hydrazine (h2nnh2) @ Olin Mathieson CHemical

Introduction:

I was fortunate enough to have been hired as a junior chemist by Olin Mathieson Chemical Corporate Research in my senior year, in high school, and into my freshman and sophomore years in college.

This was summer employment with corporate philosophy pinned on the gamble that when I graduated college I would return to work for them as a full time chemist.Certain catastrophic events took place at Olin, which precluded my return the story, needless to say, will be spun later.

Olinís interest in me, even though I never returned, was never lost.

My colleges and I have used Hydrazine over many years, on a commercial scale, and I never lost my fascination for its unique place in our chemical world.

Nor have I lost the memories I had working there, as I am still nostalgic for that place because of the latitude they gave me and what I learned and observed, I can honestly say it was like being in college because it was so demanding to be their 5 days a week on time (I had to drive 50 miles a day! from Buffalo to Niagara Falls) and learning so much. I was a mere18 year old kid hoping for this fantastically exciting career in industrial science and technology.

 

At this point I would like to describe hydrazine to those who are not familiar with its nature and handling. The best description of anhydrous hydrazine is to assume it was a mixture of anhydrous methylamine and concentrated aqueous ammonia in character.

It fumes in air, it smells ammoniacal, it is a colorless liquid somewhat more viscous than water, and to be treated with a great deal of respect. Imagine two amino groups joined back to back and even though its valence shells are filled, it seem unsatisfied with its state, it still seems to aggressively want to react, either as a reducing agent, or a highly reactive intermediate, now youíve got the whole picture. However, unlike ammonia or methylamine, anhydrous hydrazine will explode if ignited in a closed system, even at room temperature so it must always be blanketed with nitrogen.

 

The hydrates 50% and 35% monohydrate are more benign (See below).

 

In 1947 Olin Mathieson began research on its manufacture after they learned there was a large military market because the Germans were using anhydrous hydrazine with hydrogen peroxide for rocket propellants because this combination had an exceptional high-energy release when burned with hydrogen peroxide.

The manufacture of hydrazine, at Olin Mathieson followed a straightforward classic Raschig process, starting from ammonia and sodium hypochlorite with suitable modifications.

 

Reference Ė Industrial and Engineering Chemistry, Volume 45 #11, December 1953 and references therin

 

Reference: Hydrazine by Charles C. Clark, First Edition, Matheson Chemical Corporation, Baltimore, MD 1953 Pages 1-133

The very informative book gives a very large number of topics on the inorganic aspects, and the organic chemistry of hydrazine as well as a very comprehensive review on the physical property, with a multitude of early references up to 1953.

 

Olin Mathieson established themselves as a global source for Hydrazine in the early 60ís, their primary client being United States Government for use as a rocket fuel. They also manufactured large quantities of so called UDMH (unsymmetrical dimethyl hydrazine). The raw materials, in this case being dimethylamine and sodium hypochlorite with suitable modifications.

 

The pilot plant and semi-works were located across the street from the main facility. While I never went in to see the staff there, their were many reports of nasty explosions and one report where the lid was blown off a large distillation assembly and flew across the street (Buffalo Ave.) and in the process decapitated a women who was driving her car. Suffice to say, this was enough to keep me out of that buildingHowever, back in the research area where I worked I had access to the library and soon learned how versatile hydrazine was, since I was allowed a great deal of freedom, for some reasons my boss let me do virtually any project I chose, so naturally I gravitated toward mighty N2H4.

 

Now at this point I must distinguish between hydrazine anhydrous and hydrazine monohydrate and its solutions in water. If anhydrous hydrazine is diluted with water considerable heat is evolved and using the proper stochiometry either 35% or monohydrate is produced.

 

I was particularly fascinated with the two derivatives, Semicarbazide NH2CONHNH2 and thiosemicarbazine NH2CSNHNH2 both of which Olin manufactured from hydrazine not at Niagara Falls at a pilot plant they maintained at Rochester New York, the former Genesee Chemical Company. These were manufactured from sodium cyanate and sodium thiocyanate respectively. See Baker and Gilbert J.Am. Chem. Soc. 64, 2777-80 (1942).

My interest was in a series of pharmaceutical derivatives called Nitrofurans developed by Norwich Pharmaceutical Company see ref.

The nitrofurans were newly discovered potent anti-bacterials that attacked gram negative organisms and at that time were enjoying widespread popularity in everything from veterinary to hospital pharmacies.

Each one of the following compounds they

The third compound was beta-hydroxyethylhydrazine pineapples and pharma

The Wolff-Kishner Reduction is defined as the reduction of a carbonyl compound to a methylene compound by heating with hydrazine and a base. In the Huang Minlon modification diethylene glycol is used as a solvent.

RCORí+ N2H4 + KOHRCH2Rí + N2

Not mentioned in these papers was the use of hydrazine as a powerful reducing agent the use of hydrazine in the Wolff-Kishner reaction we performed many years later on a commercial scale for numerous reactions.

The compounds manufactured commercially facilitated by hydrazine would not be available by any other method. They ranged from perfume and flavor compounds to neutraceuticals.

Anydrous ammonia- I was fascinated on the use and handling of anhydrous ammonia. While I was in the research lab I went on a tour of their ammonia facility which was quite old that time, the smell on walking into that building was enough to knock you out, and I remember seeing the flow of anhydrous ammonia through a very heavy sight glass

They made their ammonia from by-product hydrogen and air the oxygen being removed by some catalytic method

HEF chlorinated derivatives, and sodium methylate