Phosgene:

At room temperature (70F), phosgene is a poisonous gas.

With cooling and pressure, phosgene gas can be converted into a liquid so that it
can be shipped and stored. When liquid phosgene is released, it quickly turns into
a gas that stays close to the ground and spreads rapidly

Phosgene can be formed when chlorinated hydrocarbon compounds are exposed

to high temperatures. Chlorinated hydrocarbon compounds are substances
sometimes used or created in industry that contain the elements chlorine,
hydrogen, and carbon.

The vapors of chlorinated solvents exposed to high temperatures have been

known to produce phosgene. Chlorinated solvents are chlorine-containing
chemicals that are typically used in industrial processes to dissolve or clean other
materials, such as in paint stripping, metal cleaning, and dry cleaning.

COCl2.

Industrially, phosgene is produced by passing purified carbon monoxide and

chlorine gas through a bed of highly porous carbon, which acts as a catalyst. The
chemical equation for their reaction is CO + Cl2 COCl2

The reaction is exothermic, i.e. the reactor must be cooled to carry away the heat
it produces. Typically, the reaction is carried out between 50C and 150C. Above
200C, phosgene decomposes back into carbon monoxide and chlorine. Upon
ultraviolet radiation in the presence of oxygen, chloroform forms significant
amounts of phosgene via a radical reaction. Brown glass flasks for chloroform
prevent this reaction.

Phosgene is produced by reacting equimolar amounts of carbon monoxide and

anhydrous chlorine in the presence of a carbon catalyst under appropriate
conditions of temperature and pressure. The great majority is used directly in
closed systems on-site.

Phosgene is used as an intermediate in the manufacture of many organic

chemicals. The largest amount (approximately 80% of world production) is used
to produce toluene diisocyanate and other isocyanates used in polyurethane foam
production, preparation of plastics, and pesticides. Accurate production figures are

hard to determine since over 99% of phosgene production is "used on site".

Approximately 3106 tonnes of phosgene are used annually worldwide.
Hydrogen Cyanide:

Hydrogen cyanide is manufactured by oxidation of ammonia- methane mixtures

under controlled conditions and by the catalytic decomposition of formamide. It
may be generated by treating cyanide salts with acid, and it is a combustion byproduct of nitrogen-containing materials such as wool, silk, and plastics and as a
fumigant to kill rats. It is also used in electroplating metals and in developing
photographic film. It is also produced by enzymatic hydrolysis of nitriles and
related chemicals. Hydrogen cyanide gas is a by-product of coke-oven and blastfurnace operations

Hydrogen cyanide is used in fumigating; electroplating; mining; and in producing

synthetic fibers, plastics, dyes, and pesticides. It also is used as an intermediate in
chemical syntheses NIOSH IDLH (immediately dangerous to life or health) = 50
ppm

NIOSH IDLH (immediately dangerous to life or health) = 50 ppm

Molecular weight: 27.03 daltons

Boiling point (760 mm Hg): 78F (25.6C)

Freezing point: 8F (-13.4C)

Specific gravity (liquid): 0.69 (water = 1)

Vapor pressure: 630 mm Hg at 68F (20C)

Gas density: 0.94 (air = 1)

Water solubility: Flammable at temperatures >0F (-18C)

Flammability: flammable limits 3.9% to 21.8% at room temperature

Flammable range: 5.6% to 40% (concentration in air)

Incompatibilities: Hydrogen cyanide reacts with amines, oxidizers, acids, sodium

hydroxide, calcium hydroxide, sodium carbonate, caustic substances, and
ammonia. Hydrogen cyanide may polymerize at 122F to 140F.

Hydrogen cyanide is produced in large quantities by two processes.

o

In the Degussa process, ammonia and methane react at 1200 C over a

platinum catalyst:

This reaction is akin to steam reforming, the reaction of methane and

water. In the Andrussov process, oxygen is added

CH4 + NH3 + 1.5O2 HCN + 3H2O

In the laboratory, small amounts of HCN are produced by the addition of

acids to cyanide salts of alkali metals:

This reaction is sometimes the basis of accidental poisonings because the

acid converts the nonvolatile salt into the gaseous HCN.

Hydrogen cyanide may be synthesized directly from ammonia and carbon

monoxide or from ammonia, oxygen (or air), and natural gas. It is a byproduct of
the production of coke from coal and is recovered (along with hydrogen sulfide)
from coke-oven exhaust gases. It may also be prepared by reacting a cyanide salt,
e.g., calcium cyanide, with a strong acid, e.g., sulfuric acid, or by thermal
decomposition of formamide. Because impure hydrogen cyanide can undergo
spontaneous explosive polymerization and decomposition, a small amount of
stabilizer (usually phosphoric acid) is added to it.

The principal use of hydrogen cyanide is in the manufacture of organic chemicals,

e.g., acrylonitrile, methyl methacrylate, and adiponitrile, that are used in
producing synthetic fibers and plastics. It is also used in the chemical laboratory,
and is sometimes used in agriculture as a fumigant. Hydrogen cyanide is found in
nature in some vegetable substances, e.g., bitter almond, peach stones, cherry and
cherry laurel leaves, and sorghum; it is usually combined in glycoside molecules
(see sugar) and is released when they are broken down by enzymes during
metabolism.

Manufacturing activities releasing hydrogen cyanide include electroplating,

metal, mining, metallurgy and metal cleaning processes. Additionally,
hydrogen cyanide has some insecticide and fungicide applications (ATSDR,
1993). Fires involving some nitrogen-containing polymers, often found in
fibers used in fabrics, upholstery covers, and padding, also produce hydrogen
cyanide (Tsuchiya and Sumi, 1977).

Sarin:

There are many different methods of manufacture, but the Tokyo product appears
to have been prepared using a procedure involving phosphorus trichloride and
methyl iodide. The product was impure and diluted with acetonitrile to improve
volatility. To stockpile Sarin, the product has to be pure ( 90-99% of the Iraqi
Sarin degraded in < 2 years, whereas US Sarin only degraded a few % over 30
years ). The standard US government procedure( aka "di-di" ) starts with dimethyl
methylphosphonate (DMMP), and ends with a distillation to remove impurities
[19].

One component in the U.S. binary is methylphosphonyldifluoride (Code DF;

CAS Registry Number 676-99-3) and the other is either isopropanol (CAS
Registry Number 67-63-0) alone or OPA, where OPA is a mixture of isopropanol
72% with isopropylamine (CAS Registry Number 75-31-0) 28%.

sarin precursors dimethyl methylphosphanate, hydrogen fluoride, and isopropyl

alcohol

In the final process, methylphosphonyl difluoride and methylphosphonyl

dichloride was mixed with isopropyl alcohol to produce Sarin

VX:

Its chemical formula is CH3CH20-P(O)(CH3)-SCH2CH2N(C3H7)2 and is

normally in its liquid state

Formal Chemical Name (IUPAC)

S-2-(diisopropylamino)ethyl O-ethyl methylphosphonothioate

The vital precursors are phosphites, phosphorous chlorides, and alkyldiethanolamines. Sales of these chemicals are restricted under the Chemical
Weapons Convention, most likely in an attempt to make synthesis of nerve gases
more difficult.

In particular, compounds containing the methyl-phosphite group are wellcontrolled, as the only known uses for these compounds are in the synthesis of
nerve agents.

The four-stage VX production process is difficult, but the Muthanna (Iraq)

scientists reverse engineered the recipe from a list of controlled chemicals issued
by the Organization for the Prohibition of Chemical Weapons in The Hague.
Saeed says he supervised production of his last two batches of liquid VX in April
1990 but that they failed to achieve his goal of 50 to 60 percent purity, and they
deteriorated within a week. "It couldn't be used as a weapon," he insists.

A dose of 10mg min/m3 of vapor is sufficient to cause death to 50 percent of individuals

exposed, while 10mg of VX liquid on the skin of a man weighing 70 kilograms (roughly
150 pounds) is fatal to 50 percent of individuals exposed.
Lewisite:

Lew-isite is 2-chlorovinyl-dichloroarsine.

Acute toxicity levels for humans are not well defined but 0.05-0.1 mg/cm2 produces erythema, 0.2 mg/cm2 produces vesication and a 15-minute exposure to a
vapor concentration of 10 mg/m3 produces conjunctivitis. About 30 drops (2.6
mg), applied to the skin and not decontaminated, would be expected to kill an
average man through systemic toxicity. With inhalation, the LCt50 in man is
estimated to be about 1500 mg min/m3.

Chemically, lewisite is dichloro-2-chlorovinyl arsine, ClCHCHAsCl2

2-Chlorovinylarsine dichloride (Lewisite 1) was produced in WW I and WW II as

chemical warfare agent by Friedel Craft's alkylation of arsenic(III)chloride with
ethine. During this production process the byproducts 2,2'-Dichlorodivinylarsine
chloride (Lewisite II) and 2,2',2''-Trichlorotrivinylarsine (Lewisite III) are built.

The earlier producers favored the Levinstein Process, which consists of bubbling
dry ethylene through sulfur monochloride, allowing the mixture to settle and
(usually) distilling the remaining material. More recent production has involved
chlorination of thiodiglycol, a relatively common material with a dual use as an
ingredient in some inks. This method does not result in the solid byproducts of the
Levinstein Process and can be more easily distilled.

Lewisite is an arsenical and as such would require unusually large amounts of

arsenates in its production.

Sulfur Mustard:

Synonyms:

H and HD: Bis(2-chloroethyl) sulfide; bis(beta-chloroethyl) sulfide; di-2-chloroethyl

sulfide; 1-chloro-2(beta-chloroethylthio)ethane; 2,2'-dichloroethyl sulfide; sulfur
mustard; Iprit; Kampstoff "Lost"; mustard gas; senfgas, S-yperite; yellow cross
liquid; yperite
HT: Mixture of bis(2-chloroethyl) sulfide and bis[2-(2-chloroethylthio)-ethyl]ether

Sulfur mustards are vesicants and alkylating agents. They are colorless when pure
but are typically a yellow to brown oily substance with a slight garlic or mustard
odor. H contains about 20 to 30% impurities (mostly sulfur); distilled mustard is
known as HD and is nearly pure; HT is a mixture of 60% HD and 40% agent T (a
closely related vesicant with a lower freezing point). Sulfur mustards evaporate
slowly. They are very sparingly soluble in water but are soluble in oils, fats, and
organic solvents. They are stable at ambient temperatures but decompose at
temperatures greater than 149C.

SELECTED PRECURSORS

2-Chloroethanol

Ethylene

Hydrochloric acid

Sodium sulfide

Sulfur dichloride

Sulfur monochloride

Thiodiglycol

Mass production was assisted by the fact that the production of dyes by I. G.
Farben had given the German chemical industry experience with the production
of the precursors used in synthesizing sulfur mustard. For instance, the mustard
precursor thiodiglycol had been produced at the Ludwigshafen works for dye
production in large lots even before the war. Thus, the initial demand was satisfied
using the existing reactors for thiodiglycol production, and the plans for these

reactors could be used to build new reactors to expand capacity (by the end of the
war, sixty new reactors had been constructed to supplement the twelve which had
existed at the beginning of the war). As a result, the Germans were able to rapidly
build up stocks of sulfur mustard after beginning production at Leverkusen in
Spring of 1917.
The table below shows how certain production processes for current
commercial products are identical to those which might be used for the
synthesis of agents used in chemical warfare.
Manufacturing

Common

process

commercial products

chlorination

Chemical weapons

Insecticides

Nitrogen and sulfur

Herbicides

mustards

Polymers, Dyestuffs

Lewisite

Pharmaceuticals

Sarin

Solvants

VX

Polymers, Solvants
Pharmaceuticals
fluorination

Pesticides, Herbicides
Cooling gases

Sarin
Soman

Anesthesic Gases
Insecticides
esterification

Solvants
Odorants
Pharmaceuticals

phosphoration

alkylation

Sarin
Tabun
BZ

Insecticides

Sarin

Flamme retardants

Tabun

Oil additives

BZ

Flamme retardants

Sarin

Oil additives

Soman

Petrol chemicals

VX