Technical Publication
TPI
Dr. J. R. Tomiinson
Gulf Research 81DevelopmentCompany
Pittsburgh, Pennsylvania
February, 1971
Reprinted 1991
6526 East 60th Street Tulsa, Oklahoma 74145 Phone: 918/4933872 FAX: 918/493.
.3875
G P A T P  1 71 3 8 2 4 6 9 9 0010587 4 6 9 E
FOREWORD
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
nButane P,T Points Number
Isochors
Temp. Range
OF A
Constants
B
 
PSATbO
psia
DSATIO
sm/=
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
T60 = (P1000) [Bo + B, (1R) + B, (1R)?] table for the correlation and a quite small severalpage
+ Ao + A1 (1R) + A, (1R)' (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 ethanepropane 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 ethanepropane
mixtures were temperatureleast squared to the linear iso
T60 = (PPSAT60) Bo + (P1000) [BI (1R) + B, chor equation using the computer. The selected value of
(lR)'] +
A, (1R) A2 (iR)* + (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 interrelated 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 ethanepropane system. Thus, it is possible A1 A,, + A11X + A12X2 + A,3X3
1 (7)
to correlate the liquid density data for the ethanepropane
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 doubleindexed 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) ethanepropanemethane data along with the ethanepropane
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 ethanepropane mixture to match up with the isochor
BI, 0.31187 1.55252 i 2.76145 1.7527 plot for ethanepropane. 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 twophase 50 0.4515 0.0035 0.5
region. 55 0.4447 0.0036 0.5
The ethanepropane 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 TPII 7 1 W 3824679 OCIL0591 9 9 T W
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 twentysix 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 selfevident from the rearrange
The equations used by Francis are: ment of the linear isochor equation to yield,
A. Linear isochor P = P, + S(TT,) PP,
B. Slope equation lnS=AD +
B s= (18)
C. Saturation density equation D, = function (T,) TT,
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.
tT,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 TP3 73 = 3824677 0030572 826

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, nbutane, and iso
Valid Range butane. His values for nbutane 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 1520°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
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
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 12% high in density, and the latter to be about Literature D a t a
G P A TPL 7L 3824b99 0030595 535
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, LC736
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 KohleErdgas
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 EthonePropane 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, ~162193,
~ 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 threeway
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 RubiconMueller 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 thyratroncontrolled 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 lightbeam galvanometer and splitcathode 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 multicomponent 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 diaphragmnull indicator.
than 1% of the pycnometer volume. The sample under Pycnometer weighings were made on a LeidererKohl
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 TPII 31 = 3824b99 0030597 308
12 ADDENDUM PROCEEDINGS OF 49th ANNUAL CONVENTION
Auxiliary equipment included a highvacuum 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 ethanepropane 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 50cc 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) (1A) 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 shutoff. 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 shutoff 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 handcranked 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 nbutane 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 predetermined 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 TP3 73 E 3 8 2 4 b 7 7 0030598 2 4 4 m
added.
W

v)
a
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Density Measurements  The Isochor Method 3
$ 1000
W
Preliminary density measurements on propane were made œ
n
using the singlepoint method. That is, a single density
pressuretemperature 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 pressuretransfer 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 singlepoint 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
ethanepropane system, a large number of densitypressure Density.
temperature points are required. By using the isochor method
of operation, a series of densitypressuretemperature 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 deadspace 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 pressuretransfer 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 suretemperature point of an isochor is made at the loading
dead space and the pycnometer. conditions. Further experimental points are determined by
The experimental pressuretemperature 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 deadspace 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 pressuretemperature 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 deadspace volume in the density
mixtures where phase separation is to be avoided. In the measuring system results in a further limitation in the
GPA TP3 73 3824b99 0030599 180 W
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 VIII1 through VIII12. The first column
i t 77°F. gives the weight of sample for a particular isochor. The
The temperaturepressure 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 deadspace 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 deadspace 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 pumpgauge
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 35 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 pressurevolume gradient as the volume is
T = bath temperature, increased at constant temperature, or by a distinct break in
P the pressuretemperature 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, (3A) 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
(4A) 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 TPL 71 3824699 O O L O b O O 7 2 2 =
 
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) (6A) 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
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
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
TABLE VIII12
Composition
91.14 Mole Percent Ethane
3.26 Mole Percent Methane