VARS Merged

Lesson
14
Vapour Absorption
Refrigeration Systems
Version 1 ME, IIT Kharagpur 1
The objectives of this lesson are to:
1. Introduce vapour absorption refrigeration systems (Section 14.1)
2. Explain the basic principle of a vapour absorption refrigeration system
(Section 14.2)
3. Compare vapour compression refrigeration systems with continuous vapour
absorption refrigeration systems (Section 14.2)
4. Obtain expression for maximum COP of ideal absorption refrigeration system
(Section 14.3)
5. Discuss properties of ideal and real refrigerant-absorbent mixtures (Section
14.4)
6. Describe a single stage vapour absorption refrigeration system with solution
heat exchanger (Section 14.5)
7. Discuss the desirable properties of refrigerant-absorbent pairs for vapour
absorption refrigeration systems and list the commonly used working fluids
(Section 14.6)
At the end of the lecture, the student should be able to:
1. List salient features of vapour absorption refrigeration systems and compare

them with vapour compression refrigeration systems
2. Explain the basic principle of absorption refrigeration systems and describe
intermittent and continuous vapour absorption refrigeration systems
3. Find the maximum possible COP of vapour absorption refrigeration systems
4. Explain the differences between ideal and real mixtures using pressure-
composition and enthalpy-composition diagrams
5. Draw the schematic of a complete, single stage vapour absorption refrigeration
system and explain the function of solution heat exchanger
6. List the desirable properties of working fluids for absorption refrigeration
systems and list some commonly used fluid pairs
14.1. Introduction
Vapour Absorption Refrigeration Systems (VARS) belong to the class of
vapour cycles similar to vapour compression refrigeration systems. However, unlike
vapour compression refrigeration systems, the required input to absorption systems is
in the form of heat. Hence these systems are also called as heat operated or thermal
energy driven systems. Since conventional absorption systems use liquids for
absorption of refrigerant, these are also sometimes called as wet absorption systems.
Similar to vapour compression refrigeration systems, vapour absorption refrigeration
systems have also been commercialized and are widely used in various refrigeration
and air conditioning applications. Since these systems run on low-grade thermal
energy, they are preferred when low-grade energy such as waste heat or solar energy
is available. Since conventional absorption systems use natural refrigerants such as
water or ammonia they are environment friendly.

In this lesson, the basic working principle of absorption systems, the maximum
COP of ideal absorption refrigeration systems, basics of properties of mixtures and
simple absorption refrigeration systems will be discussed.
14.2. Basic principle

When a solute such as lithium bromide salt is dissolved in a solvent such as
water, the boiling point of the solvent (water) is elevated. On the other hand, if the
temperature of the solution (solvent + solute) is held constant, then the effect of
dissolving the solute is to reduce the vapour pressure of the solvent below that of the
saturation pressure of pure solvent at that temperature. If the solute itself has some
vapour pressure (i.e., volatile solute) then the total pressure exerted over the solution
is the sum total of the partial pressures of solute and solvent. If the solute is non-
volatile (e.g. lithium bromide salt) or if the boiling point difference between the
solution and solvent is large (≥ 300oC), then the total pressure exerted over the
solution will be almost equal to the vapour pressure of the solvent only. In the
simplest absorption refrigeration system, refrigeration is obtained by connecting two
vessels, with one vessel containing pure solvent and the other containing a solution.
Since the pressure is almost equal in both the vessels at equilibrium, the temperature
of the solution will be higher than that of the pure solvent. This means that if the
solution is at ambient temperature, then the pure solvent will be at a temperature
lower than the ambient. Hence refrigeration effect is produced at the vessel containing
pure solvent due to this temperature difference. The solvent evaporates due to heat
transfer from the surroundings, flows to the vessel containing solution and is absorbed
by the solution. This process is continued as long as the composition and temperature
of the solution are maintained and liquid solvent is available in the container.
For example, Fig.14.1 shows an arrangement, which consists of two vessels A

and B connected to each other through a connecting pipe and a valve. Vessel A is
filled with pure water, while vessel B is filled with a solution containing on mass
basis 50 percent of water and 50 percent lithium bromide (LiBr salt). Initially the
valve connecting these two vessels is closed, and both vessels are at thermal
equilibrium with the surroundings, which is at 30oC. At 30oC, the saturation pressure
of water is 4.24 kPa, and the equilibrium vapour pressure of water-lithium bromide
solution (50 : 50 by mass) at 30oC is 1.22 kPa.

a) Initial condition
U
Valve closed
4.24 kPa 1.22 kPa
Water at 30oC 50% LiBr soln. at 30oC
A
Water vapour
o
30 C
30oC
b) Refrigeration Valve open
1.22 kPa 1.22 kPa
Water at 10oC 50% LiBr soln. at 30oC
Qe A B Qc
Water vapour
c) Regeneration
Valve open
4.24 kPa 4.24 kPa

Water at 30oC Weak LiBr soln. at Tg
Qc Qg
o
30 C
Tg > To > Te
Fig.14.1: Basic principle of vapour absorption systems

Thus at initial equilibrium condition, the pressure in vessel A is 4.24 kPa,
while it is 1.22 kPa in vessel B. Now the valve between vessels A and B is opened.
Initially due to pressure difference water vapour will flow from vessel A to vessel B,
and this vapour will be absorbed by the solution in vessel B. Since absorption in this
case is exothermic, heat will be released in vessel B. Now suppose by some means the
concentration and temperature of vessel B are maintained constant at 50 % and 30oC,
respectively. Then at equilibrium, the pressure in the entire system (vessels A and B)
will be 1.22 kPa (equilibrium pressure of 50 % LiBr solution at 30oC). The

temperature of water in vessel A will be the saturation temperature corresponding to
1.22 kPa, which is equal to about 10oC, as shown in the figure. Since the water
temperature in A is lower than the surroundings, a refrigeration effect (Qe) can
produced by transferring heat from the surroundings to water at 10oC. Due to this heat
transfer, water vaporizes in A, flows to B and is absorbed by the solution in B. The
exothermic heat of absorption (Qa) is rejected to the surroundings.
Now for the above process to continue, there should always be pure water in
vessel A, and vessel B must be maintained always at 50 percent concentration and
30oC. This is not possible in a closed system such as the one shown in Fig.14.1. In a
closed system with finite sized reservoirs, gradually the amount of water in A
decreases and the solution in B becomes diluted with water. As a result, the system
pressure and temperature of water in A increase with time. Hence the refrigeration
effect at A reduces gradually due to the reduced temperature difference between the
surroundings and water. Thus refrigeration produced by systems using only two
vessels is intermittent in nature. In these systems, after a period, the refrigeration
process has to be stopped and both the vessels A and B have to be brought back to
their original condition. This requires removal of water absorbed in B and adding it
back to vessel A in liquid form, i.e., a process of regeneration as shown in Fig.14.1(c).
Assume that before regeneration is carried out, the valve between A and B is
closed and both A and B are brought in thermal equilibrium with the surroundings
(30oC), then during the regeneration process, heat at high temperature Tg is supplied
to the dilute LiBr solution in B, as a result water vapour is generated in B. The vapour
generated in B is condensed into pure water in A by rejecting heat of condensation to
the surroundings. This process has to be continued till all the water absorbed during
the refrigeration process (14.1(b)) is transferred back to A. Then to bring the system
back to its original condition, the valve has to be closed and solution in vessel B has
to be cooled to 30oC. If we assume a steady-flow process of regeneration and neglect
temperature difference for heat transfer, then the temperature of water in A will be
30oC and pressure inside the system will be 4.24 kPa. Then the temperature in vessel
B, Tg depends on the concentration of solution in B. The amount of heat transferred
during refrigeration and regeneration depends on the properties of solution and the
operating conditions. It can be seen that the output from this system is the
refrigeration obtained Qe and the input is heat supplied to vessel B during vapour
regeneration process, Qg.
The system described may be called as an Intermittent Absorption

Refrigeration System. The solvent is the refrigerant and the solute is called as
absorbent. These simple systems can be used to provide refrigeration using renewable
energy such as solar energy in remote and rural areas. As already explained, these
systems provided refrigeration intermittently, if solar energy is used for regenerating
the refrigerant, then regeneration process can be carried out during the day and
refrigeration can be produced during the night.
Though the intermittent absorption refrigeration systems discussed above are

simple in design and inexpensive, they are not useful in applications that require
continuous refrigeration. Continuous refrigeration can be obtained by having a
modified system with two pairs of vessels A and B and additional expansion valves
and a solution pump.

Qg at Tg
Qc at To Qc at To
Condenser Wc Condenser Generator
Pc
Pc Wp
Exp.device Exp.device Pe Pump Exp.device

Pe
Evaporator Evaporator Absorber
Qe at Te
Mechanical Thermal Qa at To
compression compression
a) VCRS b) VARS
Figs.14.2: a) Vapour compression refrigeration system (VCRS)

b) Vapour Absorption Refrigeration System (VARS)
Figure 14.2(a) and (b) show a continuous output vapour compression

refrigeration system and a continuous output vapour absorption refrigeration system.
As shown in the figure in a continuous absorption system, low temperature and low
pressure refrigerant with low quality enters the evaporator and vaporizes by producing
useful refrigeration Qe. From the evaporator, the low temperature, low pressure
refrigerant vapour enters the absorber where it comes in contact with a solution that is
weak in refrigerant. The weak solution absorbs the refrigerant and becomes strong in
refrigerant. The heat of absorption is rejected to the external heat sink at To. The
solution that is now rich in refrigerant is pumped to high pressure using a solution
pump and fed to the generator. In the generator heat at high temperature Tg is
supplied, as a result refrigerant vapour is generated at high pressure. This high
pressure vapour is then condensed in the condenser by rejecting heat of condensation
to the external heat sink at To. The condensed refrigerant liquid is then throttled in the
expansion device and is then fed to the evaporator to complete the refrigerant cycle.
On the solution side, the hot, high-pressure solution that is weak in refrigerant is
throttled to the absorber pressure in the solution expansion valve and fed to the
absorber where it comes in contact with the refrigerant vapour from evaporator. Thus
continuous refrigeration is produced at evaporator, while heat at high temperature is
continuously supplied to the generator. Heat rejection to the external heat sink takes
place at absorber and condenser. A small amount of mechanical energy is required to
run the solution pump. If we neglect pressure drops, then the absorption system
operates between the condenser and evaporator pressures. Pressure in absorber is
same as the pressure in evaporator and pressure in generator is same as the pressure in
condenser.
It can be seen from Fig.14.2, that as far as the condenser, expansion valve and
evaporators are concerned both compression and absorption systems are identical.
However, the difference lies in the way the refrigerant is compressed to condenser
pressure. In vapour compression refrigeration systems the vapour is compressed
mechanically using the compressor, where as in absorption system the vapour is first

converted into a liquid and then the liquid is pumped to condenser pressure using the
solution pump. Since for the same pressure difference, work input required to pump a
liquid (solution) is much less than the work required for compressing a vapour due to
Pc
very small specific volume of liquid ( w = − ∫ v.dP ), the mechanical energy required to
Pe
operate vapour absorption refrigeration system is much less than that required to
operate a compression system. However, the absorption system requires a relatively
large amount of low-grade thermal energy at generator temperature to generate
refrigerant vapour from the solution in generator. Thus while the energy input is in the
form of mechanical energy in vapour compression refrigeration systems, it is mainly
in the form of thermal energy in case of absorption systems. The solution pump work
is often negligible compared to the generator heat input. Thus the COPs for
compression and absorption systems are given by:
Qe
COPVCRS = (14.1)
Wc
Qe Q
COPVARS = ≈ e (14.2)
Q g + Wp Q g
Thus absorption systems are advantageous where a large quantity of low-grade

thermal energy is available freely at required temperature. However, it will be seen
that for the refrigeration and heat rejection temperatures, the COP of vapour
compression refrigeration system will be much higher than the COP of an absorption
system as a high grade mechanical energy is used in the former, while a low-grade
thermal energy is used in the latter. However, comparing these systems based on
COPs is not fully justified, as mechanical energy is more expensive than thermal
energy. Hence, sometimes the second law (or exergetic) efficiency is used to compare
different refrigeration systems. It is seen that the second law (or exergetic) efficiency
of absorption system is of the same order as that of a compression system.
14.3. Maximum COP of ideal absorption refrigeration system

In case of a single stage compression refrigeration system operating between
constant evaporator and condenser temperatures, the maximum possible COP is given
by Carnot COP:
Te
COPCarnot = (14.3)
Tc − Te
If we assume that heat rejection at the absorber and condenser takes place at
same external heat sink temperature To, then a vapour absorption refrigeration system
operates between three temperature levels, Tg, To and Te. The maximum possible COP
of a refrigeration system operating between three temperature levels can be obtained
by applying first and second laws of thermodynamics to the system. Figure 14.3
shows the various energy transfers and the corresponding temperatures in an
absorption refrigeration system.

Tg
Pump
Wp
Qg
Cycle
System
Qa + Qc
Qe
Te TT
o∞
Fig.14.3: Various energy transfers in a vapour absorption refrigeration system
From first law of thermodynamics,
Q e + Q g − Q c + a + Wp = 0 (14.4)
where Qe is the heat transferred to the absorption system at evaporator temperature Te,
Qg is the heat transferred to the generator of the absorption system at temperature Tg,
Qa+c is the heat transferred from the absorber and condenser of the absorption system
at temperature To and Wp is the work input to the solution pump.
From second law of thermodynamics,

ΔS total = ΔS sys + ΔS surr ≥ 0 (14.5)
where ΔStotal is the total entropy change which is equal to the sum of entropy change
of the system ΔSsys and entropy change of the surroundings ΔSsurr. Since the
refrigeration system operates in a closed cycle, the entropy change of the working
fluid of the system undergoing the cycle is zero, i.e., ΔS sys = 0 . The entropy change
of the surroundings is given by:
Q e Q g Q a +c
ΔS surr = − − + ≥0 (14.6)
Te Tg To
Substituting the expression for first law of thermodynamics in the above equation
⎛ Tg − To ⎞ ⎛ ⎞
Qg ⎜ ⎟ ≥ Q e ⎜ To − Te ⎟⎟ − Wp (14.7)
⎜ Tg ⎟ ⎜ T
⎝ ⎠ ⎝ e ⎠
Neglecting solution pump work, Wp; the COP of VARS is given by:
Qe ⎛ Te ⎞⎛ Tg − To ⎞
COPVARS = ≤ ⎜⎜ ⎟⎟⎜ ⎟ (14.8)
⎜ ⎟
Qg ⎝ To − Te ⎠⎝ Tg ⎠

An ideal vapour absorption refrigeration system is totally reversible (i.e., both
internally and externally reversible). For a completely reversible system the total
entropy change (system+surroundings) is zero according to second law, hence for an
ideal VARS ΔS total, rev = 0 ⇒ ΔS surr , rev = 0 . Hence:
Q e Q g Q a +c
ΔS surr , rev = − − + =0 (14.9)
Te Tg To
Hence combining first and second laws and neglecting pump work, the maximum
possible COP of an ideal VARS system is given by:
Q ⎛ Te ⎞⎛ Tg − To ⎞
COPideal VARS = e = ⎜⎜ ⎟⎟⎜ ⎟ (14.10)
⎜ ⎟
Thus the ideal COP is only a function of operating temperatures similar to Carnot
system. It can be seen from the above expression that the ideal COP of VARS system
is equal to the product of efficiency of a Carnot heat engine operating between Tg and
To and COP of a Carnot refrigeration system operating between To and Te, i.e.,
Qe ⎛ Te ⎞⎛ Tg − To ⎞
COPideal VARS = = ⎜⎜ ⎟⎟⎜ ⎟ = COPCarnot .η Carnot (14.11)
⎜ ⎟
Thus an ideal vapour absorption refrigeration system can be considered to be a

combined system consisting of a Carnot heat engine and a Carnot refrigerator as
shown in Fig.14.4. Thus the COP of an ideal VARS increases as generator
temperature (Tg) and evaporator temperature (Te) increase and heat rejection
temperature (To) decreases. However, the COP of actual VARS will be much less
than that of an ideal VARS due to various internal and external irreversibilities
present in actual systems.
Tg
Qg
E WE
Qa
TT∞o
Qc
WE R
Qe
Te
Fig.14.4: Vapour absorption refrigeration system as a combination of a heat

Vapour absorption system as and
engine a combination of Heat Engine and
a refrigerator

14.4. Properties of refrigerant-absorbent mixtures
The solution used in absorption refrigeration systems may be considered as a
homogeneous binary mixture of refrigerant and absorbent. Depending upon the
boiling point difference between refrigerant and absorbent and the operating
temperatures, one may encounter a pure refrigerant vapour or a mixture of refrigerant
and absorbent vapour in generator of the absorption system. Unlike pure substances,
the thermodynamic state of a binary mixture (in liquid or vapour phase) cannot be
fixed by pressure and temperature alone. According to Gibbs’ phase rule, one more
parameter in addition to temperature and pressure is required to completely fix the
thermodynamic state. Generally, the composition of the mixture is taken as the third
independent parameter. The composition of a mixture can be expressed either in mass
fraction or in mole fraction. The mass fraction of components 1 and 2 in a binary
mixture are given by:
m1 m2
ξ1 = ; ξ2 = (14.12)
m1 + m 2 m1 + m 2
where m1 and m2 are the mass of components 1 and 2, respectively
The mole fraction of components 1 and 2 in a binary mixture are given by:
n1 n2
x1 = ; x2 = (14.13)
n1 + n 2 n1 + n 2
where n1 and n2 are the number of moles of components 1 and 2, respectively
An important property of a mixture is its miscibility. A mixture is said to be

completely miscible if a homogeneous mixture can be formed through any arbitrary
range of concentration values. Miscibility of mixtures is influenced by the
temperature at which they are mixed. Some mixtures are miscible under certain
conditions and immiscible at other conditions. The refrigerant-absorbent mixtures
used in absorption refrigeration systems must be completely miscible under all
conditions both in liquid and vapour phases.
14.4.1. Ideal, homogeneous binary mixtures
A binary mixture of components 1 and 2 is called as an ideal mixture, when it

satisfies the following conditions.
Condition 1: The volume of the mixture is equal to the sum of the volumes of its
constituents, i.e., upon mixing there is neither contraction nor expansion. Thus the
specific volume of the mixture, v is given by:
v = ξ1 .v1 + ξ 2 .v 2 (14.14)
where ξ1 and ξ2 are the mass fractions of components 1 and 2. For a binary mixture,
ξ1 and ξ2 are related by:
ξ1 + ξ 2 = 1 ⇒ ξ 2 = 1 − ξ1 (14.15)

Condition 2: Neither heat is generated nor absorbed upon mixing, i.e., the heat of
solution is zero. Then the specific enthalpy of the mixture, h is given by:
h = ξ1 .h 1 + ξ 2 .h 2 = ξ1 .h 1 + (1 − ξ1 )h 2 (14.16)
Condition 3: The mixture obeys Raoult’s law in liquid phase, i.e., the vapour pressure
exerted by components 1 and 2 (Pv,1 and Pv,2) at a temperature T are given by:
Pv ,1 = x 1 .P1,sat (14.17)
Pv , 2 = x 2 .P2,sat (14.18)
where x1 and x2 are the mole fractions of components 1 and 2 in solution, and P1,sat
and P2, sat are the saturation pressures of pure components 1 and 2 at temperature T.
The mole fractions x1 and x2 are related by:
x 1 + x 2 =1⇒ x 2 =1 − x 1 (14.19)
Condition 4: The mixture obeys Dalton’s law in vapour phase; i.e., the vapour
pressure exerted by components 1 and 2 (Pv,1 and Pv,2) in vapour phase at a
temperature T are given by:
Pv ,1 = y 1 .Ptotal (14.20)
Pv , 2 = y 2 .Ptotal (14.21)
where y1 and y2 are the vapour phase mole fractions of components 1 and 2 and Ptotal
is the total pressure exerted at temperature T. The vapour phase mole fractions y1 and
y2 are related by:
y1 + y 2 = 1 ⇒ y 2 = 1 − y1 (14.22)
and the total pressure Ptotal is given by:
Ptotal = Pv ,1 + Pv , 2 (14.23)
If one of the components, say component 2 is non-volatile compared to component

1(e.g. component 1 is water and component 2 is lithium bromide salt), then y1 ≈ 1 and
y2 ≈ 0, Pv,2 ≈ 0, then from Raoult’s and to Dalton’s laws:
Ptotal ≈ Pv,1 = x 1 .P1,sat (14.24)

14.4.2. Real mixtures
Real mixtures deviate from ideal mixtures since:
1. A real solution either contracts or expands upon mixing, i.e.,
v ≠ ξ1 .v1 + ξ 2 .v 2 (14.25)

2. Either heat is evolved (exothermic) or heat is absorbed upon mixing;
h = ξ1 .h 1 + (1 − ξ1 )h 2 + Δh mix (14.26)
where Δhmix is the heat of mixing, which is taken as negative when heat is evolved
and positive when heat is absorbed.
The above two differences between ideal and real mixtures can be attributed to
the deviation of real mixtures from Raoult’s law. Real mixtures approach ideal
mixtures as the mole fraction of the component contributing to vapour pressure
approaches unity, i.e., for very dilute solutions. Figure 14.5 shows the equilibrium
pressure variation with liquid phase mole fraction (x) of ideal and real binary mixtures
with positive (+ve) and negative deviations (-ve) from Raoult’s law at a constant
temperature. It can be seen that when the deviation from Raoult’s law is positive
(+ve), the equilibrium vapour pressure will be higher than that predicted by Raoult’s
law, consequently at a given pressure and composition, the equilibrium temperature of
solution will be lower than that predicted by Raoult’s law. The converse is true for
solutions with –ve deviation from Raoult’s law, i.e., the equilibrium temperature at a
given pressure and composition will be higher than that predicted by Raoult’s law for
solution with negative deviation. This behaviour can also be shown on specific
enthalpy-composition diagram as shown in Fig. 14.6 for a solution with negative
deviation from Raoult’s law. Refrigerant-absorbent mixtures used in vapour
absorption refrigeration systems exhibit a negative deviation from Raoult’s law, i.e.,
the process of absorption is exothermic with a negative heat of mixing.
T = Constant
P1,sat
+ve
P Ideal
-ve P2,sat
0 1
x2
Fig.14.5: Pressure-concentration behaviour of ideal and real mixtures at a constant

temperature

T = Constant
h1
Ideal solution
Δhmix
h2
Real solution
0 1
ξ2
Fig.14.6: Enthalpy-concentration behaviour of an ideal mixture and a real mixture with

negative deviation from Raoult’s law
14.5. Basic Vapour Absorption Refrigeration System

Figure 14.7 shows a basic vapour absorption refrigeration system with a
solution heat exchanger on a pressure vs temperature diagram. As shown in the figure,
low temperature and low pressure refrigerant vapour from evaporator at state 1 enters
the absorber and is absorbed by solution weak in refrigerant (state 8). The heat of
absorption (Qa) is rejected to an external heat sink at T∞. The solution, rich in
refrigerant (state 2) is pumped to the generator pressure (Pg) by the solution pump
(state 3). The pressurized solution gets heated up sensibly as it flows through the
solution heat exchanger by extracting heat from hot solution coming from generator
(state 4). Heat is supplied to this solution from an external heat source in the generator
(Qg at Tg), as a result refrigerant vapour is generated (absorbent may also boil to give
off vapour in case of ammonia-water systems) at state 5. This high-pressure
refrigerant vapour condenses in the condenser by rejecting heat of condensation to the
external heat sink (Qc at T∞) and leaves the condenser as a high pressure liquid (state
9). This high pressure refrigerant liquid is throttled in the expansion device to
evaporator pressure Pe (state 10) from where it enters the evaporator, extracts heat
from low temperature heat source (Qe at Te) and leaves the evaporator as vapour at
state 1, completing a cycle. The hot solution that is weak in refrigerant (state 6) leaves
the generator at high temperature and is cooled sensibly by rejecting heat to the
solution going to the generator in the solution heat exchanger (state 7). Then it is
throttled to the evaporator pressure in the throttle valve (state 8), from where it enters
the absorber to complete the cycle. It can be seen that though not an essential
component, the solution heat exchanger is used in practical systems to improve the
COP by reducing the heat input in the generator. A solution heat exchanger as shown
in Fig.14.7 is a counterflow heat exchanger in which the hot solution coming from the
generator comes in thermal contact with the cold solution going to the generator. As a

result of this heat exchange, less heat input is required in the generator and less heat is
rejected in the absorber, thus improving the system performance significantly.
P
Pg 5
Condenser Generator
Qg
6
Qc
9 4
Heat exchanger
7
10 3
8
Pe Evaporator Absorber
1
Qe 2
Qa Solution pump
Te T∞ Tg T
Fig.14.7: Basic
Basic vapour
vapour absorption
absorption refrigeration
refrigeration system
system withwith a solution
solution heat exchanger on a
heat exchanger
pressure vs temperature diagram
The thermodynamic performance of the above system can be evaluated by

applying mass and energy balance to each component assuming a steady flow
process. In simple theoretical analyses, internal irreversibilities such as pressure drops
between the components are generally neglected. To find the performance from the
mass and energy balance equations one needs to know inputs such as the type of
refrigerant-absorbent mixtures used in the system, operating temperatures,
composition of solution at the entry and exit of absorber, effectiveness of solution
heat exchanger etc. A simple steady flow analysis of the system will be presented in
later sections.
14.6. Refrigerant-absorbent combinations for VARS

The desirable properties of refrigerant-absorbent mixtures for VARS are:
i. The refrigerant should exhibit high solubility with solution in the absorber.
This is to say that it should exhibit negative deviation from Raoult’s law at
absorber.
ii. There should be large difference in the boiling points of refrigerant and
absorbent (greater than 200oC), so that only refrigerant is boiled-off in the
generator. This ensures that only pure refrigerant circulates through
refrigerant circuit (condenser-expansion valve-evaporator) leading to
isothermal heat transfer in evaporator and condenser.

iii. It should exhibit small heat of mixing so that a high COP can be achieved.
However, this requirement contradicts the first requirement. Hence, in
practice a trade-off is required between solubility and heat of mixing.
iv. The refrigerant-absorbent mixture should have high thermal conductivity
and low viscosity for high performance.
v. It should not undergo crystallization or solidification inside the system.
vi. The mixture should be safe, chemically stable, non-corrosive, inexpensive
and should be available easily.
The most commonly used refrigerant-absorbent pairs in commercial systems are:
1. Water-Lithium Bromide (H2O-LiBr) system for above 0oC applications such

as air conditioning. Here water is the refrigerant and lithium bromide is the
absorbent.
2. Ammonia-Water (NH3-H2O) system for refrigeration applications with
ammonia as refrigerant and water as absorbent.
Of late efforts are being made to develop other refrigerant-absorbent systems

using both natural and synthetic refrigerants to overcome some of the limitations of
(H2O-LiBr) and (NH3-H2O) systems.
Currently, large water-lithium bromide (H2O-LiBr) systems are extensively

used in air conditioning applications, where as large ammonia-water (NH3-H2O)
systems are used in refrigeration applications, while small ammonia-water systems
with a third inert gas are used in a pumpless form in small domestic refrigerators
(triple fluid vapour absorption systems).
Questions:
1. Compared to compression systems, absorption systems offer the benefits of:
a) Higher COPs
b) Lower refrigeration temperatures
c) Possibility of using low-grade energy sources
d) All of the above
Ans.: c)
2. Absorption of the refrigerant by the absorbent in a vapour absorption refrigeration

system is accompanied by:
a) Absorption of heat
b) Release of heat
c) No thermal effects
d) Reduction in volume
Ans. b)
3. An absorption system consisting of only two closed vessels:

a) Can provide continuous refrigeration
b) Provides refrigeration intermittently
c) Can work on solar energy alone
d) Has no practical application
Ans. b) and c)
4. The conventional, continuously operating single stage vapour absorption
refrigeration system:
a) Requires only thermal energy as input

b) Uses a thermal compressor in place of a mechanical compressor
c) Does not require a condenser
d) Consists of two expansion valves
Ans. b) and d)
5. For an ideal refrigerant-absorbent mixture:
a) There is neither expansion nor contraction upon mixing

b) The mixing process is exothermic
c) The mixing process is endothermic
d) Obeys Raoult’s law in liquid phase and Dalton’s law in vapour phase
Ans. a) and d)
6. For a refrigerant-absorbent mixture with a negative deviation from Raoult’s law:
a) The mixing process is exothermic

b) The mixing process is endothermic
c) The actual equilibrium temperature will be less than that predicted by Raoult’s law
d) The actual equilibrium temperature will be less more that predicted by Raoult’s law
Ans. a) and d)
7. Refrigerant-absorbent pairs used in vapour absorption refrigeration systems should:
a) Exhibit negative deviation from Raoult’s law at absorber

b) Exhibit positive deviation from Raoult’s law at absorber
c) Have large heat of mixing
d) Have large boiling point difference between refrigerant and absorbent
Ans. a) and d)
8. Which of the following statements are true:
a) Water-lithium bromide systems are used for refrigeration applications above 0oC
only
b) Ammonia-water systems can be used for refrigeration applications below 0oC only
c) Small ammonia-water systems are used in domestic refrigerators
d) Small water-lithium bromide systems are used in room air conditioners

Ans. a) and c)
9. The operating temperatures of a single stage vapour absorption refrigeration system

are: generator: 90oC; condenser and absorber: 40oC; evaporator: 0oC. The system has
a refrigeration capacity of 100 kW and the heat input to the system is 160 kW. The
solution pump work is negligible.
a) Find the COP of the system and the total heat rejection rate from the system.
b) An inventor claims that by improving the design of all the components of the
system he could reduce the heat input to the system to 80 kW while keeping the
refrigeration capacity and operating temperatures same as before. Examine the
validity of the claim.
Ans.:
a) COP = Qe/Qg = 100/160 = 0.625 (Ans.)
Total heat rejection rate = Qa+Qc = Qe+Qg = 100 + 160 = 260 kW (Ans.)
b) According to the inventor’s claim, the COPclaim is given by:
COPclaim = Qe/Qg = 100/80 = 1.25
However, for the given temperatures, the maximum possible COP is given by:
⎛Q ⎞ ⎛ Te ⎞⎛⎜ Tg − To ⎞
COPideal VARS = ⎜ e ⎟ = ⎜⎜ ⎟⎟ ⎟
⎜ Qg ⎟ ⎠⎜⎝ Tg ⎟
⎝ ⎠ max ⎝ To − Te ⎠
Substituting the values of operating temperatures, we find that:
⎛ Te ⎞⎛⎜ Tg − To ⎞ ⎛
⎟=⎜ 273 ⎞⎛ 50 ⎞
COPmax = ⎜⎜ ⎟⎟ ⎟⎜ ⎟ = 0.94
⎝ To − Te ⎠⎜⎝ Tg ⎟ ⎝ 313 − 273 ⎠⎝ 363 ⎠
⎠
Since COPclaim > COPmax ⇒ Inventor’s claim is FALSE (Ans.)

1. The following figure shows a pair of containers A & B. Container B contains an
aqueous solution of (LiBr+H2O) at a mass fraction (xi) of 0.6. Container A and
connecting pipe are filled with pure water vapor. Initially the system (A+B) is at an
equilibrium temperature of 90oC, at which the pressure is found to be 9.0 kPa. Now
water vapour starts condensing in A as cooling water starts flowing through the coil
kept in A.
A B
a) What is the temperature of the coil at which steam starts condensing in A?

b) Does the System pressure remain constant during condensation? If not, how to
maintain the pressure constant at 9.0 kPa? What happens to the temperature of
solution in B?
c) As water vapour condenses in A there will be transfer of water vapour from B
to A resulting in change of mass fraction of solution (Δx) in B. Find a relation
between Δx and f, where f is the ratio of initial mass of solution in B to the
mass of water vapour transferred from B to A.
d) What is the amount of solution required initially in B so that a mass of 1 kg of
water is transferred from B to A with a corresponding change of mass
fraction(Δx) by 0.05?
e) Neglecting the contribution of temperature changes, what is the amount of
heat transferred at A and B during the transfer of 1 kg of water from B to A? Is
energy balanced?
f) What is required to reverse the process so that initial conditions are restored?
g) Show the forward and reverse process on D ring plot.
Use the following data:

Initial enthalpy of solution = 220 kJ/kg; Final enthalpy of solution = 270 kJ/kg
Assume that the average latent heat of vaporization of water and enthalpy of water
vapour = 2500 kJ/kg
Saturation pressure of water vapour (in kPa) is given by the Antoine’s equation:
c1
ln(p sat ) = c o − ; where T is temperature in K, co=16.54, c1=3985, c2=-39.0
T + c2
Ans.:
a) Steam in vessel A starts condensing when the surface temperature of the coil falls
below the saturation temperature of water at 9.0 kPa. Using Antoine’s equation:
3985
ln(9) = 16.54 − ⇒ T = 316 .84 K = 43.7 o C (Ans.)
T − 39

b) System pressure falls as condensation of water vapour takes place in A. To keep
the system pressure constant, vapour has to be generated in B by supplying heat to
solution in B. Since the solution in B becomes richer in LiBr (i.e., concentration
increases), at the same pressure of 9.0 kPa, the solution temperature in B increases.
(Ans.)
c) From the definition of concentration for H2O-LiBr solution;
⎛ ML ⎞ ⎛ ML ⎞ ⎡ (
M W ,i − M W , f ) ⎤
Δx = x f − x i = ⎜ ⎟−⎜ ⎟ = ML ⎢ ⎥
⎜ ML + M W , f
⎝
⎟ ⎜ ML + M W , i ⎟
⎠ ⎝ ⎠ ( )(
⎣⎢ ML + M W ,i . ML + M W ,i ⎦⎥ )
Amount of water transferred from B to A = (MW,i - MW,f)
The factor f is defined as:
⎛ ML + M W , i ⎞
f =⎜ ⎟
⎜ M W ,i − M W , f ⎟
⎝ ⎠
Substituting the above in the expression for Δx and using the definition of
concentration, we find that:
⎛x ⎞
Δx = x f − x i = ⎜ f ⎟ (Ans.)
⎝ f ⎠
d) Mass of water transferred is 1.0 kg and change in concentration is 0.05. Hence the
final concentration is:
xf = xi + 0.05 = 0.60 + 0.05 = 0.65
Substituting this value in the expression for Δx, we find that
⎛ x ⎞ ⎛ 0.65 ⎞
f =⎜ f ⎟=⎜ ⎟ = 13
⎝ Δx ⎠ ⎝ 0.05 ⎠
Hence the initial mass of solution is given by:
(ML + M W ,i ) = f.(mass of water transferre d) = 13 X 1.0 = 13 kgs (Ans.)
e) From energy balance of vessel B, the amount of energy transferred to B is given

by:
Q B,in = (MB, f .h f − MB,i .hi ) + (M W ,i − M W , f )h W
Substituting the values of enthalpies and initial and final mass of solution (13 kg and
12 kg, respectively), we find that the heat transferred to B is:

QB,in = 2880 kJ (Ans.)
Neglecting the heat transferred during initial sensible cooling of vapour, the total heat
transferred at Vessel A is:
QA,out = Amount of water vapour condensed X latent heat of vapourization = 2500 kJ
(Ans.)
The difference in energy transferred at A and B is stored in the form of heat of

solution. (Ans.)
f) To reverse the process and arrive at initial condition, the condensed water in vessel
A has to be vapourized by supplying heat to vessel A. The vapour generated is
absorbed by strong solution in B. Since this is an exothermic process, heat has to be
rejected from B. (Ans.)
g) D˘hring plot of forward and reverse processese is shown below:
P x=0 xi = 0.60 xf = 0.65
i f
T
Forward process
Reverse process

Lesson
16
Vapour Absorption
Based On Ammonia-
Water Pair

The specific objectives of this lesson are to:
1. Introduce ammonia-water based vapour absorption refrigeration systems (Section
16.1)
2. Discuss the properties of ammonia-water mixtures and introduce pressure-
temperature-concentration (p-T-ξ) and enthalpy-temperature-concentration (h-T-
ξ) charts (Section 16.2)
3. Analyze some basic steady flow processes using ammonia-water mixtures such as
adiabatic and non-adiabatic mixing, throttling of solution streams and the concept
of rectification (Section 16.3)
1. Differentiate between water-lithium bromide and ammonia-water systems vis-à-

vis their properties
2. Explain the concepts of bubble point and dew point temperatures
3. Obtain thermodynamic properties of ammonia-water mixtures using p-T-ξ and h-
T-ξ charts
4. Analyze important steady flow processes involving binary mixtures
16.1. Introduction
In vapour absorption refrigeration systems based on ammonia-water pair,
ammonia is the refrigerant and water is the absorbent. These systems are more versatile
than systems based on water-lithium bromide as they can be used for both sub-zero
(refrigeration) as well above 0oC (air conditioning) applications. However, these systems
are more complex in design and operation due to the smaller boiling point temperature
difference between the refrigerant and absorbent (about 133oC). Due to the smaller
boiling point temperature difference the vapour generated in the generator consists of
both ammonia as well as water. If water is allowed to circulate with ammonia in the
refrigerant circuit, then:
i. Heat transfer in condenser and evaporator becomes non-isothermal

ii. Evaporator temperature increases
iii. Evaporation will not be complete
iv. Water may get accumulated in the evaporator leading to malfunctioning of the plant
iv. Circulation ratio increases
Since all the above effects are detrimental to the performance of the system, it is
necessary to minimize the concentration of water vapour in ammonia at the inlet to the
condenser. This requires additional components, namely a rectification column and a
dephlegmator between generator and absorber, which increases the design complexity
and cost and also reduces the system COP compared to water-lithium bromide system.

16.2. Properties of ammonia-water solutions
16.2.1. Composition
Similar to water-lithium bromide solutions, the composition of ammonia-water

solution is also expressed either in mass fraction (ξ) or mole fraction (x). However, for
ammonia-water solutions, the mass and mole fractions are defined in terms of ammonia.
For example the mass fraction ξ is defined as the ratio of mass of ammonia to the total
mass of solution, i.e.,
mA
ξ= (16.1)
mA + mW
where mA and mW are the mass of ammonia and water in solution, respectively.
Similarly, the mole fraction of ammonia-water solution is defined as:
nA
x= (16.2)
nA + nW
where nA and nW are the number of moles of ammonia and water in solution,
respectively. The number of moles of ammonia and water can easily be obtained from
their respective masses in solution and molecular weights, thus;
mA m
nA = ; and n W = W (16.3)
MA MW
where MA (= 17.0 kg/kmol) and MW (= 18.0 kg/kmol) are the molecular weights of
ammonia and water respectively.
16.2.2. Vapour pressure of ammonia-water solutions
Liquid ammonia and water are completely miscible in all proportions, hence can
form solutions of all concentrations from 0 to 1, at normal temperatures. The effect of
ammonia in water is to lower the vapour pressure of water, similarly the effect of water in
ammonia is to lower ammonia’s vapour pressure. Thus the total pressure over ammonia-
water solutions is made up of partial pressure of ammonia and partial pressure of water
vapour, and is always in between the saturation pressures of pure ammonia and water.
If Raoult’s law is applied to ammonia-water mixtures, then the total pressure at

any temperature, Ptotal is given by:
Ptotal = xPA + (1 − x ) PW (16.4)

where x is the liquid phase mole fraction of ammonia, PA and PW are the saturation
pressures of pure ammonia and pure water at that temperature.
However, similar to water-lithium bromide solutions, ammonia-water solutions also

deviate from ideal solution behaviour predicted by Raoult’s law in a negative manner,
i.e., at a given temperature of the solution the actual vapour pressure will be less than that
predicted by Raoult’s law (activity coefficient is much smaller than 1.0).
For example, at a mass fraction of 0.4 and temperature of 40oC, Raoult’s law
predicts a vapour pressure of 6.47 bar, whereas the measured vapour pressure is 3.029
bar.
The vapour pressure data of ammonia-water solutions is also available in the form
of Dühring and other P-T-ξ plots.
16.2.3. Composition of ammonia-water vapour
Since the vapour above ammonia-water liquid consists of both ammonia and
water vapour, it is essential to distinguish between the composition in liquid phase and
composition in vapour phase. The superscripts L and V will be used to distinguish
between liquid and vapour phase compositions. Thus ξL stands for liquid phase mass
fraction and ξV stands for vapour phase mass fraction. Though the vapour phase
composition, can be obtained by assuming ideal solution behaviour, it is observed that the
actual vapour composition deviates from that predicted by ideal mixture equations. Based
on experimental measurements, charts have been developed for obtaining composition of
ammonia-water mixture in vapour phase in equilibrium with a solution of ammonia and
water at different temperatures. Figure 16.1 shows the construction of such a chart using
which one can obtain the composition of mixture in vapour phase from known values of
liquid phase mass fraction (ξL) and saturated temperature of pure ammonia or pressure.

ξL
P Tsat,NH3
Mass fraction of ammonia in vapour, ξV
Fig.16.1. Vapour-liquid equilibrium chart for ammonia-water solution
16.2.4. Bubble point and dew point for ammonia-water mixtures
Figure 16.2 shows a cylinder containing mixture of ammonia and water. The
pressure on the mixture is maintained constant with the help of a free-floating piston with
fixed weights. Initially (State 1) the cylinder consists of subcooled solution of ammonia-
water mixture. Now heat is supplied to the system and the temperature of the solution is
increased steadily, the mass fraction of the solution remains constant at ξ1 initially. At a
certain temperature the first vapour bubble appears. The temperature at which the first
bubble appears is called as bubble point (=Tbubble) of the solution at that concentration and
pressure. Further heating results in increase in temperature and formation of more vapour
as shown in the figure (State 2). If heating is continued further, then the temperature

increases continuously, as more liquid is converted into vapour, and finally at a particular
temperature the last liquid droplet vaporizes. The temperature at which the last liquid
droplet evaporates is called as dew point temperature (Tdew). When heating is continued
further the mixture enters into superheated vapour state (State 3). It should be noted that
unlike pure fluids, the temperature of the ammonia-water mixture increases continuously
as the liquid undergoes vaporization. This is to say that the phase change process is
characterized by a temperature glide, which is the difference between the dew point and
bubble point temperatures. If this process is repeated with different initial concentrations
starting from 0 (pure water) to 1 (pure ammonia) and at the same pressure, different
values of bubble and dew points will be obtained. Of course when the concentration is 0
(pure water) or 1 (pure ammonia) the bubble and dew points coincide. Now if we plot the
temperatures (bubble point and dew point) against concentration and join all the bubble
points by a curve and all the dew points by another curve, then we would get the
equilibrium Temperature vs concentration curve for ammonia-water mixtures at that
pressure as shown in Fig.16.3. The loci of all the bubble points is called as bubble point
line and the loci of all the dew points is known as the dew point line. The bubble point
line is the saturated liquid line and the dew point line is the saturated vapour line for the
mixture at that pressure. The region between the bubble and dew point lines is the two-
phase region where both liquid and vapour coexist in equilibrium. Different bubble point
and dew point lines will be obtained if the experiment is carried out with different
pressures. For example, Figure 16.4 shows the bubble and dew point lines for two
different pressures, P1 and P2. The same results can also be obtained if one starts the
experiment initially with superheated vapour and then start cooling it. In this case, the
dew point is the temperature at which the first liquid droplet forms from the vapour and
the bubble point is the temperature at which the last vapour bubble condenses.
P
P
P
V
V
L L
Heat Heat Heat

(1) (2) (3)
Fig.16.2: A simple experiment illustrating the principle of bubble and dew points

P = Constant
3
Superheated
TW,Sat vapour
Tdew
Dew Point line
L+V V
2 2
Bubble Point line
T
L
2
Tbubble
1 TA,Sat
Subcooled liquid
0 ξ1L ξ2L ξ1 ξ2V ξ1V 1

ξ
Fig.16.3: Equilibrium temperature-concentration curve for NH3-H2O at a constant pressure
P2 > P1
P = P2
T
P = P1
0 ξ 1
(pure H2O) (pure NH3)
Fig.16.4: Bubble point and dew point curves at two different pressures

Now since the process is carried out in a closed system, the mass of both ammonia and
water will be conserved. The concentration of subcooled liquid will be same as the
concentration of superheated vapour. However, in the two-phase region in which the
saturated liquid exists in equilibrium with saturated vapour, the concentration of liquid
and vapour will be different. For example, at point 2 in Fig.16.3, the temperature of
saturated liquid and vapour will be same as they are in equilibrium, hence, the
concentration of liquid will be ξ2 (intersection of constant temperature line with
L
bubble point line) and that of vapour will be ξ2 (intersection of constant

V
temperature line with dew point line) as shown in the figure. Obviously the vapour
formed initially will be richer in the low boiling point substance (ammonia) and the liquid
remaining will be rich in high boiling point substance (water). For example, as shown in
Fig.16.3, the concentration of the first vapour bubble will be ξ1 and the concentration of
V
the last liquid droplet will be ξ1 .Since the total mass as well as mass of individual
L
components is always conserved, we can write mass balance for total mass (mtotal) and
ammonia (mA) mass at state 2 as:
m total = m 2 + m 2
L V
(16.5)
m A = ξ 2 L m 2 L + ξ 2 V m 2 V =ξ1 m total (16.6)
where m 2 L and m 2 V are the mass of liquid and vapour at state 2, respectively.
From the above equations it can be easily shown that:
m2
L ⎛ ξ 2 V − ξ1 ⎞
=⎜ ⎟ , or (16.7)
m2V ⎜ ξ −ξ L ⎟
⎝ 1 2 ⎠
m 2 (ξ1 − ξ 2 ) =m 2 (ξ 2 − ξ1 )
L L V V
(16.8)
The above equation is called as the mixing rule or lever rule for the binary
mixtures such as ammonia and water. It implies that the fraction of liquid and vapour in
the two-phase mixture is inversely proportional to the distance between the mixture
condition 2 and the saturated liquid and vapour states 2Land 2V, respectively.
16.2.5. Enthalpy of ammonia-water mixtures
Liquid phase:
The enthalpy of ammonia-water solution in liquid phase, hL is calculated in a

manner similar to that of water-lithium bromide solutions, i.e., by the equation:
h L = ξ. L h A L + (1 − ξ L )h W L + Δh mix (16.9)

where ξ L is the liquid phase mass fraction of ammonia, h A L and h W L are liquid phase
enthalpies of pure ammonia and water respectively. Δhmix is the heat of mixing, which is
negative (exothermic) similar to water-lithium bromide mixtures.
Using the above equation one can calculate the specific enthalpy of ammonia-
water solutions at any concentration and temperature provided the heat of mixing is
known from measurements. Thus enthalpy charts for solution are plotted as a field of
isotherms against mass fraction by taking suitable reference values for enthalpy of
ammonia and water. Since pressure does not have a significant effect on liquid enthalpy
(except at critical point), normally pressure lines are not shown on typical solution
enthalpy charts. Also enthalpy of subcooled liquid is generally assumed to be equal to
the saturated enthalpy at that temperature without loss of much accuracy.
Vapour phase:
Evaluation of enthalpy of a mixture of vapours of ammonia and water is more

complicated compared to liquid phase enthalpy. This is due to the dependence of vapour
enthalpy on both temperature and pressure. However, to simplify the problem, it is
generally assumed that ammonia and water vapour mix without any heat of mixing. Then
the enthalpy of the vapour mixture, hV is given by:
h V = ξ. V h A V + (1 − ξ V )h W V (16.10)
where ξ. V is the vapour phase mass fraction of ammonia and h A V and h W V are the
specific enthalpies of ammonia vapour and water vapour respectively at the temperature
of the mixture. However, since vapour enthalpies depend on temperature as well as
pressure, one has to evaluate the vapour enthalpy at suitable pressure, which is not equal
to the total pressure. An approximate, but practically useful method is to evaluate the
vapour enthalpies of ammonia and water at pressures, PA and PW given by:
PA = yPtotal
(16.11)
PW = (1 − y)Ptotal
where y is the vapour phase mole fraction of ammonia and Ptotal is the total pressure. It
should be noted that PA and PW are equal to the partial pressures of ammonia and water
only if they behave as ideal gases. However since ammonia and water vapour may not
approach the ideal gas behaviour at all temperatures and pressures, in general PA and PW
are not equal to the partial pressures. Using this method enthalpies of ammonia-water
mixtures in vapour phase have been obtained as functions of temperature and mass
fraction.
16.2.6. The complete enthalpy-composition diagram for ammonia-water mixtures:

Normally, charts of enthalpy-temperature-mass fraction are available which give
both liquid phase as well as vapour enthalpy of mixtures. Figure 16.5 shows one such
chart. Figure 16.6 shows the enthalpy-composition diagram at a constant pressure P. In
the figure point a represents the condition of saturated liquid mixture at a temperature T
with a liquid phase mass fraction of ξL. The liquid phase enthalpy corresponding to this
condition is given by hL. The composition and enthalpy of vapour mixture in equilibrium
with the liquid mixture at temperature T and pressure P are obtained by drawing a
vertical line from a upto the auxiliary line and then drawing a horizontal line to the right
from the intersection of the vertical line with the auxiliary line. The intersection of this
horizontal line with the dew point line a’ gives the vapour phase mass fraction ξV and the
vapour phase enthalpy hV as shown in the figure. The isotherm T in the two-phase region
is obtained by joining points a and a’ as shown in the figure. Point b in the figure lies in
the two-phase region. The specific enthalpy of this point hb is given by:
h b = (1 − ψ b )h L + ψ b h V (16.12)
where ψb is the quality or dryness fraction of the two-phase mixture at b. Since points a,
a’ and b are co-linear, the dryness fraction ψb is given by:
ξb − ξL
ψb = (16.13)
ξV − ξL
In actual enthalpy-composition diagrams the isotherms are not shown in two-phase

region as a different set of them exist for each pressure.
It is important to note that it is not possible to fix the state of the mixture
(subcooled, saturated, two-phase or superheated) just from temperature and mass fraction
alone, though one can calculate enthalpy of the mixture from temperature and mass
fraction. This is due to the reason that at a given mass fraction and temperature,
depending upon the pressure the point can be subcooled or saturated or superheated.
For example, a liquid mixture with a mass fraction of 0.4 and temperature of 80oC has an
enthalpy of 210 kJ/kg, and it will be in subcooled condition if the pressure is 4.29 bar and
saturated if the pressure is 8.75 bar.

Fig.16.5: h-T-ξ chart for ammonia-water solution
P = Constant Dew point line
Auxiliary line
a’
hfg,W hV
T
h
hfg,A
hb
b
T
hL
a
Bubble point line
0 ξL ξb ξV 1
ξ
Fig.16.6: Enthalpy-composition diagram of NH3-H2O at a constant pressure P

Determination of temperature of mixture in two-phase region:
A trial-and-error method has to be used to determine the temperature of a point in

two-phase region if its enthalpy, liquid phase mass fraction and pressure are known. The
trial-and-error method can be graphical or numerical. Figure 16.7 shows a graphical
method for finding the temperature of point x in the two-phase region which is at a
known pressure Px, liquid phase mass fraction ξx and enthalpy hx. To start with, point a’
is obtained as shown in the figure by drawing a vertical line from point x upto the
auxiliary line and then drawing a horizontal line from the intersection point a” upto the
dew point line, the intersection of which gives a’. Then a straight line a’-x-a is drawn as
shown. Next point b’ is obtained by drawing a vertical line upto the auxiliary line and
then drawing a horizontal line from b” upto the dew point line to get b’. Then line b’-x-b
is drawn passing through x. This procedure is repeated until convergence is obtained.
Numerically the temperature can be obtained from the equation, which needs to
be satisfied for each end of the isotherm passing through x, i.e.,
hV −hx hx −hL
= (16.14)
ξV − ξx ξx − ξL
To start with guess values of hL and ξL are assumed by taking some point on the bubble
point line. Then saturated vapour properties hV and ξV are obtained from the enthalpy-
composition charts using the guess values of hL and ξL. Then using the above equation,

new values of hL and ξL are obtained. Then these new values are used to obtain next set
of hV and ξV. This procedure is repeated till the values converge. Once the converged
values of hL and ξL are obtained then the temperature is read from the enthalpy-
composition chart.
Px = Constant
b’
b”
a’
h a”
hx
x
a
b
0 ξx 1
ξ
Fig.16.7: A graphical method for finding temperature of liquid-vapour mixture
16.3. Basic steady-flow processes with binary mixtures

a) Adiabatic mixing of two streams: When two streams of ammonia-water solutions are
mixed adiabatically as shown in Fig.16.8, one can write mass and energy balance
equations as:
m1 + m 2 = m 3 (16.15)
m 1 ξ1 + m 2 ξ 2 = m 3 ξ 3 (16.16)
m1 h 1 + m 2 h 2 = m 3 h 3 (16.17)
From the above equations, the mass fraction and enthalpy of the mixture at 3 are given
by:

m2
ξ 3 = ξ1 + (ξ 2 − ξ1 ) (16.18)
m3
h 3 = h1 + 2 (h 2 − h1 )
m
(16.19)
m3
3
m1/m3 h2
2
Adiabatic mixing
h
2
Chamber m2/m3
h3
3
1 h1
1
0 ξ1 ξ3 ξ2 1
ξ
Fig.16.8: Adiabatic mixing of two solution streams

Figure 16.9 shows the adiabatic mixing process with the mixture state 3 lying in
two-phase region on the enthalpy-composition diagram. The mixture state in two-phase
region implies that some vaporization has occurred during adiabatic mixing of the two
inlet streams 1 and 2. The enthalpy and composition of the two-phase mixture at 3 can be
obtained by using the equations given above. However, since this is in two-phase region,
the mixture consists of saturated liquid and vapour. The dryness fraction and temperature
of the mixture (T3) have to be obtained by trial-and-error method by applying mixing
rules. The fraction of the vapour in the mixture at 3 is then given by:
m3 V ξ 3 − ξ 3L 3 3L
= = (16.20)
m3 ξ 3 V − ξ 3 L 3 V 3L
b) Mixing of two streams with heat transfer: The process of mixing of two streams with
heat transfer takes place in absorber and generator of absorption refrigeration systems.
For example, Fig.16.10 shows the mixing of saturated refrigerant vapour (state 1) with
saturated solution of refrigerant-absorbent (state 2) in the absorber. The resulting mixture
is a solution that is rich in refrigerant (state 3). Since the process is exothermic, heat (Q)
is released during this process. Mass and energy balance equations for this process can be
written as:

3V
h
T3
h2 2
3
h3 1
h1 3L
T3
0 ξ2 ξ3 ξ1 1
ξ
Fig.16.9: Adiabatic mixing of two streams on h-T-ξ diagram

m1 + m 2 = m 3 (16.21)
m 1 ξ1 + m 2 ξ 2 = m 3 ξ 3 (16.22)
m1 h 1 + m 2 h 2 = m 3 h 3 + Q (16.23)
From the above equations, the enthalpy of the mixture at 3 is given by:
m2
h 3 = h1 + (h 2 − h 1 ) − Q (16.24)
m3 m3
Thus with heat transfer from the mixing chamber, the exit state lies at a vertical
distance of (Q/m3) below the state which would result without heat transfer (point 3’).
The exit point would lie above the state without heat transfer if heat is transferred to the
mixing chamber.
c) Throttling process: Throttling or isenthalpic expansion of ammonia-water solution

takes place in the solution expansion valve of the absorption refrigeration system. Figure
16.11 shows the throttling process on enthalpy-composition diagram. Since both mass
and energy are conserved during this process, and there is neither work nor heat transfer,
we obtain:
ξ1 = ξ 2 (16.25)
h1 = h 2 (16.26)
3
2 1
h
Absorber
3’
1 ’
Q Q/m3
2
3
0 ξ3=ξ3’ 1
ξ
Fig.16.10: Mixing of two streams with heat transfer

Hence the inlet and outlet states, points 1 and 2 are identical on enthalpy-composition diagram as
shown in the figure. However, as there is possibility of vapour generation due to flashing, the
exit condition may be a mixture of saturated liquid and vapour at the outlet pressure P2 then the
exit temperature T2 will be much lower than the inlet temperature T1. Taking point 2 as in the
two-phase region corresponding to the outlet pressure P2, one can get the vapour fraction and exit
temperature T2 by trial-end-error method as discussed earlier.
P2, Dew point line
V
h
P1 T2=TL=TV
T1 1,2
h1=h2
1 2
T2
L
P2, Bubble point line
ξ1 = ξ2
ξ
Fig.16.11: Throttling of ammonia-water solution

d) Heating and cooling process – concept of rectification: Figure 16.12 shows an
arrangement wherein an initially subcooled solution (state 1) is heated in a heat
exchanger A (HX A) in such a way that the exit condition 2 lies in the two-phase region.
This two-phase mixture then flows into an adiabatic separator (SEP A) where the
saturated liquid (state 3) and saturated vapour (state 4) are separated. The saturated
vapour at state 4 is then cooled to state 5 in another heat exchanger B (HX B) by rejecting
heat 4Q5. The resulting two-phase mixture is then fed to another adiabatic separator B
(SEP B), where again the saturated liquid (state 6) and saturated vapour (state 7) are
separated. It is assumed that the entire process takes place at a constant pressure and is a
steady-flow process.

Vapour, 7 HX (B)
5
V P=Constant
4Q5
L 4
SEP (B)
Isotherms
4 7 4Q5/m4
Saturated liquid, 6
5
2
HX (A) V 1Q2/m1
3
1 2 L 1 6
1Q2
SEP (A)
Saturated liquid, 3
Fig.16.12: Heating and cooling of NH3-H2O solution – concept of rectification
Now mass and energy balances are applied to each of the components as shown below:
Heat exchanger A:
Mass balance:
m1 = m 2 (16.27)
ξ1 = ξ 2 (16.28)
Energy balance:
1Q2 = m1 (h 2 − h 1 ) (16.29)
Separator A:
Mass balance:
m2 = m3 + m4 (16.30)
m 2 ξ 2 = m 3ξ3 + m 4 ξ 4 (16.31)
Energy balance:

m 2h 2 = m3h 3 + m 4 h 4 (16.32)
from the above equations:
m3 ξ − ξ2 h −h2 length 4 − 2
= 4 = 4 = (16.33)
m2 ξ4 − ξ3 h4 − h3 length 4 − 3
m4 ξ − ξ3 h − h3 length 2 − 3
= 2 = 2 = (16.34)
m2 ξ4 − ξ3 h4 − h3 length 4 − 3
Similar equations can be obtained for heat exchanger B and separator B. The entire
process is also shown on enthalpy-composition diagram in Fig.16.12.
It may be noted that from the above arrangement consisting of heating, cooling
and separation, one finally obtains a vapour at state 7 that is rich in ammonia. That is the
combination of heat exchangers with separators is equivalent to the process of
rectification. Heat exchanger A plays the role of generator, while heat exchanger B plays
the role of dephlegmator. To improve the process of rectification in actual vapour
absorption refrigeration systems, a rectifying column is introduced between the generator
and dephlegmator. In the rectifying column, the vapour from the separator A comes in
contact with the saturated liquid coming from separator B. As a result, there will be heat
and mass transfer between the vapour and liquid and finally the vapour comes out at a
much higher concentration of ammonia.
The practical ammonia-water based vapour absorption refrigeration system

incorporating rectifying column and dephlegmator in addition to the basic components
will be discussed in the next lesson.
Questions and Answers:

1. Presence of water vapour in the refrigerant circuit of a NH3-H2O system:
a) Decreases evaporator temperature

b) Increases evaporator temperature
c) Increases circulation ratio
d) Leads to non-isothermal heat transfer in evaporator and condenser
Ans. b), c) and d)
2. Compared to H2O-LiBr systems, a NH3-H2O system:
a) Requires additional components due to the requirement of rectification

b) Yields higher COP
c) Yields lower COP
d) Increases design complexity and system cost

Ans. a), c) and d)
3. Which of the following statements regarding the definition of concentration are TRUE:
a) A strong solution of H2O-LiBr implies a solution rich in refrigerant

b) A strong solution of H2O-LiBr implies a solution weak in refrigerant
c) A strong solution of NH3-H2O implies a solution rich in refrigerant
d) A strong solution of NH3-H2O implies a solution weak in refrigerant
Ans. b) and c)
4. Which of the following statements regarding NH3-H2O solution are TRUE:
a) The bubble point temperature is always higher than dew point temperature
b) The bubble point temperature is always lower than dew point temperature
c) At a given pressure, the bubble point and dew point temperatures are higher than the
saturation temperature of NH3 but lower than the saturation temperature of H2O
d) At a given pressure, the bubble point and dew point temperatures are lower than the
saturation temperature of NH3 but higher than the saturation temperature of H2O
Ans.: b) and c)
5. For NH3-H2O solution at equilibrium, which of the following statements are FALSE:
a) The concentration of liquid phase is lower than the concentration of vapour phase
b) The enthalpy of subcooled solution is a function of temperature and pressure
c) The enthalpy of superheated vapour is a function of temperature only
d) The state of the mixture can be uniquely determined by temperature and concentration
Ans.: b) and d)
6. When a binary solution of NH3-H2O is throttled adiabatically:
a) Temperature always remains constant

b) Temperature may decrease
c) Temperature may increase
d) Enthalpy always remains constant
Ans.: b) and d)
7. A binary mixture of NH3 - H2O is at a temperature of 40oC and a liquid phase mole
fraction x of 0.5. Find the vapour pressure of the solution, if the activity coefficient of the
solution is 0.65. The saturation pressures of ammonia and water at 40oC are 1557 kPa and
7.375 kPa, respectively.

Ans.: From Raoult’s law, the vapour pressure is given by:
Pv,Raoult = x.Psat ,NH3 + (1 − x ).Psat ,H2O = 782.19 kPa
Using the definition of activity coefficient, a; the actual vapour pressure Pv is given by:
Pv,act = a.Pv,Raoult = 0.65 X 782 .19 = 508 .42 kPa (Ans.)
8. A binary vapour mixture consisting of ammonia and water is at a mole fraction of 0.9
and 10oC. If the partial pressures of ammonia and water vapour in the mixture are 616.25
kPa and 1.227 kPa, respectively; and the specific vapour enthalpies of ammonia and
water are 1471.57 kJ/kg and 2519.9 kJ/kg, respectively, find a) the vapour pressure of the
mixture, and b) the specific enthalpy of the mixture.
Ans.:
a) Assume the vapour mixture to behave as a mixture of ideal gases, then the total
pressure of the mixture Pv is given by:
Pv = y.PNH3 + (1 − y).PH2O = 554.75 kPa (Ans.)
b) The mass fraction of the mixture ξV is given by:

mA n A .M A 17n A
ξV = = =
m A + m W n A .M A + n W .M W 17n A + 18n W
Since the mole fraction of the vapour mixture is 0.9 ⇒ nA = 9 nW
Substituting this in the expression for mass fraction, we find that ξV = 0.895
Again assuming the vapour mixture to behave as a mixture of ideal gases; the enthalpy of
the mixture is given by:
hV = ξV.hA + (1-ξV)hW = 1581.64 kJ/kg (Ans.)
9. Find the dryness fraction (quality) and specific enthalpy of the two-phase (liquid &
vapour) of ammonia-water mixture using the following data:
Liquid phase mass fraction, ξL = 0.30

Vapour phase mass fraction, ξV = 0.87
Mass fraction of 2-phase mixture, ξ = 0.50
Specific enthalpy of saturated liquid, hL = 340 kJ/kg
Specific enthalpy of saturated vapour, hV = 1640 kJ/kg

Ans.:
mV ξ − ξL
Dryness fraction, ψ = = = 0.351 (Ans.)
m V + mL ξ V − ξL
Enthalpy of the two-phase mixture is given by:
h = (1 − ψ )hL + ψh V = 796.3 kJ / kg (Ans.)
9. Two solution streams are mixed in a steady flow device. A heat transfer rate of 24 kW
takes place from the device. Find the exit concentration and enthalpy using the data given
below:
Stream 1: Mass flow rate, m1 = 0.1 kg/s

Concentration, ξ1 = 0.7
Enthalpy, h1 = 110 kJ/kg
Stream 2: Mass flow rate, m2 = 0.3 kg/s

Concentration, ξ2 = 0.4
Enthalpy, h2 = 250 kJ/kg
Ans.:
From mass balance of solution and ammonia, the exit concentration is given by ξ3 :
(m1ξ 1 + m 2 ξ 2 )
ξ3 = = 0.475 (Ans.)
(m1 + m 2 )
From energy balance of solution and ammonia, the exit concentration is given by h3:
h3 =
[(m1h1 + m2h2 ) − Q] = 155 kJ / kg
(Ans.)
(m1 + m 2 )

Lesson
17
Vapour Absorption
Based On Ammonia-
Water Pair

The specific objectives of this lesson are to:
1. Introduce ammonia-water systems (Section 17.1)
2. Explain the working principle of vapour absorption refrigeration systems
based on ammonia-water (Section 17.2)
3. Explain the principle of rectification column and dephlegmator (Section 17.3)
4. Present the steady flow analysis of ammonia-water systems (Section 17.4)
5. Discuss the working principle of pumpless absorption refrigeration systems
(Section 17.5)
6. Discuss briefly solar energy based sorption refrigeration systems (Section
17.6)
7. Compare compression systems with absorption systems (Section 17.7)
1. Draw the schematic of a ammonia-water based vapour absorption

refrigeration system and explain its working principle
2. Explain the principle of rectification column and dephlegmator using
temperature-concentration diagrams
3. Carry out steady flow analysis of absorption systems based on ammonia-
water
4. Explain the working principle of Platen-Munter’s system
5. List solar energy driven sorption refrigeration systems
6. Compare vapour compression systems with vapour absorption systems
17.1. Introduction
Vapour absorption refrigeration system based on ammonia-water is one of the
oldest refrigeration systems. As mentioned earlier, in this system ammonia is used
as refrigerant and water is used as absorbent. Since the boiling point temperature
difference between ammonia and water is not very high, both ammonia and water
are generated from the solution in the generator. Since presence of large amount of
water in refrigerant circuit is detrimental to system performance, rectification of the
generated vapour is carried out using a rectification column and a dephlegmator.
Since ammonia is used as the refrigerant, these systems can be used for both
refrigeration and air conditioning applications. They are available in very small (as
pumpless systems) to large refrigeration capacities in applications ranging from
domestic refrigerators to large cold storages. Since ammonia is not compatible with
materials such as copper or brass, normally the entire system is fabricated out of
steel. Another important difference between this system and water-lithium bromide
systems is in the operating pressures. While water-lithium bromide systems operate
under very low (high vacuum) pressures, the ammonia-water system is operated at
pressures much higher than atmospheric. As a result, problem of air leakage into the
system is eliminated. Also this system does not suffer from the problem of
crystallization encountered in water-lithium bromide systems. However, unlike water,
ammonia is both toxic and flammable. Hence, these systems need safety
precautions.

Dephlegmator
Qd
10
9
5
Rectification Qg
column
Condenser Generator
4
11 6
Qc
Heat Exchanger-I Heat Exchanger-II
12 1 7
14
8
13
Evaporator Absorber
3
2
Qe Qa
Solution pump
Wp
Fig.17.1: Schematic of NH3-H2O based vapour absorption refrigeration system
17.2. Working principle

Figure 17.1 shows the schematic of an ammonia-water absorption
refrigeration system. Compared to water-lithium bromide systems, this system uses
three additional components: a rectification column, a dephlegmator and a
subcooling heat exchanger (Heat Exchanger-I). As mentioned before, the function
of rectification column and dephlegmator is to reduce the concentration of water
vapour at the exit of the generator. Without these the vapour leaving the generator
may consist of five to ten percent of water. However, with rectification column and
dephlegmator the concentration of water is reduced to less than one percent. The
rectification column could be in the form of a packed bed or a spray column or a
perforated plate column in which the vapour and solution exchange heat and mass.
It is designed to provide a large residence time for the fluids so that high heat and
mass transfer rates could be obtained. The subcooling heat exchanger, which is
normally of counterflow type is used to increase the refrigeration effect and to ensure
liquid entry into the refrigerant expansion valve.
As shown in the figure, low temperature and low pressure vapour (almost
pure ammonia) at state 14 leaves the evaporator, exchanges heat with the
condensed liquid in Heat Exchanger-I and enters the absorber at state 1. This
refrigerant is absorbed by the weak solution (weak in ammonia) coming from the
solution expansion valve, state 8. The heat of absorption, Qa is rejected to an
external heat sink. Next the strong solution that is now rich in ammonia leaves the
absorber at state 2 and is pumped by the solution pump to generator pressure, state
3. This high pressure solution is then pre-heated in the solution heat exchanger
(Heat Exchanger-II) to state 4. The preheated solution at state 4 enters the generator
and exchanges heat and mass with the hot vapour flowing out of the generator in the
rectification column. In the generator, heat is supplied to the solution (Qg). As a result
vapour of ammonia and water are generated in the generator. As mentioned, this hot
vapour with five to ten percent of water exchanges heat and mass with the rich
solution descending from the top. During this process, the temperature of the vapour
and its water content are reduced. This vapour at state 5 then enters the
dephlegmator, where most of the water vapour in the mixture is removed by cooling
and condensation. Since this process is exothermic, heat (Qd) is rejected to an
external heat sink in the dephlegmator. The resulting vapour at state 10, which is
almost pure ammonia (mass fraction greater than 99 percent) then enters the
condenser and is condensed by rejecting heat of condensation, Qc to an external
heat sink. The condensed liquid at state 11 is subcooled to state 12 in the subcooling
heat exchanger by rejecting heat to the low temperature, low pressure vapour
coming from the evaporator. The subcooled, high pressure liquid is then throttled in
the refrigerant expansion valve to state 13. The low temperature, low pressure and
low quality refrigerant then enters the evaporator, extracts heat from the refrigerated
space (Qe) and leaves the evaporator at state 14. From here it enters the subcooling
heat exchanger to complete the refrigerant cycle. Now, the condensed water in the
dephlegmator at state 9 flows down into the rectifying column along with rich solution
and exchanges heat and mass with the vapour moving upwards. The hot solution
that is now weak in refrigerant at state 6 flows into the solution heat exchanger
where it is cooled to state 7 by preheating the rich solution. The weak, but high
pressure solution at state 7 is then throttled in the solution expansion valve to state
8, from where it enters the absorber to complete its cycle.
As far as various energy flows out of the system are concerned, heat is
supplied to the system at generator and evaporator, heat rejection takes place at
absorber, condenser and dephlegmator and a small amount of work is supplied to
the solution pump.
17.3. Principle of rectification column and dephlegmator

Figure 17.2 shows the schematic of the rectification system consisting of the
generator, rectifying column and dephlegmator. As shown in the figure, strong
solution from absorber enters at the rectification column, vapour rich in ammonia
leaves at the top of the dephlegmator and weak solution leaves from the bottom of
the generator. A heating medium supplies the required heat input Qg to the generator
and heat Qd is rejected to the cooling water in the dephlegmator.

Vapour to condenser
ξV Dephlegmator
Cooling
water
Qd
Strong solution
from absorber
ξSL
Generator
Heating
medium
F
igure ξWL Qg
Weak solution
to absorber
Fig.17.2: Schematic of the rectification column used in NH3-H2O systems
Fig.17.3: Rectification process in the generator

17.3 shows the schematic of the generator with lower portion of the rectification
column and the process that takes place in this column on temperature-composition
diagram. As shown, in this column the ascending vapour generated in the generator
and initially at a mass fraction of ξWV is enriched in ammonia to ξSV as it exchanges
heat and mass with the descending rich solution, which had an initial concentration
of ξSL. During this process the solution becomes weak as ammonia is transferred
from liquid to vapour and water is transferred from vapour to liquid. In the limit with
infinite residence time, the vapour leaves at mass fraction ξSV that is in equilibrium
with the strong solution. It can also be seen that during this process, due to heat
transfer from the hot vapour to the liquid, the solution entering the generator section
is preheated. This is beneficial as it reduces the required heat input in the generator.
Figure 17.4 shows the principle of dephlegmator (or reflux condenser) in

which the ascending vapour is further enriched. At the top of the dephlegmator, heat
is removed from the vapour so that a part of the vapour condenses (reflux). This
reflux that is cooler, exchanges heat with the hotter vapour ascending in the column.
During this process water vapour is transferred from the vapour to the liquid and
ammonia is transferred from liquid to the vapour as shown in Fig. 17.4. As a result
the vapour leaves the rectification column in almost pure ammonia form with a
concentration of ξV.
Fig.17.4: Principle of dephlegmator
17.4. Steady-flow analysis of the system

The analysis is carried out in a manner similar to water-lithium bromide
system, i.e., by applying steady flow mass and energy balance to each component.
However, since the composition is defined on the basis of ammonia in the solution,
the terms weak and strong solution concentrations have different meanings. In
ammonia-water systems, strong solution means solution that is rich in ammonia,
consequently, weak solution refers to solution that is weak in ammonia.
The circulation ratio λ is defined as the ratio of weak solution to refrigerant

flow rate, i.e.,
.
m WS . . . .
λ= ⇒ m WS = λ m and m SS = (1 + λ ) m (17.1)
.
m
By applying mass balance across the absorber and assuming the amount of
water vapour in the refrigerant vapour at the exit of evaporator as negligible, the
circulation ratio can be shown to be:
1− ξS
λ= (17.2)
ξS − ξ W
where ξS and ξW are the mass fractions of the strong and weak solutions leaving the
absorber and entering the absorber, respectively.
Mass and energy balance equations for all the components are same as
those of water-lithium bromide system, however, the thermal energy input to the
generator will be different due to the heat transfer at the dephlegmator. Taking a
control volume that includes entire rectifying column (generator + rectification column
+ dephlegmator) as shown in Fig.17.5, we can write the energy equation as:
. . .
Q g − Q d = m10 h10 + m 6 h 6 − m 4 h 4 (17.3)
writing the mass flow rates of strong (point 4) and weak (point 6) solutions in terms of
refrigerant flow rate and mass fractions, we can write the above equation as:
.
Q g − Q d = m[(h10 − h 4 ) + λ (h 6 − h 4 )] (17.4)

Fig.17.6: Control volume for calculating heat transfer rate at dephlegmator
Fig.17.5: Control volume for calculating heat input to the system
From the above expression Qg-Qd can be calculated, however, to find COP
we need to know Qg. This requires estimation of heat transferred in the
dephlegmator, Qd. This can be obtained by applying mass and energy balance
across the dephlegmator section as shown in Fig.17.6. From these equations it can
be shown that for ideal rectification with the exit vapour being pure ammonia,
the heat transferred in the dephlegmator is given by:
⎞ ⎡
( )
⎛ ⎛ V ⎞ ⎤
⎜ Q d ⎟ = ⎢h V − h + ⎜ 1 − ξ i ⎟ h V − h L ⎥ = (h V − h ) + H (17.5)
⎜ . ⎟ i 10 ⎜ V L⎟ i e i 10 L
⎝ m ⎠ ⎢⎣ ⎝ ξi − ξ e ⎠ ⎥
⎦
⎛ 1− ξ ⎞
( )
V
⎜ i ⎟ V
HL = ⎜ ⎟ hi − h e L (17.6)
⎜ξ V L ⎟
⎝ i −ξe ⎠
The above equation is applicable at any section across the upper rectification
column. If the process is plotted on enthalpy-composition diagram as shown in
Fig.17.6, it can be easily seen that the ordinate of point R (called as Pole of the
rectifier) is equal to
⎛Q
⎜
⎜
d
⎞
⎟ ⎜
. ⎟ + h 10 as HL is equal to H L = ⎜ (
⎛ 1− ξi V ⎞ V
L ⎟ i
)
⎟ h − heL .
⎝ ξi − ξe ⎠
V
⎝ m⎠
It should be noted that the line joining points L and V on enthalpy-composition

diagram need not be an isotherm. In other words, points V and L need not be in
equilibrium with each other, but they have to satisfy the mass and energy balance
across the control volume.
For rectification to proceed in the column, it is essential that at every cross-

section, the temperature of the vapour should be higher than that of the liquid. This is

possible only if the slope of the line passing through pole R is always steeper than
the isotherm in the two-phase region passing through heL and ξeL. This can be
ensured by placing the pole R at a sufficiently high level on the ξ = 1 axis. This in
turn fixes the minimum amount of reflux and the heat rejected at the dephlegmator. It
is observed that for ammonia-water mixtures the condition that the vapour must
always be warmer than the liquid is satisfied by drawing a straight line through R
steeper than the isotherm passing through the strong solution feed point (point 4).
This way the position of R is fixed and from this, the minimum amount of
dephlegmator heat Qd,min is determined. However, the actual dephlegmator heat
Qd,act will be larger than the minimum amount, and the ratio of minimum
dephlegmator heat to actual dephlegmator heat is called as rectifier efficiency, ηR
given by:
Q d,min
ηR = (17.7)
Q d,act
The rectifier efficiency depends on the design of contact surface used for the
rectification column.
Sometimes, in the absence of required data, the COP is calculated by
assuming that the dephlegmator heat is a certain percentage of generator heat
(usually 10 to 20 percent).
17.5: Pumpless vapour absorption refrigeration systems

Conventional absorption refrigeration systems use a mechanical pump for
pumping the solution from absorber pressure to generator pressure. However, there
are also absorption refrigeration systems that do not require a mechanical pump.
These systems offer several advantages over conventional systems such as:
i. High reliability due to absence of moving parts

ii. Very little maintenance
iii. Systems require only low grade thermal energy, hence no need for any grid power
iv. Silent operation
Due to the above advantages the pumpless systems find applications such as
refrigerators for remote and rural areas, portable refrigerators, refrigerators for luxury
hotel rooms etc.
Several pumpless systems using both water-lithium bromide and ammonia-

water have been developed over the last many decades. However, among these the
most popular and widely used system is the one known as Platen-Munters system or
Triple Fluid Vapour Absorption Refrigeration System (TFVARS). As mentioned in the
introduction, this system was developed by Platen and Munters of Sweden in 1930s.
It uses ammonia as refrigerant and water as absorbent and hydrogen as an inert
gas. Unlike conventional systems, the total pressure is constant throughout the
Platen-Munters system, thus eliminating the need for mechanical pump or
compressor. To allow the refrigerant (ammonia) to evaporate at low temperatures
in the evaporator, a third inert gas (hydrogen) is introduced into the evaporator-
absorber of the system. Thus even though the total pressure is constant throughout

the system, the partial pressure of ammonia in evaporator is much smaller than the
total pressure due to the presence of hydrogen.
For example: if the total pressure of the system is 15 bar, then the condenser
temperature will be 38.7oC (saturation temperature at 15 bar). If contribution of
hydrogen to total pressure in the evaporator is 14 bar, then the partial pressure of
ammonia in evaporator is 1 bar, hence ammonia can evaporate at –33oC (saturation
temperature at 1 bar), thus providing refrigeration effect at very low temperatures.
The liquid ammonia in the evaporator cannot boil in the evaporator as its
partial pressure is lower than the total pressure (no vapour bubbles form). The
ammonia simply evaporates into the hydrogen gas (just as liquid water evaporates
into the atmosphere) as long as hydrogen gas is not saturated with ammonia. The
ammonia vapour generated is carried away by the process of diffusion, hence
Platen-Munters systems are also called as diffusion-absorption systems.

Fig.17.8: Working principle of Platen-Munters system
Figure 17.8 shows the schematic of a triple-fluid Platen-Munters system.
Starting with the strong solution at the exit of the absorber (state 5), heat is supplied
in the generator; ammonia vapour is generated as a result. The vapour generated
moves up through the bubble pump due to buoyancy. As the vapour moves up it
carries the weak solution to the top of the bubble pump. At the top, the weak solution
and vapour are separated. The refrigerant vapour at state 1 flows into the
condenser, where it condenses by rejecting heat to the heat sink (condensation
takes place at high temperature as ammonia pressure is equal to the total pressure).
The condensed liquid at state 2 flows into evaporator. As it enters into the evaporator
its pressure is reduced to its partial pressure at evaporator temperature due to the
presence of hydrogen gas in the evaporator. Due to the reduction in pressure, the
ammonia evaporates by taking heat from the refrigerated space. The ammonia
vapour diffuses into the hydrogen gas. Since the mixture of ammonia and hydrogen
are cooler, it flows down into the absorber due to buoyancy. In the absorber, the
ammonia vapour is absorbed by the weak solution coming from the bubble pump.
Heat of absorption is rejected to the heat sink. Due to this, the temperature of
hydrogen gas increases and it flows back into the evaporator due to buoyancy. Thus
the circulation of fluids throughout the system is maintained due to buoyancy effects
and gravity.
Due to the evaporation process (as against boiling in conventional systems)

the temperature of the evaporating liquid changes along the length of the evaporator.
The coldest part is obtained at the end where hydrogen enters the evaporator
as the partial of ammonia is least at this portion. This effect can be used to
provide two temperature sections in the evaporator for example: one for frozen food
storage and the other for fresh food storage etc.
A liquid seal is required at the end of the condenser to prevent the entry of
hydrogen gas into the condenser. Commercial Platen-Munters systems are made of
all steel with welded joints. Additives are added to minimize corrosion and rust
formation and also to improve absorption. Since there are no flared joints and if the
quality of the welding is good, then these systems become extremely rugged and
reliable. The Platen-Munters systems offer low COPs (of the order of 0.2) due to
energy requirement in the bubble pump and also due to losses in the evaporator
because of the presence of hydrogen gas. In addition, since the circulation of fluids
inside the system is due to buoyancy and gravity, the heat and mass transfer
coefficients are relatively small, further reducing the efficiency. However, these
systems are available with a wide variety of heat sources such as electrical heaters
(in small hotel room systems), natural gas or LPG gas, hot oils etc. Figure 17.9
shows the schematic of the refrigeration system of a small commercial Platen-
Munters system.
Qc
Qe
Qa
Qg
Fig.17.9: Refrigeration circuit of a small diffusion-absorption (Platen-Munters) system

It is interesting to know that Albert Einstein along with Leo Szilard had
obtained a US patent for a pumpless absorption refrigeration system in 1930. The
principle of operation of this system is entirely different from that of Platen-Munters
system. In Einstein’s system, butane is used as the refrigerant, while ammonia is
used as pressure equalizing fluid in evaporator. Water is used as the absorbent for
the pressure equalizing fluid. However, unlike Platen-Munter’s system, Einstein’s
system has not been commercialized. Recently attempts have been made to revive
Einstein’s cycle.
17.6: Solar energy driven sorption systems

In principle, solar energy can be used to drive any type of refrigeration
system: compression or absorption. However, in most of the cases, the direct
utilization of solar thermal energy for running refrigeration systems is more efficient.
Thus solar energy based heat operated systems are attractive. Again solar energy
can be used to run a conventional absorption system with solution pump or a
pumpless absorption or adsorption system.
Solar energy driven adsorption systems that use a solid adsorbent in place of
a liquid absorbent offer certain advantages. The solid sorption systems also known
as dry absorption systems do not have a solution circuit as the vapour/gas is directly
absorbed and desorbed by a solid. Notable among the dry absorption types are the
systems based on water-zeolites/silica gel, methanol-activated carbon,
ammonia-calcium chloride, sulphur dioxide-sulphites, carbon dioxide-
carbonates and hydrogen-metal hydrides. However, some practical design
problems such as: smaller specific power outputs, poor heat and mass transfer
characteristics of the solid absorbents, unwanted side reactions, undesired
decomposition of reacting materials, swelling of solid material and corrosion of the
structural materials due to the nature of the reacting materials/reactions hamper the
development of solid sorption systems on commercial scale. Several successful
attempts have been made to build refrigeration systems that run on solar energy
only. However, several practical problems related to their cost, performance and
reliability hamper the wide-spread use of solar energy driven refrigeration systems.
17.7: Comparison between compression and absorption

refrigeration systems
Table 17.1 shows a comparison between compression and absorption
refrigeration systems.
Compression systems Absorption systems

Work operated Heat operated
High COP Low COP (currently maximum ≈ 1.4)
Performance (COP and capacity) very Performance not very sensitive to
sensitive to evaporator temperatures evaporator temperatures
System COP reduces considerably at COP does not reduce significantly with
part loads load
Liquid at the exit of evaporator may Presence of liquid at evaporator exit is
damage compressor not a serious problem
Performance is sensitive to evaporator Evaporator superheat is not very
superheat important
Many moving parts Very few moving parts
Regular maintenance required Very low maintenance required
Higher noise and vibration Less noise and vibration
Small systems are compact and large Small systems are bulky and large
systems are bulky systems are compact
Economical when electricity is available Economical where low-cost fuels or
waste heat is available
Table 17.1: Comparison between compression and absorption systems

Questions and answers:
1. In an ammonia-water system a rectification column is used mainly to:
a) To improve the COP of the system

b) To reduce the operating pressures
c) To minimize the concentration of water in refrigeration circuit
d) All of the above
Ans.: c)
2. In a reflux condenser:
a) Heat is extracted so that the vapour leaving is rich in ammonia

b) Heat is supplied so that the vapour leaving is rich in ammonia
c) Heat is extracted so that the vapour leaving is rich in water
d) Heat is supplied so that the vapour leaving is rich in ammonia
Ans.: a)
3. Due to the requirement of rectification:
a) The required generator pressure increases

b) The required generator temperature increases
c) The required generator heat input increases
d) All of the above
Ans.: c)
4. In pumpless vapour absorption refrigeration systems:
a) The evaporation process is non-isothermal

b) The system pressure is almost same everywhere
c) A pressure equalizing fluid is required to increase condenser pressure
d) A pressure equalizing fluid is required to increase evaporator pressure
Ans.: a), b) and d)
5. Which of the following statements regarding pumpless systems are TRUE:
a) Pumpless systems can use a wide variety of heat sources

b) Pumpless systems are silent, reliable and rugged
c) Pumpless systems offer high COPs
d) Pumpless systems operate at very low pressures
Ans.: a) and b)

6. Compared to compression systems, the performance of absorption systems:
a) Is very sensitive to evaporator temperature

b) Is not sensitive to load variations
c) Does not depend very much on evaporator superheat
d) All of the above
Ans.: b) and c)
7. Compared to compression systems, absorption systems:
a) Contain very few moving parts

b) Require regular maintenance
c) Offer less noise and vibration
d) Are compact for large capacities
Ans.: a), c) and d)
8. A vapour absorption refrigeration system based on ammonia-water (Figure 17.1)

has refrigeration capacity of 100 TR. The various state properties of the system
shown below are given in the table. Taking the heat rejection rate in the reflux
condenser (Qd) as 88 kW, find a) The mass flow rates of solution through the
evaporator, strong solution and weak solution; b) Enthalpy values not specified in the
table and c) Heat transfer rates at condenser, absorber and generator and solution
pump work d) System COP
Concentration (X),
State point P, bar T, oC Enthalpy, kJ/kg
kg of NH3/kg of solution
1 2.04 13.9 0.996
2 2.04 26.1 0.408 -58.2
3 13.61 26.1 0.408 -56.8
4 13.61 93.3 0.408 253.6
6 13.61 115.6 0.298 369.9
7 13.61 36.1 0.298
8 2.04 36.1 0.298
10 13.61 54.4 0.996 1512.1
11 13.61 36.1 0.996 344.3
12 13.61 30.0 0.996 318.7
13 2.04 -17.8 0.996
14 2.04 4.4 0.996 1442.3
Ans.:
a) Mass flow rate through evaporator, m1 is given by:
⎛ Qe ⎞ ⎛ Qe ⎞ ⎛ 3.517 X 100 ⎞
m1 = ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ = ⎜ ⎟ = 0.313 kg / s (Ans.)
⎝ h14 − h13 ⎠ ⎝ h14 − h12 ⎠ ⎝ 1442.3 − 318.7 ⎠
Circulation ratio λ is given by:

⎛m ⎞ ⎛ ξ 10 − ξ 7 ⎞
λ = ⎜⎜ ws ⎟⎟ = ⎜⎜ ⎟⎟ = 5.345
⎝ m1 ⎠ ⎝ ξ7 − ξ8 ⎠
Therefore, mass flow rate of weak solution, mws = m1 X λ = 1.673 kg/s (Ans.)
mass flow rate of strong solution, mss = m1 X (1+λ) = 1.986 kg/s (Ans.)
b) State points 1, 7,8 and 13:
From energy balance across Heat Exchanger –I;
(h11 - h12) = (h1 - h14) ⇒ h1 = h14 + (h11 - h12) = 1467.9 kJ/kg (Ans.)
From energy balance across solution heat exchanger:
mss(h4 - h3) = mws(h6 - h7) ⇒ h7 = 1.43 kJ/kg (Ans.)
Since expansion through expansion valves is isenthalpic,
h8 = h7 = 1.43 kJ/kg (Ans.)
h12 = h13 = 318.7 kJ/kg (Ans.)
c) From energy balance:
Heat transfer rate at condenser, Qc = m10(h10 - h11) = 365.5 kW (Ans.)
Heat transfer rate at absorber, Qa = m1h1+m8h8-m2h2) = 577.4 kW (Ans.)
Heat transfer rate at generator, Qg = m10h10+m6h6+Qd-m4h4) = 676.5 kW (Ans.)
Power input to pump, Wp = m2(h3 – h2) = 2.78 kW (Ans.)
System COP is given by:
⎛ Qe ⎞ ⎛ 351.7 ⎞
COP = ⎜ ⎟=⎜ ⎟ = 0.518 (Ans.)
⎜ Q g + Wp ⎟ ⎝ 676.5 + 2.78 ⎠
⎝ ⎠
Comments:
1. It can be seen that compared to heat input to the system at the generator, the
work input to the system is almost negligible (less than 0.5 percent)
2. The system COP is reduced as the required heat input to the generator
increases due to heat rejection at dephlegmator. However, this cannot be
avoided as rectification of the vapour is required. However, it is possible to
analyze the rectification process to minimize the heat rejection at the
dephlegmator

Lesson
15
Vapour Absorption
Based On Water-
Lithium Bromide Pair

The objectives of this lesson are to:
1. Introduce vapour absorption refrigeration systems based on water-lithium bromide

(Section 15.1)
2. Discuss properties of water-lithium bromide solution and describe pressure-
temperature-concentration (p-T-ξ) and enthalpy–temperature-concentration (h-T-ξ)
charts (Section 15.2)
3. Present steady-flow analysis of a single stage, water-lithium bromide system
(Section 15.3)
4. Discuss practical problems in actual water-lithium bromide systems (Section 15.4)
5. Describe commercial water-lithium bromide systems (Section 15.5)
6. Discuss heat sources for water-lithium bromide systems (Section 15.6)
7. Discuss typical application data for water-lithium bromide systems (Section 15.7)
8. Discuss briefly the methods of capacity control in water-lithium bromide systems
(Section 15.8)
1. Draw the schematic of the water-lithium bromide system and explain its working
principle
2. Evaluate the properties of water-lithium bromide solution using p-T-ξ and h-T-ξ
charts
3. Evaluate the steady-state performance of a single stage water-lithium bromide
system using the input data and fluid properties
4. Describe commercial water-lithium bromide systems and list practical problems in
these systems
5. List typical operating temperatures and performance aspects of water-lithium
bromide systems
6. Compare various capacity control methods in water-lithium bromide systems
15.1. Introduction
Vapour absorption refrigeration systems using water-lithium bromide pair are
extensively used in large capacity air conditioning systems. In these systems water is
used as refrigerant and a solution of lithium bromide in water is used as absorbent.
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 0oC. Hence these systems are used for air
conditioning applications. 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.

15.2. Properties of water-lithium bromide solutions
15.2.1. Composition:
The composition of water-lithium bromide solutions can be expressed either in

mass fraction (ξ) or mole fraction (x). For water-lithium bromide solutions, the mass
fraction ξ is defined as the ratio of mass of anhydrous lithium bromide to the total
mass of solution, i.e.,
mL
ξ= (15.1)
mL + mW
where mL and mW 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:
nL
x= (15.2)
nL + nW
where nL and nW 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;
mL m
nL = ; and n W = W (15.3)
ML MW
where ML (= 86.8 kg/kmol) and MW (= 18.0 kg/kmol) are the molecular weights of
anhydrous lithium bromide and water respectively.
15.2.2. Vapour pressure of water-lithium bromide solutions
Applying Raoult’s 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 )PW (15.4)
where PW 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 Raoult’s 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 Raoult’s law in a negative manner.
For example, at 50 percent mass fraction of lithium bromide and 25oC, Raoult’s law
predicts a vapour pressure of 26.2 mbar, whereas actual measurements show that it is
only 8.5 mbar.
The ratio of actual vapour pressure to that predicted by Raoult’s law is known as
activity coefficient. For the above example, the activity coefficient is 0.324.

The vapour pressure data of water-lithium bromide solutions can be very
conveniently represented in a Dühring plot. In a Dühring 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 Dühring plot. Figures 15.1 shows the Dühring plot. The Dühring plot can
be used for finding the vapour pressure data and also for plotting the operating cycle.
Figure 15.2 shows the water-lithium bromide based absorption refrigeration system
on Dühring plot. Other types of charts showing vapour pressure data for water-lithum
bromide systems are also available in literature. Figure 15.3 shows another chart
wherein the mass fraction of lithium bromide is plotted on abscissa, while saturation
temperature of pure water and vapour pressure are plotted as ordinates. Also shown
are lines of constant solution temperature on the chart. Pressure-temperature-
composition data are also available in the form of empirical equations.
P (mbar) Tsat (oC)
Solution Temperature, oC
Fig.15.1.: A typical Dühring plot

P
Pg 5
Condenser Generator
Qg
6
Qc
9 4
Heat exchanger
7
10 3
8
Pe Evaporator Absorber
1
Qe 2
Qa Solution pump
Te T∞ Tg T
Fig.15.2:
Basic H2O-LiBr
vapour system
absorption with a solution
refrigeration systemheat
withexchanger on Dühring
solution heat plot
exchanger
Fig.15.3: Pressure-Temperature-Concentration diagram for H2O-LiBr solution
15.2.3. Enthalpy of water-lithium bromide solutions
Since strong water-lithium bromide solution deviates from ideal solution

behaviour, 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 = ξ.h L + (1 − ξ)h W + Δh mix (15.5)

where hL and hW are the specific enthalpies of pure lithium bromide and water,
respectively at the same temperature. Figure 15.4 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 0 kJ/kg for liquid water at 0oC and
solid anhydrous lithium bromide salt at 25oC.
Fig.15.4: Enthalpy –Temperature - Concentration diagram for H2O-LiBr solution

15.2.4. 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, hW,liquid at any temperature T can be obtained from the equation:
h W ,liquid = 4.19 (T − Tref ) kJ / kg (15.6)

o
where Tref is the reference temperature, 0 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, hW,sup at low pressures and temperature T can be obtained approximately by
the equation:
h W ,sup = 2501 + 1.88 (T − Tref ) (15.7)
15.2.5. Crystallization
The pressure-temperature-mass fraction and enthalpy-temperature-mass

fraction charts (Figs. 15.3 and 15.4) 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.
15.3. Steady flow analysis of Water-Lithium Bromide Systems

Figure 15.5 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), kg/s
.
m ws = mass flow rate of weak solution (weak in LiBr), kg/s

1
C G
Qc
Qg
8
2
SHX
7
ER
9
3 ES
10
4
Qe A 6
E Qa
P
Fig.15.5: Schematic of a H2O-LiBr system
A: Absorber; C: Condenser; E: Evaporator; G: Generator; P: Solution Pump
SHX: Solution HX; ER: Refrigerant Expansion valve; ES: Solution Expansion valve
The circulation ratio (λ) is defined as the ratio of strong solution flow rate to
refrigerant flow rate. It is given by:
.
m ss
λ= .
(15.7)
m
this implies that the strong solution flow rate is given by:
. .
m ss = λ m (15.8)
The analysis is carried out by applying mass and energy balance across each
component.
Condenser:
. . .
m1 = m 2 = m (15.9)
.
Q c = m( h 1 − h 2 ) (15.10)
Pc = Psat (Tc ) (15.11)
where Tc is the condenser temperature

Expansion valve (refrigerant):
. . .
m2 = m3 = m (15.12)
h 2 = h3 (15.13)
Evaporator:
. . .
m3 = m 4 = m (15.14)
.
Q e = m( h 4 − h 3 ) (15.15)
Pe = Psat (Te ) (15.16)
where Te is the evaporator temperature
Absorber:
From total mass balance:

. . .
m + m ss = m ws
. . . .
(15.17)
m ss = λ m ⇒ m ws = (1 + λ ) m
From mass balance for pure water:
. . .
m + (1 − ξ ss ) m ss = (1 − ξ ws ) m ws
(15.18)
ξ ws
⇒λ=
ξ ss − ξ ws
. . .
Q a = m h 4 + λ m h 10 − (1 + λ) m h 5 (15.19)
.
or, Q a = m[(h 4 − h 5 ) + λ(h 10 − h 5 )] (15.20)
.
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 λ(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 (15.21)
. .
WP = m ws (h 6 − h 5 ) = (1 + λ) m(h 6 − h 5 ) (15.22)
however, if we assume the solution to be incompressible, then:

. .
WP = (1 + λ) m v sol (P6 − P5 ) =(1 + λ) m v sol (Pc − Pe ) (15.23)
where vsol is the specific volume of the solution which can be taken to be
approximately equal to 0.00055 m3/kg. Even though the solution pump work is small
it is still required in the selection of suitable pump.
Solution heat exchanger:
. . .
m 6 = m 7 = m ws
. . .
(15.24)
m 8 = m 9 = m ss
heat transfer rate in the solution heat exchanger, QHX is given by:
. .
Q HX = (1 + λ) m(h 7 − h 6 ) = λ m(h 8 − h 9 ) (15.25)
Generator:
. . .
m 7 = m 8 + m1 (15.26)
Heat input to the generator is given by:
. . .
Q g = m h 1 + λ m h 8 − (1 + λ ) m h 7 (15.27)
.
or, Q g = m[(h 1 − h 7 ) + λ(h 8 − h 7 )] (15.28)
.
in the above equation the 1st term on the RHS m(h 1 − h 7 ) represents energy required
to generate water vapour at state 1 from solution at state 7 and the 2nd term
.
m λ(h 8 − h 7 ) represents the sensible heat required to heat the solution from state 7 to
state 8.
Solution expansion vave:
. . .
m 9 = m 10 = m ws (15.29)
h 9 = h 10 (15.30)
The COP of the system is given by:
Qe Q
COP = ≈ e (15.31)
Q g + WP Q g

The second law (exergetic) efficiency of the system ηII is given by:
COP ⎛ Q ⎞⎛ Tg ⎞⎛ Tc − Te ⎞
η II = = ⎜ e ⎟⎜ ⎟⎜ ⎟⎟ (15.32)
COPmax ⎜⎝ Q g ⎟⎠⎜⎝ Tg − Tc ⎟⎜ Te
⎠⎝ ⎠
In order to find the steady-state performance of the system from the above set
of equations, one needs to know the operating temperatures, weak and strong solution
concentrations, effectiveness of solution heat exchanger and the refrigeration
capacity. It is generally assumed that the solution at the exit of absorber and generator
is at equilibrium so that the equilibrium P-T-ξ and h-T-ξ charts can be used for
evaluating solution property data. The effectiveness of solution heat exchanger, εHX is
given by:
(T7 − T6 )
ε HX = (15.33)
(T8 − T6 )
From the above equation the temperature of the weak solution entering the
generator (T7) can be obtained since T6 is almost equal to T5 and T8 is equal to the
generator temperature Tg. The temperature of superheated water vapour at state 1 may
be assumed to be equal to the strong solution temperature T8.
15.4. Practical problems in water-lithium bromide systems

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.
15.5. Commercial systems

Commercial water-lithium bromide systems can be:
1. Single stage or single-effect systems, and

2. Multi stage or multi-effect systems

Single stage systems operate under two pressures – one corresponding to the
condenser-generator (high pressure side) and the other corresponding to evaporator-
absorber. Single stage systems can be either:
1. Twin drum type, or

2. Single drum type
Since evaporator and absorber operate at the same pressure they can be housed in
a single vessel, similarly generator and condenser can be placed in another vessel as
these two components operate under a single pressure. Thus a twin drum system
consists of two vessels operating at high and low pressures. Figure 15.6 shows a
commercial, single stage, twin drum system.
Fig.15.6: A commercial, twin-drum type, water-lithium bromide system

As shown in the figure, the cooling water (which acts as heat sink) flows first to
absorber, extracts heat from absorber and then flows to the condenser for condenser
heat extraction. This is known as series arrangement. This arrangement is
advantageous as the required cooling water flow rate will be small and also by
sending the cooling water first to the absorber, the condenser can be operated at a
higher pressure to prevent crystallization. It is also possible to have cooling water
flowing parallelly to condenser and absorber, however, the cooling water requirement
in this case will be high. A refrigerant pump circulates liquid water in evaporator and
the water is sprayed onto evaporator tubes for good heat and mass transfer. Heater
tubes (steam or hot water or hot oil) are immersed in the strong solution pool of
generator for vapour generation. Pressure drops between evaporator and absorber and
between generator and condenser are minimized, large sized vapour lines are
eliminated and air leakages can also be reduced due to less number of joints.
Figure 15.7 shows a single stage system of single drum type in which all the four
components are housed in the same vessel. The vessel is divided into high and low
pressure sides by using a diaphragm.
Fig.15.7: A commercial, single-drum type, water-lithium bromide system

In multi-effect systems a series of generators operating at progressively
reducing pressures are used. Heat is supplied to the highest stage generator operating
at the highest pressure. The enthalpy of the steam generated from this generator is
used to generate some more refrigerant vapour in the lower stage generator and so on.
In this manner the heat input to the system is used efficiently by generating more
refrigerant vapour leading to higher COPs. However, these systems are more complex
in construction and require a much higher heat source temperatures in the highest
stage generator. Figures 15.8 and 15.9 show commercial double-effect systems.
Figure 15.10 shows the double effect cycle on Dühring plot.
Fig.15.8: A commercial, double-effect, water-lithium bromide system

Fig.15.9: A commercial, double-effect, water-lithium bromide system
Qg,in
Ph,g
Qc,out
Pc=Pl,g
Pe=Pa
Qe,in Qa,out
Te Tc = Ta Tl,g Th,g
Fig.15.10: Double effect VARS on Dühring plot

15.6. Heat sources for water-lithium bromide systems
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 120oC to produce chilled
water at 7oC when the condenser operates at about 46oC and the absorber operates at
about 40oC. The COPs obtained aor 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.
15.7. Minimum heat source temperatures for LiBr-Water

systems
Application data for a single-stage water-lithium bromide vapour absorption
system with an output chilled water temperature of 6.7oC (for air conditioning
applications) is shown in Table 15.1.
Cooling water temperature Minimum Heat source COP

(inlet to absorber & temperature
condenser) (Inlet to generator)
23.9oC 65oC 0.75
26.7oC 75 oC 0.74
29.4oC 85 oC 0.72
32.2oC 95 oC 0.71
Table 15.1. 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
15oC 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 (≈ 150oC). 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 50oC.
15.7 Capacity control

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.
Questions:
1. Vapour absorption refrigeration systems using water-lithium bromide:
a) Are used in large air conditioning systems

b) Are used in large frozen food storage applications
c) Operate under vacuum
c) All of the above
Ans. a) and c)
2. For a required refrigeration capacity, the solution heat exchanger used in water-
lithium bromide systems:
a) Reduces the required heat input to generator

b) Reduces the heat rejection rate at absorber
c) Reduces heat rejection rate at condenser
d) Reduces the required heat source temperature
Ans. a) and b)
3. In water-lithium bromide systems:
a) Crystallization of solution is likely to occur in absorber

b) Crystallization of solution is likely to occur in solution heat exchanger
c) Crystallization is likely to occur when generator temperature falls
d) Crystallization is likely to occur when condenser pressure falls
Ans. a) and d)
4. In commercial water-lithium bromide systems
a) Crystallization is avoided by regulating cooling water flow rate to condenser

b) Crystallization is avoided by adding additives
c) An air purging system is used to maintain vacuum
d) All of the above

Ans. d)
5. Commercial multi-effect absorption systems:
a) Yield higher COPs

b) Yield higher refrigeration temperatures
c) Require lower heat source temperatures
d) Require higher heat source temperatures
Ans. a) and d)
6. In water-lithium bromide systems:
a) The required heat source temperature should be higher than minimum heat
generation temperature
b) The required heat source temperature decreases as cooling water temperature
increases
c) The required heat source temperature is higher for air cooled condensers, compared
to water cooled condensers
d) All of the above
Ans. a) and c)
7. In commercial water-lithium bromide systems, the system capacity is regulated by:
a) Controlling the weak solution flow rate to generator

b) Controlling the flow rate of chilled water to evaporator
c) Controlling the temperature of heating fluid to generator
d) All of the above
Ans. a) and c)
8. 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
5oC (Psat=8.72 mbar) and a condensing temperature of 50oC (Psat=123.3 mbar). The
exit temperatures of absorber and generator are 40oC and 110oC 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) System COP and second law efficiency, and

d) Solution pump work (density of solution = 1200 kg/m3).
Given:
Refrigeration capacity : 300 kW
Evaporator temperature : 5o C
Condenser temperature : 50oC
Absorber temperature : 40oC
Generator temperature : 110oC
Weak solution concentration,ξWS : 0.578
Strong solution concentration, ξSS : 0.66
Effectiveness of solution HX, εHX : 1.0
Density of solution,ρsol : 1200 kg/m3
Refrigerant exit at evaporator & condenser : Saturated
Solution at the exit of absorber & generator : Equilibrium
Referring to Fig.15.5;
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 = 110oC
⇒ enthalpy of vapour = 2501+1.88 X 110 = 2708 kJ/kg
From the definition of effectiveness of solution HX;
εHX = [mSSCp,SS(T8-T9)]/[mSSCp,SS(T8-T6)] = 1.0 (∵ mSS < mWS)
⇒ T9 = T6 = 40oC
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 (oC) (mbar) fraction, ξ (kJ/kg)
1 110 123.3 - 2708
2 50 123.3 - 209
3 5 8.72 - 209
4 5 8.72 - 2510
5 40 8.72 0.578 -154
6 40 123.3 0.578 -154
7 - 123.3 0.578 -37.5
8 110 123.3 0.66 -13
9 40 123.3 0.66 -146
10 40 8.72 0.66 -146
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 oC.
Enthalpy of weak solution at the exit of solution HX is obtained from the energy
balance equation:mWS(h7-h6) = mSS(h8-h9) ⇒ h7 = h6+mSS(h8-h9)/mWS = -37.5 kJ/kg
a) Required mass flow rate of refrigerant, m = Qe/(h4-h3) = 0.1304 kg/s (Ans.)

Circulation ratio, λ = mSS/m = ξWS/(ξSS-ξWS) = 7.05
∴mass flow rate of strong solution, mSS = λm = 0.9193 kg/s (Ans.)
mass flow rate of weak solution, mWS = (λ+1)m = 1.05 kg/s (Ans.)
b) Heat transfer rates at various components:
Evaporator: Qe = 300 kW (input data)
Absorber: From energy balance:
Qa = mh4+mSSh10-mWSh5 = 354.74 kW (Ans.)

Generator: From energy balance:
Qg = mh1+mSSh8-mWSh7 = 380.54 kW (Ans.)
Condenser: From energy balance:
Qc = m(h1-h2) = 325.9 kW (Ans.)
Solution heat exchanger: From energy balance:
QSHX = mλ(h8-h9) = m(λ+1)(h7-h6) = 122.3 kW (Ans.)
c) System COP (neglecting pump work) = Qe/Qg = 0.7884 (Ans.)
Second law efficiency = COP/COPCarnot
COPCarnot = [Te/(Tc-Te)][(Tg-Ta)/Tg] = 1.129
∴Second law efficiency = 0.6983 (Ans.)
d) Solution pump work (assuming the solution to be incompressible)
WP = vsol(P6-P5) = (P6-P5)/ρsol = (123.3-8.72)*10-1/1200 = 0.0095 kW (Ans.)

UNIT 4 REFRIGERANTS
Structure
4.1 Introduction
Objectives
4.2 Primary and Secondary Refrigerants

4.3 Classification of Refrigerants
4.4 Designation of Refrigerants
4.5 Desirable Properties of Refrigerants
4.5.1 Thermodynamic Properties
4.5.2 Chemical Properties
4.5.3 Physical Properties
4.5.4 Safety Criteria
4.5.5 Economic Criteria
4.6 Common Refrigerants
4.7 Ozone Depletion Potential and Global Warming Potential
4.8 Secondary Refrigerants
4.9 Illustrative Problems
4.10 Summary
4.11 Answers to SAQs
4.1 INTRODUCTION
The working agent in a refrigerating system that absorbs carries or releases heat
from the place to be cooled or refrigerated can be termed as a refrigerant. This
heat transfer generally takes place through a phase change of the refrigerant. A
more complete definition of a refrigerant could be given as follows:
“Refrigerant is the fluid used for heat transfer in a refrigerating system that
absorbs heat during evaporation from the region of low temperature and
pressure, and releases heat during condensation at a region of higher
temperature and pressure.”
Objectives
In this unit, we shall learn about the different refrigerants used in various
refrigeration systems. At present, we have a large number of refrigerants available
to us depending on the requirements of the particular refrigerating system. A
detailed study of these refrigerants has thus become imperative. This unit is
intended to serve as an introductory guide to the study of refrigerants.
After studying this unit, you should be able to learn
 the different classifications of refrigerants,
 naming convention for refrigerants,
 properties of individual refrigerants, and
 environmental effects related to the use of these refrigerants.
Refrigeration and Air
Conditioning 4.2 PRIMARY AND SECONDARY REFRIGERANTS
Primary refrigerants are those which can be directly used for the purpose of
refrigeration. If the refrigerant is allowed to flow freely into the space to be
refrigerated and there is no danger of possible harm to human beings, then
primary refrigerants are used. The refrigerants used in home refrigerators like
Freon-12 are primary refrigerants.
On the other hand, there may be certain situations in which we cannot allow the
refrigerant to come in direct contact with the items being refrigerated, and then
the refrigerant used is termed as a secondary refrigerant. As for example, we
cannot allow a toxic refrigerant to be used for air conditioning in residential
buildings. There are some refrigerants which are highly inflammable and so their
direct use is forbidden for safety reasons. Again, it may so happen that if direct
refrigeration, such as in cooling a big cold storage, is allowed, then the amount of
refrigerant required may be so large that its cost becomes prohibitively high.
These are some typical situations for which we favour the use of secondary
refrigerants. Water and brine solutions are common examples of secondary
refrigerants.
4.3 CLASSIFICATION OF REFRIGERANTS

Refrigerants can be broadly classified based on the following:
Working Principle
Under this heading, we have the primary or common refrigerants and the
secondary refrigerants.
The primary refrigerants are those that pass through the processes of
compression, cooling or condensation, expansion and evaporation or
warming up during cyclic processes. Ammonia, R12, R22, carbon dioxide
come under this class of refrigerants.
On the other hand, the medium which does not go through the cyclic
processes in a refrigeration system and is only used as a medium for heat
transfer are referred to as secondary refrigerants. Water, brine solutions of
sodium chloride and calcium chloride come under this category.
Safety Considerations
Under this heading, we have the following three sub-divisions.
Safe refrigerants
These are the non-toxic, non-flammable refrigerants such as R11,
R12, R13, R14, R21, R22, R113, R114, methyl chloride, carbon
dioxide, water etc.
Toxic and moderately flammable
Dichloroethylene methyl format, ethylchloride, sulphur dioxide,
ammonia etc. come under this category.
Highly flammable refrigerants
The refrigerants under this category are butane, isobutene, propane,
ethane, methane, ethylene etc.
Chemical Compositions
They are further sub-divided as
54
Halocarbon compounds Refrigerants
These are obtained by replacing one or more hydrogen atoms in

ethane or methane with halogens.
Azeotropes
These are the mixtures of two or more refrigerants and behave as a
compound.
Oxygen and Nitrogen Compounds
Refrigerants having either oxygen or nitrogen molecules in their
structure, such as ammonia, are grouped separately and have a
separate nomenclature from the halogenated refrigerants.
Cyclic organic Compounds
The compounds coming under this class are R316, R317 and R318.
Inorganic Compounds
These are further divided into two categories: Cryogenic and Non-
cryogenic.
Cryogenic fluids are those which are applied for achieving
temperatures as low as – 160 0C to – 273 0C. Above this temperature
range, we can use a multi-stage refrigeration system to realise the
desired temperature. But below – 160 0C, this is not possible since the
COP of the cycle becomes very low. To attain temperatures below –
160 0C, we use refrigerants such as nitrogen, oxygen, helium,
hydrogen etc. and for temperatures close to – 273 0C, magnetic
cooling is employed.
The inorganic compounds which are employed above the cryogenic
temperature ranges come under the remaining sub-division of
inorganic refrigerants.
Unsaturated Compounds
Compounds such as ethylene, propylene etc. are grouped under this
head and grouped under the 1000 series for convenience.
Miscellaneous
This group contains those compounds which cannot be grouped under
the other components. They are indicated by the 700 series with the
last numbers being their molecular weight. Examples include air,
carbon dioxide, sulphur dioxide etc.
As we can see from the above sub-divisions, they are not mutually
exclusive. A compound may come under more than one sub-division.
Hence, the importance of adopting the various naming conventions to
designate the different refrigerants cannot be underestimated.
4.4 DESIGNATION OF REFRIGERANTS

The American Society of Refrigerating Engineers (ASRE) has developed certain
conventions for use in naming different types of refrigerants. These naming
conventions differ according to the type of refrigerant. Each refrigerant type is
denoted by a different series. Thus, we have separate series for halogenated
refrigerants and other types. The naming conventions are simple and easy to
55
Refrigeration and Air follow. These conventions are now accepted worldwide and help to name the
Conditioning
large variety of refrigerants available commercially nowadays.
Halocarbon Compounds
These are represented by a three digit nomenclature. Here, the first digit
represents the number of carbon atoms in the compound minus one, the
second digit stands for the number of hydrogen atoms plus one while the
third digit stands for the number of fluorine atoms. The remaining atoms are
chlorine.
As an example, let us consider the refrigerant having R22 as its three digit
nomenclature.
According to the above mentioned convention,
No. of C atoms in R22: C – 1 = 0 => C = 1
No. of H atoms in R22: H + 1 = 2 => H = 1
No. of F atoms in R22: F = 2
Since there is only one carbon atom in the compound, this compound has
originated from the methane series (CH4). From the calculation, we can see
there is one hydrogen atom and two fluorine atoms. The remaining valence
bond of carbon will be balanced by chlorine. Thus, the substance is
Figure 4.1 Graphical Representation of Monochloro-Difluoro-Methane

Therefore, chemical formula of R22 is CHClF2 and has the name
Monochloro-difluoro-methane (figure. 4.1).
Taking again the example of R134, we can calculate its chemical formula as
above which gives us
No. of C atoms: C – 1 = 1 => C = 2
No. of H atoms: H + 1 = 3 => H = 2
No. of F atoms: F = 4
Therefore, no. of Cl atoms: Cl = 0
Figure 4.2 Graphical Representation of Tetrafluoroethane
The compound is C2H2F2 and its name is Tetrafluoroethane (Figure. 4.2).

The non-halogenated refrigerants follow a different naming convention
which is dependant upon the series of the refrigerant.
56
Refrigerants
4.5 DESIRABLE PROPERTIES OF REFRIGERANTS
The vast number of refrigerants available in the market today allows us to choose
a refrigerant depending upon the operating conditions of the refrigeration system.
As such, there is no refrigerant that can be advantageously used under all
operating conditions and in all types of refrigeration systems. In spite of that, we
can state certain desirable properties that a refrigerant should posses. These
properties can be divided into favourable thermodynamic, chemical and physical
properties:
4.5.1 Thermodynamic Properties
Critical Temperature and Pressure
The critical temperature of the refrigerant should be as high as possible
above the condensing temperature in order to have a greater heat transfer at
a constant temperature. If this is not taken care of, then we will have
excessive power consumption by the refrigeration system.
The critical pressure should be moderate and positive. A very high pressure
will make the system heavy and bulky whereas in case of very low
pressures, there is a possibility of air leaking into the refrigerating system.
Specific Heat
The specific heat of the liquid should be as small as possible. This ensures
that the irreversibilities associated with throttling are small and there is
greater subcooling of the liquid. On the other hand, the specific heat of
vapor should be high to have less superheating of the vapor.
Enthalpy of Vaporization
This should be as large as possible to minimize the area under superheat and
the area reduction due to throttling. Also, the higher value of enthalpy of
vaporization lowers the required flow rate per ton of refrigeration.
Taking these three factors into account, the T-s and p-h diagrams of an ideal
refrigerant would be as shown in Figures. 4.3 (a) and 4.3 (b).
T p
3 2 3 2
4 1 4 1
s h
Figure 4.3(a) T-S Plot of an Ideal Figure 4.3( b) p-h Plot of an Ideal
Refrigerant Refrigerant
These properties are practically not found in any refrigerant. So, a trade-off
has to be done in order to achieve as high a COP as possible.
Conductivity
The conductivity of the refrigerant should be as high as possible so that the
size of the evaporator and condenser is manageable. From this viewpoint,
ammonia has a better conductivity than that of R12 or R22 and is more
57
Refrigeration and Air suitable than the latter. But, ammonia is toxic and this does not allow its use
Conditioning
in home refrigeration systems.
Evaporator and Condenser Pressure
Both the evaporator and condenser pressures need to be above atmospheric
pressure otherwise there is a possibility of air leaking into the system.
Presence of air drastically reduces the capacity of the refrigeration system.
Also, due to presence of moisture in air, acids or other corrosive compounds
may form and this may affect the tubing of the refrigeration system.
Compression Ratio
The compression ratio needs to be as small as possible otherwise the
leakage of refrigerant occurs across the piston. Also, the volumetric
efficiency is affected.
Freezing Point
It should be as low as possible or else there will be a possibility of blockage
of passages during flow of fluid through evaporator.
Volume of Refrigerant Handled Per Ton of Refrigeration
This should be as small as possible in order to have a small size of the
compressor. The type of compressor is decided by this value. For
refrigerants like R12, R500, R22 etc., a reciprocating compressor is
suitable. For others like R11 and water, a centrifugal compressor is required
to handle the large volume.
Coefficient of Performance
The Coefficient of performance or COP has a direct bearing on the running
cost of the refrigeration system. Higher the magnitude of COP, lower will
be the running cost. Since, the COP of any refrigeration system is limited by
the Carnot COP, for large operating pressures a multi-stage refrigeration
system should be employed. CO2 has a very low COP. Hence, it is not
suitable for use as a refrigerant.
Density
The density of the refrigerant should be as large as possible. In
reciprocating compressors, the pressure rise is accomplished by squeezing
the entrapped fluid inside the piston-cylinder assembly. Hence, density
decides the size of the cylinder. Again in centrifugal compressors pressure
rise is related to the density of the vapor. A high value of density results in
high pressure rise.
Compression Temperature
Whenever a refrigerant gets compressed, there is a rise in the temperature of
the refrigerant resulting in the heating of the cylinder walls of the
compressor. This necessitates external cooling of the cylinder walls to
prevent volumetric and material losses. Refrigerants having lowest
compression temperatures are thus better than others.
4.5.2Chemical Properties
Chemical Stability and Inertness
It should be chemically stable for the operating ranges of temperature. Also,
it should not react with the materials of the refrigeration system or with
which it comes into contact. Further, it should be chemically inert and must
58
not undergo polymerization reactions at either the lower or higher ranges of Refrigerants
temperatures.
Action on Rubber or Plastics
Rubber and plastics are used extensively in the refrigeration system. These
materials are mostly used in the seals and gaskets of the refrigeration
system. They help to prevent the leakage of the refrigerant and ensure the
smooth functioning of the compressor. The refrigerant should not react with
them or else there might be leakage of refrigerant from the system or loss of
functioning of the compressor.
Flammability
The refrigerant should be inert and not catch fire when subjected to high
temperatures. From this viewpoint CO2 is the most suitable as it is not only
non-flammable, but also acts as a fire-extinguisher. Ethane, butane,
isobutene are highly undesirable as they catch fire quickly.
Effect on Oil
The refrigerant should not react with the lubricating oil else, there is a
possibility of loss of lubricating action due to either thickening or thinning
of the oil. It should not be soluble in the oil else there will be reduction in
the viscosity of the lubricating oil.
Effect on Commodity
If the refrigerant is directly used for chilling, then it should not affect the
commodity kept in the conditioned space. Also, in case where direct cooling
is not employed, the refrigerant should still not affect the commodity if
there is any leakage.
Toxicity
The refrigerant used in air conditioning, food preservation etc. should not be
toxic as they will come into contact with human beings.
4.5.3 Physical Properties
Leakage and Detection
Since pressures higher than atmospheric are usually employed in
refrigeration systems, there is a possibility of leakage of refrigerants after
long period of operation. It is desirable to detect this leak early else the
system would operate under reduced capacity or stop functioning
altogether. Hence, it is desirable that the refrigerant has a pungent smell so
that its leakage can be detected immediately.
Miscibility with Oil
The refrigerant should not be miscible with the oil else the lubricating
strength will be reduced.
Viscosity
It should be as small as possible to ensure that the pressure drop in the
system is as small as possible. A low viscosity refrigerant will require less
energy for its circulation through the refrigeration system.
4.5.4 Safety Criteria
Under safety criteria, we consider the toxicity, flammability, action on perishable
food and formation of explosive compound on exposure to air. An ideal
59
Refrigeration and Air refrigerant should be non-toxic, non-flammable, have no effect on food products
Conditioning
and should not react with atmospheric air. No refrigerant satisfy these criteria
fully. We can therefore, group refrigerants into different sub-groups based on
their flammability and toxicity levels.
4.5.5 Economic Criteria
Apart from the thermodynamic, chemical, physical and safety criteria, there is
another criterion by which we judge an ideal refrigerant. The economic criterion
takes into account the cost of the refrigerant, the availability and supply levels of
the refrigerant, cost of storage and handling. We discuss each of these in detail
below.
Cost of Refrigerant
The cost of the refrigerant has a big impact on the overall cost of the
refrigeration system. Hence, its cost should be as low as possible. From this
viewpoint, ammonia and water are ideally suited, but their low
thermodynamic and chemical properties restrict their use in all types of
refrigeration systems. Particularly, for flooded type evaporator or
condenser, the refrigerant amount required is high and their cost needs to be
factored in while making the initial investments.
Availability and Supply
The refrigerant should be easily available in the market and in abundant
quantity. This ensures that the cost of the refrigerant is not prohibitive. An
abundant and free supply of the refrigerant ensures that refrigeration
systems will be designed specifically for use with them.
Storage and Handling
The refrigerant should be such that it can be conveniently stored and
handled during transportation and charging. It should be stored in as small a
pressure vessel as possible. Also, if we have to handle a toxic or flammable
refrigerant, then the cost involved will be higher compared to handling and
storage cost of non-toxic and non-flammable refrigerant.
From the above discussions of the ideal properties of refrigerants, we can
come to the conclusion that none of the refrigerants in current use and
available satisfy these conditions fully. As such, we have to make a detailed
analysis of the different factors like cost, performance of the refrigeration
system and safety issues before deciding on using a particular refrigerant.
4.6 COMMON REFRIGERANTS

The refrigerants which are available commercially in the market are numerous.
Some of them which are in common use are mentioned below:
Air
Air (molecular weight 28.97, specific heats cp = 1.04 kJ/kgK and cv = 0.712
kJ/kg-K) is one of the earliest refrigerant to be used in the refrigeration
systems. Its advantages are that it is available free of cost, is non-toxic and
non-flammable and does not affect the commodity if pure. However, air
suffers from a number of drawbacks. Air contains moisture and this reacts
with the material of the evaporator and condenser severely affecting their
working capacity. Further, there is a possibility that the passages may be
blocked by the formation of ice from this moisture. The COP of air is of the
order of 0.6 and thus, not suitable for use in refrigeration systems on a
60
commercial scale. It is mainly used for air conditioning in aircrafts where Refrigerants
efficiency of operation is of secondary importance.
Ammonia
Ammonia (molecular weight 17) is one of the oldest refrigerants and it was
commonly employed in places where toxicity effects were of secondary
importance. Its advantages are its low cost, low specific volume, high COP
(of the order of 4.0) and high refrigeration effect per unit mass of the
refrigerant. Its primary drawback is its toxicity which prevents its use in air-
conditioning and food preservation systems. Ammonia has a boiling point
of -33 0C at atmospheric pressure.
Carbon Dioxide
Carbon dioxide (molecular weight 44) is a non-toxic and non-poisonous
refrigerant. Also, it is not only non-flammable but and is an excellent
extinguishing agent as well. Its other advantages are that it is chemically
stable, immiscible with the lubricating oil and does not affect the metal used
in the system. It has a low specific volume and this requires volume
displacement per ton of refrigeration. However, its critical pressure is too
high. Also, its critical temperature is only 31 0C which makes it unsuitable
for use in countries with a hot climate like India. It is an excellent
refrigerant for low temperature refrigeration.
Sulphur Dioxide
Sulphur dioxide (molecular weight 64) is a colourless, suffocating and
irritating gas and is twice as heavy as air at atmospheric conditions. It was
mostly used as a household refrigerant in the older days, but has since been
discarded for better refrigerants. It suffers from a lot of disadvantages.
Sulphur dioxide reacts with water forming sulphurous acid, which in
presence of oxygen becomes sulphuric acid, a corrosive compound for
metals. It is non-flammable but attacks foodstuff on coming in contact with
it. It is also partially miscible with the lubricating oil.
Hydrocarbons
This group consists of colourless fluids normally in gaseous state and made
up of various combinations of carbon and hydrogen. Most of the
refrigerants from this category are suitable for low temperature
refrigeration. Isobutane falls in this category and has been suitable for
domestic refrigeration. They are non-poisonous, but are flammable and
highly explosive when exposed to air. The molecular weight and boiling
point of each gas varies according to the number of hydrogen and carbon
atoms. The larger the number of hydrogen and carbon atoms, the heavier is
the gas and higher is its boiling point.
Halocarbon Refrigerants
The halocarbon refrigerants are formed by replacing one or more of
hydrogen atoms of methane or ethane by one or more atoms of the three
halogens: fluorine, chlorine or bromine. Some of the refrigerants coming
under this category are mentioned below:
Refrigerant R12
The refrigerant R12 is the most widely used refrigerant in the
domestic and large commercial establishments. Its chemical formula
is CCl2F2 and its boiling point is -300C at 1 bar. It is a non-flammable,
non-explosive, non-irritating, non-toxic and odourless refrigerant. It
61
Refrigeration and Air remains chemically stable up to 5500C. Also, it does not affect the
Conditioning
material of the refrigeration system. It is available in abundance and is
quite cheap. However, its use is being discontinued nowadays for its
contribution to ozone depletion which will be discussed later.
Refrigerant R13
Its chemical formula is CClF3. it is a non-flammable, non-toxic and
stable refrigerant. It is very suitable for achieving low temperatures in
a cascade refrigeration system. Its specific volume is high and
therefore, it is suitable for centrifugal compressors. However, it also
has a negative effect on ozone depletion.
Refrigerant R22
Its chemical formula is CHClF2. it is also a non-toxic, non-flammable,
non-corrosive and non-irritating refrigerant. It is the most common
refrigerant for use in large refrigeration systems and is preferred to
R12.
Refrigerant R114
Its chemical formula is C2Cl2F4. Its boiling point corresponding to 1
bar is about 30C. It has properties very similar to those of R12 with
respect to water and oil combination. It is not suitable for low
temperature refrigeration since it has negative evaporator pressure
even at around 9 0C. It is non-toxic, non-explosive and non-corrosive
even in the presence of water.
4.7 OZONE DEPLETION AND GLOBAL WARMING

POTENTIAL
An issue of growing concern for the present day environment is the impact of the
various refrigerants on the ozone depletion and global warming of the
environment. The main culprits in this case are the chlorine containing
halogenated hydrocarbons, commonly known as chlorofluorocarbons or CFC
which are being used as refrigerants.
The Earth’s atmosphere is made up of various layers. The layer just above the
Earth’s surface is known as the troposphere. The troposphere extends up to 10 km
from the surface. The ozone layer is just above the troposphere and located in the
stratosphere. The stratospheric ozone is Earth’s natural protection to harmful
ultraviolet (UV) radiation from the sun. UV radiation is harmful to human, plant
and animal life. The ozone layer gets depleted by the action of these refrigerants.
CFCs, when they are released from the surface of the Earth, rise slowly into the
stratosphere. Here they are bombarded by the incoming UV light from the Sun,
which releases the chlorine atoms from the parent compound. It is this chlorine
atom which reacts with the ozone molecules. The detailed reactions are given
below:
Chlorofluorocarbon Irradiated with UV light  free Cl
Cl + O3 ClO + O2
ClO + O  Cl + O2
The free chlorine atom can again take part in the reaction with another ozone
atom. A single chlorine atom, released by the action of UV radiation on CFCs,
62
can catalytically destroy tens of thousands of ozone molecules during its Refrigerants
residence in the stratosphere Figure 4.4.
3. Chlorine atom
1. UV radiation 2. Chlorine atom hits ozone
hits CFC breaks away. molecule.
molecule
4. Chlorine atom takes one 6. Two oxygen atoms form

oxygen atom to form chlorine an oxygen molecule.
5. Oxygen atom hits
monoxide and one molecule of Chlorine atom is free and
chlorine monoxide
oxygen. repeats the depletion
molecule.
process.
Carbon atom Fluorine atom Chlorine atom Oxygen atom

Figure 4.4. Graphical Representation of the Reactions Involved in Ozone Depletion
Ozone depletion will permit UV rays to reach earth which can result in several
harmful effects on living creatures. The UV radiation can cause skin cancer,
cataracts and destruction of the body’s immune system.
Along with ozone depletion, CFC refrigerants also contribute to a large extent in
the global warming of the planet. These gases create a greenhouse effect which
traps the heat in the lower atmosphere. This makes the Earth warmer because the
green house gases do not allow infrared radiation to pas through tem. The earth
emits IR rays during its cooling when sun is not there. CO2 is the most important
green house gas but one molecule of CFC has warming potential which is more
than 1000 times the warming potential of one molecule of CO2. Sun’s rays are
allowed into the lower atmosphere, but the heat from these rays is not allowed to
escape.
The “Montreal Protocol on Substances that Deplete the Ozone Layer” signed in
1987 by several countries stipulates the gradual phase-out of CFC refrigerants.
Use of HCFC refrigerant is advocated as an interim measure, but even these are to
be eventually phased out. This therefore necessitates the need for new refrigerants
which can atleast perform as well as the refrigerants they replace without harming
the atmosphere. Based on this requirement, HFC 134a emerges as the refrigerant
of the future.
4.8 SECONDARY REFRIGERANTS

In some refrigeration systems, the refrigerant is not put into direct use. This is
done mainly out of safety considerations. As an example, it is not desirable to use
toxic refrigerants like ammonia in home air- conditioning and home refrigeration
systems. Also, in some cases the size of the refrigerated space may be so large
that direct refrigeration may be uneconomical. In such case, an indirect way is
employed. The refrigerants used in this way do not pass through the cyclic
process and are referred to as secondary refrigerants. The refrigerants commonly
used in this way are water and brine solutions of calcium or sodium. This
63
Refrigeration and Air therefore allows the use of a smaller size refrigerator with a considerably less
Conditioning
amount of refrigerant. Also, since the refrigerant does not come in direct contact,
cheaper grade materials can be used for the heat exchanger.
Due to its toxicity, ammonia cannot be used as a refrigerant in residential air
conditioners. Therefore, the usual practice is to chill brine over the evaporator coil
and then air is cooled by passing over the brine coil. This method eliminates the
dangers of toxification on account of ammonia leakage into the air streams.
Sodium chloride brine solutions are most common up to – 15 0C while calcium
chloride brine solutions can be used up to – 50 0C. However, these solutions are
very corrosive to metals such as brass, copper and aluminium. In place of them,
sometimes certain chemicals known as antifreeze are used with water to prevent
clogging.
4.9 ILLUSTRATIVE PROBLEMS

A refrigerator is to be designed to operate between 228 K (– 45 0C) and 273 K (0
0
C). The selection is to be made out of the refrigerants: R12 and ammonia. From
the data provided in the table below, calculate the following: a) COP, b) power
per ton, c) compression ratio, d) working pressure of condenser and evaporator
and e) compression temperature.
Refrigerants Sat. Sat. hf hg sf sg cpg

temp.(0C) pressure(bar) (kJ/kg) (kJ/kg) (kJ/kgK) (kJ/kgK) (kJ/kgK)
– 45 0.505 – 4.4 167.84 0.0190 0.7360 ------

R12
0 3.09 36.15 188.69 0.1420 0.7008 0.62
Ammonia – 40 0.535 – 22.4 1378.76 0.0961 6.0475 ------
0 4.242 180.88 1443.34 0.7139 5.3368 2.72
Solution
Referring to the T-s diagram given below (Figure 4.5), it can be seen:
2
3
4
0 6 5 1
10 9 8 7 s
Figure 4.5. T-S Diagram of the Problem
64
R12 (dichlorodifluoromethane) Refrigerants
T   T 
s1  0.7360  s2  s3  c p ln  2   0.7008  0.62 ln  2 
 T3   273 
i.e.T2  288.95K
Then,
h2  h3  c p T2  T 3   188.69  0.62(288.95  273)
i.e. h2  198.58 kJ kg
167.84-36.15
(a) COP  (h1  h4 ) (h2  h1 )  =4.284
198.58-167.84
(b) Power per ton is given by: 3.5 COP  0.8169kW
R717 (Ammonia)
T   T 
s1  6.0475  s2  s3  c p ln  2   5.3368  2.72 ln  2 
 T3   273 
i.e.T2  354.52K
Then,
h2  h3  c p T2  T 3   1443.34  2.72(354.52  273)
i.e. h2  1665.07 kJ kg
1378.76-180.00
(a) COP  (h1  h4 ) (h2  h1 )  =4.184
1665.07-1378.76
(b) Power per ton is given by: 3.5 COP  0.8365kW
The table for the comparison of the above refrigerants is presented below:
Refrigerants COP Power Compression Comp. Temp Compression Evaporator

per pressure pressure pressure
0
ton (p2/p1) K C (bar) (bar)
R12 4.284 817 6.19 288.95 15.95 3.09 0.505
Ammonia 4.184 837 7.93 354.52 81.52 4.22 0.535
From the tabular values, we can see that from the view of power consumption,
R12 is better than ammonia. But, it gives negative evaporator pressure which is
less than the atmospheric pressure. Ammonia, too suffers from the same problem.
Also, we can see that the difference in COP and power consumption of ammonia
and R12 is not very much. However, since ammonia is toxic, its use is very
restricted. R12 is widely used in home refrigeration systems. The problem of
negative evaporator pressures is overcome by employing a hermetically sealed
compressor which prevents the leakage of air into the evaporator.
65
Refrigeration and Air
Conditioning 4.10 SUMMARY
Here, in this chapter we have undertaken a detailed and complete study of the
various refrigerants used in the home air-conditioning and refrigeration systems
as well as those used in industrial refrigeration systems.
We have learnt the basis of nomenclature of the various refrigerants. This
nomenclature allows us to easily identify each and every refrigerant available in
the market today.
In the preceding sections, we have studied the thermal, physical and chemical
characteristics which an ideal refrigerant should posses. We have also studied the
actual thermal, chemical and physical properties of some of the common
refrigerants available commercially. From our discussion, we have realised that
no refrigerant satisfies fully the characteristics of an ideal refrigerant. Hence, we
have to make an informed choice about the refrigerant we will use depending
upon the purpose of the refrigeration system.
The field of refrigeration and air-conditioning has undergone tremendous changes
in the last century. More and more new refrigerants having improved properties
are being produced globally. Research in this field is now directed towards
producing better environment friendly refrigerants and in replacing old
refrigeration systems using halogenated refrigerants with the newer ones. We can
be sure that in the future, refrigerants will be produced which will not only match
the performance characteristics of the present day refrigerants, but also surpass
them. And all this will be done without causing any destructive effect upon the
environment.
4.11 ANSWERS TO SAQs

Refer the relevant preceding texts in the unit or other useful books on the topic
listed in the section “Further Readings” to get the answers of the SAQs.
66
Lesson
26
Refrigerants
The specific objectives of this lecture are to:
1. Discuss the importance of selection of suitable refrigerant in a refrigeration
system (Section 26.1)
2. Classify refrigerants into primary and secondary, and discuss the important
differences between primary and secondary refrigerants (Section 26.2)
3. Discuss refrigerant selection criteria based on thermodynamic, thermophysical,
environmental and economic properties (Section 26.3)
4. Describe the numbering system used for designating refrigerants (Section
26.4)
5. Present a comparison between different refrigerants (Section 26.5)
1. Explain the importance of refrigerant selection

2. Differentiate between primary and secondary refrigerants
3. List the criteria used in selecting refrigerants
4. List important thermodynamic and environmental properties influencing
refrigerant selection
5. Write the chemical formula of a refrigerant from its number
6. Compare different refrigerants and suggest replacements for CFCs and
HCFCs
26.1. Introduction:
The thermodynamic efficiency of a refrigeration system depends mainly on
its operating temperatures. However, important practical issues such as the
system design, size, initial and operating costs, safety, reliability, and
serviceability etc. depend very much on the type of refrigerant selected for a
given application. Due to several environmental issues such as ozone layer
depletion and global warming and their relation to the various refrigerants used,
the selection of suitable refrigerant has become one of the most important issues
in recent times. Replacement of an existing refrigerant by a completely new
refrigerant, for whatever reason, is an expensive proposition as it may call for
several changes in the design and manufacturing of refrigeration systems. Hence
it is very important to understand the issues related to the selection and use of
refrigerants. In principle, any fluid can be used as a refrigerant. Air used in an air
cycle refrigeration system can also be considered as a refrigerant. However, in
this lecture the attention is mainly focused on those fluids that can be used as
refrigerants in vapour compression refrigeration systems only.
26.2. Primary and secondary refrigerants:

Fluids suitable for refrigeration purposes can be classified into primary and
secondary refrigerants. Primary refrigerants are those fluids, which are used
directly as working fluids, for example in vapour compression and vapour
absorption refrigeration systems. When used in compression or absorption
systems, these fluids provide refrigeration by undergoing a phase change
process in the evaporator. As the name implies, secondary refrigerants are those
liquids, which are used for transporting thermal energy from one location to other.
Secondary refrigerants are also known under the name brines or antifreezes. Of

course, if the operating temperatures are above 0oC, then pure water can also be
used as secondary refrigerant, for example in large air conditioning systems.
Antifreezes or brines are used when refrigeration is required at sub-zero
temperatures. Unlike primary refrigerants, the secondary refrigerants do not
undergo phase change as they transport energy from one location to other. An
important property of a secondary refrigerant is its freezing point. Generally, the
freezing point of a brine will be lower than the freezing point of its constituents.
The temperature at which freezing of a brine takes place its depends on its
concentration. The concentration at which a lowest temperature can be reached
without solidification is called as eutectic point. The commonly used secondary
refrigerants are the solutions of water and ethylene glycol, propylene glycol or
calcium chloride. These solutions are known under the general name of brines.
In this lecture attention is focused on primary refrigerants used mainly in

vapour compression refrigeration systems. As discussed earlier, in an absorption
refrigeration system, a refrigerant and absorbent combination is used as the
working fluid.
26.3. Refrigerant selection criteria:

Selection of refrigerant for a particular application is based on the following
requirements:
i. Thermodynamic and thermo-physical properties

ii. Environmental and safety properties, and
iii. Economics
26.3.1. Thermodynamic and thermo-physical properties:
The requirements are:
a) Suction pressure: At a given evaporator temperature, the saturation pressure

should be above atmospheric for prevention of air or moisture ingress into the
system and ease of leak detection. Higher suction pressure is better as it leads to
smaller compressor displacement
b) Discharge pressure: At a given condenser temperature, the discharge

pressure should be as small as possible to allow light-weight construction of
compressor, condenser etc.
c) Pressure ratio: Should be as small as possible for high volumetric efficiency

and low power consumption
d) Latent heat of vaporization: Should be as large as possible so that the required

mass flow rate per unit cooling capacity will be small
The above requirements are somewhat contradictory, as the operating

pressures, temperatures and latent heat of vaporization are related by Clausius-
Clapeyron Equation:
h fg s fg
ln (Psat ) = − + (26.1)
RT R

In the above equation, Psat is the saturation pressure (in atm.) at a temperature
T(in Kelvin), hfg and sfg are enthalpy and entropy of vaporization and R is the gas
constant. Since the change in entropy of vaporization is relatively small, from the
above equation it can be shown that:
Pc ⎡ h fg ⎛ 1 1 ⎞⎤
= exp ⎢ ⎜⎜ − ⎟⎟ ⎥ (26.2)
Pe ⎢⎣ R ⎝ Te Tc ⎠ ⎥⎦
In the above equation, Pc and Pe are the condenser and evaporator

pressures, Tc and Te are condenser and evaporator temperatures. From the
above equation, it can be seen that for given condenser and evaporator
temperatures as the latent heat of vaporization increases, the pressure ratio also
increases. Hence a trade-off is required between the latent heat of vaporization
and pressure ratio.
In addition to the above properties; the following properties are also

important:
e) Isentropic index of compression: Should be as small as possible so that the

temperature rise during compression will be small
f) Liquid specific heat: Should be small so that degree of subcooling will be large
leading to smaller amount of flash gas at evaporator inlet
g) Vapour specific heat: Should be large so that the degree of superheating will
be small
h) Thermal conductivity: Thermal conductivity in both liquid as well as vapour

phase should be high for higher heat transfer coefficients
i) Viscosity: Viscosity should be small in both liquid and vapour phases for
smaller frictional pressure drops
The thermodynamic properties are interrelated and mainly depend on

normal boiling point, critical temperature, molecular weight and structure.
The normal boiling point indicates the useful temperature levels as it is

directly related to the operating pressures. A high critical temperature yields
higher COP due to smaller compressor superheat and smaller flash gas losses.
On the other hand since the vapour pressure will be low when critical
temperature is high, the volumetric capacity will be lower for refrigerants with high
critical temperatures. This once again shows a need for trade-off between high
COP and high volumetric capacity. It is observed that for most of the refrigerants
the ratio of normal boiling point to critical temperature is in the range of 0.6 to 0.7.
Thus the normal boiling point is a good indicator of the critical temperature of the
refrigerant.
The important properties such as latent heat of vaporization and specific

heat depend on the molecular weight and structure of the molecule. Trouton’s
rule shows that the latent heat of vaporization will be high for refrigerants having
lower molecular weight. The specific heat of refrigerant is related to the structure
of the molecule. If specific heat of refrigerant vapour is low then the shape of the
vapour dome will be such that the compression process starting with a saturated
point terminates in the superheated zone (i.e, compression process will be
dry). However, a small value of vapour specific heat indicates higher degree of
superheat. Since vapour and liquid specific heats are also related, a large value
of vapour specific heat results in a higher value of liquid specific heat, leading to
higher flash gas losses. Studies show that in general the optimum value of molar
vapour specific heat lies in the range of 40 to 100 kJ/kmol.K.
The freezing point of the refrigerant should be lower than the lowest
operating temperature of the cycle to prevent blockage of refrigerant pipelines.
26.3.2. Environmental and safety properties:
Next to thermodynamic and thermophysical properties, the environmental

and safety properties are very important. In fact, at present the environment
friendliness of the refrigerant is a major factor in deciding the usefulness of a
particular refrigerant. The important environmental and safety properties are:
a) Ozone Depletion Potential (ODP): According to the Montreal protocol, the ODP
of refrigerants should be zero, i.e., they should be non-ozone depleting
substances. Refrigerants having non-zero ODP have either already been
phased-out (e.g. R 11, R 12) or will be phased-out in near-future(e.g. R22). Since
ODP depends mainly on the presence of chlorine or bromine in the molecules,
refrigerants having either chlorine (i.e., CFCs and HCFCs) or bromine cannot be
used under the new regulations
b) Global Warming Potential (GWP): Refrigerants should have as low a GWP

value as possible to minimize the problem of global warming. Refrigerants with
zero ODP but a high value of GWP (e.g. R134a) are likely to be regulated in
future.
c) Total Equivalent Warming Index (TEWI): The factor TEWI considers both
direct (due to release into atmosphere) and indirect (through energy
consumption) contributions of refrigerants to global warming. Naturally,
refrigerants with as a low a value of TEWI are preferable from global warming
point of view.
d) Toxicity: Ideally, refrigerants used in a refrigeration system should be non-

toxic. However, all fluids other than air can be called as toxic as they will cause
suffocation when their concentration is large enough. Thus toxicity is a relative
term, which becomes meaningful only when the degree of concentration and time
of exposure required to produce harmful effects are specified. Some fluids are
toxic even in small concentrations. Some fluids are mildly toxic, i.e., they are
dangerous only when the concentration is large and duration of exposure is long.
Some refrigerants such as CFCs and HCFCs are non-toxic when mixed with air
in normal condition. However, when they come in contact with an open flame or
an electrical heating element, they decompose forming highly toxic elements (e.g.
phosgene-COCl2). In general the degree of hazard depends on:
- Amount of refrigerant used vs total space

- Type of occupancy
- Presence of open flames
- Odor of refrigerant, and
- Maintenance condition

Thus from toxicity point-of-view, the usefulness of a particular refrigerant
depends on the specific application.
e) Flammability: The refrigerants should preferably be non-flammable and non-

explosive. For flammable refrigerants special precautions should be taken to
avoid accidents.
Based on the above criteria, ASHRAE has divided refrigerants into six safety
groups (A1 to A3 and B1 to B3). Refrigerants belonging to Group A1 (e.g. R11,
R12, R22, R134a, R744, R718) are least hazardous, while refrigerants belonging
to Group B3 (e.g. R1140) are most hazardous.
Other important properties are:
f) Chemical stability: The refrigerants should be chemically stable as long as they

are inside the refrigeration system.
g) Compatibility with common materials of construction (both metals and non-

metals)
h) Miscibility with lubricating oils: Oil separators have to be used if the refrigerant
is not miscible with lubricating oil (e.g. ammonia). Refrigerants that are
completely miscible with oils are easier to handle (e.g. R12). However, for
refrigerants with limited solubility (e.g. R 22) special precautions should be taken
while designing the system to ensure oil return to the compressor
i) Dilelectric strength: This is an important property for systems using hermetic
compressors. For these systems the refrigerants should have as high a dielectric
strength as possible
j) Ease of leak detection: In the event of leakage of refrigerant from the system, it
should be easy to detect the leaks.
26.3.3. Economic properties:
The refrigerant used should preferably be inexpensive and easily

available.
26.4. Designation of refrigerants:

Figure 26.1 shows the classification of fluids used as refrigerants in vapour
compression refrigeration systems. Since a large number of refrigerants have
been developed over the years for a wide variety of applications, a numbering
system has been adopted to designate various refrigerants. From the number
one can get some useful information about the type of refrigerant, its chemical
composition, molecular weight etc. All the refrigerants are designated by R
followed by a unique number.
i) Fully saturated, halogenated compounds: These refrigerants are derivatives

of alkanes (CnH2n+2) such as methane (CH4), ethane (C2H6). These refrigerants
are designated by R XYZ, where:
X+1 indicates the number of Carbon (C) atoms

Y-1 indicates number of Hydrogen (H) atoms, and
Z indicates number of Fluorine (F) atoms
The balance indicates the number of Chlorine atoms. Only 2 digits indicates that
the value of X is zero.
Ex: R 22
X = 0 ⇒ No. of Carbon atoms = 0+1 = 1 ⇒ derivative of methane (CH4)
Y = 2 ⇒ No. of Hydrogen atoms = 2-1 = 1
Z = 2 ⇒ No. of Fluorine atoms = 2
The balance = 4 – no. of (H+F) atoms = 4-1-2 = 1 ⇒ No. of Chlorine atoms = 1
∴The chemical formula of R 22 = CHClF2
Similarly it can be shown that the chemical formula of:
R12 = CCl2F2
R134a = C2H2F4 (derivative of ethane)
(letter a stands for isomer, e.g. molecules having same chemical composition but
different atomic arrangement, e.g. R134 and R134a)
ii) Inorganic refrigerants: These are designated by number 7 followed by the

molecular weight of the refrigerant (rounded-off).
Ex.: Ammonia: Molecular weight is 17, ∴ the designation is R 717

Carbon dioxide: Molecular weight is 44, ∴ the designation is R 744
Water: Molecular weight is 18, ∴ the designation is R 718

Refrigerants
Pure fluids Mixtures

- Azeotropic
- Zeotropic
Synthetic Natural
- CFCs - Organic (HCs)
- HCFCs - Inorganic
- HFCs o NH3
o CO2
o H2O
Fig.26.1: Classification of fluids used as refrigerants
iii) Mixtures: Azeotropic mixtures are designated by 500 series, where as

zeotropic refrigerants (e.g. non-azeotropic mixtures) are designated by 400
series.
Azeotropic mixtures:
R 500: Mixture of R 12 (73.8 %) and R 152a (26.2%)

R 502: Mixture of R 22 (48.8 %) and R 115 (51.2%)
R503: Mixture of R 23 (40.1 %) and R 13 (59.9%)
R507A: Mixture of R 125 (50%) and R 143a (50%)
Zeotropic mixtures:
R404A : Mixture of R 125 (44%), R 143a (52%) and R 134a (4%)

R407A : Mixture of R 32 (20%), R 125 (40%) and R 134a (40%)
R407B : Mixture of R 32 (10%), R 125 (70%) and R 134a (20%)
R410A : Mixture of R 32 (50%) and R 125 (50%)

iv) Hydrocarbons:
Propane (C3H8) : R 290

n-butane (C4H10) : R 600
iso-butane (C4H10) : R 600a
Unsaturated Hydrocarbons: R1150 (C2H4)

R1270 (C3H6)
26.5. Comparison between different refrigerants:

Synthetic refrigerants that were commonly used for refrigeration, cold storage
and air conditioning applications are: R 11 (CFC 11), R 12 (CFC 12), R 22
(HCFC 22), R 502 (CFC 12+HCFC 22) etc. However, these refrigerants have to
be phased out due to their Ozone Depletion Potential (ODP). The synthetic
replacements for the older refrigerants are: R-134a (HFC-134a) and blends of
HFCs. Generally, synthetic refrigerants are non-toxic and non-flammable.
However, compared to the natural refrigerants the synthetic refrigerants offer
lower performance and they also have higher Global Warming Potential (GWP).
As a result, the synthetic refrigerants face an uncertain future. The most
commonly used natural refrigerant is ammonia. This is also one of the oldest
known refrigerants. Ammonia has good thermodynamic, thermophysical and
environmental properties. However, it is toxic and is not compatible with some of
the common materials of construction such as copper, which somewhat restricts
its application. Other natural refrigerants that are being suggested are
hydrocarbons (HCs) and carbon di-oxide (R-744). Though these refrigerants
have some specific problems owing to their eco-friendliness, they are being
studied widely and are likely to play a prominent role in future.
Prior to the environmental issues of ozone layer depletion and global

warming, the most widely used refrigerants were: R 11, R 12, R 22, R 502 and
ammonia. Of these, R 11 was primarily used with centrifugal compressors in air
conditioning applications. R 12 was used primarily in small capacity refrigeration
and cold storage applications, while the other refrigerants were used in large
systems such as large air conditioning plants or cold storages. Among the
refrigerants used, except ammonia, all the other refrigerants are synthetic
refrigerants and are non-toxic and non-flammable. Though ammonia is toxic, it
has been very widely used due to its excellent thermodynamic and
thermophysical properties. The scenario changed completely after the discovery
of ozone layer depletion in 1974. The depletion of stratospheric ozone layer was
attributed to chlorine and bromine containing chemicals such as Halons, CFCs,
HCFCs etc. Since ozone layer depletion could lead to catastrophe on a global
level, it has been agreed by the global community to phase out the ozone
depleting substances (ODS). As a result except ammonia, all the other
refrigerants used in cold storages had to be phased-out and a search for suitable
replacements began in earnest. At the same time, it was also observed that in
addition to ozone layer depletion, most of the conventional synthetic refrigerants
also cause significant global warming. In view of the environmental problems
caused by the synthetic refrigerants, opinions differed on replacements for
conventional refrigerants. The alternate refrigerants can be classified into two
broad groups:
i) Non-ODS, synthetic refrigerants based on Hydro-Fluoro-Carbons
(HFCs) and their blends
ii) Natural refrigerants including ammonia, carbon dioxide, hydrocarbons
and their blends
It should be noted that the use of natural refrigerants such as carbon dioxide,
hydrocarbons is not a new phenomena, but is a revival of the once-used-and-
discarded technologies in a much better form. Since the natural refrigerants are
essentially making a comeback, one advantage of using them is that they are
familiar in terms of their strengths and weaknesses. Another important advantage
is that they are completely environment friendly, unlike the HFC based
refrigerants, which do have considerable global warming potential. The alternate
synthetic refrigerants are normally non-toxic and non-flammable. It is also
possible to use blends of various HFCs to obtain new refrigerant mixtures with
required properties to suit specific applications. However, most of these blends
are non-azeotropic in nature, as a result there could be significant temperature
glides during evaporation and condensation, and it is also important take
precautions to prevent leakage, as this will change the composition of the
mixture. Table 26.1 shows a list of refrigerants being replaced and their
replacements.

Refrigerant Application Substitute suggested
Retrofit(R)/New (N)
R 11(CFC) Large air conditioning systems R 123 (R,N)
o
NBP = 23.7 C Industrial heat pumps
R 141b (N)
hfg at NBP=182.5 kJ/kg As foam blowing agent
Tcr =197.98oC R 245fa (N)
Cp/Cv = 1.13
n-pentane (R,N)
ODP = 1.0
GWP = 3500
R 12 (CFC) Domestic refrigerators R 22 (R,N)
o
NBP = -29.8 C Small air conditioners R 134a (R,N)
hfg at NBP=165.8 kJ/kg Water coolers R 227ea (N)
Tcr =112.04oC Small cold storages R 401A,R 401B (R,N)
Cp/Cv = 1.126 R 411A,R 411B (R,N)
ODP = 1.0 R 717 (N)
GWP = 7300
R 22 (HCFC) Air conditioning systems R 410A, R 410B (N)
o
NBP = -40.8 C Cold storages R 417A (R,N)
hfg at NBP=233.2 kJ/kg R 407C (R,N)
Tcr =96.02oC R 507,R 507A (R,N)
Cp/Cv = 1.166 R 404A (R,N)
ODP = 0.05 R 717 (N)
GWP = 1500
R 134a (HFC) Used as replacement for R 12 No replacement required
o
NBP = -26.15 C in domestic refrigerators, water
hfg at NBP=222.5 kJ/kg coolers, automobile A/Cs etc * Immiscible in mineral oils
Tcr =101.06oC * Highly hygroscopic
Cp/Cv = 1.102
ODP = 0.0
GWP = 1200
R 717 (NH3) Cold storages No replacement required
o
NBP = -33.35 C Ice plants
hfg at NBP=1368.9 kJ/kg Food processing * Toxic and flammable
Tcr =133.0oC Frozen food cabinets * Incompatible with copper
Cp/Cv = 1.31 * Highly efficient
ODP = 0.0 * Inexpensive and available
GWP = 0.0
R 744 (CO2) Cold storages No replacement required
o
NBP = -78.4 C Air conditioning systems * Very low critical temperature
hfg at 40oC=321.3 kJ/kg Simultaneous cooling and * Eco-friendly
Tcr =31.1oC heating (Transcritical cycle) * Inexpensive and available
Cp/Cv = 1.3
ODP = 0.0
GWP = 1.0
Table 26.1: Refrigerants, their applications and substitutes

Refrigerant Application Substitute suggested
Retrofit(R)/New (N)
R718 (H2O) Absorption systems No replacement required
o
NBP = 100. C Steam jet systems * High NBP
hfg at NBP=2257.9 kJ/kg * High freezing point
Tcr =374.15oC * Large specific volume
Cp/Cv = 1.33 * Eco-friendly
ODP = 0.0 * Inexpensive and available
GWP = 1.0
R600a (iso-butane) Replacement for R 12 No replacement required
o
NBP = -11.73 C Domestic refrigerators * Flammable
hfg at NBP=367.7 kJ/kg Water coolers * Eco-friendly
Tcr =135.0oC
Cp/Cv = 1.086
ODP = 0.0
GWP = 3.0
Table 26.1: Refrigerants, their applications and substitutes (contd.)
Questions and answers:
1. Which of the following statements are TRUE?
a) A primary refrigerant does not undergo phase change in a refrigeration cycle

b) A secondary refrigerant does not undergo phase change in a refrigeration
cycle
c) The freezing point of a brine is generally lower than the freezing point of its
constituents
d) The freezing point of a brine is generally higher than the freezing point of its
constituents
Ans.: b) and c)
a) The suction pressure of a refrigerant should be as high as possible

b) The suction pressure of a refrigerant should be as low as possible
c) The discharge pressure of a refrigerant should be as high as possible
d) The discharge pressure of a refrigerant should be as low as possible
Ans.: a) and d)

a) At a given temperature, as the latent heat of vaporization increases, the

saturation pressure decreases
b) For given evaporator and condenser temperatures, as the latent heat of
vaporization increases, the pressure ratio decreases
c) As the latent heat of vaporization increases, the required mass flow rate of
refrigerant, becomes smaller for a given capacity
d) For a given pressure ratio, as the isentropic index of compression increases,
the compressor discharge temperature increases
Ans.: a), c) and d)
a) A refrigerant having high critical temperature yields high COP and high
volumetric capacity
b) A refrigerant having high critical temperature yields low COP and high
volumetric capacity
c) A refrigerant having high critical temperature yields low COP and low
volumetric capacity
d) A refrigerant having high critical temperature yields high COP and low
volumetric capacity
Ans.: d)
a) Low molecular weight refrigerants have high latent heat of vaporization

b) Low molecular weight refrigerants have low latent heat of vaporization
c) For saturated state at the inlet to the compressor, a refrigerant having high
vapour specific heat may give rise to wet compression
d) For saturated state at the inlet to the compressor, a refrigerant having low
vapour specific heat may give rise to wet compression
Ans.: a) and c)
6. The chemical formula of refrigerant R11 is:
a) CCl3F
b) CClF3
c) CClHF
d)CHF
Ans.: a)

7. The chemical formula of R141 is:
a) C2H3ClF3
b) C2H2Cl3F
c) C2H3Cl2F
d) C2H2ClF3
Ans.: c)
8. Which of the following statements is TRUE?
a) Evaporation process is non-isothermal for zeotropic mixtures

b) Evaporation process is non-isothermal for azeotropic mixtures
c) Composition of azeotropic mixture changes in the event of a leak
d) Composition of zeotropic mixture changes in the event of a leak
Ans.: a) and d)
9. Which of the following refrigerants are phased-out due to Montreal protocol on

ozone layer depletion
a) R11
b) R21
c) R12
d) R32
Ans.: a), b) and c)
10. Which of the following refrigerants replace R12 in domestic refrigerators?
a) R22
b) R11
c) R134a
d) R141b
Ans.: c)
11. Which of the following refrigerants are suggested as replacements for R22 in
large air conditioning and cold storage systems?
a) R134a
b) R21
c) R410A
d) R407C
Ans.: c) and d)

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Lesson

At the end of the lecture, the student should be able to:

1. List salient features of vapour absorption refrigeration systems and compare

Version 1 ME, IIT Kharagpur 2

14.2. Basic principle

For example, Fig.14.1 shows an arrangement, which consists of two vessels A

Version 1 ME, IIT Kharagpur 3

4.24 kPa 1.22 kPa

Water at 30oC 50% LiBr soln. at 30oC

1.22 kPa 1.22 kPa

Water at 10oC 50% LiBr soln. at 30oC

4.24 kPa 4.24 kPa

Fig.14.1: Basic principle of vapour absorption systems

Version 1 ME, IIT Kharagpur 4

The system described may be called as an Intermittent Absorption

Though the intermittent absorption refrigeration systems discussed above are

Version 1 ME, IIT Kharagpur 5

Exp.device Exp.device Pe Pump Exp.device

Figs.14.2: a) Vapour compression refrigeration system (VCRS)

Figure 14.2(a) and (b) show a continuous output vapour compression

Version 1 ME, IIT Kharagpur 6

Thus absorption systems are advantageous where a large quantity of low-grade

14.3. Maximum COP of ideal absorption refrigeration system

Version 1 ME, IIT Kharagpur 7

Fig.14.3: Various energy transfers in a vapour absorption refrigeration system

From first law of thermodynamics,

From second law of thermodynamics,

Version 1 ME, IIT Kharagpur 8

Thus an ideal vapour absorption refrigeration system can be considered to be a

Fig.14.4: Vapour absorption refrigeration system as a combination of a heat

Version 1 ME, IIT Kharagpur 9

where m1 and m2 are the mass of components 1 and 2, respectively

An important property of a mixture is its miscibility. A mixture is said to be

14.4.1. Ideal, homogeneous binary mixtures

A binary mixture of components 1 and 2 is called as an ideal mixture, when it

Version 1 ME, IIT Kharagpur 10

and the total pressure Ptotal is given by:

If one of the components, say component 2 is non-volatile compared to component

Ptotal ≈ Pv,1 = x 1 .P1,sat (14.24)

Real mixtures deviate from ideal mixtures since:

1. A real solution either contracts or expands upon mixing, i.e.,

Version 1 ME, IIT Kharagpur 11

Fig.14.5: Pressure-concentration behaviour of ideal and real mixtures at a constant

Version 1 ME, IIT Kharagpur 12

Fig.14.6: Enthalpy-concentration behaviour of an ideal mixture and a real mixture with

14.5. Basic Vapour Absorption Refrigeration System

Version 1 ME, IIT Kharagpur 13

The thermodynamic performance of the above system can be evaluated by

14.6. Refrigerant-absorbent combinations for VARS

Version 1 ME, IIT Kharagpur 14

The most commonly used refrigerant-absorbent pairs in commercial systems are:

1. Water-Lithium Bromide (H2O-LiBr) system for above 0oC applications such

Of late efforts are being made to develop other refrigerant-absorbent systems

Currently, large water-lithium bromide (H2O-LiBr) systems are extensively

2. Absorption of the refrigerant by the absorbent in a vapour absorption refrigeration

3. An absorption system consisting of only two closed vessels:

Version 1 ME, IIT Kharagpur 15

a) Requires only thermal energy as input

5. For an ideal refrigerant-absorbent mixture:

a) There is neither expansion nor contraction upon mixing

6. For a refrigerant-absorbent mixture with a negative deviation from Raoult’s law:

a) The mixing process is exothermic

7. Refrigerant-absorbent pairs used in vapour absorption refrigeration systems should:

a) Exhibit negative deviation from Raoult’s law at absorber