Category Archives: Chemical Industry

Analytical Life Without NMR

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We synthetikkers live in the gilded age of NMR. This analytical method is so fast and so rich in quantitative and structural details that we may forget what it’s like to produce materials that aren’t amenable to NMR rigged for liquid samples and H, C, F, B, Si, and P.

I’ve been busy making metal oxides and various complexes for sale that lend themselves to a very short list of analytical methods. When you make compounds for sale you have a responsibility to provide an unambiguous assay of purity for the lot.  Compounds that are poorly soluble, paramagnetic, or lack NMR active nuclei can be problematic for NMR assay in a production setting. Yeah yeah, I know- get a solid state NMR. Well, we don’t have one and it ain’t gonna happen in my lifetime. Meanwhile, I have 200 g of new product that needs to get certed and into inventory.

Lately I have been taking cues from catalog company web-sites and exploring other methodologies. Complexometric titrations for metals assay, AA, gravimetric AgX for halides, Karl Fischer for water, Loss On Drying (LOD) for volatiles (water, solvents), combustion analysis (C, H, & N), Glow Discharge MS (the Big Hammer) for refractory metal oxides, XRD for anything that could be in the xtal database, melting points, TGA, and I’m turning back to FTIR. 

I haven’t been using FTIR in a quantitative way, just looking for a “Conforms to Structure” result. But nonetheless, in the preparation of new compounds for the product list it is a life saver. I can convince myself that the desired ligands are there and use other methods to try to quantitate their wt %.

I always feel better if we can come up with 3 methods that corroborate the composition. You don’t always have to come up with methods that are on the specification either. It is reasonable to report results on a Certificate of Analysis that are “Report Only” and show general conformance rather than some percentage quantity.  Examples might be appearance, color, or even an NMR spectrum.

I have only recently begun to use XRD and am a mere novice in its intracies. I have sent solid solutions where components that I knew to be there were not detectable. I have also sent samples that came back with % compositions of several xtal phases. For characterization of production lots, it has utility in the detection of certain components. Amorphous phases and random, solid solutions are a blind spot for the method. On the other hand, there is ca one half million compounds in the database so it can detect xtal phases down to ~ 1%.

I have learned an expensive lesson in regard to ICP MS. The method is quite blind or unreliable with certain elements. Sulfur and halides in particular. A sample can be loaded with sulfur (often as sulfate) and the assay will come back with a wildly low value. An ICPMS assay of rare earth metal oxides can support a claim for 99.99 % total rare earth oxides. A GDMS of the same sample may show that it is 99.8x % in metals and even lower if you include halides, sulfur, and phosphorus. 

To be fair to purveyors of ICP MS, it is quite sensitive but standards at the lower limit of detection may not be available. Sub ppm numbers without an explanation of conditions and error are to be taken with skepticism.  Everything looks like a dogs lunch once you get down to the sub ppm level.

et Al. A Gathering in Memory of Albert I. Meyers.

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Colorado State University has announced “a gathering in memory of a remarkable life” in honor of University Distinguished Professor Albert I. Meyers. It will be held Friday, February 22, 2008, at 10:30 a.m. in the Arizona Room at the Hilton Fort Collins. You may recall that this hotel is 2 blocks south of the Chemistry Building.

RSVP:       csn (at) lamar dot colostate dot edu

This event is being managed by the Director of Development at the College of Natural Sciences at CSU. (I am hesitant to post names and phone numbers that can be collated by web crawlers)

I’ll definitely be there.

The Black Art of Procurement

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The act of consumating a business deal can be very exciting and fulfilling. It can also be a moment fraught with anxiety. [A variety of unwholesome metaphors could be brought in at this point, but I’ll resist.]  A business deal requires a buyer and a seller. The buyer has to satisfy needs that have an inverse relationship with the seller. The buyer wants a low price and high value per $. The seller wants a high price and a nominal value per $.

All buyers have a list of requirements: First, the buyer has to bring home a service or a product. Second, the buyer needs some kind of assurance that the transaction won’t go afoul by slow or non-delivery, poor quality, or shabby service. The buyer often has a third need, one that may or may not be evident from the beginning to the seller. Most buyers have a need to demonstrate that they have gotten a bargain. It is not enough to have merely purchased a thing- most people have a real need to bring back a kind of buyers trophy.

What many sellers may not appreciate is the kind of pressures that may be on a buyer in the B2B world.  The value of a buyer to his/her employer is the ability to get the lowest price under the best terms. The ability to put the squeeze on vendors is a highly prized attribute among buyers.  Some organizations actually consider their purchasing department to be a kind of profit center.

A company that is involved in technology development for their own use or for licensing may have several kinds of buyers. They may have a conventional purchasing department for paper clips, hardware, and commodity chemicals. This department is charged with sourcing and buying fairly ordinary things.

But the same company may also have a procurement group that focuses on the sourcing and purchasing of specialty items. In the fabulous world of chemical industry, a procurement manager may specialize in items that must be custom made or are otherwise scarce, highly technical, patented/licensed, or just plain expensive.

Some materials are particularly critical to a company. It may be a key chemical feedstock, a special reagent, a catalyst, or something that is difficult to make or is highly specialized. The procurement of specialized materials often requires the attention of a chemist. So, it is not at all uncommon to find chemists involved as procurement managers in the chemical industry. In fact, many high level procurement people I know were chemists early in their careers. 

Procurement people are quite important players in a company. They have heavy responsibilities and are always under pressure to perform. They deal in dollars and days. Their performance is easily monitored by their superiors by the simple metrics of dollars and delivery times. To put the delivery puzzle together, they have to negotiate and enforce specifications, price schedules, supply contracts, secrecy agreements, delivery schedules, and often international multimodal logistics. 

If a procurement person flubs a detail, like delivery of raw material on a certain date, a process shutdown at the plant could be the result. Depending on the magnitude of the fiasco, this could be a career ending injury for the manager.

We live in the age of just-in-time delivery of feedstocks. Raw material inventory sitting in a warehouse is equivalent to having a big pile of money sitting there. Extended warehousing of raw material inventory means that some amount working capital is is not only unavailable, but is not earning interest in an account somewhere.

Every query a buyer issues is an opportunity to work on lowering prices. Some materials are purchased regularly while others are more episodic. Some companies have a policy of buying under contract and others are satisfied to issue a spot purchase order as needed. Some buyers may have favorite vendors and others may not. Shopping for the best price usually means that multiple vendors are tagged for quotations.

Sourcing information is increasingly dependent on the internet.  Mysterious job shops in Asia or the Ottoman Empire are as easily found on a web search as are the venerable giants BASF or DuPont.  A lot of filtration has to be done by the buyer to sort out the authentic from the wannabe’s. It has been my experience at trade shows and on the web that many Asian suppliers are so anxious to cash in on the export trade that they will say yes to virtually every query.  They are not dishonest, really. They just have a severe can-do attitude. I’d do the same thing.

In the end, a seller needs to remember this about procurement people- Always do your best to make them look good in front of their bosses. That means offering a decent price and an honest assessment of delivery dates. A good price followed by poor delivery will harm a relationship as fast as anything. Be honest, earnest, and on time and your buyer will be good to you.

Bis, Tris, Tetrakis

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For many seasons, Th’ Gaussling was the keeper of part numbers and nomenclature in his village.  Fellow peasants would stumble out from the dark and dank mines to plead for new part numbers and names for the new products. As always, outsiders are surprised to learn that this is an actual “job”, but in fact it is. When you make new stuff, eventually you have to call it something. And what you call it has to be recognizable to the barbarian tribes outside the walls.

Peasants and grandees alike would take the names in gratitude for the everpresent fear was that they themselves would be called to toil in the muck of nomenclature as I have.

The dark world of nomenclature is split into two hemispheres- IUPAC and CAS. I don’t know what the deal is with Beilstein. It seems to be a sinking ship with a few deckhands polishing the brass knobs as the bow submerges.  Arguably, CAS has become the default system for nomenclature and identification in much of the world. The CASRN is increasingly the standard for unambiguous substance identification. The US EPA relies upon CAS to keep track of the TSCA inventory. Chemical sellers all over the world rely on the CASRN system to identify products and as a search term to attract internet search engines to their websites.

The major problem that I have encountered is that nomenclature from the 9th collective index (9CI) is often incompatible with our accounting system. The system does not accomodate Greek letters (kappa and eta) and the numbering system leads to sorting and format problems with list generation and subsequent retrieval. The complex system of numbering schemes and nested hierarchies plays havoc with the system as well, if for no other reason than the character count exceeds what is permissable in the data field.

Even more troublesome, the complex names are largely inaccessable to non-chemists. It is very hard for administrative assistants and temps to comprehend accounting data when they are fundamentally unsure of what the identity of the product is and why various materials show up in the bill of materials. To non-technical folks on the business side, chemical names are often just a complicated character string that is prone to data entry errors.

I’ll have to admit that nomenclature from earlier indices (6CI to 8CI) is often more user friendly in this regard. So when it is time to choose a name, 9CI doesn’t always win. This is a propagation step in the retention of obsolete nomenclature and I am guilty as hell of keeping it going.

Unhappy Chemicals

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We all have experiences with chemicals that stick in our memory. Experiences where we have witnessed just what chemical potential really means.  Proton or electron transfer can be downright frightening sometimes. Rude and abrupt phase changes or angry exotherms. Sometimes nature rages back at our feeble attempts to take the dragon out for a walk on a short leash.

I can name many exciting materials, but I think that chlorosulfonic acid is one of the more exciting and obnoxious substances that isn’t explosive or neurotoxic.  What are your favorites?

On Expired Patents

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The website Latepatents.net has collated a top 100 list of companies with a link to their individual expired US patents.  Said patents have expired due to failure to pay maintenance fees and not due to normal expiry. I checked a random sampling at the USPTO and found that indeed the patents were expired.

Readers will have to determine for themselves the value of these heaps of company treasure lying about the Public Domain landscape like so many abandoned Buicks, tanks still full of gas.

Given the quality of the companies that have the prematurely expired patents, and the resources they surely spend on IP management, I’ll hazard a guess that most of these patents were allowed to expire on purpose.

Patents are obtained for many reasons. One invention might lead to prompt and exclusive sales and profits for its owner. Another invention might lead to possible cash flow in the future if certain circumstances align properly. Some patents may be intended to be put up for lease or sale. Still other inventions serve to block competitors from facile entry into your line of business, so called “picket fence” patents.

It is not unusual for a given bit of intellectual property to become obsolete before the natural expiration of the patent. Technology can advance sufficiently such that a process or composition is no longer competitive. A company can move away from a technology package for business reasons having nothing to do with the suitability of the patented art.

Finally, I think that some patents are obtained simply because the company has a “policy” that requires the disclosure of inventions and subsequent mechanical submission to the attorneys. If you are a hammer, everything looks like a nail. If you’re running an intellectual property office, every disclosure looks like a patent. 

If too many “improvements” turn into applications, it may not be the fault of over-eager patent attorneys. More likely, it is the result of choices made by company management. I have witnessed a few circumstances where managers have been reluctant to exercise business judgement and have heaped the decision to patent solely upon the hapless attorney. What choice does the attorney have but to prosecute the patent?

It is my opinion that business people far too frequently allow their attorneys to make IP business decisions for them. The typical excuse is that it is a “legal matter”. The question for a business person is this- Can we make a choice that prevents the issue from becoming a legal matter?  Sometimes we use lawyers because we need a surrogate to do the dirty work for us.

The common default choice found in IP is that if it can be patented it should be patented. This is an expensive and weak-minded philosophy and I’ll wager that the patents in the aforementioned list are expired as a result of some second thoughts on the value of these inventions.

The Astute and the Cagey

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It is possible to split business organizations coarsely into two camps- Old Testament and New Testament. Old Testament organizations tend to be conservative along all of the organizational degrees of freedom. Employees have conservative mannerisms and dress, decorum is strenuously observed, desktops are always neat and tidy, and the management of personnel tends to be rigid. Lots of complicated rules and no mercy.

New Testament organizations on the other hand, tend to be more tolerant of iconoclasm and Bohemian values. The New Testament company is all about redemption and mercy. Ties are hastily donned for visitors from Old Testament businesses because Friday business casual lasts all week. Startups tend to be New Testament.

New Testament businesses are like friendly Unitarians and liberal Quakers, while Old Testament businesses are like sober Pentecostals and Mormons. One is not necessarily better than the other, though if you are caught in the wrong “denomination”, you are probably very unhappy.

Having once experienced the transition from New to Old Testament management, I can say that it can be a very uncomfortable ride. This transition can cause people to elicit interesting or unexpected behaviour. One of the insights that I have had relates to the manner in which people may engage in discussion or negotiation.

Some business managers are naturally very shrewd or astute individuals. They are able to achieve penetrating insights into relationships and circumstances where others might just see a toothy grin or hear a plausible excuse. After all, even Freud had to admit that sometimes a cigar was just a cigar. But the astute business person may be able to intuit a more creative view.

Sometimes, however, astute is confused with cagey. A cagey manager can be shrewd, but the difference is that a cagey person is one who is fundamentally unwilling to reveal information. Why is this important? Because information is the currency of trust. Information truthfully (and carefully) revealed is what allows relationships to move forward. Information about your intent and interest can go a long way to make a potential customer feel better about the business decision to buy your products.

Cagey managers may go well beyond simple mistrust of everyone. They may also be convinced that they understand what the customer “really” wants or what their real intent is. It is possible for smart people to step across the line and enter a space where they believe they can see what is happening behind the curtain. It is a very dangerous thing for a manager to think he is smarter than the customer.

The time tested optimum path is to take the customers word at face value, even if it means that you will get taken advantage of now and then. Give the customer what they ask for and not what you think they really mean. You can’t fall off the floor.

Skeptical of Hydrogen as a Mass Market Fuel

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If one examines the composition of propellants and explosives, what you find is that the successful and desirable compositions are those substances that decompose to produce many more moles of decomposition products than moles of starting materials.  As a result, modern propellant compositions have not just a preponderance of nitrogen atoms, but also more skeletal C-N or N-N linkages that replace C-C linkages. Dinitrogen as a decomposition product is more atom efficient in producing PV work than is CO2 or H2O if only because a molar volume of N2 contains only 2 moles of atoms as opposed to 3. 

Designers of explosives and propellants are principally concerned with doing work (W=Fd=PV) against the environment. It could be moving soil, forming a shock wave, or a accelerating a projectile out of a tube. Some particular mass needs to be accelerated over a distance and extracting the last bit of work from the expanding gases is desirable.

PV work is performed by evolving lots of -kJ/mol from heat of formation and arranging for the expanding gas to do something useful. In the case of propellants, dinitrogen formation yields a healthy heat of formation produced from making a triple bond. Hot gases want to expand and move whatever they are in contact with. The more molar volumes of gas generated, the more work that can be done. 

Some of the above line of thinking applies to the combustion of hydrocarbons as well, though the necessary formation of triatomic gases lowers the atom efficiency. The combination of C=O and H-O bonds being formed leads to a net evolution of heat compared to heat absorbed in breaking C-C, C-H, and O-O bonds. Properly chosen fuels and oxidizers provide a net increase in moles of gaseous products leading to an increase in molar gas volume.

Now, consider the case of the combustion of hydrogen and oxygen to produce water: 2 H2 + O2 –> 2 HOH.   In this reaction three moles of gas react to produce only 2 moles of  gas. There is a net loss in molar volume of 1/3 at constant presssure.  Obviously H2 reacts violently with O2 to produce PV work.  Hydrogen can be used to power an Otto cycle engine. But the net loss of molar volume across the reaction would appear to be a drawback to this system compared to others. The question I have is, how does this figure into the overall efficiency of H2 as a fuel?? 

Hydrogen is known to be problematic in engines due to what is called a cooling effect.

One of the key issues to consider with hydrogen economics is the fact that every last molecule has to be manufactured from hydrogen rich feedstocks using energy input. Hydrocarbons have to be cracked in some way, water has to be electrolyzed, or metals have to be oxidized with acid to produce dihydrogen. 

Given that H2 has to be manufactured by cracking hydrocarbon resources or electrolysis of water, does it make sense to use H2 as an automotive fuel? Why not just combust the hydrocarbon that was cracked to give up the H2 in the first place? Better yet, combust H2 at a centrally located gas turbine power plant and distribute the energy as electricity.

Hydrogen isn’t easily liquified (like propane) and the compressed gas requires heavy containment. 

With xtal ball in hand, the more I peer into the next 50 years, the more the future appears to be electrically powered. Todays hydrogen and ethanol schemes found in the popular media result from our collective unwillingness to address the real problem: How do we modify our behaviour to consume fewer kilowatt-hours (or BTU’s) per capita?

The answer is that we need to live closer to work, drive fewer miles, divert fewer hydrocarbons into disposable products, and generally consume fewer kg of resources per capita. Hydrocarbons are a very valuable resource- we’re fighting in the middle east over access to oil output in that part of the world. 

Petroleum distillates have a wonderful combination of attributes that make them valuable. Petroleum distillates have high energy density, they are liquid in ordinary conditions and hence can be pumped and atomized, they offer a choice of flash points, and are reasonably safe for people to handle. This is a splendid set of properties! We should be more appreciative and take better care of how we use it.

For Americans, a glimse of the future can be had for the price of a plane ticket to Japan or Europe. Higher population density, smaller portions of most things, and a larger fraction of income spent on energy.

Boiling the Frog. US Export of “Chemical Problematics”.

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Recent announcements by some of the big players in chemical manufacturing are stunning in their magnitude and implication for our western hemisphere. Like the movement of tectonic plates, business landmasses are shifting and grinding their way to other parts of the world.

Last summer AstraZeneca announced that it will leave manufacturing all together. According to C&EN, Merck is downsizing its staff by 7000 jobs and reducing its number of sites by 20 %. Pfizer is reportedly closing or otherwise trimming off 29 sites.

Recently, Dow announced its departure from commodity chemicals with the upcoming US$9.5 billion joint venture with Petroleum Industrial Chemicals (PIC) of Kuwait.

Some of this migration to the far side of the world will place the companies in a better market position to compete with rising demand in the distant corners of the world. Many of the players are already multinational in structure and have existing units elsewhere, so changes amount to consolidation.

What concerns me is the extent to which R&D and product development is being transferred off-shore. Like the frog in slowly warming water, no alarm is noted because from moment to moment the comfort level changes only slightly. But eventually, the warm water becomes hot and the inattentive frog gets cooked.  It is hard to escape the notion the US and EU are the frog in a warming pot of water.

Outsourcing is a choice, not a law.  A company has to choose to outsource rather than find other options. But to be fair, a company has its hands tied in many ways by regulatory or competitive constraints that are hard to contend with economically. 

Compliance with the confusing web of overlapping jurisdictions and increasingly harsh regulations pertaining to the manufacture, transport, and consumption of chemicals is wearing down the willingness of US companies to continue to manufacture in North America. Instead, we export “Chemical Problematics”.

A chemical product can become problematic in several ways- 1) commoditization, 2) patent expiration, 3) liability blooming, 4) raw material scarcity, and 5) regulatory compliance costs. 

In the life cycle of a successful product, it is inevitable that competition will discover the market and find a way to supply competing goods and services. This is commoditization. Eventually, you will lose control of your market exclusivity and others will set up their lemonade stand next to yours and sell for a nickel cheaper.

A major issue for pharma is the near term expiration of patents protecting highly profitable products. High cost manufacturing can be sustained by suitably profitable products. Exclusivity is the keystone that keeps the entry from collapsing. But when the patents expire, the Huns storm the gate and take over with lower priced generics.

What I call liability blooming is a circumstance wherein an existing product suddenly becomes the focus of some liability problem. It can be a drug that suddenly starts showing bad side effects, or it can be a product that has come into the  radar of the regulatory agencies.  Materials that carry a penalty for their use in terms of liability exposure are difficult or impossible to continue using. If an end product carries a legal liability, it is probably dead as a product. But if materials used in its manufacture- but not final composition- develop liability issues, manufacturing under the current regulatory environment can become prohibitively expensive.

Raw material scarcity is becoming a widespread problem for US manufacturers. As outsourcing becomes more prevalent, key raw materials for a given product may become unavailable in the US. As long as one can source the materials, this is not such a bad problem. But what about strateging substances needed for national defense? I have spoken with government procurement people who are increasingly having to resort to off-shore vendors for defense-related products and materials. Electronic products have a high reliance on some rather exotic substances and national defense is increasingly reliant on such technology. Indium and neodymium are examples of elements that are becoming quite scarce and whose loss from the market would have a high impact on many products. 

For any growing chemical company, the first real expense of regulatory compliance is for staffing. Increasingly, regulatory compliance requires a staff of specialists who serve as internal watchdogs for non-compliance and manage compliance programs that trail documentation much like a cable ship pays out cable into the murky ocean deep. 

Chemical products vary in their regulatory compliance paperwork according to type. Chemicals that are not used by the public out in the open like pesticides may be generally less complex to manage. TSCA is for materials that do not meet the criteria for food, drug, or pesticide use. Compounds that are used in B2B markets and will never be darkened by the shadow of consumers are still subject to complex TSCA regulations. But TSCA registry is not forever.  The ever shifting sands of TSCA registry may place a product into further examination by EPA if a new application is contemplated.  The all-seeing-eye of compliance managers may be strained as SNUR’s affecting product use can show up in the Federal Register at any time.

There are lots of good reasons not to start a chemical business in the US these days. Public or private companies are increasingly in competition with nationalized business entities abroad. Petroleum, petroleum products, and defense in particular are markets where western companies are having to compete with nationalized organizations that can swing a big money stick as well as influence national policy.

The US and EU are sliding into a Nanny State mentality microgoverned by those schooled in the Precautionary Principle.  Timid acolytes shuffling along the hallways of regulatory agencies and cock-sure MBA’s strutting like roosters in their corporate headquarters are independently guiding US culture to an epoch of de-industrialization.