THERMODYNAMICANALYSISOFWATER

LITHIUMBROMIDEVAPOURABSORPTION
REFRIGERATIONSYSTEM

Submitted to
Dr. T. P. Ashok Babu
NITK SURATHKAL

SUBMITTED BY

VIKRAMADITYA GAONKAR-10M264


DEPARTMENT OF MECHANICAL ENGINEERING NATIONAL
INSTITUTE OF TECHNOLOGY KARNATAKA, SURATHKAL,
MANGALORE -575025



1. Abstract
Lithium bromide-water absorption cooling technologies is underpinned by the continual
circulation of water, which is the refrigerant, powered by the hygroscopic nature of aqueous
lithium bromide solution. The present energy and global warming crises engender a renewed
interest in thermally driven cooling systems, for which lithium bromide-water absorption chiller
is an archetypal example forming the focus of this report. he internal operation of a lithium
bromide-water absorption chiller is intimately influenced by the pressures and concentrations of
its working fluid. In its most basic form, there are four intrinsic components to a lithium
bromide-water absorption chiller: an evaporator, a generator, an absorber and a condenser.
2. Introduction
The first absorption chiller was developed by Edmond Carr in 1850 using water and sulphuric
acid. His brother Ferdinand Carr patented a commercial ammonia-water refrigerator in 1873.
However absorption chillers have only started to enjoy serious deployment since the late 1960s
when the standard single-effect LiBr-H2O absorption cycle was used. In 1970, Trane introduced
the first mass produced double-effect LiBr-H2O absorption chiller [1]. Ever since then LiBr-
H2O absorption chillers became an effective means to harness thermal energy. In the early years
of the twentieth century, the vapor absorption cycle using water-ammonia systems was popular
and widely used. After the development of the vapor compression cycle, the vapor absorption
cycle lost much of its importance because of its low coefficient of performance (about one fifth
of that of the vapor compression cycle). Today, the vapor absorption cycle is used mainly where
fuel for heating is available but electricity is not, such as in recreational vehicles that carry LP
gas. It is also used in industrial environments where plentiful waste heat overcomes its
inefficiency.
The absorption cycle is similar to the compression cycle, except for the method of raising the
pressure of the refrigerant vapor. In the absorption system, the compressor is replaced by an
absorber which dissolves the refrigerant in a suitable liquid, a liquid pump which raises the
pressure and a generator which, on heat addition, drives off the refrigerant vapor from the high-
pressure liquid. Some work is needed by the liquid pump but, for a given quantity of refrigerant,
it is much smaller than needed by the compressor in the vapor compression cycle. In an
absorption refrigerator, a suitable combination of refrigerant and absorbent is used. The most
common combinations are ammonia (refrigerant) with water (absorbent), and water (refrigerant)
with lithium bromide (absorbent).
Vapour absorption refrigeration systems using water-lithium bromide pair are extensively used
in large capacity air conditioning systems. Since water is used as refrigerant, using these systems
it is not possible to provide refrigeration at sub-zero temperatures. Hence it is used only in
applications requiring refrigeration at temperatures above 0
o
C. Hence these systems are used for
air conditioning applications. Water is used as the refrigerant while lithium bromide (Li Br) is
used as the absorbent. In the absorber, the lithium bromide absorbs the water refrigerant, creating
a solution of water and lithium bromide. This solution is pumped by the pump to the generator
where the solution is heated. The water refrigerant gets vaporized and moves to the condenser
where it is cooled while the lithium bromide flows back to the absorber where it further absorbs
water coming from the evaporator. The analysis of this system is relatively easy as the vapour
generated in the generator is almost pure refrigerant (water), unlike ammonia-water systems
where both ammonia and water vapour are generated in the generator.

3. PropertiesofWaterLithiumBromideSolution

3.1 Salient features of the Water-Lithium Bromide Solution

1) Lithium bromide has great affinity for water vapor, however, when the water-lithium bromide
solution is formed, they are not completely soluble with each other under all the operating
conditions of the absorption refrigeration system. Because of this, the designer must take care
that such conditions would not be created where crystallization and precipitation of the lithium
bromide would occur.
2) The water used as the refrigerant in the absorption refrigeration system means the operating
pressures in the condenser and the evaporator must be very low. Even the difference of pressure
between the condenser and the evaporator are very low, and this can be achieved even without
installing the expansion valve in the system, since the drop in pressure occurs due to friction in
the refrigeration piping and also in the spray nozzles.
3) The capacity of any absorption refrigeration system depends on the ability of the absorbent to
absorb the refrigerant, which in turn depends on the concentration of the absorbent. To increase
the capacity of the system, the concentration of absorbent should be increased, which would
enable absorption of more refrigerant. Some of the most common methods used to change the
concentration of the absorbent are: controlling the flow of the steam or hot water to the
generator, controlling the flow of water used for condensing in the condenser, and re-
concentrating the absorbent leaving the generator and entering the absorber.

3.2 Composition


The composition of water-lithium bromide solutions can be expressed either in mass
fraction () or mole fraction (x). For water-lithium bromide solutions, the mass fraction is
defined as the ratio of mass of anhydrous lithium bromide to the total mass of solution, i.e.

=
m
I
m
I
+ m
w


where m
I
and m
w
are the mass of anhydrous lithium bromide and water in solution,
respectively.
The composition can also be expressed in terms of mole fraction of lithium bromide as:
x =
n
I
n
I
+ n
w


where n
I
and n
w
are the number of moles of anhydrous lithium bromide and water in solution,
respectively. The number moles of lithium bromide and water can easily be obtained from their
respective masses in solution and molecular weights, thus:
n
I
=
m
I
N
I
anu n
w
=
m
w
N
w

where ML (= 86.8 kgkmol) and MW (= 18.u kgkmol) are the molecular weights of
anhydrous lithium bromide and water respectively.


3.3 Vapour pressure of water-lithium bromide solutions

Applying Raoults law, the vapour pressure of water-lithium bromide solution with the
vapour pressure exerted by lithium bromide being negligibly small is given by:

P = (1 - x)P
w


where P
w
is the saturation pressure of pure water at the same temperature as that of the solution
and x is the mole fraction of lithium bromide in solution. It is observed that Raoults law is only
approximately correct for very dilute solutions of water lithium bromide (i.e., as x 0). Strong
aqueous solutions of water-lithium bromide are found to deviate strongly from Raoults law in a
negative manner. Strong aqueous solutions of water-lithium bromide are found to deviate
strongly from Raoults law in a negative manner. The ratio of actual vapour pressure to that
predicted by Raoults law is known as activity coefficient. The vapour pressure data of water -
lithium bromide solutions can be very conveniently represented in a Dhring plot. In a Dhring
plot, the temperature of the solution is plotted as abscissa on a linear scale, the saturation
temperature of pure water is plotted as ordinate on the right hand side (linear scale) and the
pressure on a logarithmic scale is plotted as ordinate on the left hand side. The plot shows the
pressure-temperature values for various constant concentration lines (isosters), which are linear
on Dhring plot. Figure 1 shows the Dhring plot.

Figure 1: A Dhring plot


Figure 2: The water LiBr system [1]
The Dhring plot can be used for finding the vapour pressure data and also for plotting the
operating cycle. Figure 2 shows the water-lithium bromide based absorption refrigeration system
on Dhring plot. Other types of charts showing vapour pressure data for water-lithium bromide
systems are also available in literature.
3.4 Enthalpy of water-lithium bromide solutions

Since strong water-lithium bromide solution deviates from ideal solution behavior, it
is observed that when water and anhydrous lithium bromide at same temperature are mixed
adiabatically, the temperature of the solution increases considerably. This indicates that the
mixing is an exothermic process with a negative heat of mixing. Hence the specific enthalpy
of the solution is given by:
h = . h
L
+(1 -)h
W
+ h
mIx

where h
I
and h
w
are the specific enthalpies of pure lithium bromide and water, respectively at the
same temperature. Figure 3 shows a chart giving the specific enthalpy-temperature-mass fraction
data for water-lithium bromide solutions. The chart is drawn by taking reference enthalpy of
u k}kg for liquid water at 0
o
C and solid anhydrous lithium bromide salt at 25
o
C.

The enthalpy of pure water vapour and liquid at different temperatures and pressures can
be obtained from pure water property data. For all practical purposes, liquid water enthalpy,
h
W,IIquId
at any temperature T can be obtained from the equation:

h
W,IIquId
= 4.19 (T -T
rcI
) k} kg

where T
rcI
is the reference temperature, 0
o
C.





Figure 3: Enthalpy Temperature - Concentration diagram for H2O-LiBr solution

3.5 Enthalpy values for pure water (liquid and superheated vapour)

The enthalpy of pure water vapour and liquid at different temperatures and pressures can
be obtained from pure water property data. For all practical purposes, liquid water enthalpy,
h
W,IIquId
at any temperature T can be obtained from the equation:

h
W,IIquId
= 4.19 (T -T
rcI
) k} kg
where T
rcI
is the reference temperature, 0
o
C.

The water vapour generated in the generator of water-lithium bromide system is in super-
heated condition as the generator temperature is much higher than the saturation water
temperature at that pressure. The enthalpy of superheated water vapour, h
W,sup
at low pressures
and temperature T can be obtained approximately by the equation:

h
W,sup
= 2Su1 + 1.88 ( T - T
rcI
) k} kg

3.6 Crystallization

The pressure-temperature-mass fraction and enthalpy-temperature -mass fraction charts
show lines marked as crystallization in the lower right section. The region to the right and below
these crystallization lines indicates solidification of LiBr salt. In the crystallization region a two-
phase mixture (slush) of water-lithium bromide solution and crystals of pure LiBr exist in
equilibrium. The water-lithium bromide system should operate away from the crystallization
region as the formation of solid crystals can block the pipes and valves. Crystallization can occur
when the hot solution rich in LiBr salt is cooled in the solution heat exchanger to low
temperatures. To avoid this, the condenser pressure reduction below a certain value due to say,
low cooling water temperature in the condenser should be avoided. Hence in commercial
systems, the condenser pressure is artificially maintained high even though the temperature of
the available heat sink is low. This actually reduces the performance of the system, but is
necessary for proper operation of the system. It should be noted from the property charts that the
entire water-lithium bromide system operates under vacuum.

4. SteadyflowanalysisofWaterLithiumBromide
Systems



Figure 4: A schematic of water LiBr system; A Absorber; C Condenser; G Generator; P
Solution Pump; SHX Solution HX; ER Refrigerant Expansion valve; ES Solution Expansion
Valve
Figure 4 shows the schematic of the system indicating various state points. A steady flow
analysis of the system is carried out with the following assumptions:

i. Steady state and steady flow
ii. Changes in potential and kinetic energies across each component are negligible
iii. No pressure drops due to friction
iv. Only pure refrigerant boils in the generator.

The nomenclature followed is:

m = mass flow rate of refrigerant, kg/s

m
ss
= mass flow rate of strong solution (rich in LiBr), kgs

m
ws
= mass flow rate of weak solution (weak in LiBr), kgs

The circulation ratio () is defined as the ratio of strong solution flow rate to refrigerant flow
rate. It is given by:
=
m
ss
m

implies that the strong solution flow rate is given by:

m
ss
= m

The analysis is carried out by applying mass and energy balance across each component.

Condenser:
m
1
= m
2
= m

Q
C
= m (h
1
- h
2
)

P
C
= P
sat
(T
C
)

where T
C
is the condenser temperature

Expansion valve (refrigerant):


m
2
= m
3
= m

h
2
= h
3






Evaporator:

m
3
= m
4
= m

Q
c
= m (h
4
-h
3
)

P
c
= P
sat
(T
c
)

where T
c
is the evaporator pressure:

Absorber:

From total mass
m + m
ss
= m
ws


m
ss
= m m
ws
= (1 + )m

From mass balance for pure water:

m + (1 -
ss
)m
ss
= (1 -
ws
)m
ws


=

ws

ss
-
ws


Q
a
= m h
4
+ m h
10
- (1 + )m h
5


Q
a
= m |(h
4
- h
5
) + (h
10
- h
5
)]




The first term in the above equation m ( h
4
- h
5
) represents the enthalpy change of water as
changes its state from vapour at state 4 to liquid at state 5. The second term
m (h
10
- h
5
) represents the sensible heat transferred as solution at state 10 is cooled to
solution at state 5.

Solution pump:

m
5
= m
6
= m
ws


W
P
= m
ws
(h
6
- h
5
) = (1 + )m (h
6
- h
5
)



however, if we assume the solution to be incompressible, then:

W
P
= (1 + )m :
soI
(P
6
- P
5
) = (1 + )m :
soI
(P
c
- P
c
)

where :
soI
is the specific volume of the solution which can be taken to be approximately equal to
0.00055 mSkg. Even though the solution pump work is small it is still required in the selection
of suitable pump.



4.Practicalproblemsinwaterlithiumbromidesystems

Practical problems typical to water-lithium bromide systems are:

1. Crystallization
2. Air leakage, and
3. Pressure drops

As mentioned before to prevent crystallization the condenser pressure has to be maintained at
certain level, irrespective of cooling water temperature. This can be done by regulating the flow
rate of cooling water to the condenser. Additives are also added in practical systems to inhibit
crystallization. Since the entire system operates under vacuum, outside air leaks into the system.
Hence an air purging system is used in practical systems. Normally a two -stage ejector type
purging system is used to remove air from the system. Since the operating pressures are very
small and specific volume of vapour is very high, pressure drops due to friction should be
minimized. This is done by using twin- and single-drum arrangements in commercial systems.
Few other disadvantages are corrosion due to the reaction of LiBr with the metal tubing which
not onyl damages the piping but also makes the solution less effective. [4]

6.Heatsourcesforwaterlithiumbromidesystems

Water-lithium bromide systems can be driven using a wide variety of heat sources.
Large capacity systems are usually driven by steam or hot water. Small capacity systems are
usually driven directly by oil or gas. A typical single effect system requires a heat source at a
temperature of about 120
o
C to produce chilled water at 7
o
C when the condenser operates at
about 46
o
C and the absorber operates at about 40
o
C. The COPs obtained in the range of 0.6 to
0.8 for single effect systems while it can be as high as 1.2 to 1.4 for multi-effect systems.

7.MinimumheatsourcetemperaturesforLiBr
Watersystems

Application data for a single-stage water-lithium bromide vapour absorption system
with an output chilled water temperature of 6.7
o
C (for air conditioning applications) is shown
in Table 1.



Cooling water temperature Minimum Heat source COP
(inlet to absorber & temperature
condenser) (Inlet to generator)
23.9
o
C 65
o
C 0.75
26.7
o
C 75
o
C 0.74
29.4
o
C 85
o
C 0.72
32.2
o
C 95
o
C 0.71

Table 1. Application data for a single-stage water-lithium bromide system

The above values are simulated values, which were validated on actual commercial
systems with very efficient heat and mass transfer design. If the heat and mass transfer is not
very efficient, then the actual required heat source temperatures will be higher than the
reported values. For a given cooling water temperature, if the heat source temperature drops
below the minimum temperature given above, then the COP drops significantly. For a given
cooling water temperature, if the heat source temperature drops below a certain temperature
(minimum generation temperature), then the system will not function. Minimum generation
temperature is typically 10 to 15
o
C lower than the minimum heat source temperature. If air
cooled condensers and absorbers are used, then the required minimum heat source
temperatures will be much higher ( 150
o
C). The COP of the system can be increased
significantly by multi-effect (or mult-stage) systems. However, addition of each stage
increases the required heat source temperature by approximately 50
o
C.


8.Capacitycontrol

Capacity control means capacity reduction depending upon load as the capacity will be
maximum without any control. Normally under both full as well as part loads the outlet
temperature of chilled water is maintained at a near constant value. The refrigeration capacity
is then regulated by either:
1. Regulating the flow rate of weak solution pumped to the generator through the solution
pump
2. Reducing the generator temperature by throttling the supply steam, or by reducing the
flow rate of hot water
3. Increasing the condenser temperature by bypassing some of the cooling water supplied to
the condenser

Method 1 does not affect the COP significantly as the required heat input reduces with
reduction in weak solution flow rate, however, since this may lead to the problem of
crystallization, many a time a combination of the above three methods are used in commercial
systems to control the capacity.




9.StandardProblem

A single stage vapour absorption refrigeration system based on H2O-LiBr has a refrigeration
capacity of 300 kW. The system operates at an evaporator temperature of 5
o
C (P
sat
=8.72 mbar)
and a condensing temperature of 50
o
C (P
sat
=123.3 mbar). The exit temperatures of absorber and
generator are 40
o
C and 110
o
C respectively. The concentration of solution at the exit of absorber
and generator are 0.578 and 0.66, respectively. Assume 100 percent effectiveness for the solution
heat exchanger, exit condition of refrigerant at evaporator and condenser to be saturated and the
condition of the solution at the exit of absorber and generator to be at equilibrium. Enthalpy of
strong solution at the inlet to the absorber may be obtained from the equilibrium solution data.

Find:
a) The mass flow rates of refrigerant, weak and strong solutions
b) Heat transfer rates at the absorber, evaporator, condenser, generator and solution heat
exchanger
c) Solution pump work (density of solution = 1200 kg/m3).




Given:
Refrigeration capacity : 300 kW
Evaporator temperature : 5
o
C
Condenser temperature : 50
o
C
Absorber temperature : 40
o
C
Generator temperature : 110
o
C
Weak solution concentration,
WS
: 0.578
Strong solution concentration,
SS
: 0.66
Effectiveness of solution HX,
HX
: 1.0
Density of solution,
sol
: 1200 kg/m
3
Refrigerant exit at evaporator & condenser : Saturated
Solution at the exit of absorber & generator : Equilibrium







Assuming the refrigerant vapour at the exit of generator to be in equilibrium with the strong
solution leaving the generator

Temperature of vapour at generator exit = 110
o
C

enthalpy of vapour = 2501+1.88 X 110 = 2708 kJ/kg

From the definition of effectiveness of solution HX;

e
EX
= |m
SS
C
p,SS
(I
8
- I
9
)]|m
SS
C
p,SS
(I
8
- I
6
)] = 1.u ( m
SS
< m
WS
)

T
9
= T
6
= 40
o
C

From the above equation, the following property data at various points are obtained using
refrigerant property charts and water LiBr solution property charts

State Temperature Pressure Mass Enthalpy
point
(
o
C)
(mbar)
Fraction of
LiBr, (kJ/kg)
1 110 123.3 0 2708
2 50 123.3 0 209
3 5 8.72 0 209
4 5 8.72 0 2510
5 40 8.72 0.578 104
6 40 123.3 0.578 104
7 - 123.3 0.578 130.84
8 110 123.3 0.66 244
9 40 123.3 0.66 275
10 40 8.72 0.66 275

The enthalpy of superheated water vapour (hv) may be obtained by using the equation:

hv = 2501 + 1.88 t, where hv is in kJ/kg and t is in
o
C.
Enthalpy of weak solution at the exit of solution HX is obtained from the energy balance
equation: m
WS
(h
7
- h
6
) = m
SS
(h
8
- h
9
) h
7
= h
6
+ m
SS
(h
8
- h
9
) m
WS
= 68.7k} kg
a) Required mass flow rate of refrigerant, m = c (b4 - bS) = u.1Su4kg s
Circulation ratio, = mSS m = WS (SS -WS) = 7.uS
mass flow rate of strong solution, mSS = m = u.919Skg s
mass flow rate of weak solution, mWS = ( + 1)m = 1.uS kg s

b) Heat transfer rates at various components:
Evaporator: Qe = SuukW (input data)
Absorber: From energy balance:
Qa = mh4 + mSSh1u - mWShS = Suu.194SkW (stanuaiu answei: SS4.74kW)
Generator: From energy balance:
Qg = mh1 + mSSh8 -mWSh7 = 496.71 kW (stanuaiu answei: S8u.S4kW)
Condenser: From energy balance:
Qc = m(h1 - h2) = S2S.78 (stanuaiu answei: S2S.9kW)
Solution heat exchanger: From energy balance:
QSBX = m(h8 - h9) = m( + 1)(h7 - h6) =
-29.u2 (stanuaiu answei: 122.SkW)
c)System COP (neglecting pump work) =
c

= u.6u4u( stonJorJ onswcr = u.7884)

Error percentage =
0.6040-0.7884
0.7884
= 2S%
d) Solution pump work (assuming the solution to be incompressible)
WP = vsol(P6 - PS) = (P6 - PS) sol = (12S.S - 8.72) 1u - 1 12uu =
u.uu9SkW (stanuaiu answei = u.uu9S kW)
THEVARIATIONOFCOPANDHEATEXCHANGEDWITHT
G

10.REFERENCES

[1] Xiaolin WANG and Hui T. CHUA, Absorption Cooling: A Review of Lithium Bromide-
Water Chiller Technologies, Recent Patents on Mechanical Engineering 2009, 2, 193-213
[2] Kai WANG, Omar ABDELAZIZ, Edward A. VINEYARD, Thermophysical Properties of
Lithium Bromide + 1, 2-Propanediol Aqueous Solutions Solubilities, Densities and
Viscosities, International Refrigeration and Air Conditioning Conference 2012
[3] F L Lansing, Computer Modeling of a Single Stage Lithium Bromide-water Absorption
Refrigeration Unit, JPL Deep Space Network Progress Report 42-32
[4] Kevin D. Rafferty, ABSORPTION REFRIGERATION, Geo-Heat Centre
[5] Absorption Cooling Data Sheet, CHP Group CIBSE
[6] Vapour Absorption Refrigeration Systems Based On Water-Lithium Bromide Pair, NPTEL
[7] Reynaldo Palacios-Bereche, R. Gonzales and S. A. Nebra, Exergy calculation of lithium
bromidewater solution and its application in the exergetic evaluation of absorption refrigeration
systems LiBr-H2O, International Journal of Energy Research
[8] Guozhen Xie, Guogang Sheng, Guang Li, Shuyuan Pan, Improvement of the Performance for
an Absorption Refrigerating System with Lithium bromide-water as Refrigerant by Increasing
Absorption Pressure, HVAC Technologies for Energy Efficiency, Vol. IV-10-4