gent expiration

Fact or fktion?

By Russell

W. Phifer

f all the safety information

commonly found on a chemical reagent bottle, an expiration date is one of the few items that is
likely to change from one container of
that chemical to the next. As the only
representation of time likely to be
present, this date could mean the difference between safe storage and an accident waiting to happen. Or could it?
How accurate is an expiration date?
Who decides the appropriate date, and
what information is used to support
such a decision? Are these dates guesswork, or are they based on actual stability data? Are they there just to keep
us buying more product as frequently as
possible? A closer look at expiration
dates could leave you more dazed and
confused than ever, or it could save
your life some day. There are numerous
anecdotes about accidents involving
old peroxide forming chemicals-from
ethers to lithium aluminum hydride to
picric acid.
SETTING

EXPIRATION

quality complaints have there been?

Does the quality (purity) stand up to
analytical testing months later? Years
later? Although there is a long-standing
suspicion (voiced by numerous chemists who provided background for this
article) that expiration dates are simply
meant to help the manufacturer sell
more chemical, there are regulatory and

Qften an expiration
date is the only
indication of even
an approximate age
of a chemical,
because few
manufacturers show
a date of
manufacture on
reagent labels.

DATES

There appear to be at least four factors

that go into the establishment of an expiration date for a chemical reagent.
First and foremost is the stability of the
chemical. Experience with a chemical
can certainly give a manufacturer a
good idea of how stable it is. How many
Russell W. Phifer is Vice-President

of WC Environmental,
LLC, an
environmental consulting and
management firm in West Chester,
PA. He is a Certified Hazardous
Materials Manager, a Certified
Environmental Inspector, and a
Certified Environmental
Trainer.
1074.9098/99/$2OJJO
PII SlO74-9098(99)00030-l

dates:

liability issuesthat must be considered. As

always, there are economic factors, as
well. When these considerations are all
taken together, the prudent manufacturer
would certainly have to acknowledge the
value of being as accurate as possible in
determining expiration dates. The problem too often, however, is that those who
use and/or store reagents ignore the
many factors that contribute to degradation of a chemical.
CONTRIBUTIONS
QUALITY

TO LOSS IN

Factors that can contribute to quality

loss include temperature, humidity,

light, presence of contaminants, and exposure to air and/or other substances.

All are controlled in one way or another
by how inventory is managed-how
chemicals are stored. Table 1 provides
some examples of chemicals that are dependent on proper storage to maintain
their stability and quality.
It could easily be argued that expiration dates are insignificant for many of
these chemicals as long as basic storage
rules are followed. Nonetheless, it is
logical that the longer a chemical is
stored, the more likely that it will be
forgotten or ignored. This may be the
primary use of expiration dates, particularly for facilities that do not date incoming shipments of reagents. Often an
expiration date is the only indication of
even an approximate age of a chemical,
becausefew manufacturers show a date
of manufacture on reagent labels.

SAFETY AND LIABILITY

CONSIDERATIONS

How important is liability as a factor in

the development of an expiration date?
Clearly a manufacturer who has failed
to provide a recommended use by
date for a material such as ethyl ether is
more open to liability if there is an explosion due to peroxidesthat have accumulated. This same issue is a clear
incentive for manufacturers and distributors to be as conservative as possible in
establishing dates. One area in which
this can be a significant issue is in reagent recycling programs at universities.
Purdue University, for instance, experienced an explosion in 1998 when a 1L
bottle of 1M lithium aluminum hydride
in ethyl ether exploded as a researcher was wiring a rubber stopple
over the sure-seal cap. The container
had come from Purdues chemical

0 Division of Chemical Health and Safety of the American Chemical Society

Published by Elsevier Science Inc.

17

Table 1. Factors Contributing

to Chemical

bCompoSitiodPUrb

Chemical Compound
Acetic anhydride
Aluminum bromide
Aluminum chloride
Aminohexanol
Benzenesulfonyl chloride
Boron triiodide
Butyl ether
Calcium oxalate
Cesium fluoride
Chlorosilanes
Cobalt oxide
1,2 Dichloroethylene
Dipropylene glycol
Dysprosium
4-(Fluorosulfonyl) benzoic acid
Itaconic acid
Lithium
2-(Methylthio)phenyl
isocyanate
2-Naphthoyl chloride
Phenol
Phenyl thioproprionate
Potassium phosphate
Sodium
Stearic anhydride
Tetramethyl orthocarbonate
Tin fluoride
Vinylidene chloride

Contributing Factor
Humidity (moist air)

Possible Result
Solids convert to liquid phase or
degrade, some rapidly; liquids
degrade to useless hydrated
form; some react violently
with moist air

Acetyl peroxide
Hydrazine
Benzoyl peroxide
Tris(4-methoxyphenyl)borane-ammonia
complex
Butyllithium (and other metal hydrides)
Calcium carbide

Heat

Explode, degrade

Moisture

Pyrophoric, degrade

Acrylonitrile
2-Hydroxy-2 methylpropiophenone
Indene
Vinyl imidazole
1,4 Dioxane
Ethyl ether
Isopropyl ether
2, 4, 6 Trinitrophenol (picric acid)
Tetrahydrofuran

Light

Degrade, some violently unless

inhibited

Oxygen (other factors, including

impurities)

Form explosive peroxides

waste sections redistribution program;

an unopened bottle was stored inside
the can from the original shipment. The
bottle appeared to be new; however,
closer inspection of a cryptic ink-stamp
on the paper label of the outer can revealed that it had originally been received by Purdues Chemistry Stores
from the manufacturer ten years earlier!
Amazingly enough, there was no fire
from the event, but a full liter of 1M
lithium aluminum hydride was sprayed
all over the laboratory. The researcher
18

fortunately received only lacerations

and cuts. There was no expiration date
on the bottle.
COST CONSIDERATIONS

Some reagent sellers have discovered

that providing expiration dates is a value added service that can be extremely
beneficial, from several perspectives.
The use of expiration dates by manufacturers and distributors can enhance the
value of a reagent over time, in that the
Chemical

cost of analyzing and/or tracking the

history of a reagent to determine its purity can cost considerably more than the
original purchase price; this can be a
strong selling point. Expiration dates
also increase the frequency of reordering. If there is no shelf-life date, the material is more likely to sit around as inventory for a much longer period of
time. In addition, it prevents customers
from returning product as off-specification that might simply have degraded
due to age.

Health & Safety, SeptemberlOctober

1999

CAN EXPIRATION
BELIEVED

DATES BE

As most end users probably know,

many reagents are actually manufactured by some company other than the
one that placed the label on the bottle.
Laboratory reagents are frequently repackaged from larger stock, meaning
that the date of manufacture may have
been months or years before the final
packaging of the chemical. This additional handling presents risk of contamination of the product; the level of risk
depends on the quality-control methods utilized by the company doing the
repackaging. Is humidity control provided where necessary? Are the new
containers clean and sterile? Are airborne contaminants controlled? There
is no way of knowing the impact of handling without running purity checks;

As most end users

probably know, many
reagents are actually
manufactured by
some company other
than the one that
pluced
the label on
.
the bottk
even then, the quality of the analytical
equipment and skill of the operator may
result in an inaccurate assessment of
quality. All of these factors could result
in an expiration date being completely
arbitrary. Even if the accuracy of an expiration date is accepted, there are two
other dates that should be recorded by
the receiving laboratory--the date the
material was received and the date the
container was first opened. The date of
receipt is important for tracking usage,
and the date that the container was
opened and material removed is important, particularly for chemicals that may
degrade rapidly and those that might
form explosive peroxides. According to
the ACS publication Safety in Academic Laboratories, the principal criteria for assigning time spans to chemicals are the conditions in storage, the
Chemical

Health & Safety, September/October

rates at which the compounds are oxidized by oxygen, the rates at which the
compounds react with moisture and, in
some cases,the ways in which they may
polymerize. . . . Chemicals that have
been stored for a long period of time,
(perhaps five years), should be promptly
scheduled for disposal. (ACS Committee on Chemical Safety. Safety in Acudemic Laboratories, 6th ed.; American
Chemical Society: Washington, DC,
1995; p 53)
REGULATORY

CONSIDERATIONS

Regulatory considerations may be a factor in the development and utilization

of expiration dates. For example, FDA
regulations require expiration dates in
the case of in vitro diagnostic devices.
While shelf-life dating solely for package integrity and sterility is not usually
required for general medical devices,
regulations encourage expiration dating
when a particular component of a device, such as a battery or diagnostic reagent, has a finite useful life. Labeling
for in vitro diagnostic devices requires
an expiration date or some other means
by which users may be assured of quality at the time of use. This requirement
applies to both sterile and nonsterile in
vitro diagnostic devices. Although not
required by regulation, most manufacturers of complex devices and sterile devices voluntarily use lot or serial numbers for production control and, if the
need arises, to expedite failure investigations, repairs, modifications, or recalls. Lot, batch, or other control numbers are required for:
implantable and life-sustaining devices [820.65, Traceability];
some products subject to radiological health standards [1002.30(b)(l),
Records to be maintained by manufacturers]; and
in
vitro
diagnostic
devices
[809.10(a)(9), Labeling for in vitro
diagnostic products].
The OSHA technical manual specifies specific shelf-lives for sampling
media; these time limits were developed by the OSHA Salt Lake Technical Center, primarily for OSHAs own
workplace
regulatory
compliance
sampling. Also provided in the techni1999

cal manual are storage recommendations for some compounds, such as

bis(chloromethyl)ether
(store in a
dark bottle in a refrigerator).
Expiration dates are also referenced
in some laboratory accreditation procedures. For example, the American Industrial Hygiene Association (AIHA),
in its Laboratory Quality Assurance
ProgramApplication, references the use
of expiration dates in its Lead Laboratory, Environmental Microbiology Laboratory, and Asbestos Analyst Registry
programs. No specific reasoning is provided on why these requirements are
included.
Individuals who use certified analytical standards may also find expiration dates to be an issue, and iso 9000

The prudent
laboratory facility
will carefully
control each and
every chemical
reagent from the
time it is first
received until its
ultimate use or
disposal.
implementation has added some interesting twists on this as well. Those familiar with purchasing standards from
NIST, or with purchasing environmental reference standards, will typically
find an expiration date, perhaps based
upon date of shipment from the supplier or the date of certification. One
incident described during research for
this article involved an individual who
ordered and received several 1L bottles
(a supply suitable for a couple of years)
of ortho-tolidine for calorimetric determination of residual chIorine in water.
This individual was somewhat dismayed to find that the expiration date
was three weeks from when it was received. Needless to say, the quantity
purchased in this instance was exces19

Table 2. Reagent Distributor

Distributor
Lancaster Synthesis, Inc.
Pfaltz 83 Bauer, Inc.
Fisher Scientific, Inc.
Sigma-Aldrich
VWR Scientific, Inc.
Thomas Scientific, Inc.
Fluka Chemie AG

sive, particularly when consideringthe

publishedexpiration date.
MANUFACTURER
POLICIES
REGARDING EXPIRATION
DATES

A quick review of the policies of major laboratory chemical distributors

reveals a wide disparity in how expiration dates are used. A review of the
terms and conditions under which
chemicals are supplied provides a
lesson on why chemicals should be
inspected upon receipt-reagents
past their expiration dates are not
returnable. Failure to inspect the
container or evaluate quality immediately can result in the conclusion
on the manufacturers part that any
quality problem may have been the
result of poor handling by the user.
Manufacturers, of course, assumeno
liability for safety of a material once
it has been received. Table 2 shows
some representative policies of
chemical distributors regarding the
return of chemicals according to
terms and conditions published in
their respective catalogs.
WHAT SHOULD THE PRUDENT
FACILITY DO?

The prudent laboratory facility will

carefully control each and every

20

Policies

on Request to Return Chemicals

Return Policy
Within 10 days of receipt
Within 30 days of receipt
Will not accept reagent bottles that have been
opened for return
Per terms and conditions on packing slip; all
claims must be submitted within one year
of receipt
Within 60 days of receipt
Within 30 days of receipt
Within 5 days of receipt

chemical reagent from the time it is

first received until its ultimate use or
disposal. A major part of this inventoy control effort should be dating of
the label at the time it is first received
and on the day it is first opened. If
there is an expiration date on the container, this should be reviewed to determine if the chemical is to be used
prior to that date. These actions will
help considerably, not only in ensuring that high-quality material is available for the end user, but also in determining whether a material should
be returned immediately. Assuming
that it is not going to be used immediately, any observations regarding the
condition of the bottle or the chemical
inside should be noted at the time of
receipt and appropriate action taken.
For example, a cracked cap may be
indicative that the integrity of the
chemical has been compromised, and
the bottle should be returned immediately according to the distributors
terms and conditions. If the product
appearsto be multi-phased, dirty, or
partially decomposed, the distributor
should be notified immediately. This
inspection process should ideally be
made by an individual with some experience in handling the material.
Expiration dates are becoming a
more important part of chemical la-

Chemical

beling. Whereas some of the factors

that go into determining when a
chemicals useful life is past may be
beyond the control of the end user,
the cost of chemical reagents and the
value of a researchers time dictate
that all appropriate measuresbe taken
to assurequality and safety.
Bibliography
American Chemical Society, Committee on Chemical Safety, Safety in Academic Laboratories, 1998.
American Industrial Hygiene Association web site-www.aiha.org.
Food and Drug Administration web
site-www.fda.gov.
National Research Council, Prudent Practices for the Handling of
Hazardous Chemicals in Laboratories, National Academy Press,1998.
Occupational Safety and Health Administration web site-www.osha.gov,
Acknowledgments
The author wishes to thank Guy M.
Crawford, University of Texas-El
Paso;Dr. Linda Swihart, Purdue University; Dr. Benjamin Greene, Allied
Signal; and Mark Yanchisin, University of Florida for their contributions
to this article.

Health & Safety, September/October

1999