2.2.41.1.17

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.

2.2.41.1.18

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.

2.2.41.1.19

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.

2.2.41.1.20

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.

2.2.41.1.21

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.

2.2.41.2

Substances not accepted for carriage

2.2.41.2.1

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.

2.2.41.2.2

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).

2.2.41.2.3

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.

2.2.41.3

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.

2.2.41.4

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.

2.2.42

Class 4.2 Substances liable to spontaneous combustion

2.2.42.1

Criteria

2.2.42.1.1

The heading of Class 4.2 covers:

-Pyrophoric substanceswhich are substances, including mixtures and solutions (liquid or solid),which even in small quantities ignite on contact with air within five minutes. These are theClass4.2 substances the most liable to spontaneous combustion; and

-Self-heating substances and articleswhich are substances and articles, including mixtures andsolutions, which, on contact with air, without energy supply, are liable to self-heating. Thesesubstances will ignite only in large amounts (kilograms) and after long periods of time (hoursor days).

2.2.42.1.2

The substances and articles of Class 4.2 are subdivided as follows:

S Substances liable to spontaneous combustion, without subsidiary hazard:

S1 Organic, liquid;

S2 Organic, solid;

S3 Inorganic, liquid;

S4 Inorganic, solid;

S5 Organometallic;

S6 Articles

SW Substances liable to spontaneous combustion, which, in contact with water, emit flammable gases;

SO Substances liable to spontaneous combustion, oxidizing;

ST Substances liable to spontaneous combustion, toxic:

ST1 Organic, toxic, liquid;

ST2 Organic, toxic, solid;

ST3 Inorganic, toxic, liquid;

ST4 Inorganic, toxic, solid;

SC Substances liable to spontaneous combustion, corrosive:

SC1 Organic, corrosive, liquid;

SC2 Organic, corrosive, solid;

SC3 Inorganic, corrosive, liquid;

SC4 Inorganic, corrosive, solid.

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