Solvent Flammability Basics

The concept of flammability may seem elementary on the surface, when in

actuality, flammability and flash point measurements must be performed using
the correct standardized methods. You may be surprised when you do.

by Ronald L. Shubkin and Barbara F. Kanegsberg

There are a number of sources of confusion regarding flammability. One problem

is the application of test methods conducted outside of the range of parameters
for which the test is designed. Finally, the vapors of certain halogenated solvents
can burn within a narrow concentration range in air even though they exhibit no
flash point. They are self-extinguishing. All of these factors have led to incorrect
flammability data. As with other physical and chemical parameters, it is crucial for
manufacturers to have access to flash point data based on the appropriate
consensus standard for the material in question and performed by independent
test facilities.

Flammability Definitions and Standards

The Occupational Safety and Health Administration (OSHA) defines “Liquid,
Flammable” as “any liquid having a flashpoint below 100 °F (37.8 °C), except any
mixture having components with flashpoints of 100 °F (37.8 °C) or higher, the
total of which make up 99 percent or more of the total volume of the mixture.”i
The U.S. Department of Transportation (DOT) defines Class 3 Flammable Liquidsii
for transportation purposes on essentially the same basisiii. Both regulatory
agencies define “Flash Point” as the minimum temperature at which a liquid gives
off a vapor in sufficient concentration to ignite when tested by specific methods
as set forth in the regulationsiv. Both DOT and OSHA specify appropriate test
methods from the American Society for Testing and Materials (ASTM), specifically
ASTM D56, ASTM D93 and ASTM D3278. DOT also allows ASTM D3828.

The National Fire Protection Agency (NFPA) Code 30 is a definitive consensus

document for determining flammability. This document clarifies which
flammability tests are considered valid for particular compounds or mixtures,
referring to essentially the same ASTM test methods, as does OSHA. In Code 30,
the characteristics of a flash point are defined in section 1.7.2.2 as the minimum
temperature of a liquid at which sufficient vapor is given off to form an ignitable
mixture with the air, near the surface of the liquid or within the vessel used, as
determined by the appropriate test procedure and apparatus specified in 1.7.4.
Note that both the appropriate apparatus and the test procedure depend on the
material being tested. The use of an inappropriate approach for the chemical
under investigation, or the employment of an incorrect apparatus, may lead to an
incorrect result.

Choosing the Flash Point Test Method

A variety of Flash Point test methods have been developed to determine the
flammability of liquids. Certain of these have become industry standards and are
correct in a technical sense. However, these various methodologies are valid only
over specified temperature ranges and for liquids with viscosities within specified
ranges.

If an incorrect technique is used for the material in question, a result is obtained

that is not valid. For example, nPB has a relatively low viscosity, and independent
laboratories, using the accepted techniques for low viscosity materials, have
determined that n-propyl bromide does not have a flash point.v,vi Contrarily, a
method using the Pensky-Martens Closed Cup procedure (ISO 1523) a
methodology designed for a viscous fluid and valid only at temperatures above
+10°C obtained a flash point of –10°C for nPB.vii Following that report, an
independent testing laboratory, Chilworth Technology Ltd., determined if this
methodology gave results that differed from what was reported for other well-
established non-flammable liquids.viii,ix Tests were performed using ASTM D93, a
consensus standard that employs the Pensky-Martens Closed Cup apparatus, the
same equipment specified in ISO 1523. In addition, results obtained using ASTM
D93 were compared to those obtained using ASTM D56 (Tag Closed Cup). Unlike
ASTM D93, ASTM D56 is specified to be used for low viscosity fluids and may be
used at low temperatures. The results for nPB and for five widely accepted non-
flammable liquids are given in Table I.

Flash Point Flash Point, °C

Run Within Test Run Outside Test
Compound
Ranges Ranges
ASTM D56 ASTM D93

n-propyl bromide None -5

Trichloroethylene None + 24

Methylene
None - 5.5
chloride

HFE-72DE None -9

HFE-71 DE None - 16

HFE-71 DA None - 14

Table 1. Flash Points by Appropriate and Inappropriate Methods: The flash

point method of choice depends on the compound to be measured. If an incorrect
method for the compound being studied is employed, even solvents accepted and
used for decades as having no flash point can erroneously appear to be
flammable.

Accepting the results of a seemingly more stringent flash point determination,

which is not an industry standard, is not more conservative or protective of
workers. The reason is that the flash point apparatus is designed to start fires
under specific conditions. The use of an apparatus and a method outside the
range that it was designed for can give a flash point under conditions that are not
relevant to real-world conditions.

As indicated, a definitive, consensus document is NFPA Code 30. The relevant

method for low viscosity liquids, is that described in section 1.7.4.1, which is for
liquids with a relatively low viscosity, in other words, below 5.5 cSt at 104°F
(40°C) or 9.5 cSt at 77°F (25°C). The appropriate technique is ASTM D56,
“Standard Method of Test for Flash Point by the Tag Closed Cup Tester”. For
example, the viscosity of nPB is 0.36 cSt at 25°C., more than an order of
magnitude below the dividing line between the ASTM D56 technique (low
viscosity) and the ASTM D93 technique (Pensky-Martens Closed Cup for high
viscosity liquids). ASTM D 3278 for small-scale testing is also permitted under
certain conditions as indicated in Section 1.7.4.4.

Observing a Flash Point

Some of the confusion in reporting the results of flash point testing lies in
understanding the definition of a flash point. A flash point test consists of passing
a pilot light over the surface of the liquid being tested. If the vapors of a liquid
are flammable, in other words, capable of sustaining combustion, the flame front
will propagate from the pilot light to the liquid surface. The lowest temperature at
which this flame propagation happens is called the flash point. The NFPA gives a
number of definitions of flashpoint in its Glossary of Terms, but they all include
the phrase, “The minimum temperature at which a liquid gives off vapor sufficient
to form an ignitable mixture in air near the surface of the liquid.” In lay terms,
the flame front must move from the pilot light to near the surface of the liquid. n-
Propyl bromide does not exhibit this behavior under the conditions of the ASTM
D56 or the Cleveland Open Cup methods.7

A flash point test consists of moving a pilot light over an open cup of liquid (open
cup tests) or opening the cover of a closed container when a pilot light is
positioned over the cover (closed cup tests). Non-flammable liquids that will not
burn at the temperature of the pilot light will not affect the pilot light flame.

One source of erroneous reports of flash points consistent with inaccurate

observations is that the vapors of certain halogenated compounds, can be
combusted in an external source of ignition. The result of this characteristic in the
performance of a flash point test is that the pilot light may be briefly enhanced
before it is extinguished. In this case, the enhanced flame is above the pilot light
and not near the surface of the liquid as required by the various NFPA definitions.

Enhancement of the pilot light is typical of hydrochlorocarbons that are classified

as non-flammable (i.e., methylene chloride, trichloroethylene, etc.). The mistaken
interpretation of pilot light enhancement for flashpoint led to early, erroneous
identification of n-propyl bromide as a flammable liquid.

Flammable liquids behave quite differently in flash point tests than do non-
flammable, halogenated liquids. Specifically, in contrast with halogenated
solvents and other non-flammable liquids, the “flash” is readily apparent as it
spreads almost explosively through the flash point cup and above it.

Flammability Limits
Most hydrochlorocarbons, some hydrofluoroethers, some
hydrochlorofluorocarbons and nPB will burn when the vapor concentration in air is
within narrow limits. When such vapors begin to burn, several factors rapidly
change the vapor concentration so that it is no longer within the flammable limits.
The concentration in the vapor state is depleted by both consumption in the
oxidation process and by expansion of the vapor caused by the exothermic
combustion. The combustion rapidly self-extinguishes.

Flammability limits are usually reported as the Lower Explosive Limit (LEL) and
Upper Explosive Limit (UEL). The units are commonly the volume percent of the
vapor in air. The flammability limits of some well-known, “non-flammable” liquids
are given in Table II.

Table 2. Flammability Limits of Representative Non-Flammable Liquidsa

Compound LELx UEL12

n-propyl bromide 4.0 vol.% 7.8 vol.%

methylene chloride 13.0 23.0

trichloroethylene 8.0 10.5

1,1,1-trichloroethane 7.0 13.0

HCFC-141b 7.6 17.7

HFE 7200b 210 g/m3 1070 g/m3

a. Some non-flammable liquids can burn within narrow concentration ranges.
However, the combustion rapidly self-extinguishes.
b. Data from 3M Technical Data Sheet. The flammability range is approximately
2-10 vol.%.

When an organic solvent is the appropriate selection, an understanding of

flammability characteristics is imperative. As with other issues concerning
performance, compatibility, safety, and environment, it is important to critically
evaluate all flammability characteristics. Further, to be meaningful, available
consensus standards and methods are the ones to use.

The bottom line is safety. The use of any organic solvent, or any blend containing
volatile organic vapors, must include an analysis of potential flammability,
including the flash point. A number of additional considerations, including process
specifics and other processes performed in the vicinity must also be taken into
account.

Thanks to Battalion Chief Michael Bean of the Warminster Fire Department and
Fire Marshal’s office for reviewing the NFPA sections of this article.

About the Authors

Ronald L. Shubkin is Manager of Technical Services for Poly Systems USA, Inc, a
provider of nPB. He holds thirty U.S. patents with ten dealing with formulations
and applications for nPB-based solvents in critical cleaning. He can be reached at
shubkin@solvon.com.

Barbara Kanegsberg is President of BFK Solutions, LLC, an independent

consulting company specializing in critical cleaning issues. She is a chemist with
over eighteen years of experience in contamination control issues. She may be
reached at Barbara@bfksolutions.com.

________________________________________

i Code of Federal Regulations, 29 CFR 1910.1200(c).

ii Code of Federal Regulations, 49 CFR 173.2.
iii Code of Federal Regulations, 49 CFR 173.120(a).
iv Code of Federal Regulations, 49 CFR 173.120(c)(1) and 29 CFR 1910.1200(c).
v Joe Miller, Document No. OAR-2002-0064-0040, “Albemarle Corporation – Flash Point Data for n-
Propyl Bromide”, submitted to the USEPA on 8/4/003.
vi Richard G. Morford, Document No. OAR-2002-0064-0030 and –0031, “Enviro Tech Comment re:
Section IVD Flammability”, submitted to the USEPA on 7/25/2003.
vii Report by the German National Flammables Laboratory to the European Chemicas Bureau (ECB).
For a discussion of this report see reference no. 8, document –0031, Exhibit G.
viii Study done under contract to the International Brominated Solvents Association, IBSA.
ix Stephen M. Rowe (Chilworth Technology, Ltd., England), Reports No. 09802 (3/26/02) and No.
15302 (5/10/2002). These may be viewed at reference 8, document –0031, Exhibit H, or may be
obtained from R. Morford, Enviro Tech International, Inc.
x Ronald L. Shubkin, “normal-Propyl Bromide”, CRC Handbook for Critical Cleaning (B. Kanegsberg
and E. Kanegsberg, eds.), CRC Press, 2001, Chapter 1.7, pp. 111-131.