Samples of self-reactive substances or formulations of self-reactive substances not listed in 2.2.41.4, for which a complete set of test results is not available and which are to be carried for further testing or evaluation, shall be assigned to one of the appropriate entries for self-reactive substances type C provided the following conditions are met:
- the available data indicate that the sample would be no more dangerous than self-reactive substances type B;
- the sample is packaged in accordance with packing method OP2 and the quantity per transport unit is limited to 10 kg;
- the available data indicate that the control temperature, if any, is sufficiently low to prevent any dangerous decomposition and sufficiently high to prevent any dangerous phase separation.
Desensitization
In order to ensure safety during carriage, self-reactive substances are in many casesdesensitized by use of a diluent. Where a percentage of a substance is stipulated, this refers to the percentage by mass, rounded to the nearest whole number. If a diluent is used, the self-reactive substance shall be tested with the diluent present in the concentration and form used in carriage. Diluents which may allow a self-reactive substance to concentrate to a dangerous extent in the event of leakage from a packaging shall not be used. Any diluent shall be compatible with the self-reactive substance.In this regard, compatible diluents are those solids or liquids which have no detrimental influence on the thermal stability and hazard type of the self-reactive substance. Liquid diluents in formulations requiring temperature control (see 2.2.41.1.14) shall have a boiling point of at least 60°C and a flash-point not less than 5°C. The boiling point of the liquid shall be at least 50°C higher than the control temperature of the self-reactive substance.
Temperature control requirements
Self-reactive substances with an SADT not greater than 55 °C shall be subject to temperature control during carriage. See 7.1.7.
Solid desensitized explosives
Solid desensitized explosives are substances which are wetted with water or alcohols or are diluted with other substances to suppress their explosive properties. Such entries in TableA of Chapter 3.2 are: UN Nos. 1310, 1320, 1321, 1322, 1336, 1337, 1344, 1347, 1348, 1349, 1354, 1355, 1356, 1357, 1517, 1571, 2555, 2556, 2557, 2852, 2907, 3317,3319, 3344, 3364, 3365, 3366, 3367, 3368, 3369, 3370, 3376, 3380and 3474.
Substances related to self-reactive substances
Substances that:
(a)have been provisionally accepted into Class 1 according to Test Series 1 and 2 but exemptedfrom Class 1 by Test Series 6;
(b)are not self-reactive substances of Class 4.1; and
(c)are not substances of Classes 5.1 or 5.2;are also assigned to Class 4.1. UN Nos. 2956, 3241, 3242 and 3251 are such entries.
Polymerizing substances
Definitions andproperties
Polymerizing substances are substances which, without stabilization, are liable to undergo a strongly exothermic reaction resulting in the formation of larger molecules or resulting in the formation of polymers under conditions normally encountered in carriage. Such substances are considered to be polymerizing substances of Class 4.1 when:
(a)their self-accelerating polymerization temperature (SAPT) is 75°C or less under the conditions(with or without chemical stabilization as offered for carriage) and in the packaging, IBC ortank in which the substance or mixture is to be carried;
(b)they exhibit a heat of reaction of more than 300 J/g; and
(c)they do not meet any other criteria for inclusion in classes 1 to 8.
A mixture meeting the criteria of a polymerizing substance shall be classified as a polymerizing substance of Class 4.1.
Temperature control requirements
Polymerizing substances are subject to temperature control in carriage if their self-accelerating polymerization temperature (SAPT) is:
(a)when offered for carriage in a packaging or IBC, 50°C or less in the packaging or IBC inwhich the substance is to be carried; or
(b) When offered for carriage in a tank, 45 °C or less in the tank in which the substance is to be
carried.
See 7.1.7.
NOTE: Substances meeting the criteria of polymerizing substances and also for inclusion in Classes 1 to 8 are subject to the requirements of special provision 386 of Chapter 3.3.
Substances not accepted for carriage
The chemically unstable substances of Class 4.1 shall not be accepted for carriage unless the necessary steps have been taken to prevent their dangerous decomposition or polymerization during carriage. To this end, it shall in particular be ensured that receptacles and tanks do not contain any substance liable to promote these reactions.
Flammable solids, oxidizing, assigned to UN No. 3097 shall not be accepted for carriage unless they meet the requirements for Class 1 (see also 2.1.3.7).
The following substances shall not be accepted for carriage:
- Self-reactive substances of type A (see Manual of Tests and Criteria, Part II, paragraph 20.4.2 (a));
- Phosphorus sulphides which are not free from yellow and white phosphorus;
- Solid densitized explosives other than those listed in Table A of Chapter 3.2;
- Inorganic flammable substances in the molten form other than UN No. 2448 SULPHUR,MOLTEN.
List of collective entries
_____________________
a Metals and metal alloys in powdered or other flammable form, liable to spontaneous combustion, are substances of Class 4.2.
b Metals and metal alloys in powdered or other flammable form, which in contact with water, emit flammable gases, are substances of Class 4.3.
c Metals hydrides which, in contact with water, emit flammable gases, are substances of Class 4.3. Aluminium borohydride or aluminium borohydride in devices are substances of Class 4.2, UNNo.2870.
List of currently assigned self-reactive substances in packagings
In the column "Packing Method" codes "OP1" to "OP8" refer to packing methods in 4.1.4.1, packing instruction P520 (see also 4.1.7.1). Self-reactive substances to be carried shall fulfil the classification and the control and emergency temperatures (derived from the SADT) as listed. For substances permitted in IBCs, see 4.1.4.2, packing instruction IBC520 and, for those permitted in tanks according to Chapter 4.2, see 4.2.5.2.6, portable tank instruction T23. The formulations listed in packing instruction IBC520 of 4.1.4.2 and in portable tank instruction T23 of 4.2.5.2.6 may also be carried packed in accordance with packing method OP8 of packing instruction P520 of 4.1.4.1, with the same control and emergency temperatures, if applicable.
NOTE: The classification given in this table is based on the technically pure substance (except where a concentration of less than 100% is specified). For other concentrations, the substance may be classified differently following the procedures given in Part II of the Manual of Tests and Criteria and in 2.2.41.1.17.
|
SELF-REACTIVE SUBSTANCE |
Concen- tration (%) |
Packing method |
Control tempera- ture (°C) |
Emergency tempera- ture (°C) |
UN generic entry |
Remarks |
|
ACETONE-PYROGALLOL COPOLYMER 2-DIAZO-1-NAPHTHOL-5-SULPHONATE |
100 |
OP8 |
|
|
3228 |
|
|
AZODICARBONAMIDE FORMULATION TYPE B, TEMPERATURE CONTROLLED |
< 100 |
OP5 |
|
|
3232 |
(1) (2) |
|
AZODICARBONAMIDE FORMULATION TYPE C |
< 100 |
OP6 |
|
|
3224 |
(3) |
|
AZODICARBONAMIDE FORMULATION TYPE C, TEMPERATURE CONTROLLED |
< 100 |
OP6 |
|
|
3234 |
(4) |
|
AZODICARBONAMIDE FORMULATION TYPE D |
< 100 |
OP7 |
|
|
3226 |
(5) |
|
AZODICARBONAMIDE FORMULATION TYPE D, TEMPERATURE CONTROLLED |
< 100 |
OP7 |
|
|
3236 |
(6) |
|
2,2' -AZODI(2,4-DIMETHYL- 4-METHOXY- VALERONITRILE) |
100 |
OP7 |
-5 |
+5 |
3236 |
|
|
2,2' -AZODI(2,4-DIMETHYL- VALERONITRILE) |
100 |
OP7 |
+10 |
+15 |
3236 |
|
|
2,2' -AZODI(ETHYL- 2-METHYL-PROPIONATE) |
100 |
OP7 |
+20 |
+25 |
3235 |
|
|
1,1-AZODI(HEXAHYDROBENZONITRILE) |
100 |
OP7 |
|
|
3226 |
|
|
2,2' -AZODI(ISOBUTYRONITRILE) |
100 |
OP6 |
+40 |
+45 |
3234 |
|
|
2,2' -AZODI(ISOBUTYRONITRILE) as a water based paste |
50% |
OP6 |
|
|
3224 |
|
|
2,2' -AZODI(2-METHYLBUTYRONITRILE) |
100 |
OP7 |
+35 |
+40 |
3236 |
|
|
BENZENE-1,3-DISULPHONYL HYDRAZIDE, as a paste |
52 |
OP7 |
|
|
3226 |
|
|
BENZENE SULPHONYL HYDRAZIDE |
100 |
OP7 |
|
|
3226 |
|
|
4-(BENZYL(ETHYL)AMINO)-3-ETHOXY- BENZENEDIAZONIUM ZINC CHLORIDE |
100 |
OP7 |
|
|
3226 |
|
|
4-(BENZYL(METHYL)AMINO)-3-ETHOXY- BENZENEDIAZONIUM ZINC CHLORIDE |
100 |
OP7 |
+40 |
+45 |
3236 |
|
|
3-CHLORO-4-DIETHYLAMINOBENZENE- DIAZONIUM ZINC CHLORIDE |
100 |
OP7 |
|
|
3226 |
|
|
SELF-REACTIVE SUBSTANCE |
Concen- tration (%) |
Packing method |
Control tempera- ture (°C) |
Emergency tempera- ture (°C) |
UN generic entry |
Remarks |
|
2-DIAZO-1-NAPHTHOL-4-SULPHONYL CHLORIDE |
100 |
OP5 |
|
|
3222 |
(2) |
|
2-DIAZO-1-NAPHTHOL-5-SULPHONYL CHLORIDE |
100 |
OP5 |
|
|
3222 |
(2) |
|
2-DIAZO-1-NAPHTHOL SULPHONIC ACID ESTER MIXTURE, TYPE D |
< 100 |
OP7 |
|
|
3226 |
(9) |
|
2,5-DIBUTOXY-4-(4-MORPHOLINYL)- BENZENEDIAZONIUM, TETRACHLOROZINCATE (2:1) |
100 |
OP8 |
|
|
3228 |
|
|
2,5-DIETHOXY-4-MORPHOLINO- BENZENEDIAZONIUM ZINC CHLORIDE |
67-100 |
OP7 |
+35 |
+40 |
3236 |
|
|
2,5-DIETHOXY-4-MORPHOLINO- BENZENEDIAZONIUM ZINC CHLORIDE |
66 |
OP7 |
+40 |
+45 |
3236 |
|
|
2,5-DIETHOXY-4-MORPHOLINO- BENZENEDIAZONIUM TETRAFLUOROBORATE |
100 |
OP7 |
+30 |
+35 |
3236 |
|
|
2,5-DIETHOXY-4-(4-MORPHOLINYL)- BENZENEDIAZONIUM SULPHATE |
100 |
OP7 |
|
|
3226 |
|
|
2,5-DIETHOXY-4-(PHENYLSULPHONYL)- BENZENEDIAZONIUM ZINC CHLORIDE |
67 |
OP7 |
+40 |
+45 |
3236 |
|
|
DIETHYLENEGLYCOL BIS (ALLYL CARBONATE) + DI- ISOPROPYL-PEROXYDICARBONATE |
88+ 12 |
OP8 |
-10 |
0 |
3237 |
|
|
2,5-DIMETHOXY-4-(4-METHYL- PHENYLSULPHONYL)BENZENE- DIAZONIUM ZINC CHLORIDE |
79 |
OP7 |
+40 |
+45 |
3236 |
|
|
4-(DIMETHYLAMINO)-BENZENE-DIAZONIUM TRICHLOROZINCATE (-1) |
100 |
OP8 |
|
|
3228 |
|
|
4-DIMETHYLAMINO-6-(2-DIMETHYL- AMINOETHOXY) TOLUENE- 2-DIAZONIUM ZINC CHLORIDE |
100 |
OP7 |
+40 |
+45 |
3236 |
|
|
N,N'-DINITROSO-N,N'- DIMETHYL TEREPHTHALAMIDE, as a paste |
72 |
OP6 |
|
|
3224 |
|
|
N,N'-DINITROSOPENTAMETHYLENE- TETRAMINE |
82 |
OP6 |
|
|
3224 |
(7) |
|
DIPHENYLOXIDE-4,4'-DISULPHONYL HYDRAZIDE |
100 |
OP7 |
|
|
3226 |
|
|
4-DIPROPYLAMINOBENZENE- DIAZONIUM ZINC CHLORIDE |
100 |
OP7 |
|
|
3226 |
|
|
2-(N,N-ETHOXYCARBONYL- PHENYLAMINO)-3-METHOXY-4- (N-METHYL-N-CYCLOHEXYLAMINO) BENZENEDIAZONIUM ZINC CHLORIDE |
63-92 |
OP7 |
+ 40 |
+ 45 |
3236 |
|
|
2-(N,N-ETHOXYCARBONYL- PHENYLAMINO)-3-METHOXY-4- (N-METHYL-N-CYCLOHEXYLAMINO) BENZENEDIAZONIUM ZINC CHLORIDE |
62 |
OP7 |
+ 35 |
+ 40 |
3236 |
|
|
N-FORMYL-2-(NITROMETHYLENE) -1,3-PERHYDROTHIAZINE |
100 |
OP7 |
+45 |
+50 |
3236 |
|
|
2-(2-HYDROXYETHOXY)-1- (PYRROLIDIN-1-YL)BENZENE-4- DIAZONIUM ZINC CHLORIDE |
100 |
OP7 |
+ 45 |
+ 50 |
3236 |
|
|
3-(2-HYDROXYETHOXY)-4- (PYRROLIDIN-1-YL) BENZENE DIAZONIUM ZINC CHLORIDE |
100 |
OP7 |
+40 |
+45 |
3236 |
|
|
2-(N,N-METHYLAMINOETHYLCARBONYL)- 4-(3,4-DIMETHYLPHENYLSULPHONYL) BENZENEDIAZONIUM HYDROGEN SULPHATE |
96 |
OP7 |
+45 |
+50 |
3236 |
|
|
4-METHYLBENZENESULPHONYLHYDRAZIDE |
100 |
OP7 |
|
|
3226 |
|
|
SELF-REACTIVE SUBSTANCE |
Concen- tration (%) |
Packing method |
Control tempera- ture (°C) |
Emergency tempera- ture (°C) |
UN generic entry |
Remarks |
|
3-METHYL-4-(PYRROLIDIN-1-YL) BENZENEDIAZONIUM TETRAFLUOROBORATE |
95 |
OP6 |
+45 |
+50 |
3234 |
|
|
4-NITROSOPHENOL |
100 |
OP7 |
+35 |
+40 |
3236 |
|
|
PHOSPHOROTHIOIC ACID, O-[(CYANOPHENYL METHYLENE) AZANYL] O,O-DIETHYL ESTER |
82-91 (Z isomer) |
OP8 |
|
|
3227 |
(10) |
|
SELF-REACTIVE LIQUID, SAMPLE |
|
OP2 |
|
|
3223 |
(8) |
|
SELF-REACTIVE LIQUID, SAMPLE, TEMPERATURE CONTROLLED |
|
OP2 |
|
|
3233 |
(8) |
|
SELF-REACTIVE SOLID, SAMPLE |
|
OP2 |
|
|
3224 |
(8) |
|
SELF-REACTIVE SOLID, SAMPLE, TEMPERATURE CONTROLLED |
|
OP2 |
|
|
3234 |
(8) |
|
SODIUM 2-DIAZO-1-NAPHTHOL- 4-SULPHONATE |
100 |
OP7 |
|
|
3226 |
|
|
SODIUM 2-DIAZO-1-NAPHTHOL- 5-SULPHONATE |
100 |
OP7 |
|
|
3226 |
|
|
TETRAMINE PALLADIUM (II) NITRATE |
100 |
OP6 |
+30 |
+35 |
3234 |
|
Remarks
(1) Azodicarbonamide formulations which fulfil the criteria of paragraph 20.4.2 (b) of the Manual of Tests and Criteria. The control and emergency temperatures shall be determined by the procedure given in 7.1.7.3.1 to 7.1.7.3.6.
(2) "EXPLOSIVE" subsidiary hazard label required (Model No. 1, see 5.2.2.2.2).
(3) Azodicarbonamide formulations which fulfil the criteria of paragraph 20.4.2 (c) of the Manual of Tests and Criteria.
(4) Azodicarbonamide formulations which fulfil the criteria of paragraph 20.4.2 (c) of the Manual of Tests and Criteria. The control and emergency temperatures shall be determined by the procedure given in 7.1.7.3.1 to 7.1.7.3.6.
(5) Azodicarbonamide formulations which fulfil the criteria of paragraph 20.4.2 (d) of the Manual of Tests and Criteria.
(6) Azodicarbonamide formulations which fulfil the criteria of paragraph 20.4.2 (d) of the Manual of Tests and Criteria. The control and emergency temperatures shall be determined by the procedure given in 7.1.7.3.1 to 7.1.7.3.6.
(7) With a compatible diluent having a boiling point of not less than 150 °C.
(8) See 2.2.41.1.15.
(9) This entry applies to mixtures of esters of 2-diazo-1-naphthol-4-sulphonic acid and 2-diazo-1-naphthol-5-sulphonic acid which fulfil the criteria of paragraph 20.4.2 (d) of the Manual of Test and Criteria.
(10) This entry applies to the technical mixture in n-butanol within the specified concentration limits of the (Z) isomer.