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norganic and organic peroxides, highly reactive and unstable com- ordinary combustible materials (e.g.,
because of their exceptional reac- pounds and used “oxygen balance” to fabric, oil, wood, or some resins)
tivity and oxidative potential are predict the stability of individual com- poses significant fire or explosion haz-
widely used in research laboratories. pounds and to assess the hazard po- ards. Peroxides of alkali metals are not
This review is intended to serve as a tential of an oxidative reaction. Jack- particularly shock sensitive, but can
guide to the hazards and safety issues son et al.6 addressed the use of decompose slowly in the presence of
associated with the laboratory use, peroxidizable chemicals in the re- moisture and may react violently with
handling, and storage of inorganic and search laboratory and published rec- a variety of substances, including wa-
organic peroxy-compounds and per- ommendations for maximum storage ter. Thus, the standard iodide test for
oxide-forming compounds. time for common peroxide-forming peroxides must not be used with these
The relatively weak oxygen-oxygen laboratory solvents. Several solvents, water-reactive compounds.1
linkage (bond-dissociation energy of (e.g., diethyl ether) commonly used in Inorganic peroxides are used as ox-
20 to 50 kcal mole!1) is the character- the laboratory can form explosive re- idizing agents for digestion of organic
istic structure of organic and inor- action products through a relatively samples and in the synthesis of or-
ganic peroxide molecules, and is the slow oxidation process in the pres- ganic peroxides. They react violently
basis for their reactivity and tendency ence of atmospheric oxygen. The risk with reducing agents and with several
for spontaneous decomposition. The of explosion can be greatly reduced by classes of organic compounds to gen-
unusual weakness of the -O-O- bond following storage and handling prac- erate organic peroxide and hydroper-
is probably a consequence of the mo- tices that are compatible with the oxide products.4 Dry Caro’s reagent
lecular and electronic structure of per- properties of these materials.1,6 More (monopersulfuric acid — K2O2 " con.
oxide molecules and of the relatively recently, Kelly7 reviewed the chemis- H2SO4) reacts readily with carbonyl
high electronegative character of the try and safe handling of peroxide- compounds (in the synthesis of or-
oxygen atoms. As a class, peroxides forming chemicals and included pro- ganic peroxides) and can react explo-
are exceptionally prone to violent de- cedures on detection and removal of sively with aldehydes and alco-
composition that can be initiated by peroxides from laboratory solvents. hols.3,4,5 Similar characteristics are
heat, mechanical shock, or friction, Safety awareness, prudent handling associated with other inorganic perox-
especially in the presence of certain and proper storage are essential when ides and persalts. Peroxides may form
catalysts and promoters. working with these compounds.1,2 on the surface of finely divided alkali
The hazards of inorganic and or- metals and their amides and readily
ganic peroxides and peroxide-forming form superoxides, and ozonides such
chemicals have been long recognized INORGANIC PEROXIDES AND as KO3.8
so that most relevant information is PEROXYACIDS Inorganic per-compounds (e.g., so-
now found in text books on organic The O-O bond of hydrogen peroxide dium peroxide, sodium perborate, and
chemistry and laboratory safety. A is covalent. In solution, persalts of al- sodium persulfate) may react with in-
comprehensive three-volume series kali metals (M2O2) are ionized to the organic cobalt and copper com-
on the chemistry of organic peroxides monopositive alkali metal ion (M"), pounds, iron or iron compounds,
includes a chapter on safety issues as- and the dinegative peroxide ion metal oxide salts, and acids or bases
sociated with these materials.1,2,3,4 (O2!2). Metallic peroxides are consid- resulting in rapid, uncontrolled de-
ered to be salts of hydrogen peroxide composition reactions. Persulfates
and react with water to produce (e.g., peroxy sulfate) are highly reac-
Donald E. Clark, Ph.D., FAIC, RBP H2O2.1 tive and may ignite when in contact
is the Chemical and Biological Safety Hydrogen peroxide alone is not ex- with metals.2,4,8
Officer at Texas at A&M University, plosive and has a long shelf life if it is Perhalogen compounds (e.g., peroxy
College Station, TX, USA. handled properly and is not contami- chloride) are extremely shock sensitive
12 © Division of Chemical Health and Safety of the American Chemical Society 1074-9098/01/$20.00
Published by Elsevier Science Inc. PII S1074-9098(01)00247-7
and should be avoided unless abso- of the properties, hazards and use of agents. Each peroxide compound is
lutely necessary. They can react with perchlorates, including perchloric characterized by a specific, condition-
acids (especially organic acids) to pro- acid in the CRC Handbook of Labo- dependent rate of decomposition. A
duce near-anhydrous perchloric acid. ratory Safety. He stated that, “The change in critical parameters (e.g., in-
Perhalogen compounds of alkali metal most detailed available account of the creased temperature) can promote
and alkali earth elements are explosive, chemistry of perchloric acid and a ref- rapid increase in the decomposition
but are less sensitive than heavy metal erence highly recommended to every- rate, culminating in a violent explo-
perchlorates and organic perchlorates. one who will be working with per- sion.1 The potential energy of organic
Ammonium periodate is especially sen- chlorates is given by J. S. Schumacher peroxides is low compared to conven-
sitive to friction. Perchlorates (e.g. mag- in the American Chemical Society tional explosives, but high enough to
nesium perchlorate [Mg(ClO4)2] mar- Monograph Series 146, Perchlorates, be very hazardous.
keted as “Anhydrone”) should not be Their Properties, Manufacture, and The acute toxicity of organic perox-
used as a drying agent if in contact with Uses.” Procedures for dismantling an ides is relatively low (i.e., peracetic
organic compounds or with a strong de- exhaust ventilation system suspected acid: oral LD50, rat; 1540 mg/kg; der-
hydrating acid (such as in a drying train of perchlorate contamination are in- mal LD50, rabbit 1410 mg/kg). How-
that includes a sulfuric acid bubble cluded in the CRC Handbook.9 Pub- ever, most are highly irritating to skin,
counter) is possible.9,10 Perchlorate lication of an updated version of eyes, and mucous membranes and
hazards are multiplied by increased Schilt’s Perchloric Acid and Per- peracetic acid may be a weak carcin-
temperature, dryness and/or perchlor- chlorates is pending.11 ogen in mice. There are no data to
ate content. Abuse of any one or more Dilute hydrogen peroxide solutions suggest that exposure to peracetic acid
of these parameters accounts for nearly (i.e., 3%) are contact irritants and produces carcinogenic, reproductive
all perchlorate related incidents. higher concentrations can cause se- or developmental toxicity in humans.
Perhalogen acids (e.g., hot perchlo- vere chemical burns. Peroxide chemi- Other organic peracids (e.g., perben-
ric acid) are widely used as potent ox- cal burns should be washed gently but zoic acid and m-chloroperbenzoic
idizing agents. Cold 70% perchloric thoroughly and may require medical acid) are less toxic, less volatile and
acid is a strong acid but is not a strong attention.5,10 The acute toxicity of per- less hazardous to handle than perace-
oxidizing agent. The oxidizing power chloric acid is moderate [oral LD50 tic acid.12 Exposure to peroxides and
of perchloric acid increases with tem- (rat) 1100 mg/kg; oral LD50 (dog) 400 associated materials, including vapors
perature and hot, concentrated solu- mg/kg]. It is a potent irritant at low and aerosols, should be minimized.
tions can be very dangerous. The max- concentrations and is very corrosive Aliphatic peroxyacids have a sharp,
imum concentration of perchloric and can cause severe burns to skin, unpleasant odor, the intensity of
acid commercially available is an eyes and mucous membranes at higher which decreases with increasing mo-
aqueous solution of 70% HClO4. concentrations (especially when hot). lecular weight.1,4 Liquid peroxides
However, perchloric acid solutions Perchloric acid has not been found to may penetrate rubber gloves upon ex-
can become highly concentrated from be carcinogenic or to cause reproduc- tended exposure.5
evaporation (e.g., spill or heated di- tive, or developmental toxicity in
gestion procedure) and anhydrous humans.12
perchloric acid is capable of sponta-
neous explosion. Highly concentrated ORGANIC PEROXIDES: SYNTHESIS
AND USE
perchloric should be disposed of ORGANIC PEROXIDES AND OTHER
within 10 days or if any discoloration PER-COMPOUNDS The synthesis of organic peroxides fre-
develops. Anhydrous perchloric is ex- Organic peroxides are characterized quently begins with hydrogen perox-
plosive in contact with wood, paper, by the bivalent -O-O- structure and ide. Hydroperoxides can be prepared
carbon, and organic solvents. Diges- are considered to be structural deriv- by reaction of alkyl halides, esters of
tion of organic material in boiling per- atives of hydrogen peroxide with one sulfuric or sulfonic acids, or alcohols
chloric acid must be conducted is a or both of the hydrogen atoms re- with hydrogen peroxide in alkaline so-
chemical fume hood that is specifi- placed by an organic moiety. Because lution. Peroxy groups may be intro-
cally designed for that purpose. Per- of the weak peroxide bond, organic duced into susceptible organic mole-
chloric acid fume hoods include a spe- peroxides are predisposed to sponta- cules by treatment with a hydro-
cial wash-down feature to prevent neous decomposition. They are excep- peroxide in the presence of a catalyst
buildup of dangerous organic or me- tionally labile to catalysts and promot- such as cuprous chloride. Hydroper-
tallic (copper and copper alloys) per- ers that accelerate decomposition.1 oxides and acylperoxides are prepared
chlorates.9 Aqueous perchloric acid As a class, organic peroxides are from amyl halides or anhydrides, and
solutions are not combustible. among the most hazardous substances from amides of the imidazolide type.
Organic alcohols, aldehydes, ke- handled in the lab. Most are highly Diacyl peroxides are synthesized by
tones, ethers, and dialkyl sulfoxides flammable and extremely sensitive to treatment of carboxylic acids with hy-
can react violently with concentrated shock, heat, spark, friction, impact, drogen peroxide in the presence of di-
perchloric acid, especially at elevated and ultraviolet light. They readily re- cyclohexylcarboiimide. Mixed alkyl-
temperatures. Furr9 included a review act with strong oxidizing and reducing acylperoxides (peresters) can be made
GROUP B: Peroxide hazards on concentration. Test for peroxide formation before distillation or evaporation. Test for
peroxide formation or discard after 1 year.
GROUP C: Chemicals, which are hazardous due to, peroxide initiation of autopolymerization. The peroxide-forming
potential increases for liquids of this group, especially for butadiene, chloroprene and tetrafluoroethylene, such that
these materials should be considered as a peroxide hazard. Test for peroxide formation or discard liquids after 6
months; discard gases after 1 year.
stable products. Storage of peroxidiz- tion of volatile organic peroxidizable low extensive exposure to air or
able chemicals in open, partially compounds. However, peroxide accu- oxygen are particularly dangerous. At
empty, or transparent containers mulation may actually be enhanced by least 10% of the bottom residuals
greatly increases the risk of peroxide refrigeration if the rate of peroxide should be retained during distillation
formation. Peroxidation is accelerated degradation is slowed more than the or evaporative concentration of any
by heat, light, oxygen or air, and ele- rate of peroxide formation. If the sol- potential peroxide-former. The hazard
vated temperature. Fluctuations of vent is held near it’s freezing point, can be reduced by addition of a non-
temperature and barometric pressure peroxidation products may precipitate volatile organic liquid (e.g. mineral
facilitate infiltration of atmospheric from solution and become very shock oil) to the distillation flask. The min-
oxygen into the containers. Initial per- sensitive and dangerous. Some peroxi- eral oil will remain in the distillation
oxide buildup is usually slow because dizable organometallic compounds vessel and dilute the remaining perox-
the exchange of air (containing only (e.g., Grignard reagents) should not be ides. It is essential to always include a
20% oxygen) is gradual. A breach of refrigerated, and there is little or no magnetic stirrer, boiling chips or an
the container seal may allow sufficient evidence that refrigeration slows oxi- inert gas bleed to prevent the localized
oxygen to eliminate the inhibitor then dation of diethyl ether. The vaporiza- concentration of heat and pressure.
initiate and enhance the autoxidation tion of ether may lead to the formation Air or other oxygen-containing mix-
process. Air should always be flushed of an explosive atmosphere, even at tures should never be used for mixing
out of the free space with an inert gas freezer temperature.1,5,14 In any case, during distillation of potential perox-
(usually nitrogen) before sealing. This only completely spark-proof refrigera- ide formers.1,6
is especially critical for the chemicals tors should be used to store ethers or Peroxide impurities in higher boil-
in Groups A and B, particularly if the other volatile peroxide formers. ing point chemicals (e.g. long-chain
inhibitor has been removed (e.g. dis- Laboratory procedures (e.g. evapo- alkyl ethers and the glycol ethers) usu-
tillation) or depleted.1,5 ration, distillation, or spills) that in- ally undergo thermal decomposition
Refrigeration can retard peroxida- crease peroxide concentration or al- at distillation temperatures. However,