The first rotavap?

In this post I said that Lyman Creighton Craig invented the rotavap (1950) and that Walter Büchi made the 'modern design' (1957). I may have been wrong.

Is this alchemist using a rotavap almost 2 centuries before Craig?
The Alchemist in Search of the Philosophers Stone, by Joseph Wright of Derby, 1771.

What I hate about patents (part II)

A while ago I already told what I hate about patents. Here is another example of the 'I'm not gonna tell you'- style.

Ah, that is enlightening...

Top 5 chemists who died in really lousy ways

Chemgeek said in a comment here about Lavoisier that he could be included in the 'Top 5 dead chemists who died in really lousy ways'. A nice Top 5 to do I thought, so here we go. (Lavoisier was already number one in the Top 5 executed chemists so I decided not to include him.)

1) Ernest Julius Cohen (1869-1944) The Dutch physical chemist Cohen studied under Arrhenius, Moissan and wrote his thesis for a doctorate under J.H. van 't Hoff. Chemistry was a 'family-disease', his father Jacques was a chemist who had studied under Liebig and Bunsen. In 1901 Cohen was appointed extraordinary Professor of Chemistry at the University of Amsterdam, and Professor of Inorganic and General Chemistry at the university of Utrecht in 1902. He was the first president of IUPAC. He worked on allotropy of metals (worked out the chemistry of tin pest), photographic chemistry, electrochemistry and he wrote on science history.

In 1941 Cohen's property was seized by the German occupier and became a house for German officers. Friendly neighbors took him and his wife into their house. After May 1942 he had to wear the yellow star of David to show that he was a Jew. In 1943 he wanted to visit the laboratory but was arrested and taken prisoner because 'he wanted to enter a public building'. Cohen was taken to the concentration camp Vught. The Council of the Dutch Chemical Society approached the S.S. authorities leading to Cohen's release. Despite the advice of friends, Cohen refused to go into hiding, because 'he had done nothing wrong'. He was arrested again on Febuary 28 1944, and taken to concentration camp Westerbork. The efforts of his friends to have him released were in vain. On March 3 he was transported to Auschwitz. About 2 days later he died there in a Nazi gas chamber.

2) Thomas Midgley (1889-1944)
Chemist and mechanical engineer Midgely developed TEL additive to petrol and CFC's as refrigerants. His work on TEL resulted in lead poisoning, but he recovered. Polio disabled him in 1940. He designed a device with strings and pulleys to lift him from his bed. On November 2 1944 he was strangled by this machine.

3) Pierre Curie (1859–1906)
After a luch meeting on April 19, 1906 Pierre crosses Rue Dauphine in Paris during heavy snowfall. He was intercepted by a horse-drawn wagon with a heavy load of military supplies. Pierre's skull was crushed under the carriage wheel.

4) Karen Wetterhahn (1949-1997)
Professor of chemistry at Dartmouth College, Wetterhahn, spilled some dimethylmercury on her latex gloves on August 14, 1996. Five months later she began to have troubles with her speach and sense of balance. It turned out that the dimethylmercury had diffused through the gloves, and caused mercury poisining. she slipped into a coma and died June 8, 1997.

5) Dominique Burget (1965-2006)
A pressure vessel with ethene exploded in a research building of the Ecole Nationale Supérieure de Chimie de Mulhouse, on March 24, 2006. Burget was working in a lab above, and was killed.

Clerihew

Edmund Clerihew Bentley the inventor of the Clerihew wrote this clerihew.

Sir Humphry Davy
Abominated gravy.
He lived in the odium
Of having discovered sodium.

There should be more chemist clerihews. So I made a start.

Marie Curie,
Not hard to see,
Was glowing with pride,
And glowed in the night.

Herr Wöhler, Friedrich
He told his friend Liebig:
'Not now, sorry. See ya!
I’m pissing urea.’

Antoine-Laurent de Lavoisier,
Said : ‘Phlogiston theory is not okay,
This phlogiston theory is driving me mad,
I have to disprove it or I’ll lose my head.’

Robert H. Grubbs,
he visited pubs.
One pub let a bell ring,
That ring meant 'we're closing!'.

Ageing and poses in chemistry

Nicéphore Niépce made the first permanent photo in 1826. Thanks to the work of people like him there are pictures of a lot of chemists from the old days.

A lot of pictures from the 19th and early 20th are potraits. It seems that some poses were quite popular and I wonder whether people stole each other's pose.

Some examples:
- ‘The old wise chemist in chair’-pose
- ‘The chemist in action with Bunsen-burner’-pose
- ‘The leaning head on hand thinking’-pose (still popular) Another great thing you can do nowadays is see how chemists aged. You can see how unhealthy chemistry was back then. Chemists of nearly 70 looked like 170. The chemists of a generation later had a better life. Linus Pauling for example did have the looks that corresponded to his age.

Lovely cancer research

In Nature Reviews Drug Discovery 2007, 6, 115 there is a paper to motivate everybody who is working on oncology. 'Why is cancer drug discovery so difficult?'

'Oncology has one of the poorest records for investigational drugs in clinical development, with success rates that are more than three times lower than for cardiovascular disease. The widespread, relentless and lethal nature of cancer persists, with only incremental overall improvements in treatment outcomes, despite billions of dollars of public and private investment. The few notable successes, such as imatinib (Gleevec; Novartis) in the treatment of chronic myeloid leukaemia (CML), are, so far, exceptions.'

Somewhere else they state :'cancer models are notoriously problematic'

Should I be glad that I am not working in this field? Hmm, I do not care, I am used to failure. That is my job I think.

They have another wise remark: 'A good target is useless without a correspondingly good cognate drug.'

I would like to rephrase this to : 'I do not want your well validated target for which there is only a lousy biological assay.'

In most labs there is…

- the bastard who only stops talking about his own fantastic project to remind you of your last failed one.

- the demi-water drinker.

- the nitwit who repeats all smart things others said an hour ago.

- the gutless character who always agrees with the boss, provided that he is around.

- the compulsive dry-ice in the waterbath of your rotavap thrower.

- the retard with a ‘try the microwave'-neurosis.

- the creep you suspect to have a pyridine fetish or something like that.

- someone like me who believes to be on the right place in such a mental institution.

Top 5 dead chemists

1) Friedrich Wöhler (1800-1882)
Wöhler is the only person in the top 5 list that never received a nobel prize. He died too soon for it. But this is the third time he is number one on a 'top 5 list' (see here and here).

Wöhler did the first total synthesis and proved that organic material could be synthesized from inorganic material. He published this in 1828 (Ueber künstliche Bildung des Harnstoffs; Ann. Phys. Chem. 1828, 88, 253).
'On the artificial formation of urea '

Where he tells us this.

'this study gave the unexpected result that combining cyanic acid with ammonia creates urea'

2) Robert Burns Woodward (1917-1979)

Number one on this list.

3) Maria Skłodowska-Curie (1867-1934)

The only woman that received two Nobel prizes, and ended as number one on this top 5 list. I said something about her here as well. Besides the Nobel prizes she was 'famous' for her affair, after her husband's death, with the married Paul Langevin. This caused a press scandal in 1911.

4) Hermann Emil Fischer (1852-1919)

The founding father of carbohydrate chemistry. His name is connected to a projection, indole- and oxazole synthesis and much more.

5) Linus Carl Pauling (1901-1994)

He was the only person to win two unshared Nobel prizes. Famous for his work on the nature of the chemical bond, crystal and protein structure determination, orthomolecular medicine and much more. He was a member of the emergency committee of atomic scientists founded by Einstein.

Well, the final score was (total 372 votes) :

(My own top 5 would have included Antoine Lavoisier, Marie Curie, Dmitri Mendeleev, Jacobus Henricus van 't Hoff and Friedrich Wöhler. I am happy with this result though.)

Top 10 greatest organic chemists of all time

Paul republished his top 10 greatest organic chemists of all time post from his old blog. Woodward as number 1 (doing good here as well). He included living creatures as well.

top 5 dead chemists (score so far)

Top 5 German/Austrian physicists in chemistry

Many physicists made major contributions in the field of theoretical chemistry. Because of the abundance of such physicists I decided to restrict this list to German and Austrian physicists. The 5 physicists were ofcourse the pioneers of quantum mechanics and Nobel prize winners. The importance of their work for chemistry does not need an explanation.

1) Erwin Schrödinger (1887–1961)

Famous because of the Schrödinger equation published in 1925: Quantisierung als Eigenwertproblem; Annalen der Physik; 1926, 384, 4, 361 His papers contain impressive derivatives, integrals and differentials which confirm his image of a brilliant scientists who lives surrounded by unreadable formulas.

2) Werner Heisenberg (1901-1976)

Heisenberg published the uncertainity priciple in 1927: Über den anschaulichen Inhalt der quantentheoretischen Kinematik und Mechanik; Zeitschrift für Physik A Hadrons and Nuclei, 1927, 43, 172

The Heisenberg priciple triggered Albert Einstein to write a famous sentence to Max Born. During his career he collaborated with Niels Bohr, Max Born, Wolfgang Pauli and the Nazis. The latter caused some damage on his reputation.

3) Max Born (1882-1970)

Born formulated the now-standard interpretation of the probability density function for ψ*ψ in the Schrödinger equation. In 1926 Born received a letter from Albert Einstein about the Heisenberg uncertainity principle with the famous quote: "I, at any rate, am convinced that He does not throw dice." Born replied with the famous words: "Albert, stop telling God what He must do!"

4) Wolfgang Pauli (1900-1958)

Famous for the Pauli-exclusion principle, published in 1925: Über den Zusammenhang des Abschlusses der Elektronengruppen im Atom mit der Komplexstruktur der Spektren; Zeitschrift für Physik A Hadrons and Nuclei, 1925, 31, 765. Spin theory was another achievement.

5) Erich Hückel (1896-1980)

Devoloped a method for molecular orbital calculations for π electron systems. In 1931 he published valence bond and molecular orbital formulation for benzene: Die Elektronenkonfiguration des Benzols und verwandter Verbindungen; Zeitschrift für Physik A Hadrons and Nuclei, 1931, 70, 204 . Remebered for the 4n+2 rule as well.

Top 5 dead chemists (final)

I updated the Top 5 dead chemists poll, the votes from the qualification round will count for the final as well. You can vote again on your favourites (once a day). The poll shows the ranking from the qualification round. Very happy that Curie is number 1 now.

Top 5 chemists (qualification round)

Top 5 chemists (qualification round)

I selected some chemists that may be included in the final top 5 ranking.

There are some rules for competitors.

1) The chemists have to be dead.
2) Borderline chemists are allowed, but non-chemists with a big influence on chemistry are not allowed, e.g. physicists like Bohr. (This will be another top 5)
3) Fame is not obligatory but it helps. A dramatic story behind the person can be advantageous as well (I included Karen Wetterhahn).
4) Alchemists are not allowed, so chemists from the Lavoisier-era are probably the oldest competitors.

You can nominate another chemist with a comment here or vote on your favourite chemists in the poll on the right side. (You can select more than one chemist.)

Markovnikov's rule

I was reading an essay about named things and saw this picture. (The Road to Chemical Names and Eponyms: Discovery, Priority, and Credit, Angew. Chem. int. ed., 2004, 43, 5888)

Figure 3. V.V. Markovnikov (1838-1904). He
would hardly recognize the rule now bearing
his name.

In the text there is no reference to this Figure 3, but I thought it was probably a nice example of how things become named to people who had just 'a role in it'.

We all know Markovnikov's rule:

In elctrophillic additions of H-X to alkenes the hydrogen ends up attached to the carbon of the double bond that had more hydrogens to start with. (Clayden, Greeves, Warren and Wothers' textbook).

Nowadays we learn the reason behind this observation, which is far more important. Markovnikov's rule is not a law.

Now I wanted to know how Markovnikov formulated this rule himself so I searched for his paper and found it quite easily. The rule can be found in an addendum of a paper on isomeric buturic acid. (Ueber die Abhängigkeit der verschiedenen Vertretbarkeit des Radicalwasserstoffs in den isomeren Buttersäuren, Annalen der Chemie und Pharmacie, 1870, 153, 2, 228)

He starts to say : 'I cannot here enter into a detailed examination of the various facts that alows us to postulate this rule rule.'

Then he says (in italics): 'When an unsymmetrical alkene combines with a hydrohalic acid, the halogen adds on to the carbon atom containing the fewer hydrogen atoms, that is the carbon that is more under the influence of other carbons.'

Markovnikov said exactly the same thing as the Clayden book does. Why would Markovnikov hardly recognize the rule now bearing his name?? The only reason I can think why he would not recognize it now is because he is dead!!!

Markovnikov 's paper is quite sloppy. It contains several errors and it is not obvious which chemistry was done by himself. It is obvious he relied on the work of people like Butlerov.It took about 60 years before his rule became well known because of the work done by Maas (1924) and later Kharasch (1933). In Markovnikov's time stereochemistry was about to be born, nobody saw the important addendum in his paper, but he formulated the rule himself, Prof. Pedro can deny it, but it is true.

Mme Curie

In a comment here I said about Curie: "I do not know how important her husband was initially for her acceptance". Well I was reading in her biography again and I read that there were some people who wanted to give her first Nobel prize (physics) to Pierre and Henri Becquerel alone. Marie Curie had the luck to have the right progressive men around her.

I discovered something about her acceptance when I searched for publications of Marie.

1911 - the year she received her second Nobel prize(chemistry)
Darstellung der reinen Radiumsalze (Zeitschrift für Angewandte Chemie, 1911, 24, 8, 343)Quite weird that an author is named, 'wife of Pierre Curie' (Pierre had been dead for 5 years then).

1931 - 3 years before her death

Bericht der Atomgewichtskommission der internationalen Union für Chemie (Berichte der deutschen chemischen Gesellschaft 1931, 64, 5, 93)

Now her own initial is used with the famous 'Madame', while the others have no prefix. In 20 years she evolved from somebody's wife into an icon.

Top 5 chemist quotes

1) Friedrich Wöhler
Die organische Chemie kann einen jetzt ganz toll machen. Sie kommt mir wie ein Urwald der Tropenländer vor, voll der merkwürdigsten Dinge, ein ungeheures Dickicht, ohne Ausgang und Ende, in das man sich nicht hinein wagen mag.

(At this time organic chemistry can drive one completely crazy. It seems to me like a primeval tropical jungle, full of the most remarkable things, an amazing thicket, without escape or end, into which one would not dare to enter.)

4) Yves Chauvin
Je me sens plutôt embarrassé. (I find it embarrassing, above all.)
Answering the question : 'How does it feel' [to win the Nobel prize].

3) Dmitri Mendeleev
Work, look for peace and calm in work: you will find it nowhere else.

4) Margaret Thatcher (had another job besides being a chemist)
I am extraordinarily patient, provided I get my own way in the end.

5) Watson & Crick
It has not escaped our notice that the specific pairing we have postulated immediately suggests a possible copying mechanism for the genetic material. (Nature 1953)

Well let's do a top 5 chemistry blog quotes as well.

1) We don't need your stinkin' rankings! (carbon-based curiosities)

2) True, acetyl chloride makes me cry and carbon disulphide makes me sad. (chemical musings)

3) Hey, I never think it's a good idea to turn me out on the street. (in the pipeline)

4) Honestly, I can't think of any one who would say: "My life will be complete once I'll graduate and start my research project about gout!" (half decent pharmaceutical chemistry)

5) It clicks everything, even your mom, but she’s a slut anyway! (chem blog)

Top 5 lingua franca of science

In EMBO reports there is an article titled: Is there science beyond English? EMBO reports 2007, 8, 2, 112) The answer is ofcourse; ‘Yes, there is’. The problem is that an important study that is published in Sanskrit will not easily reach a large public and gain the appropriate recognition. The article describes some obstacles of science that is written in a foreign language, Brazil is taken as an example. (I said foreign… but I must admit that English is a foreign language for me, hope that is not too obvious.)

So here is my : Top 5 lingua franca of science

1) Latin

Latin was the academic language for a long time. A lot of books that created ‘modern’ science was written in Latin. Isaac Newton, Copernicus, Johannes Kepler, Carolus Linnaeus and many other old time heroes wrote their famous work in Latin.

2) German

German was the most important scientific language of physics and chemistry in the 19th and early 20th century. In the Wiley Backfile Collection you can find so many famous publications in German by famous scientists like Werner Heisenberg, Erwin Schrödinger, Albert Einstein, Niels Bohr, Friedrich Wöhler and Emil Fischer to name a few.

3) Greek

Ptolemy, Aristotle, Euclid, Archimedes, Plato, Pythagoras and many other ancient Greeks laid down the foundations of science.

4) English

Scientific language number one, nowadays. Two famous examples: On the Origin of Species by Means of Natural Selection, or the Preservation of Favoured Races in the Struggle for Life. by Charles Darwin. And more recent : Molecular Structure of Nucleic Acids: A Structure for Deoxyribose Nucleic Acid by Watson and Crick.

5) Russian

For chemistry Russian was a very important but somewhat ignored language. Dmitri Mendeleev published his periodic system in a Russian textbook in Osnovy Khimii (Principles of Chemistry). The importance of his work was recognised when an abstract of his work on the elements was translated (yep.. in German; see here as well). Other famous chemists that did their work in Russian : Alexander Mikhailovich Zaitsev, Aleksandr Mikhailovich Butlerov, Sergei Nikolaevich Reformatskii and others ofcource.

Rotavap

And now some unnamed lab-equipment: the rotavap.

It is said that Lyman Creighton Craig (1906-1974) invented the rotavap. He described it in 1950 (Versatile Laboratory Concentration Device; Anal. Chem.; 1950; 22(11) pp 1462 - 1462)

They even thought of another purpose besides concentration.Walter Büchi improved the design and introduced it in 1957 on the market. See here for a little bit of Büchi history and an illustration of his first commercial rotavap. I could not find a patent of this design though. I found a later patent by Walter Büchi (GB1039709) though, in the old patent tongue. Another Walter Büchi patent contains some lovely handwriting. Recently I needed dry THF (quick and dirty did not work) and the commercial stuff was all used or wet and old. I had to distill some THF. Distillation equipment is not in excess out here so I used a Dean-Stark trap. When the distilling was going well, I saw I had the perfect distilling equipment standing next to me. I realized that with minor adaptions I could use it as the perfect reduced pressure Dean-Stark distillation equipment, venting with dry argon after distillation makes it very nice for distilling solvents to dry it.

I will call it the "een of andere vent apparatus".

Hopkins & Davies wanted; Cribb found

I found two other named condensers, again a name of which I can not find the person.

A final Round-up on the condensers. (see previous post for additional links to pictures of the condensers.

Felix Richard Allihn (1854 – 1915)
German glassblower made the bulb reflux condenser at the firm Warmbrunn, Quilitz & Co in Berlin.

Otto Dimroth (1872 – 1940)
German chemist invented the reflux condeser with an internal double spiral for cooling to have the inlet and outlet at the top of the condeser. He is also known because of the Dimroth rearrangement.
Über intramolekulare Umlagerungen, Liebig's Ann. Chem. 1910, 373, 3, 336

Fritz Walter Paul Friedrichs (1882 – 1958)
German chemist. Invented the reflux condeser with the spiraled cold finger.

Some new forms of laboratory apparatus; JACS, 1912, 34 1509

Thomas Graham (1805–1869)
Scottish physical chemist. Also known from Graham’s law of diffusion. Invented the distillation condenser with the helical condensation pathway.

Cecil Howard Cribb (1864 – 1932)

Brittish chemist, described this double surface Cribb condenser in 1898.

A new form of condenser, Analyst, 1898, 23, 119 - 122

Hopkins condenser
Unable to find out which Hopkins this man was. Named a vertical distillation condenser.

Davies condenser
Unable to find out which Davies this man was.

Named an improved version of the Cribb condenser.

(You may think I have a named-glassware fetish now)