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ANTIFREEZE

An antifreeze is an additive which lowers the freezing point of a water-based liquid. An


antifreeze mixture is used to achievefreezing-point depression for cold environments and also
achieves boiling-point elevation ("anti-boil") to allow higher coolant temperature. Freezing and
boiling points are colligative properties of a solution, which depend on the concentration of the
dissolved substance.
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 efficient heat transfer and the proper functioning ofheat exchangers.
Salts are frequently used for de-icing, but salt solutions are not used for cooling systems because
they can cause severecorrosion to metals. Instead, non-corrosive antifreezes are commonly used
for critical de-icing, such as for aircraft wings.
1. Automotif and Engine Use

Fluorescent-green dyed antifreeze is visible in the radiator header tank when car radiator cap is
removed
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

ofconvective

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.
Antifreeze was developed to overcome the shortcomings of water as a heat transfer fluid.
In some engines freeze plugs (engine block expansion plugs) are placed in areas of the engine
block where coolant flows 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).
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 corrosion.
Proper engine coolant and a pressurized coolant system can help obviate the problems which
make plain water incompatible with automotive engines. With proper antifreeze, a wide
temperature range can be tolerated 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 system.
Early engine coolant antifreeze was methanol (methyl alcohol). Methanol was widely
used in windshiled fluids, however, in Europe, due to new REACH legislation, the use of
methanol in windshield fluids is limited to 5% and in the near future will be further reduced to
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 fluid is increased, permitting
higher engine temperatures and better fuel efficiency. Pressurized systems do not appreciably
change the freeze point.

2. Primary agents
Most antifreeze is made by mixing distilled water with some kind of alcohol.
2.1 Methanol
Methanol (also known as methyl alcohol, carbinol, wood alcohol, wood naphtha or wood
spirits) is a chemical compound with chemical formula CH3OH. It is the simplest alcohol,
and is a light, volatile, colorless, flammable, poisonous liquid with a distinctive odor that is
somewhat milder and sweeter than ethanol (ethyl alcohol). At room temperature, it is
apolar 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
fluid, de-icers, and gasoline additives.
2.2 Ethylene glycol

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 bypropylene glycol due to its lower
toxicity.
When ethylene glycol is used in a system, it may become oxidized to five organic acids
(formic, oxalic, glycolic, glyoxalic and acetic acid). Inhibited ethylene glycol antifreeze
mixes are available, with additives that buffer 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.
2.3 Poisoning
Ethylene glycol is poisonous to humans and other animals, 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. Ethylene glycol is difficult to detect in the body, and
causes symptomsincluding intoxication, severe diarrhea, and vomitingthat can be
confused with other illnesses or diseases. 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. Some ethylene glycol antifreeze
mixtures contain an embittering agent, such asdenatonium, to discourage accidental or
deliberate consumption.
2.4 Propylene glyco

Propylene glycol
Propylene glycol, on the other hand, is considerably less toxic than ethylene glycol
and may be labeled as "non-toxic 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 confirmation 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.
Propylene glycol oxidizes when exposed to air and heat, forming lactic acid. If not
properly inhibited, this fluid can be very corrosive, so pH buffering agents such
as dipotassium phosphate, Protodin and potassium bicarbonate are often added to propylene
glycol, to prevent acidic corrosion of metal components. Pre-inhibited propylene glycol
solutions like Dowfrost (manufactured by Dow Chemicals, US) and Tonofrost (manufactured
by Chemtex Speciality Ltd, India) can also be used instead of pure propylene glycol to
prevent corrosion.
Besides cooling system corrosion, biological fouling also occurs. Once bacterial slime starts
to grow, the corrosion rate of the system increases. Maintenance of systems using glycol
solution includes regular monitoring of freeze protection, pH, specific gravity, inhibitor level,
color, and biological contamination. Propylene glycol should be replaced when it turns a
reddish color.
2.5 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 significantly
lowered. The minimum freezing point temperature is at about 36 F / 37.8 C
corresponding to 6070% glycerol in water.
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. 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.
3. 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
refilled, the antifreeze's freeze protection will need to be considered. In other cases a vehicle may
need to be operated in a colder environment, requiring more antifreeze and less water. Three
methods are commonly employed to determine the freeze point of the solution:[15]
1. Specific gravity(using a hydrometer or some sort of floating indicator),
2. Refractometerwhich measures the refractive index of the antifreeze solution and
translates it into freeze point, and
3. Test stripsspecialized, disposable indicators made for this purpose.
Although ethylene glycol hydrometers are widely available and mass-marketed for antifreeze
testing, they give false readings at high temperatures because specific gravity changes with
temperature. Propylene glycol solutions cannot be tested using specific gravity because of
ambiguous results (40% and 100% solutions have the same specific gravity).
4. Corrosion inhibitors

Most commercial antifreeze formulations include corrosion inhibiting compounds, and a


colored dye (commonly a green, red, orange, yellow, or blue fluorescent) to aid in
identification. A 1:1 dilution with water is usually used, resulting in a freezing point of about
34 F (37 C), depending on the formulation. In warmer or colder areas, weaker or stronger
dilutions are used, respectively, but a range of 40%/60% to 60%/40% is frequently specified to
ensure corrosion protection, and 70%/30% for maximum freeze prevention down to 84 F
(64 C).
5. Maintenance
In the absence of leaks, antifreeze chemicals such as ethylene glycol or propylene glycol
may retain their basic properties indefinitely. 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 firms which take responsibility for adding corrosion inhibitors and
regulating coolant composition. For simplicity, most automotive manufacturers recommend
periodic complete replacement of engine coolant, to simultaneously renew corrosion inhibitors
and remove accumulated contaminants.
6. Traditional inhibitors
Traditionally,
there

were

two

major

corrosion

inhibitors

used

in

vehicles: silicates and phosphates. American made vehicles traditionally used both silicates and
phosphates.European makes contain silicates and other inhibitors, but no phosphates. Japanese
makes traditionally use phosphates and other inhibitors, but no silicates.
7.
Organic acid technology
Certain cars are built with organic acid technology (OAT) antifreeze (e.g., DEX-COOL),
or with a hybrid organic acid technology (HOAT) formulation (e.g., Zerex G-05), both of which
are claimed to have an extended service life of five years or 240,000 km (150,000 mi).
DEX-COOL specifically has caused controversy. Litigation has linked it with intake
manifold gasket failures in General Motors' (GM's) 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 Potassium

2-ethylhexanoate and ethylhexanoic

acid is

incompatible

with nylon

6,6 and silicone rubber, and is a known plasticizer. Class action lawsuits were registered in
several states, and in Canada, to address some of these claims. The first of these to reach a
decision was in Missouri where a settlement was announced early in December 2007. Late in
March 2008, GM agreed to compensate complainants in the remaining 49 states. GM (Motors

Liquidation Company) filed for bankruptcy in 2009, which tied up the outstanding claims until a
court determines who gets paid.
According to the DEX-COOL manufacturer, "mixing a 'green' [non-OAT] coolant with
DEX-COOL reduces the batch's change interval to 2 years or 30,000 miles, but will otherwise
cause no damage to the engine". DEX-COOL antifreeze uses two inhibitors: sebacate and 2-EHA
(2-ethylhexanoic acid), the latter which works well with the hard water found in the US, but is
a plasticizer which can cause gaskets to leak.
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.
Honda and Toyota's new extended life coolant use OAT with sebacate but without the 2EHA. Some added phosphates provide protection while the OAT builds up. Honda specifically
excludes 2-EHA from their formulas.
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).
8. 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 the benzoate inhibitor.
Additives
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, buffers and corrosion inhibitors. Because the additives in
antifreeze are proprietary, the material safety data sheets (MSDS) provided by the manufacturer
list only those compounds which are considered to be significant safety hazards when used in
accordance with the manufacturer's recommendations. Common additives include sodium
silicate, disodium phosphate, sodium molybdate, sodium borate, and dextrin (hydroxyethyl

starch). Disodium fluorescein dyes are added to antifreeze to help trace the source of leaks, and
as an identifier since some different formulations are incompatible.
Automotive antifreeze has a characteristic odor due to the additive tolytriazole, a
corrosion inhibitor. The unpleasant odor in industrial use tolytriazole comes from impurities in
the product that are formed from the toluidine isomers (ortho-, meta- and para-toluidine) and
meta-diamino toluene which are side-products in the manufacture of tolytriazole.These sideproducts are highly reactive and produce volatile aromatic amines which are responsible for the
unpleasant odor.