Refrigerants

Objectives of the lecture

1. Refrigerant development and various issues related to refrigerant

selection

The focus here is mainly on vapour compressor refrigeration systems

 At the end of the lesson the student should be able to:

1. List various refrigerants used before the invention of CFCs and theitr
limitations

2. List various CFC refrigerants and their impact on refrigeration and

environment

3. State the refrigerant development after Montreal protocol

 Refrigerant-definition

Any body or substance that acts as a cooling medium by

extracting heat from another body or substance

In closed cycle systems refrigerant is any working fluid that

undergoes cyclic changes during system operation
 Refrigerant-Classification

Primary Refrigerants

Secondary Refrigerants
 Importance of refrigerant selection

The type of refrigerant used decides:

1. System design aspects

2. Size and weight of the system
3. Initial and operation costs
4. Safety issues
5. Serviceability, and
6. Reliability
 Refrigeration development

1. Early refrigerants (prior to CFCs)

2. Chloro-fluoro-carbon (CFC) based refrigerants

3. Refrigerants after Montreal Protocol

 Early Refrigerants

 Ethyl ether is the first refrigerant to be used by Jakob Perkins in

1835
 Alexander Twining proposes use of ammonia and carbon
dioxide in 1850
 Charles Tellier tries dimethyl ether in 1864
 Raoul Pictet uses sulphur dioxide in 1874
 Linde builds ammonia system in 1877
 Windhausen uses carbon dioxide in 1885
 Hydrocarbons and their mixtures are also tried around this time
 Early refrigerants-problem faced

1. Toxicity (e.g. ethers, ammonia)

2. Flammability (e.g. hydrocarbons)
3. Material compatibility (e.g. ammonia)
4. Chemical stability (e.g. SO2)
5. Operating pressures (e.g. CO2)
6. Limited temperature range (all)
 CFCs are invented!

 Thomas Midgley Jr. and his associates take up the task of

developing refrigerants that are free from problems associated
with early refrigerants in 1928 in USA

 A systematic study of periodic table is carried out and 8

elements singled out for new refrigerant development

 CFCs are synthesized by partial or full replacement of H-atoms

in hydrocarbons
 Nomenclature of Refrigerants

ASHRAE-American Society of Heating, Refrigeration and Air

Conditioning Engineers(R or CFC,HCFC, HFC and HC)

CmHnFpClq

In which (n+p+q) = 2m+2

R(m-1)(n+1)p
 Nomenclature of Refrigerants

CCl3F

CCl2F2

CHClF2

C2Cl3F3

CH4

C2H6
 Nomenclature of Refrigerants

CCl3F R11

CCl2F2 R12

CHClF2 R22

C2Cl3F3 R113

CH4 R50

C2H6 R170
 Nomenclature of Refrigerants

Brominated Refrigerants:

additional B
number – to denote how many Cl atoms replaced

R13B1 –
 Nomenclature of Refrigerants

Brominated Refrigerants:

additional B
number – to denote how many Cl atoms replaced

R13B1 – CF3Br
 Nomenclature of Refrigerants

Isomers --- subscript a,b

Azeotropes --- mixtures of refrigerants

(behaving like pure substance)
Arbitrary designations
e.g. R 502 (48.8%R 22 and 51.2%R 115)
 Nomenclature of Refrigerants

Unsaturated compounds

In which (n+p+q) = 2m

Put digit 1 before (m-1)

e.g. ethylene is R1150

 Nomenclature of Refrigerants

Inorganic refrigerants

Molecular weight + 700

e.g. ammonia is R717

water is R718
 Nomenclature of Refrigerants

Higher hydrocarbons

n=10 (a double digit figure for C4H10)

arbitrary designation:
n-butane : R 600
isobutene: R 600a
 Commercialization of CFCs

 CFCs under the trade name of Freons enter the market in 1930s

 Freon-12 (CCl2F2) is introduced in 1931

 Freon-11(CCl3F) is introduced in 1932

 Freon-22 (CHClF2) and other CFCs are introduced

 A numbering system is introduced to denote and identify

various refrigerants
 Early refrigerants vs CFCs

CFCs are
1. Non-toxic
2. Non-flammable
3. Chemically stable
4. Compatible with common materials
5. Available for wide refrigeration temperature range
 Impact of CFCs

 All early refrigerants except ammonia are replaced by various

CFCs

 Rapid growth in refrigeration due to the widespread use of

CFCs

 Refrigeration enters households in the form of domestic

refrigerators and air conditioners, thanks to CFCs!

 Production and consumption of CFCs increases exponentially!

 Ozone layer depletion-the other side of CFCs

 In 1974, Rowland and Molina propose the theory of Ozone

Layer Depletion due to CFCs released into atmosphere

 Subsequent studies confirm ozone depletion potential (ODP)

of CFCs and related substances

 Montreal protocol banning the use of Ozone depleting

Substances (ODSs) such as CFCs is signed in 1987
 Montreal Protocol

 R11, R12, R113, R114, R502 (CFC)------------------------------- 2000

 R22 (HCFC- low ODP but high GWP) ------------------------- 2030

 R410a, R290, R600a, R134a, R32 (HC, HFC)------------------modern

 Ozone Layer Depletion- Consequences

1. In human beings, increased instances of:

i. Skin cancer
ii. Cataracts
iii. Weakened immune system
iv. Damages DNA structure
2. Adverse effect on crop yield
3. Adverse effect on terrestrial and aquatic ecosystems
 Global Warming and CFCs

 CFCs are also found to contribute significantly to global

warming

 Global warming potential (GWP) of CFCs estimated to be

thousands of times greater than carbon dioxide

 Refrigerants contribute to global warming directly (due to their

emissions) and indirectly (through their primary energy
consumption)
 Consequences of increased global warming

1. Change in weather and wind flow patterns

2. Increased sea levels due to polar ice cap melting

3. Redistribution of crops and animals

 Replacement for CFCs

 Substances replacing CFCs should

1. Be non-ozone depleting (non-ODS)
2. Have a low GWP as possible

 Several synthetic and natural refrigerants replacements have

been found for CFCs

 Some of the early refrigerants such as carbon dioxide and

hydrocarbons make a comeback
 Properties of Refrigerants

 Thermodynamic properties

 Chemical properties

 Physical properties
 Physical properties

 Dielectric strength
Important in hermetically sealed compressors (should be high to avoid
short circuit))
Compared with that of nitrogen
1.31 for R 22, CO2 – 0.88, ammonia – 0.82
 Thermal conductivity
Should be high
R 22 has higher value than R 12
 Viscosity
Low viscosity is desirable for higher heat transfer
 Physical properties

 Heat capacity
Should be low for liquid (more subcooling)
Should be high for vapour (less superheat)

 Cost of refrigerant
Should be low
Ammonia is cheapest and environment friendly but attacks food
 Physical properties

 Leak tendency
Should be nil
Ammonia can be easily detected: pungent smell
Soap bubble method Halide torch method: HC flame turns bluish green
from light blue
Ammonia leak: sulphur paper/stick forms white fumes of ammonium
sulphite
Electronic leak detector: halogen vapour is heated, positive ion
concentration is increased and this increase is suitably magnified to an
audible or visual signal.
 Chemical properties

 Flammability
Hydrocarbons, ammonia are highly explosive
CFCs are not explosive
Some of HFCs (R 152, R 152a, R 143 ) are flammable
R 134a is not flammable

 Toxicity
 CFCs are least toxic
 Ammonia is toxic: not used in domestic refrigerator
 SO2 is most toxic
 Chemical properties

 Action with water

Ammonia is highly soluble
Should be high to avoid ice formation
Highly fluorinated (R 134a) is least soluble
R 22 is fairly good soluble
silica gel drier in liquid line may be used

 Action with oil

 Oil choking in evaporator has to avoided
 Immiscible (NH3, water)
 Miscible (R12, R 1521, R 290, etc.)
 Partially miscible (synthetic oil polyester is used)
 Chemical properties

 Action with materials of construction

Ammonia attacks copper
Hence piping, fittings, etc. are made of iron and steel
Copper is used for halocarbons
Aluminium can also be used (tenacious oxide film provides protection)
 Thermodynamic properties

 Normal Boiling point

Should be low at atm. pressure

 Evaporator and Condenser pressure

Should be positive pressures at operating temperatures
Should not be too high
 Thermodynamic properties

 Critical Temperature and pressure

Critical temp. should be very high
Critical press. should be low

 Freezing point
Must be lower than operating temperatures
Water is therefore used only in A/C
 Thermodynamic properties

 Volume of suction vapour

Indication of size of compressor
Reciprocating compressor: small volumes
Centrifugal or turbo compressor: large volumes

 Latent heat
Should be high
 Mixed Refrigerants

 mixtures of two (binary) or more pure refrigerant fluids. The

refrigerant mixtures can be divided into:
1. Azeotropic refrigerant mixtures
2. Near-azeotropic refrigerant mixtures
3. Non-Azeotropic Refrigerant mixtures (NARMs), also known as
Zeotropic mixtures

 R502 is a mixture of R22 and R152a. R410a, a mixture of R32 and R125
is an important non-ODS azeotropic mixture used in place of R22.
 An example of near-azeotropic is the addition of small amount of
propane to R502 to increase its solubility in lubricating oil.
 non-ODS, zeotropic refrigerant mixture is R407c, a mixture of
(R32/R125/R134a)