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54User Guide for Thresholds and Classificationsb. where it is likely or known that more than 10% of the mass of the substance will crumble into a finerparticle form, then that finer form.The degree to which these self-reactive substances will heat up internally depends on the:surface to volume ratio of the quantity of substance presented; andnature (for example, the thermal conductivity) of the container or package it is in.Accordingly, the test procedures described in the UN Manual of Tests and Criteria are directly referred to forthis threshold.The heat of decomposition can be determined using any internationally recognised method, such asdifferential scanning calorimetry or adiabatic calorimetry. In using such techniques, special care should betaken in interpreting the results when:sampling and testing mixtures;the material of the sample vessel may influence the result;endotherms immediately precede exotherms;evaporation of constituents will lower the exothermicity;the presence of air may critically affect the measured decomposition energy;there is a large difference between the specific heats of the reactants and products; andusing rapid heating rates.Screening procedures for substances that may be self-reactive substancesA substance does not need to be evaluated as a self-reactive substance if no chemical groups present in themolecule are associated with explosive or self-heating properties. Examples of the former are groups suchas C-C unsaturation, C-metal, N-metal, N-N unsaturation, peroxides, N-O, N-halogen, O-halogen. Examplesof the latter are groups such as mutually reactive groups (for example, aminonitriles, haloanilines, andorganic salts of oxidising acids), S=O, P-O, strained rings, and unsaturation.6.2.3. Classification criteria for self-reactive flammable solids subclass 4.1.2 (equivalent toUN division 4.1(b))There are seven classification categories to subclass 4.1.2, self-reactive flammable solids, which relate tothe degree of hazard that the substances present. The criteria for inclusion in these categories are asfollows. (See also the tables in Appendix 6A.)Subclass 4.1.2A – self-reactive flammable solid category A (equivalent to UN Type A)a. The substance:i. is a self-reactive flammable solid;ii.propagates a detonation as defined in UN Test Series A (see ‗Definitions‘ in section 6.2.4 for anexplanation of ‗as defined in UN Test Series‘); andiii. propagates a detonation in confined conditions as specified in UN Test Series B.b. The substance:i. is a self-reactive flammable solid;January 2012 EPA0109
55User Guide for Thresholds and Classificationsii. propagates a detonation as defined in UN Test Series A;iii. does not propagate a detonation in confined conditions as defined in UN Test Series B;iv. propagates a rapid deflagration as defined in UN Test Series C; andv. propagates a rapid deflagration in confined conditions as defined in UN Test Series D.c. The substance:i. is a self-reactive flammable solid;ii. propagates a partial detonation as defined in UN Test Series A;iii. propagates a rapid deflagration as defined in UN Test Series C; andiv. propagates a rapid deflagration under confined conditions as defined in UN Test Series D.d. The substance:i. is a self-reactive flammable solid;ii. does not propagate a detonation as defined in UN Test Series A;iii. propagates a rapid deflagration as defined in UN Test Series C; andiv. propagates a rapid deflagration when ignited under confinement as defined in UN Test SeriesD.Subclass 4.1.2B – self-reactive flammable solid category B (equivalent to UN Type B)a. The substance is listed in the UN Model Regulations as having a classification of a self-reactiveflammable solid division 4.1 of Type B.b. The substance:i. is a self-reactive flammable solid;ii. propagates a detonation as defined in UN Test Series A;iii. does not propagate a detonation under confined conditions as defined in UN Test Series B;iv. propagates a rapid deflagration as defined in UN Test Series C;v. does not propagate a rapid deflagration under confined conditions as defined in UN Test SeriesD;vi. exhibits violent effect when heated under confinement as defined in UN Test Series E; andvii. undergoes a thermal explosion under confined conditions as defined in UN Test Series G.c. The substance:i. is a self-reactive flammable solid;ii. propagates a detonation as defined in UN Test Series A;iii. does not propagate a detonation under confinement as defined in UN Test Series B;iv. propagates a slow deflagration or does not propagate a deflagration as defined in UN TestSeries C;iv. displays violent effect when heated under confinement as defined in UN Test Series E; andv. undergoes a thermal explosion under confinement as defined in UN Test Series G.d. The substance:i. is a self-reactive flammable solid;January 2012 EPA0109
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