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Monday, January 24, 2011


i don’t imagin Mikhail Tsvet was too thrilld
by having to move from Geneva to St.
Petersburg & take his degrees all over again.
& his throat wasn’t too thrilld by
the Russian wintr.
he invented absorption
chromatography but Willstätter in Germany
tried to repeat his work using an
overly aggressiv absorbent that denaturd
the chlorophyll & said his work
wasn’t valid.

Gilbert Newton Lewis in his later years
investigated the excited electronic states of
organic molecules toward understanding
their color & phosphorescence.

i would say that Lewis is our first great
american chemist if i may use that langwij
i hav been unabl to find his later papers
but you can see the direction he is going.

i now learn that Lewis found the phos-
phorescence is due to an excited state
in hwich electrons that would normally be
paird with opposite spins are insted
excited to hav their spins in the same direction.

but bettr he hadn’t done
that last experiment with hydrogen cyanide.

Alfred Werner had just gotten his Ph.D.
in inorganic chemistry. chemists had
at this time made a larj numbr of
colord compounds containing transition
metals & ammonia or chloride ion
or cyanide ion. chemists were
unabl to explain these compounds. Werner
thot abt them night & day & one
night he dreamd the correct structur
& got up & wrote his coordination theory.
it was immediately recognized & he was
appointed professor at the University of Zurich.
highly unusual that sumone would read his
paper & act on it. i had assumed he was
German but he was Swiss. perhaps
that would explain it, Darlene said.
so he spent the rest of his life refining
his theory & giving brilliant lecturs.
happiness hold my hand.

Paul Pfeiffer was Alfred Werner’s
brightest student & became his assistant
until they had a dispute. hwat
the dispute was about i do not know.

perhaps Pfeiffer questioned Werner’s belief
that the Co-Cl bonds were a primary
valence at long distance, hwile the Co-NH3
were a secondary valence at shorter distance.

perhaps he said that there was no
theoretical justification for their existence.
perhaps he said both electrons were
supplied by the same atom.

perhaps he said that the chlorides are
ionized in solution & must
be bonded by electrovalence.
forgiv us our enmity.

there is a sadness or glory that envelops us
hwen we read the lives of the great chemists
much different from reading a textbook
& a continuity: Robert Bunsen to
Adolf Bayer to Richard Willstätter

Bunsen’s burner was before my time
Bayer made indigo & discoverd
the phthalein dyes & we expect
the glory to be past on & so it was

until at his height Willstätter resigns
because of increasing antisemitism
many questiond the wisdom of his decision
but he was adamant. & refused to go forward

like my generation hoo refused to
work for a government that bombd the Vietnamese
& became common laborers
& so we remain without glory but with honor

o weep for me in the quest for my father.
he had wanted to be a chemist
& everybody said, oh, you’re so smart
you should be a doctor!

he later told me that he regretted it.

i remembr growing up in Pass Christian
hwer he was the only doctor. fishermen
would go floundering & step on a stingray
& he would cut out the bone. the fishermen

didn’t hav any money so they would
pay him in fish. fish that would to-day
cost a thousand dollars. i thot
everybody had a seaport & an offshore breeze.

you can’t always take hwat a person
says about himself at face value
there are no chemical notes. the notes
that hav cum down are studies of how

the Commanche raised their children.
& that remaind his passion to the very end.

Calvin became interested in copper khelates
hwile working at Manchester with Michael Polanyi
& it would hav been natural for him to go on to Munich to work under
Hans Fischer had not the two cuntries been approaching war.

Calvin publisht his main work on khelates after the war
so perhaps the loss of Fischer moved him to do so.
there he says that outstanding exampls of the contribution of
a strong resonance effect to khelate stability are

the natural pigments, such as chlorophyll or heme,
in hwich a porphyrin derivativ is bonded to
a divalent metal. & shows the resonating
structur of the copper khelate of the parent

unsubstituted porphin ring, originally
synthesized by Fischer. it is
the green blood of the horseshoe trilobite.

reading Ihde, The Development of Modern Chemistry
i came across a reference to unpaird electrons in
the oxygen molecule. i drew the Lewis
structur & they look paird to me.

so i read Sidgwick Electronic Theory of Valency
& he said there was no explanation for
oxygen’s exceptional paramagnetism.
i then read Ephraim & he says

the fact that oxygen (O2) is paramagnetic,
in spite of an even number of electrons,
presents a problem regarding its electron structur.
he then goes on to say that according to Pauling,

the oxygen atoms are linkt by one
covalent bond & two three-electron
bonds :O—O:, & that this
formulation violates the octet rule.

o i don’t know hwat i am going to do.
spherical orbitals, dumbell orbitals,
& now am sinking into the morass of hybrid
orbitals, almost as ignorant as i was

hwen i began my quest for the cause of color.
Henry Miller said that he had an advantij over
most men in that he knew he was his own savior.
yeah, well, Robert the self-savior romping on.

here we are, all very happy now,
& in my dreams oxygen is blue.
& John Bartram said that the Valley was
the Eden of eastern north america.

was, & weep waterfalls.

Calvin in his memoir says Lewis
had written a chaptr on color in his book
Atom and Molecule many years earlier,
in hwich the basic ideas are already exprest.

i believe Calvin has conflated Lewis
paper “Atom and Molecule” (1916)
& his book Valence and the Structure
of Atoms and Molecules (1923).

i believe in the paper Lewis said
the atom tends to hold an even
number of electrons in the shell,
& in his book he had a chaptr on color.

i hav at last found out hwat Lewis said:
paramagnetism & color can usually be
associated with unpaired electrons.

the Scots chemist A. S. Couper thought of
valence bonds & wrote the formula for methane.
then 16 years later the 22-year-old
Dutch chemist Jacobus Hendricus

van’t Hoff said sum properties coud be
explaind by the four bonds directed toward
the corners of a tetrahedron with the
carbon atom at the center. that was

the beginning of structural chemistry.
Cooper’s editor delayed publication of
his paper & Kekulé got priority
& Couper sufferd a breakdown in health.

be grateful that Linus Pauling rememberd him.

if we look at Hofmann’s progression
from methane to CH3Cl this means
that electronegativ chlorine has been
substituted for electropositv hydrogen.

chlorine has seven electrons in its valence shell
this means that the one odd electron
is free so to speak & it is farthest
from the nucleus & so least bound

& that electron forms a covalent bond
with carbon & attains to the octet of nirvana.

i hav been meditating on the ammonium ion
for sum time now. it is represented as
four hydrogen covalent bonds with central
nitrogen atom & overall valence +1.

this doesn’t make a hol lot of sense to an amateur
because nitrogen has five electrons
in its valence shell so if anything
the overall charj should be negativ but it’s not.

i used to say that gunpowdr got me high
maybe it’s that positiv ion
i remember throwing ammonium nitrate
under the sweet potatoes watch out for copperheads
it was hot & sweaty & not nearly as much
fun as gunpowdr.

a hydrogen proton combines with the lone pair
that is to say
both electrons are supplied by the nitrogen
so it isn’t strictly speaking a co-valent bond
it is a dativ bond.

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