1
1
1
pdf
http://www.who.int/ipcs/publications/cicad/en/cicad58.pdf
http://en.wikipedia.org/wiki/Chloroform
http://en.wikipedia.org/wiki/Sodium_hydroxide
http://nj.gov/health/eoh/rtkweb/documents/fs/1706.pdf
http://www.nicnas.gov.au/publications/information_sheets/existing_chemical_informatio
n_sheets/ecis_naoh_pdf.pdf
http://motion.kodak.com/motion/uploadedFiles/US_plugins_acrobat_en_motion_support
_processing_h244_sodiHydr.pdf
Sodium hydroxide
From Wikipedia, the free encyclopedia
Jump to: navigation, search
Sodium hydroxide
IUPAC name[hide]
Sodium hydroxide
Systematic name[hide]
Sodium oxidanide
Other names[hide]
Caustic soda
Lye
Identifiers
CAS number 1310-73-2
PubChem 14798
ChemSpider 14114
UNII 55X04QC32I
EC number 215-185-5
UN number 1823
KEGG C12569
MeSH Sodium+hydroxide
ChEBI CHEBI:32145
RTECS number WB4900000
Gmelin Reference 68430
SMILES
[show]
InChI
[show]
Properties
Molecular formula NaOH
Exact mass 39.992509329 g mol−1
Appearance White opaque crystals
Density 2.13 g cm−3
Melting point 318 °C, 591 K, 604 °F
Boiling point 1388 °C, 1661 K, 2530 °F
Solubility in water 1110 g dm−3 (at 20 °C)
Solubility in methanol 238 g dm−3
Solubility in ethanol <<139 g dm−3
Vapor pressure <18 mmHg (at 20 °C)
Acidity (pKa) 13
Refractive index (nD) 1.412
Hazards
MSDS External MSDS
EU Index 011-002-00-6
EU classification
C
R-phrases R35
S-phrases (S1/2), S26, S37/39, S45
NFPA 704 0
3
1
COR
Related compounds
Other anions Sodium hydrosulfide
Caesium hydroxide
Sodium hydroxide (NaOH), also known as lye and caustic soda, is a caustic metallic
base. It is used in many industries, mostly as a strong chemical base in the manufacture of
pulp and paper, textiles, drinking water, soaps and detergents and as a drain cleaner.
Worldwide production in 2004 was approximately 60 million tonnes, while demand was
51 million tonnes.[1]
Pure sodium hydroxide is a white solid available in pellets, flakes, granules, and as a 50%
saturated solution. It is hygroscopic and readily absorbs water from the air, so it should
be stored in an airtight container. It is very soluble in water with liberation of heat. It also
dissolves in ethanol and methanol, though it exhibits lower solubility in these solvents
than does potassium hydroxide. Molten sodium hydroxide is also a strong base, but the
high temperature required limits applications. It is insoluble in ether and other non-polar
solvents. A sodium hydroxide solution will leave a yellow stain on fabric and paper.
Contents
[hide]
• 1 Properties
• 2 Reactions
• 3 Production
o 3.1 Chloralkali electrolysis
• 4 Uses
o 4.1 pH regulation
o 4.2 Paper making
o 4.3 Tissue digestion
o 4.4 Dissolving amphoteric metals and compounds
o 4.5 Esterification and transesterification reagent
o 4.6 Cleaning agent
o 4.7 Food preparation
o 4.8 Domestic uses
• 5 Safety
• 6 See also
• 7 References
• 8 Bibliography
• 9 External links
Properties
Sodium hydroxide is predominantly ionic, containing sodium cations and hydroxide
anions. The hydroxide anion makes sodium hydroxide a strong base which reacts with
acids to form water and the corresponding salts.
ΔH°dissolution for aqueous dilution is −44.45 kJ / mol; from aqueous solutions at 12.3–61.8
°C, it crystallizes in monohydrate, with a melting point 65.1 °C and density of 1.829
g/cm3. The standard enthalpy change of formation (ΔH°form) is −734.95 kJ / mol.
Reactions
With acids
Sodium hydroxide reacts with protic acids to give water and the corresponding salts. For
example, with hydrochloric acid, sodium chloride is formed:
In general such neutralization reactions are represented by one simple net ionic equation:
This type of reaction with a strong acid releases heat, and hence is referred to as
exothermic. Such acid-base reactions can also be used for titrations. However, sodium
hydroxide is not used as a primary standard because it is hygroscopic and absorbs carbon
dioxide from air.
Sodium hydroxide reacts readily with carboxylic acids to form their salts and is even a
strong enough base to form salts with phenols. It is not, however, strong enough the
quantitatively produce enolates from carbonyl compounds or deprotonate amines; this
would require a superbase.
Sodium hydroxide also reacts with acidic oxides, such as sulfur dioxide. Such reactions
are often used to "scrub" harmful acidic gases (like SO2 and H2S) produced in the burning
of coal and thus prevent their release into the atmosphere. For example,
Sodium hydroxide slowly reacts with glass to form sodium silicate, so glass joints and
stopcocks exposed to NaOH have a tendency to "freeze". Flasks and glass-lined chemical
reactors are damaged by long exposure to hot sodium hydroxide, and the glass becomes
frosted. Sodium hydroxide does not attack iron since iron does not have amphoteric
properties (i.e., it only dissolves in acid, not base). A few transition metals, however, may
react vigorously with sodium hydroxide.
In 1986, an aluminium road tanker in the UK was mistakenly used to transport 25%
sodium hydroxide solution[citation needed], causing pressurization of the contents and damage
to the tanker. The pressurization was due to the hydrogen gas which is produced in the
reaction between sodium hydroxide and aluminium:
Unlike NaOH, the hydroxides of most transition metals are insoluble, and therefore
sodium hydroxide can be used to precipitate transition metal hydroxides.
NaOH can be used for the base-driven hydrolysis of esters (as in saponification), amides
and alkyl halides. However, the limited solubility of NaOH in organic solvents means
that the more soluble KOH is often preferred.
Electrolysis
In the laboratory, with careful control of conditions, sodium metal can be isolated from
the electrolysis of the molten monohydrate according to the following reaction:
The monohydrate does not need to be heated in order to melt, as the process produces
enough heat due to ohmic heating. However, it must be initiated with a small quantity of
liquid water to create an electrically conductive electrolyte. As the system's temperature
increases, the monohydrate will start to melt at about 65 °C as stated above. Only when
the temperature reaches about 100 °C can sodium be isolated. Below this temperature, the
water produced will react with the sodium, above this point, any water formed will be
driven off in the vapour phase, creating an essentially anhydrous reaction. While this
process has some advantages over other electrolytic processes, it is not preferred by most
chemists for several reasons: a marginal quantity of sodium produced boils at the
electrode interface, the vapour thus given off consists primarily of fumed sodium oxide,
which tends to settle on any surface in close proximity with corrosive consequences.
Production
Sodium hydroxide is industrially produced as a 50 % solution by variations of the
electrolytic chloralkali process. Chlorine gas is also produced in this process. Solid
sodium hydroxide is obtained from this solution by the evaporation of water. Solid
sodium hydroxide is most commonly sold as flakes, prills, and cast blocks.[1]
In 2004, world production was estimated at 60 million dry metric tonnes of sodium
hydroxide, and demand was estimated at 51 million tonnes.[1] In 1998, total world
production was around 45 million tonnes. North America and Asia collectively
contributed around 14 million tonnes, while Europe produced around 10 million tonnes.
In the United States, the major producer of sodium hydroxide is the Dow Chemical
Company, which has annual production around 3.7 million tonnes from sites at Freeport,
Texas, and Plaquemine, Louisiana. Other major US producers include Oxychem, PPG,
Olin, Pioneer Companies (which was purchased by Olin), Inc. (PIONA), and Formosa.
All of these companies use the chloralkali process.[2]
Of historic interest is the Leblanc process, which produced sodium carbonate, followed
by roasting to create carbon dioxide and sodium oxide, which readily absorbs water to
create sodium hydroxide. This method is still occasionally used. It helped establish
sodium hydroxide as an important commodity chemical. The Leblanc process was
superseded by the Solvay process in the late 19th century.
Chloralkali electrolysis
Sodium hydroxide is produced (along with chlorine and hydrogen) via the chloralkali
process. This involves the electrolysis of an aqueous solution of sodium chloride. The
sodium hydroxide builds up at the cathode, where water is reduced to hydrogen gas and
hydroxide ion:
More accurately:
2 Na+Cl– + 2 H2O + 2 e– → H2 + 2 Cl– + 2 NaOH
To produce NaOH it is necessary to prevent reaction of the NaOH with the chlorine. This
is typically done in one of three ways, of which the membrane cell process is
economically the most viable.
• Mercury cell process (also called the Castner-Kellner process); sodium ions are
reduced to sodium metal, which forms an amalgam with a mercury cathode; this
sodium is then reacted with water to produce NaOH. There have been concerns
about mercury releases, although modern plants claim to be safe in this regard.[4]
• Diaphragm cell process; uses a steel cathode, and the reaction of NaOH with Cl2
is prevented using a porous diaphragm, often made of asbestos fibers. In the
diaphragm cell process the anode area is separated from the cathode area by a
permeable diaphragm. The brine is introduced into the anode compartment and
flows through the diaphragm into the cathode compartment. A diluted caustic
brine leaves the cell. The sodium hydroxide must usually be concentrated to 50%
and the salt removed. This is done using an evaporative process with about three
tonnes of steam per tonne of sodium hydroxide. The salt separated from the
caustic brine can be used to saturate diluted brine. The chlorine contains oxygen
and is purified by liquefaction and evaporation.[5][6]
• Membrane cell process; similar to the diaphragm cell process, with a Nafion
membrane to separate the cathode and anode reactions. Only sodium ions and a
little water pass through the membrane. It produces a higher quality of NaOH. Of
the three processes, the membrane cell process requires the lowest consumption of
electric energy and the amount of steam needed for concentration of the caustic is
relatively small (less than one tonne per tonne of sodium hydroxide).[5][7]
Uses
pH regulation
Sodium hydroxide is used in all sorts of scenarios where it is desirable to increase the
alkalinity of a mixture, or to neutralize acids.
In the same industry, poor quality crude oil can be treated with sodium hydroxide to
remove sulfurous impurities in a process known as caustic washing. As above, sodium
hydroxide reacts with weak acids such as hydrogen sulfide and mercaptans to give the
non-volatile sodium salts which can be removed. The waste which is formed is toxic and
difficult to deal with, and the process is banned in many countries because of this. In
2006, Trafigura used the process and then dumped the waste in Africa.[8][9]
Paper making
Sodium hydroxide was also widely used in making paper. Along with sodium sulfide,
NaOH is a key component of the white liquor solution used to separate lignin from
cellulose fibers in the Kraft process. It also plays a key role in several later stages of the
process of bleaching the brown pulp resulting from the pulping process. These stages
include oxygen delignification, oxidative extraction, and simple extraction, all of which
require a strong alkaline environment with a pH > 10.5 at the end of the stages.
Tissue digestion
In a similar fashion, sodium hydroxide is used to digest tissues, such as in a process that
was used with farm animals at one time. This process involves the placing of a carcass
into a sealed chamber, which then puts the carcass in a mixture of sodium hydroxide and
water, which breaks chemical bonds keeping the body intact. This eventually turns the
body into a coffee-like[10][11] liquid, and the only solid that remains are bone hulls, which
could be crushed between one's fingertips.[12] Sodium hydroxide is frequently used in the
process of decomposing roadkill dumped in landfills by animal disposal contractors.[11]
Sodium hydroxide has also been used by criminals to dispose of their victims' bodies.[13]
Strong bases attack aluminium. Sodium hydroxide reacts with aluminium and water to
release hydrogen gas. The aluminium takes the oxygen atom from sodium hydroxide
(NaOH), which in turn takes the oxygen atom from the water, and releases the two
hydrogen atoms. In this reaction, sodium hydroxide acts as an agent to make the solution
alkaline, which aluminium can dissolve in. This reaction can be useful in etching,
removing anodizing, or converting a polished surface to a satin-like finish, but without
further passivation such as anodizing or alodining the surface may become degraded,
either under normal use or in severe atmospheric conditions.
In the Bayer process, sodium hydroxide is used in the refining of alumina containing ores
(bauxite) to produce alumina (aluminium oxide) which is the raw material used to
produce aluminium metal via the electrolytic Hall-Héroult process. Since the alumina is
amphoteric, it dissolves in the sodium hydroxide, leaving impurities less soluble at high
pH such as iron oxides behind in the form of a highly alkaline red mud.
For the manufacture of biodiesel, sodium hydroxide is used as a catalyst for the
transesterification of methanol and triglycerides. This only works with anhydrous sodium
hydroxide, because combined with water the fat would turn into soap, which would be
tainted with methanol. It is used more often than potassium hydroxide because it is
cheaper and a smaller quantity is needed.
Cleaning agent
A common use of sodium hydroxide is in the production of parts washer detergents. Parts
washer detergents based on sodium hydroxide are some of the most aggressive parts
washer cleaning chemicals. The sodium hydroxide based detergent include surfactants,
rust inhibitors and defoamers. A parts washer heats water and the detergent in a closed
cabinet and then sprays the heated sodium hydroxide and hot water at pressure against
dirty parts for degreasing applications. Sodium hydroxide used in this manner replaced
many solvent based systems in the early 1990s[citation needed] when trichloroethane was
outlawed by the Montreal Protocol. Water and sodium hydroxide detergent based parts
washers are considered to be an environmental improvement over the solvent based
cleaning methods.
Food preparation
Food uses of sodium hydroxide include washing or chemical peeling of fruits and
vegetables, chocolate and cocoa processing, caramel coloring production, poultry
scalding, soft drink processing, and thickening ice cream. Olives are often soaked in
sodium hydroxide to soften them, while pretzels and German lye rolls are glazed with a
sodium hydroxide solution before baking to make them crisp. Owing to the difficulty in
obtaining food grade sodium hydroxide in small quantities for home use, sodium
carbonate is often used in place of sodium hydroxide.[15]
• The Pinoy or Filipino dessert (kakanin) called kutsinta uses a bit of lye water to
help give the rice flour batter a jelly like consistency.
• A similar process is also used in the kakanin known as pitsi-pitsi or pichi-pichi
(pit-chi-pit-chi) except that the mixture uses grated cassava instead of rice flour.
• The Scandinavian delicacy known as lutefisk (from lutfisk, "lye fish").
• Hominy is dried maize (corn) kernels reconstituted by soaking in lye-water. These
expand considerably in size and may be further processed by frying to make corn
nuts or by drying and grinding to make grits. Nixtamal is similar, but uses calcium
hydroxide instead of sodium hydroxide.
• Sodium hydroxide is also the chemical that causes gelling of egg whites in the
production of Century eggs.
• German pretzels are poached in a boiling sodium carbonate solution or cold
sodium hydroxide solution before baking, which contributes to their unique crust.
• Most yellow coloured Chinese noodles are made with lye-water but are
commonly mistaken for containing egg.
Domestic uses
Hardware store grade NaOH to be used as drain cleaner
Sodium hydroxide is used in the home as a drain cleaning agent for clearing clogged
drains. It is distributed as a dry crystal or as a thick liquid gel. The chemical mechanism
employed is the conversion of grease to a form of soap. Soap is water-soluble, and can be
dissolved by flushing with water. This conversion occurs far more rapidly at high
temperatures, so commercial drain cleaners may also contain chemicals that react with
water to generate heat. Sodium hydroxide also decomposes complex molecules such as
the protein that composes hair. Such drain cleaners (and their acidic versions) are highly
caustic and should be handled with care.
Sodium hydroxide has been used as a relaxer to straighten hair. However, because of the
high incidence and intensity of chemical burns, chemical relaxer manufacturers have now
switched to other alkaline chemicals. Sodium hydroxide relaxers are still available, but
they are used mostly by professionals.
A solution of sodium hydroxide in water was traditionally used as the most common
paint stripper on wooden objects. Its use has become less common, because it can
damage the wood surface, raising the grain and staining the colour.
Safety
Solid sodium hydroxide and solutions of more than 2% by weight (0.5 M) should be
labeled as corrosive.
Solid sodium hydroxide or solutions of sodium hydroxide may cause chemical burns,
permanent injury or scarring if it contacts unprotected human, or other animal, tissue. It
may cause blindness if it contacts with the eye. Protective equipment such as rubber
gloves, safety clothing and eye protection should always be used when handling the
material or its solutions.
Dissolution of sodium hydroxide is highly exothermic, and the resulting heat may cause
heat burns or ignite flammables. It also produces heat when reacted with acids. Sodium
hydroxide is corrosive to some metals, e.g. aluminum, which produces flammable
hydrogen gas on contact. Sodium hydroxide is also mildly corrosive to glass, which can
cause damage to glazing or freezing of ground glass joints
Chloroform
From Wikipedia, the free encyclopedia
Jump to: navigation, search
Chloroform
IUPAC name[hide]
Chloroform
Systematic name[hide]
Trichloromethane
Other names[hide]
Formyl trichloride, Methane trichloride, Methyl trichloride,
Methenyl trichloride, TCM, Freon 20, R-20, UN 1888
Identifiers
CAS number 67-66-3
PubChem 6212
ChemSpider 5977
UNII 7V31YC746X
EC number 200-663-8
KEGG C13827
ChEBI CHEBI:35255
ChEMBL CHEMBL44618
RTECS number FS9100000
SMILES
[show]
InChI
[show]
Properties
Molecular formula CHCl3
Molar mass 119.38 g/mol
Appearance Colorless liquid
Density 1.483 g/cm3
Melting point -63.5 °C
Boiling point 61.2 °C
Solubility in water 0.8 g/100 ml (20 °C)
Refractive index (nD) 1.4459
Structure
Molecular shape Tetrahedral
Hazards
MSDS External MSDS
R-phrases R22, R38, R40, R48/20/22
S-phrases (S2), S36/37
NFPA 704
0
2
0
Flash point Non-flammable
U.S. Permissible
50 ppm (240 mg/m3) (OSHA)
exposure limit (PEL)
Supplementary data page
Structure and
n, εr, etc.
properties
Thermodynamic Phase behaviour
data Solid, liquid, gas
Spectral data UV, IR, NMR, MS
(what is this?) (verify)
Except where noted otherwise, data are given for materials in
their standard state (at 25 °C, 100 kPa)
Infobox references
Chloroform is the organic compound with formula CHCl3. The colorless, sweet-
smelling, dense liquid is a trihalomethane, and is considered somewhat hazardous.
Several million tons are produced annually as a precursor to Teflon and refrigerants, but
its use for refrigerants is being phased out.[1]
Contents
[hide]
• 1 Occurrence
o 1.1 Marine
• 2 Production
o 2.1 Industrial routes
o 2.2 Deuterochloroform
o 2.3 Inadvertent formation of chloroform
• 3 Uses
o 3.1 As a solvent
o 3.2 As a reagent in organic synthesis
o 3.3 As an anesthetic
o 3.4 Veterinary use
• 4 Safety
o 4.1 Conversion to phosgene
• 5 References
• 6 External links
Occurrence
CHCl3 has a multitude of natural sources, both biogenic and abiotic. It is estimated that
greater than 90% of atmospheric CHCl3 is of natural origin.[2]
Marine
Production
Chloroform was discovered by three researchers independently of one another.
Chloroform was reported in 1831 by the French chemist Eugène Soubeiran, who
prepared it from acetone (2-propanone) as well as ethanol through the action of chlorine
bleach powder (calcium hypochlorite).[9] The American physician Samuel Guthrie
prepared gallons of the material and described its "deliciousness of flavor."[10]
Independently, Justus von Liebig also described the same compound.[11] All early
preparations used variations of the haloform reaction. Chloroform was named and
chemically characterized in 1834 by Jean-Baptiste Dumas.[12]
Industrial routes
Deuterochloroform
An archaic industrial route to chloroform involved the reaction of acetone (or ethanol)
with sodium hypochlorite or calcium hypochlorite, the aforementioned haloform reaction.
[1]
The chloroform can be removed from the coproducts by distillation. A related reaction
is still used in the production of bromoform and iodoform. Although the haloform
process is obsolete for the production of ordinary chloroform, it is used to produce
CDCl3.[citation needed] Deuterochloroform can also be prepared by the reaction of sodium
deuteroxide with chloral hydrate,[citation needed] or from ordinary chloroform.[13]
The haloform reaction can also occur inadvertently in domestic settings. Sodium
hypochlorite solution (chlorine bleach) mixed with common household liquids such as
acetone, butanone, ethanol, or isopropyl alcohol can produce some chloroform, in
addition to other compounds such as chloroacetone, or dichloroacetone.
Uses
The major use of chloroform today is in the production of the chlorodifluoromethane (R-
22), a major precursor to tetrafluoroethylene:
As a solvent
As an anesthetic
Chloroform was once a popular anesthetic; its vapor depresses the central nervous system
of a patient, allowing a doctor to perform various otherwise painful procedures. In 1847,
the Scottish obstetrician James Young Simpson first used chloroform for general
anesthesia during childbirth. The use of chloroform during surgery expanded rapidly
thereafter in Europe. In the United States, chloroform began to replace ether as an
anesthetic at the beginning of the 20th century; however, it was quickly abandoned in
favor of ether upon discovery of its toxicity, especially its tendency to cause fatal cardiac
arrhythmia analogous to what is now termed "sudden sniffer's death". Ether is still the
preferred anesthetic in some developing nations due to its high therapeutic index (~1.5–
2.2) [17] and low price. One possible mechanism of action for chloroform is that it
increases movement of potassium ions through certain types of potassium channels in
nerve cells.[18] Chloroform could also be mixed with other anaesthetic agents such as
ether to make C.E. mixture, or ether and alcohol to make A.C.E. mixture.
Veterinary use
As might be expected for an anesthetic, chloroform vapors depress the central nervous
system. It is immediately dangerous to life and health at approximately 500 ppm,
according to the U.S. National Institute for Occupational Safety and Health. Breathing
about 900 ppm for a short time can cause dizziness, fatigue, and headache. Chronic
chloroform exposure can damage the liver (where chloroform is metabolized to
phosgene) and to the kidneys, and some people develop sores when the skin is immersed
in chloroform.
Animal studies have shown that miscarriages occur in rats and mice that have breathed
air containing 30 to 300 ppm of chloroform during pregnancy and also in rats that have
ingested chloroform during pregnancy. Offspring of rats and mice that breathed
chloroform during pregnancy have a higher incidence of birth defects, and abnormal
sperm have been found in male mice that have breathed air containing 400 ppm
chloroform for a few days. The effect of chloroform on reproduction in humans is
unknown.
Conversion to phosgene