For copyright notice see final page of this file Chemistry 125: Lecture 19 Oxygen and the Chemical Revolution (Beginning to 1789) Studying the logic of the development of modern theory, technique and nomenclature helps to use them more effectively. The chronological development of organic chemistry can begin with Lavoisier, the father of modern chemistry. His “Chemical Revolution” depended upon the practices of ancient technology and alchemy and discoveries like those of Scheele, the Swedish apothecary who discovered oxygen and prepared the first pure samples of organic acids. Lavoisier’s Traité Elémentaire de Chimie launched modern chemistry with its focus on facts, ideas, and words. Lavoisier weighed gases and measured heat with a calorimeter, as well as clarifying chemical language and thought. His key concepts were conser-vation of mass for the elements, and oxidation, which could convert a “radical” or “base” into an acid. Synchronize when the speaker finishes saying “…quantum mechanics about 1925 - ‘26 actually...” Synchrony can be adjusted by using the pause(||) and run(>) controls. For copyright notice see final page of this file

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Background in Ancient Arts and Lore Noah Mosaic 12th Century Background in Ancient Arts and Lore Catedrale Monreale (Photo JMM)

Roman Glass Perfume Vial ~2000 years old Class of 1954 Chemical Research Building -5 days old Roman Glass Perfume Vial ~2000 years old

All the philosophy of nature which is now received, is either the philosophy of the Grecians, or that other of the alchemists… The one is gathered out of a few vulgar observations, and the other out of a few experiments of a furnace. from “Of Tribute: Praise of Knowledge” Works (1968) VIII p. 125 cited in Gleick, p. 206 note 10. Memorial Trinity Chapel Cambridge (photo JMM, 2007) Utraque unum : from both one Instauratio Magna : the great restoration This work contained Bacon's fundamental treatise, the Novum Organum -- a new method for scientific investigation to replace the old and faulty one of Aristotle. The book was given an imposing subtitle: "True Direction Concerning the Interpretation of Nature." The ship displayed on the book's title page, is sailing through the Pillars of Hercules. Tradition had always placed these as the limits of man's possible exploration. But instead of the traditional "ne plus ultra," Bacon's title page in fact declares, as did Coronelli's, "plus ultra.” The old oranon was Aristotle www.crs4.it/Ars/ arshtml/conclusion1.html Elizabeth accession 1558 dies 1603 Shakespeare 1564-1616 Not so much that Aristotle himself was wrong as that the scholastic reverence for his authority was misplaced. 1674 BOYLE Excell. Theol. II. iv. 170 That great Restorer of Physicks, the illustrious Verulam (OED physics) The one never faileth to multiply words, and the other ever faileth to multiply gold. Francis Bacon (1561-1626)

Title of Exhibition on Alchemy at the Beinecke Library 2009 OCCULT Bega Alchemist e.g. Newton “The Book of Secrets” Title of Exhibition on Alchemy at the Beinecke Library 2009 Newman: “a broad range of technological pursuits. These activities included metallurgical assaying, refining of salts, dye and pigment manufacture, the improvement of glass and ceramic formulas, the making of artificial gemstones, research on incendiary weapons, the study of chemical luminescence, techniques for the improvement of brewing, the study and development of artificial fertilizers, the making of perfumes and cosmetics, and a variety of medical pursuits, such as the analysis and purification of existing drugs and the discovery and manufacture of entirely new pharmaceuticals.” 1663

Mellon ms 41 Elements ~1570 Visio mystica Arnold of Villanova Emblematic Alchemy in English verse, with an English version of the Visio mystica of Arnold of Villanova Ripley scroll Ripley, George, d. 1490? Carpenter, Richard, d. 1670? England circa 1570 One roll with multiple illustrated sheets Call NumberMellon MS 41 Bibliographic Record Number1002678 Multi-image setSee all images in this set Image ID Number1002683 http://beinecke.library.yale.edu/dl_crosscollex/brbldl_getrec.asp?fld=img&id=1002683 Beinecke Library, Yale Visio mystica Arnold of Villanova 13th Century (England ~1570)

On the Philosopher’s Stone (13th Cent; Basel, 1571) Beinecke Library, Yale In two pages, every word underlined, 20 pointing fingers, 15 Nota Benes. On the Philosopher’s Stone (13th Cent; Basel, 1571)

alchemist Paracelsus (early 1500s) ©2006 Derek Ramsey Jewel Weed alchemist Paracelsus (early 1500s) Doctrine of Sympathies In nature antidotes are to be found near the source of illness. Old wives tale: see Treatment of poison ivy/oak allergic contact dermatitis with an extract of jewelweed American Journal of Contact Dermatitis, 1997, vol 8, pp. 150-153 David Long, Noel H. Ballentine, James G. Marks Jr Department of Medicine, Pennsylvania State University College of Medicine, Milton S. Hershey Medical Center, Hershey, USA.BACKGROUND: Jewelweed (Impatiens biflora) is a plant which has been used for centuries for the treatment of poison ivy/oak allergic contact dermatitis. Numerous claims for its effectiveness exist in the lay press, and over-the-counter medicaments containing jewelweed are reputed to be an effective remedy for poison ivy/oak dermatitis. Despite these claims, few scientific studies testing the effectiveness of jewelweed have been performed. OBJECTIVE: Our objective in this pilot study was to test the efficacy of an extract of jewelweed in the treatment of experimentally induced allergic contact dermatitis to poison ivy/oak. METHODS: A randomized, double-blinded, paired comparison investigation was performed. Ten adult volunteers were patch tested to urushiol, the allergenic resin in poison ivy/oak. For each volunteer, one patch test site was treated with an extract prepared from the fresh stems of jewelweed; the remaining site was treated with distilled water to serve as a control. Sites were examined on days 2, 3, 7, and 9 with reactions graded on a numerical scale. RESULTS: All subjects developed dermatitis at each patch test site. There was no statistically significant difference in the objective scores at the sites treated with jewelweed extract versus the distilled water control sites. CONCLUSION: This study demonstrated that an extract of jewelweed was not effective in the treatment of poison ivy/oak allergic contact dermatitis. Poison Ivy

Willow (Salix) found in malarial swamps hydrolyze oxidize Salicilic Acid Salicin (from bark) Willow (Salix) found in malarial swamps

“Vade mecum” Alchemical Lab Manual Beinecke Library, Yale Das Vade mecum Compiled by Caspar Harttung vom Hoff / Personal commonplace book combining skillful drawings of apparatus Page 36v-37r / Place of origin Gastein (Austria) Date1557 / Physical Description87 ff.ill.105 x 87 mm. In German and Latin. Parchment and paper codex, ff. 87 of which f. 1-3 and 6-19 are of paper, the remainder of parchment, in German vernacular with noteworthy literary character--some of them in verse--and numerous practical procedures. TextCall NumberMellon MS 38 Beinecke Rare Book and Manuscript Library, Yale University Bibliographic Record Number2037177 Multi-image setSee all images in this setImage ID Number1131955 / http://beinecke.library.yale.edu/dl_crosscollex/brbldl_getrec.asp?fld=img&id=1131955 “Vade mecum” Alchemical Lab Manual Caspar Harttung vom Hoff (Austria, 1557)

Carl Wilhelm Scheele (1742-1786) Prerevolutionary Pharmacist Carl Wilhelm Scheele (1742-1786) Carl Wilhelm Scheele (1742-1786) Woodcut frontispiece to Scheele “Chemische Abhandlung von der Luft und dem Feuer”, Upsala, 1777 (JMM, 2008) Stamp permission of Prof. Z. Rappoport.

Scheele's Acids Lactic Milk Citric Lemon Uric Urine Tartaric Tartar (purified as heavy-metal salts) Lactic Milk Bismuth, cobalt, antimony, tin, mercury, silver, and gold were attacked by lactic acid either by digestion or by boiling. After standing over tin the acid caused a black precipitate to form in a solution of gold in aqua regia. 7) Citric Lemon Uric Iron and zinc were dissolved with formation of flammable air. The iron solution was brown and gave no crystallization, but the zinc solution crystallized. 8) Urine Tartaric Tartar (wine cask residue) With copper our solution first took on a blue color, then green, finally dark blue, but it did not crystallize. 9) Benzoic Gum Benzoin Lead dissolved after several days of digestion. The solution acquired a sweet, tart taste but did not crystallize. 10) ! Oxalic Rhubarb (?) On Milk and its Acid (1780) 19 pp.

(self-contradiction) "Oxy" = Sharp What's sharp about Rhubarb? e.g. "Oxymoron" sharp dullness (self-contradiction) Acidic taste Latin "acidus" "acre" to be sour root "ac-" sharp

Scheele's Acids (purified as heavy-metal salts) Benzoic Oxalic Citric Lactic Uric Tartaric Gum Benzoin Rhubarb Lemon Milk Urine Tartar (Wine Casks)

Carbonyl vs. Carboxylic Acid Alcohol Alcohol pKa ~16 High HOMO Stabilized Higher HOMO More Stabilized Alcohol pKa ~16 Carboxylic Acid pKa ~5 pKa depends on energy difference between A-H and A- H+ (Note: there will be more to this story involving "inductive effects")

Scheele's Acids (purified as heavy-metal salts) Benzoic Oxalic Citric Lactic Uric Tartaric Gum Benzoin Rhubarb Lemon Milk Urine Tartar (Wine Casks) ?

Uric Acid pKa 5.8 (vs. 38 for NH3  NH2- + H+) Two C=O LUMOs stabilize N's High HOMO Two C=O LUMOs stabilize N-'s Higher HOMO pKa 5.8 (vs. 38 for NH3  NH2- + H+)

7 Elements Discovered or Codiscovered by Scheele gases nitrogen oxygen chlorine manganese molybdenum barium tung sten tungsten heavy stone (Swedish)

Ag2CO3 Ag2O + CO2 Ag + O2 Scheele (1771) D …since I have no large burning glass, I beg you to try with yours… Scheele (1771) Ag2CO3 Ag2O + CO2 D Ag + O2 > 340°C Feuerluft "fire air"

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The Chemical Revolution 1789 http://commons.wikimedia.org/wiki/Image:Le_Serment_du_Jeu_de_paume.jpg Bottom right Joseph Martin-Dauch, the only deputy to vote against the serment. The Chemical Revolution 1789

Werad = Root Licorice Wort Race? Wurzel Rutabega Radix Radish (glukos + rhiza) Greek Wort Old English Race? Razza Italian Wurzel German Werad Rutabega Swedish Radix Latin = Root Radish Radical: Going to the root or origin Mathematics (16th Cent) Eradicate Politics (18th Cent - England) Chemistry (18th Cent - France)

1787: Radical Introduced as a Political Term "The necessity of a substantial and radical reform in the representation..." J. Jebb

September 17, 1787

by Louis Bernard Guyton de MORVEAU (1737-1816) "Radical" Introduced as a Chemical Term 1787 by Louis Bernard Guyton de MORVEAU (1737-1816) http://commons.wikimedia.org/wiki/Image:Louis-Bernard_Guyton_de_Morveau.jpg age 50

Méthode de Nomenclature Chimique 1787 http://commons.wikimedia.org/wiki/Image:Berthollet_Claude_Louis_.jpg http://commons.wikimedia.org/wiki/Image:Antoine_François%2C_comte_de_Fourcroy.jpg Claude Louis BERTHOLLET (1748-1822) age 39 Antoine François de FOURCROY (1755-1809) age 32

Antoine Laurent Lavoisier (1743-1794) age 45 Traité Élémentaire de Chemie (1789) http://commons.wikimedia.org/wiki/Image:David_-_Portrait_of_Monsieur_Lavoisier_and_His_Wife.jpg 7,000 pounds (~$300,000)

Weighing a Gas Patm - Pgas vacuum Hg http://commons.wikimedia.org/wiki/Image:David_-_Portrait_of_Monsieur_Lavoisier_and_His_Wife.jpg And my photo from my book Hg Patm - Pgas Weighing a Gas

Lavoisier's Pneumatic Trough "Lavoisier in his Laboratory Mme. Lavoisier taking his dictation (After a sepia drawing by Mme. Lavoisier)" Facsimile from a drawing by Marie-Anne Lavoisier
Photographic reproduction of a photogravure from Edouard Grimaux (1835­1900), Lavoisier (1734­1794), Paris, 1888 Courtesy Edgar Fahs Smith Memorial Collection, Rare Book and Manuscript Library, University of Pennsylvania

Elementary Treatise of Chemistry PRESENTED IN A NEW ORDER AND ACCORDING TO MODERN DISCOVERIES With Figures 1789

Preliminary Discourse (1789) I had no other object, when I began the following Work, than to extend and explain more fully the Memoir which I read at the public meeting of the Academy of Science in the month of April 1787, on the necessity of reforming and completing the Nomenclature of Chemistry. While engaged in this employment, I perceived, better than I had ever done before, the justice of the following maxims of the Abbé de Condillac, in his System of Logic, and some of his other works:

Preliminary Discourse (1789) "We think only through the medium of words. --Languages are true analytical methods. --Algebra, which is adapted to its purpose in every species of expression, in the most simple, most exact, and best manner possible, is at the same time a language and an analytical method. --The art of reasoning is nothing more than a language well arranged."

Preliminary Discourse (1789) Thus, while I thought myself employed only in forming a Nomenclature, and while I proposed to myself nothing more than to improve the chemical language, my work transformed itself by degrees, without my being able to prevent it, into a treatise upon the Elements of Chemistry.

Preliminary Discourse (1789) The impossibility of separating the nomenclature of a science from the science itself, is owing to this, that every branch of physical science must consist of three things; the series of facts which are the objects of the science, the ideas which represent these facts, and the words by which these ideas are expressed. Like three impressions of the same seal, the word ought to produce the idea, and the idea to be a picture of the fact.

Preliminary Discourse (1789) And, as ideas are preserved and communicated by means of words, it necessarily follows that we cannot improve the language of any science without at the same time improving the science itself; neither can we, on the other hand, improve a science, without improving the language or nomenclature which belongs to it. However certain the facts of any science may be, and, however just the ideas we may have formed of these facts, we can only communicate false impressions to others, while we want words by which these may be properly expressed.

Clarity: Facts Ideas Words “impressions of the same seal”

New Order Doctrine 2) Nomenclature 3) Operations

Elements …if by the name of elements we mean to desig-nate the simple, indivisible molecules that make up substances, it is probable that we do not know what they are : but if, on the contrary, we associate with the name of elements, or of the principles of substances, the idea of the furthest stage to which analysis can reach, all substances that we have so far found no means to decompose are elements for us…they behave with respect to us like simple substances.

Traité Élémentaire de Chimie (1789) imponderable Table of Elements

Lavoisier-Laplace Calorimeter Flame Flame Completely Surrounded by Melting Ice Cage into Can Inner Can Completely Surrounded by Insulating Ice Lamp into Bucket Bucket into Cage Melted by Flame Only! 3 Feet Lavoisier-Laplace Calorimeter

Facts: Analysis

Analysis

Traité Élémentaire de Chimie (1789) Oxy-gen + Base or Radical Acid FACT THEORY ? WORD

Lavoisier's Compound Radicals Scheele Acids

End of Lecture 19 Oct. 17, 2008 Copyright © J. M. McBride 2009. Some rights reserved. Except for cited third-party materials, and those used by visiting speakers, all content is licensed under a Creative Commons License (Attribution-NonCommercial-ShareAlike 3.0). Use of this content constitutes your acceptance of the noted license and the terms and conditions of use. Materials from Wikimedia Commons are denoted by the symbol . Third party materials may be subject to additional intellectual property notices, information, or restrictions.   The following attribution may be used when reusing material that is not identified as third-party content: J. M. McBride, Chem 125. License: Creative Commons BY-NC-SA 3.0