☣️ UN 3222 • CLASS 4

UN 3222 — Self-reactive solid type B

Placard: Flammable Solid. ERG Guide 149. Training/quick-reference only — use current ERG + SOP/SOG for incident-specific actions.

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⚠️ This page is a quick-reference aid. For real incidents: stage upwind, isolate, deny entry, request Hazmat early, and consult the current ERG + SOP/SOG.

UN 3222 is Self-reactive solid type B, a thermally unstable self-reactive material. The response depends on type, package size and temperature-control data.

Hazard overview: Self-reactive substances can decompose without external oxygen. Heat, contamination or loss of temperature control can lead to rapid pressure rise, fire or explosion.

Response guidance: Isolate the area, keep people away from container ends and control temperature if safe. Use ERG 149, SDS and shipping papers to confirm SADT, emergency temperature and compatible extinguishing methods.

Firefighter training notes: Train responders to recognize self-reactive materials, SADT concerns, temperature control needs and explosive decomposition risk under fire exposure.

Regulatory context: Self-reactive substances are regulated by type and temperature-control requirements; verify classification, control temperature and emergency control temperature where listed.

Storage & handling: Store under specified temperature limits, away from heat, sunlight, contamination and incompatible chemicals. Verify stabilization and emergency temperature controls.

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UN 3222 Quick Details

UN 3222
Product name: Self-reactive solid type B
DOT Class: 4
Placard type: Flammable Solid
ERG Guide: 149 (check current ERG)
Initial isolation: ERG 149: isolate spill 25-50m all directions; for fire isolate 800m all directions and evacuate 800m in all directions; consider evacuation of 1600m downwind if tank/rail car involved in fire

Common Hazards of UN 3222

  • Self-reactive material can undergo self-accelerating decomposition if heated or contaminated.
  • May burn violently and produce large amounts of heat, smoke or gas.
  • Containers may rupture, vent or explode when decomposition begins.
  • Vapors, dust or decomposition products may be toxic or irritating.
  • Fire, friction, impact or incompatible chemicals can trigger decomposition.
  • Some formulations require temperature control; verify SADT and emergency temperature data.
  • Exact formulation and inhibitor/stabilizer status must be confirmed before response.

Chemical Identity & Physical Properties

Solid material at room temperature, typically white to off-white or colored powder or granular form. May be odorless or have characteristic chemical odor depending on specific compound. Requires temperature control during transport.

Also known asSelf-reactive solid type BOrganic peroxide type solidTemperature-controlled self-reactive substanceThermally unstable organic solid
AppearanceSolid material at room temperature, typically white to off-white or colored powder or granular form. May be odorless or have characteristic chemical odor depending on specific compound. Requires temperature control during transport.
Flash PointNot applicable (self-reactive solid)
Boiling PointNot applicable (decomposes before boiling)
Vapor DensityNot applicable (solid)
Water ReactivityGenerally no violent water reaction, but water may accelerate decomposition in some cases
Chemical details are general reference only. Always verify with current SDS, ERG, and SOP/SOG.

Fireground Response Guidance — UN 3222

Extinguishing Media

Dry chemical, CO2, sand, or inert materials; avoid water spray on bulk material

PPE Requirements

⚠️ Level B minimum for spills; SCBA and full protective clothing required for fire involvement; respiratory protection mandatory

Use SCBA and protective clothing. For active decomposition, fire involvement or unknown formulation, use remote operations and specialist hazmat support rather than close entry.

Isolation & Evacuation

ERG 149: isolate spill 25-50m all directions; for fire isolate 800m all directions and evacuate 800m in all directions; consider evacuation of 1600m downwind if tank/rail car involved in fire
Always confirm protective actions with the current edition of the Emergency Response Guidebook (ERG Guide 149).

First Actions for a UN 3222 Incident

  • Call 911 and the emergency response number on the shipping paper, if available.
  • Keep unauthorized personnel away and establish incident command before close approach.
  • Stay upwind, uphill and upstream; avoid low areas where vapors or gases may collect.
  • Avoid breathing vapors, dust, smoke or decomposition products and avoid skin or eye contact.
  • Do not touch damaged containers or spilled material without appropriate PPE and monitoring.
  • Ventilate confined spaces only if trained, equipped and authorized by incident command.
  • Use ERG, SDS, shipping papers and atmospheric/radiation monitoring for final isolation and control decisions.
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📋 Copy & Share Field Card

UN 3222 — Self-reactive solid type B
HAZMAT RADIO NOTE — UN 3222 Product: Self-reactive solid type B Class 4 / Flammable Solid / ERG 149 PPE: Level B minimum for spills; SCBA and full protective clothing required for fire involvement; respiratory protection mandatory ISOLATION: ERG 149: isolate spill 25-50m all directions; for fire isolate 800m all directions and evacuate 800m in all directions; consider evacuation of 1600m downwind if tank/rail car involved in fire ACTION: Stage upwind · Isolate · Deny entry · Request HazmatRADIO

Use for: Quick radio or face-to-face size-up. Short, structured, field-ready.

SMS WhatsApp
=== IC HAZMAT BRIEFING === UN 3222 — Self-reactive solid type B Class: 4 | Placard: Flammable Solid | ERG Guide: 149 Appearance: Solid material at room temperature, typically white to off-white or colored powder or granular form. May be odorless or have characteristic chemical odor depending on specific compound. Requires temperature control during transport. Water Reactivity: Generally no violent water reaction, but water may accelerate decomposition in some cases Extinguishing: Dry chemical, CO2, sand, or inert materials; avoid water spray on bulk material PPE: Level B minimum for spills; SCBA and full protective clothing required for fire involvement; respiratory protection mandatory Isolation: ERG 149: isolate spill 25-50m all directions; for fire isolate 800m all directions and evacuate 800m in all directions; consider evacuation of 1600m downwind if tank/rail car involved in fire — Key Hazards — • Self-reactive material can undergo self-accelerating decomposition if heated or contaminated. • May burn violently and produce large amounts of heat, smoke or gas. • Containers may rupture, vent or explode when decomposition begins. — First Actions — • Call 911 and the emergency response number on the shipping paper, if available. • Keep unauthorized personnel away and establish incident command before close approach. • Stay upwind, uphill and upstream; avoid low areas where vapors or gases may collect. • Avoid breathing vapors, dust, smoke or decomposition products and avoid skin or eye contact. SOURCE: allfirefighter.com/hazmat/un/self-reactive-solid-type-un-3222 | Always use current ERG + SOP/SOGIC BRIEFING

Use for: Incident command briefing, staging area whiteboard, or pre-entry team brief.

SMS (short)
UN3222 Self-reactive solid type B Cls4 ERG149 | allfirefighter.com/hazmat/un/self-reactive-solid-type-un-3222SMS / 160 CHAR

Use for: Quick text to command or incoming units. Fits in a single SMS.

⚠️ Quick-reference only. Always use current ERG + SOP/SOG for incident-specific actions. Page: https://allfirefighter.com/hazmat/un/self-reactive-solid-type-un-3222

Related UN Numbers in Class 4

Discovery block for training / quick reference. Always consult the current ERG + your SOP/SOG for operations.
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Frequently Asked Questions about UN 3222

UN 3222 is Self-reactive solid type B. It should be treated according to ERG 149 and the exact shipping papers or SDS.

It can self-decompose or self-ignite when heated, contaminated or destabilized.

Heat may increase pressure, worsen decomposition, release toxic or irritating gases, or intensify fire depending on the material.

Use positive-pressure SCBA and chemical-resistant protective clothing suitable for the product. Upgrade protection when the identity, concentration or release size is uncertain.

Some self-reactive materials have a self-accelerating decomposition temperature. Exceeding it can cause rapid decomposition and pressure buildup.
Sources (high level): DOT/PHMSA marking & class concepts + ERG usage principles. This page does not reproduce ERG guide text—always consult the current ERG for incident-specific protective actions.