Date: Mon, 4 Jan 2010 10:41:03 -0600
Reply-To: DCHAS-L Discussion List <DCHAS-L**At_Symbol_Here**LIST.UVM.EDU>
Sender: DCHAS-L Discussion List <DCHAS-L**At_Symbol_Here**LIST.UVM.EDU>
From: "Clark, Richard C" <rcclark**At_Symbol_Here**BEMIS.COM>
Subject: Re: Unknown Hazardous Chemical
In-Reply-To: <B6B5C68D-2380-445E-94AA-2587494A37DE**At_Symbol_Here**uvm.edu>

Just got back to work this mornin g after a week's vacation and read the postings related to this problem.
 
The chlordane speculation merits comment.  I was the works chemist for Velsicol at Marshall, IL just be fore the plant closed in the late 70's.  That was the only site in the world that manufactured chlordane; Velsicol also manufactured hexachlor at another site (Tennessee, I think).  Chlorda ne is a polychlorinated dicyclopentadiene and had lots of by-products; hexa chlor was hexachlorocyclopentadiene made by a different process and was much purer.  Chlordane was so heavy that it could only be shipped in 30-gal. drums.  It was diluted by ref ormulators with kerosene (5-10% chlordane, I think).  The kerosen e-chlordane mixture could be dispersed in water with the aid of detergent to make an emulsion for field spraying and termite treatm ent.  With the closure of the Marshall, IL plant, acquisition of Velsi col by Great Lakes Chemical (now part of Chemtura), and environmental issues, chlordane manufacture was never re-started.  This might explain the age of the drums.
 
Chlordane is an impure mixtu re containing numerous chlorination byproducts of cyclopentadiene and dicyc lopentadiene.  The EPA published a GC-MS study of it ca. 1976 in Analytical Chemistry which revealed dozens of compou nds.  Velsicol had no idea of that complexity; we were using packed co lumn GC technology for process control.  I'm not sure that GC-MS will be useful for identification given the mixture of kerosene and chlordane. That would be an identification nightmare.
 
Chlordane yellows with age.  The green flame is from the Bielstein test for chlorine.  The emulsio n of the kerosene mixture is cloudy-white.  While the initial boiling point may be 27=B0C, the boiling point may rise quickly ab ove 100=B0C.  An ASTM distillation will give some idea of that.  Infrared spectroscopy of the distillation fractions (10% volume cuts)  should show a mixture of saturated hydrocarbons and chlorination of saturated and unsaturated hydrocarbons.  I'll be surp rised if you can take the distillation to a dry point before the flask cont ents start to smoke; chlordane will likely break down before it distills.  If the low boiling components are chlorinated by-products, they won't flash.
 
Hope this helps (and my memory is n't too inaccurate).
 
Rick Clark
Sr. Research Chemist
Curwood, Inc.
 


From: DCHAS-L Discussion List [mail to:DCHAS-L**At_Symbol_Here**list.uvm.edu] On Behalf Of List Moderator
Sent: Monday, December 28, 2009 11:38 AM
To: DCHAS-L**At_Symbol_Here**LIST.UVM.EDU
Subject: Re: [DCHAS-L] Unknown Hazardous Chemical

From: Andrew Gross <gross.drew**At_Symbol_Here**gmail.com>
Date: December 28, 2009 12:02:48 PM EST
Subject: Re: [DCHAS-L] Unknown Hazardous Chemical


Hi Everyone,

My lab recieved a sample from a power plant that they do not know what
it is and wish to have it identified.  I am trying to ID it because
until I have a better idea it is on hold for all testing (read on to
find out why).  I'm hoping for some thoughts.

Sample is liquid in appearance, but lighter then di-chlo romethane.  I
think it is actually an oil of some kind.  It is transparant yellow
and some say it smells like kerosene.
It forms a white emulsion when mixed with water.< /div>
There is no flash point.  On closed cup method it flames out below
25C.  It does not ignite when exposed to direct flame.  However it
boils around 27C.
Exposed flame turns green (like copper flame), vapors al so turn flame green.
When dried, it turns to a waxy white translucent crystal .  My closed
cup flame is still green meaning it is contaminated by t he vapors.
Vapors in small quanteties (under hood) cause nausea, li ght headedness
and confusion.
pH is 6ish (litmus paper) although client claims it to b e caustic.
All PCB analysis came up negative.

The exposure effects are why all tests are on hold till we have a
better idea as to what were dealing with as well as the remaining
tests for my department involve reacting with acid and p umping
nitrogen through it.

Thoughts, ideas, experiences?  Client has 5 unidentified drums of this
stuff and has no idea what it is.  We need to identify but I am not
going to put anyone in danger until I know more about it .

Andrew Gross






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