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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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