Int. Comm. Heat Mass Transfer, Vol. 25, No. 5, pp.

711-721, 1998
Copyright @ 1998 Elsevier Science Ltd
Pergamon Printed in the USA. All rights reserved
0735-1933/98 $19.00 + .00

P I I S0735-1933(98)00058-X

A COMPARISON BETWEEN AMMONIA-WATER

AND W A T E R - L I T H I U M B R O M I D E S O L U T I O N S IN
VAPOR ABSORPTION REFRIGERATION SYSTEMS

I. Horuz
University of Uludag
Faculty o f Engineering and Architecture
Department o f Mechanical Engineering
16059 Gorukle, Bursa
Turkey

(Communicated by J.P. Hartnett and W,J. Minkowycz)

ABSTRACT
The study included an investigation to analyze the Vapor Absorption Refrigeration (VAR)
systems using ammonia-water and water-lithium bromide solutions. A fundamental VAR
system is described and the operating sequence is explained. Since the most common VAR
systems use ammonia-water solution with ammonia as the refrigerant and water-lithium
bromide solution with water as the refrigerant, the comparison of the two is presented in
respect of the coefficient of performance (COP), the cooling capacity and the maximum and
minimum system pressures. It is concluded that the VAR system using water-lithium bromide
solution provided better performance than the system using ammonia-water solution.
However, there are some points to be considered such as; the danger of crystallization and
impossibility of operating in very low temperatures because of the use of water as the
refrigerant. © 1998 Elsevier Science Ltd

Introduction

A Vapor Absorption Refrigeration (VAR) System is similar to a Vapor Compression Refrigeration

(VCR) System. In both systems the required refrigeration is provided by refrigerants vaporizing in the
evaporator. However, in the VAR System, a physico-chemical process replaces the mechanical process of
the VCR system and heat rather than a mechanical and electrical energy is used. The advantages of this
system lie in the possibility of utilizing of waste energy from industrial plants as well as of using solar
energy.
711
 712 I. Horuz Vol. 25, No. 5

As Figure 1 illustrates, the fundamental VAR cycle contains four main components; a generator,
an absorber, a condenser and an evaporator. The condenser and the evaporator function in the same manner
as they do in the VCR cycle.

E 1
I Generator ,]

i
2

Restrictor RestrictorI
9 t6: on
3 10

Evaporator I

FIG. 1
The schematic illustration of the fundamental VAR cycle

Pressure-temperature and Pressure-enthalpy diagrams of the fundamental VAR cycle are shown in
Figure 2 and Figure 3 respectively.

1
F I .~ It .~ Peon

Pevap
5: 10
il
i
1

Solution Temperature

FIG. 2
The pressure-temperature diagram of the fundamental VAR cycle
 Vol. 25, No. 5 VAPOR ABSORPTION REFRIGERATION 713

f
Pcon
T1
/1/t J
/ //
Pcvap
/ 3
/
/ /
/
I

Enthalpy

FIG, 3
The pressure-enthalpy diagram of the fundamental VAR cycle

The combination of the generator, the absorber and solution pump may be thought of as a means of
transferring refrigerant vapor from the low pressure side of the cycle back to the high pressure side, the
function performed by the compressor of the VCR system.

The VAR cycle uses a refrigerant-absorbent solution rather than pure refrigerant as the working
fluid. The absorbent acts as a secondary fluid to absorb the primary fluid which is the refrigerant in its
vapor phase.

The refrigerant-absorbent solution passing through the solution pump is referred to as strong
solution, being relatively rich in refrigerant. The solution returning from the generator to the absorber
contains only a little refrigerant and is therefore referred to as weak solution.

In the absorber, weak solution meets refrigerant vapor from the evaporator. The solution absorbs
the vapor, giving out heat as it does so, until all the vapor is absorbed to produce strong solution. The
process occurring in the absorber is normally referred to as absorption, but it can also be thought of as
condensation of a binary mixture, where the vapor phase contains predominantly one component.

Solution from the absorber (5) is transferred to the high pressure side of the circuit by the solution
pump. Between the solution pump and the generator is a solution heat exchanger (SHE) where the cold
 714 I. Horuz Vol. 25, No. 5

strong solution from the absorber (6) is in counterflow to the hot weak solution coming from the generator
(8). The strong solution is thus heated and the weak solution is cooled in this process. The strong solution
entering the generator (7) is still subcooled at the higher pressures present there. The heat source to the
generator must therefore first heat it to the state where it begins to boil. As it boils, evolving the refrigerant
vapor which passes to the condenser, the solution in the generator becomes progressively poorer in
refrigerant and finally leaves the generator as weak solution (8). After passing through the SHE (9), the
weak solution at high pressure passes through an expansion valve back to the absorber (10), completing the
cycle. It can be seen that the SHE is important in that the more heat the strong solution recovers from the
weak solution leaving the generator, the less it needs from the external sources in the generator.

The VAR cycle widely uses ammonia-water solution with ammonia as the refrigerant and water-
lithium bromide solution with water as the refrigerant.

The study will concentrate on the comparison between ammonia-water and water-lithium bromide
solutions.

The coefficient of performance (COP) is a measure of a cycle's ability to transfer heat between
various temperature levels. Since the primary use of the VAR systems has been for refrigeration purposes,
the conventional definition of the COP is:

Heat taken in at low temperature (in the evaporator)

COP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . O)
Net energy supplied (in the generator)

In the VAR system, heat energy being reduced in temperature from Tgen (in the generator) to Tabs
(in the absorber) provides the driving force to lift heat from Tevap to Tcon. Camot cycle operating between
these temperatures sets an upper limit to the COP of;

Tgen - Tabs Tevap

Camot COP ................. , ................... (2)

Tgen Tcon - Tevap
 Vol. 25, No. 5 VAPOR ABSORPTION REFRIGERATION 715

Comparison Between Ammonia-Water And Water-Lithium Bromide Solutions

The ammonia-water VAR system has been used in large capacity industrial applications requiring
low temperatures for process cooling. The water-lithium bromide VAR system is used to produce hot water
for comfort heating, process heating and domestic purposes, as well as for cooling. This system can also be
used to deliver heat at a temperature higher than that of the driving heat source, but it is predominantly for
air-conditioning applications.

The main problem with the water-lithium bromide pair is the possibility of solid formation. Since
the refrigerant turns to ice at 0°C (32 F), the pair cannot be used for low temperature refrigeration.
Furthermore, lithium bromide crystallizes at moderate concentrations. When the absorber is air cooled,
these conomtrations tend to be reached; thus, the pair is usually limited to applications in which the
absorber is water cooled. It is possible that the use of a combination of salts as the absorbent will reduce the
crystallizing tendency enough to permit air cooling. Figure 4 shows the crystallization temperature of the
water-lithium bromide solution against the Lithium bromide concentration. Other disadvantages of the
water-lithium bromide pair are those associated with low pressure and with the high viscosity of the
solution. These latter disadvantages are largely overcome by proper equipment design. The combination
does have the advantages of high safety, high volatility ratio, high affinity, high stability and high latent
heat.

300
w
250
~" 200 ~, •
150 ~
~. 1oo ~ •
50 ~
.~ 0
/-
N
N 4o ; •
, 100 [
-150
-200'
0 I'0 2'0 3'0 40 50 60 70 80 90 100
LithiumBromideConcen~afion,weightpercent

FIG. 4
The crystallization temperature of the water-lithium bromide solution
against the mass concentration of the Lithium bromide
 716 I. Horuz Vol. 25, No. 5

Probably the major disadvantages of the ammonia-water system is the fact that water is reasonably
volatile, so that ammonia vapor leaving the generator usually contains appreciable amount of water vapor,
which, if allowed to pass through the condenser and go into the evaporator, will raise the evaporator
temperature and reduce the refrigerating effect by carrying unvaporised refrigerant out of the evaporator.
For this reason, the efficiency of the ammonia-water VAR system can be improved by the use of an
analyser and a rectifier which function to remove the water vapor from the mixture leaving the generator
before it reaches the condenser. The analyser is essentially a distillation colunm that is attached to the top of
the generator.

The ammonia-water cycle must be more complex than the water-lithium bromide cycle to provide
acceptable performance. Better heat recovery means is required and because of the cycle's complexity, the
design for optimum performance, based on a set of design parameters, requires extensive calculations.

Most water-lithium bromide VAR machines meet load variation and maintain chilled water
temperature control by varying the reconcentration rate of the absorbent solution. Because of the low
operating pressures of these machines, atmospheric air can leak into units which are improperly operated or
maintained. Concentration control to avoid crystallization is required, however, they are comparatively
trouble-free and simple to operate.

All calculations and graphs are based on the system presented in Figure 1. For these calculations
the efficiency of the solution heat exchanger is chosen to be 0.6. The limitation caused by the crystallization
of the lithium bromide is also shown in the graphs. The operating range of the water-lithium bromide VAR
system is shown by solid lines.

Figure 5 shows the COP of the VAR system against the condenser temperature. As can be seen
from Figure 5, when the condenser temperature increases, the COP decreases. This is due to the fact that, if
the condenser temperature gets higher, the condensing temperature increases and hence causes less heat
transfer in the condenser. This results in an increase in the temperature and the enthalpy of the refrigerant at
the condenser outlet (state 2). Hence, the cooling capacity decreases as does the COP. The water-lithium
bromide VAR systems have better COP, but are limited by the crystallization.

Figure 6 shows the COP system against the generator temperature. If the generator temperature
increases, so also does the heat transfer to the solution in the generator and hence, the refrigerant mass flow
rate increases. As the refrigerant mass flow rate increases, the cooling capacity increases causing an
increase in the COP.
 Vol. 25, No. 5 VAPOR ABSORPTION REFRIGERATION 717

6
5.5 Tgen=75 C, Tevap=l 0 C
-A-COP(NH3-H20) -~COP(H20-LiBr) -o-COP(era'not)
4.5 ~-
8 \
~ 3~
,~ 2.5-
2-

8 1L- ..... ~ ~ _ --=

r.) 0.5
0
15 20 25 30 35 40
Condenser Temperature, Tcon ( C )

FIG. 5
The COP o f the V A R system against the condenser temperature

4
F Tevap=10 C, Teon=30 C
3.5 [- -*-COP(NH3-H20) -~COP(H20-LiBr) ~-COP(carnot)
3~-
2.5 L ,~~ ° ' j ' ~ ) ~

1.5 -

0'
45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120
Generator Temperature, Tgen ( C )

FIG. 6
The C O P o f the V A R system against the generator temperature

The effect o f the evaporator temperature on the COP system is shown in Figure 7. As can be seen
from Figure 7, when this temperature increases, the C O P o f the V A R system increases. Figures 5, 6 and 7
also show the camot C O P o f the V A R system which is formulated m Eq. 2.
 718 1. Horuz Vol. 25, No. 5

4
Tgen=75 C, Tcon=30 C
~"
© 3.5- ~-COP(NH3-H20) ~COP(H20-LiBr) ~-COP(carnot)

8
2"5~ j ~

J~ Y
~ J

1.5-
E
o -
"~ 1
N :
~ 0.5

0
4 5 6 7 8 9 10 11 12 13 14 15 16
Evaporator Temperature, Tevap ( C )

FIG. 7
The COP of the VAR system against the evaporator temperature

Figure 8 shows the cooling capacity against the condenser temperature. As Figure 8 illustrates,
when the condenser temperature increases, the cooling capacity decreases.

3500 F
Tgen=75 C, Tevap=10 C
~ 3000 ; : ~-Qevap(NH3-I-I20) -~Qevap(I4.20-LiBr)

2500 --
g
2000 F-

~ 15oo ~
U A - - & --A ~lt
~ 1000 ~
@
~ 500 ~

O'
15 20 25 30 35 40
Condenser Temperature, Teon ( C )

FIG. 8
The cooling capacity against the condenser temperature
 Vol. 25, No. 5 VAPOR ABSORPTION REFRIGERATION 719

Figures 9 and 10 show the maximum and minimum absolute system pressures. As Figures 9 and
10 indicates the operating pressures of the ammonia-water VAR system are always higher than the water-
lithium bromide VAR system's operating pressures.

2800
2600 ~- I Tgen=75 C, Tevap=10 C i '
2400 [-* Pmax(NH3-U20) ~-Pmax(mO-LiBr) ]
2200 -
2000 i
1800
1600 jJ-~ !
E 1400 ~-
1200 r- J
1000 f
Y
800 ~-
E 600 ~-
"~ 400
200 L
0
15 20 25 30 35 40 45 50 55
Condenser Temperature, Tcon ( C )

FIG. 9
Maximum system pressures against the condenser temperature

1000
| Tgen=75 C, Tevap=10 C
900 t- ]-*-Pmin(NH3-H20) -mPmin(H20-LiBr) I
800 ~_~,_~_~,~1/-A
700 ~ _ ~ _ _ . ~ i ~ -
600 -
500
oE
400 V
300 ~-
._= 200
I
100 L
0
4 5 6 7 8 9 10 I1 12 13 14 15 16
Evaporator Temperature, Tevap ( C )

FIG. 10
Minimum system pressures against the evaporator temperature
 720 I. Horuz Vol. 25, No. 5

Result And Conclusion

The VAR system using water-lithium bromide solution with water as the refrigerant, is
predominantly for air conditioning applications. The VAR system using ammonia-water with ammonia is
the refrigerant, has been used in large-tonnage industrial applications requiring low temperatures for
process work.

The ammonia-water cycle must be more complex than the water-lithium bromide cycle to provide
acceptable performance. More heat recovery means are required and the rectification is necessary.

The VAR system using water-lithium bromide solution showed better performance than the system
using ammonia-water solution. However, there are some points to be considered such as; the danger of
crystallization and impossibility of operating in very low temperatures because of the use of water as the
refrigerant.

Nomenclature

COP Coefficient of Performance ( - )

P Absolute Pressure (kPa)
T Temperature (°C)

Subscripts

abs Absorber
con Condenser
evap Evaporator
gen Generator
max Maximum
rain Minimum

References

1. L. A. McNeely, Thermodynamic Properties of Aqueous Solutions of Lithium Bromide,

ASHRAE Transactions, 8__55,No. 3, 413 (1979).
 Vol. 25, No. 5 VAPOR ABSORPTION REFRIGERATION 721

H. Perez-Blonco, Absorption Heat Pump Performance for Differ~t Types of Solutions,

Int. Journal of Refrigeration, 7, 115 (1984).
3. ASHRAE Equipment Handbook, Thermodynamics and Refrigeration Cycles, 1.21 (1977).
4. ASHRAE Equipment Handbook, Absorption Cooling, Heating and Refrigeration Equipment, 13.1
(1988).
5. R. J. Dossat, Pnneiples of Refrigeration, John Wiley and Sons, Canada, (1981).
6. B. Z¢igler and C. Tr~p, Equation of State for Ammonia-Water Mixtures, Int. Journal of
Refrigeration, 7, No. 2, 101 March (1984).
7. B. H. Je~nings, The Thermodynamic Properties of Ammonia-Water Mixtures: A Reassessment in
Tabular Format, ASHRAE Transactions, 419 (1979).
8. K. Gomm~ and G. Grossman, Performance Analysis of Stagecl Absorption Heat Pumps: Water-
Lithium bromide Systems, ASHRAE Transaction, 96, Part 1, 1590 (1990).
9. R. M. Tozer and R. W. James, Fundamental Thermodynamics of Ideal Absorption Cycles, Int.
Journal of Refrigeration, 20, No. 2, 120 (1997).
10. R. M. Tozer and R. W. James, A Review of Absorption Refrigeration Applications, CIBSE
National Conf. Chartered Institute of Building Servwes Engineers, Brighton, U. K, Voi. 1,
pp. 161-172 (1994).

Received December 15, 1997