95.0R71113
THE PRESSURE AND TEMPERATURE EFFECTS
ON THE SOLUBILITY OF NITROGEN IN DISTILLED WATER
BY THOMAS JOSEPH SPINK
A THESIS
submitted to
OREGON STATE UNIVERSITY
SUPPORTED BY THE GRADUATE FELLOWSHIP PROGRAM
ENVIRONMENTAL PROTECTION AGENCY
WATER QUALITY OFFICE
PACIFIC NORTHWEST WATER LABORATORY
CORVALLIS, OREGON
EP 660/
71-251
APRIL 1971
library

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AN ABSTRACT OF THE THESIS OF
THOMAS JOSEPH SPINK for the MASTER OF SCIENCE	
(Name)	(Degree)
in CHEMICAL ENGINEERING presented on		
(Major)	(Date)
Title: THE TEMPERATURE AND PRESSURE EFFECTS ON THE
SOLUBILITY OF NITROGEN IN DISTILLED WATER
Abstract approved: 	
C. E. Wicks
The concentration of nitrogen in distilled water was measured
using a dynamic, turbulently mixed saturation chamber. Concentra-
tions at three temperatures (1 2. 3, 19- 6, and 25. 5°C) and three
pressures (760, 1520, and 2280 mm Hg) were investigated. Results
are presented as mole fractions, XN , and Bunsen coefficients,
2
a . A comparison of concentrations obtained by turbulent mixing is
made to concentrations obtained by only surface absorption with no
mixing. Concentrations are reported on the fifth day after turbulent
bubbling ceases.
It is shown that there is a significant difference in nitrogen
concentrations between the turbulently mixed system and the unmixed
system. Values taken from the turbulently mixed system are
approximately 130 percent higher than literature values. Values taken
from the unmixed system are 7 to 9 percent higher than literature

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values. The turbulently mixed system's concentrations closely
approximate Henry's Law.

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The Pressure and Temperature Effects on the Solubility
of Nitrogen in Distilled Water
by
Thomas Joseph Spink
A THESIS
submitted to
Oregon State University
in partial fulfillment of
the requirements for the
degree of
Master of Science
June 1971
LIBRARYC'"
Environ. Prot. AgSrtC?, WP
Efaaon. Nsw Jfirssy 08811

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ACKNOWLEDGMENTS
The author wishes to express his gratitude to two very helpful
groups of people: the personnel of the Pacific Northwest Water
Quality Laboratory, and the faculty and graduate students of the Chem-
ical Engineering Department.
Special thanks are extended to Dr. Charles E, Wicks for his
technical advice and to Mr. Bill Johnson for his help in obtaining
materials. Thanks are also due to Mr, Daniel Krawczyk, Chief
Consolidated Laboratories, who provided valuable assistance at the
Federal Water Quality Laboratory. Also, Mr. John Jacobson and
Mr. Richard Whitmer are thanked for their assistance in design and
photography.
Particular thanks are shown to my wife, Mary Ellen, and son,
Joe, who provided the needed relaxation and enjoyment to make my
graduate experience a memorable one.

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TABLE OF CONTENTS
Page
INTRODUCTION	1
BACKGROUND	3
Definitions	3
Methods and Results of Nitrogen Solubility in Water	5
Surface Tension	10
EQUIPMENT	13
Saturation Chamber and Sampling Device	13
Temperature and Pressure Measurement	19
Chromatograph and Chemicals	21
PROCEDURE	24
Standardization	24
Saturation	25
Sampling	27
RESULTS AND DISCUSSION	30
CONCLUSIONS	36
BIBLIOGRAPHY	37
APPENDICES	40
Appendix A: Nomenclature	40
Appendix B: Sample Calculations	42
Appendix C: Standardization of Sample Loop	46
Appendix D: Tabulated Data	47

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LIST OF FIGURES
Figure	Page
1.	General layout.	14
2.	Saturation and sampling schematic.	15
3.	Saturation and sampling photograph.	16
4.	Column and detector arrangement.	22
5.	Drying tubes used to standardize sample loop.	26
6.	Pressure-mole fraction relationship expressing Henry's
Law.	3 5
7.	Standard curve for 8-1 to 30.	43

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LIST OF TABLES
Table	Page
1.	Literature values of nitrogen solubility in water
(ax 10^).	7
2.	Literature values of nitrogen solubility at the experi-
mental temperatures of this study (a x 10^).	10
3.	Pressure difference due to surface tension.	12
4.	Nitrogen solubility in distilled water, (mole
fraction x 10^).	30
3
5.	Nitrogen solubility in distilled water (a' and a x 10 ).	30
3
6.	Time versus concentration for mixed system (a x 10 ).	33
3
7.	Time versus concentration for unmixed system (a x 10 ).	33

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THE PRESSURE AND TEMPERATURE EFFECTS ON THE
SOLUBILITY OF NITROGEN IN DISTILLED WATER
INTRODUCTION
In the Pacific Northwest there is a great interest in the solubility
of atmospheric gases in water. A disease known as the gas bubble
disease may be harming the migrating fishes of the Columbia River
system and other locations (6, 11). This disease has been reported to
cause blindness and a subsequent loss of proper spawning capabilities
(31). Occurrence of this disease has been noted in hatcheries (15, 25)
resulting in mortality even in young fish. Investigators generally indi-
cate that the gas responsible for this disease is.nitrogen (11, 24).
Concentrations of nitrogen are reported as percent saturation. Values
associated with toxicity are usually greater than 100 percent, thus
generating the term "nitrogen supersaturation."
Supersaturated levels of atmospheric gases were observed and
first reported by Jarnefelt in 1928 (15). In 1948, Jarnefelt (15) sum-
marized his earlier work and implicated rapids and hydroelectric
installations as the principle cause of variations in the nitrogen satu-
ration of water. A stream study by Harvey and Cooper (15) showed
that the amount of supersaturation was affected by the type of stream
flow. Water plunging into a deep basin increased the gas concentra-
tion in the water while water plunging off rocks into shallow areas

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2
appeared to decrease in gas concentration. Ebel (11) correlated the
degree of super saturation to the amount of water flowing over spill-
ways on the Columbia. River hydroelectric system. At high flow over
spillways high levels of nitrogen occurred.
Since supersaturated water is toxic to fish, various means have
been devised to eliminate supersaturated gas from the water (15, 25).
These devices are meant to operate on small scale such as the water
supply to a hatchery. The problem takes on much greater proportions
when dealing with a water system such as the Columbia River.
The supersaturation of nitrogen in water is a difficult phenomena
to accept. A possible explanation of supersaturation is that incorrect
values of absolute saturation are used to calculate percent saturation.
Values up to 110 percent can be explained by the variations in absolute
values. However saturation values greater than 110 percent cannot be
explained by variation in absolute values.
This study was initiated to build a laboratory apparatus that
would explore the nitrogen-water system. The apparatus was designed .
to mix turbulently nitrogen and water and then to analyze the mixture
as the system approached equilibrium. It was hoped that the phenom-
ena of supersaturation could be observed and solubility data could be
generated for varying temperatures and pressures.

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3
BACKGROUND
The subject of gas solubility in liquids has been investigated at
great length since early in the nineteenth century. . Much work has
been done in recent times to update the knowledge of gas solubility in
liquids. Markham and Kobe (18) reviewed the literature up to 1941,
and Battino and Clever (2) have gathered together a very comprehen-
sive review up to 1965. These two reports are quite comprehensive,
including such areas as methods of measuring solubility, definitions of
terms used in expressing gas solubilities, and over 1000 references
on solubility experiments.
Three important areas will be.discussed in this text. . The topics
include definitions used in expressing gas solubility, methods and
results in determining nitrogen solubilities, and surface tension
effects.
Definitions
The Bunsen coefficient, a, is defined as the volume of gas
reduced to 0°C and 760 mm Hg which is absorbed by a unit volume of
solvent (at the temperature of the measurement) when under a gas
pressure of 760 mm Hg. When the partial pressure of the gas above
the solvent differs from 760 mm Hg, it is corrected to this pressure
by Henry's Law. One equation used to calculate the Bunsen coefficient

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4
18
273 15 _k)(J_}1Z6o
m	7/.A " V ' J TJ
S
P
g
(1)
Equation 1 obviously reduces to
(2)
s
The units of Q are usually expressed as milliliters per milliliter.
In dealing with slightly soluble gases the units lend easily to interpre-
tation as parts per million.
Equation 2 shows no explicit pressure dependence. To show a
pressure dependence a modified form of the Busen coefficient is used.
The same calculations are applied to this coefficient, a', as to a,
except that a' is not corrected to 760 mm Hg by Henry's Law. In
this report two values, a and a1, will be reported at 1520 mm Hg
and at 2280'mm Hg. Henry's Law.can be. recognized in the re-
ported data with the modified form of the Bunsen coefficient.
Another term used extensively to report gas solubilities.is mole
fraction. All three forms of expressing gas solubility are used in
this text.

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5
Methods and Results of Nitrogen Solubility in Water
A great variety of approaches have been used to determine the
solubility of gases in liquids. The methods range from the purely
qualitative to the highly precise. The methods discussed in this sec-
tion are directly related to the solubility of nitrogen in water.
There are four general methods used to study the solubility .of
gases in liquids, manometric-volumetric methods (sometimes called
gasometric methods), mass spectrometric methods, gas chromato-
graphic methods, and chemical methods. Since chemical methods are
not usually applicable to dissolved nitrogen they will not be considered.
Manometric-volumetric methods are probably the most exten-
sively^ used and undoubtedly have the longest history. There are two
general types of apparatus, those that measure gas as it is absorbed
into a degassed solvent, and those that extract and measure gas from a
saturated solvent. The Ostwald apparatus is an example of the first
type and the second type is typified by the Van Slyke method (18).
, Mass spectrometric methods require that the sample be stripped
of gas, the gas trapped and then analyzed by mass spectrometry.
This method is very useful for the study of mixed gas solubilities but
depends heavily on the extraction method used (such as a Van Slyke
method). Cantone and Gurrier (7) described a mass spectrometric
method to analyze water samples for CH^, O^, N^> and Ar. Benson

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6
and Parker (4) used a similar technique to determine the ratios of
atmospheric gases dissolved in sea water.
The major use of gas chromatography in gas solubility deter-
minations has been to separate and quantify gases extracted from
saturated solvents. As in the mass spectrometric method a means of
extraction is inherent in the method.
Swinnerton, Linnerbom, and Cheek (26, 27) determined the
amount of dissolved gases in aqueous solutions by using a chromato-
graph. The dissolved gases were extracted from solution in a glass
sample chamber divided into two parts by a coarse fritted disk. A
known quantity of saturated liquid was admitted to the sample chamber
through a rubber septum. The carrier gas was directed up through
the fritted disk thus forming small bubbles and stripping the sample of
any dissolved gas. The gases were then separated and detected in the
chromatograph. Since the extraction procedure is very important to
the chromatographic method, various types of extraction equipment
have been investigated (2).
Table 1 lists several experimenters who have obtained results
for nitrogen solubility in water. The following discussion attempts to
give some background for each experimenter listed in Table 1.
Fox (13) used a modification of the Ostwald method to determine
nitrogen solubility. Fox devised a method to completely fill the satu-
ration chamber with degassed water without contamination. The

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Table 1. Literature values of nitrogen solubility in water (a x 10 ).
Temperature (°C)

10
15
20
25
30
F ox
18.
54
16.
84
15.
54
14. 43
13.
55
Winkler
18.
29


15.
18

13.
20
Bohr and Bock
19.
25


16.
13

13.
58
Adeney and Becker
18.
-0
o
4-
16.
96
15.
55
14. 35
13.
27
Morrison and Billett
19.
2 5+
17.
36
15.
86
14. 63
13.
64
Douglas
18.
75
17.
05
15.
57
14. 41
13.
45
Klots and Benson
18.
99
17.
24
15.
84
14. 66
13.
45
Murray, Riley, and Wilson
18.
82
17.
06
15.
63
14. 46
13.
49
Farhi, Edwards, and Homma





(14
30)26. 8 (14
25)27" 1
5 (13. 37)32- 0
Weiss
18.
. 81
17.
02
15.
59
14. 41
13.
, 45
^Smoothed data taken from Battino and Clever (2)
Numbers in superscript designated the temperature (°C) of measurement.

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8
saturation chamber was shaken to allow absorption of nitrogen and
then placed in a constant temperature bath. At appropriate times,
volume measurements were taken. Winkler's apparatus (32) was the-
oretically analogous to Fox's. However, argon was discovered after
Winkler's work so corrections for this gas must be made. Bohr and
Bock (5) bubbled a stream of atmospheric nitrogen through water to
attain saturation. The absorbed gas was then extracted and measured.
Fox (13) has corrected the values of Winkler and Bohr and Bock for
the presence of argon. The corrected values given by Fox appear in
Table 1.
Adeney and Becker (1) experimented by enclosing a large gas
bubble, of known volume, in a narrow tube containing degassed water.
They allowed the bubble to pass up through the water repeatedly until
saturation was reached. The pressure in the bubble was measured
after each double passage up the tube by means of a water manometer.
The pressure measurement gave data for calculating the absorption
which took place step by step to saturation.
An apparatus described by Morrison and Billett (19, 20) was
based on the flow of a liquid film through a gas. This method com-
pared favorably with the normal Ostwald technique.
Douglas (10) determined the solubility of nitrogen in distilled
water microgasometrically. Gas free water was brought into contact
with pure gas and after equilibration the amount of gas absorbed by the

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9
water was measured volumetrically with a micrometer buret. Shaking
of the saturation chamber was done to saturate the liquid but avoidance
of bubbles was required.
Klots and Benson (17) devised a method to measure the amount of
gas absorbed into a water sample and then extracted the gas from the
same sample to obtain a comparison. Excellent comparisons were
obtained. The method allowed nitrogen to absorb through a stopcock
into degassed water. The apparatus was gently rocked while absorp-
tion was taking place.
Murray, Riley, and Wilson (22) described an improved version
of the apparatus first described by Ben Nairn and Baer (3). This
apparatus involved a gasometric technique which took advantage of a
swirling motion which forced liquid up a capillary tube into a region
where the gas to be absorbed existed. The liquid then returned to the
vortex. Saturation occurred in five to seven hours in this system.
Farhi, Edwards, and Homma (12) combined vacuum extraction
in a Van Slyke chamber and detection of the gases in a gas chromato-
graph to determine nitrogen content in blood and distilled water. A
tonometer was used to saturate.the water with nitrogen. Approximate-
ly 30 milliliters of water were entered into the 200 milliliter tono-
meter. Nitrogen was flushed through the tonometer without bubbling
for 30 minutes. The tonometer was then swirled so that a liquid film
crept half-way up the sides. Samples were withdrawn and injected into

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10
the Van Slyke apparatus for analysis on the chromatograph. Ikels (16)
used a similar devise to study the solubility of nitrogen in human fat
and in water. An interesting apparatus, using a gas chromatograph,
was explained by Tolk, Lingerak, Kout, and Borger (28) for measur-
ing trace quantities of nitrogen in aqueous solutions. Unfortunately
no results were given.
Weiss (30) has taken recent data on the solubility of nitrogen in
distilled water and fitted it to thermodynamically consistent equations
by the method of least squares.
Table 2 gives a concise review of literature reported at 12.3°C,
19. 6°C, and 25. 5°C. This table will be used to compare literature
values with values rported in the current study.
Table 2. Literature values of nitrogen solubility at the
experimental temperatures of this study
(a x 103).


Temperature
(°C)


12.
3
19. 6
25.
5
F ox
17.
, 70
15. 64
14.
33
Klots and Benson
18.
, 15
15. 94
14.
56
Murray, et al.
17.
96
15. 73
14.
35
Douglas
17.
95
15. 68
14.
31
Weiss
17.
95
15. 70
14.
32
Surface Tension
Since the current study involves the violent mixing of nitrogen

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11
babbles with distilled water, a consideration of surface tension effect
on gas bubbles was performed. The following development is de-
scribed by Vanderslice, Schamp, and Mason (29). Calculations de-
scribed by Vanderslice et al. were intended for small liquid droplets
but can be extended to small vapor bubbles in a liquid phase. The
physical basis for the calculation is that the surface acts as a tight
skin, so that the environment inside the bubble or droplet is at a
slightly higher pressure than the surroundings with which it is in equi-
librium.
Using the concept of virtual work it can be seen that the work
done to decrease the volume of a small sphere by dV is ApdV
where Ap is the excess pressure on the sphere due to surface ten-
sion. This work term is equated to trdA', where cr is the surface
tension and dA is the decrease in surface area accompanying the
decrease in volume.
(Ap)dV = crdA	(3)
For a sphere of radius r the following relations hold.
V = 4/3Trr3	dV = 4irr2	(4)
2
A = 4irr	dA = 8irr	(5)
Substituting Equations 4 and 5 into Equation 3 it can be shown that

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12
2o"	,/>
Ap = —	(6)
Thus the pressure inside the sphere increases as the radius of the
sphere decreases. Using cr values from the Handbook of Chemistry
and Physics (8) Table 3 compares sphere radius and the pressure dif-
ferences of small bubbles.
Table 3. Pressure difference due to surface tension.
Sphere Radius	Pressure Difference
(cm)	(mm Hg)
0.1	.0.-546
0.01	5.46
0.001	54.6
0.0001	546.0
Thus with very small bubbles a significant pressure difference
is generated. Since the surrounding liquid environment is subject to
Henry's Law, a?corresponding increase in liquid concentration of the
gas should be observed.

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13
EQUIPMENT
The equipment used in the experimental investigation can best
be described by subdividing it into three sections. The first section
deals with the saturation chamber and the associated sampling device.
The second section discusses the temperature and pressure measuring
equipment. The third section explains the chromatographic equipment
and a discussion of the chemicals used. Together these sections give
a description of the solubility measuring apparatus. A,schematic of
the system is given in Figure 1.
Saturation Chamber and Sampling Device
The design criteria for a saturation chamber required the cham-
ber have a cell in which water could become saturated when nitrogen
gas was bubbled into the liquid, be small enough to place in a constant
temperature bath, and have a sampling port which would transfer a
representative sample to a chromatograph. A comprehensive diagram
of this piece of equipment and a photograph are given in Figures 2 and
3, respectively.
The saturation chamber was a six inch piece of pyrex glass
pipe, four inches in diameter. The ends were flanged and sealed with
teflon seals. Each flange was tapped to accommodate two 1/4-inch
swagelok adaptors and one l/8^inch adaptor. The 1/8-inch adaptors

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WATER a HELIUM PURGE LINE
WATER TRAP f"
REFERENCE EXIT , . SAMPLE EXIT
WATER TRAP
DRYING
RESTRICTOR
WATER TRAP
OVEN
SATURATION
CHAMBER
ROTO-
METERS
MOLECULAR
SIEVE
COLUMNS
CHECK
VALVE
I FLOW
REGULATER
CONTR
3-WAY VALVE
ROTOMETER

NITROGEN
COLO
JUNCTION
EXIT NITROGEN
BALANCE	PRESSURE
MANOMETER
GALVAN
ha
OMETER
POTENTIOMETER
FIGURE 1. GENERAL LAYOUT

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.WATER a HELIUM PURSE LINE
HELIUM SUPPLY
SEPTUM
N. EXIT
STRIPPER
BALANCE
MANOMETER
iTHEROCOUPLES
SAMPLE EXIT
BUBBLER
SAMPLE
LOOP
CHECK VALVE
3-WAY VALVE
FIGURE 2 SATURATION AND SAMPLING SCHEMATIC

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SAMPLE LOOP
Figure 3. Saturation and sampling photograph

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17
held the thermocouples and the 1/4-inch adaptors connected the exit/or
entrance lines. The bottom flange held the babbler and sample exit.
The bubbler was made of 1/4-inch copper tubing. The tubing was
teed and bent so that the gas entered tangentially at the bottom. This
gave a violent mixing motion while bubbling the gas through the liquid.
The gas flow rate was measured by a Fischer and Porter rotometer,
Model 103565A, and controlled by a Nupro, Series L, fine metering
valve. A Nupro check valve directly below the bottom flange prevented
back flow of water from the saturation chamber when gas flow ceased.
An exit in the top flange provided an escape for the gas while the
water was being stripped of atmospheric gases and saturated with
nitrogen. A Nupro, Series L, fine metering valve controlled the exit
flow. This valve permitted fine adjustments of chamber pressure.
The exit line was connected to a large manometer for precise pressure
measurement.
A bulkhead adaptor and a two inch piece of 1/4-inch copper tub-
ing protruded into the sampling chamber from the bottom flange. This
made the sample exit approximately two inches above the bottom
flange (thus a sample could be taken from the middle of the chamber).
The sampling system was composed of four Whitey 3-way valves,
number 43XS4, and a stripping section. Refer to Figure 2 for correct
valve numbering.
Valve 1 was mounted directly beneath the bottom flange. This

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valve controlled the saturated water flow through the sample loop or
the nitrogen gas flow through the sample loop. Valves 2 and 3 formed
the sample loop. Valve 2 had its common port to the sample loop.
One side port was connected to the bottom of the stripping section and
the other was connected to the common port of valve 1. Valve 3 had
its common port attached to the sample loop. One side port of valve 3
was attached to the helium supply (valve 4), and the second side port
led to the top flange and the gas phase above the saturated water.
Valve 4 allowed the helium carrier gas to be directed through the sam-
ple loop and stripper or routed directly to the chromatograph. Thus,
the common port of valve 4 was connected to the helium supply, one
side port was attached to valve 3, and the other side port was con-
nected to the bottom tee on the top of the stripper.
A tap for the balance manometer, a tap for purging excess water
and helium, and a shut-off valve were located in the line between valve
3 and the gas phase in the saturation chamber. The fitting on the top
flange was teed. One branch led to the balance manometer and the
other led to the sample loop. The balance manometer tap of the satu-
ration chamber was fitted with a Nupro B-4J ball valve (valve 6). The
balance manometer tap of the sample loop was equipped with a Nupro
Series L fine metering valve (valve 7). The purge tap exit was
equipped with a Nupro fine metering Series L valve (valve 8). The
shut-off valve was a Nupro B-4J ball valve (valve 5).

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The balance manometer measured the pressure difference be-
tween the sample loop and the saturation chamber. It was made of two
pieces of six foot clear plastic tubing. All lines leading to the mano-
meters had water traps. These traps were four inch pieces of two
inch diameter pipe. These pipes were capped and taps were located
so water would settle from the lines.
The stripper was made from a 15 milliliter Buchner funnel with
a coarse fritted glass disk. The top and the bottom were blown into a
1/4-inch glass tube. Two Swagelok tees were placed on the top of the
stripper. Refer to Figure 2 for the exact arrangement. The top
swagelok fitting held a silicon rubber septum. This straight through
arrangement permitted a long needle to reach the fritted glass for re-
moval of water after stripping. The lower tee was connected to valve
4 and the top tee led to the chromatograph.
All valves, except valve land the two valves on the top flange,
valves 5 and 6, were mounted on a 14 x 14 x 1/4 inch piece of clear
plastic. All tubing used exterior to the sampling chamber was 1/4-
inch Portco polyethylene clear tubing.
A 50 gallon American Instrument Company constant temperature
bath was used. . The apparatus fitted easily into this bath.
Temperature and Pressure Measurement
A mercury manometer approximately eight feet in height was

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used to measure pressure in the saturation chamber. Atmospheric
pressure was measured, with a Princo, Fortin-type, barometer. This
barometer was calibrated using the Oregon State University Weather
Bureau barometer for the standardized reference.
The manometer was constructed from two pieces of 1/4-inch
glass tubing; one eight feet in length and one four feet in length. Male
and female nylon swagelok elbows, formed a U which supported and held
the glass tubing together at the bottom. The manometer was fastened
to a plywood backing and was protected with a clear plastic shield.
The four foot leg was connected to the gas exit stream of the satura-
tion chamber. A water trap was placed in the line so no water could
be pulled into the manometer. A millimeter scale placed behind the
manometer permitted readings to be taken in millimeters.
Four copper-constantan thermocouple beads were made on a
small arc welder. Four five inch pieces of 1/8-inch brass tubing were
soldered shut at one end. A 1/4-inch plug shut all tubes. The tubes
were filled with acetone. After preparing and drying a silicon rubber
plug at the appropriate location on each thermocouple wire, the beads
were inserted into the tubes and plugged with silicon rubber? the bead
was completely sealed, in the tube. A tube was placed in the 1/8-inch
adaptor on the top and bottom flange and swaged tight.
A Leeds-Northrup K-3 potentiometer and a Leeds-Northrup null
detector, catalog number 9834, were used to detect voltage. A cold

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reference junction was used to switch the potentiometer from one
thermocouple to the next. The junction was kept at 0°C with ice and
distilled water.
Chromatograph and Chemicals
A chromatograph was used as an analytical tool in this work. It
quantified the amount of nitrogen expelled from the stripper. There
were several important components of this system. The components
included the detector, the columns, the oven, and the recorder.
The detector was a Carle Model 100 Micro-Detector which was a
dual thermistor detector. Accordingly, two gas streams were re-
quired. One carried the sample and one stream was used as a refer-
ence.
The columns used were 20 feet by 1/8-inch aluminum tubing,
filled with 30/60 mesh Linde molecular sieve 5A. Two columns were
used to balance the flow on each side of the detector. The columns
were wound to three inch diameters and placed in the oven next to the
detector. See Figure 4 for this arrangement. A flow restrictor,
made from 30 inches of the 1/8-inch aluminum tubing was placed in the
reference side to compensate for the pressure drop through the
stripper.
A Varian Aerograph series 2100 chromatograph was used to sup-
ply the oven, flow regulator, and the supply rotometers. The oven

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Figure 4. Column and detector arrangement.

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23
on the Varian 2100 was very temperature stable and provided adequate
temperature control for the detector. The helium flow regulator and
the two carrier gas rotometers were an integral part of the Varian
2100. These devices allowed even flow and regulation of each helium
line independently of the other.
A drierite drying tube was placed between the stripper and the
detector. The 12 inch long drying tube, made out of a 1/2-inch plastic
pipe, was fitted with the appropriate reducers to adapt to the 1/4-inch
lines. Several of these tubes were made so they could be changed
daily.
A Texas Instruments Incorporated Servo/riter recorder, Model
number FS01W6D, was used. It was fitted with a Disc integrator.
The recorder had a one millivolt sensitivity over a nine inch span.
Syringes used to standardize the chromatograph were Hamilton
gas-tight microliter syringes. The sizes used were 50, 150, 250 and
500 microliters. A separate nitrogen tank was fitted with a septum
and purge valve. This septum allowed nitrogen gas to be drawn into
the micro syringes for injection into the stripper.
. Matheson High-Purity grade helium was used for the carrier
gas. This gas had a 99. 995% minimum quality requirement. Matheson
Pre-Purified nitrogen was used; it had a quality of 99. 997%. Factory
analysis of the gas proved the gas well within the specifications. The
water used in all experiments was doubly distilled.

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24
PROCEDURE
Standard! zation
After construction, the system was sealedand purged with
nitrogen. At this time two important standardizations were made.
The thermocouples were calibrated and the volume of the sample loop
was determined.
The thermocouples were calibrated using a comparison method.
A platinum resistance thermometer with a Mueller bridge and accom-
panying galvanometer measured the temperature of a water bath that
was slowly increasing in temperature. At the same time measure-
ments were made with the resistance thermometer, readings were
being taken on the thermocouples. A temperature versus millivolt
curve was generated for each thermocouple.
The volume of the sample loop was determined by using six glass
tubes filled with drierite. One end of each tube was drawn down to a
1/4-inch glass tube so it could be attached to the stripping side of
valve 2. The sample loop was filled with water and subsequently blown
out into the drierite tube. Each tube was blown into for approximately
five minutes. The difference in weight, gave the volume of water held
in the sample loop.
To check for any vapor blow-by, two tubes were connected in

-------
25
series. The weight change in the second tube was insignificant. Fig-
are 5 gives a picture of these tubes.
Saturation
Doubly distilled water was syphoned into the saturation chamber
through the bubbler exit. This water was stripped of other gases and
then saturated with nitrogen by bubbling nitrogen through the chamber
at approximately 4500 milliliters per minute. The nitrogen was al-
lowed to bubble for one hour. Various settling times were allowed
before taking the analytical samples.
One series of experiments used vacuum degassed water and
eliminated the bubbling of nitrogen gas. Absorption of the nitrogen
resulted by mass transfer through the surface. The following proce-
dure for this series was followed: a 4000 milliliter filtering flask
filled with 3000 milliliters of doubly distilled water was boiled and held
under vacuum for six hours, the water was transferred to the satura-
tion chamber by back pressuring the flask with helium. Nitrogen was
allowed to purge the saturation chamber while it was being filled with
water to the appropriate level. The system was sealed and after a
period of time, to allow for mass transfer, the liquid was sampled as
in the bubbling method.

-------
Figure 5. Drying tubes used to standardize sample loop.

-------
27
Sampling
The sampling technique involved a cycle of filling the sample
loop, stripping the sample, injecting microquantities of nitrogen to
obtain a standard curve, purging the sample loop, and filling the sam-
ple loop once again. A description of this cycle will start with the
sample loop ready to accept a sample. Refer to Figure 2 for correct
valve numbers. Arrows placed by each valve indicate possible direc-
tion of flow.
At-the start of the cycle the valves were in the following posi-
tions: valve 1 was open to nitrogen gas flow, valves 2 and 3 were
open to the saturation chamber, valve 4 was positioned so helium
flowed to the top of the stripper, valves 5, 6, and'7 were open, and
valves 8, 9, and 10, were closed.
Valve 2 was closed to flow in any direction and valve 1 was
rotated to accept water from the saturation chamber. Valve 2 was
slowly opened and the ^sample loop was allowed to fill. The sample
loop had been placed low enough so that the head pressure pushed
some water above valve 3. . This gave amore representative sample.
Valves 2 and 3 were now closed to flow in any direction. These
two valves were then rotated to allow flow towards the stripper.
Valve 4 was rotated so that the helium carrier gas forced the sample
to the stripper. The nitrogen was then stripped and carried into the

-------
chromatograph for measurement. After the nitrogen peak passed from
the chromatograph a series of nitrogen injections were made. These
injections were made through the septum on the top of the stripping
column. Hamilton microliter gas tight syringes were used. A series
of these injections gave a quantity versus peak-area curve from which
the quantity of gas in a sample could be determined. Usually two or
three injections were made per sample. By the end of the day a curve
with approximately 20 points had been generated.
To obtain an accurate measurement of the nitrogen injected, a
small quantity of water was initially drawn up into the needle. A
quantity of nitrogen was drawn into the syringe and then some more
water was drawn up. Thus, a quantity of nitrogen was isolated between
two water seals. The quantity of nitrogen was easily read. Upon in-
jection this method assured that no nitrogen would be left in the needle.
A correction for water vapor was made by knowing atmospheric tem-
perature and pressure.
Valve 4 was now rotated to direct helium to the top of the
stripping section, by-passing the fritted glass. A syringe with a
seven inch needle removed the sample water from the stripper. Valve
5 was closed and valve 1 turned to allow nitrogen flow into the sample
loop. Valve 8 was opened and valves 2 and 3 were returned to their
original positions. The excess water and helium were purged to the
atmosphere. Valve 8 was then closed.and the sample loop was

-------
29
pressurized to the same pressure as the saturation chamber. This
was done by noting the difference in mercury levels.in the balance
manometer, and adjusting sample loop pressure with valve 10. While
purging the sample loop the lines to the balance manometer were iso-
lated from the sample loop by closing valves 6 and 7. This was neces-
sary to prevent helium from flowing into these lines. The sampling
system was now ready for another sample.
Temperature and pressure readings were made immediately
after the sample was taken and before it had been discharged to the
stripper.
The recorder chart speed was 3/8-inch per minute and the
attenuation was set on 100. The gas flow rate was approximately 26
milliliters per minute with a pressure reading of 39 pounds per square
inch at the exit of the helium tank. The temperature of the oven was
50°C.

-------
30
RESULTS AND DISCUSSION
Table 4 and Table 5 give a concise report of the data collected
during this study. Three temperatures were investigated at three
pressures. The pressures are reported as absolute pressures. Table
4 gives the data in mole fraction and Table 5 gives values of the modi-
fied Bunsen coefficient, and, in parenthesis, the Bunsen coefficient.
At 760 mm Hg the modified Bunsen coefficient equals the Bunsen
coefficient.
Table 4. Nitrogen solubility in distilled water, (mole
fraction x 10^).
Temperature

Pressure (mm Hg absolute)
°(C)

760 1520 2280
12. 3
19. 6
25. 5

18.78 33.88 56.30
18.08 34.27 53.32
15.96 33.01 48.60
Table 5. Nitrogen solubility in distilled water
(a1 and ax 10^).


Pressure (mm Hg absolute)
Temperature
°(C)
76 0
a
1520 2280
a' a a' a
12. 3
19. 6
25. 5
22. 95
22. 50
19. 95
42. 15 (21.08) 70.05 (23.35)
42. 64 (21.32) 66. 34 (22. 11)
41.08(20.54) 60.47(20.16)
A comparison of Table 5 with Table 2 shows a significant

-------
31
difference in solubilities. The solubilities shown in Table 5 are
approximately 30 percent higher than values shown in Table 2.
It was interesting to note the previous means used to saturate
water with nitrogen. In only one reference (5) were the formation of
bubbles mentioned. Shaking, and gently rocking appeared to be pre-
dominant modes of saturation. Even in the flow system (19) bubbles
were not mentioned. The system described, in this study turbulently
mixed nitrogen and water. Many bubbles are formed in this process.
It can be recognized that this study is attempting to put an excess
amount of nitrogen into the liquid (either in solution or fine bubbles).
Thus equilibrium is approached from a greater than saturated level.
All bubbles and excess dissolved nitrogen must leave the liquid to have
true equilibrium. Most experiments in literature approach equilib-
rium from the unsaturated conditions.
Considering the approach from different sides of equilibrium, it
was not unusual to expect some differences in the direction noted. The
unusual situation was the time for equilibrium to be attained. The
values in Table 4 and Table 5 were taken ori the fifth day iafter bubbling
and turbulent mixing ceased. There were three reasons for selection
of the fifth day as the most appropriate day on which to take data.
Since it was desired to model the turbulent system developed at
spillways on the Columbia River and the subsequent stagnation in the
pools between dams, a time representative of the mean residence

-------
time of water between dams was determined. The flow volume on the
Columbia River varies from a low of 70, 000 cfs to 660, 000 cfs' (14).
In calculating an average travel time between dams 150, 000 cfs was
used. Morse (21) gave some valocities for the Rocky Reach pool.
These velocities were approximately 3000 feet per hour. Since the
distance between Rocky Reach Dam and Wells Dam is 41 miles (33)
the travel time is less than three days. Robeck, Henderson, and
Palange (23) gave travel times for the larger pool between McNary and
Priest Rapids Dam. At a flow of approximately 150, 000 cfs, the
travel time is 117 hours or five days. Although the mean residence
time is somewhat greater than travel time, an average residence time
of 5 days seems appropriate for the Columbia system (9).
A time dependent experiment was performed by holding tempera-
ture and pressure constant and sampling at different time intervals
from the time of bubble stoppage. It was desired to determine if
equilibrium was achieved rapidly. Table 6 gives the results of this
study. All data points are given to show possible overlap. Values are
expressed in Bunsen coefficients. The conditions of the experiment
were 25. 5°C and one atmosphere.
It appears that there is a slight decrease in concentration up to
the fifth day. However there is a 90 percent probability that data from
day 4 and day 5 could have come from the same population. Altero there
is a 90 percent probability that data from day 5 and day 7 came from

-------
33
the same population.
Table 6. Time versus concentration for mixed system
(q x 10^).
Day 3
Day 4
Day 5
Day 7
21. 30
19. 93
19. 98
20. 58
21. 71
20. 39
19. 87
21. 26
21. 71
20. 73
20.43
23. 88
21.57
19. 73
20. 10
21. 49
22. 76
22. 75
17. 57
22. 25
22. 23
23. 82
20. 20
18. 46
22. 35
21. 62
21. 86
21.35
22. 69
24. 18
	
21. 57
21. 69
21.31
19. 63
20. 01
21:99
21; 60
19. 96
i\. 20
To test the hypothesis that bubbles and turbulent mixing are in
some way responsible for the observed phenomena, a system to satu-
rate water without bubbling was devised. Mass transfer of nitrogen
into degassed water was allowed only through the surface. The same
sampling technique was used as before. Results are shown in Table 7.
Table 7. Time versus concentration for unmixed system
(a x 10^).
Day 1
Day 3
Day 5
14. 18
15. 08
15. 69
11. 94
15. 33
15. 89
12. 93
15. 55
15.66
12. 39
15.88
15. 65
13. 28
15. 98
15. 77
13. 37
	
	
13. 01
15.56
15.73

-------
Comparing the data from Table 7 with Table 2 a deviation of 7-9
per cent is observed. Also a statistical check shows that within 80 per-
cent probability day 3 and day 5 come from the same population. It is
therefore assumed that equilbrium has been achieved by day 5.
Comparing Table 6 and Table 7 a significant difference in solu-
bilities exist over the five day period. This difference can be attri-
buted directly to bubbles and turbulent mixing versus surface absorp-
tion only.
It is of interest to note that the data of Table 4 approximates
Henry's Law quite closely. See Figure 6 for this illustration.

-------
3
H- 6.15x10'
CO
-H- 5.64x10'
2
H= 5.15X10'
0
40
60
0
20
30
MOLE FRACTION x 10®
50
70
80
FIGURE 6 PRESSURE-MOLE FRACTION RELATIONSHIP EXPRESSING
HENRY'S LAW

-------
36
CONCLUSIONS
A distinct difference between concentrations in the turbulently
mixed system and the unmixed system is noted. It is highly unlikely
that these differences are due to experimental error. This difference
can be explained by surface tension effects on small bubbles.
The term "nitrogen super saturation" may have some validity
from the standpoint of turbulent mixing and bubble phenomena.

-------
37
BIBLIOGRAPHY
1.	Adeney, W.E. and H.G- Becker. The determination of the rate
of solution of atmospheric nitrogen and oxygen by water - Part II.
Philosophical Magazine and Journal of Science 39:385-403. 1920.
2.	Battino, R. and H. L. Clever. The solubility of gases in liquids.
Chemical Reviews 66:395-463. 1966.
3.	Ben Nairn, A. and S. Baer. Method for measuring solubilities of
slightly soluble gases in liquids. Transactions of the Faraday
Society 59:2735-2738. 1963.
4.	Benson, B. B. and!P.D.M. Parker. Relations among the solu-
bilities of nitrogen, argon, and oxygen in distilled water and sea
water. The Journal of Physical Chemistry 65:1489-1496. 1961.
5.	Bohr, von Chr. and Joh Bock. Bestimmung der absorption
einiger gase in wasser bei den temperaturen zwischen 9 und 100°.
Annalen der Physik und Chemie 44:318-343. 1891.
6.	Bouck, G. R. , G.A. Chapman, P.W. Schneider and D. G. Stevens.
Observations on gas bubble disease in adult Columbia river sock-
eye salmon (Oncorhynchus nerka). Unpublished manuscript,
Federal Water Quality Administration, Pacific Northwest Water
Laboratory, Corvallis, Oregon. 1970.
7.	Cantone, B. and S. Gurrieri. Determinazione dei gas disciolti
nelle acque mediante lo spetrometro di massa. Boll. Sedute
Accademy Gioenia Sci. Nat. Catania 72:681-686. I960.
8.	Chemical Rubber Company, Cleveland, Ohio. Handbook of
Chemistry and Physics. 45th ed. 1964.
9- Christianson, A. , Research Sanitary Engineer. Personal inter-
view. Federal Water Quality Administration, Pacific Northwest
Region, Corvallis, Oregon. 1970.
10. Douglas, E. Solubilities of oxygen, argon, and nitrogen in
distilled water. The Journal of Physical Chemistry 68:169-174.
1964.

-------
38
11.	Ebel, W.J. Super saturation of nitrogen in the Columbia river and
its effect on salmon and steelhead trout. U.S. Fish and Wildlife
Service, Fishery Bulletin 68(no. 1): 1 -11. 1969.
12.	Farhi, L.E., A.W.T. Edwards and T. Homma. Determination
of dissolved N£ in blood by gas chromatography and (a-A) N2 dif-
ference. Journal of Applied Physiology 18:97-106. 1963.
13.	Fox, D. J. J. On the coefficients of absorption of nitrogen and
oxygen in distilled water and sea-water, and of atmospheric
carbonic acid in sea-water. Transactions of the Faraday Society
5:68-87. 1909.
14.	Hansen, P.J. Vertical distribution of radioactivity in the Colum-
bia river estuary. Master's thesis. Corvallis, Oregon State
University, 1967. 76 numb, leaves.
15.	Harvey, H.H. and A. C. Cooper. Origin and treatment of a
supersaturated river water. International Pacific Salmon Fish-
eries Commission. Progress Report No. 9, p. 1-19. 1962.
16.	Ikels, K. G. Determination of the solubility of nitrogen in water
and extracted human fat. DDC Technical Documentary Report
No. SAM-TDR-64-1. 1964.
17.	Klots, C.E. and B. B. Benson. Solubilities of nitrogen, oxygen,
and argon in distilled water. Journal of Marine Research 21:48-
57. 1963.
18.	Markham, A.E. and K. A. Kobe. The solubility of gases in
liquids. Chemical Reviews 28:519-588. 1941.
19- Morrison, T.J. and F. Billett. The measurement of gas solubil-
ities. Journal of the Chemical Society part III, p. 2033. 1948.
20.	Morrison, T.J. and F. Billett. The salting-out of non-
electrolytes; Part II. The effect of variation in non-electrolyte.
Journal of the Chemical Society part V, p. 3819. 1952.
21.	Morse, W. L. Stream temperature prediction model. Water
Resources Research. 6(no. 1):290-318. 1970.
22.	Murray, C. N. , J. P. Riley and T.R.S. Wilson. The solubility of
gases in distilled water and sea water - I. Nitrogen. Deep-Sea
Research 16:297-310. 1962.

-------
39
23.	Robeck, G. , C. Henderson and R. C. Palange. Water quality-
studies on the Columbia river. U.S. Dept. of Health, Education,
and Welfare, Public Health Service Bureau of State Services,
(R. A. Taft Sanitary Engineering Center, Cincinatti, Ohio)
24.	Rucker, R.R. Gas bubble disease in salmonids: A critical review.
Unpublished manuscript. U.S. Bureau of Sport Fisheries and
Wildlife, Western Fish Disease Laboratory, Sand Point Naval Air
Station. Seattle, Washington. 1970.
25.	Rucker.. R.R. and K. Hodgeboom. Observations on gas bubble
disease of fish. Progressive Fish Culturist 15:24-26. 1953.
26.	Swinnerton, J.W., V.J. Linnerbom and C.H. Cheek. Determina-
tion of dissolved gases in aqueous solutions by gas chromatography.
Analytical Chemistry 34:483-485. 1962.
27.	Swinnerton, J. W. , V.J. Linnerbom and C.H. Cheek. Revised
sampling procedure for determination of dissolved gases in solu-
tion by gas chromatography. Analytical Chemistry 34:1509. 1962.
28.	Tolk, A. , W. A. Lingerak, A. Kout and D. Borger. Determina-
tion of traces of hydrogen, nitrogen, and oxygen in aqueous solu-
tions by gas chromatography. Analytica Chimica Acta 45:137-
142. 1969.
29- Vanderslice, J. T. , H.W. Schamp, Jr. and E. A. Mason.
Thermodynamics. Englewood Cliffs, N.J. , Prentice-Hall, Inc. ,
1966. 244 p.
30.	Weiss, R. F. The solubility of nitrogen, oxygen and argon in
water and sea water. Deep-Sea Research 17:721-735. 1970.
31.	Westgard, R. L. Physical and biological aspects of gas-bubble
disease in impounded adult chinook salmon at McNary spawning
channel. Transactions of the American Fisheries Society
93:306-309. 1964.
32.	Winkler, L.W. Die loslichkeit des sauerstoffs in wasser.
Berichte der Deutschen Chemischen Gesellschaft 22:1764-1774.
1889.
33.	Yearsley, J. R. A mathematical model for predicting temperature
in rivers, and river-run reservoirs. (Federal Water Quality
Administration, publication no. 65r March 1969)

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40
APPENDIX A
Nomenclature
Symbol	Explanation
A	Babble surface area
MW
H2°
H2°
H2°
atm
CH
R
T,
CH
atm
Molecular weight of water
Partial pressure of water at conditions
inside saturation chamber
Partial pressure of water at room
temperature
Atmospheric pressure
Partial pressure of gas whose
solubility is being determined
Pressure inside saturation chamber
Radius of bubble
Universal gas constant
Temperature of measurement
°C (273. 15°K)
Temperature in saturation chamber
Room temperature
Volume of a bubble
Volume of gas whose solubility is
being determined
Typical Units
2
cm
grams
gram mole
mm Hg
mm Hg
mm Hg
mm Hg
mm Hg
cm
(atm) (ml)
(gram moles)(°K)
°C
'K
'C
cm
cm
Volume of solvent (in the case of water
it is assumed 1 gram = 1 milliliter)	ml

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Symbol
V
g
1
V
Explanation	Typical Units
Volume gas injected into chromatograph ul
Corrected volume of gas injected into
chromatograph	ul
Volume of gas evolved from sample	ul
W
SL
N.
X
N.
Ap
Weight of water in sample loop
Mole fraction nitrogen in sample
(uncorrected for pressure variations)
Corrected mole fraction
Bunsen coefficient
Modified Bunsen coefficient
Surface tension water-nitrogen
Pressure difference of small bubbles
due to surface tension effects
ul
mole N.
mole N^+ ^2^
mole
mole N^+H^O
ml gas
ml solvent
ml gas
ml solvent
dyne s
cm
mm Hg

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42
APPENDIX B
Sample Calculations
The sample calculation is performed on data taken from Run
8-1 to 30. The calculations involve a general four step process. Step
1 deals with constructing a standard curve for the data collected dur-
ing a particular run. Step 2 uses the standard curve to determine the
volume of nitrogen evolved from the sample. Step 3 calculates the
mole fraction representative of the sample and Step 4 calculates the
Bansen coefficient, a, and the modified Bunsen coefficient, a1,.
Step 1:
a)	Calculate amount nitrogen injected minus water vapor present in
syringe. (Peak 8-1 is an example)
*
<762^1.20.7)
g« gi P	762-1
0	1	atm
b)	A plot of V „ versus peak area is made. An example of Run
B0
8-1 to 30 is shown in Figure 7.
Step 2:
a) Knowing a peak area for a sample the volume of nitrogen at in-
jection conditions can be determined. Consider peak 8-12 for
example.

-------
CHROMATOGRAPHIC PEAK AREA X 10
FIGURE 7 STANDARD CURVE FOR 8-1 to 8-30

-------
44
Peak area = 1362
. V = 100. 00 ul.
Step 3:
a)	Calculate the number of moles 100 ul represents (assuming the
ideal gas law)
Patm'vgs (76V61o,tm)100-0''10"3	-6
N =	 = 	;	= 4.131 x 10 gmoles
° R:Tatm 82.06**™ m 295.45°K
K mole
b)	Calculate mole fraction at injected conditions
MWh2°	-6 18-015 gioleS N2
XN = V W )= 4.121x10 (4. 2795 gr H n >
c	SL	^
= 17.39 x 10"6
c)	Correct mole fraction for pressure variations and deviations
from 760 mm Hg, 1520 mm Hg, or 2280 mm Hg. Since 8-12
was taken at approximately chamber conditions of 1 atmosphere
it is corrected to 760 mm Hg.
x -x' (	—	) - 17 39xl0~k(	^	)
N N(	0 ' 17-39x 10 7 83. 4 - 24. 5
CH HzO
= 17.40 x 10"6
d)	At pressures of two and three atmospheres the calculation is
performed with consideration to these pressures:

-------
45
at two atmospheres X = X' (
N2 N2 P -P°
CH HzO
. / 2280
at three atmospheres X = X (			)
2 2 P -P
CH HzO
Step 4:
a)	The Bunsen coefficient is calculated
(N0 R T0) r760 mm Hg
a ~ W	0 ^
SL pch-ph2o
r 4.131 x 10"6 ¦ 82.06 • 273.15 nr 760 , „, ,„-3
= [	4^9i	][ 783.4 - 24.5]= 21-71X1°
b)	At pressures of two and three atmospheres the modified Bunsen
coefficient is defined as
, ^ (Nq R Tq) r 1520 mm Hg n
a ~ W	0
SL pch" H O
or
(N„ R T ) 0
0	0_ r 2280 mm Hg
W	0 J
SL pch-ph2o

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APPENDIX C
Standardization of Sample Loop
Final Weight
(grams)
Initial Weight
(grams)
Weight of Water
(grams)
72. 8356
68.6959
4.1397
61.7959
57.6861
4.1098
63.9643
59.7638
4.2005
64.6059
60.3066
4.2993
60.2554
55.9079
4. 3475
72.9148
68.5700
4. 3448
59.0291
54. 7945
4. 2346
64.5969
60.1985
4. 3984
63.8875
59.6802
4.2073
57.0815
52. 8776
4. 2039
59,3431
55.1071
4. 23 60
63.9075
59.6614
4.2461
64.4893
60.1756
4. 3137
72.9109
68.5355
4.3754
57.1345
52.8634
4. 2709
59. 3346
55.0978
4. 23 68
59.0425
54.7622
4. 2803
59.3362
55.1061
4. 2301
64.5261
60.1729
4. 3532
57. 1334
52. 8576
4. 2758
59.0740
54.7620
4.3120
72. 9737
68.5408
4. 43 29
63.8004
59.6733
4. 1271
63.9723
59.6746
4. 2977
57. 1115
52.8549
4. 2566
72. 8930
68.5359
4. 3571
59.1607
54. 7615
4. 3992
59. 3906
55.1127
4. 2779
64.5117
60.1691
4. 3426
Average = 4. 2795

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APPENDIX D
Tabulated Data
The run number code is as follows: The first number represents a set of data taken on one
day and the second number represents the individual sample or injection number within the series.
Columns 2_to 4 and 6 to 9 are observed data and columns 5, 10, 11, and 12 are calculated data.
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11) (12)
Run
V8l
T
atm
P
atm
%
T
CH
PCH
Peak
V8s
XN Sl°6
2
6 3
X x 10 a or a1 x 10
2
No.
ul
°C
mm Hg
ul
°C
mm Hg
Area
ul
1-2
Sample
22.8
765 . 8







-3
108


105. 2


1320



-4
98


95.4


1191



-5
96


93.5


1121



-6
55


53. 6


741



-7
57


55.5


670



-8
51


49.7


649



-9
Sample

765 .7

19.6
779.7
1320
103.5
18.08
18.01 22.41
-10
80


77.8


947



-11
78


75.9


1009



-12
74


72. 0


998



-13
148


144.0


1769



-14
145


141.0


1824



-15
145


141.0


1729



-16
S ample
22.8
765.5

19.6
773.5
1314
103.0
17.98
18.06 22.47
-17
178


173.2


2125



-18
179


174.1


2145



-19
175


170.3


2078




-------
(1)
Run
No.
(2)
vsi
ul
(3)
T
atm
°C
(4)
P
atm
mm Hg
(5)
%
ul
(6)
T
CH
° C
(7)
PCH
mm Hg
1-20
S ample

765.4

19.6
772.4
-21
122


118.7


-22
119


115.8


-23
125


121.6


-24
Sample
22.8
765.1

19.6
771.1
-25






-26
90


87.6


-27
85


82.7


-28
90


87.6


-29
Sample

764.5

19.6
768. S
-30
110


107. 0


-31
106


103.1


-32
110


107.0


-33
Sample

763. 1

19.6
767.1
-34
108


105. 1


-35
105


102. 1


-36
100


97.3


2-1
S ample
24.9
760.4



-2
145


140.5


-3
103


99.8


-4
55


53.3


-5
101


98.2


-6
Sample

760. 3

19. 7
1587. 3
-7
125


121.2


-8
129
24.8

125.0


-9






-10
124


120.2


-11
Sample

760.3

19.6
1573.3
-12
155


150.1


-13
152
24.0

147.3


-14
154


149.5


(8)	(9)	(10)	(11)	(12)
Vcr	6	6	3
Peak	°s X' x 10 X x 10 a or a' x 10
Area	ul	N2	N2
1194	93.0 16.23	16.33	20.32+
1542
1445
1539
1280 100.5 17.54	17.68	21.99
1124
1186
1186
1340 105.0 18.31	18.52	23.04
1367
1361
1432
1310 103.0 17.92	18.16	22.60
1378
1330
1280
1757
1280
775
1098
2502 1 99.0 34.26	33.16	41.27
1550
1595
1530
1555 120.0 20.67	20.18	25.11+
1744
1845
1891	4^
oo

-------
(1)
Run
No.
(2)
vsi
ul
(3)
T
atm
° C
(4)
P
atm
mm Hg
(5)
v*o
ul
(6)
T
CH
°C
(7)
PCH
mm Hg
2t15
S ample
23.5
759.9

19.6
1586.9
-16
Sample

759.8

19.5
1570. 8
-17
57


55.4


-18
56


54.4


-19
80


77.7


-20
77
23.0

74.7


-21
S ample

759.4

19.3
1584. 4
-22
113


109.8


-23
175


170.1


-24
203


197.4


-25
S ample

759.0

19.5
1583
-26
S ample

759,0

19.4
1584
-27
350


340.0


-28
200


194.3


-29
174


169.0


-30
160


155.6


-31
161


156.2


-32
Sample
23.0
758.9

19.2
1586.6
-33
185


179.9


-34
185


179.9


3-1
Sample
22.8
763. 0



-2
153


148.8


-3
157


152.6


-4
ISO


145.9


-5
Sample
22.8
762. 6

19. 7
1551. 6
-6
103


100.1


-7
125


121.5


-8






-9
180


175.0


-10
S ample
23.0
762.4

19.6
1521.4
-11
S ample
23.0
762. 5

19.6
1524. 5
(8)
(9)
(10)
(U)
Peak
Area
Vg
6s
ul
no6
2
Vx '°6
2
2586
205.0
35.46
34. 20
2421
192. 0
33.19
32.47
306



73S



1069



1046



3525
283.0
48.98
47. 4y
1423



2162



2458



2645
210.0
36. 33
35.26
3020
241.0
41.69
40.44
3828



2433



2138



2000



2021



2750
219.0
37.88
36.67
2315



2346



2070



2202



2006



2713
196.0
34.09
33.77
1523



1652



2431



4160
299.0
51. 96
52.50
2630
189.0
32. 84
33.12
(12)
a or a' x
42.70
40.40
59.09
43.87
50. 31
45.63
42.06
65.32
41.21

-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Run
V8l
T
atm
P
atm
v*o
T
CH
PCH
No.
ul
°C
mm Hg
ul
°c
mm Hg
3-12
218


212.0


-13
112


109.0


-14
140


136.2


-15
Sample
22.9
762.4

19. 7
1521.4
-16
58


56.4


-17
67


65.2


-18
55


53.S


-19
77


74.8


-20
79


76.7


-21
S ample
22.9
761.5

19.7
1509.5
-22
228


221.7


-23
201


195.5


-24
173


168.0


-25
S ample
23.0
760.9

19. 7
1515.9
-26
194


188.8


-27
167


162.5


-28
148


144.0


-29
142


138.0


-30
Sample

759.8

19.7
1527.8
-31
128


124.5


-32
115


112.0


-33
100


97.5


-34
112


109.0


-35
Sample
22.9
759. 1

19.6
1491.1
-36
Sample

758.9

19.6
1494.9
-37
130


126.5


-38
157


153.0


4-1

24.8
759.5



-2
104


100.8


-3
202


195. 7


-4
150


145.4


(8)
(9)
(10)
(ID
Peak
Area
V8s
ul
X' x 106
2
\ *10'
2
2695



1620



1709



2960
213.0
37.02
37. 41
735



1025



778



868



1132



2567
185.0
32.12
32. 71
3078



2446



2382



2512
181.0
31. 39
31.83
2718



2001



2032



1998



2568
185.0
32.04
32. 23
1820



1261



1498



1594



4160
299.0
51.75
53. 36
2708
195.0
33.74
34.70
1888



2140



1430
2730
1812
(12)
a or a1 x
46.55
40. 70
39.60
40.10
66. 39
43.18

-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Run
V8l
T
atm
P
atm
Vso
T
CH
PCH
No.
ul
° C
mm Hg
ul
°C
mm Hg
4-5
Sample
24.8
759.4

19.7
1501.4
-6
227


220.0


-7
169


163.8


-8
112


108.5


-9
Sample
24.2
759.5

19.6
1508.5
-10
216


209.0


-11
163


158.0


-12
121


117.5


-13
Sample
23.7
760.0

19.6
1505.0
-14
246


238.5


-15
185


179.5


-16
138


133.8


-17
S ample
23.6
760.0

19.5
1504.0
-18
S ample
23.6
759.8

19.6
1514.8
-19
131


127.0


-20
186


180.3


-21
236


229.0


-22
S ample
23.6
759.4

19.4
1509. 4
-23
Sample
23.6
759. 2

19.4
1507. 2
-24
145


140.5


-25
165


160.0


-26






-27
195


189.0


-28
Sample
23.4
758.6

19.4
1513.6
-29
Sample
23.4
758.5

19.4
1509.5
-30
173


167.8


5-1

22.8
759.8



-2
200


194.6


-3
155


150.8


-4
118


114.8


-5
Sample
22. 9
760.0

19.7
2269
(8)	(9)	(10)	(11)	(12)
Peak	x1 x 10^ X x 10^ a or a' x
Area	ul	*2	N2
2486 187	32.17	32.94	40.99
2663
22S3
1550
2574 194	33.45	34.09	42.41
2863
1960
1710
2393 180	31.10	31.78	39.54
3026
2525
1640
2592 196	33.88	34.63	43.09
2430 182	31.45	31.92	39.71
1617
2466
3003
2922 222	38.35	39.05	48.59
2468 185	31.95	32.58	40.54
1640
2235
2450
2815 214	36.95	37.52	46.69
2558 193	33.32	33.93	42.22
2220
1791
1359
1015
2995 285	49.38	50.00	62.21

-------
(1)
(2)
(3)
(4)
(S)
(6)
(7)
Run
vsi
T
atm
P
atm
vso
T
CH
PCH
No.
ul
°C
mm Hg
ul
°C
mm Hg
5-6
255


248.0


-7
242


235.5


-8
305


296.6


-9
Sample
22.9
760.3

19.7
2267
-10
Sample

760.0

19.6
2265
-11
222


216.0


-12
168


163.5


-13






-14
191


185.9


-15
Sample
23.4
760.0

19.6.
2267
-16
135


131. 2


-17
180


174. 9


-18
215


209.0


-19
Sample
23.7
759.7

19.6
2258
-20
Sample
23.6
759.4

19.6
2258
-21






-22
285


277.0


-23
274


266. 2


-24






-25
238


231. 2


-26
Sample
23.8
758.8

19.5
2260
-27
Sample
24.0
758.7

19.6
2267
-28
150


145.7


-29
175


170.5


6-1

23.5
759.9



-2
205


199.0


-3
155


150.6


-4
100


97.1


-5
S ample
22.9
760. 2

19.7
2262
-6
255


248.0


-7
225


218.8


(8)
Peak
Area
(9)
V*s
ul
(10)
XN X'°6
2
(U)
V * '°6
2
2505



2423



3148



3375
317
54. 95
55.67
2825
271
46. 96
47.63
2183



1750



1918



2345
229
39. 61
40,14
1328



1720



2036



4165
386
66. 68
67. 84
3168
300
51.82
52. 72
2453



2071



2491



2694
259
44.67
45.40
2842
272
46.87
47.50
1392



1500



2335



1508



1073



2683
263
45.58
46. 30
2614



2407



(12)
a or a' x
69. 29
59. 26
49. 95
84. 41
65. 60
56.50
59. 10
57. 60

-------
(1)
(2)
(3)
(4)
(S)
(6)
(7)
Run
V
T -
P
V
T ,
P
Si
atm
atm
So
CH
CH
No.
ul
°C
mm Hg
ul
°C
mm Hg
6-8
225


218.8


-9
S ample
23.0
760. 3

19.6
2257
-10






-11
167


162.4


-12
175


170.0


-13
190


184.6


-14
S ample
22.8
760. 3

19.5
2249
-15
190


184.6


-16
207


201.0


-17
218


212.0


-18






-19
Sample
23.0
760.0

19.5
2263
-20
230


224.0


-21
240


233.5


-22
138


134. 2


-23
S ample
22.8
759.6

19.5
2254
-24
160


155.5


-25
170


165.5


-26
180


175.0


-27
Sample
22.7
759. 1

19.5
2257
-28
S ample
22.8
759.0

19.4
2245
-29
194


188.5


-30
205


199.7


7-1

22.7
748.1



-2
98.0


95.3


-3
150.0


145.8


-4
200.0


194.5


-5
Sample
22.6
748. 3

19.8
753.3
-6
110.0


107.0


-7
129.0


125.4


-8
135.0


131. 3


(8)
(9)
(10)
(11)
Peak
Area
6s
ul
2
XN "">
-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Run
V CT
gl
T
atm
P
atm
Vg
s0
T
CH
PCH
No.
ul
° C
mm Hg
ul
°C
mm Hg
7-9






-10
S ample
23.5
748.0

19.6
752.0
-11
72.0


70.0


-12
82.0


79. 7


-13
91.0


88. 4


-14
Sample
23.5
747.4

19.6
751.4
-15
56.0


54.4


-16
139.0


135.0


-17
160.0


155.4


-18
S ample
23.4
748.4

19.6
752.4
-19
102.0


99. 1


-20
Sample
23.4
748.2

19.5
752.2
8-1

22.7
762.1



-2
104.0


101. 2


-3
150.0


145.9


-4
125.0


121.6


-5
S ample
22.7
761.8

25.6
784.5
-6
52.0


50.5


-7
61.0


59.2


-8
74.0


72.0


-9
Sample
22.4
761.5

25.5
783.9
-10
80.0


77.9


-11
92.0


89.5


-12
Sample
22.3
761.1

25.5
783.4
-13
96.0


93.5


-14
104.0


101.2


-15
Sample
22. 2
760.7

25.5
782.9
-16
107.0


104.2


-17
113.0


110.0


-18
S ample
22.2
760.2

25.6
782.4
-19
120.0


116.8


(8)
(9)
Peak
V«»
Area
ul
1800
142.
930

1022

(10)	(11)	(12)
rJ x 106 XXT x 106 a or a1
N_	N
2S.12	31.26
1106
1197 93.5	15.90	16.46	20.48
554
1724
1962
1388 108.0 18.40	19.01	23.66
1046
1115	87.0 14,81	15.31	19.05
1312
1881
1628
1334	98.5 17.12	17.12	21.30
710
808
964
1360 1 00.0	1 7.39	1 7.40	21.71
1025
1212
1362 100.0	17.39	17.40	21,71
1274
1401
1350	99.5 17.30	17.33	21.57
1425
1543
1432 105.0 18.24	18.29	22.76
1627

-------
(1)
(2)
(3)
(4)
(S)
(6)
(7)
Run
V
gl
T
atm
P
atm

T
CH
PCH
No.
ul
°C
mm Hg
ul
°C
mm Hg
8-20
130.0


126.6


-21
S ample
22.8
759. 9

25.5
783.7
-22
150.0


145. 9


-23
100.0


97. 3


-24
Sample
22.0
759.1

25.5
781.1
-25
82.0


79.9


-26
89.0


86. 7


-27
S ample
22.0
758.9

25.5
780.9
-28
67.0


65. 3


-29
135.0


131.5


-30
Sample
22.8
758.4

25.5
781.2
9-1

22.5
756. 9



-2
102.0


99. 2


-3
151.0


147.0


-4
125.0


121.6


-5
S ample
22.7
756. 7

25.6
757.7
-6
53.0


51.6


-7
63.0


61.3


-8
70.0


68.1


-9
Sample
22.4
756.2

25.6
757.2
-10
81.0


78.8


-11
93.0


91. 7


-12
Sample
22.4
755. 9

25.6
756.9
-13
98.0


96.5


-14
114.0


112. 3


-15
Sample
22. 3
756.2

25.6
757.2
-16
121.0


118.0


-17
130.0


126.6


-18
Sample
22.1
755.8

25.5
756.8
-19
143.0


139.3


-20
157.0


152.9


(8)
Peak
Area
(9)
Vg
6s
ul
(10)
*N »106
2
(11)
v°6
2
1708



1405
103.0
17.85
17.87
1968



1303



1355
100.0
17. 36
17.43
1092



1194



1400
103.0
17.87
17.96
935



1810



1424
105.0
18.16
18. 24
1311



1195
89.5
15.45
16.02
744



804



910



1215
91.5
15.80
16.39
1061



1195



1237
93.0
16.05
16.66
1303



1501



1176
88.5
15. 29
15.86
1578



1639



1346
102.0
17.62
18.29
1830



(12)
22. 23
21.69
22.35
22.69
19.93
20.39
20.73
19. 73
22.75
2018

-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)


T
P
V„
T
P
Run
S1
atm
atm
So
CH
CH
No.
ul
°C
mm Hg
ul
°C
mm Hg
9-21
Sample
22.1
755.1

25.5
756. 1
-22
107.0


104.1


-23
111.0


108. 2


-24
S ample
22.7
755 .7

25.5
756.7
-25
66.0


64.2


-26
89.0


87.6


-27
Sample
22.3
755. 4

25.4
756. 4
-28
104.0


101. 2


-29
106.0


103.2


-30
Sample
23.8
755.5

25.4
756. 5
10-1

27.8
762.8



-2






-3
150.0


144.5


-4
127.0


122.3


-5
Sample
27.0
762.4

25.5
762. 9
-6
50.0


48.2


-7
63.0


60.8


-8
72.0


69.5


-9
Sample
26.8
762. 7

25.4
763. 2
-10
84.0


CM
w
00


-11
95.0


91.7


-12
Sample
26.8
763.0

25. 4
763.5
-13
103.0


99.5


-14
110.0


106.2


-15
Sample
.26.8
763.0

25.4
763.5
-16
121.0


118.3


-17
135.0


132.0


-18
Sample
26.8
763.3

25.4
763.8
-19
143.0


138.1


-20
86.0


83.0


-21
S ample
26.8
762. 7

25.4
763. 2
(8)	(9)	(10)	(11)	(12)
Peak	X' x 10^ X x 10^ a or a1 x
Area	ul	2	2
1256	94.5 16.49	17.12	21.31
1450
1466
1415 107.0 18.45	19.15	23.82
976
1250
1290	97.0 16.74	17.38	21.62
1381
1403
1440 109.0 18.72	19.43	24.18
1090	91.0 15.60	1 6.06	19.98
586
738
843
1087	90.5 15.53	15.97	19.87
997
1120
1123	93.0 15.97	16.42	20.43
1206
1262
1102	91.5 15.71	16.15	20.10
1390
1580
964	80.0 13.74	14.12	17.57
1650
1028
1039 86.0 1 4.76	15.18	1 9.63

-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Run
V
T
P
V
T
P
S1
atm
atm
So
CH
CH
No.
ul
°C
mm Hg
ul
°C
mm Hg
10-22
75.0


72. 4


-23
129.0


124.5


-24
S ample
26.8
762. 5

25.4
763.0
-25
152.0


146.7


-26
58.0


55.9


-27
S ample
26.8
762.8

25.7
763. 3
-28
83.0


80.2


-29
114.0


110.1


-30
Sample
26.8
762. 4

25.6
762. 9
11-1






-2






-3
152.0


147. 9


-4
128.0


124. 7


-5
Sample
22.0
759.8

26.0
759.8
-6
51.0


49.7


-7
60.0


58.4


-8
73.0


71.1


-9
Sample
22.1
759.8

26.0
759.0
-10
83.0


80.8


-11
94.0


91.6


-12
Sample
22.6
759. 3

25.9
759. 3
-13
101.0


98.3


-14
110.0


107.0


-15
Sample
23.2
759.0

25.9
759.0
-16
125.0


121.5


-17
141.0


137.0


-18
Sample
23.4
758.1

25.8
758. 1
-19
87.0


84.6


-20
98.0


95.2


-21
Sample
23.7
757. 7

25.8
757. 7
-22
79.0





(8)
Peak
Area
(9)
V*s
ul
(10)
X. * to6
2
(11)
v°6
85 9



1524



1537
128.0
21.96
22.56
17 77



708



1108
92.0
15.79
16.24
1003



1186



1200
99.5
17.07
17.57
1084



1504



1140
92.0
15.98
16.54
653



735



883



1177
95.0
16.50
17.09
1019



1258



1306
107.0
18.54
19.19
1207



1353



1191
96.5
16.68
17. 27
1470



1519



1233
100.0
17. 26
17. 89
1064



1199



1120
90.0
15.50
16.08
(12)
28. 07+
20. 20
21.86
20.58
21.26
23.88
21.49
22. 25
20. 01

-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)

V
T
P
V„
T
P
Run
Si
atm
atm

CH
CH
No.
ul
°C
mm Hg
ul
° C
mm Hg
11-23
81.0


78.6


-24
Sample
23.7
757.3

25.9
757. 3
-25
109.0


105.9


-26
135. 0


131.1


-27
Sample
23.6
756.8

25.9
756.8
-28
93.0


90.2


-29
145.0


140.7


-30
Sample
23. 7
756.4

25.8
756.4
12-1

24.8
758.6



-2
110.0


106.6


-3
152.0


147. 3


-4
200.0


193. 8


-5
S ample
25.6
758.6

25.9
1545. 6
-6
106.0


102. 6


-7
115.0


111. 3


-8
130.0


125.8


-9
Sample
26.0
758.6

25.8
1544.6
-10
237.0


229.1


-11
250.0


241. 7


-12
S ample
26.1
758.6

25.8
1544.6
-13
175.0


169.2


-14
190.0 ,


183. 7


-15
Sample
26.0
758.4

25. 7
1544.4
-16
212.0


205.0


-17
233.0


225. 3


-18
Sample
26. 2
758.4

25.7
1545.4
-19
225.0


217.5


-20
170.0


164. 3


-21
Sample
26.2
758.0

25.8
1544.0
-22
197.0


190.4


-23
205.0


198.0


(8)
Peak
Area
(9)
Vg
s
ul
(10)
X. „ 106
2
(11)
v *106
2
945



1040
83.0
14. 29
14.83
1293



1565



1188
96.0
16.52
17.16
999



1682



1200
97.0
16.68
17.33
1344



1790



2441



2612
205.5
35.22
35.21
1271



1351



1586



2410
190.0
32.52
32.53
2713



2797



2468
194.5
33.28
33.28
2163



2232



2456
193.5
33.11
33.12
2584



2830



2375
187.0
31.98
31.96
2760



2083



2535
200.0
34.18
34. 20
2443



2532



(12)
18.46
21. 35
21.57
43.81+
40.47
41.41
41. 21
39. 77
42.56

-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)

V
T
P
V„
T

Run
S1
atm
atm
g0
CH
CH
No.
ul
°C
mm Hg
ul
° C
mm Hg
12-24
220.0


212.5


13-1

22.4
768. 3



-2
156.0


151.8


-3
255.0


248. 3


-4
358.0


348.5


-5
S ample
22.9
768. 3

25.9
2289. 3
-6
275.0


267.5


-7
305.0


296.7


-8
325.0


316. 2


-9
Sample
22.9
768.4

25.8
2291.4
-10
295.0


287.0


-11
320.0


311. 3


-12
340.0


330.8


-13
Sample
23.0
766.8

25.7
2295.8
-14
375.0


364.7


-15
405.0


394.0


-16
270.0


262.6


-17
Sample
22.8
766. 4

25. 7
2295.4
-18
315.0


306.0


-19
365.0


355.0


-20
S ample
22.5
765.8

25.7
2294. 8
-21
275.0


265.0


-22
235.0


229.0


14-1

23.9
762.7



-2
54.5


52.9


-3
79.0


76.7


-4
103.0


100.0


-5
S ample
24.5
762.7

25.9
763.2
-6
41.0


39.8


-7
33.0


32.0


-8
66.0


64.0


(8)
(9)
(10)
(11)
Peak
Area
\
ul
XN * '°6
2
v - '°6
2
2703



2039



3282



4402



3821
290.0
50.80
51.15
3607



3947



4138



3833
291.0
50. 98
51. 28
3718



3885



4305



3569
266.0
46.49
46.67
4670



4843



3315



3549
264.0
46.15
46. 34
4052



4474



3635.
271.0
47.38
47.59
3628



3111



587



865



1038



690
64.0
11.07
11.40
427



347



648



(12)
63.64
63.81
58,07
57.65
59. 21
14.18

-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Run
V
T
P
V„
T
P
gl
atm
atm
g0
CH
CH
No.
ul
°C
mm Hg
ul
° C
mm Hg
14-9
Sample
24.7
762.3

25.8
762.8
-10
74.0


71.7


-11
92.0


89.1


-12
S ample
25.0
762.3

25.8
762.8
-13
126.0


122.2


-14
115.0


111.6


-15
S ample
25.0
762.0

25.6
762.5
-16
108.0


104.7


-17
88.0


85.3


-18
S ample
25.0
762.0

25.6
762.5
-19
63.0


61.1


-20
47.0


45.6


-21
S ample
25.0
761.2

25.6
761.7
-22
98.0


94.9


-23
75.0


72.7


-24
Sample
25.0
761.0

25.6
761.5
15-1

22.0
764. 2



-2
50.0


48.7


-3
72.0


70.1


-4
100.0


97.4


-5

22.8
764.3



-6
120.0


116.7


-7
65.0


63.2


-8
84.0


81.7


-9
S ample
23.4
764.5

25.8
765.5
-10
40.0


38.9


-11
58.0


56.4


-12
Sample
23.6
765.0

25.6
766.0
-13
107.0


104.0


-14
96.0


93.3


-15
95.0


92.3


(8) (9)	(10) (11)	(12)
Peak ^8	X' x 10^ X x 10^ a or a' x
,	N-.
Area ul	2 2
975	89. S 15.46	15.92	19.81+
752
965
591	54.0	9.32	9.60	11.94
1300
1206
630	58.5 10.09	10.39	12.93
1143
916
604	56.0	9.66	9.96	12.39
672
542
652	60.0 10.34	10.67	13.28
990
750
658	60.5 1 0.42	1 0.75	13.37
563
798
970
1347
708
901
860	77.5 13.48	13.84	17.22+
429
700
758	68.0 11.83	1 2.12	15.08
1093
1003
997

-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Run
\
T
atm
P
atm

T
CH
PCH
No.
ul
°C
mm Hg
ul
°C
mm Hg
15-16
Sample
23.2
765. 1

25.6
766.1
-17
125.0


121.5


-18
111.0


107.9


-19
Sample
23.2
765.1

25.5
766.1
-20
75.0


72.9


-21
57.0


55.4


-22
Sample
23. 2
765.0

25.5
766.0
-23
90.0


87.5


-24
80.0


77.8


-25
Sample
23.1
765. 1

25.5
767.1
16-1

22.6
763.8



-2
59.0


57.4


-3
84.0


81.7


-4
100.0


97.3


-5
Sample
22.9
764. 2

25.9
764.7
-6
27.0


26.3


-7
44.0


42.8


-8
68.0


66.1


-9
S ample
23.1
764.2

25.8
764.7
-10
88.0


85.6


-11
123.0


119.6


-12
Sample
23.4
764. 3

25.8
764.8
-13
111.0


107.9


-14
102.00


99.1


-15
Sample
23.6
764. 2

25.7
764.7
-16
78.0


75.8


-17
39.0


37.9


-18
S ample
23.7
764.1

25.7
764.6
-19
90.0


87.4


-20
115.0


111.7


-21
Sample
23.6
764.1

25.7
764.6
(8)	(9)	(10)	(11)	(12)
Peak	VS. x;. x 106 X„ x 1Q6 a or a' x
Area	ul	^2	^2
765	69.0 12.02	12.32	15.33
1260
1180
775	70.0 12.19	12.50	15.55
790
638
791	71.5 12.46	12.77	15.88
954
843
805	72.0 12.54	12.84	15.98
723
999
1190
1010	80.5 14.02	14.40	17.92+
456
615
845
893	70.5 12.28	12.61	15.69
1000
1520
906	71.5 12.44	12.77	15.89
1262
1312
889	70.5 12.25	12.59	15.66
1035
484
895	70.5 12.25	12.58	15.65
1116
1435
901	71.0 12.34	12.67	15.77

-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Run

T
atm
P
atm
Vgo
T
CH
PCH
No.
ul
° C
mm Hg
ul
°C
mm Hg
16-22
101.0


98.1


-23
69.0


67.0


17-1

22.1
759.6



-2
100.0


97.4


-3
49.0


47.7


-4
152.0


148.0


-5
Sample
22.3
759.3

12.2
761.3
-6
115.0


111.9


-7
131.0


127. 5


-8
141.0


137.2


-9
S ample
22.5
759. 6

12.1
761.6
-10
85.0


82.7


-11
90.0


87.6


-12
Sample
22.5
759.6

12.1
761.6
-13
99.0


96.4


-14
75.0


73.0


-IS
S ample
22.4
759.1

12.0
761.1
-16
108.0


105.1


-17
122.0


118.7


-18
S ample
22.5
758.9

12.0
759.9
-19
129.0


125.6


-20
138.0


134.4


-21
S ample
22.3
759.0

12.0
759.5
-22
65.0


63.3


-23
164.0


159.7


-24
S ample
22.3
758.8

12.0
759.3
18-1

22.5
761.8



-2
81.0


78.8


-3
100.0


97. 3


-4
153.0


148.9


-5
S ample
22.7
762.0

12.4
764.0
(8)
(9)
(10)
(11)
(12)
Peak
Area
\
ul
xk «.o6
2
v * *°6
2
a or a' :
1248




885




1001




522




1647




1083
100.0
17. 34
17.56
21.85
1205




1410




1554




1133
105.0
18. 2i
18.43
22. 92
910




916




1145
106.0
18.38
18.61
23.14
1041




787




1148
106.5
18.46
18.70
23. 26
1100




1260




1016
94.0
16.28
16.51
20.55
1345




1436




1300
120.5
20.89
21.20
26.38
692




1728




1160
107.5
18.63
18.91
23.53
1000




1273




1852




1556
121.0
21.04
21.23
26.17

-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Run
V
T
P
V
T
P
gl
atm
atm
g0
CH
CH
No.
ul
°C
mm Hg
ul
°C
mm Hg
18-6
48.0


46.8


-7
127.0


123.6


-8
Sample
23.0
762. 2

12.4
764.2
-9
114.0


110.8


-10
90.0


87.6


-11
S ample
23.0
762.0

12.4
764.0
-12
133.0


129.3


-13
141.0


137.1


-14
Sample
23.0
761. 8

12.4
763.8
-15
131.0


127.4


-16
107.0


104.0


-17
Sample
23. 2
761. 3

12.4
763.3
-18
63.0


61.4


-19
85.0


82.8


-20






-21
80.0


78.0


-22
90.0


87.7


19-1

25.5
748.3



-2
105.0


101.6


-3
150.0


145.1


-4
55.0


53. 2


-S
Sample
24.6
748.6

12.5
750.6
-6
78.0


75.6


-7
124.0


120.2


-8
S ample
24.8
748.8

12.5
750.8
-9
90.0


87.2


-10
143.0


138.5


-11
Sample
24.8
748.4

12.5
750.4
-12
116.0


112.4


-13
71.0


68.7


-14
Sample
24.8
748. 4

12.5
750.4
(8)
Peak
Area
(9)
\
ul
(10)
V * 106
2
(11)
XN *106
2
(12)
a or a'
651




1521




1444
113.0
19.63
19. 80
24.42
1463




1224




1433
112.0
19.45
19.62
24. 20
1755




1753




1310
103.0
17.88
18.04
22.46
1644




1250




1507
117.5
20.37
20.57
25. 34
745




1028




1018




1145




918




1320




451




1495
167.0
28. 34
29.12
35.26+
681




1069




1055
118.0
20.02
20. 56
24. 91
828




1292




919
104.0
17.63
18.12
21.94
967




625




987
112.0
18. 99
19.51
23. 63


-------
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Run
V
T
P
V„
T
P
gl
atm
atm
go
CH
CH
No.
ul
°C
mm Hg
ul
°C
mm Hg
19-15
161.0


156.0


-16
130.0


126.0


-17
Sample
24.8
748.2

12.5
750. 2
-18
140.0


135; 5


-19
170.0


164.7


-20
Sample
24.8
747.6

12.5
749. 6
-21
135.0


130.8


-22
70.0


67.7


-23
S ample
24.8
747. 7

12.5
749.7
20-1


749.4



-2
100.0
23.0

97.2


-3
202.0


196.3


-4
305.0


296.4


-5
Sample
23.0
748.8

12.5
1545.8
-6
130.0


126.3


-7
160.0


155.5


-8
Sample
22.9
749. 2

12.5
1545. 2
-9
236.0


230.0


-10
270.0


263.0


-11
S ample
23. 2
748.8

12.5
1544.8
-12






-13






-14
Sample
23.2
748.8

12.5
1545. 8
-15
210.0


204.1


-16
221.0


214.8


-17
Sample
23.2
748.8

12.5
1545.8
-18
240.0


233.2


-19
192.0


186.6


-20
S ample
23.2
748.6

12.5
1545. 6
CM
1
184.0


179.0


-22
174.0


169.1


(8)
Peak
Area
(9)
\
ul
(10)
X- x106
2
(11)
v°6
1365



1103



907
103.0
17.46
17.95
1237



1438



925
105.0
17. 78
18. 29
1144



606



925
105.0
17.79
18. 30
1205



2350



3454



2357
198.0
33.79
33.46
1533



1898



2596
219.0
37.41
37. 06
2765



3069



2150
180.0
30.70
30. 42
2370
199.0
33.94
33.61
2450



2525



2395
201.5
34. 37
34. 03
2740



2224



2425
204.0
34.78
34.45
2160



1980



(12)
21.72
22. 76
22. 76
41.63
46.11
37.85
41.82
42. 35
42.86

-------
(1)
(2)
(3)
(4)
(S)
(6)
(7)
(8)
(9)
(10)
(H)
(12)
Run
Vsi
T
atm
P
atm
VSo
T
CH
PCH
Peak
\
X- x106
2
X x 106
N2
a or a' :
No.
ul
°C
mm Hg
ul
°C
mm Hg
Area
ul

20-23
Sample
23.2
749.1

12.5
1546.1
2402
202.0
34. 47
34.12
42.46
21-1











-2











-3











-4











-5
Sample
22.5
763,6

12.5
2283. 6
3495
322.0
56.06
56. 24
69. 97
-6
280.0


272.5


2895




-7
330.0


321.2


3451




-8
310.0


301. 7


3112




-9
Sample
22.5
763.6

12.5
2283. 6
3427
315.5
54. 93
55.10
68.56
-10
260.0


253.0


2839




-11
350.0


341.0


3708




-12
S ample
22.5
763.6

12.5
2281.6
3564
328.5
57. 27
57.50
71.54
-13
300.0


292.0


3170




-14
322.0


313.5


3406




22-1
S ample
22.5
763. 6

12.5
2282.6
3803
320.0
55.79
55.99
69. 66
-2
290.0


282. 3


3458




-3
330.0


321. 2


3813




-4
Sample
22.5
763. 6

12.5
2283. 6
3800
320.0
55. 79
55. 97
69. 63
-5
336.0


327.0


3950




-6
300.0


292.0


3540




-7
Sample
22.5
762.8

12.5
2282. 8
3837
323.0
56.25
56.45
70. 23
-8
32C.O


311.5


3703




-9
280.0


273.0


3254




-10
S ample
22.5
762. 7

12.5
2282. 7
3860
325.5
56.68
56.88
70. 77
-11
335.0


326.0


3868




-12
310.0


302.0


3554




Experimental value disregarded. The disregarded values were thrown out on the basis of a 95% significance level test described by
J.D. Hinchen, Practical Statistics for Chemical Research, Methuen & Co. , Ltd., 11 New Fetter Lane, London 1969. p, 26.

-------