Chemistry 125: Lecture 18October 14, 2009

Oxygen and the Chemical Revolution

(Beginning to 1789)

For copyright notice see final page of this file

Studying the logic of the development of modern theory, technique and nomenclature helps to use them

more effectively. Chronological treatments of organic chemistry often begin with Lavoisier, the father of

modern chemistry. But 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.

Yale Chemistry 1901S

Greek symbols denote substituent positions.

Cf. Clairvoyant

Benzene

Sheffield Chemistry Lab (SSS)

(only quantitative tool)

Yale Chemistry 1901S

BalanceBurettes

The precious Analytical Balances were key, but were not portable

Quantitative Tools?

C. Mahlon Kline (1901S)

Kline Chemistry Laboratory

(1964)

Kline Biology Tower

(1965)

#6 in Big Pharma (2008)

Quartz

Silliman Crystal

Silliman Crystal

Boyle Lavoisier

Berzelius etc.

Wöhler/Liebig

Genealogy

GenealogyBottom

Genealogy Top

Optional bargain book: Chasing the Molecule by John Buckingham (List Price: $24.95) Daedalus Item Code: 84237 Sale Price: $6.98

Background inAncient Arts and Lore

NoahMosaic 12th Century)

“Florence”Flask

Sicily(Monreale)

Roman GlassPerfume Vial

~2000 years old

Class of 1954Chemical Research Building

-5 days 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.

The one never faileth to multiply words, and the other ever faileth to multiply gold.

Francis Bacon (1561-1626)

Bega Alchemist

1663

e.g. NewtonOCCULT

Title of Exhibition on Alchemy at the Beinecke Library

2009

“The Book of Secrets”

Mellon ms 41 Elements~1570

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neck

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Visio mysticaArnold of Villanova

13th Century

(England ~1570)

On the Philosopher’s Stone (13th Cent; Basel, 1571)

Bei

neck

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alchemistParacelsus

(early 1500s)

Poison Ivy

Doctrine of Sympathies

In nature antidotes are to be found near the source of illness.

©20

06 D

erek

Ram

sey

Jewel Weed

Double-blind Clinical Test(1997)

No better than waterOH

OH

SalicilicAcid

Willow (Salix)found in malarial swamps

Salicin(from bark)

hydrolyze

oxidize

“Vade mecum” Alchemical Lab Manual Caspar Harttung vom Hoff (Austria, 1557)

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neck

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Carl Wilhelm

Scheele (1742-1786)

Prerevolutionary Pharmacist

Carl Wilhelm

Scheele (1742-1786)

Scheele's Acids

BenzoicO

OH

H

H

H

H

H

UricN

N N

N

O

O

O

H

HH

H

CitricH

H O

OHH

HO

O

H

OH

O OH

LacticH

OH O

OH

H3C

OxalicO

OH

HO

O

Gum Benzoin

Rhubarb (?)

Lemon

Milk

Urine

(purified as heavy-metal salts)

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)

Lead dissolved after several days of digestion. The solution acquired a sweet, tart taste but did not crystallize.

10)

With copper our solution first took on a blue color, then green, finally dark blue, but it did not crystallize.

9)

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)

On Milk and its Acid (1780) 19 pp.

!

Tartaric H

OH O

OHHO

HO

O

H

Tartar(wine cask residue)

e.g. "Oxymoron"

"Oxy" = Sharp

What's sharpabout Rhubarb?

Acidic taste

"acre" to be sour

root "ac-" sharp

sharp dullness(self-contradiction) Latin "acidus”; Greek

(oxus)

Scheele's Acids (purified as heavy-metal salts)

Benzoic

Oxalic

Citric

Lactic

Uric

Tartaric

O

OH

H

H

H

H

H

N

N N

N

O

O

O

H

HH

H

H

H O

OHH

HO

O

H

OH

O OH

H

OH O

OH

H3C

H

OH O

OHHO

HO

O

H

O

OH

HO

O

Gum Benzoin

Rhubarb

Lemon

Milk

Urine

Tartar (Wine Casks)

vs. Carboxylic Acid

Alcohol pKa ~16 Carboxylic Acid pKa ~5

AlcoholCarbonyl

High HOMO Stabilized

C

O

O H

C

O

O H

C

O

O H

Higher HOMO More Stabilized

C

O

O

C

O

O

C

O

O

(Note: there will be more to this story involving "inductive effects")

pKa depends on energy difference between A-H and A- H+

Scheele's Acids (purified as heavy-metal salts)

Benzoic

Oxalic

Citric

Lactic

Uric

Tartaric

O

OH

H

H

H

H

H

N

N N

N

O

O

O

H

HH

H

H

H O

OHH

HO

O

H

OH

O OH

H

OH O

OH

H3C

H

OH O

OHHO

HO

O

H

O

OH

HO

O

Gum Benzoin

Rhubarb

Lemon

Milk

Urine

Tartar (Wine Casks)

?

Uric Acid

Two C=O LUMOs stabilize N's High HOMO

N

N N

N

O

O

O

H

HH

HN

N N

N

O

O

O

H

HH

HN

N N

N

O

O

O

H

HH

H

Two C=O LUMOs stabilize N-'s Higher HOMO

N

N N

N

O

O

O

H

HH

N

N N

N

O

O

O

H

HH

N

N N

N

O

O

O

H

HH

pKa 5.8 (vs. 38 for NH3 NH2- + H+)

tung sten

7 Elements Discovered or Codiscovered by Scheele

nitrogen

chlorine

manganese

molybdenum

barium tungsten

oxygen

gases

heavy stone (Swedish)

Scheele (1771)

Feuerluft "fire air"

Ag + O2

> 340°C

Ag2CO3

Ag2O + CO2

…since I have no large burning glass, I beg you to try with yours…

Genealogy Top

The Chemical Revolution 1789

WeradRadix

Latin

Licorice(glukos + rhiza)

Greek

RutabegaSwedish

WortOld English

Mathematics (16th Cent)

Race?RazzaItalian

Eradicate

WurzelGerman

Chemistry (18th Cent - France)

Politics (18th Cent - England)

Radish Radical: Going to the root or origin

= Root

1787: Radical Introduced as a Political Term

"The necessity of a substantial and radical reform in the representation..."

J. Jebb

September 17, 1787

byLouis Bernard

Guyton de MORVEAU(1737-1816)

"Radical"Introduced as aChemical Term

1787

age 50

Méthode de Nomenclature Chimique1787

Antoine François de FOURCROY

(1755-1809) age 32Claude Louis BERTHOLLET

(1748-1822) age 39

AntoineLaurent

Lavoisier(1743-1794)

age 45

7,000 pounds (~$300,000)

TraitéÉlémentairede Chemie

(1789)

Weighing a Gas

vacuum

HgPatm - Pgas

"Lavoisier in his Laboratory

Mme. Lavoisier taking his dictation

(After a sepia drawing

by Mme. Lavoisier)"

Lavoisier'sPneumatic Trough

Elementary Treatiseof Chemistry

1789

PRESENTED IN A NEW ORDERAND ACCORDING TO MODERN DISCOVERIES

With Figures

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

1) 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.

TraitéÉlémentairede Chimie

(1789)

Table ofElements

imponderable

Lavoisier-Laplace Calorimeter (1782)

Flame

3 Feet

Inner CanCompletelySurrounded

by InsulatingIce

Lamp into

BucketBucket into Cage

Cage into Can

FlameCompletelySurroundedby Melting

Ice

Melted by Flame Only!

End of Lecture 18Oct. 14, 2009

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