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Analytical Chemistson Postage Stamps a very popular philatelic pastime.
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electrochemistry,titrimitry, etc. The Arrhenius stamp (Figure 4) is part of a series of Swedish stamps issued on the Popular topica include flora, fauna, 60th anniversary of the awarding of Americana, stamps on stamps, and the Nobel Prize. I’ll be using several of dozens more. For scientists, it is both these stamps throughout this paper. entertaining and educational to study On the very bottom of the stamp YOU and collect stamps on themes, such aa can see the year it was issued (1963), microscopes on stamps (1.2) and which is 60 years after Arrhenius won chemistry on stamps (3).There are many chemists and other scientists on the prize. A.H. Becquerel(1852-1908) (Figstamps, but few true analytical chemurea 5-6) did a thesis on the absorpists (by training) are so honored. A tion of l i h t and especially on fluoresbroader definition of “analytical cence ana phosphoiescenk (spectroschemist,” one extended to include copy). It waa this work that led him to those who have made important conthe discovery of radioactivity. Radiotributions to the development of anaactivity is critical to activation analylytical chemistry, is needed to find a sis, radiotracer studies, isotope dilureasonable number of analytical tion, etc. Becquerel also did work in chemists on stamps. Throughout this the area of polarized light and refracpaper I’ll point out the main analytitive index. Since we’ve just mentioned cal contributions of the scientists on radioactivity, it seems appropriate to the stamps I’ve seleded. This compilook at three Russian stamps (Figures lation is not intended to be definitive, but rather to encourage others to take 7-9) that depict nuclear reactors. Our next scientist on stamps, Alexup similar study. ander G. Bell (1&17-1922), is included Scientists who have appeared on because of the early work he did on stamps are discussed in alphabetical photoacoustic spectroscopy, the detecorder. with occasional diversions to tion of light ahsorption using a microd& those stamps not depicting people. Using a broad definition of an- phone. The inventor of the telephone is remembered on hundreds of stamps; alytical chemistry and the contributions of scientists to analytical chemis- those shown here (Figures 10-13) are try, let’s begin with some stamps (Fig- merely representative. (Bell also founded the journal Science.) C.L. ures 1-3) showing A.M. Ampere Berthollet (1798-1822) (Figure 14) es(1775-1836). He is honored for his tablished the composition of ammocontributions to electricity, which of nia, pruasic acid, and a variety of other course laid the groundwork for elecmaterials. He wan one of the originatrochemistry. Notice the ammeter on tors of volumetric analysis, did a conthe Monacan stamp (Figure 3). Thin siderable amount of work on the stamp commemorates the 200th annichemistry of chlorine, and waa the versary of Ampere’s birth. Alphabetically, we next come to S.A. Arrhenius first to add chlorine to bleach. (That’s (1859-1927), who did considerable of some interest to those of us in the cleaning industry.) A namesake of his, work on the dissociation of electroP.E. Marcelin Berthollet (1827-1907) lytes in solution. He coined the term (Figure 15), devised the homb calo“activity,” which is fundamental to rimeter and did considerable work on reaction velocity (kinetics). P-ted in part at the 182nd meeting of the One of the top analytical chemists Amdun Chemical Society (History of Chemistry Division),A r t 1981. P-ne requesting of his era, J.J. Berzelius (1779-1848) rsprinta me ask to u8e mmmemoiative pastage (Figures 1617) did electrolysis experstamp on their 4 s . Collecting topical postage stamps is
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iments and was the fmt to use a mercury electrode. He determined the atomic weights of all but four of the then-known 49 elements. He did a considerable number of mineralogical analyses, making extensive use of the blowpipe. Bemlius discovered many new elements and did fundamental work in organic analysis, discovering pyruvic acid. He coined the term protein, developed the concepts of catalysis and isomerism, and was the first to introduce the use of hydrofluoric acid for dissolution. Bemliua did a considerable amount of work on improving analytical balances. and he was one of the early advocates of the international use of the French measurement system, the metric system. H. Boerhaave (1668-1738) (Figure 18)introduced the term saturation, by which he meant neutralization. This concept is critical to acid-base titrimetrv. He also wrote a verv fine chemical &&wok. From the Swediih Nobel Prize series, let ua now look a t a stamp (Figure 19)issued in 1975 for the two Braggs-W.H. Bragg (1662-1942)and his son, W.L. Bragg (1890-1971)-who formulated Bragg’s law and the Bragg equation (nX = 2dsinB) and who did X-ray crystallography. We also see a stamp (Figure 20) from the 1977 set honoring British Nobel Prize winners. This is a particularly dramatic representation of X-ray crystallography. Albert Einstein’s (1879-1955) ( F i g ures 21-23) mmt famous contribution was certainly the matter-energy equivalence, E = me*. Of course, Einstein also developed theories of Brownian motion, the “structure” of light (photons), and relativity. His Nobel Prize, however, was awarded for the law of the photoelectric effect. The photomultiplier tube is today the most common device used for the detection of light in spectroscopic instruments. C.W. Eliott (1834-1926). shown on an early US.stamp (Figure 24) that is part of a series honoring American educators, was a professor of analytical chemistry and coauthor of a very popular manual on qualitative and quantitative analysis. One of the few “real” analytical chemists noted here, he was the only student allowed to study individually with Josiah P. Cooke a t Harvard. Fritz Haber (1868-1934)(Figure 25) is famous for synthesizing ammonia; the method carries h i name. He also discovered the chemical properties of thii glass membranes, and 20 years later they were fabricated into pH electrodes. Haber ala0 appears on a stamp in the Swediih Nobel Prize series (issued in 1978).
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G.R. Kirchoff (1824-1887) (Figures 26-27) did much research in electricity, and it could be argued that this contribution to electrochemistry justifies his inclusion here, but he also studied and explained the Fraunhofer lines (the absorption spectrum of sunlight). In 1860 Kirchoff and Bunsen published fundamental work on spectroscopic analysis using the Bunsen burner, and this led to atomic emission, absorption, and atomic fluorescence spectroscopies. The Fraunhofer D lines in the solar spectrum are due to sodium, the A and B lines are due to potassium, etc. Kirchoff and Bunsen went on to construct the first spectroscope. To my knowledge, Bunsen has not been honored with a postage stamp, a glaring omission. Since we’ve been discussing spectroscopy here, I should mention the Spanish issue for the 15th Colloquium Spectroscopicum Internationale held in Madrid in 1969 (Figure 28), a simple design that readily conveys its message-and a fine way to publicize a spectroscopy conference. The next stamps (Figures 29-30), are from Hungary, part of a set that honored the 100th anniversary of the introduction of the metric system to Hungary (1876-1976). The first stamp (Figure 29) shows Istvan Krusper, a physicist, and a vacuum balance with a 1-kg standard weight. The second stamp (Figure 30) of that series is also interesting in that it shows a laser and a Fabry-Perot interferometer. Lasers are an invaluable spectroscopic light source currently used, for example, in Fourier transform infrared and Raman spectroscopies. The FabryPerot interferometer is also used in some spectroscopic applications. The next stamp (Figure 31) depicts Justus von Liebig (1803-1873), a wellknown chemist of the 19th century and an outstanding educator. His analytical contributions include carbonhydrogen analysis by combustion, with evolved COZ trapped in KOH and moisture trapped in calcium chloride. These techniques are used to this day without major change. Many of his students were also major analytical contributors, for example, J. Volhard (1834-1 910). Now we go back to the British Nobel Prize set and examine the stamp (Figure 32) honoring the Nobel Prize of A.J.P. Martin (b. 1910) and R.L.M. Synge (b. 1914) for chromatography. You see a thin-layer chromatography plate and a chromatogram. In 1941 Martin and Synge separated amino acids by countercurrent extraction. Due to the mechanical difficulties of that technique they began to 784A
work in liquid-liquid chromatography and partition chromatography, which led to modern gas-liquid and highperformance liquid chromatography. Their Nobel Prize was awarded in 1952, so it will be quite awhile before the Swedish stamp is issued. The Swedish Nobel Prize issue shown in Figure 33 honors Albert A. Michelson (1852-1931), who is famous for determining the speed of light, and who, in so doing, invented what is now called the Michelson interferometer, used today in hundreds of Fourier transform infrared spectrometers. E. Millon (1812-1867), shown on an Algerian stamp (Figure 34), is remembered for the Millon reaction to detect proteins. It is a colorimetric test in which the sample is reacted with mercurous nitrate in a mixture of nitric and nitrous acids, giving a red color to indicate the presence of tyrosine amino acid residues in a protein sample. H.W. Nernst (1864-1941) (Figures 35-36) was a famous physical chemist who, a t the turn of this century, developed many methods for measuring dielectric constants and pH. He suggested the use of buffers and was the first to advocate the use of the hydrogen electrode as the standard reference electrode. He pioneered in electrochemistry and also made considerable contributions to thermodynamics. Nernst invented an electric lamp that used a glower of zirconium oxide and became a very useful light source; you can probably find one in your lab’s infrared spectrometer. Until the carbon filament lamp supplanted it, the Nernst glower was useful in other areas as well. Notice the drawing on the Swedish stamp (Figure 36), which appears to be a Nernst glower. Fritz Pregl (1869-1930) (Figure 37) was the founder of quantitative organic microchemistry. He developed microelemental analysis for carbon, hydrogen, nitrogen, sulfur, the halogens, and methoxy and carboxyl groups. He published the classic text, “Die Quantitative Organische Microanalyse” in 1917, essentially founding the field. Many of his methods are still in use. He received the Nobel Prize in 1923. Our next stamp (Figure 38) shows C.V. Raman (1888-1970), who discovered, by visual observation, that there is a change in wavelength that accompanies the scattering of light. This, of course, is Raman spectroscopy,which became popular about 20 years after his initial discovery when more sensitive detectors could pick up the very low levels of scattered light. The field developed even more rapidly when lasers were introduced as light sources.
ANALYTICAL CHEMISTRY, VOL. 54, NO. 7, JUNE 1982
Notice the little spectrum that is part of the stamp’s design. T.W. Richards (1868-1928) (Figure 39), who received the Nobel Prize in 1914, was not an analytical chemist by training, but since his experimental work was on the accurate determination of atomic weights, he had to develop good analytical techniques. For example, he worked on rlephelometry for the determination of the end point of silver halide titrations. Interestingly enough, Richards is the academic forefather of some of today’s top analytical chemists such as J.D. Winefordner, H.V. Malmstadt, J.P. Walters, and W. Blaedel ( 4 ) . Next let’s examine some stamps (Figures 40-44), three of them from the Swedish Nobel Prize series (Figures 40-42), honoring W.K. Rontgen (1845-1923), the discoverer of X-rays. X-rays find analytical use in X-ray diffraction, X-ray crystallography, and X-ray fluorescence spectroscopy. The next stamps (Figures 45-49) honor Nikola Tesla (1856-1943), whose primary contributions were in the field of ac electricity, e.g., induction motors. His analytical-type contributions come via the Tesla coil, used to initiate inductively coupled plasmas, one of today’s prominent optical emission spectroscopy sources, and through basic study of plasmas and ac discharges such as in arc and spark source emission spectroscopy. Figure 50 shows a Hungarian stamp honoring Karoly Than (1834-1904), who made major contributions to volumetric analysis (titrations). He suggested the use of potassium biiodate to standardize sodium thiosulfate solution in iodimetry. Until that time, elemental iodine was used as the standard. He was also responsible for the use of potassium bicarbonate as a standard for acid-base titrations. Louis J. Thenard (1777-1857) (Figure 51) made contributions in the area of organic analysis, Le., elemental microanalysis techniques. He used potassium perchlorate as an oxidizing agent for these analyses. He made improvements to the conventional apparatus used for elemental analysis. His coworker, Gay-Lussac, is also remembered on postage stamps, but these are not included here. Thenard’s teacher, Louis N. Vauquelin (1763-1829) (Figure 52), was a pioneer in the production of analytically pure chemicals. He was the discoverer of beryllium and chromium and worked on the analysis of all sorts of minerals as well as publishing a text on the analysis of noble metals. While we’re talking about inorganic analyses, look at a very recent issue (Figure 53) from Christmas
Island, part of a set that honors the phosphate mining industry. It is perhaps the only stamp that actually says “analysis” on it. (Observe the auto analyzer toward the rear of the illustration.) Now we’re getting close to the end of the alphabet, and we have a series of stamps (Figures 54-58) honoring Alessandro Volta (1745-1827), the inventor of the electric hattery. His hattery was the first device that could provide currents large enough for electrolysis experiments. That is fundamental to the whole field of electrochemistry. There is another stamp (not shown), part of the same set as Figure 58, that depicts a voltaic cell. During his career, Harvey W. Wiley (1844-1930) (Figure 59) was a fanner, soldier, teacher, author, physician, administrator, politician, and analytical chemist. He is honored philatelically for his successful efforts to get the Pure Food & Drug Act passed in 1906 and for having served as first director of the Food and Drug Administration (FDA), part of the Department of Agriculture a t the time. Wiley also wrote “Principles & Practice of Agricultural Analysis,” then considered the best English language treatise on such methods. Pieter Zeeman (1965-1943) (Figure 60) discovered the “Zeeman Effect,” the splitting of atomic emission lines by a magnetic field. The Zeeman effect is now used in several commercial atomic absorption spectrometers for background correction. In addition, since the Zeeman effect demonstrated that electrons possess spin, one might argue that the development of electron spin resonance (ESR)and even of nuclear magnetic resonance (NMR) spectroscopies was aided by Zeeman’s work. Carl Zeiss (1816-1888) is the last scientist included in this discussion. His invaluable contributions to microscopy and optics are remembered on a set from the German Democratic Republic (Figures 61-63). Zeiss, the Zeiss works in Jena, and his student and later partner, Ernst Ahhe (18401905),are dl honored. That microscopy is an important analytical technique is sometimes forgotten, since it is rarely covered in our university courses, but one need only look to Walter McCrone and his associates for proof of the value of analytical micrwcopy. (If you are still not convinced that X i s made contributions to analytical chemistry, consider that the Zeiss Company sold some fine ultraviolet-visible spectrometers.) Finally, we conclude this discussion with three microscopes on stamps, Figures 64-66.
One shows an electron microscope, Figure 66, which becomes truly analytical if it is a scanning electron microscope with an X-ray emission detector option for elemental determination. (If you are interested in microscopes on stamps, I refer you to References 1and 2.) I hope this discussion of analytical chemistry on stamps has intrigued you and that you will begin studying and collecting stamps. It is a fine way to combine a hobby with our profession.
ComDuter Enhaked Spectroscopi. An international journal of instrumental methods, tech. niques and developments in all fields of computer-related spectroscopy and chromatography/ spectroscopy. EDITORS
References (1) J.G. Delly, Microscope, 24,279 (1976). ( 2 ) J.G. Delly, Microscope, 26,97 (1978). (3) Philotelio Chimica,published,hy the Chemistry on Stamps Study Unit of the American Topical Assoelahon (3306N. 50th St., Milwaukee,Wis. 53216). (4) G.D. Boutilier and A.H. Ullman, Ed. Chem.,17,108(1980).
UK and Rest of World: Or. H A . Willir (IC1 Ltd., Petrochemicals and Plastin Divisionl. Editorial Office: Computer Enhanced Spctrorcopy. Spectrum House. Hillview Gardens. London NW4 2JQ. England.
AddHionai Reading (1) R.P. Graham, Talanta, IS. 1157-61
(1971). (2) I.F. Finlsy, Chem.Ind. (London). 14. 56263 (1972). (3) I. McKinley, Chem.Br., 13,51 (1977). (4) D.A. Armitage, Chem.Br., 13,29%303
USA: Dr. Georga Lwy, Syracuse University, Dept. of Chemistry, Bowne Hail, New York. PiY 13210, USA. Supponed by an internsrional advirow board.
(1977).
(5) R.W.Truman, Ed. Chem.,15.5345 (1978). ( 6 ) F. Armitage, Eur. Spectrosc. News, 21, 53 (1978)(one of a series of regularly appearing columns).
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~Alan Ullman is an analytical chemist in the Industrial Chemicals Division of The Procter & Gamble Company. He received his PhD from the University of Delaware in 1977. His research interests include the determination of trace levels of metals, biological effects andspeciation oftrace metals, atomic spectroscopy, mass spectroscopy, and the use of enzymes as analytical reagents. Obviously, one of his hobbies isphilately.
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