C&EN REPORTS: Pittsburgh Conference on Analytical Chemistry and

Nov 5, 2010 - PITTSBURGH.-By hooking up a mass spectrometer with an electronic computer Atlantic Refining Co. has produced a new laboratory instrument...
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THE CHEMICAL WORLD THIS WEEK the industry, with an assist from t h ^ C&EN REPORTS: Pittsburgh C o n f e r e n c e on A n a l y t i c a l C h e m i s t r y and A p p l i e d Spectroscopy •Government in the form of accelerated fazx amortization, is nevertheless proceeding with one of the largest, long-term planet expansion programs on record. The charts on p a g e 1090 show production "targets'" aimed a t b y 1955 for some of the more basically needful products. I n its projection for p h t h a l i c a n h y d r i d e to an annual capacity of 367 million ASTM will assume responsibility for indexing of pounds in 1955, Washington a d m i t s spectrographs references there m a y b e a problem in timing t h e supply of raw materials, naphthalene oar P 1 T T S B U R G H . - B y hooking u p a mass fertile g r o u n d judging from the progress o-xylene. T h e p r o g r a m m e d increase of 2 8 0 m i l - spectrometer with an electronic com- reported a t this year's sessions. T h e coding system on I B M p u n c h cards suggested lion pounds of phenol anticipates a largezr puter Atlantic Refining Co. has p r o d u c e d supply of benzene b y 1955, b y whicL· t i m e *» n e w laboratory instrument t h a t will b y L . E. Kuentzel of W y a n d o t t e has been adopted b y a group of volunteers who the petroleum industry's new facilities fo:r make a complete molecular analysis of a 20-component hydrocarbon mixture in 1 0 have searched 28 journals and recorded making benzene should be operating, about 5 0 0 infrared spectra. T. V. Parke Sizable expansion for nitrogen is for t h e minutes a n d t y p e out t h e results on a of E l i Lilly, who reported this program, most p a r t in synthetic anhydrous a m - paper tape, W . S. Young told a session of said that the ASTM is interested in asmonia. T h e production goal calls for 2 . 9 the t h i r d annual Conference of Analytical suming responsibility for t h e project and million short tons of nitrogen, a rise o i Chemistry and Applied Spectroscopy h e l d here M a r c h 5 t o 7. The secret of t h e n e w Kuentzel later confirmed- t h a t they W o u l d 1.3 million tons over 1950 capacitytake it over. As t h e collection is completed Capacity goal for chlorine in 1955 ha_s device is a "selector" developed b y Conbeen set at 3,430,000 short tons, or 930,- solidated Engineering Corp. which codi- the cards will b e publicly available at cost, a b o u t $3.50—4.00 p e r thousand cards. 000 tons more t h a n 1951 a n d 1,230,000 fies t h e o u t p u t of t h e spectrometer into a tons over 1950. T h e chlorine announce^- form which c a n b e fed directly into a Kuentzel also showed t h e group sugment from the D P A said nothing with r e - digital computer which can solve t h e gested p u n c h cards for recording ultragard to caustic soda, t h e co-prodxict i x i equations necessary to determine t h e exact violet, mass spectrograph, a n d x-ray difthe electrolytic manufacture of chlorine quantities of t h e various components of fraction data, and Parke suggested a proand one of the industry's most troublesome the m i x t u r e . Previously, t h e readings from gram for ultraviolet d a t a to parallel that the spectrometer were either calculated b y supply questions. now u n d e r w a y for the infrared. An independent and complimentary proCapacity target for sulfur is set at 8.^4 hand or f e d into a simultaneous equation gram for the recording of infrared data is million long tons or 3,220,000 tons ove>r computer to obtain the analytical results. nearing completion under National Rethe 1950 supply. Of this increase it i_s The results from t h e digital computer a r e search Council auspices, E. C. Creitz of understood that 520,000 tons will b e s u p - reproduced in written form b y a simple the Bureau of Standards told t h e group. plied b y private industry without govern.- mechanical arrangement. The N R C project uses Keysort cards on ment assistance, plus t h e following p r o Young said t h a t the combined units will which t h e spectra are actually reproduced. grams with government aid: 690,000 torats make a 'complete analysis in a b o u t o n e The IBM cards carry only a code n u m b e r from n e w domes; 280,000 tons from p e - tenth the time required b y the most rapid which c a n b e traced t o a separate file of troleum and natural gas; 170,000 tortus previous methods. Only one operator will spectra o r to the general literature. T h e from pyrites; 100,000 tons from srneltesr be r e q u i r e d t o use t h e instrument. As IBM system, Creitz said, has the advantage acid; a n d 10,000 tons from "other sources-" soon as t h e initial unit h a s been p r o v e d of permitting very rapid search through Industry's own plans for expanding p r o - in t h e Atlantic laboratories, t h e speaker a large n u m b e r of spectra while the N R C duction facilities go beyond 1955 in sorrx-e said, the design will be m a d e available. chemicals. While supplying some 6O0 Mass S p e c t r o s c o p e r s J o i n C o n f e r e n c e . system will permit only limited searching but provides a file of usable absorption million pounds of acetylene in 1952, ±t \V. S . Young is t h e leader of a group of curves. T h e N R C is n o w making a comexpects to meet a n acetylene demand i:n mass spectroscopers that joined t h e Pitts1955 for one billion p o u n d s and a con- burgri conference for t h e first time this prehensive search of past publications for infrared spectra a n d h a s incorporated the sumption in 1960 of double that figure. year. T h e association of mass spectrosAmerican Petroleum Institute collection From 1,016,000 tons in 1949, privately copers is in an organizational stage. H o w of curves into their series. About 4000 operated synthetic ammonia plants aire ever, they do not plan to m e e t annually erecting facilities to m e e t a projected at Pittsburgh b u t will hold their sessions spectra a r e already available, Creitz said, and he expects to have nearly 10,000 capacity of 3,240,000 tons in 1955, a n d jointly with various analytical and physiwithin a few months. W h e n the literature 3,240,000 tons in 1956. Formaldehyde cal m e a s u r e m e n t conferences. search is completed t h e N R C will begin production may rise t o around 1 billion Trie conference is sponsored jointly b y pounds in the current year. T h e output i s the Analytical Division of the Pittsburgh to make t h e cards available at cost. expected to hit 1.2 billion pounds in 195S, section of the ACS and t h e Spectroscopy In the discussion t h a t followed the sesand 1,350,000,000 pounds in 1956. sion t h e r e were several comments on the Society of Pittsburgh. It evolved three efficacy of "negative searching" for abChemicals generally, aside from a smaJl years ago by a consolidation of t h e a n sorption spectra. In this technique the but important group h e a d e d by sulfu-r, nual local meetings held individually b y curves a r e searched for in areas in which coke-oven products, chlorine, a n d their these two groups. Since t h e consolidation, there is n o absorption rather than for abderivatives, have been large enough £ n the meeting h a s assumed national status sorption peaks. I n examining t h e spectra supply since mobilization started t o meet and a perfunctory survey of t h e registraof mixtures, which includes most analytiincreased demands. A n u m b e r of chemd- tion cards this year revealed t h a t t h e local cal samples, the points of low absorption cals that were under allocation h a v e beesn participants were greatly o u t n u m b e r e d b y are m o r e significant than the peaks, it decontrolled, and plant expansion plans representatives from most of the other was said, since t h e absorption "valleys" appear to preclude the possibility of ser-i- states, Canada, Mexico, a n d E n g l a n d . ous shortages for some time. T h e p r e C o o p e r a t i v e Indexing Mokes P r o g r e s s . must be characteristic of all t h e components whereas each of t h e absorption peaks ponderance of price reductions in recent The proposals m a d e at last year's conferof all t h e component materials will be months should now b e considered as a ence for the cooperative collection of represented in t h e compound spectra of prelude to some modification of t h e pric*e spectra a n d bibliographic references relatthe mixture. T h e point was generally well ceiling order as it affects chemicals. ing t o spectrography apparently fell on

N e w Device M a k e s Analysis And Types Out Results

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CHEMICAL

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,^©IH' ι

/ficonef has a new companion alloy r

INCOLOGY

ttë#

(32 NlCKEL-21 CHROMIUM)

. . . another addition to the Into High-Temperature alloy family

You are p r o b a b l y f a m i l i a r w i t h t h e h i g h temperature strength properties of Inconel®— its resistance to oxidation and corrosion — its acceptance by industry as a high-temperature alloy. But now NPA has restricted Inconel for certain heat-resisting applications (Schedule C to NPA Order M-80 ). And you may be wondering what metal you can now use to solve your high-temperature operating problems. Have you heard about Incoloy? I t is permissible for most high-temperature applications. And it may be the answer for you. Incoloy® is not a substitute for Inconel. It's a specially developed companion alloy with a composition of 32 Nickel — 21 Chromium. It provides a useful degree of strength at high temperatures and good resistance to oxida-

tion. And it has good workability and welding properties. Incoloy is the latest development of INCO'S Engineers in their continuous search for better high-temperature materials. Like the other INCO Nickel Alloys it is on extended delivery because of defense demands. So anticipate your needs well in advance — and when ordering, be sure to give NPA ratings and complete end use information. For more information on this newest hightemperature alloy write for our "Preliminary Report on Incoloy." And if you have a special problem on which you would like the assistance of our High-Temperature Engineers, ask us to send you a High-Temperature Work Sheet. THE INTERNATIONAL NICKEL C O M P A N Y , I N C . 67 Wall Street, New York 5, M. Y.

NICKEL ^ ™ K ALLOYS IIAOC

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THE CHEMICAL WORLD THIS WEEK

Soon NRC will distribute key-punch cards containing absorption spectra and literature references, said E. C. Creitz of NBS received a n d may influence future systems. Kuentzel h a s already modified his cards for limited negative searching. Tracing

Origin of Atmospheric

Dusts.

In order t o reduce pollution of u r b a n atmospheres it is necessary t o determine t h e source of t h e pollutant. W h e n the foreign material is solid, L. L . Schmelzer of the California D e p a r t m e n t of Public Health told the conference, it c a n b e traced by x-ray diffraction analysis. Atmospheric dusts are always mixtures of various crystalline and amorphous substances a n d industrial dusts also usually contain several components. X-ray diffraction patterns of samples having as many as three or four components are usually so complex as to defy analysis, the speaker said, so t h a t complete analysis of a sample of atmospheric dust is impractical. However, Schmelzer told t h e analysts, commercially available, recording type x-ray spectrometers m a y b e modified by putting a bias a n d bucking voltage in t h e potentiometer circuit so that t h e diffraction pattern may be shifted up or down from its normal position. Such a n arrangement permits the tracing of several patterns o n the same sheet, each pattern slightly displaced from the other. If the patterns of atmospheric dust samples and various industrial dusts are traced successively o n such apparatus, Schmelzer said that i t is quite simple to detect pattern similarities without ever knowing the composition of individual components. Analysts in Physiological Chemistry. T h e gradually increasing awareness of t h e importance of certain minor chemical constituents of t h e h u m a n b o d y is creating a new d e m a n d for t h e services of analytical chemistry in biochemistry a n d physiological chemistry, Bert L. Vallée of M I T and H a r v a r d t o l d t h e conference. Past experience with vitamins and hormones has proved t h a t what is quantitatively minute is not necessarily insignificant in body chemistry, he said. New results indicate t h a t almost imperceptible amounts of certain metals may spell t h e difference b e tween health a n d disease in m a n y cases.

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Deterrnining t h e n a t u r e a n d concentration of these elements provides a n e w a n d extensive challenge to t h e analytical chemist, Vallée said. D e t e r m i n i n g t h e infinitesimal concentration of t h e s e constituents and t h e nature of their combination will demand all t h e skill and instrumentation at t h e analysts disposal, h e warned. He also predicted t h a t these studies will demand extreme precision because the variation in t h e c o n t e n t of these metals between normal a n d abnormal conditions is often less t h a n t h e experimental error of conventional analytical procedures. He told the analysts that physical scientists too often think of physiological systems as being highly variable a n d subject to treatm e n t only b y statistical means. On the contrary, he said, m a n y of t h e physiological systems a r e t h e result of very precise equilibria and are altered only b y profound changes in the organism. T o illustrate his point, Vallée reported the recent discovery a t M I T of a zinc-

The program for recording spectral data on IBM cards, started by L . E . Kuentzel of W y a n d o t t e , will b e taken over b y ASTM containing protein which is present in normal w h i t e blood cells. In leukemic w h i t e cells t h e zinc content is depressed indicating either a l o s ^ o r transformation of this protein. Similarly, it h a s b e e n found that the copper content of t h e sera of patients suffering from certain mental diseases is abnormally high. T h e delicacy of t h e balance between the various minor metal constituents, Schmelzer said, is apparent from t h e fact that certain metal deficiencies m a y b e induced b y feeding an excess of a second metal. This situation seems t o recommend that analysis for t h e trace metals b e conducted simultaneously. Emission spectrography, n o w almost u n u s e d in biochemistry, should provide an ideal t e c h n i q u e for such analyses, according to Schmelzer. As a final suggestion Schmelzer recommended that the designation of these elements b e changed. H e rejected "trace" elements because " t r a c e " is defined as "too small to be m e a s u r e d " and this is at best an obsolescent nomenclature. T h e y are not "microelements," he said, because

CHEMICAL

some of t h e m a r e quite heavy atoms, n o r are t h e y " m i n o r " elements because t h e y are obviously very i m p o r t a n t in some cases. H e suggested "oligo-elements" derived from t h e Greek for "a small q u a n t i t y . " R a r e Earth Analysis. S o m e of t h e rare earths c a n b e d e t e r m i n e d q u a n t i t a tively in a m o u n t s smaller t h a n ever b e fore possible b y utilizing the fluorescence of their a q u e o u s solutions u n d e r short wave, ultraviolet lighfe· a c c o r d i n g to V. A. Fassel of I o w a State College.. This fluorescence has b e e n k n o w n for m a n y years a n d h a s b e e n used to some extent for qualitative analyses b u t h a s not been u s e d for quantitative determinations because t h e fluorescence is very w e a k a n d the most effective excitation radiation c o u l d not b e o b t a i n e d conveniently or uniformly from conventional ultraviolet sources. Using light from a c o n d e n s e d spark source in air, Fassel w a s able to obtain appreciable fluorescence from solutions of cerium, praseodymium, gadolinium, a n d terbium. However, even with these elements it w a s necessary to construct a specially sensitive fluorometer t o measure the weak light emitted. W i t h this e q u i p m e n t , Fassel and his coworkers w e r e able to m a k e w h a t they believe to b e t h e first q u a n t i t a t i v e d e t e r mination of t e r b i u m . T h e element w a s in the form of t h e oxide a n d was mixed w i t h other rare earth oxides. Apparently t h e other rare earths d o n o t interfere with the terbium determination. Solutions containing as little as 0 . 0 1 % t e r b i u m oxide were measured a n d t h e authors stated t h a t they believed t h e sensitivity c o u l d b e i m proved still further. This is greater sensitivity than c a n b e o b t a i n e d b y emission spectrography. Cerium a n d p r a s e o d y m i u m were also d e t e r m i n e d successfully. H o w ever, gadolinium gave a very unstable fluorescence a n d could not b e measured by this technique. Ferric, nitrate, a n d uranyl ions w e r e found to interfere with t h e determination b u t t h e authors said that they could b e easily eliminated from t h e samples.

J. R. McNally of O a k R i d g e discussed t h e utilization of emission spectroscopy as a means of differentiating b e t w e e n isotopes

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