international journal of refrigeration 32 (2009) 1123–1125

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Short Communication

A simple formulation for thermodynamic properties of steam

from 273 to 523 K, explicit in temperature and pressure

J. Pátek*, J. Klomfar
Institute of Thermomechanics, Academy of Sciences of the Czech Republic, Dolejškova 5, CZ 182 00 Prague 8, Czech Republic

article info abstract

Article history: The present formulation completes the description of the thermodynamic properties of LiBr–
Received 3 December 2007 H2O system, the solution properties of which are provided by the previous study of the authors.
Accepted 29 December 2008 The intent of the paper is to provide potential users with a simple and easily implementable
Published online 10 January 2009 tool for calculating thermodynamic properties of steam. A Gibss energy equation is presented
which was developed as an approximation of the values of the pure water vapor properties
Keywords: computed from the internationally accepted IAPWS formulation 1995. Explicit equations for
Absorption system molar volume, isobaric heat capacity, enthalpy, and entropy are given. The maximum devi-
Water-lithium bromide ations from IAPWS-95 are 0.03% for molar volume, 0.8% for isobaric heat capacity,
Calculation 0.7 kJ kg1 (i.e. 0.026%) for the enthalpy and less than 0.015 kJ kg1 K1 (i.e. 0.022%) for
Thermodynamic property the entropy. The deviations lie within the declared maximum deviation bands at temperatures
Vapour from 273 to 523 K and up to the pressure of saturation at each given temperature.
Water ª 2009 Elsevier Ltd and IIR. All rights reserved.

Une formulation simple pour les propriétés de la vapeur d’eau

entre 273 et 523 K, avec précision de la température et la
pression
Mots clés : Système à absorption ; Eau-bromure de lithium ; Calcul ; Propriété thermodynamique ; Vapeur ; Eau

1. Introduction liquid phase of the system at vapor–liquid equilibrium is

Water is used as refrigerant in absorption cycle working pairs
such as the LiBr–H2O system, which is the most common one,
or in the pairs LiCl/H2O and CaCl2/H2O studied as its alternative.
Knowledge of the thermodynamic properties of the gas and
essential for analysis and simulation of absorption cycles for
refrigeration, heat pumps, chillers and heat transformers. As
for the liquid phase of the LiBr–H2O system, recently there have
been published three descriptions of its thermodynamic prop-
erties. Two of them are given in the form of the Gibbs energy

* Corresponding author. Tel.: þ420 266053153; fax: þ420 28584695.

E-mail address: patek@it.cas.cz (J. Pátek).
0140-7007/$ – see front matter ª 2009 Elsevier Ltd and IIR. All rights reserved.
doi:10.1016/j.ijrefrig.2008.12.010
1124 international journal of refrigeration 32 (2009) 1123–1125

Nomenclature v molar volume, m3 mol1

cp molar isobaric heat capacity, J mol1 K1 Subscripts

g molar Gibbs free energy, J mol1 c at the critical point
h molar enthalpy, J mol1 p isobaric
M molar mass, kg mol1
Physical constants
p dimensionless pressure variable (p ¼ p/pc)
R 8.314371 J mol1 K1
p pressure, Pa
MH2 O 0.018015268 kg mol1
P polynomial term (P ¼ asnpm)
Tc 647.096 K
s molar entropy, J mol1 K1
Pc 22.064  106 Pa
T temperature, K
s dimensionless temperature variable (s ¼ Tc/T )

function by Yuan and Herold (2005) and by Kim and Infante simple equations for enthalpy and specific volume of the
Ferreira (2006). Pátek and Klomfar (2006) published separate superheated water declared as valid up to 455 K. Irvine and
equations for pressure, density, isobaric heat capacity, Liley (1984) developed separate approximate equations for
enthalpy, and entropy of the system. None of these works specific volume, enthalpy and entropy. Their equations are
include its own description of the gas-phase properties of the based on the steam data tables for properties of water and
system. The thermodynamic property formulation of the LiCl– steam by Keenan et al. (1969). At 500 K, the values of enthalpy
H2O system by Pátek and Klomfar (2008) has the form of two and entropy calculated using the equations by Keenan et al.
separate Gibbs energy functions for the liquid and the gas (1969) deviate by 1.8% and 3%, respectively, from those of
phase. The gas phase is described here by an approximation of IAPWS-95 while the deviation of specific volume reaches here
the Gibbs free energy of the water vapor valid up to 400 K. the value of 2.5%. Recent calculations of multi-stage absorp-
The gas phase of the above mentioned systems include tion cycles require knowledge of the steam thermodynamic
practically only pure water vapor in a superheated states. The properties at temperatures up to 500 K (Srikhirin et al., 2001).
most recent description of the thermodynamic properties of The temperature of 473 K (200  C) or higher is often mentioned
liquid and gaseous water is provided by the internationally as the maximum temperature of high-temperature applica-
accepted IAPWS-95 formulation (Wagner and Pruß, 2002). tions (Kim et al., 2002; Yuan and Herold, 2005).
Some authors still use the previous IAPS-84 formulation by The present short report provides a simple thermody-
Haar et al. (1984) or even yet more obsolete one by Keenan et al. namically consistent formulation of the thermodynamic
(1969). These formulations use as their independent variables properties of water vapor with temperature and pressure as
the temperature and density. However, the use of such the independent variables. The formulation completes the
formulations might be found to be somewhat cumbersome description of the thermodynamic properties of the LiBr–H2O
when temperature and pressure are used as input quantities of system, the solution properties of which are provided by the
the cycle calculation. That is why various partial thermody- study (Pátek and Klomfar, 2006).
namic property descriptions using temperature and pressure
as the independent variables are often used in absorption cycle
calculations. A widely used correlation for the properties of
aqueous lithium bromide by McNeely (1979) includes also
2. Gibbs potential function of the water
vapor
Table 1 – Coefficients and exponents of Eqs. (1)–(5).
i ni mi ai The Gibbs potential function g(T, p) has been developed as an
approximation of the property values generated from the
1 0 1 4.03740
IAPWS-95 formulation (Wagner and Pruß, 2002). Other ther-
2 1 0 6.66860
modynamic properties are given by the derivatives of the g(T, p)
3 0 0 8.78474
4 4 0 2.67859  102 in accordance with the standard thermodynamic relations:
5 4 1 8.24016  101
6 5 1 7.39848  101
7 6 1 2.73558  101 Table 2 – Maximum differences of values of the Gibbs
8 2 2 2.51325  101 energy, enthalpy, entropy, molar volume and isobaric
9 12 2 8.64644  102 thermal capacity calculated from equations (1)–(5),
10 13 2 4.04713  102 respectively, from the IAPWS-95 formulation.
11 12 3 2.07714
Quantity Irvine and Liley (1984) This work
12 15 3 2.48941
13 16 3 1.26382 Dg – 0.1 kJ kg1
14 15 4 6.46755 Dh 1.8% 0.026% (0.7 kJ kg1)
15 16 4 4.63404 Ds 3.0% 0.0015% (0.022 kJ kg1 K1)
16 15 5 3.59518 Dv 2.7% 0.03%
17 16 5 1.71653 Dcp – 0.8%
 international journal of refrigeration 32 (2009) 1123–1125 1125

Table 3 – Property values calculated from equations (1)–(5) for validation of computer programs.
p (Pa) T (K) v (m3 mol1) cp (J mol1 K1) h (J mol1) s (J mol1 K1) g (J mol1)

698.451 275 3.271706 33.878 45 109.5 164.036 0.3729

698.451 523 6.225648 35.471 53 633.0 186.077 43685
245 769 400 0.013153 39.914 48 916.3 127.136 1938
245 769 523 0.017541 36.414 53 491.2 137.127 18226
3 966 110 523 0.000905 72.125 50 457.4 109.403 6760

The reference values of enthalpy and entropy are

v g
2
adjusted consistently with the reference state of IAPWS-95
h ¼ T ;
vT T p formulation. Since the 5-th International Conference on the
Properties of Steam in London in 1956, the specific internal
 
vg energy and specific entropy of the saturated liquid at the
s¼ ;
vT T triple point have been arbitrarily set equal to zero (Wagner
and Pruß, 2002). This yields for the specific enthalpy and
  specific Gibbs energy of the saturated liquid at the triple
vg
v¼ ; point the value of 0.611782 J kg1. The specific enthalpy and
vp T
specific entropy of the saturated vapor at the triple point
 2  thus amounts to 2500.92 kJ kg1 and 9.1555 kJ kg1 K1
v g
cp ¼ T : respectively.
vT2 p

In order to be consistent with the formulation of the ther-

modynamic properties of LiBr–H2O solutions (Pátek and
Acknowledgements
Klomfar, 2006), the equations give molar values of the
described properties. To convert specific quantities to the
The work described in this paper has been performed under
molar ones, water molar mass of 0.018015268 kg mol1
the research intention No. AV0Z20760514 awarded by the
(Wagner and Pruß, 2002) has been used. With the following
Academy of Sciences of the Czech Republic.
notation for the dimensionless variables s, p and polynomial
terms Pi:
Tc p references
s¼ ; p¼ ;
T pc
Pi ¼ ai sni pmi ;
Haar, L., Gallagher, J.S., Kell, G.S., 1984. Steam Tables NBS/NCR.
the resultant equations are as follows:
" # McGraw-Hill, New York.
X
N Irvine Jr., T.F., Liley, P.E., 1984. Steam and Gas Tables with
gðT; pÞ ¼ RT lnp þ a1 lns þ Pi ; (1) Computer Equations. Academic Press, New York.
i¼2
Keenan, J.H., Keyes, F.G., Hill, P.G., Moore, J.G., 1969. Steam
" #
X
N Tables. Wiley, New York.
hðT; pÞ ¼ RT a1 þ ni Pi ; (2) Kim, D.S., Infante Ferreira, C.A., 2006. A Gibbs energy
i¼2
" # equation for LiBr aqueous solutions. Int. J. Refrigeration 29,
X
N
sðT; pÞ ¼ R  lnp þ a1 ð1  lnsÞ þ ðni  1ÞPi ; (3) 36–46.
i¼2 Kim, J.-S., Ziegler, F., Lee, H., 2002. Simulation of the compressor-
assisted triple-effect H2O/LiBr absorption cooling cycles. Appl.
! Therm. Eng. 22, 295–308.
RT XN
vðT; pÞ ¼ 1þ mi Pi ; (4) McNeely, L.A., 1979. Thermodynamics properties of aqueous
p i¼2 solutions of lithium bromide. ASHRAE Trans. 85, 413–434.
Pátek, J., Klomfar, J., 2006. A computationally effective
" # formulation of the thermodynamic properties of LiBr–H2O
X
N
cp ðT; pÞ ¼ R a1  ni ðni  1ÞPi : (5) solutions from 273 to 500 K over full composition range. Int. J.
i¼2 Refrigeration 29, 566–578.
Pátek, J., Klomfar, J., 2008. Thermodynamic properties of the LiCl–
Table 1 gives the coefficients ai and exponents ni and mi for the H2O system at vapor–liquid equilibrium from 273 to 400 K. Int.
equations (1)–(5). At temperatures from 273 to 523 K and at J. Refrigeration 31, 287–303.
pressures up to the saturated vapor pressure at each given Srikhirin, P., Aphornratana, S., Chungpaibulpatana, S., 2001. A
temperature, the maximum deviations of the values calcu- review of absorption refrigeration technologies. Renew.
lated from Eqs. (1)–(5) from the IAPWS-95 values lie within the Sustain. Energy Rev. 5, 343–372.
Wagner, W., Pruß, A., 2002. The IAPWS formulation 1995 for the
maximum deviation bands given in Table 2. The number of
thermodynamic properties of ordinary water substance for
significant figures given in coefficients ai in Table 1 is neces-
general and scientific use. J. Phys. Chem. Ref. Data 31, 387–535.
sary and sufficient to obtain the stated accuracy. Values Yuan, Z., Herold, K.E., 2005. Thermodynamic properties of
generated by equations (1)–(5) are given in Table 3 to facilitate aqueous lithium bromide using a multiproperty free energy
their implementation. correlation. HVAC & R Research 11, 377–393.