REFRIGERANTS

CONTENTS :-

• Definition

• History

• Classification

• Colour coding

• Properties

• Conclusion
REFRIGERANT:-

“ Refrigerant acts as a transportation medium to move

heat absorbed in the evaporator to the condenser
where it is rejected ”.
HISTORY OF REFRIGERANTS :-

Natural refrigerants:-
1) Ice blocks
2) Using nocturnal cooling
3) Use of evaporation

Artificial refrigerants :-

1) In 1835, Jakob Perkins use ethyl ether as the refrigerant ( b.p= 30’c).
(if air mixed forms an explosive gas).
2) In 1874, Raowl Piolet designs the first sulphur dioxide based system.
(forms H2SO4 when gets moisture).
3) In 1885, Fraunz Windhausen builds the first to use co2 in Germany.
(high operating pressure ).
4)In 1920, iso-butane based domestic refrigerator ( highly flammable),
General Electric first introduce “Kelvinator “ refrigerator.

5) In 1930, Introduction of CFCs .

CLASSIFICATION OF REFRIGERANTS
 Based on Working Principle :-

REFRIGERANTS

PRIMARY REFRIGERANTS SECONDARY REFRIGERANTS

1) Used directly as 1) Liquids that are used

working fluids. to transport energy.

2) Undergo phase 2) Not undergo any

change. phase change.
Eg, R134a, R404a Eg. Water , brines.
REFRIGERANT SELECTION CRITERIA:-

i. Thermodynamic and Thermo-physical properties

ii. Environmental and safety properties, and

iii. Economics
 BASED ON CHEMICAL PROPERTIES

REFRIGERANTS

PURE FLUIDS MIXTURE

1) AZEOTROPIC
2) ZEOTROPIC

SYNTHETIC NATURAL

1) CFCS 1) ORGANIC (HC)

R 12 OR FERON 12
2) HCFCS 2) INORGANIC CRYOGENIC
R134a
a) NH3
3) HFCS R23
b) CO2
c) H20 NON CRYOGENIC
BASED ON SAFETY :-
Toxicity

Class A Class B
• No Toxicity indication <= 400 ppm • Toxicity < 400 ppm
EG. CO2 , R 22 EG. NH3

Flammability
(at 21°C and 101 kPa )

Class 1 Class 2 Class 3

Do not show flame Lower flammability limit Lower flammability limit of less
propagation . more than 0.10 kg/m3 and than or equal to 0.10 kg/m3
a heat of combustion of less and a heat of combustion greater
than 19 kJ/kg than or equal to 19 kJ/kg.
 NOMENCLATURE
(synthetic) (DU PONT CORP.)
All refrigerants are designated by R followed by a number
R xyz

Where,
X+1 = Number of carbon atoms
Y -1 = Number of hydrogen atoms
Z = Number of fluorine atoms

The balance indicates number of Cl atoms

Ex: R 22

X = 0 ⇒ No. of Carbon atoms = 0+1 = 1

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

R 152a burns at 23 cm/s and R 32 burns at 6.27 cm/s
INORGANIC REFRIGERANTS:

Designated by number 7 followed by their molecular weight.

NH3= 17, R 717

Ex :- CO2, H2O, NH3.

•CO2
1. Zero ODP & GWP is 1.
2. Non Flammable, Non toxic.
3. Drawback - Operating pressure (high side) : 80 bars.
4. Low efficiency

•Ammonia
1. Toxic.
2. Flammable ( 16 – 28% concentration ).
3. Not compatible with copper (cuperic oxide)

•Water
1. Used in absorption system .
2. Cannot be used under higher working pressure.
 MIXTURES

1) Azeotropic mixture : 500 series,

• A stable mixture of two or several refrigerant .

• vapor and liquid phases retain identical compositions over a wide range of
temperatures.

Examples : R-500 : 73.8% R12 and 26.2% R152

R-502 : 8.8% R22 and 51.2% R115

2) Zeotropic mixture : 400 series,

•Composition in liquid phase differs to that in vapor phase.

•Do not boil at constant temperatures unlike azeotropic refrigerants because of dff.
Boiling points.

Examples :R404a : R125/143a/134a (44%,52%,4%)

R407c : R32/125/134a (23%, 25%, 52%)

NATURAL REFRIGERANTS :-
Hydrocarbon

Þ Their efficiency is good

Þ With no ODP and very small GWP values

Þ Compatible with lubricating oils

Þ Extraordinary reliability.

Þ Highly flammable

Examples: R170, Ethane, C2H6

R290 , Propane C3H3
R600, Butane, C4H10
R600a, Isobutane, C4H10
Blends of the above Gases
SYNTHETIC REFRIGERANTS
CFCs:
• Combination of CARBON+CHLORINE+FLUORINE.

• Also commonly know as FREONS.

• High ODP=1 and high GWP.

• CHLORINE has an excellent anti-wear characteristic.

• As ODP & GWP is high so it got banned.

• Few examples are:

 R-11
 R-12
 R-13 and many more.
CFCs:
REFRIGERANT CHEMICAL NAME APPLICATION
R-11 Trichloromonofluoromethane Centrifugal chillers

R-12 Dichlorodifluoromethane Reciprocating & rotatory

equipment

R-13 Monochlorotrifluoromethane Low stage cascade system

R-13B1 Bromotrifluoromethane Low to medium temp.

application

R-113 Trichlorotrifluoroethane Low capacity chillers

R-114 Dichlorotetrafluoroethane High capacity chillers

R-500 Refrig. 152A/12 Reciprocating compressor

R-502 Refrig. 22/115 Reciprocating equipments

R-503 Refrig. 23/13 Commercial refrigeration

HCFCs:

• Combination of HYDROGEN+CHLORINE+FLUORINE+CARBON.

• Low CHLORINE content than CFCs.

• It has ODP=0.05 & LESS but not zero.

• Low GWP value than CFCs.

• NON-FLAMMABLE & environment acceptable.

• Few examples are:

 R-123 ODP=0.02
BP= -28’C
Critical Temperature=183.68’C
 R-22 ODP=0.05
BP= -40.81’C
Critical Temperature=96.15’C
HCFCs:

REFRIGERANT CHEMICAL NAMES APPLICATION

R-22 Monochlorodifluoromethane Commercial A.C
R-123 Dichlorotrifluoroethane chillers
R-124 Chlorotetrafluoroethane Medium chillers
R-401A R-22 + R-152a + R-124 Medium temp. system
R-401B R-22 + R-152a + R-124 Transport refrigerator
R-402A R-22 + R-125 + R-290 Ice machine
R-402B R-22 + R-125 + R-290 Super market
refrigeration
HFCs:

• Combination of HYDROGEN+FLUORINE+CARBON.

• NON-FLAMMABLE, RECYCLABLE, LOW TOXICITY.

• Minimum EMISSION and maximize ENERGY-EFFICIENT.

• Its ODP=0 and LOW GWP.

• Require POE oil for the lubrication purpose.

• Few examples are:

 R-410A ODP=0
BP= -48.5’C
Critical Temperature=72.8’C
 R-134A ODP=0
BP= -26.06’C
Critical Temperature=101.08’C
HFCs:

REFRIGERANT CHEMICAL NAMES APPLICATION

R-23 Trifluoromethane Low temp.
refrigeration
R-134A Tetrafluoroethane Automative system
& commercial ref.
R-404A R-125 + R-143a + R-134a Medium & low
temp.
R-407C R-32 + R-125 + R-134a R 22 replacement
R-410A R-32 + R-125 Residential A.C
R-507 Refrig. 125/143a Commercial ref.
POE’s

o Synthetic refrigeration lubricant is used with

all HFC refrigerants such as R407A and
R407C.
o Used in Centrifugal, Screw, Scroll,
reciprocating types Compressors.
o They provide maximum protection and
lubrication at higher compressor
temperatures.
Refrigerant Acids:-

o HFC’s & POE’s are used widely.

o It causes formation of oil sludge's due to low stability.
o It leads to seize the compressors & further burn out.
o Do preventive maintenance to check inorganic acids.
COLOR CODES OF REFRIGERANTS
• Easy recognize gas cylinder

• Different refrigerant has different color coding

• Few examples are given below:

R-22 – LIGHT GREEN

R-134A – LIGHT SKY BLUE
R-404A – ORANGE

• The name label of the gases are given on the cylinder.

PROPERTIES OF REFRIGERANTS
 Thermodynamic properties
•Boiling point :- It should have low boiling point.
•Freezing point :- It should have low freezing point.
•Evaporative pressure :- It should be above atmospheric
pressure.
•Condensing pressure :- It should have low condensing
pressure.
•Latent heat of vaporization :- It should have high latent
heat of vaporization.
•Critical pressure and temperature :- It should be above the
condensing pressure and temperature.
•Thermal conductivity :- It should have high thermal
conductivity.
•Co-efficient of performance :- COP has direct effect on
running cost of refrigeration cycle so higher the COP lower
will be the running cost.
 Thermodynamic Properties
Refrigerants
Refrigerants R 12
R 12 R 22
R 22 R 134a
R 134a R 404a
R 404a R
R 407a
407a NH
NH33 HH
2O2O CO22
CO
B.P (⁰C)
B.P (⁰C) -28.8
-28.8 -40.81
-40.81 -26.2
-26.2 -46.4
-46.4 -45
-45 -33
-33 100
100 -57
-78.3
F.P (⁰C)
F.P (⁰C) -157.7 -160 -96.66 ------ ------- -77.7 0 -56.6
Latent heat
Latent heat of
of 166.95 233.75
166.95 233.75 215.9
215.9 143.68 235.57
143.68 235.57 1371.2
1371.2 2.257
2.25 571.3
571.3
vaporization
vaporization 7
(KJ/kg)
(KJ/kg)
Critical temp.
Critical temp. 112
112 96.15
96.15 100.95
100.95 72.07
72.07 82.2
82.2 132.4
132.4 374
374 30.98
30.98
(⁰C)
(⁰C)
Critical
Critical 41.15
41.15 49.9
49.9 40.6
40.6 37.32
37.32 45.15
45.15 8.88
8.88 217.7
217. 77.77
77.77
pressure (bar)
pressure (bar) 7
Specific heat
Specific heat .074
.074 .057
.057 .08754 1.03
1.03 1.520
1.520 6.91 4.18 .0374
.0374
at const.
(KJ/mol.K)
pressure
COP (@ 35’C)
(KJ/mol.K) 3.677 3.701 3.586 3.603
 Chemical properties
•Toxicity :- It should be non toxic. It should not
be harmful for humans.
•Corrosiveness :- It should not be corrosive and
should not have any effect on materials used in
equipments.
•Flammability :- It should be inert and should
not catch fire when subjected to high
temperature.
•Miscibility with oil :- It should not react with
lubrication oil.
•Chemical stability & inertness :- It should be
chemically stable for operating ranges of
temperature.
 Physical properties
•Specific volume :- It should be low in vapour
state.
•Viscosity :- It should have low viscosity.
•Leakage Detection :- It should have less
tendency to leak & if it leaking it should have a
pungent smell so that the leakage can be
detected easily.

Refrigerants R 12 R 22 R 134a R 404a R 407a NH3 H2O CO2

Viscosity(c p) .1076 .1256 .012 .001 .1 .276 1 .137

 Other properties
•Handling & Maintenance :- It should be
easy & safe to handle.
•Cost & Availability :- It should be readily
available at LOW cost.
•Performance of the System:- It should
have high COP & LOW power requirement.
OZONE DEPLETION:

• Ozone layer gets depleted by the action of CFCs.

• The greatest concentration of ozone are found from

12 km to 50 km above the earth forming a layer in
the stratosphere which is called the ozone layer.

• Few examples are given in details:

 R-12 ODP is “1”
 R-22 ODP is “0.05”
 R-134a ODP is “0”
CFC + IRRADIATED WITH UV RAYS FREE CHLORINE
Cl + OZONE ClO + OXYGEN
ClO + O Cl + OXYGEN
GLOBAL WARMING POTENTIAL

• Measurement of global warming

• Done in relation with CO2,where co2 has GWP 1

• Lower the value of GWP better the refrigerant

• Few examples are given below:

 R-11 - High chlorine content

GWP is 4000

 R-22 - Low chlorine content

GWP is 1700

 R-134A- No chlorine content

GWP is 1300
MONTREAL PROTOCOL :-

=> SIGNED IN 1987 UNDER THE ‘UNEP’, AFTER MUCH DISCUSSIONS

=> MORE THAN 170 COUNTRIES HAVE RATIFIED

=> INDIA RATIFIED ON SEPT 17,1992

=> ONE OF MOST SUCCESSFUL EXAMPLE OF INTERNATIONAL

COOPERATION IN UN HISTORY
ozone depleting developed countries developing countries
substance

CFCs phased out end of total phase out by

1995 2010

halons phased out end of total phase out by

1993 2010

HCFCs total phase out by total phase out by

2020 2040
 TEWI
• Total Equivalent Warming Impact
• TEWI = direct emission (c)+ indirect (e).
• The refrigerants have been rated according to
their LCCP(Life cycle climate performance).
• LCCP= TEWI + GWP(ID)+ GWP(D).
 CONCLUSION
• Don’t treat the today’s refrigerants with
yesterday’s techniques.
• CFC’s replaced by refrigerants blends.
• R & D of the refrigerants is in the field of
environmental acceptability.
• TEWI, the factor used to decide the overall
capability of a refrigerant.