Skip to Main Content

Letters

June 14, 2010
Volume 88, Number 24
pp. 4-6

June 14, 2010 Letters

  • Print this article
  • Email the editor

Latest News



October 28, 2011

Speedy Homemade-Explosive Detector

Forensic Chemistry: A new method could increase the number of explosives detected by airport screeners.

Solar Panel Makers Cry Foul

Trade: U.S. companies complain of market dumping by China.

Novartis To Cut 2,000 Jobs

Layoffs follow similar moves by Amgen, AstraZeneca.

Nations Break Impasse On Waste

Environment: Ban to halt export of hazardous waste to developing world.

New Leader For Lawrence Livermore

Penrose (Parney) Albright will direct DOE national lab.

Hair Reveals Source Of People's Exposure To Mercury

Toxic Exposure: Mercury isotopes in human hair illuminate dietary and industrial sources.

Why The Long Fat?

Cancer Biochemistry: Mass spectrometry follows the metabolism of very long fatty acids in cancer cells.

Text Size A A


More On Sodium Azide

It was important to read the recent letters that revisited the dangers associated with the use of sodium azide (C&EN Jan. 11, page 4; April 5, page 5; and Nov. 9, 2009, page 8). None of these letters, however, mentions the hazards of exposing sodium azide to halogenated solvents.

We earlier reported the probable production of diazidomethane when methylene chloride was used as an extraction solvent in the workup of a reaction that employed excess sodium azide as a reagent (C&EN, March 14, 1994, page 4). It is convenient for chemists to use heavier than water chlorinated solvents for extraction of reaction mixtures that are diluted with water. However, if the aqueous phase contains azide, this procedure can lead to the production of the very explosive diazidomethane (N to C weight ratio of 6). Chlorinated solvents should never come into contact with sodium azide.

Norton P. Peet
North Andover, Mass.



Chemical Safety: Dimethyl Sulfoxide Overpressurization Hazard

We would like to report an overpressurization that occurred in our laboratory while conducting a synthesis protocol for a metal organic framework structure (MOF) using the solvothermal method outlined by Shengquian Ma and coworkers (Angew. Chem. Int. Ed. 2008, 47, 4130). In this paper, DMSO (dimethyl sulfoxide) is decomposed to form sulfate in the presence of H2O2 as the bridging ligand between two metal centers.

The described reaction was conducted at 145 °C for 72 hours in a sealed Pyrex tube. This paper inappropriately references Pandey (J. Org. Chem. 2007, 72, 369) as the methodology. In their paper, Pandey and coworkers describe a derivative of the Swern reaction that is conducted at -78 °C due to the exothermic nature of this oxidation.

Referencing Ma, a researcher at Los Alamos National Laboratory scaled up this reaction from 1.5 mL to 12 mL DMSO and conducted the reaction in a Teflon-lined Parr vessel (model number 4745 ADB) that was placed on the bottom of a convection oven set to 150 °C and left for the weekend. The following Monday, the researcher saw that the bottom flange lip of the Parr vessel had sheared off as intended when overpressured. This shearing event was energetic enough to dent the bottom of the oven, causing the metal plate of the oven bottom to contact the heating elements, which resulted in an electrical shortage.

We were initially concerned that perchlorate salts formed during the chemical synthesis and may have detonated with the DMSO, but we have found no evidence supporting this hypothesis. Additional experiments were conducted with appropriate engineered controls to protect against a recurrence. Although nearly identical reaction conditions were used, the Parr vessel did not rupture. However, a thermocouple placed on the Parr vessel recorded an 11.4 °C temperature increase lasting approximately one hour after approximately 27 hours of heating.

Although the exact nature of this energetic release is uncertain, we have concluded that several events may have contributed. First and foremost, the exothermic nature of the oxidation of DMSO was not communicated in the publication, and the experiment was conducted close to the boiling point of DMSO (189 °C). Second, an old Parr vessel (manufactured between 1969 and 1973) with an uncertain history of use was used for experimental chemistry; the vessel was not equipped with a burst disk, which is now the preferred design. Finally, the Parr vessel was placed on the bottom plate of the oven, which was later found to have a temperature that may have been on the order of 
35 °C higher than the oven set temperature of 150 °C. We believe these were critical factors that resulted in the energetic release during the experiment.

Although complete oxidation of DMSO to CO2, SO2, and H2O would generate significant volumes of gas that would exceed the pressure rating of the Parr vessel, there is not enough oxygen present for this to have occurred. A thermal ignition related to the exothermic nature of the reaction and the fact that the vessel was likely to have been much hotter than the 150 °C oven set point may have generated significant moles of gas that would have exceeded the pressure capacity of the Parr vessel.

Best practices would include checking critical published references prior to proceeding with an experiment, using appropriately designed experimental vessels, not placing reaction vessels on the bottom of ovens, and not scaling up reactions until proven safe. Researchers who plan to use DMSO for chemical experiments are directed to the review by T. T. Lam and coworkers that outlines many hazards associated with the energetic decomposition of DMSO at temperatures below its boiling point in the pure phase (J. Thermal Anal. Calor. 2006, 85, 25).

Toti E. Larson and Ruqiang Zou
Los Alamos National Laboratory



PD Not The Same As Pd

I received my edition of the May 24 issue of C&EN this morning. As per usual, I took my first cursory look before breakfast. When I arrived at page 9, I could not believe what I read on the bottom half of the page: “NEW START FOR PD(III) CHEMISTRY.” I have spent over 50 years in the classroom trying to make it clear to my students that PD does not equal Pd! To see such a gross error in such a learned journal is beyond belief!

But when national news anchors do not match plural nouns with plural verbs, I guess that I am expecting too much. They also butcher the subjective tense. I try hard to overlook an individual’s errors, but this headline is beyond my level of tolerance!

Darrell H. Beach
South Bend, Ind.

Editor’s Note: The headline in question contained a typographical error.



The More Things Change

Rudy Baum’s May 3 editorial (page 3) includes the comment that the world has changed, that chemists have to get used to the idea that they will be working for several employers over the course of their careers, and that this is not a comfortable prospect for anyone.

In 1963, armed with a doctorate in organic chemistry, I began my career as a full-time chemist. After 33 years in various laboratory and supervisory R&D capacities primarily in polymer applications, I had worked for seven different chemical companies. The sectors of chemical industry I was involved with saw a constant flow of mergers and acquisitions, the birth and death of new business ventures, major relocations, internal merging of operating divisions, outright sales, complete shutdown of companies, and so on. I was one of many having to find a new job every several years. I finally found the stability I was seeking in my career when I formed my own consulting business.

In other words, the prospect of working for several different employers in a chemical career has been with us for some time.

Daniel Kruh
East Brunswick, N.J.



Chemical & Engineering News
ISSN 0009-2347
Copyright © 2011 American Chemical Society
  • Print this article
  • Email the editor

Services & Tools

ACS Resources

ACS is the leading employment source for recruiting scientific professionals. ACS Careers and C&EN Classifieds provide employers direct access to scientific talent both in print and online. Jobseekers | Employers

» Join ACS

Join more than 161,000 professionals in the chemical sciences world-wide, as a member of the American Chemical Society.
» Join Now!