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Author: Subject: Amateur/Home Chemistry: Historical Achievements
sparkgap
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[*] posted on 10-4-2008 at 23:58


franklyn,

As much as the tale warms the heart, alas! It looks to be spun yarn.

sparky (~_~)




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[*] posted on 11-4-2008 at 14:03


Quote:
Originally posted by Sauron
Shit! I post about Perkin, and no one has a word to say.
But David Hahn, a great exemplar of what NOT to do, that's a hot topic.


IIRC, Sauron, Perkin's discovery came about, in part, through the low purity of reagents available at the time.
This doesn't detract from his great achievement, in any way, since chemists other than Perkin would, in all probability, have simply dumped the products of all "failed experiments", without thinking.
What singled him out, was his great openmindedness coupled with a singlemindedness and great scientific curiosity.
At the time it was the right combination, and he had it!

'Don't think Hahn contributed anything to any science!

P
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[*] posted on 11-4-2008 at 17:42


I'm not trying to knock Perkin, far from it. However the fact remains that his lack of knowledge of structural chemistry led him into an erroenous synthetic strategy, which, along with the circumstances you mention, led seredipitously to a major commercial discovery. He was after indigo, right? He didn't get near it but he got something unexpected instead, something akin to Tyrollean purple.

Not bad for 18. What he did was screw up and come up fragrant.

Because of the economic impact on Britain, Perkin was lionized the rest of his life and beyond, and deservedly. And since his accomplishments were made under home-lab conditions his story ought to be at the vanguard of our struggle.




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[*] posted on 11-4-2008 at 18:13


Wasn't it him (or Fisher?) who had a reply to the smartasses that accused him of having luck to discover serendipitously: "My friend, I do more experiments than you."


:D:D:D

To stay on the topic, Traugott Sandmeyer did experiemnts in his kitchen, he discovered Sandmeyer reaction in 1884, he never took a doctorate degree.

[Edited on 12-4-2008 by Sandmeyer]




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[*] posted on 11-4-2008 at 20:36


Quote:
Originally posted by Sauron
I'm not trying to knock Perkin, far from it. He was after indigo, right?


I think it was quinine. He was not looking for a dye, so that part was not at all in the plan. He was, however, explicitly trying to find a way to get rich, so that part went exactly as intended. :)
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Sauron
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[*] posted on 11-4-2008 at 23:10


See the following excellent webpage.

http://www.ch.ic.ac.uk/motm/perkin.html

Contrary to what I had read, Perkin's mauvine was not 6,6'-dibromoindigotin at all. What Perkin made accidentally in 1856 and commercialized a year later was far more complex. Indeed, it was quinine he was after, and he was experimenting with oxidizing allytoluidine with dichromate. The correct structure for what he made (which turned out to anyway be a mixture) was not determined until 1994. See reference cited in site above.

Perhaps Perkin made Tyrian purple later. But it was not the foundation of his business and fortune. Mauvine was.

There is a lot of contradictory information about this on the net, but the page I linked to is by the well known chemist Henry Rzepa of the Imperial College of Chemistry, successor to the Royal College of Chemistry that Perkin attended in the 1850s.

As pointed out in this article, it is worth noting that my remark that Perkin knew nothing of structural organic chemistry, is accurate, but, no one did. The tetrahedran nature of carbon was not settled. Kekule only expounded his benzene ring theory in 1857. So Perkin's lack of such understanding was the general state of play in 1856. I meant no denigration by my comment.




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[*] posted on 12-4-2008 at 04:53


Quote:
Originally posted by Sauron
Shit! I post about Perkin, and no one has a word to say.


Perkin was in the forefront of my mind from my first glance at the thread title -- so much so, in fact, that I somehow convinced myself he'd been mentioned from the beginning! His story was certainly one of my biggest inspirations when I was first getting interested in chemistry. (In fact, I have a very clear memory of reading about his story while sitting at the base of our attic stairs -- in a house we left less than two years after I got my first chemistry set. I would've been around 10 at the time.)

On the other hand, had I started out twenty years later (and were I twenty years younger), I have no doubt that Hahn's story would have been more compelling to me. :P
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[*] posted on 12-4-2008 at 05:17


No disagreement Sauron, you have it just about right!
Your mention of Kekule and serendipity got me thinking about the large number of fortuitous accidents in chemistry.
Some seem to have come about by a combination of a lack of information and poor standards of purity of the materials worked on.
Modern practice has virtually closed the latter avenue, however!
And Wohler's "Urea Synthesis" looks like serendipity, pure and simple.

P
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[*] posted on 12-4-2008 at 05:39


The door is not completely closed on serendipity. It wasn't that long ago that a new form of elemental carbon was first observed (the fullerenes) in the soot of an alectric arc from graphite electrodes. Electric arcs and graphite electrodes were not new. It was just that no one had ever looked at them the right way. I bet the people who discovered them were not expecting what they found.

Planning an experiment, expecting result A and getting instead result Z, is serendipity, at least when result Z is useful and/or interesting. The fullerenes were certainly interesting and it seems like they will be useful as well.'

Those guys got a Nobel for their troubles. Well, I guess a million bucks isn't what it used to be. But still.

Nothey didn't do it in a home lab. How would the politics of the discovery have proceeded, if they had? Derision most likely till some academic lab replicated the work and very likely, snatched the Nobel or at least shared it. Unfair? To be sure. If you think there's nothing political in the Nobels, ask Robert Gallo or the fellow at the Pasteur Institute that Gallo plagiarized.




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[*] posted on 12-4-2008 at 05:52
The Need for Skepticism


One of my first posts here _
An abridged excerpt of an editorial from Science ( 12 October 1962 )

The synthesis of xenon tetraflouride and related compounds makes
necessary the revision of chemistry textbooks. For about 50 years,
students have been taught that noble gases are nonreactive.
Millions have absorbed this dogma and parroted it back in exams.
The first evidence that xenon might participate in chemical
combination was obtained by Neil Bartlett, who suggested that
compounds of this type might be made. The ease with which XeF4 is
made and its properties are explored is almost shocking. One can
introduce the two gases into a simple system, heat the mixture
for 1 hour at 400º C, and observe the formation of crystals.
The essential ingredient in discovering noble gas compounds was
not money or equipment, but an idea.
There is a sobering lesson here, as well as an exciting prospect.
For perhaps 15 years, at least a million scientists all over the
world have been blind to a potential opportunity to make an
important discovery. All that was required to overthrow a
respected and entrenched dogma was a few hours of effort and
a germ of skepticism.

.
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[*] posted on 12-4-2008 at 08:07


Quote:
Originally posted by Sauron
Perkin knew nothing of structural organic chemistry, is accurate, but, no one did. The tetrahedran nature of carbon was not settled. Kekule only expounded his benzene ring theory in 1857. So Perkin's lack of such understanding was the general state of play in 1856.


I have a book re the history of chemistry, 'The Development of Modern Chemistry', by Ihde, a Dover book. It mentioned Perkin amongst many others. One of the most interesting things I got from reading that book, was that for a very very long time, the understanding of what made chemistry work the way it did (bonding geometry, physical chemistry, etc.) was nearly nonexistent. It is really remarkable how much was worked out when the understanding of the 'basics' was nearly zero.
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[*] posted on 13-4-2008 at 05:27


Some further wrinkes re Perkin and mauve:

These cadged from one of the dye chem books in forum library:

1. von Hoffmann, Perkin's professor, was on holiday at the time.

2. Perkin's experimental logic was that allyltoluidine has half the MW of quinine and both contain nitrogen so why not put two mols of the allyltoluidine together? So he heated this aniline derivative with potassium dichromate and conc H2SO4.

3. He noticed that the product was colored.

4. He decided to repeat the experiment with aniline rather than allyltoluidine. The result was a tar. However alcoholic extraction gave some colored product. This initially refused to crystallize.

5. Hoffmann returned from holiday and after hearing Perkin's report, advised him to chuck the intractible product away!

Perkin however persisted and eventually managed to crystallize the substance, naming it mauve. He and von Hoffmann commercialized it the following year by that name, while in Europe it was known as aniline violet or Perkin's violet. It was distributed as an alcoholic solution, and was too expensive for any application other than dyeing silk. Fortunately the silk industry took to it immediately.

Normally we would think that experimental focus would have been a virtu and likewise, one's teacher's advise is not to be lightly cast aside. In this instance a great industry arose from a refusal of both.




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[*] posted on 28-11-2008 at 21:06


Recently I finished reading the book "Thomas Edison, Chemist," 1971, by Vanderbilt. Although he did his work in large, well staffed laboratories at Menlo Park, NJ, and Ft Meyers, Florida, it was all his. So in some ways he was a "home chemist." He did remarkable work in the following fields: magnetic iron ore separation, Portland cement manufacture, Ni-Fe battery, synthetic organic chemicals, and rubber, as well as in those of his more well-known inventions.

Another home chemist of whom I was not previously aware is Christian Shonbein, a professor of chemistry at the University of Basel in Switzerland. One day in 1846 he was performing some experiments in the kitchen of his home. He accidentally broke a flask in which he was distilling a mixture of sufuric and nitric acids, spilling it all over the floor. He wiped up the mess using his wife's cotton apron. Then he washed the apron and hung it in front of the hot stove to dry. But instead of drying the apron flared up and disappeared. It had been transformed from cotton into guncotton-the base for smokeless powder. (paraphrased from "Giant Molecules," 1966, Life Science Library)
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hissingnoise
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[*] posted on 29-11-2008 at 05:44


Most chemistry hobbyists, I'm sure, can relate to that Schonbein anecdote (mentioned on a previous thread, btw) because as I read it originally, his wife had expressly forbade experimentation in "her kitchen", so he had to wait till she went shopping, or whatever women do when they go out.
Imagine his panic on seeing acids fizzling (and releasing NO2) all over the floor, as he scrabbled for a cloth to clean up.
Imagine, too, what might have happened had the apron not ignited in front of the stove.
The version I read ended with, "Schonbein's wife's comments were not recorded".
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hissingnoise
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[*] posted on 29-11-2008 at 06:02


While on the subject, Christian Friedrich's "Eureka euphoria" was quickly dissipated by an horrific series of explosions which cost many lives; lives that were lost to his new invention.
Again, his later despondency can only be imagined. . .
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[*] posted on 30-5-2009 at 21:19
Need Proof ?


http://www.yahoo.com/s/1078775

No real relation to chemistry per se , however it invokes events largely unknown
that mathematics can presage undiscovered chemistry, as the prediction of then
yet to be named " Prions " by mathematician John Stanley Griffith, nephew of
Frederick Griffith. http://www.absoluteastronomy.com/topics/Frederick_Griffith
" Transformation was first demonstrated in 1928 by Frederick Griffith in what is
today known as Griffith's experiment, he discovered what he called a transforming
principle, which is today known to be DNA."
( They exhibiit familial traits reminiscent of the swiss Bernoulli's )
http://www.biochemist.org/bio/02704/0033/027040033.pdf

Spongiform encephalopathy such as CJD, BSE, and " Kuru "
is now generally accepted as being the result of pathogenic proteins
( without infinitive proof however, some remain unconvinced of this )
http://en.wikipedia.org/wiki/Creutzfeldt-Jakob_disease
[ The prion exhibits at least two stable conformations. One, the native state,
is water-soluble and present in healthy cells. The other conformational state
is very poorly water-soluble. The CJD prion is dangerous because it promotes
refolding of native proteins into the diseased state, producing a self-sustaining
feedback loop in which the number of misfolded protein molecules will increase
exponentially. The process leads to a large quantity of insoluble prions in affected
cells. This change in conformation disables the ability of the protein to undergo
digestion, readily accumulating into protein aggregates. The mass of misfolded
proteins disrupts cell function and causes cell death. ]

Flash Video describes Prion transmission
http://www.1lec.com/Microbiology/Prion/index.html

http://en.wikipedia.org/wiki/Kuru_(disease)
" the disease spread easily and rapidly in the Fore people ( new Guinea ) due
to their endocannibalistic funeral practices, in which relatives consumed the
deceased "
http://www.as.ua.edu/ant/bindon/ant570/Papers/McGrath/McGrat...

The culprit
http://en.wikipedia.org/wiki/Prion
" mathematician John Stanley Griffith developed the hypothesis [ in a seminal
paper in Nature entitled Self-replication and scrapie] in 1967 that some
transmissible spongiform encephalopathies are caused by an infectious agent
consisting solely of proteins "

Self-replication and scrapie
Griffith JS.
Nature ( 2 September 1967 ) Num 215(5105) pgs 1043-1044
http://www.nature.com/nature/journal/v215/n5105/pdf/2151043a...
Num 17 on this list
http://www.ncbi.nlm.nih.gov/sites/entrez?db=pubmed&cmd=D...
unrelated other important work by Griffith
http://www.amazon.com/Mathematical-Neurobiology-John-Stanley...
http://tinyurl.com/n5gnc5

Controversy continues
http://www.wired.com/wiredscience/2007/01/what_really_cau

Contemporary Investigation
http://www.ncbi.nlm.nih.gov/pubmed/17085779?ordinalpos=1&...

.
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franklyn
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[*] posted on 26-10-2010 at 09:20



http://www.livescience.com/history/top-10-mad-scientists-1.h...
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[*] posted on 26-10-2010 at 09:45


Quote: Originally posted by The_Davster  
I am wanting to use this thread for the purpose of collecting a list of great historical achievements by those doing their work outside a 'formal research setting'




A text in the Tao Tsang, entitled Chen Yuan Miao Tao Yao Lueh (Classified
Essentials of the Mysterious Tao of the True Origin (of Things)), is attributed to
Cheng Yin. Although the text available to us in the Tao Tsang is probably mostly
of the + 8th or the + 9th century, the putative author himself may have been
responsible for the older parts of the book. It mentions no less than thirty-five
different elixir formulae which the writer points out to be wrong or dangerous,
though popular in his time. ....... The book also warns against a very interesting procedure, saying
that some of the alchemists had heated sulphur together with realgar, saltpetre
and honey, with the result that their hands and faces had been scorched when
the mixture deflagrated, and even their houses burnt down. This passage is of
out standing importance because it is one of the first references to an explosive
mixture, proto-gunpowder, combining sulphur with nitrate and a source of
carbon, in any civilisation. The book also gives a test for saltpetre. Exactly how
much of all this material goes back to the days of Cheng Yin himself is extremely
difficult to determine, but future research may be expected to throw more light on
the problem. In the meantime, having regard to the general pattern of
development of chemical knowledge and use of explosives, we place the
essential passages in the Thang period.

--------
Some discoveries that may have been Sun Ssu-Mo's are embodied in short
extracts quoted in other collections. For example, the Chu Chia Shen Phin Tan
Fa (see pp. 159, 197) appears to quote him as follows:

Take of sulphur and saltpetre (hsiao shih) 2 oz. each and grind them together,
then put them in a silver-melting crucible or a refractory pot (sha kuan). Dig a pit
in the ground and put the vessel inside it so that its top is level with the ground,
and cover it all round with earth. Take three perfect pods of the soap-bean tree,
[Gleditschia sinensis] uneaten by insects, and char them so that they keep their
shape, then put them into the pot (with the sulphur and saltpetre). After the
flames have subsided close the mouth and place three catties (lb) of glowing
charcoal (on the lid); when this has been about one third consumed remove all of
it. The substance need not be cool before it is taken out-it has been 'subdued by
fire' (fu huo ) (i.e chemical changes have taken place giving a new and stable
product).

Someone seems to have been engaged here about + 650 in an operation
designed, as it were, to produce potassium sulphate, and therefore not very
exciting, but on the way he stumbled upon the first preparation of a deflagrating
(and later explosive) mixture in the history of all civilisation. b Exciting must have
been the word for that.

Joseph Needham
Science and Civilistion in China
Volume 5 chemistry and Chemical Technology
Part III: Spagyrical discovery and Invention: Historical Survey, From Cinnabar
Elixirs to Synthetic Insulin
Cambridge at the University Press 1976


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[*] posted on 26-10-2010 at 14:23
lab chemists


in the book the history of chemistry.i read that as late as the 1800's i believe.some top chemists did not even believe in compound structure symbols and were quite satisfied with archived compounds and how to derive them like recipes.something science madness shuns.the ones who believed in the structures of atoms and such werent even in agreement with each other.the non believers actually had their own notion.most of them the first ones were backyard chemists.some were persecuted even as heretics.probably by the f.b.i.
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[*] posted on 26-10-2010 at 15:55
23 000 year ago fireworks


On account that the PDF of the complete article is toooo
big, I have just scanned this. Contact me if'n you want
the complete PDF, a bit over 2-Meg.



Paleo-fireworks.jpg - 240kB

[Edited on 26-10-2010 by The WiZard is In]
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[*] posted on 26-10-2010 at 18:05


2 megabytes is no longer a significant amount of information.
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[*] posted on 26-10-2010 at 19:11


Quote: Originally posted by Mister Junk Pile  
2 megabytes is no longer significant amount of information.



Upload size limit is 2MB. Image limit is 800x3000.

Dem's da rules here.

Say .... what is the relationship between sizeand a
significant amount of information?

E=MC squared. Do be - despite its brevity a SL of information.

This could be expanded to what happens to information in a
black hole and Hawking radiation......
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[*] posted on 26-10-2010 at 19:39


But of course. I was unaware of the upload limit, hence my remark. Still, the way you worded your sentence made it look like you thought it was "tooo big" (mainly b/c of the extra 'o').

Some people's minds are like black holes except they do not emit Hawking radiation. Information flows into them never to be regurgitated. Unless, of course, there is a big bang/crunch series. But still, the information is lost.

E = mc^2. What the hell does that even mean? Just because some supposedly smart guy made it up back in the 1800s doesn't mean you have to talk about it or that it's true. I saw it on a chalk board once and I thought it was about my favorite rapper: Dr. E MC square. Why would a "smart guy" from the 1800s copy off the greatest MCs of all time?

EDIT:

What is the relationship between ANYTHING and significance? A general consensus I would say. Otherwise, it can be given individual meaning. :cool:


[Edited on 10-27-2010 by Mister Junk Pile]
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[*] posted on 27-10-2010 at 10:54
Chloroform


In 1831 Dr. [Md.] Samuel Guthrie at Sackets Harbor, New York
reading of Dutch chemists synthesis of 'choric ehter' / 'Dutch
liquid' (ethylene dichloride) reacted ethanol with chlorinated lime
used as a disinfectant in his hen house, independently discovering
chloroform. (Chloroform was that same year synthesized by
the German chemist Justus von Liebig the French pharmacist
Eugène Souberinan all three by different methods.)

For the early history of chloroform as an anesthetic —

Linda Stratmann
Chloroform : The Quest for Oblivion
Sutton Publishing Company UK 2003

Not seen by me :—

Dr. Samuel Guthrie, Discoverer of Chloroform:
Manufacturer of Percussion Pellets, Industrial Chemist 1782-1848
Jesse Randolph Pawling

Memoirs of Dr. Samuel Guthrie and the History of the Discovery of Chloroform ...
O. Guthrie, Henry M. Lyman



djh
----
The worst one [accident] was from
putting his hand into a keg containing
four pounds of percussion powder and
cracking a piece of of it between thumb
and finger. The friction set fire to the
powder and the resulting detonation
resulted in terrible burns to his hand and
arm, and tore most of the skin from his
chest, neck and face.... Altogether Gurthrie
was involved in eleven major explosions,
and was often seriously burned.
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[*] posted on 11-11-2010 at 16:44


Quote: Originally posted by Mister Junk Pile  
2 megabytes is no longer a significant amount of information.

Depends on the information , read last paragraph here _
http://www.sciencemadness.org/talk/viewthread.php?tid=6299#p...

Who would guess the difference beyween an ape and a human is a floppy disk !

.
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