Antifreeze

Fluorescent-green dyed antifreeze is visible in the radiator header

tank when car radiator cap is removed

Topping up the antifreeze solution in a cars cooling system is a

routine maintenance item for most modern cars.

1 Automotive and internal combustion engine use

An antifreeze is an additive which lowers the freezing

point of a water-based liquid. An antifreeze mixture is
used to achieve freezing-point depression for cold environments and also achieves boiling-point elevation (antiboil) to allow higher coolant temperature. Freezing
and boiling points are colligative properties of a solution,
which depend on the concentration of the dissolved substance.

Most automotive engines are water"-cooled to remove waste heat, although the water is actually antifreeze/water mixture and not plain water. The term
engine coolant is widely used in the automotive industry, which covers its primary function of convective
heat transfer for internal combustion engines. When
used in an automotive context, corrosion inhibitors are
added to help protect vehicles radiators, which often
contain a range of electrochemically incompatible metals (aluminum, cast iron, copper, brass, solder, et cetera).
Water pump seal lubricant is also added.

Because water has good properties as a coolant, antifreeze

is used in internal combustion engines and other heat
transfer applications, such as HVAC chillers and solar
water heaters. The purpose of antifreeze is to prevent
a rigid enclosure from bursting due to expansion when
water freezes. Commercially, both the additive (pure
concentrate) and the mixture (diluted solution) are called
antifreeze, depending on the context. Careful selection
of an antifreeze can enable a wide temperature range in
which the mixture remains in the liquid phase, which is
critical to ecient heat transfer and the proper functioning of heat exchangers.

Antifreeze was developed to overcome the shortcomings

of water as a heat transfer uid. In some engines freeze
plugs (engine block expansion plugs) are placed in areas of the engine block where coolant ows in order to
protect the engine from freeze damage if the ambient
temperature drops below the freezing point of the antifreeze/water mixture. These should not be confused
with core plugs, whose purpose is to allow removal of
sand used in the casting process of engine blocks (core
plugs will be pushed out if the coolant freezes, though,
assuming that they adjoin the coolant passages, which is
not always the case).

Salts are frequently used for de-icing, but salt solutions

are not used for cooling systems because they can cause
severe corrosion to metals. Instead, non-corrosive antifreezes are commonly used for critical de-icing, such as
for aircraft wings.

On the other hand, if the engine coolant gets too hot, it

might boil while inside the engine, causing voids (pockets
of steam), leading to localized hot spots and the catastrophic failure of the engine. If plain water were to be
used as an engine coolant, it would promote galvanic
1

3 PRIMARY AGENTS

corrosion. Proper engine coolant and a pressurized 3 Primary agents

coolant system can help obviate the problems which make
plain water incompatible with automotive engines. With Most antifreeze is made by mixing distilled water with
proper antifreeze, a wide temperature range can be tol- some kind of alcohol.
erated by the engine coolant, such as 34 F (37 C) to
+265 F (129 C) for 50% (by volume) propylene glycol diluted with water and a 15 psi pressurized coolant 3.1 Methanol
system.[1][2]
Early engine coolant antifreeze was methanol (methyl alcohol). Methanol was widely used in windshield uids,
however, in Europe, due to new REACH legislation, the
use of methanol in windshield uids is limited to 5% and
in the near future will be further reduced to 3%.[3] As
radiator caps were vented, not sealed, the methanol was
lost to evaporation, requiring frequent replenishment to
avoid freezing of the coolant. Methanol also accelerates
corrosion of the metals, especially aluminum, used in the
engine and cooling systems. Ethylene glycol was developed, and soon replaced methanol as an engine cooling
system antifreeze. It has a very low volatility compared to
methanol and to water. Before the 1970s, coolant systems
were unpressurized and the engine was often cooler than
modern automotive engines. By pressurizing the coolant
system with a radiator cap, the boiling point of the uid
is increased, permitting higher engine temperatures and
better fuel eciency. Pressurized systems do not appreciably change the freeze point.

Methanol (also known as methyl alcohol, carbinol, wood

alcohol, wood naphtha or wood spirits) is a chemical
compound with chemical formula CH3 OH. It is the simplest alcohol, and is a light, volatile, colorless, ammable,
poisonous liquid with a distinctive odor that is somewhat milder and sweeter than ethanol (ethyl alcohol). At
room temperature, it is a polar solvent and is used as
an antifreeze, solvent, fuel, and as a denaturant for ethyl
alcohol. It is not popular for machinery, but may be
found in automotive windshield washer uid, de-icers,
and gasoline additives.

Ethylene glycol

Other uses

The most common water-based antifreeze solutions used

in electronics cooling are mixtures of water and either
ethylene glycol (EGW) or propylene glycol (PGW). The
use of ethylene glycol has a longer history, especially
in the automotive industry. However, EGW solutions
formulated for the automotive industry often have silicate based rust inhibitors that can coat and/or clog heat
exchanger surfaces. Ethylene glycol is listed as a toxic
chemical requiring care in handling and disposal.

3.2 Ethylene glycol

Ethylene glycol solutions became available in 1926 and

were marketed as permanent antifreeze since the higher
boiling points provided advantages for summertime use
as well as during cold weather. They are used today for a
variety of applications, including automobiles, but gradually being replaced by propylene glycol due to its lower
toxicity.
When ethylene glycol is used in a system, it may become
oxidized to ve organic acids (formic, oxalic, glycolic,
glyoxalic and acetic acid). Inhibited ethylene glycol antifreeze mixes are available, with additives that buer the
pH and reserve alkalinity of the solution to prevent oxidation of ethylene glycol and formation of these acids.
Nitrites, silicates, theodin, borates and azoles may also
be used to prevent corrosive attack on metal.

Ethylene glycol has desirable thermal properties, including a high boiling point, low freezing point, stability over
a wide range of temperatures, and high specic heat
and thermal conductivity. It also has a low viscosity
and, therefore reduced pumping requirements. Although
EGW has more desirable physical properties than PGW,
the latter coolant is used in applications where toxicity
might be a concern. PGW is generally recognized as safe 3.2.1 Poisoning
for use in food or food processing applications, and can
Main article: Ethylene glycol poisoning
also be used in enclosed spaces.
Similar mixtures are commonly used in HVAC and industrial heating or cooling systems as a high-capacity heat
transfer medium. Many formulations have corrosion inhibitors, and it is expected that these chemicals will be replenished (manually or under automatic control) to keep
expensive piping and equipment from corroding.

Ethylene glycol is poisonous to humans and other

animals,[4][5] and should be handled carefully and disposed of properly. Its sweet taste can lead to accidental ingestion or allow its deliberate use as a murder
weapon.[6][7][8] Ethylene glycol is dicult to detect in the

3.4

Glycerol

body, and causes symptomsincluding intoxication, severe diarrhea, and vomitingthat can be confused with
other illnesses or diseases.[4][8] Its metabolism produces
calcium oxalate, which crystallizes in the brain, heart,
lungs, and kidneys, damaging them; depending on the
level of exposure, accumulation of the poison in the body
can last weeks or months before causing death, but death
by acute kidney failure can result within 72 hours if the
individual does not receive appropriate medical treatment
for the poisoning.[4] Some ethylene glycol antifreeze mixtures contain an embittering agent, such as denatonium,
to discourage accidental or deliberate consumption.

3.3

Propylene glycol

Propylene glycol

Propylene glycol, on the other hand, is considerably less

toxic than ethylene glycol and may be labeled as nontoxic antifreeze. It is used as antifreeze where ethylene
glycol would be inappropriate, such as in food-processing
systems or in water pipes in homes where incidental ingestion may be possible. As conrmation of its relative non-toxicity, the FDA allows propylene glycol to be
added to a large number of processed foods, including ice
cream, frozen custard, salad dressings and baked goods.

3.4 Glycerol
Once used for automotive antifreeze, glycerol has the
advantage of being non-toxic, withstands relatively high
temperatures, and is noncorrosive.
Like ethylene glycol and propylene glycol, glycerol is
a non-ionic kosmotrope that forms strong hydrogen
bonds with water molecules, competing with water-water
hydrogen bonds. This disrupts the crystal lattice formation of ice unless the temperature is signicantly lowered. The minimum freezing point temperature is at
about 36 F / 37.8 C corresponding to 6070% glycerol in water.[12]
Glycerol was historically used as an antifreeze for automotive applications before being replaced by ethylene
glycol, which has a lower freezing point. While the
minimum freezing point of a glycerol-water mixture is
higher than an ethylene glycol-water mixture, glycerol is
not toxic and is being re-examined for use in automotive
applications.[13][14] Glycerol is mandated for use as an antifreeze in many sprinkler systems.
In the laboratory, glycerol is a common component of solvents for enzymatic reagents stored at temperatures below
0 C due to the depression of the freezing temperature
of solutions with high concentrations of glycerol. It is
also used as a cryoprotectant where the glycerol is dissolved in water to reduce damage by ice crystals to laboratory organisms that are stored in frozen solutions, such
as bacteria, nematodes, and mammalian embryos.

4 Measuring the freeze point

Once antifreeze has been mixed with water and put into
use, it periodically needs to be maintained. If engine
coolant leaks, boils, or if the cooling system needs to be
drained and relled, the antifreezes freeze protection will
need to be considered. In other cases a vehicle may need
to be operated in a colder environment, requiring more
Propylene glycol oxidizes when exposed to air and heat, antifreeze and less water. Three methods are commonly
[15]
forming lactic acid.[9][10] If not properly inhibited, this employed to determine the freeze point of the solution:
uid can be very corrosive, so pH buering agents such
1. Specic gravity(using a hydrometer or some sort
as dipotassium phosphate, Protodin and potassium biof oating indicator),
carbonate are often added to propylene glycol, to prevent acidic corrosion of metal components. Pre-inhibited
2. Refractometerwhich measures the refractive inpropylene glycol solutions like Dowfrost (manufactured
dex of the antifreeze solution and translates it into
by Dow Chemicals, US) and Tonofrost (manufactured by
freeze point, and
Chemtex Speciality Ltd, India) can also be used instead
of pure propylene glycol to prevent corrosion.
3. Test stripsspecialized, disposable indicators made
for this purpose.
Besides cooling system corrosion, biological fouling also
occurs. Once bacterial slime starts to grow, the corrosion
rate of the system increases. Maintenance of systems us- Although ethylene glycol hydrometers are widely availing glycol solution includes regular monitoring of freeze able and mass-marketed for antifreeze testing, they give
protection, pH, specic gravity, inhibitor level, color, and false readings at high temperatures because specic gravbiological contamination. Propylene glycol should be re- ity changes with temperature.[15] Propylene glycol solutions cannot be tested using specic gravity because of
placed when it turns a reddish color.[11]

ADDITIVES

ambiguous results (40% and 100% solutions have the Potassium 2-ethylhexanoate and ethylhexanoic acid is insame specic gravity).[15]
compatible with nylon 6,6 and silicone rubber, and is a
known plasticizer. Class action lawsuits were registered
in several states, and in Canada,[21] to address some of
these claims. The rst of these to reach a decision was
5 Corrosion inhibitors
in Missouri where a settlement was announced early in
December 2007.[22] Late in March 2008, GM agreed to
Most commercial antifreeze formulations include compensate complainants in the remaining 49 states.[23]
corrosion inhibiting compounds, and a colored dye GM (Motors Liquidation Company) led for bankruptcy
(commonly a green, red, orange, yellow, or blue in 2009, which tied up the outstanding claims until a court
uorescent) to aid in identication.[16] A 1:1 dilution determines who gets paid.[24]
with water is usually used, resulting in a freezing point of
about 34 F (37 C), depending on the formulation. In According to the DEX-COOL manufacturer, mixing a
warmer or colder areas, weaker or stronger dilutions are 'green' [non-OAT] coolant with DEX-COOL reduces the
but
used, respectively, but a range of 40%/60% to 60%/40% batchs change interval to 2 years or 30,000 miles,
[25]
will
otherwise
cause
no
damage
to
the
engine.
DEXis frequently specied to ensure corrosion protection,
and 70%/30% for maximum freeze prevention down to COOL antifreeze uses two inhibitors: sebacate and 2EHA (2-ethylhexanoic acid), the latter which works well
84 F (64 C).[2]
with the hard water found in the US, but is a plasticizer
which can cause gaskets to leak.[17]

5.1

Maintenance

According to internal GM documents, the ultimate culprit appears to be operating vehicles for long periods of
time with low coolant levels. The low coolant is caused by
pressure caps that fail in the open position. (The new caps
and recovery bottles were introduced at the same time as
DEX-COOL). This exposes hot engine components to air
and vapors, causing corrosion and contamination of the
coolant with iron oxide particles, which in turn can aggravate the pressure cap problem as contamination holds
the caps open permanently.[26]

In the absence of leaks, antifreeze chemicals such as ethylene glycol or propylene glycol may retain their basic
properties indenitely. By contrast, corrosion inhibitors
are gradually used up, and must be replenished from time
to time. Larger systems (such as HVAC systems) are often monitored by specialist rms which take responsibility for adding corrosion inhibitors and regulating coolant
composition. For simplicity, most automotive manufacturers recommend periodic complete replacement of en- Honda and Toyotas new extended life coolant use OAT
gine coolant, to simultaneously renew corrosion inhibitors with sebacate but without the 2-EHA. Some added phosand remove accumulated contaminants.
phates provide protection while the OAT builds up.[17]
Honda specically excludes 2-EHA from their formulas.

5.2

Traditional inhibitors

Typically OAT antifreeze contains an orange dye to differentiate it from the conventional glycol-based coolants
(green or yellow). Some of the newer OAT coolants claim
to be compatible with all types of OAT and glycol-based
coolants; these are typically green or yellow in color (for
a table of colors, see[16] ).

Traditionally, there were two major corrosion inhibitors

used in vehicles: silicates and phosphates. American made vehicles traditionally used both silicates and
phosphates.[17] European makes contain silicates and
other inhibitors, but no phosphates.[17] Japanese makes
traditionally use phosphates and other inhibitors, but no
5.4
silicates.[17][18]

5.3

Organic acid technology

Hybrid organic acid technology

HOAT coolants typically mix an OAT with a traditional

inhibitor, such as silicates or phosphates.

G05 is a low-silicate, phosphate free formula that includes

[17]
Certain cars are built with organic acid technology (OAT) the benzoate inhibitor.
antifreeze (e.g., DEX-COOL[19] ), or with a hybrid organic acid technology (HOAT) formulation (e.g., Zerex
G-05),[20] both of which are claimed to have an extended 6 Additives
service life of ve years or 240,000 km (150,000 mi).
DEX-COOL specically has caused controversy. Litigation has linked it with intake manifold gasket failures
in General Motors' (GMs) 3.1L and 3.4L engines, and
with other failures in 3.8L and 4.3L engines. One of
the anti-corrosion components presented as sodium or

All automotive antifreeze formulations, including the

newer organic acid (OAT antifreeze) formulations, are
environmentally hazardous because of the blend of additives (around 5%), including lubricants, buers and corrosion inhibitors.[27] Because the additives in antifreeze

5
are proprietary, the safety data sheets (SDS) provided [8]
by the manufacturer list only those compounds which
are considered to be signicant safety hazards when
used in accordance with the manufacturers recommendations. Common additives include sodium silicate,
disodium phosphate, sodium molybdate, sodium borate,
and dextrin (hydroxyethyl starch). Disodium uorescein [9]
dyes are added to antifreeze to help trace the source of
leaks, and as an identier since some dierent formula[10]
tions are incompatible.[16]

Angela Chambers and Jon Meyersohn (2009-04-23).

Exhumed Body Reveals Stacey Castors First Husband
'Didn't Just Die': Exclusive Look Inside Anti-Freeze Murder Mystery; What Brought Two Men to Rest in Neighboring Graves. ABC. Archived from the original on 25
April 2009. Retrieved 2009-04-25.
Charles Loudon Bloxam (1873). Chemistry, inorganic and
organic: with experiments (2 ed.). H.C. Lea. p. 587.
Evaluation of Certain Food Additives and Contaminants
(Technical Report Series). World Health Organization. p.
105. ISBN 92-4-120909-7.

Automotive antifreeze has a characteristic odor due to

the additive tolytriazole, a corrosion inhibitor. The unpleasant odor in industrial use tolytriazole comes from [11] When an aqueous solution of propylene glycol in a cooling or heating system develops a reddish or black color,
impurities in the product that are formed from the toluithis indicates that iron in the system is corroding signifdine isomers (ortho-, meta- and para-toluidine) and metaicantly. In the absence of inhibitors, propylene glycol
diamino toluene which are side-products in the manufaccan react with oxygen and metal ions, generating various
ture of tolytriazole.[28] These side-products are highly recompounds including organic acids (e.g., formic, oxalic,
active and produce volatile aromatic amines which are reacetic). These acids accelerate the corrosion of metals in
[29]
sponsible for the unpleasant odor.
the system. See:

See also
Air cooling
Cryoprotectant
Heater core
Ice melt
Internal combustion engine cooling
Radiator
Water cooling

References

Notes
[1] Prestone Press Release
[2] Peak Antifreeze chart
[3]
[4] Brent J (2001).
Current management of ethylene glycol poisoning.
Drugs 61 (7): 97988.
doi:10.2165/00003495-200161070-00006. ISSN 00126667. PMID 11434452.
[5] Antifreeze Warning. The Cat Fanciers Association,
Inc. Retrieved 2007-05-15.

Glycol turning red. What does it indicate?" See:

Chemtex
Hartwick, D. ; Hutchinson, D. ; Langevin, M., A
multi-discipline approach to closed system treatment, Corrosion 2004; New Orleans, Louisiana;
March 28 - April 1, 2004; NACE (National Association of Corrosion Engineers) paper 04-322. See:
Document preview.
Kenneth Soeder, Daniel Benson, and Dennis
Tomsheck, An on-line cleaning procedure used
to remove iron and microbiological fouling from
a critical glycol-contaminated closed-loop cooling
water system, 2007 Annual Convention and Exposition of the Association of Water Technologies; Colorado Springs, Colorado; November 710,
2007.
Allan Browning and David Berry (September /
October 2010) Selecting and maintaining glycol
based heat transfer uids, Facilities Engineering
Journal, pages 16-18.
Walter J. Rossiter, Jr., McClure Godette, Paul W.
Brown and Kevin G. Galuk (1985) An investigation of the degradation of aqueous ethylene glycol
and propylene glycol solutions using ion chromatography, Solar Energy Materials, vol. 11, pages 455467.
[12] Glycerol Freezing Point
[13] Hudgens, R. Douglas; Hercamp, Richard D.; Francis,
Jaime; Nyman, Dan A.; Bartoli, Yolanda (2007). An
Evaluation of Glycerin (Glycerol) as a Heavy Duty Engine
Antifreeze/Coolant Base. doi:10.4271/2007-01-4000.
Retrieved 2013-06-07.

[6] Nash, Alanna. The Black Widow Killer: Two men. Two
murders. Too many questions.. Readers Digest. Retrieved 2009-04-26.

[14] Proposed ASTM Engine Coolant Standards Focus on

Glycerin. Retrieved 2013-06-07.

[7] Munro, Ian (2007-10-13). Death by anti-freeze 'perfect

murder'". The Age. Retrieved 2009-04-25.

[15] Engine Cooling Testing: Why use a refractometer? posted

2/7/2001 by Michael Reimer

[16] Coolants Matrix 2003_5.xls. (PDF) . Retrieved on 201101-01.

[17] Coolant Confusion: Its Not Easy Being Green ... or Yellow or Orange or .... motor.com. Retrieved 2013-06-07.
[18] Coolant Confusion. Retrieved 2013-06-07.
[19] Products: North America: Anti Freeze/Coolants. Havoline.com (2003-01-31). Retrieved on 2011-01-01.
[20] Zerex G-05 Antifreeze / Coolant. Retrieved 2013-0607.
[21] Canadian Nationwide Class Action Settlement Agreement (pdf). Retrieved 2013-06-07.
[22] Tentative Settlement of GM DEX-COOL Class Action
Suit
[23] DEX-COOL Litigation Website
[24] GM wants to dump liability for damaged engines in DexCool cases. Retrieved 2013-06-07.
[25] MACS 2001: GM and Texaco Bare All about DEXCOOL. Imcool.com. Retrieved on 2011-01-01.
[26] DraftDEX 2007, Part 3: Now Its All Up To The Judges
and Juries. Imcool.com. Retrieved on 2011-01-01.
[27] A safe and eective propylene glycol based capture liquid for fruit y traps baited with synthetic lures page
2|Florida Entomologist. Findarticles.com. Retrieved on
2011-01-01.
[28] VOGT, P. F. 2005. Tolytriazole-myth and misconceptions. The Analyst 12: 13.
[29] A safe and eective propylene glycol based capture liquid for fruit y traps baited with synthetic lures; Florida
Entomologist, June, 2008 by Donald B. Thomas

REFERENCES

Text and image sources, contributors, and licenses

9.1

Text

Antifreeze Source: https://en.wikipedia.org/wiki/Antifreeze?oldid=674903921 Contributors: CesarB, Darkwind, Jengod, Omegatron,

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9.2

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File:Antifreeze_in_the_radiator.jpg Source: https://upload.wikimedia.org/wikipedia/commons/1/16/Antifreeze_in_the_radiator.jpg

License: CC BY 2.0 Contributors: radiator Original artist: EvelynGiggles
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9.3

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