92.10 9 93.13 ? 93.13 9 93.13 ? c« . 93.10 ? •'2.01 6

- 6 6 5 6 6 6 6 6 6 6 6 6 6 6 6 6 6 7 6 6 6 6 7 7 6 6 7 6 6 7 7 7 6 7 7 7 7 7 7 7 7 6 7

i 7 7 7 7 8 7 7 7 7 7 7 7 7 7 7 7 0 ^ 0 0 3 3 1 3 2 1 2 1 0 0 1 1 2 1 2 1 2 1 2 1 2 3 2 1 2 3 1 3 2 1 1 4 2 1 2 1 1 3 1 3 2 2 0 2 1 2 3 3 0 2 1 1 3 2 1 1 4 2 1 2 1 2 1 2 3 2 1 1 3 1 3 1 4 2 3 1 3 2 1 2 3 2 3 2 3 2 1 1 3 2 1 2 3 1 1 2 1 2 1 2 1 2 1 2 1 2 1 2 3 2 1 0 1 2 3 5 5 5 5 1 2 2 5 5 1 2 2 2 2 2 2 2 1 2 1 2 2 1 1 2 5 2 2 3 2 1 2 1 2 2 2 2 2 1 1 1 2 1 2 2 2 2 2 1 2 2 1 2 2 2 2 2 2 ; z

„ 1 2 1 2 1 2 1 4 1 4 1 2 1 2 1 2 1 2 1 4 1 2 1 2 1 2 1 2 1 0 1 2 1 0 1 6 1 2 1 2 1 2 1 2 1 6 8 8 8 1 2 1 0 6 1 4 1 6 1 4 1 2 1 4 1 4 1 4 1 4 1 4 1 6 1 6 1 4 1 0 1 6 1 4 1 4 1 4 1 4 1 4 I S 1 4 1 2 1 6 1 4 1 4 1 4 1 4 1 4 1 „
• ?

- i

* 3 16.513 1 16.513 1 25.£992. , 24.434 5 16.903 7 16.513 1 16.513 1 16.513 1 16.513 1 16.903 7 16.513 1 16.513 1 16.513 1 16.513 1 16.117 6 16.513 1 16.117 6 16.852 1 16.513 1 16.513 1 16.513 1 16.513 1 16.852 1 15.722 0 15.722 0 15.722 0 16.145 0 16.117 6 15.326 4 16.513 1 16.£52 1 16.513 1 16.513 1 16.513 1 16.513 1 16.513 1 13.793 5 16.431 3 16.£52 1 16.E52 1 16.513 1 16.117 6 16.£52 1 16.513 1 16.513 1 16.513 1 16.513 1 16.513 1 16.£09 3 16.513 1 16.513 1 16.352 1 16.174 1 16.513 1 16.513 1 16.513 1 16.513 1 10.513 1

' i

. 1 4 3 3 1 i

. 5 ' 3 1

'
. * • 5'

. ~ i 2.03 0

2.00 0 3.CO O 2.£0 0 2.33 3 2.CO O 2.00 0 ' 2.00 0 2.00 0 2.33 3 2.00 0 2.00 0 2.00 0 2.00 0 1.66 7 2.00 0 1.66 7 2.28 6 2.00 0 2.00 0 2.00 0 2.00 0 2.28 6 1.33 3 1.33 3 1.33 3 1.71 4 1.66 7 1.00 0 2.00 0 2.23 6 2.00 0 2.00 0 2

. CO O 2.CO O 2.CO O 2.C3 0 2

. CO O 2.23 4 2.23 6 2.CO O 1.66 7 2.23 6 2.00 0 2.03 0 2

. CO O 2.03 0 2.CO O 2.25 0 2.CO O 1.71 4 2.23 6 2.00 3 2

. CO O 2.00 0 2.00 0 2.00 0 2.OO O

' .71 4 :.:o o r. . o o '.75 3 - •

•• • UNKNOW N•* •

•• • UNKNOW N•• • HTB E ETB E 3-METHYLPENTAN E 2-METHYL-1-PENTEN E 1-HEXEN E

•• • UNKNOW N•• •

•• • UNKNOW N•• • N-HEXAN E C6H1 2 C6H1 2 3METHY L C1S-2-PENTEN E 2METHU-2PEMTEN E 3 O R4 METHY L CYCLOPENTEN E CI S ORTRAN S 20 R3 HEXEN E C6H1 0 C7H1 6 3 METHYL-TRANS- 2 PENTEN E METHYLCYCLOPENTAN E METHYL-C1S-2-PENTEN E METHYL-TRANS-2-PENTEN E 2,4-OIHETHYLPENTAN E 2,2, 3 TRIHETHYL6UTAN E C6H 8

•• • UNKNOW N•• • C7H1 2 C6H1 0 BENZEN E C7H1 4 3, 3 DIMETHYLPENTAN E C7H1 4 CYCLOHEXAN E C7H1 4 C7H1 4 C7H14

. C6H1 0 4 METHY L TRANS-2-HEXEN E 2-METHYLHEXAN E 2,3-DIMETHYLPENTAN E 1, 1 D1METHYLCYCL0PENTAN E CYCLOHEXEN E 3-METHYLHEXAN E C7H1 4 1C1 S 3DIMETMYLCYCLG?EhTEN c TRANS-1,331METHYLCYCLCPEN1EN E URANS-2,DIMETHYLCYC:.C?EN7Es E C7H1 4 ISO-OCTAN E 2 METHYL- 2 HEXEN E VETHYLCYCLC.-.EXENE N'-HEPTAK E 3 METHY L CIS- 2 HEXEN E C7H1 4 TRANS-2-r.EPTEN E 3 ETHYL-CI S 2 PENTEN E C7H1 4
2. 3 CIHEIKYL-2-PENTEN E 07nl 2 07H1 4 2,2. 4 TRi-ETHYL-1-PENiEN E 03nl 4 1 ;

C1-.1 2 Ci-1 2 CSnlt O Ci-14 3
Ci-1 2 Cii1 2 C6H1 2 Ci-11 2 Ci.i U Ci«2. , C6K1 2 C6H1 2 C6H1 2 C6H1 0 C6H1 2 Ctvil O C7H1 6 C6H1 2 Ci.<1 2 C6H1 2 Cii1 2 C7H1 6 C7*1 6 Cip 3 CiH S C7H1 2 Cinl O Cip 6 C7p!4 C7h1 6 C7H14 06H1 2 Z7-. 1 4 07 v1 4 07*1 4 Ci-1 0 07rl 4 C7ril 6 07-11 6 07-.1 4

* " L

. • * 1 0 7.-1 6

• 0 7-14 , 0

. . i 1 4 0 7-1 4 07-1 4 ""-1 4

- ' . • o 0 7-1

- 0 " -'
. 2
:"- t

: "

- • - :*- ' -

- " - * - '.'-'-

""-'- >

'"•-' "

: " - • - '.±-'.P.3 2

**" * * ' *

\ Tabl e 1

11 6 11 7 11 3 11 9 12 0 12 1 12 2 12 3 12 4 12 5 12 6 12 7 12 8 12 9 13 0 13 1 13 2 13 3 13 4 13 5 13 6 13 7 12 3 13 ? 14 0 141 14 2 14 3 14 4 14 5 14 6 14 7 14 3 14 9 15 3 1 c 1 15 2 15 3

* C •

* > C C 1J 4 •"","*' 15 5 15 9 '6 0 16 1 1C 2 1: 3 ^i*. 16 5

... . '6 7
* / o

. Z *

• ~ - 1 7 1

* - ^

• ~ 3

- -
• 7-
•" i 110. 2

9 3 114.23 2 114.23 2 11 2 114.23 2 114.23 2 112.21 6 114.23 2 114.23 2 92.14 1 112.21 6 114.23 2 114.23 2 96.16 1 114.23 2 114.23 2 112.21 6 112.21 6 128.25 9 112.21 6 112.21 6 112.21 6 112.21 6 112.21 6 12 3 112.21 6 112.21 6 112.21 6 112.21 6 112.21 6 112.21 6 114.23 2 114.23 2 112.21 6 112.21 6 112.21 6 112.21 6 112.21 6 112.21 6 112.21 6 1* 3 123.23 ? 123.25 9 123.25 ? 112.21 6 123.25 ? 112.21 6 110. 2 123.25 9 122.25 ? 123.25 9 .* A*( 3 126.24 3 126.2- 3 106.16 3 106.16 3 123.23 ?

•
_ Z

. . 4 - " * •23.23 ? '22...'.. ? •23.23 ? 8

7 8 8 8 8 8 8 8 8 7 8 8 8 7 8 8 8 8 9 8 8 8 8 8 9 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8
Q 9 9 9 8 9 8 8 9 9 9 2
v
r s 3 9

. 9 9 2 3 2 1 4 1 1 3 1 1 3 1 1 4 1 1 3 1 0 5 2 3 2 1 3 1 1 3 1 3 1 3 21 2 1 3 1 1 3 1 2 3 2 13 1 1 3 1 1 3 1 1 4 1 1 3 1 1 4 1 1 4 1 1 4 1 1 4 1 1 4 1 1 3 1 1 4 1 1 4 1 1 4 1 1 4 1 1 4 1 4 1 3 0 ! 1 4 2 1 ; 0 ' 2 2 ; 1 4 1 4 0 2 3 1 3 0 1 3 2 1 1 3 2 1 2 3 1 3 1 3 0 3 1 1 4 1 4 3 2 3 2 1 3

' J

.- i

'
. 3

• 7 1 4

1 4 1 8 1 3 1 6 1 8 1 4 1 6 1 8 1 8 8 1 6 1 8 1 8 1 2 1 8 1 8 1 8 1 6 2 0 1 6 1 6 1 6 1 6 1 6 2 0 1 6 1 6 1 6 1 6 1 6 1 6 1 8
> 1 8 1 6 2 1 6 i 1 6 2 1 6 1 1 8 1 ' 1 6 5 1 6 2 1 4 1 2 0 5 2 0 1 2 0 2 1 6 1 2 0 2 1 6 2 1 4 1 2 0 1 2 3 5 2 0 3 1 0 IS 1 1 3 7 « n

. . i J

- j

:
. - 1

'
. 16.216 4 16.451 3 14.4212

. 16.E09 3 16.431 3 16.£39 8 16.£39 8 16.513 1 16.809 8 16.809 8 15.496 0 16.513 1 16.809 8 16.809 8 19.211 2 16.809 8 16.809 8 16.809 8 16.513 1 16.776 8 16.513 1 16.513 1 16.513 1 16.513 1 16.513 1 16.742 9 16.513 1 16.513 1 16.513 1 16.513 1 16.513 1 16.513 1 16.839 8 16.839 8 16.513 1 16.513 1 16.513 1 16.513 1 16.513 1 16.513 1 16.513 1 16.187 0 16.776 8 16.776 3 16.776 3 16.513 1 16.776 3 Is.513 1 16.216 4 16.776 5 16.7-6 3 16.771 3

• C i-T

. 16.313 1

* *

. C " 7 • 15.J.23 1 I5.i23 1 Ii

. 7 7 ; 3

- . ;.

- '
. . ~ - . 3 "-.
. 7~. S 1.75 0

2.00 0 2.2S 0 2.25 0 2.03 0 2.25 0 1.75 0 2.00 0 2.25 0 2.25 0 1.14 3 2.00 0 2.25 0 2.25 0 1.71 4 2.25 0 2.25 0 2.25 0 2.00 0

• 2.22 2 2.00 0 2.00 0 2

. CO O 2

. CO O 2.00 0 2.22 2 2.CO O 2.00 0 2.00 0 2.00 0 2.00 0 2.00 0 2.25 0 2.25 0 2.00 0 2.C3 0 2.CO O 2

. CO O 2.25 0 2.CO O 2.00 0 1.75 0 2.22 2 2.22 2 2.22 2 2.00 0 2.22 2 2.00 3 1.75 0 2.22 2 2.22 2 2.22 2 1.23 3 2.00 3

- » - - i 1.25 3 1.22 3 2 "" ^ -.*-.

.

- --- >

- - 1 - .

CSH1 4 ETHYLCYCLCPENTAN E 2, 5 DIMETHY L HEXAN E 2, 4 DIMETHY L HEXAN E TR1HETHY L CYCLOPENTAN E 3, 3 DIMETHY L HEXAN E

•• • UNKNOW N•• • TR1HETHYLCYCL0PENTEN E 2,3,4-TRIMETHYLPENTAN E 2,3,3-TRIMETHYLPENTAN E TOLUEN E METHY L HEPTEN E 2, 3 OIMETHYLHEXAN E C8H1 8 METHYLCTCLOHEXEN E 2-METHYLHEPTAN E 4-METHYLHEPTAN E 3, 4 OIMETHYLHEXAN E C8H1 6 3 METHY L HEPTAN E C£H1 6 CSH1 6 CSH1 6 CSH1 6 CSH1 6 2,2, 5 TRIMETHYLHEXAN E CSH1 6 C3K1 6 C8H1 6 C8H1 6 CEH1 6 C8H1 6 N-OCTAN E
* " UNKNOW

N•• " CSH1 6 2-CCTEN E

•• • UNKNOW N• " CSH1 6 CSH1 6 CSH1 6

•• • UNKN3W

N«* • CSH1 4 2, 3 C R 2,3, 5 TRIMETHYLhtXAN c •* * UNKNC. N•* * C9H2 0 CSH1 6 C9H2 0 03H1 6 CSH1 4 09H2 0 09H2 0

•THYLeENO'N i "SIH.ETHUCY:: . OHEXANE 01*1 3

u -mEN E "•-XUEN E 0?H2 3 .-9n2 0
•* * 'JNKNO. N

•* * :;H2 3 0 9I? 3 C3-H 4 C7H1 4 CSnI S CSrfl S C£rU 6 CS.TI S C3H1 4 C3H1 6 C3.-.1 S C3-I1 3 CT**:

- C£H1 6 C8H1 8 C8H1 8 C7H1 2 CEH1 S C£H1 8 C£n1 6 CSH1 6 C9n2 0 C3H1 6 C3.H1 6 C£.-:1 6 C3H1 6 CSN1 6 C9H2 0 CSi-1 6 C3-:i 6 CSH1 S CS.-1 6 C3.-1 S CS-il 6 CS-1 3 c e - " Q C3-1 S C3-1 S ~c^. * CS-i1 6 C3-1 6 C£n1 6 C : £-.1 i 0 c - 1 - C9.-2 3 C9-2 0 09-2 0 02- i i 09-2 0 02-' s

^ C - ' - Z z -ll Z~' 11 Z - * 11 11 -' - ' t ' - ' -

- : - ' z li ~' 1
* ; - ' J 1 * - . * - -•"•.
. 1 '• 11-

Tabl e 1

17 3 17 ? 18 3 18 1 18 2 16 3 16 4 1E 5 16 6 1£ 7 16 3 18 9 19 0

. V •- - - 19 1 -sl-r'- W v..- ' - —19 2 19 3 19 4 19 5 19 6 19 7 19 3 19 9 20 3 20 1 20 2 20 3 20 4 20 5 20 6 22 7 20 3 20 ?

•

. 21 0 21 1 21 2 21 3 21 4 21 5 21 5 21 7 21 3 21 ? 22 3 22 1 22 2 22 3 22 4 22 5 22 6 22 7 22 3 22 9 23 0 23 1 23 2 23 3 23 4

111 23 7

** * o

- • 126.24 3 106.16 6 126.24 3 126.24 3 142.23 6 126.24 3 126.24 3 126.24 3 126.24 3 128.25 9 126.24 3 126.24 3 126.24 3 126.24 3 126.24 3 120.19 5 142.28 6 142.28 6 142.2S 6 142.26 6 142.23 6 142.28 6 14 0 142.23 6 142.23 6 142.23 6 123.19 5 140.25 0 120.19 5 120.19 5 142.26 6 120.19 5 142.26 6 142.23 6 142.26 6 120.19 5 142.23 6 142.26 6 142.23 6 142.23 6 120.19 5 142.23 6 142.23 6 142.28 6 142.26 6 134.22 2 156.31 3 123.19 5 134.22 2 134.22 2 156.31 3 116.1 6 156.31 3 156.31 3 156.31 3 156.31 3 134.22 2 156.31 3 134.22 2 134.22 2 134.22 2 13,.22 2 9

8 9 9 1 0 9 9 9 9 9 9 9 9 9 9 9 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 9 1 0 9 9 1 0 9 1 0 1 0 1 0 9 1 0 1 0 1 0 1 0 9 1 0 1 0 1 0 1 0 1 0 1 1 9 1 0 1 0 1 1 9 1 1 1 1 1 1 1 1 1 0 1 1 1 0 1 0 1 0 1 0 1 3 3 2 1 4 1 4 1 3 1 4 1 4 1 4 1 4 1 1 2 1 2 1 2 1 2 1 2 1 3 1 1 3 1 3 1 3 1 3 1 3 1 3 1 3 1 3 1 3 1 3 3 1 1 4 3 2 32 1 3 3 2 1 3 1 3 1 3 3 2 1 3 1 3 1 3 1 3 3 2 1 3 1 3 1 3 1 1 3 1 1 3 3 2 3 2 3 2 1 3 3 6 1 3 1 3 1 3 1 3 3 2 1 3 3 2 3 2 3 2 3 2 1 3

2 2 2 2 2 3 1 1 1 1 1 1 1 1 1 1 3 1 3 3 1 3 1 1 1 3 1 1 1 1 3 1 1 1 1 3 1 3 3 3 1 3 1 1 1 1 3 1 3 3 3 3 1 8 1 0 1 8 1 8 2 2 1 8 1 8 1 8 1 8 2 0 1 8 1 8 1 8 1 8 1 8 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 0 2 2 2 2 2 2 1 2 2 0 1 2 1 2 2 2 1 2 2 2 2 2 2 2 1 2 2 2 2 2 2 2 2 2 1 2 2 2 2 2 2 2 2 2 1 4 2 4 1 2 1 4 1 4 2 4 8 2 4 2 4

2 4 1 4 2 4 1 4 1 4 1 4 16.513 1 15.623 1 16.5151.

. 16.776 3 16.750 4 18.611 6 16.513 1 16.513 1 16.513 1 16.776 8 16.513 1 16.513 1 16.513 1 16.513 1 16.513 1 15.722 0 16.750 4 16.750 4 16.750 4 16.750 4 16.750 4 16.750 4 16.481 3 16.750 4 16.750 4 16.750 4 15.722 0 14.149 8 15.722 0 15.722 0 16.750 4 15.722 0 16.750 4 16.750 4 16.750 4 14.149 8 16.750 4 16.750 4 16.750 4 16.750 4 15.722 0 16.750 4 16.750 4 16.750 4 16.750 4 15.801 1 16.723 9 15.722 0 15.£01 1 15.£31 1 16.723 9 15.194 2 16.723 ? 16.723 ? 16.722 ? 16.723 9 15.£31 1 16.723 ? 15.331 1 15.301 1 15.301 1 15.301 1 2

. CO

O 1.25 0 2.00 0 2.00 0 2.20 0 2.00 0 2.00 0 2.00 0 2.00 0 2.22 2 2.00 0 2.00 0 2.00 0 2.00 0 2.00 0 1.33 3 2.20 0 2.20 0 2.20 0 2.20 0 2.20 0 2.20 0 2.00 0 2.20 0 2.20 0

, 2.20 0 1.33 3 2.00 0 1.33 3 1.33 3 2.20 0 1.33 3 2.20 0 2.20 0 2.20 0 1.33 3 2.20 0 2.20 0 2.20 0 2.20 0 1.33 3 2.20 0 2.20 0 2.20 0 2.20 0 1.40 0 2.18 2 1.33 3 1.40 0 1.40 0 2.13 2 0.ES 9 2.13 2 2.13 2 2.1E 2 2.18 2 1.40 0 2.18 2 1.43 0 1.40 0 1.40 0 1.43 0 • *

C9H2 0 O-XYLEN E C9H1 8 C9H1 8 C10H2 2 C9H1 8 C9H1 8 7 C9H1 8 ? C9H1 8 7 N-NONAN E C9H1 8 7 C9H1 8 7 C9H1 8 C9H1 8 C9H1 8 ISOPROPYLBENZEN E C10H2 2 7 C10H2 2 7 C10H2 2 ? C10H2 2 7 C10H2 2 7 C10H2 2 ? C10H2 0 C10H2 2 7 C10H2 2 7 C10H2 2 7 N-PROPYLBENZEN E C10H2 0 1METHYL-3ETHYLBENZEN E 1METHYL-4ETHYLBENZEN E C10H2 2 1,3, 5 TRIMETHYLBENZEN E C10H2 2 C10H2 2 C1CH2 2 1-MET-2-ETHYLSENZEN E C10H2 2 C10H2 2 C10H2 2 C13H2 2 1,2, 4 TRIMETHYLBENZEN E C1CH2 2 C10H2 2 C10H2 2 N-DECAN E SEC-6UTYLBENZEN E C11H2 4 1,2, 3 TRIMETHYLBENZEN E C10H1 4 C10H1 4 C11H2 4 1N0EN E C11H2 4 C11H2 4 C11H2 4 ? C11H2 4 C10H1 4 011H2 4 » C10H1 4 C10H1 4 C10H U C1CH1 4 » C11H2 4 CICN K C9W2 0 C8H1 0 C9rt1 S C9H1 3 C1CH2 2 C9«1 8 C9H1 8 C9H1 8 C9H1 8 C9n2 0 C9«fte- > C9H1 8 C9H1 8 C9H1 8 C9H1 8 C9H1 2 C10H2 2 C10H2 2 C10H2 2 C10H2 2 C10H2 2 C1CH2 2 C10K2 0 C10H2 2 C1C.H22 C10H2 2 C9H1 2 C10K2 0 C9H1 2 C9H1 2 C1CK2 2 C9H1 2 C1Ch2 2 C1CH2 2 C10h2 2 C9H1 2 C1Ch2 2 C1C-i2 2 C13H2 2 C10H2 2 C9H1 2 CIO.2 2 C10n2 2 C1CH2 2 C10H2 2 C10H1 4 C11r2 4 C9H1 2 C10h1 4 ClOnl

. cr.nt

. C9- 3 C 1 ' ; f 2 - CH-2

- CllnO

Clli"

- C10-1-

. 0H-3

- : i o 1 1 - 01^-1

- - 1 r - 1 - C 1 0 - 1

.

' P.3 3i-4i-jrxirwrortroror\tforororororororo^>r\jr\irorororofo^r\ir ^ 4 ) ^ i * * * > - O •<

» •* ) 4 ) t o vo

u » t o r o t o t n t o t o i o - o - J - J -O , - ^ *^ j - J - J - g *. » o f > r > c > t > o * ^ O c ^ O i^ » */ » w » w * \/ t l/ i w » v » i ^ c n r> i > * - * ^ j - 4* " J ^ r o>^o-LAl-t^rNj^tj<Jw^(>N^*-iJM^c>M)63-^c>v^i^' " - . _. . _.„,.. . _ - _ *' ) I D N t > v/

l I ' W Iv

j - • N - O Otf l Nt > W1 M O0»MOuiM^fv)-« O

UUiMtNiAUIUiUiinuiuiui ^ j^oJ^teoooooooroJ ^ OOCTOOOOOOOOOOO O O J # ' * •|-W-*-»-*WW\fl l r j ( n O ) C

n fv j S S S •C J ••••C J OOO ' r o * - » r o r o r o •wN M wM M M r o M M w•• •rviNUiNrviWWUUuuuiMriurviMuui J rooJ*Nij;j-j-o*J-#-*^J-Jro<jf~4-j^rjWoJiw^ro^ro*>^ ^ —^ —-^^oro^roro---«- » ooooooutW'«<o«^o«o<)«^iv^<}«<>t^^^^^l^)WN«WWUWwwu(>^lM^)^lUMO l

or\jr\jr\ioo-»o**-»-*-«-*-*-*-*>oo-*oo->-»- *

0l-«0 4 UU^UOiWUUUbitlWU^-«-'^WUI-*UW*A^^ l oocjr>ooooooooooooorot-JUJoror\juiro/rororor\jrot>^r\iroc>L*J M

- •M ^^^^j^-^^u^^^^jNNfvl-«^r\l-*^r\INWWNrv|W--*N-*-»NWfv l v>o'iOoooci<->t>ooooooooooo4>^c»0tCh^0t<h<K<^^0-<>r\»0t0*C h ****>•.* * C M * ^ * * r > 4**j^r-r * ..0'>^JOe^CJOOOOOOOOOOOOOO'w/»t>l/*Cjll/»»^C>C/»t/l»4AI^ ^ »N|Onm(DN()lp>{0(D(Bn^CoapinNSN(Br9NCI||tNNNSNNS^(DSn>(D^N) S I-^co6^c>tV^5 ; c>c>c>c>ot>r>c>c>t>- ^ — 4)n«uiv^inovAvninutui^u^^uiMOOO^^oi^ui(>noitaOBnCDU^D]^^iDD)O i

.. j r

_t > e , t
. O O *.0«.JOOOOOOOOOOO-»r\J O —- * -»r\J-*- - -*- * ^-^^--^NfvJN^^rO-***WMrvlr\lrVrN'N- ' - * rv j - * - •N W W rxj-ftODr^i^J^^J^i^J^J^^f^roJ^J-^j^rj-* - S^ouiuiui&uiuiinuiuioovflvn^oc^^^ooiDOMttntttaocooooaoo u USOUUlNflN^^VlvflVOOUf^MOSSSOOMOUNN^Nrv'NNOOrgOONN N

•••••a •••• * ••••« •• •••- * r o t > »^^^^ ^ —— ^oo^^^Oi\JroroOoCO---*-*-*-»-»-*-*00-*>oo--*-*-- * x x x xxocxxxxxxxxxxxxxxxiarxxxxxxxxxxxxxxxx x C T C t ; C rCCC C C CZ C C C CZ CCCCCC-WHC--W---^^^^^--^NNlW-«-0--NWNIvlN*OW-*-'W---MWrv ) a rr-r rT

*: T T X r. -r . T. a c a : J- : Z Z zzzz^c^x*c(^(^C^O>(^(^(^(^^^JOC^C^NC^(^(^^^ffl^O>^^^^^^^M^^^^^^ ^ /*J»
. r . J»

. n * *•• n *. ^^K^^^HUKW^ A » x O 7i:ri:i:i:7:i:7:7:r**rzj:7
. zzzz z r - i c•> * -* * -*i •* » >-* * -a-si-o-oj-a-j*- ^ 9 V. ? J ? ? £

.* *.!i ? " ?. 9

9. 8 8 8 2 2 ? g 9. 2 g - zrz£Krx3 tar . a : x a c a c x n i

J wn ^ o - - o o — - • . * r o - •- » -*—«--Oii.-•-*- * <nroforocr>o-*c*>-*-*-*— »

_ - f* » - *

. „

_.J - u J C . x x x a : x u . x x - x x or oi. * x x a

o x ^ c x x ' x ' x x V x

_
—_ . _.fvj_-_ * _-_*_ *

_ . _* _._*_._ •rororo— •—ro- * —rororororvjroro- J -*'o
—- •r o r o i- o ooo^oooo-o o i**rot>oc>rvit>oo* > ' « ^ 4-~J>'C>4>'4>J>'J>'4'-** - 4 - r o 4 s * * ~ ** •* * «~ « - **

-

CA >Tabl e 1 P.3 5

33 2 30 3 33 4 30 5 30 6 33 7 30 3 30 9 31 0 31 1 31 2 31 3 31 4 31 5 316 31 7 31 3 31 9 32 3 32 1 32 2 32 3 32 4 32 5 32 6 32 7

" ! ".9 14 2 14 2 14 2

32

. 46

. 0 1 0 1 .1 9 1 .1 9 1 .1 9 1 16 4 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1 C 1 042 5 C69 6 1 0 5 1 0 5 0 3 3 3 0 0 5 0 3 3 3 3 1 1 1 3 0 5 3 0 ! 3 0 '. 3 0 ! 3 0 ! 3 0 ! 3 0 ! 3 0 ! 3 0 ! 3 0 ! 3 0 ' 3 0 3 0 3 0 3 0 3 0 3 0 3 0 3 0 1 1 2 1 0

0 I 1 0 0 1 1 0 2 8
> 0
> 0
> 0
> 0
> 0 > 0 S 0 5 0 i 0 5 0

> 0 5 0 5 0 5 0 5 0 5 0 5 0 5 0 5 0 5 4 5 6 0

0 16

. 0 16

. 16

. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 37 2 7 739 1
739 1 662 4

.721 7 .117 5 0 0 1 . 0 1 . 2 . 0 0 0 0 0 0 0 0 0 0 0 0 0

. 0 0 0 0 0 0 4 3 00 0
00 0 15 4

0 0 • • • • • • UNKNOW N UNKNOW N • • • •• • METHY L NAPHTHALEN

E • • • UNKNOW N •• • METHY L NAPHTHALEN

E N-TRIOECAN

E

• • • • • « • • • *** *• • • • * ** • •* • •* • • * • • • • • • • • • • • • • • • • *• • • • • »• • • • • UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N UNKNOW N METHANO L ETHAKO L •• • • • • • • • • • • • • • •• • «• • •• • •• « *• • •• • •• • •• * •• * •• • • • • •• * • • • • • • C13-2 3 7 ? 7 •>

7 7 7 7 7 7 ? 7 7 7 7 ->

ll-.l-