Ch1_L20-2nd 2016-2017 J

Chem 1
Chemistry of Carbon
2nd Sem 2016-2017 Organic Chemistry
Lecture 20

FCariño

Functional groups Functional groups

• Reactive sites in organic molecule • Reactive sites in organic molecule

Structure and Property

Compound Formula MW BP, °C

Chlorophyll d propane CH3CH2CH3

44 -42.1

Dimethyl CH3OCH3
Ether 46 -24.8

Ethanol CH3CH2OH 46 78
Acetaldehyde CH3CHO
44 20

Tetracycline Formic Acid HCOOH 48 100

5

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Structure and Property

Compound Formula MW BP, °C
propane Force CH3CH2CH3
London 44 -42.1

Dimethyl Ether CH3OCH3

Dipole-dipole 46 -24.8
Polymers
H-bonding
Ethanol CH3CH2OH 46 78
Acetaldehyde
Dipole-dipole CH3CHO
44 20

H-bonding
Formic Acid HCOOH 48 100
8

Polymers Natural polymers

• Greek poly = many + meros = parts cotton
• Substances containing large numbers
of repeating structural units joined by Wood
the same type of linkage
• Monomers = material that will be linked
uniformly Starch

• Repeating units after linking = segmers

• May be natural or synthetic
DNA silk
9 10

Plastics are polymers

Fig. 1. Global map with each country shaded according to the

estimated mass ofmismanaged plastic waste [millions ofmetric
tons (MT)] generatedin 2010 by populations living within 50 km
of the coast. (192 countries considered; . Countries not included
in the study shaded white.

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http://www.qualitylogoproducts.com/lib/different-types-of-
plastic.htm

http://www.thedailygreen.com/green-homes/latest/recycling-
symbols-plastics-460321?click=main_sr#slide-1

Vinyl is
rarely recycled
http://www.qualitylogoproducts.com/lib/different-
types-of-plastic.htm

http://www.thedailygreen.com/greenhomes/latest
/recycling-symbols-plastics-
460321?click=main_sr#slide-1 http://www.qualitylogoproducts.com/lib/different-types-of-plastic.htm

http://www.thedailygreen.com/green-homes/latest/recycling-symbols-
plastics-460321?click=main_sr#slide-1

low density polyethylene polypropylene – not

commonly recycled, but
- requires
acceptable in many areas
specialty recycling

http://www.qualitylogoproducts.com/lib/different- http://www.qualitylogoproducts.com/lib/different-
types-of-plastic.htm types-of-plastic.htm

http://www.thedailygreen.com/green- http://www.thedailygreen.com/green-
homes/latest/recycling-symbols-plastics- homes/latest/recycling-symbols-plastics-
460321?click=main_sr#slide-1 460321?click=main_sr#slide-1

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miscellaneous– difficult to
polystyrene– recyclable,
recycle
but difficult

http://www.qualitylogoproducts.com/lib/different- http://www.qualitylogoproducts.com/lib/different-
types-of-plastic.htm types-of-plastic.htm

http://www.thedailygreen.com/green- http://www.thedailygreen.com/green-
homes/latest/recycling-symbols-plastics- homes/latest/recycling-symbols-plastics-
460321?click=main_sr#slide-1 460321?click=main_sr#slide-1

Group Project 3: 4-page group paper

Written report by group, 4 pages maximum 1. Introduction (short paragraph )
All groups: For one whole week, gather and rinse all the 2. Methodology
disposable plastic materials that you will use staring the 3. Picture of each pile
week after Holy week (April 17-23). Air dry them and bring
4. Brief discussion
them to class on April 26, 2017 (Wednesday). Sort them
according to SPI classification, making a pile for each a) General description of collected material
classification. Take a picture of each pile. Find out which b) Pile that can be recycled
class can be sold for recycling (ask the janitors). Get more c) Pile that can be sold at household level
details, including how much is being paid for each class of d) Items that can be reused/repurposed
recyclable plastic. Prepare a group report for this activity,
identifying the classes that can be sold for recycling, 5. Summary and recommendations for plastic waste
showing pictures of the piles you have made based on the management
SPI classification, and proposing means of improving our
management of plastics. Due Wednesday 3 May, 2017

Lethal Potions:
Chemicals for War

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Warfare J

Chemical Warfare Agents (CWA)

• chemical substances which might be
employed in warfare because of their
direct toxic effects on man, animals and
plants
• Includes ammunition and equipment
Chemical for their dispersal.

Warfare

Classification of CWA

•Lung-damaging agents
•Blister agents
•Nerve agents
•Blood agents

Germans first used

poison gas in WW I
against the Allies
Lung-Damaging Agents
(choking agents) • Cl2 released into wind
by Germans vs. Allies
• burned lungs à
killed/maimed
• Cl2 caused formation
•chlorine of yellow fluid in lungs
•phosgene à death by choking

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Chlorine Gas Stockpile: ~160 tons

released from 6,000 pressurized cylinders
April 22, 1915 : Ypres

160 tons of chlorine gas (Cl2)

6,000 pressurized cylinders

Death in Ypres - 5000 died via 1915: British retaliation with Phosgene
conventional warfare, + 5000 died due to Cl2 (10X more deadly than chlorine)

Phosgene
• Major industrial chemical for plastics and pesticides. Blister Agents
• Poisonous gas at RT; with cooling and pressure à
liquid (for shipping and storage) (vesicants)
• When liquid released à turns into gas that stays close
to the ground and spreads rapidly. •sulfur mustards (H/HD)
• May appear colorless or as a white to pale yellow cloud.
• At low concentrations, pleasant odor of newly mown •arsenicals: lewisites (L)
hay or green corn (but may not be noticed). At high
concentrations, odor may be strong, unpleasant. •nitrogen mustards (HN)
• Nonflammable (not easily ignited and burned).
• Military designation is “CG.”
https://emergency.cdc.gov/agent/phosgene/basics/facts.asp

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July 1917: Mustard Gas

Skinblisters
• First used by
Germans
• blister agent
• Winston Churchill
calls it “hellish
poison”

Synthesis: Frederick
Guthrie, 1860
Eye Sores

• 113,000 tons of chemical weapons

1918: Lewisite WW I • killing around 92,000

• 1.3 million casualties.

• Synthesized by W. Lee Lewis

• blister agent
• Large scale production by US

1925: Geneva Protocol

• First efforts to control chemical and biological

weapons
• Went into force in 1928
• Protocol for prohibition of the use in war of
asphyxiating, poisonous or other gases, and of
bacteriological methods of warfare
In response to the horror of chemical • 38 nations signed initially, 130 nations signed
warfare during World War I, many
governments wished to ban chemical
weapons because of the horrendous
means by which they killed and injured
people.

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1930-1945: Invention of Nerve Gases

Loopholes: Geneva Protocol
• Does not prohibit the research, manufacture and
threat of use of chemical weapons
• rather vague in the use of the term "other gas”
• no provisions for the punishment of countries that
use such chemical weapons
• Germans invented and stockpiled the first nerve
gas from 2,000 organophosphates
• Include: tabun (1934) by Dr. Schrader
sarin (1938), soman (1944)
• They are odorless and colorless
• Attack the body muscles, including the
involuntary muscles
• The most lethal and insidious weapon of
chemical warfare

Lethal organo-phosphorus
Nerve Gases compounds inhibiting Organophosphate insecticides
cholinesterase
Sulfur analogs of organophosphate esters
Tabun (GA) Sarin (GB) Soman (GD)

Organophosphate Organophosphate
• Organophosphate-type compounds ester insecticide
• Manufactured by fairly simple techniques
• Raw materials cheap and readily available.
• Dispersed: in an droplet or mist form
Parathion Malathion

WW II: Holocaust
Blood Agents
hydrogen cyanide (cyanogens)
O Lethal gas was never employed in combat
carbon monoxide
O Germans did use gases for mass murder
during the Holocaust •hydrogen cyanide (AC)
•cyanogen chloride (CK)
•carbon monoxide

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After WWII: Nerve Gases in

Volgograd, Russia 1952:British Invention of VX

• United Kingdom discovered VX while studying

• Allied nations seized the chemical weapons
from Germany
• Many manufacturing plants moved to Russia
• A new site in Volgograd
• Prompted other nations to begin even more
research on chemical weapons
insecticides and herbicides
• A chemical agent which was many times greater
in lethal properties than any other known
chemical agent at the time it was discovered
• 1961: The United States took over the large
scale production in Dugway, Utah
• 1968: Shutdown of plant

• Comes in an oily liquid form

that is persistent for weeks
Symptoms of
or longer in the environment
Poisoning: g. Excessive
• Used to deny access to a VX perspiration
given area thus stop or slow a. Runny nose
an enemy ground advance
b. Bronchial h. Nausea, Vomiting
secretions i. Involuntary
c. Tightness in the defecation, urination
chest j. Muscle tremors,
d. Dimming of vision convulsions
e. Pin-Point Pupils k. Coma
f. Drooling l. Death – may occur in
2 minutes

• Geneva Protocol (1974): reaffirmation of the ban,

Further Use of Chemical Weapons
1930’s - 1975
• British in Afghanistan
• French and Spanish in Africa
• Japanese in China
• Italy in Ethiopia
• 1963: Egyptians in Yemen
• 1975: Laotians in internal strife
• 1975: Vietnamese in Kampuchea
extending it to the production and storage of
chemical weapons
• 1980’s : start destruction of many chemical
weapon stocks for various reasons (leakage,
political urging, etc)
• 1990: end of Cold War – US and Soviet Union
agreed to cut chemical arsenals by 80% to
discourage smaller nations from stockpiling and
using such lethal weapons

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Use of Chemical Weapons Iraqi Mustard Agent

• 1980: Iraq against Iran (confirmed)
Bomb
• 1988: Iraq against Kurdish rebels
(confirmed)
• 1991: Iraq in the Persian Gulf War (alleged)
Sarin used

Iraqi soldiers who were Nerve gas victims in Halabja, 1988...

victims of mustard gas
attack in Halabja

2013 Nobel
1993: International Treaty Peace Prize was
awarded to
the Organisation
• Convention on the Prohibition of the for the Prohibition
Development, Production, Stockpiling and Use of of Chemical
Chemical Weapons and calls for their Destruction Weapons, for
by 2007 (CWC) their "extensive
work to eliminate
• Establishment of an independent organization to chemical
verify compliance (OPCW) weapons".
• Became effective in 1997 (65 signatories, Phil.
included)
• Current Member States represent about 98% of
global population and landmass, as well as 98%
of the worldwide chemical industry.

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CWC allows regulated use of CW agents

and related substances in:
March 1995: Sarin in Japan
• Religious cult released • Chemical industries (precursors for pesticides or
a form of sarin nerve in polymer synthesis)
gas in Tokyo’s subway • Pharmaceutical companies (medical drug
system during morning production)
rush hour • Research (development of antidotes, testing
• 11 people dead, 5,500 protective equipment, development of
people wounded instruments and methods for detection/analysis
of these agents)
>>All are subject to inspection by OPCW

Toxicities of Various
Compounds Biological Toxins
Compound LD50 (µg/kg) (microbes, plants, animals,
synthetical)
glucose 35000000
sodium chloride 3700000
arsenic trioxide 45000
• Botulinum Neurotoxin (bacterial)
potassium cyanide 10000 • Staphylococcal Enterotoxin B (bacterial)
sulfur mustard 3000
Tabun 40
• Ricin (plant)
Sarin 20 • Trichthecene (fungal)
Soman 3 • Bioregulators (natural, synthetical)
VX 0.1
ricin 0.02
tetanus toxin 0.0001
botulinum toxin 0.00003 WF/WIA 1998

Destruction of CW Agents CW Threat Continues…

O Incineration: Only method allowed by CWC • CW-facilities

• thermal process to destroy toxic wastes • production
• flame-initiated, high temperature air oxidation of waste • destruction
material (1800oC) • CW-storage
• Incinerators designed for CW (US, Europe) • CW- terrorism
O Not allowed:
• Open-pit burning
>>Especially in countries
• Dumping in the sea
which have not ratified the CWC

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CW Stockpile (World) Group work 2

1. Download the video FIRES A Teacher’s Mission

at https://vimeo.com/92032364
2. Watch the video and discuss among yourselves
whether the historical judgment on Haber’s deeds
is fair, i. e., was Haber a war villain, or was he a
nationalist helping his country win a war?
3. Use the internet to gain more information on Haber
and his other contributions to Chemistry and his
country.
4. Write a paper (no more than 2 pages) on whether
your group will consider Haber as a villain or a hero
of his country. Due 21 April 2017

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