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Bull. Hist. Chem. 13 —ll t Ch 13 - 14 (199-93 7 References and Notes THE HISTORICAL DEVELOPMENT OF THE VAN ARKEL BOND-TYPE TRIANGLE Acknowledgment: h prnpl dnttn nd ttn fr th papr b fnd n th thr 197 Unvrt f nnlvn William B. Jensen, University of Cincinnati dtrl drttn "h Cht Crd h f n Indtrl Sn n Md Ar 197-19" Onl drt As the biographical sketch by James Bohning in this issue of qttn nd n trl r rfrnd bl the Bulletin reveals, one of the key events in Ted Benfey's 1 W n American Chemical Industry: A History, 6 l career was his association with Larry Strong at Earlham D. n trnd Yr Y 195-195 l p 19 College and their mutual involvement in the development of 2. n The Role of Chemists in Research on War Gases the Chemical Bond Approach (CBA) course in the late 1950s in the United States during World War I, h rttn Unvr- and early 1960s (1). CBA was undoubtedly the most innova- st f Wnn Mdn WI 199 p 1 S l br tive of the many attempts at curriculum reform in chemistry The Poisonous Cloud, Oxfrd Unvrt r Oxfrd 19 which appeared during this period in the United States and 3 " Wr G Cntrvr" Yr 7 n 191 p 1 elsewhere, and was constructed, as its name implied, around 4. Mltrztn l hd ntv fft n htr pbl the development of self-consistent models of the chemical prtlrl th rrd t hl rfr S H. R. bond, starting from a fundamental knowledge of the laws of Slttn "n Chtr r Sntf rbr? Arn electrostatics (2). By the end of Chapter 13, the CBA textbook, pn t Wrld Wr I n G 1915-193" J. Amer. Hist., Chemical Systems, had led students through a presentation of 1990, 77 7-9 the three basic models used to describe the bonding in covalent, 5 Strh nd A hr "Chtr nd bl metallic, and ionic materials, and had paused for a reflective l" Chem. Eng. News, 1987, 9 March, 19-9 Sln nd K overview of what had been accomplished up to that point. The M A Century of Chemistry: The Role of Chemists and the finale of this bonding retrospective was a brief discussion of American Chemical Society, ACS Whntn C 197 pp the possibility of intermediate bond-types using the simple - 3-3 triangular diagram shown in figure 1 (3): 6. Edr h Sth t Chrl rt 1 Aprl 193 Chrl l rt pr Wdrff brr Er Unvrt bx 3 Cvlnt tll nd n bnd prv t b fl f fldr rrdn th trtr f n btn h thr tp f 7 Sln nd rfrn 5 pp 1-17 bnd blz thr dffrnt rrnnt f t t v 8. ACS Proceedings, M 191 p 7 trtr hrtrt f prtlr btn h ndrln 9 W A r A Victorian in the Twentieth Century: prnpl fr th thr tp f bnd hvr r bd n Memoirs of W. Albert Noyes, pt f Chtr Unvrt f ltrtt n h tp Eh btn rprnt t f l x t Atn Atn 197 p 3 (p n Edr h Sth nr ntnt th th lttn pd b th l xln Clltn Unvrt f nnlvn rphl nt n W prnpl nd trl rltn f th ltrn nd nl hh A b fnd n American Philosophical Society, Year r r fndntl nt f trtr thn r t Book 1941, 397-1; W Ml d American Chemists and Wth th ndrln prnpl n t ll trtr t Chemical Engineers; J. A Chem. Soc., 1944, 15-15; nt rprn tht nt ll btn n b ntl lfd nt n National Academy of Sciences, Biographical Memoirs, l 7 pp f thr pbl tp h ttn n b blzd b trnl 179- dr [ fr] h vrt f th trnl rprntbnd tp 1W A "Ar rt" J. Ind. Eng. Chem., 1922, 14, hrtrt f th thr xtr bnd tp Aln h d f th 117-1171; nd W Wl "Ar rt" ibid., 1923, 15, 7- trnl r rprntd bnd tp hrtrt f th n b- 428. tn hh d nt hv xtr bnd tp 11. [M. C Whtr] "Anthr Grt vr" ibid., 1915, 7 7 Covalent 1 h "Chtr n pl h Erl Yr f th Chl Exptn" Today's Chemist, 1990, 3(April), - David J. Rhees is Executive Director of The Bakken Library and Museum of Electricity in Life, 3537 Zenith Ave. S., Min- neapolis, MN 55416. He is completing a book entitled "The Chemists' Crusade: The Popularization of Chemistry in Metallic Ionic America, 1900-1940." r 1 h CA nd-p rnl 48 ll t Ch 13 - 4 (199-93 The use of simple, incisive diagrams, like figure 1, lies at the spread enthusiasm and predictions of an impending chemical core of effective teaching. Yet, with the exception of the revolution (5). In the United States, it led to the development periodic table, most diagrams of this sort appear without of a polar theory of organic reactivity in the hands of such acknowledgment in the average chemistry textbook. Their chemists as Harry Shipley Fry (1908), K. George Falk and John effectiveness rapidly converts them into community property M. Nelson (1909), William A. Noyes (1909), and Julius and, like the inventors of controlled fire, the wheel, and Stieglitz. In Germany, Richard Abegg (1904) successfully metallurgy, their originators appear to be condemned to per- connected it with the periodic table, and in 1916 both the petual anonymity. Given Ted Benfey's interests in both American chemist, Gilbert Newton Lewis, and the German chemical education and the history of chemistry, I thought it physicist, Walther Kossel, reinterpreted it in tr of Ruther- might not be improper to honor him by rescuing figure 1 from ford's 1911 nuclear atom model (6). its "ahistorical" fate, both by tracing its early history and by Quantitative calculations of heats of reaction using the reviewing some recent extensions of the diagram which have model were made as early 1894 by Richarz and again in 1895 been made since its appearance in the pages of the CBA by Hermann Ebert (7). It was successfully applied to the textbook nearly three decades ago. calculation of crystal lattice energies by Max Born and Alfred Landé in the years 1918-1919 (8) and to the calculation of the h hr-ld W energies of coordination complexes by Kossel, A. Magnus, Gustav F. Hüttig, F. J. Garrick and others in the late teens and A necessary prerequisite to the development of any diagram 1920s (9). Further refinements and applications were made by purporting to represent the gradual transition between the three 'Casimir Fajans, Hans Georg Grimm, and Victor Moritz idealized limiting-cases of ionic, covalent, and metallic bond- Goldschmidt in the 1920s, culminating in the publication in ing is, of course, an explicit recognition of the existence of the 1929 of the monograph Chemische Binding als Electrostatisch three limiting-case bond types themselves. The first to receive Verschijnsel (Chemical Bonding as an Electrostatic Phenome- this recognition was the ionic bond, whose essentials were non) by the Dutch chemists, Anton Eduard van Arkel and Jan imperfectly anticipated by the German physicist, Hermann Hendrick de Boer (10). von Helmholtz, in his famous Faraday Lecture of 1881 (4). Nonpolar or electron-sharing models of the chemical bond Arguing that Faraday's laws of electrolysis implied that elec- date back to the first decade of the 20th century and the tricity itself was particulate in nature, Helmholtz opted for the proposals of the German physicist, Johannes Stark (1908), and two-fluid theory of electricity n which particles of matter the German chemist, Hugo Kauffmann (1908). Related mod- could combine with mobile particles of both positive and els were also suggested by J. J. Thomson (1907), William negative electricity. Neutral atoms contained equal numbers of Ramsay (1908), Niels Bohr (1913), Alfred Parsons (1915) and negative and positive electrical particles, whereas positive and others (6). However, the overwhelming success of the ionic negative ions contained an excess of the corresponding electri- model and its rapid quantification tended to eclipse these cal particle. Helmholtz further identified the number of excess electron-sharing models to such an extent that in 1913 G. N. electrical particles with the valence of the resulting ion, thus, Lewis felt compelled to write a paper arguing that not only in effect, postulating that all chemical combination was the were the physical properties of typical organic compounds result of the electrostatic attraction of oppositely charged ions, incompatible with the ionic model, they also strongly sug- and showed that this model was capable of accounting for the gested the necessity of a second "nonpolar" bonding mecha- magnitude of the energy release observed in typical chemical nism (11). A successful candidate for this nonpolar mecha- reactions. nism was finally provided by Lewis himself in his famous 1916 With the exception of the British physicist, Sir Oliver paper on the electron-pair bond (12). This received wide- Lodge, few physicists, and even fewer chemists, paid attention spread attention as a result of its extension and popularization to Helmholtz's suggestions until they were revived by by Irving Langmuir in the period 1919-1921 (Langmuir also Thomson in conjunction with his ill-fated plum-pudding model introduced the term "covalent bond" in place of Lewis' more of the atom in the period between 1904 and 1907 nd rntr- cumbersome electron-pair bond) and with the publication in prtd n terms of a one-fluid model of electricity in which 1923 of Lewis' classic monograph, Valence and the Structure ionic charge was due to an excess or deficiency of a single of Atoms and Molecules (13).
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