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Introduction

Chemical warfare
Part of a series on Chemical agents Lethal agents Blood agents Cyanogen chloride (CK) Hydrogen cyanide (AC) Blister agents Ethyldichloroarsine (ED)

Methyldichloroarsine (MD)

Phenyldichloroarsine (PD)

Lewisite (L)

Sulfur mustard (HD, H, HT, HL, HQ)

Nitrogen mustard

1. HN1 2. HN2 3. HN3

Nerve agents

G-Agents Tabun (GA) Sarin (GB) Soman (GD) Cyclosarin (GF) GV V-Agents EA-3148 VE VG VM VR VX Novichok agents Nettle agents Phosgene oxime (CX) Pulmonary agents Chlorine Chloropicrin (PS) Phosgene (CG)

Diphosgene (DP) Incapacitating agents

Agent 15 (BZ) Dimethylheptylpyran (DMHP) 1. EA-3167 2. Kolokol-1 PAVA spray Sleeping gas Riot control agents Pepper spray (OC) 1. CS 2. CN (mace) 3. CR

List of chemical warfare agents Weapons of mass destruction By type Biological Chemical Nuclear

Radiological By country Albania

Algeria

Argentina

Australia

Brazil

Bulgaria

Burma

Canada

China

Egypt

France

Germany

India

Iran

Iraq

Israel

Japan

Libya

Mexico

Netherlands

North Korea

Pakistan

Poland

Romania

Russia

Saudi Arabia

South Africa

South Korea

Spain

Sweden

Syria

Taiwan

Ukraine

United Kingdom

United States Proliferation Chemical Nuclear Missiles Treaties List of treaties

Book Category

Chemical warfare (CW) involves using the toxic properties of chemical substances as weapons. This type of warfare is distinct from nuclear warfare and biological warfare, which together make up NBC, the military acronym for nuclear, biological, and chemical (warfare or weapons), all of which are considered "weapons of mass destruction" (WMD). None of these fall under the term conventional weapons which are primarily effective due to their destructive potential. Chemical warfare does not depend upon explosive force to achieve an objective. Rather it depends upon the unique properties of the chemical agent weaponized. A lethal agent is designed to injure or incapacitate the enemy, or deny unhindered use of a particular area of terrain. Defoliants are used to quickly kill vegetation and deny its use for cover and concealment. It can also be used against agriculture and livestock to promote hunger and starvation. With proper protective equipment, training, and decontamination measures, the primary effects of chemical weapons can be overcome. Many nations possess vast stockpiles of weaponized agents in preparation for wartime use. The threat and the perceived threat have become strategic tools in planning both measures and countermeasures.

Definition
Chemical warfare is different from the use of conventional weapons or nuclear weapons because the destructive effects of chemical weapons are not primarily due to any explosive force. The offensive use of living organisms (such as anthrax) is considered biological warfare rather than chemical warfare; however, the use of nonliving toxic products produced by living organisms (e.g. toxins such as botulinum toxin, ricin, and saxitoxin) is considered chemical warfare under the provisions of the Chemical Weapons Convention (CWC). Under this Convention, any toxic chemical, regardless of its origin, is considered a chemical weapon unless it is used for purposes that are not prohibited (an important legal definition known as the General Purpose Criterion). About 70 different chemicals have been used or stockpiled as chemical warfare agents during the 20th century. The entire class known as Lethal Unitary Chemical Agents and Munitions have been scheduled for elimination by the CWC.1 Under the Convention, chemicals that are toxic enough to be used as chemical weapons, or that may be used to manufacture such chemicals, are divided into three groups according to their purpose and treatment: Schedule 1 Have few, if any, legitimate uses. These may only be produced or used for research, medical, pharmaceutical or protective purposes (i.e. testing of chemical weapons sensors and protective clothing). Examples include nerve agents, ricin, lewisite and mustard gas. Any production over 100 g must be reported to the OPCW and a country can have a stockpile of no more than one tonne of these chemicals.
1Disarmament lessons from the Chemical Weapons Convention

Schedule 2 Have no large-scale industrial uses, but may have legitimate small-scale uses. Examples include dimethyl methylphosphonate, a precursor to sarin but which is also used as a flame retardant and Thiodiglycol which is a precursor chemical used in the manufacture of mustard gas but is also widely used as a solvent in inks. Schedule 3 Have legitimate large-scale industrial uses. Examples include phosgene and chloropicrin. Both have been used as chemical weapons but phosgene is an important precursor in the manufacture of plastics and chloropicrin is used as a fumigant. The OPCW must be notified of, and may inspect, any plant producing more than 30 tonnes per year.

Technology
Chemical warfare technology timeline Agents 1914 Chlorine Chloropicrin Phosgene Mustard gas Lewisite Dissemination Protection Detection Smell

Wind dispersal Gas masks, urinated-on gauze Chemical shells Gas mask Rosin oil clothing Projectiles w/ CC-2 clothing central bursters

1918

smell of geraniums

1920s 1930s

G-series nerve Aircraft bombs agents

Blister agent detectors Color change paper Protective ointment (mustard) Collective protection Gas mask w/ Whetlerite Gas mask w/ water supply Improved gas Nerve gas alarm Laser detection

1940s

Missile warheads Spray tanks

1950s 1960s 1970s 1980s Binary V-series nerve agents Aerodynamic

munitions

masks (protection, fit, comfort)

1990s

Novichok nerve agents

Although crude chemical warfare has been employed in many parts of the world for thousands of years, "modern" chemical warfare began during World War I see Chemical weapons in World War I. Initially, only well-known commercially available chemicals and their variants were used. These included chlorine and phosgene gas. The methods used to disperse these agents during battle were relatively unrefined and inefficient. Even so, casualties could be heavy, due to the mainly static troop positions which were characteristic features of trench warfare. Germany, the first side to employ chemical warfare on the battlefield, simply opened canisters of chlorine upwind of the opposing side and let the prevailing winds do the dissemination. Soon after, the French modified artillery munitions to contain phosgene a much more effective method that became the principal means of delivery. Since the development of modern chemical warfare in World War I, nations have pursued research and development on chemical weapons that falls into four major categories: new and more deadly agents; more efficient methods of delivering agents to the target (dissemination); more reliable means of defense against chemical weapons; and more sensitive and accurate means of detecting chemical agents. Germany was the first to produce chemical agents.

Chemical warfare agents


A chemical used in warfare is called a chemical warfare agent (CWA). About 70 different chemicals have been used or stockpiled as chemical warfare agents during the 20th and 21st-centuries. These agents may be in liquid, gas or solid form. Liquid agents that evaporate quickly are said to be volatile or have a high vapor pressure. Many chemical agents are made volatile so they can be dispersed over a large region quickly. The earliest target of chemical warfare agent research was not toxicity, but development of agents that can affect a target through the skin and clothing, rendering protective gas masks useless. In July 1917, the Germans employed mustard gas. Mustard gas easily penetrates leather and fabric to inflict painful burns on the skin. Chemical warfare agents are divided into lethal and incapacitating categories. A substance is classified as incapacitating if less than 1/100 of the lethal dose causes incapacitation, e.g., through nausea or visual problems. The distinction between lethal and incapacitating substances is not fixed, but relies on a statistical average called the LD50.

Persistency
Chemical warfare agents can be classified according to their persistency, a measure of the length of time that a chemical agent remains effective after dissemination. Chemical agents are classified as persistent or nonpersistent. Agents classified as nonpersistent lose effectiveness after only a few minutes or hours or even only a few seconds. Purely gaseous agents such as chlorine are nonpersistent, as are highly volatile agents such as sarin. Tactically, nonpersistent agents are very useful against targets that are to be taken over and controlled very quickly. Apart from the agent used, the delivery mode is very important. To achieve a nonpersistent deployment, the agent is dispersed into very small droplets comparable with the mist produced by an aerosol can. In this form not only the gaseous part of the agent (around 50%) but also the fine aerosol can be inhaled or absorbed through pores in the skin. Modern doctrine requires very high concentrations almost instantly in order to be effective (one breath should contain a lethal dose of the agent). To achieve this, the primary weapons used would be rocket artillery or bombs and large ballistic missiles with cluster warheads. The contamination in the target area is only low or not existent and after four hours sarin or similar agents are not detectable anymore. By contrast, persistent agents tend to remain in the environment for as long as several weeks, complicating decontamination. Defense against persistent agents requires shielding for extended periods of time. Non-volatile liquid agents, such as blister agents and the oily VX nerve agent, do not easily evaporate into a gas, and therefore present primarily a contact hazard. The droplet size used for persistent delivery goes up to 1 mm increasing the falling speed and therefore about 80% of the deployed agent reaches the ground, resulting in heavy contamination. This implies, that persistent deployment does not aim at annihilating the enemy but to constrain him. Possible targets include enemy flank positions (averting possible counterattacks), artillery regiments, commando posts or supply lines. Possible weapons to be used are wide spread, because the fast delivery of high amounts is not a critical factor. A special form of persistent agents are thickened agents. These comprise a common agent mixed with thickeners to provide gelatinous, sticky agents. Primary targets for this kind of use include airfields, due to the increased persistency and difficulty of decontaminating affected areas.

Classes
Chemical weapons are inert agents that come in four categories: choking, blister, blood and nerve.2 The agents are organized into several categories according to the manner in which they affect the human body. The names and number of categories varies slightly from source to source, but in general, types of chemical warfare agents are as follows: Classes of chemical weapon agents Class of agent Nerve Agent Names Mode of Action Signs and Symptoms Rate of action Persistency VX is persistent and a contact hazard; other agents are nonpersistent and present mostly inhalation hazards.

Inactivates enzyme Cyclosarin Miosis Vapors: acetylcholine (GF) (pinpoint seconds to sterase, pupils) minutes; Sarin (GB) preventing Blurred/dim Skin: 2 to Soman (GD) the 18 hours breakdown vision Tabun (GA) of the Headache neurotransmi VX Nausea, tter VR acetylcholine vomiting, diarrhea in the Some insecticides victim's Copious synapses and secretions/sw Novichok causing both eating agents muscarinic and nicotinic Muscle twitching/fas effects ciculations Dyspnea Seizures Loss of consciousnes s

Asphyxiant/ Blood

Most Arsines Cyanogen chloride Hydrogen

Possible Arsine: cherry-red Causes intravascular skin hemolysis Possible that may cyanosis lead to renal

Immediate onset

Nonpersistent and an inhalation hazard.

2Gray, Colin. (2007). Another Bloody Century: Future Warfare. Page 269. Phoenix. ISBN 0-30436734-6.

cyanide

failure. Cyanogen chloride/hy drogen cyanide: Cyanide directly prevents cells from using oxygen. The cells then uses anaerobic respiration, creating excess lactic acid and metabolic acidosis.

Confusion Nausea Patients may gasp for air Seizures prior to death Metabolic acidosis

Vesicant/Bli ster

Agents are Persistent acid-forming and a contact Sulfur Severe skin, Mustards: compounds hazard. mustard (HD, eye and Vapors: 4 to that damages H) mucosal pain 6 hours, eyes skin and and irritation and lungs Nitrogen respiratory affected mustard Skin system, more rapidly; (HN-1, HN-2, resulting erythema Skin: 2 to 48 HN-3) with large burns and hours fluid blisters respiratory Lewisite (L) that heal Lewisite: problems. Phosgene slowly and Immediate oxime (CX) may become infected Tearing, conjunctivitis , corneal damage Mild respiratory distress to marked airway damage

Choking/Pul monary

Chlorine Hydrogen chloride Nitrogen oxides Phosgene

Similar Immediate to Nonmechanism 3 hours persistent Airway to blister and an irritation agents in inhalation Eye and that the hazard. compounds skin are acids or irritation acid-forming, Dyspnea, but action is cough more pronounced Sore throat in Chest respiratory tightness system, Wheezing flooding it and resulting Bronchospa in sm suffocation; survivors often suffer chronic breathing problems. Causes Powerful eye Immediate severe irritation stinging of the eyes and temporary blindness. Causes atropine-like May appear Inhaled: 30 inhibition of as mass drug minutes to acetylcholine intoxication 20 hours; in subject. with erratic Skin: Up to Causes behaviors, 36 hours peripheral shared after skin nervous realistic and exposure to system distinct BZ. Duration effects that hallucination is typically are the s, disrobing 72 to 96 opposite of and hours. those seen in confusion nerve agent Hypertherm poisoning. ia Nonpersistent and an inhalation hazard. Extremely persistent in soil and water and on most surfaces; contact hazard.

Lachrymato ry agent

Tear gas Pepper spray

Incapacitati ng

Agent 15 (BZ)

Ataxia (lack of coordination) Mydriasis (dilated pupils) Dry mouth and skin Cytotoxic proteins Non-living biological proteins, such as: Ricin Abrin Inhibit protein synthesis 4-24 hours; see Latent symptoms. period of 4-8 Exposure by hours, inhalation or followed by injection flu-like signs causes more and pronounced symptoms signs and Progress symptoms within 18-24 than hours to: exposure by 1. Inha ingestion latio n: naus ea, cou gh, dysp nea, pul mon ary ede ma 2. Inge stio n: Gast roin testi nal hem orrh age Slight; agents degrade quickly in environment

with eme sis and bloo dy diar rhea ; even tual liver and kidn ey failu re.

There are other chemicals used militarily that are not scheduled by the Chemical Weapons Convention, and thus are not controlled under the CWC treaties. These include: Defoliants that destroy vegetation, but are not immediately toxic to human beings. Some batches of Agent Orange, for instance, used by the United States in Vietnam, contained dioxins as manufacturing impurities. Dioxins, rather than Agent Orange itself, have long-term cancer effects and for causing genetic damage leading to serious birth deformities. Incendiary or explosive chemicals (such as napalm, extensively used by the United States in Vietnam, or dynamite) because their destructive effects are primarily due to fire or explosive force, and not direct chemical action. Viruses, bacteria, or other organisms. Their use is classified as biological warfare. Toxins produced by living organisms are considered chemical weapons, although the boundary is blurry. Toxins are covered by the Biological Weapons Convention.

Designations
Most chemical weapons are assigned a one- to three-letter "NATO weapon designation" in addition to, or in place of, a common name. Binary munitions, in which precursors for chemical warfare agents are automatically mixed in shell to produce the agent just prior to its use, are indicated by a "-2" following the agent's designation (for example, GB-2 and VX-2).

Some examples are given below: Blood agents: Cyanogen chloride: CK Hydrogen cyanide: AC Pulmonary agents: Phosgene: CG Lachrymatory agents: Pepper spray: OC Tear gas: CN, CS, CR Vesicants: Lewisite: L Sulfur mustard: H, HD, HS, HT Incapacitating agents: Quinuclidinyl benzilate: BZ Nerve agents: Sarin: GB VE, VG, VM, VX

Delivery
The most important factor in the effectiveness of chemical weapons is the efficiency of its delivery, or dissemination, to a target. The most common techniques include munitions (such as bombs, projectiles, warheads) that allow dissemination at a distance and spray tanks which disseminate from low-flying aircraft. Developments in the techniques of filling and storage of munitions have also been important. Although there have been many advances in chemical weapon delivery since World War I, it is still difficult to achieve effective dispersion. The dissemination is highly dependent on atmospheric conditions because many chemical agents act in gaseous form. Thus, weather observations and forecasting are essential to optimize weapon delivery and reduce the risk of injuring friendly forces.

Dispersion
Dispersion is placing the chemical agent upon or adjacent to a target immediately before dissemination, so that the material is most efficiently used. Dispersion is the simplest technique of delivering an agent to its target. The most common techniques are munitions, bombs, projectiles, spray tanks and warheads.

World War I saw the earliest implementation of this technique. The actual first chemical ammunition was the French 26 mm cartouche suffocante rifle grenade, fired from a flare carbine. It contained 35g of the tear-producer ethyl bromoacetate, and was used in autumn 1914 with little effect on the Germans. The Germans on the other hand tried to increase the effect of 10.5 cm shrapnel shells by adding an irritant dianisidine chlorosulfonate. Its use went unnoticed by the British when it was used against them at Neuve Chapelle in October 1914. Hans Tappen, a chemist in the Heavy Artillery Department of the War Ministry, suggested to his brother, the Chief of the Operations Branch at German General Headquarters, the use of the tear-gases benzyl bromide or xylyl bromide. Shells were tested successfully at the Wahn artillery range near Cologne on 9 January 1915, and an order was placed for 15 cm howitzer shells, designated Tshells after Tappen. A shortage of shells limited the first use against the Russians at Bolimw on 31 January 1915; the liquid failed to vaporize in the cold weather, and again the experiment went unnoticed by the Allies. The first effective use were when the German forces at the Second Battle of Ypres simply opened cylinders of chlorine and allowed the wind to carry the gas across enemy lines. While simple, this technique had numerous disadvantages. Moving large numbers of heavy gas cylinders to the front-line positions from where the gas would be released was a lengthy and difficult logistical task. Stockpiles of cylinders had to be stored at the front line, posing a great risk if hit by artillery shells. Gas delivery depended greatly on wind speed and direction. If the wind was fickle, as at Loos, the gas could blow back, causing friendly casualties. Gas clouds gave plenty of warning, allowing the enemy time to protect themselves, though many soldiers found the sight of a creeping gas cloud unnerving. This made the gas doubly effective, as, in addition to damaging the enemy physically, it also had a psychological effect on the intended victims. Another disadvantage was that gas clouds had limited penetration, capable only of affecting the front-line trenches before dissipating. Although it produced limited results in World War I, this technique shows how simple chemical weapon dissemination can be. Shortly after this "open canister" dissemination, French forces developed a technique for delivery of phosgene in a non-explosive artillery shell. This technique overcame many of the risks of dealing with gas in cylinders. First, gas shells were independent of the wind and increased the effective range of gas, making any target within reach of guns vulnerable. Second, gas shells could be delivered without warning, especially the clear, nearly odorless phosgene there are numerous accounts of gas shells, landing with a "plop" rather than exploding, being initially dismissed as dud high explosive or shrapnel shells, giving the gas time to work before the soldiers were alerted and took precautions.

The major drawback of artillery delivery was the difficulty of achieving a killing concentration. Each shell had a small gas payload and an area would have to be subjected to saturation bombardment to produce a cloud to match cylinder delivery. A British solution to the problem was the Livens Projector. This was effectively a large-bore mortar, dug into the ground that used the gas cylinders themselves as projectiles - firing a 14 kg cylinder up to 1500 m. This combined the gas volume of cylinders with the range of artillery. Over the years, there were some refinements in this technique. In the 1950s and early 1960s, chemical artillery rockets and cluster bombs contained a multitude of submunitions, so that a large number of small clouds of the chemical agent would form directly on the target.

Thermal dissemination
Thermal dissemination is the use of explosives or pyrotechnics to deliver chemical agents. This technique, developed in the 1920s, was a major improvement over earlier dispersal techniques, in that it allowed significant quantities of an agent to be disseminated over a considerable distance. Thermal dissemination remains the principal method of disseminating chemical agents today. Most thermal dissemination devices consist of a bomb or projectile shell that contains a chemical agent and a central "burster" charge; when the burster detonates, the agent is expelled laterally. Thermal dissemination devices, though common, are not particularly efficient. First, a percentage of the agent is lost by incineration in the initial blast and by being forced onto the ground. Second, the sizes of the particles vary greatly because explosive dissemination produces a mixture of liquid droplets of variable and difficult to control sizes. The efficacy of thermal detonation is greatly limited by the flammability of some agents. For flammable aerosols, the cloud is sometimes totally or partially ignited by the disseminating explosion in a phenomenon called flashing. Explosively disseminated VX will ignite roughly one third of the time. Despite a great deal of study, flashing is still not fully understood, and a solution to the problem would be a major technological advance. Despite the limitations of central bursters, most nations use this method in the early stages of chemical weapon development, in part because standard munitions can be adapted to carry the agents.

Aerodynamic dissemination
Aerodynamic dissemination is the non-explosive delivery of a chemical agent from an aircraft, allowing aerodynamic stress to disseminate the agent. This technique is the most recent major development in chemical agent dissemination, originating in the mid-1960s.

This technique eliminates many of the limitations of thermal dissemination by eliminating the flashing effect and theoretically allowing precise control of particle size. In actuality, the altitude of dissemination, wind direction and velocity, and the direction and velocity of the aircraft greatly influence particle size. There are other drawbacks as well; ideal deployment requires precise knowledge of aerodynamics and fluid dynamics, and because the agent must usually be dispersed within the boundary layer (less than 200300 ft above the ground), it puts pilots at risk. Significant research is still being applied toward this technique. For example, by modifying the properties of the liquid, its breakup when subjected to aerodynamic stress can be controlled and an idealized particle distribution achieved, even at supersonic speed. Additionally, advances in fluid dynamics, computer modeling, and weather forecasting allow an ideal direction, speed, and altitude to be calculated, such that warfare agent of a predetermined particle size can predictably and reliably hit a target.

Protection against chemical warfare


Ideal protection begins with nonproliferation treaties such as the Chemical Weapons Convention, and detecting, very early, the signatures of someone building a chemical weapons capability. These include a wide range of intelligence disciplines, such as economic analysis of exports of dual-use chemicals and equipment, human intelligence (HUMINT) such as diplomatic, refugee, and agent reports; photography from satellites, aircraft and drones (IMINT); examination of captured equipment (TECHINT); communications intercepts (COMINT); and detection of chemical manufacturing and chemical agents themselves (MASINT). If all the preventive measures fail and there is a clear and present danger, then there is a need for detection of chemical attacks, collective protection, and decontamination. Since industrial accidents can cause dangerous chemical releases (e.g., the Bhopal disaster), these activities are things that civilian, as well as military, organizations must be prepared to carry out. In civilian situations in developed countries, these are duties of HAZMAT organizations, which most commonly are part of fire departments. Detection has been referred to above, as a technical MASINT discipline; specific military procedures, which are usually the model for civilian procedures, depend on the equipment, expertise, and personnel available. When chemical agents are detected, an alarm needs to sound, with specific warnings over emergency broadcasts and the like. There may be a warning to expect an attack.

If, for example, the captain of a US Navy ship believes there is a serious threat of chemical, biological, or radiological attack, the crew may be ordered to set Circle William, which means closing all openings to outside air, running breathing air through filters, and possibly starting a system that continually washes down the exterior surfaces. Civilian authorities dealing with an attack or a toxic chemical accident will invoke the Incident Command System, or local equivalent, to coordinate defensive measures. Individual protection starts with a gas mask and, depending on the nature of the threat, through various levels of protective clothing up to a complete chemicalresistant suit with a self-contained air supply. The US military defines various levels of MOPP (mission-oriented protective posture) from mask to full chemical resistant suits; Hazmat suits are the civilian equivalent, but go farther to include a fully independent air supply, rather than the filters of a gas mask. Collective protection allows continued functioning of groups of people in buildings or shelters, the latter which may be fixed, mobile, or improvised. With ordinary buildings, this may be as basic as plastic sheeting and tape, although if the protection needs to be continued for any appreciable length of time, there will need to be an air supply, typically a scaled-up version of a gas mask.

Decontamination
Decontamination varies with the particular chemical agent used. Some nonpersistent agents, such as most pulmonary agents such as chlorine and phosgene, blood gases, and nonpersistent nerve gases (e.g., GB) will dissipate from open areas, although powerful exhaust fans may be needed to clear out buildings where they have accumulated. In some cases, it might be necessary to neutralize them chemically, as with ammonia as a neutralizer for hydrogen cyanide or chlorine. Riot control agents such as CS will dissipate in an open area, but things contaminated with CS powder need to be aired out, washed by people wearing protective gear, or safely discarded. Mass decontamination is a less common requirement for people than equipment, since people may be immediately affected and treatment is the action required. It is a requirement when people have been contaminated with persistent agents. Treatment and decontamination may need to be simultaneous, with the medical personnel protecting themselves so they can function. There may need to be immediate intervention to prevent death, such as injection of atropine for nerve agents. Decontamination is especially important for people contaminated with persistent agents; many of the fatalities after the explosion of a WWII US ammunition ship carrying mustard gas, in the harbor of Bari, Italy, after a German bombing on 2 December 1943, came when rescue workers, not knowing of the contamination, bundled cold, wet seamen in tight-fitting blankets.

For decontaminating equipment and buildings exposed to persistent agents, such as blister agents, VX or other agents made persistent by mixing with a thickener, special equipment and materials might be needed. Some type of neutralizing agent will be needed; e.g. in the form of a spraying device with neutralizing agents such as Chlorine, Fichlor, strong alkaline solutions or enzymes. In other cases, a specific chemical decontaminant will be required.

Sociopolitical climate
The study of chemicals and their military uses was widespread in China and India. The use of toxic materials has historically been viewed with mixed emotions and moral qualms in the West. The practical and ethical problems surrounding poison warfare appeared in ancient Greek myths about Hercules' invention of poison arrows and Odysseus's use of toxic projectiles. There are many instances of the use of chemical weapons in battles documented in Greek and Roman historical texts; the earliest example was the deliberate poisoning of Kirrha's water supply with hellebore in the First Sacred War, Greece, about 590 BC.3 One of the earliest reactions to the use of chemical agents was from Rome. Struggling to defend themselves from the Roman legions, Germanic tribes poisoned the wells of their enemies, with Roman jurists having been recorded as declaring "armis bella non venenis geri", meaning "war is fought with weapons, not with poisons." Yet the Romans themselves resorted to poisoning wells of besieged cities in Anatolia in the 2nd century BCE.4 Before 1915 the use of poisonous chemicals in battle was typically the result of local initiative, and not the result of an active government chemical weapons program. There are many reports of the isolated use of chemical agents in individual battles or sieges, but there was no true tradition of their use outside of incendiaries and smoke. Despite this tendency, there have been several attempts to initiate large-scale implementation of poison gas in several wars, but with the notable exception of World War I, the responsible authorities generally rejected the proposals for ethical reasons. For example, in 1854 Lyon Playfair (later 1st Baron Playfair, GCB, PC, FRS (1 May 1818 29 May 1898), a British chemist, proposed using a cacodyl cyanidefilled artillery shell against enemy ships during the Crimean War. The British Ordnance Department rejected the proposal as "as bad a mode of warfare as poisoning the wells of the enemy."

Efforts to eradicate chemical weapons


Nation CW Possession Signed CWC Ratified CWC
3Adrienne Mayor, "Greek Fire, Poison Arrows & Scorpion Bombs: Biological and Chemical Warfare in the Ancient World" Overlook-Duckworth, 2003, rev ed with new Introduction 2008 4Mayor 2003

Albania Burma (Myanmar) China Egypt India Iran Israel Japan Libya North Korea Pakistan Russia Serbia and Montenegro Sudan Syria Taiwan United States Vietnam

Known Possible Probable Probable Known Known Probable Probable Known Known Probable Known Probable Possible Known Possible Known Probable

January 14, 1993 January 13, 1993 January 13, 1993 No January 14, 1993 January 13, 1993 January 13, 1993 January 13, 1993 No No January 13, 1993 January 13, 1993 No No No n/a January 13, 1993 January 13, 1993

May 11, 1994 No April 4, 1997 No September 3, 1996 November 3, 1997 No September 15, 1995 January 6, 2004 (acceded) No October 28, 1997 November 5, 1997 April 20, 2000 (acceded) May 24, 1999 (acceded) No n/a April 25, 1997 September 30, 1998

August 27, 1874: The Brussels Declaration Concerning the Laws and Customs of War is signed, specifically forbidding the "employment of poison or poisoned weapons." September 4, 1900: The Hague Conference, which includes a declaration banning the "use of projectiles the object of which is the diffusion of asphyxiating or deleterious gases," enters into force. February 6, 1922: After World War I, the Washington Arms Conference Treaty prohibited the use of asphyxiating, poisonous or other gases. It was signed by the United States, Britain, Japan, France, and Italy, but France objected to other provisions in the treaty and it never went into effect. September 7, 1929: The Geneva Protocol enters into force, prohibiting the use of poison gas.

Chemical weapon proliferation


Despite numerous efforts to reduce or eliminate them, some nations continue to research and/or stockpile chemical warfare agents. To the right is a summary of the nations that have either declared weapon stockpiles or are suspected of secretly stockpiling or possessing CW research programs. Notable examples include United States and Russia. In 1997, future US Vice President Dick Cheney opposed the signing ratification of a treaty banning the use chemical weapons, a recently unearthed letter shows. In a letter dated April 8, 1997, then Halliburton-CEO Cheney told Sen. Jesse Helms, the chairman of the Senate Foreign Relations Committee, that it would be a mistake for America to join the Convention. "Those nations most likely to comply with the Chemical Weapons Convention are not likely to ever constitute a military threat to the United States. The governments we should be concerned about are likely to cheat on the CWC, even if they do participate," reads the letter, published by the Federation of American Scientists. The CWC was ratified by the Senate that same month. Since then, Albania, Libya, Russia, the United States, and India have declared over 71,000 metric tons of chemical weapon stockpiles, and destroyed about a third of them. Under the terms of the agreement, the United States and Russia agreed to eliminate the rest of their supplies of chemical weapons by 2012. Not having met its goal, the U.S. government estimates remaining stocks will be destroyed by 2017. [citation needed]

History
Outline of war

Ancient to medieval times


Chemical weapons have been used for millennia in the form of poisoned spears and arrows, but evidence can be found for the existence of more advanced forms of chemical weapons in ancient and classical times. A good example of early chemical warfare was the late Stone Age (10 000 BC) hunter-gatherer societies in Southern Africa, known as the San.[citation needed] They used poisoned arrows, tipping the wood, bone and stone tips of their arrows with poisons obtained from their natural environment. These poisons were mainly derived from scorpion or snake venom, but it is believed that some poisonous plants were also utilized. The arrow was fired into the target of choice, usually an antelope (the favourite being an eland), with the hunter then tracking the doomed animal until the poison caused its collapse. Ancient Greek myths about Hercules poisoning his arrows with the venom of the Hydra Monster are the earliest references to toxic weapons in western literature. Homer's epics, the Iliad and the Odyssey, allude to poisoned arrows used by both sides in the legendary Trojan War (Bronze Age Greece).

Textual and literary evidence


Some of the earliest surviving references to toxic warfare appear in the Indian epics Ramayana and Mahabharata. The "Laws of Manu," a Hindu treatise on statecraft (c. 400 BC) forbids the use of poison and fire arrows, but advises poisoning food and water. Kautilya's "Arthashastra", a statecraft manual of the same era, contains hundreds of recipes for creating poison weapons, toxic smokes, and other chemical weapons. Ancient Greek historians recount that Alexander the Great encountered poison arrows and fire incendiaries in India at Indus Basin in the 4th century BC. Arsenical smokes were known to the Chinese as far back as c. 1000 BC and Sun Tzu's "Art of War" (c. 200 BC) advises the use of fire weapons. In the 2nd century BC, writings of the Mohist sect in China describe the use of bellows to pump smoke from burning balls of mustard and other toxic vegetables into tunnels being dug by a besieging army. Other Chinese writings dating around the same period contain hundreds of recipes for the production of poisonous or irritating smokes for use in war along with numerous accounts of their use. From these accounts we know of the arsenic-containing "soul-hunting fog", and the use of finely divided lime dispersed into the air to suppress a peasant revolt in AD 178. The earliest recorded use of gas warfare in the West dates back to the 5th century BC, during the Peloponnesian War between Athens and Sparta. Spartan forces besieging an Athenian city placed a lighted mixture of wood, pitch, and sulfur under the walls hoping that the noxious smoke would incapacitate the Athenians, so that they would not be able to resist the assault that followed. Sparta was not alone in its use of unconventional tactics in ancient Greece: Solon of Athens is said to have used hellebore roots to poison the water in an aqueduct leading from the River Pleistos around 590 BC during the siege of Kirrha. Polish chronicler Jan Dugosz mentions usage of poisonous gas by the Mongol army in 1241 in the Battle of Legnica. However, his report is not firsthand, as he was born in the 15th century. According to Mukhamedzhan Tynyshpaev, Dugosz's chronicle is unclear as to what kind of device or gas was used, giving only a description of a noxious smell. Rather, he suggests, this is a repeat of the trope of the Mongols' bad smell as an excuse for their annihilation of European defenders.5 Historian and philosopher David Hume, in his history of England, recounts how in the reign of Henry III (r.1216 - 1272) the English Navy destroyed an invading French fleet, by blinding the enemy fleet with "quicklime," the old name for calcium oxide. DAlbiney employed a stratagem against them, which is said to have contributed to the victory: Having gained the wind of the French, he came down upon them with violence; and throwing in their faces a great quantity of quicklime, which he purposely carried on board, he so blinded them, that they were disabled from defending themselves.6

5M. Tynyshpaev, Istoriya Kazakhskogo Naroda, Qazaq Universiteti, Almaty, 1993. p. 219 6David Hume, History of England, Volume II.

Archaeological evidence
There is archaeological evidence that the Sasanians deployed chemical weapons against the Roman army in 3rd century AD/CE. Research carried out on the collapsed tunnels at Dura-Europos in Syria suggests that the Iranians used bitumen and sulfur crystals to get it burning. When ignited, the materials gave off dense clouds of choking gases which killed 20 Roman soldiers in a matter of 2 minutes.7

Rediscovery
During the Renaissance, people again considered using chemical warfare. One of the earliest such references is from Leonardo da Vinci, who proposed a powder of sulfide of arsenic and verdigris in the 15th century: throw poison in the form of powder upon galleys. Chalk, fine sulfide of arsenic, and powdered verdegris may be thrown among enemy ships by means of small mangonels, and all those who, as they breathe, inhale the powder into their lungs will become asphyxiated. It is unknown whether this powder was ever actually used. In the late 15th century, Spanish conquistadors encountered a rudimentary type of chemical warfare on the island of Hispaniola. The Tano threw gourds filled with ashes and ground hot peppers at the Spaniards to create a blinding smoke screen before launching their attack. In the 17th century during sieges, armies attempted to start fires by launching incendiary shells filled with sulfur, tallow, rosin, turpentine, saltpeter, and/or antimony. Even when fires were not started, the resulting smoke and fumes provided a considerable distraction. Although their primary function was never abandoned, a variety of fills for shells were developed to maximize the effects of the smoke. In 1672, during his siege of the city of Groningen, Christoph Bernhard von Galen, the Bishop of Mnster, employed several different explosive and incendiary devices, some of which had a fill that included Deadly Nightshade, intended to produce toxic fumes. Just three years later, August 27, 1675, the French and the Holy Roman Empire concluded the Strasbourg Agreement, which included an article banning the use of "perfidious and odious" toxic devices.[citation needed] In 1854, Lyon Playfair, a British chemist, proposed a cacodyl cyanide artillery shell for use against enemy ships as way to solve the stalemate during the siege of Sevastopol. The proposal was backed by Admiral Thomas Cochrane of the Royal Navy. It was considered by the Prime Minister, Lord Palmerston, but the British Ordnance Department rejected the proposal as "as bad a mode of warfare as poisoning the wells of the enemy." Playfairs response was used to justify chemical warfare into the next century:[citation needed]

7Science Daily, dated January 19, 2009 Sciencedaily.com

There was no sense in this objection. It is considered a legitimate mode of warfare to fill shells with molten metal which scatters among the enemy, and produced the most frightful modes of death. Why a poisonous vapor which would kill men without suffering is to be considered illegitimate warfare is incomprehensible. War is destruction, and the more destructive it can be made with the least suffering the sooner will be ended that barbarous method of protecting national rights. No doubt in time chemistry will be used to lessen the suffering of combatants, and even of criminals condemned to death. Later, during the American Civil War, New York school teacher John Doughty proposed the offensive use of chlorine gas, delivered by filling a 10 inch (254 millimeter) artillery shell with 2 to 3 quarts (2 to 3 liters) of liquid chlorine, which could produce many cubic feet (a few cubic meters) of chlorine gas. Doughtys plan was apparently never acted on, as it was probably[citation needed] presented to Brigadier General James Wolfe Ripley, Chief of Ordnance, who was described as being congenitally immune to new ideas.Wikipedia:Avoid weasel words A general concern over the use of poison gas manifested itself in 1899 at the Hague Conference with a proposal prohibiting shells filled with asphyxiating gas. The proposal was passed, despite a single dissenting vote from the United States. The American representative, Navy Captain Alfred Thayer Mahan, justified voting against the measure on the grounds that "the inventiveness of Americans should not be restricted in the development of new weapons."

World War I
The Hague Declaration of 1899 and the Hague Convention of 1907 forbade the use of "poison or poisoned weapons" in warfare, yet more than 124,000 tons of gas were produced by the end of World War I. The French were the first to use chemical weapons during the First World War, using the tear gases, ethyl bromoacetate and chloroacetone. One of Germany's earliest uses of chemical weapons occurred on October 27, 1914 when shells containing the irritant, dianisidine chlorosulfonate, were fired at British troops near Neuve-Chapelle, France. Germany used another irritant, xylyl bromide, in artillery shells that were fired in January 1915 at the Russians near Bolimw, nowadays in Poland.8 The first full-scale deployment of deadly chemical warfare agents during World War I, was at the Second Battle of Ypres, on April 22, 1915, when the Germans attacked French, Canadian and Algerian troops with chlorine gas. Deaths were light, though casualties relatively heavy. A total 50,965 tons of pulmonary, lachrymatory, and vesicant agents were deployed by both sides of the conflict, including chlorine, phosgene and mustard gas. Official figures declare about 1,176,500 non-fatal casualties and 85,000 fatalities directly caused by chemical warfare agents during the course of the war.
8"The First World War" (a Channel 4 documentary based on the book by Hew Strachan)

To this day unexploded World War I-era chemical ammunition is still uncovered when the ground is dug in former battle or depot areas and continues to pose a threat to the civilian population in Belgium and France and less commonly in other countries. After the war, most of the unused German chemical warfare agents were dumped into the Baltic Sea, a common disposal method among all the participants in several bodies of water. Over time, the salt water causes the shell casings to corrode, and mustard gas occasionally leaks from these containers and washes onto shore as a wax-like solid resembling ambergris.

Interwar years
In 1919, the Royal Air Force dropped arsenic gas on Bolshevik troops during the British intervention in the Russian Civil War.9 After World War I chemical agents were occasionally used to subdue populations and suppress rebellion. In 1920, the Arab and Kurdish people of Mesopotamia revolted against the British occupation, which cost the British dearly. As the Mesopotamian resistance gained strength, the British resorted to increasingly repressive measures. Much speculation was made about aerial bombardment of major cities with gas in Mesopotamia, with Winston Churchill, then-Secretary of State at the British War Office, arguing in favor of gas.1011 The Bolsheviks also employed poison gas in 1921 during the Tambov Rebellion. An order signed by military commanders Tukhachevsky and Vladimir AntonovOvseyenko stipulated: "The forests where the bandits are hiding are to be cleared by the use of poison gas. This must be carefully calculated, so that the layer of gas penetrates the forests and kills everyone hiding there."12 During the Rif War in Spanish Morocco in 19211927, combined Spanish and French forces dropped mustard gas bombs in an attempt to put down the Berber rebellion. (See also: Chemical weapons in the Rif War)

9Walter E. Grunden: Secret Weapons And World War II: Japan In The Shadow Of Big Science , Lawrence (Kansas) 2005 , S. 172. 10Was Winston Churchill really "strongly in favor of using poisoned gas against uncivilized tribes" from the Churchill Papers 16/16, 12 May 1919 at www.winstonchurchill.org [0], accessed 10 September 2013 11Libcom.org, Libcom 1804-2003: History of Iraq 12Nicolas Werth, Karel Bartoek, Jean-Louis Pann, Jean-Louis Margolin, Andrzej Paczkowski, Stphane Courtois, The Black Book of Communism: Crimes, Terror, Repression, Harvard University Press, 1999, hardcover, 858 pages, ISBN 0-674-07608-7

In 1925, sixteen of the world's major nations signed the Geneva Protocol, thereby pledging never to use gas in warfare again. Notably, while the United States delegation under Presidential authority signed the Protocol. it languished in the U. S. Senate until 1975, when it was finally ratified.

Use of Mustard Gas in Ethiopia by Fascist Italy 1935


In 1935, Fascist Italy used mustard gas during the invasion of Ethiopia in the Second Italo-Abyssinian War. Ignoring the Geneva Protocol, which it signed seven years earlier, the Italian military dropped mustard gas in bombs, sprayed it from airplanes, and spread it in powdered form on the ground. 150,000 chemical casualties were reported, mostly from mustard gas.

Germany
Shortly after the end of World War I, Germany's General Staff enthusiastically pursued a recapture of their preeminent position in chemical warfare. In 1923, Hans von Seeckt pointed the way, by suggesting that German poison gas research move in the direction of delivery by aircraft in support of mobile warfare. Also in 1923, at the behest of the German army, poison gas expert Dr. Hugo Stoltzenberg negotiated with the USSR to build a huge chemical weapons plant at Trotsk, on the Volga river. Collaboration between Germany and the USSR in poison gas continued on and off through the 1920s. In 1924, German officers debated the use of poison gas versus non-lethal chemical weapons against civilians. Chemical warfare was revolutionized by Nazi Germany's discovery of the nerve agents tabun (in 1937) and sarin (in 1939) by Gerhard Schrader, a chemist of IG Farben. IG Farben was Germany's premier poison gas manufacturer during World War II, so the weaponization of these agents can not be considered accidental.13 Both were turned over to the German Army Weapons Office prior to the outbreak of the war. The nerve agent soman was later discovered by Nobel Prize laureate Richard Kuhn and his collaborator Konrad Henkel at the Kaiser Wilhelm Institute for Medical Research in Heidelberg in spring of 1944. The Nazis developed and manufactured large quantities of several agents, but chemical warfare was not extensively used by either side. Chemical troops were set up (in Germany since 1934) and delivery technology was actively developed.

13Corum, James S., The Roots of Blitzkrieg, University Press of Kansas, USA, 1992, pp.106-107.

World War II
Use of blister agents in China by the Imperial Japanese Army since 1937
Despite article 171 of the Versailles Peace Treaty, article V of the Treaty in Relation to the Use of Submarines and Noxious Gases in Warfare and a resolution adopted against Japan by the League of Nations on 14 May 1938, the Imperial Japanese Army frequently used chemical weapons. Because of fear of retaliation however, those weapons were never used against Westerners, but against other Asians judged "inferior" by the imperial propaganda. According to historians Yoshiaki Yoshimi and Kentaro Awaya, gas weapons, such as tear gas, were used only sporadically in 1937 but in early 1938, the Imperial Japanese Army began full-scale use of sneeze and nausea gas (red), and from mid-1939, used mustard gas (yellow) against both Kuomintang and Communist Chinese troops.14 According to historians Yoshiaki Yoshimi and Seiya Matsuno, the chemical weapons were authorized by specific orders given by Emperor Hirohito himself, transmitted by the chief of staff of the army. For example, the Emperor authorized the use of toxic gas on 375 separate occasions during the Battle of Wuhan from August to October 1938.15 They were also profusely used during the invasion of Changde. Those orders were transmitted either by prince Kotohito Kan'in or general Hajime Sugiyama.16 The Imperial Japanese Army had used mustard gas and the US-developed (CWS-1918) blister agent Lewisite against Chinese troops and guerrillas. Experiments involving chemical weapons were conducted on live prisoners (Unit 731 and Unit 516). The Japanese also carried chemical weapons as they swept through Southeast Asia towards Australia. Some of these items were captured and analyzed by the Allies. Historian Geoff Plunkett has recorded how Australia covertly imported 1,000,000 chemical weapons from the United Kingdom from 1942 onwards and stored them in many storage depots around the country, including three tunnels in the Blue Mountains to the west of Sydney. They were to be as a retaliatory measure if the Japanese first used chemical weapons. Buried chemical weapons have been recovered at Marrangaroo and Columboola.

The causes of the nonuse of poison gas in World War II by Nazi Germany
14Yuki Tanaka, Poison Gas, the Story Japan Would Like to Forget, Bulletin of the Atomic Scientists, October 1988, p. 16-17 15Y. Yoshimi and S. Matsuno, Dokugasusen Kankei Shiry II, Kaisetsu, Jugonen Sens Gokuhi Shiryoshu, 1997, p.27-29 16Yoshimi and Matsuno, idem, Herbert Bix, Hirohito and the Making of Modern Japan, 2001, p.360-364

Recovered Nazi documents suggest that German intelligence incorrectly thought that the Allies also knew of these compounds, interpreting their lack of mention in the Allies' scientific journals as evidence that information about them was being suppressed. Germany ultimately decided not to use the new nerve agents, fearing a potentially devastating Allied retaliatory nerve agent deployment. Fisk, Robert (December 30, 2000), "Poison gas from Germany", Independent Wikipedia:Link rot William L. Shirer, in The Rise and Fall of the Third Reich, writes that the British high command considered the use of chemical weapons as a last-ditch defensive measure in the event of a Nazi invasion of Britain. Stanley P. Lovell, Deputy Director for Research and Development of the Office of Strategic Services, reports in his book Of Spies and Stratagems that the Allies knew the Germans had quantities of Gas Blau available for use in the defense of the Atlantic Wall. The use of nerve gas on the Normandy beachhead would have seriously impeded the Allies and possibly caused the invasion to fail altogether. He submitted the queston "Why was nerve gas not used in Normandy?" to be asked of Hermann Goering during his interrogation. Goering answered that the reason gas was not used had to do with horses. The Wehrmacht was dependent upon horse-drawn transport to move supplies to their combat units, and had never been able to devise a gas mask horses could tolerate; the versions they developed would not pass enough pure air to allow the horses to pull a cart. Thus, gas was of no use to the German Army under most conditions.

Probable use of poison gas in Crimea by the German Wehrmacht 1942


One reported incident indicates the German army eventually used poison gas on survivors of the Battle of Kerch on the Eastern Crimean peninsula. After the battle in mid-May 1942, roughly 3000 soldiers and civilians not evacuated by sea were besieged in a series of caves and tunnels in the nearby Adzhimuskai quarry. After holding out for approximately three months, "poison gas was released into the tunnels, killing all but a few score of the Soviet defenders."17

Accidental release of mustard gas after the German bombing of Bari 1943
On the night of December 2, 1943, German Ju 88 bombers attacked the port of Bari in Southern Italy, sinking several American ships among them SS John Harvey, which was carrying mustard gas intended for use in retaliation by the Allies if German forces initiated gas warfare. The presence of the gas was highly classified, and authorities ashore had no knowledge of it which increased the number of fatalities, since physicians, who had no idea that they were dealing with the effects of mustard gas, prescribed treatment improper for those suffering from exposure and immersion.
17Merridale,Catherine, Ivan's War, Faber & Faber: pp. 148-150.

The whole affair was kept secret at the time and for many years after the war. According to the U.S. military account, "Sixty-nine deaths were attributed in whole or in part to the mustard gas, most of them American merchant seamen" out of 628 mustard gas military casualties. The large number of civilian casualties among the Italian population were not recorded. Part of the confusion and controversy derives from the fact that the German attack was highly destructive and lethal in itself, also apart from the accidental additional effects of the gas (it was nicknamed "The Little Pearl Harbor"), and attribution of the causes of death between the gas and other causes is far from easy. Rick Atkinson, in his book The Day of Battle, describes the intelligence that prompted Allied leaders to deploy mustard gas to Italy. This included Italian intelligence that Adolf Hitler had threatened to use gas against Italy if the state changed sides, and prisoner of war interrogations suggesting that preparations were being made to use a "new, egregiously potent gas" if the war turned decisively against Germany. Atkinson concludes that "No commander in 1943 could be cavalier about a manifest threat by Germany to use gas."

North Yemen
The first attack of the North Yemen Civil War took place on June 8, 1963 against Kawma, a village of about 100 inhabitants in northern Yemen, killing about seven people and damaging the eyes and lungs of twenty-five others. This incident is considered to have been experimental, and the bombs were described as "homemade, amateurish and relatively ineffective". The Egyptian authorities suggested that the reported incidents were probably caused by napalm, not gas. There were no reports of gas during 1964, and only a few were reported in 1965. The reports grew more frequent in late 1966. On December 11, 1966, fifteen gas bombs killed two people and injured thirty-five. On January 5, 1967, the biggest gas attack came against the village of Kitaf, causing 270 casualties, including 140 fatalities. The target may have been Prince Hassan bin Yahya, who had installed his headquarters nearby. The Egyptian government denied using poison gas, and alleged that Britain and the US were using the reports as psychological warfare against Egypt. On February 12, 1967, it said it would welcome a UN investigation. On March 1, U Thant, the then Secretary-General of the United Nations, said he was "powerless" to deal with the matter. On May 10, the twin villages of Gahar and Gadafa in Wadi Hirran, where Prince Mohamed bin Mohsin was in command, were gas bombed, killing at least seventy-five. The Red Cross was alerted and on June 2, it issued a statement in Geneva expressing concern. The Institute of Forensic Medicine at the University of Berne made a statement, based on a Red Cross report, that the gas was likely to have been halogenous derivatives - phosgene, mustard gas, lewisite, chloride or cyanogen bromide.

The gas attacks stopped for three weeks after the Six-Day War of June, but resumed on July, against all parts of royalist Yemen. Casualty estimates vary, and an assumption, considered conservative, is that the mustard and phosgene-filled aerial bombs caused approximately 1,500 fatalities and 1,500 injuries. [citation needed]

Cold War
After World War II, the Allies recovered German artillery shells containing the three German nerve agents of the day (tabun, sarin, and soman), prompting further research into nerve agents by all of the former Allies. Although the threat of global thermonuclear war was foremost in the minds of most during the Cold War, both the Soviet and Western governments put enormous resources into developing chemical and biological weapons. There is some evidence suggesting that Vietnamese troops used phosgene gas against Cambodian resistance forces in Thailand during the 1984-1985 dryseason offensive on the Thai-Cambodian border.181920

Developments by the Western governments


In 1952, researchers in Porton Down, England, invented the VX nerve agent but soon abandoned the project. In 1958 the British government traded their VX technology with the United States in exchange for information on thermonuclear weapons; by 1961 the U.S. was producing large amounts of VX and performing its own nerve agent research. This research produced at least three more agents; the four agents (VE, VG, VM, VX) are collectively known as the "V-Series" class of nerve agents. Also in 1952 the U.S. Army patented a process for the "Preparation of Toxic Ricin", publishing a method of producing this powerful toxin.

Nonlethal gases
During the Vietnam war USA, Australia and the South Vietnamese used tear gases and to a lesser extent vomiting gases like adamsite as did the North Vietnamese and NLF later on. USA at the time argued that these were not covered by the Chemical weapons convention. During the 1960s, the U.S. explored the use of anticholinergic deliriant incapacitating agents. One of these agents, assigned the weapon designation BZ, was allegedly used experimentally in the Vietnam War.[citation needed] These allegations inspired the 1990 fictional film Jacob's Ladder.

18"KPNLF says Vietnamese Using Suffocant Gas," Bangkok World, January 4, 1985, p. 1. 19"Viets Accused of Using Gas Against Rebels," Associated Press, Feb 19, 1985. 20"Thais Report a Clash with Vietnamese Troops," Associated Press, Feb 20, 1985.

Herbicidal warfare
In 1961 and 1962 the Kennedy administration authorized the use of chemicals to destroy vegetation and food crops in South Vietnam. Between 1961 and 1967 the US Air Force sprayed 12 million US gallons of concentrated herbicides, mainly Agent Orange (containing dioxin as an impurity in the manufacturing process) over 6 million acres (24,000 km) of foliage and trees, affecting an estimated 13% of South Vietnam's land. In 1965, 42% of all herbicides were sprayed over food crops. Besides destroying vegetation used as cover by the NLF and destroying food crops the herbicide was used to drive civilians into RVNcontrolled areas.21 In 1997, an article published by the Wall Street Journal reported that up to half a million children were born with dioxin related deformities, and that the birth defects in North Vietnam were fourfold those in the South. The use of Agent Orange may have been contrary to international rules of war at the time. It is also of note that the most likely victims of such an assault were small children. A 1967 study by the Agronomy Section of the Japanese Science Council concluded that 3.8 million acres (15,000 km) of land had been destroyed, killing 1000 peasants and 13,000 livestock.

United States chemical respiratory protection standardization


In December 2001, the United States Department of Health and Human Services, CDC, NIOSH, National Personal Protective Technology Laboratory (NPPTL), along with the U.S. Army Research, Development Engineering Command (RDECOM), Edgewood Chemical and Biological Center (ECBC), and the U.S. Department of Commerce National Institute for Standards and Technology (NIST) published the first of six technical performance standards and test procedures designed to evaluate and certify respirators intended for use by civilian emergency responders to a chemical, biological, radiological, or nuclear weapon release, detonation, or terrorism incident. To date NIOSH/NPPTL has published six new respirator performance standards based on a tiered approach that relies on traditional industrial respirator certification policy, next generation emergency response respirator performance requirements, and special live chemical warfare agent testing requirements of the classes of respirators identified to offer respiratory protection against chemical, biological, radiological, and nuclear (CBRN) agent inhalation hazards. These CBRN respirators are commonly known as open-circuit self-contained breathing apparatus (CBRN SCBA), air-purifying respirator (CBRN APR), air-purifying escape respirator (CBRN APER), self-contained escape respirator (CBRN SCER) and loose or tight fitting powered air-purifying respirators (CBRN PAPR). Current NIOSH-approved/certified CBRN respirator concept standards and test procedures can be found at the webpage.22

21Anatomy of a War by Gabriel Kolko, ISBN 1-56584-218-9 pages 144-145 22CDC.gov

United States Senate report


A 1994 United States Senate Report, entitled "Is military research hazardous to veterans health? Lessons spanning a half century," detailed the United States Department of Defense's practice of experimenting on animal and human subjects, often without their knowledge or consent. This included: Approximately 60,000 [US] military personnel were used as human subjects in the 1940s to test the chemical agents mustard gas and lewisite. "Mustard" section, Between the 1950s through the 1970s, at least 2,200 military personnel were subjected to various biological agents, referred to as Operation Whitecoat. Unlike most of the studies discussed in this report, Operation Whitecoat was truly voluntary. "Seventh" section, Between 1951 and 1969, Dugway Proving Ground was the site of testing for various chemical and biological agents, including an open air aerodynamic dissemination test in 1968 that accidentally killed, on neighboring farms, approximately 6,400 sheep by an unspecified nerve agent."Dugway" section,

Project SHAD
From 1962 to 1973, the Department of Defense planned 134 tests under Project 112, a chemical and biological weapons "vulnerability-testing program." In 2002, the Pentagon admitted for the first time that some of tests used real chemical and biological weapons, not just harmless simulants. Specifically under Project SHAD, 37 secret tests were conducted in California, Alaska, Florida, Hawaii, Maryland and Utah. Land tests in Alaska and Hawaii used artillery shells filled with sarin and VX, while Navy trials off the coasts of Florida, California and Hawaii tested the ability of ships and crew to perform under biological and chemical warfare, without the crew's knowledge. The code name for the sea tests was Project Shipboard Hazard and Defense -- "SHAD" for short. In October 2002, the Senate Armed Forces Subcommittee on Personnel held hearings, as the controversial news broke that chemical agents had been tested on thousands of American military personnel. The hearings were chaired by Senator Max Cleland, former VA administrator and Vietnam War veteran.

Developments by the Soviet government


There have been numerous reports of chemical weapons being used during the Soviet war in Afghanistan, sometimes against civilians.2324 Due to the secrecy of the Soviet Union's government, very little information was available about the direction and progress of the Soviet chemical weapons until relatively recently. After the fall of the Soviet Union, Russian chemist Vil Mirzayanov published articles revealing illegal chemical weapons experimentation in Russia. In 1993, Mirzayanov was imprisoned and fired from his job at the State Research Institute of Organic Chemistry and Technology, where he had worked for 26 years. In March 1994, after a major campaign by U.S. scientists on his behalf, Mirzayanov was released.25 Among the information related by Vil Mirzayanov was the direction of Soviet research into the development of even more toxic nerve agents, which saw most of its success during the mid-1980s. Several highly toxic agents were developed during this period; the only unclassified information regarding these agents is that they are known in the open literature only as "Foliant" agents (named after the program under which they were developed) and by various code designations, such as A-230 and A-232. According to Mirzayanov, the Soviets also developed weapons that were safer to handle, leading to the development of the binary weapons, in which precursors for the nerve agents are mixed in a munition to produce the agent just prior to its use. Because the precursors are generally significantly less hazardous than the agents themselves, this technique makes handling and transporting the munitions a great deal simpler. Additionally, precursors to the agents are usually much easier to stabilize than the agents themselves, so this technique also made it possible to increase the shelf life of the agents a great deal. During the 1980s and 1990s, binary versions of several Soviet agents were developed and are designated as "Novichok" agents (after the Russian word for "newcomer"). Together with Lev Fedorov, he told the secret Novichok story exposed in the newspaper The Moscow News.

IranIraq War
The IranIraq War began in 1980 when Iraq attacked Iran. Early in the conflict, Iraq began to employ mustard gas and tabun delivered by bombs dropped from airplanes; approximately 5% of all Iranian casualties are directly attributable to the use of these agents.[citation needed]

23The Story of Genocide in Afghanistan Hassan Kakar 24Report from Afghanistan Claude Malhuret 25Yevgenia Albats and Catherine A. Fitzpatrick. The State Within a State: The KGB and Its Hold on Russia - Past, Present, and Future , 1994. ISBN 0-374-18104-7 (see pages 325328)

Chemical weapons employed by Saddam Hussein killed and injured numerous Iranians, and Iraqi kurdish. According to Iraqi documents, assistance in developing chemical weapons was obtained from firms in many countries, including the United States, West Germany, the Netherlands, the United Kingdom, and France. About 100,000 Iranian soldiers were victims of Iraq's chemical attacks. Many were hit by mustard gas. The official estimate does not include the civilian population contaminated in bordering towns or the children and relatives of veterans, many of whom have developed blood, lung and skin complications, according to the Organization for Veterans. Nerve gas agents killed about 20,000 Iranian soldiers immediately, according to official reports. Of the 80,000 survivors, some 5,000 seek medical treatment regularly and about 1,000 are still hospitalized with severe, chronic conditions. Shortly before war ended in 1988, the Iraqi Kurdish village of Halabja was exposed to multiple chemical agents, killing about 5,000 of the town's 50,000 residents.26 During the Gulf War in 1991, Coalition forces began a ground war in Iraq. Despite the fact that they did possess chemical weapons, Iraq did not use any chemical agents against coalition forces. The commander of the Allied Forces, Gen. H. Norman Schwarzkopf, suggested this may have been due to Iraqi fear of retaliation with nuclear weapons.[citation needed]

Falklands War
Technically, the reported employment of tear gas by Argentine forces during the 1982 invasion of the Falkland Islands constitutes chemical warfare.27 However, the tear gas grenades were employed as nonlethal weapons to avoid British casualties. The barrack buildings the weapons were used on proved to be deserted in any case. The British claim that more lethal, but legally justifiable as they are not considered chemical weapons under the Chemical Weapons Convention, white phosphorus grenades were used.28

Terrorism
For many terrorist organizations, chemical weapons might be considered an ideal choice for a mode of attack, if they are available: they are cheap, relatively accessible, and easy to transport. A skilled chemist can readily synthesize most chemical agents if the precursors are available.

26Death Clouds: Saddam Husseins Chemical War Against the Kurds 27The Argentine Fight for The Falklands, Lieutenant-Commander Sanchez-Sabarots 28Falkland Islanders at war, Bound, Graham, Pen and Sword Books Limited, ISBN 1-84415-4297.

The earliest successful use of chemical agents in a non-combat setting was in 1946, motivated by a desire to obtain revenge on Germans for the Holocaust. Three members of a Jewish group calling themselves Dahm Y'Israel Nokeam ("Avenging Israel's Blood") hid in a bakery in the Stalag 13 prison camp near Nuremberg, Germany, where several thousand SS troops were being detained. The three applied an arsenic-containing mixture to loaves of bread, sickening more than 2,000 prisoners, of whom more than 200 required hospitalization. In July 1974, a group calling themselves the Aliens of America successfully firebombed the houses of a judge, two police commissioners, and one of the commissioners cars, burned down two apartment buildings, and bombed the Pan Am Terminal at Los Angeles International Airport, killing three people and injuring eight. The organization, which turned out to be a single resident alien named Muharem Kurbegovic, claimed to have developed and possessed a supply of sarin, as well as 4 unique nerve agents named AA1, AA2, AA3, and AA4S. Although no agents were found at the time he was arrested in August 1974, he had reportedly acquired "all but one" of the ingredients required to produce a nerve agent. A search of his apartment turned up a variety of materials, including precursors for phosgene and a drum containing 25 pounds of sodium cyanide. The first successful use of chemical agents by terrorists against a general civilian population was on June 27, 1994, when Aum Shinrikyo, an apocalyptic group based in Japan that believed it necessary to destroy the planet, released sarin gas in Matsumoto, Japan, killing eight and harming 200. The following year, Aum Shinrikyo released sarin into the Tokyo subway system killing 12 and injuring over 5,000. On 29 December 1999, four days after Russian forces began assault of Grozny, Chechen terrorists exploded two chlorine tanks in the town. Because of the wind conditions, no Russian soldiers were injured.29 In 2001, after carrying out the attacks in New York City on September 11, the organization Al-Qaeda announced that they were attempting to acquire radiological, biological and chemical weapons. This threat was lent a great deal of credibility when a large archive of videotapes was obtained by the cable television network CNN in August 2002 showing, among other things, the killing of three dogs by an apparent nerve agent. On October 26, 2002, Russian special forces used a chemical agent (presumably KOLOKOL-1, an aerosolized fentanyl derivative), as a precursor to an assault on Chechen terrorists, ending the Moscow theater hostage crisis. All 42 of the terrorists and 120 out of 850 hostages were killed during the raid. Of the hostages who died, all but one or two died from the effects of the agent.

29 . XX : . 5: . .: , 2002

In early 2007, multiple terrorist bombings had been reported in Iraq using chlorine gas. These attacks wounded or sickened more than 350 people. Reportedly the bombers were affiliated with Al-Qaeda in Iraq,Wikipedia:Link rot and they have used bombs of various sizes up to chlorine tanker trucks.Wikipedia:Link rot United Nations Secretary-General Ban Ki-moon condemned the attacks as "clearly intended to cause panic and instability in the country."

Chemical Weapons Treaty


The Protocol for the Prohibition of the Use in War of Asphyxiating, Poisonous or other Gases, and the Bacteriological Methods of Warfare, or the Geneva Protocol, is an International treaty which prohibits the use of chemical and biological weapons in warfare. Signed into International Law at Geneva on June 17, 1925 and entered into force on February 8, 1928, this treaty states that chemical and biological weapons are "justly condemned by the general opinion of the civilised world."

Chemical Weapons Convention


The most recent arms control agreement in International Law, the Convention of the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and on their Destruction, or the Chemical Weapons Convention, outlaws the production, stockpiling, and use of chemical weapons. It is administered by the Organisation for the Prohibition of Chemical Weapons (OPCW), an intergovernmental organisation based in The Hague.

Chemical weapons destruction

India
In June 1997, India declared that it had a stockpile of 1044 tonnes of sulphur mustard in its possession. India's declaration of its stockpile came after its entry into the Chemical Weapons Convention, that created the Organisation for the Prohibition of Chemical Weapons, and on January 14, 1993 India became one of the original signatories to the Chemical Weapons Convention. By 2005, from among six nations that had declared their possession of chemical weapons, India was the only country to meet its deadline for chemical weapons destruction and for inspection of its facilities by the Organisation for the Prohibition of Chemical Weapons.30 By 2006, India had destroyed more than 75 percent of its chemical weapons and material stockpile and was granted an extension to complete a 100 percent destruction of its stocks by April 2009. On May 14, 2009 India informed the United Nations that it has completely destroyed its stockpile of chemical weapons.

Iraq
The Director-General of the Organisation for the Prohibition of Chemical Weapons, Ambassador Rogelio Pfirter, welcomed Iraq's decision to join the OPCW as a significant step to strengthening global and regional efforts to prevent the spread and use of chemical weapons. The OPCW announced "The government of Iraq has deposited its instrument of accession to the Chemical Weapons Convention with the Secretary General of the United Nations and within 30 days, on 12 February 2009, will become the 186th State Party to the Convention". Iraq has also declared stockpiles of chemical weapons, and because of their recent accession is the only State Party exempted from the destruction time-line.

Japan
During the Second Sino-Japanese War (19371945) Japan stored chemical weapons on the territory of mainland China. The weapon stock mostly containing mustard gas-lewisite mixture. The weapons are classified as abandoned chemical weapons under the Chemical Weapons Convention and from September 2010 Japan has started their destruction in Nanjing using mobile destruction facilities in order to do so.

30India declares its stock of chemical weapons - India Abroad | HighBeam Research

Russia
Russia signed into the Chemical Weapons Convention on January 13, 1993 and ratified it on November 5, 1995. Declaring an arsenal of 39,967 tons of chemical weapons in 1997, by far the largest arsenal, consisting of blister agents: Lewisite, Sulfur mustard, Lewisite-mustard mix, and nerve agents: Sarin, Soman, and VX. Russia met its treaty obligations by destroying 1 percent of its chemical agents by the 2002 deadline set out by the Chemical Weapons Convention, but requested an extension on the deadlines of 2004 and 2007 due to technical, financial, and environmental challenges of chemical disposal. Since, Russia has received help from other countries such as Canada which donated C$100,000, plus a further C$100,000 already donated, to the Russian Chemical Weapons Destruction Program. This money will be used to complete work at Shchuch'ye and support the construction of a chemical weapons destruction facility at Kizner (Russia), where the destruction of nearly 5,700 tonnes of nerve agent, stored in approximately 2 million artillery shells and munitions, will be undertaken. Canadian funds are also being used for the operation of a Green Cross Public Outreach Office, to keep the civilian population informed on the progress made in chemical weapons destruction activities. As of July 2011, Russia has destroyed 48 percent (18,241 tonnes) of its stockpile at destruction facilities located in Gorny (Saratov Oblast) and Kambarka (Udmurt Republic) - where operations have finished - and Schuch'ye (Kurgan Oblast), Maradykovsky (Kirov Oblast), Leonidovka (Penza Oblast) whilst installations are under construction in Pochep (Bryansk Oblast) and Kizner (Udmurt Republic).31 As August 2013, 76 percent (30,500 tonnes) were destroyed, and Russia leaves the Cooperative Threat Reduction (CTR) Program, which partially funded chemical weapons destruction.

United States
On November 25, 1969, President Richard Nixon unilaterally renounced the use of chemical weapons and renounced all methods of biological warfare. He issued a decree halting the production and transport of all chemical weapons which remains in effect. From May 1964 to the early 1970s the USA participated in Operation CHASE, a United States Department of Defense program that aimed to dispose of chemical weapons by sinking ships laden with the weapons in the deep Atlantic. After the Marine Protection, Research, and Sanctuaries Act of 1972, Operation Chase was scrapped and safer disposal methods for chemical weapons were researched, with the U.S. destroying several thousand tons of mustard gas by incineration at the Rocky Mountain Arsenal, and nearly 4,200 tons of nerve agent by chemical neutralisation at Tooele Army Depot.

31http://cns.miis.edu/npr/pdfs/tucker41.pdf

The U.S. ratified the Geneva Protocol which banned the use of chemical and biological weapons on January 22, 1975. In 1989 and 1990, the U.S. and the Soviet Union entered an agreement to both end their chemical weapons programs, including binary weapons. In April 1997, the United States ratified the Chemical Weapons Convention, this banned the possession of most types of chemical weapons. It also banned the development of chemical weapons, and required the destruction of existing stockpiles, precursor chemicals, production facilities, and their weapon delivery systems. The U.S. began stockpile reductions in the 1980s with the removal of outdated munitions and destroying its entire stock of 3-Quinuclidinyl benzilate (BZ or Agent 15) at the beginning of 1988. In June 1990 the Johnston Atoll Chemical Agent Disposal System began destruction of chemical agents stored on the Johnston Atoll in the Pacific, seven years before the Chemical Weapons Treaty came into effect. In 1986 President Ronald Reagan made an agreement with the Chancellor, Helmut Kohl to remove the U.S. stockpile of chemical weapons from Germany. In 1990, as part of Operation Steel Box, two ships were loaded with over 100,000 shells containing Sarin and VX where taken from the U.S. Army weapons storage depots such as Miesau and then-classified FSTS (Forward Storage / Transportation Sites) and transported from Bremerhaven Germany to Johnston Atoll in the pacific, a 46-day nonstop journey.32 In May 1991, President George H. W. Bush committed the United States to destroying all of its chemical weapons and renounced the right to chemical weapon retaliation. In 1993, the United States signed the Chemical Weapons Treaty, which required the destruction of all chemical weapon agents, dispersal systems, and production facilities by April 2012. The U.S. prohibition on the transport of chemical weapons has meant that destruction facilities had to be constructed at each of the U.S.'s nine storage facilities. The U.S. met the first three of the four deadlines set out in the treaty, destroying 45% of its stockpile of chemical weapons by 2007. Due to the destruction of chemical weapons, under the United States policy of Proportional Response, an attack upon the United States or its Allies would trigger a force-equivalent counter-attack. Since the United States only maintains nuclear Weapons of Mass Destruction, it is the stated policy that the United States will regard all WMD attacks (Biological, chemical, or nuclear) as a nuclear attack and will respond to such an attack with a nuclear strike. As of 2012, stockpiles have been eliminated at 7 of the 9 chemical weapons depots and 89.75% of the 1997 stockpile has been destroyed by the treaty deadline of April 2012.33 Destruction will not begin at the two remaining depots until after the treaty deadline and will use neutralization, instead of incineration.

32The Oceans and Environmental Security: Shared U.S. and Russian Perspectives. 33Army Agency Completes Mission to Destroy Chemical Weapons , USCMA, January 21, 2012

References
CBWInfo.com (2001). A Brief History of Chemical and Biological Weapons: Ancient Times to the 19th Century. Retrieved Nov. 24, 2004. Chomsky, Noam (Mar. 4, 2001). Prospects for Peace in the Middle East, page 2. Lecture. Cordette, Jessica, MPH(c) (2003). Chemical Weapons of Mass Destruction. Retrieved Nov. 29, 2004. Croddy, Eric (2001), Chemical and Biological Warfare, Copernicus, ISBN 0-38795076-1 Smart, Jeffery K., M.A. (1997). History of Biological and Chemical Warfare. Retrieved Nov. 24, 2004. United States Senate, 103d Congress, 2d Session. (May 25, 1994). The Riegle Report. Retrieved Nov. 6, 2004. Gerard J Fitzgerald. American Journal of Public Health. Washington: Apr 2008. Vol. 98, Iss. 4; p. 611

Further reading
Leo P. Brophy and George J. B. Fisher; The Chemical Warfare Service: Organizing for War Office of the Chief of Military History, 1959; L. P. Brophy, W. D. Miles and C. C. Cochrane, The Chemical Warfare Service: From Laboratory to Field (1959); and B. E. Kleber and D. Birdsell, The Chemical Warfare Service in Combat (1966). official US history; Gordon M. Burck and Charles C. Flowerree; International Handbook on Chemical Weapons Proliferation 1991 L. F. Haber. The Poisonous Cloud: Chemical Warfare in the First World War Oxford University Press: 1986 James W. Hammond Jr; Poison Gas: The Myths Versus Reality Greenwood Press, 1999 Jiri Janata, Role of Analytical Chemistry in Defense Strategies Against Chemical and Biological Attack, Annual Review of Analytical Chemistry, 2009 Ishmael Jones, The Human Factor: Inside the CIA's Dysfunctional Intelligence Culture, Encounter Books, New York 2008, revised 2010, ISBN 978-1-59403-3827. WMD espionage. Benoit Morel and Kyle Olson; Shadows and Substance: The Chemical Weapons Convention Westview Press, 1993 Adrienne Mayor, "Greek Fire, Poison Arrows & Scorpion Bombs: Biological and Chemical Warfare in the Ancient World" Overlook-Duckworth, 2003, rev ed with new Introduction 2008

Geoff Plunkett, Chemical Warfare in Australia: Australia's Involvement In Chemical Warfare 1914 - Today, (2nd Edition), 2013. . Leech Cup Books. A volume in the Army Military History Series published in association with the Army History Unit. Jonathan B. Tucker. Chemical Warfare from World War I to Al-Qaeda (2006)

External links
Chemical weapons and international humanitarian law ATSDR Case Studies in Environmental Medicine: Cholinesterase Inhibitors, Including Insecticides and Chemical Warfare Nerve Agents U.S. Department of Health and Human Services Russian Biological and Chemical Weapons, about the danger posed by non-state weapons transfers Gaddum Papers at the Royal Society Chemical Weapons stored in the United States The Organisation for the Prohibition of Chemical Weapons OPCW Chemical Warfare in Australia Classes of Chemical Agents U.S. National Library of Medicine Chemical warfare agent potency, logistics, human damage, dispersal, protection and types of agents (bomb-shelter.net) "'War of Nerves': A History of Chemical Weapons" (interview with Jonathan Tucker from National Public Radio Talk of the Nation program, May 8, 2006 Chemical weapons in World War II "Our Army's Defense Against Poison Gas". Popular Science, February 1945, pp. 106111.

Chemical weapon
Chemical weapon

Pallets of 155 mm artillery shells containing "HD" (distilled sulfur mustard agent) at Pueblo Depot Activity (PUDA) chemical weapons storage facility Blister Agents: (Vesicants): Phosgene oxime (CX)

Lewisite Sulfur Mustard (Yperite) Nitrogen Mustard Nerve Agents: Tabun Sarin Soman Cyclosarin VX Blood Agents: Cyanogen chloride Hydrogen cyanide Choking Agents: Chloropicrin Phosgene Diphosgene Chlorine

(L) (HD) (HN) (GA) (GB) (GD) (GF) (VX) (CK) (AC) (PS) (CG) (DP) (CI)

Soviet chemical weapons canister from an Albanian stockpile Weapons of mass destruction By type Biological Chemical Nuclear Radiological By country Albania

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Canada

China

Egypt

France

Germany

India

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Iraq

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United States Proliferation Chemical Nuclear Missiles Treaties List of treaties

Book Category

A chemical weapon (CW) is a device that uses chemicals formulated to inflict death or harm on human beings. They may be classified as weapons of mass destruction though they are separate from biological weapons (diseases), nuclear weapons and radiological weapons (which use radioactive decay of elements). Chemical weapons can be widely dispersed in gas, liquid and solid forms and may easily afflict others than the intended targets. Nerve gas and tear gas are two modern examples. Lethal, unitary, chemical agents and munitions are extremely volatile and they constitute a class of hazardous chemical weapons that are now being stockpiled by many nations. (Unitary agents are effective on their own and require no mixing with other agents.) The most dangerous of these are nerve agents GA, GB, and VX, and vesicant (blister) agents which are formulations of sulfur mustard such as H, HT, and HD. All are liquids at normal room temperature, but become gaseous when released. Widely used during the First World War, the effects of so-called mustard gas, phosgene gas and others caused lung searing, blindness, death and maiming. Under the Chemical Weapons Convention (1993), there is a legally-binding, world-wide ban on the production, stockpiling, and use of chemical weapons and their precursors. Notwithstanding, large stockpiles thereof continue to exist, usually justified as only a precaution against putative use by an aggressor.

International law on chemical weapons


Before the Second World War
International law has prohibited the use of chemical weapons since 1899, under the Hague Convention: Article 23 of the Regulations Respecting the Laws and Customs of War on Land adopted by the First Hague Conference "especially" prohibited employing "poison and poisoned arms"; also, a separate Declaration stated that in any war between signatory powers, the parties would abstain from using projectiles "the object of which is the diffusion of asphyxiating or deleterious gases." The Washington Naval Treaty, signed February 6, 1922, also known as the FivePower Treaty, aimed at banning CWbut did not succeed because the French rejected it. The subsequent failure to include CW has contributed to the resultant increase in stockpiles. The Geneva Protocol, officially known as the Protocol for the Prohibition of the Use in War of Asphyxiating, Poisonous or other Gases, and of Bacteriological Methods of Warfare, is an International treaty prohibiting the use of chemical and biological weapons. It was signed at Geneva June 17, 1925 and entered into force on February 8, 1928. 133 nations are listed as state parties to the treaty Ukraine acceded August 7, 2003 and is the most recent member nation. This treaty states that chemical and biological weapons are "justly condemned by the general opinion of the civilised world." While the treaty prohibits the use of chemical and biological weapons, it does not address the production, storage, or transfer of these weapons. Later treaties did address those omissions and have been enacted.

Modern agreements
The Chemical Weapons Convention (CWC) is the most recent arms control agreement with the force of International law. Its full name is the Convention on the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and on their Destruction. That agreement outlaws the production, stockpiling and use of chemical weapons. It is administered by the Organisation for the Prohibition of Chemical Weapons (OPCW), which is an independent organization based in The Hague. The OPCW administers the terms of the CWC to 188 signatories which represents 98% of the global population. Of the stockpiles, 44,131 of the 71,194 tonnes declared (61.99%) have been destroyed. The OPCW has conducted 4,167 inspections at 195 chemical weapon-related and 1,103 industrial sites. These inspections have affected the sovereign territory of 81 States Parties since April 1997. Worldwide, 4,913 industrial facilities are subject to inspection provisions.

Use
Chemical warfare (CW) involves using the toxic properties of chemical substances as weapons. This type of warfare is distinct from Nuclear warfare and Biological warfare, which together make up NBC, the military initialism for Nuclear, Biological, and Chemical (warfare or weapons). None of these falls under the term conventional weapons which are primarily effective owing to their destructive potential. Chemical warfare does not depend upon explosive force to achieve an objective. Rather it depends upon the unique properties of the chemical agent weaponized. A lethal agent is designed to injure or incapacitate the enemy, or deny unhindered use of a particular area of terrain. Defoliants are used to quickly kill vegetation and deny its use for cover and concealment. An agent can also be used against agriculture and livestock to promote hunger and starvation. Chemical payloads can be delivered by remote controlled container release, aircraft, or rocket. Protection against chemical weapons includes proper equipment, training, and decontamination measures.

Countries with stockpiles


CWC states with declared stockpiles
Of 190 signatory nations to the CWC, state parties listed below have also declared stockpiles, agreed to monitored disposal, and verification, and in some cases, used CW in conflict. Both military targets and civilian populations have been affectedthe affected populations were not always damaged collaterally, but rather at times, the target of the attack. As of 2012, only four nations are confirmed as having chemical weapons: the United States, Russia, North Korea and Syria.Category:Articles contradicting other articles

India
India declared its stock of chemical weapons in June 1997. India's declaration came after the entry into force of the CWC that created the OPCW. India declared a stockpile of 1044 tonnes of sulphur mustard in its possession. On January 14, 1993 India became an original signatory to the CWC. By 2005, from among the six nations that had declared possession of chemical weapons, India was the only one to meet its deadline for chemical weapons destruction and for inspection of its facilities by the OPCW. By the end of 2006, India had destroyed more than 75 percent of its chemical weapons/material stockpile and was granted extension for destroying (the remaining stocks by April 2009) and was expected to achieve 100 percent destruction within that time frame. On May 14, 2009, India informed the United Nations that it has destroyed its stockpile of chemical weapons.

Iraq
The Organisation for the Prohibition of Chemical Weapons which oversees destruction measures has announced "The government of Iraq has deposited its instrument of accession to the Chemical Weapons Convention with the Secretary General of the United Nations and within 30 days, on 12 February 2009, will become the 186th State Party to the Convention". Iraq has also declared stockpiles of CW, and because of their recent accession is the only State Party exempted from the destruction time-line. On September 7, 2011 Mr. Hoshyar Zebari entered the OPCW headquarters, becoming the first Iraqi Foreign Minister to officially visit since the country joined the CWC. On June 28, 1987, Iraqi aircraft delivered what was believed to be mustard gas in an attack against the Iranian city of Sardasht. On two separate attacks against four residential areas, victims were estimated as 10 civilians dead and 650 civilians injured.

Japan
Japan stored chemical weapons on the territory of mainland China between 1937 and 1945. The weapons mostly contained a mustard gas-lewisite mixture. The weapons are classified as abandoned chemical weapons under the CWC and Japan has started their destruction in September 2010 in Nanjing using mobile destruction facilities.

Libya
Libya used chemical weapons under Muammar Gaddafi's regime in a war with Chad. In 2003 Gaddafi agreed to accede to the convention in exchange for "rapprochement" with western nations. At the time of the Libyan uprising against Gaddafi, Libya still controlled approximately 11.25 tons of poisonous mustard gas. Because of destabilization, concerns have increased regarding possibilities and likelihood that control of these agents could be lost. With terrorism as a core concern, international bodies are seeking to ensure Libya is held to its obligations under the treaty. Libya's post-Gaddafi National Transitional Council is cooperating with the Organization for the Prohibition of Chemical Weapons regarding the destruction of all legacy chemical weapons in the country. After assessing the chemical stockpiles the Libyan government will receive a deadline from the OPCW to destroy the weapons.

Russia
Russia entered the CWC with the largest declared stockpile of chemical weapons. By 2010 the country had destroyed 18,241 tonnes at destruction facilities located in Gorny (Saratov Oblast) and Kambarka (Udmurt Republic) where operations have finishedand Shchuchye (Kurgan Oblast), Maradykovsky (Kirov Oblast), Leonidovka (Penza Oblast) while installations are under construction in Pochep (Bryansk Oblast) and Kizner (Udmurt Republic).

United States
The U.S. stored its chemical weapons at eight U.S. Army installations within the Continental United States (CONUS). The stockpiles were maintained in exclusion zones at the following Department of Army installations (the percentages shown are reflections of amount by weight): Tooele Army Depot (TEAD), Utah (42.3% of total stockpile); Pine Bluff Arsenal (PBA), Arkansas (12%); Umatilla Depot Activity (UMDA), Oregon (11.6%); Pueblo Depot Activity (PUDA), Colorado (9.9%); Anniston Army Depot (ANAD), Alabama (7.1%); Aberdeen Proving Ground (APG), Maryland (5%); Newport Army Ammunition Plant (NAAP), Indiana (3.9%); and Blue Grass Army Depot (BGAD), Kentucky (1.6%). The remaining 6.6% was located on Johnston Atoll in the Pacific Ocean. Currently stockpiles have been eliminated at Johnston Atoll, APG, NAAP, UMDA, PBA TEAD., and ANAD. PUDA will begin elimination during FY 2015, and complete in FY 2017. BGAD will be last to complete this elimination which tentative dates have not been set. The U.S. policy on the use of chemical weapons is to reserve the right to retaliate. First use, or preemptive use, is a violation of stated policy. Only the president of the United States can authorize the first retaliatory use. Official policy now reflects the likelihood of chemical weapons being used as a terrorist weapon.

Syria
Prior to September 2013, Syria was one of only 7 states which are not party to the Chemical Weapons Convention. However, it is party to the 1925 Geneva Protocol prohibiting the use of chemical weapons in war but has nothing to say about production, storage or transfer. Syrian officials have stated that they feel it appropriate to have some deterrent against Israel's similarly non-admitted nuclear weapons program when questioned about the topic, but only on July 23, 2012, the Syrian government acknowledged for the first time that it had chemical weapons Independent assessments indicate that Syrian production could be up to a combined total of a few hundred tons of chemical agent per year. Syria reportedly manufactures Sarin, Tabun, VX, and mustard gas types of chemical weapons.

Syrian chemical weapons production facilities have been identified by Western nonproliferation experts at approximately 5 sites, plus one suspected weapons base: Al Safir (Scud missile base) Cerin Hama Homs Latakia Palmyra In July 2007, a Syrian arms depot exploded, killing at least 15 Syrians. Jane's Defence Weekly, a U.K. magazine reporting on military and corporate affairs, believed that the explosion happened when Iranian and Syrian military personnel attempted to fit a Scud missile with a mustard gas warhead. Syria stated that the blast was accidental and not chemical related. On July 13, 2012, the Syrian government moved its stockpile to an undisclosed location. In September 2012, information emerged that the Syrian military had begun chemical weapons tests and was reinforcing and resupplying a base housing these weapons located east of Aleppo in August. On March 19, 2013, news emerged from Syria indicating the first use of chemical weapons since the beginning of the Syrian uprising. On August 21, 2013, testimony and photographic evidence emerged from Syria indicating a large-scale chemical weapons attack on Ghouta, a populated urban center. On October 14, 2013, Syria officially acceded to the Chemical Weapons Convention.

Non-CWC states with stockpiles

Israel
Although Israel has signed the CWC, it has not ratified the treaty and therefore is not officially bound by its tenets.34 The country is believed to have a significant stockpile of chemical weapons, likely the most abundant in the Middle-East, according to the Russian Foreign Intelligence Service.35 In a 1983 CIA Report, it was stated that Israel, after "finding itself surrounded by front-line Arab states with budding CW capabilities, became increasingly conscious of its vulnerability to chemical attack... undertook a program of chemical warfare preparations in both offensive and protective areas... In late 1982 a probable CW nerve agent production facility and a storage facility were identified at the Dimona Sensitive Storage Area in the Negev Desert. Other CW agent production is believe to exit within a well-developed Israeli chemical industry."36 In 1992, El Al Flight 1862 crashed on its way to Tel Aviv and was found to be carrying CWC schedule 2 chemical, which is a precursor to the production of sarin nerve gas, a prohibited chemical weapon of mass destruction prohibited by the CWC. Israel insisted at the time that the materials were non-toxic. This shipment was coming from a US chemical plant to the IIBR under a US Department of Commerce license.37 In 1993, the U.S. Congress Office of Technology Assessment WMD proliferation assessment recorded Israel as a country generally reported as having undeclared offensive chemical warfare capabilities.38

North Korea
North Korea is not a signatory of CWC and has never officially acknowledged the existence of its offensive CW program. Nevertheless, the country is believed to possess a substantial arsenal of chemical weapons. It reportedly acquired the technology necessary to produce tabun and mustard gas as early as the 1950s. In 2009 the International Crisis Group reported that the consensus expert view was that North Korea had a stockpile of about 2,500 to 5,000 tonnes of chemical weapons, including mustard gas, sarin (GB) and other nerve agents.

Framework For Elimination of Syrian Chemical Weapons


An agreement was reached September 14, 2013 called the Framework For Elimination of Syrian Chemical Weapons; leading to the elimination of Syria's chemical weapon stockpiles by mid-2014 .
34http://treaties.un.org/Pages/ViewDetails.aspx?src=TREATY&mtdsg_no=XXVI3&chapter=26&lang=en 35http://rt.com/news/israel-chemical-weapons-sarin-714/ 36http://www.scribd.com/doc/166817108/1NIE-on-Israeli-Chemical-Weapons 37http://web.archive.org/web/20030818042548/http://news.bbc.co.uk/2/hi/europe/185199.stm 38http://www.princeton.edu/~ota/disk1/1993/9341/9341.PDF

Manner and form


There are three basic configurations in which these agents are stored. The first are self-contained munitions like projectiles, cartridges, mines, and rockets; these can contain propellant and/or explosive components. The next form are aircraft-delivered munitions. This form never has an explosive component. Together they comprise the two forms which have been weaponized and are ready for their intended use. The U.S. stockpile consisted of 39% of these weapon ready munitions. The final of the three forms are raw agent housed in one-ton containers. The remaining 61% of the stockpile was in this form. Whereas these chemicals exist in liquid form at normal room temperature, the sulfur mustards H, and HD freeze in temperatures below 55 F (12.8 C). Mixing lewisite with distilled mustard lowers the freezing point to 13 F (25.0 C). Higher temperatures are a bigger concern because the possibility of an explosion increases as the temperatures rise. A fire at one of these facilities would endanger the surrounding community as well as the personnel at the installations. Perhaps more so for the community having much less access to protective equipment and specialized training. The Oak Ridge National Laboratory conducted a study to assess capabilities and costs for protecting civilian populations during related emergencies, and the effectiveness of expedient, in-place shelters.

Disposal
The stockpiles, which have been maintained for more than 50 years, are now considered obsolete. Public Law 99-145, contains section 1412 which directs the Department of Defense (DOD) to dispose of the stockpiles. This directive fell upon the DOD with joint cooperation from the Federal Emergency Management Agency (FEMA). The Congressional directive has resulted in the present Chemical Stockpile Disposal Program. Some places where chemical weapons were tested, such as the San Jose Project in Panama, were not included in the disposal program. Thousands of mines on the island are still full of chemical gas and can be set off by passersby.[citation needed] Historically, chemical munitions have been disposed of by land burial, open burning, and ocean dumping (referred to as Operation CHASE). However in 1969, the National Research Council (NRC) recommended that ocean dumping be discontinued. The Army then began a study of disposal technologies, including the assessment of incineration as well as chemical neutralization methods. In 1982, that study culminated in the selection of incineration technology, which is now incorporated into what is known as the baseline system. Construction of the Johnston Atoll Chemical Agent Disposal System (JACADS) began in 1985.

This was to be a full-scale prototype facility using the baseline system. The prototype was a success but there were still many concerns about CONUS operations. To address growing public concern over incineration, Congress, in 1992, directed the Army to evaluate alternative disposal approaches that might be "significantly safer", more cost effective, and which could be completed within the established time frame. The Army was directed to report to Congress on potential alternative technologies by the end of 1993, and to include in that report"any recommendations that the National Academy of Sciences makes...". In June 2007 the disposal program achieved a milestone reaching 45% destruction of the chemical weapon stockpile. The Chemical Materials Agency (CMA) releases regular updates to the public regarding the status of the disposal program. By October 2010, the program had reached 80% destruction status.

Lethality
Chemical weapons are said to "make deliberate use of the toxic properties of chemical substances to inflict death". At the start of World War II it was reported in newspapers that "entire regions of Europe" would be turned into "lifeless wastelands". However, chemical weapons were not used to the extent feared. An unintended chemical weapon release occurred at the port of Bari. A German attack on the evening of December 2, 1943, damaged U.S. vessels in the harbour and the resultant release of mustard gas inflicted a total of 628 casualties. The U.S. Government was highly criticized for exposing American service members to chemical agents while testing the effects of exposure. These tests were often performed without the consent or prior knowledge of the soldiers affected. Many Australian service personnel were also exposed as a result of the "Brook Island trials" carried out by the British Government to determine the likely consequences of chemical attack in tropical conditions, about which little was then known. Some chemical agents are designed to produce mind altering changes rendering the victim unable to perform their assigned mission. These are classified as incapacitating agents and lethality is not a factor of their effectiveness.

Unitary versus binary weapons


Unitary munitions are opposite of binary munitions. Binary munitions contain two, unmixed and isolated chemicals which do not react to produce lethal effects until mixed. This usually happens just prior to battlefield use. In contrast, unitary weapons are lethal chemical munitions which produce a toxic result in their existing state. The majority of the chemical weapon stockpile is unitary and most of it is stored in one-ton bulk containers.

External links
Organisation for the Prohibition of Chemical Weapons Home page Lecture by Santiago Oate Laborde entitled The Chemical Weapons Convention: an Overview in the Lecture Series of the United Nations Audiovisual Library of International Law The Government of Canada ""Challenge"" for chemical substances that are a high priority for action Chemical categories Chemical Warfare Agents U.S. Army Chemical Materials Agency (home page)

Nerve Agents
Nerve agent
Part of a series on Chemical agents Lethal agents Blood agents Cyanogen chloride (CK) Hydrogen cyanide (AC) Blister agents Ethyldichloroarsine (ED)

Methyldichloroarsine (MD)

Phenyldichloroarsine (PD)

Lewisite (L)

Sulfur mustard (HD, H, HT, HL, HQ)

Nitrogen mustard 1. HN1 2. HN2 3. HN3

Nerve agents

G-Agents Tabun (GA) Sarin (GB) Soman (GD) Cyclosarin (GF) GV V-Agents EA-3148 VE VG VM VR VX Novichok agents

Nettle agents Phosgene oxime (CX) Pulmonary agents Chlorine Chloropicrin (PS) Phosgene (CG) Diphosgene (DP) Incapacitating agents

Agent 15 (BZ) Dimethylheptylpyran (DMHP) 1. EA-3167 2. Kolokol-1 PAVA spray Sleeping gas Riot control agents Pepper spray (OC) 1. CS 2. CN (mace) 3. CR

List of chemical warfare agents Nerve agents are a class of phosphorus-containing organic chemicals (organophosphates) that disrupt the mechanism by which nerves transfer messages to organs. The disruption is caused by blocking acetylcholinesterase, an enzyme that normally destroys acetylcholine, a neurotransmitter. As chemical weapons, they are classified as weapons of mass destruction by the United Nations according to UN Resolution 687 (passed in April 1991) and their production and stockpiling was outlawed by the Chemical Weapons Convention of 1993; the Chemical Weapons Convention officially took effect on April 29, 1997. The use of dangerous gases in warfare was forbidden by treaty already in the Geneva Protocol of 1925. Poisoning by a nerve agent leads to contraction of pupils, profuse salivation, convulsions, involuntary urination and defecation, and eventual death by asphyxiation as control is lost over respiratory muscles. Some nerve agents are readily vaporized or aerosolized and the primary portal of entry into the body is the respiratory system. Nerve agents can also be absorbed through the skin, requiring that those likely to be subjected to such agents wear a full body suit in addition to a respirator.

Biological effects
As their name suggests, nerve agents attack the nervous system of the human body. All such agents function the same way: by inhibiting the enzyme acetylcholinesterase, which is responsible for the breakdown of acetylcholine (ACh) in the synapse. ACh gives the signal for muscles to contract, preventing them from relaxing. Initial symptoms following exposure to nerve agents (like sarin) are a runny nose, tightness in the chest, and constriction of the pupils. Soon after, the victim will then have difficulty breathing and will experience nausea and drooling. As the victim continues to lose control of his or her bodily functions, he or she will involuntarily salivate, lacrimate, urinate, defecate, and experience gastrointestinal pain and vomiting. Blisters and burning of the eyes and/or lungs may also occur.3940 This phase is followed by initially myoclonic jerks followed by status epilepticus. Death then comes via complete respiratory depression, most likely via the excessive peripheral activity at the neuromuscular junction of the diaphragm.

39A Tutorial to Chemical and Biological Agents 40Effects of Chemical Agents

The effects of nerve agents are very long lasting and increase with successive exposures. Survivors of nerve agent poisoning almost invariably suffer chronic neurological damage. This neurological damage can also lead to continuing psychiatric effects.

Mechanism of action
When a normally functioning motor nerve is stimulated, it releases the neurotransmitter acetylcholine, which transmits the impulse to a muscle or organ. Once the impulse is sent, the enzyme acetylcholinesterase immediately breaks down the acetylcholine in order to allow the muscle or organ to relax. Nerve agents disrupt the nervous system by inhibiting the function of the enzyme acetylcholinesterase via forming a covalent bond where acetylcholine would break down (undergoes hydrolysis). Acetylcholine thus builds up and continues to act so that any nerve impulses are continually transmitted and muscle contractions do not stop. This same action also occurs at the gland and organ levels, resulting in uncontrolled drooling, tearing of the eyes (lacrimation) and excess production of mucus from the nose (rhinorrhea). The structures of the complexes of Soman (one of the most toxic nerve agents) with acetylcholinesterase from Torpedo californica have been solved by X-ray crystallography (PDB codes: 2wfz, 2wg0, 2wg1, and 1som). The mechanism of action of soman could be seen on example of 2wfz.

Antidotes
Atropine and related anticholinergic drugs act as antidotes to nerve agent poisoning because they block acetylcholine receptors, but they are poisonous in their own right. (Some synthetic anticholinergics, such as biperiden may counteract the central symptoms of nerve agent poisoning better than atropine, since they pass the bloodbrain barrier better than atropine.) While these drugs will save the life of a person affected with nerve agents, that person may be incapacitated briefly or for an extended period, depending on the amount of exposure. The endpoint of atropine administration is the clearing of bronchial secretions. Atropine for field use by military personnel is often loaded in an autoinjector, for ease of use in stressful conditions. Pralidoxime chloride, also known as 2-PAM chloride, is also used as an antidote. Rather than counteracting the initial effects of the nerve agent on the nervous system like atropine, pralidoxime chloride reactivates the poisoned enzyme (acetylcholinesterase) by scavenging the phosphoryl group attached on the functional hydroxyl group of the enzyme. Though safer to use, it takes longer to act.

Revival of acetylcholinesterase with pralidoxime chloride works more effectively on nicotinic receptors while blocking acetylcholine with atropine is more effective on muscarinic receptors. Often, severe cases of the poisoning are treated with both drugs.4142

Countermeasures in development
Butyrylcholinesterase is a prophylactic countermeasure against organophosphorus nerve agents. It acts as a scavenger by binding nerve agent in the blood stream before it can exert effects in the nervous system. Because it is a biological scavenger (and universal target) it is currently the only therapeutic agent effective in providing complete stoichiometric protection against the entire spectrum of organo-phosphorus nerve agents.43

Classes
There are two main classes of nerve agents. The members of the two classes share similar properties and are given both a common name (such as sarin) and a two-character NATO identifier (such as GB).

G-series
The G-series is thus named because German scientists first synthesized them. G series agents are known as non-persistent, while the V series are persistent. All of the compounds in this class were discovered and synthesized during or soon after World War I, led by Dr. Gerhard Schrader (later under the employment of IG Farben). This series is the first and oldest family of nerve agents. The first nerve agent ever synthesised was GA (tabun) in 1936. GB (sarin) was discovered next in 1939, followed by GD (soman) in 1944 and finally the more obscure GF (cyclosarin) in 1949. GB was the only G agent that was fielded by the US as a munition, specifically in rockets, aerial bombs and artillery shells.

41http://ocw.core.org.cn/CORE/medicine/veterinarypharmacology/lecture_notes_files/notes_17.Chapter_Fifteen__Detoxicants.pdf 42Nerve Agents 43Medical Identification and Treatment Systems(MITS)

V-series
Dr. Ranajit Ghosh, a chemist at the Plant Protection Laboratories of Imperial Chemical Industries was investigating a class of organophosphate compounds (organophosphate esters of substituted aminoethanethiols). Like Dr. Schrader, an earlier investigator of organophosphates, Dr. Ghosh found that they were quite effective pesticides. In 1954, ICI put one of them on the market under the trade name Amiton. It was subsequently withdrawn, as it was too toxic for safe use. The toxicity did not go unnoticed and some of the more toxic materials had in fact been sent to the British Armed Forces research facility at Porton Down for evaluation. After the evaluation was complete, several members of this class of compounds would become a new group of nerve agents, the V agents (depending on the source, the V stands for Victory, Venomous, or Viscous). The best known of these is probably VX, with the Russian V-gas coming a close second (Amiton is largely forgotten as VG). This class of compounds is also sometimes known as Tammelin's esters, after Lars-Erik Tammelin of the Swedish Institute of Defense Research. Dr. Tammelin was also conducting research on this class of compounds in 1952, but for obvious reasons he did not publicize his work widely. [citation needed] Wikipedia:Please clarify The V-series is the second family of nerve agents and contains five well known members: VE, VG, VM, VR and VX, along with several more obscure analogues. The most studied agent in this family, VX, was invented in the 1950s at Porton Down in the United Kingdom. The other agents in this series have not been studied extensively and information about them is limited. It is known, however, that the V-series agents are about 10 times more toxic than the G-agent sarin (GB)[citation needed]. All of the V-agents are persistent agents, meaning that these agents do not degrade or wash away easily and can therefore remain on clothes and other surfaces for long periods. In use, this allows the V-agents to be used to blanket terrain to guide or curtail the movement of enemy ground forces. The consistency of these agents is similar to oil; as a result, the contact hazard for Vagents is primarily but not exclusively dermal. VX was the only V-series agent that was fielded by the US as a munition, consisting of rockets, artillery shells, airplane spray tanks and landmines.4445

44 45"U.S. Army Destroys Entire Stockpile of VX Spray Tanks" http://www.cma.army.mil/fndocumentviewer.aspx?docid=003677713, U.S. Army Chemical Materials Agency, December 26, 2007, accessed January 4, 2007

Novichok agents
The Novichok (Russian for "newcomer") agents are a series of organophosphate compounds that were developed in the Soviet Union from the mid-1960s to the 1990s. The goal of this program was to develop and manufacture highly deadly chemical weapons that were unknown to the West. These new agents were designed to be undetectable by standard NATO chemical detection equipment and to defeat chemical protective gear. In addition to the newly developed "third generation" weapons, binary versions of several Soviet agents were developed and were designated as "Novichok" agents.

Insecticides
A number of insecticides, the phenothiazines, organophosphates such as dichlorvos, malathion and parathion, are nerve agents. The metabolism of insects is sufficiently different from mammals that these compounds have little effect on humans and other mammals at proper doses; but there is considerable concern about the effects of long-term exposure to these chemicals by farm workers and animals alike. At high enough doses, however, acute toxicity and death can occur through the same mechanism as other nerve agents. Organophosphate pesticide poisoning is a major cause of disability in many developing countries and is often the preferred method of suicide.46

Dissemination
Several methods exist for disseminating nerve agents on the battlefield. These include: Uncontrolled Aerosol Munitions Smoke Generation Explosive Dissemination Atomizers, Humidifiers and Foggers The method chosen will depend upon the physical nature of the nerve agent(s) used, the nature of the target, and the achievable level of sophistication.

46"Overcoming apathy in research on organophosphate poisoning" , BMJ (former British Medical Journal) 2004;329:1231-1233 (20 November)

History
The discovery of nerve agents
This first class of nerve agents, the G-Series, was accidentally discovered in Germany on December 23, 1936, by a research team headed by Dr. Gerhard Schrader working for IG Farben. Since 1934, Schrader had been working in a laboratory in Leverkusen to develop new types of insecticides for IG Farben. While working toward his goal of improved insecticide, Schrader experimented with numerous compounds, eventually leading to the preparation of tabun. In experiments, tabun was extremely potent against insects: as little as 5 ppm of tabun killed all the leaf lice he used in his initial experiment. In January 1937, Schrader observed the effects of nerve agents on human beings first-hand when a drop of tabun spilled onto a lab bench. Within minutes he and his laboratory assistant began to experience miosis (constriction of the pupils of the eyes), dizziness and severe shortness of breath. It took them three weeks to recover fully. In 1935 the Nazi government had passed a decree that required all inventions of possible military significance to be reported to the Ministry of War, so in May 1937 Schrader sent a sample of tabun to the chemical warfare (CW) section of the Army Weapons Office in Berlin-Spandau. Dr. Schrader was summoned to the Wehrmacht chemical lab in Berlin to give a demonstration, after which Schrader's patent application and all related research was classified as secret. Colonel Rdiger, head of the CW section, ordered the construction of new laboratories for the further investigation of tabun and other organophosphate compounds and Schrader soon moved to a new laboratory at WuppertalElberfeld in the Ruhr valley to continue his research in secret throughout World War II. The compound was initially codenamed Le-100 and later Trilon-83. Sarin was discovered by Schrader and his team in 1938 and named after their initials: Schrader, Ambrose, Rdiger and van der Linde. It was codenamed T-144 or Trilon-46. It was found to be more than ten times as potent as tabun. Soman was discovered by Dr. Richard Kuhn in 1944 as he worked with the existing compounds, the name is derived from either the Greek 'to sleep' or the Latin 'to bludgeon', it was codenamed T-300. Cyclosarin was also discovered during WWII but the details were lost and it was 'discovered' again in 1949. The G-series naming system was created by the United States when it uncovered the German activities, labeling tabun as GA (German Agent A), sarin as GB and soman as GD.47 Ethyl sarin was tagged GE and cyclosarin as GF.

47https://ccc.apgea.army.mil/sarea/products/textbook/Web_Version/chapters/chapter_5.htm#hist ory, Frederick Sidell

During World War II


In 1939, a pilot plant for tabun production was set up at Munster-Lager, on Lneburg Heath near the German Army proving grounds at Raubkammer. In January 1940, construction began on a secret plant, code named "Hochwerk" (High factory), for the production of tabun at Dyherrnfurth an der Oder (now Brzeg Dolny in Poland), on the Oder River 40 km (25 mi) from Breslau (now Wrocaw) in Silesia. The plant was large, covering an area of 2.4 by 0.8 km (1.5 by 0.5 miles) and was completely self-contained, synthesizing all intermediates as well as the final product, tabun. The factory even had an underground plant for filling munitions, which were then stored at Krappitz (now Krapkowice) in Upper Silesia. The plant was operated by Anorgana GmbH, a subsidiary of IG Farben, as were all other chemical weapon agent production plants in Germany at the time. Because of the plant's deep secrecy and the difficult nature of the production process, it took from January 1940 until June 1942 for the plant to become fully operational. Many of tabun's chemical precursors were so corrosive that reaction chambers not lined with quartz or silver soon became useless. Tabun itself was so hazardous that the final processes had to be performed while enclosed in double glass-lined chambers with a stream of pressurized air circulating between the walls. 3,000 German nationals were employed at Hochwerk, all equipped with respirators and clothing constructed of a poly-layered rubber/cloth/rubber sandwich that was destroyed after the tenth wearing. Despite all precautions, there were over 300 accidents before production even began and at least ten workers died during the two and a half years of operation. Some incidents cited in A Higher Form of Killing: The Secret History of Chemical and Biological Warfare are as follows: Four pipe fitters had liquid tabun drain onto them and died before their rubber suits could be removed. A worker had two liters of tabun pour down the neck of his rubber suit. He died within two minutes. Seven workers were hit in the face with a stream of tabun of such force that the liquid was forced behind their respirators. Only two survived despite resuscitation measures. The plant produced between 10,000 and 30,000 tons of tabun before its capture by the Soviet Army and movement probably to Dzerzhinsk, USSR.48

48Suspect CW Agent Production Plants, Dzerzhinsk, USSR, Changes Since 1962, CIA/NPIC, August 1963, declassified circa 1995, Corona: America's First Satellite Program, Kevin C. Ruffner, editor.

In 1940 the German Army Weapons Office ordered the mass production of sarin for wartime use. A number of pilot plants were built and a high-production facility was under construction (but was not finished) by the end of World War II. Estimates for total sarin production by Nazi Germany range from 500 kg to 10 tons. During that time, German intelligence believed that the Allies also knew of these compounds, assuming that because these compounds were not discussed in the Allies' scientific journals information about them was being suppressed. Though sarin, tabun and soman were incorporated into artillery shells, the German government ultimately decided not to use nerve agents against Allied targets. The Allies did not learn of these agents until shells filled with them were captured towards the end of the war. This is detailed in Joseph Borkin's book The Crime and Punishment of IG Farben:

Speer, who was strongly opposed to the introduction of tabun, flew Otto Ambros, I.G.'s authority on poison gas as well as synthetic rubber, to the meeting. Hitler asked Ambros, "What is the other side doing about poison gas?" Ambros explained that the enemy, because of its greater access to ethylene, probably had a greater capacity to produce mustard gas than Germany did. Hitler interrupted to explain that he was not referring to traditional poison gases: "I understand that the countries with petroleum are in a position to make more [mustard gas], but Germany has a special gas, tabun. In this we have a monopoly in Germany." He specifically wanted to know whether the enemy had access to such a gas and what it was doing in this area. To Hitler's disappointment Ambros replied, "I have justified reasons to assume that tabun, too, is known abroad. I know that tabun was publicized as early as 1902, that Sarin was patented and that these substances appeared in patents. (...) Ambros was informing Hitler of an extraordinary fact about one of Germany's most secret weapons. The essential nature of tabun and sarin had already been disclosed in the technical journals as far back as 1902 and I.G. had patented both products in 1937 and 1938. Ambros then warned Hitler that if Germany used tabun, it must face the possibility that the Allies could produce this gas in much larger quantities. Upon receiving this discouraging report, Hitler abruptly left the meeting. The nerve gases would not be used, for the time being at least, although they would continue to be produced and tested.

Joseph Borkin, The Crime and Punishment of IG Farben

The secret gets out


At the end of World War II during the occupation of Germany, the Allies recovered weapons containing three types of German nerve agents, prompting further research into nerve agents by the former Allies. The Red Army captured a factory producing tabun at Dyhernfurth in early 1945, then dismantled the entire site and took it back to Russia. Stocks of tabun, sarin and soman were discovered by all the Allies within Germany, the Anglo-American advance seizing around 250,000 tons of chemical weapons. The subset of nerve agents (totaling around 30,000 tons)Wikipedia:Manual of Style (dates and numbers) was split with the British, who took 14,000 tons of tabun-filled bombs, while the Americans took the remaining sarin-filled devices. The British-held bombs were eventually dumped at sea over 1955-56 as Operation Sandcastle. The fourth G-series nerve agent, cyclosarin, although discovered by German scientists studying organophosphates during WWII, was seemingly not found by the Allies, but independently rediscovered in 1949. In 1952, researchers in Porton Down, England, invented the VX nerve agent, inspired by the commercial pesticide Amiton, later reclassified as VG. The UK soon unilaterally abandoned the chemical weapons and chemical weapons research. In 1958 the British government traded their VX technology with the United States of America in exchange for information on thermonuclear weapons; by 1961 the US was producing large amounts of VX and performed its own nerve agent research. The four agents (VE, VG, VM, VX) are collectively known as the "V-Series" class of nerve agents.

Post-World War II
Since World War II, Iraq's use of mustard gas against Iranian troops and Kurds (Iran-Iraq war of 19811988) has been the only large-scale use of any chemical weapons. On the scale of the single Kurdish village of Halabja within its own territory, Iraqi forces did expose the populace to some kind of chemical weapons, possibly mustard gas and most likely nerve agents. In the Gulf War, no nerve agents (nor other chemical weapons) were used, but a number of U.S. and UK personnel were exposed to them when the Khamisiyah chemical depot was destroyed. This and the widespread use of anticholinergic drugs as a protective treatment against any possible nerve gas attack, have been proposed as a possible cause of Gulf War syndrome. One of the most widely publicised uses of nerve agents was the 1995 terrorist attack in which operatives of the Aum Shinrikyo religious group released sarin into the Tokyo subway system.

Ocean disposal of chemical weapons


In 1972, The United States Congress banned the practice of disposing chemical weapons into the ocean. However 32,000 tons of nerve and mustard agents had already been dumped into the ocean waters off the United States by the U.S. Army, primarily as part of Operation CHASE. According to a 1998 report created by William Brankowitz, a deputy project manager in the U.S. Army Chemical Materials Agency, the Army created at least 26 chemical weapons dump sites in the ocean off at least 11 states on both the west and east coasts. Additionally, due to poor records, they currently only know the rough whereabouts of half of them. There is currently a lack of scientific data regarding the ecological and health effects of this dumping. In the event of leakage, many nerve agents are soluble in water and would dissolve in a few days, while other substances such as sulphur mustard could last longer. Additionally, there have been a few incidents of chemical weapons washing ashore or being accidentally retrieved, for example during dredging or trawl fishing operations.

References
Borkin, Joseph (1978). The Crime and Punishment of IG Farben. New York: Free Press. 1978. ISBN 0-02-904630-0, available for download in Australia (as it is out-of-print) see this link. Clarke, Robin (1969). We all fall down: the prospects of biological and chemical warfare. Penguin. ISBN 0-14-021121-7. E-Medicine. (June 29, 2004). CBRNE Nerve Agents, V-series: Ve, Vg, Vm, Vx. Retrieved Oct. 23, 2004. E-Medicine. (June 30, 2004). CBRNE Nerve Agents, G-series: Tabun, Sarin, Soman. Retrieved Oct. 23, 2004. Mitretek Systems. (May 2004). Short History of the Development of Nerve Gases. Retrieved Oct. 23, 2004. Paxman, J.; Harris, R. (2002). A Higher Form of Killing: The Secret History of Chemical and Biological Warfare (2002 Rando edition). Random House Press. ISBN 0-8129-6653-8. United States Senate, 103d Congress, 2d Session. (May 25, 1994). The Riegle Report. Retrieved Nov. 6, 2004.

Organisation for the Prohibition of Chemical Weapons Nerve Agents [1] History of fluorophosphates as related to the development of nerve agents in Germany, Great Britain and the U.S.A. C. H. Gunderson, C. R. Lehmann, F. R. Sidell, B. Jabbari (1992). "Nerve agents: a review". Neurology 42 (5): 946950. doi: 10.1212/WNL.42.5.946. PMID 1315942. Buckley NA, Roberts D, Eddleston M. Overcoming apathy in research on organophosphate poisoning. BMJ. 2004 Nov 20;329(7476):12313. Review. PMID 15550429

External links
ATSDR Case Studies in Environmental Medicine: Cholinesterase Inhibitors, Including Pesticides and Chemical Warfare Nerve Agents U.S. Department of Health and Human Services Nervegas: America's Fifteen-year Struggle for Modern Chemical Weapons Army Chemical Review History Note: The CWS Effort to Obtain German Chemical Weapons for Retaliation Against Japan CBIAC Newsletter Goats' Milk Used in Production of Anti-nerve Gas Agents AChE inhibitors and substrates 2wfz, 2wg0, 2wg1, 1som in Proteopedia & Warfare/Biological & Chemical E-book "Declassified Nerve Gas Production Processes"

Tabun (nerve agent)


Tabun

Identifiers CAS number ChemSpider ChEMBL Jmol-3D images 77-81-6 6254 CHEMBL1097650 Image 1

Properties Molecular formula Molar mass Appearance Density Melting point Boiling point Solubility in water Vapor pressure Hazards Main hazards Highly Toxic. Fires involving this chemical may result in the formation of hydrogen cyanide C5H11N2O2P 162.13 g mol1 Colorless to brown liquid 1.0887 g/cm at 25 C 1.102 g/cm at 20 C -50 C, 223 K, -58 F 247.5 C, 521 K, 478 F 9.8 g/100 g at 25 C 7.2 g/100 g at 20 C 0.07 mmHg (9 Pa)

NFPA 704

Flash point (verify) (what is: / ?)

78 C

Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references Tabun or GA is an extremely toxic chemical substance. It is a clear, colorless, and tasteless liquid with a faint fruity odor.49 It is classified as a nerve agent because it fatally interferes with normal functioning of the mammalian nervous system. Its production is strictly controlled and stockpiling outlawed by the Chemical Weapons Convention of 1993. Tabun is the first of the so-called Gseries nerve agents along with GB (sarin), GD (soman) and GF (cyclosarin). Although pure tabun is clear, less-pure tabun may be brown. It is a volatile chemical, although less so than either sarin or soman. Tabun can be destroyed with bleaching powder, though the poisonous gas cyanogen chloride is produced.

Synthesis
Tabun was made on an industrial scale by Germany during World War II, based on a process developed by Dr. Gerhard Schrader. In the chemical agent factory in Dyhernfurth an der Oder, codenamed "Hochwerk", at least 12,000 metric tons of this agent were manufactured between 1942 and 1945. The manufacturing process consisted of two steps, the first being reaction of gaseous dimethylamine (1) with an excess of phosphoryl chloride (2), yielding dimethylamidophosphoric dichloride (3, codenamed "Produkt 39" or "D 4") and dimethylammonium chloride (4). The dimethylamidophosphoric dichloride thus obtained was purified by vacuum distillation and thereafter transferred to the main Tabun production line. Here it was reacted with an excess of sodium cyanide (5), dispersed in dry chlorobenzene, yielding the intermediate dimethylamidophosphoric dicyanide (not depicted in the scheme) and sodium chloride (8); then, absolute ethanol (6) was added, reacting with the dimethylamidophosphoric dicyanide to yield tabun (7) and hydrogen cyanide (9). After the reaction, the mixture (consisting of about 75% chlorobenzene and 25% tabun, along with insoluble salts and the rest of the hydrogen cyanide) was filtered to remove the insoluble salts and vacuumdistilled to remove hydrogen cyanide and excess chlorobenzene, so yielding the technical product, consisting either of 95% tabun with 5% chlorobenzene (Tabun A) or (later in the war) of 80% tabun with 20% chlorobenzene (Tabun B).50

49Facts About Tabun, National Terror Alert Response System 50Lohs, KH: Synthetische Gifte. 3., berarb. u. erg. Aufl., 1967, Deutscher Militrverlag, Berlin (East).

Effects of overexposure
The symptoms of exposure include:51 nervousness/restlessness, miosis (contraction of the pupil), rhinorrhea (runny nose), excessive salivation, dyspnea (difficulty in breathing due to bronchoconstriction/secretions), sweating, bradycardia (slow heartbeat), loss of consciousness, convulsions, flaccid paralysis, loss of bladder and bowel control, apnea (breathing stopped) and lung blisters. The exact symptoms of overexposure are similar to those created by all nerve agents. Tabun is toxic even in minute doses. The number and severity of symptoms which appear vary according to the amount of the agent absorbed and rate of entry of it into the body. Very small skin dosages sometimes cause local sweating and tremors accompanied with characteristically constricted pupils with few other effects. Tabun is about half as toxic as sarin by inhalation, but in very low concentrations it is more irritating to the eyes than sarin. Also, tabun breaks down slowly, which after repeated exposure can lead to build up in the body. The effects of tabun appear slowly when tabun is absorbed through the skin rather than inhaled. A victim may absorb a lethal dose quickly, although death may be delayed for one to two hours. A person's clothing can release the toxic chemical for up to 30 minutes after exposure. Inhaled lethal dosages kill in one to ten minutes, and liquid absorbed through the eyes kills almost as fast. However, people who experience mild to moderate exposure to tabun can recover completely, if treated almost as soon as exposure occurs. The LCt50 for tabun is about 400 mg-min/m3 Treatment for suspected tabun poisoning is often three injections of a nerve agent antidote, such as atropine. Pralidoxime chloride (2-PAM Cl) also works as an antidote; however, it must be administered within a period of from minutes to a few hours following exposure to be effective.52

51http://www.encyclopedia.com/doc/1G2-3403300733.html 52Emergency Response Safety and Health Database. TABUN (GA): Nerve Agent. National Institute for Occupatinal Safety and Health. Accessed April 30, 2009.

History
Tabun was the first nerve agent to be discovered by accident in January 19365354 by the German researcher Gerhard Schrader. Schrader was experimenting with a class of compounds called organophosphates, which kill insects by interrupting their nervous systems, to create a more effective insecticide for IG Farben, a German chemical and pharmaceutical industry conglomerate, at Elberfeld. Instead of a new insecticide, he discovered tabun, a chemical enormously toxic to humans as well as insects. During World War II, as part of the Grn 3 program, a plant for the manufacture of tabun was established at Dyhernfurth (now Brzeg Dolny, Poland), in 1939. Run by Anorgana, GmbH, the plant began production of the substance in 1942. The reason for the delay was the extreme precautions used by the plant. Intermediate products of tabun were corrosive, and had to be contained in quartz or silver-lined vessels. Tabun itself was also highly toxic, and final reactions were conducted behind double glass walls. Large scale manufacturing of the agent resulted in problems with tabun's degradation over time, and only around 12,500 tons of material were manufactured before the plant was seized by the Soviet Army. The plant initially produced shells and aerial bombs using a 95:5 mix of tabun and chlorobenzene, designated "Variant A", and in the latter half of the war switched to "Variant B," a 80:20 mix of tabun and chlorobenzene designed for easier dispersion. The Soviets dismantled the plant and shipped it to Russia.[citation needed] During the Nuremberg Trials, Albert Speer, Minister of Armaments and War Production for the Third Reich, testified that he had planned to kill Adolf Hitler in early 1945 by introducing tabun into the Fhrerbunker ventilation shaft.55 He said his efforts were frustrated by the impracticability of tabun and his lack of ready access to a replacement nerve agent,56 and also by the unexpected construction of a tall chimney that put the air intake out of reach. The US once had a tabun production program, which ended many decades ago. Like the other Allied governments, the Soviets soon abandoned GA for GB and GD. Large quantities of the German-manufactured agent were dumped into the sea to neutralize the substance. Since GA is much easier to produce than the other G-series weapons and the process is comparatively widely understood, countries that develop a nerve agent capability but lack advanced industrial facilities often start by producing GA. During the IranIraq War, Iraq employed quantities of chemical weapons against Iranian ground forces. Although the most commonly used agents were mustard gas and sarin, tabun and cyclosarin were also used.57
53Chemical Warfare Weapons Fact Sheets, about.com 54Chemical Weapons: Nerve Agents, University of Washington 55Speer 1970, pp. 43031. 56 57http://abcnews.go.com/US/story?id=90722&page=1

References
Speer, Albert (1970), Inside the Third Reich [Translated by Richard and Clara Winston], New York and Toronto: Macmillan, ISBN 978-0-297-00015-0, LCCN 70119132. Republished in paperback in 1997 by Simon & Schuster, ISBN 978-0684-82949-4 (Original German edition: Speer, Albert (1969), Erinnerungen [Reminiscences], Berlin and Frankfurt am Main: Propylen/Ullstein Verlag, OCLC 639475)

Further reading
United States Senate, 103d Congress, 2d Session. (May 25, 1994). Material Safety Data SheetLethal Nerve Agent Tabun (GA). Retrieved Nov. 6, 2004. United States Central Intelligence Agency (Jul. 15, 1996) Stability of Iraq's Chemical Weapon Stockpile Norris, John (1997). NBC: Nuclear, Biological and Chemical Warfare on the Modern Battlefield. Brassey's UK. p. 20. ISBN 1-85753-182-5.

Sarin
Sarin

Identifiers CAS number PubChem ChemSpider UNII ChEMBL Jmol-3D images 107-44-8 7871 7583 B4XG72QGFM CHEMBL509554 Image 1

Properties Molecular formula Molar mass Appearance Odor Density C4H10FO2P 140.09 g mol1 Clear colorless liquid Odorless in pure form 1.0887 g/cm (25 C) 1.102 g/cm (20 C)

Melting point Boiling point Solubility in water Hazards MSDS EU classification Main hazards NFPA 704

-56 C, 217 K, -69 F 158 C, 431 K, 316 F Miscible Lethal Nerve Agent Sarin (GB) Extremely Toxic (T+) It is a lethal cholinergic agent.

LD50 (verify) (what is: / ?)

70 mg-min/m3

Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references Sarin, or GB, is an organophosphorus compound with the formula [(CH3)2CHO]CH3P(O)F. It is a colorless, odorless liquid,58 used as a chemical weapon owing to its extreme potency as a nerve agent. It has been classified as a weapon of mass destruction in UN Resolution 687. Production and stockpiling of sarin was outlawed by the Chemical Weapons Convention of 1993, and it is classified as a Schedule 1 substance. Sarin can be lethal even at very low concentrations, with death following within one minute after direct ingestion due to suffocation from lung muscle paralysis, unless some antidotes, typically atropine or Biperiden and pralidoxime, are quickly administered to a person. People who absorb a non-lethal dose, but do not receive immediate medical treatment, may suffer permanent neurological damage.

58Sarin (GB). Emergency Response Safety and Health Database. National Institute for Occupational Safety and Health. Accessed April 20, 2009.

Production and structure


Sarin is a chiral molecule because it has four chemically different substituents attached to the tetrahedral phosphorus center.59 The SP form (the () optical isomer) is the more active enantiomer due to its greater binding affinity to acetylcholinesterase. The P-F bond is easily broken by nucleophilic agents, such as water and hydroxide. At high pH, sarin decomposes rapidly to nontoxic phosphonic acid derivatives. It is usually manufactured and weaponized as a racemic mixturean equal mixture of both enantiomeric formsby the alcoholysis reaction of methylphosphonyl difluoride with isopropyl alcohol: Isopropylamine is also included in the reaction to

neutralize the hydrogen fluoride byproduct. As a binary chemical weapon, it can be generated in situ by this same reaction. A by-product of sarin production is diisopropyl methylphosphonate (DIMP), which degrades into isopropyl methylphosphonic acid (IMPA).60

Biological effects
Like other nerve agents, sarin attacks the nervous system by stopping nerve endings in muscles from switching off. Death will usually occur as a result of asphyxia due to the inability to control the muscles involved in breathing function.

59D. E. C. Corbridge "Phosphorus: An Outline of its Chemistry, Biochemistry, and Technology" 5th Edition Elsevier: Amsterdam 1995. ISBN 0-444-89307-5. 60Agency for Toxic Substances and Disease Registry, Toxic Substances Portal - Diisopropyl Methylphosphonate (DIMP)

Specifically, sarin is a potent inhibitor of acetylcholinesterase, an enzyme that degrades the neurotransmitter acetylcholine after it is released into the synaptic cleft. In vertebrates, acetylcholine is the neurotransmitter used at the neuromuscular junction, where signals are transmitted between neurons from the central nervous systems to muscle fibres. Normally, acetylcholine is released from the neuron to stimulate the muscle, after which it is degraded by acetylcholinesterase, allowing the muscle to relax. A build-up of acetylcholine in the synaptic cleft, due to the inhibition of cholinesterase, means the neurotransmitter continues to act on the muscle fibre, so that any nerve impulses are effectively continually transmitted. Sarin acts on cholinesterase by forming a covalent bond with the particular serine residue at the active site. Fluoride is the leaving group, and the resulting phosphoester is robust and biologically inactive.61 Its mechanism of action resembles that of some commonly used insecticides, such as malathion. In terms of biological activity, it resembles carbamate insecticides, such as Sevin, and the medicines pyridostigmine, neostigmine, and physostigmine.

Degradation and shelf life


The most important chemical reactions of phosphoryl halides is the hydrolysis of the bond between phosphorus and the fluoride. This P-F bond is easily broken by nucleophilic agents, such as water and hydroxide. At high pH, sarin decomposes rapidly to nontoxic phosphonic acid derivatives. The initial breakdown of sarin is into isopropyl methylphosphonic acid (IMPA), a chemical that is not commonly found in nature except as a breakdown product of sarin. IMPA then degrades into methylphosphonic acid (MPA), which can also be produced by other organophosphates.62 Sarin degrades after a period of several weeks to several months. The shelf life can be shortened by impurities in precursor materials. According to the CIA, some Iraqi sarin had a shelf life of only a few weeks, owing mostly to impure precursors. Its otherwise-short shelf life can be extended by increasing the purity of the precursor and intermediates and incorporating stabilizers such as tributylamine. In some formulations, tributylamine is replaced by diisopropylcarbodiimide (DIC), allowing sarin to be stored in aluminium casings. In binary chemical weapons, the two precursors are stored separately in the same shell and mixed to form the agent immediately before or when the shell is in flight. This approach has the dual benefit of solving the stability issue and increasing the safety of sarin munitions.

61. See . 62Ian Sample, The Guardian, 17 September 2013, Sarin: the deadly history of the nerve agent used in Syria

Effects and treatment


Sarin has a high volatility (ease with which a liquid can turn into a gas) relative to similar nerve agents, therefore inhalation can be very dangerous and even vapor concentrations may immediately penetrate the skin. A persons clothing can release sarin for about 30 minutes after it has come in contact with sarin gas, which can lead to exposure of other people.63 People who absorb a nonlethal dose but do not receive immediate appropriate medical treatment may suffer permanent neurological damage. Even at very low concentrations, sarin can be fatal. Death may follow in one minute after direct ingestion of a lethal dose unless antidotes, typically atropine and pralidoxime, are quickly administered. Atropine, an antagonist to muscarinic acetylcholine receptors, is given to treat the physiological symptoms of poisoning. Since muscular response to acetylcholine is mediated through nicotinic acetylcholine receptors, atropine does not counteract the muscular symptoms. Pralidoxime can regenerate cholinesterases if administered within approximately five hours. Biperiden, a synthetic acetylcholine antagonist, has been suggested as an alternative to atropine due to its better bloodbrain barrier penetration and higher efficacy. Sarin is 26 times more deadly than cyanide. The LD50 of subcutaneously injected sarin in mice is 172 g/kg. Treatment measures have been described. Initial symptoms following exposure to sarin are a runny nose, tightness in the chest and constriction of the pupils. Soon after, the victim has difficulty breathing and experiences nausea and drooling. As the victim continues to lose control of bodily functions, the victim vomits, defecates and urinates. This phase is followed by twitching and jerking. Ultimately, the victim becomes comatose and suffocates in a series of convulsive spasms. Moreover, common mnemonics for the symptomatology of organophosphate poisoning, including sarin gas, are the "killer B's" of bronchorrhea and bronchospasm because they are the leading cause of death,64 and SLUDGE - Salivation, Lacrimation, Urination, Defecation, Gastrointestinal distress, and Emesis.

63Centers for Disease Control and Prevention, 17 May 2004. Retrieved 23 December 2012. 64Gussow, Leon. Nerve Agents: Three Mechanisms, Three Antidotes. Emergency Medicine News. 27(7):12, July 2005.

Diagnostic tests
Controlled studies in healthy men have shown that a nontoxic 0.43 mg oral dose administered in several portions over a 3 day interval caused average maximum depressions of 22 and 30%, respectively, in plasma and erythrocyte cholinesterase levels. A single acute 0.5 mg dose caused mild symptoms of intoxication and an average reduction of 38% in both measures of cholinesterase activity. Sarin in blood is rapidly degraded either in vivo or in vitro. Its primary inactive metabolites have in vivo serum half-lives of approximately 24 hours. The serum level of unbound isopropylmethylphosphonic acid (IMPA), a sarin hydrolysis product, ranged from 2-135 g/L in survivors of a terrorist attack during the first 4 hours post-exposure. Sarin or its metabolites may be determined in blood or urine by gas or liquid chromatography, while cholinesterase activity is usually measured by enzymatic methods.65

History
Sarin was discovered in 1938 in Wuppertal-Elberfeld in Germany by scientists at IG Farben attempting to create stronger pesticides; it is the most toxic of the four G-Series nerve agents made by Germany. The compound, which followed the discovery of the nerve agent tabun, was named in honor of its discoverers: Schrader, Ambros, Gerhard Ritter and Van der Linde.

Use as a weapon
In mid-1939, the formula for the agent was passed to the chemical warfare section of the German Army Weapons Office, which ordered that it be brought into mass production for wartime use. A number of pilot plants were built, and a high-production facility was under construction (but was not finished) by the end of World War II. Estimates for total sarin production by Nazi Germany range from 500 kg to 10 tons. Though sarin, tabun and soman were incorporated into artillery shells, Germany did not use nerve agents against Allied targets. 1950s (early): NATO adopted sarin as a standard chemical weapon, and both the USSR and the United States produced sarin for military purposes. 1953: 20-year-old Ronald Maddison, a Royal Air Force engineer from Consett, County Durham, died in human testing of sarin at the Porton Down chemical warfare testing facility in Wiltshire, England. Ten days after his death an inquest was held in secret which returned a verdict of "misadventure". In 2004, the inquest was reopened and, after a 64-day inquest hearing, the jury ruled that Maddison had been unlawfully killed by the "application of a nerve agent in a non-therapeutic experiment."

65R. Baselt, Disposition of Toxic Drugs and Chemicals in Man, 9th edition, Biomedical Publications, Seal Beach, CA, 2011, pp. 1531-1533.

1956: Regular production of sarin ceased in the United States, though existing stocks of bulk sarin were re-distilled until 1970. March 1988: Over the span of two days in March, the ethnic Kurd city of Halabja in northern Iraq (population 70,000) was bombarded with chemical and cluster bombs, which included sarin, in the Halabja poison gas attack. An estimated 5,000 people died. April 1988: Sarin was used four times against Iranian soldiers in April 1988 at the end of the IranIraq War, helping Iraqi forces to retake control of the al-Faw Peninsula during the Second Battle of al-Faw. Using satellite imagery, the United States assisted Iraqi forces in locating the position of the Iranian troops during those attacks. 1993: The United Nations Chemical Weapons Convention was signed by 162 member countries, banning the production and stockpiling of many chemical weapons, including sarin. It went into effect on 29 April 1997, and called for the complete destruction of all specified stockpiles of chemical weapons by April 2007. 1994: The Japanese religious sect Aum Shinrikyo released an impure form of sarin in Matsumoto, Nagano, killing eight people and harming over 200. (see Matsumoto incident) 1995: Aum Shinrikyo sect released an impure form of sarin in the Tokyo Metro. Thirteen people died. (see Sarin gas attack on the Tokyo subway) 1998: In the US, Time Magazine and CNN ran false news stories alleging that in 1970 U.S. Air Force A-1E Skyraiders engaged in a covert operation called Operation Tailwind, in which they deliberately dropped sarin-containing weapons on U.S. troops who had defected in Laos. CNN and Time Magazine later retracted the stories and fired the producers responsible. 2004: Iraqi insurgents detonated a 155 mm shell containing binary precursors for sarin near a U.S. convoy in Iraq. The shell was designed to mix the chemicals as it spins during flight. The detonated shell released only a small amount of sarin gas, either because the explosion failed to mix the binary agents properly or because the chemicals inside the shell had degraded with age. Two United States soldiers were treated after displaying the early symptoms of exposure to sarin. 21 August 2013: Sarin was used in an attack in the Ghouta region of the Rif Dimashq Governorate of Syria during the Syrian civil war. Varying sources gave a death toll of 322 to 1,729.

External links
Material Safety Data Sheet Questions and Answers for Sarin CIA memo: The Stability of Iraq's Chemical Weapons Stockpile

CDC Sarin fact sheet CDC Sarin Emergency Response Card

Novichok agent
Part of a series on Chemical agents Lethal agents Blood agents Cyanogen chloride (CK) Hydrogen cyanide (AC) Blister agents Ethyldichloroarsine (ED)

Methyldichloroarsine (MD)

Phenyldichloroarsine (PD)

Lewisite (L)

Sulfur mustard (HD, H, HT, HL, HQ)

Nitrogen mustard 1. HN1 2. HN2 3. HN3

Nerve agents

G-Agents Tabun (GA) Sarin (GB)

Soman (GD) Cyclosarin (GF) GV V-Agents EA-3148 VE

VG VM VR VX Novichok agents

Nettle agents Phosgene oxime (CX) Pulmonary agents

Chlorine Chloropicrin (PS) Phosgene (CG) Diphosgene (DP) Incapacitating agents

Agent 15 (BZ) Dimethylheptylpyran (DMHP) 1. EA-3167

2. Kolokol-1 PAVA spray Sleeping gas Riot control agents

Pepper spray (OC) 1. CS 2. CN (mace) 3. CR

List of chemical warfare agents Novichok (Russian : "Newcomer") is a series of nerve agents that were developed by the Soviet Union in the 1970s and 1980s66 and allegedly the most deadly nerve agents ever made, with some variants possibly five to eight times more potent than VX, though this has never been proven.67 They belong to "fourth generation chemical weapons" designed as a part of Soviet "Foliant" program.68 Initially designated K-84 and later renamed A-230, the Novichok family of analogs comprises more than a hundred structural variants.69 Of all the variants the most promising, from a military standpoint, was A-232 (Novichok5).70

Design objectives
These agents were designed to achieve three objectives: To be undetectable using standard NATO chemical detection equipment; To defeat NATO chemical protective gear; To be safer to handle. Although all these objectives were claimed to have been achieved, this is yet to be proven. Some of these agents are binary weapons, in which precursors for the nerve agents are mixed in a munition to produce the agent just prior to its use. Because the precursors are generally significantly less hazardous than the agents themselves, this technique makes handling and transporting the munitions a great deal simpler. Additionally, precursors to the agents are usually much easier to stabilize than the agents themselves, so this technique also made it possible to increase the shelf life of the agents. However this has the disadvantage that careless preparation or preparation by untrained individuals may produce a non-optimal agent. During the 1980s and 1990s, binary versions of several Soviet agents were developed and are designated as "Novichok" agents (after the Russian word for "newcomer").
66Tucker, J. B.; War of Nerves; Anchor Books; New York; 2006; pp 232-233. 67Yevgenia Albats and Catherine A. Fitzpatrick. The State Within a State: The KGB and Its Hold on Russia Past, Present, and Future, 1994. ISBN 0-374-18104-7 (see pages 325-328) 68Tucker, J. B.; War of Nerves; Anchor Books; New York; 2006; pp 231. 69Tucker, J. B.; War of Nerves; Anchor Books; New York; 2006; pp 233. 70Tucker, J. B.; War of Nerves; Anchor Books; New York; 2006; pp 253.

Disclosure
Extremely potent third-generation chemical weapons were developed in the Soviet Union and Russia from the 1970s until the early 1990s, according to a publication by two chemists, Lev Fedorov and Vil Mirzayanov in Moskovskiye Novosti weekly in 1992.71 The publication appeared just on the eve of Russia's signing of the Chemical Weapons Convention. According to Mirzayanov, the Russian Military Chemical Complex (MCC) was using defense conversion money received from the West for development of a chemical warfare facility.72 Mirzayanov made his disclosure out of environmental concerns. He was a head of a counter-intelligence department and performed measurements outside the chemical weapons facilities to make sure that foreign spies could not detect any traces of production. To his horror, the levels of deadly substances were 80 times greater than the maximum safe concentration. (A full account by Mirzayanov is available online.73) The existence of Novichok agents was openly admitted by Russian military industrial complex authorities when they brought a treason case against Mirzayanov. According to expert witness testimonies prepared for the KGB by three scientists, novichok and other related chemical agents had indeed been produced and therefore the disclosure by Mirzayanov represented high treason.74
71Fedorov, Lev and Vil Mirzayanov, "Poisoned Politics," Moskovskiye Novosti weekly No. 39, 1992. Much of this information was published earlier in the newspaper "Top Secret" run by Artyom Borovik in September 1991. However the KGB did not arrest Mirzayanov earlier due to political turmoil in Russia at this time, according to a book by Yevgenia Albats. 72 73Vil Mirzayanov " Dismantling the Soviet/Russian Chemical Weapons Complex: An Insider's View" Chemical Weapons Disarmament in Russia: Problems and Prospects (Washington, D.C.: Henry L. Stimson Center, 1995), page 21. 74"the talk [by Mirzayanov] about binary weapons was no more than a verbal construct, an argument ex adverso, and only the MCC [Russian Military Chemical Complex] could corroborate or refute this natural assumption. By entangling V. S. Mirzayanov in investigation, the MCC confirmed the stated hypothesis, advancing it to the ranks of proven facts." [2] 75Kruglyak Yu L, Malekin SI, Martynov IV. Phosphorylated oximes. XII. Reactions of 2halophospholanes with dichlorofluoronitrosomethane. Zhurnal Obshchei Khimii. 1972; 42(4):81114. 76Raevskii OA, Chapysheva NV, Ivanov AN, Sokolov VB, Martynov IV. Effect of Alkyl Substituents in Phosphorylated Oximes. Zhurnal Obshchei Khimii. 1987; 57(12):2720-2723 77Raevskii OA, Grigor'ev V Yu, Solov'ev VP, Ivanov AN, Sokolov VB, Martynov IV. Electron-Donor Functions of Ethyl Methylchloroformimino Methylphosphonate. Zhurnal Obshchei Khimii. 1987; 57(9):2073-2078 78Makhaeva GF, Filonenko IV, Yankovskaya VL, Fomicheva SB, Malygin VV. Comparative studies of O,O-dialkyl-O-chloromethylchloroformimino phosphates: interaction with neuropathy target esterase and acetylcholinesterase. Neurotoxicology. 1998 Aug-Oct;19(4-5):623-8. PMID 9745921 79Raevski OA, Chistiakov VV, Agabekian RS, Sapegin AM, Zefirov NS. Formation of models of the interaction between organophosphate compound structure and their ability to inhibit cholinesterase. Bioorganicheskaia Khimiia. 1990 Nov;16(11):1509-22. PMID 2096825 80Ivanov IuIa, Sokolov VB, Epishina TA, Martynov IV. O-substituted alkylchloroformoximes as substrates and inhibitors of cholinesterases. Doklady Akademii Nauk SSSR. 1990;310(5):1253-5. PMID 2354654 81Malygin VV, Sokolov VB, Richardson RJ, Makhaeva GF. Quantitative structure-activity relationships predict the delayed neurotoxicity potential of a series of O-alkyl-Omethylchloroformimino phenylphosphonates. Journal of Toxicology and Environmental Health Part A. 2003 Apr 11;66(7):611-25. PMID 12746136

Description of Novichok agents


The first description of these agents was provided by Mirzayanov. Dispersed in an ultra-fine powder instead of a gas or a vapor, they have unique qualities. A binary agent was then created that would mimic the same properties but would either be manufactured using materials legal under the CWT or be undetectable by treaty regime inspections. The most potent compounds from this family, novichok-5 and novichok-7, are supposedly around five to eight times more potent than VX. One of the key manufacturing sites was a chemical research institute in what is now Uzbekistan, and small, experimental batches of the weapons may have been tested on the nearby Ustyurt plateau. Two broad families of organophosphorus agents have been claimed to be Novichok agents. First are a group of organophosphorus compounds with an attached dihaloformaldoxime group, with the general formula shown below, where R = alkyl, alkoxy, alkylamino or fluorine and X = halogen (F, Cl, Br) or pseudohalogen such as CN. These compounds are extensively documented in Soviet literature of the time, but it is unclear whether they are all members of the potent "Novichok" compounds.7576777879808182

Some examples of the first group of compounds reported in

the literature are shown below, Novichok 5 is 3-chloro-2-methylpropyl ((chlorofluoromethylene)amino)oxyphosphonofluoridate (CAS 16415-09-1) and Novichok 7 is 3-chloro-2methylbutyl((chlorofluoromethylene)amino)oxyphosphonofluoridate CAS 1995257-9.83 They are binary agents in which the appropriately substituted 2-methyl1,3,2-dioxaphospholane84 is reacted with dichlorofluoro(nitroso)methane (CAS 1495-28-9).85 If the binary agents are reacted in advance, they are known as A232 and A-234 respectively. Since neither of the 2 chemicals making the binary agent are controlled under the moratorium on nerve agents, it meant that the Soviet Union was not in breach of this moratorium. While neither of the precursors are common, they do find legitimate use in the chemical industry and so are commercially available. Mirzayanov gives somewhat different structures

for Novichok agents in his autobiography, as shown below. He makes clear that a large number of compounds were made, and many of the less potent derivatives reported in the open literature as new organophosphate insecticides, so that the secret chemical weapons program could be disguised as legitimate pesticide research.86

83'Compendium of Chemical Warfare Agents' by Steven L. Hoenig pages 79-80 ISBN 0-38734626, ISBN 9780387346267' 84http://www.jnhaohua.com/cgi/search-en.cgi? f=product_en+company_en_1_&t=product_en&w=product_en&n=3&terms=+2-methyl1%2C3%2C2-dioxaphosphola&imageField.x=-1269&imageField.y=-433 85http://www.chemicalbook.com/ChemicalProductProperty_EN_CB02155296.htm 86Vil S Mirzayanov. State Secrets. An Insider's Chronicle of the Russian Chemical Weapons Program. (2009) pp142-145, 179-180. ISBN 978-1-4327-2566-2

Effects
As a nerve agent, Novichok belongs to organophosphate acetylcholinesterase inhibitors. These chemical compounds inhibit the enzyme acetylcholinesterase, preventing the normal breakdown of neurotransmitter acetylcholine. Acetylcholine concentrations then increase at neuromuscular junctions to cause involuntary contraction of all muscles. This then leads to respiratory and cardiac arrest and finally death. The use of a fast-acting peripheral anticholinergic drug such as Atropine could block the receptors where acetylcholine acts to prevent poisoning (as is the treatment for poisoning by other acetylcholinesterare inhibitors). This is however quite dangerous in itself.

External links
Chemical Weapons in Russia: History, Ecology, Politics by Lev Fedorov, Moscow, Center of Ecological Policy of Russia, 27 July 1994 Vil Mirzayanov " Dismantling the Soviet/Russian Chemical Weapons Complex: An Insider's View" Chemical Weapons Disarmament in Russia: Problems and Prospects (Washington, D.C.: Henry L. Stimson Center, 1995). Russian chemical weapons and by Federation of American Scientists Vil Mirzayanov, a scientist honored by the AAAS Science and Human Rights Program in 1995 The Chemical Weapons Coverup, by J. Michael Waller, The Wall Street Journal, February 13, 1997

VX (nerve agent)
VX (nerve agent)

Identifiers CAS number PubChem ChemSpider MeSH ChEBI ChEMBL Jmol-3D images 50782-69-9 , 51848-47-6 , 53800-401 39793 36386 VX CHEBI:609247 CHEMBL483105 Image 1 Image 2

Properties Molecular formula Molar mass Density Melting point Boiling point log P Vapor pressure C11H26NO2PS 267.37 g mol1 1.0083 g cm3 -50 C, 223 K, -58 F 298 C, 571 K, 568 F 2.047 0.09 Pa

Hazards NFPA 704

Flash point (verify) (what is: / ?)

159 C

Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references VX, IUPAC name O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate, is an extremely toxic substance that has no known uses except in chemical warfare as a nerve agent. It is a tasteless and odorless liquid. As a chemical weapon, it is classified as a weapon of mass destruction by the United Nations in UN Resolution 687. The production and stockpiling of VX was outlawed by the Chemical Weapons Convention of 1993. The VX nerve agent is the best-known of the V-series of nerve agents and is considered an area denial weapon due to its physical properties.

Discovery
Ranajit Ghosh, a chemist at the Plant Protection Laboratories of the British firm Imperial Chemical Industries was investigating a class of organophosphate compounds (organophosphate esters of substituted aminoethanethiols).Wikipedia:Verifiability Like Gerhard Schrader, an earlier investigator of organophosphates, Ghosh found that they were quite effective pesticides. In 1954, ICI put one of them on the market under the trade name Amiton. It was subsequently withdrawn, as it was too toxic for safe use. The toxicity did not go unnoticed, and samples of it had been sent to the British Armed Forces research facility at Porton Down for evaluation. After the evaluation was complete, several members of this class of compounds became a new group of nerve agents, the V agents. The best known of these is probably VX, assigned the UK Rainbow Code Purple Possum, with the Russian V-Agent coming a close second (Amiton is largely forgotten as VG). This class of compounds is also sometimes known as Tammelin's esters, after Lars-Erik Tammelin of the Swedish Defence Research Agency. Tammelin was also conducting research on this class of compounds in 1952, but did not publicize his work widely.

Chemical characteristics
With its high viscosity and low volatility, VX has the texture and feel of motor oil. This makes it especially dangerous, as it has a high persistence in the environment. It is odorless and tasteless, and can be distributed as a liquid, both pure and as a mixture with a polymer in the form of thickened agent, or as an aerosol. VX is an acetylcholinesterase inhibitor, i.e. it works by blocking the function of the enzyme acetylcholinesterase. Normally, an electric nerve pulse would cause the release of acetylcholine over a synapse that would stimulate muscle contraction. The acetylcholine is then broken down to non-reactive substances (acetic acid and choline) by the acetylcholinesterase enzyme. If more muscle tension is needed the nerve must release more acetylcholine. VX blocks the of action of acetylcholinesterase, thus resulting in initial Electron violent shells contractions, chlorine (2, 8, 7) followed by sustained supercontraction restricted to the subjunctional endplate sarcoplasm and prolonged depolarizing neuromuscular blockade, the latter resulting in flaccid paralysis of all the muscles in the body. Sustained paralysis of the diaphragm muscle causes death by asphyxiation.

Synthesis
VX is produced via the "transester process". This entails a series of steps whereby phosphorus trichloride is methylated to produce methyl phosphonous dichloride. The resulting material is reacted with ethanol to form a diester. This is then transesterified with N,N-diisopropylaminoethanol to produce the mixed phosphonite. Finally, this immediate precursor is reacted with sulfur to form VX. VX can also be delivered in binary chemical

weapons which mix in-flight to form the agent prior to release. Binary VX is referred to as VX2, and is created by mixing O-(2-diisopropylaminoethyl) O-ethyl methylphosphonite (Agent QL) with elemental sulfur (Agent NE) as is done in the Bigeye aerial chemical bomb. It may also be produced by mixing with sulfur compounds, as with the liquid dimethyl polysulfide mixture (Agent NM) in the canceled XM-768 8-inch binary projectile program.[citation needed]

Solvolysis
Like other organophosphorus nerve agents, VX may be destroyed by reaction with strong nucleophiles. The reaction of VX with concentrated aqueous sodium hydroxide results in competing cleavage of the P-O and P-S esters, with P-S cleavage dominating. This is somewhat problematic, since the product of P-O bond cleavage (named EA 2192) remains toxic. In contrast, reaction with the anion of hydrogen peroxide (hydroperoxidolysis) leads to exclusive cleavage of the P-S bond., P-S cleavage NaOH(aq) reacts with VX in two ways. It can cleave VX's P-S bond, yielding two relatively nontoxic products... P-O cleavage ...or it can cleave VX's P-O bond, forming ethanol and EA 2192 (shown in red), which has similar toxicity to VX itself

Biological effects
VX is the most toxic nerve agent ever synthesized for which activity has been independently confirmed. The median lethal dose (LD50) for humans is estimated to be about 10 milligrams through skin contact and the LCt50 for inhalation is estimated to be 3050 mgmin/m. Early symptoms of percutaneous exposure (skin contact) may be local muscular twitching or sweating at the area of exposure followed by nausea or vomiting. Some of the early symptoms of a VX vapor exposure to nerve agent may be rhinorrhea (runny nose) and/or tightness in the chest with shortness of breath (bronchial constriction). Miosis (pinpointing of the pupils) may be an early sign of agent exposure but is not usually used as the only indicator of exposure.

Treatment
Primary consideration should be given to removal of the liquid agent from the skin before removal of the individual to an uncontaminated area or atmosphere. After removal from the contaminated area, the casualty will be decontaminated by washing the contaminated areas with household bleach and flushing with clean water. After decontamination, the contaminated clothing is removed and skin contamination washed away. If possible, decontamination is completed before the casualty is taken for further medical treatment. An individual who has received a known nerve-agent exposure or who exhibits definite signs or symptoms of nerve-agent exposure should immediately have the nerve agent antidote drugs atropine, pralidoxime (2-PAM), and a sedative/antiepileptic such as diazepam injected. In several nations the nerve agent antidotes are issued for military personnel in the form of an autoinjector such as the United States military Mark I NAAK. Atropine works by binding and blocking a subset of acetylcholine receptors (known as muscarinic acetylcholine receptor, mAchR), so that the build up of acetylcholine produced by loss of the acetylcholinesterase function can no longer affect their target. VX (and other organophosphates) block the enzymatic activity of acetylcholinesterase (AChE) by binding to the active site of the enzyme. The phosphate group on VX is then transferred from VX to AChE, inactivating the enzyme and producing an inactive metabolite of VX. The injection of pralidoxime (2-PAM) removes the phosphate group from AChE, reactivating it, thereby reversing the effects of VX. If pralidoxime is not given soon enough, the inactivated enzyme will "age", resulting in a much stronger AChEW-phosphate that pralidoxime cannot reverse.87

Diagnostic tests
Controlled studies in humans have shown that minimally toxic doses cause 7075% depression of erythrocyte cholinesterase within several hours of exposure. The serum level of ethyl methylphosphonic acid (EMPA), a VX hydrolysis product, was measured to confirm exposure in one poisoning victim.

History
For an in-depth discussion, see main article on nerve agent history

87Pralidoxime - Wikipedia, the free encyclopedia

The chemists Ranajit Ghosh and J.F. Newman discovered the V-series nerve agents at ICI in 1952, patenting diethyl S-2-diethylaminoethyl phosphono- thioate (agent VG) in November, 1952. Further commercial research on similar compounds ceased in 1955 when its lethality to humans was discovered. The US went into production of large amounts of VX in 1961 at Newport Chemical Depot. There was evidence of a combination of chemical agents having been used by Iraq against the Kurds at Halabja in 1988 under Saddam Hussein. Hussein later testified to UNSCOM that Iraq had researched VX, but had failed to weaponize the agent due to production failure. After U.S. and allied forces had invaded Iraq, no VX agent or production facilities were found. However, UNSCOM laboratories detected traces of VX on warhead remnants. In December 1994 and January 1995, Masami Tsuchiya of Aum Shinrikyo synthesized 100 to 200 grams of VX which was used to attack three persons. Two persons were injured and one 28-year-old man died, who is believed to be the only fully documented victim of VX ever in the world.88 The VX victim, whom Shoko Asahara had suspected as a spy, was attacked at 7:00 am on December 12, 1994 on the street in Osaka by Tomomitsu Niimi and another AUM member, who sprinkled the nerve agent on his neck. He chased them for about 100 yards (90 metres) before collapsing, dying 10 days later without ever coming out of a deep coma. Doctors in the hospital suspected at the time he had been poisoned with an organophosphate pesticide. But the cause of death was pinned down only after cult members arrested for the subway attack confessed to the killing. Ethyl methylphosphonate, methylphosphonic acid and diisopropyl-2-(methylthio) ethylamine were later found in the body of the victim. Unlike the cases for sarin (Matsumoto incident and Sarin gas attack on the Tokyo subway), VX was not used for mass murder. Some countries known to possess VX are the United States, Russia, and Syria89 A Sudanese pharmaceutical facility, the Al-Shifa pharmaceutical factory, was bombed by the U.S. in 1998 acting on information that it produced VX and that the origin of the agent was associated with both Iraq and Al Qaeda. The US had obtained soil samples identified as containing O-ethyl hydrogen methylphosphonothioate (EMPTA), a chemical used in the production of VX which may also have commercial applications. Chemical weapons experts later suggested that the widely-used Fonophos organophosphate insecticide could have been mistaken for EMPTA.

88Pamela Zurer, "Japanese cult used VX to slay member" Chemical and Engineering News 1998, Vol 76 (no. 35). 89http://www.gouvernement.fr/sites/default/files/fichiers_joints/syrie_synthese_nationale_de_rens eignement_declassifie_02_09_2013.pdf

US VX stockpile elimination
In the late 1960s, the US canceled its chemical weapons programs and began the destruction of its stockpiles of agents by a variety of methods. Early disposal included the US Army's CHASE (Cut Holes And Sink 'Em) program, in which old ships were filled with chemical weapons stockpiles and then scuttled. CHASE 8 was conducted on June 15, 1967, in which the S.S. Cpl. Eric G. Gibson was filled with 7,380 VX rockets and scuttled in 7,200 feet (2,200 m) of water, off the coast of Atlantic City, New Jersey. In fiscal year 2008, the US Department of Defense released a study finding that the U.S. had dumped at least 124 tonsWikipedia:Vagueness of VX into the Atlantic Ocean off the coasts of New York/New Jersey and Florida, between 1919 and 1970. This material consisted of nearly 22,000 M55 rockets, 19 bulk containers holding 1,400 pounds (640 kg) each, and one M23 chemical landmine. Incineration was used for VX stockpile destruction starting in 1990 with Johnston Atoll Chemical Agent Disposal System in the North Pacific with other incineration plants following at Deseret Chemical Depot, Pine Bluff Arsenal, Umatilla Chemical Depot and Anniston Army Depot with the last of the VX inventory destroyed on December 24, 2008.90Wikipedia:Link rot The Newport Chemical Depot began VX stockpile elimination using chemical neutralization in 2005. VX was hydrolyzed to much less toxic byproducts by using concentrated caustic solution, and the resulting waste was then shipped off-site for further processing. Technical and political issues regarding this secondary byproduct resulted in delays, but the depot completed their VX stockpile destruction in August, 2008. The remaining VX stockpile in the US will be treated by the Blue Grass Chemical Agent-Destruction Pilot Plant, part of the Program Executive Office, Assembled Chemical Weapons Alternatives program. The program was established as an alternative to the incineration process successfully used by the Army Chemical Materials Agency, which completed its stockpile destruction activities in March 2012. The Blue Grass Pilot Plant has been plagued by repeated cost over-runs and schedule slippages since its inception.

Worldwide VX stockpile elimination


Worldwide, VX disposal has continued since 1997 under the mandate of the Chemical Weapons Convention.

90http://www.cma.army.mil/endofvx.aspx

In Russia, the US is providing support for these destruction activities with the Nunn-Lugar Global Cooperation Initiative. The Initiative has been able to convert a former chemical weapons depot at Shchuchye, Kurgan Oblast, into a facility to destroy those chemical weapons. The new facility, which opened in May 2009, has been working on eliminating the nearly 5,950 tonsWikipedia:Vagueness of nerve agents held at the former storage complex. However, this facility only holds about 14% of Russian chemical weapons that are stored throughoutWikipedia:Vagueness seven sites. Another such destruction plant for Russia, built for 140 million and paid for by Germany, is to openWikipedia:Manual of Style/Dates and numbers#Precise language at Potshep, Bryansk Oblast, in 2009.

In popular culture
One of the best known references to VX in popular culture is its use in the 1996 film The Rock,9192 which centers on a threatened VX attack on San Francisco from the island of Alcatraz. The film uses a certain artistic license, notably with VX being ascribed corrosive powers it does not possess, permitting an early scene in which an accidental VX victim is shown with his face melting, rather than merely dying through asphyxiation. It also shows the hero applying an intracardiac injection of atropine as a defense against VX contamination, rather than the more usual intramuscular injection (eg into the thigh) of a combination of atropine and pralidoxime. Another reference to VX is found in the 2012 art-house dark comedy film It's a Disaster. The film centers around four couples that gather for a regular couples brunch and later learn about a multi-city VX attack on the United States that may threaten their lives.9394

External links
Oxford website on Nerve Agents Questions and Answers for VX CDC Facts About VX U.S. Army's Chemical Materials Agency (CMA) CBW Info National Academies: Health effects of VX
91Royal Society of Chemistry, 31 January 2012, Molecular dynamics to combat chemical terrorism 92Ilan Ben Zion, Times of Israel, 29 August 2013, Vital sarin antidote missing from gas mask kits 93It's a disaster. Dir. Todd Berger. Perf. Julia Stiles, David Cross, America Ferrera, Rachel Boston, Kevin Brennan, Jeff Grace, Erinn Hayes, Blaise Miller. Oscilloscope Laboratories, 2012. Film. 94http://www.rogerebert.com/reviews/its-a-disaster-2013

DA PAM 385-61 US Army Toxic Chemical Agent Safety Standards Decommissioning Surplus VX - Article from NYTimes.com

Mark I NAAK
The Mark I NAAK, or MARK I Kit, is United States military nomenclature for the "Nerve Agent Antidote Kit"[citation needed]. It is a dual-chamber autoinjector: Two anti-nerve agent drugs atropine sulfate and pralidoxime chloride each in injectable form, constitute the kit[citation needed]. The kits are only effective against the nerve agents tabun (GA), sarin (GB), soman (GD) and VX[citation needed]. Typically, U.S. servicemembers are issued three MARK I Kits when operating in circumstances where chemical weapons are considered a potential hazard[citation needed] . Along with the three kits are issued one CANA (Convulsive Antidote, Nerve Agent) for simultaneous use[citation needed]. (CANA is the drug diazepam or Valium, an anticonvulsant.[citation needed]) Both of these kits are intended for use in "buddy aid" or "self aid" administration of the drugs prior to decontamination and delivery of the patient to definitive medical care[citation needed]. A newer model, the ATNAA (Antidote Treatment Nerve Agent Auto-Injector),95 has both the atropine and the pralidoxime in one syringe, allowing for simplified administration. The use of a Mark 1 or ATNAA kit inhibits the nerve agents' purpose, thereby reducing the number of fatal casualties in the advent of chemical warfare[citation needed] . The kits should only be administered if nerve agents have been absorbed or inhaled[citation needed].

References
U.S. Army Medical Research Institute of Chemical Defense, Medical Management of Chemical Casualties Handbook, Third Edition (June 2000), Aberdeen Proving Ground, MD, pp 118-126.

Pulmonary Agents
Pulmonary agent
Part of a series on Chemical agents

95Meridian Meds - ATNAA Pack Insert

Lethal agents Blood agents Cyanogen chloride (CK) Hydrogen cyanide (AC) Blister agents Ethyldichloroarsine (ED)

Methyldichloroarsine (MD)

Phenyldichloroarsine (PD)

Lewisite (L)

Sulfur mustard (HD, H, HT, HL, HQ)

Nitrogen mustard 1. HN1 2. HN2

3. HN3

Nerve agents

G-Agents Tabun (GA) Sarin (GB) Soman (GD) Cyclosarin (GF) GV V-Agents EA-3148 VE VG VM VR VX Novichok agents Nettle agents Phosgene oxime (CX)

Pulmonary agents Chlorine Chloropicrin (PS) Phosgene (CG) Diphosgene (DP) Incapacitating agents

Agent 15 (BZ) Dimethylheptylpyran (DMHP) 1. EA-3167 2. Kolokol-1 PAVA spray Sleeping gas Riot control agents Pepper spray (OC)

1. CS 2. CN (mace) 3. CR

List of chemical warfare agents A pulmonary agent (or choking agent) is a chemical weapon agent designed to impede a victim's ability to breathe. They operate by causing a build-up of fluids in the lungs which then leads to suffocation. Exposure to the eyes and skin tend to be corrosive, causing blurred vision and severe deep burns. Inhalation of these agents cause burning of the throat, coughing, vomiting, headache, pain in chest, tightness in chest, and respiratory and circulatory failure. Examples of pulmonary agents include: Chlorine gas Chloropicrin (PS) Diphosgene (DP) Phosgene (CG) Disulfur decafluoride Perfluoroisobutene Acrolein Diphenylcyanoarsine Phosgene is the most dangerous commonly used pulmonary agent (although disulfur decafluoride and perfluoroisobutene are both even more dangerous, with respectively 4 and 10 times the lethality of phosgene, neither is widely used). It is a colorless gas under ordinary conditions. It has a vapor density 3.4 times greater than that of air, allowing it to remain low in the air for long periods of times. Phosgene leads to massive pulmonary edema, which reaches maximum symptoms in 12 hours after exposure, followed by death within 24-48 hours. Chlorine is an element used in industry. It is one of the most commonly manufactured chemicals in the United States. It is used to make pesticides, rubber, and solvents. It is also used in drinking water and swimming pools to kill bacteria. The extent of poisoning caused by chlorine depends on the amount of chlorine a person is exposed to.

History
The first modern history use of a pulmonary agent was by the British in the Crimean War[citation needed] and the Union in the Civil War,[citation needed] using shells filled with chlorine gas.[citation needed] The first major use of these agents came on April 22, 1915, at the Second Battle of Ypres in Belgium. The Germans opened up 168 tons of chlorine gas on the French, Canadian and British troops which created a wind-borne cloud of chemical gas that opened up a breach in the lines. However, the Germans were not prepared to exploit the opening. In 1917 the Germans also introduced the agent phosgene. By then both sides had mastered the techniques of new choking agents such as diphosgene, chloropicrin, and perfluoroisobutene which allowed numerous attacks to be made. By the end of World War I phosgene was responsible for roughly 80% of all deaths related to chemical attacks.[citation needed]

References
U.S. Army Medical Research Institute of Chemical Defense. (Sep. 1995). Medical Management of Chemical Casualties Handbook: Pulmonary Agents. Retrieved Nov. 7, 2004. Roland E. Langford, Introduction to weapons of mass destruction : radiological, chemical, and biological. (Hoboken, New Jersey: Wiley-Interscience, 2004) Reaching Critical Will.org, Chemical Weapons (11 May 2008).[56] RJ Smith.com, Chemical Agents (11 May 2008). Eric A. Croddy and James J. Wirtz, Weapons of Mass Destruction: An Encyclopedia of Worldwide Policy, Technology, and History. (Santa Barbara, California: ABC-CLIO, 2005).

Chlorine
Chlorine
17

Cl

sulfur chlorine argonF Cl Br Chlorine in the periodic table Appearance pale yellow-green gas

General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight Electron configuration [Ne] 3s2 2, 8, 7 3p5 chlorine, Cl, 17 /klrin/ KLOHR-een or /klrn/ KLOHR-n diatomic nonmetal 17 (halogens), 3, p 35.45(1)

History Discovery First isolation Recognized as an element by Physical properties Phase Density Liquid density at b.p. Melting point Boiling point Critical point gas (0 C, 101.325 kPa) 3.2 g/L 1.562596 gcm3 171.6 K,-101.5 C,-150.7 F 239.11 K,-34.04 C,-29.27 F 416.9 K, 7.991 MPa Carl Wilhelm Scheele (1774) Carl Wilhelm Scheele (1774) Humphry Davy (1808)

96Chlorine, Gas Encyclopaedia, Air Liquide

Heat of fusion Heat of vaporization Molar heat capacity Vapor pressure P (Pa) at T (K) 1 128 10 139 100 153

(Cl2) 6.406 kJmol1 (Cl2) 20.41 kJmol1 (Cl2) 33.949 Jmol1K1

1k 170

10 k 197

100 k 239

Atomic properties Oxidation states Electronegativity Ionization energies (more) 7, 6, 5, 4, 3, 2, 1, -1 (strongly acidic oxide) 3.16 (Pauling scale) 1st: 1251.2 kJmol1

2nd: 2298 kJmol1 3rd: 3822 kJmol1 Covalent radius Van der Waals radius Miscellanea Crystal structure orthorhombic 1024 pm 175 pm

Magnetic ordering Electrical resistivity Thermal conductivity Speed of sound CAS registry number Most stable isotopes Main article: Isotopes of chlorine iso
35 36

diamagnetic97 (20 C) > 10 m 8.9103 Wm1K1 (gas, 0 C) 206 ms1 7782-50-5

NA 75.77% trace 24.23%

half-life
35

DM

DE

(MeV)

DP
36

Cl Cl Cl

Cl is stable with 18 neutrons 0.709 Ar S Cl is stable with 20 neutrons

3.01105 y
36

37

37

Chlorine is a chemical element with symbol Cl and atomic number 17. Chlorine is in the halogen group (17) and is the second lightest halogen after fluorine. The element is a yellow-green gas under standard conditions, where it forms diatomic molecules. It has the highest electron affinity and the fourth highest electronegativity of all the reactive elements; for this reason, chlorine is a strong oxidizing agent. Free chlorine is rare on Earth, and is usually a result of direct or indirect oxidation by oxygen.
97Magnetic susceptibility of the elements and inorganic compounds , in

The most common compound of chlorine, sodium chloride (common salt), has been known since ancient times. Around 1630 chlorine gas was first synthesized in a chemical reaction, but not recognized as a fundamentally important substance. Characterization of chlorine gas was made in 1774 by Carl Wilhelm Scheele, who supposed it an oxide of a new element. In 1809 chemists suggested that the gas might be a pure element, and this was confirmed by Sir Humphry Davy in 1810, who named it from Ancient Greek: khlros pale green. Nearly all chlorine in the Earth's crust occurs as chloride in various ionic compounds, including table salt. It is the second most abundant halogen and 21st most abundant chemical element in Earth's crust. Elemental chlorine is commercially produced from brine by electrolysis. The high oxidizing potential of elemental chlorine led commercially to free chlorine's bleaching and disinfectant uses, as well as its many uses of an essential reagent in the chemical industry. Chlorine is used in the manufacture of a wide range of consumer products, about two-thirds of them organic chemicals such as polyvinyl chloride, as well as many intermediates for production of plastics and other end products which do not contain the element. As a common disinfectant, elemental chlorine and chlorinegenerating compounds are used more directly in swimming pools to keep them clean and sanitary. In the form of chloride ions, chlorine is necessary to all known species of life. Other types of chlorine compounds are rare in living organisms, and artificially produced chlorinated organics range from inert to toxic. In the upper atmosphere, chlorine-containing organic molecules such as chlorofluorocarbons have been implicated in ozone depletion. Small quantities of elemental chlorine are generated by oxidation of chloride to hypochlorite in neutrophils, as part of the immune response against bacteria. Elemental chlorine at high concentrations is extremely dangerous and poisonous for all living organisms, and was historically used in World War I as the first gaseous chemical warfare agent.

Characteristics
Physical characteristics of chlorine and its compounds
At standard temperature and pressure, two chlorine atoms form the diatomic molecule Cl2. This is a yellow-green gas that has a distinctive strong odor, familiar to most from common household bleach. The bonding between the two atoms is relatively weak (only 242.580 0.004 kJ/mol), which makes the Cl2 molecule highly reactive. The boiling point at regular atmosphere is around 34 C, but it can be liquefied at room temperature with pressures above 740 kPa (107 psi).

Although elemental chlorine is yellow-green, chloride ion, in common with other halide ions, has no color in either minerals or solutions (example, table salt). Similarly, (again as with other halogens) chlorine atoms impart no color to organic chlorides when they replace hydrogen atoms in colorless organic compounds, such as tetrachloromethane. The melting point and density of these compounds is increased by substitution of hydrogen in place of chlorine. Compounds of chlorine with other halogens, however, as well as many chlorine oxides, are visibly colored.

Chemical characteristics
Along with fluorine, bromine, iodine, and astatine, chlorine is a member of the halogen series that forms the group 17 (formerly VII, VIIA, or VIIB) of the periodic table. Chlorine forms compounds with almost all of the elements to give compounds that are usually called chlorides. Chlorine gas reacts with most organic compounds, and will even sluggishly support the combustion of hydrocarbons.

Hydrolysis of free chlorine or disproportionation in water


At 25 C and atmospheric pressure, one liter of water dissolves 3.26 g or 1.125 L of gaseous chlorine.98 Solutions of chlorine in water contain chlorine (Cl2), hydrochloric acid, and hypochlorous acid: Cl2 + H2O HCl + HClO

This conversion to the right is called disproportionation, because the ingredient chlorine both increases and decreases in formal oxidation state. The solubility of chlorine in water is increased if the water contains dissolved alkali hydroxide, and in this way, chlorine bleach is produced.99 Cl2 + 2 OH ClO + Cl + H2O Chlorine gas only exists in a neutral or acidic solution.

Chemistry and compounds


Chlorine exists in all odd numbered oxidation states from 1 to +7, as well as the elemental state of zero and four in chlorine dioxide (see table below, and also structures in chlorite).100 Progressing through the states, hydrochloric acid can be oxidized using manganese dioxide, or hydrogen chloride gas oxidized catalytically by air to form elemental chlorine gas.101 Oxidation Name Formula Characteristic

98Wiberg 2001, p. 409. 99Greenwood 1997, pp. 857858. 100Greenwood 1997, p. 806. 101Wiberg 2001, p. 408.

state 1 chlorides Cl

compounds ionic chlorides, organic chlorides, hydrochloric acid elemental chlorine sodium hypochlorite, calcium hypochlorite sodium chlorite chlorine dioxide potassium chlorate, chloric acid, dichloryl trisulfate [ClO2]2[S3O10]. dichlorine hexoxide (gas). In liquid or solid disproportionates to mix of +5 and +7 oxidation states, as ionic chloryl perchlorate [ClO 2]+ [ClO 4] perchloric acid, perchlorate salts such as magnesium perchlorate, dichlorine heptoxide

0 +1

chlorine hypochlorites

Cl2 ClO

+3 +4 +5

chlorites chlorine(IV) chloryl, chlorates

ClO 2 ClO 2 ClO 3 ClO+ 2 Cl 2O 6

+6

chlorine(VI)

+7

perchlorates

ClO 4

Chlorides
Chlorine combines with almost all elements to give chlorides. Compounds with oxygen, nitrogen, xenon, and krypton are known, but do not form by direct reaction of the elements. Chloride is one of the most common anions in nature. Hydrogen chloride and its aqueous solution, hydrochloric acid, are produced on megaton scale annually both as valued intermediates but sometimes as undesirable pollutants.

Chlorine oxides
Chlorine forms a variety of oxides, as seen above: chlorine dioxide (ClO2), dichlorine monoxide (Cl2O), dichlorine hexoxide (Cl2O6), dichlorine heptoxide (Cl2O7). The anionic derivatives of these same oxides are also well known including chlorate (ClO 3), chlorite (ClO 2), hypochlorite (ClO), and perchlorate (ClO 4). The acid derivatives of these anions are hypochlorous acid (HOCl), chloric acid (HClO3) and perchloric acid (HClO4). The chloroxy cation chloryl (ClO2+) is known and has the same structure as chlorite but with a positive charge and chlorine in the +5 oxidation state.102 The compound "chlorine trioxide" does not occur, but rather in gas form is found as the dimeric dichlorine hexoxide (Cl2O6) with a +6 oxidation state. This compound in liquid or solid form disproportionates to a mixture of +5 and +7 oxidation states, occurring as the ionic compound chloryl perchlorate, [ClO 2]+ [ClO 4] .103 In hot concentrated alkali solution hypochlorite disproportionates: 2 ClO Cl + ClO 2 ClO + ClO 2 Cl + ClO 3 Sodium chlorate and potassium chlorate can be crystallized from solutions formed by the above reactions. If their crystals are heated to a high temperature, they undergo a further, final disproportionation: 4 ClO 3 Cl + 3 ClO 4

102Greenwood 1997, pp. 844850. 103Greenwood 1997, p. 849.

This same progression from chloride to perchlorate can be accomplished by electrolysis. The anode reaction progression is: Reaction Cl + 2 OH ClO + H2O + 2 e ClO + 2 OH ClO 2 + H2O + 2 e ClO 2 + 2 OH ClO 3 + H2O + 2 e ClO 3 + 2 OH ClO 4 + H2O + 2 e Electrode potential +0.89 volts +0.67 volts +0.33 volts

+0.35 volts

Each step is accompanied at the cathode by 2 H2O + 2 e 2 OH + H2 (0.83 volts)

Interhalogen compounds
Chlorine oxidizes bromide and iodide salts to bromine and iodine, respectively. However, it cannot oxidize fluoride salts to fluorine. It makes a variety of interhalogen compounds, such as the chlorine fluorides, chlorine monofluoride (ClF), chlorine trifluoride (ClF 3), chlorine pentafluoride (ClF 5). Chlorides of bromine and iodine are also known.

Organochlorine compounds
Chlorine is used extensively in organic chemistry in substitution and addition reactions. Chlorine often imparts many desired properties to an organic compound, in part owing to its electronegativity. Like the other halides, chlorine undergoes electrophilic addition reactions, the most notable one being the chlorination of alkenes and aromatic compounds with a Lewis acid catalyst. Organic chlorine compounds tend to be less reactive in nucleophilic substitution reactions than the corresponding bromine or iodine derivatives, but they tend to be cheaper. They may be activated for reaction by substituting with a tosylate group, or by the use of a catalytic amount of sodium iodide.[citation needed]

Occurrence
In the interstellar medium, chlorine is produced in supernovae via the r-process. In meteorites and on Earth, chlorine is found primarily as the chloride ion which occurs in minerals. In the Earth's crust, chlorine is present at average concentrations of about 126 parts per million,104 predominantly in such minerals as halite (sodium chloride), sylvite (potassium chloride), and carnallite (potassium magnesium chloride hexahydrate). Chloride is a component of the salt that is deposited in the earth or dissolved in the oceans about 1.9% of the mass of seawater is chloride ions. Even higher concentrations of chloride are found in the Dead Sea and in underground brine deposits. Most chloride salts are soluble in water, thus, chloride-containing minerals are usually only found in abundance in dry climates or deep underground. Over 2000 naturally occurring organic chlorine compounds are known.

Isotopes
Chlorine has a wide range of isotopes. The two stable isotopes are 35Cl (75.77%) and 37Cl (24.23%). Together they give chlorine an atomic weight of 35.4527 g/mol. The half-integer value for chlorine's weight caused some confusion in the early days of chemistry, when it had been postulated that atoms were composed of even units of hydrogen (see Proust's law), and the existence of chemical isotopes was unsuspected. Trace amounts of radioactive 36Cl exist in the environment, in a ratio of about 7x1013 to 1 with stable isotopes. 36Cl is produced in the atmosphere by spallation of 36Ar by interactions with cosmic ray protons. In the subsurface environment, 36 Cl is generated primarily as a result of neutron capture by 35Cl or muon capture by 40Ca. 36Cl decays to 36S and to 36Ar, with a combined half-life of 308,000 years. The half-life of this hydrophilic nonreactive isotope makes it suitable for geologic dating in the range of 60,000 to 1 million years. Additionally, large amounts of 36 Cl were produced by irradiation of seawater during atmospheric detonations of nuclear weapons between 1952 and 1958. The residence time of 36Cl in the atmosphere is about 1 week. Thus, as an event marker of 1950s water in soil and ground water, 36Cl is also useful for dating waters less than 50 years before the present. 36Cl has seen use in other areas of the geological sciences, including dating ice and sediments.

104Greenwood 1997, p. 795.

History
The most common compound of chlorine, sodium chloride, has been known since ancient times; archaeologists have found evidence that rock salt was used as early as 3000 BC and brine as early as 6000 BC. Around 1630, chlorine was recognized as a gas by the Belgian chemist and physician Jan Baptist van Helmont.105 Elemental chlorine was first prepared and studied in 1774 by Swedish chemist Carl Wilhelm Scheele, and, therefore, he is credited for its discovery. He called it "dephlogisticated muriatic acid air" since it is a gas (then called "airs") and it came from hydrochloric acid (then known as "muriatic acid"). However, he failed to establish chlorine as an element, mistakenly thinking that it was the oxide obtained from the hydrochloric acid (see phlogiston theory). He named the new element within this oxide as muriaticum. Regardless of what he thought, Scheele did isolate chlorine by reacting MnO2 (as the mineral pyrolusite) with HCl:106 4 HCl + MnO2 MnCl2 + 2 H2O + Cl2 Scheele observed several of the properties of chlorine: the bleaching effect on litmus, the deadly effect on insects, the yellow green color, and the smell similar to aqua regia.107 At the time, common chemical theory was: any acid is a compound that contains oxygen (still sounding in the German and Dutch names of oxygen: sauerstoff or zuurstof, both translating into English as acid stuff), so a number of chemists, including Claude Berthollet, suggested that Scheele's dephlogisticated muriatic acid air must be a combination of oxygen and the yet undiscovered element, muriaticum.108 In 1809, Joseph Louis Gay-Lussac and Louis-Jacques Thnard tried to decompose dephlogisticated muriatic acid air by reacting it with charcoal to release the free element muriaticum (and carbon dioxide). They did not succeed and published a report in which they considered the possibility that dephlogisticated muriatic acid air is an element, but were not convinced.

105Greenwood 1997, p. 790. 106 107Greenwood 1997, p. 793. 108Greenwood 1997, p. 792.

In 1810, Sir Humphry Davy tried the same experiment again, and concluded that it is an element, and not a compound. He named this new element as chlorine, from the Greek word (chlros), meaning green-yellow. The name halogen, meaning "salt producer," was originally used for chlorine in 1811 by Johann Salomo Christoph Schweigger. However, this term was later used as a generic term to describe all the elements in the chlorine family (fluorine, bromine, iodine), after a suggestion by Jns Jakob Berzelius in 1842.109 In 1823, Michael Faraday liquefied chlorine for the first time, and demonstrated that what was then known as "solid chlorine" had a structure of chlorine hydrate (Cl2H2O).110 Chlorine gas was first used by French chemist Claude Berthollet to bleach textiles in 1785. Modern bleaches resulted from further work by Berthollet, who first produced sodium hypochlorite in 1789 in his laboratory in the town of Javel (now part of Paris, France), by passing chlorine gas through a solution of sodium carbonate. The resulting liquid, known as "Eau de Javel" ("Javel water"), was a weak solution of sodium hypochlorite. However, this process was not very efficient, and alternative production methods were sought. Scottish chemist and industrialist Charles Tennant first produced a solution of calcium hypochlorite ("chlorinated lime"), then solid calcium hypochlorite (bleaching powder). These compounds produced low levels of elemental chlorine, and could be more efficiently transported than sodium hypochlorite, which remained as dilute solutions because when purified to eliminate water, it became a dangerously powerful and unstable oxidizer. Near the end of the nineteenth century, E. S. Smith patented a method of sodium hypochlorite production involving electrolysis of brine to produce sodium hydroxide and chlorine gas, which then mixed to form sodium hypochlorite. This is known as the chloralkali process, first introduced on an industrial scale in 1892, and now the source of essentially all modern elemental chlorine and sodium hydroxide production (a related lowtemperature electrolysis reaction, the Hooker process, is now responsible for bleach and sodium hypochlorite production). Elemental chlorine solutions dissolved in chemically basic water (sodium and calcium hypochlorite) were first used as anti-putrification agents and disinfectants in the 1820s, in France, long before the establishment of the germ theory of disease. This work is mainly due to Antoine-Germain Labarraque, who adapted Berthollet's "Javel water" bleach and other chlorine preparations for the purpose (for a more complete history, see below). Elemental chlorine has since served a continuous function in topical antisepsis (wound irrigation solutions and the like) as well as public sanitation (especially of swimming and drinking water). In 1826, silver chloride was used to produce photographic images for the first time. Chloroform was first used as an anesthetic in 1847. Polyvinyl chloride (PVC) was invented in 1912, initially without a purpose.

109Greenwood 1997, p. 789. 110

Chlorine gas was first introduced as a weapon on April 22, 1915, at Ypres by the German Army, and the results of this weapon were disastrous because gas masks had not been mass distributed and were tricky to get on quickly.

Production
In industry, elemental chlorine is usually produced by the electrolysis of sodium chloride dissolved in water. This method, the chloralkali process industrialized in 1892, now provides essentially all industrial chlorine gas.111 Along with chlorine, the method yields hydrogen gas and sodium hydroxide (with sodium hydroxide actually being the most crucial of the three industrial products produced by the process). The process proceeds according to the following chemical equation:112 2 NaCl + 2 H2O Cl2 + H2 + 2 NaOH The electrolysis of chloride solutions all proceed according to the following equations: Cathode: 2 H+ (aq) + 2 e H2 (g) Anode: 2 Cl (aq) Cl2 (g) + 2 e Overall process: 2 NaCl (or KCl) + 2 H2O Cl2 + H2 + 2 NaOH (or KOH) In diaphragm cell electrolysis, an asbestos (or polymer-fiber) diaphragm separates a cathode and an anode, preventing the chlorine forming at the anode from re-mixing with the sodium hydroxide and the hydrogen formed at the cathode. The salt solution (brine) is continuously fed to the anode compartment and flows through the diaphragm to the cathode compartment, where the caustic alkali is produced and the brine is partially depleted. Diaphragm methods produce dilute and slightly impure alkali but they are not burdened with the problem of preventing mercury discharge into the environment and they are more energy efficient. Membrane cell electrolysis employ permeable membrane as an ion exchanger. Saturated sodium (or potassium) chloride solution is passed through the anode compartment, leaving at a lower concentration. This method is more efficient than the diaphragm cell and produces very pure sodium (or potassium) hydroxide at about 32% concentration, but requires very pure brine.

Laboratory methods
Small amounts of chlorine gas can be made in the laboratory by combining hydrochloric acid and manganese dioxide. Alternatively a strong acid such as sulfuric acid or hydrochloric acid reacts with sodium hypochlorite solution to release chlorine gas but reacts with sodium chlorate to produce chlorine gas and chlorine dioxide gas as well. In the home, accidents occur when hypochlorite bleach solutions are combined with certain acidic drain-cleaners.
111Greenwood 1997, p. 798. 112

Applications
Production of industrial and consumer products
Principal applications of chlorine are in the production of a wide range of industrial and consumer products. For example, it is used in making plastics, solvents for dry cleaning and metal degreasing, textiles, agrochemicals and pharmaceuticals, insecticides, dyestuffs, household cleaning products, etc. Many important industrial products are produced via organochlorine intermediates. Examples include polycarbonates, polyurethanes, silicones, polytetrafluoroethylene, carboxymethyl cellulose, and propylene oxide. Like the other halogens, chlorine participates in free-radical substitution reactions with hydrogen-containing organic compounds. When applied to organic substrates, reaction is oftenbut not invariablynon-regioselective, and, hence, may result in a mixture of isomeric products. It is often difficult to control the degree of substitution as well, so multiple substitutions are common. If the different reaction products are easily separated, e.g., by distillation, substitutive freeradical chlorination (in some cases accompanied by concurrent thermal dehydrochlorination) may be a useful synthetic route. Industrial examples of this are the production of methyl chloride, methylene chloride, chloroform, and carbon tetrachloride from methane, allyl chloride from propylene, and trichloroethylene, and tetrachloroethylene from 1,2-dichloroethane. Quantitatively, about 63% and 18% of all elemental chlorine produced is used in the manufacture of organic and inorganic chlorine compounds, respectively,113. About 15,000 chlorine compounds are being used commercially.114 The remaining 19% is used for bleaches and disinfection products.115 The most significant of organic compounds in terms of production volume are 1,2-dichloroethane and vinyl chloride, intermediates in the production of PVC. Other particularly important organochlorines are methyl chloride, methylene chloride, chloroform, vinylidene chloride, trichloroethylene, perchloroethylene, allyl chloride, epichlorohydrin, chlorobenzene, dichlorobenzenes, and trichlorobenzenes. The major inorganic compounds include HCl, Cl2O, HOCl, NaClO3, chlorinated isocyanurates, AlCl3, SiCl4, SnCl4, PCl3, PCl5, POCl3, AsCl3, SbCl3, SbCl5, BiCl3, S2Cl2, SCl2, SOCI2, CIF3, ICl, ICl3, TiCl3, TiCl4, MoCl5, FeCl3, ZnCl2, etc.116117

113 114 115 116 117Wiberg 2001, p. 412.

Public sanitation, disinfection, and antisepsis


Combating putrefaction
In France (as elsewhere) there was a need to process animal guts in order to make musical instrument strings, Goldbeater's skin and other products. This was carried out in "gut factories" (boyauderies) as an odiferous and unhealthy business. In or about 1820, the Socit d'encouragement pour l'industrie nationale offered a prize for the discovery of a method, chemical or mechanical, that could be used to separate the peritoneal membrane of animal intestines without causing putrefaction. It was won by Antoine-Germain Labarraque, a 44 year-old French chemist and pharmacist who had discovered that Berthollet's chlorinated bleaching solutions ("Eau de Javel") not only destroyed the smell of putrefaction of animal tissue decomposition, but also retarded the decomposition process itself. Labarraque's research resulted in chlorides and hypochlorites of lime (calcium hypochlorite) and of sodium (sodium hypochlorite) being employed not only in the boyauderies but also for the routine disinfection and deodorisation of latrines, sewers, markets, abattoirs, anatomical theatres and morgues. They were also used, with success, in hospitals, lazarets, prisons, infirmaries (both on land and at sea), magnaneries, stables, cattle-sheds, etc.; and for exhumations, embalming, during outbreaks of epidemic illness, fever, blackleg in cattle, etc.

Against infection and contagion


Labarraque's chlorinated lime and soda solutions have been advocated since 1828 to prevent infection (called "contagious infection", and presumed to be transmitted by "miasmas") and also to treat putrefaction of existing wounds, including septic wounds.118 In this 1828 work, Labarraque recommended for the doctor to breathe chlorine, wash his hands with chlorinated lime, and even sprinkle chlorinated lime about the patient's bed, in cases of "contagious infection." In 1828, it was well known that some infections were contagious, even though the agency of the microbe was not to be realized or discovered for more than half a century.

118Scott, James (trans.). On the disinfecting properties of Labarraque's preparations of chlorine (S. Highley, 1828) Accessed Nov 1, 2011.

During the Paris cholera outbreak of 1832, large quantities of so-called chloride of lime were used to disinfect the capital. This was not simply modern calcium chloride, but contained chlorine gas dissolved in lime-water (dilute calcium hydroxide) to form calcium hypochlorite (chlorinated lime). Labarraque's discovery helped to remove the terrible stench of decay from hospitals and dissecting rooms, and, by doing so, effectively deodorised the Latin Quarter of Paris.119 These "putrid miasmas" were thought by many to be responsible for the spread of "contagion" and "infection" both words used before the germ theory of infection. The use of chloride of lime was based on destruction of odors and "putrid matter." One source has claimed that chloride of lime was used by Dr. John Snow to disinfect water from the cholera-contaminated well feeding the Broad Street pump in 1854 London.120 Three reputable sources that described the famous Broad Street pump cholera epidemic do not mention Snow performing any disinfection of water from that well.121122123 Instead, one reference makes it clear that chloride of lime was used to disinfect the offal and filth in the streets surrounding the Broad Street pumpa common practice in midnineteenth century England.:296

Semmelweis and experiments with antisepsis


Perhaps the most famous application of Labarraque's chlorine and chemical base solutions was in 1847, when Ignaz Semmelweis used (first) chlorine-water (simply chlorine dissolved in pure water), then cheaper chlorinated lime solutions, to deodorize the hands of Austrian doctors, which Semmelweis noticed still carried the stench of decomposition from the dissection rooms to the patient examination rooms. Semmelweis, still long before the germ theory of disease, had theorized that "cadaveric particles" were somehow transmitting decay from fresh medical cadavers to living patients, and he used the well-known "Labarraque's solutions" as the only known method to remove the smell of decay and tissue decomposition (which he found that soap did not). The solutions proved to be far more effective germicide antiseptics than soap (Semmelweis was also aware of their greater efficacy, but not the reason), and this resulted in Semmelweis's (later) celebrated success in stopping the transmission of childbed fever ("puerperal fever") in the maternity wards of Vienna General Hospital in Austria in 1847.

119Corbin, Alain. The Foul and the Fragrant: Odor and the French Social Imagination (Harvard University Press, 1988) pp. 1212. 120Black and Veatch Corp. (2010). White's Handbook of Chlorination and Alternative Disinfectants. Hoboken, NJ:Wiley. first page, Chapter 9. 121Vinten-Johansen, Peter, Howard Brody, Nigel Paneth, Stephen Rachman and Michael Rip. (2003). Cholera, Chloroform, and the Science of Medicine. New York:Oxford University. 122Hemphill, Sandra. (2007). The Strange Case of the Broad Street Pump: John Snow and the Mystery of Cholera. Los Angeles:University of California 123Johnson, Steven. (2006). The Ghost Map: The Story of London's Most Terrifying Epidemic and How It Changed Science, Cities, and the Modern World. New York :Riverhead Books

Much later, during World War I in 1916, a standardized and diluted modification of Labarraque's solution, containing hypochlorite (0.5%) and boric acid as an acidic stabilizer, was developed by Henry Drysdale Dakin (who gave full credit to Labarraque's prior work in this area). Called Dakin's solution, the method of wound irrigation with chlorinated solutions allowed antiseptic treatment of a wide variety of open wounds, long before the modern antibiotic era. A modified version of this solution continues to be employed in wound irrigation in the modern era, where it remains effective against multiply antibiotic resistant bacteria (see Century Pharmaceuticals).

Public sanitation
By 1918, the US Department of Treasury called for all drinking water to be disinfected with chlorine. Chlorine is presently an important chemical for water purification (such as in water treatment plants), in disinfectants, and in bleach. Chlorine in water is more than three times as effective as a disinfectant against Escherichia coli than an equivalent concentration of bromine, and is more than six times more effective than an equivalent concentration of iodine. Chlorine is usually used (in the form of hypochlorous acid) to kill bacteria and other microbes in drinking water supplies and public swimming pools. In most private swimming pools, chlorine itself is not used, but rather sodium hypochlorite, formed from chlorine and sodium hydroxide, or solid tablets of chlorinated isocyanurates. The drawback of using chlorine in swimming pools is that the chlorine reacts with a human's hair and skin because hair and skin are made from protein (see Hypochlorous acid#Reaction with protein amino groups). Once the chlorine reacts with the hair and Mustard gas (bis(chloroethyl) thioether) alkylating a DNA amine skin, it becomes chemically bonded. Even base. small water supplies are now routinely chlorinated. It is often impractical to store and use poisonous chlorine gas for water treatment, so alternative methods of adding chlorine are used. These include hypochlorite solutions, which gradually release chlorine into the water, and compounds like sodium dichloro-s-triazinetrione (dihydrate or anhydrous), sometimes referred to as "dichlor", and trichloro-s-triazinetrione, sometimes referred to as "trichlor". These compounds are stable while solid and may be used in powdered, granular, or tablet form. When added in small amounts to pool water or industrial water systems, the chlorine atoms hydrolyze from the rest of the molecule forming hypochlorous acid (HOCl), which acts as a general biocide, killing germs, micro-organisms, algae, and so on.124125

124Greenwood 1997, p. 860. 125Wiberg 2001, p. 411.

Use as a weapon
World War I
Chlorine gas, also known as bertholite, was first used as a weapon in World War I by Germany on April 22, 1915 in the Second Battle of Ypres.126 As described by the soldiers it had a distinctive smell of a mixture between pepper and pineapple. It also tasted metallic and stung the back of the throat and chest. Chlorine can react with water in the mucosa of the lungs to form hydrochloric acid, an irritant that can be lethal. The damage done by chlorine gas can be prevented by a gas mask, or other filtration method, which makes the overall chance of death by chlorine gas much lower than those of other chemical weapons. It was pioneered by a German scientist later to be a Nobel laureate, Fritz Haber of the Kaiser Wilhelm Institute in Berlin, in collaboration with the German chemical conglomerate IG Farben, who developed methods for discharging chlorine gas against an entrenched enemy. It is alleged that Haber's role in the use of chlorine as a deadly weapon drove his wife, Clara Immerwahr, to suicide. After its first use, chlorine was utilized by both sides as a chemical weapon, but it was soon replaced by the more deadly phosgene and mustard gas.

Iraq War
Chlorine gas has also been used by insurgents against the local population and coalition forces in the Iraq War in the form of chlorine bombs. On March 17, 2007, for example, three chlorine-filled trucks were detonated in the Anbar province killing two and sickening over 350. Other chlorine bomb attacks resulted in higher death tolls, with more than 30 deaths on two separate occasions. Most of the deaths were caused by the force of the explosions rather than the effects of chlorine, since the toxic gas is readily dispersed and diluted in the atmosphere by the blast. The Iraqi authorities have tightened security for elemental chlorine, which is essential for providing safe drinking water to the population.

126"Battle of Ypres" The Canadian Encyclopedia

Chlorine induced cracking in structural materials


The element is widely used for purifying water owing to its powerful oxidizing properties, especially potable water supplies and water used in swimming pools. Several catastrophic collapses of swimming pool ceilings have occurred owing to chlorine induced stress corrosion cracking of stainless steel rods used to suspend them. Some polymers are also sensitive to attack, including acetal resin and polybutene. Both materials were used in hot and cold water domestic supplies, and stress corrosion cracking caused widespread failures in the USA in the 1980s and 1990s. The picture on the right shows an acetal joint in a water supply system, which, when it fractured, caused substantial physical damage to computers in the labs below the supply. The cracks started at injection molding defects in the joint and slowly grew until finally triggered. The fracture surface shows iron and calcium salts that were deposited in the leaking joint from the water supply before failure.

Health effects of the free element and hazards


NFPA 704

Chlorine is a toxic gas that irritates the respiratory system. Because it is heavier than air, it tends to accumulate at the bottom of poorly ventilated spaces. Chlorine gas is a strong oxidizer, which may react with flammable materials. Chlorine is detectable with measuring devices in concentrations of as low as 0.2 parts per million (ppm), and by smell at 3 ppm. Coughing and vomiting may occur at 30 ppm and lung damage at 60 ppm. About 1000 ppm can be fatal after a few deep breaths of the gas.127 Breathing lower concentrations can aggravate the respiratory system, and exposure to the gas can irritate the eyes. The toxicity of chlorine comes from its oxidizing power. When chlorine is inhaled at concentrations above 30 ppm, it begins to react with water and cells, which change it into hydrochloric acid (HCl) and hypochlorous acid (HClO). When used at specified levels for water disinfection, the reaction of chlorine with water is not a major concern for human health. Other materials present in the water may generate disinfection by-products that are associated with negative effects on human health, however, the health risk is far lower than drinking undisinfected water.

127

Organochlorine compounds as pollutants


Some organochlorine compounds are serious pollutants. These are produced either as by-products or end products of industrial processes which are persistent in the environment, such as certain chlorinated pesticides and chlorofluorocarbons. Chlorine is added both to pesticides and pharmaceuticals to make the molecules more resistant to enzymatic degradation by bacteria, insects, and mammals, but this property also has the effect of prolonging the residence time of these compounds when they enter the environment. In this respect chlorinated organics have some resemblance to fluorinated organics.

Bibliography
Greenwood, Norman N; Earnshaw, Alan (1997). Chemistry of the Elements (2 ed.). Oxford: Butterworth-Heinemann. ISBN 0-08-037941-9. Wiberg, Egon; Wiberg, Nils and Holleman, Arnold Frederick (2001). Inorganic Chemistry. Academic Press. ISBN 0-12-352651-5.

External links
Chlorine at The Periodic Table of Videos (University of Nottingham) Agency for Toxic Substances and Disease Registry: Chlorine Electrolytic production Production and liquefaction of chlorine

Chlorine Production Using Mercury, Environmental Considerations and Alternatives National Pollutant Inventory Chlorine National Institute for Occupational Safety and Health Chlorine Page Chlorine Institute Trade association representing the chlorine industry Chlorine Online the web portal of Eurochlor the business association of the European chlor-alkali industry

Phosgene
Phosgene128

Identifiers CAS number PubChem ChemSpider UNII EC number UN number ChEBI RTECS number Jmol-3D images 75-44-5 6371 6131 117K140075 200-870-3 1076 CHEBI:29365 SY5600000 Image 1

Properties Molecular formula Molar mass Appearance


128Merck Index, 11th Edition, 7310.

CCl2O 98.92 g mol1 colorless gas

Density Melting point Boiling point Solubility in water Solubility Structure Molecular shape Dipole moment Hazards MSDS EU Index EU classification R-phrases S-phrases NFPA 704

4.248 g/L (15 C, gas) 1.432 g/cm3 (0 C, liquid) 118 C, 155 K, -180 F 8.3 C, 281 K, 47 F decomposes in water129 soluble in benzene, toluene, acetic acid decomposes in alcohol and acid Planar, trigonal 1.17 D ICSC 0007 006-002-00-8 Very toxic (T+) R26 R34 (S1/2) S9 S26 S36/37/39 S45

Flash point Threshold Limit Value Related compounds Related compounds

non-flammable 0.1 ppm Thiophosgene Formaldehyde Carbonic acid Urea Carbon monoxide Chloroformic acid

(verify) (what is: / ?) Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references

129http://www.inchem.org/documents/icsc/icsc/eics0007.htm

Phosgene is the chemical compound with the formula COCl2. This colorless gas gained infamy as a chemical weapon during World War I. It is also a valued industrial reagent and building block in synthesis of pharmaceuticals and other organic compounds. In low concentrations, its odor resembles freshly cut hay or grass.130 In addition to its industrial production, small amounts occur naturally from the breakdown and the combustion of organochlorine compounds, such as those used in refrigeration systems. The chemical was named by combining the Greek words 'phos' (meaning light) and genesis (birth); it does not mean it contains any phosphorus (cf. phosphine).

Structure and basic properties


Phosgene is a planar molecule as predicted by VSEPR theory. The C=O distance is 1.18 , the CCl distance is 1.74 and the ClCCl angle is 111.8. It is one of the simplest acid chlorides, being formally derived from carbonic acid.

Production
Industrially, phosgene is produced by passing purified carbon monoxide and chlorine gas through a bed of porous activated carbon, which serves as a catalyst: CO + Cl2 COCl2 (Hrxn = 107.6kJ/mol) The reaction is exothermic, therefore the reactor must be cooled. Typically, the reaction is conducted between 50 and 150 C. Above 200 C, phosgene reverts to carbon monoxide and chlorine, Keq (300K) = 0.05. World production of this compound was estimated to be 2.74 million tonnes in 1989. Because of safety issues, phosgene is almost always produced and consumed within the same plant and extraordinary measures are made to contain this toxic gas. It is listed on schedule 3 of the Chemical Weapons Convention: All production sites manufacturing more than 30 tonnes per year must be declared to the OPCW.131 Although less dangerous than many other chemical weapons, such as sarin, phosgene is still regarded as a viable chemical warfare agent because it is so easy to manufacture when compared to the production requirements of more technically advanced chemical weapons such as the firstgeneration nerve agent tabun.132

130CBRNE - Lung-Damaging Agents, Phosgene May 27, 2009 131Annex on Implementation and Verification ("Verification Annex") 132https://itportal.decc.gov.uk/cwc_files/S2AAD_guidance.pdf

Adventitious occurrence
Upon ultraviolet (UV) radiation in the presence of oxygen, chloroform slowly converts into phosgene by a radical reaction. To suppress this photodegradation, chloroform is often stored in brown-tinted glass containers. Chlorinated compounds used to remove oil from metals, such as automotive brake cleaners, are converted to phosgene by the UV rays of arc welding processes. Phosgene may also be produced during testing for leaks of older-style refrigerant gases. Chloromethanes (R12, R22 and others) were formerly leak-tested in situ by employing a small gas torch (propane, butane or propylene gas) with a sniffer tube and a copper reaction plate in the flame nozzle of the torch. If any refrigerant gas was leaking from a pipe or joint, the gas would be sucked into the flame via the sniffer tube and would cause a colour change of the gas flame to a bright greenish blue. In the process, phosgene gas would be created due to the thermal reaction. No valid statistics are available, but anecdotal reports suggest that numerous refrigeration technicians suffered the effects of phosgene poisoning due to their ignorance of the toxicity of phosgene, produced during such leak testing. Electronic sensing of refrigerant gases phased out the use of flame testing for leaks in the 1980s. Similarly, phosgene poisoning is a consideration for people fighting fires that are occurring in the vicinity of freon refrigeration equipment, smoking in the vicinity of a freon leak, or fighting fires using halon or halotron.

Uses
The great majority of phosgene is used in the production of isocyanates, the most important being toluene diisocyanate (TDI) and methylene diphenyl diisocyanate (MDI). These isocyanates are precursors to polyurethanes.

Synthesis of carbonates
Significant amounts are also used in the production of polycarbonates by its reaction with bisphenol A. Polycarbonates are an important class of engineering thermoplastic found, for example, in lenses in eye glasses. Diols react with phosgene to give either linear or cyclic carbonates (R = H, alkyl, aryl): HOCR2-X-CR2OH + COCl2 1/n [OCR2-X-CR2OC(O)-]n + 2 HCl

Synthesis of isocyanates
The synthesis of isocyanates from amines illustrates the electrophilic character of this reagent and its use in introducing the equivalent of "CO2+": RNH2 + COCl2 RN=C=O + 2 HCl (R = alkyl, aryl)

Such reactions are conducted in the presence of a base such as pyridine that absorbs the hydrogen chloride.

Laboratory uses
In the research laboratory phosgene still finds limited use in organic synthesis. A variety of substitutes have been developed, notably trichloromethyl chloroformate ("diphosgene"), a liquid at room temperature, and bis(trichloromethyl) carbonate ("triphosgene"), a crystalline substance.133 Aside from the above reactions that are widely practiced industrially, phosgene is also used to produce acid chlorides and carbon dioxide from carboxylic acids: RCO2H + COCl2 RC(O)Cl + HCl + CO2 Such acid chlorides react with amines and alcohols to give, respectively, amides and esters, which are commonly used intermediates. Thionyl chloride is more commonly and more safely employed for this application. A specific application for phosgene is the production of chloroformic esters: ROH + COCl2 ROC(O)Cl + HCl

Other chemistry
Although it is somewhat hydrophobic, phosgene reacts with water to release hydrogen chloride and carbon dioxide: COCl2 + H2O CO2 + 2 HCl Analogously, with ammonia, one obtains urea: COCl2 + 4 NH3 CO(NH2)2 + 2 NH4Cl

133Hamley, P. "Phosgene" Encyclopedia of Reagents for Organic Synthesis , 2001 John Wiley, New York.

Halide exchange with nitrogen trifluoride and aluminium tribromide gives COF2 and COBr2, respectively.

History
Phosgene was synthesized by the British chemist John Davy (17901868) in 1812 by exposing a mixture of carbon monoxide and chlorine to sunlight. He named it "phosgene" in reference of the use of light to promote the reaction; from Greek, phos (light) and gene (born). It gradually became important in the chemical industry as the 19th century progressed, particularly in dye manufacturing.

Chemical warfare
Following the extensive use of phosgene gas in combat during World War I, it was stockpiled by various countries as part of their secret chemical weapons programs.134135136 In May 1928, eleven tons of phosgene escaped from a war surplus store in central Hamburg. 300 people were poisoned of whom 10 died. Phosgene was then only frequently used by the Imperial Japanese Army against the Chinese during the Second Sino-Japanese War.137 Gas weapons, such as phosgene, were produced by Unit 731 and authorized by specific orders given by Hirohito (Emperor Showa) himself, transmitted by the chief of staff of the army. For example, the Emperor authorized the use of toxic gas on 375 separate occasions during the battle of Wuhan from August to October 1938.138

Safety
Phosgene is an insidious poison as the odor may not be noticed and symptoms may be slow to appear. The odor detection threshold for phosgene is 0.4 ppm, four times the threshold limit value. Its high toxicity arises from the action of the phosgene on the proteins in the pulmonary alveoli, the site of gas exchange: their damage disrupts the blood-air barrier, causing suffocation. It reacts with the amines of the proteins, causing crosslinking by formation of urea-like linkages, in accord with the reactions discussed above. Phosgene detection badges are worn by those at risk of exposure.
134Base's phantom war reveals its secrets, Lithgow Mercury, 7/08/2008 135Chemical warfare left its legacy, Lithgow Mercury, 9/09/2008 136Chemical bombs sit metres from Lithgow families for 60 years, The Daily Telegraph, September 22, 2008 137Yuki Tanaka, "Poison Gas, the Story Japan Would Like to Forget", Bulletin of the Atomic Scientists, October 1988, p. 1617 138Y. Yoshimi and S. Matsuno, Dokugasusen Kankei Shiry II, Kaisetsu, Jugonen Sens Gokuhi Shiryoshu, 1997, p. 2729

Sodium bicarbonate may be used to neutralise liquid spills of phosgene. Gaseous spills may be mitigated with ammonia.

External links
Davy's account of his discovery of phosgene International Chemical Safety Card 0007 CDC - Phosgene - NIOSH Workplace Safety and Health Topic NIOSH Pocket Guide to Chemical Hazards U.S. CDC Emergency Preparedness & Response U.S. EPA Acute Exposure Guideline Levels Regime For Schedule 3 Chemicals And Facilities Related To Such Chemicals, OPCW website CBWInfo website Use of Phosgene in WWII and in modern-day warfare (Refer to Section 4.C of the article) An experience with accidental poisoning by heated tetrachlorethylene solvent

Blister Agents
Blister agent
A blister agent, or vesicant, is a chemical compound that causes severe skin, eye and mucosal pain and irritation. They are named for their ability to cause severe chemical burns, resulting in painful water blisters on the bodies of those affected. Although the term is often used in connection with large-scale burns caused by chemical spills or chemical warfare agents,139 some naturally occurring substances such as cantharidin are also blister-producing agents (vesicants).140 Some naturally occurring substances, such as furanocoumarin, cause vesicant-like effects indirectly, for example, by increasing skin photosensitivity greatly. Vesicants have medical uses including wart removal but can be fatal if even small amounts are ingested.

139Center for Disease Control 140Cantharidin and Meloids: a review of classical history, biosynthesis, and function

Blister agents used in warfare


Most blister agents fall into one of three groups: Sulfur mustards A family of sulfur-based agents, including the so-called "mustard gas". Nitrogen mustards A family of agents similar to the sulfur mustards, but based on nitrogen instead of sulfur. Lewisite An early blister agent that was developed, but not used, during World War I. It was effectively rendered obsolete with the development of British antiLewisite in the 1940s. Occasionally, phosgene oxime is included among the blister agents, although it is more properly termed a nettle agent.

Effects of blister agents


Exposure to a weaponized blister agent can cause a number of life-threatening symptoms, including: Severe skin, eye and mucosal pain and irritation Skin erythema with large fluid blisters that heal slowly and may become infected Tearing, conjunctivitis, corneal damage Mild respiratory distress to marked airway damage All blister agents currently known are heavier than air, and are readily absorbed through the eyes, lungs, and skin. Effects of the two mustard agents are typically delayed: exposure to vapors becomes evident in 4 to 6 hours, and skin exposure in 2 to 48 hours. The effects of Lewisite are immediate.

External links
Medterms.com Medical Aspects of Biological and Chemical Warfare, Chapter 7: Vesicants

Sulfur mustard
Sulfur mustard

Identifiers CAS number PubChem ChemSpider KEGG ChEBI ChEMBL Jmol-3D images 505-60-2 10461 21106142 C19164 CHEBI:25434 CHEMBL455341 Image 1

Properties Molecular formula Molar mass Appearance C4H8Cl2S 159.08 g mol1 Colorless if pure. Normally ranges from pale yellow to dark brown. Slight garlic or horseradish type odour141 1.27 g/mL, liquid 14.4 C, 287.6 K, 57.9 F 218 C, 491 K, 424 F (begins to

Density Melting point Boiling point

141FM 38 Chemical Reference handbook, US Army, 1967

decompose at 217 C and boils at 218 C) Solubility in water Solubility Hazards MSDS EU classification External MSDS Very toxic (T+) Dangerous for the environment (N) Vesicant Carc. Cat 1 Poison, contact hazard, inhalation hazard, corrosive, environmental hazard, carcinogenic, possibly mutagenic Negligible soluble in ether, benzene, fat, alcohol, THF

Main hazards

NFPA 704

Flash point Related compounds Related compounds (verify) (what is: / ?)

105 C Nitrogen mustard

Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references The sulfur mustards, or sulphur mustards,142 commonly known as mustard gas, are a class of related cytotoxic and vesicant chemical warfare agents with the ability to form large blisters on the exposed skin and in the lungs. Pure sulfur mustards are colorless, viscous liquids at room temperature. When used in impure form, such as warfare agents, they are usually yellow-brown in color and have an odor resembling mustard plants, garlic, or horseradish, hence the name. Mustard gas was originally assigned the name LOST, after the scientists Wilhelm Lommel and Wilhelm Steinkopf, who developed a method for the large-scale production of mustard gas for the Imperial German Army in 1916.

142Mustard Gas (Sulphur Mustard) (IARC Summary & Evaluation, Supplement7, 1987) . Inchem.org (1998-02-09). Retrieved on 2011-05-29.

Mustard agents are regulated under the 1993 Chemical Weapons Convention (CWC). Three classes of chemicals are monitored under this Convention, with sulfur and nitrogen mustard grouped in Schedule 1, as substances with no use other than in chemical warfare. Mustard agents could be deployed on the battlefield by means of artillery shells, aerial bombs, rockets, or by spraying from warplanes.

Synthesis
Sulfur mustard is the organic compound with formula (Cl-CH2CH2)2S. In the Depretz method, sulfur mustard is synthesized by treating sulfur dichloride with ethylene: SCl2 + 2 C2H4 (Cl-CH2CH2)2S In the Levinstein process, sulfur monochloride is used instead: 8 S2Cl2 + 16 C2H4 8 (Cl-CH2CH2)2S + S8 In the Meyer method, thiodiglycol is produced from chloroethanol and potassium sulfide and chlorinated with phosphorus trichloride: 3 (HO-CH2CH2)2S + 2 PCl3 3 (Cl-CH2CH2)2S + 2 P(OH)3 In the Meyer-Clarke method, concentrated hydrochloric acid (HCl) instead of PCl3 is used as the chlorinating agent: (HO-CH2CH2)2S + 2 HCl (Cl-CH2CH2)2S + 2 H2O Thionyl chloride and phosgene have also been used as chlorinating agents. It is a viscous liquid at normal temperatures. The pure compound has a melting point of 14 C (57 F) and decomposes before boiling at 218 C (424.4 F).

Mechanism of toxicity
The compound readily eliminates a chloride ion by intramolecular nucleophilic substitution to form a cyclic sulfonium ion. This very reactive intermediate tends to permanently alkylate the guanine nucleotide in DNA strands, which prevents cellular division and generally leads directly to programmed cell death,143 or, if cell death is not immediate, the damaged DNA may lead to the development of cancer. Sulfur mustard is not very soluble in water but is very soluble in fat, contributing to its rapid absorption into the skin.

143Mustard agents: description, physical and chemical properties, mechanism of action, symptoms, antidotes and methods of treatment. Organisation for the Prohibition of Chemical Weapons. Accessed June 8, 2010.

In the wider sense, compounds with the structural element BCH2CH2X, where X is any leaving group and B is a Lewis base are Mustard gas (bis(chloroethyl) known as mustards. Such compounds can thioether) alkylating a DNA amine form cyclic "onium" ions (sulfonium, base. ammoniums, etc.) that are good alkylating agents. Examples are bis(2chloroethyl)ether, the (2-haloethyl)amines (nitrogen mustards), and sulfur sesquimustard, which has two -chloroethyl thioether groups (ClH2C-CH2-S-) connected by an ethylene (-CH2CH2-) group.[citation needed] These compounds have a similar ability to alkylate DNA, but their physical properties, e.g. melting point, vary.

Physiological effects
Mustard gas has extremely powerful vesicant effects on its victims. In addition, it is strongly mutagenic and carcinogenic, due to its alkylating properties. It is also lipophilic. Because people exposed to mustard gas rarely suffer immediate symptoms, and mustard-contaminated areas may appear completely normal, victims can unknowingly receive high dosages. Within 24 hours of exposure to mustard agent, victims experience intense itching and skin irritation, which gradually turns into large blisters filled with yellow fluid wherever the mustard agent contacted the skin. These are chemical burns and are very debilitating. Mustard gas vapour easily penetrates clothing fabrics such as wool or cotton, so it is not only the exposed skin of victims that gets burned. If the victim's eyes were exposed then they become sore, starting with conjunctivitis, after which the eyelids swell, resulting in temporary blindness. Miosis may also occur, which is probably the result from the cholinomimetic activity of mustard.144 At very high concentrations, if inhaled, mustard agent causes bleeding and blistering within the respiratory system, damaging mucous membranes and causing pulmonary edema. Depending on the level of contamination, mustard gas burns can vary between first and second degree burns, though they can also be every bit as severe, disfiguring and dangerous as third degree burns.145 Severe mustard gas burns (i.e. where more than 50% of the victim's skin has been burned) are often fatal, with death occurring after some days or even weeks have passed. Mild or moderate exposure to mustard agent is unlikely to kill, though victims require lengthy periods of medical treatment and convalescence before recovery is complete. The mutagenic and carcinogenic effects of mustard agent mean that victims who recover from mustard gas burns have an increased risk of developing cancer in later life.

144Vesicants. brooksidepress.org 145Effects of mustard gas, WW1|Gas Warfare Medical Aspects|World War II Resource Centre . Vlib.us (2004-08-23). Retrieved on 2011-05-29.

Skin damage can be reduced if povidone-iodine in a base of glycofurol is rapidly applied, but since mustard agent initially has no symptoms, exposure is usually not recognised until skin irritation begins, at which point it is too late for countermeasures. The vesicant property of mustard gas can be neutralised by oxidation or chlorination, using household bleach (sodium hypochlorite), or by nucleophilic attack using e.g. decontamination solution "DS2" (2% NaOH, 70% diethylenetriamine, 28% ethylene glycol monomethyl ether). After initial decontamination of the victim's wounds is complete, medical treatment is similar to that required by any conventional burn. The amount of pain and discomfort suffered by the victim is comparable as well. Mustard gas burns heal slowly, and, as with other types of burn, there is a risk of sepsis caused by pathogens such as Staphylococcus aureus and Pseudomonas aeruginosa. A British nurse treating soldiers with mustard gas burns during World War I commented: They cannot be bandaged or touched. We cover them with a tent of proppedup sheets. Gas burns must be agonizing because usually the other cases do not complain, even with the worst wounds, but gas cases are invariably beyond endurance and they cannot help crying out.

Formulations
In its history, various types and mixtures of sulfur mustard have been employed. These include: H Also known as HS ("Hun Stuff") or Levinstein mustard. This is named after the inventor of the quick but dirty Levinstein Process for manufacture, reacting dry ethylene with sulfur monochloride under controlled conditions. Undistilled sulfur mustard contains 2030% impurities, for which reason it does not store as well as HD. Also, as it decomposes, it increases in vapor pressure, making the munition it is contained in likely to split, especially along a seam, releasing the agent to the atmosphere HD Codenamed Pyro by the British, and Distilled Mustard by the US. Distilled sulfur mustard (bis(2-chloroethyl) sulfide); approximately 96% pure. The term "mustard gas" usually refers to this variety of sulfur mustard. A much-used path of synthesis was based upon the reaction of thiodiglycol with hydrochloric acid. HT Codenamed Runcol by the British, and Mustard T- mixture by the US. A mixture of 60% sulfur mustard (HD) and 40% T (bis[2-(2-chloroethylthio)ethyl] ether), a related vesicant with lower freezing point, lower volatility and similar vesicant characteristics.

HL A blend of distilled mustard (HD) and Lewisite (L), originally intended for use in winter conditions due to its lower freezing point compared to the pure substances. The Lewisite component of HL was used as a form of antifreeze.146 HQ A blend of distilled mustard (HD) and sesquimustard (Q) (Gates and Moore 1946).

Sulfur mustard agents (class)


The complete list of effective sulfur mustard agents commonly stockpiled is as follows:[citation needed]

146The Emergency Response Safety and Health Database: Mustard-Lewisite Mixture (HL) . National Institute for Occupational Safety and Health. Accessed March 19, 2009.

History
Development
Mustard gas was possibly developed as early as 1822 by Csar-Mansute Despretz (17981863).147 Despretz described the reaction of sulfur dichloride and ethylene but never made mention of any irritating properties of the reaction product, which makes the claim doubtful. In 1854, another French chemist, Alfred Riche (18291908), repeated this procedure but he did not describe any adverse physiological properties. In 1860, the British scientist Frederick Guthrie synthesized and characterized the mustard gas compound, and he also noted its irritating properties, especially in tasting. In 1860, chemist Albert Niemann, known as a pioneer in cocaine chemistry, repeated the reaction, and recorded blister-forming properties. In 1886, Viktor Meyer published a paper describing a synthesis that produced good yields. He combined 2-chloroethanol with aqueous potassium sulfide, and then treated the resulting thiodiglycol with phosphorus trichloride. The purity of this compound was much higher, and so were the adverse health effects on exposure much more severe. These symptoms presented themselves in his assistant, and in order to rule out the possibility that his assistant was suffering from a mental illness (psychosomatic symptoms), Meyer had this compound tested on laboratory rabbits, most of which died. In 1913, the English chemist Hans Thacher Clarke (known for the EschweilerClarke reaction) replaced the phosphorus trichloride with hydrochloric acid in Meyer's formulation while working with Emil Fischer in Berlin. Clarke was hospitalized for two months for burns after one of his flasks broke. According to Meyer, Fischer's report on this accident to the German Chemical Society sent the German Empire on the road to chemical weapons.148 The German Empire during World War I relied on the Meyer-Clarke method with the 2-chloroethanol chemical structure already available from the German chemical dye industry of that time.

147By Any Other Name: Origins of Mustard Gas. Itech.dickinson.edu (2008-04-25). Retrieved on 2011-05-29. 148Mustard gas can have the effect of turning a patient's skin different colors, including reds, oranges, pinks, and in unusual cases, blues.

Use
Mustard gas was first used effectively in World War I by the German army against British and Canadian soldiers near Ypres, Belgium, in 1917 and later also against the French Second Army. The name Yperite comes from its usage by the German army near the town of Ypres. The Allies did not use mustard gas until November 1917 at Cambrai, France, after the armies had captured a stockpile of German mustard-gas shells. It took the British more than a year to develop their own mustard gas weapon. (The only option available to the British was the DespretzNiemannGuthrie process). This was used first in September 1918 during the breaking of the Hindenburg Line. Mustard gas was dispersed as an aerosol in a mixture with other chemicals, giving it a yellow-brown color and a distinctive odor. Mustard gas has also been dispersed in such munitions as aerial bombs, land mines, mortar rounds, artillery shells, and rockets. Exposure to mustard gas was lethal in about one percent of cases. Its effectiveness was as an incapacitating agent. The early countermeasures against mustard gas were relatively ineffective, since a soldier wearing a gas mask was not protected against absorbing it through his skin and being blistered. Mustard gas is a persistent weapon that remains on the ground for days and weeks, and it continues to cause ill effects. If mustard gas contaminates a soldier's clothing and equipment, then the other soldiers that he comes into contact with are also poisoned. Towards the end of World War I, mustard gas was used in high concentrations as an area-denial weapon that forced troops to abandon heavily-contaminated areas. Since World War I, mustard gas has been used in several wars or other conflicts, usually against people who cannot retaliate in kind:149 United Kingdom against the Red Army in 1919 Spain and France against the Rifian resistance in Morocco during 192127 Italy in Libya during 1930 The Soviet Union in Xinjiang, Republic of China, during the Soviet Invasion of Xinjiang against the 36th Division (National Revolutionary Army) in 1934, and also in the Xinjiang War (1937) during 193637 Italy against Abyssinia (now Ethiopia) from 1935 to 1940 Nazi Germany against Poland and the Soviet Union in a few incidents during World War II Poland against Germany in 1939 during an isolated incident, using a British product The Japanese Empire against China during 193745 Egypt against North Yemen during 196367
149Blister Agent: Sulfur Mustard (H, HD, HS), CBWinfo.com

Iraq against Iran and the Kurds during 198388 Possibly Sudan against insurgents in the civil war, in 1995 and 1997 In 1943, during the Second World War, an American shipment of mustard gas exploded aboard a supply ship that was bombed during an air raid in the harbor of Bari, Italy. Eighty-three of the 628 hospitalized victims who had been exposed to the mustard gas died. The deaths and incident were partially classified for many years. From 1943 to 1944, mustard gas experiments were performed on Australian service volunteers in tropical Queensland, Australia, by British Army and American experimenters, resulting in some severe injuries. One test site, the Brook Islands National Park, was chosen to simulate Pacific islands held by the Imperial Japanese Army.150 After WWII stockpiled mustard gas was dumped by the British in the sea near Port Elizabeth, South Africa, resulting in burn cases among trawler crews. The use of poison gases, including mustard gas, during warfare is known as chemical warfare, and this kind of warfare was prohibited by the Geneva Protocol of 1925, and also by the later Chemical Weapons Convention of 1993. The latter agreement also prohibits the development, production, stockpiling, and sale of such weapons.

Development of the first chemotherapy drug


As early as 1919 it was known that mustard gas was a suppressor of hematopoiesis. In addition, autopsies performed on 75 soldiers who had died of mustard gas during World War I were done by researchers from the University of Pennsylvania who reported decreased counts of white blood cells. This led the American Office of Scientific Research and Development (OSRD) to finance the biology and chemistry departments at Yale University to conduct research on the use of chemical warfare during World War II. As a part of this effort, the group investigated nitrogen mustard as a therapy for Hodgkin's lymphoma and other types of lymphoma and leukemia, and this compound was tried out on its first human patient in December 1942. The results of this study were not published until 1946, when they were declassified. In a parallel track, after the air raid on Bari in December 1943, the doctors of the U.S. Army noted that white blood cell counts were reduced in their patients. Some years after World War II was over, the incident in Bari and the work of the Yale University group with nitrogen mustard converged, and this prompted a search for other similar chemical compounds. Due to its use in previous studies, the nitrogen mustard called "HN2" became the first cancer chemotherapy drug, mustine, to be used.

150Brook Island Trials of Mustard Gas during WW2. Home.st.net.au. Retrieved on 2011-05-29.

Disposal
Most of the sulfur mustard gas found in Nazi Germany after World War II was dumped into the Baltic Sea. Between 1966 and 2002, fishermen have found about 700 chemical weapons in the region of Bornholm, most of which contain sulfur mustard. One of the more frequently-dumped weapons was the "Sprhbchse 37" (SprB37, Spray Can 37, 1937 being the year of its fielding with the German Army). These weapons contain sulfur mustard mixed with a thickener, which gives it a tar-like viscosity. When the content of the SprB37 comes in contact with water, only the sulfur mustard in the outer layers of the lumps of viscous mustard hydrolyzes, leaving behind amber-colored residues that still contain most of the active sulfur mustard. On mechanically breaking these lumps, e.g., with the drag board of a fishing net or by the human hand, the enclosed sulfur mustard is still as active as it had been at the time the weapon was dumped. These lumps, when washed ashore, can be mistaken for amber, which can lead to severe health problems. Artillery shells containing sulfur mustard and other toxic ammunition from World War I (as well as conventional explosives) can still be found in France and Belgium. These were formerly disposed of by explosion undersea, but since the current environmental regulations prohibit this, the French government is building an automated factory to dispose of the accumulation of chemical shells. In 1972, the U.S. Congress banned the practice of disposing of chemical weapons into the ocean by the United States. 64 million pounds of nerve and mustard agents had already been dumped into the ocean off the United States by the U.S. Army. According to a report created in 1998 by William Brankowitz, a deputy project manager in the U.S. Army Chemical Materials Agency, the army created at least 26 chemical weapons dumping sites in the ocean offshore from at least 11 states on both the East Coast and the West Coast (in Operation CHASE, Operation Geranium, etc.). In addition, due to poor recordkeeping, about one-half of the sites have only their rough locations known.

A significant portion of the stockpile of mustard agent in the United States was stored at the Edgewood Area of Aberdeen Proving Ground in Maryland. Approximately 1,621 tons of mustard agent were stored in one-ton containers on the base under heavy guard. An incineration plant built on the proving ground neutralized the last of this stockpile in February 2005. This stockpile had priority because of the potential for quick reduction of risk to the community. The nearest schools were fitted with overpressurization machinery to protect the students and faculty in the event of a catastrophic explosion and fire at the site. These projects, as well as planning, equipment, and training assistance, were provided to the surrounding community as a part of the Chemical Stockpile Emergency Preparedness Program (CSEPP), a joint program of the Army and the Federal Emergency Management Agency (FEMA). Unexploded shells containing mustard agent and other chemical agents are still present in several test ranges in proximity to schools in the Edgewood area, but the smaller amounts of poison gas (four to 14 pounds) present considerably lower risks. These remnants are being detected and excavated systematically for disposal. The U.S. Army Chemical Materials Agency oversaw disposal of several other chemical weapons stockpiles located across the United States in compliance with international chemical weapons treaties. These include the complete incineration of the chemical weapons stockpiled in Alabama, Arkansas, Indiana, and Oregon. Earlier, this agency had also completed destruction of the chemical weapons stockpile located on Johnston Atoll located south of Hawaii in the Pacific Ocean.151 The largest mustard gas stockpile, of about 6,196 tons, was stored at the Deseret Chemical Depot in northern Utah. The incineration of this stockpile began in 2006. In May 2011, the last one-ton tank of mustard gas was incinerated at the Deseret Chemical Depot, and the last mustard gas artillery shells at Deseret were incinerated in January 2012. The storage and incineration of mustard gas and other poison gasses was carried out by the U.S. Army Chemical Materials Agency.152 Disposal projects at the two remaining American chemical weapons sites, will be carried out at their sites near Richmond, Kentucky, and Pueblo, Colorado, In 2002, an archaeologist at the Presidio Trust archaeology lab in San Francisco was exposed to mustard gas, which had been dug up at the Presidio of San Francisco, a former military base. In 2008, many empty mustard gas aerial bombs were found in an excavation at the Marrangaroo Army Base just west of Sydney, Australia.153 In 2009, a mining survey near Chinchilla, Queensland, uncovered 144 105-millimeter howitzer shells, some containing "Mustard H", that had been buried by the U.S. Army during World War II.

151Milestones in U.S. Chemical Weapons Storage and Destruction, fact sheet . US Chemical Materials Agency 152The U.S. Army's Chemical Materials Agency (CMA) . cma.army.mil. Retrieved on 2011-11-23. 153Chemical Warfare in Australia. Mustardgas.org. Retrieved on 2011-05-29.

In 2010, a clamming boat pulled up some old artillery shells of World War I from the Atlantic Ocean south of Long Island, New York. Multiple fishermen suffered from skin blistering and respiratory irritation severe enough to require their hospitalization. A large British stockpile of old mustard gas that had been made and stored at M. S. Factory, Valley near Rhydymwyn in Flintshire, Wales, since World War I was destroyed in 1958.

Detection in biological fluids


Urinary concentrations of the thiodiglycol hydrolysis products of sulfur mustard have been used to confirm a diagnosis of chemical poisoning in hospitalized victims. The presence in urine of 1,1'-sulfonylbismethylthioethane (SBMTE), a conjugation product with glutathione, is considered a more specific marker, since this metabolite is not found in specimens from unexposed persons. Intact sulfur mustard was detected in postmortem fluids and tissues of a man who died one week post-exposure.154

External links
Textbook of Military Medicine Intensive overview of mustard gas Includes many references to scientific literature Detailed information on physical effects and suggested treatments Iyriboz Y (2004). "A Recent Exposure to Mustard Gas in the United States: Clinical Findings of a Cohort (n = 247) 6 Years After Exposure". MedGenMed 6 (4): 4. PMC 1480580. PMID 15775831. Shows photographs taken in 1996 showing people with mustard gas burns. An overview of the sulfur and nitrogen mustard agents (Caution: contains graphic images) Questions and Answers for Mustard Gas UMDNJ-Rutgers University CounterACT Research Center of Excellence A research center studying sulfur mustard, includes searchable reference library with many early references on sulfur mustard. Treatment of Mustard Gas Burns published in the BMJ in 1946 Nightmare in Bari surgical treatment of Sulfur Mustard Burns

154R. Baselt, Disposition of Toxic Drugs and Chemicals in Man, 9th edition, Biomedical Publications, Seal Beach, CA, 2011, pp. 15931595.

UK Ministry of Defence Report on disposal of weapons at sea and incidents arising Rhydymwyn Valley History Society

Blood agent
Part of a series on Chemical agents Lethal agents Blood agents Cyanogen chloride (CK) Hydrogen cyanide (AC) Blister agents Ethyldichloroarsine (ED)

Methyldichloroarsine (MD)

Phenyldichloroarsine (PD)

Lewisite (L)

Sulfur mustard (HD, H, HT, HL, HQ)

Nitrogen mustard 1. HN1 2. HN2 3. HN3

Nerve agents

G-Agents Tabun (GA) Sarin (GB) Soman (GD) Cyclosarin (GF) GV V-Agents EA-3148 VE VG VM VR VX Novichok agents Nettle agents Phosgene oxime (CX) Pulmonary agents Chlorine Chloropicrin (PS)

Phosgene (CG) Diphosgene (DP) Incapacitating agents

Agent 15 (BZ) Dimethylheptylpyran (DMHP) 1. EA-3167 2. Kolokol-1 PAVA spray Sleeping gas Riot control agents Pepper spray (OC) 1. CS 2. CN (mace) 3. CR

List of chemical warfare agents A blood agent is a toxic chemical agent that affects the body by being absorbed into the blood. They are fast-acting, potentially lethal poisons that typically manifest at room temperature as volatile colorless gases with a faint odor. Blood agents are either cyanide- or arsenic-based.

Exposure
Blood agents work through inhalation or ingestion. As chemical weapons, blood agents are typically disseminated as aerosols and take effect through inhalation. Due to their volatility, they are more toxic in confined areas than in open areas. Cyanide compounds occur in small amounts in the natural environment and in cigarette smoke. They are also used in several industrial processes and as pesticides. Cyanides are released when synthetic fabrics or polyurethane burn, and may thus contribute to fire-related deaths.155 Arsine gas, formed when arsenic encounters an acid, is used as a pesticide and in the semiconductor industry; most exposures to it occur accidentally in the workplace.

Symptoms
The symptoms of blood agent poisoning depend on concentration and duration. Cyanide-based blood agents irritate the eyes and the respiratory tract, while arsine is nonirritating. Hydrogen cyanide has a faint, bitter, almond odor that only about half of all people can smell. Arsine has a very faint garlic odor detectable only at greater than fatal concentrations. Exposure to small amounts of cyanide has no effect. Higher concentrations cause dizziness, weakness and nausea, which cease with the exposure, but long-time exposure can cause mild symptoms followed by permanent brain damage and muscle paralysis. Moderate exposure causes stronger and longer-lasting symptoms, including headache, that can be followed by convulsions and coma. Stronger or longer exposure will also lead to convulsions and coma. Very strong exposure causes severe toxic effects within seconds, and rapid death. The blood of people killed by blood agents is bright red, because the agents inhibit the use of the oxygen in it by the body's cells. Cyanide poisoning can be detected by the presence of thiocyanate or cyanide in the blood, a smell of bitter almonds, or respiratory tract inflammations and congestions in the case of cyanogen chloride poisoning. There is no specific test for arsine poisoning, but it may leave a garlic smell on the victim's breath.

Effects
At sufficient concentrations, blood agents can quickly saturate the blood and cause death in a matter of minutes or seconds. They cause powerful gasping for breath, violent convulsions and a painful death that can take several minutes. The immediate cause of death is usually respiratory failure.

155

Blood agents work at the cellular level by preventing the exchange of oxygen and carbon dioxide between the blood and the body's cells. This causes the cells to suffocate from lack of oxygen. Cyanide-based agents do so by interrupting the electron transport chain in the inner membranes of mitochondria. Arsine damages the red blood cells which deliver oxygen throughout the body.

Detection and countermeasures


Chemical detection methods, in the form of kits or testing strips, exist for hydrogen cyanide. Ordinary clothing provides some protection, but proper protective clothing and masks are recommended. Mask filters containing only charcoal are ineffective, and effective filters are quickly saturated. Due to their high volatility, cyanide agents generally need no decontamination. In enclosed areas, fire extinguishers spraying sodium carbonate can decontaminate hydrogen cyanide, but the resulting metal salts remain poisonous on contact. Liquid hydrogen cyanide can be flushed with water.156 Cyanide poisoning can be treated with antidotes; see the corresponding article.

List of blood agents


The information in the following table, which lists blood agents of military significance,157 is taken from Ledgard. The values given are on a scale from 1 to 10. Agent Descript Melting /Effective Persiste ion boiling ness as nce, point blood open agent area 2 Persiste Field Storage Toxicity nce, stability stability as blood enclosed agent area 9 10 8 10

Hydroge Colorles -13 / 26 10 n s gas or C cyanide liquid, almond odor, burns with a bluish flame. Cyanoge Colorles -28 / -21 9 n s gas, C almond odor, burns
156Ledgard, 73. 157

with a pinkish flame having a blue border. Cyanoge Colorles -6 / 14 n s gas or C chloride liquid, pungent and biting odor, soluble in water and alcohol. Cyanoge Colorles 52 / 62 n s needle- C bromide shaped or cubic crystals, tending to volatize on standing , hence of limited usefulne ss as a weapon. Arsine Colorles -117 / s gas, -62 C garliclike odor, slightly soluble in water. 8 3 9 9 9 8

Vinyl arsine

Colorles 124 C 7 s liquid, (boiling) irritating and bitter

odor, slightly soluble in water, also acts as a blister agent. Phosgen Colorles -118 / 8 10 e s gas and slightly yellow liquid, moldy hay odor, slightly soluble in water and soluble in most solvents, also acts as a choking agent. 6 9 5 8 6

Sodium cyanide and potassium cyanide, colorless crystalline compounds similar in appearance to sugar, also act as blood agents. Carbon monoxide could technically be called a blood agent because it binds with oxygen-carrying hemoglobin in the blood (see carbon monoxide poisoning), but its high volatility makes it impractical as a chemical warfare agent.

Cyanogen chloride
Cyanogen chloride

Identifiers Abbreviations CAS number PubChem ChemSpider EC number UN number MeSH RTECS number Jmol-3D images CK 506-77-4 10477 10045 208-052-8 1589 cyanogen+chloride GT2275000 Image 1

Properties Molecular formula Molar mass Appearance Odor Density Melting point Boiling point Solubility in water Solubility Vapor pressure Thermochemistry Std enthalpy of formation fHo298 Standard molar entropy So298 Hazards MSDS Main hazards NFPA 704 inchem.org Highly toxic 137.95 kJ mol1 236.33 J K1 mol1 CNCl 61.470 g mol1 Colorless gas acrid 2.7683 mg mL1 (at 0 C, 101.325 kPa) 6.55 C, 267 K, 20 F 13 C, 286 K, 55 F soluble soluble in ethanol, ether 1.987 MPa (at 21.1 C)

Related compounds Related alkanenitriles

Hydrogen cyanide Thiocyanic acid Cyanogen iodide Cyanogen bromide Cyanogen fluoride Acetonitrile Aminoacetonitrile Glycolonitrile Cyanogen (verify) (what is: / ?) Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references Cyanogen chloride is an inorganic compound with the formula NCCl. This linear, triatomic pseudohalogen is an easily condensed colorless gas. More commonly encountered in the laboratory is the related compound cyanogen bromide, a room-temperature solid that is widely used in biochemical analysis and preparation.

Synthesis, basic properties, structure


Although the formula is written CNCl, cyanogen chloride is a molecule with the connectivity ClCN. Carbon and chlorine are linked by a single bond, and carbon and nitrogen by a triple bond. It is a linear molecule, as are the related cyanogen halides (NCF, NCBr, NCI). Cyanogen chloride is produced by the oxidation of sodium cyanide with chlorine. This reaction proceeds via the intermediate cyanogen ((CN)2). NaCN + Cl2 ClCN + NaCl The compound trimerizes in the presence of acid to the heterocycle called cyanuric chloride.

Cyanogen chloride is slowly hydrolyzed by water to release hydrogen cyanide ClCN + H2O HCN + HOCl

Applications in synthesis
Cyanogen chloride is a precursor to the sulfonyl cyanides and chlorosulfonyl isocyanate, a useful reagent in organic synthesis.

Safety
Also known as CK, cyanogen chloride is a highly toxic blood agent, and was once proposed for use in chemical warfare. It causes immediate injury upon contact with the eyes or respiratory organs. Symptoms of exposure may include drowsiness, rhinorrhea (runny nose), sore throat, coughing, confusion, nausea, vomiting, edema, loss of consciousness, convulsions, paralysis, and death. It is especially dangerous because it is capable of penetrating the filters in gas masks, according to U.S. analysts. CK is unstable due to polymerization, sometimes with explosive violence.

Cyanogen chloride is listed in schedule 3 of the Chemical Weapons Convention: all production must be reported to the OPCW.

External links
Murphy-Lavoie, H. (2011). "Cyanogen Chloride Poisoning". eMedicine. MedScape. "National Pollutant Inventory Cyanide compounds fact sheet". Australian Government. "NIOSH Pocket Guide to Chemical Hazards". Centers for Disease Control and Prevention.

Hydrogen cyanide
Hydrogen cyanide

Identifiers CAS number PubChem ChemSpider UNII EC number UN number KEGG MeSH ChEBI RTECS number 3DMet Jmol-3D images 74-90-8 768 748 2WTB3V159F 200-821-6 1051 C01326 Hydrogen+Cyanide CHEBI:18407 MW6825000 B00275 Image 1

Properties Molecular formula Molar mass Appearance Odor Density Melting point Boiling point Solubility in water Solubility in ethanol kH Acidity (pKa) Basicity (pKb) Refractive index (nD) Viscosity Structure Molecular shape Dipole moment Thermochemistry Std enthalpy of formation fHo298 Std enthalpy of combustion cHo298 Standard molar entropy So298 Specific heat capacity, C Hazards EU Index EU classification 006-006-00-X
F+ T+ N

CHN 27.03 g mol1 Very pale, blue, transparent liquid or colorless gas Oil of bitter almond 0.687 g mL1 -14--12 C, 259-261 K, 7-10 F 25-26 C, 298.5-299.5 K, 78-79 F Miscible Miscible 75 mol Pa1 kg1 9.21 4.79 1.2675 201 Pa s Linear 2.98 D 109.9 kJ mol1 -426.5 kJ mol1 113.01 J K1 mol1 71.00 kJ K1 mol1 (at 27 C)158

158NIST Chemistry WebBook

R-phrases S-phrases NFPA 704

R12, R26/27/28, R50/53 (S1/2), S16, S36/37, S38, S45, S53, S59, S61

Flash point Autoignition temperature Related compounds Related alkanenitriles

17.8 C 538 C

Hydrogen isocyanide Isocyanic acid Thiocyanic acid Cyanogen iodide Cyanogen bromide Cyanogen chloride Cyanogen fluoride Acetonitrile Aminoacetonitrile Glycolonitrile Cyanogen (verify) (what is: / ?) Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references Hydrogen cyanide (HCN), sometimes called prussic acid, is an inorganic compound with chemical formula HCN. It is a colorless, extremely poisonous liquid that boils slightly above room temperature, at 26 C (79 F). HCN is produced on an industrial scale and is a highly valuable precursor to many chemical compounds ranging from polymers to pharmaceuticals.

Structure and general properties


Hydrogen cyanide is a linear molecule, with a triple bond between carbon and nitrogen. A minor tautomer of HCN is HNC, hydrogen isocyanide. Hydrogen cyanide is weakly acidic with a pKa of 9.2. It partially ionizes in water solution to give the cyanide anion, CN. A solution of hydrogen cyanide in water is called hydrocyanic acid. The salts of the cyanide anion are known as cyanides. HCN has a faint, bitter, almond-like odor that some people are unable to detect owing to a genetic trait. The volatile compound has been used as inhalation rodenticide and human poison. Cyanide ions interfere with iron-containing respiratory enzymes.

History of discovery
Hydrogen cyanide was first isolated from a blue pigment (Prussian blue) which had been known from 1704 but whose structure was unknown. It is now known to be a coordination polymer with a complex structure and an empirical formula of hydrated ferric ferrocyanide. In 1752, the French chemist Pierre Macquer made the important step of showing that Prussian blue could be converted to iron oxide plus a volatile component and that these could be used to reconstitute it.159 The new component was what we now know as hydrogen cyanide. Following Macquer's lead, it was first prepared from Prussian blue by the Swedish chemist Carl Wilhelm Scheele in 1782,160 and was eventually given the German name Blausure (lit. "Blue acid") because of its acidic nature in water and its derivation from Prussian blue. In English it became known popularly as Prussic acid.

159Pierre-Joseph Macquer (presented: 1752 ; published: 1756) "xamen chymique de bleu de Prusse" (Chemical examination of Prussian blue), Mmoires de l'Acadmie royale des Sciences , pages 60-77. 160See:

Carl W. Scheele (1782) "Frsk, betrffande det frgande mnet uti Berlinerbl" (Experiment concerning the coloring substance in Berlin blue), Kungliga Svenska Vetenskapsakademiens handlingar (Royal Swedish Academy of Science's Proceedings), 3: 264-275 (in Swedish). Reprinted in Latin as: "De materia tingente caerulei berolinensis" in: Carl Wilhelm Scheele with Ernst Benjamin Gottlieb Hebenstreit (ed.) and Gottfried Heinrich Schfer (trans.), Opuscula Chemica et Physica (Leipzig ("Lipsiae"), (Germany): Johann Godfried Mller, 1789), vol. 2, pages 148-174.

In 1787 the French chemist Claude Louis Berthollet showed that Prussic acid did not contain oxygen,161 an important contribution to acid theory, which had thitherto postulated that acids must contain oxygen (hence the name of oxygen itself, which is derived from Greek elements that mean "acid-former" and are likewise calqued into German as Sauerstoff). In 1811 Joseph Louis Gay-Lussac prepared pure, liquified hydrogen cyanide.162 In 1815 Gay-Lussac deduced Prussic acid's chemical formula.163 The radical cyanide in hydrogen cyanide was given its name from cyan, not only an English word for a shade of blue but the Greek word for blue, again owing to its derivation from Prussian blue.

Production and synthesis


Hydrogen cyanide forms in at least limited amounts from many combinations of hydrogen, carbon, and ammonia. Hydrogen cyanide is currently produced in great quantities by several processes, as well as being a recovered waste product from the manufacture of acrylonitrile. In 2006 between 500 million and 1 billion pounds were produced in the US.164 The most important process is the Andrussow oxidation invented by Leonid Andrussow at IG Farben in which methane and ammonia react in the presence of oxygen at about 1200 C over a platinum catalyst: 2 CH4 + 2 NH3 + 3 O2 2 HCN + 6 H2O The energy needed for the reaction is provided by the partial oxidation of methane and ammonia. Of lesser importance is the Degussa process (BMA process) in which no oxygen is added and the energy must be transferred indirectly through the reactor wall: CH4 + NH3 HCN + 3H2 This reaction is akin to steam reforming, the reaction of methane and water to give carbon monoxide and hydrogen. In the Shawinigan Process, hydrocarbons, e.g. propane, are reacted with ammonia. In the laboratory, small amounts of HCN are produced by the addition of acids to cyanide salts of alkali metals:
161See:

Berthollet (presented: 1787 ; published: 1789)


"Mmoire sur l'acide prussique" (Memoir on prussic acid), Mmoires de l'Acadmie Royale des Sciences, pages 148-161.

Reprinted in: Berthollet (1789) "Extrait d'un mmoire sur l'acide prussique" (Extract of a memoir on prussic acid), Annales de chimie 1: 30-39.
162Gay-Lussac (1811) "Note sur l'acide prussique" (Note on prussic acid), Annales de chimie, 44: 128 - 133. 163Gay-Lussac (1815) "Recherche sur l'acide prussique" (Research on prussic acid) Annales de Chimie 95: 136-231. 164[3]. EPA. Retrieved on 2013-01-31.

H+ + NaCN HCN + Na+ This reaction is sometimes the basis of accidental poisonings because the acid converts a nonvolatile cyanide salt into the gaseous HCN.

Historical methods of production


The demand for cyanides for mining operations in the 1890s was met by George Thomas Beilby, who patented a method to produce hydrogen cyanide by passing ammonia over glowing coal in 1892. This method was used until Hamilton Castner in 1894 developed a synthesis starting from coal, ammonia, and sodium yielding sodium cyanide, which reacts with acid to form gaseous HCN.

Applications
HCN is the precursor to sodium cyanide and potassium cyanide, which are used mainly in gold and silver mining and for the electroplating of those metals. Via the intermediacy of cyanohydrins, a variety of useful organic compounds are prepared from HCN including the monomer methyl methacrylate, from acetone, the amino acid methionine, via the Strecker synthesis, and the chelating agents EDTA and NTA. Via the hydrocyanation process, HCN is added to butadiene to give adiponitrile, a precursor to Nylon 66.

Occurrence
HCN is obtainable from fruits that have a pit, such as cherries, apricots, apples, and bitter almonds, from which almond oil and flavoring are made. Many of these pits contain small amounts of cyanohydrins such as mandelonitrile and amygdalin, which slowly release hydrogen cyanide. One hundred grams of crushed apple seeds can yield about 70 mg of HCN. Some millipedes release hydrogen cyanide as a defense mechanism, as do certain insects, such as some burnet moths. Hydrogen cyanide is contained in the exhaust of vehicles, in tobacco and wood smoke, and in smoke from burning nitrogen-containing plastics. So-called "bitter" roots of the cassava plant may contain up to 1 gram of HCN per kilogram.

HCN and the origin of life


Hydrogen cyanide has been discussed as a precursor to amino acids and nucleic acids. For example, HCN is proposed to have played a part in the origin of life. Although the relationship of these chemical reactions to the origin of life theory remains speculative, studies in this area have led to discoveries of new pathways to organic compounds derived from the condensation of HCN.

HCN in space
HCN has been detected in the interstellar medium. Since then, extensive studies have probed formation and destruction pathways of HCN in various environments and examined its use as a tracer for a variety of astronomical species and processes. HCN can be observed from ground-based telescopes through a number of atmospheric windows. The J=10, J=32, J= 43, and J=109 pure rotational transitions have all been observed. HCN is formed in interstellar clouds through one of two major pathways: via a neutral-neutral reaction (CH2 + N HCN + H) and via dissociative recombination (HCNH+ + e HCN + H). The dissociative recombination pathway is dominant by 30%; however, the HCNH+ must be in its linear form. Dissociative recombination with its structural isomer, H2NC+, exclusively produces hydrogen isocyanide (HNC). HCN is destroyed in interstellar clouds through a number of mechanisms depending on the location in the cloud. In photon-dominated regions (PDRs), photodissociation dominates, producing CN (HCN + CN + H). At further depths, photodissociation by cosmic rays dominate, producing CN (HCN + cr CN + H). In the dark core, two competing mechanisms destroy it, forming HCN+ and HCNH+ (HCN + H+ HCN+ + H; HCN + HCO+ HCNH+ + CO). The reaction with HCO+ dominates by a factor of ~3.5. HCN has been used to analyze a variety of species and processes in the interstellar medium. It has been suggested as a tracer for dense molecular gas and as a tracer of stellar inflow in high-mass star-forming regions. Further, the HNC/HCN ratio has been shown to be an excellent method for distinguishing between PDRs and X-ray-dominated regions (XDRs).

As a poison and chemical weapon


A hydrogen cyanide concentration of 300 mg/m3 in air will kill a human within 1060 minutes.165 A hydrogen cyanide concentration of 3500 ppm (about 3200 mg/m3) will kill a human in about 1 minute. The toxicity is caused by the cyanide ion, which halts cellular respiration by inhibiting an enzyme in mitochondria called cytochrome c oxidase. Hydrogen cyanide has been absorbed into a carrier for use as a pesticide. Under IG Farben's brand name Zyklon B (German >Cyclone B, with the B standing for Blausure - "Prussic Acid"), it was used in the Nazi concentration camp murders during the Holocaust. The same product is currently made in the Czech Republic under the trademark "Uragan D2." Hydrogen cyanide was also the agent used in gas chambers employed in judicial execution in some U.S. states, where it was produced during the execution by the action of sulfuric acid on an egg-sized mass of potassium cyanide.

165Environmental and Health Effects. Cyanidecode.org. Retrieved on 2012-06-02.

Hydrogen cyanide is commonly listed amongst chemical warfare agents known as blood agents. As a substance listed under Schedule 3 of the Chemical Weapons Convention as a potential weapon which has large-scale industrial uses, manufacturing plants in signatory countries which produce more than 30 tonnes per year must be declared to, and can be inspected by, the Organisation for the Prohibition of Chemical Weapons. During the First World War, USA and Italy used hydrogen cyanide against the Central Powers in 1918. France had used it in combat already in 1916, but was ineffective due to physical conditions.166 Under the name prussic acid, HCN has been used as a killing agent in whaling harpoons.167 Hydrogen cyanide gas in air is explosive at concentrations over 5.6%. This is far above its toxicity level.

External links
Institut national de recherche et de scurit (1997). " Cyanure d'hydrogne et solutions aqueuses". Fiche toxicologique n 4, Paris:INRS, 5pp. (PDF file, in French) International Chemical Safety Card 0492 Hydrogen cyanide and cyanides (CICAD 61) National Pollutant Inventory: Cyanide compounds fact sheet NIOSH Pocket Guide to Chemical Hazards Department of health review

166Markus Schnedlitz (2008) Chemische Kampfstoffe: Geschichte, Eigenschaften, Wirkung. GRIN Verlag, ISBN 364023360-3, p. 13 167Poison Hand Darted Harpoons and Lances.

Non-Lethal and Riot Control


Riot control
Riot control refers to the measures used by police, military, or other security forces to control, disperse, and arrest civilians who are involved in a riot, demonstration, or protest. If a riot is spontaneous and irrational, actions which cause people to stop and think for a moment (e.g. loud noises or issuing instructions in a calm tone) can be enough to stop it. However, these methods usually fail when there is severe anger with a legitimate cause, or the riot was planned or organized. Law enforcement officers or soldiers have long used less lethal weapons such as batons and whips to disperse crowds and detain rioters. Since the 1980s, riot control officers have also used tear gas, pepper spray, rubber bullets, and electric tasers. In some cases, riot squads may also use Long Range Acoustic Devices, water cannons, armoured fighting vehicles, aerial surveillance, police dogs or mounted police on horses. Officers performing riot control typically wear protective equipment such as riot helmets, face visors, body armor (vests, neck protectors, knee pads, etc.), gas masks and riot shields. However, there are also cases where lethal weapons are used to violently suppress a protest or riot, as in the Boston Massacre, Haymarket Massacre, Banana Massacre, Hungarian Revolution of 1956, Kent State Massacre, Soweto Uprising, Mendiola Massacre, Bloody Sunday (1972) and Tiananmen Square Massacre.

Equipment
For protection, officers performing riot control will often wear protective helmets and carry riot shields. These are designed to protect the wearer from those dangers that come from direct melee and hurled objects such as bottles and bricks. To provide even greater protection, the protective equipment often provides ballistic protection. If tear gas or other riot control agents are to be used, gas masks may also be worn. One of many additional concerns is to prevent people in the crowd from snatching officers' side arms, which may be stolen or even used against the police. In a very heavy crowd, the officer may not be able to see who is responsible for snatching a weapon, and may not even notice that it has happened. For this reason, riot police may have holsters with positive locking mechanisms or other extra means of retention, if their agencies can afford such tools. However, this can be a trade-off that increases the amount of time needed to draw the sidearm in an emergency. Alternately, riot police may not carry sidearms at all.

The initial choice of tactics determines the type of offensive equipment used. The base choice is between lethal (e.g. 12 gauge shotgun) and less-than-lethal weaponry (e.g. tear gas, pepper spray, plastic bullets, tasers, batons, and other incapacitants). The decision is based on the perceived level of threat and the existing laws; in many countries it is illegal to use lethal force to control riots in all but the most extreme circumstances. Special riot hand weapons include the wooden or rubber baton; the African sjambok, a heavy leather or plastic whip, and the Indian lathi, a 6 to 8-foot (2.4 m) long cane with a blunt metal tip. Vehicle-mounted water cannons may serve to augment personal weapons. Some water cannons let police add dye to mark rioters or tear gas to help disperse the crowds. In major unrest, police in armoured vehicles may be sent in following an initial subduing with firepower. Occasionally, police dogs, fire hoses, or mounted police are deployed.

Riot control agent (RCA)


Riot control agents (sometimes called RCAs) are non-lethal lachrymatory agents used for riot control. Most commonly used riot control agents are pepper spray and various kinds of tear gas. These chemicals disperse a crowd that could be protesting or rioting, or to clear a building. They can rapidly produce sensory irritation or disabling physical effects which usually disappear within 15 minutes (for tear gas) and up to 2 hours (for pepper spray) following termination of exposure. They can also be used for chemical warfare defense training, although their use in warfare itself is a violation of Article I.5 of the Chemical Weapons Convention. Article II.9 of the CWC specifically authorizes their use for civilian law enforcement.168

Pepper spray
The active ingredient in pepper-spray is capsaicin, which is a chemical derived from the fruit of plants in the Capsicum genus, including chilies. A synthetic analogue of capsaicin, pelargonic acid vanillylamide (desmethyldihydrocapsaicin), is used in another version of pepper spray known as PAVA spray which is used in the United Kingdom. Another synthetic counterpart of pepper spray, pelargonic acid morpholide, was developed and is widely used in Russia. Its effectiveness compared to natural pepper spray is uncertain and it reportedly has caused some injuries. When undesirables threaten an area, such as a riot after a soccer game, riot police are called in to subdue them. In these situations, the police may use pepper spray, or water cannons to neutralize the threat.

1689. "Purposes Not Prohibited Under this Convention" means

Pepper spray typically comes in canisters, which are often small enough to be carried or concealed in a pocket or purse. Pepper spray can also be bought concealed in items such as rings. There are also pepper spray projectiles available, which can be fired from a paintball gun. Having been used for years against demonstrators, it is increasingly being used by police in routine interventions.

Tear gas
Tear gas is a non-specific term for any chemical that is used to temporarily incapacitate through irritation of eyes and/or respiratory system. It is used as a hand-held spray or can be fired in canisters that heat up spewing out an aerosol cloud at a steady rate.169170 Popular tear gases include the eye irritants ortho-chlorobenzylidenemalononitrile (CS gas), chloroacetophenone (CN gas), and dibenz (b,f)-1,4oxazepine (CR gas). Among a long list of substances, these three have become of greater importance than the others because of their effectiveness and low risks when used. Today, CS has largely replaced CN as the most widely used tear gas internationally. [citation needed]

Decontamination
At room temperature, tear gases are white, solid substances. They are stable when heated and have low vapor pressure. Consequently, they are usually dispersed as aerosols. All of them have low solubility in water but can be dissolved in several organic solvents. Hydrolysis of CN is very slow in a water solution, especially if alkali is added. CS is rapidly hydrolyzed in water solution (half-life at pH 7 is about 15 min. at room temperature) and extremely rapid when alkali is added (half-life at pH 9 is about 1 min.). CR is hydrolyzed only to a negligible extent in water solution. CN and CR are, thus, difficult to decompose under practical conditions, whereas CS can easily be inactivated by means of a water solution. Skin is suitably decontaminated by thorough washing with soap and water. CS is then decomposed, whereas CN and CR are only removed.

169http://www.eco-action.org/dod/no7/cs_gas.html 170http://www.google.co.uk/search?sourceid=navclient&aq=t&ie=UTF8&rlz=1T4GGLJ_enGB226GB226&q=cs+gas+effects

Decontamination of material after contamination with CS can be done with a 5 10 percent soda solution or 2 percent alkaline solution. If this type of decontamination cannot be accomplished (e.g., contaminated rooms and furniture), then the only other means is by intensive air exchangepreferably with hot air. Exposed streets and sidewalks will have toxic[citation needed] and irritating CS powder that will be stirred into the air by traffic and pedestrians long after the cloud has dissipated, and should be washed away with water. In contrast to human beings, domesticated animals generally have lower sensitivity to tear gases. Dogs and horses can therefore be used by police for riot control even when tear gas is used.[citation needed]

Dispensing large quantities


Backpack dispensers for riot control agents, when the intent is to use a larger quantity than possible with grenades, are one type of device used by organizations that might, for example, need to cover a prison yard 171 Dispensers are also made for attachment to helicopters; see CBU-19.172

Tactics
The front-line officers in a riot control are often fully armored and carry weapons such as batons, designed to be in direct contact with the crowd. These officers subdue rioters and subsequently allow the less heavily armoured, more mobile officers to make arrests where it is deemed necessary. In face of a greater threat, the riot police will be backed up with other officers equipped with riot guns to fire tear gas, rubber bullets, plastic bullets or "beanbag" rounds. As a less aggressive step, mounted police may first be sent into the crowd. The might and height offered by the horse are combined with its training, allowing an officer to more safely infiltrate a crowd. Usually, when front-facing a riot, officers slowly walk in a line parallel to the riot's front, extending to both its ends, as they noisily and simultaneously march and beat their shields with their batons, to cause fear and psychological effects on the crowd. The French CRS's tactics against a long demonstration march is to attack it at several points and chop it into segments, rather than to merely try to block it at its front end. Since the advent of artillery, straight roads have been of notable importance in city defense and control. Upon coming to power, Napoleon III built great avenues, referred to as anti-riot streets, into the troublesome quarters of Paris.173 The wide straight roads also allowed for cavalry charges to subdue rioters.

171Commercial Backpack Blower / Sprayer System , US Army CBDCOM,June 1998. 172Operation TAILWIND Review Extract of U.S Air Force Report, Air Force Historical Office, July 1998 173Kostof, Spiro: "The City Shaped," p. 230. Bulfinch Press, 1991

In the United Kingdom, usually when large demonstrations take place that are deemed unstable, the territorial police force responsible for the demonstration in that area will usually deploy Police Support Unit personnel who are trained in riot tactics, along with normal divisional officers. If the demonstration turns violent, police will seal roads and other exits to contain protesters in a single area (known as kettling) to prevent widespread damage and wait until the protesters tire. These tactics were seen during the 2009 G-20 London summit protests and the 2010 student protests in London. Tear gas and other more offensive tactics are used as a last resort. Throughout police will be videoing or photographing protesters for future arrests, "snatch squad" tactics might also be used.

Research
Research into weapons that are more effective for riot control continues. Netguns are non-lethal weapons designed to fire a net which entangles the target. Netguns have a long history of being used to capture wildlife, without injury, for research purposes. A netgun is currently in development for non-lethal riot control. Pepper-spray projectile launchers are projectile weapons that launch a fragile ball which breaks upon impact and releases an irritant powder called PAVA (capsaicin II) pepper. The launchers are often slightly modified .68 caliber paintball guns. Stink bombs are devices designed to create an extremely unpleasant smell for riot control and area denial purposes. Stink bombs are believed to be less dangerous than other riot control chemicals, since they are effective at low concentrations. Sticky foam weapons are being tested, which cover and immobilize rioters with a gooey foam.174 Low frequency sound cannons are weapons of various types that use sound to injure or incapacitate subjects using a focused beam of sound or infrasound. Active denial systems (ADS) are a non-lethal, directed-energy weapon developed by the U.S. military. The ADS directs electromagnetic radiation, specifically, high-frequency microwave radiation, at a frequency of 95 GHz, which causes the water in the upper epidermis to boil, stimulating a "burning" sensation in the nerve endings and generating intense pain. Dazzler lasers are directed-energy weapons that use intense light to cause temporary blindness or disorientation of rioters.

CS gas
CS gas

174How It Works Magazine - Experimental Riot Control: Riot Foam , How It Works, August 2011

Identifiers CAS number ChemSpider Jmol-3D images 2698-41-1 16644 Image 1

Properties Molecular formula Molar mass Appearance Density Melting point Boiling point Vapor pressure C10H5Cl N2175 188.6 g/mol176 White crystalline powder Colourless gas when burned 1.04 g/cm3 93C, (366.15 K), (199.4 F) 310 C, (583.15 K), (590 F) (mm Hg) 3.4 105 at 20 C

175Williams, Kenneth E. " Detailed Facts About Tear Agent O-Chlorobenzylidene Malononitrile (CS)." U.S. Army Center for Health Promotion and Preventive Medicine. Retrieved on September 23, 2007. 176Heinrich, U. " Possible lethal effects of CS tear gas on Branch Davidians during the FBI raid on the Mount Carmel compound near Waco, Texas." www.veritagiustizia.it.] September 2000. Retrieved on September 23, 2007

Hazards MSDS NFPA 704 External MSDS

Related compounds Related compounds Supplementary data page Structure and properties Thermodynamic data Spectral data (verify) (what is: / ?) Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references The compound 2-chlorobenzalmalononitrile (also called o-chlorobenzylidene malononitrile) (chemical formula: C10H5ClN2), a cyanocarbon, is the defining component of a "tear gas" commonly referred to as CS gas, which is used as a riot control agent. "CS gas" is actually an aerosol of a volatile solvent (a substance that dissolves other active substances and that easily evaporates with it) and 2-chlorobenzalmalononitrile, which is a solid compound at room temperature. CS gas is generally accepted as being non-lethal. It was discovered by two Americans, Ben Corson and Roger Stoughton, at Middlebury College in 1928, and the chemical's name is derived from the first letters of the scientists' surnames.177 CS was developed and tested secretly at Porton Down in Wiltshire, England, in the 1950s and 1960s. CS was used first on animals, then subsequently on British Army servicemen volunteers. Notably, CS has a limited effect on animals due to "under-developed tear-ducts and protection by fur".178 n, r, etc. Phase behaviour Solid, liquid, gas UV, IR, NMR, MS SDBS

177" CS, chemical compound." columbia.thefreedictionary.com. Retrieved on September 23, 2007 178" Orthochlorobenzylidenemalononitrile ClC6H4CHCCN(CN)2." Zarc International. Retrieved on September 23, 2007

Production
CS is synthesized by the reaction of 2-chlorobenzaldehyde and malononitrile via the Knoevenagel condensation:

1. ClC6H4CHO + H2C(CN)2 ClC6H4CHC(CN)2 + H2O The reaction is catalysed with weak base like piperidine or pyridine. The production method has not changed since the substance was discovered by Corson and Stoughton. Other bases, solvent free methods and microwave promotion have been suggested to improve the production of the substance. The physiological properties had been discovered already by the chemists first synthesising the compound in 1928: "Physiological Properties. Certain of these dinitriles have the effect of sneeze and tear gases. They are harmless when wet but to handle the dry powder is disastrous."

Use as an aerosol
As 2-chlorobenzalmalononitrile is a solid at room temperature, not a gas, a variety of techniques have been used to make this solid usable as an aerosol: Melted and sprayed in the molten form. Dissolved in organic solvent. CS2 dry powder (CS2 is a siliconized, micro-pulverized form of CS). CS from thermal grenades by generation of hot gases. In the Waco Siege, CS was dissolved in the organic solvent dichloromethane (also known as methylene chloride). The solution was dispersed as an aerosol via explosive force and when the highly volatile dichloromethane evaporated, CS crystals precipitated and formed a fine dispersion in the air.

Effects
Many types of tear gas and other riot control agents have been produced with effects ranging from mild tearing of the eyes to immediate vomiting and prostration. CN and CS are the most widely used and known, but around 15 different types of tear gas have been developed worldwide e.g., adamsite or bromoacetone, CNB, and CNC. CS has become the most popular due to its strong effect and lack of toxicity in comparison with other similar chemical agents. The effect of CS on a person will depend on whether it is packaged as a solution or used as an aerosol. The size of solution droplets and the size of the CS particulates after evaporation are factors determining its effect on the human body.179 The chemical reacts with moisture on the skin and in the eyes, causing a burning sensation and the immediate forceful and uncontrollable shutting of the eyes. Effects usually include tears streaming from the eyes, profuse coughing, exceptional nasal discharge that is full of mucus, burning in the eyes, eyelids, nose and throat areas, disorientation, dizziness and restricted breathing. It will also burn the skin where sweaty and or sunburned. In highly concentrated doses it can also induce severe coughing and vomiting. Almost all of the immediate effects wear off within an hour (such as exceptional nasal discharge and profuse coughing), although the feeling of burning and highly irritated skin may persist for hours. Affected clothing will need to be washed several times or thrown away.

Secondary effects
Persons or objects contaminated with CS gas can cause secondary exposure to others, including healthcare professionals and police. In addition, repeated exposure may cause sensitisation.180

Toxicity
Although described as a non-lethal weapon for crowd control, many studies have raised doubts about this classification. As well as creating severe pulmonary damage, CS can also significantly damage the heart and liver.

179" Safer Restraint: A report of the conference held in April 2002 at Church House, Westminster." Police Complaints Authority. Retrieved on September 23, 2007 180Management of the effects of exposure to tear gas

On September 28, 2000, Prof. Dr. Uwe Heinrich released a study commissioned by John C. Danforth, of the United States Office of Special Counsel, to investigate the use of CS by the FBI at the Branch Davidians' Mount Carmel compound. He concluded that the lethality of CS used would have been determined mainly by two factors: whether gas masks were used and whether the occupants were trapped in a room. He suggests that if no gas masks were used and the occupants were trapped, then, "...there is a distinct possibility that this kind of CS exposure can significantly contribute to or even cause lethal effects." Many reports have associated CS exposure with miscarriages. This is consistent with its reported clastogenic effect (abnormal chromosome change) on mammalian cells. When CS is metabolized, cyanide can be detected in human tissue. According to the United States Army Center for Health Promotion and Preventive Medicine, CS emits "very toxic fumes" when heated to decomposition, and at specified concentrations CS gas is an immediate danger to life and health. They also state that those exposed to CS gas should seek medical attention immediately. In Israel, CS gas was reported to be the cause of death of Jawaher Abu Rahmah on December 31, 2010, although the Israel Defense Forces have questioned the veracity of the report. In Egypt, CS gas was reported to be the cause of death of several protesters in Mohamed Mahmoud Street near Tahrir square during the November 2011 protests. The solvent in which CS is dissolved, methyl isobutyl ketone (MIBK), is classified as harmful by inhalation; irritating to the eyes and respiratory system; and repeated exposure may cause skin dryness or cracking.

Decontamination
CS contamination can be removed by washing with an alkaline solution of water and 5% sodium bisulfite.

Use
CS is used in spray form by many police forces as a temporary incapacitant and to subdue attackers or persons who are violently aggressive. Officers that are trained in the use and application of CS spray are routinely exposed to it as part of their training. Recently, blank pistol cartridges carrying CS in powder form have been released to public. These, when fired in relatively close ranges, fully expose the target to the effects of CS, and are employed as a potent defensive weapon in regions where blank firing pistols are legally permitted for such use.

Although predominantly used by police it has also been used in criminal attacks in various countries.181182183184 Use of CS in war is prohibited under the terms of the 1997 Chemical Weapons Convention, signed by most nations in 1993 with all but five other nations signing between the years of 1994 through 1997. The reasoning behind the prohibition is pragmatic: use of CS by one combatant could easily trigger retaliation with much more toxic chemical weapons such as nerve agents. Only five nations have not signed the Chemical Weapons Convention and are therefore unhindered by restrictions on the use of CS gas: Angola, Egypt, North Korea, Somalia, and Syria.185 Domestic police use of CS is legal in many countries, however, as the Chemical Weapons Convention prohibits only military use.

Bahrain
CS gas has been used extensively by Bahrain's police since the start of the Bahraini uprising.(p260) The Bahrain Independent Commission of Inquiry concluded that Bahrain's police used a disproportionate amount of CS gas when dispersing protests, and that in a number of situations, police fired CS gas into private homes in an "unnecessary and indiscriminate" manner.(p277) In one particular incident witnessed by Commission investigators, police fired "at least four tear gas canisters (each containing six projectiles) ... from a short range into the kitchen and living room of a home."(p261) According to opposition activists and families of the deceased, ten individuals have died as a result of CS gas between 25 March 2011 and 17 December 2011. One allegedly died from the impact of the CS gas canister, and the remainder are said to have died from the effects of inhaling the gas. The Bahrain Independent Commission of Inquiry received information that a further three deaths may have been attributable to the use of CS gas.(pp23940,253) Of these three, one allegedly died from the impact of the canister, and two from the effects of inhaling the gas.

Egypt
CS has been widely used by Egyptian Police/Military Forces from January 2011 onwards.
181Kelso, Paul. " CS gas attack by former pupil injures 68 children." The Guardian. October 1, 1999. Retrieved on September 23, 2007 182Condon, Deborah. " Gas attack at Dublin hospital." www.irishhealth.com. May 14, 2004. Retrieved on September 23, 2007 183" Shopkeeper attacked with CS gas." BBC News. December 1, 2005. Retrieved on September 23, 2007 184" Car thieves spray gas at motorist." BBC News. January 4, 2006. Retrieved on September 23, 2007 185United Nations Treaty Collection. Convention on the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and on their Destruction . Retrieved 19 January 2009.

Canada
Quebec
Since 2008, the SPVM police force in Montreal has increased its use of CS Gas for crowd control, although Police policy is to only use it as a "last resort". On Montreals riot squad, each officer is equipped with an MK-9 aerosol projector, which sprays the irritant at a distance of up to six feet. A number of incidents where protesters have been seriously injured by having CS gas fired at them from point-blank range has raised concerns about the methodology and training of Officers in the Montreal Riot Squad, particularly in relation to "Use of Force". Youtube Video of March 8 2012 incident

Cyprus
CS was first tested in the field by the British army in Cyprus in 1958. At this time it was known by the code name T792.186

Iraq
Iraq successfully developed CS during the 1970s and during the 1980s produced tons of the substance firstly at Salman Pak and later at al-Muthanna.187 Blackwater Worldwide, acting as an agent of the United States, deployed CS in the Iraq War from a helicopter hovering over a checkpoint in the Green Zone in Bagdhad.

Israel
Israel Police forces spray CS gas at riot control situations. It is widely used at demonstrations within the Palestinian Territories and at the Israeli West Bank barrier.

Philippines
CS tear gas was used in suppression of the mutiny in Makati that was led by Sen. Antonio Trillanes. The tear gas was fired in the building and all the people in the building including reporters were affected. [citation needed]

186" Final Report of the Expert Panel to Review SAS Veterans Health Concerns (Appendix D)." Retrieved on September 23, 2007 187" WMD Profiles: Chemical." Iraq Watch. Retrieved on September 23, 2007

Sri Lanka
The LTTE, also known as Tamil Tigers of Sri Lanka, an insurgent group in Sri Lanka used CS gas against government forces that were on an offensive to flush and defeat these insurgents during September 2008. Its use hindered the army's progress but ultimately proved ineffective in preventing the army from overrunning LTTE positions. This is one of the first few cases of insurgents using CS gas as an insurgent weapon.

United Kingdom
Northern Ireland
CS gas was used extensively in the Bogside area of Derry, Northern Ireland during the "Battle of the Bogside", a two-day riot in August, 1969. A total of 1,091 canisters containing 12.5g of CS each, and 14 canisters containing 50g of CS each, were released in the densely populated residential area.188 On 30 August the Himsworth Inquiry was set up to investigate the medical effects of its use in Derry. Its conclusions, viewed in the political context of the time, still pointed towards the necessity of further testing of CS gas before being used as a riot control agent. During the rioting in Belfast, the following year, known as the Falls Curfew, the Army fired up to 1,600 canisters into the densely populated Falls Road area. It was also used in Lenadoon on 9 July 1972 on the breakdown of the IRA ceasefire. Not long after, the British Army and RUC ceased using CS in Northern Ireland. Up to this point, it had been used in crowd control scenarios in Derry and Belfast.

Great Britain
CS gas
CS gas has never been routinely deployed on the British mainland. It has seen usage in a number of exceptionally rare cases. The first use of CS gas on the UK mainland that was not part of military training was carried out in 1944 during a hostage siege at a north London address. Soldiers were asked to throw CS grenades through the skylight in hope of bringing the incident to a speedy conclusion, however, the hostage-taker had brought his civilian-issue gas mask with him, negating the effect.[citation needed] The siege of Trough Gate 1973 in Oldham was the second non-military use of CS gas on the UK mainland. During a four-hour standoff, Frank Alan Stockton shot at police but was flushed from his home with CS gas and police dogs.
188(extracts available online)

In 1981, CS gas was used to quell rioting in the Toxteth area of Liverpool.189 Following the 2011 England riots, there was consideration given to making CS gas, water cannon and other riot control measures available to police for use in the event of serious disorder. The British Armed Forces use CS gas annually to test their CBRN equipment. During initial training they introduce recruits to CS gas by introducing them into a small enclosed space known as a Respirator Test Facility (RTF) and igniting chemical tablets to induce CS production. After recruits have carried out their CBRN drills, they must remove their respirators so that they are exposed to the CS for up to 20 seconds to experience its effects and become confident their masks work.

CS spray
CS incapacitant spray has been used routinely by the British police since its introduction in 1996. It is issued as an item of equipment to police officers for protection and to assist in dealing with violent incidents. A six-month trial by sixteen police forces in England began on the 1 March 1996. On 16 March 1996, a Gambian asylum seeker, Ibrahima Sey, was taken to Ilford Police Station in east London. Whilst incapacitating Sey, who was suffering from excited delirium, police sprayed him with CS spray and held him on the ground for approximately 15 minutes, and he subsequently died.190 In 1999, the mental health charity MIND called for a suspension in the use of CS spray on mentally ill people until it was proved to be safe.191 The CS spray used by police forces is in the form of a hand-held aerosol canister containing a 5% solution of CS dissolved in methyl isobutyl ketone and propelled by pressurized nitrogen. The CS spray used by UK police is generally more concentrated than that used by American police forces that use CS spray, depending on the particular city/state. The liquid stream is directed where the user points the canister, being accurate up to 4 metres. For an officer to be authorised to carry CS spray as part of their personal protection equipment, they have to have completed a training course in use of the spray, which includes being sprayed with a 3% solution of CS. They are also trained in helping the incapacitated person recover once successfully restrained. Under UK firearm law, CS and other incapacitant sprays are classed as prohibited weapons, making it unlawful for a member of the public to possess such an item. Some forces have opted to replace CS spray in favour of Captor or PAVA spray, with 60% of forces now estimated to be using PAVA.
189" On This Day: 20 May 1965: British police to be issued with tear gas." BBC News. Retrieved on September 23, 2007 190" Report on the death of Ibrahima Sey." Inquest. 1997 191" Experts fear unknown CS spray risks." BBC News. September 24, 1999. Retrieved on September 23, 2007

In February 2006, Dan Ford, from Wareham in Dorset, received permanent scarring to his face after being sprayed with CS during the course of an arrest by police. Ford was subsequently advised by doctors to stay out of sunlight for at least 12 months. After the incident, his cousin, Donna Lewis, was quoted as saying, "To look at him, it was like looking at a melting man, with liquid oozing from his face."192 It has not been confirmed that Ford's injury was a reaction to having been exposed to the CS spray, or whether an unrelated chemical exposure caused the injury. To give an indication as to the frequency of use of CS sprays by police, officers in the town of Reading, Berkshire deployed personal incapacitant spray on 486 occasions over a two-and-a-half year period from April 2009. CS spray was used in the UK more than 10,000 times in the period between its introduction in 1996 and September 1998.

United States
CS is used by many police forces within the United States. It was most famously used as one of a number of techniques by Federal Bureau of Investigation law enforcement officials in the 1993 Waco Siege.193 Riot police in Pittsburgh, Pennsylvania in September, 2009 used CS gas and riot control techniques to disperse assemblies in the vicinity of the 2009 G-20 Pittsburgh summit. In Berkeley, California during the Bloody Thursday events in People's Park on Wednesday, May 21, 1969, a midday memorial was held for student James Rector, a non-protester shot to death by police, at Sproul Plaza on the University campus. In his honor, several thousand people peacefully assembled to listen to speakers remembering his life. Without warning, National Guard troops surrounded Sproul Plaza, donned their gas masks, and pointed their bayonets inward, while helicopters dropped CS gas directly on the trapped crowd. No escape was possible, and the gas caused acute respiratory distress, disorientation, temporary blindness and vomiting. Many people, including children and the elderly, were injured during the ensuing panic. The gas was so intense that breezes carried it into Cowell Memorial Hospital, endangering patients, interrupting operations and incapacitating nurses. Students at nearby Jefferson and Franklin elementary schools were also affected.194195

192" CS spray man 'scarred for life'." BBC News. February 2, 2006. Retrieved on September 23, 2007 193" A Primer on CS Gas." Public Broadcasting Service. 1995. Retrieved on September 23, 2007 194Nation: Occupied Berkeley. TIME (1969-05-30). Retrieved on 2011-02-02. 195The Sixties and Seventies from Berkeley to Woodstock. Fsmitha.com. Retrieved on 2011-0202.

Members of the United States armed forces are exposed to CS during initial training, and during training refresher courses or equipment maintenance exercises, using CS tablets that are melted on a hotplate. This is to demonstrate the importance of properly wearing a gas or protective mask, as the agent's presence quickly reveals an improper fit or seal of the mask's rubber gaskets against the face. Following exposure while wearing a mask, recruits are ordered to remove the masks and endure exposure in the room for one minute. These exercises also encourage confidence in the ability of the equipment to protect the wearer from such chemical attacks. Such an event is a requirement for graduation from United States Army Basic Training, Air Force Basic Military Training, Navy Basic Training, and Marine Corps recruit training.196 CS gas in the form of grenades is also used extensively in the United States Marine Corps in some service schools. CS gas is used during the final field exercise of the Scout Sniper Basic Course to simulate being compromised. In addition, it is used during the 25 km (16 mi) escape-and-evasion exercise ("Trail of Tears"), the last event before graduation from the course. It is also used during several events in the Marine Corps Basic Reconnaissance Course (BRC) including some rucksack runs and escape-and-evasion exercises. While students going through the course are given the opportunity to bring and wear a gas mask for the event, usually none are worn because once donned, gas masks could not be removed until the end of the exercise. This could last anywhere from 312 hours and would make running 25 km while wearing 125 lb (57 kg) of gear virtually impossible.

Vietnam
It has been reported that thousands of tons of CS gas were used by the U.S. forces in Vietnam to bring Viet Cong into the open.[citation needed] It was also used by the North Vietnamese forces in some battles like Hue in 1968 or during the Easter Offensive in 1972.197Wikipedia:Verifiability

Elsewhere
CS gas has been and is still routinely used by Greek riot police (MAT) in order to quell student and labor protests, as well as riots by hooligans. In some cases gas had expired for more than thirty years. The legality and safety of the use of CS by policemen has been challenged both by people within Greece and the European Union.[citation needed] CS was used to quell a protest in Lusaka, Zambia in July 1997 and the 1999 WTO riots in Seattle. Amnesty International reported that it had been manufactured by the UK company Pains-Wessex. Subsequently, Amnesty called for an export ban when the receiving regime is either not fully trained in the use of CS, or had shown usage "contrary to the manufacturers instructions".198
196TRADOC Regulation 350-6 TRADOC 2007. Retrieved on October 13, 2008 197Bryce, Robert. " Lethal Weapon: FBI's Use of Tear Gas Questioned at Davidian Trial." The Austin Chronicle. July 7, 2000. Retrieved on September 23, 2007 198" Stopping the Torture Trade: 3 Chemical Control."Amnesty International. Retrieved on

In September 2000, the Guardian newspaper revealed how a UK company, HPP, used legal loopholes to export CS to a private security company in Rwanda, in breach of United Nations sanctions.199 The Guardian also reported that CS was used by the Hutu militia in Rwanda to flush Tutsis out of buildings before hacking them to death. CS has been used by the government in South Africa; by Israel against Palestinians and Israelis; by the South Korean government in Seoul, and during the Balkan conflicts by Serbia. In Malta it was used by Police between 1981 and 1987 to the detriment of Nationalist Party Supporters. CS tear gas was used at the G8 protests in Genoa, Italy200 and Quebec City, Canada201 during the FTAA anti-globalization demonstrations during the Quebec City Summit of the Americas. The Malaysia Federal Reserve Unit has also been known to use CS tear gas against its citizens who rallied for clean and fair elections under what were called Bersih rallies in 2011202 and 2012.203 The Canadian, Norwegian and Australian Armies train their soldiers with CS gas in a manner similar to that of the USA, as it is a basic part of CBRN (Chemical, Biological, Radiological, Nuclear) training. Gas is released by burning tablets, usually in a building reserved for this purpose (a "gas hut"). In the training, the person enters the building unprotected, and must fit and clear the gas mask before leaving. Other drills such as drinking and under-mask decontamination are also practiced. Some Norwegian units are exposed to CS-gas while engaged in physical activity such as push-ups.

External links
Salem H, Gutting B, Kluchinsky T, Boardman C, Tuorinsky S, Hout J (2008). Medical Aspects of Chemical Warfare, Chapter 13 Riot Control Agents, US Army Medical Institute, Borden Institute, pp. 441-484 (2008). Carron P-N, Yersin B (2009). "Management of the effects of exposure to tear gas". BMJ 338 (7710): 15541558. doi: 10.1136/bmj.b2283.

September 23, 2007 199Burke, Jason; Johnson-Thomas, Brian. " British firms trade in torture." The Guardian. September 10, 2000. Retrieved on September 23, 2007 200Tartarini, Laura. " Genova Update." italy.indymedia.org. April 13, 2003. Retrieved on September 23, 2007 201Di Matteo, Enzo. " Foggy Over Tear Gas Safety." NOW Online Edition. May 17723, 2001. Retrieved on September 23, 2007 202" Malaysia cracks down on protesters." Al Jazeera. July 10, 2011. Retrieved on April 30, 2012 203Shukry, Anisah " Probe violence against press, media groups urge Najib." The Malaysian Insider. April 29, 2012. Retrieved on April 30, 2012

Hout J, Hook G, LaPuma P, White D (2010). "Identification of compounds formed during low temperature thermal dispersion of encapsulated ochlorobenzylidene malononitrile (CS riot control agent)" Journal of Occupational and Environmental Hygiene, June 2010 Hout, Joseph; Kluchinsky, Timothy; LaPuma, Peter; White, Duvel (2011). "Evaluation of CS (o-Chlorobenzylidene Malononitrile) Concentrations During U.S. Army Mask Confidence Training", Journal of Environmental Health, October 2011 Gas Chromatography NIST U.S. Army Center for Health Promotion and Preventive Medicine General Facts About Tear Agent O-Chlorobenzylidene Malononitrile (CS) {pdf} CDC - NIOSH Pocket Guide to Chemical Hazards - o-Chlorobenzylidene malononitrile Patten report recommendations 69 and 70 relating to public order equipment A Paper prepared by the Steering Group led by the Northern Ireland Office April 2001 Committees on toxicity, mutagenicity and carcinogenicity of chemicals in food, consumer products and the environment statement on 2-chlorobenzylidene malononitrile (CS) and CS spray, September 1999. (pdf) Journal of Non-lethal Combatives, January 2003 Noxious Tear-Gas Bomb Mightier in Peace than in War. "Crowd Control Technologies: An Assessment Of Crowd Control Technology Options For The European Union" The Omega Foundation (pdf) Health and safety in policing University of Nottingham paper on CS use in the UK. Information and effects of CS and CN gas BBC 'wiki' site entry on CS gas eMedicine Information on irritants: Cs, Cn, Cnc, Ca, Cr, Cnb, PS

Pepper spray
Part of a series on Chemical agents Lethal agents Blood agents Cyanogen chloride (CK)

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