Properties of

Hazardous
Mixtures

N. Sanei
October 2017
Properties of Hazardous Mixtures

 The Triangle

Oxygen

Ignition Flammable
Source Material
Properties of Hazardous Mixtures

 Conventional Ignition Source

Flammable Vapor/
Flashing Liquid/ Dust

Spark/ Ignition Source

Properties of Hazardous Mixtures

 Auto-Ignition Temperature

Leaking Liquid/
Flammable Vapor

HOT
SURFACE
Properties of Hazardous Mixtures

 Liquid Fuels – Definitions

Flash Point:
Lowest temperature, at which a flammable liquid gives off
enough vapor to form an ignitable mixture with air:
“a surface phenomenon”;

Flammable Liquids (NFPA):

Liquids with a flash point < 100°F
(NFPA: Class IA, IB, IC)

Combustible Liquids (NFPA):

Liquids with a flash point  100°F
(NFPA: Class II, Class III)
Properties of Hazardous Mixtures

 Flash point – Illustrations

Ignition can only occur when the material is in the vapor
state, liquids cannot burn;
Properties of Hazardous Mixtures

 Liquid Fuels – Definitions

Boiling point:
Temperature, at which the vapor pressure of the liquid
equals the surrounding atmospheric pressure;

Boiling is a volume phenomenon;

Not a factor in Hazardous Area Classification;

Properties of Hazardous Mixtures

 NFPA Definition, Class I Flammable Liquid

Any liquids with a flash point < 37.8°C (100°F):

- When released at ambient temperature, will readily

evaporates and forms a gas-vapor mixture;

- Tends to disperse rapidly to below their LEL;

- Behave like heavier than air gases;

Properties of Hazardous Mixtures

 NFPA, Flammable Liquids Classification

Properties of Hazardous Mixtures

 NFPA, Combustible Liquids Classification

Properties of Hazardous Mixtures

 NFPA, Liquid Classification Overview

200
IIIA
Combustible
140
Flash Point (oF)

(FP > 100oF)

II
100
IC Flammable
73
(FP < 100oF)
IA IB

100

Boiling Point (oF)

Properties of Hazardous Mixtures

 Chemical Management in the EU

EU regulations on Chemicals is based on two main pillars:

- REACH:
The Regulation (EC) No 1907/2006 of the European
Parliament and of the Council of 18 December 2006
concerning the Registration, Evaluation, Authorization
and Restriction of Chemicals, (came into force on June
1st 2007);
- CLP:
The Regulation (EC) No 1272/2008 on the Classification,
Labeling and Packaging of substances and mixtures,
introducing the United Nations globally harmonized
system (UN GHS) for classification and labeling of
chemicals into Europe (entered into force on 20th
January 2009);
Properties of Hazardous Mixtures

 Chemical Management in the EU (cont’d)

Both CLP and REACH are “Chemical Hazards Management &
Communication” tools:

♨ CLP
Applies to all substances irrespective of the annual usage;
Internationally agreed classification criteria (UN GHS) and
labelling elements are used for classification, labelling and
packaging of chemicals, i.e. the same hazards will be described and
labelled in the same way all around the world resulting in ease of
trade/ contributing towards global efforts to protect humans and
the environment from hazardous effects of chemicals;
 Physical hazards (H200 series);
 Health hazards (H300 series);
 Environmental hazards (H400 series);
 EUH Series (Supplemental Hazard Information);
Properties of Hazardous Mixtures

 Chemical Management in the EU (cont’d)

Other non-EU countries have started implementing the
GHS into their domestic law, e.g. the US, Canada, New
Zealand, Brazil, China, Russia, Japan, Mexico, South Africa,
etc.;
Properties of Hazardous Mixtures

 Chemical Management in the EU (cont’d)

And concerning health hazards:
Properties of Hazardous Mixtures

 Chemical Management in the EU (cont’d)

Both CLP and REACH are “Chemical Hazards Management &
Communication” tools:

♨ REACH
Provides procedures and criteria for safe use of chemicals, in
particular for manufacturers and importers (in the EU), but it
cover the whole supply chain, i.e. the manufacturers, the
distributers/ traders, the importers and the end-users;

REACH is applicable on all chemicals which are supposed to be put

on the market with an annual tonnage of more than 1 tone;

The main focus of the REACH is on the proper communication of

chemical hazards along the supply chain in an interactive way
through SDS (Safety Data Sheet);
Properties of Hazardous Mixtures

 Chemical Management in the EU (cont’d)

There is a clear link among SEVESO III, CLP and REACH,
with a clearly defined roles & responsibilities for each
single party involved in the chemical supply chain & the
associated authorities (both EU level and local):
Properties of Hazardous Mixtures

 Gaseous/ Vapor Mixtures – Definitions

Flammable/ Explosive Limits
Range of composition of material in air, which will burn:
UFL – Upper Flammable Limit
LFL – Lower Flammable Limit
UEL – Higher Explosive Limit
LEL – Lower Explosive Limit

See for further details:

www.gexcon.com//handbook/GEXHBcontents.htm

Measuring These Limits for Vapor-Air Mixtures

Known concentrations are placed in a closed vessel
apparatus and then ignition is attempted;
Properties of Hazardous Mixtures

 Differences, LEL/ LFL, UEL/ UFL

There is a quantitative difference between flammability
limits and explosive limits;
In an explosive mixture the fuel oxidizer mixture is closer
to stoichiometric proportion, but this difference has no
practical application in safety engineering as the flammable
vapor cloud is turbulent and the exact mixture of fuel and
oxidizer varies greatly;
Therefore, many references use the term flammability
limit (LFL, UFL) and explosive limit (LEL, UEL)
interchangeably;
Hydrogen: 30 (vol.%) Stoichiometric Conc.
4/ 75 (vol.%) LFL/ UFL
15/ 59 (vol.%) LEL/ UEL
Properties of Hazardous Mixtures

 Graphical Explanation of LFL and UFL

100 %
Flamm. vapor
Concentration Too Rich to Burn
(% by volume)

UFL

Flammable Range
LFL

Too Lean to Burn

0%
Properties of Hazardous Mixtures

 LEL and UEL for Selected Materials

Properties of Hazardous Mixtures

 Flammable/ Explosive Limits

Flammable Limits Change With:

 Temperature;
 Pressure;
 Inerts existing;
Properties of Hazardous Mixtures

 Effect of Temperature on LEL

Properties of Hazardous Mixtures

 Effect of Temperature on UEL (C2H6-Air)

Properties of Hazardous Mixtures

 Effect of Pressure on LEL & UEL

Natural Gas, volume %

UEL

Natural Gas in Air at 28 °C

LEL

Initial Pressure, Atm.

Properties of Hazardous Mixtures

 Effect of Pressure on UEL (C3H8–Air)

Properties of Hazardous Mixtures

 Minimum Ignition Energy

Lowest amount of energy required for ignition, dependent
on:

 Temperature;
 Concentration of the combustible;
 Type of compound;
Properties of Hazardous Mixtures

 Minimum Ignition Energy

Effects of Stoichiometry
Properties of Hazardous Mixtures

 Auto-Ignition Temperature (AIT)

The lowest temperature of a heat surface, at which, under
specified conditions, the ignition of a flammable substance
in the form of a gas or vapor mixture with air will occur;
API RP 505, IEC 79-10 – Mod

The minimum temperature required to initiate or cause

self-sustained combustion of a solid, liquid or gas
independently of a heated or heating element;
NFPA 497

Difficult to estimate – Must be determined experimentally;

Properties of Hazardous Mixtures

 Flammability Relationships
CONCENTRATION OF FUEL

Auto
Ignition
FLAMMABLE REGION
FLAMMABLE REGION
MIST

AIT
Flash Point TEMPERATURE
AIT
Properties of Hazardous Mixtures

 Factors affecting AIT

 Molecular structure of the hydrocarbon mixture;
 Concentration,
% composition of the vapor in air mixture;
 Hot surface material,
Type and reactivity of other materials present;
 Rate and duration of heating;
 Environmental Conditions,
Initial temperature and the atmospheric pressure;
Properties of Hazardous Mixtures

 AIT, Examples

Material Variation Autoignition

Temperature
Pentane in air 1.50% 1018 °F
3.75% 936 °F
7.65% 889 °F
Benzene Iron flask 1252 °F
Quartz flask 1060 °F
Carbon disulfide 200 ml flask 248 °F
1000 ml flask 230 °F
10000 ml flask 205 °F
Properties of Hazardous Mixtures

 Adiabatic Compression
Fuel and air will ignite if the vapors are compressed to an
adiabatic temperature that exceeds the autoignition
temperature;

Adiabatic Compression Ignition (ACI);

Diesel engines operate on this principle; pre-ignition

knocking in gasoline engines;

E.g. flammable vapors sucked into compressors;

Properties of Hazardous Mixtures

 More Definitions
Fire
A slow form of deflagration;

Deflagration
Propagating reactions, in which the energy transfer from
the reaction zone to the unreacted zone is accomplished
through ordinary transport processes such as heat and
mass transfer;

Detonation/ Explosion
Propagating reactions, in which energy is transferred from
the reaction zone to the unreacted zone on a reactive shock
wave having a velocity higher than the sonic velocity in the
reactant;
Properties of Hazardous Mixtures

 Two Special Cases

There are two special phenomena, to which special attention
shall be paid:

 Unconfined Vapor Cloud Explosion (UVCE);

 Boiling Liquid Expanding Vapor Explosion (BLEVE);
Properties of Hazardous Mixtures

 Unconfined Vapor Cloud Explosion (UVCE)

An overpressure caused when a gas cloud detonates or
deflagrates in open air rather than simply burns;
Steps by a vapor cloud:
 Cloud will spread from too rich, through flammable
range to too lean;
 Edges start to burn through deflagration (steady state
combustion);
 Cloud will disperse through natural convection;
 Flame velocity will increase with containment and
turbulence;
 If velocity is high enough, cloud will detonate;
 If cloud is small enough with little confinement it
cannot explode;
Properties of Hazardous Mixtures

 What Favors High Overpressures?

Following factors favor high overpressures:

 Confinement: Prevents escape, increases turbulence;

 Cloud composition: Unsaturated molecules (e.g. all
ethylene clouds explode), low ignition energies, high
flame speeds;
 Good weather: Stable atmospheres, low wind speeds;
 Large Vapor Clouds: Higher probability of finding
ignition source, more likely to generate overpressure;
 Source: Flashing liquids, high pressures, large, low or
downward facing leaks;
Properties of Hazardous Mixtures

 Impact of a VCE on People

Peak Equivalent Wind Effects

Overpressure (psi) Velocity (mph)
1 Knock personnel down
2 70
5 160 Rupture eardrums
10 290
15 Damage lungs
20 470
30 670
35 Threshold fatalities
50 940 50% fatalities
65 99% fatalities
Properties of Hazardous Mixtures

 Impact of a VCE on Facilities

Peak Typical Damages

Overpressure (psi)
0.5 – 1 Glass windows break
1 –2 Common siding types fail:
- corrugated asbestos shatters;
- corrugated steel panel joints fail;
- wood siding blows in;
2 –3 Unreinforced concrete, block walls fail;
3 –5 Self-framed steel panel buildings
collapse, Oil storage tanks rupture;
7 Loaded rail cars overturn;

7 –8 Unreinforced brick walls fail;

Properties of Hazardous Mixtures

 UVCE vs. TNT

World of explosives is dominated by TNT impact which is
understood:

 Vapor clouds, by analysis of incidents, seem to respond

like TNT if we can determine the equivalent TNT;
 1 pound of TNT has a LHV of 1890 BTU;
 1 pound of hydrocarbon has a LHV of about
19000 BTU;
 A vapor cloud with a 10% efficiency will respond like a
similar weight of TNT;
Properties of Hazardous Mixtures

 Boiling Liquid Expanding Vapor Explosion

(BLEVE)
The result of a vessel failure in a fire and release of a
pressurized liquid rapidly into the fire;

A pressure wave, a fire ball, vessel fragments and burning

liquid droplets are usually the result;
Properties of Hazardous Mixtures

 MESG of Mixtures
Application of Le Chatelier’s Principle:

1
 n
 

 xi
MESGMix .    

 i 1
 MESGi  

Where xi denotes the volume % of the species “i” and

MESGi is the MESG of the species “i”;
Properties of Hazardous Mixtures

 Approximating UFL and LFL of a Mixture

Le Chatelier’s Principle applies again, just the flammable
limit components must be considered (revising the mixture
composition by not-considering the non-flammables);

Applies only to mixtures with air:

1 1
 n
 yi    n
 yi  
LFLMix . 



i 1
  
 LFLi  
UFLMix . 



i 1
  
 UFLi  

Where yi denotes the volume % of the species “i” and LFLi/

UFLi is the LFL/ UFL of the species “i”;
Properties of Hazardous Mixtures

 Hazardous Atmospheres
Hazardous atmospheres could cause:

 Fatalities (risk of death);

 Incapacitation;
 Impairment to self-rescue (i.e., unaided escape);
 Injury;
 Acute illness;
Properties of Hazardous Mixtures

 Hazardous Atmospheres (cont’d)

A Hazardous atmosphere is:

 Gas, vapor or mist in excess of 10% of the LFL;

 Dust that equals or exceeds its LFL;
 Oxygen below 19.5%, or above 23.5%;
 A concentration of any substance that could result in
death, incapacitation, impairment to self-rescue, injury
or acute illness;
 Any atmospheric condition that is IDLH
(Immediately Dangerous to Life and Health)
Maximum concentration a person can be exposed to for
up to 30 minutes while escaping from a hazardous area;
Properties of Hazardous Mixtures

 Hazardous Mediums
A medium (a substance/ a mixture of substances) is
considered hazardous if it has one or more of the following
properties:
 Flammable/combustible
Can easily be set on fire;
 Explosive/reactive
Can detonate or explode through exposure to heat,
sudden shock, pressure or incompatible substances;
 Corrosive
Chemical action can burn and destroy living tissues or
other materials when brought in contact;
 Toxic
Capable of causing injury or death through ingestion,
inhalation, or skin absorption;
Properties of Hazardous Mixtures

 Material Safety Data Sheet (MSDS)

A Material Safety Data Sheet (MSDS) lists all the
ingredients in a hazardous product, the hazards to safety
and health, and the precautions to follow when using the
product;
If the manufacturer claims its product is a trade secret,
the ingredients will not be listed on the MSDS;
Do not entirely rely on the word “nontoxic” on a product's
label, a product that qualifies as nontoxic can still contain
hazardous ingredients, but not in large enough amounts to
cause an acute reaction;
Chronic hazards often are not considered, read the entire
label for additional health warnings;
Properties of Hazardous Mixtures

 General Rules for Identifying Product Hazards

Regarding the MSDS for a product following points have to
be considered:

 If a product does not have sufficient information on

the label, contact the manufacturer for an MSDS;
 Carefully read all sections of the MSDS prior to using
the product and follow all precautionary advice;
 Do not consider an MSDS to be the complete source of
hazardous information on a product;
 Do not assume that a section left blank signifies the
lack of potential harm, if a product is not very
hazardous, the sections should contain information
showing that this is the case;
Properties of Hazardous Mixtures

 MSDS, Sections
A Material Safety Data Sheet (MSDS) comprises of the
following sections:

 Material manufacturer and identification;

 Hazardous ingredients/identity information;
 Physical/ chemical characteristics;
 Fire and Explosion Hazard data;
 Reactivity data;
 Health hazard data;
Properties of Hazardous Mixtures

 MSDS, Material Manufacturer and

Identification
This section identifies the product and gives the name,
address, and emergency telephone number of its
manufacturer;
The product may be listed by its chemical name or trade
name;
The product also may have a CAS (Chemical Abstract
Service) number;
CAS is an organization that indexes information about
chemicals;
Properties of Hazardous Mixtures

 MSDS, Hazardous Ingredients/ Identity

Information
This section lists the product ingredients subject to
regulations and standards, and lists the percentage of each
ingredient by total weight;
Information may also be provided on ingredient
concentration levels that could produce a health hazard;
This concentration may be stated in terms of:

 PEL (ppm, mg/m3, Skin, mg/kg);

 LD50;
 LC50;
 TLV (ppm, mg/m3, Skin, mg/kg);
Properties of Hazardous Mixtures

 MSDS, Hazardous Ingredients/ Identity

Information (cont’d)
PEL
PEL (Permissible Exposure Limit), established by OSHA, is
the amount of an airborne substance that most healthy
adult workers can be exposed to at work without adverse
effect, PELs are enforceable by law in the workplace;

LD50
LD50 represents the lethal dose that will kill 50 percent of
the test animals in laboratory experiments through either
skin contact or ingestion;
Properties of Hazardous Mixtures

 MSDS, Hazardous Ingredients/ Identity

Information (cont’d)
LC50
The LC50 is the lethal airborne concentration that will kill
50 percent of the test animals when administered in a
single exposure in a specific time period, usually one to four
hours;

TLV
TLV (Threshold Limit Value), established by the American
Conference of Governmental Industrial Hygienists
(ACGIH), is the recommended airborne concentration of a
substance that nearly all workers can be exposed to
without adverse effects, in general, the lower the TLV, the
greater the potential for adverse health effects;
Properties of Hazardous Mixtures

 MSDS, Hazardous Ingredients/ Identity

Information (cont’d)
There are three types of TLVs:
 TLV/TWA
Time Weighted Average is the recommended exposure
concentration for a normal 8-hour workday, 40-hour
workweek, if an MSDS lists only "TLV," it usually refers
to this value;
 TLV/STEL
Short Term Exposure Limit is the recommended
exposure concentration above the TWA for a limited
number of 15 minutes exposure periods;
 TLV/C
Ceiling Exposure Limit is the recommended exposure
concentration that should not be exceeded at any time
during the work period;
Properties of Hazardous Mixtures

 MSDS, Hazardous Ingredients/ Identity

Information (cont’d)
The following table illustrates how a chemical can be
classified as a Highly Toxic or Toxic, depending on the
results of the appropriate animal tests:

Animal Test Highly Toxic Toxic

Oral LD50 < 50 mg/kg 50-500 mg/kg
Dermal LD50 < 200 mg/kg 200-1000 mg/kg
Inhalation LC50 < 200 ppm 200-2000 ppm
(gases, vapors)
Inhalation LC50 2 mg/l 2-20 mg/l
(mists, fumes or dust)
Properties of Hazardous Mixtures

 MSDS, Physical/ Chemical Characteristics

This section describes the physical characteristics of the
product, such as whether it is liquid, solid, or gas at room
temperature; how much vapor it forms; whether the vapor
rises or settles; and whether the product dissolves in
water:

 Vapor pressure;
 Boiling point;
 Specific gravity;
 Melting point;
 Evaporation rate: Normal butyl acetate (n-BuAc)=1, less
than 0.8 slow evaporation rate (water is 0.3), greater
than 3.0 fast evaporation rate is considered (acetone
5.6);
Properties of Hazardous Mixtures

 MSDS, Physical/ Chemical Characteristics

(cont’d)
 Solubility in water
The quantity of a product that will dissolve in water at
room temperature, it is expressed either as a
percentage or by one of the following terms:

* Negligible: less than 0.1 percent

* Slight: 0.1 to 1 percent
* Moderate: 1 to 10 percent
* Appreciable: more than 10 percent
* Complete: 100 percent

 Appearance and odor;

Properties of Hazardous Mixtures

 MSDS, Fire and Explosion Hazard Data

This section describes the circumstances under which the
product may ignite or explode and provides instructions on
how to deal with these hazards:

 Flash point;
 Flammable limits;
 Extinguishing media;
 Special fire fighting procedures;
 Unusual fire and explosion hazards;
Properties of Hazardous Mixtures

 MSDS, Reactivity Data

This section tells how the product will react under
particular environmental conditions:
 Stability, indicates whether the product will decompose
over time and the environmental conditions, such as
heat or direct sunlight, that may cause a dangerous
reaction;
 Incompatibility, indicates which chemicals should not
come in contact with the product,
 Hazardous decomposition products, indicates which
hazardous substances might be released during fires or
from decomposition;
 Hazardous polymerization, is a process by which the
molecules of a chemical can combine to form larger
molecules (polymerize), if this chemical reaction
happens too quickly, it may produce a great amount of
heat, which may result in a fire or explosion;
Properties of Hazardous Mixtures

 MSDS, Health Hazard Data

This section provides a combined estimate of the total
known hazard of the product;
It describes routes of exposure and effects of acute and
chronic exposure, including the signs, symptoms and
diseases that may result from excessive exposure, any
medical conditions that are generally recognized as being
aggravated by exposure to the product, and emergency and
first aid procedures to follow in case of overexposure;

 Ingestion;
 Inhalation;
 Skin contact/absorption;
Pain, irritation, coma, death, etc.
Properties of Hazardous Mixtures

 Additional Topic: ERPG

Emergency Response Planning Guidelines (ERPGs) are widely
used by many industries in gas dispersion consequence
analyses to determine levels of exposure of workers and
the public to vapors from toxic chemicals, ERPGs are often
used during Process Hazards Analyses (PHA);

As defined by The American Industrial Hygiene Association

(AIHA), ERPGs provide estimates for concentration ranges
where a person may reasonably anticipate observing
adverse effects as a consequence of exposure to the
chemical in question;
Properties of Hazardous Mixtures

 ERPG Levels
Three ERPG values are provided for each of the substances
that have been researched:

 ERPG – 1
The maximum airborne concentration, below which it is believed
nearly all individuals could be exposed for up to one hour without
experiencing other than mild transient adverse health effects or
perceiving a clearly defined objectionable odor;
 ERPG – 2
The maximum airborne concentration, below which it is believed
nearly all individuals could be exposed for up to one hour without
experiencing or developing irreversible or other serious health
effects or symptoms that could impair an individual’s ability to
take protective action;
 ERPG - 3
The maximum airborne concentration, below which it is believed
nearly all individuals could be exposed for up to one hour without
experiencing or developing life-threatening health effects;
Properties of Hazardous Mixtures

 ERPG Levels
ERPG values for some widely used chemicals (ppm by vol.):

Chemical ERPG-3 ERPG-2 ERPG-1

NH3 1000 200 25
Cl2 20 3 1
HCl 100 20 3
H2S 100 30 0.1
MeOH 5000 1000 200