THANKS TO INSTRUMENTATION, THE ANALYTICAL CHEMIST OF TODAY HAS AT HIS COMMAND HIGH-SPEEDTOOLSOFPHENOMENALPRECISION
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“Analytical chemistry, or the art of recognizing different substances and determining their constituents, takes a prominent position among the applications of the science, since the questions which it enables us to answer arise wherever chemical processes are employed for scientific or technical pur oses. Its supreme importance has caused it to be assiduously cuytivated from a very early period in the history of chemistry, and its record comprises a large part of the quantitative work which is spread over the Scientific Foundation of whole domain of the science”-“The Analytical Chemistry” by Wilhelm Ostwald, 1895.
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LTHOUGH the Division of Analytical Chemistry is the third youngest of the 20 A.C.S. divisions, the history of analytical chemistry is, in many ways, so integrated with the story of chemistry itself that it is properly regarded as “the oldest branch of the subject.’’ ks chemistry developed, the need for 1;nowledgP concerning the composition of all kinds of matter was a necessity. Consequently, “it came about that many, if not most, of the great chemists of the time were of necessity analysts and the analytical branch of chemistry stood in high repute” (6). Little wonder that Robert Bunsen stated earlier: “He who is not an analyst is no chemist.” I n order to detect and determine the constituents or purity of substances, chemists had to develop a large number of methods, both gravimetric and volumetric. It is true that many were long tedious procedures and subject to many factors which were not understood. But they served their purposes. Volumetric methods were available for some determinations of acids, alkalies, oxidants, and reductants. Common gaseous mixtures also were capable of separation and analysis. But this “high estate” of analytical chemistry did not maintain itself. I n the latter half of the nineteenth century, this branch “came to be looked upon more or less as a handy tool for ulterior ends, a tool, moreover, which need not for most purposes be of the sharpest or the best, or entrusted only t,o the most careful and skilled operators” (6). The three chief reasons for the apparent loss of interest, in analytical chemistry itse:f was the newer and more appealing development of ( 1 ) the use of voltaic batteries in electrolysis studies and the subsequent speculations and experimental researches in electrochemist~ry; (2) the synthesis of urea, resulting in the era of organic chemistry, its theoretical concept,ions, and the discovery of many new types of reactions; and (3) the interest in the borderline studies between physics and chemistry, giving rise to physical chemist>ry. All these appeared as unesplored fields and thus gave greater promise of new achievements and discoveries. More glamor and far more spectacular result8 seemed to be associated with these neK fields. Some chemists felt that the field of analytical chemistry “was an exhausted onewit,h lit,& reward for the research worker.” Three quarters of a century ago, practically no graduatc work in chemistry was done in this country. I t was still considered highly desirable to obtain a degree from a foreign university. Therefore, most American students went to study a t Gottingen, Berlin, or Bonn. Although a majority of them studied organic chemistry, a few sought to do analytical work with K. R. Fresenius at Wureburg. Many preferred to publish their articles in the older and more established European journals.
Another remon given for the pro-European trend w a ~that laboratory instruction had not yet, become a part of the American college curriculum. Frequently, chemistry professors who suggested that some provisions be made for the installation of laboratory equipment were rebuffed. In some schools, students were forbidden to enter and vrork in laboratories. In other schools, if they did work in laboratories set u p by aasistants, such work was optional and not considered a part of the regular college training. The instruction usually was given in experimental and analytical chemistry. The majority of students in these colleges were preparing either for law or divinity schools. Privately owned laboratories offered the best openiugs to students-especially those interested in analytical and applied chemistry. Here the first lessons were given in the art of chemical analysis and research. Outstanding examples of such laboratories were those of J. C. Booth in Philadelphia and C. T. Jackson in Boston, founded in 1836 and 1838, respectively. By training individuals and by encouraging Americans t o examine and develop their native resources, these laboratories helped to establish a strong school of analytical chemists in this country. Aside from the numerous contributions by Booth, Jackson, and their coworkers, many others contributed significantly to analytical chemistry. Included in this group were J. Lawrence Smith, T. H. Garrett, Wolcott Gibbs, C. F. Chandler, John W. Draper (first A.C.S. president), and Augustus A. Hayes. PERIODIC TABLE
Another factor that aided the development of analytical chemistry was the first foreshadowing of the periodic law by the historic memoirs presented to the French Academy of Sciences in 1862 and 1863 by Alexandre E. Bkguyer de Chancourtois. B6guyer’s concept of a cylindrical spiral arrangement of the elements in the order of their increasing atomic weights went unnoticed for some time. The first clear statements of this periodicity were made independently by Idthar Meyer and Dmitri Mendeleev about 8 years before the founding of the A.C.S. This led a number of chemists, both abroad and a t home, to study the relations between the atomic weights and more especially the physical properties of the elements and their con~pounds. This revival of interest in studies of the elements resulted in attemptp not only to discover new elements (those missing in these arrangements), but to develop more detailed or exacting methods of separation. It was soon recognized that the rarest and least investigated elements were as important as the well-known ones However, this latter aspect was not developed fully until the second decade of the twentieth century With the growing importance, from both industrial and scicntific standpoints, of the presence of small amounts of elements in a given material, it became highly desirable to review many methods of determination which heretofore had been considered reliable and accurate. In time, these c r i t h ) studies revealed defects or errors. Analytical chemists soon discovered that these errors often compensated each other or that the presence of rarer elements, either known or unknown, must be sought. Quantities of constituents which heretofore werr considered too smail
C. K. Deischer, University of Pennsylvania, Philadelphia, Pa. 1283
C. K. Deiiwter
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Sketch indicates size and layout of quantitative chemistry laboratory supervised by H . C. Bolton in 1878
for determination or thought to be unworthy of determination, had to be determined with some degree of accuracy. Obviously, new tests or methods were required. Toward the close of the nineteenth century, Wilhelm Ostwald’s volume, “The Scientific Foundations of Analytical Chemistry,” was the first real attempt to systematize the mass of data and put analytical chemistry on a sound theoretical basis. Physicochemical researches, demanding more exacting methods, shed new light on such phenomena as solubilities, hydrolysie, and equilibria, and thus opened up new fields of research. These investigations later proved to be immensely fruitful and helped restore analytical chemistry to a high plane. Textbooks on analytical chemistry used in the United States during this same period were, for the most part, either translations or reprints of foreign volumes. The most widely used texts were those of K. R. Fresenius, “A Manual of Qualitative Chemistry” and “A System of Instruction in Quantitative Chemical Analysis.” Various English editions of this latter work appeared in this country. Another text, “Elementary Quantitative Analysis,” written by Alexander Classen, was translated in 1878 by Edgar F. Smith (a three-time president of the A.C.S.) and somewhat later by W. Hale Herrick. By 1890 ‘.,4 Systematic Handbook of Volumetric Analysis” by Francis Sutton had reached its sixth edition. Clemens Winkler’s “Handbook of Technical Gas Analysis,” printed in 1884, was translated into English by G. Lunge in 1885. Within a short time several other volumes written by Bmericans began to receive recognition and adoption as textbooks in analytical chemistry. The development of analytical chemistry was further influenced by the researches of American chemists in the introduction of electrolytic methods for the determination of metals by Wolcott Gibbs and extended shortly thereafter by E. F. Smith; studies in double and complex salts by Wolcott Gibbs, E. F. Smith, and Allen Rogers; atomic weight determinations by Frank W. Clark, J. P. Cooke, Jr., J. W.Mallet, T W. Richards, and G. P. Baxter; rare earth and rare element separations and determinations by W. L. Dudley, J. Lawrence Smith, T. H. Norton, and Charles James; liquid ammonia systems by H. SeeIey, E. C. Franklin, and H. P. Cady; and the important generalizations on solvates by H. C. Jones. I n addition, the ever-expanding chemical industries in our country necessitated the development of new techniques and instruments for rapid determinations.
I n m i d - 1 8 8 0 ’ ~ undergraduates ~ posed for photograph in assay room at the University of Pennsylvania
Wolcott Gibbs was one of the first scientists to apply electrolytic methods to the determination of metals
USE OF INSTRUMENTATION
The older slogan of “dry, ignite, and weigh” no longer served &B a satisfactory conclusion to a day’s work in analytical chemistry. New analytical toole, in the form of instrumentation, were found to be applicable in the solution of special problem. With the extensive and impressive development of instruments, the analytical chemist had to “become familiar with a bewildering array of techniques and a t least become moderateIy acquainted with the dialect of the physicist and engineer” (9). These newer developments and applications of instrumentation seemed t o folIow four general directions. First were those dealing with the classical methods. Improved and more highly refined methods, combined with the use of instruments, gave greater speed, higher precision, and, in some cases, a degree of automatic operation. Second was the introduction of self-recording devices to the study of second-order effects or feeble reactions. Third were the conductometric, refractometric, and thermal methods applied to determinations of constituents. Fourth were the purely experimental and theoretical studies which led to a more intelligent use of instruments, a wider applicability, and incomparabiy better analytical tools. Some of these studies were extended by the constant flow of smalI technical improve ments in the instrument itself and by changes in technique. I n the first quarter of the twentieth century, a few special analytical instruments were known, but their acceptance as such was very limited. Chromatographic adsorption, discovered by 1284
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the Russian botanist M. Tswett and published in 1906, did not become an important tool until 1931, when Kuhn and his coworkers used it to separate certain isomeric substances. Since 1939 many significant improvements of apparatus and procedure have been made. Many new absorbents, solvents, and methods of separating the bands or zones have made the resolution of mixtures possible. Spectroscopic methods, as late as 1910, were of little quantitative value and appeared to be impractical. Great advances have resulted since 1940. Electroanalysis, one of the older methods of analysis, was considered as “belonging to the museum class” a t the close of this quarter of the century, but since has become very useful. New compact, portable instruments employing new techniques have aided greatly in the development of the field of polarographic analysis. Polarography, one of the five most popular instrumental methods of analysis (15), was originated by the pioneer work of Heyrovskj. and Shikata of Prague in 1925. Polarographic references did not appear in American journals until 1937. The end of the “unaccountable incubation period” was marked by the appearance of the Kolthoff and Lingane monograph, “Polarography,” and the E. H. Sargent & Co. “Bibliography of Polarographic Literature,” both in 1941. Because so many diverse substances are subject to electrolytic oxidation-reduction, the instrument is useful in the rapid determination of trace impurities or in the amperometric titration of relatively small concentrations of various metal ions. Microchemistry, introduced into the United States in the late twenties or early thirties, began its more rapid growth about 1935. This was due t o the introduction of the methods of Pregl and Emich by Benedetti-Pichler and Niederl; the pioneer work of Chamot and Mason in chemical microscopy; the applications and extension of new techniques to the problems of American industry by B. L. Clarke, H. W. Hermance, G. L. Royer, L. T. Hallett, and others; the offering of courses of instruction in certain schools; and the appearance of suitable textbooks (1, 2,11). Bibliographies in recent reviews of inorganic and organic microanalysis contain extensive listings of references. Quantitative ultramicroanalysis, currently considered by some to be in the developmental stage, has been highly useful in work with radioactive analytical tracers. These tracers make it possible for investigators to determine the completeness of analytical reactions. So rapid was the growth of instrumentation in analytical analysis that by 1946, Soy0 of all the analytical papers were on instrumental methods of analysis. This indicated their future importance in chemistry. AB W. J. Murphy stated a t the Symposium on Modern Analytical Methods a t Baton Rouge in 1950: “We may rejoice that recognition by analysts of the latent possibilities of instrumentation has brought almost a renaissance in analytical chemistry.. Instrumentation will not supplant, but will rather supplement, wet methods.”
A t Argonne National Laboratory, chemist titrates dangerously radioactive sample by remote control
Analyst, watching deJlection of light beam, runs potentiometric titration of sorghum starch with iodine solution
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ANALYTICAL EDITION
Because of the ever-increasing activity in chemistry and the growing numbers of original papers of an analytical nature, it became necessary in 1929 to issue a supplement to INDUSTRIAL AND ENGINEERING CHEMISTRY known as the Analytical Edition. This was a quarterly publication. Eight years later (1937), it became a monthly supplement. By this time, the Analytical Edition had “attained a world-wide circulation and, because it is a tool of great utility and immediate value, it has achieved an enviable place in chemical literature” (6). A survey made by the Opinion Research Corp. prior to 1948 disclosed that 57% of the A.C.S. members read or referred regularly t o the Analytical Edition. E. J. Crane, editor of Chemical Abstracts, reported in 1950 that the analytical chemistry section in Chemical Abstracts rated third highest among the sections most regularly read Qr scanned. The long established and familiar Apparatus at N e w Brunswick Laboratory i s used to detername, Analytical Edition, was changed in 1947 to Analytical Chemistry. Circulation was made independent of INDUSTRIAL mine minute amounts of radium or radon in ore samples 1285
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INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 43, No. 6
The first official meeting as a new division was held a t Baltimore in April 1939. No sooner had t’hisgroup begun t o functiou when in September 1939 a comniit,tee representing the Ana1ytic:il Section (Willard, Furman, Kolthoff, and G, F. Smith) held a joint iiiceting with the Executive Committee of the new division. This arialytical group had voted to separate from the Divkion of I ~ h y ~ i c aand l Inorganic Chemistry and accordingly out,lined i t proposal for merging their membership with the Division of Microchemistry. Both coinmit’teesagreed that “a change of tjitlc and bylaws of the microchemical group should be made (provided this was approved by the membership of the latter group).” At the Division of Microchemistry’s husinws meeting in Rost,on in 1939, the merger which had been suggested by the analytical group was announced to the membership of the Microchemical Division. The minutes stated that ”in general t,his discusrion \vas favorable.” The secretary was asked Lo “write a 1ett.csr to the members to gct, an opinion on the matter.” The qu~stion was to he finally voted upon in Detroit i n the fall of 1940. The opinions expressed by a postcard qucationnaire gave an overD I V I S I O N O F A N A L Y T I C A L CHEMISTRY n-hclniing 76-to-’2 r o t e in favor of combining the groups. ArAbout 20 years aft,er the appea~anceof Fritz Pregl’s note~vort~hy cordingly, pet.itions were prepared by the joint executive conimittem and presented to the Council in Detroit, suggesting that monograph on quantitative organic niicroanalgsis, interest, in this the name of the division br subject had increared t.0 changed to the Division of such an extent that by SepOfficers of the Division of Analytical Chemistry“, inalytiral and hlirmcliemtember 1935aSymposiumon 1938-1951 ]%try Microchemistry constituted T l i ~ Council L ~ p p r o v ~ ~ ( l a half-day session of the the iririger and on St.ptcwAnalytical Chemistry Secher 11, 1940, the two gioiip rA.T. IiaiIett 1938 tion of the Divisionof Physimet to elect officers for tliii: G. L. Royei cal and Inorganic Chem1939 lien division. The minuteq G I,. Ro~e’r 1940 istry. In February 1936, qtated that “it is to be an F. m l’o\\e1 1941 the News Edition comunmitkn undemtanding I‘ I\- P O l V P ? 1042 mented: “Since microchemthat the chairman and vice F. R Power 1043 istry cannot be included ehaiinim be elected t o repC . 11 Alter wholly within the scope of 1044 rwent the two fi~lds.” C hl. .4ltei 1945 any of the existing divisions iccordingly, G. E P. LunR. A. Huidett of the A.C.S. and because of 1946 dell was elected chairman R . A. Rurdett 1947 the general applicability of of t h b newly amalgamated R. A. Rurdett this technique to almost all 1948 group, 0.L. Itoyer, vice IT‘ G. Batt 1940 of the major branches of chairman, and F IT. \Ir.G Batt chemistrv. a separate divi1950 IT’. G. Batt Power, wcretary-treasurer. sion of the *A.C.S. devoted 1951 If. H. \l-illavcl The first notice to proentirely to microchemistry spective authors of the diviis under consideration.” sion bore evidence of a retained individuality. It was proporcd Accordingly, a group of chemist^, 11c:itled 115, A . -1.J3c.licdcttithat the division hold separate HP 1?-011 us joint sessions. Thus? Pichler and F. Schneider, WIP :iuthorized to arrange :i separnte planning to present papers were requested to underscore the program for the Bpril meeting in l- the division or joint’ly port, which was the first of a series aimed a,t standardizing microwith ot,hers, have appeared on the nat,ional programs of the chemical apparatus for the gravimet,ric determination of carbon h.C.S. in the past 15 years. Some of the more important titles and hydrogen. deserve mention.
ENGINEERING CHEMISTRY and the scope was broadened 1.0 include editorials, news items of interest to analytical chemists, and other feature material. Since 1949, the publication has issued an annual review of developments in analytical chemistry. The first group of papers in 1939 not only reviewed theoretical and fundamental material from the previous year but provided :I five- to ten-year reviem. of each field of analyt,ical chemistry and a survey of the development of vtwious analytical tools. A total of forty articles appeared. The second progress report in 1950 included tiz-ent,y-~cvcri articles on fundamental developmcnts and eleven 011 prwtic;il applications during the previous year. The third annual revivnin 1951 contained eighteen reports on theoretical and iuiiditmeiital material and eight reviews of applications of new devclo1)ments in a number of industries and fields of specialization. That there is renenwl interest in analytical chemistry is evidenced by the nppcararice of cxcellentlj- written articles on this subject within the past six months (4,7 , 8, 10, 12--14). AND
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a Originally called t h e nil-ision of Microchemistry, t h e division changed its n a m e to t h e Division of Analytical and Llicrochemistry in 1940 a n d t o t h ? Dirision of rinalytical Chemistry in 1949.
Recent advances in methods for the determination of traces Application of micro and semimicromethods to industry
dtttndard chemicals and reagents Purity and identity of organic compounda Statistical methods in experimental and industrial chemistry Spectrochemical methods of analysis Polarography, electrolysis, and overvoltage Teaching of analytical chemistry Infrared s p t r o s c o p y Determination of functionality in organic compounds Adsorption Microchemistry and the petroleum industry -11~0 in this period, numerous committees made studies and rendered reports on such subjrcts as the standardization of apparatw, both macro- arid microchemical; the naming of analytical methods; nomenclature in analytical chemistry rind in chemical microscopy; and the precision of microbalances. E’urther evidence of divisional activity, not associated with the national meetings of the Society, was the selection and p r e p aration of e list of speakers on topics pertaining to analytical and microchemistry. Prepared in 1948 by a special committee of the division, this list included, in addition to analytical chemmts, some nonanalytical chemists. Of the nonanalysts, all of the listed speakers were workers in fields closely allied to analytical chemistry. It was felt that such a list, in the hands of the secretaries of A.C.S. local sections, would be an aid in the preparation of stimulating programs. Some of the topics included electroanalysis, polarography, the electron microscope, fundamentals oi analytical chemistry, instrumentation, nucleonics, chromatography, fluoreseenee, spectroscopy (x-ray, infrared, ultraviolet, emission, absorption, mass, or Raman), metallurgical analysis, organic reagenb, electrometric methods, optical methods, lowpressure techniques, and extractions. rill these varied activities initiated by the division or other A.C.S. divisione and ably championed by many persons interested in chemistry have EO extended the scope of analytical chemistry that it has become a part of every branch of chemistry. Much of the progress can be credited to the individuals who have been leadew in the division’s activities or who have served on cwimittees appointed by these officers. As we reflect and pay our respects “to the great, the near great, and the unnamed workers who laid the foundations and built the atiucture that has brought analytical chemistry t o its present high estate” (a), we must also accept the challenge of tomorrow. Analytical chemistry of today is but a promise of what is to come. Ita future must of necessity Ire “influenced by the thoughts and actions of the analytical chemist himself; it will take skillful driving and attention to the road if one is to avoid the ditches on the bumpy roads the analytical chemist has ridden in the past” (14). A s analytical chemists were the men who helped make the pa& most certainly they mwt also be tfie men who are making the tomorrow.
Wearing film badge, researcher at National Institutes of Health begins analysis of radioactive product
LITERATURE CITED
Benedetti-Pichler, A. A., and Spikes, W. F., “Introduction to the Microtechnique of Inorganic Qualitative Analysis,” Douglaston, New York, Microchemical Service, 1935. (2) Chamot, E. M., and Mason, C. W., “Handbook of Chemical Microscopy,” New York, John Wiley & Sons, 1940. (3) Churchill, H. V., Anal. Chem., 22, 1 (1950). (4) Elving, P. J., Ibid., 22, 411 (1950). (5) Hillebrand, W. F., “Our Analytical Chemistry and Its Future,” New York, Columbia University Press, 1917. ( 6 ) IND. ENG.CHEM.,NEWSED.,15, 47 (1937). (7) Kolthoff, I. M., Chem. Eng. News, 28, 2882 (1950). (8) Miner, C. S., Ibid., 28, 3762 (1950). (9) >hiller, R. H., IND. ENG.CHEM.,ANAL.ED., 13, 667 (1941). (10) Murphy, W. J., Chem. Eng. News, 28, 1997 (1950). (11) Niederl, J. E., and Niederl, V., “Micromethods of Quantitative Organic Elementary Analysis,” New York, John Wiley & Sons, 1938. (12) Rather, J. B., Moore, R. W., and Renedetti-Pichler, A. A., Chem. Eng. News, 28, 1724 (1950). (13) Rosenblum, C., Ibid., 28, 3578 (1940). (14) Seaman, W., Ibid., 28, 2258 (1950). (15) Strong, F. C., Anal. Chem., 19,968 11947). (1)
I n Eastman Kodak control laboratory, analyst weighs out small sample of sodium sulfite 12817
