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jpcrd617|Views: 5|Likes: 0

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https://www.scribd.com/doc/110162316/jpcrd617

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In this section, three further synthetic data sets used to

develop IAPWS-95 are described. Two of these data sets

cover thermal properties p T data and were ‘‘produced’’to

inﬂuence the extrapolation behavior of IAPWS-95. The third

data set consists of data for the isochoric heat capacity in the

critical region, and was intended to support the development

of IAPWS-95 regarding this difﬁcult region.

The entire development process of IAPWS-95 was started

by establishing preliminary wide-range equations of state in

the following way. The equations were ﬁtted only to p T

data of the gas region determined from the gas equation, Eq.

3.2 and to the selected experimental p T data of the entire

ﬂuid region including the p T data in the saturation

state see Tables 4.4 and 4.1 . In this way, in the ‘‘difﬁcult’’

parts of the entire thermodynamic surface e.g., critical re-

gion, subcooled liquid the preliminary equations of state

were not negatively inﬂuenced by data of properties other

than the very accurate p T data. The aim of establishing

such an equation was to achieve a reasonable description of

the high-pressure and high-temperature range, where few if

any reliable experimental data exist.

In this way we succeeded in determining preliminary

equations that showed a physically meaningful behavior

when we calculated simultaneously the Hugoniot curve and

the p T behavior in the high-pressure high-temperature

range, for further details see Sec. 7.3.3.1. In order to ensure

that the positive behavior that had been achieved at this stage

of development could be retained in the following genera-

tions of equations, 50 p T data were calculated from the

respective preliminary equations in the temperature range

from 555 to 5300 K at densities from 1500 to 2500 kgm 3

to

support the behavior of the Hugoniot curve. Further, 120

p T data were calculated from these preliminary equations

for temperatures between 448 and 1273 K and densities from

1000 to 2500 kgm 3

to ensure that IAPWS-95 did not pro-

duce any crossing of isotherms or even a bending of iso-

therms in the extrapolation range at pressures up to 100000

MPa. In the ﬁnal stage of the equation development leading

to IAPWS-95, any of the preliminary equations could be

used to calculate the 170 synthetic p T data, because all

these equations yielded basically the same reasonable p T

surface in this high-pressure high-temperature region. Thus,

the 170 synthetic p T data can also be calculated from the

ﬁnal equation, the IAPWS-95 formulation itself.

The behavior of caloric properties in the critical region of

water is covered insufﬁciently by existing experimental data.

On the one hand, the experimental data near the critical point

were not free of systematic errors so that these data had to be

adjusted using the ‘‘revised and extending scaled equation’’

of Levelt Sengers et al. 1983 , and therefore considerable

corrections in the temperature values given by the experi-

menters for their data were made. This is the case for the

isochoric heat capacity data of Amirkhanov et al. 1969 and

the speed of sound data of Erokhin and Kal’yanov 1979 ,

1980 . Thus, the real information content of these data is

**418
418
**

**W. WAGNER AND A. PRUß
**

**J. Phys. Chem. Ref. Data, Vol. 31, No. 2, 2002
**

questionable, see also Secs. 4.3 and 4.4. On the other hand,

the measurements of reliable caloric data end far before the

range of interest in the critical region; this is the case for the

cv data of Baehr and Schoma¨cker 1975 .

Nevertheless, in order to achieve a consistent description

of the critical region it was necessary to calculate synthetic

cv values in the near-critical region using suitable equations

from the literature. When IAPWS-95 was being developed,

the scaled equation developed by Luettmer-Strathmann

1992 was the obvious choice for this procedure; this equa-

tion corresponds to a parametric crossover model. For the

critical region and a greater range outside the critical region,

namely for temperatures from 628 to 800 K (Tc

647.096K) and densities from 115 to 635 kgm 3

( c

322kgm 3

), Luettmer-Strathmann ﬁtted the coefﬁcients

of her equation to p T, cv , cp , and p T data calcu-

lated from the equation of state of Saul and Wagner 1989 ,

taking into account the temperature conversion to ITS-90

temperatures.

Besides the crossover equation of Luettmer-Strathmann

1992 , cv values were also calculated from the equation of

state of Hill 1990 . This was done because Hill’s equation

yields better results for the extended critical region than

Luettmer-Strathmann’s equation. The reason for this is that,

in the transition region between the critical and extended

critical region, Hill’s equation is better than that of Saul and

Wagner 1989 on which Luettmer-Strathmann’s equation

was based.

After careful investigation of Hill’s and Luettmer-

Strathmann’s equations in the critical and extended critical

region, the following input data for the development of

IAPWS-95 were used: 176 cv values along seven isochores

in the critical region for temperatures between 646.24 and

654.92 K and densities from 267 to 400 kgm 3

calculated as

follows: The equation of Luettmer-Strathmann 1992 was

used to calculate the cv values for T 648K, while for T

648K the values were determined from the equation of

Hill 1990 . When calculating these synthetic cv data, we

made allowance for the fact that the two equations and

IAPWS-95 are based on different critical parameters and dif-

ferent temperature scales.

**5. Details of the Development
of the IAPWS-95 Formulation
**

The new equation of state for ordinary water substance is

an empirical description of the Helmholtz free energy. For

the development of such empirical formulations, the applica-

tion of linear optimization procedures and nonlinear multi-

property ﬁtting algorithms is state-of-the-art. Although this

strategy has already been presented in the literature e.g.,

Setzmann and Wagner 1989 , 1991 , Wagner and de Reuck

1996 , and Span 2000 , this section summarizes the basic

elements of this strategy along with the special features nec-

essary when developing the new equation of state for H2O.

**5.1. Basic Structure of an Equation of State
Explicit in the Helmholtz Free Energy
**

The equation of state described in this article is a funda-

mental equation explicit in the Helmholtz free energy f with

the independent variables density and temperature T. The

function f( ,T) is commonly split into a part f° that repre-

sents the properties of the ideal gas at given T and and a

part fr

that takes into account the residual ﬂuid behavior.

This convention can be written as

f ,T f° ,T fr

,T .

5.1

Usually, the Helmholtz free energy is used in its dimension-

less form f/(RT) so that Eq. 5.1 becomes

, ° , r

, ,

5.2

where / c is the reduced density and Tc/T is the

inverse reduced temperature with c and Tc the critical den-

sity and the critical temperature, respectively.

Since the Helmholtz free energy as a function of density

and temperature is one of the four fundamental forms of an

equation of state, all thermodynamic properties of a pure

substance can be obtained by combining derivatives of Eq.

5.2 . For the relations between Eq. 5.2 and its derivatives

and the thermodynamic properties considered in this paper,

see Table 6.3.

**5.2. The Equation for the Helmholtz Free Energy
of the Ideal Gas
**

The Helmholtz free energy of the ideal gas is given by

f° ,T h° T RT Ts° ,T . 5.3

For the ideal gas, the enthalpy h° is a function of tempera-

ture only, and the entropy s° depends on temperature and

density. Both properties can be derived from an equation for

the ideal-gas heat capacity cp

(T). When cp

is inserted into

the expression for h°(T) and s°( ,T) in Eq. 5.3 , one ob-

tains

f° ,T

T

0

T

cp

dT h0

RT

5.4

T T

0

T cp

R

T dT R ln

0

s0

,

where all variables with the subscript ‘‘0’’ refer to an arbi-

trary reference state.

In order to obtain the equation for f°( ,T) and ° , ,

the well-established equation of Cooper 1982 was used for

the isobaric heat capacity in the ideal-gas state, cp

(T). This

equation, which is a sum of so-called ‘‘Planck–Einstein’’

functions, is:

cp

R b0

i 1

5

bi

i /T 2

e i /T

1 e i /T

2 . 5.5

**419
419
**

**THERMODYNAMIC PROPERTIES OF ORDINARY WATER
**

**J. Phys. Chem. Ref. Data, Vol. 31, No. 2, 2002
**

Cooper determined the coefﬁcients b0, bi , and the expo-

nents i by nonlinear least-squares ﬁtting to the cp

values of

Woolley 1980 , where he took into account only the data for

temperatures between 130 and 2000 K. After rearranging the

coefﬁcients and exponents, namely n3

b0 1, and for

i 1 to 5 ni 3

bi and i 3

i /Tc, one obtains from

Eq. 5.5

cp

R 1 n3

i 4

8

ni

i

2

e

i

1 e

i

2

5.6

with Tc/T. Equations 5.5 and 5.6 represent the cp

values of Woolley 1980 very accurately. The values of the

coefﬁcients of Eq. 5.6 are given in Table 6.1. In the tem-

perature range from 250 to 2000 K, the deviations in cp

/R

between the values of Woolley 1980 and the values from

Eqs. 5.5 and 5.6 are less than 0.0005%, and from 140 to

240 K they do not exceed 0.001%.

After inserting cp

(T) according to Eq. 5.6 in Eq. 5.4 ,

working out the integrations and proceeding to the dimen-

sionless form of the Helmholtz free energy in the ideal-gas

state ° see Eq. 5.2 , one obtains the ﬁnal ° equation,

given as Eq. 6.5 .

**5.3. Basic Statements for Fitting and Optimizing
the Structure of an Equation for the
Residual Part of the Helmholtz Free Energy
**

While statistical thermodynamics can predict the behavior

of ﬂuids in the ideal-gas state with high accuracy, no physi-

cally founded equation is known which accurately describes

the real thermodynamic behavior of ﬂuids in the whole ﬂuid

region. Thus, for this purpose an equation for the residual

ﬂuid behavior, in this case for the residual part of the Helm-

holtz free energy r

, must be determined in an empirical

way where, as a matter of course, as much physical under-

standing as possible is taken into account. Since the Helm-

holtz free energy itself is not accessible to direct measure-

ments, it is necessary to determine the unknown

mathematical structure and the unknown coefﬁcients of the

residual part of the dimensionless Helmholtz free energy

from properties for which experimental data are available.

In this context, the following steps for the development of

the ﬁnal form of an equation for r

must be performed:

1 selection of the ﬁnal data set, see Secs. 2–4;

2 weighting of the data;

3 precorrelation of auxiliary quantities;

4 linear least squares ﬁtting in connection with the struc-

ture optimization method; and

5 nonlinear least squares ﬁtting.

In this section, basic statements on items 2 – 5 are made.

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