MOLLIERS CHART &

REFRIGERANTS
 Temperature-Enthalpy Chart

Compressor
outlet/Condensor inlet
Temperature deg C

Condensor outlet/
Expansion valve inlet

Expansion valve Evaporator

outlet/Evaporator inlet outlet/Compressor inlet

(Heat)Specific Enthalpy KJ/Kg

Pressure – Enthalpy Chart (Phase Diagram)
Critical Pressure Critical Point

Critical Temperature Line

Constant Temperature Lines
Physical State Line

Vapour
Phase
Liquid
HP Phase
Compressor
Condensor outlet/ outlet/Condensor inlet
Expansion valve inlet
Saturated
Mixture Phase
Pressure (bar)

Dryness Faction lines

Constant Temperature Lines

LP
Expansion valve Evaporator
outlet/Evaporator inlet outlet/Compressor inlet

(Heat)Specific Enthalpy KJ/Kg

Critical Point: Conditions at which substances stop obeying Gas laws. Distinction between liquids
and gases does not exist. Only homogeneous supercritical fluid exists. Gases cannot be
 Molliers Chart
• Diagrammatic Representation of properties of
Refrigerant. Useful for designing the Refrigeration
system
• Gives enthalpy of refrigerant at various pressures
and physical states (liquid, vapour, mixture)
• Also called Pressure-Enthalpy Chart.
• Enthalpy is the total heat content in a substance
BTUs or KJs
• Specific Enthalpy is Enthalpy per unit mass BTU/lb
or KJ/kg
Constant
Entropy
LInes

Constant
Temperature
Lines
 Pressure-enthalpy (P-H) or Mollier diagram
• Line A to B represents the change from high
to low pressure, or expansion process
• Line B to B’ represents the amount of liquid
‘flashed-off’ in the expansion valve cooling
the remaining liquid.
• Line B to C represents the evaporation
process at constant saturation temperature
and pressure in the evaporator. At point C
the refrigerant is a dry saturated vapour.
• Line C to C’ represents the superheat
absorbed by the dry saturated vapour
• Line C’ to D represents the compression
process.
• Line D to E represents the superheat given
up by the vapour in the condenser. At point E
the refrigerant is a dry saturated vapour.
• Line E to F represents the condensation
process at constant saturation temperature
and pressure. At point F the refrigerant is a
saturated liquid.
• Line F to A represents the sub cooling of the
condensed liquid
 Refrigerating effect
• The amount of heat absorbed by each unit mass of
refrigerant as it flows through an evaporator is known as
the refrigerating effect, and is equal to the difference
between the enthalpy of the vapour leaving the
evaporator and the enthalpy of the liquid at the flow
control.
• Thus, for the system shown in Fig 3, refrigerating effect,
 Refrigerating capacity
• The rate at which a system will absorb heat from the
refrigerated space or substance is known as the
refrigerating capacity, and is expressed as, refrigerating
capacity,

• where m = mass flow of refrigerant through the evaporator

(kg/s).
• To achieve a specified refrigerating capacity of 15OkW, say,
the required mass flow rate is
 Compressor capacity
• The capacity of a compressor must be such that it removes
the vapour from the evaporator at the same rate as that at
which it is formed. To maintain a specified operating
condition, a compressor must have a swept volume equal to
the volume of vapour formed in the evaporator per unit time
(m3/h).
• To maintain constant operating conditions and produce the
required refrigeration duty would require a compressor with a
swept volume:
• V = m x v m3
• where v = specific volume of the vapour at the compressor
suction inlet, m3/kg, and v at -25°C and 1.32 bar
• = 0.18m3/kg.
• i.e. V = 0.94 x 0.18 x 3600 = 609 m3/h.
 Heat of compression
• The energy input from the compressor motor to
raise the pressure of the vapour to the required
condensing temperature is known as the heat of
compression, and is equal to the difference
between the enthalpy of the vapour at the
compressor outlet and inlet.
• Heat of compression,
 Condenser duty
• The rate of heat transfer from the refrigerant in
the condenser to the cooling medium is known as
the condenser duty, and is expressed as,

• = 0.94 (470 – 230.3) = 225.3 kW

 Coefficient of performance
• The ratio of refrigerating effect to the heat of
compression is known as the coefficient of
performance (COP).
• Thus for the system shown in Fig 3,
 Generation of Refrigerants
• First Generation 1830-1930s ex: CO2; NH3;
HCs;SO2 etc. usefulness of volatile compounds
• Second Generation: 1931-1990s ex: CFCs;
HCFCs; safety & durability
• Third Generation; 1990-2010s ex: HCFCs and
HFCs; Ozone Layer protection
• Fourth Generation; 2010 onwards ex: Pure &
Blended HCs; Global warming; high efficiency
 Refrigerant selection criteria
• Selection of refrigerant for a particular
application is based on the following
requirements:
1. Thermodynamic and thermo-physical
properties
2. Environmental and safety properties, and
3. Economics
 Thermodynamic and thermo-physical
properties
• The requirements are:
1. 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
2. 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.
3. Pressure ratio: Should be as small as possible for
high volumetric efficiency and low power
consumption
4. Latent heat of vaporization: Should be as large as
possible so that the required mass flow rate per
unit cooling capacity will be small
5. Isentropic index of compression: Should be as small
as possible so that the temperature rise during
compression will be small
6. Liquid specific heat: Should be small so that degree
of subcooling will be large leading to smaller
amount of flash gas at evaporator inlet
7. Vapour specific heat: Should be large so that the
degree of superheating will be small
8. Thermal conductivity: Thermal conductivity in both
liquid as well as vapour phase should be high for
higher heat transfer coefficients
9. Viscosity: Viscosity should be small in both
liquid and vapour phases for smaller
frictional pressure drops
10. The freezing point of the refrigerant should
be lower than the lowest operating
temperature of the cycle to prevent blockage
of refrigerant pipelines.
11. High critical temperature
 Environmental properties
• The important environmental properties are:
1. Ozone Depletion Potential (ODP)
2. Global Warming Potential (GWP)
3. Total Equivalent Warming Index (TEWI)
4. Atmospheric Lifetime
5. Chlorine Leading Potential
 Safety and Other Properties
1. TLV (Threshold Limit Value)
2. Toxicity
3. Flammability
4. Chemical stability
5. Compatibility with common materials
6. Miscibility with lubricating oils
7. Dielectric strength
8. Ease of leak detection
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
 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.
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.
 Atmospheric Lifetime
• HFC125, the major component of HFC blend
refrigerants, has an atmospheric life of 29
years, while the atmospheric life of HFC32 is
only five years.
 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.
 Toxicity
• 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).
 Toxicity
• In general the degree of hazard depends on:
1. Amount of refrigerant used vs total space
2. Type of occupancy
3. Presence of open flames
4. Odor of refrigerant, and
5. Maintenance condition
• Thus from toxicity point-of-view, the usefulness of a
particular refrigerant depends on the specific
application.
 Flammability
• The refrigerants should preferably be non-
flammable and non-explosive. For flammable
refrigerants special precautions should be
taken to avoid accidents.
 Chemical stability & Compatibility
• The refrigerants should be chemically stable as
long as they are inside the refrigeration
system.
• Compatibility with common materials of
construction (both metals and non-metals)
 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
 Dielectric 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
 Ease of leak detection
• In the event of leakage of refrigerant from the
system, it should be easy to detect the leaks.
 Economic properties
• The refrigerant used should preferably be
inexpensive and easily available.
 Halocarbon Refrigerants
• Methane (CH4)Based will have a two-digit number ex:R22 First
figure shows no. of Hydrogen atoms plus 1 Second figure shows
no. of fluorine Atoms R22=CHClF2 Chlorofluoromethane. The
total number of Hydrogen and replacement atoms should be 4;
R11; R12; R13; R23 etc.
• Ethane (C2H6) Based will have a three-digit number ex: R113.
First figure shows no. of Carbon atoms minus 1; Second figure
shows no. of Hydrogen atoms plus 1; Third figure shows no. of
fluorine Atoms R113 =CCl2FCClF2 Tricholorofluoroethane;
R114; R115 etc.
• R134a=C2H2F4 Tetrafluoro ethane The letter a signifies isomer (
having same chemical composition but different atomic
arrangement)
• Refrigerants starting with 4 and 5 indicate blended refrigerants
• The most important members of the group
have been –
• Chlorofluorocarbons (CFC)
• Hydrochlorofluorocarbon (HCFC)
• Hydrofluorocarbon(HFC)
 Chlorofluorocarbons (CFC)
• CCl2F2 - Dichlorodifluoromethane (Freon 12 or
R12)
• CCl3F - Trichlorofluoromethane (Freon 11 or
R11)
• C2Cl2F4 - Dichlorotetrafluoroethane (Freon 114
or R114)
• C2Cl3F3 - Trichlorotrifluoroethane (Freon 113
or R113)
 Hydrochlorofluorocarbon (HCFC)
• CHClF2 – monochlorodifluoromethane (Freon
22 or R22)
• R123 – C2HCl2F3
• R124 - C2HClF4
 Hydrofluorocarbon(HFC)

• C2H2F4 - R134a
• C2H4F2 - R152a
• C2HF5 - R125
• CH2F2 - R32
• C2H3F3 - R143a
 Inorganic refrigerants
• These are designated by number 7 followed by
the molecular weight of the refrigerant (rounded-
off).
 Mixtures
• Azeotropic mixtures (containing two gases
with same boiling point ) are designated by
500 series, where as zeotropic (containing two
or more gases not having same boiling point )
refrigerants (e.g. non-azeotropic mixtures) are
designated by 400 series.
Pure Hydrocarbon Refrigerants
 Depletion of stratospheric ozone layer

• The depletion of stratospheric ozone layer was

attributed to chlorine and bromine containing
chemicals such as CFCs, HCFCs. If released to
atmosphere, they are broken down by
photolysis to release chlorine atoms, which
catalytically destroy ozone, the stratospheric
gas which acts as a filter to ultra violet (UV)
light from the sun.
 Effect of UV light
• Scientists predict that increased UV light on
earth as a result of ozone depletion will,
amongst other possible consequences, cause
skin cancer, interfere with immune systems
and harm aquatic systems and crops. Strong
pressure was exerted to phase out CFCs and
HCFCs, resulted in the Montreal Protocol
being adopted in 1987.
 Regulation 12(2) of Annex VI of MARPOL
73/78
• New installations which contain ozone-
depleting substances shall be prohibited on all
ships, except that new installations containing
hydrochloroflourocarbons (HCFCs) are
permitted till 1 January 2020.
 Alternate refrigerants
• They can be classified into two broad
groups:
1. Non-ODS, synthetic refrigerants based on
Hydro-Fluoro-Carbons (HFCs) and their
blends
2. Natural refrigerants including ammonia,
carbon dioxide, hydrocarbons and their
blends
 Refrigeration oils
Lubricating oils for refrigeration compressors are
selected for their suitability with the different
refrigerant, compressor type and the plant’s
operating temperatures. Refrigeration oils should
possess the following properties:
1. Good chemical stability
2. Good thermal stability
3. Low viscosity
4. Low wax content
5. Low pour point
6. Low Floc Point
7. Moisture free
 Good chemical and thermal
stability
• Good chemical stability: There should
be little or no chemical reaction with
the refrigerant or materials normally
found in the system.
• Good thermal stability: They should not
form hard carbon deposits at hot spots
in the compressor (such as valves or
discharge ports).
 Low viscosity
As the oil particles are carried along with the
refrigerant through out the system, the oil is
subjected to extreme temperatures - low
temperature in the evaporator and high in the
cylinder head. Therefore it should be in a position
to flow freely at both low and high side
temperature. This is the ability of an oil to maintain
good lubrication properties at high temperatures
and good fluidity at low temperatures, i.e. to
provide a good lubricating film at all times.
Low wax content & low pour point

• Low wax content. Plants are operating at low

evaporating temperatures, as separation of
wax particles from the refrigerant-oil
mixture may cause problems by blocking
expansion and regulating valves.
• Low pour point. Ability of the oil to remain in
a fluid state at the plant’s lowest evaporating
temperature.
 Low Floc Point
The refrigerant oil may contain certain amount of
paraffin which will precipitate at low temperature.
The floc point is the temperature at which wax will
start to precipitate from a mixture of 90% of
refrigerant and 10% of oil by volume. If an oil of high
floc point is used, wax will separate at expansion
valve and restrict flow of refrigerant. So a low floc
point is necessary for an oil to be used in the
refrigeration system.
 Moisture free
Any moisture added with oil may cause
corrosion, and in the case of CFC and HCFC
refrigerants would form as ice in a choked
expansion or regulating valve.
• When adding oil to a compressor, or doing an oil
change, it is therefore important that only the type
specified in the manufacturer’s operating manual is
used. The oil must be clean and have no moisture
content. Oil should always be stored in tightly sealed
containers, in a warm place, to ensure it does not
absorb moisture from the atmosphere. It is
important that the procedures given in the
compressor operating manual for changing and
topping- up the oil are strictly followed.