International Journal of Mechanical Engineering and Technology (IJMET)

Volume 8, Issue 8, August 2017, pp. 1430–1440, Article ID: IJMET_08_08_148

Available online at http://iaeme.com/Home/issue/IJMET?Volume=8&Issue=8
ISSN Print: 0976-6340 and ISSN Online: 0976-6359

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THERMODYNAMIC PROPERTY FUNCTIONS

OF NH3-H2O MIXTURE
K. Deepak
Department of Mechanical Engineering,
Vardhaman College of Engineering, Hyderabad, India

M. Ashok Kumar
Department of Mechanical Engineering,
Vardhaman College of Engineering, Hyderabad, India

V. Mahidhar Reddy
Department of Mechanical Engineering,
Institute of Aeronautical Engineering, Hyderabad, India

B. Subramanyam
Department of Mechanical Engineering,
MLR Institute of Technology, Hyderabad, India

ABSTRACT
The use of NH3-H2O mixture as working fluid in power cycle gives higher thermal
performance of power generating systems. The thermodynamic analysis and
simulation of NH3-H2O based power cycle require computation of thermodynamic
properties at various state points in the cycle. In this work, simple functions based on
Gibbs free energy for computing thermodynamic properties of NH3-H2O mixture have
been presented. Computer codes have been developed to compute the properties for
any given pressure, temperature and concentration of NH3 in the mixture. The results
have been validated by comparing with the values presented in the literature in
graphical form and are found to be reasonably accurate. The results are presented in
the form of charts are useful for the analysis of NH3-H2O based power and
refrigeration cycles.
Key words: NH3-H2O mixture, thermodynamic properties, simple functions, Gibbs
free energy, equilibrium properties.
Cite this Article: K. Deepak, M. Ashok Kumar, V. Mahidhar Reddy,
B. Subramanyam, Thermodynamic Property Functions of NH3-H2O Mixture,
International Journal of Mechanical Engineering and Technology 8(8), 2017, pp.
1430–1440.
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 Thermodynamic Property Functions of NH3-H2O Mixture

1. INTRODUCTION
The analysis of NH3-H2O based power and refrigeration system need simple and efficient
functional forms to evaluate the thermodynamic properties of NH3-H2O mixture at various
conditions of pressure, temperature and concentration. Ziegler and Trepp [1] described an
equation for the thermodynamic properties of NH3-H2O mixture. They proposed Gibbs free
energy equation for determining the specific enthalpy, specific entropy and specific volume
and developed the properties up to a pressure of 50 bar and temperature of 227 °C. El-Sayed
and Tribus [2] have reviewed and extended data on properties of NH3-H2O mixture up to 316
°C and 210 bar. The maximum pressure for the correlations has been set to 115 bar which is
slightly above the critical pressure of ammonia Stecco and Desideri [3]. The critical pressure
and temperature of the mixture vary with the mass fraction of ammonia. Patek and Klomfar
[4] presented five simple equations to determine the vapour liquid equilibrium properties of
NH3-H2O mixture. Although the equations used by them are of completely empirical nature,
the results obtained are quite acceptable for industrial use up to 30 bar. Abovsky [5] used the
thermodynamic perturbation theory to determine the properties of pure substance and their
mixture for temperature up to 370 oC and pressure ranging from 0.2 to 230 bar. The deviation
from one-fluid approximation of the mixture has been studied considering the effects of
mixing enthalpy and volume. Xu and Goswami [6] used the Gibbs free energy for evaluating
equilibrium properties in combination with the bubble and dew point temperature. Nag and
Gupta [7] used the Peng-Robinson equation for vapor-liquid equilibrium and the Gibbs free
energy equations presented by Zielger and Trepp [1] for the vapor and liquid phase properties.
Barhoumi et al. [8] presented modelling of the thermodynamic properties. The values of
constants in the functions for the Gibbs excess energy have been recalculated with
experimental data at higher temperatures and pressures (up to 210 bar and 316 °C). Senthil
and Subbarao [9] presented fast calculation for determining enthalpy and entropy of the
mixtures. Ganesh and Srinivas [10] developed a flow chart to understand the computation of
the NH3-H2O mixture properties in Matlab.
The main objective of this work is to develop functional forms to facilitate the calculation
of the thermodynamic properties of NH3-H2O mixture for a wide range of temperature,
pressure and concentration through computer. In this work, the Gibbs free energy method is
considered for determining the properties of NH3-H2O mixture. The Gibbs free energy
equation form Ziegler and Trepp [1] has been utilized for determining the specific enthalpy,
specific entropy and specific volume of the NH3-H2O mixture. The bubble point and the dew
point of the mixture has been calculated by the correlations presented by Patek and Klomfar
[4] and Soleimani [11]. The Gibbs excess energy of liquid mixture is calculated from the
empirical relations proposed by Xu and Goswami [6]. The coefficients presented by Taleb et
al. [12] have been considered.

2. DERIVATIONS OF FUNCTIONS
2.1. Gibbs Free Energy
The Gibbs free energy of a pure substance has been derived considering the known
relations of volume and heat capacity as a function of temperature and pressure.
Equation (1) shows Gibbs free energy of a pure substance in integral form.
𝑇 𝑃 𝑇 𝐶𝑃
ℎ𝑂 − 𝑇𝑠𝑂 + ∫𝑇 𝐶𝑃 𝑑𝑇 + ∫𝑃 𝑣𝑑𝑃 − 𝑇 ∫𝑇 𝑑𝑇 (1)
𝑂 𝑂 𝑂 𝑇

The empirical correlations of heat capacity at constant pressure for the liquid and vapour
phase of both pure water and pure ammonia presented in [1] can be derived as:

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 K. Deepak, M. Ashok Kumar, V. Mahidhar Reddy, B. Subramanyam

𝑣 𝑙 = 𝑎1 + 𝑎2 𝑃 + 𝑎3 𝑇 + 𝑎4 𝑇 2 (2)
𝑅𝑇 𝐶2 𝐶3 𝐶 4𝑇2
𝑣𝑔 = + 𝐶1 + + + (3)
𝑃 𝑇3 𝑇 11 𝑇 11

𝐶𝑃𝑙 = 𝑏1 + 𝑏2 𝑇 + 𝑏3 𝑇 2 (4)

𝑔 𝑃 𝜕2𝑣
𝐶𝑃 = 𝑑1 + 𝑑2 𝑇 + 𝑑3 𝑇 2 − ∫0 𝑂 ( 2 ) 𝑑𝑃 (5)
𝜕𝑇 𝑃

The Gibbs free energy for liquid and gaseous phase has been obtained by substituting the
values of v and CP from equations (2-5) in equation (1). For generalization the Gibbs free
energy at reduced state has been considered.
Liquid Phase:

𝐵2 𝐵3 𝑇𝑟
𝐺𝑟𝑙 = ℎ𝑟,𝑜
𝑙 𝑙
− 𝑇𝑟 𝑆𝑟,𝑜 + 𝐵1 (𝑇𝑟 − 𝑇𝑟,𝑜 ) + (𝑇𝑟2 − 𝑇𝑟,𝑜
2
)+ (𝑇𝑟3 − 𝑇𝑟,𝑜
3
) − 𝐵1 𝑇𝑟 𝑙𝑛 ( )
2 3 𝑇𝑟,𝑜
𝐵3
− 𝐵2 𝑇𝑟 (𝑇𝑟 − 𝑇𝑟,𝑜 ) − 𝑇 (𝑇 2 − 𝑇𝑟,𝑜
2
) + (𝐴1 + 𝐴3 𝑇𝑟 + 𝐴4 𝑇𝑟2 )(𝑃𝑟 − 𝑃𝑟,𝑜 )
2 𝑟 𝑟
𝐴2 2 2
+ (𝑃 − 𝑃𝑟,𝑜 )
2 𝑟

(6)

Gas Phase:

𝑔 𝑔 𝑔 𝐷2 𝐷3 𝑇𝑟
𝐺𝑟 = ℎ𝑟,𝑜 − 𝑇𝑟 𝑆𝑟,𝑜 + 𝐷1 (𝑇𝑟 − 𝑇𝑟,𝑜 ) + (𝑇𝑟2 − 𝑇𝑟,𝑜
2
)+ (𝑇𝑟3 − 𝑇𝑟,𝑜
3
) − 𝐷1 𝑇𝑟 𝑙𝑛 ( )
2 3 𝑇𝑟,𝑜
𝐷3 𝑃𝑟
− 𝐷2 𝑇𝑟 (𝑇𝑟 − 𝑇𝑟,𝑜 ) − 𝑇𝑟 (𝑇𝑟2 − 𝑇𝑟,𝑜
2
) + 𝑇𝑟 𝑙𝑛 ( ) + 𝐶1 (𝑃𝑟 − 𝑃𝑟,𝑜 )
2 𝑃𝑟,𝑜
𝑃𝑟 𝑃𝑟,𝑜 𝑃𝑟,𝑜 𝑇𝑟 𝑃𝑟 𝑃𝑟,𝑜 𝑃𝑟,𝑜 𝑇𝑟
+ 𝐶2 ( 3 − 4 3 + 3 4 ) + 𝐶3 ( 11 − 12 11 + 11 12 )
𝑇𝑟 𝑇𝑟,𝑜 𝑇𝑟,𝑜 𝑇𝑟 𝑇𝑟,𝑜 𝑇𝑟,𝑜
3 3 3
𝐶4 𝑃𝑟 𝑃𝑟,𝑜 𝑃𝑟,𝑜 𝑇𝑟
+ ( 11 − 12 11 + 11 12 )
3 𝑇𝑟 𝑇𝑟,𝑜 𝑇𝑟,𝑜
(7)

The reduced thermodynamic properties are:

𝑇 𝑃 𝐺 ℎ 𝑠 𝑣𝑃𝐵
𝑇𝑟 = , 𝑃𝑟 = , 𝐺𝑟 = , ℎ𝑟 = , 𝑠𝑟 = and 𝑣𝑟 =
𝑇𝐵 𝑃𝐵 𝑅𝑇𝐵 𝑅𝑇𝐵 𝑅 𝑅𝑇𝐵

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 Thermodynamic Property Functions of NH3-H2O Mixture

Table 1 Coefficient Values of Equations (6-7)

Coefficient Water Ammonia

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 1.634519.101 1.214557.101

B2 -6.508119 -1.898065

B3 1.448937 2.911966.10-1

C1 -1.049377.10-2 2.136131.10-2

C2 -8.288224 -3.169291.101

C3 -6.647257.102 -4.634611.104

C4 -3.045352.103 0

D1 3.673647 4.019170

D2 9.989629.10-2 -5.175550.10-2

D3 3.617622.10-2 1.951939.10-2
𝑙
ℎ𝑟,𝑜 4.878573 21.821141

𝑔
ℎ𝑟,𝑜 26.468879 60.965058

𝑙
𝑠𝑟,𝑜 1.644773 5.733498

𝑔
𝑠𝑟,𝑜 8.339026 13.453430

𝑇𝑟,𝑜 3.2252 5.0705

𝑃𝑟,𝑜 2 3

The values of the constants 𝑅, 𝑇𝐵 and 𝑃𝐵 are 8.314 kJ/kmol-K, 100 K and 10 bar
respectively. The values of coefficients Ai, Bi, Ci, and Di used in equations (6-7) are presented
in Table 1.

2.2. Thermodynamic Properties of Pure Component

The Gibbs free energy is related to the molar specific enthalpy, entropy and volume of a pure
component in terms of reduced variables as

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 K. Deepak, M. Ashok Kumar, V. Mahidhar Reddy, B. Subramanyam

𝜕(𝐺𝑟 ⁄𝑇𝑟 )
ℎ = −𝑅𝑇𝐵 𝑇𝑟2 [ ] (8)
𝜕𝑇𝑟 𝑃𝑟

𝜕𝐺𝑟
𝑠 = −𝑅 [ ] (9)
𝜕𝑇𝑟 𝑃
𝑟

𝑅𝑇𝐵 𝜕𝐺𝑟
𝑣= − [ ] (10)
𝑃𝐵 𝜕𝑇𝑟 𝑃
𝑟

2.3. Thermodynamic Properties of NH3-H2O Mixture

The Gibbs free energy of NH3-H2O liquid mixture is obtained by adding the Gibbs excess
energy of the liquid mixture with the Gibbs free energy of the ideal solution mixture. The
deviation of NH3-H2O liquid mixture from ideal solution mixture is compensated by adding
Gibbs excess energy of the liquid mixture [1]. The Gibbs excess energy of liquid mixture is
determined by the empirical relations [6].
𝐺𝑟𝐸 = 𝑥(1 − 𝑥)[𝐹1 + 𝐹2 (2𝑥 − 1) + 𝐹3 (2𝑥 − 1)2 (11)

𝐸5 𝐸6
𝐹1 = 𝐸1 + 𝐸2 𝑃𝑟 + (𝐸3 + 𝐸4 𝑃𝑟 )𝑇𝑟 + + (12)
𝑇𝑟 𝑇𝑟2

𝐸11 𝐸12
𝐹2 = 𝐸7 + 𝐸8 𝑃𝑟 + (𝐸9 + 𝐸10 𝑃𝑟 )𝑇𝑟 + + (13)
𝑇𝑟 𝑇𝑟2

𝐸15 𝐸16
𝐹3 = 𝐸13 + 𝐸14 𝑃𝑟 + + (14)
𝑇𝑟 𝑇𝑟2

Table 2 Coefficient Values of Equations (12-14)

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

The Coefficients for equations (12-14) have been taken from Taleb et al. [12] and are
given in Table 2. The excess specific enthalpy, entropy and volume of the liquid mixture are
given by the following equations.

𝜕(𝐺𝑟𝐸 ⁄𝑇𝑟 )
ℎ𝐸 = −𝑅𝑇𝐵 𝑇𝑟2 [ ] (15)
𝜕𝑇𝑟 𝑃𝑟

𝜕𝐺𝑟𝐸
𝑠 𝐸 = −𝑅 [ ] (16)
𝜕𝑇𝑟 𝑃
𝑟

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 Thermodynamic Property Functions of NH3-H2O Mixture

𝑅𝑇𝐵 𝜕𝐺𝑟𝐸
𝑣𝐸 = − [ ] (17)
𝑃𝐵 𝜕𝑇𝑟 𝑃
𝑟

Therefore, the specific enthalpy, entropy and volume of the liquid mixture are given as:
𝑙 𝑙 𝑙
ℎ𝑚 = 𝑥ℎ𝑁𝐻3
+ (1 − 𝑥)ℎ𝐻 2𝑂
+ ℎ𝐸 (18)
𝑙
𝑙
𝑠𝑚 = 𝑥𝑠𝑁𝐻3
+ (1 − 𝑥)𝑠𝐻𝑙 2 𝑂 + 𝑠 𝐸 + 𝑠 𝑚𝑙 (19)
𝑙
𝑙
𝑣𝑚 = 𝑥𝑣𝑁𝐻3
+ (1 − 𝑥)𝑣𝐻𝑙 2 𝑂 + 𝑣 𝐸 (20)

𝑠 𝑚𝑙 = −𝑅[𝑥𝑙𝑛(𝑥) + (1 − 𝑥) ln(𝑙 − 𝑥)] (21)

The specific enthalpy, entropy and volume of the vapour mixture is also obtained in the
similar way but since the NH3-H2O vapour mixture nearly forms an ideal solution, the Gibbs
excess energy for the vapour mixture is assumed to be zero.
𝑔 𝑔 𝑔
ℎ𝑚 = 𝑦ℎ𝑁𝐻3 + (1 − 𝑦)ℎ𝐻2 𝑂 (22)
𝑔 𝑔 𝑔
𝑠𝑚 = 𝑦𝑠𝑁𝐻3 + (1 − 𝑦)𝑠𝐻2 𝑂 + 𝑠 𝑚𝑔 (23)
𝑔 𝑔 𝑔
𝑣𝑚 = 𝑦𝑣𝑁𝐻3 + (1 − 𝑦)𝑣𝐻2 𝑂 (24)

𝑠 𝑚𝑔 = −𝑅[𝑦𝑙𝑛(𝑦) + (1 − 𝑦) ln(𝑙 − 𝑦)] (25)

2.4. Bubble and Dew Point Temperatures

It is assumed that, in the gas phase above the saturation temperature of water the superheated
NH3-H2O mixture behaves as an ideal solution. When the temperature is between the pure
water saturation temperature and the mixture dew point Td, in the gas phase, the water
component is assumed in a meta-stable vapour state at the considered pressure. Similarly, in
the liquid region, between the saturation temperature of pure ammonia and the bubble point of
the mixture Tb, a meta-stable liquid state for ammonia is assumed. In the wet vapour mixture
region Td > T > Tb we have a saturated vapour mixture with ammonia mass fraction x and a
saturated liquid mixture with ammonia mass fraction y. In the liquid region, below the bubble
point of the mixture Tb, a Gibbs excess function for the departure from ideal-solution
behaviour is assumed.
𝑃 𝑛𝑖
𝑇𝑏 (𝑝, 𝑥) = 𝑇𝑜 ∑𝑖 𝑎𝑖 (1 − 𝑥)𝑚𝑖 [𝑙𝑛 ( 𝑜 )] (26)
𝑃

𝑚⁄ 𝑃 𝑛𝑖
𝑇𝑑 (𝑝, 𝑦) = 𝑇𝑜 ∑𝑖 𝑎𝑖 (1 − 𝑦) 4 [𝑙𝑛 ( 𝑜 )] (27)
𝑃

𝑑
𝑦(𝑥, 𝑃) = 1 − exp [𝑎𝑃𝑏 𝑥 + (𝑐 + ) 𝑥 2 ] (28)
𝑃

The bubble point and dew point temperatures of the NH3-H2O mixture are evaluated using
the equations (26-27) given by Patek and Klomfar [4] and equation (28) presented by
Soleimani [11]. The variation of bubble point and dew point temperatures with ammonia-
mole fraction up to 110 bar is shown in Fig. 1.

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 K. Deepak, M. Ashok Kumar, V. Mahidhar Reddy, B. Subramanyam

600

550

500

110 bar
450 90 bar
70 bar
Temperature (K)

50 bar
400
30 bar

350 10 bar

300

1 bar
0.5 bar
250 0.2 bar

200
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Ammonia Mass Fraction

Figure 1 Variation of bubble point and dew point temperatures with ammonia mass fraction up to 110 bar

3. RESULTS AND DISCUSSIONS

3.1. Specific Enthalpy of NH3-H2O Mixture in Liquid Phase

1100
Present work
1000 Xu and Goswami (1999)

900
Specific Enthalpy (kJ/kg)

800

700

600

500

400

300

200
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Ammonia mass fraction

Figure 2 Specific enthalpy of saturated NH3H2O solution at 34.47 bar

The specific enthalpy and entropy of the NH3-H2O mixture both in liquid and vapour
phase is calculated from equations (18-24). Fig. 2 shows the variation of specific enthalpy of
saturated liquid with ammonia mass fraction at 34.47 bar pressure. The results closely match
with the results of Xu and Goswami [6]. The maximum error is found to be 2.7%.
Considering the high value of pressure, this deviation may be allowed for specific calculation.
It is clear that the specific enthalpy of liquid mixture decreases with ammonia mass fraction
up to a certain point. This is due to the fact that the specific enthalpy of water is much higher
than that of liquid ammonia and as the mass fraction of water decreases slowly with the
increase of mass fraction of ammonia, the specific enthalpy decreases. After a certain point
the specific enthalpy increases with ammonia mass fraction. This is because the excess

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 Thermodynamic Property Functions of NH3-H2O Mixture

enthalpy due to mixing of the two liquids becomes predominant and increases the specific
enthalpy of the mixture.

3.2. Specific Enthalpy of NH3-H2O Mixture in Vapour Phase

2900
Present work
2700 Xu and Goswami (1999)
Specific Enthalpy (kJ/kg)

2500

2300

2100

1900

1700

1500

1300

1100
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Ammonia mass fraction

Figure 3 Specific enthalpy of saturated NH3H2O vapour mixture at 34.47 bar

Fig. 3 shows the variation of specific enthalpy of saturated vapour with mass fraction of
ammonia at 34.47 bar pressure. The results are compared with the results of Xu and Goswami
[6] and are seen to be consistent. The maximum error is found to be 3.4 %. The enthalpy
value decreases continuously with the increase in the concentration.

3.3. Specific Entropy of NH3-H2O Mixture in Liquid Phase

Fig. 4 shows the variation of specific entropy of saturated vapour with ammonia mass fraction
at 37 bar. The computed values of entropy show a good agreement with the data published in
literature [6]. The deviation is nominal and is found to be 4.2%.

4
Present work
Xu and Goswami (1999)
Specific Entropy, kJ/kg-K

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Ammonia mass fraction

Figure 4 Specific entropy of saturated NH3H2O solution at 37 bar

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 K. Deepak, M. Ashok Kumar, V. Mahidhar Reddy, B. Subramanyam

3.4. Specific Entropy of NH3-H2O Mixture in Vapour Phase

The variation of specific entropy of saturated vapour with ammonia mass fraction at 37 bar
has been presented in Fig. 5. The computed values of entropy show a good agreement with
the values presented in literature [6]. The deviation is nominal and is found to be 4.9%.

8
Present work
Xu and Goswami (1999)
7
Specific Entropy, kJ/kg-K

3
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Ammonia mass fraction

Figure 5 Specific entropy of saturated NH3H2O vapour mixture at 37 bar

4. CONCLUSIONS
The equations presented in this paper, combines the Gibbs free energy method for the mixture
properties and the bubble and dew point temperature equations for the phase equilibrium. The
merit of these fast approximation equations include their simplicity, which facilitates to be
used in any computer code. When employed in this alternative way, they provide a substantial
reduction in the number of iterations. The equations are valid for a wide range of temperature
and pressure (230<T<600 K and 0.2<P<110 bar). A computer code has been developed to
generate thermodynamic properties of ammonia water mixture for both liquid and vapour
phase.
The computed results obtained by this work are validated by comparing with the
published data in the literature. The graphs obtained from this work, show a very close trend
of comparison. The maximum error for the enthalpy at 34.47 bar is found to be 2.7% for
saturated liquid and for saturated vapour at the same pressure of 34.47 is found to be 3.4%.
The deviation of saturated specific entropy of the liquid and vapour mixture is found to be
slightly higher with a maximum error of 4.2% and 4.9% at the same pressure 37 bar. Though
the graphs show some variation but it is quite acceptable as the pressure is quite high. Thus
the data generated can be used further for the analysis of NH3-H2O based refrigeration and
power generating systems.

NOMENCLATURE
P pressure (bar)
T temperature (°C)
v molar specific volume (m3kmol-1)
h molar specific enthalpy (kJkmol-1)

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 Thermodynamic Property Functions of NH3-H2O Mixture

s molar specific Entropy (kJkmol-1K-1)

R molar gas constant (kJkmol-1 K-1)
CP heat capacity at constant pressure (kJkg-1K-1)
x ammonia mole fraction in liquid phase
y ammonia mole fraction in vapour phase
a, b, c, d coefficients
A, B, C, D, E, F dimensionless coefficients

REFERENCES
[1] Ziegler, B. and Trepp, C., Equation of state for ammonia-water mixtures. International
journal of refrigeration, 7, 1984, 101-106.

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[15] Abhinav Kumar, Sarbjeet Singh, Ramesh Chand, Vishnu Saini and Raja Sekhar
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