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mewrox99
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Iodoform
Hi Chemists.
I haven't really dabbled much in organic. But I am aware of the haloform reaction and would like to try it out.
I've seen a video on making Iodoform and it seems very easy, but I have some questions.
http://www.youtube.com/watch?v=XoG-suAkI68
1. How do I dispose of the Iodoform. Is there anyway to convert it into safer products
2. How toxic are the vapors? If I work out in the backyard without a mask will I expose my self to too excessive amounts
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Neil
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A good starting point in this journey is...
http://www.jtbaker.com/msds/englishhtml/i3480.htm
Brought to you buy the power of the all knowing all crawling Google bots.
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mewrox99
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Yes, I read the oxford university MSDS. I find the JTBaker ones a bit overzealous and I'm sure the safety officer at one of the world's most
prestigious universities is reliable
In chemistry you need a balance from being overly scared of everything to make phosgene outside without a mask stupidity.
Anyway back to the reaction. One more question most of the texts I have read state to use I2 not his in situ I2. Is his fine
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woelen
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Why dispose of the iodoform? Keep this chemical, it is quite interesting on its own. I also made some and kept it. I have done some other experiments
with it, such as pyrolysing the material and doing some organic experiments with it in non-aqueous solvents.
It can be isolated easily, it simply drops out of solution and you can decant the aqueous layer from it and rinse another time with water. I then
extracted the material with diethyl ether and let the ether evaporate (outside, while there was a little breeze). The result is a nice glittering
solid.
I made a picture of this while it is in its vial.
The procedure, used for making the iodoform is the following:
Dissolve KI in dilute hydrochloric acid and add a slight excess of hydrogen peroxide. This results in formation of solid iodine.
Decant the liquid from the iodine and add water. Stir somewhat and decant again.
Add water again.
Now you have a suspension of iodine in water.
Add some acetone to this and mix well.
Finally, add just enough solution of NaOH, while stirring all the time, such that the brown color of the iodine just disappears. Add one or two drops
extra.
Allow the precipitate to settle.
You can do this synth at a scale of a few grams.
[Edited on 19-5-11 by woelen]
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The WiZard is In
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Quote: Originally posted by mewrox99  | Hi Chemists.
I haven't really dabbled much in organic. But I am aware of the haloform reaction and would like to try it out.
I've seen a video on making Iodoform and it seems very easy, but I have some questions. |
Wow Iodoform brings back a childhood memory —
STRICTLY GERM-PROOF
THE ANTISEPTIC BABY and the Prophylactic Pup
Were playing in the garden when the Bunny gamboled up;
They looked upon the Creature with a loathing undisguised;—
It wasn't Disinfected and it wasn't Sterilized.
They said it was a Microbe and Hotbed of Disease;
They steamed it in a vapor of thousand-odd degrees;
They froze it in a freezer that was cold as Banished Hope
And washed it in permanganate with carbolated soap.
In sulpureted hydrogen they steeped its wiggly ears;
They trimmed its frisky whiskers with a pair of hard-boiled shears;
They donned their rubber mittens and they took it by the hand
And 'lected it a member of the Fumigated band.
There's not a Micrococcus in the garden where they play;
They bathe in pure iodoform a dozen time a day;
And each imbibes his rations from a Hygienic Cup--
The Bunny and the Baby and the Prophylactic Pup.
Authur Guiterman
-------
Monograph Number: 0005033
Title: Iodoform
CAS Registry Number: 75-47-8
CAS Name: Triiodomethane
Molecular Formula: CHI3
Molecular Weight: 393.73
Percent Composition: C 3.05%, H 0.26%, I 96.69%
Literature References: Prepn from acetone, sodium hypochlorite, potassium iodide, and sodium hydroxide: Glass, Q. J. Pharm. Pharmacol. 8, 351
(1935); from chloroform + methyl iodide: Soroos, Hinkamp, J. Am. Chem. Soc. 67, 1642 (1945); by electrolysis: Glasstone, Ind. Chem. 7, 315 (1931).
Description of the iodoform reaction: Seelye, Turney, J. Chem. Educ. 36, 572 (1959). Toxicity study: Kutob, Plaa, Toxicol. Appl. Pharmacol. 4, 354
(1962).
Properties: Yellow powder or crystals; mp ~120°; dec at high temp with evolution of iodine. Unctuous touch; characteristic, disagreeable odor.
Volatile with steam. d 4.1. Very slightly sol in water. One gram dissolves in 60 ml cold alcohol, 16 ml boiling alcohol, 10 ml chloroform, 7.5 ml
ether, 80 ml glycerol, 3 ml carbon disulfide, 34 ml olive oil; freely sol in benzene, acetone, slightly sol in petr ether. LD50 s.c. in mice: 1.6
mmoles/kg (Kutob, Plaa).
Melting point: mp ~120°
Density: d 4.1
Toxicity data: LD50 s.c. in mice: 1.6 mmoles/kg (Kutob, Plaa)
CAUTION: Potential symptoms of overexposure are irritation of eyes and skin; lightheadedness, dizziness, nausea, incoordination, CNS depression;
dyspnea; liver, kidney and heart damage; visual disturbances. See NIOSH Pocket Guide to Chemical Hazards (DHHS/NIOSH 97-140, 1997) p 172.
Therap-Cat: Anti-infective (topical).
Therap-Cat-Vet: Antiseptic, disinfectant for superficial lesions and in the female reproductive tract.
[Dispose of it on your GF.]
Keywords: Antiseptic/Disinfectant; Halogens/Halogen Containing Compounds.
Whatever happen'd to — Mercurochrome.
I remember when you couldn't be a Boy Scout if you didn't have it in your first aid kit.
Monograph Number: 0005867
Title: Merbromin
CAS Registry Number: 129-16-8
CAS Name: (2¢7¢-Dibromo-3¢,6¢-dihydroxy-3-oxospiro[isobenzofuran-1(3H),9¢-[9H]xanthen]-4¢-yl)hydroxymercury disodium salt
Additional Names: [2,7-dibromo-9-(o-carboxyphenyl)-6-hydroxy-3-oxo-3H-xanthen-4-yl]hydroxymercury disodium salt; mercurochrome;
dibromohydroxymercurifluorescein disodium salt
Manufacturers' Codes: no. 220 sol
Trademarks: Chromargyre; Planochrome; Flavurol; D.O.M.F.; Mercurophage; Mercurocol; Gallochrome; Gynochrome; Mercurome; Asceptichrome;
Mercuranine
Molecular Formula: C20H8Br2HgNa2O6
Molecular Weight: 750.65
Percent Composition: C 32.00%, H 1.07%, Br 21.29%, Hg 26.72%, Na 6.13%, O 12.79%
Literature References: Prepd by treating dibromofluorescein with mercuric acetate and sodium hydroxide: White, J. Am. Chem. Soc. 42, 2355 (1920);
also prepd by the action of mercuric acetate on dibromofluorescein sodium: Rymill, Corran, Q. J. Pharm. Pharmacol. 7, 543 (1934), see also US 1535003
(1925).
Properties: Trihydrate, iridescent green scales or granules. Freely sol in water, giving a carmine-red soln. Very dil solns (1:2000) possess a
yellow-green fluorescence. pH of 0.5% soln: 8.8. One gram dissolves in 50 grams of 94% alcohol, in 8.1 grams methanol: Denoel, J. Pharm. Belg. 22,
423 (1940); 23, 75 (1941). Practically insol in alcohol, acetone, chloroform, ether. Incompat. Acids, most alkaloidal salts and most local
anesthetics. Colors the skin carmine-red. The stains may be removed by washing first with permanganate soln and then with oxalic acid soln.
Therap-Cat: Antibacterial.
Therap-Cat-Vet: Antiseptic.
Keywords: Antiseptic/Disinfectant; Mercurial compounds.
http://www.straightdope.com/columns/read/2518/what-happened-...
[Tincture of] Merthiolate —
Monograph Number: 0009317
Title: Thimerosal
CAS Registry Number: 54-64-8
CAS Name: Ethyl[2-mercaptobenzoato(2-)-O,S]mercurate(1-) sodium
Additional Names: [(o-carboxyphenyl)thio]ethylmercury sodium salt; sodium ethylmercurithiosalicylate; thiomersalate; mercurothiolate
Trademarks: Merthiolate (Lilly); Merzonin (Takeda); Vitaseptol (Faure)
Molecular Formula: C9H9HgNaO2S
Molecular Weight: 404.81
Percent Composition: C 26.70%, H 2.24%, Hg 49.55%, Na 5.68%, O 7.90%, S 7.92%
Literature References: Prepd by reacting ethylmercuric chloride (or ethylmercuric hydroxide) with thiosalicylic acid: Kharasch, US 1672615 (1928);
Trikojus, Nature 158, 472 (1946); Swirska et al., Przem. Chem. 39, 371 (1960), C.A. 55, 3507a (1961). Toxicity: Mason et al., Clin. Toxicol. 4, 185
(1971). Review of health effects from vaccine exposure: M. Bigham, R. Copes, Drug Saf. 28, 89-101 (2005).
Properties: Cream-colored, crystalline powder. Stable in air, but not in sunlight. One gram dissolves in about 1 ml water, in about 8 ml alcohol.
Practically insol in ether and benzene. Stabilization of solns with EDTA: Davisson, US 2864844 (1958 to Lilly). pH of 1% aq soln: 6.7. LD50 s.c.
in rats: 98 mg/kg (Mason).
Toxicity data: LD50 s.c. in rats: 98 mg/kg (Mason)
Use: Pharmaceutic aid (preservative).
Therap-Cat: Anti-infective.
Therap-Cat-Vet: Antibacterial, antifungal (topical).
Keywords: Antiseptic/Disinfectant; Mercurial compounds.
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mewrox99
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Just tried the synth.
Worked great, will upload a yt video later
Here is my product:
Has a real strong nasty mothball sorta odour and gave me a slight headache
Disposed of it by heat to decomposition, small batches at a time
[Edited on 22-5-2011 by mewrox99]
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woelen
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Nice to see that you succeeded in making this chemical.
Please post the exact procedure you have used, so that others also can learn from your interesting experience and can repeat the experiment.
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mewrox99
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I made it as per this youtube video
http://www.youtube.com/watch?v=XoG-suAkI68
I'm uploading my own video soon.
Here are my notes:
Sunday 22nd May - Synthesis of Iodoform
In a 250mL beaker, 12g of KI is dissolved in 100mL H2O
4mL of pharmacy grade propanone is added
150mL of 4% NaClO is added slowly
Initially brown iodine is produced, but this rapidly reacts with the propanone via the haloform reaction to form a yellow precipitate of Iodoform
The solution was left to settle for ca. 10mins
The solid has separated as a big clump at the bottom and filtering is not needed
Iodoform has a sharp mothball like odor that is hard to describe.
When heated strongly with a propane blow torch, Iodoform rapidly decomposes into Iodine and Carbon. It also melts into a red liquid. I do have my
concerns about toxic organoiodine compounds, but under extreme heat they SHOULD decompose into elemental iodine and HI. As far as I know there is no
risk of a halocarbonyl being formed due to the instability of I2C=O. The oxford msds mentioned an explosion hazard of heating iodoform so it is
important to be cautious. The decomposition appeared exothermic.
My iodoform was desposed of by cautious heating to thermal decomposition
AN IMPORTANT WARNING:
Iodoform has CNS effects and special care should be taken to avoid its vapors. I got a sharp but short lasting headache from it
EDIT: Here is my video on Iodoform 
http://www.youtube.com/watch?v=vyQmF08tSFY
[Edited on 23-5-2011 by mewrox99]
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woelen
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What you made almost certainly is not pure iodoform. I now clicked the image to see more detail in it, but normally iodoform does not appear in this
form. It appears in the form of many beautifully glittering yellow crystals and the type of yellow color also is more intense.
The headache you had might be due to the iodoform, but I suspect that it at least partly is due to breathing of chloroform.
You added bleach to a solution of KI + acetone and you had quite some excess acetone. Now think of what happened. Part of the bleach indeed oxidizes
iodide, forming iodine and/or hypoiodite. The alkaline properties of the bleach then allow further reaction and the iodoform is formed. BUT... there
is a side reaction. At least part of the bleach will react directly with acetone, giving another haloform reaction. Chloroform is formed as well. And
I can imagine that also mixed products are formed being CHClI2 and CHCl2I. The chloroform is a liquid and when mixed with the iodoform it makes a
clump which contracts and becomes sticky. The mixed products also could add to this clump-formation and also might make the material look somewhat
lighter.
You could try to repeat the experiment as follows:
Dissolve the KI in water
Add some dilute acid (assure there is excess acid, either H2SO4 or HCl or HNO3, does not matter)
Add just enough bleach for complete oxidation of all iodide to iodine. Do not add too much bleach, because that will result in further oxidation of
the iodine to iodate. It is better to have a slight excess of KI than an excess of bleach.
Add acetone to the still acidic solution.
Slowly pour solution of NaOH into the solution and stir and keep on adding NaOH until the liquid becomes slightly alkaline.
Now you will see precipitation of the CHI3, it will be more golden yellow and it will form a fine powder or even nice glittering crystals.
The smell will be different, it does not smell like mothball, but it has the typical hospital smell.
Just try it on a small scale.
Why do you use such large quantities of chemicals? I think 12 grams of KI is quite a lot. An amount of 1.2 grams also does the job, especially if you
do not intend to keep the result of your synthesis but instead destroy it. Using smaller quantities results in less cost, less waste and less risk in
destroying stuff after the experiment.
I would feel quite uncomfortable if 5 to 10 grams of some (for me) uncommon compound starts decomposing exothermically and gets out of control. If
only appr. 0.5 grams do the same, then I just would put the test tube in a sink and allow it to roar at me for a few seconds until it dies ;-)
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mewrox99
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Ok. Moral of the story, follow a proper textbook rather than someone kid on youtube's synth.
Also since i heated the iodoform i probably got some phosgene :O
It's been 26hours with no symptoms
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mewrox99
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This is scaring me and I'm having a panic attack.
Do you think i breathed in a dangerous amount of phosgene, It's been 26hours no symptoms
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woelen
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Please read my U2U. No, there is no need to panic!
And yes, some kid with a kewl video on YouTube is not a proper source for information about potentially risky syntheses. In this case you need not
worry about your health, but of course, things can turn out less pretty with other syntheses.
There simply is too much crap on YouTube. Only a few channels have good information and most of these good channels are from sciencemadness members
And no, I do not have a channel on YouTube, I have enough work with my own website.
[Edited on 23-5-11 by woelen]
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Jor
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Please tell me how you get phosgene by heating iodoform
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mewrox99
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@jor it had chloroform in it
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Jor
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You mean as a byproduct of the reaction? If you filtered and dried it properly, it should be free of chloroform. On the phosgene: heating chloroform
in glass from below will simply produce chloroform vapours, not phosgene. Unless you direct the flame directly on the vapours or strongly heat the
vapours.
What I don't understand is why you destroy the iodoform after you have made it.
And there is no need to panic attack. Unless you get in pain the chest and/or difficulty breathing I would not worry.
And even then the difficulty breathing might be a mental thing  . I exposed
myself to a LITTLE bromine (just smelling it) the first time I made it. Then I started thinking about every breath I took and tried to breath in very
deeply. Then you will get the impression you can't breath properly Quite funny,
as other one other time I overexposed myself to bromine (this was my only overexposure to an acute poison in my almost 5 years of home chemistry, when
I didn't have a fume hood). This happened when I was making it outside, and my sense of smell was lost, and there was slight irritation all the time
(for IIRC 30-45 minutes). So I would guess this was an exposure level of about 5ppm. Left me with a light pain in the chest for the evening wich
dissappeared after sleeping.
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woelen
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If you read how mewrox99 made the CHI3, then you imemdiately see how it can be contaminated with CHCl3. If this synthesis is done in the proper way,
then no CHCl3 will be formed at all.
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Jor
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Yes sorry, my mistake. I guess I read it too fast and skipped over the chloroform part 
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mewrox99
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its morning now and i'm fine. At the time of my last post it had been 32 hours after exposure not 26. Now its 40hours and i havent coughed so im def.
fine. Given also i decanted the iodoform and made sure it was almost completly dry. the amount of CHCl4 would be neglible
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The WiZard is In
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| Quote: Originally posted by mewrox99 | This is scaring me and I'm having a panic attack.
Do you think i breathed in a dangerous amount of phosgene, It's been 26hours no symptoms |
If you die — can I have your chemistry set?
If you want to know how a chemist would make idoform —
Vogel's Practical Organic chemistry has it laid out step by step.
You can DL it from the forum's library.
"If you download only one book of practical organic chemistry,
make it this one. It is a classic of laboratory chemistry, well-suited
to the advanced home experimenter."
Being an Analogue person I just purchased a copy of the
3rd ed. US $19.95. I sold another one of the children for medical
experiments so I have a few spare bucks to spend on books &c.
Phosgene. Ye old EB Vedder The Medical Aspects of
Chemical Warfare 1925 sez.
... the results of gassing are more insidious in their action. [Compared to chlorine.]
"After the second or third day if death has not occurred,..."
you still have to pay your credit card bills.
One of quickest easiest ways of producing phosgene is with
carbon tetrachloride and hot metal. In my youth all NYC
subway cars had CCl4 fire-extinguishers....!
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Jor
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''One of quickest easiest ways of producing phosgene is with
carbon tetrachloride and hot metal. In my youth all NYC
subway cars had CCl4 fire-extinguishers....!''
Even more easy is heating a mixture of a dichromate in conc. H2SO4 and chloroform. The gas simply bubbles out of solution, below the boiling point of
the chloroform.
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mewrox99
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Just under 48hours with not a single cough. I'm fine
I looked it up, Phosgene takes no longer than 48hours to take effect with most symptoms usually occurring within 12hrs after exposure,
@Jor
Is that what myfanwy94 did
[Edited on 23-5-2011 by mewrox99]
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Jor
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Now that I think of it, I read on wikipedia that phosgene reacts with sulfur dioxide to form thionyl chloride and carbon dioxide. Now this is very
interesting as phosgene is so easily produced. I recently bought a lot of glassware, so I might be able to do this on a small scale.
My idea, generating phosgene from chloroform in a SMALL apparatus (such there is very low space volume except for the liquids, meaning that little
phosgene just hangs around in the apparatus making opening the apparatus after the rxn a hazard), and leading it into ice cold xylene (or toluene, but
seperating the SOCl2 might be hard). There will have to be a tube from this leading into ammonia.
Next take this solution in a 3-neck with a condensor and CaCl2-guard and bubble in dry SO2 dried with H2SO4. Boil the solution briefly to eliminate
all excess COCl2 from the system, during this step I will put a large dish containing hot ammonia in the hood so most COCl2 will leave as urea.
A few question though:
-Does anyone have a reference how fast this reaction with SO2 is? Do they also react in the gas phase? I don't want the bubbling into the xylene cause
COCl2 to leave unreacted, wich would mean dimished yeilds and phosgene release. If they react in the gas phase, the SOCl2 will condense and drip back.
-Besides from CaCl2 in the guard tube in the condensor, is there a solid wich I can also put next to the CaCl2 (with cotton in between) wich will
effectively remove all phosgene from the exit stream? I was thinking some solid alcohol, but I don't have any. Will tartratic acid or malic acid do
fine?
-Does the reaction also work with Na2SO3 anhydrous? This is much more convenient than bubbling SO2 in the liquid, wich will cause excessive
evaporation of SOCl2 and some COCl2.
Ofcourse if I do this I will do it in my hood at full power and sash down. Besides, when I open the apparatus, I will boil a dish of ammonia just
below the duct to destroy all phosgene so hardly any is release in the air outside. And I will wear a wetted (with water or maybe 10% EtOH) powder
mask (how do you call it in English  ) around my mouth. Maybe overkill, but this
gas is so lethal that I can't take risks.
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ScienceSquirrel
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You should not consider making and reacting phosgene without a schlenk line, gas scrubbers, an efficient hood, gas testers and all the other gear that
makes really nasty chemistry safe in a professional environment.
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mewrox99
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I thnk you should make a difrent thread for that. So just to confirm 44 hours and nothing means im fine? I also forgot 2 mention that after heating it
with the blowtorch there was some mess on the pan. I cleaned it with a paper towel and burnt said paper strongly with the bt. I hope that doesnt
change anything. I have NO symptoms but still concerned. Should i get my lungs x-rayed?
[Edited on 24-5-2011 by mewrox99]
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Sedit
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Jor please do make another thread for that and if possible leave the title open for other Sulfur halide synthesis
I really want to try my hand at SO2Cl2 synthesis some time and it would be great to see some other synthesis for these form of materials. I recently
found a patent that makes it seem as simple as feeding SO2 and Cl2 into Ethylacetate solution as a catalyst. My computer is crashed so Ill have to
look for it again but it should be no problem.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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