1. 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.
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For copyright notice see final page of this file

2. Genealogy Top

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

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

5. 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 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
arshtml/conclusion1.html
Elizabeth accession 1558 dies 1603
Shakespeare
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 ( )

6. 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

7. 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 One roll with multiple illustrated sheets
Call NumberMellon MS 41 Bibliographic Record Number
Multi-image setSee all images in this set Image ID Number
Beinecke Library, Yale
Visio mystica
Arnold of Villanova
13th Century
(England ~1570)

8. 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)

9. 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
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

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

11. “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 Number Multi-image setSee all images in this setImage ID Number /
“Vade mecum” Alchemical Lab Manual
Caspar Harttung vom Hoff (Austria, 1557)

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

13. 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.

14. (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

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

16. 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")

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

18. 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 (vs. 38 for NH3  NH2- + H+)

19. 7 Elements Discovered or Codiscovered by Scheele
gases
nitrogen
oxygen
chlorine
manganese
molybdenum
barium
tung sten
tungsten
heavy stone (Swedish)

20. 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"

21. Genealogy Top

22. The Chemical Revolution 1789
Bottom right Joseph Martin-Dauch, the only deputy to vote against the serment.
The Chemical Revolution

23. 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)

24. 1787: Radical Introduced as a Political Term
"The necessity of a substantial and radical reform in the representation..."
J. Jebb

25. September 17, 1787

26. by Louis Bernard Guyton de MORVEAU (1737-1816)
"Radical"
Introduced as a
Chemical Term
1787
by Louis Bernard Guyton de MORVEAU ( )
age 50

27. Méthode de Nomenclature Chimique 1787
Claude Louis BERTHOLLET
( ) age 39
Antoine François de FOURCROY
( ) age 32

28. Antoine Laurent Lavoisier (1743-1794) age 45
Traité
Élémentaire
de Chemie
(1789)
7,000 pounds (~$300,000)

29. Weighing a Gas Patm - Pgas vacuum Hg
And my photo from my book Hg
Patm - Pgas
Weighing a Gas

30. 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, Courtesy Edgar Fahs Smith Memorial Collection, Rare Book and Manuscript Library, University of Pennsylvania

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

32. 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:

33. 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."

34. 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.

35. 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.

36. 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.

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

38. New Order
Doctrine
2) Nomenclature
3) Operations

39. 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.

40. Traité Élémentaire de Chimie (1789)
imponderable
Table of
Elements

41. 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

42. Facts: Analysis

43. Analysis

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

45. Lavoisier's Compound Radicals
Scheele
Acids

46. End of Lecture 19 Oct. 17, 2008
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