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org/OPRD Article

Study on Autocatalytic Decomposition of Dimethyl Sulfoxide

(DMSO)
Yoshikuni Deguchi,* Masafumi Kono, Yuto Koizumi, Yu-ichiro Izato, and Atsumi Miyake
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ABSTRACT: Dimethyl sulfoxide (DMSO) is widely used due to its excellent solvent properties; however, several serious incidents
have been reported related to the use of DMSO. DMSO can decompose autocatalytically, but we have no consensus with respect to
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the chemical structure and function of the autocatalyst. Thermal decomposition of DMSO was carried out in an inert atmosphere,
and analysis of the nonvolatile fraction indicated the presence of several organic and inorganic acids. DMSO was believed to act as an
oxidizer as well as a reactant in the formation of these acids. The same acids were found in an isothermal heating test, and their
concentrations increased over heating time. Addition of acids to DMSO before starting isothermal heating significantly shortened the
induction period indicating that the acids generated in situ served as autocatalysts for the thermal decomposition of DMSO.
KEYWORDS: dimethyl sulfoxide (DMSO), thermal hazard, decomposition, autocatalyst, acid, induction period

■ INTRODUCTION
Dimethyl sulfoxide (DMSO) is an aprotic solvent with a high
Among the incompatible compounds above, the influence of
acids has been studied most extensively. Traynelis and
dissolving ability as well as other excellent properties, such as a Hergenrother15 reported that the addition of acid accelerated
high dielectric constant, a high boiling point, low vapor DMSO decomposition, with the generation of formaldehyde,
pressure, and free miscibility with water.1,2 In addition to these while the addition of base retarded decomposition.
Santosusso and Swern16 found that an acid was required for
solvent properties common to aprotic solvents, DMSO has low
the oxidation using DMSO and oxygen or hydroperoxide
biological toxicity, unlike the other compounds in this group.3
served to generate an acid catalyst in situ. They determined the
Accordingly, DMSO is the preferred solvent used for a wide
strong acids formed when oxidation was performed using
range of purposes and applications in both laboratory work and
DMSO as an oxidizer in the presence of air or peroxide.17
various industries. DMSO manufacturers have provided
Head and McCarty18 discovered the conditions that brought
product information covering various data, such as its physical
about the complete decomposition of DMSO, and the
and chemical properties, thermal stability, chemical stability,
proposed decomposition mechanism is as follows: (1) A
and safety requirements for handling.1,2
radical cation is formed by the reaction of DMSO and oxygen,
However, despite its wide use, severe incidents associated
(2) the radical cation reacts with another molecule of DMSO
with the runaway reaction of DMSO have been reported.4−6
to produce the dimethyl sulfonium cation, and (3) the
Safety concerns have been stated in industries where DMSO is
dimethyl sulfonium cation acts as a key intermediate in the
used as a solvent or reactant.7−11 Since DMSO is frequently
thermal decomposition of DMSO.
recycled for economic as well as environmental reasons in
The influence of foreign organic acids has been studied, and
industries, many incidents take place during steps in the
it was found that even weak acids accelerated the
recycling process, such as evaporation and distillation.6 The
decomposition of DMSO.19 As such, it is important to note
risks in DMSO distillation have been addressed, and a risk
that DMSO is not an inert solvent, as suggested by Bollyn.20
assessment was conducted.12 When a power failure takes place
The other important aspect observed in DMSO decom-
during distillation, heat removal ceases immediately, while
position is its autocatalytic nature. Although the definition of
heating continues; this scenario may cause a temperature
an autocatalyst or autocatalytic decomposition may vary by
increase to trigger DMSO decomposition resulting in potential
author, the overview described by Stoessel21 is widely
runaway reaction. It is important to understand the heat
acknowledged: “A reaction is called autocatalytic when a
generation process in DMSO decomposition.
reaction product acts as a catalyst on the reaction course”. The
DMSO itself is stable at temperatures below 150 °C, and it
begins to decompose slowly near its boiling temperature (189
°C).1,2 In contrast, DMSO reacts with various chemicals, such Received: March 21, 2020
as oxidizers, reducing agents, organic and inorganic acids, acid Published: August 20, 2020
halides, acid anhydrides, halogens, halogenated organics, and
sodium hydride. In the presence of these incompatible
chemicals, DMSO decomposition begins at a much lower
temperature.1,2,4,13,14

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.oprd.0c00113

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characteristic profile of autocatalytic decomposition is thermal decomposition of DMSO. The review provides a
illustrated in Figure 1. Decomposition proceeds slowly in the thorough explanation of DMSO decomposition, and details of
kinetic analysis were discussed. However, the discussion did
not cover the chemical nature of the autocatalyst function.
This study was performed to elucidate the chemical nature
of the autocatalyst.

■ EXPERIMENTAL SECTION
General. DMSO (99.98%) was purchased from Fujifilm
Wako Pure Chemical Corporation, Japan. Other chemicals
used for analysis were reagent grade, and water was deionized
and distilled in the laboratory.
The analytical gases used were highly purified gases
designated for GC−MS analysis.
Procedure for the Thermal Treatment of DMSO and
the Analysis of the Nonvolatile Fraction. DSC was
utilized to carry out the thermal treatment of DMSO. A small
portion (ca. 2 mg) of DMSO was poured into a high-pressure
Figure 1. Characteristic profile of autocatalytic decomposition. DSC pan made of stainless steel, which was sealed using a
dedicated press machine. All sample preparations were carried
out in a nitrogen glove box.
flat portion called the induction period, and this period lasts for Thermal treatment was performed using a DSC 7000X from
a relatively long time without an exotherm. Rapid exothermic Hitachi High-Technologies Japan under a constant heating
decomposition exceeds slow decomposition at a certain point, rate of 10 °C/min from room temperature to 430 °C.
leading the reaction mixture to undergo a runaway reaction. Completion of DMSO decomposition was verified by the
Prolonged storage of DMSO at elevated temperature may absence of an exothermic peak in a second run. After cooling,
cause the accumulation of decomposed substances, which the stainless pan was mechanically opened under cooling using
catalyze further decomposition. However, it is difficult to liquid nitrogen, and the inner wall was washed with distilled
predict sudden heat evolution given the unexpected timing of deionized water (DDW). The resulting extract was subjected
initiation. As a result, it may be too late to return to normal to ion chromatography (IC) in an instrument equipped with
conditions by the time one notices an abnormality in an electroconductivity detector and mass detector.
temperature and/or pressure. DMSO handling risks in Analytical instruments for qualitative analysis are as follows:
industrial settings may arise from this characteristic decom- The ion chromatograph was a Thermo Scientific DX-600
position profile. equipped with an electroconductivity detector. For TOFMS,
Brogli et al.5 reported that the autocatalytic decomposition an Agilent LC/MSD TOF was used. The columns used were
of DMSO occurred when aliphatic bromide was mixed with Thermo Scientific IonPac AG11-HC and AS11-HC. Experi-
DMSO and that small amounts of zinc oxide extended the ments were conducted in ESI-negative mode.
induction period and moderated the self-accelerating decom- Isothermal Heating Test and Analysis of the
position process once it occurred. Hall6 reported seven Resulting Material. The isothermal heating test was carried
incidents associated with DMSO decomposition in his paper, out using ARC, and the detailed experimental conditions are as
and some cases were related to autocatalytic decomposition or follows. For ARC, a TIAX accelerating rate calorimeter was
lacked an adequate thermal history for DMSO. used, conducted in a nitrogen atmosphere at temperatures of
In the early stage of popularization of accelerating rate 160, 170, and 185 °C. The sample bomb was an SUS316. The
calorimetry (ARC), Cardillo and Girelli22 carried out DMSO sample amount was 3.5 g. The minimum sensitivity was 0.02
decomposition experiments using ARC both in a nitrogen K/min. The cutoff temperature was 200 °C. The test period
atmosphere and in the air. In their results, the ARC self-heating was 10000 min maximum.
curve of DMSO in a nitrogen atmosphere showed a long Samples isothermally heated in the bomb at 185 °C for
induction period, whereas DMSO thermolysis in the air 2000, 4000, and 6000 min were quantitatively analyzed to
showed no such induction period. They realized that some determine the acid concentration. The isothermal heating test
acids were formed when decomposition was carried out in the was repeated from the beginning every time because
air; notably, they mentioned that DMSO decomposed in the intermediate sampling from the closed vessel was difficult.
air through a non-autocatalytic radical-like mechanism, After cooling, the resulting solution was diluted 10 times
although the detailed mechanism was not discussed. with DDW and subjected to IC analysis. For IC, a Thermo
Several others have studied DMSO decomposition to Scientific Integrion RFIC was used, with an electroconductivity
address industrial concerns,7−14,23 but we have no consensus detector and columns of IonPac AG18-4 μm + AS18-4 μm (4
with respect to the chemical structure and function of the mm φ × 150 mm). The eluent was the KOH gradient with the
autocatalyst. Dien et al.24 showed that the adiabatic behavior of use of an eluent generator.
autocatalytic decomposition could be expressed using kinetic Effect of Acid Addition on DMSO Decomposition. A
parameters deduced from the isothermal differential scanning small portion of acid was added to DMSO before starting the
calorimetry (DSC) curve. ARC is used to assess the thermal isothermal heating test using ARC. The concentrations of the
hazard potential of energetic chemicals, including DMSO, as representative acids were taken from the data point at 6000
ARC can provide near-perfect adiabatic conditions.8−10 min and 185 °C. In the acid investigation, the headspace was
Brandes and Smith25 reviewed the literature discussing the filled with helium, and the temperature was set to 185 °C. To
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Figure 2. Ion chromatograms obtained for the nonvolatile fraction. Upper: data recorded by the electroconductivity detector, lower: total ion
chromatogram (TIC) recorded by the mass detector.

determine the effect of the environmental gas, air and carbon volatile fraction after DMSO decomposition.15 Similarly, acetic
dioxide were separately introduced into DMSO using a small acid and formic acid were thought to be the oxidized products
tube as a bubbler, and the headspace of the ARC bomb was of the corresponding aldehydes.
carefully sealed with the same gas. An isothermal heating test Santosusso and Swern16 observed the in situ generation of
was also conducted on these samples at 185 °C. Detailed ARC the strong acids, methanesulfonic acid and sulfuric acid, when
experimental conditions are as follows. For ARC, a THT Euro DMSO was heated with peroxide. The same authors claimed
ARC was used, under a helium atmosphere for acid that they carried out qualitative analysis of the acids by the ion-
investigation and at a temperature of 185 °C. The sample exchange isolation technique, but unfortunately, no detailed
bomb was an SUS316. The sample amount was 3.0 g. The information regarding the analysis was provided.17 The
minimum sensitivity was 0.02 K/min. The cutoff setting was generation of these strong acids was confirmed in our
400 °C or 12.0 MPa. The test period was 250 h maximum. experiment. It has been reported that peroxide or air is

■ RESULTS AND DISCUSSION

Analysis of the Nonvolatile Fraction after DMSO
necessary to generate sulfuric acid from DMSO;16,17 however,
nothing other than DMSO existed in our experiment. A simple
question arises with respect to the identity of the oxidizer in
Decomposition. Ion chromatograms of the nonvolatile this inert atmosphere. Named organic reactions such as
fraction after complete decomposition are shown in Figure 2. Kornblum oxidation27 and Swern oxidation,28,29 both of
Sulfuric acid (H2SO4) and methanesulfonic acid were which utilize DMSO as a selective oxidizer, suggest an answer:
identified by their retention times. Two peaks with relatively it is rational to conclude that DMSO can be an oxidizer as well
short retention times were analyzed by time-of-flight mass as a reactant in an inert atmosphere at elevated temperature.
spectrometry (TOFMS), as shown in Figure 3, and the Many authors have analyzed the volatile fraction in DMSO
identification data are summarized in Table 1. decomposition; however, the nonvolatile fraction seems to
Sulfuric acid was considered to be the oxidized product of have been a blind spot in prior studies.
sulfurous acid (H2SO3), while H2SO3 itself was not detected. Isothermal Heating Tests and Analysis. Isothermal
Sulfurous acid was considered to be formed by the addition of heating tests were carried out at three temperatures, and no
sulfur dioxide (SO2) and water because formation of sulfur exothermic peak appeared at 160 and 170 °C within the
dioxide was reported by Thyrion and Debecker26 while water standard testing time of 10000 min. When the isothermal
was found by Traynelis and Hergenrother in the analysis of the heating test was performed at 185 °C, a steep exothermic peak
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Figure 3. TOFMS data obtained for the carboxylic acids. Upper: Peak #1, lower: Peak #2.

Table 1. Identification Data of Carboxylic Acids

peak number m/z, detected estimated ion estimated composition calculated mass matching ratio (%)a estimated compound
−
n1 59.0142 [M−H] C2H4O2 60.0211 86.04 acetic acid
n2 44.9987 [M−H]− CH2O2 46.0055 97.52 formic acid
a
The matching ratio was calculated from the combination of three factors: (1) difference between the detected m/z and the calculated one, (2)
difference between the detected isotope ratio and the calculated one, and (3) mass difference between the detected isotope and the calculated one.

appeared at approximately 9000 min, as shown in Figure 4. It is

worthwhile to note that DMSO finally underwent exothermic
decomposition near but below its boiling temperature in this
closed system without any foreign impurities. The thermal
behavior was regarded to be characteristic of autocatalytic
decomposition with a long induction period.
The acid concentrations in the intermediate samples are
summarized in Table 2. Several kinds of acids were found in
MS analysis, and the number of acidic species detected here
was greater than that detected in the DSC experiment above.
The reason for this is assumed that the isothermal heating
sample was carried out at 185 °C, much lower than the final
temperature of ramp DSC, and the intermediate sample was
collected in the early point of the induction period where most
part of DMSO remained unreacted. Limited acids were
supposed to remain after the complete decomposition of Figure 4. Isothermal heating test (1): temperature and pressure time
DMSO owing to their thermal stability. The concentrations of course obtained for DMSO.
acids increased over heating time, suggesting that acids were
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Table 2. Acid Concentrations in the Intermediate Samples Heated at 185 °C

acid concentration (mg/L)
time elapsed (min) lactic acid acetic acid methanesulfinic acid formic acid methanesulfonic acid sulfuric acid
2000 <10 <10 <10 67 9.8 <8
4000 <10 <10 14 220 24 8.4
6000 21 <10 23 2100 130 38

generated and gradually accumulated in the inert atmosphere strength of these acids in water, sulfuric acid (pKa −3.19 ±
during the induction period. Formic acid showed the highest 0.15) 30 is many orders of magnitude stronger than
concentration followed by methanesulfonic acid and sulfuric methanesulfonic acid (pKa 1.75 ± 0.50),30 but methanesul-
acid. These acids were generated and accumulated during the fonic acid unexpectedly showed a larger acceleration effect on
induction period, and they acted as catalysts in the DMSO decomposition. Similarly, although formic acid is a
decomposition of DMSO. weak acid with a pKa of 3.74 ± 0.10,30 the sample containing
Effect of Acid Addition on DMSO Decomposition. The 2000 ppm formic acid showed the largest acceleration effect on
effect of formic acid was compared to that of blank DMSO, as the induction period among the acids investigated.
shown in Figure 5. The sample containing 2000 ppm formic The effects of the environmental gas were notable, as shown
in Figure 7. Bubbling coupled with filling of air in the

Figure 5. Isothermal heating test (2): effect of formic acid.

Figure 7. Isothermal heating test (4): effect of environmental gas.

acid exhibited a steep exothermic peak shortly after 50 h, while

blank DMSO exhibited a peak shortly after 200 h. Thus, the
acceleration effect of formic acid became obvious, approx- headspace of the ARC bomb showed the largest acceleration
imately 1 4 of the way through the induction period. effect in this study, confirming Cardillo and Girelli’s results.22
Oxygen in the air was believed to play an important role in acid
Similarly, 130 ppm methanesulfonic acid and 40 ppm
generation, as described by Santosusso and Swern.16,17
sulfuric acid were compared to blank DMSO, as shown in
Regarding the effect of carbon dioxide, two explanations may
Figure 6. Both acids exhibited an acceleration effect, and the
be possible: (1) Carbonic acid (H2CO3) was formed in the
steep exothermic peak of the sample containing 130 ppm
ARC bomb due to the addition of carbon dioxide with existing
methanesulfonic acid began much earlier than that of the
water and acted as an acid or (2) CO2/DMSO worked
sample containing 40 ppm sulfuric acid. Considering the
effectively in the reaction as this combination has recently been
found to significantly advance DMSO oxidation.31 Regardless,
it is suggested that the combination of CO2/DMSO be
avoided when DMSO is recycled.
Although the reason for change near the turning point in
Figure 1 remains unclear, there is no doubt the accumulation
of acids that shortened the induction period of DMSO
decomposition. The generation of acids in situ seems to meet
Stoessel’s definition of an autocatalyst.21

■ CONCLUSIONS
In this work, the analytical study was combined with
isothermal heating tests to elucidate the autocatalysts involved
in DMSO decomposition. The relevant findings were as
follows:
(1) Several kinds of acids were found in the nonvolatile
Figure 6. Isothermal heating test (3): effects of methanesulfonic acid fraction after complete DMSO decomposition in an
and sulfuric acid. inert atmosphere.
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