SAFETY MANAGEMENT
Vapor Hazard Ratio
The
The Health
Health Hazards
Hazards of
of Solvents
Solvents
Nicholas
Nicholas Kob,
Kob, Ph.D.,
Ph.D., R&D
R&D Chemist
Chemist DuPont
DuPont Nylon
Nylon Intermediates,
Intermediates,
Gerald
Gerald Altnau,
Altnau, Ph.D.,
Ph.D., Business
Business Manager
Manager DuPont
DuPont Nylon
Nylon Specialty
In order to understand the health
risks of working with solvents there
is a need to evaluate their potential
risk to the health and safety of the
user. This article describes the use of
a vapor hazard ratio (VHR) based on
the TLV-Values used in the U.S.A. to
help employers and workers evaluate
the potential health risks of using a
solvent. Included in this article is an
example of how the VHR can aid in
the selection of a replacement solvent
blend for a paint stripping
application.
Introduction
In the United States of America there is
an increased awareness about environ-
mental protection and worker safety,
which has led to debate about which sol-
vents are appropriate and safe to use in
a number of applications and situations.
The american government has taken the
lead regulating the use of several sol-
vents under the Clean Air Act of 1990;
for these chemicals it is clear what the
hazards are, and that their use presents
a potentially unsafe working environ-
ment. However, a clear understanding by
the user of a solvent’s safety or potential
health risk is the exception rather than
the rule. In some cases it is extremely
difficult to accurately evaluate the work-
place health hazards created by using
one solvent versus another. Many times
the perceived health hazard of working
with a solvent is a factor in determining
the amount and type of PPE (Personal
Protection Equipment) required for a
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worker to safely work with a chemical.
This can make working with one solvent
appear economically unattractive as well
as presenting a higher potential health
risk as compared to another solvent. Ge-
neric phrases such as low toxicity, high
flash point, and low VOC are terms used
by many solvent manufactures to des-
cribe solvents, but these descriptions are
relative and are not based on scientific
definitions. Extensive customer interac-
tion with those in the solvents business
has revealed to the authors the need for
additional approaches to aid solvent
users in the selection of solvents or
blends for a process. In most cases more
than one solvent or blend is acceptable
on a performance basis. In these cases
another deciding factor in the selection
of a solvent or solvent blend is the safety
and health aspects.
Large companies many times rely on
their own internal SHE department (sa-
fety, health, and environmental) to com-
municate and establish information on
the safe handling of a solvent or chemi-
cal. However, small to medium-sized
companies often can not afford to have a
SHE expert employed to guide solvent se-
lection. External consultants are an op-
tion, but many times they are also too
costly for smaller companies. In order to
assist in the protection against the health
effects of chemical exposure several ex-
posure limits have been established. Ex-
posure limits refer to airborne concen-
trations of a substance and represent
conditions under which it is believed that
nearly all workers may be repeatedly ex-
posed day after day without adverse he-
alth effects. Exposure limits are not in-
tended for use as a comparison metric of
one solvent versus another. However, in
practice we have found that in many ca-
ses exposure limits are being used to
compare the health and safety aspects of
using one solvent versus another.
This article describes a parameter
that can easily be calculated to aid in the
evaluation of the risk potential of sol-
vents. The parameter, VHR (vapor ha-
zard ratio), is based on existing exposure
guidelines and on the physical properties
of the solvent. The VHR can help to com-
pare solvents and solvent blends for their
potential health risk to workers at wor-
king conditions, and aid in the selection
of a safer solvent/blend.
Discussion
Numerous lists have been established
which serve as guides for the selection of
safe solvents. These include Volatile Or-
ganic Compounds (VOC), Hazardous Air
Pollutants (HAP), Clean Air Act Amend-
ments (CAAA) of 1990, and others. In ad-
dition a number of different exposure li-
mits have been established. OSHA sets
permissible exposure limits (PELs) to
protect workers against the health ef-
fects of exposure to hazardous substan-
ces. PELs are regulatory limits on the
amount or concentration of a substance
in the air, and PELs are enforceable.
Threshold limit values (TLV) are develo-
ped as guidelines by The American Con-
ference of Governmental Industrial Hy-
gienists (ACGIH) to assist in the control of
health hazards. These recommendations
 SAFETY MANAGEMENT

Fig. 1: Hansen Solubility Parameter Map Fig. 2: Low Risk Solvent Blends for Paint Stripping

are intended for use in the practice of in- to evaluate a solvent’s health hazard po- have ceiling limit values that it is never
dustrial hygiene, and are not developed tential. Other countries establish their permissible to exceed.
for use as legal standards. TLV’s are the own exposure limits for chemicals, which Many times evaluation of one solvent
method most commonly used in the U.S. are used similarly to the TLV in the U.S. versus another by comparison of the ex-
Exposure limits are not neces- posure limit is used to evaluate the safety
Tab. 1: Risk Potentials of Commonly Used Solvents sarily an indication of a chemi- aspects of using a solvent. Despite the
cals toxicity, they are establis- fact that exposure limits are not intended
Solvent Exposure limit Vapor Saturation VHR
hed to prevent any adverse to be used in this manner it has been our
*TLV/AEL pressure Conc.
effect on health. For example, experience that many times this is the
(ppm) (mmHg) (ppm)
one chemical’s exposure limit case. For example, if solvent A has an ex-
TPM 100 0.03 39 0.39 of 25 ppm may be established posure limit of 100 ppm and chemical B
Propylene 20 0.02 26 1 due to carcinogenic concerns has an exposure limit of 10 ppm, a con-
Carbonate and another chemical may clusion could be drawn that chemical A
*DB 5 0.02 26 5 have an exposure limit of 25 is safer. However, this may or may not be
DPM 100 0.6 723 7 ppm set due to skin irritation. correct since the exposure limit does not
DMPD 5 0.07 92 18 Therefore, exposure limits do reflect the ease at which that airborne
*Solvesso 50 1 1316 26 not reflect the consequences of concentration can be achieved. Many ti-
150 exceeding them, and many ti- mes exposure limits are used to help
**NMP 10 0.3 394 39 mes chemicals with the same guide the selection of PPE worn by wor-
Mineral 100 3 3947 39 exposure limit will have signifi- kers. Failing to consider the ease at
Spirits cantly different consequences. which an exposure limit can be reached
*d-limonene 50 2 2632 53 Exposure limits refer to air- could result in the employee not having
*DMSO 10 0.6 789 79
borne concentrations of sub- the proper PPE and hence have an incre-
*DBE 1.5 0.1 131 87
stances, but in order to under- ased health risk. Also, a chemical with a
DMAc 10 2 2632 263
stand the potential of that low exposure limit may be inaccurately
Xylene 100 20 26316 263
substance to be airborne at a deemed unsafe requiring the employee
MIBK 50 15 19737 395
given set of conditions the va- to wear excessive PPE that may result in
DMF 10 3 3947 395
por pressure must be conside- an unnecessary increased production
MEK 200 70 92105 460
red. The vapor pressure of a cost to the employer. Clearly, in addition
Acetone 500 248 326316 652
substance changes depending to vapor pressure considerations many
Toluene 50 28 36842 737
on the temperature and pres- other factors need to be considered such
Methanol 200 127 167105 835
sure conditions, hence chan- as the size of the room, and the ventila-
Methylene 50 350 460526 9210
ging the airborne concentra- tion system.
chloride
benzene 1 95 125000 125000
tion of the substance. If one Further complicating the assessment
elects to use exposure limits to of a chemicals safety relative to another
* DuPont AEL exposure limits were used since no TLV values available. guide them in the selection of a is that not all chemicals have established
** WEEL exposure limit used. solvent then the vapor pres- exposure limits. DuPont internally evalu-
TPM – tripropylene glycol methyl ether sure of that solvent should also ates the safety of chemicals for its wor-
DB – diethylene glycol butyl ether be taken into consideration. kers and the environment. Through its
DPM – dipropylene glycol methyl ether Most exposure limits are ex- Haskell Laboratory, DuPont has been
NMP – N-methyl-2-pyrrolidone pressed as a time weighted studying for the last 20 years the acute,
DMPD – Dimethyl-2-Piperidone average (TWA) for an 8 hour or subchronic, reproductive, mutagenic,
DMSO – Dimethyl Sulfoxide 12 hour workday. TWA’s permit and other toxicological effects of chemi-
DBE – DuPont’s dibasic ester excursions above the exposure cals. From these studies DuPont determi-
DMAc – N,N Dimethyl acetamide limit provided that the average nes AEL (acceptable exposure limits) for
MIBK – methyl isobutyl ketone exposure over 8 hours is below chemicals, which are DuPont’s internal
DMF – N,N Dimethylformamide the exposure limit. However, in exposure limits. AEL’s are guidelines ba-
MEK – methyl ethyl ketone some cases exposure limits sed on informed judgment, and are not

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 SAFETY MANAGEMENT
fine limits between safe and dangerous
concentrations. They are not for use as
relative toxicity indexes, limits for conti-
nuous uninterrupted exposure, or proof
or disproof of health effects. TLV values
for many chemicals have not been estab-
lished, and for those chemicals AEL va-
lues are used to guide worker safety in
DuPont, and will be used in this report.
As previously described, many times
high exposure limits (PEL, TLV, or AEL)
for a solvent give a safe impression des-
pite the fact that the solvent is low boi-
ling (fast evaporating). The evaporation
rate of a solvent is often overlooked by
many people who do not recognize that a
high exposure limit may be reached
quite quickly at ambient temperature
and pressure conditions. People feel
much more comfortable working with a
chemical that has an exposure limit of
200 ppm verses one that has an expo-
sure limit of 5 ppm. It is counter intuitive
to many people that the solvent with the
5 ppm exposure limit may be safer to
work with because its limit is reached
more slowly or may never be reached at
a given set of conditions. The challenge is
that no easy method exists to help them
evaluate solvents based on the exposure
limit, and the physical properties. We re-
commend the use of the vapor hazard ra-
tio (VHR) which is the quotient of the sa-
turated vapor concentration of a
chemical (at a given temperature and
pressure) and its exposure limit to aid in
the evaluation of one solvent versus an-
other. However, it should be made very
clear that we do not intend for the VHR
to be used as the only criteria in the eva-
luation of the hazard potential of one sol-
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vent verses another. It can be used as a
tool in the assessment of one solvents sa-
fety relative to another based on the ex-
posure limit and physical properties. The
vapor hazard ratio for a chemical can be
easily calculated by using simple arith-
metic in the following equations:
Saturation Concentration of chemical,
ppm = (vapor pressure, mmHg / 760)*106
Then the VHR is:
VHR = (saturation concentration, ppm) /
(exposure limit, ppm)
Different VHR’s can be calculated for the
same chemical under different condi-
tions since the vapor pressure changes
with temperature and pressure. Such a
comparison of using a solvent safely at
varying conditions is not possible with
exposure limits alone, and this provides
another piece of information that can be
used in the evaluation of solvent safety.
This is because the vapor hazard ratio
reflects the risk potential of a solvent in
terms of not only the exposure limit but
also the potential ease at which that limit
is achieved at a given set of conditions.
Table 1 lists a number of the more com-
monly used solvents and their associated
VHR; solvents with lower VHR values
have a lower potential health risk (are
safer to use). In contrast many view sol-
vents with lower TLV/exposure limits va-
lues as having a higher potential health
risk. It is important to notice in Table 1
that solvents with a low TLV/exposure li-
mit do not necessarily have a high VHR.
The concept of the vapor hazard ratio
is currently being used globally to aid in
the evaluation of the potential health ha-
zards of chemicals. Occupational expo-
sure standards are derived and impli-
mented from country to country [1].
Several countries have guidelines that
include vapor pressure considerations in
addition to exposure limits. In Germany
the vapor hazard ratio is described and
recommended as “Gefahrdungszahl Gz”
in the technical guidelines of the German
“Gefahrstoffverordnumg” (TRGS 420, the
German technical rule for hazardous
materials). The Danish MAL system re-
flects the cubic meters of fresh air requi-
red for ventilation of 1 liter of chemical
to below the exposure limit. This number
is modified by a constant, depending on
the evaporation rate or vapor pressure.
Higher vapor pressures imply a greater
hazard so the multiplier is larger. Other
metrics in addition to exposure limits
have been generated to help evaluate
risks by inclusion of vapor pressure con-
siderations. A Danish publication compa-
ring several of these is available. The Da-
nish MAL codes define which safety pre-
cautions are required for each of a large
number of processing operations and
conditions. The purpose of such a system
is to suggest that possible substitutes to a
current solvent can be found with a lo-
wer potential health risk. As mentioned
previously, in the U.S. it has been our ex-
perience that exposure limits are being
used as the metric for comparison of one
solvent versus another. The additional
consideration of the vapor pressure, as
done with the VHR, will help solvent
users to consider additional metrics in
their evaluation.
Although the VHR describes the risk
potential based on exposure limits; it
fails to describe other hazards which em-
ployer and employee may wish to consi-
der to insure the safest workplace possi-
ble. A common concern when using
solvents is the risk of fire. Every year nu-
merous injuries occur which are the re-
sult of a fire involving a solvent. Other
possible hazards/factors include chemi-
cal incompatibility, reaction with the pro-
cess or other solvents, and the biodegra-
dability of the solvent. One must also
consider that many chemicals have cei-
ling limits of exposure. Employers/wor-
kers, in addition to looking at the VHR
should consult the MSDS to determine
the human health effects associated with
exceeding the exposure limit.
The following example shows how
the VHR can be easily and proactively
used to develop safer solvent formula-
tions. Hansen solubility parameters are
used to classify solvents in terms of
their non-polar, polar, and hydrogen
bonding characteristics, and are used
extensively to determine the appropri-
ate solvent or solvent blend for a coa-
tings or cleaning application. Every sol-
vent is unique in its characteristic
Hansen solubility parameters, and
hence has a unique place on the Han-
sen Solvent map as shown in Figure 1.
Hansen parameters provide a systema-
tic method that is used to identify sub-
stitute solvents, or determine the solu-
bility of a resin in a solvent or solvent
blend. The suitability of a solvent to dis-
solve a particular coating or resin in
based on the principle of “like dissolves
like”. Therefore, in developing a repla-
cement solvent or solvent blend it is cri-
tical to the performance that the Han-
sen parameters for the replacement
blend be similar to those of the current
solvent blend. For further discussion on
the use of Hansen parameters in sol-
vent selection we refer the reader to re-
ference [1].

Replacement of a solvent blend in a Paint
Stripping Application
A typical paint stripping blend (labeled
current blend in Fig. 2) may be:
Solvent Solvent Solvent
VHR TLV/Exposure limit
(ppm)
30% 9210 50
Methylene
Chloride
40% Xylene 263 100
30% MIBK 395 50
An exposure limit (TLV or AEL) for a li-
quid mixture can be calculated on a
time-weighted average exposure basis
assuming the atmospheric concentration
is similar to that of the original mixture
(all the liquid mixture eventually evapo-
rates). When the percent composition (by
weight) is known the exposure limit of
the mixture is:
Exposure limit mixture =
1/[(fa/TLVa) + (fb/TLVb) + (fc/TLVc) +…(fn/TLVn)]
Where fn is the weight fraction of compo-
nent n and TLVn is the exposure limit of
component n. An alternative method is
using the VHR in place of the TLV/expo-
sure limit to reflect the health risk a sol-
vent mixture poses based on the not only
the exposure limit but the potential ease
at which that limit could be achieved at a
given set of conditions:
Exposure limit mixture =
1/[(fa/VHRa) + (fb/VHRb) + (fc/VHRc) +…(fn/VHRn)]
Using a solvent formulation program
(DuPont as well as many other compa-
nies offer such services to customers),
the Hansen parameters for the above hy-
pothetical solvent blend is found to be
non-polar 9.1, polar 2.3, and hydrogen
bonding 2.1 (Fig. 2 shows the location of
the blend on a solubility map). The Han-
sen parameters show the solvency of the
solvent blend and it is desired that a re-
placement solvent blend has similar
Hansen parameters and present less of a
health risk. As is almost always the case
there is not one single correct answer for
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SAFETY MANAGEMENT
a replacement solvent in a blend, rather the VHR regards the current blend as
many are possible. A few possible ans- being more hazardous due to the fact the
wers could be: vapor pressure shows it to be more vola-
tile, and hence its exposure limit may be
Blend # Solvents Solvents Solvents more easily achieved. Since the exposure
VHR TLV/Exposure limit alone does not reflect the potential
limits (ppm) volatility of a solvent blend that informa-
Blend 1 40% d-limonene 53 50 tion is not considered if one compares
35% DuPont DBE 87 1.5 solvent blends using only exposure limits.
Clearly, the type of information provided
10% propylene 1 20
by the VHR is of value since it provides
carbonate 16 25
another approach to aid in the evaluation
15% NMP
of the relative hazards of using one sol-
Blend 2 40% DuPont DBE 87 1.5
vent blend versus another.
20% NMP 16 25
40% Solvesso 150 26 50
Blend 3 30% DuPont DBE 87 1.5 Conclusion
20% DMSO 79 10
15% DB 5 5 Worker safety and environmental pre-
35% mineral spirits 39 10 servation are two of the most important
parameters used in the selection of sol-
vents for processes. We propose the use
The Hansen parameters for the proposed of an easily calculated metric, the VHR
solvent blends 1–3 have similar and ac- (vapor hazard ratio), as a tool for wor-
ceptable solvency to the current blend, kers and employers to access a solvent’s
as shown in Figure 2. Comparison of the potential health hazards based on expo-
VHR values of the individual solvents in- sure limits and physical properties for a
dicates that the proposed formulations given chemical. Further, many countries
are solvent blends of lower hazard po- establish their own exposure limits so
tential than the current blend. The VHR this approach can and is being used glo-
are TLV/exposure limits for the blends bally (using local exposure limits) to eva-
were calculated: luate and compare solvents. We also ad-
vise that in addition to the VHR
Solvent Blend Blend exposure Blend exposure parameter, one should read the chemica-
limit (using VHR) limit (using TLV) l’s MSDS and consider other risk factors.
Current Blend 432 63
Reference
Blend 1 9 4
Blend 2 31 3 [1] Jankovic, J.; Drake, F.: Am. Ind. Hyg. Assoc. J.
Blend 3 22 4 57, 641 (1996)
The Authors
The calculations show that by inspection Nicholas Kob, Ph.D.
of only the TLV/exposure limits of the R&D Chemist DuPont Nylon Intermediates
blends (the lower the TLV the more ha- DuPont Experimental Station E302/316
P.O. Box 80302
zardous the blend) one may conclude that
Wilmington, DE. 19880, USA
the current blend has the lowest potential
Nicholas.e.kob@usa.dupont.com
health risk. However, by calculating the
VHR of the blends (the higher the VHR Gerald Altnau, Ph.D.
the more hazardous the blend) one may Business Manager DuPont Nylon Specialty Intermedia-
conclude that the current blend has the tes Europe
highest potential health risk to the user. DuPont-Str. 1
61352 Bad Homburg, Germany
This example highlights the fact that a
Gerald.altnau@deu.dupont.com
different conclusion on the relative safety
http://www.DBE-dupont.com
of using one solvent blend versus another
can be reached depending on how the
evaluation method used. In this example Easy Info Nr. • 201
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