Sciencemadness Discussion Board

Mercury Acetate Synthesis

BlackDragon2712 - 23-12-2012 at 00:05

Hi! Well this is actually my first post so... xd
Anyway, going with the topic now.

I’m going to attempt this reaction in a close future so I need some advices, I’ve worked with some mercury salts before but still wants to hear someone else opinion.
I’ll begin with mercury metal and nitric acid as the following reaction:

Hg + 4HNO3 -> 2NO2 + 2H2O + Hg(NO3)2

I’ll add some copper (II) chloride that I must synthesize:

Cu + H2O2 + 2HCL -> CuCl2 + 2H2O

It’ll react with the mercury nitrate interchanging ions as the following equation:

Hg(NO3)2 + CuCl2 -> HgCl2 + Cu(NO3)2

Then I’m going to separate both chemicals by solubility as mercury chloride is soluble in ethyl acetate and copper nitrate is not, then in order to take the mercury chloride out of the solution once it was separated from de copper nitrate I’m going to add some benzene that is miscible in ethyl acetate and mercury chloride doesn’t dissolve very well in benzene.
Once I get my mercury chloride out of solution I will make it react with a solution of calcium (II) hydroxide prepared from calcium oxide and water:

CaO + H2O -> Ca(OH)2

Reaction with mercury chloride:

Ca(OH)2 + HgCl2 -> Hg(OH)2 + CaCl2

Since calcium chloride is very soluble in water at 0 Celsius and mercury hydroxide is not it will precipitate out. Once I get my mercury hydroxide I will make it react with glacial acetic acid to finally form my mercury acetate just as you can see in this reaction:

Hg(OH)2 + 2CH3COOH -> Hg(CH3COO)2 + 2H2O

Then I will dry my crystals and store my final product
I know that I’m losing a lot of product in the separation of the chemical, for example in the separation of the calcium chloride some mercury hydroxide stains in the solution, but well I think is better that nothing, I will be searching how to recuperate that anyway.

If there is a problem with this or an easier or safer way to make this please let me know, any information will be welcome so fell free to comment.

I will post some pictures or probably a video of my reaction if you're interested

Thanks

kavu - 23-12-2012 at 00:59

Well you can ppt "mercury hydroxide" from mercury nitrate solution with say NaOH, skipping most of the steps this way. Using poorly soluble calcium hydroxide with even more poorly soluble mercury(II)chloride I would bet that this proposed reaction is very hard (or impossible) to carry out:

Ca(OH)2 + HgCl2 → Hg(OH)2 + CaC2l

There is also another problem with this mercury hydroxide business. Mercury(II)hydroxide can't be isolated by treating an aqueous solution of Hg(II) ions with a base. Instead you will get a hydrated oxide HgO · 3H2O. Luckily this oxide dissolves in warm dilute acetic acid to give mercury(II)acetate.

Another possibility might be to try and dissolve mercury metal in a mixture of hydrogen peroxide and acetic acid.

[Edited on 23-12-2012 by kavu]

Poppy - 23-12-2012 at 07:12

Hydrogen peroxide is messy and dangerous. Adding a lil too much makes you solution Over react, spilling the precious mercury all around the basement.
Such diffult to measure reaction rates should never be attemp´t with precious metals.

BlackDragon2712 - 23-12-2012 at 07:56

Yep that's the reason I discard hydrogen peroxide, but well, thanks for the help anyway I think I'll try to oxidize it first an then add acetic acid

Poppy - 23-12-2012 at 08:26

Y'cud save the nitric acid stuff
Well if this is really Hg that you have, yoou can react sulfur with calcium hydroxide, then pour a little water over Ca(SH)2 and bubble escaping H2S gas into molten Hg which is covered by a little water. This should react vigorously, the product having a high surface area as a powder. Subsequent addition of acetic acid would then displace H2S.

Eddygp - 23-12-2012 at 08:29

Basically,
Hg(NO3)2 + 2NaOH = HgO·H2O + 2NaNO3

Then:
HgO + 2CH3CO2H = Hg(CH3CO2) + H2 (oops I think I forgot H2O2...)

kavu - 23-12-2012 at 08:40

Quote: Originally posted by Eddygp  

HgO + 2CH3CO2H = Hg(CH3CO2) + H2 (oops I think I forgot H2O2...)


More likely as follows: HgO + 2 HOAc → Hg(OAc)2 + H2O

[Edited on 23-12-2012 by kavu]

Poppy - 23-12-2012 at 08:45

Quote: Originally posted by kavu  
Quote: Originally posted by Eddygp  

HgO + 2CH3CO2H = Hg(CH3CO2) + H2 (oops I think I forgot H2O2...)


More likely as follows:

HgO + 2 HOAc → Hg(OAc)2 + H2O


and if HgS + 2 HOAc → Hg(OAc)2 + H2S goes wrong you can try lemon jiuce.

Eddygp - 23-12-2012 at 10:03

Quote: Originally posted by Poppy  
Quote: Originally posted by kavu  
Quote: Originally posted by Eddygp  

HgO + 2CH3CO2H = Hg(CH3CO2) + H2 (oops I think I forgot H2O2...)


More likely as follows:

HgO + 2 HOAc → Hg(OAc)2 + H2O


and if HgS + 2 HOAc → Hg(OAc)2 + H2S goes wrong you can try lemon jiuce.

Why...?

Random - 23-12-2012 at 11:11

if you are planning to use it for organometallic chemistry please think twice..

Poppy - 24-12-2012 at 06:04

Quote: Originally posted by Eddygp  
Quote: Originally posted by Poppy  
Quote: Originally posted by kavu  
Quote: Originally posted by Eddygp  

HgO + 2CH3CO2H = Hg(CH3CO2) + H2 (oops I think I forgot H2O2...)


More likely as follows:

HgO + 2 HOAc → Hg(OAc)2 + H2O


and if HgS + 2 HOAc → Hg(OAc)2 + H2S goes wrong you can try lemon jiuce.

Why...?


Not sure, lemon juice corrodes from rust to stones, having both HOAc and citric acid would buff the acid strenght

And you do not have to worry about costs. If you find a good tree you then have plenty of citric acid for "free"!

[Edited on 12-24-2012 by Poppy]

Eddygp - 24-12-2012 at 06:20

Ummmm, lemon juice contains ascorbic acid and citric acid, but not acetic acid in large quantities... Lemon would taste of vinegar then!

Poppy - 24-12-2012 at 07:09

Quote: Originally posted by Eddygp  
Ummmm, lemon juice contains ascorbic acid and citric acid, but not acetic acid in large quantities... Lemon would taste of vinegar then!


Mercury salad?
Lemon jiuce as a preferance of choice over citric acid, as for it contains ascorbic acid and other enzimes that might help digesting stuff.

Eddygp - 24-12-2012 at 08:01

Wait, what? Ummm, I don't see any relationship between that and mercury acetate synthesis.
To make mercury acetate, acetic acid will be needed. Why would you want a lemon???

Poppy - 24-12-2012 at 09:02

Personal experience with similar guys such as lead, shows that a lot of waste is accompanied in dissolving the metal.
Once you get Hg ions in solution, you can do whatever you want with them!!
Watch that multistep is wasteful, in fact it could not be worse than that.
Why all that lemon-phobia dude?
The guy is expecting to obtain such an ultra-pure sample of Hg acetate, though the procedure does not seem to provide any basis for such, IMHO

BlackDragon2712 - 18-3-2013 at 16:31

Thanks all for answering the question! the synthesis was made with a razonable purity and a middle good yield :D

Eddygp - 19-3-2013 at 00:55

I'm glad to hear that!

puzzled about reaction, also organometallicmercury?

quantumcorespacealchemyst - 13-12-2014 at 04:07

Quote: Originally posted by Poppy  
Y'cud save the nitric acid stuff
Well if this is really Hg that you have, yoou can react sulfur with calcium hydroxide, then pour a little water over Ca(SH)2 and bubble escaping H2S gas into molten Hg which is covered by a little water. This should react vigorously, the product having a high surface area as a powder. Subsequent addition of acetic acid would then displace H2S.


is this a serius reaction? does this actually occur?
also, what about organometallic mercury compounds? i read that methl,dimethyl mercury are real toxic/deadly, but realistically, being scientists and using judgement, what are the parameters of toxicity regarding other carbon/metal compounds containing mercury such as sandwich compounds? after all, there are organo, sulphur, mercury disinfectants still used in other countries. and finally what are the compound compositions, reactions to watch out for/be aware of regarding mercury such as when using organic solvents such as ether, and chloroform (this especially) in presence of acids/bases, aluminum (this especially, as NaOH, CHClX, Al, seems to give of COX2, i have noticed this with chloro and iodoform, so i am guessing that mercury will enter into reactions with a haloform end run, ie: hydroxide, haloform whwn in presence of an aluminum catalyst/or reactant, or mercury itself acting in that role.)

DrMario - 13-12-2014 at 04:53

Quote: Originally posted by quantumcorespacealchemyst  
Quote: Originally posted by Poppy  
Y'cud save the nitric acid stuff
Well if this is really Hg that you have, yoou can react sulfur with calcium hydroxide, then pour a little water over Ca(SH)2 and bubble escaping H2S gas into molten Hg which is covered by a little water. This should react vigorously, the product having a high surface area as a powder. Subsequent addition of acetic acid would then displace H2S.


is this a serius reaction? does this actually occur?
also, what about organometallic mercury compounds? i read that methl,dimethyl mercury are real toxic/deadly, but realistically, being scientists and using judgement, what are the parameters of toxicity regarding other carbon/metal compounds containing mercury such as sandwich compounds? after all, there are organo, sulphur, mercury disinfectants still used in other countries. and finally what are the compound compositions, reactions to watch out for/be aware of regarding mercury such as when using organic solvents such as ether, and chloroform (this especially) in presence of acids/bases, aluminum (this especially, as NaOH, CHClX, Al, seems to give of COX2, i have noticed this with chloro and iodoform, so i am guessing that mercury will enter into reactions with a haloform end run, ie: hydroxide, haloform whwn in presence of an aluminum catalyst/or reactant, or mercury itself acting in that role.)


I'll just chime in on the safety of mercury acetate: stay away from that motherfscker. It's only a tad less toxic than dimethylmercury. It's usually really good for murdering people, usually yourself.

I would feel extremely worried about using, or just having people use, mercury acetate in a research lab setting, let alone a home lab.

gdflp - 13-12-2014 at 08:25

Is it, I thought that mercuric acetate was of similar toxicity to other mercury(II) salts? http://www.sciencelab.com/msds.php?msdsId=9924614 I'm not saying it's a good idea to use an mercury salts in a home lab, but I didn't think it was on the level of dimethylmercury.

DrMario - 13-12-2014 at 08:51

Quote: Originally posted by gdflp  
Is it, I thought that mercuric acetate was of similar toxicity to other mercury(II) salts? http://www.sciencelab.com/msds.php?msdsId=9924614 I'm not saying it's a good idea to use an mercury salts in a home lab, but I didn't think it was on the level of dimethylmercury.


Mercury acetate is WAY more toxic than the inorganic salts. Different leagues of toxicity.

DrMario - 13-12-2014 at 08:59

For one thing, it's nearly as neurotoxic as dimethyl-mercury. Similarly to dimethyl-mercury, it's absorbed through skin. Of course, ingestion and inhalation are equally hazardous.

As a scarily neurotoxic compound, it'll fuck you up even if it doesn't kill you. It will fuck you up so badly that you wish you were dead.

S.C. Wack - 13-12-2014 at 09:34

I think you're confusing inorganic mercuric acetate with organic phenylmercuric acetate, which was actually widely used up to fairly recently, and so is never mentioned in the way the hazards and regulatory situation of lead paint are, like the mercury in fluorescent bulbs, savior of the world.

DrMario - 13-12-2014 at 14:12

Quote: Originally posted by S.C. Wack  
I think you're confusing inorganic mercuric acetate with organic phenylmercuric acetate, which was actually widely used up to fairly recently, and so is never mentioned in the way the hazards and regulatory situation of lead paint are, like the mercury in fluorescent bulbs, savior of the world.


I am aware of phenylmercury acetate. I was not confusing it with mercury acetate. I did a fairly deep study into the toxicity of dimethylmercury, and mercury acetate was cropping up in my document review, in scary fashion.


By the way, mercury acetate is just as organic as phenylmercury acetate.

dermolotov - 13-12-2014 at 14:18

Quote: Originally posted by DrMario  

By the way, mercury acetate is just as organic as phenylmercury acetate.


Definitively, of course.

Relatively, i would say that phenylmercury acetate is "more" organic (whatever the hell that means). I would imagine its absorption rate would be much quicker than HgAcO.

Remember not to play with organic mercury without proper (more than just gloves) equipment fellas!

S.C. Wack - 13-12-2014 at 15:04

Quote: Originally posted by DrMario  
By the way, mercury acetate is just as organic as phenylmercury acetate.


Bullshit.

Mercuric acetate is a salt. Organomercurials such as phenylmercuric acetate have C-Hg bonds. I wish you luck in providing references that puts soluble inorganic mercury salts such as mercuric acetate in the same league as organomercurials.

dermolotov - 13-12-2014 at 15:12

Quote: Originally posted by S.C. Wack  
Bullshit.

Mercuric acetate is a salt. Organomercurials such as phenylmercuric acetate have C-Hg bonds. I wish you luck in providing references that puts soluble inorganic mercury salts such as mercuric acetate in the same league as organomercurials.

Wouldn't this just be an argument on pedantries?

Hg(AcO)2. It is my guess that they would produce O-Hg bonds where as what you define as organohydroargentous would need an Hg-C bond.
Isn't it organic by virtue of the AcO?
Take Morphine for example... It is absolutely certain that freebase morphine is an organic molecule. Is morphine sulphate still organic? Is the sulphate organic?

gdflp - 13-12-2014 at 15:53

Mercury acetate is organic, but it's not an organomercury compound. There's a big difference between those two designations. Morphine sulfate is most certainly organic.

dermolotov - 13-12-2014 at 15:56

Quote: Originally posted by gdflp  
Mercury acetate is organic, but it's not an organomercury compound. There's a big difference between those two designations. Morphine sulfate is most certainly organic.

I felt like we all knew that but were just bickering for the sake of bickering... hehehe

S.C. Wack - 13-12-2014 at 17:44

Quote: Originally posted by dermolotov  
Wouldn't this just be an argument on pedantries?


No. And I'm not the one who started arguing. You cannot redefine organometallic. You will not find mercuric acetate, benzoate, whatever, listed in toxicology references or journals as "organic" mercury, just as you will not find phenylmercuric chloride listed as inorganic. You will find mercuric acetate listed under "inorganic" mercury.

Comparing mercuric acetate to morphine sulfate is...well I'm not going to argue on the internet with you. Mercuric acetate is not, never has been, and never will be organic.

BTW some years ago I made probably an ounce of the acetate with Brauer's method, taking no precautions of any kind, other than not eating it. And, my comment on toxicology references earlier would have been better phrased as a challenge to provide references showing that the acetate is more dangerous than the chloride, nitrate, and such.

Random - 13-12-2014 at 18:05

Definition says that organomercury compound contains C-Hg bond. End of story.

DrMario - 13-12-2014 at 21:41

Quote: Originally posted by S.C. Wack  


Bullshit.

Mercuric acetate is a salt. Organomercurials such as phenylmercuric acetate have C-Hg bonds.


You are right, mercury acetate is indeed a salt and doesn't have C-Hg bonds.

Back in those days when I was looking at various organic compounds containing mercury, mercury acetate popped up on my radar as being extremely toxic. Good for you for synthesizing an ounce of the stuff and keeping yourself safe. I am sure you used good lab practices and safety equipment.

Random - 14-12-2014 at 01:33

Mercury acetate is probably as extremly toxic as other soluble mercury salts.

forgottenpassword - 14-12-2014 at 01:53

Quote: Originally posted by DrMario  
Quote: Originally posted by S.C. Wack  
I think you're confusing inorganic mercuric acetate with organic phenylmercuric acetate, which was actually widely used up to fairly recently, and so is never mentioned in the way the hazards and regulatory situation of lead paint are, like the mercury in fluorescent bulbs, savior of the world.


I am aware of phenylmercury acetate. I was not confusing it with mercury acetate. I did a fairly deep study into the toxicity of dimethylmercury, and mercury acetate was cropping up in my document review, in scary fashion.


I used to work in an analytical laboratory where people routinely handled mercury acetate as part of some test. It was weighed out on a shared balance, without gloves, on a daily basis. If dimethyl mercury were handled in such a manner, everyone who worked in the laboratory would be dead. Your estimation of the toxicity of mercury acetate as being comparable to dimethyl mercury is well off.

Please provide the source for your claims. Either your source is in error, or your interpretation of it is in error.



[Edited on 14-12-2014 by forgottenpassword]

dermolotov - 14-12-2014 at 15:11

Quote: Originally posted by S.C. Wack  
No. And I'm not the one who started arguing. You cannot redefine organometallic. You will not find mercuric acetate, benzoate, whatever, listed in toxicology references or journals as "organic" mercury, just as you will not find phenylmercuric chloride listed as inorganic. You will find mercuric acetate listed under "inorganic" mercury.

Little argumentation, mate :). Just hoping for (as always) informative debate. Originally, I was just backing up Dr.M's view that it is considered somewhat organic.

Seeing the quotes below, it's hard to say that it is, now... I seemed to have defended it's organic nature by virtue of its toxicity. Noting its mild (in comparison to C-Hg bonded molecules) toxicity, it's nice to see that I was originally wrong.

I enjoy and appreciate the following two pieces of evidence, though:
Quote: Originally posted by S.C. Wack  
BTW some years ago I made probably an ounce of the acetate with Brauer's method, taking no precautions of any kind, other than not eating it. And, my comment on toxicology references earlier would have been better phrased as a challenge to provide references showing that the acetate is more dangerous than the chloride, nitrate, and such.

Quote: Originally posted by forgottenpassword  

I used to work in an analytical laboratory where people routinely handled mercury acetate as part of some test. It was weighed out on a shared balance, without gloves, on a daily basis. If dimethyl mercury were handled in such a manner, everyone who worked in the laboratory would be dead. Your estimation of the toxicity of mercury acetate as being comparable to dimethyl mercury is well off.


[Edited on 14-12-2014 by dermolotov]