The International Association for the Properties of Water and Steam

Doorwerth, The Netherlands September 2009 Revised Release on the IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use
©2009 International Association for the Properties of Water and Steam Publication in whole or in part is allowed in all countries provided that attribution is given to the International Association for the Properties of Water and Steam President: Dr. D. G. Friend Thermophysical Properties Division National Institute of Standards and Technology 325 Broadway Boulder, CO 80305-3328, USA Executive Secretary: Dr. R. B. Dooley Structural Integrity Associates, Inc. 2616 Chelsea Drive Charlotte, NC 28209, USA email: bdooley@structint.com This revised release replaces the corresponding release of 1996 and contains 18 pages, including this cover page. This release has been authorized by the International Association for the Properties of Water and Steam (IAPWS) at its meeting in Doorwerth, The Netherlands, 6-11 September, 2009, for issue by its Secretariat. The members of IAPWS are: Britain and Ireland, Canada, the Czech Republic, Denmark, France, Germany, Greece, Japan, Russia, and the United States of America, and associate members Argentina and Brazil, Italy, and Switzerland. The formulation provided in this release is recommended for general and scientific use; further details about the formulation can be found in an article “The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use” by W. Wagner and A. Pruß [1]. This formulation provides the most accurate representation of the thermodynamic properties of the fluid phases of water substance over a wide range of conditions available at the time this release was prepared. IAPWS also has a formulation intended for industrial use. This revised release is identical to the original release issued by IAPWS in 1996, except for o o inclusion of the calculated triple-point pressure, improved values for the coefficients n1 and n2 in Table 1 to match more accurately the arbitrary conventions for the zeros of energy and entropy. The improved coefficients produce slight changes in the numerical values of u, s, h, f, and g; other properties (and all measurable differences in properties) are unchanged. Minor editorial corrections have also been made, including corrections in the last digits of a few calculated values in Tables 6-8 and updates to references. In 2010, a reference for estimated uncertainties in enthalpy was added. Further information about this release and other releases issued by IAPWS can be obtained from the Executive Secretary of IAPWS or from http://www.iapws.org.

τ = Tc / T Note: T denotes absolute temperature on the International Temperature Scale of 1990. δ = ρ / ρc Isothermal throttling coefficient Dimensionless Helmholtz free energy.2 The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use 1 Nomenclature Thermodynamic quantities: B cp cv f h M p R Rm s T u w Second virial coefficient Specific isobaric heat capacity Specific isochoric heat capacity Specific Helmholtz free energy Superscripts o r ′ ″ Ideal-gas property Residual Saturated liquid state Saturated vapor state βs δ δT φ κT μ ρ τ Specific enthalpy Molar mass Pressure Subscripts Specific gas constant c critical point Molar gas constant σ saturation Specific entropy t triple point Absolute temperature Specific internal energy Speed of sound Isentropic throttling coefficient Reduced density. . φ = f /( RT ) Isothermal compressibility Joule-Thomson coefficient Mass density Inverse reduced temperature.

This equation is expressed in dimensionless form. (3) by about 1 part in 60 000. Due to the use of the specific gas constant. T ) = φ (δ . In order to convert values of specific properties to molar properties. Eq. (5). 3 The Formulation The formulation is a fundamental equation for the specific Helmholtz free energy f. (1) and (3). φ = f /(RT ).096 K ρc = 322 kg m–3 R = 0. which differ slightly from the accepted values of these quantities at the time this release was prepared. τ ) + φ r (δ .461 518 05 kJ kg–1 K–1 (1) (2) (3) The numerical values for the critical temperature Tc and critical density ρc are identical to those given in the IAPWS revised release on the critical parameters of ordinary water substance [2]. and is separated into two parts. Eq. (2). The use of the more recent values would yield a specific gas constant which is greater than the value given in Eq. τ ) .3 2 Reference Constants Tc = 647. (6). (4). ⎢ ⎥ ⎣ ⎦ i=4 o 8 (5) where δ = ρ /ρc and τ = Tc /T with ρc and Tc according to Eqs. (3) has been used in obtaining the coefficients in the residual part φ r . Tc and R given by Eqs. Since the value of R in Eq. an appropriate value for the molar mass should be used (see [5]). an ideal-gas part φ o and a residual part φ r . then this value of R must be used in obtaining property values from the formulation. so that : f ( ρ. RT where δ = ρ /ρc and τ = Tc /T with ρc. τ ) = φ o (δ . . The ideal-gas part φ o of the dimensionless Helmholtz free energy is obtained from an equation for the specific isobaric heat capacity in the ideal-gas state developed by Cooper [6] and reads: (4) φ = lnδ o o + n1 o + n2 τ o + n3 lnτ + ∑ nio ln ⎡1 − e −γ i τ ⎤ . Table 1 contains the coefficients and parameters of Eq. The value of the specific gas constant R is derived from values of the molar gas constant Rm [3] and the molar mass M [4]. Eq. (2) and (1). (4) corresponds to a mass-based formulation.

the specific internal energy and the specific entropy of the saturated liquid at the triple point have been set equal to zero. small changes in density along an isotherm cause large changes in pressure. where δ = ρ /ρc and τ = Tc /T with ρc and Tc according to Eqs. s ′ = 0. a particular computer code may fail to return the zeros in Eq. u ′ = 0 . Eq. (4) by using the appropriate combinations of the ideal-gas part φ o . Eq. and the residual part φ r . Thus. (7) for the saturated liquid density at the triple-point temperature. the constants o o n1 and n2 in Eq. (6) are listed in Table 2. The coefficients and parameters of Eq. t t (7) o o In order to meet this condition. (6). . t (8) In the liquid-water region. 4 Relations of Thermodynamic Properties to the Dimensionless Helmholtz Free Energy All thermodynamic properties can be derived from Eq. (4) yields pt = 611.16 K. (5) have been adjusted accordingly. Eq. (5). (7) more precisely.654 771 Pa. For this reason. due to an accumulation of small errors. (5) may be readjusted by imposing the condition u ′ = 0. If a user wants to reproduce the zeros of Eq.611 782 J kg−1. (4) yields for the specific enthalpy of the saturated liquid at the triple point: h′ = 0. at the triple-point1 temperature Tt = 273. As a consequence. s ′ = 0 with the t t desired accuracy. Since the 5th International Conference on the Properties of Steam in London in 1956. after calculating for Tt the saturated liquid density ρ ′t via the phase-equilibrium condition (see Table 3).4 The form of the residual part φ r of the dimensionless Helmholtz free energy is as follows: φ = r ∑ niδ i =1 7 di ti τ + ∑ niδ i =8 51 di ti −δ ci τ e + i = 52 ∑ niδ 1 54 di ti −α i ( δ − εi ) − βi (τ −γ i ) τ e 2 2 + i = 55 ∑ niΔb δψ i 56 (6) with 2 Δ = θ 2 + Bi ⎡( δ − 1) ⎤ ⎣ ⎦ ai 2 θ = (1 − τ ) + Ai ⎡( δ − 1) ⎤ 2βi ⎣ ⎦ ψ = e − Ci (δ −1) 2 − Di (τ −1) 2 . the coefficients n1 and n2 in Eq. of the dimensionless Helmholtz free energy and their derivatives. Relations between thermodynamic 1 The calculation of the triple-point pressure pt from Eq. (2) and (1).

the lowest temperature on the meltingpressure curve is 251. These features involve second order and higher derivatives of the dimensionless Helmholtz free energy and properties obtained from them. the formulation can also be extrapolated beyond the limits given under item (1). ( ) (2) In the stable fluid region. within a temperature range from 20 mK below Tc up to Tc. (4). ρ ′ and ρ ′′ . 5 Range of Validity IAPWS has tested the formulation and endorses its validity in the following way: (1) The formulation is valid in the entire stable fluid region of H2O from the melting-pressure curve [8] to 1273 K at pressures up to 1000 MPa. respectively. Although Eq. Eq. Eq.5 properties and φ o and φ r and their derivatives are summarized in Table 3. Note: IAPWS has issued the Supplementary Release on Saturation Properties of Ordinary Water Substance [7] containing a set of simple equations which yield values for the vapor pressure as well as the density. the properties calculated on the saturation curve are thermodynamically consistent with the properties of the single-phase region. (4) behaves reasonably when extrapolated to pressures up to about .566 MPa) [8]. the formulation also covers the liquid-vapor saturation curve. In this way. (4) represents the experimental data available at the time the release was prepared (except for very few data points) to within their uncertainties. (6) yields the thermal saturation properties pσ . In this entire region. For given saturation temperature and solving simultaneously the three equations of the phase-equilibrium condition (see Table 3) by iteration. In addition.5 mK above Tσ . all the other properties can be derived from Eq. the isochoric heat capacity cv exhibits a maximum and the speed of sound w exhibits a minimum not at the saturation temperature Tσ of the corresponding isochore (as it should be) but in the single-phase region up to 2. the isothermal compressibility κT κT = ρ −1 ( ∂ρ /∂ p )T and the specific isobaric heat capacity cp exhibit unphysical behavior which occurs in a region from Tc to 5 K above Tc for densities ± 0. see Fig. The values calculated from these equations are not identical with the corresponding values derived from Eq. Tests show that Eq. Then.5 % from ρc. Specifically. but agree with them within the uncertainties of the simple equations for the saturation properties. Besides the single-phase region. (4) is also in satisfactory agreement with the experimental data in the critical region. (4). All required derivatives of the ideal-gas part and of the residual part of the Helmholtz free energy are explicitly given in Table 4 and Table 5. the equation has some unsatisfactory features in the immediate vicinity of the critical point. 1.165 K (at 208. specific enthalpy and specific entropy of the saturated vapor and liquid.

an alternative equation (the so-called gas equation) is given in reference [1]. and in the enthalpy of vaporization are given in IAPWS Advisory Note No. (4) produces reasonable values close to the saturation line. attention must be paid to numerical problems. saturated liquid density. Equation (4) represents the currently available experimental data of the subcooled liquid (solid-liquid metastable region) and of the superheated liquid (liquid-gas metastable region) to within the experimental uncertainty. “tolerance” means the range of possible values as judged by IAPWS. no experimental data are available. in enthalpy differences in the single-phase region. In this region. The statement “no definitive uncertainty estimates possible” for the high-pressure region in Figs. 6 Estimates of Uncertainty Estimates have been made of the uncertainty of the density. This holds at least for the density and enthalpy of undissociated H2O. As used here. These estimates were derived from comparisons with the various sets of experimental data together with the judgement of the Working Group on Thermophysical Properties of Water and Steam of IAPWS. Eq. In the gas region at pressures below the triple-point pressure. (4) behaves reasonably when extrapolated to the sublimation-pressure curve [8] for temperatures down to 200 K. the formulation behaves reasonably when extrapolated into the metastable regions. 1 to 3. For the single-phase region. Eq. 2 and 3. (3) As far as can be tested with experimental data. speed of sound. Estimated uncertainties in enthalpy. and isobaric heat capacity when calculated from the formulation. . 4. 1 [9]. which give the estimated uncertainties in various areas. In the case of the subcooled gas (gas-liquid metastable region). For calculations further away from the saturation line. Eq. (4). it should be noted that the uncertainties for these properties increase drastically when approaching the critical point. and saturated vapor density are shown in Fig. the estimates of the uncertainties of vapor pressure. For further details see reference [1]. Due to the extremely low densities in this region which go down to about 10−6 kg m−3. For the saturation properties. 2 and 3 is based on the lack of experimental data in this region. and no statistical significance can be attached to it.6 100 GPa and temperatures up to about 5000 K. for pressures below 10 MPa. these tolerances are indicated in Figs. With regard to the uncertainty for the speed of sound and the specific isobaric heat capacity. see Figs.

[7] IAPWS. 783-787 (1993). Representation of the Ideal-Gas Thermodynamic Properties of Water.7 7 Computer-Program Verification To assist the user in computer-program verification. specific enthalpy h″ and specific entropy s″ for the saturated vapor. Using Macroscopic Quantum Phase Coherence in Superconductors: Implications for Quantum Electrodynamics and the Fundamental Physical Constants. B. [5] IAPWS. and Langenberg. Data 31. Revised Release on the Pressure along the Melting and Sublimation Curves of Ordinary Water Substance (2008).. Effects of Isotopic Composition. [2] IAPWS. J. H. Phys.org.. Revised Supplementary Release on Saturation Properties of Ordinary Water Substance (1992). Available from http://www. J. [8] IAPWS.. and Density of Ordinary and Heavy Water Substances at Their Respective Critical Points (1992). (4) by using the phase-equilibrium condition (see the corresponding comment in Section 4). G. 8 References [1] Wagner. values for the density ρ ′ . Available from http://www.iapws. and Pruß. 3. 375-496 (1969). International Equations for the Saturation Properties of Ordinary Water Substance – Revised According to the International Temperature Scale of 1990. 1: Uncertainties in Enthalpy for the IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use (IAPWS95) and the IAPWS Industrial Formulation 1997 for the Thermodynamic Properties of Water and Steam (IAPWS-IF97) (2003). 387-535 (2002). Guideline on the Use of Fundamental Physical Constants and Basic Constants of Water (2001). Available from http://www.iapws. Mod.. T. Phys. W. R. Riethmann.. Feistel. Rev. [3] Taylor. J. S. Table 6 contains values of the ideal-gas part φ o and the residual part φ r of the dimensionless Helmholtz free energy together with the corresponding derivatives.. and the specific entropy s calculated at selected values of temperature T and density ρ . Pressure. J. H.org. R. W. Ref. and values for the density ρ ′′ .. Table 8 gives values for the vapor pressure pσ . and Harvey. Chem. W.iapws.iapws.. Release on the Values of Temperature. See also Wagner. Data 6. Chem. [9] IAPWS Advisory Note No. [6] Cooper. Ref.. and Dissolved Gases on the Density of Liquid Water. The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use. Phys. W. Available from http://www. Parker. Chem.iapws.. D. and Pruß. Phys. N. Data 22. Int. Thermophys. A. A. Phys. 41... three tables with test values are given. Temperature. the speed of sound w.org. All these saturation values have been calculated with Eq. specific enthalpy h′ and specific entropy s′ for the saturated liquid. 1109-1131 (1977). Determination of e / h.org . 35-43 (1982). to be submitted to J. the specific isochoric heat capacity cv. Chem. [4] Kell.org. Available from http://www. See also Wagner. N. A.. Ref. Ref. Data. Table 7 lists values for the pressure p. J. Pressure.

287 289 67 i 5 6 7 8 nio 0.969 56 0.320 446 483 749 7 6.012 436 γ io – – – 1.244 377 96 27.006 32 0.248 73 γ io 3.683 210 527 593 2 3. (5) i 1 2 3 4 nio –8.537 342 22 7. Numerical values of the coefficients and parameters of the ideal-gas part of the dimensionless Helmholtz free energy.279 50 0. Eq.507 510 5 .8 Table 1.740 737 08 9.973 15 1.

257 090 430 034 38 0.21 1.5 0.875 1 0.5 bi 0.199 057 183 544 08 0.75 0.204 338 109 509 65 –4 –0.562 509 793 518 88 × 10 –4 –0.132 511 800 746 68 × 10 –9 –0.136 364 351 103 43 –1 0.318 025 093 454 18 –0.626 897 104 146 85 × 10 –9 –0.386 150 855 742 06 × 10 –1 –0.107 936 009 089 32 –1 0.118 411 824 259 81 –1 i 52 53 54 ci – – – di 3 3 3 ti 0 1 4 –0.743 159 297 103 41 0.221 322 951 675 46 –0. (6) i 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 ci – – – – – – – 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 3 3 3 3 4 6 6 6 6 di 1 1 1 2 2 3 4 1 1 1 2 2 3 4 4 5 7 9 10 11 13 15 1 2 2 2 3 4 4 4 5 6 6 7 9 9 9 9 9 10 10 12 3 4 4 5 14 3 6 6 6 ti –0.436 136 157 238 11 × 10 –1 0.252 131 543 416 95 × 10 ni αi 20 20 20 βi 150 150 250 γi 1.313 587 007 125 49 × 10 –0.199 555 719 795 41 × 10 –3 0.160 748 684 862 51 –1 –0.261 455 338 593 58 –2 –0.3 0.192 327 211 560 02 –0.878 032 033 035 61 × 10 0.880 894 931 021 34 × 10 –0.349 940 054 637 65 × 10 –1 –0.148 746 408 567 24 0.21 1.375 1 4 6 12 1 5 4 2 13 9 3 4 11 4 13 1 7 1 9 10 10 3 7 10 10 6 10 10 1 2 3 4 8 6 9 8 16 22 23 23 10 50 44 46 50 ni 0.557 111 185 656 45 × 10 –0.393 434 226 032 54 × 10 –5 –0.141 806 344 006 17 × 10 –2 0.9 Table 2.499 691 469 908 06 × 10 –1 –0.781 997 516 879 81 × 10 –2 0.833 265 048 807 13 × 10 –1 –0.5 0.205 279 408 959 48 × 10 –0.365 821 651 442 04 × 10 –11 –0.789 576 347 228 28 × 10 1 –0.478 073 299 154 80 –1 0.315 461 402 377 81 × 102 4 –0.313 062 603 234 35 × 102 0.165 540 500 637 34 × 10 –2 0.156 086 522 571 35 × 10 –8 0.317 774 973 307 38 –0.203 934 865 137 04 × 10 –2 –0.3 .318 061 108 784 44 Ci 28 32 Di 700 800 Ai 0.668 565 723 079 65 0.662 126 050 396 87 × 10 –0.163 885 683 425 30 × 10 –1 0.32 0.626 395 869 124 54 × 10 –0.580 833 999 857 59 –2 0.2 ni –0.5 3.767 881 978 446 21 × 10 –1 0.125 335 479 355 23 × 10 1 0.224 462 773 320 06 × 10 –4 –0.25 εi 1 1 1 i 55 56 ai 3.290 523 360 095 85 × 10 –1 0. Numerical values of the coefficients and parameters of the residual part of the dimensionless Helmholtz free energy.158 703 083 241 57 × 10 –4 –0.95 Bi 0.2 0.759 413 770 881 44 × 10 –3 0.85 0.400 928 289 258 07 × 10 –6 0. Eq.402 476 697 635 28 0.115 379 964 229 51 × 10 –6 0.176 114 910 087 52 × 10 0.32 βi 0.

τ ) r r = 1 + 2δφδ + δ 2φδδ − o r RT τ 2 φττ + φττ ( ) 2 Isothermal throttling coefficient δT = ( ∂h /∂ p )T r r 1 + δφδ − δτφδτ Isentropic temperaturepressure coefficient β s = ( ∂T /∂ p ) s βs ρ R = r (1 + δφδr − δτφδτ ) 2 o r r r − τ 2 φττ + φττ 1 + 2δφδ + δ 2φδδ ( )( ) Second virial coefficient B (T ) = lim ∂ ( p /( ρ RT ) ) /∂ρ ( ρ →0 )T r B (τ ) ρc = lim φδ ( δ . φτ = ⎢ ⎥ ττ ⎢ ∂τ ⎥δ ⎢ ∂δ ⎥τ ⎣ ⎦ ⎣ ⎦ . τ ) o r = τ φτ + φτ − φ o − φ r R ( Enthalpy h = f − T ( ∂ f /∂T ) ρ + ρ ( ∂ f /∂ρ )T h (δ . φττ = ⎢ 2 ⎥ . τ ) − φ ( δ ′′. φ r = ⎢ 2 ⎥ . pσ r = 1 + δ ′′φδ ( δ ′′. τ ) RT ρ ′ . φτ = ⎢ ∂ τ ⎥δ ⎢ ∂ δ ∂τ ⎥ ⎣ ⎦ ⎣ ⎦ ⎡ ∂ 2φ o ⎤ ⎡ ∂φ o ⎤ o ⎢ ⎥ . τ ) ⎠ ⎝ ⎠ RT ⎝ ⎡ ∂ 2φ r ⎤ ⎡ ∂ 2φ r ⎤ o r ⎢ 2 ⎥ . τ ) ( ∂ f /∂ρ )T ρ RT r = 1 + δφδ Internal energy Entropy u = f − T ( ∂ f /∂T ) ρ u (δ . τ ) R c p (δ . τ ) RT ρ ′′ pσ ⎛ 1 ⎛ ρ′ ⎞ 1⎞ r r ⎜ ρ ′′ − ρ ′ ⎟ − ln ⎜ ρ ′′ ⎟ = φ ( δ ′. τ ) R ( ) ) r (1 + δφδr − δτφδτ ) + 2 r r 1 + 2δφδ + δ 2φδδ Isobaric heat capacity c p = ( ∂h /∂T ) p o r = −τ 2 φττ + φττ ( Speed of sound w = ( ∂ p/∂ρ ) s 1/ 2 Joule-Thomson coefficient μ = ( ∂T /∂ p ) h ) r r r − ( δφδ + δ 2φδδ + δτφδτ ) μ Rρ = r 2 o r r (1 + δφδr − δτφδτ ) − τ 2 (φττ + φττ ) (1 + 2δφδr + δ 2φδδ ) ( δT ρ = 1 − r r 1 + 2δφδ + δ 2φδδ r r 1 + δφδ − δτφδτ r r 1 + δφδ − δτφδτ w2 ( δ . τ ) RT o r r = 1 + τ φτ + φτ + δφδ o r = −τ 2 φττ + φττ ( ) Isochoric heat capacity cv = ( ∂u /∂T ) ρ cv ( δ .10 Table 3. τ ) δ →0 Third virial coefficient ⎡1 C (T ) = lim ⎢ ∂ 2 ( p/( ρ RT ) ) /∂ρ 2 ρ→0 ⎣ 2 ( ) ⎤ T⎥ ⎦ Phase-equilibrium condition (Maxwell criterion) pσ r = 1 + δ ′φδ ( δ ′. τ ) o r = τ φτ + φτ RT ( ) ) s = − ( ∂ f /∂T ) ρ s( δ . τ ) δ →0 2 r C (τ ) ρc = lim φδδ ( δ . φδτ = ⎢ ⎥ . Relations of thermodynamic properties to the ideal-gas part φ o and the residual part φ r of the dimensionless Helmholtz free energy and their derivativesa Property Pressure p=ρ 2 Relation p (δ . ⎢ ∂τ ⎥ δ ⎢ ∂τ ⎥δ ⎣ ⎦ ⎣ ⎦ r a φ r = ⎡ ∂φ ⎤ . φ r = ⎢ ⎥ δ δδ ⎢ ∂δ ⎥τ ⎣ ⎦ r ⎡ ∂ 2φ r ⎤ r ⎡ ∂φ ⎤ .

φ o = ⎡ ∂φ ⎤ . φ o = ⎡ ∂ φ ⎤ . φ o = ⎡ ∂ φ ⎤ .11 Table 4. φ o = ⎡ ∂ φ ⎤ . ⎢ 2 ⎥ ⎢ 2 ⎥ ⎢ ⎥ τ ττ ⎢ ∂δ ⎥ ⎢ ∂τ ⎥ δ δδ δτ ⎣ ⎦τ ⎣ ⎦δ ⎣ ∂δ ⎦τ ⎣ ∂τ ⎦ δ ⎣ ∂δ ∂τ ⎦ . The ideal-gas part φ o of the dimensionless Helmholtz free energy and its derivativesa φo o φδ = = lnδ + + + + + + o n1 + o n2 τ + o n3 lnτ + + + + i=4 ∑ nio ln 1 − e−γ τ 8 ( o i ) ) 1/δ 0 0 0 0 0 + + + + + 0 0 o n2 + + + – + 0 0 o n3 / τ o n3 0 0 o ⎡ ∑ nioγ io ⎢ 1 − e−γ i τ ⎣ i=4 o φδδ = o φτ − 1/δ 2 0 0 0 8 = = ( −1 φττ o 0 0 /τ 2 – + i=4 ∑ 8 nio ( ) 2 o γ io e −γ i τ (1 − e−γ τ )−2 o i ⎤ − 1⎥ ⎦ o φδτ = 0 0 o 2 o o 2 o 2 o a φ o = ⎡ ∂ φ ⎤ .

2 Table 5. The residual part φ r of the dimensionless Helmholtz free energy and its derivativesa φ r = ∑ niδ di τ ti + ∑ niδ di τ ti e −δ + ∑ niδ di τ ti e i =1 i =8 i = 52 7 51 ci 54 − α i ( δ − ε i ) − βi ( τ − γ i ) 2 2 + i = 55 ∑ 56 ni Δ bi δψ 2 2 with Δ =θ + Bi ⎡( δ − 1) ⎤ ⎣ ⎦ ai 1 2 θ = (1 − τ ) + Ai ⎡( δ − 1) ⎤ 2βi ⎣ ⎦ 2 2 ψ = e − Ci (δ −1) − Di (τ −1) ci φδr = ∑ ni diδ di −1τ ti + ∑ ni e−δ ⎡δ di −1τ ti di − ciδ ci ⎤ + ∑ niδ diτ ti e−αi (δ −ε i ) ⎣ ⎦ 7 51 i =1 7 i =8 ( ) 54 2 − βi (τ −γ i ) ci r φδδ = ∑ ni di ( di − 1) δ di −2τ ti + ∑ ni e−δ ⎡δ di −2τ ti ⎢ 51 i =1 i =8 ⎣ (( d − c δ )( d − 1 − c δ ) − c δ ) i i ci i i ci 2 ci i i =52 ⎤ ∂ψ ⎞ ∂Δbi ⎡ di ⎤ 56 ⎡ ⎛ δψ ⎥ − 2α i (δ − ε i )⎥ + ∑ ni ⎢ Δ bi ⎜ψ + δ ⎟+ ⎢δ ∂δ ⎠ ∂δ ⎣ ⎦ i =55 ⎢ ⎝ ⎥ ⎣ ⎦ 54 2 2 −α δ −ε − β τ −γ ⎤+ ∑ n τ ti e i ( i ) i ( i ) ⎥ i =52 i ⎦ 2 bi 2 2 bi 56 ⎡ ⎛ ⎤ ⎞ ⎡ −2α δ di + 4α 2δ di (δ − ε )2 − 4d α δ di −1 (δ − ε ) + d ( d − 1) δ di −2 ⎤ + ∑ n ⎢ Δ bi ⎜ 2 ∂ψ + δ ∂ ψ ⎟ + 2 ∂Δ ⎛ψ + δ ∂ψ ⎞ + ∂ Δ δψ ⎥ ⋅⎢ i i i i i i i i i ⎜ ⎟ ⎥ ⎣ ⎦ i =55 ⎢ ⎜ ∂δ ∂δ ⎠ ∂δ 2 ∂δ ⎝ ∂δ 2 ⎟ ⎥ ⎠ ⎣ ⎝ ⎦ φτ = ∑ ni tiδ τ i =1 7 r 7 di ti −1 + ∑ ni tiδ τ i =8 51 di ti −1 −δ ci e + i =52 ∑ 54 −α δ −ε − β τ −γ niδ diτ ti e i ( i ) i ( i ) 2 2 ⎡ ti ⎤ 56 − 2β i (τ − γ i )⎥ + ∑ niδ ⎢τ ⎣ ⎦ i =55 2 ⎡ ∂Δbi ∂ψ ⎤ ψ + Δbi ⎢ ⎥ ∂τ ⎥ ⎢ ∂τ ⎣ ⎦ r φττ = ∑ ni ti ( ti − 1) δ diτ ti −2 + ∑ ni ti ( ti − 1) δ diτ ti −2e−δ + ∑ niδ diτ ti e−αi (δ −ε i ) ci 51 54 − βi (τ −γ i ) 2 i =1 i =8 i =52 2 ⎡⎛ t ⎤ t ⎞ i − 2βi (τ − γ i ) ⎟ − i2 − 2βi ⎥ ⎢⎜ ⎠ τ ⎢⎝ τ ⎥ ⎣ ⎦ + 7 ⎡ ∂ 2 Δbi ∂Δbi ∂ψ ∂ 2ψ ⎤ + Δbi ψ +2 niδ ⎢ ⎥ ∑ 2 ∂τ ∂τ ∂τ 2 ⎥ ⎢ ∂τ i =55 ⎣ ⎦ 56 51 r φδτ = ∑ ni ditiδ di −1τ ti −1 + ∑ ni tiδ di −1τ ti −1 di − ciδ ci e−δ + ∑ niδ diτ ti e−αi (δ −ε i ) ci i =1 i =8 ( ) 54 2 − βi (τ −γ i ) 2 i =52 ⎡ di ⎤ ⎡ ti ⎤ ⎢ δ − 2α i (δ − ε i )⎥ ⎢ τ − 2βi (τ − γ i )⎥ ⎣ ⎦⎣ ⎦ + ⎡ ⎛ ∂ψ ∂2 ψ +δ ni ⎢ Δ bi ⎜ ∑ ⎜ ∂δ ∂τ i =55 ⎢ ⎣ ⎝ ∂τ 56 ⎞ ∂Δbi ∂ψ ∂Δ bi +δ + ⎟ ⎟ ∂δ ∂τ ∂τ ⎠ ⎤ ∂ψ ⎞ ∂ 2 Δ bi ⎛ δψ ⎥ ψ +δ ⎜ ⎟+ ∂δ ⎠ ∂δ ∂τ ⎝ ⎥ ⎦ .

Continued Derivatives of the distance function Δbi: ∂Δbi ∂δ ∂ 2 Δbi ∂δ 2 Derivatives of the exponential function ψ : ∂ψ ∂δ ∂ 2ψ ∂δ ∂ψ ∂τ ∂τ 1 −1 2 βi 2 = bi Δbi −1 ∂Δ ∂δ = − 2 C i (δ − 1 )ψ = 2 C i (δ − 1 ) − 1 2 C iψ 2 2 ⎧ ∂ 2Δ ⎪ ⎪ ⎛ ∂Δ ⎞ ⎫ = bi ⎨Δbi −1 2 + ( bi − 1) Δ bi −2 ⎜ ⎟ ⎬ ∂δ ⎝ ∂δ ⎠ ⎪ ⎪ ⎩ ⎭ { { } ∂Δbi = −2θ bi Δbi −1 ∂τ ∂ 2 Δbi ∂τ 2 = − 2 D i (τ − 1 )ψ 2 = 2bi Δ bi −1 + 4 θ bi ( bi − 1) Δ 2 bi − 2 ∂ 2ψ = 2 D i (τ − 1 ) − 1 2 D iψ 2 } ∂ 2 Δbi 2 2 = − Ai bi Δbi −1 (δ − 1) ⎡(δ − 1) ⎤ ⎣ ⎦ βi ∂δ ∂τ ∂Δ − 2θ bi ( bi − 1) Δbi −2 ∂δ ∂ 2ψ = 4 C i D i (δ − 1 )(τ − 1 )ψ ∂δ ∂τ with 1 ⎧ ⎫ ∂Δ 2 ⎡ ⎪ 2 ⎤ 2 β −1 2 ai −1 ⎪ i δ − 1) = (δ − 1) ⎨ Aiθ + 2 Bi ai ⎡ (δ − 1) ⎤ ( ⎬ ⎦ ⎣ ⎦ βi ⎣ ∂δ ⎪ ⎪ ⎩ ⎭ ⎧ 2 a −2 1 ∂Δ ∂ Δ 2⎪ ⎡(δ − 1)2 ⎤ i + 2 A2 ⎛ 1 ⎞ = + (δ − 1) ⎨ 4 Bi ai ( ai − 1) ⎟ i ⎜ ⎣ ⎦ ∂δ 2 (δ − 1) ∂δ ⎝ βi ⎠ ⎪ ⎩ 2 1 ⎫ ⎞⎡ 4 ⎛ 1 2 ⎤ 2 β −2 ⎪ i − 1 (δ − 1) + Ai θ ⎬ ⎦ βi ⎜ 2 βi ⎟ ⎣ ⎝ ⎠ ⎪ ⎭ 1 ⎧ ⎫ ⎪⎡ 2 ⎤ 2 β −1 ⎪ i ⎨ ⎣(δ − 1) ⎦ ⎬ ⎪ ⎪ ⎩ ⎭ 2 a r φδ = ⎢ ⎡ ∂φ r ⎤ ⎡ ∂ 2φ r ⎤ ⎡ ∂φ r ⎤ ⎡ ∂ 2φ r ⎤ ⎡ ∂ 2φ r ⎤ r r r r ⎥ . φδτ = ⎢ ⎥. φττ = ⎢ 2 ⎥ . φδδ = ⎢ 2 ⎥ .3 Table 5. φτ = ⎢ ⎥ . ⎢ ∂δ ⎥τ ⎢ ∂δ ⎥τ ⎢ ∂τ ⎥δ ⎢ ∂τ ⎥δ ⎢ ∂δ ∂τ ⎥ ⎣ ⎦ ⎣ ⎦ ⎣ ⎦ ⎣ ⎦ ⎣ ⎦ .

255 071 625 × 104 0.241 200 877 × 10 0.435 000 0 0. by applying the phaseequilibrium condition (Maxwell criterion).100 530 8 × 10 500 0.201 933 608 × 10 4 4 4 3 3 4 4 3 3 3 4 s/(kJ kg–1 K–1) 0.166 991 025 × 10 0.698 451 167 × 10–3 0.147 637 878 1 1 = – 0.550 664 919 × 10–2 0.453 200 0 × 10 0.358 000 0 × 10 0. Eq.932 203 564 0. Eq.193 510 526 × 10 0.307 437 693 × 10 0.916 653 194 × 10 0.220 384 756 × 10 0.999 938 125 0.393 062 643 0. For this reason.200 000 690 × 10 0.150 817 541 × 10 0.244 357 992 × 10 0. Table 8. a particular computer code or a particular PC may fail to reproduce the pressure value with nine significant figures.175 890 657 × 10 0.127 128 441 × 10 0.342 693 206 × 10 = – 0.169 082 693 × 102 0.406 798 347 × 10 0. .417 223 802 × 10 1 1 1 1 1 1 1 1 0.346 135 580 × 10 0.618 315 728 × 10 0.203 237 509 × 10 0. Eq.204 797 733 × 10 0.999 679 423 × 10 1 3 4 3 –1 2 3 –1 a cv /(kJ kg K ) 0.660 921 221 × 101 T = 625 K 0.118 290 280 × 103 0.526 150 0 × 10 0.775 972 202 × 101 0.266 422 350 × 10 1 1 1 1 1 1 1 1 1 1 1 –1 –1 w/(m s–1) 0.384 236 747 0. due to an accumulation of small errors.870 769 0 × 10 0.200 022 515 × 10 0.890 341 250 × 103 0.700 004 704 × 10 0.025 kg m–3 φo o φδ o φδδ o φτ o φττ o φδτ = = = 0.256 690 919 × 10 0.223 440 737 × 10 = – 0. φ o φr r φδ r φδδ r φτ r φττ r φδτ and = – 0.150 151 914 × 10 0.252 145 078 × 10 0. (5). and for the residual part φ r .700 000 405 × 10 0.193 249 185 × 10 = 0 a For the abbreviated notation of the derivatives of 5.794 488 271 × 10 0.413 018 112 × 10 0.481 200 360 × 101 0.432 092 307 × 10 0.380 194 683 × 101 0.581 403 435 × 10 = – 0.168 626 976 × 104 0.241 000 0 0.838 025 0 × 10 0. (4).700 000 006 × 10 2 3 2 2 3 2 3 a In the liquid-water region at low pressures small changes in density along an isotherm cause large changes in pressure.548 314 253 × 10 0.210 865 845 × 101 0.698 445 674 × 10 0.364 366 650 = 0.322 106 219 × 10 0.910 660 121 × 101 T = 450 K 0.535 739 001 × 10 0.682 502 725 × 10 0.153 492 501 × 10 0.14 Table 6.724 027 147 × 10 0.112 176 915 × 10 r 1 1 1 1 φ see the footnotes of Tables 4 and Table 7. Values for the ideal-gas part φ o .387 405 401 0.283 094 670 × 10–1 0.132 609 616 0.277 441 078 × 104 0.659 070 225 × 10 0.999 887 406 × 103 0.100 003 858 × 10 0.250 428 995 × 104 0. Thermodynamic property values in the single-phase region for selected values of T and ρ T/K 300 ρ / (kg m–3) 0. Thermodynamic property values in the two-phase region for selected values of temperaturea T = 275 K pσ /MPa ρ ′ / (kg m–3) ρ ′′ / (kg m–3) h′/(kJ kg–1) h″/(kJ kg –1) s′/(kJ kg–1 K–1) s″/(kJ kg–1 K–1) 0.749 161 585 × 103 0.567 090 385 × 103 0.518 506 121 × 101 a All these test values were calculated from the Helmholtz free energy. respectively.856 063 701 = – 0.100 062 559 0.118 820 2 × 10 3 4 4 p/MPa 0.996 556 0 × 10 0.992 418 352 × 10 0. of the dimensionless Helmholtz free energy together with the corresponding derivativesa for T = 500 K and ρ = 838.904 611 106 × 10 1 = – 0.108 456 4 × 10 647 900 0. (6).

In the enlarged critical region (triangle). Δ p /p. The positions of the lines separating the uncertainty regions are approximate.15 Fig. estimated for Eq. Uncertainties in density. the uncertainty is given as percentage uncertainty in pressure. 1. . (4). This region is bordered by the two isochores 527 kg m−3 and 144 kg m−3 and by the 30 MPa isobar. Δ ρ /ρ.

estimated for Eq. see the remark in Section 6. . (4). see Fig.16 Fig. 1. Uncertainties in speed of sound. Δ w/w. For the uncertainty in the triangle around the critical point. for the definition of this region. The positions of the lines separating the uncertainty regions are approximate. 2.

3. for the definition of the triangle around the critical point. see the remark in Section 6. see Fig. (4). For the uncertainty in the immediate vicinity of the critical point. 1. estimated for Eq. The positions of the lines separating the uncertainty regions are approximate. Δ cp /cp.17 Fig. . Uncertainties in specific isobaric heat capacity.

in saturated liquid density.18 Fig. Uncertainties in vapor pressure. estimated for Eq. . Δ pσ /pσ . Δ ρ ″/ρ ″. 4. and in saturated vapor density. Δ ρ ′ /ρ ′ . (4).

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