Applications of Chemical Education in the ‘Real World’ David M. Manuta, Ph.D., FAIC, President,...

Applications of Chemical Educationin the ‘Real World’

David M. Manuta, Ph.D., FAIC, President,

Manuta Chemical Consulting, Inc.

Waverly, OH 45690-1208

Tel: 740-947-7998

Fax: 740-947-1565

http://www.dmanuta.com

E-mail: dmanuta@dmanuta ormc2@dmanuta.com

June 10, 2005 at the Chemical Heritage Foundation in Philadelphia, PA

Mission Statement:

• The Application of Fundamental Chemical Principles to Solve Problems.

Vision Statement:

• To Solve Problems That Aren’t in Any Book.

Business Objective:

• Have I Applied My Specialized Knowledge to Help Others Who Under Other Circumstances Wouldn’t Be Able to

Help Themselves?

Manuta Chemical Consulting, Inc. (MC2) has been involved in many interesting scientific investigations.

Among these investigations are:

Follow Up to the Shut Down of a Chemical Manufacturing Plant in Nevada

Unusual Chemical Reactions in a Chemical Release at a Rail Yard in Texas

Follow Up to the Shut Down of aChemical Manufacturing Plant in Nevada

Advanced Specialty Gas (ASG) facility in Dayton, NV was a manufacturer of nitrogen trifluoride (NF3).

This gas has been used as a rocket propellant and has an application in the manufacture of circuit boards.

With the phase out of sulfur hexafluoride (SF6), due to greenhouse gas and global warming issues, the demand for NF3 has grown in recent years.

Nevada Counties

Lyon County, NV 

Nitrogen Trifluoride

F F

\ /

N:

|

F

NF3

ASG obtained a special use permit from the Lyon County (NV) Board of Commissioners to manufacture NF3. The special use permit allowed ASG to keep ammonia (NH3) and hydrogen fluoride (HF) on site.

The balanced chemical reaction to produce NF3 is:

NH3 (g) + 3 HF (g) NF3 (g) + 3 H2 (g) (1)

where: (g) = gas

The special use permit indicated the amounts of NH3 and HF that Lyon County would allow ASG to store on-

site.

In my investigation, among other findings:

I was surprised to learn that ASG was allowed to keep more NH3 on-site than HF.

The HF became the limiting reagent in the NF3 manufacturing process.

I was also surprised to learn that the H2 was vented out a smoke stack. No attempt, to the best of my knowledge, was made to recover it.

ASG had three releases to the environment and one explosion which blew the roof off of their lab between 1997 and 2000. The explosion also started a brush fire in the immediate area of the plant.

It was after the explosion and brush fire that my expert services were requested.

The owner of the real estate contiguous to the plant recognized that he would be unable to sub-divide his land for residential housing as long as the ASG plant continued to operate in Dayton, NV. I was retained, primarily, to protect this man’s investment.

Lyon County had previously hired experts who did not have experience in fluorine chemistry. As a result, little progress had been made regarding ASG.

I testified before the Lyon County commissioners in their chambers and I was specific in identifying the unsafe practices at the facility.

The Lyon County commissioners one week later voted 3-2 in October 2001 to revoke ASG’s Special Use Permit. This action effectively shut the ASG facility down.

Copies of my technical report plus articles from the Carson City and Reno newspapers are available.

Population Increases between July 1, 2003, and July 1, 2004

http://geography.about.com/od/obtainpopulationdata/a/fastcounties04.htm

# County Increase

1 Flagler Co., FL 10.1%

2 Kendall Co., IL 8.3%

3 Loudon Co., VA 8.1%

4 Hanson Co., SD 7.9%

5 Lincoln Co., SD 7.5%

6 Lampasas Co., TX 7.3%

7 Lyon Co., NV 7.2%

Wrap-Up on Lyon County, NV Plant Shutdown

I had been to Lyon County, NV twice. The first time was in October 2001 (shut the plant down). I returned in March 2003 for an Appeal.The Lyon County Commissioners voted 3-2 to maintain the revoked status of the Special Use Permit.

For 2 years, I hadn’t heard from my client.He’s been busy building houses!

Unusual Chemical Reactions in a Chemical Release ata Rail Yard in Texas

Acid Catalyzed Hydrolysis of Ethyl Acrylate in Maverick County (Eagle Pass), Texas

Texas County Locator

Eagle Pass, TX

Multiple Expert Case

Medical/Toxicology Expert

Another Chemical Expert

Computer Modeler and Simulation Expert

Ethyl Acrylate

O

CH2=CHC-OCH2CH3

C5H8O2

Ethyl Acrylate in Rail Car

Toxicologist reports that Acrylamide is the chemical agent that the Plaintiffs were exposed.

Union Pacific Railroad Was the Key Defendant

Railroad denies responsibility for the January 2001 incident in the US-Mexico

border crossing in Eagle Pass, TX.

Chemical Reactions of Ethyl Acrylate

1. Hydrolysis - generate acrylic acid

2. Polymerization

Acrylic Acid

O

CH2=CHC-OH

C3H4O2

Hydrolysis Reaction of Ethyl Acrylate

C5H8O2 (l) + H2O (g) C3H4O2 (l) + C2H5OH (l) (2)

where: (l) = liquid

Acid Catalyzed Ester Hydrolysis

 Reversible Equilibrium

http://www.wou.edu/las/physci/ch336/lecture/lect18.htm

Polymerization Reaction in Ethyl Acrylate

n CH2=CH + heat or light to initiate --(CH2—CH)n-- + heat (3)

| |

G G

Where: n is an integer (n = 1,2,3,…) and G is a pendant group.

In this instance G is C3H5O2

Polymerization Reaction Inhibition

The liquid ethyl acrylate in the rail car is inhibited in order to mitigate the polymerization reaction.

The inhibitor most frequently used to suppress the polymerization reaction is monomethyl ether

hydroquinone or MEHQ or 4-methoxyphenol

Polymerization Reaction Vapor Pressure

Ethyl Acrylate has a finite vapor pressure.

It is not unusual for the temperature to reach 80 degrees Fahrenheit in January in Eagle Pass TX.

The safety valve on the rail car actuated to relieve the excess pressure. Valve then reseated itself when the excess pressure had been vented.

Witnesses noticed that the rail car appeared to be leaking. Union Pacific contractor called in to secure the rail car.

Polymerization Reaction Contribution

Contractor, apparently, charged rail car with high pressure nitrogen.

Inhibitor was blown out of rail car along with a substantial quantity of the liquid ethyl acrylate.

Liquid ethyl acrylate in resulting plume then reacts with moisture (relative humidity) in the air.

Acid Catalyzed Ester Hydrolysis

Acid

Ester + Water Acid + Alcohol (4)

Source of the Acid Needed for Catalysis

Emissions from Diesel Engine

http://www.nett.ca/faq_diesel.html

Table of Diesel Emissionshttp://www.nett.ca/faq_diesel.html

CO HC DPM NOx SO2

vppm vppm g/m3 vppm vppm

5-1,500 20-400 0.1-0.25 50-2,500 10-150

Diesel Particulate Matter and Sulfur Dioxide http://www.nett.ca/faq_diesel.html

Diesel particulate matter (DPM), as defined by the EPA regulations and sampling procedures, is a complex aggregate of solid and liquid material.

Sulfur dioxide (SO2) is generated from the sulfur

present in diesel fuel. The concentration of SO2 in the

exhaust gas depends on the sulfur content of the

fuel.

High Temperature Oxidation of Sulfur Dioxide

http://www.nett.ca/faq_diesel.html

At high temperatures, above 400°C, a counterproductive process may occur in the catalyst. It is the oxidation of sulfur dioxide to sulfur trioxide, which combines with water forming sulfuric acid: 

2 SO2 (g) + O2 (g) 2 SO3 (g) + 2 H2O (g) 2 H2SO4 (l) (5)

Acrylic Acid Formation

In excess of 10,000 tractor-trailer trucks cross the border between Piedras Negras, Mexico and Eagle Pass, TX each day.

There is an ample supply of diesel particulate matter (substrate) and sulfur-bearing chemicals to convert a finite amount of the ethyl acrylate released from the rail car to acrylic acid.

Acrylamide

O

CH2=CHC-NH2

C3H5NO

Formation of Acrylamide

C3H4O2 (l) + NH3 (g) C3H5NO (s) + H2O (g) (6)

where: (s) = solid

Source of the Ammonia

The property that the Union Pacific rail yard occupies is on the grounds of the former wastewater treatment plant in Eagle Pass, TX.

I had requested that air and soil samples of the area be taken. In the Fall of 2003, more than 2 years after this release, there were still measurable quantities of ammonia percolating from the soil.

At my Deposition, I calculated for the opposing counsel that there was enough available ammonia to generate the necessary quantity of acrylamide to induce the Plaintiff illnesses.

On-going work

Our current work is focused in:

Chemical Consultations

Expert Witnessing in the Physical Sciences

Fire Investigations

Insurance Subrogation Cases

Mediating Disputes

Nuclear Chemistry Issues

Making a difference for our clients is our goal.