viernes, 8 de marzo de 2013

CHEMISTRY'S SURPRISES

Chemical engineering is an uneasy amalgam of industrial chemistry and mechanical engineering. In the U.S., it had its rudimentary beginnings with a course taught at the Massachusetts Institute of Technology by Lewis N. Norton in 1888. Since then, our profession has expanded away from its roots. Today, I think most chemical engineers are more comfortable with mechanical engineering than chemistry. So, let's consider some of the chemistry that you might want to re-remember. 

Here's one of my favorites: the Brønsted–Lowry theory of acids. Strictly speaking, it states that a compound is an acid if it can donate a proton (H+) and a base if it can accept a proton. Sounds like cash flow from senior economics, doesn't it? In simple terms, Brønsted–Lowry means that to every other compound or material, a compound is either an acid or a base. When I worked at Anheuser-Busch, I was fascinated by the large craters etched into our otherwise impervious concrete pads. Acid produced by bacteria-eating molasses that had spilled during tank filling created them. That was Brønsted at work! Concrete has a pH of about 12. A typical organic acid produced by bacteria is probably in the 5–6 range. To concrete, even pH-7 rain is an acid.
Now and then, Le Chatelier's principle — a stress imposed on a chemical system at equilibrium will shift the equilibrium to relieve the stress — has bitten a few forgetful engineers in the hindquarters. At Millennium Inorganic Chemicals, we inherited a 1,500°C gas-phase reactor designed by DuPont; flue gas, oxygen and titanium tetrachloride, caged in nitrogen, are heated in the middle of the plug-flow reactor. Jamming so much nitrogen on the reactant side of an equation, with only oxygen present, caused mischief: nitric acid ate our lined tank at the other end of the process. So, we switched from nitrogen to argon during startup.

Our gas-phase reactors proved another interesting chemical principle: gas-phase reactions always are the purest, except possibly for gas/solid reactions with selective catalysts. 

Biocatalytic processes can pose special complications. Jim Dye briefly touched upon this in his kinetics class: In 1778, Carl Wilhelm Scheele introduced Schweinfurter (Prussian) green. This copper arsenate dye became popular in wallpaper — even more so when it was discovered that the dye killed bedbugs! In places with a cool, damp climate (like much of Europe), mold can grow on the wallpaper. The mold consumes the starch used in the paste to put up the wallpaper. It also takes up arsenic from the dye, which through a complex series of biochemical reactions is turned into trimethylarsine oxide and then reduced to poisonous trimethylarsine, which is excreted as a gas. People living in rooms with the wallpaper grew sick and even died. Prussia banned the dye in 1838, England and France much later. It was not until 1945 that a chemist identified trimethylarsine as the culprit. For more information on this tale, see: www.cas.umt.edu/geosciences//faculty/moore/G431/lectur17.htm
Water solubility often gets chemical engineers in trouble. Members of upper Group 1 in the periodic table, e.g., Na–K, are nearly always soluble. Away from Group 1, carbonates, phosphates, sulfates, and hydroxides generally are insoluble. In the transition elements, with the exception of Pb and Ag, chlorides, nitrates and acetates are soluble. 

Then, there's the eruption that results when you drop a Mentos candy into a carbonated beverage. Some chemists argue it stems from bubbles forming on the surface of the Mentos, but I think they're all wet. I've seen the same effect with a root beer float and by adding saccharine to hot tea: it's surface tension. When two soluble components are added together, surface tension decreases (per the Gibbs isotherm equation). The opposite result occurs when two insoluble or semi-soluble components are mixed together. Because Mentos are soluble in the pop, the surface tension drops and a geyser erupts. TV's MythBusters concluded that the pitting of the Mentos candy creates abundant sites for nucleation (http://dsc.discovery.com/tv-shows/mythbusters/videos/diet-coke-and-mentos-minimyth.htm). They forgot that you still have to get the carbon dioxide to form. The extensive surface area is a factor, just like the saccharine in my tea. This may seem far afield from our business but it isn't. Improper use of a surface-tension-decreasing foam was to blame for a fatality at Millennium.



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GREEN CHEMICALS

The Green Seal certification is granted by the organization with that name and has a great number of members contributing with the requirements to pass a raw material or a chemical product as "green". Generally for a material to be green, has to comply with a series of characteristics like: near neutral pH, low volatility, non combustible, non toxic to aquatic life, be biodegradable as measured by oxygen demand in accordance with the OECD definition.
Also the materials have to meet with toxicity and health requirements regarding inhalation, dermal and eye contact. There is also a specific list of materials that are prohibited or restricted from formulations, like ozone-depleting compounds and alkylphenol ethoxylates amongst others. Please go to http://www.greenseal.com/ for complete information on their requirements.
For information on current issues regarding green chemicals, see the blog from the Journalist Doris De Guzman, in the ICIS at: http://www.icis.com/blogs/green-chemicals/.
Certification is an important — and confusing — aspect of green cleaning. Third-party certification is available for products that meet standards set by Green Seal, EcoLogo, Energy Star, the Carpet & Rug Institute and others.
Manufacturers can also hire independent labs to determine whether a product is environmentally preferable and then place the manufacturer’s own eco-logo on the product; this is called self-certification. Finally, some manufacturers label a product with words like “sustainable,” “green,” or “earth friendly” without any third-party verification.
“The fact that there is not a single authoritative standard to go by adds to the confusion,” says Steven L. Mack M.Ed., director of buildings and grounds service for Ohio University, Athens, Ohio.
In www.happi.com of June 2008 edition, there is a report of Natural formulating markets that also emphasises the fact that registration of "green formulas" is very confused at present, due to lack of direction and unification of criteria and that some governmental instittion (in my opinion the EPA) should take part in this very important issue.