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Thermodynamic properties of ammonia–water mixtures for power-

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Article  in  Energy · June 1999

DOI: 10.1016/S0360-5442(99)00007-9

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 Energy 24 (1999) 525–536
www.elsevier.com/locate/energy

Thermodynamic properties of ammonia–water mixtures for

power-cycle applications
Feng Xua, D. Yogi Goswamib,*
a
Donlee Technologies, Inc., 693 North Hills Road, York, PA 17402, USA
b
Department of Mechanical Engineering, University of Florida, Gainesville, FL 32611, USA
Received 28 July 1997

Abstract
Ammonia–water mixtures have been used as working fluids in absorption–refrigeration cycles for several
decades. Their use as multi-component working fluids 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 equa-
tions 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 vapor–liquid equilibrium (VLE) and the thermodynamic
properties of ammonia–water mixtures, including p–t–x–y data and caloric properties. For enthalpy
data, see Refs. [1–3]. Ref. [4] published new values of enthalpy and entropy from ⫺ 70 to 370°F
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. [12–16] 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 proper-
ties and bubble and dew point temperature equations for phase equilibrium is used. This method

* Corresponding author. Fax: ⫹ 1-352-392-1701; e-mail: solar@cimar.me.ufl.edu

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
526 F. Xu, D.Y. Goswami / Energy 24 (1999) 525–536

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

冕 冕 冕
T P T

G ⫽ h0 ⫺ Ts0 ⫹ Cp dT ⫹ v dP ⫺ T (Cp/T) dT, (1)

T0 P0 T0

where h0, s0, T0 and P0 are the specific enthalpy, specific 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:
GLr ⫽ hLr,o ⫺ TrsLr,o ⫹ B1(Tr ⫺ Tr,o) ⫹ (B2/2)(T 2r ⫺ T 2r,o) ⫹ (B3/3)(T 3r ⫺ T 3r,o)
⫺ B1Tr ln(Tr/Tr,o) ⫺ B2Tr(Tr ⫺ Tr,o) ⫺ (B3/2)(T 2r ⫺ T 2r,o) ⫹ (A1 ⫹ A3Tr ⫹ A4T 2r)(Pr (2)
⫺ Pr,o) ⫹ (A2/2)(P2r ⫺ P2r,o).
For the gas phase:
Ggr ⫽ hgr,o ⫺ Trsgr,o ⫹ D1(Tr ⫺ Tr,o) ⫹ (D2/2)(T 2r ⫺ T 2r,o) ⫹ (D3/3)(T 3r ⫺ T 3r,o)
⫺ D1Tr ln(Tr/Tr,o) ⫺ D2Tr(Tr ⫺ Tr,o) ⫺ (D3/2)(T 2r ⫺ T 2r,o) ⫹ Tr ln(Pr/Pr,o) ⫹ C1(Pr (3)
⫺ Pr,o) ⫹ C2(Pr/T 3r ⫺ 4Pr,o/T 3r,o ⫹ 3Pr,oTr/T 4r,o) ⫹ C3(Pr/T 11
r ⫺ 12Pr,o/T r,o
11

⫹ 11Pr,oTr/T 12
r,o) ⫹ (C4/3)(Pr /T r ⫺ 12Pr,o/T r,o ⫹ 11Pr,oTr/T r,o).
3 11 3 11 3 12

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 specific enthalpy, entropy and volume are related to Gibbs free energy, in terms of
reduced variables, by

h ⫽ ⫺ RTBT 2r 冋 ∂
(G /T )
∂Tr r r 册 Pr
, (4)
 F. Xu, D.Y. Goswami / Energy 24 (1999) 525–536 527

Table 1
Coefficients of Eqs. (2) and (3)

Coefficient Ammonia Water

A1 3.971423 ⫻ 10−2 2.748796 ⫻ 10−2

A2 ⫺ 1.790557 ⫻ 10−5 ⫺ 1.016665 ⫻ 10−5
A3 ⫺ 1.308905 ⫻ 10−2 ⫺ 4.452025 ⫻ 10−3
A4 3.752836 ⫻ 10−3 8.389246 ⫻ 10−4
B1 1.634519 ⫻ 10+1 1.214557 ⫻ 10+1
B2 ⫺ 6.508119 ⫺ 1.898065
B3 1.448937 2.911966 ⫻ 10−2
C1 ⫺ 1.049377 ⫻ 10−2 2.136131 ⫻ 10−2
C2 ⫺ 8.288224 ⫺ 3.169291 ⫻ 10+1
C3 ⫺ 6.647257 ⫻ 10+2 ⫺ 4.634611 ⫻ 10+4
C4 ⫺ 3.045352 ⫻ 10+3 0.0
D1 3.673647 4.019170
D2 9.989629 ⫻ 10−2 ⫺ 5.175550 ⫻ 10−2
D3 3.617622 ⫻ 10−2 1.951939 ⫻ 10−2
hLr,o 4.878573 21.821141
hgr,o 26.468873 60.965058
sLr,o 1.644773 5.733498
sgr,o 8.339026 13.453430
Tr,o 3.2252 5.0705
Pr,o 2.000 3.000

s⫽⫺R 冋 册
∂Gr
∂Tr Pr
(5)

and

v⫽ 冋 册
RTB ∂Gr
PB ∂Pr Tr
. (6)

4. Ammonia–water 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:
GEr ⫽ [F1 ⫹ F2(2x ⫺ 1) ⫹ F3(2x ⫺ 1)2](1 ⫺ x), (7)
where x is the ammonia mass fraction
F1 ⫽ E1 ⫹ E2Pr ⫹ (E3 ⫹ E4Pr)Tr ⫹ E5/T4 ⫹ E6/T 2r,
528 F. Xu, D.Y. Goswami / Energy 24 (1999) 525–536

F2 ⫽ E4 ⫹ E8P4 ⫹ (E9 ⫹ E10Pr)Tr ⫹ E11/Tr ⫹ E12/T 2r

and
F3 ⫽ E13 ⫹ E14Pr ⫹ E15/Tr ⫹ E16/T 2r
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 2r 冋∂
(GE/T )
∂Tr r r 册 ,
Pr, x
(8)

sE ⫽ ⫺ R 冋 册
∂GEr
∂Tr Pr, x
(9)

and

vE ⫽
PB ∂Pr冋 册
RTB ∂GEr
.
Tr, x
(10)

In addition, the enthalpy, entropy and volume of a liquid mixture are given by:
hLm ⫽ xfhLa ⫹ (1 ⫺ xf)hLw ⫹ hE, (11)

sLm ⫽ xfsLa ⫹ (1 ⫺ xf)sLw ⫹ sE ⫹ smix, (12)

smix ⫽ ⫺ R[xf ln(xf) ⫹ (1 ⫺ xf) ln(1 ⫺ xf)] (13)

and
vLm ⫽ xfvLa ⫹ (1 ⫺ xf)vLw ⫹ vE, (14)

Table 2
Coefficients of Eq. (7)

E1 ⫺ 41.733398 E9 0.387983
E2 0.02414 E10 0.004772
E3 6.702285 E11 ⫺ 4.648107
E4 ⫺ 0.011475 E12 0.836376
E5 63.608967 E13 ⫺ 3.553627
E6 ⫺ 62.490768 E14 0.000904
E7 1.761064 E15 24.361723
E8 0.008626 E16 ⫺ 20.736547
 F. Xu, D.Y. Goswami / Energy 24 (1999) 525–536 529

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

5. Ammonia–water vapor mixture

Ammonia–water vapor mixtures are often assumed to be ideal solutions. The enthalpy, entropy
and volume of the vapor mixture are computed by:
hgm ⫽ xghga ⫹ (1 ⫺ xg)hgw, (15)

sgm ⫽ xgsga ⫹ (1 ⫺ xg)sgw ⫹ smix (16)

and
vgm ⫽ xgvga ⫹ (1 ⫺ xg)vgw. (17)

6. Vapor–liquid 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:
f̂ La ⫽ f̂ga, (18)

f̂ Lw ⫽ f̂gw, (19)
where f̂ is the fugacity of each component in the mixture at equilibrium. The fugacities of
ammonia and water in liquid mixtures are given by [17]:
f̂ La ⫽ ␥af 0ax␦a (20)
and
f̂ Lw ⫽ ␥wf 0w(1 ⫺ x)␦w, (21)
where ␥ is the activity coefficient, 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
f̂ ga ⫽ ␾aPy (22)
and
530 F. Xu, D.Y. Goswami / Energy 24 (1999) 525–536

f̂ gw ⫽ ␾wP(1 ⫺ y), (23)

where ␾ is the fugacity coefficient 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 ammonia–water 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 coefficient of a component in a
mixture to determine the bubble (Tb) and dew point (Td) temperatures.

冘 冘
7 10

Tb ⫽ Tc ⫺ (Ci ⫹ Cij xj )[ln(Pc/P)]i (24)

i⫽1 j⫽1

and

冘 冘
6 4

Td ⫽ Tc ⫺ (ai ⫹ Aij [ln(1.0001 ⫺ x)]j [ln(Pc/P)])i, (25)

i⫽1 j⫽1

where

冘
4

Tc ⫽ Tcw ⫺ aixi, (26)

i⫽1

冘
8

Pc ⫽ Pcw exp( bixj ), (27)

i⫽1

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 ammonia–water 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) 525–536 531

avoids the iterative solution necessary to solve Eqs. (18)–(23), thereby reducing the compu-
tational 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 ammonia–water mixtures as compared with the
data from Ref. [11].
For temperatures less than 406 K, the computational results fit 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.

532 F. Xu, D.Y. Goswami / Energy 24 (1999) 525–536

Fig. 2. Saturation pressures of ammonia–water mixtures at 333.15 K.

Fig. 3. Saturation pressures of ammonia–water mixtures at 405.95 K.

 F. Xu, D.Y. Goswami / Energy 24 (1999) 525–536 533

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 figure 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 first.

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 ammonia–water mixtures at 34.47 bar.

534 F. Xu, D.Y. Goswami / Energy 24 (1999) 525–536

Fig. 5. Saturated vapor enthalpy of ammonia–water mixtures at 34.47 bar.

Fig. 6. Entropy of saturated liquid at 310.9 K.

 F. Xu, D.Y. Goswami / Energy 24 (1999) 525–536 535

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 difficult 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 ammonia–water 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 vapor–liquid 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 experi-
mental 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.
536 F. Xu, D.Y. Goswami / Energy 24 (1999) 525–536

[3] Wucherer J, Gesamt Z. Kalte-Ind 1932;39:97.

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

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