Groihim,ro L,! Ciwwh,m,w Ac!u Vol. 53, pp. 3-8 0016.7037/89/%3.

00
t .X3
Copyright 0 1989 Pergamon Press plc. Printed in U.S.A

Synthetic fluid inclusions: IX. Critical PVTX properties of NaCI-Hz0 solutions

C. L. KNIGHT and R. J. BODNAR
Department of Geological Sciences, Virginia Polytechnic Institute & State University, Blacksburg, VA 2406 I, II&A.

(ReceivedAugust 4, 1988;accepted in Te~ised~r~ October 17, 1988)

Abstract-Critical PVTX properties of NaCl-Hz0 fluids having compositions ofO-30 wt% NaCl have been determined
using the synthetic fluid inclusion technique. Critical temperatures and pressures increase from 374. I C and 220 bars
for pure H20, to 820C and 1574 bars for 30.0 wt% NaCl. Critical specific volumes decrease from 3. I 1 to 1.44cm3/g
over this same salinity range.
Critical temperatures of NaCl-Hz0 fluids over the range O-30 wt% NaCl are described by the equation
7= 374.1 + 8.800@ + 0.1771+ 0.02113~-+ 7.334. lO-4#
where Tis the critical tempemture in degrees Celsius (+4.OC) and Cpis fluid com~sition in weight percent NaCl. The
critical pressure, determined from the intersection of the critical isochore with the critical temperature in P-T space,
is expressed as a function of the critical temperature according to the relationship
P = 2094 - 20.56T + 0.06896T2 - 8.903 X IO-T3 + 4.214. 10-8T4
where P is the critical pressure in bars (f21 bars) and T is the critical temperature in degrees Celsius. The critical
specific volume is given as
SV = 3.106 - 0.59679 - O.O1066P*+ 0.01267@
where SV is the critical specific volume in cm/g (?O.OZ cm/g) and YI is related to the salinity as
~=ln(wt%NaCl+l)
The slopes @P/AT) of P-T projections of the critical isochores increase regularly with increasing salinity, from -2.8
bars/Y for pure H20 to -6.8 bars/Y for a 30 wt90 NaCl solution.

INTRODUCTION
THE SYSTEM NaCI-Hz0 may be used to model fluid com-
position in a wide variety of geologic en~ronment~ inclu~ng
porphyry copper and epithermal precious metals deposits and
submarine and terrestrial geothermal systems. Recent studies
have documented rather conclusively that boiling or immis-
cibility plays an important role in the evolution of these var-
ious hydrothermal systems. A better understanding of fluid
evolution in these environments, therefore, requires knowl-
edge of phase equilibria in NaCl-Hz0 fluids over a range of
PTX conditions. One of the more important aspects of phase
equilibria that is poorly understood at present is the Iocation
of the critical point for NaCl-H20 fluids, particularly those
with salinities greater than 15 wt% NaCl. Of equal or greater
importance, but even more poorly constrained, are the vol-
umetric properties (densities or specific volumes) of NaCI-
Hz0 solutions at the critical point, and the P-T projection
of the critical isochore.
Important features of the phase behavior of NaCI-HZ0
solutions in P-T space are illustrated on Fig. 1. Shown on
this distorted schematic diagram is the large field of immis-
cibility in which two fluid phases (liquid + vapor) may coexist.
This held is bounded by the NaCl-H20 ice-liquid boundary,
which extends from the eutectic point in the NaCl-HZ0 sys-
tem (E; Fig. I) to the triple point of pure H20 [T(H,O); Fig.
11,the pure Hz0 liquid-vapor curve, which extends from the
triple point of pure H20 [T(H,O); Fig. I] to the critical point
of pure Hz0 [C(H~O); Fig. 1J,the P-7 projection of the NacI-
H20 critical curve, which extends from the pure HZ0 critical
point to the pure NaCl critical point [C(NaCl); Fig. 11, the
3
pure NaCl liquid-vapor curve, which extends from the triple
point of pure NaCl [T(NaCl); Fig. l] to the critical point of
NaCl, and the liquid + vapor + solid (L + V + S) curve for
NaCl-HZO, which extends from the NaCl-H20 eutectic (E;
Fig. 1) to the pure NaCl triple point. Between the NaCI-HZ0
eutectic (E; Fig. 1) and the NaCl-HZ0 peritectic (P, Fig. I),
the stable solid phase along the L + V + S curve is hydrohalite,
NaCl - 2H20. From the peritectic to the triple point of NaCl,
the stable solid phase along the L + V + S curve is halite.
The pure Hz0 liquid field is bounded at lower temperatures
by the solid-liquid curve [S(HzO)]L(H20); Fig. 11, which
originates at the Hz0 triple point and extends to higher pres-
sures with a negative slope. Dashed lines labelled [S(E) 1L(E);
Fig. l] and [S(NaCl-H20)]L(NaCl-H*O); Fig. I] represent
solid-liquid equilibrium for NaCl-HZ0 solutions of the eu-
tectic composition and some intermediate composition be-
tween pure Hz0 and the eutectic composition, respectively.
For any given NaCl-HZ0 composition, a smaller field of
immiscibility exists within the larger immiscibility field for
the entire NaCI-1120 system described above. The limits of
immi~ibility for a low to moderate salinity composition (less
than approximately 25 wt% NaCl) are shown schematically
by the shaded portion of Fig. 1. The liquid-vapor field for
this composition [L + V (NaCI-H,O); Fig. I] is bounded by
the ice-Iiquid-va~r curve, which extends from the NaCl-
Hz0 eutectic (E; Fig. 1) to the freezing temperature (or ice-
melting temperature) for the NaCI-HZ0 composition chosen
[Tm(ice) (NaCl-HZO); Fig. I], the bubble-point/dew-point
curve for the NaCl-HZ0 composition chosen, which extends
from the freezing temperature [Tmfice) (NaCl-H,O); Fig. I],
through the critical point for that composition [C(NaCl-H20);
 C. L. Knight and R. J. Bodnar
TEMPERATURE -
RG. 1. Distorted schematic P-T projection of phase equilibria in
the NaCl-HZ0 system modified from BODNAR etnf.(1985). Shown
are the Hz0 triple point [T(H20)] at O.OlC and 0.006 bar, the Hz0
ice-liquid curve [S(H,O) 1L(H*O)], the Hz0 liquid-vapor curve
[L(H*O) /V(H*O)], the Hz0 critical point [C(H20)] at 374.1 C and
220 bars, the NaCl triple point [T(NaCI)] at 801C and - 1 bar, the
NaCl squid-va~r curve extending Born the triple point to the critical
point of NaCl [C{NaCl)] at -3600C and -258 bars, the NaCl-
Hz0 solubility curve (L + V + S) extending from the NaCl triple
point to the NaCl-Hz0 eutectic (E) at -20.8C and 0.001 bar [note:
hydrohalite is the stable phase along the solubility curve from the
NaCI-Hz0 eutectic to the pet-hectic (P)], the NaCl-Hz0 vapor-halite
field (V + NaCl), the liquid-vapor field [L + V (NaCl-H,O), shaded]
for an NaCl-Hi0 fluid of low or moderate salinity, and the critical
point [C(NaCl-H*O)] for that salinity. See text for description of other
symbols.
Fig. l] to its intersection with the L f V + S curve (point A;
Fig. I). At low pressures the immiscibility field is bounded
by that portion of the L + V + S curve extending from the
eutectic point (E; Fig. 1) to its intersection with the dew-
point curve (A; Fig. 1). At any P-T point within this immis-
cibility field, an NaCl-Hz0 fluid having the bulk composition
defining that field will split into a liquid phase having a salinity
greater than the bulk salinity and a vapor phase having a
salinity less than the bulk salinity.
Note that the critical point [C(NaCl-H,O); Fig. l] for an
NaCl-Hz0 fluid is not the terminus of the liquid-va~r loop
as it is in a single component system, such as pure H20.
Rather, the critical point for a particular NaCI-HZ0 com-
position simply represents a unique specific volume (and P-
T point) along an otherwise continuous liquid-vapor curve.
In this paper we present new data on the critical properties
of NaCl-Hz0 solutions having salinities 530 wt% NaCl. These
data were obtained using the synthetic fluid inclusion tech-
nique combined with an empirical equation describing PVTX
relationships of NaCl-Hz0 solutions. We have extended the
range of available data to higher salinities than was previously
available, and we provide the first published data on the vol-
umetric properties and P-Tprojections ofthe critical isochores
for NaCl-HZ0 solutions.
PREVIOUS STUDIES
Critical properties of the NaCl-HZ0 system have been ex-
amined by a number of workers using a variety of experi-
mental and theoretical approaches. Most of these studies have
yielded data over limited ranges in temperature and salinity
(e.g., BISCHOFFand ROSENBAUER,1984; BI~CHOFFet al.,
1986; KHAIBULLINet al., 1979; MARSHALLand JONES, 1974;
OLANDERand LIANDER, 1950; ROSENBAUERand BISCHOFF,
1987; and URUSOVA, 1974). SOURIRAJANand KENNEDY
(1962) conducted one of the more detailed early studies of
phase equilibria in the NaCl-HZ0 system, and report critical
temperatures and pressures for salinities to 26.4 wt% NaCl.
Additionally, BISCHOFFand PITZER (1989) provide a com-
prehensive summary of NaCl-HZ0 PTX properties to 500C.
While the data of these reports form a consensus on the
P-T coordinates of the NaCl-HZ0 critical curve, there is a
marked disagreement in terms of composition corresponding
to a given P-T point. Fu~he~ore, owing to ex~~rnen~l
difficulties, none of these studies have determined critical
properties for compositions in excess of room temperature
saturation (26.4 wt% NaCl).
EXPLEMENTAL PROCEDURE
Critical properties of NaCl-HZ0 fluids were determined using the
synthetic fluid inclusion technique described by BODNAR and STER-
NER (1987). In brief, fluid inclusions are synthesized by healing fmc-
tures in natural, inclusion-free quartz in the presence of fluids of
known composition at controlled pressures and temperatures. This
is accomplished by placing thermally fractured inclusion-free quartz
cores into platinum capsules along with dry amorphous silica powder
and a few tens of microliters of NaCI-H20 solution. Samples of fluids
with NaCl content greater than rim-tem~mture saturation are
prepared with additional solid NaCl added to achieve the desired
fluid bulk composition by weight. The capsules are sealed, placed in
cold seal pressure vessels and taken rapidly to the desired P-T con-
ditions, Pressures are read to the nearest 5 bar increment on a factory-
calibrated Heise gauge (traceable to NBS) with an estimated accuracy
of + 10 bars. Temperatures are measured and controlled to the nearest
l.OC with chromel-alumel thermocouples and are estimated to be
accurate within +2.OC. Run durations are typically three to seven
davs at conditions ranaina from 550 to 850C and 1 to 2 kb.
Upon cooling to ro~rn-tem~rature, runs are depressurized and
samples are prepared and examined using a petrographic microscope
equipped with a Fluid Inc. adapted USGS-type gas-flow heating/
freezing stage. Samples requiring observation at temperatures greeter
than 700C are examined on a Leitr Model 1350 microscope heating
stage. Samples are frozen to verify their salinity, and approximately
six to ten homogenization temperatures are measured across each
sample. Critical temperatures recorded have an associated accuracy
of +0.2C at the critical point of pure water (374.1 C), 42.OC at
573C and an estimated *5.OC at 66OC, based upon prior cali-
bration of the heatin~fm~ing stage and observations of the &3 quarts
transition.
Run conditions were chosen on the basis of known or estimated
fluid phase equilibria in P-Tspace for the NaCl-Hz0 system. Figure
2 shows the limits of immiscibility for some low to intermediate
salinity in the NaCl-Hz0 system-this field of imm~ibility corre-
sponds to the shaded region shown on Fig. 1. Also shown on Fig. 2
are the isochoric P-T paths followed by three fluid inclusions of dif-
ferent densities as they are heated from room temperature (R.T.; Fig.
2). Fluid inclusions synthesized along an isochore of less than critical
specific volume (as at point 1; Fig. 2) will homogenize to the liquid
phase (L + V --, L; Fig. 2) at a subcritical temperature [Th( 1); Fig.
21 defined by the intersection of the isochore with the liquid-vapor
curve. Fluids trapped at P-T conditions yielding a specific volume
greater than the critical value (as at point 2; Fig. 2) will homogenize
by expansion of the vapor phase (L + V + V, Fig 2) at a temperature
above the critical temperature fTh(2); Fig. 21, defined by the inter-
section of its isochore with the liquid-vapor curve. Fluids of critical
specific volume can only be trapped at the critical point (C; Fig. 2)
or along the critical isochore (as at point 3, Fig. 2). Fluid inclusions
of the critical specific volume will homogenize neither by evapomtion
of the liquid phase nor by condensation of the vapor phase. Rather,
the density of the vapor will increase towards the critical value as the
density of the liquid decreases until each phase occupies an equal
volume within the inclusion. This mutual approach ofphysical prop
 NaCl-Hz0 critical properties 5

Fig. 3) is defined as the pressure at the point of intersection of the

critical isochore with the critical temperature (Tc; Fig. 3).

RESULTS

Critical temperatures were determined for NaCl-H,O bulk

compositions from 0 to 30 wt% NaCl (Fig. 4). For all salinities
except 22.5 and 30 wt% NaCI, inclusions homogenizing by
critical behavior were trapped at two different P-T points
along the critical isochore. All critical temperatures deter-
mined from samples synthesized at two points along each
critical isochore were reproduced to within C 1.OC, with the
exception of the 25 wt% salinity sample, which was repro-
ducible to +4.OC. Only one critical-density sample was ex-
amined for fluid compositions of 22.5 and 30.0 wt% NaCl.
R r. Th(1) Th(3) TW Formation conditions and measured homogenization tem-
TEMPERATURE - peratures of c~ti~i-density NaCI-Hz0 synthetic fluid inclu-
sions are listed in Table 1.
2. Distorted schematic phase diagram of the low salinity NaCl-
HZ0 composition illustrated in Fig. 1showing the PTpaths followed Critical temperatures of NaCl-HZ0 solutions determined
by fluid inclusions of three different densities upon heating from in this study are described by the empirical equation:
room temperature (RT) to their homogenization temperatures [Th( 1),
Th(2), Th(3)], and the relationship between homogenization modes T = 374.1 -t 8.8OOr#~+ 0.1771#
(L + V -* L, L + V + V) of NaCl-Hz0 fluid inclusions and trapping
conditions relative to the location of the critical isochore (see text - 0.021 1343 + 7.334. lo-4#4 (I)
for explanation).
where T is the critical temperature in C and d, is fluid com-
position in wt% NaCl. This equation was fitted to experi-
mentally determined critical temperatures for NaCl-Hz0 so-
erties causes the meniscus separating liquid from vapor to gradually
fade and disappear upon homogenization at the critical temperature lutions of 0 to 30 wt% NaCI, and should not be used to cal-
[Th(3); Fig. 21. culate critical temperatures for salinities > 30 wt% Nat2
As a result of the long-range nature of the ionic forces between Critical tem~mt~es calculated from Eqn. ( 1) reproduce our
Na and Cl- in solution, variations in specific volume in the vicinity measured critical temperatures within i4.0C and are com-
c f a critical point are not as large in the NaCl-Hz0 system as in the
HZ0 system (BISCHOFF et al., 1986). In other words, the temperature-
pared with other published critical temperatures in Fig. 5.
density projection of the solvus becomes more rounded, or less flat, Critical specific volumes for all compositions studied (Fig.
with increasing salinity as the critical temperature is approached. 6) were calculated using an empirical equation of state de-
Thus, there is a much narrower range of density or specific volume veloped by BODNAR (1985) which relates molar volumes of
over which ~ud~~ti~ behavior may occur For higher salinity
NaCl-HZ0 fluids to PTX conditions over the range 100 to
compositions as compared to lower salinities (see for example KHAI-
BULLIN and BORISOV,1965, their Fig. la; ROEDDER,1984, his Figs. 900C and 1 to 5 kb. Critical specific volumes (Table 1) were
4-5 and discussion on pages 89-90). Still, some gradational behavior determined at the point of sampling along each critical is-
in fluid inclusions of near-critical specific volume is expected near ochore, eliminating the need to correct these values for ther-
the critical isochores. Indeed, inclusions trapped adjacent to but not mal expansion of the host quartz, as described by BODNAR
on a critical isochore will Frequently display near-critical behavior
(ROEDDER,1984), manifest in the boiling appearance and fading
men&i of inclusions homogenizing at near-critical ~rn~mtu~. Slow
heating rates and careful observation of those fluid inclusions exhib-
iting pseudocritical behavior reveals the true homogenization mode;
menisci of inclusions of less than critical specific volume will fade
greatly prior to shrinking while those of inclusions with greater than
critical specific volume will fade as they expand.
The relationship between specific volume and fluid inclusion be-
havior upon heating to the homogenization tem~rature described
above was used to define the critical properties of NaCl-Hz0 solutions.
Runs are placed along isobaric P-Ttrajectories designed to intercept
the critical isochore for the composition studied, as indicated by the
dots bracketing the critical &chore on Fig. 3. Initially. P-Ttrajectories
for the NaCI-HZ0 system are planned on the basis of critical points
reported by SOURIRAJAN and KENNEDY(I 962), with isochores as-
sumed to have positive siopes and to be straight lines over relatively
short ranges in pressure and temperature. This PVT sampling tech-
nique allows us to obtain a rough approximation of the position of
the critical isochore. In subsequent runs, homogenization behavior TC
of these synthetic fluid inclusions is used to determine the relative TEMPERATURE -
position of the critical isochore. The brackets thus defined are de-
creased in each successive run until fluid inclusions displaying critical FIG. 3. Distorted schematic diagram of a particular NaCI-H20
behavior (i.e., of critical specific volume) are obtained. The entire composition illustrating the P-T trajectory sampling technique used
process is repeated along a second isobaric section in order to confirm to locate the critical isochore, and the graphical definition of the
the observed critical temperature and to obtain P-T coordinates of critical pressure (PC) at the intersection of the critical isochore with
two points along each isochore. Once the position of the critical is- the critical temperature (Tc). Black dots represent hypothetical sample
ochore has been determined in this manner, the critical pressure (PC; run conditions.
 C. L. Knight and R. J. Bodnar

W
650 - ; 650

z
550
!!

E
I- 450

ITICAL TEMPERATURES .

0 5 10 15 20 25 30 0 5 10 15 20 25 30

SALINITY (wt.% NaCI) SALINITY (wt.% NaCI)

FIG. 4. Critical temperatures in the NaCI-H20 system determined
using the synthetic fluid inclusion technique. Line represents critical
temperatures predicted by Eqn. (1).
and STERNER (198.5). Specific volumes calculated for criti-
clay-homogenizing fluid inclusions of identical composition
trapped at different points along the same isochore vary by
less than 0.46%. Larger variations in specific volume between
fluid inclusions samples of the same composition result in
differing homogenization behaviors and tem~mtur~. For
example, one 10 wt% NaCl fluid inclusion sample with a
specific volume 1.34% (0.025 cm3/g) above the critical specific
volume homogenized to the vapor phase at a temperature
9C greater than the critical temperature. Thus, in the vicinity
of the critical specific volume, small variations in the specific
volume result in easily observable and measureable differ-
ences in both the mode and temperature of homogenization
of inclusions. An empirical equation relating critical specific
volume to composition is given by:
SV = 3.106 - 0.5967?T! - 0.01066\k2 + 0.01267q3
FIG. 5. Comparison of critical temperatures calculated with Eqn.
(1) (solid line) with data of MARSHALLand Jo?%s (!974) (M&J (1974),
open circles); GLANDERand LIANDER(1950) (O&L (1950), open
squares); ROSENBAUERand BISCHOFF (1987) (R&B (1987), open
triangles); SOURIRAJANand KENNEDY (1962) (S&K (1962), filled
circles); and URUSOVA(1974) (U (1974), filled squares).
where SV is the critical specific volume in cm3/g and 9 is
related to the salinity as:
~=ln(~%NaCl+ 1). (3)
Critical specific volumes calculated with Eqn. (2) reproduce
those obtained from the equation of BODNAR (1985) within
kO.020 cm3/g.
Synthetic kid inclusions of the critical specific volume
display a decrease in the vapor to liquid volume ratios with
increasing salinity at room temperature (Fig. 7), as predicted
by the observed decrease in critical specific volume with in-
(2)

SPECIFIC VOLUMES
Table 1: Measured critical temperatures (Tc), formation

temperatures (TO and pressures (Pfk specific volumes

(SW, and critrcal pressures (PC) of N&-H20 synthetic

fluid inclusions which homogenize by critical behavior.

-.-

Sahnity Tc Tf
(WI.% ) (C) (0
_

0.0 374 ROO 1350 3.11 220

3.2 405 621 108.5 2.26 298
3.2 404 701 139s 2.25 298
5.0 421 591 1000 2.08 337
5.0 421 670 1315 2.09 337
IO.0 467 599 1025 1.80 458
1O.O 4hb 675 137.5 1.80 4.58
15.0 513 621 1060 1.64 598
15.0 514 1200 1.64 598
20.0 566 $2 1205 1.53 755
20.0 565 701 1400 I .53 755
22.5 611 784 1740 ISi 840
25.0 845 2ooo 1.49 945
25.0 Ez 782 L60.5 1.49 94s FIG. 6. Plot of NaCI-Hz0 critical specific volume as a fun&on of
27.5 730 785 1520 1.46 1184 0, where P = In (wtW NaCl + 1), determined using the equation of
27.5 729 842 1885 1.47 1184
30.0 820 825 1605 1.45 I574
BODNAR(1985). Line represents critical specific volumes predicted
by Eqn. (2).
 NaCI-Hz0 critical properties

FQG.7. N&l-H20 synthetic fluid inclusions of critical specific volume at 20C: (A) Pure I&O; scale bar = 50 gm.
(B) 5.0 wt% NaCl; scale bar = 20 pm. (C) 10.0 wt% NaCI; male bar = 10 pm. (D) 20.0 wt% NaC1; scale bar = 15pm.
(E) 25.0 wt% N&l; scale bar = 20 pm.

creasing salinity shown on Fig. 6. A pure Hz0 fluid inclusion
with the critical density (Fig. 7A) contains -69 volume per-
cent vapor at room temperature, while an inclusion with a
salinity of 25 wt% NaCl and the critical density contains only
44 volume percent vapor at room temperature (Fig. 7E).
Thus, a pure Hz0 inclusion with a density only shghtly greater
than the critical density might contain 65 volume percent
vapor at room temperature and would homogenize to the
liquid phase when heated. Similarly, a 25 wt% NaCl
inclusion with a density only sligbtly less than the critical
density might contain 46 volume percent vapor at room
temperature and would homogenize to the vapor phase when
heated. Determining ~~o~aphically whether a fluid inclu-
sion is vapor-rich or liquid-rich is not easy, even under
the best of conditions, and is particularly difficult if the liquid
and vapor phases are present in approximately equal
amounts. However, as the discussion above indicates, even
if the liquid-to-vapor ratio can be determined petrographi-
tally, it is still not possible to predict the mode of homoge-
nization without knowledge of the inclusion composition.
Thus, descriptions of inclusions as being liquid-rich or
vapor-rich, which usually implies the mode of homoge-
nization, must be used cautiously if these petrographic de-
scriptions have not been confirmed by micro~e~om~c
analysis.
The positions of the critical isochores above 1000 bars and
below 1000C were determined using the equation of BOD-
NAR (1985). In all cases, these calculated critical isochores
are coincident with the P-Tformation conditions ofcritically
homogenizing synthetic fluid inclusions. Furthermore, syn-
thetic fluid inclusions that homogenize by non-critical be-
havior provide close brackets on all critical &chores. For
example, a 10 wt% NaCl fluid inclusion trapped a few los
of bars above its critical isochore homogenized to the liquid
phase at a temperature 4C below the critical temperature.
With increasing salinity, the slopes of NaCl-Hz0 critical is-
ochores (averaged over 2000 bars) increase rapidly as fluid
compressibility decreases with increasing NaCl content (Fig.
8). As the critical isochores are slightly concave upwards, the
slope of an isochore near the critical point will be less than
the calculated value shown on Fig. 8. At pressures and tem-
peratures far removed from the critical point, the slope will
be greater than that shown on Fig. 8.
Critical pressures in the NaCl-HZ0 system were determined
from the intersection of the critical isochore with the critical
1600 * I . I I - I -
A BISCHOFF & PITZER (1989)
1400 l ThisStudy

6.0 -

CRITICAL CURVE

CRITICAL lSOCH&E SLOPES 350 450 550 650 750 850

* - * . I. * TEMPERATURE (C)
0 5 10 15 20 25 30
SALINITY (wt% NaCI) BIG.9. Critical pressures and temperatures in the NaCI-Hz0 system
to 30 wt% NaCI. The line represents critical pressures as a function
FIG. 8. Slopes of NaCl-Hz0 critical isochores averaged over a 2000 of critical temperature calculated from Eqn. (4). Data of BISCHOFF
bar range above tbe critical pressure. and PITZER(1989) are shown (triangles) for comparison.
8 C. L. Knight and R. J. Bodnar

temperature in P-T space (see Fig. 3). Because the equation and ROSENBAUER and BISCHOFF(1987) and differ signifi-
of BODNAR (1985) is only valid for pressures above 1000 bars cantly from those of SOURIRAJAN and KENNEDY (1962) and
and because of the experimental difficulties nosed by the close URUSOVA (1974). Although critical specific volumes pre-
proximity of immiscibility fields to the critical isochores at sented in this study agree with the volumetric data of h&AI-
lower pressures (Figs. 2 and 3f, it is necessary to ~phi~lly BULLIN d al. (1979) as to the general shape of the critical
extrapolate the isochores below 1000 bars to their respective volume~omposition curve, there is disagreement among the
critical points. Consequently, the accuracy of the critical data sets as to the values of critical specific volumes.
pressures so obtained (Table 1) is estimated to be within +50
Acknow~edgemenfs-We would like to thank members of the senior
bars. Critical pressures were regressed with critical temper- authors thesis committee, Don Rimstidt and Bob Tracy. for support
atures calculated from Eqn. (1) to yield the following empir- and encoumgement during this study. We are gratefid to Jim Bischoff
ical relationship for compositions of 0 to 30 wt% NaCI: for providing a preprint of his paper on the critical properties of
NaCt-H20 solutions. We also thank Jim Bischoff, Phil Brown, and
P = 2094 - 20.56T + 0.06896T2 - 8.903 Roberto Pabalan for their thoughtful reviews of this manuscript. We
are indebted to Sharon Chiang for drafting the figures,and to S. M.
x 10+T3 + 4.214. IO-*p (4) Sterner for his assistance in the design and conduct of the lab exper-
iments. Partial funding for this study was provided by grants from
where P is the critical pressure in bars and T is the critical the Earth Sciences Section of the National Science Foundation (EAR-
temperature obtained from Eqn. (If. Critical pressures cal- 8607356 and EAR-8657778) to RJB.
culated with Eqn. (4) reproduce those obtained ~phi~~ly
from the intersection of the critical isochore with the critical Editorial handling: T. S. Bowers
temperature within rt2 1 bars; note, however, that the exper-
REFERENCES
imental uncertainty associated with pressures obtained
BISCHOFFJ. L. and ROSENBAUER R. J. (1984)The critical point and
graphically is iSO bars. Critical pressures and tern~mtu~s
two ohase boundarv of sea water, ZOO-500C. E&I P/anef. Sci.
determined in this study (Fig. 9) agree very well with the data Ldt. 68, 172-180._
of BIsCHoFF and PITZER(1989). A summary of critical pres- BISCHOFFJ. L. and PITZER K. S, (1989)Liquid-vapor relations for
sures, temperatures, and specific volumes for NaCl-H20 fluids the svstem NaCI-H& Summarv of the P-T-x surface from 300
calculated from Eqns. (l), (2), and (4) is iisted in Table 2. to S&C. Amer. J.Sci. (in press).
BISCHOFFJ. L., ROSENBAUERR. J. and P~TZERK. S. (1986) The
system NaCl-H20: Relations of vapor-liquid near the critical tem-
SUMMARY perature of water and of vapor-liquid-halite from 300 to 500C.
Critical pressures, temperatures and volumetric properties Geochim. Cosmochim. Acta 50, 1437- 1444.
BODNAR R. J. (1985) P~ssure-volume-tem~mtu~m~sition
of NaCLH20 solutions have been determined for composi- (PVTX) properties of the system HzO-NaCI at elevated tempera-
tions of 0 to 30 wt% NaCl using the synthetic fluid inclusion tures and pressures. Ph.D. dissertation, Pennsylvania State Uni-
technique. Critical pressures and temperatures of this study versity.
agree with published data for compositions of less than ap BO~NARR. J. and STERNERS. M. (1985) Synthetic Buid inclusions
in natural quartz. II. Application to PVT studies. Geochim. Cos-
proximately 10 wt% NaCI. At higher sahnities, there is a
moc~im. Acta 49, 1855-1859.
marked scattering of critical P-X and T-X data. Our results BODNARR. J. and STERNERS. M. (1987) Synthetic fluid inclusions.
agree most closely with those of BISCHOFFand PITZER (1989) In hydrothermal Experimental Techniques (eds. G. C. ULMER
and H. L. BARNES),Chap. 17, pp. 423-457. Wiley Interscience.
BODNARR. J., BURNHAMC. W. and STERNERS. M. (1985) Synthetic
fluid inclusions in natural quartz. III. ~te~ination of phase
equiIib~um properties in the system H,O-NaCl to 1000C and
1500 bars. Geochim. Casmochim. Acza 49, 186 1- 1873.
KHAI~ULLINI. IQ-t. and BORJSOVN. M, (1965) Diagrams of phase
P
~uilib~um of the sodium chloride-water and the potassium chlo-
(bars)
ride-water systems. I>&. Acad. Nuuk SSSR 165, 1135-l 137.
-- ~AIBULLIN 1. KH., NOVIKOVB. YE., COPEL~OVICIJ A. M. and BE-
0.0 374 217 3.11 SEDIN A. M. (I 979) Phase diagrams for steam solutions and caIoric
10 383 240 2.69 properties of two- and three-component systems: H20-NaCI, H@-
2.0 392 263 245
3.0 402 290 2.29 Na2S04 and H@-NaCI-Na#O,. In Water and Steam (eds. J.
4.0 411 314 2.17 STRA~~B and K. SCHEFFLER),pp. 641-647. Pergamon Press.
5.0 420 339 2.08
6.0 430 366 2.00 MARSHALLW. L. and JONESE. V. (1974) Liquid-vapor critical tem-
7.0 439 391 1.93 peratures of aqueous electrolyte solutions. f. Inorg. Ntcci. Chem.
80 448 416 I.88
90 457 441 1.83 36,23 13-23 18.
10.0 466 466 1.79 SLANDERA. and LIANDERH. (1950) The phase diagram of sodium
110 475 491 175
12.0 484 516 1.72 chloride and steam above the critical point. Acta C&m. S&and. 4,
13.0 493 540 1.69 1437-1445.
14.0 502 564 1.66
15.0 512 1.64 ROEDDERE. (1984)Fluid Inclusions, Minerai. Sot. Amer., Reviews
16.0 522 162 in MineraIogy 12,644~.
17.0 532 1.60
180 545 1.58 ROSENBAUER R. J. and BISCHOFFJ. L. (1987) Pressure-composition
19.0 5.56 1.56 relations for coexisting gases and liquids and the critical points in
20.0 569 1.55
21.0 584 1.53 the system NaCI-HZ0 at 450, 475, and 500C. Geochim. Cos-
22.0 1.52 mochim. Acta 51,2349-2X4.
23.0 E ii9 1.51
24.0 639 910 1.50 SOURIRAJANS. and KENNEDY G. C. (1962) The system H20-NaQ
25.0 661 966 1.49 at elevated temperatures and pressures. Amer. J. Sci. 260, I15-
26.0 686 1033 148 141.
27.0 715 1118 1.47
28.0 746 1223 1.46 URUS~VA M. A. (1974)Phase equilibria in the sodium hydroxide-
29.0 782 1370 1.45 water and sodium chloride-water systems at 350-550C. Russian
30.0 x21 1574 1.44
J. Inorg. Chem. 19,450-454.