Sciencemadness Discussion Board - Black humour (?) of Victorian chemists

Black humour (?) of Victorian chemists

Pumukli - 26-12-2018 at 11:08

I love reading the work of chemists of the 1800-ies. I found e.g. "porous plate" a few days ago.

Now I came across the following:

"The alcoholic solution, now deep-brown in colour, and smelling very strongly of hydrocyanic acid, was filtered from the potassium chloride, ..."

They were braves, weren't they? :-) And this man, J. William James Ph.D., F.C.S, University College of South Wales, Cardiff survived and published several other articles too. :-)

Sulaiman - 26-12-2018 at 12:56

I like that many substances were idntified by TASTE !

Pumukli - 26-12-2018 at 13:05

In the above article can be found the following too:

"Ethylic potassiocyanacetoacetate crystallyzes from 90 per cent. alcohol in long, colourless needles, which have a bitter taste."

:-)

I read more and more such articles and feel less and less guilty when can't resist the temptation to smell the products of my flasks. :-)

Ubya - 26-12-2018 at 15:32

in my highschool years a kid licked some yellow lead iodide that he spilled on the bench (classic potassium iodide+lead nitrate experiment), the lab supervisor was quite shocked, the kid must have been a time traveler from 1800

fusso - 26-12-2018 at 18:23

Quote: Originally posted by Pumukli

"Ethylic potassiocyanacetoacetate crystallyzes from 90 per cent. alcohol in long, colourless needles, which have a bitter taste."

So what actually Ethylic potassiocyanacetoacetate is?

UC235 - 26-12-2018 at 20:43

Quote: Originally posted by fusso

Quote: Originally posted by Pumukli

"Ethylic potassiocyanacetoacetate crystallyzes from 90 per cent. alcohol in long, colourless needles, which have a bitter taste."

So what actually Ethylic potassiocyanacetoacetate is?

I would assume the potassium enolate salt of ethyl cyanoacetoacetate. Contrary to the name, not containing KCN, merely an organic nitrile and probably not terribly toxic. Given that it is the salt of a strong base and weak acid, I am unsurprised that it is bitter, since it's aqueous solution would be alkaline.

happyfooddance - 26-12-2018 at 22:21

I taste nearly everything. No heavy metals, but organics, strong acids, bases, I've tasted nearly everything I've encountered.

Dilution is key.

Some flavor compounds will throw your head back faster than a strong mineral acid, if they aren't diluted. And some of them don't go away; piercing, agonizing bitterness... You wish you could throw it up, but it's just there, seeping through your tongue, around your cheeks, down your throat...

I don't see real danger in smelling small amounts of things like cyanide, either.

Like putting a small (10mg) spatula of KCN in a test tube with a few drops of acid.

Some would argue that that is a good way to find out if you can even smell cyanide, since if you can't smell it you are definitely at greater risk while working with it.

I mean, but what do I know? Everyone be safe

Pumukli - 27-12-2018 at 00:40

"So what actually Ethylic potassiocyanacetoacetate is?"

It is the following compound:

CNCH₂COCHKCOOEt

It is the potassium enolate salt of the ethylester of cyanoacetylacetic acid as UC235 wrote.

In those years the term "ester" had not yet been invented, they referred to the esters as "etheric salts" of the corresponding acid. Which makes sense, sort of. When they start mixing it abbreviated to "ether" then things start get confusing though. :-)

VSEPR_VOID - 27-12-2018 at 01:53

I dont think it would be that dangrous to taste most things. Just do it on the tip of your tong, then rinse it with water before putting it back in your mouth.

I recall a video where Cody drink a lethal dose of cyanide, along with the antidote.

j_sum1 - 27-12-2018 at 02:22

Nope. Cody drank a calculated sub-lethal dose. IIRC, around 1% of LD50.

mayko - 27-12-2018 at 07:24

If Merck is to be believed, chemists have sniffed (and lived to tell the tale) such substances as fluorine nitrate ("moldy, acrid odor"), chlorine trifluoride ("somewhat sweet, suffocating odor") and dimethylcadmium ("disagreeable odor")

nitro-genes - 27-12-2018 at 08:08

Always interesting to read the work of these early chemists, describing practical chemistry usually in a much more extensive way than nowadays, usually involving all senses in order to maximally experience the beauty of chemistry indeed!

(All of the below is bad lab practice, so ignore if you are offended by it)

Performed a steelwool/ethanol/HCl mediated reduction of 2,4 dinitrotoluene once... during the workup using sodium acetate neutralization and filtering, I noticed a slightly sweet taste in my mouth. After some searching, found an article describing the sweetness of 2-amino 4-nitrotoluene as 330 times as sweet as sugar.

After reading that, I just had to experience this for myself and tasted a few ug's on my tongue and washing it off immediately. (https://doi.org/10.1002/recl.19460650504), Most nitro amino benzenes are pretty toxic, so definitely not something to repeat! I was working cautiously and was wearing gloves at the time, though somehow a small droplet or aerosol still found it's way into my mouth...makes one think about the importance of a respirator.

Also took an extremely small wiff of hydrazoic once, just curious what it would smell like...it was very foul and almost metallic.. also noticed that the smell was immediately followed by a slight buzz in my head, maybe from bloodpressure change or just psychosomatic. If it was truly a physiological effect, it was unbelievably fast, considering it had to diffuse over my lungs, taken into the blood and excert the change in blood pressure!

Something more recent, while working with 2-amino 4,6 dinitroresorcinol and it's diazo derivative, I started noticing a slightly bitter taste in my mouth from just being in the same room as the drying compound. My best guess is that this is due to traces of 4,6 dinitropyrogallol, which can sublime....or maybe I imagined it...anyway since I couldn't find anything about the potential toxicity of any of these compounds I won't be working with this stuff anymore.

[Edited on 27-12-2018 by nitro-genes]

Abromination - 27-12-2018 at 18:16

I made small amounts of chlorine on accident during an experiment in 8th grade science. I asked my friend "Does it smell like chlorine in here to you" and he had the audacity to stick his head up to the reaction vessel and deeply inhale as a joke. He wasn't hurt seriously and walked away only with a raging headache, but this always reminded me of a victorian era chemist.

barbs09 - 28-12-2018 at 04:27

The misadventures of Earnest Glitch and his unfortunate lab assistant Hodges, in the following link poke a fair amount of satire at Victorian era science:

http://lateralscience.blogspot.com/2012/07/ernest-glitch.htm...

phlogiston - 28-12-2018 at 13:32

Still, considering they were able to discover things like thallium, phosgene, etc without killing themselves...
Not bad if you consider that the first person to prepare/isolate these substances, did so completely without advance warning of their dangerous properties.

Vomaturge - 28-12-2018 at 21:52

I would suppose the chemists searching for new unknown compounds had a bit more caution, although not necessarily enough...

Speaking of the odors of things you shouldn't be smelling, a week ago I had a somewhat relevant experience: I use a Thames & Kosmos C3000 chemistry set as part of an educational program. One of the experiments involves heating a few "small spoonfuls" (1 cc, roughly) of sodium hydrogen sulfate with a similar volume of salt to create hydrogen chloride, which is bubbled into water to make hydrochloric acid. They say to do it outside or by an open window. We put a fan in the window, before even lighting the spirit burner The fan cleared out most of the vapors which made it past the water, but then, when it was time to clean it up, I aired the apparatus out outside, as recommended in the book of experiments. It had a 20-30 ml test tube full of hydrogen chloride gas. Anyhow, as I was opening it 50 or 60cm from my face (and watching white drops of hydrochloric acid form from air humidity), the wind swirled and I got a whiff of it. It hurt my nose and made me cough, but didn't seem to have any smell. I'm sure the concentration was something that would be really hazardous if you breathed it for any length of time, which fortunately I didn't.

TL;DR I breathed some hydrogen chloride through my nose by accident, it didn't really have a scent so much as feeling...well, like my nose was getting acidified. Has anyone else noticed this about HCl, or is my nose just bad at picking up its scent?

[Edited on 29-12-2018 by Vomaturge]

happyfooddance - 29-12-2018 at 07:29

Quote: Originally posted by Vomaturge

TL;DR I breathed some hydrogen chloride through my nose by accident, it didn't really have a scent so much as feeling...well, like my nose was getting acidified. Has anyone else noticed this about HCl, or is my nose just bad at picking up its scent?

[Edited on 29-12-2018 by Vomaturge]

In high conc. HCl vapor is just smells like "choke and cough". The taste, too, of strong acids is hard to detect, it just tastes like sour as all hell. H2SO4 tastes a little more "plain", in a strange way, but they are all more sensation than actual flavor. I think this is probably related to what you experienced.

S.C. Wack - 29-12-2018 at 10:59

...read before the Cambridge Philosophical Society on April 19th, see their Transactions, vol. ix., part iii., p. 149

The substances isolated by Wood, Spivey, and Easterfield were passed on to me for pharmacological investigation.

...on the afternoon of Feb. 19th last, whilst engaged in putting up an apparatus for the distillation of zinc ethyl, I took from 0.1 to 0.15 gramme (from 1 1/2 to 2 grains) of the pure substance from the end of a glass rod. It was about 2.30 P.M. The substance very gradually dissolved in my mouth; it possessed a peculiar pungent, aromatic, and slightly bitter taste, and seemed after some time to produce slight anaesthesia of the mucous membranes covering the tongue and fauces. I forgot all about it and went on with my work. Soon after the zinc ethyl had commenced to distil — about 3.15 — I suddenly felt a peculiar dryness in the mouth apparently due to an increased viscidity of the saliva. This was quickly followed by paraesthesia and weakness in the legs, and this, in turn, by diminution in mental power and a tendency to wander aimlessly about the room. I now became unable to fix my attention on anything and I had the most irresistible desire to laugh. Everything seemed so ridiculously funny; even circumstances of a serious nature were productive of mirth. When told that a connexion was broken and that air * was getting into the apparatus and an explosion feared I sat upon the stool and laughed incessantly for several minutes. Even now I remember how my cheeks ached. Shortly afterwards I managed to collect myself sufficiently to aid in the experiment, but I soon lapsed again into my former state. This alternating sobriety and risibility occurred again and again, but the lucid intervals gradually grew shorter and I soon fell under the full influence of the drug. I was now in a condition of acute intoxication, my speech was slurring, and my gait ataxic. I was free from all sense of care and worry and consequently felt extremely happy. When reclining in a chair I was happy beyond description, and afterwards I was told that I constantly exclaimed, "This is lovely!"...

* Zinc ethyl takes fire on contact with air and consequently must be distilled in an atmosphere of carbon dioxide.

BY C. R. MARSHALL, M.B. VICT.,
ASSISTANT TO THE DOWNING PROFESSOR OF MEDICINE IN THE UNIVERSITY OF CAMBRIDGE.
Cambridge.
THE LANCET, JAN. 23, 1897.
235-238
THE ACTIVE PRINCIPLE OF INDIAN HEMP: A PRELIMINARY COMMUNICATION.

lordcookies24 - 6-1-2019 at 13:31

humphry davy was known for inhaling various gasses and taking notes of their effect. he loved nitrous oxide

Pumukli - 7-1-2019 at 12:19

Nice find, S.C.Wack! :-)

I found this today:

"The pure metanitrobenzoic acid melts at 145 C, from water it crystallizes in short needles, but by spontaneous evaporation of an alcoholic solution, it is obtained in yellowish, large, well-defined prisms or rhombic plates. The acid and its salts are distinguished by their intensely sweet taste, whilst its isomerids, in common with most nitro compounds, taste intensely bitter."
(P. Griess, Journ. pr. Chem, 2, VI, 384-389, in Journal of the Chemical Society, Abstracts, 1873, 26, 610)

I synthetised m-nitrobenzoic acid ethylester a few months ago. Maybe its time to hydrolize some. :-)

Pumukli - 26-1-2019 at 09:04

They could devote the proper ammount of time for a measurement:

"The ammonium nitrate used was purified as follows. Merck's extra pure reagent was twice recrystallised from conductivity water, filtered, and left on porous tile in a sulphuric acid desiccator for four days. The middle portion of these crystals was put in a Pyrex beaker, which was kept in an air oven at 120 C for four days. The solid was then finely powdered and kept in a shallow vessel over phosphoric oxide under vacuum for a year."

(The decomposition of ammonium nitrate by Madhavlal Sukhlal Shah and Trambaklal Mohanlal Oza, J. Chem Soc, 1932, 725. DOI: 10.1039/JR9320000725)

Hey, this is 1932, not really the Victorian era. But still.

Pumukli - 26-1-2019 at 13:50

I like very much reading the "obituary notices" of the (Royal) Chemical Society too. They are really valuable if you would like to learn more about those great chemists whose work we (amateurs) can replicate and maybe follow in a way or another.

Although mostly sad, sometimes they are humorous too. In that pleasant Victorian way.

Here are some examples:

"I consider that I received the most useful part of my chemical education in Muir's laboratory. He used to go away in the vacation and leave me with the laboratory boy, the keys, and a set of orders ready signed. My experience was that under this system I was able to do about ten times as much work as I was able to do in the splendid Strasbourg Laboratory. Muir was also very good in encouraging anybody with any chemical ideas to work in his laboratory; indeed I once assisted him in some work that he was doing himself, but nothing ever came of it."

Muir commenting on lab work of students:"...Of a student distinguished neither for clear thinking nor for tidy working, he observed 'brains in a muddle, place in a puddle.'"

" 'Patty' Muir was always a favourite as lecturer and demonstrator. His style was clear and forcible and his Scottish accent was marked when he was emphasising important conclusions. In his lectures, which were well attended, he was always at pains to take a broad view of the subject and to insist on principles rather than details. It is related that after one of his discourses the following lines were found on a scrap of paper left on a desk:

Here is a little lecturer

Quite of the smallest size.

Let's put him in a beaker glass

And bid him generalise."

Muir was also very friendly and approachable to the students:

"I first met Pattison Muir when I entered as a student at Cambridge, and worked in his laboratory during all the time I was an undergraduate. We soon became close personal friends and his house was always open to his students. ... The dons' wifes were always objects of terror to the undergraduate. Formal calls had to be made with fear and trembling. Pattison Muir's house was a real home to the shy undergraduate. ... He never lost his courageous grip on life and his capacity to meet old age and suffering with a bright, slightly amoused outlook both on himself and the universe. Of his home life I can only say that when I wrote to tell him that I was getting married he replied that no one knew what love really was until they had been married twenty years."

(M. M. Pattison Muir, 1848 Manchaster - 1931 Epsom)

unionised - 27-1-2019 at 02:57

Quote: Originally posted by Sulaiman

I like that many substances were idntified by TASTE !

A few are named because of their taste.
picric acid is named from the Greek pycros meaning bitter and, perhaps it'; just as well that beryllium is no longer named after the sweet taste of its soluble compounds.
"For about 160 years, beryllium was also known as glucinum or glucinium (with the accompanying chemical symbol "Gl",[68] or "G" [69]), the name coming from the Ancient Greek word for sweet: γλυκύς, due to the sweet taste of beryllium salts.[70]"
From WIKI

The alchemists used to refer to lead acetate as "sugar of lead" because it's sweet.
And, of course, there's saccharine.

AJKOER - 2-2-2019 at 08:39

Quote: Originally posted by unionised

..........
The alchemists used to refer to lead acetate as "sugar of lead" because it's sweet.
And, of course, there's saccharine.

Per the web (see https://www.google.com/search?source=hp&ei=6cZVXIvnEJLy5... ), to quote:

"Romans used an artificial sweetener, Sugar of Lead, to sweeten and preserve their foods without taking on additional calories. Sugar of Lead, likely the first artificial sweetener, is now known as the chemical compound Lead (II) Acetate, and it's a poisonous crystalline solid that resembles table salt."

And, like saccharine, both compounds where once viewed as likely harmless in moderation.

[Edited on 2-2-2019 by AJKOER]

unionised - 2-2-2019 at 09:39

Quote: Originally posted by AJKOER

And, like saccharine, both compounds where once viewed as likely harmless in moderation.

[Edited on 2-2-2019 by AJKOER]

The important distinction is that lead acetate is definitely rather toxic, and saccharin isn't.