International Maritime Dangerous Goods Code Amendment 37-14 Training Part 2 Classification
. CLASSIFICATION Class 1 Explosives Class Class 9 Miscellaneous dangerous substances and articles Marine pollutants MSC BASIC IMO training(amdt. 37-14) 2
Responsibilities: Classification: by shipper/consignor or competent authority (the list is in chapter 7.9) Classes, divisions, packing groups UN Numbers and Proper Shipping Names Classification of substances, mixtures and solutions with multiple hazards MSC BASIC IMO training(amdt. 37-14) 3
WHAT ARE DANGEROUS GOODS? PHYSICAL STATE SOLID LIQUID GAS 1. FLAMMABILITY 2. REACTIVITY 3. TOXICITY 4. AGRESSIVENESS MSC BASIC IMO training(amdt. 37-14) 4
PHYSICAL STATE SOLID: melting point > 20 C at normal pressure LIQUID: melting point 20 C at normal pressure GAS: vapor pressure at > 50 C > 300 kpa (normal air-pressure = 100 kpa = 1 bar = 1 atm) Compressed gas (pressured air) Liquified (cooled) gas (ammonia) Dissolved gas (acetylene gas in acetone) Aerosols MSC BASIC IMO training(amdt. 37-14) 5
PHYSICAL PROPERTIES Air = 1 < 1 Hydrogen ammonia > 1 ± all vapors MSC BASIC IMO training(amdt. 37-14) 6
FLAMMABILITY THE FIRE TRIANGLE To have a fire you require 3 elements: - oxygen - fuel / flammable substances - energy MSC BASIC IMO training(amdt. 37-14) 7
FLAMMABILITY OXYGEN Maintains fire 20.9% in normal ambient air is also released by oxidizing substances ENERGY temperature from hot surface friction flame spark (e.g. static electr. ) exothermic chemical reaction MSC BASIC IMO training(amdt. 37-14) 8
FLAMMABILITY Flash point, in C: the lowest temperature of a liquid at which its vapour forms an ignitable mixture with air What is flash point? The flash point of a fuel is essentially the lowest temperature at which vapours from a test portion combine with air to give a flammable mixture and 'flash' when an ignition source is applied. Which flash point test? In general flash point is measured by apparatus named "open cup" or "closed cup". "Open cup" tests are required in some specifications and regulations, and are intended to mimic conditions in open spaces whereas "closed cup" tests are closer to most situations, where space is restricted. "Closed cup" tests are more usually specified as the test results are less affected by laboratory conditions and give a more precise and lower (safer) result. There are 4 major "closed cup" flash point tests which are specified nationally and internationally for testing fuels and other materials: Pensky-Martens, Small Scale (Setaflash), Abel and Tag. MSC BASIC IMO training(amdt. 37-14) 9
FLAMMABILITY Auto ignition temperature, in C is the lowest temperature (at normal air pressure) at which a flammable substance will spontaneously ignite in a normal atmosphere without an external source of ignition, such as a flame or spark. This temperature is required to supply the activation energy needed for combustion. The temperature at which a chemical will ignite decreases as the pressure increases or oxygen concentration increases. It is usually applied to a combustible fuel mixture. Autoignition point of selected substances Temperatures vary widely in the literature and should only be used as estimates. Factors which may cause variation include partial pressure of oxygen, altitude, humidity, and amount of time required for ignition. Triethylborane: -20 C (-4 F) Diesel or Jet A-1: 210 C (410 F) Paper: 218-246 C (424-474 F) [4] Silane: <21 C (70 F) White phosphorus: 34 C (93 F) Gasoline (Petrol): 246-280 C (475-536 F) [5] Carbon disulfide: 90 C (194 F) Magnesium: 473 C (883 F) Butane: 405 C (761 F) [6] Hydrogen: 536 C (997 F) [7] Diethyl ether: 160 C (320 F) [3] Instantaneous snapshots of autoignition of ethylene MSC BASIC IMO training(amdt. 37-14) 10
FLAMMABILITY Product Flash point Auto ignition temperature Ether - 45 C 160 C Gasoline < - 20 C > 220 C Acetone - 19 C 540 C Thinner 0 21 C > 300 C Toluene 4 C 535 C Ethanol 12 C 370 C Diesel oil +/- 55 c +/- 220 C MSC BASIC IMO training(amdt. 37-14) 11
FLAMMABILITY Self- Combustion Exothermal reaction in contact with water or air. Temperature can until > auto ignition temperature ( cotton, flax, fishmeal,... ) Sufficient quantity of flammable gas (vapour) mixed with air, explosively combusts with spark, flame (e.g. empty barrel acetone, gasoline leakage, ) MSC BASIC IMO training(amdt. 37-14) 12
FLAMMABILITY Acetone: explosive limits LEL: 2.5% UEL: 13% 100% air 0% flammable gas LEL UEL 100% flammable gas 0% air MSC BASIC IMO training(amdt. 37-14) 13
REACTIVITY EXPLOSIVES explosive substances pyrotechnic substances explosive objects IN CONTACT WITH WATER evolving flammable gas OXIDIZING SUBSTANCES contains a lot of oxygen cause combustion of other material organic peroxides: even reactive (Refrigerate!) MSC BASIC IMO training(amdt. 37-14) 14
TOXICITY COLOR - ODOR - TASTELESS NOT TOXIC! CO... a serial killer every year dozens of CO-deaths every year numerous people in hospital MSC BASIC IMO training(amdt. 37-14) 15
TOXICITY HARMFUL solvents nickel pesticides Generally full recovery possible (VERY) TOXIC isocyanates potassium cyanide phenol pesticides Irreversible Damage possible MSC BASIC IMO training(amdt. 37-14) 16
AGRESSION ph STRONG Sulphuric acid, hydrochloric, nitric acid 0 ACID Acetic acid, gastric juice 1 vinegar 2 ACID Formaldehyde-solution 3 Soda water 4 Rainwater 5 milk 6 NEUTRAL Clean water 7 eggwhite 8 Self-rising flour 9 soapwater 10 BASIC Soda-sulution 11 Lime water, diluted ammonia 12 STRONG Concentrated ammonia 13 BASIC Concentrated lye 14 MSC BASIC IMO training(amdt. 37-14) 17
AGRESSION IRRITATING CAUSTIC Not Transport hazardous Redness, can be painful,... Only in plastic packaging Chemical burns Long-term rinsing with water MSC BASIC IMO training(amdt. 37-14) 18
PACKING GROUPS Packing Group I: high danger Packing Group II: medium danger Packing Group III: low danger Flash Point Boiling Point Packing group - 35 C I < 23 C > 35 C II 23 C to 60 C > 35 C III MSC BASIC IMO training(amdt. 37-14) 19
IMDG: UN-NUMBER UN numbers or UN IDs are four-digit numbers that identify hazardous substances, and articles (such as explosives, flammable liquids, toxic substances, etc.) in the framework of international transport COSTISCHE SODA SOUTH COUSTIQUE KOOLSTIK SODA SUD CUSTIC SODA COUTIC SODIUM HYDRATE LYE ATZNATRON LESSIVE DE SOUDE 1823 MSC BASIC IMO training(amdt. 37-14) 20
PROPER SHIPPING NAMES Single entries UN 1090 acetone Generic entries UN 1133 adhesives Specific N.O.S entries UN 2757 alcohols, N.O.S. General N.O.S entries UN 1993 flamable liquid, N.O.S. Not Otherwise Specified MSC BASIC IMO training(amdt. 37-14) 21
EXERCISES 1. To cause a fire following elements must be present: a) Flammable substance + heat+ spark b) Flammable substance + oxygen c) Flammable substance + oxygen + source of heat 2. The flashpoint of pentane is -40 C. This means that: a) at 40 C pentane will inflame at the least flame b) pentane will burn spontaneous in contact with air without spark or flame c) pentane inflames at the least spark MSC BASIC IMO training(amdt. 37-14) 22
EXERCISES 1. Sulphuric acid is a corrosive fluid. This means that sulphuric acid: a. has a caustic effect on eyes and skin b. is very toxic when inhaled or swallowed c. can cause infections at contact with the skin 2. Calcium nitrate is an oxidizing solid. This matter: a. is flammable b. is not flammable but stimulates fire of other products c. reacts dangerous with water. MSC BASIC IMO training(amdt. 37-14) 23
EXERCISES 1. The Dangerous Goods List can be found in: Volume 1 ( part 3 ) Volume 2 ( part 3 ) The supplement Volume 1 ( part 5 ) 2. Where can you find the classification of dangerous products? MSC BASIC IMO training(amdt. 37-14) 24
EXERCISES 1. All acids can be found in: Volume 1 (part 2: CLASSIFICATION) Volume 1 (part7: SEGREGATION) The supplement Volume 2 (chapter 3.1: SEGREGATION GROUPS) 2. Right or wrong? Regulations transport documents: vol.1 part 5 Dangerous labels: vol.1 part 5 MSC BASIC IMO training(amdt. 37-14) 25
EXERCISES 1. Packing group II stands for: a. Very dangerous b. Dangerous c. Less dangerous d. Indicates the sort of packing 2. An example of a unit load is: a. A packing including it s content b. A tank container or a truck c. Inside packing inside a cardboard box d. A pallet on which several boxes are settled MSC BASIC IMO training(amdt. 37-14) 26
EXERCISES What is the meaning of EmS in the IMDG-code? a. Entire material Safety data sheets b. Emplacement Schedules for dangerous goods c. Emergency Response Procedures for Ships Carrying Dangerous Goods d. Emergency and Safety rules for dangerous products MSC BASIC IMO training(amdt. 37-14) 27
EXERCISES Is the following statement correct? Flash Point, C: the highest temperature (at normal air pressure) where a fluid deposits so much flammable fume (at or nearby the fluid surface) that this fume, intensive or mixed with air, can be inflamed by a hot surface. MSC BASIC IMO training(amdt. 37-14) 28
EXERCISES What is the Proper Shipping Name? UN1037 UN1263 UN1935 UN1955 UN2786 MSC BASIC IMO training(amdt. 37-14) 29
EXERCISES What is FP for UN 1922, UN 2789? What is the Packing Group (PG) for UN 2024? What is the danger of AZODICARBONAMIDE? (UN3242) Are CO (UN1016) and chloride (UN 1017) marine pollutant? MSC BASIC IMO training(amdt. 37-14) 30
» VOLUME 1 PART 2 p. 41 9 different classes Classes, divisions Responsible: shipper/consignee Where to find? Material Safety Data Sheet MSC BASIC IMO training(amdt. 37-14) 31
1. IDENTIFICATION PRODUCT, ENTERPRISE 2. COMPOSITION, INFO COMPONENT 3. RISKS 4. EHBO 5. FIREFIGHTINGMEASURES 6. MEASURES FOR ACCIDENTAL RELEASE 7. HANDLING AND STORAGE 8. CONTROL, EXPOSURE? PBM S 9. PHYSICAL,CHEMICAL QUALITIES 10. STABILITY, REACTIVITY 11. TOXICOLOGICAL INFORMATION 12. ECOLOGICAL INFORMATION 13. INSTRUCTIONS FOR DISPOSAL 14. INFORMATION FOR TRANSPORT 15. REGULATORY MANDATORY INFORMATION 16. ADDITIONAL INFO For professional user At first delivery Free Very complete information? Language user, recent version! IMDG/ADR/RID/ADNR MSC BASIC IMO training(amdt. 37-14) 32
IMDG- Classes IMDG-CLASS 1: EXPLOSIVES RESTRICTED CLASS 1.1MASS EXPLOSION HAZARD 1.2PROJECTION HAZARD 1.3FIRE HAZARD (MINOR BLAST HAZARD / PROJECTION HAZARD) 1.4EFFECTS LARGELY CONFINED TO THE PACKAGE 1.5VERY INTENSIVE SUBSTANCES WHICH HAVE A MASS EXPLOSION HAZARD 1.6EXTREMELY INSENSITIVE ARTICLES WHICH DO NOT HAVE A MASS EXPLOSION HAZARD UN < 1000! MSC BASIC IMO training(amdt. 37-14) 33
IMDG- Classes IMDG-CLASS 2: GASES 2.1 2.2 2.3 COMPRESSED-LIQUEFIED-REFRIGERATED- DISSOLVED MSC BASIC IMO training(amdt. 37-14) 34
IMDG- Classes IMDG-CLASS 2: GASES UN 1075 CLASS 2.1 petroleum gases, liquefied UN 1963 CLASS 2.2 helium, refrigerated liquid UN 1079 CLASS 2.3 (8) sulphur dioxide MSC BASIC IMO training(amdt. 37-14) 35
IMDG- Classes IMDG-CLASS 3: FLAMMABLE LIQUIDS FLASHPOINT BOILING POINT PACKING GROUP 35 C I < 23 C > 35 C II 23 C to 60 C > 35 C III + temperature controlled liquids > flashpoint + Heated substances in liquid state that release an explosive vapour MSC BASIC IMO training(amdt. 37-14) 36
IMDG- Classes IMDG-CLASS 4.1: FLAMMABLE SOLIDS, SELF-REACTIVE SUBSTANCES AND SOLID DESENSITIZED EXPLOSIVES IMDG-CLASS 4.2: SUBSTANCES LIABLE TO SPONTANEOUS COMBUSTION IMDG-CLASS 4.3: SUBSTANCES WHICH, IN CONTACT WITH WATER, EMIT FLAMMABLE GASES MSC BASIC IMO training(amdt. 37-14) 37
IMDG- Classes IMDG-CLASS 4.1 FLAMMABLE SOLIDS READILY COMBUSTIBLE SOLIDS + SOLIDS CAUSING FIRE THROUGH FRICTION EXAMPLE: UN 1331 MATCHES STRIKE ANYWHERE EXAMPLE: UN 1334 NAPHTALENE, CRUDE SELF-REACTIVE SUBSTANCES THERMALLY UNSTABLE SUBSTANCES LIABLE TO UNDERGO A STRONGLY EXOTHERMIC DECOMPOSITION EVEN WITHOUT PARTICIPATION OF OXYGEN (AIR) EXAMPLE: UN 3236 2,2 -AZODI(2?4-DIMETHYLVALERONITRIL) CONTROL TEMP. + 5 C EMERGENCY TEMP. + 10 C SOLID DESENSITIZED EXPLOSIVES EXPLOSIVE SUBSTANCES WETTED WITH WATER OR ALCOHOLS OR DILUTED WITH OTHER SUBSTANCES TO SUPPRESS THEIR EXPLOSIVE PROPERTIES EXAMPLE: UN 1310 AMMONIUM PICRATE, WETTED MSC BASIC IMO training(amdt. 37-14) 38
IMDG- Classes IMDG-CLASS 4.2 SUBSTANCES LIABLE TO SPONTANEOUS COMBUSTION EXAMPLE: UN1365 COTTON, WET MSC BASIC IMO training(amdt. 37-14) 39
IMDG- Classes IMDG-CLASS 4.3 SUBSTANCES WHICH, IN CONTACT WITH WATER, EMIT FLAMMABLE GASES EXAMPLE: UN 1402 CALCIUM CARBIDE MSC BASIC IMO training(amdt. 37-14) 40
IMDG- Classes IMDG-CLASS 5.1 OXIDIZING SUBSTANCES SUBSTANCES WHICH MAY CAUSE OR CONTRIBUTE TO THE COMBUSTION OF OTHER MATERIAL EXAMPLE: UN2067 AMMONIUM NITRATE FERTILIZER MSC BASIC IMO training(amdt. 37-14) 41
IMDG- Classes IMDG-CLASS 5.2 ORGANIC PEROXIDES THERMALLY UNSTABLE SUBSTANCES WHICH MAY UNDERGO EXOTHERMIC SELF-ACCELERATING DECOMPOSITION EXAMPLE: UN3115 ORGANIC PEROXIDE TYPE D, LIQUID, TEMPERATURE CONTROLLED (DIACETYLPEROXIDE) MSC BASIC IMO training(amdt. 37-14) 42
IMDG- Classes Self-Accelerating Decomposition Temperature is the lowest temperature at which an organic peroxide in a typical vessel or shipping package will undergo a self-accelerating decomposition. The SADT is the point at which the heat evolution from the decomposition reaction and the heat removal rate from the package becomes unbalanced. Class 4.1: 75 C for a 50 kg package Class 5.2: 45 C or 50 C MSC BASIC IMO training(amdt. 37-14) 43
IMDG- Classes IMDG-CLASS 6.1 TOXIC SUBSTANCES SUBSTANCES LIABLE TO CAUSE DEATH OR SERIOUS INJURY OR TO HARM HEALTH IF SWALLOWED OR INHALED OR BY SKIN CONTACT EXAMPLE: UN1671 PHENOL, SOLID EXAMPLE: UN2992 CARBAMATE PESTICIDE, LIQUID, TOXIC MSC BASIC IMO training(amdt. 37-14) 44
IMDG- Classes IMDG-CLASS 6.2 INFECTIOUS SUBSTANCES SUBSTANCES CONTAINING PATHOGENS (BACTERIA, VIRUSES, PARASITES, FUNGI, ), WHICH CAN CAUSE DISEASE IN HUMANS OR ANIMALS EXAMPLE: UN3291 CLINICAL WASTE N.O.S. MSC BASIC IMO training(amdt. 37-14) 45
IMDG- Classes TOXICITY ORAL TOXICITY LD 50 mg/kg DERMAL TOXICITY LD 50 mg/kg INHALATION TOXICITY LD 50 mg/kg PG I 5 50 0,2 PG II > 5 and 50 < 50 and 200 <0.2 and 2 PG III > 50 and 300 > 200 and 1000 > 2 and 4 LD 50 : dose administered to rats during 24h, necessary to kill 50% of the test animals within 14 days. LC 90 : dose administered to rats during 4h, necessary to kill 50% of the test animals within 14 days. MSC BASIC IMO training(amdt. 37-14) 46
IMDG- Classes IMDG-Class 7 RADIOACTIVE MATERIAL ANY MATERIAL CONTAINING RADIONUCLIDES WITH AN ACTIVITY CONCENTRATION AND TOTAL ACTIVITY EXCEEDING SPECIFIED VALUES MSC BASIC IMO training(amdt. 37-14) 47
IMDG- Classes IMDG-Class 7 Unit for radiant energy that is being absorbed: SIEVERT (Sv) Regulatory dose limit: 1mSv/j (exclusive medical exposure) Limit value for further investigation: 5 µsv/u 500 µsv/u 2 msv/u (on the packaging) MSC BASIC IMO training(amdt. 37-14) 48
IMDG- Classes IMDG-Class 8 CORROSIVE SUBSTANCES SUBSTANCES CAUSING SEVERE DAMAGE WHEN IN CONTACT WITH LIVING TISSUE OR IN THE CASE OF LEAKAGE WILL MATERIALLY DAMAGE OR EVEN DESTROY OTHER GOODS OR THE MEANS OF TRANSPORT no irritating products acids and bases products that become corrosive in contact with water EXAMPLE: UN2794 BATTERIES, WET, FILLED WITH ACID EXAMPLE: UN2672 AMMONIA SOLUTION MSC BASIC IMO training(amdt. 37-14) 49
IMDG- Classes IMDG-Class 9 MISCELLANEOUS DANGEROUS SUBSTANCES AND ARTICLES AND ENVIRONMENTALLY HAZARDOUS SUBSTANCES SUBSTANCES WHICH, DURING TRANSPORT, PRESENT A DANGER NOT COVERED BY OTHER CLASSES health threatening substances substances which may form dioxins when on fire substances which evolve flammable vapors marine pollutant substances heated substances solid: 240 C; liquid: 100 C MSC BASIC IMO training(amdt. 37-14) 50
IMDG- Classes IMDG-Class 9 MARINE POLLUTANTS» If only environmentally hazardous: UN 3077 (solid) UN 3082 (liquid)» If there are also other hazards: other class Class 1 till 8 + (symbol marine pollutant) MIXTURES, SOLUTIONS: 10% P = MP MSC BASIC IMO training(amdt. 37-14) 51
IMDG- Classes IMDG-Class 9 MARINE POLLUTANTS» absorbed in the Food Chain» toxic for fishes, shellfish,. Amdt. 36-12 MSC BASIC IMO training(amdt. 37-14) 52
IMDG- Classes IMDG-Class 9 MARINE POLLUTANTS Potential to bioaccumulate in seafood High toxicity to aquatic life P : pollution potential Solutions, mixtures: 10% P = marine pollutant MSC BASIC IMO training(amdt. 37-14) 53
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