Author Archives: gaussling

About gaussling

Gaussling is a senior scientist in the chemical business. He occasionally breaks glassware, spreads confusion and has been known to generate new forms of hazardous waste. Gaussling also digs aerospace, geology, and community theatre.

Adiabatic Delta T

We ran our first experiments in the reaction calorimeter today. They were very elementary, involving only the metering one reactant into another at constant reaction temperature.  The results suggested strongly that the reactants were consumed promptly and that good control of temperature is obtained by adjustment of the feed rate. Halt the feed and Qr falls off promptly. This is a very desirable attribute in semi-batch processing. 

From the data workup we determined the adiabatic ΔT, or ΔTad, and were able to follow the heat evolution measured in several ways, but most interestingly in watts per liter. It is desirable to know how many watts of heat evolution your reactor is capable of removing. Engineers think in terms of heat evolution as watts per unit volume. Calibration of a reaction vessel can tell you how many watts of heat the reactor can remove at a defined level of fill and agitator speed.  RC1 data can tell engineering how many watts per liter the reaction mass is capable of. 

Next we ran the reactor in adiabatic mode where the jacket temperature is programmed to follow the reaction mass temperature. The idea is to exert dynamic temperature control via the jacket to make the vessel behave as a Dewar.  We predicted the maximum reaction temperature  by simply adding the ΔTad to the initial temperature. We allowed the reaction enthalpy to ramp the temperature.

The actual endpoint temperature was within two degrees of the predicted temperature and below the bp of THF. This is a measure of the potential for runaway.  If the Maximum Temperature of the Synthetic Reaction (MTSR) is below the solvent bp, then you are in a lesser hazard zone. This temperature would be achieved in an adiabatic system.

A few observations- the heat capacity, Cp, is not constant over the course of a reaction. A little reflection should suggest this.  But it does not automatically follow that the Cp increases in magnitude over the reaction progress, which would offer some thermal buffering capacity.

A Fine Caloric

I’m getting to know the RTCal software that animates my RC1.  Thinking about reactions in terms of their enthalpy profile continues to provide deeper insights for an organikker like me.  It is yet another indication that P-Chem is the central pillar of the central science.  

Our culture is driven foreward by exothermicity. We energize the machines of progress and of war by harnessing the exothermic drivers, be they nuclear or chemical.  

Our exothermic sun pumps a global weather machine that provides the motive force to spin the wind turbines to energize our iPads. The sun evaporates water for it’s eventual depostion at high gravitational potential for the release of hydroelectrically accelerated electrons.  Hydroelectric power is an expression of stellar nuclear exothermicity.

The thermal web of our world is an eternal equilibrium of latent and sensible heat flows.  Water’s latent heat of condensation helps to ramp up thunderstorm formation with the result of flowers and high fructose corn syrup and tornados.  The metabolic heat of formation of water and CO2 warms our bodies and provides animation for our desires and our many methods of locomotion.   Dancing and laughter and lust thrive because of exothermicity.

Our lives are spent in the semi-fluid atomic matrix of our bodies while a continual stream of energy flows through them, energizing  metabolism through the magic of ATP and then diffusing into the surroundings.  This energy has resulted in the universe becoming self-aware through the sentience of material beings.

Eventually, because of the disorder accumulated by the large number of exothermic transformations inherent to continuous metabolism, our legs will stiffen and our jaws will lock shut in death as the stream of energy ceases to issue from us. The transience of sentience is rooted in thermodynamics.  How this can be is still quite mysterious.

Borders Books to close its doors this week.

The Borders books chain is set to liquidate, possibly this Friday according to this link. But, like the elk with a broken leg, if the grizzlies don’t get it, the winter surely will. According to reports, the firm was beset with poor management, superior competition, a paradigm shift in buying behavior, and a crummy overall economic picture. The creditors- publishers to a large extent- must be satisfied.

As a frequent patron of Amazon, I hold some personal responsibility for this. I did enjoy browsing in the local store. I bought my issues of Nuts and Volts, Asimov’s Science Fiction, and Kitplanes. But in the end, Amazon had the selection I wanted to spend money on. Obscure print-on-demand books from the 19th century. Not your basic consumer fare at a Borders.

For we browsers of the world, this is a definite loss. Of course, the lesson for browsers is to actually buy something while in the store. That way they can keep the doors open. Or so I’ve heard.

Afganistan: US Fights While China Mines Copper

From an article by reporter Alex Rodriquez in the Tuesday, July 12, 2007, LA Times entitled “History succumbing to the allure of ore”.  The article describes efforts by archeologists to dig sites in an area southeast of Kabul soon to be razed by bulldozers in preparation for copper mining.

So, I understand the part about saving the archeology.

What I fail to understand is why the US is fighting in Afganistan, expending national treasure consisting of the lives of soldiers, equipment, and mountains of cash, while the China Metallurgical Group is busily extracting copper.

USA fights for “freedom”, expending vast treasure.  China’s communism overrides freedom yet digs and extracts treasure.  Really now.

Are we congenital fools?  Are the Chinese at least thanking us for making Afganistan safer for them?  The wars in Afganistan, Iraq, and Pakistan are estimated to cost the US 3.7 trillion dollars.  These wars have produced wealth for defense contractors and for China through it’s mining.  At home republicans are busy sheltering corporations and the wealthy from tax liability while trying to apply wingnut libertarian economic theory to justify why we can’t commit resources at home. 

Most republicans are not wealthy. Yet, republican ranks are jam packed with people of modest means who support a doctrine and a silent power base of wealth who will not reciprocate the support.  It’s utterly irrational.

This is too crazy for words.

Ways to be a chemical entrepreneur

I had a discussion with some professor friends recently about the subject of entrepreneurialism among chemists.  I made my usual points about how people become captains of industry. Be more like an engineer. Preferably one with an MBA.  Naturally, my professorly friends were unmoved. Having spent their entire careers in academia, they just didn’t know about this. I didn’t expect them to.

After I made a gross generalization about the lack of entrepreneurialism among chemists, one prof pointed out that in her field of research, there were indeed people who were starting ventures.  I do not doubt this. But it made me think.  People, perhaps especially those in higher education or just advanced technology, naturally conclude that an entrepreneurial venture has to be based on new technology.  Yes, we need people to start businesses in nanotechnology or what ever you call the latest iteration of biochemistry. We need to have a constant churn of people trying to put new products and capabilities on the table.

But we also need businesses who are able to make polysubstituted phenols, anilines, pyridines, alcohols, ketones, aldehydes, halides, and all of the other “ordinary” raw materials and intermediates that are now largely made in Asia. We need companies who will make 100 kg or 1 MT of some obscure organic material.  Entrepreneurialism isn’t just about the bleeding edge. It is about having a dream and seizing opportunity.  It can be cookies or chemicals.

For the most part, intermediates have moved to Asia because of the economics of batch processing fine chemicals. And a moribund approach to chemical manufacturing in the USA. Chemical manufacturing in the USA is complicated. There are environmental permits, TSCA, high waste disposal costs, high labor costs, expensive processing equipment, and layers of business structure to manufacture safely and with high quality. A chemist faced with navigating the maze of regulations, engineering details, and business operations is a busy person indeed.  Few people can do all of it alone.

There are two fundamental approaches to starting a technology company- Market pull and technology push.  Market pull is an activity where one builds manufacturing capacity with the intent of filling it by making exsting items of commerce. Technology push is where one intends to construct a new kind of technology in the form of a service or widget. Market pull is an approach wherein customers buy known technology. Technology push is the activity where the customer is asked to buy into a new product or service. In this case, you’re necessarily asking customers to be first adopters or to find new forms of value.

I’ve seen startups fail because their one-act pony didn’t work. Instead of trying to make a go of it with a one-act pony, a whole circus of acts should be going at once.  A batch reactor is capable of making many things. A plant built around one product is entirely dependent on that one product.  Batch reactors occupied with products from many market segments are batch reactors that will remain busy over a variety of market conditions.

Pharmaceutical intermediate manufacturing is a business weighed down with substantial overhead and structural immobility.  It is not automatically a great place to start. The GMP world is very complex and peppered with many operational land mines. Many early intermediates are not covered under GMP. That is a good place to start. 

ISO certification is another area where I take issue. While ISO certification brings good business practices, it also brings layers of administrative structure. It is possible to mimic this structure without formally adopting it. The ISO label on you advertising will impress some buyers, but a surprising niumber will be indifferent. If you want to be in pharma intermediates, this will be necessary.  What an ISO certification says is that you will do what you say you are going to do. That is a good idea regardless.

What has to change is the economics of manufacturing in the USA. One way to do this is automated synthesis.  A good example of a problem:  How would one automate the synthesis of an OLED chemical like 1 MT of 8-hydroxyquinoline? This is an existing item of commerce, so entry into the market means taking share from someone else. You’ll probably have to best the market price by 10 % at minimum to induce someone to switch vendors. 

The chemistry isn’t cutting edge, but the processing economics may be. This is an example of how entrepreneurialism can and should  tackle manufacturing problems and gain a competitive edge. Since labor cost is a huge driver, find a way to shave off labor. An entrepreneur’s competitive edge may be process cost savings alone. You don’t have to wait for a scientific paradigm shift.

Part of success is just showing up. Just having capacity and a knack for a particular transformation can attract buyers. If you are handy with borylation and are flexible, somebody will call and want a quote. And maybe a sample. Pretty soon you have a PO and a deadline.

It is good to consider that an advance may be in the form of processing economics, not just the science.

35th Parallel

Th’ Gaussling and family have dropped down to a fault zone near the 35th parallel for some much needed vacation time.  The happiest place on earth is located here. It is a confederation of attractions called Disneyland and California Adventure.  By day we stand in line and by night we watch a fireworks display featuring incendiary flares in brilliant pastel.  Clever monkeys, these Disney pyros.  A delay time of 1-2 seconds between flare and concussion gives an indication of the proximity of the conflagration to our room.  All is well.

EAA Fly-in at Vance Brand

Last Saturday the local chapter of the EAA held a fly-in at Vance Brand Airport in Longmont, Colorado.  We got there late, so we missed most of the show. Did see some good aerobatics though.  This is the airport where yours truly learned to fly.

On the tie-down ramp at Vance Brand, June 25, 2011.

 What is most interesting about attending an EAA fly-in is the variety of airplanes that are on display.  But the show was a bit lean this year. Only one warbird was there. Usually there is more action with the relics.

Vance Brand used to have excellent air shows, but A**en built a pharmaceutical plant adjacent to the airport and caused the airspace to be unsuitable for aerial displays.  To add insult to injury, certain products were black boxed a few years back with the result that good people have been let go and much of the production hit the skids. So, what was a rich culture of aviation at this field has been chased away by a marginal pharma plant that can’t seem to either thrive or shut down. It’s pathetic, but it’s what happens when you build a business plan on technology that is as complex as what they were trying to do. Pharma companies- never in doubt but frequently wrong.

Travel-Aire

Patent links

The blog Patently-O is a worthwhile site to visit periodically.  That is if you’re interested in the arcane cosm of patents like I am. The fellow who writes the blog is Dennis Crouch, Asst Prof. at the University of Missouri School of Law. The post on USPTO guidelines on obviousness is particularly interesting.  I find this to be the most vexing part of patent law. 

EDTexweblog documents patent litigation in the East Texas district. I especially like the litigation haiku.  Reference and comparison is made to Vogon poetry.

Anything Under the Sun, by Russ Krajek, is another useful site to visit if you want to glean useful tidbits on patent practice.  These sites are maintained by people interested in their field and are happy to share insights with others.

Thoughts on Process Development. Outsourcing.

I have not put pen to paper (Okay. Fingers to keys) on process development lately. I can’t discuss much in the way of specifics. But there are some generalizations that can be put on the table for discussion.

When should you outsource a raw material? Depends. Does the process for the raw material match your skill set? Namely, does it require, say, bromination of an olefin or an aromatic ring? This can be deceptively troublesome. It is easy to scribble down a reaction mechanism for a bromination. It can seem like a no-brainer to say “yeah, we can do that”. Same is true for a Sandmeyer or a Friedel-Crafts reaction or some oxidation reaction for instance.

You may not do much of a particular kind of transformation or handle certain reagents enough to have an institutional expertise to safely handle some materials. You may have safety kingpins who will nix some reagents because they don’t like the looks of the MSDS.  Or, your pots and pans may be booked well into the future and you have no opportunity to make the raw material.

The trouble with outsourcing a raw material is that the supplier’s price is your cost which must be passed along to your customer. You may or may not have the margin to play with to do much outsourcing.  If you suddenly need to outsource a raw material, you will have to find a shop that will make the stuff.  Preliminaries include doing a secrecy agreement, a disclosure of the desired material, and possibly disclosing a technology package.  After the disclosures it might transpire that the vendor isn’t interested, they can’t do the job in the desired time frame, or they want too high of a price. Lots of things can go wrong.  Meanwhile, you’re relentlessly screaming down the timeline towards you’re own delivery date. You should be planning your outsourcing 6 to 12 months in advance. Or even 18 months.  Outsourcing always involves the discovery of new failure modes.

Let’s say that they agree to work up a quote. There is the matter of specifications. They’ll need to know some specifications even before they quote a price.  What kind of purity are you needing? Be reasonable now. There is what you want and what you can get by with. OK, you can live with “97 % purity”. What does that mean? Does it include solvent residuals? What about color and haze or mesh size and appearance? If it comes in at 96.8 %, are you sure you want to reject it?  If it can be easily reworked, and you have the time to spare, rejecting the material might be the best choice. But if they are late and you are late, you may have to take the material on waiver.

Apart from the mere chemistry is the matter of TSCA regulations and/or import restrictions. Will your vendor have to file for an LVE (low volume exemption) or is the material already on TSCA?  An LVE will take time even if everything goes well. Need to put these regulatory filings into the timeline.  Want to import bulk Hazardous When Wet materials? Plan on a boat ride across the ocean.

Asking a company to develop a new product for you requires good communication, person to person relationships, and lots of patience.  Your custom vendor may be smaller than you are and may have considerable resources tied up in your order. They’re taking some risks as well. Shoot for win-win.

Salmagundi

The world wide web is a never ending source of wonderment … for the curious.  It’s just email for everyone else.

A 3-D priniting device has been demonstrated using concentrated sunlight to fuse sand into sintered glass structures. In the Sahara. Where there is a lot of sand and sunlight, naturally.

Think you understand why the Soviet Union collapsed in 1991?  Think it was the dynamic duo of Ronnie Reagan, Maggie Thatcher, and their SDI that done em’ in? Well, these two characters had a part in it certainly. But the USSR was at the peak of its power by that time.  And they knew that SDI was decades from implementation. What was the real reason that the powerful and influential USSR collapsed? The article in the July/August issue of Foreign Policy by Aron Leon gives some interesting insights into that period of history,

Malcom Gladwell on spaghetti sauce.

Whither tellurium?