REFRIGERANTS

ME115
REFRIGERATION
ENGINEERING

WEEK 8
2019-2020/4T

Prepared by:
Engr. Manuel B. Rustria
July 24, 2020
 OBJECTIVES
 Explain the importance of refrigerant selection.
 Differentiate between primary and secondary refrigerants.
 List the basis of choice of refrigerant.
 List important thermodynamic and environmental properties influencing
refrigerant selection.
 Explain the effect of CFC’s on the ozone layer.
 Explain the characteristics of secondary refrigerants.
PRIMARY AND SECONDARY REFRIGERANTS
 PRIMARY AND SECONDARY REFRIGERANTS
 Primary refrigerants – refrigerants used in vapor-compression systems
 Secondary refrigerants (antifreezes and brines) – liquids used for
transporting low-temperature heat energy from one location to another

 The most common refrigerants are the fluorinated hydrocarbons, but

numerous other substances also function well as refrigerants, including
many inorganic compounds and hydrocarbons.
HALOCARBON COMPOUNDS
 HALOCARBON COMPOUNDS
 The halocarbon group includes refrigerants which contain one or more of
the three halogens chlorine, fluorine, and bromine.
 The numerical designation, the chemical name, and the chemical formula of
some of the commercially available members of this group are shown in
Table 15-1.
 HALOCARBON COMPOUNDS
 The numbering system in the halocarbon group follows this pattern:
 the first digit on he right is the number of fluorine atoms in the
compound;
 the second digit from the right is one more than the number of hygdrogen
atoms in the compound; and
 the third digit from the right is one less than the number of carbon atoms.
– When third number is zero, it is omitted.
 HALOCARBON COMPOUNDS
Table 15-1 Some halocarbon refrigerants
Numerical
designation Chemical name Chemical formula
11 Trichloromonofluoromethane
12 Dichlorodifluoromethane
13 Monochlorotrifluoromethane
22 Monochlorodifluoromethane
40 Methyl chloride
113 Trichlorotrifluoroethane
114 Dichlorotetrafluoroethane
INORGANIC COMPOUNDS
 INORGANIC COMPOUNDS
 Many of the early refrigerants were inorganic compounds, and some have
maintained their prominence to this day.
 These compounds are listed in Table 15-2.
 INORGANIC COMPOUNDS
Table 15-2 Some inorganic refrigerants
Numerical
designation t Chemical name Chemical formula
717 Ammonia
718 Water
729 Air
744 Carbon dioxide
764 Sulfur dioxide
HYDROCARBONS
 HYDROCARBONS
 Many hydrocarbons are suitable as refrigerants, especially for service in the
petroleum and petrochemical industry.
 Several such refrigerants are listed in Table 15-3.
 HYDROCARBONS
Table 15-3 Hydrocarbon refrigerants
Numerical
designation t Chemical name Chemical formula
50 Methane
170 Ethane
290 Propane
Follows same principle as the halocarbon scheme.
AZEOTROPES
 AZEOTROPES
 An azeotropic mixture of two substances is one which cannot be separated
into its components by distillation.
 An azeotrope evaporates and condenses as a single substance with
properties that are different from those of either constituent.
 The most popular azeotrope is refrigerant 502, which is a mixture of 48.8
percent refrigerant and 51.2 percent refrigerant 115.
 The properties of saturated refrigerant 502 are given in Table A-8, and the
properties of superheated vapor are shown in Fig. A-5.
COMPARISON OF SOME COMMON REFRIGERANTS
 COMPARISON OF COMMON REFRIGERANTS
 Some thermodynamic and efficiency characteristics of several common
refrigerants are presented in Table 15-4.
 The pressures, refrigerating effect, volume flow per unit refrigeration
capacity, and the coefficient of performance (COP) are based on the
standard vapor-compression cycle with an evaporating temperature of -15°C
and a condensing temperature of 30°C.
 COMPARISON OF COMMON REFRIGERANTS
Table 15-4 Thermodynamic characteristics of several refrigerants
Operation on a standard vapor-compression cycle with an evaporating
temperature of -15°C and a condensing temperature of 30°C.
Evapo- Conden- Refri- Suction vapor
rating sing gerating flow per kW of
Refri- pressure, pressure, Pressure effect refrigeration,
gerant kPa kPa ratio kJ/kg L/s COP
11 20.4 125.5 6.15 155.4 4.90 5.03
12 182.7 744.6 4.08 116.3 0.782 4.70
22 295.8 1192.1 4.03 162.8 0.476 4.66
502 349.6 1308.6 3.74 106.2 0.484 4.37
717 236.5 1166.6 4.93 1103.4 0.462 4.76
 COMPARISON OF COMMON REFRIGERANTS
 The operating pressures should be low enough for lightweight vessels and
pipes to contain the refrigerant.
 On the other hand, pressures below atmospheric pressure, which occur in
refrigerant 11 evaporators, have the disadvantage of drawing air into the
evaporator if there are any leaks.
 Systems using this refrigerant should be equipped with purger to eliminate
any air that leaks in.
 A low pressure ration is desirable from the standpoint of any type of
compressor—reciprocating, screw, or centrifugal.
 COMPARISON OF COMMON REFRIGERANTS
 The refrigerating effect would at first seem to be a good indicator of the
cycle efficiency, but this property must be considered in combination with
the work of compression.
 Refrigerant 717 (ammonia), for example, has a refrigerating effect much
larger than the other refrigerants but the work of compression of ammonia
is also high, so that its COP is of the same order of magnitude as that of the
other refrigerants shown.
 COMPARISON OF COMMON REFRIGERANTS
 The flow rate of suction vapor per kilowatt of refrigeration influences the
pumping rate and/or the type of compressor.
 refrigerants 22, 502, and 717 show comparable values of this term, while
refrigerant 12 is less dense than those three and requires a higher vapor
flow rate.
 The high volume flow rate of refrigerant 11 indicates why it is used in
centrifugal compressors.
 COMPARISON OF COMMON REFRIGERANTS
 The coefficient of performance of a standard refrigeration cycle using
refrigerant 11 is higher than the other, but this advantage is not sufficient to
permit its application in any but systems using centrifugal compressors.
 The COP’s of refrigerant 12, 22, and 717 are nearly the same, and while that
of refrigerant 502 is the lowest shown, this refrigerant has some other
advantages.
 As a basis of comparison the COP of the Carnot cycle operating at the
evaporating and condensing temperatures of Table 15-4 is 5.74.
PHYSICAL AND CHEMICAL COMPARISON
 PHYSICAL AND CHEMICAL COMPARISON
 Two important characteristics of refrigerants from a safety standpoint are its
flammability and toxicity.
 Of the refrigerants listed in Table 15-4, ammonia is listed as flammable with
16 and 25 percent ammonia by volume in air, while the others are
considered nonflammable.
 With respect to toxicity, refrigerant 12 is considered nontoxic in
concentrations up to 20 percent by volume for an exposure period of less
than 2 h, while ammonia is assigned to a group of refrigerants considered
injurious or lethal in concentrattions of ½ to 1 percent for exposures of ½ in
duration.
 Refrigerants 11, 22, and 502 are in a class slightly more toxic than refrigerant
12.
 PHYSICAL AND CHEMICAL COMPARISON
 How the refrigerant combines with oil in the system is a factor in its
selection.
 No chemical reaction between the refrigerant and the lubricating oil of the
compressor is anticipated, but the miscibility of the oil and the refrigerant is
of concern.
 In reciprocating and screw compressors some oil carries out of the
compressor with the refrigerant discharge gas.
 The oil passes through the condenser and on to the evaporator, where the
refrigerant vaporizes off, leaving the oil to reduce the heat-transfer
effectiveness of the evaporator.
 PHYSICAL AND CHEMICAL COMPARISON
 Several procedures are available to prevent oil from reaching the evaporator
or to remove it after it collects.
 An oil separator placed in the discharge gas line removes oil comtinuously
and returns it to the compressor, where it belongs.
 Refrigerant 12 and oil are miscible, whereas refrigerant 22 is partially
miscible and ammonia is not miscible with oil.
 Oil in the the evaporator of refrigerant 12 system is not nearly so
detrimental to heat transfer as in ammonia system, where it separates.
 Oil can be drained from ammonia evaporators, but in refrigerant 12 systems
the velocity in the suction line must be kept high enough to carry oil back to
the compressor.
 PHYSICAL AND CHEMICAL COMPARISON
 The popularity of several refrigerants rises and falls over the years;
refrigerant 12 was most popular and was then supplanted in popularity by
refrigerant 22 because of its lower volume flow rater per unit capacity.
 Refrigerant 502 has become popular lately, because it has comparable
volume flow rates to refrigerant 22 but oil is more miscible in it and because
it has lower discharge temperaures.
 PHYSICAL AND CHEMICAL COMPARISON
 When a leak occurs in a refrigeration system, the refrigerant may come in
contact with the product, such as food.
 The halocarbons are generally considered to have negligible effect on foods,
furs, or fabrics for short exposures.
 Prolonged exposure to ammonia could result in food tasting or smelling of
ammonia, although it should be remembered that a small amount of
ammonia (0.01 to 0.1 percent) is present in foods naturally.
 PHYSICAL AND CHEMICAL COMPARISON
 Reaction of a refrigerant with a material of construction used in the piping,
vessels, and compressors does not usually influence the selection of the
refrigerant, but the refrigerant used does frequently dictate the material
employed in the system.
 Certain metals may be attacked by refrigerants.
 Ammonia, for example, reacts with copper, brass, or other cuprous alloys in
the presence of of water.
 Iron and steel are therefore used in ammonia systems.
 The halocarbons may react with zinc but not copper, aluminum, iron, or
steel.
 PHYSICAL AND CHEMICAL COMPARISON
 In the presence of a small quantity of water, however, the halocarbons form
acids which attack most metals,
 The halocarbons attack natural rubber; therefore synthetic material should
be used as gaskets and for other sealing purposes.
THERMAL CONDUCTIVITY AND VISCOSITY
 THERMAL CONDUCTIVITY AND VISCOSITY
 Occasionally the engineer will need viscosity and thermal-conductivity data
for making heat transfer and/or flow calculations; Table 15-5 presents a
summary of these properties.
 THERMAL CONDUCTIVITY AND VISCOSITY
Table 15-5 Thermal conductivities and viscosities
of saturated refrigerant liquid and vapor.
Viscosity, Pa ∙ s Conductivity, W/m ∙ K
Refrigerant Liquid Vapor Liquid Vapor
-40 0.000922 0.106
-20 0.000694 0.100
0 0.000546 0.0943
11
20 0.000441 0.0000103 0.0890
40 0.000367 0.0000119 0.0832 0.00841
60 0.000312 0.0000127 0.0777 0.0093
 THERMAL CONDUCTIVITY AND VISCOSITY
Table 15-5 Thermal conductivities and viscosities
of saturated refrigerant liquid and vapor. (Cont.)
Viscosity, Pa ∙ s Conductivity, W/m ∙ K
Refrigerant Liquid Vapor Liquid Vapor
-40 0.000409 0.0931
-20 0.000325 0.0000108 0.0857 0.00734
0 0.000267 0.0000118 0.0784 0.00838
12
20 0.000225 0.0000126 0.0711 0.00938
40 0.000194 0.0000135 0.0637 0.0105
60 0.000169 0.0000148 0.0564 0.0118
 THERMAL CONDUCTIVITY AND VISCOSITY
Table 15-5 Thermal conductivities and viscosities
of saturated refrigerant liquid and vapor. (Cont.)
Viscosity, Pa ∙ s Conductivity, W/m ∙ K
Refrigerant Liquid Vapor Liquid Vapor
-40 0.000330 0.0000101 0.120 0.0069
-20 0.000275 0.0000110 0.110 0.00817
0 0.000237 0.0000120 0.100 0.00942
22
20 0.000206 0.0000130 0.090 0.0107
40 0.000182 0.0000144 0.0805 0.0119
60 0.000162 0.0000160 0.0704 0.0133
 THERMAL CONDUCTIVITY AND VISCOSITY
Table 15-5 Thermal conductivities and viscosities
of saturated refrigerant liquid and vapor. (Cont.)
Viscosity, Pa ∙ s Conductivity, W/m ∙ K
Refrigerant Liquid Vapor Liquid Vapor
-40 0.000356 0.0000100 0.0898 0.00796
-20 0.000284 0.0000111 0.0820 0.00907
0 0.000233 0.0000120 0.0742 0.0102
502
20 0.000193 0.0000132 0.0665 0.0114
40 0.000153 0.0000146 0.0585 0.0124
60 0.000117 0.0000161 0.0486 0.0144
 THERMAL CONDUCTIVITY AND VISCOSITY
Table 15-5 Thermal conductivities and viscosities
of saturated refrigerant liquid and vapor. (Cont.)
Viscosity, Pa ∙ s Conductivity, W/m ∙ K
Refrigerant Liquid Vapor Liquid Vapor
-40 0.632
-20 0.000236 0.0000097 0.585 0.0204
0 0.000190 0.0000104 0.540 0.0218
717
20 0.000152 0.0000112 0.493 0.0267
40 0.000122 0.0000120 0.447 0.0318
60 0.000098 0.0000129 0.400 0.0381
OZONE DEPLETION
 OZONE DEPLETION
 An alarm was sounded in the mid-1970s that the chloine from halogenated
hydrocarbons released to the environment was using up ozone in the
stratosphere.
 A reduction in the ozone composition of the stratosphere would permit
more ultraviolet radiation to reach the earth and might cause cancer.
 The initial reactions to the warnings were to stop using the offending
halocarbons as the propellent in aerosol containers and to reduce their use
in foam insulation.
 OZONE DEPLETION
 Although the application of halocarbons as refrigerants is only one of the
uses of these substances, on a worldwide basis considerable quantities of
halocarbons are used for refrigeration purposes, and the immediate
response of the refrigerant industry has been to tighten on procedures for
preventing spills into the atmosphere.
 Refrigerants 11 and 12, with their three and two chlorine atoms,
respectively, have a greater impact than refrigerant 22 which has one
chlorine atom.
 During the coming years the situation will be monitored carefully and the
need for protection of the environment may demand that still more care be
exercised and/or new refrigerants be employed.
BASIS OF CHOKE OF REFIGERANT
 BASIS OF CHOKE OF REFRIGERANT
 The characteristics of refrigerants presented in this chapter are dominant
factor in the choice.
 The following is a brief and rough review of the principal applications of
some refrigerants.
Air. The major use of air as a refrigerant is in aircraft, where the light weight
of an air system compensates for its low COP.
Ammonia. Large industrial low-temperature installations are the
applications where ammonia is most frequently used. Many new
ammonia systems come into operation each year.
 BASIS OF CHOKE OF REFRIGERANT
Carbon dioxide. This refrigerant is sometimes used for direct-contact
freezing of food. Its high condensing pressure usually limits its
application to the low-temperature side of the cascade system where a
different refrigerant operates in the high temperature section.
Refrigerat 11. Along with refrigerant 113 this refrigerant is popular for
centrifugal compressor systems.
Refrigerant 12. This refrigerant is used primarily with reciprocating
compressors for service in domestic refrigeration appliances and in
automotive air conditioners.
Refrigerant 22. Because a smaller and lower-cost compressor can be used
with refrigerant 22 than with refrigerant 12, this refrigerant has taken
over many air-conditioning applications from refrigerant 12.
 BASIS OF CHOKE OF REFRIGERANT
Refrigerant 502. This is one of the newer refrigerants, with some of the
advantages of refrigerant 22 but with the further advantage of better
behavior with oil and lower compressor discharge temperature than
refrigerant 22.
SECONDARY REFRIGERANTS
 SECONDARY REFRIGERANTS
 Secondary refrigerants are fluids that carry heat from a substance being
cooled to te evaporator of a refrigeration sytem.
 The secondary refrigerant experiences a change in repeature when I
absorbs the eat and liberates it at the evaporator, and the secondary
refrigerant does ot change phase.
 Technically speaking, water could be a secondary refrigerant, but the
substances explored here are brines and antifreezes, which are solutions
with freezing temperatures below 0°C
 Several of the most widely used antifreezes are solutions of water and
ethylene glycol, propylene glycol, or calcium chloride.
 SECONDARY REFRIGERANTS
 Propylene glycol has the unique feature of being safe in contact with food.
 The properties of these antifreezes are similar; those of ethylene glycol will
be presented so that some quantitative implications can be derived.
 One of the most important properties of antifreeze solutions is the freezing
point, shown in Fig 15-1.
 The freezing points form the classical phase diagram shown in skeleton form
in Fig. 15-2.
 The curves of the freezing points show that the solution of the two
constituents has a lower freezing point than either substance individually.
 Figure 15-2 shows possible phases and mixtures that can exist at various
concentrations and temperatures.
 SECONDARY REFRIGERANTS
0

-10

Freezing point, °C
-20

-30

-40

Figure 15-1 -50

0 10 20 30 40 50 60 70 80 90 100
Freezing point of Ethylene glycol, % by mass
ethylene glycol solutions.
 SECONDARY REFRIGERANTS

Liquid

Temperature, °C
Liquid
and
Liquid and ice salt

Solid

Figure 15-2 0 100

Concentration, % solute in mixture
Phase diagram of an antifreeze.
SECONDARY REFRIGERANTS
SECONDARY REFRIGERANTS

15-1

15-2
SECONDARY REFRIGERANTS
 SECONDARY REFRIGERANTS
1.12

1.10

Specific gravity based on water

1.08

1.06

1.04

1.02
Figure 15-3
Specific gravity of ethylene glycol- 1.00
-40 -30 -20 -10 0 10 20
water solution based on water at Antifreeze temperature, °C
4°C (density = 1000 kg/m3)
 SECONDARY REFRIGERANTS

0.65

0.60

Thermal conductivity, W/m ∙ K

0.55

0.50

0.45

0.40

0.35
Figure 15-4 0.30
Thermal conductivity of 0.25
-40 -30 -20 -10 0 10
ethylene glycol-water Antifreeze temperature, °C
solution.
SECONDARY REFRIGERANTS
0.10
0.08
.0.06
0.05
0.04
0.03

0.02

Viscosity, Pa ∙ s
0.010
0.008
0.006
0.005
0.004
0.003

0.002

0.001
-40 -30 -20 -10 0 10
Antifreeze temperature, °C
Figure 15-5
Viscosity of ethylene glycol-water solutions.
 SECONDARY REFRIGERANTS

4.5

10%

20%

Specific heat, kJ/kg ∙ K

4.0

30%

40%
3.5

50%

3.0 60%

Figure 15-6 2.5

-40 -30 -20 -10 0 10
Specific heat of ethylene glycol- Antifreeze temperature, °C
water solutions.
SECONDARY REFRIGERANTS

15-3
SECONDARY REFRIGERANTS

15-4
SECONDARY REFRIGERANTS
 SECONDARY REFRIGERANTS
 For all antifreezes the addition of the antifreeze to water has an adverse
effect upon pressure drop and heat transfer.
 Antifreezes of high concentration have high viscosity, low thermal
conductivity, and low specific heat—all detrimental.
 A good operating rule, therefore, is to concentrate the antifreeze no more
than is necessary to prevent its freezing.
PROBLEMS
 PROBLEMS
15-1

The machine room housing the compressor and condenser of a

refrigerant 12 system has dimensions 5 by 4 by 3 m. Calculate the mass
of the refrigerant which would have to escape into the space to cause a
toxic concentration for a 2-h exposure. Ans. 76 kg

63
 PROBLEMS
15-2

Using data from Table 15-4 for the standard vapor-compression cycle
operating with an evaporating temperature of -15°C and a condensing
temperature of 30°C, calculate the mass flow rate of refrigerant per
kilowatt of refrigeration and the work of compression for (a) refrigerant
22 and (b) ammonia. Ans. (b) 0.000906 kg/s, 0.210 kW

64
 PROBLEMS
15-3

A 20% ethylene glycol solution in water is gradually cooled.

a) At what temperature does crystallization begin?
b) If the antifreeze is cooled to -25°C, what percent will have frozen into
ice? Ans. 51%

65
 PROBLEMS
15-4

A solution of ethylene glycol and water is to be prepared for a minimum

temperature of -30°C. If the antifreeze is mixed at 15°C, what is the
required specific gravity of the antifreeze solution at this temperature?
Ans. 1.06

66
 PROBLEMS
15-5

For a refrigeration capacity of 30 kW, how many liters per second of 30%
solution of ethylene glycol-water must be circulated if the antifreeze
enters the liquid chiller at -5° and leaves at -10°C? Ans. 1.54 L/s

67
 PROBLEMS
15-6

A manufacturer’s catalog gives the pressure drop through the tubes of a

heat exchanger as 70 kPa for a given flow rate of water at 15°C. If a 40%
ethylene glycol-water solution at -20°C flows through the heat
exchanger at the same mass flow rate as the water, what will be the
pressure drop be? Assume turbulent flow. At 15°C the viscosity of
water is 0.00116 Pa ∙ s. Ans. 131 kPa

68
 PROBLEMS
15-7

Compute the convention heat-transfer coefficient for liquid flowing

through a 20-mm-ID tube when the velocity is 2.5 m/s if the liquid is (a)
water at 15°C, which has a viscosity of 0.00116 Pa ∙ s and a thermal
conductivity of 0.584 W/m ∙ K; (b) 40% solution of ethylene glycol at -
20°C. Ans. (b) 2182 W/m2 ∙ K

69
REFERENCE
 REFERENCE
• Stoecker, W. F., Jones, J. W. (1982). Refrigeration and Air Conditioning, 2nd
ed., McGraw-Hill, Inc.

71
END