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.

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. 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.

τ ) . φ = f /(RT ). (1) and (3). (3) has been used in obtaining the coefficients in the residual part φ r . The use of the more recent values would yield a specific gas constant which is greater than the value given in Eq. τ ) = φ o (δ . RT where δ = ρ /ρc and τ = Tc /T with ρc. ⎢ ⎥ ⎣ ⎦ i=4 o 8 (5) where δ = ρ /ρc and τ = Tc /T with ρc and Tc according to Eqs. 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 ⎤ . (4) corresponds to a mass-based formulation. Tc and R given by Eqs. so that : f ( ρ. an ideal-gas part φ o and a residual part φ r . . In order to convert values of specific properties to molar properties. Since the value of R in Eq. (2) and (1). (4). Due to the use of the specific gas constant.096 K ρc = 322 kg m–3 R = 0.461 518 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]. 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]. an appropriate value for the molar mass should be used (see [5]). τ ) + φ r (δ . (5). Eq. Table 1 contains the coefficients and parameters of Eq. (6). then this value of R must be used in obtaining property values from the formulation. T ) = φ (δ . 3 The Formulation The formulation is a fundamental equation for the specific Helmholtz free energy f.3 2 Reference Constants Tc = 647. and is separated into two parts. Eq. Eq. which differ slightly from the accepted values of these quantities at the time this release was prepared. (3) by about 1 part in 60 000. (2). This equation is expressed in dimensionless form.

(6). (7) more precisely. u ′ = 0 . Eq. the specific internal energy and the specific entropy of the saturated liquid at the triple point have been set equal to zero. Relations between thermodynamic 1 The calculation of the triple-point pressure pt from Eq. If a user wants to reproduce the zeros of Eq. As a consequence. Since the 5th International Conference on the Properties of Steam in London in 1956. 4 Relations of Thermodynamic Properties to the Dimensionless Helmholtz Free Energy All thermodynamic properties can be derived from Eq.16 K. t t (7) o o In order to meet this condition. (5) may be readjusted by imposing the condition u ′ = 0.654 771 Pa. Eq. The coefficients and parameters of Eq. Eq. (5). Thus. after calculating for Tt the saturated liquid density ρ ′t via the phase-equilibrium condition (see Table 3). the coefficients n1 and n2 in Eq. due to an accumulation of small errors. s ′ = 0 with the t t desired accuracy. a particular computer code may fail to return the zeros in Eq.611 782 J kg−1. s ′ = 0. where δ = ρ /ρc and τ = Tc /T with ρc and Tc according to Eqs. (2) and (1). (4) yields for the specific enthalpy of the saturated liquid at the triple point: h′ = 0. of the dimensionless Helmholtz free energy and their derivatives. the constants o o n1 and n2 in Eq. and the residual part φ r . at the triple-point1 temperature Tt = 273. (7) for the saturated liquid density at the triple-point temperature. . (4) yields pt = 611. t (8) In the liquid-water region. (6) are listed in Table 2. (5) have been adjusted accordingly. small changes in density along an isotherm cause large changes in pressure. (4) by using the appropriate combinations of the ideal-gas part φ o . For this reason.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 .

Eq. 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. (4) represents the experimental data available at the time the release was prepared (except for very few data points) to within their uncertainties. These features involve second order and higher derivatives of the dimensionless Helmholtz free energy and properties obtained from them. Eq. 1. Then. but agree with them within the uncertainties of the simple equations for the saturation properties. the formulation also covers the liquid-vapor saturation curve. In addition.566 MPa) [8]. In this way. the equation has some unsatisfactory features in the immediate vicinity of the critical point. see Fig.5 mK above Tσ . the formulation can also be extrapolated beyond the limits given under item (1). In this entire region. Although Eq. ( ) (2) In the stable fluid region. 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. (4) behaves reasonably when extrapolated to pressures up to about . (4). the lowest temperature on the meltingpressure curve is 251.5 properties and φ o and φ r and their derivatives are summarized in Table 3. ρ ′ and ρ ′′ . 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. For given saturation temperature and solving simultaneously the three equations of the phase-equilibrium condition (see Table 3) by iteration. the properties calculated on the saturation curve are thermodynamically consistent with the properties of the single-phase region. Tests show that 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 2.5 % from ρc. within a temperature range from 20 mK below Tc up to Tc. specific enthalpy and specific entropy of the saturated vapor and liquid. The values calculated from these equations are not identical with the corresponding values derived from Eq. (6) yields the thermal saturation properties pσ . respectively. Specifically. (4). (4) is also in satisfactory agreement with the experimental data in the critical region.165 K (at 208. Besides the single-phase region. all the other properties can be derived from Eq. 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.

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

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

740 737 08 9.248 73 γ io 3.537 342 22 7.973 15 1. Numerical values of the coefficients and parameters of the ideal-gas part of the dimensionless Helmholtz free energy.244 377 96 27.969 56 0.006 32 0. Eq.507 510 5 .287 289 67 i 5 6 7 8 nio 0.279 50 0.012 436 γ io – – – 1.8 Table 1.320 446 483 749 7 6.683 210 527 593 2 3. (5) i 1 2 3 4 nio –8.

204 338 109 509 65 –4 –0. Eq.95 Bi 0.668 565 723 079 65 0.2 ni –0.315 461 402 377 81 × 102 4 –0.400 928 289 258 07 × 10 –6 0.318 061 108 784 44 Ci 28 32 Di 700 800 Ai 0.148 746 408 567 24 0.562 509 793 518 88 × 10 –4 –0.192 327 211 560 02 –0.224 462 773 320 06 × 10 –4 –0.199 057 183 544 08 0.261 455 338 593 58 –2 –0.499 691 469 908 06 × 10 –1 –0.5 bi 0.25 εi 1 1 1 i 55 56 ai 3. Numerical values of the coefficients and parameters of the residual part of the dimensionless Helmholtz free energy.163 885 683 425 30 × 10 –1 0.580 833 999 857 59 –2 0.158 703 083 241 57 × 10 –4 –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 –0.257 090 430 034 38 0.176 114 910 087 52 × 10 0.878 032 033 035 61 × 10 0.156 086 522 571 35 × 10 –8 0.349 940 054 637 65 × 10 –1 –0.375 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 0.3 0.626 897 104 146 85 × 10 –9 –0.402 476 697 635 28 0.365 821 651 442 04 × 10 –11 –0.880 894 931 021 34 × 10 –0.165 540 500 637 34 × 10 –2 0.317 774 973 307 38 –0.5 0.125 335 479 355 23 × 10 1 0.136 364 351 103 43 –1 0.626 395 869 124 54 × 10 –0.767 881 978 446 21 × 10 –1 0.833 265 048 807 13 × 10 –1 –0.313 062 603 234 35 × 102 0.115 379 964 229 51 × 10 –6 0.32 βi 0.160 748 684 862 51 –1 –0.557 111 185 656 45 × 10 –0.252 131 543 416 95 × 10 ni αi 20 20 20 βi 150 150 250 γi 1.759 413 770 881 44 × 10 –3 0.436 136 157 238 11 × 10 –1 0.789 576 347 228 28 × 10 1 –0.21 1.393 434 226 032 54 × 10 –5 –0.318 025 093 454 18 –0.221 322 951 675 46 –0.203 934 865 137 04 × 10 –2 –0.875 1 0.132 511 800 746 68 × 10 –9 –0.75 0.781 997 516 879 81 × 10 –2 0.478 073 299 154 80 –1 0.5 0.21 1.141 806 344 006 17 × 10 –2 0.290 523 360 095 85 × 10 –1 0.9 Table 2.85 0.199 555 719 795 41 × 10 –3 0.5 3.118 411 824 259 81 –1 i 52 53 54 ci – – – di 3 3 3 ti 0 1 4 –0.313 587 007 125 49 × 10 –0.3 .205 279 408 959 48 × 10 –0.662 126 050 396 87 × 10 –0.32 0.743 159 297 103 41 0.107 936 009 089 32 –1 0.386 150 855 742 06 × 10 –1 –0.2 0.

φ r = ⎢ ⎥ δ δδ ⎢ ∂δ ⎥τ ⎣ ⎦ r ⎡ ∂ 2φ r ⎤ r ⎡ ∂φ ⎤ . τ ) o r = τ φτ + φτ RT ( ) ) s = − ( ∂ f /∂T ) ρ s( δ . φδτ = ⎢ ⎥ . τ ) RT ρ ′′ pσ ⎛ 1 ⎛ ρ′ ⎞ 1⎞ r r ⎜ ρ ′′ − ρ ′ ⎟ − ln ⎜ ρ ′′ ⎟ = φ ( δ ′. ⎢ ∂τ ⎥ δ ⎢ ∂τ ⎥δ ⎣ ⎦ ⎣ ⎦ r a φ r = ⎡ ∂φ ⎤ . φτ = ⎢ ∂ τ ⎥δ ⎢ ∂ δ ∂τ ⎥ ⎣ ⎦ ⎣ ⎦ ⎡ ∂ 2φ o ⎤ ⎡ ∂φ o ⎤ o ⎢ ⎥ . τ ) ⎠ ⎝ ⎠ RT ⎝ ⎡ ∂ 2φ r ⎤ ⎡ ∂ 2φ r ⎤ o r ⎢ 2 ⎥ .10 Table 3. φττ = ⎢ 2 ⎥ . τ ) − φ ( δ ′′. 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 →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 ) δ →0 2 r C (τ ) ρc = lim φδδ ( δ . pσ r = 1 + δ ′′φδ ( 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 ρ ′ . 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 . τ ) ( ∂ f /∂ρ )T ρ RT r = 1 + δφδ Internal energy Entropy u = f − T ( ∂ f /∂T ) ρ u (δ . φ r = ⎢ 2 ⎥ . φτ = ⎢ ⎥ ττ ⎢ ∂τ ⎥δ ⎢ ∂δ ⎥τ ⎣ ⎦ ⎣ ⎦ . 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 . τ ) o r = τ φτ + φτ − φ o − φ r R ( Enthalpy h = f − T ( ∂ f /∂T ) ρ + ρ ( ∂ f /∂ρ )T h (δ . τ ) R c p (δ .

11 Table 4. φ o = ⎡ ∂ φ ⎤ . ⎢ 2 ⎥ ⎢ 2 ⎥ ⎢ ⎥ τ ττ ⎢ ∂δ ⎥ ⎢ ∂τ ⎥ δ δδ δτ ⎣ ⎦τ ⎣ ⎦δ ⎣ ∂δ ⎦τ ⎣ ∂τ ⎦ δ ⎣ ∂δ ∂τ ⎦ . φ o = ⎡ ∂ φ ⎤ . φ o = ⎡ ∂ φ ⎤ . φ o = ⎡ ∂φ ⎤ . 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 ⎝ ⎥ ⎦ .

φδδ = ⎢ 2 ⎥ . ⎢ ∂δ ⎥τ ⎢ ∂δ ⎥τ ⎢ ∂τ ⎥δ ⎢ ∂τ ⎥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 ⎥ . φτ = ⎢ ⎥ . φττ = ⎢ 2 ⎥ . φδτ = ⎢ ⎥.3 Table 5.

150 151 914 × 10 0.548 314 253 × 10 0.618 315 728 × 10 0.358 000 0 × 10 0.255 071 625 × 104 0. Table 8. Values for the ideal-gas part φ o .193 249 185 × 10 = 0 a For the abbreviated notation of the derivatives of 5. For this reason.203 237 509 × 10 0.223 440 737 × 10 = – 0.700 000 006 × 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.749 161 585 × 103 0.387 405 401 0. (4). respectively.999 679 423 × 10 1 3 4 3 –1 2 3 –1 a cv /(kJ kg K ) 0.283 094 670 × 10–1 0.118 820 2 × 10 3 4 4 p/MPa 0.132 609 616 0. and for the residual part φ r .220 384 756 × 10 0.100 003 858 × 10 0.14 Table 6.346 135 580 × 10 0.150 817 541 × 10 0.932 203 564 0.193 510 526 × 10 0.992 418 352 × 10 0.384 236 747 0.241 000 0 0.108 456 4 × 10 647 900 0.550 664 919 × 10–2 0.406 798 347 × 10 0.700 004 704 × 10 0.169 082 693 × 102 0.393 062 643 0.200 000 690 × 10 0.100 530 8 × 10 500 0. due to an accumulation of small errors. by applying the phaseequilibrium condition (Maxwell criterion).700 000 405 × 10 0.910 660 121 × 101 T = 450 K 0.118 290 280 × 103 0.535 739 001 × 10 0. .904 611 106 × 10 1 = – 0. Eq.204 797 733 × 10 0.250 428 995 × 104 0. φ o φr r φδ r φδδ r φτ r φττ r φδτ and = – 0.166 991 025 × 10 0. a particular computer code or a particular PC may fail to reproduce the pressure value with nine significant figures.794 488 271 × 10 0.266 422 350 × 10 1 1 1 1 1 1 1 1 1 1 1 –1 –1 w/(m s–1) 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) 0.996 556 0 × 10 0.916 653 194 × 10 0.277 441 078 × 104 0.417 223 802 × 10 1 1 1 1 1 1 1 1 0.201 933 608 × 10 4 4 4 3 3 4 4 3 3 3 4 s/(kJ kg–1 K–1) 0.364 366 650 = 0.481 200 360 × 101 0.518 506 121 × 101 a All these test values were calculated from the Helmholtz free energy.307 437 693 × 10 0.698 451 167 × 10–3 0. Eq.526 150 0 × 10 0.890 341 250 × 103 0.682 502 725 × 10 0.453 200 0 × 10 0.567 090 385 × 103 0.660 921 221 × 101 T = 625 K 0.241 200 877 × 10 0. of the dimensionless Helmholtz free energy together with the corresponding derivativesa for T = 500 K and ρ = 838.210 865 845 × 101 0. (6). (5).127 128 441 × 10 0.175 890 657 × 10 0.775 972 202 × 101 0. Thermodynamic property values in the single-phase region for selected values of T and ρ T/K 300 ρ / (kg m–3) 0.025 kg m–3 φo o φδ o φδδ o φτ o φττ o φδτ = = = 0.100 062 559 0.435 000 0 0.168 626 976 × 104 0.147 637 878 1 1 = – 0.724 027 147 × 10 0.698 445 674 × 10 0.112 176 915 × 10 r 1 1 1 1 φ see the footnotes of Tables 4 and Table 7.999 887 406 × 103 0.342 693 206 × 10 = – 0.153 492 501 × 10 0.581 403 435 × 10 = – 0.856 063 701 = – 0.838 025 0 × 10 0. Eq.413 018 112 × 10 0.256 690 919 × 10 0.244 357 992 × 10 0.432 092 307 × 10 0.870 769 0 × 10 0.322 106 219 × 10 0.659 070 225 × 10 0.999 938 125 0.252 145 078 × 10 0.380 194 683 × 101 0.200 022 515 × 10 0.

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

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

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

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