Dke345 Sec1

SECTION 1
INDUSTRIAL ORGANIC SOLVENTS
ALCOHOLS
Alcohols contain a hydroxyl functional group (-CH,OH). Monohydric alcohols are

among the most common in this class of solvents. These are straight or branched
chain aliphatic hydrocarbons that contain one hydroxyl group on:
a primary carbon atom (RCH,OH),

a secondary carbon atom (RR,CHOC), or
a tertiary carbon atom (RR,R,COH).
An important cyclic alcoholic solvent is cyclohexanol. An important aromatic

alcoholic solvent is benzyl alcohol.
The high hydrogen bonding character of alcoholic solvents makes these substances
valuable solvents for dissolving many polymeric and resin-like materials. Alcoholic
functional groups are also valuable reaction sites for a large number of synthetic
reactions of commercial importance.
No gaseous alcohols are known. The lower members of the homologous series of
aliphatic alcohols (containing C I to CIo) are clear colorless liquids at room
temperature. They have varying solubility in water, the higher alcohols being less
soluble. The alcohols higher than CIZare solids and are insoluble in water.
Methanol, ethanol and propanol are miscible with water. The alcohols are miscible in
all proportions with most organic liquids. As we pass up the series, the specific
gravity increases.
The boiling points of the straight chain alcohols increase as the number of carbon
atoms in the molecule increases. For a given molecular weight, there is a decrease in
the boiling point when branching of carbon atoms occurs. Thus, the primary alcohols
boil at a higher temperature than the secondary alcohols of the same molecular
weight, and similarly, secondary alcohols have higher boiling points than the tertiary
alcohols. The boiling points are much higher than is to be expected from their
molecular weights. For example, the boiling point of ethanol, 7S°C, can be explained
by the attraction of ethanol molecules by means of hydrogen bonds to form extended
groups of molecules.
Hydrogen bonds can arise in ethanol because the area around the oxygen atom is
relatively rich in electrons and can attract hydroxyl hydrogen from a neighboring
ethanol molecule. These intermolecular bonds are considered to be intermediate in
strength between weak van der Waals' forces and the strong forces between ions. The
extra energy required to break the hydrogen bonds leads to an increase in boiling
point. Alcohols react with sodium and potassium with the evolution of hydrogen.
TM
Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.
MARCEL
DEKKER,
INC.
270 MadisonAvenue, New York, New York 10016
4 Industrial Solvents Handbook
Ethylene glycol, CH,0HCH20H, is the most important dihydric alcohol and

approximately 75% of that produced is used as an anti-freeze agent. An example of
a trihydric alcohol is glycerol. Glycerol, CH,OHoCHOHoCH,OH, is the most
important trihydric alcohol and it is an important industrial chemical having many
uses in war and peace. Glycerol is used in the production of explosives, as a
moistening agent for tobacco, as a softening agent for cellophane films, in
cosmetics, in food products, as a commercial solvent, and in the manufacture of
plastics known as alkyd resins, which are used in paints.
The chemical properties of any given aliphatic alcohol depends on the nature of the
alkyl group in the molecule and on the properties of the hydroxyl group. Alcohols
react with organic acids to form esters. The reaction proceeds slowly but the rate of
esterification is increased by the presence of hydrogen ions, which act as a catalyst
in the reaction. Sulfi~ric acid in addition to acting as a source of hydrogen ions also
helps to increase the yield of ester by absorbing the water as it is formed in the
reaction. Alcohols are very weak acids, intermediate in strength between acetylene
and water. They undergo substitution with strongly electropositive metals such as
sodium. Alcohols react with phosphorus pentachloride, when the hydroxyl group is
replaced by a chlorine atom. Thus, when the hydroxyl group is replaced by a
chlorine atom from phosphorus pentachloride fumes of hydrogen chloride are
evolved and this is used in testing for the presence of the hydroxyl group in a
compound.
Common names for alcohols are Methanol, Ethanol, Isopropanol, n-Butanol,

Isooctanol, Methyl Isobutyl Carbinol, Isoamyl Alcohol, Isobutyl Alcohol,
Cyclohexanol, Methyl Cyclohexanol. The alcohols are versatile solvents that are
used in many products from antiseptics and cough syrups to coatings and adhesives.
Alcohols are used extensively as base materials for further processing into other
chemicals such as esters, plasticizers and synthetic lubricants. Methyl alcohol is a
strongly toxic material used in glass cleaners, shellac, NGR stains, dyes, inks,
lacquer solvents, fuel additives and as an extractant for oils. Isopropanol (also
known as Rubbing Alcohol) is used in cosmetics, perfumes, some types of
coatings, cleaners, liniments, antiseptic solutions, liquid soaps and medications.
Nomenclature
The common name for an alcohol involves naming the longest chain that includes
the carbon atom attached to the hydroxyl group, and affixing the suffix "01" to the
hydrocarbon name. The proper nomenclature numbering assigns the lowest number
to the position of the hydroxyl group and other numbers to indicate the alkyl or
others groups associated with the main hydrocarbon chain. Table 1 provides a list
TM
DEKKER,
MARCEL INC.
Properties and Selection of Organic Solvents 5
of common chemical names along with Chemical Abstract Index names (CA -
Chemical Abstract Index, American Chemical Society) and CAS numbers
(Chemical Abstract Service, American Chemical Society). CAS numbers in this
case refer to the major alcohol component.
Table 1. Nomenclature for Common Alcohols

1 Chemical Name I CA Index I CAS I Chemical Name I CA Index I CAS
I propanol
rerr-Butanol 1 2-methyl 2- 1 75-65-0 1 Decyl alcohol I I-decanol 1 112-30-1
propanol
n-Amyl alcohol I-pentanol 71-41-0 Benzyl alcohol 100-51-6
Isoamyl alcohol 3-methyl 1- 123-51-3 Allyl alcohol 2-propen- 1-01 107-18-6
butanol
sec-Amyl alcohol 2-pentanol 6023-29-7 Diacetone 4-hydroxy 4- 123-42-2
methyl 2-
pentanone
ten-Amyl alcohol 2-methyl 2- 75-85-4 Furfuryl alcohol 98-00-0
butanol
11-Hexyl alcohol I-heaxanol 111-27-3 Tetrahydrofur- 97-99-4
General Properties
Physical properties for many alcohols can be found among the chemical-specific
profiles provided in Part 2. Some data are reported in Tables 2 and 3. Table 2
shows alcohols with minimum boiling azeotropes with water. Table 3 reports
evaporation rates for common alcohols.
Table 2. Alcohol and Water Azeotropes

Alochol Azeotrope Boiling Point Weight Percent Water
VC> in Vapor Phase
Ethanol 78.0 4.0
n-Propanol 87.0 28.3
Isopropanol 80.3 12.6
n-Butanol 92.7 42.5
sec-Butanol 87 .O 26.8
Isobutanol 89.8 33.0
TM
MARCEL INC.
DEKKER,
270 Madison Avenue, New York, New York 10016
Alochol Azeotrope Boiling Point Weight Percent Water

("(3 in Vapor Phase
Amyl alcohol 95.8 54.4
Cvclohexanol 97.8 80.0
Methyl isobutyl carbinol 94.3 43.3
2-Ethyl 1-hexanol 99.1 80.0
Diacetone alcohol 99.6 87.0
Table 3. Alcohol Evaporation Rates (relative to rz-Butyl Acetate; i.e., n-Butyl

Acetate = 1.O)
Alcohol BP ("C) Evap. Rate
Methanol 65 2.100
Ethanol 78 1.600
2-Propanol 82 1.400
tert-Butyl alcohol 83 0.950
tert-Amyl alcohol 102 0.930
n-Propyl alcohol 97 0.860
2-Butanol 100 0.810
2-Methyl 1-propanol 108 0.620
1-Butanol 118 0.440
Methvl isobutvl carbinol 132 0.300
1-Pentanol (n-amyl alcohol) 137 0.200
Diacetone alcohol 166 0.140
2-Ethyl 1-butanol 146 0.110
Hexanol 148 0.096
Cvclohexanol 161 0.050
Tetrahydrofurfuryl alcohol 178 0.030
2-Ethyl 1-hexanol 185 0.020
2-Octanol 177 0.018
1-0ctanol 196 0.007
Benzyl alcohol 205 0.007
1-Decanol (decyl alcohol) 23 1 0.001
The low surface tension of alcohols is a property which favors their use in coating
formulations. Alcoholic solvents afford a wide range of evaporation rates and
excellent solvency for various resins and polymer compositions. The four lowest
molecular weight alcohols are completely miscible with water and with most
organic solvents. Tertiary butyl alcohol, diacetone alcohol, furfuryl alcohol, and
tetrahydrofurfuryl alcohol are also completely soluble in water. A compilation of
general physical properties data is reported in Table 4. Table 5 reports solubility
data.
TM
MARCEL
DEKKER,
INC.
Table 4. General Physical Properties of Alcohol Solvents

Solvent Molecular BP (T) Specific Viscosity Surface
Weight Gravity (cP at 25°C) Tension
(60160°F) (20°C)
dyneslcm
Methanol 32 ( 65 1 0.7965 1 0.56 22.6
Ethanol 46 78 0.7937 1.1
n-Propyl 60 97 0.809 2
alcohol
Isopropyl 60 82 0.79 2.4
alcohol
n-Butanol 74 1 118 1 0.814 1 2.6
sec-Butanol 74 99.5 0.811 2.9
Isobutanol 74 108 0.806 1.8
tert-Butanol 74 83 0.779 3.35
n-Amvl alcohol 88 133 0.82 3.7
a~cohd~
sec-Amyl 88 119 0.811 4.1
alcohol
tert-Amy1 88 102 0.81 3.5
alcohol
n-Hexyl 102 157 0.821 5.4
alcohol
Cyclohexanol 100 161 0.953 52.7
2-Ethyl-1 - 102 146 0.832 5.9
butanol
Methyl 102 132 0.802
isobutyl
carbinol
2-Ethyl-l- 130 184 0.833 7.7
hexanol
n-Octyl alcohol I 130 / 196 1 0.827 1 8.9
Sec-Octyl 1 130 1 177 1 0.818 1 6.2
alcohol
- - - - - ~ I I I I
Nonyl alcohol 144 215 0.812 14.3
Decyl alcohol 158 23 1 0.838 13.8
Benzyl alcohol 108 205 1.05 0.05
Allyl alcohol 58 97 0.854 1.07
Diacetone 116 166 0.94 3.2
alcohol
Furfuryl 98 1 170 1 1.135 1 5
alcohol
Tetrahydro- 102 178 1.054 6.2
furfuryl
alcohol
TM
MARCEL DEKKER, INC.

Industrial Solvents Handbook
Table 5. Solubilitv Data

Solvent Solubility (g1100 g)
Solvent in water Water in solvent
Methanol Complete Complete
Ethanol Complete Complete
n-Propyl alcohol Complete Complete
Isopropyl alcohol Complete Complete
11-Butanol 7.7 20.1
Isobutanol 8.7 15
Comnlete Com~lete
I 11-Amyl alcohol 1.7 9.2
Isoamyl alcohol 2
sec-Amy l alcohol 8.2
tert-Aniyl alcohol 13.7 20.9
I 11-Hexvlalcohol 1 I 1
Cyclohexanol 3.8 11.8
2-Ethyl-1-butanol 2.9 9.2
Methyl isobutyl carbinol 1.7 6
n-Octyl alcohol 0.06 3.4

Sec-Octyl alcohol 0.13
Nonyl alcohol 0.06 0.99
Decyl alcohol 0.01 2.3
Benzyl alcohol 0.08 8.4
Allyl alcohol
Diacetone alcohol Comolete Cornnlete
Furfuryl alcohol Complete Complete
Tetrahydrofurfuryl alcohol Complete Complete
The following are descriptions of some of the uses of and synthesis routes for
several important alcoholic solvents.
Methanol
One of the major end uses of methanol is for the production of methyl tertiary-butyl
ether (MTBE), a motor gasoline oxygenate for octane enhancement. Continued use
of MTBE in the U.S. IS, however, questionable. Environmental concerns related to
high groundwater contamination has caused the US EPA (Environmental Protection
Agency) to reverse its position on the toxic risks associated with MTBE and has
more recently recommended replacernent with ethanol. Despite this, the prospects
for MTBE demand growth in Europe and Asia continue to be promising. New
gasoline specifications were introduced by the European Union on January 1, 2000
TM
MARCEL DEKKER, INC.

and more stringent specifications will become effective in 2005. These new
regulations phase out lead content and reduce the amount of sulfur and aromatics
such as benzene, a known carcinogen. The octane provided by the lead and
aromatics will have to be replaced. MTBE would be the easiest and most
economical source of octane. This would result in additional methanol demand
growth for MTBE in Europe. Industry consultants expect methanol demand for
MTBE in Asia to grow at about 7% per year for the next few years. MTBE
demand will be driven by strong economic growth in the region and a focus on
better air quality in the major industrial centers. For example, China has started to
phase out lead in gasoline and Thailand, Korea and Taiwan require the use of
oxygenates in gasoline.
Miscellaneous uses of methanol form the basis for many products including
silicones, refrigerants, adhesives, specialty plastics and coatings, textiles, and
water-treatment chemicals. Winter driving is made safer by methanol-based
windshield antifreeze. Acrylic plastic light-coverings in homes and cars are based
on another methanol derivative, methyl methacrylate. Other acrylic polymers are
used in water-based interior and exterior coatings where superior durability is
required. Paper products are usually bleached using chlorine dioxide, a process
which produces significantly fewer pollutants than traditional bleaching methods.
Similar to formaldehyde and acetic acid, overall growth of other derivatives is
largely driven by general economic growth with some indicators including housing
starts, new car production and industrial production. The largest solvent use for
methanol is as a component of windshield wash antifreeze, where it can account for
up to 50% of the solution depending on local climatic conditions. While not
showing substantial growth, the expanded use of summer windshield cleaning
solutions has changed the seasonal nature of this market. Methanol's purity and
physical properties enable it to be used to extract, wash, dry and crystallize
pharmaceuticals and agricultural chemicals. It also acts well as a solvent in the
production of ethyl cellulose, polyvinyl acetate, nitrocellulose, dyes, shellacs and
numerous other chemicals.
Formaldehyde - Methanol is also used as a raw material for producing

formaldehyde, which is used extensively in the construction industry to
manufacture strand board and fiberboard. Formaldehyde continues to be the largest
single end use for methanol, representing 36% of 1999 demand. Changes in the
market mix of wood panel products, coupled with high growth in plastics and fibers
derivatives, are providing new growth potential for formaldehyde beyond the
traditional demand stemming from the construction industry. Phenol formaldehyde
resins (PF) for plywood and oriented strandboard (OSB), and urea formaldehyde
resins (UF) for particleboard and medium density fiberboard (MDF) are the largest
markets for formaldehyde. The declining availability of old-growth timber has
accelerated the switch to engineered wood products such as particleboard, OSB and
MDF. Engineered wood products can use lower quality woods and wood wastes as
feedstocks, providing unique advantages over solid timber products. The non-
TM
MARCEL
DEKKER,
INC.
structural panels industry has addressed the health concerns related to formaldehyde
emissions by using re-engineered UF resins that have reduced emissions to one-
tenth the level typical of older resins. Non-structural panels continue to grow and
have had particular strength due to the popularity of "ready to assemble" (RTA)
furniture and cabinetry markets. Particleboard overlaid with wood veneer or plastic
laminates has been a mainstay for these applications. MDF is the fastest growing
segment of the wood panel adhesives market. MDF is beginning to replace
traditional particleboard in many applications. The unique properties of MDF - its
small particle size and uniform density - allow it to be machined or pressed into
complex shapes. MDF applications include construction molding trim (baseboards,
copings), architectural shapes (pillars, columns), and interior automotive trim parts
(interior door panels and head liners). The urea formaldehyde adhesives used to
bind the wood fibers in particleboard and MDF use a high proportion of
formaldehyde in comparison to other resins. Industry forecasts suggest that MDF
output will continue to grow. Plywood has been the traditional structural panel, but
the declining availability of high-quality veneer timber is accelerating its
replacement with cost advantageous products such as OSB. OSB uses lower quality
and faster growing woods which are "waferized" into small chips, combined with a
phenol-formaldehyde adhesive and pressed into finished panels. OSB uses
approximately twice the amount of phenol-formaldehyde adhesive per board
relative to plywood. OSB is forecast to continue gaining increasing share of the
structural panel market.
There are a wide range of other formaldehyde specialty products and applications
such as:
1,4 Butanediol is used in the production of tetrahydrofuran, a solvent used

in the manufacture of "Spandex" fibers. This market has expanded rapidly
with the increased sale of specialty sport and leisure clothing.
Acetyl thermoplastics are made using formaldehyde resins and offer high
impact and durability. They continue to find increased use in automotive
and plumbing applications including molded parts, gears and pump
housings.
Formaldehyde is also used in the manufacture of methylene di-para-phenylene

diisococyanate (MDI) which is used to produce rigid urethane foams and
elastomers. High impact resistance and the ability to recover its original shape
make this the ideal material for construction of bumpers and body panels.
Markets and Miscellaneous lrlfornzation - Methanol is methyl alcolzol and at the

present 99% of the production of methanol in the world is produced either from
natural gas or gases out of oil. The reformed gas is compressed and passed to a
methanol reactor. Carbon monoxide and carbon dioxide react with hydrogen over a
catalyst to produce methanol. Also it is possible to produce methanol and ammonia
TM
MARCEL INC.
DEKKER,
in one complex by using CO,, which is produced from an ammonia plant to

produce methanol and urea. Methanol can be made from renewable resources such
as municipal solid waste and biomass crops.
Methanol production is a major market for U.S. natural gas, using over 194 trillion
Btu of domestic natural gas in 1995. The United States produces almost one-quarter
of the world's supply of methanol. In 1998, U.S. methanol production capacity
totaled more than 2.2 billion gallons. Methanol plants meet three-quarters of U.S.
methanol demand. The remaining supply comes from imports, of which Canada
supplies well over one-half. In 1998, 90% of methanol supplied to the U.S. was
produced in North America, 8% from Trinidad, Venezuela and Chile, with the
remaining 2% produced in Europe, Asia and the Middle East. The largest market
for methanol in the U.S. is for the production of MTBE. Produced in nearly 50
U.S. plants in 14 states, it is estimated that 3.3 billion gallons of MTBE was made
in 1996 for blending in clean, reformulated gasoline serving 30% of the U.S.
gasoline market. MTBE displaces 10 times more gasoline than all other alternative
vehicle fuels combined.
The single largest use of methanol is in formaldehyde and dimethyl terephthalate

production. Methanol is also used in the manufacture of methyl acrylate, methyl
methacrylate, methyl chloride, dimethyl ether, dimethyl sulfate, and various other
intermediates and dyes. Methanol is useful in dissolving phenolic laminating resins,
ethyl cellulose, cellulose nitrate, and a variety of other resins. Low-viscosity resin
solutions are possible using methanol.
Methanol burns with lower emissions than hydrocarbon fuels and is used as a fuel
for many gasoline and diesel-type engines, stationary and aircraft turbines,
industrial boilers, and in fuel cells. Methanol burns with a pale-blue, non-luminous
flame to form carbon dioxide and steam.
Manufacture - Most of world methanol is manufactured from natural gas by a steam

reforming process. Methane of natural gas is first mixed with steam at a 311 ratio.
It is then reformed to carbon oxides and hydrogen under nickel catalyst at 1000°C
and 20 atm. Carbon oxides and hydrogen react exothermically at about 70 atm
pressure in the gas phase to form mainly methanol and water mixture. This reaction
takes place in the presence of Cu, Al and Zn based catalyst. Crude methanol is
cooled and condensed and fed through a distillation process to achieve 99.9 mole-
percent product purity. The process is highly integrated. It uses state-of-the-art
technologies to achieve low capital cost and higher conversion efficiency. As an
alternative, a partial oxidation process is also used.
Methanol production economics highly depend on the feedstock selection and

feedstock prices. Methanol can be manufactured from any hydrocarbon source:
naphtha, oil, coal, wood, biomass, LPG, etc. The naphtha, fraction of crude oil
TM
MARCEL DEKKER, INC.

distillation, is used as a raw material in many older facilities for the manufacture of
methanol. When naphtha is reacted with a high steam ratio, under pressure and at
high temperature, synthesis gas of low methane content is obtained. Most of the
carbon from the naphtha is converted to carbon monoxide and carbon dioxide:
1000°C
CH,+ H,O = CO + 3H,
CO + H,O = CO, + H,
The mixture of hydrogen and carbon oxides is compressed and is passed over a
catalyst under high pressure and at high temperature, methanol is formed.
The mixture of methanol, water, and other impurities is distilled to produce 99.95
mole-percent methanol product purity.
Oxidation - Methanol is oxidized with acidified Potassium Dichromate, K2Cr,0,, or
with acidified Sodium Dichromate, Na,Cr,O,, or with acidified Potassium
Permanganate, KMnO,, to form formaldehyde.
CH,OH = HCHO + H,O
If the oxidizing agent is in excess, the formaldehyde is further oxidized to formic

acid and then to carbon dioxide and water.
HCHO = HCOOH = CO, + H,O
Catalytic Oxidation - The catalytic oxidation of methanol using platinum wire is of
interest as it is used in model aircraft engines to replace the sparking plug
arrangement of the conventional petrol engine. The heat of reaction is sufficient to
spark the engine.
Dehydrogerzation - Methanol can also be oxidized to formaldehyde by passing its

vapor over copper heated to 300°C. Two atoms of hydrogen are eliminated from
each molecule to form hydrogen gas and hence this process is termed
dehydrogenation.
Cu
300"C
CH30H = HCHO + H,
TM
MARCEL
DEKKER,
INC.
Dehydration - Methanol does not undergo dehydration reactions. Instead, in

reaction with sulfuric acid the ester, dimethyl sulfate is formed.
Conc.
H W 4
2CH,OH = (CH,),SO, + H,O
EsterGcation - Methanol reacts with organic acids to form esters
H +
CH,OH + HCOOH = HCOOCH, + H,O

Substitution of Methanol with Sodium - Methanol reacts with sodium at room
temperature to liberate hydrogen. This reaction is similar to the reaction of sodium
with ethanol.
Substitution of Methanol with Phosphorus Pentachloride - Methanol reacts with

phosphorus pentachloride at room temperature to form hydrogen chloride, methyl
chloride (i.e. chloroethane) and phosphoryl chloride.
CH30H + PC1, = HCI + CH3C1 + POCl,
Substitution of Methanol with Hydrogen Chloride - Methanol reacts with hydrogen
chloride to form methyl chloride (i.e. chloromethane) and water. A dehydrating
agent (e.g. zinc chloride) is used.
ZnCI,
CH,OH + HCl = CH,CI + H,O
Ethanol
Ethanol is a monohydric primary alcohol. It melts at -1 17.3"C and boils at 78.5"C.

It is miscible (i.e., mixes without separation) with water in all proportions and is
separated from water only with difficulty; ethanol that is completely free of water is
called absolute ethanol. Ethanol forms a constant-boiling mixture, or azeotrope,
with water that contains 95 % ethanol and 5 % water and that boils at 78.15 "C; since
the boiling point of this binary azeotrope is below that of pure ethanol, absolute
ethanol cannot be obtained by simple distillation. However, if benzene is added to
95% ethanol, a ternary azeotrope of benzene, ethanol, and water, with boiling point
64.g°C, can form; since the proportion of water to ethanol in this azeotrope is
greater than that in 95% ethanol, the water can be removed from 95% ethanol by
adding benzene and distilling off this azeotrope. Because small amounts of benzene
may remain, absolute ethanol prepared by this process is poisonous.
Ethanol acts as a drug affecting the central nervous system. Its behavioral effects
stem from its effects on the brain and not on the muscles or senses themselves. It is
a depressant, and depending on dose can be a mild tranquilizer or a general
TM
MARCEL INC.
DEKKER,
anesthetic. It suppresses certain brain functions. At very low doses, it can appear to
be a stimulant by suppressing certain inhibitory brain functions. However, as
concentration increases, further suppression of brain functions produce the classic
symptoms of intoxication: slurred speech, unsteady walk, disturbed sensory
perceptions, and inability to react quickly. At very high concentrations, ethanol
produces general anesthesia; a highly intoxicated person will be asleep and very
difficult to wake, and if awakened, be unable to move voluntarily. Alcohol levels in
the brain are difficult to measure, and so blood alcohol levels are used to assess
degree of intoxication. Most people begin to show measurable mental impairment at
around 0.05 percent blood alcohol. At around 0.10%, mental impairment will show
obvious physical signs, such as an unsteady walk. Slurred speech shows up at
around 0.15 % . Unconsciousness results by 0 . 4 % . Above 0.5 % , the breathing
center of the brain o r the beating action of the heart can be anesthetized, resulting
in death. Reaching this level of blood alcohol by ingestion is unlikely, however. In
a 150-pound human, it would require rapid consumption of a fifth gallon of a 100-
proof spirit.
Ethanol is used extensively as a solvent in the manufacture of varnishes and

perfumes; as a preservative for biological specimens; in the preparation of essences
and flavorings; in many medicines and drugs; as a disinfectant and in tinctures
(e.g., tincture of iodine); and as a fuel and gasoline additive. Denatured, or
industrial, alcohol is ethanol to which poisonous or nauseating substances have been
added to prevent its use as a beverage; a beverage tax is not charged on such
alcohol, so its cost is quite low. Medically, ethanol is a soporific, i.e., sleep-
producing; although it is less toxic than the other alcohols, death usually occurs if
the concentration of ethanol in the bloodstream exceeds about 5 %. Behavioral
changes, impairment of vision, or unconsciousness occur at lower concentrations.
Ethanol is the alcohol of beer, wines, and liquors. It can be prepared by the
fermentation of sugar (e.g., from molasses), which requires an enzyme catalyst that
is present in yeast; or it can be prepared by the fermentation of starch (e.g., from
corn, rice, rye, or potatoes), which requires, in addition to the yeast enzyme, an
enzyme present in an extract of malt. The concentration of ethanol obtained by
fermentation is limited to about 10% (20 proof) since at higher concentrations
ethanol inhibits the catalytic effect of the yeast enzyme. (The proof concentration of
an alcoholic beverage is numerically double the percentage concentration.) For
nonbeverage uses ethanol is more commonly prepared by passing ethylene gas at
high pressure into concentrated sulfuric or phosphoric acid to form the
corresponding ester; the acid-ester mixture is diluted with water and heated,
forming ethanol by hydrolysis, and the alcohol is then removed from the mixture
by distillation, usually with steam. Ethanol is used in the following ways:
Methylated Spirits - This a very common industrial solvent, used in many

processes. It is also the solvent often used in paints, resins, soaps and
dyes. Methylated spirits is actually ethanol, with 10-15% methanol added.
TM
DEKKER,
MARCEL INC.
Both alcohols are poisonous in such quantities, so a purple dye is added to

stop people drinking it.
After-Shaves, Perfumes and Cosmetics - The active ingredients (usually

smelly!) in these products are dissolved in the ethanol solvent. As the
product is 'splashed all over', the ethanol evaporates, leaving behind the
ingredients.
Industrially produced ethanol has many uses including use in solvent based paints,
pharmaceuticals, perfumes, cleaning products for home and car, lacquers, and inks.
Ethanol and other alcohols have been added to gasoline to produce alcohol-
containing fuels. Since ethanol contains only one partially oxidized carbon atom, it
is flammable and can be used as a fuel. The usual ratio of ethanol to gasoline is
ninety parts gasoline to 10 parts ethanol while that for methanol is 97 parts gasoline
to 3 parts methanol. Some cars have been designed to run on pure methanol.
Gasohol has higher antiknock properties (higher octane) than gasoline, burns more
slowly, coolly, and completely. However, it is more expensive and energy
intensive to produce and may produce environmental hazards to the individual and
to the atmosphere.
Ethanol burns in air with a blue flame, forming carbon dioxide and water. It reacts
with active metals to form the metal ethoxide and hydrogen, e.g., with sodium it
forms sodium ethoxide. It reacts with certain acids to form esters, e.g., with acetic
acid it forms ethyl acetate. It can be oxidized to form acetic acid and acetaldehyde.
It can be dehydrated to form diethyl ether or, at higher temperatures, ethylene.
Manufacture - Ethyl alcohol is derived from two main processes, hydration of

ethylene and fermentation of sugars. Hydration of ethylene is the primary method
for the industrial production of ethyl alcohol, while fermentation is the primary
method for production of beverage alcohol. Traditionally, industrial ethanol is
manufactured via the acid catalyzed hydration of ethylene. One synthetic route of
alcohol by hydration of ethene involves the use of concentrated sulfuric acid
(HJO,). Unfortunately the use of sulfuric acid complicates the process due to
concerns about safety, corrosion, and the environment. Current technology allows
alcohol to be produced by utilization of zeolites or silica aerogels impregnated with
phosphoric or tungstic acid. The distinct advantages of this process are that the
reaction can be a one stage process, the catalyst is regenerated, and concerns about
safety, corrosion, and the environment are diminished. This method has been
chosen due to the relative low cost of the ethylene.
9
Ethanol is particularly useful in industrial applications because of its relatively high 5
affinity for both water and organic compounds. The composition of other alcohols
E
limits their flexibility as compared to ethanol. For example, methanol with one B
carbon (CH,OH) has reduced solubility in hydrocarbons, while increasing the chain
length such as in pentanol with 5 carbon units reduces its solubility in water. Thus,
Z4
5
8-
TM
Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved. 8

2
0
sDO
'%
6
DEKKER,
MARCEL INC.
varying the chain length of the alcohol modifies its solubility in different
compounds making it more or less useful dependent on the situation.
One problem with the industrial production and utilization of ethanol is that ethanol
is the alcohol found in beverages. Thus, industrial alcohol could be the source of
large amounts of beverage alcohol. But it has been the practice to tax and control
alcohol for beverages and industrial ethanol could be the source for a large amount
of illegal alcohol.
In order to reduce the need for strict control and heavy taxation on industrially
produced ethanol, the alcohol is denatured. Denaturing is a process of adding other
compounds to the ethanol to render it unfit for consumption. Denaturants are
selected to give the ethanol a disagreeable taste or odor and in some cases a
distinctive color. In some cases the substances added are toxic and produce gastric
disturbances upon ingestion andior other unpleasant symptoms. A large number of
different "denaturants" are utilized dependent upon the use for which the ethanol is
intended. These denaturants include methyl isobutyl ketone, pyronate, kerosene,
acetone, turpentine, amyl alcohol, methyl alcohol, and various butyl alcohols. In
some cases more than one denaturant is utilized.
All beverage alcohol and much of that used in industry is formed through
fermentation of a variety of products including grain such as corn, potato mashes,
fruit juices, and beet and cane sugar molasses. (In earlier years, until about 1947,
the largest proportion of the production of industrial alcohol was from
fermentation, but as noted above the hydration of ethene now provides the greatest
source of industrial alcohol). Fermentation can be defined as an enzymatically
anaerobic controlled transformation of an organic compound. With respect to
alcohol, we are referring to the conversion of sugars to ethanol by microscopic
yeasts in the absence of oxygen. The equation for the fernlentation of glucose is:
C,H,>O, (in preseilce of qcast) = 2CH,CH20H + 2C0,

The initial fermentation mixture contains approximately 3 to 5 % ethanol such as in
beer and up to 12 to 15% ethanol as in wine and sherry. Higher concentrations of
ethanol cannot be achieved by fermentation, because the yeast becomes inactivated.
In this case distillation is required to generate higher alcohol concentrations.
Distillation is a process that uses differences in boiling points to separate

compounds. In the case of alcohol and particularly ethanol, knowledge that the
boiling point of pure water is 100°C while that of ethanol is 78.3"C allows the
separation of the ethanol from the water by adjusting the distillation temperature to
a point higher than that for ethanol but lower than that for water. Thus, the
concentration of ethanol can be enhanced by removing it as a distallate from the
ethanol-water solution. Sp~ritssuch as gin, scotch, bourbon, and vodka, as well as
liqueurs, cordials, and bitters are examples of beverages made from distillation.
TM
DEKKER,
MARCEL INC.
The distillation procedure also allows for the concentration of components of the
beverage which provide some distinctive flavor.
Pure ethanol (200 proof) cannot be obtained via conventional distillation of a water-
ethanol mixture because a constant boiling mixture forms consisting of 95% ethanol
and 5% water (190 proof). Such a mixture is referred to as an azeotrope
(azeotropic refers to a liquid mixture that is characterized by a constant
concentration and constant minimum or maximum boiling point which is lower or
higher than any of the components). Further concentration of the ethanol can be
achieved by shifting the azeotropic point via vacuum distillation or addition of
another substance to the mixture. Often times the compound added is highly toxic
such as benzene, therefore absolute alcohol must never be consumed. The amount
of ethyl alcohol in any one beverage varies. Thus, there are differences in the
amount of alcohol between beer, wine, champagne and distilled spirits. The amount
of alcohol is given as a percentage and also in "proof". The proof of an alcohol
beverage is equal to twice the percentage of ethyl alcohol contained therein. Thus,
100 proof ethanol is 50% and 50 proof ethanol is 25 % , etc.
The process of making alcohol has been around since virtually as long as man has
been on this earth, though it has been immensely refined and upgraded in recent
years leading to much improved efficiency. As noted, there are three main uses for
ethanol (industrial, beverage, and fuel) and the production processes vary slightly
for each of them, but the main steps are the same. Examples of industrial uses of
ethanol would include ethanol used in perfumes, aftershaves and for cleaners.
Beverage ethanol is used for drinking and must meet strict production standards
because it will be used for human consumption. A vast majority of ethanol
produced in the U.S. is used for fuel. It is blended with gasoline to increase the fuel
blend's octane or to produce a cleaner burning fuel. Most of the ethanol plants in
the country utilize a dry milling process. The major steps are outlined below.
Milling: The corn (or barley or wheat) will first pass through hammer
mills, which grind it into a fine powder called meal.
Liquefaction: The meal will then be mixed with water and alpha-amylase,
and will pass through cookers where the starch is liquefied. Heat will be
applied at this stage to enable liquefaction. Cookers with a high
temperature stage (120-150°C) and a lower temperature holding period
(95°C) will be used. These high temperatures reduce bacteria levels in the
mash.
Saccharification: The mash from the cookers will then be cooled and the
secondary enzyme (gluco-amylase) will be added to convert the liquefied
starch to fermentable sugars (dextrose), a process called saccharification.
Fermentation: Yeast will then be added to the mash to ferment the sugars
to ethanol and carbon dioxide. Using a continuous process, the fermenting
TM
MARCEL
DEKKER,
INC.
mash will be allowed to flow, or cascade, through several fermenters until

the mash is fully fermented and then leaves the final tank. In a batch
fermentation process, the mash stays in one fermenter for about 48 hours
before the distillation process is started.
Distillation: The fermented mash, now called "beer," will contain about
10% alcohol, as well as all the non-fermentable solids from the corn and
the yeast cells. The mash will then be pumped to the continuous flow,
multi-column distillation system where the alcohol will be removed from
the solids and the water. The alcohol will leave the top of the final column
at about 96% strength, and the residue mash, called stillage, will be
transferred from the base of the column to the co-product processing area.
Dehydration: The alcohol from the top of the column will then pass
through a dehydration system where the remaining water will be removed.
Most ethanol plants use a molecular sieve to capture the last bit of water in
the ethanol. The alcohol product at this stage is called anhydrous (pure,
without water) ethanol and is approximately 200 proof.
Denaturing: Ethanol that will be used for fuel is then denatured with a
small amount (2-5%) of some product, like gasoline, to make it unfit for
human consumption.
Co-Products: There are two main co-products created in the production of

ethanol: carbon dioxide and distillers grain. Carbon dioxide is given off in
great quantities during fermentation and many ethanol plants collect that
carbon dioxide, clean it of any residual alcohol, compress it and sell it for
use to carbonate beverages or in the flash freezing of meat. Distillers
grains, wet and dried, are high in protein and other nutrients and are a
highly valued livestock feed ingredient. Some ethanol plants also create a
"syrup" containing some of the solids that can be a separate production
sold in addition to the distillers grain, or combined with it. Ethanol
production is a no-waste process that adds value to the corn by converting
it into more valuable products.
Propyl Alcohol
11-Propanol is a chemical intermediate used in the synthesis of n-propyl amines and

n-propyl acetate. n-Propyl acetate is used in conjunction with n-propyl alcohol as a
solvent blend in printing inks. n-Propanol is also widely used in the manufacture of
various textile chemicals, photographic chemicals, surfactants, and fatty esters such
as oleate and propyl stearate. 11-Propanol is widely used in the printing ink industry
as a solvent for tlexographic inks to control solvent evaporation and ink drying
times. Isopropanol has similar applications as an intermediate and solvent.
TM
MARCEL
DEKKER,
INC.
Propyl alcohol, 1-propanol, is a colorless liquid with an odor similar to ethanol. It

is polar, soluble in water, and has a specific gravity of 0.8, which is lighter than
water. It is a dangerous fire risk with a flammable range of 2 to 13% in air. The
vapor density is 2.1, which is heavier than air. The boiling point is 207OF, the flash
point is 74OF, and the ignition temperature is 77OF. It is toxic by skin absorption
with a TLV of 200 ppm in air. The four-digit UN identification number is 1274.
The NFPA 704 designation is health 1, flammability 3, and reactivity 0. The
primary uses are in brake fluid, as a solvent, and as an antiseptic.
Butyl Alcohols
n-Butanol is widely used to produce plasticizer-type esters (e.g., phthalates,

phosphates, sebacates, oleates, stearates). Two important ester derivatives are n-
butyl acetate and n-butyl acrylate. These are used coating applications and are made
from n-butanol. Glycol ether derivatives (e.g., ethylene glycol monobutyl ether,
EB) is used in the coating industry. It is the product of the n-butyl reaction with
ethylene oxide in the presence of an acid catalyst. Other important n-butyl
derivatives are butyl amines and butyl esters. These are used in formulations for
herbicides, as butyl xanthate ore floatation acids, butylated urea, and melamine-
formaldehyde resins. n-Butanol (n-butyl alcohol), a four carbon straight chain
alcohol, is a medium-boiling liquid that is useful as a chemical intermediate and
solvent. The future of n-butanol is tied to surface coatings, either through its
derivatives or in direct solvent uses. Butanol and its derivatives continue to benefit
from the long-term growth of water-based coatings formulations of all kinds.
Analysts estimate that nearly 70% of all exterior architectural paints and as much as
85% of interior paints are now water-based. Therefore butanol, butyl acrylate and
butyl acetate, become increasingly important.
Another use of n-butyl alcohol is in pesticide residue analysis. Also, it is a solvent

for liquid chromatography, machinery manufacture and repair, metal degreasing,
rubber manufacture, and varnish. It is also an alcohol solvent in paint. It is used in
the manufacture of lacquers, dyestuffs, rayon, detergents, plasticizers, and is a
dehydrating substance. Aerosol paint concentrates, automobile refinish paints,
general performance sealants, herbicides, inks, insecticides for crawling insects,
markers, nail enamels and polishes, paints, sealants, clay, finger paint, paint
removers and thinners, scatter rugs, and bathmats may contain this chemical. The
total butanol produced was approximately 21 1,262 Ibs in 1997.
Other uses of n-butanol include a latent solvent and coupling aid in nitrocellulose
lacquer formulations to improve blush resistance, flow and leveling properties of
the lacquers. It is also used for urea-formaldehyde and melamine-formaldehyde
resins in surface coatings and in wood laminating adhesives. In the pharmaceutical
industry n-butanol is used as an extraction solvent.
TM
DEKKER,
MARCEL INC.
Isobutanol serves as a chemical intermediate in the making of isobutyl esters,

isobutyl amines, and in isobutylated urea or melamine-coating resins. It is used as a
solvent in coating formulations with or without the cosolvent n-butanol. Also
nitrocellulose lacquers employ isobutanol as a latent solvent, while the alcohol is an
active solvent in automotive and furniture finishes, lacquers, thinners, and hot
spray lacquers.
Secondary-butanol is used as an intermediate in the synthesis of methyl ethyl ketone

(MEK) and sec-butyl acetate. Both are good solvents used for coating formulations.
sec-Butanol is an active solvent for ester gum, and in natural and synthetic resins
such as alkyds and urea or melamine-formaldehyde resins. It is also a useful latent
solvent for nitrocellulose lacquers. It is a useful coupling agent in cleaning
formulations, oil field chemical blends, and in emulsion breakers.
Furfuryl Alcohol Derivatives
Synonyms include Furyl Carbinol, 2-Hydroxy Methyl Furan, 2-Furan Methanol,

Furfuryl alcohol resin. Furan resin, FA resin, Poly(furfury1 alcohol), Prepolymers
of FA. It is a raw material for organic synthesis, producing levulic acid, resin of
various furane kinds in different properties, furfuryl alcohol urea formal resin and
phenolic resin. It is a fine solvent for furane resin and oil varnish and pigment as
well as used in rocket fuel. It is also used in the production of synthetic fibers,
rubber, agricultural chemicals and foundry products. Furfuryl alcohol resins are
derivatives of agricultural waste products and complex polymers that are formed in
a condensation reaction that occurs when the furfuryl alcohol is acidified. The
resins have low viscosity with an odor of furfuryl alcohol. The resin systems are
highly reactive and can be catalyzed using a variety of active and latent acidic
catalysts. When thermoset, the resins produce polymers that are heat resistant and
extremely corrosion resistant to acids, bases and solvents.
Furfuryl alcohol-based resins are used as binding agents in foundry sand and as
corrosion inhibitors in mortar, grout, and cement. Because of their heat resistance,
furan resins are used in the manufacture of fiberglass-reinforced plastic equipment.
Derivatives of furfuryl alcohol (chemical formula: C,H,O,) include tetrahydro
furfuryl alcohol, furane resins and organic furfural.
The direct conversion into furfuryl alcohol, methylfuran and furan via metal-
catalyzed hydrogenation, reduction and decarbonylation positions furfural as a
strategic and ultimate industrial source for the production of a wide range of
derivatives. Furfuryl arnine, furoic acid, alpha-methylfurfuryl alcohol can be
produced in one step from furfural. Other important fine chen~icals are 2-
acetylfuran, 2,5-dimethoxydihydrofuran, 5-dimethylaminomethylfurfuryl alcohol,
and others.
TM
MARCEL INC.
DEKKER,
Polyhydric Alcohols
The most common trio1 is glycerol (1,2,3-propanetriol or 1,2,3-trihydroxypropane).

You will also encounter the name glycerine, or glycerin, which is not as acceptable
but has become familiar from its derivative nitroglycerin(e) (more properly called
glycerol trinitrate). The common name for 1,2,3,4-tetrahydroxybutaneis erythritol.
The 5-carbon tetrol tetra(hydroxymethy1)methane is called pentaerythritol;
pentaerythritol tetranitrate (PETN) is a powerful explosive. Specific optical isomers
(to be defined later) of the straight-chained 5-carbon and 6-carbon polyols
analogous to glycerol are arabitol and mannitol. Polyhydric alcohols (polyols) can
also form ethers and polyethers, in the same way as diols (glycols).
Two molecules of an alcohol in reality form an ether by losing a molecule of water

between them; one molecule loses a hydrogen atom H* and the other loses a
hydroxy group *OH:
RO-H + H0.R = ROR + HOH

Since this is the case, it is possible for a molecule with two hydroxyls on different
carbon atoms to form internal ethers:
0
HOCH,CH,OH = / \ + H,O
H2C - CH,
The product in this case is called ethylene oxide, and is an important monomer and
reactive intermediate. A catalyst RXM (not specified here) can open the ethylene
oxide ring, which then adds to itself to form polyethylene glycol (PEG):
RXM +x
H,C-
'CH,
= RX(CH2CH,0),M
If RXM is an alcohol ROH, the product is an ethoxylated derivative of the alcohol,

RO(CH,CH,O),H. A simple example of this type of derivative, when RXM is
CH30H and x = 2, is CH30CH,CH,0CH2CH,0H, Methyl CarbitolB.
Ethylene oxide is an epoxy compound, and can also be named 1.2-epoxyethane.

Diepoxy compounds are commercially important as components of epoxy
adhesives. The simplest diepoxy compound is erythritol anhydride, or 1,2,3,4-
diepoxybutane:
TM
MARCEL DEKKER, INC.

0 0
/ \ / \
H,C--- CH CH- CH,
Terminological purists will name compounds with 3-membered epoxy rings as

derivatives of oxirane, the internationally recognized (IUPAC) name for ethylene
oxide. Some properties of polyhydric alcdho~sare given in Table 6.
Table 6. Properties of Polyhydric Alcohols

Solvent Molecular BP "C @ Specific Viscosity Surface Water
Weight 760 mm Gravity (cP at Tension Sol.
"g (25°C) 25°C) (25°C) (wt.%)
I dyiieslcm
Ethylene glycol I 62 1 197.4 1 1.11 1 16.9 1 48 Comp.
1 Diethylene 1 106 1 245.5 1 1.1 11 1 25.3 1 44 Comp.
glycol
Triethylene 150 1 287.8 ( 1.12 1 39.4 1 45 Comp.
glycol
Tetraethylene 1 194 1 325.6 1 1.123 / 43 Comp.
glycol
Propy lene 76 / 187.4 1 1.032 / 48.6 1 36 Comp.
glycol
Dipropylene I 134 / 232.2 1 1.022 1 75 35 Comp.
glycol
Tripropylene 1 192 / 265.1 ( 1.019 1 57.2 1 34 Comp.
glycol-
Glycerol 92 / 198(40 1 1 . 2 6 2 @ 1 945 1 63.3
Comp.
Comp.
/ @20T j
Neopenty l 104 / 210 / 1.06@ 1 Comp.
glycol 1 20°C I
Hexylene 118 1 198 10.923@ 1 34.4 1 33.1 Comp.
1 glycol 1 20C 1
ALDEHYDES
Aldehydes are organic compounds that have an acyl group, R-C=O with a
Hydrogen bonded to the carbonyl or acyl carbon (double bonded carbon).
Aldehydes and ketones have similar chemistry activity because of the fact that they
TM
MARCEL DEKKER, INC.

both have a carbonyl carbon. The bond is polar with the oxygen atom the negative
end and the carbon end being positive. This results in nucleophiles being attracted
to the carbonyl carbon and bonding with it. This similarity in nucleophilic attack
makes the chemistry very close as we will see. Aldehydes are named by using the
following rules:
1. Identify the longest continuous chain of carbons with the acyl or carbonyl
carbon as part of the chain.
2. Number the carbon chain so that the carbonyl (acyl) carbon is always # I .
3. Locate and identify alphabetically the branched groups by prefixing the

carbon number it is attached to. If more than one of the same type of
branched group is involved use the Greek prefixes di for 2, tri for three,
etc.
4. After identifying the name, number and location of each branched group,
use the alkane name corresponding to the number of carbons in the
continuous chain.
5 . Drop the "e" and add the characteristic IUPAC ending for all aldehydes,
"al".
6 . Alkenals involving pi bonding will require that the pi bond is located but
the ending will still be "al".
Figure 1 provides some examples. Consider the structure in Figure 1(A).
We find the longest continuous chain of carbons with the acyl carbon
involved is five.
Numbering the carbons beginning with the acyl carbon on the extreme
right as carbon # I .
Identifying the branched groups, there is a methyl group on carbon #3 and

a bromine on carbon #2 so we would name and locate them: 2-Bromo-3-
methyl.
Use the alkane name corresponding to the number of carbons in the chain
(5) which would be pentane.
Drop the "e" and add "a]" so the name is: 2-Bromo-3-methylpentanal.
Consider the structure in Figure 1(B).
1. Notice that there is a benzene ring with the characteristic functional group
attached to the ring. This would be the parent aromatic aldehyde
benzaldehyde.
TM
DEKKER,
MARCEL INC.
2. Since we have three substitutions on the benzene ring we must use

numbers and number the ring carbons beginning with the carbon with the
aldehyde functional group attached to it as carbon # I . We then proceed to
number clockwise.
3. We notice a chlorine attached to carbon #3 and a methyl group attached to

carbon #4.
4. Locate and identify these branches: 3-Chloro-4-methyl.
5. Add the parent name ben~aldehyde and we have: 3-chloro-4-

methylbenzalclehyde.
CH, Br H
Figure 1. Structural examples of common aldehydes.
Consider the last example in Figure l(C).
1. Identify the longest continuous chain of carbons with the acyl carbon as
one of the carbons and the double bond must be between two of the
carbons in the continuous chain, which would be six carbons.
TM
MARCEL DEKKER, INC.

Properties and Selectiou of Organic Solvents
Number the carbons in the chain so that the acyl carbon is carbon # I .
Locate and identify all branches, which is only a methyl attached to carbon
# 2-2-methyl.
Locate the pi bond in the chain. It is between the carbons #4 and 5.
Use the alkene name corresponding to the number of carbons (6): hexane.
Locate the pi bond by prefixing the lowest carbon # in which the pi bond is
between. It is between carbon #4 and 5 so it would be: 4-hexene.
Add to the name and it becomes: 2-methyl-4-hexene.
Drop the "e" and add the characteristic "a]" and it becomes: 2-methyl-4-
hexenal.
None of the hydrogen atoms connected to an aldehyde (or ketone) are bonded to an
oxygen or nitrogen so they do not attract other molecules with the strong hydrogen
bonding. For this reason the aldehydes do not have as high a boiling point for the
same sized alcohol that has a hydrogen bonded to an oxygen. However aldehydes
do have the carbonyl structure which is polar since the oxygen is much higher in
electronegativity than the carbon atom. Therefore, aldehydes will exhibit dipole-
dipole interactions as well as the weak London dispersion intermolecular forces
which make them have higher boiling points compared to the hydrocarbons and the
ethers. For example, propanal and acetone have boiling points of 49°C and 56"C,
respectively. The difference is due to the slightly higher molecular mass of acetone.
This is to be compared with 1-propanol of 97°C and ethyl methyl ether at 8°C and
butane at 0°C. The extra strong hydrogen bonding between the 1-propanol
molecules would account for its higher boiling point.
The carbonyl oxygen with its lone pairs allows aldehydes to hydrogen bond with
hydroxylic compounds like water and alcohols. Therefore, the low molecular mass
(up to four carbons) of aldehydes allows them to be very soluble in water. This
solubility is similar to alcohols and ethers which also have oxygen atoms with lone
pairs of electrons. Aldehydes (and ketones) of greater than five carbons generally
will not be soluble in water as are the alcohols. This is because the increased size of
the hydrocarbon portion will prevent water molecules from being attracted to the
organic molecules. In other words the solvation process is hampered and the water
molecules are not capable of surrounding each organic molecule and separating
them. The polar water molecules have little attraction for hydrocarbons.
We can transform an alkene into an alkane by adding an H, molecule across the

C = C double bond.
TM
MARCEL DEKKER, INC.

The driving force behind this reaction is the difference between the strengths of the
bonds that must be broken and the bonds that form in the reaction. In the course of
this hydrogenation reaction, a relatively strong H H bond (435 kJ/mol) and a
moderately strong carbon-carbon ].bond (270 !d/mol) are broken, but two strong
C H bonds (439 kJimol) are formed. The reduction of an alkene to an alkane is
therefore an exothermic reaction.
What about the addition of an H, molecule across a C = O double bond?
I I Pt
I I
H- C- C-H + H , H- C- C- H
Once again, a significant amount of energy has to be invested in this reaction to

break the H - H bond (435 kJ/mol) and the carbon-oxygen nbond (375 kJ/mol).
The overall reaction is still exothermic, however, because of the strength of the
C - - H bond (439 kJlmol) and the 0 - H bond (498 kJlmol) that are formed.
The addition of hydrogen across a C = O double bond raises several important

points. First, and perhaps foremost, it shows the connection between the chemistry
of primary alcohols and aldehydes. But it also helps us understand the origin of the
term aldehyde. If a reduction reaction in which H, is added across a double bond is
an example of a hydrogenation reaction, then an oxidation reaction in which an H,
molecule is removed to form a double bond might be called dehydrogenadon.
Thus, using the symbol [0]to represent an oxidizing agent, we see that the product
of the oxidation of a primary alcohol is literally an "al-dehyd" or aldehyde. It is an
alcohol that has been dehydrogenated.
TM
MARCEL DEKKER, INC.

This reaction also illustrates the importance of differentiating between primary,

secondary, and tertiary alcohols. Consider the oxidation of isopropyl alcohol, or 2-
propanol, for example.
The product of this reaction was originally called aketone, although the name was
eventually softened to azetone and finally acetone. Thus, it is not surprising that
any substance that exhibited chemistry that resembled "aketone" became known as
a ketone.
Aldehydes can be formed by oxidizing a primary alcohol; oxidation of a secondary

alcohol gives a ketone. What happens when we try to oxidize a tertiary alcohol?
The answer is simple: Nothing happens.
There aren't any hydrogen atoms that can be removed from the carbon atom
carrying the - OH group in a 3' alcohol. And any oxidizing agent strong enough
to insert an oxygen atom into a C C bond would oxidize the alcohol all the way
to CO, and H,O.
A variety of oxidizing agents can be used to transform a secondary alcohol to a

ketone. A common reagent for this reaction is some form of chromium(V1) -
chromium in the +6 oxidation state in acidic solution. This reagent can be
prepared by adding a salt of the chromate (CrO:) or dichromate (Cr,O?~) ions to
sulfuric acid. Or it can be made by adding chromium trioxide (CrO,) to sulfuric
TM
MARCEL DEKKER, INC.

28 Industrial Solvents Ha~idbook
acid. Regardless of how it is prepared, the oxidizing agent in these reactions is

chromic acid, H,CrO,.
The choice of oxidizing agents to convert a primary alcohol to an aldehyde is much

more limited. Most reagents that can oxidize the alcohol to an aldehyde carry the
reaction one step further they oxidize the aldehyde to the corresponding
carboxylic acid.
A weaker oxidizing agent, which is just strong enough to prepare the aldehyde
from the primary alcohol, can be obtained by dissolving the complex that forms
between CrO, and pyridine, C,H,N, in a solvent such as dichloromethane that
doesn't contain any water.
The common names of aldehydes are derived from the names of the corresponding
carboxylic acids.
HCOH HCH CH,COH CH,CH

Formic A rid Formaldeh yile Acefic A cid Aceraldehyde
The systematic names for aldehydes are obtained by adding -01 to the name of the
parent alkane.
TM
MARCEL DEKKER, INC.

HCH CH3CH
Methanal Ethanal Acid
The presence of substituents is indicated by numbering the parent alkane chain from
the end of the molecule that carries the - CHO functional group. For example,
The common name for a ketone is constructed by adding ketone to the names of the
two alkyl groups on the C = O double bond, listed in alphabetical order.
CH,CCH,CH3 Ethyl methyl ketone
The systematic name is obtained by adding -one to the name of the parent alkane
and using numbers to indicate the location of the C = O group (e.g., 2-Propanone).
A common aldehyde is formaldehyde. Formaldehyde has a sharp, somewhat

unpleasant odor. The aromatic aldehydes in the figure below, on the other hand,
have a very pleasant "flavor." Benzaldehyde has the characteristic odor of almonds,
vanillin is responsible for the flavor of vanilla, and cinnamaldehyde makes an
important contribution to the flavor of cinnamon.
Benzalde/zyde Vanillin Cinnamaldehyde
TM
DEKKER,
MARCEL INC.
Aldehydes play an important role in the chemistry of carbohydrates. The term

carbohydrate literally means a "hydrate" of carbon, and was introduced to describe
a family of compounds with the empirical formula CH,O. Glucose and fructose, for
example, are carbohydrates with the formula C,H,,O,. These sugars differ in the
location of the C = O double bond on the six-carbon chain, as shown in the figure
below. Glucose is an aldehyde; fructose is a ketone.
H- C- C- C- C- C- C- OH Glucose
.. ..
I.....'
H O H H H H
HO- c.7 c- C- C- C- C- OH Fructose
... ..-
H """' O H H H H
Aldehydes are mainly formed by the oxidation of alcohols, for example with
acidified dichromate(VI),,,, ions. Aldehydes are formed by the partial oxidation of
primary alcohols, e.g. :
ethanol ethanal
Various properties of common aldehydes are reported in Table 7.
TM
DEKKER,
MARCEL INC.
Table 7. Properties of Aldehydes

Solvent Mol. BP "C @ Specific Viscosity Surface Solubility
Wt. 760 rnrn Gravity cP at Tension Solvent in
Hg (20°C) 25°C (25°C) water,
dyneslcm gllOOg
Formaldehyde 30 -2 1 0.816 95
37% Aqueous 30 98.3 1.1129
formaldehyde
solution
Acetaldehyde 41.1 20 0.7778 0.2 21.2 Complete
Propion- 58.1 48 0.802 0.4 21.8 35
aldehyde
Butyr-aldehyde 72.1 75 0.7982 0.45 24.6 7.6
Isobutyr- 72.1 64 0.7938 0.45 23.2 6.7
aldehyde
2-Furaldehyde 96.1 161.7 1.15% 1.49 41.1 8.3
AMINES
Amines are organic derivatives of ammonia, NH,. They are classified as primary,
secondary, and tertiary, just like the alcohols, based on how many alkyl groups are
bonded to the nitrogen. Refer to the illustrations below.
ammonia primary (lo) amine secondary (2")amine tertiary (3") amine
The lone pair of electrons on all amines makes them nucleophiles and also bases.
Simple amines are commonly named by naming the alkyl groups attached to the
nitrogen followed by the word -amhe. As examples:
methyl m i n e ethyl m i n e ethyl methyl m i n e
TM
MARCEL INC.
DEKKER,
270 Madison Avenue. New York. New York 10016
Aromatic amines are named as derivatives of aniline. As examples:
aniline 0-ethyl aniline N-methyl aniline
Another way of naming amines is by the Clrerrliccrl Ahstrwcts system, in which the
suffix -anline is used after the name of the longest alkane chain attached to the
nitrogen. Primary and secondary amines are capable of forming hydrogen bonds with
each other. The following cxaniple illustrates this:
Tertiary amines can not form hydrogen bonds with each other, but can form
hydrogen bonds with other primary or secondary amines. The ability to form
hydrogen bonds imparts primary and secondary amines' relatively high boiling
points for their molecular weights, although the H- - N - - H hydrogen bond is not
as strong as the H- - 0 - - H hydrogen bond. A comparison of the boiling points of
trimethylarnine, (CH,),N, (B.P. = 2.9"C) and propylamine, CH,CH,CH,NH,,
(B.P. = 48.7"C), which have the same molecular weights, illustrates the effects of
hydrogen bonding. All amines, including tertiary amines, are capable of forming
hydrogen bonds with water molecules, so most light amines are highly soluble in
water.
Ammonia, or an amine, reacts with an alkyl halide to form an alkyammonium salt,

from which the resultant alkylated amine can be obtained by treatment with a strong
base. Primary, secondary, and tertiary amines can also be alkylated.
Alkylation can also be intermolecular as in the formation of nicotine
TM
MARCEL
DEKKER,
INC.
270 Madison Avenue. New York. New York 10016
nocotine
R-
.
Amines will react with strong acids to form alkylammonium salts.
NH2 + HCI -
Tertiary amines react with primary or secondary alkyl halides to form quaternary
R-
+
NH, + CI
ammonium salts.
CH, choline CH, acetylcholine
Demand for amines in the U.S. is expected to grow to nearly $2 billion in 2004.
Advances in volume terms will be led by specialty amines which offer stronger
performance characteristics. The mature fatty and commodity amines are expected
to post more modest gains. Good growth opportunities will exist in the water
treatment and plastics market, while demand in the larger amines markets, which
include detergents, cleaning products, personal care products and agricultural
chemicals, are expected to advance more moderately. For commodity amines,
service and reliability are instrumental in customer satisfaction, while product
performance is paramount for more specialized products. The export market,
TM
MARCEL DEKKER, INC.

traditionally important to U.S. producers, is expected to be more critical as industry

participants strive to expand despite the relative maturity of U.S. end-use markets.
In general, the U.S. amines market is quite concentrated, with about a dozen firms
supplying over 90% of demand. The top four participants are Union Carbide, Air
Products and Chemicals, Huntsman and Dow Chemical. The proposed merger of
Dow and Union Carbide is likely to reshape the market considerably, either by
creating greater concentration, by redistributing market share by way of
divestiture/acquisition, or by introducing one or more new market leaders.
Traditional uses of amines are in the production of powder and liquid detergents,
personal care products, automobile waxes and furniture polishes. Other uses
include urethane foam for furniture and automobile seat cushions, cement additives,
metal workmg tluids, herbicides and natural gas cleaning agents for cleaner burning
fuel. Amines are also used to produce shampoos, shaving creams, cosmetics, fuel
and lubricant additives, dyes, pharmaceutical products, sealants and corrosion
inhibitors.
Table 8 provides some typical properties of aliphatic amines
Table 8. Properties of Aliphatic Amines

Solvent Mol. Wt. BP "C @ 760 m m Specific Gravity
Hg (20°C)
Ethyl 45.1 16.6 0.6829
Diethvl 73.1 56.3
.. . 0.7056
Triethyl 101.2 89.3 0.7275
Propyl 59.1 47.8 0.7173
Dipropyl 101.2 109.2 0.74
Tripropyl 143.3 156 0.7558
Isopropyl 59.1 32.4 0.6886
Diisopropy 1 101.2 84 0.7169
Butyl 73.1 77.8 0.7414
Dibutyl 129.2 159 0.767
Tributyl 185.4 213 0.7771
Isobutyl 73.1 68 0.736
Diisobutyl 129.2 139 0.745
Trisobutyl 185.4 191 0.7684
Hexyl 101.2 130 0.766
Cyclohexyl 99.2 134 0.8647 (25°C)
ESTERS
Esters are compounds formed, along with water, by the reaction of acids and
alcohols. Because this process is analogous to the neutralization of an acid by a
base in salt formation, esters were formerly called ethereal salts. This term is
misleading because esters, unlike salts, are not ionized in solution. Esters can be
TM
MARCEL DEKKER, INC.

formed from both organic and inorganic acids. For example, the simple ester ethyl
nitrate may be obtained from ethyl alcohol and nitric acid (an inorganic acid), and
the ester ethyl acetate may be obtained from ethyl alcohol and acetic acid (an
organic acid). Another method of preparing esters is to employ not the acid itself
but its chloride. For example, ethyl acetate may be prepared by the action of
alcohol upon acetyl chloride, the chloride of acetic acid. Another important method
of preparation is by the reaction of the silver salts of acids with an alkyl halide
(usually iodine). For example, ethyl acetate may be prepared from silver acetate
and ethyl iodide.
Esters are broken up by the action of water into their component acids and
alcohols, a reaction greatly speeded by the presence of acids. For example, ethyl
acetate is broken up into acetic acid and ethyl alcohol. The conversion of an acid
into an ester is termed esterification. The reaction between an ester and a metallic
base is known as saponijication. When the decomposition of an ester occurs upon
its reaction with water, the ester is said to be hydrolyzed.
The esters of organic acids are usually colorless, neutral liquids, pleasant-smelling
and generally insoluble in water but readily soluble in organic solvents. Many
esters have a fruity odor and are prepared synthetically in large quantities for
commercial use as artificial fruit essences and other flavorings and as components
of perfumes (e.g., essential oils).
All natural fats and oils (other than mineral oils) and most waxes are mixtures of
esters. For example, esters are the principal constituents of beef fat (tallow), hog
fat (lard), fish oils (including cod-liver oil), and flaxseed oil (linseed oil). Esters of
cetyl alcohol are found in the head oil of the sperm whale, and esters of myricyl
alcohol in beeswax. Nitroglycerin, an important explosive, is an ester.
Nitroglycerin (formula C,H,(NO,),) is derived from glycerin by treatment with a
mixture of concentrated sulfuric and nitric acids. It is a heavy, oily, colorless or
light-yellow liquid, of specific gravity 1.60, with a sweet, burning taste. It gives
two crystalline forms, one melting at 223°C (37"F), the other at 13S°C (56.3"F).
It solidifies at 12°C (53.6"F). Nitroglycerin burns quietly when heated in air, but
explodes when heated above 218°C (424°F) or when heated in a closed vessel. It is
very sensitive to shock and therefore dangerous to transport. Nitroglycerin is a
common explosive and is usually mixed with an inert, porous material such as
sawdust. When detonated, it produces about 10,000 times its own volume of gas. It
is 8 times as powerful as gunpowder in proportion to relative weight, and 13 times
as powerful in proportion to relative volume. Nitroglycerin is used medically, in
doses of 0.2 to 0.6 mg, as an agent to cause dilation of blood vessels.
Esters such as amyl acetate (banana oil), ethyl acetate, and cyclohexanol acetate are
the principal solvents for lacquer preparations. Other esters, such as dibutyl
phthalate and tricresyl phosphate, are used as plasticizers in lacquers. Amy1 acetate
is employed as odor bait in grasshopper poisons, and several of the formates are
TM
MARCEL DEKKER, INC.

good fumigants. Esters also have an important function in organic synthesis. Esters
are best described as a functional group in organic chemistry and biochemistry
consisting of an organic radical united with the residue of any oxygen acid, organic
or inorganic. The most common esters found in nature are fats, which are esters of
glycerine and fatty acids, oleic, etc., resulting from the condensation of a carboxyl
acid and an alcohol. The process is called esterification:
Esters can participate in hydrogen bonds as hydrogen bond acceptors, but cannot
act as hydrogen bond donors, unlike their parent alcohols. This ability to participate
in hydrogen bonds leads them to be more water soluble than their parent
hydrocarbons. But the limitations on their hydrogen bonding also make them more
hydrophobic than either their parent alcohols or parent acids. Their lack of
hydrogen-bond donating ability means that they can't form hydrogen bonds between
ester molecules, which makes them generally more volatile than an acid or ester of
similar molecular weight. Many esters have distinctive odors, which leads to their
widespread use as artificial flavorings and fragrances. Esters also participate in
ester hydrolysis - the breakdown of an ester by water. Esters may also be
decomposited by strong acids or bases. As the result they are decomposited into
alcohol and salt of carboxyl acid.
Thousands of different kinds of esters are commercially produced for a broad range
of applications. Within the realm of synthetic lubrication, a relatively small but still
substantial family of esters has been found to be very useful in severe environment
applications. Esters have been used successfully in lubrication for more than 50
years and are the preferred stock in many severe applications where their benefits
solve problems or bring value. For example, esters have been used exclusively in
jet engine lubricants worldwide due to their unique combination of low temperature
flowability with clean high temperature operation. Esters are also the preferred
stock in the new synthetic refrigeration lubricants used with CFC replacement
refrigerants. Here the combination of branching and polarity make the esters
miscible with the HFC refrigerants and improves both low and high temperature
performance characteristics. In automotive applications, the first qualified synthetic
crankcase motor oils were based entirely on esters and these products were quite
successful when properly formulated. Esters have given way to PAOs in this
application due to PAOs, lower cost and their formulating similarities to mineral
oil. Nevertheless, esters are nearly always used in combination with PAOs in full
synthetic motor oils in order to balance the effect on seals, solubilize additives,
TM
MARCEL DEKKER, INC.

reduce volatility, and improve energy efficiency through higher lubricity. The
percentage of ester used in motor oils can vary anywhere from 5 to 25 % depending
upon the desired properties and the type of ester employed.
Like PAOs, esters are synthesized from relatively pure and simple starting
materials to produce predetermined molecular structures designed specifically for
high performance lubrication. Both types of synthetic basestocks are primarily
branched hydrocarbons which are thermally and oxidatively stable, have high
viscosity indices, and lack the undesirable and unstable impurities found in
conventional petroleum based oils. The primary structural difference between esters
and PAOs is the presence of multiple ester linkages (COOR) in esters which impart
polarity to the molecules. This polarity affects the way esters behave as lubricants
in several ways. First, the polarity of the ester molecules causes them to be
attracted to one another and this intermolecular attraction requires more energy
(heat) for the esters to transfer from a liquid to a gaseous state. Therefore, at a
given molecular weight or viscosity, the esters will exhibit a lower vapor pressure
which translates into a higher flash point and a lower rate of evaporation for the
lubricant. Generally speaking, the more ester linkages in a specific ester, the higher
its flash point and the lower its volatility. Second, polarity also causes the ester
molecules to be attracted to positively charged metal surfaces. As a result, the
molecules tend to line up on the metal surface creating a film which requires
additional energy (load) to penetrate. The result is a stronger film which translates
into higher lubricity and lower energy consumption in lubricant applications. Third,
the polar nature of esters also makes them good solvents and dispersants. This
allows the esters to solubilize o r disperse oil degradation by-products which might
otherwise be deposited as varnish or sludge, and translates into cleaner operation
and improved additive solubility in the final lubricant. Fourth, while stable against
oxidative and thermal breakdown, the ester linkage provides a vulnerable site for
microbes to begin their work of biodegrading the ester molecule. This translates
into very high biodegradability rates for ester lubricants and allows more
environmentally friendly products to be formulated.
Another important difference between esters and PAOs is the versatility in the
design of ester molecules due to the high number of commercially available acids
and alcohols from which to choose. For example, if one is seeking a 6 cSt (at
100°C) synthetic basestock, the choices available with PAOs are a "straight cut" 6
cSt product or a "dumbbell" blend of a lighter and heavier PAO. In either case, the
properties of the resulting basestock are essentially the same. With esters, literally
dozens of 6 cSt products can be designed, each with a different chemical structure
selected for the specific desired property. This allows the "ester engineer" to
custom design the structure of the ester molecules to an optimized set of properties
determined by the end customer or defined by the application. The performance
properties that can be varied in ester design include viscosity, viscosity index,
volatility, high temperature coking tendencies, biodegradability, lubricity,
hydrolytic stability, additive solubility, and seal compatibility.
TM
MARCEL INC.
DEKKER,
A common concern when formulating with ester basestocks is compatibility with

the elastomer materials used in the seals. All esters will tend to swell and soften
most elastomer seals; however, the degree to which they do so can be controlled
through proper selection. When seal swell is desirable, such as in balancing the seal
shrinkage and hardening characteristics of PAOs, more polar esters should be used
such as those with lower molecular weight and/or higher number of ester linkages.
When used as the exclusive basestock, the ester should be designed for
compatibility with seals or the seals should be changed to those types which are
more compatible with esters. Another potential concern with esters is their ability
to react with water or hydrolyze under certain conditions. Generally this hydrolysis
reaction requires the presence of significant amounts of water and heat with a
relatively strong acid or base to catalyze the reaction. Since esters are usually used
in very high temperature applications, high amounts of water are generally not
present and hydrolysis is rarely a problem in actual use. Where the application
environment may lead to hydrolysis, the ester structure can be designed to greatly
improve its hydrolytic stability and additives can be selected to minimize any
effects.
ETHERS
The chief functional group for the ether family is the 0 - R group called the alkony
group. The general structure for ethers is R-0-R'. Symmetrical ethers are those
where the alkyl groups, R and R ' , are the same. Asymmetrical ethers are those
where the R and R' are different. Simple ethers can be named by naming the alkyl
groups alphabetically followed by the word "ether". For example, CH,-0-CH,-CH,
would be called using this common name approach as ethyl methyl ether. However
for more complex ethers that have branching, using this common name approach is
considerably more difficult. The IUPAC has come up with some rules that allow
the naming of complex ethers. The rules are similar to those used in naming
alcohols except the 0 - R group is named as any other branched group. Using the
rules for alkanes, alkenes, or alkynes with the alkoxy groups identified on the
longest continuous chain. The rules are as follows:
1. Determine the longest continuous chain of carbons with the other less
complex alkyl group.
2. Number the carbons so that the 0 - R group is attached to the lowest

numbered carbon.
3 . Determine the name of the 0 - R group attached to the carbon number.
4. Identify all the branched groups including the alkoxy group and hyphenate
the carbon number they are attached to the front of the branch name.
TM
MARCEL
DEKKER,
INC.
Properties and Selection of Organic Solvents
5 . Identify and locate each group alphabetically.
6. Add the normal alkane name corresponding to the longest continuous

chain.
The boiling points of alcohols are in general much higher than comparably sized
ethers. That can be explained by the extra intermolecular forces between the
alcohol molecules due to the hydrogen bonding. There is no such hydrogen bonding
between the ether molecules because all the hydrogen atoms are not bonded to an
oxygen or a nitrogen atom. Since there is not any possibility of hydrogen bonding
the forces between the ether molecules are much weaker and can be much more
easily vaporized. As an example, the boiling point of ethanol, CH,-CH,-0-H, is
78°C. The boiling point of the constitutional isomer dimethyl ether, CH,-0-CH,, is
only -24"C, more than 100 degrees lower. Since the size of the molecules of the
two compounds are approximately the same, this dramatic difference can only be
explained by the presence of hydrogen bonding with the alcohol. Branching will
tend to decrease the boiling point since a more symmetrical molecule will have less
London dispersion forces and with more hydrocarbon branching around the
carbinol carbon (carbon bonded to the hydroxyl group) the hydrogen bonding of
fewer molecules results, and therefore the compound can be vaporized at a lower
temperature. A dramatic example of this is found in the four carbon alcohols, 1-
butanol, 3-methyl-1-propanol, 2-butanol, and 2-methyl-2-propanol. They have
boiling points of 118, 108, 100, and 8 3 T , respectively.
The water solubility of alcohols and ethers are more similar. Low molecular weight
alcohols and ethers are water soluble such as methanol, ethanol, and dimethyl
ether. But four carbon alcohols and higher and three carbon ethers or higher have a
much lower water solubility. This can be explained by considering the way that
water molecules can disperse solute molecules into a solution. The polar water
molecules are attracted to the hydroxyl group by hydrogen bonding that occurs
between the hydrogens of the water molecules and the oxygen of the alcohol or
ether. With smaller molecules water can more easily surround the ether or alcohol
molecules effectively separating them from one another. This is called solvation
and each ether or alcohol molecule is encapsulated in a water "cage". As the
hydrocarbon portions of the alcohol or ether become more extensive as they would
be in a higher molecular weight ether, it takes far more water molecules to achieve
the same goal (solvation) if it is possible at all. The larger the solute molecules, the
less likely that will occur. Increased branching will increase water solubility. This
can be explained by the fact that increased branching around the caribinol carbon
will mean that water molecules will have a smaller molecular surface area to
surround in trying to encapsulate the organic molecule.
As noted, ether molecules are not capable of forming hydrogen bonds with other
ether molecules, although they can form hydrogen bonds to water. See the
following example.
TM
MARCEL DEKKER, INC.

This accounts for the fact that the boiling points of ethers are similar to the B.P.'s
of alkanes of approximately the same molecular weight. It also accounts for the
high solubility of the smaller ethers in water.
Ethers are excellent solvents for a variety of substances due to their generally non-
polar nature combined with the ability to form hydrogen bonds with certain types of
molecules. They are also relatively unreactive, so they make good solvents for
chemical reactions to occur in. Unfortunately, they are also highly flammable and
susceptible to slow oxidation by air to form peroxides which are highly explosive.
As noted symmetrical ethers with the alkyl hydrocarbon groups linked through the
ether oxygen atom can be named dialkyl ethers or, more commonly, just the alkyl
ether. Unsymmetrical ether structures with two different alkyl groups are named to
reflect both the different alkyl groups. The name of the alkylene oxide corresponds
to the hydrocarbon chain with the cyclic ether linkage being signified by the
designation of oxide. The larger cyclic structures are usually classified as a
heterocyclic structure such as furan, 1,4-dioxane, or 1,3-dioxolane. A series of
aliphatic diether structures bear the common name "glyme" to which is attached the
prefix "mono-," "di-," "tri-," or "tetra-" that denotes the number of (-CH,CH,O)
groups in the molecule. The first member in the glyme series is the dimethyl
ether of ethylene glycol (CH,OCH,CH,OCH,) o r monoglyme. Addition of
a (CH,CH,O) group to the monoglyme yields diglyme o r the dimethyl
ether of diethylene glycol (CH,OCH,CH,OCH,CH,OCH,). Addition of one
o r two (-CH,CH,O) groups to diglyme yields the tri- and tetraglyme
solvents. The simplest ethyl ether analog is ethylene glycol diethyl ether
o r ethyl glyme. T h e corresponding diethylene glycol diether solvent is
ethyl diglyme. The Grant Chemical Division of the Ferro Corporation
produces diethylene glycol dibutyl ether o r butyl diglyme solvent.
Table 9 lists the common chemical names for the dialkyl, alkyl-vinyl, and
the cyclic ether solvents along with the C A index names (Chemical
Abstract Index, American Chemical Society) and the CAS numbers
(Chemical Abstract Service, American Chemical Society). T h e C A S
numbers refer to the major ether component. Refer to the Material Safety
Data Sheet (MSDS) for C A S numbers of any minor impurities in the
solvent.
TM
MARCEL DEKKER, INC.

Table 9. Common Names of Aliphatic and Cyclic Ethers

Common Name CA Index Name CAS Number
Methyl ether Methane, oxybis- 115-10-6
Ethyl ether Ethane, 1,1'-oxybis- 60-29-7
Isopropyl ether Propane, 2,2'-oxybis- 108-20-3
n-Butyl ether Butane, 1, 1'-oxybis- 142-91-1
n-Amvl ether Pentane., 1.1
, '-oxvbis- 693-65-2
n-Hexyl ether Hexane, 1,1'-oxybis- 112-58-3
Methyl terbutyl ether Propane, 2-methoxy-2- 1634-04-4
methyl-
Ethyl vinyl ether Ethene, ethoxy- 109-92-2
n-Butyl vinyl ether Ethene, n-butoxy- 11 1-34-2
Isobutyl vinyl ether Ethene, Isobutoxy- 109-53-5
2-Ethylhexyl vinyl ether Ethene, 2-ethylhexoxy- 103-44-6
Propylene oxide 1,2-epoxypropane 75-56-9
1.2-Butvlene oxide Oxirane. ethvl- 106-88-7
1,3-dioxolane 1,3-Dioxolane 646-06-0

Anisole Benzene, methoxy- 100-66-3
Furan Furan 110-00-9
2-Methylfuran Furan, 2-methyl- 534-22-5
Tetrahydrofuran Furan, tetrahydro- 109-99-9
Preparation and Chemical Reactivity
Diethyl ether is the most important commercial ether. It can be prepared by the
following reaction:
Ethers can also be prepared by the acid catalyzed addition of an alcohol to an

alkene.
CH3-0-H -t
\
/
C- C
/
\
- H+
CH3- 0-
I
C-
I
CH,
Ethers with two different R groups attached to the 0 atom are sometimes called
TM
MARCEL DEKKER, INC.

-
unsymmetrical ethers. This type of ether is most commonly prepared by the
following method:
2ROH
2RO-H'
+
+
2Na
R' - X- 2RO-Na'
sodium alkoxide
ROR' +
+
NafX
H,
Cleavage of ethers can occur, initiated by the attack of a Lewis acid on one of the
lone pairs of electrons on the 0 atom of the ether.
R - O R ' + C1-B-C1- R-0-R'

I I
C1 C1 - B - C1
I
C1
These intermediates can then undergo cleavage.
Most ethers, particularly the dialkyl ethers, react with atmospheric oxygen in a
radical-chain process to form unstable, shock-sensitive, and generally explosive
peroxide (-COO-) and hydroperoxide ( - 0 0 0 H ) compounds. Some of the widely
used ethers like ethyl and isopropyl ethers, furan, and tetrahydrofuran can rapidly
accumulate dangerous amounts of the peroxide compounds. Use of a dry, inert
nitrogen atmosphere over the ethers and the use of a phenolic antioxidant such as
2,6-di-tertbutyl-4-methyl phenol (BHT) will prevent the formation of dangerous
amounts of the peroxides. The 1,4-dioxane, 1,3-dioxolane, and glyme diethers
while susceptible to air oxidation tend not to form dangerous amounts of the shock-
sensitive peroxides. Light and heat will accelerate the peroxide formation. Since the
peroxides will concentrate upon solvent distillation one should test for the peroxide
content of the solvent prior to any distillation. The common analytical method for
peroxide determination involves reduction of the peroxide functional group with an
excess of a reducing agent followed by back-titration of any excess reducing agent.
The solvent manufacturer can supply the exact details on the peroxide
determination procedures. Coated paper test strips for approximate peroxide
determinations are also available from chemical supply houses. Any concentrations
above minimum levels ( > 0.1 % peroxide) must be chemically destroyed prior to
the distillation process. No distillation process should be carried to dryness because
TM
MARCEL
DEKKER,
INC.
of the dangers of concentrating trace amounts of the shock- and heat-sensitive

peroxides. All ethers will form peroxides due to atmospheric oxidation reactions,
some dialkyl ethers (e.g., ethyl and isopropyl ether) and the cyclic ethers (e.g.,
furan and tetrahydrofuran) are particularly prone to peroxide formation. The use of
an inert nitrogen pad over the ether solvents, the addition of an antioxidant, and the
exclusion of light and excessive heat will aid in preventing excessive peroxide
formation.
Uses
The dialkyl ethers are often used as inert solvents in organic synthesis processes
since the carbon-oxygen bond in the ethers is not readily cleaved by normal acid or
basic reagents. Strong acids (e.g., sulfuric acid, perchloric acid, or hydrobromic
acid) will form unstable oxonium salts with the ethers. Relatively stable complexes
are formed between ethers and Lewis acids such as boron trifluoride and aluminum
chloride; however, the cyclic three-member epoxy compounds (e.g., propylene
oxide, 1,2-butylene oxide), and the furan derivatives are readily cleaved by acidic
reagents. The epoxy ether on contact with hydrochloric acid undergoes ring
opening to yield the chlorohydrin derivative (e.g., RCH,(OH)CH,CI). Reaction of
propylene oxide with an alcohol o r phenol yields the monoether of propylene
glycol. Acid hydrolysis of furan and its homologs yields ring cleavage to give
dicarbonyl compounds and polymer formation.
Dimethyl ether is used as a solvent in aerosol formulations. Diethyl ether as a

commercial product is available in several grades and is used as an extraction
solvent, reaction solvent, and as a general anesthetic. Ethyl ether is an excellent
solvent for alkaloids, dyes, fats, gums, oils, resins, and waxes. Blends of ethyl
ether and ethanol are excellent solvents for cellulose nitrate used in the manufacture
of guncotton, in collodion solutions and pyroxylin plastics. Ethyl ether is used in
the recovery of acetic acid from aqueous solutions in the cellulose acetate and
plastic industry. It is used as a starter fuel for diesel engines and as a denaturant in
denatured ethanol formulations. Grignard and Wurtz-Fillig synthesis reactions use
diethyl ether as an anhydrous, inert reaction medium. n-Butyl ether is used in
synthesis reactions that require an anhydrous, inert solvent. This ether is a valuable
extraction solvent for aqueous solutions because of its low water solubility. n-Butyl
ether when mixed with ethanol or butanol is an excellent solvent for ethyl cellulose.
Isopropyl ether is a solvent of minor importance since its boiling point is
intermediate between the two widely used solvents diethyl ether and acetone.
Hazardous peroxides are formed more readily in isopropyl ether than in other
dialkyl ethers. The commercial diamyl ether consists of a blend of di-n-amyl and
di-iso-amyl ether, a small amount of isomeric amyl ethers and diamylene. A blend
of diamyl ether and 20% ethanol will dissolve ethyl cellulose. n-Hexyl ether can
replace n-butyl ether in many of its applications.
TM
MARCEL
DEKKER,
INC.
Methyl tert-butyl ether (MTBE) is used as an octane enhancer in gasoline. EPA

regulations allow up to 2.7 wt.% oxygen in gasoline which allows 15 v o l . %
MTBE in gasoline. Other alkyl ethers can also be blended into gasoline up to the
2.7 wt% oxygen requirement. The stability of MTBE to oxidation and peroxide
formation gives this unsymmetrical ether an advantage over other ethers in various
extraction and reaction solvent applications.
Furan is a valuable chemical intermediate for pharmaceuticals, insecticides, and

other organic compounds. The furan ring is cleaved by aqueous acid which can lead
to polymer formation. Tetrahydrofuran (THF), the saturated derivative of furan,
when used as a solvent for high molecular weight polyvinyl chloride (PVC), vinyl
chloride copolymers, and polyvinylidene chloride copolynlers at ambient
temperatures yields solutions of high solids content. Blends of THF and methyl
ethyl ketone are often used for increased solvency in certain polymer compositions.
Applications for THF polymer solutions include PVC top coatings of automotive
upholstery, audio tape coatings of polyurethanelmetal oxides on polyester tape,
polyurethane coatings for fabric finishes, water-vapor barrier film coatings of PVC,
and polyvinylidene chloride copolymers onto cellophane film. Tetrahydrofuran is
an excellent solvent for many inks used for printing on PVC film and on PVC
plastic articles. Polyvinyl chloride pipe welding cements are made by dissolving the
resin in THF solvent. Other adhesive applications include cements for leather,
plastic sheeting, and for molded plastic assemblies. Other uses of THF are as a
chemical intermediate and as a complexing solvent for various inorganic,
organometallic, and organic compounds. These THF complexes are important as
Grignard reagents, catalysts for organic reactions, and in stereo-specific
polymerizations. Tetrahydrofuran is the solvent of choice in many pharmaceutical
reactions and applications. The excellent solvency of THF makes this solvent ideal
for solvent cleaning of polymer manufacturing and processing equipment.
1,3-Dioxolane is used to dissolve a wide spectrum of polymeric materials such as

acrylates, alkyds, cellulosics, epoxies, polycarbonates, polyesters, urethanes, and
vinyl resins. In many cases, 1,3-dioxolane solvent can replace the chlorinated
solvents that were used previously to dissolve many of these polymers. The
excellent solvency of 1,3-dioxolane for polymeric compositions makes this cyclic
ether a valuable component in paint remover formulations. 1,3-Dioxolane is used to
treat polyester fibers for improved dye retention, application of cross-linking agents
to cellulosic fibers, and bonding of acrylonitrile polymers. 1,3-Dioxolane is used in
metal working and electroplating formulations, as a complexing solvent for
organometallic and inorganic salts, and in the preparation of lithium battery
electrolyte solutions. 1,3-Dioxolane is a valuable reactant in the polymerization
reactions to produce polyacetals. Polymerization reactions of dioxolane with itself
or with aldehydes and ethers are catalyzed by a Lewis acid to yield the polyacetal
polymers. The methylene group (CH,) bonded to the two oxygen atoms in
dioxolane is susceptible to radical abstraction of a hydrogen atom and the resultant
dioxolane radical species can be added across various double bond configurations.
TM
MARCEL
DEKKER,
INC.
1,3-Dioxolane is also used as an inhibitor for certain chlorinated solvents. 1,4-

Dioxane, the six-member cyclic diether, is used as an aluminum inhibitor in
chlorinated solvents like 1,1,1-trichloroethane and as a solvent for certain resins
and polymers.
Propylene oxide and 1,2-butylene oxide cyclic ethers find their largest use as
chemical intermediates. Both oxides react readily with dilute amounts of mineral
acids (e.g., hydrochloric acid) to form the chlorohydrin addition product. This
reactivity with acid makes these epoxy solvents valuable acid acceptor-type
stabilizers for several chlorinated solvents. Trace amounts of hydrogen chloride
from chlorinated solvent degradation are immediately neutralized by reaction with
the propylene or 1.2-butylene oxide stabilizer. Reaction of propylene oxide with
an alcohol or phenol in the presence of an acid catalyst yields the monoether of
propylene glycol.
Among the aliphatic diethers, methylal or dimethoxymethane is used as an

intermediate in the manufacture of ion exchange resins. The diether is also used as
an active or latent solvent for a wide variety of gums, resins, and waxes. Methylal
is a valuable extraction solvent for pharmaceutical products and a stable,
inexpensive solvent for Grignard reactions. Methylal is stable under alkaline and
mild acidic conditions. Diethoxymethane (DEM) is offered by Eastman Chemical
Company as a cost-effective replacement solvent for monoglyme (1,2-
dimethoxyethane) and methylal. The DEM diether is stable under alkaline
conditions, but can be cleaved by strong acids. Diethoxymethane can be used as a
chemical intermediate in many organic synthesis reactions. Diethoxymethane is
useful as a solvent in lithium batteries with nonaqueous electrolytes, as a solvent
for polymeric materials, and as a fuel additive. As a chemical intermediate DEM
can act as an ethoxymethylating reagent for alcohols and phenols and serve as a
source for formaldehyde in organic synthesis. DEM reaction with an acid
chloride yields the ethyl ester of the acid, RCOCI + C,H,OCH,OC,H, - -RC
OOC2H5.
The glyme diethers marketed by the Grant Chemical Division, Ferro

Corporation, are used in a wide variety of industrial applications. Most of the
glyme diethers are miscible with water and hydrocarbon-type solvents. The steric
arrangement of the oxygen atoms at regular intervals gives these solvents the
ability to complex many metal cations. The glyme solvents are used in industrial
gas purification processes. Acidic gases like carbon dioxide and hydrogen sulfide
can be removed from natural gas and other gas feed stocks. Hydrogen gas can be
recovered from refinery effluent gas streams by a glyme and isopropanolamine
solvent blend. Catalysts for the polymerization of olefins can be prepared in
glyme ether slurries. The glyme solvents will dissolve any unreacted monomer
for removal from the polymer product. Butyl diglyme is used to extract gold from
hydrochloric acid solutions containing other metals. Treatment of the diglyme
extract with hydrogen or oxalic acid precipitates the ionic gold as gold powder.
TM
MARCEL INC.
DEKKER,
Other industrial applications that use glyme diethers as solvents include textiles,
adhesive and coating formulations, and various pharmaceutical processes. Glymes
are used as solvents in the production of thin photoresist films for semiconductor
circuits in the electronic industry. Glymes are used also as solvent developers for
photo-sensitive polymer films after exposure and transfer of the circuit pattern to
the electronic chip. Butyl diglyme is used in the production of printed circuit
boards. Monoglyme is used in the electrolyte solutions for lithium batteries.
Glymes are used often as the reaction media for various organic reactions, as a
solvent in cleaning formulations, and as a solvent in ink formulations.
GLYCOL ETHERS
Ethylene glycol ethers are a group of chemicals with a wide variety of uses.
Primary uses include solvents in paints, cleaners and inks. Some ethylene glycol
ethers are recommended for use only in industrial applications; others have wide
use in industrial, commercial and consumer applications. Ethylene glycol
monoethyl ether is used in varnish removers, lacquers, and as a solvent for printing
inks, duplicating fluids, and epoxy. Ethylene glycol monobutyl ether is used in
hydraulic fluids, as a coupling agent for water-based coatings, in vinyl and acrylic
paints and varnishes, and as a solvent for varnishes, enamels, spray lacquers, dry
cleaning compounds, textiles, and cosmetics.
Propylene glycol ethers are extremely good solvents having a bifunctional nature
(ether-alcohol). Due to the miscibility with both polar and non-polar substances
they are often used as coupling agents in, for example, water-based paints. Glycol
ether acetates are clear liquids that often have a pleasant, fruity odor. Methyl
proxitol acetate is widely used in the surface coatings industry as a solvent and to
regulate flow and coalescence. The Shell range of propylene glycol ethers and
acetates is sold under the trade name: proxitol. So methyl proxitol and methyl
diproxitol are Shell names for the monomethyl ether of propylene glycol and
dipropylene glycol respectively. Methyl proxitol is sometimes called MP or PM.
Propylene glycol ethers and acetates are mainly used in surface coatings, printing
inks, cleaners, cosmetics and agrochemical formulations. They are also used as
extractants, and as coalescing agents and flow improvers in water-based paints.
Propylene glycol monomethyl ether is primarily used in the manufacture of
lacquers and paints, as an anti-freeze in industrial engines, a tailing agent for inks
used on very high-speed presses, a coupling agent for resins and dyes in water-
based inks, and a solvent for celluloses, acrylics, dyes, inks, and stains. It is also
used in cleaning products such as glass and rug cleaners, carbon and grease
removers, and paint and varnish removers; and in pesticide formulations as a
solvent for applications to crops and animals.
Glycol ethers are general solvents, also known as cellosolves, which are used in the
semiconductor industry. They are also used in surface coatings, such as lacquers,
TM
MARCEL
DEKKER,
INC.
paints, and varnishes; fingernail polishes and removers; dyes; writing inks;
cleaners; and degreasers. Three important glycol ethers are ethylene glycol
monoethyl ether (CAS #110-80-5), ethylene glycol monobutyl ether (CAS #I 11-76-
2), and propylene glycol monomethyl ether (CAS #107-98-2).
Ethylene glycol can form ethers with alkyl groups in the same way as ethyl alcohol:
HOCH,CH,O* *CH, = HOCH,CH,OCH, +

Ethylene glycol monomethyl ether
The following is a list of representative glycols and polyglycols.

HOCH2CH20H
H(OCH2CH2),0H Polyethylene glycol; poly(ethy1ene glycol)
Ethylene glycol monomethyl ether; 2-
CH,0CH2CH20H
methoxyethanol; Methyl CellosolveQD
Ethylene glycol monoethyl ether; 2-ethoxyethanol;
C2H50CH2CH20H
Cellosolve@
Ethylene glycol dimethyl kther; l,2-dimeth~x~ethane;
CH30CH2CH20CH3
monoglyme
C2H50CH2CH20C2H, -Ethylene glycol diethyl ether; 1,2-diethoxyethane
HOCH2CH20CH2CH20H Diethylene glycol
Diethylene glycol monomethyl ether; Methyl
CH30CH2CH20CH2CH20H carbitol@
C2H,0CH2CH,0CH2CH20H Diethylene glycol monoethyl ether; Carbitola
CH3(0CH,CH2)20CH, Diethylene glycol dimethyl ether; diglyme
As solvents, the major uses of glycol ethers include formulation of water- and
solvent-based coatings, as ingredients in household and industrial cleaners, and as
solvents for inks, textile inks and dyes, agricultural pesticides, cosmetics, and
adhesives. The choice of solvent is determined by the desired water-organic
solvency balance, degree of solvent-water coupling capacity, rate of evaporation,
any perceived health hazards, ability to perform product function, and cost.
Concerns over the toxicity problems of certain E-series glycol ethers has
encouraged formulators to switch to the relatively less toxic P-series glycol
ethers. The propylene glycol ether derivatives propylene glycol n-butyl ether -
(PnB) and dipropylene glycol n-butyl ether (DPnB) are alternatives for the
ethylene glycol n-butyl ether (EB) and diethylene glycol n-butyl ether (DB). The 9
PnB and DPnB and corresponding E-series EB and DB glycol ethers have similar 5
evaporation rates, the P-series solvents have good oil solvency, better ability to E
lower surface tension of water, excellent oil-water coupling ability, and lower B
toxicity than the E-series glycol ethers. All of these factors give the P-series
glycol ethers excellent formulation possibilities in both old and new applications.
Z4
5
8-
TM

2
0
sDO
'%
6
DEKKER,
MARCEL INC.
Solvents are an important ingredient of protective coatings along with the resins,
pigments, and additives. Water-based coatings include resin emulsions and
dispersions while solvent-based coatings include enamels, lacquers, and
varnishes. Subdivisions in solvent-based coatings include conventional low-solids
and high-solids coatings. The largest single use for glycol ethers and acetates are
in protective coatings. Ideal properties of these solvents include their
compatibility with water and other organic solvents like alcohols, esters,
aromatics, and naphtha solvents. The glycol ethers are good resin solvents,
provide excellent coalescing with latexes, and good coupling of oil and water
phases, offer a wide range of evaporation rates, provide low surface tension for
improved wetting, and promote adhesion to porous surfaces.
Based on comparative toxicity studies the lower toxicity of the P-series glycol
ethers and acetates has encouraged many of the large paint companies to
reformulate coatings that contain the E-series solvents ethylene glycol methyl ether
(EM), ethylene glycol ethyl ether (EE), ethylene glycol methyl ether acetate
(EMA), and ethylene glycol ethyl ether acetate (EEA).
Restrictions of Volatile Organic Compounds (VOC) emissions has encouraged the
growth of high-solids coatings and water-borne coatings. The P-series glycol ethers
and acetates are excellent candidate solvents for these coating systems.
Water is used in water-borne coatings as a diluent or latent solvent in combination
with an active solvent such as a glycol ether. A latex emulsion (individual resin
particles) gives a continuous protective film after the resin particles coalesce during
the drying process. Successful film formation requires a solvent coalescent aid that
softens the resin particles allowing individual particles to form a continuous film.
The coalescent solvent must remain in the film until after the water evaporates from
the coating. The P-series glycol ethers and acetates and the E-series ethylene glycol
mbutyl ether (EB) and diethylene glycol n-butyl ether (DB) are excellent coalescent
solvents for latex coatings. The type of latex coatings often determine which
coalescent solvents afford the best film properties. Temperature is important in
achieving ideal latex film formation. Each latex resin has a specific minimum film-
formation temperature (MFFT); the proper coalescent solvent will provide a lower
MFFT (at least 40°F) for ideal film formation. The amount of coalescent solvent
necessary will vary and depend on resin type and the solvent's coalescent
efficiency.
The proper water (hydrophilic) and organic (hydrophobic) balance found in many
glycol ether derivatives makes them ideal coalescent solvents. The longer C, alkyl
carbon chain in propylene glycol r~-butyl elher (PnB) affords more organic
solvency as cornpared to the shorter methyl side chain group found in dipropylene
glycol methyl ether (DPM). The PnB solvent is a better choice for a coalescent
solvent than the DPM since the DPM solvent is completely water soluble.
Complete water solubility liniits the all important organic solubility necessary for
good latex film formation.
Water-reducible resins that have been chemically modified to increase their water
TM
DEKKER,
MARCEL INC.
solubility can be completely solubilized in water by the addition of cosolvents such

as alcohols and glycol ethers. A typical water-reducible coating contains
approximately 15% solvent, 55% water, and 15% resin solids. Coupling of the
organic resin and the aqueous phase is an important property of the glycol ethers.
Ethylene glycol n-butyl ether (EB) is used widely as a coupling solvent because of
its superior coupling efficiency and excellent solvency for resins. Practical
alternative cosolvents include dipropylene glycol methyl ether (DPM), blends of
DPM with propylene glycol methyl ether (PM), and propylene glycol n-butyl ether
(PnB) along with blends of these solvents with secondary butyl (sec-BuOH).
Solvent-based coatings can be classified as conventional low-solids and high-solids
( > 60% solids) coatings. Glycol ethers and acetates act as active solvents to
dissolve the film-forming resins and to suspend pigments and additives.
Conventional low-solids coatings contain alkyd, epoxy, nitrocellulose, polyester,
and polyurethane-type resins and find use in coil coating, metal and wood furniture,
automotive coatings, and machinery finishes. These coatings can be classified as
thermoplastic or thermoset. Evaporation of the solvents yields the thermoplastic
film while the thermoset coating is cured by a chemical cross-linking reaction or by
air oxidation in a high temperature oven. Selection of the proper glycol ether
depends on how the coating is cured. Ambient cured coatings often utilize EB, PM,
and DPM glycol ethers and propylene glycol methyl ether acetate (PMA). For
thermally cured coatings the above mentioned glycol ethers as well as blends can be
used. In high temperature coil coating processes the diethylene glycol n-butyl ether
and dipropylene glycol methyl ether acetate (DPMA) are often used as tailing
solvents (these solvents prevent pinholes and other film defects during the last
stages of cure).
Low-cost hydrocarbon solvents are often added to these coatings as diluent
solvents. The excellent solvency of the glycol ethers allow high hydrocarbon
dilution while still maintaining resin solubility. The use of glycol ethers also helps
prevent film defects such as moisture and resin blush, pinholes, orange peel, and
film cracking.
In the electrodeposition coating process electrically charged resin particles are
deposited onto a conductive metal surface from a water dispersion. Glycol ethers
serve as a resin solvent in the coating preparation step and as a coalescent solvent
during film formation. Glycol ethers used in the electrodeposition process include
EB, DB, and PM.
Glycol ether evaporation rates, resin solvency, and surface tension effects on the
coating are all important considerations when selecting the solvent system for 9
automotive primers, enamel base and top coats, in industrial maintenance coatings, 5
and wood coatings. Selection of the proper solvents for resin solvency can be E
greatly simplified by utilizing the Hansen solubility parameter theory. B
Glycol ethers and surfactants couple organic soils into the water phase and keep the Z4
soil suspended in the cleaner. Cleaner formulations can be classified as glass
cleaners, hard surface cleaners, and industrial or heavy duty cleaners. Water is the 5
8-
TM

2
0
sDO
'%
6
DEKKER,
MARCEL INC.
50 Industrial Solvents Hanclbook
principal solvent in the glass and hard surface cleaners while the heavy duty
industrial cleaners contain lower water content. Glycol ethers and various
surfactants provide the oil-water coupling necessary for cleaning soiled surfaces.
The available glycol ethers provide a wide range of evaporation rates and afford
effective reduction of solution surface tensions. Glass cleaners require a fast
evaporating glycol ether to prevent streaking of the giass. Hard surface cleaners
utilize the slower evaporating solvents and the resultant longer residence time that
allows the cleaner to penetrate the soils.
Alcohols, ketones, acetates, and hydrocarbons are used as the principal solvents in
printing inks while the glycol ethers are used as tailing solvents to control
evaporation rates. The glycol ethers PM and DPM are effective in gravure and
flexographic inks while the two acetates PMA and DPMA are useful in silk screen
inks. In vat dyeing of textiles glycol ethers help the dyes to penetrate and saturate
the fabric as well as serve as coupling aids. Glycol ethers often used in vat dyeing
include DPM, TPM, PPh, DB, and DM. The surface tension reduction from the
glycol ether allows deep penetration of the dyes into the fabrics during textile
printing of cellulose acetate and polyester fabrics. Glycol ethers like DPM, DM,
and EPh are used in floor polish formulations. The coalescing action of the glycol
ethers allows the latex emulsion to dry into a smooth continuous film. The resultant
film has high gloss, resistance to detergents, good adhesion and is mar resistant.
Agricultural pesticides are often formulated with blends of glycol ethers and
surfactants that wet and couple the active ingredients into the water phase. Certain
glycol ethers are acceptable as inert ingredients in pesticide formulations. Exact
information on using glycol ethers in agricultural products should be obtained from
the solvent producer. Cosmetic and personal care products use glycol ethers as
solvents and coupling aids. Dipropylcne glycol methyl ether is often used in
combination with propylene glycol in cosmetics. Ethylene glycol phenyl ether at a
1.0% level acts as a preservative in personal care products.
Properties
All glycol ethers have a low vapor pressure and a high potential for dermal
absorption. They are nonflammable. Ethylene glycol monoethyl ether is a colorless
liquid with a sweet, mild odor and slightly bitter taste. It is miscible in all
proportions of acetone, benzene, carbon tetrachloride, ethyl ether, methanol, and
water. It dissolves many oils, resins, and waxes. Ethylene glycol monobutyl ether
is a colorless liquid with a mild, rancid, ether-like odor. It is soluble in most
organic solvents and mineral oil. It mixes with acetone, benzene, carbon
tetrachloride, ethyl ether, n-heptane and water; it is miscible with many ketones,
ethers, alcohols, aromatic paraffin, and halogenated hydrocarbons. A synonym for
ethylene glycol monobutyl ether is ethylene glycol mono-n-butyl ether.
Propylene glycol monomethyl ether is a colorless liquid with a sweet ether-like

odor and bitter taste. It is soluble in water, ether, acetone, and benzene. A
synonym for propylene glycol monomethyl ether is 1-methyl-2-hydroxypropane.
TM
MARCEL DEKKER, INC.

Inhaling glycol ethers can result in dermatitis with erythema, edema, and weeping;
hyperpigmentation; and photosensitization. Exposure to ethylene glycol monoethyl
ether can cause depression of the central nervous system, resulting in headaches,
drowsiness, weakness, slurred speech, tremor, and blurred vision. Ethylene glycol
monobutyl ether is regarded as the most toxic glycol ether used as a solvent.
Exposure can result in bone marrow damage, headaches, drowsiness, weakness,
slurred speech, tremor, and blurred vision. Exposure to vapors can result in
respiratory, nose, throat, and eye irritation. Exposure to propylene glycol
monomethyl ether can cause eye, nose, and throat irritation. High levels become
objectionable because of the chemical's odor.
HALOGENATEDHYDROCARBONS
Halogenated hydrocarbons are solvents formed by reacting fluorine, chlorine,

bromine, or iodine with a hydrocarbon molecule. The largest share of the
commercially important halogenated hydrocarbon solvents are aliphatic in nature.
The chlorinated solvents make up the largest portion of the aliphatic solvents. The
fluorinated solvents are the second largest segment in commercial use, while the
bromine and iodine derivatives have a very minor use in industry.
Chlorinated solvents are colorless, volatile liquids that exhibit high solvency for
greases, oils, waxes, resins, and polymers. Although cleaning processes are the
largest single use of the chlorinated solvents other uses include adhesives, the
electronic industry, as extraction solvents, paint and coating solvents,
pharmaceuticals, textile processing, and as reaction media. The solvents most often
used in these applications include methylene chloride, 1,1,1-trichloroethane,
trichloroethylene, and perchloroethylene. The largest use of perchloroethylene
("perc") is as a dry-cleaning fluid. Solvents like 1.2-dichloroethane, 1,l-
dichloroethane, chloroform, and carbon tetrachloride are feed stocks for the
manufacturing of other chlorinated and fluorinated solvents.
Environmental pressures like the stratospheric ozone depletion issue have forced the
phasing out of certain halogenated solvents. For years, 1,1,1-trichloroethane
(methyl chloroform) solvent has been a widely-used cold cleaning solvent and a
popular vapor degreasing solvent. The other solvent being removed from the
cleaning process because of the ozone depletion issue is 1,1,2-
trichlorotrifluoroethane (CFC 113).
Commercial uses of chlorinated solvents cause serious stresses on the stability of
the solvent. These stresses include heat, hydrolysis (reaction with water), metal 9
contact, and air induced oxidation. The addition of selected organic inhibitors 5
E
(stabilizers) to the solvent helps ensure solvent stability in the most stressful
applications. The organic inhibitors used in proprietary chlorinated solvents include B
antioxidants, acid acceptors, and metal stabilizers. The unsaturated solvents like
trichloroethylene and perch loroethylene require amine or phenolic-type
Z4
antioxidants to minimize the potential oxidative degradation. Acid acceptors are low 5
8-
TM

2
0
sDO
- - '%
6
DEKKER,
MARCEL INC.
molecular weight epoxy compounds that neutralize or react with trace amounts of
hydrogen chloride (an acid) that may be formed in a chlorinated solvent
application. Metal stabilizers are organic compounds that contain certain functional
groups capable of reacting with trace amounts of the metal chloride formed in the
solvent-metal reaction.
Most of the chlorinated solvents are reactive with metals, are susceptible to
hydrolysis, and undergo oxidation degradation. Perchloroethylene is the only
commercially used solvent that does not normally require a metal inhibitor.
However, atnine or phenolic-type inhibitors are added as antioxidants. An acid
acceptor may be added to perchloroethylene for very stressful applications to
remove trace amounts of hydrogen chloride and to protect against metal
degradation in high temperature application uses. Trichloroethylene and 1,1,1-
trichloroethane both require acid acceptors and metal inhibitors. An antioxidant is
always added to the trichloroethylene formulations. The solvent application and
type of possible metal contact will determine which inhibited grade of these two
solvents is needed. Aluminum metal contact with improperly inhibited 1,1,1-
trichloroethane or trichloroethylene can cause catastrophic metal-solvent reactions
with the resultant release of enormous amounts of gaseous hydrogen chloride. The
gaseous hydrogen chloride can cause extensive equipment corrosion and require
employee evacuation from the work site. Use of properly stabilized grades of the
solvents will allow the safe use of the solvent with aluminum metal. The presence
of large amounts of finely divided aluminum or aluminum chips is a reason
however for concern of possible metal reaction. Proper inhibition of the solvents
toward aluminum will allow safe use of the solvents with other less reactive metals.
The presence of excessive amounts of water in the form of a separate water phase
will in many cases increase solvent-induced corrosion of metals. The presence of
low molecular weight alcohols added to l , l , l - T r i can cause increased metal
corrosion. The presence of aromatic hydrocarbons (e.g., toluene or xylene) in
methylene chloride formulations in contact with aluminum can cause catastrophic
release of gaseous hydrogen chloride. The trace amounts of aluminum chloride
produced by the normally very slow aluminum-solvent reaction acts as a catalyst
for the Friedel-Crafts reaction between the aromatic hydrocarbon and methylene
chloride. The resultant reaction produces hydrogen chloride which reacts with
aluminum to give more aluminum chloride and resulting in a runaway autocatalytic
reaction. The addition of an acid acceptor or proper metal stabilizer will greatly
reduce the reactivity of aluminum with methylene chloride-containing aromatic
hydrocarbon diluents. Carbon tetrachloride and 1,2-dichloroethane are very
reactive with aluminum. These normally uninhibited feed stock solvents should
not contact any aluminum metal. Carbon tetrachloride can be inhibited against
aluminum attack with the same types of stabilizers used with l , l , 1-Tri. 1,2-
Dichloroethane reacts with magnesium to give a Grignard reaction-type product.
Thermal stability of the chlorinated solvents is excellent at their respective boiling
points. However, the solvent vapors can be thermally decomposed to produce
TM
DEKKER,
MARCEL INC.
gaseous hydrogen chloride in high temperature environments (e.g., hot metal

surfaces in ovens and gas fired space heaters). The amount of hydrogen chloride is
neither excessive nor dangerous, but can cause metal corrosion. A welding
operation in the presence of chlorinated solvent vapors can cause thermal
degradation with the formation of oxidation products and gaseous hydrogen
chloride. Fluorinated hydrocarbons are also susceptible to thermal breakdown and
production of corrosive gaseous hydrogen fluoride.
Polychloro hydrocarbons can react with certain amines to produce an ammonium
salt of the amine, a chloride ion, and an organic free radical species from the
chlorinated reactant:
Methylene chloride, chloroform, carbon tetrachloride, and 1,2-dichloroethane

exhibit some reactivity with amines like piperidine. The most noticeable sign of
reaction is the precipitation of the amine hydrochloride salt from the solvent.
Trichloroethylene and perchloroethylene are susceptible to oxidative breakdown
which is accelerated by high temperatures and exposure to ultraviolet (UV) light.
The addition of antioxidants eliminates the potential of oxidative degradation.
Hydrolysis reactions of the chlorinated solvents with water occur at a very slow but
finite rate. The biggest problem is the presence of a separate water phase in contact
with a metal surface and the solvent phase. The presence of the water phase
encourages removal of small amounts of metal chloride salts formed by any metal-
solvent reaction. The initial reaction sites are often sealed by the extremely small
amounts of insoluble metal salt deposits. Removal of these insoluble and protective
salt deposits into the water phase encourages further metal-solvent corrosion. A
pitting-type of corrosion is often seen at the boundary line between the water and
solvent phases.
1,1,2-Trichlorotrifluoroethane(CFC 113) is generally a stable molecule not prone
to the reactivity that is often shown by the chlorinated hydrocarbons. The solvent
blends that contain the fluorinated hydrocarbon and an alcohol display some metal
reactivity which is inhibited by adding nitromethane as a stabilizer (e.g., the Freon
blends discussed in Table 14.5). The vapors of a fluorinated hydrocarbon undergo
thermal degradation in a high temperature oven or flame. The bromine and iodine
derivatives show increased metal reactivity. The rate of metal reactivity for the
halogenated hydrocarbons in increasing order is: fluoro < < chloro < < bromo
< < iodo. Many of the iodohydrocarbons show a slight brown discoloration due 9
to the liberation of minute amounts of iodine from the compound. 5
Each halogenated solvent has distinct physical and chemical properties as well as
E
specific toxicology characteristics. Specific toxicology information on a halogenated B
solvent is available in the solvent's MSDS and from the solvent producer. The most
common health and overexposyre hazard of these solvents is due to vapor
Z4
inhalation. Overexposure may produce an anesthetic effect and depression of the 5
8-
TM

2
0
sDO
- - - '%
6
DEKKER,
MARCEL INC.
central nervous system, and is characterized by dizziness, loss of coordination, and

the feeling of being lightheaded. A rapid reversal of the anesthetic effects occurs
when the individual moves out of the area of exposure. Entrance into an area of
high vapor concentrations of any organic solvent (e.g., an unventilated storage
tank) can quickly lead to unconsciousness and death through respiratory failure.
Specific safe tank entry instructions are available from the solvent producers. Since
the halogenated solvents are heavier than air their vapors will concentrate in low
areas such as pits and basements. Detection equipment is available to measure
vapor concentrations of solvent. Other routes of solvent overexposure include
ingestion, skin, and eye contact. Use the proper chemical gloves as recommended
in the MSDS.
The discussions below provide profiles on some of the more widely used
chlorinated hydrocarbons.
Methylene Chloride
Methylene chloride is used as a solvent, especially where high volatility is required.

It is a good solvent for oils, fats, waxes, resins, bitumen, rubber and cellulose
acetate and is a useful paint stripper and degreaser. It is used in paint removers, in
propellant mixtures for aerosol containers, as a solvent for plastics, as a degreasing
agent, as an extracting agent in the pharmaceutical industry, and as a blowing agent
in polyurethane foams. Its solvent property is sometimes increased by mixing with
methanol, petroleum naphtha, or tetrachloroethylene.
Studies indicate that there is suggestive, but not absolute, evidence that methylene
chloride is a human carcinogen. Long-term respiratory exposure in excess of 25 parts
per million (ppm) is reported to be associated with an increased risk of cancer of the
bile duct and brain. Short term (acute) airborne exposures to high concentratidns over
125 ppm may cause mental confusion, light-headedness, nausea, vomiting, and
headache. Continued exposure may also cause eye and respiratory tract irritation.
Exposure to methylene chloride may make symptoms of angina (chest pain) worse.
Skin exposure to liquid methylene chloride may cause irritation. Liquid methylene
chloride placed on the skin may cause chemical burns. Activities where exposure to
methylene chloride is possible are in using paint strippers, working in laboratories,
and parts degreasing. These areas sho~lldbe initially and periodically assessed for
exposures.
Methylene chloride is a widely used chemical solvent with a diverse number of
applications. It was introduced as a replacement for more flammable solvents over 60
years ago. Methylene chloride is commonly used in paint removers and industrial
adhesive formulations. It also is employed in the production of flexible urethane
foams, pharmaceutical products, and plastics, as a cleaning agent for fabricated metal
parts, and as an extraction solvent.
Methylene chloride is a member of a family of saturated aliphatic halogenated
compounds. It is a colorless, volatile liquid, completely miscible with a variety of
other solvents. It is produced in the United States by The Dow Chemical Company
TM
DEKKER,
MARCEL INC.
and Vulcan Materials Company. Total U.S. demand for the chemical in 1996 was
estimated at about 285 million pounds (129,000 metric tons) of which about 20
million pounds (9000 metric tons) was imported. About 130 million pounds (59,000
metric tons) were exported. It is a highly desirable chemical for many applications
because of the following characteristics:
Its aggressive solvency makes it an ideal paint remover that does not harm
wood in the removal process.
It has no flash point under normal use conditions and can be used to
reduce the flammability of other substances, decreasing the chance of in-
plant fire or explosion.
It is an effective vapor pressure depressant in aerosols.
It does not contribute significantly to atmospheric pollution through the

formation of smog, to the depletion of the stratospheric ozone layer, or to
global warming.
Methylene chloride is the active ingredient in many formulations of paint removers

including industrial paint and commercial furniture strippers, home paint removers,
and products used for aircraft maintenance. The chemical has a unique ability to
penetrate, blister, and lift a wide variety of paint coatings. Formulations of the
chemical are used extensively in both flow-over and immersion (dip) tanks in
furniture refinishing operations. For the maintenance of military and commercial
aircraft, a methylene chloride-based product is often required to inspect the surface
for damage.
Since the mid- 1990s methylene chloride has replaced 1,1,1-trichloroethane in
nonflammable adhesive formulations for industrial applications, including
fabrication of upholstery foam. It provides adhesive formulations with strong,
instant bonding characteristics and efficacy under extremes of temperature and
humidity. In foam applications, use of methylene chloride eliminates the possibility
of hard seams and allows for ready compliance with flammability requirements for
upholstered furniture.
Methylene chloride is used in aerosols as a strong solvent, a flammability
suppressant, vapor pressure depressant, and viscosity thinner. Current aerosol uses
of methylene chloride include spray paints and lubricants.
Methylene chloride is a leading auxiliary blowing agent used in the production of
slabstock flexible polyurethane foams for the furniture and bedding industries.
Evaporation of the solvent during production of the urethane polymer expands the
cells of the foam, reducing its density without making it stiff or rigid. The
auxiliary blowing agent also helps to control the reaction temperature, which
otherwise could get sufficiently high to burn or scorch the foam interior.
TM
MARCEL DEKKER, INC.

Methylene chloride is used as an effective reaction and recrystallization solvent in

the extraction of several pharmaceutical compounds and in the production of many
antibiotics and vitamins. The chemical also has been used as a carrier for
pharmaceutical tablet coatings. In these applications, essentially no methylene
chloride is left in the coating of the tablet. Residue tolerances have been
established by the Food and Drug Administration (FDA) for this particular use.
Methylene chloride is employed in the manufacture of polycarbonate resin used for
the production of thermoplastics. It is used as a solvent in the production of
cellulose triacetate which serves as a base for photographic film. Other applications
include its use in the solvent welding of plastic parts, and as a releasing agent to
prevent the manufactured part from permanently bonding to the mold.
It is often necessary to remove grease, oil, or similar substances used as lubricants
or temporary protective coatings during metal fabrication. Methylene chloride is
used extensively for this purpose, both for cold (room temperature) cleaning and
vapor degreasing of metal parts.
Methylene chloride is used as an extractant in the recovery and purification of a
wide variety of materials including oils, fats, and waxes. The chemical is used for
the decaffeination of coffee and tea, oleoresin extraction from a variety of spices,
and for the extraction of hops. As with tablet coatings, little or none of the
chemical remains in the finished product.
Methylene chloride, also known as dichloromethane, evaporates easily, but does
not burn easily. It does not appear to occur naturally in the environment. It is made
from methane gas or wood alcohol. As noted it is widely used as an industrial
solvent and as a paint stripper as well as in the manufacture of photographic film.
The chemical may be found in a variety of household products including spray
paints, automotive cleaners and some pesticide formulations.
Most of the methylene chloride released to the environment results from its use as
an end product by various industries and the use of aerosol products and paint
removers in the home. Because methylene chloride evaporates easily, the greatest
potential for exposure occurs when people breathe air contaminated as a result of
the use of consumer products, such as paint strippers, that contain methylene
chloride. Exposure can also result from direct contact of the liquid material with the
skin. The highest and most frequent exposures to methylene chloride usually occur
in workplaces where the chemical is made or used. The following summarizes
pertinent information on methylene chloride.
Chemical Formula CH,CI,

Molecular Formula 84.9
CAS Number 75-09-2
Flammable Limits (@ 25°C) 147%-22% solvent in air
OSHA PEL
TM
MARCEL DEKKER, INC.

8-hour TWA
15-minute STEL 125 ppm
ACGIH TLV
8-hour TWA
15-minute STEL
IARC Classification
CERCLA Reportable Quantity (RQ) lo00 pounds

Maximum Contaminant Level 5 microgramstliter (5 parts per
(Drinking Water) billion)
RCRA Hazardous Waste Number U 080
DOT Hazard Classification 6.1 (packing g o u p 111)
DOT ID Number UN1593
Trichloroethylene
Trichloroethylene is used widely by industry as a metal degreaser. It is especially

valuable because of its cleaning properties, low flammability, and lack of a
measurable flash point. Trichloroethylene also is used as a chemical process
intermediate in fluorochemical and polyvinyl chloride (PVC) production. It has
been used worldwide for more than 70 years. It is a colorless, volatile liquid, and is
an unsaturated aliphatic halogenated hydrocarbon. In the United States, it is
produced by The Dow Chemical Company and PPG Industries, Inc. In 1998, U.S.
demand was about 171 million pounds (77,700 metric tons) of which about 15
million pounds (6,800 metric tons) were imported. About 84 million pounds
(38,000 metric tons) were exported. The use of trichloroethylene in 1999 can be
broken down into the following categories:
chemical intermediate ( -54%)
metal cleaning and degreasing ( 4 2 % )
miscellaneous ( -4 %)
High-purity grades of trichloroethylene are used as a feedstock in the synthesis of

the refrigerant hydrofluorocarbon 134a. In this process', the trichloroethylene
molecule is destroyed to form the new fluorinated compound. It also is used in the
production of such chlorinated end products as polychlorinated aliphatics and
flame-retardant chemicals. In polyvinyl chloride (PVC) manufacture,
trichloroethylene is used as a molecular weight control agent.
Among the properties that have contributed to trichloroethylene's wide acceptance
as a metal cleaner and degreaser are the following:
TM
MARCEL
DEKKER,
INC.
Industrial Solveuts Handbook
high solvency
low flammability
non-corrosiveness
high stability
low specific heat
low boiling point
low latent heat of vaporization
Trichloroethylene's advantages for metal cleaning include the ability to degrease

more thoroughly and several times faster than alkaline cleaners, and its
compatibility with smaller equipment that consumes less energy. Trichloroethylene
is an important solvent for degreasing aluminum and for cleaning sheet and strip
steel prior to galvanizing. Trichloroethylene also is used for cleaning liquid oxygen
and hydrogen tanks. Commercial trichloroethylene formulations include a stabilizer
system to help prevent solvent breakdown caused by contaminants, such as acids,
metal chips, and fines, and exposure to oxygen, light, and heat.
Trichloroethylene is also used as a solvent in some nonflammable adhesive and
aerosol formulations, and as a low temperature heat-transfer medium. Other
applications of trichloroethylene include its use as a solvent in the metal processing,
electronics, printing, pulp and paper, and textile industries.
Acute (short-term) overexposure to trichloroethylene vapor can cause central
nervous system effects (e.g., light-headedness, drowsiness, headache, giddiness)
which may lead to unconsciousness or prove fatal in extreme circumstances. Also,
at very high exposure levels, trichloroethylene can sensitize the heart to the effects
of adrenaline and similar agents, which may lead to sudden cardiac arrest. In
addition, trichloroethylene may irritate the respiratory tract at high vapor
concentrations. Repeated or lengthy contact with the chemical in liquid form can
cause irritation of the skin and eyes. Chronic (repeated) overexposure, well in
excess of recommended occupational limits, has been associated with damage to the
liver and kidneys, although this is less well documented in humans than in animals.
The carcinogenic potential of trichloroethylene in laboratory animals and in humans
(through epidemiology studies) has been well studied. It has been shown to cause
an increased incidence of liver and lung tumors in certain laboratory mice, and
small increases in kidney tumors in male rats in some studies. Because of species
differences in metabolism of trichloroethylene, the relevance of these results to
humans is uncertain.
The Clean Air Act Amendments of 1990 significantly revised the provisions of
Section 112 relating to the regulation of emissions of hazardous air pollutants.
TM
MARCEL
DEKKER,
INC.
Under the new law, EPA is required to develop national emission standards based
on maximum achievable control technology, or MACT, for sources of
trichloroethylene and 188 other substances within 10 years. The revised Section
112 also requires EPA to review the need for additional control of regulated
sources within 8 years of the implementation of the MACT standard.
Trichloroethylene also is regulated as an air toxic in most states. A standard for
halogenated solvent cleaning (degreasing) with trichloroethylene and the other
chlorinated solvents was promulgated in December 1994 and became effective for
existing sources in December 1997. As a result, all degreasing sources using
trichloroethylene will be required to obtain an operating permit from the state
regulatory agency. Permitting for small degreasing sources may be deferred until
2004. EPA has determined that trichloroethylene is an acceptable alternative in
many applications for methyl chloroform and chlorofluorocarbon (CFC) 113,
solvents whose production has been phased out because of their potential to deplete
stratospheric ozone. Trichloroethylene is controlled as a volatile organic compound
(VOC) under state regulations implementing the national ambient air quality
standard for ozone (smog). The available information suggests, however, that
trichloroethylene exhibits relatively low photochemical reactivity when compared to
many other hydrocarbon solvents.
EPA has also established national drinking water regulations setting a maximum
contaminant level of 5 micrograms per liter (pgil), equal to 5 parts per billion
(ppb), for trichloroethylene. The maximum contaminant level goal (MCLG) for
trichloroethylene is zero. EPA has indicated that "[tlhe establishment of an MCLG
at zero does not imply that actual harm necessarily occurs to humans at a level
somewhat above zero, but rather that zero is an aspirational goal, which includes a
margin of safety, within the context of the Safe Drinking Water Act." Various
states also may have drinking water regulations that apply to trichloroethylene. For
various industry categories, EPA has established effluent limitation guidelines,
which may contain effluent limitations for trichloroethylene. EPA also has
published ambient water quality criteria for trichloroethylene for use by states in
developing water quality standards.
Trichloroethylene waste is considered hazardous under the federal Resource
Conservation and Recovery Act (RCRA) and many state laws. The waste must be
stored, transported, and disposed of in accordance with applicable RCRA and state
requirements. The reportable quantity (RQ) for releases of trichloroethylene under
the Comprehensive Environmental Response, Compensation, and Liability Act
(Superfund) is 100 pounds. It is one of several hundred chemicals subject to
material safety data sheet (MSDS), inventory, and release reporting under the
Emergency Planning and Community Right-to-Know Act (Title I11 of the 1986
Superfund Amendments and Reauthorization Act, or SARA).
In 1989, the U.S. Occupational Safety and Health Administration (OSHA) lowered
the permissible exposure limit (PEL) for trichloroethylene from 100 ppm to 50 ppm
for an 8-hour time-weighted average (TWA). OSHA also established a short-term
TM
MARCEL DEKKER, INC.

(15-minute) exposure limit, or STEL, of 200 ppm. These actions were overturned
by a federal court in 1993, and the PELS reverted to the former limits of 100 ppm
@-hour TWA), 200 ppm (ceiling), and 300 ppm (peak). Several states that adopted
the lower 1989 limits, however, have not adopted the higher limit. ACGIH
currently recommends threshold limit values (TLVs) of 50 ppm for an 8-hour TWA
and 100 ppm for a 15-minute STEL. Trichloroethylene is subject to the OSHA
Hazard Communication Standard, which imposes labeling, material safety data
sheet (MSDS), and other requirements on employers and their suppliers.
The following is pertinent information on trichloroethylene.
Chemical Formula C2HC13
Molecular Weight 131.4

CAS Number 790 1-6
Boiling Point 189°F (87°C)
Weight per Gallon (077°F) 12.1 1 pounds
Flash Point none
Flammable Limits @77"F (% solvent in air, by volume)
Lower Limit 8.0
Upper Limit 9.2 (vapor saturation point)
Flammable Limits @212"F (70 solvent in air, by volume)
Lower Limit
Upper Limit
Solubility @77"F (grams1100 grams)
Trichloroethylene in water
Water in trichloroethylene
OSHA PEL (see discussion in text)
8hr TWA 100 pprn
Ceiling 200 ppm
Peak 300 ppm
ACGIH TLV
8hr TWA
15min STEL
Cancer Classification
ACGIH A5
IARC 2A
NTP "reasonably anticipated"
CERCLA Reportable Quantity (RQ) 100 pounds
Maximum Contaminant Level (MCL) 5 ppb (5 microgramsiliter)
RCRA Hazardous Waste No. U 228
Department of Transportation
Hazard Classification 6.1 (packing group 111)
ID Number U N 1710
TM
DEKKER,
MARCEL INC.
Perchloroethylene
Perchloroethylene is a member of a family of aliphatic halogenated hydrocarbons.

It is a colorless, volatile liquid that is essentially nonflammable and has no
measurable flash point. In the United States, perchloroethylene is manufactured by
the Dow Chemical Company, PPG Industries, Inc., and Vulcan Materials
Company. Total U.S. demand for the chemical in 1998 was estimated to be about
344 million pounds (156,000 metric tons), of which about 30 million pounds
(13,600 metric tons) were imported. An additional 40 million pounds (18,100
metric tons) were exported. It is the primary solvent used in commercial and
industrial dry cleaning. Since being introduced to the dry cleaning industry in the
late 1930s, it has replaced most other solvents because of its relatively low toxicity
and nonflammability. Its other major uses are as a metal cleaning and degreasing
solvent, as a solvent in automotive aerosols, and as a chemical intermediate in the
production of several fluorinated compounds. For 1998, the use of
perchloroethylene can be broken down into the following categories:
dry cleaningltextile processing ( -25 %)
automotive aerosols (-10%)
metal cleaningldegreasing ( -10%)
Perchloroethylene is used as a basic raw material in the manufacture of

hydrofluorocarbon (HFC) 134a, a popular alternative to chlorofluorocarbon (CFC)
refrigerants. It also is used in the synthesis of hydrochlorofluorocarbon (HCFC)
123 and 124 and HFC 125.
Perchloroethylene is used by more than 80 percent of commercial dry cleaners, as
well as some industrial cleaning establishments. It had replaced other synthetic
solvents, such as carbon tetrachloride, by the late 1940s or early 1950s. A gradual
shift from petroleum derivatives to perchloroethylene began in the late 1940s. This
shift in solvents increased in the 1950s and early 1960s. However, in the period
before 1960, petroleum derivatives were still the dominant solvents.
In addition to its nonflammability and relatively low toxicity, the popularity of
perchloroethylene in the dry cleaning industry can be attributed to the following
properties:
safe to use on all common textiles, fibers, and dyes
effective at removing fats, oils, and greases
free of residual odor
TM
MARCEL DEKKER, INC.

chemically stable under all common use conditions
noncorrosive to the metals and other materials used in dry cleaning

machinery
easily removed from clothes
energy and cost efficient (can be easily distilled and reused)
The textile industry uses perchloroethylene as a spotting agent for the removal of
spinning oils and lubricants. It also is used in wool scouring and as a solvent carrier
in dyes and water repellents.
Perchloroethylene has replaced 1,1,1-trichloroethane in aerosol formulations for the
automotive aftermarket, particularly for brake cleaning. These formulations provide
auto repair shops with highly effective, nonflammable products.
Many industries, including aerospace, appliance, and automotive manufacturers,
use perchloroethylene for vapor degreasing metal parts during various production
stages. Its high boiling point and resultant longer cleaning cycle are advantageous
in removing "difficult" soils such as waxes with high melting points. The ability of
the chemical to remove water during vapor degreasing is useful to jewelry
manufacturers and other metal finishers. Perchloroethylene's nonflammability and
low vapor pressure make it an effective cold (room temperature) metal cleaner,
when used in compliance with applicable regulatory requirements. Its low vapor
pressure contributes to reduced emissions from cold cleaning operations where it is
employed.
Perchloroethylene is used as an insulating fluid in some electrical transformers as a
substitute for polychlorinated biphenyls (PCBs). Relatively small quantities of
perchloroethylene are used in printing inks, aerosol specialty products, adhesive
formulations, paper coatings, and silicones. In addition, perchloroethylene is a
component of chemical maskant formulations used to protect surfaces from
chemical etchants used in the aerospace and other industries.
Under certain conditions, overexposure to perchloroethylene may cause central
nervous system (CNS) and liver effects. Prolonged exposure to concentrations of
200 parts per million (ppm) or more has been associated with dizziness, confusion,
headache, nausea, and irritation of the eyes and mucous tissue. At higher exposures
( > 600 ppm) these symptoms are intensified. Prolonged exposure to extremely high
levels ( > 1,500 ppm) may lead to unconsciousness due to anesthesia and, in
extreme cases, death from respiratory depression. Changes in the liver and kidney
of laboratory animals have been observed following prolonged exposure to
concentrations of 200 ppm or more. In humans, reversible effects in liver function
have been noted in persons exposed to high levels of perchloroethylene vapor for
extended periods of time. No effects on the liver or kidney were seen in human
volunteers exposed to up to 150 ppm, 7.5 hours per day, 5 days per week for 11
TM
MARCEL DEKKER, INC.

weeks. For occupational exposures, there are reports of mild alterations of liver or
kidney function in a few studies, but other studies have found no detectable effect.
The following summarizes pertinent information on perchloroethylene.
Chemical Formula C2C14
Molecular Weight 165.9
CAS Number 127184
Boiling Point 250 OF
Weight per Gallon ( a 6 0 OF) 13.6 pounds
Flash Point none
Flammable Limits none
Solubility
perc in water 150 ppm
water in perc 105 ppm
OSHA PEL
8hr TWA
Ceiling
Peak
ACGIH TLV
8hr TWA 25 PPm
15min STEL 100 ppm
Cancer Classification
ACGIH A3 ("animal carcinogen")
IARC 2A ("probably carcinogenic to
humans ")
NTP "reasonably anticipated to be a human
carcinogen"
CERCLA Reportable Quantity (RQ) 100 pounds
Maximum Contaminant Level (MCL) 5 microgramslliter (5 ppb)
RCRA Hazardous Waste No. u 210
DOT Hazard Classification 6.1 (packing group 111)
DOT ID No. UN 1897
Methyl Chloroform
Methyl chloroform is a versitile, all purpose solvent, popular with industry because
of its powerful cleaning properties, low flammability, and low relative toxicity. It
was introduced in the mid 1950s as a cold cleaning solvent substitute for carbon
tetrachloride. Today, methyl chloroform is used primarily for vapor degreasing and
cold cleaning of fabricated metal parts and other materials. The chemical also is
used in fluoropolymer synthesis, as a solvent in adhesive and aerosol formulations,
for the production of certain coatings and inks, for a variety of textile applications,
and for dry cleaning leather and suede garments. Methyl chloroform is a member
of a family of saturated aliphatic halogenated hydrocarbons. The colorless, volatile
liquid is produced in the United States by Dow Chemical U.S.A., PPG Industries,
TM
MARCEL DEKKER, INC.

Inc., and Vulcan Materials Company. Total U.S. demand for the solvent in 1989
was 308,000 metric tons (680 million pounds) of which a small percentage was
imported.
Permissible levels of methyl chloroform in the workplace have been established in
several countries. In the United States, OSHA limits worker exposure to the
chemical to a time-weighted average concentration of 350 parts per million (ppni)
in the workplace air in any 8-hour work shift of a 40-hour week. This 350-ppm
standard is well above the concentration at which presence of the chemical is
noticeable (odor threshold = 100 ppm), and at or below EPA's estimated no-
observed-effect level for short-term exposure of humans (350 to 500 ppm). OSHA
also has established a short-term exposure limit, or STEL, of 450 ppm for any 15-
minute period. No adverse health effects are likely to arise from the industrial use
of methyl chloroform when i t is handled in accordance with the manufacturer's
instructions.
Among the properties that have contributed to the widespread use of methyl
chloroform as an industrial solvent are the following:
low toxicity
high solvency
low flammability
relatively high stability
low boiling point
non-photochemical reactivity (does not form ozone in the lower

atmosphere)
low solubility in water
ability to be recycled
In addition, all commercial formulations of methyl chloroform are stabilized to

retard or prevent solvent breakdown caused by contaminants, such as acids,
alkalies, ~netalchips, and fines, and overexposure to oxygen, light, and heat. The
stabilizers also help to protect the surface being cleaned. In 1989 industrial use of
methyl chloroform could be summarized as follows:
metal degreasing ( -32%)
cold cleaning ( -19%)
aerosols ( -1 1 %)
TM
MARCEL DEKKER, INC.

adhesives ( -9%)
electronics ( -7 %)
coatings and inks ( -6 %)
textiles ( -3 %)
Metal vapor degreasing is an important process in industrial manufacture, used to

remove oils and oil-borne soils (i.e., chips, metal fines, and fluxes) from objects
that have been stamped, machined, welded, soldered, molded, or diecast. Vapor
degreased parts vary from tiny transistors to aircraft and spacecraft assemblies.
Methyl chloroform is an excellent solvent for the cold (room temperature) cleaning
of a wide variety of manufacturing equipment and products including yarns,
threads, finished cloth, reinforced fiberglass, plastics, and common and exotic
metals. The solvent removes most greases, oils, lubricants, waxes, adhesives, inks,
fluxes, paints, stamping and drawing compounds, tars, and other soils.
As an aerosol solvent, methyl chloroform can be used in conjunction with either
carbon dioxide or hydrocarbon propellants to reduce the flammability of the aerosol
package. The solvent can solubilize many of the active ingredients in aerosol
formulations, improving the spray characteristics and reducing valve clogging.
The main reasons for the use of methyl chloroform in formulations for urethane and
neoprenelphenolic contact adhesives, mastics, sealants, and natural rubber tire
repair cements are its ability to substantially reduce flammability, its non-
photochemical reactivity, and the favorable characteristics of the resulting adhesive
formulation.
The main applications of methyl chloroform in the electronics industry are in circuit
board fabrication, where it is used to develop dry film photoresist, and in the
semiconductor industry where it is used for secondary cleaning.
Methyl chloroform serves as a raw material for the manufacture of polyvinylidene
fluoride fluoropolymer. It also can be used as a raw material for the production of
certain hydrochlorofluorocarbons having relatively short atmospheric residence
times.
In the coatings manufacturing industry, methyl chloroform is used as a solvent in
the formulation of protective and decorative coatings and as a thinner to reduce the
viscosity of high-solid content coatings for spray application. The chemical also can
be used in the production of rotogravure and flexographic inks. In addition to the
above uses, methyl chloroform is used to dry clean leather and suede products and
to clean motion picture film.
TM
MARCEL INC.
DEKKER,
The health effects of methyl chloroform are well characterized after many years of
industrial use. The primary effects of acute overexposure to the chemical are to the
central nervous system (e.g., light-headedness, drowsiness, headache). Lethal
effects of excessive concentrations (at 10,000 ppm) of the chemical have been
reported after accidental exposure or abuse. In these cases, death resulted from
respiratory and cardiac failure caused by depression of the central nervous system.
Cardiac sensitization also may have contributed. Prolonged exposure (15 minutes o r
more) to high concentrations (1000 to 2000 ppm) of the solvent in the air results in
mild irritation of the eyes and respiratory tract. In its liquid form, methyl
chloroform causes irritation to the skin and eyes upon contact. Studies of workers
occupationally exposed to methyl chloroform for up to 6 years have demonstrated
no adverse health effects. Animal studies of chronic exposure to the chemical at
levels ranging up to 1750 ppm similarly have found no adverse health effects.
Under EPA's accelerated phase-out schedule adopted pursuant to the Clean Air
Act, production (and import) of methyl chloroform for other than feedstock uses
will be phased out in accordance with the following schedule (allowable production
expressed as a percentage of 1989 production)
1994 - 50%
1996 - essential uses only
The accelerated phase-out schedule contains somewhat more stringent production

limits than the amended Montreal Protocol, allowing only 30 percent of 1989
production (instead of 5 0 percent) in 1995. Both the accelerated phase-out schedule
and the amended Protocol, however, require a 50 percent reduction in 1994, and
phase out production of methyl chloroform in 1996. Replacement of methyl
chloroform in various uses, including metal cleaning, adhesives and coatings, and
aerosols, will be directly affected by the significant new alternatives policy (SNAP)
program, which EPA is in the process of implementing. A number of acceptable
and unacceptable alternatives to methyl chloroform have been identified in these
use sectors. EPA has provisionally designated perchloroethylene, trichloroethylene,
and methylene chloride as acceptable alternatives for most methyl chloroform
applications. Effective May 15, 1993, containers of and products containing methyl
chloroform introduced into commerce must bear a "clearly legible and conspicious"
label stating that they contain a substance which harms public health and
environment by destroying ozone in the upper atmosphere. Products made using
methyl chloroform must bear a label so stating unless: (i) they were manufactured
solely for export and are clearly identified as such, (ii) their manufacturer has
achieved a total reduction of solvent use of methyl chloroform and/or CFC-113 of
95 percent or more, or (iii) EPA determines that no acceptable substitute product o r
processes exists. Methyl chloroform is generally unaffected by the bans on non-
TM
MARCEL INC.
DEKKER,
essential products adopted by EPA in 1993 and 1994. The following summarizes
pertinent information on methyl chloroform.
Chemical Formula
Molecular Weight
CAS Number
ACGIH TLV
DOT ID Numbe
Chloroform
Chloroform (CHCI,) is the name given to trichloromethane, CHCI,, because of its

supposed relation to formic acid. A colorless liquid, half as dense as water and of
about the same viscosity, chloroform has a heavy, ether-like odor and a burning
sweetness of taste, being about 40 times as sweet as cane sugar. It is almost
insoluble in water, but it is freely miscible with organic solvents and is an
important solvent for gums, resins, fats, elements such as sulfur and iodine, and a
wide variety of organic compounds. Common synonyms are trichloromethane,
trichloroform, freon 20, Cobehn Spray-Cleaner solvent, formyl trichloride,
methane trichloride, methenyl trichloride, and methyl trichloride. Its CAS number
is 67-66-3. Chloroform is nonflammable and does not form explosive mixtures at
atmospheric temperatures and pressures. It is used primarily in the production of
Chlorofluorocarbon (CFC-22) and plastics like vinyl chloride. Other uses include
extraction and purification of some antibiotics, alkaloids, vitamins, and flavors. It
has been used as a solvent in lacquers, floor polishes, artificial silk manufacture,
resins, fats, greases, gums, waxes, adhesives, oils, and rubber; used as a solvent in
TM
DEKKER,
MARCEL INC.
photography and dry cleaning; used in fire extinguishers; and used in the
preparation of dyes and pesticides. It also was once used as a general anesthetic in
surgery but has been replaced by less toxic, safer anesthetics, such as ether. It now
has limited use.
Chloroform evaporates quickly and in its concentrated gaseous form, it will tend to
settle to the ground before dispersing. It produces poisonous gas in a fire and is
unstable when exposed to air, light, and/or heat, which cause it to break down to
phosgene, hydrochloric acid, and chlorine. When heated to decomposition,
chloroform emits toxic fumes of hydrochloric acid and other chlorinated
compounds. Fire may also cause containers of it to explode. Violent reactions will
occur if chloroform makes contact with strong caustics and chemically active metals
such as aluminum, magnesium powder, sodium, or potassium.
Contact with it can irritate skin, causing a rash or burning feeling. The liquid can
cause severe eye burns. Exposure to the vapor can irritate the nose and throat.
Higher levels of exposure can cause coma and even death. Immediately or shortly
after exposure to chloroform, the heart may beat irregularly or stop. Exposure can
also cause dizziness, lightheadedness, nausea, confusion, and headache. 100,000
ppbv (488,000 mg/m3) is the maximum airborne concentration below which it is
believed that nearly all individuals could be exposed for up to one hour without
experiencing or developing irreversible or other serious health effects or symptoms
that could impair their abilities to take protective action. Long term health effects
may include damage to the liver, kidney, and nervous system. Alcohol consumption
can increase the liver damage caused by chloroform. US EPA has classified
chloroform as a Group B2, probable human carcinogen. US EPA estimates that, if
an individual were to breathe air containing chloroform at 0.0088 ppbv (0.043
mg/m3) over his or her entire lifetime, that person would have no more than a one-
in-a-million increased chance of developing cancer.
Chloroform is produced by reaction of chlorine with ethanol and by the reduction
of carbon tetrachloride with moist iron. It was once used as a general anesthetic in
surgery but has been replaced by less toxic, safer anesthetics, such as ether.
Chloroform is produced as a byproduct of water, sewage, and wood pulp
chlorination.
Carbon Tetrachloride
Carbon tetrachloride (CAS 56-23-5) is a clear, heavy liquid with a strong, aromatic
odor. Its formula is CCI,. It is produced in large quantities for use in the
manufacturing of refrigerants and propellants for aerosol cans. It is also used as a
feedstock in the synthesis of chlorotluorocarbons and other chemicals, in petroleum
refining, pharmaceutical manufacturing, and general solvent use. Until the mid-
1960s, it was also widely used as a cleaning fluid, both in industry, where it served
as a degreasing agent, and in the home, where it was used as a spot remover and in
fire extinguishers.
TM
DEKKER,
MARCEL INC.
Carbon tetrachloride is a highly volatile liquid with a strong etherial odor similar to
chloroform. It mixes sparingly with water and is not flammable. When heated to
decomposition, it emits highly toxic fumes of phosgene and hydrogen chloride.
There is strong evidence that the toxicity of carbon tetrachloride is dramatically
increased by its interaction with alcohols, ketones, and a range of other chemicals.
Carbon tetrachloride is known to deplete the ozone layer, where it is responsible
for 17% of the ozone-destroying chlorine now in the stratosphere due to human
activities. Carbon tetrachloride has a half-life of between 30 and 100 years.
Synonyms for carbon tetrachloride are carbona; carbon chloride; carbon tet;
methane tetrachloride; methane, tetrachloro-; perchloromethane; and
tetrachloromethane. Its DOT Label is Poison, its CAS number is 56-23-5, and its
UN number is 1846.
Carbon tetrachloride is listed in the National Toxicology Program's Fifth Annual
Report on Carcinogens as a "substance which may reasonably be anticiprtted to be
carcinogen. " Short-term exposure by inhalation or ingestion can cause death. Short
and longterm exposure also affect the brain, the liver, and the kidneys, in some
cases causing death. There is some evidence that exposure to carbon tetrachloride
causes liver cancer in humans; there is limited evidence that exposure may damage
the developing fetus. Repeated contact can cause thickening and cracking of the
skin. Effects on the brain are usually quite rapid. The most common effects are
dizziness, lightheadedness, nausea and vomiting, which can cause permanent
damage to nerve cells. In severe cases, these effects can lead rapidly to stupor,
coma, unconsciousness or death. Exposure can make the heart beat irregularly or
stop. The chemical may irritate the eyes on contact. When carbon tetrachloride is
emitted into the air, it rises to the atmosphere and depletes the ozone layer.
Depletion of the ozone layer is believed to increase human exposure to ultraviolet
rays, leading to increased skin cancer, eye diseases and disorders, and possible
disruption of the immune system. Persons who are moderate to heavy drinkers are
at greatly increased risk of liver andlor kidney injury following ingestion or
inhalation of carbon tetrachloride. Substantial exposures to alcohols and ketones
which increase the toxicity of carbon tetrachloride may occur in occupational
settings, or in certain instances in the use of household products containing these
chemicals.
Five U.S. companies manufacture carbon tetrachloride: Akzo-America, formerly
Stauffer Chemical, Chicago, IL; Dow, Midland, MI; LCP Chemicals and Plastics,
Edison, NJ; Occidental, Dallas, TX; and Vulcan Chemical, Birmingham, AL. In
1988, 761 million pounds of carbon tetrachloride were produced in the United
States.
EPA offices overseeing regulations and guidelines applicable to carbon
tetrachloride are Air Quality Planning and Standards, Water Regulations and
Standards (for the National Pollutant Discharge Elimination System), Drinking
Water, Emergency and Remedial Response, Solid Waste, and Pesticide Programs.
The Occupational Safety and Health Administration (OSHA) has established
TM
MARCEL DEKKER, INC.

permissible exposure limits for carbon tetrachloride. The Federal Drug

Administration has listed it as a banned hazardous substance. Under Section 313 of
the Emergency Planning and Community Right-to-Know Act of 1986, releases of
more than one pound of carbon tetrachloride into the air, water, and land must be
reported annually and entered into the Toxic Release Inventory (TRI).
Carbon tetrachloride, CCI, (i.e., tetrachloromethane) is prepared by the action of
chlorine on carbon disulphide in the presence of iodine, which acts as a catalyst.
CS, + C1, = CCI, + S,CI,
Carbon tetrachloride may also be prepared by the free radical substitution of the
hydrogen atoms of methane by chlorine.
CH, + 4C1, = CCI, + 4HC1
The bonding in carbon tetrachloride is covalent, as in methane.
Chlorobenzene
Chlorobenzene, also called monochlorobenzene, is a monocyclic aromatic

compound. It is a colorless liquid with an aromatic almond-like odor and is
manufactured for use as a solvent, is used in the production of other chemicals
(pesticides), and in making certain other chemicals, rubber, dyes and grease
solvents. It is used as a feedstock to produce ortho- and para- nitrochlorobenzenes
and aniline; as a solvent for paints; and as a heat transfer medium. In the past,
chlorobenzene was used as an intermediate in phenol and DDT production.
Chlorobenzene enters the environment from industrial and municipal discharges.
Another potential source is the formation and emission of chlorobenzene as a
product of incomplete combustion in waste incinerators.
Occupational exposure occurs primarily through breathing the chemical. Personnel
engaged in the production and handling of chlorobenzene would be at greatest risk.
Chlorobenzene is moderately soluble in water; up to 1,000 milligrams will mix
with a liter of water. Chlorobenzene is slightly persistent in water, with a half-life
of between 2 to 20 days. Chlorobenzene persists in soil (several months), in air (3.5
days), and water (less than 1 day). About 99.25% of chlorobenzene will eventually
end up in air; the rest will end up in the water.
Chlorobenzene is a flammable liquid and a fire hazard. It is unreactive towards
water and decomposes only at high temperatures. When heated to decomposition
this compound emits toxic fumes of hydrogen chloride gas, CO and CO,. Common
synonyms are Monochlorobenzene, Benzene Chloride, and Chlorobenzol. It is
incompatible with strong oxidizing agents and dimethyl sulfoxide.
Chlorobenzene (also best known as monochlorobenzene or MCB) is a flammable
liquid. It is produced in large amounts (231 million pounds in 1992) in the United
States by three companies. U.S. demand is likely to remain constant over the next
TM
DEKKER,
MARCEL INC.
several years. Because of environmental concerns for chlorinated organic chemicals

in general, future U.S. demand for MCB is likely to decline. The largest users of
MCB are companies that make nitrochlorobenzene. Companies also use MCB to
make adhesives, paints, paint removers, polishes, dyes, and drugs. In the past
companies have used MCB to make phenol and related chemicals, pesticides (like
DDT), and aniline.
Chlorobenzene can evaporate when exposed to air. It dissolves slightly when
mixed with water. Most releases of chlorobenzene to the U.S. environment are to
air. MCB also can evaporate from water and soil exposed to air. Once in air,
MCB breaks down to other chemicals. Because it is a liquid that does not bind well
to soil, MCB that makes its way into the ground can move through the ground and
enter groundwater. Plants and animals are not likely to store chlorobenzene.
Effects of chlorobenzene on human health and the environment depend on how
much chlorobenzene is present and the length and frequency of exposure. Effects
also depend on the health of a person or the condition of the environment when
exposure occurs.
Dichlorobenzene
The compound 1,4-dichlorobenzene (CAS 106-46-7) is most commonly referred to

as para-DCB or p-DCB. It is widely used as a moth killer, in space deodorizers,
and in the production of polyphenylene sulfide. It is also used in the manufacture of
certain resins, in the pharmaceutical industry, and as a general insecticide in
farming. Synonyms for 1,4-dichlorobenzene are 1,4-dichlor-B; benzene, 1,4-
dichloro; benzene, p-dichloro; dichlorobenzene, para, solid; p-chlorophenyl
chloride; p-DCB; p-dichlorobenzene; p-dichlorbenzol; parazene; PDB; para-DCB;
paradichlorobenzene; and paradichlorobenzol. At room temperature, 1,4-
dichlorobenzene is a white or colorless crystalline solid with a characteristic
penetrating odor. When exposed to air, it is slowly transformed from its solid state
into a vapor; the released vapor then acts as a deodorizer and insect killer. It is
practically insoluble in water and is soluble in alcohol, acetone, ether, chloroform,
carbon disulfide, and benzene. Its chemical formula is C,H,Cl,.
There is limited evidence that 1,4-dichlorobenzene can damage a developing fetus.
Exposure can damage the lungs, liver, kidneys, and blood cells, causing anemia; it
can also cause swelling of the eyes, hands, and feet. It can damage the nervous
system, causing weakness, trembling, and numbness in the arms and legs. It may
cause a skin allergy, which when developed can cause itching and a skin rash.
Higher levels of the chemical in air, such as the levels that are sometimes
associated with industrial exposure, can cause headaches, nausea, clumsiness,
slurred speech, and dizziness. Levels that would result in death would be associated
with an odor so intense that it would be very unpleasant, if not intolerable, and
would serve as a danger warning. In industrial situations, workers exposed to 1,4-
dichlorobenzene at high levels are usually directed to wear respirators. Workers
TM
MARCEL DEKKER, INC.

involved in the production of the chemical may be exposed to concentrations

significantly higher than those encountered by the general population. High
exposure levels may result from some consumer products of moth repellents and
room deodorizers. Approximately 95% of the environmental release of 1,4-
dichlorobenzene occurs during its use, rather than during its manufacture or
processing.
1,2-Dichlorobenzene (DCB, o-Dichlorobenzene, ODB, Orthodichlorobenzene),
C,H,CI,, is a colorless to pale yellow liquid with a pleasant aromatic odor. It is a
combustible liquid and can form explosive mixtures with air at or above 151°F.
Combustion and thermal decomposition products include hydrogen chloride gas,
phosgene and chloro-carbons. Its flammable (explosive) limits are as follows:
Lower 2 . 2 % , Upper 9.2%.
Ethylene Dichloride
Ethylene dichloride (1,2-dichloroethane), otherwise known as EDC, is produced by

reacting chlorine or anhydrous hydrochloric acid with ethylene. The largest single
use for EDC is the production of vinyl chloride monomer, which is used to produce
polyvinyl chloride (PVC). EDC can also be used in the manufacture of other
organic compounds, and as a solvent. Ethylene dichloride is a colorless, oily liquid
with a chloroform-like smell. It has many uses in industry, with principal ones
being the following:
As an intermediate in the manufacture of methyl chloroform,

perchloroethylene, ethylene amines, polyvinyl chloride (PVC), sulfide
compounds, vinyl chloride, and trichloroethane.
As an additive in gasoline (used as a lead scavenger), pharmaceutical

products, color tilrn, and pesticides.
As a solvent for rubber, tobacco extract, paint, printing inks, and varnish.
Miscellaneous uses include as an ingredient in fingernail polish, for metal

degreasing, in extracting spices, and as a dry cleaning agent.
Two of the major uses for this chemical are the manufacture of PVC and as a lead
scavenger in gasoline. The process for making EDC begins with crude oil or
natural gas and sodium chloride. The hydrocarbon raw materials are converted to
ethene (ethylene), and sodium chloride is electrolyzed to pruduce chlorine.
2 NaCl + 2 H,O = CI, + 2 NaOH + H2
This electrochemical process is also the major industrial route for sodium hydroxide
production, so essentially the only side product from this initial reaction is
hydrogen gas, which is later converted to water. Once the ethylene is produced
from the crude hydrocarbons, it is reacted with chlorine gas:
TM
MARCEL DEKKER, INC.

C,H, + CI, = C,H,CI (1,2-dichloroethane)
Although its common name would lead one to believe otherwise, EDC does not
contain a double bond. In one of its major industrial processes, the manufacture of
PVC, the following reaction is carried out:
C,H,CI = C,H,CI (vinyl chloride) + HCI

The HCI produced in this reaction is recycled to be used in the first reaction by
oxidation of the hydrogen-chlorine bond. Ethylene dichloride is produced
domestically by ten manufacturers. Approximately 1.2 billion Ibs. is produced in
the United States per year. In 1989 nine million pounds of 1,2-Dichloroethane were
released as pollution, 43.22% into the air, 2.34% into surface water, . 0 l % onto
land, 11.01% underground, 16% into public sewage, and 27.43% off site. Its EPA
hazardous waste classification is DO01 (ignitable waste), and its DOT hazard class
is flammable liquid, with a reportable quantity of 5000 Ibs. It should be stored in a
cool, dry, well-ventilated flammable liquid storage area, away from oxidizers,
strong acids, chemically active metals, strong caustics, and dimethyl-
aminopropylamine, as violent reaction can occur.
1,2-dichloroethane is regulated in the workplace under OSHA. Its legal airborne

permissable exposure limit (PEL) over an &hour shift is 50 ppm, with a 100-ppm
ceiling not to be exceeded at any time, except for an allowable peak up to 200 ppm
for 5 minutes in any 3 hours of a workshift. This 50-ppm PEL is not detectable by
the human nose; its odor threshold is 88 ppm. EDC is a carcinogen and a mutagen.
Assessments of 1,2-dichloroethane are in progress under the authority of the Clean
Air Act, Safe Drinking Water Act (SDWA), Toxic Substances Control Act
(TSCA), and the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA).
EDC is also listed under CERCLA as a hazardous material, and is required to be
reported as such under Title I11 of SARA, otherwise known as the Community
Right-to-Know Act.
Ethylidene Dichloride (1,l-Dichloroethane)

Ethylidene dichloride is primarily used as an intermediate in chemical synthesis.
Acute (short-term) inhalation exposure to high levels of ethylidene dichloride in
humans results in central nervous system (CNS) depression and a cardiostimulating
effect resulting in cardiac arrhythmias. Studies in animals have reported effects on
the kidney. No information is available on the chronic (long-term) reproductive,
developmental, or carcinogenic effects of ethylidene dichloride in humans. An oral
animal study reported a significantly positive dose-related trend in
hemangiosarcomas, mammary tumors, liver tumors, and endometrial stromal
polyps. EPA has classified ethylidene dichloride as a Group C, possible human
carcinogen.
TM
MARCEL DEKKER, INC.

Primary uses are:
Ethylidene dichloride is primarily used as an intermediate in the

manufacture of other chemicals such as vinyl chloride and 1,1,1-
trichloroethane, and to manufacture high vacuum rubber.
Ethylidene dichloride has limited use as a solvent for plastics, oils, and
fats.
In the past, ethylidene dichloride was used as an anesthetic, but that use has been
discontinued.
Ethylidene dichloride is a colorless oily liquid which is very volatile. It has an odor
similar to ether; the odor threshold is 120 parts per million (ppm). The chemical
formula for ethylidene dichloride is C,H,CI,, and the molecular weight is 98.97
glmol.
HYDROCARBON SOLVENTS (ALIPHATIC AND AROMATIC)
General Information
As noted by Archer, hydrocarbon solvents are compounds containing only carbon

and hydrogen atoms. A large number of both aliphatic and aromatic solvent blends
are produced by various petrochemical companies from the distillation refining of
petroleum stock, the alkyiation of certain distillation products, and the selective
catalytic hydrogenation of hydrocarbon fractions. The hydrogenation process
eliminates unwanted components from the hydrocarbons and also converts
undesirable fractions into useful hydrocarbons. Typical reactions include the
removal of nitrogen, oxygen, and sulfur containing compounds and the conversion
of acetylene and aromatic and olefin hydrocarbons into saturated normal paraffins,
isoparaffins, and cycloparaffins. These petroleum solvents find wide use in the
chemical industry and many other industrial application uses that require solvents.
The solvents are used both as active solvents to dissolve an ingredient and as
inexpensive diluents for coatings and paints.
Several grades of dearomatized aliphatic hydrocarbon solvents find use in industrial
and institutional cleaning products. Synthetically produced isoparaffin (branched
chain) and normal paraffin (straight chain) blends also find use in cleaning
formulations. These paraffinic solvents are often blended with oxygenated and other
solvents for effective cleaning performance. The hydrocarbon solvents offer
effective cleaning power, excellent wetting ability, low corrosion, low toxicity, and
low odor. A wide range of evaporation rates offers formulation flexibility.
Industrial soils removed by cleaners containing the hydrocarbon solvents include
petroleum- and aqueous-based metal working fluids, buffing and polishing
compounds, mold-release agents, acrylic adhesives, lubricating greases, and
waxes. Many of the cleaning operations may also require the use of agitation,
TM
MARCEL DEKKER, INC.

immersion spraying, ultrasonic energy, o r heat (with the proper safety features in
place).
The synthetic isoparaffins are suitable solvents for alkyd and acrylic paint
formulations. These virtually odorless solvents and their low surface tensions offer
improved flow and wetting properties to the paints. The excellent wetting
characteristics of these solvents are desirable in formulations such as furniture
polishes, car polishes, and waterless hand cleaners. The low surface tension of
these solvents reduces the amount of surfactants needed in emulsified products and
affords improved wetting of pigments in ink and coating formulations. The
isoparaffins are used as an inert process solvent in the manufacture of polyolefins
and certain rubbers. In the slurry polymerization process the isoparaffins afford
solvency for the Ziegler-type catalyst and the ethylene monomer, but no solvency
for the polyolefin polymer product.
The hydrocarbon blends with high cycloparaffin content have higher solvency than
the straight chain paraffin hydrocarbon blends. The cycloparaffin blends find use in
architectural coatings, original manufactured equipment (OME) and automotive
refinish coatings, industrial metal and wood coatings, and maintenance and marine
coatings. The hydrocarbon blends with high aromatic content afford slow
evaporation rates and good flow and leveling performance in coil coatings. These
solvents offer good solvency for acrylic, alkyd, epoxy, maleic, methacrylic, natural
phenolic, polyester, polyurethane, styrene, urea and vinyl resins in industrial metal
coatings, and maintenance and marine coatings. The Aromatic 100 blend is an
effective chain transfer process solvent for acrylic polymerization.
Other miscellaneous uses for the isoparaffin solvents, dearomatized paraffinic

solvents, normal paraffinic fluids, and aromatic blends include pesticide
formulation applications, wood preservatives, fat and oil extractions, cosmetic and
notion formulations, paper coatings, and textile coatings and printing. Inks, paints
varnishes, and lacquers are among the largest uses of the hydrocarbon solvents.
Suppliers
Exxon Chemical and Shell Chemical are the two largest suppliers of aliphatic and
aromatic hydrocarbons, however there are a number of other players on the world
market. Some of these are noted in the discussions throughout this subsection.
Exxon offers catalytically synthesized isoparaffinic solvents under the tradename of
Isopar, a family of dearomatized aliphatic hydrocarbon solvents under the
trademark of Exxsol, while the tradename Norpar signifies three grades of high
content normal paraffinic solvents with relatively narrow boiling-point ranges. Shell
Chemical offers a wide range of hydrotreated hydrocarbons under the trademark of
Tolu-Sol where the letter designation "HT" denotes solvents which contain very
few aromatic hydrocarbons. Other nontrademark names for Shell hydrocarbon
solvents include the designation "Sol," VM&P Naphtha, and Mineral Spirits.
TM
MARCEL DEKKER, INC.

Properties and Characteristics

The Exxon Isopar series of solvents cover a distillation range of 98 to 311°C,
have flash points from 18°F to a high of 239"F, have low surface tensions in the
range of 20 to 30 dynesicm, and recommended allowable vapor exposure threshold
limit values (TLV) of 300 to 400 ppm. The isoparaffinic solvents have inherently
low solvency for most resins and plastic materials (no Hansen polarity or hydrogen
bonding values). The flammable limits (vol. % in air) at 25°C of the isoparaffinic
solvents range from a low 1.1 vol. % to an upper limit of 11.6 vol. % solvent in air.
The dearomatized aliphatic hydrocarbons sold by Exxon under the trademark
Exxsol are solvents that boil in the range of 159 to 316"C, have moderately high
flash points, low surface tensions, low evaporation rates, and high (300 ppm)
occupational exposure limits (OEL). The presence of high cycloparaffin
(naphthene) content in the Exxsols improves their solvency for certain resins.
Archer's orginal volume contains chemical-specific information on these solvents
(see Industrial Solverzts Handbook, W . L. Archer, Marcel Dekker Inc., New York,
1996). The Tolu-Sol solvents produced by Shell Chemical are fast- to medium-
evaporating hydrocarbon solvents. They are blends of aliphatic paraffins and
cycloparaffins. The Tolu-Sol W HT and 6W solvents with their higher
cycloparaffin content show higher solvency than the straight and branched chain
paraffin solvent blends. Many of these solvent blends have large percentages of
cycloparaftins and have evaporation rates much slower than the Tolu-Sol blend
series. Refer to Archer's volume for chemical-specific data.
Totalfina offers a comprehensive portfolio of light SBP fractions within its
Hydrosol aliphatic hydrocarbon solvents range. These products have an extremely
low aromatic content, typically 10 ppnl, giving the user greater flexibility when
formulating products. Typical applications include:
HYDROSOL PENTANE: Expandable polystyrene, aerosols
HYDROSOL ISOHEXANE: Adhesives, extraction agents, aerosols,

process fluids
HYDROSOL HEXANE: Oil seed extraction, extraction of essential oils

for perfumes, process fluids and adhesives
0 HYDROSOL ESS. A: Stain remover
HYDROSOL HEPTANE: Glues, adhesives, tires, cleaning
HYDROSOL ESS. 60195: Glues, spot remover
HYDROSOL ESS. C: Household cleaning products, rubber manufacture,

fuel for catalytic burners
Table 10 provides some properties of these solvents.
TM
MARCEL DEKKER, INC.

Solvents ( H drosol Serie
1l-
PROPERTIES UNITS METHOD I I
Density at lS°C kgim3 ASTM D
14052 1 "I"
Saybolt Color
3oiling Range:
1 ASTM D
156
hitial Point
Dry Point
ASTM D
1078
Flash Point
\be1
IoC I NF EN
IS0 13736
3vaporation
Iate
rota1 Aromatic %
Zontent
Ultra
weight Violet -
1
ether= DIN 53 170
Total IL
013
3enzene
zontent Ip m ASTM
ID4367
Gas-
chromato.
hiline Point 1 'C /ASTM D

61 1
TM
MARCEL
DEKKER,
INC.
PROPERTIES UNITS METHOD
Refractive
Index at 20°C
20°C
Carbon Content
CAS Number
IRMN I I I
C5
E.1.N.E.C.S / EEC Number 203- 265- 295-

692-4 151-9 570-2
TOTALFINA also offers a comprehensive portfolio of heavy SBP fractions within

its HYDROSOL atiphatic hydrocarbon solvent range. These products have an
extremely low aromatic content, typically 100 ppm, and a benzene level of less
than Ippm, giving the user greater flexibility when formulating products. Typical
applications include:
HYDROSOL ESS. 80/110: Rubber processing, adhesives
HYDROSOL ESS. E < 5 : Rubber processing, paints
HYDROSOL ESS. 1001140: Rubber processing
HYDROSOL ESS. F < 5 : Paints, rubber processing, degreasing, dry

cleaning
HYDROSOL ESS. 75195 Naphthenic: Adhesives and degreasing
HYDROSOL ESS. 1001130 Naphthenic: Paints, varnishes, rubber

processing, degreasing
Table 11 provides some properties for this series.
TM
MARCEL
DEKKER,
INC.
Table 11. Properties of Heavy Commercial Solvents (Hydrosol Series).
PROPERTlES UNITS METHODS
Density at 15°C - -I- <g/m3 ASTM D 4052
Saybolt Color
[nitial Boiling Point 'C

-t--- I
ASTM 0 156
ASTM D 86
Dry Point 'C ASTM D 86
Flash Point Abel "C NF EN IS0 13736
Evaporation Rate :ther = 1 DIN 53 170
rota1 Aromatic % Ultraviolet - Total

Clontent xeight IL013
Benzene Content jpm ASTM D4367
I-Hexane Content % Gas-chromato.

xeight
iniline Point ASTM D 61 1
Vapor Pressure at
!O°C
:+
--I--
- - - - -
Surface Tension at iynelcm De Nouy

!O°C
iefractive Index at lo units ASTM Dl218

!O°C
Viscosity at 20°C nm2/s ASTM D 445
3arbon Content
TM
MARCEL DEKKER, INC.

80 Industrial Solvents Halidbook
Uses
The Isopar isoparaffinic hydrocarbon blends sold by Exxon have low odor,
selective solvency, good oxidation stability, low electrical conductivity, and low
skin irritation. The Isopar solvents are well suited for the nlanufacture of
electrostatic copying fluids, odor-free paints, waterless hand cleaners, and many
proprietary household products. The low solvency of these isoparaffinic
hydrocarbons for most resins and plastics nlinimizes any marring of surfaces to
which the proprietary formulations are applied. The Isopar solvents and competitive
products are ideal for photocopy applications since the solvents will not attack
plastic or rubber components in the equipment. The Isopar solvents have lower
latent heats of evaporation and faster evaporation rates than the other aliphatic
hydrocarbons of equivalent boiling points. These properties provide faster drying
and rapid release of the solvent from the application or process. The fast
evaporating Isopar solvents reduce energy requirements in applications such as
polyoletin manufacture, adhesive manufacture and in the electrostatic copying
process. The low surface tensions of the Isopar solvents contribute excellent wetting
characteristics to various applications such as ink and paint manufacture. The
amount of expensive surfactant required for a forniulation or process can often be
reduced because of the low surface tensions of the Isopars. In polyolefin
manufacture the Isopar solvents act as an inert solvent for the slurry polymerization
of ethylene in the presence of a Ziegler catalyst. The absence of any polar or olefin
impurities in the solvent avoids any poisoning of the polymerization catalyst. The
polymer is insoluble in the solvent which facilitates the rapid recovery and drying
of the polymer. FDA regulation 21 CFR 178.3650 allows the use of Isopar G, H,
K, and L in the manufacture of polyolefin articles for food contact. Isopar grades
H , K, and L are recomn~endedas solvents in alkyd paint and enamel forniulations.
Coatings formulated with Isopar solvents exhibit good color depth, resistance to
sagging, and good leveling charac~eristics.Isopar solvents are useful in organosol
formulations (particles of vinyl resins suspended in a plasticizer). The solvents have
low solvency for resins and thus have little tendency to swell the resin. This
behavior provides good prolonged storage characteristics, good viscosity control,
and easy application of the coating.
The low solvency, low heat of vaporization, and fast evaporation rates of the Isopar
solvents are advantages in the manufacture of pressure sensitive elastomer
adhesives. The low solvency toward the elastomers permits higher solids loading
and keeps the solution viscosities low for easy application. The higher solids
loading and faster drying evaporation rates reduce drying times. The use of Isopar
solvents as diluents in flexigraphic and gravure inks eliminates solvent damage of
rubber and composition printing plates. The solvent's low surface tension allows
rapid migration of the solvent and ink into the paper which provides improved
brightness. The fast evaporation rates of the solvents are another advantage in the
printing process. The purity of the Isopar solvents makes them suitable for many
TM
MARCEL DEKKER, INC.

direct and indirect food related applications. The Food and Drug Administration
(FDA) regulations governing the use of the Isopar solvents can be obtained from
the Exxon Chemical Company. Isopar solvents have been recommended as
substitute solvents for certain chlorinated solvents, mineral spirits, and kerosene-
type cleaners. The Isopar solvents are effective in removing petroleum-based oils
including stamping oils, cutting oils, and rust preventative oils. The low surface
tension of the Isopar solvents provides good wetting of engineering plastic
components. The excellent wetting action permits their use as water displacement
fluids for metal parts with small clearances. The Isopar solvents are compatible
with many of the nonionic surfactants used in industrial cleaning formulations.
The high flash points of Isopar M and V allow these solvents to be formulated
into noncombustible (flash point > 200°F) solvent and emulsion cleaners.
Exxsol solvents are a series of dearomatized aliphatic hydrocarbons useful in
solvent- and emulsion-type industrial and institutional cleaning and degreasing
formulations. The Exxsol solvents effectively remove petroleum type oils and
greases, stamping oils, cutting oils, and rust preventative oils. The Exxsol solvents
also remove buffing and polishing compounds, mold release agents, acrylic
adhesives and waxes. Cleaning efficiency of the Exxsols is similar to the mineral
spirits, kerosene and terpene products. The Exxsol solvents are noncorrosive
toward metals and leave very low residues on cleaned metal parts. The high flash
points of Exxsol 13110 and Dl30 allow their use in noncombustible solvent and
emulsion cleaners. The Exxsol solvents are useful in numerous home, garden, lawn,
and agricultural pesticide formulations because of their very low phytotoxicity. The
low surface tension of the Exxsols facilitates the spreading of the pesticide rapidly
across a surface. Agrichemical professionals at Exxon Chemical are available to
assist pesticide formulators in selecting the proper solvent. The low odor and
evaporation rates as well as good substrate wetting of Exxsol D40 and D60 are
features which make them useful solvents for architectural coatings, OME, and
automotive refinish coatings, industrial metal and wood coatings, and maintenance
and marine coatings. The solvents also have higher OELs (e.g., 300 ppm) as
compared to mineral spirits (OEL = 100 ppm).
The normal paraffinic solvent blends sold by Exxon under the tradename of Norpar
are also used in industrial and institutional cleaners and degreasing formulations.
This series of solvents is similar in many respects to the Isopar and Exxsol solvent
blends also used in cleaners and degreasers. The Norpar 13 and 15 can be
formulated into noncombustible cleaners. The Norpar solvents may be used in
certain applications involving incidental food contact under several FDA
regulations. Exxon Chemical can supply details about the regulated applications.
The Aromatic 100 solvent blend marketed by Exxon has high solvency for acrylic,
alkyd, epoxy, and polyester resins, and is an effective chain transfer solvent for
acrylic polymerization. The Aromatic 100 solvent is a high purity aromatic solvent
that contains only a low level of Hazardous Air Pollutants (HAPS) as defined in the
Clean Air Act. Aromatic 100 is an effective solvent for removing water by
azeotropic distillation during an alkyd resin preparation. In the past xylene has been
TM
DEKKER,
MARCEL INC.
the solvent of choice for the alkyd resin process. Xylene is on the HAP list. The
Aromatic 100 solvent has only small amounts of reportable HAP components
(calculated by Exxon to be 3.4 wt%). Calculations by Exxon using the Hansen
solubility parameter theory showed that Aromatic 100 has improved solvency over
xylene for several acrylic, alkyd, epoxy, and polyester resins. The aromatic nature
of these solvents gives some polarity and hydrogen bonding character to the
molecule. The reported parameters for Aromatic 100 are S,, = 17.2, S,, = 1.0, and
S, = 3.1. The Aromatic 150 and 200 solvents are effective tail solvents for
polyester coil coating applications. The combined good solvency for the resins and
slower evaporation rates allow good flow and leveling of the coating during the
rapid high temperature curing process. The Aromatic 150 and 200 solvents are
economically attractive substitutes for high boiling point oxygenated solvents often
used as tailing solvents.
The Shell Chemical product lines are blends with boiling points ranging from 61 to
204°C. These find use as solvents in adhesives, agricultural formulations,
automotive undercoating, cleaning and polishing formulations, cosmetics, drugs
and pharmaceuticals, inks, paints, varnish, lacquers, paper coatings, resin and
plastic applications, textile coatings, printing, and other miscellaneous uses. The
Shell Sol B HT is a mixture of 90% C, and 10% C, hydrocarbons with 9 0 % of the
hydrocarbons being straight and branched chain paraffins and the remaining content
being cycloparaffinic (naphthenes). The Sol B HT is a good replacement for
commercial hexane. The Shell Tolu-Sol A HT and W H T hydrocarbon blends
contain C, and C, paraffins along with cycloparaffins. The Sol B HT and Tolu-Sol
A HT and W HT solvents are used in adhesives, inks, paints, coatings, and as
solvents for certain resins and plastics. Other Tolu-Sol hydrocarbon blends
available from Shell include the 3, 5, 6W 10, 19EC, and 25 grades. Only the W
HT and 6W grades have a high cycloparaffinic content. All of the Tolu-Sol grade
solvent blends can be classified as fast to medium evaporating solvents which find
wide use in coatings, lacquers, paints, and varnishes. The VM&P naphtha, mineral
spirits, and Sol 340HT, 142HT, and 71 hydrocarbon solvent blends are slower
evaporating solvents. All of these solvents have high cycloparaffinic contents and
thus higher solvency for certain resins. These solvents find uses in coatings and
paints, dry cleaning, industrial and institutional cleaners, and pesticide
formulations, and as solvents for certain resins.
Safety Considerations
The health hazards of many hydrocarbon solvents are less than many other types of
solvents. Proper ventilation should be provided in areas where the volatile solvents
are used and skin contact with the petroleum solvents should be minimized.
Inhalation of high concentrations of the hydrocarbon vapors will cause an anesthetic
effect and depression of the central nervous system, and is characterized by
dizziness, loss of coordination, and the feeling of being lightheaded. Removal of
the individual from the exposure area and into fresh air will reverse the anesthetic
TM
DEKKER,
MARCEL INC.
symptoms. Prolonged exposure in areas of high vapor concentrations can quickly

lead to unconsciousness and death through respiratory failure. Repeated
overexposure to normal hexane can cause peripheral polyneuropathy, a progressive
and potentially irreversible disorder of the nervous system. The American
Conference of Governmental Industrial Hygienists (ACGIH) recommended
maximum exposure level for hexane is a time weighted average (TWA) of 5 0 ppm
for an 8-hr day and 40-hr work week. Other studies have indicated that the
excessive inhalation of other hydrocarbon vapors can also cause degenerative
changes to the nervous system.
Benzene has the ability to damage the bone marrow and to cause anemia and
leukemia. This hematopoietic toxicity shown by benzene is unique as the
myelotoxic effect disappears when one or more alkyl groups are attached to the
benzene structure. Toluene and xylene are examples of the aromatic solvents which
do not show the hematopoietic toxicity. The OSHA regulation 29 CFR 1910.1028
allows a Permissible Exposure Limit (PEL) of 1.0 ppm benzene in the work area
for an 8-hr day and 40-hr work week. The current documents of both the OSHA
and ACGIH organizations consider benzene as a suspected human carcinogen.
Proper ventilation will aid in reducing vapor concentrations of solvents to
acceptable exposure limits. In areas of higher vapor concentrations workers should
be trained and equipped with appropriate respirators as per the recommendations of
the solvent manufacturer. Proper safe handling procedures will be outlined in the
Material Safety Data Sheet (MSDS).
KETONES
Ketones are a class of functional groups that contain an internal carbonyl (C=O)
group and are connected to two alkyl groups. In contrast, aldehydes are a class of
functional groups that contain an external carbonyl group, attatched to alkyl
substituent and a hydrogen. Examples of ketones are acetone, cyclohexanone,
diacetone alcohol, diisobutyl ketone, isophorone, methyl amyl ketone, methyl ethyl
ketone (MEK), methyl isoamyl ketone, methyl isobutyl ketone, and methyl propyl
ketone. The general form of a ketone is as follows:
Ketone common names are formed by naming the two alkyl substituents on the
carbonyl group. Substituent locations are given using Greek letters, beginning with
the carbon next to the carbonyl group.
TM
MARCEL DEKKER, INC.

84 Industrial Solveuts Handbook
Methyl ethyl ketone

'
P-Bromoethyl isopropyl ketone
CH,
To name ketones using the IUPAC system, find the largest carbon chain containing
the ketone. Use numbers to give the position of the ketone and chain the -ane
ending to -moue.
Table 12 provides the boiling points for the various ketones ranging from 3 to 9
carbons.
Table 12. Boiling Points of Some Ketones

Ketones Number Number Boiling Molecular
of of Point Weight
Carbons Carbons ("C) (glmol)
TM
MARCEL DEKKER, INC.

The ketones consist of some of the most toxic elements of essential oils. Some of
these include thujone and pulegone. The toxic chemicals in this group can cause
epileptic seizures, convulsions, abortive effects, and mental confusion. However,
not all ketones are toxic. The non-toxic ketones may aid in dissolving mucus,
dissolving fats, and wound healing. Some common chemicals in this group are
jasmone (Jasmine), fenchone (Fennel), carvone (Coriander, Peppermint, Tagetes),
menthone (Peppermint, Spearmint, Rose Geranium), and pinocamphone (Hyssop,
Juniper Berry).
The majority of the ketones are straight and branched chain aliphatic hydrocarbons
that contain the double bonded carbon-oxygen functional group. This carbonyl
group gives the ketones high solvency for a wide variety of natural and synthetic
resins. This high solvency feature makes the ketones valuable solvents in the
coating industries and in other applications involving the dissolving of an organic
substance. The ketones as a class are miscible with most other organic solvents.
Many of the ketones possess a high diluent tolerance for the less expensive aliphatic
and aromatic solvents. In many coating formulations the ketone solvents provide
the lowest practical solution viscosity for a certain percent resin solids. The ketones
generally have lower densities than other oxygenated solvents, which allows more
volume per unit weight formulations. This desirable feature enables the formulation
of higher-solids coatings that can better meet Volatile Organic Compound (VOC)
regulations and have the lowest practical solution viscosities. The lower surface
tension values of the ketones help reduce the high surface tensions of the high-
solids coating formulations. Diisobutyl ketone is particularly effective in reducing
the surface tensions of high-solids coating formulations.
The industrially available ketones offer a wide range of evaporation rates for the
various coating applications. A solvent with excellent solvency and a fast,
intermediate o r slow evaporation rate for a particular coating application is
available in the commercially produced ketones. Major producers of the ketones
include Eastman Chemical Company, Exxon Chemical Company, Hoechst
Celanese Company, Shell Chemical Company, and Union Carbide Corporation.
BASF Corporation produces the cyclic ketone cyclohexanone. Acetone the
lowest boiling-point ketone is produced by The Dow Chemical Company,
Exxon Chemical Company, and Texaco Chemical Company.
The largest single use for ketones is as solvents in the wide spectrum of coatings
and lacquers. The low density, low surface tension, low viscosity, and high resin
solvency of the ketones make these solvents ideal for a wide range of resin and
polymeric compositions. The ketones with their wide range of evaporation rates
enable the coating and lacquer manufacturers to select a solvent blend that will
allow the formation of a suitable coating or lacquer film. Many of the solvent
blends will contain one or two ketones along with diluents like the cheaper aliphatic
and aromatic hydrocarbons. Many of the ketones have high aliphatic and aromatic
hydrocarbon dilution ratios that allow high percentages of the cheaper hydrocarbon
TM
MARCEL DEKKER, INC.

diluents in the coating and lacquer formulations. Some of the ketones used as fast
and slow evaporating solvents in cellulose ester lacquers include acetone, methyl
isobutyl ketone (MIBK), ethyl n-amyl ketone, diisobutyl ketone, and
cyclohexanone. Cyclohexanone with its high aromatic dilution ratio imparts good
blush resistance, flow, and working qualities to lacquers. Methyl isobutyl ketone is
often blended with methyl ethyl ketone (MEK) for high-solids lacquers. High-solids
coatings of acrylic, polyesters, alkyd, and acryliclurethane resins often use solvent
blends of MIBK and MEK.
Nitrocellulose lacquers can be formulated with a large number of ketone solvents.
Acetone, a fast evaporating solvent, will tolerate large additions of cheaper
aromatic diluents to the nitrocellulose lacquers. The low viscosity of acetone and
the hydrocarbon additions affords low solution viscosities. Other ketones that are
useful as nitrocellulose solvents and that have high aliphatic and aromatic dilution
ratios include MEK and MIBK. Additional ketones that find use in nitrocellulose
lacquers include methyl n-arnyl ketone, methyl isoamyl ketone, dipropyl ketone,
diisobutyl ketone, and cyclohexanone. Selection of the ketone often will depend on
the desired evaporation rate.
Diacetone alcohol is available in two grades: a commercial grade containing 15%
acetone and an acetone-free grade. Both solvent grades of diacetone alcohol may
acquire a yellow color on aging; both are good solvents for nitrocellulose, cellulose
esters, and several other types of resins. The much slower evaporating diacetone
alcohol is similar to acetone in its solvency. It is used in brushing-type cellulose
ester lacquers to produce hard and brilliant gloss films. Diacetone alcohol is also
used as lacquer thinner and in coating compositions for paper and textiles. Mesityl
oxide, the unsaturated medium boiling point ketone that is prepared by the
dehydration of diacetone alcohol, will darken and form a solid residue on aging.
Mesityl oxide is a good solvent for nitrocellulose, cellulose esters, polyvinyl
chloride, and vinyl resins. Mesityl oxide is used in lacquers and thinners where its
presence lowers solution viscosity and gives the solutions high diluent tolerance for
hydrocarbons. Isophorone is an excellent solvent for cellulose esters, nitrocellulose,
natural and synthetic resins. Isophorone has a very high aromatic hydrocarbon
dilution ratio in nitrocellulose forn~ulations:5.7 for toluene and 5.1 for xylene. The
excellent solvency of isophorone allows the preparation of 45% solids nitrocellulose
solutions at room temperatures.
Methyl tl-hexyl ketone is used as solvent for vinyl compounds and dyes and is
suitable for dispersing dyes in light-weight petroleum oils for newsprint inks. High
boiling point ethyl 11-butyl ketone is used as a tailing solvent in lacquers and
synthetic resin coatings. The solvent is also used in high temperature baked
coatings.
Acetone and methyl ethyl ketone are valuable solvent components in
acryliclnitrocellulose automotive lacquers. Acetone is the solvent of choice in film
coatings operations which use vinylidene chloride-acrylonitrile copolymer
formulations. Othcr ketones that may be used in these film coating operations
TM
MARCEL
DEKKER,
INC.
include methyl isobutyl ketone, ethyl n-amyl ketone, and diisobutyl ketone. Vinyl
acetate and vinyl chloride-vinyl acetate copolymer compositions utilize a large
number of ketones as solvents. Acetone, blends of MIBK and MEK, methyl n-
amyl ketone, ethyl n-amyl ketone, and diisobutyl ketone are all useful solvents
for vinyl resin copolymers. The presence of one of the slower evaporating
ketones in the solvent blend prevents quick drying, improves flow, and gives
blush resistance to the coating. Acetone is also used as a resin thinner in polyester
resins and as a clean up solvent for the resin reactor kettle.
Adhesives - Acetone and methyl ethyl ketone are components of solvent blends in
urethane, nitrile rubber, and neoprene industrial adhesives. Acetone is the
primary solvent in resin-type adhesives and pressure sensitive chlorinated rubber
adhesives. Methyl isobutyl ketone is a solvent component for nitrile rubber and
acrylic adhesives as well as in polyvinyl chloride and polyvinyl chloride-poly-
vinyl acetate copolymer bonding adhesives. Again, the desired evaporation rate
of the adhesive formulation will often determine the ketone selected.
Solvent Extraction - Acetone is used to extract fats, oils, waxes, and resins from
natural products, to dewax lubricating oils, and to extract certain essential oils.
The pharmaceutical industry uses acetone to extract B-vitamin complexes,
alkaloids, antibiotics and enzymes. Methyl ethyl ketone is used to dewax lube oil.
Methyl isobutyl ketone is used to dewax mineral oil, refine tall oil, and in
extractive distillation and separation of isopropyl alcohol from ethyl and butyl
alcohols. The extraction and purification of antibiotics and other pharmaceutical
products utilize MIBK. Methyl isobutyl ketone is used in the extraction of rosin
from pine wood and the extraction of heavy metal ion complexes from water
solutions.
Miscellaneous Uses - Acetone is an important chemical intermediate in the

preparation of several oxygenated solvents including the ketones, diacetone alcohol,
mesityl oxide, methyl isobutyl ketone, and isophorone. Self-condensation of two
molecules of acetone yields the diacetone alcohol [(CH,),C(OH)CH,C(O)CHJ, a
molecule with both the alcoholic and ketone functional groups. Dehydration
(splitting out of water) of diacetone alcohol yields the unsaturated ketone, mesityl
oxide [(CH3)2C=CHC(0)CH3]. Hydrogenation of mesityl oxide yields the very
useful ketone, methyl isobutyl ketone [(CH,),CHCH,C(O)CH,]. The cyclic
condensation of three molecules of acetone yields the high boiling point solvent,
isophorone. Other uses of acetone include the reaction of two molecules of phenol
with acetone to form bisphenol-A, which when condensed with epichlorohydrin
forms an epoxy resin. Acetone will condense with a large number of organic
compounds that contain an active hydrogen atom. Acetone is used in the
manufacture of acetate rayon, photographic film, explosives, and is used as a
solvent for absorbing acetylene gas for storage and shipment in gas cylinders.
Methyl ethyl ketone is used in the production of smokeless powder, printing inks,
degreasing and cleaning fluids, antioxidants, perfumes, and catalysts. Methyl
isobutyl ketone is a solvent used in insecticides, fungicides, electroplating
TM
MARCEL
DEKKER,
INC.
solutions, leather finishing, and textile coatings. Faster condensation reaction

rates are claimed in the polymerization of ply-(ethyleneterephthaiate) when
MIBK is added as a catalyst solvent. Cyclohexanone is used in paint removers,
metal degreasing formulations, printing inks, and as an activator in oxidation
reactions (e.g., benzene oxidation to give phenol). Cyclohexanone is a chemical
intermediate in the manufacture of Nylon 6.
NITROPARAFFINS
Nitroparaffins are commonly referred to as nitroalkanes and are versatile solvents

which have an electronegative nitro (-NO,) group attached to a methane, ethane, or
propane molecule. Attachment of the nitro group is through a bond between the
nitrogen atom and the alkane carbon atom. Nitromethane, nitroethane, 1-
nitropropane, and 2-nitropropane are coln~nercial solvents used in coatings, as
solvents for chemical synthesis work, and as chemical intermediates for a wide
variety of products. The nitroalkanes have unusually high Hansen polarity character
and low hydrogen bonding which can be useful in the solubilization of a large
number of resins. Solvent blends based on the nitroparaffins are useful for
dissolving polyurethane elastomers. Nitromethane is the solvent of choice for u-
cyanoacrylates. The nitroalkanes, which are miscible with aromatic hydrocarbons,
alcohols, esters, and ketones, afford many solvent blends useful in the coating
industry. The nitroalkanes are useful in extractive distillation processes based on
the azeotropes the nitroalkanes form with many industrial solvents. Use of the
nitropropanes in solvent blends result in shorter drying times for flexographic and
gravure inks. Nitroparaffins afford an unique reaction medium for Friedel-Crafts
reactions since these solvents will dissolve Lewis acid catalysts such as anhydrous
aluminum chloride, boron tritluoride, titanium tetrachloride, and stannic
tetrachloride. The role of nitromethane as a metal stabilizer for various
chlorinated and fluorinated solvents involves its ability to complex with metal
salts like aluminuni chloride from the solvent-metal reaction.
Other miscellaneous uses for the nitroalkanes include their use as fuels in racing
cars and model engines, their ability to displace water from metal surfaces during
metallic pigment grinding operations. and as chemical intermediates. The
nitroparaffins produced by the vapor phase nitration of propane or ethane are
available from two United States production facilities: Angus Chemical Company
(Sterling, LA) and W. R. Grace and Company (Deer Park, TX). The nitroalkanes
are named as derivatives of the hydrocarbon with the prefix "nitro." The primary
or secondary position of the nitro group on propane is indicated by the number 1 or
2. The structure of nitromethane is CH,N02, CH,CH,NO, is nitroethane,
CH,CH,CH,NO, is 1-nitropropane, and CH,CH(NOJCH, is 2-nitropropane.
The nitroparaffins are excellent solvents for various resins and polymer com-
positions in the coating industry. Few solvents have the high polarity character and
low hydrogen bonding values shown by the nitroalkanes. Nitromethane is the
TM
DEKKER,
MARCEL INC.
solvent of choice for a-cyanoacrylates. Polyurethane elastomers may be dissolved

easily in solvent blends' containing a nitroparaffin. Improved solvency for resins
and polymer compositions is afforded by the fact that nitroalkanes are miscible with
aromatic hydrocarbons, alcohols, esters, and ketones often used as components in
solvent blends. Nitroparaffins are excellent solvents for use in electrostatic spray
coatings because of their high dielectric constants. Nitropropane is useful for
adjusting the resistivity of coating formulations in order to achieve maximum
electrostatic efficiency. The mid-range evaporation rates (0.88-1.39; n-butyl acetate
= 1.O) of the four nitroalkanes help avoid the coating problems of solvent popping
and blushing which are often caused by faster evaporating solvents. The azeotropes
of nitroalkanes with a wide variety of industrial solvents allow decreased drying
times in flexographic and gravure printing inks. Nitropropane improves the wetting
of pigments during the grinding operation.
Friedel-Crafts reaction catalysts like anhydrous aluminum chloride are readily
soluble in the nitroalkanes. Solutions containing up to 50% aluminum chloride are
easily prepared in nitroalkane solvents. These catalytically active complexes,
AIC1,-RNO,, can be isolated and used in solvents other than the nitroalkane. The
reactants in the Friedel-Crafts reaction are often soluble in the nitroalkane reaction
medium. Other catalysts like boron trifluoride (BF,), titanium tetrachloride (TiCl,),
and stannic tetrachloride (SnCI,) are also soluble in the nitroalkane solvents.
Reaction types which use nitroparaffins as solvents include alkylation of aromatics,
acetylation of aromatics, halogenations, nitrations, and the reaction of olefins and
hydrogen sulfide to yield mercaptans. Nitroparaffins are used with catalysts such as
alkyl-metal (e.g., triethylaluminum, vanadium, or titanium) salts in the
polymerization reactions of alkylene oxides, epichlorohydrin, propylene,
butylene, vinyl chloride, and vinyl ethers. The nitroparaffin acts as an activator
for the catalyst or can serve as the reaction solvent.
The nitroparaffins are used as solvents in separation processes because of their
compatibility with aromatic hydrocarbons, alcohols, esters, ketones, and carboxylic
acids. 2-Nitropropane is used as a crystallization solvent for the separation of oleic
acid from polyunsaturated acids. Cetyl and oleyl alcohols may be separated because
of the lower solubility of cetyl alcohol in the nitropropanes at room temperature.
Nitromethane can be used in an extractive process to separate aromatic
hydrocarbons from aliphatic hydrocarbons due to the lower solubility of the
aliphatic fractions in nitromethane. Nitroparaffins are used to separate lactic acid
from fermentation beers, nitrocellulose from the nitrating solution, and plutonium
(IV) from aqueous solutions. Nitropropane is used to extract rosin from pine
lumber at elevated temperatures. Toluene can be separated from similar boiling
point aliphatic paraffins by azeotropic distillation with nitromethane. Ethylbenzene
forms an azeotrope with nitromethane which allows its separation from styrene
through a distillation process.
The primary and secondary nitroalkanes exist in tautomeric equilibrium with an
"aci" or nitronic acid form.
TM
MARCEL DEKKER, INC.

RCH,NO, = RCH = N02H (aci form)
Many of the reactions involving a nitroalkane will proceed through the "aci"
structure. Nitroalkanes react slowly with strong bases to form the nitronate salt.
Nitromethane reaction with strong bases (e.g., sodium hydroxide) proceeds rapidly
to form the sodium salt of methazonic aci,
2CH,N02 + NaOH = HON=CHCH=NO,Na + 2H,O

The dry sodium methaonate salt is highly shock-sensitive and can explode violently.
Never treat or wash nitromethane with an aqueous basic solution o r solid caustic-
type material. Another hazardous material, mercury fuminate, is formed from the
reaction of the sodium salt of nitromethane with mercuric chloride.
The nitroalcohols are stable at ordinary temperatures, but decompose under heat.
Under alkaline conditions the nitroalcohols release formaldehyde at a rate
dependent on pH and temperature. As a formaldehyde donor the nitroalcohols are
useful with adhesive and foundry resins where a controlled release of formaldehyde
is needed for cross-linking of the resins. Several nitroalcohol products are available
from Angus Chemical Company.
Primary nitroalkanes in the presence of hot concentrated mineral acids yield the
carboxylic acid and hydroxylamine. Exhaustive chlorination of nitromethane under
alkaline conditions yields chloropicrin (trichloronitromethane, CI,CN02).
Secondary nitroparaffins, formaldehyde, and primary or secondary amines react in
a Mannich-type reaction to give the Mannich base.
While nitroparaffins are resistant to oxidation, they are easily reduced to the
corresponding amine. Nitroalkanes can be added across an activated double bond
structure in the presence of a basic catalyst.
Nitroparaffins are not explosives as determined by tests approved by the U.S.
Department of Transportation (DOT) for shipping classifications. However,
nitromethane when sensitized by small amounts of amines can be detonated by a
Number 8 blasting cap. Nitromethane is used as a fuel component in ammonium
nitrate explosives. Nitroparaffins are used in diesel fuel to increase power output of
engines. Nitropropane is completely miscible in diesel fuel, nitroethane solubility is
18 wt%, and nitromethane is only a 2 wt%. Nitromethane is used as a fuel in
racing cars and in model engines. A blend of nitromethane and methanol is said to
produce increased power output over regular hydrocarbon fuels. I-Nitropropane is
used as a grinding solvent for the production of aluminum powder because of its
ability to displace surface moisture on the aluminum and the solvent aids in the
dispersion of the aluminum powder. Nitromethane is used as a metal stabilizer for
TM
MARCEL
DEKKER,
INC.
various chlorinated and fluorinated hydrocarbon solvents. The primary role of the
nitromethane is to complex the metal salt from the solvent-metal corrosion reaction.
Each nitroalkane solvent has distinct physical and chemical properties as well as
specific toxicology characteristics. Specific toxicology information on a nitroalkane
solvent is available in the solvent's MSDS and from the solvent producer. The most
common health and overexposure hazard of these solvents is due to vapor
inhalation. Overexposure may produce an anesthetic effect and depression of the
central nervous system, and is characterized by dizziness, loss of coordination, and
the feeling of being lightheaded. A rapid reversal of the anesthetic effects occurs
when the individual moves out of the area of exposure. Entrance into an area of
high vapor concentrations of any organic solvent (e.g., an unventilated storage
tank) can quickly lead to unconsciousness and death through respiratory failure.
Specific safe tank entry instructions are available from the solvent producers. The
American Conference of Governmental Industrial Hygienists (ACGIH guidebook
1994-1995) have recommended a Threshold Limit Value (TLV) of 20 ppm for
nitromethane, 100 ppm for nitroethane, 25 ppm for 1-nitropropane, and 10 ppm for
2-nitropropane. The United States Occupational Safety and Health Administration
(OSHA) also sets vapor exposure limits for solvents which may or may not be the
same values set by the ACGIH organization.' These allowable vapor exposure
values should be included in solvent's MSDS. Other routes of solvent overexposure
include ingestion, skin, and eye contact. The use of the proper chemical gloves as
recommended in the MSDS should be considered if prolonged skin exposure is
possible. The nitroalkanes will remove natural oils from the skin and cause
irritation of the skin and possible dermatitis. Nitrobenzene has a 1 ppm allowable
TLV (ACGIH guidebook 1994-1995) based on the real danger of absorption of
nitrobenzene through the skin. Gloves of the material recommended on the MSDS
of nitrobenzene must be worn when handling the solvent. Chemical workers
goggles or safety glasses with side shields should be worn when handling any
solvent.
MISCELLANEOUS SOLVENTS
Two important sulfur-containing solvents are dimethyl sulfoxide (DMSO) and

sulfolane, and two nitrogen-containing solvents are pyrrole and aniline. Dimethyl
sulfoxide, a product of an oxidation reaction on dimethyl sulfide, contains a very
polar sulfoxide functional group. This highly polar functional group enables DMSO
to form complexes with many metal ions, to act as a reaction medium for synthetic
reactions, and to dissolve a large number of organic resins and polymers.
Sulfolane is the most common commercially available sulfone solvent. The solvent,
also known as tetrahydrothiophene-1,l-dioxide,is a colorless, highly polar liquid
consisting of a fully hydrogenated five-member sulfur-carbon heterocyclic
thiophene ring. The solvent is available as both anhydrous sulfolane and as
sulfolane containing 3 wt% deionized water. Sulfolane is used as a reaction
TM
MARCEL DEKKER, INC.

medium, as a solvent for a wide variety of organic chemicals and polymers, and as
an extraction solvent.
Pyrrole is a five-member nitrogen heterocyclic ring that contains two carbon-carbon
double bond configurations which gives the solvent a pronounced aromatic
character. Pyrrole is an intermediate in the synthesis of a variety of commercial
chemical derivatives.
Aniline, the simplest primary aromatic arnine, consists of a nitrogen atom with two
attached hydrogen atoms affixed to a benzene ring. This aromatic amine is a
weaker base than the aliphatic amines but aniline does undergo many of the same
reactions in the realm of synthetic chemistry. Aniline is used to prepare agricultural
chemicals, antioxidants, fungicides, herbicides, isocyanates, and other
commercially important chemicals. This chapter discusses the naming nomenclature
for the four organic solvents, their physical properties, the various industrial uses,
possible environmental concerns, and the safe handling of these solvents.
The CA index name (Chemical Abstract Index, American Chemical Society) for
DMSO is sulfinylbismethane, sulfolane is tetrahydrothiophene-1 ,1-dioxide, while
pyrrole and aniline retain the same names under the CA index naming system.
The two sulfur heterocyclic solvents, DMSO and sulfolane, are high boiling point
liquids which are both miscible in water. Dimethyl sulfoxide is more viscous than
many organic solvents and has a rather high surface tension value of 42.3
dyneslcm. The most outstanding property of DMSO is its very high polarity
character. Sulfolane is a very high boiling point, colorless liquid with a very high
viscosity (10.3 centipoises) and medium surface tension value (35.5 dyneslcm). Al-
though the structure and reactions of sulfolane show the molecule to be very polar
in nature, no Hansen solubility parameters have been reported in the literature for
this solvent. Sulfolane is miscible with water and many organic solvents. The two
nitrogen-containing solvents, pyrrole and aniline, both have only limited solubility
in water but are miscible with many organic solvents. Pyrrole when freshly distilled
is a colorless liquid, but the solvent can rapidly acquire a brown coloration due to
air oxidation. Prolonged standing in the air will promote slow polymerization of the
pyrrole to give a dark brown polymer. Pyrrole has a viscosity of 1.31 centipoise
and a medium surface tension value of 37.1 dyneslcm, while aniline has a much
higher viscosity of 3.75 centipoise and a higher surface tension of 42.0 dyneslcm.
The aromatic primary arnine has a medium Hansen polarity value of 5.1 and a
high hydrogen bonding character of 10.2.
Dimethyl sulfoxide is used as a reaction solvent in the polymerization of
acrylonitrile with a vinyl monomer (e.g., styrene). Reaction of diisocyanates and
polyols or polyamines dissolved in DMSO yield solutions of the polyurethanes.
Mixtures of DMSO and water are used as a spinning solvent for polymer fibers.
Polyaryl ether polymers are formed from DMSO solutions containing the reactants
bis(4,4-chlorophenyl sulfone) and the disodium salt of dihydroxyphenol.
Dimethyl sulfoxide is a favored solvent for displacement reactions in synthetic
TM
MARCEL DEKKER, INC.

chemistry. The rates of reaction in DMSO are many times faster than in an alcohol
or aqueous medium. Dimethyl sulfoxide is the solvent of choice in reactions where
proton (hydrogen atom) removal is the rate determining step. Reactions of this type
include olefin isomerizations and reactions where an elimination process produces
an olefin. Another application that uses DMSO is its use as an extraction solvent to
separate olefins from saturated paraffins. Several binary and ternary solvent
systems containing DMSO and an amine (e.g., methylamine), sulfur trioxide,
carbon disulfidelamine, or sulfur trioxidelammonia are used to dissolve cellulose,
and act as spinning baths for the production of cellulose fibers. Organic fungicides,
insecticides, and herbicides are readily soluble in DMSO. Dimethyl sulfoxide is
used to remove polymer residues from polymerization reactors.
Sulfolane, another highly polar solvent, is used to separate aromatic hydrocarbons
from aliphatic hydrocarbons. The extraction process first developed by Shell Oil in
1959 and which is referred to as the "Sulfolane" process is used worldwide. The
solvency of sulfolane for certain fatty acids and fatty acid esters is the basis for
upgrading animal and vegetable fatty acids used in food products, paints, plastics,
resins, and soaps. Aqueous solutions containing 30-70 wt% sulfolane are used to
remove lignin from wood chips. Sulfolane is used to remove acidic components like
hydrogen sulfide and carbon dioxide from gas feed stocks. Sulfolane is used as a
polymerization solvent for the production of polysulfones, polysiloxanes,
polyphenylene ethers, and other polymers. Sulfolane is said to increase the
reaction rates, afford easier polymer purification, and improved thermal stability.
Sulfolane is a solvent for dissolving a variety of polymers for use in the fiber-
spinning process. Cellulose and cellulose ester polymers can be plasticized with
sulfolane to give improved flexibility and other physical property improvements.
Other application areas that have used sulfolane include electronic and electrical
uses, textile dye uses, curing of polysulfide sealant, and as a catalyst in certain
synthetic reactions.
Aniline is used as a chemical intermediate to prepare isocyanates for making poly-

urethanes, antioxidants, and vulcanization accelerators, as well as in the manu-
facture of agricultural fungicides, herbicides and insecticides and in the preparation
of certain dyes. Similarly, pyrrole is used as a chemical intermediate in the
preparation of electrically conducting polypyrrole by means of an electrochemical
polymerization process. Pyrrole has few other industrial uses.
Water
Water is a unique solvent with many unusual physical properties such as its very
high heat of vaporization of 539.7 callg as measured at the boiling point. The
properties and nature of water are due largely to the strong intramolecular
hydrogen bonding within the water molecule and intermolecular hydrogen bonding
between water molecules. The high boiling point and very high heat of vaporization
is due to the intermolecular hydrogen bonding between water molecules. As a
TM
MARCEL DEKKER, INC.

comparison, consider the higher molecular weight sulfur analog of water, hydrogen
sulfide (H,S), which is a gas at room temperature (boiling point = -60.8"C) and
which has much lower heat of vaporization (130.8 callg). Any intramolecular
hydrogen bonding between the hydrogens and sulfur atom in hydrogen sulfide is
minimal and does not affect the compound's physical properties. Without the
hydrogen bonding phenomenon water would exist in the gaseous state at room
temperature. The solubility parameters of water are important where water is the
principal solvent in latex and water reducible coatings and in many cleaning
formulations. The literature has reported considerable variations in the water
solubility parameters. Many references report very high values for the hydrogen-
bonding character of water. Similarly, polarity values of 16-31 have been
reported for water. Water in the presence of miscible organic solvents might
display less polarity and hydrogen bonding character. The organic solvents would
partially break up the strong intermolecular hydrogen-bonding between water
molecules.
TM
MARCEL INC.
DEKKER,

Dke345 Sec1

Uploaded by

Copyright:

Available Formats

You might also like

Dke345 Sec1

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Dke345 Sec1

Uploaded by

Copyright:

Available Formats

SECTION 1

INDUSTRIAL ORGANIC SOLVENTS

Alcohols contain a hydroxyl functional group (-CH,OH). Monohydric alcohols are

a primary carbon atom (RCH,OH),

An important cyclic alcoholic solvent is cyclohexanol. An important aromatic

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

Ethylene glycol, CH,0HCH20H, is the most important dihydric alcohol and

Common names for alcohols are Methanol, Ethanol, Isopropanol, n-Butanol,

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

Table 1. Nomenclature for Common Alcohols

Table 2. Alcohol and Water Azeotropes

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

Alochol Azeotrope Boiling Point Weight Percent Water

Table 3. Alcohol Evaporation Rates (relative to rz-Butyl Acetate; i.e., n-Butyl

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

Table 4. General Physical Properties of Alcohol Solvents

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

MARCEL DEKKER, INC.

Table 5. Solubilitv Data

n-Octyl alcohol 0.06 3.4

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

MARCEL DEKKER, INC.

Formaldehyde - Methanol is also used as a raw material for producing

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

1,4 Butanediol is used in the production of tetrahydrofuran, a solvent used

Formaldehyde is also used in the manufacture of methylene di-para-phenylene

Markets and Miscellaneous lrlfornzation - Methanol is methyl alcolzol and at the

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

in one complex by using CO,, which is produced from an ammonia plant to

The single largest use of methanol is in formaldehyde and dimethyl terephthalate

Manufacture - Most of world methanol is manufactured from natural gas by a steam

Methanol production economics highly depend on the feedstock selection and

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

MARCEL DEKKER, INC.

CH,OH = HCHO + H,O

If the oxidizing agent is in excess, the formaldehyde is further oxidized to formic

Dehydrogerzation - Methanol can also be oxidized to formaldehyde by passing its

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

Dehydration - Methanol does not undergo dehydration reactions. Instead, in

CH,OH + HCOOH = HCOOCH, + H,O

Substitution of Methanol with Phosphorus Pentachloride - Methanol reacts with

Ethanol is a monohydric primary alcohol. It melts at -1 17.3"C and boils at 78.5"C.

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

Ethanol is used extensively as a solvent in the manufacture of varnishes and

Methylated Spirits - This a very common industrial solvent, used in many

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

Both alcohols are poisonous in such quantities, so a purple dye is added to

After-Shaves, Perfumes and Cosmetics - The active ingredients (usually

Manufacture - Ethyl alcohol is derived from two main processes, hydration of

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved. 8

C,H,>O, (in preseilce of qcast) = 2CH,CH20H + 2C0,

Distillation is a process that uses differences in boiling points to separate

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.

mash will be allowed to flow, or cascade, through several fermenters until

Co-Products: There are two main co-products created in the production of

11-Propanol is a chemical intermediate used in the synthesis of n-propyl amines and

Copyright n 2003 by Marcel Dekker, Inc. All Rights Reserved.