The pyrolysis of naphthacene
by John Charles Philip
A thesis submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree of
MASTER OF SCIENCE in CHEMICAL ENGINEERING
Montana State University
© Copyright by John Charles Philip (1967)
Abstract:
The pyrolysis of naphthacene was studied in a Thermogravi-metric Analysis (TGA) apparatus in order
to obtain information which might be useful in the manufacture of commercial pyrolytic graphite.
During the pyrolysis runs, data was obtained concerning amount of weight loss, temperature, and rate
of evolution of the gases produced by pyrolysis. Following the runs, the products were analyzed. The
final temperature of all runs used for quantitative purposes was 625-630°C. The results of the product
analysis were used to form a stoichiometric equation for the overall reaction of naphthacene.
Four compounds and unreacted naphthacene were found to be present in the condensate. One of these
was 5,12-dihydronaphthacene. The other compounds appear to be two oxygenated compounds and one
compound that maybe the result of further reaction of dihydronaphtha cene. THS PYROLYSIS OF NAPHTHALENE .
by
JOHN CHARLES PHILIP
A thesis submitted to the Graduate Faculty in partial
.fulfillment of the requirements for the degree ■
of
MASTER OF SCIENCE
in
•CHEMICAL
ENGINEERING
Approved:
/(
Head, Major Departrneniy^
Ihairman ^Examining Committee
Dean
MONTANA STATE UNIVERSITY
Bozeman,, Montana
December, I 9S 7.
iii
Acknowledgement
The author wishes to thank the staff of the Chemical Engineer­
ing Department at Montana State University for the help which they
gave him during the course of this project.
Special thanks go to
Dr. Robert L. Nickelson, who served as thesis adviser, and to Dr.
Michael Schaer 1 who did a great deal of the work involved in the
building of the chromatograph used to analyze the reaction■gases and
who also did most of the troubleshooting when things went wrong with
the chromatograph used to analyze the condensate.
He also wishes to thank Dr. Robert Currie, who built the TGA
apparatus which was used in the experimental work; Mr. William War,’
who also helped with the building of the chromatograph used to analyze
the gaseous products; Dr. Graeme Baker, who provided assistance with
the interpretation of spectra obtained during the analytical work; and
Dr. Joseph Kiovsky, for his information about industrial preparation
of pyrolytic graphite.
For their financial aid during the course of this project, the
author wishes to thank the Continental Oil Company and the National
Aeronautics and Space Administration.
Finally, he would like to thank his wife, Anita, for her
assistance in getting his experimental data onto cards for computer
input.
iv
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-■ Table of Contents
'Page
List of Tables
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List of Figures
Abstract
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Introduction
Equipment
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Experimental and Analytical. Procedures. . . . . . . . .
Results and Discussion .
Conclusions
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Appendix
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Literature Cited .
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V
List of Tables
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Page
Table I
Compounds Involved in this Work .
Table II
Points in Calibration Curves .
Table III
Program to Read Calibration Curves .
Table IV ''
Interpolation'Subroutine
Table V
Program for Integration of Gas Evol­
ution D a t a ............. ..
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'.36
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Table VI
Program to Graph Tables VII-X
Table VII
Ex-NA-7 ...................................
Table
VIII
Ex-NA -8 .......................... ...
Table
IX
Ex-NA-10
................................ 58
.: Ex-NA-Il
................ 65
'Table X
Table
XI
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35
4-2
. 44
51 •
Results ofIndividual R u n s ................. 72
Table XII
' -.
Products of the' Pyrolysis of One Mole
of Naphthacene
Table XIII
Variable Names in the Computer Programs
'73 '
74:
vi
List of Figures
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Figure I
Thermogravimetric Analysis Apparatus
Figure 2
Equipment Modifications and Product
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L o c a t i o n s ................... ..................
Figure
3
Ex-NA-7" "Results .
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Figure
4
Ex-NA -8 Results- .
•* . .
Figure 5
' Ex-NA-IO Results
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Figure
6
Ex-NA-Il Results
Figure
7
Chromatogram of Gaseous Products
Figure
8
Condensate Chromatogram - .
Figure 9
Figure 10
Figure 11
'Infrared Spectrum
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' Ultraviolet Spectrum
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. yy
. yg
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79
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gg
8l
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ofCompound II
Infrared Spectrum of Compound I
75
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Page
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. 82
83
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of Compound
I .
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Figure 12
Infrared Spectrum of Compound T H -.
:
Figure 13
Infrared Spectrum of Compound IV
Figure I4
Ultraviolet Spectra of Compounds III and
IV in E t h a n o l . .. . .
.......
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84
.. " 85
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* ■.
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86'
.87
. 88
vii-'
Abstract
. T h e .pyrolysis of naphthacene was studied in a Thermogravime.tric Analysis .(TGA) apparatus in order to obtain information which,
might be useful in the manufacture of commercial pyrolytic graphite.
• During the pyrolysis runs, data was obtained concerning amount
of weight loss, temperature, and rate of evolution of the gases pro­
duced by pyrolysis. Following the runs, the products were analyzed.
The final temperature of all runs used for quantitative purposes was
625-630 0C.' The" results of the product- analysis were used to form a
stoichiometric equation for the overall- reaction of naphthacene .• ■ - Four compounds and unreacted naphthacene were found to be
present in the condensate.
One of these was 3,12-dihydronaphthacene.
The other compounds appear to be two oxygenated compounds and one
compound that may'be the result of further reaction of dihydronaphtha
cene.
Introduction
Pyrolysis or thermal decomposition is the process- of breaking
chemical bonds by means of thermal energy.
Unless pyrolysis occurs
in the presence of catalysts, it is known to proceed by a free radical
mechanism and the products of pyrolysis may be predicted to some ex­
tent by means of the application of the knowledge of free radical -•
chemistry.
The manufacture of pyrolytic graphite involves the pyrolysis
of a feed stock that is primarily aromatic in character.
The compon­
ents of this feed that end up in the finished graphite are primarily
polynuclear aromatic hydrocarbons or compounds which are capable of
undergoing reactions which form this class of compounds.
Lighter com­
pounds will distill off during the process of heating the feed to the
temperatures required to form graphite.
Other classes of compounds'
besides polynuclear aromatic hydrocarbons.can undergo pyrolysis and
yield a high molecular weight carbonaceous residue, but ordinarily
this residue will not yield a high-oriented graphite (I).
There are
two primary considerations which determine whether a given compound
will give a well-oriented graphite.
The first of these involves the
structure of the original molecule.
If the starting compound is not
planar or has a great deal of steric crowding, it is not likely to
form a well-oriented graphite.
of the starting material.
The second involves the melting point
Brooks and Taylor found that well-oriented
graphites did not result unless fusion of the starting compound occurred
prior to the reactions producing graphite-like structures (2). . For
-2i
'
these same reasons, if the. mechanism of thermal decomposition for a
molecule involves intermediates with the characteristics mentioned
above, the compound is likely to form a graphite that is not welloriented.
Compounds which form graphites react in the following manner:
First, an aryl radical is formed by the rupturing of a carbon-hydrogen
bond or by the attack of a radical on an aryl hydrogen.
molecule can then form in one of two ways.
A diaryl
The first and least prob­
able way is by combination of two aryl radicals.
A more likely mech­
anism is the.addition of an aryl radical to an aromatic molecule fol­
lowed by the removal of hydrogen to give-a-diaromatic ,system.
In
order to get compounds with structures similar to that of graphite,
cyclodehydrogenation takes place to give a more completely aromatic
system.
For-example, in the tar formed by flow, pyrolysis of anthra­
cene at 7000C are 9 19 1-bianthryl, 1,2:11,12-dibenzpperylene, .and.other
compounds which could be formed by cyclodehydrogenation, of the above
or of compounds formed by some of the other possible radicals of
anthracene (3 )• . The .structures of these.compounds are.shown in
Table I.
.
......
The commercial manufacture of pyrolytic graphite involves a
two-step process.
During.-the first step of the. process,, a ,coke.is....
formed by heating the feed stock slowly to approximately SOO0F.- Dur- ■
ing this' heating period, the temperature may be allowed to level off .'
at various intermediate points in order to help to remove impurities
-3which may be present in the feed.
After the temperature reaches its
final value, it is kept there for a predetermined length of time.
The
resultant coke is then made into electrodes and heated in an electric
furnace to the 25006C temperatures which are required in order to
produce graphitic products (4).
At the present time it is not possible to tell in advance what
the quality of the final graphite ..resulting from a given coker feed
stock will be without taking a sample of the feed and actually making graphite from it.
It would be desirable to be able to obtain enough'
.information from the initial coking process to be able to tell what \
the ultimate graphite quality from the feed would be (4).
■ •
Most of the literature oriented toward the preparation of
graphite from polynuclear aromatic hydrocarbons is based on work done
by the Union Carbide Corporation for the Air Force Materials Laboratory.
They took a large number of compounds and heated them to 750°C in a
-
Differential Thermal Analysis (DTA) unit and classified these compounds
as either thermally "reactive" or "unreactive", depending on whether
they gave a measurable
the DTA run..
amount of carbonaceous residue at the end of
These runs were made at •atmospheric -pressure (5) •
Out. ..
of those compounds which were found to' be "reactive", they selected
approximately 100 compounds to convert to graphite by .heating to '3000°C.
The orientation of the resultant graphite was then studied by means of
x-ray diffraction.
The 002 lattice spacing was selected to reflect the
orientation of the graphite.
The lower the value of this spacing, the -
better is the orientation of the graphite (l)=
Graphites with a
value for this spacing greater than 3«366Angstroms a r e 'poorly oriented
(I).
■
The purpose of this study was to study the reactions of com­
pounds similar to those which would be found in coker feed stocks used
in the manufacture of pyrolytic graphite with the hope that the in­
formation resulting might be useful in coker design and also might
provide a useful way of testing a coker feed stock in order to predict
how good a graphite it would make.
Two compounds were selected for this study: ■ 1,2,5,6-dibenz- .
— anthracene and naphthacene.
The first compound was selected because
information available in the literature (6 ) indicated that the only
gaseous products present in significant quantities after pyrolysis of ..
this compound in a sealed glass ampoule were hydrogen and methane.
This
would make analysis and subsequent determination of kinetic information
much simpler than if more gaseous products resulted.
The chief dis­
advantage of this compound is that we wanted to know how well-ordered
a graphite would result from the compounds selected and dibenzanthra­
cene was classified in the work done by Union Carbide as thermally
"unreactive" (5)•
DTA of this compound showed a boiling point at 520 0C.
In the equipment used for this study, it was possible to obtain
a 35$ yield of carbonaceous residue based on original sample size when
the pyrolysis of dibenzanthracene was being investigated.
In the DTA
work done by Union Carbide, the heating rate used was ten degrees per
Equipment
A drawing of the'equipment used to conduct the pyrolysis is
shown in Figure I.
Basically, it consists of a.stainless steel re­
action chamber which is suspended from a continuous recording balance.
The piece of tubing from which the reactor is suspended is also the
thermowell for measurement of reactor -temperature.
The balance is
the same one which E. A-.. Currie built for-his' study on the pyrolysis
of acenaphthylene and bifluorenyl (7).
Figure I shows the equipment
as it appeared while -Currie was doing his work.
Figure 2 shows some
of the modifications which were necessary in order to make the equip-ment-perform satisfactorily for naphthacene. - Comparison of Figures-
--
I and -2 shows that the design of the cap which fits over the heated
zone was changed.
This was done for two reasons.
It was felt that-
the amount of oxygen getting to the reacting materials would be de­
creased sharply by increasing the length of the path required for its
•diffusion.
The primary reason, however, for the change in design was
to allow the installation of an additional heater.
The purpose of this
heater was to prevent the condensation of the heavier products which
distilled off during the funs.
In the early runs which were made on
naphthacene, heavy solid products would condense on the thermowell and
along the tube leading from the condenser to the reactor.
result in the fouling, of the balance.
This would
The heater was installed in
order to raise the temperature of the gas coming in contact with these
products to a value sufficiently high to. prevent condensation from
occurring until they reached the condenser region.
The heater consisted
of nichrome wire with ceramic bead insulation wrapped around this cap
-7‘and the beginning of the nipple'leading away from the cap.
In addition to the equipment shown in. Figures I and 2,- there
is a chromatograph built especially for this project hooked up to the
outlet in order to analyze for the non-condensable gases produced.
The chromatograph, which contains a thermal conductivity detector, uses
a 1
A -inch diameter column that is packed with Porapak Q 100/120.to sep­
arate and analyze the gaseous products of naphthacene pyrolysis._ This
column is six feet six inches in length.
Immediately, before the
chromatograph is located a glass wool filter to remove the last of the
solid products from, the gas stream and -a-tube of drierite to remove any
water that may be contained in the stream.
chromatograph was nitrogen at 65 cc/min.
ll8.5°C.
The carrier gas used in' the
The column temperature was
Nitrogen'was used because helium, which is the preferred gas
for methane and ethane chromatography, is. very poor f o r ■hydrogen.
Nitrogen is also inexpensive enough to use as a purge for the system..'.
,.
The chromatograph wasxprovided with an automatic sampling valve
in order to have exactly the same sample size at every injection.
This
was very important.since it was necessary to have information about
absolute concentration of the individual components of the gas being
analyzed.
This uniformity in sample size can not ordinarily be
achieved with a syringe.
The last piece of equipment used during"the reaction was a posi­
tive displacement pump which was used to pull the gases leaving the
condenser through the sample valve.at a constant rate.' ..It did this by
-
8-
pumping water out of a sealed bottle which was connected to the out­
let end of the sample valve at the required rate..
The remainder .of- the equipment is that which was used for
analysis and identification of the products.
An Aerograph 660 gas
chromatograph equipped'^with’"a ’flame’ionization detector was used to
analyze the condensate.
The column that was used was a 1/8-inch
diameter, twenty-five foot .column packed with 3% SE-30 on 50/60 mesh
Anakrom ABS. .The carrier gas was nitrogen at 25 cc/min.
The column
temperature was 2k2°C.
‘ The infrared spectra used to identify one of the products and
to aid in the characterization, of one of the other products, in the.
condensate were run in a Beckman IS-4 Infrared Spectrophotometer.
The
infrared spectra of another condensate fraction were run by. Huffman
Laboratories in Vheatridge 1 Colorado.
'
..
Ultraviolet spectra were run in a Beckman BK-2 Ultraviolet and
Visible Spectrophotometer.
-
-
■ Preparative- Chromatography was done in- an Aerograph 200 gas
chromatograph in a /-inch column,, fifteen, feet" long, packed with the
same material as that used to analyze the condensate using hydrogen
as carrier gas at 30 cc/min.
The column temperature was 250 9C.
I
Experimental: and Analytical Procedures
The sample size used in the pyrolysis runs under discussion
here was between.0.9 and 1.1 grams.
Prior to the beginning of the
runs, the nitrogen supply to the reactor and that used to provide a
continuous purge to the reaction chamber shown- in Figure I was turned
..on.
During .the., progress, of the run, the rate of supply of nitrogen
- was kept slightly.higher, than the rate, of ..its.removal through the
sample valve in order to help to cut down on the amount of oxygen en­
tering the system.
On the day of the .run, samples of the calibration gas were run
through, the sample valve at' approximately the same rate.at which the • ■
reaction gases would be pulled through the valve during the run'in ■
order to check the calibration curve and to provide a means of correc- '
tion for the normal variation in atmospheric pressure that occurs.
■ The calculation of gas evolution rates was done by using the
.peak heights shown on the reaction-monitoring gas chromatograph.
A
calibration curve was made using a calibration gas purchased from the
Matheson Company 'which contained 5«27 mol% hydrogen, 5•33/o methane, and
5•^3% ethane in nitrogen.
samples of
The calibration curve was made by injecting-
I, 2 , and 4 cc through the sampling valve at approximately
the same rate at which the gases are pulled through it during the pyrol­
ysis runs.
This gas contains hydrogen, methane, and ethane at approxi­
mately the same concentrations in which they, appear■in the gaseous
product mixture.
Since the.sample loop is not connected to carrier gas
pressure- until the moment of injection and the sample loop is'outside
-10the' chromatograph" and "far 'enough from the reaction area for' the gases
to cool to room temperature, the calibration curve.was based, on am­
bient temperature and pressure.
Twenty-five degrees centigrade was assumed as the temperature
and the pressure was'measured prior to every run "in order to make
corrections on the calibration curve. 'Since the calibration curve was
based on a flow rate through the sample valve of 65 cc/min, it was
.
necessary to correct for deviations from this value which occurred
during the runs.
The variations in ambient temperature were not cor­
rected for since the original .calibration.curve was made using the ■
assumption that sample valve temperature: was the same as that in the
chromatograph.
-The 4-cc sample loop was used during all of the runs.
The gas evolution rate could then be calculated by means of the follow­
ing equation:
"moles
x flow rate
sample
moles
min ■
In this equation the flow rate must be expressed as the number of 4-cc
samples per minute. • The points used to make the .calibration curve are
"shown in Table II.
A computer program which was used to read the cali­
bration curves is shown in Table III.
The subroutine which will do.the
necessary interpolations is shown in Table IV.
This subroutine takes
the four point's on the calibration curve nearest to the desired value
and fits a fourth order polynomial through them and then calculates the
desired intermediate value.
The input to the curve reading program
-11inclydes. -calibration -curve data taken from a graph which was drawn of
the calibration for approximately every five units of peak height.
It
also includes the values' of peak height for the gases taken, during the .
run being analyzed.
,Another.program was written to integrate the gas evolution rate
curves in order to obtain stoichiometric coefficients for the gases.
It is shown in Table V that the output of this -program was time, tern-
-
perature, fraction of original sample corresponding to the amount of
weight lost -since the beginning of the run, total amount of gas evolved
per gram of sample, and per gram of material remaining in the reactor.
Gas evolution rate was expressed in both of these ways in order to
decide which of the two values to present in the form of graphs.
The-
values in the individual runs are affected by so many other variables
other than temperature, such as the rate of temperature -increase at the
time at which the sample is taken, that the rates at a given temperature
do not agree very well with those from other runs, no matter which.basis
is chosen as' a means of expression of the rate.
The rate per gram-of
sample was chosen as the expression to present.
The rate per gram re­
maining in the reactor can easily be calculated from the other.
The
output of this program also provided the input to the program shown in
Table VI which made the graphs shown in Figures 3-6.
. ..During the. progress of the -runs, ..an attempt was made to keep the
rate of temperature increase as close as possible to 1 . 6 7 -degrees Centi­
grade per minute in order to -get a better comparison between the re-
—
12
—
suits of the different runs.' The rate of temperature increase 'prior
to the- temperature at which naphthacene melts ,(357°G) was found to
be not critical since there does not appear to be any significantamount of reaction prior to that temperature.
■After melting had occurred, the gas was sampled every five
minutes until propane began to be evolved. . It was then necessary to
wait six minutes in order to allow the pen to get back to the base­
line before injecting a new sample.
At the time of sample injection, a record was made of pumping
"""rate:
For the compounds which were used for this study, this was
.necessary because at the time during the run during which large quan­
tities of condensate were coming off, (420-5000C). enough condensate
would collect in the tubing leading to the chromatograph to cause a
great increase in resistance to flow.
Since the calibration curve which
gives gas evolution rate from the chromatograph peak height is based on
a constant flow rate of 65 .cc/min, any "significant deviation from this
flow rate must be corrected for..
■•■
..... .
The complete runs'were terminated after the temperature of the
reactor had remained constant at 6250C to 635°G for 15 minutes.
The
interrupted
runs ■were -terminated either
after
15 minutes at- * some de.Jm
,
- signated temperature if weight loss had not yet begun, or when the
reactor had reached approximately constant weight.
-13After the''runs had"been completed, the final weight of the
reactor was recorded and the carbonaceous residue was scraped out.
This residue was extracted for 24 hours in a Soxhlet Extraction
Apparatus to measure the amount o f .benzene-soluble material present
in the.residue.
The condensate was first separated manually into two fractions:
unreacted naphthacene and other condensate.
It was necessary to make
this separation before chromatography because the chromatograph column
used would not resolve naphthacene and some of the other compounds
present in_ the.condensate.
This separation could be made with little
difficulty, provided that enough condensate was present, since an inter'
face forms in the condenser between naphthacene, which is red, and one
of the other compounds, which forms yellow crystals.
Tlie fraction
from which the naphthacene had been removed was then analyzed in the
chromatograph..
Additional work was done on the condensate from some of the runs
in .order to identify some of the products.
The most important thing that was done was manual preparative
chromatography, which allowed condensate samples to be separated into
fractions containing some of the compounds making up the condensate in
high purity..
Some of these were.sent to Huffman Laboratories for an­
alysis of molecular weight and carbon and hydrogen content.
Infrared
and ultraviolet spectra and melting point were taken with equipment
available on this campus.
The infrared spectra that were obtained
were- run in approximately ~L%■concentration in .KBr micropellets in
a Beckman Ik-4 Infrared Spectrophotometer.
The ultraviolet spectra
were run"in an"approximately saturated solution in ethanol in a
Beckman' DK-2 Spectrophotometer.
Results and Discussion
A total of 13 pyrolysis runs were made on naphthacene.
of these were terminated at 623-630*0.
Eleven
The last two runs weife made
to intermediate temperatures' in order to obtain information about when
different reactions were- occurring.
For the complete runs (termina­
tion temperature 623-630*0), the' supplier"of"the naphthacene was K & K'
Chemical Company.
The supplier for the interrupted runs (those termin­
ated at intermediate temperatures), was the Distillation Products
Division of the Eastman Kodak Company.
It was not possible to use the
same- supplier for a l l .of the runs because K 8c K ran out of naphthacene
shortly before the time that the naphthacene required for the inter­
rupted runs was- ordered. - Only the last- four of the complete runs will
be- discussed here since information obtained in these last four runs
indicated that the results of the first six runs was not truly repres­
entative of the reaction of naphthacene at the measured temperatures^
of reaction.
The main problem which had to b e .solved in order to get data
representing.a true picture of the reactions occurring at the indi­
cated temperatures was getting the high molecular weight vaporizable
compounds produced by the pyrolysis into the condenser region without
condensing prematurely or undergoing further reaction.
When the equip­
ment was set up as shown in" Figure I, the temperature of the gases
entering the condenser region'w a s 'only l40*C, well below the melting
points of all but one of the compounds which were isolated during this,
study.
This resulted in the condensation of the solid products as soon
-16as they left the hot- reaction zone.
The- products would then collect
'
on top of the reactor, on the walls of the passageway leading to the
condenser, .and on the outside of the thermowell.
Eventually enough
of them would collect to foul the balance and no meaningful weight loss
data -could be obtained.
This-problem was first solved by putting an
additional resistance heater around the cap, as shown in Figure 2.
With this' heater it was possible to raise the gas temperature to 318 0C,
which was sufficient to get all of the solid products at least as far
as the nipple leading away from the cap.
Unfortunately, the surface
temperature of the cap necessary to produce this gas temperature intro­
duced some materials problems.
This temperature was high enough to
produce scale on the surface which was difficult to keep- from dropping
into the product when cleaning the apparatus at the end of the run.
Evidence was also obtained that the cap was hot enough so that the un­
reacted naphthacene which distilled off and collected in the nipple
continued to react and give off products.
The final solution came from
the installation of another preheater external to the apparatus.
This
made it possible to heat the gases entering the condenser to 270°C with­
out making the nipple region hot enough to cause the continuation of
pyrolysis there.
The information obtained during the complete runs is shown in
Figures 3-6.
Tables VII-X.
The same information is presented in tabular form in
The gas evolution rates which were obtained directly
from the chromatograms made during- the runs are underlined.
-17On a qualitative basis, the results■obtained during the runs
are quite similar.
They all show maxima in hydrogen evolution rate .
at 425-^350C and a smaller maximum toward the end of the run near ■
where the temperature began to level off.
The curves for methane show
maxima a t -470-4850C and one run (Ex-NA-7) shows another maximum at
5l8°C.
(Note that the value of moles of gas/min. gm of sample at the ■
first maximum for this run was considerably lower than that for the
other runs.
at 460-485 0C.
All of the runs show maxima in ethane evolution rates
In addition to the results shown on these graphs, there
is -a maximum evolution rate for propane at 460-475°C (although Ex-NA -8
showed its propane maximum at 485°C) and for ethylene at 450-460°C .
There was also, good agreement between the runs in the temperatures at
which a weight loss first appeared.
Ex-NA-Il began at 403-4o4°C.
Weight loss in all runs- except
It began at 407°C in Ex-NA-Il.' This
could easily be due to the lower sample size■in this run since the bal­
ance has a finite sensitivity and the lower sample size could result in
a longer lag until the balance was able to detect a change in weight.
It should be mentioned here that in all of the runs, some material had
appeared in the glass filter located just ahead of the chromatograph
at least ten degrees before the balance first showed a loss.
After the
runs, the residue was put into a Soxhlet extraction apparatus using
benzene for solvent.for 24 hours.
None of the runs taken to completion
showed a significant quantity of benzene-soluble material present in
the carbonaceous residue.
- 18In addition to the gases mentioned above, a small amount of
propylene was observed.
Propane, propylene, and ethylene were not
analyzed quantitatively since they were present in much smaller amounts
than the others.
A chromatogram which -is typical of those taken dur­
ing the portion of the run when all of the gases by propylene are pre­
sent (when propylene is present it appears as a shoulder on the propane
peak) is shown in Figure ?•
Peak I is at an attenuation of 100 x.
Hydrogen, methane,, and ethane were identified by means of com­
parison of retention time with that resulting from injection of a
sample containing these compounds in approximately the same composition
as that resulting from reaction.
Propane and propylene were identified
by comparison of retention time with that of pure samples.
The dif­
ference in retention time between propane and propylene was used to
identify ethylene by analogy by comparing the retention time observed
for the peak suspected to be ethylene with that for ethane.
Peak I
was found to-be hydrogen, peak 2 was methane, peak 3 was ethylene,
peak 4 was ethane, peak 5 was propane.
These same gases are reported
in the literature as products when naphthacene is pyrolyzed at 4750G
in a sealed glass ampoule (6 ).
This same reference listed CO and CO^
as products and there are unidentified peaks between peaks 2 and J>.
Water was also given off and was removed from the stream ahead of the
chromatograph because it has the same retention time in the column
used as does propane.
.
.
.
—
19
—
A chromatogram similar to that which results from chromato­
graphy of the condensate after the unreacted naphthacene is removed
is shown in Figure 8 .
The actual resolution which results is much
better than that indicated.
The only purpose of this figure is to
indicate the peaks that result.
from left to right.
The order of retention times is read
The first peak is solvent, the second is an un­
identified light compound and the peaks labeled I, II, III, and.IV
are the ones which were used to obtain quantitative results.
Some of the ■compounds represented by these peaks were isolated
for further study.
Compound I appears in the condensate far enough
separated from the other components that it was readily available in
sufficiently high purity for further analytical work.
The sample of
it that was obtained showed only one peak in the l/8-inch column which
was used for condensate analysis.
preparative .chromatography.
Peak II was isolated by means of
Peaks III and IV were obtained in the
same fraction by preparative chromatography and were then separated by
hand since the 1
A-Inch. column used for the preparative work was not
capable of resolving these two compounds.
Figure 2 shows the regions in which unreacted naphthacene,
compound I, and compound II collect when passing through the condenser.
Compounds III and IV collect primarily in the tubing leading from the
condenser to the chromatograph and in th.e glass wool filter at the
end of this tubing.
-20The problem of identification of these compounds proved to be
very difficult.
The only compound appearing in the condensate which
was positively identified besides unreacted naphthacene was 5 ,12-'
dihydronaphthacene.
Table XII.
The structure of this compound is shown in
It is reported in the literature as one of the pyrolysis
products of naphthacene (5 )•
A considerable amount of information was obtained to aid in the
characterization of compound I.
It has a melting point of 145-150 0C.
The molecular weight measured by Huffman Laboratories by the Rast method
indicated that it has the same number of carbon atoms as naphthacene.
The result of the carbon and hydrogen determination which was also done
by Huffman Laboratories is:
carbon, 92.5%; hydrogen, 7.5%;
Calcul­
ated values for benzyl naphthalene and methyl-benzylnaphthalene are
6.46 and 6.94% H.
The ultraviolet and infrared spectra of this compound
are presented in Figures 10 and 11.
The infrared appears to be similar
to that of a disubstituted naphthalene.
that for 2-benzylnaphthalene.
shown in Table I.
It is also quite similar to
The structure of 2-benzylnaphthalene is
The ultraviolet spectrum also appears to be similar
to that of 2-benzylnaphthalene and calculation of .extinction coefficient
for this compound indicate two or more fused rings.
An attempt was
made to run a NMR spectrum of this compound but not enough material
-was available to get a good spectrum.
Compound II was positively identified as 5 i12-dihydronaph­
thacene.
The melting point of compound II was measured in our labora­
-21tory as 205-210 0C.
The melting point reported in the literature for
5,12-dihydronaphthacene is 206*0.
Huffman Laboratories ran a carbon
and a hydrogen determination on compound II and reported' 93'.55$>
carbon and 6.22% hydrogen.
The calculated value for dihydronaph-
thacene is 6.08% hydrogen.
The molecular weight by the East method
also agrees with that expected for dihydronaphthacene.
The most con­
clusive, evidence, however, comes from.infrared..spectroscopy.
The
spectrum for compound II shown in Figure 9 is identical to that re?
ported in the literature for 5 i12-dihydronaphthacene (8 ).
The part of the condensate identified as unreacted naphthacene
is identical in appearance, retention time on the chromatograph, and
infrared spectrum to that for the starting material.
Some information was obtained about the natures of compounds
III and IV.
Both compounds appear to have approximately the same
molecular weight■as naphthacene.
Compound III is yellow and sublimes
at 241-2420C without leaving a residue.
Its infrared and ultraviolet
spectra are shown in Figures 12 and l4.
The curve marked "C" in
Figure l4 is that for compound III.
Compound IV is red and sublimes
at 260-270°C,. leaving a carbonaceous residue.
violet spectra are shown in Figures 13 and 1.4.
in Figure I4 is that for compound IV.
Its infrared and ultra­
The curve marked ftB i1 ■
The column used will not re­
solve either of. these compounds from naphthacene.
According to Huff­
man Laboratories, both of these compounds appear to be esters.
-22The method of calculation of the stoichiometric coefficients
for the gaseous products was-mentioned in the previous section.
The
points which went into the program for integration of gas evolution
rate data in order to get the total amount of the gas which had been .
given off during the run came from smoothed data obtained from the"
various runs.
The results from the different runs were compared in
order to determine which points were to be thrown out.
From this
smoothed data, gas evolution rates, temperature, and amount of weight
loss since the beginning of the run was obtained at intervals of one
minute.
In order to integrate the gas evolution curves it was assumed
that the curves were linear over the one-minute intervals.
The method which was used to obtain the stoichiometric co­
efficients for the solid products is probably not the best method to
use, but it was the only one which was capable at all of giving any
idea of what the composition of the reaction products was.
The first-
major weakness of the method is that it depends on the manual separa­
tion between the 5 ,12-dihydronaphthacene and the unreacted naphthacene.
The reason that it was necessary to make this separation manually is
that naphthacene is so much less soluble than the other components of
the condensate in the CS^ used as solvent for the work done with the
flame detector, that if the solution contained"a representative amount
of naphthacene, it would be so dilute in the other components that they
would not show up at all due to the tailing of the peaks which becomes
very pronounced if the amount of a component in the sample falls below
-23a certain value.
The result of a poor separation between unreacted
naphthacene and 5 112-dihydronaphthacene may be seen .in Table XI.
The
sample size in Ex-NA-Il was approximately 25% less than in the other
runs which resulted in the amount of condensate being much less.
When
there was less, condensate, it was more difficult to make the separation
accurately and evidently some of the 5 ,12-dihydronaphthacene was in­
cluded with the unreacted naphthacene, resulting in a calculated con­
version to 5 ,12-dihydronaphthacene that was much lower than that found
for other runs.
This run was not included in the average values used
for the stoichiometric coefficients.
Even if it can be assumed that the manual separation was exact,
there is still some weakness in the calculation method itself.
Since
for a flame ionization detector, peak area is proportional to carbon
number and the products found in the condensate have approximately the
same molecular weight and contain over 90% carbon, it was assumed that,
area fraction was proportional to weight fraction.
In order to check
this assumption, a known amount of 9 ,10-dimethylanthracene was added to
a sample of one of the condensates and run through the chromatograph.
The sample was 4.44 weight percent dimethylanthracene and two samples
run through the chromatograph showed 3 »54% and 4.06% dimethylanthracene
by -area.
This agreement is as close as the certainty with which the
weight of the dimethylanthracene was known, since the sample only con­
tained 0.2 milligrams of dimethylanthracene.
-24The chief problem with using the chromatograph to do quan­
titative analysis of this type of compound is that they appear.to be
adsorbed quite strongly which results in peak broadening and decreased
resolution.
A silanized support was used to try to reduce this effect,
but it was still quite pronounced.
If the samples were diluted enough
some of the peaks would be broadened enough so that they didn't show
at all.
A great deal of the time which was spent on this project was
spent in trying to find a gas chromatograph column which would be use­
ful for separating polynuclear aromatic hydrocarbons. ' The first col­
umn that was tried was a fifteen-foot, l/8-inch diameter column packed
with 20# LiCl on Chromosorb W.
literature (9 )•
This column was recommended in the
For the pyrolysis products of naphthacene, however,
it did not work very well.
The main problem was that unless it was
operated at quite high temperatures, it would adsorb all of the sample,
especially naphthacene.
Vhen it was operated at sufficiently high tem­
peratures (greater than 300C>C), resolution was not very good, retention
time was still quite high' for naphthacene, and the high temperature was
very hard on equipment.
The column that was finally used was 3% SE-30
on 50/60 mesh Anakrom ABS.
This column could be operated at lower tem-
^peratures at lower carrier gas flow rates and still allow all of the
sample to come out in thirty minutes.
The actual operating conditions
that were used were a column temperature of 2420C, injector temperature
of 330°C and a nitrogen flow rate of 25 cc/min.
The same, support and
-25operating conditions were used in a 1
A -inch column for preparative ■
chromatography..
It was also found that the detector temperature could
be as low as 2000G without causing flooding of the detector.
■The 1/8-inch column used for condensate analysis gave good
resolution for all of the products in the condensate except between
compounds III, IV, and naph-thacene.
The 25-foot column did not do any
better at this job than did the 15-foot column which was originally
tried.
The most interesting thing that was discovered while working
on the chromatography of the condensate is that if naphthacene is added
to the condensate in large quantities, compounds II, III, and IV form
one peak.
The retention time of compound II is increased and that of
III and IV is decreased.
It appears that naphthacene may interact
strongly with these- compounds.
By means of the analytical methods which have been discussed,
the stoichiometric equation shown in Table XII was calculated for the
overall reactions of naphthacene to 625°C.
The stoichiometric coefficients shown in this equation were
obtained by taking the arithmetic mean of the results of Runs 7-10.
The value from Ex-NA-10 was not included in the calculation of the co­
efficient for ethane.
The results from Ex-NA-Il were not included be­
cause the separation between unreacted naphthacene and 5 ,12-dihydronaphthacene was not made correctly and because the smaller sample size
used for this run appeared to cause some of the differences.
-26Examination of Table XI and Figures 3-6 shows that there are
some significant differences in the quantitative information obtained
from the various runs.
Before these are discussed, it should be
pointed out that the minor differences between the runs in the loca­
tion of the maxima in gas evolution rates is probably due to variation
in heating rate, since this was controlled manually. - The same reason
would also explain the differences in value of evolution rate at the
maximum except for the very large difference in the value of the
hydrogen first maximum in Ex-NA-8 as compared to the values of this
maximum rate in the other runs.
be mentioned later.
A few possible reasons for this will
For reasons mentioned earlier-in this paper, the
results from Ex-NA-Il will not be counted.
After the stoichiometric
coefficients from Run 11 are discounted, there is pretty good agree­
ment between the other runs in the methane coefficients.
Comparison
of the ethane curve from Ex-NA-10 with that of the other runs shows
that its shape is different from that appearing for the others.
This
difference in shape could be corrected by throwing out the ethane
evolution rate at 92 minutes for that run.
This would result in an
ethane coefficient more in line with, that for other runs.
There is a possible explanation for the large hydrogen co­
efficient for E x -NA -8 and for the unusually large value for the evolu­
tion rate at the maximum.- Table XI shows that for this run, more of
the naphthacene ended up in the condensate as unreacted naphthacene
than in the other runs.
The remainder of the condensate was less than
-27in the other run's. ■ Since the analysis of the condensate indicates
that the conversion of naphthacene to these compounds requires hydrogen,
it appears that these results are related.
A' possible explanation
might come from the free.radical nature of the reactions which occur
during pyrolysis.
The- production of hydrogenated compounds depends on
the attack of hydrogen radicals-on naphthacene or on some other com­
pound present in the reaction mixture.. It might have been possible
for something to have been present during this run to cut down on the
reactivity of the other compounds to'hydrogenation by addition of a
hydrogen radical.
This would make abstraction of hydrogen from com­
pounds present.in the. mixture by the hydrogen radicals more likely.
Since this would result in more aromatic radicals, a larger conversion
.to carbonaceous material might, .be expected.
The amount of carbon­
aceous matter present in the reactor at the end of Ex-NA-8 was greater
than in the other runs.
is what happened.
There is no real evidence, however, that this
The preceding discussion is only a possible explana­
tion for what occurred.
Two interrupted runs were made in order to help determine when
the compounds present in the condensate were produced.
Ex-NA-12 was
terminated at 405°C, shortly after the weight loss started.
Ex-NA-13
was terminated at 450°C, shortly before the end of the weight loss.
The residue from each of these runs was put into a Soxhlet extraction
apparatus.
The residue from the first run, which amounted to 89.5% of
I
the original sample, contained 68% benzene-soluble material and re­
quired only 24 hours for the benzene around the thimble to become clear.
- 28The residue from Ex-NA-12 appeared to contain carbonaceous
material, unreacted naphthacene, and a yellow crystalline substance.
Chromatography of the residue extract showed the presence of all four
peaks labeled in Figure 8 .
The relative peak areas were similar to
those resulting from chromatography of the complete runs except that
peak IV was relatively smaller than it appeared in the chromatograms
of the complete run condensates.
The condensate appeared to contain
unreacted naphthacene and a yellow powdery material.
Chromatography of the condensate showed some unidentified light
.compounds which only appeared because the sample used was much more
concentrated than that used for chromatography of the complete run'
condensates and a large percentage of compound III.
No 5,12-dihydro-
n aphthaeene appeared to be present.
The residue from Ex-NA-13 was mostly carbonaceous material and
contained some unreacted naphthacene.
Chromatography of the extract
showed the presence of the same compounds as in the previous run.
The
fraction of compound II appeared to be less in this run than in the
previous and peak IV was more pronounced.
The condensate from this run
looked the same as that from the complete runs.
Chromatography of the
condensate showed the presence of some compound I, a small amount o f '
compound II, and the remainder was compounds III- and IV.
There was
more compound I present than compound II.
The data obtained in this work agree well with information avail­
able in the literature.
The boiling point of dihydronaphthacene by.
.
-
DTA is given as 4200G (5)•
29
-
The same reference shows that naphthacene
■has a weak exothermic reaction at 480°C- which is close to the tempera­
tures at which the evolution rates of methane and ethane had maxima.
Dihydrpnaphthacene did not show .up in the 405°C condensate but was
present in the 4-500C condensate
From the data obtained from the interrupted runs, the following
information..,abo.ut the course .of the production of the solid materials
present in the condensate may be concluded:
1.
All-of the compounds which appear in the condensate
during the complete runs are first formed at some
temperature below 400°C. This evidence indicates
that production of these compounds is continuing .......
in the temperature range of 400-450°C. Most of the
production of compound IV occurs above 405°C.
2 . ' Compounds I-IV still make up a significant part
of the residue at 4$0°C, although most of the
compound I has distilled off by this.time.
These results indicate that since one of the major components
of the residue.that has not.already reacted to form carbonaceous matter
at 4500C is dihydronaphthacene, it might be possible for some of the
non-condensable gases which begin to appear in the temperature range
between the two interrupted runs to be formed by cracking of dihydro­
naphthacene (or of any of the other compounds found in the condensate).
The presence of such a large quantity of oxygenated compounds in
the products resulting' from the pyrolysis of a hydrocarbon in an inert
atmosphere is quite puzzling.
This has also occurred in pyrolysis
1
■studies appearing in the literature.
For example, the gaseous products
/
-
30
-
'
of the pyrolysis of naphthacene in a sealed glass ampoule contain 1 .59° '
CO' and CO^ (6 ),- The presence of some, oxygenated product is not too
surprising, since no method.is provided.for purging.the reactor itself
at the beginning, of the run and polynuclear aromatic hydrocarbons form
quinones quite readily. ' These quinones could undergo further reaction
at high temperatures to form other oxygenated materials-.
Conclusions
The purpose of this work was to study the reactions occurring ■
during the pyrolysis of naphthacene in order to help obtain a better
understanding of how compounds which form a well-ordered graphite
react.
Qualitatively, the results obtained from the four complete runs
under discussion here agree with each other quite well.
It is probable
that the first peak in. the hydrogen evolution curve is the result of
the beginning of a period of rapid removal of hydrogen by reaction to
form hydrogenated products.
At the end of the runs, the evolution rate
of the hydrogen was increasing as cyclodehydrogenation reactions form­
ing graphite-like molecules probably was occurring in the residue.
The methane, ethane, ethylene, propane, and propylene which were given
off were products of cracking reactions of hydrogenated products formed
earlier in the run.
The weight loss curves appear to be caused simply by distil­
lation of products formed earlier in the run and do not reflect what
is happening in the reactor at the time during which the loss is takingplace . . .
Table I shows that there was considerable variation in the
stoichiometric coefficients obtained from the different runs, so theaverages-presented elsewhere in this paper should not be regarded as
exact values
-32There is much room for future work to be done on this compound.
Since.the weight loss curves provide, little.information as to the.rate,
at which reactions are occurring, more interrupted runs should be made.
At least one run should be made to a temperature below 357°C, the melt­
ing point of..naphthacen 5 in order to see whether reactions, forming new
products occur in the solid phase.
Some hydrogen evolution is evident at these lower temperatures
but it could be due to small amounts of residue from previous runs
which were not completely cleaned out.
It would also be desirable to
make a series of interrupted runs with K & K naphthacene and obtain
stoichiometric coefficients for a number of intermediate temperatures.
More runs should also be made to completion in order to obtain more valid values for the stoichiometric coefficients.
In order to get more information about the 'oxygenated compounds
which were produced, some runs should be made in which a nitrogen purge
Is provided directly to the interior of the reactor prior to making
the run.
This would help to show the source of the oxygen.
Appendix
-34-
Table I.
Compounds Involved in this Work.
Compound
Structure
Naphthacene
5,12-dihydronaphthacene
2-benzyl naphthalene
9,9'-bianthryl
a
1,2:11,12-dibenzoperylene
™
K
-35-
Table II. .Points in Calibration Curves.
■Hydrogen
Methane
■ • Ethane
Peak H t .
Moles/Min
4
. times 10
435
.00488
107
.00492
1320
.0194
354
.0196
149.0
.0197
266?
.0391
692
.0394
283.O
.0400
4213
.0780
1063
.0788
473.0
.0801
Peak H t .
Moles/Min
4
times' 10
Peak H t .
53.2
Moles/Min
4
times 10
.00497
Table III.
Program to Read Calibration Curves
C DATA REDUCTION PROGRAM
DIMENSION HHT (125), HRT (125), CH4HT(125), CHART(125)
I , C2 H T (125), C2RTI125)
READ I, HCAL,COAL,C2CAL,PRESS,NUX
C THESE ARE FROM CALIBRATION DONE ON DAY OF RUN C IS METHANE C2 ETHANE
C NUM IS RUN NUMBER NOW READ CALIBRATION CURVE
DO 2 1=1,122
2 READ 3, H H T ( I), H R T ( I), CH4HT ( I),CHART( I) ,C2HT(I) »C2RT II )
C HT IS PEAK HEIGHT RT IS MOLES/M IN*10**4
3 FORMAT (6 F IO .0)
I FORMAT (AF 10.0, 12)
NOW MAKE CALIBRATION CURVE CORRECTIONS
CALIBRATION CURVE CORRECTION IS FROM THE L ML LOOP
CALL TERPOL (CHRT,HHT,HRT,HCAL,122 )
CORVAL = .218*PRESS/623.4
HFACT = CORVAL/CHRT
CALL TERPOLtCC H-M'.T ,CHAHT ,CHART ,CC AL,122 I
CORVAL = .2 20 * PR _SS/62 3 •A
CFACT = C0RVAL/CCN4RT
CALL TERPOL(C2H6RT , C2 H T ,C 2R T ,C2CA L ,I22)
CORVAL = .22 I*PRESS/62 3•A
C2 FACT = C0RVAL/C2H6RT
(continued)
Table III (continued)
PRINT 6 , NUM
6 FORMAT (IH , 20X, 6 HEX-NA-, 12//)
PRINT 7» HFACT,CFACT,C2FACT
7 FORMAT( IH , I6 HCORRECT ION FACTORS ,5 X ,2H H2 ,F10.3,2X,3HCHA,F 10. 3 ,
I2 X , AHC2 H 6 ,F10.3//)
PRINT 8
8 FORMAT (IH ,8 H T IM E ,M IN ,2 X ,9) iT ,DEG . C. ,1X,7HH2 RATE ,3X,
I 8 HCHA RATE ,2X ,9HC2H6 RATE )
PRINT 9
9 FORMAT (IH ,23 X ,2AHMOLES/MINUTE TIMES 10**A//)
C TAKE EXPERIMENTAL DATA
DO 50 1=1,60
READ 3,TIME,TEMP,HPKHT,ClPKHT,C2PKHT,GASRT
CALL TERPOL (HRATE,HHT,HRT,HPKHT,122)
CALL TERPOL (C IRA TE ,CH AliT ,CHAR T ,C IPKHT ,I2 2 )
CALL TERPOLt C2RATE,C2HT,C2RT,C2PKHT,122)
RTFACT =60./GASRT
C
GASRT IS SEC/65CC
HRATE = HR A TE*-HFACT *RT FACT
ClRATE = C IRATE*CFACTORTFACT
C2RATE = C2RATE*C2FACT*RTFACT
PUNCH 5 1 ,T IM E ,TEMP,HRATE,C IRAT E ,C2RATE
50 PRINT 51, TIME,TEMP,HRATE ,C IRATE ,C2RATE
51 FORMAT (IH ,5FIO •A )
CALL EXIT
END
This program is Fortran II written for the IBM 1620
Table IV.
19
20
26
41
29
27
22
Interpolation Subroutine.
TABLE INTERPOLATION PROGRAM
SUBROUTINE TERPOL (AiOtCtDiI)
DIMENSION BI 125) tC(125)
I F lD -BU ) ) 18 119 119
IFtD-Bl I) ) 20t33t21
IF ID-Bl2) )26 t27 t27
N= 2
GO TO 23
IF IN - I+ 1) 23 t29 t29
N=N-I
GO TO 23
N=O
N = N+ I
%
"ISIIIIIIIIIIIE
I )-B IN ) )* IB (N + 2 )-B IN + I) > )
(continued)
I
Table IV (continued)
RETURN
18 A = C (I )
PRINT 5 »D
5 FORMAT(45H ERROR IN TERPOL,ARGUMENT TOO SMALL FOR TABLE»E12.6)
RETURN
21
A=C(I)
PRINT 6 ,D
6 FORMAT(45H ERROR IN TERPOL,ARGUMENT TOO LARGE FOR TABLE»E12.6
RETURN
25 A = C (N+ I )
RETURN
33
A=C(I)
RETURN
END
This program is Fortran II written for the IBM 1620.
)
^
Y
Table V.
Program for Integration of Gas -Evolution Data
n n
C PROGRAM FOR GAS EVOLUTION INTEGRATION AND NORMALIZATION
READ I* N U M »SLWT
SUMH =0.
SUMCl=O.
SUMC2=0.
HRTO=O.
ClRTO=O.
CZRTO=O.
PRINT 4,NUM
PUNCH 6 , NUM
CARDS = 0.
DO 50 1=1,500
READ Z , TIME,TEMP,V/TUN,HRT,ClRT,CZRT
RWT =SLWT-.01105*WTUN
SLH = H R T/S L W T
SLCl =ClRT/S L W T
SLCZ=CZR t /SLWT
RH = HRT/RWT
RCl=ClRTZRWT
RCZ=CZRTZRWT
W T L FR =. 0 110 5'*w TU N / S L W T
SL IS RATE NORMALIZATION BASED ON SAMPLE SIZE,R IS BASED ON REACTANT
PRESENT AT THE TIME
SUMH = SUMH+(HRTO+HRT)/Z.
SUMCl= SUMCl +(C 1RT0 + C IRT)/Z •
SUMCZ = SUMCZ+(CZRTO+CZRT)Z Z .
SSUMH = SUMHZSLWT
SSUMCl =SUMC IZSLWT
SSUMCZ=SUMCZZSLWT
IF(TIME)
48,43,49
48 PRINT 8 ,CARDS
GO TO 50
4 9 PUNCH 7, TIME, TEMP,WTLFR ,S L H »SLC I »SLCZ,SSUM h ,SSUMC I.SSUMCZ
Table V (continued)
PRINT 3 iT IM E iTEMP »R W T »WT L FR »SLH »RH *SUMH »S S U M H »SLC I »RC I »SUMC I »
ISSUMCl*SLC2»RC2»SUMC2» SSUMC2
PRINT 5
CARDS = CARDS + I.
HRTO=HRT
ClRTO=ClRT
50 C2 RTQ = C2RT
1 FORMAT ( I2 »F 8 •0)
2 FORMAT (6 F 10.0)
3 FORMAT (IH ,2F5.0,14F9.4)
4 FORMAT ( IH *6 0 X ,6HEX-NA-♦I2 » I7H COMPLETE RESULTS//)
5 FORMAT(5H T IME *6 H TEMP »3X ,3HRWT,7X,5HWTL F R ,6 X ,3HSLH,7X,21 iRH,5X ,
14HSUMH » 4X »5HSSUMH» 5X»4HSLC1 , 6 X » 3HRCI , 4 X ,5H5UMCI » 3 X , 6 HSSUMCI , 5 X,
24HSLC2♦6X»3HRC2»4X» 5HSUMC2 »3 X ♦6HSSUMC2)
'
6 FORMAT (34X,6HEX-NA-,12)
7 FORMAT (2F6.0,7F5.4)
8 FORMAT (IH , I O H T H E R E ARE ,F4.0,34H PUNCHED CARDS FOR PLOTTER PROGR
IAM )
CARD WITH ZEROES IS REQUIRED AT END TO PRINT CARD COUNT
CALL EXIT
END
•
U
•
O
•
O
e
O
»
This program is Fortran II written for the IBM 1620.
O
e
Table VI.
Program to Graph Tables VII-X
C PROGRAM TO MAKE PLOTS
DIMENSION
DIMENSION
T I M E (200) ,TEMPI 2 0 0 ) , W T L F R C 2 0 0 ) , S L H ( 200) ,SLCl (200)
S L C 2 !200)
READ I ,T IMAX,TIMIN,NUM ,NUMB
C NUM IS NUMBER OF DATA CARDS TO BE PLOTTED,T IM IN = T IMAX-2 00
C NUMB IS RUN NUMBER
1 FORMAT (2F1J.0,215)
DO 10 I= I,NUM
READ 2, TIME(I) ,TEMPI I) ,WTLFR( I) ,SLHt I) ,SLCK I) ,SLC2( I )
10 WTLFR(I) = -I.* WTLFRt I I
2 FORMAT (2 F 6 •0, 4FS.4)
TPMIN =-300.
TPMAX = 700.
WM IN = -I.
WMAX = 0.
GASMIN = 0.
GASMAX = .05
TIMED = 20.
TEMPO = 100.
WTLD = .1
GASD = .005
XL = 4.5
YL = 7 .
PUNCH 9,NUMB,TI H IN,T IMAX
9 FORMAT ( 6HEX-NA-,13,6H TIM IN=,F7.0 ,6 H T IMAX=,F7.0)
C
PLOT TEMPERATURE
(continued)
Table VI (continued)
3
I
C
4
C
6
7
8
CALL
DO 3
CALL
CALL
PLOT
CALL
DO 4
CALL
CALL
PLOT
CALL
DO 6
CALL
DO 7
CALL
DO 8
CALL
CALL
CALL
CALL
END
PLOT ( 101 »11 M IN » 11 MAX »XL »11 MED »I PM IN »I PNiAX »YL ♦TEMPO )
1=1,NUM
PLOT (9 ,T IM E ( I) ,TEM P( I) )
PLOT(90,TIM IN,T PM IN )
WEIGHT LOSS FRACTION
PLOT(2 0 1,T IM IN ,T IM A X ,XL ,T IM E D ,WM IN ,WMAX,Y L ,WT L D )
I= I *NUM
PLOT(9,T IM E ( I) ,WTLFRI I) )
PLOT (90,TIM IN,WM IN)
HYDROGEN,METHANE,ETHANE
PLOT( 201,TIM IN,T IMAX ,XL ,TIMED,GASM IN ,GASMAX,Y L ,GASD )
I= I,NUM
PLOT (9 ,T IM E ( I) ,S L H ( I) )
I= I,NUM
PLOT(9,TIME( I) , S L C K I) )
1=1,NUM
PLOT(9,TIMEl I) ,5LC2( I) )
PLOT (90,TIM IN,GASMIN)
PLOT(99)
EXIT
This program is Fortran II written for the IBM 1620.
i
-c-
Vl
I
• Table VII
EX-NA- 7
TIME
TEMP
WTLFR
SLH
SLCl
SLC2
MIN DEG C CM/GM SPLE MOLES/M IN GM SPLE*10**4
135.
136.
137.
138.
139.
14n .
14 I .
142.
14 3.
14 6.
14 7.
14 e .
14 9.
150.
151 .
152.
153.
154.
15 5.
15 6.
157.
156.
159.
160.
161.
386.
388.
391 .
393.
3 96.
39 7.
399.
4T .
4n 3 .
498.
4^8.
409.
410.
411.
412.
413.
4 13.
4 I4 .
414 .
414.
414.
415.
416.
417.
418.
0.0000
0.0000
o .norm
0.0000
0.0000
0.0000
,"ien o a ^
.00?n
n -ic,
:30<n
.0040
.0^50
.'19 70
.0100
.0130
.0160
.0201
.024 1
."3oi
.0 372
.0432
.0 583
.0 794
.0814
.1025
. 1408
0.0000
0.9000
.0091
.OOn I
,On n I
.0002
.OOn2
.nnnO
.no fI4
nnn/.
.OOO^
.Onnf,
. OOn 7
.0 9 0 8
.O n 0 9
.OOln
.0011
.0013
.0015
.09 1 8
.002]
. 09 22
.002 7
.0031
.00 3 5
.0040
.0045
0.0000
9.900"
n .9909
n noon
'"‘.noon
O 09 9"!
n .n n 9 n
^ .n n n ^
n .9 0 9 ^
n nn9r>
n * nO 6 9
n .n 0 0 9
n.nnn^
9.0099
n .n n n n
n ,no9^
9.0000
9.0000
n .0090
9 .oon0
r> n n ^ n
9.009"
0.0099
.009 1
.0002
.0003
.0093
9.0090
n .no9"
n .n 0 0 9
9.0099
n .n nn o
0,090"
".900 O
0 .n 0 n 9
o.noon
0 onon
0.0090
n .noon
0 .noon
O.nnnn
" .009 9
9.9090
0.0000
0.0000
o.noon
n ,0 0 0 0
^ 0 n0 0
9.90,90
9.009"
n .OQ 0 0
9.9000
9.9000
0 .onon
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10%*4
0.0000
0 .oono
.0001 •
.0903
.0004
.0007
.0 0 0 O
.90]3
.9016
.002 1
.9026
.9032
.9038
.9046
.0054
.9 064
.9075
.0038
.9 103
.9120
.n I49
.9 161
.0186
.0216
.0249
.9288
.9031
0.0000
9.0990
O.noon
o.nnnn
0.0000
9 ,OOOQ
o.nnnn
O .0090
o.nnnn
0.9000
9.0000
o.nnnn
0 .non 0
0.9990
0.9000
9.OQOO
P.OnnQ
0.0000
O .nQno
0 .noon
o.nnnn
0.0 0 9 Q
0.0000
.OOQl
.0003
."006
.9009
0.0000
9.0000
n.noon
0 .onon
0 .n 0 0 0
0.0000
O.9000
9.9 O O 9
O .9000
0.9000
0 .nOOO
n.nnno
n .n900
0 .nOOO
0 .nooo
0.nOOO
0.0000
0.0000
O.nOOO
0 .9^00
0.9900
0.9000
o.noon
n.nnno
0.0000
0.0000
0.0000
i
4r
Jr-
Table VII
TIME
TEMP
WTLFR
SLH
EX-NA- 7 (continued)
SLCl
SLC2
M IN DEG C GM/CM SPLE MOLES/M I N GM 5PLE*10**4
162.
163.
I64.
165.
166.
167.
I6 d .
169.
170.
171.
172.
173.
174.
175.
176.
177.
17 6.
I 7V.
180.
181.
182.
I S3.
134.
165.
156.
187.
168.
4 20.
421 .
422.
424.
42 6.
42 6.
431 .
4 3 3.
436.
4 3 8.
441 .
4 44 .
448.
451 .
4 54.
457.
460.
462.
463.
464.
465.
467.
468.
469.
471 .
4 72.
473.
. I81o
.2112
.2393
.2 534
.2836
.3107
. 3339
.3 560
.3741
.3912
.4033
.4234
.4395
.4525
• 4666
.4757
.4827
.4918
.5028
.5209
.5259
. 52 59
. 5330
.5 340
. 5350
.5 360
.5 380
. O A c, O
.0064
.3102
.0102
.0101
.009 5
.009u
.0086
.0083
.0078
.0075
.0071
.00 68
.0065
.00 62
.00 59
. 0056
.0053
.0051
.004 9
.004 9
.004 7
.004 6
.0045
.0044
.0042
.0040
.nm3
.OOriS
.0004
.0004
.0004
.000 5
.0006
.0006
.0007
.0008
.0009
.0011
.0016
.0023
.0024
.0024
.0325
.0025
.002 5
.0326
.0026
.0027
.0028
.0028
.0028
.0029
.0029
r .onnn
0.0300
0.90^0
0.0000
0.0000
0.0000
0.0000
0.0000
0.3000
.0002
. rTi n O
.O n o 4
.0005
.0005
.non 6
.3006
.0036
.0006
.0006
.000 7
.0037
.'"'007
.0007
.0037
.0007
.0007
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
.3379
.0437
.0520
.3622
.0724
.0823
.3916
. I005
. I090
.1171
. 1248
.1921
.13 91
.1458
.15 2 2
.1582
.1640
.16 9 5
. I 748
.1798
. I848
. 1896
. 194 3
. I900
.2335
.2078
.2120
.3312
.0016
.0020
.3025
.0029
.0035
.0040
.004 7
.0354
.0063
.0072
.0383
.0397
.0117
.0140
.016 5
.0190
.0216
.0241 ,
.0268
.0294
.0 322
.0350
.0378
.3407
.0436
.0465
0 .noon
n. n n n o
0.3000
0.3030
0.0000
0.3000
0.0000
O .nnoo
0.0000
.0001
.9002
.3005
.3010
.0015
.0021
.9027
.0033
.0039
.0046
.0053
.0060
.0067
.3074
• 0981
.0088
.0095
.0103
Table VII
TIME
TEMP
WTLFR
SLH
EX-NA- 7 (continued)
SLCl
SL C 2
M IN DEG C GM /CM SPLE MOL ES/M IN GM SPLE #10**4
16V.
190.
191.
192.
193.
194 .
193.
196.
I9 7.
196.
199.
200.
201 .
202.
203.
204.
205.
206.
207.
206.
20 9.
210.
211.
212.
213.
214.
215.
474.
475.
4 76.
477.
478.
4 80.
481 .
482 .
464 .
465.
487.
4 8b .
491 .
49 3.
494.
496.
500 .
502.
50 5 .
506 .
510.
512.
514.
516.
517.
518.
52 0.
. 5400
.5410
.5420
. 5430
.5434
.5439
.5443
.5447
.5451
.3471
.5476
.5481
.5484
.5487
.5 490
.5493
.5496
.5499
.5502
. 5505
.5508
.5511
.5514
.5517
.5520
.5523
.5526
.0038
.0035
. 0083
.003 1
.0028
.0026
.0025
.0023
.00 21
.0019
.OC I 8
.0017
.0016
.0016
.0016
.0017
.0018
.002 0
.0022
.0026
.0032
.0035
.00 3 6
.0037
.0038
. 0039
.0039
.0029
.0029
.0029
.0027
.002 5
.0024
.0024
.0023
.0023
.0022
.0022
.0021
.0021
.3021
.0021
.0022
.° 0 2 3
.0024
.0025
.0027
.0029
.0030
.0031
.0032
.0033
.0033
.0033
•0 0 b 7
.0007
.1007
.0006
.00-6
.0036
.000 5
.000 3
.000 3
.1312
.0002
.0002
.000?
.000?
.0012
.0002
.0002
.0002
.1002
.0002
.Oil?
.0002
.0002
.0002
.0002
.0002
.0002
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
.2160
.2 197
.2232
.2264
.2294
.2322
.2848
. 2372
.2395
.2415
.2436
.2453
.2470
.2487
.2 504
.2521
.2 5 39
.2559
.2 58 I
.2605
.2635
.2669
.2705
.2742
.278 1
.2820
.28 59
.0495
.0524
.0553
.0582
.060 8
.0634
.0658
.0682
.0706
.0729
.0751
.077 ^
.0795
.0816
.0838
.0860
.9883
.090 7
.0932
.0958
.0987
.1017
. I048
. 1080
.1113
.114 7
.1181
.0110
.0117
.0124
.0131
.0138
.0144
.0150
.115 5
.0158
.0161
.0164
.0167
.0169
.0171
.0174
.1176
.1170
.0181
•018 3
.0186
.0189
.0192
.0195
.0197
.0200
.1203
.0206
Table VII.
TIME
TEMP
WTLFR
SLH
EX-NA- 7 (continued)
SLCl
S LC 2
M IN DEG C GM/GM SPLE MOLES/M IN GM SPLF « 19**4
216.
217.
216.
219.
220.
221.
222.
223.
224.
225.
226.
227.
228.
229.
2 30.
231 .
232.
233.
234.
235.
236.
2 3 7.
23d.
235.
240.
241.
242.
521.
522 .
523 .
524.
52 5.
526.
52 7.
52 8 .
530.
532 .
533 .
535.
536.
538.
539.
541 .
542 .
544.
547.
548.
550.
5 52 .
553.
5 54.
5 5 6.
558 .
560.
.5529
.5532
.5535
.5538
.5541
.5541
.5541
.5 54 I
.5541
.5541
.5 54 I
.5541
.5541
.5541
.5541
.5542
•5543
.5544
.5545
.5546
.5547
.5548
.5549
.5 5 50
.5551
.5553
. 5555
.0040
.004 0
.0040
.0041
.0041
.0041
.0041
.0041
.0042 '
.0042
.0037
.00 3 I
.0024
. 0 0 16
.0014
.0015
.0019
.0023
.0025
.0026
.0026
.00 2 7
.0027
.002 8
. 0028
.00 2 8
.0020
.0033
.0033
.0033
.0033
.0032
. 0 0 32
.0031
.0031
.0031
.0033
.9029
."029
.0028
.0027
.0027
.0026
.0025
.0024
.0023
.0022
.3021
.0021
.0020
.0020
.002 3
.0019
.9018
.0092
.0002
.0002
.0032
.9001
.9001
.3391
.900 1
O."000
9.0000
0.0000
0.3909
0.9090
0.0900
0.0000
0.0000
0.0000
0.9993
0.3399
9 ."099
3.909 0
0.9000
0.0000
9.0999
0.9000
0.9999
9.0090
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*I0**4
.2899
.2940
.2980
.3021
.3062
.3 194
.3145
.3187
.3229
. 3271
.3311
.3345
.3373
.3394
.3410
.3425
.3442
.3464
.3488
.35 13
.3540
.3 R 6 7
.3594
.3622
.3650
.3679
. 3708
.1215
.12 4 8
.1282
.1315
. 134 8
.1380
.1412
.14 4 4
.14 7 5
.1506
.1537
.1566
.1595
.1623
.1651
.1678
. 1704
.1728
.175 2
. 1775
.1797
.1818
.I8 3 9
.1860
. I 880
.1900
.1920
.0209
.0211
.0214
. 0 2 16
.0218
.0220
.0221
.0223
.0224
.0224
.0225
.0226
.0226
.0226
.0227
.0227
.0227
.0227
.0227
.0228
.9228
.0228
.0228
.0228
.3223
.0228
.0228
Table VII.
TIME
TEMP
WTLFR
SLfI
EX-NA- 7 (continued)
SLCl
S LC 2
M IN DEG C G M /CM SPLE MOLES/M IN GM SPLE*10**4
243.
2 44.
24 5.
246.
247.
246.
24 V .
-250.
251.
252.
253.
254 .
255.
256.
25 7.
250.
259.
260.
261 .
262.
263.
264.
265.
266.
267.
268.
269.
5 61.
563.
565.
566.
567.
560.
5 69.
571 .
573.
577.
5 78.
575.
5 80.
562.
563.
565.
58 7.
5 6 6.
5 90.
592.
592 .
593.
595.
596.
597.
599.
601 .
.5557
.5559
.5561
.5563
.5565
.5567
.5569
.5571
.5571
. 5571
.5571
.5571
. 5571
.5571
.5571
.5571
.5571
.5571
.5572
.5573
.5574
.5575
.5 576
.5577
.5578
.5 579
.5560
.00 29
.0029
.002 9
.002 9
.0029
. 00 30
.0030
.0030
.0030
.0030
.0030
.0033
.0031
.00 31
.0031
.0031
.003 1
.0031
.0031
.00 31
.0031
.0032
.0032
.0032
.0033
.0033
.00 3 4
.0017
.0016
.0014
.0015
.0016
.0017
.0016
.0018
.0016
.0018
.0018
.001 8
.9018
.0018
.0018
.0017
.0017
.0017
.0017
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.0016
0.0000
. 0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
O .O n "io
0.0000
o.oonn
o .noon
O .noon
n.ionn
0.0000
0.0000
0.0onO
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
n .n o O O
n.nnnn
0.0000
0.0000
0.0000
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
.3737
. 3766
. 3796
.862 5
. 3855
.38 3 5
.3916
.3946
. 3977
.A n o 7
.4038
.4069
.4 100
.4131
.4 I62
.41 94
.4225
.4 2 56
.4288
.4320
.4 3 5 2
.43 84
.4416
.4648
.44 8 I
.4 5 15
.4 5 49
.19 3 8
.1955
.19 71
.1986
.2002
.2019
.2037
.2056
.2074
.2093
.2111
.2130
.2 14 8
.2167
.2185
.2203
.2221
.2238
.2256
.2273
.2290
.2306
.2323
.2340
.2356
.23 73
.2390
.0228
.0228
.0228
.0228
.0228
.0228
.0228
.0223
.0228
.0228
.0228
.n228
.0228
.0226
.0222
.0228
.0228
.0228
.0228
.0228
.0228
.0223
.0223
.0228
.022 8
.0228
.0228
Table VII. EX-NA- 7 (continued)
TIMF
TCMP
WTLFR
SLH
SLCl
S LC 2
M IN DEG C C M / GM SPLE MOLES/M IN GM SALE*10**4
270.
2 71 .
272 .
273.
274.
275.
276.
277.
2 76.
279.
2 60.
261 .
282.
283.
284.
285.
286.
267.
268.
269.
290.
291 .
292.
2 93.
294.
295.
296.
632.
603.
604 .
60 6.
60 o .
605.
611.
6 13 .
615.
617.
618.
615.
621 .
623.
623.
623.
624.
624.
624.
62 4.
62 5.
62 5.
62 6.
626.
62 7.
62 7.
627.
.5581
.5532
.5583
.3584
.5585
.3586
.5587
.5 588
.5 589
.5 590
.5591
.5592
.5592
.5 593
.5593
. 5594
. 5594
.5595
.5 5 9 5
.5 596
.5 596
.5597
.5597
.5598
.5593
.5599
.5599
.0035
.0035
.0036
.0037
. 0038
. 0039
.00 4 0
.0041
.0043
.004 3
.0043
.0043
. 004 3
.004 3
.0043
.0043
. 0042
.0042
. 0041
.0040
.0038
.0936
. 00 3 5
. 00 34
.0033
.0032
. 0031
.0016
.0016
.0016
.0016
.0016
.0016
.9016
.3017
.0017
.no I 7
.0017
.0017
.0017
.0016
.0016
.0016
.0016
.0015
.0015
.0015
.0014
.0014
. no 14
.0013
.0013
. 0012
. 0012
0.0000
0.0000
0.0090
0.0000
0.0030
0.0009
0.9090
0.0090
0.9000
O .9 n O O
O .O O n o
9.0090
n .0090
0.3090
0.0000
O .0090
0.0099
0.9000
n .9 9 9 0
O .0900
0.0000
9 . 9099
0.0000
9.0000
0.0000
0.0000
9.0090
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
.4584
.4619
.4655
.4 692
.4730
.4 769
.48 09
.4850
.4 893
.4936
.4980
. 5023
. 5067
.5110
.5154
.5197
.5240
. 5283
.5 3 2 5
.5 ^ 66
.54 06
. 54 4 3
. 54 7 9
.5514
. 5548
. 5580
.5612
.2407
.2423
.2440
.2457
.24 74
.2 4 9 I
.2508
.2525
.2542
.2 560
.2 577
.2594
.261 I
.2628
.2645
.2661
.2678
.2694
.2709.
.2725
.273 9
.2754
.2766
.2782
.2795
.2808
.2821
.0228
.0228
.0228
.0228
.0228
.0228
.9228
.0228
.0223
.02 28
.0228
.0228
.0228
.0228
.0228
.0228
.0228
.0228
.0228
.0228
.92 28
.9228
.0228
.0228
.0228
.0228
.0228
TIME
TCMP
WTLFR
Table VII
CX-NA-
SLH
SLCl
7
(continued)
SLC2
M IN DEG C GM/GM FPLE MOLCS/MT N GM SPLE*10**4
297.
298.
2 99.
300.
627.
628.
628.
62 9.
.5 600
.5 600
.5601
.5601
.0030
.no 3 0
.0029
.0028
.0012
.non
.0011
.0011
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
0.0000
0.0000
0.0000
o.OOnn
.5 644
.5674
. 5704
.5733
.2833
.2845
.2857
.2868
.0228
.0228
.0228
.0228
This program is Fortran II written for the IBM 1620.
I
Vn
?
Table VIII
EX-NA-
T IME
TEMP
WTLFR
SLH
SLCl
8
SLC2
MIN IDCG C 'C M/GM GPLE MOLCS/M IN GM SPLE * 10**4
92.
93.
94.
95.
96.
97.
98.
'99.
190.
101 .
102.
103.
104.
195.
196.
10 7.
108.
109.
no.
111.
112.
113.
114.
115.
116.
117.
118.
401 .
403.
4 n6 •
408.
41n.
412.
413.
413.
4 14 .
415.
416.
417.
418.
419.
42 0.
421 .
422 .
423.
425.
426.
42 8.
429.
431 .
43 3 .
43 5 .
436.
433.
0.0003
.0010
.3023
.302 5
.0030
."3 72
.0103
. OI 8 5
.0237
.036 1
.3505
.3673
.0846
.10 9 3
.1330
.1537
. I74 3
.2042
.2321
.2 620
.2961
.3239
.3476
. 3652
.3807
.3951
.4096
.0002
.0 005
.0 3 0 2
.3 0 ^ 2
. nno4
.090 7
.0011
.0017
.0038
.0061
.0083
.0136
.0129
.0152
.O I7 5
.0198
.02 21
.02 44
. 02 4 5
. 0244
.0225
.0206
.0187
.0168
.0156
.0144
.0132
3.0000
0.0000
3.003"
3.3033
3.3030
3.00""
3.0000
0.030^
". OOO"
0 . 0 0 O9
.0001
.03"2
.0003
.0003
.0004
.003 5
.0036
.0007
."007
.0007
.0007
.0008
.0008
.0008
.3308
.0009
.0009
0.0030
O. 0 0 0 3
A 1PZ-I1
-IA
O .3 A A A
3 *3 "3 3
3.0930
0.0000
0.393)3
9.3339
0.0000
0.3970
9 .a n a n
0.0000
0.0030
9.7003
0.0009
0.0039
O .0090
9.0000
0.0000
o.oooo
0.009-0
0.0000
0.0000
0.0000
9.3 099
0.0000
SSUMH
SSUMCl
SSUMC2
TOTAL MULES/GM SPLE*10**4
.0001
.0003
."995
.9937
."911
.09] 6
.0926
.0040
. 0 968
.0117
.0190
.0295
.04 04
.O r'4 5
.0700
.0896
.110 7
.1340
. 158 5
.18 3 0
.2065
.2281
.2477
.2655
.2817
.2968
.3107
0.0000
0.0000
3.7739
9.9039
0.9099
0.0399
0.0009
0.9009
0.0000
0.0000
.000 1
.0093
.0006
.0013
.9014
.0019
.0025
.0032
.0039
.0047
.0054
.0062
.0071
.0079
.0087
.0096
.0105
O. 3 0 0 0
0.0000
0.9909
0.9909
9.9000
0.9900
0.0900
0.3909
0.9909
O .0900
O .0000
o.oono
0.0000
0.0000
0.9000
0.9900
0 .0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0900
O. 0 0 0 0
0.0000
Table VIII
TIME
TEMP
WTLFR
SLH
EX-MA- 8 (continued)
SLCl
SLC2
MIM DEG C CM/GM SPLE MOLES/MI N GM SPLE*10**4
119.
120.
121.
122.
123.
124.
125.
126.
12 7.
128.
129.
130.
131 .
132.
133.
134.
13 5.
136.
13 7.
138.
139.
140.
141 .
142.
143.
144.
145.
439.
441.
442 .
44 4.
4 4 6.
4 48.
4 50.
4 52 .
453.
455.
457.
460.
462 .
464.
4 66.
467.
4 69.
471 .
4 74.
4 76.
470.
480.
4 02 .
483.
485.
487.
488.
.4219
.433 3
.4415
.4498
.4 580
.4663
.4725
.4 776
.4849
.4869
.4931
.4983
.5034
.5055
.5086
.5127
.5138
.5158
.5189
.5210
. 5230
.5241
. 5272
.5282
.5207
.5292
.5303
.0121
.0109
.0106
.0103
.0100
.0097
.0095
.'''091
.0006
.0000
.0075
.0071
.0067
.0065
.0064
.00 63
.0062
.0061
.0060
.0059
.0058
.0057
.0055
.0053
.0049
.0041
. 0036
.0010
.0011
.0012
.0013
.0014
.0015
.0016
.0017
.0019
.0020
.0021
.0023
.0024
.0026
.0027
.0029
.0031
.0034
.0035
.0037
.0036
.0038
.0038
.0039
.0039
.0039
.0039
0.0000
0.0000
0.0000
.0001
.OOr'I
.00"!
.0002
.0002
.0003
.0003
.0004
.0004
.0005
.0006
.0006
.0007
.000 7
.0008
.0009
.0009
.0010
.0010
.0011
.0011
.0011
.0011
.0011
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM 5PLE*10**4
.3234
.3 349
.3457
.3561
.3663
.3762
. 3858
.3° 51
.404 1
.4125
.4203
.4276
.4 345
.44 12
.4477
.4541
.4 604
.4666
.4727
.4787
.4846
.4904
.4961
.5016
.5067
.5113
.5151
.0116
.0127
.0 138
.0151
.0165
.0179
.0195
.0212
.02 30
.0250
.0271
.0294
.0317
.0343
.0370
.0399
.0429
.0462
.0497
.0534
.0572
.0610
.0649
.0688
.0727
.0767
.0806
.0001
.0001
.0002
.0003
.0004
.0006
.0008
.0011
.0014
.0017
.0022
.0026
.0031
.0037
.0043
.0050
.0058
•0066
.0075
.0085
.0095
.0106
.0117
.0128
.0139
.0151
.0162
Table VIII. EX—NA- 8 (continued)
TEMP
WTLFR
SLII
SLCl
SLC2
MIN DEG C GMZGM SPLE MOLESZM IN GM SPLE*10**4
146.
14 7.
148.
149.
150.
151 .
152.
153.
154. .
155.
156.
157.
158.
159.
160.
161 .
162 .
16 5.
164.
165.
166.
167.
168.
169.
170.
171 .
172.
4 89.
491 .
492 .
492 .
49 3.
494 .
496.
497.
49 6.
499.
501 .
502.
503.
504.
507.
509.
511 .
513.
514.
516.
516.
519.
52 0.
522.
524.
525.
526.
.5308
.5323
.5 344
. 5 354
.5365
.53 75
.5 360
. 5 390
.5396
.5397
.5 398
.5399
.5401
.5402
.5403
. 5405
.5406
.5406
.5407
.5408
. 5403
.5409
.5410
.5419 '
.5411
.5413
.5414
.0032
.0029
.0026
.0023
.0021
.0016
.0015
.OO I3
.0010
.0009
.0008
.0008
. 000 9
.0009
. OOlO
.0010
. OO I1I
.00 11
.0011
.0011
.0011
.0011
.0011
.nO I I
.0010
.0010
.0011
.9011
.0038
.0010
.0038
.0037
.0010
.0035
.000 9
.0034
.0008
.0032
.0006
.0030
.0005
.0028
.0002
.0001
.0027
0.0090
.0026
.0024
0.0000
n.oooo
.0022
0.0000
.0021
.0029
0.0000
.9019
0.9000
.0019 1 0.0090
.0019
c.ooco
.0020
0.0000
.0021
0.0000
.0021
0.0000
.0020
0.0000
O.OO^n
.0020
.0019
0.0099
.0019
0. "iOOO
0.0009
.0018
.0018
0.9000
0.0009
.0018
SSUMH
SSUMCl
SSUMC2
TOTAL MOLESZGM SPLE*10**4
.5186
.5217
.5245
.5270
.5293
.53 13
. 5330
. 5344
. 5356
.5366
. 5375
.5383
. 5392
. 5402
.5412
.5422
.5433
.5445
. 54 5o
. 5468
. 54 8 0
. 5491
.5502
.5514
. 5525
. 5536
.5547
.0845
.0883
.0921
.0958
.0993
.10 2 6
.1058
.1067
.1116
. 1142
.1167
.1191
.1213
.1234
.12 5 5
.12 74
.12 94
.1314
.1335
.1356
.1377
.1398
.1418
.1437
.14 5 6
.1475
.14 9 3
.0173
.0164
.0195
.0204
.0213
.0221
.0227
.0231
.0232
.0233
.0234
.0235
.0236
.0236
.0237
.0238
.0239
.0239
.0240
.0240
.0241
.9241
.0241
.0242
.0242
.0242
.0242
-CS-
TIME
Table VIII.
TIME
TEMP
WTLFR
SLH
EX-NA- 8 (continued)
SLCl
SLC2
MIN DEG C GM/GM SPLE MOLES/MI N GM SPLE*10**4
173.
174.
175.
176.
17 7.
178.
17V.
180.
181.
18V.
183.
184.
18b.
186.
18 7.
188.
189.
190.
191 .
192.
193.
194.
19b.
196.
197.
198.
199.
527.
528.
52 9.
5 30.
531 .
532 .
53 3.
534.
535.
536.
5 37.
538.
54 0.
542 .
543.
54 5.
54 7.
54 8.
5 50.
552 .
5 53.
555 .
95 7 .
558.
559.
561.
562 .
.5416
.5417
.5419
. 5420
.5422
.5423
.5425
.542 6
.542 7
.542 8
.5428
.5429
.5429
.5430
.5430
.5431
.5431
.5432
.5432
.5433
. 5433
.543 4
• 5434
.8435
.5435
.54 36
.5436
.0011
.0011
.0011
.00 I I
.0011
.00 I I
.00 I I
.0011
.0010
.0010
.0009
.000 5
.0009
.0009
.000 9
.0009
.0009
.0009
.0005
.0009
.000 9
.0010
.0010
.0011
.0011
.0011
.0011
.0017
.0017
.0017
.0017
.0016
.0016
.0015
.0015
.0015
.0015
.0015
.0015
.0015
.00 15
.0015
.0018
.0015
.001 5
.0018
.0015
.0015
.0015
.0015
.0015
.0015
.0015
.0015
0.0000
0.0000
o.~ooo
0.0000
O .0OCio
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
noon
O •n 0 O O
0.0000
0.0000
0.0000
o.nooo
0.0000
0.0000
0.0000
0.0COO
0.0000
0.0000
0 . nono
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
.5,5 58
.5 569
.5580
.5591
. 5603
. 56 14
.5626
. 5637
.5649
.3659
.5669
.5679
.5689
.5698
.5707
.5717
. 5726
.5736
.5745
. 5755
.5765
. 5775
.5785
. 5.796
. 5807
.5819
.5830
.1511
. I 529
.15 4 7
.1564
. 1502
.1598
.1614
.1630
.1645
.1660
.1675
.1691
.1706
. 172 I
.1736
.1751
.1766
.1781
. I79 6
.1811
.1826
.1842
.1657
.1872
. 1887
.1903
.1918
.0243
.0243
.0243
.0243
.0243
.0243
.0243
.0243
.0243
.0243
.0244
.0244
.02 44
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.02 44
.0244
.0244
.0244
Table VIII.
TIME
TEMP
WTLER
SLH
CX-NA-
SLCl
8 (continued)
SLC2
>11N IDEG C GM/CM SPLE MOLES/MI N GM SPLE*10**4
200.
201 .
202.
203.
204.
205.
206.
207.
208.
209.
2 10.
211.
212.
2 13.
214.
215.
216.
217.
216.
2 19.
22 0.
221.
222.
223.
224.
22 6 .
226.
563.
564.
565 .
566.
56 7.
5 68.
570.
571 .
572.
5 74 .
575.
5 76.
578.
580.
562.
584.
58 7.
589.
591 .
593.
59 5.
597.
596.
600.
602.
603.
604.
.5437
.5437
.5438
.5438
.5439
.5439
.5440
.54 4 ■I
.544 I
.5441
.5442
.544 2
.54 4 3
.5 4 4 4
.5444
.5445
.5445
.5446
. 544 6
. 54 4 7
.5447
.5448
• 544 8
. 544 9
.54 4 9
. 5450
.54 50
.0011
.0011
.0011
.0011
.0011
.0011
.0011
.0011
.0012
.0012
.0012
.0012
.0013
.00 13
.00 I4
.0015
.0017
.00 18
.0019
. 002 0
.0021
.0021
.0021
.0022
.0022
.0022
.0023
.0015
.0015
.0015
.0015
.0015
.0014
.0014
.0014
.0015
.0015
.0015
.0015
.0019
.0015
.0015
.0015
.0015
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.0016
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
O .0000
0.0000
O .0000
0.0onO
0.0000
0.0000
0.0000
0.0000
0.0000
o.oooo
n .noon
O .norm
r.nnnn
n. OOOO
0.0000
o.oooo
0.0000
0.0000
0.0000
0.0000
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
.5842
.5853
.5865
.5876
. 5888
. 5 900
.5912
.5° 2 3
.5935
.5948
.5960
. 5972
.5985
.5999
.6013
.6028
.6045
.6063
.6082
.6102
.6 I2 3
.6144
.6166
.6188
.6211
.6234
.6257
.1933 .
.1948
. 1963
.1979
. I994
.2009
.2024
.20 39
.2054
.2069
.20 84
.2099
.2114
.2130
.2145
.2 161
.2176
.2193
.2209
.2226
.2242
.2259
.2276
.2293
.2310
.2327
.2344
.0244
.0244
.0244
.0244
.0244
.0 244
.0244
.0244
.0244
.0244
.0244
.0 244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
Table VIII.
T IME
TEMP
WTLFR
SLH
E X— N A - 8 (continued)
SLCl
SLC2
M IN DEG C CM/GM SPLE MOLES/M IN GM SPLE*10**4
227.
228.
22 b/.
230.
231 .
232.
288.
2 34.
235.
236.
2 3 7.
2 3 8.
239.
240.
241.
242.
24 3.
244.
24 3.
246.
24 7.
246.
249.
250.
251 .
2 32.
253.
60 6.
60 7.
603 .
611 .
612.
614.
61b.
618.
61 V.
622 .
623.
62 3 .
624.
623.
626.
62 7.
627.
62 7.
62o.
62 6.
62 5.
630.
630.
630.
63 0.
630.
631 .
.5451
.5451
.3452
. 5452
. 3453
.5453
.343 4
.5454
• 5455
.5455
.34 36
. 3456
.545 I
.5437
.5457
.5457
.5437
.545 7
. 5457
.545 7
.545 7
.5457
.545 7
.5457
.545 7
.5457
.5457
.0023
.0024
.0024
.002 5
.0026
.0026
.00 27
.0028
.0028
.002 9
.0029
.0030
.00 3 I
.0030
.00 3O
.00 3 0
.00 29
.0-29
.0028
.0027
.0026
.0025
.0024
.002 4
.0023
.00 2 3
. 0022
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.00 16
.0015
.0015
.0015
.0015
.0019
.0014
.0014
.0014
.0014
.0013
.0013
.0012
.0012
.0011
.0011
n.nnon
0.OOOO
0.0000
O.o000
0.0000
0.0000
0.0000
0.0030
0.0000
0.0000
0.0000
o .0000
O .OOOO
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
C.0000
3.0000
0.0000
0.0000
o.nono
0.0000
0.0000
0.0000
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
.6280
.6305
.6329
.6355
.6381
.6407
.64 34
.64 6 2
.6491
. 6520
.6550
.6580
.66 10
.6641
.6672
.6702
.6732
.6762
.6790
.6818
.6845
.6871
.6896
.69 20
.6944
.6968
.6901
.2360
.2377
.2394
.2411
.2428
.2 444
.2461
.2473
.2495
.2511
.2528
.2544
.2 560
.2576
.2591
.2607
.2622
.2637
.2652
.2666
.2681
.2695
.2709
.2722
.2734
.2746
.2758
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.0244
.02 44
.0244
Table VIII.
TIME
TEMP
WTLFR
SLH
EX-NA- 8 (continued)
SLCl
SLC2
M IN DEG C GM/GM SPLE MOLES/MI N GM SPLE*10**4
254.
255.
256.
257.
25b.
25%.
260.
631 .
6 31.
632 .
632 .
632 .
633.
63 3.
.5457
. 5457
. 5457
.5457
.5457
.5457
.5457
.0021
.0021
.0020
.0019
.0018
.0017
.0017
.0011
.0011
.0010
.0010
.001 .
.0009
.0009
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
This program is Fortran II written for the IBM 1620
.7013
. 7034
'.7056
.7075
. 7094
.71 12
.7130
.2769
.2780
.2791
.2802
.2812
.2822
.2832
.0244
.0244
.0244
.0244
.0244
.0244
.0244
i
o
Vl
Table IX
EX-NA-IO
TIME
TEMP
WTLFR
SLIT
SLCl
S LC 2
M 11'I DEG C GM/CM SPLE MO LES/MI N GM 5PLE*10**4
40.
41.
42.
43.
44 .
43.
4 6.
47.
4 6.
4V.
50.
51.
52.
53.
54.
55.
56.
57.
38.
55.
6 0.
61.
62.
63.
64 .
65.
6 6.
375.
376.
377.
3 79.
381 .
3 82 .
3 84.
38 5.
387.
388.
389.
391 .
392.
395.
397.
399.
4f0.
402 .
4^3.
404 .
404.
40 5.
406.
40 7.
408 .
408.
410.
0.0000
0.0000
0.0000
0.0000
0.9099
0.0OOO
9.0099
0.0090
0 .OOOO
9.9909
0.0090
0.0009.
O . 0000
o.oooo
0.0000
0.0009
0.0000 . n . 9 9 0 0
9.0900
0.0900
0.0990
0.0OOO
0.090'
0.0000
O.9909
0.0000
0.0000
0.099'
O.nnno
0.9900
.0091
0.0000
0.0900
.0091
.0001
0.0900
.9901
0.0900
.0919
.00 0 I
.0016
.0002
.00 30
.0002
.00 70
.000 3
.0 Ill
.009 5
.0161
. 0003
.0212
.0014
.0033
.0292
0.9000
0.0000
9.9909
9.9009
9.0990
0.9009
9.9000
0.0000
9 .9009
9.0000
9.9099
9.OOfP
O .O099
o.oooo
9.0099
0.0099
9.9900
0.0000
9.0099
9.900^
9.0090
0.0000
0.0000
0 . 0 0 OO
0.900,9
.0001
.0001
O .0999
0.0000
9 .0099
9,999 "V
0.9009
9.9099
0.9000
0.0000
9.0000
9.0009
9.9990
0.0090
0.9999
9.0090
0.0909
o.oooo
0.0000
o.oooo
0.9900
0.0000
9.000 9
0.0000
0.0090
0.0090
9.0990
0.0009
0.0000
SSUMH
SSUMCl
SSUMC 2
TOTAL MOLES/GM SPLE*10**4
0.0900
0.0000
0.0090
0.0099
0.0909
0.0000
0.0000
0.0000
0.0900
0.9000
0.0900
0.0000
0.0000
0.0000
0.0000
9.0000
.0 0 0 J
.0001
.0001
.0002
.000 2
.0002
.0093
.00 03
.0004
. 9005
.9906
.0007
.9008
.0009
.0011
.0013
.0015
.0017
0.0000
.0021
0.9000
.0025
0.0000
.0030
.0001
.0002
.00 39
.0062
o.oooo
o.oooo
0.9009
0.0900
0.0009
o.oooo
0.0000
0.0000
0.0900
.0003
O .0000
0.0000
0.0000
0.0000
0.0000
0.0900
0.0000
0.0000
0.0000
O.oooo
O .0000
0.0000
9.0000
0.0000
0.0900
0.0000
O .0000
0.0900
0.0000
0 .0009
0.0000
0.0000
0.0000
0.0000
0.9000
O. 0000
0.0000
Table IX.
TIME
TEMP
WTLFR
SLH
EX- NA- 10 (continued)
SLCi
SLC2
MIN IDEG C iCjM/ GM SPLE MOLES/M I N GM S P L E * 1 0 * * 4
67.
6 6.
69.
70.
71.
72.
.73.
74.
7 6.
76.
77.
76.
79.
30.
61 .
'Xj
CO
3 3.
34.
Sb.
3 6.
87.
3d.
39.
90.
91 .
92.
9j .
411.
413.
414.
414.
416.
4 17.
41b.
42 I .
422 .
424.
427.
430.
4 32 .
4 34.
4 3 7.
44 0 .
44 3 .
447 .
4 60.
4 61 .
464.
4 56.
4 5 7.
4 53.
460.
4 61.
461 .
.0403
.0685
.0767
.0969
.1171
.1403
• I 666
.19 73
.2261
.2514
.2806
. 304 9
.3311
. 3604
. 3836
.40 38
.41 o I
.433 1
. 4 4 72
.4583
.4664
. 4 725
.4 785
.4656
.4896
.4937
.4957
.0043
. 0057
.0072
.008 6
.0094
.0 102
. OI I O
.0119
.0127
.0138
.0150
.0161
.0173
.0173
.0173
.0159
.0146
.0133
.012 J
.0107
.0107
.0108
.0106
.0110
.0111
.0110
.0108
.8002
.0003
.0003
.0003
.0004
.0004
.0004
.0004
.0004
.0004
.0005
.0006
.0006
.O O ll
.0012
.0016
.0019
.0021
.002 3
.002 6
.0028
.0030
.0031
.0033
.0035
.0036
.0038
0.0000
0. DOO ''
0.0000
0.0000
0.0000
0.0000
0.0000
O eOdO O
0.0000
O.dQOO
O. o d O
O .0000
0.^000
o .OOOO
.0001
.000 I
.0002
.0003
.0004
.0006
.0008
.0010
.0013
.0015
.0019
.0020
.0020
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM S P L E * 1 0 * * 4
.0100
.0151
.0216
.0295
. 0 386
.0485
.0592
. 0 707
.083 O
.0963
.1107
.1263
.1430
.1603
.1776
.1943
.2096
. 2.2 36
.2364
.2478
.2586
.2694
.2803
.2913
.3024
.3135
.3244
.0005
.0008
.0012
.0015
.0020
.0024
.0028
.0033
.0037
.0042
.0047
.0053
.0061
.00 71
.0063
.0097
.0115
.0136
.0159
.0184
.0211
.0240
.0271
. 0 304
.0339
.0375
.0412
O. n o o n
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
O . 0000
O .0000
o .n n o o
o . noon
o.nnoo
0.0000
.OOQl
.0002
.000 3
.0005
.0008
.0012
.0017
.0024
.0034
.0046
. 0061
.0078
.0098
.0113
Table IX.
TIME
TEMP
WTLFR
SLII
FX-NA-ID
SLCl
(continued)
SLC2
M IN DEG C GM/CM SPLE MO L ES/M IN GM SPLE*10**4
94.
99.
96.
97.
96.
99.
100.
IDl .
102 .
103.
104.
103.
106.
10 7.
10 6.
I0 9.
I 10.
111.
112.
113.
114.
119.
116.
117.
11 o .
119.
120.
462 .
464.
466.
46 7.
46o .
4 69.
4 70.
4 71.
4 73.
4 74 .
4 74 .
4 7 9.
476.
477.
476.
4 00.
480.
4 00.
462.
484.
466.
4 89.
492 .
49 3.
4 9 9.
497.
496.
.4977
.4 9 9 7
.9028
.904 6
.9078
.9109
.9129
.9149
.5179
.5199
.5209
.5230
.5240
.5260
.5270
.5269
.5 310
.532 I
.5331
.5341
.5351
.5361
.5371
.a3 8 I
•9 3 c I
.5361
.5301
.009 7
.0066
.0075
. 0064
.0052
.0042
.0035
.0031
. 002 9
.0027
.0025
.0024
.0022
.0021
. 0019
.0016
.001 I
.0016
.0016
.0015
.0014
.0014
.OCI j
. 0013
.0014
.0014
.0014
.00 39
.0040
.0042
.0043
.0043 •
.0042
.0041
.00 4 D
.0039
.0038
.0037
.0034
.0033
.0031
.0029
.0028
.0027
.0025
.0025
.0024
.002 3
.0022
.0022
.0021
.0021
.0022
.0022
.0017
.0015
.0014
.0013
.DOl I
.0011
,0010
.0009
.000 8
.0007
.000 7
.0006
.0006
.000 5
.000 5
.0004
.0004
.0003
.000 3
.0002
.0002
.0002
.0001
.0001
.0001
.0001
.0001
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
.3347
.3439
.3 520
.3589
. 364 8
. 3696
.3 73 5
.3769
.3799
.3828
. 3854
. 3679
.3902
. 3924
.3945
.3964
.3982
. 3999
.4016
.4032
.4047
.4061
.4075
.4089
.4103
.4117
.4132
.0452
.0492
.0533
.0576
.0619
.0662
.0705
.0746
.0 786
.0826
.0863
.0o99
.0933
.0966
.0996
.1025
. 1052
.10 79
• 1104
.112 9
.1153
.1176
.1199
.12 2 1
.1248
.1265
.12 8 7
.0137
.0153
.0168
.0182
.0194
.0206
.0217
.0226
.0236
.0244
.0252
.0259
.0265
.0271
.0276
.0281
.0285
.0289
.0292
.0295
.0298
.0300
.0302
.0304
.0306
.0307
.0309
Table IX.
Ql
:•
LJ
TIME
WTLFR
SLH
EX-NA-10 (continued)
SLCl
SLC2
M IN DEG C CM/GM SPLE MOLES/NI N GM SPLE#10**4
513.
515.
516.
517.
515.
520.
521.
522.
523.
524.
52 6.
526.
52 7 .
534.
533.
537.
53o .
.5362
.5363
. 5364
.3365
.5 366
.5367
.5388
.5369
.5 390
.5 J v I
.3392
.5393
.5354
. 3395
.5396
.5.33 7
.5 398
.5399
.54 00
.54 9 1
.5402
. 5405
.5406
.5407
.3406
.0015
.0015
.0015
.00 I 5
.00 15
.0015
.0013
.0015
.0014
.0014
. OC 14
.0014
.0013
.0013
. 09 13
.OOlo
.0013
.00 ib
.3012
.0012
. 73 12
.0011
.0011
O
O
501 .
50 3.
504 .
50 5.
507.
510.
511.
TM
in
121 .
122.
123.
124.
125.
126.
127.
I2 o .
129.
130.
131.
132.
133.
134.
135.
136.
137.
13U.
139.
140.
141.
144.
145.
146.
147.
.0012
.0001
.0022
.0022
.0001
.0001
.0022
.0022
.0001
.0021 . .0001
. ^0 9 I
.0020
.002 0
.9001
.000 1
.0019
.0019
.0001
.0019
.0001
.0018
.0001
.0018
'0.0000
.0018
0.0000
.0017
0.0000
.0017
0.9090
.0017
0.0000
9.0009
.0017
0.0099
.0017
0.9 0 O O
.0017
9 .0090
.0016
0.0090
.0016
.0016
0.0000
0.0009
.0016
.0016
0.0090
.0015
0.0000
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SOLE*10**4
.4147
.4163
.4176
.4 194
.42 09
.4225
.4240
.4255
.4270
.4263
.4300
.4314
.4326
.4342
.4355
.4 369
.4382
.4395
.4408
.4421
.4433
.4470
.4482
.4494
.4507
.130 9
.1332
.1354
.1377
.1396
.1420
. 1440
.1460
.14 80
. I 500
.1519
.IbJl
.1556
.1574
.1592
.1609
.1627
.1644
.1661
.1676
.1695
.1744
.1761
. 1777
.1793
•0310
.0312
.0313
.0315
.0316
.0317
.0319
.9320
.0322
.0323
.0325
.0326
.0326
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
Table IX.
T IME
TEMP
WTLFR
SLH
EX-NA-IO (continued)
SLCl
SLC 2
M IIxl DEG C GM/GM SPLE MOLES/M IN GM SPLE*10**4
148.
149.
130.
131 .
132.
133.
154.
153.
156.
157.
15 8.
159.
160.
161 .
162.
163.
164.
16 3.
166.
16 7.
168.
169.
I 70.
171 .
172.
173.
174 .
541 .
5 4 3.
544.
546.
54 7.
346.
5 50.
531 .
553 .
5 54 .
5 56.
357.
5 38.
5 59.
560.
561 .
562.
563 .
5 63.
565.
567.
569.
570.
5 71.
5 73.
573.
5 76.
.5409
.5410
.5411
.5414
.54 1 7
.3421
. 5424
.542 7
.5430
.5433
.5436
.54 39
.5442
.5443
. 5444
.5445
.5446
•5 4 4 7
.5 4 4 8
.5 44 9
. 54 50
.3451
.545 2
.5434
.5456
.5458
.5 4 60
.00 I 3
.0013
.0014
.0014
.0014
.0015
.0015
.0015
.0015
.0015
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.0017
.00 17
.0017
.0017
.0017
.0017
.0018
.0016
. 0019
.0020
8. p q n o
.0015
0.0000
.001 5
0.0000
.0015
0.0000
.0015
.0015
0.0000
.0015
0.0000
0.0000
.0015
.0016
0.0000
.0016
0.0000
.0016
0.0000
0.000o
.0016
o.oooo
.0016
.0016
0.0000
0.0000
.0 0 I5
.0013
0.0000
0.0000
.0013
0.0000
.0014
.0014
0.0000
.0014
0.0000
.0014
0.0000
.0014
0.0000
.0014 . 3 . DOOO
.0014
0.0000
.0014
O.oooo
.0014
O.0000
.0015
3.3030
.0015
0.0000
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
.4520
.45 34
.4548
.4562
.4 5 7 7
.4592
.4607
.4622
.4638
.4 6 54
.4670
.4686
.4702
.4719
.4735
.47 52
.4769
.4 786
.4803
.4821
.4838
.4856
.4873
.439 I
.4910
.4929
.4949
.1809
.1825
.184 0
.1355
.1871
.1667
.1902
.1918
.1934
.19 51
.19 6 7
.1983
.1999
.2015
.203 1
.2046
.2061
.2076
.2090
.2 104
.2119
.2133
.2148
.2163
.2176
.2193
.2208
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
TIME
TEMP
WTLFR
SLH
EX-NA- 10
SLCl
(continued)
SLC2
MIN DEG C GM/GM SPLE MOLES/M IN GM SPLE*I0**4
.54 62
.5464
. 5466
. 5466
.54 70
.54 72
.54 73
.5475
.5476
.5477
. 5479
.54 60
•9 4 tiI
.5 4b 5
.546 4
•54 6 5
.548 7
.5 4 o 6
.5469
.5491
.5492
.5494
. 5495
. 5496
.5498
.5499
.5 500
.0021
.0022
.0024
.002 6
. 0027
.002 9
. I '3 I
. 0034
.0037
.0041
. 004 5
.00 4 9
.00 52
.0055
.00 5 6
. 0056
.00 56
.0057
.00 56
.00 54
.00 51
.004 9
.004.8
.0047
.0046
. 0046
.004 5
.0015
.0015
.0015
.0016
.0016
.0018
.0019
.0020
.0021
.0021
.0021
.0022
.0022
.0022
.0022
.0022
.0022
.002 0
.onzr
.0019
.0018
.0016
.0017
.0017
.0016
.0016
.0016
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.000 )
0.0000
0.0000
0.0000
0.0000
0.0000
• 0.0000
0.0000
C
C
C
C
t>7 v .
660.
663.
56 6.
569.
591 .
592 .
5 96.
59o .
601 .
604.
60 7.
609.
611.
614.
615.
616.
617.
616.
6 Io .
619.
620.
622.
622 .
62 6.
624.
62 5.
C
17b.
176.
177.
I 7a.
I 7b.
160.
161 .
162 .
163.
164.
185.
186.
167.
loo.
18V.
IVO.
191.
192.
193.
194.
19 6.
196.
19 7.
196.
19V.
2 00.
201 .
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE--10**4
.4970
.4992
.5016
.5041
.5068
.5097
.5127
.5160
.5196
.52 3o
. 5280
. 5327
.5376
. 54 32
. 5489
.5548
.5606
.5664
.5721
.5.776
.5829
.5880
. 5929
.5977
.6024
.6070
.6116
.2223
.2236
.2254
.2270
.22 86
.2304
.2323
.2343
.236 4
.2385
.2407
.2429
.2451
.24 74
.2496
.2519
I'D
VT
Table IX.
.2563
.2584
.2603
.2622
.2641
.2659
.2676
.2 694
.2710
.2727
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
Table IX.
TIME
TEMP
WTLFR
SLM
EX-NA-IO
SLCl
(continued)
SLC2
M IN DEG C G M /CM SPLE MOLES/MJN GM SPLE*10*>4
202.
203.
204.
2 0 3.
206.
2 0 /.
20 o .
2 0 9.
2 10.
211.
2 12.
213.
214.
215.
626.
627.
62 b.
62 V .
62V.
6v v .
6 31.
632.
63 2 .
632.
632.
632 .
632 .
632 .
.5 502
. 5503
. 5 504
.5506
. 5507
. 3506
.5510
.5511
.5512
.5512
.5512
.5512
.5512
.5512
.0044
.0043
. 0042
.00 42
.004 V
.003 V
.003d
.0037
.0036
.0035
.00 3 4
.0032
.00 3 I
.0030
.0015
.0015
.0013
.0014
.0014
.0014
.0014
.0013
.0013
.0013
.0012
.0012
.001 I
.0011
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0030
0.0000
o .noon
0.0000
0.0000
0.0000
o . o OFio
SSUMH
f
SSUMCl
SSUMC2
TOTAL MOLESZGM SPLE*10**4
.6160
.6204
.6247
.6290
.6331
.6372
.6411
.64 49
.6487
.6522
.6557
.6591
.6623
.6653
This program is Fortran II written for the IBM 1620
.2743 .
.2759
.2773
.2 788
.2602
.2617
.2 o 3 I
.2845
.2856
.2872
.2884
.2 697
.2909
.292 I
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
.0327
Table X
EX-MA-11
TIME
TEMP
WTLFR
SLH
SLCl
S LC 2
M IN DEG C GM/GM SPLE MOLES/MI M GM SPLE*10**4
0.0000
0 .O 0 <00
0.0000
0 .OOOO
o.0000
O.0000
r. .no n n
^ .o o O o
O .O n0 n
0 .on OO
0 . 0 000
0.0000
0.0000
0 .o O o 0
0.0000
o.oooo
0 . 0 On o
O .n o o o
O .n o o 0
0.0000
O.OQOO
.0012
.0032
.0064
.0102
.0205
.0333
0.0000
n.nooo
o.oooo
O .ooon
0.0000
n.nooo
o .o n 0 0
0.300^.
0 .0 ~ n "
^ A '
O.OOOO
n.nooo
0.0000
n . o O 0 r’
0.0000
0 .onno
o', noo n
n ,0 n n 0
0 .noon
.0 0 0 1
.0001
.0 0 0 1
.0 0 0 2
.000 3
.00 06
.0013
.0030
0 .0 0 0 "
n.nooo
0.0000
n .nnno
n.OQon
n.nooo
n.nonn
0 .0 0 0 °
n.nnnn
n .noon
0 . non"
n .noon
0.0000
n.OOOn
0.0000
n.nooo
' ° .0 on "
0 .0 0 0 "
n.oo ° "
o.non "
0.0000
0.0000
n.nooo
n.noo"
0 .0 0 0 °
n.nooo
0 .0 0 0 °
o.oooo
o.oooo
0.0000
n.nnnn
0.0000
n.nooo
n.nnnn
n .OOOO
".on~ ^
n.nnnn
n.nooo
n.nnnn
n.nooo
n.nnnn
0.0000
n.nnnn
n.nnnn
".^n^n
".OO" "
". 0 0 ""
n .noon
O.OOOO
n.nooo
".nonO
0.0000
n.nnnn
0 .n n n n
SSUVCC
TOTAL MOLES/GM SPLE*10**4
n.onno
n.nooo
.0001
.0 n n 1
.0001
.0002
.0002
.0003
.0003
.0004
.0004
.0004
.0 005
.0005
.0006
.non?
.non-/
.0008
.nnnq
.0010
.O O 11
.0013
.0015
. 0 0 13
.002 3
. '033
.0 n 5 6
n.nnnn
n.nnnn
o.oooo
n.onno
n.nnnn
O.OOOO
0.0000
o.oooo
n.nnnn
n.nnnn
o.oooo
n.onno
0.9009
n.nooo
0.0000
n.onno
o.nnno
n.nnnn
n.nnnn
n.nnnn
0 .0 0 " 0
0.0000
O.OOOO
T.90"'
0.00 MO
n.o non
C
364.
365.
365.
36 6 .
369.
373.
376.
378.
381 .
383 .
384.
386.
388.
390.
392.
394.
396.
39o.
401 .
404.
405.
40 7.
410.
412.
413.
414 .
416.
SSUMCl
C
C
C
C
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
3 7.
38.
39.
40.
41.
42.
43.
44.
45.
46 .
SSUMH
n.nnnn
0.0000
0.0000
0 .n n n n
o.nnno
n . 0 n 0n
n .nr,on
" . 0 no n
•"•'"00
0 ." 0 o"
0 .0 :V),0
0 .nr on
n.nooo
n.nnoo
o.oooo
n.nooo
n.nnnn
n . " n -n
O ."Of O
".no "n
"."•" O0
I . 0 0 0,0
n.o-n
■0 .n n n n
0 .0 n n n
n .n n n n
'•.n • n
Table X
TIME
TEMP
' WTLFR
SLH
E X - N A - 11 (continued)
SLCl
SLC2
MIN DEG C GM/GM SPLE MOLES/M I N GM S P L E * 1 0 * * 4
47.
4d.
49.
53.
51.
52.
53.
54.
55.
56.
57.
56 .
5V.
67.
6 i'.
62.
63.
64 *
65.
66.
67.
66.
69.
70.
71 .
72 •
73.
416.
417.
417.
417.
419.
421 .
423.
425.
426.
42 7 .
430.
433.
435.
436.
439.
441 .
443.
445.
446.
446.
450.
451 .
453.
4 55.
456.
457.
45b .
.0512
.0704
.0999
.1176
.1537
.1922
.2255
.2550
.2896
.3165
. 3370
.3575
. 3754
.3908
.4062
.4190
.4344
.4510
.4664
.4779
.4862
.4933
.4972
.4997
.5048
.5100
.5125
.0047
. 0 0 64
.0081
.0098
.0115
.0131
.0148
.0165
.0182
.0187
.0189
.0191
.0191
.0192
.0191
. 0190
.0189
.0187
.0185
.0181
.0177
.0173
.0168
.0162
.0156
.0149
.0143
0.0000
0.0000
.0001
.0001
.0002
.0003
.0004
.0005
.0006
.0007
.000 7
.0008
.000 9
.0010
.0011
.0013
.0015
.0017
.0019
.0021
.0024
.0027
.003 "
.0033
.0035
.0037
.0039
0.0000
0.0000
0.0000
n.oono
n .0000
0.0000
0.0000
0.0000
O . OO^iO
0.0000
0 . oooo-*
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
.0001
. 0001
.0002
.00^3
.OOOA
.000 5
.000 7
.0009
.0012
.0015
SSUMH
SSUMCl
S SUMC2
TOTAL MOLES/GM S P LE* 1 0 * * 4
.0095
.0151
.0224
.0314
.0420
.0544
.0684
.0841
.1016
.1201
.1389
.1579
.1771
.1963
.2155
.2346
.2537
.2725
.2912
. 3095
.3275
.3451
. 3622
.3763
.3948
.4101
.4248
0.0009
.0001
• 0002
• 0003
.0006
.0009
.0013
.0018
.0024
.0033
.0038
.0046
.0055
.0065
. 0 0 76
.0089
.0103
.0120
.0138
.0158
.0181
.0208
.0237
.0269
.0333
. 0 3a9
.0378
0.0000
O• n OOO
0.9000
0 . nn0 O
0.0000
O• Oo o 0
C.^COO
0.9930
O. 9. ~ o o
O. 9 0 3 0
0.0300
0.0000
0.0000
0.0000
0.0000
.0001
.0002
. 000 3
. 0 004
.000 7
. 9009
.0013
.0019
. - ' 02 5
. 0 ' ?4
• -<•6
. 3C59
Table X.
TIME
TEMP
WTLFR
SLH
EX-NA-Il (continued)
SLCl
SLC2
M IN DEG C GM/GM SPLE MOLES/MI N GM SPLE*10**4
74.
75.
76.
77.
73.
77.
80.
61.
32 .
6 3.
84.
6 5.
86.
87.
88.
69.
90.
91 .
92.
93.
94.
95.
96.
9 7.
96.
460.
461.
462.
463.
464.
46 5.
467.
466 .
469.
471 .
473.
475.
477.
4 76.
478.
479.
432 .
435.
4 6 6.
46o •
489.
49 0.
492.
494.
99.
496.
499.
100.
500.
.5151
.5177
.5202
.5228
.5241
.5266
.5279
.5296
.5318
.5343
.5356
.5369
.5362
.5 394
.5407
.5414
.5420
.5426
.5433
.5442
.5452
.5462
.5471
.54 78
.5464
.5491
.549 7
.0136
.0130
.0123
.0117
.0110
.0103
. 0097
.0090
.3083
.0072
.0061
.0049
.0038
.0326
.0015
.0012
.0011
.0009
.0009
.0003
.0006
.0009
.0011
.0013
.0013
.0013
.0014
.0041
.0042
.0044
.0045
.0047
.3048
.0049
.0050
.00 50
.0053
.00 50
.0049
.0048
.0047
.0046
.0044
.0043
.0041
.0039
.0036
.0032
.0029
.0027
.0325
.0024
.002 3
.0022
.0016
.0016
.0017
.0017
.0017
.0017
.0017
.0016
.0016
.3316
.0315
.3014
.0013
.0011
•O 0 n 9
.00^8
.000 5
.0003
.0002
.3001
.30 0 I
.OOn.I
.0001
.0001
.0002
.0002
.0002
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SFLE*10**4
.4388
.4521
.4648
.4 768
.4882
.4989
. 5090
.5184
.527 1
.5349
.5416
.5471
.5515
.5547
.5568
.5582
.5594
.5605
.56 14
.5623
.5632
.5641
.5651
.5663
.5677
.5691
.5705
.0416
.0463
.0503
.0543
.0595
.0643
.0652
.0742
.0793 .
.0844
..0894
.0944
. .3993
.1040
.1067
.1133
.1177
.12 19
.1260
. 1296
.1332
.1362
.1391
.0075
.0092
.0109
.0126
.0143
.n ISl
."173
.0 19 5
.0212
.3228
.02 44.
.3259
.3273
.-285
.n2 96
.0305
.0312
.0317
.-320
.-321
.0323
.0324
.0 325
. 14 I 7
.0327
.0329
.0331
.1442
.14 6 7
.1490
.0324
Table X.
TIME
TEMP
WTLFR
SLH
EX-NA-Il
SLCl
(continued)
SLC2
GM/GM SPLE MOLES ZMIN GM SPLE*10**4
MIN I
DEG C '
IJl .
102.
10 3.
104.
105.
106.
107.
106.
109.
I 10 .
111.
112.
11 j.
I In.
115.
116.
117.
116.
119.
120.
121.
122.
12 3.
124.
125.
12 6.
12 7.
502.
503.
504.
506.
508.
509.
510.
512.
514.
514.
516.
517.
519.
520.
521 .
522.
52 4.
526.
526.
527.
528.
529.
531 .
532.
533.
534.
536.
.5501
.5505
.5508
.5512
.5516
.5 520
.5524
.5528
.5532
.5535
.5544
.5538
.5539
.5541
.5542
.5543
.5 544
.5 546
.5547
.5548
.5550
.5552
.5554
.5556
.5558
.5560
.5562
.0014
.00 14
.0014
.0013
.0013
.0013
.0013
.0013
.0013
.0013
.0013
.0012
.0011
.0010
.0010
.0010
.0010
.0010
.0010
.0010
.00 10
. 3010
.0010
.0010
.0010
.0010
.0010
.0022
.0021
.0020
.0020
.0019
.0019
.0019
.0019
.0019
.0020
.0020
.0020
.0019
.0019
.0019
.0019
.0018
.0018
.0017
.0017
.0016
.0016
.3016
.0016
.0016
.0016
.0016
.0001
.3001
0.0000
0.0030
0.0000
0.3000
-.00-0
0.0003
0.0033
0.0030
■0.000 0
0.0000
3.3000
0.0000
0.3030
0.3000
0.3000
0.0000
0.0030
0.0000
0.0000
0.0000
3.3000
0.0030
0.0000
0.0000
0.0000
SSUMH
SSUMCl
SSUMC2
TOTAL MOLESZGM SPLE*I0**4
.57 19
.5733
.5747
.5761
. 5775
.5768
.5802
.58:6
.5830
.5843
.5856
.5369
.5861
.5892
.5903
.59 13
.5924
.59 34
.5944
.5955
.5965
.5975
.1513
.1534
.1555
.1575
.1595
.1615
.1635
.1655
.1675
.1695
.1715
.1735
.1755
.1775
.1795
.1615
.1834
.1652
.1370
.1383
.1905
. 1922
.0336
.0337
.0333
.0339
.0340
.03-40
.0341
.0341
.0 342
.0 3-42
.0343
.0343
.0334
.0 344
.03 +5
.0345
.0 346
.0 346
.03-46
.03^6
.0347
.0 34 7
. 59 86
. I5j 9
. 0 5 l, 7
.5996
.6006
.601 7
.6027
.19 5 5
.1972
.1989
.200 5
.0 347
.0347
.03-7
»0 3•+/
I
Table X.
TIME
TEMP
WTLFR
SLH
EX-NA- 11 (continued)
SLCl
SLC2
M I N DEG C C M / GM SPL E MOLE S / M I N GM S P L E * 1 0 * * 4
126.
129.
130.
131.
132.
133.
134.
135.
136.
137.
133.
139.
140.
141.
142.
143.
144.
145.
146.
147.
Ho.
14 9.
150.
151 .
152.
15 3 .
154.
538.
540.
541 .
543.
544.
546.
547.
546.
549.
552 .
554.
556.
557.
559.
561 .
563.
564.
565.
566.
568.
571 .
573.
573.
574.
575.
576.
582 .
.5564
.5566
.5567
.5569
.5571
.5573
.5575
.5577
.5579
.5561
.5583
.5585
.5567
.5587
.5588
.5569
.5589
.5590
.5590
.5 5 9 1
.5592
. 5592
. 5593
.5594
. 5 594
.5595
. 5596
.0010
.0010
.0011
.0011
.0011
.0011
.0 0 1 0
.0010
.0011
.0011
.0012
.0012
.0013
.0013
.0013
.0014
.0014
. 0 0 I '4
.0014
.0015
.0015
.0016
.0017
.0017
.0017
. 0017
.0017
.0016
.0016
.0016
.0016
.0016
.0016
.0016
.0017
.0017
.0017
.0017
.0017
.0017
.0017
.0017
.0017
.0017 *
.0017
.0017
.0017
.0017
.0017
.0017
.0017
.0017
.0017
.0017
o.oooo
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
H O O -IO
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
3.0000
3.0000
0.0000
0.0000
0.0000
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM S P L E * 1 0 * * 4
.6038
.6349
. 6060
.6071
.6082
.6093
.6104
.6115
.6126
.6138
.6149
.6162
.6175
.6188
.6202
. 6 2 16
.6230
.6245
.6259
.6274
.6290
.6306
.6323
. 6 ?4 O
.6357
.6375
.6392
.2022
.2039
.2056
.2073
.2090
.2107
.2124
.2141
.2158
.2175
.2192
.2209
.2226
.2243
.2260
.2278
.2295
.2312
.2330
.2347
.2365
. 2 382
.2400
.2418
.2436
.2454
. 2 4 72
.0347
.0347
.0347
.0347
.0347
.0347
.0347
• 0 3<+7
.0347
.0347
.0347
.0347
.0347
.0347
.0347
.0347
.0347
.0347
-.0347
.0347
.0347
.0347
.0347
.0347
.0347
.0347
.0347
Table X.
TIME
TEMP
WTLFR
SLM
E X-i\A- 11
SLCl
(continued)
SLC 2
M I,N DEG C GM/GM SPLE MOl ES/M I,N GM SPLE*10**4
155.
156.
157.
156.
159.
160.
161.
162 .
1 6 -'.
164.
165.
166.
I6 7.
166.
I6 •>.
170.
171.
I "2.
173.
174.
175.
176.
177.
I 76.
179.
160.
I6 i .
584.
586.
586.
586.
586.
587.
586.
559.
5 90.
591 .
592.
593.
594.
5 9 7-.
598.
600.
601 .
602.
604.
60 7.
607.
606.
610.
611 .
612.
614.
614.
.5596
.5597
.5596
.5598
.5 599
.5599
.5 600
.5601
.5601
.5602
.5603
.5603
.5604
.5605
.5605
.5 60 6
.5607
.5607
.5608
.5608
.5609
.5610
.5610
.5611
.5612
.5612
.5613
.0017
.0017
.0018
.0018
.0018
.0019
.0019
.0019
.3019
.0019
.00 19
.0019
.0319
.0019
.0019
.00 I9
.0319
.0020
.0023
.0020
.0021
.0021
.0022
.0022
. 0323
.0023
. 0023
.0017
.0017
.0017
.0017
.0016
.0015
.0015
.0015
.0015
.0015
.0015
.0015
.0015
.0015
.0015
.0015
.0015
.0015
.3015
.0015
.0015
.0015
.0015
.0014
.0014
.0014
.0014
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
0.0000
^.00^0
0.0000
0.C000
3.0000
conn
0.0000
0.C033
n.nnnc
0 . noon
0.0000
o.oooo
0.0000
•2.000 o
0.0000
0.000n
0.0000
0.0000
T .OOOC
SSUMH
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
.6410
.6427
.6445
.6463
.6482
.6501
.6520
.6539
.6559
.6578
.6597
.6616
.6635
.6655
.66 74
.6693
.6713
.6733
.6754
.6775
.6796
.6817
.68 39
.6861
.6854
.6928
.6931
.2490
.2507
.2525
.2543
.2560
.2576
.2592
.2607
.2623
.2633
.2653
.2669
.2 684
.2699
.2714
.2733
.2745
.2760
.2 775
.2790
.2305
.252 I
• O 3D
.2 O 5 I
.2866
•2d ,II
.2 3 9 5
.0347
.0347
.0347
.0 347
.0 347
.03 ^
*' , "
• —
.O i*’
.03 t.
.0 34 i
.CO-'
.0 3.r Z 'i~
.0 3.034 7
.0347
.0 3-7
. .03-7
.03-7
.0347
.0347
.0 3-7
.0 3 -7
.On'- i
.0347
.0347
.
Table X.
TIME
TEMP
WTLFR
SLH
E X - w A - I I (continued)
SLC I
M IN DEG C GM/GM SPLE MOL ES/M I,N GM SPLE*13**4
182.
183.
CO
r-H
185.
186.
187.
180.
139.
190.
191.
192.
195.
194.
195.
196.
197.
19 6.
199.
200.
201 .
202.
203.
204.
205.
615.
616.
617.
616.
619.
62 I .
622 .
623.
623.
623.
623.
624.
624.
624.
625.
62 6.
6 2 6.
62 7.
62 7.
627.
627.
627.
62b.
62 o .
.5614
.5614
.5615
.5615
.5616
.5617
.5617
.5618
.5619
.5619
.5620
.5621
.5621
.5622
.5623
.5623
.5624
.5624
.5625
.5625
.5625
.5625
.5625
.5625
.0023
.0022
.0022
.0021
.0021
.3021
.0021
.0021
.0021
.0021
. 0021
. 00 2 0
.0020
. 00 2 0
.0020
.0019
.0019
.0016
.0016
.0018
.0317
.0017
.0016
.0016
.0014
.0014
.0014
.0013
.0013
.0312
.0012
.0012
.0012
.0012
.0012
.0012
.0012
.0012
■ .0011
.0011
.0010
.0010
.0009
.0009
.0039
.0008
.0008
.0006
SSUMH
S LC 2
SSUMCl
SSUMC2
TOTAL MOLES/GM SPLE*10**4
0.0030
0.0000
3.0000
0.0000
0.0000
0.0000
3.0003
o.ooon
0.0000
0.0000
O.0000
0.0000
0.0000
o.oooo
0.0000
0.0000
' .0000
0.0300
0.0000
0.0000
o.oooo
0003
0.3000
0.0000
This program is Fortran II written for the IBM 1620
.6955
.6978
.7000
.7022
. 7044
. 7066
. 7087
.7109
.7130
.7152
.7173
.7194
.7215
.7235
. 7256
. 7276
.7296
.-315
. 7334
. 7352
. 7370
. 7398
. 7405
.7422
.2910
.2925
.29.59
.2953
.2966
.2979
.2992
.3004
.3017
.3029
.3041
.3053
.3065
.3077
.3089
.3101
.3112
.3122
.3132
.3142
.3151
.3160
.3169
.3178
.034 7
.0347
.03*7
.0 347
.03*7
." 3 4 7
.0347
•0 3*7
.0347
.0347
.0347
.0347
.03*7
.03*7
.0347
.0347
.03*7
.0347
.0 5 +7
.0347
.0347
.0347
.0347
.0347
Table XI.
Run
No.
Residue
gm/mol
Unreacted
Naphthacene
mol/mol
Results of Individual Runs
Total
Condensate
gm/mol
I
gm/mol
II
mol/mol
III
H2
CH 4
C2%
gm/mol
mol/mol
mol/mol
mol/mol
7
98.7
.1928
82.6
3-2
.0556
66.9
.01214
.00616
.000513
8
101.9
.2602
63.7
3.82
.0465
49.2
.0149
.00579
.000548
10
100.0
.1885
81.5
3.26
.0497
68.0
.0140
.00612
.000737
11
98.5
.294
60.5
3.02
.0381
46.6
.0163
.00694
.00078
-73-
Table XII.
Products of the Pyrolysis of One Mole of Naphthacene
Product
Amount in Moles
or Grams____
•unreacted naphthacene
.214 moles
compound I
5 ,12-dihydronaphthac ene
Weight Percent of
Original Sample
21.4
3.48 grams
1.52
.0508 moles
5.12
compounds III and IV
62.3 grams
27.28
carbonaceous residue
102.0 grams
44.66
hydrogen
.0137 moles
.012
methane
• .00614 moles
.043
ethane
".00054 moles
■
.007
■ -74-
Table XIII.
Variable Names in the Computer Program
HFACT
pressure
correction term for
CFACT
pressure
correction term for CH^
C2FACT
Pressure
correction term for C^Hg
TIME
time recorded during run in order to connect time
of sample injection with the continuously measured
variables
SL
rate normalization according to sample size —
S
rate normalization according to material remaining
in reactor — RH
SUM- —
total .amount of gas evolved
SSUM
amount of gas evolved/weight of sample
WTUN
units from the recorder measuring reactor weight
WTLFR
amount of weight lost since the beginning of the
run/weight of the sample
XL, YL
length of x and y axes
TIMED
TEMPO
WTLD
GASD
MIN,
amount of change in variable value between
grid lines
MAX
value of variable at endpoints of the grid
SIH
-75-
L & M Recorder
;e Ies
Reaction Chamber
Figure I.
Thermogravimetric Analysis Apparatus
-76-
unreacted naphthacene
— naphthacene-II interface
r I
x H I and IV
resistance
heater
location
// S /// / ~// / 77~T~77~?~77
reactor outlet
heating coils
thermowell
Mg inlet
Figure 2.
Equipment Modifications and Product Locations
Percent Weight Loss
H
M
H-
c
VjJ
b
-O
Time, Min
W
CS
m
3
tC
i
'O
:I j .
Gas Evolution Rate
Temperature, °C
4
moles/min gm sample x 10
-78-
/,Clg it lo:>s
te mpera ture
k " .
---\
\
'
I
f
:v:<
\
L
Z
X
'
• ./M - .M .V v .w .
X-XU-XtVXUMU..
f
f
i
'
f
f
f
--- h; fdrogc n
i
me the ne
X
ethar e
4
'
. I
/
Al
-I(
i
Is
90
'
.. ■vX'
130
)
— --C,:,.:.
170
...-.!
210
Time, Min
Figure 4.
Ex-NA-S Results.
v~'»
250
290
-79-
-- 4^^
i
weigh t los 5
**
temj eratu. '6 — \
*.
*
S
*
f
*
I
V.,
X v
-JV.-jut.
yJJ-LJJjfXUfJt*.
<f
i
f
f
h y d r )gen
I
I
;
_
m e bhane
^
— eth m e
*
*
*
-- ***M*-^ ....
30
f
*
Jjt-
-< >
70
/ \
J
S- "~
j
i
HO
Time,
Figure 5«
's
Ex-NA-IO Results
150
Min
190
230
-So­
.... I
:
'ight loss
ten iperat are
I
:
:
/
i
'
X .
—
.«v
-■
■y.w..vyxA.
v^,••
1
•
!■''
Hroge n
.
-me the ne
rr
f
z;
eths ne
/
7
''i x „
-.
lo
50
90
-"!*CZ3
130
Time, Min
Figure 6.
Ex-NA-Il Results
170
210
2
-Sii
4
Figure 7.
Chromatogram of Gaseous Products
Ill
I]
IV
i
00
1
ro
Solvent
Figure 8.
Condensate Chromatogram.
W AVELENGTH
IN
M ICRONS
- 83-
'2000
1900
'1800
170C
1600
1500
W AVENUMBER
Figure 9*
Infrared Spectrum of Compound II
1400
IN
1300
KAYSERS
) 1600
1500
W AVENUMBER
Figure 10.
Infrared Spectrum of Compound I.
1400
1300
IN KAYSERS
1200
1100
1000
900
-85-
Path length I era
Concentration
.00001 g/cc in
EtOH
Wavelength -- millimicrons
Figure 11.
Ultraviolet Spectrum of Compound I.
- 8
9.0
__I__I
100
IU
h:::
6
-
MICRONS
10.0
P -X
Hi-
^
IiilH
V=-
I
1200
1100
1000
n:
: T t M i H H H H i T T I r H H i t 80
i i T #
L f t rH T n il
H i i I U 11 T L I H H
i i H H H 11L U i H l N H j T
U H U i H HH T i
H ftLjTf
T T u r H I L- H U
: T T i- T i H T T I J i T iiM
I Li!
T i T T T TTTTfu I i
U U T H i n H i ; l i 111 11 H i i T
I-I I I t i i T ; : E U i T T - T U i r i
T i i i T n i l Li HJ ILii
T i I H l t i T U i U i i U i : : n ftTT
Hj T H ! ; ! . T i I T i H n
1
i u T UU T L IiLi- T i IHL i Hi
U t i T i 1.91 U l i I-Lii T i n n
Ti
T i T i iiii
0
ffit
ilii
1300
1 -T iT Y lT llT T T
;
ftI
LiH
I
Z
t
25.0
100
E iu
U
20.0
IiUi-
/I:IU - / T H U T
; ' IjiJJf U I: TTh T
Hf! T l
IM ffitH
I HI H Li
#
H i : Hi: U i L HH HH iiii
:!j I i i i H i i H i I H i t T F T i i i i i
I
#
H i i : l H J J i L 11H T l u
n i l HH -T l
# H lii1 HH
H i i m I - HTj H ; H
HH i l i i HH ! H i i i H -UH- Hi i U U ' : '
H r !i l l H U H I i i l i i
Hi! U Li: ULi 111 ! #
J i i • W Hi! J i i L #
U i TuT T i!
- I i l U i i H i : I Li! I Hi i l i i U i i ilii! H i i l H U
: Hi H i ! iH-i H i ! H i t
i U H JU i Uii
[77 i ill H H H i i !I:!i i n i i i i i
U U U i T U : I In
; Hi. i i - i H J U U U J J i L
-I hI hh : i H i
: - I U 4 T IHiHTTT
I Hi H i i U j I Hi i i i i #
h;i
t i i i m U i i J H i. H H i H-i I B i ! - T : I ' M
V i n T i T !.iji
iiij
H f i 1 11 U i
3
]5.o
900
800
700
600
500
400
MICRONS
2.5
'Too-
I
I
RANSMI'
100
Tt-Jli -EE j f t I LH= LUL
'
T
i i T T i T I i J t Li I I : I I i
L ; : I : I : : I I L I I i iJ L i I i T .
I Li i T i i T ii1
. „r_-— — — I T I T T R f J V /
:
I I : I I- U T T T i I T i I i L T ! ' I U J : I H I T '
J
T
LI I W
: 'I L i U
80
I IrUIH -I ! T i I I I i - N I ! I : i- r ---- '
- r I : • f t T ; i i T j,' I ; : i : iI L
: i:V
T i i ^ K T D I L / V i I I J- T i T H T I J f t I i i i T T i ' F l l T
. ! T i i - T
T T T i i
Jr l ; i t H T - I
r; I E U
: T:
T T : - I T i JIn U r n
; I Lii
I
I
:
I
i
I
J
r
H
I
I
I
!
U
c
N
c
T
Ti I nr
O 60
: TUiTHUki
I j iJ r i : : : I I I H r J I t it U N L f t i J r
Z
I -LJft T LJ i i Ui I
I I : IJ -T ftI
UU I H J U . I f t l Lr
I I I HULL i L i T T F T r F iF i N H
i=
l T i i I f t
U r i n LU
I I T T I:
: Li I J - J I i r k J H U t T f t I f t r L k J r H f t H N
: T T T I I.. Lr T r T : I : T T T T T T T I J T F i - 1 ; I J i : I T f t : ; T : : n r ;
HiLiT- ;Lu I i I I i I ! I t
T TH 1T
■
I t i t Li I I I I I I Ht tU
E r E
: I I Ln N J r N U T L r
J ! : -LUI f t f T HjH T i T T j f t f t T I
J J I UU T t T
U J T r T : Li l r i t m : r IrjU ; I I J T 1 LJ T T I N J J T N U t U i T
I I I T - I i I ; Li- I i n E t J T T i ! :
I I T 1J I Li NJ L f t
i i n I T i ! : -Jr1T t t U I-Jr T T I T r 1 ! : 1 : N r t T !rift- i I L H i U t J L t r i J f t l U JH
i l i i T i I : Er - E j h t f t r f f t : J i J J U U T l T I | I I I i L J J J T i J f t i . l . T t i I H
- UULr
T T - : : I : : : : :-lTT.S I j : —Hr ! r e t s
ft :
T ft I I ! I ! i
: : T T T T T T lf t r T H J ftiftN H
4000
3500
I
3000
2500
2000
FlEQUiNCY (CM-1I
Figure 12.
Infrared Spectrum of Compound III.
1500
-87MICk ONS
3.5
_L— .
S
4.0 MICRONS 5.0
6.0
.i.
100
-i 4 - -I
U iU
■ K- UU : : Li I ^ I i I I T I I U L k TTv ;
M iT
UtiL
4 : 1 . ii
i i M- ITL
i 11 I L:U i t Li I4 i ii i
M M :
M UMMi
Mill:.::
I !UUk
i M U z U: i T yv ! M TTi
■
T i F i l T u u ITTiiIiI I
l u m m
UU U I
: i
--Li-: ! I UU I
/
M i
i.U U .n i
U.| I UUU Li MUIU LU . U i i i :
LU
U- - M L U : UU I: I 4 I=I I i I i LI I I : !UiLU U
:Tr
-K u - I i I-T U M m - i A m e i / M ^ L U _ -.M/ 4.: L
-M I
UK
4:
i -i I TU
M f K L M = M M
ri - U I
i
UUU MUU- -.-L- :
i ; Ulu i : I I I-1 I r- I- I jlML LU.
U ' I:
■ U U
UUi-I 3 t JUU Li. I
U= U MUJ
M i M i i =U= LU
i U
u - : U=f 4-i
i Li. U i L
-I-: i-U- : M I I I I" Ml JEtMi
M
:
M
h : UUMUUM- K M .1. I i i I Li I l K U U M UM=
JLt U I i 4 Ui
4LU. U k U:i.L i TUMiiK- - :- i LI- L U :
MMMiM= -MTU
I K
: .
MiMU
m u
r
i u - LU J L L k
I : i K UTTi ri T U T I
: I I
iii
LU I Li UUM I K ■ : L i . L i I = Ii M M M M = I
T
#
I U - M U I : i I •: U - M I !.: I I T t l - M
LU i i U=LTt-L: MU I TM T i 3:
i h i
4000
3500
3000
2500
2000
1500
J : J lLu
. ' : 'I
■ ! Li^-—,i :
\i
m u
S
i LU
+i :I'
G 60
U j Mi Z
i U ::
E
m u 4
"t'
«
m
FREQUENCY [Cm ')
Figure 13.
Infrared Spectrum of Compound IV
::r r.r
: I1 I-
I
00
O O
1
:\ it:
I=-I--F
Figure 14.
Ultraviolet Spectra of Compounds III and IV in Ethanol
-89-Literature Cited
1. ' Bushongj E. M., et. al. Improved Graphite Materials for High
• Temperature Aerospace Use. Volume I. Research and -Development
for Improved Graphite Materials. Technical Documentary Report No.
ML-TDR-^-l’
25 Air Force Materials Laboratory Research, Patterson
Air Force Base, Ohio (1964) pp. 4l-4j5.
2.
Brooks, J. D . , and Taylor, G. H. "The Formation of Graphitizing
Carbons from the Liquid Phase." Carbon, 3. (1965), 185.
3.
Badger, G. M., Donnelly, Jillian K., and Spotswood, T. M.
"The Formation of Aromatic Hydrocarbons at High Temperatures
XXIII. The Pyrolysis of Anthracene." Australian Journal of
Chemistry, I? (1964), 1147-1156.
4.
.
5.
Personal Communication, Dr. J. R. Kiovsky, Continental Oil Company
1966.
.
Lewis, Irwin C., and Edstrom, T. "Thermal Reactivity of Poly­
nuclear Aromatic Hydrocarbons." Journal of Organic Chemistry, 28
(1963)., 2050-2054.
6 . ■ Madison, John J., and Roberts, Richard M.
and Related Heterocyclics."
50 (1958), 242.
"Pyrolysis of Aromatics
Industrial and Engineering Chemistry,
7«
Currie, Robert A. A_ Kinetic Study of the Pyrolysis Reactions of
Acenaphthylene and Bifluorenyl. Ph.D. thesis, Montana State
University, Bozeman, Montana, 1966.
••
8.
Infrared Spectral Data of American Petroleum Institute Research
Project~*44^ Serial No. 2230.
9«
Guvernator 1 C . , et. al. "Electron Capture Detection of GasChromatographed Polycyclic Hydrocarbons." Journal of Gas
Chromatography, 3. (1965), 363-367•
MONTANA STATE UNTVE/rSTTV I m o t a Tc<r
3 1762 100 5188 3
»
•
*
H378
• cop. 2
-
Philip, J. C.
The pyrolysis of naphthacene.
h i A M E A F i D AODRSS®
/KJ 7J
7