will be considered a s a single phase in the following

discussion.
The system is in a single phase a t temperatures and
pressures correspondnig to F. A drop in pressure on
the system from F to C, will cause a tiny bubble of lessdense phase to appear in the system, ant1 point G is
called the "bubble point." A f u r t h e r drop in pressure
from G to H will cause vaporization of constituents
from the more-dense ( o r liquid) phase and the enlargement of the less-dense (or vapor) phase. A t a n y temperature between A and C, a drop in pressure on the
system in the single-phase area above curve A-B-C will
cause the formation of the tiny bubble of vapor a s the
pressures represented by the curve A-B-C a r e reached.
Accortlingly, this curve is called the "bubble-point
curvt:." Other ways of esprcssinp this phenolnenon h a ~ , c
beer] to consider the liquid a s saturated a t the pressures
and temperatures on line A-B-C, because a slight reduction in pressure will allow the formati011 of a 17apor
phase. As the vapor pressure of thc entire systenl a s
a liquid must equal the total pressure a t tht. bubblc or
boiling point, the curve A-B-(: has bee11 called thc
"vapor-pressure curve." The us(: of several names to
represent the same phenomenon results in confusion,
but either of the terms "bubblc point" or "saturation
pressure" a t a given t e n ~ p s r a t u r emay be paltlcularly
descriptive of the phenomchnon. The recommt,nded nomellclature is to refer to the. system a s a saturated liquid
011 cul
A-B-C.
The systeni a t the tempt:rature and pressure of J is
ln a single phase. Pressure increase or] the systeni
from J to K will cause a small quantity of more-dense,
or liquid, phase to condensc in the form of tiny droplets. The resemblance of the droplets to dew gave the
name of "dew point" to the pressure and temperature
represented by K. A f u r t h e r increase in pressure from
K to L \rill cause more liquid to be formed, but a t
temperatures between C arid D pressure increases beyond some point L will cause the disappearance of the
more-dense, or liquid, phase a t point M. This vaporization upon pressure increase is opposed to the behavior
from (; to H, and so is called "retrograde vaporization."
Similarly, the drop in prcJssure on thts system in a
single phase a t N to conditions a t M will cause t h e
formation of a small quantity of more-dense, or liquid,
phase; and this phenomenon is called "retrograde condensation" because the change i n pressure causing the
condellsation is opposite to that usually encountered f u r
condensation such a s from J to I(. Tho systenl is erltirely In the vapor state a t K and a t M, and so both
poinrs a r e dew points. Curve E-K-D-M-C represents the
dew points for thc systc.m or. the saturated-vapor curve.
The measurement of the bubble point f o r increasing
temperatures along curve A-G-B will show a unique
pheriomenor~ a t (;. the critical temperatnrt,. Instead of
the bubble disappearing by gradual diminution, the
meniscus between the vapor a n d liquid phases disappears--creating a single phase. The single-phase formation a t a critical temperature h a s been observed by
Roess * a s a color change. A plot of the density of the
system a s vapor a t its dew point and liquid a t its

bubble point a s a function of temperature u - i l l silow

t h a t the saturated liquid density a t t e n ~ p e r a t u ~ . cjust
s
below C approaches the density of the saturated valinr
a t temperatures just above C. The temperature and
pressure where the dew-point anti bubble-point c u ~ . v ~ . meet is called the "critical t e n ~ p e r a t u r eand 1)ressurt.~'
of the system.
The system divides into liquid and vapor phases
within the bubble-point and dew-point curve, a s indicated by the percentage-liquid lines. In describing the
system in the single-phase a r e a outside the liquid-vapor
region, the term "liquid" o r "vapor" has been used to
represent the single phase when it was similar to n
liquid or vapor within the two-phase area. Thus, a t conditions of F and G, the system is similar; and becausc
a t G the system is in the liquid state, the tern1 "liquid"
has been applied to the system in the single phase a t F.
Likewise the system a t J is similar to the system in
the vapor s t a t e a t K, and h a s been called "va1)or" or
"super-heated vapor" a t J. The similarity between the
vapor and liquid in the two-phase a r e a a s the critical
temperature and pressure a r e approached malies t h t ~
extension of this practice to the single-phase a r e a
around the critical temperature and pressure vtxry
confusing.
The behavior of the average sub-surface sample of
crude oil is represented somewhere in the a r e a of Fig. 1
enclosed by a temperature near C, and a pressure higher
than t h a t corresponding to about 30 per cent liquid, If
the sample is removed a s a liquid from a reservoir containing two phases, i t likely will have its bubble-point
pressure a t the reservoir temperature correspond to tho
lowest pressure existing on the liquid prior to sampling.
As this pressure is often considerably above 1,000 lb., a
considerable portion of the natural-gas constituents is
present in the sample. A lowering of the pressure on
the sample, such a s from G to H i n Fig. 1, accompanied
by sufficient agitation o r time to bring equilibrium con
ditions, %-ill result in a liquid a t its bubble point and :I
vapor a t its dew point a t conditions of H. The pro1)erties of the liquid a t H will be different from tho
properties of the liquid a t G because of t h e changes 11:
composition due to the vaporization. The properties of
high-bubble-point-pressure-sub-surface samples, o r solutions of large quantities of natural g a s in crude oil,
have been shown' to depend on composition just a s
other hydrocarbon oils depend on composition. Thc
properties of t h e natural-gas constituents art. con
siderably different from the high-boiling colistituents.
and, therefore, the inclusion of large proportions of
these volatile constituents in t h e liquid phase will lo\\-ci.
the density, viscosity, and surface tension of the ligui(l
considerably below the corresponding property for th.,
high-boiling portion.
The attainment of equilibrium conditions betm-eer:
liquid and vapor phases requires intimate contact o!,
long periods of time."' A drop in pressure below t h r
bubble point of a liquid under quiescent conditions ma)
not cause vaporization to occur immediately. However,
the rising of vapor bubbles through the liquid, once
vaporization starts, provides considerable agitation, and

brings t h e vapor and liquid towards equilibrium. A rise

in pressure on a n equilibrium liquid and vapor phase
i n t h e sub-surface-sample a r e a of Fig. 1 tends t o transf e r vapor into t h e liquid phase. Under quiescent conditions t h e surface of t h e liquid would interchange constituents with the vapor, a n d possibly reach equilibrium
in a few hours. However, t h e diffusion of the liquid a t
t h e surface into the main body of t h e liquid i s so slow
t h a t years of time will not always assure equilibrium
between all t h e liquid and all t h e vapor. This behavior
shows t h e necessity of agitation of vapor and liquid
phases to reach equilibrium, especially f o r the cases
of t r a n s f e r r i n g vapor constituents into t h e liquid phase.
The phase diagram represents conditions f o r t h e
entire system in equilibrium. I t shows the quantities
of the two phases present f o r t h e case of equilibrium
or flash vaporization illustrated i n Fig. 2. Flash vapori-

-*

VAPOR

Flash Vaporization.
FIG. 2

zation brings, a t a constant temperature and pressure,

all the liquid into equilibrium with all t h e vapor either
i n a batch process o r i n a continual-flow process.
If t h e pressure is reduced on a system a t i t s bubble
point, vapor is formed. Continuous removal of t h e
vapor a s soon a s i t h a s formed, with continuous loweri n g of t h e pressure, is "differential vaporization." This
process, illustrated in Fig. 3, occurs f o r a graduallychanging system because the vapor is being removed,
and no single-phase diagram could give t h e phase
relations f o r a series of systems. Vaporization of a
constituent from a liquid causes the liquid t o shrink,
and a t r u e differential-vaporization process requires a
reduction i n volume such a s t h e introduction of a second
inert liquid if t h e vapor space i s to remain very small.
Vaporizations of sub-surface samples give off n a t u r a l
g a s a s t h e vapors, and so t h e nomenclature used is with
this f a c t i n mind. The quantity vaporized o r g a s liberated i s measured i n terms of g a s coming out of solution.
The liquid is considered to shrink f r o m t h e g a s evolution r a t h e r t h a n having a volume fraction vaporized.

Sampling Procedure
The choice of a well will depend on t h e nature of t h e
problem being studied, b u t usually includes consideration of previous production history, clean tubing set
close t o t h e producing formation, and surface equipment in condition a n d arrangement suitable f o r t h e
proposed auxiliary measurements.
Sub-surface samples a r e intended normally t o approximate t h e reservoir liquid phase if two phases a r e
present in t h e reservoir and the single phase, if a
single phase i s present. A liquid in equilibrium with a
g a s phase in t h e reservoir might be a t some point on
t h e phase diagram f o r t h e contents of t h e reservoir,
such a s point H of Fig. 1; but the separation of the
liquid from t h e g a s places the liquid on t h e bubblepoint curve of i t s phase diagram. Accordingly, the press u r e drop which causes t h e flow f r o m the reservoir to

7VAPOR

MERCURY

Differential Vaporization.
FIG. 3

the well bore "* '"ill

cause a corresponding vaporization of t h e liquid, reducing t h e bubble point of t h e
liquid t o t h e flowing pressure. A single-phase reservoir
fluid considerably removed from t h e two-phase a r e a will
have a corresponding degree of freedom in reduction of
t h e bottom-hole pressure without separation of the
second phase.
The flowing period prior to sampling should be controlled t o have a maximum bottom-hole pressure, and
corresponding maximum saturation pressure of the
liquid phase, without having by-passing of g a s and
liquid i n the flow string. A pressure measurement, prior
t o sampling, should be made a t the sampling depth a t a
steady flow state. Also i t may be advisable t o r u n a
bailer to the sampling depth to check t h a t wash or
formation w a t e r is not present a t t h e contemplated
sampling depth. Following these precautions, a well
may be sampled a t a slow flow rate, or may be s h u t in
just prior to sampling. Sampling during flowing conditions, i n a well having both g a s and liquid phases a t
the sampling point, may include all o r p a r t of the g a s
phase-depending on t h e dispersion of the two phases.

Static samples a r e considered to be liquid a t the point

of sampling. The prerequisites for sub-surface samplers
a r e means f o r introduction of representative well fluid
into t h e sampler and positive valve mechanisms which
enclose the sample, bringing the fluid from the sampling
point to the surface without loss. Thermal shrinkage
of the liquid in the sampler, a s it leaves the bottom of
the well and comes to the surface, will create a vapor
phase in t h e sampler.
The auxiliary d a t a taken with sub-surface samples
should be a s complete a s possible if fullest utilization
of sub-surface sample data is to be made. Flow tests,
well history, and especially gas-oil ratio measurements
arc. considered important.

Transferring of Samplen
The transferring of samples requires t h a t the entire
sample be in a single phase if the sample is to be
divided. The vapors formed during the thermal shrinkage must be returned t o the liquid phase by pressure increase above the bubble-point pressure a t the temperat u r e of the sample. This formation of a single phase
-y
and agitausually is accomplished by ~ ~ i e r c u i injection
tion to assure equilibrium. Samples may be transported
t o the laboratory in the sampler or in pressure containers. Transfer from the sampler t o containers must
be conducted a t pressures sufficient t o allow a pressure
reduction during flow without reaching the bubble
point. Leaks while transporting a r e serious; f o r a n
aliquot proportion of the two phases is not likely to
escape, and thus the composition i n the container is
changed.

Analyses of Samples
The analysis of the sub)-surface samples by l o a tenlperature fractionation should be included a s one of
the tests on t h e sample; for t h e analysis and proper
equilibrium d a t a l' " will permit the computation of the
behavior of the sample under a n y series of vaporizations. The a p p a r a t u s required is a double-stage distillation unit t o remove the volatile constituents from the
crude, preferably two or three a t a time, and subsequent separation into pure compounds.
The analytical procedure is similar t o t h a t used for
g a s analyses, but especial precautions must be made
t h a t the volatile constituents a r e removed from t h e
crude oil, and absolute quantities of the pure constituents must be measured. A sample in the range of
50 t o 200 ml. should be analyzed f o r nitrogen, methane,
ethane, propane, isobutane, normal butane, pentanes,
and hexanes-with
determination of volume, density,
and molecular weight '' of the heptanes and heavier
fraction. The distillation of hexanes through nonanes
on a high-temperature distillation column, with gravities
and molecular weights of t h e cuts, h a s been found a n
improvement over the usage of heptanes plus a s a
single fraction. Analyses should be reported a s both
mol and weight fractions, or percentages, with inclusion

of the properties of constituents of higher boiling point

t h a n pentane or hexane.

The initial vaporization o r saturation pressure of

a sample a r e generally desired. A portion of the sample
is compressed to a single phase a t some temperature
such a s the reservoir temperature. The volume on this
single phase i s increased gradually, with measurement
of pressure decreases. A s the saturation pressure is
reached, the pressure decreases a t a slower r a t e for
given increments of volume increase. A plot of pressure
decrease vs. volume increase will show the bubble-point
pressure a t the intersection of the two curves. Agitation
in some form is necessary for accurate bubble-point
determinations. The saturation pressure normally is
reported a s pounds per square inch absolute, and must
include the temperature of the measurement.
The pressure decrease with increases in volume of
the system provides compressibility data on t h e sample,
provided t h e a p p a r a t u s containing the sample is
calibrated f o r volume changes with pressure. Reporting
of d a t a may be directly a s volume changes with pressure based on the volume of the sample a t the bubblepoint pressure and temperature. A uniform method
of reporting compressibility d a t a is per cent decrease
in volume of the sample f o r 100-1b.-per-sq.-in. increase
in pressure based on the volume a t t h e bubble point,
expressed a s applying a t a temperature and over a
given pressure interval.
Following the bubble-point measurement, t h e sample
may be vaporized either a s a flash vaporization or by
differential vaporization. Two procedures have been
used for each method.
The differential vaporization adopted by Lindsy '
deviated from a truly differential process, because t h e
constant volume employed caused a large vapor space
to be formed due to t h e shrinkage of t h e liquid. This
constant-volume differential vaporization may be closer
to the t r u e conditions in a constant-volume reservoir
t h a n a t r u e differential vaporization. The customary
reporting of results1, h i v e s pressure vs. solubility of
g a s measured a s cubic feet a t 60 deg. F. and 14.7 lb. per
sq. in., absolute, f o r a barrel of t h e crude oil which
remains a t the end of the vaporization process (residual
crude oil) but measured a t 60 deg. F. This method
presents difficulty if the equilibrium pressure a t t h e end
of the vaporization is not exactly 14.7 lb. per sq. in.,
absolute, a s the total quantity of vapors is sensitive
to small differences in final pressures. However, the
difference in solubility between two pressures considerably above atmospheric is not dependent on this
final pressure, and should check between laboratories
even if the total quantity does not. Solubility curves
drawn from the measurements a t pressure intervals
approach straight lines above 300 t o 500 lb. per sq. in.,
and may be extrapolated short distances, such a s from
sub-surface-samplesaturation pressure u p to the static
reservoir pressures.

The shrinkage or liquid volume fraction vaporized is

reported a s per cent of the volume of residual crude
oil which was vaporized, and includes the thermal
shrinkage of the residual crude oil from the test temperature down to 60 deg. F. The reporting of shrinkage
is subject to the same difficulties as solubility. Shrinkage from 40 per cent to 30 per cent for a pressure drop
from A to B lb. means that the volume of liquid a t
pressure A was 1.40 parts; a t pressure B i t was 1.30
parts; and a t the end of the vaporization, with residual
crude oil cooled to 60 deg. F., it would be 1.00 part.
This use of residual crude oil as a basis appears awkward, but allows correlation of data for similar subsurface samples having different bubble-point pressures.
A variation of the "constant-volume" differential
vaporization is used, and will be designated a s the
"approximate differential" vaporization." This method
eliminates the vapor space developed in the chamber
due to shrinkage a t the several pressure decrements
used. Mercury injection a t the end of each pressure
decrement brings the contents of the vaporization chamber to a single phase. The bubble-point pressure is determined for the system in a manner similar to the
initial value. This method would be a true differential
vaporization if very small pressure decrements were
used. I t eliminates the computation of the quantity of
vapor in the vapor space, which must be added to the
evolved gas when computing the solubility data for
the constant-volume differential vaporization. There
appear to be no more differences between the approximate-differential and the constant-volume-vaporization
results than between results of different laboratories
and equipment using the constant-volume-differential
method. However, future work conducted accurately a t
low pressures may require a distinction between the
two methods.
Flash vapom'zations always tend to bring all the gas
and oil into equilibrium a t a temperature and pressure,
but different methods may be employed or measurements
made.
The measurement of a unit volume of sub-surface
sample a t its bubble-point pressure a t a given temperature, with subsequent measurements of the volume of
the two-phase system a t several pressure decrements
down to atmosphere, give data for a pressure vs. volume
(PV) curve" a t a specified temperature. The relative
volumes reported a r e based on the bubble-point volume.
The reduction in pressure to some lower pressure,
often atmospheric, on a given quantity of sub-surface
sample a s it passes through a gas-liquid separator approaches the conditions in the field separators. The
quantity of vapor formed is reported a s cubic feet a t
60 deg. F. and 14.7 lb. per sq. in., absolute, per barrel
of oil in the liquid phase, but subsequently brought to
60 deg. F. The shrinkage from the volume of the subsurface sample to the volume of the residual crude oil
a t 60 deg. F. may be expressed a s per cent of the
volume of the residual oil a s in differential vaporizations, but there appear to be advantages in this case
of reporting per cent of the bubble-point liquid volume
which was lost by vaporization.

A third variety of tests on the sub-surface sample

is to measure the flash vaporizations a t a constant pressure on a series of liquids having bubble-point pressures
from the sub-surface-sample value down to low pressures-the reduction in the bubble-point pressure being
accomplished by the approximate differential-vaporization process.
I n all vaporization measurements the residual crudeoil gravity, the gas gravity, and possibly the gas analysis should be determined.
Interpretation of Results
The choice of measurements on sub-surface samples is
guided by the uses contemplated for the data. Subsurface-sample data must be accompanied by auxiliary
information in order to be utilized to the greatest advantage. Plans a r e made for having separate discussions on the application of sub-surface-sample information in several directions, but a few examples will be
enumerated.
The greatest contribution which sub-surface-sample
work has made to the production industry is the development of our concepts of the behavior of oil and gas
in the reservoir. Not until sub-surface samples were
obtained did we have a clear idea of the phase relations
i n the sand-which is necessary in order to make intelligent decisions on many daily production problems.
Sub-surface-sample data make possible a n alternate
method of estimating the oil in place in a constantvolume pool, without knowledge of sand extent.". '' A
complete production history of the pool with sub-surface
pressures is the auxiliary information needed.
Fractional analyses of sub-surface samples and equilibrium constants are used to predict surface separations of oil and gas a s to gas-oil ratio and naturalgasoline content 'of the gas. Stage separation and
natural-gasoline reserves now a r e understood more
completely.
Better identification of horizons is permitted by the
combined use of equilibrium data and sub-surfacesample analyses. Because of the high concentration
of the more volatile constituents in high-bubble-point
pressure samples, a n added criterion for identifying a
reservoir liquid is available. Sub-surface sample analyses and equilibrium data assist in identifying gas zones
a s being the equilibrium phase for a reservoir oil or
not of the proper composition to be the equilibrium
phase.

BIBLIOGRAPHY

' B.

E. Lindsy, U . 8. Bur. Mines R p t . Investigation 321s (1933).

'B. E. Lindsy, Petroleum Engr. 7, 34 (1936).
' D . L. K a t r and K. H. Hachmuth. Ind. Eng. Chem. 29. 1072

11QR7b
,- - . ,.
'B. H. Sage, .J. G . Schaafsma, and W. N. Lacey, Ind. Eng.
Chem. 26, 214 (1934).
' W. B. Kay Ind. Eng. Chem 30 459 (1938).
OS. von P i l i t Oil Gas J 35 [10j 54 (1936)
' D. L. ~ a t z ,Am.
'
~ n s t . 'Mining Met. ~ n g r s .Tech. Pub. 971,
Oct. (1938).
Roes8 J . Inst. Petroleum Tech. 22 665 (1936).
* W ~ ' ~ a c eProc
y
API 13 [IV
1932).
lo K: D: ~ o r n e i o y .
N. Lacey
E: Scudder, and F. P. Stapp.
Ind. En$: Chem. 25. 1014 (193d).
" S.
Buckley, Trans. Am. Inst. Mining Met. Engrs. 127,
178 (1937).

+.

d. 16

"1).

i$A<,.,,
ln9r

I..

K:tte, Trans. Am. Inst. Mining Met. Enyrs. 127, Is!)

i
r.

'"I. T. Itall and H. 11. Smith. Ind. ISng. ('hem., dtlol. Edn. 8.
436 ( 1 9 3 6 ) .
K. J . Schilthuis Drilling and Production Practicr 1995 120.
It. J. ~ c h i l t h u i s ,Trans.
'
Am. Inst. Mining Met. ~ ' n & s .( b e t r o leum Development and Technology) 118, 33 ( 1 9 3 6 ) .
leD. 1,. Katz, Trans. Am. Inst. Minin Met. Engrx. (I'etroleum
Deue;opment and Technology) 118 19 9 1 9 3 6 ) .
" 1 . (;. Exline, Drilling and ~ r d d u c t i o nProcticc, 1!?,?6, 1%.
lH1-.T. Moore. l'roc. API 11 [IV] 27 ( 1 9 3 0 ) .
lY
3I. I*. 1Iaidl.r. Drilling and I'rodrrction 1'ruc.tirc. l!?dli, 181.

''

DISCUSSION

H. H. Power (Universitb of Texas) : Thc Subcommittee on Fundamentals of Sampling, Transporting, and

Analyzing Sub-surface Samples of Crude Oil, of the
Topical Committee oli I'roduction Technology, was
organized under Dr. Katz a s chairman for the purpose of determining the fundamentals involvcti, and to
develop a sound basis for reporting and correlating reliable sub-surface crude-saniple data. Accordingly, a f t e r
several committee meetings, a 'eport has heen prepared
in accordance with the summary just delivered by
Dr. Katz. After approval hy the topical committee and
the Central Committee on Drilling and Production l'ractice, this report will serve a s a (tentative) code f o r
sampling, transporting anti analyzing samples of oil
and g a s taken under pressure from the reservoir. Standa r d methods developed should enable investigators di
rectly to compare the results obtained.
\Villiam N. Lacey (California Institute of Technology) (written) : I had the privilege of discussing the
subject of this paper with Dr. Katz' committee the
other day, and my comments now will be confined to a
few minor points, mentioned mostly f o r emphasis. I f
sub-surface sampling is to be of greatest value to the
industry, there must be a general understanding of principles, and the use of terms and experimental methods
must be reasonably consistent. This is a goal toward
which the committee is working, and commendation is
deserved.
I t is desirable to re-emphasize the f a c t t h a t the diagram in Fig. 1 applies only to a system of a single total
composition. If material is added to or removed from
the system, this diagram, or set of curves, would no
longer apply, but one would have to shift to another
diagram of similar character. The one shown purports
only to be a representative one. In this connection, no
unusual significance should be attached to the fact
t h a t the 30-per-cent-liquid curve reaches the coordinate
origin. I t just happens so f o r the particular mixture
Dr. Katz has chosen to consider. Although the diagram
sho~vn is representative of many field inistures, one
should not lose sight of the cases of mixtures f o r which
the point C lies a t a lower temperature than t h a t f o r
point B. I t should be remembered also t h a t the phase
diagrams of many field mixtures probably a r e complicated a t the high pressures corresponding to points B
and C (8,000 to 10,000 Ib. per sq. in., or higher in many
cases) by the appearance of a second liquid or a semisolid phase which would require a significant alteration
of the diagram.
When Dr. Katz says t h a t when the state of the system

corresponds to point H i n Fig. 1 i t consists of liquid a t

its bubble point and vapor a t its dew point, he does not
mean t h a t the system a s a whole is either a t bubble
point or dew point; but t h a t if the liquid phase ( f o r
example) were isolated, it then would correspond to
bubble-point liquid for a different set of curves representing a new total composition. A similar statement
applies to the g a s which is a t dew point for a still
different diagram.
I t might be worthwhile to voice a word of cautlon t h a t
the job of bringing the two-phase coiltents of a long
narrow chamber to a uniformly-mixed single licluid
phase is a difficult one by the rocking method mentioned
in the paper.
I n most cases which involve the presence of two phases
a t the place of sampling, it i s my belief t h a t precautions
must be taken to obtain only one of the phases in the

FIG. 1 (BURNETT)
sampler, or correct interpretation of results becomes
extremely difficult. It must be certain also t h a t the one
phase sampled comes entirely from one producing zone.

E. S. Burnett (U. S. Bureau of Mines) : Fig. 1

(Burnett) represents my conception of the diagrammatic phase relations f o r a complex hydrocarbon system; t h e absolute zeros of the coordinates of this figure
a r e a t t h e point 0.
Through comparison and analogy with various phase
diagrams f o r single-component fluids, I conclude t h a t
all quality lines, which indicate constant-phase proportions, should meet a t the point C of the envelope
A B C D E, and t h a t they should meet t h a t envelope
tangentially a s shown in Fig. 1 (Burnett) r a t h e r than
a t various angles, a s suggested by the author's Fig. 1.
Thus, apparently, t h e 20-per-cent line with t h e 80-percent line should appear a s one continuous curve tangent
to the envelope a t t h e point C; the 30-per-cent line with
the 70-per-cent line, and t h e 40-per-cent line with the
60-per-cent line should have similar appearances; the
50-per-cent line thus would be a double line, doubling
back on itself a t the point C and, hence, having a tangent
common to all lines shown through t h a t point. ( F o r example, compare t h e quality lines on the familiar "steam
dome" of a Mollier chart of the properties of stearn.)

With regard to the terminations o r "footings" of these

several quality lines on either axis of t h e diagram: It
is my understanding of these relations t h a t if the
point 0 represents absolute zero of pressure and temperature, then, physically, all of these lines must foot
on the temperature axis r a t h e r t h a n on t h e pressure
axis, or a t t h e origin 0. Fig. 1 ( B u r n e t t ) shows them
extending to footings a t temperatures ranging from a
lower value R (never zero) f o r 100 per cent liquid, to a
higher value S f o r 100 per cent vapor, with no mutual
intersections except a t the point C.
Actual locations of these curves, of course, depend
upon the particular system investigated. F o r some systems the interval R to S may be relatively small; a n d
possibly f o r some R and S conceivably might coincide,
in which case the quality lines would all meet a t t h a t
point on t h e temperature axis a s well a s a t point C.
Should a solid phase develop, modifications of Fig. 1
(Burnett) would be required t o depict t h e behavior a t
low temperature.
Support f o r the arrangement indicated in Fig. 1
( B u r n e t t ) is afforded by the concept of a lower temperature limit of vaporization a t zero absolute pressure,
the so-called "Nullpunkt der Verdampfung" discussed
by Dr. C. von Rechenberg i n his book, Einfache und
Fractionerte Destillation, 337 t o 344, Schimmel and
Company, Leipzig (1923).
Referring to Fig. 1 ( B u r n e t t ) , isothermal pressure
reduction on the liquid phase from a condition represented by the point F' would not result in evolution of a
vapor phase, even if the liquid were exposed to a vacuum.
Confirmation of this effect is t h e use of certain liquids
recently developed f o r "vacuum" monometers.
Isothermal pressure reduction on t h e liquid phase

from a condition represented by a point F' would result

i n partial vaporization and a n ultimate non-volatile
residue, a situation indicated by the results of isothermal
"vacuum" distillation of many hydrocarbon mixtures.
Mr. Katz: With regard to the shape of the quality
lines on t h e pressure-temperature diagram, I do not
believe they necessarily should be symmetrical a s indicated in Fig. 1 ( B u r n e t t ) . F i r s t , there can be no analogy
between a pure substance a n d a complex mixture on
quality lines of a pressure-temperature diagram; f o r
pure substances have a single (vapor-pressure) curve
when these coordinates a r e used. Second, the computed
phase diagram f o r the methane-propane system indicated a complete lack of symmetry f o r the quality lines
based on mol per cent. As no experimental d a t a have
been reported on t h e phase behavior of a complex mixt u r e adjacent to the critical conditions, I do not wish to
imply the lines of Fig. 1 a r e correct, but I also do not
believe they can be shown t o be incorrect-especially
when considering t h a t the per-cent-liquid lines might be
either weight, mol, or volume percentages.
With regard to the behavior of the system a t low pressures and temperatures (Fig. 1 ) the scales were not intended to be absolute scales because of lack of information a t low pressures and because of the appearance of a
solid phase a t low temperatures. The appearance of a
solid phase would eliminate any significance of the conditions a t F i n Fig. 1 ( B u r n e t t ) , a s any mixture containing methane surely would contain solids if the temperature were so low t h a t methane would not vaporize
a t low pressures. Fig. 1 was intended to cover only the
range of pressures and temperatures a t which a singleor two-fluid ( g a s and liquid) phase was present.