You are on page 1of 27

Chap

9
Refrigerants and Brines

The refrigerant, as discussed earlier, is Lhe medium Lhat absorbs the heat from the substance t
cooled and d iscards the heat so absorbed to the atmosphere. In this process the Refrigerant doe~
undergo any chemical change; the change is only physical. IL only alternately vaporizes from the lie
state (to absorb Ll1e heal in the evaporator) and condenses to its liquid state (for reuse in
evaporator) by rejecting to atmosphere its superheat and latent heat of vaporization through
condenser. These processes occur in the vapour compression as well as in the vapour absorp1
sy terns.
The refrigerants hould have cenain chemical, physical and thermodynamic properties tom
it safe and energy efficient.
No single refrigerant satisfies all the qualities desired of a refrigerant and that can be used
all types of applications. So no ideal refrigerant exists. Ifa refrigerant has certain advantages, it s1
will have some disadvantages as well. So a refrigerant that has greater advantages than disadvanta
is chosen. The selection of a refrigerant for an application is based on characteristics, such as,
pressure-temperature characteristics, density, viscosity, flammability, toxicity, miscibility with '
energy efficienl, etc.
DESIRABLE PROPERTIES

The Pressure - Temperature Characteristics


To limit the energy consumption to the minimum, we have seen that compression ratio of the syste
should be low. For this, the saturation pre sure of the refrigerant at the evaporating temperatu
should be high and condensing pressure (i.e. condensing temperature obtainable with respect to ti
maximum ambient conditions) hould be as low as practicable.

Power requirement to produce unit refrigeration (Bhp/ton) should be Im\. Latent he


of vaporization, compression ratio, specific heat and density of vapour are the main factors whic
influence power requirement.
Economic

If the critical pressure of the refrigerant is low, the power required for con
pressing the vapour goes up. Further with very low critical pressure (like C0 2) it is not possib

Critical Pressure

Refrigerants and Brines

73

condense the vapour in the condenser at higher ambient tempe1ature. So the refrigerant
H have high critical pressure (see para on 'Critical pressure/temperature' in the chapter on
nenta/,s').

Critical Pressure/Temperature

As condensing temperature approaches the critical pressure


the critical temperature) of the refrigerant, COP and refrigeration capacity of the refrigerant
reduced significantly. So the refrigerant should have higher critical pressure and critical
rature.

Safety It should be non-toxic, non-explosive, non-inflammable and chemically inert, i.e. should

oes not
e liquid
in the
ugh the
orption

e to use. ASH RAE standard classifies refrigerants according to their toxicity and flammability.
lassification uses a capital letter to denote toxicity of the refrigerant and its flammability is
~ated by a numeral, as under:
,ass A-no toxicity identified (not toxic) even at a low concentration of 400 ppm, by volume
,ass B-where evidence of toxicity is identified (i.e. toxic)
!ass 1-does not propagate flame in air at 18.3C(65F) and atmospheric pressure
'lass 2-lower flammability
lass 3-highly flammable.
So there are six groups viz Al, A2, A3, B 1, B2 & B3 in the safety classification. Refrigerants with
1'Cn low/nil toxicity and non-flammable are least hazardous, identified as group Al and those com, under group B3 are most hazardous. Table 9.3 shows some of the relevant physical properties of
commonly used refrigerants along with their safety classification.

to make

LOW FREEZING POINT

ed for
, it sure
antages
has, its
,ith oil,

lf the refrigerant has high freezing point, it will freeze under operating condition, hindering the
continuous operation of the plant. So freezing point should be very much below the expected
C'\""aporator temperature.
Stability
1

It should not breakdown or decompose under the operating conditions of the refrigeran system. Also it should not react with the materials used in the system.

Oieledrlc Strength Should have high dielectric strength. As this is also indicative of the moisture
<.untent in the refrigerant. it becomes an important factor, particularly for hermetic svstems-as discu,sed under lubrication also.(see: 'Dielectric strength' in Chapter on 'Lubrication') .
'Solubility of Water in Refrigerants

system
rature
t to the
nt heat
which
r comossible

Except for ammonia, the solubility of water in the commonly


ed refrigerants is low.
Solubility is expressed in ppm by weight of water/moisture present in the refrigerant.
The solubility of moisture in the refrigerants varies with refrigerants; also solubility decreases
ubstantially) with temperature of the refrigerant. When moisture or water present in the system
r refrigerant) at a particular temperature, exceeds the solubility limit for the refrigerant at that
1 mperature, the excess separates out as free water/moisture.
It follows, therefore, that as the temperature of the refrigerant falls (for example, as it enters the
low side of the system) the quantity of moisture it can hold too comes down and the excess if any,
parates as free water/moisture.
If the temperature of the refrigerant falls down below the freezing point (0C) of water, (as it
n ppens at the throttling device and evaporator in cold store and low temperature applications) the

74

Basic Refrigeration and Air Conditioning

excess water/moisture will freeze as ice at the throttling device. This restricts or even totally blocb
the refrigerant flow through the throttling device, affecting refrigeration capacity or can even resull
in complete cessation ofrefrigeration.
Free water/moisture reacts with the refrigerant at higher temperatures (in the high side of thr
system) forming acids, which attacks the system components and causes corrosion.
Where the evaporating temperature is above 0C(32F), obviously, the freezing will not take placr
at the throttling device. But the acidic reaction does take place, attacking the system. This unfortir
nately, will become evident only when the system fails, that is, after the havoc has occurred. In hermeac
compressors, excess moisture renders the polyester or paper motor insulation brittle and weak, leading to premature motor failure, high re-operating costs and in many cases, a system that can never be
brought back to a really clean condition - an irreparably contaminated system. Therefore the water
moisture content in the system has to be kept very low (see: Chapter on 'Evacuation & dehydration"\
Solubility of water in ammonia is so high that free water separating out from the refrigerant never
happens.
In the field it is not possible to ascertain the moisture content in the refrigerant system. The
moisture left in the system could be the sum of: (l) faulty drying of components/system durin
manufacturing; (2) moisture left in the system after evacuation/dehydration during installation'
service; (3) moisture content in refrigerant; (4) in oil; and (5) formation of moisture/water due
chemical reaction within the system.
Some important precautions for keeping the moisture content in the system at a very low level~
therefore:
~ strict quality control at manufacturing stage,
~ adopting proper deep evacuation procedures at pre-commissioning stage and during service
operations,
~ procuring refrigerant and oil from reliable sources and ensuring a clean system during
erection/service.

( Table 9.1) Solubility (in ppm by weight) of water in liquid refrigerants


Temperature
37.8C (100F)
4.4C (40F)
-17 .8C (0f)
-40C(- 40F)

R 11

R 12

R22

R 123

R 134a

168
44
15
4

165
22
8
2

1800
690
308
120

1200
470
220
90

1800
600
250
89

MISCIBILITY OF REFRIGERANT WITH LUBRICATING OIL AND OIL RETURN

Gas velocity in equipment and refrigerant lines coupled with miscibility of oil with refrigerant aid in
return of oil from the system to the compressor (see: 'Lubricant-refrigerant compatibility' and 'Oil return
in Chapter on 'Lubrication').
In flooded evaporators, special oil bleeder line is provided for oil return, as oil entrainment b'
gas velocity is not possible (see: Chapter 32-Suction line).
In centrifugal compressor, by construction, the possibility of oil coming in contact with refrigerant being minimal, carry over of oil is very low. In some makes ofcentrifugal, the small amount of oil

Refrigerants and Brines

75

~e~ carried, collects at the bottom of the discharge volute, from where the oil is returned to
:hmiber by a venturi arrangement
nia systems, because of its extremely poor/nil miscibility in oil, oil does not return, but
the oil legs provided in the evaporator from where it is drained periodically. [see
-refrigerant compatibility' in Chapter on 'Lubrication'; also see details on 'Oil return' in Chapgerant piping'.]

the refrigerant gases are heavier than air. So gas escaping to the plant room from a gas leak
~ ...ervice operations, drops down, fills up and displaces atmospheric air from the room.
c...ise asphyxiation (unconsciousness or even death) by lack of oxygen, to personnel in the
~ Therefore plant rooms should have positive ventilation to limit the concentration level
111 the room much below the 'Acceptable Exposure Level' (AEL) of the refrigerant in use
monitor can be used to detect presence of gas in the plant room. These monitors are
:'!S:::~to detect even very low concentration of 1 to 3 ppm of refrigerant and thus help in alerting
a very minute leak and concentration level in the plant room .

...-=-m-ies of Refrigerants in Common Use


? ~ves the chemical names, chemical symbols, group, 'Ozone Depletion Potential'
al Warming Potential' (GWP) and 'Acceptable Exposure Limit' (AEL) of (single sub::di-i~erants commonly in use.

"U

3Ja

()()

()()

50
g

Symbol

Group

ODP

GWP100

AEL

(CCI 3 F)

CFC

1.00

3800

1000

(CHCIF2 )

HCFC

0.05

1700

1000

(CHCl2CF3 )

HCFC

0.02

90

50

(CH2 FCF3)

HFC

1300

1000

(C4 H10)

hydrocarbon

3.

1000

(NH3)

inorganic
compound

50

- Olloro Fluoro Carbons -no hydrogen atom in the molecule- have great stability and so
m a;mosphere for many years; ultimately enters into the stratosphere, where they break
~ing chlorine which depletes the ozone
- Hvdro Chloro Fluoro Carbons - replacement of one or more of the halogen atoms
-.rith hydrogen atoms in the molecule considerably reduces its life in the atmosphere and

so has less impact on the environment than the CFCs, yet with the chlorine content han
ozone.
HFC - Hydro Fluoro Carbons (no chlorine, contain hydrogen and fluorine atoms)-n
substance.
AEL - Acceptable Exposure Level in parts per million (ppm).
Halon - This is not a refrigerant but is mentioned here because of its impact on the ozone I
the stratosphere. A compound containing bromine, fluorine and carbon is used as a fire exti1
ing agent. On break down, releases bromine, which is more destructive than chlorine.

(Table 9.3 ) Some important properties of the commonly used refrigerants


Refrigera11t

- - -- -

Boiling point

oc
OF
Kglcm2
psig

CriticalPressure
Critical
Temp.
NRE**

oc

OF
kcal/kg
Btu/lb

Comp.displacement
per TR**

m3/m
:cfm

oc
Discharge gas
OF
Temperature**
Bhp/TR (theoretical)**
COP**
Safety@
Miscibilty with
mineral oil
Synthetic oil

Rll

R 12

R22

R 123

R 134a

R 600a

23.80
74.90
43.9
625
198
388
37.33
67.2

-29.80
-21.60
40.9
582
112
234
27.86
50.15

-40.80
-41.40
49.7
707
96
205
38.83
69.89

27.87
82.20
36.44
518
184
363
34.01
61.22

-26.20
-15.20
40.44
575
101
214
36.02
64.83

-11.73
10.9
36.2
514
135
275
62.82
113.07

1.033
36.5
40
104
0.939
5.09
Al

0.165
5.83
38.3
IOI
0.992
4.69
Al

0.10
3.55
53.3
128
1.011
4.75
Al

1.3
46.02
34.44
94
0.974
4.36
Bl

0.17
6.021
43
109.4
1.07
4.42
Al

0.321
11.36
45
113
1.07
4.55
A3

good

good

fair
good

good

nil
good

nil
good

2
4

.. al -l 5C (5F) evaporating and 30C(86F) condensing temperatures


Note: The discharge temperatu1e indicated is for open type compresso1: This will be higher in semi-hermetics a
higher in hermetics.
@Safety classification (see para on Safety in this chapter).

Toxicity
Class A: no toxicity at concentration
of 400 ppm by volume
Class B: tocxicity identified

Flammability

---

--

Class I: no flame propagation at l 8C(6.


Class 2: practically not inflammable
Class 3: highly inflammable

Refrigerants and Brines

77

S' IMPACT ON ENVIRONMENT


refri~erants in

use for the past several decades have impact on the environment, in two
effect) .

~um auf Global wanning (greenhouse

:ariant of oxygen, the ozone molecule having three atoms of oxygen while the oxygen
made up of two atoms (0 3 and 0 2). An ozone layer surrounds the earth's stratosphere,
11 kilometers above the surface of earth at the equator and 5 to 6 kilometers up at the
ozone la\ er absorbs sun's ultra-violet (UV) rays substantially, thus acting as a protective
life on earth from the harmful effects of high concentration of UV radiation. If depleozone layer occurs in the stratosphere, UV radiation to the earth will increase. Consecan be health hazards such as, skin cancer, severe infectious diseases, environmental
-:lobal warming, melting of polar ice caps, rising of sea level, droughts etc.-a matter
---.-<"r....,..m for life on earth.
.&

115.5

1642
133
271
263.43
474. 18
0.097
3.44
98.9
210
0.989
4.84

B2
nil
nil

COO' muously

being produced and destroyed in a natural cycle, but in this cycle the

_______ __..t <if ozone remains essentially stable. However the gases, chlorine and bromine, react

ua. ozone to oxygen and can destroy it much faster than the natural cycle of its creation,
ozone depletion in the stratosphere. Chlorine is present in many compounds in regular
".>contain bromine.
c:nh l qsos and until a few years ago, most of the refrigerants in use with mechanical
re ion systems were the Chlorofluorocarbons (CFC) and Hydro chloro Ouoro car. These compounds contain the ozone depleting chlorine.
lhe:.e compounds (CFCs & HCFCs) are heavier than air, some eventually migrate to the
once they are released to the atmosphere. The time taken to reach the stratosphere may
h \ery long (may be a decade or much more). But the fact remains that, being very
===ll~nds (among the most stable compounds developed) they do reach the stratosphere,
s rong ultra-violet radiation breaks the compound and converts to chlorine monoxide,
ozone at a very rapid rate. It is estimated that one chlorine atom can destroy 100,000
_Jes. Higher the chlorine content of a compound longer will be its atmospheric life, so
ill be its impact on the ozone layer. CFCs have more chlorine content than HCFCs; so
hinher potential for ozone depletion. It is estimated that CFCs contribute nearly 70% of
-~===~ozc ne depleting chemicals in the atmosphere.
teed to extinguish fire) are compounds containing bromine, fluorine, and carbon. Like
break down in the stratosphere releasing bromine. Bromine is even more destructive
la\er than chlorine.

The potentials of compounds for ozone depletion, obviously,


ing to their chlorine/bromine content and the period of their stability in the atmosphere.
;;:cential known as 'Ozone Depletion Potential'. (ODP) is a factor based on the percentage weight
e in a compound and its lifetime (stability) in the atmosphere.
".!the refrigerants, (CFC) R 11, with 3 atoms of chlorine in a molecule, has the maximum
and its ODP is fixed at 'one'. ODP of all others are relative to that of R 11. e.g. ODP of

eia111eDepletion Potential (ODP)

(65F)

78

Baste Rejrigeralion and Air Con.dttioning

R 22 (a HCFC) is 0.05, so its destruction potential is only 5% that ofR I I.This is because it has l
chlorine content(one chlorine atom per molecule) and also the hydrogen in it decreases its stabilt
making it difficult to last long enough in the atmosphere to reach the ozone layer, while R 11 with
hydrogen content has very high stability and so longer atmospheric lifetime. Hydro Fluoro Car
(HFC) have no chlorine content, so ODP is zero. CFCs have the highest ODP, HCFCs have comparr
tively less and HFCs (no chlorine content) have zero ODP.

Greenhouse Effect-Global Warming Potential (GWP)


Some of the heat absorbed by the earth from the sun is reflected back to the space thus notallowin
the earth temperature to rise above an average level. A film ofgases envelops the earth's atmosphere.
Certain of these gases trap some of the reflected heat preventing it to reflect back to space, there~
increasing the earth's average temperature leading to 'Global Wanning'. This is known as thegre~
house effect and so the gases that trap the heat are known as greenhouse gases [green house: a room
house of glass walls and roof for the cultivation of plants at controlled (high/tropical) temperatu
and (high) humidity conditions]. Obviously higher concentration of the greenhouse gases in
atmosphere will lead to a warmer earth and consequent harmful ecological changes.
The impact of the emission of the various greenhouse gases on the climate varies according
their atmospheric life. The impact of the various gases is compared with that ofC0 2, which is one
the main greenhouse gases in the atmosphere. So an index relative to the impact ofC02 is used
is known as the Global Wanning Potential (GWP). The GWPofC02 is fixed as 'one'. GWPs have a ti
component, since the atmospheric lifetime of the greenhouse gases varies. So the time compone
spreads from 20 to I 00 years and written as GWP20 (for 20 years), GWP 100 (I 00 years lifetime) etc..
For example, emission of one kgofR 134a is roughly equivalent to emission of 1300 kgofC0 2 in I
years, so GWP 100 ofR 134a is 1300. Thus the Global Warming Potential (GWP) ofa greenhouse
is an index of its ability, relative to that of C02, to trap heat radiated from earth to space.
The main greenhouse gases in the atmosphere are cabondioxide (C02 }, methane and nitro
oxide. All halogenated refrigerants (CFCs, HCFCs and the chlorine free HFCs too) are found to
greenhouse gases. HCFCs (e.g. R 22) and HFCs (such as R l 34a) have shorter atmospheric life th
CFCs. They are destroyed in the lower atmosphere itself by chemical reaction and so they have low
ODP and GWP values. However, though the GWP values of these are lower than those of the CFU.
their emissions do contribute to global warming and their influence is much greater in compariS09
with C02 (their GWP 100 values ranging between 1000 and 3500).
C02 (one of the main greenhouse gases) is generated and emitted to the atmosphere by the fuel m
generating energy in power plants. Thus any equipment or gadget using energy (in the generation
which C02 is released to the atmosphere) for its operation, contributes to global warming, we caa
say, indirectly.
The average C0 2 release from an electrical power plant (based on fossil fuel) is estimated to be
0.6 kg per unit (kWh) of electrical energy produced (in developed countries).
The refrigeration and air conditioning system contributes to global warming in two ways. (1) Thr
direct impact is by the escape of refrigerant gas to the atmosphere from the system, while servicing
and also due to leak; (2) Indirectly by way of consumption of energy (in the generation of which C~
is released) for its operation.
Thus the toLal effect on global warming, known as, Total Environmental Wanning Index-TEW!, is
the sum of the direct and indirect effects.

Refrigerants and Brines

79

comumption of refrigeration and air conditioning systems is reckoned to be about


the total electrical consumption. So a significant greenhouse effect occurs during their
e_ Thi- indirect effect on power consumption is found to be comparatively larger than
dfea due to escape of the refrigerants to the atmosphere while servicing and through
(i) to minimize the effect of indirect warming, the refrigeration and air conditioning
be enerm efficient (low BhpfrR), i.e. high efficiency compressor and ancillaries. (ii)
<&ea warming, the refrigeration system has to be leak tight and also calls for very careful
~fri....erants.
:Jemenl ofsystems' energy efficiency and maintaining it through the life of the system,
role m reducing the greenhouse effect

.._.-:;w and Control Measures on Ozone Depletion-Montreal Protocol, London and

-cgn Amendments
Since the effect of CFCs, CFCs etc on the Ozone layer is a global
been a live issue in the international forums. In the international conference held in
H

-~--ahas

7, the famous 'Montreal Protocol' (an international treaty) was signed by number of
"m:;.=::;.--noolbl} the developed countries-followed by amendments/revisions, agreed to at the
Copenhagen conferences in 1990 and 1992 respectively.
treal protocol and the subsequent amendments/revisions call for, as a first step freezing
_..._..........,n levels of all 'Ozone Depleting Substances' (ODS). This is to be followed by complete
their production. Ultimately all these substances are to be completely phased out. A
--~-. Table 9.4 applicable to the developed nations with a different time frame for the develop:==:::=::s.. has also been agreed upon.

e.
nd nitrous
found to be
ric life thaa
have lower
fthe CFCs.

Developed nations

Developing nations

100% phase out by


January 1996
production frozen at
1989 level by Jan 1996
35% cut by 2005,65% cut by 2010
90% cut by 2015,99.5% by 2020
100% phase out by 2030

production frozen at 1996 level by


Jan '99;100% phase out by Jan 2010*
additional time limit
up to 2040 for 100% phase out

complete cessation of production by

Jan 1994

Indian industry :production of CFCs frozen at mean 1996 level from July 1999, I <>%consumption cue by end
b\ 2005; 85% by 2007; 10~ by end 2009, OEMs (own equipmem manufacturers) to effect 100% phase out

-TEW!, is

all countries have similar strict comrols no import (and also export) of CFCs or CFC containing equipment
possible. Though there are no such controls as yet on HCFCs, better performing/more efficient HFC systems
me competitive.
the H CFC, R 22 in new equipment is being completely prohibited (by the respective authorities of each
in Germany from Jan 2000, in Sweden since 1998 and in olher European union countries, expected to
effective from Jan 2000. R 141 b(a H CFC)-a substitute for R 11 for foam blowing of thermal insulation-is
phased out in USA by 2004 [ODP - 0.1 l and GWP20 - 1800].

80

Basic Refrigeration and Air Conditioning

Production/use of HFCs (R 32, 125, l 34a, l 43a and their blends- R 404A, 407 & 410) is not regulated by the Montreal Protocol, but may be regulated by individual countries.
Control on Greenhouse Effect- KYOTO Agreement Since many of the refrigerants are found
to be greenhouse gases also, TEWI (total equivalent warming impact i.e. direct + indirect warming
impact), in addition to ODP, has become an important criteria for developing environmentally safe
alternate refrigerants. This aspect formed part of the KYOTO summit held in Dec 1997.
The KYOTO summit agreed that by 2010, greenhouse gas emissions from industrialized countries
be reduced to a level below that of 1990. The gases covered are: C02 , nitrous oxide, methane (CH4),
chloro-fluoro-carbon, sulphur-hexa-fluoride and hydro-fluoro-carbons (HCFCs). The agreement
envisages developed countries to finance emission reduction projects in developing countries and
receive credit for it. As of now, the controls are applicable only to developed countries. Enforcement
of the controls and as how to penalize defaulting countries has been postponed till the next meeting.
The Montreal protocol was signed by number ofnations notably developed countries. Some ofthe
developing countries, capable of (and which are) producing CFCs in large quantities, like India,
China etc, refrained from signing the protocol, because of their reservations on the economic feasibility and back-up for developing and producing substitute refrigerants and consequent design
changes in equipments. Equally important was their concern about the technology transfer from
western nations for the manufacture of the substitutes in the developing countries. Subsequently in
the London conference, held in June 1990,attended by about 100 nations, India indicated its willingness to sign the Montreal Protocol, since the developed countries agreed to set up a global fund
to help the developing countries ease the burden of switching over to environmentally safe alternate
refrigerants. An agreement on the important issue of technology transfer for the manufacture of the
alternates was reached.
Corrective Steps

Steps in correcting the harmful effects ofchlorine on the environment obviously


are:
- first to reduce the consumption of refrigerants with high chlorine content and to use alternatives of less chlorine content, followed by
- (or concurrently) a cut on the use of refrigerants with less chlorine content also and use
chlorine free substitutes
- in the long-term, use only chlorine/halogen free alternates, with minimum of GWP.
The threat of global warming has the chlorine free HFCs also included in the list of gases to be
regulated The control on the greenhouse gases (Kyoto protocol) has changed the ACR industry even
more fundamentally than the Montreal protocol.
Chlorine free single substitute refrigerants appear to be limited to a few such as, R 134a, R 600a
and the oldest refrigerant of all, ammonia. Other alternatives, presently available, are all 'refrigerant
blends'.

REFRIGERANT BLENDS
A blend is a mixture of two or more refrigerants in various proportions. Blends were earlier developed to combine the good properties of its constituents. A typical example is R 502 (a blend of R 22
and R 115) -its discharge gas temperature is lower than thatofR 12,so, much less than thatofR 22
and has near about the same cycle values as R 22.

Refrigerant.s and Brines

is not regu-

t:;are found

let warming

ientally safe

;
~countries

lane (CH4),
agreement
ntries and
forcement
tmeeting.
me of the
like India,
(1mic feasient design
sfer from
quently in
red its willlobal fund

'.gerant blends now developed are as alternates for refrigerants in existing plants and also
~ ones. They have properties similar to the refrigerants they replace and have zero ODP and
(;1,\P. Most of the first category contain HCFC as the main constituent to replace the CFCs in

., plants (immediate step to minimize ozone depletion). Others are chlorine free longThese blends have been and still undergoing extensive trials and some have been
nl commercially.
nds are of two types, auolr<>jlic and uolropic. Azeotropic blends behave as single substance
_e rants in the evaporating ('liquid to vapour phase' change) and condensing ('vapour to liquid
change) processes. That is, at a pressure, the evaporating (boiling) and the condensing tem'\.res are the same.or in other words, the saturation temperatures of liquid and vapour at a
' re are same e.g. these temperatures of the azeotropic blend R 502 at a pressure of 138 psig are
a t 70F.
~bstitutes.

hotropic Blends
...... zeotropic blends, however, at constant pressure, the phase changes (boiling and condensing)
.xcur at different temperatures, that is, the saturation temperatures of liquid and vapour (both at the
pressure) are different. The difference between the two is known as the 'temperature glide'
e means 'to pass gradually'). Table 9.5 shows a few excerpts from the saturation pressure-temture charts of'liquid' and 'vapour' of the zeotropic blend R 401A, to high light the different
!:!mperatures at which the phase changes occur, at constant pressure .
T.ble9.5 )
P c<>sure (psig)
a :idensing. point F

tling point F

3.4
-7.6
-18.4

7
0.5
-10.3

14
13. l
2.3

2 1.5
23.9
13. l

101
88.7
79.7

145
104
95

159
116.6
107.6

Example 9.1

stryeven
a, R600a

frigeranl

ier develd ofR 22


t ofR 22

- At a suction pressure of 14psig,the saturation (boiling) temperature of liquid is 2.3 F and the
reference point for superheating is 13. 1F [i.e. the saturation temperature of vapour at the end
of the liquid to vapour phase change (boiling/evaporating)].
- At a condensing pressure of 145 psig the saturation (condensing) temperature of vapour is
104F and the reference point for liquid sub-cooling [i.e.the saturation temperature of the liquid
at the end of the vapour to liquid phase change (condensing) is 95F].

Thus vapour and liquid 'temperature-pressure' charts are essential to determine suction gas
- ;>erheat and to assess the liquid sub-cooling available at the start of the liquid line.
Some important points to be noted in handling systems with zeotropic blend refrigerants:
,. Possibility of a change in the concentration of the constituents, when leakage occurs in the
system, Leakage in the pure liquid or vapour state may not be critical. But in the phase change
areas, namely, after the throttling device in the evaporator and the condenser, the shift can be
quite significant; so only brazed joints to be used to minimize leakage possibilities.
~ Charge the system only with liquid refrigerant; if charged in the vapour state, shift in the
concentration of the constituents in the system can occur.

82
)>
)>
)>
)>

I Basic

Refrigeration and Air Conditioning

Some blends have one flammable constituent and hence entry of air into the system should be
prevented.
Blends with wide temperature glide is not suitable for flooded evaporator systems.
Special charging hoses with nylon core should be used.
Adopt deep vacuum procedures.

Alternate Refrigerants
Following is an approximate summary of commercially adopted alternates and potentials under
active consideration (single substances and blends):

Transitional (first step)-(HCFC)- single : R 123; R 22


Partly chlorinated (all R 22 based) blends : R 402A; R 403 B;R 408A
Mediumlermandlongtenn
R401A; R401B; R409NB; R413A
(i) Chlorine free : HFC single: R l 34a; R 125
blends : R404A; R507A; R410A; R407C; R508B
(ii) Halogen free : single: R 717, R 600a, R 290,
blends : R 290/R 600a
Above data is not exhaustive. Investigations/tests are continuing for new alternatives.
R 123 ( CHCl 2CFJ); a HCFC; ODP-0.02; GWP 100 -93, AEL- 50 ppm Some manufacturers have
adopted R 123, a HCFC, as a replacement for the CFC, R 11, for their centrifugal. Like R 11,it is a
low-pressure refrigerant. It is compatible with most of the materials and mineral oil used in R 11
machines, except motor winding and gasket materials. Physical-thermodynamic properties are
similar to R 11 and has same operating efficiency.
It is classified as carcinogen (long time exposure to which can cause cancer) category 3 and
maximum recommended 'Acceptable Exposure Limit' (AEL) is 50ppm. This calls for caution against
long term exposure and good plant room ventilation.
Because of this negative aspect, there is international pressure for banning its use immediately. At
the same time there is also the strong stand against its immediate phase out or even along with other
HCFCs. The arguments in its favour are:
)> it has comparatively a short atmospheric life time of 17 months (against 12 years for R 22, 14.6
years for R l 34a) and so it is not going to make it to the stratosphere;
)> being a low pressure refrigerant and with an efficient purge recovery system, the emissions can
be contained at very low levels. Further, with positive plant room ventilation, exposure level in
equipment room can be held at a very low level.
)> high refrigeration cycle efficiency combined with very low, or possibly, 0 emission level, the
indirect and direct greenhouse effects or TEWI are quite low.

R 123 can be a retrofit refrigerant for R 11 centrifugal system. Since gaskets are to be changed and
motor windings too in hermetic/semi-hermetic systems, the retrofit however cannot be just a simple
straight change over.
R 22 (CHCIFJ; a HCFC; ODP- 0.05; GWP 100 -1700,AEL-1000 ppm R22 has been (still is) the
widely used HCFC refrigerant. Here it is analyzed as a transitional replacement for CFCs.

Refrigerants and Brines

__ a n be an alternative to R 12 and R 502, but with limitations, such as:

tern should be
,..
. ms.
,,

,
tentials und er

""

""

facturers have
keR 11,itisa
used in R 11
roperties are
tegory 3 and
ution against
mediately. At
ng with other
for R 22, 14.6
emissions can
sure level in
ion level, the
changed and
JUSt a simple
n (still is) the
fFCs.

~ has over 40% more

refrigerating capacity than R 12. So the compressor size will have to be


e r, to match with the system capacity with the R 12 compressor.
compressor displacement required per TR with R22 is lower than that of R 12. So the velocity
R 22 in refrigerant lines, evaporator, condenser etc of the R 12 system will be lower and this
c:r.a lead to oil return problems.
ause of its higher pressure and discharge gas temperature levels (than R 12), it is not
i...:.ble for transport refrigeration-such as cars, buses, train, trucks etc.
the- higher discharge gas temperature also becomes a draw back in low temperature applicaoo~. Due to higher compression ratios associated with these applications, d ischarge gas tempc rature is naturally higher; more so with R 22 and consequent possibilities oflubricating oil
.u J refrigerant breakdown, system turning acidic, etc.
d- :- tiling device needs changing.
usly R 22 is not a straight replacement for R 12.

BB

es.

83

34o (a HFC); CH2'CF3 ; ODP- O; GWP-1300 , AEL- 1000 ppm R l34a is chlorine free and
.'le very few single substance replacement refrigerants. It is mainly a substitute for R 12 and
ted range for R 22. It is also used as a component for a variety ofblends. Its toxicity is very
eptable Exposure Limit (AEL) is 1000 ppm- same as ofR 12.
harge gas temperature [at -l5C (5F) evaporating and 30C (86F) condensing] for R l34a
i-. between the values for R 12 (38.3C) and R 22.(53.3C).
Thermodynamic properties are similar to that of R 12; refrigeration capacity, energy requirepressure-temperature characteristics are comparable in air conditioning and medium temre refrigeration applications However, in applications with lower evaporating temperatures it
. .:>wer refrigeration capacity. Compared to R 12 system, the capacity will be about 90% and 82%
~ ;:>orating temperatures of-20C(-4F) and -30C(-22F), respectively, while the corresponding
e requirements will be about 89% and 83%, COP being practically the same. Up to evaporator
==perature of -10C(l4F) same compressor si1e as for R 12 system is satisfactory and for lower
perature applications larger compressor size is required.
R 134a is not miscible with mineral oils. So synthetic oil, Polyolesters (POE) or Polyalkylene glycol
:\G has to be used. PAG oils are used mainly in car air conditioning systems. Both these oils
~ t.1ghly hygroscopic. So special larger sited R 134a drier (molenilar sieve matched to the
:Jal er molecule size of R l 34a) has to be used (see: Lubricant-refrigerant compatibility in Chapter on

,1/ion).
... r ecial refrigerant hoses are required for R l 34a (in Car/transport air conditioning).
r retrofitting (converting) an existing refrigeration system with R 12- mineral oil pair to R 134aolester oil pair, it is enough to drain the mineral oil and R 12 from the system. The system
e\er has to be clean, to avoid reaction of oil, refrigerant and moisture with remnant contamit:. in the system. So before charging R l 34a and polyolester oil into the system, it is always better
ll:l horoughly evacuate the system for removal of remnant traces ofchlorine compound and for deep
hvdration. As mentioned above special R l 34a drier has to be provided and moisture indicator is
a "":lUSt.
.\s R 22 is progressively phased out, R 134a can be a substitute for it, but to a limited range of
applications. A larger compressor is needed for R l 34a as it requires higher compressor displacement

84

Basic Refrigeration and Air Conditioning

per TR than R 22 [at-15C (5F) evaporator & 30C (86F) condensing, R 134a needs 0.17 m 3 'm
(6.02 cfm) and for R 22, it is O. lm3/m(3.55cfm)].
Centrifugal with R l 34a as the refrigerant (its impeller and tip speed different from the R : _
design), gives same or marginally better capacity than the centrifugal with R 12.
R 12 centrifugal system can be retrofitted with R 134a, (with POE oil). There will be 25 to 33<K
reduction in capacity.
Some of the important measures to be taken during installation ofR 134a systems are:
}i> thorough cleaning of pipes/components,
}i> brazing/soldering only with a nitrogen bias in the pipes,
).. provide good suction filter on compressor, particularly for steel pipe jobs,
}i> use of only dry nitrogen for pressure/leak testing,
}i> charge/add oil only from originally sealed containers,
}i> while servicing, every time the system is opened utmost care is to be taken to prevent ingression
of moisture and carry out evacuation.
R 125; a HFC (CF3CHF,); ODP- O;GWP 100 - 3200,AEL- 1000 ppm

This is used asacomponem


for blends, though it can be, to a limited range, a replacement for R 502 and R 22.0nly ester oils are
compatible.
The plus points are: is non- flammable; low isentropic compression exponent (so lower discharge
gas temperature); high volumetric efficiency in reciprocating compressors, requires high mass flo"'
rate - advantageous for suction gas cooling.
The disadvantages: relatively high GWP; steep pressure curve (so higher compression ratios); lo"
critical temperature of 66C; COP drops, as the condensing temperature approaches the critical
temperature. These negative characteristics render it suitable only to a limited range ofapplications.
not suitable for air-cooled applications. In cooler temperate zones, relatively efficient operation in
low temperature applications can be achieved, particularly with water-cooled systems.

(Table9.6 )
HCFC- blends

R 402A

R403B

R 408A

Only short term

Constituents ODP
GWP100
Temp.glide C
AEL (ppm) -

R 22/125/290
0.02
2570
2
1000

R 22/218/290
0.03
3680
2.4
1000

R 22/ 143a/125
0.026
3050
0.6
IOOO

service
replacements
for R 502

R 22, though low in proportion, makes these blends, ozone depletion substances and also their
GWP are comparatively high. Hence they are only short-term replacements.
The high discharge gas temperature associated with R 22 is reduced by the addition of chlorine
free R 125 and 143a and also due to the low isentropiccompression exponent ofR 125, R 143a and
R 218. All the blends have great similarity to R 502.and are miscible with mineral oils. Synthetics
also can be used, as R 22 is present.
Components of the R 502 system need not be changed on conversion with these blends. However
the system should be quite clean, to avoid reaction and consequent poor chemical stability. Liberall'

Refrigerants and Brines

s 0.17 m 3 /m

I 85

J suction gas filter and liquid line drier should be provided and an oil change after 100 hours
ieration.
-

le9.7)
HCFC blends

re:
,tituents
P100

nt ingression

.,... .p.glide C
- -ppm

HFC blend

R 40JA/B*

R 409A!B*

R 413A

Sero ice

R 22/l24/ l52a
0.03
1080
6.4/6.0
1000

R 22/l24/142b
0.05
1440
8. l/7.2
1000

R 218/ l 34a/600a
0
1770
6.9
1000

replacement
for R 12

IA & 40 I B have same components but only % of constituents varies slightly. Similarly in R 409A &
_ also].

a component
ester oils are

) slwrt term

service
placements
or R 502

nd also their
n of chlorine
, R 143a and
. Synthetics
ds. However

lity. Liberally

me compressors in existing R 12 systems (particularly older models and in systems of doubtful


_mess) may not be suitable for straight conversion to R 134a. Also it may not be that easy to drain
il from hermetics and carry out repeated oil flushing necessary for the R l 34a conversion. For
cases, these are available as straight Service (transitional) replacements, instead ofR 134a.
'.neral oils are compatible with R 40 lA,R 401 B and R 409NB. Alkyl- benzene or POE oils also
It! used. Alkyl benzene does not readily absorb moisture and so can be handled in the same way
-neral oils
-l l 3A is compatible with mineral oils. Ester oils also can be used. This is particularly suitable for
cstic refrigerators, car air conditioning, refrigerated transport, cold stores etc
~ all the cases, for conversion, the oil will have to be drained and after 100 hours of running, oil
.ng a couple of times is recommended; new liberally sized liquid line drier has to be provided;
C n conversion the expansion valve will need fine adjustment. These being azeotropic blends,
temperature glide-so expansion valve adjustment has to be done carefully, using vapour tables.
under Refrigerant Blends in this chapter)
22 being the main component in the HCFC blends, the discharge temperature can go high..cularly in low temperature applications. Therefore the application limit of the compressor
er conversion should be checked before carrying out the conversion.

C nstituents
DP
C ".\'P100

T.. :np.glide C
.IL-ppm

R 404A

R 507A

R 125/ 143a/134a
0
3750
0.7
1000

R 125/143a
0
3800
0
1000

long term
alternative
for R 502

:-he component R 143a is of flammable category. However in combination with R 125, the flamin both the blends.

~ility is effectively suppressed

861 Basic Refrigeration and


__A_ir_ Co
_ nd
_ i_tio
_ n_ing
_ _ _ _ _ _ _ _ _ _ __ __ _ _ __

_ _ _

All the components have low 'isentropic compression exponent' . Hence the blends have dischar):'
gas temperature, even lower than that ofR 502. Thus these blends are suitable for low temperatu
applications, that too in single stage compression.
R 143a and R 125 have same boiling point (-48C) and the proportion of the third component
134a in R 404 being very low (4%) its temperature glide is less than l C. Thus R 404 is a 'ne..
azeotrope' and acts practically as a single substance.
With only the firsl two components, obviously, R 507A has azeotropic characteristic (no temper.
ture glide). So this is even better than R 404A as an alternative to R 502.
These blends resemble R 502 in capacity and COP. Both are compatible with the materials, exce~
mineral oil used in R 502 system. POE oil is used.
The relatively high global warming potential (GWP 100- 3750 & 3800) is a disadvantage, but bette
compared to 5600 of R 502.
In converting existing R 502 systems with these blends, the mineral oil in the system has to bot.
flushed out with POE oil. The usual precautions as mentioned earlier in handling POE oils have t
be taken, including provision of liberally sized drier.
R407C- Blend of R 32/125/134a; ODP-0; GWP100-1610, Temp. Glide 7.4CAEL-1000 ppm,
Short-term Replacement for R 22 Its properties are very much similar to that ofR 22,in term-

of pressure, mass flow rate, vapour density and refrigeration capacity- compatible with the material
used in R 22 systems, but not with mineral oils. POE lubricants are used.
Its wide temperature glide, however, is a big disadvantage. Applications are very much limited tc
air-conditioning systems and to a narrow range of mediu m temperature refrigeration. In low temperature applications, capacity and COP drop down significantly; so not suitable. It is not recommended for use with flooded evaporators, as there will be a significant shift in concentration and
layer formation in the evaporator. Thus its scope ofapplication is very much limited and so canno1
be considered as alternate replacement.
R 410A-HFC Blend of R 32/125;0DP-0; GWP 100-1800, Glide < 0.2 C; AEL-1000 ppm
Alternative for R22 and Potential Substitute for R 13B 1 It is a near azeotropic HFC blend and
is compatible with materials used in R 22 systems, except mineral oil. POE oil has to be used. Ir

comparison with R 22, it gives about 40% more capacity and about 92% of COP. The temperature
glide (less than 0.2C) is very low- a near azeotropic blend, behaves practically like a single substance
refrigerant.
It is also considered as a potential substitute for R 13B 1 in low temperature applications, particularly in cascade systems-shows less capacity below -60C.
Against these very advantageous characteristics, there are two distinct disadvantages, viz:
(i) relatively low critical temperature of73C(l63F), limits the scope ofapplication witl1 respect t
condensing temperature and (ii) pressures much higher than that of R 22, necessitating, in many o
the applications, design changes in compressors, heat exchangers, piping, flexible hoses etc, to suit
the higher operating pressures.
Saturation pressure at
R 410A
R22

43C(l09F)
25.5kg/cm 2 (362 psig)
15.7kg/cm 2 (223 psig)

37.8C(l00F)
23.6 kglcm2(336psig)
13.8 kg/cm 2 (196 psig)

Perhaps it may be long bjore suitable equipments are available. Obviously none of these altematives(R
407C,R 410A,R 134a) can replace R 22 in all respects.

Refrigerants and B rines

ave discharge
temperature
component R
404 is a 'near
no temperaterials, except
ge, but better
rem has to be
E oils have to

87

~ e some European countries are for earlier phase out ofR 22,other developed countries like
J a?an, Canada etc and many of the developing countries are for the phase out dates stipulated
p rotocols. The scheduled phase out date (for R 22) is still about 30 years away and it may be
le for some more years after the phase out dates by way ofreclamation/ recovery. So R 22 can
pected to continue to play a vital role in the ACR industry.

5C8B- HFC Blend of R 23and116- ODP-0, Temp. Glide 0C, AEL- 1000 ppm

This is
as a long term substitute for R 13, R 503 and R 23 in very low temperature applications, such
de refrigeration, environmental chambers, etc. It is a good match for R 503, delivers higher
t' than R 13. It is a retrofit for R 23-gives better energy efficiency. POE oil has to be used with
usual precautions mentioned earlier.

er Applications of CFCs
Cs ere also used for a wide spectrum of other applications, like: as propellant for aerosols, foam
i'In"T agents for

-1000ppm,
R 22,in terms
he materials

ch limited to
. In low temnot recomntration and
ld so cannot
-1000 ppm
FCblendand
be used. In

ons, particu, viz:


ith respect to
g,inmanyof
--es etc, to suit
F)
2

(336psig)
(196 psig)

altematives(R

insulation/packaging boards, solvent for the electronic industry, stabilizers in the


uction of medicines, in scientific studies, etc. Environmentally safe substitutes such as butane,
e have been established for these applications.

OGEN FREE REFRIGERANTS


i 7- Ammonia -NH3- inorganic compound - ODP:O; GWP:O; AEL: SOppm

A halogen
rubstance, with zero ODP and zero GWP. It is not a manmade compound, but of natural
rr-t-.a.,,,nces-nitrogen and hydrogen. Ammonia is the first successfully used refrigerant in USA,
pe etc, since the last century ( 1870-1880). Therefore it is not a new or a substitute refrigerant
!has been in use mainly in industrial, food processing and some cold store applications. Ammomcreasingly lost its significance particularly in the air conditioning sector, with the advent of
refrigerants in 1930s, as CFCs have practically no toxicity and flammability, no reaction with
and materials used in the machinery, facilitate use of the compact-energy efficient hermetics/
e rmetics and automatic oil return. The increasing environmental concern over ozone deplea."ld global warming, has revived the importance of ammonia as a refrigerant, in the developed
nes also.
Ammonia has very positive features; at the same time has some strong negative aspects as well,
had restricted its much wider use in refrigeration-air conditioning.
Bt.t for its negative points (considering only its thermodynamic and thermo-physical properties)
a:most the nearly perfect refrigerant. Incidentally it is the earliest refrigerant to be manufacin India; it is a by-product in fertilizer manufacturing.
antages

, Environment friendly: its atmospheric lifetime is only days to weeks and thus no ozone depletion and direct global warming potentials.
, The compressor displacement required per TR is much less, compared to other CFC, HCFC,
HFC and Hydrocarbon refrigerants now in use (refer Table 9.3). Thus for the same capacity,
compressor size will be smaller than for other refrigerants.
, BhpfTR is less than that of the other refrigerants (CFC, HCFC, HFC, etc.) in use.
, Because of the lower power requirement, the indirect global warming potential is less.

88

Basic Refrigeration and Air Conditioning

(Table 9.9

) Alternate Refrigerants

AEL

Temp.
glide c

ppm

93

50

1300

1000

AB/ POE

0.03

1080

6.4

1000

-34

MO/AB/POE

0.05

1440

8.1

1000

R 2 l 8/ l 34a/600a

-35

MO/AB/ POE

1770

6.9

1000

R407C
HFC

R 32/125/134a
23/25/52%

-43.7

POE

1610

7.4

1000

R 410A
HFC

R 321125

-52.7

POE

1800

< 0.2

1000

R402A
HCFC

R 22/ 125/290
38/60/2%

-47.4

MO/AB

0.02

2570

1000

R 4038
HCFC

R 22/290/218
56/5/39%

-50.6

MO/AB

0.03

3680

2.4

1000

R 404A
HCFC

R l 25/l 43a/ l 34a


44/52/4%

-46.5

POE

3750

0.7

1000

R 408A
HCFC

R 22/125/l 43a
47/7146%

-44.5

MO/AB/ POE

0.026

3050

0.6

1000

R 507A
HFC

R 125/ 143a
50/50%

-46.5

POE

3800

1000

-88

POE

n/a

1000

substitute
for

Alternate
and type

Chemical
composition

Boiling
pomtC

Compatible
lubncants

ODP

R 11
CFC

R 123
HCFC

dichloroLrifluoroethane

27.84

MO

0.02

Rl l/R 12
CFCs

R 134a
HFC

tetrafluoroethane

-26.5

POE

R401A
HCFC

R 22/152a/124
53/13/34%

-33

R 409A
HCFC

R 22/124/142b
60/25/15%

R 413A
HFC

GWP

Blends
R 12
CFC

R 22
HCFC

R 502
CFC

50150%

R 13,503
&
R 5088
R 23/l 16
R 23-CFC
HFC
MO- mineral oil; AB- alkylbenzene
AEL-'Acceptable Exposure Limit' in ppm

,,.

POE- polyolesters
composition of blends

Good heat transfer coefficients (approximately four times that ofR 22) results in smaller (more
compact) evaporator, condenser, heat exchangers; so reduction in capital cost of the system.
Further the operating temperature differences (ofcondenser and evaporator) can correspondingl} be changed; for the compressor to operate at higher evaporator and lower condensing
temperatures, thereby improving COP of the system.

Refrigerants and Brines

Temp.
glukC

ppm

50

1000

6.4

1000

8. l

1000

6.9

1000

7.4

1000

< 0.2

1000

1000

2.4

1000

0.7

1000

0.6

1000

1000

1000

, friction losses are very low. So requires comparatively smaller diameter refrigerant connecting
pipe of the refrigeration plant; so lower material and installation costs.
, There is no necessity of double suction/discharge gas risers for oil return during partial load
operation, as ammonia is not miscible with oil.
,,.. Thi~ is the cheapest refrigerant- incomparably low in cost and a\'ailable worldwide.
,, :here 'plate heat exchangers are used for condenser and evaporator, the refrigerant charge
ammonia) is substantially reduced, thus chances ofleakage is minimized and initial and maintenance, Costs come down.
~2 1s many times costlier than ammonia. As only about 10% of ammonia produced world
m.le is used for refrigeration, its price is not likely to rise, while the new refrigerants may
ho me still costlier, as they are produced only for refrigeration duty.

AEL

smaller (more
of the system.
corresponder condensing

89

dvantages
,,. Th most serious drawback, the importance of which cannot be minimized, is its high toxicity
.and ll is dangerous in excessively high concentrations. However its very unbearable punge nt
self-alarming smell (ammonia is its own warning agent) will drive away people even at nond.angerous concentrations of about 5 ppm, The bad effects, like, irritation, panic reaction,
cot.~hing, cramps, suffocation, etc. are felt only, as its concentration in air exceeds 250 ppm.
,. Ith also classified as oflowe1 flammability.
(an.mania-air mixtures are flammable, but only within a relatrvely narrow range of concenlral1on of
l~
25% by volume in air]. However, as it requires high intensity of ignition source of around
6.: ,- C, possibilities of explosion are very remote or non-existent, also it cannot sustain comb..~uon by itself, but need an outside source of fuel. Hence ammonia is not a fire and explosion
hazard. It is significant to note that ammonia installations do not require special frame proof
ele meals.
e" er, it is advisable to bleed nitrogen through the system, when using acetylene flame during
t" an ammonia system.
,,.. Be a use of these negative factors, it is generally not used for comfort, pharmaceutical applications, etc. Ammonia plants are usually manned by experienced personnel.
,,. Cc: mparatively high 'isentropic exponent' (NH3-l .3 l ,R 22-1.18,R 12-1 .14), resulting in higher
dh:harge gas temperature and consequent increase in valve reeds and oil temperatures. This
c;,'.ls for good thermal stability of the lubricant and steps to limit condensing temperature. So
range of single stage compression is restricted [generally not for evaporating temperature
below(-) 10C] To limit the condensing (and so the discharge gas temperature), only water
cc-c>led systems are adopted - so air cooled application is not favourable at all and reciprocating
ccmpressors should have watercooled cylinder heads and oil cooler.
Hm' ever, with screw compressor, it has been possible to have small air cooled system, as efficient
cooler is a must with this compressor and discharge gas temperature does not exceed safe limits
the ">Crew compressor.
, .\mmonia-oil miscibility being extremely poor, oil does not return automatically to the compressor, but accumulates at the bottom of the evaporator. It has to be drained periodically from
11 legs provided in the evaporator and oil has to be replenished in the compressor. Special
hook-up arrangements can be provided for the automatic draining- transport of the oil from
the evaporator to the compressor; but manual oil retrieval is generally adopted. Oil separator
0

90

)>

)>

)>

)>

Basic Refrigeration and.Air Conditioning

is usually provided to minimize oil carry over to the system, thus reducing the frequency of the
oil draining/replenishment work. The brighter aspect of the oil immiscibility (as indicated
under 'advantages') is the redundancy of double risers; this means, less pressure drop in the
refrigerant lines.
Reacts with copper and copper alloys and is incompatible with certain plastics. Hence copper
and copper based bearing materials cannot be used in the compressor and in the equipment in
the system and the refrigerant lines can be only of carbon steel.
Totally soluble in water and vice versa - a water presence of even 5% would not even be detectable in a large ammonia refrigeration system by the indications of pressures and temperatures.
Ammonia, oxygen, and moisture react forming harmful acids which attacks the materials in
the system, causes degradation oflubricant, forming sludge, thus ruining the system. Hence
the system has to be evacuated/dehydrated to a deep vacuum before charging the system with
refrigerant and the system has to be kept clean.
Has high electrical conductivity and presence of moisture increases the conductivity. Because
of the high conductivity, incompatibility with materials (copper and insulation materials) and
solubility in water, hermetic compressor, with copper (motor) winding and insulation materials, is not possible with ammonia.
Oflate, special hermetic has been developed, to be used with ammonia
It is not economical to have ammonia centrifugal compressor. Multi-staging required for the
temperature lift (compression) makes it expensive for a light gas like ammonia.

Ammonia has the unique distinction of being used as a refrigerant both in vapour compression
and vapour absorption systems of refrigeration.
Ammonia leak is detected by the use of burning sulphur stick, which gives a dense white smoke in
the presence of ammonia. Litmus paper also can be used. As ammonia is soluble in water, soap sud
test cannot be adopted.
The many advantages of ammonia as a refrigerant are evidently very solid. So it should be endeavoured to find ways to minimize the disadvantages. In this context, ASHRAE issued a policy statement on ammonia refrigerant in 1991, which says that the continued use of ammonia is necessary for
food preservation and air conditioning with proper risk management. Further, as per the reclassification of refrigerants by 'ASHRAE standard 34 -1997' or British standard BS4434 -1995' (see the fooc
notes in Table 9.3) ammonia can be used with a charge up to 500kg in indirect dosed system even for
air-conditioning of public places, like, hospitals, theaters, supermarkets, hotels, schools, lecture
halls, dwellings etc. Even where the refrigerant charge exceeds 500kg, the only extra stipulation is,
that all compressors and equipments should be located at ground level in a separate plant room. A
typical recent example of a high capacity air conditioning system with ammonia is, the OSLO air
port (1998); capacity 1800 TR, 2500 kg refrigerant charge. Majority oflarge capacity air conditioning systems the world over use the indirect chilled water system, using chilled water packages. So
such plants with ammonia are increasing.
Also thermal storage (ice accumulation) system with ammonia is getting popular.
R 744 -Carbon Dloxlde(C021; Inorganic Compound-ODP:O; GWP: 1; AEL:SOOO ppm

am monia carbon dioxide too has been in use as refrigerant since the last century. Positive features
are:no ODP, negligible direct global warming effect with a GWP of l ,chemically inactive, nonflammable, harmful only on high concentration in the air, low requirement of compressor displacement of0.0206 m~/min( 0. 727 cfm) per TR, quite cheap, no necessity for recovery/disposal, etc.

Refrigerants and Brines

e frequency of
ility (as indicat
ssure drop in

d temperatur
the materials
he system. Hen
g the system wi

uctivity. Becau

on materials) ancl
msulation materi-

should be endeaved a policy stateia is necessary for


per the reclassifi1995' (see the foot
system even for
. schools, lecture
xtra stipulation is.
te plant room. A
is, the OSLO air
city air conditionater packages. So

OOOppm

Like

~.. Positive features

iilly inactive, nonrnpressor displace!"\" disposal, etc.

91

strong negative features:


:::itical temperature of 31C(87 .8F) which is below the water temperature obtainable
~ 2C(90F)] from an operating cooling tower with an outside wet bulb temperature of
r generally prevalent during peak periods in the coastal regions of India and possittOiPJcal regions; so can be used only in cooler regions.
___ _e pressure is excessively high (72.7 kg/cm 2 (1034psig) at 30C (86F) condensing tem1 necessitating very strong construction of the equipment, increasing the capital cost.
- -h it has positive points as a refrigerant but because of the severe limitations oflow
rature and high operating pressures, it is of very little commercial use.
II can be used as the low stage refrigerant in a cascading refrigeration system for low
llmim:111.""':::;:::::::::e applications.

l--15.o bvtane-( C4 H 1oJ - Hydrocarbon - ODP: O; GWP: <3; AEL: 1000 ppm Ahydround, with 'O' ODP and very low GWP-has good thermodynamic properties, easily
much less cost than other refrigerants. But its application is limited, because, like other
, 1t is flammable and listed as hazardous.
ma, hydrocarbons, Propane and Isobutane have been in use as refrigerants for a long
...:=ited only to applications where expertise and facilities in handling flammable fluids are
--~~'Och as in petroleum refineries.
countries of European union, however, on the phase out of CFCs, isobutane has been
----~~.as an alternative to R 12 for the domestic refrigerator, by most of the leading refrigerator
rs. The contention is that it requires a concentration of 17 to 39 gm of isobutane in one
cf air to form an explosive mixture, while the charge of isobutane required for the
the biggest domestic refrigerators is extremely small. So, even if a big enough leak develrdea.se the full charge of the refrigerator instantly, the risk of an explosion is practically nil
em. The 'Greenfreeze' refrigerators- a popular European manufactured product-are
tw,e a charge of only 30 to 70 gm ofR 600a (i.e. only roughly 33% of the required charge
:34a). But other developed countries like USA, Japan etc, have not adopted R 600a as
fi r the refrigerator because ofits flammability.

--~~elv

necessary to have full global compliance of the Montreal Protocol and Kyoto agreestop further damage to the environment, that has been happening for the last several
fr m the emission of ozone depleting substances and greenhouse gases. To achieve these,
perating refrigeration systems with CFCs, have to be completely converted to or re~ wstems using environment friendly refrigerants. Obviously this is going to take a very
In the meantime, every one ofus in the ACR industry, particularly personnel engaged in
---=-~ring, erection and service should be fully aware of the impact of the CFCs and other
---c-;;m on the environment and make conscious efforts to stop/minimize their escape to the
_ __.,._.e [see: Look detection used chapter 34-special tools]

on-Service Sector
5rm...ted that only about 30% of the CFCs used as refrigerants, is consumed for charging new
n systems; the balance 70% being utilized for service purposes. Obviously quite a lot is

92

Basic Refrigeration and Air Conditioning

lost through leaks, such as from equipments, defective cylinder valves, poor handling practices, etc.
So erection/service sector has a major role in reducing damage to the environment.
Having been accustomed to handling mainly otherwise safer CFC refrigerants(which have noy,
been found to be not environment friendly) for the last several decades, there was not that much
concern about safety. But now the service personnel have to get fully acquainted with and strict!\
follow the precautionary measures, with a commitment to safety and enforce the programme to
conserve, recover and recycle CFCs.
One can easily list out the steps in this direction-to cite a few, such as:
- Maintaining the refrigeration system leak tight. Regular leak check and prompt rectification of
the gas leaks in the systems, have been quite important in ACR service and maintenance, so as
to have the system properly charged for keeping up the efficiency of the system, for proper oil
return, to limit discharge gas temperature, to keep down cost of maintenance (refrigerants
being very costly), etc. Now this has acquired much greater significance, than ever before.
- To minimize the chances of gas leaks from the system, have the absolute minimum of mechanical joints; brazed /welded joints are very much less susceptible to gas leaks.
- Open the refrigeration side of the system only when it is absolutely inescapable and if the
system has to be opened for repairs, refrigerant reclaim unit should invariably be used for
removal of refrigerant from the system.
- No gas should be purged out to the atmosphere from the system.
- Replace and tighten all seal caps on service valves and also on refrigerant cylinders; this is one
item many service personnel miss to do.
- Do not use CFCs as tracer gas for leak testing systems.
- Do not use CFCs for cleaning contaminated systems (R 11 had been in use for cleaning burnt
hermetic systems).
- Improve the efficiency of the purge unit in negative pressure chillers (R 11 centrifugal chiller),
to minimize the quantity of refrigerant getting purged along with the non-condensables
purged from the chiller system It is said that in an average purge unit, 3 to 8 kg of refrigerant
gas gets purged along with every kg of non condensibles purged out from the system (i.e. 3 to
8 times). By improving the purge unit, the refrigerant purged out can be brought down to
0.5 kg per kg of non condensibles purged from the system. It will be advantageous to replace
the conventional type of purge with the thermal (refrigerated) type, which works at very much
lower purge discharge pressure and thus the loss of refrigerant on purging is substantially
reduced (see 'thennal purge' in chapter on 'Centrifugal compressor').

Short Term and Long Term Plans-Options


Around 70% of CFCs consumed as refrigerants, is estimated to be used for service purposes. Obviously, the service requirement will go up as more plants get added every year and many may require
more frequent servicing as they age. Thus, with their requirement going up, side by side with the
planned progressive curtailment of their production and ultimate total phase out by 2009, the price
of CFCs can/will escalate and eventually impossible to obtain.
In this scenario, the options available for users of existing equipments with CFCs are:
(i) Make existing plant nearly leak proof. Jn normaJly leak proof systems, like the domestic refrigerator and medium siLed hermetic systems, which are running satisfactorily, there is no technical reason to replace the CFC and so can be allowed to live its useful life period.

Refrigerants and

as not that much


with and strictly
e programme to

..(JR- Convert (retrofit) the existing plant with medium term alternate (interim) refrigerant, as
rtage of CFC refrigerants tends to become acute.
-OR- Plan to replace the existing plant with new equipment using long term alternate refriger.a:nt at the earliest, depending upon the age of the existing plant. This is applicable particularly
industrial applications, where the industrial process is completely dependant on refrigeraoon Evidently it will be prudent to plan complete replacement of the plant long before a
major breakdown of the plant due to old age or as CFC refrigerants become scarce.
d

aintenance, so as
m, for proper oil
ce (refrigerants
n ever before.
num ofmechani-

nders; this is one

r cleaning burnt
mrifugal chiller),
on-condensables
kg of refrigerant
e system (i.e. 3 to
brought down to
geous to replace
irks at very much
g is substantially

purposes. Obviany may require


e by side with the
v 2009, the price

jCsare:
domestic refrig~. there is no techkriod.

le

Brinetl 9!_

Indian context, even with the tapering domestic production ofR 11 and R 12, these CFCs
pected to be available for quite sometime, though at escalating prices. So, probably retrofitexisting R 11 or R 12 systems with interim alternates may not be warranted. This line of
his because, that many of the interim refrigerants are HCFCs and HCFC based blends, all of
-e not manufactured in India and so will have to be imported. Further, because of their
content, their production too is being progressively reduced and they ultimately will be
out in due course in the countries where they are being manufactured now.
eYer, existing systems with CFCs, like, R502, Rl3, Rl J.l, etc. will need retrofitting with
.Jternates, as these are not manufactured in the country and imports too will dry up, since
are already phased out in other countries.
re it is planned to convert an existing CFC system with an interim or long term alternate
_ rant, thorough discussions should be held with the designer, also manufacturer or supplier
equipment and the supplier of the alternate refrigerant, to ensure that the alternate is compatoith the existing system in every detail and suitable for the application.
deciding whether to convert a system with a even a long term alternate refrigerant or complete
ement with new non-CFC system, an important aspect is the comparison of costs of replace;..nd conversion. Sometimes the cost ofconversion (retrofitting) may turn out to be a very high
t of the cost for complete replacement with new equipment using long term non CFC re frig!.. ..\lso on conversion with interim alternate refrigerant, the efficiency of the system can drop,
~~..-... to increased power costs, while the efficiency of the new systems with non CFC refrigerant
been found to be much better. Thus the power requirement comparison too becomes a vital
m determining the action plan.
(; ..1ally conversion calls for elaborate internal cleaning of the existing system. There are some
.He refrigerants, claimed to be straight replacements i.e. nor needing elaborate internal flusha"!d cleaning. Such claims are on the assumption that the existing system is quite clean and in
condition. So, unless one is quite sure about the condition of the system, it is better, as an
dant precaution, to carry out even component wise flushing co clear the system of all traces of
o.! and refrigerant. [see 'Lubricant - Refrigerant Compatibilit/ in chapter on 'Lubricatwnl
Further, there are some (interim, as well as, long-term) alternates that are compatible with the oil
materials used in the CFC system, except for some specific items, like, gasket materials, electrical
tion material , shaft seal etc. So, before doing a retrofit, detailed discussions with the alternate
,..erant supplier is necessary to clear all details.
f ;om the above points, it will be abundantly clear that the refrigerants and lubricants should be
ned only from long term well established, reliable and knowledgeable suppliers, who have
..ence in the country.
Retrofit instructions are usually given by the refrigerant manufacturer. The relevant instructions
the refrigerant selected to be used, should be obtained and followed.

94

Basic Refrigeration and Air Conditioning

A summary of points collected from the recommendations ofleading manufacturers of refri


ants and compressors voicing a cautious approach is given in the lt.ppendix' section, as an exarr
SECONDARY REFRIGERANTS-BRINES

In large capacity refrigeration plants with evaporators located at widely spread out areas/locatio1
application of cooling, it becomes necessary to run long lengths of refrigerant lines to the evap
tors, which will raise the refrigerant charge, increase the pressure drop in the refrigerant side
also increase the chances ofrefrigerant leakage.
For such applications, a liquid is chilled in a centrally located chiller package and it is circul
by pumps between the chiller and the various cooling coils(in AH Us) or heat exchanger jacke
industrial processing, located at the cooling application points, for effecting transfer of of heat f
the substance to be cooled . Thus the liquid becomes a carrier of refrigeration and so is kn
as'Secondary refrigerant'. As is evident the secondary refrigerant does not undergo any change of s
Water is used as the secondary refrigerant for temperature applications above its freezing poi1
0C and for sub-zero applications brines or glycols are employed.
Brine is a solution formed by dissolving a soluble substance in water. The soluble substance C<
be a salt, like, sodium chloride or calcium chloride or a glycol. On mixing a soluble substanc
water, its freezing point is lowered, or in other words, the solution so formed has a lower free
point than water.
( Table 9. 10 ) Application of Various Brines

Application
Dairies
Food processing
Ice cream
Breweries
Meat packing
Special low temp.
Skating ring
Ice plants
Chemical plants

Salt brines
Sodium-chloride
Calcium-chloride

""

""

Glycols
Ethylene glycol

propylene gl;

"""
""
"'

The weight of the salt or glycol in the solution, expressed as a percent of the total weight of
solution, is known as the 'strength' or 'concentration' of the brine. As the concentration of the solw
increases, its freezing point goes down. Thus for a particular concentration of a solution, there
definite freezing point. When a solution at a particular concentration is cooled below its freei
point, some portion of water in the solution will freeze out as pure ice. With the reduced w:
content, the remaining solution attains higher concentration and consequently a lower freei
point. Ultimately on further cooling the solution itself freezes and the temperature at which
happens is known as its eutectic point.
With the addition ofa soluble substance in water, the density or specific gravity of the resul1
solution will be higher; but its specific heat becomes lower than that of water. Since both spe

1~fucturers

95

Refrigerants and Brines

of refrigeron, as an example

and specific heat of water are one, the specific gravity of a brine I solution will always be
than one, while its specific heat will be less than one. Further, the specific gravity of a brine
pnicular concentration decreases as its temperatu re is increased, while its specific heat in(fable 9. 11 ). T herefore, wh ile calculating the heat removal from a brine, its specific gravity
~cheat values for the particular concentration should be used.

utareas/locationsof
Imes to the evapora-efrigerant side and

.1 1) Prope rties of Brines and G lycols

e and it is circulated
exchanger jackets in
~,sfer of of heat from
n and so is known
any change of state.
its freezing point of

Freezing
point

Specific
gravity

Specific
heat

Viscosity
centpoise

- 1.l C
(30F)
-9.4C
(15F)

12

-SC
( 17 .5F)
-17.2C
( IF)

1.093

0.86

2.2

1.166

0.8

4.2

1. 109

0.83

2.4

1.199

0.72

4.8

1.256

0.67

10.3

1.3 16

0.63

27.8

1.037

0.92

3.7

l.058

0.86

6.8

1.08

0.79

17.2

1.106

0.73

75

1.034

0.94

1.046

0.89

20

1.066

0.83

80

1.077

0.77

700

- 1.l C
(30F)
-9.4C
(15F)
- 20.6C
(-5F)
-34.4C
(-30F)

propylene glycol

'1
'1
'1
'1
Jene
I

v of the resulting
mce both specific

Concentration
% by weight

- 1.I C
(30F)
-9.4C
(15F)
-20.6C
(-5F)
-34.4C
(-30F)

' le substance could


Jubie substance in
as a lower freezing

total weight of the


uon of the solution
olution, there is a
' below its freezing
the reduced water
. a lower freezing
:nu n~ at which this

Application
temperature

-1.IC
(30F)
-9.4C
(15F)
-20.6C
(-5F)
-34.4C
(-30F)

21
12
20

-7.2C
(19F)
- 17.2C
( l f)

25
30
25
35
45
55
30
40
50
60

- 29.4C
(-21F)
-44C
(-47F)
- 10.6C
(12.9F)
-1 7.SC
( 0 F)
-26.4C
(- 15.5 F)
-41.7C
(-43F)
-10.6C
(13F)
-20. l C
(-4.2F)
-33.9C
(-29F)
-48.3C

, ~mpl~ ~.2

Ca curate the heat to be removed, to cool 1000 litres of calcium chloride brine at 20% concentran, from Oto-10c.

aj Basic Refrigeration and Air Conditioning


sc

Mean temperature of brine - Y:z ((0 + (-) 1OJ =(-) 0


Range of cooling = 10 C
Sp. gravity of brine at 20% concentration at - 0 =1.193
Sp. heat of 20% brine at - s0 c o.73
Heat to be removed [1000 x 1.193 x 0.73 x 10] 8709 kcal
(see under Table A.14 in Appendix section for 'Liquid chilling calculation']

sc

=
=

Following are the important factors to be considered in selecting the brine.


Freezing point: The brine should have a concentration for which the freezing point has neces
to be lower than the brine temperature to be maintained for the application - generally by abou
8C. This difference is to prevent sudden crystallization of the brine, if the temperature of the 1
falls down accidentally.
Safety: The brine should be non-inflammable and non-toxic.
Suitability: Should be compatible with the materials of the equipment.
pH value: Ideally should be neutral, to minimize corrosion. But neutral or near neucral brin
become corrosive with contamination during the operation.
Specific heat: determines the rate of flow of brine required - higher the specific heat, lower v

the rate of flow required.


Density: has no bearing on heat transfer aspects, but is helpful in finding the strength of a brine

the help ofa hydrometer and thermometer.


Viscosity: again does not influence the heat transfer aspect; but where the viscosity of a brine ris

as its temperature falls, the pumping head and so the pumping horsepower will go uneconorr
high. A typical example is propylene glycol - its viscosity rises very high below a temperature<
C (20 F).
The brines in common use are of sodium chloride, calcium chloride and glycols, such as eth
glycol, propylene glycol, etc.

Salt Brines (Sodium Chloride and Calcium Chloride Brines) Sodium chloride (commo
is cheaper than calcium chloride. But since the freezing point of sodium chloride brine is corr
tively high, it can be used only in applications requiring brine temperature not lower than
-12 C ( 10 F). Calcium chloride brine is favoured for most applications, because of its lower
ing point. Where contact with calcium chloride brine is not permitted, sodium chloride b1
used, such as in fast freezing I glazing of fresh catch of fish in fishing trawlers and other foo
Ideal pH value for sodium and calcium chloride brines is 7.5 to 8.5; a brine slightly alka
considered safer than being slightly acidic. To correct acidic condition of these brines, causti
(an alkaly) dissolved in warm water is added, while for correcting an alkaline condition, ac
chromic or hydro-chloric acid is used.
Standard steel pipes can be used for brine piping- copper pipe cannot be used.
Glycols Ethylene and propylene glycols are widely used in cooling as well as heating a pp lie;
Ethylene glycol solution is usually preferred, as it has more desirable properties at lower ten
tu res, but operation below-50C(-60F) is not advisable. However for food and beverage cc

Re.fiigerants and Brines

97

bcations, \'>here there are chances of the g\yco\ so\ution coming in contact with the

only propylene glycol is employed, as propylene glycol is not toxic as ethylene


arculated by centrifugal pumps, with rubber impregnated asbestos or equivalent for
ng. However, to prevent/minimize drip losses of glycol solution through the pump
=marucal seal is preferable.
ck galvanized surfaces, forming sludge, so should be avoided. Standard steel and
-z ran be used for glvcol lines.
has necessarih
\ by about 5 to
.re of the brine

tral brine can

:;.r""'.':~7e

The salt brines can become corrosi\ e, due to


n, m handling and operation, like, when too much air gets mixed with the brines. So
.arrauon ofbrines is to be avoided - as far as possible, should be kept in closed systems, the
ould be kept cO\ered etc These brines attack copper and steel parts, resulting in
ces. If preventi\e measures are not adopted, the copper tubes in the chiller can
If brine enters the refrigeration system, it will naturally affect the system, calling for
hing. cleaning, dehydrating, etc. So, in addition Lo correcting the pH of the brines,
e to be added to combat corrosion. Inhibiters, like sodium chromate or sodium-dichroto be effective with these brines in overcoming corrosion. The recommended inhibitor
Effect of Brines and Glycol Solutions

-~-....~n1:

. lower will be

m chloride brine- - - - 2 kg per 1000 litres (l.67lb per 100 US gals) of brine
m chloride brine - - - - 3.2 kg per 1000 litres(2.67lbi IOOUS gal) of brine
-~._...,...te comes

ofa brine with


brine rises fust
economically
rature of - 7
has ethylene
ommonsalt)
e 1s comparar than about
lower freezride brine is
er foods.
Iv alkaline is
causLic sod a
on, acetic or

ipplications.
er tempera1ge cooling/

in granular form and it dissolves ver> slowly in cold brine. So it should not be
th to low temperature brine; dissolve it in warm water and add the solution away from
pump suction take off point in the brine tank, so that only dilute solution reaches the
i\ ore! of caution-if the chromate or its solution comes in contact ''ith skin, rashes can
_ _,.-\\~sh skin immediate!} with water.
eth' lene and propylene glycols, when pure, are less corrosive than even water, but due to
of water used for preparing the solution the} can turn to be corrosive, particularly when
mixed. Soft water or if possible distilled water or condensate water should be used for
~-"TTTl,,T he solution to avoid the effects of bad water quality. In any case, inhibited glycols, which
ble, should be used. Ifinhibited glycol is not available, the glycol manufacturer should be
~--.--hed for recommending the suitable inhibitor.
rhromate or chromate should not be wed as inhibitors with glJcols, as oxidation ofglJcol can occur,
solutwn more corrosive.
orrf solution is used here to cover both the salt brines and glycol solutions).
To ensure fair!) non-corrosive solutions for a long period of time, it is
portant to monitor the inhibitor concentration and replenish the inhibitor as necessary. For
lhe pH readings should be regularly recorded follo""ed with pe1iodical analysis of solution
le. This systematic approach also will prevent indiscriminate addition of inhibitor. which is
e~ harmful.
The rate of depletion of the inhibitor in a solution depends upon the usage of the plant- this may
fi Gm job to job.Hence in the initial stages on commissioning the plant, it may be necessary to do
analvsis of the solution frequently to establish a pattern for the maintenance schedule.
mce these solutions are generally used in industrial applications as secondary refrigerants, it
Id not be difficult to adhere to these simple yet very important maintainence steps. Plant failures
itor Maintenance

98

Basic Refrigeration and Air Conditioning

due to corrosion can be attributed to ignorance or callous negligence of these maintenance stepsthe necessisty of these steps has to be overemphasized.
Other Secondary Refrigerants Many of the halocarbon refrigerants have been in use as secondan
refrigerants also, because of their favourable properties such as, low freezing points, good heat
transfer coefficients, non-flammability, stability, low viscosities, etc. But because of environmental
considerations now these cannot be used.
Chilled special grade oils for heat treatment purposes, chilled kerosene oil as coolant for machining cast iron, etc. are others in this category.

You might also like