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Chemical Warfare:
History and Chemistry
Stephen L. Morgan
Professor
Department of Chemistry & Biochemistry
The University of South Carolina
Columbia, SC 29208
Email: morgan@mail.chem.sc.edu
URL: http://www.chem.sc.edu/faculty/morgan
Lecture material URL: http://www.chem.sc.edu/faculty/morgan/cw
Chemical and Biological Warfare (CBW)
Compared to other weapons of mass destruction, CBW has seen very
little use.
The potential threat of CBW is terrifying:
blinded, disoriented, clutching your chest, gasping for breath,
drowning in mucus fluids pouring from the lungs, choking to death
CBW is silent, invisible, pervasive, and deadly. You may not be able to
hide from it.
Chemical warfare (CW) agents use poisons that kill, injure, or
incapacitate. CW agents can be gases or liquids or, more commonly,
dispersed as aerosols.
Biological warfare (BW) agents use living bacteria (e.g., Bacillus
anthracis, the causative agent of anthrax) or viruses (e.g., Variolae, the
virus that causes smallpox).
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CW agent Use
CW use in the trenches of World War I allowed attacks to break through
fortifications. Heavier-than-air gases would fill the trenches and tunnels,
rendering them useless for defense.
Modern precision-guided conventional weapons render this classical
motive for CW obsolete.
Suiting up an army in CBW protective gear is expensive, time-
consuming, degrades communications and fighting ability, and causes
panic and chaos. Creating massive casualties requiring medical aid
further impairs effectiveness by spreading uncertainty and, ultimately,
fear. CBW is the ultimate terror weapon.
Another argument: If the enemy has it, we must have it.
CW (or BW) agents are said to have a large footprint and are cheaper
than conventional weapons.
Chemical weapons are a kind of
poor mans atomic bomb.
Iranian President Ali Akbar Hashemi, 1988,
at the end of Irans war with Iraq.
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Routes of entry for CW agents
inhalation through lungs
ingestion by mouth
injection through puncture wound
absorption on skin
Classes of CW Agents
Choking gases and lung irritants)
Blister agents (vesicants)
Blood agents
Nerve agents
Incapacitants and psychoactive chemicals
Harassing or riot-control agents (RCAs)
and vomiting agents
Herbicides
Napalm
Obscurant smoke and masking agents
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Choking gases and lung irritants Choking gases and lung irritants
CW agents that irritate the respiratory system causing formation
of water in the lungs, resulting in death from lack of oxygen
Chlorine (Cl
2
): A new form of warfare
Use: by Germany against
Allied troops on 22 April 1915
at 5 pm near Ypres, Belgium.
Result: 5,000 dead, 10,000 wounded.
Logistics: 5,730 90-lb cylinders
buried in concealment along a 6-km
front; 160 tons of gas were
manually released when the wind
was favorable.
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Description and effects of chlorine
Description: Greenish yellow gas; amber liquid. Odor is suffocating,
pungent, and irritating.
Health effects: Causes burning of nose and mouth with rhinorrhea,
respiratory distress with coughing fits, choking, wheezing, rales,
retching, hemoptysis, substernal pain, dyspnea, and cyanosis. Strips
and inflames the mucous lining of the bronchial tubes and lungs,
allowing fluid to enter the lungs from the bloodstream. May cause
bronchitis, progressing to pulmonary edema and occasional
pneumonitis. Causes Chronic respiratory and pulmonary dysfunctions.
Other symptoms include salivation, anxiety, sneezing.. Pallor or redness
of the face, weakness, hoarseness, headache, dizziness, and general
excitement and restlessness. Massive inhalation may alos cause death
by cardiac arrest. May irritate skin and cause burning and pricking
sensations, inflammation, and blisters.
Oil on canvas 231 611.1
Imperial War Museum, London
John Singer Sargent, Gassed (Aug. 1918)
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Phosgene (carbonyl chloride, COCl
2
)
Use: At 5:30 am on 19 December 1915, the Germans
attacked at Ypres (again) using phosgene in artillery shells.
Results: Panic and disruption as men were caught unawares.
1,069 men gassed; 116 dead.
At the Somme in J une 1916, the Allies used both chlorine and
phosgene: men, vegetation, insects, and animals were wiped
out. Over the next 19 months, the British discharged over
1,500 tons of phosgene.
Gassed and Wounded, Oil
Eric Henri Kennington(1888-1960), English
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Other choking gases
Liquid at room temperature,
thus persistent, WW1
Discovered in 1848, used by Russians in
WW1, attacks rubber, dual-use as odor in
pesticides
Volatile, fast acting, WW1
Industrial use, gas decomposition
product from Teflon

; 10 more
lethal than phosgene; latency 1-4 hr
before pulmonary edema; prepared
by Russia as CW
diphosgene
(trichloromethyl chloroformate )
chloropicrin
(trichloronitromethane)
ethyldichloroarsine
(DICK)
perfluoroisobutylene
(PFIB)
Blister agents (vesicants) Blister agents (vesicants)
CW agents that affect eyes, lungs, and skin,
causing formation of large blisters
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Mustard
(bis-(2-chloroethyl)sulphide, (ClCH
2
CH
2
)2S )
Use: On 12 J uly 1917, about
10 pm, at Ypres, Belgium, the
Germans shelled the British
with 77 and 105 mm gas
shells.
Result: Initial effect was just
sneezing; within hours eye
irritation, vomiting, and blisters
appeared.
Also called Lost,Yperite, H or HD
Gas attack by artillery in WW1
Description and effects of mustard
Description: A yellow-brown liquid in crude preparation; colorless in pure
form. An oily unpleasant smell like mustard, tasting like garlic (perhaps
due to impurities).
Health effects: On skin contact, the fat-soluble liquid penetrates the skin
and destroys interior tissue in a delayed reaction (up to 24 hr), causing
blisters that take a long time to heal. Death may occur from toxic shock
within 24 hr of massive exposure.
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Other blister agents
nitrogen mustard
Lewisite
(2-chlorovinyl dichloroarsine)
phosgene oxime
phenyldichloroarsine
(PD)
Oily persistent liquid, more toxic
than sulfur mustard, some medical
applications.
The dew of death, prepared in 1918 by
W. Lee Lewis (Catholic Univ.) for WW1;
nonflammable; fast acting blistering.
Nettle gas or Red cross (WW2): acute
damage to lungs, eyes, and skin; chronic
systemic effects.
Liquid, persistent, extremely irritating
to nose and throat, also a vomiting
agent; developed as CW by Haber.
Growing use of CW in WWI
Year Amount of gas discharged, tons
1915 3,870
1916 16,535
1917 38,635
1918 65,160
J . B. S. Haldane, CallinicusA Defence of Chemical Warfare,
KeganPaul: London, 1925, pp. 28-38.
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In no future war will the military
be able to ignore poison gas.
It is a higher form of killing.
Professor Fritz Haber, pioneer of gas warfare,
on receiving the Nobel Prize for chemistry, 1919.
Blood agents Blood agents
CW agents that interfere with the bodys ability to transport
oxygen in the blood stream
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Blood agents
Poisons that block oxygen use or uptake from the blood, causing
asphyxiation.
Hydrogen cyanide (HCN, prussic acid): Liquid at room
temperature, but evaporates rapidly. Used in Zyklon B made by
IG Farben for use in German WW2 extermination camps.
Unstable due to rapid polymerization and thus considered
unsuited today for CW.
Unconfirmed reports:
1980s, HCN used by Syria
against uprising in Hama;
1988, Iraqi attack on
Kurdish town of Halabja; in
Shahabad, Iran, during the
Iran-Iraq war.
J apanese WW2
HCN grenade
Other blood agents
cyanogen chloride (CK)
arsine (AsH
3
)
carbon monoxide
(CO)
hydrogen sulfide
(H
2
S)
Toxic flammable gas, destroys red blood cells,
widespread organ injury; powerful reducing agent,
strong affinity for hemoglobin; hemolysis of red blood
cells causes renal failure.
Volatile, but less flammable than HCN
Common pollutant, by product of heating systems;
binds to hemoglobin with an affinity 250-300 that of
oxygen; victims die by asphyxiation and take on a
cherry red skin color.
More toxic than HCN, used in WW1; by-product of
decaying organic matter or volcanic activity; 1997:
planned use in a diversionary explosion in white
supremacist robbery plot foiled by the FBI.
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Nerve agents Nerve agents
CW agents that interfere with the bodys nervous system by
disrupting the acetyl cholinesterase process
Nerve agents
First developed by Gerhard Schrader of IG Farben in 1936 as an outgrowth of
organophosphate pesticide development. Routes: inhalation and skin contact.
Health effects: Nerve agents act by paralyzing the respiratory muscles by
attacking acetyl cholinesterase which blocks muscle relaxation; extreme muscle
twitching, fast breathing, followed by bronchoconstriction result. Severe fatigue
and mucosal and salivary excretion, stopping breathing.
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G-series nerve agents
Tabun
(ethyl NN-dimethyl-
phosphoramidocyanidate, GA)
Sarin
(isopropyl methylphosphono-
fluoridate, GB)
Soman
(1,2,2,-trimethylpropyl
methylphosphonefluoridate,
GD)
First nerve agent
discovered, colorless
liquid which turns to
vapor at room
temperature.
Non-persistent, causes
death in 1-2 min
through skin, 15 min
inhaled.
Semi-persistent,
primary agent for
Soviets, 3 more toxic
as tabun.
V-series nerve agents
VX
o-ethyl S-2-
diisiopropylaminoethyl
methylphosphonothiolate
Health effects: The V-series agents (VE, VG, VM, and VX) are more
toxic than the G-series. 10-15 mg of VX, less than a drop, in contact
with skin will kill a man of average weight unless medical attention is
provided; takes several hours for effects.
Delivery: These agents are also more persistent than the G-series: less
of vapor hazard, more of skin hazard. High persistence means they can
be used to contaminate (or in military jargon, slime) surfaces(roads,
equipment, etc.) to harass and immobilize.
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Taliban, al Qaedamight havenervegas, The State,
pA7, 1/23/02
Incapacitants and psychoactive chemicals
CW agents that can incapacitate, disorient, or paralyze
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Incapacitants - 1
Desired characteristics: effects will endure over time (hours, days);
not endanger life or cause permanent injury; recovery not require
medical attention; agents must be deliverable, potent, and easy to
store.
Belladonna (glycolate alkaloids such as atropine): derived from
belladonna, a poisonous plant of the nightshade family, these
poisons have been known since 200 BC. Pupil dilation, dryness,
fever, and sight impairment are typical symptoms.
3-quinuclidinyl benzilate (BZ): Belladonna-based incapacitant that
attacks the CNS, depressing the nervous system, causing
hallucinations; designed to be delivered in aerosol form.
Manufactured at Pine Bluff Arsenal (AR); most stocks destroyed in
the 1980s. 1988: alleged report of use against Bosnian refuges.
Incapacitants - 2
Ergot and lysergic acid diethylamide (LSD)
1951, France: The calls from stricken new patients kept flooding in. By Monday,
August 14, the town's hospital was swamped. Seventy homes had also been turned
into emergency wards. That first night the first victim died in agonizing convulsions.
Raving patients were held in their beds or escaped from their homes, mad, frantic, to
run in the streets. The terror grew as the news broke that a demented eleven-year old
boy had tried to strangle his own mother. The mood of the peopleand the
atmosphere of the place began to resemble that of a plague-swept town of the Middle
Ages. ...Finally, the chief toxicologist of Marseilles sent his report to Pont-St.-Esprit
and the anxious nation. The bread contained twenty alkaloid poisons, three of them
Virulent, and all came from the same source. The poisons could be found in fungus
growth that changed normal kernels of rye to purplish cockspurs called ergot.
Carefoot, G. L.; Sprott, E. R. Famine on the Wind: Plant Diseases and
Human History, Angus and Robertson: London, 1967; pp. 17-18.
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Harassing or riot-control agents (RCAs)
and vomiting agents
CW agents used to combat public disturbances as a non-
lethal means to disperse unruly crowds
Description and effects of RCAs
Some compounds are lacrimators (tear-producing agents); some
are sternutators (sneezing agents). Most are not lethal unless
ingested in high doses. Vomiting agents can cause death in
constrained spaces or if the victim chokes.
Tear gases or RCAs irritate the eyes and mucosal tissues of the
nose and mouth, causing extreme discomfort.
Debate has continued about the ethics of using riot-control agents
in warfare. Current international agreements prohibit use of RCAs
in wartime.
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RCA examples
ethylbromoacetate
chloroacetone
Xylyl bromide
(T-stoff)
Acrolein
Strong lacrimator, used by the French in WW1 for both
rifle grenades and regular grenades.
Used for French rifle grenades in WW1.
The first CW agent produced by Germany in WW1;
corrodes most metals, requires lead canisters for
storage; less toxic but more powerful lacrimator than
ethylbromoacetate. Iodine analog also used.
Relatively toxic and potent lacrimator made form
glycerine (cheaper); however, produces acrylic acid on
exposure to air which quickly polymerizes to inert gel.
Stability prevents it being used as an effective CW
agent.
RCA examples (continued)
Bromobenzyl cyanide
(CA, camite)
chloroacetophenone
(CN)
Synthesized by halogenating phenyl
cyanide in 1914. First used by the French
in J uly 1918; manufactured in quantity by
the U.S. starting in 1918. Corrodes metals,
prone to decomposition, and heat sensitive;
requires special handling and storage.
CN is one of the most potent lacrimators known.
Difficult to manufacture, not used in WW1.
J apan may have bee the first to use CN in
Taiwan in 1930.
Mace

, Methylchloroformchloro acetone, a
related compound is sold commercially as a
liquid spray to use against an attacker. Pepper
spray, made from capsaicin from chili peppers,
is largely replacing CN.
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RCA examples (continued)
o-chlorobenzylidene
malononitrile (CS)
CS is now the tear gas of choice in the U.S.
Delivered as 3-10 microencapsulated
particles in aerosols, or as a thermal grenade
producing CS fumes.
Typically, men leave the exposure with tears, nasal
secretions, and saliva pouring out, and towels rather than
handkerchiefs are needed to cope with the fluids. In 5-15
minutes, the irritation ceases.
Possible Long-term Health Effects of Short-term Exposure to Chemical Agents,
Volume 2. Cholinesterase Reactivators, Psychochemicals, and Irritants and
Vesicants, National Research Council: Washington, D.C., 1984; p. 159.
Herbicides
Common agents include:
Herbicide Compound
Paraquat bipyridylium
Agent White picloram, 2,4-dichlorophenoxyacetic acid
Agent Orange 2,4,5-trichlorophenoxyacetic acid and 2,4-D
(defoliant used
in Vietnam)
Agent Blue dimethyl arsenic acid
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2,3,7,8-tetrachlorodibenzo-p-dioxin
(dioxin or TCDD)
Health effects: acute and chronic: distorted perceptions,
changes in motor activity, nausea, respiratory irritation, CNS
depression, liver, kidney and lung damage, severe eye and skin
irritation. Highly toxic.
Napalm
Obscurant smoke
Masking agents
Early incendiaries were J ellied mixtures of gasoline and rubber; the
M-47 bomb was gasoline jelly mixed with white phosphorus for
ignition. NAPALM is a mixture of aluminum soaps of naphthenic and
coconut fatty acids and palm oil.
In WW1, white phosphorus was often used to generate smoke, but
its toxicity has led to replacement by titanium tetrachloride for
obscurant smoke.
Malodorous compounds are often used to mask the presence of
other gases or to force the enemy to suit up when no CW is present.
Mercaptans Skatole (rotting offal)
3-methyl-1-butanethiol (skunk)
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Steps to chemical warfare
1. Acquisition of CW materials
2. Production of CW agents
3. Delivery of CW weapons
Acquisition of CW materials
Develop from raw materials (or precursors), purchase outright,
or combine home-grown with store-bought.
Many precursors to CW weapons are materials with legitimate
commercial uses:
Compound Commercial use CW use
Thiodiglycol Plastics, textile dyes, ink Mustard
Phosphorus trichloride Plasticizers, insecticides G-series
Sodium cyanide Dyes, pigments, metal hardening GA, AC, CK
Methylphosphonic difluoride Organic synthesis VX, GB, GD
Crody, E.; Perez-Armendariz, C.; Hart, J . Chemical and Biological Warfare,
Springer-VerlagNew York Inc.: New York, 2002.
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Production of CW agents
Synthesis in small batch quantities in a pilot plant to solve
technical difficulties in chemistry, scale-up, handling.
Use of standard chemical engineering equipment (reactors,
distillations apparatus, heat exchangers, pumps, valves, filters,
etc.). Obtaining and maintaining this equipment may be
problematic.
Specialized equipment (e.g., glass lines or steel reactors) may
be needed to handle corrosives.
Making the product into a suitable form to use as a weapon
(weaponizing) usually requires some technical expertise. Issues
include: design of unitary or binary CWs; stability; handling;
storage; dissemination as liquid, powder, spray, or aerosol;
dispersal; thermal and shock lability.
Delivery of CW agents
The effectiveness of CW agents is influenced by a combination
of the choices made in delivery and environmental conditions.
CW delivery:
point source with munitions;
line source with sprayer.
Form:
Liquid, aerosol, or vapor.
Atmospheric conditions:
temperature (and patterns of temperature), time of day;
wind, sun, rain, altitude.
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Iraq CW Program 1988-1991
In possession: 1,000-4,000 tons mustard gas and nerve agents: tabun
(GA), sarin(GB), GF (cyclosarin).
In development: soman(GD), persistent nerve agent VX, hallucinogen
agent BZ.
Delivery: Soviet-purchased 122-mm
multiple rocket launchers, helicopter-
launched 90-mm rockets with
chemical warheads, 250/500 kg aerial
chemical bombs, chemical projectiles
for 155-mm artillery guns, Scud
chemical warheads. Monthly
production : 150 tons mustard, 5-10
tons tabun, 20 tons sabin.
Mauoroni, A. J . Chemical-Biological Defense: U.S. Military Policies and
Decisions in the Gulf War, Praeger Publishers: Westport, CT, 1998.
CW terrorism
1974: MuharemKerbegovicwas arrested in Los Angeles after mailing toxic material
to a Justice of the Supreme Court and threatening to kill the president with nerve gas
1991: German authorities thwarted a neo-Nazi plot to pump hydrogen cyanide into a
synagogue.
1992: the FBI arrested two members of the Patriots Council in Minnesota for
possession of less than one gram of ricin, under the Biological Weapons Anti-
Terrorism Act of 1989.
1993: First World Trade Center Bombing led by Ramsi Yousef. The use of cyanide
was considered, but delivery was considered too expensive.
1994: AumShinrikyo, an apocalyptic religious cult based in J apan, used a
refrigerated truck to spray sarinon several magistrates who were to rule against them
in a legal dispute. The judges survived, 7 bystanders were killed, and 144 were
seriously injured.
1995: Attack on Tokyo subway by AumShinrikyoused sarin. 12 people killed, 1,000
injured in 16 stations. Would have been worse if they had not diluted their sarinstock
with acetonitrile.
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The future threat
Comment 1:
Many of the chemical weapons discussed here are
considered obsolete for military purposes.
Many of them require some expertise and cost to
make, produce in quantity, handle correctly,
weaponize, and deliver.
CBWs are simply not as available as bullets and
bombs.
The future threat
Comment 2:
Chemical or biological weapons provide more
bang for the buck,killing their victims with less
cost than bullets or bombs.
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The future threat
Comment 3:
The level of knowledge required to manufacture
chemical weapons is on the order of a competent
organic chemistry graduate studentmuch less
knowledge than required for biological weapons.
Most of the starting materials and equipment can
be commercially purchased without notice or
alarm.
We [have] the ability to make and use chemicals
and poisonous gas. And these gases and poisons
are made from the simplest ingredients, which are
available in the pharmacies; and we could, as well,
smuggle them from one country to another as
needed. And this is for use against vital institutions
and residential populations and drinking water
sources and others
Ramsi Yousef, , 1995, convicted terrorist bomber
for first World Trade Center bombing
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The future threat
Comment 4:
The large amounts of industrial chemicals manufactured
and shipped (e.g., chlorine) offer themselves as low-tech
weapons of opportunity and terror.
Obsoletefor the strategic or tactical military operations is
not the same as unusable for terrorism.
The events of 11 September 2001 show that even
ordinaryitems of our high-tech world can be transformed
into weapons.