Vapor Liquid Eqqilibria

VAPOR-LIQUID EQUILIBRIA IN BINARY
HYDROCARBON-WATER SYSTEMS
By
Rikl Kobayashi
A dissertation submitted in partial fulfillment

of the requirements for the degree of
Doctor of Philosophy in the
University of Michigan
1951
Committee in charge:
Professor D.L. Katz, Chairman
Professor R.P. White
Associate Professor L.O. Case
Associate Professor G.B. Williams
Assistant Professor C.M* Sliepceyich
Acknowledgment
I wleh to gratefully acknowledge all those who so

generously aided in the course of this investigation,
especially to express my appreciation to:
Professor D.L. Katz, the Chairman of this doctoral

committee, for his guidance in the work.
Professor Cedomlr M. Sliepoevlch for his assistance

in the thermodynamic analysis of the data and the purchase
of equipment.
Profeseor L.O. Csse for his assistance in developing

an understanding of the Phase Rule as applied to hydrocarhon-
water systems.
Professor R.R. White and Professor G.B. Williams

for their participation as members of this doctoral
committee•
Mr. George A. Foster, Mr. Cleatis Bolen, and Mr.

William E. Hines for their continual aid in solving the
mechanical difficulties encountered.
Professor J.J. McKetta of the University of Texas

for the use of unpublished data on the methane-water and
ethane—water systems.
ii
Dr. H.J. Aroyan, my laboratory partner.
The Stanollnd Oil and G-os Company of Tulsa,

Oklahoma for their generous fellowship grants In the
years, 19*4-7- 19^ 9 *
The Phillips Petroleum Company of Bartlesville,

Oklahoma for furnishing the propane.
Mrs. Ruth Lesko for handling the purchase of ex

perimental materials and equipment.
Mrs. Kathyrn Michael and Miss Joanne Meredith for

their help in the preparation of the manuscript.
i
My Family for their patience, encouragement, and
financial assistance through the years.
TABLE OF CONTENTS
Sub .1ect Page

Title Page ................................ *■
/i-cknov/ledgement ........ ^
Table of Contents ..... iv
List of Tables ............................. v il
Table of Figures .....................
Statement of Problem ...................... xil
Summary .................................... xlil
Part I Vapor— Liquid Equilibria in Binary
Hydrocarbon-Water Systems
Introduction .......................... 1
Phase Rule and Its Relation to Experi
mental Procedure ................. *+
Experimental Method ................... 7
Presentation of D a t a .................. 10
Phase Rule Analysis of the Propane-
Water System .............. 33
The Saturated Y/ater Content of Hydrocarbon
Gases and Liquids. ............... M-3
Thermodynamic Analyls of the Solubility
of Pure Light Hydrocarbons in Water
at High Pressures and the Extrapo
lation of the Propane-Water Data to
10,000 Psl ........................ 52
Calculation of the Effect of Dissolved
Hydrocarbon Gases on the Density of
Water at High Pressures .......... 7*+
TABLE OF CONTENTS (Cont.)
Sub.1 ect Page

Part I (cont.)
The Interrelation of Minimum Solubility,
Henry* 8 Law, and the Volumetric Be
havior of the Solute-Rich Phase ... 80
Part II Experimental Equipment, Procedures, and
Techniques for the Determination of
Propane—Water Vapor-Liquid Equilibria
Relationships
Experimental Equipment ................. 86
Vapor-Liquid Equilibria Apparatus • . 86
. Analytical Train for the Propane-
Rich Phases .................... 88
Apparatus for the Analysis of the
Water-Rich Phase .............. 89
Pressurizing and Pressure Maintenance
Unit 90
Experimental Measurements ............. 96
Temperature Control' and Measurement 96
Pressure Control and Measurement ... 96
Analytical Weighings .............. 97
Chemicals Used ......................... 98
Propane ............................. 98
Distilled Water .................... 98
Mercury ............................. 98
Experimental Procedure ................ 100
Charging and Equilibrating ........ 100
Sampling and Analysis of the Propane-
Rich Phases 101
TABLE OF -CONTENTS (Cont.)
Subj eot . Page

Part II (Cont.)
Sampling and Analysis of the
Water-Rich Phase ............... 107
Part III Appendix

Laboratory Data and Sa.mple Calculations . • . 109
Propane-Rich Phases ................... 109
Water-Rich Phase ...................... Ill
Calibrations ...................... (....... 117
Bibliography ............................... 123
LIST OF TABLES
Table No. Subject Page

I Experimental Data in the 3-Phase
Region: Concentration of Water In
the Vapor Phase 14-
II Experimental Data in the 3-Phase
Region: Concentration of Water in
the Propane-Rich Liquid Phase 15
III Experimental Data in the 3-Phase
Region: Concentration of Propane
In the Water-Rich Phase 16
IV Smoothed Data in the 3-Phase Region
for all Three Phases. 17
V Experimental Data in the 2-Phase
Region: Concentration of Water in
the Propane-Rich Phases 18
VI Experimental Data in the 2-Phase
Region: Concentration of Propane
in the Water-Rich Liquid Phase 20
VII Graphically Smoothed Data in the
2-Phase Region: Concentration of
Water In the Propane-Rich Phases 22
VIII Graphically Smoothed Data in the.
2-Phase Region: Concentration of
Propane in the Water-Rich Phases 23
IX Solubility of Methane in Water:
Comparison of Graphically Smoothed
Data with Thermodynamically
Smoothed Values 63
X Solubility of Ethane in Water:
Smoothed Values 64-
XI Solubility of Propane in Water:
Smoothed Values 65
vii
LIST OF TABLES (Cont.)
Table N o . Subject Page

XII Modified Henry's L a w Constants
and Partial Molal Volumes of
Dissolved Gases 67
XIII (A): Composition of Natural Gas A 77
(B): Solubility of Natural Gas A
in Water 77
(C): Comparison of Experimental
and Calculated Densities of
Water Saturated with. Natural
Gas A 77
vili
TABLE OF FIGURES
Figure No* Sub .1eot Page

1 Vapor Pressure of the Propane—
Water System In the 3-Phase
Region 21+
2 Concentration of Water In the

Propane-Rich Phases In the 3—
Phase Region 25
3 Concentration of Propane in the
Water-Rich Liquid Phase in the
3-Phase Region 26
Concentration of Water In the

Propane—Rich Phases In the 2—
Phase Region Showing the Ex
perimental Points Along Iso
therms 27
5 Concentration of Prepane In the
Water—R ich Liquid Phase In the
2 -Phase Region Showing Experi
mental Points Along Isotherms 28
6 Smoothed Plot of the Concentration
of. Water in the Propane-Rich
Phases in the 2-Phase Region Al ong
Isobars 29
7 Smoothed Plot* of the Concentration
of Propane in the Water— Rich
Liquid Phase In the 2-Ph£.ee
Region Along Isobars 30
G Smoothed Plot of the Concentration
of Propane In the Water-Rich
Liquid Phase In the 2-Phase
Region at Low Pressure 31
9 Equilibrium Vaporization Constants
Between the Hydrocarbon-Rich
Phases In the 3-Phaee Region 32
10 Pressure-Temperature Projection
for the Propane— Water System 39
lx
TABLE OF FIGURES (Cont.)
Figure N o » Sub.1 eot Page

11 Temperature-Composltlon Diagrams
for the Propane Water System at
Several Pressures 4-0 ,4-1
12 An Isometric Drawing of the
Pressure-Temperature—Composition
Relations for the Propane-Water
System 4-2
13 Water Content of Light Hydrocarbon

Vapors and Liquids as a Function of
Molal Volume along Isotherms (Cal
culated Points Shown) 4*9
14- Water Content of Light Hydrocarbon
Vapors and Liquids as a Function of
Molal Volume along Isotherms (For
Even Values of Molecular Weight) 50
15 Composition of the Hydrocarbon-

Rich Phase at the 3-Phase Critical
for Light Hydrocarbon-Water Systems
as a Function of the 3-Phase
Critical Temperatures $1
16 PIo 1 8 for the Determination of Con
stants in the Thermodynamic Equation
for the Solubility of Methane in
Water 68
17 Plots for the Determination of

Constants in the Thermodynamic
Equation for the Solubility of
Ethane in Water 69
18 , Plots for the Determination of
18B Constants in the Thermodynamic
Equation for the Solubility of
Propane in Water 70,71
19 Modified Henry’s Law Constants as
a Function of Temperature for Pure
Light Hydrocarbons, Hydrogen, and
Nitrogen Dissolved In Water 72
I
TABLE OF FIGURES (Cont.)
Figure No. Sub.1 ect Page
20 Partial Molal Volumes of Pure

Light Hydrocarbons, Hydrogen,
and Nitrogen Dissolved in Water 73
21 Experimental and Calculated

Densities of Water Saturated with
a Natural Gas 79
22 Minimum and Maximum Solubility for

Henry* s Law Constant Decreasing
with Temperature 83
23 Minimum and Maximum Solubility for

Henry'e Law Constant Increasing
with Temperature ‘ 8U-
24- Minimum Solubility for the Temper
ature Region of Maximum Henry* e Law
Constant 85
25 Flow Sheet of the Vapor-Liquid

Equilibria Apparatus 92
26 Analytical Train for the Analysis
of the Hydrocarbon-Rich Phases 93
27 Apparatus for the Analysis of the

Water-Rioh Liquid Phase 9L
28 Pressurizing and Pressure Main
tenance Unit 95
29 Compressibility Factor for Propane

at Room Temperature Below Atmos
pheric Pressure 115
30 Henry* s Law Constants for the

Solubility of Propane in Water 116
31 Calibration Curve for the Copper-

Conetantan Thermocouples 120
32 Calibration Curve for the Upper
Section of the Gas-Water Burette 121
33 Calibration Curve for the Lower

Section of the Gas-Water Burette 122
xi
STATEMENT OF PROBLEM
The objects of this investigation weres

(1 ) To obtain experimental vapor-liquid equilibria
data for the binary system propane-water from the hydrate
region to 3 00 deg. F. and pressures up to 3000 pel.
(2 ) To make a study of the phase relations for the
propane-water system through the application of the ex
perimental data and the phase rule*
(3) To study and correlate the available vapor-
liquid equilibria data on hydrocarbon-water systems using
the thermodynamic data of pure hydrocarbons wherever
possible.
SUMMARY
Vapor-liquld equilibria data were obtained in the

two and three— phase regions for the system Propane— Water
at temperatures from 5^ deg. F to ~$00 deg. F and pressures
from 100 to 2800 psla. The system was studied with
relative thoroughness, especially in the region surrounding
205.7 deg. F and 6 37 peia * the conditions at which the
vapor phase and the propane-rich liquid phase become
continuously identical.
Experimental data on the solubility of water in
the propane-rich phases were obtained for the three-phase
envelope, and in the two-phase region for isotherms of
100 , 150, 190, 205.7, 2 3 °> 260, and 300 deg. F up to
2800 psla. The solubility of propane in water was de
termined experimentally in the three-phase region, and in
the two-phase region for isotherms of 5b, 100, I33, I90,
2o 5 »7t2 3°* 260, and 30 ° deg# F up to 2800 psla. The ex
perimental data are presented graphically using pressure,
temperature, and composition as variables. The graphical
representation of the data illustrate clearly the relation
of the volumetric properties of propane on the mutual
solubilities of propane and water. Excepting at low
pressures and high temperatures, the solubility of water
in propane is very low. The concentrations encountered
were generally lees than 5 per cent water in propane.
The solubility of propane in liquid water was extremely
low, never exceeding O.07 mol per cent propane over the
range of conditions covered in this experimental investi
gation.
A qualitative analysis of the phase relations for
the complete propane-water system, based on the Phase Rule
of Willard Gibbs and the experimental data has been made.
A correlation showing the solubility of water in
light hydrocarbon liquids and vapors as a function of
temperature, molal volume, and the molecular weight to
a lesser extent, has been developed. For complex hydro
carbon mixtures the water content can be predicted
successfully in the vapor phase, in the hydrocarbon— rich
liquid phase in the three-phase region at low pressures,

and in the compressed hydrocarbon fluid phase. The
limitations of this correlation, when applied to complex
hydrocarbon-water systems, are discussed a n d ’are illus
trated graphically.
A thermodynamic equation relating the solubility
of a pure hydrocarbon in water to the partial volumetric
properties of that hydrocarbon in the coexisting phases
and the Henry* s Law constant has been applied to the
methane-water, ethane-water, and the propane-water systems.
The solubility of propane in water has been calculated
from 3OOO to 10,000 pel by the application of this
equation to the experimental vapor-liquid equilibria
data of the propane-water system below 3OOO pel and
the volumetric data of pure propane from 0 to 10,000 psi.
The validity of the extrapolation is supported by the
conclusions drawn from the thermodynamic study of the
methane-water and the ethane-water systems. The partial
molal volumes of the dissolved hydrocarbons obtained from
this study have been applied to estimate the effect of
dissolved hydrocarbons on the density of water.
Minimum and maximum isobaric solubilities of gases
in water at high pressures are dlsoussed qualitatively
in relation to Henry's Law and the volumetric behavior of
the solute-rich phase.
A detailed discussion of the experimental equipment,

procedures, and techniques used in the determination of
the propane-water vapor-liquid equilibria relationships
is given.
PART I
VAPOR— LIQUID EQUILIBRIA IN BINARY
HYDROCARBON-WATER SYSTEM
-1-
INTRODUCTION
The general purpose of this study Is to contribute

to the fundamental understanding of the subject of
hydrocarbon—water vapor—liquid equilibria* The appearance
of water with hydrocarbons in nature and in commercial
processes is quite common. New processes and refine
ments in natural gas transmission and in petroleum pro
duction methods have increased the need for a thorough
understanding of hydrocarbon-water systems.
Work on hydrocarbon— water phase relations was
initiated by Scheffer in 1913. Studies were then made
of the hexane-water (4-0 ) and the pentane-water (4-1 )
systems up to their respective 3-phase critical conditions.
Hydrocarbon—water systems have been investigated more ex
tensively in regard to the formation of gas hydrates (6),
(17 )* (18 ), (3*0 * (4-4-), (4-8 ) than in regard to vapor-
llquld equilibria. Lauhlere and Briscoe (24-) and Deaton
and Frost (13) determined the concentration of water in
natural gas up to 100 deg. F and 600 pel in connection
with natural gas dehydration processes. These data have
been supplemented by those of Russell, Thompson, Vance,
and Huntington (35) up to 2000 psi.
Sage, Lacey and co—workers have determined the dew-

point compositions of the methane-water (30) and the
*
ethane—water (32) systems over a wide range of

temperatures up to 10,000 psi. Sage and Lacey (33)
have also determined the composition of water In the
nrbutane-ivater system in the butane-rich phases in the
3-phase region. Data on the water content of a natural
gas saturated with water, and the solubility of a
natural gas in water and in brine solutions up to 250
deg. F and 5000 psi have been presented by Dodson and
Standing (14-)•
McKetta and Katz (2 8 ), (29) made an extensive
study of the methane-n-butane-water system and developed
general plots for the estimation of the solubility of
water in hydrocarbon gases and liquids (28 ). Culberson,
Horn, and McKetta (9) reported data on the solubility of
ethane in water up to 1200 psi and for methane in rater
at 77 deg. F up to 10,000 psi. Culberson and McKetta (10 )
(11) have recently extended their data on the solubility
of methane and ethane in water in the temperature range
from 100 deg. F to 34-0 deg. F and up to 10,000 psi for
both systems.
After a consideration of the existing data, a binary
system, propane-water, was chosen so that fundamental studies
and observations could be made on the behavior of hydro—
carbon-water mixtures. The location of the 3-phase vapor-
liciuid— liquid region for the propane-water system along the
-3-
t ampere ture scale, relative to other binary hydrocarbon

systems, allows it to be studied much more completely.
This part covers the general subject of vapor-
llauid equilibria in binary hydrocarbon systems, which
includes the presentation and analysis of the experi
mental data obtained in this work. Part II is a detailed
discussion of the experimental eouipment, prooedures, and
techniques used in the determinetion of the propane-water
vapor— llnuid equilibria relationships. The laboratory
data taken and the sample calculations are discussed in
the Appendix, Part III.
-Ju
ra AS E RULE AND ITS RELATION TO EXPERIMENTAL PROCEDURE '
The selection of* the dependent end independent var-

lebles which sr° required to completely define en eoullibri
um system must be made in accordance with the reauirernents
of the Phase Rule of Willard Gibbs. Within this limitet ion
the choice of dependent end independent variables ere Re
lented in relation to the informntion desired and to experi
mental convenience.
The Pheae Rule of Willard Gibbs is simply stated as:
V =C - P + 2 (1)
%
where V = the degrees of freedom or the number of inde

pendent variables required to express the phase
equilibria,
C = the number of components, propane and water in
the present case,
P = the number of coexisting equilibrium phases.
For a binary system with 3 coexisting phases V = l t
It follows th*»n that the dependent variables concerning
vapor-liquid equilibria may be expressed uniquely in terms
of a singleindependent variable. If T Is chosen as the
independent variable, the following functions suffice to
describe the system completely, as far as vapor-llauid
equilibria are concerned:
P = f1 (T) (2 )
x 2 = f2 (T) (3)
yl = f3 (T)
*1 = fU.(T> (5 >
in which T = temp^rature,
P = pressure,
Xp = mol fraction hydrocarbon in the water-rich
liquid phase,
= mol fraction of v/ater inthp vapor ohase, and
Zn = mol frnotion of water in the propane— richor
lighter liouid phase.
Thus, setting the temperature of the cell, injecting
propane and water into it in quantities that will produce
3-phases, and agitating the mixture until equilibrium is
reached will produce unique values of pressure and phase
concentretions. The latter are determined by 'sampling nnd
analyzing the phases. . The 3— Phase region terminates at the
3—phase critical where the vapor phase and the propane— rich
liouid phase become continuously identical.
For the coexistence of 2 phases, since V = 2 , the
variables in which we are interested may be expressed by:
x2 = 1*5 (T,P) (6)

7l = f6 (T,P) ' (7 )
zx = f? (T,P) (8)
where the variables are defined as before, realizing that

y x = fg(T,P) is continuous with = fy(T,P) along iso
therms for T greatf»r than the 3~phfia® critical temperature,
205.7 deg.F, and along isobars for P greater than the
3—phase critical pressure, 637 psie* To determine the
compositions experimentally, the cell temperature wes set
at a selected isotherm, the cell charged with wat°rf and
propane added to th" desired pressure tîth the existence
of two phases. The mixture wnR then enuilihrated, and the
coexisting ohases sampled and analyzed to give the equi
librium relationship. In this case, the cell pressure,
pb well «s the temperature, must be controlled by adding
the proper amount of propane and water.
-7 -
EXPERIMENTAL METHOD
This vapor-liquid equilibria study was conducted

using a batch operation. Propane and water were placed
in a pressure cell surrounded by a thermostatically con
trolled bath and brought to phase equilibrium by mechanical
agitation. The resulting equilibrium phases were sampled
under equilibrium conditions. Mercury was injected into
the cell to maintain the equilibrium within the cell
during the sampling of all phases except the vapor phase
in the three-phase region. In the three-phase region, the
vapor phase was sampled from the cell with the stirrer
running, but without mercury injection. The cell was
equipped with a glass window which was used to detect
the number and quantities of the coexisting phases.
The samples were transferred directly from the cell
to the analytical apparatus through small diameter steel
i
tubing. High pressure pycnometers were used for the
first few runs in an attempt to obtain the phase densities
as well as the phase compositions. Their use was dis
carded in order to obtain more accurate analytical re-
*
suits and to permit adjustment of sample sizes with

varying conditions. Since the mutual solubilities of
propane and water are generally very small, the phase
densities must be observed by more refined techniques than
high pressure pycnometers will permit, to be of any value.
-g-
The use of pycnometers to determine the phase densities

of the hydrocarbon-rich phases in binary hydrocarbon-
water systems in the three-phase region is entirely im
possible because of the similarity of the behavior of
these phases in the three-phase region to that of the
saturated liquids and vapors of the pure hydrocarbons.
In the sampling operation each phase was sampled
through a different port, appropriately located in the
ovm phase, in order to avoid contamination of the sample
lines by a second phase. The vapor sample lines were
heated above the equilibrium temperature to prevent the
condensation of the vapor in the sample lines and the
resulting loss of water from the sample during the
transfer through the lines.
The hydrocarbon—rich phases were analyzed by ab
sorbing the water from the expanded gas with Dehydrite
(magnesium perchlorate) and measuring the corresponding
amount of dehydrated gaseous propane. The necessary
precautions for the handling and weighing of the U-tubes
were observed. The compressibility factors of propane
gas at atmospheric and lower pressures were applied in the
calculation of the final phase compositions.
The water-rich liquid phase was analyzed by measuring
the volumes of liquid and gas formed by an equilibrium
flash expansion conducted at substantially room temperature
and at one atmosphere. The dissolved propane remaining
-9-
ln the flash liouid was computed using the solubility

data of propane in water at atmospheric pressure (25)
and the Henry's Law Constants obtained from the thermo
dynamic cslculr.tlons on the propane-water system, po. 57 .
The vapor pressure data of water was used to correct for
the v-'ater vapor present in the equilibrium flash vapor*
A material balance of the propane and water made on the
overall sample yielded the final composition of the
sample.
For any given isotherm, the pressures at which the
rune were made were determined from the trend suggested
by previously obtained data.
The detailed-discussion of the experimental
equipment, procedures and techniques used in this vapor-
liquid equilibria study are presented in Part II and the
sample calculations are presented In Part III, the
Appendix.
-10-
PRESENTATION OF EXPERIMENTAL DATA
Experimental vapor-liquld equilibria data for the

propane-water system are presented in the 3-phase region
from 54- deg. F to the 3-phase critical of 205.7 deg. F and
637 peia in Tables 1, 2 , 3 and Figures 1 , 2, 3. Vapor-
liquld equilibria data in the 2-phase region from 100 to

2800 psia are presented at Isotherms of 100 , I50, I90,
205.7, 230, 260 , and 300 deg. F for the propane-rich
phases in Table 5 and Figure 4-, and at isotherms of 54-,
100 , I33, I90, 205.7, 2 6 0 , and 300 deg. F for the
water-rich phase in Table 6 and Figure 5 *
The Solubility of Water in the Hydrocarbon-Rich Phases

In the 3-phase region, the solubility of water In
the propane-rich phase and in the vapor phase describes
a continuous envelope, Figure 2 , which closes at the
3-phase critical conditions where the composition and
the other intensive properties of the two phases become
continuously identical. In this region, both the solu
bility of water in the propane-rich phase and the
volumetric properties of that phase are very sensitive
functions of pressure and temperature.
In the 3-phase region, the highest equilibrium
*
ratio, K, of the concentration of water in the vapor to

the concentration of water In the equilibrium propane-
rich liquid, Figure 9, occurs at the lowest temperature.
-11-
The ratio becomes 1.0 at the 3-phase critical condition

of 205.7 deg. F and 637 psia.
A study of Figure U- combined with an understanding
of the volumetric behavior of pure constituents in their
critical regions Indicate that the solubility of water
in the propane— rich phases is related to the temperature
and the volumetric behavior of the propane-rich phases.
»
Thus, the Isotherms of the propane-rich phase relating

solubility to pressure and the isotherms relating the
volumetric behavior of the same phase to preeaura are
both discontinuous below 205.7 deg. F, but continuous
at that and higher temperatures.
Raoult’s Law (2 6 ) predicts the Isotherm on a log
concentration versus log pressure plot at a given tempera
ture to be a line of slope -1 passing through the point
representing the vapor pressure of pure water at that
temperature. The dotted lines, Figure U-, indicate portions
of the ideal isotherms predicted by R a o u l t 1s Law. These
ideal Isotherms have been used whenever appropriate to
aid in drawing the "best curve11 through the experimental
points and to extrapolate the data. The data indicates
both positive and negative deviations from the law, both
in the vapor and propa.ne-rich liquid phases.
Figure 5 shows a plot of water concentration as a
function of temperature along several Isobars ranging from
100 psia to 3OOO psia. The vapor pressure data for pure
-12-
w&ter has been used to develop Figure 6 from Figure 4-.

The greatest Inaccuracies in the cross-plot, Figure 6 ►
are expected to occur in the 3-phase critical region
■where the concentration change with respect to pressure
and temperature is greater than for other regions.
The S o l u b i l i t y of Propane in Water

Figure 5 presents the data on the solubility of
propane in water. The Isotherms are shown from 5*4- to
300 deg. F. The solubility of propane in water in the
3-phase region le shown as a concaved curve, shoving a
minimum at about 250 psia, on which the. discontinuities
of the isotherms below 2 0 5 .7 de§>* F occur. The 3-phase
solubility locus terminates at that temperature, the
3-phase critical temperature. The solubility isotherms
are continuous functions of pressure at and above 205.7

while the solubility isobars, Figure 7, are continuous
functions of temperature at and above 637 psia, the
3-phase critical pressure.
As in the case of the solubility of water in the
propane-rich phases, the solubility of propane in the
water-rich phase 1 b associated with the volumetric pro
perties of the propane-rich phase. Thus, the continuity
and discontinuity in the Isothermal and isobaric solu
bility curves above and below the 3-phase critical con
dition are related to the continuity and discontinuity
-13-
Qf the volumetric behavior of the propane—rloh phases

along the corresponding Isotherms and Isobars* The
effect of pressure upon the solubility of propane In
water Is directly related to the effedt of pressure
on the volumetric behavior of the coexisting propane-
rich phase. If the compressibility of the propane-rich
phase is high, e.g., that of a gas, the effect of the
pressure on the solubility of propane in water is high*
A low compressibility, e.g., that of a liquid, is marked
by a small effect of pressure on the solubility. These
relations are quantitatively revealed in the section
entitled "Thermodynamic Analysis of the Solubility of
Hydrocarbon in Water at High Pressures," pp 58 •
To preserve the clarity of Figure 5, some of the
isotherms for temperatures greater than 170 °F at low
pressures have been ommitted* An expanded plot of this
region, Figure 8, has been prepared to present all the
isotherms determined experimentally In this region*
a
-14-
Experimental Data In the 3” P*lae® Region:

Concentration of Water in the Vapor Phase
Temperature Pressure Composition of

°F psia the Vapor Phase
Mol Fraction
________________ ___________ ._____________________ Water______
63.0 113*8 .002322

64.1 114.6 .002370
83.1 151.8 ‘ .003582
87.O 159*7 .OO37O8
102.5 195*0 .004855
111.6 220 ' .00552
111.8 220 .00549
127.7 270 ' .00696
128.2 271 .OO696
144.1 328 .00854
144.1 328 .00863
170.0 437 .OIO97
179*0 488 .01175
179*2 487 *01177
187.6 529 .01263
188.6 535 .01278
190.3 540 .01282
192.8 561 .01282
193*0 562 .01270
201.6 6I3 .01212
201.7 612 .01208
TABLE II
Experimental Data in the 3-Phaee Region:
Concentration of Water in the Propane-Rich
Liquid Phase

®F psia the Propane-Rich
Liquid Phase
Mol Fraction
Water
58.4 107.1 .OOOI368

78.5 142.5 .OOO3340
78.7 142.5 .OOO3403
101.9 195*0 .000614
101.9 195*6 .000626
128.5 272 .OOI368
128.8 271 .OOI378
144.6 330 .OOI995
170.0 438 *003555
171.0 443 .003682
188.6 535 .00542
191*4 551 .00605
191.6 549 .00544
195*6 572 .00659
201.7 oil .00764
202.1 612 .OO769
• 205.4 633 .01001
• 206.1 638 .00995
* Critical Region
- 16-
TABLE III
Experimental 'Data in the 3-Phase Region:
Concentration of Propane in the Water— Rich
Liquid Phase

psia the"Water-Rich
Liquid Phase
Mol Fraction
Propane
42.3 82.2 .OOO366

53*9 101 .0002913
78.1 142 .0002208
79*1 1^3 .0002208
100.2 191 .00002045
100.6 191 .0002001
132.9 284 .0002046
137-7 399 .0002003
154.2 366 .0002063
160.3 391 .0002107
172.2 446 .0002298
179-7 482 .0002360
18 9-6 538 .0002495
191-1 543 .0002489
201.7 608 .0002638
205.4 632 .0002726
* Quadruple point by extrapolation

-17-
table IV
Smoothed Data in the 3-Phase Region

for all Three Phases
Temperature Pressure Composition

M.F. M.F. M.F.
°F psia Water in the Water in the Propane in
Vapor Phase Propane—Rioh the Water—
Liquid Phase Rioh
Liquid Phase
42.3 82.2 .0014-0 .00010c .OOO366

60.0 108.5 .00218 .OOOI87 .000264
80.0 146.0 .00335 .OOOlM-it .000219
100.0 .00465 .00061c .000203
120 .00625 .00109 .OOOI99
140 311 .OO8I3 .00184 .000202
160 389 .01002 .00291 .000212
170 432 .OIO97 .OO358 .000223
180 483 .01191 .00446 .OOO236
I90 538 .01280 .00558 .000250
195 658 .OI278 .00to32 .000256
200 602 .01237 .00723 .000264
205.7 637 .OO998 .00998 .000272
* 3-Phase Critical.
-lg-
TABLE V
Experimental Data In the 2- Phase Region:
Concentration of Water In the Propane-Rich
Phases

the Propane-Rich
Phase, Mol Fraction
psia____________________ Water________
100 102 .00954
100 l4l .00696
100 533 .00492
100 818 .000587
100 1015 .000673
100 2018 .OOO5M-O
100 2023 .OOO6U.3
100 2798 .000591
100 2798 .000623
150 146 .026M-9
150 217 .01702
150 289 .01200
150 856 .002328
150 156*4- .00222*4-
150 248*4- .002060
150 2803 •0020*4-6
190 1 90 .0*1-967
190 309 .02910
190 465 .01722
190 1342 .00502
190 2003 .00475
190 2803 .00463
205.7 207 *0637
205.7 ^5 .02639
205.7 603 .OI568
205.7 637 .OO998
20§.7 696 .OO8I3
205.7 755 -00779
205.7 1217 .00726
205.7 2023 .00674
205.7 2803 .00640
-19-
TABLE V (Cori't)
Experimental Data In the 2-Phase Region:
Concentration of Water in the Propane-Rich
Phases

the Propane-Rich
Phases, Mol Fraction
°F psia Water
230 2R2 .080 94

230 446 .04325
230 630 .02659
230 718 .02028
230 823 .OI366
230 1530 .OIO33
230 2023 .OO959
230 270$ .OO9I9
260 ^•39 .07856
260 675 .04660
260 812 .03599
260 996 .024 99
260 1411 .01843
260 2023 .01646
260 2023 .01649
260 2755 .01490
.10146
K\K\K\r<M'r\r<\
000000
622
OOOOOO
928 .06350
1217 .04496
i44 i .03875
2023 .03105
2803 .02684
-20-
TABLE VI
Experimental Data in the 2— Phase Region:
Concentration of Propane in the Water— Rioh
Liquid Phase

the Water-Rich
Liquid Phase
Mol Fraction
°F____________________ psia________________ Propane
54.0 .0002963
54.0 I 17
617 .0003029
54.0 1222 .0002906
54-.0 1988 .000294.8
100 72 .OOOO863
100 .OOOI532
100 ,
117
428 .0002046
100 622 .0002175
100 .0002151
100 II I I .0002239
100 2687 .0002304
133.0 188 .00014-99
133-0 1199 .0002249
133-0 1810 .0002267
133.0 2787 .0002364
181 .0001146
HH
OO
307 .OOOI763
190 .OOOO796
190 224 .OOOI33O
190 359 .OOOI96O
190 990 .0002580
190 1523 .0002703
190 2012 .000274-5
190 2787 .0002880
TABLE VI (cont»d)
Experimental Data in the 2-Phase Region:
Concentration of Propane in the Water— Rich
Liquid Phase

the Water— Rich
Liquid Phase
Mol Fraction
°F psia Propane
205. 7 230 .0001261

§.
20 7 M-oo .0002162
205. 7 U-7Q .000214-M-9
205. 7 910 •00028M-2
205. 7 1810 .0003008
205. 7 2787 .00031314-
230 222 .0001301
230 504- .0002633
230 810 ;000324-3
230 1128 0003415
230 1810 •.0*00351P2
230 2787 .OOO3765
260 170 .0001001
260 332 .00019614-
260 511 .0002802
260 .OOO3665
260 ilfl .0004-197
260 1810 .OOOI4-393
260 2787 .0001I-766
300 265 .0001666
300 I47I .OOO3O3I
300 69M -
.0004-130
300 .00014-876
300 156* .0005801
300 1810 .0006078
300 2787 .0006861
-22-
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r^vr^-vo o 1 0 0 cq p h o on co o v d - oSs*-
<D I—II—t ■t'Of'—rH CQ r»MjTMD p-—ON,—(CQ.=}-
Graphically Smoothed Data in the 2-Phase Region:
O ca UNrH rH CQ CQ r^NKNKNKM^M^NJ^N^-^d-S-
UN cti 0 0 0 O O O O O O O O OO) O O
CQ XJ 00 0 O O O O O O O O O O O O
Concentration of Propane in the Water-Rich
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PROPANE-WATER SYSTEM
P R O P A N E
ON
F R A C T I
IV! O I
D 205.7 'F
V 230 'F
260'F
6 300 'F
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000
PRESSURE, PSIA
FIGURE 5 CONCENTRATION OF PROPANE IN THE WATER-RICH LIQUID PHASE IN THE 2-PHASE REGION |
-29- i
\
100
090
060
050 \ \
VAPOR COMPOSITION
040
OF VAPOR-LIQUID REGION
fed 3 X V M
fvj O I
3-PHASE
CRITICAL
.007
3-PHASE ENVELOPE
LIQUID-LIQUID
REGION
'320 300 280 260 240 220 200 180 160 140 120 100 8(
TEMPERATURE, DEG. F
FIGURE 6 CONCENTRATION OF WATER IN THE PROPANE-RICH PHASES IN THE 2-PHASE REGION

f
0005
,0004
L IQ U ID LIQUID
,0003 REGION 00^° 0#
m 400 PSIA
300
200 PSIA
VAPOR LIQUID
REGION
lOOPSlA
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
TEMPERATURE, °F ^
^ I
FIGURE 1 CONCENTRATION OF PROPANE IN THE WATER-RICH LIQUID PHASE IN THE 2-PHASE REGION H
ALONG ISOBARS H
0
0
0
0
0
0
IM
0
W
0
0
N
0
0
0
0
(M
0
0
0
It)
0
0
0
0
0
0
N
3NVdOHd NOIlOVHd 10W

0
0
0
K
FIGURE 8 CO NCENTRATION OF PRO PA N E IIM THE WATER — RICH LIQUID
PHASE IN THE 2 —PHAS E REGI ON AT LOW PRESSURES
50
0< ■I■
3 F>R0 PANE-WA T E R
O
SYSTEM
:2 o
10
8
6
2 4 %
N(DTE; T EMPI ERATURE VAR IES

W IT H 13RESSURE
j}
i•
!j
I
20 40 6 0 80 100 200 400 600 1000 *i
PRESSURE, PSIA
35
I*
FIGURE 9 EQUILIBRIUM VAPORIZATION CONSTANTS
FOR T H E HYDROCARBON-RICH PHASES IN 1
T H E 3 - P H A S E REGION
- 33-
phase RULE ANALYSIS OF THE

A general understanding of the phase relations of

the propane-water system may be developed through the
application of the phase rule to the existing data on
the binary propane-water system, Including the data of
the pure components propane and water. The emphasis on
such a study are qualitative relationships expressing
phase rule principles rather than on quantitative ones.
The implications of the phase rule certainly extend be
yond the scope of the data, but the qualitative relation
ships thereby expressed are no longer actual but logical
relationships.
The variables which are required to express 2-phase
and 3-phase vapor-liquid equilibria has been discussed
under "Phase Rule and Its Relation to Experimental Pro
cedure" on pp k- to 6 o Also listed in the section are
the functions, Equation (2 ) through Equation (8), whioh
are necessary to describe 3-phaee and 2-phase vapor-liquld
equilibria completely. Since all the compositions of a
binary system may be expressed along a common axis, the
variables pressure, temperature, and compositions may
be represented for all conceivable phase equilibria with
a Pressure— Temperature— Composition Diagram (P—T—X diagram).
Two— phase equilibria are represented by a pair of
surfaces, one for each phase. Three-phase equilibria are
represented by three space curves, each formed by the
intersection of two surfaces. The condition of the
uniformity of pressure and temperature for an equilibrium
system requires that the space curves for all 3-phases
^yield the same projection on the pressure-temperature
(P-T) plane. - »
Further, M— phase equilibria are rep

resented as four unique polnte in space at their re
spective phase compositions, which fall on a straight
line perpendicular to the P-T plane. From each of such
polnte, there must radiate three space curves. The IP
space curves originating from the U— phase equilibria

points appear as four 3-phase curves emanating from an
Invariant U— phase point or quadruple point ,when projected
on the P-T plane. For the pure components, 2-phase
equilibria appear as. lines in the pure component planes
of the P-T-X figure#
The termination of a 3-phase locus for a 2-com-
ponent system may occur in the three following ways if
the appearance of solid-solid solubilities is rejected:
(1) by the addition of another phase to give an
invariant quadruple point,
(2) by the loss of a component in which the end
point is identified as an invariant triple point of the
other pure component, and
(3) by critical behavior in which any two of the co
existing liquid or vapor phases become continuously
identical. I
- 35-
aii the above implications of the phase rule are to be

followed in the development of the phase rule analysis*
The development of the analysis is initiated by
drawing the P-T projection. Figure 10, for the propane-
water system, including that for the pure constituents
propane and water.
Throughout this discussion, the following phase

designations are used:
H for hydrate,
for the water-rich liquid phase,

Lg for the hydrocarbon-rich liquid phase,
I for ice,
V for the vapor phase, and
P for solid propane

The appearance of only one hydrate of propane and the
absence of solid-soli’d solubilities is assumed in the
foregoing treatment. No attempt has been made to keep
an exact scale in the diagrams utilized in this dis
cussion because many of the lines shown would coincide
indlstlngulshably with others. The concentrations are,
in most cases, so small that they could not be illus
trated clearly unless exaggerated. On the other hand,
the correct or logically correct relative positions of
the lines and the phase compositions have been maintained.
Figure 11 shows a series of T-X diagrams taken at
seven different pressures which were considered pertinent
to the development of the phase rule analysis and to the ,
construction of Figure 12 . Figure 12 is an Isometric
drawing of the propane-water system representing its
pressure-temperature-composltion relationships. Thus,
the seven T-X diagrams of Figure 11 reappear on Figure
12 in isometric positions.
The P-T projection prove to be of considerable aid

in drawing the T-X diagrams of Figure 11 . The intersection
of the constant pressure planes, shown as dotted lines on
Figure 10 , with a line of the P-T projection define a
temperature at which the phase compositions are to be lo
cated on the T-X dlagra.ms of Figure 11 . Empirical data
are used to determine the relative location of the phase
compositions at that temperature. These phase compo
sitions represent the terminal points of the lines re
lating temperature and composition on the T-X diagrams.
Some of the constant pressure planes were chosen
for their distinctive features:
Pn for the existence -of the triple point
I-Ia-V,
Pji for the existence of the quadruple point
H-4-Lg-V,
P,- for the existence of the 3-phase critical at
^ which Lg and V become continuously identical, and
Pg for the existence of the 2-phase critical of water,

the initial point of the critical loci for the
binary in which and V become continuously
identical•
A method of designating the space curves in Figure 12
and in the discussion has been devised. As an example,
- 37-
for the 3-phase equilibria L-^-H— V the three space curves

are designated In Figure 12 by (L^-H-V), HCI^-H-V),
and V(L 1-H-V). The letter or letters before the pa
renthesis designate the phase whose composition is de
fined by the space curve, and the letters within the
parenthesis designate the coexisting equilibrium phases
for that equilibria* Thus, 2-component 2-pheee vapor- and
liquid equilibria lines, which appear on the T-X planes
of Figure 12 , are designated by <*a-V) for the liould
phase and V(L^-V) for the vapor phase*
The vapor pressure curve of water is designated by

L^,V(L^-V) and terminates at the criticel point B. The
vapor pressure curve for propane is labelled Lg,V(Lg-V)
and terminates at its critloal E* The critical loci in
volving the water-rich liquid phase and the vapor phase
is labelled L-^ = V, (L^-V) and the critical loci involving
the propane-rich liquid phase and the vepor phase is de
fined by the line DE*
The equilibria (Lj-V-Lg), which exists between
and Pj., are designated L^fL^-V-Lg), V(L^-V-Lg), and
Lg(L^-V-Lg). The experimental deta, it may be recalled,
of these loci are plotted on Figures 2 and 3 * At P^,
4- phases are in equilibrium, phase H disappearing imme
diately as the pressure is increased along L^(L^-V-Lg).
VOj-V-Lg), and Lg <4 -^- 1^).

-38-
The surface through the traces labelled L ^ L ^-V)

represent the liquid compositions In equilibrium with
the vapor compositions on the surface through the traces
labelled VfL ^ V ) . Lines at constant preseure and temper
ature pierce the respective surfaces at the vapor and
liquid compositions in equilibrium. The experimental
work of this study has been to determine these two sur
faces precisely.
Also of practical interest are the space curves
for the equilibria involving gas hydrates. Of these the
most important are the ones involving the (L-^-H-Lg),
(L^—H— V), and the (H-V-Lg) equilibria. Their space
curves may be traced in Figure 12 . Other equilibria may
be followed on Figure 12 by following the general desig
nations used and through the use of Figures 10 and 11 .
The presentation of complete phase relationships
immediately becomes much more complex when a third com
ponent is added, in fact, three dimensions are then
needed to represent a single isotherm or a single isobar.
An understanding of simple binary systems can be applied
to special cases approaching binary systems and indirectly
applied to the understanding of complex systems. Quite
frequently, the application of the phase rule and phase
equilibria principles to a limited amount of data will
enable predictions to be made intelligently for conditions
not covered by experiment.
- 39-
8000
. _ 6 0 0 0 _ PSIA '
5000
3 2 0 6 PSIA
WATER CRITICA
3-P H A S E
IO O O C R IT IC A L
PSIA
PROPANE
CRITICAL
82. 8_ PSIA _ n
p __
-----------------------
9.0 PSIA
1.0 P S IA
NOTE: SEE TEXT FOR

PHASE DESIGNATIONS
(0 .0 8 8 ) > 0 .0 8 8 PSIA
- 400 -2 0 0 O 200 400 600 800
T E M P E R A T U R E ,°F
FIGURE 10 P R E S S U R E -T E M P E R A T U R E PROJECTION
CTM T U C P P A P A M F — M/ATFP QY^TF M
-40-
B
P = R * 0 . 0 8 8 P S IA P = P2 , 1.0 PSIA
800 800
UJ
UJ od
EJ 4 00 ^400
l- <
< ad
or UJ
LlI o. L .-V
CL l-V -L /
UJ
UJ
O V
I l 2- v
l 2- v
p-L* p-L‘
-400 -4 0 0
MOL % PROPANE 100 0 M O L % PROPANE 100
P = P3 , 9 .0 PSIA P = I 4 , 8 2 .8 PSIA
800 800
UJ
cd
=>
400
< > 1 -v
Cd
UJ r —-__
Q_
2 l 2- v
UJ
-4 0 0
O MOL % PROPANE 100
-4 0 0
-
O
-- i
L,
H
MOL % PROPANE
A P -L 2
p
100
2
FIGURE II TEMPER AT UR E -COMPOSITION DIAGRAMS

FOR T H E P R O P A N E -W A T E R S Y S T E M
AT S E V E R A L PRESSURES
-41-
P= R , 6 3 7 PSIA 3 2 0 6 PSIA
800
L .-V ll.
40 0 £400
Z>
P -L
-400 -4 0 0
0 MOL % PROPANE 100 0 M O L % PROPANE 100
P = P7 , 6 0 0 0 PSIA
800
CRITICAL
Li-
UJ
400
UJ
i—
P -L
-4 0 0
0 MOL % PROPANE 100
FIGURE II T E M P E R A T U R E -C O M P O S IT IO N DIAGRAMS
FOR THE PROPANE-WATER SYSTEM
AT SEVERAL PRESSURES
-42-
PROPANE-WATER
SYSTEM
.1
TEMPERATURE, DE6.F
LEGEND
PRESSURE SECTIONS'
P, • OjOSS PSIA
I.OPSIA
S O PSIA
0 2 .8 PSIA
P^ • 8ST PSIA
3 2 0 6 PSIA
• 0 0 0 PSIA
DESI6NATI0N OF L IN E S :
■ VISIBLE EDGES OF SOLID FIGURE
AND VISIBLE TRACES OF THE
TEMPERATURE-COMPOSITION SECTIONS
INVISIBLE PHASE COMPOSITION
LOCI OF THE SOLID FIGURE
INVISIBLE TRACES OF THE
TEMPERATURE—COMPOSITION SECTIONS
CRITICAL LOCI
FIGURE 12 ISOMETRIC DRAWING OF PROPANE —WATER SYSTEM

-U -3 -
THE SATURATED V.TA T E R CONTENT OF HYDROCARBON GASES AND
LIQUIDS
Several Investigations have been made to calculate
or correlate the saturated wat er content at high pressures
of "non-polar gases" such as nitrogen, hydrogen, methane,
ethane, and natural gases (3)* (28 ), (30)» (32).
The simplest relation expressing the saturated water
concentration in the vapor-phaee, which is generally valid
at l o w pressures for the non-polar gases is that
where y s mol fraction of water in the vapor at the

temperature of the system*
p° = vapor pressure of water at the temperature

of the system, and
P ss the total pressure of the system.
Equation (9) results from the use of Dalton* s La w of
partial pressure and Raoult's L a w (2 6 ), and the fact that
the liquid phase is substantially pure water.
Saddington and Krase (36) have found that at high
pressures, the water content of nitrogen greatly exceeds
the theoretical value as. predicted from the application
of P oyn tlng*8 Relationship (2 6 ). This may be interpreted
to mean that the effect of Increased pressure on the vapor
pressure of water is greater than predicted from Poynt lng 1e
Relation which is stated as follows:

dp _ V
3T ” v (10)
where p as the vapor pressure of water at the

temperature T,
P = the total pressure on the system,
V s the specific volume of the liquid at T,and
v * the specific volume of the vapor at T
Equation (1 0 ) is Integrated over a finite pressure range
to obtain the corresponding change in the vapor pressure
of water.
That the Poyntlng effect cannot explain the in
creased volatility of water wi th increased pressure at a
given temperature, indicates that the non-polar gases
actually have a solvent effect upon the water molecules
at high pressures. It is evident that the eame attractive
and intermolecular forces come to play at high pressures
in the "solubility of a liquid in a gas" as for the
solubility of a gas in a liquid.
Figure and •»the discussion of the data in the
section entitled "Experimental Data" show that the
volumetric behavior of the hydrooarbon-rlch phases is
related to the solubility of water In them. This suggests
a correlation whi ch is based upon the volumetric behavior
of the hydrocarbon-rich phases.
An empirical correlation in which the mol fraction
of water in the hydrooarbon-rlch phases is plotted against
the anhydrous molal volume of those phases for several
lit*
I
-U -5 -
isotherms is presented on Figure 13 and Figure 1U-. The
molal volume is expressed in cc/gm. mol and is obtained
from
where vm = the molal volume of the anhydrous hydrocarbon,
M ss the anhydrous molecular weight of the phase,

gnis/gm. mol.
d =s the density of the phase, gms/cc.
The effeot of molecular weight on the isotherms
is almost non-existent at high molal volumes (low
pressures); but become appreciable as the molal volumes
ap proach those of normal light hydrocarbon liquids.
All the experimental data used in the development
of the correlation are shown on Figure 13. The saturated
solubility of wa ter in methane was obtained from the work
of Olds, Sage and Lacey (30). The solubility of water
in ethane for 220 , 280 , and 310 deg. F were obtained from
the data of Reamer, Olds, Sage, and Lacey (32). The
ethane data of the latter for the 100 and 160 deg. iso
therms have been readjusted to account for the proximity

k
of those isotherms to the 3-phase critical of the ethane-
water system. The data on the water composition of the
hydrocarbon-rich phase for the systems propane-water,
n-butane-water, n-hexane— water, and methene-n-butane-
water have been plotted on Figure 15 to estimate the
3-phase critical composition of the ethane-water system -
used in the readjustment of the ethane— water data.

The solubility of water in propane was obtained
from this work, and the 3-phase data of the n-butane
water system from Reamer, Olds, Sage, an| Lacey ((33)
The raethane-n-butane-water data were obtained from ti/e
work of McKetta and Katz (29). The 3-phase points of
the l at ter have b een distinguished from the 2-phase

1
points in Figure 13, Additional experimental points
on the solubility of water in I90 molecular weight *'**

* •*i
kerosene (17) and 95 molecular weight gasoline (8)
appear on the correlation. The numbers opposite the 1*
methane-n-butane-water points Indicate the anhydrous
molecular weight of the phase.
Figure 13 has been cross-plotted to locate the
position of the curves for even values of molecular
weight up to a molecular weight of 70, Figure 1^•
Figure 5 shows that the solubility isotherms for
propane below the 3- P kaee critical temperature becomes
discontinuous at the 3-phase pressure where two hydrocarbon
rich phases of different water concentrations coexist.
This discontinuity does not appear in the isotherms of
Figure 13 because the molal volumes of these two co
existing phases differ in the same proportions as their
water concentrations. That is to say, that considered
on a molal volume basis, there is a continuity in the
solubility of water in the hydrocarbon-rich liquid and
vapor phases for temperatures below the 3—phase critical
as well as for temperatures above. The 230 deg. F iso— ||Sfc

therm for propane on Figure h and the 220 deg. F iso
therm for propane on Figure 13 may be compared to in
dict e that the inflection in the former has disappeared
in the latter.
The saturated vapor phase water content of com
plex hydrocarbon-water systems can be estimated from
this correlation to presrures very near to the 3-phase
critical to within 5^ the total water concentration
in that phase. The solubility of water in the 3-phase
hydrocarbon-rich liquid phase cannot be predicted with
the same degree of success. Here, the maximum error,
which iB again to be expected in the 3-phase critical
region, is about 2o£ of the total water concentration in
that phase. The predicted value for this region is about
20^ lower than the actual concentration.
The use of the correlation 1b predicting the water

content of the compressed lighter liquid phase, i.e., well
within the 2-phase region, is quite satisfactory as the
calculated points on Figure 13 indicate. The water con
tent of saturated, hydrocarbons at temperatures other
than those plotted on Figure lH- can best be obtained by
a cross plot of log composition versus T, or l/T, holding
the molal volume and the molecular weight constant.
The use of Figure 1 *J- presupposes a knowledge of the
phase density and the phase molecular weight of the an
hydrous hydrocarbon-rich phase under the equilibrium
conditions. MoKetta (29) has shown the effect of water

-U-8-
on the vapor-liquid equilibria relationship of the
methane— n-butane system. Since such data are generally
unavailable, the calculation of phase compositions, if
there should be two coexisting hydrocarbon-rich phases,
should be made by the conventional method (U-3) for cal
culating the coexisting phases using suitable equilibrium
constants for the system (k), (15)# (X9), (37).
The vapor phase densities may be calculated by the
law of corresponding states (5)* The liquid phase den
sities may be calculated by the method of apparent specific
weights (5) or by the method using the partial molal

volumes of condensed hydrocarbons (38).
y-
v_~ ^2 Lu
Uj CO
c c o c
5 00 CO a
-*~ < Uj
U.' : CO
< £ *— »—
2 <
CT CO
_J <
o £
i_
O <
o C
o o
o
^JS
CL
>
o - ZL
O LU f—
LC ^
A
n '
X
_u CD
O o
CD UJ o ^ ___1
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^ _J u_
c O
_J
o 1—
UJ
o
o
ITS'
cr
UJ
h- <
ro
CXL
ZD
O
30NO0 m
Will
y -w n
{/) 00 0
02 0J
Oo 0 <
ItJ
4 0 0 00
NOIlOVHd 10W NOayVOOHQAH Nl N31VM JO NOIJM N30NO O

IS)
1
0
Q.
2 III
f t
i s
h. 51
?o
12
%
hL
10
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52
Sk, z"
ViVT
0(0
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K(0
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o o o
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N0I10VH310W 'N09HV00HGAH Nl M M JO N 0IM N 3Q N 0G
-51-
H Y D R O C A R B O N -W A TE R WATER
SYSTEMS
C,-C
cr
LU
z
o
cr
LL
.001
C2 (ESTIMATED)
10002
100 200 300 400 500 600 700
3 - PHASE CRITICAL TEMPERATURE, °F
IGURE 15 COMPOSITION OF THE HYDROCARBON-RICH
PHASE AT THE 3 -P H A S E CRITICAL CONDITIONS
T H E R M O D Y N A M I C A NAL Y S I S OF T H E S O L U B I L I T Y OF PURE
HYDROCARBONS IN W A T E R
Success ful methods of c a l c u l a t i n g the s olu bil ity of
sl ig h t l y soluble ga ses In w a t e r at h i g h or» seu re from low
p r ess ur e s o l u b i l i t y data and the t h e r m o d y n a m i c data of
the p u r e gas at high ore ssuras h a v e been developed.
K r l c h e v s k y and K a s a r n o v s k y (2 0 ) u t i l i z e d the f u g a c l t y data
of com pre s s e d nit rogen and the a t m o s o h a r l c solubi lit y data
of ni tr o g e n in w a t e r t o ' c o m o u t e its s o l u b i l i t y from 2S deg.
C to 100 deg. C u p to p res sur es of 1000 atmospheres. The
agreement of t h e calculated values w i t h the experimental
Is excellent. T h e y repeated the calcu lat ion s f or similar
data on h y d r o g e n for several isotherms fr om 0 deg. C to
100 deg. C u o to 1000 atmosph ere s with enual success.
Wl ebe and G a d d y (^-6), (^-7 ) co mou ted the solubi lit y
of carbon d i o x i d e In w a t e r from 12 deg. C to 100 deg. C
for pressures uo to J O O at mosp her es w i t h fair success,
using the t h e r m o d y n a m i c data of carbon d i o x i d e o v e r the
range of conditions. The equation d e v e l o p e d b y Krlchevsky
and K a s a r n o v s k y and the equation u s e d b y Wlebe and Gaddy
are d e r i v e d and discuss ed. The equation In the form p r e
sented b y K r l c h e v s k y an d K a s a r n o v s k y Is applied to the
fo llowing study.
-5 3 -
Derlvstlon of W l e b e e nd Q-addy:
Wi e b e and G a d d y (U-6), (U-7 ) d e v e l o p their equation
aa follows:
The g e n e r a l eq uat ion for a b i n a r y isothermal system
with two p h a s e s in e q u i l i b r i u m is given by:
where an<^ F 2 ° r,? ^îal ^ ola l free energies of the

carbon d i o x i d e in the liquid e.nd gas phases, respectively.
P, is t h e p res s u r e , and
N.p and ^ r e the c o n c e n t r a t i o n s of carbon dio xid e
in the liquid and gas phases, respectively.
Since
and b y d e f i n i t i o n
and dNp — Npd In Np (15 )
poufltion 12 b e c o m e s
d In f, d In f^
VpdP + RT k l dNg v ^ d P + RT £1 £!& (1 6 )
d In N d In N'
-55-
vhere the v'» end *he f's are the partial wlfll volumes and Kasarnovsky (20) is rederlved here in a slightly different
fugaclties
of cprbor: dioxide in the two chases. manner, Combining equations (17) and (111)
Since we m defiling with e dilute solution of RTd In ?2 = 72dP (19)

cerbon dioxide in the liquid phase, at constant tpmpera-
whloh may be integrated at constant temnerature, under
ture and cressur*
the suoposition that v2 is independent of pressure and is
d In ?2 = d In (17) Ref, (2g) unaffeoted by the small ohange in N2 with orsssure.
and since the concentration of carbon dioxide is almost tf

2
RT JH-t, dP
unity, 5 is small relative to so that ecuation 16
*2 2 •
reduces to:
mlves In -2. = ~ (P - P )
dP (IS) js RT
RT 2
solubilities o' carbon dioxide in water at 27 where 7^ is the partial molal fugacity of the solute gas
atmospheres for several t9!?i)eratur?s were used as refer at the saturation pressure of water,
ence points in the integration of equation (IS) to compute For an infinitely dilute solution Henry's Law (26)
the solubilities of carbon dioxide in water for several
(22)
isotherms uo to 700 atm, Other data used in the integration
epolies, so that ecuation (21) becomes
of ecuation (IS) were the volumetric properties of carbon
log L l o g H (2?)
dioxide and the molal volume of carbon dioxide dissolved 7 2.707 RT
in water at atmospheric conditions, The calculated solu
Ecuation (21) has been rewritten as
bilities for the isotherms at 50 , 75, end 100 deg, (1
1°K log K 1 + — - - M
were generally lower than the experimental ones by 1 to \i N2 2,707 RT
of the solubility, the greatest deviation ocourring at by setting log K 1 = log I - -J l L . , By combining eoua-
2.1C7RT
the highest pressure,
tlons (17) and (lb) with ecuation (13), the latter may be
Method of Krlchevsky end Kasarnovsky: converted into the form of ecuation (2b), Ecuation (2b)
The final equation derived by Krlchevsky and was applied to the study on the solubility of cure
i
mm
-5 6 -
hydro c p rbons in water. The terms of equation (2 k ) are

redefined as f o l l o w s ;
= the fugsclty of the solute gas, psla,
the mol fraotion of solute in the water-rioh

C
VJ
liquid phase,
K1 =r the modified Henry's Law conatant,
V2 the partial molal volume of the solute gas

dissolved in the water-rich phase, ou.ft./lb.mol,
P = pressure, psia,
R r= gas constant, 10.73, and
T = the absolute temperature, °R
Krlchevsky and Kasarnovsky (20) computed the solu
bilities of nitrogen in water at 25, 50, 7 5 , and 100 deg. C
and of hydrogen in water a.t 0, 25 , 5 0 , and 100 deg. C up to
1000 atm. pressure. The agreement of the computed solu
bilities with the experimental are exceptionally good with
the greatest deviations less than 1% of the total solubility,
and in roost instances the deviations are within the range
of accuracy of the experimental measurements.
Application of the Method of Krlchevsky and Kasarnovsky to

the Systems. Methane—weter, Ethane— weter, and Propane—water
The partial volumetric properties of dissolved hydro
carbons in water were not available to permit a direct
calculation of the solubility of the pure hydrocarbons in
water. Therefore, the existing thermodynamic data for the
pure components and the vapor-llquid enullibria data for the

-5 7 -
binery hydro c p rbon-water systems were epplied to compute

the cherpcterist 1c ipothermal oonstents, K's pnd ^ ' s ,
for the systems methane—we.t °r, ethane—wetpr, end propane—
water.
Since the concentrations of water in the hydrocarbon-

rich phese8 ere quite smell, or become large only at rela
tively low pressures, ideal solutions may be assumed. Then,
the fugaoity of the hydrocarbon, f^, in equation (2U-) may
be estimated from
*2 = ^2y2 (25) Ref* (26)
where f£ = the fugaoity of the pure hydrocarbon at the

equilibrium pr es s u r e and temperature, and
Y2 = the mol fraction of h y d r o ca rbo n in the h y d r o

ca rbo n-r ich phase.
The concentration of w a t e r in the dew point gas for
the m ethane— w e t e r system (30) end the ethane— w e t e r system
(3 2 ) were ob tained from the date of Sage and Lacey and
ap pli ed in equation (2 f>). The fugecity date of the pure
hydrocarbons methane, ethane, and o rop pne were obtained
from the date pr ep a r e d by Sage and Lacey (3 9 )* The con
centration of w a t e r in the propane— rich phases and the
solubility of pr opane in w a t e r w ere obtained from this in
vestigation. The solubility of methane and ethane in
w^ tar were obtained from the works of Culberson, Horn, and
McKetta (9) and Culberson and McKetta (1 0 ), (1 1 ).
The modified Henry's Law constant, K', and the

partial molal volumes of the dissolved hydrocarbons were
Jptllly'
-58-
determined by en isothermal plot of "log ZjL " against

2
? 7ft3~E[T * ^he from which the constants for the
three systems were determined are shown on Figure 16 , 17 ,
ISA and l g B . For any given isotherm, v 2 , the slope of
the isotherm,was found to be substantially constant with
some scattering of the points at the lower pressures.
The greater inaccuracy of the experimental solubility data
at low pressures and the higher water concentrations in
the hydrocarbon-rich phase at low pressures may account
for the increased deviations. With increased wa ter con
centrations in the hydrooarbon-rlch phase, the assumption
of ideal solutions in that phase probably loses its validity.
Equation (2 *0 , however, is found to be a very sensitive re
lationship, and what appears to be serious deviations from
a straight line on Figure l6, 17 , and IB are produced by
relatively small changes in the values of Ng, the concentra
tion of hydrocarbon in the water-rich phase. The results
show that the agreement between the graphically smoothed
experimental data and the thermodynamically smoothed data
for the solubility of the hydrocarbons in water is sur
prisingly good, as may be seen from Tables 9 , 10 * and 11 .
It should be mentioned that the thermodynamic calculations
were made using the graphically smoothed experimental data,
so that the thermodynamio smoothing is not an Independent
operation. In addition, the fugaoity of the hydrocarbon

-5 9 -
in the solution, f 2 , calculated from equation (?9) has
"been assumed correot in obtaining the smoothed values from
equation The application of the same calculations
to the original experimental points presents a possible
means of smoothing the data Independently. In view of
the assumptions made in the derivation of the thermodynamic
equation, an independent smoothing of the data was not felt
to be Justified.
The calculated solubilities of propane in water for
pressures from 3000 to 10,000 psla are Included in Table ,

7T .
The validity of the extrapolation is supported by the
thermodynamic calculations made on the methane— water and the
ethane-water systems up to 10,000 pel. Both of the methane-
wster and ethane-water show a remarkable

% isothermal con-
stancy of v2 throughout the pressure range from 1000 to

10,000 psi.
Since the isotherms of Figures 17 > IS, and 19 yield
straight lines, it appears that v2 , the partial molal
volume of the dissolved hydrocarbon, for a given temperature
is Independent of pressure, at least at high pressures.
Though this is mathematically the case, this may not be so
as far as the Internal constitution of the solution is con
cerned. It must be remembered that v 2 v/as determined by
the integration of equation (19) with the supposition that
v2 was independent of the change in concentration of the
dissolved hydrocarbon from zero to the saturated

-6o-
concentretion. Primarily v2 is to be considered as a
quantity defined in terns of other and directly measurable
quantities, and as a quantity of practical Importance in
thermodynamic calculations. In this respect, a question
was raised as to the constancy of v2 over the pressure
range when an attempt was marjp to use it to calculate the
density of w a t e r saturated with hydrocarbons at high p res
sures in the following section. The assumption of ideal
solutions in the water— rich liquid phase may not be valid,
so far as the density calculations are concerned.
Figure ip gives the plots of modified Henry's Law
constants, K', <>0 p function of temperature for the solu
b i l i t y ‘of methane, ®thane, -propane, hydrogen, and nitrogen
in water. The partial molel volumes of the same pure con
stituents dissolved in water are plotted as functions of
temperature in Figure 2 0 . In Figure 20 , no explanation has
been found to explain the trends of the curves for ethane
and propane, both of which exhibit maxima. The maxima can
not bp associated, even qualitatively, with the criticals
of qure ethane, since the maximum for ethane occurs at
shout 31 C deg. F as compared to 200 deg. F for propane.
The Inability to predict v 2 for the individual hydrocarbons
is not completely discouraging because v2 need not be de
termined with gre^t accuracy for calculations at low and
moderate pressures, e. g. up to 2000 pal, for under these

-61-
ccnditlons the dexîationr from. henry's Law which Is oon-

11 TT P ”
tributed by the term ... _ .2 ip generally Fmell.
T .303 R t
Sufficient date on the solubility of hydrocarbons
in water at low pr^SBur^s are not available to permit a
genprsl relationship for estimating Henry's Law constant.
However, the Henry's Law constants presented and discussed
here do follow similar trends and indicate their similarity
for gnseB of widely different critical conditions.
The maxima in the curves of Figure lb are associated
with the appearance of the isobaric minimum solubilities
discussed on pp 80.
The thermodynamic calculations show thr-t the solu
bility of pure light hydrocarbons can be predicted from
accurate atmospheric solubility data, the partial molal
volume of the hydrocarbons dissolved in water, the volumetric
behavior of the pure hydrocarbons at the elevated pressure
conditions, and the concentration of the hydrocarbon in the
solute-rich phase. The latter may be determined accurately
through the use of the generalized plot of the water content
of saturated hydrocarbon llaulds end gases given in Figure
1U-.
Unfortunately, the partial molal volumes of the
hydrocarbons dissolved in water ere extremely difficult to
determine by direct measurements. There remains, however,
the possibility of obtaining the partial molal volumes
-62-
ir.d ir^ct ly es In the present snelysls. A few experimental

values of tha solubilities nf hydrocarbon in water accurately
determined at arch temperature ov^r a moderate pressure
r m g ? will provide the necessary information to predict the
solubilities at higher pressures. No accurate data on the
solubilities of complex light hydrocarbon mixtures in water
on which the thermodynamic calculations may be made are
available.
These calculations provide a method for smoothing
the experimental date thermodynamically. The assumptions
which are necessary to make the calculations appear to be
most valid r t high pressures. The comparison of the ex
perimental data vrith the thermodynamically smoothed data
indicate that graphical smoothing of the data is preferred
to the thermodynarric smoothing of the data excepting at
high pressures.
-63-
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- 60 -
M ETH AN E-W ATER SYSTEM
340°F
100 °F
2.303 RT
FIGURE 16 PLOTS FOR THE DETERMINATION OF CONSTANTS IN THE THERMODYNAMIC EQUATION

FOR THE SOLUBILITY OF METHANE IN WATER
6.6
-69-
ETHANE-W ATER SYSTEM

6.5
6.4
6.3
6.2
A
6.1
D
0
\0°
6.0
0 100 °F
A 160 "F
59 0 220 °F
280 °F
0 340 “F
5.6
2303RT
FIGURE 17 PLOTS FOR THE DETERMINATION OF CONSTANTS IN THE THERMODYNAMIC EQUATION
FOR THE SOLUBILITY OF ETHANE IN WATER
-7 0 -
190 °F
160 °F
130 °F
o 100 °F
o
j
100 °F
130 °F
160 °F
190 °F
P
2.303 RT
FIGURE 18A PLOTS FOP THE DETERMINATION OF CONSTANTS IN THE THERMODYNAMIC EQUATION
FOR THE SOLUBILITY OF PROPANE IN WATER
280
310
0 .02 .04 .06 .08 .10 12 ■16 .18 .20 .22 .24 .26
2.303 RT
FIGURE 18 B PLOTS FOR THE DETERMINATION OF CONSTANTS IN THE THERMODYNAMIC EQUATION

FOR THE SOLUBILITY OF PROPANE IN WATER
NITROGEN
6 .7
CONSTANT
6.6
HYDROGEN
LAW
6 .5
DIVIDED SCALE
HENRY'S
PROPANE
6.0
MODIFIED
METHANE
K',
LOG
5.8
5.7
50 100 150 200 250 300 350
TEMPERATURE, °F
F IG U R E 19 M O D IF IE D H E N R Y 'S LAW CONSTANTS

FOR T H E S O L U B IL IT Y OF P UR E L IG H T
H Y D R O C A R B O N , H Y D R O G E N , AND NITROGE
IN WATER
GASES
vv-ruuivic. ur UlSbULVED
CU. F T ./L B . MOL
1.0
ETHANE
0.8
j
t METHA
J 0.6
- O
N IT R O G E N
j
L
0 .4
HYDROGEN
0.2
50 100 150 200 250 300 350
T E M P E R A T U R E ,°F
F IG U R E 2 0 PARTIAL M O LA L V O L U M E S OF
PURE HYDROCARBONS, HYDROGEN, AND
N ITR O G E N D IS S O L V E D IN W A T E R
- 74 -
CALCULATIONS OF THE. EFFECT OF DISSO LV E D HYDROC A RB O N

G AS E S ON THE D E N S I T Y O F W A T E R AT HIGH PRESSURES
The partial molal v o lu m e of the pure hydrocarbons
d is s ol v ed in w a t e r has been applied to oaloulste the effect
of d i s s o l ve d hyd rooerbons on the de n sity of water. The
computed densities h a v e been compa re d with the experimental
densities of w a t e r saturated with a natural gas un d er pres
sure. T h es e experimental densities were obtained b y Dodson
and Standi ng (lU-) for several isotherms up to 50 00 psl.

«
The composition of the na tu ral gas, its solubility In water,
the experimental d en s ities and the calculated de nsities ere
listed in T a b l e 13.
Dodson and St anding did not determine the phase
compositions. Since th e natural gas was pr e do m i n a n t l y
methane, the concentration of each constituent in water is
taken to b e p r o p o rt i o na l to its concentration In the orig
inal gas. B y applying the law of additive volumes, the
specific v o l u m e o f the mixture, V, was calculated from the
fo llowing relati o n sh i p (2 7 ):
V = v1x1 + v^Xg + v^x-j + vj|X^ (26)

w here subscripts 1, 2, 3, and *!■ designate water, methane,
ethane, and pr o pane and h e a v i e r mo l ec u la r weight h y d r o
carbons, respectively. The v ’s d enote the pa rt ial molal
volumes, and the x's d enote the concentrations. Since

- 75 -
all the concentrations encountered were less than 0.000*1-
mol fraction hydrocarbon, v-^, was taken as the specifio
volume of pure w at e r at the saturation temperature and

preseure.
The oomouted and experimental densities for the

water solutions and the densities for oure water are
clotted for isotherms et 100, 150, 200 , and 250 deg. F
up to 5000 psi In Figure 2 1 . In general, the agreement
between tbe experimental and the computed densities is
good up to 3000 psi. With increased pressure the de
viation inoreaseB until at 5000 osl, the calculations
are Only able to account for 6o^- of the density decrease
resulting from the solution of the hydrocarbons in the
water.
It may be recalled that Figures 16, 17, and IS
show that the slopes of the isothermal curves from which
the hydr ocarbon v's were determined are most representative at
high pressures. Contrary to this observation, is the
observation that the deviations between the experimental
and calculated densities of water saturated with hyd ro
carbons increase wit h pressure. Hence, the values of v's
w hich describe the v a por-liauld equilibria relationships
best, I. e. at the high pressures, are the poorest in
describing the volume ohanges caused by the solution of
the hy drocarbons in water.

- 76 -
There 1 b a further ooint of Interest. At high
pressures, the deviations between the experiment el end
calculated densities ere in a direction which indicates
that the partial molal volumes of the hydrocarbon in
crease with increasing pressures. Although the present
investigation should not be taken as a conclusive evidence
of this astonishing fact, beoause of its limited treat
ment, the partial molal volumes of some substances have
been known to Increase with pressure at constant tempera
ture and composition (l). There also remains the likely
alternative that the partial molal volume of âter, v-^,
undergoes a change under the elevated pressure conditions.

-7 7 -
table xiii
Compo sition of Natural Gas A, Solubil ity of

Natural Gas A in Water, an d Comparison
of Experimental and Calcula ted Densities of
Wa ter Sa t urated wi t h Natural Gas A
(A)
Com position of Natural Gas A:
Constit uents Mol Fraction

Me thane O . 885 I
Ethane 0.0602
Propane 0.0310
Isobutane 0.0046
Normal Butan e O.OO 85
Is opentanes & He avier 0.00Q8
1.0000
G ra v i t y = 0 . 6 55
(B)
Solubi l it y of Natural Gas A in Water:
Pressure T emperature °F
100 150 200 250
psla Mol Fraction Gas in Liquid
1000 .00121 .00106 .00100 .1
2000 .OOI 87 .00162 .00164 .1
3000 .00238 .00206 .00209 .<00219
4000 .00275 .00238 .00244 .100258
5000 .OO 3 O 9 .00262 .00272 .1
O CO O OMTNCO
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- 79
-
1.02
NATURAL GAS-
LOI WATER SYSTEM PURE
WATER
CALC.
E X P T 'L
1.00
PURE
WATER
CA LG.
.9 9 E X P T *L "
.98 PURE
WATER
CALC.
DENSITY, GMS./CC.
E X P T 'L
.9 7
.9 6 PURE
WATER
CALC.
E X P T 'L
.9 5
E X P E R IM E N T A L DATA FROM
.94 DODSON AND S T A N D IN G (1 4 )
IOOO 2000 3000 4000 5000

P R E S S U R E , P S IA
F IG U R E 21 E X P E R IM E N T A L AND CALCULATED
NSITIES O F WATER SATURATED WITH NATURAL GAS
«
-80-
T HE I N TE RRELATION O F MI Y IM UM SOLUBILITY, H EN RY'S LAW

AND T H E V O L U M E T R I C B E H A V I O R OF THE SOLUTE-RICK PHASE
The p h en o me n on of m inimum isobario solubility has
been wi d el y reported end discussed for various systems b y
8 everrl authors (g), (P), (10), (36), (U-6), (*J-7). Keunen
(21), (22) appl ied his u n de r st a nd i ng of the b eh a v i o r of
b i n a r y mixtures in the critical .retion to predict the
ex istence of e region of m i ni m u m solubility.
Aroyan (2) has d i s c u s s e d isobnrlo minimum solubility
on a g e neral basis by Inte rrelating it with reverse solu
bility, ma x i m u m solubility, and isobaric retrograde con
densation. M i ni m um isobaric solubi l it y is said to occur
when the concentration of a solute in a solution under
goes a m i n i m u m at some temperature. In reverse solTibility
there is an increa se in th® s ol u bi l i t y of the solute with
temperature. Ma ximum solubility occurs when a relative
m aximum appears in the isobaric s olubility curve at the
point where there is a transition f r om reverse solubility
to norm al solubi lity w it h increased temperature.
Aroyan's conclusions m ay be summarized as follows:
(1) that reverse so l ub i li t y always occurs whenev e r

min i mu m solub i li t y occurs,
(2) that the o cc u rr e nc e of reverse solubility does

ngt n e c e s s a r i l y mean that a minimum solubility
exists for some lower temperature, (there re
ma ining the p os s i b i l i t y that a third phase is
encountered b e f o r e the minimum sol ubility
occurs, as In the h y d r og e n- n — but ane system).
-81-
(3) that a m a x i m u m 3n the bubblp point cotT^pponrlfl

to a minimum solubility, hence reverse solu
b i l i t y end m i n i m u m solubility may b e expected
in oertain regions of the phase di agrem'for all
two component systems,
(U) that a mi n im u m in the b u bble point c u m m cor

responds to e m a ximum in the solubility curve,
(5) that the region of reverse solubility is in

creased as the extent of the h ubble-rolnt-dew
point envelope in the critical region is in
creased ,
(6) that a region of reverse solubility is a region

of isobario retrograde v a p o r i z a t i o n .
The phenomenon of min imum solubility may be illus
trated g e o m et r ic a ll y b y the w a y in whi ch the solubility
Isotherms cross on a p r e s s u r e — compos ition diagram for a
b i n a r y system (2). T h e same approach may be extended to
relate m i n i m u m and m ax i mu m solubility to Henry's Law and
to the v o lu m et r io b e h a v i o r of the so lute-rich phase.
Figure 19 shows that the Henry's Lav oonstants, K, for
pure non p o l a r gases, such as those treated h er e,increase
with increasing temperature, go through a maximum, then
decrease. These three sections of the curve are to be
d is c us s ed in relation to minimum and maximum solubility.
F o r K de c re a s i n g w i t h increasing temperature, either

✓
a m i n i m u m Isobaric solubility, Figure 22A, or a maximum
Isobaric solubility. Figu re 22B, can occur, depending on
the ma nn er in which the lines o r the isothermal elements

N
of the sur face cross. The mi nimum solubility exhibited
-62-
by me t h a n e in w a t e r high temperatures and low pressures
illustrated in Figure 2 2 A is of this type.
F ig u re 2 2 A end °2B h«v« been drawn showing the
system to ob ey H e n r y ’s I.aw, however, non-idenl behavi or
in the s o l u t e - r i c h p h a s e give the seme relative crossing
of the lines to oroduoe r'lniraum solubility for some tem
perature end maximum s ol u bi l it y at some h i g h e r temperature.
For the region in w h ic h K increases with t e m p e r a
t u r e , however, i t is n ec e ss a ry that the s olute-rich phase
b e h nve as a n o n — i d e a l g P s in o r d e r to pr od uce a maximum or
minimum s olubility as nay b e sên from Figure 2 3 A and 23B.
The effect of non— ideal b e h a v i o r of the solute-rich phase
on the isothermal solubi li t y curves is illustrated, most
clearly in Figure B.
Finally, there remains the case in w hi c h H e n r y ’s
Law constants undergo r ma x i m u m value. In this case,
Figu re 2h, if ideal pas b eh a v i o r is assumed In the solute-
rich phase, the mi n i m u m .solubility is produced at the
temperature where K un dergoes a maximum.
Thus, the ex istence of ma x im u m solubilities may be
p r e d i c t e d o u a l i ta t iv e ly from the solubi l it y data obtained
at a tmospheric conditions e nd the v olumetric b eh a v i o r of
the so l ut e — ri oh phase > which, for the h y d r o c e r b o n — vater
systems can be estimated from the volumetric be h avior of
t he anhydrous solute.
-83-
P = R
Q.
2
O
O o
o
PRESSURE TEMPERATURE
M IN IM U M S O L U B IL IT Y
T, < T> < T P* Po
cn
o
o.
o
o
0
M A X IM U M S O L U B IL IT Y
F IG U R E 2 2 M IN IM U M A ND MAXIMUM S O L U B IL IT Y
FOR H E N R Y ' S LAW C O N S TA N T DECREASING
W IT H T E M P E R A T U R E
-84-
T, < To < T, p=p3
CO to V
O o I
CL CL
2
O o
o o I
M IN IM U M S O L U B IL I T Y
M A X IM U M S O L U B IL I T Y
F IG U R E 2 3 M IN IM U M AND M A X IM U M SO LU B ILITY
FOR H E N R Y 'S LAW C O N S T A N T INCREASING
W IT H T E M P E R A T U R E
T, < T* < TV P= R.
COMPOSITION
• cn
o
O
M IN IM U M S O L U B IL IT Y
FIGURE 2 4 M IN IM U M SOLUBILITY FOR T H E

T E M P E R A T U R E REGION OF MAXIMUM
H E N R Y 'S LAW C O N S T A N T
PART II
EXPERIMENTAL EQUIPMENT, PROCEDURES, AND TECHNIQUES
FOR THE DETERMINATION OF PROPANE-WATER
VAPOR-LIQUID EQUILIBRIA RELATIONSHIPS
-86-
EXPERIMENTAL EQUIPMENT
Th e experimental pquipmftnt used in this work con
sisted of the fo l lowing basic units:
(1) p h i g h Pr e ss u re vepor- ll q ul d enullibria

arparfltus,
(2) an analy tical train for the analysis of the

h y d r o c a r b o n — rioh phases,
(3) an apparatus for the analysis of the water-

rich phase, and
(U-) a souroe of h i g h p re s s u r e mercury used for

ch arging pnd sampling operations.
Sc hematic f l ow diagrams of each unit is presented in
Figures 25, 26, 27, and 28, respectively.
V ap o r Ljould Equilibria A p p a r a t u s :
The h i g h p r e s s u r e equilib r iu m cell used in this in
vestigation was co n st r uc t ed b y Ohaddook (7). The vapor-
liquid equilibria apparatus u se d was const ructed b y MoKetta
and has been t h or o ug h ly d i sc u s s e d b y him (27). Some re
vi sions of the apparatus ha ve be en made b y the author In
o r d e r to adapt the equipment to the study of the propene-
w a t e r system. Only the de t a i l e d di scussion of the revi
sions are given hero, otherw ise the r e ader is referred to
(2 7 ) for d e t a i l s .
The oell was ma c hined from a forged steel billet and
de signed f or a p r es s ur e of 5000 osl. Its net capacity is
a p p r o x i m a t e l y 1000 cc. The oell was constr uc t ed with a
J e r g u s o n - t y p e w i n d o w so that the relative quantities of

-8 7 -
the coexisting phases could ho obs°rvRfl. A th e rm o staticslly
c ontrolled air b a th surrounding the oell served to maintain
it at thermal equilibrium.
Phese equilibria were'socomplished by means of an
eleotricslly powe red stirrer mounted entirely within the
cell. A midget induction motor powers the Impeller which
rotates within a closely fitting steel conf ining tube. The
h ea v i e r liquid phase is lifted in this tube to the top of
the oell b y the action of the impeller and dropped through
the hy drocarbon phase or phases. In order to minimize the
lo calized h e a t i n g b y the induction motor, it was operated
intermittently b y an electronic on- off timer.
The induction m o t o r us e d was a KYAB 2115 (10V —60
cycles A.C.) v a cu u m Impregnated motor manufa ctured by the
Barber— Oolraan Company of Rockford, Illinois. The metallic
surface b ea r in g s w e r e rep laced b y the b a ll bearings in
order to mi n im i ze the friction. No lubrication was used
In the motor d uring operation. The Impeller b e a r i n g was
ma chined from s'niece o f soft Iron Oil ite obtained from
the Amplex Division of the Chrys ler Corporation in Detroit,
Michigan. The stirrer arrangement was a source of con
siderable difficulties.
Ports located at U different and appro priate posi
tions in the cell were u se d for charging, sampling, and
d is c ha r gi n g the contents of the oell. Figure 25 gives a
flow d ia g r a m of the apparatus showing the relative positions

-86-
of t he s a m p l i n g ports, the a u x i l i a r y valves, the gauges,
and the f l o w lines.
T he v a p o r p h a s e s a m p l i n g line, V - T ^ — 16, was w r a o p e d
w i t h a r e s i B t n n c e h e a t e r in o r d e r to s u pp r he a t the v a p o r
s a m p l e l e a v i n g th e oell. It was especially irrroortant that
the c o n d e n s a t i o n of the v a p o r p h a s e b e p r e v e n t e d w h e n
s a m p l i n g in the 3 “ Ph n 8 R region. T h e h e a t e r also h a s t e n e d
t he p u r g i n g of a n y excess w a t e r r e m a i n i n g in the lines
from previous runs.

I-
A n a l y t i c a l Tr a in f o r the P r o p a n e — Rich P h a s e s :
Th e f l o w d i a g r a m f o r the a n a l y t i c a l train used in
t he a n a l y s i s of the h y d r o c a r b o n — rioh p h a s e is shown in
F i g u r e 2 6 .. W it h th e e x c e p t i o n o f th e b l o c k n e e d l e valves
A and B and t he r u b b e r t u b i n g c on n ec t io n s, the entire
train was c o n s t r u c t e d of glass.
A glass case w a s p l a c e d a round the d e h y d r l t e — filled
U— tubes to pr event d us t f r o m s e t t l i n g on the tubes. A
m e r c u r y b u b b l e r p l a c e d d i r e c t l y b e h i n d the U — tubes served
t o i n d i c a t e th e s a m p l i n g rate. The r u b b e r t u b i n g connections
p r e c e d i n g t h e U — tubes w e r e s p e c i a l l y p r e p a r e d to prevent the
absorption of w a t e r f r o m t h e a t m o s p h e r e . No f le x i b l e rub
b e r or plastic tubing impervious to t he d i f f u s i o n of w a t e r
c o u l d b e found. A s a t i s f a c t o r y m e t h o d of t r e a t i n g rubber
to p r e v e n t the d i f f u s i o n of w a t e r to l o w e r c on c en t ra t io n s
h as b e e n d e v e l o p e d b v P r eg l (3 1 ).
.
jsH
A wooden scale, c h e c k e d fo r a c c u r a c y b y means of
a h i g h p r e c i s i o n c a t h e t o m e t e r , was u s e d to m a k e t h e
manometer readings. A c a l i b r a t e d b o t t l e of 1 1 .56 l i t e r
c a p a c i t y was u s e d as a r e c e i v e r f o r the m e a s u r e m e n t of
the quantity of dried propane in t he sample. As 8 s a f e t y
precaution, a h e a v y w i r e g u a r d wa s p l a c e d o v e r t h e b o ttle.
The t e m p e r a t u r e of the gas w i t h i n the b o t t l e was regis
t e r e d on a c a l i b r a t e d t h e r m o m e t e r w h o s e b u l b x*/as l o c a t e d
in t h e c e n t e r o f b o t t l e M, F i g u r e 26.
A i r d r i e d b y p a s s a g e t h r o u g h an a s o a r i t e t o w e r and
t h r e e d e h y d r a t i o n t o w e r s was u s e d to f l u s h the train and
t h e U - t u b e s at t h e b e g i n n i n g and end of each run, Just
p r i o r to w e i g h i n g the tubes.
App a r a t u s f o r t h e A n a l y s i s of t h e W a t e r - R i c h Phase:
F i g u r e 27 is a f l o w d i a g r a m o f t h e a p p a r a t u s u s e d
f o r t he a n a l y s i s o f the w a t e r — r i c h phase.
The c o n c e n t r i c — t u b e c o o l e r w sa c o n s t r u c t e d of 1"
I.D. b r a s s t u b i n g U- f t . l o n g on t h e o u t s i d e and. a l / U "
O.D. b y 3 / 3 2 ” I.D. stainless steel tubing concentric with
t he b r a s s t ub ing. T he i nn e r t u b e s e r v e d to t r a n s p o r t the
s a m p l e t h r o u g h t h e cooler. W s t p r at s u b s t a n t i a l l y r o o m
t e m p e r a t u r e wa s u s e d as t h e c o o l i n g medium. T h e s am p l e
was e x p e n d e d to a t m o s p h e r i c p r e s s u r e t h r o u g h v a l v e S,
F i g u r e 27, l o c a t e d at t h e to p of t h e cooler.
I
- 90-
The p r e s s u r e in the bu rette was pie into ined ore-
clsely at the ba r om e tr i c value b y adjusting the mercury
lev e lling bulb. A scale wpb fastened to the side of the
v p t e r Jacket so that the w pt s r h e ad within the b ur e tt e
could b° measured and taken into account in the adjustment
of the levelling bulb. The b u rette was telescoped from a
100 cc gas burette to a 5F>0 cc bu r e t t e to give flexibility
in the seleotion of sample sizes. A glagg pyrex tube
equipped vrith the p r o p e r inlets and outlets served as an
isothermal Jaoket for the burette. Air was b le d into the
b o t t o m of the w a t e r Jacket to minimize the temperature
gradients in the a n n u l u s . A t h e r m o me t er placed in the
nnnuluB r egistered the t em p er a tu r e of the w a t e r in the
Jaoket.
/
Pressurizing and P r essure Maintenance U n i t :
The flow d i ag r am of the p r e s s u ri z in g and pressure ,
m ai n te n an c e eouipment is presented in Figure 2$. The
pre s s u r i z i n g unit, w h o s e b o u n d a r y is shown b y the dotted
line in Figure 2&, has been d i s c u s s e d at length b y Aroyan
(2 ).
The press ur i zi n g unit has b e en combined vrith an
auxiliary mercury chamber f o r use in charging and sampling
operations. High pressure me rcury obta ined from the com
pression unit is aocomvnnied b y a trace of oil. By using
the p r essurizing unit solely for the purpose of compressing

-9 1 -
nitrogen gas and combining its use with the auxiliary

chamber, absolutely clean mercury could be charged to
the cell.
-92-
0 - 1 5 0 OR 0 - 1 0 0 0 PSI 0 - 3 0 0 0 PSI GAUGE

GAUGE
EQUILIBRIUM
CELL
T T
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CO,
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■{j}— [ y P H i H js H g F 1 r 16
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i
TO T R A IN TO T R A IN
TO B U R E T T E "
F R O M M ERCU RY SO U R C E
FIGURE 2 5 FLOW S H E E T OF T H E V A P O R -L IQ U ID (g*

E Q U IL IB R IA A P P A R A TU S
<r
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THE
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( n i l I I II II II ll I I . fl II ll ■ I I I I ... ■ 1.1. I I n H I . I I I I . H . I ■ I. . I I I I I I I I I II. H i 1
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I V I I 1 1 I I I I'l l I 1 1 I I I I I I I I I 1 1 1 1 1 1 1 1 1 1 | | 1 1 1
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it i i t i it t it i
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cr
27
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- 3 0
AHVONOOg H1V9 o oc
ro •> OC 3 or
CD ZD
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PRESSURIZING
3m 4m
GAS RELEASE
r— BLOWDOWN
pi TO CELL AND C E L L -
^ CHARGING CYLINDER
TO W A TER -R IC H
T H T t X l i q u id s a m p le
L 6 - 5 - 6 J LINE
PRESSURIZING
U N IT "
A VARIABLE SPEED MOTOR H HIGH PRESSURE MERCURY

B SIMPLEX OIL PUMP J MERCURY-GAS CHAMBER
C OIL RESERVOIR M ELECTRICAL CONNECTORS
D OIL-MERCURY CHAMBER N NITROGEN CYLINDER
E PRESSURE G AUG E,0 - 3 0 0 0 PSI 0 PRESSURE GAUGE, 0 - 5 0 0 0 PSI
F PRESSURE GAUGE, 0 - 1 0 , 0 0 0 PSI P AUXILIARY MERCURY-GAS CHAMBER
G MERCURY CHARGING CYLINDER Q MERCURY CHARGING BULB
FIGURE 28 PRESSURIZING AND PRESSURE MAINTENANCE UNIT

- 96-
EXPERIMENTAL MEASUREMENTS
T e m p e r at u re Control and M e a s u r e m e n t :
The a i r b a t h s u r r o u n d i n g th e e qu i li b ri u m cell was
c o n t r o l l e d t h e r m o s t a t i c a l l y fo r all te mperatures above
r o o m t emperature. The s m a l l e r of two v a ri ables load re
s is t a n c e h e a t e r s in the a ir b a t h was oonnected to a
b i m e t a l l i c t h e r m o r e g u l a t o r w h i c h r eg u lated t he tempera t ur e
at the d e s i r e d level. F or t e m p e r a tu r es b e l o w r o om te m
p er a tu r e d r y ice ohips were d r o p p e d into t h e b a t h to m ai n
tain the t e m p e r a t u r e at a constant value.
The t e m p e r a t u r e of the cell was m e as u r e d b y means
of two ca l i b r a t e d o o pp e r- c o n s t a n t a n therm o co u pl e s inserted
well Into the walls of the e q u i l i b ri u m cell. The thermo
couples w e r e calibr a te d to 0.1 deg. F in a w a t e r ba t h and
in an oil b a t h w i t h h i g h pr e cision t h ermometers w h i c h are
p e r i o d i c a l l y calibr at e d b y the N a ti on a l B u r e a u of S t a n d a r d s .
The t e m p e ra t ur e of the oell d ur i ng the course o f a run did
not v a r y o v e r 0.3 deg. F up to 200 deg. F and 0.5 deg. F
f o r h i g h e r temp eratures. The E. M. F . 's of the thermo-
oouples w e r e me a su r ed wi th a Leeds a n d N o rt h r u p Hi gh
P re c is i on P o r t a b l e Potentiometer.
P r e s s u r e Control and M e a s u r e m e n t s :
The eauillbrlum pressures w e r e measured b y means of
steel tube ga ug es of the B ou r do n type. Gauges of the

-5 7 -
i
following ranges were used: 0—150 psi, 0— 1000 psi, and

0—3000 p s i . The Accuracies ere estimated to:be: it 1$ of
the readingB taken with the O— 150 psi gauge, 2/3$ of the
readings taken with the 0-1000 psi gauge, end 1/2$ of
the readings taken with the O— 3000 psi gauge.
W h i l e e q u i l i b r a t i n g an d sampling, v i t h the aid of
the p r e s s u r i z i n g and p r e s s u r e m a i n t e n a n c e u ni t the pressures
w e r e ma intained, in general, at a. g i v e n p r e s s u r e w i t h
v ar i at i on s not e x o e e dl n g the above m e n t i o n e d aocuraoles
of the g a u g e readings. For the runs co n ducted from 2000
to 2S00 psi, the pr e s s u r e d u ri n g sa mpling operati o ns was
m ai n ta i n e d w i t h i n 2 / 3$ of the enullibrlura pressure.
Analyt i ca l W e i g h i n g s :
All analytical we i gh i n g s w e r e made on Depart m en t al
B a l a n c e B l — 31 u s i n g a set of c a l i b r a t e d weights. The
w eights w e r e calibrated u s i n g the m ethod of transposition
(1+9 ).
T e m p e r a t u r e v ar i at i o n s in th e room were mi n imized
d ur i ng each run. A c o u n t e r p o i s e was us e d in m aking the
weighings of the U - t u b e to eliminate, as far as possible,
the b o u y a n c y and h a n d l i n g effects. It is b e l i e v e d that
the w ei g hings u n d e r t h es e conditions were made w i t h an un
cer t ainty not g r e a t e r than i 0.2 mg. of the recorded
values.
-9°-
O H O ’-'IC AL3 USED
PropenRi
The propane used in this investiget ion wps ob
tain ed fro™ the Phillips P e t r o l e u m of Bartlesville,
Oklahoma. The "Pure G r n d e Pro n a n a ” wee reported to con
tain not lees then °9 mol $ propsn®. The pr i nciple im
p ur i ti e s ere e p p r o x i m a t e l y 0.2^ ol* other hydr ocarbons,
m a i n l y ethane end lsobutene. The su l fu r content is
p r o b a b l y less then 0.005 w t . # end its v e o o r p re s s u r e at
60 deg. F is 123 psie.
B e f o r e ch a rging the p r o p a n e into the cell, it was
run t h ro u gh a h i g h p re s s u r e f ilter consisting of activated
carbon, ascarite, s o di u m hydroxide, and dehydrlte.
Distilled W a t e r :
T he d i s t i l l e d water, o b t a i n e d from the d e pa r t m e n t a l
source, was boiled se ve ral minutes p rior to us e and in
jected into the oell w h il e still ab o ve 160 deg. F.
Mercury:
Bp f o r e the m e r c u r y removed from thp cell was reused,
it was c l e a n e d and d r l ° d b y w a s h i n g it twice v'lth benzene,
then wi t h acetone, and f i nally b y reducing the pressure
above the m e r c u r y to a few millimeters u n ti l all b ub b l i n g
at its su r fa c e oeased. In case the m er c ur y did not present
a clean, scum— free surfacp, it was agitated in the presence

-9 9 -
of d i l u t e nitric acid .with an air s tr e am for 3 hours. The
m e r c u r y was then w a s h e d w i t h w a t e r and d r ie d as before.
By a combination of these procedures the mercury was main

tained in a clean, dry state.
- 100 -
EXP SRI MENTAL PROCEDURE
T he ex p e ri m en t al p r oc e d u r e was Improved and simpll-
fi ed b y r u n n i n g each p h a a e c o m p l et e ly b efore g o i n g on to
the next, b o t h in the 3 - P h a e e and the 2 - ph a s e regions.
T h e a ctual or d e r of the d e t e r m i n a t i o n s was:
(1 ) 3~ p h a s e region;
(a) v a p o r phase
(b) p r o p a n e — rich liquid phase
(c) w a t e r — rich— liauid ohsse
(2 ) 2— phase region;
(a) p r o p a n e - r i c h chas es
(b) w a t e r — rich liquid phase
This o r d e r was p e r m i s s i b l e since all the n e c e s s a r y re
s tricti o ns of the phase rule, c o n s t a n c y of t e m p e r a t u r e
and n u m b e r of c o e x i s t i n g phases for the 2— p h a s e region,
w er e co m p l i e d with d u r i n g each run.
C ha r g i n g and E q u i l i b r a t i n g ;
T he oell was e v a cu at e d and f l ushed several times
wit h p r o p a n e gas at the b e g i n n i n g of each series of iso
thermal runs and w h e n e v e r the cell was c o n t a mi n at e d wit h
o t h e r gases. The indivi du al constituents, pr o p a n e and
water, we re c h a r g e d into the oell in such quantities that
w o u l d sa t is f y the d e s i r e d conditions of pressure, t em p e r a
ture, n u m b e r of phases, and qu a n t i t y of each phase. The

- 101 -
last requirement was fulfilled so that each phase could be

sampled from its assigned port.
B e f o r e the b e g i n n i n g of the stirring operation the
liquid s am p l i n g lines were always filled with clean, dr y
m e r c u r y to d i s p l a c e any liquid present in them and to b l o c k
o ff the lines d u r i n g the a gi t ating period. The wateri-rich
p hs s e sa m pl i n g line was filled with m e r c u r y t h r o u g h valves
13— 1^— 15/ Fi g ur e 25, and valve S, Figure 27. The pr o pane-
rich liquid phase sample line was filled t hr ough I— T-l-2— Tg-
T^— 1 1 , F ig ur e 25. The content of t h e oell was br o u g h t to
e qu i li b ri u m u n d e r constant conditions of pressu re and tem
pe rature b y the agitation of the stirrer. The period of
agitation was from l-l/? to 2 hours. Time tests conducted
at the o utset of the study indicated this to be mo re than
sufficient f or at t aining equilibrium.
S a mp l in g of the P r o p a n e — Rich Phases in the 3-phase R e g i o n ;
During the sampling operation with 3-Phases present,

a state of exact equilibrium may not be retained within
the oell even though the temperature and pressure are
maintained constant. In the 3— phase region ohanges in the
quantities of the phases cannot be detected by pressure
measurements. Differential condensation and evaporation
can easily take place at constant temperature and pressure
while sampling, unless the rate of mercury injection and
sampling are precisely equal. Since the two rates could
-102-
not b e enuflt°d with the experimental a rrangement used, this
d i f f i c u l t y wap a ct u a l l y e ncountered d uring the 7— phase
samplingôperations. It was necessary, therefore, to leave
the s t i r r e r on c o n t i n u o u s l y whi l e r e mo v in g the v a p o r p hase
from the t op of the cell. The v a p o r — phase s a mple was re
m o v e d at the rate of p.7 moles per h o u r in the 7— phase
region, co m pared to the general sa m pling rate of 0.5 moles
p e r h o u r for the h y d r o c a r b o n — rich phases. The ra te of
s t i r r i n g was caref u ll y a d ju s te d and the amount o f h y d r o
c a r b o n - r i c h phase redu ced in o r d e r to prevent any entrain—
pent of th e liauld phases in the v a p o r samp le line. No
merc\»ry was injected into the cell while s am p l i n g the v a po r
in the 3 *~PhflS® region.

A r e s i s t a n c e h e a t e r was w o u n d around the va p or
s am p li n g lines to superheat the v a p o r l ea v in g the cell.
Any condensation of the vapor phase would reduce the carry

ing capacity of the vapor for water and yield a low con
centration for that run. This precaution had to be es
pecially taken in the 3— phase region where condensation
can be complete with an undetectable drop below the equi
librium temperature. One heater extended from the top of
the oell to the needle valve l6, Figure 25, snd another
from the latter to the analytical train. The vapor phase
was sampled through V and Tj^. and expanded down to the
pressure of the train at needle valve 1 6 .
-1 0 3 -
In t h e h y d r o c a r b o n — rich liquid p ha s e runs, the
amount of w a t e r rich phase was reduced and the amount of
the former increased. In s a mpling the h y d r o c a r b o n — rich
p ha s e m ercury was injected Into the oell at a p p r o x i m a t e l y
the same rate that the liquid was b e i n g r e m o v e d in o r d e r
to m in i m i z e the c on d en s at i on or v ap o ri z at i on t a k i n g pl a ce
vrlthin the cell. The cuant it y of liauid ph a se present
was Increased to make this d a n g e r less critical. The m er
cury was injected into the cell t hr o u g h 1C— T 7— J— M and the
p ro p a n e — rich liquid p h a s e sa mpled t h r o u g h L^-ll-lB, Figure
25. At n e ed l e valve 1 ? the p r o p a n e — rich liquid phase was
expanded down to the pr e ss u re of the a na l yt i c a l train.
In the 2-phase region, the propane— rich phase was

sampled through the vapor port while mercury was injected
into the bottom of the equilibrium cell. The vapor
sample line was turned on slightly to prevent any loss
of water during the passage of the sample through the
lines, and to hasten the purging of the lines prior to the
removal of the sample. The sample was removed from the
cell at the rate of about 0.5 moles per hour and passed
through the analytical train.
Analysis of the Hyd r o c^rbon-rich P h a s e s :
P r e l i m i n a r y literature studies (^2 ), (27) *nd ex
perimen t al work on d eh y d r i t e (mpgnesium perchlorate)

- 10 M --
ehowed that It could be used as an e f fe c ti v e d r y i n g agent
for the q u a n t i t a t i v e d e t e r mi ne t io n of w a t e r in p r o p a n e gas.
M ag n e s i u m p e r c h l o r a t e has been k n ov m to d e c o m p o s e
violently in the pr e s e n c e of h y d r o o ° r b o n gases for reasons
w h i c h ere not d e f i n i t e l y k n o w n . High tempe r at u re s and the
p re s en c e of c o m b u s t i b l e gases are two factors w h i c h increase
the t e n d e n c y for the spontaneous decomp os i ti o n o f m a g n e s i u m
perc hlorate. Tîs g a v e an a d d i t i o n a l reason for s a mpling
th e h y d r o c a r b o n phases at a slow rate. It gave the d r y
ing tubes suffici ent timp to lose the heat of absorption
to the atmosphere. The d r y i n g tubas wpre also shlaided
from the e x p e r i m en t er in o r d e r to pr o te c t against explosion

ha ?prd 9 .
The effe ctiveness of m a g n e s i u m pe r c h l o r a t e as a
d r y i n g agent un d er reduced pressure was studied. No loss
In w ei g h t of p re v io u s l y used d r yi n g tubes could be d e t e c t e d
a f t e r m a i n t a i n i n g the p r e s s u r e at less than P.l me rc ury
p re s su r e for. 12 hours. Thus, the absor ption of w a t e r from
the p r o p a n e gas could be conducted u n d e r v ar y i n g p r e s s u r e
conditions, from 0.1 mm m ercury to a t m o s p h er i c Pressure.
P r o p a n e v a p o r w h i c h had be en pa s s e d through a series
of abporbents, ac t iv a t e d carbon, sodi um hydroxide, escprite,
and d e h y d r l t e u n d e r pressure, was then passed through the
d e h y d r i t e — filled U-tubes to d e t e r m i n e Its e^f^ct on the
wei ght of the U— tubes. !?yen a f t e r the tubes should have

-105-
.been well "saturated" with propane, the tubas continued

to gain a milligram or so of weight. Many materials were
tried for the flexible connections, Including all kinds of
rubber tubing and tygon tubing.
The g a i n in w e ig h t of the U -t u be s was t r ac e d to the
d if f usion of w a t e r th rough the tubing into the gas stream,
and the su bsequent absorpt i on of the w a t e r b y the m a g n e s i u m
p e r c h l o ra t e. A s a t i s fa c to r y m e th o d of treating rubber to
prevent d i f f u s i o n of w a t e r to lower concentrations has b e en
d e v e l o p e d b y Pregl (31). A good g r a d e of India ru bb er
t u b i n g was out to the d e s i r e d lengths, aged in U-0— 50 '?!- p o t a s
sium h y d r o x i d e at 60 deg. C for two hours, and steamed for

two m o r e h ours. T h e t u b i n g was d r i e d and then p l a c e d in
pure molten pa r af f in wa x in a flask evaouated on a b o i l i n g
w a t e r bath. As soon as th e contents of the flask ceased to
foam, a i r was readmitted into the flask to force the molten
paraffin into the interstices of the rubber. Successive
evacuations and rea dmissions of air w e r e made until b ubbles
w e r e no l o n g e r seen on the surface of the tubing. Th e
tubes were d r a i n e d w h i l e warm, w i p e d on the outside, and
on the inside by means of a tobacco pipe cleaner. The
tubes w e re wiped on the inside w i t h g l y c e r i n e on a. pipe
c l e a n e r and the excess g l yc e r i n e r e mo v ed with a dry p ip e

%
cleaner. The treated pieces of rubber tube wera stored In

a desiccator while not in use. During use it was necessary
-106-
to remove th» excess paraffin from the ends end the bore
of the tubes from time to time vrith a p i p e cleaner.
B ef o re each w e i g h i n g the U— tubes were flushed with
d ry nlr, b l e d to at m o s p h e r i c pressure, and the glass con
n e c t i n g stems w i p e d free of a n y foreign material. The
IJ— tubes w e r e w ei g he d irrm'ediately b e f o r e and after the
sa mpling operations.
P r o p a n e vap ors equivalent to two to three times the
v olume o f the stagnant h y d r o c a r b o n in the s a mo l e line was
b l e d slowly thr ough the train, t h e two IJ— tubes b ei n g sub
s ti tuted b y a glass t u b i n g by-pass. The train end lines
were first re— evacuated to valve l6 for v « p o r phase sampling,
or valve 12, F lgur® 2 5 , for the pro pane-rich liquid phase
sampling, then fill ed vrith dry a i r to at m os p he r ic pressure.
T?V“ U — tubes were inserted into the train, which was then
e vacuated to 0.1 mm mercury, the s am p li n g v a l v e op ened
carefu lly and the gas a dj u st e d to a s a t i s f a c t o r y rate by
o bs e r v i n g the action of the m e r c u r y bu bbler. The sample
sizes we re va ri ed in a c c o r d a n c e with the e o c u r s o y desired
and the amou nt of phase a v ai l ab l e for sampling. The varia
tion in the sam ple sizes was from 0 o15 gr am mols to 0.9
grr rr. m o l s .
When the d es i re d amount of p ro p a n e had been passed
t hr o ug h the train, valve 16 or v a l v e 12 , Figure 25, d e
p e n d i n g on the ohase b e i n g sampled, was closed. The train
w p s a ll o we d t^ fall b a c k to r o o m t e mp e ra t ur e and the final

- 107 -
temper.-ture and p re s su r e of the gas in the iPOfhorlc
b o t t l e read or m a n o m e t e r K, Flgurp 26. The train was
then evacuated, and the U — tubes flushed. and filled
Ttflth dry air. T h e d r y i n g tubes %/ere removed fro™ the
train, cleansed, bled to the atmosphere, and w eighed °s
before. Th e gain in w e i g h t of the IT— tubes r epresented
the w a t ^ r a.bsorbed from the propane gas c o ll ected in
the train.
Analysis o f the W a t e r — Rich P h a s e :
The wnter- r lc h sample was d i s p l a c e d slo wly at the
e qu i li b ri u m p r e s s u r e and tempera tu r e through valves 15-
lU— 13 , Fi g ur e 25 , and expanded at v a l v e S, Figure 27, to
a t m o s p h e r i c pressure. The fl ashed gas and liquid were
colle ct e d in the gas burette, U, F igure 2 7 . The ma rcury
l e v e l l i n g b u l b was ad j us t ed c o nt i nu a ll y to maintain the
gas p r es s u r e in the b u r e t t e at p r ec isely the p r e s s u r e of
the atmosphere.
V a l v e lh, Figure 25, was closed when the desi red
amount of s a m p l e was d i s p l a c e d from the cell, and the
sample in the lead lines from v alve 1^., F igure 25, to
v a l v e 9, F igure 27, a llowed to cool to room temperature.-

Then v al v e S was o p e n e d s l o w l y to a l l o w the liquid in
the lead lines to expand to a t m o s p h e r i c pressure. Finally,
m e r c u r y was introduced through v al v e 17, Figure 27 , to
d is p la c e all the liquid and gas in the lead lines into

the b u re t t e . In this wny, any gas l e a v i n g the w a t e r — rioh
phase b e f o r e v al v e S, was u l t i m a t e l y caug ht in the g a s —
w a t e r b u re t t e . The m a g n i t u d e of the error c a u s e d b y the
n eg l e c t of this p r o c e d u r e was found to be q u i t e a p p r e
ciable for a n y runs c o n d u c t e d a bo v e or b e l o w r oo m tem
p er a t u r e , e s o e c i a l l y those at h i g h t em p er a tu r es .
PART III
APPENDIX
-1 0 9 -
LABORATORY DATA AND SAMPLE CALCULATIONS
P r o p a n e — Rloh P h a s e s :
The data tabulated d ur i ng the c ourse of a run In the
d e t e r m i n a t i o n of the p r o p a n e — rloh phases were:
1. Cell conditions:
(a) E q u i l ib r iu m pr e ss u re
(b) T h e r m o c o u d e E.M.F. at end o f stirring

p eriod and at the end of the sampling
p eriod
2. R o o m conditions:
(a) B a ro m et r ic pressure
(b) Room t e m p e r at u re
*3. Analyt i ca l Train Conditions:
(a) Initial and final gas pressure
( b) I nitial and final train te mperature
(c) Initial and final U— tube we ights
Cd) Analytical train vo l um e
The m o l e c u l a r w e ight of w a t e r was taken to be I S . 02.
A c o m p r e s s i b i l i t y factor chart for mu r e propane gas at
several o r o b a b l e values of ro om te m p e r a t u r e u p to 000 mm.
m er c ur y p r e s s u r e was p r epared and app lied to convert
p r e s s u r e — v o l u m e — te m p e r a t u r e data to moles of propane.
F igure 29 shows Z = PV/nRT as a function of pr e ss u re for
se ve ral te mper^tures .
C orrections or conve r si o n factors applied to the
t a b u l a t e d data w e r e as follows:
-110-
(1) Cnufre readings converted to ab solute pressure,

psia
(2) T h e r m o c o u p l e E . K . F . , millivolts, conver t ed to

temperature, deg. F. u s i n g Figure 31.
(3) Calibr at i on s appl ied to th e r m o m e t e r readings
(U-) T e m p e r a t u r e corrections a oplied to manometer

readin gs
(5) Weight calibrations a p plied to U - t u b e weights
(6) Barometer corrections applied to barometric

readings
T he Co r re c t e d L a b o r at o ry Data and Sample Calculations
for Run No. 1285 is presented below.

C or r e c t e d L a b o r a t o r y D a t a :
E q u i l i b r i u m pr e ss u re = 8523 psla
- Equilibrium temperature = 230.1 deg. F

B ar o me t ri c p re s s u r e = 73^.1 mm me r c u r y
R oo m t e m p e r a t u r e at analytical b al a nc e = 85^.6 deg.
Pr e s su r e rise in train, A P = 73^ mm me rcury
Train temperature, T, = 5 L 7 .5 deg. R
Weight of w a t e r ab s or b ed = 0.11727 gms
C om p re s s i b i l i t y factor, Z, = 0.9^6
V ol u me of train, V, = 11,950 00
Gras oonstant, R, = 3 ^ . 6 R mm mproury, oc. p e r

gm.-mol, deg. R
Caloulations:
P V
G-m.-mols anhydrous propane = ^
( 7 ^ ) ( H , opi0)________
~ (O.Q856 ) (5^7.9)
= 0.^6859 rrols
-111-
O m . — mo Is w s t e r . wptpr
13 .0°
0 .1 1 7 p7
t o t
~ C .00651
Mole w p t ^ r plus p r o p o n e = O.U.75U
Mol F r a c t i o n w a t e r = 0.01369
T he c a l o u l a t e d data for the p r o p a n e — rloh phases in
the 2 - p h a s e r egion w e r e oo r re o t e d f or email d e vi a t i o n s of
the t e m p e r a t u r e f r o m the exact t e m p e r a t u r e of the isotherm
by evaluating fr om th e u n a d j u s t e d data and a no l y i n g
it to the c a l c u l a t e d points. In the e xp r es s io n above,
v = mol f ra ction o f w a t e r in the p r o p a n e — ric h liquid

or vapor phase
T = temperature
P = oressure
T h e s e a d j u s t e d dat a are t e r m e d "Experimental P oi n ts " in thlR
work.
W a t e r — Rloh P h a s e :
The data t a b u l a t e d du r i n g the c o u r s e of a run in the
d e t e r m i n e t i o n of the w a t e r — rloh c h a s e were:
1. Cell conditions:
(a) Equilibrium pressure
(b) T h e r m o c o u p l e E.M.F. at eq u i l i b r i u m and

at the end of the sa m p l i n g peridd
2. Room conditions:
(a) B a r o m e t r i c o re s s u r e
(b) Room temperature r

-1 1 2 -
■* . Analy tical A o o a rntus ;
(©) Burette Jacket tempir e tu r e
(b) Finpl b u r e t t e ropdlng of w p +,«»r-gP8

interface
(c) Finpl b u r e t t e re eding of v a t p r — mercury

Int erfn ce
Temp erature, pressure, barometric, end b u r e t t e volume cor
rections verfi epplied to the t ab u la t ed data. The bu r e t t e
v olume c alibration is given in Figures 32 and 7 3 . The
vfllues of Henry's Lev? constants fo r propane d i s s o l v e d in
w a t e r ere plo tted over the ne o es sa r y t e m p e r a tu r e range on
Figures 3 ? and 33*
The c o rr ected l a b o r a t o r y data and esmple calcula
tions for the w a t e r - r i c h phase f o r Run 232 are given below.
Corrected Laboratory D a t a :
E o u l l l b rl u m pressure = 1120 psla
E q u i l i b r i u m te m pe r at u re = 230.2 F
Barometric pr e ss u re = 73^.6 mm m er c ur y -
Room t e m p e r a t u r e = 07«2 deg. F

B ur e t t e Jacket t e m p e r a t u r e = 06.6 deg. F
= 5 ^ 6.2 deg. R
V ol u me of e oulllbrlum flash gas, Vp = 31*22 co
Volume of eo u ll lb r lu m flash liould, V-j_ = 67.26 cc

’
p £
Henry's Law constant, K = L. = 20.0 x 10
Tv
w h e r e P = p a rtial pressure of propane
In mm of me rcury
N = mol fraction o f pr opane In

Compress i bl l l t y factor, Z, = 0.9365
F. rtini p r e s s u r e of w a t e r In flesh gas at 36.6

deg. F - 3 2 . 0 mm m e r c u r y
P a r t i a l o r e s s u r e of o r o m n e In flash gas, P = 7 0 4 .
P e n a l t y of f lash li q u i d at 36.6 deg. F , P = O .0956

g ms/co
Calouletions:
P Vo
G m . — nols p r o p a n e in the f l a s h gas =
Z H *
(70*l .6) (71. ??)

“ ( .9365 )(3^.65 )(RU-6.2 )
= 0.001173
M ol s w a t e r In the f l a s h gas is n e gl i g i b l e as f a r as
th° m a t e r i a l b a l a n c e for w a t e r is concerned.
V*i p
G m . — mols w a t e r in f l a s h l iquid = 07
=
(6 7— .? 6 ) (0,°996)
— -----
= 3.716
G m . — mols p r op a ne d i s s o l v e d in flash llnuld
= (mole f lash liquid) " T

P
= (3.716)(704.6)
(23.3 x 106 )
= 0 . 0 0 0 0 0 0 9 mols
Mol f r a c t i o n p r op a ne - IT.?AS- PF?.P?10;f:.
t otal mols
_ 0.0012560
3.717
0 . 0 0 0 3 41 7 aol f r ac t io n
orooflne
-114-
The c a l c u l a t e d data for t h e w a t e r - r i c h p h a s e In
th e 2 — chase region w e re co r re c t e d f o r small d e v i a t i o n s of
the t e m p e r a t u r e f r o m the exact t e m p e r a t u r e of the i s otherm
by evaluating from th e u n a d j u s t e d d a t a and a p p l y

1 ^ *p
M
ing it to t h e c a l c u l a t e d points. In the e x pr e ss i on above,
Xg = mol fr a c t i o n p r o p a n e in the w a t e r — rloh phase
T = temperature
P = pressure
T h e s e a d j u s t e d d a ta are t e r m e d "Experimental P o i n t s " in
this work.
- 115-
1
-1 1 7 -
C AL I BR A TI O NS
Pr°Bflur«» G-Pugp Calibretions :
Three steel tub® Bourdon pr e ssure gauges were u°ed
In this investigation.
Dent. Mo. Range
c ?-309 0-150 psi

C?-og 0-1000 osi
CP -100 0-3000 psi
^he gauges were calibrated at the b e g i n n i n g of the
investi gation and several times d u r i n g its course b y means
of the dead weight t en t er in the Sohma Precision Laboratory
at the U n i v e r s i t y of Michigan.
Thermocouple Calibrations:
T h r e e ther mocouples vrere used in the coursp of the
experimental work. T h e i r locations w er e as follows:
T h e r m o c o u p l e No. Position
1 To p right side, in wall

of ecu ilibrium cell
P V a p o r ph a se ss*nnle line
3 B o t t o m left side, In wall

of e nulllbrium cell.
ê calib ration curves for the copper— constenten
thermocouples are p r es e n t e d In Flgur® 31.

C alibration of A na l yt i ca l W e i g h t s :
The analyt i ca l weights u«®d In the fine w ei g hings
m ad e in this i nv e st i ga t io n w e re calibrated u s i n g the
m et h od of trans-position (*19) . The calibrations of the
we ights w e r e made against s ta ndard weights in th e Sohma
Laboratory. The calibrations of the weights are be l ieved
to be a cc u ra t e to C.03 mg.
Calibration of G a s — W a t e r B u r e t t e :
The b u r e t t e was ca l ib ra t ed b y w ei g h i n g th e amount
of m e rcury d ra i ne d from the b u r e t t ® and taki ng the cor-
resoond i ng b u r e t t e readings. The c a libration curves for th
b u r e t t e are given in Figures ^2 and 33.
Vo l u m e C a li b ra t io n of the Analytical Train f o r the

Analysis of the H y d r o p a r b o n - R l o h Phase:_____________
The v o l u m e of the train was d e t e r m i n e d in three
sections whose volumes w e r e as follows:
Seotion Location
1 Vo l u m e from last ne e dl e valve 2 1 U- oc*

to 1st Tl-tube
0 Volume of d r y i n g tubas filled,

bubbler, and lines to b o t t l e 169 cc
3 Volume of b o t t l e in p la c e 11,367 00
Total Volume 11,Q30 oc
Sections 1 and 2 were c a l i b r a t e d b y n o t i n g th® pressu r e

change a o c o m n a n y i n g the expansion of gas in sections 1
*Note: For runs in w h i c h the w a t e r oo n centration exceeded

5 mol water, the v o l u m e of the h y d r o c a r b o n was taken to
be th e t o t a l train v o l u m e minus th e v o l u m e of w a t e r v a p o r
in Seot ion 1 .
-1 1 9 -
a n d / o r 2 Into n third e va c uated c h a m b e r of known and ootp-
o a r s b l e volume. A simple p r e s s u r e — v ol u me — t e m p e r a t u r e re-
let io nship wes set ur> to compute the vo l um e of the unknown
sections o f the trnin. Section 3 wes calibrated b y finding
the weight of w a t e r co n ta i n e d in the b o t t l e when filled.

!
IIQ
[UCfKE tliTOlN C0< HO.'J15 D

-121-
l±j^±h
i - -
a .!
r 5
■fc&P
±: umt?-
cr
- 123-
B-IBLIOGFAPHY
1. AdamB, L.H., J. Am. Chem. Soc. 33,* 37^9* (I 93I)
2. Aroyan, H.J., Ph.D. Thesis, Univ. of M i ch i ga n (194-9)
3. Bartlett, E.P., J. Am. Chem. Soc. ita. 6 5 , (19 2 7 )

4-. Blllman, Sage, and Lacey, A.I.M.E. Trans. 174-, 1 3 ,
(1927)-
5* Brown, Katz, Oberfell, end Alden, "Natural Ga soline
a n d the V o l a t i l e Hydrocarbons", Section I,
Chap. II, M i dwest P r i n t i n g Co., Tulsa, Okla.
6. C a r s o n a n d Katz, A.I.M.E. Trans. 1 4 6 . 1^0, (1942)
7* Chad dock, R.E., Ph.D. Thesis, Univ. of M ic higan (I9M-0 )
8. Clifford, C.W., Ind. Eng. Chem. 13* 6 3 1 , (I921 )
9. Culbers on, Horn, a n d McKetta, A.I.M.E. Trans. 189.

1, (1950)
10. C u l b e r s o n a n d McKetta, A.I.M.E. Trans. 1 8 9 . 3I 9, (I950 )
11. Cul-berson an d McKetta, P r i v a t e Communications, Univ.

of Texas (I9 5 0 )
12. D e a t o n and Frost, Am. Gas Assoc. Proc., Nat. Gas

Dept., p p 122, (19M-0)
13» Deaton and Frost, Proc. Am. Gas Assoc, pp. 1^3 , (19!i-l)
14-. D o d s o n and Standing, Proc. A.P.I., D r i l l i n g and Prod.
Pract., pp. I 7 3 , (l^M-M-)
15« Dourson, Sage, a n d Lacey, A.I.M.E. Trans. 1 5 1 . 206,

(I 9M-3 )
16. G o o d m a n a nd Krase, Ind. Eng. Chem. 2 3 , 4-01, (I93 I)
17. G r i s w o l d a n d Kasch, Ind. Eng. Chem. ^4, 804-, (194.2 )
18. H am m er s ch m id t , E.G., Ind. Eng. Chem. 26, 851 , (1934)
19. Hanson, G . H . , Ph.D. Thesis, Univ. of Mi c h i g a n (1942)
20. K r i c h e v s k y a n d Kasarnovsky, J. Am. Chem. Soc. 57.

2168, (1935)
- 124 -
BIBLIOGRAPHY (Cont.)
21. Kuenen, J.P., Proc. Roy. Soc. Edinburgh, 21,

312 , (1900 )
22 . Kuenen, J.P., "Verdampfung and V e r f l u s s l n g von
Gemischen", J o h a n n Ambros ius Barth,
Lelpslg, pp. 82, (1906 )
23- L a r s e n and Black, Ind. Eng. Chem. 1 7 . 714, (I925 )
24. L au h le r e and Briscoe, Proc. Pa cific Coast Gas

Assoc., 3 0 , 121, (1939)
25. Lebeau, Comot. Rend, (de l'instltut de France)

140, 1454, 1572 , (I905 )
26 . Lewis and Randall, "Thermodynamics" M c G r a w Hill

B o o k Co., Inc., N.Y., (I923 )
27. McKetta, J.J., Ph.D. Thesis, Univ. of Michigan (1946)
28. M cK e tt a and Katz, A.I.M.E. Trans. 1 7 0 . 34, (1947 )
29. M c K e t t a and Katz, Ind. Eng. Chem. 40, 853 , (1948)
30. Olds, Sage and Lacey, Ind. Eng. Chem. 3 4 , 1223, (1942)
31- Pregl (translated by Grant), "Quantitative Organic

Microanalysis", D p . 36 , The Blakiston Co.,
Phlla. (1946)
32. Reamer, Olds, Sage, and Lacey, Ind. Eng. Chem., 15,
790 , '(19^ 3 )
33 - Reamer, Olds, Sage, and Lacey, Ind. Eng. Chem., 3 6 ,
381, (1944)
3^* Roberts, Brownscombe, a n d Howe, Oil and Gas Journal,

2 3 . 37 . (19^0)
35 - Russell, Thompson, Vance, and Huntington, A.I.M.E.

Trans., l 6 o . 151 * (I945 ).
36. Saddington a n d Krase, J. Am. Chem. Soc. 3 6 , 353 , (1934)
37 - Sage, Hicks, and lacey, A.P.I. Drill, and Prod. Prao.

PP. 386 * (1938 )
Ref. and Nat. Gaso. Mfr. 1 7 . 350, (I938 )
-125-
BIBLIOGRAPHY (Cont.)
38. Sage and Lacey, A.p.I. Drill, and Prod. Prac.,

pp. 3 O 8 , (19^1)
39 * Sage and Lacey, "T h ermodynamic P r op e r t i e s of

Hy drocarbons", A m e r i c a n P e t r o l e u m
Institute, N e w York
4-0. Scheffer, F.E.C., K. Akad. Wet., Proc. 16, 4-04-,

(1913 )*
4-1. Scheffer, F.E.C., K. Akad. Wet. Proc. 1J.* 83^> (1914-)
4-2. Smith, G.F. "Dehydration Studies U s i n g A nh y dr o ud
M a g n e s i u m Perchlorate", a pamphlet b y the
G.F. S m i t h Co., Columbus, Ohio
^3* Soudere, Selhelmer, a n d Brown, Ind. Eng. Chem., 24-,

517 , (.1932 )
4-4-• Vlllard, Compt. rend. 106, l 6 o £ # (1888)
i
4-5 . W i e b e and Gaddy., J. Am. Chem. Soc., 1984-, (I9 3 7 )
4-6 . W i e b S and Gaddy, J . Am. Chem. Soc., 6jL, 3 I 5 , (1939)
4-7 * W i e b e and Gaddy, J. Am. Chem. Soc., 6 2 , 8 I 5 , (194-0)
4-8. Wilcox, Carson, and Katz, Ind. Eng. Chem., 662,

(194-1 )
4-9. W i l l a r d and Fur m m , " E l e m e n t a r y Q u a n t i ta t iv e Analysis",
PP- 59> D* V an N o strand Co., Inc., N e w York,
Pd^0
94-0)

Vapor Liquid Eqqilibria

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VAPOR-LIQUID EQUILIBRIA IN BINARY

A dissertation submitted in partial fulfillment

I wleh to gratefully acknowledge all those who so

Professor D.L. Katz, the Chairman of this doctoral

Professor Cedomlr M. Sliepoevlch for his assistance

Profeseor L.O. Csse for his assistance in developing

Professor R.R. White and Professor G.B. Williams

Mr. George A. Foster, Mr. Cleatis Bolen, and Mr.

Professor J.J. McKetta of the University of Texas

The Stanollnd Oil and G-os Company of Tulsa,

years, 19*4-7- 19^ 9 *

The Phillips Petroleum Company of Bartlesville,

Mrs. Ruth Lesko for handling the purchase of ex­

Mrs. Kathyrn Michael and Miss Joanne Meredith for

Sub .1ect Page

Sub.1 ect Page

Subj eot . Page

Part III Appendix

Table No. Subject Page

Table N o . Subject Page

Figure No* Sub .1eot Page

2 Concentration of Water In the

Concentration of Water In the

Figure N o » Sub.1 eot Page

13 Water Content of Light Hydrocarbon

15 Composition of the Hydrocarbon-

17 Plots for the Determination of

TABLE OF FIGURES (Cont.)

Figure No. Sub.1 ect Page

20 Partial Molal Volumes of Pure

21 Experimental and Calculated

22 Minimum and Maximum Solubility for

23 Minimum and Maximum Solubility for

25 Flow Sheet of the Vapor-Liquid

27 Apparatus for the Analysis of the

29 Compressibility Factor for Propane

30 Henry* s Law Constants for the

31 Calibration Curve for the Copper-

33 Calibration Curve for the Lower

The objects of this investigation weres

Vapor-liquld equilibria data were obtained in the

liquid phase in the three-phase region at low pressures,

A detailed discussion of the experimental equipment,

The general purpose of this study Is to contribute

Sage, Lacey and co—workers have determined the dew-

ethane—water (32) systems over a wide range of

t ampere ture scale, relative to other binary hydrocarbon

ra AS E RULE AND ITS RELATION TO EXPERIMENTAL PROCEDURE '

The selection of* the dependent end independent var-

where V = the degrees of freedom or the number of inde­

x2 = 1*5 (T,P) (6)

where the variables are defined as before, realizing that

This vapor-liquid equilibria study was conducted

suits and to permit adjustment of sample sizes with

The use of pycnometers to determine the phase densities

ln the flash liouid was computed using the solubility

PRESENTATION OF EXPERIMENTAL DATA

Experimental vapor-liquld equilibria data for the

liquld equilibria data in the 2-phase region from 100 to

The Solubility of Water in the Hydrocarbon-Rich Phases

ratio, K, of the concentration of water in the vapor to

The ratio becomes 1.0 at the 3-phase critical condition

Thus, the Isotherms of the propane-rich phase relating

years, 194-7- 19^ 9

Mrs. Ruth Lesko for handling the purchase of ex

where V = the degrees of freedom or the number of inde

Further, M— phase equilibria are rep