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Published online in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/er.1790

and its application in the exergetic evaluation

of absorption refrigeration systems LiBr-H2O

Reynaldo Palacios-Bereche1,2, R. Gonzales3 and S. A. Nebra2,,y

1

Interdisciplinary Centre of Energy Planning, University of Campinas, UNICAMP, Campinas, Brazil

3

Petrobras Energa Peru, Amador Merino Reyna 285, San Isidro, Lima, Peru

2

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.

useful refrigeration [2,3]. They differ from compression

systems due to the use of a heat source as energy input

to operate; on the other hand, the refrigeration devices

based on compression systems need mechanical energy

to operate. This is the main advantage of absorption

systems; which can run on burning fuel or using waste

heat, recovered from other thermal systems.

In exergy studies, it is necessary to calculate the

exergy of the working uid at different points of the

system. In some studies found in the literature [36],

the exergy of the solution is calculated considering the

thermal component only (physical exergy), without

considering the chemical exergy.

In the literature there are some studies about

exergetic evaluation of absorption systems considering explicitly the chemical exergy for the pair

H2O/NH3 [7,8], but not many studies on absorption

R. Palacios-Bereche et al.

solution.

In terms of exergy destruction calculation (irreversibilities), the balance of physical exergies gives correct

results due to the Gouy Stodola equation being

implicitly applied [3].

Moreover, the choice of reference species to obtain

chemical exergy does not inuence the values of

internal exergy losses but inuences distinctly the

values of external losses, and hence also the calculated

values of the degree of thermodynamic perfection or

the exergetic efciency [9].

On the other hand, in the analysis of components

such as absorbers or desorbers (generators), where

there are processes of separation and mixture, the

consideration of the chemical exergy of LiBr/H2O

solution would give differences in the results of

exergetic ratio of inlet and outlet type due to its

dependence on the numeric values of the exergy.

Moreover, values of exergy of the LiBr/H2O solution reported in the literature are widely varied; for this

reason there is the need to standardize the procedure

for exergy calculation of the LiBr/H2O solution

adopting a unique and general environment reference

system.

Thus, this study presents a methodological proposal

for the exergy calculation of a LiBr/H2O solution

adopting the reference environment proposed by

Szargut et al. [10] considering their physical and chemical components. This methodology represents a

useful tool for exergy analysis of mixture and separation process in absorption systems LiBr/H2O owing to

permit expanding the control volume including other

thermal systems such as direct-red or cogeneration

systems; hence, an integrated analysis based in a

unique reference system can be performed.

presented correlations for the calculation of enthalpy,

entropy, osmotic coefcient and Gibbs free energy

of the LiBr/H2O solution (01CoTo2101C and

0%oxo70%).

Figure 1 shows the solubility of pure LiBr in water as a

function of the temperature. The values are from

Boryta [15].

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

BROMIDEWATER SOLUTION

For exergy calculation of the LiBr/H2O solution, the

thermodynamic properties are essential. The specic

enthalpy and entropy are indispensable to calculate

physical exergy, while the consideration of the

components activities is necessary to calculate the

exergy of the mixture [10,11].

Some studies in the past intended to describe

the properties of the lithium bromide solution. The

most known study is probably the research by

McNeely [12].

Chua et al. [13] published an interesting study

correlating entropy and enthalpy of LiBr/H2O solutions. In that paper, tables with values for enthalpy

and entropy were presented for a range of temperatures and concentrations (01CoTo1901C and

0%oxo75%).

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.

DOI: 10.1002/er

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.

j50

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

147.5562 (kJ kmol1)

273.15 K

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.

2

X

cj

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

reference values herein used for enthalpy are: null values at 01C for pure water and for the solution at

50 wt%. Enthalpy in mass basis is calculated using

Equation (11). Results of the enthalpy, calculated with

the previous equations, are presented in Figure 2.

M

sol

h h=

11

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.

DOI: 10.1002/er

R. Palacios-Bereche et al.

based on the molar fraction and molar mass of the

components.

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

LiBrT;p is the molar entropy of the

ideal LiBr uid, and slH2 OT;p is the molar entropy of

pure water.

The third term is the entropy generation in

an ideal mixture (m0 is the standard molality:

m0 5 0,001 kmol kg1 of solvent) and the last term

sET;p;m is the additional entropy generation for a real

mixture process. These terms can be calculated by

Equations (13), (14) and (15). Values of the constants

employed are shown in Table I.

Z T 1

CpLiBr

1

s1

dT

LiBr sLiBr;0 1

T

T0

Z p

1

@VLiBr

dp

13

@T p

p0

slH2 O slH2 O;0 1

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.

f 11

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

Point 1: General state, yLiBr

Point 2: Saturated state corresponding to the maximum solubility, yLiBr;sat

This upper limit of the integral was considered

because the solution at this state is in equilibrium with

pure lithium bromide, then the reference value for LiBr

activity at this point (point 2) corresponds to the pure

LiBr (aLiBr_2 5 1).

Substituting Equations (17), (18) and (19) into

Equation (20), after of operating and integrating,

Equation (21) is obtained. The results are presented in

Figure 4:

"

yLiBr

lnaLiBr v ln

:

H2 O

1 yLiBr M

6

X

i12

p bi

1

ai 1i

2v

i

i1

i=2 #yLiBr;sat

yLiBr

21

H2 O

1 yLiBr M

y

LiBr

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

Physical exergy is the maximum work available when

the system is driven from its initial state (T, p) up to the

reference state (T0, p0) by means of a reversible

process, exchanging heat and work with the reference

environment only. If kinetic and potential components

of exergy are neglected, the physical exergy can be

calculated through the following expression:

exph h h0 T0 s s0

23

Equation (23) for mass fractions of LiBr, x, ranging

from 0 to 70% and different T temperatures. The

reference state considered was T0 5 251C and p0 5

101.325 kPa. Enthalpies and entropies were calculated

according to the procedure described in the previous

section.

Chemical exergy is the maximum work that can be

achieved when a substance is driven from its equilibrium state at the environment pressure and temperature (dead restricted state) to the equilibrium state of

equal chemical potentials (dead unrestricted state) by

means of processes that involve heat, work and mass

transfers with the environment. Because the LiBr/H2O

solution is not ideal, the following expression [11] is

used for chemical exergy calculation, as a function of

the activities and standard exergies of pure species:

"

#

n

n

X

X

0

sol

ex ch 1=M

yi e~ 1R T0

yi ln ai 24

i

i1

a function of the mass fraction of LiBr.

i1

the LiBr concentration.

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.

sol yH2 O

exch 1=M

e~0H2 O 1yLiBr

e~0LiBr 1R

25

as follows:

Standard chemical exergy of pure species:

sol yH2 O e~0 1yLiBr e~0

exch;0 1=M

H2 O

LiBr

26

exch;dis

R~ T0

y

lnaH2 O 1yLiBr lnaLiBr 27

sol H2 O

M

calculate the exergy components for LiBr/H2O solution. The path from initial solution at x, p and T to

reach the dead state according to Kotas can be

observed [11].

The

values 2.5 105

and

4

1

8.7 10 mol kg H2O in Figure 6 are the conventional standard molarities of the reference species dissolved in sea water: Li1 and Br, respectively,

according to [10].

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

according to this studyExergy components of LiBr/H2O

solution.

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.

DOI: 10.1002/er

chemical exergy due to the dissolution process (exdis) and total

chemical exergy at 251C of LiBr/H2O solution as a function of

LiBr concentration (mass basis).

solution as a function of LiBr concentration (mass basis).

R. Palacios-Bereche et al.

4. STUDY OF CASES

COMPARISON WITH OTHER

APPROACHES

of pure water and the reference solution at x0. The

path to the reference state is shown in Figure 10.

approaches and studies

calculation of LiBr/H2O solution, which considers that

the least potential of a solution for doing useful work is

given when it is in a saturated state at T0 and p0 (the

minimum free energy state denes the zero exergy level

at T and p dened). Thus for a given environmental

state, the exergy c can be treated as a state function

and it can be chosen as a convenient path from any

given state to the dened dead state. The path to the

reference state is shown in Figure 9.

cT; p; x cx T; p1c0 x

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.

The rst is an absorption heat pump and the second

and third are absorption refrigeration systems. Calculations were performed using equation engineering

solver (EES) [22].

The absorption heat pump evaluated in Koehlers

study [1] is presented in Figure 11. The model considered by these authors consists of an internal and an

external system. The external system represents the

connection between the internal system and the

surroundings. The internal system is a standard

absorption cycle containing: evaporator, condenser,

absorber, generator, pump, two expansion valves and

two heat exchangers.

Table II shows the operational conditions of this

system. Specic exergies reported by Koehler et al. [1]

are compared with specic exergies calculated by

Oliveira and Le Goff [21] approach and calculated by

the procedure proposed in Section 3 of this study.

Enthalpies and entropies were calculated using the

procedure described in Section 2 according to Kim and

Infante Ferreira [14].

The reference temperature adopted by Koehler et al.

[1], in exergy calculation, was T0 5 51C. On the other

hand, the methodology proposed in this study as well

Oliveira and Le Goff [21] also present an approach for

exergy calculation of LiBr/H2O solutions. These

authors consider a reference state at T0 and p0 and

equilibrium compositions of the mixture at T0 and p0.

The reference conditions adopted for the LiBr/H2O

solution were T0 5 251C, p0 5 100 kPa, pure water

(x 5 0) and a solution at x0 5 20 wt%. Hence, the

state according to the approach of Koehler et al. [1]Exergy

components of LiBr/H2O solution.

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.

as reference temperature.

In Table II, negative values for enthalpies of LiBr/

H2O solution (points 5, 6PU, 6, 7G, 7, 8) can be

observed, which indicate that the references for enthalpy

are different from that adopted by McNelly [12] and

Kim and Infante Ferreira [14]. For the next cases some

constants were adjusted in Koehlers exergy equation in

order to get exergy values according to the graphics

reported by these authors [1] using correlations of Kim

and Infante Ferreira [14] to calculate properties.

It can be observed that specic exergies for pure

water are negative in points: 1S and 1 for Oliveira and

Le Goff approach [21] as well as this study approach

due to these points are below the reference state. On

the other hand, Koehler et al. [1] reported the highest

values of exergy for pure water and lower exergies

values of LiBr/H2O solution (negatives values in points

7 and 8). The approach of this study shows the highest

values for LiBr/H2O solution.

It was not possible to compare irreversibilities and

exergetic efciencies reported by these authors, in this

case, because they neither inform mass ows nor the

pressure of the external points of the system (points

EWI, EWE, CWI, CWE, AWI, AWE, GWI, GWE).

In the second case, the absorption refrigeration

system of single effect evaluated by Sencan et al. [5] is

shown in Figure 12. This system is composed of a

condenser, generator, solution heat exchanger, absorber, evaporator, pump, solution expansion valve and

refrigerant expansion valve.

Table III shows operation conditions for the system

as well as specic exergies reported by the authors [5]

and calculated by approaches described in the previous

sections. For all approaches the reference temperature

was adopted as T0 5 251C.

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.

DOI: 10.1002/er

et al. [5].

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.

report negative values at outlet of condenser, expansion valve of refrigerant and evaporator (points 8, 9

and 10).

In a recent study Arora and Kaushik [3] evaluated

an absorption refrigeration system of single and double

effect. The conguration of the absorption refrigeration system of single effect studied by these authors is

the same as the conguration shown in Figure 12.

Table IV shows the operational conditions for this

system. Specic exergies in each point of the cycle were

calculated by the approaches described in previous

sections. Arora and Kaushik [3] do not report values of

exergy in each point of the cycle.

Unlike the previous cases, Arora and Kaushik [3]

evaluate irreversibilities in each system component

considering only the internal circuit, calculating the

exergy of the heat ows.

In this study irreversibilities generated in each system component are calculated by means of exergy

balance.

I

X

m_ in exin

m_ out exout Q_

T0

_ vc

W

1

Tr

32

surface where the heat transfer is taking place. Arora

and Kaushik [3] dene the temperature Tr for each

component; thus, for the generator Tr 5 Tg 5 87.81C,

for the evaporator Te 5 7.21C and for the condenser

and the absorber Tr 5 Tc 5 Ta 5 37.81C.

To calculate exergetic efciencies, the rational efciency concept [11] is used:

roduct

33

Fuel

This denition is applied to components where it is

possible to dene a product. This denition follows that

recommended by Szargut et al. [10] and Kotas [11].

The latter one being named rational efciency. On the

Zex

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

y

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.

ratio z as exergetic effectiveness of inlets and outlets.

The inlet exergy, in this ratio, corresponds to the

exergy of all the exergy carriers that get into

the control volume considered. On the other hand, the

outlet corresponds to the exergy of all the exergy

carriers that go out the control volume.

The ratio z is dened in Equation (34).

P

_ out 1Q_ out Zcarnot

m_ out exout 1W

zex P

34

_ in 1Q_ in Zcarnot

m_ in exin 1W

For instance, in the absorber, it is dened as:

m_ 1 ex1 1Q_ a 1 T0 =Ta

zex;a

m_ 10 ex10 1m_ 6 ex6

35

and Kaushik [3] and by exergy balances according to

the methodology proposed in Section 3 and according

to the approaches of Koehler et al. [1] and Oliveira and

Le Goff [21]. Furthermore, irreversibilities are calculated by Gouy Stodola equation (Equaiton (36)) using

the correlations reported in item 2 of this study.

Table VI shows the ratio, z, calculated by each

approach.

From Table V it can be observed small differences

between irreversibilities reported by [3] and reevaluated using the procedure of Kim and Infante

Ferreira [14] for property calculations. The highest

difference is in absorber (5.68%). Regarding irreversibilities calculated considering the different approaches,

it can be observed that differences are not signicant;

owing to the fact that exergy balances the references

can be performed without calculating exergies, considering the Gouy Stodola equation:

"

#

X

X

X Q_ r

I T0

36

m_ out Sout

m_ in : sin

Tr

r

IN

OUT

Rational exergetic efciency (Zex) resulted in the

same value for all the approaches. It was calculated in

generator, evaporator and heat exchanger of solution

resulting in 89.3, 42.3 and 63%, respectively.

The ratio of inlet and outlet (x) resulted high in all

the cases. There were little differences due to the

different values of the different approaches. In

Table VI it can be observed that this study presents the

highest values of x in system components where LiBr/

H2O solution is involved. This a consequence of the

high value of the standard chemical exergy considered.

Exergetic efciencies calculated by the approach of

Oliveira and Le Goff [21] present intermediate values

between this study and the Koehler approach [1].

Thus, it can be observed that, in the literature, the

values of exergy for LiBr/H2O solution are widely

varied because the reference conditions and chemical

composition of the reference environment are unlike in

the different approaches. There are also some differences in property values such as enthalpy or entropy of

the LiBr/H2O solution.

For instance, Sencan et al. [5] report ex 5 c 5 19.95 kJ kg1 for x 5 57.59% and T 5 401C; and

ex 5 c 5 21.52 kJ kg1 for x 5 58.15% and T 5 521C. In

[4], Talbi and Agnew report ex 5 c 5 227.817 kJ kg1

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.

differences in temperatures and concentrations the value

reported by Talbi and Agnew [4] is quite big in comparison with that reported by Sencan et al. [5].

Misra et al. [6] consider the physical exergy and the

chemical exergy of the pure water contained in the solution. They report ex 5 33.91 kJ kg1 for x 5 56.43%

and T 5 341C which is almost two times the value

reported by Sencan et al. [5] under similar conditions.

Consequently, there is the need to standardize the

procedure for exergy calculation of LiBr/H2O solution

and this study intends to contribute to this objective

proposing a methodology of exergy calculation considering the reference environment of Szargut et al. [10].

Furthermore, this proposal permits an integrated

analysis considering the external losses of exergy or

considering a control volume that includes more pieces

of equipment as the direct-red system. For instance,

Figure 13 shows an absorption refrigeration system of

single effect together with a cooling tower. The heat

duty in the condenser and absorber is removed by the

water ow of the cooling tower. The local temperature

considered is 291C but for exergetic analysis standard

conditions

are

considered:

T0 5 251C

and

p0 5 101.325 kPa. The temperature T7 is calculated

considering the boiling temperature of the solution at

concentration x3, on the other hand, the temperature

T4 is the equilibrium temperature at concentration x4

according to Herold and Radermacher [24].

Furthermore, the exergetic evaluation of a direct

red system can be accomplished. In this case streams

of natural gas, air and exhaust gases should be considered according to Figure 14 (25, 26 and 27). In order

to take into account heat losses to the environment,

an efciency of heat transfer Zht;g in the generator is

adopted as 0.84 [25]:

Q_ g Zht;g v_gas LHVgas

37

balance of enthalpies using JANAF tables of EES,

cooling tower.

the temperature of exhaust gases resulted as 202.51C.

Table VII shows the results of the exergy calculation

with the proposed methodology in each point of this

system. Table VIII shows the heat exchanged, irreversibilities and exergetic efciencies. It can be

observed the low value of the exergetic efciency for

the direct-red system (2.5%), which indicates that the

absorption refrigeration systems are more appropriate

to operate together with cogeneration systems or

utilizing of some waste heat. The values of zex are very

high owing to the high numerical values of input and

output exergy and the consideration of adiabatic

devices. In the case of a hot-water-driven system, the

element with higher irreversibility is the cooling tower,

due to the high loss of mass that occurs in this element.

The irreversibility of cooling tower represents 20.97%

of the total irreversibility of the system.

Still in this analysis there are some values of negative

exergy for water streams because the pressure of these

streams is below the reference pressure p0. This effect

can be observed in rows 9 and 10 of Table VII.

In relation to the reference states chosen by other

authors for exergy calculation of LiBr-H2O solution,

there are some issues that deserve mention. Koehler

et al. [1] approach considers the minimum exergy level

for the maximum solubility state of the solution while

the highest values of exergy correspond to pure water.

Hence, the minimum exergy level corresponds to the

minimum of free energy at the reference temperature

and pressure adopted. These authors preferred to

adopt the local environmental conditions as reference

state. In order to obtain consistent results, the exergy

of pure water should be calculated with an appropriate

equation reported by [1]; this equation takes into account the properties of the solution at saturated state,

of pure water and pure LiBr, at the reference

temperature. Exergy negatives values can be obtained

depending on the solution temperature and concentration compared with the reference conditions.

This effect can be observed in Table II, points 7 and 8.

Different from Koehler, the Oliveira and Le Goff [21]

approach adopts as reference conditions xed values of

temperature and pressure: T0 5 251C, p0 5 100 kPa, and

also pure water and a solution concentration of 20%.

Adopting variable reference conditions of temperature and pressure to calculate exergy has positive and

system.

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.

DOI: 10.1002/er

R. Palacios-Bereche et al.

Pto.

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

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 (%)

Condenser

Evaporator

Absorber

Refrigerant expansion valve

Solution expansion valve

Cooling water pump

Solution pump

Cooling tower

Generator: hot-water-driven system

Generator: direct fired system

Global system: hot water driven system

Global system: direct fired system

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

refrigeration system adopting the local temperature

and pressure can be useful. But this selection will be

difcult for any comparison between system performances working in different conditions.

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.

DOI: 10.1002/er

5. CONCLUSIONS

In this paper, a methodology for the exergy calculation

of the lithium bromidewater solution, used in

absorption refrigeration systems, was presented. The

currently called physical and chemical exergy, taking

into account the dissolution exergy [10,11].

The thermodynamic properties of the solution,

enthalpy and entropy, were obtained from the bibliography. Owing to the fact that the LiBr/H2O solution

is not ideal, to calculate chemical exergy the concept of

activity must be applied. Water activity was obtained

through the osmotic coefcient, while for LiBr activity

in the solution, a correlation was developed from water

activity by using the GibbsDuhem equation. The

results show that LiBr activity in the solution is almost

null for low concentrations, but increases abruptly

close to the solubility limit.

In relation to chemical exergy, the term calculated

with standard chemical exergies is the highest and

presents a great increase with LiBr concentration. The

term of chemical exergy related to the dissolution

process was negative due to the exergy destruction,

inherent to this process, following the trend of the

Gibbs free energy reduction for the solution. This

indicates that the work input is necessary to separate

the dissolution components.

Regarding total exergy, which is the sum of physical and

chemical exergies, it increases with LiBr concentration.

The lack of a pre-established methodology has led

several authors to perform exergy calculations reporting widely varied exergy values for the LiBr/H2O

solution. Some of these studies are limited to the calculation of irreversibilities and exergetic efciency of

the overall system considering only pure water properties. Thus, there is the need to adopt a unique

methodology for exergy calculation of LiBr/H2O solution. Koehler et al. [1] and Oliveira and Le Goff [21]

deal with this topic proposing different reference systems. This study proposes the adoption of a universal

reference system, which permits extending the control

volume to more complex systems, including the hot

source, doing a unique integrated analysis based in a

unique reference system for exergy calculations.

Thus, it is possible to compare on the same basis a

direct-red absorption system, burning some fuel, or a

cogeneration system that could operate jointly with the

absorption system.

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

T0 5 273.15 K, R 5 8.314 kJ kmol1 K1

1

h1

LiBr hLiBr;0

1

1

c1

1

1

1

R c0

T T0

T2 T20

2

c2

1

1

b02

p p0

12

1R

b

1

01

T3 T30

3

T

10 983 kJ kmol1

hHl 2 O hHl 2 O;0 1R

d1

d2

d0 T T0 1 T 2 T02 1 T3 T03 1R

2

3

e0 2 e2 T1e2 T 2 p p0

2853 kJ kmol1

h E yLiBr v R T 2

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=

1

s1

LiBr sLiBr;0 R

c0

1

1

c1

1

1

c2

1

1

1

1

2 T 2 T02

3 T 3 T02

4 T 4 T04

b02

R b00 2 pp0

T

l

l

sH

1R

sH

2O

2 O;0

T

d2

2

2

d0 ln

1d1 TT0 1 T T0 R

T0

2

9:783 kJ kmol1 K1

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

sol yH2 O e~0 1yLiBr e~0

exch;0 1=M

H2 O

LiBr

1=32:13 0:795 90010:205 101 600

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

R~ T0

y

lnaH2 O 1yLiBr lnaLiBr

exch;dis

sol H2 O

M

8:314 298:15=32:13 0:795

1:940210:205 3:204

169:67 kJ kg1

Chemical exergy

s s=M

Total exergy

solution considered: T0;r 25 C, p0;r 101:325 kPa

and xLiBr 5 55.42%

h0;r 66:83 kJ kg1

s0;r 0:1495 kJ kg1 K1

exph hh0;r T0;ref ss0;r

92:3166:83251273:150:23350:1495

NOMENCLATURE

a

Cp

C p

0:44 kJ kg1

Osmotic coefcient

f 11

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

(kJ kmol1)

5 difference

5 efciency

5 dissociation number for the solute

5 density

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

5 ideal uid for solute species

5 excess property

5 liquid phase

ACKNOWLEDGEMENTS

The authors wish to thank CNPq (PQ 10-307068/20064) and FINEP (Contract FINEPFUNCAMP Nr.

01/06/004700).

REFERENCES

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analysis of lithium bromide/water absorption systems. Renewable Energy 2005; 30:645657.

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21.

22.

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Rivero R, Garas M. Standard chemical exergy of

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Oliveira S, Le Goff P. Analyse exergetique des

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