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SUMMARY
The aim of this study is to present a methodology to calculate the exergy of lithium bromidewater solution
(LiBr/H2O) widely used in absorption refrigeration systems, absorption heat pumps and absorption heat
transformers. As the LiBr/H2O solution is not ideal, it is necessary to take into account the activity of the
constituents in the chemical exergy calculation. Adopting the reference environment proposed by Szargut et al.,
the chemical exergy of pure LiBr was obtained as well as the chemical and physical exergy of the LiBr/H2O
solution. Results are reported in the temperature range between 5 and 1801C. In the literature, exergy values for
LiBr/H2O solution are widely varied. This fact is due to different reference systems adopted to calculate exergy.
Some cases in the literature are compared with that obtained with the methodology proposed in this study and
with the approaches of Koehler, Ibele, Soltes and Winter and Oliveira and Le Goff. Copyright r 2010 John
Wiley & Sons, Ltd.
KEY WORDS
absorption system; exergy; lithium bromide; chemical exergy; reference system
Correspondence
*S. A. Nebra, NIPE/UNICAMP, Cidade Universitaria Zeferino Vaz, P.O. Box 1170, Campinas, SP, 13084-971, Brazil.
y
E-mail: Silvia.nebra@pq.cnpq.br
Received 23 April 2010; Revised 3 September 2010; Accepted 7 September 2010
1. INTRODUCTION
The bromide lithiumwater (LiBr/H2O) solution is
widely used as working uid in absorption refrigeration systems because of its nonvolatile and non-toxic,
besides being environmentally friendly by not contributing to ozone depletion. Employing this solution
avoids the use of CFC refrigerants and its consequent
environmental damage.
Low cost and easy handling are the advantages
of using water as refrigerant (despite its high
freezing point). On the other hand, low crystallization
temperature, high absorption capacity and low
viscosity are the advantages of LiBr/H2O solution as
absorbent [1].
Absorption refrigeration systems are attractive and
of increasing interest because they can be driven by
low-temperature heat sources and provide an excellent
Copyright r 2010 John Wiley & Sons, Ltd.
R. Palacios-Bereche et al.
2.2. Enthalpy
The enthalpy of LiBr/H2O solution was evaluated
following the procedure described by Kim and Infante
Ferreira [14],
l
E
h yLiBr h1
LiBrT;p 11 yLiBr hH2 OT;p 1hT;p;m 1
where h1
LiBrT;p is the molar enthalpy of the ideal LiBr
uid, hlH2 OT;p is the molar enthalpy of pure water and
hET;p;m is the enthalpy excess. These terms can be
calculated by Equations (2)(4). Values of the constants employed are presented in Table I.
Z T
1 1
h
C1
h1
LiBr
LiBr;0
pLiBr dT
T0
1
@VLiBr
V1
p p0
LiBr T
@T
hHl 2 O hHl 2 O;0 1
p0
h E yLiBr v R T2
T0
4Vl
ClpH2 O dT
H2 O
T
@VHl 2 O
@T
! 3
5 dp
6
X
2 @ai
i @bi
1
p mi=2 4
i @T 2:v @T
j1
R. Palacios-Bereche et al.
j51
1
j52
3
a1j
a2j
a3j
a4j
a5j
a6j
b0j
b1j
b2j
cj
dj
ej
2.19631610
3.810475 103
11.228085 105
1.471674106
17.765821 106
1.511892 107
4.417865 105
13.074104
4.080794 104
9.440134105
11.197193 101
12.66299 103
14.937232 10
12.611535 106
7.718792 107
19.195285 108
4.937567109
19.839974 109
13.1149002
1.86321 101
12.1608101
5.842326108
1.83055 102
3.865189 106
6.5548406 105
3.6699691 108
11.039856 1010
1.189450 1011
16.317555 1011
1.27379 1012
4.36112260
12.738714 101
2.5175971 101
0
12.870938105
17.464841 109
h1
LiBr;0
s1
LiBr;0
T0
hlH2 O;0
slH2 O;0
p0
0
0
0.6108 kPa
Figure 2. Enthalpy of lithium bromidewater solutions as a function of the concentration for different temperatures.
C p1LiBr R T 2
j0
Tj
ai
5
C pl H2 O R
2
X
dj T j
ej T j
j0
V Hl 2 O R
2
X
j0
aij T j
bij T j
10
j0
bi
1
V LiBr
R T b0
2
X
2
X
j0
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
R. Palacios-Bereche et al.
2.3. Entropy
For the entropy evaluation of the LiBr/H2O solution,
the correlation proposed by Kim and Infante Ferreira
[14] is used:
l
s yLiBr s1
LiBrT;p 11 yLiBr sH2 OT;p yLiBr
m
1 1sET;p;m
n R ln
12
m0
p
p0
ClpH2 O
T0
@VlH2 O
@T
T
!
dT
dp
p
14
s E yLiBr v R
6
X
i bi
@ai
i @bi
p1T
1
p mi=2 15
ai 1
2v
@T 2:v @T
j1
l
Values of s1
LiBr;0 and sH2 O;0 are shown in Table I. The
same reference values of enthalpy were used (01C for
pure water and solution at 50 wt%). The validity range
for Equation (12) is: mass fraction of LiBr, x, from 0 to
70% and solution temperatures, T, from 0 to 2101C.
Entropy in mass basis is calculated using Equation
(16). The results of entropy are presented in Figure 3.
sol
s s=M
16
2.4. Activities
Water activity in the solution can be calculated by the
following expression [16]:
H2 O
lnaH2 O f v m M
17
2.4.1. Molality. Molality is normally dened as the
number of moles of solute per kilogram of solvent. In
the calculation, following the procedure reported in
[14], the molality is redened as kilomole of solute per
kilogram of solvent.
Then, the molality can be calculated from the LiBr
mole fraction (yLiBr) or the LiBr mass fraction (xLiBr)
as shown by the following equation:
xLiBr
yLiBr
m
18
H2 O
1 xLiBr MLiBr 1 yLiBr M
2.4.2. Osmotic coefcient. Kim and Infante Ferreira
[14] present the following expression to calculate the
osmotic coefcient of the LiBr/H2O solution. The
Figure 3. Entropy of lithium bromidewater solutions as a function of the concentration for different temperatures.
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
R. Palacios-Bereche et al.
6
X
ai :mi=2 1
i1
2
p X
i bi :mi=2
2:n i1
19
2.4.3. Calculation of the LiBr activity in the solution. The LiBr activity in the solution can be
calculated from the water activity, applying the
GibbsDuhem equation, Equation (20), following the
method described in [17]. This method is utilized to
calculate the activity of a non-volatile component
when the activities of the other species are known:
Z
1
d ln aLiBr
yH2 O
dln aH2 O
yLiBr
20
where b3 b4 b5 b6 0.
3. EXERGY CALCULATION
OF LIBR/H2 O SOLUTION
Exergy of the lithium bromide solution can be
calculated as the sum of both physical and chemical
exergy:
22
ex exph 1exch
23
i1
i1
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
R. Palacios-Bereche et al.
In Equation (28), n indicates the number of elements, while subscript el indicates the element.
e~0H2 O 1yLiBr
e~0LiBr 1R
25
26
R~ T0
y
lnaH2 O 1yLiBr lnaLiBr 27
sol H2 O
M
Li 1 12 Br2 ! LiBr
29
30
where
Dg~0LiBr 342:0 kJ mol1 20
The result of Equation (28) is: e~0LiBr 101:6 kJ=mol.
This value will be used later in Equation (25) for chemical exergy calculation of the LiBr/H2O solution.
Figure 7 presents the chemical exergy calculated as a
function of standard chemical exergies of solution
components (exch;0) as indicated in Equation (26), the
variation of chemical exergy due to the dissolution
process (exdis), calculated according to Equation (27)
and the total chemical exergy at 251C calculated by the
sum of previous terms according to Equation (25).
Figure 8 presents the total exergy by summing up
both physical and chemical terms, calculated according
to Equation (22).
3.2.1. Standard chemical exergies. The standard chemical exergies for water, lithium and bromide were
found in [10]. Rivero and Garas [19] accomplished a
revision and re-calculation of the standard chemical
exergies of elements but their results, for the substances
Li and Br, do not present signicant differences
(deviations around 0.2%) in comparison with the
values reported in [10].
e~0H2 O 0:9 kJ=mol
e~0Li 393 kJ=mol
e~0Br2 101:2 kJ=mol
The standard chemical exergy for the LiBr compound
can be calculated following Kotass proposal [11]:
e~0 Dg~0f 1
n
X
e~0el
28
i1
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
R. Palacios-Bereche et al.
4. STUDY OF CASES
COMPARISON WITH OTHER
APPROACHES
31
The term cx (T, p) is the temperature- and pressuredependent part of the exergy (thermal term) while the
term c0(x) represents the exergy of dissolution. To nd
c0(x), these authors imagine a mixture at T0 and p0
undergoing a change of state from a given concentration x to the dead state xsat by admitting an amount of
solute at T0 and p0. Applying the rst and second law
of thermodynamics to this process, the authors get
an equation for exergy calculation of the LiBr/H2O
solution.
Thus, the minimum level of exergy corresponds to
the saturated solution xsat while the highest value
corresponds to pure water. In order to maintain the
consistency in exergy balances, these authors should
calculate the exergy of pure water according to their
correlations, which consider the saturate state xsat of
LiBr/H2O solution as reference state.
Figure 10. Path from initial state at xM, T and p to the reference
state according approach of Oliveira and Le Goff [21].
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
R. Palacios-Bereche et al.
Table II. Operational conditions for absorption heat pump evaluated by Koehler et al. [1]Comparison of specific exergy values with
other approaches.
1S
1
2
3S
3
4
5
6PU
6
7G
7
8
Oliveira and
Le Goff [21]
This study
M (kg/s)
T (K)
P (kPa)
vfrac
x%
h (kJ kg1)
c (kJ kg1)
1
1
1
1
1
1
4.713
4.713
4.713
3.713
3.713
3.713
280.2
304.2
357
328.2
317.4
280.2
303.2
303.2
330.9
388.2
345.7
331.1
1
1
15.73
15.73
15.73
1
1
15.73
15.73
15.73
15.73
1
1
1
1
0
0
0.063
0
0
0
0
0
0.009
0
0
0
0
0
0
51.1
51.1
51.1
64.9
64.9
64.9
2513.76
2558.96
2656.09
230.46
185.26
185.26
174.05
174.04
113.92
20.02
96.36
96.33
8.9610
9.1332
8.1181
0.7686
0.6276
0.6597
0.2831
0.2831
0.4721
0.6848
0.4680
0.4672
647.72
645.03
1024.51
643.15
637.18
628.22
53.74
53.76
61.30
9.87
6.14
5.92
157.6
158.6
229.4
5.834
2.4
8.529
87.48
87.49
91
214.5
200.2
199.8
107.7
108.6
279.4
55.79
52.36
41.43
447.7
447.7
451.2
658.6
644.3
643.8
Values of enthalpies, entropies and specic exergies reported by Koehler et al. [1].
y
Enthalpies and entropies were calculated by equations of Kim and Infante Ferreira [14] according to item 2 of this study.
Sencan et al. [5] also indicate 251C as reference temperature but they do not indicate the reference pressure
nor the chemical composition of reference state. The
internal system pressures were calculated considering the
temperature at condenser outlet and evaporator outlet.
Thus, the lower and the higher pressures obtained for
the system were 1.002 and 7.381 kPa, respectively. It was
not possible to compare the results of irreversibilities or
exergetic efciencies reported by the authors [5] as
they did not report values of pressure for points of the
external circuit (11, 12, 13, 14, 15, 16, 17, 18).
From Table III it can be observed that specic
exergies of LiBr/H2O solution in Sencan et al. [5] study
are lower in comparison with the values obtained from
approaches of this study and Oliveira and Le Goff [21].
In comparison with Koehler et al. [1] approach, specic exergies of LiBr/H2O solution of Sencan et al. [5]
are lower than Koehler et al. values [1] for x 5 57.59%
but they are higher for x 5 58.15%.
R. Palacios-Bereche et al.
balance.
I
X
m_ in exin
m_ out exout Q_
T0
_ vc
W
1
Tr
32
Table III. Operational conditions for absorption heat pump evaluated by Sencan et al. [5]Comparison of specific exergy values with
other approaches.
1
2
3
4
5
6
7
8
9
10
This study
m (kg s1)
T (1C)
x (%)
c (kJ kg1)
cy (kJ kg1)
0.5
0.5
0.5
0.495
0.495
0.495
0.005
0.005
0.005
0.005
40
40
67.6
80
52
52
80
40
7
7
57.59
57.59
57.59
58.15
58.15
58.15
0
0
0
0
12.95
12.95
22.09
29.73
21.52
21.52
99.07
3.12
3.12
161.7
20.87
20.87
25.67
26.29
19.59
19.59
745.7
622.6
614.5
463.8
130.8
130.8
135.6
143.3
136.6
136.6
124.6
1.432
6.601
157.3
530.4
530.4
535.2
546.3
539.6
539.6
174.5
51.39
43.36
107.4
Values calculated in this studyProperties calculated according Kim and Infante Ferreira [14] procedure.
Table IV. Operational conditions for absorption refrigeration system evaluated by Arora and Kaushik [3]Comparison of specific
exergy values for different approaches.
1
2
3
4
5
6
7
8
9
10
Oliveira and
Le Goff [21]
This study
m (kg s1)
T (1C)
p (kPa)
Vfrac
x (%)
h (kJ kg1)
c (kJ kg1)
9.035
9.035
9.035
8.035
8.035
8.035
1
1
1
1
37.8
37.8
66.2
87.8
53.08
53.08
87.8
37.8
7.2
7.2
1.016
6.558
6.558
6.558
6.558
1.016
6.558
6.558
1.016
1.016
0
0
0
0
0
0.002251
0
0
0.05155
0
55.42
55.42
55.42
62.32
62.32
62.32
0
0
0
0
91.539
91.543
148.953
221.19
156.635
156.635
2664.211
158.301
158.301
2513.751
0.2288
0.2288
0.4054
0.4787
0.2905
0.2906
8.58
0.5428
0.5661
8.968
32.56
32.57
37.35
10.42
1.882
1.881
731.9
622.2
615.2
465.7
114.9
114.9
119.7
180.4
171.8
171.8
110.8
1.021
5.911
155.4
501.4
501.4
506.2
608.7
600.2
600.2
160.7
50.98
44.05
105.5
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
R. Palacios-Bereche et al.
35
Table V. Irreversibilities in kW for each component of the systemComparison of results in system evaluated by Arora
and Kaushik [3].
Gouy Stodola
equation
Absorber
Condenser
Evaporator
Generator
Heat exchanger of solution
Arora and
Kaushik [3]
(1)
(2)
(3)
66.24
6.60
86.25
57.15
27.69
70.48
6.61
86.28
55.57
25.08
67.24
6.60
86.25
57.15
25.36
Koehler
et al. [1]
Oliveira and
Le Goff [21]
This study
66
6.60
86.25
57.39
25.36
66.28
6.60
86.25
57.12
25.36
66.47
6.60
86.25
56.93
25.36
(1) Values calculated in this studyEntropy calculated according Kim and Infante Ferreira [14] procedure. (2) Values reported by
Arora and Kaushik [3]Properties calculated according to Patek and Klomfar [23] (3) Values calculated in this studyProperties
calculated to according Kim and Infante Ferreira [14] procedure.
Table VI. Exergetic ratio of inlets and outlets xComparison with approaches of Koehler et al. [1] and Oliveira and Le Goff [21].
Absorber
Condenser
Evaporator
Generator
Heat exchanger of solution
This study
86.27
99.10
85.98
93.43
93.29
94.59
94.04
96.47
98.98
98.59
95.89
98.89
99.73
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
R. Palacios-Bereche et al.
37
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
R. Palacios-Bereche et al.
m (kg s1)
P (kPa)
T (1C)
X (%LiBr)
h (kJ kg1)
1.177
1.177
1.177
1.042
1.042
1.042
0.135
0.135
0.135
0.135
16.55
16.55
20.46
20.46
20.46
20.46
13.58
13.58
14.37
14.64
0.266
20.46
20.46
20.46
0.0097
0.1894
0.1983
0.84
7.5
7.5
7.5
7.5
0.8
7.50
7.50
0.84
0.84
424.7
145.2
424.7
274.05
274.05
145.2
424.7
145.2
101.3
101.3
101.325
101.325
101.325
424.7
101.325
101.325
101.325
32.9
32.9
62.1
89
53.1
47.3
73.5
40.3
4.5
4.5
95
89
29
33.8
33.8
37.7
12
6.5
29
35
29
37.7
29
29
29
29
202.5
54.9
54.9
54.9
62
62
62
0
0
0
0
80.6
80.7
140.4
221.1
153.7
153.7
2637
168.8
168.8
2508.7
398.2
372.8
121.9
141.6
141.6
157.9
50.8
27.5
74.4
128.9
121.6
157.9
121.6
121.9
8.3
74.4
197.5
0.205
0.205
0.391
0.489
0.293
0.300
8.441
0.576
0.608
9.038
1.250
1.181
0.423
0.488
0.488
0.541
0.180
0.099
5.870
6.050
0.423
0.541
0.423
0.423
10.840
5.870
7.701
0.117
0.123
4.3
11.2
2.2
0.1
124.9
1.5
8.1
181.3
30.2
25.3
0.4
0.7
0.7
1.1
1.5
2.5
0.1
1.9
0.1
1.1
0.1
0.4
0.057
0.092
42.76
494.2
494.2
494.2
593.2
593.2
593.2
49.96
49.96
49.96
49.96
49.96
49.96
49.96
49.96
49.96
49.96
49.96
49.96
0
0
49.96
49.96
49.96
49.96
51254
0
65.4
494.3
494.3
498.4
604.4
595.4
593.3
174.9
51.45
41.86
131.3
80.13
75.22
50.39
50.66
50.66
51.1
51.5
52.51
0.09224
1.897
50.07
51.09
50.07
50.39
51254
0.09224
108.2
Table VIII. Heat transfer, irreversibilities, exergetic efficiency (Zex) and exergetic ratio (zex) for the absorption refrigeration system of
single effect shown in Figure 13.
Component
Q (kW)
I (kW)
Zex (%)
zex (%)
70.29
333.25
315.93
403.92
737.17
421.23
421.23
4.46
7.67
9.764
13.3
1.29
2.242
3.126
0.0053
14.95
14.45
410.7
71.26
467.50
52.35
58.24
60.44
47.45
82.22
13.38
14.29
2.65
99.63
99.28
98.62
99.18
81.37
99.64
99.70
99.99
96.08
99.25
60.2
97.28
60.99
5. CONCLUSIONS
In this paper, a methodology for the exergy calculation
of the lithium bromidewater solution, used in
absorption refrigeration systems, was presented. The
APPENDIX A: NUMERICAL
EXAMPLE OF EXERGY
CALCULATION FOR A SPECIFIC
POINT
It considered the general point: T 5 37.81C, p 5
1.016 kPa, xLiBr 5 55.42%
LiBr 86:85 kg kmol1
M
H2 O 18:02 kg kmol1
M
x1w xLiBr =100 0:5542
R. Palacios-Bereche et al.
Molar fraction
LiBr =1 x1w
yH2 O 1 x1w M
LiBr 1x1w M
H2 O 0:795
M
yLiBr 1 yH2 O 0:205
Molar mass of solution
sol yH2 O M
H2 O 1yLiBr M
LiBr 32:13 kg kmol1
M
Molality
m x1w =1 x1w MLiBr 0:01431
6
X
2 @ai
i @bi
1
p mi=2
i @T 2:v @T
j1
2950 kJ kmol1
l
E
h yLiBr h1
LiBrT;p 11 yLiBr hH2 OT;p 1hT;p;m
2966 kJ kmol1
M
sol 92:31 kJ kg1
h h=
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
R. Palacios-Bereche et al.
sE yLiBr v R
6
X
ibi
@ai
i @bi
p1T
1
p
ai 1
2v
@T 2v @T
j1
mi=2
670:6 kJ kg1
1
l
s yLiBr sLiBrT;p
11yLiBr sH
yLiBr n R
2 OT;p
m
1 1sET;p;m 7:503 kJ kmol1 K1
ln
m0
NOMENCLATURE
a
Cp
C p
0:44 kJ kg1
6
X
ai mi=2 1
i1
2
p X
i bi mi=2 3:762
2 n i1
Activity H2O
H2 O
lnaH2 O f v m M
3:762 2 0:01431 18:02
1:9402
aH2 O 0:1437
Molality in saturated state xLiBr,sat 5 62.23%
xLiBr;sat
msat
0:01897 kmol kg1
LiBr
1 xLiBr;sat M
Activity LiBr
Substituting m in Equation (21)
"
6
X
i12
ln aLiBr v ln m1
i
i1
!
#msat
p bi
i=2
m
3:204
ai 1i
2v
m
aLiBr 0:04062
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
ex
h
h
I
LHV
m
m
p
Q_
R
s
s
T
v
v_gas
_
W
V
vfrac
x
y
5 activity
5 specic heat at constant pressure
(kJ kg1 K1)
5 molar specic heat at constant pressure
(kJ kmol1 K1)
5 specic exergy (kJ kg1)
5 enthalpy (kJ kg1)
5 molar enthalpy (kJ kmol1)
5 irreversibility (kW)
5 lowing heating value (kJ m3)
5 molality (mol kg1 of solvent)
5 molecular mass (kg kmol1)
5 pressure (kPa)
5 heat ow rate (kW)
5 universal gas constant
(kJ kmol1 K1)
5 entropy (kJ kg1 K1)
5 molar entropy (kJ kmol1 K1)
5 temperature (K)
5 dissociation number ( 5 2 for LiBr)
5 volumetric ow of natural gas
5 power (kW)
5 molar specic volume (m3 kmol1)
5 vapour fraction
5 concentration of solute in mass
5 mole fraction
Greek letters
e~0
D
Z
n
r
f
Dg~0f
c
x
5 osmotic coefcient
5 standard molar Gibbs free energy of
formation (kJ kmol1)
5 specic exergy calculated by Koehler
et al. [1] and Sencan et al. [5]
5 exergetic ratio of inlet and outlet
Subscripts
0
1,2y
a
Br2
c
ch
dis
e
ex
g
gas
H2O
ht,g
in
Li
LiBr
M
out
ph
sat
sol
to
vc
5 reference state
5 points of the cycle
5 absorber
5 molecular bromide
5 condenser
5 chemical
5 dissolution
5 evaporator
5 exergetic
5 generator
5 natural gas
5 water
5 heat transfer in the generator
5 inlet
5 lithium
5 lithium bromide
5 mixture
5 outlet
5 physical
5 saturation
5 solution
5 total
5 control volume
Superscripts
*
N
E
l
ACKNOWLEDGEMENTS
The authors wish to thank CNPq (PQ 10-307068/20064) and FINEP (Contract FINEPFUNCAMP Nr.
01/06/004700).
REFERENCES
1. Koehler WJ, Ibele WE, Soltes J. Availability
simulation of a lithium bromide absorption heatpump. Heat Recovery Systems and CHP 1988; 8:
157171.
2. Khalid A, Kumar R. Exergy analysis of double effect
vapour absorption refrigeration system. International
Journal of Energy Research 2008, 32:161174.
R. Palacios-Bereche et al.
R. Palacios-Bereche et al.
19.
20.
21.
22.
Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er