Exploring Hazardous Chemical Reactions

(What you don’t want to happen at your removal)By Doug Ferguson and Megan Schuette

Objectives

Learn the general classes of hazmat Determine a material’s hazmat class Use tools to avoid hazardous reactions Apply tools in a removal scenario

Welcome to your site!Welcome to your site!

How do we safely and efficiently dispose of all of this?

What types of hazardous materials? How much of each type?

Are the containers in a stable condition? How do we segregate them? Do we treat or transport?

What types of hazardous materials?

• Class 1 Explosives• Class 2 Gasses• Class 3 Flammable

Liquids• Class 4 Flammable

Solids

• Class 5 Oxidizers• Class 6 Toxics • Class 7 Radioactive

Material• Class 8 Corrosives• Class 9 Miscellaneous

(Use DOT classes for simplicity)

DOT Hazard Classes Review

EXPLOSIVES

CLASS 1: EXPLOSIVES

1.1 Explosives with mass explosion hazard1.2 Explosives with a projection hazard1.3 Explosives with predominantly a fire hazard1.4 Explosives with no significant blast hazard1.5 Very insensitive explosives; blasting agents1.6 Extremely insensitive detonating articles

Explosives (Class 1) Placards

Non-Flammable Gas

Gases

CLASS 2: GASES

2.1 Flammable gases (LEL less than 13% or flammable range of at least 12%)

2.2 Non-flammable, non-toxic compressed gases (LC50 greater than 5000 ml/m3)

2.3 Gases toxic by inhalation (LC50 less than 5000 ml/m3)

Gases (Class 2) Placards

FLAMMABLE GASES

CLASS 3: FLAMMABLE & COMBUSTIBLE LIQUIDS

Flammable Liquid = flash point between 100oF and 141oF

Combustible Liquid = flash point above 141oF and below 200oF

CLASS 4: FLAMMABLE SOLID

4.1 Flammable solids-desensitized explosives, self-reactive materials, or may cause fire by friction (matches)

4.2 Spontaneously combustible materials-can self ignite when exposed to air for less than 5 minutes (yellow phosphorous) or self-heats above 200oF over a 24-hr period

4.3 Dangerous when wet materials-gives off flammable or toxic gas faster than 1L/kg/hr

Flammable Solid (Class 4) Placards

Water Reactive

CLASS 5: OXIDIZERS AND ORGANIC PEROXIDES

5.1 Oxidizers-a material that may, generally by yielding oxygen, cause or

enhance the combustion of other materials

5.2 Organic peroxides-an organic compound containing the bivalent R-O-

O-R structure

CLASS 5: OXIDIZERS AND ORGANIC PEROXIDES

CLASS 6: TOXIC MATERIALS & INFECTIOUS SUBSTANCES

6.1 Toxic = A liquid with oral LD50 of 500mg/kg or lower and solids with oral LD50 less than 200 mg/kg. Also, dermal LD50 of less than 1000 mg/kg. Finally, a dust with LC50 less

than 10 mg/L.6.2 Infectious = A viable microorganism, or its

toxin, that causes or may cause disease in humans or animals.

Poisonous & Infectious Substances (Class 6) Placards

CLASS 7: RADIOACTIVE MATERIALS

Radioactive = Specific reactivity is greater than 70 Bq per gram (0.002 microcurie

per gram)

CLASS 8: CORROSIVE MATERIALS

Corrosive = a liquid or solid that causes full thickness destruction of human skin at the site of contact with in 14 days or exhibit a corrosion rate on steel or aluminum exceeding 1/4 inch per year

pH of Common Items14.0 Strong Bases: NaOH, KOH, Ca(OH)2

12.5 RCRA haz. wasteBASIC 12.0 Household ammonia

10.0 Detergents and Baking Soda8.0 Seawater

7.4 BloodNEUTRAL 7.0 Pure water

6.0 Rain4.0 Beer3.0 Orange juice, vinegar, wine, acid rain

ACIDIC 2.0 RCRA haz. waste/lemon juice, stomach acid1.0 Strong acids: HCl, HF, HI, H2SO4, HNO3

0.0 Very acidic

CLASS 9: MISCELLANEOUS HAZARDOUS MATERIAL

Presents a hazard during transportation but doesn’t meet any of the definitions of the other

hazard classes (e.g. anesthetic, noxious) Elevated temperature material (liquids being

shipped at or above 212oF, liquid heated above its flash point while transported or solids

above 464oF.

Miscellaneous Hazardous Materials (Class 9) Placards

Mixed Load Placards

When the total weight of two or more Table II materials is 1,001 lbs. or more Table II Includes classes: 1.4, 1.5, 1.6,

2.1, 2.2, 3, 4.1, 4.2, 5.1, 5.2, 6.1, 8 & 9

DEMONSTRATIONS

How do you know what hazards?

Placards/label Shipping Papers Chemical Testing Devices Field Screening Tests

Use References

ERG NIOSH WISER MSDS

Compatibility Charts

DOT Etc. (see handouts)

Things to NOT mix!

Acids and Bases Fuels (organics) and

Oxidizers/Peroxide Metals and Acids Water Reactive and

anything containing Water

Metals and Oxidizers/Peroxide

Cyanides/Phosphides/ Hydrides/Sulfides with Water or Acids

Energy and Explosives

How do I know what it is? Field Screen

Acids H followed by non-metal (left side of

periodic table) Bases begin with metal

and end in OH Oxidizers/Peroxide end

in at least 2 oxygens/halogens

Metals on left side of periodic table

Water reactive metals in first column of periodic

table. Cyanide = end in CN Hydride = end in H Sulfide =end in S Phosphide =end in P Fuels have carbon (C) Explosives generally

contain nitrogen(N)

The Periodic Tablemetals

non-metalsnoble gases

1 2

3 4 5 6 7 8 9 10

11

1

H He

B C N O F Ne13

Al14

Si15

P16

S17

Cl18

Ar

H

Li Be

Na Mg

K Ca19 20

12

37

Rb38

Sr

Cs55

Ba56 57

La

58

Ce59

Pr60

Nd61

Pm62

Sm63

Eu64

Gd65

Tb66

Dy67

Ho68

Er69

Tm70

Yb71

Lu

87

Fr88

Ra89

Ac

90

Th91

Pa92

U93

Np94

Pu95

Am100

Fm101

Md102

No103

Lr96

Cm97

Bk98

Cf99

Es

21

Sc22Ti

23

V24

Cr25

Mn26

Fe27

Co28Ni

29

Cu30

Zn31

Ga32

Ge33

As34

Se35

Br36Kr

39

Y40

Zr41

Nb42

Mo43

Tc44

Ru45

Rh46

Pd47

Ag48

Cd49

In50

Sn51

Sb52

Te53

I54

Xe72

Hf73

Ta74

W75

Re76

Os77

Ir78

Pt79

Au80

Hg81

Tl82

Pb83

Bi84

Po85

At86

Rn104

Rf105

Db106

Sg107

Bh108

Hs109

Mt

1.008

6.941

22.9897

39.0983

85.4678

132.905

(223)

9.012

24.3050

40.078

87.62

137.327

(226)

44.9559

88.9058

138.90

(227)

47.867

91.224

178.49

(261)

50.9415

92.906

180.947

(262)

51.9961

95.94

183.84

(263)

54.938

(98)

186.207

55.845

101.07

190.23

58.9332

102.905

192.217

58.6934

106.42

195.078

63.546

107.868

196.966

65.39

112.411

200.59

10.811

26.9815

69.723

114.818

204.383

12.0107

28.0855

72.61

118.710

207.2

14.00

30.9737

74.921

121.760

208.980

15.9994

32.066

78.96

127.60

(209)

18.9984

35.4527

79.904

126.904

(210)

4.0026

20.1797

39.948

83.80

131.29

(222)

1.007

140.116

232.0381

140.90765

231.03588

144.24

238.0289

(145)

(237)

150.36

(244)

151.964

(243)

157.25

(247)

158.92534

(247)

162.50

(251)

164.93032

(252)

167.26

(257)

168.93421

(258)

173.04

(259)

174.967

(262)

(262) (265) (266)

Chem Fam

Oxidizers

-ClO3-NO3

Fire Gases

SOX NOX

Organic

peroxides

RCRA/DOT Storage/Segregation

Not as concerned with packaging as materials are stored Use segregation chart form DOT where “X”

or “O” means you should separate them Also, separate acids from bases Information on MSDS sheets or label may

list specific incompatibilities to follow Use field screening chart for unknowns

Segregation (DOT)

Notes: O = Must have a separation between the materials

X = Must not be shipped in the same vehicle

* = See Compatibility Table for Class 1 (Explosive) Materials

A = Ammonium Nitrate and ammonium nitrate fertilizer may be loaded or stored with Division 1.1 or 1.5 materials

Other Hazard Considerations Auto ignition Organic compounds

(hydrocarbon) BLEVE Decomposition Polymerization Cryogens Hot

Applications

Work several scenarios

Example Reactions at Sites

Treatment or Disposal

Combine similar waste streams (bulking) for disposal

On-site treatment (reacting or neutralizing)

Bulking/Treatment Considerations

Cost/Benefit Analysis Hazardous Reactions—heat, gas

(toxic, oxidizing, flammable) evolved, fire, explosion Changing site conditions (temp,

moisture, pressure—vacuum pump) Bench scale compatibility tests