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DA-13-025

New Correlation Equations for Ammonia-

Water Vapor-Liquid Equilibrium (VLE)
Thermodynamic Properties

M.A.I. El-Shaarawi, PhD S.A.M. Said, PhD M.U. Siddiqui

ABSTRACT extension in pressure and temperature ranges was made over

Ammonia is widely used as a refrigerant in absorption
systems. Water is used as a solvent. For an adequate and accu-
rate analysis of an absorption systems performance, it is
important to be able to determine the thermodynamic proper-
ties of such a refrigerant-absorbent solution. This paper pres-
ents a set of seven polynomial forms of property correlations
developed based on experimental data. The developed corre-
lations are simple, easy to use, and explicitly defined, and they
best describe the thermodynamic properties of an ammonia-
water mixture. Also, this paper presents the results of the devel-
oped correlations compared with the results of other correla-
tions reported in the literature.
INTRODUCTION
An ammonia-water mixture is used as a refrigerant in
absorption refrigeration cycles and as the working fluid in
modern power generation cycles, such as the Kalina cycle.
The mixture has no environmental impact; i.e., it does not
contribute to ozone depletion. The knowledge of thermody-
namic properties of ammonia- water mixtures is essential for
design, simulation, and performance analysis of absorption
refrigeration systems.
The thermodynamic properties of ammonia-water
systems have been determined by a number of researchers.
The vapor-liquid equilibrium (VLE) has been of primary
interest due to the requirements of the absorption cycle. Park
and Sonntag (1990) used a generalized equation of state,
based on a four-parameter corresponding-states principle, to
determine the thermodynamic properties of the ammonia-
water mixtures with pressure and temperature ranges up to
200 bar (2910 psia) and 377C (710F), respectively. The
that considered by the Institute of Gas Technology (IGT)
(Macrisis et al. 1964) to cover the operating ranges of pres-
sure and temperature of power cycles. Ibrahim and Klein
(1993) used separate equations of state for liquid and gas
phases for pure ammonia and pure water. They assumed the
mixture to behave as an ideal solution in the liquid phase,
while Gibbs excess energy was used to allow a shift from ideal
solution behavior in the gas phase. Their correlation covers
VLE pressures and temperatures up to 110 bar (1595 psia)
and 327C (620F), respectively. Patek and Klomfar (1995)
constructed correlations describing VLE properties of ammo-
nia-water mixtures by fitting experimental data using simple
functional forms. Tillner-Roth and Friend (1998) presented a
thermodynamic model incorporating a fundamental equation
of state for the Helmholtz free energy of the ammonia-water
mixture, covering the thermodynamic space between the
solid-liquid-vapor boundary and the critical locus. Their
model presented the VLE properties for pressures up to
400 bar (5800 psia).
CORRELATIONS
Most of the reported correlations for ammonia-water
mixture thermodynamic properties used formulations with
complicated mathematical structures, such as the Helmholtz
free energy formulation and the Gibbs excess energy formu-
lation (Tillner-Roth and Friend 1998). Such formulations
cannot be readily used for simulation in industrial applica-
tions. Therefore, the aim of this study is to present the ammo-
nia-water VLE thermodynamic properties in a simple
polynomial form that is easy to use in all applications. Hence,
the experimental data (Gillespie et al. 1987), as well as data by

M.A.I. El-Shaarawi and S.A.M. Said are professors and M.U. Siddiqui is a masters student in the Department of Mechanical Engineering,
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia.

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Ibrahim and Klein (1993), have been used to develop simple, enthalpy is explicitly presented as a function of ammonia
easy-to-use thermodynamic property correlations. vapor mass concentration and saturation pressure of the
The first correlation pertains to the saturation temperature mixture. The polynomial form of the correlation is given as:
of an ammonia-water mixture in the liquid state. The satura-
tion temperature is explicitly presented as a function of ammo- n n n1
nia liquid mass concentration and saturation pressure of the hv = A + Bi y i + C i P i + y Di P i
mixture. The polynomial form of the correlation is given as: i=1 i=1 i=1
(5)
n1 n1
n n n1 + y2 Ei Pi + y3 F i Pi
T l = A + Bi x i + C i P i + x Di P i i=1 i=1
i=1 i=1 i=1
(1)
n1 n1 The sixth correlation pertains to the saturation entropy of
+ x2 Ei Pi + x3 Fi Pi an ammonia-water mixture in the liquid state. The saturation
i=1 i=1
entropy is explicitly presented as a function of ammonia liquid
The second correlation pertains to the saturation temper- mass concentration and saturation pressure of the mixture.
ature of an ammonia-water mixture in the vapor state. The The polynomial form of the correlation is given as:
saturation temperature is explicitly presented as a function of
ammonia vapor mass concentration and saturation pressure n n n1
of the mixture. The polynomial form of the correlation is sl = A + Bi x i + C i P i + x Di P i
given as: i=1 i=1 i=1
(6)
n1 n1
n n n1
+ x2 Ei Pi + x3 F i Pi
T v = A + Bi yi + Ci Pi + y Di Pi i=1 i=1
i=1 i=1 i=1
(2) The seventh correlation pertains to the saturation entropy
n1 n1 n1
+ y2 Ei Pi + y3 Fi Pi + y4 Gi Pi of an ammonia-water mixture in the vapor state. The satura-
i=1 i=1 i=1 tion entropy is explicitly presented as a function of ammonia
vapor mass concentration and saturation pressure of the
The third correlation pertains to the ammonia vapor mixture. The polynomial form of the correlation is given as:
mass concentration of an ammonia-water mixture. The
ammonia vapor mass concentration is explicitly presented as n n n1
a function of ammonia liquid mass concentration and satu- sv = A + Bi y i + C i P i + y Di P i
ration pressure of the mixture. The polynomial form of the i=1 i=1 i=1
(7)
correlation is given as: n1 n1 n1
+ y2 Ei Pi + y3 F i Pi + y4 G iP
i

n n n1 i=1 i=1 i=1

y = A + Bi x i + C i P i + x Di P i
i=1 i=1 i=1 The correlations cover the complete range of mass
(3) concentration and saturation pressure of up to 100 bar
n1 n1
+ x2 Ei Pi + x3 F i Pi (1450 psia) with correlation coefficients of greater than 0.99.
i=1 i=1 The coefficients pertaining to the study correlations are
listed in Table 1.
The fourth correlation pertains to the saturation enthalpy
of an ammonia-water mixture in the liquid state. The satura- RESULTS AND DISCUSSIONS
tion enthalpy is explicitly presented as a function of ammonia
A comparison is carried out between the ammonia-water
liquid mass concentration and saturation pressure of the
VLE thermodynamic properties determined using the devel-
mixture. The polynomial form of the correlation is given as:
oped correlations and the ones reported in the literature. A
number of these properties have been determined for different
n n n1
hl = A + Bi x i + C i P i + x Di P i ammonia mass concentrations. The properties determined
i=1 i=1 i=1 include bubble- and dew-point temperatures, vapor pressure,
(4) equilibrium composition of the components, enthalpy, and
n1 n1
+ x2 Ei Pi + x3 F i Pi entropy of the mixtures at saturation pressures.
i=1 i=1 Engineering Equation Solver (EES) is used to perform
calculations and generate the comparison curves (Klein 2009).
The fifth correlation pertains to the saturation enthalpy of EES has an internal function to determine the properties of
an ammonia-water mixture in the vapor state. The saturation ammonia-water mixtures. This internal function is based on

2 DA-13-025
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Table 1. Coefficients for Present Study Correlations (Equations 1-7)

Correlation n A B1 B2 B3 B4 B5

1 4 370.8 272.3 93.74 99.21 54.83

2 5 365.7 127.3 1045 3733 5228 2530

3 4 0.1435 5.694 12.33 10.53 2.988

4 4 405.1 1758 166.9 2598 1245

5 4 2651 538.53167 3617 6302 3539

6 4 1.261 2.21 5.845 10.58 4.37

7 5 7.48 1.056 9.391 39.19 55.02 26.3

Correlation C1 C2 C3 C4 C5

1 10.11 0.2768 0.003686299 0.00001785

2 13.25 0.5531 0.01268 0.0001395 0.000000583

3 0.001178057 0.0002992 3.0203E-06 0.00000001

4 44.06 1.195 0.015999011 0.0000779

5 13.58 0.4555 0.006558325 0.00003351

6 0.1162 0.003638 0.00005275 0.000000273

7 0.1369 0.006572 0.0001601 0.000001833 7.89E-09

Correlation D1 D2 D3 D4 E1 E2 E3 E4

1 0.7369 0.05012 0.0004538 5.851 0.0470549 0.00007047

2 3.711 0.07897612 0.001022 0.000005033 9.538 0.1524 0.001717 0.000007935

3 0.01574 0.0001743 0.00000197 0.101 0.000863 0.000003258

4 4 0.3508 0.002959 15.94 0.251 0.003846

5 1.766 0.01591 0.00002691 13.7 0.06589 0.0007111

6 0.04415 0.000176 0.000000865 0.03866 0.000358 7.6646E-06

7 0.01428 0.0006243 0.000008639 4.38E-08 0.07947493 0.003291 0.00004413 0.000000221

Correlation F1 F2 F3 F4 G1 G2 G3 G4

1 4.564 0.06016 0.000141

2 17.53 0.2862 0.00322449 0.00001503 8.4 0.1174 0.001222 0.000005517

3 0.07766 0.0008663 0.000004077

4 12.76 0.04592 0.001865

5 14.77 0.1091 0.0009271

6 0.008434 0.000355 0.000005891

7 0.1461 0.006177 0.0000834 0.000000421 0.07477 0.003363 0.000045612

DA-13-025 3
 2013 ASHRAE (www.ashrae.org). For personal use only. Additional reproduction, distribution, or
transmission in either print or digital form is not permitted without ASHRAE's prior written permission.

the correlations developed by Ibrahim and Klein (1993). (725 psia). The figure indicates that the results obtained using
Hence, EES implicitly uses the Ibrahim and Klein correlations different correlations are in good agreement with each other
in order to determine the thermodynamic properties of ammo- and with those from this study. The bubble-point tempera-
nia-water mixtures. The following equations reported by tures, obtained using the correlation developed by Ibrahim and
Patek and Klomfar (1995) are similarly used to determine the Klein (1993) and Tillner-Roth and Friend (1998), exhibit very
thermodynamic properties: close agreement with those obtained using the correlations
developed by Park and Sonntag (1990) and Patek and Klomfar
p ni
ln -----0-
mi (1995). The maximum deviation observed between the values
T p x = T 0 a i 1 x
i
p of bubble-point (incipient boiling) temperatures, obtained
using the present correlation and those developed by Park and
mi Sonntag (1990), are less than 3% in the range of 0.3 to 0.5
p
----- ni
T p y = T 0 a i 1 y 4 ln -----0- ammonia liquid mass concentrations.
i
p
The second comparative property is the dew-point temper-
ature. Figure 2 shows a comparison of dew-point temperatures
y p x = 1 exp ln 1 x a i ------ i x i
p m n 3 of ammonia-water mixtures plotted against ammonia vapor
i
p 0 mass concentration at a pressure of 50 bar (725 psia). It is clear
from the plot that all the results, with the exception of those by
h l T x = h 0 a i ------ 1 i x i
T m n Tillner-Roth and Friend (1998), are in good agreement with
i
T each other. In other words, the dew-point temperatures of Ibra-
0
him and Klein (1993), Park and Sonntag (1990), and Patek and
Klomfar (1995) are in good agreement with those determined
h g T y = h 0 a i 1 ------ i 1 y i
T m n 4
i
T by the present correlation. However, the values by Tillner-Roth
0
and Friend (1998) are slightly different from the others at low
The data reported by Park and Sonntag (1990) and the ammonia vapor mass concentrations. The average deviation
data reported by Tillner-Roth and Friend (1998) have been between the dew-point temperatures of Tillner-Roth and
entered into the look-up tables of EES to determine the Friend (1998) and others can be more than 3% for ammonia
required properties. Finally, after all the data were entered vapor mass concentration values less than 0.6.
into EES, parametric tables were generated to compare the The third comparative property is the liquid enthalpy. In
thermodynamic properties determined by different thermodynamic analyses, usually the enthalpy difference is
approaches. The final results are presented in graphical form used rather than the absolute value of the enthalpy. Thus, one
in Figures 16. should be aware that values of enthalpies given in property
The first comparative result pertains to the bubble-point tables and/or charts in different references might refer to
(incipient boiling) temperature. Figure 1 shows a comparison different data (for zero enthalpy). Therefore, comparisons
of bubble-point temperatures of ammonia-water mixtures, for enthalpies from different sources should be based on
determined using different correlations, plotted against enthalpy changes rather than individual enthalpy values.
ammonia liquid mass concentration at a pressure of 50 bar Figure 3 shows a comparison of saturated liquid enthalpy

Figure 1 Bubble-point temperatures of ammonia-water Figure 2 Dew-point temperatures of ammonia-water

mixture at a pressure of 50 bar (725 psia). mixture at a pressure of 50 bar (725 psia).

4 DA-13-025
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change of ammonia-water mixtures with respect to the
enthalpy at zero ammonia mass concentration and plotted
against ammonia liquid mass concentration at a pressure of
50 bar (725 psia). The figure indicates that the results deter-
mined using the correlation from Park and Sonntag (1990)
show the highest enthalpy change, whereas the results deter-
mined using correlations by Patek and Klomfar (1995) show
the lowest enthalpy change. The result obtained using differ-
ent correlations exhibits the same trend; i.e., an increase in
the enthalpy change until the point of inflection and then a
decrease in the enthalpy change afterwards. The negative
values in the enthalpy change signify the fact that the
enthalpy at zero ammonia mass concentration is higher than
the data under consideration. The enthalpy change by Ibra-
him and Klein (1993) is in good agreement with the results
of the present study, with a deviation of less than 0.7%. Other
enthalpy change results show greater deviations from both
Ibrahim and Klein (1993) and those of the present work.
Figure 4 shows a comparison of saturated vapor enthalpy
change of ammonia-water mixtures with respect to the
enthalpy at zero ammonia mass concentration and plotted
against ammonia vapor mass concentration at a pressure of
50 bar (725 psia). The figure indicates that the results by Ibra-
him and Klein (1993), Park and Sonntag (1990), and Patek and
Klomfar (1995) shows good agreement with the results of the
present study. However, the values of enthalpy change deter-
mined using the Tillner-Roth and Friend (1998) correlation are
less compared to the others values. The average deviation
between the enthalpy change values for saturated vapor
mixtures determined by the present study, Ibrahim and Klein
(1993), Park and Sonntag (1990), and Patek and Klomfar
(1995) is less than 2%.
The fifth comparative property pertains to the saturated
liquid entropy. It is similar to enthalpy in thermodynamic
analysis in that usually the entropy difference is used rather
than the absolute value of the entropy. Figure 5 shows a
Figure 3 Enthalpy change for saturated liquid ammonia-
water mixture at a pressure of 50 bar (725 psia).
DA-13-025
comparison of entropy change of saturated liquid ammonia-
water mixtures with respect to the entropy at zero ammonia
mass concentration and plotted against ammonia liquid mass
concentration at a pressure of 50 bar (725 psia). The figure indi-
cates that the results obtained using the Park and Sonntag (1990)
correlation show the highest entropy change values, whereas the
results obtained using the Tillner-Roth and Friend (1998) corre-
lation show the lowest value of entropy change. The point of
inflection occurs at around 0.75 ammonia liquid mass concen-
tration for the properties, using the correlations from Ibrahim
and Klein (1993) and Park and Sonntag (1990). However, it
occurs at around 0.6 ammonia liquid mass concentration for the
value obtained using the Tillner-Roth and Friend (1998) corre-
lations. The negative values in the entropy change signify that
the entropy at zero ammonia mass concentration is higher than
the data under consideration. In general, the entropy change
obtained using that of Ibrahim and Kleins data (1993) is lower
than that of Park and Sonntag (1990). However, at the saturation
lines (i.e., at pure water and pure ammonia), the values of
entropy change are identical for both.
Figure 6 shows a comparison of entropy change of satu-
rated vapor ammonia-water mixtures with respect to the
entropy at zero ammonia mass concentration and plotted
against ammonia vapor mass concentration at a pressure of
50 bar (725 psia). The figure indicates that the results by Ibra-
him and Klein (1993) and Park and Sonntag (1990) show good
agreement with the present studys correlation. However, the
results of entropy change obtained using the correlation
developed by Tillner-Roth and Friend (1998) are less
compared to the other values. The average deviation between
the entropy change data for saturated vapor mixtures obtained
by the present study, Ibrahim and Klein (1993), and Park and
Sonntag (1990) is less than 5%.
Figure 4 Enthalpy change for saturated vapor ammonia-
water mixture at a pressure of 50 bar (725 psia).
5
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Figure 5 Entropy change for saturated liquid ammonia- Figure 6 Entropy change for saturated vapor ammonia-
water mixture at a pressure of 50 bar (725 psia). water mixture at a pressure of 50 bar (725 psia).

(KACST) through NSTIP project number 08-ENE56-4 and

CONCLUSIONS King Fahd University of Petroleum and Minerals in conduct-
A set of seven polynomial forms of correlations that are ing this study.
simple, easy to use, and explicitly defined and that best
describe the thermodynamic VLE properties of ammonia- REFERENCES
water mixture has been developed based on experimental data. Klein, S.A. 2009. Engineering Equation Solver. Academic
These correlations give results that are in excellent agreement Professional version 8.427-3D. Department of Mechani-
with the results obtained using the correlations from Ibrahim cal Engineering, University of Wisconsin-Madison,
and Klein (1993). Madison, WI.
NOMENCLATURE Gillespie, P.C., W.V. Wilding, and G.M. Wilson. 1987.
Vapor-liquid equilibrium measurements on the ammo-
hl = saturation enthalpy of ammonia-water solution in
nia-water system from 313K to 589K. AIChE Sympo-
liquid state, KJ/kg
sium Series 83:256.
hv = saturation enthalpy of ammonia-water solution in
Ibrahim, O.M., and S.A. Klein. 1993. Thermodynamic prop-
vapor state, KJ/kg
erties of ammonia-water mixtures. ASHRAE Transac-
P = saturation pressure of ammonia-water solution, tions 99(1):1495.
bar (psia)
Macrisis, R.A., B.E. Eakin, R.T. Ellington, and J. Huebler.
sl = saturation entropy of ammonia-water solution in
1964. Physical and thermodynamic properties of
liquid state, KJ/kg K
ammonia-water mixtures. Research Bulletin 34, Insti-
sv = saturation entropy of ammonia-water solution in tute of Gas TechnologyChicago, IL.
vapor state, KJ/kg K
Park, Y.M., and R.E. Sonntag. 1990. Thermodynamic prop-
Tl = saturation temperature of ammonia-water solution erties of ammonia-water mixtures: A generalized equa-
in liquid state, K tion-of-state approach. ASHRAE Transactions
Tv = saturation temperature of ammonia-water solution 97(1):150.
in vapor state, K
Patek, J., and J. Klomfar. 1995. Simple functions for fast cal-
x = mass concentration of ammonia in liquid state culations of selected thermodynamic properties of the
y = mass concentration of ammonia in vapor state ammonia-water system. International Journal of Refrig-
eration 18(4):228.
Tillner-Roth, R., and D.G. Friend. 1998. Survey and assess-
ACKNOWLEDGEMENT ment of available measurements on thermodynamic
The authors would like to acknowledge the support of properties of the mixture (water-ammonia).
both King Abdulaziz City for Science and Technology J.Phys.Chem. Ref Data 27(1):45.

6 DA-13-025
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