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

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 Lehesbt fr Thermadgnumil, Rahr-Universitis Baxhaon, DAA7BO Docu, Germany Ressned 25 May 1998 ‘This work reviews the avaslable data on thermodynamic properties of carbon dioxide and presents a new equation of state inthe form of a fundamental equation explicit inthe Helmholtz free energy. The function forthe residual part of the Helmholtz free energy was fiied to selected data of the following properties: (a) thermal properties of the single-phase region (ppT) and (b) of the liquid-vapor saturation curve (p,, p', p") including the Maxwell criterion, (€) speed of sound w and (4) specific isobaric heat capacity cy of the single phase region and ofthe saturation curve, (e) speciticisochoric heat capacity c,, (0) specific enthalpy f, (g) specific intemal energy u, and (h) Joule ‘Thomson coefficient. By applying moder strategies forthe optimization ofthe math ‘ematical form of the equation of state and forthe simultaneous nonlinear fit to the data of tll theve propertsn, the roulting formulation io ablo to roprecent even the moctacourate data to within their experimental uncertainty. Inthe technically most important region up to pressures of 30 MPa and up to temperatures of $23 K, the estimated uncertainty of the ‘equation ranges from 0.03% to 0.08% in the density, 0.03% to > 1% in the spoed ‘of sound, and 0.156 to *1.S% in the isobaric heat capacity. Special intrest 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 formulation yiclds @ reasonable description even of the caloric properties in the immediate Vicinity of the eritical point. Atleast fr the basic properties such as pressure, fugacity and enthalpy, the equation can be extrapolated upto the limits ofthe chemical stability of ‘carbon dioxide. Independent equations for the vapor pressure and forthe pressure on the sublimation and melting curve, for the saturated liguid 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 Institue of Physics and American Chemical Society. Xe wor: carbon dixie; coneaton: etl region; da evan; equation of sate; extaplton: fendamentl equation: ming ines pope Ube subiaton line: thea end elec popes: and Contents Nomenclature, <-. 1513-3. Phase Equilibria of Carbon Dioxide. 1519 Physical Constants for Carbon Dioxide 1513 3.1 Triple Point 1519 1. nedvetion 1514 3.2 Critical Point, 1519 1.1 Background 151433. Melting Pressure 1520 1.2 Prior Correlations of Carbon Dioxide 3.4 Sublimation Pressure... 1521 Proesties and Demands on the New 3.5. Vapor Pressure 1521 Correlation 1514 3.6 Saturated Liquid Density TL) sz 1.3 Organization of the Anicte. 1516 3:7 Saturated Vapor Density 1525 2. Basie 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 Helmboltz Function 15164, Experimental Basis of the New Equation of 2.2. Helmholtz Energy of the Ideal Gas. 1516 State esis) 2.3 Residual Part of dhe Helubolue Energy..---. 1517 4.1. Thetuual Properties a2 2.31 Fitting an Empirical Equation for 42 Specific Isobaric Heat Capac 1528 to Data. 1517 42.1 Experimental Results forthe Specific 23.2 Optimizing the Mathematical Form... 1518 Isoharic Heat Capacity 1398 23.3 The Procedure of Weighting, 1518 4.2.2 Results for the Specific Isobaric Heat 0047. 2899/96725(6y1509/61820.00 1509 4 Phys. Chem, Ref. Data, Vo. 25, No. 6, 19961510 Capacity in the Mdeal-Gat State 43 Specific Isochoric Heat Capacity 44 Speed of Sound. . 45 Enthalpy 46 Internal Eneray. 47 Joule~Thomson Coeficien. 48 Visi Coeficiens,. 49 Liquid Vapor Equilibria, 4.10 Adjustment of Data 4.10.1 Adjustment of Data Sets Describing the Critical Region... 4.102. Adjustment of ppT Data. 4.103 Correction of Isobaric Heat Capacities. 2. Deswstion of Thetnnaly a Critical Region, 5.1 Limitations of Analytical Equations of State. ‘52 Use of Nonanalvtic Terms as an ntezral ‘Component in an Empirical Wide-Range Equation of State aes 6. New Equation of State. 46. eal-Gas Pat of the Helmbotez Energy. 662 Residual Part of the Helmholtz Energy... 7. Comparisons of the New Equation of State with Experimental Data and Other Fayations of State 111 Liquid Vapor Boundary... 7.11 Thermal Properties on the Coexistence Curve... 1.42 Catone Properties on he Coeiistence Curve. 72 Single-Phase Region... 71 Thermal Properties in the Single Phase Region 7.22 Caloric Properties in the Single-Phise Region 1.8 Extrapolation Behavior af the New Fundamental Equation, 73.1. Extrapolation Beyond the Range of 7.3.2. Representation of “Ideal Curves”. 8. Uncertainty of the New Fundamental Equation. 9. Conclusions 10, Appendix: Thermodynamic Properties of Carbon Dioxide. LL. Acknowledgments Pagyesies inthe List of Tables tathon dioxide Selected scaled equations of state for carbon dioxide 3. Relations of thermodynamic properties to the dimensionless Helmholtz function ¢ consisting of 8 and 6 see Eq, (2.1), 4 Suteste data fr dhe ple poi of easbon dioxide te for 4. Phys. Chem. Ret. Date, Vol. 25, No.6, 1996 1529 1530 1532 1532 1532 1332 1333, 1532 1534 1534 154 1535 1335 1536 1537 1541 381 1543, 1546 1546 1546 S47 1547 1847 1353) 1356 1557 1559 1559 1359 1393 Isis Isis 1317 1320) s. 16. R. SPAN AND W. WAGNER Selected data forthe extical point of carboa, dioxi Summary ofthe dat sets for the sublimation ‘ressure of carbon dioxide ‘Summary of the data sets for the vapor pressure of carbon dioxide Summary of the datasets forthe saturated Tigi ‘density of carbon dioxide ‘Summary of the datasets for the saturated vapor ensity of earbon dioxide Suumnary of the dala sets for calenie properties ‘on the liquid-vapor phase boundary of carbon dioxide sommary Af the date cate menlable for the pr relation of carbon dioxide Summary of selected pp 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. ‘Summary of the data sets avalable for the specific isobaric heat capacity of carbon dioxide. ‘Summary of selected data forthe specific Feobarc host capacity of carbon dionida; detailed information is given on the uncertainty values estimated by the authors and those estimated by ‘oaselves and used in the weighting procedure. ‘Datasets for the isobaric heat capacity in the ideal-gas state of carbon dioxide calculated by ‘theoretical approaches. Summary of the datasets available forthe specific isochoric heat capacity of carbon dioxide isochoric heat capacity of carbon dioxide; detailed informatin is given on the uncertainty values estimated by the authors and those estimated by ourselves and used in the weighting procedure, Summary of the data sets available forthe speed ‘of sound of carbon dioxide Summary of selected data forthe speed of sound ‘of earbon dioxide; detailed information is given ‘on the uncertainty values estimated by the used in the weighting procedure Summary of the datasets available for enthalpy differences of carbon dioxide. ‘Summary ofthe datasets available for diferences (ofthe internal energy of carbon dioxide. ‘Summary ofthe data sets available forthe Joule— ‘thomson coeticient of carbon dioxide, Summary of data available forthe second and third virial coefficient of carbon dioxide. For reasons explained in the tent ne data were assigned to Group 1 1520 1591 1322 1523, 1324 1526 1327 1329) 1330) 1330 1530 131 1331 1531 1532 1332 1532 oss 1333)24, 2, 26, 2, 2% 2, 0 3L 32. 33 35 ANEW EQUATION OF STATE FOR CARBON DIOXIDE Summary of selected data describing the liquid-vapor phase equilibrium 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. ‘Temperature dependent conection of isobaric teat capacity data Examples for power laws describing thermodynamic properties along certain paths throughout the extical region. Cocficint of the corelation equations, Eg (6.2) and Bq, (6.3), for c® and $°, respectively... ‘The ideal-gas part of the dimensionless Helmholtz ‘energy @* and Hs oenvacives. Summary of the data used forthe linear ‘optimization proceduse and for the nonlinear ft. Parameters of the nonanalytic terms in the bank of terms. . Coeficients and exponents of Eq (63). ‘The residual part of the dimensionless Helmholtz energy "and is denwvatves. ‘The definition of the zeroth- and first-order ideal ceurves of the compression factor Z. ‘Thermedynamic properties of saturated carbon dioxide 7 “Thermodynamic properties of cazbon dioxide. List of Figures Relative deviations of experimental meking pressure data from values calculated from the melting pressure equation, Ba, (3.10). In this figure, both the conected and the uncorrected data are ploted (see Sec. 3.3). Absone deviations Aun (Damap~Dasnae) Of selected experimental sublimation pressure data from valves calculated from the sublimation pressure equation, Ea. (3.12). In this figure, both the corrected and the uncorrected data ot Bitkadi era” are plotted (see Sec. 34). Relative deviations of selected experimental sapor preccune dats From waluceealatod from the vapor pressure equation, Eq. (3.13) ‘Vapor pressures calculated from the corresponding equation of Angus eta” are plotted for comparison Relative deviations 1003 9°10 agp" ca) exp Of selected experimental saturated liquid entity data from values calelated from Eq, (3.14), Saturated liquid densities calculated from the coresponding equation of Angus ‘ral are pleted for comparison Relative deviations of selected experimental saturated vapor density data from values calculated from Eq. (3.15). Saturated vapor densities caleslated from the coresponding equation of Angus eral? are plated for 1534 1535 1535 1540 ii sat 1343 1544 as 1357 1560 1562 1321 1522 1323 1524 1511 comparton 1598 Relative deviations 1008 p= 100(payPea)/Besp ‘of experimental pp data fom values calculated from Eq (6.1). This figure illustrates the reason for adjusting the dats of Kisii ea! and Michels etal (see See. 4.102) Relative deviations 1003¢,=100(cp exp = Cpe! Of expetinnental Gp dat front specific isobaric heat capacities calculated from Eg. (61). Tis figure illustrates the reason for correcting the data of Ernst etal" and Bender etal” (see Sec. 4.103). Relative deviations 1008p 1004p Pate) Peay of experimental pp data on the crite isotherm from values calculated from Eq. (6.1). Values calculated from the crossover equation of Chen etal” and from refitted equations using the {Cll and Opn (ue Sees 5.1) ave pote for ‘comparison. Representation of representative isochorie heat capacity data inthe critical resion. The oloted curves correspond to values calculated from the crossover equation of Chen eta” and from refed equations using the CHy- and Oy form (ee See. 9.1. ‘While preliminary equations of sate showed 2 iscontinuous plot ofthe thied density derivative ofthe reduced Helmbolts energy, the new equation of sate Eg. (6.1), yields continuous plots forthe third derivatives Representation of representative isochorc heat capacity data inthe critical region. The ploted curves correspond to values calculated from Eq, (6.1, the crossover equation of Chen er al.” ana refiued equation using de CHfou {see Sec. 5.1), Representation of the speed of sound on icone in the evel region ‘The pleted eurere correspond to values caleulated from Eq (6.1), the crossover equation of Chen eta.” and a refitted equation using the CH-form (see Sec. 5.1). Representation of the isochovic heat capacity on isotherms inthe eritial region. The ploted curves coreapond to values calculated from Da (6-1), the erossover equation of Chen eral.” and &refited equation using the CH form (see Sec. 5.0. Representation of experimental isochoric heat capacity data inthe single phase (T>T,) and two phase (TT,) region in a double logarithmic agram. ‘the plotted curves correspond 10 data onthe critical isochore calculated from Ea (6.1), the erossover equation of Chen ea” and a refted equation using the Opsform (00 Sec. 5.0. 1534 1334 1536 1338 1538 1538 1538 1539 1339 4. Phys. Chem. Ret. Data, Vo. 25, No.6, 1996,1612 15, For temperatures betwoon 7, and Te 1 K Ea (6.1) results in an oscillating plot forthe ‘isobaric heat capacity around te ral densi. 16 Relative deviations ofc ta frm vales calculted frm Eq, (6.2. The upper diagram shows data calculated from statistical thermodynamics (se Table 18) and the lower iagram shows data extrapolated fom experimental ress (See Table 13). Vales of & calculated from the comesponding equations of Angus etal? and Ely eal are ploted for comparison 17, Disibution ofthe experimental data used for te establisianent of die residual pat of the sew fundamental equation, Ea. (63), in a pT diagram, 18, Relative deviations 1008)=100 ay.) Dey = Pasp' sp") of the experimental Saturation data of Dusebek eral from values calculated from Bq. (6.1). Values caleulated from the auxiliary equations presented in See, 3, the ‘equation of state of Ely eal andthe auxiliary extn of Angus ar poe fer 100053) exp p's p) of the near ertical experimental saturation data of Duschek et al from values calculated from Eq, (6.1). Values calculate from the auxiliary equations presented in See Lan fm the emnecoueronwation af Chen eral” are pleted for comparison 20. Relative deviations 1008y=1004ap—Yoi) ep (9=W".w',c)) of experimental caloric data at saturation from values calculated from Eq. (6.1) Data calculated fom the wide-ange equations ‘of Ely eral and Angus etal? are ploted for companson. 21, Relative density deviations of very curate pp data at suboriicl temperatures from values ‘sleslated from Eq, (61). Vaioo aleuetod from the wide-range equations of Ely etal and Angus etal are ploted for comparison. 22. Relative pressure deviations of very accurate oT daa in the extended eitical region from ‘alues calculated from Eq, (6.1). Values calculated from the wide-range equations of Ely fal” and Pitzer and Schreiber and from the crossover equation of Chen eral are plated for comparison 29, Relive density Ueviaios UF very secutae py Gata at superertical temperatures from values, caleulated from Eq, (6.1). Values calculated from the wide range aquatione af Ely ofa 8 and [Angus etal ae plod for comparison. 4 Phys. Chem. Re. Data, Vol. 25, No 6, 1896 1539 1540 1542 1546 - 1546 sas 1549 1350 . SPAN AND W. WAGNER 24, Relative density deviations of selscted pe date from values calculated from Eq, (6.1). Values calculate from the wide-range equations of Ely ct al" and Angus etal” areploted for comparison. . 25, Relative density deviations of selected pp data at high temperatures from values calculated from By, (6.1). Values ealetated from the ‘wide-range equations of Ely et at and Angus ‘etal are pled for comparison. 26, Relative density deviations of selected po data at high pressures from values calculated! from Eq, (6.1). Values calculated from the wide-range equations of Ely er al'® and Angus etal? are plotted for comparison; in ths pressure range, these two equations of state are atleast partly extrapolated (see Table 1... 27. Relative deviations of sessed faerie het capecity data from values calculated from Eg, (6.1). Values calculated from the wide-range equations of Ely eral and Angus eal? are plotted for comparison, 28, Representation ofthe iobarc heat capacity on {sobars in the gos region and in states onthe cublimation curve (saturated vapor). Values calculated from the wide-range cqutions of Ely ff aL” and Angus ta? are plate for comparison. 29, Relative deviations of isobaric heat capacity data thigh temperatares from values calculated fom Eq, (61), Values clelied fom the a" are plated for comparison. Relative deviations of seleted isocovie heat capacity data from values calculated from Ee, (6:1). Values calculated from the wide-range equations bf Ely era. and Angus etal are plotted for comparison 21. Represematon OF te tic eat Capac high-density isochores. For each ofthe isochores the ploted pressure range stars at the comespontng vapor pressure. Values calculated from the wide-range equations of Ely eal! and Angus el” are ploted for comparison. Relative deviations of speed of sound data at soperertal temperatures trom values calculated from Fa (6.1). Values calculated from the wide-range equations of Ely eral and of Pitzer and Schreiber gin the ange its vat, rom the crossover equation of Chen ‘eral are ploted for comparison, 33. Relative deviations of speed of sound data at high pressues fom valves cafcolated fom Eq, (6.1). Values caleulated from the wide-range equations of Ely etal and Angus eta! are {ese two equations of state are st least party 3, 1551 1582 1552, 1353 1353 1354 1354 1354 15583. 38. 36. 4h 38. 2%. 40, Symbol ANEW EQUATION OF STATE FOR CARBON DIOXIDE extrapolated (see Table I)... fo 15s5) Relative deviations of experimentally determined Joule—Thomson coefcints from values ‘aleulated from Ea, (6.1) Values calculated ‘hun de wide-range equation of Bly ef ul a ‘Angus tal are plotted for comparison. The data of Vukalovich eral were not used when establishing Ea, (6.1)... Representation of experimentally determined fugacities on isotherms at very high temperatures, and pressures, Values calculated ftom the ‘wide-range equations of Ply erat!" and Angus ral? are ploted for comparison. Representation of experimental data describing the Higoniot ene of earhon dioxide Hugoniot curves calculated from the wide-ange equations of Ely eta and Angus etal? are plotted for comparison... {ne so-called ial curves calculated trom (6.1) and ploted ina pipe, log.) diagram. ‘The Joule~Thomson inversion curve and the Joule inversion curve exceed the temperature range in which Ea, (6.1) is fited to experimental data... ‘Tolerance diagram for densities calculated from (6.1) gion B the uncertainty in pressure seven Tolerance diagram foe speed of sound data calculate from Eq, (6.1). Inthe immediate icinity of the ential point (region Giffcut to estimate an uncertainty in w because of the growing influence of uncertainties in temperature and pressure measurement ‘Tolerance diagram for isobaric heat capacities caleulated from Eq, (6.1). Inthe immediate Vicinity of the critical point (region ) it is ofthe growing influence of uncertainties in ‘temperature and pressure measurement, 1556 1356 . 1557 1357 p98 1558 1558 Nomenclature Description .B.C.D.a,b.d.n.t Adjustable parameters A Specific Helmholtz energy B Second viral coefficient, op Specific isobaric heat capacity c ‘pectic isochoric heat capacity fe Specific heat capacity along the saturated liquid line s Specific Gibbs energy ‘ Specific enthalpy ikl Serial numbers i ‘Maximum numberof the serial numbers i, M Number of data, molar mass > Pressure 1513 R Gas constant 5 Specific entropy Tr ‘Thermodynamic temperature, TTS.90 u Specific internal energy : Spee vole ” Speed of sound xy Independent variables z ‘Any thermodynamic property Zz (Compression fator Greek a,B,7.4,0 Adjustable parameters ap.70 CCuitical exponents a Difference in any quantity saw Functions a Reduced density (= ala @ Partial difereatil, ° Fugacity 6 Dimensionless Helmholtz energy (o=anenyy “ Joule—Thomson coefficient ° Mass density 7 Variance + Inverse reduced temperature (r=1,/7) x ‘Weighted sum of squares Superseripts ° teat gas property t Residual a Saturated liquid state " Saturated vapor state - Denotes a vector Subscripts e A the critical point calle Calculated corr Corrected exp Experimental san Indioce m Denotes the melting pressure s Denotes te vapor pressure sub Denotes the sublimation pressure t At the triple point we Weighting e ‘Along the saturated liquid curve 0 In the reference state on In the initial state of Hugoniot curve 90 Temperatures according to the ITS.90 68 ‘Temperatures according tothe IPTS-68 48 ‘Temperatures according tothe IPTS-48 Physical Constants tor Carbon Dioxide -M Molar mass: M= (44.009 80.001 6) g/mol; see Ref. 1 4 Phys. Chem Ret Data, Vol. 25, No.6, 19961514 Ry Molar gas constant Immo K); see Ref. 2 R Specific gas constant: 0.000 011 6) kM(kg K) T. Caitcal temperature: 7. Sec. 32 Pe Citical pressure: p,=(7.377 30.003 O)MPu; see Sec 32 pe Citcal density: p,=(467.6:0.6) kg/m’; see Sec. 3.2 T, Tiple-point temperature: T,=(216.592+ 0.002) K; see See. 3.1 ‘P< Tniple-point pressure: p,=(0.517 950.000 10) MPa; see Sec. 3.1 Ty Reference temperature: Ty=298.15 K -pa._ Reference presse: y=01 101 495 MPa ij Reference enthalpy inthe ideal gas state at Tp AS=0 kik 58 Reference entropy in the ideal gas slate at Ty, po: sj=0 iilkg K) R=(8314 $100.000 210") 188 9241 304.128 2=0.013)K: wee 1. Introduction 1.1 Background Over the past fifteen years great intrest inthe properties of carbon dioxide has developed. hus interest as evolved from both industrial and scientific applications, From an en- ineering angle, carbon dioxide has proved to be the most commonly used salvent for supercritical fi extraction nd to be an excellent too! for enhanced oil recovery. Carbon dioxide processing and pipelining technologies have become ‘of considerable commercial importance. Furthermore, the sliscussion on the greenhouse effect has focused technical interest on catbon dioxide as the most significant combustion product which effets the atmosphere ‘From a thermodynamie point of view, carbon dioxide wsu- ally serves as the best known reference for a molecule with @ strong quadrupole moment and as a testing fluid for ealibra- ‘ion purposes. However, in sciences related t0 thermodynam- ies, interest is mainly based on the widespread occurrence of carbon dioxide. Geophysical calculations of chemical equilibria, under outer mantle conditions for example, require teliable theamodynamie dat of carbon dionide at vor high pressures and temperatures. Besides this, investigations of thermodynamic properties of carbon dioxide have always been influenced by the loca- tion ofthe critical region. On the one hand, the critical temperature of approximately 304 K allows many'technical processes, for example pipelining processes, to be caried out Therefore, from a technical point of view a sufficiently accurate calculation of thermodynamic properties is more difficult for carbon dioxide than for other substances. On the ‘other hand, the data situation inthe critical region is excep- tionally good, which makes carbon dioxide a reference sub- "Refowmce 2p wandid devin of 21000070 sina 4. Phys. Chem. Ret Data, Vol 25, No.6, 1996 R. SPAN AND W. WAGNER stance for theoretical approaches dealing with the erica r- tion of pure Aids, Almost every physical model for the ‘description of the esta region has been tested for carbon dioxide. 11965, an international research project onthe thermodynamic properties of carbon dioxide was established a the instigation ofthe Iteration Union of Pare and Applied Chemistry (TUPAC). In 1976, Angus ef a! published a ‘monograph which reviewed the experimental data available ‘upto 1973 and presented extensive tables ofthe thermal and calorie properties derived from the selected equation of sate eventiless, knowledge ofthe thermodynamic properties of carbon dioxide remained unsatisfactory. Ths, since 1973 numerous experiments including state-of e-aftexperiments ‘with significanly improved accuracy have bee performed in fonder 1o improve the quality ofthe entire data seta thisd of the data sets available today belongs to this group Tn ation to the increased amount of experinentl data, aniston tines have significantly improved during the last” decade, Sophisicated “mullrpropery” fing procedures** and anew strategy for optimizing the structure fof empirical corelaton eguations* have rested in @ new basis forthe development of an empirical equation of state 1.2 Prior Correlations of Carbon Dioxide Properties and Demands on the New Correlation Since 1940 numerous correlation equations for the hoe rmadynamic properties of carbon dioxide have been devel- ‘oped, bu ony few of them describe the properties within a sufficiently laze range including the gas, liquid, and super rvcal states, Table | summarizes the equations of state for catbon dioxide which have been developed since 1970. After examining the wide-range equations of state availble in 1973, Angus eu discussed three equations in the TUPAC ‘monograph, namely the equations of Bender,” Altunin and Gadetskii and Stein? which form the beginning of Table 1. Finally. Angus etal. decided to use the eauation of Altunin and Gadeiski as a basis forthe IUPAC monograph. At that time, none of the existing wide-range equations of state of fered a reasonable description of the eitical region. Thus, Angus erat’ combined ihe wile-iige equation wil © sealed equation of state developed by Schofield! and a switching function developed by Chapela and Rowlinson.” Although it wos knowin that the evaluation of the combined correlation equations causes numerical problems and yields ‘incorrect results for derived properties in the switching re sion, the equation was generally accepted as a reference for fatbon dioxide. in 1788, Fiver ad Searetbet"* wk up dl TUPAC compilation again and showed that very similar re sults ean be achieved with less numerical expense if special tarme fo the decerition of the ertcal region are added to the equation of Altunin and Gadetski." ‘The only correlations which really improve the esults of ‘Angus et alate the equations developed at the National Insitute of Standards ang teennoiogy by rly"* and Ely‘A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1515 Toa |, Available wideige equations of te for atom done TTenperue——Presure Suture of ‘Number of ef ——Data wd in the Auton Yer range (K) ange MPs) the ogtoe ined at oneaion ‘Ania and Gates 19nL5-1300 0-300 Polyaomal 2 pore, Sein? wr > . Polonia a Pot.peo'o* Siting a wr 4 as Extended BWR! ny potinns Meyer” iT Oe Polyaomia uw Pet ase eeu h Angorer al (UAC) — 1976 220-1100 0-100 Combine sosses porey Hoang el? Is 216-230-810 Extended BWR es bet s'o" By" Ios 216-1023 0-300 Schad Wapser 2 DoT De Pc.ce By erat iw iets O30 Schnitand Wapner™ 2 Petra pc PiuerandSchrcbe’® 1968 -230-1080 100 Extaled polyoma 3 patna Bye” om 216-103 0-316 scab td Sew 2 DoT ps’ pc Poe andStene™ 199M 720-2000 0-10000__—Fratoal form Ey pet pao BS ' Se ifomaton palate Ferns developed ty Eves and Wagnee or he description fhe el regon were abo we, ‘peri some exert at, enya rom th TUPAC tale were asd opt dat ps et al? These equations take into acount almost ll ofthe Published expenmental resus. However, some ofthe most important state-ofthe-at experiments on carbon dioxide were not yet available at that ine. A. deusled comparison" ‘howe thet the pation given in Rafe and 14 cing the form developed by Schmidt and Wagner is superior tothe equation given in Ref, 17 which uses the form developed by Jacobsen and Stewart." “Tests ofthese corelatons have yelded tat all of the ex- ising equation of state, independent oftheir diferent qual iy, show the following limitations: State-of-the-art daw for the pp relation are not represented to within their experimental uncertainty + State-ofthe-at data describing. the liquid-vapor phase ‘ailibrinen are not repreeeatel to within their experenen- fal uncertain. + Within the critical region, the calculation of caloric prop- centies yields unreasonable results. + Unreasonapte benavior can be observed in regions with a oor data situation + Extrapolation to temperatures and pressures outside the range of valcity yields unreasonable results, + The temperature values used do not correspond to the cur- ‘ent International Temperature Scale of 1990 (ITS-90). “Tue eyalou oF Fees aad Stexnes™” ca uialy be come sidered to be an example for an empirical equation of state with reasonable extrapolation behavior; the authors do not lam that this equation improves the description of thermo Aynamic properties in the region where accurate data exist ‘The problems elated to the description of properties within the critical region can essentially be solved by using scaled equations of state: Table 2 shows Selected correlations with such sealing approaches forthe description ofthe critical region of carbon dioxide, However, the relatively small range af validity and the mathematically complex strate Of these equations limit thei use ‘An exception with regard to the range of validity is the empirical equation of Erickson etal This equation uses an Improved torm of the tanstormation procedure, orginally developed by Fox,” to achieve a reasonable but not an as- ‘Tae 2, Slee led eon of sae for cron oxi Tenperare Deny ‘ember of fd fo Your ‘ane ange he eficients Soa , 138 = Sine wale 5 Vient-Misonl 1939 moras 31-48 Simple saiag ‘ Maphy eal i973 36-598 Simple sang 5 Albright eral 1987 2as- enlarge the infuence of ata pont ith espesto he sum of guares and Weighing hc Unally fy equal ne wd va in some cases, bowever differen weighting factors are ised fo compensate Tor eects caused by the stricture ofthe dataset. These effets may be divided into the following groups trina special region there are only afew > 1) or excep- tionally many {f<1 datapoints « Iarentinive ttc wage expen ve an be transformed in a sale, but more eonssien at‘A NEW EQUATION OF STATE FOR CARBON DIOXIDE set by suitable data selotion (fag D. + After correcting systematic deviations, a data set yields results much bette than expected from its original experi- rental uncertainty (fu.> I. + In-a special region, enlarged, but difficult assignable un- certtinties ofthe selected data are expected (fue 1). To achieve as much transparency with regard to the data sot as possible, the tables presenting the selected data (see ‘See, 4) contain additional information on the uncertainties ‘used in the weighting procedure as well as onthe mean value vf the weighting factor, Weighting factors deviating sigaifi- cantly from f=1 are discussed. 3. Phase Equilibria of Carpon Uioxiae ‘An accurate description of phase equilibria by auxiliary equations Is au inpurtaut acta fr Un devehyieat ofa wide-range equation of stat ad is also helpful for users who are only interested in phase equilibria. Therefore, all available experimental information on the tiple point, the eritical point, the melting pressure, the sublimation pressure, the vapor pressure, the densities of saturated liquid and va- or, and on caloric properties on the liquid-vapor phase boundary have teen reviewed, With the execption of the calorie properties, simple corelation equations have been developed for the temperature dependency of these quantities ‘To condense the description ofthe dat situation, the char- acteristic information on the single data sets is summarized in tables for the coresponding property. The datasets have ‘een aivided into tree groups. The assignment considers the critically assessed uncertainty ofthe data ize ofthe data set, and covered temperature range. In addition, attention is paid wo the data situation forthe respective property. Group 1 contain the datasets used forthe development of the corresponding corelation equation. Group 2 contains data sets suitable for comparisons, Compared with group I data, these data dene a eat under one o he tree aspects mensonea above. Group 3 contains very small datasets and data sets With rather high uncertainty. Consideration of these data is not eonconahle on the love af accuracy aspired ta hear New ertheless this means no devaluation of these datasets — the ‘whole ranking is influenced more by the quality in relation to the best available reference data than by an absolute level of. Uncertainty: for other purposes even group $ datasets may be very useful Since the new correlation equations and all temperature values in this article eorespond t the TTS.90 temperature scale. the temperature values ofthe available data, based fon older temperature scales, were converted to ITS-80. The conversion ffom the IPTS-68 temperature scale to 1TS-90. Temperatures. was caried out based on the internationally agreed procedure of Preston-Thomas eal.” explained by Rusty.” The number of digits of the converted values was inrensed by one digit in order to guarantee sumercally con sistent reconversion, but not more than four digits othe right 1519 ‘of the decimal point were used. Data corresponding to the IPTS-48 temperature scale were converted to IPTS-68 ac- ‘cording to the procedure given by Bedford and Kisby.”” For temperatures between 90K and 900K, the temperature scales ITS-27 and IPTS-48 do not deviate from each other and data older than 1927 were not used. The algorithm used for the conversion from IPTS-68 to the ITS 90 temperature scale" causer an additional uncer tainty of 1.5 mK for temperatures below 273.15 K and 1 mK for temperatures above 273.15 K. This additional uncertainty i not considered inthe uncertainties given inthe tables ofthis section, since these uncertainties were mainly used for consistency tests between data of different authors, In this case, the uncertainty in the absolute temperature, fst is iucived Uy te uncstainty ut Une auroras i> less important. The comparison between two very similar temperature values is not influenced by the uncertainty of the conversion if both temperatures are converted with the same procedure. 3.1 Triple Point During the last YO years, tne tnple-pount temperature ot carbon dioxide has been determined by numerous authors but the data situation forthe tiple-point pressure is rather poor. Fortinately, the few messirements sealable are very ‘consistent with each other. Table 4 shows selected data of the tiple point of carbon dioxide. After a comprehensive review of the existing data, we have chosen the following: Ty=(216.592+ 0.003)K, en e= (0.51795 0.00010) MPa @2) Data of the density of the saturated Liquid and the satu rated vapor a the triple point are not available, but the evalu ation of the coresponding correlation equations given in Sees. 86 and 5.7 yields pf (1178 53* 0.18)kgfa, 63 i= (LS 1014 VUUS4)KBIM way 3.2 Critical Point Altogether, data ofthe critical point of earbon dioxide are given in 75 papers. Table 5 shows selected values of the critical temperature, che critical pressure, and the ctitcal den sity. Ihe values Tound for the eniteal density agree welt within the expected uncertainties, but the values forthe ert cal temperature show significant differences, far beyond the ‘uncertainties given by some of the authors. Essentially, the differences in the critical pressures can be explained by the variation ofthe vapor pressure with the assumed critical tem perature. Tithe course ofthis work, no new attempt has been made to determine the erical parameters of carbon dioxide, but the evaluation of Duschek er al® was tested under different fepects. No reason for altering the data became obvious, Thus, we have used 4. Phys. Chem, Ref. Data, Vo. 25, No.6, 1996,1820 R. SPAN AND W. WAGNER “Toa 4, Slt dao te ipl pi feo nde = Yar TORY ATKP pNP) Ap PH) Mow mn Daa 9s aiesig 000s OSS HOmOB Antone sr dress Soon vey toe) less 0001 Hoot a® vw aieses 0002 Stree el” tet east sina leer a toa dieses 0008 Paves an Fe Ise 2igss15, 00 Bot ea ives ess 0001 Desc toe ates 00m 0siss 200001 ae Fivcapaume wee caved w SS0 Up oan excommy 01 AK w aio Gir aed “Fe unctrany ofthe comvenion fom W081 11S (304.1282 0.015)K, (3.5) temperature assumed by ae ‘et al! and Chusius er al. Sete nee (0 yO.) at es pe (7.3773 0,0030)MPa, (3.6) perature values were corrected teeordng ri pen 4676 Ok en ps Tanr-008K es (Te aos! gin. spent pete mune essay nay etna to te IPTSG8 temperate Typ Thaw 008K eo) seale) 3.3 Melting Pressure ‘There ae only two availble sets of measurements describing the meting pressure oF estou dais tn 4B Michels eral measured 25 melting pressures at tempera: tures between 217 K and 266 K, coresponding t pressures hetween 0.9 MPs and 284 MPs. In 1960, Clusus eta jpoblished 21 data, covering the range from 217 K to 222 K, ‘omesponding to 0.5 MPa to 24 MPa ‘Unfortunately, these dala sels ar inconsistent with each ther nd with soon data of dhe tiple point presse. In oth ‘experiments, the thermometers were calibrated a the tile- point of carbon dioxide. Since the values ofthe tple-point ater el conerion 17.90 enprties Se cach tan we srt ine expec cers td were wed esl snc Colon gunn freeing pose 7 (t (Fa) +olZ-1) Pn pe ert ter) a G10) with Te=210.92 K, PiEUD1/9 NAFB, 4) =1939.390, ant ‘a;92055.4593, The equation is constrained to the wiple- point pressure by its funetional form. The representation of both the corrected and uncorrected data is shown in Fi. ‘The uncertainty of Eq. (310) is estimated to. be pulpy 15% fr T= 7225 K and App y= 20.5% for “Tat 5. Skt da oh it eto one ‘Sea Yer Te Pera) 0, i) aagemae on Novae” isn asya22 ng 6 oe fase ‘983 as ‘ Sener and Leet Segen* 1986 an ‘ho ‘980 as Brea fn ui he Conca om noon amie Gren? temo Sakt102 tas Dest topo nian2=o01s 737730008 ae a” "Ftenpermer new convened TT-90 Up w or “ipa beyond he ial pt orl ‘dts gnc ott sven TS tee ity he ene fa TS 48 TS os ee 4: Phys. Chem, Ret. Date, Vl. 25, No.6, 1866ANEW EQUATION OF STATE FOR CARBON DIOXIDE i Z i * 4 é Se a f m0 03a) 350 60 TO Teupessane 77 © chasusetal", © Chui eal co: ay 1G Michels eral wm Michels et a” (corr. data) Fa. Relative deviations of experimen meting presue data rom va ues clue rom th meting psu equation, (310, In ths Hue, ‘ht be corcted und he uncoreced dat re plod ae Se. 33) 205 K85 K and (0.0001 Pa for 7-285 K. respectively 3.5 Vapor Pressure Information on the vapor pressure of carbon dioxide is siven by 36 datasets; the coresponding information is sum: ‘marized in Table 7 (repeatedly published data sets were only ited once). The very accurate data set of Duschek eta. describes the vapor pressure from the triple-point tempera: ture up to the critical temperature. Only this data set was selected t0 develop the new vapor pressure equation. For the data converted to the ITS.90 temperature seal, the opti No.of Temp rng, Source Yeu dea TAR) AT (MK) Aan Group Kuesen and Robson? wa 6 2 2 (Ones aed Weber po 8 3 Siemens wo 20 3 Haig Big is S103 Hevse and Oo!* Ba 18 IShI8s 3 ease sn Ono wo 7 Bs a Gianque an Egan™ 19% 1254-196 sam} Tks an Leng B51 1 tO6cise 3 Ambre BS 16 TBAI98 “mL Bila erat gt asta ' Bryon lS We @ —TO08 2 Beard al we es ' FerunderFassuc end dt Ro 198421 194-249 =10P 4. Phys. Chem. Re. sta, Vol. 25, No.6, 1996,1522 R. SPAN AND W. WAGNER -500 SOF 0) 14170) ee 180) 11190 2200) e027 101s 220) Temperature T/K 1 Ambrose © Bedford eral.” es © Giauque and ‘© Fermander-Fasgnacht and del Rio Y Bitkaat eta.” 2. sikaah eta (cor. dala) 2 Absolute devitions pap Pano ~ Pana) of let expeimenlsbination pes ita from vals cake from the lito pressure eon (121 Ta ie Here Hoh Cte a he ned dats Blt of os pon fo oe ‘agus 7, Summary ofthe dat st forthe vapor pes ofeatoo die Neof Temp. ces. Kosnen and Rotson™ 02 Ts 3 enon” 10 20 3 Jenkin and ye eo ary 1 Bndseman™ ‘wr 3 Meets and Van Dasa m6? 2 Michels 9359 ss0 3 Roshi eo! we 3 Michels? 0 182-76 2 Reamer eal Wl 2mm tk sta 3 Biv an Webs 5509 MeN sm] zag 2 cook ws 9 MD 3 Cock ss SD 3 Schmid and Thon ist 6a 3 Went 5 8a 1 3 esti” Wet 2260, 256, ; {reg and vasson™ wee 3 ade and Jobo" Iss 28 3 alate al” 8 3 iia ra 9 3 esl Senger nd Chen war 2 Fredenshnd and Moog is 3 (Gast e al” a3 7 Davalos era™| 3 ‘ Sead and Wits” 1m 9 3 Kang Bae al" 2S 3 1983 4 a et =I zim ot 1988 3 Eomse 2 1988 =” 3 wor 20 3 ora a as = 2 J. Phys. Chem. Ret. ata, Vol 25, No.6, 1996,‘A NEW EQUATION OF STATE FOR CARBON DIOXIDE 00s 190 ( Peesp-Pasate! / Paese 0.05 = 296 298 ito 302 304 Temperature 7/1 Bierein and Webster" Hola al © Fernandes Faenach ang dol Rio™ © Krts , X Meyergand Van Dusen 4 Levelt Sengers and Chen 0 Bude 1 Michels etal © Duschek eral = = Angus eral? (aux. eq.) 1523 ‘ho. 3. Relative devon of selected epee vap pss fom ves case om he vapor rete eget, (3.5), Vapor rests ‘Ste fromthe eomespnding usin of ANE e ae plated for comparison. Tos 8 Sommary ofthe eside 9 othe Satria est carbon sovece Bein Michels eta Reamer eal” Berk and Webster Vekalove rat? Aisa o Year To No.of Temp. se is Tiki AT (mk) Ape) Group % 7-308 3 3 3 hs 3 Tie dan wo a Hobie oo ae ile 4. Phys. Chem. Ret. Data, Vol. 25, No.6, 1986,1524 R. SPAN AND W. WAGNER 100 Ap” 20 240 260 280 Temperature T/K Holst eral © thay! D Esper! © Dunchck eeu” = == Angus etal” (aux.e4.) ic 4. Relative deviations 100 4p'=100 (yp of selected experimental surat gid des dar from ales caleuted rom E19) Sts gut costes ene fom te Sepang egeanon of Anger a are pos fr sonar, ‘zation procedure yields the same mathematical rorm usea oy DDuschek eta to describe this dataset in the IPTS-68 tem perature scale; only the coefiicients a, have changed. The ‘vapor: pressure equation can he written as Ps\_Te 7 oa wl) -2 13 0(1-7)| an gemtneto in fe eee tion of the data measured by Duschek et al. Considering 3) te expenmenta uncertainty of ese data, tne uncertainty of Eq, (3.13) is estimated to be Ap,= 0.012% for the whole temperature range. ‘The dashed lin in Fig. 3 comesponds to values calculated from the vapor pressure equation of Angus et al after con version o TTS-90, The results of this correlation are remark ably good but, of course, the most accurate data available foday are not represented to withn tne experimentas uncertainty, 3.6 Saturated Liquid Density ‘Table 8 shows information on the 17 datasets ofthe saturated liquid density of carbon dioxide. Again, only the data ‘Taaue 9. Summary ofthe ts et fo the stra vepr dey of cabo oxide “Temp ange Tek) AT (mK) 49°C) Grup No of Source Yer ote wry and rekon = 19278 Mitts ol rr) Reamer cra! SL Coa sso ‘halve af? 6 holon a al wm. Seat wn Reverand Robinos” 1075 Baste Ms Exet"* wes Hale al wars Duss et at™ 108 Abdlagson eral 19 269-296 2e_a08 7 e 220-308 33 3 3 3 aan 3 3 2 2as-304 3 1 3 [ihe dan sen of Be” and Hae al are Geen ealon of te rane mesures 4 Phys. Chem. Ret. Data, Vol 25, No.6, 1986,ANEW EQUATION OF STATE FOR CARBON DIOXIDE 1525 os she a goes a ° . a 3-05 & 28 005 & gs =o 0.05 220 240 260 280 300 ‘Temperature 7/K 4 Hose gral" o Bawet X_ Kholodov eal ‘Angus etal? (aux. 69.) > Boe beet © Abdulagatoy era.” © Duschek eta. 1 Michels eral” 5. Relive devisions of sled experimental saute vp density dal fom values cla rom (3.15) Seuted vag denies cle from he crespoeing eqn of ANS e are plated fe compan. set of Duschek er a is used to develop a simple saturated liquid density equation. Group 2 is restricted to data sets ‘which deliver uncertainties comparable with common uncer. tainies in the single phase region, that means Ap’ =+0.2% ouside the critical region. Unfortunately, this etiterion is only met by the datasets of Haynes, Esper, and Holste etal; all the ether data proved tobe less cut For the whole temperature ange, the simple conelaton a, 3 e(1-F) G14) with T=3011282 K, 9,467.6 gl, a, 1.215108, ay 0162385555, 032731127, 39245142, 1°48 and 14= 1) describes the data of Du- schek ef a within their experimental uncertainty. For this equation, both the coefficients and the exponents differ from the formulation given by Duschek etal, which is valid for temperatures on IPTS-68. The changed functional form of tho correlation reclted in slightly improved results in the critical region. According to the uncertainty of the selected data, the uncertainty of Eq. (3.14) is estimated to be Ap’ S=0015% for T- ferent stations, his section is divided into two subsections. J. Phys, Chem. Rt. Dat, Vo. 25, No. 8, 1886 421 Experental Reauits for the Specie Iebaric Heat ‘cect, ‘Today, calorimetric measurements performed with low apparatses provide accurate data of the specific isobaric heat capacity over wide ranges of temperature and press In the low density region, these resuls are usually mote ac curate than isochoric heat capacity measurements ‘Since state-of the-art data on the speed of sound for car tun dionite ave available only within a vor imited tempers ture ange and ony up to pressures of 09 MPa, the data Ses tiven in Table 13 and especialy the selected datasets shown in Table {4 represent the most important source of informa tion on the ealorc behavior of carbon dioxide. Wile the dataset of Bender et al” provides an accurate description of the low density region, te data of Emst and Hochbera!™ find Brat eal" allow a praise drserition of ealrc prop cies up f0 90 MPa. At least for subcritical pressures, the accuracy of these data sets is improved by suitable correc tions; see See. 49.3‘A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1529 “Trout 12, Summary of sled pdt fo cation done; stale infrmsion is given on he uncer valves estimated bythe abies a those ‘td Wy oules and ed tthe weiehing prose ‘Uncrsint exiated by te athe Wy he hors Sauce Mean fi ‘owes source" Mesm ty ews iste 3 NRE nd Mice 400 Ap=l00n Pa do=028 Law a Mier Se 08% S21 Pat mK, 8p=0.028, ao 100 Ap=OMN%, Ap=01% Exe! 4s ‘ap=003-010% Wenort*= ° IK, Sp=132 Pa, AprO028 Lop AT #10 mK. 39-0015, & on ‘AK. 8p=s00 Pa dp=000% Holset al"™ 80 AP=I0mK, dp=00158, Vualoich * ‘p20 18-0358 080 AT=I0 mK. Ap O08, dpm 0.05% nein 107 ‘encase amc 2s NRE. Velloich i NRE. 08 ATS aK, Ap=O18, Apa snd rani’ 109 ap=028 Jere 7, NRE okalovie at’ 32 Kee 1 AT=S mk, Ap=O05R, ap=005% 100 padre Magee 5) AT=30mK. Sp=001%, Sp=01% Voli er al™ 36 NRE snd Ey 016 T=B0aK.dp-001%, ap=O1% ; se ap=0% Byer at” 2 100 AT=O2K.Ap=? MPa Sp=O4% Hoik™* 2 alos 10S AT=80 mK, p=0088, dp 135 snd Toymary™ 225 Duschck a 382 AT =IiMK, Sp =OMNKR Ap —DOISS 96s Duss erat a7 ‘apeois-02ia" orn et t™ 9 22s 40 Sete et 258 Kin erat" 66 Go era 0 ‘p-605-001% 100 225 as a ° genera 364 tin erat 2 Bachhive® “39 AP=LSiaK. Sp=0000R Ap=0015% soo Apd0s, bp-01% 10 ‘p=016-0081% Popo m NRE: Fenghowre al! a0 Spm0016-0081 raSwpoe™ 1.0 mK, p05, do 0 o=005-0108 olaoicher at? sg isped.o-01% teak erat" "6 ‘ap=0108 100 AT=15 mK, 4p 00088, 100 AT6mK, Ap-O0.006, Ap=02-0045 Sp=O08-018% AT=6 mK gp =0 06%, ip =002-D04% stmoroy Ey ‘49=025-15% Nowak erat! 21" ST=1 Sk p= 00008, dp=0015% nt Shmaovich"* ak ATO. KpeO.tR Apr 1.0% too AT=1s Ap=000se, Ap-0Ise {RE No ronal eimaron ge by he ator “Consineney is gen instead of ue. Caceres gen fr be couesponding Sarat Lil nd saat age densities “The data sets of Rivkin and Gukov'”" describe the supercritical region af carbon dioxide. Since empirical equae tions of state may produce misleading results reganding ea- Toric properties within this region, these data sets were considered to be of great interest for the development of the new fundameetsl equation. Unfortunately, the data proved to be inconsistent wth each other and with state-of-the-art ppT data, Since the data given in Ref. 174 were deduced from ‘measurements ofa mixture with high carbon dioxide content, this dataset was classified in group 3. The dataset given in Ref. 171 was used only with a reduced weighting factor. 4422 Results forthe Specie lzobaric Het Capacty nthe ‘dea-Gas State According to Fa, (24). knowledge of the specifi isobaric heat capacity in the idel-gas state forms the basis for the 4. Phys. Chem. Ref. Data, Vol. 25, No.6 19961530 R. SPAN AND W. WAGNER Taos (8 Sar of eds es vale rhe perf babe spciy fearon doe see Yer tun iain’ Goud meic> ioe ga Schock wr Koppel and Sich? Io ‘alan oa It Wisloih sd Gue® 186 Viton a at sine aon” ‘ot ‘unio and Kuso"? 18635 ‘Ani and Kummer" st ‘ns sod Kupmeov® 19723) Sige ‘as ‘ewer ea" mi Pret Harte = 9s rm eal os. ei a ™* ow Temp. pe, Rese mgs 70 OP 70 0-30 ao an 03 ia mm 10-60 9-60 aici 03.500 sist ms "Th ape ao oti ergs vas or he ea bw tapos fern de nl Dac case om mete he pean. ‘Stesuements fs mite wits gh cron Soe Cm he Scone ie wae eng ‘rom be mur eprint ye cab a Aescition ofthe ideals pa of the Helmholtz energy, A%(g.T. Ress for & obtained by the extrapolation of themes 2 esse (Tae 3) ae Rees urate enough fortis pplication ot do they cover a sa- iemly wide range of temperature. Therefore oe ap- Droaches which describe the eslore behavior of carbon ‘fone in the ie gas state were reviewed Infomation onthe fundamental fequenis ofthe carbon Aixide molecule en be found in various compilations bt Tha. Summary of lata df te si ari est py eb Soe; enema pen on he vce as si te stad core sd ‘Urseainy ates vaca ees ‘mae fino ago cme acne ian SS) areivnt* paints -28 Siu Gn Arai apcaise: aca ‘i areino'apcoe sonia 192 aremnmk, dpeot,8ey002-09% “Cec at wt athe i Ses 410. 4L Phy. hem, Ret, Daa, Vo, 25, Ho 6,198 ‘only few papers contin reliable data onc, where comections to the simple rigid rotator, harmonic osilator model were taken into account in order fo achieve high accuracy. ‘Table 1S summarizes these dota ses, of which he data set of ‘Chao! is the most recent one. Chao considers fist order conectons 10 te Tig FORNOF, RaMMOME-oseAKOY Mode, Which were developed by Pennington and Kobe! he esti mates that the uncertainty of is results is less than 4.3 Specific sochorie Heat Capacity Seven data sets are available fr the isochoric heat capacity of earbon dioxide. The information on these data ses is summarized in Table 16. More detied information on the ‘aa 1S, Data tte cari at aac nh estate of ton die ate yeasts Souce Yor Temp. (6) Garvic 99 wo-joon, Gun roo ‘so-sa Cha 1386 wet 500ANEW EQUATION OF STATE FOR CARBON DIOXIDE 1531 ‘Tus 16, Surry of the da Sts vale forte speci sochorc hat apy of carbon dixie ‘Noof Temp. range, Densy rane, Source You den TUK) Pile) Grae Mics an Sand" bse) a3 mus ‘Aidan era im 22a 50-831 ‘Anihanoe snd Pokhonid™ = Tt 7" TBs 512-505, wat fe Baas ‘Magee and Ey"* iiss Arslgao eat eB es ae. S10 ‘Abela eal Ist ss? 308357 ‘0-510 Hi “Adalat > ot 2a 2800387 wos 19 ‘Sralution of be da b deed by water empertare signe "Sone of te dis ar ine two-ghte regan ‘Praletd vuelve provided by Senger™ 97 mexanements deeb sates within the twophase “Tse data ar elected fom the dts given a Abalagato eal “132 dt ae inthe smote repo: BS of the OE dts the sige pase region a ley own fom Abul al selected data is given in Table 17, For carbon dioxide, measurements of the isochoric heat capacity ae of great impor tance inthe two regions discussed below. The dataset of Magee and Ely" yields the only compre- tensive description of calorie properties within the high density region. At liquid densities, this data set is limited to pressures above the critical pressure, leaving @ gap between the available caloric data in the homogeneous region and on the saturated liquid curve (see Sec. 72.2). At densities below 600 kg/m these data can only be represented with systematic deviations clearly outside the uncertainty estimated by the authors. On the other han, inthis region several accurate equations of state?” agra with each other and with the ‘new equation of state within about 2% for the isochoric heat capacity, and data of the isobaric heat capacity are met “Tam 17, Summary fected di forthe spi crs est cacy of eatoa done: dealt ifomaton pen on th uncer values ‘ined by the abies and tne exited by ous and en the ‘wegmang procure ‘reer exited Source "Mean fi ‘yoann ‘anor it ted Pighonii™ 0) Binarae i 016 Magee ang E50 Se =t5-28 Alerter ef” 238 nas Abaulpatowerot™ 8 Andere 10 the pelonscoen nse ofthe urea within less than 0.55 bythe new equation of state. Based on these faci, we concluded that deviations up to 8% in the ‘Sochore heal apaciy were probably due to shortcomings in the data set, Thus, the weighting factors were stongly 1e- diced forthe low density measuremen'. ‘Within the extended critical region, the date sete of ‘Edwards™ and of Abdulagatov er al.*°*5 had great influence on the development of the new equation of sat, (Ed- ‘wards's thesis! only contains graphical illustrations of the results. The data used here were provided by Sengers.'*) ‘The reduced weighting factors given in Table 17 were chosen because of he large number of data poins within a smal tnd very sensitive region, Thee of thece data eat with ‘would have resulted in an veremphass ofthe ertcal region; details are given in Sec. 5 "The recent data of Abdulagatov et al were first presented in the Proceedings ofthe 11th Symposium on Ther- ‘mophysical Properties in Boulder in 1991. When the corresponding. paper™™ was published three years tater, i lntine only 00 date pint selected foun the 291 date points ven inthe proceedings. Tn the ame yes, another paper was publised which contains the 88 points published before, 10 additonal points on one isochore in the homogeneous phase, and 132 addtional poins inthe 60 Toots 18, Summary of he dats ses avble for he speed of sud of carton die Temp. Mesure No.of range. range source Year daa THK) piMPe) Group Novikov and Tein!® 1662 236 288-373 30-100 | Pioeskaya and Bilevci™ 1973 196. 298473 SDO4SD0 Leomian™ 199950 2an-H0 0409 Srooted ae 4 Phys. Chem, Ret, Oats, Vol. 25, No. 6, 19961532 “Tame 19, Summary of selected dat forte sped of sou of carton te autos and those esa by ouslvs and wed a the welghng ne by te author No.of dts ‘ner estimated Soae Mean f, by ouneher Nekor ae NRE andTrein"® 77 AT AO K.Ap=018, Aw=05% Pruestaya 1a NRE? tnd Bileik™ 225, 6 "NRE: No vessonbleemaon given By the atbor phase region. The uncertainty of the data of Abdulagatov tal. was estimated to be at least as big asthe scatter visible inthe original data set.” ‘The papers of Lipa et al,'*? which are often cited in literature on carbon dioxide, do not contain numerical re- ult. Since tho data of Edwards cover the same region, ‘were measured with the same equipment, and ar les ilu. enced by impurities, the data of Lipa eral, were not considered in this work. 4.4 Speed of Sound ‘Three of the four datasets available for the speed of sound ‘of carbon dioxide were used forthe development ofthe new ‘equation of state. Table 18 contains the available data sets and Table 19 gives addtional information on the selected data. The data sets of Novikov and Trelia™ and of Pitaev- skaya and Bilevich!” provide important information on the ‘extended critical region andthe high pressure region, respee- tively. Though the quality of the data published by Lemming™ is superior tothe other data sets, these data were used only with reduced weighting factors. Inthe gas region, the residual part ofthe speed of sound is less than 2% ofthe total speed of sound at pressures below 1 MPa. Since the uncertainty of measurements is related to the total value of the speed of sound and not only to the residual part, the ‘eonuibuti UF diese dau fo the development Uf at empl cal comelation describing the residual fuid behavior is very limited. ‘Tas 2. Summary of he dat ses avatble for eny dferenes of Temp Pres Neat singe, rags Searce Yer dua TAK) piMPa) Group Keppel and Sou!” 9002 291-892 72-833 Volaiovih até Maslov™* 54 St 24-523 25-98 2 Volaiovch and Maelo 196668 STTTE 25-982 J. Phys. Chem. Ret. Data, Vol 25, No.6, 1996 R. SPAN AND W. WAGNER, ‘Tanur2 Summary ofthe da se for difereces of he nl ener of| No.of Temp. rags, Desity range, Yeu aa) p gi) Dams «19-870 21-316 6 Source ee ea Biche 196847 "Some of he mesure temperate intra ply och i te two pase sin Besides the data prosented in Table 18, five papers™5- are available which deal with the speed of sound in the im- ‘mediate vicinity ofthe critical point. None of these papers, \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 ‘connected with experimental work in the eritcal region were twat edbquatly wnalered at dit ie 45 Enthalpy ‘The literature sources which deal with enthalpy measure ‘ments are summarized in Table 20, The data of Vukalovich and Masalov*"'2 and of Mller er al were considered in this work, but only the data of Moller era. were used with the uncertainties given by the authors (10 data selected, mean value of (29278, Ak=0.7% or MN=0.6 KUke. whichever Is greater). These data provide imporant informa: tion at high densities where the data situation for calorie Properties is poor. The data of Vukslovich and used to ft the quality of the news egy tion with regard to caloric properties at high temperatures 4.6 Internal Energy ‘Table 21 lists the general information on the two data sets ‘which are available for differences of intemal energy. The data measured on the critical isochore by Bache” were not used since the temperature displacement of the (34/37), ‘maximum observed by Baehr could not be explained. The 150 eslacted data of Kiger? which do-not reach into the ‘vvo-phase region, were used with estimated uncertainties of AT=40 mK, Ap=0.2%, Mu=2%-4%, and a mean weighting factor of f2,0.88. The uncertainties given by the author (A7=10 mK, Ap=0003%, Au=1.4%-34) are to0 small to explain the seater of the daa 47 Joule-Thomson Coetticient Since data of the Joule~Thomson coefficient can only be used in the nonlinear fiting procedure and not inthe linear algorithms of the optimization procedure, their influence on the development of an empirical fundamental equation is fairly small. The data of Bender et a.” are the only ones which were included in the data set used for the nonlinear fitANEW EQUATION OF STATE FOR CARBON DIOXIDE 1533 “Tame 2, Sumy ofthe dt sets nal forthe Joue-Thomn coat of carbon xi No.of Temp.rangs, Presse ange Source Yeu da TK) POMP) Group Roetack eal 2st ‘os-s73 onan 3 de Grooeand Mices"* 1948922983 01-2065 3 ‘stove aL? bm 28.388 2 ‘Alain and Garces we 923-300 2s Bendre a We 35 aaa t (Caen a> (958 380-800 3 ‘Feae- Thomo coficnns cased from mens po a. “Tetra Josie Thoms coe, 5 (4 Gat were seleved wide AT—10 sulk, Ay—0.01%, 4y=0.8%, and f2,=0.36). The data of Vukalovich et al® proved to be a sensitive test forthe consistent description of "he gae eoginn Tabla 99 gives a curuny ofthe data se deal ‘ng with the Joule-Thormson coefMicient 4.8 Virial Cooffisionte ‘The literature on carbon dioxide contains many papers in which information on the second and third virial coefficient Is glven, Table 23 summarizes dhe eoespouding sources. “Tasue 23. Summary of he hase valle rhe sec a hie i ‘fen fearon dase, Foeaseas expined in fete, a were signet 9 Gop | Ne of ne Temp. ge, Source Yee ae Fa Group ‘chasse ree mery Sehter™ on We 203-203 Cotte and Ham” ea Pte oa 2a ee onl He 50-30 9 Misia an Pos os Bucher and Dason™ iis 2a ut and Red” Ws 28-510 ‘Yolk apd Maslov ™ wie eer Dasson eal? oe ate Ko and Dae! in E Sas eal HMB “Tineshenko eat?” ever Yotaloweh or a ono 3-38 Vakalvch er a> MWe 238-308 Waxman ea Gra Bender et a aes e368 (nga a be ascals Holt wie 2r-ass Mall ea ye aD Hownkis™ a eas Me Ely ea as nas Desc er a 1 moo Recently, Span*® pointed out that it wae not very uceful to inclde experimental second snd hid viral coetents into the daa set wed forthe development of wide-range equa sion, Most of the data seis descend from ppT measurements stich have been evaluated m oder fo determine vil coe ficients. Thos, the use ofthe orginal measurements yields much beter acess othe desired experimental information. Funhermors, fing an equation of cute we vial eeffcome is only useful ifthe terms ofthe equation coresponding (0 the viral coefficient are independent of eachother, 8s he casein a simple vr expansion However. fan equation of state contsins exponential fonctions, this condition is no Jonger met. Ths, in this atl, the availabe valves fr vir coefciens were only used for comparison; none of the data at was eng C0 g0Up 1 "At tempersturs below 720 K, however, the whole conti bution of the third virial coefficient [p/(pRT) =... +Cp*+...] is smaller than the uncertainty of the ‘most recent ppT data'™ throughout the gas region. Therefore, flow temperatres a pysialy unreaonthle representation Othe third viral coefficient ealelaed from an equation of Sate may occur if the easton wan Sted only tp data Since reliable values of the third viral cocfcen cannot be established by an evaluation of expenmenal po data in his temperature range. 13 valves of the third vial cosfcen were caletlted from a simple polynomial equation which Assrbes all the selected data of the different thermody. namie properties inthe gas region within ther experimental tnceatny ang yells reese plo oft ia coefficient at low temperatures. These “aril” data of the thn! viral coofcen ere then used daring the devel pment of he new eqation af ae 4.9 Liquid—-Vapor Equi Dring the procedure of optimizing the structure of the ‘new equation of state, the liquid—vapor equilibrium was used in a lincatized way.*© The data set used for this purpose consists of values ofp, (7) p'(), and p"(T) at 205 tempera tures which were calculated from Eqs. (3.13) 0 (3.15). These data cover the whole liguid-vapor phase boundary with tem perature intervals which decrease when approaching. the ‘4. Phys. Chem. Ret, Data, Vol. 28, No.6, 1996,1534 That 24 Suomary of sloved dita decrbing he ligt-vepor pie ‘ny ves emt by th auth and hoses by euseves ad ‘ed in the weighting procedure 1 he store No of its Uncen einated Source Progeny Mean i, By oes Nevkor nd Tein NRE 10) AT = 10K Bw" = 05% Peceu and Van Dat" w! 8 et 123 ar=atk.aw'=05% Magee ma By!" cy NRE" 208 romk ae usc ea" an) 100 usc ) Duschek a* ph 2 AT=3mK ap" = 005% 100 _aT=3mK Ap" = 005% on gen by he aor Pinte Sal da set ante vac were Ue Se Se “Only dna st 7-295 K were conse: Se. 38 critical temperature. Additionally, the group 1 caloric data already presented in Table 10 were used to fit the new equation of sate, ‘The final equation was nonlinearly fited directly to the phase equilibrium data of Duschek et al® and othe caloric data, Table 24 gives detailed information on the experimental caloric and thermal data used for the description of the Jiquidvapor equilbsium. 4.10 Adjustment of Data Inorder to achieve a final dataset which i as consistent as possible, some of the Selected data Rad "0 De adjused. As a result, three groups of data can be distinguished which were ccorected for different reasons, These three groups are ex- 430; Adjustment of DataSets Describing the Crteal Region For the desciption of the thermedynamis enface inthe immediate vicinity of the critical point, the difference between the measured temperature and the critical temperature is more important than the absolute temperature, and this temperature difference is probably also less intuenced by systematic deviations or by impurities ofthe sample. Ifthe corresponding critical temperature i given, the absolute temperature enn be corrected by the difference betwose. thi value and the value used in this work [ef. Eq. (35)) This technique was used for two important sets of caloric data: ay Ty=Tyo-44mK. (42) ‘Wentoet did not give any information onthe critical temperature corresponding to his pp data, bo a similar correc Novikov and ‘Treli'™ 4 Phys. Chem. Re, Data, Vol. 25, No, 1096 R. SPAN AND W. WAGNER 29 K-23 1004p 7 so a0 50 100 Pressure p/MPa © Duschek eq" a33K - 240%) © igen eat uo 325%) © Kirill et al" (233K - 243K) © Michels er al" (323K) Fi, 6 Reatve devions 100 39100 (ogi expeien ‘pp dat vals cls rom Eg (6). Ths Age snes te fenton fr asing the data of Kline ™ and Mh a a See 4102) tion can be established based on the pressure onthe critical ‘isochore. In reasonable accordance with eatlier suggestions," we used Wentor; Ty=Tye-27 mK. 43) 4.102 Adjustment of ppT Data Reasonable adjustments can be applied to pp measurements ifsyetematic deviations ooour in a region where a data set and a st of reference data overlap. In this way, accurate information on the ppT relation can be obtained up to pres sures of approximately 100 MPa, whereas, the two-sinker data of Dusehek fal and Gilgen eta are limited 9 MPa and 13 MPa, respectively and the single-sinker data of Brachthiusee!™ and Klimeck eral! are limited 10 30 MPa. ‘Such simple corrections were used forthe data sets of the following: pny 09995, an) ‘or T 10 “oo Pressure p/ MPa 2 Punserut!™ 008) Bender seat ™ 63K) 0.7, Relative deviations 100 8¢y 100 (Een fe ‘etl edit fom specie fede Bet cpus cited frm Ea. (6)" This fre lg the rensn o carian the Ga of Est eal gd Benker et al ee Soe 4105,‘A NEW EQUATION OF STATE FOR CARBON DIOXIDE “Tan 25, Teper dependent conection of sabre heat cape data Temperature, foe r00, 7) cs Beier eral 233 090% 283 025% m3 40138 4363 +0315 3 yous 3 +0.10% rst and Hochberg 203 +0368 ter al"™ 363 20.00% 23 037% Michels etal! Lal: 10.999 5, as) = pia0:999 3. (46) Figure 6 shows an example forthe justification ofthese adjustments by combining two very different isotherms in a single deviation plot. The 99 measurements published by Kinllin etal. only in Ref. 138 cannot be adjusted according to Eg. (44). The corrected data of Michels er al were used only at plessulcs above 18 MPa, In regions where the temperature and. presse dependence of the density is strong, the data adjusted according to Eq, (4.5) also yield _nsatisfactory results. s During the last 20 years, diferent authors®=!2*27 have suggested comections for the temperature scale used by Michels etal? and Michels and Michels." Possible cor rections wete woted in his wurk, but uo teasonable temper ture shift between the ITS-27 temperature scale and the temperature scale used atthe Van der Waals laboratory at that time could he estalished, If the ssstematic deviation of these data is de to errors inthe temperature scale, different scales have tobe assumed forthe measurements published in diferent papers of Michels. Since the data situation in the fas ana extenaea erica region nas improvea signincanty, it was decided not to use Michels’ data within these regions ‘Tam 26, Examples for pve laws desing termodyamie 4102 Correction of tsbaric Heat Capacities Since the low pressure limit of the isobaric heat capacity, «is known very well for carbon dioxide (see Sec. 6.1), \emperatute depeudent enors of measured isobaric beat cae paciies can be determined easly. Figure 7 shows systematic deviations of data measured by Bender etal." and by Ernst etal Again, to differen isotherms are combined in Single deviation plot. A systematic eror of the new equation for the residual part of the Helmholtz energy, Eq. (6.5), ‘would result in deviations which increase with pressure since te residual contibutlon 10 the isobaric heat capacity in- To compensate for these temperature-dependent devia- finns, the ata cots nf Remfor eral!” Fenct and Hochberg.!” and Emst etal!” were corrected according to the values given in Table 25, 5. Description of Thermodynamic Properties in the Critical Region 35208 Its well known®®* that thermodynamic properties ean be described by socalled “power laws” along certain paths throughout the critical region of a pure fluid. This kind of description, which was originally introduced in 1896 by Verschafft22” as an empiseal alent, has been supported by recent theoretical results. In particular, the renormaiza- tion group approach introduced by Wilson” extended knowledge on the behavior of pure fluids inthe critical e- ion and resulted in “universal values for the critical ex: ponents. These values are defined as power-law exponents in the limit of vanishing distance tothe ertical point. Table 26 slows some of dhe most important power laws and gives different values for the coreesponding critical exponents, Which were established by evaluation ofthe normalization sronn theory hy expansion of a classical equation with x sovcalled three-point contact at the critical point, and by ex: pansion of a classical equation with a so-called five-point ‘contact atthe eitial point. None ofthe classical equations is, abet reproauce ine Vales preaite by the enormalzation sr0up theory: opis long conan ps troughou the rie ein ‘Valu deermioed by evhaton of rica Property Descited pa __eapunent “RO than? _pomeg” —_—_Spomege ‘Deets auton ‘ose bounday 2 ine ry Isothermal compres ci sochre y haies0002 1 Isochore heat capeity rt isochore @ 8.110203 o "coring we Senger and Levelt Senge *Sishan equine conte ih ial pat by he enon 3p Stnadtion othe condor given in ont 5p), = 0 ab plop ~ he Pep, 8. ‘uabere i prp'yy > 0. 4. Phys. Chem. Ret. Data, Vol. 25, No.6, 19961536 a sos. K. a E 3 : 0 pe0ensae———————-esaesssiseo-—] b 0005, 80 60 480) 30 Density p/ (kg/m’) © sump" = ~—~ Chen eral” (CHetype equation Ove eaton| Fo 8 Relative deviations 100 87100 (Pay ~ Pa! Pa of expe: tl pp dna on he real ater fo vs cua rn a, 61 ‘etd equston ain the CH, and Orform e Ss 31 apt r 5.1 Limitations of Analytical Equations of State Usually it is concluded that analytic equations of state aunt epnesei de propetdes Ut pure Mui wid weer cal region because they do not yield comet critical exponents. For most ofthe properties considered inthis acl, this conclusion is incoret if state-of-the-art equations are consideved. In this Seton, dhe results obuined within the critical re- son from two wide-range equations are compare with ex- erimemta fess and With values which Were calculated from a nonanalytic equation especially designed forthe description ofthe extended exteal region. For this purpose, we choke the erosover equation of Chen 41 al? The eri! parameters of the crossover equation Were changed to the ‘ales used in tis work because otherwise the comparison of equations with diferent ertcal parameters would produce rmsleading esuls sn the smmedite vit of the enti point To give an example, which is typical for a modem wide-range equation, we fted the equation published by “Schist and Wagner! for oxygen tothe data ct wed i thie \work: this equation is refered to as Orsype equation. The equations of Ely! and Ely e al use the same functional form but these equations are constrained to different exical parameters. To iastrate the limit of an analytic equation of state. we refed the formulation published by Seamann and Wagner® for methane whichis refered to as a CHytype equation. Aa fara concerned. ths equation is probably the most eficient ana: Istc equation avaiable today Figue 8 shows the relative deviation between pressures calculated fiom the ew equation of sate for carbon dioxide (9. (6.1), fom the refed CH, and Ortype equations, and fom the rossover equation of Chen e al.” compared ‘withthe very consent data measured by Staub! dvecy (on the critical isotherm of carbon dioxide. (None of the ‘wide-range equations was fied to the data of Straub these data only served as a consisteney check for the etal re sone. See 41.) Inthe resolution chosen in Fig. 8, ony the 4. Phys. Chem. Ref. Dats, Vo. 25, No.8, 1996 R. SPAN AND W. WAGNER ‘ * === Chen era — optpeequaion 5 Jme=_Clcyp eqn a 1 0 Edward a 1B Abdulaguoy era” < I 5 i = 7 > Seal 2 \ 50030238306 —<308 310 ‘Temperature T/K a. 9. Repetto of reesetsive Sacorc heat epi dt in he tcl region. The pote curvescesgond values cult fo he hig and Oy fom ee S51 ype equation snows me 00 step course oF me ena isotherm which sto he expected from an analytic equation of sate, The analyte CH-ype equation andthe new equ tion of state yield almost identical resale and represent the data as aocurately asthe erossover equation, even though they do not resol inthe imi for the comesponting cial exponent & whichis predicted by the renomliation group tear ‘long the etal isotherm, pp data can be very aceo- rately dese with wide-range equation because the cor responding power law desis presi difrences which Canish wen approaching the ental point (cf, Table 26) “Thos, ilferet values for the critical exponent 8, which is dein 2s limit pn, hardly fet the representation ofthe pp surface, Most of the properties considered i hs cle show asimiar behavior when approaching the erical eit owevar, there ae propeniae which baka plesly ifferent way: the specific isocori heat capaci and the speed of sound, ve, The evaluation of analy aston yields aerial exponent a=0, which ress ina ft value ofc, a he cial pont, whereas the normal ination group theory petits a-=0.10, resting in slow divergence ofthe specif sacri heat eapacity the ert sal point Figure 9 shows measured specific isochori eat capes ‘on the critical isochore of carbon dione and the come sponding values calculated from the O>-type equation, the CHsype equation, and the crossover equation, When 3p proaching the erica temperature, ony the crossover equa tion is able to follow the steep course of te data. The {liege equation fis within a interval of appronimately “105K sound the cra temperature and the ORE qution fails within an interval of approximately =2 K Similar revsits can be obtained forthe spect of sound since it related othe epoca vale of he nochors heat,ANEW EQUATION OF STATE FOR CARBON DIOXIDE capacity. From a theoretical point of view, the speed of sound is expected to vanish at the critical point, whereas analytic equations yield only a fiite minimum. Again, the temperature interval, where the analytic equations fa tends over approximately 0.3 K und +2 X, respectively, around the critical temperature. 5.2 Use of Nonanalytic Terms as an Integral Component in an Empirical Wide-Range Equation of State ‘The performance of a sophisticated analytic equation of state, sch aa dhe Clg type equation, i completely sufficiat for any technical application within the critical region. How- ever, because of the scientific importance of the eriical e- szion of carbon dioxide, an improved description of ealoric properties was regarded as desirable atleast as long as the ‘numerical expense for the evaluation of the resulting correlation remains justifiable. Therefore, we rejected models rls wimplug a Hocative proved for the elation between the physical variables 7 and p and the mathematical vai- ables used, like switching" and tansformation* approaches In the context where the fundamental equation presented in this anicle is clearly empirical, an asymptotic behavior corresponding to the predictions of the renormalization ‘pup ieory was consideied w be of minor importance, mixing up theoretical and empirical approaches may even produce misleading results. Therefore, the attempt was made to extend the qualitatively correct betavior of an empirical ‘wide-range equation to the immediate vicinity ofthe critical point by introducing special nonanalytic terms. The development of such formulations started with an ex- ‘ainstion of the relations between die reduced HelmbolLz ‘energy and caloric properties. The specific isobaric heat eapacity can be expressed as (a7, &p o cat ya LF S85= F765)? RAL Bt TET I Gg OD Fe where R corresponds to the specific gas constant, to the ‘deal (Superscript o} and residual (Superscript) part of the reduced Helmholtz energy. + tothe inverse reduced temperature, and 4 t0 the reduced density. The quantities 7 and 3 used as subserips indicate the corresponding derivative of 1b, see the foutunne of Table 3. Sine (@p/apye! grows much faster when approaching the critical point than ¢., in Eq. (5.1) the specific isobaric heat capacity is dominated by the fraction, which is closely related to the representation of pT data, Thus. an equation which yields an accurate de- 1837 scription ofthe ppT surface within the erical region should also yield reliable values of the specific isobaric heat capacity. ‘The situation is different for the isochoric specific heat capacity which is given by PrP GA he) (52) Ibe second derivative of theresa pr ofthe Helmholtz energy with respect 10 7 is fit a the crtal point, the Value ofthe specific isochoric heat capacity i also fit Only an equation witha nonanalyic behavior in can reproduce the expected divergence in cy At the sume time, Such a fomlaion would result in vanishing values ofthe Speed of sound since w coresponds (ae zh w ce apap OF 805 rb) Br 142604 bees) Ty oe 53) i, [At the critical point, the expression (p/p) becomes zero and (3p/4M), is finite value, Thus, if c, becomes infinite, the speed of sound becomes zero Consequently, a formulation has been developed which can be included into an empirical wide-range equation of state as a regular contribution to the usual sum of terms and hich yields the intended nonanalytic behavior of ¢,. Such 2 formulation has 10 Full Wee aduiional vondiions + The values resulting for 6, have to be finite everywhere except atthe critical point. + Singular behavior of the other second derivatives and al 0s+s, (55) and 1 a1 b) +2 Equations (5.5) and (5.6) result from the condition that singular behavior has to be avoided everywhere except for Gerivatives of at least second degree with respect to temperature atthe critical point. Unpublished preliminary equations id not fulfill these conditions and resulted in a discontina- tous plot of i ied deity Unsvative of Ma raved Hele haltz energy. (#"6136"),, atthe critical sochare. Figure 10 shows an example for this possible misbehavior and shows that the final equation, Ea (6.1), results in a continuous plot ‘ofthe crucial third derivatives ry 4. Phys. Chem, Ret. Data, Vol. 25, No.6, 1906 © Abdulagutoy et a.” 6,1 4ikg K)) soo Sr —=308—=306 «30810 Temperate TK oI Retestutin of eeseztive ocho acuity dat the ‘ital region. The plot eves comespond to values clued rom E, Ter, te erosover easton of Chen a. and ett ecuton ig the Choon (ee Se. 8.1). The smallest exponent b, occuring in the equation of state is related to the critical exponent a, which deseribes the divergence of the specific isochoric heat capacity, by the expression (5.7) basal — (6.1) ~=-Gitieeguioe (aT aceeal vs SQ. Fz05K df s e \ g ee Ss we, 3 “Y a | & ) ns j i Bt too} i to. aa 7 ae oa Density p/ (kgm!) Fa. 12 Reptseitin ofthe sped of sou om ethers in ect ‘exon The plod cares comespond to vl alae frm Eq (6) fievemwmer apatan of Chemo a apd # seed equation wine (Cir oe Ste 5.‘A NEW EQUATION OF STATE FOR CARBON DIOXIDE Ti i s i a4 { z i 3 { Tet, : . Lg & boo cy 300 %o Dessity p/ (het?) — hon = CHetpe equation = Chen etal Fo. 15, Reretention of the score et cpecly on Sates nthe fic region The pated cues eoespod fo vahes cau oak (61), the cosover equston of Chen ta.” and efi equsion tig the CH form ne So. 5.1) However, in combination withthe sum ofall terms of the nts equation of state, the azymptotially expected loading value of b,=0.945 yielded unsatisfactory results. This dis- crepancy is discussed later in this setion. The final equation of state for carbon dioxide, which is preseoted in detail in Sec, 6, has been developed by the use of nonanalytic terms corresponding to Eq, (5.4). The proce dure optimizing the structure of the equation of state was restricted to a maximum of four nonanalytic tems within « total umber of 42 terms. Preliminary cortelations with more than four nonanalytic tems tended to have en unreasonable behavior conceming the dependence of c, and w on density in the critical region; moreover, when using more than four of such complex terms, the numerical expense would have been increased without a significant improvement in the \yuality uf die equation Anticipating Seu. 6 wid vegand wy the critical region, Eq, (6.1) willbe discussed in this section to avoid repeating a discussion of the representation of caloric ‘ropes in the critical region later in this paper. Figure 11 shows the plot of ¢, on the critical isochore; for analytic equations of state this plot was already shown in Fig. 9. In this figure, however, the solid line corresponds to Eq, (6.1) In comrast wo the analye CH,-type equation, the ‘new formulation is able to follow the strong curvature ofthe , plot in the immediate vicinity of the critical temperature and yields an infinite value for the specific isochoric heat capacity atthe critical point. Accordingly, the evaluation of 1539 ,/(kI(ke K)) octet “Se tas ty TUK = 6D © Bawants® Chen al” 5 Abdlagaoy era Ossype equation Frc, 6, Reorsentaton of exoeinen choi ea cacti he Sng ase (72-7) and pase (TT) region i dole loge lag, Te plots carves cosy 0 da om thee ochre {sled om Ey (1) the craves aguion of Chen ef and rf ‘uation wing the O, orm te Ss. 8.1) Eq. (6.1) yields a vanishing speed of sound at the critical point. Figure 12 shows the curve of the speed of sound, plotted on two isotherms as function of density. At the isotherm T_+0.5 K, the analytic CHy-type equation, the cross- ‘over equation of Chen etal. and Eq. (6.1) result in very 000 — 46.0) g 3 & Iscbaric heateapacity ¢, /(kJ(bE K) 8 8 t L ‘so ao as 300 «SD Density p/ (kg/m') 15. For temperate hewcen Tan 7,11 (6) rin an eligi or the oar heat apc run be rea dey. 4. Phys. Chem, Ref, Data, Vol. 25, No.6, 1986,1540 Toate 27, Cocfcemts of he cretion exution, (62) and B62), are} and 9 especly 2 -Rorses08 6 pail9s205 Gara 3250000000 7 tovo22 113284 4 lgeamaer susie § no at6rs 06792 similar values for the speed of sound. However, on ap- prosching the erica wemperatare, both the crossover equ tion and the nonanalytic wide-range equation, Eq. (6.1), develop a sharp minimum in the speed of sound, whereas the snced of sound calelated from the analytic envation does not change significantly when approaching the ertical temperature, Within the same density range, Fig. 13 shows the corresponding plots of the specific isochoric heat capacity ‘catcutated trom the same set ot equations. ‘Thus, Eq, (6.1) is the fist wide-range equation which yields nonanalytie behavior ofthe isochoric heat capacity And the speed of conn inthe immediate vicinity of the oii R. SPAN AND W. WAGNER cal point and which i sill explicit in the physical variables 7 and p. In Seo. 7 i wil be shown that this nonanalytic be havior doesnot affect the quality ofthe equation with respect tothe representation of other properties anywhere outside the cal gion Nevertheless, empirical equations of state contining nonanalyte terms have certain limits if an exat Fulfillment ofthe asymptotic power laws is required. The nonanaltie tem in Eq. (61) do not replace the contribution ofthe analytic tems in the surounding of the erical point but they fil the increasing gap between the analytic and nonan Iytic behavior. Therefore, eMcient values of the exponent 4; are smaller than theoretically expected ad result nae cal exponent which i too large ftom an asymptotic point of view fre Fa (69) Figure 14 shows that Eq. (6.1) represents the measured and theoretically predicted values of c, without significant deviations for temperatures in the region [7 ‘wun about 10% for U2 KU=T,) 203 mK in the ho rogeneous phase and for ~0.2 Ke(7—T7,)=—10 mK inthe two-phase region. The ploted c, courses correspond to the jeachore inthe pe (TR) and two phase (77) 7 300 600 900 1200, 1500 ‘es 05 g a a g = 0 aq v 05 200-250 300350 400 450500 ‘Temperature T/ K © Chao™ © Cho! -Kistakowsky and Rice™ X Bachr eral + Wooley™ & Bender eral” J DeGroot and Michels™ © Gurvich engl" © Masi and Petkof"* 'Y Emstand Hochberg™ © A Emst er al"™ = = = Angus er? =a Blyerat® of Angi cal an Ely er a ae pond fr compere, 4. Phys. Chem, Re, Data, Vol. 25, No.6, 1996ANEW EQUATION OF STATE FOR CARBON DIOXIDE 1541 ee ° 0 FOF Oo + OF ° “ oan + et eeeeeeOR Ogee cyte "= (207001, region. However, within a region of about +0.1 mK (outside where = p/p. and r = T/T with p. = 467.6 kg/m? and ‘the temperature range shown in Fig. 14) and —10 mK around T_= 308.1282K. the oritisal temperature, Eq, (6:1) yielde opesific ieoshori heat capacities which are significantly larger than the values predicted by the crossover equation of sae Figure 15 shows a problem which is related to a small ‘oscillation in the derivative (ep/dp), close to the ctitical point, Since the numerical value of this derivative i small, close tothe critical pont, even a very small oseillaton inthis, deciative results in a significant oscillation of properties re Tated to its reciprocal value like the isobaric heat capacity {see Eq, (5.1)] or the isothermal compressibility. Derivatives, of these properties [e-, (3cy/0p)z] should not be used in the range 440 kyfm'< p'=500 kyle’ and (T—T,)$2 K. Os- cilations are also observed in the devivaive (3c, /@T)q for approximately 420 kg/m' “the dts pubis in the TUPAC ables use tempers aconig to be IPTG rmerstre wl, Pt repaint eqsins here sot 0 Me ‘ams oct nth pert sae iI eal ee he peblsedeocore Ret cgay dae ay dried ric “ice the ceimon ofthe embos! eqsion ys uessoaghe sul 4. Phys. Chem. Ret. Dat, Vol 25, No.6, 1996 (ppp) of tener eal experimen station dat of usc ata canons presen in Se. 3 and fom the cove Chen parisons in the extended critical region. This formulation yields very similar results © the IUPAC equation but at ‘leary tess numerical expense. All the figures presenting th i dls segion ako comin values calelated ue ie crossover equation of Chen etal” which isthe most sophis- tieated scaled equation of state published for carbon dioxide ‘The representation of the specific isochoric heat capacity and the speed of sound in the eitcal region was discussed in etal in Seo. 5 None of the existing equations of state for carbon dioxide 4s valid on the ITS-90 temperature stale. Therefor, tempest tures were reconverted 10 the IPTS.G8 scale by using the procedure of Preston-Thomas et al.” before values were eslenlated from these equations. 7.1 Liquid—Vapor Boundary 7.14 Thermal Properties on the Cooxstence Curve [As shown in See. 3, the discussion of thermal properties on the Higuid—vapor boundary can be restcted 0 the ep tween these data and values calculated from Eq, (6.1) by using the phase equilitrium condition [see Eq. (2.2) is shown in Fig. 18. The additional lines in this deviation plot correspond to values calelated from the auxiliary equations‘A NEW EQUATION OF STATE FOR CARBON DIOXIDE 100 Aw" 100 Av" 100 Aci eS 20260280 Temperature T/K 1B Novikow and Trin" © Magee and Ely" Fo 20, Relive deviations 1008" 100 op ~ Yugo") ‘of expeimontl calc dit ation fm values Seu om (0), Datel frm the wdeange esion of Eye a ad [Age a plod fo mgr. prevented in this work (9 See.3), t values calulated from the equation of state of Ely era." by using the phase equilibrium condition and to values calculated from auxiliary ‘equations forthe saturation properties established by Angus eral” Angus etal. recommend the use of their auxiliary ‘equations for phase equilibrium calculations since they yield better results than the IUPAC equation of state gute 10 shows that Eq, (6-1) eepresents the very accurate vapor pressure data of Duschek eta to within 0.006% in pressure. Saturated liquid and vapor densities are repre sented to within =0.01% in density up to 3036 K and 297.0 K, respectively. Approaching the critical point the de~ Viations in density increase, but these deviations are still within the experimental uncertainty ofthe dat; thus, all the (ea ae server Go wid it eapetimental wncoay None of the equations hitherto known is able to reproduce the dat at last roughly within their uncertainty (the uncer: tainty values are given in Tables 7-9), Figure 19 shows the representation of the saturation prop: ‘nies in the critical region where a larger deviation scale is used. The very good representation of the vapor pressure data Is practically not affected when approaching the critical temperature nd the density deviations increase only slighty except for the last point measured for the saturated liquid density. Duschek eval“ do not give any estimation for the luncersinty of this point, but only 36 mK below the ertcal 1547 temperature a deviation of 0.48% in the saturated liquid density can be considered to be within the experimental uncertainty. ‘The crossover equation of Chen etal.” is able to reproduce Ge vapor pressure date within dheir experimental un certainty but it cannot represent the saturated vapor and liguid densities within the uncertainty of these state-of the-art measurements. The auxiliary equations presented in See3 reproduce the experimental data slightly beter than Eq (6.1) does. If one is interested in thermodynamically consistent values forall properties on the phase boundary, the evaluation of Eq. (6.1) in combination with Eq, (2.2) should be used and not the simpler auxiliary equations given in See. 3. 71. Colare Propenion on the Coonietonee Curse Figure 20 shows the representation of group | data pro Viding information on the caloric behavior on the phase Sound. The speed vf sound usta of He stated apo. state measured by Novikov and Telin'” are reproduced Wwithia 08% for T=301 K and to *3% for T>301 K. Only the last point 30 mK below the etal temperature exceeds this lit, but since the temperature scale of NO- vikov and Trelin is uncertain by more than 30 mK (see Seo. 410}, we didnot rely on this data point. The, analytic equations of sate of Angus eral? and Bly eral are not ale to follow the decreasing speed of sound when approaching the ential point Equation (6.1 represents bo the speed of sound and the speci isobaric het capacity in the saturated Liquid state to within +15 the greater deviations ofthe w data of Peccew and Van Dac! at temperatures between 249 K and 261 K ane ue to systematic ost the dataset. The equation of Fly era. yields resolts which are atleast similar to those calculated from Eq. (6.1, but the formulation of Angus 1 al? fils in describing caloric properties inthe saturated Tigi state (Se als the representation ofc, inthe homogeneous liquid region; See. 72.2 and Fig. 31) ‘The new equation of state was fited 10 the ¢} data of Magee and Ely" up to temperatures of 295 K ‘ince the conversion of cy toc, seem tobe uncertain for higher temperatures (ee Ser. 3.8). Above 295 K the deviations between {he converted dats and tho new fundamentsl equation emain within about +24; keeping in mind that c, i stronly di verging when approaching the rtcl point, this result un- delines the consistent description ofthe eritical region by Eq(6.) 7.2 Single-Phase Region 7.2.4 Thermal Properties inthe Single-Phase Region For carbon dioxide, the region where ppT data in refer- cence quality are available extends up w pressures of 13 MPa at temperatures up to 360 K. Within this region, the datasets, ‘of Duschek er al. *" Gilgen etal. Nowak eta"! and Guo etal describe the pp surface with an uncertainty of approximately = 0.02% in density and inthe extended criti 4. Phys. Chom. Ra. Data, Vol. 25, No.6, 1986,R. SPAN AND W. WAGNER 1548 oe 217K -220K g a a e905. g 0.05 . 299-301 K 0.05.7 erie Pressure p/ MPa © Duschek eral —D-_Jaeschke er al Phase boundary © Dusehek eral —-y_Taesebke et al™ fe index) ‘Angus ea © Guoetal™ 4. aeschke tal" (Burnet) Bly eral Gilgen eral” 5 Klimeck” Fi, Relative density devin of very acute pT ha at sabi empties see om (6), Va ae fom he idesong etaons of Bly ta and Angora ar pled for coopsnon 0.05% in density. None ofthe existing equations of state had access to these data sets because the data have been published since 1990, Equation (6.1) is able to reproduce these data within their experimental uncertainty (forthe nu cal region of =0.02% in pressure. In an extended region reaching up to pressures of 30 MPa and temperatures of 523 K, the data of Brachthauser"™ and Klimeck et al! Aeseribe the ppT surface with an uncertainty of 0.02% to 4 Phys. Chem, Ref, Data, Vol. 25, No.6, 1096A NEW EQUATION OF STATE FOR CARBON DIOXIDE 304K 1549 00s 0.05 0.05 g 313. K 100 (Pesp * Pease) / Pesp ° 005599300 400—~—~—~SOD~S~S~«ROS*C*«TOD Density p/ (kg/m*) © Duschek et at 4 Blyeral.” ~ Pitzer and Schreiber © vuscnex erat xX wentort = ply etal." D Gilgen er at!” B Nowak eral.“ == Chen eta” the widesange equations of Bly ol and Pier and Sehesibee® aod from the ‘merical values of the uncertainty see Table 12), Figures 2 t0 23 show the representation of some reference data on typical isotherms in order to ilustrate tis statement Figure 21 additionally containe data nf TaecchkeOtSS ‘which also give a high-quality description ofthe ppT surface * Corrected data, see Sec. (4.10) eon at vale alae fn By (6) Val alate Gn Crosor equation f Chane a ae plot fr compan, 1m the gas and superentical region, ‘The equation of Ely etal." yields a suitable description of the gas region at low temperatures but it has problems for temperatures above shout 250K The eqation of Angus er al ie not able to reproduce the state-of-the-art data in the gas region. In the 4. Phys. Chem, Ref, Data, Vol 25, No, 6, 1996A. SPAN AND W. WAGNER ar ~ S375 344 K 1850 321-340 K 100 (Pap -2. 5 6 7 8 910 20, 30 Pressure p/ MPa 4 Hosta otal "© Fenghour eal" = Angus etl? Hoinkis'* 8 Klimeck" ~ Bly eral. © Gilgen erat" 2 Brachthiuser"™ (© Duschek etal" 28 Relive density deviations of very acute pT dt at pecs emperaaesfom vaes calcaatsen E,(6) Ve cleat fo he eng equtns Bye land Ange le pts fo compan High-quality ppT data inthe extended critica region are liquid region, none of the existing equations of state is able to represent the reference data of Duschek etal! and Gilgen er al at least roughly o within their experimental wncerainty. Phys. Chem. Ret. Data, Vol. 25, No 6, 1986, shown in Fig. 22. The data of Duschek eral" and Gilgen cr al are supplemented by the selected data of Wentort™ sand by die dats of Ely eta whic are eoisent withtheA NEW EQUATION OF STATE FOR CARBON DIOXIDE 1851 548K .350K 00 (Pag Pe)! Po Pressure p/MPa Pressure p / MPa © Dusgek rat A wwaca™ © Gilgen eral" a > ine 4H Michels and mune, Golows ang Tsymarnyl + Vikaovich ral YVukaovi and Ati © Kirin eat © Peper. _ A. Vakalvich ang Attunin'™ gy Jaeshe ea™ Secs © Dusehekerel” 2 Eee So by erat & Yuraionen 8 Gboera”, © Kirin erat" © Kirin go Hoste al 3 Michels erat"? Hoinkis™ °¥ Fens al" 1B Magee and Ely © Kinin ea."™* 3 Klimeck Phase boundary * Corected dt, 8 See. 410 Angus er Elyeral Fe. 24, Relive deny eviton of sito pp dt rom vale acs fam Ba... Vas called fom te wideaige eto f Ely reference data by approximately +0.03% in pressure. Even in this region, Eq, (6.1) represents the reference data 10 within thir experimental uncertainty. The deviations between the data and values calculated from the equation of Ely cea! increase up to 0.1% in pressure, which comesponds to five times the uncertainty of the data, while the equation of Pitzer and Schreiber deviates by up t0 0.2%. ‘The eavation of Chen et al. which is especially dsisned for the description of this region, vies avery suitable ep resentation of the ppT data inthe surrounding of the eitical ‘sochore. However, at lower and higher densites, but clearly within the range of its validity, the crossover equation does ‘ot reproduce the reference data within their experimental uncertainty. Figure 23 shows the representation of high-quality data at higher temperatures and pressures, Up to 523 K and 30 MPa, the voT surface js defined bythe dst of Brachthiuser"™ and Klimeck ea" with an uncertainty of less than = 0.084% 4. Phys. Chem, Ret. Date, Vol. 25, No.6, 1996,R. SPAN AND W. WAGNER 1552 se oonK ao 03 > 03 7 a d g Lo 3 os “ 03! g mK 03 03 ed wt ab a3 03 T 7 im 5 ie to Pressure p/MPa Pressure p/ MPa ‘¥ Fenghour et al." A. Vokalovich and Attunin™ -— Angus erg? ayerat % Volalowich erat” ‘Bo. 25, Relative deny deviations felted po dae high temperate from vals cake fo By (6.1), Vale acted fom he wie-ange ‘Shans of Byer” and Ange ae pled fo eam 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 al" improve the uncertainty of the ppT sur- state describes the reliable data beter than the older equa- face to less than 0.1% in density tions. The comparison with the datasets of Duschek eral! ‘A representative view on the complete group 1 set of the and Gilgen eta" shows thatthe use of adjusted data (see (POT data up to tomporatus of 473 K and proanues of Eee. 4.10) was reasonable 573K 398K, 613 K-789K 100 (Posy Pose)! Pr Pressure p/ MPa Pressure p/ MPa © Michels erapt®* 8 Suznetat™ wu mine Angus eg? © Teikls ral” © ShinonovanéShmuloveh Biya * Corected dase Sec. 410 Fro. 26, Relive deny devon of selected dita a high resus Hom vals cated rm Eq (6.1) Valo cated from he wie cnge Te 4. Phys. Chem, Ret. Dat, Vol. 25, No.6, 1996,ANEW EQUATION OF STATE FOR CARBON DIOXIDE 1580 ; sa £ “3 Pie — pee eons a ml 2 A ° : a a lmeiea maa Presse p/ MPa Presse p/ MPa ist and Hoghere"™** Emsteral'™* ‘Angus er gl” 3 imran 8 Rate ayeae *Comected dua sce Sec 410 ‘he. 27. Balan deviation of lcd iesorc hst eperity tn rm vale aad fF, (61) Vie aa fen he wing ai of Ely eral ant Ang ae ped fer compan ‘At temperatures above 608 K, Eq. (6.1) ic sosontaly based on the same data sets asthe equations of Ely eta ‘and Angus eal” Nevertheless, the three equation show significantly different courses for pressures above 15 MP2. Fig- lute 25 shows that the equation of Angus eral.” yields the best representation of the data of Vukalovich and Altanin."*8" However, in order to achieve @ consistent description of the calorie and thermal properties in other re sions, we had to assume that this dataset exhibits system- je emor. The data of Fenghour etal! support our interpretation of the poT surface for temperatures up t0 68 K. Figure 26 shows how the ppT data at very high pressures are represented. Since the range of validity is limited to 100 MPa for tke equation Uf Aus et a® aid 2 300 PAP for the equation of Ely etal! these equations are already extrapolated when ploting values calculated from these ‘equations in Fig. 26. With an estimated uncertainty ranging from 1% to 25 in density, the data of Tsiklis eral!” and Shmonov and Shmulovich'** represent the transition to the ‘extrapolation range of Eq, (61) which is discussed in Sec. 7.9, Equation (0.1) yields Sutable representauon OF ese data 7.2.2 Calorie Proper in the Single.Dhaee Begion Inthe gas ad the superertial region, the caloric behavior ofan equation of sae for carbon dioxide canbe discussed tmnt advantageously bythe exanple uf the specific isobaric heat capacity. Figure 27 shows the deviation between values calculated from Eq. (6.1) and reliable measurements of cy The data of Bender et al.!”” Ems and Hochbere. and of Ent tal were corrected according othe descriptions in $00: 4.10. The oncllnt rprecontaton ofthe data within the 488 region, where the wellknown contribution of cis pre= soo snk_s0K © 000 naan : “eanee® f Cpe UN 2 RMagguegseserr® a es ? 2 a sak Sa ase oank 2 z oy Z p22 22 no08ou0. g 5028 3° J 4 = (ransom ‘039 —sto"—a00 0 Pressure p/ MPa Pressure p/ MP (© Novikov and Tela” ‘32, Keane demons o pnd sound data t sapere emg Tues fom vaesclaed fom Eq (61). Vales called fo the trse-ange ston of Bly a and of Peer ad Slee an. the ange of vl, from he rosover equation of Che ea" a ple Fig. 29. Up to 473 K, the data of Bender etal. support the results of the equations of state. At higher temperatures and moderate pressures, the influence of the residual part of cp decreases. Since the uncertainty of cf(T) is very small (See See, 6.1) and ot least some information on the residual part ‘of the equations of state is available from ppT data the ‘equations seem tobe more reliable than the available data inthis region, Deviations with regard to the specific isochoric heat ce pacity at gas and liquid densities are presented in Fig. 30. In the gas region, the behavior ofthe new fundamental equation ovenuing valent ynuyensos io based ur le yaesine data uf ty and ithe deviations between the c, data of Magee and Ely!!® and values calculated from Eq. (6.1) and from the other equations of sate, respectively, probably reflect the uncertainty in the data. This fact has resulted in the low average weighting factor listed in Table 17. At high dens ties, however, the cy experiments of Magee and Ely!'® Yleidedreinable results whe form ake oN Ra source of information on te caloric properties at liquid den- Unformnately. these ¢, data only descrhe states at supercritical pressures (see Fig. 17), so that there is a wide gap between caloric data in the single-phase region and in the saturated liquid state. Figure 31 shows absolute values ofthe specie isochorie heat capacity on two liquid isochors. plot ted versus pressure. Equation (6.1) follows the measurements fm the 880 kg/m. 970 kg/m*, and L0SO kg/m isochors and yale rth deoreseing ponseura lighily inrnsacing Aavatinne from the c, values atthe 1140 kg/m’ isochore. In contrast to © Pitaevskaya and Bilevich”™ mono Bly Fro, 33, Reve devitions of spat of sound dt thigh press fom ates clei roe Eg (6), Vacs caated fom the wie-nge (enton of yo land Aton a a re plata or compares init ye oe sf a pyc (we Tae 1. this behavior, the equation of Ely eral follows the couse of the 1140 kg/m? isochore, but it yields slightly too low spe: cific isochoric heat capacities at lower densities. In spite of these different tendencies, the deviations between cy values, ‘calculated from these equations do not exceed 1.5% through ‘ut the extrapolation down to the vapor pressure. Since the tuncersinyy im the specific heat capacity calculated from. Eq, (6.1) is estimated to be =+1.5% in the whole high density region for pressures up to 40 MPa (see Sec. 8), we believe thatthe uncertainty at subertical pressures does not Jncrease due to the gap in the data set. New data which descrie the caloric behavior of liquid carbon dioxide more accurately would be desirable in order to prove whether tis ‘The equation of Angus er al fails completly in the description of the specific isochoric heat capacity at high densities. In the liquid region, the deviation between Eq, (6.1) ‘and this formulation grows to 16%, For carbon dioxide, the representation of speed of sound measurements is a sensitive test for the quality of an equa- Hot oF site In ie Rolling wo seglons. ‘The date Of vikov and Trelin™? describe the caloric behavior within the as and supereritical region. Figure 32 illustrates the representation of w values on two representative isotherms of this data set. While all the considered formulations represen the data within their uncertainty at 373 K, only Eq, (6.1) is able to reproduce the measurements at 308 K; in the extended. critical region, the deviatlons do not exceed =0.7%%, On the 308 K isotherm the erossover equation of Chen eta” yields ‘deviations up t0 2% At tamporatunes horunon 208 K and 47% K Pitaevskaya and Bilevich'” measured speed of sound data at pressures to 4. Phys. Chem. Ret. Dat, Vl 25, No.6, 1896,1556 263 K-209.K R. SPAN AND W. WAGNER 359K-360K S ooog ak Hes) ay 100 (4, ie | a| oF i to “OF it io Pressure p/MPa Pressure p/MPa © Vuatovie et a™ Bender ral" ~ = ~ Phase boundary A Ain and Gees ™ eral” Bg, 34, Relive vito of rity deep Je Tomo ofc res cen fm Ba, (), Vater cei fo he Wideage equi o Be 450 MPa. These data are represented by Eq. (61) to within their expected uncertainty of approximately =2%. Figure 33, shows representative deviation plots covering the lowest and hhighect tompersturec of thio data eet. None of the previous equations of state is able to yield a reasonable representation ofthese data, The equation of Angus etal 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 eta should yield roliable results at least within the range of its valicity, namely up to 300 MPa, ‘At pecsuces opto 1-8 MPs, the Joule. Thomson mesure iments of Bender eral” were used in the nonlinear fit but these data could not be represented without systematic, slightly temperature dependent deviations, Afler work oa the ‘new equation of state had been completed, the isothermal Joule-Thomson coefficients measured by _Vukalovich ‘eral were converted into differential Joule—Thomson co- cicicnts by the use of the specific isobaric heat capacity calculated from Eq. (6.1). The new equation represents the ‘converted data of Vukalovich etal. without systematic de- vations (see Fiz. 34; the very accurate poT data se in the ‘gas region prevented the representation of the measurements ‘of Bender etal. which deviate from the correlation by approximately 0.5% to 1%, 7.3 Extrapolation Behavior of the New Fundamental Equation shop on Equations of State, which took place in Bochum in 1990, the extrapolation behavior of empirical equations of state was examined in some detail during the work on carbon dioxide, Since these results cover leatues of diferent sub- J. Phys Chem, Ref, Data, Vo. 25, No. 8, 1986 Ange are ond fr opal Vile a ™ woe owed when sain Eg stances and general approaches, they will be discussed elsewhere." Here, the considerations are restricted to the new fundamental equation for carbon dioxide; the following subsections wil give only u bier survey on we extapolauon behavior of Eq, (6.1), 250) 200] ET In @/ (mol) = Angus er = Byerat 3000 7000 Pressure p/ MPa Fro, 35. Representation of experimentally detsmied fugctis on i therm t very igh pera abd pees. Valus cles om th iderange uso a Eye al abl Angus eal re pled person[ANEW EQUATION OF STATE FOR CARBON DIOXIDE 1587 20000 eer ay === Angus et gl? % — F461) 25000 | = Ely etal" | ad 2 nats gat™ oF © Ey ; 24 > iso . < g boo a g 224 a) ie 2 ‘, ! . 3 2, soo0 / oe is 6 ol = g 16001900 2200 2500 Density p/ (kg/m’) Fro. 36. Remesenton of experimen Gta erring he Huger sue can dni, gore carver elated fom he wide-range Ste fons of ly eo and Aga ea are ted fr comparison. 7300 1734 Extrapolation Beyond the Range of Primary Data ‘The range of validity of Ba. (6.1) is based on the range ‘where reliable data of thermodynamical properties exist However, two kinds of data exceed this range up {0 approximately 3000 MP wt eu 1200 K and 1600 K, The data of Haselton et al were not used when developing Eq. (6.1) since itis dificult to esi- rate the uncertainty of data originating from measurements ‘of chemical equilibria and since the logarithmic structure of the dependency between the fugacity » and the reduced Helmholtz energy (see Table 3) prevents an inclusion into tne linear optimization proceuure, eventctess, By. (6.1) follows the course of the measurements, whereas both the equation of Angus etal’ and the equation of Bly etal! yield fugaciies which are significantly too large. AC least at Tow pressures, the remaining systematic deviations cannot be explained by @ misbehavior of the equation of stat. AIL ‘equations of sate which have been investigated result in very Similar fogaeities at pressures below 1000 MPs I dis 1 sion, the experimental results are inconsistent with ppT data at lower temperatures, Atoven highor poccuene. shack wave measurements result in data forthe Hugoniot relation “Tame 3. Ta denon ofthe so an fs ore ea eves othe compression fae are of he sal cane Defation Ble cone JoudeThonses inversion carve Ze pie (iiphe=0 og geet reas ene Ogee Reduced temperature 7/7, rn 37. The salle ea curves cleat from Ea, (1) and pote in {pipe og.) gam. The foul Tomson iverson cme abd Ce Tote inverse curve excel the terperateenge In which Ey (6.1) fist exponent h—hou=05(p~Pox)(Upow* Vip), (7.1) where ft isthe enthalpy, p the pressure, and p the density after releasing the shock wave and gg. Pas 80d po at the initial values, Even though it isnot yet clear whether these ‘measurements describe equilibrium states at all, comparisons with these data are the only source of experimental informs- thon on tne extrapuason Healer Of at equation vf sate a very high pressures, Figure 36 shows Hugoniot plots calc lated from Eq, (6.1) and from the other two equations of state considered here. compared with the data of Nellis etal? fand Schott" At approximately 34000 MPa, Nellis etal ‘observed kink i the course of the Hugoniot curve which is, interpreted as an indication of a spontaneous disintegration reaction. So iC can be seen that Bq (6.1) yiekls a reaswuable description of the Hugoniot curve of carbon dioxide up to the limits of chemical stability. A Tp plot, which is not given, Ther, chowe shat the Hugoniot curves ealeulated from the equations of Ely et al”* and Angus 2a." run into low temperature solutions corresponding to solid states above densities of about 1400 ke/m’ 17.32 Representation of “Ideal Curves" Various authors (see Refs. 234 to 238) have discussed plots of 20 walled ideal curvec? as» wnivereal hahovion of deal carves re ves wich oma sates where a pci propery ‘ofa fd equal te coreonang prope of the yptiet ea 4: Phys. Chem, Ret, Data, Vol. 25, No, 8, 19961558 Pressure p/NPa R. SPAN AND W. WAGNER, Pressure p/MPa a) | io, —— 1B BB 50% ing, , ice | = © 206% ing i ay ye v0 D 215% ing i oo. aE 2208 ing jR 2108 inp F 240m ing, re ! G_ +205 in 7 G es20% ng 20a) 500 08D 1000 2m) 300400 S00 cao 8001000 ‘Temperature T/K ‘a6, Team dngram frat eneunen Rom 54} 8 ep ‘ke uaceraty in rere en, pure substances. In 1991, de Keuck’” gave a bnet survey on this topic ‘The most common ideal curves are the zeroth and fist the relations given in Table 33. Figure 37 shows the plot of W we A - 2 D g al | St] gop 2 — fA 200% nw i Bo 2025% nw 2 re EE ———- b 2058-2108 in w E £108-#20% inw A F 2208-2408 inw io! G psi ny 200300000 600.1000 Temperature T/K Fo, 39, Toleance diagram fo sped of sound data caus from 5 (1). nthe iret vit ofthe cial poi (gion G) is «iat io eximat am once in beso ofthe sowing nen | serine temgerte nd reve nec 4 Phys. Chem, Ret. Data, Vol 25, No.6, 1996, ‘Temperature T/K Ep (1) le the sade vcly ofthe cea! pot (esion O) ss cient estimate an uncer nc, bese of te growing iene of ‘ncaa tegen ad reste mearerent these \urves calulated fio By. (6.1). "The new Funan equation was fited 10 data up to reduced pressures of pip.=108 and up to reduced temperatures of T/T35, ‘Thus, the course of the ideal curves does not significantly ‘exceed the pressure range covered by data, but both the Joule-Thomson inversion curve and the Joule inversion curve reach up to temperatutes which clearly exceed the Frage OF de dts use Wo A. EA. (01) Preliminary. equations showed an unreasonable plot of the Joule inversion curve at very high temperatures. In order to force the equation to form a maximum in the course of the second viral coefficient and to ensure thatthe equation of| state yields an intersection of the Joule inversion curve with the zero pressure line at that temperature, 27 Tp data were etermined by graphical extrapolation of the Joule inversion curve in 8 pT plot (see Ref. 35). At these values ofthe state variables, the condition of the Joule inversion eure, 45, = 0) we introvincd int the data set used during the adjustment of Eq. (6.1). Since itis dificult to estimate the uncertainty of the inversion condition, the weight of these data was determined by using estimations for the uncertainty ofthe independent variables T and p in combination with the Gaussian error propagation formula [see Eq. (2.6) Equation (6.1) shows reasonable plots of the ideal curves inthe high temperatne segion, see Fig. 47 The temper at which the Joule inversion curve intrseots the zero pressure line and at which the second virial coefficient pases ‘through a maximum corresponds to about T/T. = 269. Thus, the reasonable behavior of Eq. (6.1) reaches even up to temA NEW EQUATION OF STATE FOR CARBON DIOXIDE peratures beyond the limits of the chemical stability of earbon dioxice 8. Uncertainty of the New Equation of State Estimates for the uncertainty of an empirical equation of. state have to be guided by comparisons with experimental data, In regions where no data are available, comparisons ‘with existing equations of state can be used as a substitu A conservative estimation of the uncertainty of pp, w, and value calculated from Eq, (6.1 is illustrated in the tolee- ance diagrams Figs, 38 to 40, Uncertainties inc, correspond to the uncertainties given for c, in the liquid and gas region In the extended critical retion, the uncertainty in ¢,, may ‘exceed the uncertainty in cp. The uncertainty of Ait or Au values calculated from Eq, (6.1) is less than or equal to the ‘uncertainty in c, of ¢, » respectively. ‘GUISE He Fange OF Hs valllty, Fay (G1) should yietd reasonable results for the basic thermodynamic properties like pressure, enthalpy, and fugacity within the whole chemi- cally stable region of carbon dioxide. Of course. the extrao- lation results have an increased uncertainty which cannot be estimated, The calculation of derived properties such as the speed of sound or specific heat capacities is not recom- mended beyond the limits of validity. If such data are needed, the results should be checked carefully 9. Conclusions Based on a comprehensive study on the experimental data forthe thermodynamic properties of carbon dioxide, a new fundamental equation in the form of the Helmholtz energy has been developed. This empirical formulation is valid in the fuid region up to temperatures of 1100 K and at pres sures up to 800 MPa, The equation is able to represent al- ‘most all the reliable data ia the homogeneous region and on 1859 the liguid-vapor phase boundary within their experimental uncertain. The consideration of state-f-tie-art dara as resulted ina previously unequalled accuracy forthe regions of ‘major technical interest. Intensive work onthe consistency of the data set used has led to reasonable results in regions with ‘poor data situation. ‘Special interest has been focused on the behavior of calorie properties in te critical region and on the extrapolation behavior of empirical equations of state, The introduction ot ronanalytic terms enables the new wide-range equation of state to represent the isochoric het capacity andthe speed of sound even inthe immediate vicinity of the critical point: up to now, tis attribute has only been a domain of scaled equa tions of state which introduce iterative dependencies between iferent sets of variables and a limited range of validity. An examination of the extrapolation behavior of empirical equa tions of state has resulted in new approaches which have been used for the new formulation, For the basic properties of carbon dioxide ouch ae proseure, enthalpy, and fuzecity. the new fundamental equation should yield reasonable results within the whole egion of chemical stability. 10. Appendix: Thermoaynamic Properties. of Carbon Dioxide In onder w preserve thermodynamic consistency all values 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 input data warrant, but a strict adherence to this principle is ificul, and possible conflict has always been avoided by including more figures than are strictly necessary. Especially Jn the extended critical region, interpolation between values given may result in uncertainties which are significantly larger then the uncertainties of Eq. (6.1). For sophisticated applications, values shoud he calculated directly from Fa, (6.1); @ compoter-code suitable for such applications can be ‘obiained from the suthors. 4. Phys. Chom. ef, Data, Vol. 25, No.6, 1996,1560 R. SPAN AND W. WAGNER Trots 4. Themadyamicproperiss of sauratdcarbon docde Tempeame ——Pesswe Density ‘Enis Estoy e o Speedo 00 our Gate) an une) fe) KNT soni) 216590 05196 —~TITRA —678 277 rr 19530 Iss B76 “res ~OS00H0 eat osu Zan aie ssn 1730 3.98 =220s1 grass 19566 os.86 20 osm 68 12008 “2187 3 19618 sit 18a =1sa2 061987 ase asso ms m esi = s881 aig 21607 96707 19696 679 Ey ome S140 #1046 Lise 096087 1979, 16530 =r —o6aias son ssso7 26 ove aa 40819 Sane 096174 19810 Ey onm = est aoeat Tans 95017 Takes 21595 nen —n6aier 0.68350 ones 20 sms 2k 00.21 2108 095067 1997 27 “nie ~osn06 osrant Loos am esas anon s68 “tone, ooses 2061 25050 =m. aes ers hos a 0363 ni3o8 326 2066 5190 20160 26036 “mae ~ospae7 ene Lon 26 nua sos. 8 “20082 e563 2st 28935 ons, oe 1 ae 1961 vos7as 20323 nes 2a 31.052 Ho7isas new sis 20 Lass tose7 ~aniss sss asta 3295 Sams 70s 11033, 22 1am 108056 19968 903s 2067 35670 Honass ona ines se 074807 ‘v7 hist us 1.593 1063.6, 19688 id 20956 “0s 076 o7s9 Liv 13662 076806 ors 106) 20 1.7850 so4s97 A193 053683 210 ett =m ost L366 “301 Lanner o7sat9 1263 at on wom =19991 093380 2st ‘shld Sopacsr 07601 30e 286 283 rons = 896 93300 21098 sas Coase nk 13409 a 22806 1008.71 =18650 ssaua 22@ 0.38 moss 073390 ass «0 ass ong = 18095 ass? 22554 ‘ai? mons (026 Taass 2 2630 mss “1g sms 2am ss600 “ossi67 osmies| ater ms ans om ~14162 ose 253206 Tia 8 Osteo ssa 26 24701 6192 1998 ose 23617 mat ~1sse3 ox T3919 8 3034 sts =i 093693 2050 m0 32083 isa =13686 09399 24534 sus74 “ase, Ossi68 ino m asa 9326 186 098s a8 mm sor omx0 -1787 054659 25604 10032 nose osrsot 30s7 26 3855 0890 cana oso 25396 4. Phys. Chem. Ref. Data, Vol. 25, No 6, 1096ANEW EQUATION OF STATE FOR CARBON DIOXIDE 1561 ‘Thais 36. Thermodynamic pope of stra carton dnride—Cotinsed Tempers rene ——Dewigg —‘Emalpy "Eno e & ‘Speed of © mr) Gaia) an) Dts] vk] ] sud ae 3952 pro Dae =i oasis aim ‘wore nor asi 50719 2isat 20807 200 ana e586 =i e046 zeit ams tai oso asi6 anne ann Ey as 9.32 aoe Ls eset 29u6 $5219 15005 =a73 ~n9uere own Dass 2168 2 asm sie =a 1.608 asri6s se me 15909 “ess 091006 nese 2600 aon 25 aan 9.12 “73.08 =i gras a2iet ana aos cere ast tusrs 2079 23.10 28 06s m0 26194 = 1a 98528 Sais in 987 ~9926 0989 1.02 532108 2oist 20 sai77 eae Aas “ise cess 5.556 s7195 202 S161 78533 “28076, 15657 100s 0145 33083 sss 5599 10228 1.3 4558 78 a8 sean 16809 aun H1sus 10177 4834 am185 296 mm 1028 0.56 15183 osm Sits sake 21934 10574 10628 16 ora 1249 298 sia m7 “m6 =14906 ans 63403 642 00 e731 oma Cao Thast 198 son 280 25658 =11970 otis 1296 tiga 16533 01 e088 oe 21803 10 est huss mais 28515 Han A136 tam 15889 26 om ones oo, 11176 1426 12316 Isi86 21808 5os.is ~1s10s =11588 3616 23.800 ast a 1890 3086 20373 108 iam 30233 ta 339.00 ~13991 S807 Lanns 59) mn 20 73885 5030 =a 13509 20531 sas Bate ana ~s88 =1386 20679 5558 782 sou a3 35100 =i7653 =o Tape por "Cate po 4. Phys. Chem. Ret, Data, Vol. 25, No.6, 19961562 . SPAN AND W. WAGNER “Tams 35. Themadvnimic oer of cabo ide Tempenmwe ——Desty—sUmemal eegy——Ealpy ——_Enopy ee @ ‘Sret of « there) tng) (ng hemy)—_Gke ——S KT——_s sae a0 =i cao 0ST oso os Tao 160 14098 Hin Teen 022s 04651 7466) 21890 0 1339 A162 sn ~o.8801 ossins 7506 126 io io =n Shs Colastt 086598 ad moat 20 uz 1068s -ss2 “ois srs 176897 Das 20 Lises “90s “sae “007mg sai? ese boa Xo 108 Sans Seog ona 30473 ‘78s dost 30 oss Hse Stoo “ons asta foes bana 0 toate “e578 Snow “eonons sie 08s aaa m0 096360 arnt nai now 060579 sient o123 0 oust “esa Ona ‘ona Et a8 ‘ase “ane 0st “omnes 073168 oon ist 4. Phys. Chem. Ret. Dat, Vol. 25, No.6, 1996,ANEW EQUATION OF STATE FOR CARBON DIOXIDE 1565 ‘Tate 35. Themodyoamic ropes of arom diwie Contin Tengen ———Dessty—‘Untemal energy ———Enulpy Ey | ee o ‘Speed ot «© (aim) we) jams) he) K))——— ve KN]_——_soa iy O30 Ma hota ry Tame ma Ti3a0 onan oma ry 3352 “0 3410 S048 mn aor oir ose? 52406 5 33523 73097 19259 22st ston sone sms 505 30099 as 2148 a6 ose 0340 31830 0 29011 13876 23953 osm, oss 10992 5508 S15 2766 Ista ese osisss osm 0638 36549 0 22687 27038 03.07 nese os370 Line e800 00 os 36638 ‘i802 are seo Le» ou 00 17635 san 3685 zt 1013s 20s pat ho 1426 ose 13.63 11780 Lom 12596 a5a58 (050 MP haber 0 aims ae 12896 ars 00s ‘as0s22 393 20 ass 10478 ~s4010 Hoss osese7 ers 23138 20 686 98202 33200 050124 ostrs0 1 231065 260 10.605 85.086 37901 0.43188 063782 ‘186526 24758 0 soxst 18487 29281 ~039920 osutst oas7i0, ast 20 97568 —1180 Han “036761 os255 ‘x70 25127 290 93864 55.133 ~1n865 “axe saont oxrsy7 aa 50 S36 339 ~3oui6 03072 fret sans 25635 bs 296 19.19 “ons ‘sos oss mos 350 16736 268 a3 ~o6eo2 ones ois rene ms 1383 51305 ‘6905 =o10si4 7353 oss70 29635 0 sar 13393, asa78 =noas0 bis ‘55208 5813 es sans 0197 ors os7010 iso? 4 91st oo 79197 oes? aan os 5505 0126 0s oot 33210 a0 ptze sauny 17870 una on 31028 2s 5556 naot ones onan 10363 6 550 am 1353 oars oss ost 3591 15 45108 isto ose ors ss 36347 oo rid 907 oa6its sist ton suas 0 ami 7058 oss 99 11289 a0 0 33067 366.5 055090 voa0n 107 2505 500 25383 6631 0087 Loist ‘ns 354 00 24083 61351 tones toms 12600 515 Vol. 25, No.6, 19961566 R. SPAN AND W. WAGNER ‘Thats 3S. Themodyaumic prope of cubon oxide Continued Tomperre ———Deasly somal ewmgy——otapy Eawopy e & ‘Spee of wo sim) (oa) cy Chg KHER] EK} av (75 MP abar zee a1787 68 ar ry T9518 wa 20 esas ~eno “ale oor 96a os20 ns nan ‘i047 095306, lm 91536 ssas 19.60 “T3389 “ons O6s887 90s mst 20 19095 2.068 ~ossig 58257 ssa 2553 2s S35 e435 Hosiors 05047 ows mo oe 018 Seat nso Gates ser pas as 11536 55082 ‘Speed of is) om tun) ang) (see x) ) a KN] ss) =e wat Hae —aar8s —Ta rey Ie waar BS 1958 261.86 25250 = 553 56658 3335 39087 x m9 =a a0 =1so01 ons asso anak as as cna “5198 Tham 15317 sis 16k 310 25336 =n 3510 10811 ons $5173 aoe 315 mat =11830 He198 =1o03s os4en0 2.5805 2599 x0 2an3.04 =10522 68283 nse ‘sos 2076 ma 3 i992 as -si20 sms) OStTS9 oats 2079 30 vast =e a2 “oem RSET 1as98 246 3 16970 sao asi osm OBasi3 171% 223 30 02 16430 30204 ~omsis —ox3i9 631 20706 3S 15580 ad cae chen ese is Bet 350 15013 ~o402 ar ~oniss ‘ist 1469 23593 360 ost “stoi “stig 076161 1370 13768 28 30 1260 -am aes some aso ery mos 30 12006 337 3109 “oss oaoT36 2302 23395 0 49s 149s 50.293 Kner nes Lame boss a0 now ~sn101 em masons sion? iss 2540 20 10360 ass 5580 =osia2 ese isso sass 40 ‘spas 2487 37080 Hosisis os ass siozt 0 6102 oust 10850 oasort osna0 Liss sas ro ons aan mts Toaioss a ies or “0 sa072 26 wna soa ste07 ast man 0 5707 617 15360 M0330 oss iss 2s 3 jase ors 1298 Toatest osca8t Lis 3678 530 74368 018 nto 0260s star si 55607 55 70592 tasr 2021 sont oases knot 36403 on eins 1658.96 mss “oss svar Last sae as 4201 88 600 Contos = Oa1010 aes 3163 “ 6164 2283 ss Soorss 92186 Lust 954 as sio72 23631 339 Hoo sass hisrs soa 0 sea 2522 0252 901128 aaa gst 0846 m0 193 S582 S103 16st? euas hiss anes 00 330 934 a8 31141 os? aus 4836 ‘000 33083 6346 73836 oaarts os 12995 aan ho 58s ‘7008 salad 086100, Lom fe 05.03 ‘SMP tar TSI? —_ueTaS 287 ~aias ~ane ‘onan 9120 T0089 20 si A207 41796 22065 osrast ous 93256 Bs ees caisa3 Tat disse os 133 sss 20 huss 5.70 39872 -21010 96483 lous szaot bs 2826 9610 =36901 20092 opsras 197 wun J. Phys. Chem. Ret. Data, Vol. 25, No.6, 19961578 . SPAN AND W. WAGNER ‘Tague 35. Themodynamic properties of earn dloxke—Contiued Tempernure Deity “Tiel nergy Ely Enron ce ‘Speed of ‘s (hoi) cy ung) Dts) OG KT] KT] sud os 2a Toba ~a9m ao ‘951K 968i ioe as 09995 30.32 1902 asians 19806 275 250 106.70 -35930 =19567 oss 2o18t 11907 BS tower =M913 =19t6 93676 2osi6 3255 0 1633 3877 m1s162 ossa7 20925 1627 2s ro9s2 Sm =1I59 53036 2109 67891 m0 786 =3032 =13982 oszs52 22000 22 2s 55186 06:10 =1sat Bonet 22867 ‘589 0 ona ~24a =17n9 155010, 23081 srs as 9092 =72.10 16634 93400 25108 i217 0 sia 2888 ~19n8 aoa 27633 48296 Bs 100 38022 a1 sst03 Sun ‘tso8 sao 737 23650 =15138 se634| 39m 366 ms 677 =a 1301 Lose sa138 23500 310 st 284 =a 11999 93864 19428 33. ates “ss =thnso see sos zoe x0 nist wrt ton 093636 2750 baa as 2290 65909-06100 90103 23st amas 30 19837 ns ~192836 osm 20894 me Mo ies 3618 masi239 oss ims m499 us 08 5097 aise 38 2s Dotsas oa eo ois 58617 no sir oat us sir saa 4. Phys. Chem, Ret. Data, Vol. 25, No. 6, 1986,1582 . SPAN AND W. WAGNER, ‘Toa 3, Theamyanmic ropes of abn oxide Coen Tempore Dewy Tera negy ‘Ely roe = ‘Sree © es) i) kg) eg) EK) soot) "00M ar = was ry ~raas =r aos 2s wai a m6 2808 Sane a4 91938 a9 09 Bs 86 ~ms2 <8 =m asa2se 2524s Prats 0 a8 15129 “1608 “1340 aoa asm Secor Ms ‘i630 ary isis 00 a8 ase seas 5 sisi Shant0 Tiiase isa ‘sists 2550, sss m ois “ins “eae “Lie ‘s0n10 23976 hese x tos HI “sis tas ‘so1es 2218 une 0 a8 “nie em “lo asa 2am so Bo x50 ark Sais = Sgsioe a? wast sors a0 sar ~ems =s33i0 “91301 ame Thets iba m8 ey oa tt Sse suas ace areas same sa ae Tse San ee etd Bet ssi Sins 51989 bara vam man mon “077 nso oes tau mn 2am 0336 sa esi 13985 ns base si 358 areas Seo Meo ns fam 131 “oer am 5023 on ‘os ‘98 Mossi7—oss7 asst woos Pret wae use cea adnate 1a sme ha 630 m0 Coss Osseo (a6 sas ia30 ras 29s Maser 0sisa8 hae sas mas 96 man Cost gga se sony len 79 sis comes omsu86 Ease sea Hse 2a sen ona uae? tee ier 927 288 Ht iss osstss ss in toss 3800 er Soom aseied Lan oar mot wat aan oun tone 1asis 580 Stas faim 0% asses burst oie S08 500 ar se Ties 2301 fear thas ana Histss <3 erry ors tsar tors tnes92 cc08 ons aaa 031 re asa Tosa one sso sue tina 678 2s hosass set Saws Holas sat Hise asain He ass roses Saunt Tos Ziise eats ss wis 1096129 Seton Sas ad aes te) mee Phys. Cham. Ret. Date, Vo. 25, No.6, 1096‘ANEW EQUATION OF STATE FOR CARBON DIOXIDE 1883 ‘Taat 3.Temndyaumic popes of to die—Contiud Fempenue ‘Deny ‘nema comgy ‘tly ary a ‘pet in gm tans) ks) eK] EK) Ks 7250 Ps ok rm i eT Tian Tier oa Tae wise Ds tosis 38350, Ses a a8 out ross co Toisas, 3245 one TU on t5as9 7898 as wx) 31855 nat ay osm tsar mee 0 sa 30623 ~2anss =t7I68 asa 150 ese Bs SSS 2697 7081 stom ‘asi is ws Ms bas ~s 2080 are) 91997 done 61336 30 ws =mkeo ~2nst =i 091387 29s S090 sis mm ~28899 030 =1399 avian do 50003 Bs sss 285 =m87 ar atest 2109 ist x 0180 “29m “inst =Late ootoes 2s an 3 mm 268 sis a ‘9108 2st 98 0 wan alba =1687, = 086 das sas xs mis 188090 Hiss Tides ‘0% hws dea 390 m2 ~1m991 Tsaat H13313 0059 225 B07 x sim ~1T00 are =m ‘03 2254 sat = fein 18099 Woe 1068 ‘90800 22167 sat a Sras “1148 cals 10588 ‘aoe 2am ss86 a 15s “s03 Sas307 1008 oxe7es 1613 Boe a0 $5035 “2686 ee rT Tete sat bo ion sts Bisrs 0910552 tee aaa 0 a ~0363 nisms agra nN? tao 3603 0 sero) a0 aon ~omseT ——osses0 ts Maio o uss cise. see ‘mom iad tm 3090 mo mast aro vr ‘amon bases? ane 3302 py ann 308 feos = “oma aae ass aie Po eset es 10036 Tonme aks tas wast Py sao nm i839 “oasis 8089 1367 3695 2s met seme taka Shsiis NS Bar m8 0 er bon ass “oss 490348 130 aL 2 kos inso2 293 “basses a9tibs vous soot oo nest 149 ssa “bails O9aiKe 189 aan 0 aman Tas sows Tosa B80 as fs oss ines ons Toss 09859 1s 290 0 ‘90 B02 mas Toasts 098 aes ‘ost 6 nee. san aia ‘web tise 13083 este roy sot sor 018 aon asia nao so it) ae e758 sso omsss Tes 1964 S195 4 Phys. Cham. Rt. Dat, Vo. 25, No.6, 19051584 R. SPAN AND W. WAGNER, ‘Tague 35. Themodynumic ope of carbon dxide—Comtinued ‘Temperie ——Deaity—Inemal ney Etnpy py ee a ‘Speed ot © gi) ng) ks) (uses) ] ee Ks) as Tag —s6 —aaa as Tae Tosa ns 120506 ~20108 “22135 6968 251 roms 20 so3s =s9197 ~2T4 8193 Lana 10839 Bs 339 Teens Ta omer 18 fois 20 eos on 20958 ers 42s 988.76 2s sss 36459 ~2oset 96167 te 05 250 11930 5545 ~20001 095550, sir 7559 250 so9757 08 =19891 nour ssi0 S801 2s tosis cms 1900 5000 ass 35770 m0 os “sige =19996 93s Lass0 225 20 tostos 29097 tite oozes ry yaa 2S toss ~29088 aim 924s Lat 15165 rt ‘58601 ~a.s 17456 sass age raat x0 558.70 “a0 1809 091689 13i86 en >is 98108 ~2248 =1691 foster gaz e331 310 smo “2076 16176 091301 968 64095 mo 0 Spas 15853 90073 3is6 ‘mas m5 299 21325 ~1s2as 090830, 3198 smisé 30 sh ams tana osm 2001 ssi78 a 1206 14639 090688 2019 3880 30 sat Tas os0si5 Ty son Ms 7017 1001 90560 20132 s0n.62 30 15498 =r ‘oss 20509 ast Pt ness = 1366 09087 20618 5595 0 onus mer’ Sons is? S331 380 sus} =ra0s9 oomis 2m pre 30 ‘9658 =11599 509 0173 0 6150 “ais =1hoss 89970 9099 20 0050 20317 “10136 0698 808 0 7848 mss -a97a00 oxsssi 3555 “0 816 104s? “osm 5000 sae 60 sta S000 oss x50 or = 5452 58593 82682 sais m4 0 ss 7783 “arose ssa sma ‘0 aesat sen S036 B06 moss 0 2st sis Tore s5en4 38192 05 52503 near ~0.0885 oom839| eka sso 50237 ms ~osnnss sion, 39590 a Ru rd Caste aor? wana 4 Phys. Chem, Ret. Data, Vol. 25, No.6, 1996ANEW EQUATION OF STATE FOR CARBON DIOXIDE 1585 ‘Hate. Themed pepe of on ide Contnet Femme “Deny —~—Cemeey——“Eatpy nop = s Syed e om) i} kg) gtk) a somd e 30.0 MPa ta = en ae mes oases asa ve ai es as 13222 moss “oasis agate ase ais ct ox aot fmm “esa sase tas haat es now a6 3036 Laws she a1939 mee sess Oss Lest tase 0 tasas saat “azn atest 13680 suas 00 ties isa oleae an sae fey rr an ams 107 13006 sans 00M ae mea —aie Tana wo98rs Tas 2 taa33 A399 cnn ane 93ean tas 2 ‘angst S100 Hama bits snes is 2 ine “oak Sms Th oon tye es eats 98s 36139 20808 eae Ua 0 Hse “ant Seas aoe 890056 ten as sis cae S305) “ass fessa0 ed ie Tess THs Sous Tish ‘soa tee des hoses S579 See -1900 fees Ue m 15093 Se3 Siesta oar i Bs linsse ord Css Lae oases 1399 13k 2s ts35 2156 ate) tH ‘nas (scat 30 nas Ssipst Sms Lime sas ss 2s toiai6 307 cme “ie oem tates 8 sa ad Te Chas Ooteas ist Mo wos 575 er) bo1ee ts as 008 a3 casa Lier fois Leet = mse “aes cee isa oto tie = seas “eat Sant “15 ‘nme fea BS rg ae cas 106 sani rr Mo unas Sas Ciwas Chae oasis sam i ea cae om 18 ‘90360 vaste eo 2s “ana His sis ons as05 » 1308, a8 finn Shan tone tsi io ra ci isa) “Lasts fso1n0 tsa sue io mse se “es “LB fomia tae sm ie 08 =isk32 76 Ls soos ry ins to S094 ay sas “hss tonto Ls 690 4: Phys Chom, Ret Data, Vo. 28, No 6,1961586 R. SPAN AND W. WAGNER ‘Tame 38. Themodynnic popes of carbon dxide—Contined ‘Tempeae ——Deasty—sInenal enya Erp a a ‘Spel ) aie (uae) (une) (uv Ky] ee KK] sa it) “OI Ma nar ary sas —oate ons Lani ‘oom e990 “996 “0 5098 “6.8 7506 098436 osa70 Less 07 “0 sar “3278 nee muss osmst 16123 218) ay ss —nor ss.6 ~basi22 oonsts issie as ‘0 a3 =a rossi “08952 oomni7 isa a6 500 45294 23559 35.959 081899 50882 1581 be 50 05 ss sae “osetia 191995 4013 sin a5 eos 09 928s 061959 oor? 13402 381 ao 560 nua 22576 ~0ssiKs 9360 13451 07 0 31136 toss als “oss ‘stor 1319 ‘an es ao ize Sasa “oasis 095957 1308 ‘sao 00 2429 21770 55840 035885 56810 lasts 97 0 2e mat asia “outs on 10 ose 0 21466 011 ies “oss? oss 13906 si 10% 3 25 ase 10210 osts me S598 00 i46t oa 57698 2676 osm 137 S15 mse? nT 07 ~ 005 ~2a37 rom Ts Teo 20 ait Msi = 2119 o9ms12 7 1308 as rams ar assa1 A238 098640 yes Moss ao vioea Thos 659 Tae osmis U6is 10882 2s histoe 00.13 =35199 2100s agra 19st tasea 20 hier9 err =oo ~20650 9609 17586 isto as hasear 356 34023 =20303 920 Hiss rows 20 haat “Asa a Tio bss tsi e210 bs hna6s0 S09 chan =i96009 99s Ls07 moa? m0 misas A588 31396 9201 ous 19500 bie ns om 321 15980 oso 17496 on os ons A339 conn = 13s sms? 1408 i610 20 vost 52526 =m97 = 10st ‘sm010 17502 605 bs 008 ais “rai “urs 91392 135007 we 2105 101467 301.98 25270 17168 092039 Lat ns 310 100035 “29392 2596 = 16388 09179 Ls 70.25 us 96597 258 “217 1608 sists Lass mo ms 957.10 260.88 1764 1.6055 991193, 127840 ast x0 a6 = =n? srs 091030 1s mak 35 ost =28397 200.10 =15503 ‘sa590| si 659 an ona Sais Cio. sted naar 7509 1a M5 909 =u L157 =15007 8 Hs0 fret 4 Phys, Chem, Rel. Dat, VoL 25, No.6, 1996ANEW EQUATION OF STATE FOR CARBON DIOXIDE 1587 “Tye 3. Themodyannic pope fern dxide—Contiaed Temper Densiy—Interal ergy Enalpy 7 ee ‘Sheet of « oie ake) (sk) (ase K)) eg A )——_sd i) WaT ~H032 =a Tras aos 17807 ear 603 =n =is632 =1426s ‘ss 17469 eet 61 ~i999 = 13858 Hiss seo tne 124s ‘962 18403 Hin ots, tse C0 Soane mau 16895 ~ 10421 ar ‘asa? tras s12 sas =15410 ~s70ns =123 suis HI0 ssa i958 1947 -es7 =12016 st 3970 son cos Hiss “Siu rd Sisonas orm po ous Hoss 36392 11216 ‘0s ry sis13 oom —s.068 9998 =r? 50612 Lape 0s? 2620 “e482 “3605s —LosTi oso 6190 511 58625 56968 nin 0976 asia ts 43000 50295 oon 3965 mossaTs oie ssi ane 5088 31396 S000 ~091230 091363 15333 ama ane 1456 1190 080939 oszi01 tas ars 6618 sows 53 Hour osm 14308 m3 5 3078 ws 180 “067907 assaio 180 7296 o fee Sat pik chao foaise tas 1532 os an 13535 29381 “osens —pasa4 13561 500 “ 5315.08 127 e002 ~ositsi 9574 13a 48300 os 38033 i987 31940 ~oasi01 096837 1330 5182 om waar cas 5254 ~o.4231 osm3ss 321s ws m0 Bs Siuae aan =n3159 ass 13068 Sine x0 oss ao 61833 00837 10347 ‘370 sur 10» 399 S157 ust onsias| 1.060 11e0 sss 100 2266 sizo8 es errs os es) 51578 7500 MPa abe Bae 1906 Ta008 = ~200 T0098 aire a tana Las7 Stat “22187 s0028 bos 0 taste ins 35022 is Soar uss 2S 121650, 10930 67 M21 our? hes 250 aosat “40138 “016 21098 stant 1406 255 oss 3350 =3308t “ore osmis 1206 x0 32 = 3866 Snr 22 Oou689 1010 2 is6a6 -sras a7 “ron 9612 vos x0 sna “008 30529 =19098 9563) tos Ds boast ey —29888 =o 093179 toa 20 13889 Ase as =i nisess tus as i224 M69? 29013 13a nose too80 20 111020 =n933 “178 =r woo ec3 ss ast =i Hagia ats ns mn 4. Phys. Chem. Ret. Dat, Vol 25, No.6, 18961500 co teem vesian me woe sos sa SPAN AND W. WAGNER ‘rte 35. Tema prope fbn deConin ee ae ec a ae a @ Cases 1868 16508 cae “ie ie Ee eae Ea “sa fae Ga 1S “lon. ~1sL as1010 15360 ean cme eS pan et ea 2S oes = Ue car ote Bo Poy Chem Ra. at, Vt. 25, No.8, 886‘A NEW EQUATION OF STATE FOR CARBON DIOXIDE 1589 “Tue 35, Memadynani ropes of eon owe Conia TTempeuue ——Dewaty dma nergy ——‘Empy Eno | © & ‘Speed of © aie) cy tune) gO] ] RG Ks ls) ro —0m ie ~aas 0087 119 nsi2i =a ~ 3492 2102 1.0087 Lasse 28637 Ha1674 3651 ais 55659 6778 nist Tan.07 =m sun e657 16705 12480 aos Haier 98383 es 12408 oan 20624 asmsi2 Lss73 ram36 38633 20509 osm 1612 118205 om 1990 195335 16599 nimss 36395 =19608 095913 ise 160.90 3659 1936 95508 97 ness M190 =155 3 1208 navas 3463 =r 94508 else niga om138 =1g07 a9 suis to9ea8 31299 1368 936) tase ings. 30534 =i sists 992 10791 “wen =1796 093386 3988 rosres 8 Ooi 1 se76 rote ams6 oss) 1 sa38 loses 2057 oz 10 os 25361 one ste rook 2 2078 sass S087 e880 23607 ose 15612 369.90 -ma sz 15537 513 ~20900 tome 15461 saat Hiss iaszass 15386 14a 1239 ‘saat issn wat 169.25 one 13237 mn =15635 sasa2 ie tans? That 2650 15082 700 13048 sar smi Las ann 2970 a9se sisst 10515 093157 vaste 7580 =o 7108 rose 93578 Lars m3 ~ersiz Sunk 10587 ‘93001 14688 55 138 “3261 53st “oer o9ui2 Lasse 15 Gran asm 7030 0886 95765 Least 0 oan sis 877 ~o79610 o9eu80 aT es um 0901 24098 73867 osmit Laois 4 Phys. Chem. Ret, Oats, Vo 25, No.6, 19961590 R. SPAN AND W. WAGNER ‘Thais 35. Thermodynamic popes of carbon doxsde—Contand TTemperme Demy —temal energy Etalpy py ee 5 ‘sped of «© gm) cae) wap (aris) YIN] sun a) 0000 MP oar os ‘ane E32 3103s Onaiss ra 13 eas 0 56093 16616 sasoe ~058138 snus 13160 68195 ca 96 mst B18 039900 ost sr 10 00 us 183 sie 023962 Loe 1380s 5125 1000 aoa sos? rs191 009737 hos sm 6239 00 57136 61785 awe onsis2 0931 13s srsa8 2000 MPa ar Tash has Tae —aaas ~aae Toa Ter aes 455 ass ~a3.09 =m099 “2214 oes 14096 ten Ey Hea ‘teas 309% Xen 1M iste tesa 2s 9811 20908 ~35897 “21697 oR 1590 08 a0 ras94 ana.08 Sinn =2400 ois 1386 1266 Bs nsL6t 39515 =n9.10 =2ino or sr uns 2s 16s43 aaa -ma37 20s 1.000 1566 bas 0 sas asst -2183 20076 ass 1608 brs bs Hamas Sens “mn ~20010 19539 5s Bsr sas 123379 38438 192.28 19493 0.99981 134 i333 310 608 “a7 ~18es7 19263 6735 13381 rato us iss “310s =17690 1997 9512 tsar bas Rs an cs Frets “18519 seat 15235 Das 0 19s “m1 ~istar Laos ass 15190 iraa Bs nis622 ~aan Husa 13059 oor 15146 bea 5 1333 301.38 =13132 = 17618 097539 1.5064 ini 350 6627 29528 = =i ost sons ia “0 sto oa 108s Hts osm 14850 mua a0 hista6 m9 67 “93996 18 fosmid ass0 hisz 330 rant 35598 700 crane sim ass uns 300 moat ~n4838 ~ 68265 A188 056555 Lass ses 00 9708 “ass = =r sais 14695 hao “10 109331 =20.9 SB —1 5083 146s 1263 0 tna =n Cant cha esse Hoos 60 10ss36 1946 “Sem 14358 97080 14339 10953 “0 tossae ia Rais raat osm Lawn 10m 40 Tossa =1019 2236 13099 osm aes 10692 470 ios 14391 32099 =130 9777 14367 10457 60 ‘9453 =1n385 607 =i 091607 4320 ros. 0 ome mins e758 = 13495 nor Lass 28s 305 942 80.086 13039 = 1693 98451 Latss: 9279 50 96 “soa 16s97 Loses paps 1120 mst S15 so974 21.088 20120 Lo 5559 165 soa

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

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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

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