IPOL 8559 Science and Technology NPTS Chemistry Segment Instructor: Mark Bishop “If…in the future wars we are to avoid gross mismanagement in high places and panic…among the masses, it is essential that everyone should learn elementary science, and that politicians and soldiers should not be proud of their ignorance of it...” J. B. S. Haldane It’s All About Communication. • Goal: To get you to the place where you can – Follow (and contribute to) discussions of chemistry-related issues, such as those related to explosives and chemical weapons. – More easily read papers and books that include descriptions of these topics. • For example, by the end of the chemistry segment, you will be better equipped to understand the information found in articles you read this week on the possible use of chemical weapons in Syria. thecable.foreignpolicy.com 1/15/13 • Exclusive: Secret State Department cable: Chemical weapons used in Syria Posted by Josh Rogin • United States diplomats in Turkey conducted a previously undisclosed, intensive investigation into claims that Syrian President Bashar al-Assad used chemical weapons, and made what an Obama administration official who reviewed the cable called a "compelling case" that Assad's military forces had used a deadly form of poison gas. • The cable, signed by the U.S. consul general in Istanbul, Scott Frederic Kilner, and sent to State Department headquarters in Washington last week, outlined the results of the consulate's investigation into reports from inside Syria that chemical weapons had been used in the city of Homs on Dec. 23. http://thecable.foreignpolicy.com/posts/2013/01/15/secret_state_department_cable_ chemical_weapons_used_in_syria thecable.foreignpolicy.com 1/15/13 • Many believe that Assad is testing U.S. red lines. • Experts say the symptoms match the effects of Agent 15, known also by its NATO code BZ, which is a CX-level incapacitating agent that is controlled under schedule 2 of the Chemical Weapons Convention, to which Syria is not a party. • "The symptoms of an incapacitating agent are temporary. If someone is exposed to BZ, they are likely to be confused, perhaps to hallucinate," said Amy Smithson, a senior fellow with the James Martin Center for Nonproliferation Studies. "While it is not good news that a chemical agent of any kind may have been used in the Syrian conflict, this Agent 15 is certainly on the less harmful end of the spectrum of chemical warfare agents believed to be in the Syrian arsenal." http://thecable.foreignpolicy.com/posts/2013/01/15/secret_state_department_cable_ chemical_weapons_used_in_syria thecable.foreignpolicy.com 1/15/13 • The lightly affected people exhibited gastrointestinal symptoms, nausea, vomiting, and abdominal pain. • "The main symptom of the respiratory ailments was bronchial secretions. This particular symptom was the cause of the death of all of the people. All of them died choking on their own secretions." • "They all had miosis -- pinpoint pupils. They also had generalized muscle pain. There were also bad symptoms as far as their central nervous system. There were generalized seizures and some patients had partial seizures. In addition, there was acute mental confusion presented by hallucinations, delusions, personality changes, and behavioral changes." http://thecable.foreignpolicy.com/posts/2013/01/15/secret_state_department_cable_ chemical_weapons_used_in_syria thecable.foreignpolicy.com 1/15/13 • The doctors on the scene said they were not able to pinpoint the poison because they lacked the advanced laboratory equipment needed. They took blood, hair, saliva, and urine samples, but those samples are no longer viable for testing because too much time has passed, they said. http://thecable.foreignpolicy.com/posts/2013/01/15/secret_state_department_cable_ chemical_weapons_used_in_syria thecable.foreignpolicy.com 1/16/13 • State Dept.: We do not believe chemical weapons used in Syria Posted By Josh Rogin • Today, [State Department spokeswoman Victoria Nuland] publicly acknowledged the existence of the secret cable for the first time but said that The Cable's report "did not accurately convey the anecdotal information that we had received from a third party regarding an alleged incident in Syria in December." • "At the time we looked into the allegations that were made and the information that we had received, and we found no credible evidence to corroborate or to confirm that chemical weapons were used," she said. http://thecable.foreignpolicy.com/posts/2013/01/16/state_dept_we_do_not_believe_c hemical_weapons_used_in_syria Agent 15 • • • • An incapacitant Similar, if not identical, to BZ. Little information is known publicly In February 1998, the British Ministry of Defense accused Iraq of having stockpiled large amounts of Agent 15. http://en.wikipedia.org/wiki/3-Quinuclidinyl_benzilate BZ • 3-Quinuclidinyl benzilate (BZ) - military incapacitating agent. • Related to atropine • Competitive inhibitor of acetylcholine at receptor sites in smooth muscle, exocrine glands, autonomic ganglia, and the brain • Decreases the effective concentration of acetylcholine seen by receptors at these sites. • Opposite of effects in nerve agent poisoning. • Effects include stupor, confusion, and hallucinations. • Schedule 2 of the Chemical Weapons Convention http://en.wikipedia.org/wiki/3-Quinuclidinyl_benzilate Physostigmine - BZ Antidote • An anticholinesterase, which temporarily raises acetylcholine concentrations by binding reversibly to acetylcholinesterase, the enzyme responsible for the breakdown of acetylcholine in the synaptic cleft of the neuromuscular junction. http://en.wikipedia.org/wiki/3-Quinuclidinyl_benzilate Nuclear Threat Initiative – Syrian Chemical Weapons • The Nuclear Threat Initiative (NTI) is a nonprofit, nonpartisan organization with a mission to strengthen global security by reducing the risk of use and preventing the spread of nuclear, biological, and chemical weapons and to work to build the trust, transparency, and security that are preconditions to the ultimate fulfillment of the Non-Proliferation Treaty’s goals and ambitions. • “Between late November and early December 2012, Western intelligence agencies obtained clear evidence that Syrian government units were preparing chemical weapons for potential use. At one base, soldiers were observed to be mixing precursor chemicals and taking other steps to make the chemical weapons battlefield ready. Surveillance photos further confirmed another army unit loading chemical weapons onto special military transport vehicles.” http://www.nti.org/country-profiles/syria/chemical/ Sarin (GB) • Most easily prepared from methylphosphonyl difluoride and isopropyl alcohol. CH3P(O)F2 + (CH3)2CHOH → [(CH3)2CHO]CH3P(O)F + HF + P H3C O H2N O H Isopropyl amine F F methylphosphonic difluoride Isopropyl alcohol + H F P O H3C O F O-isopropyl methylphosphonofluoridate “Sarin” US asks Turkey, Jordan to secure chem weapons if Syria crisis worsens (1/17/13) • Syria devised its nerve weapons as binary agents, in which two less toxic chemicals are routinely stored in large, separated canisters and then loaded into separate compartments inside a bomb. For example, sarin uses a formulation of alcohol, plus another chemical. The agents combine to pose their most lethal threat only when launched or during flight, making them relatively easy to handle or transport before then – by the Syrian military or by terrorists and militant groups. http://openchannel.nbcnews.com/_news/2013/01/17/16549397-us-asks-turkeyjordan-to-secure-chem-weapons-if-syria-crisis-worsens?lite Common CW Munition Types Unitary Munitions • Easier to produce • More dangerous to store, handle & transport VX Binary Munitions (sarin) Separator MD Burster Alcohol, promoter Two non-lethal compounds • Firing, spin flight & detonation mix compounds to form agent Fuse • Relatively safer to handle & store • Munition challenging to manufacture • Methylphosphonyl difluoride + 72% isopropanol and 28% isopropylamine U.S. Wants to Move Syrian Chemical Arms to Nearby States for Incineration • The United States is in talks with the governments in Iraq, Jordan and Turkey on potentially relocating Syrian chemical weapons to protected armed forces installations on their territory for destruction, the Center for Public Integrity reported on Thursday. • Under the envisioned plan should Syria's Bashar Assad government collapse, the United States and allies would set up over six months to a year incinerating equipment in the host countries that could eliminate the large majority of chemical warfare materials in about a year. http://www.nti.rsvp1.com/gsn/article/us-providing-turkey-jordan-cw-protection-gearcase-crisis/?mgh=http%3A%2F%2Fwww.nti.org&mgf=1 Destruction of VX • VX can be converted into safer substances by combining it with a concentrated solution of sodium hydroxide, NaOH. • The reaction is called hydrolysis, in which water, H2O, divides into H, which combines with one part of a molecule, and OH, which combines with another part of the molecule, splitting the molecule into two parts. Deeper Understanding of What You Read • Syria articles issues – – – – – – What are the different chemical weapons? What is the Chemical Weapons Convention? What is an incapacitating agent? What are the symptoms of exposure? Are they difficult to make? How carefully do they need to be handled? How difficult are they to transport? – How are chemical agents dispersed? – What are the treatments for exposure? – What happens to chemical agents as they age? Deeper Understanding of What You Read • Syria articles issues (cont.) – What are Agent 15 and BZ? What are their effects of exposure? – How are molecular structures described symbolically? – What is atropine? What does it mean to be a competitive inhibitor of acetylcholine at receptor sites? – What are nerve agents? – What are the schedules for the Chemical Weapons Convention? Deeper Understanding of What You Read • Syria articles issues (cont.) – What does the following mean? An anticholinesterase, which temporarily raises acetylcholine concentrations by binding reversibly to acetylcholinesterase, the enzyme responsible for the breakdown of acetylcholine in the synaptic cleft of the neuromuscular junction. – What are precursor chemical? – What are binary weapons? – How are chemical weapons destroyed? Example 1: Octanitrocubane (ONC) • Detonation equation C8(NO2)8(s) → 8CO2(g) + 4N2(g) • The volume expansion is about 1150 fold. • The energy released is about 3475 kJ/mol. General Information Email mbishop@chiralpublishingcompany.com mbishop@miis.edu Web Sites http://preparatorychemistry.com http://institutebishop.org/science_technology.htm Recommended Reading • An Introduction to Chemistry – Atoms First by Mark Bishop http://preparatorychemistry.com/Bishop_Payment_MIIS.htm http://preparatorychemistry.com/Bishop_Atoms_First.htm • War of Nerves – Chemical Warfare from World War I to Al-Qaeda by Jonathan B. Tucker ISBN 978-1-4000-3233-4 • Toxic Terror by Jonathan B. Tucker ISBN 978-0262700719 • The Chemistry of Explosives by Jacqueline Akhavan ISBN 978-1-84973-330-4 Assignment • This will begin after the fifth chemistry module lecture. • You will divide yourselves into groups of four. • Two people in each group will pretend to be either terrorists or a country’s military leaders and plan a simulated chemical weapons attack...choosing the target, the chemical weapon, the means of delivery, the source of the chemical weapon, and the means of transporting the chemicals. • Two people in each group will act as the security team attempting to stop the attack. • The terrorists or military leaders will provide subtle clues to the security people. Assignment 1 • The security pair can tell the terrorists what they are looking for, and the terrorists will provide clues based on these searches. • Based on the clues they have received, the security team will develop a plan to stop the attack, and failing that, a plan to minimize the effects of the attack. • Each group of four will make a 5-minute presentation describing their experience.