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G P A T P - 1 71 3824677 001058b 5 2 2

Technical Publication
TP-I

Liquid Densities of Ethane, Propane,


and Ethane-Propane Mixtures

Dr. J. R. Tomiinson
Gulf Research 81DevelopmentCompany
Pittsburgh, Pennsylvania
February, 1971

Reprinted 1991

6526 East 60th Street Tulsa, Oklahoma 74145 Phone: 918/493-3872 FAX: 918/493.
.3875
G P A T P - 1 71 3 8 2 4 6 9 9 0010587 4 6 9 E

FOREWORD

This publication is a complete report o f a research


investigation b y Dr. J. R. Tomlinson, Gulf Research &
Development Company, which was originally presented in
summary f o r m t o NGPA Technical Section H o n Measure-
ment, M a r c h 17, 1970. As presented herein, it includes
additional experimental data and correlation results com-
pleted after i t s original presentation, and is published as
a supplement t o t h e Proceedings o f the 49th Annual NGPA
Convention.

The rapid growth o f commerce in ethane-propane


mixtures has created a critical need for precise experi-
mental data, a n understanding o f the pressure-volume-
tempe rat ure re1a t ions hips, and acceptable i ndust ry prac-
tices for accurate measurement o f these volatile streams.
This report is a major step toward f i l l i n g these needs.

The N a t u r a l Gas Processors Association and the gas


processing industry gratefully acknowledge this signifi-
cant technological contribution by Dr. Tomlinson; sincere
appreciation is also extended t o Gulf Research & De-
velopment Company and Warren Petroleum Corporation
for release o f this report t o the industry.
GPA T P - 1 7 2 3824699 0030588 3 T 5

NATURAL GAS PROCESSORS ASSOCIATION 3

LIQUID DENSITIES OF ETHANE, PROPANE,


AND ETHANE-PROPANE MIXTURES
J. R. TOMLINSON
Gulf Research i% Development Company,
Pittsburgh, Pennsylvania

SUMMARY ment of liquid densities and bubble points of ethane, propane,


and a series of mixtures. These basic data were used to de-
1. Liquid density measurements of ethane, propane, and velop a correlation which allowed the printing of tables for
ethane-propane mixtures have been made over the normal application in the field. Having measured temperature, pres-
metering range. The effect of adding small amounts of sure, and composition, one can look up the correction factor
methane and/or n-butane was also investigated. All of the in these tables to reduce a metered flow to 60°F and satura-
original density data have been presented in this paper. Bub- tion.
ble point measurements have also been made on these sam-
ples. These data have been presented in the original form In this paper the following items are presented:
for ethane and in equation form for the remaining composi- 1. The experimental methods used which allow an evalua-
tions. tion of the precision of the measurements (Appendix A ) .
2. Interpolative equations were developed which allow 2. A presentation of the basic data points collected.
ethane-propane density tables to be printed. Equations were
presented which allow the calculation of density for a given 3. A description of the correlation procedures used to
pressure, temperature, and composition. This allows metered check data and prepare tables, and the equations which can
flows of ethane-propane mixtures with small amounts of be used to generate a complete set of tables.
methane measured at line conditions to be corrected to a 4. A description of a second type of correlation which
standard state. A computer program for making these calcula- yields simple equations for calculating both saturated and
tions is available on request from the NGPA. compressed liquid density data. This method is applied to
3. It was found that large volume shrinkage occurs when the ethane and propane data only, for which accurate values
ethane and propane are mixed. This effect, which may of the critical temperatures are available.
amount to a 5% deviation from ideal (no shrinkage) mixing, 5. A discussion of the results in terms of present litera-
will manifest itself as a volume decrease on blending or as ture data.
volume gain on fractionation. Use of the tables generated
in the present work allows the accurate calculation of this
effect. CORRELATION OF DATA
4. The liquid density data for all compositions (in the Development of Ethane-Propane Density Tables
form of isochors) have been extrapolated to the bubble point
curve to yield liquid saturation density data. In the special The liquid density data for each individual sample were
case of ethane and propane, density equations of the type correlated by computer assuming linear isochors. Several
suggested by Francis’ were developed. These equations different equations were evaluated which showed about the
enable a quite accurate comparison of the data of this work same degree of fit to the data. The following equation was
with those of other investigators for both the saturated and used:
compressed state. T-60 = (P-1000) (Bo -E BID + B,D’)
5. The density of pure propane determined in this work (1)
agrees well with other literature data, including the value + A, + AID + A,DZ
published in the NGPSA Engineering Data Book (1966)l:.
The selected density value for 60°F and saturation pressure The coefficients were developed by least squaring the tem-
resulting from these studies is 0.5069 gm/cc, specific gravity perature. The density at a given temperature and pressure
60/60 = 0.5074. was calculated by a computerized quadratic solution. The
density fit of the experimental points to those calculated was
6. The density measurements of pure ethane show that excellent for propane (2.02%) and quite good for mixtures
the value commonly accepted13 for the standard state of containing up to 70% ethane. For the 90% ethane mixture
60°F and saturation pressure is about 6% too high. The best and pure ethane, the density fit was the order of 0.1% for
value for ethane density a t saturation pressure and 60°F temperatures up to 100°F. At higher temperatures, the den-
resulting from this work is 0.3563 gm/cc, specific gravity sity fit gradually increased to 0.3% at 120°F as the result of
60/60 = 0.3567. isochor curvature.
The addition of terms cubic in density to the slope and
INTRODUCTION intercept functions showed no improvement to the fit for the
Several years ago it was recognized by Warren Petroleum low ethane mixtures and only slight improvement for the
that no reliable density data existed for ethane-propane high ethane mixtures.
mixtures. Since this material is an item of commerce fre- The above equation was used to determine values of the
quently transferred between companies by measuring a saturation density at 60°F (DSATGO) for each sample using
liquid volume flow at line conditions, accurate density data the saturation pressure at 60°F (PSATGO) calculated from
are needed to correct the metered flow at line conditions to the bubble point equation for the particular composition. The
a standard state, normally 60°F and saturation pressure. At resulting values of PSAT6O and DSATGO, along with the
Warren Petroleum’s suggestion, we undertook the measure- bubble point equations, are listed in Table I.
GPA TP-1 7 1 3 8 2 4 b 9 9 0010587 231

4 ADDENDUM -PROCEEDINGS OF 49th ANNUAL CONVENTION

TABLE I
Eauation Evaluation for PSAT 60 and DSAT 60
Sample Composition Extent of Density
Mole Percent Measurements Bubble Point Data
Experimental Equation1

Ethane

-
Propane Methane

-
-- Number
n-Butane P,T Points -Number
Isochors
Temp. Range
OF A
Constants
B
- -
PSATbO
psia
DSATIO
sm/=

100.0 - 40 11 56-120 12.495 4060 108.0 0.5069


- 97.58 2.42 - 21 6 50-120 11.0130 3068 165.6 0.5017
- 99.11 - 0.89 17 5 68-122 11.4606 4043 107.8 0.5078
37.00 63.00 - - 37 11 55-135 11.8854 3352 229.4 0.4678
49.89 50.11 - - 22 8 90-120 11.8980 3624 275.4 0.4515
48.28 48.49 3.23 - 29 9 36-113 11.3081 2843 342.9 0.4434
71.71 28.29 - - 37 10 45-115 12.0560 3204 361.7 0.4186
70.05 27.64 2.31 - 24 7 72-114 11.6235 2915 409.2 0.4129
69.52 27.47 2.18 0.83 21 6 43-109 11.5194 2863 407.5 0.4155
89.97 10.03 - - 35 10 60-90 12.2767 3210 445.9 0.3823
100.00 - - - 61 14 40-86 12.41002 32272 493.5 0.3563
97.74 - 2.26 - 30 8 42-79 12.1440 3043 538.4 0.3502

I...Dafa wcrr f i t to the rquufton: Ln P ( p s i a ) = A - B/T('R).


2 . For highest accuracy, correction should be applied a t higher temperatures, Table I X .

Because the coefficients of the above equation change too auxiliary table or an equation must then be provided to
rapidly with composition, the saturation density at 60°F was determine DSAT6O from the compbsition.
used as a density base for composition correlation. In the
revised equation given below the coefficients show only a Correlation against DSAT6O instead of composition has
moderate change with composition. three advantages. It was anticipated that the correlation
would be converted to tabular form yielding a voluminous
T-60 = (P-1000) [Bo + B, (1-R) + B, (1-R)?] table for the correlation and a quite small several-page
+ Ao + A1 (1-R) + A, (1-R)' (2) auxiliary table for the conversion'of composition to DSAT6O.
In this case, the first advantage would be that the correlation
where R = D/DSAT60. itself would be applicable to any units of composition. A
Substituting the saturation conditions at 60"F, change in the definition of composition would require only
modification of the auxiliary table. Second, the correlation
R = l could be used for a sample of unknown composition if
T = 60 DSAT6O is known. Finally, the correlation is applicable to
P = PSATGO ethane-propane samples containing small quantities of me-
thane. In this case a small temperature correction must be
into the equation, the coefficient A, can be expressed as a made. This temperature correction and the effect of methane
function of Bo, on DSAT6O can be included in an auxiliary table which is
discussed later.
A, = Bo (1000 - PSATGO)
and can be eliminated from the revised equation. Hence, The experimental density data for the six ethane-propane
mixtures were temperature-least squared to the linear iso-
T-60 = (P-PSAT60) Bo + (P-1000) [BI (1-R) + B, chor equation using the computer. The selected value of
(l-R)'] +
A, (1-R) A2 (i-R)* + (3) DSAT6O and PSAT6O for each mixture was also used as
input data.
It should be emphasized that equation (3) is identifiable
with equation (1). The coefficients of these two equations The following equations were used to express the co-
are inter-related through the conversion from density to efficients as a function of DSAT6O which is represented by x.
relative density. One coefficient has been eliminated by the
introduction of PSAT6O into the revised equation. B, = Bo, + BolX + BoZXZ + B,,X3 (4)
A correlation of the relative densities of the ethane-
propane mixtures can now be made by defining PSATGO, Bi + B11X +
= BI, (5)
DSATGO, Bo, BI, B?, A,, and A, as functions of composition. B2 = Bzo + B,,X + (6)
However, DSATGO is itself a definition of composition for the
two component ethane-propane system. Thus, it is possible A1 A,, + A11X + A12X2 + A,3X3
1 (7)
to correlate the liquid density data for the ethane-propane
system with no reference to composition whatsoever. An A, = A,, + A,,X + A , F J +- A2,X3 (8)
GPA T P - 1 71 akl 3824699 0010590 T53 m

Values of the double-indexed coefficients are tabulated in The addition of a small quantity of methane to an ethane-
Table II. Two additional equations are necessary for the propane mixture has the effect of reducing the density and
preparation of tables from the correlation. These are, raising the saturation pressure. The coefficients of the com-
puter isochor equation were redetermined by including the
PSAT6O = GI> + G,X + G,X? + G:,X" (9) ethane-propane-methane data along with the ethane-propane
H = HI, + H,X + H.,X- + H,X" + H,X' (10) data in the computation. The redetermined coefficients showed
little deviation from those previously determined. The density
with their coefficients tabulated in Table II. The PSAT6O check was somewhat poorer but still quite adequate. How-
equation is used in place of the selected values of PSAT6O ever, in the preparation of the main tables, the PSAT6O
in retrieval of relative densities from the correlation. value corresponding to a DSAT6O value was calculated from
an equation based upon these selected values for ethane-
TABLE II propane without methane. Since the addition of one mole
percent methane will raise the PSAT6O value of an ethane-
Coefficients for Isochor Equation propane mix about 15 psi, this discrepancy must be taken
into account in the use of the main tables for mixtures con-
taining methane. The simplest method of correcting this
Coefficient Exponent of M A T 60 discrepancy is to reduce the tabulated pressures in the main
tables by 15 psi for each mole percent methane present. Iii
O 1 2 3 4 effect, this pressure reduction will shift the isochor plot
for the ethane-propane mixture to match up with the isochor
BI, 0.31187 -1.55252 i 2.76145 -1.7527 plot for ethane-propane. Alternatively, this isochor shift can
be achieved with a temperature increase. The relationship
BI 0.40284 -1.19324 1.0959 - - between these two alternatives is,
B, -2.7001 12.9797 -14.517 - - AT -Bo A P (14)
A, -146.52 17.51 1,440.8 3,367.0 - where B,, is the coefficient corresponding to the DSAT6O
A2 10,754.6 -69,588.9 146,637.0 -106,391.0 value of interest. We chose to use the temperature correction
which is tabulated in the auxiliary table and must be added
PSAT 60 685.6 530.2 -2,280.00 -2,000.0 - to the temperature before entering the main tables.
H 853.08 -7,903.47 27,710.62 -43,273.6 25,401.0
TABLE III
The equation for H defines the second constant, B, in the Conversion of Composition' to DSAT60 and Methane Effect
bubble point equation in the following manner.
Effect per
B 1.0 Mole Percent
= H (11) Added Methone
519.67 ADSAT 60
Mole Percent
Ethane
M A T 60
sm/cc gm/cc 4T"
-
so that the natural logarithm of the ratio of a saturation
pressure at temperature T can be expressed in terms of the O 0.5070 -0.0028 0.4
saturation pressure at 60°F in the form, 5 0.5021 -0.0028 0.4
PSAT (T) H[T("F) - 601 10 0.4971 -0.0029 0.4
In -
- 0.4
15 0.4920 -0.0029
PSAT6O [TíOF) + 459.671 20 0.4868 -0.0031 0.4
The above equation and the equation for H permit the cal- 25 0.4814 -0.0031 0.4
culation of the approximate saturation curve as a function 30 0.4758 -0.0032 0.4
of temperature for any DSAT6O value. In the preparation of 35 0.4701 -0.0033 0.4
tables, the calculated relative density for any input pressure
and temperature which fel! below the saturation curve was 40 0.4641 -0.0033 0.4
blanked to indicate the location of the saturation curve and 45 0.4579 -0.0034 0.4
to preclude density calculations in the vapor or two-phase 50 0.4515 -0.0035 0.5
region. 55 0.4447 -0.0036 0.5
The ethane-propane correlation in tabular form consists 0.4375 -0.0037 0.5
60
of two sections, the main tables and an auxiliary table. The
main tables tabulate relative density as a function of tem- 65 0.4299 -0.0038 0.5
perature and pressure for a series of DSAT6O values. These 70 0.4218 -0.0039 0.5
values are spaced at constant intervals for interpolative 75 0.4130 -0.0040 0.5
purposes. The auxiliary table is a tabulation of DSAT6O as 80 0.4036 -0.0041 0.5
a function of composition. For this purpose, the selected
85 0.3934 -0.0043 0.5
values of DSAT6O were fitted to a power series equation in
mole fraction ethane to yield, 90 0.3823 -0.0044 0.5
95 0.3701 -0.0046 0.5
DSAT6O (gm/cc) = 0.5070 - 0.1031Y + 0.0093Y2 100 0.3568 -0.0048 0.6
-O.O632Y:{ +
0.03575YJ - 0.02860Yj (13)
where Y = mole fraction ethane. The auxiliary table was I . Mole Pcrceat Propane = 100 - (mole perccnf ethane + niole perceni
also used to incorporate the effect of small amounts of ntethairr) .
methane. 2 . Tcinpcrali6rr corrcrtion i s added to obrerizd temperaliire.
GPA TP-II 7 1 W 3824679 OCIL0591 9 9 T W

6 ADDENDUM -PROCEEDINGS OF 49th ANNUAL CONVENTION

The second effect of the addition of methane to an ethane- where D,.(; = the approximate critical density calculated by
propane mixture, that of reduction of the DSATGO, requires the equation, T, = saturation temperature in OR, T,. = critical
no correction in the main tables. Assuming DSATGO is linear temperature in OR, and D, = saturation density. Calculated
with methane content over the short range of compositions values of D,.c, for many light compounds invariably show a
considered, the reduction in DSATGO for the addition of one trend with T,. To avoid any connection with critical density,
mole percent methane is also tabulated in the auxiliary table. D,, is redefined as normalized density, D,. The normalized
It must be emphasized that these corrections at the density is then,
50% ethane, 1 % methane level amount to about 1 7 ~in
DSATGO and about 0.5% in relative density (AT correction).
+
D, = D,/ (1 1.75 t$l +
0.75 (j:3) (16)
The actual auxiliary table used in field application tabulates where,
DSATGO for each 1% change in ethane content to 50 mole
percent ethane and for each 0.5 change in mole percent T,
t$l = (1 - -
)1/3 (17)
above that. It also supplies density and temperature cor-
rection for 1.0, 2.0, 3.0 and 4.0 mole percent methane. A Te
shortened form of this tabulation is given in Table III. For the purpose of exhibiting a correlation check or fit,
the normalized density, D,, is plotted against 6. The use of
8 in place of T, expands the temperature scale in the neigh-
Development of Density Equations for Ethane and Propane
borhood of the critical temperature. It is in this plot that
In view of the special interest in the experimental den- judgment must be used in the location of the curve to
sity data for ethane and propane, a n alternate approach represent the data.
was used for the correlation of these data. The approach is The second type of plot used in the correlation is the
a modification of one suggested by Francis2 who tabulated slope plot in which the natural logarithm of the slope is
the coefficients of two equations for twenty-six hydrocar- plotted against density. This plot is used only to determine
bons. These equations, along with vapor pressure data, the slope coefficients A and B. Slopes determined from
enable the prediction of saturation liquid densities and com- experimental points which lie far from the saturation curve
pressed liquid densities for the hydrocarbons. are given more weight than those which lie close to the
saturation curve. This is self-evident from the rearrange-
The equations used by Francis are: ment of the linear isochor equation to yield,
A. Linear isochor P = P, + S(T-T,) P-P,
B. Slope equation lnS=AD +
B s=- (18)
C. Saturation density equation D, = function (T,) T-T,
D. Vapor pressure equation P, = function (T,) The reiterative process can best be described by a flow
diagram,
where P = pressure, T = temperature, S = isochor slope,
P, = saturation pressure, T, = saturation temperature, Revised T, -Ps ----+ S
D, = saturation density, and D, = D = density along isochor.
The two equations for which Francis tabulated coefficients
are the slope equation and the saturation density equation. Slope Plot
For the latter, the saturation density equation, Francis tabu- Density Plot
lated the coefficients of two equations, one to be used for
saturation temperature well below the critical temperature
and the other to be used in the neighborhood of the critical
temperature.
t-T,-Revised S d
The four equations listed above and used by Francis can
also be used for a correlation of the ethane and propane In the calculations, the experimental density is always
density data of this investigation. In fact, one equation can used. The calculations of P,, S, and normalized density are
be eliminated from the correlation with the stipulation that then direct. The calculations of T, involve a backward or
the two variables it defines are a smooth function of each reverse solution to the equations. From the normalized
other. density curve, the appropriate normalized densities are
The obvious selection for elimination is the saturation read off for selected values of 6 corresponding to 1°F inter-
density equation. In place of this equation, we use an ap- vals. The saturation densities are calculated and the revised
proximate saturation density equation merely for plotting saturation temperature, T,, corresponding to the experi-
purposes. The deviations of calculated saturated densities mental density is interpolated. For the calculation of T,
from a smooth curve in this plot indicate the degree of fit used as input to the normalized density plot, the linear
for the correlation. isochor equation and t.he vapor pressure equation are solved
However, because of the simplicity of the equations, a simultaneously by first assuming a value for T, and calcu-
reiteration process using an electronic desk calculator can lating P,. Using these values along with the slope and the
be used instead of a computer. This method is preferred experimental P and T, a new value of T, is calculated. This
over the least square techniques of the computer in that each process is repeated until T, is determined to 0.01"F. Usually
data point is handled individually and thus small experimen- the process needs to be repeated only a few times.
tal errors in the data are easy to spot. In order to initiate the reiterative process, either the
slope constants or the normalized density curve must be
The approximate saturation density equation used in the approximated. Although the experimental apparent isochors
correlation is one suggested by Guggenheim3 for the calcu- appear quite linear, their slopes are poor estimates of the
lation of critical density. This equation is: slopes of the true isochors. On the other hand, a linear extra-
rn rn
polation of an apparent isochor to the saturation curve to de-
termine T, and the subsequent estimation of the small den-
sity increase in this extrapolation yield a good approxima-
G P A TP-3 73 = 3824677 0030572 826

tion of the saturation density. These extrapolated satura- TABLE LV


tion densities are then used to prepare the first normalized
density curve. Further calculations involve the individual Liquid Propane Density Equations
data points of each isochor.
The key to the correlation is the location and shape of
A. P = Ph + S(T-T,).
the curve drawn through the points in the normalized den- B. 1nS = 7.343 D, + 0.1233.
sity plot. The best curve through the points is not neces-
sarily the right approach. Three types of deviation must be C. InP, = 12.495 - 4060/T, (OR).
considered. The first is the slope error which must be cor- D. D, = (0.21670 + 0.0356 0 + 0.027 02) (1.0 + 1.75 0
rected and the slope coefficients revised in the subsequent
slope plot. A slope error is evidenced by a trend in the $- 0.75 6:s)
deviation of points from a single apparent isochor. In this
case, more weight must be given to the highest density points TS
0 = (1 - -)'I'' T,. I 665.68"R
which require a shorter extrapolation to the saturation
curve. In fact it may be necessary to visually extrapolate T,
the points from an apparent isochor beyond the highest Valid Range
density point to the approximate location of zero tempera-
ture extrapolation. This approximation requires the con- Pressure Saturation 2000 psia
sideration of the values of (T-T,) for each point. A second
type of deviation is that produced by a single point of the Temperature 30" +120°F
isochor which indicates a pressure or temperature error. The Density 0.45 40.53 gm/cc
third type of deviation is when all points from a single ap-
parent isochor deviate to the same extent from the curve.
This indicates a density error and such errors invariably in- yield pressure and temperature checks of the above magni-
dicate low densities. The source of these errors may be a tude. In addition, the saturation density equation predicts a
slow leak in the pycnometer between disconnnection and critical density ( 0 = O) which agrees quite well with a
weigh in g. recent selected value4 of 0.217 gm/cc.
The final normalized density plot for propane is given The experimental ethane density data were exceedingly
in Figure 1. The deviations of the individual points from the more difficult to correlate into equation form. In the case
smooth curve show directly the density check. Density of propane, the experimental densities ranged from 2 to
errors as the result of pycnometer leaks are apparent in two 2.5 times the critical density. For ethane, the density range
isochors occurring to the extent of 0.02% or less. The curve was from 0.5 to 2.0 times the critical density. As the density
in Figure 1 is well represented by, approaches critical, the accuracy of the extrapolation to the
saturation curve is considerably reduced. A further compli-
D, I= 0.21670 + 0.0356 0 - 0.027 62 (19) cation is introduced by the evidence of positive curvature of
the apparent isochors at high temperatures. In the computer
approach these high temperature points were ignored and
linear isochors assumed. For the new correlation) the high
temperature points were accounted for by the addition of
a quadratic term in the isochor equation. This addition re-
quired the assumption of two additional slope constants.
In view of the complications associated with the devel-
opment of correlation equations for ethane, it was neces-
sary to apply an additional restraint to facilitate the calcu-
lations. The normalized density curve was assumed to be
linear. This assumption is not unreasonable in that the
normalized density curve for propane deviated only several
hundredths of a percent from linearity, Figure 1.
Eleven ethane isochors were used to develop the liquid
ethane equations tabulated in Table V. Three isochors had
to be eliminated from the correlation even though their
O2275 t I data are considered to be quite good. The densities of these
O 50 o 55 O 60 0.65 0.70 three isochors were either very close to, or well below,
B critical density.
Figure 1 As in the case of propane, two of the eleven ethane iso-
Plot of Normalized Density Against 6 for Liquid Propane chors showed evidence of pycnometer leaks which resulted
in low densities to the extent of 0.05 and 0.08%. The other
The equations developed for liquid propane are given in densities are considered to be precise to .03%. The pressure
Table IV along with other pertinent information. and temperature fits are about 1-2 psia and 0.05"F, respect-
ively, The normalized density equation predicts a critical
The equations in Table IV predict the experimental pro- density of 0.2035 which agrees quite well with the recently
pane data to 0.01% in density and to approximately 0.03"F in selected value4 of 0.203.
temperature. The pressure fit varies from about 1 psi at the It should be pointed out that a comparison of the slope
low densities to 2 psi at the high densities. This variation is equations of this investigation and those tabulated by Francis
the result of the change in isochor slope of about a factor is not justified. In the metering range, the data available
of two over the density range. The experimental densities to Francis were quite meager. In the case of the saturation
of the two low isochors mentioned above must be corrected to densities of propane, the agreement is quite good. His
~- ~

GPA T P - 1 71 3824699 0030593 7 b 2

8 ADDENDUM -PROCEEDINGS OF 49th ANNUAL CONVENTION


__ .- -__ .- __
.-

saturation densities for ethane are about 5% too high as is Propane


the case for several data tabulations. This point will be
discussed in the following section. In the case of propane, there is a wealth of saturation
density data in the literature. Table VI lists a comparison of
TABLE V the saturation density data since 1937. Cragoe? reviews the
data prior to 1943 and tabulates selected data for the satu-
Liquid Ethane Density Equations rated hydrocarbon liquids from propane through n-pentane
including propene and the butenes. He particularly criticizes
A , P = P, +
SI (T-T,) +
S2 (T-T,)? the NGAA investigation(;, which neglects a compressibility
B. InSI = 8.00 D, 0.321 + correction for propane and thus yields high densities. ASTM
C. Sz = 0.05107 - 0.1044 D,
109AT also lists selected data at three temperatures. The
remainder of Table VI lists the experimental data for five
D. lnP, = 12.410 - 3227/T, (OR) (above about 70°F investigations including this research.
a positive pressure correction must be added - see Table
1x1 Upon inspection of Table VI, it is noted that only two
of the selected and experimental sets of data of the six listed
E. D, = (0.20353 + 0.014188 8 ) (1.0 + 1.75 8 -t 0.75 8") show any appreciable difference from those of this research.
They are the NGAA values, about 0.1% high as explained by
T* Cragoe, and the saturation densities published by Sliwinski,"

-
8 = (1 - - ) I / : < T, = 549.77"R which are about 0.1% low. The latter also has determined
T,. the saturation density data for ethane, n-butane, and iso-
Valid Range butane. His values for n-butane and isobutane are also
about 0.1% lower than the values selected by Cragoe over
Pressure saturation 2000 psia the temperature range 50+ 140°F. Therefore, one would
expect Sliwinski's values for propane would be about 0.1%
Temperature 30" 120°F low. The values for propane listed by Seeman and Urban!'
Density 0.27 + 0.41 gm/cc show a slight temperature trend upon comparison with
those of this research, but agree quite well in the 15-20°C
range. Since their investigations used 20°C as a temperature
DISCUSSION OF RESULTS base for their volume corrections, better agreement at 20°C
The ethane and propane liquid density data of this re- is expected.
search can be compared to the literature in two ways. First, Four investigations tabulate compressed liquid propane
the compressed liquid data may be compared by interpolat- density data over the metering range. Three of these tabu-
ing either set of data to obtain identical conditions of tem- lated isotherms at widely spaced temperature intervals and
perature and pressure. Second, the extrapolated saturation the fourth tabulated isochors. The 70" and 100°F isotherms
density data of this investigation may be compared to other of Sage, Schaafsma, and Laceyin (1934) indicate densities
saturation density data requiring only a temperature inter-
polation. In view of the excellent fit of the experimental about 1.0% higher than this research. The 30" and 45°C
data to the equations developed in the preceding section, isotherms of Deschner and Brownil (1941) are about 0.25%
it was unnecessary to interpolate or extrapolate the experi- higher. Saturation density data reported in these papers are
mental data. Densities for comparison were calculated di- also high, the discrepancies being of the same magnitude as
rectly from these equations at the conditions of interest. that of the compressed liquid data.

TABLE VI
Saturation Densities of Propane, gm/cc

Seeman This
Crag& ASTW Van der Vetm NGAAs and Urbano Sliwinskis Research
Temperoture (1945) (1963) (1937) (1942) (1963) (1969) (1970)

-
41
OF
- OC

5
Selected Data Experimental Data

0.5226 0.5219
50 10 0.5152 0.5150 0.5157 0.5153 0.5143 0.5150
59 15 0.5080 0.5076 0.5078 0.5077

60 15.56 0.5072 (0.5068) 0.5073 0.5074 (0.5070) (0.5065) 0.5069

68 20 0.5005 0.5005 0.5004 0.5007 0.5002 0.4999 0.5003


77 25 0.4928 0.4928 0.4929 0.4929 0.4922 0.4926
86 30 0.4847 0.4848 0.4850 0.4843 0.4846
95 35 0.4764 0.4768 0.4768 0.4764
104 40 0.4676 0.4678 0.4682 0.4674 0.4678
113 45 0.4584 0.459 0.4595 (0.4587)
122 50 0.4486 0.449 0.4506 0.4487 (0.4493)
~ ~~ ~

1. 60°F NGPSA Engineering Data Book15 (0.5072 grnicc or specific gravity 60/60 =
.1077).
2 . Saturation densities in parenthesis bave been obtained b y interpolation or extrapolation.
G P A T P - 1 71 = 3824b99 0010594 bT9

NATURAL GAS PROCESSORS ASSOCIATION 9


__

Reamer, Sage, and Laceyi- (1949) have reinvestigated


the propane system. Their 100°F isotherm is about 0.1% low
at 400 psia and 0.1% high at 2000 psia compared to the present
results. The isochoric data of Dittmar, Schuh, and Stresels
(1962) were plotted for interpolation and extrapolation to
the saturation curve, Although they report pressures to the
nearest kg/sq cm (14 psia), the isochors were quite linear.
Both the compressed liquid densities and the saturation den-
sities agreed to 0.1% with this research.
In summary, it can be said that the agreement for the
liquid density data for propane in the metering range is
very satisfactory.
Ethane
In the case of ethane, there are serious discrepancies in
the reported saturation liquid densities. The NGPSA com-
pilationlz (1966) reports a value at 60°F about 6% higher
than that determined in this investigation. The correlations
of Tester"; (1961) and Barkelew, Valentine, and Hurdl'
(1947) report values about 3% higher. The source of these , I , I , I , I , 10.34
high values appears to be the International Critical Tables18
(1928), which are based on a series of studies by Kuenenl" 0.2 0.4 0.6 0.8 1.0
(1895-1902). The work of Kuenen was not specifically cen- MOLE FRACTION ETHANE
tered on saturation densities, but rather on a study of the Figure 2
law of rectilinear diameters. In his second paper, Kuenen
Variation of DSATóO for Ethane-Propane Mixtures. Circles (O)
recognized and acknowledged the fact that the sample was Represent Data from this Research. Corresponds to the Ethane
impure. Value Presently Accepted by NGPSAl".
A recent study by Sliwinskis (1969) furnished the only
good comparison with the data of this investigation. In Table 1% low. Saturation densities reported by the former are
VII, this comparison is made both on the basis of density and about 1% high. The vapor pressures also reported in the
temperature deviations. former paper are about 10 psia higher than those determined
in this investigation.
TABLE VI1 Beattie et al.22 and Michels et al.23 have reported the
Comparison of Experimental Saturation Densities densities of ethane at 25°C intervals for 50°C and higher.
of Liquid Ethane Fortunately, Michels has developed equations to express his
data as isotherms. These two sets of data check within them-
selves to about 0.1% at least to 150°C, the temperature limit
Equivalent of Michels' data. Reamer, Olds, Sage, and Lacey21 have
Temp. Sliwinski This Research Temp. Dif.
OC sm/cc gm/cc % Difference oc interpolated Beattie's data to calculate compressibilities at
their conditions. On a density basis, their values are about
10.05 0.3736 0.3739 0.08 0.10
15.04 0.3577 0.3581 0.11 0.12 APPROXIMATE DENSITIES
20.03 0.33G9 0.3395 0.18 0.15 027 O30 O 33 O 6
+ 0100 I 1 I
22.52 0.3277 0.3285 0.24 0.18
25.02 0.3149 0.3158 0.28 0.15
27.51 0.2988 0.3001 0.43 0.17
29.01 0.2867 0.2880 0.45 0.14

As in the case of propane, Sliwinski's value for the satura-


tion density of ethane in the vicinity of 60°F is about 0.1%
.
t

lower than ours.


Further evidence for the validity of the present DSATGO,
60°F value for ethane arises from its consistency with the and DENSITY IS ON 122'F (50'C) ISOTHERM
values obtained for propane and for ethane-propane mixtures. - ETHANE EQUATION
This is displayed in Figure 2. The saturation density value at EXPERIMENTAL
60°F of 0.3563 gm/cc or a specific gravity of 0.3567 60/60 DENSITIES

taken from the ethane equations in the preceding section THIS RESEARCH
O B E ATTI E
is suggested. o MICH E LS
The only published data on compressed liquid ethane in I I I I I 1 I l l I
the metering range were reported by Sage, Webster, and 1000 1500 2000
PRESSURE ( P S I A I
Laceyi" (1937). Ethane was reinvestigated by Reamer, Olds,
Sage, and Laceyzl in 1944 for temperatures 100°F and higher. Figure 3
A comparison with this investigation indicates the former to Comparison of Present High Temperature Ethane D a t a to
be about 1-2% high in density, and the latter to be about Literature D a t a
G P A TP-L 7L 3824b99 0030595 535

10 ADDENDUM -PROCEEDINGS OF 49th ANNUAL CONVENTION

0.5% lower than Beattie's. Thus, the reported data of Beattie


also indicates the data of Reamer, Olds, Sage, and Lacey to
be low.
90 F
With an isochoric extrapolation of only 2"F, ethane den-
sities of this investigation can be compared with those of
Beattie22 and of Michels.23 The 50°C (122°F) isotherm is
plotted in Figure 3 as a deviation plot. Also shown is the
deviation calculated using the ethane equations of the pre-
ceding section. The two highest densities reported by Beattie
fall in the range of the ethane equations. Pressures calculated
by these equations are in each case about 2 psi smaller than
those reported by Beattie.
The excellent check of the data of this investigation with
Beattie and with Michels at 122"F, and the check with
Sliwinski at saturation, tie the isochors at two positions.
Thus, the ethane equations are recommended for the meter-
ing range.

Ethane-Propane Mixtures - Volume Shrinkage


Prior to the present investigation, no density data of
ethane-propane mixtures in the metering range existed. For
this reason, it is not possible to compare these results with
literature data. Our results revealed that substantial volume
83
82 1 .I .2 .3 .4 .S .6 .7
M O L E FRACTION E T H A N E
.8 .9 1.0

change occurs when ethane and propane are mixed. This


effect is displayed for two conditions of temperature and Figure 5
pressure in Figures 4 and 5. The straight line connecting Volume Shrinkage for Ethane-Propane Mixtures at 80"F, 750 psia
pure ethane and pure propane is that expected for ideal
mixing-no volume shrinkage-while the curve represents ACKNOWLEDGMENT
the measured data. It is noted that the magnitude of the
effect becomes larger at lower pressures as the bubble point The author of this paper wishes to acknowledge the con-
is approached. This volume change, on mixing, ranges up to tribution of Warren Petroleum Corporation for suggesting
5 or 6 percent depending on composition, temperature, and these studies and for their release of the data for publication.
pressure. The precise amount of volume decrease to be The author also wishes to acknowledge the assistance of
expected on blending, either pure ethane and propane or Arthur V. Fareri and Ralph L. Pivirotto in making the ex-
different ethane-propane mixtures, can be calculated from perimental measurements, and the guidance of John K.
the equation given elsewhere in the paper. Similarly, volume Rodgers who constructed and tested the experimental density
increases expected during fractionation may be calculated. equipment.
It should be emphasized that the volume changes which have
been found with the ethane-propane system are much larger REFERENCES
than those usually encountered with higher hydrocarbons.
1. Kell, G. S., and E. Whalley, National Research Council
(Canada), No. 7607 (1965).

w
88
I 80.F. 1000 PCIA
2. Francis, A. W., Ind. Eng. Chem. 49, No. 10, 1779 (1957).
3. Guggenheim, E. A., J. Chem. Phys. 13, 253 (1945).
4. Kudchadker, A. V., G. H. Alani, and B. J. Zwolinski,
Chem. Reviews 68, 659 (1968).
5. Cragoe, E, S., National Bureau of Standards, LC-736
4
O (1943).

-t
u
W
6. Technical Committee, Natural Gasoline Association of
America, Ind. Eng. Chem. 34, No. 10, 1240 (1942).
7. "Physical Constants of Hydrocarbons C, to C,O>', ASTM
1
a Special Technical Publication No. 109A (1963).
J
O 8. Sliwinski, P., Z. Phyik. Chem. N. F. 63, 263 (1969).
>
9. Seeman, F. W.,and M. Urban, Erdol und Kohle-Erdgas
4
K 83tc
82
\ Petrochemie 16, No. 2, 117 (1963).
10. Sage, B. H.,J. G. Schaafsma, and W.N. Lacey, Ind. Eng.
Chem. 26, No. 11, 1218 (1934).
11. Deschner, W. W.,and G. G.Brown, Ind. Eng. Chem. 32,

81 t
1 I I I I I I I I I I
No. 4, 836 (1941).
12. Reamer, H. H.,B. H. Sage, and W. N. Lacey, Ind. Eng.
Chem. 41, No. 3, 482 (1949).
13. Dittmar, P.,F. Schulz, and G. Strese, Chemie. Ing. Tech.
O .I .2 .3 4 .S .6 .7 .8 .9 1.0
MOLE FRACTION E T H A N E 34,437 (1962).
Figure 4 14. Van der Vet, A. P., Congress Modid du Petrole, Vol. II,
Volume Shrinkage for Ethone-Propane Mixture at 80°F, 1000 psia p. 515, Paris, 1937.
G P A T P - 1 71 I3 8 2 4 6 9 9 0030596 471 I

15. NGPSA Engineering Data Book, 8th Edition, Natural 20. Sage, B. H., D. C. Webster, and W. N. Lacey, Ind. Eng.
Gas Processors Suppliers Association, Tulsa, Okla., 1966. Chem. 29, No. 6, 658 (1937).
16. Tester, H. E., “Ethane” in Thermodynamic Functions of
G ~ 111,~pp, ~162-193,
~ vol, , edited by F. ~ i ~ ~ ~ , t t 21. ~ - H. H., R. H. Old% B. H. Sage, and W. N. Lacey,
~ Reamer,
worth, London, 1961. Ind. Eng. Cliem. 35, No. 10, 956 (1944).
17. .‘ H., J. L. and c. O . Trans.
Hurdy
22. Beattie, J. A., G. Su,and G. L. Sirnard, J. Am, Chem. Soc.
A.1.Ch.E. 43, 25 (1947). 61, 926 (1939).
18. International Critical Tables, Vol. III, p. 231, 1928.
19. Kuenen, J. P., Phil Mag. 151, 40, 173 (18951, [5j, 44, 23. Michels, A., W. Van Straaten, and J. Dawson, Physika
174 (1897) and [6], 3, 628 (1902). 20, 17 (1954).

APPENDIX A

EXPERIMENTAL APPARATUS AND CALIBRATION Omitted from Figure 6 for clarity are the constant tem-
perature bath, the dead weight tester, and the pressure
Density and Bubble Point Apparatus gauges on the displacement pumps.
The density and bubble point apparatus are shown sche- The pycnometer was constructed of stainless steel and
matically in Figure 6. The density apparatus (top of Figure includes valves 5, 6, and 7. Valves 5 and 7 are three-way
6) is described as two distinct sections, the sample storage valves which close only the lines leading to the main
section and the density measurement section. pycnometer volume. The other two connections of each of
these valves form a common line in which the closed needle
is centered. This arrangement allows an efficient purge of
DENSITY APPARATUS DEAD WEIGH the line. Valve 6 is a vent valve used in this purge. The
pycnometer had a nominal volume of 308 cc and weighed
TESTER
9 approximately 1235 grams.
PRESSURE NUL Valve 3 was used for evacuation or venting. Valve 4 was
I N D ICATOR used to isolate the storage system and null detector for
subsequent disconnection of the pycnometer. It was also
used for purging by venting liquid sample contained be-
tween it and valve 6.
The constant temperature bath contained naphtha E as
- a fluid and was fitted with cooling coils, a bare nichrome
ribbon heater, a stirrer, a platinum resistance thermometer.
RESERVO1 R and a Wheatstone bridge thermoregulator sensor. The bath
was thermostated to ‘-c 0.03”F. The temperature of the bath
was continuously monitored by the platinum resistance
thermometer and a Rubicon-Mueller bridge set to the se-
lected temperature according to the resistance thermometer’s
calibration. During the course of a measurement, the un-
balance of the Mueller bridge was periodically corrected by
minor adjustments to the automatic regulation system. This
system included a thyratron-controlled heater and manually-
controlled cooling supplied by a refrigeration unit. For tem-
peratures above 90’F no cooling was needed. I n the auto-
DISPLACEMENT
PUMP BUBBLE POINT matic regulation system, bath temperature was sensed by
CELL one arm of a Wheatstone bridge. A variable adjacent arm
outside the bath furnished coarse and fine temperature con-
Figure 6 trol. The unbalance of this Wheatstone bridge was ampli-
Density and Bubble Point Apparatus fied by a light-beam galvanometer and split-cathode photo-
tube detector combination, and was fed to a thyratron regu-
lator for proportional control of the heater current.
The storage section consists of two sample storage reser-
voirs where components may be confined over mercury and Room temperature was controlled to t 1°F by monilor-
two mercury displacement pumps. Dual storage was neces- ing the temperature and manually adjusting the air condi-
sary for the preparation of the multi-component samples. tioning controls.
The density measurement section consists of the pycnom- Pressure measurements were made with a Ruska Model
eter, the pressure null indicator, and the connecting line to 2400 dead weight tester. The dead weight tester pressure \vas
the storage section. The volume of this section, which is ex- nulled to system pressure from both directions and an ;v:>r-
ternal to the pycnometer, is termed “dead space” and is less age taken using a diaphragm-null indicator.
than 1% of the pycnometer volume. The sample under Pycnometer weighings were made on a Leiderer-Kohl-
measurement is confined in two interconnecting volumes: the busch analytical balance. This balance has a capacit:, of
pyconometer which is thermostated at the selected tempera- 2000 grams and a sensitivity of 0.2 mg. The weight of thc
ture for the measurement, and the “dead space” which is fluid was determined to & 1.0 mg using NBS calibrated
maintained a t 77°F (25°C). weights.
G P A TP-II 31 = 3824b99 0030597 308
12 ADDENDUM -PROCEEDINGS OF 49th ANNUAL CONVENTION

Auxiliary equipment included a high-vacuum system for Purging the lines was accomplished by flushing. The reser-
evacuation of the pycnometer, and a n evacuation chamber voir was cooled with ice to effect maximum transfer.
to remove traces of bath solvent from the external inter- The ethane-propane mixtures were prepared by weight.
stices of the pycnometer (primarily the exposed machine Ethane from a reservoir was transferred to the evacuated
threads of the valves and the assembly). pycnometer using the associated displacement pump. The
The bubble point apparatus is quite simple and is also pycnometer was placed in the bath and a n equilibration
shown in Figure 6. The bubble point sample was contained made at 77" and a selected pressure. The pycnometer was
in an inverted 50-cc cell and confined over mercury. The closed, disconnected, and weighed. The remaining ethane
evacuated cell was loaded with sample from the sample in the storage reservoir was discarded. The pycnometer
storage reservoir, disconnected from the density apparatus, was reconnected, placed in a bath at 77°F) lines were evacu-
and mercury introduced from a third displacement pump. It ated, and the sample transferred back to the reservoir. By
was then immersed in the constant temperature bath for cooling the reservoir to 40"F,the ethane remaining in the
bubble point measurements. Pressure measurements were pycnometer was gaseous and amounted to approximately 12
made with a calibrated Bourdon gauge. grams. When the system pressure approached that of the
vapor pressure of ethane at 40"F, transfer was complete.
Calibrations and Settings The pycnometer and storage reservoir were closed off and
For temperature measurement, a National Bureau of the pycnometer weighed. The difference in the two pycnom-
Standards calibrated platinum resistance thermometer was eter weighings yielded the quantity of the ethane in the
used, along with standard techniques for the operation and storage reservoir and the connecting lines or dead space.
checking of the Mueller bridge. Since the dead space and pycnometer are at the same con-
The volume of the pycnometer was determined by filling ditions of temperature and pressure, and their volumes are
with distilled water at 15 points (all combinations of 40, known, the quantity of ethane remaining in the dead space
60, 90, 120"F, and 500, 1000, and 1500 psig with three points can be calculated and amounts to less than 0.1 gram.
repeated) and subsequent weighing. The procedure used was From the quantity of ethane introduced into the first
identical to that used for hydrocarbon density measure- reservoir and the composition of the desired resultant mix-
ments with the exception that the water was loaded directly ture, the quantity of propane to be introduced into the
into the reservoir and only one point determined for each second reservoir was calculated. To this value was added
weighing. The pycnometer volumes were calculated using a n estimate of the quantity of propane which would remain
the water density data of Kell and Whalleyl, and were fitted in the pycnometer after the transfer or second weighing.
by least squares to the linear equation: Propane from the second reservoir is then introduced into
Volume (cc) = 307.814 +0.008776 T('F) the evacuated pycnometer to a n extent exceeding the de-
+ 0.0002111 P(psia) (1-A) sired amount. The pycnometer was weighed and the excess
successively vented until the desired pycnometer weight
with a n average deviation for 15 points of 2 .O04 cc and a was approximately attained. The remaining propane in the
maximum deviation of + . O l l cc. second reservoir was discarded, the pycnometer reconnected
The volume of the dead space was determined to be to the system, lines evacuated, and the propane transferred
2.38 cc by filling with liquid propane, equilibrating at 1000 to the second reservoir using the same procedure as for
psia and 77"F, and allowing the propane to be drawn into ethane. The quantity of propane remaining in the pycnom-
the evacuated pycnometer for weighing. eter could be controlled from 3 to 5 grams depending upon
The pressure gauge for the bubble point measurements the system pressure a t shut-off.- This allowed the calcu-
was calibrated against the dead weight tester using nitrogen lated amount of propane to be transferred. From gasous
gas as a pressure transfer fluid. The spread of the pressure propane density data and the pycnometer volume, the de-
points was about & 1 psia, the reading accuracy of the 1500- sired pycnometer shut-off pressure was calculated and the
pound gauge. reservoir slowly cooled until this pressure was achieved.
For the purpose of a good estimate of sample remaining in The correction for gasous propane left in the connecting line
a storage reservoir, the zero reading of the displacement was made as in the case of ethane.
pump w a s periodically checked and occasionally readjusted. Mixing of the ethane and propane in the reservoirs was
This was accomplished by disconnecting the top fitting on achieved by pumping one component from its reservoir into
the reservoir and handcranking the displacement pump the reservoir containing the other component. The resultant
until mercury was just visible a t the position previously mixture then was pumped back into the first reservoir. This
occupied by the fitting ferrule. In order to take into account process was repeated 20 times with about 99% of the sample
the compression of mercury and the possibility of trapped transferred in each pass. The displacement pumps were
air in the pumps, the fitting hole was plugged and the operated simultaneously, one in the forward and one in the
pump hand-cranked until a pressure of 1000 psia was ob- reverse direction, with a continual observance of the total
served on the gauge. This position on the pump scale was system pressure and the quantity remaining in each reser-
taken as the zero reading. voir as indicated by 'the displacement pump readings.
Samples containing the small amounts of methane and/or
MEASUREMENTS n-butane were prepared in a different manner. ,Weighing of
the major components into the system was unnecessary. The
Sample Preparation quantity of the major component in a reservoir could be
estimated to better than 1% from the pump readings and
Table I lists the compositions of the twelve hydrocarbon the pre-determined density if one used 1000 psia and 77°F
samples on which density and bubble point data were de- as conditions. The minor component was then quantitatively
termined. Also indicated in this table are the number of introduced by weighing. For a minor component at the 2%
data points determined for each composition. level, an error in the quantity of the major components
The hydrocarbons used were Phillips Research Grade. of 1% leads to an error of only 0.02% in the calculated
A pure component was transferred to a storage reservoir by composition. Since methane is not condensable under our
connecting the cylinder in the.place of the pycnometer. conditions, the reservoir was not cooled during the transfer,
G P A TP-3 73 E 3 8 2 4 b 7 7 0030598 2 4 4 m

NATURAL GAS PROCESSORS ASSOCIATION 13

but maintained at 77°F. In this case, the transfer to the


storage reservoir was made approximately on a volume
basis. A second weighing of the pycnometer was made for
2000
a quantitative determination of the transfer.
One ethane-propane mixture (71.7 mole percent ethane),
for which a large original sample was prepared, was used
for two consecutive additions of minor components. For
the calculations of each new composition, the quantity of the
previous sample in the reservoir was estimated from pump
readings and density, and the minor component quantitatively
-0 I500

added.
W
-
v)
a

œ
Density Measurements - The Isochor Method 3
$ 1000
W
Preliminary density measurements on propane were made œ
n
using the single-point method. That is, a single density-
pressure-temperature point was obtained from each loading
and subsequent weighing of the pycnometer. During equili-
bration the pycnometer was open to a line leading to the 500
pressure null indicator for the measurement of system pres-
sure. For the density determination the pycnometer was
closed off and weighed. The sample contained in this ex-
ternal line which we term “dead space” was used merely
as a pressure-transfer medium. The presence of this line O
in the system had no effect on the density measurements. 50 60 70 80 90 IO0 110 120
It did, however, limit the system pressure to values larger TEMPERATURE (‘FI
than the saturation pressure of the sample at ambient tem-
perature or 77°F. The single-point method yielded simple Figure 7
and direct density calculations, but was quite time con- Experimento1 Ethone Isochor Plot; Stroight t i n e s Connecting Circle (O)
suming. Points are Isochors (Lines of Constont Density); Triangle (A) Points
Define Soturation Curve which Terminates a t the Criticol Point.
In order to establish the metering characteristics of the Squore (0)Points Define Isochors with Densities Less than the Criticol
ethane-propane system, a large number of density-pressure- Density.
temperature points are required. By using the isochor method
of operation, a series of density-pressure-temperature points case of mixtures, the saturation line becomes an envelope.
can be obtained from a single loading and weighing of the For temperatures below critical, there are two saturation
pycnometer at no sacrifice of accuracy or versatility and, lines. The higher pressure line is the bubble point curve
most important, a considerable saving of time. In this and the lower pressure lines the dew point curve, Since
method, the dead-space volume is included in the measuring we are concerned only with the liquid state, any further
system. The sample contained in the dead space is no use of the terms saturation conditions, saturation pressure,
longer merely a pressure-transfer medium, but must be saturation temperature, or saturation density will refer to
considered in the density calculations. The densities associ- the bubble point saturation curve.
ated with this single loading show a small change (approx. In the isochor method, the pycnometer is loaded with
0.2%) with temperature along an isochor, which results from sample at a selected temperature and pressure which is
the change of volume of the pycnometer with temperature termed the loading conditions. The first experimental pres-
and pressure, and from the transfer of sample between the sure-temperature point of an isochor is made at the loading
dead space and the pycnometer. conditions. Further experimental points are determined by
The experimental pressure-temperature points for ethane raising or lowering the temperature and measuring the
are plotted in Figure 7. Lines of constant density or isochors equilibrium pressure for each temperature. At the last
are represented by the straight lines in the figure. The equilibration, the pycnometer is closed off and weighed.
saturation curve for the sample, which defines the low tem- If, in the course of these measurements, the temperature
perature limit of the isochors, is also shown. The upper of the pycnometer is reduced to such an extent that satura-
temperature limit of the saturation curve is the critical point. tion conditions are met, any further temperature reduction
The linear continuation of this curve is the critical isochor. will yield equilibria pressures which define the saturation
Isochors corresponding to a density less than the critical curve rather than the isochor. For bubble point measure-
density intersect the saturation curve from the low pressure ments, this procedure was actually used. On the other hand,
or vapor side. Isothermal data can be obtained from an for density measurements, saturation conditions are to be
isochor plot by determining for each isochor the pressure at avoided to prevent bubble formation or phase separation
which the isochor intersects a perpendicular line drawn at in the pycnometer or dead-space volume. If bubble forma-
the temperature of interest. The density associated with the tion takes place, it will result in erroneous densities and,
determined pressure must be interpolated from the experi- in the case of mixture samples, concentration gradients. By
mental densities. This interpolation is not critical because plotting the experimental pressure-temperature points as
of the very small change of density along an experimental they are determined, the temperature intersection of the
isochor. isochor with the saturation curve can be estimated, and a
Figure 7 was included in this paper as an aid in the low temperature limit selected to insure the absence of
description of the isochor method. The density behavior of bubble formation.
the sample must be anticipated, especially in the case of The inclusion of the dead-space volume in the density
mixtures where phase separation is to be avoided. In the measuring system results in a further limitation in the
GPA TP-3 73 3824b99 0030599 180 W

14 ADDENDUM -PROCEEDINGS OF 49th ANNUAL CONVENTION


- .
- _. ._ __ _ _ _ _ ~

minimum temperature at which an isochor point can be de- the most of 0.05%. The sign of this correction becomes
termined. This limitation involves only the isochors which negative if the system pressure at the weigh point is less
intersect the saturation curve below 77°F. In this case, bubble than the system pressure a t the initial point.
formation will take place in the dead space if the system The density data for the twelve compositions studied
pressure drops below the saturation pressure of the sample are given in Tables VIII-1 through VIII-12. The first column
i t 77°F. gives the weight of sample for a particular isochor. The
The temperature-pressure points determined for an iso- second and third columns give the temperature and pressure,
chor are termed an “isochor series”. The last point of the respectively, for a data point. The fourth column gives the
isochor series, at which time the pycnometer is closed off pycnometer volume for the measurement conditions. The
and weighed, is termed the “weigh point” of the series. The iifth column represents the dead-space correction to density,
weigh point is unique in that the density can be immediately and the final column gives the real density after applying
calculated from the weight of sample in the pycnometer and the dead-space correction to the apparent density.
thc volume of the pycnometer at the conditions of weigh
point. All other points in the isochor series are termed initial
points. For the initial points, the quantity of sample in the Bubble Point Measurements
dead space must be considered.
In preparation for bubble point measurements, the dis-
Since the dead space is maintained at 77”F, the quantity placement pump and pressure gauge were filled with mer-
of sample in this dead space can be calculated with a cury under pressure. The bubble point cell was cleaned to
knowledge of its volume, and the density of the sample at insure the absence of mercury, attached to the pump-gauge
77°F as a function of pressure. This 77°F isotherm can combination and to the density apparatus in place of the
easily be determined in the course of the measurements by pycnometer. The cell was evacuated and 3-5 cc of liquid
selecting 77°F for the loading and weighing conditions for sample introduced by cracking valve 4 and handcranking
ali isochors having a density greater than the saturation the reservoir displacement pump. Valve 8 was then closed
ciensity at 77°F. By defining the following quantities at the and the cell disconnected from the density apparatus. Mer-
time of an equilibration as follows, cury was then introduced into the cell through valve 9 until
Q = quantity of sample in the pycnometer, the sample was compressed back into liquid form. The cell
was then placed in the constant temperature bath for bubble
q = quantity of sample in the dead space,
point measurements.
V = volume of the pycnometer,
Bubble point formation is evidenced by either a distinct
P = system pressure, break in the pressure-volume gradient as the volume is
T = bath temperature, increased at constant temperature, or by a distinct break in
P the pressure-temperature gradient as the temperature is de-
DVr= density of the sample a t temperature, T, and pres- creased at constant volume. The latter method is preferred in
sure, P, and further indexing Q, q, P, and T with the sub- that it yields data of the same type as were obtained in the
script i or w to denote these variables for an initial point density measurements.
or the weigh point, respectively, we can express the density As the temperature of the sample is decreased, the sys-
calculations in mathematical form. At the weigh point, the tem pressure decreases linearly so that we are, in fact,
sample density is determining an isochor for a liquid sample of unknown
density. Upon the formation of a‘ bubble, the system pres-
sure becomes the bubble point pressure. The pressure con-
tinues to decrease with temperature, but with a reduced slope.
A plot of pressure versus temperature yields two straight
The total loading of the system is constant for all points in lines, the intersection of which is the initial bubble point
an isochor series. Thus, of the sample. For pure compounds, all points obtained
at temperatures below this intersection are also true vapor
Qi + qi = Q,T + ,q or pressures or bubble points. In the case of mixtures, any
bubble formation will alter the liquid composition and may
Qi = Q, + q,v - q, (3-A) yield low values due to the loss of the more volatile com-
ponents. However, it was found that this effect was neg-
At an initial point, the sample density is, then, ligible, and all points a few degrees below the intersection
could also be considered true bubble points. In the experi-
(4-A) ment, the sample volume is nearly constant, and any slight
change of volume during the course of the measurements did
not affect the bubble point measurements nor the position
The quantities of sample in the dead space may be caku- of the intersection of the bubble point curve with the isochor
lated from the volume (2.38 cc) and the 77°F isotherm which curve. The slight change in volume of the cell results from
P the difference in thermal expansion of the cell proper and of
is expressed as D,, as a function of P. Substituting, we the mercury it contains.
obtain, The mechanics of the bubble point determination are
quite simple. The temperature and pressure are selected
for the highest temperature point on the isochor. The pres-
sure is adjusted using the displacement pump. The remaining
points are determined with the displacement pump un-
In the above equation, the first term on the right ignores touched or isolated to achieve a constant volume system.
any transfer of sample from the dead space to the pycnom- The bath temperature is then successively lowered in incre-
eter, and the second term quantitatively corrects for this ments and the equilibrium pressure read off the gauge for
oversight. This second term yields a density correction at each temperature. Anticipating the approach to the bubble
G P A TP-L 71 3824699 O O L O b O O 7 2 2 =

NATURAL GAS PROCESSORS ASSOCIATION 15


~ ~-

point, the temperature increments were reduced to 1°F.After TABLE VIII-1


bubble formation as indicated by a sharp decrease in slope.
sufficient additional points were determined to establish Composition
the position of the second straight line through the data. 100.00 Mole Percent Propane
Additional series of measurements are made by raising the
bath temperature and adding or removing mercury from the Deod Spoce Exp.

- --
cell with the displacement pump to achieve a new sample Moss Temperoture Pressure Volume Correction Density
sm OF psi0 cc gm/cc gm/cc
volume or density. The observed gauge pressures were cor-
rected by the calibration. Further pressure correction was 163.680 65 1999.8 308.806 0.00000 0.53004
made for the difference in mercury levels at the sample-
mercury interface and for the position of the mercury- 55 1476.2 308.607 +0.00005 0.53043
nitrogen interface during the calibration of the gauge. The 45 953.9 303.409 +0.00011 0.53083
estimated uncertainty of the bubble point data is I3.0 psia.
The bubble point data for each composition were fit to 161.384 77 1998.5 308.911 o. ooooo 0.52243
the equation: 65 1404.9 308.680 +0.00005 0.52287
Ln P(psia) = A - B/T("R) (6-A) 55 906.5 308.487 +0.00012 0.52327
40 153.2 308.196 +0.00023 0.52387
The constants A and B are given in Table I along with the
temperature range over which the measurements were made.
As noted in the table, a correction should be applied at 86 1925.6 308.974 -0.00004 0.51563
higher temperature for ethane for best results. Deviation 159.328 77 1503.1 3O 8.8O 6 0.00000 0.51595
from the equation results because the critical temperature is 65 933.8 308.581 +0.00005 0.51637
being approached. Because of the special interest i n ethane,
the experimental data are given in Table IX. 52 311.6 308.335 +0.00015 0.51689
49 168.6 308.279 +0.00018 0.51701

TABLE IX 96 1858.3 309.048 -0.00009 O. 5O 788


Ethane Bubble Point Data 86 1409.7 308.865 -0.00004 0.50823
80 235.1 308.389 +0.00009 0.50917
Tempeioture Pressure, F i 0 Deviation 156.988 77 1004.7 308.701 0.00000 0.50854
OF Experimento1 Calculated1 , psi0
110 1959.4 309.192 -0.00016 0.49970
90.1 7082 693 +15 95 1322.2 308.926 -0.00009 0.50020
86.0 672 663 9 154.552 77 552.6 308.605 0.00000 0.50081
85.0 664 656 8
68 166.0 308.445 +0.00006 0.50113
83.0 648 641 7
81.0 632 628 4 120 1898.4 309.267 -0.00022 0.49173
78.0 610 607 3
105 1296.2 309.008 -0.00015 0.49221
76.0 596 594 2
90 690.6 3O 8.749 -0.00008 0.49269
75.0 591 587 4
590 587 3
152.142 77 163.0 308.523 o. ooooo 0.49313
75.0
70.0 556 554 2 120 1473.1 309.177 -0.00007 0.48395
70.0 557 554 3 149.646 104 861.7 308.908 0.00000 0.48444
68.0 543 542 1
88 248.4 308.638 +0.00009 0.48495
67.0 536 535 1
66.0 530 529 1 147.208 127 1362.1 309.215 0.00000 0.47607
65.0 524 523 1 117 1002.0 309.051 +0.00004 0.47636
62.0 507 505 2 107 639.1 3O8.8 87 +0.00009 0.47667
61.0 500 499 1 97 277.6 308.723 +0.00014 0.47697
60.0 494 493 1
60.0 494 493 1 144.564 130 1106.8 309.187 0.00000 0.46756
54.0 459 458 1 118 696.5 308.996 +0.00005 0.46790
53.0 453 453 O 105 252.1 3o8.7aa +0.00012 0.46829
52.0 447 447 O
51.0 441 442 -1 142.158 130 819.8 309.127 0.00000 0.45987
42.0 394 394 O 122 560.4 309.002 +0.00003 0.46009
41.0 389 387 O 114 302.6 308.877 +0.00007 0.46031
40.0 384 384 O
139.752 130 575.4 309.075 0.00000 0.45216
_ _ ~
125 422.2 308.999 +0.00002 0.45229
i. Calculated from the euqation: Ln P(psja) = 12.41 - 3227/T(OR).
121 301.3 308.938 +0.00004 0.45240
2. Selected value (Reference 4).
16 ADDENDUM -PROCEEDINGS OF 49th ANNUAL CONVENTION

TABLE VIII-2 TABLE VIII-4


Composition Composition
97.58 Mole Percent Propane 37.00 Mole Percent Ethane
2.42 Mole Percent Methane 63.00 Mole Percent Propane

Dead Space Ex. Dead Space Exp.


---
Mass
gm
Temperature Pressure
OF psia
Volume
cc
Correction
gm/cc
Density
sm/Cc
Moss
---
gm
Temperoture Pressure
OF psia
Volume
CC
Correction
gm/cc
Density
gm/cc

159.721 77 1992.1 308.909 0.00000 0.51705 150.598 77 1998.4 308.911 0.00000 0.48751
57 1021.2 308.529 +0.00011 0.51780
44 387.8 308.281 +0.00020 0.51830 67 1547.9 308.728 +0.00006 0.48786
57 1094.8 308.545 +0.00012 0.48821
88 1906.6 308.989 -0.00006 0.50849
157.136 77 1404.2 308.785 0.00000 0.50889 42 413.0 308.269 +0.00025 0.48878
66 899.2 308.582 +0.00006 0.50928
55 390.3 308.378 +0.00013 0.50969 147.989 77 1501.9 308.806 0.00000 0.47923
67 1075.0 308.628 +0.00006 0.47957
103 1924.0 309.123 -0.00013 0.49840
90 1363.9 308.891 -0.00006 0.49885 60 778.8 308.504 +0.00009 0.47979
154.108 77 805.3 308.659 0.00000 0.49928
65 286.5 308.444 +0.00007 0.49970 83 1500.7 308.858 -0.00004 0.47444
146.547 77 1253.9 308.753 0.00000 0.47464
115 1823.5 309.207 -0.00020 0.48817
100 1223.7 308.949 -0.00014 0.48864 66 798.8 308.561 +0.00007 0.47500
88 742.5 308.744 -0.00007 0.48903 55 346.3 308.369 +0.00016 0.47539
151.O07 77 301.3 308.552 0.00000 0.48940
90 1500.0 308.920 -0.00008 0.46860
120 1471.1 309.177 -0.00015 0.47773
115 1285.3 309.094 -0.00013 0.47788 144.786 77 979.3 308.696 0.00000 0.46903
147.749 90 351.9 308.677 0.00000 0.47865 70 702.3 308.576 +0.00005 0.46926
120 745.4 309.023 -0.00006 0.46009 100 1498.7 309.007 -0.00014 0.46022
114 548.8 308.929 -0.00003 0.46026
142.197 108 351.9 308.835 0.00000 0.46043 90 1127.2 308.841 -0.00009 0.46052
142.255 77 638.0 308.624 0.00000 0.46093
70 389.9 308.510 +0.00005 0.46115

TABLE VIII-3 110 1501.7 309.096 -0.00020 0.45167


99 1113.3 308.917 -0.00014 0.45199
Composition
99.11 Mole Percent Propane 88 725.8 308.739 -0.00008 0.45232
0.89 Mole Percent n-Bühne 139.672 77 339.9 308.561 0.00000 0.45266
Dead Space EXF. 120 1500.4 309.183 -0.00018 0.44261
Mass Temperature Pressure Volume Correction Density
--- sm OF psi0 cc gm/cc gm/cc 105 1002.3 308.946 -0.00011 0.44302
161.608 77 1995.8 308.910 0.00000 0.52315 136.904 88 443.1 308.679 0.00000 0.44352
66 1452.7 308.699 +0.00006 0.52357
55 903.5 308.486 +0.00012 0.52399 120 1201.5 309.120 -0.00014 0.43371
44 351.2 308.273 +0.00020 0.52444 108 830.8 308.937 -0.00008 0.43403
98 1946.0 309.084 -0.00010 0.50846 134.113 95 426.5 308.737 0.00000 0.43439
86 1407.1 308.865 -0.00005 0.50887
157.187 77 1003.5 308.701 0.00000 0.50919 125 1081.1 309.139 -0.00011 0.42419
60 232.9 308.389 +0.00011 0.50981 115 801.3 308.992 -0.00006 0.42444
157.230 77 1005.0 308.701 0.00000 0.50933 131.167 105 503.4 308.841 0.00000 0.42471
60 233.7 308.389 +0.00011 0.50995
130 959.8 309.157 -0.00010 0.41313
120 1923.0 309.272 -0.00029 0.49297 120 690.6 309.012 -0.00005 0.41337
105 1315.9 309.012 -0.00022 0.49346
90 707.7 308.752 -0.00015 0.49394 127.753 110 425.3 308.868 0.00000 0.41362
152.530 77 177.2 308.526 0.00000 0.49438
130 750.6 309.113 --0.00002 0.40231
144.873 130 1107.4 309.188 0.00000 0.46856 124.366 125 626.9 309.043 0.00000 0.40242
118 697.2 308.996 +0.00006 0.46891
0.46929 120 508.0 308.974 +0.00003 0.40254
105 250.9 308.787 +0.00002
GPA T P - L 71 I 3824699 00LOb02 5 T 5 I

NATURAL GAS PROCESSORS ASSOCIATION 17


. ._ ~ .~ .__ - - -.- .- ~

TABLE VIII-5 TABLE VIII-6


Composition Composition
49.89 Mole Percent Ethane 48.28 Mole Percent Etliane 48.49 Mole Percent Propane
50.11 Mole Percent Propane 3.23 Mole Percent Methane

Dead Space Exp. Dead Space ExP


Mass Temperature Pressure Volume Correction Density Mass Temperature Prerrure Volume Correction Density
---
gm OF psi0 cc gm/cc gm/cc ---
gm psi0 OF cc gm/cc gm/cc

62 914.3 308.550 -0.00010 0.46552 57 1500.0 308.630 -0.00014 0.47297


56 668.3 308.445 -0.00006 0.46571 48 1102.8 308.467 -0.00007 0.47329
143.666 50 425.3 308.342 0.00000 0.46593 147.939 40 748.9 308.323 0.00000 0.47358

90 1500.0 308.919 -0.00008 0.4531 1 77 2000.0 308.911 -0.00027 0.46604


139.998 77 559.3 308.701 0.00000 0.45351 65 1473.9 308.699 -0.00020 0.46643
65 1005.3 308.501 $0.00009 0.45389 55 1072.9 308.523 -0.00013 0.46677
145.971 41 484.7 308.276 0.00000 0.46727
95 1500.0 308.963 -0.0001 1 0.44894
138.740 77 849.3 308.668 0.00000 0.44948 77 1500.0 308.806 -0.00016 0.45621
65 406.8 308.469 +0.00010 0.44987 65 1030.4 308.601 -0.00009 0.45658
142.851 55 636.4 308.430 0.00000 0.45692
108 1500.0 309.077 -0.00019 0.43668
90 893.3 308.791 -0.00011 0.43717 90 1500.0 308.920 -0.00008 0.44460
135.028 77 437.3 308.585 0.00000 0.43757 139.293 77 1028.3 308.706 0.00000 0.44499
62 485.4 308.460 +0.00012 0.44547
118 1500.0 309.165 -0.00015 0.42704
110 931.9 308.888 -0.00013 0.42744 105 1500.0 308.052 -0.00018 0.43027
132.071 90 621.9 308.734 0.00000 0.42778 92 1074.5 308.848 -0.00011 0.43062
134.952 77 584.5 308.6 13 0.00000 0.43106
120 1250.0 309.130 -0.00014 0.41641
108 899.3 308.951 -0.00008 0.41671 120 1500.0 309.183 -0.00019 0.41531
128.768 95 523.8 308.757 0.00000 0.41705 102 975.4 308.914 -0.00010 0.41576
130.385 87 531.4 308.689 0.00000 0.41616
120 900.0 309.056 -0.00005 0.40102
123.953 110 644.5 308.914 0.00000 0.40125 125 1350.0 309.195 -0.00013 0.40408
112 995.5 309.006 -0.00007 0.40439
125 750.0 309.068 -0.00004 0.38398 126.899 100 671.5 308.832 0.00000 0.40468
118.689 118 593.8 308.974 0.00000 0.38414
125 1000.0 309.121 -0.00008 0.38643
120 882.5 309.053 -0.00005 0.38654
115 764.0 308.984 -0.00003 0.38665
121.396 110 646.4 308.915 0.00000 0.38676

130 900.0 309.144 -0.00005 0.37106


125 795.7 309.078 -0.00002 0.37117
116.644 120 691.7 309.013 0.00000 0.37127
GPA TP-Ii 7L = 382Yb99 O O L O b 0 3 q3L

18 ADDENDUM -PROCEEDINGS OF 49th ANNUAL CONVENTION

TABLE V m - 7 TABLE Vm-8


Composition Composition
71.71 Mole Percent Ethane 70.05 Mole Percent Ethane 27.64 Mole Percent Propane
28.29 Mole Percent Propane 2.31 Mole Percent Methane

Dead Space Exp.


Dead Space Exp. Moss Temperature Pressure Volume Correction Density
---
Mass
gm
Temperature Pressure
OF pio
Volume
cc
Correction
gmkc
Density
sm/cc
sm OF - Ph cc sm/cc sm/cc

136.350 77 2001.2 308.911 0.00000 0.44139


137.921 77 1997.8 308.910 0.00000 0.44648 65 1533.1 308.707 +0.00008 0.44176
65 1518.6 308.704 +0.00008 0.44686 55 1142.0 308.537 +0.00017 0.44210
55 1117.3 308.531 +0.00015 0.44718 45 750.7 308.366 +0.00029 0.44246
40 522.6 308.274 +0.00032 0.44772
88 1897.6 308.986 -0.00007 0.42946
84 2001.9 308.973 -0.00004 0.44073 132.718 77 1501.9 308.806 0.00000 0.42978
136.187 77 1734.3 308.855 0.00000 0.44094 66 1105.8 308.626 +0.00008 0.43012
65 1274.4 308.652 +0.00008 0.44131 55 714.3 308.447 +0.00021 0.43049
45 606.6 308.315 +0.00028 0.44200
100 1740.2 309.058 -0.00016 0.41376
90 1977.8 309.020 -0.00007 0.43499 90 1418.7 308.902 -0.00010 0.41403
134.442 77 1499.6 308.805 0.00000 0.43536 127.925 77 1002.3 308.700 0.00000 0.41440
65 1055.9 308.606 +0.00013 0.43577 65 618.0 308.515 +0.00013 0.41478
54 658.4 308.426 +0.00020 0.43610
123.316 110 1598.6 309.116 0.00000 0.39893
98 1998.6 309.095 -0.00012 0.42840 95 1166.2 308.893 +0.00008 0.39931
85 1540.4 308.884 -0.00005 0.42877 77 652.2 308.626 +0.00025 0.39981
132.454 77 1257.8 308.754 0.00000 0.42900
60 662.0 308.479 +0.00015 0.42953 119.762 120 1608.8 309.206 0.00000 0.38732
100 1075.0 308.918 +0.00012 0.38780
1O0 1760.8 309.062 -0.00014 0.42027 80 551.0 308.631 +0.00029 0.38833
90 1430.0 308.905 -0.00009 0.42050
129.933 77 997.7 308.699 0.00000 0.42091 116.416 120 1382.4 309.158 0.00000 0.37656
105 1013.5 308.948 +0.00009 0.37690
110 1775.6 309.153 -0.00019 0.41084 90 650.5 308.740 +0.00021 0.37728
99 1435.0 308.985 -0.00016 0.41111
88 1093.1 308.816 -0.00009 0.41140 110.696 120 1092.8 309.097 0.00000 0.35813
127.076 77 751.7 308.647 0.00000 0.41172 110 885.4 308.965 +0.00006 0.35834
100 676.2 308.833 +0.00013 0.35856
120 1792.7 309.244 -0.00028 0.40126
105 1357.9 309.021 -0.00022 0.40162
90 924.2 308.798 -0.00011 0.40202
124.175 77 549.3 308.605 0.00000 0.40238

120 1500.3 309.183 -0.00022 0.38997


105 1098.8 308.966 -0.00014 0.39033
95 833.3 308.823 -0.00008 0.39057
120.641 85 571.1 308.679 0.00000 0.39083

116.349 120 1231.6 309.126 0.00000 0.37638


110 989.6 308.987 +0.00005 0.37660
100 750.8 308.849 +0.00012 0.37684

120 1000.4 309.077 -0.00004 0.36023


1 11,349 112 831.0 308.971 0.00000 0.36039
105 683.5 308.879 +0.00004 0.36054
GPA TP-II 71 3 8 2 4 b 9 9 0010b04 378

NATURAL GAS PROCESSORS ASSOCIATION 19


-___~__. -. ~~

TABLE VIII-9 TABLE VITI-10


Composition
69.52 Mole Percent Ethane 27.47 Mole Percent Propane Composition
2.18 Mole Percent Methane 0.83 Mole Percent n-Butane 89.97 Mole Percent Ethane
10.03 Mole Percent Propane
Dead Space Exp.
Mass Temperature Pressure Volume Correction Density Dead Space Exp.
am OF cc gm/cc gm/cc Mass Temperature Pressure Volume Correction Density
gm OF psia cc gm/cc gm/cc
136.922 77 1996.2 308.911 0.00000 0.44324
65 1527.4 308.706 +0.00008 0.44361 129.605 77 2000.3 308.911 0.00000 0.41955
55 1132.8 308.535 +0.00017 0.44395 65 1562.3 308.713 +0.00009 0.41991
45 739.8 308.364 +0.00028 0.44431 50 1012.0 308.465 +0.00025 0.42041

88 1900.2 308.986 -0.00007 0.43156 127.593 77 1751.2 308.858 0.00000 0.41311


133.367 77 1502.8 308.806 0.00000 0.43188 65 1331.9 308.665 +0.00010 0.41347
66 1104.2 308.625 +0.00009 0.43222 50 809.7 308.423 +0.00029 0.41399
55 707.0 308.445 +0.00021 0.43259
90 1875.9 308.999 -0.00010 0.40367
103 1844.3 309.106 -0.00018 0.41607 124.763 77 1451.9 308.795 0.00000 0.40403
90 1422.9 308.903 -0.00010 0.41642 65 1061.5 308.607 +0.00011 0.40440
128.666 77 1001.1 308.700 0.00000 0.41680 55 734.6 308.451 +0.00026 0.40474
65 613.6 308.513 +0.00013 0.41718
110 1825.6 309.164 -0.00018 0.38079
115 1751.4 309.192 -0.00028 0.40101 90 1270.9 308.871 -0.00011 0.38121
96 1196.8 308.908 -0.00016 0.40150 117.781 77 912.7 308.681 0.00000 0.38156
124.075 77 647.5 308.625 0.00000 0.40202 65 584.2 308.507 +0.00020 0.38198

117.540 120 1395.6 309.161 0.00000 0.38019 110 1451.5 309.085 -0.00031 0.36251
105 1020.2 308.950 +0.00009 0.38054 90 962.1 308.806 -0.00016 0.36299
90 650.4 308.740 +0.00021 0.38092 112.142 77 650.6 308.626 0.00000 0.36336

111.963 120 1107.7 309.100 o. ooooo 0.36222 110 2144.2 309.231 -0.00023 0.39207
110 890.2 308.966 +0.00006 0.36244 1O0 1841.6 309.079 -0.00017 0.39233
1O0 675.5 308.833 +0.00013 0.36266 90 1539.4 308.928 -0.0001 1 0.39257
121.310 77 1149.7 308.724 0.00000 0.39294
70 939.8 308.626 +0.00008 0.39315

120 1250.0 309.130 -0.00014 0.33203


110 1056.6 309.001 -0.00008 0.33223
102.684 100 865.9 308.873 0.00000 0.33245

120 1000.1 309.077 -0.00010 0.29527


110 854.7 308.959 -0.00004 0.29544
91.292 105 783.4 308.900 0.00000 0.29554

115 1272.7 309.091 -0.00007 0.34286


105.997 105 1059.8 308.958 0.00000 0.34308
95 853.3 308.827 +0.00009 0.34332
85 650.3 308.696 +0.00020 0.34357

96.443 120 1087.7 309.096 0.00000 0.31202


110 921.7 308.973 +0.00006 0.31220
1O0 760.4 308.851 +0.00014 0.31241
GPA T P - 1 71 m 3824699 0010605 204 m

20 ADDENDUM -PROCEEDINGS OF 49th ANNUAL CONVENTION

TABLE Ym-11 TABLE VIII-11 (Continued)


Dead
Correction
Space EXP:
Composition Mass
gm
Temperature Pressure
OF psi0
Volume
cc gm/cc
Density
gm/cc
100.00 Mole Percent Ethane
120 1408.5 309.163 -0.00041 0.31921
Dead Spoce Exp. 100 1034.9 308.909 -0.00032 0.31961
Mass Temperature Pressure Volume Correction Density
gm OF psi0 cc gm/cc gm/cc 86.79 793.2 308.742 -0.00018 0.31992
124.739 77 2001.3 308.911 0.00000 0.40380 80 672.2 308.657 -0.00008 0.32011
66 1620.1 308.734 +0.00008 0.40411 98.828 77 620.6 308.620 0.00000 0.32023
55 1237.9 308.557 +0.00019 0.40446
120 1200.2 309.119 -0.00030 0.29222
85 1998.0 308.981 -0.00006 0.39539 105 970.0 308.939 -0.00019 0.29248
122.187 77 1733.9 308.855 0.00000 0.39561 90 747.5 308.761 -0.00007 0.29279
65 1341.7 308.667 +0.00010 0.39595 90.423 85 675.7 308.702 0.00000 0.29292
45 694.7 308.355 +0.00043 0.39668
120 1100.1 309.098 -0.00016 0.27018
119.703 77 1500.6 308.805 0.00000 0.38763 105 903.4 308.925 -0.00006 0.27043
67 1191.7 308.653 +0.00009 0,38792 83.561 97 802.7 308.834 0.00000 0.27057
55 826.0 308.470 +0.00027 0.38833 90 715.3 308.754 +0.00007 0.27071
50 674.4 308.394 +0.00040 0.38855
125 1000.1 309.121 -0.00016 0.20493
1O0 2000.2 309.113 -0.00016 0.38009 110 872.5 308.962 -0.00009 0.20511
85 1560.4 308.888 -0.00006 0.38046 63.398 92 721.7 308.773 0.00000 0.20532
117.541 77 1328.0 308.769 0.00000 O.38O 68
66 1006.3 308.605 +0.00012 0.38100 120 879.8 309.052 -0.00013 0.15013
54 667.6 308.428 +0.00035 0.38145 110 820.7 308.952 -0.00009 O.15022
100 761.4 308.852 -0.00005 0.15030
90 1502.5 308.920 -0.00011 0.37145 46.438 90 701.3 308.751 0.00000 0.15041
80 1226.0 308.774 -0.00003 0.37171
114.783 77 1144.0 308.730 0.00000 0.37179 120 799.9 309.035 -0.00011 0.11467
70 955.4 308.629 +0.00008 0.37199 105 737.7 308.890 -0.00007 0.11477
60 684.4 308.484 +0.00027 0.37236 35.472 90 674.1 308.745 0.00000 0.11489

120 1901.2 309.267 -0.00032 0.35270


106 1562.0 309.073 -0.00025 0.35299
92 1225.4 308.879 -0.00016 0.35331
109.178 77 870.0 308.672 0.00000 0.35370
68 659.7 308.549 +0.00017 0.35401

120 1632.9 309.255 -0.00038 0.33681


110 1416.0 309.077 -0.00033 0.33705
100 1202.6 308.944 -0.00026 0.33726
85 886.5 308.746 -0.00012 0.33762
80 781.6 308.680 -0.00005 0.33776
104.276 77 720.7 308.641 0.00000 0.33786
74 658.3 308.601 +0.00006 0.33796
73 637.2 308.588 +0.00009 0.33800

120 1487.5 309.180 -0,00042 0.32612


105 1190.1 308.986 -0.00033 0.32642
90 898.2 308.792 -0.00020 0.32675
100.961 77 650.5 308.626 0.00000 0.32713
NATURAL GAS PROCESSORS ASSOCIATION 21

TABLE VIII-12
Composition
91.14 Mole Percent Ethane
3.26 Mole Percent Methane

Dead Space .xE


Mass Temperoture Pressure Volume Correction Density
gm OF - pria cc gm/cc gm/cc

122.994 77 1995.9 308.910 0.00000 0.39815


61 1459.8 308.656 +0.00013 0.39861
50 1086.6 308.481 +0.00026 0.39897
40 757.6 308.324 +0.00048 0.39939

85 1736.6 308.925 -0.00006 0.38114


117.763 77 1499.0 308.805 0.00000 0.38135
65 1143.1 308.625 +0.00012 0.38170
52 759.6 308.430 +0.00036 0.38218

90 1572.7 308.935 -0.00011 0.36823


113.793 77 1221.3 308.747 0.00000 0.36856
60 766.1 308.501 +0.00028 0.36912

95 1438.7 308.950 -0.00017 0.35434


85 1196.4 308.811 -0.00009 0.35458
109.526 77 999.8 308.700 0.00000 0.35480
67 759.5 308.561 +0.00017 0.35513

110 1577.7 309.111 -0.00030 0.34073


99 1332.5 308.963 -0.00023 0.34097
88 1089.5 308.817 -0.00014 0.34122
105.417 77 850.2 308.668 0.00000 0.34152

120 1613.5 309.207 -0.00040 0.32782


100 1205.9 308.945 -0.00023 0.32823
88 975.5 308.793 -0.00017 0.32849
101.487 77 750.8 308.647 0.00000 0.32881

120 1300.2 309.141 -0.00022 0.29568


105 1060.4 308.958 -0.00014 0.29595
91.480 90 826.6 308.777 0.00000 0.29627

120 1220.6 309.124 -0.00019 0.28233


110 1075.8 309.005 -0.00012 0.28250
100 931.9 308.887 -0.00005 0.28268
87.332 95 857.2 308.828 0.00000 0.28279