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Energy 24 (1999) 525536

Thermodynamic properties of ammoniawater mixtures for power-cycle applications

Feng Xua, D. Yogi Goswamib,*
b a Donlee Technologies, Inc., 693 North Hills Road, York, PA 17402, USA Department of Mechanical Engineering, University of Florida, Gainesville, FL 32611, USA

Received 28 July 1997

Abstract Ammoniawater mixtures have been used as working uids in absorptionrefrigeration cycles for several decades. Their use as multi-component working uids for power cycles has been investigated recently. The thermodynamic properties required are known or may be calculated at elevated temperatures and pressures. We present a new method for these computations using Gibbs free energies and empirical equations for bubble and dew point temperature to calculate phase equilibria. Comparisons of calculated and experimental data show excellent agreement. 1999 Published by Elsevier Science Ltd. All rights reserved.

1. Background Many studies have been published on vaporliquid equilibrium (VLE) and the thermodynamic properties of ammoniawater mixtures, including ptxy data and caloric properties. For enthalpy data, see Refs. [13]. Ref. [4] published new values of enthalpy and entropy from 70 to 370F and pressure up to 300 psia using experimental data from [2,3,5]. Ref. [6] created tables of VLE and caloric properties that were used by other researchers to propose computational models [7 9]. In Ref. [10], measured data from [11] were used to give correlations for pressures of 0.2 to 110 bar and temperatures of 230 to 600 K. Refs. [1216] also presented models for calculating the thermodynamic data at elevated temperatures and pressures. In the present study, a method that combines the Gibbs free energy method for mixture properties and bubble and dew point temperature equations for phase equilibrium is used. This method
* Corresponding author. Fax: 1-352-392-1701; e-mail: 0360-5442/99/$ - see front matter 1999 Published by Elsevier Science Ltd. All rights reserved. PII: S 0 3 6 0 - 5 4 4 2 ( 9 9 ) 0 0 0 0 7 - 9


F. Xu, D.Y. Goswami / Energy 24 (1999) 525536

combines the advantages of the two and avoids the need for iterations for phase equilibrium by the fugacity method.

2. Gibbs free energy equation for a pure component The Gibbs free energy of a pure component is given by G h0 Ts0


Cp dT


v dP T (Cp/T) dT,


where h0, s0, T0 and P0 are the specic enthalpy, specic entropy, temperature and pressure at the reference state. Use of empirical relations for v and Cp [9] leads to the following equations. For the liquid phase:
L L 2 2 3 3 GL r hr,o Trsr,o B1(Tr Tr,o) (B2/2)(T r T r,o) (B3/3)(T r T r,o) 2 2 B1Tr ln(Tr/Tr,o) B2Tr(Tr Tr,o) (B3/2)(T 2 r T r,o) (A1 A3Tr A4T r )(Pr 2 Pr,o) (A2/2)(P2 r Pr,o).


For the gas phase:

g g 2 2 3 3 Gg r hr,o Trsr,o D1(Tr Tr,o) (D2/2)(T r T r,o) (D3/3)(T r T r,o) 2 D1Tr ln(Tr/Tr,o) D2Tr(Tr Tr,o) (D3/2)(T 2 r T r,o) Tr ln(Pr/Pr,o) C1(Pr 3 4 11 11 Pr,o) C2(Pr/T 3 r 4Pr,o/T r,o 3Pr,oTr/T r,o) C3(Pr/T r 12Pr,o/T r,o 3 11 3 11 3 12 11Pr,oTr/T 12 r,o) (C4/3)(Pr /T r 12Pr,o/T r,o 11Pr,oTr/T r,o).


Here, the superscripts are L for liquid and g for gas, while subscript o is for the ideal gas state. The reduced (subscript r) thermodynamic properties are Tr T/TB, Pr P/PB, Gr G/RTB, hr h/RTB, sr s/R and vr vPB/RTB. The reference values for the reduced properties are R 8.314 kJ/kmol K, TB 100 K and PB 10 bar. The constants in Eqs. (2) and (3) are given in Table 1.

3. Thermodynamic properties of a pure component The molar specic enthalpy, entropy and volume are related to Gibbs free energy, in terms of reduced variables, by h RTBT 2 r

(G /T ) Tr r r



F. Xu, D.Y. Goswami / Energy 24 (1999) 525536 Table 1 Coefcients of Eqs. (2) and (3) Coefcient A1 A2 A3 A4 B1 B2 B3 C1 C2 C3 C4 D1 D2 D3 hL r,o hg r,o sL r,o sg r,o Tr,o Pr,o Ammonia 3.971423 102 1.790557 105 1.308905 102 3.752836 103 1.634519 10+1 6.508119 1.448937 1.049377 102 8.288224 6.647257 10+2 3.045352 10+3 3.673647 9.989629 102 3.617622 102 4.878573 26.468873 1.644773 8.339026 3.2252 2.000 Water 2.748796 102 1.016665 105 4.452025 103 8.389246 104 1.214557 10+1 1.898065 2.911966 102 2.136131 102 3.169291 10+1 4.634611 10+4 0.0 4.019170 5.175550 102 1.951939 102 21.821141 60.965058 5.733498 13.453430 5.0705 3.000


sR and v

Gr Tr





4. Ammoniawater liquid mixtures The Gibbs excess energy for liquid mixtures allows for deviation from ideal solution behavior. The Gibbs excess energy of a liquid mixture is expressed by the relationship proposed in [9], which is limited to three terms and is given by:
2 GE r [F1 F2(2x 1) F3(2x 1) ](1 x),


where x is the ammonia mass fraction F1 E1 E2Pr (E3 E4Pr)Tr E5/T4 E6/T 2 r,


F. Xu, D.Y. Goswami / Energy 24 (1999) 525536

F2 E4 E8P4 (E9 E10Pr)Tr E11/Tr E12/T 2 r and F3 E13 E14Pr E15/Tr E16/T 2 r The constants for Eq. (7) are given in Table 2. The excess enthalpy, entropy and volume for the liquid mixtures are given as: hE RTBT 2 r

(GE/T ) Tr r r

Pr, x


sE R and vE

GE r Tr


Pr, x


Tr, x


In addition, the enthalpy, entropy and volume of a liquid mixture are given by:
L L E hL m xfha (1 xf)hw h ,

(11) (12) (13) (14)

L L E mix , sL m xfsa (1 xf)sw s s

smix R[xf ln(xf) (1 xf) ln(1 xf)] and

L L E vL m xfva (1 xf)vw v ,

Table 2 Coefcients of Eq. (7) E1 E2 E3 E4 E5 E6 E7 E8 41.733398 0.02414 6.702285 0.011475 63.608967 62.490768 1.761064 0.008626 E9 E10 E11 E12 E13 E14 E15 E16 0.387983 0.004772 4.648107 0.836376 3.553627 0.000904 24.361723 20.736547

F. Xu, D.Y. Goswami / Energy 24 (1999) 525536


where subscripts a and w refer to ammonia and water, respectively and subscript f refers to the saturated liquid condition.

5. Ammoniawater vapor mixture Ammoniawater vapor mixtures are often assumed to be ideal solutions. The enthalpy, entropy and volume of the vapor mixture are computed by:
g g hg m xgha (1 xg)hw,


g g mix sg m xgsa (1 xg)sw s


g g vg m xgva (1 xg)vw.


6. Vaporliquid equilibrium At equilibrium, binary mixtures must have the same temperature and pressure. Moreover, the partial fugacity of each component in the liquid and gas mixtures must be equal: g (18) fL a fa , g (19) fL w fw , where f is the fugacity of each component in the mixture at equilibrium. The fugacities of ammonia and water in liquid mixtures are given by [17]: 0 (20) fL a af a xa and
0 fL w wf w(1 x)w,


where is the activity coefcient, f0 is the standard-state fugacity of the pure liquid component corrected to zero pressure, is the Poynting correction factor from zero pressure to saturation pressure of the mixture and x is the ammonia mass fraction in liquid phase. Assuming an ideal mixture in the vapor phase, the fugacities of the pure components in the vapor mixtures are given by (22) fg a aPy and


F. Xu, D.Y. Goswami / Energy 24 (1999) 525536

fg w wP(1 y),


where is the fugacity coefcient and y is the ammonia mass fraction in vapour phase. Eqs. (18) and (19) are used to calculate the boiling and dew point temperatures given the pressure and ammonia concentration in the liquid mixture. However, these two equations must be solved iteratively to produce the VLE properties of ammoniawater mixtures. Alternatively, the bubble and dew point temperatures can be calculated using the explicit equations developed in Ref. [14].

7. Bubble point and dew point temperature equations Eqs. (24) and (25), developed in [14], determine the start and end of the mixture phase change and compute the mass fractions of ammonia and water in the liquid and vapor phases, respectively. This avoids the complicated method of calculating the fugacity coefcient of a component in a mixture to determine the bubble (Tb) and dew point (Td) temperatures. Tb Tc and Td Tc where Tc Tcw




10 4

Cij xj )[ln(Pc/P)]i





Aij [ln(1.0001 x)]j [ln(Pc/P)])i,





Pc Pcw exp(


bixj ),


P in psia and T in F.

8. Results In this study, the Gibbs free energy method is used to calculate the properties of pure ammonia and water [Eqs. (2)(6)]. The properties of the ammoniawater mixture are also calculated from the Gibbs free energy method using Eqs. (7)(17). In order to determine the phase quilibrium, bubble and dew points are calculated using the alternative method of Eqs. (24)(27) instead of the conventional method of equating the fugacities [Eqs. (18)(23)]. Using the alternative method

F. Xu, D.Y. Goswami / Energy 24 (1999) 525536


avoids the iterative solution necessary to solve Eqs. (18)(23), thereby reducing the computational time. The property data generated in this study have been compared with available experimental and theoretical data in the literature. 9. Comparison of bubble and dew point temperatures Fig. 1 shows that the bubble and dew point temperatures generated by this study compare favorably with the data from Ref. [6]. The differences between our computed values and the data are less than 0.3%. Refs. [9,10] are reported to have differences of up to 2% from these data. 10. Comparison of saturation pressure at constant temperature Figs. 2 and 3 show the saturation pressures of ammoniawater mixtures as compared with the data from Ref. [11]. For temperatures less than 406 K, the computational results t the experimental data well, except at saturated liquid pressures. At higher temperatures, our computed values are within 5% of the data even at pressures higher than 110 bar, while Ref. [9] has reported a difference of more than 15%. Ref. [10] reported an error of less than 5% under 110 bar and higher errors over 110 bar.

Fig. 1.

Bubble and dew point temperatures at a pressure of 34.47 bar.


F. Xu, D.Y. Goswami / Energy 24 (1999) 525536

Fig. 2.

Saturation pressures of ammoniawater mixtures at 333.15 K.

Fig. 3.

Saturation pressures of ammoniawater mixtures at 405.95 K.

F. Xu, D.Y. Goswami / Energy 24 (1999) 525536


11. Comparison of saturated liquid and vapor enthalpy 1. Saturated liquid enthalpy. The saturated liquid enthalpy of this work is compared with the data from Ref. [6], as shown in Fig. 4. The differences are less than 2% for all the data. 2. Saturated vapor enthalpy. The saturated vapor enthalpy at constant pressure is shown in Fig. 5. The agreement with the data is within 3%. Ref. [10] reported a 5% maximum difference. The mass fraction of ammonia vapor shown in this gure is the ammonia liquid mass fraction when the mixture reaches a saturated state. So, in order to compute the saturated vapor enthalpy, the ammonia vapor mass fraction must be determined rst.

12. Comparison of saturated liquid and vapor entropy The value of entropy is very important in predicting the performance of a turbine in a power cycle. Entropy data are also essential to the second-law analysis of thermal systems. Ref. [4] published saturated liquid and vapor entropy data based on experimental data from [2,3,5]. Ref. [16] published calculated entropy. The entropy data from the present study are compared with the experimental data in Ref. [4] and the computational data of Ref. [16]. 1. Saturated liquid entropy. Fig. 6 shows saturated liquid entropy data compared with those of

Fig. 4.

Saturated liquid enthalpy of ammoniawater mixtures at 34.47 bar.


F. Xu, D.Y. Goswami / Energy 24 (1999) 525536

Fig. 5. Saturated vapor enthalpy of ammoniawater mixtures at 34.47 bar.

Fig. 6.

Entropy of saturated liquid at 310.9 K.

F. Xu, D.Y. Goswami / Energy 24 (1999) 525536


Fig. 7. Entropy of saturated vapor at 310.9 K.

Ref. [4]. Our data agree with the experimental data of [4] much better than the data generated by the method of Ref. [16]. 2. Saturated vapor entropy. Fig. 7 shows an excellent agreement of our computed values of saturated vapor entropy with the data of Ref. [4]. Data computed by Ref. [16] are consistently lower. Since it was very difcult to identify saturated vapor entropy data from Ref. [16], we did not compare our results with them.

13. Conclusion Different methods for calculating the properties of ammoniawater mixtures are studied. A practical and accurate method is used in this study. This method uses Gibbs free energy equations for pure ammonia and water properties, and empirical bubble and dew point temperature equations for vaporliquid equilibrium. The iterations necessary for calculating the bubble and dew point temperatures by the fugacity method are avoided. Therefore, this method is much faster than using the fugacity method. The computational results have been compared with accepted experimental data in the literature and show very good agreement. References
[1] Jennings BH, Shannon FP. Refrig Eng 1938;44:333. [2] Zinner KZ, Gesamt Z. Kalte-Ind 1934;41:21.

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F. Xu, D.Y. Goswami / Energy 24 (1999) 525536 Wucherer J, Gesamt Z. Kalte-Ind 1932;39:97. Scatchard G, Epstein LF, Warburton J, Cody PJ. Refrig Eng 1947;53:413. Perman EP. J Chem Soc 1901;79:718. Macriss RA, Eakine BE, Ellington RT, Huebler J. Research bulletin no 34. Chicago (IL): Chicago Institute of Gas Technology, 1964. Gupta CP, Sharma CP. ASME paper 75-WA/PID-2. New York (NY): ASME, 1975. Schulz SCG. Proc XIIth Int Cong Refrig 1972;2:431. Ziegler B, Trepp C. Int J Refrig 1984;7:101. Ibrahim OM, Klein SA. ASHRAE Trans 1993;99:1495. Gillespie PC, Wilding WV, Wilson GM. AIChE Symp Ser 1987;83:97. Kalina AI. ASME paper 83-JPGC-GT-3. New York (NY): ASME, 1983. Herold KE, Han K, Moran MJ. ASME Proc 1988;4:65. El-Sayed YM, Tribus M. ASME special publication AES 1. New York (NY): ASME, 1985:89. Kalina AI, Tribus M, El-Sayed YM. ASME paper 86-WA/HT-54. New York (NY): ASME, 1986. Park YM, Sonntag RE. ASHRAE Trans 1992;97:150. Walas SM. Phase equilibria in chemical engineering. Stoneham (MD): Butterworths, 1985.