ANACHEM AWARD ADDRESS
The Pains and Pleasures of The personal reminiscences of Dr. Stenger as related in his Anachem Award Address, October 25, 2970, provide interesting insight into the sort of problems that challenge industrial analytical chemists. The contributions of the analytical chemist are essential in many areas of industry.
HE PVRPOSE OF THIS PAPER is twoTEold . First, I should like to show students of chemistry that industrial analysis is not necessarily a routine, boring occupation. I t can be frustrating a t times, but it can also be fascinating, instructive, humorous, and even exciting. It is usually pleasant, and it is always worthwhile if one dedicates himself to learning about what goes on in chemical systems. I n this usage, perhaps, the term “chemical systems” may also include people. Secondly, I hope to encourage every analytical cheniist as to the value of his or her individual efforts. The key to enjoying analytical work lies in knowing that the results will be useful and important. I n industrial chemical analysis there are pleasures to be enjoyed, and pains both to be taken and to be suffered. Hence, the title of the paper. It might have been “Thirtyfive Years of Industrial dnalytical Chemistry.” but nobody would want to hear or read something of that durfition. I n any case. it is necessary to draw from personal experiences to illustrate my points. One of the great pleasures of
36A
being an analytical chemist is that of being able to associate with exceptionally fine people. We have many in our own organization, our competitors and customers have others, and, of course, there are many in government labs and in the universities. For a person working in an industrial laboratory the opportunities for outside contacts are greatly increased by activity in technical organizations. It has been my privilege to work with the ACS Committee on Analytical Reagents and also to work earlier with the A S T N Committee on Chemical Analysis of Metals. Memories of tlic di.tinguished chemists who became my friends in those groups will always be treasured. The list would start with G. E. F. Lundell, \Ir.D. Collins, and Edward Wichers, and would include many of the previous Anachem Award winners. Through the Analytical Division of the ACS I encountered many others. One of these was 9. H. Furman of Princeton University. H e had translatcd the first German edition of Kolthoff’s “Volumetric Analysis,” b o we could commiserate on the difficulty of trying to keep Professor
ANALYTICAL CHEMISTRY, VOL. 43, NO. 3, MARCH 1971
Kolthoff satisfied with our slow progress. I got a real lift from Furman’s confession that whenever he spent an evening Lyith the Saturday Evening Post, he felt guilty knowing that, in the meantime, Kolthoff had probably written three papers. Initial Challenges
When I first came to the Dow Chemical Co. a t Midland, Mich., it vas my intention to gain a year of industrial experience and later go into teaching. Several things happened that first year to change my mind. A number of us were hired a t about the samc time, and the company, still a fairly small organization, arranged for us to tour some of the operating plants and to hear a few lectures on what was being done. I n one of the lectures, Ivan Harlow, then chief chemist, spoke about the composition of brines occurring in different geological strata t)eneath JIidland. I t was quite intercsting to learn that the brines varied in thcir bromine contents, and also that one could identify thc boiirce. independent of dilution, by tletermining the ratio of calcium t o
REPORT FOR ANALYTICAL CHEMISTS
VERNON A. STENGER Analytical Laboratories, The Dow Chemical Co., Midland, Mich. 48640
Industrial Analytical Chernistrv J
magnesium. Previously I had been interested in rock analysis and had not thought much about brines. Later t h a t year I visited a wellknown university to apply for a teaching position. During the interview I told the professor about those Midland brines. H e did not seem impressed and I did not get the appointment, but he did me quite a favor by asking a simple question which I could not answer. H e wanted to know how much fluoride was present in any of the brines. I still do not have a n exact answer, but there is less fluoride than we can detect by any sensitive method tried. T h e reason I appreciated the question is that it opened my eyes to the possibility of learning much more about brines than I then knew, and it gave me a n added interest in trace analysis. Subsequently, in about 1938, the company drilled into a deeper stratum yielding brine with a higher bromine content. Walter Kramer and I carried out the first complete analysis of this brine and discovered t h a t it contained about 40 ppm of iodine. Others a t Dow developed a process for recovering the iodine, and as a result, Michigan has become the leading state for iodine production in the U. S. We found significant concentrations of strontium and lithium in the brine, too. Later, Robert Goodenough, working in our group, developed processes for the recovery of those elements. T h e processes have not been used commercially but they are available in case a demand should arise. Yeed-
less to say, one of the pleasures of m y career has been the opportunity to participate in developments such as these. During t h a t same first year Willard Dow sent a man over to the laboratory who said he could extract gold from sand. T h e sand could be taken from a river bank, or almost anyplace. A. W . Beshgetoor, our lab director, asked me to look over the process with him. T h e man had a big iron bowl, rather flat but rounded, into which he would put the sand, some water, and a little mercury. After stirring the mixture, he would pour off the sand and water, and the mercury remained as a surface layer on the iron. With a rubber spatula he would scrape off the mercury, dissolve it in nitric acid, and end up with a small golden crystal in the acid. We sent a crystal t o a spectroscopist, who soon reported back t h a t it was, indeed, gold. Meanwhile, we found t h a t the metal would dissolve only in aqua regia, and t h a t i t would give the Cassius purple test. Obviously the man was showing us gold, but was i t actually coming from the sand? M r . Beshgetoor took him out to lunch, and while they were gone I operated the process a little myself. First I found t h a t sand was not necessary. Just putting mercury and water in the bowl would produce gold. Then I found t h a t the bowl, water, and spatula were not necessary either. Our man was using mercury which contained just enough gold to be interesting. When they returned
from lunch I reported my findings, much to M r . Beshgetoor’s enjoyment. T h e promoter packed up his equipment and left, saying, “Here I have a valuable discovery, and you chemists are just too damned skeptical to appreciate it !I’ T h e incident made me wonder why a capable executive like D r . Dow would allow such a fellow to take up our time. I may have speculated also that chemical company management might occasionally need the aid of a chemist to screen out bad proposals from good ones. Back in Minneapolis I had sought a job with a paper mill, and had been told t h a t they could afford a chemist only in periods of great prosperity. Be t h a t as it may, the gold affair also taught me t h a t a n analytical chemist should not be content with carrying out a qualitative or quantitative analysis alone, but should look a t the whole problem. Later I had an opportunity to talk with D r . Dow about the incident. H e said t h a t the man had been a company customer, but had evidently taken on some new partners who had involved him in this shady deal. I said, “Then you did know all the time that it was probably a fake?” H e laughingly replied, “Yes, but wasn’t it fascinating?” Problem-Solving in Analytical Chemistry
The point about an analytical chemist looking a t the whole problem can stand some belaboring; D r . Laitinen editorialized upon i t rather gently in the September 1970 issue
ANALYTICAL CHEMISTRY, VOL. 43, NO. 3, MARCH 1971
37A
.-
The Nester/Faust 1240 introduces a new concept in high speed analytical liquid chromatography . . . a complete and self-contained precision instrument with features and capabilities that, until now, were only available on more complex and more costly units. To make our point, let's look at the 1240's outstanding features, one by one. First, easy operation and reproducible analyses are due, principally, to an adjustable 1,000 psi pump, with continuous degassing of solvent, and a zero dead-volume, zero back pressure pulse damper. Second, for gradient elution analysis, there's a precision gradient former available. Third, separation is enhanced by a standard, ambient to 125°C forced air oven with nitrogen purge. Fourth, fountain effect is eliminated by the zero dead-volume oncolumn septum injector. Fifth, we assure highest resolu-
tion by designing and manufacturing ali our own columns and fittings. Sixth, the 1240 unit is supplied with a 2000 psi, 12 uI U.V. detector, with internal calibration. Ultimate detector sensitivity is 0.0002 0.13.units. In addition, a complete line of column packings is available, All of these features, plus more that we don't have room to discuss here, add up to some of the reasons why the 1240 is a unique analytical L.C. base priced at $4,900 , , , but don't let the price fool you, we haven't sacrificed quality anywhere in this instrument. For more information about the 1240 and its optional accessories, write or call today. NESTER/FAUST MFG. CORP., Instrument Products Division, 2401 Ogletown Road, Newark, Deiaware 1971 1 , (302) 737-6330. In Europe, contact: Steinengraben 44, 4000 Basel, Switzerland.
High speed...self contained...easy to operate high resolution...zero dead volume...and more
Report for Analytical Chemists ~~
of ASALTTICALCHEMISTRY.H i s points were t’liat a n analytical cheniist should know enough about existing methodologies to choose the hest oiie for application to a given sainl)le, perhaps modifying it if necessary to fit the particular situation, aiid that there is also ai1 analytical science which seeks, as its own goal, the improvement of analytical iiicthodologies without regard to >lwcific problems. Years ago, D r . I,uiitIell wrote about the “analysts” and the “determinators.” The analysts w r e those who could take a sample as it was, apply suitable methods allowing for interferences, a n t i coiiic up with a correct analThe tlcteriiiinators were e who preferred to develop iiicthods for single substances. Tlicy generally worked with pure ,solutions aiitl !!.ere not concerned about interferences. Towadays, with niorc and more instrumental methods in vogue, the analysts aiid (1cteriiiiii:itors are coming closer togctlicr. Soiiie map only be syringcliaiitllers. button-pushers, or turnt:ihlc-fecclcrs ; the interferences are sul)posecl to be taken care of autoniaticnlly. Before a deterininntor c:in use n i i automatic system, hohym ~ r ;a, gootl analytical chemist has 1)roI):il)ly heen needed t o set it’ u p , 1)erliap with the aid of a computer cs])cart.
I like t o tliiiik of :In industrial nnnlyticd cheniist t:tking on a whole i)roblem, in tlie following A product is found to depart from t.pecifications in some ~ v ~ perhaps y , showing a n off -color, turbitlity, or Ion- melting point, or l)o,wil)ly a foreign peak in a spectriiin or clironiatograrn. T h e first q u t ~ t i o n sfor the chemist are: what is it, ancl hon- much? For the pro( I II c t i on s~p crvisor , i:hou gh , t h e qucstions are: bow does it get in, :inti how can it he kept out or reniovctl? The complete answer requires characterization, ineasureinciit, some chemical detective v o r l i , 2nd a linoxledge of tlie physical and chemical properties of the inipurity and of t h e rest of the systcin. That the answcr lie reached promptly iF usually quite urgent; t o produce had nintcrinl is uncconomicnl, and t o shut :I plant d0.cr-n is almost unt1iiiilial)le. Prohlems of this kind can he pretty denlanding. The
analytical cheniists who can handle them will be treated with respect. I alii coiicerned t h a t chemistry students these days inay be led to rely too much upon 1ii:,trumeiits, n itliout learning enough about classical separation methods and the descriptive chemistry t h a t ~ l i o u l d be taught in analytical course:, These kinds of kiion ledge are needed to solve our chemical problems We should face this fact in our technical organizations and 111 our dealing:, with colleges and universitic. There is a n old saying: To be a good cheinist oiie must firat lie a gootl analytical chemist The coiiverse niay be even inore true-to lie a good analytical chemist one must fir.t be a good cheniist \Ye c:tn teach iiiztruiiiental analysis in i iiclu s t r y , liu t we shou lcl not h ave to teach 1i:i.ic chemistry SevertlieIebs, rve all must continue to be \tudents of chemistry. Contributions in Product Development
It should not he thought t h a t inchemic a 1 ana 1y si s d e a Is only Jvith quality control. Often the prolilem is with tlie use of a 1)rotluct. Years ago I was asked t o 1)articipate in the early development of iiictliyl bromide as a funiigant. Alethy1 bromide was a nenand mysterious compounci, volatile and quite toxic, and people were afraid to use it. 11r. Beshgetoor inay have selected me for the assigiiiiicnt thinking tliat I n’as expendable. Questions arose a s to lion. t o determine whether, during a funiig:ation, the vapor would reiiiaiii in a vault or n-arehouse long cnougli to be lethal to insects. whether it might poison soineonc outside, and how much might remain as :t residue in a fumigated food. S. A. Shrader, A h . Beshgetoor, and I developed methods for usc in ansn-ering such questions, and published them. The necessary toxicological data were determined in the Biochemical Research Laboratory established somewhat earlier wider Don Irish. One of my pleasures during t h a t period conPisted in receiving supplies of fine fresh foodstuffs, fumigating them, and preparing samples after periods of airing. I would carry out separations of t h e organic and inorganic hromide, and nr. Shrader
t i u st r i a 1
would determine the bromide in each fraction using Kolthoff and Yutzy‘s inodificatioii of the van der lfeuleii method. \Ye established that practically any food would lose all of its methyl broiiiitle within two days and t h a t only a trace quantity of inorganic bromide a-ould remain. For a given food, tlic amount of inorganic liroinicle remaining nould be fairly proportioiial to the concentration of fuiiiig u t aiid the duration of exposure. Incidentally, we could also carry home a fair amount of the food. T h e Steiigers and Shraders ate uiiusually well in those days. =It one time we hac1 over 100 111 of fine IYisconsiii cheese in the lab. A - h o n g other foods teated w r e lmiis, dchytlr~itctlvegetables, cereals, 1i:tkery products, h i t t e r , ice crcain, chocolate>, various kinds of iiuts, etc. Thus, we estnl)lis!ictl, not only hy analyses. but liy practical eating tests, t h a t the foods were ssui t a b 1e for c oiiciiiiip t i on. We, a ncl others, recognized a problein in the fumigation of wheat flour: if a i l cscessiw concentration of iiictliyl broiiiide were used, or if the s:iiiie flour i w r e fumigated repeatedly, a lint1 odor might lie protliiced ivheii it TYRS lialied into bread or ivheii tlie brcacl w:a> toasted. The odor was eventually attriliutecl to the ine t hyla t ion of sul f Ii y dry 1 grou1)s in tlic protein, releasing a trace of iiict 11y 1 iiiercn p t a n or t liio- e t licr upon heating. We got t o lie pretty good a t recognizing such odors in compiaiiit wiiipies, aiid could confirm the cause', wlieii it iva> overfiiiiiig;itioii, by detcriiiiniiig the hroniidc resitlue. l l y vifc took p ~ r t in this kind of work a t hoiiie. lialiiiig tlic flour into hrcad or rolls which TTC tasted aiid saielled. JIost coniniercial niillers arc liiglilp relialilc and n-lien presented with o w (lata n-ould accept t h e fact that the flour had heen overexposed. Tliere ivere n few L>nialloutfits, hon-ever, t h a t tried t o h h m e fumigation for prohlems caused by old or liioldy 11-hcnt. Our tcsting program thus :i v ed t 11e c om 11any c onsi d cr nhl c money in ‘the early (lays. I t has bcen continued as :I service to funiigator,
