1072 INDUSTRIAL AND ENGINEERING CHEMISTRY
9
cal properties of a mixture of immiscible liquids can be pre-
dicted, such a theoretical solution may be possible. More in-
formation is also needed on the surface properties of metals.
Nomenclature
= coefficient of heat transfer for mixture, B. t. u./(hr.)
(" F.)(sq. ft.)
= coefficient of heat transfer for water, B. t. u./(hr.)( " F.)
(sq. ft.)
-
= coefficient of heat transfer for second component,
B. t. u./(hr.)(" F.)(sq. ft.)
quantity of heat transferred by water, B. t. u./hr.
= quantity of heat transferred by second component,
B. t. u./hr.
= y t i t y of heat transferred by mixture, B. t. u./hr.
= t erma conductivity, (B. t. u.)(ft.)/(hr.)(" F.)(sq. ft.)
= acceleration of gravity, 4.18 X lo8 ft./(hr.j(hr.)
= mean temperature drop through the film, F.
= specific heat, B. t. u./(lb.)(" F.)
= latent heat of vaporization, B. t. u./lb.
= viscosity of condensate, lb./(ft.)(hr.)
= density of condensate, lb./cu. ft.
Vaporization Equilibrium Con=
stants in a Crude Oil-Natural
Gas System
D. L. KAT21 AND K. H. HACHMUTH
Phillips Petroleum Company, Bartlesville, Okla.
T HE vaporization of the gaseous hydrocarbons from crude
oil occurs in all stages of crude oil production, from the
movement in the reservoir until it reaches the refinery.
The vaporization characteristics of the volatile hydrocarbons
methane through hexane which are in solution in crude oil
under pressure are of interest in crude oil production and in
the natural gasoline and natural gas industries. The most
suitable measure of the vaporization characteristics of pe-
troleum mixtures is the equilibrium constants developed by
Souders, Selheimer, and Brown (6). They defined the equilib-
rium constant as the ratio of the mole fraction of a constitu-
ent in the vapor phase to the mole fraction of that constituent
in the liquid phase a t a defined temperature and pressure:
At equilibrium: y/x = K (1)
where y = mole fraction of a constituent in the vapor phase
x = mole fraction of the constituent in the liquid phase
K = equilibrium constant of the constituent at equi-
librium temperature and pressure
These K values were studied further (3, 6) and were found
to be extremely useful in calculating vapor-liquid equilibria
for hydrocarbon systems.
The purpose of this paper is to describe the experimental
methods used in determining the equilibrium constants of the
volatile hydrocarbons in a crude oil-natural gas system and to
present the results of the measurements. The earlier work on
1 Present address, Unlversity of Michigan, Ann Arbor, Mioh.
VOL. 29, NO.
Literature Cited
(1) Churchill, J. E., Refrig. Eng., 26, 85-7 (1933).
(2) Cogan, C.A., M. S. Thesis, Mass. Inst. Tech., 1934.
(3) Hodgman-Lange, Handbook of Chemistry and Physics, 18th
ed., Cleveland, Chemical Rubber Publishing Co., 1933.
(4) Jeffrey, J. O.,Cornel1 Univ. Eng. Expt. Sta., Bull. 21 (1936).
(5) Keenan, Steam Tables, Am. Soc. Mech. Engrs., 1930.
(6) Kirkbride, C.G., IND.ENQ.CHEM.,25, 1324 (1933).
(7) Langen, Forsch. Gebiete Ingenieurw., 2, 359 (1931).
(8) McAdams, "Heat Transmission," New York, McGraw-Hill
Book Co., 1933.
(9) Nagle, Bays, Blenderman, and Drew, Trans. Am. I n s t . Chem.
Engrs., 31, 593 (1935).
(10) Nesselmann, K.,and Dardin, F., Wiss. Verdfent. Siemena-
Konzern, 10,No. 2, 129-54 (1931).
(11) Nusselt, W.,2. VeT. deut. Ing., 60, 541 (1916).
(12) Ibid., 60, 569 (1916).
RECEIVED June 8,1937. Presented before the meeting of the American Insti-
tute of Chemical Engineers, Toronto, Canada, May 26 t o 28, 1937. Sub-
mitted by Alfred C. Mueller in partial fulfillment for the. Ph.D. degree,
University of Miohigan.
Experimental vaporization equilibrium
constants of constituents methane
through hexane in a mixture of natural
gas and crude oil are presented. The
data were observed over a pressure range,
from atmospheric to 3000 pounds per
square inch and a temperature range
from 40" to 200" F. The rise of the equi-
librium constants at high pressures ap-
proaching the critical pressure of the mix-
tures were shown for the first time
in complex mixtures of this wide range of
volatility. The smoothed data are pre-
sented in equilibrium constant charts
which are very useful tools in predicting
vaporization phenomena. Descriptions
of the apparatus used, the analytical
procedure, the materials used, and the
equilibrium measurements are included.
K values (3, 6) was based on meager data and considerable
theory, such as the assumption of ideal solutions. For this
reason it was thought that experimental K values would be
desifible for accurate work a t high pressures. The pressure
range chosen for the investigations was from atmospheric to
above 3000 pounds per square inch, and the temperature
SEPTEMBER, 1937 INDUSTRIAL AND ENGINEERING CHEMISTRY 1073
range was from 40" to 200" F. These conditions were con- used with ice as the cooling medium. A high-speed stirrer gave
sidered to include most reservoir and surface oil-gas separation rapid circulation of the bath fluid.
systems. The mercury reservoir C had a capacity of 1 liter and was
initially filled with nitrogen gas a t 1200 pounds er square inch.
Materials
Mercury was pumped by means of an all-steer remodeled hy-
draulic jack into the reservoir until the nitrogen in the reservoir
The crude oil was a Midcontinent crude from the Wilcox exerted a pressure of 1500 to 2000 pounds in excess of the pres-
sure desired in the equilibrium bomb. A regulating valve, L,
sand of the Oklahoma City field. A sample of crude contain- allowed close control of the mercury flow into the equilibrium
ing dissolved gas was obtained from the well head of a flowing bomb during the withdrawal of samples or transfer of fluid. The
well under a pressure of about 400 pounds per square inch. pressure gage, M , on the reservoir served as index of the mercury
This crude contained the major proportion of the volatile withdrawal. The lines leading to the manifold below the bath
were always filled with mercury, and the manifold was so ar-
constituents, except methane and ethane, that were originally ranged that all lines and valves could be purged with mercury.
present in the reservoir crude a t the initial conditions of 2600 The temperature of the contents of the equilibrium bomb was
pounds and 132" F. A sample of natural gas was obtained assumed to be the same as t,hat of the bath after a suitable length
from the same field a t a pressure of 1100 pounds per square of time t o permit the temperatures to equalize. The bath tem-
inch. These materials were not analyzed-
previous to the equilibrium measurements,
since the purpose of the experimental work
was to obtain K values on typical mix-
tures of natural gas and crude oil. For
convenience and general information only,
the initial Oklahoma City Wilcox crude
was approximated.
The analysis of the higher boiling por-
tion of the crude oil used is given by a
U. S. Bureau of Mines distillation of a sam-
a 2 DOUBLE-POLE
ple of Wilcox crude that was separated -
DOUBLE THROW
from natural gas at atmospheric pressure. SWITCHES
Table I shows the pertinent data obtained
from this standard d i s t i l l a t i o n . The
moisture present in the crude and natural

P
gas as sampled was not r e m o v e d until
after the vapor and liquid were in equilib-
rium or in the first step of the analytical
procedure.
Equilibrium Apparatus 5000 LB.
PRESSURE
The apparatus used to bring the oil GAGE
and gas into equilibrium a t c o n s t a n t
t e m p e r a t u r e and pressure is shown in
Figure 1:
The primary components of the equipment
were the equilibrium bomb, A , the constant-
temperature bath, B, and the mercury pres-
sure reservoir, C .
The equilibrium bomb had a capacity of 1
liter (1 quart) and was bored from solid
hexagonal stock. The dimensions were 41/*
inches outside and 21/1 inches inside for the
lower portion, and 6 inches outside and 31/4
inches inside for the cap. A soft copper
gasket, F, compressed between a '/$*-inch
tongue and groove, served as a satisfactory
seal between the cap and the body of the
bomb. A small electric motor, G, with stirring
shaft and paddles, was mounted inside the
bomb so that equilibrium between the phases
could be obtained quickly and positively.
The motor was built with a minimum of brass
and copper parts and had integral speed-
reducing gears to give the stirring shaft a
speed of about 60 r. p. m. when applying 12
volts. The electricity was conveyed to the ,QUID ANALYZING
APPAR*TUS
motor by means of one high-pressure electrical
connection, H , and a ground wire to the bomb.
Fluid lines to the bomb consisted of a vapor
line, I,a liquid line, J , and a mercury line, K.
These lines were l/s-inch 0. d. seamless steel
tubing with soft iron cones and followers form-
ing the joints.
The constant-temperature bath was heated FIG. I
with two 1000-watt heaters with suitable
rheostats for control. Oil was used in the EQUILIBRIUMBOMB
A N D AUXILIARY EQUIPMENT
bath at temperatures above 100" F.; the
temperature was regulated by manual control MERCURY PUMP
of the heat input. A t 40" F. water was
 1074 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 29, NO. 9
perature was read with a total immersion thermometer, D,gradu- motor was observed to raise the pressure in the bomb a small
ated in 0.1' C . The accuracy of these thermometers was checked amount without any change in bath temperature. In turn or
by comparison with standards of like scale. The pressures were
measured with 500,1000, or 5000 pounds per square inch, 10-inch simultaneously, vapor and liquid samples were withdrawn
dial Bourdon tube gages, E, from a common manifold. The gages from the bomb, the pressure being maintained constant by al-
were calibrated with a dead-weight tester, and the pressures re- lowing mercury to enter from the reservoir. The vapor
ported were corrected according to the calibration scales deter- sample was conveyed through a trap to ascertain that no
mined.
liquid phase was withdrawn. The vapor passed from the
trap through a small tube to the gas analysis apparatus. The
CITY WILCOX
OF OKLAHOMA
TABLEI. DISTILLATION size of gas samples varied from a maximum of 22 liters a t
CRUDEOIL standard conditions for the high-pressure samples to 6
Saybolt Index of liters for low-pressure determinations. Liquid samples were
Per Cent Gravity Viscosity Refraction" either conveyed directly through a steel tube to the liquid
Temp. over Fraction at 100' F . at 20' C.
F. " A . P . I. Sec. analysis apparatus or transferred by mercury displacement
90 Initial ... .. into a bomb and thence into the analytical apparatus. The
167 3.9 76:3 ... .. latter method had the advantage of giving the volume of the
257 14.0 64.5
347 23.1 53.7 ,.. ... sample from which the density might be calculated. Liquid
392 28.2 48.3 ... ...
482 37.9' 43.0 ... samples were of the order of 40 to 60 ml. which provided ample
527 44.9 39.0 ... :
1 466 material for analysis.
Distillation at 40 Mm. Pressure
Up to 392 48.0 34 2 The atmospheric pressure determinations were carried out
437
482
52.6
58 7
32 6
30 6
45
56
1 469
1 475
in a 3-liter Pyrex glass flask with a suitable manometer and
527 64 5 28 7 85 1 480 connections instead of the bomb because of its limited capacity.
572 71 7 26 8 151
Equilibrium was obtained by shaking in a large constant-
Gravity of crude, 'A. P. I. 3 8 . 4 Conradson oarbon of temperature bath. The liquid and vapor phases were satu-
Sulfur % 0.22 still residue 4.1
Pour dest of crude Below Oo F. Gravity of still resi- rated with water in these cases and samples were taken by
Saybolt viscosity of crude at due, OA. P. I. 19.2
loODF., see. 43.5 water displacement. The pressure of the equilibrium was
a Abbe refractometer. corrected for the vapor pressure of the water. Atmospheric
pressure runs were made only for the 40' and 120' F. series.
The sequence of pressures for the samples at any tempera-
Equilibrium Vapor and Liquid Samples ture started with the highest pressure and was controlled by
the quantities of oil and gas removed. It happened that the
Equilibrium between the vapor and the liquid phases was size of samples chosen gave the desired drop in pressure when
obtained in the bomb, and a sample of each phase was with- the mercury which had been injected during the previous
drawn a t constant pressure by simultaneously admitting an sampling operation was withdrawn. This method of obtain-
equal volume of mercury. Initially the bomb was evacuated. ing samples corresponds as closely as possible to that of ob-
Then about 600 cc. of the well-head crude oil were flashed into taining samples which would come from an oil reservoir of
the chamber. The high-pressure natural gas was then in- falling pressure, when considering the over-all objective of
jected through the gas connection and the stirring motor measuring equilibrium constants.
started. When the crude oil became saturated with gas, a t
about 1100 pounds per square inch, it became necessary to Analytical Methods
pump the high-pressure gas into the bomb, using an auxiliary
bomb and the mercury from the reservoir. Gas was forced The volatile hydrocarbons in both vapor and liquid samples
into the bomb until an equilibrium pressure in excess of 3000 were separated by low-temperature fractionation. The vapor
pounds was reached with the system a t the temperature to be analyses were carried out on a two-column apparatus similar
used in the determinations. to the one described by Fitch (2) and by Oberfell and Alden
Previous to taking each set of equilibrium samples, the (4). The vapor sample was dried and injected into the bot-
bomb was maintained a t the desired temperature for several tom of the larger column. Methane was fractionated and re-
hours, and the stirrer was operated first continuously and then moved overhead while the last portion of the sample was
intermittently. The stirrer was not operated just prior to the being admitted into the column. Ethane and propane were
removal of the equilibrium samples, as the energy input to the usually fractionated in turn in the large column, and the

TABLE11. PHME EQUILIBRIUM

DETERMINATIONS
AT 40' F.
Compn*l ExPtl* K +om Compn., Mole Exptl* K from Compn., Mole ExPtl. K from
K v!! Finished vapor Finished
Component
%
Liquid Vapor - Finished
Vapor
= Liquid
Charts Liquld %Vapor Liquid Charts Liquid% Vapor __ILiquid Charts
Y E x p t . 18, 3422 Abs.--
Lb./Sq. In. -Expt. 19, 1216 Lb./Sq. In. .4bs.- --Expt. 20, 846 Lb./Sq. In. Abs.--
43.20 86.60 2.00 1.98 28.25 92.29 3.27 3.34 21.20 91.70 4.32 4.3
7.24 5.68 0.785 0.78 7.95 4.85 0.610,a 0.65 8.01 5.62 0.7020 0.67
6.20 3.52 0.568 0.55 7.78 1.81 0.253 0.23 8.43 1.85 0.219 0.215
4.91 1.89 0.385" 0.35 6.15 0.65 0.105" 0.094 6.71 0.56 0.083 0.081
3.57 0.95 0.26Ba 0.25 4.70 0.17 0.036 0.036 5.14 0.15 0.029 0,027
3.44 0.59 0.171 0.164 4.60 0.07 0.015 0.0163 5.05 0.07 0,014" 0.0113
0.48 0.13 ... .... 0.0088 ... 0.0055
Heptanes
Heptanes and heavier 3i.'44 0.77 o.'oiis5 0.0195 :
40 67 0.16 0.0039" 0.00132 45:46 0.05 0.'00114 0.00083
Y E x p t . 21. 538 Lb./Sq. In, Ab%--? Y E x p t . 22, 198 Lb./Sq. In. Abs.- F E x p t . 16, 1 4 . 5 Lb./Sq. In. Absa-
Methane 14.24 89.83 6.31 6.3 5.35 80.81 15.1a 16.0 0.17 37.25 219 221
Ethane 7.94 7.04 0.887" 0.84 6.96 13.00 1.87 1.86 1 . 0 5 22.80 21.70 23.5
Propane 8.82 2.28 0.258" 0.24 9.56 4.60 0,481 0.46 4.43 25.12 5.67" ' 5.4
Butane 7.58 0.62 0.082 0.081 8:55 1.20 0.140 0.143 7.42 10.78 1.455 1.6
Pentanes 5.72 0.15 0.026 0.025 6.48 0.21 0.032a 0.038 7.21 2.89 0.40" 0.42
Hexanes 5.40 0.04 0.0074 0.0094 6.25 0.08 0.013 0.0137 79.726 0\75 ... ....
Heptanes ... .... 0.0043 0,0057 ... 0.25 ... ....
...
. . I

Heptanes and heavier 50:30 0.04 0,0008 0.00065 56,'85 0.10 O'OO18' 0.00086 0.41 ... ....
0 Values lie outside the limits of probable error.
b Heptane and heavier.
SEPTEMBER, 1937 INDUSTRIAL AND ENGINEERING CHEMISTRY 1075

butanes, pentanes, hexanes, heptanes, and heavier were de-

termined by distillation in the smaller column.
The liquid samples were analyzed in a double-column com-
bination. The first column had a bulb with electric coil
heater a t the bottom for boiling the oil vigorously. The
methane, ethane, propane, and some isobutane were removed
as a group from the first column and condensed in the bulb a t
the base of the second column. These vapors passing to the
second column were dried in a PzOb drying tube between the
columns. The second column was then shut off from the
first column and operated as a regular gas analysis column
separating the methane, ethane, and propane until the isobu-
tane provided the reflux. The fractionation in this column
was then discontinued, and the remainder of the butanes,
pentanes, hexanes, and some heptanes were distilled from the
oil in the first column into the bulb of the second column.
These constituents were separated in turn until the heptane
became the reflux in the hexane-heptane separation. The
heptane residue was distilled from the column, condensed,
and added to the residual oil drained from the first column.
The quantities of the fractions separated were determined as
gases in carefully calibrated 1- and 3-liter bottles. Correc-
tions for the volume of the top of the column and transfer
lines and for room temperature were applied to the several
fractions.
The volume of the residual oil removed from the first col-
umn was measured and its density determined. As molal
analyses were desired, the molecular weight of the crude oil
residue was determined. The lowering of the freezing point
of benzene was used (1) for determining the molecular weight
of several of the residue liquids. An average molecular
weight of 225 was obtained by extrapolation to zero concen-
tration. This value was used for all samples. The molal
composition of the liquid-phase samples was calculated, using
ideal gas volumes for the more volatile constituents and the
volume, density, and molecular weight for the liquid residue.
The liquid analysis apparatus was designed for routine analy-
sis of high-vapor-pressure crude oils and was especially suit-
able in these analyses, owing to the absence of measurable
quantities of gases more volatile than methane.

Results Obtained
A total of twenty-three pairs of liquid- and vapor-phase
samples were analyzed. The equilibria at three temperature
levels (40", 120°, and 200" F.) were investigated. The pres-
sures ranged from above 3000 pounds per square inch down to
atmospheric. The data obtained are given in Tables 11, 111,
and IV as mole fraction vapor analyses with the corresponding
mole fraction liquid analyses. At the time the liquid analyses
were obtained (April to July, 1934) they were particularly in-
teresting because of the high concentrations of methane found
in the liquids of high vapor pressure. The liquid analyses
show that they provide a more reliable method of analyzing
for several of the volatile constituents than do gas analyses
because there is a higher concentration of these constituents
in the liquid phase, and hence no small quantities must be
separated or measured.
The ratios of the mole fraction of each constituent in the
vapor phase to the mole fraction of that constituent in the
liquid phase at the indicated temperature and pressure are
also given in Tables I1 to IV. These equilibrium constants
were the desired data of the project. A convenient way of
plotting the data is as an isotherm showing the logarithm of
the equilibrium constant K against the logarithm of the abso-
lute pressure. The data are plotted as circles on Figures 2,3,
and 4 for the three temperatures investigated. The rise in K
for all constituents except methane with increasing pressure
above 600 to 1200 pounds per square inch shows clearly the
 1076 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 29, NO. 9

111. PHASBEQUILIBRIUM
TABLB AT 120' F.
DETERMINATIONB
Compn.i Exptl. K from Compn Mole Exptl.K from Compn., Mole ExDtl. K from
% K Vapor F i n i s h 4 A Vapor K - Finished jy - Vapor Finished
Component Liquid Vapor Liquid Charts Liquid Liquid Charts Idquid%Vapor Liquid Charts
c E x e t . 6, 3212 Lb./Sq. In, Abs.- -Expt. 7, 2125 Lb./Sq. In. A b s . 7 T - E x p t . 8, 1226 Lb./Sq. In. Abs.-
Methane 4 3 . 2 1 - 87.02 2.01 2.00 33.53 88.21 2.62 2.60 22.08
7.39 87.79
7.03 3.97
0.951 3.9
Ethane 7.61 6.56 0.862" 0.82 7.70 6.35 0.8250 0.86 0.99
Propane 6.27 3.38 0.539" 0.58 6.71 3.04 0.453a 0.48 7.75 3.08 0.3974 0.45
Butanes 4.40 1.55 0.362" 0.37 5.49 1.32 0.2400 0.260 6.23 1.31 0.210 0.212
Pentanes 3.11 0.69 0.222'3 0.240 3.56 0.51 0.143 0.143 4.40 0.40 0.91 0.092
Hexanes 3.47 0.28 0.084" 0.170 3.78 0.26 0.069° 0.086 4.77 0.20 0.0420 0.049
Heptanes 0.32 0.126 ... 0.058 ... 0.0288
Heptanea and heavier 35:40 0.52 0:0i47a 0,0189 39:2l 0.31 0:0079" 0.0087 47:38 0.19 0:0040 0.0043
---ExDt. . . In. Abs.-
1. 863 Lb./Sq. -Expt. 2, 530 Lb./Ss. In. Abs.- --ExrJt. 3, 312 Lb./Sq. 1 n . i A b s . p
Methane 1 7 . 2 8 85 .'52 4.95 5.0 11.40 81.87 7.78- 7.6 6.36 75.46 11.86a 12.5
Ethane 7.19 8.54 1.19 1.17 6.99 10.51 1.50 1.53 5.90 13.90 2.36 2.40
Propane 8.35 3.67 0.439'3 0.46 8.64 4.92 0.570 0.56 8.34 6.91 0.829 0.81
Butanes 7.06 1.52 0.215 0.202 7.75 1,83 0.236 0.23 7.60 2.57 0.338a 0.316
Pentanes 5.18 0.51 0.098" 0,083 5.68 0.50 0.088 0.086 6.27 0.61 0.097a 0.112
Hexanes 0.09 0.038 6.04 0.20 0.033 0.038 6.27 0.32 0.051 0.048
Hentanes
Heptanes and heavier
54:94b
... 0.24'~
0.15
0.0233
.... 53 50
0.10 .... 0.020 0.13 0.0243
0.17 0.0032 0.0030 59: 26 0.23 0: 039 0.0037
--Exot. . - In. Abs.-
4. 135 Lb./Sa. -Exut. . - In. Ab&-
6.49.6 Lb./Sa. -Exot. 9. 1 2 . 8 Lb./Sa.
. - In. -4bs.-
Methane 2.48
4.48
. 60:18 24.3"
4.54"
28.9 0.37 28196 . 7 8 . 3 79.0 0.106 30.87 208.7 310.0
Ethane 20.35 5.2 1.69 27.47 16.3a 14.0 0.226 14.22 62.9a 54.0
Propane 7.97 12.60 1.58" 1.68 6.85 26.18 4.47 4.4 1.222 20.13 16.5 16.8
Rutanes 7.77 4.69 0.604 0.63 7.34 12.17 1.66 1.65 3.282 18.39 5.61° 6.1
Pentanes 6 20 1.28 0.206 0.215 6.46 3.42 0.530 0.54 4.82 9.44 1.96 2.00
Hexanes 6.53 0.49 0,075" 0.088 6.93 0.96 0.138" 0.22 5.97 4.30 0.720" 0.83
Heptanes 0.28 0.044 0.65 0.106 1.92 0.40
Heptanes and heavier 6k:b7 0.41 0:064 0.0066 7i:h 0.85 o:oii9 0.0159 2.65 0:03140 0.060
a Values lie outside the limits of probable error.
Hexanes and heavier.

range of retrograde condensation and the effect of the ap-
proaching critical pressure on K a t the higher pressures.
Correlation of Experimental K Values
The method of analysis did not allow checking of experi-
mental results.' Errors in either the liquid or vapor analysis
would be reflected in K . The possibilities of error in K for
any one constituent demanded that a thorough method of
correlation be devised which would eliminate any doubtful
This type of chart was developed by Brown and co-workers
(6). A cross plot of the curves on Figures 2, 3, and 4,using
temperature vs. logarithm of K with lines of constant pressure
is the form employed. The X chart for pentane is shown by
Figures 5 and 6. The two plots are desirable for all constitu-
ents which have the same value for K a t two different pres-
sures. Figures 5 and 6 were plotted using the general equa-
tion covering the data and extrapolating the data to -30"
and 270" F. by means of the equation. The charts for meth-
ane, ethane, propane, butanes, hexanes, heptanes, and heavier
were similarily plotted. The charts giving the K values over
the range of temperature -30" to 270" F. and pressures 5
to 3000 pounds absolute cover most vaporization conditions
encountered in crude oil and natural gasoline production and
are the essence of the entire project.
The possible errors in each step of the analytical procedure
were evaluated and the probable error was calculated for
vapor and liquid analyses in terms of each constituent. I n
Tables 11,111,and IV the smoothed K values taken from the
charts are tabulated opposite the experimental values.
Those experimental K values which deviate from the smoothed
data more than the probable error are marked a. Figures
2, 3, and 4 also give a clear picture of the consistency and ac-
curacy of the data.
0.5
O.?
0.2

01
007
0.08

values. A statistical study of the data in the form of Figures 00 3

2, 3 , and 4 showed that a n empirical equation could be de- 0 02

vised between K , total pressure, temperature, critical pressure 0.01

of the mixture, critical temperature of the pure components, 0.007
and molecular weights of the constituents. This equation is 0.006

represented by the curves drawn through the data on Figures
2 to 4. The irregularity of the data increased with the con-
stituents of higher molecular weight which were present in the
vapors in decreasing amounts, in most cases. The data were
in rather good agreement for analyses of this type, especially
as shown by the heptanes and heavier in Figure 4.
I n the use of K , it is convenient to have a plot covering all
pressures and temperatures for the several constituents.
TEMPERATURE ' F
No rigorous separation of the isomeric butanes or of the
pentanes was made in the analysis, and hence K is not given
for the separate isomers. A few analyses were run more care-
fully to determine the relative quantities of isomers present in
the Oklahoma City crude oil. A value of 27 per cent for the
percentage of isobutane in the total butane vapor may be
SEPTEMBER, 1937 INDUSTRIAL AND ENGINEERING CHEMISTRY 1077

ane and fractions heavier

IV.
TABLE EQUILIBRIUM
PHASE DETERMINATIONS
AT 200” F. than heptanes, b u t s u ?-
Exptl. K from Exptl. K from prisingly good agreement
Compn., Mole % ’ K =V ! ! Finished Compn., Mole % ’ K = !%!E Finished has been obtained between
Component Liqmd Vapor Liqmd Charts Liqmd Vapor Liquid Charts
Y E x p t . 23,3527 Lb./Sq. In. Abs.- Y E x p t . 24,2399 Lb./Sq. In. Abs.-
calculated and experimental
Methane 4 83.33 ... ... 33.98 84.32 2.48 2.50 vaporizations on s e v e r a 1
Ethane
Propane
...
... 6.62
5.15’
...
...
...
...
6.72
6.72
7.15
4.01
1.066
0.5970
1.01
0.64
Midcontinent and a few .
Butanes ... 2: 45 ... ... 5.15 2.14 0.4166’ 0.39 Gulf Coast crudes of similar
Pentanes
Hexanes
...
...
1.24
0.90
... ...
...
4.14
4.14
1.03
0.62
0.2496
0.150b
0.24
0,158 v ol a t i l i t y . Equilibrium
... ... ... ....
I . .

Heptanes 0.59 0.32 0.116 constants for materials with

Heptanes and heavier ... 1.31 ... ... 39:i5 0.73 0.0186 0.0174
a critical pressure less than
Y E x D -t . 25.. 1744 Lb./Sa.
. - In. -4bs.- Y E x D t . 26. 1369 Lb./Sa. In. Abs.- that of the above mixture
Methane 27.52 84.24 3.06 3.1 22.29 83.29 3.74- 3.7 will be expected to conform
Ethane 6.57 7.52 1.14 1.13 6 22 7.98 1.28 1.30
Propane 6.66 4.05 0.6096 0.65 6 83 4.49 0.658 0.68 to a convergence of K values
Butanes 5.84 2.17 0.872 0.37 6.13 2.23 0.364 0.36 to unity a t that critical
Pentanes 4.54 0.95 0.209 0.207 5.00 0.93 0.186 0.188
Hexanes 4.32 0.52 0.120 0.126 4.88 0.52 0.107 0 110 pressure.
Heptanes ... 0.083 0.29 .... 0.070
A wide variety of uses
Heptanes and heavier 44:56 0.55 0:0123 0.0124 48.’65 0.56 0.0115 0,105
may be made of the K in
Y E x p t . 27, 928 Lb./Sq. In. Abs.---- c-Expt. 28, 579 Lb./Sq. In. Abs.- calculating the equilibrium
Methane 15.54 81.69 5,260 5.0 9.83 77.88 7.926 7.5 vaporization of all mix-
Ethane 5.58 8.63 1.55 1.58 4.35 10.20 2.346 2.2
Propane 6.63 5.07 0.765 0.76 6.26 6.25 1.006 0.96 tures for which they apply.
Butanes 6.47 2.55 0.3946 0.38 6.63 3.14 0.473b 0.45
Pentanes 5.50 0.93 0.1696 0.175 5.74 1.20 0.209b 0.200 Dew points of gases, vapor
Hexanes 5.46 0.61 0.1126 0,094 6.24 0.77 0.123b 0.101 p r e s s u r e s of liquids, the
Heptanes . I . 0.058 . . . 0.054
Heptanes and heavier 54.‘82 0.52 0.’00956 0.0087 60.‘95 0.56 0 .‘Od92b 0.0081 quantities flash-vaporized
a t a n y temperature and
---Expt. 29, 284 Lb./Sq. In. Abs- -Expt. 30, 118 Lb./Sq. In. Abs.- pressure along with com-
Methane 4.55 70.30 15 4b 14.7 1.50 56.29 37.5 36.0
Ethane 3.00 11.84 3.95 4.0 1.50 13.59 9.07 9 3 p o s i t i o n s of vapor and
Propane 5.23 8.77 1.68 1.67 3.57 13.42 3.76 3.8 liquid (S), liquid composi-
Butanes 6.41 4.88 0.762 0.74 5.47 8.87 1.62 1.62
Pentanes 6.12 1.90 0.310 0.31 6 40 .4.05 0.633 0.64 tions from the vapor com-
Hexanes 7.90 1.17 0.148 0.147 5.77 1.89 0.328 0.31
Heptanes ... 0 082 .... 0.165 positions or vice versa, and
Heptanes and heavier 65‘79 1.14 o’Oi7ib 0.0123 75 :79 i.’& 0.0249 0.0248 gas solubilities may be cal-
0 Sample lost.
b Values lie outside the limits of probable error.
c u l a t e d a t temperatures.
and pressures in the range
I
of t h e d a t a . The mate-
rials and phases present in
used. Correspondingly, an approximate value of 20 per cent an oil reservoir, in a flowing column of oil and gas, in oil and
of the liquid butanes as isobutane may be used. Approxi- gas separators, and in many other systems are shown by the
mately 35 per cent of the pentane fraction may be considered data presented.
isopentane. The data will aho find considerable use in refinery and natu-
ral gasoline plant calculations either by direct use for mix-
Significance of the Results tures similar to those studied or by adaptation to other mix-
The outstanding feature of the data is the convergence of tures. Experimedtal equilibrium constants are powerful
K towards a critical pressure as shown by Figures 2, 3, and 4. tools in research or engineering problems involving vaporiza-
It was expected that this approach to the critical would ap- tion phenomena.
pear ( 5 ) , but the position of the critical and behavior of the
several constituents were shown for the first time. This criti- Acknowledgment
cal pressure is not for the definite mixture under its own vapor The writers wish to acknowledge their indebtedness to
pressure but is the pressure a t which only one phase exists A. F. Jirous for valuable aid in precise analytical work, to
when vapor in equilibrium with the liquid is dissolved in the Legatski, Oberfell, and Alden for constructive criticism and
liquid by increasing the pressure a t constant temperature. supervision, and to the Phillips Petroleum Company for per-
As the density of the liquid decreases and that of the vapor mission to publish the material.
increases, they finally meet a t the critical pressure, and be-
cause they are in equilibrium as they approach the critical, Literature Cited
they approach the same composition and K approaches unity. (1) Findlay, “Prantical Physical Chemistry,” London and New York,
The increase in K a t increasing pressures shows quantita- Longmans, Green & Co., 1928.
( 2 ) Fitch, L. H., Natl. Petroleum News, 28, No. 25, 66-8, 70-1
tively the effect of retrograde condensation when expanding a (1931).
gas that has been separated from a liquid a t high pressure. (3) Kate and Brown, IND.ENQ.CHBIM., 25, 1373 (1933).
The behavior of those natural gases which produced a distil-
late upon expansion is explained by the rapid increase in K of
--.
(4) Oberfell and Alden, Oil Gas J . . 27. No. 22.
~.
--- (1928)
142
\----I-
( 5 ) Sage, Lacey, and Schaafsma, I N D . ‘ E NCHWM., 26, 214 (1934).
the heavier constituents and hence an increase in the concen- (6) Souders, Selheimer, and Brown, Ibid., 24, 517 (1932).
tration in the vapor of the high-boiling constituents. RECEIVEDMay 21, 1937. Presented before the 14th Midwest Regionax
The data can be used to give a close approximation of the Meeting of the American Chemical Society, Omaha, Nebr., April 29 to M a y
composition of the liquid and vapor phases in the Wilcox sand 1, 1927.
a t 132” F. and pressures from initial pressure of 2600 pounds
to atmospheric. K as determined on the Wilcox crude should
be applicable to any mixture of crude oil and natural gas if the
concentrations and chemical characteristics had no effect on
K . It is known that concentrations and chemical composi-
tion will have some effect, especially on the K values of meth-