~

Applied Thermal Engineering Vol. 16, No. 1, pp. 71 79, 1996

Copyright 1995 Elsevier Science Ltd
1359-4311(95)00009-7
Printed in Great Britain. All rights reserved
1359-4311/96 $9.50 + 0.00

Pergamon

FAST

EVALUATION

OF THERMODYNAMIC

OF SUPERHEATED

STEAM:

A CUBIC

PROPERTIES
EQUATION

OF STATE

J. L. M. Fernandes
Applied Thermodynamics Division, Department of Mechanical Engineering, Turbomachinery Building,
Instituto Superior T6cnico, Av. Rovisco Pais, 1, 1096 Lisboa, Portugal

(Received in retqsed form 7 January 1995)

Abstract--In this article, a cubic equation of state to estimate the thermodynamic properties of
superheated steam is presented. It is based on a truncated form of the virial expansion. The constants
involved are determined to correlate with heat capacity data. This equation of state seems adequate for
use when a large number of property evaluations is necessary within the limited range of operation of
most steam power plants. It can be applied in thermodynamic cycle design optimization, in dynamic
simulations of power plants and other industrial calculations of a repetitive nature involving steam at
moderate pressures.

K e y w o r d ~ T h e r m o d y n a m i c properties,

equation of state,

steam,

virial coefficients,

water.

INTRODUCTION
The wide use of steam in power conversion and other applications in industry makes the evaluation
of its thermodynamic properties an important issue. The widespread use of small computers, and
the continuous increase of their application in calculations related to power plants, created the
demand for reliable approaches for the fast evaluation of thermodynamic properties of steam.
An important part of the calculations involved in the computer analysis of power cycles consist
of the evaluation of thermodynamic properties of superheated steam at subcritical pressures.
Indeed, in about 40% of the power cycle points the steam is superheated.
Recent formulations for producing tables of water properties cover a wide range of conditions,
are consistent from the thermodynamic point of view and accurate for experimental data [1]. They
are based on a fundamental equation, the Helmholtz free energy function from which all other
properties can be determined. This approach was introduced by Keenan and co-workers, see
references in Keenan et al. [2]. However, such formulations are, in most instances, orientated
towards the production of tables rather than to meet the needs of engineering computations. Two
more recent formulations by Saul and Wagner [3] seem adequate from the accuracy point of view
and they considerably extend the range of applicability when compared to previous formulations.
The faster of their formulations, however, still has a 38-coefficient expansion. As small computers
become more powerful these formulations are expected to be increasingly used. There are several
applications, though, where a large number of thermodynamic property evaluations are needed;
for example, in the analysis of power cycles [4], in their dynamic simulation, in their optimization
[5], in turbomachinery flow calculations [6] and in the design of other industrial equipment. In some
of these applications, millions of property evaluations might be necessary. Therefore, the
above-mentioned procedures may not be appropriate, due to the large processing time they actually
require when the number of thermodynamic states wanted is large and only small computers are
available.
Cubic equations of state have been known for a long time. The van der Waals gas model, which
dates back to the last century, is an example of a cubic equation of state. Most modern cubic
equations are essentially variants of the Redlich-Kwong-Soave and Peng-Robinson equations of
state [7]. These equations have been widely used in the estimation of vapour-liquid equilibria of
pure substances and mixtures, particularly in refrigeration cycles and in the petroleum industry [8].
Young [6] considered a cubic equation of state derived from the virial expansion and applied it
ATE

16/l--V

71

72

J.L.M.

Fernandes

to the determination of steam properties. The International Association for the Properties of Water
and Steam, IAPWS, is now preparing a set of fast formulations for use by industry which will be
available soon.
In this study, a cubic equation of state was developed and applied to superheated steam. A simple
formulation that allowed the computation of a large number of thermodynamic states in small
machines within modest computing times was needed. The number of constants involved in the
equations of state would have to be small. The properties evaluated should be in good agreement
with an internationally recognized formulation. A computer program published with the
N B S / N R C steam tables [1] was used to generate the properties of steam. The range needed was:
pressures from 2 kPa (0.02 bar) up to 20 MPa (200 bar) and temperatures from 20 to 600C. The
upper bound temperature, however, was easily extended to 800C. The region close to the critical
point is out of the scope of this work. The sequence used to obtain the constants is presented and
discussed in the paper.
The equation of state is to be employed in the energy and exergy analysis of several existing steam
power plants. It is also to be used in component (such as heaters, condensers, turbines, boilers,
etc.) diagnosis calculations.
NOTATION
The set of properties used in this article, their symbols and units are indicated in Table 1.
Subscript r denotes scaled quantities.
At any point, two independent properties are needed to characterize a thermodynamic state.
Most equations of state use T and v (or p = 1/v) as the main independent variables. The remaining
properties can be obtained by a set of fundamental thermodynamic relations involving partial
derivatives and some calculus. Another interesting approach describes the thermodynamic surface
using a Gibbs function and (T,p) as the input variables [9].
The variables and constants are presented in non-dimensional form. This has the advantage of
enabling the user to choose the more appropriate units for his particular application, as well as
the fact that scaled constants have reasonably small magnitudes (close to unity). From the
numerical point of view, scaling the equations is also important whenever there is a non-linear
system to be solved by an iterative process.
For the superheated vapour properties the scales are: the gas constant (R = 0.461522 kJ/kg K)
for specific entropy and specific heats; RTc for specific internal energy and enthalpy and the
pseudo-critical volume; and RTc/p~, for the specific volume.
SPECIFIC HEAT DATA FOR STEAM
It is known [6] that a good correlation of specific heat to experimental data is a more stringent
criterion than the correlation of the basic properties. In other words, we should be more concerned
with a good representation of the thermodynamic coefficients associated with derivatives of the
second and first order. As the main independent variables chosen are T and v (or p = l/v), the
specific heat at constant volume is the thermodynamic coefficient linearly related to a second order
derivative of the equation of state. Therefore it plays a central role in the determination of other
properties. The main concern here should be to ensure that a proposed model for Cv correlates
with reliable data, particularly at the higher pressures in the working range. We could fit p T-v
data to an equation of state instead. This would yield a lower error fit to pressure data. However,
Table l.Thermodynamic properties
Superheated property

Symbol

Units

Scale

Vapour specific enthalpy

Pressure
Density
Vapour specific entropy
Temperature
Vapour specific volume
Specific heats

h
p
P
s
T
v
Cv, Cp

kJ/kg
bar
kg/m 3
kJ/kg/K
K
m3/kg
kJ/kg/K

RT c

Function
hr

Pc

Pr

Pc/RTc

Pr

R
Tc

sr
Tr

RTc/pc

vr

Cvr, Cpr

Fast evaluation

of thermodynamic

properties

of steam

73

to compute other properties,

for example the two specific heats, a large error would be found.
Consequently,
unacceptable
errors in enthalpy and entropy will show up and thus inappropriate
energy and exergy balances will be made.
As a computer program by Haar et al. [I] was available, we decided to use its output data for
the specific heat at constant volume. This data has good accuracy within the range we operate in.
However, it uses temperatures
on the IPTS-68 scale. Note that C, data could be obtained directly
from experiments.
Inspection
of graphic plots for the specific heat at constant volume as a function of density at
constant temperature
shows that, except in a region close to the critical point, a quadratic model
in density,

will adequately fit data over an isotherm. Optimized quadratic fits along isotherms to pressures up
to 20 MPa (200 bar) support this assertion, the maximum error being less than about 2%. This
is an acceptable level because the experimental
data uncertainty
is of this order in the high pressure
zone close to the critical temperature.
This justifies the equation of state presented in the next
section.

TRUNCATED
Consider

the following

equation

VIRIAL

OF STATE

of state:

pr = T,p,[l
or, using

EQUATION

+ W,)P,

c(T,)dl,

(2)

the specific volume,

(3)

This is a cubic equation of state based upon a truncated virial expansion.

are, respectively,
the second and third virial coefficients.

Specific

heat at constant

From

Functions

b (T,) and c (T,)

volume

basic thermodynamic

relations,

we have
=(S)

= T@).+-

(4)

This establishes the way the specific heat C, is related to the p(T, v) equation of state. It is an
important
relation, from which an accurate equation of state can be obtained by integration
once
a good correlation
for C, is found. From equation (3), we obtain

~~(~)~,=~[I~~b~~)l+I~~~~,]
and, by substitution

Integration

in equation

at constant

(4),

temperature
c

(T

yields

v ) = ~C&T,)
R

VT r3 r

(5)

7J~rcUr)I ~r[~rFrWr)I
2vf

0,

(7)

where C,, the specific heat at low density, is a function of temperature

only. Equation (7) confirms
that, when considering
a truncated
three-term virial expansion
(2) the specific heat at constant
volume becomes a quadratic
function of the density.

74

J.L.M. Fernandes

The equality of equations (1) and (7) gives

B(L)= -L[Lb(L)]",

(8)

A(rr) = -Tr[Trc(Tr)]".

(9)

Thus, once appropriate representations for the functions A(Tr) and B(Tr) are found, the virial
coefficients can be determined by integration through equations (8) and (9). In addition, a
correlation for the specific heat at low density, Cvo(T~), has to be supplied. A cubic model is accurate
enough to fit the specific heat values in the range 1-800C. The determination of the associated
constants must be consistent with the fits of functions A(Tr) and B(Tr).

Specific heat at constant pressure

The two specific heats are related by

/apr\ 2 //ap~\

Cpr(Zr, Ur) = Cvr(Zr, Ur) -- Tr~rr ) /~Ur)Tr'

(lo)

where

(OPr~

Z ~

~OTrJvr

ur

aV~/rr

1-t [Trb(Tr)]

--~.2Ur 1 +

(II)

jt

Ur

1)~

vr

3'

v~ J"

(12)

The validation of the specific heat at constant pressure computed through equation (10) also
enhances the importance of the first order partial derivatives of pressure. From equation (10) it
is apparent that a good correlation of Cp is possible only if Cv, (Op/OT)v and (dp/Ov)r are well fitted.
This requirement also holds true for the evaluation of internal energy, enthalpy and entropy.
Moreover, the fit of these three quantities is sufficient to determine all the constants of the model.
This explains why a good correlation of both the specific heats is essential in the validation of any
equation of state. Therefore, we can state that to obtain all properties to good accuracy we must
accurately fit the specific heat at constant volume together with the first order partial derivatives
of the pressure.
Equation (10) was also used by Haar et al. [1] to compute the specific heat at constant pressure.
Therefore, it was possible to make accurate values of the partial derivatives available and use them
to determine the constants of the equation of state.

A P P R O X I M A T I O N S FOR V I R I A L C O E F F I C I E N T S
In this section we outline the method used to develop simple forms for the virial coefficients. We
look for attractive approaches from the computational point of view. A simple approximation for
the second virial coefficient was introduced by Pitzer, as quoted in Reid et al. [7]. It can be recast
into the more general form
b2

b3

b(Tr)=b, +-~rr+~r,

(13)

where, for convenience, we set constants b~, b2, b 3 and parameters a, fl free (the only restrictions
being a ~ 1, fl :~ 1 and a ~ 0, fl ~ 0) for appropriate fitting. This allows one to investigate which
can be the most adequate inverse powers of the temperature in the virial coefficient expansion.
Similarly, we propose the following model for the third virial coefficient:
c2
c3
c(Tr) = c, + ~6 -~ Trr '

(14)

Fast evaluation of thermodynamic properties of steam

75

where constants c~, c2, c3 and parameters 3, 7(3 #- 1, 7 4= 1 and & ~ 0, 7 :~ 0) are to be determined.
This yields

T~[Trb(T~)]" - ~(ct - 1)bz

T~

rr[Trc(T~)] "

~-

fl(fl - 1)b3
T~
'

(15)

6(6 -- 1)C2 ?()' -- 1)C3

T~

(16)

Tr'

Thus, referring to equation (1), we seek approximations of the form

A( r)

Al

A2

Bl

B2

(17)

O(Tr) = ~r~ -t- ~ rfl .

(18)

The model for the specific heat at constant volume becomes

Cv ( T r ) ( _ ~

Cvr(Tr, Pr) - ~ -

02)

( "41

A2~ 2

"}-\Tr+~r Pr-}- ~r"k-~rrjPr

(19)

The first step should be directed to ensure a proper fit of equation (19) to data within the target
working range, particularly at high pressure. Also, it should be optimized to some error criterion.
After having determined functions A (Tr) and B(Tr) of the form of equations (17) and (18) using
specific heat data, we face another interesting feature--the integration process for the virial
coefficients b(Tr) and C(Tr) through equations (8) and (9) introduces a new additional constant for
each function, as follows:

b(Tr)-

~(~ - I)T~

B2
B4
/3(/3 - 1)T~ + B3 + ~ '

c(Tr)=

2Al
6(6-1)T~

7(~_l)T~+A3+~-.lr

B1

2A 2

(20)

A4

(21)

These new constants play an important role to fit (Op/~v)r. The full equation of state then becomes

[(C2C3C4~[/cC6C7C8X~2

,+

"]

This is a cubic equation of state. It is computationally attractive since only a few terms and simple
operations are involved in the calculation.

DETERMINATION

OF T H E C O N S T A N T S

The N B S / N R C formulation companion program was used to supply the data needed. Thus we
accepted its accuracy level for experimental data and refer to 'error' as the numerical deviation from
that formulation. The constants do not have to be simultaneously determined. Indeed, we will
illustrate a sequence of simpler problems to obtain them. As stressed before, the crucial issue is
the fit of Cv to reliable data in the target range. The determination of the constants for Cv is the
only non-linear optimization problem to be solved. Constants are found ultimately by a direct
search process. However, we first solve a sequence of linear least-squares problems where
parameters ~, /3, 3, 7 are allowed to vary. The parameters can be optimally chosen to minimize
the maximal error. The linear least-squares fit is a simple process. It helps to generate a first
approximation which yields indications on constants, parameters and associated errors. However
its overall performance strongly depends on the way the equations are weighted or scaled. For that
reason, a direct search collocation method was ultimately used. The process is as follows. We select
a number of interior points to the working range equal to the number of unknown constants, while
keeping parameters unchanged. Then we move these points to minimize the m a x i m u m error. The
sensitivity to the parameters is then tested and they are also optimized using the same criterion.

76

J.L.M. Fernandes

As shown before, a correlation for the specific heat at low density has to be supplied. A cubic
model is accurate enough to fit the specific heat values in the range 1-800C. The following model:
Cv0(Tr) = - 5.3290329 x 10 2T~ + 0.3189217T 2 - 6.7330668 x 10-2Tr + 1.3710226,

(23)

has an agreement level estimated in 0.83% in that range.

The specific heat at constant volume is fitted to data using
Cv0(Tr)
Cvr(Tr,Pr)--~

C(~-1)C2

~/3(/3~rr~1)C3) Pr--\{6(~5--1)C6
2T~

,(Y-1)C7"~2
fTTr )Pr,

(24)

the maximum deviation in the working range was below 3.1%. However, the r.m.s, deviation is
about 0.7%. Equation (24) determined the dimensionless constants (72, C3, C6, C7 and parameters
~, fl, 6, 7 given below.
Next, we have, from equation (11),

(63pr~

k~T~jv r = Pr +

C,

(0~ -- 1)C2
T~

(fl

T ~)C3 / p: + ( C5
r

( ~ - 1)C6
T~

-)P~"
(~ --TT1)C7~
_ 3

(25)

From the program by Haar et al. [1] we computed accurate values for the partial derivative and
used them to fit equation (25). The previously determined constants, (72, C3, C6 and C7 , remained
unchanged, while a weighted linear least-squares procedure was used to obtain constants Cl and
C5. This first derivative was fitted to a maximum of about 2.2% error, the r.m.s, error being 0.61%.
Finally we fit

(OPr~
= __Trp2EI"~-2(C'"%~rr"]-'~r"FZ)
C3Pr-{'-C2C4"~ 31/C[k5"q---~rr+
C6 CT-l-'~r)P2]T' --~r
\OVdr,

(26)

This fit is used to determine constants C4 and C8. This first derivative can be fitted to a maximum
error of about 3.5% and a r.m.s, of 0.35%. With the fits from equations (24)-(26) we obtain the
specific heat, Cp, accurate to errors below 5.8%, while the r.m.s, error is 0.71%.
The full equation of state becomes

I(

C2C3C4~1'/Cc6c7C8~2]__
__
,+~+~+~)Pr|,

pr = Zrp r 1"~- C I --]-T~-~--~r~--~-Z)pr-]- [k

(27)

where the dimensionless constants are

c~=0.562,

/3=4.20,

Cj = 0.10052348,
Ca = -0.51121127,

6=4.97,

(72 = 0.21589098,

7=9.22
C3 = -0.16400788,

C5=6.82878135x 10 -2 ,

C7 = -2.44119951 10 -2 ,

C6=0.100147264,

C8 = -9.75556323 10 -z.

(28)

The final fit for the pressure was below 0.86% in error while the r.m.s, error is about 0.18%.
However, the pressure can be estimated with some extra accuracy using a device which is discussed
next.

ERROR RECOVERY PROCEDURE

In the analysis of two-phase engineering cycles, many saturation property evaluations are needed.
The simplest way to do so seems to be to interpolate by low degree polynomials from stored points
along the saturation line. Their computation can also be done by other fast processes [10, 11].
Therefore, it is reasonable to assume that there is a fast process to accurately compute the
saturation vapour properties. In this case, the properties of any superheated point below the critical
isochore can be evaluated by integration at constant volume, starting from the saturation line. The
pressure, for example, can be computed by

frr t~pr(O, vr) dO.

P~(Tr'vr)=ps(Trs'Vr)+ Jr~
~0

(29)

Fast evaluation of thermodynamic properties of steam

77

The pressure estimated by this process has a maximum error of about 0.55% in the same range
as before, the r.m.s, error being inferior to 0.22%. This process maintains full consistency between
saturation and superheated properties. Also, it alleviates a common feature of cubic equations to
display large errors in the region close to the saturation line at high pressures.
OTHER SUPERHEATED VAPOUR PROPERTIES
For the model chosen, the internal energy, enthalpy and entropy are quadratic functions of the
density. Their partial derivatives require the knowledge of C~, (Op/OT)~ and (Op/Ov)r. The
determination of the enthalpy and entropy is made by integration, this is an accurate process.
Observe that the error level is reduced when we integrate.

Enthalpy
The specific enthalpy can be determined by integration as follows:

f Tr ahr(0, /')Or)

hr(Tr, Pr) = ho(To. Vo,) + JT0,

T0

f vr 0hr (Tr,

dO q- JV0r

OV

v)

dv.

(30)

The derivation of the final expression is straightforward and is not shown here for brevity. The
errors found are below 0.53%, the r.m.s, being about 0.25%. Similar expressions apply to entropy
and other properties. However, for the reasons explained above, we only need to integrate at
constant volume starting from the saturation line. Therefore, we only need the partial derivatives
at constant volume,
(0hr~

\aTr].,

= C v r . . ~ - Ufr /~pr'~
__| ,

(31)

\6GTrJ,,

Ohr']

'

(71r.
] ' ~ . v r = Cvr -I'- 1 -[- [T~b(Tr)] -t
Vr

( 0hr'] = 1 + - - +
I,kOTr)vr
R

[Trc(Tr)]'

C 1 --

(32)

2
Or

/'
(6 + 2)(6 - 1 ) C 6
+ t C5 2 T~

Pr
(y + 2)(7 -1)C7"~
2-Ti
)P ~"

(33)

The enthalpy at any point becomes

~T, Ohr(O, vD
hr(Tr, vr) = hs(Tr~, vr) + JT~
~0
dO.

(34)

where subscript s stands for saturated properties.

hr(Tr, Vr) = Tr + (C, T r-k

(Ct+I)C2 (fl+l)C3"~
(
(6+2)C6
(7+2)C7"~ 2
Tr~_, +
~rr-~ ) P r + Cs rr + 2 T~r_ ' F -2-TF i )Pr

~
(
Ts-(C, Ts+(~ T~+ 1)Cl 2 + (fl ~+z i1)C3")Pr--CsTs-~

+ hs(Ts, v,) + frs C'(O)

R dO.

(6 + 2)C 6 (y + 2)C7"~ 2
2T~_ l -2-~7~-S )pr
(35)

The final fit for enthalpy has an error inferior to 0.26%, the r.m.s, error being about 0.085%; this
is quite a good error level.

78

J. L. M. Fernandes

Entropy
The partial

derivatives

of the specific entropy

are
(36)

The entropy

at a given point

becomes
(38)

The final fit for entropy

0.056%.

has a maximum

error

inferior

to O.lS%,

the r.m.s.

error

being

about

DISCUSSION
The specific heat at constant volume fit was found to be a critical issue. It was fitted to deviations
below 3.1%. The remaining
constants
have been determined
to fit the partial derivatives
of
pressure, (ap/aT),. with an error level below 2.2% and (ap/&), below 3.5%. The specific heat at
constant pressure was determined
for deviations
less than 5.8%. The pressure is estimated with
errors below 0.86% in the considered range. However, with the integration
device introduced
it
becomes estimated as 0.55% error. The final fits for enthalpy and entropy display errors inferior
to 0.26 and 0.18% respectively. The error levels referred to above are upper bounds in the target
range, the average error being significantly
lower. The overall accuracy level seems quite good for
a cubic equation of state.
The range considered
was: pressures from 2 kPa (0.02 bar) up to 20 MPa (200 bar) and
temperatures
from 1 to 800C. While extrapolation
at low pressures poses no difficulty, it is a source
of appreciable
errors at high pressure.

CONCLUDING

REMARKS

In this article, a cubic equation of state has been presented. It is based upon a truncated virial
expansion. The associated specific heats at constant volume, internal energy, enthalpy and entropy
are quadratic functions of density. Simple forms for the virial coefficients were adopted. The result
is an equation of state with a notably small number of constants. We found that the simple model
thus built can predict superheated
steam propeties to an acceptable error level within the range
of operation
of most steam power plants.
To obtain a good correlation
to all thermodynamic
properties it is essential to ensure a good
fit of C,, (ap/dT),. and (apjdv),. In addition, it was found that these quantities
are sufficient to
determine all the model constants. To summarize the main steps of the method used: (1) select a
model for C, that guarantees a proper fit to data in the target range; (2) fit, by this order, (ap/dT),
and (apjav),; (3) monitor the accuracy of C, and the remaining
properties,
such as enthalpy,
entropy, pressure, etc.
This approach yields a compact representation
of steam properties in the range considered and,
while retaining good accuracy, their computation
is indeed fast. It seems particularly
adequate for
use in small computers, when a large number of evaluations
is needed or whenever more elaborate
codes prove to be time-consuming.
It can be applied in cycle design optimization,
in dynamic
simulations
of power cycles, in component
analysis and design and in other calculations where from
several thousands
to millions of property evaluations
are performed. The equation should not be
used outside the range it is designed for because extrapolation
at high pressures can be highly
inaccurate.
Other techniques
to further accelerate the computation
exist and can be used [6, 121.

Fast evaluation of thermodynamic properties of steam

79

T h e a d d i t i o n o f h i g h e r o r d e r t e r m s in t h e virial e x p a n s i o n c a n be c o n d u c t e d a l o n g t h e s a m e lines
as d e s c r i b e d in t h e p a p e r . T h e p o s s i b l e a p p l i c a t i o n o f this e q u a t i o n o f state to o t h e r fluids d e s e r v e s
further consideration.
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3. A. Saul and W. Wagner, A fundamental equation for water covering the range from melting ice to 1273 K at pressures
up to 25,000 MPa. J. Phys. Chem. Ref Data 18 (4), 1537 1564 (1989).
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(1991).
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Turb. Power 110, 1 7 (1989).
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8. J. Vidal, Equations of state--reworking old forms. Fluid Phase Equilibria 13, 15 33. (1983).
9. J. Juza, Teploenergetika 10, 80 (1960).
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Nov., 346-351 (1986).
11. J. L. M. Fernandes, Correlations for fast computation of thermodynamic properties of saturated water and steam. Int.
J. Energy Res. (to appear).
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151-161 (1977).