Electroneutrality is dead?

Gerald Pollack

That is the highly controversial claim made by Kate Ovchinnikova and Gerald Pollack in Langmuir earlier this year.^[Langmuir] Electroneutrality is a guiding principal in electrochemistry and is a method to understanding electrolytic cells (Pt electrodes in dilute aqueous NaCl solutions). It stipulates that any charge imbalance across an electrochemical system is quickly (~ns) balanced by the salt present in the water being driven by the electric field in such a way to neutralize that charge imbalance. Thus the need for salt bridges and all that wonderful G-chem stuff we have learned. There is even a cool little applet you can play with electroneutrality by the Harvey Project. When I tried to sit down with electrochemists to discuss the claims by O&P they quickly dismissed them out of hand after reading the beginning of their paper. So the big question is, did O&P stumble across something amazing or did they spectacularly overstate the results of their experiment.

I can summarize their paper succinctly:

1. Insert electrodes into electrolytic cell
2. Turn on power supply
3. Disconnect the electrodes from the circuit
4. Remove the bridge between beakers
5. Reconnect electrodes to measure residual charge in the two beakers.

The design seems thoughtful enough, but before I get into the merits of their results I need to take time to mention a few gems in their paper. Here is a quote from them.

Bubble formation occurred in all experiments (n > 20), although position and growth rate were inconsistent. In most cases, formation began during the charging phase and continued through discharge. Characteristics of bubble formation were not pursued in any detail, but may warrant future study.

But it doesn’t warrant further study,  all chemists know where their bubbles came from.

An other eye catcher is that they didn’t use a standard electrochemical setup. They used my trusty NI USB-6009, I know that product well as a chunk of my thesis was acquired with it. It doesn’t make the experiment invalid, but why use crap when you are trying to disprove such a time honored concept as electroneutrality. Maz and I know from experience that the USB-6009 floats if their isn’t a sufficient load on it or if their isn’t an appreciable external voltage.

Here is a quote from them contemplating that HCl solutions have an overall positive charge.

One might speculate, for example, whether ordinary acidic solutions, which have low pH, might contain net positive charge, while ordinary basic solutions might contain net negative charge.

So far everything has been “quirky”, it isn’t until the end when you perceive something really odd.

Water appears able to adopt two structural networks that have mirror symmetry to one another. The fact that these networks are macro phenomena deserves further study.

A second and related issue is the potential for disturbance of these structural networks. It is now established that when water is left standing for long periods, it develops thixotropic properties, implying macrostructure.7 Such macrostructure is expected to be fragile. The fact that removing and inserting electrodes did not apparently ruin the charge-containing structure implies that, once formed, the structural network can re-form rather readily. This is an additional subject requiring further study.

7:Vybiral, B. Water and the Cell; Pollack, G. H., Cameron, I., Wheatley, D., Eds.; Springer: New York, 2006; pp 299-314.

It is with that last statement you say to yourself, “Oh, I get it. This is a homeopathy paper.” Water being able to adopt structures of the solutes that were dissolved in it is a hallmark of the quackery that is homeopathy. O&P’s claim isn’t that bold, but it has hints of the same idea. Claiming macrostructures (~mm) of water that extend past the picosecond domain is absurd.

Although I haven’t discussed the results of their paper, would you really trust it anyways?

Horacio Corti and Agustin Colussi have done an excellent job dissecting the technical irregularities of the paper and I encourage you to read their comments on the article (link below). If you come to a different conclusion or find me in error, please leave a comment and join the discussion.

Links

• Can Water Store Charge? (Ovchinnikova and Pollack)
• Do Concentration Cells Store Charge in Water? Comment on Can Water Store Charge? (Corti and Colussi)
• Reply to Comment on Can Water Store Charge? (Ovchinnikova and Pollack)
• Response to Reply to Comment on Can Water Store Charge (Corti and Colussi)

Mitch

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Like Natalie Imbruglia’s One Hit Wonder, I’m Torn

So it’s been a while since my last entry, but grad school has eaten me up. But over the past several months, I have been getting seduced by the Dark Side of the Force. No, I’m not talking about industry, I’m talking about another entity entirely.. the world of intellectual property law.

OMGWTFBBQ? That’s probably your response right now, but as someone who has been rather myopic in my career path due to academe being the only thing I know, (and me not really feeling like a perfect fit in industry), the seductive path of law school is in the way.

One of the things I have learned through informational interviews with my local alumni is that law schools LOVE technical backgrounds and patent law is one of the hottest and fastest growing fields at the moment. Of course, things are cyclical which means it might not be great later, but the past 5 years has seen tremendous growth.

There are lots of other scientists going to the other side, but here’s my dilemma…

There are firms that offer patent agent programs to seduce scientists to law. What is this patent agent program? You work at a firm (with zero to little experience in law) and get trained as you work. You get paid a great salary (think average 2.5 to 4 times the highest grad student stipend depending on where you go), with amazing benefits (401k plan, full medical/dental/vision benefits, etc), get to work in a fancy office, feel like a real world adult, get to dress up in fancy clothes and get trained. After a year, you’re probably ready for the patent agent exam, and if you pass, said firm will offer tuition reimbursement if you attend law school.

Yes, they’ll pay for expensive law school. Then you go back to the firm as a full J.D/(M.S. or PhD) as well, get promoted and commit for a few years, then you can go around to other firms as well!

So what’s a chemist to do? I do love research and academe, but my pragmatic side is telling me to join the dark side.

I know I’m not the first to be seduced, and I definitely won’t be the last! Intellectual property law, when it concerns chemistry, is actually quite fascinating. It’s like being a grad student with all the reading, researching and writing you have to do, but you get paid way more and you’re not inhaling chemical fumes. It’s another career path available out there for grad students in chemistry, and I know I hadnt considered it before and just recently learned about it, so I’m throwing it out there, so like me, perhaps your blinders can be taken off and you might consider more options post PhD!

That’s all! I’ll let y’all know what I do in the coming months! For now I have lots of thinking to do.

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Condensed Print Format

My boss has pointed out this piece of news covered by C&EN. Apparently, starting from July, all ACS journals will be printed in a “rotated and condensed” format, that is two pages on one printed page in landscape format. This is an effort to reduce printing and distribution costs.

In my opinion, this change is just one further step towards purely electronic journals that are not printed at all. I think this will deeply affect the way we present our data and how we look at formatting. Preparing a manuscript in a way meant for printing is different from one which will never appear in print. Some may welcome this change because it saves paper, others will probably miss the possibility of flicking through a new issue of JACS. Although I rarely go to the library to pick up a printed journal, I admit to reading printouts very often (see this post).

Update: Apparently, in 2010 the print versions will stop completely, with the exception of JACS, Acc. Chem. Res. and Chem. Rev. See also Nature News.

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Shifting Constants

“]One of the first things that pops up in chemical education at the high school level is stoichiometric equations where a student is supposed to determine such things as yields, coefficients, and amounts of substance on a purely theoretical basis. This quickly becomes old hat for many students. In high school, my stoichiometric technique (if you could call it that) left a lot to be desired. I tended to “divine” my answers on tests and quizzes by playing with numbers until an answer made sense- then using it. It worked surprisingly well- and I got through classes learning very little but with decent grades. At the time, I wasn’t terribly interested in chemistry, and the class really was boring up until the end, where we got to learn about electrochemistry. I didn’t realize at the time that the subject matter wasn’t being done any justice. To me a mole was a mole was a mole. I just knew there were these numbers that I used to divine answers.

Read more »

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Printing

Most of the printing of our group (~30 people) is done on just one laser printer. I often find myself walking from the lab to the group library, where the printer is located, and back because of paper jams or printing orders that have misteriously vanished into the digital nirvana. This is making me crazy! Somehow I am unable to proofread a manuscript on my computer screen, so I always need a printout. Maybe I should try and get my own printer.

This leads me to my question: Do you often print papers for reading, or do you always read the PDFs directly? I try to read most things directly, but the papers I cite the most, I also keep in printed form.

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Chemistry Journalism

Recently, Chemical and Engineering News had to cut 16% of their staff due to decreasing ad revenue.^[CS] Advertisers have been trending towards less spending, but this is often attributed to a lower subscription base. The number of C&EN’s subscribers do not fluctuate enough to account for this type of lost revenue, so what is causing the decrease?

After the layoffs there are now 48 C&EN’s staffers. If I assume the average salary is ~$5,000 per month, I have no clue if this is valid but it seems like a lower limit dollar value, then C&EN needs to make $240,000 per month to just cover payroll. Our dues pay for their paper, printing, and distribution costs. So let’s compare C&EN’s revenue model to Chemistry Blog. First we need to define some terms.

• Uniques, defined as the number of unique people that read a website/magazine in a given week.
• Revenue per unique per month. Average amount of revenue generated per unique reader in a month

With a weekly subscription volume of ~140,000, C&EN has a monthly unique volume of 560,000. Which means C&EN needs to make a minimum revenue per unique of $0.43 per month to cover my lower estimate of their payroll costs. On the other end of the spectrum, Chemistry Blog generated $15.00 in April from 20,000 uniques, this translates to ~$0.0008 of revenue per unique per month. The gist of this story is uniques are cheap online.

We at Chemistry Blog fully admit that C&EN is a better news source, better journalism, and a better target audience for advertisers. But from a purely marketing angle, Chemistry Blog is cheap at a cost of one fifth of one percent for what C&EN sells their uniques. I would guesstimate $0.10-$0.20 of revenue per unique per month is a more sustainable model that a huge niche journalism outlet like C&EN will be force to aim for in 10-20 years. Unfortunately, this means many more painful cuts in C&EN’s future.

Below are my suggestions to shore up C&EN balance sheets.

• Expand to non-ACS web advertising: C&EN already has a relationship with advertisers, if they initiated an affiliate program where independent chemical websites get a share of what advertisers are willing to pay for adspace. This expands the audience they can tell advertisers will see their ads.
• Many journalism outlets are scuttling their science sections. C&EN could sell their stories to these papers at a marked discount for what it costs to staff science journalists.
• Participate more strongly in ACS membership drives, more members equals more subscriptions which will hopefully be proportional to more ad revenue.
• Get a larger chunk of the budget subsidized from ACS.

None of these ideas are going to be the savior of chemical journalism, but it might ease the coming pain.

Mitch

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Re-issuing Classic Chemistry

I recently bought a 2009 re-issued copy of Pearl Jam’s first album “Ten,” originally released back in 1991.  Those who know me well are also aware of my interest in Pearl Jam; I enjoy collecting demos or live versions of their music.  Anyhow, their officially released re-issue contains a remixed version of their 1991 album and (in my opinion) parts of it sound distinctly different than the original mix.  For you music buffs out there in internet land, Brendan O’Brien—the original producer—dumped the supplemental reverb applied to the original tracks in this newer version.  As a result, the guitars and drums sound much cleaner and less wet (I recommend listening to both versions of “Why Go” or “Oceans” for a good example of the remixing).

Thinking about the whole concept of “re-issue” got me thinking about organic chemistry (big surprise).  How often do scientists report fantastically optimized results, table the idea, and then revisit it at a later date (to make vast improvements)?  Or better yet, how much “new” chemistry has derived from “re-issuing” processed developed in the late 19^th or early 20^th century?  My PI calls refers to this particular phenomenon as, “teaching an old dog new tricks.”  In writing my dissertation (an ongoing process) I had the pleasure of reading Lipshutz’s recent review about cuprate chemistry (Synlett 2009, 509-524; DOI: 10.1055/s-0028-1087923).  This personalized narrative discusses the Lipshutz group efforts and contributions to the field of copper(I) hydride chemistry. 

This article is of particular interest apart from discussing it at length in the ‘ol thesis.  A few months back, I had a conversation with a colleague of mine who claimed that since Stryker’s contributions, “conjugate reduction chemistry has (basically) fallen to the wayside.”  I recall laughing out loud at his remark.  “What about Lipshutz or Riant or even Buchwald,” I asked.  He claimed, with a sense of arrogance, that their work was “just a new twist on Stryker’s original work.”  Based off of this logic, if someone successfully synthesized Taxol from table sugar in three steps, would it be considered a new twist on Nicolau or Holton’s contributions?  Arrogance aside, this idea of “re-issuing” is a common phenomenon in research chemistry.  It’s done frequently, often to the tune of 10-20 additional printed publications (apart from the seminal contribution).  Perhaps, it’s these instances that call into question the process of “re-issuing” chemistry. 

That said, re-issued chemistry can result in significantly new discoveries and improvements on original methods.  Taking the conjugate reduction example, Stryker’s catalytic reactions, performed under a high pressure of H₂, were plagued with over-reduced products.  In switching the stoichiometric hydride source from hydrogen gas to PMHS, Lipshutz reported a vast improvement in reaction times and overall yields (Tetrahedron 2000, 56, 2779-2788; doi: 10.1016/S0040-4020(00)00132-0).  This change has spawned a whole new area of carbon-carbon bond formation, particularly in the field of reductive alkylation reactions. 

While I’m genuinely interested in the idea of inventing new and exciting reactions, the thought of tweaked processes resulting in “re-issued” chemistry is largely appealing (when done responsibly).  A prominent neutron chemist once told me that real chemistry lies in unexplored places.  “We want to be doing things that others aren’t,” he said.  I agree.  But on occasion, it’s necessary to explore the landscapes previously claimed by others for the betterment of the (scientific) community as a whole.

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Elemental analysis

What analytical data are necessary to characterize a new compound in organic synthesis? In the times before NMR, melting points, elemental analysis and IR used to be the available methods (and UV, if applicable). Nowadays, EA isn’t required by the journals anymore andv IR is probably going to disappear soon. Additionally, the significance of melting points is quickly decreasing because mostly people take the product as it comes off the column without recrystallizing it. Are we losing something there?

A number of people argue that the ability to get crystalline compounds is essential to be a good chemist, so recrystallization should always be done if possible. As a reward, you get EA-pure solids that are also easy to handle and may give you the occasional X-ray crystal structure (if you want to grow crystals). On the other hand, an additional effort is required: you need substantial amounts of material, which is no problem in a short synthesis, but can be a problem if it takes twenty steps to get to the product. If I have tediously made 50 milligrams of a material, I don’t really want to give ten away to be burned.

I wonder if elemental analysis is still a necessity today. In most cases you get all the information you need from NMR (identity and purity). What EA gives you is confirmation that your compound is pure as well as dry. Still, is it worth the trouble or just a waste of time? I suppose it all depends on the kind of research you’re doing. If you are “target-oriented”, as medicinal chemists like me are, I do not think it is worth it, as long as the final compounds being tested are pure. I suppose this is being sloppy, but I want to get a series of compounds in a reasonable amount of time. It might be a bit different in a total synthesis project, where the focus is on the pathway rather than the target compound per se.

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Is convenience costing chemists? Part 1

Times are tough and few if any are untouched by the recent economic woes. While profits have fallen, research costs for a variety of fields have remained the same if not increased, especially in the chemical industry. Academia too is feeling the crunch and many universities are making policy changes to minimize expense. At most universities, chemistry is usually the department hardest hit by budgetary strangulation for the simple reason that doing chemistry often comes at a hefty price (I.e. reagents, apparatus, instrumentation maintenance and standards, heating/cooling expenses due to fume hood usage). Many chemistry departments burn through consumables, most of which are not exactly cheap. Unfortunately, even in the present age of microscale labs and experiments, there is still a significant amount of waste both in industry and in academia with respect to energy and research material. Thankfully, there are many simple solutions that involve a little extra time but pay dividends.

Progressive steps are being made. An example: at a nearby university, the chemistry department is implementing an energy saving program, modeled on an existing program at Harvard. It is being done because heating and cooling the chemical building is expensive, and energy costs have risen. According to the Harvard program’s estimates, leaving a typical fume hood (whatever that may be) wide open 24/7 all year long uses three times the energy of an average home! Now reflect upon how many fume hoods are in your laboratory.

For my part, I hope it doesn’t stop at simply closing the sash–there are numerous other things that scientists ought to be doing. Still, it’s a start. For those of you thinking “well, we itemize our budget to account for energy, consumables, and other ancillary costs. We have the money,” you might analyze it from a perspective of using only what you must. Considering that Harvard’s 30 some billion dollar endowment is the largest of any university and they somehow find the moral responsibility to simply close the fume hood sash when not in use, is it not something all chemists ought to do? Surely they can afford a few hundred thousand dollars per year for the convenience of forgetting to close their hood.

Pinching pennies is important now, historically, and probably more so in the future. Scientists pay for convenience. Many research in an atmosphere of high throughput, intensive research with demanding deadlines. For most chemists, it’s a simple matter of putting in a purchase order for the reagent you need and paying through the nose on hazmat, fuel, and packaging surcharges to have it overnighted for your trial synthesis. Easy? Yes. Cheap? No.

So, what to do?

In the next installment, I’ll discuss a few commonsense ways to save money, possibly a few natural resources, and most importantly, time.

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