Category Archives: Chemistry

Isotope Mojo Blues

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Near as I can tell, there is some kind of demand in the marketplace for all of the elements from 1 through 92, with the exceptions of Pm, At, and Rn, I suppose. It is hard to gauge the trade in actinides since precious little gets outside the realm of government regulatory frameworks. Clearly there is demand for certain isotopes of Th, U, and Pu.  But the nuclear regulatory people keep a tight reign on that stuff.

I remember a pottery class I took some years back in a nearby town. I was snooping through the pottery stockroom looking for glazes and what did I find? I found a sizeable quantity of Thorium nitrate.  These hapless middle-aged, post-hippy era, meadow muffin starving artisans running the co-op clearly had no idea that they had an actinide a nuclear-age artifact in their midst. Obviously, it had been secured for colored glaze applications.  I warned them about it but was met with the cow-in-the-headlights-look. I call it the “bovine stare”.  So, I brought a GM survey meter the next week and opened up the jar with a few of them standing there. As the clicks ramped up from the beta’s and as I switched the attenuation to keep the needle on scale, I thought I heard the unmistakeable faint slapping sound of multiple sphincters slamming shut.

The first question was “Would I like to have it?”.  Pppffffttttt!  “Hell no!” says I.  Nuclear cooties. Jesus H. Crimony!!  I did a careful survey with the GM counter and found that the surrounding area was clean. The material (early 1960’s vintage by the looks of the label) had hardly been used, so I was confident that contamination was not too bad, if indeed there was any. There may have been alpha emitters but this counter wouldn’t pick them up.  I gave some names of hazardous waste vendors and a stern warning not to drop it or spill it.  That’s the last I heard of it.

I remember a seminar in grad school when a visiting rock star from ETH gave an organic seminar detailing the use of Li-6 in NMR studies.  The fellow lamented in his fastidious German/Swiss accent that it was difficult to get Li-6.  He also said that for a time much of the refined Lithium in the market place was depleted of Li-6.  It would be interesting to hear someone comment on the accuracy of this. 

Bloggenvolk- ACS Chicago Meeting Minus Gaussling

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Sadly, regrettably, and with heavy heart Th’ Gaussling must disclose that he was asked to cancel his trip to the ACS meeting in Chicago. The clarion call of duty has sounded for all hands on deck.  Mister midshipman Gaussling will take heed and report to battle stations.  Ours is not to wonder why.

It is probably a good thing. I always spend way too much money on books at these meetings anyway.   There is always the Gordon Conference ….

Perhaps other bloggenvolk can meet in Chicago.  I think it is important for people to socialize.

Cash is King

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It is tough being a small company or start-up.  You have perpetual cash flow concerns and maintaining a big enough plug of working capital is always difficult. Add to this the fact that larger companies tend not to take you seriously on either the buy or sell side. 

Selling to a company that is much larger is often challenging.  They are often skeptical of your ability to deliver; they want to throw their weight around by dumping outrageous terms and conditions on the table; and they may want you to “invest in the relationship” with freebies like holding inventory, unpaid R&D, free R&D samples, or a dozen other things. 

One of the common purchasing tricks is to ask for wide range of volume pricing. That is, ask for the pricing of 1, 10, 100, and 1000 kg of a product.  What they will do is to look at the largest volume price as a sort of floor or asymptote price and then begin to ask for lower quantities at that price.  They know that you can offer the material at the low unit price one way or another, so why not ask for smaller quantities there as well?  This can be a very effective leverage when negotiating price with a vendor, that is, the knowledge of their fall-back pricing. 

As the manufacturer you are well aware that the economy of scale only works if you actually manufacture at scale.  Many manufacturers of specialty chemicals may not actually keep certain products in inventory. If their sales history is spotty or if it is relatively obscure, there is no way to predict demand.  So, dumping capital into finished goods that sell poorly is a bad decision most of the time.  When you do not carry a product in inventory, that is, you only make it on demand, your hands are tied in price negotiations.  You just can’t rationally offer 10 kg at 1000 kg pricing.

Another difficulty is invoicing.  It is almost always the case that the vendor will have to pay for raw material in advance, hopefully with commercial credit terms like 30 days net.  And no matter what, payroll has to be met.  So the manufacturer has to commit resources up front for a given sale. Only when the product goes on the truck can the vendor issue an invoice.  This is all reasonable and expected.

It is possible to go to your banker with a purchase order in hand and apply for a short term loan to fund the manufacturing costs.  It is important to get to know your banker well. If they have confidence in you they can help you out during tough times.

Typically, payment is due 30 days after the product ships.  Some companies will insist on starting the clock when the shipment arrives. For shipments in the states, this isn’t such a problem. But for shipments involving boats it can present cash flow problems given the month-long transit time.  Incidentally, companies that use the SAP accounting system will have requirements that will be as fixed and unchangeable as the very ground you stand on. 

It will usually transpire that the manufacturer will have to pay for raw materials and payroll well in advance of payment.  This is normal.  One of the ways you get into trouble is when raw mats show up too early or too late. Raw mats that show up too early will require payment sooner and raw mats that show up too late will delay manufacture.  Timing is important. 

Another kind of financial trouble you can encounter is from late payment or even nonpayment from a customer. Late payment gives rise to all kinds of trouble for any company, but especially for small, capital-deficient companies.  Receivables accountants maintain an aging chart for invoices.  After 30 days, the receivables person will begin to get nervous and get on the phone to roust the customer for payment. After 60 days, people are getting jumpy about payment and after 90 days there may be calls to the customers president or controller. 

When a company has a cash flow problem, they will direct whatever cash they have into their most critical expenses in order to keep the place running.  Your invoice may not be at the top of the list.  When you encounter this problem with a customer, it is important to keep your cool and try to get whatever they can afford to send. Chances are good that they are already twittered about it so threats and heavy handedness may be a waste of time.  But often it is the squeaky wheel that gets the grease (or lucre) in these circumstances. So it is always worth talking to the customer about payment.

This whole business of pricing, invoicing, and getting paid is deadly serious and the inability to do it well will shut a company down quickly.  We technical people often discount the accounting end of our business, perhaps believing that it is the domain of lesser skilled persons.  Successful companies, however, know that a good accounting group and clear policies are crucial for stable operation.

Start-up companies, however, may not pour resources into accounting systems as generously as they should.  Often, it is the founders who do the accounting themselves in the early days.  Eventually, the founders realize that they need book keepers and accountants to manage all of the cash flow issues.

Purchasing- The Dark Side of Business

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All sales people have to deal with purchasing people in some way or other.  In the B2B chemical business, where you never really meet the ultimate end user, sales people can be found to populate two levels.  Non-technical and technical.  Non-technical sales people are, in my experience, relatively scarce in the chemical field.  Yes, you do find people with degrees in business doing chemical sales, but without any technical savvy they are at a distinct disadvantage.  Most of the people in chemical sales tend to be technical types of one stripe or another- engineers, technicians, or chemists.

What has always struck me about business is the dramatic differences in culture and operating policies between companies in a given market.  Some companies make it nearly impossible for sales people to contact employees and other companies seem indifferent.  I have noticed that pharma companies are particularly stringent about employees meeting with sales people.  Of course, this may just be an artifact of my sampling experience.

There is a reason, of course, for a company to make it difficult for sales people to contact its staff.  They want their purchasing “professionals” to be present and/or in control during such encounters.  This is not unreasonable.  Some large pharma houses for instance have contracted other companies to do their purchasing for them.  This being the case, uncontained or off-line purchasing may be redundant, uneconomical, or a breach of contract. 

But the other reason for discouraging staff from meeting with sales people is this- purchasing people are skilled in the art of procurement.  They are familiar with company policies regarding suppliers and negotiation.  And, not insignificantly, they tend to be a bit more refractory to the enchanting ways of sales folk. 

A well run purchasing department is a type of profit center.  Not only are they required to get the cheapest and most stable supplier, but they are also tasked with extracting other concessions as well. Other concessions may include custom shipping & packaging details; custom specifications; an agreement to maintain inventory; special price/volume arrangements; or long term pricing agreements. A good purchasing manager is worth their weight in gold.  Over their career a good procurement staff can save a company vast sums of money and secure strateginc reserves of raw materials for competitive advantage. 

I joke about purchasing as the “dark side” because a good purchasing person can be a really tough sell.  They make sales people work hard for their money but in the end everyone is better off because it makes businesses more resilient and competitive.  They raise the bar and, painful as it may be, in the end we all benefit from excellence in business.

Bloggenvolk Chicago ACS Meeting

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A group photo at the Chicago ACS meeting.  That would be fun and blessedly easy.  If bloggenvolk want to linger and talk, they could do that. (If you haven’t been to the Art Institute, I heartily advise a visit.)  It’ll be Chicago in March, so that means outdoors may be nasty.  We just need someone to shoot the photo and post it somewhere on the web. 

What about monday noon, at the convention center, in the entrance near that rotating product literature carosel they always have? Any takers?? C’mon.  Be a sport! I’ll be wearing a badge that says “Gaussling”. 

Bloggenvolk

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It would could be fun to meet other bloggers at the ACS meeting in Chicago.  Eventually we’re going to have to have some kind of official (ACS sanctioned) function where bloggers can get together at these meetings.  We’re all driven to write about chemistry in one way or other and I’d say, for the most part, we’re all smitten with this science.  Chemistry bloggers are science writers.  We write because we are driven to do it.

It would have to be done in a way that is not threatening to anyone.  Basically we’re all anonymous writers.  I suppose that fact could be viewed as kind of creepy in some way- I don’t want to run into some wacko either.  But wouldn’t it be fun to sit with other bloggenvolk at the convention hall and chat?  I think it could be lots of fun. The pseudonym stuff wears thin. 

Eventually it’ll happen. This mode of communication isn’t going to disappear anytime soon.

New Failure Modes

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Chemistry can be very humbling.  A person can be absolutely sure of how a new reaction or process will turn out and yet be absolutely dead wrong.  Process research is an engine that consumes dollars and churns out new failure modes in one big pile and positive results in a smaller, steaming heap. 

I have been working with ionic compounds that have weakly coordinating anions.  I’m finding that my finely honed intuition built from years of shame, suffering, and cruel humiliation is turning up flat wrong more times than I care to admit. A house of cards.

More than a few of these compounds seem to participate in the formation of a liquid phase in the right combination of solvents.  If I were keen on monkeying with ionic liquids, this would be just dandy.  But the product is a solid and I want to purify it by xtallization.  I’m tempted to categorize these liquid phases as clathrates, but I’m unclear if the definition will acommodate such a thing. In each case, a normally miscible solvent pair is required to split out the new phase when the weakly coordinating ion pair is dissolved in the more polar solvent. 

There is a happy ending to this.  I was able to isolate solid product from a 2-solvent system, but sadly, I would be hunted down and shot like an egg-sucking dog if I disclosed it.  Bummer.

UV-Vis Spectrum of POM Pomegranate Juice

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Below is a link to a UV-Vis spectrum of POM brand Pomegranate Juice.  The graph shows two spectra- one is a simple dilution of POM-brand pomegranate juice. The other, lower extinction, spectrum was a simple dichloromethane (DCM) extraction of undiluted pomegranate juice as it comes out of the bottle. The extraction was done with a 1:1 v/v ratio of DCM to juice. Notably, the DCM extract contained no visible color. The layers emulsified and had to sit for ~10 minutes to separate. The DCM extract was dried over a bit of magnesium sulfate and filtered.  The undiluted extract was submitted directly to analysis. The dashed curve is the spectrum of the extract.

What is interesting about the extract is that the absorption maxima do not align with the maxima of the whole juice.  The DCM soluble fraction is quite different electronically from the balance of the components. Indeed, the extinction drops off to 0.026 by 350 nm and drops to near zero thereafter.  It is important to note that the absorbance of the extract is based on a much more concentrated solution, so a direct comparison of absorbances with the highly diluted whole juice is not valid. Focus instead on the wavelength of the maxima.

I ran the spectrum of the whole juice as a 500 to 1 dilution in distilled water.  No attempt was made to buffer the pH of the water or to filter the juice. I fully realize that there are experimental control issues to contend with here- i.e., pH dependence, turbidity, oxidative degradation due to air exposure, etc. 

POM Pomegranate Juice UV-Vis

According to the literature, pomegranate juices contain varying amounts of polyphenolic, tannin-type species not just from the juice, but also material that is released from the rind in the pressing process.  So further experiments should try to obtain juice that is pressed in a way to discourage the inclusion of materials from other plant tissues.

According to one source, the components of pomegranate juice can stabilize the level of PSA in men who have prostate cancer.  Whether it works via the anti-oxidant properties or some other more specific interaction is unclear.

Just what is the point of running these spectra?  My original interest related to the visible part of the spectrum. I wanted to know what the visible spectrum of this intensely colored juice looked like.  What is evident is that for all of the extinction in the visible part of the spectrum (>350 nm), the UV band is much more intensely “colored”. That is, the extinction is much higher in the UV range (<350 nm). Why UV-Vis spectra?  Because, silly, I don’t have an NMR. But I do have a UV-Vis spectrometer.

Well, that’s not quite true. I can run a proton NMR of the crude material, but given that pomegranate juice is a plant fluid, all I’m going to see is a forest of peaks.  Actually, more to the point, others have isolated components from this fruit.  My interest is in the reduction capacity of the pigments.

Extracting structural data from a UV-Vis spectrum is not really possible. UV-Vis spectroscopy is about electronic transitions and a wide variety of species overlap appreciably, so structural determinations of components in complex mixtures is out of the question.  Furthermore, pomegranate juice is sensitive to oxidative degradation and is likely to be quite sensitive to pH (next on the agenda), so it’s thermal and O2 exposure history may be important (i.e., has it been Pasteurized, etc).  So it’s back to the drawing board.  

Lanthanide Contractions and a Dog’s Lunch

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The rare earths are a curious group of elements from the commercial point of view.  There are a variety of lanthanide products available from a handfull of vendors, most of whom cater to a small group of users. Some of the catalog houses have respectable collections of them.  My friends at GFS offer lanthanides- specializing somewhat in cerium products.  Aldrich, Gelest, and Strem, of course, offer a variety of rare earths (RE). Hard to say if they are big sellers-I’m guessing they are on the slow side of the 80/20 rule.  I’m aware of a single American company that actually refines Scandium Oxide and manufactures Scandium Triflate as well. They are one of the few, if not the only, companys in North America that refines any RE’s. Most everyone else imports from Estonia, Russia, or China.

From my perusal of the literature it seems that the field partitions roughly into reagents for chemical transformations and oxides for material science.  The material science side is way beyond my reach, so I’ll pass on that segment.

The least expensive and most basic RE products are the oxides. If you spend some time shopping around for various RE’s, what you’ll find is a sliding scale of purity specs, 99%, 99.9%, 99.99%, 99.999%, etc.  If you look even closer to the specs, what you’ll find is some sleight of hand in regard to what the number of nines actually represents.  Most vendors will offer a number of 9’s that are TREO, Total Rare Earth Oxides. So if you are keen on Scandium Oxide, 99.99 % (or 4N), chances are that the 4 nines really represents the total of all of the RE oxides present.  In reality, 99.99 % TREO Sc2O3 will be 99.9 % in Scandium and the balance of the 4 nines is a dogs lunch of Ln Oxides. 

As we all know, when you analyze for more and more 9’s, you eventually find most of the periodic table present in your material.  But if you really want 99.99% in Scandium, it can be relatively hard to sort from the TREO products.  You are forced to swim through spec sheets to find material that meets your need. BSC offers 4N in Scandium, and some others do as well.

One of the interesting applications of RE triflates is as a water tolerant acid catalyst.  Essentially all of the RE triflates have been reported, with the possible exception of Promethium. The lanthanides show a general decrease of ionic radius as one increases atomic number. This is the lanthanide contraction. It has been shown that the catalytic activity in certain acid catalyzed reactions (i.e., with a Ln(III) triflate) correlates with the charge-to-radius ratio in this group.  Not surprising, I suppose. 

So, for an ambitious person with designs of bringing rare earth reagents to the marrket, this is a classic “technology push” situation.  In order to convince people to buy RE triflates as acid catalysts, you first have to offer a value proposition.  They can use conc H2SO4 or they can use Yb(OTf)3 as an acid catalyst. Hmmm.  So which is cheaper in my application?  Given the sparse literature on Ytterbium Triflate chemistry, for instance, it could be hard to convince a customer to adopt your RE product beyond R&D use.

So, whaddaya hafta do to sell a boat load of this stuff? You probably have to come up with a killer application for the RE Triflate to convince people to buy it and try it. If you as the purveyor lack this application, they you have to rely on the customer to do it for you.  In the mean time, you could get very hungry.