12

Vapour-Absorption System

12.1 SIMPLE VAPOUR-ABSORPTION SYSTEM

The function of the compressor in the vapour-compression system is to continuously

withdraw the refrigerant vapour from the evaporator and to raise its pressure and
hence temperature, so that the heat absorbed in the evaporator, along with the work
of compression, may be rejected in the condenser to the surroundings.
In the vapour-absorption system, the function of the compressor is accomplished
in a three-step process by the use of the absorber, pump and generator or reboiler as
follows:
(i) Absorber: Absorption of the refrigerant vapour by its weak or poor solution
in a suitable absorbent or adsorbent, forming a strong or rich solution of the
refrigerant in the absorbent/adsorbent.
(ii) Pump: Pumping of the rich solution raising its pressure to the condenser
pressure.
(iii) Generator or Desorber: Distillation of the vapour from the rich solution
leaving the poor solution for recycling.
A simple vapour-absorption system, therefore, consists of a condenser, an
expansion device and an evaporator as in the vapour-compression system, and in
addition, an absorber, a pump, a generator or desorber and a pressure-reducing valve
to replace the compressor. The schematic representation of the system is shown in
Fig. 12.1 in which various components of the system are arranged according to their
pressures and temperatures. The refrigerating effect is shown as Q0 at temperature
T0 and the heat rejected in the condenser as Qc at temperature Tc = Tk of the
environment. The compressor work is replaced by the heat supplied in the generator
Qh plus pump work QP. Cooling must be done in the absorber to remove the latent
heat of the refrigerant vapour as it changes into the liquid state by absorption by the
weak solution. Let this heat rejected in the absorber be QA at absorber temperature
TA = Tk. Then the energy balance of the system is
Q0 + QP + Qh = QC + QA = Qk (12.1a)
where Qk represents the net heat rejected to the environment.
 Vapour-Absorption System 403

1 5

pk C G Qh
6
QC 2
7
Q0 8

Hot Body
p0 E
3
p

Cold Body

Ambient
P
4 QA

To TA = TC = Tk Th
T
Fig. 12.1 Schematic representation of simple vapour absorption system

The pump work QP = – z v d p, is very small compared to the compressor work in

the vapour compression system, as the specific volume v of the liquid is extremely small
compared to that of the vapour (vf << vg). The energy consumption of the system is
mainly in the generator in the form of heat supplied Qh.
Generally, calculations for the vapour-absorption system are based on a unit mass
of the refrigerant vapour distilled from the generator. All heat and mass flow quan-
tities per unit mass of the vapour are then referred to as specific quantities. Thus, if
D is the mass of the vapour distilled, then the various specific heat quantities are
Q0 Q
, qP = P , and so on.
q0 =
D D
The energy balance equation per unit mass of the vapour distilled is then
q 0 + q P + q h = q C + QA = q k (12.1b)
The overall coefficient of performance may be denoted by z and is expressed as
Refrigerating effect
z=
Energy supplied
q0 q0
= = (12.2)
qh + q P q k - q0
@ q0/qh, neglecting pumpwork which is small compared to qh.

12.2 MAXIMUM COEFFICIENT OF PERFORMANCE OF A

HEAT OPERATED REFRIGERATING MACHINE

The vapour-absorption system is a heat-operated refrigerating machine. It may

be considered as a combination of a heat engine and a refrigerating machine as
404 Refrigeration and Air Conditioning

illustrated in Fig. 12.2. The energy supplied to the system is in the form of heat Qh at
temperature Th. The thermodynamic cycle is considered to comprise of a heat-en-
gine E cycle, operating between the heat source temperature Th and the temperature
of heat rejection Tk, and a refrigerator R cycle operating between the refrigeration
temperature T0 and temperature of heat rejection Tk. The work done in the heat
engine part of the cycle is equal to the work requirement of the refrigeration part of
the cycle. Thus, one may write for the COP of the cycle

· 0 = hth · Ec
Q W Q
z= 0 =
Qh Qh W
which implies that the COP of a heat-operated refrigerating machine is equal to the
product of the thermal efficiency of the heat engine part of the cycle and the coeffi-
cient of performance for cooling of the refrigeration part of the cycle. Accordingly,
COP z of vapour absorption system expressed by Q0/Qh should not be compared
with COP E of vapour compression system which is Q0/W.
Temperature of
Th Heat Source
Qh

QA
Tk Condenser and Absorber
Temperature
QC

Q0
T0 Refrigeration
Temperature
Fig. 12.2 Representation of a heat-operating machine as a combination
of a heat engine and a refrigerator

The COP of a heat-operated refrigerating machine should, therefore, be maxi-

mum when each of the two terms has a maximum value which would be so when
both are equal to their respective Carnot values. Thus

zmax = hthCarnot · Ec Carnot =

FG T - T IJ FG T IJ
h k 0
H T KH T - T K
h k 0

= 1-
FG Tk IJ F 1 I (12.3)
H Th K GG T - 1JJ
k
HT K
0

It can be seen from the above expression that the COP depends on temperatures
Th, Tk and T0 and in order for it to be high one should have:
(i) Temperature Th of the heat source as high as possible,
(ii) Temperature Tk of the heat sink as low as possible, and
(iii) Temperature T0 of refrigeration as high as possible.
 Vapour-Absorption System 405

Note However, absorption system is not a reversible cycle. There is a degree of irrevers-
ibility due to mixing of refrigerant and absorbent. Its COP, first, increases with increase in
generator temperature, it reaches an optimum value, and then it starts decreasing as a
result of increase in irreversibility at high generator temperatures.
In the vapour-absorption cycle, the system formed by the generator-valve-
absorber-pump may be considered to represent the heat engine part of the cycle.
This part in which only the refrigerant-absorbent solution circulates, is named as the
solution circuit. On the other hand, the condenser-expansion device-evaporator form
the usual refrigeration part of the cycle. This part is named as the refrigerant circuit.
It may be noted that, in case, the condenser and absorber temperatures are not the
same and are equal to TC and TA respectively, then the maximum possible COP is
given by
T - TA T0
zmax = h · (12.4)
Th TC - T0

Example 12.1 In a vapour-absorption refrigeration system, the refrigeration

temperature is – 15°C. The generator is operated by solar heat where the tem-
perature reached is 110°C. The temperature of the heat sink is 55°C. What is the
maximum possible COP of the system?

Solution T0 = 273 – 15 = 258 K

Th = 273 + 110 = 383 K
Tk = 273 + 55 = 328 K
383 - 328 258
zmax = · = 0.0914 · 3.69 = 0.34
383 328 - 258

Note Thus, the COP of 0.34 of the heat-operated vapour absorption system is equivalent
to COP of 3.69 of vapour compression system in this case.

12.3 COMMON REFRIGERANT-ABSORBENT SYSTEMS

Some of the desirable characteristics of a refrigerant-absorbent pair for an absorp-

tion system are low viscosity to minimize pump work, low freezing point and good
chemical and thermal stability. Irreversible chemical reactions of all kinds, such as
decomposition, polymerization, corrosion, etc., are to be avoided.
In addition to the above, two main thermodynamic requirements of the mixture are:
(i) Solubility requirement: The refrigerant should have more than Raoult’s law
solubility in the absorbent or adsorbent so that a strong solution, highly rich
in the refrigerant, is formed in the absorber by the absorption of the refriger-
ant vapour.
(ii) Boiling points requirement: There should be a large difference in the nor-
mal boiling point of the two substances, at least 200°C, so that the absorbent
exerts negligible vapour pressure at the generator temperature. Thus, almost
absorbent-free refrigerant is boiled off from the generator and the absorbent
alone returns to the absorber. If absorbent vapour goes with the refrigerant
406 Refrigeration and Air Conditioning

vapour to refrigerant circuit, the refrigeration produced will not be isother-

mal. In case a solid adsorbent is used, it does not exert any vapour pressure.
Thus, pure refrigerant vapour only will go to the refrigerant circuit.
The two commonly used pairs are those of refrigerant NH 3 + absorbent H2O, and
refrigerant H2O + adsorbent LiBr2.
In the ammonia-water system, ammonia is the refrigerant and water is the absorb-
ent. Ammonia forms a highly non-ideal solution in water. Hence, from the point of
view of the solubility requirement, it is satisfactory. But the difference in their boil-
ing points is only 138°C. Hence the vapour leaving the generator contains some
amount of water.
Thus, the ammonia-water system is not suitable from the point of view of the
boiling point requirement.
In the water-lithium bromide system, water is the refrigerant and lithium bromide
is the adsorbent. Hence the mixture is used only in air-conditioning applications
since water freezes at 0°C. The mixture is again non-ideal and is satisfactory from
the point of view of the solubility requirement. Since lithium bromide is a salt, it
exerts no vapour pressure. So the vapour leaving the generator is a pure refrigerant.
The mixture, therefore satisfies the boiling point requirement also. However, it is
corrosive and the plant works under high vacuum, both in condenser and evaporator.
Hence, a purge unit is used.
The thermodynamic properties of the aqua-ammonia system are available in the
form of Jennings and Shannon7 tables. These tables give values of saturated liquid
and vapour enthalpies, equilibrium temperatures and vapour compositions as a func-
tion of pressure and liquid composition. Kohloss and Scott8 developed a diagram
based on similar data by Scatchard.16
The enthalpy composition (h – x ) diagram for the aqua-ammonia system is due to
Merkel and Bosnjakovic.12 An advantage of this diagram is that it makes it possible
to geometrically represent the complete vapour-absorption cycle. There are auxil-
iary lines on this diagram which are used to locate the equilibrium vapour state, say
A†, corresponding to a certain liquid state, Say A¢, by drawing a tie line and vice
versa, as shown in Fig. 4.19.
The properties of H2O – LiBr 2 system were established by Rosenfeld and
Karnaukh 15, Lower and McNeely.11 An enthalpy-composition diagram is available
for the liquid mixture. The vapour phase consists of pure water only. Some data in
the form of vapour pressure, specific heat, specific weight and differential heat of
mixing have been given by Niebergall.13
Research work is in progress on various other refrigerant absorbent combina-
tions 1, 2, 5, 6, 10, 17, 18, 21.

12.4 MODIFICATIONS TO SIMPLE VAPOUR-

ABSORPTION SYSTEM

There are two drawbacks in the simple vapour-absorption cycle. These are:
(i) Low temperature of the rich solution entering the generator and high tempera-
ture of the poor solution entering the absorber.
 Vapour-Absorption System 407

(ii) Presence of absorbent in the vapour leaving the generator and going to
refrigerant circuit.
The two are separately discussed along with proposed modifications.

12.4.1 Using Liquid-Liquid Heat Exchanger in the Solution Circuit

Referring to Fig. 12.3, it is observed that in th pk = Const.
the simple system, saturated rich solution at 4 2

Cooling of Poor
at refrigerant concentration xrL in the liquid 1
phase must be heated from the absorber

Rich Solution
1a

Heating of
Solution
temperature tA to the bubble temperature t1 at
the generator pressure, whereas the saturated
poor solution at 2 from the generator at tem-

t
perature th and refrigerant concentration xaL p0 = Const.
again in the liquid phase must be cooled to 3
temperature t3 in the absorber. This is ineffi-
tA 4
cient since useful heat must be added in the
generator and the same must be rejected in the
x aL x Lr
absorber.
x
The system can be improved by incorpo-
rating a regenerative heat exchanger between Fig. 12.3 Diagram showing cooling
of poor solution and
the poor and rich solutions. This will reduce heating of rich solution
the amount of heat added in the generator and
hence increases the COP, and decrease the amount of heat rejected in the absorber.
The sizes of the generator and absorber will also be reduced. This heat exchanger is
called a liquid-liquid heat exchanger. In such a case, the state after heating of the
rich solution at 1a will be a subcooled state below the saturation temperature at 1 at
pressure pk.

12.4.2 Using Analyser—The Exhausting Column, and Dephlegmator—The

Rectifying Column
In a system like that of ammonia-water, the vapours distilled from the generator
contain a considerable amount of absorbent vapour which subsequently reaches the
evaporator after condensation. As a result, evaporation would not be isothermal and
the required low temperature would not be reached in the evaporator as illustrated
in Fig. 12.4.
The temperature entering evaporator at the beginning of evaporation is t01, and
leaving evaporator is t02 which is equal to maximum permissible refrigeration tem-
perature. The temperature after complete evaporation is very high, equal to the dew
point temperature at evaporator pressure and composition.
Let p0 be the required evaporator pressure with pure refrigerant corresponding
to evaporation temperature t0 . With the mixed vapour at V with concentration
xaV leaving the generator in equilibrium with the boiling poor solution at L with
concentration xaL, the condensate is at point 6 at pressure pk and temperature tC of the
condenser.
408 Refrigeration and Air Conditioning

L V

6
pk = Const. tc
t0

p0 = Const.
p*0 = Const.
t

4* 4 9*
tA
t0 = t02
8* 7, 8
t01
7*

L *
0 a r r xVa Pure
1
NH 3 Refrigerant
Fig. 12.4 Effect of presence of absorbent in evaporator

The temperature at the end of throttling to p0 and complete evaporation is t9 in the

case of refrigerant mixed with absorbent instead of t 7 = t8 = t01 = t02 with the pure
refrigerant at pressure p0. In order to obtain maximum permissible refrigeration tem-
perature t0 = t02, at the end of evaporation, it is necessary to have expansion to a
lower evaporator pressure p0* instead of p 0. The liquid entering the evaporator at
first evaporates somewhat like a pure substance at pressure p 0* corresponding to
temperature t01 = t7*. The liquid gradually becomes weaker in the refrigerant and at
the end of partial or incomplete evaporation to 8*, it reaches temperature t02 = t8*.
Thus, evaporation is incomplete.
Not only is the evaporator pressure reduced due to concentration xaV being less
than unity, it can be seen that the rich solution concentration at the given absorber
temperature tA is also reduced, say, from xr to xr*, because of a lower absorber
pressure. This will ultimately result in a smaller difference in the rich and poor solu-
tion concentrations and hence a lower COP as explained in Sec. 12.5.3.
We thus see that there are three adverse effects of the absorbent vapour from the
generator entering the refrigerant circuit. These are the following:
(i) Evaporator pressure has to be lowered from p 0 to p0* to attain the required
refrigeration temperature of t0 = t02.
(ii) Rich solution refrigerant concentration decreases from xr to xr*, thus increas-
ing rich solution circulation f and decreasing COP.
(iii) Evaporation is incomplete. All the liquid does not evaporate. Part of the
liquid has to go to the absorber without producing any refrigerating effect.
Hence, COP decreases further.
 Vapour-Absorption System 409

Example 12.2 With assumed numerical values, examine the effect of pres-
ence of water in vapour leaving generator in NH3—H 2O system on solution
circulation rates, refrigeration temperature and COP.

Solution Consider following condenser and evaporator temperatures:

tk = tC = 50°C, t0 = – 17.5°C
Assuming pure ammonia vapours are evolved in generator, we have for pressures
from the table of properties of ammonia:
p k = (psat)50°C = 20.33 bar
p 0 = (psat)–17.5°C = 2.25 bar
Now, if generator temperature is th = 156°C, we have for poor solution concentra-
tion of NH 3
xaL = 0.2 (sat. liq. at 20.33 bar, 156°C)
and if absorber temperature is tA = 40°C, we have for rich solution concentration of
NH3.
xrL = 0.34 (sat. liq. at 2.25 bar, 40°C)
The concentration of NH3 in vapour leaving generator
xd = xaV = 0.73 (sat. vap. at 20.33 bar, 156°C)

Specific Solution Circulation Rates Then, from Eqs (12.7) and (12.8), we have
per unit mass of vapour leaving generator, circulation rates of rich solution leaving
absorber and poor solution leaving generator respectively as
xd - xa 0.73 - 0.2 0.53
f= = = = 3.8 kg/kg vapour
xr - xa 0.34 - 0.2 0.14
f – 1 = 2.8 kg/kg vapour
But, the difference in N.B.P. of NH3(–33°C) and that of H2O (100°C) is small,
only 133°C. The consequences of the same are the following:
(i) Considerable amount of absorbent water is present in the vapour leaving
generator. This goes to the refrigerant circuit. It is equal to (1 – xd) = 1 – 0.73
= 0.27 (27%) in this case.
(ii) As a result, temperature of – 17.5°C would not be attained after throttling to
2.25 bar.
(iii) To attain this temperature, an evaporator pressure lower than 2.25 bar would
be required.
(iv) Let the throttling be done to an evaporator pressure of p*0 = 1 bar. Even with
this low pressure, the temperature attained after throttling would be t01 = –
19°C only.
(v) After complete evaporation, the temperature of this liquid-vapour NH3/H2O
mixture would be as high as t9* = 76°C (Fig. 12.4). As the maximum refrigera-
tion temperature required is t02 = –17.5°C, it is seen that only a small fraction
of the mixture could be allowed to evaporate. The rest would have to go to the
absorber, along with vapour, without producing any refrigerating effect.
Hence, Q0 would be very much reduced.
410 Refrigeration and Air Conditioning

(vi) Further, with the lowering of absorber pressure to 1 bar, the new rich solution
concentration would be
xr* = 0.234 (sat. liq. at 1 bar, 40°C)
Thus, xr* – xa = 0.235 – 0.2 = 0.035 would become very small resulting in
extremely large solution circulation rates f and (f – 1), and hence large quantity
of heat added in generator, as seen from Eq. (12.9), and very low COP.
To return the absorbent to the generator and to allow, as far as possible, only
the refrigerant vapour to enter the condenser, two elements are added to the simple
absorption system. These are:
(i) The analyser or the exhausting column.
(ii) The dephlegmator and rectifier or the rectifying column.
The analyser or the exhausting column is installed on top of the generator as
shown in Fig. 12.5. The vapour, leaving the generator with refrigerant concentration
V
x a in equilibrium with the boiling poor solution having concentration xaL, enters the
analyser at 2V (Fig. 12.7). As it travels upwards, counterflow to the entering rich
solution at 1 with concentration xrL, the vapour encounters heat and mass exchange
with the falling rich solution ultimately leaving the analyser enriched in the refri-
gerant with vapour concentration x d = x5 £ x Vr in equilibrium with the rich solution
having concentration x rL.

1a, x rL
5, = xVr = 5

An: Analyser or 7V, e

Exhausting Column

QR D: Dephlegmator

7L

2L 2V, x Va
R: Rectifier or
Liquid Vapour Rectifying Column

2, xaL 6 5, xd
Qh Drip
Fig. 12.5 Analyser or exhausting Fig. 12.6 Dephlegmator and
column rectifying column

We see from Fig. 12.7 that this method has the additional advantage of returning
some heat from the vapour to the generator in the form of preheating of the rich
solution from t1a to t1 to t2 with simultaneous cooling of the vapour from t2 to t5 = t1.
The enriched vapour from the generator-analyser now enters the dephlegmator or
the rectifying column as shown in Fig. 12.6 wherein heat is removed from the vapour
by the circulation of a cooling medium. The leaving state 7V of the vapour is deter-
mined by the temperature t7 = tR of the cooling medium (Fig. 12.7) at the end of the
 Vapour-Absorption System 411

rectifying column. A part of the vapour is condensed at 7L and is returned as drip 6 to

the analyser. The leaving vapour having concentration xe (higher than xd) goes to the
refrigerant circuit. In the rectifying column, heat QR is rejected to the cooling medium.

V
pk = const a
V
r
2V
5

7V

st
on
=c

st
th

c on

st
on
t1 =

=c
TR
h

2L

1 6 7L
1a

L L d e
a r

Fig. 12.7 Thermodynamic processes of analyser and exhausting and

rectifying columns on h–x diagram

The latter method of increasing the refrigerant concentration of the vapour has a
drawback in that it involves a loss of useful heat added in the generator which is
rejected to the cooling medium in the dephlegmator. The drip returns to the genera-
tor and has to be evaporated again. The conditions under which the use of a
dephlegmator would improve the COP would depend on the working pair being
used and the operating conditions.

Note It may be noted that the use of analyser and dephlegmator is not necessary in the
case of systems such as lithium bromide-water in which case the absorbent does not exert
any significant vapour pressure at all.

12.5 ACTUAL VAPOUR-ABSORPTION CYCLE AND

ITS REPRESENTATION ON ENTHALPY-
COMPOSITION DIAGRAM3,11

Figure 12.8 shows the schematic arrangement of the actual vapour-absorption cycle
and Fig. 12.9 presents its thermodynamic cycle on the h – x diagram. The system
consists of generator G, analyser AN, dephlegmator D and condenser C on the high
412 Refrigeration and Air Conditioning

pressure side, and evaporator E and absorber A on the low pressure side. Pump P,
expansion valve VI and pressure-reducing valve VII separate the two sides. In
addition, liquid-vapour heat exchanger HE I and liquid-liquid heat exchanger HE II
are also provided.

7, D kg, e = 7

QR

6
5

1a F kg,
L AN
r

C QC G

2, (F – D) kg, L
a
8 Qh
12
HE II
HEI

3
9
VII
11
VI 3a
10
4a

E A

4
Q0 QA
P
Fig. 12.8 Schematic diagram of actual vapour absorption system

The vapours at 5, distilled from the generator-analyser, enter the dephlegmator.

The vapours from the dephlegmator with higher concentration of the refrigerant at 7
then enter the refrigerant circuit, whereas the drip at 6 returns to the generator-
analyser. The vapours are condensed to 8 in the condenser, precooled to 9 in the
liquid vapour regenerative heat exchanger and throttled to 10 before entering the
evaporator. The state 10 is at the same point as state 9 on the h-x diagram as both
enthalpy and composition remain the same before and after throttling. The
refrigerant entering the evaporator at 10, leaving the evaporator at 11 and the liquid
vapour heat exchanger at 12, comprises of a liquid plus vapour mixture. The
refrigerant is finally absorbed by the poor solution at 2 returning from the generator
 Vapour-Absorption System 413

after being cooled in the liquid-liquid heat exchanger to 3 and throttled to 3a,
whereas the rich solution from the absorber at 4 is pumped to 4a and heated to 1a
before entering the analyser.

pk

p0 d

5
7V

12V 11V
10V
12

t7
11

qh
q0
h

th 8

qA
2
pk
1 6 (Drip) 7L
1a
9, 10

H
p0 tA 11L
3, 3a 12L
10L
4, 4a
t0 = t02 t0 1 A

a r xe
1 (f – 1)

Fig. 12.9 Representation of vapour-absorption cycle on h-x diagram

The state points 1, 2, 3 and 4 can be located on the h-x diagram according to their
temperatures and compositions as the enthalpy of liquid is independent of pressure.
Also, point 3a lies at 3 only (isenthalpic process) and point 4a lies approximately at
4 itself as the pump work is very small. State point 5 of the vapour is along the
isothermal tie line drawn from 1. State point 7 is on the tie line corresponding to the
dephlegmator temperature t7 and condenser pressure pk. Point 8 is the saturation
state at pk and at the same composition as 7. Point 9 after subcooling of the liquid
can be plotted according to the temperature and composition and point 10 is at 9
itself (isenthalpic process). Point 11 is on the tie line corresponding to the evapora-
tor leaving temperature t02 = t 0 and pressure p0. The composition is same at 7, 8, 9,
414 Refrigeration and Air Conditioning

10, 11 and 12. Point 12 can be similarly located by knowing the temperature from
the energy balance of the heat exchanger.

12.5.1 Absorption-System Calculations

The thermodynamic analysis of the vapour-absorption cycle is based on the
following three equations which can be applied to any part of the system.
(i) Mass balance Sm = 0
(ii) Material balance (or partial mass balance) Smx = 0
(iii) Energy balance SQ + Smh = 0
Thus, if the mass handled by the pump is F and the refrigerant vapour distilled is
D, then by mass balance, the weak solution returning to the absorber is (F-D).
Also, applying material balance to the generator-analyser-dephlegmator taking
the refrigerant, say ammonia, as the material under consideration, we have
Fxr = (F – D) xa + Dxe (12.5)
in which xr = x 1a, xa = x2 and xe = x7
represent the refrigerant concentrations of rich solution, poor solution and vapour
respectively. The superscripts L and V have been dropped. This gives.
F x - xa
f= = e (12.6)
D x r - xa
Also, when the rectifier is not used, the vapour concentration is xd = x5,
xd - xa
f= (12.7)
xr - xa
Now, f represents the quantity of rich solution handled by the pump per unit mass of
the vapour distilled. This quantity is termed as the specific rich solution circulation.
The specific weak solution circulation is similarly given by
F -D x - xr
(f – 1) = = e (12.8)
D xr - xa
It must be pointed out that these quantities are of great practical importance from
the point of view of the COP of the system. The lower solution circulation rates will
ensure a higher COP. It can be seen that f mainly depends on the value of (xr – xa).
The latter quantity is called degasing range. This quantity should be as large as
possible. This means that xr should be as high as possible, and xa should be as low as
possible. This will happen when refrigerant has more than Raoult’s law solubility in
absorbent at the absorber temperature (negative deviation from Raoult’s law), and
when the N.B.Ps of the refrigerant and absorbent are wide apart.
Accordingly, both the thermodynamic requirements as stated in Sec. 12.3 would
be satisfied.
Further, we see that if the N.B.P. of the absorbent is very high, or if the absorbent
which is used exerts no vapour pressure at all, then pure refrigerant vapour only will
leave the generator, so that x e = x d = 1, and we have:
1 - xa 1 - xr
f= and f–1=
xr - x a xr - x a
 Vapour-Absorption System 415

We shall now apply energy balance to the individual components of the system
based on unit mass of the vapour distilled from the generator.
Solution Circuit Energy Balance Generator without dephlegmator States 5
and 7 are the same.
qh + f h1a = h5 + (f – 1) h2
whence
qh = h5 – h2 + f (h2 – h1a) (12.9)
Introducing an auxiliary quantity defined by
hH = h2 – f(h 2 – h1a) (12.10)
we get
qh = h 5 – h H (12.11)
Equation (12.9) shows that the heat added in the generator depends upon specific
solution circulation f.
Generator with dephlegmator qh + f h 1a = h7 + (f – 1) h2 + q R
whence
qh = h7 – h2 + f (h 2 – h1a), + qR
= (h7 – hH) + qR (12.12)
Liquid-liquid heat exchanger II Points 3, 4a and 1a represent subcooled liquid
states at pressure pk. Let qII represent the heat transfer in heat exchanger II. Then
qII = (f – 1) Ca (th – t3)
= fCr (t1a – tA) (12.13)
where th and tA are generator and absorber temperatures, and Ca and Cr are the spe-
cific heats of the poor and rich solutions respectively. Thus
f - 1 Ca
t1a = tA + (t – t ) (12.14)
f Cr h 3
Similarly
f -1
h1a = h4 + (h2 – h3) (12.15)
f
Since the specific heat of weak ammonia solution is smaller than that of the strong
solution and also since (f – 1) is less than f, it is seen that
(t1a – tA) < (th – t3)
Absorber qA + fh 4 = h12 + (f – 1) h3
whence
qA = h12 – h3 + f (h 3 – h4) (12.16)
Introducing another auxiliary quantity for the absorber defined by
hA = h3 – f (h 3 – h4 ) (12.17)
we get
qA = h12 – hA (12.18)
Since h3a = h3 and h4 » h4a, we can see from Eqs (12.10) and (12.17) that hA » hH.
Pump The pump work is given by
qP = fv4 ( pk – p0)/hP (12.19)
where hp is the pump efficiency.
416 Refrigeration and Air Conditioning

Refrigerant Circuit Energy Balance The mass flow rate as well as the composi-
tion is the same at all sections.
Condenser
qC = h7 – h8 (12.20)
Liquid-vapour heat exchanger I
qI = h8 – h9 = h12 – h11 (12.21)
Expansion valve V I
L
h9 = h10 = (1 – z) h 10 + z hV10 (12.22)
This along with the material balance equation
L V
x 9 = x10 = (1 – z) x10 + z x10 (12.23)
can be solved by trial and error to get the temperature t 10 = t01 after expansion and at
inlet to evaporator. Symbol z is used here for vapour dryness fraction (instead of x)
since x denotes liquid mole fraction in the case of mixtures.
Evaporator
q0 = h11 – h10 (12.24)
The overall energy balance gives
qh + q0 + qP = q C + qA + q R = q k

12.5.2 Auxiliary Quantities

It can be seen from Fig. 12.9 that if points 2 and 1a are joined by a line and the
straight line is extended to meet the vertical line corresponding to the leaving vapour
concentration x e at H, then the projections of 2-1a, 1a-H and 2-H on the abscissa are
proportional to 1, (f – 1) and f respectively. Also, the enthalpy at H is given by
hH = h2 – f (h2 – h1a ) (12.25)
which is the same as the auxiliary quantity for the generator as defined in Eq. (12.10).
Similarly, if one joins points 3 and 4 and extends the line to meet the same verti-
cal at A, then we get the auxiliary quantity for the absorber
hA = h3 – f (h3 – h4) (12.26)
as defined by Eq. (12.17).
These auxiliary quantities make it possible to geometrically represent the genera-
tor and absorber heat quantities on the h-x diagram as shown in Fig. 12.9.

12.5.3 Rich and Poor Solution Concentrations

As stated earlier, the specific solution circulation f is a very significant quantity. The
larger the value of f, the more is the pump work. Higher solution circulation rates of
both rich and poor solutions involve larger pressure drops in the system and hence
still more pump work. In addition, as seen from Eq. (12.9), a higher value of f results
in a larger heat input to the generator qh and hence a lower COP. Also, the heat
rejected in the absorber qA is more. And hence high f implies larger sizes of both
generator and absorber and accompanying losses in addition to a lower COP.
It is, therefore, desirable to have f as small as possible. It is seen from Eq. (12.6)
that for f to be small, the degasing range (xr – xa ) should be as large as possible.
In other words, the rich-solution concentration xr should be as high, and the poor-
solution concentration x a should be as low as possible.
 Vapour-Absorption System 417

The absorber pressure in the absorption system is equal to the evaporator

pressure p0 and the generator pressure is similarly equal to the condenser pressure
pk. Hence at a given generator pressure, the poor solution concentration is deter-
mined by the heating temperature th, and at a given absorber pressure, the rich solu-
tion concentration is determined by the cooling temperature tA. The higher the th, the
lower is x a. And lower the tA, the higher is x r. Hence the generator temperature
should be as high as possible, whereas the absorber temperature should be as low as
possible.

Example 12.3 In an ammonia-absorption system with an analyser but with-

out a dephlegmator the following data are given:
Condenser pressure 20.3 bar
Evaporator pressure 2.1 bar
Generator temperature 156°C
Absorber temperature 40°C
Determine, per unit mass of the vapour distilled:
(a) Specific solution circulation rates.
(b) Temperature t01 at inlet to evaporator if the liquid from the condenser is
cooled by 13°C in the liquid-vapour heat exchanger.
(c) The refrigerating effect if the maximum refrigeration temperature is 5°C.
(d) The heat transfer in the liquid-liquid heat exchanger.
(e) The heat added in the generator.
(f) The pump work.
(g) The coefficient of performance.
(h) The heat rejected in the absorber and condenser.
(i) Energy balance of the system.

Solution Refer to Figs 12.7 and 12.8.

At 20.3 bar and 156°C
Poor solution concentration, xa = 0.2
At 2.1 bar and 40°C
Rich solution concentration, xr = 0.34
Also, the concentration of vapour leaving the analyser, in equilibrium with the
entering rich solution is
x5 = x rV = 0.913
It is convenient to put the thermodynamic properties and flow rates at various
sections in a tabular form as in Table 12.1.
(a) Specific rich solution circulation rate
x - xa 0.913 - 0.2
f= 5 = = 5.1 kg/kg of vapour
xr - xa 0.34 - 0.2
Specific poor solution circulation rate
f – 1 = 5.1 – 1 = 4.1 kg/kg of vapour
(b) Temperature after condensation
t8 = 53°C (Saturated liquid at 0.913 composition and 20.3 bar).
418 Refrigeration and Air Conditioning

Temperature after subcooling

t9 = 53 – 13 = 40°C
For the throttling-expansion process
L V
(1 – z) x10 + z x10 = x10 = x9 = 0.913
L V
(1 – z) h10 + z h 10 = h10 = h9 = 444 kJ/kg

Table 12.1 Data for Example 12.3

State Pressure Temperature Concentration Enthalpy Flow rate

Point p t x h m&
bar °C kg NH3/kg mixture kJ/kg kg/s
1 20.3 — 0.34 — —
2 20.3 156 0.2 616 4.1
3 20.3 67 0.2 205 4.1
3a 2.1 67 0.2 205 4.1
4 2.1 40 0.34 63 5.1
4a 20.3 40 0.34 63 5.1
1a 20.3 — 0.34 — 5.1
5.7 20.3 — 0.913 1947 5.1
8 20.3 53 0.913 507 5.1
9 20.3 40 0.913 444 5.1
10 2.1 –16 0.913 444 5.1
11 2.1 5 0.913 1281 5.1
12 2.1 — 0.913 — 5.1

There are two variables, temperature t10 and vapour fraction z. A trial and error
solution can be obtained by assuming t10 . But in such a solution with the h-x dia-
gram, point 10 fluctuates greatly. A simpler and quite accurate method is to assume
the vapour state 10 V at x10V = 1 and then join the point 10V to 9 and extend the line to
intersect the saturated liquid line for 2.1 bar at 10L which gives the temperature after
expansion and the temperature at inlet to evaporator as
t01 = t10 = – 16°C
(c) Temperature after the evaporator
t02 = t11 = 5°C
Draw the isothermal tie line for 5°C and 2.1 bar. The intersection with x11 = 0.913
locates point 11.
Refrigerating effect
q0 = h11 – h10 = 1281 – 444 = 837 kJ/kg
(d) Heat transfer in the liquid-liquid heat exchanger
q = (f – 1) (h2 – h3) = 4.1 (616 – 205) = 1685 kJ/kg
= f (h1a – h4) = 5.1 (h1a – 63)
whence
h1a = 393 kJ/kg
(e) Heat added in the generator
qh = h5 – h 2 + f (h2 – h 1a) = 1947 – 616 + 5.1 (616 – 393)
= 2468 kJ/kg vapour
 Vapour-Absorption System 419

(f) Specific volume of the solution at 40°C, at the inlet to the pump
v4 = xr vNH3 + (1 – x4) vH2O = 0.34 (1.726 · 10–3 ) + 0.66 (1.008 · 10–3)
= 1.251 · 10–3 m3/kg
Pump work
qP = f v4 (pk – p0) = 5.1 · 1.251 · 10–3 (20.3 – 2.1) · 105
= 11,600 J/kg = 11.6 kJ/kg refrigerant
(g) Coefficient of performance
q0 837
COP = = = 0.34
qh + q P 2468 + 11.6
(h) Enthalpy of vapour entering absorber
h12 = h11 + (h8 – h9)= 1281 + (507 – 444) = 1344 kJ/kg
Heat rejected in the absorber
qA = h12 – h3 + f (h3 – h4) = 1344 – 205 + 5.1 (205 – 63)
= 1865 kJ/kg vapour
Heat rejected in the condenser
q C = h5 – h8 = 1947 – 507 = 1440 kJ/kg
(i) Energy balance
Heat rejected
qk = qA + qC = 1865 + 1440 = 3305 kJ/kg vapour
Heat received
q0 + qh + qP = 837 + 2468 + 11.6 = 3316.6 kJ/kg refrigerant
Thus the energy balance checks very closely.

12.6 REPRESENTATION OF VAPOUR ABSORPTION

1
CYCLE ON ln p – DIAGRAM
T
For the representation of the processes of vapour absorption machines, it is
necessary to develop state diagrams that contain composition. Enthalpy-concentra-
tion diagram, used for ammonia-water system, is already well-known in this respect.
Similarly, ln p – 1/T diagram, with composition of the mixture as parameter, has
been adopted for the representation of the vapour absorption cycle, particularly for
water-lithium bromide system.
We know that the saturation pressure versus saturation temperature relationship
of pure substances can be expressed in the form
hf g
ln p = a – b
T
In the case of binary mixtures, also, the above relationship can be used for
composition separately. And, in case there is any heat of mixing of the solution Dhm,
the above equation will assume the form
420 Refrigeration and Air Conditioning

h fg + D h mB
ln p = a¢ – b¢ or ln p = A –
T T
It is to be noted that both hfg and Dhm have been assumed to be independent
of temperature T. It has also been assumed that during boiling in the generator,
no appreciable quantity of the absorbent is evaporated, meaning that the solvent
exerts a negligible vapour pressure. This assumption is true for water-lithium
bromide mixture.
1
Thus, ln p versus relation, to a great extent, follows a straight line for a pure
T
substance as well as for a mixture. We have one such line for the refrigerant and
another for the absorbent. We can obtain such straight lines for each composition of
the mixture. The constant composition lines are parallel if D hm = 0. They diverge
towards higher temperatures if D hm is positive, and converge if D hm is negative as
shown in Fig. 12.10. The absorption system refrigerant-absorbent pairs have nega-
tive heat of mixing. Hence, these lines are convergent for absorption system.
The Appendix gives the ln p –1/T diagram for H2O – Li Br 2 system.

=C
=

=
on
C

C
st.
on

on
st

st
.

.
ln p

ln p
ln p

1/T 1/T 1/T

T T T
Positive Dhm = 0 D hm Negative
(a) (b) (c)
Fig. 12.10 Nature of ln p – 1/T lines for mixtures

Figure 12.11 shows a simple absorption system of Fig. 12.1 with the liquid-liquid
heat exchanger incorporated in it in addition. The ln p –1/T diagram of the cycle in
Fig. 12.12 represents its working. It is a single-effect H2O – LiBr 2 vapour absorption
system since it has one-stage of generation of vapour. The double-effect is described in
Sec. 12.8.
Line R on this diagram represents ln p sat versus 1/T sat relationship of the refriger-
ant (x = 1). Then, we draw the two horizontal lines corresponding to the condenser
pressure pk at condenser temperature Tc, and evaporator pressure p 0 at evaporator
temperature T0. The various state points are located as follows:
State 6 Saturated liquid refrigerant at condenser temperature TC on x = 1 line.
States 7 & 8 Liquid plus vapour state 7 after throttling, and saturated vapour state
8 at T0 on x = 1 line.
State 4 Saturated liquid mixture leaving absorber at p0 and absorber temperature
tA. This gives the refrigerant rich solution concentration xr.
State 4a It lies at 4 itself since its temperature and composition are the same.
However, it is at pressure pk. Hence, it represents a sub-cooled liquid state.
 5
1a

pk C G Qh

6 2

QC
Liquid-Liquid
7 Heat Exchanger
8
Q0
p0 E
3

3a
Hot Body

4a A

p
P

Cold Body
4 QA
Ambient

To TA = TC = T K Th
Vapour-Absorption System

Fig. 12.11 Schematic representation of simple vapour absorption system with

liquid-liquid regenerative heat exchanger
421
422 Refrigeration and Air Conditioning

Tc
Vapour 1 pk = Const.
6 2

1a

=1

ng

r
ttl i

=
ro
Th

a
R

=
ln p

Pump

7, 8 Vapour p0 = Const.
4, 4a 3, 3a

T0 TA Th
1/ T
Fig. 12.12 Representation of absorption cycle on ln p – 1/T diagram

Note For binary mixtures, we have three independent properties. On a two-dimensional

plane, the state cannot be exactly represented unless it is a saturation state.
State 2 Saturated liquid mixture leaving generator at pk and generator temperature
th. This gives the refrigerant poor solution concentration xa.
State 5 Superheated refrigerant vapour at pk and Th. It cannot be shown on this
diagram.
State 3 Subcooled liquid leaving regenerator after cooling at p k and xa. It is as-
sumed the hot solution from generator is cooled from T2 to T3, the saturation tem-
perature of the solution of composition xa and absorber pressure p0.
State 3a Saturated liquid mixture after throttling to absorber pressure p0.
State 1a Subcooled liquid leaving regenerator after heating at pk and xr. Tempera-
ture T1a is obtained from energy balance of regenerative heat exchanger. Note that
T1a is lower than T1 which is the saturation state at pressure pk for mixture of refrig-
erant concentration xr.

12.6.1 Representation of Carnot Processes for Absorption Machines on

ln p – 1/T Diagram
It is seen from Fig. 12.12 that temperature changes in the generator from T1a to T2 =
Th as the refrigerant vapour is boiled off. Similarly, the temperature changes in the
absorber from T3a to T4 as the absorption of refrigerant vapour takes place. For
process to be reversible, both generation and absorption should be isothermal. It is
seen from Fig. 12.13 that under these conditions of Carnot processes, we have x r =
x a. Thus, degasing breadth/range is zero. The machine would, therefore, need an
infinite solution circulation rate f. Such a machine would have maximum COP,
which is impossible to have.
 Vapour-Absorption System 423

6 1, 2
pk

Tc

=1

a
=
r
ln p

p0
7, 8 4, 3

T0 TA Th min
1/T

Fig. 12.13 Carnot processes for absorption machines on ln p – 1/T diagram

12.6.2 Minimum Generator Temperature for Absorption Machines

Pressures pk and p0 are decided by condenser temperature TC and evaporator tem-
perature T0. Then state 4 in Fig. 12.13 at absorber pressure p 0 is located from given
absorber temperature TA. This decides the rich solution concentration x r, and state 1.
In a Carnot cycle machine, x a = x r and state 2 is at 1 itself. This T2 is equal to Th, the
theoretically minimum generator temperature required for given TC, T0 and TA. It is
much above the ambient temperature. On account of other irreversibilities, the re-
quired minimum temperature in generator is still higher.

Note It is thus seen that an absorption cycle cannot be devised simply from a heat source
having temperature higher than the ambient temperature. To make the absorption system
possible, its temperature should be above this T hmin.

12.7 PRACTICAL SINGLE-EFFECT WATER–LITHIUM

BROMIDE ABSORPTION CHILLER

Several Inc., U.S.A. developed an absorption machine which uses solution of lithium
bromide in water, water being the refrigerant and lithium bromide which is a highly
hygroscopic salt-the adsorbent. Thus the solution leaving the absorber, being rich in
refrigerant water, is a weak solution of salt in water. But for the sake of consistency,
we shall continue to use xr to denote the refrigerant concentration which, in this
case, will mean the concentration of water in the solution leaving the absorber. Simi-
larly, the solution returning from the generator is a strong solution of lithium bro-
mide in water, but it being still poor in refrigerant water, xa will, therefore, denote
the concentration of water in the solution leaving the generator. The corresponding
lithium bromide concentration will then be (1 – xr) and (1 – xa) respectively.
424 Refrigeration and Air Conditioning

The salt does not exert any vapour pressure. So the vapour leaving the generator
is a pure refrigerant (water vapour). Therefore, the analyser and dephlegmator do
not form a part of the system. The equipment is normally designed for chilled-water
applications with a flash system as shown in Fig. 12.14.
1

2
Cooling Water
3
Refrigerant
Water

Steam
Generator
Condenser

Weak Brine, r
Strong
Bring, a

5 7

13 6

8
12
Chilled 9
Water
Refrigerant 10
Water

Cooling Water

Evaporator
Absorber
11
Weak Brine
14
Fig. 12.14 Single-effect water-lithium bromide absorption chiller

The generator and condenser are housed in the single-cylindrical vessel 1 and the
flash evaporator and absorber in another similar vessel 6. Water is boiled off from
vessel 1 by the steam coils 4. The vapour is condensed over the condenser cooling
water coils 2 and collected in the tray 3. The condensate is flashed through expan-
sion valve 5 into the vessel 6. The refrigerant water is collected in the tray 8. Chilled
water is circulated by the pump 12 and is returned to the system at 13.
The strong brine from vessel 1 flows by gravity through the heat exchanger 7 and
the pressure reducing valve 9 to the vessel 6. The flashed water vapour filling the
 Vapour-Absorption System 425

space in 6 is absorbed by this solution. The absorber heat is removed by the cooling
coils 10. Again, there is separate cooling water line for the absorber. The weak salt
solution leaving the absorber is then returned to the generator by the pump 11
through the liquid-liquid regenerative heat exchanger 7.
Thus, we see that there are three kinds of water flowing in the system:
(i) Refrigerant water.
(ii) Chilled water (secondary refrigerant).
(iii) Cooling water.
The chilled water, used as a secondary refrigerant, and refrigerant water are kept
separate. If refrigerant water itself is used as chilled water, and it goes to the air
conditioning plant and returns to the sealed system, it will bring in air with it. And
thus it will break the vacuum.
Both the vessels 1 and 6 are maintained under high vacuum, vessel 1 correspond-
ing to the condensing temperature (e.g., 55.3 mm Hg pressure at 40°C) and vessel6
corresponding to the flashed refrigerant water temperature (e.g., 4.9 mm Hg pres-
sure at 1°C). To remove air and other non-condensables that may enter the sealed
system through pump glands, a two-stage purge unit is provided. To avoid corro-
sion, the temperature in the boiler should not be higher than 120°C. The overall COP
of the system is reported to be approximately 0.7. The lithium bromide-water system
is thus found to be more suitable in applications involving low heat-source tempera-
tures such as are obtained with low-pressure (1 to 8 bar) or even exhaust (say
0.4 bar) steam, waste heat, solar energy, etc.
Absorption chillers are available in capacities from 100 TR upwards up to
7500 TR.

Example 12.4 Calculations for Single-Effect Water-Lithium Bromide System

The operating conditions for a water-lithium bromide chilled-water plant for air
conditioning are as follows:
Generator temperature 97°C
Condenser temperature 40°C
Chilled-water temperature 10°C
Absorber temperature 40°C
Find temperature of the solution entering generator assuming hot solution is
cooled to the saturation temperature at absorber pressure. Determine for one
ton refrigeration capacity, the following:
(a) Thermodynamic conditions at all points.
(b) Coefficient of performance.
(c) Mass flow rates at all sections.
(d) Energy balance of complete system.

Solution (a) Refer to Figs 12.11 and 12.12. From table of water vapour pressures
in the Appendix, we obtain the condenser and evaporator pressures corresponding
to their respective temperatures.
Condenser and generator pressure
pk = 55.32 mm Hg (At 40°C)
426 Refrigeration and Air Conditioning

Flash chamber and absorber pressure

p0 = 9.21 mm Hg (At 10°C)
Now, from ln p–1/T diagram we get first the LiBr 2, and then the refrigerant water
concentration in rich and poor solutions at states 4 and 2.
State 4. Saturated cold solution from absorber at
p = 9.21 mm Hg and t = 40°C
xLiBr2 = 0.55
h4 = 93.5 kJ/kg (From h – x diagram)
Rich solution concentration of water (refrigerant)
x r = 1 – xLiBr2 = 1 – 0.55 = 0.45
State 2. Saturated hot solution from generator at
p = 55.32 mm Hg and t = 97°C
xLiBr2 = 0.65
h2 = 248 kJ/kg (From h – x diagram)
Poor solution concentration of water (refrigerant)
xa = 1 – 0.65 = 0.35
State 1. Saturated solution at condenser pressure and 0.55 LiBr2 concentration
t1 = 74°C (From ln p–1/T diagram)
h1 = 166 kJ/kg (From h – x diagram)
State 3. Saturated solution at evaporator pressure and 0.65 LiBr2 concentration
t3 = 60°C
h3 = 180 kJ/kg
State 3a has the same enthalpy, temperature and composition as state 3. But it is at
the generator pressure. It represents a state subcooled from 2 to 3 at 55.32 mm Hg
pressure
State 4a. t = 4°C and xLiBr 2 = 0.55
h4a @ h4 = 93.5 kJ/kg (Neglecting pump work)

Note The enthalpy is read against temperature and composition for all solution states as
it is independent of pressure. It may be noted that point 4a after pumping represents a
subcooled state at 55.32 mm Hg pressure.
Specific solution circulation rates
1 - 0.35
f= = 6.5 kg/kg vapour, f – 1 = 5.5 kg/kg vapour
0.45 - 0.35
Heat available in hot solution for transfer
= (f – 1) (h2 – h 3) = 5.5 (248 – 180) = 374 kJ
Heat required by cold solution for heating
= f (h1 – h4) = 6.5 (166 – 93.5) = 471 kJ > 374 k
Hence, cold solution at 4a cannot be heated to 1. Let it be heated to 1a.
State 1a. Energy balance of the liquid-liquid heat exchanger gives
f (h1a – h4) = (f – 1) (h2 – h3)
( f - 1) 5.5
whence h1a = h4 + (h2 – h3) = 93.5 + (248 – 180) = 151 kJ/kg
f 6.5
 Vapour-Absorption System 427

State 5. It is that of water vapour at 55.32 mm Hg pressure and 97°C temperature.

At these conditions it represents a superheated vapour state. The enthalpy of water
vapour above the reference state of saturated water at 0°C can be found either from
steam table having reference state hf = 0 at t = 0°C or from the empirical relation
h = (2501 + 1.88 t) kJ/kg
Using the latter procedure
h5 = 2501 + 1.88 (97) = 2683 kJ/kg
State 6. Saturated water at 40°C
h6 = 4.1868 (40) = 167.5 kJ/kg
State 7. p = 9.21 mm Hg and t = 10°C (liquid + vapour)
h7 = h6 = 167.5 kJ/kg
State 8. p = 9.21 mm Hg at t = 10°C (saturated vapour)
h8 = 2501 + 1.88 (10) = 2520 kJ/kg
(b) Refrigerating effect
q0 = h8 – h7 = 2520 – 167.5 = 2352.5 kJ/kg
Heat added in the generator per unit mass of vapour distilled
qh = h5 – h 2 + f (h2 – h 1a)
= 2683 – 248 + 6.5 (248 – 151) = 3066 kJ/kg vapour
q 2352.5
Coefficient of performance COP » = 0 = = 0.77
qh 3066
(c) Water vapour distilled per ton refrigeration
211 211
D= = = 0.09 kg/min
q0 2352.5
Mass flow rate of cold solution from the absorber
F = fD = 6.5 (0.09) = 0.585 kg/min
Mass flow rate of hot solution from the generator
F – D = 0.585 – 0.09 = 0.495 kg/min
(d) Head rejected in the condenser
D 0.09
QC = (h5 – h6) = (2683 – 167.5) = 3.77 kW
60 60
Heat rejected in the absorber
QA = DqA = D[h8 – h3) + f (h3 – h4)]
0.09
= [(2520 – 180) + 6.5 (180 – 93.5)] = 4.35 kW
60
Heat supplied in the generator
0.09
Q h = Dqh = (3066) = 4.6 kW
60
Heat absorbed by chilled water (per ton refrigeration)
Q0 = 3.5167 kW
Net heat received = Qh + Q0 = 4.6 + 3.5167 = 8.12 kW
Net heat rejected = QC + QA = 3.77 + 4.35 = 8.12 kW
Again, the energy balance checks very closely.
428 Refrigeration and Air Conditioning

12.8 DOUBLE-EFFECT H2O – LiBr 2 ABSORPTION SYSTEM

A single-stage like the single-effect absorption system is not suited to utilize a heat
source at a temperature higher than a certain point unlike other heat-operated refrig-
erating machines that follow the Carnot trend, viz., the higher the temperature of the
heat source, the higher the COP. In fact, the COP decreases as the heat source tem-
perature increases beyond a point. This is because the absorption system is not a
reversible refrigerating machine. Because of the mixing process of refrigerant and
absorbent, a degree of irreversibility is involved. That is why, the COP of an absorp-
tion system levels with the increase in generator temperature, and then it starts
decreasing.
It is found that the single-effect system gives best results upto a heat source
temperature of 105°C. Above that temperature, it is worthwhile to switch over to
double-effect system as illustrated in Figs 12.15 and 12.16.

Example 12.5 Calculations for Double-Effect H2O-LiBr 2 System

The high pressure generator of a double-effect H2O-LiBr2 vapour absorption
system, shown in Fig. 12.15 operates on steam supplied at 8 bar pressure. The
following conditions are specified:
Pressure in high-pressure generator 100 kPa
Temperature in high-pressure generator 150°C
Condenser temperature 40°C
Absorber temperature 35°C
Evaporator temperature 10°C
The water vapour from the high-pressure generator I is condensed in the low-
pressure generator II. The temperature of solution leaving generator II is 95°C.
(i) Show all the thermodynamic states on ln p – 1/T diagram.
(ii) Find enthalpies at all state points.
(iii) Determine the heat added in generator I per kg of water in refrigerant circuit.
(iv) Determine COP.
(v) What would have happened if a single-effect system were to be used?

Solution (i) The thermodynamic states are shown on ln p – 1/T diagram in

Fig. 12.16. All states are saturation states except 3a and 4a.
(ii) Condenser pressure at 40°C = 55.32 mm Hg
Evaporator pressure at 10°C = 9.27 mm Hg
Solution Circuit (Enthalpy is found from composition and temperature)
State 1 p1 = 9.27 mm Hg, t1 = 35°C xLiBr 2 = 0.525, xH2O = x1 = 0.475
h1 = 77.4 kJ/kg @ h2
State 3 p3 = 55.32 mm Hg, xLiBr2 = 0.525 t3 = 68°C
h3 = 146.5 kJ/kg
State 4 p4 = 100 kPa, xLiBr2 = 0.525 t4 = 137°C
h4 = 295.7 kJ/kg
 Vapour-Absorption System 429

State 5 p5 = 100 kPa, t5 = 150°C xLiBr2 = 0.578, xH2O = x5 = 0.422

h5 = 324.5 kJ/kg
State 6 p6 = 55.32 mm Hg, xLiBr2 = 0.578 t6 = 80°C
h6 = 184 kJ/kg = h17
State 7 p7 = 55.32 mm Hg, t7 = 95°C xLiBr2 = 0.642, xH2O = x7 = 0.358
h7 = 240 kJ/kg
State 8 p8 = 9.27 mm Hg, xLiBr2 = 0.642 t8 = 59°C
h8 = 162.9 kJ/kg

12 10
QC

Generator I
Condenser High Press. QG
13 Generator II
Low Press. 5 4
1 kg 14
11
QHE Heat
I
Exchanger I
17
6
7 3
(f – 1) kg
15 QHE Heat
II
Exchanger II

16 8
Evaporator Absorber
9 2
1 kg
1
QA
QE
f kg
Fig. 12.15 Double-effect vapour absorption system

Refrigerant Circuit (Enthalpies of Water)

h10 = 2776.4 kJ/kg (Superheated vapour at 100 kPa, 150°C from steam table)
h11 = (hf)100 kPa = 417.5 kJ/kg = h13 (Liquid-Vapour Mixture at 55.32 mm Hg)
h12 = 2501 + 1.88 (95) = 2680 kJ/kg (Low pressure vapour)
h14 = (hf ) 40°C = 167.6 kJ/kg = h15
h16 = (hg) 10°C = 2501 + 1.88 (10) = 2519.8 kJ/kg
(iii) Solution Circulation Rates Rich in refrigerant (weak in LiBr2) solution
circulation rate
f = m1 = m2 = m3 = m4
1 - xa 1 - x8 1 - 0.358
= = = = 5.487 kg/kg refrigerant
xr - xa x1 - x9 0.475 - 0.358
Poor in refrigerant (strong in LiBr2) solution circulation rate
f – 1 = m9 = m8 = m7 = 5.487 – 1 = 4.487 kg/kg refrigerant
430 Refrigeration and Air Conditioning

100 °C
150 °C
137 °C

100 kPa 11 4 5

5
.52

8
=0

.57
=0
r2
r

Li B
te
Wa

2
r
Li B
ln p

55.32 mm Hg 14 3 7
6
2
.64
r2
=0
Li B

9.27 mm Hg 8
16 1, 2

10°C 35°C 40°C 59°C 80°C 95°C

1/T T
Fig. 12.16 ln p-1/T diagram for double-effect H 2O – LiBr2 system for Example 12.3

Mass Balance of Generator II

m10 = m11 = m13 = 1 – m12 m12 = 1 – m10
m17 = m12 + 4.487 = 1 – m10 + 4.4487 = 5.487 – m10
Enthalpy Balance of Generator II
m10 h10 + m17 h17 = m12 h12 + m13 h11 + m7 h 7
Substituting values and solving, we get
m10 = 0.774 kg
m12 = 1 – m10 = 0.226 kg
m17 = m12 + 4.487 = 4.713 kg
Heat added in Generator I (From enthalpy balance)
(QG)I = m5 h5 + m10 h10 – m4 h4
 Vapour-Absorption System 431

= 4.713 (324.5) + 0.774 (2776.4) – 5.487 (295.7)

= 2065.2 kJ/kg refrigerant
(iv) Refrigeration produced
Q0 = h16 – h14 = 2519.8 – 167.6 = 2352.2 kJ/kg refrigerant
Q0 2352.2
COP = = = 1.14
(QG ) I 2065.2
(v) If a single-effect system were used, then we would find:
(a) Line 5-6 when extended to absorber pressure-since the solution is very
strong in LiBr 2-would end up at point 8¢.
(b) Further, xa would be 0.422 instead of 0.358. Degasification breadth
would be very small. Hence, COP would be very low.

12.9 ELECTROLUX REFRIGERATOR

Electrolux principle works on 3-fluid system. There is no solution circulation pump.

Total pressure is the same throughout the system. The third fluid remains mainly in
the evaporator thus reducing partial pressure of refrigerant to enable it to evaporate
at low pressure and hence low temperature.
The schematic diagram of the electrolux refrigerator working on NH 3–H 2O
system with H2 as the third fluid is shown in Fig. 12.17. Liquid NH 3 evaporates in
the evaporator in the presence of H2. Hydrogen is chosen as it is non-corrosive and
insoluble in water.
A thermosyphon bubble pump is used to lift the weak aqua from the generator to
the separator. The discharge tube from the generator is extended down below the
liquid level in the generator. The bubbles rise and carry slugs of weak NH3–H2O
solution into the separator.
Two U-bends are provided as vapour-locks to prevent H2 from getting into the
high side or solution circuit.
Partial pressure of H2 provides the pressure difference of NH3 between the con-
denser and the evaporator. Accordingly, we have:
In condenser Pure NH 3 vapour pressure = Total pressure
In evaporator NH3 vapour pressure = Total pressure – Partial pressure of H2
For example, consider the condenser temperature as 50°C, and evaporator
temperature as – 15°C. The corresponding vapour pressures of NH3 are:
Condenser, p k = 20.33 bar
Evaporator outlet, p02 = 2.36 bar
432 Refrigeration and Air Conditioning

er
ns
de
C on
it y
NH3 + H2 av
Gr
E A
H2 uid NH 3
Liq
NH3 + H2
Vapour

Evaporator
ua
Aq Separator
H2 k
ea
W
Heat Exchanger
(NH3 + H2O Vapour Lift
Heated by H2 Pump
Which gets Cooled) (Thermosyphon
Absorber
Bubble Pump)

H2

Generator
Strong Aqua

Heat
Fig. 12.17 Electrolux refrigerator

The approximate pressures in various parts of the system, then will be as given in
Table 12.2.

Table 12.2 Partial pressures in electrolux refrigerator in bar

Section NH 3 H2O H2 Total

Condenser 20.33 0 0 20.33
Evaporator inlet 1.516 0 18.814 20.33
Evaporator exit 2.36 0 17.97 20.33
Generator top 15.54 4.79 0 20.33

It has been assumed that vapours leaving generator top are in equilibrium with
entering rich solution at 40°C, at which temperature saturation pressure of NH3 is
15.54 bar. It has also been assumed that the temperature at evaporator inlet is – 25°C
at which temperature saturation pressure of NH3 is 1.516 bar.

12.10 NEW MIXTURES FOR ABSORPTION SYSTEM

We know that NH3 and H2O do not form an ideal pair for absorption system because
the difference in their N.B.Ps is not large enough. And, although, H2O and LiBr2
 Vapour-Absorption System 433

form a very good pair from the points of view of solubility and N.B.P. requirement,
but the system suffers from the problems of corrosion, and of maintaining high
vacuum both on the low pressure side as well as on the high pressure side. Hence, the
efforts are on to find the most suitable pair for the system.
Zellhoeffer et al.21 determined the solubility of R 21 and R 22 in a number of
solvents such as ethers, esters, amides and amines. They found that dimethyl ether of
tetraethylene glycol (DME–TEG) with chemical formula CH3O (CH2CH2O)4CH3 is
an extremely good solvent for these refrigerants. Mastrangelo made a further study
of the solubility of various fluorocarbons in DME-TEG.
Ever since the pioneering work of Zellhoeffer et al., the investiga-
tors2, 3, 5, 6, 10, 17, 18 have been trying to find suitable R 22 based refrigerant-absorbent
mixtures to replace NH3–H2O system. For a study, Arora et al 1. chose DME-TEG,
isobutyl acetate, dimethyl formamide (DMF) with the chemical formula HCO.
N (CH 3)2 and diethyl formamide (DEF) with the chemical formula HCON (C2 H5)2
as absorbents for R 22. The basic ln p–1/T data for the study was obtained for NH 3–
H2O and R 22 – Isobutyl acetate systems from Sellerio 17, for R 22-DME-TEG sys-
tem from Mastrangelo and R 22-DMF and R 22-DEF systems from Thieme and
Albright 18.

Table 12.3 Solution circulation rates

System D(N.B.P.), °C xr xa f
NH 3 + H2O 133 0.5 0.22 3.78
R 22 + DME-TEG 316.6 0.496 0.264 3.18
R 22 + Isobutyl
Acetate 158.8 0.52 0.34 3.67
R 22 + DMF 193.8 0.623 0.409 2.76
R 22 + DEF 218.3 0.563 0.433 4.36

Calculations were done for the operating conditions

th = 120°C, tC = tA = tk = 40°C, t0 = 5°C
It was assumed that only pure refrigerant circulates in the refrigerant circuit. The
rectification losses were assumed negligibly small. Table 12.3 gives the differences
between the N.B.Ps of refrigerant and absorbent, and the results of calculations for
rich solution circulation rates. From the table, DMF with minimum solution circula-
tion rates appears to be the best absorbent. Another suitable asbrobent is DME-
TEG. Using Eisman method of calculation, it was also shown by Arora et al., that
R 22-DMF system gives high COP. Recently, Bapat2 and Das5 have done detailed
study of properties and analysis of R 22-DMF and R 22-DEF respectively.
Many studies have, however, been conducted on the use of solid adsorbents/
dessicants.
Ammonia as refrigerant in combination with solid adsorbents such as calcium
chloride, sodium thiocyanate, lithium thiocynate, lithium nitrate, etc., is being tried
in vapour absorption system. All these solid adsorbents are, however, highly
corrossive in nature.
434 Refrigeration and Air Conditioning

References
1. Arora C P, A K Mittal and A K Gupta, ‘An analysis of the properties of
mixtures for vapour absorption refrigeration’. Reprint No. 2.57, Proc. XIII
International Congress of Refrigeration, Washington, 1971.
2. Bapat S L, Thermodynamic Properties of Dimethyl Formamide and R 22 for
Vapour Absorption Refrigeration System, Ph. D. Thesis, IIT Delhi, 1982.
3. Berestneff A A, ‘A new development in absorption refrigeration’, Refrigerat-
ing Engineering, Vol. 57, No. 6, June, 1945, p. 553.
4. Bosnjakovic F, Technical Thermodynamics, Holt, Reinhert and Winston,
1965, pp. 255–279.
5. Das M S, A Thermodynamic Study of Diethyl Formamide and R 22 Combina-
tion for Vapour Absorption Refrigeration System, Ph D. Thesis, IIT Delhi,
1984.
6. Eisemen B J. Jr, ‘Why R 22 should be favoured for absorption refrigeration’,
ASHRAE J., Vol. 1, No. 12, Dec. 1959, pp. 45–50.
7. Jennings B H and F P Shannon, ASRE Handbook, 1951, p. 187.
8. Kohloss F H Jr and G L, Scott in ‘Equilibrium properties of aqua-ammonia in
chart from’, Refrigerating Engineering, Vol. 58, No. 10, Oct. 1950, p. 970.
9. Lower H, ‘Thermodynamic and physical properties of aquous lithium–
bromide solution’, Report of Technical University, Karlsruhe, Germany, 1961.
10. Mastrangelo S V R, ‘Solubility of some chlorofluoro-hydrocarbons in
tetraethylene glycol dimethyl ether’, ASHRAE J., Vol. 1, No. 10, Oct. 1959,
pp. 64–68.
11. McNeely L A, ‘Thermodynamic properties of aquous solutions of lithium
bromide’, ASHRAE Trans. 1979, Part One, pp. 413–434.
12. Merkel-Bosnjakovic, Diagrams and Tables Relating to Absorption Refrig-
erators, Springer, Berlin, 1929.
13. Neibergall, W, ‘Absorption refrigerating machines’, Händbuch der
Kältetechnik, Vol. VII, Edited by R. Plank, Springer, Berlin, 1959.
14. Richter K H, ‘Multistage absorption refrigeration systems’, Journal of
Refrigeration, Sept/Oct. 1962, pp. 105–111.
15. Rosenfeld L M and M C Karnaukh, Kholodilnaya Tekhnika, 1958, No. 1,
pp. 37–42.
16. Scatchard G, et al., ‘Thermodynamic properties saturated liquid and vapour
of ammonia-water mixture’, Refrigerating Engineering, Vol. 53, No. 5, May,
1947, pp. 38.
17. Sellerio, U L, ‘Impiego di idro carburi alognetied in particolarlara dell’r 22.
nelle machine frigorifere and assorbimento a funzionamento continuous’,
Estratto da Il CALORE Ressegna Technical Mensile Dell Associazione
Naxionale per Il Controllo Della Combustion, 1965, N-7.
18. Thieme A and L F Albright, ‘Solubility of Refrigerants 11, 21, and 22 in
Organic Solvents Containing a Nitrogen Atom and in Mixtures of Liquids,’
ASHRAE J., July 1961, p. 71.
20. Threlkeld J L and G F Zellhoefer, Thermal Environmental Engineering,
Prentice Hall, 1962, pp. 96-104.
 Vapour-Absorption System 435

21. Zellhoefer G F, ‘Solubility of halogenated hydrocarbon refrigerants in

organic solvents’, Industrial and Engineering Chemistry, Vol. 29, May 1937,
pp. 548–51.

Revision Exercises
12.1 For a simple ammonia-absorption system, the following are given:
Condenser pressure 12.5 bar
Evaporator pressure 1.8 bar
Rich solution concentration 0.36
Poor solution concentration 0.25
Find on the basis of 1 ton refrigerating capacity:
(a) The temperature at the end of the evaporator if the vapour is assumed to
be dry saturated.
(b) The mass rate of flow of the refrigerant absorbent mixture in the evapo-
rator.
(c) The mass rate of circulation of the rich and poor solution.
(d) Generator and absorber temperatures.
(e) Heat added in the generator if the rich solution is assumed to be heated
in the heat exchanger to 80°C.
12.2 (a) For an ammonia absorption system:
p k = 10 bar, th = 130°C, xr = 0.38
t02 = – 12°C, p0 = 2.75 bar
Find the temperature and concentration of the vapour leaving the gen-
erator-analyser. Assume the specific heats of the rich and poor solutions
as same. Calculate the cooling energy ratio for a system in which there is
no rectifier.
(b) Calculate the same if there is a rectifier which cools the vapours to 60°C
and the evaporator pressure is raised to 3.4 bar.
12.3 In a lithium bromide-water system the condenser and evaporator temperatures
are 35 and 8°C respectively. The generator temperature is 85°C and the ab-
sorber temperature is 30°C. Assume a pressure drop of 2.5 mm Hg between the
generator and condenser and 1 mm Hg between the evaporator and absorber.
Determine the heat rejection rates in the condenser and absorber per unit of
refrigerating capacity. Also find the heat input to the generator, and COP.
12.4 Let an analyser be added in the system of Prob. 12.1, and do the calculations
for (a) to (e).
12.5 For an NH3 absorption cycle, we have
Condenser pressure 14 bar
Evaporator pressure 1.4 bar
Absorber temperature 36°C
Generator temperature 110°C
(a) Find out if such a cycle is possible or not.
(b) Change the evaporator pressure to 2.8 bar. Check if the cycle is possible
now.
436 Refrigeration and Air Conditioning

(c) Assume temperature leaving evaporator is t02 = 5°C. What is the refrig-
erating effect?
(d) Also find the COP.
(e) Add analyser in the system, and find COP.
(f) Add a dephlegmator which cools the vapour to 40°C. Determine the
effect on COP.
12.6 (a) Find the temperature range through which liquid ammonia containing
(a) 1% water, (b) 10% water will evaporate at a pressure of 2 bar.
(b) It is proposed to design a solar refrigeration NH 3–H2O vapour absorp-
tion system operating under the following conditions:
Condenser pressure 16 bar
Evaporator pressure 2 bar
Absorber temperature 35°C
Hot water from flat plate solar collector can be obtained at a temperature
of 80°C at the most. Examine the feasibility of operating the refrigera-
tion system with this hot water.
(c) If not feasible, then suggest suitable measures to make it feasible.
12.7 (a) The operating conditions in a H2O – LiBr 2 vapour absorption system are
as follows:
Condenser and absorber temperatures 45°C
Evaporator temperature 5°C
Determine the minimum temperature of heat source required to produce
any refrigeration at all.
(b) Saturated liquid mixture of 80% NH3 plus 20% H2O at 16 bar is throttled
to 2 bar pressure. What is the temperature after throttling, and the
temperature after complete evaporation of the mixture after throttling?
12.8 Introduce double-effect generation in Prob. 12.3, and find the new COP.