Working together for a world free of chemical weapons
REGIONAL TRAINING COURSE
FOR CUSTOMS AUTHORITIES OF STATES PARTIES IN ASIA
ON TECHNICAL ASPECTS OF THE TRANSFERS REGIME
OF THE CHEMICAL WEAPONS CONVENTION
NEW DELHI, INDIA
10 – 13 DECEMBER 2012
Chemicals to be monitored under CWC
Declarations Branch/Verification Division
ORGANISATION FOR THE PROHIBITION OF CHEMICAL WEAPONS
www.opcw.org
1
Objectives
 By the end of this session participants should:
– Be aware of the key CWC definitions of a chemical
weapon and a toxic chemical
– Understand the concept of the dual use nature of
chemicals
– Be familiar with the 3 Schedules of chemicals monitored
by the CWC
– Be familiar with some of the uses of the most common
scheduled chemicals
2
What is a chemical weapon?
?
Chemical Weapon
(Article II, Para 1)
Means the following, together or separately:
a) Toxic chemicals and their precursors, except
where intended for purposes not prohibited under
this Convention (*)
b) Munitions and devices, specifically designed to
cause death or other harm through the toxic
properties of those toxic chemicals specified in
paragraph a)
c) Any equipment specifically designed for use
directly in connection with the employment of
munitions and devices specified in paragraph b)
(*) General purpose criterion defined by purpose and not by properties
4
Toxic Chemicals
(Article II, Para 2)
TOXIC CHEMICAL means any chemical
which through its chemical action on life processes
can cause death, temporary incapacitation or
permanent harm to humans or animals. This includes
all such chemicals, regardless of their origin or of the
method of production, and regardless of whether
they are produced in facilities , in munitions or
elsewhere.
5
Article VI of CWC
 Establishes the right of a State Party to
manufacture and use toxic chemicals and their
precursors for activities not prohibited under the
Convention
 Creates legal bases for Declaration, Verification and
Transfer regimes related to such chemicals,
facilities and activities.
 Verification Annex Parts VI to IX
6
Activities not Prohibited under the Convention
ARTICLE II, P9
 Industrial, agricultural, research, medical,
pharmaceutical or other peaceful purposes
 Protective purposes
 Military purposes not connected with the use of
chemical weapons
 Law enforcement including riot control purposes
7
Dual Use Nature of Chemicals
 Many chemicals covered by CWC can be used for
legitimate peaceful purposes as well as chemical
weapons (CW) purposes.
 Cannot just define a list of “banned” chemicals.
– Need to define chemicals and activities to be monitored
 Remember the CWC does not just cover toxic
chemicals but also many non-toxic precursors that
can be used to make toxic chemicals for CW
purposes.
8
Annex on Chemicals to the CWC
Sched 1
Sched 2
Activities
not
prohibited
Sched 3
DOC
9
Schedule 1 Chemicals
 It has been developed, produced, stockpiled or
used as a chemical weapon ...;
 It poses otherwise a high risk to the object and
purpose of this Convention by virtue of its high
potential for use in activities prohibited under this
Convention … ;
 It has little or no use for permitted purposes
10
Schedule 1 Chemicals
 12 entries – families or individual chemicals
 Schedule 1A: toxic chemicals - Includes well known
chemical weapons agents such as
– Sarin, Soman, VX
– Sulfur and nitrogen mustards
 S1A also includes toxins Ricin and Saxitoxin
 Schedule 1B - key precursors
11
Examples of Schedule 1A
Schedules 1A01-03 – Large Families
1A01
1A02
O-Alkyl (C10, incl. cycloalkyl) alkyl (Me, Et, nPr or i-Pr)-phosphonofluoridates
e.g. Sarin (CAS No.: 107-44-8)
Soman
(CAS No.: 96-64-0)
O
P
R1
O-Alkyl (C10, incl. cycloalkyl) N,N-dialkyl (Me,
Et, n-Pr or i-Pr) phosphoramidocyanidates
e.g. Tabun: (CAS No.: 77-81-6)
F
R
O
R2
N R1
O
P
R
O
N
1A03
O-Alkyl (H or C10, incl. cycloalkyl) S-2-dialkyl
(Me, Et, n-Pr or i-Pr)-aminoethyl alkyl (Me, Et,
n-Pr or i-Pr) phosphonothiolates and
corresponding alkylated or protonated salts
e.g. VX:
(CAS No.: 50782-69-9)
R1
O
R2
P
N
S
O
R3
R
Throughout R1, R2, R3 = Me, Et, n-Pr or i-Pr
R=alkyl or cycloalkyl, with C10
12
Effect of Nerve Agents
13
Examples of Schedule 1A
Sulfur Mustards 1A04 – 9 Specific Chemicals
(4) Sulfur mustards:
S
2-Chloroethylchloromethylsulfide
(2625-76-5)
Mustard gas: Bis(2-chloroethyl)sulfide Mustard or HD (505-60-2)
Bis(2-chloroethylthio)methane
Sesquimustard: 1,2-Bis(2-chloroethylthio)ethane
1,3-Bis(2-chloroethylthio)-n-propane
Cl
S
Cl
Cl
(63869-13-6)
(3563-36-8)
(63905-10-2)
1,4-Bis(2-chloroethylthio)-n-butane
(142868-93-7)
1,5-Bis(2-chloroethylthio)-n-pentane
(142868-94-8)
Bis(2-chloroethylthiomethyl)ether
Cl
(63918-90-1)
14
O-Mustard: Bis(2-chloroethylthioethyl)ether
(63918-89-8)
Examples of Schedule 1A
Lewisites 1A05 – 3 Specific Chemicals
Cl
Cl
As
Lewisite 1: 2-Chlorovinyldichloroarsine
Cl
Cl
As
Cl
Lewisite 2: Bis(2-chlorovinyl)chloroarsine
Cl
Cl
Lewisite 3: Tris(2-chlorovinyl)arsine
As
Cl
Cl
15
Examples of Schedule 1A
Nitrogen Mustards 1A06 – 3 Specific Chemicals
N
Cl
HN-1 = Bis(2-chloroethyl)ethylamine
Cl
N
HN-2 = Bis(2-chloroethyl)methylamine
Cl
Cl
Cl
N
HN-3 = Tris(2-chloroethyl)amine
Cl
Cl
16
Effect of Mustard Gas
17
Saxitoxin 1A07
O
NH2
O
N
H2N
R
S
HN
HO
HO
S
H
N
N
Saxitoxin is a neurotoxin naturally produced by
certain species of marine dinoflagellates
(Alexandrium sp., Gymnodinium sp.,
Pyrodinium sp.) and cyanobacteria (Anabaena
sp., some Aphanizomenon spp.,
Cylindrospermopsis sp., Lyngbya sp.,
Planktothrix sp.).
NH2
Ingestion of saxitoxin (usually through shellfish contaminated by
toxic algal blooms) is responsible for the human illness known as
paralytic shellfish poisoning (PSP).
18
Red tides
Castor Bean (Ricinus communis)
Ricin (1A08)
is a protein toxin extracted from Castor
Beans. It is found in many countries
around the world
Schedule 1 Chemicals
B.
Precursors:
O
O
DF: Methylphosphonic difluoride
P
P
 (9) Alkyl (Me, Et, n-Pr or i-Pr) phosphonyldifluorides
e.g. DF:
F
F
(CAS No.: 676-99-3)
 (10) O-Alkyl (H or <C10, incl. cycloalkyl) O-2-dialkyl
(Me, Et, n-Pr or i-Pr)-aminoethyl alkyl
(Me, Et, n-Pr or i-Pr) phosphonites and
corresponding alkylated or protonated salts
e.g. QL:
(CAS No.: 57856-11-8)
F
F
N
O
P
O
QL: Ethyl 2-diisopropylaminoethyl methylphosphonite
 (11) Chlorosarin: O-Isopropyl methylphosphonochloridate
(CAS No.: 1445-76-7)
 (12)Chlorosoman: O-Pinacolyl methylphosphonochloridate
(CAS No.: 7040-57-5)
21
Uses of Schedule 1 Chemicals
 No large scale uses
 Ricin
– Anticancer research
 Saxitoxin
– Diagnostic kits for Paralytic Shellfish Poisoning
 Nitrogen Mustard
– Small quantities for skin cancer treatment
 Sarin – Sulfur Mustard – VX
– Small quantities used for developing protection and
detection methods
22
Schedule 2 Chemicals
 ... it possesses such lethal or incapacitating toxicity
as well as other properties that could enable it to
be used as a chemical weapon;
 It poses a significant risk ... by virtue of its
importance in the production of a chemical listed
in Schedule 1 or Schedule 2, part A;
 It is not produced in large commercial quantities
for purposes not prohibited under this Convention.
23
Schedule 2 Chemicals
A.Toxic chemicals:
 (1) Amiton: O,O-Diethyl S-[2-(diethylamino)ethyl]
phosphorothiolate
(78-53-5)
and corresponding alkylated or protonated salts
 (2) PFIB:
1,1,3,3,3-Pentafluoro-2-(trifluoromethyl)-1-propene
(382-21-8)
 (3) BZ: 3-Quinuclidinyl benzilate (*)
(6581-06-2)
Virtually never traded
24
Schedule 2 Chemicals
?
?
B.


Precursors:
R
P
?
?
R
?
P
R
?
(4) Chemicals, except for those listed in Schedule 1, containing a
phosphorus atom to which is bonded one methyl, ethyl or propyl
(normal or iso) group but not further carbon atoms,
e.g.
Methylphosphonyl dichloride
(676-97-1)
Dimethyl methylphosphonate
(756-79-6)
Exemption: Fonofos:
(944-22-9)
...
(10) N,N-Dialkyl (Me, Et, n-Pr or i-Pr) aminoethyl-2-chorides
and corresponding protonated salts

(13) Thiodiglycol: Bis(2-hydroxyethyl)sulfide

(14) Pinacolyl alcohol: 3,3-Dimethylbutan-2-ol
P
?
?
(111-48-8)
(464-07-3)
?
R= Me, Et,
Pr or iPr
Examples of Uses of a Specific Schedule 2
HO
Chemical
Thiodiglycol
S
OH
 Carrier for Dyes in Textile & Printing Industry
 Co-solvent in Water-based Pen Inks
 Manufacture of Some Types of Plastics, Resins
and Adhesives
 Lubricant Additive
BUT 1 STEP FROM MUSTARD GAS
26
Examples of Uses of a Specific Schedule 2
O
Chemical
P
O
O
Dimethyl methylphosphonate (DMMP)
 Used as flame retardant for foamed polyurethane
plastics and as flame retarding impregnant e.g. for
textiles
 Several other chemicals from Schedule 2B04 used in
similar applications (e.g. diethyl ethylphosphonate)
BUT KEY PRECURSORS FOR THE NERVE AGENTS
27
Examples of Sch 2 Commercial Uses
Amiton
Was a commercial pesticide withdrawn
due to toxicity
PFIB
Waste Constituent
BZ
Pharmaceuticals, Medical Research
Schedule 2B4 Family
Flame retardants, Anti-Foam agents,
Gasoline/Oil Additives
Viscosity depressants, Textiles, Drugs,
Dialkylphosphoramidic
Dihalides Family
None
Dialkyl N,N-dialkylPhosphoramidates Family
Polyamide Fibers, Fireproofing agents
28
Examples of Sch 2 Commercial Uses
Arsenic Trichloride
Diphenyl-2-hydroxyacetic
acid
Quinuclidin-3-ol
Purifying Arsenic, Semiconductor manuf.
Catalyst in CFC Manuf.
Organoarsines/Chloroarsines
Polishing stainless steel, Catalyst for
Urethanes, Hydantoin manufacture
Antichigger Clothing Treatment
Organic Ammonium Bromides
Drug Research
Laboratory Reagent/Catalyst
N,N-Dialkylaminoethane2-ols Family
Manufacturing organic thiols
N,N-Dialkylaminoethane2-thiols Family
Drugs, Food Flavourings, Antibacterials
29
Examples of Sch 2 Commercial Uses
N,N-Dialkylaminoethyl2-chlorides Family
Drugs, Agrochemicals, Dyes,
Calcium Filler for Paper/Plastics
Thiodiglycol
Wetting agent in textile dyeing,
Dye solvent,
Antioxidant, Anticorrosives,
Inks, Epoxy resins, Fabrics
Pinacolyl alcohol
Organic synthesis
30
Schedule 3 Chemicals
 It has been produced, stockpiled or used as a
chemical weapon;
 … it possesses such lethal or incapacitating toxicity
as well as other properties that might enable it to be
used as a chemical weapon;
 It poses a risk by virtue of its … importance in the
production of one or more chemicals listed in
Schedule 1 or Schedule 2B;
 It may be produced in large commercial quantities
for purposes not prohibited under this Convention.
31
Schedule 3 Chemicals
A.Toxic chemicals:




(1)
(2)
(3)
(4)
Phosgene: Carbonyl dichloride
Cyanogen chloride
Hydrogen cyanide
Chloropicrin: Trichloronitromethane
(75-44-5)
(506-77-4)
(74-90-8)
(76-06-2)
B. Precursors:
 (5)
 (6)
Phosphorus oxychloride
Phosphorus trichloride
(10025-87-3)
(7719-12-2)
...
 (16) Methyldiethanolamine
 (17) Triethanolamine
(105-59-9)
(102-71-6)
32
Examples of Uses of a Specific Schedule 3
Chemical
Triethanolamine (1)
 Desulfurisation in Petroleum Refining
 Intermediate in Manufacture of Surface Active
Agents, Textile Specialties, Waxes, Polishes,
Herbicides, Petroleum Emulsifiers, Cement
Additives, Cutting Oils
 Making Emulsions with Mineral & Vegetable Oils,
Paraffin & Waxes
 Solvent for Dyes
33
Examples of Uses of a Specific Schedule 3
Chemical
Triethanolamine (2)
 Manufacture of Synthetic Resins
 Increasing Penetration of Organic Liquids into
Wood & Paper
 Production of Lubricants for the Textile Industry
 PH balancer in cosmetics
BUT 1 STEP FROM NITROGEN MUSTARD
34
Examples of Sch 3 Commercial Uses
Phosgene
Polyurethanes, Polycarbonates, Drugs,
Perfumes, Fumigants, Dyes,
Chlorinating agent
Cyanogen chloride
Herbicides, Dyes, Vitamins,
Rubber vulcanization, Laboratory reagent
Hydrogen cyanide
Adiponitrile, Acetone cyanohydrin, Drugs,
Sodium Cyanide, Cyanuric chloride,
Methionine, Plastics, Pesticides, Bleaches,
Sanitizers, Fumigants
Chloropicrin
Fumigants, Rodenticides, Antioxidants
35
Examples of Sch 3 Commercial Uses
Phosphorus trichloride
Flame retardants, Plasticizers, Plastics,
Elastomers, Surfactants, Pesticides,
Lube Oils, Greases, Catalyst
Phosphorus pentachloride
Catalyst, Chlorinating agent, Polymers,
Flame retardants, Surfactants, batteries
Trimethyl phosphite
Insecticides, Adhesives, Polyolefins,
Flame retardants, Other phosphites
Phosphorus oxychloride
Triethyl phosphite
Dimethyl phosphite
Pesticides, Plastic additives, Antioxidants,
Flame retardants, Corrosion inhibitors,
Viscosity depressant
Corrosion Inhibitor, Antioxidant, Stabilizer
Adhesives, Pesticides, Antifungals,
Fire retardants
36
Examples of Sch 3 Commercial Uses
Diethyl phosphite
Catalyst, Antifungals, Insecticides,
Lube oil additives, Color preventative
Sulfur monochloride
Vulcanizing rubber, Lube oil additives,
Antioxidants, Crosslinking, Solvent,
Catalyst
Sulfur dichloride
Thionyl chloride
Chlorinating agent, Antibiotics, Pesticide,
Lube oil additives, Antioxidants,
Funguicide
Acid chlorides, Herbicides, Insecticides,
Fumigants, Thermoplastics, Surfactants,
Drugs, Vitamins, Dyes, Catalyst, Batteries,
Chlorinating agent, Photography
37
Examples of Sch 3 Commercial Uses
Surfactants (cosmetics, detergents,
cleaners)
Gas Purification
Electroplating
Ethyldiethanolamine
Lubricants
Derusting
Pickling steel
Coagulants
Methyldiethanolamine
Softening agents
Antistatic agents
Synthetic fibers
Triethanolamine
Flame retardants
Urethanes
Pesticides
Propellants
38
Scheduled Chemicals
 Schedule 1 - 12 families or individual
chemicals
– Theoretically over 2 million individual chemicals
– approx 950 individual chemicals declared
– Traded in very small amounts (often grams or less)
 Schedule 2 - 14 families or individual
chemicals
– Theoretically millions of individual chemicals
– 300 individual chemicals declared
– 20 regularly traded in moderate volume
 Schedule 3 - 17 individual chemicals
– 15 regularly traded - some very large volume
– Other 2 not generally traded but produced and used
onsite.
39
DOC/PSF Chemicals
 DISCRETE ORGANIC CHEMICAL
Any chemical belonging to the class of chemical
compounds consisting of all compounds of carbon
except for its oxides, sulfides and metal
carbonates, identifiable by chemical name, by
structural formula, if known, and by Chemical
Abstracts Service registry number, if assigned
 PSF-Chemical
Any unscheduled discrete organic chemical
containing the elements phosphorus, sulphur or
fluorine
40
DOC/PSF Chemicals (2)
 Vast range of chemicals – interest in capabilities
of plants producing them rather than chemicals
themselves
 Hence no import/export provisions
41
Questions
?