Methanol, Ethanol and Isopropyl Alcohol

I. Properties
Methanol Ethanol Isopropyl Alcohol

Chemical CH3OH C2H6O C 3 H8 O

Formula
Molar Mass 32.04 g/ mol 46.07 g/mol 60.10 g/mol
Appearance Colorless liquid Colorless liquid Colorless liquid
Density 0.792 g/cc 0.789 g/cc 0.786 g/cc
Melting Point −97.6 °C −114 °C −89 °C
Boiling Point 64.7 °C 78.37 °C 82.6 °C
Flash point 11°C to 12 °C 14 ˚C 11.7 °C to 13 °C
Other names Carbinol Absolute alcohol Propan-2-ol
Columbian spirits Alcohol Isopropanol
Hydroxymethane Cologne spirit Rubbing alcohol
Methyl alcohol Drinking alcohol sec-Propyl alcohol
Methyl hydrate Ethane monoxide s-Propanol
Methyl hydroxide Ethylic alcohol iPrOH
Methylic alcohol EtOH IPA
Methylol Ethyl alcohol
Pyroligneous spirit Ethyl hydrate
Wood alcohol Ethyl hydroxide
Wood naphtha Ethylol
Wood spirit Grain alcohol
Hydroxyethane
Methylcarbinol
 II. Reactions of Alcohol
strong base RO- Na+ + H2O/H2
sodium alkoxide
(NaOH, NaH)

aq. Strong mineral acid (H2SO4) R Ö+H + HSO4-

room temperature H
oxonium ion

oxidizing agent OH
(KMnO4, Na2Cr2O4/H+) R-C=O (if 1o ROH)
carboxylic acid

R
ROH R-C=O (if 2o ROH)
ketone

strong mineral acid , heat R

(H3PO4, H2SO4, HNO3) C=C + H2O
alkene

R-O-R + H2O
ether
(at higher temp.)

HX , heat RX + H2O
alkyl halide

O2 , source of ignition CO2 + H2O

carbon dioxide

Example:
Methanol Ethanol Isopropyl alcohol
+ NaOH Sodium methoxide Sodium ethoxide Sodium isopropoxide
+H2SO4 (room temp.) Oxonium ion
+ H2SO4 (heat) Ethylene Propylene
Dimethyl ether Diethyl Ether Di-isopropyl ether
+ KMnO4 Formaldehyde Acetaldehyde Acetone
[o]→ Formic acid [o]→ Acetic acid
+HCl Methyl chloride Ethyl chloride Isopropyl chloride
For combustion:
2 CH3OH (l) + 3 O2 (g) → 2 CO2 (g) + 4 H2O
C2H5OH (l) + 3 O2 (g) → 2 CO2 (g) + 3 H2O
2 (CH3)2OH (l) + 9 O2 (g) → 6 CO2 (g) + 8 H2O
III. Natural Occurrence
 Methanol
Methanol is poisonous to the central nervous system and may cause
blindness, coma, and death. However, in small amounts, methanol is a natural
endogenous compound found in normal, healthy human individuals, concluded
by one study which found a mean of 4.5 ppm in the exhaled breath of the
subjects.
 Ethanol
Ethanol is a by-product of the metabolic process of yeast. As such, ethanol
will be present in any yeast habitat.
Ethanol can commonly be found in overripe fruit. Ethanol is also produced
during the germination of many plants as a result of natural anerobiosis.
Ethanol has been detected in outer space, forming an icy coating around
dust grains in interstellar clouds.
Minute quantity amounts (average 196 ppb) of endogenous ethanol and
acetaldehyde were found in the exhaled breath of healthy volunteers.
Auto-brewery syndrome, also known as gut fermentation syndrome, is a
rare medical condition in which intoxicating quantities of ethanol are produced
through endogenous fermentation within the digestive system.

IV. Toxicology
 Ethanol
When alcohol reaches the brain, it has the ability to delay signals that are
sent between nerve cells that control balance, thinking and movement. Ethanol
is classified as a teratogen or an agent that interrupts or alters the normal
development of a fetus, with results that are evident at birth. International
Agency for Research on Cancer (IARC) list ethanol in alcoholic beverages as
Group 1 carcinogens (cancer-causing sunstances) and arguments "There is
sufficient evidence for the carcinogenicity of acetaldehyde (the major
metabolite of ethanol) in experimental animals." Frequent drinking of alcoholic
beverages has been shown to be a major contributing factor in cases of elevated
blood levels of triglycerides.
 Methanol
Methanol has a high toxicity in humans. If as little as 10 mL of pure
methanol is ingested, for example, it can break down into formic acid, which
can cause permanent blindness by destruction of the optic nerve, and 30 mL is
potentially fatal. Methanol is toxic by two mechanisms. First, methanol can be
fatal due to its Central Nervous System (CNS) depressant properties in the same
manner as ethanol poisoning. Second, in a process of toxication, it
is metabolized to formic acid (which is present as the formate ion). The initial
symptoms of methanol intoxication include CNS depression, headache,
dizziness, nausea, lack of coordination, and confusion. Sufficiently large
doses can cause unconsciousness and death. Once the initial symptoms have
 passed, a second set of symptoms arises, 10 to as many as 30 hours after the
initial exposure to methanol, including blurring or complete loss of
vision, acidosis and putaminal hemorrhages, an uncommon but serious
complication. These symptoms result from the accumulation of toxic levels
of formate in the blood, and may progress to death by respiratory failure.
 Isopropyl Alcohol
Isopropyl alcohol and its metabolite, acetone, act
as CNS depressants. Symptoms of isopropyl alcohol poisoning
include flushing, headache, dizziness, CNS depression, nausea,
vomiting, anesthesia, hypothermia, hypotension, shock, respiratory
depression, and coma. Poisoning can occur from ingestion, inhalation, or skin
absorption; therefore, well-ventilated areas and protective gloves are
recommended. However, it is not nearly as toxic as methanol or ethylene glycol.
Isopropyl alcohol does not cause an anion gap
acidosis unlike ethanol and methanol.

V. Uses
 Methanol
A. Feedstock
About 40% of methanol is converted to formaldehyde, and from
there into products as diverse as plastics, plywood, paints, explosives, and
permanent press textiles. Other chemical derivatives of methanol
include dimethyl ether, which has replaced chlorofluorocarbons as
an aerosol spray propellant, and acetic acid. Dimethyl ether (DME) also can
be blended with liquified petroleum gas (LPG) for home heating and
cooking, and can be used as a diesel replacement for transportation fuel.
B. Fuel for vehicles
Methanol is used on a limited basis to fuel internal combustion
engines. Methanol is also used, as the primary fuel ingredient since the late
1940s, in the power plants for radio control, control line and free
flight airplanes (as methanol is required in the engines that primarily power
them), cars and trucks, from such an engine's use of
a platinum filament glow plug being able to ignite the methanol vapor
through a catalytic reaction.
C. Other applications
Methanol is a traditional denaturant for ethanol. Methanol is also
used as a solvent, and as an antifreeze in pipelines and windshield washer
fluid. Methanol was used as an automobile coolant antifreeze in the early
1900s. Methanol is also a widely used fuel in camping and boating stoves.
Methanol is also useful as an energy carrier. It is easier to store than
hydrogen and burns cleaner than fossil fuels. Pure methanol has been used
in open wheel auto racing since the mid-1960s. Unlike petroleum fires,
methanol fires can be extinguished with plain water.
 Isopropyl Alcohol
A. Solvent
It is used widely as a solvent and as a cleaning fluid, especially for
dissolving oils. Examples of this application include
cleaning electronic devices. Isopropyl alcohol is used in keyboard, LCD
and laptop cleaning, is sold commercially as a whiteboard cleaner, and is a
strong but safer alternative to common household cleaning products. In
addition, it can also be used to clean paint or other oil-based products so
that they may be reused, commonly known as "repainting."
B. Intermediate
Isopropyl alcohol is esterified to give isopropyl acetate, another
solvent. It reacts with carbon disulfide and sodium hydroxide to
give sodium isopropylxanthate, an herbicide and an ore flotation reagent.
Isopropyl alcohol reacts with titanium tetrachloride and aluminium metal to
give titanium and aluminium isopropoxides.
C. Medical
Rubbing alcohol, hand sanitizer, and disinfecting pads typically
contain a 60–70% solution of isopropyl alcohol in water. Water is required
to open up membrane pores of bacteria, which acts as a gateway inside for
isopropyl. A 75% v/v solution in water may be used as a hand sanitizer.
D. Automotive
Isopropyl alcohol is a major ingredient in "gas dryer" fuel additives.
In significant quantities, water is a problem in fuel tanks, as it separates
from the gasoline, and can freeze in the supply lines at cold temperatures.
Alcohol does not remove water from gasoline; rather, the alcohol
solubilizes water in gasoline. Isopropyl alcohol is often sold in aerosol cans
as a windshield de-icer.
E. Laboratory
As a biological specimen preservative, isopropyl alcohol provides a
comparatively non-toxic alternative to formaldehyde and other synthetic
preservatives. Isopropyl alcohol solutions of 70–99% are used to preserve
specimens. Isopropyl alcohol is often used in DNA extraction. It is added
to a DNA solution in order to precipitate the DNA into a 'pellet' after
centrifuging the DNA. This is possible because DNA is insoluble in
isopropyl alcohol.
 Ethanol
A. Medical
1. As an Antiseptic
Ethanol is used in medical wipes and in most common antibacterial
hand sanitizer gels.
2. As an Antitussive agent
Ethanol is also widely used, clinically and over the counter, as an
antitussive agent.
3. As an Antidote
Ethanol may be administered as an antidote to methanol poisoning.

B. Recreational
Ethanol is commonly consumed as a recreational drug, especially
while socializing, due to its psychoactive effects.

C. Fuel
1. Engine Fuel
The largest single use of ethanol is as an engine fuel and fuel
additive. A percentage of ethanol is combined with gasoline. This is
beneficial because the ethanol:
a. decreases the fuel's cost
b. increases the fuel's octane rating
c. decreases gasoline's harmful emissions
Any amount of ethanol can be combined with gasoline, but the
most common blends are E10 and E85 in US and E25 in Brazil. More
than 20% of Brazilian cars are able to use 100% ethanol as fuel, which
includes ethanol-only engines and flex-fuel engines. Flex-fuel engines
in Brazil are able to work with all ethanol, all gasoline or any mixture
of both. In the US flex-fuel vehicles can run on 0% to 85% ethanol
(15% gasoline) since higher ethanol blends are not yet allowed or
efficient.
2. Rocket Fuel
Ethanol was commonly used as fuel in early bipropellant rocket
(liquid propelled) vehicles, in conjunction with an oxidizer such as
liquid oxygen. The German V-2 rocket of World War II, credited with
beginning the space age, used ethanol, mixed with 25% of water to
reduce the combustion chamber temperature. The V-2's design team
helped develop U.S. rockets following World War II, including the
ethanol-fueled Redstone rocket which launched the first U.S. satellite.
 3. Fuel Cells
Commercial fuel cells operate on reformed natural gas, hydrogen
or methanol. Ethanol is an attractive alternative due to its wide
availability, low cost, high purity and low toxicity.

4. Household Heating
Ethanol fuels flue-less, real flame fireplaces. It provides almost the
same visual benefits of a real flame log or coal fire without the need to
vent the fumes via a flue as ethanol produces very little hazardous
carbon monoxide, and little or no noticeable scent. An additional
benefit is that, unlike a flue based fireplace, 100% of the heat energy
produced enters the room. This serves to offset some of the heat loss
from an external air vent, as well as offset the relatively high cost of
the fuel compared to other forms of heating.

D. Feedstock
Ethanol is an important industrial ingredient. It has widespread use
as a precursor for other organic compounds such as ethyl halides, ethyl
esters, diethyl ether, acetic acid, and ethyl amines.

E. Solvent
Ethanol is miscible with water and is a good general purpose
solvent. It is found in paints, tinctures, markers, and personal care
products such as mouthwashes, perfumes and deodorants.

 Grades of Ethanol
A. Denatured alcohol
Most industrial ethanol is denatured to prevent its use as a
beverage. Pure ethanol and alcoholic beverages are heavily taxed as
psychoactive drugs. To relieve the tax burden on these uses, most
jurisdictions waive the tax when an agent has been added to the ethanol to
render it unfit to drink. These include toxins such as methanol, naphtha,
and pyridine.

B. Absolute alcohol
Absolute or anhydrous alcohol refers to ethanol with a low water
content. There are various grades with maximum water contents ranging
from 1% to a few parts per million (ppm) levels. Absolute alcohol is not
intended for human consumption. Absolute ethanol is used as a solvent for
laboratory and industrial applications and as fuel alcohol. Pure ethanol is
classed as 200 proof in the US.
 C. Rectified Spirit
Rectified spirit is highly concentrated ethanol which has been
purified by means of repeated distillation, a process that is called
rectification. It typically contains 95% alcohol by volume (ABV) (190 US
proof). The purity of rectified spirit has a practical limit of 95.6% ABV
when produced using conventional distillation processes, because a
mixture of ethanol and water becomes an azeotrope at this concentration.
Neutral spirits can be produced from grain, grapes, sugar beets,
sugarcane, or other fermented plant material. Neutral spirits are used in the
production of blended whiskey and cut brandy or is sometimes added to
cocktails in place of vodka or rum. It is also used in cooking because its
high concentration of alcohol acts as a solvent to extract flavors. Rectified
spirits are also used for medicinal tinctures.

VI. Production
 Methanol
Methyl alcohol is obtained by the oxidation of methane. This includes
zinc, chromium, manganese, or aluminum oxides as catalysts, 300oC, 250 to
300atm (3000 to 5000 psi).
3 CH4 + 2 H2O + CO2 → 4 CO + 8H2
CO + 2 H2 → CH3OH
Using a composition for wood of 50% carbon, 42% oxygen, 6%
hydrogen we can represent wood with the formula C11H16O7 (we could also
use C8H12O5). Then some combination of the following two formal reactions
will occur:
3 C11H16O7 + 22 H2O → 46 H2 + 23 CO + 10 CO2 → 23 CH3OH + 10 CO2
2 C11H16O7 + 11 O2 → 16 H2 + 8 CO + 14 CO2 → 8 CH3OH + 14 CO2

 Isopropyl Alcohol
This compound is primarily produced by combining water and propene in
a hydration reaction.
CH3CH=CH2 + H2SO4 → CH3CH(OSO3H)CH3
CH3CH(OSO3H)CH3 +H2O → CH3CH(OH)CH3 + H2SO4

 Ethanol
Synthetic ethanol: from Ethylene, coal (non-renewable)
C2H4 + H2SO4 → CH3CH2SO4H
CH3CH2SO4H + H2O → CH3CH2OH + H2SO4
Fermentation ethanol: from Grains, sugar crops, wood, etc. (renewable)
C6H12O6 → 2 CH3CH2OH + 2 CO2
C12H22O11 + H2O → 4 CH3CH2OH + 4 CO2
References
Speight, J. G. (2002). Chemical and process design handbook.
http://www.scifun.org/chemweek/pdf/ethanol.pdf
http://www.wormbook.org/chapters/www_ethanol/ethanol.pdf
http://www.energyjustice.net/files/ethanol/pimentel2003.pdf
https://en.wikipedia.org/wiki/Ethanol
https://en.wikipedia.org/wiki/Denatured_alcohol
https://en.wikipedia.org/wiki/Carcinogen
https://en.wikipedia.org/wiki/Direct-ethanol_fuel_cell
https://en.wikipedia.org/wiki/E85
https://en.wikipedia.org/wiki/Rectified_spirit
https://en.wikipedia.org/wiki/Scrubber
https://en.wikipedia.org/wiki/Isopropyl_alcohol
https://en.wikipedia.org/wiki/Methanol
https://en.wikipedia.org/?title=Ethanol_fuel
https://www.utdallas.edu/~parr/chm1316/ethanol.ppt
https://www.triumf.info/wiki/tuda-tactic/images/4/42/ETHANOL.ppt
http://web.missouri.edu/~plainr/PowerPoints/EthanolOutlook8-07.ppt
http://ethanolrfa.3cdn.net/a85a9af3965b5dc691_hsm6y1n9a.ppt
https://en.wikipedia.org/wiki/Hydrolysis
https://en.wikipedia.org/wiki/Ethanol_fermentation
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