Canadian Minerologist

Vol. 29, pp.767-790(1991)

H2O-CO2MIXTURES:A REVIEWOF P-V-T-X DATA

AND AN ASSESSMENTFROMA PHASE-EOUILIBRIUM POINTOF VIEW

URSK. MADER'
Department of Geological Sciences,The University of British Columbia, Voncouver, British Columbia V6T 284

ABSTRAcT H2O-CO2. Les donndes de Greenwood et Gehrig

concordentgrossomodo, mais ne ddpassentpas 600bars,
les i pressions
A resolution is suggested among inconsistencies et ne contraignent aucunement activit6s
plus 6lev€es.La correction pour l'association chimique
between and within data sets, including P-V-T-X
(1974) et adoptde par
measurements, phase-equilibriumexperimentsand equa- propos€e par de Santis et al.
(1977) er par Bowers et Helgeson (1983) ne
tions of stalefor H2O-CO2mixtures.The P-V-T-X data Holloway
justifi6e. Une r6solution des incompatibilitds
of Franck & Tcidheide(1959)are inconsistentwith data semblepas
phases
obtained by Greenwood(1973)and Gehrig (1980), and parmi les rdsultats des dtudes des 6quilibres de
cannot be reconciledwith measuredphase-equilibriain ndcessiterade nouvellesexp6rienceset des ajustements
H2O-CO2 fluid mixtures. The data of Greenwoodand aux propridtdsthermophysiquesdes mindraux, en m€me
phasefluide.
Gehrig are in loose agreement,but extend only to 600 tempsqu'aux propri€tdsde mdlangedansla
bars and do not constrain activities at higher pressures. Un protocole est 6tabli pour appliquer les contraintesdes
The correction for chemicalassociationproposedby de 6quilibres de phasesafin d'dtablir des limites sur les
Santisel ol. (1974)and adoptedby Holloway (1977)and fugacit6s des composantesdu m6lange dans la phase
Bowers& Helgeson(1983)doesnot appearto bejustified. fluide. La banquede donn€esn'est pas encoread6quate
Resolution of the inconsistenciesamong phase-equi- pour d6river une 6quationd'6tat fiable pour les mdlanges
librium studies will require further experiments and H2O-CO2.Les travaux futurs devrontinclure desmesures
adjustments of thermophysical propenies of minerals despropri6tdsP-V-T-X jusqu'ir au moins l0 kbar, et de
simultaneouslywith firs of the mixing propefties of the nouvelles 6tudes des dquilibres de phases afin de
fluid phase. A procedure is developedfor the use of contraindre davantage les 6carts a I'idealitd dans le
experimentalphase-equilibriumconstraintsto put limits mdlange et de resoudre les incompatibilit€s parmi les
on the fugacitiesof componentsin the fluid mixture. It donndesexistantes.
is concluded that the data-base available is not yet
adequate to derive a reliable equation of state for (Traduit par la Rddaction)
H2O-CO2mixtures.Future work must include P-V-T-X
measurements to at least l0 kbar and phase-equilibrium Mots-clds:m6langesd'eau et d'oxyde carbonique,fluides,
studiesto further constraindeviationsfrom ideal mixing propri6t6s thermophysiques,propri6t6s thermodyna-
and to resolve inconsistenciesamong existing measure- miques, 6quationsd'6tat, dquilibresde phases.
ments.
INTRODUCTION
Keywords: water - carbon dioxide mixtures, fluids,
thermophysicalproperties,thermodynamicproperties,
equationsof state, phaseequilibria. C-O-H fluids are important in the study of
metamorphism, fluid inclusions, properties of
SoMMAIRE magmas, and evolution of oil and gas. Much of
our present knowlege of H2O-CO2 mixtures at
Cet arricle porte sur une r6conciliation parmi les elevated pressures and temperatures was established
incompatibilit6sinternesaux banquesde donn€eset entre during the late 1960s and early 1970s, and was
celles-ci, portant sur les mesuresP-V-T-X, les exp6- stimulated by the study of progressive metamor-
riencessur les 6quilibresde phases,et les dquationsd'6tat phism of impure limestones.
pour les m€langes H2O-CO2. Les donn€es de type Theoretical and experimental contributions com-
P-V-T-X publi6es par Franck & T6dheide (1959) ne bined with constraints from field observations were
concordentpas avecles donndesde Greenwood(1973)et provided by Greenwood (1967a, b, 1969, 1973),
de Gehrig(1980),et sontirreconciliablesavecles€quilibres
Skippen (1971), Johannes (1969), Eugster &
de phasesmesur€simpliquant une phase fluide mixte
Skippen (1967), Trommsdorff (1972), Tromms-
dorff & Evans (1974), Metz (1967, 1970), among
"Present address: Geological Survey of Canada, 601
many more. About a decade earlier, P-V-T-X
Booth Street,Ottawa, Ontario KIA 0E8.
measurements on H2O-CO, mixtures were ex-
767
768 THE CANADIAN MINERALOGIST
tended to 2 kbar pressure (Franck & Tddheide
1959),and the t\ryo-phase regionwasmappedto 3.5
kbar (Tddheide & Franck 1963, Takenouchi &
Kennedy 1964). Spectroscopicddta and measure-
ments of dielectric permittivity were collected in
Karlsruheby Kruse (1975)and Holzapfel & Franck
(1966). Equations of state for fluid mixtures
suitablefor the computation of phaseequilibria in
geological systemswere developedby Holloway
(1917), Flowers (1979) and by Kerrick & Jacobs
(1981). Continued efforts have steadily increased
the experimentaldata-base(e.g., Sterner& Bodnar
1991, Chernosky & Berman 1991) and supple-
mented field occurrencesof low-variancemineral
assemblages coupled with measuredcompositions
of minerals (e.9., Bucher-Nurminen 1988). With
the availability of fast microcomputers and im-
proved thermodynamic data-bases(e.g., Berman
1988), efforts have been made most recently to
compute petrogenetic grids for metacarbonate
rocks (Carmichael1991,Connolly& Trommsdorff
l99l).
In light of these continued efforts, it is
appropriate to critically examinethe very founda-
tions of thermophysical properties of HrO-CO,
mixtures, namely P-V-T-X measurements,equa-
tions of state and experimentally determined
phase-equilibria.The purpose of this paper is to
help focus on the most important measurements
needed to improve and resolve the numerous
inconsistencies.
THE SYSTEM
CO2-H2O
The systemCO2-H2Ohas three components,C,
H, O, and containsnumerousspecies:CO2,H2O,
CO, 02, H2, CHa, H2CO3,complexhydrocarbons,
and the condensedphasesgraphite, diamond and
clathrate hydrates. Despite the existence of
numerous species, it is possible to take a
stoichiometricapproach for the binary join H2O-
CO2, which considersonly two species,CO2 and
H2O. The experimentaldata, however, on which
the equation is calibrated, must be known to
containonly thosetwo species.The bulk composi-
tion of the fluid may be displacedfrom the binary
join if the fugacity of one or more speciesis
buffered, or sourcesor sinks for C-H-O species
exist. This is particularly significant in the case
wheregraphite or diamond is stable(e.g., Skippen
& Marshall1991,Ulmer & Luth l99l). Gain or loss
of hydrogen is the most common problem en-
counteredin experimentalstudies.It may be solved
by buffering the fugacity of hydrogenat a very low
partial pressure,removing likely sourcesor sinks
for hydrogen, and keeping experimental run
durations as short as possible. Experimentally
measured volumes of COr-H2O mixtures may
suffer from oxygenlossdue to the oxidation of the
steelpressurevesselor from hydrogen loss due to
diffusion or formation of metal hydrides. Under
sufficiently oxidizing conditions, methane,
hydrogenand carbon monoxideare presentonly in
trivial amounts, and a binary CO2-H2O fluid
consistschiefly of the speciesCO2 and H2O (e.g.,
Holloway 1987,Eugster& Skippen1967).
The two-phaseregion of the COr-H2O binary
systemis encounteredgeologicallyunder conditions
up to lower-greenschist-grade metamorphism.The
critical curve that bounds the two-phase region
extends from the critical point of pure H2O
(374,15"C,221.3bar) to a temperatureminimum
(266-269'C, 2000-2450 bar, 0.37 < X(CO2)
<0.43), and then probably to higher temperatures
with increasing pressure and increasing X(COz)
(T6dheide& Franck 1963,Takenouchi& Kennedy
1964,Sterner& Bodnar 1991).The lower branch
of the critical curve extendsfrom the critical point
of pureCO2(31.05"C,73.86bar) to a lowercritical
end-point at somewhat higher temperature and
pressure. Equations of state designed for the
computation of phase equilibria at temperatures
below the critical point of water must therefore
accountfor the two-phaseregion.
CoxsrnarNrs oN EeUATIoNSoF SrATEFRoM
THsonv ANDExPERIMENT
It is fair to state that the problem of the
predictionof P-V-T propertiesof fluids and their
mixtures is not so much due to the lack of theories
and models,but to the lack of our ability to assess
their relative merits. Models based on first
principlesare not yet sufficiently developedto test
equations of state, and the body of experimental
data is not large enoughto distinguishbetweenthe
extrapolationpropertiesof the numeroussemi-em-
pirical equations.As a consequence, the computa-
tion of properties of fluid mixtures relies heavily
on experimentally measuredquantities, semi-em-
pirical equations of state, and, in many cases,
arbitrarily chosenrules for the mixing of end-mem-
ber fluids.
The exact shapeof the intermolecularpotential
as a function of temperatureand pressureis not
known, nor are the potentials resulting from their
mutual interaction in mixtures. For this reason.
most equationsof state applicableto real systems
are basedon macroscopicmodels,with parameters
related to the dominant intermolecular forces of
attraction and repulsion. Examplesare the virial-
type equations,the van der Waals equationand the
Redlich-Kwong (Redlich & Kwong 1949)equation
with its numerousmodifications.
 WATER - CARBON DIOXIDE MIXTURES
The behavior of mixtures of gasesmay in some
cases be described by equations in which the
parametersare formed by somecombinationof the
parameters for the pure gases. However, the
equationsmust be mathematicallyand physically
compatible. These "mixing rules" may be inde-
pendentof the nature of the end-membergasesin
that they simply account for geometrical effects
upon mixing. If one or more of the end-member
gases deviate substantially from ideal behavior,
mixing rules may be adjusted for nongeometrical
effectsupon mixing, suchas induceddipole effects,
polarizability, strong electronic interactions and
chemicalassociation(e.9., Prausnitz et al. 1986),
In most cases, only a two-body interaction
parameteris developedto accountfor theseeffects.
The requirementthat equationsof the end-member
gasesbe compatibleputs severeconstraintson the
possibility of introducing modifications to either
end member to fit experimental data. Several
equationsintendedfor geologicalapplicationshave
beenfit piecewiseto data in order to keepequations
simple [e.g., Bottinga & Richet (1981)for COr;
Holloway (1977, l98l) for H2O; Saxena & Fei
(1987)for H2O and COr; Powell& Holland (1985)
and Holland & Powell (1990)for the logarithm of
the fugacity of H2O and CO2l. The tradeoff in this
approach is the introduction of discontinuitiesto
the thermodynamic functions derived from these
equationsof state.
An important point that is easilyunderestimated
is the dependencyof the parametersin the equation
of stateon the mathematicalform of the equation
itself. The same rules of mixing applied to a van
der Waalsequationand a Redlich-Kwongequation
will result in different excessproperties for a
mixture, eventhough the physicaljustification and
the underlying assumptions may be identical.
Increasedflexibility to fit measuredvolumes may
be introducedby making the attractive term or the
repulsive term more flexible. Thus, an equation
with a simplehard-sphererepulsiveterm can mimic
increased compressibility at high pressure by
introducing a volume (or pressure)dependencyon
the attractiveterm (e.g., the equation of Kerrick &
Jacobs).The quality of fit to observeddata alone
implies nothing about the physicalmeaningof the
variation of the parameterswith P, V and T, or
about the correctnessof the mixing rules.
The number of parametersin an equation of
state is not alwayscorrelatedwith the goodnessof
fit to data. In most equations, one or more
parameters,suchas the excludedvolume, are fixed
prior to regressionto measured volumes (e.9.,
Kerrick & Jacobs1981,Holloway 1977).For some
of the mathematicallymore complex equations,a
simultaneousfit of all Darametersis not oossible
769
owing to problemswith numerical stability during
optimization (e.9., Bottinga & Richet l98l). An
equation with few parametersfit simultaneously,
such as the five-parameterequation presentedby
Miider & Berman (1991) for COr, may achievea
fit comparableto a ten-parameterequation, such
as that proposedby Kerrick & Jacobs(1981).A
many-parameter equation may not extrapolate
well, particularly if the parametersare combined
empirically, for examplein a power-seriesexpan-
sion.
Carbon dioxide
Raman spectroscopicmeasurementsto 490'C
and 2.5 kbar (Kruse 1975)indicate no significant
changesin the spectrumfrom dataat low densities.
Not much is known about the extent of dissocia-
tion, ionization, or dimerization of pure COt at
high temperaturesand very high densities.
Water
Whereasthe peculiar nature and properties of
water compared to other liquids are well known
(e.g.,Franks 1972-1984, vols. I-VII), it is not well
understood how these properties change with
increasing pressure and temperature. Insight is
gainedfrom experimentalmeasurements of P-V-T
properties, dielectric permittivity, Raman and
infrared spectroscopy,thermodynamicproperties,
and, more recently, from simulations using
molecular dynamics(seealso Tddheide 1972).
Water at low pressuresand temperatures is
dominatedby hydrogenbonding, which leadsto a
highly structuredliquid dominatedby tetrahedrally
coordinated molecules with an open structure
similar to that in the correspondingsolid, ice-I. The
hydrogen bond persists to high pressuresin ice
(e.9., ice-VII at pressures>21 kbar), with an
increase in density due to distortion of the
framework. The relatively low compressibilityof
liquid water despitethe open framework indicates
that the structuredominatedby the hydrogenbond
may persist to high pressurein the fluid state as
well. There is evidencethat water starts to assume
compressibilitieslike those of unstructuredliquids
at a pressurebetween4 and 8 kbar (Franck 1981).
The tetrahedrallycoordinatednetwork probably
does not persist to high temperatures at low
pressures. Spectroscopic data indicate that at
supercriticalconditions,H2O has lost many of its
structured characteristics.Supercritical water is,
however, still polar in nature, which is important
for its ability to interactwith other species.No data
are availableon structural changesas a function of
temperature at high pressures. At very high
770 THE CANADIAN MINERALOGIST
temperature and pressure (100-200 kbar), water
may be largely an ionic fluid, in view of the
observedmonotonic increaseof the ion product
with pressureand temperature(Holzapfel & Franck
1966, Mitchell & Nellis 1979, and discussionin
Franckl98l).
Recent progress in simulations based on
moleculardynamics(Brodholt & Wood, 1990)at a
densityof I g,/cm3and temperaturesup to 2100"C
(38 kbar) leads 1o reasonable agreement with
measuredvolumes and transport properties. This
approach may allow testing of intermolecular
potential formulations and equationsof statein the
near future. Resultsof numericalsimulationsalone
are not yet accurate enough for the purpose of
thermodynamiccomputations.
The Haar et al. (1984)equation used to express
the thermodynamic properties of supercritical
waterby Berman(1988)and in this studyis thought
to be reliableto at least2500K and 30 kbar. The
equation is based on a formulation of the
Helmholtz free energyas a function of temperature
and density.The theoreticalmodel and its empirical
extensions obey the first and second laws of
thermodynamicsand thus allow for computation
of any thermodynamicfunction by differentiation.
The equation is consistent with virtually all
experimental observations. Most recently, the
propertiesof H2O in the critical region have been
addressed by Johnson& Norton (1991).
Mixtures of water and cqrbon dioxide
As a first approximation, inferences from
P-V-T-X measurementsabout interactions be-
tween CO2 and H2O may be tested against what
limited spectroscopicand other data exist. From
the strong depressionof the critical composition
curve to lower temperaturescompared to water
mixed with an inert gas (e.9., argon, Greenwood
196l), onemight expectstrong chemicalassociation
up to at least 400oC and 4 kbar. The positive
deviation of the volume from ideality on mixing,
stemmingfrom dispersionforces, may be reduced
or even reversedby slrong chemical association.
Greenwood's(1969)P-V-T-X measurements indi-
cate distinct negative volumes of mixing at
temperaturesabove 600'C and pressuresbelow
300-400bat (e.g., seebelow, in Fig. 7). This would
indicate that chemical association remains sig-
nificant beyond 800oC,but decreases with increas-
ing pressure.Franck & T0dheide(1959)interpreted
their P-V-T-X measurementsin terms of devia-
tions from a van der Waals equation of state with
"geometric" rules of mixing and estimated the
maximum amount of chemicalassociationin terms
of carbonic acid. De Santiset al. (1974)usedthese
data to formulate a temperature-dependent equi-
librium constant (CO2 + H2O + H2CO, that is
incorporated into their modified Redlich-Kwong
equationof stateand adoptedby Holloway (1977),
Flowers& Helgeson(1983)and Bowers& Helgeson
(1983).The P-V-T-X data by Franck& T6dheide
are consideredsuspectfor reasonsexplainedbelow,
and the de Santis et al. (1974) correction is not
justified.
Infrared absorptionand Ramanspectroscopyon
fluids at elevatedtemperatureand pressurearerare,
owing to obvioustechnicaldifficulties arising from
the use of sapphire windows. The data available
up to 2-3 kbar (Kruse 1975, and summary by
Franck l98l) only show a weak band on a Raman
spectrum at low temperatures, which may be
assigned to carbonic acid. Spectra at higher
temperaturesand pressureslack clear evidencefor
chemicalassociation.Read's(1975)measurements
on electrical conductance suggestat least some
chemical association up to the limits of his
experimentsat 250"C and 2 kbar.
ExrsrrNc EeuerroNs oF SrATE
In many early applications to geological
problems, water and carbon dioxide have been
assumedto mix ideally (e.g., Eugster & Skippen
1967, Greenwood 1967b)owing to the lack of
constraints on nonideality, This may result in
distorted topologiesin phasediagramsover a wide
rangeof temperature,pressureand fluid composi-
tion. The mosl commonly used equationsof state
that predict P-V-T-X properties of H2O-CO2
mixturesinclude that of Kerrick & Jacobs(1981)
and the Holloway(1977)- Flowers(1979)equation,
which are both modifications of the equation of
Redlich& Kwong (1949).Holloway's equationsare
basedon work by de Santis et al. (1974). Powell
& Holland (1985)and Holland & Powell (1990)
fitted a polynomial function for the logarithm of
the fugacity to data computed with existing
equations of state. The mixture is modeled by a
subregular, asymmetrical solution-model for the
activities,which are fitted to valuescomputedwith
the Kerrick & Jacobsequation. Shmulovich el a/.
(1980) presented a virial equation and used a
Margules formulation to model the excessvolume
of mixing as a function of composition,from which
they derivedthe fugacities.Spycher& Reed(1988)
devised a pressure-explicit virial equation ap-
plicable to calculations of hydrothermal boiling,
with upper limits at I kbar and 1000"C. Connolly
& Bodnar (1983) presenteda modified Redlich-
Kwong equation for the range 0-10 kbar and
100-1000oC, designedfor applicationsto fluid-in-
clusionstudies.Sterner& Bodnar(1991)deriveda
 WATER - CARBON DIOXIDE MIXTURES 771

three-coefficientMargulesexpansionfor the excess Wood & Fraser 1977,Anderson 1977,Skippen&

volume of mixing from their measurementson Carmichael 1977), they do not provide the
syntheticfluid-inclusionsbetween2 artd6 kbar and necessarydetails relevant to this treatment of the
400 to 700"C. Tabulationsof P-V-T-X properties phase-equilibrium experiments. The thermody-
and fugacitiesof CO2-H2Omixtures were offered namic notation usedhereis summarizedin Table 1.
by Franck& Tddheide(1959),Greenwood& Barnes In order to derive simple expressionsfor the
(1966), Greenwood (1969, 1913), Ryzhenko & excessproperties of a mixture (e.9., partial molar
Volkov (1971),Wood & Fraser(1977),Shmulovich excessvolume V"), the fugacity coefficient yi of a
et al, (1980),and Sterner& Bodnar (1991).Recent componentin a mixture is best related to its pure
review articles on equations of state for fluids stateat temperatureand pressureof interest,which
include those by Ferry & Baumgartner(1987)and yields:
Holloway (1987). 2P
1P
u"(P,ndP=lx, =
v.,(T)itP
I
Jrr* 7 JIl b s (1)
THsnrraonvNaMlc
RELATIoNSHIPS
FOR FLUID MIXTUNES Dw]-'tt(P,T,xr)'
i

Whereasmost standard texts cover the subject The activity of a component with respectto the
adequately(Prausnitzet q|.1986, Chatterjee1991, same state becomesai = XiI. Equation I also

EQUATIONS
TABLE1. NOTATIONFORTHERMODYNAMIC

P pressure
T absolutetemperaturein Kelvin
AnG Gibbspotentialof a reaction
g Gibbspotentialof a reactiondiminishedby the "R?ln/
terms of the fluid species
Cp heat capacityat constantpressure
a isobaricexpansivity
I isothermal compressibility
Uo molar volumeof pure componentd
U partial molar volumeof componenti in a mixture
V^ molar volume of a mixture
i' molar volume of a mechanical(ideal)fluid mixture
U molar excessvolume of a mixture
V", partial molar excessvolumeof componenti in a mixture
X; mole fraction of componenti in a mixture
f; fugacity of componenti in a mixture
f: fugacity of pure componenti
''li fugacity coefficient of component i relativeto ideal
mixing at pressureand temperatureof interest
ai activity of componentI in a mixture relativeto its pure
state at pressureand temperatureof interest
vi stoichiometric coefficient of component a in a reaction
R gas constant

Superscript* refersto a variableat somestandardstate

Superscriptid refersto a variablein a state of ideal mixing
SuperscriptexPrefersto an experimentallymeasuredvariable
'772
THE CANADIAN MINERALOCIST

*T T Paofi = Ptotol = cot[tta'nt

experimental
daturn

V""
ideal
T,N i
I
U.^
I
url Lv; I

F xr ---Fx"-.| Ezo Qoz

Xerp Xia
BA
Frc. 2. Schematic diagram of a single fluid species
Frc. 1. Ceometricalinterpretationof the partial molar equilibrium. The experimentally determined equi-
excessvolume in a binarv fluid mixture with librium curve and the computedcurve assumingideal
componentsA and B. mixing in the fluid phaseare shown as a thick line
and a thin line, respectively.

implies the approximate equality of unit pressure The volume integral of the partial molar excess
and unit fugacity. A simple geometric interpreta- volume with respect to pressure for this case is
tion of the partial molar excessvolume in a obtained from equation l:
two-componentmixture is provided in Figure l. 1P rld
In order to relate an experimentallydetermined x?* I UJT).]P =.ffilnftp =
Jr bsr ^a
phase-equilibriumposition at F"p, Zexp,)(expto a (5)
hypothetical reference-position assuming ideal ETltl;(P,7,XqP).
mixing at Pd, Td and Xd, one formulates first the
P-V_T_X PROPERTIES CONSTRAINED BY
Gibbspotentialof the reactionfor both states:
PHess-Eeurr-TBRIUM DATA
AnG= 0 = g(P.-P,f'r)lvt,W,Sl, El, (Cplt,or, 9rl From the requirement for a reaction at equi-
(2\ librium that ApGez be equal to 0, it follows that
*T**rd]ff each experimental half-bracket leads to an in-
equality,ARGP,Td 0 or ARGer > 0, depending
whether products or reactantsare stable, respec-
and an analogousequation with f andf at states tively. Provided reliable thermodynamic data for
Pd, ?tdand Xd. SubscriptTdenotesalt species(solid all solid phases are available, each measured
or fluid) that take part in the reaction, k relatesto half-bracket of an equilibrium involving a fluid
solid phasesonly, and I is the subscript for all mixture will put an inequality constraint on the
gaseous species. The function I contains all fugacities of the fluid speciesby combining the
contributions to the Gibbs potential from the solid above inequalitieswith equation 3:
phasesand the contributions from the fluid species xf )
with the exceptionof the volume integral (RT ln f nT ,,'\-Gil u xid- ?*4 h t(f:!-
--? )
.f1o(Po'n,2ur; ,l
term). Equation 2 and its analog are combinedto (6)
obtain the generalexpression: i e1r*,r-; - g1l",Cu;,
ggq,r'p)_g(Pta,t'd)=
where the "less than" refers to the case where
rl ",(*.rrl. _n*r" r3t products are stable. The combined bounds from
ffi). many experimental half-brackets will confine an
equation of statewithin feasiblelimits with respect
Figure 2 is an exampleof the specialcasewhere
measuredphase-equilibria.This fact may be used
only one fluid componentin the mixture takespart to
in a reaction. The deviation from ideality in an to test existing equations of state or to constrain
adjustable parameters of a new equation using
isobaric-isothermalsectionsimplifies to:
techniquesof numerical optimization. Details of
4iA,#=ar(P,r,xiP)=xld= this method are outlined by Berman et ol. (1986),
(4) and applied to the derivation of an equation of
?r(P, Xf'D)XtrP. statefor pure CO2by Miider & Berman(1991).
",
 WATER - CARBON DIOXIDE,MIXTURES 773

The validity of this approach hinges on the uncertainties compared to the small effect on
availability of accuratethermophysicalproperties volume of mixing at high pressures. These
of minerals and pure fluids, as well as P-V-T-X uncertainties are the resultof not reportingP-V-T
measurementsand phase-equilibriumexperiments. data on the pure fluids. For the computation of
Improvements on equations of state can only the excessvolume below 1.4 kbar, the data on the
proceedin conjunction with improvementsto the pure gases of Kennedy (1954) and Holser &
experimentaldata-base.Carefully documentedas- kennedy (1958, 1959) were used; Franck &
semblages of natural mineralscanprovide addition- Tddheide stated that theseagreeto within l9o of
al constraints and are the ultimate test in their measurements. The sameprocedurehad to be
applicationsof computedphase-equilibriato rocks. adopted for the data of Gehrig (1980), who
Thermophysicalproperties of minerals that are reported data on mixtures between0'l <X(CO2)
dependent on fluid properties by virtue of the <b.9, but none for the pure fluids. Error bars in
available phase-equilibrium data must be fitted Figures 3-7 representmy best estimate of uncer-
simultaneouslywith fluid properties in order to tainty, except for measurementsby Sterner &
maintain self-consistency and to avoid the propaga- Bodnar (lgtl), where experimentalprecision is
tion of systematic errors into fluid properties. depicted.
Whereasthere is somecircularity in this process,it The most striking feature apparentfrom inspec-
is anticipated that every new experimentaldatum tion of Figures3-7 is the substantialinconsistency
of high quality will guide the numerical best fit amongthe data setsof Franck& Tddheide(1959)'
toward consistencywith all availabledata. Greenwood(1973),Gehrig (1980)and Shmulovich
et ql. (1979,1980).Thereis reasonable agreement'
P-V-T-X Dere oN HP-CO2 MIxTURES although not within stated experimental uncertain-
ties, betweenthe data of Greenwood(1973)and
Gehrig (1980)(Figs. 4, 5). The Kerrick & Jacobs
Figures3 to 7 comparemeasuredexcessvolumes (1981)
equation of state, which reproducesex-
of mixing with volumes computed by several perimentally measuredphase-equilibriaquite well
equations of state. Parametersfor equations of (Berman 1988, Jacobs & Kerrick l98lb' and
state and computer codesfor their evalution were
discussionbelow), loosely approximatesthe data
obtained from the following sources: Kerrick &
by Greenwoodand Gehrig between400 and 600'C
Jacobs(1981),Jacobs& Kerrick (1981a),Holloway (Figs. 3-6). I concludethat the volumes measured
(1981) and a computer code obtained by written
by Franck & Tddheide are most likely in error'
communicationfrom J.R. Holloway (July, 1990). pirticularly at pressuresbelow I kbar, and should
The van der Waals equation was evaluatedusing
not be used. Their volumes are systematically
the following parametersand mixing rules: a(H2O)
: 55.0 x 105,,(H20) : 30.3,a(CO) : 36.8 x smallerthan thosemeasuredby Greenwood,Gehrig
: = and Schmulovichet a/. It is not possibleto relate
105, b(co, 43,0, Qmix X(HzO)2a(HzO) +
apparentlyerroneousmeasurementsof Franck
X(co )2o(Co) + 2x(Wo)x(co )'/ o(Hzo)a{QoJ' the a tOaneiOe to a single cause. The most likely
and D*o = 6I(HzO)X(H2O)+ -b(CO)X(CO)' in
problems in the experimentalmethod that lead to
units iif Kelvin, bar, and cm3/mol. A positive volumes are thermal gradientsover
pressurespike at 2l0bar (Figs. 3A-E) in the curves underestimated or determination of the
volumes of connections,
computed with the Kerrick & Jacobs equation is volume of the pressure vessel by the mercury
the result of nonconvergenceof the iterative
method, or creepof Bridgman seals.
root-finding procedurecodedby Jacobs& Kerrick
(1981a). These erroneous volumes do not affect Shmulovichet al. (1979,1980) measuredvolumes
compuledfugacity coefficientsfor a pressureabove of several fluid compositions at 400 and 500"C
250 bar sincethe volume integration is performed between0.15 and 5.7 kbar (Figs. 3' 5). Measure-
algebraically, but volumes between 325 arrd cq. mentsby Shmulovichet al. (1979)at 400 and500'C
4l5oC cannot be computed reliably below a and 400-5700bar showexcessvolumessignificantly
pressureof 250 bars. larger than data by Shmulovich et ol. (1980) and
good
Measuredvolumesare representedby smoothed Franck & T6dheide, with the exception of
by
data provided by the individual authors where agreementin the region of overlap with data
primary measurementsare not reported or do not Greenwood and Gehrig at 500-600 bar (Fig' 5). At
plot into the selected figures (e.g., Franck & 400'C and 150-200 bar, the excessvolumes of
Tddheide 1959, Greenwood 1973, Gehrig 1980, Shmulovich et al. (1979) are smaller than those
Sterner & Bodnar l99l). Only a representative measured by Gehrig (Fig. 3). Excess volumes
amount of data is plotted to avoid renderinggraphs measuredby Shmulovich et al. (1979) above 700
illegible. The data of Franck & Tddheideabove 1.4 bar pressureat 700'C (Figs. 5,{, B) are difficult to
kbar are not included in the figures owing to large reconcilewith theory or phase-equilibriumdata.
tt4 TTIE CANADIAN MII..ItsRALOGI'ST..

Excess volume (cm3/mole)

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excessmolar volume
diagrams(E, F) of H2O-CO2mixrures at 400oC. Seetext for discussion.
 WATER. CARBON DIOXIDE MIXTURES
775

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FIG.4. Pressureyersusexcessmolar volume diagrams(A, B, C, D) and fluid composition
diagrams(E, F) of H2O-CO2 mixtures at 450'C. Seetext for discussion'
7'76 THE CANADIAN MINEIIALOCIST

Excess volume (cm3/mole)

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Ftc. 5. Pressurev?rsrsexcessmolar volume diagrams(A, B, C, D) and fluid compositionyelsal excessmolar volume
diagrams(E, F) of H2O-CO2 mixruresar 500oC.Seerexr for discussion.
 WATER - CARBON DIOXIDE MIXTURES 777

Excess volume (cm3/mole)

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Frc. 6. Pressureyersasexcessmolar volume diagrams(A, B, C, D) and fluid compositionversrsexcessmolat volume

diagrams(E, F) of H2O-CO2 mixtures at 600oC.Seelext for discussion.
778 THE CANADIAN MINERALOCIST

Excess volume (cm3/mole)

;&iN 6 6 A S O N A O € @os*o*606

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Ftc. 7. Pressureversrsexcessmolar volume diagrams(A, B, C, D) and fluid composition versr.rexcessmolar volume
diagrams(E, F) of H2O-CO2mixtures at 700 and 800"C. Seetext for discussion.
 WATER - CARBON DIOXIDE MIXTURES
Greenwood (1969, 1973) measured negative
volumes of mixing at temperaturesabove 600oC
and pressuresbelow 300-400bar (Fig. 7). If these
measurementsare correct, significant chemical
association must occur in order to reverse the
positive volume-effect resulting from dispersion
forces alone. The Holloway - Flowers equation,
which accountsfor formation of carbonic acid (de
Santise/ a/. 1974),doesnot representGreenwood's
(1973)data well in this region.
Sterner& Bodnar (1991)derivedexcessvolumes
of mixing from measurementson synthetic fluid
inclusionsin quartz (2-6 kbar, 400-700'C, 0.125
<X(CO, <0.875). Only data at 2kbar are shown
in Figures3 and 5-7. The authors computed ideal
volumes with the Haar et al, (1984) equation of
state for water and the equation of Shmonov &
Shmulovich (1974) for carbon dioxide. Excess
volumeswere inferred to be positive, smaller than
1.3 cm3lmol, with the exceptionof slightly negative
excessvolumes for water-rich compositionsat 600
and 700'C. Uncertainties are difficult to assess
becauseof the lack of sufficient measurementson
pure fluids determined by the same method.
Uncertainties of 2-30/o in the measurementsof
Shmonov & Shmulovich (1974) on pure CO2
(Miider & Berman l99l) will lead to uncertainties
in the excessvolumes of the mixtures that are of
the samemagnitudeas the excessvolumesthemsel-
ves. The important conclusion remains that
fugacity coefficients up to at least l0 kbar and
700oC are dominated by relative large deviations
from ideal mixing at pressuresbelow 2 kbar.
The Kerrick & Jacobs(1981)equationis most
compatiblewith the P-V-T-X data of Greenwood
(1973),Gehrig (1980)and Shmulovichet al. (1980),
and most phase-equilibriumdata between450 and
700oC(seebelow). The Holloway (1977, 1981)-
Flowers(1979)equationis constrainedto agreewith
data by Franck & Tddheide (1959), but underes-
timates deviationsfrom ideal mixing comparedto
most other da1a.
CoNsrnatNrs oN AcTIvITY -
COMPOSITION RELATIONSHIPS
As an alternative approach to P-V-T-X meas-
urements,one can determinedirectly activity-com-
position relationshipsby the useof fugacity sensors
and buffering techniques.Joyce& Holloway (1987,
1989)buffered the fugacity of HrO and analyzed
the fluid mixture to obtain equilibrium X(H2O) at
2 kbar fluid pressureand 550-850oCand observed
near-ideal activities for HrO. Chou & Williams
(1977, 1979a,b) used a hydrogen fugacity sensor
and reported negativedeviations from ideality at
X(CO) >0.4, 2-6 kbar and 600 and 700'C. A
779
re-evaluation of the technique revealed that the
data in the 1979 paper are incorrect and that
deviationsfrom ideal mixing are positive over the
entire rangeof composition(Chou & Cygan 1990).
Note that Sterner & Bodnar (1991) measured
negativeexcessvolumes on mixing for water-rich
compositionsat these pressuresand temperatures
(seeabove).
Walter(1963c),Shmulovich& Kotova(1980)and
Ziegenbein & Johannes (1982) constrained the
fugacity of CO2 in a H2O-CO2 mixture from
experimentally measured phase-equilibria. The
resultsare limited by the considerationof a single
equilibrium, which leadsto curvesof activity versas
fluid composition at constant pressurethat are
polythermal, i.e., the temperature is rising with
increasing X(CO). Eggler et ol. (1979) placed
constraintson the deviation from ideal mixing at
26 kbar using experimentsperformed in a piston-
cylinder apparatus.
PHASE.EQUILIBRIUM DATA
INvot-vtNc H2O-CO2MIxruREs
Whereasthe body of experimentaldata including
H2O-CO2mixtures is substantial,there are several
incompatibilitiesamongexperimentalstudiesof the
sameequilibrium (Table 2). One reasonfor this is
that such experimentsare technically difficult to
control. Thereareamplepossibilitiesfor errorsthat
remain undetected.This placesobvious difficulties
on selectionof experimentsthat place reasonable
constraintson the deviation from ideal mixing of
the fluid phase.
The following is a summary of problemswithin
the experimental data-base,as well as the ther-
modynamic data-basethat Berman (1988)derived
from these experiments(see also Berman 1988).
Numbered phase-equilibriaare keyedto Table 2.
Phase equilibria with the most disturbing
inconsistenciesbetween studies that examine the
same reaction include calcite + andalusite +
quartz + anorthite + CO2 (3), calcite + quartz
r: wollastonite + CO2 (l), wollastonite + calcite
+ anorthite + grossular + CO2 (5), and calcite
+ quartz + tremolite + diopside + H2O + CO2
(26). Equilibria that show only a discrepancy
between experiment and thermodynamic data of
Berman (1988) include dolomite + tremolite +
calcite + forsterite + CO2 + H2O Q1), quartz +
dolomite + Hp + calcite + talc + CO2 (29)'
magnesite+ talc + forsterite + H2O + CO2(31)'
magnesite+ quartz + H2O e talc + CO2 Q2)'
muscovite + quartz : sanidine + andalusite +
H2O (40), and rutile + quartz + calcite + titanite
+ CO2 (46). Experimentsby Manning & Bohlen
(1991) corroborate the thermodynamic data for
780 THE CANADIAN MINERALOGIST

T A B L E2 . E X P E R I M E N TS
ATL U D I EO
S F P H A S EE Q U I L I B RI N
A V O L V I NHGZ O - C OM
Z IXTURES

Systemor Equilibrium No Author P [ k b a r ]r f c l x(co2) 888 TD PH

Ca-Si-C-O * HzO
cal+Qtz:=wo*coz Zi&Jo,7A 2,4,6 580-850 0.2-0.8 8 G
Gr,67a L,2 500-720 0.0-0.9 8 ZJ
J a & K e , 8 1 b6 870 0.8-0.9 8 (i)-
pure CO2 Ha&Tu,56 0.3-3 570-800 - 11

Ca-AI-Si-C-O * HzO
Cal+Ky+Qtz:= An*COz 2 Ke&Gh,79 6 550-570 0.7 8
Ja&Ke,81b6 450-580 0.0-0.8 8 (i)+
Cal+And+Qtz:=An*COz 3 Ke&Gh,79 2 410-450 0.5 I i+ cB
Ja&Ke,81b2 370-450 0.1-0.7 8 i+ cB
Ch&Be,91 1,2 340-410 0.5-0.8 KG,JK
An+Cal+Qtz:=Grs*COz 4 Go&Gr,7l 2 530-570 0.1 8
Wo*Cal+An r= Grs*COz 5 Ho,74 L,4 710-840 0.1-0.5 9 i+
sh,78 1,2,4,6 610-730 0.0-0.3 9 i+ GG
Go&Gr,7l 2 580-850 0.0-0.4 9 s
A n * C a l + C r n : =G h + C O l 6 Ho,74 1 760-840 0.2-0.6 10
pureCO2 sh,74 0.5-0.7 780-860 11
An*Cal ;+ Grs*Gh*COz 7 Ho,74 I 719-880 0.1-0.7 10 (i)-
An*Cal ;= Grs*Crn*COz 8 Ho,74 I,4 750-840 0.1-0.2 10
Ke&Gh,79 2 680-710 0.1 10
Grs+Cal*Crn+ Gh+CO2 9 Ho,74 1,4 700-840 0.0-0.2 10
An*Cal := Wo*Gh*COe 10 Ho,74 1 760-900 0.4-0.9 10 (i)-
pureCO2 sh,74 0.5-0.7 830-890 11
Grs*Cal;+ Wo+Gh*COz 11 Ho,74 1 730-800 0.1-0.2 10

Ca-Al-Si-C-H-O
Zo*COz:= Cal*An*H:O L2 St&Ni,72 2,5 430-670 0.0-0.3 e (i)+
Al&Fa,82 5 480-650 0.1-0.3 9
Cal+Prl+H2O:=
Lws*Qtz*CO: 1 3 Ni,72 4,7 310-390 0.0

Ca-Mg-Si-C-O + H2O
Cal+Ak=: Mer*COz t4 2h,77 1 790-950 0.0-0.2 24
Fo*Di+Cal ;+ Mtc*COz 15 2h,77 I 680-850 0.0-0.3 24
pureCO2 Wa,63a 0.1-0.5 720-880 25
Fo*Cal+ Mtc*Per*COz 16 2h,77 I 730-930 0.0-0.2 24 (i)-
pureCO2 Wa,63b 0.1-0.7 750-900 25 i-
Di+Cal:= Ak*COz L7 2h,77 I 740-880 0.1-0.4 24
pureCO2 Wa,63a 0.1-0.7 720-930 25
Qtz+Dol=r Di+CO2 18 51,75 L,2 420-540 0.9 26
Ja&Ke,81b5 570-580 0.7 26
Eg&Ke,81 6 600-630 0.8 26
Dol+Qtz+Tlc+ Tr*COz 19 Eg&Ke,8l 6 480-560 0.1-0.2 26
Di+Dol =: Fo+Cal*COz 20 K a & M e , 8 0 1 , 3 , 5 , 1 0530-870 0.9 26
 WATER - CARBON DIOXIDE MIXTURES 781

T A B L E2 . C O N T I N U E D

Systemor Equilibrium No Author P [kbar] T f Cl X(CO2) 888 TD P

Ca-Mq-Si-C-H-O

Qtz+Tfc+Cal:= Tr+H:O+COz 2l 51,75 2 47A470 0.5 26

Cal+Tr = Dol+Di+HzO+CO: 22 51,75 5 640 0.5-0.8 26
Dol+Tlc = Fo+Di+HzO+CO: 23 Sk,71 1,2,2.6 500-590 0.7-0.8 26
Cal+Qtz+Tlcr= Di+HzO+COz 24 Sk,71 1,2,3 430-550 0.5-0.6 26
Dol+Qtz+HzO+ Cat*Tr*COz 25 51,75 2 460-500 0.8-0.9 27
Eg&Ke,8l 6 490-600 0.1-0.7 21
Cat+Qtz+Tr+ Di+HzO+COz 26 Me,70 1,5 430-660 0.0-0.6 27 i+ S
s1,75 1,5 460-650 0.F0.9 27 M
Dol+Tr;= Fo+Cal*HzO*COr 27 Me,67,76 0'5,1 430-550 0.0-0.8 27 i+
Cal*Tr + Fo+Di+HzO+COz 28 Ch&Be,86a 1 520-570 0.1-0.5 27
Dol+Qtz+HzO+ Cal+Tlc*COz 29 Me&Wi,63 2 440-510 0.3-0.9
Go&Gr,70 L,2 390-520 0.2-0.9 28 i+
Me&Pu,70,71 L,2,3,5 390-590 0.1-0.9 28 i(1)+
sk,71 1,2 410-460 0.5-0.6 28 i(1)+
Eg&Ke,8l 6 440-560 0.0-0.3 28

Me-Si-C-O * HzO
Mgs*En= Fo*CO: 30 Jo,69 2 560-580 0.9-1.0 35
E1,79 26 1000-11800.3-1.0

Ms-Si-C-H-O

Mgs+Tlc:+ Fo*HzO*COz 31 Gr,67b 7,2 480-580 0.1-0.8 34 i*+ J

Jo,69 0.5,1,2,4,7 470-670 0.1-0.7 34 i*A G
Mgs+Qtz*HzO:= Tlc*cOz 32 Jo,69 t,2,4,7 330-620 0.0-0.9 34 i-
Mts+Tlc+H2O r= Ctl+CO2 33 Jo,69 I,2,4 330-480 0.0-0.1 35 (i)-
Mgs+CtlF: Fo+HzO+CO2 34 Jo,69 1,2,4 440-480 0.0-0.1 35
Mgs*Ath = En+HzO*COu 35 Jo,69 2 530-560 0.9-1.0 35

Ms-Al-Si-C-H-O
Caf+Chl+ DilFo+Spl*HzO+COz 36 Ch&Be,86a L,2,4 550-690 0.1-0.7 33
Dol*chl + Fo+cal+5pl*Hzo*coz 37 wk,80 1,2,3 540-620 0.7-0.8 33 i+
Ch&Be.86a 1,2 540-630 0.1-0.7 33
Mgs*Chl + Fo+Spl*HzO*COz 38 Ch&8e,86b,89 1,2,3,4 530-670 0'2-0'7 34

Na-Al-Si-H-O * COr
Pg + Ab*Crn*H2O 39 Sv.83 r 460-510 0.1-0.4 40
p u r eH 2 O cj,70 r-7 520-670 - 37

K-AI-Si-H-O * Coz
Ms+Qtz = Sa*And*HzO 40 5v,83 450-510 0.2-0.5 40 r-
pureH2O Ev,65 L4 490-680 - 39
Ah,70 1-4 560-690 - 39
Ke,72 2 600-640- 39
Cj&Jo,74 0.5-5 530-720 - 39

K-Ca-Al-Si-C-H-O
Sa+An*HzO*COz4t
Cal+Ms+Qtz:= He,73 2,4,5,6,7440420 0.1-0.9 40
+ Zo*Kfs*HzO+COz 42
Cal+Ms+Qtz Jo&.Qr,72
782 THE CANADIAN MINERALOGIST

T A B L E2 . C O N T I N U E D

Systemor Equilibrium No Author P[kbar] Tfcl x(co2) B88 TD PH

K-Mg-Al-Si-H-O + CO2
Phl+Qtz= EnlSa*HzO 43 8o,83 5 780-800 0.6-0.7 41
pureH2O Wo,76 0.4-0.5 750-800 - 42 i- WD
Wn&Do,77 0,5 820-850 - 42 i-w

K-Ca-Mg-Al-Si-C-H-O
Phl+Qtz+Cal
= 5a*Tr*H:O*COr Ho,73 2,4,6 500-650 0.1-0.7 4l
He,75 2,4 450-520 0.6-0.7 411
Dol+Kfs+HzO
= Phl+Cal+COz 45 Pu&Jo,74 2 420-540 0.1-0.9 4t (i)+
Pu,78 4,6 460-650 0.1-0.9 41 (i)+
Ca-Ti-Si-C-O * HrO
Rt+Qtz+Cal= Ttn+COz 46 Ja&Ke,81b2,6 420-620 0.1-0.8 45 i(2)+

Key: Numbersin column'No'are usedin the text. Column'888' indicates the igure numberof Berman(1988).
Notationfor column 'TD' which indicatesthe consistency with the thermodynamic data baseof Berman(1988):
inconsistent('i'); slightlyinconsistent,
withinuncertainties
of the mineralpropertiesor fluid properties
['(i)']; numbersin
parenthesesspecify pressureat whichinconsistenciesareobserved; experimentsareat too hightemperatures compared
to Berman(1988) (+); experiments are at too low temperatures comparedto Berman(t9S8) (-); includesrevised
magnesitepropertiesof Mider & Berman(1991)(*); Column'PH' specifies inconsistencies amongststudiesof the
sameequilibrium.The one-letterabbreviations keyto the authorswithin the samegroup. Abbreviations for minerals
arethoseof Kretz(1983). Abbreviations for authors:Allen& Fawcett19S2(Al&Fa),Althauset,al. t970 (Ah), Bohlen
et aI. 7983(Bo), Chernosky & Berman1986a,b, 1989,1991(Ch&Be),Chatterjee1970(Ct, Chatterjee& Johannes
197a(Cj&Jo), Eggert& Kerrick1981(Eg&Ke),Egglerel aL t979 (El), Evans1975(Ev), Gordon& Greenuood1970,
1971(Go&Gr),Greenuood 1967a,b (Gr), Harker& Tuttle1956(Ha&Tu),Hewitt1973,1975(He), Hoschek 1973,
1974(Ho), Jacobs& Kenick1981b(Ja&Ke),Johannes 1969(Jo), Kiise& Metz 1980(Ka&Me),Kerrick1972(Ke),
Kenick& Ghent1979(Ke&Ge),Metz1967,1970,L976 (Me), Metz& Puhan,1970,1971(Me&Pu),Metz& Winkler
1963(Me&Wi),Nitsch1972(Ni), Puhan1978(Pu), Puhan& Johannes 197a(Pu&Jo),5hmulovich 1974,1978(5h),
Shvedenkov eJ a/. 1983(5v), Skippen1971(Sk), Slaughteret al. Lg75(51),Stone & Nitsch 1972(St&Ni), Walter
1963a,b (Wa), Widmark 1980(Wk), Wones& Dodge1977(Wn & Do), Wood 1976 (Wo), Zharikovet al. L977
(Zh), Ziegenbein& Johannes$7a (Zi&Jo).

titanitesuggestedby Berman(1988),who couldnot negativedeviations from ideal mixing in the fluid

fit the measurementsat2kbar on equilibrium (46).
Revisedproperties of magnesite(Trommsdorff &
Connolly 1990,Mdder & Berman 1991)result in
new inconsistencieswith equilibria (37, 38) that
wereconsistentwith the Berman(1988)data-base.
All thesediscrepanciescannot be explainedsolely
by deviationsof the propertiesof the fluid mixture
from those computed from the Kerrick & Jacobs
(1981) equation of state, and thus must reflect
errors in experimentsor thermodynamic data on
the solid phases.
Slight inconsistenciesthat indicate possible
phaseat temperaturesabove750-800oC at I kbar
pressure include brackets on equilibria in the
Ca-Al-Si system(6, 7, 10, I l) and in the Ca-Mg-Si
system(14, 15, 16). Considerationof the calcite
I-IV transition at approximately 800"C will
enhance these inconsistencies. Thermodynamic
properties of the calcite polymorphs are not well
constrained at present (Miider & Berman 1991).
Negative deviations from ideal mixing are consis-
tent with Greenwood's (1969) measurednegative
volumes on mixing at 700 and 800'C (Fig. 7).
At temperatures below 430oC,wheredeviations
 WATER - CARBON DIOXIDE MIXTURES 783

from ideal mixing become most pronounced, ideal mixing where P-V-T-X data are not
constraintsfrom phase-equilibriumdata are not in available.
accord. New data on the reaction calcite + (c) There are very few constraintsfrom phase-
andalusite + quartz + anorthite + CO2 (3) equilibrium data on the activity of H2O in a
(Chernosky& Berman 1991)seemto agreewith the H2O-CO2mixture.
Kerrick & Jacobs(1981)equation,whereasdata on
dolomite + quartz ;. calcite + talc + CO2 Q9) Minerql properties
demand more positive deviations from ideality.
Data on reaction (32) cannot be reconciled with More extensivemeasurements areneededon heat
existing constraintson the minerals involved. The capacity, expansivity,and compressibilityof mag-
Kerrick & Jacobs(1981)equation appearsto yield nesite,calcite, brucite and talc.
reasonabledeviations from ideal mixing at these
low temperatures.The equation cannot be utilized Theoreticsl work
below 325'C for mathematicalreasons.
None of the equationsof stateavailablefor fluid
CoNcr-usloNsANDFuruRE WoRK mixtures at higher pressuresand temperaturesare
applicable to subgreenschistmetamorphic condi
I conclude that at present, insufficient ex- tions becausethey do not accountfor the two-phase
perimentaldata and inadequatetheoreticalfounda- region.
tions are availableon which to build a constrained
empirical model that allows one to compute The concluding paragraphs are devoted to
fugacitiesof H2O-CO2mixtures over the range of specific experimental projects that are aimed at
pressureand temperatureof interestto petrologists. constraining the mixing properties of the fluid
The de Santise/ al. (1974)correction for chemical phase and at improving on the thermodynamic
associationused by Holloway (1977) and Bowers data-basefor solid phases.
& Helgeson(1983)is not supportedby available
experimentaldata. The Kerrick & Jacobs(1981) 5 magnesite+ I talc + 4forstefite + 1H2O
equation of state yields the most reasonable +5CO2
fugacity coefficients, even at temperaturesas low
as 350-400'C. Experimentalbracketsby Greenwood(1967)and
half-bracketsby Johannes(1969) constrain the
The existingbody of data is sufficiently extensive
that with some effort, the experimentaldata-base equilibrium position tightly at 1 and 2 kbar (Fig.
shouldbe amenableto the proposedapproach.The 8), but are difficult to reconcile with the ther-
following problems or lack of data deserve modynamic data-baseof Berman (1988) and the
particular attention. revised enthalpy of magnesite(Miider & Berman
1991).Ifthese data are accurate,then somemineral
properties must show temperature dependencies
P-V-T-X dato
(e.g., heat capacity, expansivity) that are very
different from the Berman (1988)data-base'or the
Inconsistensiesamong existing setsof.P-V-T-X deviations from the Kerrick & Jacobs (1981)
measurementsmust be resolved,and the range of equation of state are larger than estimated at
pressuremust be increasedto at least l0 kbar by present. New brackets on this equilibrium would
a complete series of P-V-T-X measurements, resolvetheseinconsistenciesand place constraints
includingpure H2Oand pure CO2.A determination on the deviation from ideal mixing in the fluid
of the exact shape of the Z.*""r, versasP hump phase.
below 2 kbar pressureis crucial.
Equilibria involving margarite
Phase-equilibrium dsta
This project would aim to provide constraints
(a) Severalinconsistenciesamongst studies on on the activity of H2O in a H2O-CO2mixture in a
phase-equilibriainvolving H2O-CO2mixtures need temperaturerange where deviations from ideality
to be resolved in order to permit refinement of are expectedto be significant (Fig. 9). Equilibria
thermophysicalproperties of solid phases,which with margarite in pure HrO have been studied by
will then provide better constraints on the fluid Jenkins(1984),Storre & Nitsch (1974),Nitsch et
mixture. al. (1981),Chatterjeeet al. (1984),and Chatterjee
(b) Phase-equilibriainvolving H2O-CO2 mix- (1974). The two equilibria suitable for study in a
tures can be utilized to constrain deviations from fluid mixture are: I margarite + I quartz + I
784 THE CANADIAN MINERALOGIST

- Kerrick & ,lacobs (1981) equqtion of state

. '. cot - tdeal mixitg

nso*Sfr-(-
^ 600
i-: ,rn

o {- -{- n oq \1 2kbar
k
= ttn
=
q
k
o 500
FI
-(D
F{
d00
4JO
(1969)l, 4 fbu
A Johanne.e
(1969)
tr Johaues 0.5,2,? kbar
'. {\C
5 NgS (1967)
Q Greenwood I kbar
(1967)
O creeoreood 2 tba

x(c0,) at P = 2000bat
X(COJ
Ftc. 8. Fluid compositionyersastemperaturephase Frc. 9. Fluid compositionversrs temperaturephase
diagramof the equilibriummagnesite+ talc = diagramof equilibriainvolvingmargarite,andalusite,
f o r s t e r i t+e H 2 O+ C O 2 a t 0 . 5l,, 2 , 4 a n d 7 k b a r . corundum,quartz,anorthite,H2OandCO2at2kbar
Filled symbolsdepictexperimental chargeswith the pressure.The solid curveswerecomputedwith the
reactant-stable phaseassemblage, opensymbols depict Kerrick & Jacobs(1981)equationof state and
product-stable charges.Curveswerecomputedwith lhermodynamic dataof Berman (1988).
Dashed curves
the Kerrick& Jacobs(1981)equationof srate,rhe werecomputedassumingideal mixing in the fluid
thermodynamic dataof Berman(1988),andmagnesite phase.Reactionswith zoisiteor grossular
thatmodify
properties revised by Miider& Berman(1991).Seetext the diagramat verywater-richcompositions are not
for discussion of inconsistencies. The diagramwas shown.Thediagramwasproducedwith GEO-CALC
computedwith GEO-CALC(Brownet al. 1988). (Brownel a/. 1988).

andalusite+ I anorthite + I H2O and I margarite studies include the reactions: 2 diaspore €
+ I anorthite + I corundum + I H2O. Therange corundum + H2O (580'C at 20 kbar), forsterite
accessibleto experimentationat a fluid pressureof + tremolite +senstatite + 2diopside + H2O
2 kbar spans400-500'Cand 0.1 < X(CO) < 0.7. (650'C at 20 kbar), talc + forsterite + enstatite
+ H2O (700'C at 20 kbar), talc + 3 enstatite +
quartz + H2O (800'C at 20 kbar), brucite ..
Equilibria at pressuresgreater than 15 kbar
periclase+ H2O (950"Cat 20 kbar), magnesite+
quartz + enstatite + CO2 (900'C at 20 kbar),
Such studies, performed in a solid-media ap- magnesite+ enstatite+ forsterite+ CO2(1100'C
paratus, would aim to constrain deviations from at 20 kbar), and calcite + quartz + wollastonite
ideal mixing in the fluid phase at pressuresnot + CO2 (1350'C at 20 kbar).
accessibleby P-V-T-X mesurements(e.9., Eggler
et al. 1979). The obvious disadvantagesare the
ACKNOWLEDGEMENTS
small volume of sample and the difficulty in
controlling fluid composition, speciation in the
fluid phase and diffusion of hydrogen at high The author is indebted to Hugh J. Greenwood
temperatures.Becauseonly the relative displace- (University of British Columbia) and Robert G.
ment from the equilibrium in the presenceof the Berman(GeologicalSurveyof Canada)for support
pure fluid is sought, some of the uncertainties and adviceduring his Ph.D. research.Hugh also
arising from extrapolation of thermodynamic ensuredcompletionof my Ph.D. on time by setting
properties cancel. In order to resolve deviations sail and venturing into new dimensions,exploring
from ideal mixing in the fluid phase, the best fluid properties.For that, and much more, I thank
precision possible has to be achieved, which is him. Financial support by NSERC to Greenwood
about t 5 K for piston-cylinder work. Feasible (67-4222)and Berman (OGP 0037234)for part of
 WATER - CARBON DIOXIDE MIXTURES 785

this projectis acknowledged.

J.R. Hollowaykindly pressures.Trans. Am. Geophys. Union (EOS) 11,
supplied computer codesfor the evaluation of his 621 (abstr.).
equation of state.The manuscriptwas improved at
variousstagesby R.G. Berman,H.J. Greenwood BnowN,T.H., Bsnrr.reN, R.C. & PEnrtNs,E.H. (1988):
GEO-CALC: software package for calculation and
and T.H. Brown. Terry Gordon provided stimulus
display of pressure - temperature - composition
by organizing an exciting "Greenwood Sym- phase diagrams using an IBM or compatible
posium" during the Vancouver 1989 GAC-MAC personal computer. Comp. Geosci. 14, 279-289,
Annual Meeting. The comments made by E.L.
Johnson,R.F. Martin and an anonymousreviewer Bucuen-NunptrNrN,K. (1988): Metamorphism of
were constructiveand helpful. ultramafic rocks in the central Scandinavian
Caledonides. Nor. Geol. Unders., Spec. Publ. 3,
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