Chemistry for Everyone
Leopold’s Workbench: The Hapsburg-Lorraine Grand Duke and Chemistry Gianfranco Scorrano* Dipartimento di Chimica Organica, Università di Padova, 35131 Padova, Italy;
[email protected] Nicoletta Nicolini Dipartimento di Chimica, Università degli Studi „La Sapienza“, 00185 Roma, Italy Ida Maria Masoner Institut für Organische Chemie, Leopold-Franzens Universität, Innsbruck, Austria.
In our hectic times it is inconceivable to think of one of the rulers of the world, say the president of the United States, doing chemistry in his spare time. Things were different at the end of the 18th century. The Hapsburg-Lorraine Grand Duke Leopold (1747–1792), ruler of Tuscany and later to become Roman Emperor in Austria, was in fact very interested in the so-called nützliche Wissenschaften (useful sciences) to the point where he himself did chemical experiments (1) using a work bench that now stands in the Museum of History of Science in Florence, Italy (Fig. 1). On the bench and in the glass cabinet standing near the workbench, several unlabeled glass bottles and glass jars filled with chemicals, very likely used by the Grand Duke, have been preserved up to this day. We have analyzed and identified these chemicals and we wish to report their identity and their probable use, in the context of a brief overview of Leopold, the Museum of History of Science, and chemistry of the 18th century.
Figure 1. Leopold‘s workbench.
Leopold, Grand Duke of Tuscany 1765–1790 Peter Leopold (2, 3) (Fig. 2) was born in Vienna in 1747. The third son of the Hapsburg queen Maria Theresia and the Lorraine duke Franz Stephan III, better known as the Roman German emperor Franz I, Leopold obtained a good and wide-ranging education in Vienna within his family. In 1765, at the age of 18, he both married and became Grand Duke of Tuscany. He inherited this country from his father, who succeeded the Medici in Florence. Leopold spent most of his life in Tuscany, which he governed for 25 years. When his brother Joseph died in 1790, Leopold left Tuscany for Vienna, where he was crowned Roman-German emperor. He died only two years later at the age of 45. Leopold was one of the most progressive sovereigns of his time: his government in Tuscany was characterized by a large number of reforms and Tuscany served as a political and economic model for other countries. Leopold was an active promoter and patron of the natural sciences. For instance, he supported Felice Fontana (1730–1805) (4) and Giovanni Fabbroni (1752–1822) (5), two eminent natural scientists, and it was Leopold who inaugurated the Royal Museum of Physics and Natural History in Florence. Leopold’s very special interest was chemistry. He did experiments in the laboratory on the ground floor of the Royal Museum of Physics and Natural History, together with Felice Fontana, Giovanni Fabbroni, and Uberto Francesco Hoefer (6 ). Several chemicals of that time have been preserved
Figure 2. Leopold at the time of his rising as the Roman German Emperor.
and are exhibited in the Museum of History of Science in Florence. It is conceivable that at least some of them were prepared by Leopold himself. Museum of History of Science in Florence The Museum of History of Science in Florence (7) dates back to 1763, when Giovanni Targioni Tozzetti (1712–1783) cataloged the scientific instruments that remained from the Medici collection in Florence after the accession to power
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Chemistry for Everyone
of the Lorraines. In connection with the collection a new educational institution was formed. From 1769 on, Fontana took care of the Physical Cabinet. In 1775 Grand Duke Leopold inaugurated the Imperiale e Regio Museo di Fisica e Storia Naturale (Imperial and Royal Museum of Physics and Natural History). The Museum was managed by Fontana and was located in Palazzo Torrigiani in Via Romana, beside Palazzo Pitti. The initial collection was enlarged by new acquisitions, some of which were brought to Florence by Fontana and Fabbroni from their journeys abroad (e.g., optical lenses from London obtained in exchange for thermometers made in Florence). The museum housed physical, botanical, and other natural scientific exhibits. The museum was also dedicated to research and the teaching of scientific matters. The teaching was reorganized in 1859, giving rise to the Istituto di Studi Superiori Pratici e di Perfezionamento (Institute of Practical Advanced Studies and of Specialization) with different sections located in different parts of the town. The Natural Sciences section remained in Palazzo Torregiani. Beginning in 1872 the Institute increasingly acquired an official status, becoming, in 1923, the University of Florence. It was then necessary to separate the museum activity from the teaching and research one, and in 1929, the scientific collections were housed in Palazzo Castellani, close to the River Arno, under the name of The Institute and Museum of History of Science. There both the medicean and the lorennaise collections were saved. The museum was damaged during World War I; it was restored with support from Harvard University, the Rockefeller Foundation, and the Sloan Foundation. Some exhibits were damaged by flooding of the nearby Arno in 1966 and by the bomb attack near the Uffizi in 1993. The Sala di Chimica (Hall of Chemistry) was formerly located on the ground floor in the Museum of Physics and Natural History in Palazzo Torregiani. In Palazzo Castellani the chemical exhibits were again placed on the ground floor. The flood mainly affected them in 1966 and some of the chemicals were destroyed. Since then, the chemical exhibition has been located on the second floor. It contains several chemicals in their authentic vessels placed in a glass cabinet and on a finely worked wooden workbench, which was the workbench of Grand Duke Leopold.
Chemistry in the 18th Century. A Brief Overview The 18th century, especially the second half of it, was a turbulent period of new inventions and new political, economic, and social ideas, of which the revolution in France is the most important outcome. Enormous changes also took place in science. Again, France was the center of the new ideas. The formation of new disciplines was necessary because knowledge was increasing immensely. One of these new disciplines was chemistry (8). It was the end of the 18th century when Antoine Laurent Lavoisier’s (1743–1794) ideas revolutionized this newly forming discipline. It was he who overcame the old phlogiston theory, which was an obstacle to the understanding of the new experimental results. The development of chemistry as an autonomous natural science was the result of many factors: the experiments and experiences in the laboratory became the base of the theory, and the analysis and synthesis of chemical substances became the aim of this science. Not only discovery but also utilization of the discovery was declared to be a main interest of the new discipline. In Florence, Grand Duke Leopold was a passionate chemist and a well-informed contemporary. According to Ugo Schiff (1834–1915), “he ordered the examination of the natural products of Tuscany with the intention to find substances which could be useful for industry and agriculture” (9). The most important research was that of Uberto Francesco Hoefer leading in 1777 to the discovery of boric acid in the lake of Monterotondo. The words at the bottom of the Table of Affinities, also stored in the Museum and attributed to Geoffroy (10)—Non fingendum aut excogitandum sed videndum quid natura ferat aut faciat (not to invent and think out but to see what nature bears and makes)—illustrate well the pragmatic attitude of Leopold and his time. Analysis of the Samples The analyses of the 38 samples were carried out in several laboratories of the University of Padova using several methods: X-ray fluorescence, X-ray diffraction, gas chromatography– mass spectrometry, IR spectroscopy, thermal analysis, and chemical tests. For brevity, Tables 1 and 2 report only the
Table 1. Results for the Liquid Samples No. Identified as 1
Oil of parsley seeds (oleum petroselini seminis, olio di semi di prezzemolo, Petersiliensamenöl)
Identified Compounds α-pinene,a camphene, 1,4-cineole, p-cymene, limonene, fenchyl alcohol, 2-borneol, norpinene-2-carboxaldehyde, α-terpineol, myristicine,a 1-allyl2,3,4,5-tetramethoxybenzene,a apiolb
2
Olio espresso dalle formiche (oil pressed out of ants)
butyric acid, heptane, pentanoic acid, heptanoic acid, palmitic acid, oleic acid GC–MS,1H NMR
3
Ethanol
4 5
31
ethanol a a Oil of a plant of the family Umbelliferae, probably oil α-pinene, camphene, p-cymene, limonene, carvone of caraway (oleum carvi, olio di comino, Kümmelöl)
GC–MS,1H NMR GC–MS
Olio di Dippel (olio animale fetido di Dippel, animal oil, Dippelöl, Thieröl)
dodecane, 1-tridecene, tridecane, 1-tetradecene, tetradecane, 1-pentadecene, GC–MS pentadecane, 1-hexadecene, hexadecane, 2-pentadecanone, heptadecane, octadecane, 2-heptadecanone, nonadecane, 1-eicosene, 3-octodecanone, pentadecylheptanoic ester, pentadecyloctanoic ester, branched pentadecylheptanoic ester, branched pentadecyloctanoic ester, pentadecylnonanoic ester, pentadecyldecanoic ester, branched pentadecylnonanoic ester
Oil of celery fruits (oleum apii graveolentis seminis, olio di semi di sedano, Selleriesamenöl)
limonene,a α-terpineol, carvone, β-selineneb
aTypical
48
Technique GC–MS
compound of this oil. bCharacteristic compound of this oil.
Journal of Chemical Education • Vol. 79 No. 1 January 2002 • JChemEd.chem.wisc.edu
GC–MS
Chemistry for Everyone
The Probable Use of These Compounds
Figure 3. X-ray fluorescence of sample 40 (sodium and oxygen, with some silicon).
Figure 4. X-ray diffraction of sample No. 40 (borax).
identity of the compounds in the numbered bottles. Details are reported in the Diploma thesis of Ida Maria Masoner. Space limitations prevent detailed discussion of all the analyses. We will report, as an example, how we identified sample No. 40. Sample No. 40 is a fine, white homogeneous powder. It is stored in a glass jar on the workbench. Its elemental composition was determined by X-ray fluorescence (Fig. 3): sodium and oxygen (boron cannot be detected by X-ray fluorescence) were found. Additionally some silicon was found. Sodium was also indicated by the yellow color in the flame test. Borate was indicated by the basic character of the sample and by the following specific reaction. A dry sample was treated with methanol and concentrated sulfuric acid in a flat plate. A methyl ester of boric acid forms by the reaction of methanol with borate, catalyzed by concentrated sulfuric acid; the ester burns with a characteristically green flame. This analytical procedure was also used by Hoefer to determine boric acid. Hoefer, Leopold’s court pharmacist, discovered boric acid in Tuscany. Disodium tetraborate pentahydrate Na2B4O7⭈5H2O (mineral name, tincalcoite; trivial name, borace, borax) was then identified by X-ray diffraction (Fig. 4) as sample No. 40. The upper curve was obtained for our sample; the vertical lines indicate the pattern obtained under the same conditions for a pure sample of borax.
The question “what were these compounds used for?” is connected with the question “why were they stored in this collection by Leopold?” To investigate the probable use (11–14), the history, and the importance that each sample might have had to Tuscany and the 18th century, is, in addition to the analyses, a very complex task that would require a detailed knowledge of applied chemistry and the type of chemical manufacturers in Tuscany at that time. We did make use of the Relazioni di Viaggi per la Toscana (Travel Experiences in Tuscany) by Targioni Tozzetti, who, beginning in 1742, spent many years visiting various parts of the region to analyze the resources that could have been of use to the House of Lorraine to build a good industrial, economic, and social policy (15). From our chemical analysis we can say that all the compounds in Leopold’s bench are “local” products. We will discuss, as groups of compounds, some of their probable uses. A remarkably large number, nearly one third of the solid samples, are coloring materials (16 ) (Nos. 8, 16–19, 23, 27, 29, 30, 33, 34, and 37). Leopold’s interest reflects the importance of these coloring matters in the textile industry and in the fabrication of paints in Florence in the 18th century. These samples are colors that have been used since antiquity, such as indigo (No. 19) (17) and cinnabar (No. 30); natural minerals such as malachite (No. 8), or artificially prepared colors. Some of them were new colors of the 18th century—for example, Berlin blue (No. 29) and copper arsenate (No. 16); some of them were paint pigments used on a large scale, such as iron oxides (Nos. 23 and 33). To these samples we may add alum (No. 19), which already in 1745 had attracted the interest of the Regent, Count of Richecourt, so that excavation in the Monterotondo mines was increased in an attempt to get rid of the papal monopoly through the Tolfa’s mine (18). Numbers 13, 14, and 20 are tartaric acid and products of it. They may be connected with studies on wine, which was an important export of Tuscany then as now. Another possibility is that these substances were of medical interest. Numbers 7, 11, 21, and possibly 15 were probably used as medicine. All of them were known for their purgative effect. Sample No. 7, powder of Algarotti, is an antimony compound, as is sample No. 15. Antimony compounds have been applied in medicine since antiquity (19) and antimony minerals are especially found in Tuscany. Myrrh (No. 11) and mercury(I) chloride (No. 21) also have a long history as medicinal substances. The remaining samples are not related to such general topics as colors, wine, and medicine. Each of them has to be seen in its special meaning. Possibly, molybdenum sulfide (No. 32) and graphite (No. 35), which were used in pencils, were connected with the fabrication of pencils in Volterra, Tuscany; this industry was established during Leopold’s time (20). Borax (No. 40) is likely to be associated with Umberto Francesco Hoefer’s contemporary discovery of boric acid (21) in the lakes of Monterotondo in Tuscany. Sample No. 37 is simply earth that may have been taken from a part of Tuscany where Leopold was working on a soil-improvement project (22). Probably sodium chloride (Nos. 24, 26, 36) originated from the salterns near Volterra (23) and was used for crystallization experiments as well as for a material in pharmacy, medicine,
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50
11
copper hydroxy carbonate tripotassium sodium sulfate copper hydroxide chloride
potassium aluminum sulfate dodecahydrate 2,2′-biindolinyliden-3,3′-dion
2,3-dihydroxybutane dioic acid calcium oxalate
—
iron(III) oxide hydrate
sodium chloride
—
dried plant (Rubia tinctorum?)
copper sulfide copper
CuCO3⭈Cu(OH)2 K3Na(SO4)2 Cu2(OH)3Cle
KAl(SO4)2⭈12H2O
C4H4O6 CaC2O4f
Hg2Cl2
—
Fe2O3⭈H2O
NaCl
SiO2 (mixture)g
—
Cu2S Cuh
17
18
20
21
22
23
24 26 36
25
27
28
mercury(I) chloride
tripotassium sodium sulfate copper hydroxide chloride
K3Na(SO4)2 Cu2(OH)3Cle
16
C16H10N2O2
potassium sulfate copper arsenate
K2SO4 Cu3(AsO4)2d
15
19
antimony oxide antimony oxide
Journal of Chemical Education • Vol. 79 No. 1 January 2002 • JChemEd.chem.wisc.edu chalcocite —
—
—
—
goethite
—
— —
—
—
malachite aphthalite paratacamite
aphthalite paratacamite
arcanite lammerite
— valentinite senarmontite
K2C4H4O6⭈0.5H2O potassium tartrate hydrate
Sb2O3 (rhombic) Sb2O3 (rhombic)b
— aphthalite
—
—
— —
— —
malachite paraspurite
—
arcanite
Mineral Name
14
13
furan eudesma-1,3-diene isofuran germacrene
C15H18O C14H18O
10
tripotassium hydrogen sulfate
iron iron oxide
Fe Fe oxide
9
potassium sodium tartrate tripotassium sodium sulfate
tripotassium hydrogen sulfate potassium nitrate
K3H(SO4)2 KNO3
8
K3H(SO4)2
copper carbonate hydroxide calcium silicate carbonate
CuCO3⭈Cu(OH)2 Ca5(SiO4)2CO3
KNaC4H4O6 K3Na(SO4)2c
antimony chloride oxide
Sb4O5Cl2b
12
potassium sulfate
K2SO4
7
Systematic Name
6
No. Formula
FT, XRD, XRF
GC–MS
XRD, XRF
FT, WC, XRD, XRF
FT, WC, XRD, XRF
FT, WC, XRD, XRF
FT, WC, XRD, XRF
Analytical Techniquea
Spurstein —
robbia, Krappwurzel
—
common salt, rock salt, sale da cucina, salgemma, Kochsalz, Steinsalz
ochre, ocra, Ocker, Rubinglimmer
pieces of colored glass
calomelano, Kalomel, Quecksilberchlorür, hydrargyrum muriaticum, mite Mercurius dulcis or mitigatus
tartaric acid, acido tartarico, Weinsäure —
indigo, indaco
alum, allume, Alaun
verde di Brunswick, verde di Brema, verde di montagna artificiale — —
— —
— —
antimony white, flowers of antimony, fiori argentini di antimonio, Weißspießglanz, Antimonblüte, flores antimonii, nix stibii
tartar, potassa tartrica, tartaro solubile, tartaro cristallizzato, sale vegetale, Weinstein
— continued
FT, WC, XRD, XRF
EM
WC, XRD, XRF
FT, WC, XRF
WC, XRD, XRF
XRF
WC, XRD, XRF
WC, XRD, XRF, IR
FT, XRD, GC–MS, IR, UV
FT, WC, XRD, XRF
FT, WC, XRD, XRF
FT, WC, XRD, XRF
WC, XRD, XRF
FT, XRD, XRF, TA
Rochelle salt, tartarus natronatus, sal polychretum Seignetti, Natro-Kali tartaricum, sale policreste solubile FT, WC, XRD, XRF —
—
compounds of myrrh, mirra, Myrrhe
— —
— nitre, salnitro, (Kali)Salpeter
verde di Brunswick, verde di Brema, verde di montagna artificiale —
polvere dell' Algarotto, polvere d' Algarotti, polvere angelica, Algarotpulver
arcano duplicato, sale de duobus, tartaro vetriuolato
Trivial Name
Table 2. Results for the Solid Samples
Chemistry for Everyone
in nearly all samples, but the percentage of these materials was not determined. is X-ray fluorescence; GC–MS is gas chromatography–mass spectrometry; TA is thermal analysis; IR is IR spectroscopy; UV is UV spectroscopy; EM is electron microscopy. bAlso contains an Sb–S compound. cAlso contains Na2CO3. dContains traces of Ca–Cl compounds and possibly CuSO4. eAlso contains Ca, Al oxides. fAlso contains traces of Mg, Fe, K compounds. gAlso contains oxides and carbonates of Mn, Fe, Al. hAlso contains soil. iAlso contains S, K, and P compounds. jAlso contains traces of Mg compounds. kAlso contains traces of an Fe compound. lAlso contains traces of S, P, Cl, Ti compounds. mAlso contains traces of compounds of S, Cl, Fe. NOTE: In addition, silicon dioxide and aluminum oxide were detected aFT is flame test; WC is wet chemistry; XRD is X-ray diffraction; XRF
FT, WC, XRD, XRF borax (pentahydrate), borace (pentaidrato) tincalcoite disodium tetraborate pentahydrate Na2B4O7⭈5H2O 40
WC, XRD, XRF — — — plumbago, black lead, piombaggine, Reißblei anorthite calcite quartz graphite calcium aluminum silicate calcium carbonate silicon dioxide carbon CaAl2Si2O8 CaCO3 SiO2 Cm 37
WC, XRD, XRF 35
FT, WC, XRD, XRF bianco di piombo innocuo, cerussa di Mülhausen, Vetriolbleierz, Bleisulfat
quartz albite calcite phlogopite
— — — —
anglesite lead sulfate
silicon dioxide calcium aluminum silicate calcium carbonate —
PbSO4
SiO2 (Na,Ca)Al(Si,Al)O8 CaCO3 KMg3(OH,F)2[AlSi3O10]l
34
33
WC, XRD, XRF hematite gypsum iron(III) oxide calcium sulfate hydrate Fe2O3 CaSO4⭈2H2O
32
caput mortum, colcotar, Englisch Rot gypsum, gesso, Gips
WC, XRD, XRF
WC, XRD, XRF cinnabar, vermillion, cinabro, vermiglione, Zinnober
MoS2 SiO2k
30
Molybdänglanz, Wasserblei —
—
molybdenite quartz
mercury sulfide
molybdenum sulfide silicon dioxide
HgSj
29
Analytical Techniquea
— katoite iron(III) hexacyanoferrate calcium aluminum oxides FeIII[FeIIIFeII(CN)6]3 Al6Ca4O13⭈3H2O Ca3Al2(OH)12i
Table 2. —Continued
Mineral Name Trivial Name Systematic Name Formula No.
Prussian blue, Berlin blue, azzurro Berlino, azzurro di Parigi, azzurro di Prussia, Berlinerblau, Turnbulls Blau — XRD, XRF, IR
Chemistry for Everyone
soap making, etc. Samples of iron (No. 10) and copper sulfide (No. 28) illustrate the importance of the extraction of metals in Tuscany—in particular, in Elba Island and the Metallifer Hills. Sample No. 25, which is assumed to be a raw material for glass or an additive to the raw material, and sample No. 22, which consists of colored glass sticks, are connected to glass manufacture in Tuscany— which, although promoted and protected by the Medici family, was economically threatened by the Murano glassblowers. The liquid samples are assumed to be in connection with medical and pharmaceutical studies. Three liquid samples were identified as essential oils (24): oil of parsley seeds (No. 1), oil of caraway (No. 4), and oil of celery (No. 31). Oil of parsley seeds was known as an aphrodisiac (25). Sample No. 3 was identified as ethanol, of dubious origin. Sample No. 5 was identified as a rancid oil; it was stored in the bottle with the inscription Olio di Dippel, which was an animal oil (26 ) used to dye fabric a brown color and also used in medicine. Some compounds of sample No. 2 were identified. This sample is designated by the label Olio espresso delle Formiche (oil pressed out of ants). Analytical Procedures and Instrumentation
Flame Test and Classical Wet Analysis The flame tests gave an indication of the nature of the atoms present. The samples were dissolved in the appropriate solvent (water, acid, or basic solution) and then treated with the reagent able to qualitatively recognize the groups present (e.g., silver nitrate to precipitate silver chloride). Thin-layer chromatography of the organic samples was used to provide information on the presence of several different compounds. Melting points were taken on a Buchi 510 melting-point apparatus. X-ray Fluorescence The incident X-ray beam (of a Philips Scansion Electronic Microscope, SEM) ionizes a core level of the elements and one electron is emitted. The resulting electron hole is refilled by one electron from a higher level. The energy difference between the electrons of the two levels is balanced by the emission of radiation, known as fluorescence. Each element emits fluorescence with specific energy values and can therefore be identified. The spectra were interpreted with the aid of the computer program’s bibliographic data. X-ray Diffraction The sample is prepared by grinding it to a fine powder that is then spread uniformly over the surface of a glass slide, using a small amount of adhesive binder. The instrument (Philips Diffractometer W 3710) is so constructed that this slide, when clamped in place, rotates in the path of a collimated X-ray beam while an X-ray detector, mounted on an arm, rotates about it to pick up the diffracted X-ray signal. The spectra were interpreted with the aid of the computer program’s bibliographic data.
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Other Instrumentation GC–MS: Hewlett-Packard 5890A gas chromatograph coupled to a 5970 mass selective detector. UV: Perkin-Elmer Lambda 16. IR: Perkin-Elmer FTIR 1600. NMR: Bruker 200 MHz. Thermal analysis: Netsch Thermal Analyzator Model 409 STA. Conclusions The various compounds and their individual history and importance to the 18th century and to Tuscany may be a good example to illustrate the state of chemistry during this period. Though absolute certainty about their intended use by Leopold cannot be attained, their possible purpose may be deduced from their general application. It is impossible to know why exactly these compounds are in Leopold’s bench. It might be that the main reason is their availability, and this is convenient for the researches of the Grand Duke. Certainly, the very same origin from Tuscany of all the compounds seems to embrace Targioni Tozzetti’s thesis on the intertwining of scientific research and economic purposes of developing tuscanian resources. “Lo studio dell’istoria naturale ben regolato, non è balocco d’oziosi ingegni, come alcuni si pensa, ma può influire moltissimo sui vantaggi di una società (the study of natural history, well regulated, is not the toy of lazy minds, as someone thinks, but may very well influence the economical advantages of a society)” (27 ). Acknowledgments IMM wishes to thank the Erasmus Office of the E.U. for a grant to prepare her thesis in Padova, and J. Schantl, University of Innsbruck, for help and encouragement. We thank Paolo Galluzzi and Mara Miniati, Istituto and Museo di Storia della Scienza, Firenze; Giampaolo De Vecchi and Roberto Menegazzi, Dipartimento di Mineralogia; Mauro Gobbin, Dipartimento di Ingegneria Meccanica; Umberto Vettori, Consiglio Nazionale delle Ricerche; and Claudio Furlan and Moreno Rossi, Centro Grandi Apparecchiature Scientifiche, all of the University of Padova, for help at various stages of sampling and analyzing. We thank the editor for all the efforts to improve the manuscript. Financial support from the Progetto Finalizzato Beni Culturali of the CNR is gratefully acknowledged. Literature Cited 1. Abbri, F. Kos, Mensile di Cultura e Storia delle Scienze Mediche, Naturali e Umane (Milan); 1994, 4, 91–108. 2. Wandruszka, A.; Leopold II; Herold: Wien-Munich, 1965. 3. Peham, H. Leopold II. Herrscher mit weiser Hand; Styria: Graz, Austria, 1987.
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4. Guareschi, I. Supplemento Annuale alla Enciclopedia di Chimica, Annuario di Chimica Scientifica e Industriale; Unione Tipografico-Editrice Torinese: Torino, 1908–1909; Vol. 8, Part I, p 413. 5. Ibid., p 451. 6. Guareschi, I. Supplemento Annuale alla Enciclopedia di Chimica, Annuario di Chimica Scientifica e Industriale; Unione Tipografico-Editrice Torinese: Torino, 1912; Vol. 28, Part III, p 412. 7. Il Museo di Storia della Scienza a Firenze, 2nd ed.; Righini Bonelli, M. L., Ed.; Electa: Milan, 1976. 8. Thorpe, E. Storia della Chimica, English translation; Società Tipografico-Editrice Nazionale: Torino, 1911; Chapter VII, p 100 and Chapter III, p 112. 9. Schiff, U. Il Museo di Storia della Scienza a Firenze, 2nd ed.; Righini Bonelli, M. L., Ed.; Electa: Milan, 1976; p 219. 10. Abbri, F. Ann. Ist. Museo Storia Sci. Firenze 1979, 4 (1), 36. 11. Guareschi, I.; Garelli, F. Nuova Enciclopedia di Chimica Scientifica, Tecnologica e Industriale; Unione TipograficoEditrice Torinese: Rome–Torino–Naples, 1906–1927. 12. Erdmann, H. Lehrbuch der Anorganischen Chemie; Friedrich Vieweg und Sohn: Braunschweig, 1898. 13. Hofmann, K. A. Lehrbuch der Anorganische Chemie, 6th ed.; Friedrich Vieweg und Sohn: Braunschweig, 1928. 14. Villaveccchia, V.; Fabris, G.; Rossi, G.; Belasio, R. Dizionario di Merceologia e di Chimica Applicata, 5th ed.; U. Hoepli: Milan, 1929. 15. Targioni Tozzetti, G. Relazioni d’Alcuni Viaggi Fatti in Diverse Parti della Toscana per Osservare le Produzioni Naturali e gli Antichi Monumenti di Essa; Stamperia Reale: Firenze, 1751–1754. 16. Guareschi, I. Nuova Enciclopedia di Chimica Scientifica, Tecnologica e Industriale; Unione Tipografico-Editrice Torinese: Rome–Torino–Naples, 1913; Vol. 6, pp 1103–1189. 17. Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed.; Wiley: New York, 1979; pp 365–367. 18. Arrigoni, T. In Siderurgia e Miniere in Maremma tra ’500 e ’900; Tognarini, I., Ed.; All’insegna del Giglio: Firenze, 1984; p 62. 19. Giormani, V. In Il Farmaco nei Tempi; Zanca, A., Ed.; Farmitalia Carlo Erba: Parma, 1990; pp 35–50. 20. Peham, H. Op. cit., p 108. 21. Mori, G. Studi di Storia dell’Industria, 2nd ed.; Riuniti: Rome, 1967; pp 383–425. 22. Peham, H. Op. cit., p 113. 23. Peham, H. Op. cit., p 154. 24. Gildemeister, E.; Hoffmann, F. Die Ätherischen Öle, 2nd ed.; Schimmel: Miltitz bei Leipzig, 1910. 25. Steinegger, E.; Hänsel, R. Pharmakognosie, 5th ed.; Springer: Berlin, 1992. 26. Guareschi, I.; Garelli, F. Nuova Enciclopedia di Chimica Scientifica, Tecnologica e Industriale; Unione TipograficoEditrice Torinese: Rome–Torino–Naples, 1913; Vol. 6, p 1129. 27. Targioni Tozzetti, G. Op. cit.; Vol. 9, p 31.
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