1

LEVL 'J AD

0 PHYSICAL AND CHEMICAL CHARACTERIZATIONOF MILITARY SMOKES

Part II - Fog Oils and Oil Fogs

Final Report

gBy

Sidney KatzAlan SnelsonRonald Butler

" -. Raleigh Farlow #Roger Welker

Stephen Mainer -

!. .June 1980

Supported by

US Army Medical Research and Development CommandFort Detrick, Frederick, Maryland 21701

Contract No. DAMDl7-78-C-8085

lIT Research Institute10 West 35th Street

Chicago, Illinois 60616

Contract Officer's Technical Representative: J. J. Barkley, Jr.US Army Medical Bioengineering Research and Development Laboratory

Fort Detrick, Frederick, Maryland 21701

>:3 Approved for public release; distribution unlimited

The findings in this report are not to be construed as an officialDepartment of the A-iy position unless so designated by other

LU1i authorized documents.

0 22,0 24 ! 2 9

EXECUTIVE SUWARY

The present inventory of military obscuration smokes includes the oil

fogs generated by the thermal evaporation and condensat4cn of SGF-2 hydro-

carbon oils. The field operation employs a gasoline powered M3-A3 fog gen-

erator which uses about 1 gallon of oil per minute to generate a dense aerosol

cloud. The present study has been concerned with the characterization of the

fog oil and the product fogs to determine the particle size and physical sta-

bility of the product fog and also to identify both oil and oil fog compo-

sition of possible biological significance.

Fog oils from three different sources and three fog generators were used

in the tests. Oil fogs were generated with all nine oil-generator combina-

tions and samples were collected for particle size determination, aerosol

aging and chemical composition.

The physical appearances of the three oils varied considerably from clear

light amber to dark black-brown. All three oils contained very small traces

of copper and zinc at the parts per billion level, 40 ppb of zinc and 20-100

ppb of copper. The oil densities were in the 0.89-0.93 g-ml- range.

The oil fogs were generated using the recommended military procedure. A

fraction of the aerosol in the exhaust was collected for chemical analysis. A

second fraction was led into a 14 cu.m. (512 cf) cubical holding tank for

aging studies. The remainder of the aerosol was incinerated.

Varying the generators appeared to have little effect on either the phys-

ical or chemical properties of the aerosols; additionaly the physical proper-

ties of the aerosols were not greatly altered from one oil to the next. An

average initial mass diameter for all oil fogs was 1.16 pm with a standard de-

viation of 0.14 .im. The size distributions were all close to log normal and

the particle contert above the 10 im size was negligible. A number count ass-

essment indicated a bimodal distribution caused by a high level of very small

ii

i'lI

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I III. SUPPLEMENTARY NOTES

I9. KEY WORDS (Cont on tree oid. if nec..aamy and Identify by block n.mber)

smoke, screening smoke, obscuring smoke, oil fog, oil fog generation, fog oilcomposition, oil fog composition, oil fog stability, gas chromatography,I analysis, mass spectrometry analysis,

20. A.SRACT (Cauthwo m Fears* ftl if nmeeoay and idenity by block nmmbor)2'This report describes a study of U.S. Army SGF-2 Fog Oils and the

corresponding Oil Fogs using the Army M3-A3 Fog Generator to produce thefogs. The investigation included studies of the generation process, physicaland chemical analysis of the oils and their fogs, and observations of thefog stability and persistence. It was noted that fog oil compositions variedfrom source to source and that this was reflected in the fog compositions.The generators did not appear to contribute significantly to fog variations. -.7 .9J'

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UNCLASSIFIEDSECURITY CLASSIFICATION OF THIS PAGE{Ifheo Des EnIttld

Block 20 (cont.)

t, >The fog oils and the fogs contained almost equal amounts of aljPhatic andaromatic hydrocarbons with acids, alcohols and esters at the 1seV ee' levelor less and nitrogen derivatives in the parts per million range. Both theoils and their fogs proved to be too complex for complete chemical resolutionby gas chromatography and mass spectrometry. Of the several hundred identi-fiable chemical species, aliphatic hydrocarbons were in the CM - Q0 range.The observed aromatics included one- through four-membered ring structures

' "The fogs were examined to determine size and stability. Size determin-ations indicated a mass median diameter of 1.164 with a standard deviation

yZ., o i "n-thbasis of single particle counting, a bimodal distributionwas observed with high levels of submicron particles. The aerosols wererelatively stable; after aging for one hour:.typical systems showed median

particle size increases of the order of l2',eeWt with a decrease in themass of suspended particles of about 30pfe.

' 0t

UNCLASSIFIEDSICUPI'Y CLASSIFICATION O THIS PAGErtlen Dta Entereld)

U

[

particles in the low submicron region. Aerosol aging consistently involved

particle growth caused by collision, accompanied by a decrease in particle

j concentration, although median particle growths rarely exceeded 10% over a

one-hour interval.

Chemical analysis of the oil fogs was based on liquid and gas chroma-

tography fractionation and gas chromatography and mass spectrometry identifi-

cation. The gas chromatography traces consistently indicated the presence of

very large numbers of unresolved components with a relatively small number of

identifiable structures. Initially the oils and oil fogs were separated into

class fractions of aliphatics, aromatics, alcohols, acids and esters. The

aliphatic and aromatic fractions predominated in both the oils and the fogs,~at 95-99% of the total,with aromatics and aliphatics in near equal amounts.

In general, the aliphatic, aromatic and ester fractions of the oil fogs appear

to parallel the parent oil compositions, suggesting only moderate alteraticn

in the fog-forming processes, with however, a tendency toward a slightly in-

creased aromatic content in the oil fogs.

The aliphatic fractions contain identifiable straight and branched chain

saturated hydrocarbons in the C1 4-C2 2 range. The aromatic fractions were in

a similar molecular weight range but many more species were identified in-

cluding substituted benzenes, naphthalenes, anthracenes, phenanthrenes,

fluorenes, phenalenes, ionols and others. No cyclic structures beyond tetra-

cyclic groups were observed among the identifiable compounds.

A considerable number of nitrogen base materials was identified in the

oils and oil fogs, including quinoline, benzoquinoline and indole derivatives.

It should be noted that these nitrogen compounds are present at parts per mil-

lion levels.

It must again be stated that the several hundred species identified with

reasonable assurance are only a small fraction of the total number which were

resolved but not identified or which could not be detected against the mas-

sive background of unresolved material.

The high aromatics contents of both oils and oil foqs, approximately 50%

of the total, may represent a potential hazard.

lli

FOREWORD

This report on the physical and chemical characterization of oil fogs

and their precursor oils is the second in a series of investigations of mili-

tary smokes. This investigation was started on October 1, 1978 and the ex-

perimental work was completed on February 29, 1980.

Other studies in the series include the Physical and Chemical Character-

ization of Hexachloroethane Smokes, completed on May 31, 1979 and the Physical

and Chemical Characterization of White Phosphorus Smoke, presently in progress.

These studies are phases of a program titled "Physical and Chemical Character-

ization of Military Smokes," U.S. Army Contract No. DAMD-17-78-C-8085

Citation of trade names in this report does not constitute an official

Department of the Army endorsement or approval of the use of such items.

The close cooperation of Mr. Jesse J. Barkley, Jr. of the U.S. Army Med-

ical Bioengineering Research and Development Laboratory is gratefully acknow-

!edged.

V

TABLE OF CONTENTS

Pa~e

EXECUTIVE SUMMARY ......... .............................

FOREWORD ....... ... ................................. iv

LIST OF FIGURES ........ .. .............................. vi

LIST OF TABLES ....... ... ............................... vii

SYMBOLS AND ABBREVIATIONS ........ ......................... xii

1. INTRODUCTION ......... ........................... 1

2. CONCLUSIONS ......... ........................... 2

2.1 Fog Oil Compositions ....... .................... 22.2 Reaction Products ....... ...................... 2

3. OIL FOG GENERATION ....... ........................ 3

3.1 Fog Oils ................................ 33.2 Oil Fog Generators and Fog Generation. ............ 33.3 Experiment Designation ....... ................. 7

4. CHEMICAL ANALYSIS ...... ........................ .15

4.1 Discussion........ .. ... .. .. ... .. ... 154.2 Sample Preparation ......... . . ........... ....... 154.3 High Pressure Liquid Chromatography Class Fractionation. . 174.4 Chemical Separation, Liquid Chromatography - Heavy

Aromatics. ................................... 184.5 Chemical Separation - Nitrogen Bases .............. .204.6 High Resolution Gas Chromatography ...... ........... 204.7 Gel Permeation Chromatography ................... .234.8 Gas Chromatography/Mass Spectrometry .... ............ 24

5. RESULTS ........ .. ............................. 26

5.1 Class Fractionation ...... ................... 265.2 Gel Permeation Liquid Chromatography .... ............ 285.3 Metal Analysis 29.......................5.4 High Resolution Gas Chromatography. ............. 295.5 Gas Chromatography/Mass Spectrometry .... ............ 31

6. OIL FOG AEROSOL CHARACTERIZATION .................... .33

6.1 Procedure and Instrumentation .................... .33

7. RESULTS AND DISCUSSION ....... ...................... 38

APPENDIX A: Fog Oil Military Specification MIL-F-12070A .......... A-I

APPENDIX B: Gas Chromatography Data .... .................. .B-i

APPENDIX C: Mass Spectrometry Data ..... .................. .C-i

APPENDIX D: Aerosol Data from Experiments 3 through 12 ............ D-1

V

L ......____

LIST OF FIGURES

Number Page

1 Oil Fog Generator, Generator Controls ..... ............... 4

2 Oil Fog Generator, Fog Exhaust Ports ..... ............... 53 Oil Fog Generation ....... .. ........................ 84 Fog Generation and Sampling System .... ............... .11

5 Flow Chart of Chemical Analysis .... .................. .16

6 HPLC Class Fractionation of Fog Oil No. 3. ......... ... 27

7 Aerosol Sampling Line and Dilution System .... ............. 348 Histogram of Mass Median Particle Size Distribution ........... 41

9 Log Probability Plot for Experiment No. 6 .... ............. 4210 Log Probability Plot for Experiment No. 11 .... ............ 4311 Experiment No. 4. Oil Fog Particle Size (am) and Concentration

(TSP) Variation with Time ....... ..................... 4512 Experiment No. 4. Particle Number Concentration Change

vs. Time ....... ... ............................. 4813 Experiment No. 5 (C-2) Particle Size Distribution by ASAS

Aerosol Spectrometer ..... ....................... .4914 Experiment No. 11 (B-I, HT) Particle Size Distribution by ASAS

Aerosol Spectrometer ..... ....................... .50

D-1 Histogram of Mass Median Particle Size Distribution ExperimentNo. 3. 30 minutes after to .................... D-13

D-.2 Histogram of Mass Median Particle Size Distribution ExperimentNo. 4. 10 minutes after to ................. D-14

D-3 Histogram of Mass Median Particle Size Distribution ExperimentNo. 5. 13 minutes after to* ................. . D-15

D-4 Histogram of Mass Median Particle Size Distribution ExperimentNo. 6. 9 minutes after to . . . . . . . . . . . . . . . . . . . .D-16

D-5 Histogram of Mass Median Particle Size Distribution ExperimentNo. 7. 10 minutes after t. ....... .................... D-17

D-6 Histogram of Mass Median Particle Size Distribution ExperimentNo. 8. 12 minutes after to, ................. D-18 I

D-7 Histogram of Mass Median Particle Size Distribution ExperimentNo. 9. 9 minutes after to .................. D-19

vi

Mm

LIST OF FIGURES (CONT.)

Number Page

D-8 Histogram of Mass Median Particle Size Distribution ExperimentNo. 10. 8 minutes after to ..... .................... D-20

D-9 Histogram of Mass Median Particle Size Distribution ExperimentNo. 11. 8 minutes after to . ................... 0-21

D-10 Histogram of Mass Median Particle Size Distribution ExperimentNo. 12. 12 minutes after to ..... ................... D-22

vii

_ _ _ _ _-

LIST OF TABLES

Number

1 Physical and Chemical Requirements for Type SGF-2 Fog Oil ....... 6

2 SGF-2 Fog Oil Source Identification ..... ................ 6

3 M3A3 Oil Gog Generators ....... ...................... 6

4 Aerosol Generator Exhaust Temperatures. Thermocouple ProbeInserted About 6 in. Into Generator Exhaust ................ 12

5 Fog Oil Experiments ........ ........................ 14

6 Compositions of Standard Mixtures Used in GC InstrumentCalibration ......... ............................ 22

7 Gel Permeation Standard Test Mixture ..... ............... 24

8 Results of HPLC Class Fractionation ..... ................ 26

9 Results of Gel Permeation Liquid Chromatography ............. 23

10 Results of Metal Analysis ..... ..................... 29

11 Piezoelectric Counter Stages ...... ................... 35

12 ASAS Size Range Data ...... ....................... 37

13 Summary of Initial Particle Size and Concentration Measurements.

14 Dependence of TSP, dnm and n on Time t .... ............... 43

1 Calculated Values of Agglomeration Coefficient ... .......... 46

C-1 Oil No. 1, Aliphatic Fraction ...... ................... C-4

C-2 Oil No. 2, Aliphatic Fraction ...... ................... C-6

C-3 Oil No. 3, Aliphatic Fraction ...... ................... C-9

C-4 Oil No. 1, First Aromatic Fraction ..... ................ C-12

C-5 Oil No. 2, First Aromatic Fraction ..... ................ C-18

C-6 Oil No. 3, First Aromatic Fraction ..... ................ C-21

C-7 Oil No. 1, Middle Aromatic Fraction ................... .C-26

C-8 Oil No. 2, Middle Aromatic Fraction ................... .C-30C-9 Oil No. 3, Middle Aromatic Fraction ................... .C-34

C-IO Oil No. 1. Heavy Aromatic Fraction ..... ................ C-39

C-11 Oil Fog Run No. 2 (B-I), Heavy Aromatic Fraction ... ......... C-41 1C-12 Oil Fog Run No. 11 (B-1[HT]), Heavy Aromatic Fraction ......... C-45

C-13 Oi' No. 2, Heavy Aromatic Fraction ...... ................ C-47C-14 Oil Fog Run No. 4 (B-2), Heavy Aromatic Fractiot ............. C--50

C-15 Oil Fog Run No. 11 (B--I[HT]), Heaviest Aromatic Fraction ..... C-5I

viii I

IJLIST OF TABLES (CONT.)

j Number P ae

C-16 Oil No. 2, Nitrogen Bases Fraction ..... ................ .C-54

C-17 Oil Fog Run No. 9 (A-2), Nitrogen Bases Fraction ... ......... C-57

D-1 Experiment No. 3 .......... ......................... D-3

D-2 Experiment No. 4 .................................. D-4

D-3 Experiment No. 5 ....... .......................... D-5

D-4 Experiment No. 6 ....... .......................... D-6

D-5 Experiment No. 7 .................................. D-7

D-6 Experiment No. 8 .................................. D-8

D-7 Experiment No. 9 .................................. D-9

D-8 Experiment No. 10 ....... ......................... D-10D-9 Experiment No. 11 . . . . . . . . . . . . . . . . . . . . . . . . . D-11

D-10 Experiment No. 12 . . . . . . . . . . . . . . . . . . . . . . . . . D-12

ix

A.

GAS CHROMATOGRAPHY CHARTS

Chart 1. Gas Chromatography Standards .... ............... .B-4

Chart 2. Aliphatic Fraction: Oil No. 1 and CorrespondingOil Fogs ........ .. ........................ B-6

Chart 3. Aliphatic Fraction: Oil No. 2 and CorrespondingOil Fogs ........ ........................ .B-3

Chart 4. Aliphatic Fraction: Oil No. 3 and CorrespondingOil Fogs ......... ........................ B-10

Chart 5. First Aromatic Fraction: Oil No. I and CorrespondingOil Foos ........ ......................... B-12

Chart 6. First Aromatic Fraction: Oil No. 2 and CorrespondingOil Fogs ........ ........................ .B-14

Chart 7. First Aromatic Fraction: Oil No. 3 and CorrespondingOil Fogs ........ ......................... B-16

Chart 8. Middle Aromatic Fraction: Oil No. 1 and CorrespondingOil Fogs ........ ........................ .B-18

Chart 9. Middle Aromatic Fraction: Oil No. 2 and CorrespondingOil Fogs ........ ........................ .B-20

Chart 10. Middle Aromatic Fraction: Oil No. 3 and CorrespondingOil Fogs ........ ........................ .B-22

Chart 11. Heavy and Heaviest Aromatic Fraction,: Oil No. 1 andCorresponding Oil Fogs ..... ................. .B-24

Chart 12, Heavy and Heaviest Aromatic Fractions: Oil No. 2 andCorresponding Oil Fogs ..... ................. .B-26

Chart 13. Heavy and Heaviest Aromatic Fractions: Oil No. 3 andCorresponding Oil Fogs .... ................. ... 9-27

Chart 14. Ester Fraction: Oil No. 1 and Corresponding Oil Fogs. . B-28

Cha rt 15. Ester Fraction: Oil No. 2 and Corresponding Oil Fogs. B-29

Chart 16. Ester Fraction: Oil No. 3 and Corresponding Oil Fogs. . B-30

Chart 17. Alcohol Fraction: Oil No. 1 and Corresponding Oil Foys . B-31

Chart 18. Alcohol Fraction: Oil No. 2 and Corresponding Oil Fogs, B-32

Chart 19. Alcohol Fraction: Oil No. 3 and Corresponding Oil Fogs. B-33

Chart 20. Acid Fraction: Oil No. I and Corresponding Oil Fogs . . B-34

Chart 21. Acid Fraction: Oil No. 2 and Corresponding Oil Fogs . . 3-35

Chart 22. Acid Fraction: Oil No. 3 and Corresponding Oil Fogs . . B-36

Chart 23. Nitrogen Base Fraction: Oil No. 2 and CorrespondingOil Fogs ........ ......................... B-38

Chart 24. Aliphatic Fraction: Oil No. 1, Normal Run, HighTemperature Run ...... ..................... ..- 40

',

GAS CHROMATOGRAPHY CHARTS (CONT.)

PageChart 25. First Aromatic Fraction: Oil No. 1, Normal Run, High

Temperature Run ......... ...................... B-42

Chart 26. Middle Aromatic Fraction: Oil No. 1, Normal Run, HighTemperature Run ......... ...................... B-44

Chart 27. Heavy Aromatic Fraction: Oil No. 1, Normal Run, HighTemperature Run ......... ...................... B-46

Chart 2e. Heaviest Aromatic Fraction: Oil No. 1, Normal Run, HighTemperature Run ......... ...................... B-48

Chart 29. Ester Fraction: Oil No. 1, Normal Run, HighTemperature Kun ......... ...................... B-49

Chart 30. Alcohol Fraction: Oil No. 1, Normal Run, HighTemperature Run . .... ......................... B-50

Chart 31. Acid Fraction: Oil No. 1, Normal Run, High Temperature Run B-51

xi

SYMBOLS AND ABBREVIATIONS

A Angstrom unit; (l0- ° meter)AREA area under a MS chart peakASAS Active Scattering Aerosol Spectrometerb constant term in the linear regression equation, y mt + bBTU British Thermal UnitBz benzenec intercept in aerosol growth correlation equationCi aerosol mass concentration in Stage i (P/Z counter)

C, 0C Celsius, degrees Celsius

cf cubic feetcm centimeter

cc cubic centimeter

di midrange diameter (ASAS particle counter)dm mass median diameter

DMS0 dimethyl sulfoxided particle diameter

Dp 50 50% cutoff size (diameter) for a P/Z counteret ac ethyl acetateF, -F Fahrenheit, degrees FahrenheitF/D flame ionization detection (GC) IA fi frequency shift for stage 1 (P/Z counter)ft foot 3g gramGC gas chromatography 3

GC/MS gas chromatograph-mass spectrometer

HPLC high pr ssure liquid chromatographhr hour.., internal diametercompound identification (MS) 3

xii

SYMBOLS AND ABBREVIATIONS (cont.)

in inches

K, K* particle agglomeration coefficient

ki P/Z counter stage constant

ln natural logarithm

m meterslope in linear regression equation Y = mt + b

Mi between-stage midpoint particle diameter (P/Z counter)

min minutes

ml milliliter

MS mass spectrometer

n aerosol number concentration per ml

N normal (concentration)

ni number of particles in the i th level

nm nanometer (10- 9 m)

n aerosol number concentration at to.

N/P nitrogen-phosphorus selective detection (GC)

PK # arbitrary peak number (MS)

ppb parts per billion

P/Z Piezo-electric Particle Cascade Impactor Counter

R correlation coefficient

sec second

SPEC spectrum number (MS)

t time in aerosol time history correlation

to time zero of an experimentAt sampling time (P/Z counter)

TIC total ion current (MS)

TICRAT percentage peak after correction for background (MS)

TSP total suspended particles

UV ultraviolet

V volume rate of air flow

X i mass fraction per stage (PZ counter)

Wm micrometer (10- 6 m)

1a. sensitivity factor for stage i (P/Z counter)

Ixiii

j1. INTRODUCTION

This investigation is a study of a number of military obscuration smokescurrently in the inventory of the U.S. Army. The investigation consisted of

the examination of the generating materials, the generating process and thephysical and chemical properties of the product smokes. Since physiological

consequences of smoke exposure are believed to be primarily a result of in-

halation, interest in the product smoke has been limited to particle sizes

below 10 pm.

Lprt 1 of this series, dated January 1, 1980,1 was a report on smokes pro-

duced by the Army HC smoke generator in a process involving the thermal inter-

action of hexachloroethane, zinc oxide and aluminum.

The present report, Part 2 of the series, describes an investigation of

oil fogs.

Oil fogs are formed by the thermal evaporation of hydrocarbon oils andthe subsequent condensation of the vapor to form a fog. Physical character-

ization of the fog involved its generation followed by successive sampling to

determine the size distribution and the number concentration of the smoke par-

ticles as well as the effects of aging, concentration and variations in the

generation process. Chemical studies were used in attempts to identify repre-

sentative members of the vast number of constituents of both the oil and the

fog and where possible, to identify possible hazardous materials. As noted

above, sampling was limited to particle sizes below 10 -pm.

The standard oil fog generator yields a very large volume of oil fog.

Initial experiments were conducted in a remote rural area. Several problems

arose including the severe environmental consequences of the generation even

far from the urban environment. In addition, the heated vapor and smoke rose

rapidly in a manner that made sampling very difficult and almost certainly

L . ..... 1

of dubious reproducibility. It was therefore decided to conduct all subse-

quent experiments in a controllable laboratory environment.

2. CONCLUSIONS

2.1 Fog Oil Compositions

The fog oils were all almost pure hydrocarbons, predominantly mixtures

of aliphatic and aromatic components in almost equal amounts with small amounts

of alcohols, organic acids and esters and very small traces of organic nitrogenderivatives. Aliphatic hydrocarbons were in the C12-C2 2 range and aromatics

consisted of one- through four-member rings, also in the C1 2-C22 range. All

oils contained traces of copper and zinc, the former near 40 ppb and the lat-

ter varying between 20 and 100 ppb.

The oils were physically distinct ranging from light yellow to almost fblack with densities between 0.89 and 0.93 g ml.

2.2 Reaction Products

The generated aerosols were very similar in composition to their parent

oils and indicated very little dependence on the different generators.

The aerosols from all sources and generators were closely similar on a

weight distribution basis with a log normal distribution and a mass mean size

of 1.16 Lim and a standard deviation of 0.14 pm. Over a pe'iod of about onehour, the median sizes increased very slightly, ranging from virtually no

increase to as much as 50%, and averaging about 12%.

On a number basis, the size distributions were bimodal with very large

numbers of particles in the submicron range below 0.08 jim, the lower limit

of the counter. These large numbers represented a very small fraction of the

total aerosol weight.

F

~I

3. OIL FOG GENERATION

3.1 Fo Oils

The fog oils used in this study are designated as "petroleum oil for use

in mechanical smoke generators" of the class Type SGF-2. Thev are described

in Military Specification MIL-F-12070A*. The chemical and physical standards

are given in Table 1.

Three lots of foq oil were used in the investiqation. Each lot was de-

livered in two steel drums. They were identified initially as SGF-No, 2 Lots

No. 1, 2 and 3. Initially each drum in a lot was characterized by the desig-

nation 1-1, 1-2, etc., but this differentiation was discontinued when the oils

from each source were found to be indistinguishable in all tests. The oils

are identified by producer and identification code in Table 2.

3.2 Oil Fog Generators and Fog Generation

Three U.S. Army M3A3 foq generators were supplied to IIT Research Insti-

tute. They are listed and described by serial number in Table 3. Each gen-.

erator was equipped with a tool kit and spare parts, principally replacement

butterfly valves. Figure 1 shows the fog generator and Figure 2 shows the

generator controls and the three exhaust nozzles from which the smokeemerges.

The M3A3 smoke generator consists of a small gasoline powered ram jet

engine. The fog oil is metered into the exhaust manifold of this engine at a

predetermined rate partially controlled by a manually operated valve. The

heat of the exhaust vaporizes the oil and ejects it through the three nozzles

shown in Figure 2 into the atmosphere where rapid condensation of the oil to

dense fog occurs. The U.S. Army demonstrated the operation of the smoke gen-

erator to IITRI personnel and provided copies of the "Operator and Organiza-

tional Maintenance Manual Generator, Smoke, Mechanical, Pulse Jet, M3A3,'

*Appendix 1. Fog Oil Military Specifications

3

--

PIP pWR 1. 'PP I

Figure 1. Army M3A3 Oil Fog Generator

II

Fi-iure 2. Oil Fog GeneratorGenerator Controls (above)Fo Exhaust Ports (below)

I

...4. . . . . .. . . .....--1 ... _ . -

TABLE 1. PHYSICAL AND CHEMICAL REQUIREMENTS FOR

TYPE SGF-2 FOG OIL

Property Maximum Minimum

Flash point, "F (°C) - 320 (160)

Viscosity, Saybolt Universal,at IO0°F (38°C), sec. 110 I00

Carbon residue, Conradson, % 0.1 -

Neutralization number 0.1

Pour point, 'F (°C) -40 (-40)

TABLE 2. SGF-2 FOG OIL SOURCE IDENTIFICATION

IITRI Lot No. 1 2 3

Source Delta Petroleum Co. Witco Chemical Co. Phipps Product Corp.

Source Lot No. - DLA 600-78-C1088 DLA 800-78-C-1087

Batch 3580 8050 78208

Date May 1978 May 1978 May 1978

iTABLE 3. M3A3 OIL FOG GENERATORS

IITRI Identification Government Identity Number iGenerator Serial No. Tag Serial No.

A US 1500 4 M3A3-1722 EUR 800 535 1B US 1500 5 M3A3-1305 EUR 800 364 1C US 1500 6 M3A3-1278 EUR 800 472

64 ____ _____

Department of the Army Technical Manual, TM-3-1040-202-12. Except where other-

wise noted in this report, the f13A3 generators were operated in the desionated"normal mode", usinq about 40 gallons of fog oil and 3 gallons of qasoline pFr

lour.

3.3 Experiment Designation

The experimental program required a comparison of the oil fogs Formed by

each oil in conjunction with each generator. Thus a minimum of 9 cil-foo gen-

erator combinations were required. Each run was designated by a sequential

ron number and was further identified by the oil batch number and the gener-

ator letter. For example, the run designated No. 1 (B-2) was the first run of

the series, and involved Fog Oil No. 2 and Generator B.

Oil Fog Generation Field Test

Preliminary field tests were conducted at IIT Research Institute's KinQs-

bury field" facility to evaluate equipment performance, to study the smoke

cloud and, hopefully, to obtain some preliminary data.

The field tests were made using Fog Oil Lot No. I and Generator B. The

first test was on December 18, 1979, a winter day with overcast sky and 2-C

temnerature. The cloud was very large but it lifted rapidly and attempts to

savple at a station about 200 yards downwind failed.

The followinq day the test was repeated and the cloud was samplej with

a Roycn notical particle counter and an Anderson impactor. A siall amount of

fci material was detected but nothing larger. It was evident that the

particle content of the foq in the 10 cm and larger range was negligible.

The oil fog cloud formed during the December IS field test, is shown in

Fiqut& ".

Oil FogDispersed

It was not considered feasible to conduct the experimental program in

ofen terrain because of the instability of the field environment, both for

f , geeneration and sampling. The large quantities of fog produced in the

* ield mP ,hasized the maonitude of the fog disposal problem that would he en-

-r'j,ntre in the laboratory.

7

'a

1I

- - - IFigure 3 Oil Foq (enerat'on I

2 1

U

Under normal operatinu conditions the M3A3 generator converts abo.;t 2/

-allon of oil foq per, minute into a highly visible dense white cloud. Tr.

* rder to sample a typical foo for analytical purposes, it was deemed desirable

tC' allow the smoke qenerators to attain thermal equilibrium. Preliminary

tests in which a thermocouple was inserted a distance of about 8 in. into one

of the fog qeneratinq nozzles indicated steady temperature conditions after

approximately 10 minutes of operation. Assuming that an analytical samplino

period of 10 to 15 minutes was necessar-, a minimum of about 13 gallons of oil

would be conve,,ted to foq and would have to be disposed of in an acceptable

manner.

The oil fog disposal problem was the subject of a detailed study. The

preliminary particle size measurements made on the oil fog generated at the

K'inq.bury Ordnance facility indicated a mean particle size considerably less

than q i:m and theorctical considerations led to similar conclusions.

ihe possibility that a filter/impaction collection technique miqht he

suitable was considered even though the sheer volume of material inviolved

riqht p,'esent a problem. Discussions with several industrial suppliers cf

particle 3ir filtration systems indicated that this approach might be viable.

.Arran qements were made to obtain on loan, pending proof of satisfactory oper-

ation, of a large capacity industrial Balston Filter !-Init. A few short dur-

ation trial runs with this unit connected to the smoke generator showed less

than satisfactory operation and after a total runnin, time of less than 5

minutes the filter units were pluqged, restricting air flow throuah the unit

almost completely.

In light of the above experience the filtering concept was abandoned and

a decision was made to burn off the excess oil fog in a large incinerator

rated at 7 x 10 ' BTU/hr situated in an open area 30 melers from the aerosol

chan,bet "laboratory. The room air conditioning ductino system was modified to

car' thu oil fog from the aenerator to the incinerator. Some prel irnar.y

tpqq involvir abcut minutes of generator operation inr;;icated that the in-

cinreraotr was able to burn off. completely the smoke generator's outol;t.

'nft-wrtunately, on the first full scale test an explosion occurred causion

,ao dnaqe to the ductinq system and blowers. Thp cause nf th ex!uOnscn

was not ascertained oith certainty but considerable fog was obzerved swirling

around the heated parts of the smoke generator and it seemed possible that the

exhaust blower capacity may have been inadequate for its removal, anti thaT the

ignition might have started in this way. It was established that ignition had

not occurred at the incinerator with the flawe front travelling back down the

ducting to the generator area.

Although the incineration approach itself was feasible,modification of

the building's air conditioning system to increase its blower capacity to en-

sure that no oil fog would contact the hot parts of the smoke generator would

have been a substantial undertaking. Based on cost and safety considerations

it was deemed preferable to move the smoke generator with its own blower and

ducting system as close to the incinerator as possible. A blower of 450 cu

ft min -' was found adequate to handle the generator's smoke output. This ap-

proach was implemented successfully. A schematic drawing of the arrangement

is shown in Figure 4.

Fog Collection for Anajlytical Procedures

a. General

With the arrangement for disposal of the oi' fog aerosol from the M3A3

generator resolved, it was possible to run the generators for an indefinite

period of time. To collect oil fog samples for the chemical and physical

characterization of the aerosol, the generators were run under standard or).ar-

atino conditions until steady temperature conditions were attained in the ex-

haL.st manifold of the generators as indicated by a thermocouplc insertea into

one of the three fog exhaust nozzles. A total of twelve rims were made. In

all experiments but ore, Experiment il, thermal equilibrium was attained in

less than 10 minutes with a mean operating temperature of 375°C. All teinp-

eratures are included in the tabulation of all runs in Tab)le 4.

In Experiment No. 11, a generator was deliberately run under conditions

designed to increase the normal operating temperature. This was done with

the object of magnifying any effects thaT the generator operating temperature

might have on oil degradation or aerosol size characteristics. The increase

in operating temperature was achieved by reducing the rate of fog oil feed to

110 1

c 0c

LnI

0~ z

00~

00

LLC 7 o0 z

ac 4-

00ER0)0

020

LL CL-

W

TABLE 4. AEROSOL GENERATOR EXHAUST TEMPERATURES. THERMOCOUPLEPROBE INSERTED ABOUT 6 IN INTO GENERATOR EXHAUST

Experiment Generater Time to Average

No. - Oil equilibrium, min. temperature, C

1 B-2 712 350

2 E-1 8 375

3 B-3 9 360

4 B-2 6 359

5 C-2 d 390

6 C-I 3 371

7 C-3 4 37C

8 A-3 6 399

9 A-2 6 380

10 A-1 6 366

11* B-I 5 572

12 B-i 5 410

High temperature experiment

12

the generator, and reducing the gasoline supply to the ram jet motor. The re-

sulting operating temperature was 5720C, almost 2(0 higher than the average

of the other 11 "normal" runs.

b. Sampling for Chemical Analysis

To obtain analytical samples, the oil fog was collected using a simple

impaction filter technique. A "high volume" filter pump (approximately 50 cu

ft min -) was used to draw a sample of oil fog from the manifold on the low

pressure side of the blower connected to the incinerator, (Fig. 4) through a

5 liter glass flask packed with glass wool. To keep the collection flask cool

it was set in a bucket filled with ice. With this arranciement, between 50 and

100 cm3 of the oil was collected in 10 minutes. The oil in the flask was then

subjected to the analytical procedures to be described shortly.

c. Sampling for Aerosol Analyses

The original intent in the program was to use IITRI's 6 meter (18 ft)

diameter spherical chamber to contain the oil fog aerosol for particle size

measurements. However, the arrangements necessary for disposal of the excess

oil fog precluded use of this facility. Instead a "mobile" aerosol holding

tank was constructed, consisting essentially of a 2 meter cubic wooden struc-

ture mounted on casters. This holding tank was moved close to the smoke gen-

erator and was connected to the up stream side of the blower unit for collec--

tion of the aerosol sample via a valved duct of 5 cm diameter. A small suc-

tion blower attached to the chamber provided the necessary negative pressure

required for sample collection. As in sample collection for chemical anal-

ysis, aerosol was sampled after attainment of thermal equilibrium in the

smoke generator exhaust manifold. An aerosol sample was collected by orening

the samplinq valve for about 1 sec. The holding tank was then disconnected

from the generator and was moved into an adjacent building for aerosol Dar-

ticle size analyses. Elapsed time from sample collection to the start of

aerosol measurement was approximately 3 minutes.

Table 5 is a generator-fog oil matrix correlating the experiments with

the corresponding M3A3 generator and fog oil.

13

TABLE 5. FOG OIL EXPERIMENTS

M3A3 ____Fog Oil ___

Generator 12

A #i10 #9 #8

B #2; #11; #12 #1, #4 #31

C #6 #5 #7

14I

4. CHEMICAL ANALYSIS

4.1 Discussion

The chemical analysis of natural hydrocarbn oils is a problem of extreme

complexity. Even relatively simple oil fractions may be composed of many

thousands of species. In the present investigation it was of interest to iden-

tify potentially toxic or hazardous constituents. These might be, for example,

polycyclic aromatic hydrocarbons or their derivatives.

The analytical procedures were similar for both the oils and their deriv-ative fogs. The methods used are described as follows:

1) separate the oil or oil fog sample into classes using eitherchemical separation or liquid chromatography or a combinationof both,

2) analyze the resulting fractions using high resolution gaschromatography,

3) analyze selected fractions by gas chromatography/mass spec-trometry, and

4) subject the oils and fogs to gel permeation liquid chroma-tography to determine size distribution.

This method is summarized as a flow chart in Figure 5. The details of the

chemical analysis are presented in the following sections.

4.2 Sample Preparation

The oils were withdrawn from their metal containers and were delivered

to the laboratory with no prior preparation.

The oil fogs were received for analysis as liquid condensates on glass

wool in 5 liter glass round bottom flasks. Each oil fog was separated fromthe glass wool by three successive extractions with 300 ml aliquots of methylene

dichloride, CH2C12. The extracts were combined and the solvents were removed

with a rotary evaporator. Prior to liquid chromatographic fractionation theoils and oil fogs were filtered using a Millipore Corporation filter with

0.2 um pore size.

15

w 0 0

US C

,'.-i 0 LLL

ILLI II 1

.0 ExU

4.3 High Pressure Liquid Chromatography Class Fractionation

Compound class fractionation was performed by normal phase high pressure

liquid chromatography (HPLC). This was accomplished by utilizing the Waters

Associates Liquid Chromatograph, described in Table 6. The mobile phase

flow rate was 2 ml/min at ambient temperature. The mobile phase, Burdick

and Jackson solvent, was initially n-hexane but after 8 minutes a linear

gradient was established with the second solvent consisting of ethyl acetate/

methanol/benzene in the volume ratio 50/25/25. The gradient was set so as to

achieve 80% of the second solvent in I hour, however, after 31.5 minutes the

gradient was interrupted and the mobile phase was switched to 100% of the

second solvent.

For each run 200 vil of oil or oil fog were injected into the HPLC using

a 250 ujl Precision Sampling Pressure Lock syringe. 2 Iil fractions of the

elutant were continually collected up to a total of 30 fractions. The 31st

fraction was collected until it totalled 20 ml. At that point each run was

terminated. During the run, the elutant was monitored by both the absorbance

detector (set at 254 rim) and the refractometer The detectors were connected

in series, with the absorbance detector being the first to "see" the elutant.

Using this system the chemical classes were separated and given initial

classification as follows:

Fraction Class

4-6 Aliphatic

4-10 Aromatic

19-22 Ester

26-28 Alcohol

31 AcidIAfter fractionation and collection, each fraction was blown down with

J a nitrogen stream until 3ll of the solvent was evaporated. At this point the

fractions were weighed using the following method. First, the fractions were

examined visually and those containing the largest amolunts of material were

17

TABLE 6. HIGH PRESSURE LIQUID CHROMATOGRAPH (hPLC)

Units: Waters Associates Model 244 HP Liquid Chromatograph.

Modules: Model 6000A Solvent Delivery System (2 units).

Model 660 Solvent Programmer.

Model 440 Absorbance Detector.

Model R401 Differential Refractometer.

Columns: 25 gm x 6.2 mm I.)., 10 pm particle size and60 A pore size Lichtrosorb column.

4I

II

I

diluted with 1.0 ml of CH2 C12. The remaining fractions were diluted with

I00 1I of CH2C12. Second, weighing pans were constructed cut of one inch

square sections of aluminum foil The pans were rinsed with CH2C12 and dried

thoroughly before use. Third, a pan was selected and weighed on a Mettler

balance. Immediately after weighing, one quarter of the volume (either 25 or

250 wl) of the fraction to be weighed was removed with a Hamilton syriny

and placed in the pan. The CH2C12 was allowed to evaporate, the pan was

weighed again and the weight was determined by differences. Lastly, the

measured weight was multiplied by four to give the total weight of the fraction.

In Fractions 4, 5 and 6 both the aliphatic and aromatic components eluted.

In order to separate the two classes it was necessary to repeat the separation.

To accomplish this the liquid chromatograph was set up as before with the

following two exceptions: First, no gradient was necessary and the separation

was accomplished isocratically using hexane as the mobile phase. Second, the

chromatograph was operated in the recycle mode in order to pass the components

through the column as many times as necessary to achieve separation. For

these runs 20-iPl volumes were injected using a 100 pl Precision Sampling syringe.

In the case of Fraction 6, not enough material was present to oroviae for a

20 vil injection so the fraction was diluted to 20 -Il using hexane. To achieve

separation of the aliphatic and aromatic components it was never necessary

to recycle the samples through the column more than twice. Once the components

were deemed separated they were collected, blown down, ana weighed as described

previously. The aliphatic and aromatic components of Fractions 4-6 were

designated -A and -B, respectively (e.g., 4-A, 4-B).

4.4 Chemical Separation, Liquid Chromatography - Heavy Aromatics

The liquid chromatography technique described previously did not yield

a large enough quantity of heavy aromatics to provide for good chemical char-

acterization. To correct this situation it was necessary to extract the

aromatics chemically from a comparatively large volume of oii or condensed

oil fog, and then separate the heavy aromatics using preparatcry liquid

chromatography.

To initiate the chemical separation, 30 ml of the oil or condensed oil

fog was dissolveo in 75 ml of n-pentane and then extracted three times with

19.ig

i.

105 ml portions of dimethyl sulfoxide. The dimethyl sulfoxide extracts were

then combined in a large separating funnel followed by the addition of 300 'Ti

of Millipore Milli-Q purified H20. 'he aromatics were then extracted twice

from the dimethyl sulfoxide/aqueous mixture using two 600 ml portions of n-

hexdne. The extracts were combined, concentrated to -5 ml using a rotary

evaporator, washed three times with 5 ml portions of Milli-Q water and dried

over anhydrous Na2SO4 . The resulting aromatic fraction was then blown down

with nitrogen to remove the solvent and filtered with a Millipore 0.2 Lm pore

filter. This extraction procedure would typically yield an aromatic extract

with a volume of 1 to 3 ml, the volume depending on both initial aromatic

content and extraction efficiency.

At this point, the extract was subjected to preparatory liquid chroma-

tography in which two late fractions were collected to obtain the heavy aro-

matics. For this purpose the Dupont Liquid Chromatograph described in

Table 7 was used. The chromatograph was run isocratically with n-hexane

as the mobile phase. The flow rate was 28 ml/min. For each run

400 ,il of extract was injected using a Precision Sampling 1.0 ml syringe.

Collection was begun 21 minutes into the run. At a, elapsed time of 27

minutes collection of the first fraction was terminated and collection of

the second fraction was initiated. Collection was stopped dt the end of the

run which was allowed to proceed until the detector trace showed a flat base-

line (usually about 60 min elapsed time). The collected frictions were

concentrated using a rotary evaporator and were then blown down with nitrogen

to evaporate the remaining solvent. Unlike previous fractions, these fractions

were not weighed as uncertainties in both extraction efficiency and reproduc-

ibility precluded meaningful quantitative significance. The first fraction

in each run was designated DMSO-i and the second fraction DMSO.2.

A mixture of benzene!napthalene/anthracene in the approximate ratio of j1:1:1 was injected into the chromatograph under the same conditions as the

oils and oil foqs. Anthracene was the last component to elute with a retention

time of 19.5 minutes. This indicated that fraction DMSG-! contained aromatics

with more than three rings with DMSO-? containing even larger ?romatic oroups.

I

I

TABLE 7. PREPARATORY LIQUID CHROMATOGRAPH

Unit: DuPont Model 830 Liquid Chromatograph.

Modules: 254 pm UV absorbance detector.

Columns: 50 cm x 20 mm i.d. packedwith 10 pm Spherosil. (2columns in series)

2i

4.5 Chemical Separation - Nitrogen Bases

Chemical separation of the nitrogen base- was achieved using the followtin;

extraction technique. 10 ml of oil or condense-d oil fog were dissolved in

250 ml of CHC1 3 and were extracted three times with 200 ml of 0.5 N HC1. The

extracts were combined and washed once with 250 ml of CHC13. The aqueous

acidic extracts were then made basic to pH 11 with 2.5 N NaOH and extracted

three times with 250 ml of CH2Cl2 . The combined extracts were dried over

Na.C0 3, filtered, concentrated with a rotary evaporator and finally the solvent

was evaporated using a stream of dry nitrogen. As with the heavy aromatics

these fractions were not weighed because of the many uncertainties in separation

reproducibility.

4.6 High Resolution Gas Chromatography

All fractions obtained from liquid chromatographic and chemical separations

were analyzed using high resolution capillary column gas chromatography. This

was accomplished with a Hewlett-Packard Model 5840 A chromatograph equipped

with a flame ionization detector and a capillary column carrier gas inlet

system described in Table 8. The inlet system was operated in thc "splities"

mode for greater sensitivity. In this mode the ,..issoived saMple is injected

into a hot (180 0C) injector block from which the column protrudes into a cool

(301C) column oven. After injection the components of the zan.ple with high

boiling points condense into the column while most of the s(,Ivert remains in

the vapor phase in the injector block. After a designated time peri d valves

are switched to allow the vaporized solvent to be flashed from the injector

into the atmosphere. During this time the carrier gas pressure is maintained

at the head of the column to insure that carrier gas flow down the column re-

mains continuous and stable. With this system virtually all of the smpe ends

up in the column while a large portion of the solvent is purged : way. The

splitless" system was particularly suitable for the oil/fog analbsis as all

of the components were high boiling oils.

The aromatic, aliphatic, nitrogen base and ester fractions were analyzed

under the conditions described in Table 8-A and the polar alcohols and acids

ds described in Table 8-B.

22

____ I

TABLE 8. HIGH RESOLUTION GAS CHROMATOGRAPHY UNITHEWLETT-PACKARD MODEL 5840 rAS CHROMATOGRAPH

A. Analytical Procedures for Aliphatics, Aromatics, Nitroaen Base and Ester Fractions

Column = 12 meter x 0.25 mm I.D. glass capillary column

coated with SE-30 (chrompak)

Carrier Flow = 1.0 ml/min (He)

Purge Flow = 30 ml/min (He)

Make-up Flow = 24 ml/min (He)

Injector Temp. = 180'C

Detector Temp. = 280'C

Oven Temp. = 30C for 7 min, program at 30°C/nin for 3 mins,then program at 6°C/min to 270°C, hold untilelapsed time reaches 60 mins.

Purge Initiation = 2 rins after injection

B. Analytical Procedures for Polar Alcohol and Acid Fractions

Column = 25 meter x 0.2 mm I.D. fused quartz capillarycolumn coated with Carbowax 20M (Hewlett-Packard)

Carrier Flow = 1.0 mi/mn (He)

Purge Flow = 30 ml/min (He)

Make-up Flow = 24 ml/min (He)

injector Temp. = 180C

Detector Temp. = 275°C

Oven Temp. = 300C for 7 mins, program at 30'. for 3 mins thenprogram at 5°C/min to 225°C, hold until elapsedtime reaches 60 mins.

Purge Initiation = 1 min after injection

Three standard mixtures were prepared for the purpose of determining

the retention times of characteristic compounds under the analytical conditions

employed. These standards also served the purpose of periodically checking

instrument performance and reporducibility. The compositions of these stan-

dards are listed in Table 9. The normal hydrocarbon standard was used in

conjunction with the SE-30 column while the alcohol and acid standards were

used with the Carbc,,ax 20M column.

Be-ore gas chromatographic anal., s, the ester fractions were combined

into one fraction as were the alcohol fractions. Althou,. both the esters

and alcohols were collected over several fractions, no resolmtion was observed

23

-• . . .. . .. .. . ... .. .. - - -. -

--

:-- "- " ' -+-

TABLE 9. COMPOSITIONS OF STANDARD MIXTURESUSED IN GC INSTRUMENT CALIBRATION

Standard Hydrocarbon Mixture in n-hexane

n-C10 H22 104 ,ig/mi

n-C1 21A 2 G10 1 ji g/mi

n-CiiHio104 jig/nil

n-C16H34103 pg/milni-C,91H38 78 uo/mi

n-C20H2 95 wg,'min-C 2 114 104 pg/nil11-C2 41Hs 100 1pg/mi

ri-C211 ,3100 lig/mi

n-C291i~o94 jig/rpl

n-(.--,HF,6101 pig/mnil

Standard Alcohol Mixture in HC.

C1 ,1123011 84.5 wg/m-il

C12H,50H 73.5 Ipg/mrI

C14H2 90H 74.0 jig/pil

C16V330H 89.5 ,ig/ml,C I8H 3 7 H 101.5 pig'n

Staiidard Acid Mixture in CHO0H

C7H1:3CO0H 71.5 11g/mi

C2-H1qCOOH 54.5 pig/ill

Ci1H2 ,C0OH 46.5 pjg/n!

CmIH 27CCOH 85.5 plg/ni

C1 5H3 1C00H 88.0 yIm

C 17 1-11 SC00O 107.'3 p:Q/rn

C1911, 9C0OH 70.0 j-g/mil

24

among fractions of the same class. Therefcre, the fractions were combined

to provide a larger amount of material for analysis.

Prior to injection, the fractions were diluted with solvent. The aliphatic

and aromatic fractions were diluted with n-hexane while the remaining fractions

were diluted with CH2C12. The fractions obtained from the liquid chromatographic

separations were diluted with either 50 or 100 il of solvent depending on the

amount of material collected in the fraction. Those fractions collected

during chemical separation required up to 3 nil of solvent as some of those

fractions contained considerably larger amounts of material.

Injection was accomplished using a 1.0 1fl Hamilton syringe. The size of

each ir;jection varied from 0.1 to 0.5 ll depending on the concentration of

material in the fraction being analyzed. In some cases two or three injec-

tions were necessary before the gas chromatogram was acceptable for visual

inspection and comparison with chromatograms of other oils and oil fogs. To

be acceptable, the chromatogram had to exhibit peaks well above the baseline

but not run off the top of the chart.

In addition to Flame ionization detection, the nitrogen bases were s:;h-

jected to GC analysis using a nitrogen/phosphous selective detector. Con-

version to the N/P mode required only replacement of the F/D collector witn

the N/P collector and an adjustment in the hydrogen and air flow rates. All

other run parameters were retained.

4.7 Gel Permeation Chromatography

Gel permeation chromatography was utilized to determine the size-molecular

weight distribution of the components making up the unfractionated oils and

oil fogs. The Waters Associates HPLC described in Table 6 was used for this

purpose. The chromatograph was fitted with aWaters 30 crux 0.78 cm I.D.

Stvraqel column with a particle size of 10 lim and a pore size of 100 A.

Analysis was performed isocratically with CH2 Ci2 used as the mobile phase.

Flow rate was 1.0 ml/min at ambient temperature. Prior to injection the

sample was filtered through the 0.2 lim filter previousiy described. A

Precision Sampling 1.0 jl syrince was used to inject from 0.1 to 0. 1, of

sample. The actual volume of injectinr, was adjusted so that the peak L'.V.

25

absorbance had a value between one and two absorbance units. Before each

analysis 10 il of a standard test mixture was injected. The standard mixt.ire

had the composition listed in Table1O and it also was used with CH-,Cl? as the

solvent phase.

TABLE 10. GEL PERMEATION STANDARD TEST MIXTURE

Component Molecular Weight Concentration

polyethylene 23 iauryl ether 1200 10 mc/ml

cholesteryl stearate 653 10 mg/ml

eicosanoic acid 313 ]0 mg/ml

cholesterol 386 10 mg/ml

ei cosane 285 10 mg/ml

decane 142 10 mg/ml

anthracene 178 1 rig/ml

4.8 Gas Chromatography/Mass Spectrometry

For GC/MS analysis of selected fractions, tie following system w as used.

A Varian NAT 311A mass spectrometer was used featurinq a double-focusina anal-

yzer system with Nier-Johnson geometry and a differentially ptimpe vacuum

system utilizing two high-speed turbomolecular pumps. For s'-mple introduction

the system used a Varian Aerograph Model 2740 gas chromatograph equipped with

a Hewlett-Packard Model 18835A injection system for splitless capillary column

analysis. The capillary column was directly interfaced with the mass spec-

trometer via a microneedle valve regulator and glass lined tube.

-ie ion source of the mass spectrometer consisted of a combined electron

impact/electron impact ionization detector for simultaneous registration of

electron impact mass spectra and total ion current (TiC) gas chromatograms.

The TIC signal was fed to an electronic integrator to monitor the progress of

the chromatogram in real time.

The capillary column and the gas chromatcg~aphic parameters were identical

to those used earlier in the high resoulition cis chromatographic analysis.

As in the earlier analysis, the column and Paraqveters we re matched to tho

particular class being analyzed.

?64

I

In a typical analysis run, the magnet of the mass spectrometer was set

to scan repetitively over a preset mass range. Data were acquired on a disk

by the data system and stored on magnetic tape for subsequent examination.

The raw GC/MS data was then routinely processed through a data-enhancement

algorithm. Program "Clean-up"* automatically extracted mass spectra free of

background and of contributions of unresolved (overlapping) GC peaks by the

application of a tabular peak-modeling technique to mass chromatograms in

the data file (Rindfleisch deconvolution). The resolved spectra were then

identified by means of a library-matching search algorithm. Compounds which

did not yield acceptable identifications in this way were sought manually

by comparison of their spectra with published compendia of mass spectral data.

* Developed at Stanford University Medical School and

modified at IITRI

27

5. RESULTS

5.1 Class Fractionation

A representation of a typical HPLC class fractionatior run is shown inFigure 6. The severe overlap of the aromatic and aliphatic fractions is quite

clear and demonstrates the need of the recycling technique used to separate

these two classes. For completeness, the mobile phase gradient profile is

presented at the top of the page.

The complete results of the HPLC class fractionation are presented in

Table 11. The calculated percentages are based on the total amount of materialeluted from the HPLC. For Oil #2, three identical runs were performed todetermine the reproducibility. From these three runs the means arnd standard

deviations were calculated. The error quoted in Table 11 represents ore

TABLE !I. RESULTS OF HPLC CLASS FRACTIONATION

Sample % Aliphatics % Aromatics % Esters Alcohols .Acds

Oil #1 58.2 40.0 0.7 1.1 0.0Run #10 (I-A) 55.1 42.0 1.1 1.2 1.6Run #2 (I-B) 59.7 37.5 0.9 1.0 0.Run 46 (1-C) 57.8 39.4 1.0 1.3 0.6Run #11 (1-BHT) 57.7 39.8 0.9 1.1 0.4

Oil #2 42.7 ± 5.7 50.0 ± 6.4 4.1 ± 0.7 2.7 +_ 1.2 0.5 ± 0.1Run #9 (2-A) 43.1 52.5 2.,, 1.3 0.4Run #4 (2-B) 54.6 41.0 2.9 1.3 0.3Run #5 (2-C) 44.4 50.9 3.3 1.0 0.4

Oil #3 54.1 43.5 0.9 0.7 0.7Run #8 (3-A) 42.4 55.2 1.4 0.6Run #3 (3-B) 47.5 50.4 1.0 0,6 0.6Run 7 (3-C) 54.5 43.8 1.1 0.3 0.2

28 -.

00

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standard deviation. The primary source of error in the aliphatic and dror,atics

fractions was probably the failure to separate absolutely the two classes.

Although the three oils vary in composition, the production of the fogs

seemed to have very little significance on the oils'class compositions.

5.2 Gel Permeation Liquid Chromatography

The results of the gel permeation chromatography are presented in Table 12.

The results are presented in two ways, as a ratio between absorbance units

and refractive index units and as the retention time of the peak maximum

using the refractive index detector. The data presented as a ratio give

an indication of the relative quantities of U.V. absorbing materials (aromaticsi

in the oils and fogs. An increase in the value of the ratio could indicate a

real increase in the relative concentration of aromatics or it could indicate

an increase in the sizes of the aromatics or both. The peak maximum column

is an indication of the average size of the compounds contained in the oils.

For comparison, the retention times of decane and eicosane are presented at

the bottom of the table. As with the HPLC fractionation, Oil #2 was run

TABLE 12. RESULTS OF GEL PERMEATION LI.!UID CHROMATOGRAPHY

Absorbance/Refractive Peak Maximum forIndex Units Refractive Index

Sample (minutes,

Oil #1 1.96 ± 0.09 x 10" 7.7Run #10 (I-A) 2.26 x 10" 7.7Run #2 (l-B) 2.31 x 10" 7.8!run E (1-C) 2.33 x 10" 7.8

Run 411 (1-BHT) 7.54 x 10" 7.9

Gil 2 3.88 ± 0.02 x 10" 8.4 t 0.1Run 49 (2-A) 3.95 x 10" 3.3Run #4 (2-B) 4.08 x 10" 8.3Run 4 (2-C) 3.94 x I0 8.4 1

Oil e3 2.55 x 10" 3.!Run *8 (3-A) 3.15 x 10" 3.1Run '3 (3-A) 2 97 x 10" 9.i

Run fi7 (3-C) 2.98 x 10' 8.1

- Eicosane M.235T 7.6Decane (M.W.142) 9.0

30

I T

three times to determine the reproducibility with the quoted errcr being

equal to one standard deviation.

All of the oil fog runs show a slight increase in the ratio column over

the values for the corresponding oils with the exception of run #11 which

shows a dramatic increase. These increases are not reflected in the peak

maximum column.

5.3 Metal Analysis

Trace metals in the oils were determined by atomic absorption using a

Perkin Elmer Model 403 Spectrometer. The analysis is summarized in Table 13

which includes the detection limits for each metal.

TABLE 13. RESULTS OF METAL ANALYSIS

Oil #1 Oil #2 Oil #3 Detection Limit(PPB) (PPB) (PPB) (PPB)

Cd ND ND NO 9Cr ND ND ND 9Co ND ND ND 9Cu 46 (± 25%) 46 48Pb ND NO ND 93Mn ND ND ND 9Mo ND ND ND 95Ni ND ND ND 9Sr ND ND ND 9Sn ND ND ND 93V ND ND ND 95Zn 55 (± 25%) 19 104As ND ND ND 95Hg ND ND ND 2

ND- Not Detected

5.4 High Resolution Gas Chromatography

The gas chromatographic data are presented in Appendix B in Charts No.

2-31. Charts No. 2-23 present gas chromatograms of each class fraction of

each oil along with those of the corresponding oil foas. In most cases three

oil fog chromatograms appear with each oil chromatogram, corresponding to

the three generators used in the study. In the case of the heavy aromatics,

heaviest aromatics, and' nitrogen bases, only one oil fog chromatograin appears

31

with that of the oil. This results from the fact that the chemical extraction

techniques were applied to only one fog from each oil. In the case of the

heavy and heaviest aromatics, the fog from generator B was used and in the

case of the nitrogen bases only the fog from generator A was used. For the

nitrogen bases fraction only the chromatogram from Oil #2 is included in the

data as it was the only one of the three oils to contain enough nitrogen bases

to produce a meaningful chromatogram.

The second section of Appendix B, Charts No. 24 to 31, contains chroma-

tograms of oil fogs obtained from high temperature Run #11. Along with each

of these chromatograms is a chromatogram obtained from a normnal run (#2) and

a chromatogram obtained from the starting oil. No nitrogen bases fractionswere included in the section because of the lack of material (condensed oil

fog) to make the necessary chemical extraction.

Preceding the two sections is Chart No. 1 containing three typical

qualitative calibration runs, one for each of the calibration standards

described previously.

Portions of the class fractions from each oil and many of the oil fogs were

selected for gas chromatograph/massspectrometry (CC/MS) analysis. Where oossiblethe results were used to make positive identification of some of the larger

peaks present in the chromatograms. Complete matching of mass spectrometr 4 cdata to gas chromatographic data was not possible because of sample complexity

and some loss of resolution in the GC/MS interface. However, where identifi-

cation was positive it is indicated with alphabetically labelled peaks and

accompanying compound listings.

In the section of Appendix B containing the normal runs it is clear that

the chromatogram of the aliphatic, aromatic and ester fractions of the oil foqsdiffer very little if any from their corresponding oil chrometogr3ms. Thechromatograms of the alcohol and acid fractions of the oil fogs show somedifference from those of the starting oils, particularly in the early sectionof the chromatograms. To a large degree these differences are characte-izedby sharo individual peaks rather than a gross change in chromatographicpattern. Because of this it is probable that these peaks reoresent inuritiesconcentr3ted from the solvents used in separation rather than represerting

32

real differences. The acid and alcohol fractions were particularly vulnerable

to contamination because of their relatively small masses compared to the other

fractions. The nitrogen base fraction from the fop shows some difference

from the oil and can be presumed to be real.

In the section of Appendix B devoted to the high temperature run (li])

many differences appear in comparing the aromatic fractions to the corresponding

oil and the corresponding normal run (#2). These differences are almost

certainly real and may represent changes in concentrations, composition or

both.

5.5 Gas Chromatography/Mass Spectrometry

The 17 Tables presented in Appendix C are summaries of all the GC/MS

data for the aliphatic, aromatic and nitrogen bases fractions selected for

analysis. Several ester, alcohol and acid fractions were selected and

analyzed, but failed to provide useful data. The class identification of

these three groups must still be regarded as tentative.

The tables themselves contain an arbitrary peak number (PK#), an arbitrary

spectrum number (SPEC), tne compound identification (ID), the total ion

current (TIC) which is equivalent to peak height in gas chromatography, the

area under each peak in arbitrary units (AREA) (this coluinr is not always

included), and the percentage of each peak remaining after computer subtrac-

tion of the background (TICRAT). The last three columns (RELCON, RETIND, and

TYPE) were not used in this study.

The ID column contains both the formula and the compound name of peaks

which have been positively identified. Identifications enclosed in parenthesis

indicate tentative identificaticn. Those compounds identified as "silanated"

are the result of GC column bleed and are not components of the sample itself.

In some cases broad obvious peaks are missed by the clean-up program as they

fail to meet peak model criteria. These compounds identified as "silanated"

are noted at the end of each Table. Additional explanations of some of the

data are also noted at the ends of the corresponding Table.

33

L.. -.... A -

It should be stressed that the absence of any compound in the Tables lnc-s

not preclude its presence in the sample. Low concentrations or lack of GC

separation may mask a peak and make its identification impossible.

IIIIII

34 U

L._ _ _ __i__,_ _ _ _ _ _ _ _ _ _ _ __l__I

6. OIL FOG AEROSOL CHARACTERIZATION

6.1 Procedure and Instrumentation

Oil fog generation and collection were described in Section 3 with tab-

ulations of the experimental runs in Tables 4 and 5. During both Experiments

No. I and 2, aerosol collection was prolonged for 2 to 3 minutes, resulting

in an excessively dense aerosol in the holding chamber. Experiment No. 11

was run at a low oil feed rate to observe the effects of hiqh temperature,

on the chemical and physical characteristics of the aerosol.

The aerosol was drawn from the holding chamber with dilution at succe-;sive

intervals to observe particle size and concentration and the effects of aging

on the aerosols. The aerosol dilution system is shown in Figure 7. An

important function of this system was the reduction of the chamber aerosci

concentration to a level suitable for measurecnt by the two aerosol monitors.

A dilution of lO00(-riO):l was used with a total transit time from chamber to

detector of somewhat less than 1! min. A feature of the system is the use of

recirculated air for dilution to nreserve the physical characteristics of

the sample. The aerosol particles were analyzed using The two instruments

described below.

A California Measurements, Inc. Piezo Electric (P/Z) Particle Cascade

Impactor Model PC-Z was used for the direct measurememt of the mass concentra-

tion of air-suspended particles between 0.05 and 25 tLm. lhe aerosol-laden air

stream, sampled at 240 ml/min, is impacted sequentiall on 10 quartz crystal

impactor stages. The mass accumulated by each stage causes a proportional

frequency shift on each impactor crystal, which -s electronically compared to

a matching clean reference crystal. Table 14 lists the S 1 cutcff sizes (jp 50)

for the ten stages for a particle dencity of 2 1 cm-. Th? values, o a. -re

the between-stage midpoint diameLers used to compute the Cerodynamc ecqivalent

mass median diameters for each distrmution.

35

Sample in (Qs)

Dilu t ion Air

Stoge i

Mixing Chamber

Dilution 4.ir

Q2

IF, ?F 2 Fiowmeter

Sta1ge 2 W i g C o beM~xig Cambr 1Absolute Fi ter

To Meosurement

Instruments

Pump

I" CO'irig Baith

Uce ~ ~ ~ ~ Ae, o iolo'- o-

36

L . _ _ _ _ _ _ _ _ _ _ _ _ _ _ _2__6

TABLE 14. PIEZOELECIRIC COUNTER STAGES

Stage Dp50 Mi

1 25.02 12.5 18.753 6.4 9.64 3.2 4.85 1.6 2.46 0.80 i 87 0.40 0.608 0.20 0.309 0.10 0.1510 0.05 n.075

After passing through the 10th, lowest, staoe, the air flows through a

flowmeter to a pump where it is exhausted to the atmosphere. The rate of fre-

quency shift in each stage is related to the mass concentration of aerosol

particles captured in that stage, and can be expressed by the following

equation:

Af i

where

Af i = frequency shift for stage i, Hz

At = sample time, min

a. = sensitivity factor for stage i

V = volume flow rate of air sample, 240 ml/min

Ci = aerosol mass concentration in stage i, g/m'

Thp sensitivity factor, a i , deperds on the resonant frequency of the crystal

and the area of the sensitive portion of the crystal compared to the area of

the impinging air jet, but is czherwise a constant for each stage. The con-

centration may therefore be calculated from the mea5ured frequency shift by

the equation:

Af.

i i 2.t

37

where

ki = stage constant

lhe data reported from the P/7 cascade impactor are the total suspendeoparticles (TSP) in mg/m 3 and the mass median dianrrter, Iri. in jln. The TSP is

determined by adding the masses per stage and multiplying by the Ji'ution

factor:

TSP = 1000 SC. 1

The dm are computed by summing the products of the ass fractions cr stdqe,X times the midpoint cutoff size between stages, i:

dm = 2X.M.

wh ere

X. C i/TC.Xi 1- Ci 2

M. =as indicated in Table 14

The Pdrticle Measuring Systems, Inc. Active Scattering Aerosol Spectrr.,e;-er(ASS) Model AS,4S-300-PMT was used for sizing oarticles within the size rangeoF 0.083 to 3.00 pjm. Particles passing through tie Iaser cavity of a contin-uous He-Ne laser produce pulses of light proportional only to their size indposition in the beam. A pair of photomultiplier detectors image the light

impulses and select pulses produced by particles in the corrc-c sample space.A pulse height analyzer then determines the particle sizes.

The output of the ASAS is grouped into size classes as showr, in Table 15.

!

I38!

TABLE 15. ASAS SIZE RANGE DATA

ASAS Size Interval Interval Width di, MidrangeRange Channel pm um Diameter, iim

3 1-7 0.088-0.144 0.056 0.A16

3 8-15 0.144-0.208 0.364 O.7C

2 4-15 0.210-0.390 0.180 0.300

1 4-8 0.388-0.503 0.115 0.445

1 9-15 0.508-0.676 0.168 0.592

0 2 0.690-0.855 0.165 0.772

0 3 0.855-1.020 0.165 0.938

0 4 1.020-1.185 0.165 i.102

0 15 2.835-3.000 0.165 2.918

39

7. RESULTS AND DISCUSSION

A summary of the analysis data is given in Table 16. In experiments 1 and

2 the dense smoke concentrations overloaded both the P/Z cascade impactor and

the aerosol spectrometer and the data are not reliable. Even with a dilution

of approximately 10,000 to 1 the smoke samples were still too concentrated for

the aerosol spectrometer, making the number concentration measurements erroneous.

Since large numbers of particles are present in the lower range, Range 3, of

the spectrometer, counting errors are most severe in the lower channels. How-

ever the mass contribution from particles in lower ranges to the total mass

distribution is small and the error is also minimal. Therefore the data from

the aerosol spectrometer are presented as a mass distribution. From the rest

of the data the following conclusions can be made:

1) The use of different generators or different oils does riot affect tme

particle size characteristics of the oil fogs. Tae average mass mean diameter

ds determined by the P/Z cascade impactor for Runs No. 3 through 10 aid 12 is

1.16 pm with a standard deviation of 0.14 pim.

2) Running the oil fog generator at the low oil feed rate of 0.5 gpm,

half the normal rate (Experiment No. 11) decreases the TSP and also the parti-

Jie size. Reduction in TSP is attributed simply to the reduction in oil Feed

rate and is in approximately the same ratio to oil feed as in Lhe TSP of oil

fogs generated under normal operating corditions (Experiment No. 12). The

smaller particle size is probably due to less agglomeration at the reduced

paticle concentration.

3) Very little effect on the fog characteristics seems attributable to I

the 3ii. For a given generator, for example gererato- B, cl,an inq tile oil frorm

Oil 3 to oil 1 changed the TSP from 0.52 grn/mr3 tc 0.70 gn/m3 and the mcan dia-

reter froin 1.42 --n to 1.05 ;m.

4) (einerator C produces fewer:,? compared to the other two -,eneratrs

fr a] threp oils. T1.e particle Size uoes noL show any trenid.

4(",

- -.... -

4-VI) a)~

1-j E0

of (t fl .Q Lo Cf (J C',J m) ~-1 -4 0 (Nj C:0

LU

V) zt U) Cl -;- -d 0 ).

o E

< -4

4-)-

4- 0) C N ~ 4D U ~ 0 0

0L (a-0 En inr.N -.- c~U ')a) E

Ei:3o E-4C4 4 3

LU (A I- 0)F - ' -

4m 4-)

4-) -

LL c) l

00) -

o. 0) 7a0

0 >- 4-'0 0 Wiu

(V 5--4~ CD COW3

5-L L ( C 20a10)) 4)0C+

L/) 0) Q))

4-) 1

CL~~

LUJ

41

5) The mass mean diameter dm. calculated From ligt scatter nq measure-

m2nts by the ASAS is consistently lower than te measured value by the P/Z cascade

impactor.

The following assumptions involved in the transformation of number dis-

tribution to mass distribution may be the causes of the difference.

" The particles are assumed to be spherical.

" The refractive index of the oil fog particles is presumed to be uniform.

. All the particles are of uniform density. The coarseness inthe cutpoints of the impactor stages also may contribute toerror in mass mean diameter measurements.

Ficures ,3 and 9 show typical histogram and cumulative log probability

plots of the particle size distribution obtained in E,-weriment 6. Exceot for the

extreme ends of the distribution the data follow log normal behavior very

well. This was true for all experimental runs.

Figure 10 shows the cumulative plot for the high temperature run

(Experiment 11). The mass median diameter for this run (0.70 pm,) is

smaller than the mass median diameter obtained under normal operating

conditions.

Time histories of mass mean diameter and TSI2 were obtained for Experiments

3 through 12. As an example, the complete data obtained uQ to one hour after the

generation of smoke in Experiment 4 are given in Table 17. The decrease in

mass concentration and the growth in particle mass mean diameter are plotted

versus time in Figure 11. The mean diameter increases and the mass concen-

tration decreases linearly. Table 17 also gives the slope, m, intercept b,

and correlation coefficient R for the equation

y = mt + bwhere

y = dm in um )r TSP in mg/m 3 as appropriate It = time

Taile 14 and the correspondin date for Experiments -14 are given in

Appendix D.

I

U

C

CU

4L-

2.3

1 43

Partcle liat~te, d ~, mI -

4-)u

1-: 0o L-

M oA

C.' 0

-o eo~ 0

t.0 Lr

(W..- (/P

444

ML0

0

4-)0u

cjjia--

C=.,

rro

r-Jc

-0-

C):

45-

momE

TABLE 17. DEPENDENCE OF TSP, dm AND n ON TIME t.

EXPERIMENT NO. 4

P/Z Impactor ASAS

Time (t) TSP dm Time (t) dm No. ofmin mg/m 3 (urn) min IrI Particles (n)2 144 .686 2 .776 45622

10 739 .842 4 .853 52368

18 667 .876 10 .813 46992

36 634 .824 15 .823 42884

44 566 .831 36 846 33/18

52 598 .878 44 .850 31352

60 506 1.00 52 .888 22506

60 .893 13774

STATISTICAL ANALYSIS" FOR STATISTICAL /,N4LYSIS: FORLINEAR REGRESSION: CURVE n = n e-kt

CURVE=n558n61) TSP vs t slope = - 3.9 n0 55826

intercept = 763 K = .0184correlation coef. - -.944 correlation coef. = -0.93

2) dm- vs t Equation:slope = .00313 .0!84t

intercept = .749 n 55826 e- Iccrreiation coef. .744 1Irnn 10.93 - .0184t

fEpati n: 9 significance level Iy = Olt + c

i = slope and c intercept I

II!i ,, ',

CLJ

.-

0 0

CCC

0

C)

4-)

0'U

1-3

Ln

C

0

C)

+ 0

40

'

o*- i

...

" ....,.- ..

The number coucentration n of the aerosols ir, the holding chamber will

decrease exponentially due to coagulation. The rate of change ,of n is governed

by the equation

dn (1)

where K is the effective agglomeration coefficient. Integration of Equation 1

yields

In n = In n - Kt0

where n is the number concentration at time t = 0. Use of regression equations

of the above type to correlate the data obtained from the aerosol spectrometer

provided good correlation coefficients. The regression coefficient, K, has a

physical significance and denotes the effective agglomeration constant of the

polydispersed aerosol under study. In order to compare the agglomeration cor-

stants obtained from various experiments it is necessary to normalize K with

respect to initial concentration. The normalized constant K*, determined by

K* = vol - n-1 . t -

is given for all experimer.ts in Table 18.

Figure 12 shows the particle concentration change with time for

Experiment 4.

III|1

48

TABLE 18. CALCULATED VALUES OFAGGLOMERATION COEFFICIENT

Agglomeration Coefficient, K*Experiment cm n-I x I - 7

3 1.4

4 3.29

6 4.38

7 5.98

8 12.0

9 3.37

10 12.0

11 1 .03

12 5.82

Because of the overloading of the aerosol spectrometer the fine detailS

of the number distribution were not observed. From those experimental runs

which involved aerosol concentrations within the operating limit of the spcCtro-

meter it appears that the size distribution is bimodal with fine and coarse

modes. The fine mode extends below the low limit of the spectrometer. Figures

13 and 14 show the number distributions of fog in Experiments 5 and I. The

bimodal nature of the aerosol is due to the dual fog fcrming processes of com-

busion and condensation. The fine mode corresponds to the excess condensation

nuclei and the coarse mode corresponds to the nucleated aerosol. UndEr normal

generator operation the modal value of the coarse mode is approximately 0.93 i m.

For high temperature runs the modal diameter of the coarse mode decreases to

0.45 m

49

i

3.0

5~ .0

00 IF-'uE 12 xeien o . atc]K w,0r ie

05

2.0

1 .0

O 0.2 Patce 0.5 -1.0 2.0

Figure 13. Experiment Nlo. 5 (C-2) Particle Size DistrioLftiorl b." / SASAerosol Spectrometer.

2.0

C

1 1.0 00

O.I 0.2 0.5 1 .0 2.0

Particle Piameter dr- prm

Figure 14. Experiment io. II , IT) Particle Size Distribution by ASAAerosol Spectrometer.

i 5::

APPENDIX AFOG OIL

MILITARY SPECIFICATION MIL-F-12070A

A-]

MI L-F-12070A8 JANUAIRT 1354SUPERSEDING

5 Jane 195Z

IJall 1946

MILITARY SPECUXA4TIN

FOG OILThte 9peodfloatim, haa been apsroved by the Deptirtment of Defeefor *8@ by the Departnsent of the ArmV, Mhe NYtvy, and the Air Yoroe

1. SCOPE (Appication for copies obciiid be addred to the1.1 cop.-Ths seciicaton over pero- Superintendent of Documents, Government Priating1.1 cop.--: s seciicaton over pero- Offce, Washington 25, V. C.)

leumn oil for use in mechanical smoke gen-eratorg- 3. REQUIREMENT'S

1.2 Claasification.-Fog oil shall be of the 3.1 Material.-The material shall be anfollowing types, as specified (see 6.1):- overhead petroleum fraction and shall conm~ain

Type SGF.-For use at temperatures no additives. The material shall be free fromabove 4Q0 F. water, sedliment, grit, or other foreign matter.

Type SGF2-For vso at 400 F. or lower. 3.2 Chemical and physical.-Tha material

2. APPLICABLE DOCUMENTS shall conformn to Table 1.

2.1 The following specifications and stand- 4. Q U A L I T Y ASSURANCE PROVI-ard, of the issue in effect or date of invitation SIONSfor bids, form a part of this specification: 4.1 Lot.-A lot shall consist of th6 fog oil

SPECIFICATIONS produced by one manufacturer with no changeFEDFRALin process or materials in no more than 24 con-FEDERALsecutive hours.

FF-W-556--Wool; Steel. 4.2 Sampling-The Goveennment inspectorVY-L--791-Lubricanta, Liquid Fuels, and shall take a representative one-liter specimen

Related Products; Methods of Sampling from each o" .5 containers selected at random orand Testing. 5 representative one-liter specimens ding the

STANDARDS filling operations. The specimens shall beMnJTARTplaced in clean, dry containers and labeled to

MIL-TD-29--Maring f Sipmets. identify the container with the lot represented.MIL.STDi29-Maring f Sipmets. Each specimen shall be separatey tested as

(Copies of specifications, standards, drawings, and specified in 4.4.pobUcationA required by contractors in connection with 4. Ispcinspecific procurement functions should be obtained 4. rpcinfrom the procuring agency or as directed by the con. 4.3.1 Packing and markinq.-The inspectortracting ocer.) shall inspect the packing 9.nd marking for comn-

2.2 Other publications.-The following plianlce with Section 5.doc:ument forms a part of this specification; 4.3.2 Certiptate.-The ins.pector shall ascer-unless otherwise indicated, the issue in eifect on tamn by certification or other %p.provpd mieansdate of invitation for bids shall apply. that the oil is an- overhead petmuro , fra.tion

I.VrMBTATN COMMxanc CONXISSIoNr containinig no0 additi ves.Regulations for Transportation of !9v 4.3.3 Imp u ritie.v.-T he imspectot sha!l in-

plosives and Other Dangerous Articlez. spect the niatEiii for the presence of vwter,jetc. sediment, grit, or other foreign mcatte~r.

A-2

FIFMU.-F-12070A

Table I.-C lsmical and physical

PrprtI Type 8GFI ype SGF2

Maximura Mlnimunm Maxitour Minimum

Flah point, *F -- - - - - - - - - - - - - - - - - - - - - - - -- - - - - - - - - -- 320Vistouity, Sayboit Universal

At 100" F. ',second&) 110-- - - - - -- - - - - --- - -- --- - - - - - 100At 210* F. (seconds) -- - - - - - -- - - - - - - - 6 - - - - - --- - - - - - --- - - -

Carbon residue (Coanmdoon), pecn ---------- 0 ..... L 0. 1------Neutralization n ur-b-------r-- _ ---- 0.1 ------- 0. 1 -----Pour point, F---------------------------------------- u0 -40 ------Vapor temperature, *F. at:

10 percent distillation------------------------------------3............ 0.......... -- _-50 percent distilatioc ------------------------------ 40----------- ------------90 percent distillation ------------------------- GfO ------

*A viscosity of 65 see., at 2100 F. will be the maximum permissible for oils having a viscosity index of 50 ormore.

4.4 Tests. inches by 5 inches by 1,4 inch, having a hole mn4.4.1 Metho'd&.-T he following tests shall be the center 2% inches in diameter.

conducted in accordance with the applicable 4-4±1.4 C a n d e n 8 e r.-The condenser (amethod of Specification VV-L-491 specified in Friederichs- or Hopkins-type condenser is sat -Tabie IL. isfactory) shall be its shown in figure 2.

Tabl'll.Tes metods4.4.2..5 Receiv~er.-The recei-ier shall be- aTable11.-eat etho. 10-mi. graduated cylinder constricted at the

Test ethod top to rereive a stopper. The cylinder shall beTest ethod calibrated at all points to within = 0.5 ml.

4.4.21.6 Suction flaek.-The suction flaskFlash point ---------------------------- 110. 3. 4 shall be a 1000-mi., borosilicate glass flask.Viscosity, Saybolt Universal----------------30. 4. 4.42-L7 Preeu,-e g' a u g e.-The pressureCarbon residue (Conradson) --------------- 500. 1. 5

t_ Neutralization number ---------------------- 4. gauge shall be a Dulbrovin Vacuum G-Lugs. orPour point---------------------------- 20. 1. 7 equivalent.

_________________________4.4.2.1.8 Vacuum purmp.-The vacuum pumpmay be of any design capable of secuing and

4.4.2 Distillation, maintaining the reduced pressure desired.4.4± Apparatua.-The apparatus shall 4.4.2.1.9 Vacuumr control apparatu4e.-Amn

conform to this paragraph and 3gures 1 and 2. automatic vacuum control apparatus or a tand-4.4.1.1 Diitillation flask.The distillation controlled bleeder velve shall be used to mairi-

flask shall be a 250-milliliter (nml.), Saybolt tamn a steady pressure.flask, of borosilicate glass, conforming to 4.42.1.10 Therniometer.-The thermomreterSpecification VV-L-791, Method 100.2.1. ex- shall be an ASTM High Distillation Therruom-cept that the outlet tube internal diameter ;hall eter, 300 to 760* F. or 00 to 4000 C.be 8.0 ±t 0.5 millimeter (mm.). 4.1.11 Heater.-An electrc heater shall

4.4±1.2 Shield.-The flask shall be encased be used for the dist'lation (see 6' 4)

in. a shield constructed of "'Sil-O-Cel" brick as 4.4.2.1.12 Connectiont. -T h s conn,!tionsshown in figure 2 (see 6.3). shall be made by means of netal or glass- iubing

4.4.2.123 Board or support.-The flask 9*hil]j having a~n inside diameter of S to 9 mm. AN~resc on a transite or hard asbestos board. 5 joints shall li< tight and ~I~t e seled with a

2

A-3

MIL.F-1 20"0A

D~St~~t~.. R ~- Wafer outlet

II,, 8kWWIILD

0000000 heater~

Flask c@lTtnln§

ceiet uc a wte las soiu sliat)or itjonsik ncko C~e ork Gasst Woeolp

P. mrixture of 75 percent collodion and 25 Iwreent paratus and maintain the absolute pressure atcastor oil. 10--2 min. by r.eans of the vacuum contro! ap-

4.4.2.2 Procedure.-Place approximately 1() paratus. Apply heat to the distillation flaskgruat ( gM.) of dry, clean, grade No.-1 steel wool at a rate sufficient. to start the dlistillation Nvith-cunforming to Specification FF-W-.-56 in the in 26 to 30 minutes. Tiereafter distillationbulb of the dist illation flask, and spiread to near- should Proceed at a uiorm rate of 4 to 5 nIl.ly fill the bulb. Measure exactly 100 nil. of the per minute. Rteord the temperatures r-egis-spec~mine into the graduated cylinder. Pour tered by the distillation thermonieter when thethe specimen from the graduated vyliader into quantity of distillate in the reciving flaskthe distillation flask. Allow the specimien to amiounts tc, I I. 50. and N0 percent respectivelydrain from) the eylird-r into the flaksk unvtil not of the charge (see 6.5). With proper caire andmore than 1 ml of oil remains in the cylindler. attention to detail, daxplicatc i-esiilts nhouldiThe same grad afte'i cylin~der, without being Clieuk within 10O F.cleaned, shall be us,.ed fujr receiving (ie djiit- 4.5 Rejection and resubmission.-If anylate. Assemble the apparatus i.- ,ho wni on ti,- cci mcllli fall" to con form :i thIis spec if alrlltire 1. Fit th~e thermornie:Lr t ightly inito the thte lo ,hall he rejected. 'The ci.it rawc-,, at&4~., center properly in the neck withi the lo'Ner aoxes ~th,,Governruewi. shall lia'e flne cp-end of tire capillary tube on a level with the in- -ion of 1 t:~ : ;tril1' %[- uIle oil ealch i'o~in'-ideof tleie,ttoni of the vrporoutlet tihe %%here tont r ' rev',Vl L!(1 hc .9f! 111

A -4

MIL-F-12070A

5hleld

block A or B Assembigfront End ble.U~s A aM 8

r

pj4LTe Glass

LLiGI1 As~ emOIyblot.ls A, 5cd C

front End boonm

block C

Condener

li Sto.5 men

Cooling Tubet -14ket

A-5

311L,-F-12070A

material. and resubmitting ohw remnaining por- pling' al)d test~w, proi~vturms specified in thistion of the lot for aecce; tance testing. If riny specilf~aticoiI

specimen taiken front tilt, resubmitted portion 6.3 Shield brick.-Tlie brick is obtainableof the lot fad-;~ to cooin fin to this speciticati'in, fronm Johns 'Manyi lle Co., New York.tile lot shall be fi'ialls retjectedl. 6.4 Electric heater.-The 500-watt electric

1water of u(he Prc,i-oi Scientific Co., or equiva-5. PREPARATION FOR DELIVERY lent. is satisfactory.

5.1 Packing. 6.5 Distillation.-The distillation should5.1.1 Fcr domtadtc "hpm 1t.-Fof oil shiall not be continued beyond 6200 F. because of the

be packed in drums conforming to Specification dancer involved to the apparatus and the op.37E of the Interstate Commnerce Coniinissioni eintr dite to the poisible softening of the bcLt-Regulations for Transportation of Explosives t0nU of tile distillation flask and the exist.ingand Other Dangerous Articles, etc. low pressure in the apparatus.

5.1.2 For overseas shipment LFog oil shall 6.6 Stock numbers.-SGF1 and SGF2 arebe packed in drums con foring to '-peciIicat ion QII;rtkerin1aSte, Corps itemisof sutpply and carry

37D of the Interstate Commerce Commission the followitng Quartermaster Corps stock nuni-Regulations for Transportation of Explosives besnd Other Dangerous Articles. etc..- _ ___-

5.2 Marking.-In addition to any special Type tP G-Gaive dr:I11o S-Gage (tr-Imr

marking requiredl by tile contract or order, all

shipping containers shall be matrked in accord- 1 4-0-871-51l) 4o8.tjt

lance with Standard MfIL-STD-129. 1~ 4-O--SSt-50 I 4-s-8S)--5

6. NOTES----6.1 Ordering data.-Prooireniett (locu- Notice.-Wtien (GoveriinIt iIrw% iia:,,, *'tith'at liImv,

iieir (lIrT aro uqs, (,, ,ill vw riwse oi hr thian iniiients should specif y tile following:ctliv;i ~t id~tt!.rltdGvrivaPo

(a) Title, nuitiber, and (late of this speci liremient oiwr.ation. tle tUnited StflteS: t;overiiuit

wvha tsoever: an d 0-. fi t that ot (;overn ineat. may(h) Type of nuiteriatl requi red (see 1.2 and hiare foriaIiilnted, furir,iel, ur ini au~y %v;! swirplied

3.2). 1I.- .aidtrl wiiS ,-. ; i otther iata is .Iot

(c) Type of imckinl, reilii red (seet 5.1). t,- Iw \guvril v i pia .: w' TMivrw;s> ti.s in avYI i1:1Ii-r tjtiISO T, r r ;i. T tier person cr

6.2 Sampling and test ing.-Wiiez tille conl- criooratioli. .r l ;Vii :- right,' .i~ ihrinission~ tot:-ittor conisi.? eiit v protdulces hiigli-qjmlitv 111.- iII:IitifaictuI it #. 5, ot seil 1 li a. it I mie.iiufl thatL

tei'ial and operates uinder a sYr em of quality tiia in tin), way Ihe ieltiti dtliereto.

control acc eptable to thel ( ivinnowt the Gov- Custodians:erment, at its (hiscri.?ion. Tii m itoh vy. : ii % hol Army-Chemical Corp.s-,r in -at h :ti-jl et~I~~~t~ Navy-Bureau of Ordnancepat ti. 11. v tIgpoew Air Forcesp ecified herein. Ilb 'wtver. ti III Iii- omtiIt ii- Mh-''r in~terest:serves the ri'hlt to ret urn at allY I tizne wc boat. Amy-Mpreviuis not ii' to the cotractor. to ihe S,111- Navy-Sh S.

A-6~ daum

MIL-F-12070AAMENDMENT i

10 MAY 1956

MILITARY SPECIFICATION

FOG OILThik amerdftent forms a porf of Militrj Specifleatiu MiJlL-F- 2 070A,8 Jasna-ary 19.4, and has been approved by the Departcez! of Dc .ensr and im man-datory for use by the Departments of the Army, the Navy, and the Air Force.

Pagc 3, paragraph 4.4.2.2, line 20: Delete "10 -t 2 mm." and substitute "16 :t 0.2 mm."

Custodians:

Army-Chemical CorpsNavy-Bureau of Ordnance

Air Force

Other interests:

Arty-MNav, -ShS

FED. SUP. CLA]915o

A-7

APPENDIX B

GAS CHROMATOGRAPHY DATA

B-1

VI

GAS ChROMATOGRAPHY DATA

Gas chromatograms of 27 oil fractions and their related oil fogs

are included in this section. Preceding the oil/oil fog charts is a

"Chromatographic Standards" chart, obtained with synthetic mixtures of

alcohols, acids and hydrocarbons.

The standard chart is preceded by a Table describing the compositions

of the three mixtures.

Oil/oil fog Chart Nos. 2-23 show the GC's of the oil fractions

together with charts of the corresponding oil fog fraction. Where com-

positions have been identified, they are indicated on the chart and listed

on the accompanying Table.

Chart Nos. 24-31 show representative oil fractions compared with

corresponding normal and high temperature generated oil fog fractions.

B-2

CHART 1. GAS CHROMATOGRAPPY STANDARDS

Key

Alcohol Standard

A. CIIH 2 30H 1-undecanol

B. C12H250H I-dodecanolC. C14H29OH T-tetradecanolD. C16H330H 1-hexadecanol

E. C18H3 70H I-octadecanol

Acid Standard

A. CAH5COOH octanoic acid (caprylic acid)B. CgR19COOR decanoic acid (capric acid)

C. CIIH 2 3COOH dodecanoic acid (lauric acid);3. C13H427C00H tetradecanoic acid (myristic acid)E. CjsH 31C00H hexadecanoic acid (palmitic acid)F. C17H'35C00H octadecanoic acid (stearic acid)

Hydrocarbon Standard

A. ClOH 22 n-decane

B- C12H2 6 n-dodecane

C. C10H3 0 n-tetradecane0. C16H3 4, n-hexadecane

E- C17H36 n-heptadecane

F. CIBH 3 8 n-octadecane

G. CiqH40 n-nonadecane

H- C 0H42 n-eicosane

L. C21HI1. n-heneiCOSiane

3. C22 Hdf n-docosaneK. C2 3H48 n-tricosare

L.- C24P5 n- tetra coa n eM. C28Hq n-octaco:-sne

N.C"~HC n-nonacosane

B---

IA

p D

-~ cr.

.'.

oN

ALCOHOL STANDARD

te A

B

- C

I WD

G H

HYDROCARBON STANDARD

~~CHART 1. GAS CHROMIATOGRAPHY STil

f -- 9-4

VIA

A"DARD

ACY STANDARDS

a

CHART 2. ALIPHATIC FRACTION; OIL No. I AND CORRESPONDING OIL FOGS

Key

A. C n-tetradecarie

B. C1 0H 3 1 n.-hexadecaneC. C17H36 branched alkane0. CISH 38 n-octadecaneE. C19H4t0 n-nonadecane

F. C20H42 n-e-icosaneG. C2 I K 4 branched alkaneH. C21H±4, n-heneicosane

I- C22H4.6 branched alkane

E,-5

Aw-t

4I4 .

OI ORU No, 1 B-

CHR . LPAICFATIN IIB-6

*NO -

I1",

II'NI.-.

OIL FOG RUN No. 10 (A-i)

IT_

•.,-' 4

OI tOGRN yo 6 ' C -

,A % SPNDN. OIL FOGS

CHART 3. ALIPHATIC FRACTION; OIL NO. 2 AND CORRESPONDING OIL FOGS

Key

A. n-ClqH4 0 n-nonadecane

B- 7

r -rOIL FOLU No. 2 B2

r-B-8

OILFO RUN N-9(A2

OIL FOG RUN No. 5 (-2)

IL NO. 2 AND CORRESPONDING OIL FOGS

B-8

CHART 4. ALIPHATIC FRACTION; OIL NO. 3 AND CMRESPONDING O)IL FOGS

Key

A. C14 H-30 n-tetradecane

B. C17H36 n-heptadecare

C. C20H42 n-eicosaneD. C2 1H44. n-heneicosane

Q>9

____ -~"*kww"~

------

B-1

vt e

OIL FOG RUN No. 8 (A-3)

6-10

CHART 5. FIRST AROMATIC FRACTION: OIL NO. 1 AND CORRESPONDING OIL FOGS

Key

A. C12 H16 2,6.-diinethyl-1,2,3,4-tetrahydroniaphthaleiie

B.- C13 H 16

C.- C13 :14 + C14H20 + C15H24

0. C13H160 or C14H20

t4t

OIL No, 1

t.f-

OI O U N.2 (-

CHR 5 FIRS ARMTCFRCIN

Mf-

oz Th

OIL FOG RUN NO. 10 (A-1)

OI FO U O C1

...-. OIL NO N ORSPNIGOLFG

CHART 6. FIRST AROMATIC FRACTION! OIL NO. 2AND CORkRESPON'D1N" FOC

Key

A. C20H2 4 3,6,9,9,lO,10-hexamethy1-9,1O-dihdrophenanthrele

B. C2 oH32C. C16H18

B-13

F.OI No.~ 2 T

U",'- -a

-,, "" l

OL OIL No. 2

B-14

U-' r

OI.FG RU.....(B 2

/ HATl. RIIICFRCTO:lILNO 2l

17~ f

- irl -p

OIL FOG RUN No, 5 (-2)

L NO 2 AD CORESPNDIN OILFOG

CHART 7. FIRST AROMATIC FRACTION; OIL NO. 3 AND CORESPONDI'JG OI11OO

Key

A. C 1 5H2 2B. CisH 18 dimethyl isopropy~naplihtIalene

C- C1 4H, 6

-4

r,.V. 4. f, .,

If7.

OIL No. 3

I nlIL Foe RUN 4o, 3 (P-3)

I CHART 7. FIRST AROMATIC FRACTION: 0i

L I / 3-16

OIL FOG RUN No. 8 (-3)

SIL .3A-L FOGSi

, OIL. FOG RUN No. 7 (-3)

-.. -. : j -, -, --- -- --- ,, ,

OIL NO. 3 COR.POIRG OIL FOGS

• _ _

CHART 8. MIDDLE AROM4ATIC FRACTION; OIL NO. 1 AND CORRESPONDING OIL FOR~S

Key

A. CISH240 methyl-di-tert-butyiphenoli

B. Clr3H 34 n-hexadecaneC. C14H1 4 dimethylbiphenyl + Cj5H16 dimethylbenzylberizene

D. C10H12 methyifluoreneE. C15H14 dimethyifluorene

F. C15H12 methyl phenanthrene

G. C15H120 9-methoxyanthracene or CISH 16

H. C16H14 dimethyiphenanthreneI. C20H32 n-butyl-n-hexyl tetrahydronaphthalene

B-17

II

C H

OIL o R No. 2 B1

CHRI.MDL RMTCFATO:OLN.

5.wi

- rr

OIL FOG RUN No, 10 (A-i)

OIL FOG RUN No, 6 (C-i)

IL NO. 1 AND CORRSPONDING OIL FOGS

C)L

CHART 9. MIDDLE AROMATIC FRACTION; OIL NO. 2 AND CORRESPONDING OIL FOGS

Key

A. C16H1 4 dimethyiphenanthrene + C15H14, dimethyifluorene

B. C17H,6 trimethyiphenanthreneC. C18Hs alkyiphenanthrene

B-19

C

. j

kil

* CD

MAN

f wa

CD~i/

%V OIL FOG RUN NO, 9 (A-2)

VIPT

iOIL No. 2 MD CORRESPONDING OIL FOGS3-2 6

CHART 10. MIDDLE AROMATIC FRACTION; OIL i40. 3 AND CORRESPONDING OIL FOCS

Key

A. C14H,2 methylif IuorenejB. C10H10 phenanthrene or anthracene

C. C15H1 4. dimethyifluorene[D. C15H,2 methyiphenanthrene or methylanthraceneE. C15H12 methyiphenanthrene or methylanthracene

F. C15HI20 9-methoxyanthraceneG. C18H18 1-methyl-7-isopropylphenanthrene

H. C20H32 probably n-butyl-n-hexyltetrahydronaphthalene

B-21

I ti )n

.4

OI Fo Ru o B3

WAT1.MDL RMAI1RCIN I

ii -22

'17-

40::

.It

OIL FOG RUN No. 7 (A-3)

OIL O. 3MD CRRESONDIj OI FOG

CHART 11. HEAVY AND HEAVIEST AROMATIC FRACTIONS: OIL NO. 1 AND CUHRUSPNViG OIL FUiiS

Ke y

.. C12HI2 dimethylnaphthalene

B. C12H8 acenaphthalene

C. ClSH 2 40 2,6-di-t-butyl-4-methylphenol (ionol)

El. C13H1 4. trimethylnaph'thalene

E. C13Hjo fluorene or phenaleneF. C14H12 1-methyl fluorene

G. C14H16 C4-alkylnaphthalene

H. CIAO1 anthracene or phenanthrene

I. C15H14 dimethyifluorene

J. CjsH 14 alkeny] dibenzene

K. CjsH12 methyiphenanthrene or, methylanthracene

L- C1 5H12 methylphenanthrene or methylanthracene

M. CjsH,20 methoxyanthracene or C16H16 isomer

N. C16H1 4, dimethyiphenanthrene

0. C16H1 4, ethyl or dimethylanthra,.ene

P. C18H18 C4-alkylphenanthrene or C4-alkylant~rzcene

Q. C18H18 C4-alkylphenanthrene or C4--alkyitanthracene

R- C19H30 2-n-butyl-5-hexylindan

B -23

FL

im

cc

OIL NO. I HEAVY FRACTION

EF

K L

cM

N0

I~Im

A R

OIL FOG RUN No, 2 (B-i) HEAVIEST FRACTION

CHART 11. HEAVY AND HEAVIEST AROM'ATIC FRACTIONS:

/ B-24

. 6.

OI O U o B-)HAYFATOOIL ~ ~ ~ ~ ~ ~ ~ g NO N ORSPNIGOLFG

8-24

CHART 12. HEAVY AND HEAVIEST AROMATIC FRACTIONS; OIL NO. 2 AND CORRESPONDING OIL FOAGS

Key

A. C13HIO fluorene or phenalene

IB. C14HI2 1-methyifluoreneC. C14H10 phenanthrene or anthracene

D. C15H14 dimethyifluorene

E. C15H12 methylphenathrene or methylanthracene

F. CjsH 120 methoxyanthracene or C1 7H,6 trimethylphenanthrene

G. C15H120 methoxyanthracene or other isomer

H. ClOH 1 4, C2-alkylphenanthrene or C2-alkylanthracene

I- C17H,6 C3-alkyphenanthrene or C3-alkylanthracene

J. C17HI4 2-benzylnaphthalene or C18H18C4-alkylphenanthrene

K. C I ei I C4-alkylphenanthrene or C4-alkylanthracene

B-25

CD J 0c

Ln NA, UY' -r4

OI No 2 -Ev RA7O

r. 4-r j * . ro.40

V.-4

AL

E

rr

OIL FG R No. 2 HEAVIEST FRACTIO N

O. F.,i

F.-;-

" L7 , ...

L.' "-. TI

OIL Foe RuN Ito. I (B-?) HEAVIEST FRACTION

FRATIONI: OIL NO. 2 AN CO~RESPONDiN6 OIL FOGS

r.

I

"'! ; tiT

I 'I. . .

I

IL 1O. 3 HEAVY FRACTION

I

III

I

o~

I

F. L i

I

I/ OIL FoG RUN No. 3 (B-3) HEAV

FRACTI~ON

I3C

A T 1. H A Y R E-E T A

OI A I R C J N

OIL No. 3 1HEAVIEST FRACTION

4IOLFG RN. 39.3 HAIS FATO

IONS:~~~ ~ ~ ~ OI O N OREPNIGOLFG

B-27%

I"

~ r~rt *

OIL NO-.1

r .4

Im

OIL FOG Ruw No. 2 (B-i)

I CHART 14. ESTER FRACTION: OIL NO. 1

SUN----

4 lit;

r~I.

C'rITI

r. 0t-..py m.'

OI FGRmNo (-

I~~~ ~ ~ ~ AN NRSODN6OLF6

rv

I OIL No. 2

OI o u o B2

CHRI5 SE RCIN I O

I-2

OIL FOG RUN NO. 9 (A-2)

Nr'f

OIL FOG RUNi No. 5 (C-2)

2 AND CORRESPONDING OIL FOGS

01

OIIo

If: ,r.OD

OIL oG Rm N. 3 B-3

CHAR 16 SE.FATO: I O

IB 30

,2v.

OIL FOG RUN No. 8 (C-3)

NO. 3 MND CORRESPOM4ING OIL FMG

M.-..

01 LJo U No.2(-

MAT1.AC,'LFATON I O

B-3

c'-

-3I

OIL FoG. RuN No. 10 (-1)

IL N. 1 ND CRRESOMIN OILFOG

S1

C.p

g a.OIL No. 2

OIL FOG Ruw No. 4 (B-2)

CHART 18. ALCOHOL FRACTION: OIL NO. 2,/ S-32

4.

rv

OIL FOG RUN No. 9 (A-2)

60 t

CL

OIL FOGs RUN No. 5 (C-2)

2 AND CORRESPONDING OIL FOGS8-32

I

I

-I :.J, ;';- i , "> .. -,t:"L" .. .

CL r N P

, *

I Fo RL. No. 3 B

I"

-I

i, I 0- Fo- u o (-

CHART 19. ALCOHOL FRACTION: OIL NO.'I OILFoe RN No.0-B33

"1

.. ... ... . . . . . . .. . , -...... ..- . ... . - _- - . . - .

0* M

-7ZOIL ~ ~ 'r Fo RU N. (-3

OIL Foe Ru No. 7 (-3)

3 AND CORRESPONDING OIL FOGS

Ie

OIL NtO. 1

Ic

IL

OI 0 RmN. B1

CI0 CDFATIN I O

IM B-3

or

r

OIL For. Ruk No. 10 (A-i)

OIL Foe Ruw No. 6 (C-1)

OIL NO. I AND CORKSPOWDIN6 OIL FOGS

U, -

C.

OIL No. 2

II

I.0I U,

eq

* N

OL Fo6 RuN No. 4 (B-2)

9-3S

IN=

nIl. FOG, RuN Nlo. 9 (A-2)

AY&A

OIL Foe Ruts No. 5(C-2)

L 0. 2 AM CORWSPOWIN6 OIL F06S

OIL No. 3

'..

rmm

OIL FO6 PAM No. 3 (B-3)

CHART 22. ACID FRACTION: OIL NO, 3I,) -36

OIL For. RN No. 8 (A-.3)

C,.,

,'r..

OIL For RUN No. 7 (C-3)

NO- 3 AND CORRESPONDIN6 OIL FOGS C

a- --*-. -

CHART 23. NITROGEN BASE FRACTION; OIL NO. 2 AND CORRESPONDJNG OIL FOGS

Key

A. Cj0HqN methylquinoline

B. CIIHIIN dimethyiquinoline

C. CIIHIIN dimethyiquinoline

D. C12H13N trimethylquinoline

E. C13H15N probably tetramethyiquinoline

F. C13H15N probably tetramethyiquinoline

G. C14H17N probably pentamethylquinoline

H. C1 5H19N probably hexamethyiquinoline

1. C15H19N probably C6-alkylquinoline with at least one ethyl group

J. C15H15N probably dimethyl-9,10-dirniethylbenzoquinoline

K. C15H13N nethylphenylindole or dimethylbenzoquinoline

L. C16H,5N or C15HIIN0

8-37

Oil FogOiu No. 2

CHART23. ITROGN BA E FCIN I O NDCREPNT, I

"N B-38

CHART 24. ALIPHATIC FRACTION; OIL NO. 1, NORMAL RUN, HIGH TEMPERATURE RUN

Key

A. C14H 30 n-tetradecane

B. C16H3 n-hexadecane

C. C17H36 branched alkane

D. C18H38 n-octadecane

E. C19H40 n-nonadecane

F. C20H42 n-eicosaneG. C21H4, branched alkane

H. C2 1H4, n-heneicosane

I. C2 2H46 branched alkane

B-39

...... . . *... -, . . . . .. . . 2.- - ' ''

'I

OIL NO. 1

Lrr,

p OIL For.RmNo. 11(B-MI

CHART 241. ALIPHIATIC FRACTION4: OIL NO. 1, NOMIA/ 8-40

-TP*

-7m

CHART 25. FIRST AROMATIC FRACTION; OIL NO. 1, NORMAL RUN, HIGH TEMPERATURE RUN

Key

A. 2,6-dimethyl- ,2,3,4-tetrahydroriaphthalene

B. C13H1 6

C. C13 + C14H20 + Ci5H24D. C13H,60 or C14H20

B3-41

I .

c

g.OIL No.1

I

I -7,'.

17!~

U

I '

OIL FoG RuN No. 11

CHART 25. FIRST AROMATIC FRACTION: OIL NO.( 6-42

i li -

.. . . .... . . .. . .. III .. .. . .. . . ... . . .. .. l . .. . .. . II .. . | . . . . .. . .

r~.

No. U'I " ,"T-IL N " N

i, ',

OIL FOG RUN NO. 2 (B-i)

iiii. 1fl (B-i[HT))

]L It0. 1, NIORMAL RUN, Hi6H TE1IPERATUI£ RUN

2(

CHART 26. MIDDLE AROMATIC FRACTION; OIL NO. 1, NORMAL RUN, HIGH TEMPERATURE RUN

Key

A. C1.SH240 rethy1-di-tert..butylphenol

B. C16H34 n-hexadecaneC. C10H14 dimethylbiphenyl + C15H16 dimethylbenzylbenzeneD. Cj ,H12 methyl fl uoreneE. C15H14 dimethyifluoreneF. C15H12 methyiphenanthreneG. C15HI20 9-methoxyanthracene or C16H18H. C16H14 direthyiphenanthrene1. C2 1H32 n-butyl -n-hexyl tetrahydronaphthal ene?

B-43

IFG H K m

II LE

DON. 0I T

IrsMMrr

I A ,

,cc"N •

M\

!...o. ,r, ,-

V )C

I|

OILR No. IEV RMTCFATO:OLN.1

| //LI_ i N l

cy cc,

rtz.

-4t-

OIL Fos Rim No. 11 (B-1(NTii QCHART 27. HEAVY AROMIATIC FRACTION: OIL NO. 1, NORMi I

prj

OI FoFU o.2(-

L

jr'j

lwI a' HIHTMERTR U

CHART 27. HEAVY AROMATIC FRACTION; OIL NO. 1, NORMAL RUN, HIGH TEMPERATURE PUN

Key

A. C12H12 dimethylnaphthalene

B. C12He acenaphthalene

C. C15H240 2,6-di-t-butyl-4-methyl phenul (ionol)

D. C I 3H14 trimethyl naphthaleneE. C1 3H10 fluorene or phenaleneF.C14H12 1-methylfluorene

G. C14H16 C4-alkylnaphthalene

H. C14H10 anthracene or phenanthrene

I.- C15H1 4. dimethyilluoreneJ. C15H14 alkenyl dibenzene

K. C1 5H12 methyiphenanthrene or methylanthracene

L. C15H12 methyiphenanthrene or methylanthracene

M. C,1 H120 ,methoxyanthracene or ClrH 16, isomer

N. C16H14 dimethyiphenanthrene

0. C1 6,l ethyl or dimethylanthracene

P. C17H1 6 C3-alkylphenanthrene or C%-alkylanthracene

Q. C17H12 methylpyrene or benz [ci] anthracene

R. C1 8 H, 8 C4-alkylphenanthrene or C,-alkylanthracene

S. C18H18 C4-alkylphenanthrene or C.,-alkylanthracene

T. C19H30 2-n-butyl-5-n-hexyl indan?

B-d5

71

OIL NO.1

D E i * &

0- ; 61

OIL FOG Ruw ft. n

CHART 28. HEAVIEST AROMIATIC FRACTION: OIL NO. 1

T~~ ~ ~ ~ 1.11 N1;p

OIL FOG RUN No. 2(B)

hc

.442

CHART 28. HEAVIEST AROMATIC FRACTION; OIL NO. 1, NORMAL RUN, HIGH TEMPERATURE RIJN

Key

A. C,0H8 naphthalene

B. C21Hj0 methylnaphthaleneC. C11HIG methylnaphthalene

0. C12H12 dimethylnaphthalene

E- C1z.H10 phenanthrene or anthracene

B-47

D EF G H

OIL NO.1I

OI O uNN.1

CHR 6 BDJ RMTCFATO:OLN.1

6-4

rr~

OUL FOG RU No, 2 CE-i

5-48OIL NO. 1, NORMAL RUN, NIGH TEMPERATURE RUN

IIo

tr X'

'Vr

IIOI o

OIL FoG RUNi NO. 11

I / CHART 29. ESTER FRACTION: OIL NO. 1,( B-49

I-Ak" l

ru rl) (q

Lo 4 ,

%V

OIL FOG RUN No. 2 (B-1)

abm No. 11 (B-1[HTI)

IL NO. 1, NORAAL RUN, HIGH TEWiERATURE RUNB-49

r-

OIL NO. 1

Ce'

km

I -n.~ ~ ~ , 1CO

OIL FoG RuN No. 11

CHQART 30. ALCOHOL FRACTION. OIL NO., I

"Cr.r.

OIL FoG RUN No. 2 (B-i)

11 (B-1IHT])

NORML RUN, HIGH TEMPERATURE RUN

I-50

AlA

OIL No. 1u o 1(-

ClAT3. AI RCIN I O ,NRA8-5

IL

OIL FOG RUN No. 2 (B-i)

NNO. 11 (B-irHll)

1, NORMAL RUN, HIGH TEMPERATURE RUN

8-51

"OR

APPENDIX C

MASS SPECTROMETRY DATA

C-1

MASS SPECTROMETRY DATA

Seventeen oil and oil fog fractions were analyzed using gai chromatography

separation followed by mass spectrometry (GC/MS). The fractions are listed be-low and are followed by the MS tabulations of the identifiable components.

As noted in the text, the tables show the following headings, an arbitrary

peak number (PKO), an arbitrary spectrum number (SPEC), the compound identifi-

cation (ID), the total ion current (TIC) which corresponds to the peak height

in gas chromatography and is a qualitative indication of relative concentration,

the area under each peak (AREA) (this column is not always included) and the

percentage of each peak remaining after computer subtraction of the background

(TICRAT). The last three columns of the table were not used in this study. I"Silanated" compounds are of column origin rather than from the compound.

Where additional compounds were identified by further processing of the data,I

they are listed on data sheets accompanying many of the charts.

A number of characteristic families of ion peaks whose ;dentities were not

established are also listed on the data sheets.

I!

I ,Ik-

OIL AND OIL FOG FRACTIONS SELECTED FOR MASS SPECTROMETRY

Table C-1 Oil No. 1, Aliphatic Fraction

Table C-2 Oil No. 2, Aliphatic Fraction

Table C-3 Oil No. 3, Aliphatic Fraction

Table C-4 Oil No. 1, First Aromatic Fraction

Table C-5 Oil No. 2, First Aromatic Fraction

Table C-6 Oil No. 3, First Aromatic Fraction

Table C-7 Oil No. 1, Middle Aromatic Fraction

Table C-8 Oil No. 2, Middle Aromatic Fraction

Table C-9 Oil No. 3, Middle Aromatic Fraction

Table C-10 Oil No. 1, Heavy Aromatic Fraction

Table C-11 Oil Fog Run No. 2 (B-l), Heavy Aromatic Fraction

Table C-12 Oil Fog Run No. 11 (B-I[HT]), Heavy Aromatic Fraction

Table C-13 Oil No. 2, Heavy Aromatic Fraction

Table C-14 Oil Fog Run No. 4 (B-2), Heavy Aromatic Fraction

Table C-15 Oil Fog Run No. 11 (B-I[HT]), Heaviest Aromatic Fraction

Table C-16 Oil No. 2, Nitrogen Bases Fraction

Table C-17 Oil Fog Run No. 9 (A-2), Nitrogen Bases Fraction

r-

C -3

* ------------ . .

f 2 I o

w, 2 I I I I "* 1' i i ' 10~i ' -1

o2 I I 2 I

tim' l r l I 0,.i i, 0 n r s g Io ti- 20 - I 2 I2f n I-

1. D1 2y I) m s it i i g, i I Iv I 2v I I f 21 q 2o m ru II -T OD i 2 2) 2 I 2 2

1i 0 2 2 d 2 1 I i1 2 2 2 I 2l I l i 2 , 2 2 ' 2 ! MIr 2 2 o 0 I o2,I i n r2 . 0 Cs ' g2 r . l 4 4 io t i-. . . i t r q .- I . r mv 2 zi (- i t 2 , ' 0 -

till I I I 2 I , 2

ii~~rl 3 ' I 2 2

< ii:2 i 2 i 2 2 I 2 i 2 2 2 2

El I :Nr~t2 02~i~g 2 i'~iir24 2v-- l'2 'q N n u e' 'e-LII sa'2 gvim 2 I 2 I n ~ - 2

12~~~Z J a- 2 2 ' 2 1

1I 0 I I C -j 2 I 2 2 i

l l I 2I I I It 02 2 I 1 1 1ill I 2 2 2 2 2 I I 2 2Iia,

Iii~~" 2Z 2 2 I 2 22

241 lI.2*2 iN2 iu'i~rj0':r 2~l 2r'.fl: 2Ni~42no~n''n'

Il * 2 2 2 li 2 i 2 I t s I , 2 2 2

23 a I j I a 2 2 i 2III~ ~ m 2j ' -2 I I I I I I I S

I , c 1 w I r 4 j 'a 252 L2

III 2 :2 m m 2 : 2III z I 2W o

ill 2 I 2 i 2 2 I I '2 '2 I I ' 2L

- ii 2 2 2 I ' 2 '4 2

4r 2 2 2 I ' 24 +, 2 2 S I I l M

'ii ~ ~ ~ ~ ~ ~ ~ E a, 2, L 'I ,i 2 0

I2' 2 2 2 2 .

li I 2 ' 2 2 20 2 24 lai ' : I i. 4

U.2 ' II 5

k722 v ' r i n Q 2 O 2 , 2 . 0 0 (n 't i

IU l I P I PI >22 2 2' 2 2 2O

222 2 2 2 2 : 2 22'J'C-4

r- ~ ~ ~ ~ ~ ~ ~ ~ ~ r '- u9 C ' ' ' 9

. . r ., (' 9C0 C. - . r .. -1''.

0 9o 0 ~ M in~ 0 r)- 1~ 0 F0N

r. 0d 01 rd mCfIC i09

a ., i '' c I I I

:1 .z 1 c I z z z I

C, 0 0 9l n 0 r V, m 0 IDn 0 d f

rod 0 M V w V It

9X 9 I 9

- 9C-5

r. m n F I) I F I I I I ' v F v

0 ' 1 F 1 N v ,' F 1 IL I , F F

4)J F iWF I MP NFI F 1 F 1 -CI I F I

't IFF 1 1 1 F I I Fe ,1 io I ' e I N- 1 IF

OD ' F 1 ,1 , 1

2 It CiUF~lI EF t Q SF 4Fr~ 4 ' - Ft o~r~'F rW F 'FC'~r' ZS'~n

-~ ~ ~ ~ ~~~~~ IV I 1 - 1 , .. ' -1.. F'Fr1vF ~~ s rIu t

C~~ ~ z I I F ' i F ' F I F

-, I) 1 F5 1 I I -C 1 1 F L II I 1 F F F EFI

Fl F0 ?1 fI I0 I I ' :I (. F m I0I F F , I -Iv rd ) ci1 (7 f. I V V I v r vW I C I F ft w ( I F I I I f 1 F I F 'L F f I w I 1 1r I F It I I F ' F4F1V I w ft qI f V FW d

IF5 F F~ tF I I ,S ' b rI ~ F ~ F 0t ~ FS O t 0 ~ ~ F I ~ t . , b

U'r c ' 0 r ) . N u FO C..* (') U)CF ~ F F VF F~.F t f rF IFO F. W .0 CDF '-f I- SF4 Iq rd~ fli Ir- nOdI I~E4 N nF twr N~ N

F1 1 N ' S C i d F F F N N I . F . F I l N F . F I f F . F I I . F . F

IF I F 'V i S tI iq F F F F F F I I I I~C-6l I

' 0,.rw

cl I

* 1 OMI

Li w ilie i i

qrtn r

TABLE C-2. J31L NO. 2, ALIPHATIC FRACTON

Key

UNK* Spectra with this designation contain some or allof the runs of the followings masses whose parentstructures have not been resolved: 41, 42, 55, 67,69, 81, 83, 95, 109, 123, 137, 165, 179, 193.

N I, -p Io o vI q -o t I. v a , w q , o o r r

I in I 6 II In I N I. p I m W I I t-I o I c - o n c r

01 ll 1 I Ir 1 I d) 4. 0 'a

I t

CIE, N 101 111 1 I 1 l~~ 0 0 1 0 0101 01 10 10 Inb 0 0 1C 0

0, -4 D I V I -I -I r, I I, , in I 0

;r'1 II 1; 1 I ~ j ar f' 10 1 w I r. I ~ w 1 I Cd:C'd m 1 I I r) I do 1 0' I ,, I I I m I t 1 I I N I N I I I I ) I :: I

0 1 01 I n I I I I0 1o Io I I ' I I I I v I I I I I N

fit I

I I I LL I 1 0 ~ I I - 1 1 .. 1 I I I - I -II ~ ~ ~ ~ ~ ~ ~ I I

4, I I z I I z Z I W Z

Z11 I I I I I I - I I e I Ii

DZ ZD :Z 1I I I D l I Ic t I I I I z I I -I I I Z

1 1 1 1 % O,'I I' It AnIn 1 1 O 0 ' r I 1 I, Ir I c I Cc CC)I I I'l I ru I I I v y N Iu Ii N Ii I I C' I M I I I I"

Il) If n I I Ir 0 in In It e) 4) in I I I , I) r. I I.L l I I I

II 1*1 I 1*1*1 .I .I 0, 1 I I I .III* ((11 *I *I( II.~l0 lf l~l 0IW 4 -'l0l0 NI"10I0 NOI I% Or- 0o

a- ' ' I . I . V I C I 0 I I (I ' 1 I . I I (S (1 .

I S I 'S - I * * I (I I 0 I I 0 I I 0 I IS I 4 I C I . I (' I (' V I V I N I I' I( I? V

I- I I I0 C I* * I IN - N I I0 - I ISI 'II 4 VI I ~I ISI S - I I- V IMai C

o I a o o i 0 0 0 0 I

t I I I 2 I I

2 0 0 a, Ion 2 I I I I IIt I I I I I I

I o 2 d I I I I N I rdrd I , C2 r, F F I

I I 1 F 2 t F e I I I IV I F I I

U. L, I I F . I F 2 F

I I - I

rd I IN202c I0-W FIn l I 1201020I

or1 1! 2 ; " 1:0 W ;:;

.n I2I in A ir ii in A i in F in in 2 o

2 2 I I I I 2 I I I0

TABLE C-3. OIL NO. 3, ALIPHATIC FRACTION

Key

UNK* Spectra with this designation contain some or allthe runs of the following masses whose parentstructures have not been resolved: 41, 43, 55,67, 69, 81, 83, 95, 109, 123, 137, 165, 179, 193.

Additional alkanes (not found by the cleanup) werepresent at spectra numbers 5352 and 5417.

C-l1

9'r- ;1- 1 1

I I w I I I o In I) I I I I I IV m Io.

t I m I o I i i Ii cu In Io I I 1, 0

> 1 I I Im 0. 11 v m I I I I I I I I I i I I ID II 1 , 1 o I ed I I I C, I I IW 1 I I I) in Am I

I l l I I I I I I d I rd I I I I I

0 1 1 1 I I I ~ ~~I X I I I I I I I I I I I I I I I I I I

wII I I I I I I I I I I IT I I IN- I I I I I I I I I I 1 R l I

t i l I I I I I I I I I I I I I I I I

( I I I I z I I I I ; I +

'- 11 I I I I I I II; I I I I I I I * Il l I I I I I I I I I I III I I I I I I w

III~ ~ I I I Iv I I

111 1 I I I I I I.. . .x11 1 I I I

I IClCl ml I IQI Iq q C I IC- 1-114f112 II~ ~ 1 .I C f

Il1 1 I1 a I U I OD I I

ill I w I" rd I 1 I *1 I * I I0 ~ l *- I ii I I I I I I I I I ; I _j . -I I I t . I

a - ~ i I I I I I i I I I I l I I I Id vC

N rd l. I 04 I ItI I I 1- I1. I I 101 I1

1. 3: X r 1

u I- I I I I a, 1 0 -'I4 0 1t I C u' I i IC

w II t 1410 10.14 I I') 't I I rdI I I vI r j ('1 I I .. (V I I rvI CI v r

ill I -11 1 10. I I : ,I I" ! o 1 1 d IV rds N 1 I

a I I 0.1 1 1 1 I I I I I I I I I I. I- IN I1

IW I D I f m ai a0 -e v a 0 0 n m 'a a a0 a. l, iAn a e. *d nl a as s,0 a., "I0a, ; ID 0' * a1 , C0 a t1 0 r I rC a1r a N M V I1 CD I o. x rd 0 wa

aD f CPI t ir I D, c I m a I aV a C, 0 1a O i Ir I , oI rd I aw I I I I 1 a 1 1 1 1 I I I I I

a' I

a It I I: : a a a a a* a a a a a a :a a I a I a i

a I I d I a aI

a~w r I 0 I I a a a aaa

CL1 a a a a a a , a a a a a w a I a I M aIa v a am

a a CL a a , a a , In a1 21 a a a a a a aa t a aK a' aM a a aa 0- 0- -- w -a a0aN a aaa aV aa- a a aN 0~C ~ -

a~~aa~aa~aca- I m-aaa-aaI 1ra-a a"4aa aa~0-~a~~~a~ 0a a-a,a~a0a0-4-a-Iqaa~a--.0-ala~aaa~~a~ N

av 1a~ 2awa. a. a a a Na a .1 - .. -a~ a , am a!

a T a a a a a a a a a a aa a a a aa a a aX a, av a a v aa aa a X a a a a a a a aa~ ~ ~~~~ a 1 an a am

a a a a a a a a a a aaCa a a a a I a; a a aICl I a a a a a a a a a a aari a -

a + at a W , aZ a a a a aa~~~aaP a a0 a a a aI -

araa~ ~ ~~~~~~~~ ad a aI a a a rla a ao 0 a aw a0 a1 ae a a a au a a. a. a a aa a a I a I a a Ia a

a -a aI a I a-I a a 0ain a, a a-- a 1 a a 1a w

ij a a a Io a a a a a I a aI- a a a a aa.) I a a a I~ a) a a0 a a a' u- a a0 a aC a ao I a Ia C i )I 1-9 1u Iu Ifv I uC

aw a a I a fa, aD av an ev a an aN a .a a a a a

v av aV av ar..l ak a a mID-- I a a a A a M" a ai a (A a al a) Inaw 1 m 2 a a1 a -r-- aW aV It m- m a1 m M lr) a I a a a

ala a a a a lgl r-- I I -. l I f I aI - a a a a aa, 0~ a, m e I a aa aD a, a d a- ) a a 0 r, a o a a a a a a aa~ m.- I p a a-.. a7 a 0 waaui ~ m a M a 1 M M oa n n ra a I a a aa a

a a a- ra a a a- a a a -- a a a I a a a a

6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 0 0 1 6 6 6 o

ic 6o o i ; i 0 0 0 0 6 6 6 6 6 6 6 6 6 6 6 6 * 6 6 6 .0 101* ~ 1 1 6 * 6 * 6 1 6 6* 6 , I* I I* I I I*6

I 6 6 6 6 I I -I I I 1 .0 1 1 1 Ow IOf 1 14 1 1, 1 06 1 1, - 1 1 11 0 1I I I in I Vo I I I I 1 1 4 1 1 1 1 1

6~ ~ 6 -6 6 6 6 6 6 6 6

60~0 060 0I0 060 0606 606 606 6OI 606O 060 060 06C 6060 060 C~C~I

6 c 6 I 6 6 6 6 6 6 6 6rv 6 rd 1 6 1 Vol 6 6 6 6 6 6 6

-C o I w I I 6 I I I M M 1 6" itIt ! 61 6 ! 6 . a 1 0 1 6 66

w ; ; 6 : C, 0 C, a C 66 6 6 6

6ii . 'i . ' 6 1 v; 6 r" ! 6 6 4 - 6 Z 6 r, I6n I LL I 6 c- I I &L I

6 1 CU 1 0 1 W t 6l d ro (V rd It : XM m 6 l m 6 0 6m 6 ) m 6) 6 Lot 6 6 6 6

6~~~~~' 61 it 6 6 6 6 66I x I 1 2 6 I I I 6 x 6 x I 6 x

6 ~ ~ 11 6 1 a. 1 6 6 t66 . 1 6'd 06.1 coo N6I.II26I; INI46t666..IqI I I

6U Q * 6 6W ~ . 6~ L,~N~' U IN 0 r' 1 U )Iu IU I IuI noI II I I I I

606N~6D.II60.O60 VP.6 6 6u 6 6V6.. M m 1 0 N.V6 6'CDI) C, a N o1 tlm 0 " 0 P - T r -

10 0 60 4 c 4 a a P, P, 1' 6, I P, P I 6 6 P 6 I M 6 W M M M M M Ma Ma 6

6 6 6 6 6 6 6 6 6 6 6 6 66 6 1 4

I I II I I F

* 9, .9 I 9: SI II F I I I I F ' I I

I I I I I I I

* F I I I I I F I I I I

F I I I I F I F I I I I I I

- 0 & ~0 OFOFOOOFOFOF9)~FOFOF0IQFO9OIQ9~F0I0IOFD* F I I I I I

I I I F I I

* F I F I I I F II F FFIFFFFFFF I

F F I I F F 9- C 0 0 0 QFOOOIOFOFOOFOFOFOFGOF OFOIOFOIC

F F F F F

I I F F F * FF ' I F F * F

* * F F I F F I F F

F F * . F F I F F

- - -. *. .,,0F~0.O...F0FOFOFOFOFOFOFOF.FOFF~FF F I F F , F F F I

F F I FF F F I I F F

I F F F F F FF I F F I I I F F 9

F F I F F F F I I

F F F F I I F F F F I- ~2 q ~ ~

\ F~* -~ FfF - - t~ ~F F I I I 9 I F I I I I

* F F F F F I 9 9 F I I 9 I* F 9 F F 9 9 9 I 9 F 9 I 9 F

9 F F I F IF F I F 9 I I F F F I

* F I F F I 9 9 F F I IF F F F F F F I I I F I F I

* F F F F F F F 9 I F F F 9 FF F I F F I F F

F I F F F F F I I F FF F F F F F F I

F * F F F F F F * FF F * F I F F I F F F

* * F F F F F F F F F * F FF I * F F

* F ' F F FFFFFFFF F

F F F F F * F F F F F

F F F ' F F F F F F F F FF F F F F F F F F * F F F

- F ' F F F F F F

* F * * F F F F F* *F,.FFF F F F F * F F F F F F

F . F I * * F FFFIFFF F F F F F

F F F F F F F F F* F F F * I F F F F F F F F F F F

- * F F FFFFFF F F F F* * F I F FFFFFFFFFF F* F F F F F F F F F F F F F

F F'FFFF I F FF1 F

F..........., F F F F F F FF * FFFFFFIFFF' * F F F F

F . F F F ' F F F F F F F F F F IF ' F F F F F F ' ' F F F 9

* ' I F F F 1 F F F F F F F F F F F F * * F* F F F F F F F F F F F I F F ' F F F FF * * F F I F F F * F F F F F F F * F F

F F F F I F I F F F F F F F

- F FFFFFI- F F F F F F F F

* I , F I F ' - F F ' F F F F F F * F F F F* . F I F F F F F F F I I F

* * . F F ,F F F F F F ' F F F F F . F F F FF F F F F . F F F F F F

* * 1 F * ' F F F F F F F F F

F F F F IF F F F F F F I * F I I ' F F F *F ' F , F F F F F F F F ' F I F F F F F F F

F -~ F F F F F F F F F F F I F I F F ' F * Fo * F F F F F F F F F F * F * F F F F F F F F F

* F F F F F F F F F F F F F I * F * F * FF - -* F F 1 F F F F F F F F F F F F F F F F

F F 0 4 F F F * F F F F F F F F F F I I F F FF t.9 JJF I F F F F F F F F F I F 9 F F F F F F

0 . FF'~.0..F F F F F F F I * F F F F F F F F F F F*I~~F ~I-. FC~F~F~F F F~F~F ~ OlDF ~Fl~F *FF~F~FF~Fl~F F FIs~FwI FW,9~FIMFIA~IIJ~IUJlIAJLIFFWFIIJW~JFF9Fr- J~; FOF)FFFF * F1F1FFFFF F~FFF. -~ F ~

F ** - *F4F9*~Fr~Fr~FCF-F9--F~F ~4 QFZ.OF FZ.ZFZFI~F.FZFZt~IZFZ9ZFZFZFZFZFZ~FZFZF2

~ FWFWIWFIaJILIFW FWF .U~F h.IF~F~.lO,~~FOFOOFOF4F9OFOF ~

F F F FF F FFFFZ .9FI F.FFFFFF9F9~FFFI.e~FZFI~FFI..FZFZIZ.4I0F 2 FZF,09Z ~

FFF F 9 I F 9 9 F F F F F 9

FF FF~F F F FIflF-I F I.F F I 9 F I 9 F F 9 9

F F F F F F F F F I I F F F 9 9 F F F F II F F F F F F F F F F F 9 F I 9 9 I F F 9 F F 9 9F F F F I F F F F * F F I I F F F I F

F F F F F F F F 9 F F I F 9 9 F 9 I 9 I F F

~F ,~

F~FVIFd~Fi~F.CF 4F~-9'IN9~FC~IO~FOFOFOIO *~~9~FI~ F.~F £'.014F4F4~

~I* F F F F F F F F F F F I 9 9 F I F 9 9 F 9 I F F

F ' F I I F F * F F I F I F 9 F I F FF F F F F F I F F F F F F F F 9 I I F

F F F F F F F F F 9 I I I F F 9 F F I F F

F F F F F F I F F I 9 F I I F F 9 9F F F F F 9 9 F I F F F F 9 I F I I I F F

F F I 9 F F F F F I I * I 9 9 9 9 9 F

F ~ .OIISF~FOFO1 F F I FF F F F F F I I F I F 9 9 1 I F 9 I FF F F F F 9 I I 1 9 9 F 9 I F F F I

1C-.; 5

TABLE C-4. MS OF OIL NO. 1, FIRST AROMATIC FRACTION

Key

@ in the ID column are identified below by the Spectrum No.Structures shown are compounds with similar spectra

10233 C1 3H, 6 (such as 2-heptynyl benzene)

H3C CH3

10234 C12H16 0 1,7-dimethyl tetralin

or

C11H1 20 0 3-methyl-3,4-dihydroCH3 naphthalenone

and

C1 3HL Trimethyl tetralin

10242 C13H16 (similar to 10233)

10243 C12HIE Dimethyl tetralin

and

C12H12 Dimethyl naphthalene

and Bu-t

C14H20

or CH3 CH3

H 3

C1 3H 60 C -

H3C 0

10244, C12 H1 6 0 Cyclohexyl phenol

10249 C12H I2 Dimethyl naphthalene

and

C14H2 0 or C1 3H, 0, (s2e 10243)

I

TABLE C-4 (cont.)

10254 c 13H 18 Trimethyl tetralin

andCH

C I5H2 ; t-Bu-e

or H3C CH C 3 IC1,H180 0

H3C0

CH310258 C15H22 or CIARO8 (esee 10254)

and

C14H22 Alkylberizene

and

Alkene cr alkylcycloalkane

10267 C14H22 HCCH 2CH2CH(CH3)2

H3C CH3

CH3

10274 C15H2 2 0

H3CPr-i,

CH3, 0 0

'02,13 C14H 8 0o0

CH3

H. >- .r CH42C(Cf' 3) 310296 C 1IH2S 0-k

CH310301 C15H2 2 (simi-lar to 10274)

ii C-17

I I I f I I I I I I I I

0 0 0 0 0 I0 90 1 0 o o 0 o I 0 Q CI 0 a I 0o C 0 0 0

Iii Iat 9 9 I I I I 9 9 9 I

09 uI a I In Ii q I I, I -a I 9 I o- CP v

In99 I in f 0 1 9)9C I 9 11 9 0 9 I m I

In 9 IV9 I I~ I I I C1 I VII( I I N 1 1,

f r i l 9 9 I 9 9 9 9 9 9 9 9 9 I 9

4 9 9 I I 9 9 I 9 I 9 9

9~~~~~-I~~~~ 99 I

999 ~ ~ ~ ~ ~ ~ ~ i I I 9 9 9 9 9 9

I Ij I I I I in I I I I I I I

- 9 9 9 9 9 I I I > I I I 9 9

999~ ~~~~~ M I I

99 9 I I I IL I V I I _j 9i Iv I , I ; I L 9

I I 9 I 9 I I I I 9 I - I 9 n o M f LnII I

II 9 9 9 9 9w I I w 0a9 1 0 1 1- 1 CD I I I I a I C -C .99 9 9

9 9 9 9 9 I I I I . 9 9 9 9 9 9 99

1. 99 4 9 9 9 I I I 9 1 4 9r n in1 v 91 9 9 99 9 9 9 9 9 9 9 9 9 9 I 9 9 9 9 1 I 9 9 9 9 I

0 99 9 rd 9 9 V. i P, m I 9 I 9 9 9 9 9q.' 999 Am 9 99 9 9 9 9 I 9 9

o ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ r 99 - 9II 999 9 9 9

999i Si 9 24 N 1N9 IN Id I 9 9 9 9 Ii 9M9- 9 9 9 9 9 9 I I I 993I 9-9 V9

I I - u I N N w 0

' 11 4I 1 1 1*1 I I I D I IC It I I I ICtM f n t ,, : t I I I I r I

I t I I I I I I tv I Il I I I 1 1 I I N N I I

I ~ ~ 9 I IrdI I I I c I I I I

I I I I I I I I II I I I P, I I I I

I I I II I I I

I~ I I

I ( A o. I I I I I

91 1 w 1 I 1I I I I

Ia z z 0 1 I I z I Z w W IL w11 Ir ~ WO iu Ix fI fl C II

I1 0 N s m i I PI 1 1 a w C, It 'aIO -0 1, P, P I P, OD 0 0 (O II 6

0 v I M 1, 1C I1 r I rd r- I -W I r f 0 I I, 1 I-I I I I I I in I I I

TABLE C-5. MS OF OIL NO. 2, FIRST AROMATIC FRACTION

KEY

1 Numbers in parentheses indicate ions whikh leew, to oeak siwmultaneouslj.

2) @ in the ID column are explained below according to Spectrum Nu;ilber. The

structures shown are compounds which exhibit similar spectra.

11332. alkane + C.Hjp(171,186) or CiH20(186,200) + CH10 16(169,164) +

Me Me M Me Me

C 8 H2 6, 0 (227.242)

Me

11335. C:;H.o(209,224) + C, H,,(195,210) + Cj- H P(171,186) + C,,H-( 19521j) +

Me ..y Me

C qH, 2 0 CH - CH2 '" (223,238,,93)

11356. CisH 18 "195,210) + CIIH 3 1

Me - (CH,) O (145,i19 ,6,258) + (228)

Me - (CH2 ).

S- I I> C 0

> I

E 0 0 o 1: o o o o oo0o o o o cIt I I I I I I I I I I

1" 0 0 0 - i 1 . "1 0 0 in D0 1 0 1 1 0 i 0, co 0Q m n

I I I

I I I t I . . . I

lo I ,

ro

2 )20 0 020 020 202 0 0 0 0 0 0J 0 0 0 2 C 0 .o IC

2 + + 2 2 2 . + 2 2 2 2 2, 2 2 2 -

iV o... .

a t I I I I I (i

N 0

I I I i I I I I m I 2

II" Z VIN m

0.22 20 r, 2-2. 1 0 m I

i 6- In

022~~~~~ I2).. N~I~ 2r 22 2'- N .2 2 2 2 2 .2~u2 I I N I 2N -1 IV I 2 u

I2 I

u uIu-22IQ I22 m- uqW (1.r 2 2 ' I) L.2)dO 0 W2.2 I02 2g ) I2 2-2I W Q

m2 0 2 1: In ! r2 2 2 2 20 ! Po2 r, I I~2.. M I M 1 2D j2. 11 12 -22 - N I N N I' y N 2V 2v N 'V C% N Co 2v N 2d N N N 2~ M

O 2 2 2 2 2 2 2 2 2 2 22 2WE I 2 2 2 2 2 2 2 2 2

2N. In2 2t I 2D I a, 2 M2 I" 2o 1, 0 2v 2, a m

222- 2w 2o 2w N rw N I 2 2 2 2 2 2 2

222 I

w i I I I I i 1 0 f 0 0 m I 0 0 I 9 0

a m I y I o I I 9v 9 I

COD . . . . . ... .. 10, 1

F m 0 ) 0 i 0 I V I m I N 0 ' I I I I N 1 0'

IW

II I II I I I .. .. . .. . ..I 9

I 9 I 9 9 9 I!

*I I I I I I I I II I II I 9 I9 9 99 9 9

i ro

a I I 1 0 1'I I I I I 0

I I N I I f ' I a I

I A I

t (I

15 CO.0 x

r, v, ro, I I

"d I rd I IV 1 4 N

I- I D tV~- I8 N-r2 0 I8, ItN I N9I9 1'0 I 1v

,, n .. . .. .. .. . (v . .. . i .... .. i . .i . .. .... . . . ... c •i tl

9 9 I 9 . 9 9 9 9 9

.. . . . . . . . .rt Irv Mm .. .. .. r .. . ..e i W. ..in i in in I' ..

9 9 9 9 99 9 9 9 9 9 9 I 9 I I 9 I 9 I 9

I 9 I 9 9 9 9 9 9I I 9 9

9 II 9

C-22I

9~~~A 9 9 9 9 9

* ~ I 1 1 1 0 1 * , I0 i I S I * I 0 I * ICI* I 4 I I I 4 1

rd I I I V 1 01 1 N I I II

1 M I

I m I Io I

cl i

r, 11 I Iw

N I CI IItm Ix 1 1I 110 (1 1m I'i : I 1 1 I

c ,a o NNI ICC I Q IZ Q n

IL I II I t

II 1 7 I , I ! I f:

I, WZ Z CO 1 0 1 1 Ib I 1 0 1 I I ~ I W w

If 1 I D 0 0 ZI I .

C, Co tM 'o I I I n 1 0110 1' I (r o N

CM Iv q I II

in (D I. 0I 0 1f I CD I 1 0 N r 'tc~~~ 4 z - o r l ( D 0

I~~f CI a' I I It

I I I I Ad

t"

o o o o 1

I" V orl IV I o I o ', rI o o . o o o ,

I t IIt I

I I I

'o o o o 0 o o o o

I o 1

1 4 f I I

Q I! C

I 4 i I to"'

I t 4 I I in4

I 4 4 I z I I 6 4

I M I I II

A, ro , rI 1-

cl I I ! I I I . i I I i x 4

I I 4 I

I I I "I I

n InI 4 14

I I , ( I I v I I I rd

I II

* 4 4

I I 44 II I I I i4 44 III I I I

I 4 4

4 i -I I 4 I 4

TABLE C-6. MS OF OIL NO. 3, FIRST AROMATIC FRACTION

KEY

I) UNK* These spectra contain some or all of the following ions: 41, 43, 55,

67, 69, 81, 83, 95, 109, 123, 137, 165, 179, 193, 207 structures have not

been determined.

2) Numbers in brackets [ ] indicate the corresponding spectra numbers in

Table C-4, Oil No. 1, First Aromatic Fraction.

3) Numbers in pareFitheses indicate ions which seem to peak together.

4) Additional peaks not included by the Cleanup program are:

12243 C12H or CIH,0 r10234]

12291 C13H1 !

12347 CjHjs

C-25

-mo-

C, IQ ,~.7 0 -A 14. LC L a 1 4) to

rl. v74 i .-- I- o- - f 6) m~ in: (Ii)in C M) r, 4 -0-0

-a r m ri. o,( N cD r r - -r Q .'r' *.7 M - -

17 4 rd-~f m -'o-- q CI -C nC-3 a~~i C- %

LLI

ILI

Z 7 7 ,j L* w 4 i

z <7 *a , 7 7 > LI<

or o 5'ni

- I I - C-26

p~C r r, .

*~~~ ') N .g ' I C ) q ' f.

- r' - -'X -

-' - - - - - -- - - - - - - - - - - C u 'C ~ ~ C'-.2 C .7' L C -. - 4 L - C' 'C'. .- ' h .

'C C ft (CL CL L CC CL C' C " & CC C --. F' 7 -~- - CLC'

I z

4~ IU

aC 'j C LCL L I - -' I I '

It -T iWj ' ' '

C- a7

4 0 * I

- z

Ir *y C, I

oru~'cC - 2

TABLE C-7. MS OF OIL NO. 1, MIDDLE AROMATIC FRACTION

KEY

Peaks not included by CLEANUP program:

7246 C11 H10 Methylnaphthalene

7247 C12 H1

7257 C1 2 H10 Biphenyl

7258 C1 3 H1 2 Methylbiphenyl + C12 His

7267 C1 2 Hiz Dimethylnaphthalene

7287 C1 3 H, Trimethylnaphthalene

7419 Cis Hj, or Cis H16

7479 C17 H16 Trimethylphenanthrene

If the "Identification" slot is empty, then no specific compound couldbe identified, although a definite peak exists.

C-29

., . .-J

rwr

2 0 a C S S

C, .f rj V 0 - .0 174

1, W1 :4 u.

4 z, I

1. 2! '- 1 ' , Ct.- ~ C 7 4 0

C' C

Qt w j>

cm)4. 4 4jL'

f7, aT t1

o~ ' .. r ' 'a-

u 'U Q I 4l < 4; u Q

0, q z cc - 4 rj i 4 'i I It 'I o '3) x , u m cu L

4 .l cIto - 4

I I

I i 1 0 1 I 8 4

II I I

0 4 4 4 a 4 4 a 4 0 1 V I , I c

1 I 0C A I I M 1 4 ro I I rd I4 I rd I ID I tv I I N 1 1 1 V I I I M

ItI I I~ 4 g g i ~ It I I 4 4 44 4 4 I 4 4 4 4

II

It

I I I

w

I 4 4 I I I I I w 4 z-x 4 I w I 4 4 4 4 I 4 I

I

ii~~~~~~~ IK I I I 4 I 4

I I I I 1 4 1 1

I 4 4 I I z I I z I I 4- W i 4 i

II 1 . . . CL I I I I

T 1 I

0 0 I 4 4 I 4 9 I I I w I 4 I r 4 ) 4 4 4 4 4 4 0a I CA

I I 4 I a

I -W i 4- 4 0 4 -I N I N 2

I n I i I I I I . I z I 4

I w 4 I 4I 4 1 1 1 4 I I

+ I -I -C 4 . I I I I I I w III I + I 4 4 4 - 1 0 1 4 I q 4 44 4

I x 4 4 I ; -x 1 1 x I 4 I x 1 4 I 4 I 4 1 1 4 I x 4 x 1 2 1 4

I- i .0 i S i Z I Z i Z i 44 I I I rd I I : I I I I

I I I IL I v I 4 I u I u I I I L) 4 Q I

I ~ ~ ~ R 4 4t4 4 I V 'I I I 4r I

4 0 1C I ID I OD I 1 0 1 4 1 4 1 4 ID:ID 4 0 4. 4 m W q ID w 4 W W 4 M CD 4 W 4 1 4 1 4 4 D W D C

M 1 4 1 4m 4 4 -n In s 1 4-4 1~ 4o

4 24 4 4 4 4 4 4C 4 431-

IL

I

11 IZ

I It

1 x

Iz

I II

C-3

VP I

TABLE C-8. MS OF OIL NO. 2, MIDDLE AROMATIC FRACTION

KEY

Peaks not included by CLEANUP program

8431 CIE H1 Dimethylphenanthrene

8563 C:9 H-. Isomer

If the "Identification" slot is empty, then no specific compoundcould be identified, although a definite peak exists.

rC-I

I!II

MF 0 F F Fn Fr Fn Ig I F M I N F CI r- F M I F C I f I

4' I r) m

L.d F Fu I4F C F F F I F ) F o I F I F I rd F I 'a

a : F F F .'F F F F F F F F F F F F F F F F

CF ~ ~ ~ ~ ~ l Fw F FZ F ' F F ' F.F'-F~~~dFOu FZ.e Q C ~ F . N I F O F ' D FC a U . t 1 C F. r F j r F F '

cm: ' F O t F -0 0 FF il C F F F F .- FF ' ~ l W t C C r F

F~~~~~~~~~ IFFPFC zFF ' . . ' F ' S F d F ' F )F l C C C C F F . F F F F

W~ ~ ~~~~~~~~~~~~~~~ Ft -

aI F* w ' ' ' F

z F F >FF F F (. F> FF.C ~ ~ ~ ~~~~ F F FIFF . . F

a ~ ~ ~ ~ ~ ~ ~ L L.F IF' ' F C F' F " F ' JF I'' 'FL w' a' . 'm F I C' F NF ' W FC

FCFF"FF z zF4 F~ qFTF F 'F-~ zJ FF FI Fz- z F FlEF F F F ; F F1 F-c F F F F F

F F'F F Fz Fz

F ~ ~ ~ ~ ~ ~ ~ ~ r F F F7

F~~~4 FI F F F F F F F F F

F F c F F F F, Fo Fr F Fo F Fr F FF F F FI Fm F F F F F F FC FD F F F F F F

a. I Ff F. IO FFl olf lF0I FD FC1 jF0.C(YF oF0. C.FqF2'a tFS t aFClr. o . 0

F4 Q XF F F FF F F I~F Fo N r. ao 5 c r ~ C trF CF-

.- ~ ~ ~ ~ ~ r Fn F FPF FIU FdFF FI F2F Fk'F FI vFI'UcFI dlc F2'F'.FncC2',FFmF FI F'FF Fd Fv Fw Fd Fv F - F F F F F F F

F F F F F F F ' F F F F-3FF4

v I P F F F I F F Fl F F l M M F l F i I F FF F4 I F

... ... . .... ... ... m, a). r. --j r) o o- m.. . . ' ' " -

l, "o q -T : - ! ,0 ra %

ac I, 10 u w'i ir i n ni m r m N m N m 7

zI

I I

CLI

I~ ~ ~~~ FZ I I Z1 F F F F

0 1F.: I F I F F-

I I I I Z F

I F F N F C F C - F - F0 F - l F N F - F F) F - F 0 F C I ' FNF'), C, F,, C F C F I F4

LL Ij .j

Z z i .

" <z z - " Lo .J . ., C .

F ' F F '"FrF- F-F F ml F

F ! Z F

t a I Uz m Z' 1 ' " m ,m r, L m m

F~~~~~~~ I I F F: FZ

I I Fl I ' I

F 51 1 0 I F. 1 F0 - F D o- F 0C F C- F Nl F D- F 1 F, 1 F 1-F F C 0 F 0- t C F 0' 0F F 0 F F'- 0 -

.It

r I OD F - 1 0 1 1 r I M I 9 I r I F) 1 0F f F I M R I n I F F , F F O 1 F F I IFgI M

FFFFC-35

0' C Y I h n C FIlFN dFfIC) m Fm Fm F - F V F F F i C - - -

F

I F F F F F F

CF z a) I- Fc m F F

FL- r) cF r, CC'' a * T ~ I 1- FC F-I.. Z. -

C- C) 2 2 0 0 0 00 00 C 00 07 CO .

0 Z C, C) C, . . F

I ~~ ~ , I I F * I IFu m Fr q F . FF

* . F, F F I F F F IZI

F I F , F ' I F F 1 I F I , F F Z* I F F F F F , F F

F ~ ~ ~ ~~~~~~ Z

-7 z , I z

* 4>'Y F 2? ,' I C F t'F O F 'nI IN F0 N~r N F O ~ FC -FL

0.4 'CF . 02 F',410 7 -Ft 0 tF7~r~I -Ff~ra j2F~ 0FtD5F

F F I .O .r FI

. N *r a- F F F F F01r

't IT F ,vv V eF, F F . 0* * , F. 0 * F F F. F F F . F . F . F , a- F F * F F F

z -) Fc F Fo mF FD FD Fr Fa

F F F F F . F F F FC -F3F

0 I - F 0 0IIII I I I I v4 1 10 1 I I V, 1 10 14 I 1 1 , I - I o I I 4 4 £ 4

.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . .I . ... . . . . . .. I. Id 1, Md 0 0 A* 4C4IY 4 I. 0 0 4 0I0 I Il 0 I CVW ! -M, h I0 1, ow U 0 - v I 4

lt InI I le i-i- rdl 4I 1 I I O I 4 i I in4 I

( V 4C V I C C I rdd (wC I IV 4 1 tv tv I rd I d 4d rV4C d CV I Cd 4 CV IV 4 it rd I C V ru CV r. CV 4v Cd I rd I rd I cd I Cd III

*I 4i fl 1 6 6 4i 6 o i 6 4i i i 4i In .6 6 In a co o r 0.

4 A 0 P, I 1 0 I q I N - I m I . 2 0 PI 1 0 - IDC I C I P4 CV 4 I Cd 4 I II I. I CDA 0 1, I'4 4 In N ID 4M 1 01 1 11 4 1 1 CV 4 I 4 I t, 0 Rm rol , Au 4v I ro 'r In I I I e I Il I rd I 4 4 I -I I d

II

I WI

It I I 1 7- 1 1I f c

. . . . I .I. l • . . • 4 • i

O I .

14 w It4 4

I I 4 4 4 -4 4 4 4 4 I I It It

a It a 0 a 0 It 0 It c a I In 1 0 1 a 4 In a

2 1 LL U I I of 1 . I u I LL I L 4 I u. L- I IL I 4

Z?Z I Z I Z Z Z Z , 4u Z Z Z Z Z I Z I L4 I I Z Z LZU4 4I It 1 9 1 1 1 I In 1 0 4 1 4r- I 4Q ~ I4C O IU 4 1 1 a 'C I < Q I La I I'4~~ z I z 1 4 1 1

I Zz 1 0

fu I"I

V V. I, V I ,1V IO ,1 1 I c. I I a I I 0 I 0 l I a, 1 (1 1 I w I to 1 0. 1 4.1a Iv

I I I

C-37

TABLE C-9. MS OF MIDDLE AROMATIC FRACTION, OIL NO. 3

Key

Peaks not included by CLEANUP program

9253 C12H1 2 Dimethylnaphthalene

9262 C13H12 (2)Methylbiphenyl

If the "identification" slot is empty, then no specificcompound could be identified from the data.

C-38

__ii

21 1O? :O 0o~O?010101010l:0'O'OIoIOr l OI l o!oioIOIO1 1,

6 o -- , r 0 111 t I I MI V - I M

P, I . ' fl.' ' M , 1!r I N MI 4 .

-C I I I C I in 1 I7 I o- a II I 1 0 I in 1 0 mIP 0 1 I I I I I 1 I , 1W~I tI 1, 41 km I I t I I I I P I II Ij 1 ; I 'a t : : I I It In Im Ia m In I c I I 1 I1

I I in ! I Id -t GO k IM I ID 1 I4 IY . I in I M I M rd I IN11 t 41 1 l n I D I ri I 1 I - I I I 1A in I rwI 1 .0 aM i I

I I II I I I I I I I I I I I I I I I

40 I 3 I z ct a

I I I I I W I I i i a a

I~ ~ ~ ~ ~~~~~~ I Ia

La ; i ! I I I I I I I

1 I I I I a

cI I I I I I I II) I

IU W + 4- II Ir Id L Z 4 a: I

IL + C Z I I I z I I I II I z J Iz I j I I I IW : I I

-j U. X I IL I I I> LU I 1 I I z I I I I I Iaf, f- x I Z. I I XI r -. I z 1 I

x I 0. 'L X x :, l, o I I CI w A Ic a CL S I I I

I a a , 4 LL _I- I3U IL I IL I I I

I I: 1 z4 > I v > I > I IC I

Il-- W M _j 1- l- I -I -j I a

W in I I i I I I I I I FA IX: 0 Z2 0.. (n u Q r I I I I Il v Q I

I T I x I I I W x a !a

O.I I -j I u u u I I-) I vl C I E I I a 1a

I I ()r N 1 0 0C I In V 0) -I d I OJ I m 0 1 1 0 1 it

.1' a. r, I Io I I , I I , 1 1 ILI1J P 1011'n(A CV l I~ Id r ' d d C V I 1d I I d r I %dI V I IN- I rdI dfN N 1t* r I aFIII.v)I I 4

I~ I I I I I I-. I I 14 1 I I I I I I I Ird m 014 N C t 11.10: 141 v I r I i I ' ,Io I .1 1 0I V I In111 41111C

CM 'KL ItJ'' ''0. CO 1 V rt ' I CI IZ CO I I Id rd d

''L' ' Z LI IW ' ',1: 4; -'IJ' I' 11 ZC-39I

I 9 IlOb 109

*1 I I II I I

I I I II I 9

I I I 910901099 9 9 9I I I II I I II I I I

I I I II I I I

lot

I I I II I I I

I .1 .1 .1IV I I WI

I0IC~9WIIVI~'I~~II-I~I I9 9 I II I I I

I I9 I I I9 I I I

I I I1 .1

IVl~I~tI-I-I-Iit-9r-9(~I9~9tVI-I

I I II 9 I I

I I I

I I I9 9 I II I 9

I I9 9 9 99 9 9I I I II I I II 9 I I9 I I 9

I I9 9

I I I II I I C

II I I I9 I II 9

.1 I I'I 9 I 9'I I I I

I I I 9I I ~I II I I II I 9 I9 9 I9 I I* 9 9 I

I 9 99 I II I II I I

ii I 9 9I I II I I9 9I I I

I 9 9 I9 9 I

I I I II I

I I II 9 I 9

9 9 99 9

9 I 9I I II I I 99 9 9 9I I I 9

9 99 I 9

* 9 II 9 9 9

9 9I I I 9I I 9 99 9 I I I9 9 99 I 9 9I I 9 I9 I I 9 rI~J 9~Il~JII - I -I IbululmI

in14 I49~-IItII'I~'I

* Ift9rIr4II I I 9

I I I I

~ i8i~i- I

SOAS*1.II-

I

I 0 0 0 0 - 1 0 1 101. 0 0 O 0 :0 .0 -- l 0IS i 0m 01' 0Im m in

1 N1 I I d

CV a I I 1 11"C a I I as - ii a I I a a a a a | I I a a Ia I I !

c a I I a a a a a a I ' I I I I I I I I I I I I I I I I I

N- I I I I I I o I I I I i I W I a I a -a a I

II .I I I I I I . I 1 a 1 .a . 1 1 1 1 1 1 1

i tl I I 1 I I I I I I I I 1 1 1 I I I

I I I I I I I I I 1 I I I I I I II I I I I I I III I I I I I I I I I I I I II I I ItI I I I I

" I Iw I I - I I II I I I I1I I tI I I I I I I I I I

I I I I I I I I I I I I I I I I I I I I I 1 I1 I. I. 1 1 1

1 x f I I I I I I II I I I I I I I I I I I

I I I I I I t I s Z I I I I I

I I I I I I I I a I I I ma It aW I aI I a aI I I III + I

II I I I I I I I I I I I I I I I I I I III I I I I I II I I I I 3I I > S. I I * I 1 I 1 j OI I I I I II 1 I I I z I f I I I I I I IC I I I I I I I I I I I I I" I I I I I I I I I I I I I w Iw I- I I zI I

I t I I I I I I I I I WI I I I I I I I I I I I I I I I I

I I 11 > E : I 1 v l I I III I I 01 I >X 1 Ic 1 Iw I - x I1 + I 1 I I 1 I I

ama 1 a I JI I I I- I Iaa

U, 1 W I I J I z I -

WII i 1- I-I a Ia I a Iaoa I It a i I a l i IC Z" a -a a a a a I1- 1 I a I I a a a 1 a I a I aa a a a9I n 1 > I m m > I I - a I In a I 1 i I I naa .a .a a., .a .1.1 .a ~ ~~.. . . . . a . a .9 . 9 1 1 9 a . 1

CII I 1 I I S 1 0 1 1 M 1 0 1 1 1 1 11 1 1 I i f, I I | II I I " IM IN . .~ I I 'i nI I$ I I I -1 I l I ~ l I I I I I1 I 1 : A : I I 111 I I r, I I I I "N . A 1 1 1 ;I N i K I n K I0I I~ cv 11 A l l , I l I I I I I I Im I I I I I .

I I9 1 11 91I I I It I M I l I I I I I I I I 9

VII V V** I I w I n I , 1a 1 0 10 , I1 to I 1 m I 1 10 I 4 1 N Il l I 1 I I1 1II I I I I ~ (I I t II ' I( I 1 I I 1 IV 1 I N IV

IIaIa II IfIa Ila awc Iaaaa~ amama--aslal-a a aIal l awamacan

- alma-a a I~l~l~l~lq-I IIa l al I a naga cC-4

I satIa a I ISl Iaa -aI a-aI IaIaoalaIaI I a aZa-aI a

II.aaZa U ama taIa a laI99aama IaIaIa Blaama Iama lala lZI a IaIamamaa a a a1 . I I a Ia a aII a a a) a a a a a) a I• I I I l l I a a a a a a aI a aU al a aIU a a al I a Ua

a a a a a. ai..i .. ai..i .... i.ai.i.ai a..i.ai....i..a a..i ai.. .i a " a i aa la a al a l l la~bl i l ~ l l l I l - l l ~ b l la a al 9 al l al a al al a a a a a a all l ~ l l ~ la1 a10 at 1 a1 1 0 01 1a a1 1 a110 a110 1 1

I a 9 9 a I I a I aa a a a a a a a a 9

aI

I 10,010101010101010101010 101010;I010100101 0101010101 0I101010101C

i , V I i , i, I i I I I I' i ' * V V - V V1, 1 P 1 I I 1 Iv 1 1, 1 I ev 1 - 1 u 1 1 i I 11 i 1 10 i I w Iv 1 m 1 1 1. Iv I 1 *1

It 10 rd 1 1 1. 1 1 C, I I I t 1 It I 1 1 1 1 1 1

ot I r I v I I n in 0 w I I I I I 40 1 0 -100 101010It0i 1 0' a 01 01111 :C R010101010 1000000000I CD I v rd m I I 9 !I l 1I 1 I re 0. 1 .0 1 or- I I I I I I I I, 1 0 1 1

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I t I I I I I I I I I I I I I I I I I I I

I ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 4 I 111 1 1

IC i ri vi~I .6 ai~I rI I I It - 11 1 I

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I I I I I I I I I I I I I I I I I I I I I I I tI I I

I~~~~~~~1 cI I I I I I I I I I I I I I I I I I I I I I I I I 1 I I I I I I A

I I I I I I I I I I I I I I I I I I I +

I I I I I I I I I I I I I IC I i i i I I II ~ ~ I1 1 aI I I I I I I I I I- I I I I I I I I

I~ - I I I I I I I I I I I :

I~1 11 -I I I I I I I I I I I I i I I I I II I I I I I I I I I I I I I I I I I I

I ~ ~~ ~~~ o I I + I- 1 0CI ! I I I I I I = I I I I1 1 1I I I I 1 1 III I I I - 1 0 1 It I 1 0 z IC It Z I I I

I I W 1 0IL I ~ I I II I I I I I I I 1 .1 I I I I

, I - ; 0 2 2! I i I I x I m I I IjI I z II I I I 1I I I I II z 'C I~ I 1 1 I I I I I I I I I I I I I -C

Z 0 Z I .JI I '(1) 0 I I I X I I I X> z O Ii x 1 V I I I I I~ l)I I I I I I II rd I 1! )- 4 I 10 I I W I I

I1 I*ILI I OK I I11 I I I I I i , . 1 I l l I I I I 1111 It W W I l- I I m 1 1 i

I~~~~~a 1 I I. I..1l- lI I I I Il.? I I I l l I I I(I 11 W U II I I I II I >2 0 I I I I I 1 1 K I I > 4 I

I 2 w I I P l I l l II' I I I-Li I I I II I -j IX Ei VI I z 1 I.l l.J . 2 2 ~ ~ I I I >2 III I I aXZ >. 1 . I m I a.1 I I I IlI I I I . I I

3 I 1w, 11-I x I- I a i I ->z *2 14 w I- > i ~I~~~~~~~~~~~ W I ZwilI~l I 2 ~ l I I I I 11 -I

I~l' I J U K r I I II- 1 ~ 0 1~ ~ I P I I I5-j 1 ; cm~I I I In 1+ I '1- I I I I

lo 4 0 I .11 14 1 I I 1W 0 1 LL Ip uI i : L1z 10. u 140 . 00 1 . 0C I W W 1 4 1 1 2 I I L 0 I I ..

1W I 1 1w m I P I rd I tI -Zt Z I?? 1 w' 1 - W

1 2 1 ? W % W 0' I-? I. U 1* 12 1. -a.J 1 4 I- 1

.3! j I I t ! lZII 4' Ilx l>? Z4 ll I-I lI

I* u l~ ~ 4 1I u1.2 Il- Lo) 0' IC u I.lhs1 1 ;~I ind I M. 12 I in I in I I ?0 1 1 1 II 11 I on lop

o 0 1'aI a I' 12 1 1,11.1 1It 1 M? I I~ 1I1 10 It 11 It1 1 1 11 11 I.1 11 0 1 01 11101 1

i~i~ U) IUIi UUI I IUI IUI~ I I~IUIOII I ILI IUI UIUUC-4I2

I~~~~~~~~~~~~~ I I I I I I I I I I I I I I I I I

* aaa" aa a

100010 o0i 0ii 0 a ag a

I I a a a a

a a I I I a a

I1 I I a I a a a a a aI. a .a a .a a i a -

I a ' a 1 ~aaaMa~I ~ a ~ I Iaa~

a . .. . . . .a a a a a a a a*aa aa............a.. . . . . . . . . . .

11. aaI . a.1.afa4 aa d-Ia amaaa Ia

apaI aa.p*q ~a a a a

aa a aa.

a a a a a aa a aa -a

aaaaaa !a a aa a a a a aaa a a a a"a a a,

a al a I a

I I I I

I I a a a a a a a a a I

-a a a a a a_-a a a a. a a aIaI

TABLE C-1l. MS OF OIL FOG RUN NO. 2 (B-1), HEfAVY AROMATIC FRACTION

Key

C H3

2a **30287 C13H,2 methylbiphenyl

C-44

I

Z I0 010 0 l lo o ol ~ io o ol l &, ; ;0001010001 lO010 0 0 0 00

;: ! ! ! i ! ! i 1 i i 1W I I I I I I IIII I I I f I Ir , N I I I I I f I D 1 0 m I ; IMI I 8

I 1'0 1 1 ! 1 1 10 10 I o I I M I I I I I I I I I I mI I I I I I I Id I I I I I I I I I I

LIIt

I I I I I I I I I I I I . I I I I I I I I I I I IL I 1 rod I I I -or, I R I I I ' I I I I I I I v I I I ISI m 1 I I I I r , , ,

. I I I I I I I I I I I I I I I I I I I I I I I I I I I a

I I I I I I I I I I I I I I I I I I I I I I I I I I

I I I I I I i I I I I . I I I ievi I I I I II I I I I I I I I I I I I I I I I I 1 I I I I I I I -- t I I

III

I I 1 1 I I I 1 1 I I I I W" I I I II I I I I I I I I I I I I I I I I I I I I I I I I I I I I

-- , 1.1.1"" 1 I -"i" . ., i 1- . .... ." i'" 1' ." .1."1'" .1i -,' i ".'"'".1 ". ".II I l l I . I l l ~ ~ l l l l~l lI I l~l-I l4 .l.UI I# -I ,~

I > I I 11 I I Z I I ev I I I 1.0lu I I I I I l lI II I I I I I I I I I I I I I I I I I I I I I I I II I I I I I I I I I 1 I I I I I I I I I I I I I I I I I I

C)II I I I I I !II I I I II II III II I I I I I

T I I I I I I I I

J I I I I I I I I I I II II I I I I I I I I I I I

I I I I I I I I I I - I II I I I I I I I I I I I I I I I II II3c I I I I I I I I I I* I I I I I I I I I I iI I I I I I I I

I I I I I I I I I I I I II I I I I I I I I I I I II r I I I I I I I I I I I I I I II I I I i I I I I I I I I I I I I I I I I I I I I

! I I I I ! I I I I I I II I I I I I I I I II I I I I I I I I I I I I I I I I I I

II 1 1 1 I I I I I I I III I I I I I I I I I

I I I I I I I I I I

I I z zI I I I -1I I II It4 I I I , I I 0 1 I I , I i :II I

W I I IcI ( I I III1III W 1I0I I I I I I I I 1 1 I I 1 I III I

I 1 I I I N D3 I II I I I I I I lI lI 1I! I W 3I I:T I I I I 1 I I + I

I I I 11 IlI L I I II I 11 > Lt 01 I I C 1 ! I I3 J I I >1 >I I12 I WE I I I I > 1.0I I.JI II N > II I

I I I i Iz I I 1 1 I I I 1 11 .1 1 1 1I w I I I M I I II 1 1 I I I I t I I I I I

,I I I I Z J I0 1 11 1) . III I I l I a I J I I 1 . 1 I I

. I I I z I I I I II-12121 2 I I I

0> I I : I.1 : (I i. !.0 I ! Il jA! gu! I 1 e i 11 i 1 1 I d e

I I Ii

I I 11 I 2II I K II I I I

X> i 0 1 In I i In InI I 1 nI I I I 1 I I I I I

I I1 I u I I u I u2 4 I $ 1 1 1 I1 1 IJ i I I p1 .. I I IZ I . I Ii I 'I'

0ll 0 I I I)I0 I I 1ZI 1 0 N 0 0 aIN a 1W,! a

u ~ ~~ ~ ~ ~ 12r1; ; ;011 3 1 ;z P

I l i CPI. 1 0 1 1 a a I a, 1 IIl V, I1I C I I IkJC IC.IZ' Z Z I I Ird I d I Cd I •WI

I IU) rd u u v CI I rd rd Cu I u I uV Cd Cd rd (V tv u "u •

I I ml I I I I I I I I I I I 0 1 1 I I I I I

III I vIi 111 0 I D.110 1 01 1)1 0 14e11J2 t Z I CD .

9=1 I I I11 I I I I $ I I I I I I II I

C-45

LI "Il~lI I

a rd a a a a 4 a a a a1 a a av

a1 M 1 a 11 1 1 1 a0 '1 CD I CV 'I a a a 1 a I IM

0 1 P. do d I d I I I c I I I I I I I I I

I I I a I I I| i I I I a a a I I a I a a a a I a

I | I II I i I I I iy X

1 1 ) 1 I I"I I I I I Ir l I' f z . P ' i q l q I I I iz ti I

11 1 Z 'on . '-

I I I a 11 1 1 1 a 1 1 1 a

, . . : -, ; 1 " -r I W |

li I I'C I ! 1 1 K mI

OXa It i a-faaa1aa2 tava~aardaaaav

1 1* 1" f I !

11a I a I a sa I a a I a I w I ac a I I a 1 a a ax a

ad.

w a w I -an -aa a w I ~ r~ aK aI- Ic Irwa

I

- 1

av r v! a a

4 1 1 0 f I K IN I N I I I N I I I J I

I Cl I 4 I e in I a 1 a 1 a I I a 0 N I a I ( I I I v I a

A I 1 1 a I a a a IaI I M I 1 o I a I a a a a a a I a a

It s iII a a a a I a a a a a a a a a

aa aa.aaa -acaat - -a a a a a a a a a a a a a a a -ao a aa a a a a a i a a a a a a a a a a a

ia la .1 1.1 1 .a.a 1 .a.1 a .a.a a .a.a a .a-li

IIWi~I It ' I I

Zr, "I cc 0 0 11 W 1 1 1 t 1

m ~ ~~~~ ~ ~ ~ rd I A MIM MIV V1 4 C 01 0 0 0' 0 1mIM I ,I m I C I IV1

0 1 0, 0 , 1 n I, 6 0 M I) 1 I 1 I I& It PwI I I I I M OD OD i p 4 n 0 1 1a:1 1 4 1 0 1! I r, I I r) 1 0 I ) I0 n 1 i IN 10 14 11 1 I i 1 4 1 ( I I I I I I I I I I I I I I I I I I

rv I Ion I

Id 1 I I I I I I 1 0I Id I I rm I I N, I

M ~I ~ I I I I I I I I OIr, W 0 1V I v I N t V)(V I t I r 'n.in 1 ' I I fl i I I I ) ri : Im 3 1 o P , . -. in I I I I I I t I I I I I I i I I

I M

I I " 1 1

I I II I I I

I O . 1.1 .1 ItUS Ii

I I WI .I -Ir .I -. rII I I~I .1 11 I I It 1 I 1

~ ~ I I I I I I I I I I I I I I I I I I

II I I I I I I 0 ~ JII I I I I I Ic I 1 31I I I

I I Iz *6 I I

I wuI z I 01 1 > W

I I V -C W v I I r I 1 1 1 I I I I IZPr~~~I I I I I I l I I9 W~ I I I I r

Ia Ix EI IX 4 I I I I I1 I I I I I I I 1 )

oz 1 0: Iz I 3m I.- Ix I 1 0:l 1I III II I L I l I I i I 1 9

w II I I I 10 I I I cc t s, I I I t IZI

II ~~~ ~ I I x ~ I I I I I I I 1 I ! j I

WZII I ill III-III I E < ~ I I-C IZI I W I I I. .I j I* ZI I I z I*In I I I z, l I 11 .1

0~~~ i I I w 1JZ ~- I 1. 0 1 0 P- I I I IW rI II UP I 1111141

I z I

-I I I I I I I I4 C41I1 4 4 Z L I 14 1 I I 1 1r 'I W Il W I I I IW t I IL

I I I I: I I I2 IX Ii I- II 12 I 1

I 1 -0~J 4 4 41 1 - 2 * >C > 141 - I jI

I -j 101 21 z2I3 I J I w I -I

I wIw wIw I w w ' 1 4 1 1 1 + I ~ WE1 m0 I wI C) I I I I~. I l 0 I I I I

Z' 0 M F 1 Il I0llIIlMI.JII3WI II0VI t1114 tal U 1 1I1 'Z M I I- I IW I I-->III~~aIJ I0>- Z tal IA0

II~~~ ;Z02>IIZ~0IJ Z 2 M 2 1 NI Ii I Z< ~ I ~ . h~I I - 2 W 0

III RrI I aJ r4 1 31 1 14 4 I 10 lI 1 I I I1

D I> ) I U IlJ U I~ I.rIDIlIII I 1. I IU I V IlI)' 0 m IV t 14V11 101 O I0I>rdi R ).I>WIa. I NI i I(v1 1- 1 1 i 1 1KIe

r, I, I I1 I 0 i on 10 M .3 AI.J 1 ..0I..Jl..lI.1.. : 1.1 It I I .Ii Me

0 'j 0 00 0 0 0 1 )l v4M~ 4 w4 4 W IWQ C 41 1 1 1IIIJIAIIIIIAIJIJI- I n10 ,inir inii ni i i 1 1 In 1 I ininI i I I~ la inI Z 1 19 1 1 011n11 1 InIi

rdI I I I I' I Ial Id Ia I (VI I rdI I CVI r 2 I1 1 CMIC a dIr VIr

U) I T ol 0 1 1 0 0 0V 14V Iw I d I I I 101 1 - 1 0 4 1 f IdI r V d I v

I v e I2 - - - -n 0 1 1 C* M 0I Ilp 1 0 t-I4 I-l I4I 1 a.- JI-4tN C

IUIIX

II I I I I I I I I I I I I I I I I I I-4 7

.t I I I I i I9 ' I I I

0 090109091090909091090?090 0 0 0 0010110 o, lo, l io

V I A *0 9 9 I 9 9I In I P, 1 .4 1

Pol 9 1 1 In 41 M- 9 9 I I I I. V

1 9 9 I i el I XV 1 i 90 i i I tv I* 1 -4 1 9 1 I

9 9 9 9 9 9 9 9 9 9 9 I 9 w

.9.9 9.9 1.9. .9- .1.1 1 9 9 9 9Z

9-~9( 9O9 9 9 . 9Go

9C~m9~9q9C~,949t)9~.9t-0 I~U U--9.- 991i l.O

(..19999)- 1~ 919 1 1 1 9~9 I I 9 9 9 9 9 9 9 9 9 9 9 9 I In

9 ~ ~ ~ ~ 4 91 1 1

IL .l.9. 1*. . . .1.1.93.9.It.9. It .9 9. I I I

9 9 I I -C I I It 9 9

11 - i 1 09 1 1 1c t 1 4 : I I I 9 I 941291. 1 i I

49 9 I 9 9 9 9 9 I x i1 I l I I I9~~~ w I 9 9 9 9

99 1010 :U I I Z I Ir I W I ; I Ij

i I I I J 9 9 '.

1 w I I -> 91 w I " I 9- I I W

SI ;; i I II-i T~ 9 1 M. I 9 9 I1I 9 9 9 9 9 9 9 9 ll I I 'I

Z- I I U) I ) I I I 1z 1 2 W I 1 1 Z4

K9 l 9 9 9 I I t I CL rd 1I z, 1 9

9 9 9 9 9 I I 1 9 . . .I I > J .

9~x 10 IL IL ICI 9 9 9 I 9 9 ;>I I i 9 I

1! II I I I v I IL I 2I . I I I I I I w w

@I92 I I I 4 I s4I I M IWMI .1 949 IZ I - 9jI I I

1~ 0 "- ~ 19191 1 92 I 2 Iu t- 1 D 1 I to I n

9 9 1I 9 1 -0 1In II I In9.99-I I n 1 I 1 : I i $rvI I I IZICEftI 92 2IIcv r~ I N~ N0 I I Wv I f I V

el9 4 91 It 91 12 1 1WII I I I

5 TABLE C-13. MS OF OIL NO. 2, HEAVY AROMATIC FRACTION

1 *1 Key

12 O7 -CH2 - H

*3 Molecule with a CH3- Ph - CH2- Or Ph -CH -moiety

or' C15H240 with a Ph -C- moiety

0

*4 CH2

*6 0 0

C- .19

0 1 4: 1 4 1 4 i ; i .' 1 1 1 : I I I I , 1, 1 !

l.4 41 a, it 10 1 I M it .4 v I I 1 1C 4 t Iw 4( 4 1 ON 1 0,1n I 'n

i 4m g 06 -i a. ti : 4i 4i 46 .6 .6 1 0 ,10 -

3 4 4 4 4 41 4l ~ 1 1S ,1 1e v I- IV I? w I in M 1 0 4 I r. tC 4 10

ow l I I w I I W

.0 It II 4Z 41 1 CM 4 4 4 4 4 4 I 4 4 4

1 - 1 4 I I 4 4 4 4 4 4 I 4 4 4 I I 4 4 4 4 4 4 4

II . .4 .4 4 .1 .4 4 . .4 .4 . .4 .4 1 . .4 4 4.4 4 . .4 4 . .4 . 7441434241- -> W0C44414.l 404~~~~~ ~~~~~ 4 4 4 ' i I 4rI 0 - 4 4 4O U -(' WqW4)4

44~~ J I I a" 4 4 4 4 4 4 4

44 4 I 4 4 4 4 I I 4 5 Ix i or x I I I IS4 4

14~~ I W I 4 4 4 4 4 IF 4 Z X> 4 4 4

i-I ~ 10440 401I ii ;4 40404-0 040 4.0 40 Wi 4.

II I I I I I I 4 I I W 4 4 I I 4

WJ 4 I I 4

W W In 4 44t 4 1 1 1 4 Z

a: IT I 1.1 I I , , z 2 W I I LL IiI~ le4 44 4 -jI Iz

> I LL 1 1 It I a p &L I I f ,I Ia

4Ll w > > 4 l' , , 44

Z4X W ;r l

I vI I~ W I I- I I I I0 A 4 I I 0> 4v 1 > 4

44 0 C I IV I 4m 1 4 04 4 d v I w 4w 441 4, 4' 4 40 4 ' I IV I I. l' 1 40 v

I4 I 4 11 x .4 4 4 4 4 4 4 4 4 4

4 1 It I -v I - I -w I * IW - w I q 10 4 4 1 V 4 4 44WL r4 1 40 1 a 4M44 i Ia -4 1 40 1W 4- a I a I+ 44a) a a I *aIIgo S 4 4

-v I4 e4 I 4d rd I2 IV I4.I44Ic I I It I 4rd 4 .4 .I r4 1 U4.dI-'Ic IId I e IN I I r I 4d 1 41 1 IV44- I

o 4 , -0 4. co C1 4 0 0 0 0, 10 -1 1 t4 4IL 44 It It 41 C4 4d (V4 424 IV I 0 4

O 44 4 4 4 4 4 44-4 44444 4 4 240.4 4 4 4 4)4 4-

01 11

I

' ' t , I' I I f I I I 1 1 f

I 1 0 m I o I t, ; r ; r, r .1 i m I ," 0 m I v 'D

I 1 I t 1 1 11 I 1 I I I I It I I

0-1I rl I CD I v m I m 1 .0 1 1 1 1 1

w w I I I I I I 4 I I I ' I r I I tln

t, I r, in J4 C0.4 1 I 4 I (D OD N & I 4 i I I

I ID 1 It 1 F I N I1 11 "a IV 11 M I III I I ,I

M 4d ro fV OD 4l r d r

* I 1 I I d I

Uzi I 4 4 4 ~ i I II 4 1 1 4I r I: : I I f I I I

I z 1- N101 4 24 -I I I I IZ

2-.1 I W4 4 1 4 I I w~ I2 I 4

44 a: Ir t .1 11.1 ! 1 4 w4 21 4 1 1 01 I I I II I I

00:.1 I0 I 4 1 4 4 I I I I12. I 14 12 I I I z

I 10. w I 1 I I 1 1 iI.1 I I w t 1 4 I I

+ )- I I 40 II) I 5 1 I i4 1 1; I

m 6.1 1W IZI I2 I I I 1 I-CcI I I0

11.14 '~0 , 10 40 IZ 12 U I I I> 0 ~ ~ 2 1.1 X

X X >l 1141 1 40 '0 I I >. Z

14W 4140 no I ~ I 4 I I I wI LrI rI I t4U n Cd c L 111.1 Q 2 cl iJ 0 1 1& a It4.14 , 4 - 14 IC~ 12 .J 1 4 I

rd 0 I - I 1d411 ;;: I- !4.4 II' r1 10 1 1 - O t - IP Im ( l I O"Io-1 W414 Z Zi z 1 x I I I)'! 42 0 I 4 i I I 4

441.- 0. I4 I0. 11- 1.I I 4 441I0 I 0 42 1 II 4 2' Ir I-. ?I I 4 4

4-l Sl- U) m4 1 4) 4 I W

o0I4' '1 t11 a I M I n , 0 a11 2 1 . .2 . C . . . .I. -' 'Z 2 r)v V i In' .0 IP ' WI I ; (or -0 I0- w m

w, , o, o, ,n 1, 91 o 1 0 en I 4 I f In 0 Ion" in 0 - 0 -D 4

4210' '40. 10 1Z 0. ' 0 1.1 4 O'.I I IIW I C> 4.4 1>4 .1e rd4 I ' d .d 1>VrI2Ic I C. CIr Itv r v C

I Z E 0. 0.4 I V.' a. 11 t2v)'Z40.4 1 .4.-l I' '0. .J'' ' W I~14lI'4 In'1U4 )-)-~ 2' 4j). .4 III .. 42I-.- I 4

Am -I 'I I0 Q 1 2 E1I 1 1 4. '4'01 .4 0

TABLE C-14. MS OF OIL FOG RUN NO. 4 (B-2), HEAVY AROMATIC FRACTION

Key

0

II

C-52

mj I A 0C Iv v i - c iv

L* 0r . LI 'i r -

o Co 0'0 00 0 t0 CA00 0 0 0 0 0 0

U !~ ~ I F F I FI F F I

0 CD CA r m I 0 I 0 'r ' w I I

u m rdcjr in-I ~ r J F) i InI - .I I F F F F X

I ~~1 F 'IF

F Fcc F I F I I I

Q L7.A fl h

ul w I

It zI T I w I

I I I 'i F F I I< F

CA- I

z .

F. r rC D 0 1. C I I C

r- 0* M C FOM C D CO W c

r l CA I. Ii r A r A C A C A C A C V

IC--

10;0:0010;001000;001010010;;040;0.4o0:,

f 4d I 1 0 W)1 0

rd4 I I I I In I 4l I I 4 1 44 1 v I M 4y 4 d

cc4 4 4 4 & 4 4 4 4 4 4 4W4 4 4 4 4 4 4 4 4 4 4 4

94x4 4 4 4 4 I 4 4 4

1.-I 4 4(4 4 4 ~I 40

05 W I. I I. I W I W I I W i W 4 4 1 4 4 1 W W f I -CI I W I 4~ O r

.1 1 4 1 1 - ; 1 : .

44 I I 4 I I v I Q I u I u I v I u I 4 I I v p

a, If .0 ?1 4il in I m I K 1 0, C, o- 0 '0 4

W 4 I 1 9 1 4 It r) 0 i 4 I A A R v I m I v * iM44 I 1 10 W Ca IV 9 10 1 W 1 1) 1 9 0, 1 0. 1 a. l 4 0. a

m4 4 0 in I K w 4 2 i t2 i 0 1 0 1 4 m . (v , n '044~~~~~C 4v : i

a - 4 4 4 4 I 4 4 4 4 44 4 4 4 4 4 4 4 4 4 4 4 4 4 I 4 4 4 4 I

4 4 4 4 4 4 4 4 4 C - 5 4 4 4 4 4 4 4 4 4I

4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4

It I I I a I It a a a a a

V I D. 1 a o a a al I 0 i In .1 I I m I

I a a o a a a 1 1 a a 1 1 a a 1 1 1 1

zaa~ 0 i 11~~t-~t~~ It a~oq~ OW I

icamll ar- a awaaa I0 iep~ I Oa i aai i h wa~-- ; ;n-a~ " a 1 1 w11 WiWIa a a I0 I~u~ Iaa~ I P~~- I~a a~I-a~Tfa-1v 4L a-- - 0 aaannawn aaa a-- aa !m- a- aIw ana a aax a a a at at a- _5 a a a a a

a a a a a a a a a a at

a a1 a' l Z o a a at a. 1 a1 a1 a I aa CD I a a a a a av a a a a aIa a a a a a a a a a a at

a am .0 a a 1 1 a1 a a a a a a a a a

av a n Itaa . . a . a a . aoa, o o- aq o-0 I a- t c i at-a .m a , Va. l~oa. @I 1 0

lia~~~~~~~au~~e amn ca0aai~o~aaaa0gaa

tiaa aqaa~afa naa~ara~a-~a aa ara a

TABLE C-16. MS OF OIL NO. 2, NITROGEN BASES FRACTION

Key

C13H,5N Type A (184,185,157,156) -loss of Hprobably tetramethylquitiol ine

Type B (185,170,186) -loss of CH3probably C5-alkylquinoline with at leastone ethyl group

C1 4H 1 7N Type A (198,199,171,200,172) --loss of Hprobably pentamethylquinoline

Type B (184,199,200) -loss of CH.probably C5-alkylquinoline with at leastone ethyl group

CL5HjqN Type A (212,213,185,198,214) -loss of Hprobably hexamethylquinol ine

Type B (198,185,213,212,199) -loss of CH3probably C6-alkylquinoline with at leastone ethyl group

CIbH2IN Type B (212,227,226) -loss of CH.3probably C7-alkylquinoline with at leastone ethyl group

C1 5H 13N (207,208,206,165)Methylphenyl indole ordimethylbenzoquinol ine

C16H,1 N (221,222,220,178,206)Dimethylphenylindole ortrimethylbenzoquinol ine orC15H1INO as diphenyloxazole or I

phenylquinoline oxide

C-56

I

C- 56

Laj P I I I I It I I I I I I I I I

u a a a a P a a a a p a

maP it a a a I I I I ID N I I I I p

.4 1 IS a I a a i I av i a a m p m i A w- a av P )i t lr PIId Na~~raaaaa-ra.c~st~ 1aapyaa- 4 1P .P'Ijay', P4- t -oa a a Ina~a- a - a1aaa a*

Iaa I I I

It1 1. .U. . .It It t.1. I P I I

4v I ~~

II C I I I IL I CL L a p a a a aZZl I M

1 01

ua I

It I lxi m I N a. I1 1 I 1ii I ; I ;; I g I g p I M .I I , M p p

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TABLE C-17. MS OF OIL FOG RUN NO. 9(A-2) NITROGEN BASES FRACTION

Key

C13,h5N Type A (184,185,157,156) -loss of Hprobably tetramethylquinol ine

Type B (185,170,186) -loss of CH3probably C5-alkylquir'oline with at leastone ethyl group

C14H17N Type A (198,199,171,200,172) -loss of Hprobably pentamethylquinol ine

Type B (184,199,200) -loss of CH3probably C5-alkylquinoline with at leastone ethyl group

C15H1 gN Type A (212,213,185,198,214) -loss of Hprobably hexamethylquinol ine

Type 8 (198,185,213,212,199) -loss of CH3probably C6-alkylquinoline with at leastone ethyl group

C1 6H2 1N Type B (212,227,226) -loss of CH3probably C7-alkylquinoline with at leastone ethyl group

C15H13N (207,208,206,165)Methylphenyl indole ordimethylbenzoquinol ine

C16H1 sN (221,222,220,178,206)Dimethylphenylindole ortrimethylbenzoquinoline or IC1 sH,,NO as diphenyloxazole or

Phenylquinoline oxide II

C-6fl

L7,!

APPENDIX D

AEROSOL DATA FROM EXPERIMENTS 3 THROUGH 12

D-1

AEROSOL EXPERIMENTAl. DATA

The following Tables D-.! to i-10 Jive the complete experimental data

on aerosol aging as measured with the P/Z imractcr and the ASAS particle spectro-

meter, including data analysis and correlations for Experiment Nos. 3-12. Table

17 in -he body of the report appears here 3s Table D-2.

Figures D-1 to 0-10 are histograms of the particle size distribution in

Experiments 3 to 12 as measured at the initiated time after to. Note the change

in distribution in Experiment No. 6, from 9 min in Figure D-4 to 16 min in

Figure 8 in the body of the report.

II

II

II

D-2 I

TABLE D-1

EXPERIMENT NO. 3

P/Z Impactor ASAS

Time (t) TSP d6 Time (t) di No. ofmin mg/m (1rm) min Jm Particles (n)

30 616 .960 5 1.21 372229 1.27 30886

40 536 1.35 15 1.25 2795620 1.25 29985

50 664 1.33 26 1.26 3138029 1.24 30318

60 854 1.343 43 1.37 2587456 1.28 26954

STATISTICAL ANALYSIS: FOR STATISTICAL ANALYSIS: FOR

LINEAR REGRESSION CURVE n = noe -kt

1) TSP vs t n =33860slope = 8. no

intercept = 289, K = .005correlation coef. = .805 correlation coef. = 0.747

2) dm vs t Equation:slope = .0113 -.O 5

intercept = .7377 n = 33869 e

correlation coef. = .764Inn = 10.43 - .005t

Equation: 95% significance level

y =mt + c

m = slope and c intercept

D-3

.1 ... .... --- . -TT- -i -" --- ..

TABLE D-2

EXPERIMENT NO. 4

PiZ Impactor ASAS

Time ,t) TSP d6 Time (t) d No. ofmin mgi/,, 3 (wm) min Pm Particles (n)

2 144 .686 2 .776 4562210 739 .842 4 .853 52368

18 667 .876 10 .813 46992

36 634 .324 15 .823 42884

44 566 .831 36 846 33718

52 598 .878 44 .850 31352

50 506 1.00 52 .888 22506

60 .893 13774

STATISTICAL ANALYSIS: FOR STATISTICAL ANALYSI-: FORLINEAR REGRESSION: CURVE n = noe-kt

slope = - 3.9 n0 55826

intercept = 763 K = .0184correlation coef. = -.944 correlation coef. = -0.93

2) dm vs t slope = .00313 Equation:

Intercept = .749 n = 55826 e " Icorrelation coef. = .744

Inn = 10.93 - .0184tEquation: 95% significance level 5

y =rMt -~c

m = slope and c = intercept I

DII

D- 4

TABLE D-3

EXPERIMENT NO. 5

P/Z Impactor ASAS

Time (t) TSP 6 Time (t) d6 No. ofmin mg/m3 (um) min pm Particles (n)

13 236.7 .821 2 .899 4907

17 184.2 .733 7 .880 4436

28 303 .734 14 .947 4622

37 372 .773 26 .926 5129

46 262.8 .790 36 .900 5432

56 283 .702 45 .906 5179

54 .916 5527

STATISTICAL ANALYSIS: FOR STATISTICAL ANALYSIS: FORLINEAR REGRESSION CURVE n = n0e

-kt1[ ) TSP vs t n=48

slope = 1.786 no 4582

intercept = 214.98 K = 0.0034correlation coef. = 0.47 correlation coef. = .8294

2) dm vs t Eguation:slope = -0.0011 0034t

intercept = 0.795 n = 4582 e'correlation coef. = -.425

Inn = 8.43 + .0034tEquation: 95% significance level

y = mt + c

m slope and c = intercept

D-5

TABLE D-4

EXPERIMENT NO. 6

P/Z Impactor ASAS

Time (t) TSP d6 Time (t) d6 No. of

min mg/m 3 (vim) min Pm Particles (n)

2 359 .6675 4 .888 32737

9 432 .6585 7 .870 24418

16 340 .7020 13 .872 33053

26 449 .7060 23 .873 26424

35 476 .724 32 .875 20506

44 489 .7712 41 .895 18356

51 440 .7607 58 .935 13532

60 450 .8270

SrATISTICAL ANALYSIS: FOR STATISTICAL ANALYSIS: FORLINEAR REGRESSION CURVE n = n0e'kt

1) TSP vs t no = 34200slope : 1.3o

intercept = 394. K = .015correlation coef. = .5049 correlation coef. = -.9212

2) d6 vs t Equation:slope = .00262 015t

intercept = .6576 n = 34200 ecorrelation coef. = .958

lnn = 10.44 - .015tEquation: 99% significance level

y =at + c

m slope and c = intercept _

I

TABLE D-5

EXPERIMENT NO. 7

P/Z Impactor ASAS

Time (t) TSP dm Time (t) dm No. ofmin mg/m 3 (lim) min Pm Particles (n)

2 384 .796 2 1.158 6283

6 462 .767 6 1.113 6354

10 558 .7847 10 1.185 6810

16 605 .8235 16 1.168 6366

28 529 .834 24 1.185 5646

34 503 .8512 34 1.171 5480

44 567 .8167 44 1.071 5746

52 597 .8374 52 1.069 5480

60 514 .883 60 1.053 5326

STATISTICAL ANALYSIS: FOR STATISTICAL ANALYSIS: FORLINEAR REGRESSION CURVE n = noe-kt

1) TSP vs t slope 0.5 no= 6687

intercept = 570 K = 104

correlation coef. = -.2272 correlation coef. = -0.848

2) d6 vs t Equation:slope = .0014 - .04t

intercept = .7821 n = 6687 ecorrelation coef. = -.2272

Inn = 8.808 - .0004t

Equation: 99/ significance level

y = Mt + c

M slope and c = intercept I

D-7

TABLE D-6

EXPERIMENT NO. 8

P/Z Impactor ASAS

Time (t) TSP d& Time (t) d No. ofmin mg/m3 (11m) min i1m Particles (n)

12 748.2 .7726 2 .990 9046

20 778.9 .796 6 .987 9425

28 729.6 .792 12 .961 8116

38 714.6 .795 19 .900 6502

48 602.4 .792 27 .932 6677

58 604.2 .828 36 1.00 5668

45 0.928 5640

54 0.944 5423

STATISTICAL ANALYSIS: FOR STATISTICAL ANALYSIS: FORLINEAR REGRESSION CURVE n = n0e-kt

il) TSP vs t slope = 3.947 no = 9118

intercept = 830.34 K = .011correlation coef. = -.913 correlation coef. = -0.941

12) 6 vs t sloDe = Equation:

intercept = .768 n = 9118 e - Ollt

correlation coef. = -.913inn = 9.118 - .Ollt

Equation: 99% significance level

y = Mt + c -

m1: slope and c : intercept

I

I

TADLE D-7

EXPERIMENT NO. 9

P/Z Impactor ASAS

Time (t) TSP d6 Time (t) d& No. of

min mg/M 3 (Ijm) min Pm Particles (n)

9 586.8 .739

17 791.4 .863

27 849.3 .799 17 .919 37207

35 621.9 .834 26 .934 31712

44 698.4 .797 35 .920 28020

54 736.2 .810 44 .933 25129

54 .917 19551

STATISTICAL ANALYSIS: FOR STATISTICAL ANALYSIS: FOR

LINEAR REGRESSION CURVE n = noe-k t

1) TSP vs t n = 49662slope = .7894 o

intercept = 689.53 K = .0166correlation coef. = .133 correlation coef. = .991

2) d6 vs t Equation:slope = .00056 - 0166t

intercept = .790 n = 49662 ecorrelation coef. = .226

Inn = 10.813 - .0166t

Equation: 99% significance level

y = mt + c

m = slope and c = intercept

D-9-

TABLE D-8EXPERIMENT NO. 10

P/Z Impactor ASAS

Time (t) TSP 6 Time (t) d6 No. ofmin mg/m3 (rm) min Pm Particles (n)

14 550.2 .7604 4 .928 12857

22 580.5 .761 8 .932 14037

32 543.9 .737 14 .921 11516

42 538.5 .742 22 .933 9058

51 542.7 .776 32 .936 8320

60 629.7 .798 42 .937 5957

51 .933 5931

60 .944 5770

STATISTICAL ANALYSIS: FOR STATISTICAL ANALYSIS: FORLINEAR REGRESSION CURVE n = noekt

1) TSPUVSE n = 141861) TSP vs t slope = .8216 o

intercept = 534.0 K = .017correlation coef. = .405 correlation coef. = -0.9656

2) dm vs t Equation:slope = .00072-

intercept = .736 n = 14186 e -0 17t

correlation coef. = .561Inn = 9.56 - .017t

Equation: = M + c 99% significance level I

m = slope and c intercept .

III

D-10

TABLE D-9

EXPERIMENT NO. 11

P/Z Impactor ASAS

Time (t) TSP di Time (t) dm No. ofmin mg/m (um) min Jm Particles (n)

14 377.7 .535 5 .748 5950

22 299.1 .576 11 .754 5687

32 328.8 .563 18 .763 5627

41 345 .642 28 .767 5751

51 381 .629 37 .759 5713

60 327.6 .611 45 .797 5676

54 .774 5638

STATISTICAL ANALYSIS: FOR STATISTICAL ANALYSIS: FORLINEAR REGRESSION CURVE n -kt

1) TSP VS t n £2slope = .0774 no = 5826

intercept = 340.4 K = .0006

correlation coef. = .0426 correlation coef. = -0.643

2) dii vs t Equation:slope = .0019

intercept = .524 n = 5826 e- 'O 006tcorrelation coef. = .790

Inn = 8.67 - .0006tEquation:

y = mt + c

m slope and c = intercept

D- 11

TABLE-D-I0

EXPERIMENT NO. 12

P/Z Impactor ASAS

Time (t) TSP d6 Time (t) d6 No. ofmin mg/m3 (um) min Jm Particles (n)

12 805.2 .741 3 .8840 21870

20 867 .776 8 .8815 23754

30 888.3 .749 16 .8900 20126

40 811.5 .777 25 .8762 18160

50 673.8 .778 34 .912 14061

60 797.1 .795 44 .8823 14309

55 .8920 10671

STATISTICAL ANALYSIS: FOR STATISTICAL ANALYSIS: FORLINEAR REGRESSION CURVE n = n e-kt

1) TSP slope = -2.11 no = 25084

intercept = .738 K = .0146correlation coef. = -.512 correlation coef. = -.966

2) d6 vs t Equation:slope = .0009 -.0146t

intercept = .738 n = 25084 ecorrelation coef. = .794

Inn = 10.13 - .0146tEquation: 99% significance level

y :mt + c

m slope and c intercept

DII

D-1?

t-

U

0

°4--

o .4

C

C,

.2

l2 3 4 "

Particle Diameter, dpn pr)

Fijure 0-1. Histogram of Mass Median Particle Size Distrlbutior Expr rimentNo. 3. 30 minutes after to.

D-13

4--

0

r

w

.2.

o2 3

Particle Diameter, do , "M

0!

Figure D-2. Histograrl of Hlass tiedian Particle Size Distribution ExperimentIC,0. 4. 10 minutes aft3r t o . I

D-14L_ l3*

t6CO)

4--0

Cra)

L

.2

12 3 4 5 6

Particle Diameter d -*---1-

Figjure D-11. Histogjram of Hlass Median Particle Size Distribution lxperimerntNlo. 5. 13 minutes after t,).

D- 15

.6

w .5

Q .40

C.--

.3

.2

* .1

II I2 3

Particle Dianeter, d , In 10*' 0

IFigure D-4. 'istogra;,i of Miass Miedian Part-ie §_izv .i stribut/iol, E>perirent

Nlo. 6. 9 ninutes after t.

D 16

.6

U

n

cm .4

.3

Particle ,iarnter, d,, i

Pigure D-5. Histogram of (lass Mediin Particle Size f ictribution [,e- ntlo. 7. 10 minutes a-,er to.

I0-17.3

t 6

.5

U

:=U

UC> .4

0

UCc=

- 30CiS.-

.2

*.I

r- u F Ii- -i

1 2 3Particle Diarieter, dp, Jm

Fiqure 0-6. 'iistograv., of Mass Median Particle Size Distribution Experime!', 'No. 2. 12 miniJtes after to.

r-18

t.6

CaU

C

C

0

U 4Cj

U~.

.3

.2

2 3

Particle Diameter,dpJr

Figure D-7. Histogram of Hass Median Particle Size DistrilhutionExperinent No. 9. 9 minutes after to.

D- 1.'

S.6

.5

0

S.4

S.-Li- .3

1 3

Particle Diameter, dp~jimI

Figuire D-8. Histogram of Miass Median Particle Size Distribution ExperimientNo. 10. 8 minutes after t.

-2 0

7

1.6

S 5

C)

4

S-

3

.2

0~

2.3

Particle Diameter, dp ,IJM

Figure P-9. Histogram ot: Mass Median Particle Size DistributionExperiment No. 11. 8 minutes after t0 .

D-2 1

1.6

C

4-c .4

UC

3

.2

Particle Diameter, dp~iIM=1

Fij,,ue D-10. Histogram of Mass 1Mian Particle Size Distribution [xperilleitNIo. 12. 12 minutes after to.

D-22I-idiom MA

ttI AhBR)L U

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