Lecture 3

Organic Compounds

Acetaldehyde Isopropanol

Acetone Chloroform

Methanol Trichloroethanol

Ethanol Dichloroethane

Carbon terachloride Toluene

Benzene Formaldehyde

Commonly Found Volatiles

methanol

ethanol

isopropanol

present in some drinks (“Kirsch”)

technical alcohol mixtures

Additional problem: mixed intoxication of ethanol and drugs

1. acetaldehyde2. methanol3. acetone4. ethyl formate5. ethanol6. ethyl acetate7. n-propanol8. sec-butanol9. isobutanol10. active amyl alcohol11. isoamyl alcohol12. n-amyl alcohol

Rum

Scotch

formaldehyde

acetone

methyl ethyl ketone

1. methanol2. ethanol3. diethyl ether4. isopropanol5. methylene chloride6. acetone7. methyl tert-butyl ether8. hexane

9. chloroform10. ethyl acetate11. methyl ethyl ketone12. benzene13. trichloroethylene14. toluene15. methyl isobutyl ketone

Headspace

in blood – metabolic disorder,after an accident, etc.

Diethyl Ether Propanal Allyl ether

Propanol,

Butanol, Pentanol

Methyl Acetate, Ethyl Acetate, Propyl Acetate

Hexane, Heptane

Octane

Propionitrile Diethylamine Acetonitrile

Dichloromethane Xylene Cyclohexane

Tetrahydrofuran Acrylonitrile Camphor

Dioxane Carbon Disulfide Acrolein

Dichloropropane Methyl isobutyl ketone Methylcyclohexane

Infriquently found volatiles

GC headspace

“Semivolatile” hazardous substances

1. 2-fluorophenol 2. phenol3. 1,4-dichlorobenzene-d4 (IS)4. nitrobenzene5. napthalene-d8 (IS)6. 2-fluorobiphenyl 7. acenaphthene-d10 (IS)8. 1-naphthalenamine9. 2-naphthalenamine10. 5-nitro-o-toluidine11. diphenylamine12. 2,4,6-tribromophenol 13. 4-aminobiphenyl14. phenanthrene-d10 (IS)15. p-terphenyl16. p-dimethylaminoazobenzene17. 2-acetylaminofluorene18. chrysene-d12 (IS)

hazardous substances + internal standard mixture

GC-MS

N

N +

+

Paraquat NN

+ +

Diquat

N+

MMP+

Peak List: Peak time (min.)1. diquat 7.52. paraquat 8.8

acetonitrile, 95:5 (v/v)Flow: 1.0 mL/min.Temp.: 27°CDet.: UV @ 257nm (paraquat)UV @ 308nm (diquat)

HPLC

Herbicides:

OOH

O

ClCl

2,4-Dichlorophenoxyacetic acid (2,4-D)

OOH

O

ClCl

Cl

2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)

O

O1

2

34 6

7

89

O

OCl

Cl

Cl

Cl

2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)

1. 1,4,7,8-TCDD2. 2,3,7,8-TCDD3. 1,2,3,4-TCDD4. 1,2,3,75. 1,2,3,8-TCDD6. 1,2,7,8-TCDD

GC: 2.0μL splitless injection of TCDD isomers,approximately 0.5ng each isomerSplitless hold: 0.45 min ECD detector

CCl3

ClClDDT

Aldrin

1. 2,4,5,6-tetrachloro-m-xylene (ss) 2. α-BHC3. γ-BHC4. β-BHC5. δ-BHC6. heptachlor7. aldrin8. heptachlor epoxide9. γ-chlordane10. α-chlordane11. endosulfan I

12. 4,4'-DDE13. dieldrin14. endrin15. 4,4'-DDD16. endosulfan II17. endrin aldehyde18. 4,4'-DDT19. endosulfan sulfate20. methoxychlor21. endrin ketone

Organochlorine Pesticides

F

PO

O

OO

PS

SOO

OO

OO

PS

OOO

OO

sarin

Malathion

Malaoxon

warfare agent

Organophosphorus Pesticides

GC

30. fenthion31. aspon32. parathion-ethyl33. chlorpyrifos34. trichloronate35. chlorfenvinphos36. merphos37. crotoxyphos38. stirofos39. tokuthion40. merphos oxidation product41. fensulfothion42. famphur43. ethion44. bolstar45. carbophenothion46. triphenyl phosphate (IS)47. phosmet48. EPN49. azinphos-methyl50. leptophos51. tri-o-cresyl phosphate52. azinphos-ethyl53. coumaphos

2. hexamethylphosphoramide3. mevinphos4. trichlorfon5. TEPP6. thionazin (IS)7. demeton-O8. ethoprop9. tributyl phosphate (SS)10. dicrotophos11. monocrotophos12. naled13. sulfotepp14. phorate15. dimethoate16. demeton-S17. dioxathion18. terbufos19. fonophos20. phosphamidon isomer21. diazinon22. disulfoton23. phosphamidon24. dichlorofenthion25. parathion-methyl26. chlorpyrifos methyl27. ronnel28. fenitrothion29. malathion

Organophosphorus PesticidesOven temp.: 100°C to 180°C @ 10°C/min. (hold 2 min.), to 300°C @ 18°C/min. Inj. / det. temp.: 250°C / 280°C FPDSolvent: hexane

Carbaryl (1-naphthyl methylcarbamate)

Methyl isocyanate (MIC)

H3C-N=C=O

Bhopal accident

1. aldicarb sulfone2. aldicarb sulfoxide3. oxamyl4. methomyl5. 3-hydroxycarbofuran6. aldicarb7. propoxur8. carbofuran9. carbaryl10. methiocarb11. 4-bromo-3,5-dimethylcarbamate

HPLC Mobile phase: A: 90:10 water:methanolB: 90:10 methanol:acetonitrile

UV @220 nm

Pesticides (Carbamates)

N

N

N

Cl

NN

HH

Atrazine

N

N

NH H

H

O

O Ocyanuric acid

Triazine Herbicides

Cl

O

chloroacetophenone, “tear gas”, “Mace”

Cl

CN

CN

2-chlorobenzalmalononitrile, CS gas

HO

ONH

O

Capsaicin , “pepper spray”

Yperite

C4H8Cl2S NN

O

OO

Carfentanil

chemical warfare agent, has industrial usepotential chemical warfare agent

Tear gases: