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Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Second law-based thermodynamic analysis of ammonia/sodium

thiocyanate absorption system
Linghui Zhu*, Junjie Gu
Department of Mechanical & Aerospace Engineering, Carleton University, 1125 Colonel by Drive, Ottawa, K1S 5B6, Canada

a r t i c l e i n f o a b s t r a c t

Article history: In this study, the first and second law of thermodynamics are used to analyze the performance of a novel
Received 3 November 2008 absorption system for cooling and heating applications. The active component of the sorbent used in this
Accepted 19 January 2010 study is sodium thiocyanate (NaSCN). Ammonia (NH3) is chosen as sorptive. A mathematic model based
Available online xxx
on exergy analysis is introduced to analyze the system performance. Enthalpy, entropy, temperature,
mass flow rate and exergy loss of each component and the total exergy loss of the system are evaluated.
Keywords:
Furthermore, the coefficient of performance (COP) and exergetic efficiency of the absorption system for
Absorption
cooling and heating processes are calculated from the thermodynamic properties of the working fluids
Ammonia-sodium thiocyanate
Enthalpy under different operating conditions. The results show that the COP of cooling and heating increases with
Entropy the heat source temperature and decreases with the cooling water inlet temperature, but the system
Exergy exergetic efficiency does not show the same trends for both cooling and heating applications. The
simulation results can be used for the thermodynamic optimization of the current system.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Nowadays, with the rapid technology development, advanced
absorption cooling and heating systems have become an accepted
and sound alternative for cooling residential, light commercial and
industrial applications. The air-cooled NH3–H2O and H2O–LiBr cycle
continue to offer many distinct advantages to this field. However,
both working fluid mixtures have some disadvantages that limit
their applications.
In our recent research, the sorbent used is a salt-mixture that has
been developed by DY Refrigeration Inc. and has been used in the
ice-maker fishery industry [1]. The major active component of the
sorbent is sodium thiocyanate (NH3–NaSCN). Ammonia (NH3) is
used as sorptive [2]. The advantages provided by this system over
other absorption units include lower generator and evaporator
temperatures, a higher coefficient of performance (COP). Compared
with NH3–H2O system, the NH3–NaSCN adsorption system doesn’t
need the rectifier because there are only NH3 in the vapor phase and
the salt (NaSCN) doesn’t evaporate at all, that makes the system
simpler and cheaper. Among the first studies on an NH3–NaSCN
system are those of Blytas and Daniels [3] and Sargent and Beckman
[4]. Tyagi [5] and Aggarawal et al. [6] provided a review on ammonia-
salts absorption refrigeration systems. Thermodynamic and physical
* Corresponding author.
E-mail address: lzhu2@connect.carleton.ca (L. Zhu).
properties for the NH3–LiNO3, and NH3–NaSCN solutions have been
presented by Ferreira [7], while interesting energy performance
comparisons between NH3–H2O, NH3–LiNO3 and NH3–NaSCN
absorption systems may be found in the works of Sun [8].
This paper differs from the other literature studies in that the
second law based thermodynamic analysis is carried out to eval-
uate the thermodynamic performance of an NH3–NaSCN absorp-
tion system. Second law analysis is based on the concept of exergy,
which can be defined as a measure of work potential or quality of
different forms of energy relative to environmental conditions
[9,10]. A number of researchers have conducted various analyses for
refrigeration systems. A theoretical analysis was given by Bejan [11]
based on entropy generation minimization. Szargut et al. [9] pre-
sented energy and exergy balance of an NH3–H2O absorption
refrigerator. Exergy analysis of an absorption LiBr–H2O refrigera-
tion cycle was carried out by Sencan et al. [12] and Talbi and Agnew
[13]. However, there is no academic work on exergy analysis for the
NH3-NaSCN system found in open literature. This study focuses on
performing an exergy analysis on a NH3–NaSCN absorption system
at different operating conditions.
2. Thermodynamic analysis
In this study, energy and mass balances are applied to each
component and combined with the state equations for the ther-
modynamic properties of the working fluids to provide with a set of
equations to describe the system characteristics. In order to

0960-1481/$ – see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.renene.2010.01.022

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2 L. Zhu, J. Gu / Renewable Energy xxx (2010) 1–7

determine the heat and mass transfer properties of the system, The relation between temperature and specific enthalpies of
each component is taken as a single unit, the balance equations of superheated vapor ammonia is given as:
mass, energy and exergy for the generator, condenser, evaporator ZT2
and absorber were calculated separately. hsuperheated ðT2 Þ ¼ hsaturated ðT1 Þ þ cp dT (12)
T1

2.1. Fluid properties where T1 is the saturated temperature corresponding to the pres-
sure of this superheated vapor ammonia, and hsaturated(T1) is the
The performance and efficiency of the absorption refrigeration corresponding enthalpy, T2 is temperature of the superheated
system are determined to a large degree by the properties of the vapor ammonia, hsuperheated(T2) is the corresponding enthalpy. Cp is
working fluids. In this analysis presented here, ammonia is the the specific heat and is given as:
refrigerant, and sodium thiocyanate is the absorbent, therefore the
thermodynamic properties for ammonia and ammonia/sodium 6
X
thiocyanate solution were studied. Except for entropy, the proper- Cp ¼ di ðT  273:15Þi (13)
ties of ammonia-sodium thiocyanate solution have been studied by i¼0

Ferreira [7], and the properties of vapor and liquid ammonia The above equations were collected by Zhu et al. [2] with source data
properties are provided by Sun [8]. taken from the properties of R-717 (ANHYDROUS AMMONIA)
The relation among saturation equilibrium pressure, concen- handbook presented by Industrial Refrigeration Consortium at
tration and temperature is given as: University of Wisconsin [15], and the coefficient di is listed in Table 1.
Unlike the above property values, for which the correlations are
B
ln P ¼ A þ (1) normally based on experimental data, the entropy of NH3–NaSCN
T solutions has not been studied before. The entropy data used in this
where paper are collected by the author based on the theory used by
Koehler et al. [16] and Aphornratana and Eames [17] for the entropy
A ¼ 15:7266  0:298628X (2) of LiBr–H2O solutions.
In order to simplify the entropy equations offered by the above
B ¼ 2548:65  2621:92ð1  XÞ3 (3) mentioned researchers, the pressure dependence of the entropy
may be neglected, thus the reference entropy is a function of the
The relation among temperature, concentration and enthalpy is solution concentration and the related temperature only. Based on
as follows: this assumption, at constant concentrations, the entropy of NH3–
NaSCN at 25  C is calculated as:
h ¼ A þ BðT  273:15Þ þ CðT  273:15Þ2 þDðT  273:15Þ3
(4) hsol  gsol
S25 ¼ (14)
298:15
where
The Gibbs’ free energy of solution can be obtained as partial
A ¼ 79:72  1072X þ 1287:9X 2  295:67X 3 (5) molar quantities [18]:

X 1X
B ¼ 2:4081  2:2814X þ 7:9291X 2  3:5137X 3 (6) gsol ¼ m þ m (15)
MNH3 NH3 MNaSCN NaSCN
  The chemical potential of ammonia and sodium thiocyanate
C ¼ 102 1:255X  4X 2 þ 3:06X 3 (7)
components in the solution are:
 
D ¼ 105  3:33X þ 10X 2  3:33X 3 (8)
mNH3 ¼ ðhv  298:15$Sv ÞNH3 (16)

within the ranges of pressure and temperature concerning refrig- mNaSCN3 ¼ 596:3R$lnðmNaSCN $gÞ þ 298:15K (17)
eration applications, the two phase equilibrium pressure and
temperature of the refrigerant ammonia are linked by the relation: where, K ¼ 0:1922kJ=kmol K. And the mean ionic activity coeffi-
cient g is obtained by Meissner’s method [19].
6
X The entropy of solution at the temperature T can be obtained from:
P ¼ 103 ai ðT  273:15Þi (9)
i¼0 R h  i
St ¼ S25  X NaSCN logðX NaSCN $gÞ þ X NH3 log P=P * (18)
The specific enthalpies of saturated liquid and vapor ammonia Msol
are expressed in terms of temperature as follows:

6
X Table 1
hl ¼ bi ðT  273:15Þi (10) Coefficients of equations (9)–(11) and (13).
i¼0
i ai equation (9) bi equation (10) ci equation (11) di equation (13)

6 0 4.2871  101 1.9879  102 1.4633  103 1.7467  104

X i 1 1.6001  102 4.4644  100 1.2839  100 3.3129  102
hv ¼ ci ðT  273:15Þ (11)
2 2.3652  104 6.2790  103 1.1501  102 2.6189  100
i¼0
3 1.6132  106 1.4591  104 2.1523  104 1.1045  102
The above three equations are fitted by Sun [8] with source data 4 2.4303  109 1.5262  106 1.9055  106 2.6214  105
5 1.2494  1011 1.8069  108 2.5608  108 3.3202  108
taken from ASHRAE handbook [14]. The coefficients are listed in 6 1.2741  1013 1.9054  1010 2.5964  1010 1.7539  1011
Table 1.

Please cite this article in press as: Zhu L, Gu J, Second law-based thermodynamic analysis of ammonia/sodium thiocyanate absorption system,
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L. Zhu, J. Gu / Renewable Energy xxx (2010) 1–7 3

QG
QC
1
condenser generator

8 7
2

V1

9
Generator Absorber
V2 6 Exchanger (HEX)
3
10

4 Circulation
5
evaporator absorber pump
QE

QA
Fig. 1. The schematic of a single stage NH3-NaSCN absorption cycle.

2.2. System description and analysis The energy balance of each component based on the first law of
thermodynamic is:
Fig. 1 illustrates the main components of the system. High- X  X  X 
pressure liquid refrigerant (2) from the condenser passes into the m_ i hi  m_ o ho þ Qi  Qo þ W ¼ 0 (21)
evaporator through an expansion valve V1 that reduces the pressure
of the refrigerant to the low pressure level as in the evaporator. The where m_ is the mass flow rate, X is the mass concentration of
liquid ammonia vaporizes in the evaporator by absorbing heat from ammonia in the solution, and h is the enthalpy of the working fluid.
the material being cooled and resulting low pressure vapor The system cooling and heating COP can be written as:
ammonia (4) passes to the absorber, where it is absorbed by the
strong solution (10) coming from the generator through the gener- QE m_ 4 ðh4  h3 Þ
COPcooling ¼ ¼ (22)
ator absorber exchanger (HEX), and form the weak solution (5). The QG _ 1 h1 þ m
m _ 8 h8  m
_ 7 h7
weak solution is pumped to the HEX and then the generator, and the
solution is boiled in the generator. The remaining solution (8) flows Q A þ QC m_ ðh  h2 Þ þ m _ 10 h10  m
_ 4 h4 þ m _ 5 h5
COPheating ¼ ¼ 1 1
back to the absorber and the superheated vapor ammonia (1) passes QG _ _ _
m1 h1 þ m8 h8  m7 h7
into the condenser and liquefied to high-pressure liquid ammonia (23)
by releasing heat to the cooling material and, thus, completes the
cycle. The function of HEX is to improve system performance. The circulation ratio of the system can be defined as:
Based on the properties of the working solution pair, the
equations of mass and energy conservation are determined to _7
m
f ¼ (24)
describe the heat and mass transfer in every component. The _1
m
governing mass conservation equations for a steady state are:
X X The second law analysis can be used to calculate the system
_i
m _o ¼ 0
m (19) performance based on exergy. Exergy analysis is the combination of
the first and second laws of thermodynamics and is defined as the
X  X  maximum amount of work potential of a material or an energy
m_ i Xi  m_ o Xo ¼ 0 (20)
stream, in relation to the surrounding environment [20,21].

Table 2
Absorption system data obtained from the thermodynamic analysis.

Point T ( C) h (kJ/kg) s (kJ/kg K) m (kg/s) x (% NH3) e (kJ/kg) P (kPa)

1 90 1689.7 4.337 0.0038 100 411.979 1002.6
2 25 315.88 1.123 0.0038 100 0 1002.6
3 25 315.88 1.123 0.0038 100 0 290.76
4 10 1449.5 5.473 0.0038 100 166.979 290.76
5 25 101.847 0.726 0.03 0.4618 0 290.76
6 25 101.847 0.726 0.03 0.4618 0 1002.6
7 67.92 15.767 1.033 0.03 0.4618 26.08 1002.6
8 90 71.783 1.056 0.0262 0.3843 52.072 1002.6
9 38 62.767 0.747 0.0262 0.3843 9.62 1002.6
10 38 62.767 0.747 0.0262 0.3843 9.62 290.76

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Table 3
Energy transfer rates at the various components and performance parameters of the
system.

Component Energy transfer

rates (kW)
Generator (QG) 7.7899
Condenser (QC) 5.1877
Evaporator (QE) 4.2809
Absorber (QA) 6.8832
HEX (QHEX) 3.5284

Performance parameters
Coefficient of performance for colling 0.5495
(COPcooling)
Coefficient of performance for heating 1.5495
(COPheating)
Circulation ratio (f) 7.9445

The exergy of a fluid stream can be defined as [10]:

e ¼ ðh  h0 Þ  T0 ðs  s0 Þ (25)
Fig. 2. Variation of the COP and exergetic efficiency of the system with the generator
where e is the exergy of the fluid at temperature T. The terms h and temperature for cooling application (TE ¼ 10  C, TC ¼ TA ¼ 25  C).
s are the enthalpy and entropy of the fluid respectively, ho and so are
the enthalpy and entropy of the fluid at environmental temperature
To. In this study, To was taken as 298.15 K. Based on above heat and mass balances, heat transfer equations
The exergy loss in each component and the total exergy loss for and the state equations for thermodynamic properties, a computer
the system are due to exergy destruction and heat transfer under simulation program was built to investigate the energy and exergy
temperature and unrestricted expansion and can be written as: analysis of the system. The initial conditions used in this program
include the heating, cooling and chilled water inlet temperatures,
DE_ G ¼ m
_ 8 e8  m _ 1 e1 þ Q_ G ð1  T0 =TG Þ
_ 7 e7  m (26) mass flow rate and the heat exchanger efficiency. In order to
simplify the simulation process, the work input to the solution
DE_ A ¼ m
_ 4 e4 þ m _ 5 e5  Q_ A ð1  T0 =TA Þ
_ 10 e10  m (27) pump and the friction losses of the system are neglected.

DE_ C ¼ m _ 2 e2  Q_ C ð1  T0 =TC Þ
_ 1 e1  m (28) 3. Results and discussion

_ 4 e4 þ Q_ E ð1  T0 =TE Þ With the given parameters, the simulation program calculates

DE_ E ¼ m
_ 3 e3  m (29)
the values of temperature, enthalpy, entropy, mass flow rate,
concentration exergy of the fluid at all points of the absorption
DE_ GAX ¼ m
_ 6 ðe6  e7 Þ þ m
_ 8 ðe8  e9 Þ (30) cycle. The results are listed in Table 2.
The simulation results of the first law analysis of current system
DE_ T ¼ DE_ G þ DE_ A þ DE_ C þ DE_ E þ DE_ GAX (31) are presented in Table 3. In the simulation, the input parameters are
taken as TG ¼ 90  C, TC ¼ TA ¼ 25  C, TE ¼ 10  C, 3GAX ¼ 0.80. It is
The second law efficiency of the absorption system is measured by shown that the highest heat load occurs in the generator and the
the exergetic efficiency, ECOP, which is defined as the ratio of the
useful exergy gained from a system to that supplied to the system.
Therefore, the exergetic efficiency of the absorption system for
cooling and heating purpose can be expressed as:

_ 4 ðe4  e3 Þ
m
ECOPcooling ¼ (32)
_ 1 e1 þ m
m _ 8 e8  m_ 7 e7

_ 1 ðe1  e2 Þ þ m
m _ 4 e4 þ m_ 10 e10  m
_ 5 e5
ECOPheating ¼ (33)
m_ 1 e1 þ m_ 8 e8  m_ 7 e7

Table 4
Exergy loss rates of the components.

Components Exergy loss Non-dimensional

rate (kW) exergy loss (%)
Generator 0.4107 14.91
Condenser 1.5655 56.85
Evaporator 0.0651 2.37
Absorber 0.3825 13.89
HEX 0.3299 11.98
Fig. 3. Variation of the COP and exergetic efficiency of the system with the generator
Total 1.9887 100
temperature for heating application (TE ¼ 10  C, TC ¼ TA ¼ 25  C).

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Fig. 4. Variation of the COP and exergetic efficiency of the system with the condenser
and absorber temperature for cooling application (TG ¼ 90  C, TE ¼ 10  C).
load in the condenser is slightly higher than that in the evaporator,
this is primarily due to the superheating property of the inlet vapor
ammonia in the condenser.
Table 4 shows the simulation results of the second law analysis.
At this working condition, the condenser has the highest exergy
loss, and then the generator and the absorber, the evaporator has
the lowest exergy loss. Variation of the exergy loss rate for each
component for various operating conditions will be comprehen-
sively examined below.
Fig. 2 presents that the variation of the coefficient of perfor-
mance and exergetic efficiency of the absorption system for cooling,
versus different generator temperatures. It is shown that the
cooling exergetic efficiency initially increases and declines contin-
uously as the generator temperature increases. It also should be
noted that the COP initially exhibits significant increase with an
increasing generator temperature, and when the generator
Fig. 5. Variation of the COP and exergetic efficiency of the system with the condenser
and absorber temperature for heating application (TG ¼ 90  C, TE ¼ 10  C).
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5
Fig. 6. Variation of the COP and exergetic efficiency of the system with evaporator
temperature for cooling application (TG ¼ 90  C, TC ¼ TA ¼ 25  C).
temperature is higher than 75  C, the slope of the COP curves
becomes almost flat. This suggests that, increasing the generator
temperature higher than a certain value will not provide much
improvement in COP. This can be explained by the fact that
although a system with a high generator temperature can produce
more hot ammonia vapor, more input exergy is supplied; it also
generates more exergy losses in the generator, condenser and
absorber as their average temperatures rise up. This contributes
negatively to the exergetic efficiency of the system. Since this
negative effect of increasing the generator temperature is more
dominant on the exergetic efficiency of the system, while the
system COP stays almost constant. This negative result on the
exergetic efficiency and COP trades off the beneficial effect of the
generator temperature increase.
Fig. 3 shows variation of the COP and exergetic efficiency of the
absorption with the generator temperature for heating applica-
tions. In this case, compared with cooling applications, the system
heating COP has the same trend of curve, but the trend of exergetic
efficiency curve is reversed. It can be explained that when the
Fig. 7. Variation of the exergy loss percentage of different components with generator
temperature (TE ¼ 10  C, TC ¼ TA ¼ 25  C).
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6 L. Zhu, J. Gu / Renewable Energy xxx (2010) 1–7

generator temperature is lower than a certain value, a higher of exergy losses in order to increase the exergetic efficiency of the
generator temperature can produce more exergy loss, otherwise, system.
when the generator temperature is higher than that value, the Finally, the results of the energy and exergy analysis presented
generator temperature increase will cause the increase of the in this paper can be applied as a useful tool for evaluation and
absorber and condenser output temperatures, furthermore, the improvement of the absorption systems, it provides a simple and
exergy output from the condenser and absorber will increase. effective method to identify how losses at different devices are
Fig. 4 shows variation of the COP and exergetic efficiency of the interdependent and where a given design should be modified for
absorption with the condenser and absorber temperature for the best performance.
cooling applications. In this case, both COP and exergetic efficiency
decrease with the increase of the condenser and absorber Acknowledgements
temperature. The reason for this behavior is that, as the increase of
the condenser and absorber temperature, the system pressure in This study was supported by NSERC (Natural Sciences and
the generator part will increase, and as a result, less ammonia vapor Engineering Research Council, Canada), OCE (Ontario Centres of
will be released from the generator. At the same time, a lower Excellence) and Thermalfrost Inc. (Ottawa, Canada).
condenser and absorber temperature has a bigger potential to
crease cooling effect at the same flow rate.
Nomenclature
Fig. 5 shows variation of the COP and exergetic efficiency of the
absorption with the condenser and absorber temperature for heating
applications. This can be explained by the fact that, the condenser and
COP coefficient of performance
absorber temperature are decided by the cooling water temperature,
ECOP exergetic efficiency
and the cooling water with higher inlet temperature will produce
f circulation ratio
outlet water with higher temperature, and the water at a higher
X liquid phase concentration (kg NH3/kg solution)
temperature has a bigger potential to extract energy for heating
cp specific heat (kJ/kg K)
application. And because the higher cooling water temperature can
T temperature ( C)
decrease the mass fraction slightly, the effect of condenser and
h specific enthalpy (kJ/kg)
absorber temperature in COP and exergetic efficiency is small.
S specific entropy (kJ/kg K)
Fig. 6 shows variation of the COP and exergetic efficiency of the
P absolute pressure (k Pa)
absorption system with the evaporator temperature for cooling
Q heat transfer rate (kW)
applications. As it can be seen, the cooling COP increases when the
m_ mass flow rate (kg/s)
evaporator temperature increases. The reason is that a higher
h specific enthalpy (kJ/kg)
evaporator temperature will cause a higher absorbing pressure,
m molarity (mol/mol)
which will greatly increase the absorption efficiency of the strong
e specofoc exergy (kJ/kg)
solution. Unlike COP, the exergetic efficiency of the system
g Gibbs’ free energy (J/mol)
decreases with the increase of the evaporator temperature. It can
also be explained by the definition of the second law of thermo-
DE exergy loss rate (kW)
M molecular weight (kg/kmol)
dynamics that the lower evaporator temperature has a bigger
R universal gas constant (kJ/kmol K)
potential to create cooling effect.
Fig. 7 shows variation of the exergy loss percentage of different
components versus different generator temperatures. It is shown
that the exergy losses of the generator and condenser are major Greek letters
fractions of the total exergy loss in the system. The sum of the non- m chemical potential (kJ/kmol)
dimensional exergy losses of these two components is about 80%, 3 heat exchanger effectiveness (%)
which is remarkably a high value. The values of the exergy loss for g mean ionic activity coefficient
the evaporator and HEX remain approximately stable. When the
generator temperature increase, the non-dimensional exergy losses
of the condenser and absorber will increase gradually, while the Subscripts
corresponding exergy value of the generator will decrease A absorber
remarkably. Therefore, in order to decrease the total exergy loss of C condenser
the system, the condenser, generator and absorber should be E evaporator
regarded as system components that need improvement. G generator
i inlet stream
4. Conclusion o outlet stream
v vapor ammonia
In this paper, the first and the second law of thermodynamics l liquid ammonia
are applied to a single stage NH3–NaSCN absorption system for
cooling and heating applications, the performance analysis and
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