Augustus Matthiessen and His Contributions to ... - ACS Publications

Article pubs.acs.org/jchemeduc

Augustus Matthiessen and His Contributions to Chemistry Simón Reif-Acherman* School of Chemical Engineering, Universidad del Valle, A. A. 25360 Cali, Colombia ABSTRACT: The British scientist Augustus Matthiessen (1831−1870) is widely known for his investigations on the influence of temperature on the electric conductivity of metals and alloys. However, his contributions to other areas of science throughout his career are not widely acknowledged. His research on the electrolytic decomposition of metallic salts resulted in the isolation of pure alkali and alkaline earth metalsincluding calcium, magnesium, strontium, and lithiumas well as the identification of some of their properties. His studies on the definitive composition and formulas of a group of alkaloids and the products resulting from their decomposition contributed to the establishment and definition of a general and consistent system of nomenclature for organic compounds in the 19th century. KEYWORDS: General Public, Second-Year Undergraduate, History/Philosophy, Organic Chemistry, Electrochemistry, Metals

■

alkaline-earth metals were not known as “elements” at that time, and only two common compounds, calcium oxide and magnesium oxide, were called “alkaline earths” because of their insolubility in water. Electrolysis had been introduced as a new field of chemistry by the British scientist Humphrey Davy (1778−1829) at the beginning of the century. His success in decomposing water into gaseous hydrogen and oxygen led him not only to obtain potassium by decomposing a slightly moistened piece of potash by passing an electrical flow through it but also to observe that a similar basic procedure that yielded sodium from soda ash required stronger electric currents. The migration of salts that Davy observed during electrolysis in an experimental apparatus equipped with an early voltaic battery resulted in the decomposition of compounds by electricity and led him to assume that the force of combination, or chemical affinity, was an electrical property of the constituent particles of matter.7 Decades later, Bunsen was involved in electrolytic research. Bunsen used a carbon electrode instead of the expensive platinum electrode utilized in Grove’s battery, which facilitated his research in this field and resulted in his first paper on the electrolytic preparation of alkaline-earth metals, which was published in 1854.8 Matthiessen continued Bunsen’s investigation on the preparation and physical properties of alkali and alkaline-earth metals. This work has been considered as one of the best known investigations conducted by Bunsen and his pupils.9 Calcium was Bunsen’s and Matthiessen’s first interest. Davy was inspired by his own effective isolation of sodium and potassium and attempted, with some success, the same with calcium through the decomposition via electric current of either lime in the presence of mercury or a mixture of wet lime and mercury oxide.10 The resulting product later proved to be not the pure metal but a calcium amalgam. Mercury removal was so difficult a task that Davy himself was doubtful as to whether the recovered compound was pure calcium. In addition to the isolation of calcium and the study of procedures, Matthiessen’s first publication on the subject included a confirmation of Bunsen’s statement regarding the action of the electric current

FORMATIVE YEARS Augustus Matthiessen was born in London on January 2, 1831. He suffered a paralytic seizure when he was a child of two or three years of age that resulted in permanent and severe twitching in his right-hand.1−3 In early adulthood, he traveled to Giessen to obtain instruction in experimental chemistry under the direction of Justus Liebig (1803−1873) and began his studies on April 24, 1852.4 By successfully incorporating teaching and research, Matthiessen began to understand the importance of precision and rigorous quantification in scientific work. With professors such as Johann Heinrich Buff (1805− 1878) and Heinrich Will (1812−1890) in physics and chemistry, respectively, Matthiessen began to understand there the importance of precision and rigorous quantification in scientific work. After graduating on June 18, 1853,5 Matthiessen spent nearly four years at Heidelberg, where he was tutored by Robert Wilhelm Bunsen (1811−1899) and Gustav Robert Kirchhoff (1824−1877). His fellow students at Giessen and Heidelberg included the chemists Henry Roscoe (later Sir) (1833−1915), August Dupré (1835−1907), and Jacob Volhard (1834−1910). Bunsen, with an excellent scientific reputation and a special focus on practical work, and Kirchhoff, who combined exceptional mathematical talent and experimental knowledge, likely had a significant influence on Matthiessen’s scientific activity and molded his work style.

■

ELECTROLYTIC PREPARATION OF ALKALINE-EARTH METALS The most well-known aspect of Matthiessen’s work are his studies on the influence of temperature on the electrical conductivity of metals and alloys in approximately 1861. His earlier contributions to chemistry concerning on the preparation and different properties of certain metals have been often overlooked. However, these contributions, which had begun five years before, were the foundation for the later electrical investigations. His work on both subjects were factors that contributed to his election as a Fellow of the Royal Society in 1861, as shown in the corresponding certificate (Figure 1).6 In the 18th century, any substance not soluble in water and unaffected by heat was called “earth.” The currently recognized © XXXX American Chemical Society and Division of Chemical Education, Inc.

A

DOI: 10.1021/ed5004993 J. Chem. Educ. XXXX, XXX, XXX−XXX

Journal of Chemical Education

Article

Figure 1. Matthiessen’s certificate for election as a Fellow of The Royal Society. (Provided by and reproduced with permission from the Centre for History of Science, Royal Society.)

density employed in the electrolytic decomposition of metallic salts. Although Bunsen successfully electrolyzed calcium chloride moistened with hydrochloric acid,8 Matthiessen was responsible for isolating calcium with optimum purity by electrolyzing a mixture of two equivalents of calcium chloride and one of strontium chloride in the presence of a small quantity of ammonium chloride (Scheme 1).11 The simple isolation apparatus included a carbon positive pole placed in a small porcelain melting pot in which the aforementioned mixture of salts were melted, and a thin

Scheme 1. Chemical Reactions in the Isolation of Calcium

harpsichord wire, dipped just under the surface of the melted salt, that was connected to the zinc of the battery. Color, specific gravity, atomic volume, specific behaviors upon heating, and the place of calcium in the electric series were established by Matthiessen. Although the experimental procedure exhibited a low yield, the purity of the obtained product was not B



Article

silica, and formation of baryta. The behavior of barium when exposed to water and air, as well as the possibility of alloy formation with platinum as a consequence of the electrolytic procedure, were some of the properties of this metal studied by Matthiessen. Lithium completes the list of these new metals investigated in their pure state by Matthiessen using electrolytic methods. Davy17 and Williams Thomas Brande (1788−1866)18 first attempted to isolate lithium from its molten carbonate and oxide through electrolysis and were only partially successful; very small amounts of lithium were obtained. In 1854, Bunsen and Matthiessen were the first to obtain lithium in quantities sufficiently large to allow investigation of its properties. The method included fusing lithium chloride in a porcelain melting pot and subsequently passing a current through the mixture from six carbon−zinc cells connected in series (Scheme 4).19

improved until four decades later by Ferdinand Frederick Henri Moissan (1852−1907).12 By using water as the liquid, which acted on just one of the metals and was then known as the “exciting fluid,” Matthiessen was able to identify that calcium was electropositive to magnesium and electronegative to sodium and potassium. The proof Matthiessen provided to explain why calcium could not be obtained by the reduction of its chloride and the action of these metals at high temperatures indicated that the products obtained with this process by other chemists were not calcium. In addition, this explanation became relevant for understanding related electrochemical procedures. Similar investigations of three new metals were conducted over the next few years. First, Matthiessen described an improved procedure by which strontium pieces weighing half a gram were obtained using a small melting pot with a porous cell containing a mixture of strontium and ammonium chlorides.13 A very fine iron wire wound around a thicker wire and covered with a piece of tobacco-pipe stem served as the negative pole; an iron cylinder placed in the melting pot and around the cell served as the positive pole. The metal was then collected under the crust formed in the cell (Scheme 2).

Scheme 4. Chemical Reactions in the Isolation of Lithium

Scheme 2. Chemical Reactions in the Isolation of Strontium This investigation ended Matthiessen’s activities on the electrolytic preparation of metals and simultaneously initiated the next step in his career in physicsspecifically, investigations of the electrical conductivities and thermoelectric powers of metals. The practical skills Matthiessen obtained while working with Bunsen were critical in his new experimental activities, which were carried out under the direction of Kirchhoff in Heidelberg. The initial stage, from 1856 to 1857, included recently isolated metals20 and was followed by studies of tellurium, bismuth, and antimony, as well as several alloys, later in Matthiessen’s career.21 This successful investigation, which likely contributed to his first recognition by the scientific community, led to his election as a Fellow of the Chemical Society of London on February 18, 1858.22 This marked the culmination of Matthiessen’s cycle abroad and his return to his homeland, where he remained almost uninterruptedly from that point forward.

Additionally, a new preparation of magnesium using a mineral called carnallite (a mixture of potassium and magnesium chlorides, MgCl2·KCl·6H2O) was presented. This method successfully replaced the difficult method originally used by the French chemist Antoine Bussy (1794−1882) to obtain anhydrous magnesium chloride 25 years earlier.14 The anhydrous ore obtained by heating the carnallite in a current of hydrogen chloride was fused with calcium or sodium chloride and later electrolyzed following Bunsen’s methodology using the current of ten zinc−carbon cells for 55 min to yield metallic magnesium.15 Upon decomposition of potassium chloride, the following reactions occurred during electrolysis (Scheme 3):

■

Scheme 3. Chemical Reaction in the Isolation of Magnesium

ALKALOID CHEMISTRY After his return to England, Matthiessen devoted himself to studies in organic chemistry to complement his thorough knowledge of methods in inorganic chemistry and physics, and he worked for a short time at the Royal College of Chemistry, then under the direction of August Wilhelm von Hofmann (1818−1892). Matthiessen’s new mentor, as well as the newly opened field of knowledge, very likely influenced his work, at least initially, in new areas. His initial activities at the Royal College of Chemistry could have gone unnoticed if not for a particular investigation of the chemical action of nitrous acid on aniline. After Hofmann’s isolation of aniline from coal tar in 1845, it became the central subject of investigation at the Royal College.23 One report by the American geologist and chemist Thomas Sterry Hunt (1826−1892) reported phenol, free nitrogen, and water as the products of the aforementioned reaction.24 The short account Matthiessen published about aniline described an intermediate reaction, which was initially determined to result in the formation of ammonia; later, the reaction was applied to ethyl and diethylaniline to produce ethylamine and diethylamine.25 This relatively small study opened a new direction for Matthiessen’s studies on the

The second new metal studied was barium,16 a metal that neither Davy10 nor Bunsen8 was able to isolate from baryta or barium chloride in the presence of mercury, either with or without diluted hydrochloric acid. Davy and Bunsen found similar results: an amalgam, from which barium was obtained as a silver-white residue, when mercury was separated through a distillation process. Matthiessen encountered similar difficulties isolating this metal using electrolytic methods. Although he separated barium as a finely divided powder, he noted that it could not be isolated in a pure state using the same basic isolation procedure previously reported for other metals. Matthiessen stated that the powder did not melt as a result of phenomena at chloride’s fusion temperature, such as the chemical attack of the metal on the pipe-stem and the simultaneous decomposition of small quantities of alumina and C



Article

chemistry of opium bases, particularly narcotine. Matthiessen was initially close to the discovery of the first diazonium compounds, which were first reported and prepared in 1858 by the German organic chemist Johann Peter Griess (1829− 1888)26 by treating aniline and other aromatic amines with nitrous acid.27 These reactions would later become the basis of one of the most important processes in the synthetic dye industry. A number of studies on opiates had been completed by the beginning of the 19th century, largely due to their clinical applications and the necessity of adequately understanding their complex structures in order to develop low-cost processes for their procurement in the greatest-possible purity.28 By the 1850s, approximately 25 alkaloids contained in raw opium had been identified. The properties of narcotine, the second most abundant alkaloid in the poppy, with an approximate average content between 0.7 to 6.4%, prompted further investigation into the compound itself and into the numerous derivatives it was known to yield when subjected to different chemical reagents. Alkaloids were extraordinarily challenging subjects for the emerging practice of quantitative organic analysis, and chemists pursued their analysis to understand the general features of their composition. Although narcotine had been extracted by the French chemist and pharmacist Charles Louis Derosne (1774−1855) in 180329 and its isolation and classification as a vegetable alkaloid had been confirmed by Pierre Jean Robiquet (1780− 1840) 14 years later,30 its constitution and the products derived from it had not been fully elucidated by the middle of the 19th century. Agreement on the relative proportions of its constituents existed; however, independent analyses of narcotine performed by Liebig,31 Dumas and Pelletier,32,33 and Regnault34 resulted in different molecular formulas, primarily because of the group of atomic weights accepted by each scientist. The first adopted formula for narcotine was C46H25NO14, proposed in 1844 by the physician J. Blyth,35 which agreed with the most trustworthy results of previous investigators, such as those of the German chemist Friedrich Wohler (1800−1882).36 In addition, this formula adequately accounted for the formation of the decomposition products known at the time. Later studies conducted by Theodor Wertheim (1820−1864)37 supported the existence of two additional varieties of the compound, C44H23NO14 and C48H27NO14, which would become homologous with that reported by Blyth (i.e., where an atomic weight of C = 6 was used for carbon). A fourth variety, represented by the formula C42H21NO14, was considered in a similar manner by the apothecary F. Hinterberger.38 Therefore, Matthiessen, now working in his private consulting laboratory, began to investigate the chemical nature of narcotine to understand the variety of proposed compositions and to establish the definitive formula, or formulas, associated with the alkaloid. The first stage of the investigation, performed jointly with George Carey Foster (1835−1919),39 established the formula for narcotine that is currently accepted by the chemical community, C22H23NO7.40 The remaining work was devoted to the study and discussion of the chemical reactions that yielded opianic acid (C10H10O5) and cotarnine (C12H15NO4), which result from narcotine oxidation through heating with manganese dioxide and sulfuric acid. The initial chemical reaction involving these three compounds is shown in Scheme 5.

Scheme 5. Opianic Acid and Cotarnine from Narcotine

With respect to opianic acid, Matthiessen and Foster identified its correct formula and properties, including its degradation into meconine (C10H10O4) and hemipinic acid (C10H10O6), which is induced by heating with concentrated potash (Scheme 6). Scheme 6. Meconine and Hemipinic Acid from Opianic Acid

Upon gentle heating of cotarnine with nitric acid, a new compound, cotarnic acid (C10H8O7), was obtained (Scheme 7). In the late 19th century a well-ordered and stable chemical taxonomy did not exist in quantitative organic analysis Scheme 7. Oxidation of Cotarnine

D



Article

Figure 2. Liebig’s combustion assembly, which is similar to that used by Matthiessen; the kaliapparat is shown on the right. Reprinted with permission from Wiley-VCH (ref 42).

procedure in European chemical laboratories by the 1850s and remained in use during the rest of the 19th century, with only minor improvements in the design and heating methods. Furthermore, current methods used in specialized commercial laboratories regarding macrodeterminations are still fundamentally the same as those of Liebig and Dumas.44 Accordingly, and considering Matthiessen’s German educational background, it is likely that Matthiessen also followed these experimental procedures. The graphical structure diagrams in the Schemes 5 to 14, which are presented here for educational purposes, correspond to those known today but were not known until years after Matthiessen’s time of study. The first half of the 19th century was primarily devoted to determining the composition of chemical compounds, especially organic compounds, through formulas rather than chemical structures. Cooke recently stated that “it was not possible using the symbolism of the time to represent them [chemical compounds] such that any significant structural meaning was conveyed, if indeed any clear idea of the structure was known.”45 The development of the concept of valence by the middle of the 19th century, which would not be finalized until the distinction between equivalent, atomic, and molecular weights was established, delayed the use of structural diagrams as a means of representing compounds. Other facts also prevented the use of chemical structures. The lack of uniformity in graphical representations was one of the most important limitations. Drawings based on Dalton’s symbols, atomic symbol notation using circles containing the initial letters of atom names, and different color croquet balls representing atoms with arms representing units of attraction were only some of the different notations used to represent the first graphical chemical structures in the 1850s and 1860s. Bonds between atoms were interchangeably represented by continuous lines, dotted lines, or two lines separated by a dot. Combinations of circles mixed with ring structures were used to represent aromatic compounds. Generic groups to represent radicals, halogens, or metals were not used until approximately 1880, and the three-dimensional nature of structures was not understood until the last two decades of the 19th century. Furthermore, the representation and communication of information within the chemical community was hindered by typographical limitations in printing structural diagrams because of the complexity of the symbols used for early representations of atoms. In most cases, only the reader’s ability allowed him to translate the names and formulas into structures either mentally or on paper. Therefore, patents and volumes of scientific publications in chemistry lacked structural diagrams before 1870, and the chemistry community, which was not accustomed to seeing structures in print, used linear empirical formulas at the close of the century.

compared to the established experimental methods in inorganic chemistry; however, it was slowly evolving. The old, slow, and unreliable methods available at the beginning of the century, which scarcely allowed the separation of mixtures of related substances, involved procedures that often resulted in significant chemical alterations, and which produced misleading results, were replaced decades later by fast, simple, and precise techniques that laid the foundation for elemental organic analyses. A chemist’s glassblowing skills during the early decades of the century stand out, among other factors, as responsible for the creation of the novel glassware that was required for the implementation of new methods and was essential to later organic chemists’ development of constructive syntheses.41 These techniques were mainly introduced by two men, Justus von Liebig (later Baron) (1803−1873) of Germany and Jean-Baptiste-André Dumas (1800−1884) of France, in the 1830s. In Liebig’s standardized method of combustion, a packing of copper oxide was heated, and the sample was slowly vaporized under a current of air or oxygen, which passed through a piece of hollow glassware shaped like a triangle with five bulbs (kaliapparat) that was specially designed for this purpose (Figure 2).42 The gravimetric measurement of carbon and hydrogen was performed by weighing the carbon dioxide and water that resulted from combustion and that were absorbed into a caustic potash solution and calcium chloride, respectively. Volumetric measurement of nitrogen was unsuccessful, despite Liebig’s efforts to improve it. Liebig’s lack of success was likely due to the oxidizing conditions, which ensured the complete conversion of carbon to carbon dioxide during the combustion but which also oxidized the nitrogen. Armed with a good analytical balance, carbon and hydrogen analyses were completed using a 0.5 g sample with an accuracy of 1−2% in approximately 1 h, whereas the volumetric determination of nitrogen was typically accurate to within 10%. Dumas improved nitrogen measurement by substituting the carbon dioxide generated by heating lead carbonate in an extension of the combustion tube for the flow of air and by using an eudiometer tube filled with alkali hydroxide to collect the gases, thus eliminating the need for the separate absorption of carbon dioxide.43 The carbon dioxide flushed out the residual air and was absorbed by the potash with the water vapor from the sample, theoretically leaving the nitrogen unaltered. The determination of the oxygen content, another common element of organic compounds, was another challenge that was solved by calculating the difference after the amounts of other elements had been determined. Matthiessen did not clearly report the experimental procedures he followed to determine the elemental composition of the different compounds. However, historians have concluded that the aforementioned techniques were a common E



Article

methyl nor-meconic acid, or methyl nor-meconine, (C9H8O4), respectively, from the first step, and subsequently nor-opianic acid and nor-meconine (Schemes 11 and 12).48 The use of the prefix “nor” by Matthiessen and Foster for these new products is the first reported example of its use in organic chemistry nomenclature to identify demethylated compounds. This rule in nomenclature was later generalized to denote the replacement of one or more methyl groups by a hydrogen or the removal of an ethyl group from a carbon chain.49 Later studies conducted jointly by Matthiessen and his new assistant, Charles Romley Alder Wright (1844−1894),50 examined the action of concentrated hydrochloric acid on two alkaloids: morphine (Scheme 13) and codeine (Scheme 14). These studies led to the discovery of apomorphine (C17H17O2N), an agent that, although differing from morphine by only one equivalent of water, exhibited substantial differences from it. Apomorphine quickly became one of the most powerful and valuable emetics available and a valuable adjunct in medical practice.51 Simultaneously, Matthiessen and Wright reported the production of apomorphine from codeine in two steps. First, a derivate they called chlorocodide was formed, which decomposed into methyl chloride and apomorphine upon heating with hydrochloric acid at 150 °C.52 Wright continued to work on this topic in the four years following Matthiessen’s death and published nine additional reports on the derivatives of these alkaloids.

Matthiessen’s investigations between 1860 and 1862 yielded hypogallic acid (C7H6O4) (Scheme 8) and methylhypogallic acid (C8H8O4) (Scheme 9) via the reaction of hemipinic acid with hydroiodic acid or hydrochloric acid, respectively.46 Scheme 8. Hypogallic Acid from Hemipinic Acid

Scheme 9. Methylhypogallic Acid from Hemipinic Acid

Five years later, Matthiessen and Foster focused their investigations on the combined action of heating and an excess of concentrated hydrochloric or hydroiodic acid on narcotine, opianic acid, and meconine. Different homologous compounds were prepared by the successive elimination of one, two, or three methyl groups from the original compound.47,48 The following sequence of reactions (Scheme 10) summarizes the process (for the case of hydrochloric acid) using the established chemical structures. The heating of opianic acid or meconine, separately, at 100 or 110 °C with concentrated hydrochloric or hydroiodic acid yielded two new acids, methyl nor-opianic acid (C9H8O5) and

■

CHEMISTRY AND THE ESTABLISHMENT OF ELECTRICAL RESISTANCE STANDARDS Two other notable chemical studies by Matthiessen include his theory concerning the chemical nature of alloys and his preparation of specific metals of high purity. Matthiessen’s interest in alloys emerged as a result of two personal circumstances: first, his investigations into both the electrical

Scheme 10. Demethylation of Narcotine

F



Article

Scheme 11. Demethylation of Opianic Acid

Scheme 12. Demethylation of Meconine

observed among several published measurements for the magnitude of copper’s electrical conductivity were due to the presence of minute quantities of other elements. A full report on this subject was presented in 1860 to the Committee appointed by Government to investigate the construction of submarine telegraph cables; this report was later published in a scientific journal.56 From a theoretical perspective, Matthiessen’s most important conclusions were directly associated with the chemical nature of alloys. In addition to identifying remarkable differences in the behavior of alloys of some metals, such as lead, tin, zinc, and cadmium, compared with others, Matthiessen posed two important and general considerations.57 The first consideration implied that the presence of small amounts of impurities in a metal was responsible for significant changes in the metal’s physical properties as well as in its allotropic state. The second consideration addressed the chemical nature of alloys and established that they could be either mixtures of chemical substances with an excess of one metal or solutions of a particular alloy with an excess of one of the metals, which form, in their solid condition, what Matthiessen termed a “solidified solution.” This latter consideration became a useful theory that led to numerous developments related to alloys. Between 1864 and 1869, Matthiessen was the Head of a Committee sponsored by the British Association for the Advancement of Science to study the true chemical nature of pure cast-iron and the influence of commonly associated elements on its physical properties. The committee included Frederick Augustus Abel (later Sir) (1827−1902) and David Forbes (1828−1876) and, with the assistance of S. PrusSzczepanowski, evaluated different techniques to prepare cast iron and obtained nearly pure iron (free from silicon, calcium, and phosphorus, and with only a trace of sulfur) from ferrous sulfate.58 Matthiessen’s work on the physical and electrical properties of metals and alloys earned him the Royal Medal from the Royal Society in 1869, which identified this work as one of “the two most important contributions to the advancement of natural knowledge” in chemistry. Shortly thereafter, Matthiessen committed suicide by poisoning himself on October 6, 1870 with prussic acid while under severe nervous strain, thus ending his short scientific career.

Scheme 13. Apomorphine from Morphine

Scheme 14. Apomorphine from Codeine

conductivities of materials and the influence of other compounds on the magnitude of the conductivity of pure metals,53 and second, the preference he had for using alloys over pure metals because of the optimal physical properties of certain alloys54 Some alloys were being used successfully at the time, and Matthiessen understood that the limited information available about their behavior needed to be expanded. As a result, over a period of several years, he reported specific properties, such as the specific gravity, thermal expansion, electrical conductivity, and chemical activity, for both pure metals and alloys.55 The first reports concerned copper, likely because of the necessity of its purity for conducting electricity and the importance of its use as wires in telegraphy and related applications. Matthiessen concluded that the discrepancies G



■

Article

(10) Davy, H. Electrochemical researches on the decomposition of the earths; with observations on the metals obtained from the alkaline earths, and on the amalgam procured from ammonia. Philos. Mag. 1808, 32, 193−223. (11) Matthiessen, A. Electrolytische darstellung der metalle der alkalien und erden. Justus Liebigs Ann. Chem. 1855, 93, 277−286. (12) Moissan, H. Recherches sur le calcium et ses composes. Ann. Chim. Phys. 1899, 18, 289−343. (13) Matthiessen, A. On the preparation of strontium and magnesium. Q. J. Chem. Soc. 1856, 8, 107−108. (14) Bussy, A. A. B. Mémoire sur le radical métallique de la magnésie. Ann. Chim. Phys. 1831, 46, 434−437. (15) Bunsen, R. W. Darstellung des magnesiums auf electrolytischem. Justus Liebigs Ann. Chem. 1852, 82, 137−145. (16) Matthiessen, A. A few notes on barium. Q. J. Chem. Soc. 1856, 8, 294−296. (17) Anonymous. An account of the new alkali lately discovered in Sweden. Q. J. Sci., Lit., Arts 1818, 5, 337−340. (18) Webster, J. W. A manual of chemistry, on the basis of professor Brande’s, 2nd ed.; Richardson and Lord: Boston, 1828; pp 286−287. (19) Bunsen, R. W. Darstellung des lithiums. Justus Liebigs Ann. Chem. 1855, 94, 107−111. Bunsen, R. W.; Matthiessen, A. Préparation du lithium. J. Pharm. Chim. 1855, 28, 155−157. (20) Matthiessen, A. Preliminary notice on the electric conducting power of the alkaline metals. Philos. Mag. 1856, 12, 199; On the electric conducting power of the metals of the alkalies and alkaline earths. 1856, 13, 81−90. (21) Kirchhoff, G. R. Ueber die leitungsfähigkeit für elektricität von kalium, natrium, lithium, magnesium, calcium und strontium. Ann. Phys. (Berlin, Ger.) 1857, 100, 177−194. Matthiessen, A.; Kirchhoff, G. R. Ueber die thermo-elektrische spannungsreihe. Ann. Phys. (Berlin, Ger.) 1858, 103, 412−428. (22) Anonymous. Proceedings at the Meetings of the Chemical Society. Q. J. Chem. Soc. 1859, 11, 52. (23) Hofmann, A. W. Researches on the volatile organic bases. Q. J. Chem. Soc. 1849, 1, 317; Researches on the volatile organic bases. 1850, 2, 300−335. (24) Hunt, T. S. On the decomposition of aniline by nitrous acid. Am. J. Sci. Arts 1849, 8, 372−375. (25) Matthiessen, A. On the action of nitrous acid on aniline. Proc. R. Soc. London 1857−1859, 9, 118−119. On the action of nitric acid and of bioxide of manganese and sulphuric acid on the organic bases. 635− 638. (26) Heines, S. V. Peter Griess − Discoverer of diazo compounds. J. Chem. Educ. 1958, 35, 187−191. (27) Griess, P. Vorläufige notiz über die einwirkung von salpetriger säure auf amidinitro− und aminitrophenylsäure. Justus Liebigs Ann. Chem. 1858, 106, 123−125. (28) Morson, A. Operative chymist; Rodopi: Amsterdam, 1997; pp 83−84, 111. (29) Derosne, Ch. L. Mémoire sur l’opium. Ann. Chim. Phys. 1803, 45, 257−285. (30) Robiquet, J. P. Observations sur le Mémoire de M. Sertuerner, relatif à l’analyse de l’opium. Ann. Chim. Phys. 1817, 5, 275−288. (31) Liebig, J. Ueber die zusammensetzung des narcotins und piperins. Ann. Pharm. (Lemgo, Ger.) 1833, 6, 35−37. (32) Dumas, J.-B. A.; Pelletier, P.-J. Recherches sur la composition élémentaire et sur quelques propriétés caractéristiques des bases salifiables organiques. Ann. Chim. Phys. 1823, 24, 163−191. (33) Pelletier, P.-J. Nouvelles recherchés sur l’opium. Ann. Chim. Phys. 1832, 50, 240−261, 262−280. (34) Regnault, H. V. Nouvelles recherches sur la composition des alcalis organiques. Ann. Chim. Phys. 1838, 68, 113−160. ReifAcherman, S. The contributions of Henri Victor Regnault in the context of organic chemistry of the first half of the nineteenth century. Quim. Nova 2012, 35, 338−343. (35) Blyth, J. On the composition of narcotine, and some of its product of decomposition by the action of bichloride of platinum. Mem. Proc. Chem. Soc. London 1843, 2, 163−179.

CONCLUDING REMARKS Matthiessen has been unjustly ignored by historians of science. He was characterized by perseverance, an acute power of observation, a distinct power of generalization, and a marked degree of manipulative skill, despite his physical limitations. A critical examination into the 28 memoirs he published during the 15 years that compose his scientific career, more than half of them in chemistry, reflects a great fondness for experimental inquiry, an obsession with accuracy, and a sound choice of worthy subjects for study, according to the scientific and technical requirements of his times. In addition, he often utilized the most direct means for investigating these subjects. Although his investigations on the properties of pure metals and alloys had immediate practical applications, his investigations on alkaloids, specifically the studies with Foster, represented a great and definitive advancement of the knowledge regarding these substances. The establishment of unique and definitive formulas for the alkaloids and the products obtained from their decomposition contributed to a coherent nomenclature in organic chemistry and the subsequent resolution of a long scientific dispute on the subject. Additionally, this work facilitated the later successful applications of these substances in numerous physiological and pharmacological investigations.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS I thank Joanna Hopkins, the Picture Curator of the Centre for History of Science at the Royal Society, for kindly authorizing inclusion of Matthiessen’s Certificate of Election as a Fellow of that Institution; Eva-Marie Felschow, from the Archives of the University of Giessen, for historical information about Matthiessen’s time as a student there; and the anonymous reviewers of this paper for their precise and helpful comments and suggestions.

■

REFERENCES

(1) Augustus Matthiessen. J. Chem. Soc. 1871, 24, 615−617. (2) Augustus Matthiessen. Chem. News J. Phys. Sci. 1870, 22, 188−189. (3) Augustus Matthiessen. Nature (London, U.K.) 1870, 2, 517−518. (4) Felschow, E.-M. Justus Liebig University Giessen. Personal communication, 2010. (5) Kössler, F. Verzeichnis der Doktorpromotionen an der Universität Giessen von 1801−1884; Giessen Universitätsbibliothek: Giessen, 1970; p 65. (6) Archives of the Royal Society of London. (7) Davy, H. On some chemical agencies of electricity. Philos. Trans. R. Soc. London 1807, 97, 1−56; On some new phenomena of chemical changes produced by electricity, particularly the decomposition of the fixed alkalies, and the exhibition of the new substances which constitute their bases; and on the general nature of alkaline bodies. 1808, 98, 1−44. (8) Bunsen, R. W. Notiz über elektrolytische gewinnung der erd- und alkalimetalle. Ann. Phys. (Berlin, Ger.) 1854, 92, 648−651. (9) Robert William Bunsen (1811−1899). Proc. R. Soc. London 1904−1905, 75, 46−49. H



Article

(36) Wöhler, F. Untersuchungen über das narcotin und seine zersetzungsproducte. Justus Liebigs Ann. Chem. 1844, 50, 1−28. (37) Wertheim, T. Weitere mittheilungen über das narkotin. J. Prakt. Chem. (Leipzig) 1851, 53, 431−435. (38) Hinterberger, F. Beitrag zur kenntniss der quecksilberverbindungen der alkaloide. J. Prakt. Chem. (Leipzig) 1852, 56, 144−159. (39) George Carey Foster (1835−1919). Proc. R. Soc. London 1920, 96, xv−xviii. (40) Matthiessen, A.; Foster, G. C. Preliminary notice of researches into the chemical constitution of narcotine and of its products of decomposition. Proc. R. Soc. London 1860−1862, 11, 55−61. (41) Jackson, C. M. Analysis and Synthesis in Nineteenth-Century Organic Chemistry. Ph.D. Thesis, The University of London, December 2008. (42) Liebig, J. Ü ber einen neuen Apparat zur Analyse organischer Kö rper, und ü ber die Zusammensetzung einiger organischen Substanzen. Ann. Phys. (Berlin, Ger.) 1831, 21, 1−47 DOI: 10.1002/ andp.18310970102;See also Sur un nouvel appareil pour l’analyse des substances organiques; et sur la composition de quelques-unes de ces substances. Ann. Chim. Phys. 1831, 47, 147−197. (43) Dumas, J.-B.-A. Recherches de chimie organique. Ann. Chim. Phys. 1833, 53, 198−213. (44) Rocke, A. J. Organic analysis in comparative perspective: Liebig, Dumas, and Berzelius, 1811−1837, in Holmes, F. L., Levere, T. H. (eds.), Instruments and experimentation in the history of chemistry; MIT Press: MA, 2000; p 273−310, on 298;. Szabadváry, F. History of Analytical Chemistry; Gordon & Breach: Langhorne, PA, 1992; pp 293, 296;. Ihde, A. J. The development of modern chemistry; Dover: Mineola, NY, 1984; pp 179, 182. A recent replication of Liebig’s experiments confirms the technique’s accuracy regarding carbon and hydrogen; see Usselman, M. C.; Reinhart, C.; Foulser, K. Restaging Liebig: A study in the replication of experiments. Ann. Sci. 2005, 62, 1−55. (45) Cooke, H. A historical study of structures for communication of organic chemistry information prior to 1950. Org. Biomol. Chem. 2004, 2, 3179−3191. (46) Matthiessen, A.; Foster, G. C. Researches into the chemical constitution of narcotine, and of its products of decomposition. Part I. Philos. Trans. R. Soc. London 1863, 153, 345−367. (47) Matthiessen, A. Researches into the chemical constitution of narcotine, and of its products of decomposition. Part III. Philos. Trans. R. Soc. London 1869, 159, 661−665. (48) Matthiessen, A.; Foster, G. C. Researches into the chemical constitution of narcotine, and of its products of decomposition. Part II. Philos. Trans. R. Soc. London. 1867, 157, 657−667. (49) Gaddum, J. H. The prefix “nor” in chemical nomenclature. Nature (London, U. K.) 1956, 177, 1046. Verkade, P. E. A history of the nomenclature of organic chemistry; Delft University Press: Delft, Netherlands, 1985; p 397. (50) Charles Romley Alder Wright. Proc. R. Soc. London 1894−1895, 57, v−vii. (51) Matthiessen, A.; Wright, C. R. A. Researches into the chemical constitution of the opium bases. Part I. On the action of hydrochloric acid on morphia. Proc. R. Soc. London 1868−1869, 17, 455−460. (52) Matthiessen, A.; Wright, C. R. A. Researches into the constitution of the opium bases. Part II. On the action of hydrochloric acid on codeia. Proc. R. Soc. London 1868−1869, 17, 460−462; Researches into the constitution of the opium bases. Part III. On the action of hydrochloric acid on codeia. 1869−1870, 18, 83−88. (53) Matthiessen, A. On the electric conducting power of alloys. Philos. Trans. R. Soc. London 1860, 150, 161−176. (54) Matthiessen, A. On alloys and their uses. Proc. R. Inst. G. B. 1869, 5, 335−338. (55) See, for example: Matthiessen, A. On the electric conducting power of alloys. Philos. Trans. R. Soc. London 1860, 150, 161−176, On the specific gravity of alloys. 177−184; 1866, 156, 861−881; Note on Messrs. Calvert and Johnson’s paper “On the action of acids upon metals and alloys. J. Chem. Soc. 1866, 19, 502−504.

(56) Matthiessen, A.; Holzmann, M. On the effect of the presence of metals and metalloids upon the electric conducting power of pure copper. Philos. Trans. R. Soc. London 1860, 150, 85−92. (57) Matthiessen, A. On alloys. J. Chem. Soc. 1867, 20, 201−220. (58) Matthiessen, A.; Szczepanowski, S. P. Report on the chemical nature of cast iron. Br. Assoc. Adv. Sci., Rep. 1868, 38, 342−343.

I


Augustus Matthiessen and His Contributions to ... - ACS Publications

Recommend Documents