Fundamental Phase Behavior of Hydrocarbons

By JOHN E. SHERBORNE, * JUNIOR MEMBER A.I.M.E.

(Los Angeles Meeting, October 1939)

MUCH valuable scientific research has been performed in recent years

on the subj ect of phase behavior of hydrocarbons. t 1-11 Engineers em ployed
in petroleum production are interesting themselves in this work as well
as in methods of applying the fundamental data available to the solution
of their various problems.
Recently a number of papers have been published in which applica-
tions of phase behavior have been made to specific cases pertaining to
critical phenomena. 12- 16 Little effort, however, has been made in the
literature to show the relation between changes occurring in the critical
region and the more common phase behavior, therefore it is believed that
a presentation of the fundamentals of phase behavior with reference to
hydrocarbons is timely.
Study of phase behavior is not new. In the metallurgical field,
knowledge of heterogeneous equilibria has advanced tremendously,
particularly with reference to solid-solid and solid-liquid behavior.
Much is known about vapor-liquid equilibria too, but few engineers are
familiar with this subject.t
DEFINITION OF TERMS

In a discussion of this sort, a definition of terms used is most impor-

tant. Such terms as "pressure," "temperature" and "volume" need
little definition other than mention of the units in which they are con-
sidered. Pressure is expressed in pounds per square inch absolute.
Temperature is usually expressed as degrees Fahrenheit or degrees
Rankine. In considering thermodynamic and phase behavior, the use
of the absolute, Rankine, scale is desirable. Volume is expressed as
specific volume, such as cubic feet per pound. This will be recognized
as the reciprocal of the specific weight. In considering systems composed
of more than one component, it is sometimes desirable to consider molal

Manuscript received at the office of the Institute Oct. 24, 1939. Issued as T.P.
1152 in PETROLEUM TECHNOLOGY, February 1940.
* Petroleum Engineer, Union Oil Company of California, Compton, California.
t Notable among the various investigators are Sage, Lacey and co-workers, Katz
and Lindsly. Only a few selected references of these and other authors will be used.
1 Numbers refer to references at end of paper.
t Several books dealing with phase behavior are included in the bibliography. 1&-20,"
119
120 FUNDAMENTAL PHASE BEHAVIOR OF HYDROCARBONS

or weight composition rather than volume. This will be considered more

fully in discussing two-component systems.
System.-A system may be classified as a one, two, three, or multi-
component system. From a strictly scientific point of view a component
must be defined as a pure substance. Thus a system containing nothing
but propane would be of one component, while one consisting of methane
and propane would be of two components. It follows that even the
simplest of crude oils and natural gases are multi-component systems.
However, it is sometime practical, under a wide range of conditions, to
consider naturally occurring hydrocarbon mixtures as two-component
systems in which natural gas and crude oil are the respective components.
Phase.-Under the proper conditions, any system may exist as one or
more phases. In the language of Willard Gibbs, a portion of matter
homogeneous in the sense that its smallest mechanically isolable parts
are indistinguishable from one another physically or chemically is
a phase.
ONE-COMPONENT SYSTEM

In Fig. 1 is shown a generalized pressure-temperature diagram for a

one-component system. * In it the lines represent the loci of equilibrium
points. For example, any point on the line AB represents a condition
of equilibrium between the solid and vapor phases for the particular
pressure and temperature chosen. In like manner BD represents the
solid-liquid equilibrium line while along the line Be liquid and vapor
coexist. At no place does more than one phase exist except for the con-
dition occurring at the boundary lines or their extensions, BF and BE,
which represent the metastable states of supercooling and superheating,
respectively. Thus, for the pressure P gas and liquid can exist together
only at the temperature T.
Phase Rule
Fig. 1 shows that as long as only one phase exists there are within the
limits of the boundaries of that phase for a given pressure an infinite
number of values for the temperature. If two phases coexist, there is
only one value of temperature for each value of pressure. Under such a
condition, the system is said to have only one degree of freedom. In
order for three phases to exist for a one-component system, the pressure
and temperature are both fixed and the system is said to have no degrees
of freedom. Physical behavior of this nature may be expressed as the
phase rule, which may be given as:
P+F=3 [1]
Fig. 1 represents projections of curved surfaces onto a plane. The diagram has
been generalized in order to show various points of interest, consequently it is not
drawn to a scale applicable to any given system.
 JOHN E. SHERBORNE 121

where P = number of phases present

and F = number of degrees of freedom.
This rule can be more generally expressed as:
P+F=C+2 [2]
where C = number of components.

."
"5
~pa~ _____ ~b _________ ~ __ ~_
:) ~
<Il "0
<Il VI
W
a:
0... SOLID LIQUID

1
ASolid-Va r Bound.
F-----
VAPOR
e
T
--_. TEMPERATURE ...
FIG. I.-GENERALIZED PRESSURE-TEMPERATURE DIAGRAM FOR A ONE-COMPONENT
SYSTEM.

While the phase rule in itself is of little practical significance, it

clearly demonstrates that with an increasing number of components the
number of possible combinations rapidly increases.
In this figure, there are two other points, Band C, which are of
interest. Point B, commonly referred to as the" triple point," represents
the state in which gas, liquid and solid phases all exist simultaneously.
Here, it will be noted, there are no degrees of freedom, the pressure and
temperature being fixed. Point C represents the critical state of the
system. It is the temperature at which the properties of the liquid are
identical with those of the gas. Since the pressure and temperature are
fixed, here again no degrees of freedom exist and the state of the system is
fixed. For a one-component system, the critical temperature is the
highest temperature at which gas and liquid phases can both exist.
 122 FUNDAMENTAL PHASE BEHAVIOR OF HYDROCARBONS

Since Fig. 1 shows only changes in pressure and temperature, an

attempt has been made to show in Fig. 2 a series of surfaces representing
the relation between changes taking place in the temperature, pressure
and volume. *
Whether the system be in the solid, liquid or gaseous phase, a knowl-
edge of the pressure, temperature and specific volumet is necessary
and sufficient to completely establish the volumetric behavior of a one-
component system. The relation may be expressed as
F(v, p, T) = 0 [3]
For obvious reasons the surfaces in Fig. 2 have been restricted to
finite values of the three variables. Hence, for the limited range of

So ID

UJ
ct
:;;)
Vl
Vl
'"
a:
0..----------
------------

SPECIFIC VOLUME

FIG. 2.-GENERALIZED PRESSURE-TEMPERATURE-VOLUME DIAGRAM FOR A ONE-

COMPONENT SYSTEM.

pressure, temperature and volume covered by the surface ABGF only

the solid phase exists, and in like manner, for the conditions represented
by the surface BDHG, only solid and liquid phases coexist, and so on.
The points GHI determine the triple-point line, all three points coinciding
to form the point B in Fig. 1.

This diagram does not represent all known cases of one-component systems,
water being one exception. However, it is applicable to most of the known pure
substances.
t External fields of force, such as gravitational, electrical and magnetic and sur-
. face forces are assumed to be negligible. Unless otherwise noted, these assumptions
will apply throughout this paper.
 JOHN E. SHERBORNE 123

In general, only liquid, liquid-vapor and vapor phases need be

investigated in considering hydrocarbon reservoir systems. Of particular
interest is the region bounded by HCI, which represents the two-phase
region, liquid plus vapor. Starting with the system at point a, in which
condition it is all liquid at high pressure, holding the temperature con-
stant at tl and reducing the pressure from a to b results only in a change
in the volume of the liquid until at b evaporation starts. The volume of
the system increases at constant pressure from b to d until at d only an
infinitesimal amount of liquid remains. Isothermal expansion of the gas
takes place from d to e.
From the slope of the lines ab and de the compressibility of the liquid
and gas respectively can be obtained. In the two-phase region the
compressibility derivative becomes infinite. This derivative may be
expressed as follows:

Compressibility ({3) = - (~;) 2' [4]

In a similar manner, from the slopes of the lines shown by mn, no, ob,
bd and dq, which represent isobaric changes in the volume of the system
with temperature, the coefficients of expansion of the system for the
conditions existing in the respective region chosen can be obtained. That
is, from the slope of a line such as ob we obtain the expression:

Thermal expansion (a) = (:~)p [5]

In Fig. 2 the critical point is given by C. At and above the critical

temperature t. it is not possible to distinguish between liquid and vapor.
The fact that at the critical point the pressure, temperature and volume
are fixed is shown.

TWO-COMPONENT SYSTEM

The phase rule shows that for a two-component system it is possible

for four phases to coexist. These may be any combination of liquid,
solid or vapor, including four solid or four liquid phases. However,
there have never yet been found more than two liquid phases coexisting
in a two-component system. Although the production of oil from deeper
zones of higher pressures and temperatures may disclose the coexistence
of two or more liquid phases, this discussion will be restricted to the
behavior of systems more common at the present time, those having only
one liquid phase. Specifically, hydrocarbon systems as they occur in
the reservoir will be considered to consist of varying mixtures of the
component natural gas and the component crude oil.
124 FUNDAMENTAL PHASE BEHAVIOR OF HYDROCARBONS

Phase changes of a two-component system can best be shown by

pressure, temperature and composition diagrams. While in some cases
the use of molal composition is desirable, for practical purposes weight
composition is most convenient. Using weight composition the crude
oil or natural gas may be expressed as a percentage of the total weight of
the system. This can be directly related to the gas-oil ratio providing
the system is always assumed to be composed of two components. Unless
it is stated otherwise, the weight composition will be used throughout the
remainder of the paper.

FIG. 3.-GENERALIZED PRJilSSURE-TEMPERATURE COMPOSITION DIAGRAM FOR A TWO-

COMPONENT SYSTEM.

In Fig. 3, based on a diagram by Roozeboom,20 is shown a three-

dimensional representation of the pressure, temperature, composition
relations of a two-component system for which there is only one liquid
phase. * The graph is plotted -in rectangular coordinates in which the
ordinate is pressure while the abscissae are composition and temperature.
Point A represents 100 per cent of the pure substance A, natural gas,
while point B represents 100 per cent of the pure substance B, crude oil.
Point X represents a mixture of A and B of which the fraction XB/ AB is
component A, and the fraction XAj AB is component B. It should be

* Fig. 3 is a generalized diagram and is not drawn to scale for any specific binary
system. The pressure and temperature of points A and B are shown at some value
above zero, and in order to avoid confusion resulting from too many lines, many of
the details pertaining to the solid and associated phases in the region of low pressures
have been omitted.
 JOHN E. SHERBORNE 125

realized that the solid-liquid equilibria depicted in Fig. 3 are not descrip-
tive of crude oil-natural gas systems.
A plane through the points GANIAODG represents the pressure-
temperature diagram for the pure substance A; likewise the points
GBQHBPFE represent the pressure-temperature diagram for the pure
substance B. These points, if projected onto one plane, give the diagram
shown in Fig. 4. The similarity between Fig. 4 and Fig. 1 can be seen
readily. Since for a given temperature the vapor pressure of the sub-

/G E
I
I
I
I
I
I CA Cs
I /
o ____ ...1 __ s----~---------- Q
IR
I /
I /
w
cr:
::J I
I l
/1
I/)
I/) I I I
w I / I
cr: / I
0. I / I
I I
I /
I / I
j/ I
;;:----1 I

B H

Tl
TEMPERATURE
FIG. 4.-PROJECTION OF LIMITING COMPOSITION CURVES FOR TWO-COMPONENT SYSTEM
ONTO PRESSURE-TEMPERATURE PLANE.

stance A is greater than that for B, A is the more volatile and, conse-
quently, represents gas in the gas-crude oil system.
Before considering pressure-temperature diagrams for mixtures of
A and B, it is desirable to orient the phases on an isobaric graph of com-
position .and temperature taken at pressure P. This is represented by
the plane MNOPQK in Fig. 3 and is shown in Fig. 5. Choosing a
composition represented by point a, Fig. 5, and following the changes of
state that take place when the temperature is increased, one follows the
line abcdefgp. The region ab represents a solid composed of a mixture
of the two components in the proportion given by the composition a.
At b, liquid of the composition y starts to appear until the solid in equi-
126 FUNDAMENTAL PHASE BEHAVIOR OF HYDROCARBONS

librium with the liquid is pure, solid B. As the system changes from b
to d the composition of the liquid follows the path yhd until at d all of the
solid B disappears and liquid of the composition a exists from d to e.
At point c, liquid of the composition given by h occurs in equilibrium with
the solid B. The weight fraction of liquid present is given by the ratio
ci: hi, while the proportion of the mixture that is solid is ch: hi. At
PRESSURE = Pz
point e gas of composition shown
M by 0 starts to form and from e to
GAS
g the composition of the vapor
m
phase follows the path omg, while
L+G
the liquid in equilibrium with it
o ----------- e
I follows the path enq. At J an
I
I amount of gas of composition m,
I
the weight fraction of which is
1
I
I
I
I
expressed by the ratioJn/nm, is in
lJJ
IX
;:)
LIQUID Id equilibrium with liquid of the
I-
..: I composition n, which exists in the
0: I
lJJ h
----,-----
Ie i proportion given by the ratio
Do
::;;
ILl
I Jm/mn. A trace of liquid of the
I
f-
16
composition q coexisting with gas
of composition a exists at g.
From g to p there is only gas.
SOLID Two points, e and g, have
special significance in petroleum
o a P
100"/. 100"/. production, for they represent the
A COMPOSITION B bubble point and the dew point,
FIG. 5.-IsOBARIC COMPOSITION-TEM- respectively. The bubble-point
PERATURE SECTION SHOWING CONDITION
OF TWO-COMPONENT SYSTEM SHOWN IN FIG. state .is that in which an infinitesi-
3 WHEN PRESSURE EQUALS P. mal amount oj gas exists in equi-
librium with the liquid phase, and in like manner, the dew-point state
is that in which an infinitesimal amount oj the liquid is in equilibrium with
the vapor phase. The temperature at point e is commonly known as the
"bUbble-point temperature" and is defined as follows:
The bubble-point temperature is that temperature at which there is an
infinitesimal amount oj gas in equilibrium with the liquid phase, Jor a given
pressure and composition.
In like manner, the temperature at point g is known as the "dew-point
temperature," and is defined as follows:
The dew-point temperature is that temperature at which there is an
infinitesimal amount oj liquid in equilibrium with the vapor phase, Jor a
given pressure and composition.
It also is possible to speak of bubble-point pressure and bubble-point
composition. Bubble-point composition may be expressed as bubble-
point gas:oiI ratio. The dew point may be treated in the same manner.
 JOHN E. SHERBORNE 127
In Fig. 6 is shown a temperature-molal composition diagram of the
vapor-liquid region for the system methane-propane as it is at a pressure

200
VA OR
O~ ~ -Z
I..L.
0

UJ
0:
:J
100

0
/
/
"
,,/ -- ---
V POR
I+- /
/
V

t--
-100
I
I 1I ~UID l,~;-/
0: ;/
W I Vci'{\).
a. I
I'> :tl'll}.e,:-- ~
::; -200 I
w
------
-- - ---
I- I
I
lIQ 10
-300

-400
o 20 40 60 80 100
METHANE PROPANE
MOLAL COMPOSITION
FIG. 6.-TEMPERATURE-COMPOSITION DIAGRAM FOR TWO-COMPONENT SYSTEM,
METHANE-PROPANE AT 600 LB. PER SQ. IN. PRESSURE.
Solid lines based on data from Sage, Lacey and Schaafsma (methane value from
J. H. Perry, Handbook Chern. Eng., 619. New York, 1934. McGraw-Hill Book
Co.).
of 600 lb. per sq. in. absolute. Only the value for pure methane 22 and
the values above 70F.IO are experi-
mentally correct. The dotted lines
are used solely to show the general
nature of the vapor-liquid region.
A three-dimensional diagram of
the liquid-vapor region for a two-
component system is shown in Fig.
7. In it, the lines DLE, FMG,
HNI, etc., represellt bubble-point UJ
curves for the temperatures To, TJ en
and T 2, respectively. A movement a:~
along anyone of these lines would C>.
represent an isothermal change in
bUbble-point pressure with compo-
sition for the particular temper-
ature chosen.
In like manner, the lines DQE,
FPG, HOI, etc., represent the dew- COM POSI TlON

point curves for the respective FIG. 7 .-GENERALIZED PRESSURE-

TEMPERATURE-COMPOSITION DIAGRAM OF
temperatures. TWO-COMPONENT SYSTEM IN RANGE OF
Fig. 8 shows an isothermal sec- CONDITIONS USUALLY FOUND IN PETRO-
LEUM RESERVOIRS.
tion of composition versus pressure
at the temperature T I, Fig. 7. Here again the ordinate AF represents
pure component A and BG represents pure substance B. Points F and G
128 FUNDAMENTAL PHASE BEHAVIOR OF HYDROCARBONS

are the vapor pressures of the pure substances A and B, respectively, at

the temperature for which the section is taken.
If a composition X is chosen and the pressure increased, the system
starts as a gas and undergoes no change, except in volume, until at the
point P where an infinitesimal volume of liquid of composition d forms.
This is the dew-point pressure. A further increase in pressure results
in the formation of more liquid of a composition given by some point
on the curve from d to M in equilibrium with gas given by some point

TEMPERATURE = TI

UJ
a:
::>
(fl
(fl
w
a:
0..

A X B
(GAS) COMPOSITION (OIL)
FIG. S.-ISOTHERMAL PRESSURE-COMPOSITION DIAGRAM FOR HYPOTHETICAL CRUDE
OIL-NATURAL GAS SYSTEM AT TEMPERATURE T t

on the curve between P and e. At b the weight fraction bc/ac of gas of

composition a is in equilibrium with the weight fraction ab/ac of liquid
of composition c. The total composition of the system is still given by X.
By increasing the pressure still more~ further quantities of the gas are
liquefied, until at M there is only an infinitesimal amount of gas in
equilibrium with the liquid. This is the bubble-point pressure, for
the temperature and composition in question.
Referring again to Fig. 7, the line DFC A represents the vapor-pressure
curve for the component A and the line EGIC B the vapor-pressure curve
for the component B. If a mixture of A and B having a composition X
is selected, the vapor-temperature relations will be expressed by the
 JOHN E. SHERBORNE 129

COMPOSITION X

TCp TCx

TEMPERATURE - -
FIG. 9.-PRESSURE-TEMPERATURE SECTION FOR CONSTANT COMPOSITION X OF HYPO-
THETICAL CRUDE OIL-NATURAL GAS SYSTEM.

:i
d
C/)
1200
eli
ex

t
LIQUID'

.....,
VI 900
<Xl
...J

LU
a:
::>
VI 600
VI
LU
a:
a.

300

40 55 70 85
MOL PERCENT PROPANE
FIG. lO.-PRESSURE-COMPOSITION DIAGRAM FOR METHANE-PROPANE SYSTEM.
(After Sage, Lacey and Schaafsma.)
130 FUNDAMENTAL PHASE BEHAVIOR OF HYDROCARBONS

plane LMNCxCROPQ instead of a line. Points CA and CB are the critical

points of the pure components A and B, respectively. The critical
point of the mixture is Cx; and for the example given it occurs at a
higher pressure and temperature than that of the more volatile com-
ponent. The behavior shown in Fig. 7 is typical of that generally
encountered in binary paraffin hydrocarbon systems.
Line CACRC B is the locus of points of maximum temperature for the
two-phase region. Point C R, which is known as the cricondentherm, l
or critical condensation temperature, is the highest temperature at which
liquid and vapor coexist for the mixture of composition X. As previously
defined, for a one-component system the critical temperature was the
highest temperature at which the liquid and gas could occur together
in equilibrium. It was also defined as the temperature at which the
liquid and vapor phases were identical.
For a system composed of any number of components, the critical
temperature is always the temperature at which the liquid and vapor phases
have identical properties. That it is not the maximum temperature at
which the liquid and vapor phases can coexist for systems of two or more
components is illustrated in Fig. 9, which is a pressure-temperature
section for the system in Fig. 7 at the composition X. The critical
point, Cx, occurs at a lower temperature than does the cricondentherm CR.
Because it is not possible to show by means of Fig. 9 that the proper-
ties of the liquid and gas are not identical at the cricondentherm, a
pressure-composition diagram, Fig. 10, for the two-component system
methane-propane9 was constructed using two constant-temperature
curves which were selected so that the points Cx and CR correspond to the
composition X of Fig. 9. By the use of ratios, as employed in the dis-
cussion of Figs. 3 and 5, it can be shown that at Cx the composition of the
liquid is identical with that of the gas. This occurs at 89F., while
the cricondentherm CR occurs at 130F. At this latter point there is an
infinitesimal amount of liquid of composition given by point a in equilib-
rium with gas of composition X. Fig. 10 fails to show that the liquid
and gas can coexist at a pressure higher than that at the critical point.
This point, the maximum pressure at which two phases can coexist, is
shown by Cp in Fig. 9. For a one-component system, the points Cp ,
Cx and CR coincide to form one point.

ILLUSTRATIVE PHASE CHANGES IN OIL AND GAS PRODUCTION

It is convenient to assume that Fig. 9 represents a system of natural

gas and crude oil, in considering what happens in production from a
reservoir. In one case, illustrated by the line abc, there is liquid* (oil)
Near the critical region it is difficult to distinguish between liquid and gas in the
single-phase region. However, since at the bubble point b there forms an infinitesimal
 JOHN E. SHERBORNE 131

under a high pressure and at a temperature higher than surface tempera-

ture but not higher than the critical temperature. No free gas exists.
As the fluid rises in the well there is a decrease in pressure, from a to b,
until at b gas starts to separate. This is the bubble point for the pressure
and temperature shown. As fluid approaches the surface, the pressure
continues to decrease and more and more gas comes out of solution until
at the surface the point c is reached. While it is recognized that a
temperature decrease occurs in the system between the reservoir and
the surface, this change has been considered negligible for the purposes of
this and the following illustrations.
In the second case, one in which the reservoir has a pressure similar
to that of the first but a temperature above the critical temperature of
the hydrocarbon system, only the gaseous phase* exists in the reservoir.
This condition is shown bye. In coming to the surface the gas undergoes
only a relatively small drop in pressure and no fluid appears. This is
represented by some point z on the path of ef. If the pressure is decreased
more, liquid starts to condense at f and greater quantities of liquid form
with further decrease in pressure, until at some point g a maximum
amount of liquid condenses. Any further decrease in pressure results
in a decrease in the amount of the liquid phase until the dew point is
reached at h. At this point, the final drop of liquid vaporizes and only gas
remains. This phenomenon, resulting in the formation of a liquid phase
followed by its disappearance as a result of progressive increase or
decrease in pressure, under these conditions of restraint, on a system of
constant composition, has been called retrograde condensation. IS
It is important to note that retrograde phenomena may occur as a
result of change in pressure or temperature, but only when the composi-
tion of the system remains constant. Changes in the reservoir condition
that result from the selective withdrawal of either gas or oil cannot be
classed as retrograde phenomena, although there is an apparent similarity.
Formation Volumes.-While the use of composition is convenient in
illustrating changes that take place in multi-component systems, the
effects that changes in pressure and temperature have on the volume of
constant or variable composition systems are of particular practical
significance. The term "formation volume" as used is the ratio of the
volume occupied by the hydrocarbons at subsurface equilibrium tempera-
ture and pressure to a unit volume of oil as measured at 60F. and a
pressure of 14.73 lb. per sq. in. abs. Liquid shrinkage is sometimes used
instead of formation volume and may be defined as its reciprocal.

amount of the vapor phase, and at the dew point f there forms an infinitesimal amount
of the liquid phase, it is convenient to assume that the single-phase fluid at the point
a is liquid and that the phase at e is gaseous.
See preceding footnote.
132 FUNDAMENTAL PHASE BEHAVIOR OF HYDROCARBONS

VISCOSITY

Closely allied with phase behavior in the treatment of petroleum-

production problems is the effect upon the viscosity of the crude resulting
from changes in pressure, temperature and composition. Since a number
of papers have been published regarding this effect,7,2a-aO it will suffice
at this time to point out that as much as eightfold changes in viscosity
can occur throughout the ranges in pressure, temperature and composition
commonly occurring under producing conditions.
PRACTICAL ApPLICATIONS

The applications of phase behavior to practical field problems are

numerous, and have been discussed by many writers. 31- 43 A review of
these applications is beyond the scope of this paper, but it should be
noted that in studies of reservoir conditions, in volumetric estimate of
reserves, and in problems involving both homogeneous and hetero-
geneous flow, a knowledge of phase behavior for the hydrocarbon system
involved is requisite.
SELECTED BIBLIOGRAPHY
1. L. W. T. Cummings, F. W. Stones and M. A. Volante: Ind. and Eng. Chern. (1933)
26,728.
2. P. Duhem: Jnl. Phys. Chern. (1897) 1,273.
3. J. E. Gosline and C. R. Dodson: Amer. Petro lnst. Drill. and Prod. Practice (1938)
423.
4. J. P. Kuenen: Ztsch. Phys. Chern. (1893) 11,38.
5. Ibid. (1897) 24, 667.
6. B. E. Lindsly: Petro Engr. (Feb., 1936) 7, 34.
7. B. H. Sage and W. N. Lacey: Amer. Petro lnst. Drill. and Prod. Practice (1935)
141.
8. Ibid. (1936) 158.
9. B. H. Sage, W. N. Lacey and J. G. Schaafsma: Ind. and Eng. Chern. (1934) 26,
214.
10. B. H. Sage, W. N. Lacey and J. G. Schaafsma: Amer. Petro lnst. Prod. Bull. 212
(1933) 119.
11. H. S. Taylor, G. W. Wald, B. H. Sage and N. N. Lacey: Oil and Gas Jnl. (Aug. 10,
1939) 38,46.
12. E. O. Bennett: Petro Engr. (mid-year, 1939) 10,50.
13. C. R. Horn: Oil Weekly (Sept: 11, 1939) 96, 27.
14. D. L. Katz: Amer. Prod. lnst. Drill. and Prod. Practice (1938) 435.
15. D. L. Katz and C. C. Singleterry: Trans. A.I.M.E. (1939) 132, 103.
16. F. V. L. Patten and C. I. Denny: Oil Weekly (Dec. 12, 1938) 92,21.
17. A. Findley and A. N. Campbell: The Phase Rule and its Application. New York,
1938. Longmans, Green and Co.
18. J. P. Kuenen: Verdampfung und Verfliissigung von Gomishen. Leipzig, 1906.
Barth.
19. A. C. D. Rivett: The Phase Rule. London, 1923. Oxford Univ. Press.
20. B. Roozeboom: Die Heterogenen Gleichgewichte vom Standpunkte der Phasen-
lehre, II. Braunschweig. Viewig und Sohn.
134 FUNDAMENTAL PHASE BEHAVIOR OF HYDROCARBONS

N. JOHNSTON, * Los Angeles, Calif.-There has long been a need for a clear, general
treatment of the theory of phase behavior, to assist in the understanding and utiliza.-
tion of the voluminous and excellent contributions of Sage and Lacey, Katz and others.
The present paper by Sherborne certainly appears to fill that need admirably, and will
be used as a reference or introductory chapter to much of the work that is being
presented in the literature.
Many applications of data on phase behavior can be cited now, and others undoubt-
edly will appear when annual withdrawals begin to exceed discoveries. The following
are typical questions, which can best be answered by phase-behavior computations:
What minimum bottom-hole pressure must be maintained to avoid bubble resistance
in the sand? What reservoir volume was occupied by known quantities of oil and gas
produced from a given zone? Under what conditions of withdrawal will retrograde
condensation occur in the sand? The design of equipment, such as vapor recovery
systems, pressure vessels, traps, gas anchors, etc., should be improved by a broader
knowledge of the physical behavior of gas-oil mixtures, and Mr. Sherborne's article
will certainly tend to broaden that knowledge.

W. L. JARVIS, Los Angeles, Calif.-The application of phase behavior is an integral

part of estimating reserves of industrial properties or fields by means of volumetric
methods. Under former methods of production where properties were rapidly devel-
oped and production allowed to continue at relatively unrestricted rates, production-
decline curves could be satisfactorily used in making reserve estimations. Under
conditions prevalent in the oil industry at the present time, low rates of withdrawal
from fields are necessary. Coupled with this fact, new productive areas are not, in
general, developed as rapidly as under former conditions. Since it is necessary to
have reliable reserve data for orderly planning of the exploitation of reserves, for
depreciation and depletion purposes, and for general long-range planning and policy
making, it is now necessary to replace the production rate, decline-curve method of
estimating reserves, by some other method. This of course, applies mainly to the
newer productive areas.
The soundest way to estimate these newer reserves is believed to be by volumetric
methods. This procedure consists of determining an estimate of the amount of oil
underlying a field or property and then applying a recovery factor to obtain an estimate
of the producible reserves. These recovery factors can be estimated in a number of
ways. We believe this estimation of recovery factor is the weakest point in estimating
reserves by volumetric methods. It is beyond the scope of this discussion to comment
further on recovery factor except to say that we are working on this subject for some
of the older fields and may at some future time have enough data to present
in paper form.
In determining the amount of oil and/or gas in place, the void volume is computed
from average porosity figures. Allowance is then made for the amount of water that is
connate within the sands. Data on fluid content, porosity, and permeability are
obtained through the 'medium of core analysis. The connate water content, unless
tracers in the drilling fluid or oil base mud are used, is usually available only from
generalized correlations.
The next step in estimating reserves by volumetric methods is where the pressure,
volume, and temperature relationships are used. Mr. Sherborne has described the
terms "formation volume factor" and "liquid shrinkage factor," the latter being the
reciprocal of the formation volume factor. Since a barrel of oil, measured under sur-
face conditions when in the reservoir with its constituent gas, occupies more than a
barrel of space within the reservoir, the void volume in the reservoir available to oil and

* General Petroleum Corporation of California.

 DISCUSSION 135
gas must be divided by the average formation volume factor, or multiplied by the
shrinkage factor, in order to obtain the barrels of oil present under reservoir conditions.
The formation volume factor depends on the formation pressure, temperature, and
composition and relative amounts of the oil and gas contained in the reservoir. From
this point in the estimation, only a recovery factor is needed to obtain an estimate of
the reserves.
A knowledge of "P.V.T." data is important in determining the number of phases
present within the reservoir. If the bubble-point or saturation pressure is below or
lower than the bottom-hole producing pressure, gas does not separate from the liquid
phase until it has risen in the hole and reached a depth where the pressure has been
reduced to or below the bubble point. Under such conditions the motivating force
causing the oil to enter the well bore is due to water drive. Since recovery from water-
flushed sands is higher than from sands where gas drive alone has operated, under the
above condition, a higher recovery factor in estimating reserves would be applicable.
In the distillate fields of the Gulf Coastal area, where there is no evidence of
black oil in contact with the gas phase, and for wells producing from gas caps,
where no liquid phase is present under reservoir conditions, a knowledge of pressure-
volume-temperature relations, while necessary in the estimate of reserves by volu-
metric methods, may have additional value. A particular added value applies when
retrograde condensation is possible, for the system may be outside the range of retro-
grade phenomena. If such flow conditions are present, it should be possible to regulate
the well so that the maximum amount of liquid will occur at or near the gas traps, with
a consequent justification of enlarging the recovery factor. In any event, if conditions
are maintained so that no liquid separates in the formation, this added enlargement of
recovery factor is justified. This is true because of the fact that less formation energy
is expended in gas flow as compared with oil flow.
To date, volumetric behavior and solubility relation work have not been extensive
and the results published or made available for general use have been confined to but
few fields. At present the California Institute of Technology at Pasadena and the
Standard Oil Company of California, at its West Coyote field in Orange County, have
the only equipment in the West capable of satisfactorily determining these data. This
equipment is elaborate and rather expensive, but the data obtained are so valuable for
numerous applications that there is certainly justification for further installations so
that a larger volume of data can be obtained. At present, if pressure-volume-tem-
perature data are not available on the field in question, it is necessary to use data
obtained under similar conditions of temperature, pressure, gravity, and gas-oil ratio
from fields where such work has been performed and is available. This practice is
likely to introduce some error, for the results would not necessarily be identical. For
this reason pressure-volume-temperature work should be performed on the oil and gas
from all fields where volumetric estimates are to be made, in order to obtain accurately
their solubility relations and volumetric behavior.