Two-Phase Isentropic Compressibility

and Two-Phase Sonic Velocity for

Multicomponent-Hydrocarbon Mixtures
Abbas Firoozabadi, SPE, and Huanquan Pan,* SPE, Reservoir Engineering Research Inst.
Summary
Two-phase compressibility and two-phase sonic velocity of hydrocarbon mixtures are needed for a variety of applications in well
testing, metering, and seismic exploration. In this work, a thermodynamic model is presented to estimate the two-phase isentropic
compressibility and two-phase sonic velocity. The model accounts
for the mass transfer between the equilibrium phases and the effect of capillary pressure. The results reveal that isothermal and
isentropic compressibilities can be different by a factor of 20 in
the two-phase near the retrograde dewpoint. With the exception of
the retrograde dewpoint, the difference between the isentropic
compressibility in the single phase and two phase is less than the
corresponding difference for the isothermal compressibility.
The sonic velocity in the two phase can be either less or more
than the single phase. For the hydrocarbon mixtures that the sonic
velocity decreases in the two phase, the decrease is much less
pronounced than in nonhydrocarbon systems such as water-steam
and water-air.

Introduction
Fluid compressibility and sonic velocity are used for a wide range
of problems in the production and exploration of hydrocarbon
reservoirs. These include well testing, metering, and seismic exploration. Various methods are available for the estimation of
compressibility and sonic velocity in the single phaseboth gas
and liquid states.1 For hydrocarbon mixtures in the two-phase
state, the available methods are unreliable.
Compressibility is often defined on the basis of the thermodynamic path. For an isothermal process, the compressibility relates
volume change to pressure change at constant temperature. In an
isentropic path, the volume and pressure changes are given by
isentropic compressibility. These two compressibilities in the
single-phase state are related by2
c T c P /c V c S ,

where c T is the isothermal compressibility and c S is the isentropic

compressibility; c P and c V are the heat capacity at constant pressure and volume, respectively. Since c P c V , then c T c S . The
difference between c T and c S depends on pressure, temperature,
and composition, and may vary from 10 to 300% in the single
phase for pure hydrocarbons. Available techniques are adequate
for the reliable estimation of c T and c S for hydrocarbon mixtures
in the single-phase state. For reservoir engineering applications,
c T represents the fluid compressibility in the reservoir away from
the wellbore. In the wellbore, due to expansion, the fluid may
undergo heating or cooling and the process may become nonisothermal. If the heat loss can be neglected, the isentropic compressibility may better represent the pressure and volume changes. In
many real applications, the compressibility is perhaps between the
two limits.
Fluid compressibility in the two-phase gas-liquid state can be
very different from the single-phase gas and liquid states. While
*Now with Incyte Genomics.
Copyright 2000 Society of Petroleum Engineers
This paper (SPE 65403) was revised for publication from paper SPE 38844, first presented
at the 1997 SPE Annual Technical Conference and Exihibition, San Antonio, Texas, 58
October. Original manuscript received for review 25 July 1997. Revised manuscript received 3 April 2000. Paper peer approved 14 April 2000.

SPE Reservoir Eval. & Eng. 3 4, August 2000

the gas-phase compressibility is higher than the liquid phase, the

two-phase gas-liquid compressibility can be higher than the gasphase compressibility. The procedure for the calculation of the
isothermal two-phase compressibility of hydrocarbon mixtures is
presented in Ref. 3. It is clear from the work of Ref. 3 that any
averaging technique based on individual phase compressibilities is
unacceptable, and may lead to an order of magnitude error. The
results presented in Ref. 3 are based on the assumption that the
interface between the gas and liquid phases is flat. In porous media, the interface is curved and, therefore, capillary pressure may
affect the two-phase compressibility. One purpose of this work is
to account for the effect of capillary pressure on two-phase compressibility.
Similar to the single phase, where two types of
compressibilityisentropic and isothermalare defined, in the
two phase, one can also define isothermal and isentropic compressibilities. To our knowledge, there is no rigorous procedure in
the literature for the estimation of two-phase isentropic compressibility of hydrocarbon mixtures. In the two phase for a constant
entropy path, mass transfer between phases becomes important. A
main objective of this work is to propose the methodology for the
calculation of the two-phase isentropic compressibility using a
cubic equation of state to describe all the physical parameters.
Two-phase isentropic compressibility may be more appropriate
than two-phase isothermal compressibility for well-testing applications in two-phase flowing conditions; around the welbore due
to expansion, temperature may rise or may fall.2
Closely related to compressibility is the sonic velocity, which is
an important parameter in seismic and well-logging technologies.
The sonic velocity and the compressibility are related by a
v /c S , where a is the sonic velocity, v is the fluid molar volume, and c S is the isentropic compressibility.
The sonic velocity of a single-phase liquid is higher than the
sonic velocity in the single-phase gas. However, the sonic velocity
can be much lower in the two-phase gas-liquid mixture than in
either the gas or the liquid. A substantial difference exists between
the sonic velocity of the air-water, and steam-water systems. Twophase water-air and water-steam data reveal that:4 the presence of
1% by volume air in the form of gas bubbles reduces the sonic
velocity from 1500 to 100 m/s, and the sonic velocity in the
water-steam system can be as low as 10 m/s. Thermodynamic
models have been developed to describe sonic velocity both for
the steam-water4,5 and air-water mixtures.4,6 These models accurately predict the sonic velocity in the two phase. It should be
pointed out that the sonic velocity in a two-phase system depends
on the fluid distributions.5 In this work, we assume that the phases
are homogeneously distributed. As an example, when, below the
bubblepoint, the gas phase appears, it will be in the form of gas
bubbles uniformly distributed in the liquid. Most of the experimental data on sonic velocity in the two phase are for the homogeneous two-phase flow systems. The homogeneous two-phase
model is proper for porous media in the two-phase flow regime.
While most models for water-air and water-steam assume a flat
interface, Kieffer4 takes into account the effect of capillary pressure. She, however, assumes that the interface curvature and the
interfacial tension do not change as a result of pressure disturbance. Based on these two assumptions, the sonic velocity increases as the gas-bubble radius decreases. The work of Kieffer
reveals a strong effect of capillary pressure on the sonic velocity
of water-air mixtures when the bubble radius is less than 105 cm.
Since for water-air the interfacial tension, 72 dyn/cm, the cor1094-6470/2000/34/335/7/$5.000.50

335

V j z j n j,t RT/p j ,

where n j,t is the total number of moles of phase j, and z j is the

compressibility factor of phase j. From Eqs. 5 and 6,
2

V t RT

z n

j j,t

j1

/p j .

The key term in the above is ( V t / p 2 ) S,n ; the procedure for its
estimation is provided in Appendix A.

Fig. 1Schematics of changes associated with the calculation

of c S .

responding P c 210 psi for bubble radius of 105 cm is very

high for the porous media unless it is very tight. The published
thermodynamic models are mostly intended for single-component
fluids such as water-steam, and for two-component fluids such as
water and air where the mass transfer between the phases is negligible. These models may not be suitable for hydrocarbon mixtures and petroleum fluids in the two phase. The mass transfer
between the phases may be a key factor in the estimation of the
sonic velocity.
In this work, we first present a thermodynamic model for the
calculation of isentropic compressibility and sonic velocity in the
two phase. The effect of interface curvature and the changes of
interfacial tension in an isentropic path are taken into account.
Then, the isothermal and isentropic compressibilities for a number
of hydrocarbon mixtures and a crude are compared. Next, sonic
velocity in the two phase and the single phase is presented for the
same hydrocarbon systems. The paper ends with a number of
conclusions on the two-phase compressibility and sonic velocity.
Problem Formulation
The isentropic compressibility of a single-phase fluid, c S , is defined as
c S 1/V V/ p S,n ,

where V is the volume, p the pressure, S the entropy, and n is the

composition vector. The composition vector n is defined by n
(n 1 ,n 2 ,n 3 ,...,n c ), where c is the total number of components
and n i is the number of moles of component i. The expression for
the two-phase gas-liquid compressibility is similar to Eq. 2,
c S 1/V t V t / p 2 S,n .

In the above equation, V t is the total volume; i.e., the volume of

the gas and liquid phases. Fig. 1 shows the schematics of the
process for the estimation of c S by decreasing the pressure of
phase 2 by a small amount. In this work, we define the two-phase
compressibility using the liquid-phase pressure p 2 . For a flat interface, the gas-phase pressure p 1 is equal to the liquid-phase
pressure p 2 . For a curved interface, the two pressures are related
by the well-known Young-Laplace equation of capillarity,
P c p 1 p 2 2 /r,

where P c is the capillary pressure, and r, the radius of the curvature of the interface.
Similar to the above, in the following, subscripts 1 and 2 denote the gas and liquid phases, respectively. The expression for V t
is
V t V 1 V 2 ,

where V 1 is the volume of the gas phase and V 2 is the volume of

the liquid phase. The volume of phase j, V j , is given by
336

A. Firoozabadi and H. Pan: Multicomponent-Hydrocarbon Mixtures

Solution Procedure
When the interface between the gas and liquid phases is flat that
is, r in Eq. 4, ( p 1 / p 2 ) S,n1. In this case, there are (2c
1) equations and (2c1) unknowns; Eqs. A-6, A-9, and A-18
provide the unknowns. For a curved interface, the number of unknowns and the equations increase to 2(c1). The additional
relationship is provided by Eq. A-13. In this work, we use an
iterative procedure to calculate the effect of capillary pressure
variation on the isentropic compressibility and the sonic velocity.
We first assume the interface is flat, and compute the phase volume and compositions, then use Eq. A-14 to estimate the interfacial tension. The amount and the composition of the phases are
again calculated using
f 1,i T,p 1 ,n 1,1 ,n 1,2 ,...,n 1,c f 2,i T,p 2 ,n 2,1 ,n 2,2 ,...,n 2,c ,
i1, . . . ,c,
p 1 p 2 F S L ,

8
9

and the material balance.

Note that in Eq. 9, is a function of composition and of phase
pressures, and therefore, we may need to perform the flash iteratively. Using the calculated phase data, Eqs. A-6, A-11, and A-13
are used to calculate the unknowns and proceed to calculate
( z j / p 2 ) S,n . Then all the parameters are available to calculate
( V t / p 2 ) S,n , and c S . Once c S is estimated, the sonic velocity is
calculated from
a v t /c S .

10

In the two phase, we use the two-phase molar volume v t . In the

single phase v t becomes the molar volume of the single phase v .
Results
The model presented above and in Appendix A was used to calculate the isentropic compressibility and the sonic velocity of a
number of binary and ternary hydrocarbon mixtures, and a North
Sea crude both in the single phase and in the two phase. The
isothermal-compressibility model in the two phase has been previously verified with experimental data see Ref. 3. In this work,
the predicted sonic velocity in the single-phase gas and liquid
states for nitrogen gas, methane gas, and n-hexane liquid was
compared with the experimental data. The agreement is very good
and is similar to those in Ref. 2. We are not aware of isentropic
compressibility and sonic velocity in the two-phase region for
hydrocarbon mixtures to verify the model. Very limited data by
Wang, Nur, and Batzle7 on two live oils show that in the two
phase, sonic velocity does not decrease. These authors do not
provide either the composition or the manner in which the pressure was reduced below the bubblepoint. Therefore, their data
cannot be used to verify the methodology.
We present in this paper the estimation of c S and a in the
two phase. Such estimates for hydrocarbon fluids which have
unique features may be useful. The unique features include volume change on mixing and retrograde behavior that can affect
compressibility and sonic velocity drastically. In the following,
the results for various systems are presented.
C1 C3. Two different mixtures for the C1 /C3 are selected; one
mixture with a C1 content of 30% mole, and another mixture
with a C1 content of 20%.
Fig. 2 shows the isothermal and isentropic compressibilities
and the sonic velocity for the C1 /C3 mixture 30% C1 and 70%
SPE Reservoir Eval. & Eng., Vol. 3, No. 4, August 2000

point, the difference is at a maximum. This figure reveals that the

variation of c S in the two phase is much less than the variation of
cT .
The effect of capillary pressure on the two-phase c T is examined in Fig. 2b. We use a simple linear relation to describe the
saturation dependency of P c see Eq. A-12,
F SL SL ,

Fig. 2Calculated compressibilities and sonic velocity for the

C1 C3 mixture 30% C1 and 70% C3 at 130F. a c T and c S ; b
effect of capillary pressure; c effect of capillary pressure; and
d effect of capillary pressure.

C3 at 130F both in the single phase and two phase. In Fig. 2a,
the isothermal compressibility c T and the isentropic compressibility c S are presented. The two-phase compressibilities are based on
the assumption of a flat interface between the gas and liquid
phases. Fig. 2a reveals that in the single-phase liquid, the isothermal compressibility is a factor of 2 to 4 more than the isentropic
compressibility. In the single-phase gas, the difference is less, but
it is still substantial. Close to the bubblepoint, the two-phase compressibilities are close, but as the amount of the gas phase increases, the difference between c T and c S increases. At the dew-

11

where and are constants of the capillary pressure model. One

could use other models for capillary pressure. Capillary pressure
affects the phase behavior. This effect is generally small for porous media. Due to capillarity, the saturation pressure of hydrocarbon mixtures may increase or decrease, whereas for singlecomponent fluids the saturation pressure decreases as the capillary
pressure increases.2 In this work, we are concerned only with the
positive P c where gas is the nonwetting phase and liquid is the
wetting phase.
For the system of Fig. 2b the capillary pressure at the bubblepoint is 4 psi and it is 50.9 psi at the dewpoint. The bubblepoint
pressures of the flat and curved interfaces are 977.2 and 966.4 psi,
respectively see Table 1. The dewpoint pressures of the flat and
curved interfaces are 453.4 and 389.3 psi, respectively. The parachors used in the calculation of the interfacial tension are taken
from Ref. 8 for C 1 , C 3 , and C 4 and from Ref. 9 for the plus
fraction of the crude to be discussed later. We make no attempt
to adjust either the parachors or the exponent of the interfacial
tension expression to match the predicted interfacial tension with
data in the literature. The results presented in Fig. 2b show that
the capillary pressure does not alter the shape of isothermal compressibility. In this and subsequent examples, the parameters assigned to the capillary pressure model may provide higher P c than
that encountered in porous media. This is done intentionally to
examine the effect of capillarity for extreme cases.
Fig. 2c depicts the isentropic compressibility for the flat interface and the curved interface. Fig. 2c reveals that there is a significant effect of capillarity on the isentropic compressibility. The
capillary pressure reduces the changes in the isentropic compressibility around the dewpoint. As stated above, the assigned capillary pressure may be higher than that encountered normally in
porous media.
Fig. 2d plots the sonic velocity; in the single-phase liquid, the
sonic velocity decreases as the pressure decreases. In the singlephase gas, the sonic velocity increases as the pressure decreases.
The predicted results are in line with experimental data for pure
component fluids. There is a sharp decrease in the sonic velocity
at the bubblepoint; the sonic velocity decreases from 370 to 100

TABLE 1 DATA ON VARIOUS FLUIDS

System

Composition

T
(F)

b
(dyn/cm)

P c,b
(psia)

Pb
(psia)

d
(dyn/cm)

P c,d
(psia)

Pd
(psia)

(psia cm/dyn)

(psia cm/dyn)

C1 /C3
C1 /C3
C1 /C3
C1 /C3
C1 /C3
C1 / n C10
C1 / n C10
C1 / n C10
C1 / n C10
C1 / n C4 / n C10
Crude
Crude
Crude

30/70
30/70
20/80
20/80
20/80
70/30
70/30
95/5
95/5
70/23.5/6.5

130
130
50
50
50
130
130
130
130
160
224.6
224.6
224.6

0.18
0.2
5.5
5.51
5.53
0.85
0.94
0.64
0.63

1.68
1.72
1.78

0
4
0
5.6
29
0
18.7
0
0.6
0
0
17.3
35.7

977.2
966.4
523.5
516.6
480.7
4,170.3
4,093.2

2,988.4
4,317.2
4,271.6
4,222.3

2.2
2
10.1
10
9.9

0
50.9
0
60
98.1

453.4
389.3
119.7
59.6
21.5

5,146.7*
5,151.3*
6.3

20

1
5

20

10
20

5
5

5
5

*Retrograde dewpoint.

A. Firoozabadi and H. Pan: Multicomponent-Hydrocarbon Mixtures

SPE Reservoir Eval. & Eng., Vol. 3, No. 4, August 2000

337

Fig. 4Calculated compressibilities and sonic velocity for the

C1 n C10 mixture 70% C1 and 30% n C10 at 160F. a c T and
c S ; b effect of capillary pressure; c effect of capillary pressure; and d effect of capillary pressure.
Fig. 3Calculated compressibilities and sonic velocity for the
C1 C3 mixture 20% C1 and 80% C3 at 50F. a c T and c S ; b
effect of capillary pressure; c effect of capillary pressure; and
d effect of capillary pressure.

m/s. At the dewpoint, the sonic velocity increases from 190 to 240
m/s. The capillary pressure dampens the change of the sonic velocity at the dewpoint.
The compressibility and the sonic velocity for the second
C1 /C3 system are plotted in Fig. 3. For this system, the composition is 20% C1 and 80% C3, and the temperature is 50F. Fig. 3a
reveals that the isentropic compressibility varies much less than
the isothermal compressibility in the two-phase region. The effect
of capillary pressure on c T is shown in Fig. 3b; on the bubblepoint
side the effect is small. However, on the dewpoint side, capillarity
reduces the difference between the single- and two-phase compressibilities. Table 1 provides the saturation pressures and P c for
this system. Note that on the dewpoint side, P c is larger than on
the bubblepoint side due to the pressure effect. Fig. 3c shows the
effect of P c on the c S ; there is no decrease in c S as the fluid
enters the single-phase gas. Fig. 3d shows the sonic velocity for
the C1 /C3 system; the trends are similar to Fig. 2d.
C1 nC10. Two different mixtures of C1 /nC10 were studied; one
has a bubblepoint at high pressures and the other has a retrograde
dewpoint.
Fig. 4 shows the compressibility and the sonic velocity for the
mixture of 70% C1 and 30% nC10 at 160F. Fig. 4a shows that in
the two-phase region close to the bubblepoint, c T and c S are different by a factor of 3. Unlike the c T where there is a sharp
increase, cS increases much less when the fluid enters the two
phase. Figs. 4b and 4c show that the effect of capillarity on the
two-phase compressibility is negligible in the pressure range of
the plot. Note that similar to the C1 /C3 system, the bubblepoint
pressure decreases due to capillary pressure see also Table 1.
Fig. 4d depicts the sonic velocity which has a trend similar to the
C1 /C3 system. Capillarity increases the sonic velocity for the system of Fig. 4, but not appreciably.
338

A. Firoozabadi and H. Pan: Multicomponent-Hydrocarbon Mixtures

Fig. 5 shows the compressibility and sonic velocity for a mixture of 95% C1 and 5% nC10 . As was pointed out earlier, this
system has a retrograde dewpoint of 5,146.7 psia. At the dewpoint, c T increases while c S decreases. This behavior is different
from the bubblepoint systems which were presented in Figs. 2
through 4. As a result, we observe a significant difference between
c T and c S a factor of 20. Note that for this system, the change
for c S at the dewpoint is more than for c T . The effect of capillary
pressure on c T and c S is not very pronounced results not shown
due to low P c 0.6 psi. It is interesting to note that the capillary
pressure increases the dewpoint pressure see Table 1. The sonic
velocity is plotted in Fig. 5b; it increases in the two phase. This
behavior is in contrast to the sonic velocity of water-air and watersteam mixtures. Fig. 5b also shows that the sonic velocity decreases initially due to the P c effect.

Fig. 5Calculated compressibilities and sonic velocity for the

C1 n C10 mixture 95% C1 and 5% n C10 at 160F. a c T and c S
and b sonic velocity a .
SPE Reservoir Eval. & Eng., Vol. 3, No. 4, August 2000

Fig. 6Calculated compressibilities and sonic velocity for the

C1 n C4 n C10 mixture 70% C1, 23.5% n C4, and 6.5% n C10 at
160F. a c T and c S and b sonic velocity a .

C1 nC4 nC10. Fig. 6a shows the c T and c S , and Fig. 6b shows

the sonic velocity for the ternary mixture. The dewpoint pressure
for this system is very lowaround 6.3 psiaand c T and c S
compressibilities are very high. Fig. 6a shows that the difference
between cT and c S stays nearly constant in the pressure range
shown. The sonic velocity has a trend similar to the previous
nonretrograde systems.
North Sea Crude. The North Sea crude from Ref. 2 was used in
this work. Composition and characterization of the plus fractions
are provided in Ref. 2. Fig. 7a shows that similar to some of the
binary systems, c S does not change appreciably at the bubblepoint. Fig. 7a also shows that the difference between c T and c S is
appreciable in the two-phase region. Figs. 5b and 5c reveal that
the capillary pressure has a small effect on both c T and c S . The
effect of capillary pressure on the bubblepoint is provided in
Table 1. Fig. 5d plots the sonic velocity both in the liquid and in
the two phase. The effect of capillary pressure on sonic velocity is
also plotted in Fig. 5d. The results show that capillary pressure
does not change the sonic velocity appreciably, and there is not a
significant drop in the sonic velocity as the crude enters the twophase region.
Discussion and Conclusions
In the calculation of c T and c S we have assumed that the fluids are
in thermodynamic equilibrium. This is a good assumption for reservoir fluids both in the reservoir and in the wellbore. In the
reservoir, the flow is very slow, and the isothermal conditions are
attained. In the wellbore due to flow, mixing helps to achieve
equilibrium. On the other hand, the sonic velocity in the two
phase may not allow the establishment of equilibrium. In this
case, one may neglect the mass transfer between the phases as a
result of pressure fluctuations. This greatly simplifies the calculation.
The main conclusions drawn from this work are as follows.
A thermodynamic methodology has been established to calculate the isentropic compressibility in the two phase. From the
isentropic compressibility, the thermodynamic sonic velocity in
the two phase is readily estimated.
There is a significant difference between the isothermal and
isentropic compressibilities in the two phase. The isothermal compressibility generally changes at the phase boundaries, while the
change in isentropic compressibility may be less significant. In the
retrograde region, both compressibilities in the two phase may be
significantly different from that in the single phase.
The sonic velocity in the two phase may be either less than or
more than the sonic velocity in the single phase. However, when
the sonic velocity decreases at the phase boundary, the decrease is
much less than in water-air and water-steam systems.
A. Firoozabadi and H. Pan: Multicomponent-Hydrocarbon Mixtures

Fig. 7Calculated compressibilities and sonic velocity for the

North Sea crude at 224.6F. a c T and c S ; b effect of capillary
pressure; c effect of capillary pressure; and d effect of capillary pressure.

The capillary pressure generally decreases the sharp contrast of

the single-phase and two-phase isentropic compressibility and
sonic velocity.
In addition to the work on the two-phase compressibility and
two-phase sonic velocity, in this paper we have set out the procedure to calculate the effect of capillary pressure on phase behavior
of multicomponent mixtures of highly nonideal behavior. Important steps in the proposed procedure include: variations of surface
tension as a function of gas- and liquid-phase composition
changes due to curvature, and variations of gas- and liquid-phase
compositions as interface curvature changes. The examples show
that: the retrograde dewpoint pressure increases as the capillary
pressure increases, and the normal bubblepoint pressure decreases
with capillary pressure increase. These results are based on the
assumption of a liquid-wet system in porous media.
Nomenclature
a
aj
Bj
c
cS
cT
cP
cV
j
f j,i
Mj
n

sonic velocity
defined in Eq. B-4
defined in Eq. B-3
total number of components
isentropic compressibility
isothermal compressibility
heat capacity at constant pressure
heat capacity at constant volume
mass density of phase j ( j1,2)
fugacity of component i in phase j
molecular weight of phase j ( j1,2)
vector of overall mole numbers

SPE Reservoir Eval. & Eng., Vol. 3, No. 4, August 2000

339

n j vector of mole numbers in phase j

n j,l vector of mole numbers in phase j excluding component k; lk
n t, j total number of moles of phase j
p j pressure of phase j ( j1,2)
P parachor
P c capillary pressure
r radius of curvature
R universal gas constant
S entropy
S L liquid saturation
T temperature
V volume
v molar volume
x j,i mole fraction of component i in phase j
z compressibility factor
constant of the capillary pressure model see Eq. 11
constant of the capillary pressure model see Eq. 11
interfacial tension
density

Various derivatives in Eq. A-1 are evaluated in the following.

compressibility
factor
zj
zj p2 S,n . The
z j (T,p j ,n j,1 ,n j,2 ,...,n j,c ) can be written in differential form as
dz j z j / T p,n j dT z j / p j T,n j dp j
c

z /n
j

i1

z j / p j T,n j p j / p 2 S,n
c

1. Batzle, M. and Wang, Z.: Seismic Properties of Pore Fluids, Geophysics 1992 57, No. 11, 1396.
2. Firoozabadi, A.: Thermodynamics of Hydrocarbon Reservoirs,
McGraw-Hill Book Co. Inc., New York City 1999.
3. Firoozabadi, A. et al.: EOS Predictions of Compressibility and
Phase Behavior in Systems Containing Water, Hydrocarbons, and
CO2, SPERE May 1988 673.
4. Kieffer, S.W.: Sound Speed in Liquid-Gas Mixtures: Water-Air and
Water-Steam, J. Geophys. Res. 1977 82, No. 20, 2895.
5. Michaelides, E.E. and Zissis, K.L.: Velocity of Sound in Two-Phase
Mixtures, Int. J. Heat Fluid Flow 1983 4, No. 2, 79.
6. Nguyen, D.L., Winter, E.R.F., and Greiner, M.: Sonic Velocity in
Two-Phase Systems, Int. J. Multiphase Flow 1981 7, 311.
7. Wang, Z., Nur, A.M., and Batzle, M.L.: Acoustic Velocities in Petroleum Oils, JPT February 1990 192; Trans., AIME, 289.
8. Katz, D.L. et al.: Handbook of Natural Gas Engineering, McGrawHill Book Co. Inc., New York City 1959.
9. Firoozabadi, A. et al.: Surface Tension of Reservoir Crude-Oil/Gas
Systems Recognizing the Asphalt in the Heavy Fraction, SPERE
February 1988 265.
10. Peng, D.Y. and Robinson, D.B.: A New Two-Constant Equation of
State, Ind. Eng. Chem. Fundam. 1976 15, No. 1, 59.
11. Weinaugh, C.F. and Katz, D.L.: Surface Tension of MethanePropane Mixtures, Ind. Eng. Chem. 1943 35, 239.

Appendix ACalculation of V t p 2 S ,n
From Eq. 7, one obtains
2

z /p n
j

j,t

/ p 2 S,n n j,t /p j

j1

/ p 2 S,n,
A-3

z j n j,t /p j T/ p 2 S,n .

nj,t p2 S,n . The expression for ( n j,t / p 2 ) S,n is given by

c

n j,t / p 2 S,n

n
i1

j,i

/ p 2 S,n ,

j1, 2.

A-4

Note that ( n j,i / p 2 ) S,n also appeared in Eq. A-3. Eqs. A-1, A-2,
and A-4 define the 2(c1) unknowns that are required to calculate ( V t / p 2 ) S,n . These unknowns are: ( p 1 / p 2 ) S,n ,
( n j,i / p 2 ) S,n and ( T/ p 2 ) S,n , which are obtained from the following equations based on material balance, equilibrium criteria,
entropy constraint, and capillary pressure relationship.
Material Balance. The component material balance provides
n i n 1,i n 2,i i1,...,c,

A-5

which can lead to

n i / p 2 S,n n 1,i / p 2 S,n n 2,i / p 2 S,n0,

i1,...,c.
A-6

Equilibrium Criterion. The equilibrium criterion provides other

c equations,
f 1,i f 2,i

A-7

i1,...,c,

where f is the fugacity. The differential form of the above equation is df 1,i df 2,i . Fugacity of each component in a given phase
is a function of temperature, phase pressure, and moles in the
phase. Therefore,
df j,i f j,i / T p j ,n j dT f j,i / p j T,n j dp j

z j / p 2 S,n z j n j,t /p 2j p j / p 2 S,n

2

j,i T, p j ,n j,k n j,i

where ( z j / T) p j ,n j , ( z j / p j ) T,n j , and ( z j / n j,i ) T, p j ,n j,k coefficients can be calculated from an equation of state EOS. In this
work we use the Peng-Robinson10 PR EOS. Note that once
( T/ p 2 ) S,n , ( p 1 / p 2 ) S,n , and ( n j,i / p 2 ) S,n are estimated,
then ( z j / p 2 ) S,n will be established, as will be shown shortly.

References

j1

j1, 2,

Acknowledgments
This study was initiated while one of the authors A.F. was a
visiting professor at the U. of Texas, Austin, in the Fall of 1996.
The help of graduate student Ganesh Narayanaswamy of the U. of
Texas, Austin, in the initial stage of the work is appreciated.

340

z /n
i1

V t / p 2 S,nRT

A-2

j1,2,

z j / p 2 S,n z j / T p j ,n j T/ p 2 S,n j

gas phase
liquid phase
bubblepoint index
dewpoint index
component index
phase index
component index
component index
total

where n j (n j,1 ,...,n j,c ); n j,i is the number of moles of component i in phase j, and n j,k n(n j,1 ,...,n j,k ,...,n j,c ) and ki. By
dividing Eq. A-2 by p 2 at constant n and S,

Subscripts
1
2
b
d
i
j
k
l
t

j,i T, p j ,n j,k dn j,i

A-1

A. Firoozabadi and H. Pan: Multicomponent-Hydrocarbon Mixtures

k1

j,i

/ n j,k T, p j ,n j ,l dn j,k ,

j1, 2,

i1,...,c,
A-8

SPE Reservoir Eval. & Eng., Vol. 3, No. 4, August 2000

where n j,l (n j,1 ,...,n j,l ,...,n j,c ) and lk. Dividing Eq. A-8 by
p 2 , keeping S and n constant, and using the criterion of equilibrium, one obtains
f 1,i / T p 1 ,n1 f 2,i / T p 2 ,n2 T/ p 2 S,n
f 1,i / p 1 T,n1 p 1 / p 2 S,n f 2,i / p 2 T,n2

k1

f 1,i / n 1,k T, p 1 ,n1,l , n 1,k / p 2 S,n

k1

2,i

/ n 2,k T, p 2 ,n 2,k n 2,k / p 2 S,n 0

F/ p 2 S,n dF/dS L S L / P 2 S,n .

i1,...,c.
A-9

In the above equation, the coefficients ( f j,i / T) p j ,n j ,

( f j,i / p j ) T,n j , and ( f j,i / n j,k ) T, p j ,n j,l can be obtained from an
EOS.
Entropy Constraint. From S j 2j1 S j , one readily obtains

V 1 V 2 / p 2 S,nV 2 V 1 / p 2 S,n
.
V 1 V 2 2

Appendix BPhase Entropy from the PR-EOS

The entropy of phase j is given by2
S j

Vj

j1

2 S,n0.

A-10

Writing the expression for dS j , dividing it by p 2 at constant S

and n, and substituting the results in Eq. A-10,
2

j1

ln V j / n j,i RT

S /n

k1

j,k T, p j ,n j,l n j,k

/ p 2 S,n 0.

S j n j,t R ln
A-11

The
coefficients
( S j / T) p j ,n j ,
( S j / p j ) T,n j ,
and
( S j / n j,k ) T,p j ,n j,l can be estimated from the expression of the
phase entropy derived in Appendix B.
Capillary Pressure Effect. According to Eq. 4, if and r stay
constant as p 2 changes, ( p 1 / p 2 ) S,n1. However, with change
in p 2 , the temperature and the composition of the phases may
change. The curvature also may change. One may express the
capillary pressure in porous media as
P c p 1 p 2 F S L ,
A-12
where S L represents the liquid saturation. Then,
p 1 / p 2 S,n1F S L / p 2 S,n F/ p 2 S,n .

P x
i1

2,i 2

/M 2 x 1,i 1 /M 1 .

A-14

In Eq. A-14, x 2,i and x 1,i are mole fractions of component i in the
liquid and gas phases, respectively, and and M represent the
density and the molecular weight; P i is the parachor of component i.
A more useful form of Eq. A-14 is
c

1/4

P n
i1

2,i

/V 2 n 1,i /V 1 .

A-15

From Eq. A-15,

c

/ p 2 S,n4 3/4

P n
i1

2,i

n
i1

B-1

o
j,i s i T .

z j B j da j T /dT z j 1& B j

ln
zj
2&b j
z j 1& B j

i1

x j,i ln

zj

x s 0 T .
x j,i p j i1 j,i j

B-2

Parameters B j and a j are given by

B j b j p j / RT ,
c

a j

B-3

x
i1 k1

j,i x j,k a ik

B-4

In Eqs. B-3 and B-4 b j and a ik are the parameters of the PR-EOS.

A-13

Kieffer neglected the last two terms on the right side of Eq. A-13
in her work.4 The interfacial tension between the gas and liquid
phases in a mixture can be represented by the Weinaugh-Katz
model,11

1/4

In Eq. B-1 s io (T) is the ideal gas molar entropy of component i.

Combining Eq. B-1 and the PR-EOS, one obtains

S j / T p j ,n j T/ p 2 S,n j S j / p j T,n j p j / p 2 S,n

n j,t R
p j / T V j ,n j dV j R
n j,i
Vj
i1
c

S /p
j

A-18

We have already shown how to calculate ( V 2 / p 2 ) S,n and

( V 1 / p 2 ) S,n .

S/ p 2 S,n

A-17

Since S L V 2 /(V 1 V 2 ),
S L / p 2 S,n

The second derivative term in Eq. A-13 is estimated from

/V 22 V 2 / p 2 S,n

n 1,i /V 21 V 1 / p 1 S,n
n 2,i / p 2 S,n /V 2 n 1,i / P 2 S,n /V 1 .
A-16
A. Firoozabadi and H. Pan: Multicomponent-Hydrocarbon Mixtures

SI Metric Conversion Factors

dyn 1.0*
F
(F32)/1.8
F
(F459.67)/1.8
psi 6.894 757
*Conversion factor is exact.

E02

E00

mN
C
K
kPa
SPEREE

Abbas Firoozabadi is Senior Scientist and Director at the Reservoir Engineering Research Inst. (RERI) in Palo Alto, California.
e-mail: AF@rerinst.org. He has taught previously at Stanford U.
and the U. of Texas at Austin. His research interests include
equilibrium, non-equilibrium, and irreversible thermodynamics,
multiphase flow in fractured and layered permeable media,
and tidal-force-influenced pressure transients for the estimation of key parameters of fractured reservoirs. Firoozabadi
holds a BS degree from the Abadan Inst. of Technology, Iran,
and MS and PhD degrees from the Illinois Inst. of Technology,
Chicago, all in gas engineering. He has served on various SPE
Committees. Huanquan Pan is a software developer at Incyte Genomics in Palo Alto, California. Previously, he was a
scientist with the Reservoir Engineering Research Inst. (RERI),
where he worked on the modeling of asphaltene and wax
precipitation and the development of efficient phaseequilibrium algorithms for compositional reservoir simulation.
Pan holds a PhD degree in chemical engineering from Zhejiang U. in Hangzhou, China.
SPE Reservoir Eval. & Eng., Vol. 3, No. 4, August 2000

341