A New Equation of State for Carbon Dioxide Covering the Fluid Region

from the Triple-Point Temperature to 1100 K at Pressures up to 800 MPa

R. Span and W. Wagner

Lehrstuhl fur Thermodynamik, Ruhr-Universitat Bochum, D-44780 Bochum, Germany

Received 25 May 1994

This work reviews the available data on thermodynamic properties of carbon dioxide
and presents a new equation of state in the form of a fundamental equation explicit in the
Helmholtz free energy. The function for the residual part of the Helmholtz free energy
was fitted to selected data of the following properties: (a) thermal properties of the
single-phase region (ppT) and (b) of the liquid-vapor saturation curve (Ps> p', p")
including the Maxwell criterion, (c) speed of sound w and (d) specific isobaric heat
capacity c p of the single phase region and of the saturation curve, (e) specific isochoric
heat capacity c v' (f) specific enthalpy h, (g) specific internal energy u, and (h) Joule-
Thomson coefficient /-t. By applying modern strategies for the optimization of the math-
ematical form of the equation of state and for the simultaneous nonlinear fit to the data of
all these properties, the resulting formulation is able to represent even the most accurate
data to within their experimental uncertainty. In the technically most important region up
to pressures of 30 MPa and up to temperatures of 523 K, the estimated uncertainty of the
equation ranges from ± 0.03% to ± 0.05% in the density, ± 0.03% to ± 1% in the speed
of sound, and ± 0.15% to ± 1.5% in the isobaric heat capacity. Special interest has been
focused on the description of the critical region and the extrapolation behavior of the
formulation. Without a complex coupling to a scaled equation of state, the new formu-
lation yields a reasonable description even of the caloric properties in the immediate
vicinity of the critical point. At least for the basic properties such as pressure, fugacity,
and enthalpy, the equation can be extrapolated up to the limits of the chemical stability of
carbon dioxide. Independent equations for the vapor pressure and for the pressure on the
sublimation and melting curve, for the saturated liquid and vapor densities, and for the
isobaric ideal gas heat capacity are also included. Property tables calculated from the
equation of state are given in the appendix. © 1996 American Institute of Physics and
American Chemical Society.

Key words: carbon dioxide; correlation; critical region; data evaluation; equation of state; extrapolation;
fundamental equation; melting line; property tables; sublimation line; thermal and caloric properties; and
vapor-liquid coexistence curve.

Contents

Nomenclature. . . . . . . . . . . . . . . . . . . . . .. . . . . . .. 1513 3. Phase Equilibria of Carbon Dioxide. . . . . . . . . . .. 1519

Physical Constants for Carbon Dioxide. . . . . . . .. 1513 3.1 Triple Point. ........................... 1519
1. Introduction................................ 1514 3.2 Critical Point. . . . . . . . . . . . . . . . . . . . . . . . . .. 1519
1.1 Background............................ 1514 3.3 Melting Pressure. . . . . . . . . . . . . . . . . . . . . . .. 1520
1.2 Prior Correlations of Carbon Dioxide 3.4 Sublimation Pressure. . . . . . . . . . . . . . . . . . . .. 1521
Properties and Demands on the New 3.5 Vapor Pressure ....................... " 1521
Correlation. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1514 3.6 Saturated Liquid Density. . . . . . . . . . . . . . . .. 1524
1.3 Organization of the Article. . . . . . . . . . . . . . .. 1516 3.7 Saturated Vapor Density. . . . . . . . . . . . . . . . .. 1525
2. Basic Elements of the Development of Equations 3.8 Caloric Data on the Liquid-Vapor Phase
of State in Form of a Fundamental Equation. . . .. 1516 Boundary. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1526
2.1 Helmholtz Function. . . . . . . . . . . . . . . . . . . . .. 1516 4. Experimental Basis of the New Equation of
2.2 Helmholtz Energy of the Ideal Gas. . . . . . . .. 1516 State. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1526
2.3 Residual Part of the Helmholtz Energy. . . . .. 1517 4.1 Thermal Properties .................... " 1527
2.3.1 Fitting an Empirical Equation for ¢r 4.2 Specific Isobaric Heat Capacity. . . . . . . . . . .. 1528
to Data ......................... " 1517 4.2.1 Experimental Results for the Specific
2.3.2 Optimizing the Mathematical Form .... 1518 Isobaric Heat Capacity. . . . . . . . . . . . .. 1528
2.3.3 The Procedure of Weighting. . . . . . . .. 1518 4.2.2 Results for the Specific Isobaric Heat

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 1510 R. SPAN AND W. WAGNER

Capacity in the Ideal-Gas State. . . . . .. 1529 5. Selected data for the critical point of carbon
4.3 Specific Isochoric Heat Capacity. . . . . . . . . .. 1530 dioxide ................................. " 1520
4.4 Speed of Sound. . . . . . . . . . . . . . . . . . . . . . . .. 1532 6. Summary of the data sets for the sublimation
4.5 Enthalpy............................... 1532 pressure of carbon dioxide. . . . . . . . . . . . . . . . . .. 1521
4.6 Internal Energy. . . . . . . . . . . . . . . . . . . . . . . .. 1532 7. Summary of the data sets for the vapor pressure
4.7 Joule-Thomson Coefficient. ............. , 1532 of carbon dioxide. . . . . . . . . . . . . . . . . . . . . . . . .. 1522
4.8 Virial Coefficients. . . . . . . . . . . . . . . . . . . . . .. 1533 8. Summary of the data sets for the saturated liquid
4.9 Liquid-Vapor Equilibrium. . . . . . . . . . . . . . .. 1533 density of carbon dioxide. . . . . . . . . . . . . . . . . . .. 1523
4.10 Adjustment of Data. . . . . . . . . . . . . . . . . . . .. 1534
9. Summary of the data sets· for the saturated vapor
4.10.1 Adjustment of Data Sets Describing
density of carbon dioxide .................. " 1524
the Critical Region. . . . . . . . . . . . . .. 1534
10. Summary of the data sets for caloric properties
4.10.2 Adjustment of ppT Data. . . . . . . . . .. 1534
on the liquid-vapor phase boundary of carbon
4.10.3 Correction of Isobaric Heat
dioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1526
Capacities. . . . . . . . . . . . . . . . . . . . .. 1535
5. Description of Thermodynamic Propert.ies in the 11 _ Sllmm~ry of the dat~ sets available for the ppT
Critical Region. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1535 relation of carbon dioxide ................... , 1527
5.1 Limitations of Analytical Equations of State. 1536 12. Summary of selected ppT data for carbon
5.2 Use of Nonanalytic Terms as an Integral dioxide; detailed information is given on
Component in an Empirical Wide-Range the uncertainty values estimated by the authors
Equation of State. . . . . . . . . . . . . . . . . . . . . . .. 1537 and those estimated by ourselves and used
6. New Equation of State. . . . . . . . . . . . . . . . . . . . . .. 1541 in the weighting procedure .................. , 1529
6.1 Ideal-Gas Part of the Helmholtz Energy. . . .. 1541 13. Summary of the data sets available for the
6.2 Residual Part of the Helmholtz Energy. . .. .. 1543 specific isobaric heat capacity of carbon dioxide.. 1530
7. Comparisons of the New Equation of State with 14. Summary of selected data for the specific
Experimental Data and Other Equations of State_ ] 54() isobaric heat capacity of carbon dioxide; detailed
7.1 Liquid-Vapor Boundary .................. 1546 information is given on the uncertainty values
7.1.1 Thermal Properties on the Coexistence estimated by the authors and those estimated by
Curve. . . . . . . . . . . . . . . . . . . . . . . . . . .. 1546 ourselves and used in the weighting procedure. .. 1530
7.1.2 Caloric PropertIes on the CoeXIstence 15. Data sets for the isobaric heat capacity in the
Curve ............................ 1547 ideal-gas state of carbon dioxide calculated by
7.2 Single-Phase Region. . . . . . . . . . . . . . . . . . . .. 1547 theoretical approaches. . . . . . . . . . . . . . . . . . . . . .. 1530
7.2.1 Thermal Properties in the Single-Phase 16. Summary of the data sets available for the
Region. . . . . . . . . . . . . . . . . . . . . . . . . .. 1547
specific isochoric heat capacity of carbon
7.2.2 Caloric Properties in the Single-Phase
dioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1531
Region. . . . . . . . . . . . . . . . . . . . . . . . . .. 1553
17. Summary of selected data for the specific
7.3 Extrapolation Behavior of the New
isochoric heat capaci~y of carbon dioxide; detailed
Fundamental Equation. . . . . . . . . . . . . . . . . .. 1556
information is given on the uncertainty values
7.3.1 Extrapolation Beyond the Range of
Primary Data. . . . . . . . . . . . . . . . . . . . .. 1557 estimated by the authors and those estimated by
7.3.2 Representation of "Ideal Curves"..... 1557 ourselves and used in the weighting procedure. .. 1531
8. Uncertainty of the New Fundamental Equation... 1559 18. Summary of the data sets available for the speed
9. Conclusions................................ 1559 of sound of carbon dioxide. . . . . . . . . . . . . . . . . .. 1531
10. Appendix: Thermodynamic Properties of Carbon 19. Summary of selected data for the speed of sound
Dioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1559 of carbon dioxide; detailed information is given
11. Acknowledgments. . . . . . . . . . . . . . . . . . . . . . . . .. 1593 on the uncertainty values estimated by the
12. References.... . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1593 authors and those estimated by ourselves and
used in the weighting procedure. . . . . . . . . . . . . .. 1532
20. Summary of the data sets available for enthalpy
List of Tables
1. Available wide range equations of state for differences of carbon dioxide. . . . . . . . . . . . . . . .. 1532
carbon dioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1515 21. Summary of the data sets available for differences
2. Selected scaled equations of state for carbon of the internal energy of carbon dioxide. . . . . . . .. 1532
dioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1515 22. Summary of the data sets available for the Joule-
3. Relations of thermodynamic properties to the Thomson coefficient of carbon dioxide. . . . . . . . .. 1533
dimensionless Helmholtz function cP consisting 23. Summary of data available for the second and
of cPo and d/; see Eq. (2.1). . . . . . . . . . . . . . . . . .. 1517 third virial coefficient of carbon dioxide. For
4. Selected data for the triple point of carbon reasons explained in the text, no data were
dioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1520 assigned to Group 1. . . . . . . . . . . . . . . . . . . . . . . .. 1533

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1511

24. Summary of selected data describing the comparison:. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1525

liquid-vapor phase equilibrium of carbon dioxide; 6. Relative deviations 100Llp = 100(Pexp - Peale)/ Pexp
detailed infonnation is given on the uncertainty of experimental ppT data from values calculated
values estimated by the authors and those from Eq. (6.1). This figure illustrates the
estimated by ourselves and used in the weighting reason for adjusting the data of Kirillin et al. 140
procedure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1534 and Michels et al. 123 (see Sec. 4.10.2).. . . . . . .. .. 1534
25. Temperature dependent corrections of isobaric 7. Relative deviations WOLle p = 100( e p,exp
heat capacity data. . . . . . . . . . . . . . . . . . . . . . . . . .. 1535 - e p,ealc)/ e p,exp of experimental e p data from
26. Examples for power laws describing specific isobaric heat capacities calculated from
thermodynamic properties along certain paths Eq. (6.1). This figure illustrates the reason for
throughout the critical region. . . . . . . . . . . . . . . . .. 1535 correcting the data of Ernst et al. 179 and Bender
27. Coefficients of the correlation equations, Eq. eta!.l77 (see Sec. 4.10.3) ..................... 1534
(6.2) and Eq. (6.3), for e~ and cjJ0, respectively... 1540 8. Relative-deviations 100Llp= 100(Pexp - Peale)/Pexp
28. The ideal-gas part of the dimensionless Helmholtz of experimental ppT data on the critical isotherm
energy cpo and its derivatives. . . . . . . . . . . . . . . . .. 1541
from values calculated from Eq. (6.1). Values
29. Summary of the data used for the linear calculated from the crossover equation of Chen
optimization procedure and for the nonlinear fit.. 1541
et at. 27 and from refitted equations using the
10 Prlrameters of the non analytic terms in the bank
CII4 - and Orform (see Sec. 5.1) arc plotted for
of terms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1543
comparison.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1536
31. Coefficients and exponents of Eq. (6.5) ......... 1544
9. Representation of representative isochoric heat
32. The residual part of the dimensionless Helmholtz
capacity data in the critical region. The plotted
energy cpr and its derivatives. . . . . . . . . . . . . . . . .. 1.'54.'5
curves correspond to values calculated from
33. The definition of the zeroth- and first-order ideal
the crossover equation of Chen et a!. 27 and from
curves of the compression factor Z. . . . . . . . . . . .. 1557
refitted equations using the CH4 - and Or form
34. Thermodynamic properties of saturated carbon
dioxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1560 (see Sec. 5.1).. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1536
35. Thennodynamic properties of carbon dioxide. . .. 1562 10. While preliminary equations of state showed a
discontinuous plot of the third density derivative
of the reduced Helmholtz energy, the new
List of Figures equation of state, Eq. (6.1), yields continuous
1. Relative deviations of experimental melting
plots for the third derivatives. . . . . . . . . . . . . . . . .. 1538
pressure data from values calculated from
11. Representation of representative isochoric heat
the melting pressure equation, Eg. (3.10). In this
capacity data in the critical region. The plotted
figure, both the corrected and the uncorrected
curves correspond to values calculated from
data are plotted (see Sec. 3.3). . . . . . . . . . . . . . . .. 1521
Eq. (6.1), the crossover equation of Chen et al.,27
2. Absolute deviations LlPsub=(Psub,exp-Psub,eale) of
and a refitted equation using the' CH4-form
selected experimental sublimation pressure data
(see Sec. 5.1) .. o,'.' • • • • • • •..• • • • • • • • • • • • • • • • • •• 1538
from values calculated from the sublimation
12. Representation ·of the speed of sound on
pressure equation, Eq. (3.12). In this figure, both
the corrected and the uncorrected data of isotherms in the critical region. The plotted curves
Bilkadi etal. 74 are plotted (see Sec. 3.4) ........ 1522 correspond to values calculated from Eq.
3. Relative deviations of selected experimental (6.1), the crossover equation of Chen et al.,27
vapor pressure data from V::thlf''' c-::tklllatf'O and a refitted equation using the CH4-form (see
from the vapor pressure equation, Eq. (3.13). Sec. 5.1) ................................... 1538
Vapor pressures calculated from the 13. Representation of the isochoric heat capacity on
corresponding equation of Angus et al. 3 are isotherms in the critical region. The plotted
plotted for comparison.. . . . . . . . . . . . . . . . . . . . .. 1523 curves correspond to values calculated from Eg.
4. Relative deviations 100Llp' = 100(p' exp - p' eale)/ (6.1), the crossover equation of Chen et al.,27
p' exp of selected experimental saturated liquid and a refitted equation using the CH4 -form (see
density data from values calculated from Sec. 5.1).. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1539
Eg. (3.14). Saturated liquid densities calculated 14. Representation of experimental isochoric heat
from the corresponding equation of Angus capacity data in the single phase (T> Te) and
et al. 3 are plotted for comparison.. . . . . . . . . . . . .. 1524 two phase (T < Te) region in a double logarithmic
5. Relative deviations of selected experimental diagram. The plotted curves correspond to
saturated vapor density data from values data on the critical isochore calculated from Eq.
calculated from Eq. (3.15). Saturated vapor (6.1), the crossover equation of Chen et al.,27
densities calculated from the corresponding and a refitted equation using the 02-form (see
equation of Angus et al. 3 are plotted for Sec. 5.l). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1539

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 1512 R. SPAN AND W. WAGNER

15. For temperatures between Tc and Tc + 1 K Eq. 24. Relative density deviations of selected ppT data
(6.0 results in an oscillating plot for the from values calculated from Eq. (6.0. Values
isobaric heat capacity around the critical density.. 1539 calculated from the wide-range equations of Ely
16. Relative deviations of c~ data from values et al. 15 and Angus et ai. 3 are plotted for
calculated from Eq. (6.2). The upper diagram comparison.. . . . . . . . . . .. . . . . . . . . . . . . . . . . . . .. 1551
shows data calculated from statistical 25. Relative density deviations of selected ppT data
at high temperatures from values calculated from
thermodynamics (see Table 15) and the lower
Eq. (6.1). Values calculated from the
diagram shows data extrapolated from
wide-range equations of Ely et ai. 15 and Angus
experimental results (see Table l3). Values of c~ 3
et al. are plotted for comparison.. . . . . . . . . . . . .. 1552
calculated from the corresponding equations
26. Relative density deviations of selected ppT data
of Angus et ai. 3 and Ely et ai. 15 are plotted for at high pressures from values calculated from
comparison.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1540 Eq. (6.1). Values calculated from the wide-range
17. Distribution of the experimental data used for equations of Ely et ai. 15 and Angus et ai. 3 are
the establishment of the residual part of the plotted for comparison~ in this pressure range,
new fundamental equation, Eq. (6.5), in apT these two equations of state are at least partly
diagram.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1542 extrapolated (see Table 0.. . . . . . . . . . . . . . . . . . .. 1552
18. Relative deviations 1OOLly = 100(Yexp -Yca1c)/Yexp 27. Relative deviations of selected isobaric heat
(y = p s ,p I , p") of the experimental saturation capacity data from values calculated from
data of Duschek et ai. 58 from values calculated Eq. (6.1). Values calculated from the wide-range
from Eq. (6.1). Values calculated from the equations of Ely et al. 15 and Angus et al. 3 are
auxiliary equations presented in Sec. 3, the plotted for comparison ..................... " 1553
equation of state of Ely et al. 15 and the auxiliary 28. Representation of the isobaric heat capacity on
equations of Angus et al. 3 are plotted for isobars in the gas region and in states on the
sublimation curve (saturated vapor). Values
comparison ................................ , 1546
calculated from the wide-range equations of Ely
19. Relative deviations 100Lly= 100(Yexp -Yca1c)IYexp
et al. 15 and Angus et al. 3 are plotted for
(Y=Ps' p', p") of the near critical experimental
comparison.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1553
saturation data of Duschek et ai.58 from
29. Relative deviations of isobaric heat capacity data
values calculated from Eq. (6.1). Values
at high temperatures from values calculated from
calculated from the auxiliary equations presented Eq. (6.1). Values calculated from the
in Sec. 1 ann from the cro~~()ver equation of wide-range equations of Ely et al. 15 and Angus
Chen et ai.27 are plotted for comparison.. . . . . . .. 1546 et ai. 3 are plotted for comparison.. . . . . . . . . . . . .. 1554
20. Relative deviations 100Lly=100(Yexp-Ycalc)IYexp 30. Relative deviations of selected isochoric heat
(y = w" , w', c;) of experimental caloric data at capacity data from values calculated from Eq.
saturation from values calculated from Eq. (6.1). (6.1). Values calculated from the wide-range
Data calculated from the wide-range equations equations-bf Ely et cit. IS and Angus et ai. 3 are
of Ely et al. 15 and Angus et ai. 3 are plotted for plotted for comparison.. . . . . . . . . . . . . . . . . . . . .. 1554
comparison ................................ , 1547 31. Representatiun uf the isuchurk heat L:apadty UIl

21. Relative density deviations of very accurate ppT high-density isochores. For each of the isochores
data at subcritical temperatures from values the plotted pressure range starts at the
calculated from Eq. (6.1). Values calculated from corresponding vapor pressure. Values calculated
the wide-range equations of Ely et al. 15 and from the wide-range equations of Ely et al. 15
Angus et al. 3 are plotted for comparison ........ , 1548 and Angus et al. 3 are plotted for comparison.. . .. 1554
32. Relative deviations of speed of sound data at
22. Relative pressure deviations of very accurate
supercritical temperatures from values
ppT data in the extended critical region from
calculated from Eq. (6.1). Values calculated
values calculated from Eq. (6.1). Values
from the wide-range equations of Ely et al. 15 and
calculated from the wide-range equations of Ely of Pitzer and Schreiber,16 ::InrI, in the range of
et al. 15 and Pitzer and Schreiber 16 and -from
its validity, from the crossover equation of Chen
the crossover equation of Chen et al. 27 are plotted et aZY are plotted for comparison.. . . . . . . . . . . .. 1555
for comparison ............................. , 1549 33. Relative deviations of speed of sound data at
23. Relative density deviatiuns uf velY aL:L:uUtte fJpT high pressures from values calculated from
data at supercritical temperatures from values Eq. (6.1). Values calculated from the wide-range
calculated from Eq. (6.0. Values calculated from equations of Ely et al. 15 and Angus et al. 3 are
the wide-range equations of Ely et 0/ 15 ::Ind plotted for comparison; in this pressure range,
Angus et ai. 3 are plotted for comparison.. . . . . . .. 1550 t~ese two equations of state are at least partly

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1513

extrapolated (see Table 1).. . . . . . . . . . . . . . . . . . .. 1555 R Gas constant

34. Relative deviations of experimentally determined s Specific entropy
J oule-Thomson coefficients from values T Thermodynamic temperature, ITS-90
calculated from Eq. (6.1). Values calculated u Specific internal energy
from the wide-range equations of Ely et al. 15 and v Specific volume
Angus et al. 3 are plotted for comparison. The w Speed of sound
data of Vukalovich et ai. 206 were not used when x,y Independent variables
establishing Eq. (6.1) ........................ 1556 z Any thermodynamic property
35. Representation of experimentally determined Z Compression factor
fugacities ,on isotherms at very high temperatures Greek
and pressures. Values calculated from the a,/3, y,Ll, () Adjustable parameters
wide-range equations of Ely et al. 15 and Angus a,/3,y,o Critical exponents
et ai. 3 are plotted for comparison.. . . . . . . . . . . . .. 1556 Ll Difference in any quantity
36. Representation of experimental data describing Ll, (), l/J Functions
the Hugoniot curve of carbon dioxide. Hugoniot o Reduced density (0= pi pc)
curves calculated from the wide-range a Partial differential
equations of Ely et al. 15 and Angus et al. 3 are cp Fugacity
plotted for comparison.. . . . . . . . . . . . . . . . . . . . .. 1557 cP Dimensionless Helmholtz energy
j/. The so-called ideal curves calculated from Eq. [¢=A/(RT)]
(6.1) and plotted in a pi Pc> 10g(T/Tc) diagram. f.L Joule-Thomson coefficient
The Joule-Thomson inversion curve and the Joule P Mass density
inversion curve exceed the temperature range (J Variance
in which Eq~ (6.1) is fitted to experimental data... 1557 T Inverse reduced temperature (T= Tc IT)
38. Tolerance diagram for densities calculated from 2 Weighted sum of squares
X
Eq. (6.1). In region B the uncertainty in pressure Superscripts
is gIven.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1558 o Ideal gas property
39. Tolerance diagram for speed of sound data r Residual
calculated from Eq. (6.0. In the immediate Saturated liquid state
vicinity of the critical point (region G) it is " Saturated vapor state
difficult to estimate an uncertainty in w because of Denotes a vector
the growing influence of uncertainties in Subscripts
temperature and pressure measurement.. . . . . . . .. 1558 c At the critical point
40. Tolerance diagram for isobaric heat capacities calc Calculated
calculated from Eq. (6.1). In the immediate corr Corrected
vicinity of the critical point (region G) it is exp Experimental
difficult to estimate an uncertainty in cp because i,j,k, I,m Indices
of the growing influence of uncertainties in m Denotes the melting pressure
temperature and pressure measurement.. . . . . . . .. 1558 s ·'Denotes the vapor pressure
sub Denotes the sublimation
pressure
Nomenclature At the triple point
Symbol Description wt Weighting
A,B,C,D,a,b,d,n,t Adjustable parameters
(J Along the saturated liquid curve
A Specific Helmholtz energy o In the reference state
B Second virial coefficient OH In the initial state of Hugoniot curve
C Third virial coefficient measurements
Specific isobaric heat capacity 90 Temperatures according to the ITS-90
Specific isochoric heat capacity 68 Temperatures according to the IPTS-68
Specific heat capacity along 48 Temperatures according to the IPTS-48
the saturated liquid line
g Specific Gibbs energy
h Specific enthalpy
i.j.k.l.m Serial numbers PhYSical Constants for Carbon Dioxide
1,J Maximum number of the serial
numbers i,J
M Number of data, molar mass M Molar mass: M=(44.009 8±0.001 6) g/mol; see Ref. 1
p Pressure

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 1514 R. SPAN AND W. WAGNER

Rm Molar gas constant: R m=(8.314 510±0.000 210a) stance for theoretical approaches dealing with the critical re-
J/(mol K); see Ref. 2 gion of pure fluids. Almost every physical model for the
R Specific gas constant: R=R mIM=(0.188 9241 description of the critical region has been tested for carbon
± 0.000011 6) kJ/(kg K) dioxide.
Tc Critical temperature: Tc =(304.1282±0.015)K; see In 1965, an international research project on the thermo-
Sec. 3.2 dynamic properties of carbon dioxide was established at the
Pc Critical pressure: Pc=(7.377 3±0.003 O)MPa; see Sec. instigation of the International Union of Pure and Applied
3.2 Chemistry (IUPAC). In 1976, Angus et al. 3 published a
Pc Critical density: Pc=(467.6±0.6) kg/m3 ; see Sec. 3.2 monograph which reviewed the experimental data available
Tt Triple-point temperature: T t =(216.592± 0.002) K; see up to 1973 and presented extensive tables of the thermal and
Sec. 3.1 caloric properties derived from the selected equation of state.
Pt Triple-point pressure: Pt=(0.517 95± 0.000 10) MPa; Nevertheless, knowledge of the thermodynamic properties of
see Sec. 3.1 carbon dioxide remained unsatisfactory. Thus, since 1973
To Reference temperature: T o=298.15 K numerous experiments including state-of-the-art experiments
Po Reference pressure: Po=0.101 325 MPa with significantly improved accuracy have been performed in
hg Reference enthalpy in the ideal gas state at To: order to improve the quality of the entire data set; a third of
hg=O kJ/kg the data sets available today belongs to this group.
sg Reference entropy in the ideal gas state at To, Po: In addition to the increased amount of experimental data,
s3=0 kJ/(kg K) correlation techniques have significantly improved during
the last decade. Sophisticated "multi-property" fitting
procedures4 ,5 and a new strategy for optimizing the structure
1. Introduction of empirical correlation equations6 have resulted in a new
basis for the development of an empirical equation of state.
1.1 Background

Over the past fifteen years great interest in the properties

of carbon dioxide has developed. This interest has evolved
from both industrial and scientific applications. From an en- 1.2 Prior Correlations of Carbon Dioxide
gineering angle, carbon dioxide has proved to be the most Properties and Demands on the New Correlation
commonly used solvent for supercritical fluid extraction and Since 1960 numerous correlation equations for the ther-
to be an excellent tool for enhanced oil recovery. Carbon modynamic properties of carbon dioxide have been devel-
dioxide processing and pipelining technologies have become oped, but only a few of them describe the properties within a
of considerable commercial importance. Furthermore, the sufficiently large range including the gas, liquid, and super-
discussion on the greenhouse effect has focused technical critical states. Table 1 summarizes the equations of state for
interest on carbon dioxide as the most significant combustion carbon dioxide which have been developed since 1970. After
product which effects the atmosphere. examining the wide-range equations of state available in
From a thermodynamic point of view, carbon dioxide usu- 1973, AIlgU:S et uf. 3 discussed three equations in the IUPAC
ally serves as the best known reference for a molecule with a monograph, namely the equations of Bender,7 Altunin and
strong quadrupole moment and as a testing fluid for calibra- Gadetskii,8 and Stein,9 which form the beginning of Table 1.
tion purposes. However, in sciences related to thermodynam- Finally. Angus et al. decided to use the equation of Altunin
ics, interest is mainly based on the widespread occurrence of and Gadetskii 8 as a basis for the IUPAC monograph. At that
carbon dioxide. Geophysical calculations of chemical equi- time, none of the existing wide-range equations of state of-
libria, under outer mantle conditions for example, require fered a reasonable description of the critical region. Thus,
rcliablcthcrmodynamic data of carbon dioxide at very high Angus el al. 3 combined lht: widt:-range equation with a
pressures and temperatures. scaled equation of state developed by Schofield 19 and a
Besides this, investigations of thermodynamic properties switching function developed by Chapela and Rowlinson.
2o
of carbon dioxide have always been influenced by the loca- Although it was known that the evaluation of the combined
tion of the critical region. On the one hand, the critical tem- correlation equations causes numerical problems and yields
perature of approximately 304 K allows many technical pro- incorrect results for derived properties in the switching re-
cesses, for example pipelining processes, to be carried out gion, the equation was generally accepted as a reference for
within the critical or at least in the extended critical region. carbon dioxide. In 1988, Pitzer and Schrdbt:l l () luok up the
Therefore, from a technical point of view a sufficiently ac- IUPAC compilation again and showed that very similar re-
curate calculation of thermodynamic properties is more dif- sults can be achieved with less numerical expense if special
ficult for carbon dioxide than for other substances. On the tp.rm" for the description of the critical region are added to
other hand, the data situation in the critical region is· excep- the equation of Altunin and Gadetskii.
8
tionally good, which makes carbon dioxide a reference sub- The only correlations which really improve the results of
Angus et al. 3 are the equations developed at the National
"Reference 2 gives a standard deviation of ::!::O.OOO 070 J/(mol K). Institute ot ~tandards and Technology by Ely14 and Ely

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1515

TABLE 1. Available wide-range equations of state for carbon dioxide

Temperature Pressure Structure of Number of coeff. Data used in the

Authors Year range (K) range (MPa) the equation in residual part correlation

Renner7 1970 216-1076 0-50 Extended BWRa 20 ])oT.])so' Oil

A1tunin and Gadetskii 8 1971 215-1 300 0-300 Polynomial 50 ppT,c p
Stein9 1972 ... b ••. b Polynomial 44 ppT,psp' p"
Starling et at. 10 1972 243-413 0-48 Extended BWR a II ppT,h,ps
Meyer-Pittroffll 1973 200-1 273 0-60 Polynomial 84 ppT,psp' p",C V ,h
Angus et at. 3 (IUPAC) 1976 220-1 100 0-100 Combined 50+5+4 ppT,c p
Huang et at. 12 1985 216-423 0-310 Extended BWR a .c 27 ppT,PSp'p"
Elyl4 1986 216-1 023 0-300 Schmidt and Wagner4 32 ppT,psp' p",c v ,c"
Ely et al. 15 1987 216-1023 0-300 Schmidt and Wagner4 32 ppT,psp' p",c v ,c"
Pitzer and Schreiber l6 1988 230-1030 0-100 Extended polynomial 53 ppT,psp' p",c v d
Ely et al.17 1989 216-1 023 0-316 Jacobsen and Stewart l8 32 ppT,psp' p",c v ,c"
Pitzer and Sterner18a 1994 220-2000 0-10 000 Fractional form 28 ppT,psp' p",B,f e

"Benedic(-Webb-Rubin.
bNo information published.
cTerms developed by Ewers and Wagner l3 for the description of the critical region were also used.
dBesides some experimental data, mainly data from the IUPAC tables 3 were used as input data.
CRp~inp<.: mmp pxpprimpntal nata, mainly clata calculated from the equation of Ely et al. 17 were used as input data.

et a1. 15 ,17 These equations take into account almost all of the • Extrapolation to temperatures and pressures outside the
published experimental results. However, some of the most range of validity yields unreasonable results.
important state-of-the-art experiments on carbon dioxide • The temperature values used do not correspond to the cur-
were not yet available at that time. A detailed comparison21 rent International Temperature Scale of 1990 (ITS-90).
shows that the: N]natinn givf':n in Re:f~ 14 :lno 1'i lI~ine thf> Tht: ~4ualiull uf Pilz~l ami Sl~m~I lX~ L:aIl mainly be L:UIl-
form developed by Schmidt and Wagner4 is superior to the sidered to be an example for an empirical equation of state
equation given in Ref. 17 which uses the fonn developed by with reasonable extrapolation behavior; the authors do not
Jacobsen and Stewart. 18 claim that this equation improves the description of thermo-
Tests of these correlations have YIelded that all of the ex- dynamic properties in the region where accurate data exist.
isting equations of state, independent of their different qual- The problems related to the description of properties
ity, show the following limitations: within the critical region can essentially be solved by using
• State-of-the-art data for the ppT relation are not repre- scaled equations of state; Table 2 shows selected correlations
sented to within their experimental uncertainty. with such scaling approaches for the description of the criti-
• State-or the-art data describing the liquid-vapor phase cal region of carbon dioxide. However, the relatively small
equilibrium are not represented to within their experimen- range of validity and the mathematically complex structure
tal uncertainty. of these equations limit their use.
• Within the critical region, the calculation of caloric prop- An exception with regard to the range of validity is the
erties yields unreasonable results. empirical equation of Erickson et at. 26 This equation uses an
• Unreasonable behavior can be observed in regions wIth a Improved form of the transtormatIOn procedure, originally
poor data situation. developed by Fox,29 to achieve a reasonable but not an as-

TABLE 2. Selected scaled equations of state for carbon dioxide

Temperature' Densityb Scaling technique Number of fitted

Authors Year range (K) range (kg/m'l used coefficients

Schofield 19 1969 Simple scaling

Vicenti-Missoni el al. ~~ 1969 301-313 327-608 Simple scaling 6
Murphy er af.~3 1973 304-314 336-598 Simple scaling 5
Albrighl er al. J~ 1987 301-323 290-595 Revised and ex[ended 13
Albright et af. ~s 1987 298-322 245-600 Crossover 12
Erickson el af.:26 1987 Transformation 32+7
Chen el al.:' 7 1990 291-373 193-712 Crossover 19
Kiselev el al. 28 1991 298-395 280-655 Crossover 12

"Range of validity for P == Pc .

bRange of validity for T== T ...
eNo information published.
dScaled wide-range equation. valid for pressures up to 300 MPa at temperatures from 212 K to 1000 K.

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 1516 R. SPAN AND W. WAGNER

ymptotically correct description of the caloric properties in 2. Basic Elements of the Development of
the critical region. Like other parametric approaches, this Equations of State in Form of a
equation still requires complicated iteration procedures, but
Fundamental Equation
it is valid in a range which is sufficiently wide for engineer-
ing application~. Tests cdllieu uut by Erkbun e( al. '"
showed that outside the critical region the transformed equa- The new equation of state, developed for the representa-
tion based on the form developed by Jacobsen and Stewart 18 tion of the thermodynamic properties of carbon dioxide, is an
is inferior to Ely's equation. 14,lS empirical representation of the fundamental equation explicit
The purpose of this article is to present a new equation of in the Helmholtz energy. Since the application of optimiza-
state for carbon dioxide explicit in the Helmholtz energy, tion procedures. and the technique of mUlti-property fitting
which is designed to overcome the disadvantages of the ex- were extensively discussed by Setzmann and Wagner6 ,30 and
isting correlations. The consistent use of sophisticated Saul and Wagner,S this section is restricted to some basic
fitting 30 and optimization6 procedures allows the representa- facts giving a rough understanding of the procedures used for
tion of even the most accurate data within their experimental the development of the new equation. However, those facts
uncertainty. Extensive investigations of the ci::lt~ set prevent which have not previously been published are outlined in
the equation from unreasonable behavior within the fitting more detail.
region, and new procedures are introduced to guarantee a 2.1 Helmholtz Function
reasonable extrapolation behavior of the new equation. The
representatIOn ot calonc properties in the critical region has The fundamental equation given in this article IS expressed
been improved by an empirical approach which yields rea- in form of the Helmholtz energy A with the two independent
sonable results even in the immediate vicinity of the critical variables density p and temperature T. The dimensionless
point. Helmholtz energy ¢J=A/CRT) is commonly split into a part
All the correlation equations given in this article corre- depending on the ideal-gas behavior ¢J0 and a part which
spond to the ITS-90 temperature scale. takes into account the residual fluid behavior ¢Jr, namely
r/J( 8, 'T) = r/J 0 ( 8, 'T) + tll( 8, 'T), (2.1)
1.3 Organization of the Article where o=p/Pc is the reduced density and 7=TcIT is the
inverse reduced temperature. Both the density p and the tem-
In Sec. 2 we give a brief review of the application of perature T are reduced with their critical vallles, Pc ~mci To;,
empirical equations of state explicit in the Helmholtz energy respectively.
as a function of density and temperature; this combination of Since the Helmholtz energy as a function of density and
variables is one form of a fundamental equation. The tech- temperature is one form of a fundamental equation, all the
niques used for the development of the new equation (multi- thermodynamic properties of a pure substance can be ob-
property fitting, optimization procedure) are described tained by combining derivatives of Eq. (2.1). Table 3 gives
briefly. Section 3 deals with the liquid-vapor, solid-vapor, the relations between Eq. (2.1) and the properties considered
and solid-liquid phase equilibria of carbon dioxide. The in this article. The vapor pressure and the densities of satu-
available data are discussed. In addition to the equation of rated liquid and saturated. vapor can be determined from an
state, short supplementary equations have been developed equation explidt in ¢J by simultaneous solution of the equa-
for the temperature dependence of the melting pressure tions
Pm' the sublimation pressure P sub' the vapor pressure p s ,
the saturated liquid density p', and the saturated vapor den-
sity p". The experimental information available for the
R~~' = I + 0' ¢J~( 8',7), (2.2a)

single phase region of carbon dioxide is discussed in Sec. 4.

In Sec. 5 a detailed description of the new approach for ~=l+o".4.r(o"
RTp" 'f'8,7 ) , (2.2b)
representing the critical region is given. Possibilities and
limitations of the use of nonanalytic terms in empirical wide-
range equations of state alC uullillCd. Thc uew coudutiull Ps (1 1
1 (p') _ r " r'.'"
RT p"-{l)-ln p" -¢(6,7)-¢(O ,7),
equations for both the ideal and the residual part of the
(2.2c)
Helmholtz free energy are presented in Sec. 6. The final data
set and the bank of terms used for the development of the which correspond to the equality of pressure,· temperature,
new equation are given. Comparisons of properties calcu- and specific Gibbs energy (Maxwell criterion) in the coexist-
lated from the new equation of state for carbon dioxide with ing phases.
selected experimental data and those values calculated from
prior correlations are presented in Sec. 7. A discussion of the
extrapolation behavior of the new fundamental equation is 2.2 Helmholtz Energy of the Ideal Gas
included in this section. Finally, the uncertainties of the new
The Helmholtz energy of the ideal gas is given by
formulation are estimated and tahles of the thermodynamic
properties of carbon dioxide are listed in the Appendix. AO(p,T)=hO(T)-RT-TsO(p,T). (2.3)

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1517

TABLE 3. Relations of thermodynamic properties to the dimensionless Helmholtz function 4> consisting of cpo and cpr; see Eq. (2.1)

Property and common

thermodynamic definition Relation to the reduced Helmholtz energy cp and its derivatives a
Pressure: p(8,r) = 1 + 84>r
p(T,p)= -(aAlavh pRT t5
Entropy:
s(T,p)= -(aAlaT)v
-+- =
s(8 r)
r( 4>~+ 4>~) - 4>0- 4>r
Internal energy: u(8,r) _ 0 r

u(T,p)=A - T(aAlaT)u liT- r{4>".+4>r)

Isochoric heat,capacity: , c u(8,r) = _ ~(.I,.O +.I,.r )
cv(T,p) = (aul aT)v R 'PrT 'PTT
Enthalpy: h(8,r) 0 r r
h(T,p)=A - T(aAlaT)v
liT = 1 + r(4)T + 4>T)+ 84>8
-v(aAIJvh
(1 + 84>~- 8r4>~r)
2
Isobaric heat capacity: c p( 8, r) _ 0 r
cp(T,p) = (JhIJT)p -R---~(4)rr+4>,,.,,.)+ 11281>81 821>8t5
Saturated liquid heat capacity: c u( r) 1 + 84>~- 8r4>~".
cu(T) = (ahIJT)p + T(JplaT)v -R- = - ~(4)~T + 4>~T)+ 1 +284>~+ 824>~t5

(l+&/J~-8rdJ~~)-:~ ?;]
. (dPs/dT)/(apIJvhlu=v'
.[

Speed of sound: 2
w ( 8, r) _ r 2 r (1 + 84>~- 8r4>~".)2
w(T,p) = ~(Jplap)s ~ -1 +284>0+ 84>00- ~(4)~T+ 4>~".)
J oule-l homson coefficient: - (OcfJ8T 0 2 cfJ80 T orcfJ8T)
/-t(T,p)=(aTIJph
Fugacity:

In(~T,p))= J: [v~:) -~ldPT In ~ 8, r) = 4>r + 84>'8-ln( 1+ 84>~

Second virial coefficient: B(r)pc= Iim4>~(o,7")

B(7)= lim(J(p/(pRT)lap)T 0->0
p->O

Third virial coefficient:

1
e(T) = 2" 2
lim{a [pl(pRT)]lap2h C( r) p~ = lim 4>~O< 8, 7")
p->O 0->0

The enthalpy hOof the ideal gas is a function of temperature stance. Thus, the equation for the residual part has to be
only, and the entropy SO of the ideal gas depends on tempera- determined in an empirical way by optimizing its functional
ture and density. Both properties can be derived from an form and fitting its coefficients to experimental results. b
equation for the ideal-gas heat capacity c~. When c~ is in- Since the Helmholtz energy is not accessible to direct mea-
serted into the expression for hO(T) and SO(p, T) in Eq. (2.3) surements, a procedure has been developed which allows the
one obtains establishment of an empirical equation for the residual part
of the Helmholtz energy by using data of different proper-
ties.

2.3.1 Fitting an Empirical Equation for cfJr to Data

- RT[ln(p/ Po)] - Ts8, (2.4)
where Po=pol(RTo) is the density, h8 the enthalpy, and sg the An empirical equation for the residual part of the Helm-
entropy of the ideal gas in a reference state. The final equa- holtz energy can be written as cjJf(8,T, ii), where nrepresents
tion for cjJ°=Ao/(RT) is given in Sec. 6.1. the vector of coefficients to be fitted. Ahrendts and Baehr3 !
showed that the determination of an optimum set of coeffi-
cients results in the minimization of a sum of squares, de-
2.3 Residual Part of the Helmholtz Energy
fined as the sum of partial sums of squares belonging to the
In contrast to the Helmholtz energy of the ideal gas, no different properties included into the fit:
theoretical approach is known which yields a sufficiently ac-
curate equation for the residual part of the Helmholtz energy ~hroughout this article the word "data" is used to characterize such ex-
and which is valid in the whole fluid region of a pure sub- perimental results.

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 1518 R. SPAN AND W. WAGNER

x' = j~l XJ= j~ '~l

A sophisticated correlation equation for the residual part
[[Z"p-',..e(;;,p ,Y"p,il)]'] ,(2.5) of the Helmholtz energy consists of an extensive sum of
tot j,11l terms. Hence, the mathematical form of a single term can be
where J is the number of properties involved in the fit Mj the associated with different functional groups ranging from
number of data points used for the jth property, zexp the value simple polynomials of the reduced density 8 and the inverse
measured for any property z(x,y), and Zeak the value calcu- reduced temperature 'T to complicated exponential expres-
lated for xexp ' Yexp from the correlation equation with the sions (see the bank of terms given in Sec. 6.2). In the known
parameter vector n: The universal variable x usually corre- optimization procedures, only the total number of terms of
sponds to T, but Y can correspond to p [e.g., p(T,p)] or to p the optimized equation is limited to a preselected value. Dur-
[e.g., w(T,p)] and can even vanish [e.g., Ps(T)]. The variance ing this work, additional limitations with respect to the num-
O"~ot is explained in Sec. 2.3.3. ber of terms belonging to special functional groups have
The determination of it by minimizing ¥ results in a lin- turned out to be usefuL The actual revision of the optimiza-
ear system of normal equations if z depends on T and p and tion procedure allows the definition of such limits to special
if the relations between z and (1/ and the derivatives of ¢/ are term forms. The new equation for carbon dioxide has been
Imear (see Table J). If these conditions are not fulfilled, the developed With a limit to four nonanalytic terms to aVOId
data have to be linearized by suitable procedures 32 ,5 or non- unreasonable behavior in the critical region (cf. Sec. 5.2) and
33 eight polynomial terms to improve the extrapolation behav-
linear algorithms have to be used. A detailed description of
the iterative fitting process resulting from the use of data ior Ccf. Sec. 7.3 and Span and Wagner35 ).
with nonlinear relation to cpr is given by Setzmann and As pointed out by Setzmann and Wagner,6,30 the optimi-
30 zation procedure only works with linear or linearized data.
Wagner. In this article, the linear data of the ppT relation,
30
. of the internal energy ll, of the isochoric heat capacity C u , of This restriction leads to the previously described cyclic
the third virial coefficient C, and linearized data of the en- process, consisting of linearizing the data, optimizing the
thalpy h, of the isobaric heat capacity cp of the homogeneous mathematical structure of the correlation equation, and non-
region and the saturated liquid, of the speed of sound w of linear fitting of the coefficients; these steps are typical for the
the homogeneous region, the saturated liquid, and the satu- development of such fundamental equations of state.
rated vapor, and of the Maxwell criterion were used in linear
fitting algorithms. Within the nonlinear fitting process, data 2.3.3 The Procedure of Weighting
of all these properties and of the Joule-Thomson coefficient
When data sets of different properties are used for the
f.l, which cannot be linearized in a reasonable way, were
development of a correlation equation, it is necessary that the
used directly which means without any linearization.
residual (Zexp - Zeak) in Eq. (2.5) is reduced with a suitable
2.3.2 Optimizing the Mathematical Form measure for the uncertainty of the data point. According to
the Gaussian error propagation formula, the uncertainty of a
The fitting procedure described above supposes that the
measured data point is given by
mathematical form of a correlation equation is already

u~,p=([ d::Lu;+[ d~I,(T;+[ d!T,u~),

known and only thf' cOf'ffi~if'nt, 11 havp to be determined.
(2.6)
Since a universal form for an equation describing the re-
sidual part of the Helmholtz energy is not known, this re-
quirement is not satisfied. Thus, a suitable mathematical where u x ' u y ' and o"z are the uncertainties with respect to
structure has hrst to be established. With the exception of the the uncorrelated single variables x, y, and Z; the partial de-
equation of state developed by Ely and co-workers,14.15 the rivatives of Z can be calculated from a preliminary equation
form of the equations existing for carbon dioxide has been of state.
determined in a subjective way, based on the experience of In order to have an additional influence on the data set, a
the equation maker by trial and error. To improve this pro- weighting factor f wt is introduced. The total variance a tot of
cedure. Wagner and co-workers developed different optimi- a data point used in Eq. (2.5) is defined as
zation strategies 3-+. I .i.6 by introducing objective criteria for the (2.7)
selection of a mathematical structure. The mathematical
structure applied by Ely and co-workers was developed by In this way, weighting factors f wt> 1 enlarge the influence of
Schmidt and Wagner-+ for oxygen by the use of the "evolu- a data point with respect to the sum of squares and weighting
tionary optimization method," EOM. 13 factors f wt< 1 reduce it. Usually f wt is equal to one and a?ot is
In this work. the optimization method developed by Setz- equal to u~xp; in some cases, however, different weighting
mann and Wagner6 was used for the determination of a suit- factors are used to compensate for effects caused by the
able mathematical structure. Minor improvements were in- structure of the data set. These effects may be divided into
troduced. concerning the stochastic part of the optimization the following groups:
procedure. More important. however, are the changes made • In a special region there are only a few (j wt> I) or excep-
in the Setzrnann- Wagner procedure with regard to the han- tionally many (j wt< 1) data points.
dling of different functional forms from thc "bank of • An cAlcnsivc data :'>ct with largc cxpcrimcntal uncertainties
t.erms. can be transformed into a smaller, but more consistent data

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1519

set by suitable data selection if wt> O. of the decimal point were used. Data corresponding to the
• After correcting systematic deviations, a data set yields IPTS-48 temperature scale were converted to IPTS-68 ac-
results much better than expected from its original experi- cording to the 'procedure given by Bedford and Kirby.39 For
mental uncertainty if wt> 1). temperatures between 90 K and 900 K, the temperature
• In a special region, enlarged, but difficult assignable un- scales ITS-27 and IPTS-48 do not deviate from each other
certainties of the selected data are expected if wt < 1). and data older than 1927 were not used.
The algorithm used for the conversion from IPTS-68 to
To achieve as much transparency with regard to the data
the ITS-90 temperature scale 38 causes an additional uncer-
set as possible, the tables presenting the selected data (see
tainty of ± l.5 mK for temperatures below 273.15 K and
Sec. 4) contain additional information on the uncertainties
± 1 mK for temperatures above 273.15 K. This additional
used in the weighting procedure as well as on the mean value
uncertainty is not considered in the uncertainties given in the
of the weighting factor. Weighting factors deviating signifi-
tables of this section, since these uncertainties were mainly
cantly from fwt= I are discussed.
used for consistency tests between data of different authors.
In this case, the uncertainty in the absolute temperature,
3. Phase Equilibria of Carbon Dioxide which is influenced by the uncertainty of the conversion, is
less important. The comparison between two very similar
temperature values is not influenced by the uncertainty of the
An accurate description of phase equilibria by auxiliary
t::Ljualium; i~ an important precondition for the development
conversion if both temperatures are converted with the same
procedure.
of a wide-range equation of state and is also helpful for users
who are only interested in phase equilibria. Therefore, all 3.1 Triple Point
available experimental information on the triple point, the
critical point, the melting pressure, the sublimation pressure, Uunng the last YU years, the trIple-pomt temperature ot
the vapor pressure, the densities of saturated liquid and va- carbon dioxide has been determined by numerous authors
por, and on caloric properties on the liquid-vapor phase but the data situation for the triple-point pressure is rather
boundary have been reviewed. With the exception of the poor. Fortunately, the few measurements available are very
caloric properties, simple correlation equations have been consistent with each other. Table 4 shows selected data of
developed for the temperature dependency of these quanti- the triple point of carbon dioxide. After a comprehensive
ties. review of the existing data, we have chosen the following:
To condense the description of the data situation, the char- T t = (216.592± 0.003)K, (3.1)
acteristic information on the single data sets is summarized
in tables for the corresponding property. The data sets have Pt=(O.51795± O.OOOlO)MPa. (3.2)
been divided into three groups. The assignment considers the
critically assessed uncertainty of the data, size of the data set, Data of the density of the saturated liquid and the satu-
and covered temperature range. In addition, attention is paid rated vapor at the triple point are not available, but the evalu-
to the data situation for the respective property. Group I ation of the corresponding correlation equations given in
contains the data sets used for the development of the corre- Sees. 3.6 and 3.7 yields
sponding correlation equation. Group 2 contains data sets p;'=(1178.53± O.18)kg/m 3 , (3.3)
suitable for comparisons. Compared with group I data, these
data decline at least under one of the three aspects mentioned p;' = (13.76l4::!:: O.0034)kg/m 3 • (3.4)
above. Group 3 contains very small data sets and data sets
with rather high uncertainty. Consideration of these data is 3.2 Critical Point
not rt':lson:lhle on the level of accuracy aspired to here. Nev-
ertheless this means no devaluation of these data sets - the Altogether, data of the critical point of carbon dioxide are
whole ranking is intluenced more by the quality in relation to given in 75 papers. Table 5 shows selected values of the
the best available reference data than by an absolute level of critical temperature, the critical pressure, and the critical den-
uncertainty; for other purposes even group J data sets may SIty. The values found for the CrItIcal denSIty agree well
be very useful. within the expected uncertainties, but the values for the criti-
Since the new correlation equations and all temperature cal temperature show significant differences, far beyond the
values in this article correspond to the ITS-90 temperature uncertainties given by some of the authors. Essentially, the
scale. 36 the temperature values of the available data, based differences in the critical pressures can be explained by the
on older temperature scales, were converted to ITS-90. The variation of the vapor pressure with the assumed critical tem-
conversion from the IPTS-68 temperature scale to ITS-90 perature.
temperatures was carried out based on the internationally In the course of this work, no new attempt has been made
agreed procedure of Preston-Thomas et al.,37 explained by to determine the critical parameters of carbon dioxide, but
Rusby.38 The number of digits of the converted values was the evaluation of Duschek et al. 58 was tested under different
increased by one digit in order to guarantee numerically con- aspects. No reason for altering the data became obvious.
sistent reconversion. but not more than four digits to the right Thus, we have used

J. Phys. Chem. Ret. Data, Vol. 25, No.6, 1996

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 1520 R. SPAN AND W. WAGNER

TABLE Selected data for the triple point of carbon dioxide

Source Year T (K)a aT p (MPa) I1p (MPa)

40
Meyers and Van Dusen 1933 216.5885 ±O.OOS 0.517 99 ±O.OUU 06
Ambrose41 1957 216.5885 ±O.OO2
Lovejol2 1963 216.591 5 ±O.OOI
Haro et a1. 43 1979 216.5945 ±O.OO2
Staveley et al. 44 lY81 216.::591 0.517
Blanes-Rex et al. 45 1982 216.5945 ±O.OOl
Pavese and Ferri 46 1982 216.5915 ±O.OO2
Bedford et al. 47 1984 216.5905 ±O.OOl
Bonnier et aJ. 48 1984 216.591 7 ±O.OOO2
Duschek 49 1989 216.5915 ±O.OO3 0.51795 ±O.OOO 1

aAll temperatures were converted to ITS-90. Up to an uncertainty of 0.1 mK an additional digit is added to
consistent reconversion to IPTS-68 temperatures.
uncertainty of the conversion from IPTS-68 to ITS-90 is not considered here.

Tc= (304.1282± O.015)K, temperature assumed Michels et al. 6o and Clusius et al. 61
deviate from the rel.:t:.Ill valul;; [eI. Dg. (J.l»), llll their tem-
Pc= (7.3773± O.0030)MPa, (3.6) perature values were corrected according to
Pc=(467.6± (3.7)
K, (3.8)
(The additional digit in Tc is given to guarantee numerical
consistency in any reconversion to the IPTS-68 temperature K (3.9)
scale.)
after their conversion to ITS-90 temperatures.
3.3 Pressure The corrected data are consistent within the expected un-
certainties and were used to establish a simple correlation
There are only two available sets of measurements de- equation for the melting pressure:
sen bing the metring pressure uf cwbun dioxide. In 1942
Michels et al. 60 measured 25 melting pressures at tempera- Pm
tures between 217 K and 266 K, to pressures
(3.10)
Pt
between 0.9 MPa and 284 MPa. In Clusius et al. 61
published 21 data, covering the range from 2t7 K to 222 K, with 1~=:Z16.592 K, pt=O.51795 MPa, 01 = 1955.5390, and
corresponding to 0.5 MPa to 24 MPa. a2=2055.4593. The equation is constrained to the tripIe-
Unfortunately, these data sets are inconsistent with each point pressure by its functional form. The representation of
other and with recent data of the triple point pressure. In both both the corrected and uncorrected data is shown in Fig. L.
experiments, the thennometers were calibrated at the triple- The uncertainty of Eq. (3.10) is estimated to be
point of carbon dioxide. Since the values of the triple-point tiPmIPm~± 1.5% for Tt~T~225 K and :!:O.S% for

TABLE 5. Selected data for the critical point of carbon dioxide

Source Year Tc Pc (MPa) Pc (kglm3)

and Chen so 1972 304.182

1974 304.1192±O.OO4 467.8:t2.2
3
Angus et al. 1976 304.202:± 0.05 7.3858:tO.OO5 468±5
Lipa et 1977 303.9170:± 0.005
Moldover et al. 53 1979 304.122 7.375 467
8aade 54 1983 304.122 7.375 467
Edwards 5S \9S4. 3M.09'64.:t 0.0001
Sengers and Levelt Senger,,,S<> 1986 304.122 7.372 468
Albright et 1987 304.0992 7.3719 467.67
Ely e! aJ. 21 1987 304.1192 7.37479 466.5
Chen al. 57 1990 304.0992 7.3916 467.69
Chen et at.·27 1990 304.1192 7.3753 467.83
Duschek el 01.58 1990 304.1282± 0.015 7.3773±0.O03 467.6±O.6
Abdulagatov et al. 51 1991 304.1272:.:0.010 4675

'All temperatures converted to ITS-90. Up to four digits beyond the decimal point an additional digit is
added to guarantee consistent reconversion to IPTS-68 terntper'atures.
trrhe uncertainty of the conversion from [PIS-68 to not considered here.

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1521

10~----------------------------~ T 90= T Bi.90 - 0.049 K. (3.11)

The sublimation pressure can be described by the correla-
ft
~ O~--~~~. .~~ar..,~..~----~~ tion equation

-I::l...

Tt
~ -lOL---~mH~~~--~--~--~--~--~
In (
PSUb)Tt ( (
Pt = T' all - ~
T)
+ a2 ( 1 - ~
T) L9

~ 216 217 218 219 220

ft T) 2.9) ,
(

-:~
~ +a3 1-~ (3.12)
I::l...

..
:! :
with Tt =216.592 K, pt=0.51795 MPa, al = -14.740846,
!

~
0
! a2=2.4327015, and a3= -5.3061778. The equation is con-
I
strained to the triple-point pressure by its functional form.
Figure 2 compares group 1 and group 2 data with values
220 230 240 250 260 270 calculated from Eq. (3.12). The uncertainty of the new equa-
Temperature T / K tiul1 is csLilllaLcll Lo uc ~Psub:::S -'- 2.50 Pa fur 18.5 K::::::: T~ Tt ,
61 61 ± 100 Pa for 170 K::::::; T::::::; 185 K, and dPsub::::::; ± 50 Pa
dPsub::::::;
o Clusius et al. • Clusius et al. (corr. data)
6O for T::::::; 170 K. Bedford et al. 47 concluded that the most recent
o Michels et al. 60 • Michels et al. (corr. data)
value for the sublimation temperature at normal pressure
FIG. 1. Relative deviations of experimental melting pressure data from val- (P0=0.101325 MPa) is T= 194.6857 K±0.0030 K~ iteration
ues calculated from the melting pressure equation, Eq. (3.10). In this figure, with Eq. (3.12) yields T=194.6855 K.
both the corrected and the uncorrected data are plotted (see Sec. 3.3).
Equation (3.12) was fitted to data at temperatures above
1.54 K. The low temperature data of Bryson er ai. 75 are not
represented to within the uncertainty given by the authors,
225 K < T~ 270 K. The simple form of the equation should
but the deviations do not exceed 0.01 Pa for T >85 K and
ensure reasonable extrapolation to higher temperatures.
0.0001 Pa for T::::::; 85 K, respectively.

3.4 Sublimation Pressure

3.5 Vapor Pressure
Due to the widespread use of solid carbon dioxide, the
data situation for the sublimation pressure is exceptionally Information on the vapor pressure of carbon dioxide is
good. The available data sets for the sublimation pressure of given by 36 data sets; the corresponding information is sum-
carbon dioxide are given in Table 6. The data are classified marized in Table 7 (repeatedly published data sets were only
according to the procedure described above. The data set of listed once). The very accurate data set of Duschek et al. 58
Bilkadi et az.7 4 had to be corrected due to a difference be- describes the vapor pressure from the triple-point tempera-
tween the recent triple-point temperature and the one used by ture up to the critical temperature. Only this data set was
Bilkadi et al. for calibration purposes. The corrected tem- selected to develop the new vapor pressure equation. For the
perature is given by data converted to the ITS-90 temperature scale, the optimi-

TABLE 6. Summary of the data sets for the sublimation pressure of carhon dioxid~

No. of Temp. range,

Source Year data T(K) IlT(mK) IlPsub Group
62
Bois and Wills 1899 8 149-196
Kuenen and Robson63 1902 6 195-215 :t 32
Onnes and Weber64 1913 9 90-106
Siemens 65 1913 29 118-195 :t20
Wcbcr and Onncs 66 19lJ 15 104-138
67
Henning 1914 18 192-195 :t 100 Pa
Heuse and Ott068 1931 19 193-195 :t2
Heuse and Otto69 1932 7 195 :tl
Meyers and Van Dusen 40 1933 28 195-217 :to.02%
Giauque and Egan 70 1936 12 154-196 :tl :t3 Pa 2
Tickner and Lossing71 1951 13 106-154 :t 300 3
Ambrose 72 1955 16 179-198 ±I :t4 Pa
Hiza 7 :' 1970 216 :t1O
Bilkadi et al. 74 1974 132 154-217 :t20 1
Bryson et al. 75 1974 62 70-103 2
Bedford et al. 47 1984 1 195 :t3
Fernandez-Fassnacht and del Rio 76 1984 21 194-243 :tl :t 100 Pa

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 1522 R. SPAN AND W. WAGNER

500
~
0...
........
.0
;:l 0
~
<'J

-500
150 160 170 180 190 200 210 220
Temperature T / K
o Ambrose 72 • Bedford et al. 47
o Giauque and Egan 70 o Fernandez-Fassnacht and del Rio 76

V Bllkadl et al. 7.1 .6. Bilkadi hat. 74 (corr. data)

FIG. 2. Absolute deviations ~Psub= (Psub.exp - Psub.calc) of selected experimental sublimation pressure data from values calculated from the sublimation pressure
equation (3.12). In this figure. both the corrected and the uncorrected data of Rilkarli pf 0174 ~re plotteti (see Se~ ~4)

TABLE 7. Summary of the data sets for the vapor pressure of carbon dioxide

No. of Temp. range,

Source Year data T(K) ~T(mK) ~Ps Group
63
Kuenen and Robson 1902 l3 217-273 ±32
Keesom 77 1903 4 298-304 ±20 ± 1000 Pa
Jenkin and pye 78 1914 23 222-296 ±1O ±0.2%
Bridgeman79 1927 30 273 ± 140 Pa
Meyers and Van Dusen-+o 1933 67 217-304 ±0.01% 2
Michels et al. 8O 1936 9 276-304 ~±1O ~ ± 100Pa 3
Roebuck et al. 81 1942 10 223-304
Michels et af. 82 1950 19 217-276
Reamer et al. 83 1951 2 279, 294 ± 14 ± 0.1 CJc
Bierlein and Webster 8-+ 1953 9 274-304 ±20 ±0.01% 2
Cook85 1953 9 293-'304 ± 10 3
Cook 86 1953 6 293-303 ± 10 ± 1000 Pa
Schmidt and Thomas 87 1954 6 274-304 ::1::0.05%
Wentorf88 1956 304 ±I ± 132 Pa
Kletskii 89 1964 2 260, 266
GreIg and Uadson 9O lY66 1 273 ±o.om 4 G7c
Edwards and Johnson 91 1968 28 273
Vukalovich et al. 92 1968 4 301-304
Kirillin et al. 93 1969 3 283-303
Q
KiluluLluv el al. .1 1972 5 243-283
Levelt Sengers and Chen so 1972 37 267-304 ±2 ±500 Pa
Fredenslund and Moll erup 95 1974 5 223-293 :=20 : :': : 2000 Pa
Gugoni et al. 96 1974 241-269
BC:iscrcr and Robinson 97 1975 274 :'::60 :':: 24000 Pa
Da\'alos ef £11.98 1976 230-270 ± 10 ± 3000 Pa
Stead and Williams 99 1980 9 220-300 : :': : 10 ± 0.1 CJc
'-'S
Kwang-Bae ef al. loo 1982 5 263-298 :::':::30 ±3500 Pa
Al-Sahhaf ef al. IOI 1983 4 219-270 ±0.141K
Baade s4 1983 227 220-304 :::':::3 ±80 Pa
Fernandez-Fassnacht and del Rio 76 1984 21 217-243 ::'::1 ± 100 Pa
Kratz lO2 1984 289-294 :::':::3 ±0.OO5%
Holste et al,IO.1 1987 12 250-303 :::':::10
Brown et al. 104 1988 4 220-270 ±20 ±O.I%
Duschek ef al,ss 1990 109 217-304 ±3 '-'S :::':::0.005%
Shah ('f al. 105 1991 276+293 ±20 :::':::0.5%
Yurttas et al. lOs " 1994 230-280 :::':::3 :::':::0.01%

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1523

0.05~--~~~--~~~----------------------------~~--------~~~~~~

0.
x
0
0

-..~
u
(;l
u. -0.05
,~
I
, p"
x
l!- 0.05
~ I> <I
'-"'
0
a
-"
0

296 298 3 0 302 304

Temperature T / K

t> Bierlein and Webster84 <l Holste et al. 103

102
<>Fernandez-Fassnacht and del Rio 76 o Kratz
X Meyers and Van Dusen40 L::,. Levelt Sengers and Chen so
o Baade54 "V Michels et ai.
82

• Duschek et al. S8
3
- - - Angus et al. (aux. eq.)

FIG. 3. Relative deviations of selected experimental vapor pressure data from values calculated from the vapor pressure equation, Eq. (3.13). Vapor pressures
calculated from the corresponding equation of Angus et al. 3 are plotted for comparison.

TABLE 8. Summary of the data sets for the saturated liquid density of. carbon dioxide

No. of Temp. range,

Source Year data T(K) ~T (mK) ~p' (9'c) Group
l06
Amagat 1892 35 273-304
Behn 107 1900 11 215-297
Lowry and Erickson 108 1927 8 267-296 ::to.1
Michels et al. 8o 1936 9 276-304 ~::tlO
Reamer et al. 8:1 1951 2 279+294 ::'::20 ::'::0.2
Bierlein and WebsterX~ 1953 9 274-304 ::t20 ::'::0.5
Cooks) 1953 11 293 303 ±1O ±O.5
Vukalo\'ich et al. 92 1968 4 301-304 ::'::0.5
Straub lO9 1972 34 294-304
Gugoni et al. 96 1974 3 241-269
Be;~erer and Robinson 97 1975 274 ::'::60
Baade5~ 1983 115 220-304 ::t3
Haynes llO 1985 17 220-300 ::t30 ::to. I
EsperlI !." 1987 266-303 ::to.2
Holste et al. lo .<." 1987 266-303 ::t 10 2
Duschek et al. 5~ 1990 50 217-304 ::t3 ::'::0.015°
Abdulagato\' et al. 59 " 1994 304

"The data sets of Esperlll and Holste et al. 103 are different evaluations of the same measurements.
h At temperatures above 300 K. the uncertainty rises to :!: 0.2«<.

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 1524 R. SPAN AND W. WAGNER

0.1~------------------------------------------~~----------------~
----~~£>­
Q..
<1
o
<>
,/
,,--0- <>
<><>
<>
<><>
<> •
o
~

-0.1~~~~~~~~~~--~~~~--~~~~--~~~~
220 240 260 280 30
Temperature T / K
lll 3
<l Holste et at. 103 t> Esper - - - Angus et at. (aux. eq.)
llO 58
<> IIayncs • Duschek et al.

FIG. 4. Relative deviations 100 dp'=100 (p~xp-P~alc)lp~xp of selected experimental saturated liquid density data from values calculated from Eq. (3.14).
Saturated liquid densities calculated from the corresponding equation of Angus et at. 3 are plotted for comparison.

zation procedure yields the same mathematical form used by the experimemal uncenaimy of (hese data, (he uncenaimy of
Duschek et al. 58 to describe this data set in the IPTS-68 tem- Eq. (3.13) is estimated to be APs~::t 0.012% for the whole
perature scale; only the coefficients ai have changed. The temperature range.
vapor pressure equation can be written as The dashed line in Fig. 3 corresponds to values calculated
from the vapor pressure equation of Angus et al. 3 after con-
version to ITS-90. The results of this correlation are remark-
(3.13) ably good but, of course, the most accurate data available
today are not represented to within their experimental uncer-
with Tc=304.1282 K, Pc=7.3773 MPa, al=-7.060 2087, tainty.
a2= 1.9391218, a3= -1.6463597, a4 = -3.2995634, tl = 1.0,
t 2=1.5, t3=2.0, and t4=4.0. 3.6 Saturated Liquid Density
Figure 3 shows both the good agreement between the data
sets marked as group 1 and group 2 data and the representa- Table 8 shows information on the 17 data sets of the satu-
tion of the data measured by Duschek et al. 58 Considering rated liquid density of carbon dioxide. Again, only the data

TABLE 9. Summary of the data sets for the saturated vapor density of carbon dioxide

No. of Temp. range,

Source Year data T (K) dT(mK) dp" (%) Group

Amagat lO6 1892 35 273-304

Lowry and Erickson 108 1927 8 267-296 ±0.7 3
Michels et al. 8o 1936 9 276-304 :o.:;±10 3
Reamer et al. 83 1951 2 279,294 ±20 ±0.2
Bierlein and Webster 84 lQ"~ Q 274-~O4 ±20 ±0.5
COOk85 1953 11 293-303 ::t1O ::to.5
Vukalovich et al. 92 1968 4 301-304 ±0.8
Kholodov et al. 94 1972 5 243-283 3
Straub 109 1972 34 294-304
Besserer and Robinson 97 1975 274 ±60
Baade5~ 1983 145 220-304 ::t3
Esper lll .a 1987 5 245-304 ::to.5
Holste et al. 103a 1987 5 245-304 ± 10
Duschek et al. 58 1990 42 217-304 ±3 ::to.025 D
Abdulagatov et al. 59a 1994 2 304

aT he data sets of Esperlll and Holste et al. 103 are different evaluations of the same measurements.
b At temperatures above 295 K, the uncertainty rises to ± 0.25%.

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1525

0.5~---4RH~~r-----~~------------~~-------------t

e.. 0
:: ~
~
.........
,-..... Tt
u
:] -0.5
,~
..e..
220 240 260 280 300
:: ~ 0.05
~
'-'
0
0
,...-t
0

-0.05
Tt •
220 240 260 280 300
Temperature TIK
<l Holste et al. 103
0 BaadeS4 D.. Straub109
I> Esper
l11
•• Duschek et al. 58
Michels et at. 80
94
X Kholodov et al. <> Abdulagatov et al. S9
3
_ _ _ Angus et at. (aux. eq.)

FIG.5. Relative deviations of selected experimental saturated vapor density data from values calculated from Eq. (3.15). Saturated vapor densities calculated
from the corresponding equation of Angus et ai. 3 are plotted for comparison.

set of Duschek et al. 58 is used to develop a simple saturated Figure 4 shows the poor situation regarding group I and
liquid density equation. Group 2 is restricted to data sets group 2 data and the highly accurate representation of the
which deliver uncertainties comparable with common uncer- group 1 data. The dashed line corresponds to values calcu-
tamtIes in the single phase region, that means lated from an auxiliary equation given by Angus et al. 3 for
Llp'::S±0.2% outside the critical region. Unfortunately, this the saturated liquid" density. .
criterion is only met by the data sets of Haynes, 110 Esper, III
and Holste et al.; 103 all the other data proved to be less ac- 3.7 Saturated Vapor Density
curate.
For the whole temperature range, the simple correlation Data on the saturated vapor density of carbon dioxide are
given in 15 sources, which are listed in Table 9. If the same
In ( ~') =? 4
ai
( T;
1-- t·
1 (3.14) criterion as mentioned in Sec. 3.6 is used to distinguish be-
Pc 1=1 Tc tween group 2 and group 3 data, only the data of Michels
et al. 80 can be assigned to group 2. While numerous authors
with Tc=304.1282 K, Pc=467.6 kg/m3, al = 1.9245108 1

a2=-0.62385555, a3=-0.32731127, a4=0.39245142, published accurate ppT data for the homogeneous gas re-
gion, even recent data sets of the saturated vapor density
t l =0.34, t2=~' t3=~' and t 4=Jt describes the data of Du-
schek et al. 58 within their experimental uncertainty. For this scatter by up to ± 0.5% in density.
equation, both the coefficients and the exponents differ from The new correlation equation for the saturated vapor den-
the formulation given by Duschek et al.,58 which is valid for sity,
temperatures on IPTS-68. The changed functional form of
the correlation resulted in slightly improved results in the In ( ~") =;.?
5
ai
( T)
1 - - f·" (3.15)
Pc ,-I Tc
critical region. According to the uncertainty of the selected
data, the uncertainty of Eq. (3.14) is estimated to be with Tc=304.1282 K, Pc=467.6 kg/m3, al = -1.7074879,
Llp' ::s±0.015% for Tt ::ST::S295 K, Llp'::S±0.04% for a2=-0.82274670, a3=-4.6008549, a4=-10.111178,
295 K< T::S 303 K, and Llp'::S ± 1% for 303 K < T::S Tc. a5= -29.742252, t[ =0.340, t2=~' t3= 1, t4 =~, and t5= ¥,

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 1526 R. SPAN AND W. WAGNER

TABLE 10. Summary of the data sets for caloric properties on the liquid-vapor phase boundary of carbon
dioxide

No. of Temp. range,

Source Year Property data T(K) Uncertainty Group

Eucken and Hauck"2 1928 C(T 223-293

Novikov and Trelin l13 1960 w" 18 293-304
Amirkhanov et al. 114 1972 C 'a
v 11 304
Pecceu and Van Dael 115 1972 w 23 217-293 Llw'=±I%
Magee and Elyll6 1986 Ca 77 220-303
Abdulagatov et al. 59a 1994 c~/<a 8 304

aThe specific isochoric heat capacity on the phase boundary cannot be measured directly; such data can only be
determined by extrapolation from the homogeneous regions.

describes the group 1 data of Duschek et aI. 58 within their ap ) dps

T ( aT dT
experimental uncertainty. Compared with the corresponding
equation of Duschek et al., 58 both the coefficients and the (3.16)
exponents of the correlation have been revised in order to c;(T)=cO"(T)- (p')2 (a:)
achieve a slightly improved representation of the data set up T
which has been converted to the ITS-90 temperature scale.
Again, the estimation of uncertainty can be guided by Up to temperatures of 295 K, the fraction in Eq. (3.16)
the experimental uncertainties. We expect the uncertainty of remains smaller than 20% of CO" and can be determined from
Eg. (3.15) to be ap"~±0.025% for Tt~T~295 K, a preliminary equation of Slate with an estimated uncenaimy
ap"~±0.08% for 295 K<T~303 K, and ap"~± 1% for
of less than 0.5%. Thus, the uncertainty caused by the trans-
303 K<T~Tc'
formation is less than 0.1 % in c;
and is therefore negligible
Figure 5 shows the inexplicably poor data situation, al- compared with the experimental uncertainty of the CO" data
though only measurements published since 1970 and the measured by Magee and Ely.116 At temperatures above
older data of Michels et al. 80 are plotted. The data set of 295 K, the influence of the fractional term increases rapidly
Duschek et al. 58 is the only one which enabled the develop- and likewise the uncertainty of the derivative cap/aph.
ment of an accurate correlation for the saturated vapor den- Therefore, converted CO" data at temperatures above 295 K
sity. The correlation equation of Angus et al. 3 yields reliable were used only for comparison; see Fig. 20.
results at temperatures above 275 K, where it mainly de-
pends on the data set of Michels et al. 80
4. Experinlental Basis of the New Equation
3.8 Caloric Data on the Liquid-Vapor Phase
of State
Boundary
In this section, the data sets which describe the thermody-
Table 10 lists information on the data sets which contain namic properties in the single-phase region of carbon dioxide
measurements of different caloric properties on the liquid- are presented. For each property considered in this work,
vapor phase boundary of carbon dioxide. No auxiliary equa both general information on all available data sets and more
tions have been developed for the description of these data. detailed information on the selected data sets is given in
Instead, group 1 data have been taken into account in the corresponding tables. Again, the data sets are classified into
development of the new equation of state, namely in the three groups as explained in Sec. 3. Since the data situation
linearized form during the optimization and in the direct in the homogeneous region is less unequivocal than the situ-
form during the nonlinear fit. More detailed information on ation of the different properties on the phase boundaries,
these data is given in Sec. 4.9 together with the selected data numerous data sets are associated with more than one group.
describing thc Maxwcll criterion. Usually these data sets are selected in regions with a poor
The only data which have not been taken into account by data situation, but they are used only for comparison in re-
direct nonlinear fitting are the data for the specific heat ca- gions in which more reliable data exist.
pacity CO" along the saturated liquid line. Table 3 shows that The information given for the selected data sets comprises
the relation between the dimensionless Helmholtz energy the uncertainties estimated by the authors, the uncertainties
and CO" contains the first derivative of the vapor pressure. estimated by ourselves, and the mean square value of the
Therefore, the inclusion of this property into the nonlinear fit weighting factor f wt, defined by Eq. (2.7). Particularly for
in a direct way would involve an interlocked relation to the some data sets which are more than 20 years old, the uncer-
Maxwell criterion according to Eq. (2.2). To avoid numerical tainties estimated by the authors and by ourselves differ con-
problems, the specific heat capacity along the saturated liq- siderably. The reason for this different assessment might be
uid line has been transformed to the specific isobaric heat based on the difference between the scatter and the uncer-
capacity at saturated liquid density according to the relation tainty of data, which was not considered by many of the

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1527

authors in the past. The uncertainties which we reviewed uncertainties. Nevertheless, in the region of overlapping
resulted from extensive comparisons and should be at least a (mainly at pressures between 8 MPa and 9 MPa) the data sets
reasonable estimation. These values were used in the weight- of Duschek et(1l. 154 and Gilgen et ai. 159 show small system-
ing procedure. atic deviations of up to about ± 0.01 % in density.
Section 4.9 contains the corresponding information on all On seven isotherms between 233 K and 523 K the two-
data used for the description of the liquid-vapor equilibrium. sinker measurements are supplemented by recent
measurements l60 ,160b with a new "single-sinker"
4.1 Thermal Properties
apparatus l60,16Oe which allows measurements up to pressures
Since 1903, the temperature and pressure dependence of of 30 MPa. On principle, for densities above 100 kg/m 3, the
the density of carbon dioxide has been investigated in 59 accuracy of this apparatus is comparable with the accuracy
papers, coveririg the single-phase region with a total of 5508 of the two-sinker apparatus, but since the measurements for
data points. Table 11 presents information on the available carbon dioxide were partly made in the test phase of the new
data sets including their classifica~ion. apparatus, slightly enlarged uncertainties had to be assumed.
For temperatures of up to 360 K and pressures of up to At pressures above 13 MPa, the adjusted data sets of
13 MPa, the description of the ppT relation is based mainly Lau,149 Kiril1in pt oL 93 ,137,140 ::mcl Mlchp.ls et 01 123 (see
on the data sets of Duschek et al. 154 and Gilgen et al. 159 Sec. 4.9.2) yield a smooth continuation of the course given
These data sets are supported by the Ps' p', p" data mea- by the data of Gilgen et ai. 159 Up to 30 MPa the adjusted
sured by Duschek et al.,58 by ppT data of the gas phase sup- data are generally consistent with the new single-sinker data
plied by Guo et al. 157 and by ppT data on the 313 K isotherm within ± 0.05% in density, but the adjusted data reach up to
measured by Nowak et al. 160d All these measurements were significantly higher pressures. Due to their high quality,
performed using the "two-sinker" buoyancy method,161 these adjusted data sets are used with substantially increased
which probably provides the most accurate ppT data avail- weighting factors; details are given in Table 12. For tempera-
able today. The data from the different two-sinker appara- tures between 523 K and 698 K and pressures up to 34 MPa,
tuses are consistent with each other far within their estimated the recent data of Fenghour et ai. 160a improve the data situ-

TABLE 11. Summary of the data sets available for the p p T relation of carbon dioxide

No. of Temp. range, Pressure range,

Source Year data T(K) p (MPa) Group
77
Keesom 1903 151 298-333 6.0-14.2
Jenkinll7 1920 82 236-303 1.4-9.7
Maas and Mennie 118 1926 16 203-373 0-0.1
Cooper and Maas 119 1930 30 273-297 0-0.1
Cooper and Maas l20 1931 47 242-350 0-0.1
Cawood and Patterson l21 1933 8 273 0-0.4
Michels and Michels 122 1935 190 273-423 1.6-25.3 1-2
Michels et al. 123 1935 140 298-423 7.5-315.8 1-2
Michels et al. 8o 1936 179 276-413 3.6-9.9 2
Reamer et alY.J, 1944 147 344-510 0-70.0
Bottomley et al. 125 1950 1 295 01 3
Batuecas and Losal 26 1954 32 280-282 0-0.1 3
Kenned y l27.a 1954 273-1273 2.5-140.0 3
WentorrB 8.b 1956 106 304 7.4 1-2
Vukalovich and Altunin l28 1959 120 348-773 2.7-32.7 \-2
Vukalovich and Altunin 129 1962 205 473-1023 1.1-60.0 1-2
Vukalovich et al. 13D 1963 22 923-1076 2.1-15.0 1
Vukalovich et at. 131 1963 124 313-423 2.1-60.0 1-2
Juza et at. 132.c 1965 82 323-748 70.0-400.0
Ku and Dodge IJj 1967 13 373 0.6-25.1
Sass et at. 134 1967 47 348-398 0.8-25.3
Vukalovich et at. 135 1968 168 273-308 0.8-30.0 2
Golovskii and Tsymarnyi 136 1969 129 217-303 13.0-60.0 1-2
Kirillin et al.137 1969 21 433-473 2.0-69.0 1-2
Kirillin et al. 93 1969 39 283-308 1.6-49.2 1-2
Kirillin et al. 138 .d 1969 99 223-473 1.6-54.0 1-2
Tsiklis et al. 139 1969 50 323-673 200.0-700.0
Kirillin et al. ]-10 1970 24 223-273 2,0-56.0
Popov and Sayapovl-l] 1970 117 223-303 0.7-30.0 1-2
Vukalovich et al. ].J,2 1970 95 238-268 0.7-19.0 1-2
Schonmann] 43.e 1971 85 373-573 0.4-5.9 3
Kholodov et al. l44 1972 141 293-363 0.5-4.8

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 1528 R. SPAN AND W. WAGNER

TABLE 11. summary of me Ul1l:1 ))Cl:s :1vailauk fvr the I'pT relation of eurbQn diOJ'i.ide- Continued

No. of Temp. range, Pressure range

Source Year data T(K) p (MPa) Group

Kholodov et al. 94 1972 85 243-283 0.5-4.4

Levelt Sengers and Chen50 1972 22 304-319 7.4-10.0 2
S traub 109 1972 24 304 7.4 2
Besserer and Robinson I46 1973 76 310-394 0.7-11.0 3
Rasskazov et aI. 147 1974 148 248-303 0.5-5.6 2
Shmonov and Shmulovich 148 1974 64 681-980 50.0-800.0 1
Lau l49 1986 69 240-350 1.6-70.0 1-2
Esperlll,f 1987 73 246-320 0.1-47.7 1-2
IIobte et a1. 103 .f 1987 236 215-4.48 01-500 1-1
laeschke lso 1987 245 260-360 0.2-28.5 1
Jaeschke isl 1987 27 273-353 0.2-30.0 1
Magee and El/ 52 1988 10 250-330 5.8-27.1 1-2
Ely et al. 17 1989 61 250-330 2.2-35.4 1-2
HoinkisI4S 1989 186 298-423 0.2-58.0 1-2
McElroy et al. 153 1989 44 303-333 0.8-6.0 3
Duschek et ai. 154 1990 362 217-340 0.3-9.0
Duschek et al. 58.g 1990 87 295-304 6.0-7.4
laeschke et al. D.:l 11)90 '270 :.UU-32U 0.2-12.0
Nebendahl 156 1990 21 337-413 1.9-4.4
Guo et al. IS7 1992 40 273-293 1.0-3.3 1
Weber I 58 1992 12 320 0.1-6.0 2
GUgeu el «i.''il) 1993 264 220 360 0.3 13.0
Brachthauser 160 1993 29 233-523 0.8-30.1
Fenghour et at.160a 1995 120 330-698 3.0-34.2
Klimeck et al. 16Ob 1995 60 300-430 0.5-30.1
Gokmenoglu et at. 160c 1996 142 297-425 6.1-66.6
Nowak et al. l60d 1997 21 313 8.4-12.1

aproperty tables derived from measurements.

bData partly within the two-phase region,
eWe used the smoothed data Originally published; the unsIIlomheu uala puulhhcu by Angus ct at. 3 cannot be
used because of very large scatterings.
dThis paper also contains all data given in Refs. 137, 91 and 140.
"The data of Schonmann l43 were reevaluated by Hoinkis;145 the reevaluated data were considered in this work.
fThe data published by Esperll J are reevaluations of the measurements published by Holste et al.!03 as experi-
ment III.
gDuschek et al. S8 pUblished ppT data in the vicinity of the phase boundary which were used to determine
saturated Jiquid- and vapor-densities in the near critical region.

ation significantly. The data set of Straub 109 was not included 4.2.1 Experimental Results for the Specific Isobaric Heat
in the data set used for the development of the final equation, Capacity
but it was used as a sensitive test for the description of the Today, calorimetric measurements performed with flow
critical region. apparatuses provide accurate data of the specific isobaric
heat capacity over wide ranges of temperature and pressure.
In the low density region, these results are usually more ac-
curate than isochoric heat capacity measurements.
4.2 Specific Isobaric Heat Capacity Since state-of-the-art data on the speed of sound for car-
bon dioxide are available only within a very limited tempera-
As regards the specific isobaric heat capacity, the descrip- ture range and only up to pressures of 0.9 MPa, the data sets
tion of the data situation has to be split up into data sets given in Table 13 and especially the selected data sets shown
which describe the caloric behavior of the ideal gas and data in Table 14 represent the most important source of informa-
sets which in addition contain the residual behavior. While tion on the caloric behavior of carbon dioxide. While the
the data situation for the caloric properties of the ideal gas is data set of Bender et al. l77 provides an accurate description
dominated by theoretical approaches, the description of the of the low density region, the data of Ernst and Hochberg I78
real gas behavior, where both the ideal and the residual part and Ernst et al. 179 allow a precise description of caloric prop-
of the heat capacity are considered, is virtually restricted to erties up to 90 MPa. At least for subcritical pressures, the
experimental investigations. In order to account for these dif- accuracy of these data sets is improved by suitable correc-
ferent situations, this section is divided into two subsections. tions; see Sec. 4.9.3.

J. Phys. Chem. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1529

TABLE 12. Summary of selected ppT data for carbon dioxide; detailed information is given on the uncertainty values estimated by the authors and those
estimated by ourselves and used in the weighting procedure

Uncertainty estimated Uncertainty estimated

by the authors by the authors
No. of data Uncertainty estimated No. of data Uncertainty estimated
Source Mean f~1 by ourselves Source Meanf~1 by ourselves

Ylichels 9 N.R.E.a
and Michels 122 4.00 dp= 1000 Pa, dp=0.2% Lau l49.c 42 dp=O.I%
Michels et af. 123.c 75 dpb=0.05% 3.71 dT=lO mK, dp=O.02%, dp=O.I%
1.00 dp=0.02%, dp=O.l% Esperlll 45 dp=0.03-0.l1 %
WentorrB s.c 87 dT=l mK, dp=132 Pa, dp=0.02% 1.00 dT=lO mK, dp=0.015%, dp=0.05%
0.09 dT=2 mK, dp=500 Pa, dp=0.09% Holste et al. 103 80 dT=lO mK, dp=0.015%,
Vukalovich 44 dp=0.15-0.35% 0.80 dT=lO mK, dp=0.015%, dp=0.05%
and Altunin l28 1.07 dp=O.4% Jaeschke l50 245 N.R.E.
Vukalovich 134 N.R.E. 0.69 dT=5 mK, dp=O.I%, dp=O.I%
and Altunin 129 1.00 dp=0.2% Jaeschke lSI 27 NKE.
Vukalovich et af. uu 22 N.R.E. 1.14 dT=5 mK, dp=0.05%, dp=0.05%
1.00 dp=0.2% Magee 9 dT=30 mK, dp=O.Ol%, dp=O.l%
Vukalovich et al. 131 36 XR.E. and Elyl52 0.16 dT=30 mK, dp=O.Ol%, dp=O.I%
0.64 dp=O.l % Ely et af,'? 52 dT=30 mK, dp=O.Ol%, Llp=O.1-0.15%
Juza et af. IJ2 ~:2 Ap=:2 MPa, Ap=U.j% l.UU Al=jU mK, Ap=U.Ul%, Ap=U.I-U.lS%
1.00 LlT=0.2 K, Llp=2 MPa, Ap=O.4% Hoinkis l45 72 LlT=lO mK, Llp=O.Ol%, Llp=0.16%
GoJovskii 108 LlT=80 mK, Llp=0.08%, 6.p=0.15% 1.83 6.T=lO mK, dp=O.OI%, 6.p=0.16%
and Tsymamyi 136 2.25 dT=80 mK, Llp=0.08%, dp=O.15% Duschek et al. 154 362 dT=3 mK, dp=0.006%, dp=0.015%
Kililliu t<[ ul.1"l7c 17 Af}~O.I% 1.88 AT-3 lllK, Ap-O.006%, Ap-O.015%
9.65 dp=0.05%, dp=O.2% Duschek et al. 58 87 Ap=0.03-0.25%d
Kirillin et af. 93.c 29 N.R.E. 2.25 6.p=0.03-0.25%
4.00 Llp=0.05%, dp=0.2% Iaeschke et af. 155 268 N.R.E.
0.75 6.T=5 mK, Llp=0.05-0.1%,
Kirillin et af. 138 66 6.p=0.15-0.2% Guo et af. 157 40 6.p=0.05-0.01 %
1.00 6.p=0.05%,6.p=0.2% 2.25 dT=3 mK, dp=0.005%, dp=O.OI%
Tsiklis et af. 139 49 Llp=O.3% Gilgen et aZ. 159 264 6.T=3 mK, Llp=0.005%, 6.p=O.Ol %
1.00 6. T=0.5 K, 6.p = I MPa, 6.p= 1.0% 2.18 AT=1.5 mK, dp=0.006%, dp=0.015%
Kirillin et al. 14O.c 24 Llp=O.l% Brachthauser l60 29 LlT=1.5 mK, dp=0.006%, dp=0.015%
4.00 Llp=0.05%,6.p=0.1% 1.00 6.p=0.016-0.051 %
Popov 73 N.R.E. Fenghour et af. 16Oa 120 6.p=0.016-0.051 %
and Sayapovl~1 1.00 LlT=30 mK, Llp=0.05%, Llp=0.15% 1.00 Llp=0.05-0.1O%
Vukalovich et af. 142 86 Llp =0.08-0.15% Klimeck et af. 16(Jb 60 Llp=O.lO%
1.00 AT= 15 mK, Ap =0.005%, 1.00 dT=6 mK, Llp=0.006%, Ap=0.02-0.04%
Ap=0.08-0.15% 6. T=6 mK, Llp =0.006%, Llp =0.02-0.04%
Shmonov 60 dp=0.25-0.5% Nowak et af. 160d 21 dT=1.5 mK, dp=0.006%, dp=0.015%
and Shmulovich 148 1.44 AT=O.4 K, Llp =0.2%, Llp= 1.0% 1.00 AT=1.5 mK, Ap=0.006%, dp=0.015%

aN.R.E.: No reasonable estimation given by the authors.

"Consistency is given instead of uncertainty.
C Adjusted values were used in the final data sets, see Sec. 4. 10.
dUncertainties given for the corresponding saturated liquid and saturated vapor densities.

The data sets of Rivkin and GUkov l 71.174 describe the su- this data set was classified in group 3. The data set given in
percritical region of carbon dioxide. Since empirical equa- Ref. 171 was used only with a reduced weighting factor.
tions of state may produce misleading results regarding ca-
loric properties within this region, these data sets were
considered to be of great interest for the development of the
new fundamental equation. Unfortunately, the data proved to 4.2.2 Results for the Specific Isobaric Heat Capacity in the
be inconsistent with each other and with state-of-the-art ppT Ideal-Gas State

data. Since the data given in Ref. 174 were deduced from According to Eq. (2.4), knowledge of the specific isobaric
measurements of a mixture with high carbon dioxide content, heat capacity in the ideal-gas state forms the basis for the

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 1530 R. SPAN AND W. WAGNER

TABLE 13. Summary of the data sets available for the specific isobaric heat capacity of carbon dioxide

No. of Temp. range, Pressure range,

Source Year data T(K) p (MPa) Group

Keyes and Collins l62 1932 300 0.2

Kistiakowsky and Rice l63.a 1939 300-367 0.1
de Groot and Micheis J64 ,a,b 1948 92 298-423 0.1-206.5
Masi and Petkofl65 ,a 19.'i2 17 2.:13-363 0.05-0.t5 1
Schrock l66 1952 26 311-783 0.1-7.0 2-3
Koppel and Smirh l67 1960 102 291-322 7.2-8.3 3
Vukalovich et at. 168 1964 23 295-355 0.4-8.2 2-3
Vukalovich and Gureev 169 1964 8 313-333 0.8-8.0 2-3
Vukalovich et al. ltV 1965 86 293-493 1.0-22.2 2-3
Rivkin and GUkOV 171 1968 221 283-403 8.8-24.5 1
Altunin and Kuznetsov 172 1969 36 293-333 1.0-5.0 2-3
Altunin and Kuznetsov 173 1970 54 283-373 1.0-6.0 2-3
Rivhlll ~uu Ou.il.lJy l7dc 1971 46 .306-33Z 8.8-11.8 .3
Altunin and Kuznetsov 175 1972 30 253-323 0.9-6.0 2-3
Saegusa et al. 176 1980 35 245-346 0.3-3.7 3
Bender et al.177,a 1981 60 233-473 0.1-1.5
Ernst ancl Hochherel78.a 1<)~9 9 30:? 0 .3-52.2
Ernst et at. 179,a 1989 55 333-393 0.2-90.0
Dordain et al. 179a 1994 40 327-416 5.1-25.1

aThe paper also contains extrapolated values for the specific isobaric heat capacity of carbon dioxide in the ideal
gas stare. .
bData calculated from measurements of the p p T relation.
cMeasuremems of a mixture with high carbon dioxide content; the results considered here were extrapolated
from the mixture experiments to pure carbon dioxide.

description of the ideal-gas part of the Helmholtz energy, only a few papers contain reliable data on c~, where correc-
AO(p,T). Results for c~ obtained by the extrapolation of cp tions to the simple rigid rotator, harmonic-oscillator model
measuremeIllS (0 zero pressure (cf. Table 13) are neirher ac- were taken into account in order to achieve high accuracy.
curate enough for this application nor do they cover a suffi-
Table 15 summarizes these data sets, of which the data set of
ciently wide range of temperature. Therefore, theoretical ap-
Chao l84 is the most recent one. Chao considers first order
proaches which describe the caloric behavior of carbon
corrections LO Lhe rigid roraror, hannonlc-osc1l1aror model,
dioxide in the ideal-gas state were reviewed.
which were developed by Pennington and Kobe; 185 he esti-
Information on the fundamental frequencies of the carbon
dioxide molecule can be found in various compilations, but mates that the uncertainty of his results is less than
±O.02%.

TABLE 14. Summary of selected data for the specific isobaric heat capacity
of carbon dioxide; detailed information is given on the uncertainty values
estimated by the authors and those estimated by ourselves and used in the
weighting procedure
4.3 Specific Isochoric Heat Capacity
Uncertainty estimated
by the authors Seven data sets are available for the isochoric heat capac-
No. of data Uncertainty estimated ity of carbon dioxide. The information on these data sets is
Source Meanf~l by ourselves
summarized in Table 16. More detailed information on the
Kistiakowsky ~cp==0.3o/c
and Rice l63 1.00 ~T==30 mK, Ac p =0.3o/c
Masi 12 ~T==30 mK, ACp=O.lo/c
and Petkof l65 1.00 ~T==30 mK, ~cp=O.I%
Rivkin 220 AT= 10 mK: Ap=0.OSC70,Acp==2% TABLE 15. Data sets for the isobaric heat capacity in the ideal-gas state of
and GUkOV l71 0.17 I:1T==25 mK, I:1p=0.05%, AC p ==2% carbon dioxide calculated by theoretical approaches
Bender e1 aJ. I 77.o 60 ~C p ==0.1 %-0. 15%
1.00 I:1T=lO mK, Ap==O.OI%, AC p ==0.12% Source Year Temp. range, T (K)
Ernst 9 ~cp=G.2o/c-O.99C
and Hochberg l78 .b 2.25 AT===20 mK, 6.p===O.I'K,Ac p ==0.2-0.9% WOOl ey l80 1954 50-5000
Ernst eC ai. 179 .h 55 6.c p:=:0.2'K-0.9% Baehr el al. 181 1968 10-6000
1.92 IJ.T==20 mK, IJ.p=O.l9'c, AC p ===0.2-0.99'c Gurvich lS2 1979 10-10 GOO
Chao l83 1983 50-5 000
"The consistency is given instead of the uncertainty. Chao l8 -l 1986 10- t 500
bCorrected values were used in the final data set, see Sec. 4.10.

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1531

TABLE 16. Summary of the data sets available for the specific isochoric heat capacity of carbon dioxide

No. of Temp. range, Density range,

Source Year data T(K) p (kg/m3) Group

Eucken and Hauck 112 1928 8 223-293

Michels and Strijland l86.a 1952 50 297-313 274-839
Amirkhanov et al. 187 1970 214b 280-393 500-831 2
Amirkhanov and Polikhronidi J88 1971 733 b 276-403 512-903 1-2
Edwards 55 1984 221 c 301-312 434-467
Magee and Elyl16 1986 113 223-330 88-1140 1-2
Abdulagatov et al. 59 1991 331 304-357 460-510 1-2
Abdulagatov et al. 59 .a 1994 88d 304-357 460-510
Abdulagatov et al. 59 .b 1994 230c 280-357 460-519 1-2

aEvaluation of the data is hindered by unclear temperature assignment.

bSome of the data are in the two-phase region.
cPreselected numerical values provided by Sengers; 189 97 measurements describe states within the two-phase
regIOn.
dThese data are selected from the data given in Abdulagatov et at. 59
e132 data are in the two-phase region; 88 of the 98 data in the single-phase region are already known from
Abdulagatov et al.59.59a

selected data is given in Table 17. For carbon dioxide, mea- within less than 0.5% by the new equation of state. Based on
surements of the isochoric heat capacity are of great impor- these facts, we concluded that deviations up to 8% in the
tance in the two regions discussed below. Isochonc heat capaCIty were probably due to shortcommgs III
The data set of Magee and Elyl16 yields the only compre- the data set. Thus, the weighting factors were strongly re-
hensive description of caloric properties within the high den- duced for the low density measurements.
sity region. At liquid densities, this data set is limited to Within the extended critical region, the data sets of
pressures above the critical pressure, leaving a gap between Edwards 55 and of Abdulagatov et al. 59,59a.59b had great influ-
the available caloric data in the homogeneous region and on ence on the development of the new equation of state. (Ed-
the saturated liquid curve (see Sec. 7.2.2). At densities below wards's thesis 55 only contains graphical illustrations of the
600 kg/m 3, these data can only be represented with system- results. The data used here were provided by Sengers.189)
atic deviations clearly outside the uncertainty estimated by The reduced weighting factors given in Table 17 were cho-
the authors. On the other hand, in this region several accurate sen because of the large number of data points within a small
equations of state 3,15-17 agree with each other and with the and very sensitive region. The use of these data sets with
new equation of state within about 2% for the isochoric heat f wt= 1 would have resulted in an overemphasis of the critical
capacity, and data of the isobaric heat capacity are met region; details are given in Sec. 5.
The recent data of Abdulagatov et al. 59 were first pre-
sented in the Proceedings of the 11 th Symposium on Ther-
TABLE 17. Summary of selected data for the specific isochoric heat capacity
mophysical Properties in Boulder in 1991. When the corre-
of carbon dioxide; detailed information is given on the uncertainty values
estimated by the authors and those estimated by ourselves and used in the sponding paper 9a was published three years later, it
weighting procedure contained only 88 data points selected from the 331 data
points given in the proceedings. In the same year, another
Uncertainty estimated paper59b was published which contains the 88 points pub-
by the authors
No. of data Uncertainty estimated
lished before, 10 additional points on one isochore in the
Source Mean f~.! by ourselves homogeneous phase, and 132 additional points in the two

Amirkhanov 18 I:l.T=5 mK, I:l.c v =2-4%

and Po Ii khronidi 188 1.00 I:l.T=50 mK. I:l.p=O.05%, I:l.c v =2.5%
Edwards 5)." 124 .lc v =O.75%b
0.16 ~T=l mK I:l.p=0.05%, I:l.c v =2%
TABLE 18. Summary of the data sets available for the speed of sound of
Magee and Eli 16 80 I:l.T= 10 mK, I:l.p=O.1 %, I:l.c,.=0.5-2% carbon dioxide
0.37 I:l.T=IO mK,l:l.p=O.l%,
I:l.c c' =0.5-29'c Temp. Pressure
Abdulagatov et al. 59 233 Llp =0.023%, I:l.c" = 2-3.59C No. of range, range,
0.25 tJ.T= 10 mK, ~p=0.05CJc, I:l.c v =59C Source Year data T (K) p (MPa) Group
Abdulagatov et ai. 59" 88 tJ.p=0.0239C, I:l.c,.=2-3.59C
0.25 I:l.T=IO mK, I:l.p=O.OSCJc. ~c['=5% Herget 19 I 1940 195 301-311 7.0-10.3 2
Abdulagatov ef 01.5% 10 I:l.p=0.023%, Llc v =2-3.59C Novikov and Trelin l92 1962 236 288-373 3.0-10.0
0.25 LlT=lO mK, tJ.p=0.OSC7c, ~cc,=5CJc Pitaevskaya and Bilevich I93 ." 1973 176 298-473 50.0-450.0 1-2
Lemming l94 1989 50 240-360 0.4-0.9 I
"Adjusted values were used in the final data set: see Sec. 4.10.
bThe precision is given instead of the uncertainty. "Smoothed data.

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 1532 R. SPAN AND W. WAGNER

TABLE 19. Summary of selected data for the speeds of sound of carbon TABLE 21. Summary of the data sets for differences of the internal energy of
dioxide; detailed information is given on the uncertainty values estimated by carbon dioxide
the authors and those estimated by ourselves and used in the weighting
procedure No. of Temp. range, Density range,
Source Year data T(K) p (kg/m3) Group
Uncertainty estimated
by the authors
Kriiger204 1964 454a 274-325 190-870 1-2
Baeh~o5 1968 47 291-316 466
No. of data Uncertainty estimated
Source Meanl"wt by ourselves
aSome of the measured temperature intervals partly reach into the two-phase
Novikov 234 N.R.E.a region.
and Trelin l92 0.77 LlT=O.1 K, Llp=O.I%, Llw=0.5%
Pitaevskaya 144 N.R.E.a
and Bilevich 193 2.25 LlT=O.1 K, Llp=0.2%, Llw=2%
Lemming 194 44 LlT=8 mK, Llp=4.2 mbar, Llw=0.015%
Besides the data presented in Table 18, five papersl95-199
0.06 LlT=8 mK, Llp=4.2 mbar, Llw=0.OI5% are available which deal with the speed of sound in the im-
mediate vicinity of the critical point. None of these papers,
aN.R.E.: No reasonable estimation given by the author.
which were published between 1951 and 1970, contains nu-
merical results. We did not try to evaluate the graphical. rep-
resentations given in these papers since the special problems
phase region. The uncertainty of the data of Abdulagatov
connected with experimental work in the critical region were
et ai. was estimated to be at least as big as the scatter visible
not adequately considered at that time.
in the original data set. 59
The papers of Lipa et ai., 190,52 which are often cited in
literature on carbon dioxide, do not contain numerical re-
4.5 Enthalpy
sults. Since the dutu of Edwards 55 cover the sume region,
were measured with the same equipment, and are less influ- The literature sources which deal with enthalpy measure-
enced by impurities,55 the data of Lipa et al. were not con- ments are summarized in Table.20. The data of Vukalovich
sidered in this work. and Masalov 201 ,202 and of Moller et ai. 203 were considered in
this work, but only the data of Moller et al. were used with
4.4 Speed of Sound the uncertainties given by the authors (10 data selected,
mean value of f~t=2.78, b"h=0.7% or b"h=0.6 kJlkg,
Three of the four data sets available for the speed of sound whichever is greater). These data provide important informa-
of carbon dioxide were used for the development of the new tion at high densities where the data situation for caloric
equation of state. Table 18 contains the available data sets properties is poor. The data of Vukalovich and
and Table 19 gives additional information on the selected Masalov 2ol ,202 were used to test the quality of the new equa-
data. The data sets of Novikov and Trelin 192 and of Pitaev- tion with regard to caloric properties at high temperatures.
skaya and Bilevich 193 provide important information on the
extended critical region and the high pressure region, respec-
tively. Though the quality of the data published by 4.6 Internal Energy
Lemrning 194 is superior to the other data sets, these data were
used only with reduced weighting factors. In the gas region, Table 21 lists the general information on the two data sets
the residual part of the speed of sound is less than 2% of the which are available for differences of internal energy. The
total speed of sound at pressures below 1 MPa. Since the data measured on the critical isochore by Baehr20J were not
uncertainty of measurements is related to the total value of used since the temperature displacement of the (aul aT) L'
the speed of sound and not only to the residual part, the maximum observed by Baehr could not be explained. The
contribution of thc:o.c data fOl the Lievdut'llleIll u[ all empiri- 150 selected data of Kriiger,204 which do not reach into the
cal correlation describing the residual fluid behavior is very two-phase region, were used with estimated uncertainties of
limited. b"T=40 mK, b"p=0.2%, b"u=2%-4%, and a mean weight-
ing factor of l;'t=0.88. The uncertainties given by the author
(~T= 10 mK, b"p =0.03%, b"u= 1.4%-3%) are too small to
TABLE 20. Summary of the data sets available for enthalpy differences of explain the scatter of the data.
carbon dioxide

Temp. Pressure
No. of range, range,
4.7 Joule-Thomson Coefficient
Source Year data T (K) p (MPa) Group
Since data of the Joule-Thomson coefficient can only be
Maas and Barnes 20n 1926 4 212-298 0.1 used in the nonlinear fitting procedure and not in the linear
Koppel and Smith l6i 1960 102 291-322 7.2-8.3 algorithms of the optimization procedure, their influence on
Vukalovich and Masalov 201 1964 54 423-523 2.5-9.8
the development of an empirical fundamental equation is
Vukalovich and Masalov 202 1964 68 573-773 2.5-9.8
Moller et al. 203 1993 10 233-358 15.5 fairly small. The data of Bender et al. 177 are the only ones
which were included in the data set used for the nonlinear fit

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1533

TABLE 22. Summary of the data sets available for the Joule-Thomson coefficient of carbon dioxide

No. of Temp. range, Pressure range,

Source Year data T(K) p (MPa) Group

Burnett207 1923 127 273-393 2.0-7.7

Roebuck et al. 8l 1942 151 198-573 0.1-20.7
de Groot and Michels 164.a 1948 92 298-423 0.1-206.5
Yukalovich et al. 206.b 1970 131 253-343 0.6-5.9 2
Altunin and Gureev 208 1972 92 293-500 1.5-22.0 2-3
Bender et al. 177 1981 35 233-473 0.1-1.5
Cusco et al. 208a.b 1995 33 350-500 1.0-4.6

"Joule-Thomson coefficients calculated from measured ppT data.

bIsothermal Joule-Thomson coefficients, 8 T = C pj)-.

(34 tiala Wt;It; selected with 6.T= 10 mK, 6.p=O.Ol %, Recently, Span225 pointed out that it was not very useful to
~p,=0.4%, and f~t=0.36). The data of Vukalovich et al. 206 include experimental second and third virial coefficients into
proved to be a sensitive test for the consistent description of the data set used for the development of a wide-range equa-
the B:l~ region. Tahle 22 gives a survey of the data sets deal- tion. Most of the data sets descend from ppT measurements
ing with the Joule-Thomson coefficient. which have been evaluated in order to determine virial coef-
ficients. Thus, the use of the original measurements yields
much better access to the desired experimental information.
4.8 Virial Coefficients Furthermore, fitting an equation of state to virial coefficients
is only useful if the terms of the equation corresponding to
The literature on carbon dioxide contains many papers in the virial coefficients are independent of each other, as is the
which information on the second and third vitial coefficient case in a simple virial expansion. However, if an equation of
is given. Table 23 summarizes the corresponding sources. state contains exponential functions, this condition is no
longer met. Thus, in this article, the available values for
virial coefficients were only used for comparison; none of
TABLE 23. Summary of the data sets available for the second and third virial
coefficient of carbon dioxide. For reasons explained in the text, no data were
the data sets was assigned to group 1.
assigned to Group I At temperatures below 220 K, however, the whole contri-
bution of the third virial coefficient [p / (pR T)
No. of data Temp. range, = ... + C p2+ ... ] is smaller than the uncertainty of the
Source Year S/C T(K) Group
most recent ppT data l54 throughout the gas region. Therefore,
Michels and Michels122 1935 13/13 273-423 3/3 at low temperatures a physically unreasonable representation
Schafe?09 1937 16/· .. 203-273 3/··· of the third virial coefficient calculated from an equation of
MacCormack and Schneide?1O 1950 9/9 273-873 3/3 state may occur if the equation was fitted only to ppT data.
CoHre! and Hamilton 211 1955 7/· .. 303-333 3/ .. ·
Pfeff':!rJe et al. 212 1955 212
Since reliable value~. of the th~rd virial coefficient cannot be
303 3/3
Cottrell et al. 213 1956 3/ .. · 303-363 3/ .. · established by an evaluation of experimental ppT data in this
Cook214 1957 6/· .. 213-303 3/ .. · temperature range, 13 values of the third virial coefficient
Masia and Pena llS 1958 6/ .. · 298-423 3/· .. were calculated from a simple polynomial equation which
Butcher and Dadson 216 1963 13/13 263-473 3/3 describes all the selected data of the different thermody-
Huff and Reed 217 1963 10/ .. · 298-510 3/···
Vukalovich and Masalov 218 1966 18/18 423-773 2/3
namic properties in the gas region within their experimental
Dadson et al. 219 1967 9/· .. 263-398 3/··· uncenainty and yields a reasonable plot of the lhird virial
Ku and Dodge 133 1967 III 373 3/3 coefficient at low temperatures. These "artificial" data of
Sass et af.I:I... a 1967 3/··· 348-398 3/·· . the third virial coefficient were then used during the devel-
Timoshenko et al. 22o 1970 9/· .. 224-313 3/· .. opment of the new equation of state.
Yukalovich et af. J4l 1970 10110 253-343 3/3
Vukalovich et al. 206 1970 14/ .. · 238-308 3/···
Waxman et al. 221 1973 6/ .. · 273-423 2/· ..
Bender et af.177 1981 4/··· 233-263 3/·· .
Ohgaki et al. 222 1984 2/ .. · 423-473 3/· .. 4.9 Liquid-Vapor Equilibrium
Holste et af. 1~3 1987 18/16 217-448 2/2
Mallu et al. 223 1987 3/··· 323-423 3/ .. · During the procedure of optimizing the structure of the
Hoinkisl~5 1989 4/4 298-423 2/2 new equation of state, the liquid-vapor equilibrium was used
Mallu et af. 22~.h 1989 .. ·/3 323-423 · .. /3 in a linearized way.32,30 The data set used for this purpose
Me Elroy et al.15:' 1989 4/4 303-333 3/3 consists of values of Ps(1), pi (T), and pl/(1) at 205 tempera-
Duschek et af. 15" 1990 7/4 220-340 2/2
tures which were calculated from Eqs. (3.13) to (3.15). These
"Yirial expansion developed in pressure. data cover the whole liquid-vapor phase boundary with tem-
hThis paper additionally includes the values already published!23 in 1987. perature intervals which decrease when approaching the

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 1534 R. SPAN AND W. WAGNER

TABLE 24. Summary of selected data describing the liquid-vapor phase

equilibrium of carbon dioxide; detailed information is given on the uncer- 233 K - 323 K
tainty values estimated by the authors and those estimated by ourselves and 0.1.---------------------------------~

used in the· weighting procedure

~
<1
Uncertainty estimated
by the authors 8....
No. of data Uncertainty estimated
Source Property Meanf~t by ourselves

Novikov and Trelin 113.b

5 10 W ~ 100
w" 18 N.R.E.a
1.00 6.T = 10mK,6.w il = 0.5% Pressure p I MPa
Pecceu aI1d Van DaeJII5 w' 23 6.w'=l%
1.23 6.T= 0.1 K,6.w' = 0.5%
o Duschek et al. 154 (233K - 240K)
o Gilgen et al. 159 (240K + 323K)
Magee and Elyll6 C(J' 73 c N.R.E.a 140
2.04 6.T= 10mK,6.c(J'= 1 % <> Kirillin et al. (233K - 243K)
Duschek et al. 58 109 6.T= 3 mK,6.ps == 0.005% [!] Michels et al. 123 (323K)
Ps
1.00 6.T= 3 mK,6.ps= 0.005%
Duschek et al. 58 p' 50 6.T=3mK,6.p' =0.015% FIG. 6. Relative deviations 100 6.p= 100 (Pexp-Pcalc)fPexp of experimental
1.00 6.T= 3 mK,6.p' == 0.015% ppT data from values calculated from Eq. (6.1). This figure illustrates the
Duschek et al. 58 p" 42 6.T= 3 mK,6.p" = 0.025% reason for adjusting the data of Kiriilin et al. 140 and Michels et al. 123 (see
Sec. 4.10.2).
1.00 6.T= 3 mK,6.p" = 0.025%

aN.R.E.: No reasonable estimation given by the authors.

bIn the final data set adjusted values were used; see Sec. 4.10.
COnly data at T<295 K were considered; see Sec. 3.8.
tion can be established based on the pressure on the critical
isochore. In reasonable accordance with earlier
suggestions,154,24,17,50 we used
critical temperature. Additionally, the group 1 caloric data Wentorfl8: T4S= T we.-27 mK. (4.3)
already presented in Table 10 were used to fit the new equa-
tion of state. 4.10.2 Adjustment of pp T Data
The final equation was nonlinearly fitted directly to the
phase equilibrium data of Duschek et al. 58 and to the caloric Reasonable adjustments can be applied to ppT measure-
data. Table 24 gives detailed information on the experimen- ments if systematic deviations occur in a region where a data
tal caloric and thermal data used for the description of the set and a set of reference data overlap. In this way, accurate
liquid - vapor equilibrium. information on the ppT relation can be obtained up to pres-
sures of approximately 100 MPa, whereas the two-sinker
data of Duschek et al. 1:54 and Oilgen et al. I :59 are limited to
4.10 Adjustment of Data
9 MPa and 13 MPa, respectively and the single-sinker data
In order to achieve a final data set which is as consistent as of Brachthauser l64 and Klimeck et al. 160b are limited to
pOSSible, some of the selected data had to be adjusted. As a 30 MPa.
result, three groups of data can be distinguished which were Such simpl~, corrections were used for the data sets of the
corrected for different reasons. These three groups are ex- following:
plained in the following suhsections. Kirillin ct al.137.93,140: P- PKl.· 0.999 5,

4.10.1 Adjustment of Data Sets Describing the Critical Region

For the description of the thermodynami~ snrfl'lce in the

immediate vicinity of the critical point, the difference be-
333 K + 363 K
tween the measured temperature and the critical temperature
is more important than the absolute temperature, and this
'..J"'-
temperature difference is probably also less influenced by <1
systematic deviations or by impurities of the sample. If the o 0
corresponding critical temperature is given, the absolute tem- 8
perature can be corrected by the difference between this -1
value and the value used in this work [cf. Eq. (3.5)]. This 0.1 10 100
technique was used for two important sets of caloric data: Pressure p / MPa
Edwards 55 : (4.1) o Ernst et at. 179 (3J3K) 0 Bender ct ai. 177 (363K)
l13
Novikov and Trelin : T 48 =T No .-44mK. (4.2) FIG. 7. Relative deviations 100 6.c p = 100 (cp.exp-cp.calc)/Cp.exp of experi-
mental Cp data from specific isobaric heat capacities calculated from
WentorP8 did not give any information on the critical tem- Eq. (6.1). This figure illustrates the reason for correcting the data of Ernst
perature corresponding to his ppT data, but a similar correc- et al.179 and Bender et al. m (see Sec. 4.10.3).

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1535

TABLE 25. Temperature dependent corrections of isobaric heat capacity data 4.10.3 Correction of Isobaric Heat Capacities

c p.cor. - c p.exp.
Temperature, Since the low pressure limit of the isobaric heat capacity,
T(K) cp.e,p. c/' is known very well for carbon dioxide (see Sec. 6.1),
Bender et at. 177 temperature dependent errors of measured isobaric heat ca-
233 +0.40% pacities can be determined easily. Figure 7 shows systematic
243 +0.25% deviations of data measured by Bender et al. 177 and by Ernst
273 +0.13% et al. 179 Again, two different isotherms are combined in a
323 +0.05%
+0.31%
single deviation plot. A systematic error of the new equation
363
393 +0.l4% for the residual part of the Helmholtz energy, Eq. (6.5),
423- +0.l0% would result in deviations which increase with pressure since
473 -0.17% the residual contribution to the isobaric heat capacity in-
l78
Ernst and Hochberg creases.
303 +0.36%
To compensate for these temperature-dependent devia-
Ernst et al. 179
JJJ 0.18% tions, the data sets of Bender P.t a/., 177 Ernst ~nrl
363 :::1::0.00% Hochberg,178 and Ernst et al. 179 were corrected according to
393 -0.37% the values given in Table 25.

Michels et al. 123 : P = PMi.· 0.999 5, (4.5)

5. Description of Thermodynamic
Lau L49
: p= PLa.' 0.9993. (4.6) Properties in the Critical Region
Figure 6 shows an example for the justification of these
adjustments by combining two very different isotherms in a It is well known 56,226 that thermodynamic properties can
single deviation plot. The 99 measurements published by be described by so called "power laws" along certain paths
Kirillin et al. only in Ref. 138 cannot be adjusted according throughout the critical region of a pure fluid. This kind of
to Eq. (4.4). The corrected data of Michels et al. I23 were description, which was originally introduced in 1896 by
used only at pressures above 18 MPa. In regions where the Verschaffelt227 as an empirical attempt, has been supported
temperature and pressure dependence of the density is by recent theoretical results. In particular, the renormaliza-
strong, the data adjusted according to Eq. (4.5) also yield tion group approach introduced by Wilson 228 extended
unsatisfactory results. knowledge on the behavior of pure fluids in the critical re-
During the last 20 years, different authors 5o ,21,24,27 have gion and resulted in "universal" values for the critical ex-
suggested corrections for the temperature scale used by ponents. These values are defined as power-law exponents in
Michels et a1. 80 ,123 and Michels and Michels. I 22 Possible cor- the limit of vanishing distance to the critical point. Table 26
rections were tested in this work, but no reasonable tempera- shows some of the most important power laws and gives
ture shift between the ITS-27 temperature scale and the tem- different values for the corr~sponding critical exponents,
perature scale used at the Van der Waals laboratory at that which were established by evaluation of the renormalization
time could be established. If the systematic deviation of group theory.56 by expansion of a classical equation with a
these data is due to errors in the temperature scale, different so-called three-point contact at the critical point, and by ex-
scales have to be assumed for the measurements published in pansion of a classical equation with a so-called five-point
different papers of Michels. Since the data situation in the contact at the critical point. None of the classical equations is
gas and extended critical region has improved significanrly, able to reproduce the values predicted by the renormalization
it was decided not to use Michels' data within these regions. group theory.

TABLE 26. Examples for power laws describing thermodynamic properties along certain paths throughout the critical region

Values determined by evaluation of

Critical
Property Power law Described path exponent RG theorya 3-point eq.h 5-point eq.c

Densities at saturation (p' - p")~(Tc- T)f3 phase boundary f3 0.326:::1::0.002 0.5 0.25
Isothermal compressibility KT~IT-Tcl-Y crit. isochore ')' 1.239:::1::0.002 1 J
Pressure ;p-Pcl-Ip-Pcl" crit. isotherm Ii 4.80:::1::0.02 3 5
Isochoric heat capacity cu-IT-Tcl- a crit. isochore a 0.110:::1::0.003 0 0

"According to Sengers and Levelt Sengers. 56

bSuch an equation of state is constrained at the critical point by the conditions (apl op) T = 0 and (1;2 pi opl) T = 0, where «(J3 p/ apJ) T > O.
cIn addition to the conditions given in footnote b this equation yields (a 3p/a p 3)T = 0 and (o~p/rJp.J,)r = O. where (asp/op:')! > O.

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 1536 R. SPAN AND W. WAGNER

;005 304.1282 K 6
Chen etal.
27

E
02-type equation
1
5 '1-'-'- CH4-type equation
g 0 _,._
0 1
...... g ~ 1 0
1 D
Edwards
55

OJ) 4 Abdulagatov et al. 59

1
-0.005 I C 1
440 460 480 500
g <D
Density P / (kg/m3) 3 @
rJ" I P=Pc I
109 27 CD
o Straub Chen et al.
CH4-type equation 2
02-type equation

FIG. 8. Relative deviations 100 !::.P = 100 (Pexp - Pcalc)/P exp of experimen-
1'------'---'---'-----'---'---'----'---'-----''----'
tal ppT data on the critical isotherm from values calculated from Eq. (6.1). 300 302 304 306 308 310
Values calculated from the crossover equation of Chen et aZY and from
refitted equations using the CH4 - and OTform (see Sec. 5.1) are plotted for Temperature T / K
comparison.
FIG. 9. Representation of representative isochoric heat capacity data in the
critical region. The plotted curves correspond to values calculated from the
rrm:<:nvpr f'qu::Ition of Ch~n I?t (I/. 27 and from refitted equations using the
CH4 - and 02-form (see Sec. 5.1).
5.1 Limitations of Analytical Equations of State

Usually it is concluded that analytic equations of state

ci:uI11ullC1-'H;~Clll lhc 1-'lU1-'CIlk~ uf 1-'urc fluius wiLhin lhe criti- Oz-type equation shows the 1O0 steep course of [he critical
cal region because they do not yield correct critical expo- isotherm which is to be expected from an analytic equation
nents. For most of the properties considered in this article, of state. The analytic CH4-type equation and the new equa-
this conclusion is incorrect if state-of-the-art equations are tion of state yield almost identical results and represent the
considered. data as accurately as the crossover equation, even though
In this section, the results obtained within the critical re- they do not result in the limit for the corresponding critical
gion from two wide-range equations are compared with ex- exponent 8 which is predicted by the renormalization group
perimental results and with values which were calculated theory.
from a nonanalytic equation especially designed for the de- Along the critical isotherm, ppT data can be very accu-
scription of the extended critical region. For this purpose, we rately described with a wide-range equation because the cor-
chose the crossover equation of Chen et al. 27 The critical responding power law describes pressure differences which
parameters of the crossover equation were changed to the vanish when approaching the critical point (cf. Table 26).
values used in this work because otherwise the comparison Thus, different values for the critical exponent 8, which is
of equations with different critical parameters would produce defined as limit Ip - pcl---* 0, hardly effect the representation
misleading results in the immediate vicinity of the critical of the ppT surface. Most of the properties considered in this
point. To give an example, which is typical for a modem article show a-similar behavior when approaching the critical
wide-range equation, we fitted the equation published by point.
Schmidt and Wagner4 for oxygen to the data set used in this However, there are two properties which behave in a com-
work; this equation is referred to as Oz-type equation. The pletely different way: the specific isochoric heat capacity,
equations of Elyl4 and Ely et al. 15 use the same functional c v ' and the speed of sound, w. The evaluation of analytic
form but these equations are constrained to different critical equations yields a critical exponent a=O, which results in a
parameters. To illustrate the limits of an analytic equation of finite value of Cu at the critical point, whereas the renormal-
state. we refitted the formulation published by Setzmann and ization group theory predicts a=O.1l0, resulting in a slow
Wagner30 for methane which is referred to as a CH4 -type divergence of the specific isochoric heat capacity at the criti-
equation. As far as the description of the critical region is cal point.
concerned. this equation is probably the most efficient ana- Figure 9 shows measured specific isochoric heat capacities
lytic equation available today. on the critical isochore of carbon dioxide and the corre-
Figure 8 shows the relative deviation between pressures sponding values calculated from the Ortype equation, the
calculated from the new equation of state for carbon dioxide CH4-type equation, and the crossover equation. When ap-
[Eq. (6.1)]. from the refitted CHr and 02-type equations, proaching the critical temperature, only the crossover equa-
and from the crossover equation of Chen et al.,n compared tion is able to follow the steep course of the data. The
v,'ith the very consistent data measured by Straub, 109 directly CH4-type equation fails within an interval of approximately
on the critical isotherm of carbon dioxide. (None of the ±: 0.5 K around the critical temperature and the Oz-type
wide-range equations was fitted to the data of Straub; these equation fails within an interval of approximately ±: 2 K.
data only served as a consistency check for the critical re- Similar results can be obtained for the speed of sound
gion: cf. Sec. -+.1.) In the resolution chosen in Fig. 8, only the since it is related to the reciprocal value of the isochoric heat

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1537

capacity. From a theoretical point of view, the speed of scription of the ppT surface within the critical region should
sound is expected to vanish at the critical point, whereas also yield reliable values of the specific isobaric heat capac-
analytic equations yield only a finite minimum. Again, the ity.
temperature interval, where the analytic equations fail, ex- The situation is different for the isochoric specific heat
tends over approximately ±O.5 K and ±2 K, respectively, capacity which is given by
around the critical temperature.
(5.2)

If the second derivative of the· residual part of the Helmholtz

5.2 Use of Nonanalytic Terms as an Integral energy with respect to 7 is finite at the critical point, the
Component in an Empirical Wide-Range Equation value. of the specific isochoric heat capacity is also finite.
of State Only an equation with a nonanalytic behavior in cjJ~T can
reproduce the expected divergence in cu. At the same time,
The performance of a sophisticated analytic equation of such a formulation would result in vanishing values of the
state, such as the CH4-type equation, is completely sufficient speed of sound since w corresponds to
for any technical application within the critical region. How-
ever, because of the scientific importance of the critical re- ~(~12
aT p
gion of carbon dioxide, an improved description of caloric
properties was regarded as desirable at least as long as the
numerical expense for the evaluation of the resulting corre-
lation remains justifiable. Therefore, we rejected models (5.3)
which employ an iterative procedure for the relation between
the physical variables T and p and the mathematical vari-
abIes used, like switching3,229 and transformation 26 ap-
proaches.
At the critical point, the expression (apIa ph becomes zero
In the context where the fundamental equation presented
and (apl aT) p is a finite value. Thus, if c u becomes infinite,
in this article is clearly empirical, an asymptotic behavior
the speed of sound becomes zero.
corresponding to the predictions of the renormalization
Consequently, a formulation has been developed which
group theory was considered to be of minor importance;
can be included into an empirical wide-range equation of
mixing up theoretical and empirical approaches may even .
state as a regular contribution to the usual sum of terms and
produce misleading results. Therefore, the attempt was made
which yields the intended nonanalytic behavior of ¢~T. Such
to extend the qualitatively correct behavior of an empirical
a formulation has to fulfill three additional conditions:
wide-range equation to the immediate vicinity of the critical
• The values resulting for cjJ~T have to be finite everywhere
point by introducing special nonanalytic terms.
except at the critical point.
The development of such formulations started with an ex-
• Singular behavior of the other second derivatives and all
amination of the relations between the reduced Helmholtz
derivatives with respect to 8 has to be avoided everywhere.
energy and caloric properties. The specific isobaric heat ca-
However, there are no further restrictions for the behavior
pacity can be expressed as
of these derivatives-the complete equation of state has to
~(~)2 be designed to behave in a special way and nor only a
.aT p
single term in the equation.
• Within the 8,7 surface of the critical region, the maximum
of <P~T has to follow the course of the saturated vapor ann
saturated liquid line in order to avoid unreasonable C u
maxima in the single-phase region.
These conditions can be fulfilled if a formulation of the
following mathematical form is introduced as the ith term in
an equation for the residual part of the Helmholtz energy,
where R corresponds to the specific gas constant, cjJ to the
namely
ideal (superscript 0) and residual (superscript r) part of the
reduced Helmholtz energy, 7 to the inverse reduced tempera- (5.4)
ture, and 8 to the reduced density. The quantities 7 and 8
used as subscripts indicate the corresponding derivative of with
$; see the footnote of Table 3. Since (apl c7p) ~ I grows
much faster when approaching the critical point than c v ' in
Eq. (5.1) the specific isobaric heat capacity is dominated by The exponential function damps the influence of this expres-
the fraction, which is closely related to the representation of sion outside the critical region. The distance function fl. hi
ppT data. Thus. an equation which yields an accurate de- introduces the nonanalytic behavior and ensures that the

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 1538 R. SPAN AND W. WAGNER

1.80 6
T=305 K
~ 1.78 _._0_.-'-'_'_°,0-.-.-
I
0-._,_.-
Chen et at. 27
(0
N~ 1.76 I Eq. (6.1)
e 1.74 5 CH4 -type equation
"'~ 1.72 ---
---
~ 0 Edwards 55
~ 1.70
0.0 4 0 Abdulagatov et at. S9
~

.:
......
I '-"

~ .
I 3
I
~ I P=P c I

2
467.60 467.65
Density p I (kg/m3)
Eq. (6.1) -.-.- Preliminary eq.
Temperature T I K
FIG. 10. While preliminary equations of state showed a discontinuous plot
of the third density derivative of the reduced Helmholtz energy, the new FIG. 11. Representation of representative isochoric heat capacity data in the
equation of state, Eq. (6.1), yields continuous plots for the third derivatives. critical region. The plotted curves correspond to values calculated from Eq.
(6.1), the crossover equation of Chen et aI., 27 and a refitted equation using
the CH4-form (see Sec. 5.1).

maximum in Cu follows the phase boundary. Finally, the re-

duced density in the product of ~r guarantees a physically
The smallest exponent b i occurring in the equation of state
correct behavior in the low-density limit.
is related to the critical exponent a, which describes the
Besides the coefficients ni' Eq. (5.4) introduces seven
divergence of the specific isochoric heat capacity, by the
"internal" parameters (Ai, B i , Ci , D i , ai' b i , f3i) for each
expression
of the terms i; in principle, these parameters can be included
into a nonlinear fit of the entire equation. However, because (5.7)
of the highly correlated influence of these parameters, a si-
multaneous nonlinear fit turned out to be very difficult.
Therefore, we decided to determine reasonable starting val-
ues for B i , Ci , ai' and bi with our optimization strategy. The
subsequent nonlinear fit of bi , Ci , and Di resulted only in 200
- - Eq. (6.1)
minor improvements of the equation. Bi and ai were not
- - - CH4-type equation
refitted in the current project. On principle, Ai and f3i corre- 27
~ . - . Chen et al.
spond to the proportionality factor and to the critical expo-
Ilent uf the IJuwer law desl:ribing the densities of saturated 175 ~ .~
liquid and saturated vapor (see Table 26) and can be inde-
.. ~

pendently determined. In the final bank of terms (see Table

30) a value for f3i was used which is slightly smaller than the ~
value expected for the corresponding critical exponent in or- ; 150
der to fulfill the conditions
(5.5)
and
1
(5.6)
,B/< 2a i(l-b i )+2·
100
Equations (5.5) and (5.6) result from the condition that
singular behavior has to be avoided everywhere except for
derivatives of at least second degree with respect to tempera-
ture at the critical point. Unpublished preliminary equations
400 500 600
did not fulfill these conditions and resulted in a discontinu-
ous plot of the third density derivative of the reduced Helm- Density pI (kg/m3)
holtz energy, (a 3 <PI a83 ) TO at the critical isochore. Figure 10
FIG. 12. Representation of the speed of sound on isotherms in the critical
shows an example for this possible misbehavior and shows region. The plotted curves correspond to values calculated from Eq. (6.1),
that the final equation, Eq. (6.1), results in a continuous plot the crossover equation of Chen et al.,27 and a refitted equation using
of the crucial third derivatives. CH..\-form (see Sec. 5.1).

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1539

20~~-~--------------------~
6....----------------;.....- - - - - - - - - ,

10

I .

0.5
3 1..----------, 1....
0·-:-6...........L..I..I.IJ1w,0-:·s:-'--'....L.LIJJ.J1O"-.-:-4.L....L.J...L.LIlwO-:·3:-'---'L...L.LJWl1L0·-2...L......L..J...LLWJ1O' I
T= Tc + 0.5 K IT - Tel I Te
, " ',,"I! "II""! II",," ",,'"'' II''''''
0.0003 0.003 0.03 0.3 3 30
2 IT - T) I K
55
Eq. (6.1) o Edwards
27
Chen et al. o Abdulagatov et ai.•u
Pc 02-type equation
1~~~-L-~~-~~~~~~-~~

300 400 500 600

FIG. 14. Representation of experimental isochoric heat capacity data in the
Density p/ (kg/m3)
single phase (T>Tc) and two phase (T<Tc) region in a double logarithmic
- - Eq.(6.1) -.-.- CH4-type equation diagram. The plotted curves correspond to data on the critical isochore cal-
.. - .. Chen et ai. 27 culated from Eq. (6.1), the crossover equation of Chen et aI., 27 and a refitted
equation using the 02·form (see Sec. 5.l).
FIG. 13. Representation of the isochoric heat capacity on isothenns in the
critical region. The plotted curves correspond to values calculated from
Eq. (6.I), the crossover equation of Chen et al.,27 and a refitted equation Eq. (6.1) yields a vanishing speed of sound at the critical
using the CH 4-fonn (see Sec. 5.1). point. Figure 12 shows the curve of the speed of sound,
plotted on two isotherms. as function of density. At the iso-
therm Tc +0.5 K, the analytic CH4 -type equation, the cross-
However, in combination with the sum of all terms of the over equation of Chen et al.,27 and Eq. (6.1) result in very
entire equation of state, the asymptotically expected leading
value of bi =0.945 yielded unsatisfactory results. This dis-
crepancy is discussed later in this section. 5000~----------------------------~

The final equation of state for carbon dioxide, which is - - Eq. (6.1)
presented in detail in Sec. 6, has been developed by the use
of nonanalytic terms corresponding to Eq. (5.4). The proce- 2000
dure optimizing the structure of the equation of state was ~
-
OJ)
restricted to a maximum of four nonanalytic terms within a 1000
C
total number of 42 terms. Preliminary correlations with more -.
than four nonanalytic terms tended to have an unreasonable
behavior concerning the dependence of Cu and w on density
in the critical region; moreover, when using more than four
-
~

0
\.)~
500

of such complex terms, the numerical expense would have 'uro 200
0..
been increased without a significant improvement in the ro
u
quality of the equation. Anticipating Sec. 6 with regard to the 100
~
Q)
critical region, Eq. (6.1) will be discussed in this section to ...0
U
avoid repeating a discussion of the representation of caloric 50
properties in the critical region later in this paper.
Figure II shows the plot of C u on the critical isochore; for
.~
on
~
0 )IillJ
analytic equations of state this plot was already shown in 20
Fig. 9. In this figure, however, the solid line corresponds to Pc
Eq. (6.1). In contrast to the analytic CH 4-type equation, the to
350 400 450 500 550 600
new formulation is able to follow the strong curvature of the 3
Cz; plot in the immediate vicinity of the critical temperature
Density pi (kg/m )

and yields an infinite value for the specific isochoric heat FIG. 15. For temperatures between Tc and T, + 1 K Eq. (6.1) results in an
capacity at the critical point. Accordingly, the evaluation of oscillating plot for the isobaric heat capacity around the critical density.

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 1540 R. SPAN AND W. WAGNER

TABLE 27. Coefficients of the correlation equations, Eq. (6.2) and Eq. (6.3), cal point and which is still explicit in the physical variables T
for c~ and cPo, respectively
and p. In Sec. 7 it will be shown that this nonanalytic be-
havior does not affect the quality of the equation with respect
to the representation of other properties anywhere outside the
8.373 044 56 0.62105248 6.11190 critical region.
-3.70454304 6 0.411 95293 6.777 08
Nevertheless, empirical equations of state containing
2.50000000 7 1.040 289 22 11.323 84
4 1.994 27042 3.151 63 0.083 27678 27.087 92 non analytic terms have certain limits if an exact fulfillment
of the asymptotic power laws is required. The nonanalytic
terms in Eq. (6.1) do not replace the contribution of the
analytic terms in the surrounding of the critical point but
similar values for the speed of sound. However, on ap- they fill the increasing gap between the analytic and nonana-
proaching the critical temperature, both the crossover equa- lytic behavior. Therefore, efficient values of the exponent
tion and the nonanalytic wide-range equation, Eq. (6.1), de- hi are smaller than theoretically expected and result in a criti-
velop a sharp minimum in the speed of sound, whereas the cal exponent a which is too large from an asymptotic point
speed of sound calculated from the analytic equation does of view [see Eq. (5.5)].
not change significantly when approaching the critical tem- Figure 14 shows that Eq. (6.1) represents the measured
perature. Within the same density range, Fig. 13 shows the and theoretically predicted values of Cv without significant
corresponding plots of the specific isochoric heat capacity deviations for temperatures in the region IT-Tel> 0.2 K and
calculated from the same set of equations. withm about :i: 10% tor U.2 K~(1'-1~)~O.3 mK in the ho-
Thus, Eq. (6.1) is the first wide-range equation which mogeneous phase and for -0.2 K::::;(T-TJ::::; -10 mK in the
yields a nonanalytic behavior of the isochoric heat capacity two-phase region. The plotted Cv courses correspond to the
and the speed of sound in the immerliilte vicinity of the criti- critical isochore in the one- (T> TJ and t,vo-phase (T< Tc)

0.1 r-----------------~----~----------------------_r------------_.

I \ I
I I [J
c
c x x x
0..
*
><
o Ill.
'i..Jr::.. • •
---
".-...,

~ -0.1L---~--~~~---L--~--~--~--~~--~--~--~--~---L--~--~

0'i..J~
U 0 300 600 900 1200 1500
10.. 0.5 ~----------------------------------------------------------~
><
<I.)

0'i..J~ -A
'-" [!]
oo r> .-.-.-.-.
.,.-.--.-
~ - - - - -
[!]
[!]
<l <l
c;]<1 <l
v
-0.5 L....-----J--+4------L_-----'-_---l..._---L.._---l...._--'-_---L...._--I....-_---L..-_---'--_

200 250 300 350 400 450 500

Temperature T / K
o Chao
l84
• Chao
l83
t> Kistiakowsky and Rice 163
X Baehr et al. 181 + Woole/
80
o Bender et ai.177
65
<l De Groot and Michels 164 o Gurvich et at. 182 o Masi and Petkof
~ Ernst et al.
l78 179
V Ernst and Hochberg
3
Angus et al.
15
-.-.- Ely et al.

FIG. 16. Relative de\'iations of c~ data from values calculated from Eq. (6.2). The upper diagram shows data calculated from statistical thermodynamics (see
Table 15) and the lower diagram shows data extrapolated from experimental results (see Table 13). Values of c~ calculated from the corresponding equations
of Angus et af.·l and Ely et af.ls are plotted for comparison.

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1541

TABLE 28. The ideal-gas part of the dimensionless Helmholtz function c/J0 and its derivatives a

8
c/J0 In 8 + aOI + a~r + a~ In(r) + L a~ln(1-e-e:T)
i=4

c/J~ 1/8 + 0 + 0 + 0 + 0

c/J 8S -lIU + 0 + 0 + 0 + 0
0
c/J~T 0 + 0 + 0 + 0 +
8

c/J~ 0 + 0 + aO2 + a~/r + ~ a7 07[ ( 1 - e - (J~ T) - I - 1]

i=4
8

4>~T = 0 + 0 + 0 a~/~ ~ a~(On2e-(J~T(1-e-(J»-2

i=4

ac/J8= [ac/J°la8]T' c/J 8S = [a 2c/J°la82]T' c/J~= [ac/J°larJs. c/J~T= [a2c/J°la~]s.andc/J8T= [a 2c/J°la8ar].

region. However, within a region of about +0.1 mK (outside where 8 = pI Pc and r = TclT with Pc = 467.6 kg/m3 and
the temperature range shown in Fig. 14) and - 10 mK around Tc = 304.1282K.
the critical temperature, Eq. (6.1) yields specific isochoric The formulations which describe the ideal-gas part of the
heat capacities which are significantly larger than the values Helmholtz energy, Eq. (6.3), and the residual part of the
predicted by the crossover equation of state. Helmholtz energy, Eq. (6.5), are introduced in this section.
Figure 15 shows a problem which is related to a small
oscillation in the derivative (op/ op h close to the critical
point. Since the numerical value of this derivative is small 6.1 Ideal-Gas Part of the Helmholtz Energy
close to the critical point, even a very small oscillation in this
According to Eq. (2.4), the ideal-gas part of the Helmholtz
derivative results in a significant oscillation of properties re-
energy can be easily obtained if the function c~(T) is known.
lated to its reciprocal value like the isobaric heat capacity
A correlation equation for c~(T) has been established by
[see Eq. (5.1)] or the isothermal compressibility. Derivatives
means of a nonlinear fitting routine using the 150 c~ data of
of these properties [e.g., (ocp/oph] should not be used in
the range 440 kg/m3:::;p:::;500 kg/m3 and (T-Tc):::;2 K. Os- Chao l84 as input values (cf. Sec. 4.2.2). With the coefficients
given in Table 27, the obtained equation
cillations are also observed in the derivative (oc v / oT) p
for approximately 420 kg/m3:::;p:::;550 kg/m3 and
(T-Tc):::; 15 K. TABLE 29. Summary of selected data used for the linear optimization pro-
cedure and for the nonlinear fit
The quality of Eq. (6.1) should be sufficient for any appli-
cation which requires numerical values of thermodynamic Number of data
properties in the critical region. Equation (6.1), however, is Details of the
data set are Linear Nonlinear
not suitable to investigate the asymptotic behavio{ of ther-
Property given in. optimization fit
modynamic properties and the derivatives mentioned above
should not be used in the regions indicated. p(T,p) Table 12 2824 2824
cu(T,p) Table 14 553 553
a
cp(T,p) Table 17 359 359
c;(T) Table 24 7Y 73
6. The New Equation of State w(T,p) Table 19 422" 422
w'(T) Table 24 2~" ?l
w"(T) Table 24 18" 18
As discussed in Sec. 2.1 the new equation of state for !1h(T,p) Sec. 4.5 10" 10
carbon dioxide is a fundamental equation expressed in form !1u(T,p) Sec. 4.6 ISO ISO
of the Helmholtz energy ~" J.L(T,p) Sec. 4.7 34
p(T,p') 205 b
A (p, T)/(RT) = ¢( 8, r) = ¢O( 8, r) + ¢r( 8, r), (6.1) p(T,p") 20S b

Maxw.-crit. 205 b
p,(T) Table 7 109
CThe recent experimental results of Wagner et al. 230 for the "thermal" criti- p'(T) Table 8 50
cal exponents f3. y. and 8. derived from ppT measurements in the imme- p"(T) Table 9 42
diate vicinity of the critical point show clear differences from the corre-
sponding values predicted by the renormalization group theory. These
suprising results might be caused by an extended validity range of the Total number of data points 5047 4667
so-called explicit influence of gravity (the implicit influence of gravity, e.g.,
the averaging errors based on density stratifications. was taken into account aLinearized data used in the optimization procedure; see Setzmann and
when evaluating the experimental ppT data). Thus. we think that the Wagner. 30
"true" asymtotic behavior at the gas-liquid critical point of a pure fluid is bLinearized solution of the Maxwell criterion when usin2: data calculated
not yet finally clarified. from the auxiliary Eqs. (3.13) to (3.15); see Wagner. 32 ~

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 1542 R. SPAN AND W. WAGNER

103 .-------------~~----------------------------------~

cPo~
d'0o
~ I ~ ~ gig ~ ~ In~L~g III
0
0
§
g e 0
0 g e
0
0
0
0 0
0 0 0 0 0 0 0 0
0
0
0
0
0
0
0

~OO~8 ~H~!~
g§gO§8ggg
t
00
<§D
00

~
()
0
00000.0.0
0

888000
0 0 0.0 0

o (). o8J .oO 0 0 0 0 0 0 0

00 8 "CID 0 .0 0 .0 0 0 .0
lit.aaI~ § 0 0 00000.0.0.0.0
o g .0
o 8 0 .0 0 0 o .0 0

o § 0
o 0 0
o § 0
o
o ppTdata
10- 1 ~_________0~~~____~____~____~____L -__~__L-~_____
200 300 400 500 600 800 1000

103 =---------------~--------------------------------------~

-.....

o c, data
• u data
o cp data
QQ o o..tl o 0 0 o
• h data
\1 f-1 data
QO o 0 o 0 0 o wdata L::..
o o 0 o
10- 1 L -_ _~~_G~~~~~~&__£-L----~---L---L--~~----~

200 300 400 500 600 800 1000

Temperature T / K
FIG. 17. Distribution of the experimental data used for the establishment of the residual part of the. new fundamental equation, Eq. (6.5), in a pT diagram.

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1543

cO(T) 8 exp( efr) discussed in Sec. 2.3. The selected data which form the ex-
-p--= 1 +a~+ ~ af(efr)2 [ (eO )-1]2 perimental basis of the new equation of state for carbon di-
R i=4 exp i r
oxide have been presented in Sec. 4. Table 29 gives a brief
(6.2)
summary of the data used and refers to the corresponding
represents Chao's data with deviations less than ± 0.005% tables, where detailed information is given. Figure 17 shows
for 10 K~T<21O K and less than ±0.002% for the distribution of the experimental data used. In addition,
210 K~ T~ 1500 K. This means that the uncertainty of Eq. data have been calculated from auxiliary equations and from
(6.2) is almost equal to the uncertainty of the data which was preliminary equations of state in order to guarantee reason-
estimated by Chao to be less than ± 0.02%. Extrapolation of able behavior in regions where the existing measurements
Eq. (6.2) yields results which are reliable to ± 1 % for yield insufficient information. In detail, these are
T~ 4000 K and to ± 2 % for 4000 K < T~ 5000 K. Figure 16
shows deviations between values calculated from the
relations given by Angus et al. 3 and by Ely et at., I data
cor- c; • 13 values of the third virial coefficient, which have been
calculated from an auxiliary equation (see Sec. 4.8),
• 23 values of the specific isochoric heat capacity, which
obtained by theoretical approaches and by extrapolation of have been calculated from the crossover equation of Chen
ex Pp.ri mp.n t::l 1 rp..;mlts, ::Inn v::Ill1es c::Ilcl11ated from Eq. (6.2). et al. 27 in order to guarantee a reasonable dependence of
which correspond to the zero line. c v on density in the critical region,
The expression for cpO( 8, r), which has been derived from • 27 Tp points describing the course of the Joule curve,
Eq. (6.2) by integration, is which have been determined by graphical extrapolation
</J
0
( 8, r) = In( 8) + a~ + a~ r+ a3 In( r) (see Sec. 7.3.2),
8 • and 70 ppT data, which have been calculated from a pre-
+L
;=4
a?ln[l-exp(-re?)]. (6.3) liminary equation of state with an exceptionally good ex-
LrapulaLiull ut;haviul ill ullkr Lv prt;~t;lVt; Lhi~ prugrt;~~ (~t;t;

The coefficients a? and e? are given in Table 27. The Sec. 7.3.1).
coefficients a~ and a~ were adjusted to give zero for the ideal All these "artificial" data are neither considered in Table 29
gas enthalpy at To = 298.15 K and the ideal gas entropy at nor in Fig. 17. The consequences of the absence of caloric
T o=298.15 K and Po = 0.101 325 MPa. In Table 28, all de- data within the liquid region and at temperatures above 500
rivatives of the ideal-gas part cpo required for the calculation K are discussed in Sec. 7.2.2.
of thermodynamic properties are explicitly given. The bank of terms which was used in the optimization of
the final equation of state (see Sec. 2.3.2) contained a total of
6.2 Residual Part of the Helmholtz Energy
860 terms. As far as parameter ranges are predetermined by
The formulation for the residual part of the Helmholtz this general form, these ranges have been established in ex-
energy has been developed with the help of the procedure tensive tests. This bank of terms can be written as

4 20 6 10 8 8 8 16 10 12

cpr=?
1=1 J=O
4 n;,j 8 i r jl4+ 4 4 1=1 J=O
n;,j 8 i r jI2e-8+ 44
1=1 J=O
n;,j 8 i r j e-
82
+~ 4 !l;,j 8 i r j e-. 83 + ~
I-I J=O
~
1-1 J-O
ni,j 8 i~je-04
10 16 15 16 48
+" "
£..; £..;
n· .
I,J
8 i~je-b·5 + "~ "~ n· .
I.J
8 i~je-b<5 + "~ n.
I
8 dirie-CXi(O-fi)2_f3i(T-Yi)2
;= 1 j=5 1=8 J=5 1= 1
2 2 3 3

(h4)

The parameters of the modified Gaussian terms originally

introduced by Setzmann and Wagner30 have been slightly
changed for carbon dioxide; 48 of these expressions were
TABLE 30. Parameters of the nonanalytic terms in the bank of terms used in the bank of terms covering the following parameter
ranges: 1 ~di~3, 0~ti~3, 15~ai~25, 275~{3i~325, and
i.j.k.l.1I1 bj Bk C, Dill A" f3a
1.16~ 'Yi~ 1.25 with C; = 1. The values which have been
ai

3.00 0.875 0.30 10.00 225.0 0.700 0.300 used for the parameters of the 108 nonanalytic terms in Eq.
3.50 0.925 1.00 12.50 250.0 (6.1) are given in Table 30. The values used for b j' C I' and
4.00 15.00 275.0
D In resulted from a nonlinear fit of a preliminary formula-
"Predetermined from a simultaneous fit to saturated liquid and vapor densi- tion.
ties in the critical region. Proceeding from the bank of terms defined by Eq. (6.4),

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1544 R. SPAN AND W. WAGNER

TABLE 31. Coefficients and exponents of Eq. (6.5)a

t;

0.38856823203161 x 10° 0.00

0.293 854759427 40X 10 1 0.75
3 -0.55867188534934x10 1 1.00
4 -0.767531 995924 77x 10° 2.00
5 0.317 290 055 804 16X lOll 2 0.75
6 0.548033 158977 67x 10° 2 2.00
0.122 794 112 203 35X 10° 3 0.75

t;

1
8 0.216589615432 20X 10 1.50
9 0.158417351097 24X 10 1 2 1.50
10 -0.231327054055 03x 10° 4 2.50
11 0.581 169164 314 36X 10- 1 5 0.00
12 -0.553691372 053 82X 10° 1.50
13 0.489 466 159 094 22 x 100 5 2.00
14 -0.24275739843501 x 10- 1 6 0.00
15 0.624947905016 78X 10- 1 6 1.00
10 -U.11.1 "/)) {)U:l'.l)140X IUo b 2.UU
17 -0.370556852700 86x 10° 1 3.00
18 -0.167758797004 26x 10- 1 1 6.00
19 -0.119607366379 87X 10° 4 3.00 2
20 -0.456193625087 78x 10- 1 4 6.00 2
21 0.35612789270346XlO- 1 4 8.00 2
22 -0.744 277271 320 52x 10- 2 7 6.00 2
23 -0.173957049024 32X 10- 2 0.00
24 -0.21810121289527XIO- 1 2 7.00
25 0.243321 665592 36X 10- 1 3 12.00
26 -0.374401 334 234 63 x 10- 1 3 16.00
27 0.l43 387 l57568 78x 10° 22.00 4
28 -0.134919690832 86x 10° 24.00 4
29 -0.231 512250 53480xlO- 1 16.00 4
30 0.123631 25492901 x 10- 1 7 24.00 4
31 0.210583219729 40X 10- 2 8 8.00 4
32 -0.33958519026368xlO- 3 10 2.00 4
33 0.559936517715 92X 10- 2 4 28.00 5
34 -0.303351 180556 46X 1O-3 8 14.00 6

Ct; {3; I'i Ej

3
35 -0.213654886883 20X 10 2 1.00 25 325 1.16 1.00
36 0.266415691492 nx L0 5 0.00 25 300 1.19 1.00
37 -0.240272 [22045 57X 105 l.00 25 300 1.19 1.00
38 -0.283416034239 99x 103 3.00 IS 275 1.25 1.00
39 0.212472 844 001 79X 103 3.00 20 275 1.22 1.00

11; bi f3i A; Bi Ci Dj

40 -0.666422 765 4Q7 51 x 10° 3.500 0.875 0.300 0.700 0.3 10.0 275
41 0.726086323498 97x 10° 3.500 0,925 0.300 0.700 0.3 10.0 275
42 0.55068668612842xlO- 1 3.000 0.875 0.300 0.700 1.0 12.5 275

"R = 0.188924 I kJI(kg K); Tc == 304.1282 K; Pc = 467.6 kg/m 3 .

the modified optimization method (see Sec. 2.3.2) was used

to determine the combination of terms which yields the best (6.5)
representation of the linearized data set. The resulting formu-
lation for (he residual pan of (he Helmholtz energy is
7 34 with ~={(l-'T)+Ai[ (8- 1 )2J 1I(2{3)iF + Bi[(b'-1)2]Qi.
(pr~ 2: nj8"i"";i+ 2: lli8"i"";ie-O<'j After this linear optimization process, the final values of
i= J i='8 the coefficients ni of Eq. (6.5) have been determined by a
39 direct nonlinear fit to the linear and nonlinear data. These
+ I. ni~irie-ai(O-EiJ2_{3i(T- Yi)2 values are given in Table 31 together with the parameters
i=35 resuiting from the optimization process. No further improve-

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1545

TABLE 32. The residual part of the dimensionless Helmholtz energy (f/ and its derivatives'
7 34 39 42
4l= ~ n;oJiri+ ~ n;oJirie-~i+ ~ n;;oJirie-ai(li-Ei)2_f3i(T-y)2 + ~ njAbiOW- with A= (P+B;[(8-1)2]a i
;= 1 ;=8 ;=35 ;=40

'l' = e -C;(li-I )2-D;(T-I)2

¢~= ±
i= I
n;d;oJ;-lri+ f
i=8
n;e-~'[oJi-lri(d;-c;OCi)]+ f n;oJ;rie-ai(li-<'i)2-f3i(T-Yi)2[~-2a;(8- EJ]
;=35 8
+ ~
i=40
n;[Abi('l'+ 8 a'l') + aAb;
a8 a8
ow-]
7 34 39
¢~li= ~ n;~;(d;-l)oJi-2r;+ ~ nje-~'[oJi-2r;«dj-cjOCi)(dj-l-cjOC;)-cJOCi)]+
;= 1 j=8
2: njrie-ai(li-<'i)2_f3i(T-Yi)2
;=35

~
+.LJ n·
;=40'
[ ab ,.( -
fh
2
'l')
a'l'+ 8a- - + 8
otJor
bi
aa - -
b
a'l'+ -aa ; ( 'l'+8-
otJ or or
a'l') + -
otJ
2 b
a a-; 8'l' 1
otJor

Derivatives of the distance function Ab;:

Derivatives of the exponential function '1':

a'l'
a8 = -2C (8-1)'l'j

a2'l'
iAb; . a82 = [2C j ( S 1)2 1 ]2C j '¥
aT =2b abi - 1+4ffb;(b -l )ab;-2
j j a'l'
. a; = -2D;(,r-l)'l'
ia b; 2 aa a2'l'
-alXJr = - A.b. - Ab;-1(8-1 )[(8-1 )2]1/(2f3;)-1_2Bb (b -1 )Ab i - 2 _ -;;-:r =[2D,( T-l )2-1 ]?DiW
' , {3j ( ( a8
a2'l'
a8ar =4C;D;C8-1)(r-l)'l'

ment was achieved by refitting the b i' C i ' and D i of the 216 K:%;T~ 1100 K and 0 MPa:%;p:%; 800 MPa.
nonanalytic tenns.
The new fundamental equation for carbon dioxide,
Eq. (6.1), in combination with the fonnulations according to Estimations for the uncertainty of Eq. (6.1) are given in Sec.
Eqs. (6.3) and (6.5), is constrained to the critical parameters 8; the quality of the new equation of state is discussed in Sec.
given in Sec. 3.2. It is valid for the entire fluid region cov- 7 Th~ n~c.~"::lry rl~riv::ltives of Eq (6 S) are given in Table
ered by reliable data, namely for 32.

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 1546 R. SPAN AND W. WAGNER

0.02
~
<]
0 0
~
Tt
-0.02

00';

Q..
<],
0 0
0
......
T\
I •
-0.05

0.05

~ _:"}.-.-~-.-.~-.:.~.~?~~,
~
<J
0 0
0

Tl
I
-0.05
220 240 260 280 30 . 300 301 302 303 304 305
Temperature T J K Temperature T J K
58 58
o Duschek et al. o Duschek et al.
Aux. eqs. (see Sec. 3) Aux. eqs. (see Sec. 3)
15
-.-.- Ely et al. -. - . - Chen et al. 27
3
- .. - .. - Angus et at. , aux. eqs.
FIG. 19. Relative deviations 100Ay= 100 (Yexp-Ycaic)IYexp
FIG. 18. Relative deviations 100Ay= 100 (Yexp-Ycalc)IYexp(Y=Ps,P',p") (y = P s' p' ,p") of the near critical experimental saturation data of Duschek
of the experimental saturation data of Duschek at al. 58 from values calcu- et al. 58 from values calculated from Eq. (6.1). Values calculated from the
lated from Eq. (6.1). Values calculated from auxiliary equations presented in auxiliary equations presented in Sec. 3 and from the crossover of Chen
Sec. 3, the equation of state of Ely et al. 15 and the auxiliary equations of et al. 27 are plotted for comparison.
Angus et at. 3 are plotted for comparison.

parisons in the extended critical region. This formulation

7. Comparisons of the New Equation of yields very similar results to the IUPAC equation but at
State with Experimental Data and clearly less numerical expense. All the figures presenting
data in this region also contain values calculated from the
Other Equations of State crossover equation of Chen et al. 27 which is the most sophis-
ticated scaled equation of state published for carbon dioxide.
In this section, the quality of the new equation of state is The representation of the specific isochoric heat capacity and
discussed based on comparisons with selected experimental the speed of sound in the critical region was discussed in
data. In addition, most figures also show values calculated detail in Sec. 5.
from the equation of state published by Angus et al} which None of the existing equations of state for carbon dioxide
is commonly accepted as an international standard for carbon is valid on the ITS-90 temperature scale. Therefore, tempera-
dioxide, and by Ely et al., 15 which proved to be the best of tures were reconverted to the IPTS-68 scale by using the
the available equations of state for carbon dioxide. procedure of Preston-Thomas et al., 37 before values were
For the extended critical region, comparisons should be calculated from these equations.
performed with the complete IUPAC equation (Angus
et al. 3 ) which consists of an analytic wide-range equation, a 7.1 Liquid-Vapor Boundary
switching function, and a scaled equation for the description
of the critical region (see Sec. 1.2). Since the evaluation of 7.1.1 Thermal Properties on the Coexistence Curve
the combined equation causes numerical problems,d we de-
As shown in Sec. 3, the discussion of thermal properties
cided to use the equation of Pitzer and Schreiber l6 for com-
on the liquid-vapor boundary can be restricted to the repre-
sentation of the data of Duschek et al 58 The de\l1::ltinns he-
JThe data published in the rUPAC tables use temperatures according to the tween these data and values calculated from Eq. (6.1) by
IPTS-68 temperature scale, but regarding the equations there seems to be
using the phase equilibrium condition [see Eq. (2.2)] is
some inconsistency in the temperature scales used. In the critical region, the
published isochoric heat capacity data are partly determined graphically. shown in Fig. 18. The additional lines in this deviation plot
since th~ ~\'aluation of the combined equation yields unreasonable results. correspond to values calculated from the auxiliary equations

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1547

2 temperature a deviation of 0.48% in the saturated liquid den-

./

-~
<:] -.- .--- .-'
-.-- j
sity can be considered to be within the experimental uncer-
tainty .
0
s::
0
- -~ - - - - - -- Cb@
The crossover equation of Chen et ai. 27 is able to repro-
duce the vapor pressure data within their experimental un-
Tc certainty but it cannot represent the saturated vapor and liq-
-2 300 310
270 280 290 uid densities within the uncertainty of these state-of-the-art
2 .j measurements. The auxiliary equations presented in Sec.3
\ !/ reproduce the experimental data slightly better than Eq. (6.1)
~~
<:]
0
-' \- .... 0
_Cb-ro /

.f
does. If one is interested in thermodynamically consistent
values for all properties on the phase boundary, the evalua-
§ 000 \. 00
tion of Eq. (6.1) in combination with Eq. (2.2) should be
Tt 0060 Tc
"- used and not the simpler auxiliary equations given in Sec. 3.
-2 300
220 240 260 280
2 7.1.2 Caloric Properties on the Coexistence Curve
\
~cJ

<:]
Figure 20 shows the representation of group 1 data pro-
0 0 viding information on the caloric behavior on the phase
9 buundary. Tht; spt;t;d uf suund dala uf lilt; salulalt;d vapul
state measured by Novikov and Trelin 113 are reproduced
-2~2~2-0~--2~40~L-2-6~0~L-2~8-0~--3~0~
within ±0.5% for T<301 K and to ±3% for T>301 K.
Temperature T / K Only the last point 30 mK below the critical temperature
1s exceeds this limit, but since the temperature scale of No-
o Novikov and Trelin 113
llS
- - - Elyetal.
3 vikov and Trelin is uncertain by more than 30 mK (see
o Pecceu and Van Dael -.-.- Angus et al.
<:) Magee and Ely116 Sec. 4.10), we did not rely on this data point. The analytic
equations of state of Angus et ai. 3 and Ely et ai. 15 are not
FIG. 20. Relative deviations 100Lly= 100 (Yexp - Yca\c)IYexp (y=w",w',c;) able to follow the decreasing speed of sound when approach-
of experimental caloric data at saturation from values calculated from ing the critical point.
Eq. (6.1). Data calculated from the wide-range equations of Ely et al. 15 and Equation (6.1) represents both the speed of sound and the
Angus et al. 3 are plotted for comparison.
specific isobaric heat capacity in the saturated liquid state to
within ::t 1 %; the greater deviations of the w' data of Pecceu
and Van Dael l15 at temperatures between 249 K and 261 K
presented in this work (see Sec.3), to values calculated from
are due to a systematic offset in the data set. The equation of
the equation of state of Ely et al. 15 by using the phase equi-
Ely et ai. 15 yields results which are at least similar to those
librium condition and to values calculated from auxiliary
calculated from Eq. (6.1), but the formulation of Angus
equations for the saturation properties established by Angus
et ai. 3 fails in describing caloric properties in the saturated
et al. 3 Angus et al. recommend the use of their auxiliary
liquid state (see also the representation of c v in the homoge-
equations for phase equilibrium calculations since they yield
neous liquid region,' Sec. 7.2.2and Fig. 31).
better results than the IUPAC equation of state.
Figure 18 shows that Eq. (6.1) represents the very accurate
The new equation of state was fitted to the c;
data of
Magee and Elyl16 up to temperatures of 295 K since the
vapor pressure data of Duschek et aI. 58 to within ± 0.006%
in pressure. Saturated liquid and vapor densities are repre-
conversion of c c;
(J" to seems to be uncertain for higher tem-
peratures (see Sec. 3.8). Above 295 K the deviations between
sented to within ± 0.01 % in density up to 303.6 K and the converted data and the new fundamental equation remain
297.0 K, respectively. Approaching the critical point the de-
viations in density increase, but these deviations are still
within about ± 2 %; keeping in mind that c;
is strongly di-
verging when approaching the critical point, this result un-
within the experimental uncertainty of the data; thus, all the
derlines the consistent description of the critical region by
data are represented to within their experimental uncertainty.
Eq.(6.1).
None of the equations hitherto known is able to reproduce
the data at least roughly within their uncertainty (the uncer-
tainty values are given in Tables 7-9). 7.2 Single-Phase Region
Figure 19 shows the representation of the saturation prop- 7.2.1 Thermal Properties in the Single-Phase Region
erties in the critical region where a larger deviation scale is
used. The very good representation of the vapor pressure For carbon dioxide, the region where ppT data in refer-
data is practically not affected when approaching the critical ence quality are available extends up to pressures of 13 MPa
temperature and the density deviations increase only slightly, at temperatures up to 360 K. Within this region, the data sets
except for the last point measured for the saturated liquid of Duschek et al.,58.154 Gilgen et al., 159 Nowak et aI., 160d and
density. Duschek et al. 58 do not give any estimation for the Guo et al. 157 describe the ppT surface with an uncertainty of
uncertainty of this point. but only 36 mK below the critical approximately ± 0.02% in density and in the extended criti-

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 1548 R. SPAN AND W. WAGNER

217 K - 220 K
0.051"'""""""'"-..;:::---------------------------.
il
/ 1

o~~~~--~~~~~~--~~~~~--------------~
1 -. D .. _.~- .. -O- .. 8·-
··-·· _.. - .. - .. - .. _.. _.. - .. - .. - .. - .. .::::-..,.:.:.... -.. -
-0.05
r
'-
260K
0.05 I
1

I 1"- "-" -._- "- .. '-" .. --.-

.....
" -'~
0 -·(j··-O_ ..
0..
;.< 0 .-' D
c:t
........
-"-
,.-. /"
U [> /"
tau ./

~ -0.05
I
0..
;.<
290 - 292 K
0.05
~ / /
.- .....
.-' -.-
'-" / /

0
0
,.....-I
D D
0
,/

\ ,/
,/
\

-0.05
299 - 301 K
0.05 ./
.. ---

-0.05
0 2 4 6 8 10 12 14
Pressure p / MPa
15O
0 Duschek et al. 154 t> Jaeschke et al. Phase boundary
155 J
0 Duschek et at. 511 'l Jaeschke et al. (refr. index) Angus et al.
e Guo et a1.
1S7
~
l5S
Jaeschke et ai. (Burnet) Ely et al.
1S

159 l60b
0 Gi1gen et ai. tsl K1imeck
FIG. 21. Relative density deviations of very accurate ppT data at subcritical temperatures from values calculated from Eq. (6.1). Values calculated from the
wide-range equations of Ely et at. 15 and Angus et at. 3 are plotted for comparison.

cal region of ~ 0.02% in pressure. In an extended region ~ 0.05o/c in density. None of the existing equations of state
reaching up to pressures of 30 MPa and temperatures of had access to these data sets because the data have been
523 K, the data of Brachthiiuser l60 and Klimeck et al. 160b published since 1990. Equation (6.1) is able to reproduce
describe the ppT surface with an uncertainty of ~0.02% to these data within their experimental uncertainty (for the nu-

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1549

304K
0.05

-0.05
305 K
0.05

o
%
0..
>< 0 ....... .' - - .. -0 . _- -0 - . \ .. ··--··0·.
a,)

~ : 00 '.
-.... '-. >- •
,;
\<l
.-....u
~
u -0.05
~

0.. 313 K
><
a,) 0.05
~
---
0
0
.,......(

.. .............. ~.--
/

-0.05
318 K - 320 K
0.05
.. - .. -."-'.
<l
o ~~~~~~~~~~~~~~~D~D~~____~____~
QlDD
<J
'. <l \
\

-0.05 200 300 400 500 600 700 8 0

Density pi (kg/m3)
o Duschek et ai. 154 <l Ely et at. 17 Pitzer and Schreiber '6
15
@ Duschek et at. 58 x Wentorf RlI. a Ely et al.
o Gilgen et al. 159 c::J Nowak et ai. 160d Chen et ai.27
a Corrected data, see Sec. (4.10)
FIG. 22. Relative pressure deviations of very accurate ppT data in the extended critical region from values calculated from Eq. (6. I). Values calculated from
the wide-range equations of Ely et al. 15 and Pitzer and Schreiber l6 and from the crossover equation of Chen et aZY are plotted for comparison.

merical values of the uncertainty see Table 12). Figures 21 to in the gas and supercritical region. The equation of Ely
23 show the representation of some reference data on typical et al. 1S yields a suitable description of the gas region at low
isotherms in order to illustrate this statement. temperatures but it has problems for temperatures above
Figure 21 additionally contains data of Jaeschke l50 ,155 about 250 K. The equation of Angus et al. 3 is not able to
which also give a high-quality description of the ppT surface reproduce the state-of-the-art data in the gas region. In the

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 1550 R. SPAN AND W. WAGNER

337 K - 344 K
0.1
.' f
'W •/ I:
I :
'.

1SJlS1 1SJlS1 1SJ

.. - .. - ... - .. - .. - .. _.. -.......... ..'

.. _.
-0.1
423 K - 430 K
0.1 ,.,
W _.-.-.-.-._"",.,
'-'-'-'-' ~" ........ "", .. ~'-'-'- X .-.-.-
-.- ~ ....... lSI X ~ ~·--XX·-·-X·-·~ ---.f\]
.. ..- .. ~ ~ ~
o .. - .. ~.~ .. --
".

x x
X

-0.1
521 K- 540 K
0.1

_.' ......
o ~.,.. •• ,.., •• "*
o
~ o ~- .. - .. -"- .. -" .,..."

IZI
~.-.-.-.-.-.-.-.-.-'-.-.-.
f-
I-
I
'-
-0.1 I I I

681 K - 698 K
0.1

.. w··-··-

I-
I I I I l I
-0.1
5 6 7 8 9 10 20 30
Pressure pI MPa
103 l6011 3
In. Holste et al. W Fenghour et al. Angus et al.
15
X Hoinkis
145
lSl KIimeck 160b Ely et al.
160
o Gilgen et at. 159 IZl Brachthauser
154
o Duschek et ai.
FfG. 23. Relative density deviations of very accurate ppT data at supercritical temperatures from values calculated from Eq. (6.1). Values calculated from the
wide-range equations of Ely et af. 15 and Angus et af. 3 are plotted for comparison.

liquid region, none of the existing equations of state is able High-quality p p T data in the extended critical region are
to represent the reference data of Duschek et al. 154 and shown in Fig. 22. The data of Duschek et al. 58, 154 and Gilgen
8
Gilgen et al. 159 at least roughly to within their experimental et al. 159 are supplemented by the selected data of Wentort8
17
uncertainty. and by the data of Ely et al. which are consistent with the

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1551

240K- 245 K 348 K- 350K

.-' " ..,.

0.2 ;---------""T/.-r-.------.---...-:

*~: =... ~:...::/

O~ee~~~~~~
~X

0.2 r - -_ _ _ __=2.:::..;80:;..;K~-_=2=83::....;K~ _ _ __r____, 398 K

0.2 ; - - - - - - - - - - - - - - - - - - / : U .
I

.e
~:<
.

-
\

0.2 .----_ _ _ _ _----:..:42=3;...:K:.:...-_ _ _ _ _---.

323 K 448 K-473 K

0.2 ;--------....;.;.;...---'-~'-------_x__1
0.2 r---------:X~-~:-r-r----------,,.....,
X ~X I:'. /
........~.-....... ., ..
/.!~:)(_..
"..c.!~-..
-....'"'::::..:~:::.: ..
"-./.
o
.. -.
'.- .. - .. - ..J Ay

Pressure p I MPa Pressure p IMPa

0 Duschek et al. 154 1:::. J uza et al. 132 0 Gilgen et al. 159
~
L 149, a 8 Michels and Michels 122 e Golovskii and Tsymamyi
136
au
140
+ Vukalovich et at. 142 141 y Vukalovich and Altunin 128 Kirillin et al. , a
<>
~ POPOV al}~o Sayapov A Vukalovich and Altunin 129 V Jaeschke et at. ISS
111
I> Jaeschke 17 0 Duschek et al. 58 ~ Esper
m
<J bly et al. X Vukalovich et at. 131 e Guo etal.
103
0 Kirillin et al. 93, a ~ Kirillin et al. 138 'ill Holste et al.
14S
0 Michels et al. 123, a II Hoinkis -'W Fenghour et al. 1608
137
EB Magee and Ely 152 ~ Kirillin et al. , a lSI Klimeck 160b

Phase boun1ary a Corrected data, see Sec. 4.10

Angus etl~l.
Elyetal.

FIG. 24. Relative density deviations of selected ppT data from values calculated from Eq. (6.1). Values calculated from the wide-range equations of Ely
t:{ u/.I'i and AIlt;u:\ t:{ uf.' alC 1l1ultc;d fur cU1l11l<l1i:'UIl.

reference data by approximately ± 0.03% in pressure. Even resentation of the p p T data in the surrounding of the critical
in this region, Eq. (6.1) represents the reference data to isochore. However, at lower and higher densities, but clearly
within their experimental uncertainty. The deviations be- within the range of its validity, the crossover equation does
tween the data and values calculated from the equation of not reproduce the reference data within their experimental
Ely et al. 15 increase up to 0.1 % in pressure, which corre- uncertainty.
sponds to five times the uncertainty of the data, while the Figure 23 shows the representation of high-quality data at
equation of Pitzer and Schreiber l6 deviates by up to 0.2%. higher temperatures and pressures. Up to 523 K and 30 MPa,
The equation of Chen et al.,27 which is especially designed the p p T surface is defined by the data of Brachthauser l60 and
for the description of this region, yields a very suitable rep- Klimeck et al. 160b with an uncertainty of less than ± 0.05%

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 1552 R. SPAN AND W. WAGNER

0.3

o ..

773K 973K
0.3r-----------------------------~--~ 0.3 r-------------------------------...,.,
./ X X X ./
...... /
)...
X X ~-.-.-.-. /
1-'-'-'-'- )... ):-~

)...)..../
._)...

-0.3 L....-_....I....-----L...---L....l-J.....1-L....L.L.._----J_--'--....I....-.L.....L.....L.J...J.J
10 100 1 10 100
Pressure p / MPa Pressure p / MPa
l60a
'W Fenghour et al. )... Vukalovich and Altunin 129 Angus eta!.3
x Yukalovich et at. uo Ely et at.tt;

FIG. 25. Relative density deviations of selected ppT data at high temperatures from values calculated from Eq. (6.1). Values calculated from the wide-range
equations of Ely et al. 15 and Angus et al. 3 are plotted for comparison.

in density. For temperatures up to 698 K, the recent data of 200 MPa is given in Fig. 24. Generally, the new equation of
Fenghour et ai. 160a improve the uncertainty of the ppT sur- state describes the reliable data better than the older equa-
face to less than ± 0.1 % in density. tions. The comparison with the data sets of Duschek et ai. 154
A representative view on the complete group 1 set of the and Gilgen et ai. 1S9 shows that the use of adjusted data (see
ppT data up to temperatures of -173 K and pressures of Sec. 4.10) was reasonable.

373 K - 398 K 673 K -789 K

4r-------------------------------,

473 K - 573 K 883 K - 981 K

~t·~:~~·;:·~·;:~~-~-,,,~.
o
o

,I
100 300 500 700 900
Pressure p / MPa Pressure p / MPa

132 3
[!] Michels et al. 123, a 6. Juza et al. -.-.- Angus et at.
15
o Tsiklis et at. 139 o Shmonov and Shmulovich 148 _.. - .. - Ely et al.
a Corrected data, see Sec. 4.10

FIG. 26. Relative density deviations of selected ppT data at high pressures from values calculated from Eq. (6.1), Values calculated from the wide-range
eqllationc; of Fly pf 11/ 15 ann Angm pf 111 3 ar~ pl()tt~n for ('ompari~on: in thic; prec;c;lIr~ ranee, thec;e two eqllations of state are at least partly extrapolated (see
Table I),

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 A NEW EQUATION OF STArE FOR CARBON DIOXIDE 1553

303 K
2
.,/~
~ •• - •• -
.. '" 0'1
-.: / •• ":..!. •• ......... _.
-'.J~ 0
- ........
, -..,
u
]
(,,)~
-2

Q.,
333 K 393 K
:l 2
~
0
2! ., . _1

~: ,~,,::".~'::",~~::~~
0
...... 0

-2
0.1 10 100
-: 0.1 1 10 100
Pressure p / MPa Pressure p / MPa

o Ernst and Hochberg

l78
, a o Ernst et at. 179, a -.-.- Angus et ISat.
3

o Bender et al. 17'T, M <> Masi and Petkof 165 - .. - .. - Ely et al.
a Corrected data, see Sec. 4.10

FIG. 27. Relative deviations of selected isobaric heat capacity data from values calculated from Eq. (6.1). Values calculated from the wide-range equations of
Ely et at. 15 and Angus et at. 3 are plotted for comparison.

At temperatures above 698 K, Eq. (6.1) is essentially Sec. 4.10. The excellent representation of the data within the
based on the same data sets as the equations of Ely et al. 15 gas region, where the well-known contribution of c~ is pre-
and Angus et al. 3 Nevertheless, the three equations show sig- dominant, justifies this correction. In the region of the super-
nificantly different courses for pressures above 15 MPa. fig- critical maximum of c p' the deviations increase to about
ure 25 shows that the equation of Angus et al. 3 yields the ± 1% (+ 1.3% for a single data point) but the authors esti-
best representation of the data of Vukalovich and mate that the uncertainty of their data also increases to
Altunin. 128 ,129 However, in order to achieve a consistent de- ± 0.9% in this region.
scription of the caloric and thermal properties in other re- In Fig. 28, absolute values of the specific isobaric heat
gions, we had to assume that this data set exhibits a system- capacity in the low temperature gas region are plotted. When
atic error. The data of Fenghour et al. 160a support our approaching the sublimation curve, Eq. (6.1) yields a reason-
interpretation of the p p T surface for temperatures up to
698 K.
Figure 26 shows how the p p T data at very high pressures
are represented. Since the range of validity is limited to
100 MPa for the equation of Angus et al. 3 and to 300 MPa
for the equation of Ely et aI., 15 these equations are already
extrapolated when plotting values calculated from these 0.78
equations in Fig. 26. With an estimated uncertainty ranging ,-..,

from 1% to 2% in density, the data of Tsiklis et al. 139 and g

0.76

--
OJ)
Shmonov and Shmulovich 148 represent the transition to the ~
'-"
extrapolation range of Eg. (6.1) which is discussed in Sec. ~

7.3. Equation (6.1) yields a suitable representation of these ~ 0.74

o Bender et at. 177
data. (,,)"'-
o Masi and Petkof 165
I
0.72 Eg. (6.1) 3
7.2.2 Caloric Properties in the Single-Phase Region Angus etl/I.
Ely et at.
In the gas and the supercritical region, the caloric behavior
of an equation of state for carbon dioxide can be discussed
most advantageously by the example of the specific isobaric Temperature T / K
heat capacity. Figure 27 shows the deviation between values
FIG. 28. Representation of the isobaric heat capacity on isobars in the gas
calculated from Eq. (6.1) and reliable measurements of c p .
region and in states on the sublimation curve (saturated vapor). Values cal-
The data of Bender et al., 177 Ernst and Hochberg,l78 and of culated from the wide-range equations of Ely I2t ar 15 and Angl1~ et aT 3 are
Ernst et al. 179 were corrected according to the descriptions in plotted for comparison.

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 1554 R. SPAN AND W. WAGNER

OMPa- 3 MPa 1.00

o
_<>. _<>. - . - . - . -
~o
- . - . - . -<)
0.95

~ _.------
bl) ...-
...!:.d ...-
~
0.90 /'
...-
- --
...- ...-
'-'
./

cJ .,
0.85 \bc\)'f.~Itt'- - <> Magee and Ely116
\/
/ Eq. (6.1) 3
/ Angus et at.
500 550 600 650 700 r- Ely et ai.
IS

Temperature T / K 0.80
0 5 10 15 20 25 30
3
o Bender et al. 177, a Angus et at. Pressure plMPa
15
<> Schrock 166 Ely et al.
a Corrected data, see Sec. 4.10 FIG. 31. Representation of the isochoric heat capacity on high-density iso-
chores. For each of the isochores the plotted pressure range starts at the
FIG. 29. Relative deviations of isobaric heat capacity data at high tempera- corresponding vapor pressure. Values calculated from the wide-range equa-
tures from values calculated from Eq. (6.1). Values calculated from the tions of Ely et al. 15 and Angus et a1. 3 are plotted for comparison.
wide-range equarions of Ely er at. 15 and Angus et at. 3 are plOtted for com-
parison.
baric heat capacity on the sublimation line at temperatures
below T t . Due to the high triple-point pressure of CO 2
able extrapolation of the plotted isobars. The equation of (Pt = 0.51795 MPa) and the widespread use of dry ice, an
Angus et at. 3 also shows a reasonable extrapolation behav- unreasonable behavior in this region is less acceptable for
ior, but comparisons with recent data l77 at a temperature of carbon dioxide than for other substances.
233 K indicate that the resulting values are too high. In con- At ten1peratures above 400 K, the values calculated from
trast to this, the isobars calculated from the equation of Ely the different equations of state agree much better with each
et al. 15 intersect with each other and with the specific iso- other than with the data of Schrock l66 which are plotted in

3
265 kg/m
10 ! 000
Ii 00000
o
o
I; .. _.. -,,-,,_ .. _,,_,,_,,_
O~--------~I~'~~~'~~'~~~·~~

1/
-1 0 '----'----'-----'(~._ " - - - - - - - - - L _ - ' - - _ L - - _
280 300 320 340 280 300 320 340
Temperature T / K Temperature T / K

/:). Amirkhanov and Polikhronidi 188 o Magee and Ely116 Phase boundary
187 3
"V Amirkh::mnv pt nl Angus et a1.
I5
Ely et al.

FIG. 30. Relati\'e de\'iations of selected isochoric heat capacity data from values calculated from Eq. (6.1). Values calculated from the wide-range equations
of Ely el (//. I" and Angus ef al.·' are plotted for comparison.

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1555

308K 4~_________
29_8_K_-_3_2~3_K~______- ,
2~----------~~----~/~\-.----'

a ; \
a a a a CLO-O-fl..0 r!: '"' 'fa a
.. - .. - ..-.:.:.:::Y ::=,'t '-'r:'::"'.-. . .....
Y! "
~~ _2L---~--~--~--~---L--~~~--~
i '--
~: 373 K
io
o.......

4 6 8 10
Pressure p / MPa

o Novikov and Trelin

192
o Pitaevskaya and Bilevich 193
16 '3
Pitzer and Schrciber Angus ef{;l.
15
Ely et al. Ely et al.
27
Chen et al. FIG. 33. Relative deviations of speed of sound data at high pressures from
values calculated from Eg. (6.1). Values calculated from the wide-range
FIG. 32. Relative deviations of speed of sound data at supercritical tempera- equations of Ely et at. 15 and Angus et al. 3 are plotted for comparison; in this
tures from values calculated from Eq. (6.l). Values calculated from the pressure range, these two equations of state are at least partly extrapolated
wide-range equations of Ely et al. 15 and of Pitzer and Schreiber,16 and, in (see Table l).
the range of validity, from the crossover equation of Chen et alY are plot-
ted for comparison.
this behavior, the equation of Ely et al. follows the course of
the 1140 kg/m3 isochore, but it yields slightly too low spe-
Fig. 29. Up to 473 K, the data of Bender et al. support the cific isochoric heat capacities at lower densities. In spite of
results of the equations of state. At higher temperatures and these different tendencies, the deviations between c v values
moderate pressures, the influence of the residual part of c p calculated from these equations do not exceed 1.5% through-
decreases. Since the uncertainty of c~(T) is very small (see out the extrapolation down to the vapor pressure. Since the
Sec. 6.1) and at least some information on the residual part uncertainty in the specific heat capacity calculated from
of the equations of state is available from p p T data, the Eq. (6.1) is estimated to be ~:±: 1.5% in the whole high-
equations seem to be more reliable than the available c p data density region for pressures up to 40 MPa (see Sec. 8), we
in this region. believe that the uncertainty at subcritical pressures does not
Deviations with regard to the specific isochoric heat ca- increase due to the gap in the data set. New data which
pacity at gas and liquid densities are presented in Fig. 30. In describe the calori<;:, behavior of liquid carbon dioxide more
the gas region, the behavior of the new fundamental equation accurately would be desirable in order to prove whether this
concerning calOl·ic properties is based on the precise data of assessment is correct.
C p and w; the deviations between the c v data of Magee and The equation of Angus et al. 3 fails completely in the de-
El y 116 and values calculated from Eq. (6.1) and from the scription of the specific isochoric heat capacity at high den-
other equations of state, respectively, probably reflect the sities. In the liquid region, the deviation between Eq. (6.1)
uncertainty in the data. This fact has resulted in the low and this formulation grows to 16%.
average weighting factor listed in Table 17. At high densi- For carbon dioxide, the representation of speed of sound
ties, however, the C u experiments of Magee and Elyl16 measurements is a sensitive test for the quality of an equa-
yietded. reliable resulls which fmIll lhe Illusl illlpulLauL liuIl uf slale ill the fulluwiug lwu legiuus. The data of No-
source of information on the caloric properties at liquid den- vikov and Trelin 192 describe the caloric behavior within the
sities. gas and supercritical region. Figure 32 illustrates the repre-
Unfortunately. these C v data only describe states at super- sentation of w values on two representative isotherms of this
critical pressures (see Fig. 17), so that there is a wide gap data set. While all the considered formulations represent the
between caloric data in the single-phase region and in the data within their uncertainty at 373 K, only Eq. (6.1) is able
saturated liquid state. Figure 31 shows absolute values of the to reproduce the measurements at 308 K; in the extended
specific isochoric heat capacity on two liquid isochors. plot- critical region, the deviations do not exceed 2:: 0.7%. On the
ted versus pressure. Equation (6.1) follows the measurements 308 K isotherm the crossover equation of Chen et al. 27 yields
on the 880 kg/m3, 970 kg/m3, and 1050 kg/m3 isochors and deviations up to 2%.
yields with decreasing pressure ,li£htly incrpa,inB npviatinn, At tf'mperatllfe, hetween 29~ K and 473 K. Pitaevskaya
from the C L' values at the 1140 kg/m 3 isochore. In contrast to and Bilevich l93 measured speed of sound data at pressures to

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 1556 R. SPAN AND W. WAGNER

263 K - 283 K 353 K - 363 K

2~------------------------------~ 2r-----------------~~._--.--------~

o
DODO
O~------------------------------~
.. - .. - .. - .. - .. _.. - .. - .. - .. - "

2 r 323 K - 335 K I l 0 ~23 K: ~ ~: 1

-: f:~·:~·:~·:~·~,~·,~·~~~·: J. -.~. ~. ~. ,-,. ,;.,~ .: ~. -=.~~~:
0.1 10 0.1 10
Pressure p / MPa Pressure p / MPa

o Vukalovich et ai.206 o Bender et at. 177 Phase boun~ary

.6.. Altunin and Gureev 208 Angus et ltl.
Elyetal.

FIG.34. Relative deviations of experimentally determined Joule-Thomson coefficients from values calculated from Eq. (6.1). Values calculated from the
wide-range equations of Ely et al. 15 and Angus et al. 3 are plotted for comparison. The data of Vukalovich et al. 206 were not used when establishing Eq. (6.1).

450 MPa. These data are represented by Eq. (6.1) to within stances and general approaches, they will be discussed
their expected uncertainty of approximately::!:::: 2 %. Figure 33 elsewhere. 35 Here, the considerations are restricted to the
shows representative deviation plots covering the lowest and new fundamental equation for carbon dioxide; the following
highest temperatures of this data set. None of the previous subsections will give only a brief survey on the extrapolation
equations of state is able to yield a reasonable representation behavior of Eq. (6.0.
of these data. The equation of Angus et al. 3 is only valid up
to 100 MPa, and extrapolated values of the speed of sound
are expected to be uncertain. But the equation of Ely et aZ. 15
should yield reliable results at least within the range of its
validity, namely up to 300 MPa.
At pressures up to 1.5 MPa, the Joule Thomson measure
ments of Bender et al. 177 were used in the nonlinear fit but
these data could not be represented without systematic,
slightly temperature dependent deviations. After work on the
new equation of state had been completed, the isothermal
Joule-Thomson coefficients measured by Vukalovich ~ 200
et af. 206 were converted into differential J oule-Thomson co-
efficients by the use of the specific isobaric heat capacity ~
'-"
calculated from Eq. (6.1). The new equation represents the ~
converted data of Vukalovich et at. without systematic de- ..s o 1200 K
viations (see Fig. 34); the very accurate ppT data set in the Eo-. 150 o 1-100 K
~
gas region prevented the representation of the measurements • 1600 K
of Bender et al. which deviate from the correlation by ap- Eq. (6.1) 3
proximately 0.5% to 1%. Angus et at.
15
Ely et al.
7.3 Extrapolation Behavior of the New Fundamenta.1
Equation 100 "---1oo...l...-0-l.--2oo-L--- . L . . - -....1.- --'----400--'--0-
0 3oo0

Tm~pin~rl hy thf': rlil;r.n""ion ~t thf': Fifth Tntp.m~ti()n~l Work- Pressure p / MPa

shop on Equations of State, which took place in Bochum in
FIG. 35. Representation of experimentally determined fugacities on iso-
1990, the extrapolation behavior of empirical equations of therms at very high temperatures and pressures. Values calculated from the
state was examined in some detail during the work on carbon wide-range equations of Ely et al. 15 and Angus et al. 3 are plotted for com-
dioxide. Since these results cover features of different sub- parison.

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1557

30000 . - - - - - - - - - - - - - - - - " 1 3.5.-----r--------------,

Eq. (6.1) 3 o
Angus etgl. o - Eq. (6.1)
25000 Ely et ai. I
o Nellis et al. 232
o Schott 233

-~
4)
I-c
::s
15000
I
I
o
CI)
CI)

~ 10000 I
0..

"0 1.5r
5000 / 0
C,)
~
.L_._. "0
!U
O~~~I-~~~-L-L~~~~~~ cz:::
1300 1600 1900 2200 2500 1.0r-

Density p / (kg/m3)
FIG. 36. Representation of experimental data describing the Hugoniot curve
of carbon dioxide. Hugoniot curves calculated from the wide-range equa- 0.5
tions of Ely et af. 15 and Angus et af. 3 are plotted for comparison.

0
5 10 20
7.3.1 Extrapolation Beyond the Range of Primary Data
Reduced temperature T / 1'c
The range of validity of Eq. (6.1) is based on the range FIG. 37. The so-called ideal curves calculated from Eq. (6.1) and plotted in
where reliable data of thermodynamical properties exist. a piPe' log(T1Tc) diagram. The louIe-Thomson inversion curve and the
louIe inversion curve exceed the temperature range in which Eq. (6.1) is
However, two kinds of data exceed this range.
fitted to experimental data.
Figure 35 shows the representation of fugacities reaching
up to approximately 3600 MPa at temperatures between
1200 K and 1600 K. The data of Haselton et at. 231 were not h - hOH= 0.5(p - POH)' (lIPOH+ lip), (7.1)
used when developing Eq. (6.1) since it is difficult to esti- where h is the enthalpy, p the pressure, and P the density
mate the uncertainty of data originating from measurements after releasing the shock wave and hOH , POH' and POH are the
of chemical equilibria and since the logarithmic structure of initial values. Even though it is not yet clear whether these
the dependency between the fugacity 'P and the reduced measurements describe eqUilibrium states at all, comparisons
Helmholtz energy (see Table 3) prevents an inclusion into with these data are the only source of experimental informa-
the linear optimization proct:llurt:. Nevertheless, Eq. (6.1) tion on (he extrapulaliun behavior of an equation of state at
follows the course of the measurements, whereas both the very high pressures: Figure 36 shows Hugoniot plots calcu-
equation of Angus et ai. 3 and the equation of Ely et al. IS lated from Eq. (6.1) and from the other two equations of state
yield fugacities which are significantly too large. At least at considered here, compared with the data of Nellis et al. 232
low pressures, the remaining systematic deviations cannot be and Schott. 233 At approximately 34000 MPa, Nellis et al.
explained by a misbehavior of the equation of state. All observed a kink in the course of the Hugoniot curve which is
equations of state which have been investigated result in very interpreted as an indication of a spontaneous disintegration
similar fugacities at pressures below 1000 MPa. In this re- reaction. So it can be seen that Eq. (6.1) yields a reasonable
gion, the experimental results are inconsistent with p p T data description of the Hugoniot curve of carbon dioxide up to the
at lower temperatures. limits of chemical stability. A Tp plot, which is not given
At even highp.r pressures, shock wave measurements result here, shows that the Hugoniot curves calculated from the
in data for the Hugoniot relation equations of Ely et ai. 15 and Angus et al. 3 run into low tem-
perature solutions corresponding to solid states above densi-
ties of about 1400 kg/m 3.
TABLE 33. The definition of the zeroth- and first-order ideal curves of the
compression factor 7.3.2 Representation of "Ideal Curves"

Name of the ideal curve Definition Various authors (see Refs. 234 to 238) have discussed
plots of so-called ideal curvese as a lml"'~r"::tl hehavlOf of
Classical ideal curve Z=pv/RT= 1
Boyle curve caZlap)T=o
louie-Thomson inversion curve (aZlaT),,=o e"Ideal curves" are curves which connect all states where a special property
louie inversion curve «(')Z/(Ip),,= 0 of a fluid is equal to the corresponding property of the hypothetic ideal gas
in the same state.

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 1558 R. SPAN AND W. WAGNER

G F

: . _ _ ._., F
E
! ~.-.-.-.-.-. r'-'-'-'-'-'-'-'-'-'-'
._.J D i
._._._._._ ....L _._.-,
E t;\l
Q..
._.L._.-,
c
'-'-l~'"
. ~/
j
D i'-._._. -
~
t::l.. 101
~
D
G
('-)
. E/'
/. /'./'
/'
/'
/././

::s /' A ± 0.15% in cp

00
00
~ B B ±O.3% in cp
Q..
._._._._._ C ± 0.6% in cp
10° D ± 1.S%
E ±2.0%
A
F ±4.0%
G ~± 2.0%

300 400 SOO 600 800 1000

Temperature T / K

FlU. 38. Tult:ram;e diagram fur densiLies calculared from Eq. (6.1). In region FlU. 40. Tolt:rance diagram fur isobaric heal capaciLies cai<.:Uiared [rum
B the uncertainty in pressure is given. Eq. (6.1). In the immediate vicinity of the critical point (region G) it is
difficult to estimate an uncertainty in c p because of the growing influence of
uncertainties in temperature and pressure measurement.

pure substances. In 1991, de Reuck239 gave a brief survey on

this topic.
The most common ideal curves are the zeroth and first
ornp.r r.nTVp.c;; of thp. compresc;;ion factor which are defined by these curves calculated from Eq. (G.l). The new fundamental
the relations given in Table 33. Figure 37 shows the plot of equation was fitted to data up to reduced pressures of
plpc= 108 and up to reduced temperatures of TIT c=3.5.
Thus, the course of the ideal curves does not significantly
103~---------------------------------, exceed the pressure range covered by data, but both the
F loule-Thomson inversion curve and the louIe inversion
curve reach up to temperatures which clearly exceed the
range uf Lhe uaLa useu Lu fiL Eq. (G.l).
E
Preliminary..equations showed an unreasonable plot of the
louIe inversion curve at very high temperatures. In order to
force the equation to form a maximum in the course of the
t;\l
~ D second virial coefficient and to ensure that the equation of
~ state yields an intersection of the louIe inversion curve with
t::l.. 101 the zero pressure line at that temperature, 27 T P data were
·~'-'-'I'-'-'-'-'-'
~ G determined by graphical extrapolation of the louIe inversion
::s
00 c A ±0.03% in w curve in a pT plot (see Ref. 35). At these values of the state
00
Q)
I-c B ±0.2S% in w variables, the condition of the louIe inversion curve,
~ B
C ±O.S% in w cb~r = O. was introduced into the data set used during the
loU -_.---.- adjustment of Eq. (6.1). Since it is difficult to estimate the
D ± O.S% - ± 1.0% in w
E ± 1.0% - ± 2.0% in w uncertainty of the inversion condition, the weight of these
A data was determined by using estimations for the uncertainty
F ± 2.0% - ± 4.0% in w
of the independent variables T and p in combination with the
G ~ _±_....L...-----L_...l....-.....L...-.I-....I
10- 1 L....-_ _ _ _ _...I...-_ _..L...-_....J.... 1.0% in w
Gaussian error propagation formula [see Eq. (2.6)].
200 300 400 SOO 600 800 1000 Equation (6.1) shows reasonable plots of the ideal curves
Temperature TIK in thp. high tp.mpp.r~tnn~ region, see Fig. ~7. The temperature
at which the louIe inversion curve intersects the zero pres-
FIG. 39. Tolerance diagram for speed of sound data calculated from sure line and at which the second virial coefficient passes
Eg. (6.1). [n the immediate vicinity of the critical point (region G) it is
difficult to estimate an uncertainty in w because of the growing influence of through a maximum corresponds to about T1Tc = 26.9. Thus,
uncertainties in temperature and pressure measurement. the reasonable behavior of Eq. (6.1) reaches even up to terh-

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1559

peratures beyond the limits of the chemical stability of car- the liquid-vapor phase boundary within their experimental
bon dioxide. uncertainty. The consideration of state-of-the-art data has re-
sulted in a previously unequalled accuracy for the regions of
8. Uncertainty of the New Equation of major technical interest. Intensive work on the consistency of
State the data set used has led to reasonable results in regions with
a poor data situation.
Estimates for the uncertainty of an empirical equation of Special interest has been focused on the behavior of ca-
state have to be guided by comparisons with experimental loric properties in the critical region and on the extrapolation
data. In regions where no data are available, comparisons behavior of empirical equations of state. The introduction of
with existing ~quations of state can be used as a substitute. A nonanalytic terms enables the new wide-range equation of
conservative estimation of the uncertainty of ppT, w, and state to represent the isochoric heat capacity and the speed of
c p values calculated from Eq. (6.1) is illustrated in the toler- sound even in the immediate vicinity of the critical point; up
ance diagrams Figs. 38 to 40. Uncertainties in c v correspond to now, this attribute has only been a domain of scaled equa-
to the uncertainties given for c p in the liquid and gas region. tions of state which introduce iterative dependencies between
In the extended critical region, the uncertainty in c v may different sets of variables and a limited range of validity. An
exceed the uncertainty in c p' The uncertainty of 6.h or 6.u examination of the extrapolation behavior of empirical equa-
values calculated from Eq. (6.1) is less than or equal to the tions of state has resulted in new approaches which have
uncertainty in c p or c v' respectively. been used for the new formulation. For the basic properties
Outside the range of its valilliLy, Ell. (6.1) shvulll yield of carbon dioxide such as pressure, enthalpy, and fugacity,
reasonable results for the basic thermodynamic properties the new fundamental equation should yield reasonable re-
like pressure, enthalpy, and fugacity within the whole chemi- sults within the whole region of chemical stability.
cally stable region of carbon dioxide. Of course, the extrapo-
lation results have an increased uncertainty which cannot be , O. Appendix: ThermOdynamic properties
estimated. The calculation of derived properties such as the of Carbon Dioxide
speed of sound or specific heat capacities is not recom-
mended beyond the limits of validity. If such data are In order to preserve thermodynamic consistency all values
needed, the results should be checked carefully. presented in Tables 34 and 35 were calculated only from the
new equation of state, Eq. (6.1). Ideally, each entry in the
table should be given to one more significant figure than the
9. Conclusions input data warrant, but a strict adherence to this principle is
difficult, and a possible conflict has always been avoided by
Based on a comprehensive study on the experimental data including more figures than are strictly necessary. Especially
for the thermodynamic properties of carbon dioxide, a new in the extended critical region, interpolation between values
fundamental equation in the form of the Helmholtz energy given may result in uncertainties which are significantly
has been developed. This empirical formulation is valid in larger then the uncertainties of Eq. (6.1). For sophisticated
the fluid region up to temperatures of 1100 K and at pres- applications, values should be calculated directly from Eq.
sures up to 800 MPa. The equation is able to represent al- (6.1); a computer-code suitable for such applications can be
most all the reliable data in the homogeneous region and on obtained from the authors. .

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1560 R. SPAN AND W. WAGNER

TABLE 34. Thermodynamic properties of saturated carbon dioxide

Temperature Pressure Density Enthalpy Entropy Cu Cp Speed of

(K) (MPa) (kglm 3 ) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

216.592a 0.51796 1178.46 -426.74 -2.2177 0.97466 1.9532 975.85

13.761 -76.364 -0.59999 0.62921 0.90872 222.78
218 0.55042 1173.40 -423.98 -2.2051 0.97264 1.9566 965.66
14 ..'584 -7.'5.847 -0.6081.'5 0.63318 0.91743 222.94
220 0.59913 1166.14 -420.05 -2.1873 0.96983 1.9618 951.21
15.817 -75.142 -0.61957 0.63894 0.93032 223.15
222 0.65102 1158.81 -416.11 -2.1697 0.96707 1.9676 936.79
17.131 -74.473 -0.63080 0.64485 0.94386 223.31
224 0.70621 1151.40 -412.16 -2.1522 0.96437 1.9739 922.37
18.530 -73.840 -0.64185 0.65091 0.95807 223.44
226 0.76484 1143.92 -408.19 -2.1348 0.96174 1.9810 907.95
20.016 -73.2.:16 -0.6527.:1 0.65712 0.97302 223.52
228 0.82703 1136.34 -404.21 -2.1175 0.95917 1.9886 893.53
21.595 -72.692 -0.66347 0.66350 0.98875 223.57
230 0.89291 1128.68 -400.21 -2.1003 0.95667 l.9970 879.09
23.271 -72.178 -0.67406 0.67004 1.0053 223.57
232 0.96262 1120.93 -396.19 -2.0832 0.95425 2.0061 864.63
25.050 -71.708 -0.68452 '0.67675 1.0228 223.54
234 1.0363 1113.08 -392.16 -2.0661 0.95190 2.0160 850.14
26.936 -71.283 -0.69487 0.68363 1.0412 223.46
236 1.1141 1105.12 -388.11 -2.0492 0.94963 2.0267 835.61
28.935 -70.903 -0.70511 0.69068 1.0608 223.33
238 1.1961 1097.05 -384.04 -2.0323 0.94745 2.0384 821.02
31.052 -70.573 -0.71526 0.69792 1.0814 223.17
240 1.2825 1088.87 -379.94 -2.0155 0.94535 2.0510 . 806.38
33.295 -70.293 -0.72532 0.70534 1.1033 222.96
242 1.3734 1080.56 -375.82 -1.9988 0.94335 2.0647 791.67
35.670 -70.066 -0.73533 0.71297 1.1265 222.70
244 1.4690 1072.13 -371.68 -1.9821 0.94145 2.0795 776.87
38.184 -69.894 -0.74527 0.72081 1.1513 222.40
246 1.5693 1063.56 -367.51 -1.9654 0.93965 2.0956 761.97
40.845 -69.780 -0.75518 0.72889 1.1778 222.06
248 1.6746 1054.84 -363.30 -1.9488 0.93797 2.1131 746.95
43.662 -69.726 -0.76506 0.73725 1.2061 221.66
250 1.7850 1045.97 -359.07 -1.9323 0.93643 2.1320 731.78
46.644 -69.736 -0.77492 0.74591 1.2366 221.22
252 L9007 1036.93 -354.80 - L9157 O.9350h 71"077 71h44
49.801 -69.813 -0.78479 0.75489 1.2693 220.72
254 2.0217 1027.72 -350.50 -1.8991 0.93390 2.1751 700.88
53.144 -69.960 -0.79467 0.76421 1.3047 220.17
256 2.1483 1018.32 -346.15 -1.8826 0.93300 2.1995 685.08
56.685 -70.181 -0.80458 0.77388 1.3429 219.56
258 2.2806 1008.71 -341.77 -1.8660 0.93244 2.2262 668.99
60.438 -70.480 -0.81453 0.78390 1.3844 218.90
260 2.4188 998.89 -337.34 -1.8495 0.93227 2.2554 652.58
64.417 -70.862 -0.82456 0.79426 1.4295 218.19
262 2.5630 988.83 -332.86 -1.8329 0.93258 2.2874 635.84
68.640 -71.332 -0.83467 0.80498 1.4787 217.41
264 2.7134 978.51 -328.33 -1.8162 0.93344 2.3226 618.75
73.124 -71.896 -0.84488 0.81604 1.5326 :2l6.YJ
266 2.8701 967.92 - 323.74 -1.7995 0.93488 2.3617 601.31
77.891 -72.561 -0.85523 0.82749 1.5919 215.70
268 3.0334 957.04 -319.09 -1.7827 0.93693 2.4050 583.54
82.965 -73.334 -0.86573 0.83935 1.6575 214.76
270 3.2033 945.83 -314.37 -1.7658 0.93959 2.4534 565.46
88.374 -74.223 -0.87641 0.85168 1.7307 213.75
272 3.3802 934.26 -309.57 -1.7488 0.94283 2.5079 547.11
94.140 75.240 0.88732 0.86454 1.8128 212.68
274 3.5642 922.30 -304.70 -1.7317 0.94659 2.5694 528.51
100.32 -76.395 -0.89849 0.87801 1.9057 211.55
276 3.7555 909.90 -299.73 -1.7144 0.95082 2.6396 509.71
106.95 -77.702 -0.90995 0.89218 2.0117 210.35

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1561

TABLE 34. Thermodynamic properties of saturated carbon dioxide-Continued

Temperature Pressure Density Enthalpy Entropy Cu cp Speed of

(K) (MPa) (kg/m 3) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

278 3.9542 897.02 -294.66 -1.6969 0.95545 2.7203 490.72

114.Q7 -79.177 -0.92178 0.90719 2.1341 209.07
280 4.1607 883.58 -289.48 -1.6792 0.96046 2.8141 471.54
121.74 -80.840 -0.93401 0.92316 2.2769 207.72
282 4.3752 869.52 -284.17 -1.6611 0.96584 2.9246 452.19
130.05 -82.713 -0.94674 0.94029 2.4458 206.28
284 4.5978 854.74 -278.71 - 1.6428 0.97166 3.0569 432.63
139.09 -84.825 -0.96006 0.95878 2.6490 204.74
286 4.8289 839.12 -273.08 -1.6239 0.97806 3.2181 412.81
148.98 -87.214 -0.97407 0.97895 2.8979 203.10
288 5.0688 822.50 -267.24 -1.6046 0.98528 3.4189 392.63
159.87 -89.926 -0.98894 1.0012 3.2104 201.34
290 5.3177 804.67 -261.15 -1.5846 0.99373 3.6756 371.95
171.96 -93.02:5 -1.0049 1.0260 3.6142 199.45
292 5.5761 785.33 -254.76 -1.5637 1.0041 4.0145 350.49
185.55 -96.599 -1.0221 1.0543 4.1558 197.38
294 5.8443 764.09 -247.97 -1.5418 1.0177 4.4834 327.85
201.06 100.77 1.0411 1.0872 4.919U 195.09
296 6.1227 740.28 -240.68 -1.5183 1.0371 5.1813 303.44
219.14 -105.74 -1.0624 1.1269 6.0741 192.49
298 6.4121 712.77 -232.64 -1.4926 1.0675 6.3473 276.42
74090 -11183 -1.0872 Ll774 &.012& 1&9.3&
300 6.7131 679.24 -223.40 -1.4631 1.1199 8.6979 245.67
268.58 -119.70 -1.1 175 1.2476 11.921 185.33
301 6.8683 658.69 -218.03 -1.4460 1.1631 11.053 228.18
286.15 -124.73 -1.1361 1.2972 15.859 182.61
302 7.0268 633.69 -211.76 -1.4261 1.2316 15.786 208.08
308.15 -131.05 -1.1588 1.3676 23.800 178.91
303 7.1890 599.86 -203.73 -1.4004 1.3702 30.233 182.14
339.00 -139.91 - I.l897 1.4925 47.599 172.71
304 7.3555 530.30 - 188.42 -1.3509 2.0531 386.88 134.14
406.42 -158.84 -1.2536 2.0679 555.58 147.62
304.I282 b 7.3773 467.60 -174.53 - 1.3054

'Triple point.
bCritical point.

J. Phys. Chern. Ret. Data, Vol. 25, No.6, 1996

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 1562 R. SPAN AND W. WAGNER

TABLE 35. Thermodynamic properties of carbon dioxide

Temperature Density Internal energy Enthalpy Entropy Cv Cp Speed of

(K) Ckg/m3) (kJlkg) , (kJlkg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

0.05 MPa hVUdi'

a 1.4370 -123.74 -88.944 -0.23757 0.54404 0.74495 216.947

186.436
190 1.4089 -121.78 -86.286 -0.22345 0.54661 0.74660 218.90
200 1.3359 -116.22 -78.792 -0.18501 0.55478 0.75266 224.26
210 1.2704 -110.59 -71.228 -0.14811 0.56398 0.76029 229.41
220 1.2112 -104.86 -63.582 -0.11254 0.57386 0.76897 234.38
230 1.1575 -99.044 -55.846 -0.07816 0.58417 0.77834 239.20
240 1.1084 -93.125 -48.014 -0.04483 0.59473 0.78815 243.88
250 1.0634 -87.104 -40.082 -0.01245 0.60542 0.79823 248.44
260 1.0219 -80.978 -32.049 0.01906 0.61612 0.80845 252.88
270 0.98360 -74.747 -23.913 0.04976 0.62679 0.81871 257.23
280 0.94810 -68.412 -15.675 0.07972 0.63737 0.82895 261.49
290 0.91510 -61.973 -7.3344 0.10899 0.64782 0.83912 265.67
300 0.88434 -55.432 1.1072 0.13761 0.65812 0.84917 269.77
325 0.81585 -38.641 22.645 0.20655 0.68307 0.87366 279.71
350 0.75726 -21.246 44.781 0.27216 0.70681 0.89707 289.27
375 0.70656 -3.2771 67.489 0.33481 0.72932 0.91933 298.50
400 0.66224 15.237 90.738 0.39483 0.75063 0.94046 307.42
425 0.62317 34.268 114.50 0.45245 0.77081 0.96051 316.08
450 0.58847 53.788 138.76 0.50789 0.78995 0.97953 324.50
475 0.55743 73.774 163.47 0.56134 0.80811 0.99760 332.69
500 0.52951 94.201 188.63 0.61295 0.82537 1.0148 340.67
525 0.50426 115.05 214.20 0.66286 0.84179 1.0312 348.46
550 0.48130 136.29 240.18 0.71120 0.85744 1.0468 356.08
575 0.46035 157.92 266.54 0.75806 0.87236 1.0616 363.53
600 0.44115 179.92 293.26 0.80354 0.88660 1.0758 370.83
700 0.37809 271.21 403.45 0.97331 0.93747 1.1266 398.65
800 0.33081 367.15 518.30 1.1266 0.97994 1.1690 424.64
900 0.29404 466.98 637.03 1.2664 1.0155 1.2045 449.13
tOOO 0.26463 570.06 759.01 1.3949 1.0452 1.2342 472.37
1tOO 0.24057 675.87 883.71 1.5137 1.0702 1.2592 494.54

0.10 MPa Isobar

194.525" 2.7796 -120.24 -84.267 -0.34184 0.56013 0.76998 219.98

200 2.6980 -117.11 -80.049 -0.32046 0.56339 0.77091 223.00
210 2.5617 -111.36 -72.323 -0.28276 0.57062 0.77476 228.33
220 2.4394 -105.54 -64.547 -0.24659 0.57907 0.78067 233.45
230 2.3288 -99.645 -56.705 -0.21173 0.58833 0.78795 238.38
240 2.2282 -93.664 -48.785 -0.17803 0.59811· 0.79618 243.15
250 2.1363 -87.589 -40.780 -0.14535 0.60818 0.80501 247.79
260 2.0519 -81.419 -32.684 -0.11360 0.61843 0.81424 252.31
270 1.9741 -75.151 -24.494 -0.08269 0.62872 0.8237\ 256.72
280 1.9021 -68.784 -16.209 -0.05256 0.63900 0.83330 261.03
290 1.8352 -62.317 -7.8279 -0.02315 0.64922 0.84293 265.25
300 1.7730 -55.751 0.64941 0.00559 0.65932 0.85253 269.39
325 1.6348 -38.911 22.260 0.07477 0.68392 0.87619 279.42
350 1.5167 -21.479 44.452 0.14054 0.70743 0.89903 289.04
375 1.4147 -3.4815 67.203 0.20332 0.72978 0.92090 298.31
. lOa 1.3257 15.056 90.488 0.26342 0.75099 0.94173 307.28
425 1.2472 34.105 114.28 0.32111 0.77109 0.96156 315.97
450 1.1776 53.640 138.56 0.37661 0.79017 0.98041 324.41
475 1.1154 73.639 163.29 0.43011 0.80829 0.99835 332.62
500 1.0594 94.076 188.47 0.48175 0.82552 1.0154 340.62

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1563

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m 3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

0.10 MPa Isobar

525 1.0088 114.93 214.06 0.53169 0.84192 1.0317 348.43

550 0.96283 136.19 240.05 0.58005 0.85755 1.0473 356.06
575 0.92087 157.82 266.42 0.62693 0.87245 1.0621 363.52
600 0.88242 179.82 293.15 0.67243 0.88668 1.0762 370.83
700 0.75619 271.13 403.38 0.84226 0.93752 1.1269 398.68
800 0.66158 367.09 518.24 0.99558 0.97997 1.1692 424.68
900 0.58803 466.93 636.99 1.1354 1.0155 1.2046 449.19
1000 0.52921 570.02 758.98 1.2639 1.0452 1.2343 472.43
1100 0.48109 675.83 883.69 1.3827 1.0702 1.2593 494.61

0.101325 MPa Isobar

194.685 a 2.8147 -120.18 -84.180 -0.34383 0.56049 0.77056 220.03

200 2.7345 -117.14 -80.083 -0.32307 0.56362 0.77141 222.97
210 2.5963 -111.38 -72.352 -0.28535 0.57080 0.77516 228.30
220 2.4722 -105.56 -64.573 -0.24916 0.57921 0.78098 233.42
230 2.3601 -99.661 -56.728 -0.21429 0.58845 0.78821 238.36
240 2.2581 -93.678 -48.806 -0.18057 0.59820 0.79639 243.14
250 2.1649 -87.602 -40.798 -0.14789 0.60826 0.80519 247.78
260 2.0793 -81.431 -32.701 -0.11613 0.61849 0.81440 252.30
270 2.0004 -75.162 -24.509 -0.OS522 0.62S7S 0.82384 256.71
280 1.9274 -68.793 -16.223 -0.05508 0.63905 0.83341 261.02
290 1.8597 -62.326 -7.8410 -0.02567 0.64925 0.84303 265.24
300 1.7966 -55.760 0.63726 0.00307 0.65935 0.85262 269.38
325 1.6565 -38.918 22.250 0.07226 0.68394 0.87625 279.41
350 1.5369 -21.486 44.443 0.13803 0.70745 0.89908 289.03
375 1.4335 -3.4869 67.196 0.20082 0.72980 0.92094 298.31
400 1.3433 15.051 90.482 0.26092 0.75100 0.94177 307.28
425 1.2638 34.100 114.28 0.31862 0.77110 0.96159 315.97
450 1.1932 53.637 138.55 0.37412 0.79018 0.98044 324.41
475 1.1302 73.635 163.29 0.42761 0.80829 0.99837 332.62
500 1.0735 94.073 188.46 0.47926 0.82552 1.0155 340.62
525 1.0222 114.93 214.06 0.52920 0.84192 1.0317 348.43
550 0.97559 136.18 240.04 0.57756 0.85755 1.0473 356.06
575 0.93308 157.82 266.41 0.62444 0.87246 1.0621 363.52
600 0.89412 l79.82 293.14 0.66994 0.88668 1.0762 370.83
700 0.76621 271.13 403.38 0.83977 0.93752 1.1269 398.68
800 0.67035 367.09 518.24 0.99309 0.97997 1.1692 424.69
900 0.59582 466.93 636.99 1.1329 1.0155 1.2046 449.19
1000 0.53622 570.02 758.98 1.2614 -i.0452 1.2343 472.44
1100 0.48746 675.83 883.69 1.3803 1.0702 1.2593 494.61

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1564 R. SPAN AND W. WAGNER

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cu cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (mls)

0.20 MPa Isobar

a -116.97 -79.973 -0.44750
203.314 5.4054 0.58210 0.80842 222.32
210 5.2116 -112.95 -74.577 -0.42138 0.58456 0.80597 226.10
220 4.9495 -106.93 -66.522 -0.38391 0.58993 0.80556 231.52
2:;U 4.7152 -lUUJn -5~.456 -U.:;4~U6 U.51J6':J:l U.~u!HIJ 2:;6.7U
240 4.5039 -94.758 -50.352 -,0.31357 0.60502 0.81291 241.68
250 4.3120 -88.575 -42.193 -0.28026 0.61383 0.81906 246.49
260 4.1369 -82.313 -33.967 -0.24800 0.62310 0.82618 251.16
270 3.9761 -75.967 -25.667 -0.21668 0.63264 0.83396 255.69
280 3.8280 -69.534 -17.286 -0.18620 0.64231 0.84219 260.l0
290 3.6909 -63.010 -8.8222 -0.15650 0.65203 0.85070 264.42
300 3.5636 -56.394 -0.27188 -0.12751 0.66174 0.85938 268.64
325 3.2819 -39.454 21.487 -0.05786 0.68562 0.88131 278.83
350 3.0423 -21.947 43.792 0.00825 0.70867 0.90300 288.58
375 2.8360 -3.8914 66.631 0.07127 0.73072 0.92405 297.95
400 2.6562 14.692 89.987 0.13156 0.75170 0.94429 306.99
425 2.4981 33.778 113.84 0.18939 0.77166 0.96367 315.74
450 2.3580 53.344 138.16 0.24500 0.79062 0.98219 324.23
475 2.2328 73.368 162.94 0.29858 0.80865 0.99986 332.49
500 2.1204 93.827 188.15 0.35030 0.82582 1.0167 340.53
525 2.0188 114.70 213.77 0.40030 0.84217 1.0329 348.37
550 1.9265 135.97 239.79 0.44871 0.85776 1.0482 356.02
575 1.8424 157.62 266.18 0.49563 0.87263 1.0630 363.51
600 1.7653 179.63 292.93 0.54117 0.88684 1.0770 370.83
700 1.5124 270.99 403.22 0.71109 0.93761 1.1274 398.74
800 1.3230 366.97 518.13 0.86447 0.98003 1.1696 424.78
900 1.1759 466.82 636.91 1.0043 1.0155 1.2049 449.30
1000 1.0582 569.93 758.93 1.1329 1.0452 1.2345 472.56
1100 0.96197 675.75 883.66 1.2517 1.0702 1.2594 494.75

0.30 MPa Isobar

208.79r 8.0141 -115.37 -77.936 -0.51088 0.59903 0.84154 223.07

210 7.9594 -114.62 -76.925 -0.50605 0.59918 0.84031 223.78
220 7.5367 -108.37 -68.563 -0.46715 0.60144 0.83277 229.53
230 7.1633 - 102.13 -60.253 -0.43021 0.60593 0.82996 234.98
240 6.8298 -95.878 -51.953 -0.39488 0.61219 0.83067 240.18
250 6.5292 -89.579 -43.632 -0.36091 0.61964 0.83382 245.17
260 6.2564 -83.222 -35.271 -0.32812 0.62n~ U.~:;~6:; 241J.1J~

270 6.0072 -76.795 -26.855 -0.29636 0.63662 0.84459 254.64

280 5.7785 -70.293 -18.376 -0.26553 0.64567 0.85136 259.17
290 5.5675 -63.710 -9.8262 -0.23553 0.65488 0.85869 263.58
300 5.3723 -57.043 -1.2010 -0.20629 0.66418 0.86640 267.88
325 4.9416 -40.000 20.709 -0.13615 0.68733 0.88653 278.24
350 4.5770 -22.417 43.128 -0.06970 0.70992 0.90702 288.1 I
375 4.2638 -4.3028 66.057 -0.00643 0.73165 0.92723 297.58
400 3.9916 14.326 89.485 0.05404 0.75242 0.94687 306.70

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1565

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kglm3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (rn/s)

0.30 MPa Isobar

425 3.7526 33.450 113.40 0.11202 0.77222 0.96580 315.52

450 3.5410 53.048 137.77 0.16774 0.79107 0.98397 324.06
475 3.3523 73.097 162.59 0.22141 0.80902 1.0014 332.36
500 3.1829 93.578 187.83 0.27320 0.82612 1.0180 340.43
525 3.0299 114.47 213.48 0.32326 0.84242 1.0340 348.30
550 2.8911 135.76 239.53 0.37172 0.85797 1.0492 355.98
575 2.7646 157.42 265.94 0.41868 0.87282 1.0638 363.49
600 2.6487 179.45 292.71 0.46426 0.88699 1.0778 370.84
700 2.2687 270.84 403.07 0.63428 0.93770 1.1279 398.80
800 1.9844 366.84 518.02 0.78771 0.98009 1.1699 424.87
900 1.7635 466.72 636.83 0.92761 1.0156 1.2052 449.41
IOOO 1_'iR70 "itiQR4 7"iR 87 L0562 L0453 1.2347 472.69
1100 1.4426 675.67 883.63 1.1750 1.0703 1.2596 494.88

0.50 MPa Isobar

216.075 a 13.282 114.05 76.405 -0.59404 0.62692 0.90323 222.86

220 12.974 -111.42 -72.876 -0.57785 0.62625 0.89522 225.33
230 12.265 -104.78 -64.010 -0.53843 0.62547 0.87913 231.38
240 11.646 -98.202 -55.270 -0.50124 0.62750 0.86991 237.06
?"iO 110Q7 -91650 -46_594 -0_46582 0.63186 0.g65g3 242.44
260 10.606 -85.086 -37.941 -0.43188 0.63782 0.86526 247.58
270 10.161 -78.487 -29.281 -0.39920 0.64484 0.86710 252.51
280 9.7568 -71.840 -20.594 -0.36761 0.65255 0.87063 257.27
290 9.3864 -65.133 -11.865 -0.33697 0.66071 0.87537 261.87
300 9.0456 -58.359 -3.0836 -0.30721 0.66916 0.88096 266.35
325 8.2996 -41.105 19.139 -0.23606 0.69081 0.89726 277.05
350 7.6736 -23.365 41.793 -0.16892 0.71244 0.91523 287.18
375 7.1393 -5.1305 64.905 -0.10514 0.73353 0.93370 296.85
400 6.6770 13.593 88.478 -0.04430 0.75386 0.95209 306.13
425 6.2725 32.793 112.51 0.01397 0.77335 0.97010 315.07
450 5.9154 52.453 136.98 0.06991 0.79197 0.98757 323.72
475 5.5975 72.554 161.88 0.12376 0.80975 1.0044 332.10
500 5.3126 93.079 187.19 0.17570 0.82672 1.0207 340.25
525 5.0558 114.01 212.91 0.22588 0.84292 1.0363 348.18
550 4.8229 135.33 239.00 0.27443 0.85840 1.0512 355.91
575 4.6108 157.02 265.46 0.32148 0.87318 1.0656 363.47
600 4.4168 179.07 292.28 0.36713 0.88731 1.0794 370.85
700 3.7814 270.54 402.76 0.53734 0.93789 1.1289 398.92
800 3.3067 366.60 517.81 0.69090 "0.98022 1.1707 425.06
900 2.9383 466.51 636.68 0.83087 1.0157 1.2057 449.64
1000 2.6439 569.65 758.77 0.95947 1.0453 1.23.52 472.94
1100 2.4033 675.51 883.56 1.0784 1.0703 1.2600 495.15

J. Phys. Chem. Ref. Data, Vol. 25, No.6, 1996

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 1566 R. SPAN AND W. WAGNER

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJlkg) (kJlkg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (rnIs)

0.75 MPa Isobar

b
216.642 1178.77 -427.22 -426.58 -2.2178 0.97489 1.9518 976.77
220 1166.48 -420.66 -420.01 -2.1878 0.97002 1.9607 952.10
225 1147.71 -410.82 -410.17 -2.1435 0.96306 1.9772 915.26
225.50Y 1145.78 -409.83 -409.17 -2.1391 0.96238 1.9192 911.52
225.505 c 19.640 -111.58 -73.389 -0.65006 0.65557 0.96925 223.51
230 19.095 -108.34 -69.068 -0.63108 0.65297 0.95402 226.53
235 18.535 -104.80 -64.335 -0.61073 0.65047 0.93952 229.79
240 18.018 -101.29 -59.668 -0.59107 0.64888 0.92783 232.92
245 17.536 -97.821 -55.052 -0.57204 0.64826 0.91866 235.94
250 17.087 -94.371 -50.477 -0.55356 0.64852 0.91161 238.87
255 16.665 -90.937 -45.933 -0.53556 0.64951 0.90630 241.70
260 16.269 -87.513 -41.1112 -0.51800 0.65110 0.902-11 2-1-1.116
265 15.894 -84.094 -36.907 -0.50084 0.65318 0.89969 247.14
270 15.540 -80.676 -32.414 -0.48404 0.65565 0.89792 249.76
275 15.204 -77.256 -27.927 -0.46757 0.65844 0.89696 252.32
280 14.884 -73.831 -23.443 -0.45141 0.66150 0.89665 254.83
285 14.580 -70.399 -18.959 -0.43554 0.66478 0.89691 257.29
290 14.290 -66.957 -14.473 -0.41994 0.66824 0.89764 259.70
295 14.013 -63.505 -9.9821 -0.40458 0.67184 0.89878 262.07
300 13.747 -60.041 -5.4847 -0.38947 0.67556 0.90026 264.41
305 13.493 -56.564 -0.97908 -0.37457 0.67937 0.90202 266.70
310 13.249 -53.072 3.5360 -0.35989 0.68326 0.90404 268.96
315 13.015 -49.566 8.0617 -0.34540 0.68720 0.90627 271.19
320 12.789 -46.044 12.599 -0.33111 0.69120 0.90868 273.39
325 12.572 -42.507 17.149 -0.31701 0.69523 0.91126 275.56
330 12.363 -38.952 21.712 -0.30307 0.69928 0.91397 277.70
335 12.162 -35.381 26.289 -0.28931 0.70336 0.91680 279.82
340 11.967 -31.793 30.880 -0.27570 0.70744 0.91973 281.91
34,) 11.I1Y -:L~.1~/ 3,).480 -U.:LoU') U./11:)4 0.92274 283.98
350 11.597 -24.563 40.107 -0.24896 0.71562 0.92583 286.02
360 11.251 -17.262 49.397 -0.22279 0.72378 0.93217 290.05
370 10.927 -9.8882 58.751 -0.19716 0.73188 0.93869 294.00
380 10.621 -2.4415 68.171 -0.17204 0.73991 0.94532 297.88
390 10.333 5.0782 77.658 -0.14739 0.74784 0.95202 301.68
400 10.062 12.671 87.212 -0.12321 0.75568 0.95875 305.42
410 9.8042 20.336 96.833 -0.09945 0.76340 0.96549 309.11
-120 9.5603 28.072 106.52 -0.07610 0.77101 0.97221 31273
430 9.3287 35.880 116.28 -0.05315 0.778~0 0.97890 316.31
440 9.1085 43.758 126.10 -0.03057 0.78586 0.98554 319.83
450 8.8987 51.706 135.99 -0.00835 0.79310 0.99212 323.30
460 8.6988 59.723 145.94 0.01353 0.80022 0.99864 326.73
470 8.5079 67.807 155.96 0.03508 0.80722 1.0051 330.12
480 8.3254 75.957 166.04 0.05631 0.81409 1.0115 333.46
490 8.1508 84.174 176.19 0.07723 0.82084 1.0178 336.76
500 7.9835 92.455 186.40 0.09785 0.82748 1.0240 340.03

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1567

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m 3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (mls)

0.75 MPa Isobar

525 7.5946 113.43 212.19 0.14818 0.84355 1.0391 348.03

550 7.2425 134.79 238.35 0.19686 0.85893 1.0537 355.83
575 6.9222 156.52 264.87 0.24401 0.87363 1.0678 363.44
600 6.6294 178.60 291.74 0.28974 0.88769 1.0813 370.87
625 6.3608 201.02 318.93 0.33415 0.90115 1.0943 378.14
650 6.1133 223.76 346.45 0.37732 0.91402 1.1068 385.26
675 5.8846 246.82 374.27 0.41931 0.92634 1.1188 392.23
700 5.6725 270.16 402.38 0.46021 0.93812 1.1302 399.08
800 4.9589 366.29 517.53 0.61391 0.98037 1.1716 425.30
900 4.4056 466.25 636.49 0.75398 1.0158 1.2064 449.93
1000 3.9639 569.43 758.63 0.88265 1.0454 1.2357 473.27
1100 3.6030 67:'5.32 883.47 1.0016 1.0704 L:L6U4 4Y5.5U

1.00 MPa Isobar

b -427.26 -426.41
216.695 1179.10 -2.2180 0.97514 1.9503 977.76
220 1167.03 -420.80 -419.95 -2.1884 0.97034 1.9589 953.55
225 1148.32 -410.99 -410.11 -2.1442 0.96337 1.9751 916.83
230 1128.97 -401.08 -400.19 -2.1006 0.95680 1.9959 879.82
233.028 c 1116.90 -395.02 -394.12 -2.0744 0.95303 2.0111 857.18
233.028° 26.006 -109.94 -71.484 -0.68986 O.MOLt> l.UJ:L:L 223.50
235 25.665 -108.42 -69.459 -0.68120 0.67819 1.0220 224.93
240 24.857 -104.64 -64.408 -0.65993 0.67332 0.99915 228.46
245 24.117 -100.92 -59.460 -0.63953 0.66959 0.98058 231.84
250 23.435 -97.266 -54.595 -0.61987 0.66716 0.96579 235.08
255 22.803 -93.650 -49.797 -0.60087 0.66588 0.95411 238.19
260 22.215 -90.065 -45.050 -0.58243 0.66557 0.94495 241.19
265 21.664 -86.503 -40.344 -0.56450 0.66605 0.93783 244.10
270 21.147 -82.957 -35.669 -0.54703 0.66718 0.93235 246.91
275 20.660 -79.422 -31.018 -0.52996 0.66884 0.92821 249.66
280 20.199 -75.892 -26.385 -0.51326 0.67092 0.92518 252.33
285 19.763 -72.364 -21.765 -0.49691 0.67335 0.92307 254.93
290 19.349 -68.836 -17.153 -0.48087 0.67607 0.92172 257.49
295 18.955 -65.303 -12.547 -0.46512 0.67902 0.92103 259.98
300 18.579 -61.765 -7.9420 -0.44964 0.68217 0.92089 262.43
305 18.221 -58.220 -3.3370 -0.43442 0.68547 0.92121 264.83
310 17.878 -54.665 1.2707 -0.41943 0.68890 0.92192 267.20
315 17.549 -51.100 5.8828 -0.40467 0.69243 0.92298 269.52
320 17.234 -47.523 10.501 -0.39013 0.69605 0.92433 271.80
325 16.932 -43.934 15.126 -0.37578 0.69974 0.92594 274.06
330 16.641 -40.331 19.761 -0.36163 0.70349 0.92777 276.28
335 16.361 -36.715 24.405 -0.34767 0.70729 0.92981 278.46
340 16.092 -33.084 29.059 -0.33387 0.71112 0.93200 280.62
345 15.832 -29.438 33.725 -0.32025 0.71498 0.93435 282.76
350 15.581 -25.777 38.403 -0.30679 0.71885 0.93681 284.86

J. Phys. Chern: Ref. Data, Vol. 25, No.6, 1996

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 1568 R. SPAN AND W. WAGNER

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m 3 ) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

1.00 MPa Isobar

360 15.105 -18.406 47.797 -0.28033 0.72664 0.94206 289.00

370 14.659 -10.970 57.245 -0.25444 0.73442 0.94763 293.05
380 14.241 -3.4677 66.750 -0.22909 0.74217 0.95345 297.02
390 13.848 4.1027 76.315 -0.20425 0.74988 0.95944 300.91
400 13.477 11.741 85.939 -0.17988 0.75751 0.96555 304.72
410 13.127 19.449 95.626 -0.15596 0.76505 0.97174 308.47
420 12.796 27.224 105.37 -0.13247 0.77251 0.97798 312.16
430 12.482 35.068 115.19 -0.10939 0.77986 0.98423 315.79
440 12.183 42.979 125.06 -0.08669 0.78710 0.99049 319.37
450 11.899 50.957 135.00 -0.06436 0.79424 0.99673 322.89
460 11.629 59.001 144.99 -0.04238 0.80126 1.0029 326.37
470 11.371 67.112 155.05 -0.02075 0.80817 1.0091 329.79
480 11.125 75.287 165.18 0.00056 0.81497 1.0152 333.18
490 10.889 83.526 175.36 0.02156 0.82166 1.0213 336.52
500 10.664 91.829 185.60 0.04225 0.82823 1.0273 339.81
525 10.141 112.86 211.47 0.09273 0.84418 1.0420 341.9U
550 9.6675 134.26 237.70 0.14154 0.85946 1.0563 355.76
575 9.2375 156.02 264.28 0.18879 0.87408 1.0700 363.42
600 8.8449 178.14 291.19 0.23462 0.88808 1.0833 370.90
625 8.4849 200.58 318.44 0.27910 0.90149 1.0901 378.20
650 8.1535 223.35 345.99 0.32233 0.91432 1.1084 385.36
675 7.8474 246.42 373.85 0.36438 0.92660 1.1202 392.37
700 7.5638 269.79 402.00 0.40533 0.93835 1.1315 399.24
800 6.6102 365.98 517.26 0.55918 0.98053 1.1725 425.54
900 5.8718 465.99 636.29 0.69934 1.0159 1.2071 450.22
1000 5.2826 569.20 758.50 0.82807 1.0455 1.2362 473.59
1100 4.8014 675.12 883.39 0.94708 1.0704 1.2608 495.84

2.00 MPa Isobar

b
216.908 1180.41 -427.40 -425.70 -2.2187 0.97612 1.9443 981.71
220 1169.23 -421.39 -419.68 -2.1911 0.97160 1.9517 959.33
225 1150.73 -411.63 -409.89 -2.1471 0.96458 1.9667 923.07
230 1131.64 -401.78 -400.01 -2.1037 0.95796 1.9858 886.59
235 1111.85 -391.82 -390.02 -2.0607 0.95178 2.0100 849.70
240 1091.24 -381.73 -379.90 -2.0181 0.94610 2.0404 812.17
245 1069.65 -371.47 -369.60 -1.9756 0.94098 2.0786 773.73
250 1046.88 -361.01 -359.10 -1.9332 0.93660 2.1271 733.93
253.647 c 1029.36 -353.20 -351.26 -1.9021 0.93409 2.1710 703.64
253.647c 52.540 -107.99 -69.929 -0.79292 0.76254 1.2983 220.27
255 51.941 -106.69 -68.187 -0.78607 0.75793 1.2773 221.55
260 49.914 -102.04 -61.969 -0.76192 0.74331 1.2130 226.07
265 48.129 -97.586 -56.031 -0.73930 0.73233 1.1646 230.27
270 46.533 -93.285 -50.304 -0.71789 0.72439 1.1276 234.21
275 45.090 -89.098 -44.742 -0.69748 0.71881 1.0987 237.93

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1569

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy C - cp Speed of

u
(K) (kg/m3 ) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJf(kg K)] sound (m/s)

2.00 MPa Isobar

280 43.772 -84.999 -39.308 -0.67789 0.71503 1.0758 241.45

285 42.560 -80.969 -33.977 -0.65902 0.71265 1.0574 244.82
290 41.438 -76.992 -28.728 -0.64076 0.71135 1.0425 248.05
295 40.395 -73.058 -23.547 -0.62305 0.71092 1.0305 251.15
300 39.420 -69.155 -18.420 -0.60581 0.71116 1.0206 254.15
305 38.506 -65.278 -13.338 -0.58901 0.71195 1.0125 257.06
310 37.645 -61.420 -8.2920 -0.57260 0.71317 1.0059 259.89
315 36.832 -57.577 -3.2763 -0.55655 0.71475 1.0005 262.63
320 36.063 -53.744 1.7152 -0.54083 0.71664 0.99621 265.31
325 35.333 -49.917 6.6872 -0.52541 0.71879 0.99276 267.93
330 34.639 -46.095 11.644 -0.51028 0.72117 0.99008 270.49
335 33.977 -42.2TJ 16.~ts9 -U.49~41 U.I:LJ73 U.9/StsU) 212.99
340 33.346 -38.451 21.526 -0.48078 0.72645 0.98659 275.45
345 32.743 -34.627 26.456 -0.46638 0.72929 0.98561 277.85
350 32.165 -30.798 31.382 -0.45221 0.73225 0.98506 280.22
360 31.078 -23.121 41.232 -0.42446 0.73841 0.98503 284.83
370 30.075 -15.414 51.087 -0.39746 0.74484 0.98616 289.30
380 29.143 -7.6685 60.958 -0.37113 0.75144 0.98819 293.64
390 28.276 0.12033 70.853 -0.34543 0.75815 0.99093 297.87
400 27.'16'1 7.9565 80.778 -0.32030 0.76'194 0.99423 301.99
410 26.704 15.843 90.739 -0.29571 0.77175 0.99798 306.02
420 25.989 23.782 100.74 -0.27161 0.77856 1.0021 309.96
430 25.314 31.775 110.78 -0.24798 0.78535 1.0064 313.83
440 24.678 39.824 120.87 -0.22479 0.79211 1.0110 317.61
450 24.075 47.929 131.00 -0.20202 0.79881 1.0158 321.33
460 23.504 56.091 141.18 -0.17964 0.80545 1.0207 324.99
470 22.961 64.310 151.42 -0.15763 0.81202 1.0256 328.58
480 22.444 72.587 161.70 -0.13599 0.81852 1.0307 332.12
490 21.952 80.920 172.03 -0.11468 0.82493 1.0358 335.60
500 21.482 89.311 182.41 -0.09371 0.83126 1.0409 339.03
525 20.396 110.54 208.59 -0.04261 0.84670 1.0537 347.41
550 19.419 132.11 235.10 0.00670 0.86158 1.0664 355.52
575 18.536 154.02 261.91 0.05438 0.87589 1.0790 363.39
600 17.733 176.26 289.04 0.10056 0.88964 1.0912 371.05
625 16.999 198.82 316.47 0.14535 0.90284 1.1031 378.52
650 16.325 221.69 344.20 0.18884 0.91550 1.1147 385.81
67:5 1:5.70:5 244.8:5 372.20 0.23112 0.92764 1.1259 392.94
700 15.130 268.30 400.49 0.27227 0.93928 1.1367 399.92
800 13.207 364.75 516.19 0.42670 0.98114 1.1762 426.52
900 11.724 464.95 635.54 0.56724 1.0163 1.2099 451.40
1000 10.544 568.30 757.99 0.69622 1.0459 1.2384 474.89
1100 9.5815 674.33 883.06 0.81542 1.0707 1.2625 497.22

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1570 R. SPAN AND W. WAGNER

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJI(kg K)] sound (mls)

3.00 MPa Isobar

217.121b 1181.71 -427.54 -425.00 -2.2193 0.97705 1.9386 985.63

220 1171.40 -421.97 -419.41 -2.1938 0.97282 1.9449 965.03
225 1153.10 -412.25 -409.65 -2.1499 0.96576 1.9587 929.22
230 1134.25 -402.46 -399.82 -2.1067 0.95909 1.9763 893.25
235 1114.74 -392.57 -389.88 -2.0639 0.95286 1.9986 856.93
240 1094.46 -382.56 -379.82 -2.0216 0.94711 2.0265 820.08
245 1073.29 -372.40 -369.61 -l.9795 0.94190 2.0613 782.45
250 1051.02 -362.05 -359.19 -1.9374 0.93737 2.1051 743.69
255 1027.42 -35l.46 -348.54 -l.8952 0.93383 2.1608 703.23
260 1002.13 -340.55 -337.56 -l.8526 0.93209 2.2331 660.22
265 974.65 -329.24 -326.16 -1.8091 0.93362 2.3306 613.45
267.598 c 959.25 -323.15 -320.03 -1.7861 0.93647 2.3959 587.14
267.598 c 81.919 -109.79 -73.169 -0.86360 0.83693 1.6438 214.95
270 79.807 -106.92 -69.327 -0.84931 0.82029 1.5582 217.92
275 76.011 -1Ol.35 -61.879 -0.82197 0.79485 l.4301 223.53
280 72.805 -96.166 -54.960 -0.79703 0.77747 1.3423 228.55
285 70.025 -91.258 -48.416 -0.77387 0.76520 1.2784 233.14
290 67.568 -86.550 -42.151 -0.75207 0.75645 l.2300 237.39
295 65.368 -81.993 -36.099 -0.73138 0.75024 1.1923 24l.37
300 63.376 -77.552 -30.215 -0.71160 0.74589 1.1623 245.13
305 61.556 -73.203 -24.466 -0.69260 0.74293 1.1380 248.70
310 59.881 -68.927 -18.827 -0.67426 0.74101 1.1181 252.12
315 58.332 -64.710 -13.280 -0.65650 0.73994 1.1016 255.40
320 56.890 -60.540 -7.8071 -0.63927 0.73955 1.0878 258.56
325 55.544 -56.409 -2.3975 -0.62249 0.73974 1.0763 261.61
330 54.281 -52.309 2.9594 -0.60614 0.74041 1.0667 264.56
335 53.092 -48.233 8.2721 -0.59016 0.74148 1.0586 267.43
340 51.970 -44.178 13.548 -0.57453 0.74287 1.0518 270.21
345 50.908 -40.137 18.792 -0.55921 0.74453 1.0462 272.93
350 49.901 -36.108 24.011 -0.54419 0.74643 1.0414 275.58
360 48.031 -28.073 34.387 -0.51496 0.75077 1.0343 280.71
370 46.327 -20.052 44.705 -0.48669 0.75568 1.0296 285.63
380 44.765 -12.030 54.986 -0.45928 0.76102 1.0269 290.37
390 43.326 -3.9958 65.247 -0.43262 0.76667 1.0256 294.95
400 41.992 4.0597 75.502 -0.40666 0.77255 1.0255 299.39
410 40.752 12.143 85.760 -0.38133 0.77858 1.0263 303.70
420 39.594 20.261 96.030 -0.35658 0.78472 1.0279 307.90
430 38.509 28.416 106.32 -0.33237 0.79093 1.0301 312.00
440 37.491 36.613 116.63 -0.30866 0.79717 1.0327 316.00
450 36.531 44.854 126.98 -0.28542 0.80343 1.0358 319.91
460 3::5.625 53.141 137.3::5 -0.26261 0.&0967 1.0392 323.74
470 34.768 61.475 147.76 -0.24023 0.81589 1.0428 327.50
480 33.956 69.858 158.21 -0.21823 0.82207 1.0467 331.19
490 33.185 78.291 168.69 -0.19661 0.82821 1.0507 334.81
500 32.451 86.774 179.22 0.17534 0.83429 1.0549 338.37

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1571

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg 19] [kJ/(kg K)] sound (m/s)

3.00 MPa Isobar

525 30.761 108.20 205.73 -0.12361 0.84921 1.0656 347.04

550 29.252 129.95 232.51 -0.07378 0.86369 1.0768 355.39
575 27.893 152.01 259.57 -0.02567 0.87769 1.0880 363.46
600 26.661 174.38 286.91 0.02087 0.89118 l.0992 371.30
625 25.540 197.06 314.53 0.06597 0.90418 1.1102 378.92
650 24.513 220.03 342.42 0.10972 0.91667 1.1211 386.34
675 23.569 243.29 370.58 0.15223 0.92868 1.1316 393.58
700 22.697 266.82 399.00 0.19357 0.94020 1.1419 400.65
800 19.789 363.53 515.13 0.34859 0.98175 1.1799 427.55
900 17.556 463.91 634.79 0.48950 1.0168 1.2126 452.61
1000 15.783 567.41 757.48 0.61874 1.0462 1.2405 476.21
1100 14.340 673.54 882.75 0.73811 1.0710 1.2642 498.61

4.00 MPa Isobar

b -427.67
217.334 1182.98 -424.29 -2.2200 0.97796 1.9330 989.53
LlU 11'13.:'::\ -422.54 -419.13 -2.1964 0.97402 1.9384 970.66
225 1155.43 -412.87 -409.41 -2.1527 0.96691 1.9510 935.29
230 1136.80 -403.13 -399.62 -2.1096 0.96020 1.9673 899.79
235 1117.56 -393.31 -389.73 -2.0671 0.95391 1.9878 864.02
240 1097.60 -383.37 -379.73 -2.0250 0.941310 2.0134 1327.80
245 1076.81 -373.30 -369.59 -1.9832 0.94281 2.0452 790.92
250 1055.01 -363.06 -359.26 -1.9415 0.93814 2.0849 753.10
255 1032.00 -352.60 -348.72 -1.8997 0.93435 2.1348 713.89
260 1007.49 -341.86 -337.89 -1.8577 0.93199 2.1986 672.67
265 981.06 -330.78 -326.70 -1.8150 0.93201 2.2823 628.62
270 952.10 -319.22 -315.02 -1.7714 0.93573 2.3972 580.72
275 919.56 -306.99 -302.64 -1.7259 0.94504 2.5660 527.52
278.450c 894.05 -297.98 -293.51 -1.6929 0.95655 2.7401 486.42
278.450c 115.74 -114.09 -79.534 -0.92449 0.91069 2.1642 208.78
280 113.08 -111.66 -76.288 -0.91286 0.89131 2.0294 211.36
285 106.02 -104.65 -66.920 -0.87969 0.84827 1.7461 218.60
290 100.47 -98.453 -58.641 -0.85089 0.82129 1.5780 224.72
295 95.884 -92.766 -51.048 -0.82493 0.80299 1.4657 230.14
300 91.965 -87.427 -43.932 -0.80101 0.79011 1.3850 235.04
305 88.543 -82.340 -37.165 -0.77864 0.78082 1.3244 239.56
310 85.508 . -77.445 -30.665 -0.75750 0.77402 1.2773 243.77
315 82.781 -72.697 -24.376 -0.73737 0.76906 1.2397 247.73
320 80.306 -68.066 -18.256 -0.71809 ,0.76551 1.2092 251.49
325 78.043 -63.529 -12.275 -0.69955 0.76308 1.1842 255.07
330 75.958 -59.068 -6.4078 -0.68163 0.76156 1.1633 258.49
jj) 74.U2~ -54.670 -0.63601 -0.66427 0.76076 1.1459 261.78
340 72.231 -50.322 5.0556 -0.64741 0.76054 1.1312 264.95
345 70.552 -46.017 10.679 -0.63099 0.76080 1.1187 268.01
350 68.976 -41.746 16.245 -0.61497 0.76145 1.1080 270.98

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1572 R. SPAN AND W. WAGNER

TA.BL.E 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kgim 3) (kJlkg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] (kJ/(kg K)] sound (rnIs)

4.00 MPa Isobar

360 66.092 -33.284 27.237 -0.58400 0.76371 1.0912 276.67

370 63.509 -24.899 38.084 -0.55428 0.76695 1.0789 282.06
380 61.l73 -16.562 48.826 -0.52564 0.77091 1.0700 287.22
390 59.045 -8.2521 59.493 -0.49793 0.77542 1.0637 191.11
400 57.094 0.04711 70.107 -O.47lO5 0.78032 L0595 296.93
410 55.294 8.3478 80.688 -0.44493 0.78553 1.0569 301.53
420 53.627 16.660 91.249 -0.41948 0.79097 1.0555 305.99
430 52.076 24.990 101.80 -0.39465 0.79657 1.0552 310.31
440 50.628 33.346 112.35 -0.37039 0.80228 L0556 314.52
450 49.?70 4171? 122.92 -0.34665 0.80808 1.056% 318.63
460 47.995 50.151 133.49 -0.32341 0.81391 1.0585 322.64
470 46.794 58.607 144.09 -0.30062 0.81978 1.0607 326.55
480 45.659 67.W2 154.71 -0.27826 0.82564 1.0633 330.39
490 44.585 75.638 165.35 -0.25631 0.83150 1.0661 334.15
500 43.566 ~4.L17 lIb.Uj -U.L3474 0.83733 1.0692 337.154
525 41.233 105.86 202.87 -0.18237 0.&5173 1.0779 346.77
550 39.160 127.79 229.93 -0.13201 0.86580 1.0873 355.36
575 37.302 (50.00 257.24 -0.08346 0.87948 1.0971 363.63
600 35.625 172.51 284.79 -0.03655 0.89272 l.iQ72 371.63
625 34.103 195.30 312.60 0.00885 0.90551 1.I l74 379.39
650 32.712 218.38 340.66 0.05287 0.91784 1.1274 386.93
675 31.437 241.73 368.97 0.09561 0.92971 1.1314 394.28
700 30.262 265.35 397.52 0.13715 0.94111 1.1471 40L45
800 26.355 362.32 514.09 0.29274 0.98236 1.1835 428.62
900 23.367 462.88 634.07 0.43402 l.0172 1.2153 453.84
1000 21.001 566.52 756.99 0.5635 t 1.0465 1.2425 477.55
1100 19.077 672.77 882.44 0.68306 1.0712 1.2658 500.01

5.00 MPa Isobar

217.546h 1184.25 -427.80 -423.58 -2.2206 0.97883 1.9275 993.41

220 1175.62 -423.10 -418.85 -2.1990 0.91518 1.9321 976.23
225 1157.72 -413.4-8 -409.16 -2.1554 0.96803 1.9436 941.27
230 1139.31 -403.79 -399.41 -2.£125 0.96127 1.9586 906.23
235 1120.32 -394.03 -389.57 -2.0702 0.95493 1.9775 870.97
240 1100.66 -384.17 -379.62 -2.0283 0.94906 2.0011 835.35
245 lO80.22 -374.18 -369.55 -1.9868 0.94369 2.0302 799.17
250 IUj~U~6 -3M.\).) -3:59.31 -1.9454 O.9389l 2.0663 762.21
255 1036.39 -353.69 -348.87 -1.9041 0.93492 2.1112 724.10
260 1012.57 -343.12 -338.18 - 1.8626 0.93209 2.1678 684.39
265 987.07 -332.23 -327.16 -1.8206 0.93107 2.2407 642.50
170 Q'iq ~q -,2004 -315.73 -1.7779 0.93262 2.3377 597.75
275 928.78 -309.11 -303.72 -1.7338 0.93765 2.4735 549.26
280 893.90 -296.47 -290.88 -1.6875 0.94778 2.6797 495.52
285 852.04 -282.54 -276.67 -1.6373 0.96716 3.0437 433.50

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1573

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cu cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)1 [kJ/(kg K)] sQund (mls)

5.00 MPa Isobar

287.434c 827.32 -274.96 -268.91 -1.6101 0.98314 3.3572 398.39

287.434c 156.67 -121.04 -89.122 -0.98464 0.99465 3.1142 201.86
290 148.41 -115.58 -81.892 -0.95959 0.94334 2.5783 207.56
295 136.85 -106.98 -70.445 -0.92044 0.88615 2.0671 216.24
300 128.40 -99.772 -60.830 -0.88811 0.85258 1.8025 223.25
305 121.69 -93.344 -52.258 -0.85977 0.83051 1.6378 229.28
310 116.13 -87.423 -44.367 -0.83411 0.81508 1.5246 234.66
315 111.37 -81.856 -36.961 -0.81041 0.80388 1.4418 239.55
320 107.22 -76.552 -29.917 -0.78822 0.79562 1.3786 244.08
325 103.53 -71.448 -23.153 -0.76724 0.78951 1.3289 248.32
330 100.22 -66.502 -16.612 -0.74727 0.78505 1.2890 252.30
jjJ ':J/.221 -61.651 -10.251 -0.72814 0.78185 1.2564 256.08
340 94.478 -56.961 -4.0388 -0.70973 0.77963 1.2294 259.68
345 91.955 -52.325 2.0498 -0.69195 0.77820 1.2067 263.13
350 89.619 -47.757 8.0342 -0.67473 0.77739 1.1875 266.45
360 85.418 -38.785 19.750 -0.64172 0.77727 1.1573 272.74
370 81.726 -29.974 31.205 -0.61034 0.77863 1.1349 278.64
380 78.440 -21.276 42.467 -0.58030 0.78109 1.1182 284.23
390 75.484 -12.655 53.584 -0.55142 0.78436 1.1058 289.55
-100 72.804 -4.0846 64.593 -0.52355 0.78824 1.0965 294.63
410 70.355 4.4545 75.523 -0.49656 0.79259 1.0898 299.52
420 68.104 12.978 86.396 -0.47036 0.79729 1.0850 304.24
430 66.024 21.498 97.228 -0.44487 0.80226 1.0818 308.79
440 64.094 30.024 108.03 -0.42003 0.80743 1.0798 313.21
450 62.295 38.564 118.83 -0.39578 0.81274 1.0788 317.50
460 60.613 47.123 129.61 -0.37207 0.81817 1.0787 321.68
470 59.035 55.707 140.40 -0.34886 0.82367 1.0792 325.75
480 57.550 64.320 151.20 -0.32613 0.82921 1.0804 329.73
490 56.150 72.964 162.01 -0.30384 0.83478 1.0820 333.62
500 54.826 81.644 172.84 -0.28196 0.84035 1.0840 337.43
525 51.807 103.51 200.02 -0.22893 0.85423 1.0903 346.63
550 49.140 125.62 227.37 -0.17803 0.86790 1.0979 355.43
575 46.761 147.99 254.92 -0.12904 0.88126 1.1064 363.88
600 44.621 170.64 282.69 -0.08177 0.89425 1.1153 372.04
625 42.685 193.55 310.69 -0.03605 0.90684 1.1245 379.93
650 40.921 216.73 338.92 0.00823 0.91900 1.1338 387.59
675 39.307 240.17 367.38 0.05120 0.93073 1.1431 395.04
700 37.823 263.87 396.07 0.09293 0.94202 1.1523 402.30
800 32.904 361.11 513.07 0.24911 -0.98296 1.1871 429.72
900 29.156 461.86 633.35 0.39075 1.0176 1.2179 455.10
1000 26.196 565.64 756.51 0.52048 1.0469 t.2446 478.91
1100 23.793 671.99 882.14 0.64021 1.0715 1.2674 501.43

J. Phys. Chem. Ref. Data, Vol. 25, No.6, 1996

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 1574 R. SPAN AND W. WAGNER

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

6.00 MPa Isobar

b
217.758 1185.49 -427.93 -422.87 -2.2212 0.97967 1.9222 997.26
220 1177.69 -423.65 -418.56 -2.2015 0.97632 1.9260 981.74
225 1159.97 -414.07 -408.90 -2.1581 0.96912 1.9366 947.17
230 1141.77 -404.44 -399.19 -2.1154 0.96232 1.9504 912.57
235 1123.02 -394.73 -389.39 -2.0733 0.95593 1.9678 877.80
240 1103.65 -384.94 -379.50 -2.0316 0.95000 1.9894 842.74
245 1083.55 -375.03 -369.49 -1.9903 0.94456 2.0162 807.22
250 1062.59 -364.98 -359.33 -1.9493 0.93968 2.0491 771.04
255 1040.62 -354.75 -348.99 -1.9083 0.93551 2.0897 733.92
260 1017.43 -344.31 -338.42 -1.8673 0.93233 2.1402 695.50
265 992.74 -333.60 -327.56 -1.8259 0.93057 2.2042 655.38
270 966.16 -322.55 -3HU4 -1.7~4U 0.93070 2.2873 613.08
275 937.12 -311.04 -304.64 -1.7410 0.93321 2.3994 568.01
280 904.68 -298.90 -292.27 -1.6965 0.93889 2.5598 519.20
285 867.13 -285.81 -278.89 -1.6491 0.94979 2.8131 464.94
290 820.77 -271.08 -263.77 -1.5965 0.97135 3.2947 401.70
295 753.39 -252.51 -244.55 -1.5308 1.0250 4.7540 317.23
295.128 c 751.03 -251.92 -243.93 -1.5288 1.0277 4.8386 314.35
295.128 c 210.88 -131.91 -103.46 -1.0528 1.1086 5.5056 193.67
300 1&2.31 -1l7.53 -g4.623 -0.98943 0.96413 2.9858 207.78
305 166.26 -107.73 -71.643 -0.94650 0.90457 2.3038 217.07
310 154.99 -99.750 -61.037 -0.91200 0.87020 1.9705 224.44
315 146.25 -92.751 -51.726 -0.88220 0.84761 1.7687 230.73
320 139.11 -86.373 -43.243 -0.85548 0.83170 1.6322 236.30
325 133.08 -80.425 -35.341 -0.83098 0.82010 1.5335 241.37
330 127.87 -74.792 -27.869 -0.80816 0.81151 1.4588 246.04
335 123.27 -69.398 -20.726 -0.78668 0.80512 1.4004 250.39
340 119.18 -64.191 -13.846 -0.76629 0.80035 1.3536 254.48
345 115.48 -59.133 -7.1762 -0.74682 0.79684 1.3154 258.36
350 112.12 -54.197 -0.68096 -0.72812 0.79430 1.2837 262.05
360 106.19 -44.606 11.897 -0.69269 0.79142 1.2346 268.98
370 101.10 -35.295 24.054 -0.65937 0.79070 1.1988 275.41
380 96.643 -26.182 35.903 -0.62778 0.79152 1.1722 28l.43
390 92.694 -17.210 47.519 -0.59760 0.79347 1.1521 287.12
400 89.155 -8.3384 58.960 -0.56863 0.79627 1.1368 292.53
410 85.954 0.46261 70.268 -0.54071 0.79971 1.1252 297.71
420 83.036 9.2162 81.474 -0.51371 0.80365 1.1164 302.67
430 80.360 17.940 92.604 -0.48752 0.80797 1.1099 307.45
440 77.892 26.648 103.68 -0.46206 0.81258 1.1051 312.07
450 75.605 35.351 114.71 -0.43726 0.81742 1.1018 316.54
460 73.477 44.059 125.72 -0.41307 0.82242 1.0996 J:2U.~~

470 71.488 52.778 136.71 -0.38944 0.82755 1.0984 325.10

480 69.625 61.513 147.69 -0.36632 0.83277 1.0980 329.21
490 67.874 70.271 158.67 -0.34367 0.83805 1.0983 333.23
500 66.22J 79.054 169.66 -0.32148 0.84337 1.0991 337.1.3

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EaUATION OF STATE FOR CARBON DIOXIDE 1575

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (rn/s)

6.00 MPa Isobar

525 62.477 101.14 197.18 -0.26777 0.85672 1.1030 346.60

550 59.186 123.45 224.82 -0.21633 0.86998 1.1087 355.60
575 56.264 145.98 252.62 -0.16690 0.88302 1.1157 364.23
600 53.645 168.76 280.61 -0.11925 0.89577 1.1234 372.54
625 51.282 191.80 308.80 -0.07323 0.90815 1.1317 380.56
650 49.136 215.09 337.20 -0.02868 0.92015 1.1402 388.32
675 47.176 238.62 365.81 0.01451 0.93174 1.1488 395.86
700 45.377 262.41 394.64 0.05645 0.94292 1.1574 403.20
800 39.435 359.91 512.06 0.21320 0.98356 1.1906 430.87
900 34.924 460.85 632.65 0.35520 1.0181 1.2206 456.39
1000 31.368 564.76 756.04 0.48518 1.0472 1.2466 480.28
1100 28.486 671.23 881.83 0.60507 1.0718 1.2691 502.86

7.00 MPa Isobar

b
217.969 1186.73 -428.06 -422.16 -2.2218 0.98048 1.9170 1001.1
nu lUIJ:t:2 -424.1IJ -4UU6 -2.2040 0.97743 1.9202 987.18
225 1162.17 -414.66 -498.64 -2.1607 0.97018 1.9298 952.99
230 1144.18 -405.07 -398.96 -2.1182 0.96334 1.9425 918.81
235 1125.67 -395.42 -389.21 -2.0763 0.95691 1.9585 884.52
240 1106.56 -385.69 -379.36 -2.0348 0.9j092 1.9785 1349.9':1
245 1086.78 -375.85 -369.41 -1.9938 0.94542 2.0030 815.07
250 1066.20 -365.89 -359.33 -1.9530 0.94045 2.0330 779.62
255 1044.69 -355.77 -349.07 -1.9124 0.93613 2.0699 743.39
260 1022.07 -345.46 -338.61 -1.8718 0.93267 2.1152 706.11
265 998.11 -334.91 -327.90 -1.8310 0.93037 2.1718 667.47
270 972.50 -324.07 -316.87 -1.7898 0.92952 2.2439 627.14
275 944.77 -312.83 -305.42 -1.7478 0.93042 2.3383 584.70
280 914.25 -301.09 -293.43 -1.7045 0.93353 2.4674 539.49
285 879.80 -288.61 -280.65 -1.6593 0.94003 2.6565 490.42
290 839.25 -275.01 -266.66 -1.6107 0.95290 2.9683 435.61
295 787.63 -259.35 -250.47 -1.5553 0.97893 3.5994 371.18
300 706.06 -238.25 -228.34 -1.4810 1.0529 5.9775 281.10
301.833 c 638.31 -223.87 -212.90 -1.4297 1.2173 14.685 211.72
301.833 c 304.03 -152.89 -129.87 -1.1546 1.3535 21.953 179.63
305 243.08 -131.34 -102.55 -1.0644 1.0602 5.0681 199.60
310 210.63 -116.70 -83.469 -1.0024 0.95569 3.0512 212.29
315 191.97 -106.54 -70.071 -0.95947 0.90676 2.3936 221.05
320 178.74 -98.192 -59.029 -0.92468 Q,87690 2.0539 228.16
325 168.48 -90.870 -49.322 -0.89458 0.85650 1.8433 234.30
330 160.11 -84.207 -40.487 -0.86760 0.84183 1.6992 239.80
335 153.0) -7~WU4 -32.266 -0.84287 0.83102 1.5942 244.81
340 146.95 -72.139 -24.503 -0.81987 0.82293 1.5144 249.45
345 141.59 -66.532 -17.094 -0.79823 0.81682 1.4517 253.79
350 136.82 -61.129 -9.9662 -0.77772 0.81220 1.4012 257.89

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1576 R. SPAN AND W. WAGNER

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

7.00 MPa Isobar

360 128.61 -50.782 3.6440 -0.73937 0.80615 1.3254 265.47

370 121.75 -40.880 16.616 -0.70383 0.80311 1.2718 272.42
380 115.86 -31.289 29.127 -0.67046 0.80216 1.2325 278.88
390 110.73 -21.922 41.298 -0.63885 0.80271 1.2030 284.94
400 106.18 -12.716 53.210 -0.60869 0.80437 1.1805 290.66
410 102.11 -3.6281 64.925 -0.57976 0.80688 1.1632 296.11
420 98.436 5.3748 76.487 -0.55189 0.81003 1.1499 301.31
430 95.090 14.318 87.932 -0.52496 0.81369 1.1396 306.30
440 92.024 23.220 99.287 -0.49886 0.81773 1.1317 311.11
450 89.200 32.097 110.57 -0.47350 0.82208 1.1258 315.75
460 86.584 40.960 121.81 -0.44880 0.82666 1.1214 320.24
470 84.151 49.820 133.00 0.42472 0.83141 1.1183 324.Gl
480 81.880 58.684 144.18 -0.40120 0.83631 1.1162 328.85
490 79.752 67.559 155.33 -0.37820 0.84130 1.1150 332.98
500 77.753 76.450 166.48 -0.35568 0.84636 1.1145 337.01
525 73.239 98.773 194.35 -0.30129 0.85919 1.1158 3-16.69
550 69.294 121.27 222.29 -0.24930 0.87205 1.1196 355.89
575 65.807 143.97 250.34 -0.19942 0.88478 1.1250 364.68
600 62.694 166.90 278.55 -0.15140 0.89727 1.1316 373.12
62:'i :'i9.R92 190.05 306.93 -0.10506 0.90945 1.138R 381.25
650 57.354 213.45 335.50 -0.06025 0.92129 1.1465 389.12
675 55.041 237.08 364.26 -0.01683 0.93275 1.1545 396.75
700 52.922 260.95 393.22 0.02530 0.94382 1.1625 404.16
800 45.945 358.71 511.07 0.18262 0.98415 1.1942 432.04
900 40.668 459.84 631.96 0.32498 1.0185 1.2232 457.70
1000 36.517 563.89 755.58 0.45520 1.0475 1.2486 481.67
1100 33.158 670.46 881.58 0.57527 1.0720 1.2707 504.30

7.50 MPa Isobar

218.074b 1187.34 -428.12 -421.80 -2.2221 0.98087 1.9145 1003.0

220 1180.72 -424.46 -418.11 -2.2052 0.97797 1.9173 989.88
225 1163.26 -414.95 -408.50 -2.1621 0.97071 1.9265 955.88
230 1145.37 -405.39 -398.84 -2.1196 0.96384 1.9387 921.90
235 1126.97 -395.76 -389.11 -2.0777 0.95738 1.9541 887.83
240 1107.99 -386.06 -379.29 -2.0364 0.95138 1.9732 853.55
245 1088.36 -376.26 -369.37 -1.9955 0.94584 1.9967 ' 818.94
250 1067.96 -366.34 -359.32 -1.9549 0.94083 2.0254 783.82
255 1046.67 -356.27 -349.10 -1.9144 0.93644 2.0605 748.00
260 1024.32 -346.02 -338.70 -1.8740 0.93286 2.1036 711.24
265 1000.70 -335.55 -328.05 -1.8334 0.93034 2.1570 673.27
270 975.52 -324.79 -317.10 -1.7925 0.92912 2.2243 633.7':)
275 948.38 -313.68 -305.78 -1.7510 0.92943 2.3115 592.46
280 918.68 -302.10 -293.94 -1.7083 0.93163 2.4284 548.71
285 885.48 -289.88 -281.41 -1.6640 0.93668 2.5947 501.67

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1577

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cu cp Speed of

(K) (kglm 3) (kJ/kg)· (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

7.50 MPa Isobar

290 847.07 -276.69 -267.84 -1.6168 0.94689 2.8557 449.91

295 799.88 -261.88 -252.50 -1.5643 0.96694 3.3335 390.87
300 733.90 -243.62 -233.40 -1.5001 1.0115 4.5507 317.38
305 389.85 -171.22 -151.98 -1.2323 1.5317 67.567 168.55
310 253.36 -129.11 -99.510 -1.0611 1.0261 4.5173 204.64
315 222.11 -115.30 -81.528 -1.0035 0.94620 2.9805 215.79
320 203.04 -105.22 -68.283 -0.96181 0.90445 2.3876 223.97
325 189.27 -96.845 -57.220 -0.92750 0.87759 2.0648 230.79
330 178.52 -89.456 -47.442 -0.89764 0.85879 1.8598 236.76
335 169.70 -82.714 -38.518 -0.87080 0.84513 1.7176 242.13
340 162.24 -76.430 -30.204 -0.84616 0.83499 1.6131 247.06
345 155.80 -70.486 -22.346 -0.82322 0.82734 1.5331 251.64
350 150.13 -64.802 -14.845 -0.80163 0.82151 1.4699 255.93
360 140.52 -54.014 -0.64140 -0.76161 0.81370 1.3768 263.84
370 132.60 -43.777 12.785 -0.72482 0.80942 1.3121 271.05
3~0 125.~~ -33.Y21 25.660 -0.6Y04~ 0.~0754 1.2652 277.72
390 120.06 -24.337 38.129 -0.65809 0.80736 1.2302 283.95
400 114.95 -14.951 50.293 -0.62729 0.80844 1.2036 289.83
410 110.40 -5.7101 62.222 -0.59783 0.81047 1.1832 295.40
420 106.31 3.4250 73.971 -0.56952 0.81323 1.1673 300.72
430 102.60 12.483 85.580 -0.54220 0.81654 1.1550 305.81
440 99.215 21.487 97.080 -0.51576 0.82030 1.1454 310.71
450 96.102 30.454 108.50 -0.49011 0.82440 1.1381 315.43
460 93.227 39.399 119.85 -0.46516 0.82877 1.1325 319.99
470 90.558 48.331 131.15 -0.44085 0.83334 1.1284 324.42
480 88.072 57.262 142.42 -0.41713 0.83807 1.1254 328.72
490 85.747 66.197 153.66 -0.39394 0.84291 1.1235 332.91
500 83.566 75.143 164.89 -0.37126 0.84785 1.1224 336.99
525 78.652 97.585 192.94 -0.31651 0.86041 1.1223 346.78
550 74.369 120.18 221.03 -0.26425 0.87307 1.1251 356.07
575 70.592 142.97 249.21 -0.21414 0.88565 1.1297 364.93
600 67.225 165.96 277.53 -0.16594 0.89802 1.1357 373.44
625 64.201 189.18 306.00 -0.11944 0.91010 1.1424 381.63
650 61.464 212.63 334.65 -0.07450 0.92186 1.1497 389.54
675 58.972 236.31 363.49 -0.03096 0.93325 1.1573 397.21
700 56.691 260.22 392.52 0.01126 0.94426 1.1651 404.66
800 49.193 358.12 510.58 0.16887 0.98445 1.1959 432.65
900 43.532 459.34 631.63 0.31141 }.0187 1.2245 458.36
1000 39.083 563.46 755.36 0.44175 1.0477 1.2496 482.37
1100 35.485 670.08 881.44 0.56190 1.0722 1.2714 505.03
8.00 MPa Isobar
b
218.180 1187.95 -428.17 -421.44 -2.2224 0.98126 1.9120 1004.9
220 1181.72 -424.73 -417.96 -2.2065 0.97851 1.9145 992.56
225 1164.35 -415.23 -408.36 -2.1634 0.97122 1.9233 958.75
230 1146.54 -405.70 -398.72 -2.1210 0.96433 1.9349 924.97
235 1128.26 -396.10 -389.Ql -2.0792 0.95786 1.9497 891.12

J. Phys. Chern. Ret. Data, Vol. 25, No.6, 1996

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 1578 R. SPAN AND W. WAGNER

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Intemal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

8.00 MPa Isobar

240 1109.41 -386.43 -379.22 -2.0380 0.95182 1.9681 857.09

245 1089.93 -376.66 -369.32 -1.9972 0.94626 1.9906 822.75
250 1069.70 -366.78 -359.30 -1.9567 0.94120 2.0181 787.97
255 1048.62 -356.76 -349.13 -1.9164 0.93676 2.0516 752.55
260 1026.53 -346.57 -338.77 -1.8762 0.93307 2.0925 716.27
265 1003.23 -336.16 -328.19 -1.8359 0.93036 2.1429 678.91
270 978.46 -325.50 -317.32 -1.7952 0.92882 2.2060 640.22
275 951.86 -314.51 -306.10 -1.7541 0.92864 2.2867 599.89
280 922.92 -303.08 -294.41 -1.7119 0.93010 2.3931 557.45
285 890.82 -291.08 -282.10 -1.6684 0.93400 2.5408 512.17
290 854.20 -278.25 -268.88 -1.6224 0.94218 2.7633 462.96
295 810.40 -264.09 -254.22 -1.5722 0.95803 3.1417 408.04
300 753.17 -247.44 -236.82 -1.5138 0.98934 3.9320 343.66
305 656.77 -223.65 -211.47 -1.4301 1.0822 7.3125 255.09
310 327.71 -149.25 -124.84 -1.1485 1.1499 9.5864 194.28
31.'5 261.29 -126.27 -95.650 -1.0550 0.990L4 4.UJUU 210.19
320 231.91 -113.35 -78.854 -1.0021 0.93636 2.8750 219.80
325 212.90 -103.49 -65.909 -0.96190 0.90103 2.3574 227.35
330 198.87 -95.152 -54.926 -0.92836 0.87714 2.0594 233.83
335 187.79 -87.747 -45.146 -0.89894 0.86009 1.8648 239 ..'57
340 178.65 -80.965 -36.184 -0.87239 0.84758 1.7274 244.79
345 170.89 -74.629 -27.814 -0.84795 0.83820 1.6253 249.61
350 164.16 -68.627 -19.893 -0.82515 0.83106 1.5463 254.10
360 152.93 -57.348 -5.0372 -0.78329 0.82137 1.4326 262.32
370 143.82 -46.747 8.8792 -0.74516 0.81579 1.3552 269.78
380 136.18 -36.607 22.140 -0.70979 0.81295 1.2998 276.65
390 129.63 -26.793 34.923 -0.67659 0.81202 1.2588 283.05
400 123.90 -17.218 47.348 -0.64513 0.81251 1.2277 289.07
410 118.84 -7.8163 59.501 -0.61512 0.81406 1.2038 294.76
420 114.31 1.4561 71.442 -0.58634 0.81641 l.l852 300.19
430 110.21 10.634 83.219 -0.55863 0.81939 1.1708 305.37
440 106.49 19.742 94.868 -0.53185 0.82286 1.1594 310.36
450 103.07 28.802 106.42 -0.50589 0.82671 1.1506 315.15
460 99.928 37.829 117.89 -0.48068 0.83087 1.1438 319.79
470 97.016 46.837 129.30 -0.45614 0.83525 1.1386 324.28
480 94.307 55.834 140.66 -0.43221 0.83982 1.1348 328.64
490 91.778 64.831 152.00 -0.40884 0.84452 1.1321 332.88
500 89.410 73.833 163.31 -0.38599 0.849-33 1.1302 337.00
525 84.085 96.397 191.54 -0.33090 0.86163 l.l288 346.90
550 79.458 119.09 219.78 -0.27835 0.87409 1.1306 356.28
575 75.385 141.96 248.08 -0.22802 0.88651 1.1345 365.22
600 71.762 165.03 276.51 -0.17963 0.89876 l.I398 373.78
625 68.511 188.31 305.08 -0.13298 0.91075 l.1460 382.03
650 65.573 211.81 333.82 -0.08790 0.92242 1.1529 389.98
of') bL901 25).54 362.73 -0.04425 0.93375 1.1601 397.69

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1579

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv Cp Speed of

(K) (kg/m3) (kJ lk&) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m1s)

8.00 MPa Isobar

700 60.457 259.50 391.82 -0.00193 0.94470 1.1676 405.18

800 52.435 357.53 510.10 0.15596 0.98474 1.1977 433.26
900 46.389 458.84 631.29 0.29867 1.0189 1.2257 459.03
1000 41.644 563.03 755.14 0.42913 1.0478 1.2506 483.08
1100 37.807 669.71 881.31 0.54937 1.0723 1.2722 505.75

10.00 MPa Isobar

218.600b 1190.34 -428.40 -420.00 -2.2235 0.98274 1.9023 1012.5

220 1185.63 -425.77 -417.34 -2.2113 0.98061 1.9039 1003.1
225 1168.59 -416.36 -407.80 -2.1685 0.97323 1.9111 970.04
230 1151.15 -406.91 -398.22 -2.1264 0.96625 1.9208 937.02
235 1133.28 -397.41 -388.59 -2.0849 0.95969 1.9333 904.01
240 1114.92 - 387.85 -378.88 -2.0441 0.95356 1.9488 870.91
245 1095.99 -378.22 -369.09 -2.0037 0.94788 1.9679 837.63
250 1076.42 -368.49 -359.20 -1.9637 0.94269 1.9910 804.05
255 1056.11 -358.64 -349.18 -1.9240 0.93803 2.0189 770.05
260 1034.95 -348.66 -339.00 -1.8845 0.93400 2.0524 735.50
265 1012.80 -338.51 -328.64 -1.8450 0.93072 2.0930 700.25
270 989.46 -328.16 -318.06 -1.8055 0.92828 2.l425 664.15
1/j Y64./l -317.56 -3U7.2U -1.7656 0.92676 2.2034 627.04
280 938.22 -306.65 -296.00 -1.7253 0.92632 2.2798 588.67
285 909.56 -295.36 -284.36 -1.6841 0.92734 2.3782 548.68
290 878.06 -283.55 -272.16 -1.6416 0.93072 2.5108 506.63
295 842.67 -271.03 -259.16 -1.5972 0.93777 2.7009 461.99
300 801.62 -257.46 -244.98 -1.5496 0.94964 2.9906 414.28
305 751.67 -242.25 -228.94 -1.4965 0.96817 3.4711 363.01
310 685.77 -224.06 -209.48 -1.4333 0.99962 4.4460 307.04
315 586.02 -199.41 -182.35 -1.3465 1.0487 6.6962 249.42
320 448.28 -166.19 -143.88 -1.2253 1.0577 7.6175 219.14
325 358.04 -140.73 -112.80 -1.1289 1.0095 4.9438 219.84
330 310.25 -124.28 -92.049 -1.0655 0.96291 3.5312 225.91
335 280.11 -112.06 -76.359 -1.0183 0.92780 2.8165 232.23
340 258.62 -102.06 -63.396 -0.97991 0.90255 2.4017 238.14
345 242.11 -93.404 -52.100 -0.94692 0.88431 2.1341 243.58
350 228.80 -85.626 -41.921 -0.91762 0.87083 1.9480 248.62
360 208.25 -71.776 -23.756 -0.86644 0.85262 1.7065 257.77
370 192.74 -59.374 -7.4896 -0.82186 0.84146 1.5574 265.97
380 180.38 -47.885 7.5523 -0.78174 .0:83458 1.4570 273.47
390 170.18 . -37.015· 21.746 -0.74486 0.83060 1.3856 280.40
400 161.53 -26.584 35.325 -0.71048 0.82867 1.3327 286.88
410 154.05 -16.473 48.443 -0.67809 0.82827 1.2927 292.99
420 147.48 -6.5998 61.208 -0.64733 0.82901 1.2616 298.77
430 141.63 3.0936 73.698 -0.61794 0.83064 1.2373 304.28
440 136.39 12.651 85.972 -0.58972 0.83297 1.2181 309.55
45U 131.63 22.106 98.073 -0.56252 0.83584 1.2028 314.60
460 127.30 31.483 110.04 -0.53623 0.83915 1.1906 319.48
·+70 123.32 40.803 121.89 -0.51073 0.84280 1.1809 324.18

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1580 R. SPAN AND W. WAGNER

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

10.00 MPa Isobar

480 119.65 50.083 133.66 -0.48595 0.84672 1.1732 328.74

490 116.24 59.335 145.36 -0.46183 0.85085 1.1671 333.16
500 113.07 68.569 157.01 -0.43830 0.85516 1.1624 337.45
525 106.01 91.633 185.97 -0.38178 0.86644 l.1552 347.71
550 99.930 114.74 214.81 -0.32811 0.87812 1.1527 357.39
575 94.626 137.95 243.63 -0.27686 0.88993 l.1533 366.58
600 89.941 161.31 272.49 -0.22773 0.90169 1.1561 375.37
625 85.761 184.84 301.45 -0.18045 0.91329 1.1603 383.79
650 81.999 208.57 330.52 -0.13485 0.92464 1.1655 391.91
675 78.592 232.49 359.73 -0.09075 0.93571 1.1714 399.76
700 75.486 256.61 389.09 -0.04804 0.94645 1.1777 407.36
800 6.3.349 355.17 508.20 0.11097 0.98:591 1.2046 435.79
900 57.759 456.85 629.99 0.25438 1.0198 1.2308 461.77
1000 51.825 561.32 754.28 0.38532 1.0485 1.2545 485.94
1100 47.040 668.21 880.79 0.50588 1.0728 1.2753 508.69
15.00 MPa Isobar

219.644b 1196.11 -428.91 -416.37 -2.2260 0.98604 1.8799 1030.9

220 1194.96 -428.25 -415.70 -2.2230 0.98548 1.8801 1028.7
225 1178.64 -419.02 -406.29 -2.1807 0.97789 1.8841 99/.14
230 1162.02 -409.76 -396.86 -2.1392 0.97070 1.8900 965.81
235 1145.06 -400.49 -387.39 -2.0985 0.96394 1.8980 934.61
240 1127.73 -391.17 -377.87 -2.0584 0.95760 1.9081 903.50
245 1109.98 -381.82 -368.30 -2.0190 0.95169 1.9206 872.40
250 1091.77 -372.40 -358.66 -1.9800 0.94623 1.9358 841.27
255 1073.03 -362.92 -348.94 -1.9415 0.94121 1.9539 810.04
260 1053.71 -353.35 -339.12 -1.9034 0.93667 1.9752 778.68
265 1033.73 -343.69 -329.18 -1.8655 0.93264 2.0002 747.13
270 1013.01 -333.92 -319.11 -1.8279 0.92914 2.0294 715.36
275 991.45 -324.01 -308.88 -1.7903 0.92619 2.0635 683.32
280 968.93 -313.95 -298.47 -1.7528 0.92381 2.1034 650.96
285 945.30 -303.70 -287.83 -1.7152 0.92211 2.1501 618.23
290 920.40 -293.25 -276.95 -1.6773 0.92132 2.2055 585.07
295 894.00 -282.54 -265.76 -1.6390 0.92183 2.2727 551.45
300 865.82 -271.52 -254.20 -1.6002 0.92380 2.3557 517.40
305 835.48 -260.12 -242.17 -1.5604 0.92683 2.4583 483.07
310 802.54 -248.27 -229.58 -1.5195 0.93036 2.5830 448.77
315 766.51 -235.86 -216.30 -1.4770 0.93449 2.7343 414.97
320 726.83 -222.81 -202.18 -1.4325 0.93978 2.9188 382.22
325 683.09 -209.02 -187.06 -1.3857 0.94662 3.1280 351.34
330 635.51 -194.51 -170.91 -1.3363 0.95475 3.3309 323.89
335 585.40 -179.47 -153.85 -1.2850 0.96004 3.4748 301.72
340 535.55 -164.42 -136.41 -1.2333 0.95711 3.4738 286.11
345 489.42 -150.03 -119.38 -1.1836 0.94688 3.3164 276.63
350 449.20 -136.79 -103.39 -1.1376 0.93439 3.0688 271.76
360 387.08 -114.04 -75.292 -1.0584 0.91214 2.5672 270.06
370 343.43 -95.274 -51.596 -0.99347 0.89468 2.1949 273.34

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1581

TABLE j). Thennodynamic propenles of carbon dioxide--CUlllillueu

Temperature Internal energy Enthalpy Entropy Cv Speed of

(K) (kJlkg) (kJlkg) [kJ/(kg K)] [kJ/(kg K)] K)] sound (mls)

15.00 MPa Isobar

380 311.48 -79.159 -31.001 -0.93853 0.88143 1.9402 278.46

390 286.97 -64.804 -12.533 -0.89055 0.87178 1.7638 284.22
400 267.42 -.51.6.52 4.4406 0.84757 0.86502 1.6376 290.12
410 251.33 -39.353 20.329 -0.80833 0.86053 1.5445 295.97
420 237.78 -27.678 35.405 -0.77200 0.85782 1.4739 301.68
430 226.14 -16.471 49.860 -0.73798 0.85650 1.4192 307.22
440 215.98 -5.6217 63.828 -0.70587 0.85630 1.3761 312.59
450 207.D1 4.9509 77.410 -0.67534 0.85698 1.3416 317.79
460 199.00 15.307 90.682 -0.64617 0.85839 1.3138 322.83
470 191.79 25.492 103.70 -0.61817 0.86037 1.2911 327.70
480 185.24 35.541 116.52 -0.59119 0.86283 1.2725 332.43
490 179.26 45.484 129.16 -0.56511 0.86568 1.2572 337.03
500 173.76 55.342 141.67 -0.53985 0.86884 1.2445 341.50
525 161.74 79.733 172.48 -0.47972 0.87776 1.2218 352.18
550 151.63 103.91 202.83 -0.42323 0.88763 1.2080 362.24
575 142.97 128.01 232.93 -0.36972 0.89803 1.2002 371.77
600 135.43 152.12 262.88 -0.31873 0.90867 1.1963 380.86
625 128.78 176.29 292.77 -0.26992 0.91936 1.1953 389.55
650 122.86 200.57 322.66 -0.22303 0.92998 1.1963 397.91
675 111.)4 224.98 352.59 -0.17784 0.94044 1.1987 405.96
700 112.72 249.53 382.60 -0.13418 0.95067 1.2022 413.74
800 97.199 349.41 503.73 0.02753 0.98876 1.2213 442.71
900 85.740 452.00 626.95 0.17264 1.0218 1.2430 469.01
1000 76.856 557.14 752.31 0.301170 1.0501 1.2639 493.37
1100 69.730 664.55 879.66 0.42606 L0741 1.2828 516.21

20.00 MPa Isobar

220.677 b 1201.53 -429.34 412.70 2.2203 0.9BB84 1.8600 1048.9

225 1188.00 -421.49 -404.66 -2.1922 0.98212 1.8614 1022.8
230 1172.07 -412.41 -395.34 -2.1513 0.97475 1.8644 992.92
235 1155.89 -403.31 -386.01 -2.1111 0.96780 1.8690 963.24
240 1139.41 -394.20 -376.65 -2.0717 0.96128 1.8753 933.74
245 1122.62 -385.07 -367.25 -2.0330 0.95519 1.8833 904.38
250 1105.47 -375.91 -357.81 -1.9948 0.94951 1.8932 875.14
255 1087.95 -366.70 -348.32 -1.9572 0.94426 1.9050 845.98
260 1070.01 - 357.45 -338.76 -1.9201 0.93944 1.9188 816,88
265 1051.60 -348.15 -329.13 -1.8834 0.93504 1.9349 787.84
270 1032.69 - 338.77 -319.41 -1.8471 .0.93107 1.9533 758.85
275 1013.23 -329.33 -309.59 -1.8110 0.92753 1.9742 729.90
280 993,16 -319.80 -299.66 -1.7753 0.92441 1.9979 701.00
285 972.43 -310.17 -2S9.6t -1.7397 0.92176 2.0245 672.16
290 950.97 -300.44 -279.41 -1.7042 0.91964 2.0543 643.38
295 928.71 -290.59 -269.06 -1.6688 0.91824 2.0881 614.69
300 905.57 -280.61 -258.52 -1.6334 0.91763 2.1267 586.17
j05 881.46 -270.47 -247.78 -1.5979 0.91763 2.1709 537.91
310 856.27 -260.16 -236.80 1.5622 0.91780 2.2204 530.04
315 829.92 -249.67 -225.57 1.5262 0.91794 2.2743 502.71

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1582 R. SPAN AND W. WAGNER

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJlkg) [kJl(kg K)] [kJl(kg K)] [kJ/(kg K)] sound (m/s)

20.00 MPa I~obar

320 802.33 -238.98 -214.05 -1.4900 0.91835 2.3324 476.13

325 773.46 -228.09 -202.24 -1.4533 0.91938 2.3952 450.59
330 743.30 -217.00 -190.10 -1.4163 0.9209) 2.401U 420.44
335 711.96 -205.72 -177.63 -1.3788 0.92254 2.5246 404.10
340 679.68 -194.29 -164.87 -1.3410 0.92342 2.5778 384.01
345 646.90 -182.80 -151.88 -1.3030 0.92298 2.6122 366.45
350 614.18 -171.35 -138.79 -1.2654 0.92115 2.6207 351.52
360 551.54 -149.10 -112.84 -1.1923 0.91549 2.5511 329.54
370 496.14 -128.36 -88.048 -1.1243 0.90910 2.3976 316.94
380 449.68 -109.47 -64.990 -1.0628 0.90195 2.2129 3J1.J6
390 411.63 -92.347 -43.760 -1.0077 0.89472 2.0369 309.69
400 380.50 -76.728 -24.165 -0.95804 0.88827 1.8868 310.75
410 354.77 -62.306 -5.9310 -0.91301 0.88304 1.7645 3[3.29
420 333.(9 -48.819 11.205 -0.87171 0.87912 1.6664 316.66
430 314.83 -36.064 27.462 -0.83346 0.87643 1.5878 320.52
440 2Yl:S.99 -LUl:Sl 43.U11 -0.79771 0.87484 1.5244 324.64
450 285.14 -12.151 57.989 -0.76405 0.87419 1.4729 328.91
460 272.92 -0.78247 72.500 -0.73215 0.87434 1.4307 333.22
470 262.02 10.296 86.627 -0.70177 0.87517 1.3959 337.54
480 252.21 21.140 100.44 -0.67269 0.87657 1.3671 341.84
490 243.34 31.794 113.98 -0.64476 0.87845 1.3430 346.09
500 235.24 42.292 127.31 -0.61783 0.88074 1.3228 350.29
525 217.77 68.036 159.88 -0.55427 0.88779 1.2852 360.49
550 203.30 93.302 191.68 -0.49509 0.896l8 1.2606 370.28
575 191.06 118.30 222.98 -0.43943 0.90540 1.2446 379.65
600 180.50 143.15 253.95 -0.38670 0.91508 1.2344 388.65
625 171.28 167.96 284.73 -0.33644 0.92499 1.2284 397.29
650 163.l2 192.79 315.40 -0.28833 0.93496 1.2254 405.62
675 155.83 217.68 346.02 -0.24210 0.94487 1.2246 413.67
700 149.27 242.66 376.64 -0.19756 0.95465 1.2253 421.46
800 128.34 343.83 499.67 -0.03329 0.99149 1.2370 450.47
900 113.04 447.31 624.23 0.11340 1.0238 1.2545 476.80
LOOO 101.27 553.10 750.60 0.24652 1.0516 1.2727 501.16
1100 91.857 661.01 878.74 0.36864 1.0754 1.2898 523.98

25.00 MPa Isobar

b
221.701 1206.79 -429.71 -409.00 -2.2303 0.99124 1.1'5421 1066.4
225 1196.78 -423.81 -402.92 -2.2031 0.98601 1.8419 1047.3
230 1181.45 -414.87 -393.71 -2.1626 0.97846 1.8427 1018.6
235 1165.92 -405.93 -384.49 -2.1230 0.97135 1.8448 990.21
240 \\50.17 -396.99 -375.26 -2.0841 0.96468 1.81182 962.06
245 1134.16 -388.05 -366.00 -2.0460 0.95843 1.8530 934.14
250 1117.90 -379.09 -356.73 -2.0085 0.95259 1.8591 906.41
255 1101.35 -370.11 -347.41 -1.9716 0.94717 1.8666 878.88
260 1084.49 - 361.11 -338.06 -1.9352 0.94215 1.8755 851.52
265 1067.29 -352.08 -328.65 -1.8994 0.93752 1.8859 824.34

J. Phys. Chem. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUArlON OF STATE FOR CARBON DIOXIDE:. 1583

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJlkg) (kJlkg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

25.00 MPa Isobar

270 1049.74 -343.Ql -319.20 -1.8641 0.93329 1.8978 797.36

275 1031.80 -333.90 -309.67 -1.8291 0.92943 1.9111 770.56
280 1013.45 -324.75 -300.08 -1.7946 0.92595 1.9259 743.98
285 994.67 -315.55 -290.41 -1.7603 0.92283 1.9422 717.64
290 975.42 -306.29 -280.66 -1.7264 0.92013 1.9600 691.56
295 955.68 -296.97 -270.81 -1.6927 0.91792 1.9794 665.77
300 935.42 -287.59 -260.86 -1.6593 0.91623 2.0008 640.35
305 914.62 -278.13 -250.80 -1.6260 0.91497 2.0242 615.36
310 893.25 -268.60 -240.61 -1.5929 0.91387 2.0495 590.90
315 871.29 -258.99 -230.30 -1.5599 0.91273 2.0760 567.03
320 8-18.72 -249.31 -219.85 -1.5270 0.91162 2.1032 543.81
325 825.55 -239.55 -209.27 -1.4942 0.91081 2.1309 521.34
330 801.80 -229.72 -198.54 -1.4614 0.91044 2.1592 499.77
335 777.50 -219.83 -187.68 -1.4287 0.91042 2.1876 479.28
340 752.73 -209.88 -176.67 -1.3961 0.91046 2.2143 460.05
345 727.58 -199.90 -165.54 -1.3636 0.91032 2.2369 442.23
350 702.22 -189.91 -154.31 -1.3313 0.90989 2.2525 425.97
360 651.72 -170.10 -131.74 -1.2677 0.90829 2.2554 398.41
370 603.10 -150.79 ·109.34 -1.2064 0.90620 2.2187 377.41
380 557.99 -132.28 -87.474 -1.1480 0.90373 2.1495 362.54
390 517.36 -114.74 -66.415 -1.0933 0.90075 2.0598 352.86
400 481.55 -98.223 -46.307 -1.0424 0.89744 1.9613 347.18
410 450.35 -82.696 -27.183 -0.99520 0.89418 1.8644 344.41
420 423.27 -68.058 -8.9932 -0.95136 0.89131 1.7753 343.67
430 399.72 -54.187 8.3578 -0.91053 0.88902 1.6967 344.32
440 379.13 -40.963 24.978 -0.87232 0.88742 1.6290 345.93
450 361.01 -28.279 40.971 -0.83637 0.88650 1.5713 348.19
460 344.95 -16.042 56.432 -0.80239 0.88624 1.5222 350.90
470 330.61 -4.1769 71.440 -0.77011 0.88657 1.4806 353.92
480 317.72 7.3809 86.066 -0.73932 0.88744 1.4453 357.14
490 306.07 18.683 100.36 -0.70983 0.88878 1.4153 360.5 I
500 295.46 29.772 114.39 -0.68150 0.89052 1.3897 363.96
525 272.64 56.782 148.48 -0.61496 0.89633 1.3407 372.76
550 253.87 83.077 181.55 -0.55341 0.90365 1.3073 381.59
575 238.08 108.92 213.93 -0.49583 0.91195 1.2845 390.28
600 224.54 134.50 245.84 -0.44152 0.92086 1.2689 398.77
625 212.77 159.92 277.42 -0.38994 0.930tZ 1.2586 407.04
650 202.40 185.28 308.80 -0.34072 0.93954 1.2520 415.08
675 193.J8 210.63 340.05 -0.29354 0.94899 1.2483 422.90
700 184.90 236.02 371.23 -0.24818 0.95838 1.2465 430.51
800 158.65 338.44 496.02 -0.08J56 0.99409 1.2516 459.06
900 139.62 442.77 621.83 0.06661 1.0258 1.2653 485.14
1000 125.04 549.l9 749.14 0.20073 1.0532 1.2810 509.32
liDO 113.42 657.58 878.01 0.32355 1.0766 1.2964 531.99

J. Phys. Chem. Ref. Data, Vol. 25, No.6, 1996

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 1584 R. SPAN AND W. WAGNER

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kglm 3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)l [kJ/(kg K)] sound (m/s)

30.00 MPa Isobar

b
222.715 1211.77 -430.02 -405.26 -2.2321 0.99332 1.8259 1083.4
225 1205.06 -425.99 -401.09 -2.2135 0.98964 1.8251 1070.6
230 1190.25 -417.17 -391.97 -2.1734 0.98193 1.8241 1043.0
235 1175.29 -408.37 -382.85 -2.1342 0.97467 1.8242 1015.8
240 1160.15 -399.58 -373.72 -2.0958 0.96786 1.8254 988.76
245 1144.83 -390.80 -364.59 -2.0581 0.96147 1.8277 962.05
250 1129.30 -382.01 -355.45 -2.0211 0.95550 1.8311 935.59
255 1113.55 -373.22 -346.28 -1.9848 0.94994 1.8355 909.37
260 1097.57 -364.42 -337.09 -1.9491 0.94478 1.8410 883.41
265 1081.34 -355.61 -327.87 -1.9140 0.94000 1.8475 857.70
270 1064.86 -346.78 -318.61 -1.8794 0.93559 1.8550 832.25
275 1048.09 -337.94 -309.32 -1.8453 0.93153 1.8635 807.08
280 1031.04 -329.07 -299.97 -1.8116 0.92783 1.8729 782.21
285 1013.68 -320.18 -290.58 -1.7784 0.92446 1.8831 757.65
290 996.01 -311.26 -281.14 -1.7456 0.92145 1.8942 733.44
295 978.02 -302.32 -271.64 -1.7131 0.91882 1.9060 709.61
300 959.70 -293.34 -262.08 -1.6809 0.91659 1.9186 686.21
305 941.04 -284.33 -252.45 -1.6491 0.91471 1.9322 663.31
310 922.04 -275.29 -242.76 -1.6176 0.91301 1.9464 640.96
315 902.69 -266.22 -232.99 -1.5863 0.91135 1.9610 619.20
320 883.00 -257.12 -223.15 -1.5553 0.90973 1.9756 598.05
325 862.99 -248.00 -213.23 -1.5246 0.90830 1.9899 577.56
330 842.66 -238.85 -203.25 -1.4941 0.90721 2.0041 557.78
335 822.06 -229.69 -193.19 -1.4639 0.90648 2.0179 538.80
340 801.21 -220.51 -183.07 -1.4339 0.90599 2.0312 520.72
345 780.17 -211.34 -172.88 -1.4041 0.90560 2.0432 503.62
350 758.98 -202.17 -162.64 -1.3746 0.90520 2.0529 487.58
360 716.55 -183.92 -142.05 -1.3166 0.90427 2.0618 458.95
370 674.75 -165.93 -121.47 -1.2602 0.90323 2.0517 435.21
380 634.51 -148.37 -101.09 -1.2059 0.90215 2.0224 416.28
390 596.59 -131.36 -81.073 -1.1539 0.90099 1.9781 401.73
400 561.50 -114.99 -61.559 -1.1045 0.89970 1.9233 390.99
410 529.46 -99.289 -42.627 -1.0577 0.89833 1.8625 383.45
420 500.50 -84.257 -24.317 -1.0136 0.89698 1.7995 378.49
430 474.48 -69.860 -6.6324 -0.97200 0.89581 1.7378 375.55
440 451.16 -56.044 10.452 -0.93272 0.89494 1.6799 374.14
450 430.25 -42.746 26.982 0.89557 0.89446 1.6270 373.89
460 411.46 -29.901 43.010 -0.86034 0.89440. 1.5796 374.49
470 394.52 -17.449 58.593 -0.82682 0.89476 1.5378 375.74
480 379.18 -5.3349 73.783 -0.79484 0.89554 1.5011 377.47
490 365.24 6.4911 88.629 -0.76423 0.89671 1.4689 379.56
500 352.51 18.071 103.18 -0.73484 0.89824 1.4409 381.92
525 325.03 46.167 138.47 -0.66595 0.90339 1.3857 388.60
550 302.37 73.376 172.59 -0.60245 0.91002 1.3465 395.90
575 283.31 99.995 205.89 -0.54324 0.91767 1.3187 403.46

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1585

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cu cp Speed of

(K) (kg/m 3 ) (kJl1cg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)J. [kJI(kg K)] sound (mls)

30.00 MPa Isobar

600 266.99 126.23 238.59 -0.48756 0.92601 l.2990 411.10

625 252.82 152.22 270.88 -0.43483 0.93476 1.2852 418.70
650 240.36 178.08 302.89 -0.38462 0.94374 1.2757 426.21
675 229.30 203.86 334.70 -0.33660 0.95281 1.2695 433.60
700 219.39 229.64 366.38 -0.29051 0.96185 1.2657 440.86
800 188.05 333.24 492.77 -0.l2174 0.99658 1.2650 468.48
900 16:5.44 438.40 619.73 0.02779 1.0277 1.2752 494.02
WOO 148.15 545.42 747.91 0.16283 1.0547 1.2887 517.84
llOO t34.40 654.27 877.48 0.28631 1.0778 1.3026 540.25

40.00 MPa Isobar

224.715 b 1221.l2 -430.49 -397.73 -2.2352 D.99675 1.7975 1116.0

225 1220.33 -429.99 -397.22 -2.2329 0.99628 1.7973 1114.5
230 1206.41 -421.40 -388.24 -2.1935 0.98829 1.7937 1088.7
235 1192.39 -412.82 -379.28 -2.1549 0.98078 1.7910 1063.3
240 1178.27 -404.28 -370.33 -2.1172 0.97373 1.7892 lO38.2
245 1164.03 -395.75 -361.39 -2.0804 0.96713 1.7881 1013.4
250 1149.68 -387.24 -352.45 -2.0442 0.96096 l.7877 988.91
255 1135.19 -378.74 -343.51 -2.0088 0.95520 1.7881 964.76
260 1120.58 -370.26 -334.56 -1.9741 0.94983 1.7892 940.93
265 1105.83 -361.79 -325.61 -1.9400 0.94484 1.7908 917.41
270 1090.93 -353.32 -316.65 -1.9065 0.94022 1.7931 894.22
275 1075.88 -344.86 -307.68 -1.8736 0.93594 1.7959 871.38
280 1060.68 -336.41 -298.69 -1.8412 0.93198 1.7991 848.90
285 1045.33 -327.96 -289.69 -1.g093 O.92g35 1.8027 826.79
290 1029.82 -319.51 -280.67 -1.7779 0.92502 1.8066 805.09
295 1014.16 -311.07 -271.62 -1.7470 0.92201 1.8108 783.81
300 998.35 -302.62 -262.56 -1.7166 0.91930 1.8152 762.99
305 982.39 -294.19 -253.47 -1.6865 0.91688 1.8198 742.65
310 966.29 -285.76 -244.36 -1.6569 0.91467 1.8245 722.85
315 950.05 -277.33 -235.23 - 1.6277 0.91261 1.8291 703.59
320 933.68 -268.91 -226.07 -1.5988 0.91069 1.8334 684.89
325 1,1 17:l 1 -L6U.:'U -:L16.~SI -1.5704 0.90894 1.8375 666.75
330 900.63 -252.11 -207.70 -1.5423 0.90743 1.8412 649.20
335 883.97 - 243.73 -198.48 -1.5146 0.90618 1.8444 632.25
340 867.25 -235.37 -189.25 -1.4872 0.90518 1.8473 615.94
345 850.50 -227.04 -180.01 -1.4602 0.90437 1.8497 600.32
350 833.72 -218.73 -170.76 -1.4336 0.90369 1.8514 585.39
360 800.23 -202.22 - 152.23 -1.3814 -b.90261 1.8525 557.71
370 767.03 -185.87 -133.72 -1.3307 0.90182 1.8492 533.02
380 734.39 -169.74 -115.27 -1.2815 0.90130 1.8400 511.44
390 702.64 -153.87 -96.942 -1.2339 0.90102 1.8242 493.01
400 672.08 -138.32 -78.806 -/.1880 0.90094 1.8021 477.59
410 642.96 -123.13 -60.917 -1.l438 0.90101 1.7750 464.90
420 615.44 -108.31 -43.316 -1.1014 0.90123 1.7446 454.60
430 589.59 -93.874 -26.030 -1.0607 0.90157 1.7123 446.38

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1586 R. SPAN AND W. WAGNER

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cu cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (mls)

40.00 MPa Isobar

440 565.45 -79.814 -9.0735 -1.0217 0.90206 1.6790 439.96

450 542.98 -66.118 7.5496 -0.98436 0.90270 1.6457 435.07
460 522.12 -52.769 23.842 -0.94855 0.90351 1.6129 431.49
470 502.79 39.744 39.812 0.91420 0.90452 1.5814 429.01
480 484.89 -27.017 55.476 -0.88122 0.90574 1.5516 427.45
490 468.31 -14.563 70.851 -0.84952 0.90717 1.5238 426.63
500 452.94 -2.3539 85.959 -0.81899 0.90882 1.4981 426.42
525 419.10 27.259 122.70 -0.74727 0.91383 1.4435 427.89
550 390.67 55.849 158.24 -0.68114 0.91996 1.4013 431.27
575 366.46 83.699 192.85 -0.61959 0.92697 1.3692 435.81
600 345.60 111.02 226.76 -0.56185 0.93462 1.3451 441.07
625 327.40 137.98 260.16 -0.50733 0.94271 1.3271 446.76
650 311.36 164.69 293.16 -0.45555 0.95107 1.3139 452.71
675 297.09 191.24 325.88 -0.40615 0.95957 1.3043 458.80
700 284.29 217.70 358.40 -0.35885 0.96810 1.2975 464.97
800 243.83 323.44 487.49 -0.18646 1.0012 1.2880 489.58
900 214.66 430.11 616.45 -0.03457 1.0313 1.2926 513.34
1000 192.37 538.25 746.18 0.10210 1.0575 1.3024 535.98
1100 174.67 647.97 876.98 0.22676 1.0802 1.3137 557.53

50.00 MPa hobar

b -2.2377 0.99951 1146.9

226.679 1229.78 -430.78 -390.13 1.7735
230 1221.01 -425.19 -384.24 -2.2119 0.99412 1.7700 1130.8
235 1207.74 -416.81 -375.41 -2.1739 0.98640 1.7654 1106.8
240 1194.42 -408.45 -366.59 -2.1368 0.97918 1.7615 1083.2
245 1181.04 -400.l3 -357.79 -2.1005 0.97242 1.7582 1059.9
250 1167.59 - 391.83 -349.01 -2.0650 0.96609 1.7556 1037.0
255 1154.07 -383.56 -340.23 -2.0303 0.96020 1.7534 1014.4
260 1140.47 -375.31 -331.47 -1.9962 0.95470 1.7518 992.10
265 1126.80 -367.09 -322.71 -1.9629 0.94958 1.7507 970.17
270 1113.05 -358.88 -313.96 -1.9301 0.94483 1.7500 948.60
275 1099.22 -350.70 -305.21 -1.8980 0.94042 1.7496 927.39
280 1085.32 -342.53 -296.47 -1.8665 0.93634 1.7496 906.55
285 1071.33 -334.39 -287.72 -1.8355 0.93257 1.7498 886.10
290 1057.27 -326.26 -278.97 -1.8051 0.92910 1.7502 866.05
295 1043.14 -318.15 -270.21 -1.7752 0.92592 1.7507 846.42
300 1028.94 -310.05 261.46 1.7458 0.92303 1.7514 827.23
305 1014.67 - 301.98 -252.70 -1.7168 0.92039 1.7521 808.50
310 1000.35 -293.92 -243.94 -1.6883 0.91799 1.7527 790.25
315 985.97 -285.88 -235.17 -1.6603 0.91578 1.7533 772.50
320 971.55 -277.87 -226.41 -1.6326 0.91376 1.7538 755.25
325 957.10 -269.88 -217.64 -1.6055 0.91193 1.7540 738.51
330 942.63 -261.91 -208.87 -1.5787 0.91030 1.7539 722.28
335 928.14 -253.97 -200.10 -1.5523 0.90890 1.7536 706.59
340 913.66 -246.06 -191.33 -1.5263 0.90769 1.7529 691.43
345 899.19 -238.17 -182.57 -1.5007 0.90668 1.7520 676.84

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1587

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg .K)] [kJ/(kg K)] sound (m/s)

50.00 MPa Isobar

350 884.76 -230.32 -173.81 -1.4755 0.90581 1.7507 662.81

360 856.03 -214.73 -156.32 -1.4263 0.90448 1.7469 636.48
370 827.61 -199.29 -138.88 -1.3785 0.90360 1.7414 612.45
380 799.62 -184.03 - 121.50 -1.3321 0.90311 1.7340 590.70
390 772.18 -168.96 -104.21 -1.2872 0.90297 1.7243 571.22
400 745.45 -154.10 -87.024 -1.2437 0.90314 1.7120 554.02
410 719.54 -139.47 -69.977 -1.2016 0.90357 1.6970 539.02
420 694.59 -1:Z~.m~ -:'53.092 -1.1609 0.90423 1.679U .526.11
430 670.67 -110.94 -36.392 -1.1216 0.90508 1.6602 515.13
440 647.87 -97.069 -19.893 -1.0837 0.90612 1.6394 505.87
450 626.20 -83.452 -3.6055 -1.0471 0.90732 1.6180 498.11
460 605.67 -70.087 12.466 1.0118 0.90868 1.S'J64 491.68
470 586.26 -56.964 28.322 -0.97766 0.91018 1.5749 486.40
480 567.95 -44.071 43.965 -0.94473 0.91184 1.5538 482.14
490 550.68 -31.396 59.400 -0.91290 0.91363 1.5333 478.77
500 534.42 -18.926 74.634 -0.88213 0.91557 1.5136 476.18
525 497.78 11,454 111.90 -0.80939 0.92101 1.4687 472.48
550 466.18 40.875 148.13 -0.74197 0.92723 1.4308 471.73
575 438.78 69.547 183.50 -0.67907 0.93410 1.3999 472.96
600 4.14.84 97.051 218.18 -0.62003 0.94148 1.3753 475.52
625 393.77 125.33 252.31 -0.56429 0.94924 1.3561 479.00
650 375.06 152.71 286.02 -0.51141 0.95724 1.3412 483.09
675 358.33 179.87 319.40 -0.46101 0.96537 1.3300 487.62
700 343.27 206.88 352.54 -0.41281 0.97355 1.3215 492.43
800 295.34 314.44 483.74 -0.23759 1.0055 1.3064 513.16
900 260.55 422.42 614.33 -0.08378 1.0347 1.3070 534.47
1000 233.89 531.57 745.34 0.05425 1.0603 1.3140 555.44
1100 212.66 642.08 877.19 0.17991 1.0825 1.3232 575.78

75.00 MPa Isobar

231,448 b 1249.06 -430.98 -370.94 -2.2420 1.0049 1.7265 1217.6

235 1240.63 -425.27 -364.81 -2.2157 0.99929 1.7213 1202.5
240 1228.76 -417.26 -356.22 -2.1795 0.99178 1.7146 1181.5
245 1216.90 -409.30 -347.67 -2.1442 0.98477 1.7083 1160.9
250 1205.04 -401.38 -339.14 -2.1098 0.97824 1.7025 1140.6
255 1193.18 -393.50 -330.64 -2.0761 0.97215 1.6972 1120.6
260 1181.32 -385.66 -322.17 -2.0432 0.96649 1.6922 1101.0
265 1169.46 -377.85 -313.72 -2.0110 0.96122 1.6876 1081.7
270 1157.60 -370.08 -305.29 -1.9795 -6.95633 1.6833 1062.7
275 1145.74 -362.34 -296.88 -1.9487 0.95179 1.6793 1044.1
280 1133.89 -354.64 -288.50 -1.9184 0.94758 1.6756 1025.9
285 1122.04 -346.97 -280.13 -1.8888 0.94369 1.6720 1008.0
290 1110.20 -339.33 -271.78 -1.8598 0.94010 1.6687 990.43
295 1098.37 -331.72 -263.44 -1.8313 0.93680 1.6654 973.27
JUU 1086.56 -324.15 -2.5.5.12 -1.8033 0.93370 1.0023 95G.50

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1588 R. SPAN AND W. WAGNER

75.00 MPa Isobar

305 -316.60 0.93097 940.12

310 1062.97 -309.09 924.14
315 1051.22 -30'1.60' -230.25 0.926IO 1.6534 908.56
320 1039.49 -222.00 0.92399 1.6504 893.38
-2£3.75 -1.6708 0.92.208 1.6474 878.62
330 101G.lJ 0.92037
1004.51 -27l.97 0.91884 1.6413
340 992.95 -264.64 -I89.I1 -1.5967 0.91750 1.6381 836.84
345 981.43 -257.35 -\80.93 -1.5728 0.9\632 1.6348 '(1,23.15
350 -172.76 -1.5493 1.6314 8Il.OS
360 947.28 -235.66 -156.48 -1.5035 0.91369 1.6:L44 nfl.l)\)
370 924.90 -221.36 :-140.27 - L4591 0.91262 1.6170 764.58
380 902.87 -207.21 -1.4160 0.91202 1.6091
390 881.23 -193.20 -108.09 -1.3744 0.91184 1.6009
-100 1560.03 -179.33 -911"2'; 091204 1.5924 706.78
410 839.31 -165.61 -76.246 -1.2947 0.91258 1.5836 690.47
-60.456 0.91342 1.5745 675.53
430 799.37 -138.58 661.90
440 780.21 -125.28 -29.152 0.91585 1.5557 649.53
4S0 761.62 -1\'2..U. \.34GO (,)\'3.34
460 743.60 -99.093 1.7669 ~L1151 0.91910 1.5360 628.29
-86.204 -1.0822 0.92098 6J9.3J
480 709.36 611.32
dQf) fi91.14 -60.8It) 41.387 -1.0190 1.5052 604.25
500 677.52 -0.98873 0.92742 1.4949 598.02
525 641.03 -17.555 99.444 -0.91641 0.93352 1.4699 585.62
608.02 12.545 l35.90 0.94012 \.4468 576.92.
575 171.80 0.94711 1.4260 571.08
oW "-'1.22 71.1.')6 207.22 - 0.72443 0.95439 1.4077
-0.66130 0.96187 1.3920
650 504.66 128.22- 276.84 -0.61297 0.96949 1.3786 565.16
675 484.49 156.36 311.16 -0.56116 0.97717 1.3675 565.73
700 466.06 184.31 345.23 -0.51159 0.98486
800 405.95 295.12 479.87 -0.33177 J.0149 l.337Y YII.bl
900 1.0424 592.07
1000 326.23 516.83 746.72 ~0.O3403 (,0668 ~{H~.(W
1100 298.11 628.97 b~O.55 0.09352 1.0880 1.3414

J. Phys. Chern. Ref. Data, VoL 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1589

TABLE 35. Thermodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) . (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m/s)

100.00 MPa Isobar

b -2.2443
236.031 1265.83 -430.62 -351.62 1.0097 1.6919 1280.4
240 1257.21 -424.46 -344.92 -2.2162 1.0037 1.6854 1265.1
245 1246.37 -416.74 -336.51 -2.1815 0.99659 1.6778 1246.2
250 1235.57 -409.07 -328.14 -2.1477 0.98997 1.6706 1227.6
255 1224.80 -401.45 -319.80 -2.1147 0.98383 1.6637 1209.4
260 1214.06 -393.87 -311.50 -2.0824 0.97812 1.6573 1191.4
265 1203.36 -386.33 -303.23 -2.0509 0.97282 1.6512 1173.7
270 1192.69 -378.83 -294.99 -2.0201 0.96790 1.6454 1156.4
275 1182.06 -371.37 -286.77 -1.9900 0.96335 1.6399 1139.3
280 1171.46 -363.95 -278.59 -1.9605 0.95913 1.6347 1122.6
285 1160.90 -356.57 -270.43 -1.9316 0.95524 1.6297 1106.2
290 1150.37 -349.22 -262.29 -1.9033 0.95164 1.6249 1090.2
295 1139.89 -341.90 -254.18 -1.8755 0.94833 1.6203 1074.5
300 1129.45 -334.63 -246.09 -1.8484 0.94528 1.6158 1059.1
305 1119.04 -327.38 -238.02 -1.8217 0.94249 1.6115 1044.0
310 1108.69 -320.17 -229.97 1.7955 0.93993 1.6073 1029.3
315 1098.38 -312.99 -221.94 -1.7698 0.93760 1.6032 1015.0
320 1088.12 -305.84 -213.94 -1.7446 0.93548 1.5992 1001.0
325 1077.91 -298.72 -205.95 -1.7198 0.93356 1.5953 987.36
T~O IOn77n -?QI t'i4 -IQ7 C)C) -16955 0.93183 1.5914 974.07
335 1057.66 -284.59 - 190.04 -1.6716 0.93028 1.5876 961.13
340 1047.62 -277.56 -182.11 -1.6481 0.92891 1.5838 948.54
345 1037.64 -270.57 -174.20 -1.6250 0.92769 1.5800 936.31
350 1027.73 -263.61 -166.31 -1.6023 0.92663 1.5762 924.42
360 1008.12 -249.78 -150.58 -1.5580 0.92495 1.5687 901.70
370 988.80 -236.07 -134.93 -1.5151 0.92378 1.5612 880.34
380 969.80 -222.47 -119.36 -1.4736 0.92309 1.5537 860.31
390 951.13 -209.00 -103.86 -1.4333 0.92283 1.5461 841.58
400 932.81 -195.64 -88.438 -1.3943 0.92295 1.5386 824.08
410 914.87 -182.39 -73.089 -1.3564 0.92341 1.5311 807.78
420 897.31 -169.26 -57.815 -1.3196 0.92418 1.5237 792.60
430 880.14 -156.23 -42.614 -1.2838 0.92522 1.5164 778.51
440 863.37 -143.31 -27.486 -1.2490 0.92650 1.5092 765.42
450 847.00 -130.49 -12.430 -1.2152 0.92801 1.5021 753.30
460 831.05 -117.77 2.5559 -1.1823 0.92970 1.4952 742.08
470 815.51 -105.15 17.473 -1.1502 0.93157 1.4884 731.73
480 800.39 -92.616 32.324 -1.1189 0.93359 1.4817 722.18
490 785.67 -80.171 47.108 -1.0884 0.93574 1.4752 713.39
500 771.37 -67.812 61.828 -1.0587 0.93801 1.4688 705.34
525 737.38 -37.261 98.354 -0.98741 0.94412 1.4534 688.12
550 705.86 -7.1663 134.50 0.92014 0.95070 1.4388 674.60
575 676.71 22.527 170.30 -0.85649 0.95763 1.4251 664.18
600 649.77 51.872 205.77 -0.79610 0.96480 1.4127 656.31
625 624.90 80.921 240.95 -0.73867 0.97211 1.4016 650.49
fl'iO fl01 c)1 109 77 275.86 -0.68389 0.97951 1.3918 646.36

J. Phys. Chem. Ref. Data, Vol. 25, No.6, 1996

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 1590 R. SPAN AND W. WAGNER

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cu cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (mls)

100.00 MPa Isobar

675 580.64 138.32 310.55 -0.63153 0.98693 1.3833 643.59

700 560.93 166.76 345.04 -0.58135 0.99434 1.3760 641.95
800 494.96 279.54 481.58 -0.39900 1.0231 1.3573 643.10
900 444.32 391.83 616.89 -0.23962 1.0494 1.3505 651.25
1000 404.15 504.47 751.91 -0.09737 1.0728 1.3507 662.59
1100 371.36 617.86 887.14 0.03152 1.0931 1.3544 675.48

200.00 MPa Isobar

b
252.864 1318.45 -426.12 -274.43 -2.2449 1.0320 1.6131 1476.5
255 1314.84 -423.09 -270.99 -2.2314 1.0295 1.6096 1470.1
260 1306.44 -416.05 -262.96 -2.2002 1.0240 1.6016 1455.4
265 1298.11 -409.04 -254.97 -2.1697 1.0188 1.5940 1440.8
270 1289.84 -402.08 -247.02 -2.1400 1.0141 1.5867 1426.6
275 1281.64 -395.15 -239.10 -2.1110 1.0097 1.5797 1412.5
280 1273.50 -388.27 -231.22 -2.0826 1.0057 1.5730 1398.7
285 1265.43 -381.42 -223.37 -2.0548 1.0020 1.5666 1385.1
290 1257.43 -374.61 -215.55 -2.0276 0.99855 1.5604 1371.8
295 1249.48 -367.83 -207.77 -2.0010 0.99539 1.5545 1358.7
300 1241.61 -361.09 -200.01 --1.9749 0.99248 1.5488 1345.9
305 1233.79 -354.38 -192.28 -1.9493 0.98981 1.5434 1333.3
310 1226.04 -347.70 -184.57 -1.9243 0.98736 1.5381 1321.0
315 1218.35 -341.05 -176.90 -1.8997 0.98512 1.5331 1308.9
320 1210.72 -334.43 -169.24 -1.8756 0.98307 1.5282 1297.1
325 1203.16 -327.84 -161.61 -1.8519 0.98121 1.5235 1285.5
330 1195.66 -321.28 -154.01 -1.8287 0.97952 1.5190 1274.2
335 1188.22 -314.74 -146.42 -1.8059 0.97799 1.5146 1263.1
140 lIRO_R4 -10R_2':1 -118.86 -1.7835 0.97662 1.5104 1252.2
345 1173.53 -301.75 -131.32 -1.7615 0.97539 1.5064 1241.6
350 1166.27 -295.28 -123.80 -1.7398 0.97430 1.5025 1231.2
360 1151.94 -282.43 -108.81 -1.6976 0.97249 1.4950 1211.2
370 1137.86 -269.67 -93.896 -1.6568 0.97114 1.4880 1192.1
380 1124.01 -256.98 -79.049 -1.6172 0.97020 1.4815 1173.9
390 1110.41 -244.38 - -64.266 -1.5788 0.96963 1.4753 1156.5
400 1097.04 - 231.85 -49.543 -1.5415 0.96940 1.4695 1140.0
410 1083.91 -219.39 -34.876 -1.5053 0.96947 1.4640 1124.3
420 1071.02 -207.00 -20.262 -1.4700 0.96981 1.4588 1109.4
430 1058.36 -194.67 -5.6992 -1.4358 0.97040 1.4539 1095.3
440 1045.94 -182.40 8.8159 -1.4024 0.97121 1.4492 1081.9
450 1033.74 -170.19 23.286 -1.3699 0.97222 1.4448 1069.2
460 1021.78 -158.02 37.713 -1.3382 0.97341 1.4406 1057.1
470 1010.04 -145.91 52.099 -1.3072 0.97477 1.4367 1045.7
480 998.53 -133.85 66.447 -1.2770 0.97627 1.4329 1034.8
490 987.24 -121.83 80.758 -1.2475 0.97791 1.4294 1024.6
500 976.16 -109.85 95.035 -1.2187 0.97967 1.4260 1014.9
525 949.42 -80.066 130.59 -1.1493 0.98451 1.4185 992.79
550 923.96 -50.491 165.97 -1.0835 0.98986 1.4120 973.51
575 899.74 -21.088 201.20 -1.0208 0.99559 1.4065 956.68
600 876.69 8.1703 236.30 -0.96106 1.0016 14019 94200

J. Phys. Chern. Ref. Data, Vol. 25, No. G, 1 ggG

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1591

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m 3) CkJ(kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m1s)

200.00 MPa Isobar

625 854.75 37.312 271.30 -0.90391 1.0078 1.3980 929.18

650 833.86 66.359 306.21 -0.84915 1.0140 1.3948 918.02
675 813.97 95.331 341.04 -0.79656 1.0204 1.3922 908.32
700 795.00 124.25 375.82 -0.74597 1.0267 1.3900 899.91
800 727.46 239.61 514.53 -0.56073 1.0513 1.3851 876.78
900 671.10 354.93 652.94 -0.39771 1.0740 1.3836 865.84
1000 623.57 470.58 791.32 -0.25192 1.0942 1.3841 862.60
1100 583.00 586.76 929.81 -0.11992 1.1119 1.3860 864.16

400.00 MPa Isobar

b
281.544 1392.45 -410.72 -123.46 -2.2315 1.0894 1.5590 1732.5
285 1388.17 -406.23 -118.08 -2.2125 1.0870 1.5546 1724.6
290 1382.04 -399.75 -110.32 -2.1855 1.0838 1.5485 1713.3
295 1375.97 -393.30 -102.59 -2.1591 1.0808 1.5426 1702.1
300 1369.95 -386.88 -94.895 -2.1332 . 1.0780 1.5369 1691.2
30S 1364.00 -380.48 -87.224 -2.1078 1.07j4 l.j314 1680.4
310 1358.11 -374.11 -79.581 -2.0830 1.0729 1.5260 1669.9
315 1352.28 -367.76 -71.964 -2.0586 1.0707 1.5209 1659.5
320 1346.50 -361.44 -64.371 -2.0347 1.0686 1.5160 1649.3
325 1340.78 355.14 56.803 2.0112 1.0667 1.5112 1639.3
330 1335.11 -348.86 -49.259 -1.9882 1.0650 1.5067 1629.5
335 1329.50 -342.60 -41.737 -1.9656 1.0633 1.5022 1619.8
340 1323.95 -336.36 -34.236 -1.9433 1.0618 1.4980 1610.3
345 1318.44 -330.14 -26.757 -1.9215 1.0605 1.4939 1601.1
350 1312.99 -323.94 -19.297 -1.9000 1.0592 1.4899 1591.9
360 1302.24 -311.60 -4.4362 -1.8582 1.0570 1.4824 1574.2
370 1291.69 -299.32 10.353 -1.8177 1.0552 1.4754 1557.2
380 1281.33 -287.10 25.074 -1.7784 1.0537 1.4690 1540.8
390 1271.16 -274.94 39.733 -1.7403 1.0525 1.4630 1525.0
400 1261.17 -262.83 54.335 -1.7033 1.0516 1.4574 1509.8
410 1251.35 -250.77 68.883 -1.6674 1.0510 1.4522 1495.3
420 1241.70 -238.76 83.381 -1.6325 1.0506 1.4475 1481.2
430 1232.22 -226.78 97.833 -1.5985 1.0504 1.4430 1467.7
440 1222.89 -214.85 112.24 -1.5654 1.0503 1.4389 1454.8
450 1213.72 -202.95 126.61 -1.5331 1.0505 1.4352 1442.3
460 1204.70 -191.08 140.95 -l.5016 1.0508 1.4317 1430.3
470 1195.83 -179.25 155.25 -1.4708 1.0513 1.4285 1418.8
480 1187.10 -167.44 169.52 -1.4408 1.0519 1.4255 1407.7
490 1178.51 -155.65 183.76 -1.4114 1.0526 1.4228 1397.1
500 1170.05 -143.89 197.97 -1.3827 1.0534 1.4203 1386.9
525 1149.47 -114.58 233.41 -1.3135 1.0559 1.4149 1363.0
550 1129.67 -85.361 268.72 -1.2478 1.0588 1.4106 1341.4
575 1110.59 -56.223 303.94 -1.1852 1.0622 1.4072 1321.8
600 1092.21 -27.143 339.09 -1.1253 1.0659 1.4045 1304.1
625 1074.47 1.8990 374.18 -1.0681 1.0698 1.4025 1288.1

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 1592 R. SPAN ANDW. WAGNER

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (m1s)

4.0000 MP:! T<:ob:!r

650 1057.35 30.916 409.22 -1.0131 1.0739 1.4011 1273.5

675 1040.82 59.921 444.23 -0.96022 1.0781 1.4001 1260.4
700 1024.84 88.926 479.23 -0.90931 1.0825 1.3995 1248.5
800 966.02 205.09 619.16 -0.72246 1.0999 1.3997 1211.0
900 914.22 321.71 759.24 -0.55747 1.1165 1.4023 1185.7
1000 868.27 438.97 899.65 -0.40954 1.1316 1.4060 1168.7
1100 827.20 556.88 1040.44 -0.27535 1.1451 1.4098 1157.6

600.00 MPa Isobar

b
305.996 1448.66 -391.42 22.754 -2.2128 1.1462 1.5467 1910.7
310 1444.64 -386.39 28.939 -2.1927 1.1442 1.5427 1903.0
315 1439.67 -380.12 36.640 -2.1681 1.1419 1.5377 1893.5
320 1434.75 -373.88 44.317 -2.1439 1.1397 1.5329 1884.2
325 1429.88 -367.65 51.970 -2.1201 1.1376 1.5283 1875.1
330 1425.06 -361.44 59.600 -2.0969 1.1357 1.5238 1866.1
33) 141U.l~ -j55.24 67.208 -2.0740 1.1338 1.5194 1857.3
340 1415.56 -349.07 74.794 -2.0515 1.1321 1.5152 1848.6
345 1410.88 -342.91 82.360 -2.0294 1.1305 1.5111 1840.1
350 1406.25 -336.76 89.905 -2.0077 1.1290 1.5071 183L7
360 1397.12 -324.52 104.94 -1.9653 1.1263 1.4996 1815.4
370 1388.16 -312.33 119.90 -1.9243 1.1240 1.4925 1799.7
380 1379.38 -300.19 134.79 -1.8846 1.1219 1.4858 1784.5
390 1370.75 -288.10 149.62 -1.8461 1.1201 1.4796 1769.8
400 1362.28 276.05 164.38 1.8087 1.1186 1.4738 1755.6
410 1353.97 -264.05 179.09 -1.7724 1.1174 1.4683 1741.9
420 1345.79 -252.08 193.75 -1.7371 1.1163 1.4633 1728.7
430 1337.76 -240.15 208.36 -1.7027 1.1154 1.4585 1715.9
4.4.0 1329.R7 -22R.25 222.92 -1.6692 1.1 V17 1.4541 1703.6
450 1322.10 -216.38 237.44 -1.6366 1.1142 1.4500 1691.6
460 1314.46 -204.54 251.92 -1.6048 1.1139 1.4462 1680.1
470 1306.94 -192.72 266.37 -1.5737 1.1136 1.4427 1668.9
480 1299.54 -180.92 280.78 -1.5434 1.1135 1.4394 1658.1
490 1292.26 -169.15 295.16 -1.5137 1.1135 1.4363 1647.7
500 1285.08 -157.39 309.50 -1.4847 1.1137 1.4335 1637.5
525 1267.60 -128.07 345.26 -1.4149 1.1144 1.4275 1613.7
550 1250.74 -98.828 380.89 -1.3487 1.1157 1.4226 1591.6
575 1234.45 -69.645 416.40 -1.2855 1.1174 1.4187 1571.3
600 1218.69 -40.503 451.83 -1.2252 1.1195 1.4157 1552.5
625 1203.43 -11.386 487.19 -1.1675 1.1218 1.4134 1535.1
650 1188.63 17.720 522.50 -1.1121 1.1243 1.4117 1519.1
675 1174.27 46.825 557.78 -1.0588 1.1271 1.4106 1504.2
700 1160.32 75.938 593.04 -1.0075 1.1299 1.4099 1490.5
800 1108.23 192.61 734.02 -0.81926 1.1419 1.4103 1445.3
900 1061.27 309.84 875.20 -0.65298 1.1538 1.4134 1412.4
1000 1018.66 427.73 1016.74 -0.50386 1.1649 1.4175 1388.8
1100 979.76 546.30 1158.69 -0.36856 1.1749 1.4216 1371.9

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1593

TABLE 35. Thennodynamic properties of carbon dioxide-Continued

Temperature Density Internal energy Enthalpy Entropy Cv cp Speed of

(K) (kg/m3) (kJ/kg) (kJ/kg) [kJ/(kg K)] [kJ/(kg K)] [kJ/(kg K)] sound (mls)

800.00 MPa Isobar

b -369.91 164.96 -2.1926 1.1961 1.5477

327.673 1495.70 2052.8
330 1493.71 -367.02 168.56 -2.1817 1.1951 1.5457 2048.9
335 1489.46 -360.83 176.28 -2.1585 1.1931 1.5415 2040.7
340 1485.25 -354.66 183.97 -2.1357 1.1912 1.5373 2032.6
345 1481.08 -348.50 191.65 -2.1132 1.1894 1.5333 2024.6
350 1476.96 -342.35 199.31 -2.0912 1.1877 1.5294 2016.8
360 1468.83 -330.09 214.56 -2.0482 1.1846 l.5218 2001.6
370 1460.85 -317.88 229.74 -2.0066 1.1817 1.5147 1986.8
380 1453.03 -305.72 244.86 -1.9663 1.1791 1.5080 1972.5
390 1445.35 -293.59 259.90 -1.9272 1.1769 1.50J6 1958.7
400 1437.82 -281.51 274.89 -1.8893 1.1748 1.4956 1945.4
410 1430.42 -269.46 289.82 -1:8524 1.1730 1.4899 1932.4
420 1423.15 -257.45 304.69 -1.8166 1.1714 1.4845 1919.9
430 1416.00 -245.46 319.51 -1.7817 1.1699 1.4795 1907.8
440 1408.98 -233.51 334.28 -1.7478 1.1687 1.4748 1896.0
450 1402.08 221.58 349.01 1.7147 1.1676 1.4703 1884.G
460 1395.29 -209.67 363.69 -1.6824 1.1667 1.4661 1873.5
470 1388.60 -197.79 378.33 -1.6509 1.1659 1.4622 1862.8
480 1382.03 -185.93 392.93 -J.6202 1.1652 1.4586 1852.4
400 1375.55 -174.0g 407.50 -1.5001 1.1647 1.4551 Ig-1:2.3
500 1369.17 -162.26 422.04 -1.5608 1.1642 1.4519 1832.5
525 1353.64 -132.76 458.24 -1.4901 1.1636 1.4448 1809.1
550 1338.65 -103.33 494.29 -1.4230 1.1636 1.4389 1787.4
575 1324.16 -73.959 530.20 -1.3592 1.1640 1.4340 1767.1
600 1310.14 -44.627 566.00 -1.2982 1.1648 1.4301 1748.1
625 1296.54 -15.319 601.71 -1.2399 1.1659 1.4269 1730.4
650 1283.34 13.975 637.35 -1.1840 1.1673 1.4244 1713.8
675 1270.52 43.267 672.93 -1.1303 1.1688 1.4225 1698.2
700 1258.04 72.565 708.47 -1.0786 1.1706 1.4211 1683.6
800 1211.18 189.94 850.45 -0.88900 1.1785 1.4193 1633.6
900 1168.47 307.80 992.46 -0.72175 1.1868 1.4212 1594.8
1000 1129.16 426.25 J 134.74 -0.57184 1.1948 1.4247 1564.9
1100 1092.77 545.32 1277.40 -0.43587 1.2020 J .4286 1542.2

"Sublimation temperature.
bMelting temperature.
'Saturation temperature.

11. Acknowledgments 10K. E. Starling, P. N. Batdorf, and Y. C. Kwok, Hydrogen Proc. 51, 2, 86
(l '172).
1I R. Meyer-Pittroff, Dissertation, TC Miinchen (1973).
The authors are grateful to the Deutsche Forschungsge-
12F. H. Huang, M. H. Li, L. L. Lee, K. E. Starling, and F. T. H. Chung, J.
meinschaft for their financial support of this project. Chern. Eng. Jpn. 18. 490 (1985).
13 J. Ewers and W. Wagner, A Methodjor Uptimizing the Structure ofEqua-

tions of State and its Application to an Equation of State for Oxygen, in

12. References Proc. 8th Syrnp. Thermophys. Prop. - Vol. 1, J. V. Sengers, coordinating
editor (Am. Soc. Mech. Eng .. New York, 1982).
I ILTAC Commi~sion on Atomic \Vcights imd Isotopic AbulIddll\;C:>, J. 11 J. F. Ely, An Equation Of State Model for Pure CO 2 and CO Rich MIX-
2
Phys. Chern. Ref. Data 24. 1561 (1995). tures, in Proc. 65th Annu. Convention Gas Proc. Assoc. (San Antonio,
"E. R. Cohen and B. N. Taylor. The 1986 Adjustment of the Fundamental Texas, 1986).
Plnsical Constants, CODATA Bull. No. 63 (Pergamon. Oxford, 1986). 151. F. Ely, 1. W. Magee, and W. M. Haynes. C02PAC, Program available
:; S. Angus. B. Armstrong. and K. M. de Reuck, fnternational Tables of the
at the NatL Bur. Stand. (Boulder, Colorado, 1987).
Fluid State-3: Carbon Dioxide (Pergamon. Oxford. 1976).
16 K. S. Pitzer and D. R. Schreiber, Fluid Phase Equilibria 41, I (1988).
-l R. Schmidt and W. Wagner. Fluid Phase Equilibria 19, 175 (1985).

) A. Saul and W. Wagner. 1. Phys. Chern. Ref. Data 18, 1537 (1989). 171. F. Ely. W. M. Haynes. and B. C. Bain, 1. Chern. Thermodyn. 21, 879
flU. Setzrnann and W. Wagner. lnt. J. Thermophys. 10.1103 (1989). (1989).
7 E. Bender. "Equatiolls of State ExactlY Represellling the Phase Behavior
18R. T. Jacobsen and R. B. Stewart, J. Phys. Chern. Ref. Data 2,757 (1972).
of Pure Substances." in Proceedings of the Fifth Symposium 011 711ermo- 18a K. S. Pitzer and S. M. Sterner. 1. Chern. Phys. 101, 4, 311 J (1994).
phnics Properfles. C. F. Bonila. coordinating editor (AS ME. New York, 19p. Schofield. Phys. Rev. Lett. 22. 606 (1969).
1970). 20G. A. Chapela and J. S. Rowlinson. 1. Chem. Soc .. Faraday Trans. (I) 70,
Sy. Y. Altunin and O. G. Gadetskii. Teploenergetica 18, 81 (1971). 584 (1974).
9W. A. Stein. Chern. Eng. Sci. 27. 1371 (1972). 2: J. F. Ely. 1. W. Magee. and W. M. Haynes, Tlzennophysical Properties of

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

Downloaded 12 Jan 2013 to 152.14.136.96. Redistribution subject to AIP license or copyright; see http://jpcrd.aip.org/about/rights_and_permissions
1594 R. SPAN AND W. WAGNER

::,pecial High CO 2 Content Mixtures, Research Report RR-110 (National 60 A Michels, B. Blaisse, and J. Hoogschagen, Physica 9, 565 (1942).
Bureau of Standards, Boulder, 1987). 61K Clusius, U. Piesbergen, and E. Varde, Helv. Chim. Acta 43, 1290
22M. Vicenti-Missoni, J. M. H. Levell Sengers, and M. S. Green, J. Res. (1960).
1\'at1. Bur. Stand. A 73, 563 (1969). 62H. Bois and A. P. Wills, VerhandL der Deutschen Phys. Ges. 1, 168
23T. A. Murphy, J. V. Sengers, and J. M. H. Levelt Sengers, Analysis of the (l899).
Pressure of Gases Ncar the Critical Point ill Terms of a Scaled Equation 001. P. Kuenen and W. G. Robson, Philos. Mag. 6, 149 (1902).
of State, in Proc. 6th Symp. Therrnophys. Prop., P. E. Liley. coordinating MK. H. annes and S Weber, Com. Phys. Lab. Univ. Leidcn 137b. 8
editor (AS ME, New York, 1973). (1913).
24p. C. Albright, T.J. Edwards, Z. Y. Chen, and J. V. Sengers, J. Chern. 65H. Siemens, Ann. Phys. 42, 871 (1913).
Phys 87, 1717 (1987). 66S. Weber and H. K annes, Com. Phys. Lab. Univ. Leiden 137c, 26
25p. C. Albright, Z. Y. Chen, and J. V. Sengers, Phys. Rev., Rapid Com- (1913).
mun. 36. 877 (1987). 67F. Henning, Ann. Phys. 43, 282 (1914).
26
0. D. Erickson, T. W. Leland, and J. F. Ely, Fluid Phase Equilibria 37, 68W. Heuse and J. Otto, Ann. Phys. 9, 486 (1931).
185 (1987). wW. Heuse and 1. Otto, Ann. Phys. 14, 185 (1932).
27Z. Y. Chen, A Abbaci, S. Tang, and J. V. Sengers, Phys. Rev. A 42, 70W. F. Giauque and C. J. Egan, J. Chern. Phys. 5, 45 (1936).
4470 (1990). 71 A. W. Tickner and F. P. Losing, J. Phys. Colloid Chern. 55, 733 (1951).
28 S. n. Kiselev, 1. G. Kostyukova, and A. A Povodyrev, Int. J. Thermo- 72D. Ambrose, Trans. Faraday Soc. 52, 772 (1955).
phys. 12, 877 (1991). 73M. J. Hiza, Cryogenics 10, 106 (1970).
29R. Fox, Fluid Phase Equilibria 14,45 (1983). 74Z. Bilkadi, M. W. Lee, and J. Biegeleisen, J. Chern. Phys. 62, 2087
30U. Setzmann and W. Wagner, J. Phys. Chem. Ref. Data 20,1061 (1990). (1974).
31 J. Ahrendts and H. D. Baehr, Forseh. lng. Wes. 45, 1, 1 (1979). 75c. E. Bryson, V. Cazcarra, and L L. Levenson, J. Chern. Eng. Data 19,
l2W. Wagner, Cryogenics 12, 214 (1972). 107 (1974).
33J. Ahrendts and H. D. Baehr, Forseh. lng. Wes. 45, 2, 51 (1979). 76B. Fernandez-Fassnacht and F. del Rio, J. Chern. Thermodyn. 16, 469
34W. Wagner, VDI Fortschritt-Ber., Reihe 3, Nr. 39 (VOl-Verlag, Dussel- (1984).
dorf, 1974). 77W. H. Keesom, Com. Phys. Lab. Univ. Leiden 88, I (1903).
35 R. Span and W. Wagner, Int. 1. Therrnophys. (submitted). 78C. F. Jenkin and D. R. Pye, Philos. Trans. R. Soc. 213, 67 (1914).
36H. Preston-Thomas, \1etrologia 27,3 (1990). 79 0. C. Bridgeman, J. Am. Chern. Soc. 49,1174 (1927).
37H. Preston-Thomas, P. Bloembergen, and T. J. Quinn, Supplementary 80 A. Michels, B. Blaisse, and C. Michels, Proc. R. Soc. A160, 358 (1936).
Information for the /Illernational Temperature Scale of 1990 (Bureau 81 J. R. Roebuck, T. A Murell, and E. E. Miller, J. Am. Chern. Soc. 64, 400
lnternationale des Poids et Mesures, Sevres, 1990). (1942).
38R. L. Rusby, J. Chern. Themlodyn. 23, 1153 (1991). 82 A. Michels, T. Wassenar. Th. Zwietering, and P. Smits, Physica 16,501
39R. B. Bedford and C. G. M. Kirby, Metrologia 5, 83 (1969). (1950).
4DC. H. Meyers and M. S. Van Dusen, Bur. Stand. J. Res. 10, 381 (1933). S3H. H. Reamer, B. H. Sage, and W. N. Lacey, Ind. Eng. Chern 43, 2515
41 D. Ambrose, Brit. J. AppL Phys. 8, 32 (1957). (1951).
42D. R. Lovejoy, Nature 197, 353 (1963). 84J. A Bierlein and B. K. Webster, Ind. Eng. Chern. 45, 618 (1953).
43E. Haro, E. Fernandez-Fassnacht, and F. del Rio, Rev. Soc. Quim. Mex. 85 D. Cook, Proc. R. Soc. 219, 245 (1953).
23, 369 (1979). 86 D. Cook, Trans. Faraday Soc. 49, 716 (1953).
44L A. K. Staveley, L. Q. Lobo, and J. C. G. Calado, Cryogenics 21, 131 B7E. Schmidt and W. Thomas, Forseh. lng. Wes. 20, 161 (1954).
(1981). 8SR. H. Wentorf, J. Chern. Phys. 24, 607 (1956).
45R. Blanes-Rex, E. P. A Fernandez, and F. Guzman, Cryogenics 22, 113 89 A B. KIetskii, lng. Phys. Zeitschr. 7, 40 (1964).
(1982). 90R. G. P. Greig and R. S. Dadson, Brit. J. Appl. Phys. 17, 1633 (1966).
46F. Pavese and D. Ferri, TMCSI 5, 217 (1982). 91 J. L Edwards and D. P. Johnson, J. Res. Nat!. Bur. Stand. Sec. C 72,27
47R. E. Bedford, G. Bonnier, H. Maas, and F. Pavese, Metrologia 20, 145 (1968).
(1984). 92M. P. Vukalovich, V. P. Kobelev, and N. 1. Timoshenko, Teploenergetica
48G. Bonnier, Y. Hermier, and W. B. Qin, "Triple Point of Carbon Dioxide 15, 6, 80 (1968).
in a Multicompartment Sealed Cell," in Proceedillgs of the 2nd IMEKO 90y' A. Kirillin, S. A. Ulybin, and E. P. Zherdev, Teploenergetica 16, 6, 92
Symposium on Temperature Measuremelll in Industry and Science, B. (1969).
Suhl, coordinating editor, GDR 1984. 94E. P. Kholodov, N. I. Timoshenko, and A L. Yaminov, Teploenergetica
49W. Duschek, VDI Fortschritt-Ber., Reihe 3, Nr. 187 (VOl-Verlag, Dus- 19,4, 84 (1972).
seldorf, 1989). 95 A. Fredenslund and J. Mollerup, J. Chern. Soc. Farraday Trans. (1) 70,
50 J. M. H. Levelt Sengers and W. T. Chen, J. Chern. Phys. 56, 595 (1972). 1653 (1974).
51 M. R. Moldover, J. Chern. Phys. 61, 1766 (1974). 96R. J. Gugoni, J. W. Eldridge, V. C. Okay, and T. 1. Lee, A1.Ch.E. J. 2(1,
52 J. A. Lira, c. Edwards, and M. J. Bnckingham, Phys. Rev. A 15, 778 93 (1974).
(1977). 97 G. J. Besserer. and D. B. Robinson, J. Chern. Eng. Data 21, 81 (1975).
53M. R. Moldover, J. V. Sengers, R. W. Gammon, and R. J. Hocken, Rev. 981. Davalos, W. R. Anderson, R. B. Phelps, and A J. Kidnay, J. Chem.
Mod. Phys. 51, 79 (1979). Eng. Data 21,81 (1976).
54H. J. Baade, Dissenation, TV Brannschweig (1983). 99K. Stead and J. M. Williams, J. Chem. Thermodyn. 12, 265 (1980).
SST. J. Edwards, Ph.D. Thesis, University of Western Australia (1984). 1ooH. Kwang-Bae, N. Nagahama, and M. Hirata, J. Chern. Eng. Data 27, 25
56 J. V. Sengers and J. M. H. Level! Sengers, Annu. Rev. Phys. Chern. 37, (1982).
189 (1986) 100T. A Al-Sahhaf, A. J. Kidnay, and E. D. Sloan, Ind. Eng. Chem. Fund.
57Z. Y. Chen, P. C. Albright, and J. V. Sengers, Phys. Rev. A 41, 3161 22, 372 (1983).
(1990). 102H. G. Kratz, Dissertation, Ruhr-Universitat Bochum (1984).
5SW. Duschek, R. Kleinrahm, and W. Wagner. J. Chern. Thermodyn. 22, I03J. C. Holste, K. R. Hall, P. T. Eubank, G. Esper, M. Q. Warowny, D. M.
841 (1990). Bailey, J. G. Young, and M. T. Bellamy, J. Chern. Thermodyn. 19, 1233
59!. M. AbduJagatov, 1. M. Abdurakhamov, R. G. Batyrova, and N. G. (1987).
Polikhronidi, "Isochoric Heat Capacity and Liquid-Gas Coexistence 104T. S. Brown, A. J. Kidnay, and E. D. Sloan, Fluid Phase Equilibria 40,
Curve of Carbon Dioxide in the Region of Critical State," paper pre- 169 (1988).
sented at 11th Symp. on Therrnophys. Prop., Boulder, Colorado, 1991. 105 N. N. Shah, 1. A Zollweg, and W. B. Streett, J. Chern. Eng. Data 36, 188
59ar. M. Abdulagatov, N. G. PoIikhronidi, and R. G. Batyrova, Ber. Bun- (1991).
senges. Phys. Chem. 98, 1068 (I 994). lOS'L. Yurttas, J. C. Holste, K. R. Hall, B. E. Gammon, and K. N. Marsh, 1.
59br. M. Abdulagatov, N. G. Polikhronidi, and R. G. Batyrova, J. Chenl. Chern. Eng. Data 39, 418 (1994).
Thermodyn. 26, 1031 (1994). 106M. E.-H. Amagat, C. R. Acad. Sci. 114, 1093 (1892).

J, Phys, Chern. Ref, Data, Vol. 25, No.6, 1996

Downloaded 12 Jan 2013 to 152.14.136.96. Redistribution subject to AIP license or copyright; see http://jpcrd.aip.org/about/rights_and_permissions
 A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1595

107U. Behn, Ann. Phys. 3, 733 (1900). 153p. J. McElroy, R. Battino, and M. K. Dowd, J. Chem. Therrnodyn. 21,
108H. H. Lowry and W. R. Erickson, J. Am. Chem. Soc. 49, 2729 (1927). 1287 (1989).
109 J. Straub, Wiirme und Stoffubertragung 5, 56 (1972). 154W. Duschek, R. Kleinrahm, and W. Wagner, J. Chem. Therrnodyn. 22,
1I0W. M. Haynes, Orthobaric Liquid Densities and Dielectric Constants of 827 (1990).
Carbon Dioxide, paper presented at the Cryog. Eng. Conf., Mass. Inst. of. 155M. Jaeschke, A. E. Humphreys, P. Van Caneghem, M. Fauveau, R.
Tech., Cambridge, 1985. Janssen-Yan Rosmalen, and Q. Pellei, GERG Technical Monograph
III G. J. Esper, Dissertation, Ruhr-Universitiit Bochum (1987). 4-The GERG Databank of High Accuracy Compressibility Factor Mea-
112 A. Eucken and F. Hauck, Z. Phys. Chem. 134, 161 (1928). surements, edited by Group Europeen de Recherches Gazieres (YDI-
113 1. 1. Novikov and Y. S. Trelin, Zur. Prik. Mech. Tech. Fiz. 2, 112 (1960). Verlag, Dusseldorf, 1990).
114K. I. Amirkhanov, N. G. Polikhronidi, B. G. Alibekov, and R. G. Baty- 156p. Nebendahl, YDI Fortschritt-Ber., Reihe 3, Nr. 212 (YDI-Yerlag, Dus-
rova, Teploenergetica 19, 1,61 (1972). seldorf, 1990).
IISW. Pecceu and W. Van Dae1, Physica 63, 154 (1972). 157X. Y. Guo, R. Kleinrahm, and W. Wagner, Experimentelle Untersuchung
1161. W. Magee and J. F. Ely, Int. J. Thermophys. 7, 1163 (1986). der systematischen Me[3fehler von Betriebsdichteaufnehmernfiir Erdgas-
117 e. F. Jenkin, Proc. R. Soc. A 98, 170 (1920). Me[3trecken - Tei! 1: Me[3ergebnisse for Stickstoff, Kohlendioxid. Argon.
1180. Maass and J. H. Mennie, Proc. R. Soc. A 110, 198 (1926). Neon. Ethan und Ethen, Report Lehrstuhl fur Thermodynamik, Ruhr-
1l9D. LeB. Cooper and O. Maass, Can. J. Res. 2, 388 (1930). Universitat Bochum, Bochum, 1992.
120D. LeB. Cooper and O. Maass, Can. J. Res. 4, 283 (1931). 158L. A. Weber, Int. J. Thermophys. 13, 1011 (1992).
121 W. Cawood and H. S. Patterson, J. Chem. Soc., 619 (1933). 159R. Gilgen, R. Kleinrahm, and W. Wagner, 1. Chem. Therrnodyn. 24, 1493
122 A. Michels and e. Michels, Proc. R. Soc. A 153, 201 llY~5). (1992).
123 A. Michels, e. Michels, and H. Wouters, Proc. R. Soc. A 153, 214 160K. Brachthauser, R. Kleinrahm, H.-W. Losch, and W. Wagner, YDI
(1935). Fortschritt-Ber., Reihe 8, Nr. 371 (YDI-Yerlag Dusseldorf, 1993).
124H. H. Reamer, R. H. Olds, B. H. Sage, and W. N. Lacey, Ind. Eng. Chem. 160a A. Fenghour, W. A. Wakeham, and J. T. R. Watson, J. Chem. Thermo-
36, 88 (1944). rlyn 27, ?lQ (lQQ'i)
l2SG. A. Bottomley, D. S. Massie, and R. Whitlaw-Gray, Proc. R. Soc. A 160b J. Klimeck, R. Kleinrahm, and W. Wagner (private communication)
200,201 (1950). (1995).
126T. Batuecas and e.G. Losa, An. Fis. Quim. B 50, 845 (1954). 160cZ. Gokmenoglu, Y. Xiong, and E. Kiran, 1. Chem. Eng. Data 41, 354
I27G. e. Kennedy. Am. 1. Scie. 252. 225 (954). (1996).
128M. P. Yukalovich and Y. Y. Altunin, Teploenergetica 6, 11,58 (1959). IOOtlp. Nowak, T. Tielkes, R. Kleinrahm, and W. Wagner (unpublished).
129M. P. Yukalovich and Y. Y. Altunin, Teploenergetica 9,5, 56 (1962). 160ew. Wagner, K. Brachthiiuser, R. KIeinrahm, and H.-W. Losch, Int. J.
130M. P. Yukalovich, Y. Y. Altunin, and N. 1. Timoshenko, Teploenergetica Therrnophys. 16, 399 (1995).
161 R. Kleinrahm and W. Wagner, YDI Fortschritt-Ber., Reihe 3, Nr. 92
10, 2, 92 (1963).
(YDI-Yerlag, Dusseldorf, 1986).
131 M. P. Yukalovich, Y. Y. Altunin, and N. 1. Timoshenko, Teploenergetica
162F. G. Keyes and S. e. Collins, Proc. N. A. S. 18,328 (1932).
10, 1, 85 (1963).
163G. B. Kistiakowsky and W. W. Rice, J. Chem. Phys. 7, 5, 281 (1939).
132 J. Juza, Y. Kmonicek, and O. Sifner, Physica 31, 1735 (1965).
I64S. R. de Groot and A. Michels, Physica 14, 218 (1948).
I33p. S. Ku and B. F. Dodge, J. Chem. Eng. Data 12, 158 (1967).
165J. F. Masi and B. Petkof, J. Res. Natl. Bur. Stand. 48, 179 (1952).
134 A. Sass, B. F. Dodge, and R. H. Bretton, J. Chem. Eng. Data 12, 168
166y. E. Schrock, Calorimetric Determination of Constant-Pressure Specific
(1967).
Heats of Carbon Dioxide at Elevated Pressures and Temperatures, Na-
135M. P. Yukalovich, Y. P. Kobelev, and N. 1. Timoshenko, Teploenergetica
tional Advisory Committee for Aeronautics, Tech. Note 2838 (1952).
15, 4, 81 (1968).
167L. B. Koppel and J. M. Smith, J. Chem. Eng. Data 5,437 (1960).
136E. A. Golovskii and Y. A. Tsymamyi, Teploenergetica 16, 1,67 (1969).
168M. P. Yukalovich, Y. Y. Altunin, and A. N. Gureev, Teploenergetica 11,
my. A. Kirillin. S. A. Ulybin, and E. P. Zherdev, Teploenergetica 16, 2, 94
9, 68 (1964).
(I969).
169M. P. Yukalovich and A. N. Gureev, Teploenergetica 11, 8, 80 (1964).
l38y. A. Kirillin. S. A. Ulybin, and E. P. Zherdev, "Experimental Investi-
170M. P. Yukalovich, Y. Y. Altunin, and A. N. Gureev, Teploenergetica 12,
gation of Carbon Dioxide Density at Temperatures from -50 to +200
7,58 (1965).
°C and Pressures up to 500 bar," in Proceedings of the First Interna- 171 S. L. Rivkin and Y. M. Gukov, Teploenergetica 15, 10, 72 (1968).
tional Conference on Calorimetry and Thermodynamics, Warsaw, 1969. l72y. Y. Altunin and D~D. Kuznetsov, Teploenergetica 16, 8, 82 (1969).
139D. S. Tsiklis, L. R. Linshits, and S. S. Tsimmermann, "Measurement and l73y. Y. Altunin and D. O. Kuznetsov, Teploenergetica 17, 11,91 (1970).
Calculation of the Molar Volume and Thermodynamic Properties of Car- I7-lS. L. Rivkin and Y. M. Gukov, Teploenergetica 18, 10,82 (1971).
bon DIOxide at High Pressures and Temperatures," in f'roceedlllgs Of the 175y' Y. Altunin and D. O. Kuznetsov, Teploenergetica 19, 6, 67 (1972).
1st International Conference on Calorimetry and Thermodynamics, War- I76S. Saegusa, T. Kobayashi, Y. Takaishi, and K. Watanabe, Bull. JSME 23,
saw. 1969. 2055 (1980).
l.lOy. A. Kirillin. S. A. Ulybin. and E. P. Zherdev, Teploenergetica 17, 5, 69 I77R. Bender, K. Bier, and G. Maurer, Ber. Bunsenges. Phys. Chern. 85. 778
(1970). (19151).
1,\1 Y. N. Popov and M. K. Sayapov. Teploenergetica 17,4.76 (1970). 178G. Ernst and U. E. Hochberg, 1. Chem. Thermodyn. 21. 407 (1989).
I·e M. P. Yukalovich. N. 1. Timoshenko. and Y. P. Kobelev, Teploenergetica 179G. Ernst, G. Maurer. and E. Wiederuh. 1. Chern. Thermodyn. 21. 53
17. 12.59 (1970). (1989).
1-1< W. Schonmann. Dissertation. TH Karlsruhe (971). 179aT JJmrbin. T _Y rm::1m. ~nrl J -P E. Colier. Rev. Sci In~trl1m. 65. 10,
I-I-IE. P. Kholodov. l\. l. Timoshenko. and A. L. Yamnov. Teploenergetica 3263 (1994).
19.3.84 (1972). 180H. W. Wooley. 1. Natl. Bur. Stand. 52. 289 (1954).
1-1 5 1. Hoinkis. Dissertation. TH Karlsruhe (1989). 181 H. D. Baehr, H. Hartmann, H.-e. Poh!. and H. Schomacker, Thermody-
1-I6 G.1. Besserer and D. B. Robinson. 1. Chem. Eng. Data 18. 137 (1973). l1amisc/ze FlIllktionen idealer Gase fiir Temperatllren bis 6000 oK, edited
1-17 D. S. Rasskazov. E. K. Petrov. G. A. Spiridonov. and E. R. Ushmaikin. by H. D. Baehr (Springer-Verlag, Berlin, 1968).
Teploenergetica 21. l. 80 (1974). 182L. V. Gurvich. Thermodynamic Properties of Characteristic Substances
l-l~ V. \1. Shmono\" and K. I. ShmulO\ich. Akad. Wouk SSSR 217. 935 (Nauka. Moskwa. 1979), Vol. II, Part II.
( 19741. 183 J. Chao. in TRC ThermodYllamic Tables Hydrocarbons. K. W. Marsh,
1-l'iW._W. R. Lau. Ph.D. Thesis. Texas A&~I University (1986). coordinating editor (Texas A&M University, Austin. 1983). Vol. YIII.
I~O \1. laeschke. ppT Data from Refractive Index Measurements (private 18-11. Chao (private communication) (1986).
communication) ( 19871. 185R. E. Pennington and K. A. Kobe. 1. Chern. Phys. 22, 1442(954)
I~I ~t Jaeschke. ppT Data from Burnett ~1easurements (private communica- 186 A. Michels and 1. Strijland. Physica 18, 613 (1952).
tion 1 ([ 9871. 187 K. I. Amirkhanov. N. G. Polikhronidi, and R. G. Batyrova, Teploener-
1~2 1. W. Magee and 1. F. Ely. rnt. 1. Thermophys. 9. 547 (J 9881. getica 17. 3. 70 (1970).

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

Downloaded 12 Jan 2013 to 152.14.136.96. Redistribution subject to AIP license or copyright; see http://jpcrd.aip.org/about/rights_and_permissions
 1596 R. SPAN AND W. WAGNER

188K. I. Amirkhanov and N. G. Polikhronidi, Teploenergetica 18, 12, 59 2l3T. L. Cottrell, R. A. Hamilton, and R. P. Taubinger, Trans. Faraday Soc.
(1971). 52, 1310 (1956).
189 J. V. Sengers (private communication) (1986). 214D. Cook, Can. J. Chem. 35, 268 (1957).
19OJ. A. Lipa, C. Edwards, and M. J. Buckingham, Phys. Rev. Lett. 25, 1086 215 A. P. Masia and M. D. Pena, An. Fis. Quim. B 54, 661 (1958).
(1970). 216E. G. Butcher and R. S. Dadson, Proc. R. Soc. 227, 448 (1963).
191C. M. Herget, 1. Chern. Phys. 8, 537 (1940). 217 J. A. Huff and T. M. Reed, J. Chern. Eng. Data 8, 306 (1963).
1921. 1. Novikov and Y. S. Trelin, Tepioenergetica 9,2, 79 (1962). 218M. P. Vukalovich and Y. F. Masalov, Teploenergetica 13, 5, 58 (1966).
193L. L. Pitaevskaya and A. V. Bilevich, Russ. J. Phys. Chem. 47, 126 2l9R. S. Dadson, E. J. Evans, and 1. H. King, Proc. Phys. Soc. 92, 1115
(1973). (1967).
194W. Lemming, VDI Fortschritt-Ber., Reihe 19, Nr. 32 (VDI-Verlag, Dus- 220N. I. Timoshenko, V. P. Kobelev, and E. P. Kholodov, Teploenergetica
seldorf, 1989). 17,9,64(1970).
195 J. Noury, Etude de la vitesse des ultrasons dans les flu ides au voisinage 221 M. Waxman, H. Davis, and 1. R. Hastings, "A New Determination of the
du point critique (Academy of Sciences, 1951). Second Virial Coefficient of Carbon Dioxide at Temperatures Between
196y' S. Trelin and E. P. Sheludiakov, J.E.T.P. Lett. 3, 2, 63 (1966). 0° and 150°C, and an Evaluation of Its Reliability," in Proceedings of
\97R. W. Gammon, H. L. Swinney, and H. Z. Cummins, Phys. Rev. Lett. 19, the Sixth Symposium on Thermophysical Properties (ASME, New York,
1467 (1967). 1973).
198G. T. Feke, K. Fritsch, and E. F. Carome, Phys. Rev. Lett. 23, 1282 222K. Ohgaki, N. Sakai, Y. Kano, and T. Katayama, 1. Chern. Eng. Jpn. 17,
(1969) 545 (1984).
199 K. Fritsch and E. F. Carome, Behavior of Fluids in the Vicinity of the 223B. V. MaUu, G. Natarajan, and D. S. Viswanath, J. Chern. Thermodyn.
Critical Point, NASA Research Report CR-1670 (1970). 19,549 (1987).
2000. Maass and W. H. Barnes, Proc. R. Soc. A 111, 224 (1926). 224B. V. MaUu, G. Natarajan, and D. S. Viswanath, 1. Chern. Thermodyn.
201 M. P. Vukalovich and Y. F. Masalov, Teploenergetica 11, 7, 78 (1964). 21, 989 (1989).
202M. P. Vukalovich and Y. F. Masalov, Teploenergetica 11, 11, 75 (1964). 225R. Span, VDI Fortschritt-Ber., Reihe 6, Nr. 285 (VDI-Verlag, Dusseldorf,
203D. Moller, B. E. Gammon, K. N. Marsh, K. R. Hall, and J. C. Holste, J. 1993).
Chern. Thermodyn. 25, 1273 (1993). 226 J. M. H. Levelt Sengers, W. L. Greer, and J. V. Sengers, J. Phys. Chern.
204K. KrUger, VDl Fortschritt-Ber., Reihe 6, Nr. 1 (VDI-Verlag, Dusseldorf, Ref. Data 5, 1 (1976).
1964). 227 J. E. Verschaffelt, Com. Phys. Lab. Leiden 28 (1896).
205 H. D. Baehr, "Measurements of the Internal Energy and the Influence of 228K. G. Wilson, Phys. Rev. 4, 3174 (1974).
Gravity Near the Critical Point of CO 2, " in Proceedings of the Fourth 229p. Hill, J. Phys. Chem. Ref. Data 19, 1233 (1990).
Symposium on Thermophysical Properties (ASME, New York, 1968). 230W. Wagner, N. Kurzeja, and B. Pieperbeck, Fluid Phase Equilibria 79,
206M. P. Vukalovich, V. V. Altunin, K. Bulle, D. S. Rasskazov, and D. 151 (1992).
Ertel, Teploenergetica 17, 5, 60 (1970). 231 H. T. Haselton, W. E. Sharp, and R. C. Newton, Geophys. Res. Lett. 5,
207E. S. Burnett, Phys. Rev. 22, 590 (1923). 753 (1978).
208V. V. Altunin and A. N. Gureev, Teploenergetica 19, 1, S9 (1972). 232W. J. Nellis, A. C. Mitchell, F. H. Ree, N. C. Holmes, and R. J. Trainor,
208aL. Cusco, S. E. McBain, and G. Saville, 1. Chern. Thermodyn. 27, 721 J. Chern. Phys. 95, 5268 (1991).
(1995). 233 G. L. Schott, High Pres. Res. 6, 187 (1991).
209K. Schafer, Z. Phys. Chern. B 36, 85 (1937). 234E. H. Brown, Bu!. lnt. Inst. Refrig. 1, 169 (1960).
210K. E. MacCormack and W. G. Schneider, J. Chem. Phys. 18, 1269 21ST. E. Morsy, Dissertation, TH Karlsruhe (1963).
(1950). 236D. Straub, Dissertation, TH Karlsruhe (1964).
211 T. L. Cottrell and R. A. Hamilton, Trans. Faraday Soc. 51, 156 (1955). 237 A. Schaber, Dissertation. TH Karlsruhe (1965).
212W. C. Pfefferle, J. A. Goff, and J. G. Miller, J. Chern. Phys. 23, 509 238D. G.Miller, Ind. Eng. Chern. Fund. 9, 585 (1970).
(1955). 239 K. M. de Reuck (private communication) (1991).

J. Phys. Chern. Ref. Data, Vol. 25, No.6, 1996

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