Author Topic: Synthesis of chromic acid  (Read 99 times)

reDEEMed

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Synthesis of chromic acid
« on: July 19, 2011, 10:21:59 PM »
I'm having a really hard time locating relevant refs for this procedure. I am interested in using potassium dichromate and concentrated H2SO4. I know the problem is I don't yet understand the more subtle language used in theoretical write ups and even patents. I really don't have an aversion to reading, I just can't find what I need to read. I did UTFSE and not surprisingly the thread about Caro's acid is the only one that showed a hit, even though the word chromic only appears in an old rhodium document about Caro's acid, the author's name was Chromic. It is sheer coincidence that Caro's acid and chromic acid are somewhat used along the same lines as a strong oxidizer.

I found this, but would still appreciate any advice or critiques of these methods as none of them make use of the chemicals I have.
Quote
The Preparation Of Chromic Acid

Chromic acid (H2CrO4) is produced by two or three methods. In one, 2 parts (by measure) of a cold saturated solution of bichromate of potassia are mixed with 3 parts of sulphuric acid: on cooling, the chromic acid is deposited in crystals, The mother liquor being then decanted. Perhaps the method of producing chromic acid more generally followed commercially is to decompose chromium sulphate with lime and to heat to redness the resultant paste of lime, gypsum, and chromium oxide. The chromate of lime formed is treated with sodium sulphate to yield soluble sodium chromate and gypsum. The addition of sulphuric acid liberates the chromic acid. A less wasteful process than this is the electrolytic one now being worked in Germany by Lucius & Bruning. In a solution of chromium sulphate in sulphuric acid are immersed both lead anode and lead cathode, chromic acid being liberated on the former and hydrogen on the latter. A current at 3'5 volts with a current density of 300amperes per square metre is required, the cells being at the temperature of 50° C. (122o F.).


Source hxxp://chestofbooks.com/crafts/mechanics/Cyclopaedia/The-Preparation-Of-Chromic-Acid.html

The wiki article on chromic acid says I should be able to obtain my acid by reaction of a dichromate with sulfuric acid. I see no mention of that in the previous methods.

From the wiki on chromic acid
Quote
The term chromic acid is usually used for a mixture made by adding concentrated sulfuric acid to a dichromate, which may contain a variety of compounds, including solid chromium trioxide. This kind of chromic acid may be used as a cleaning mixture for glass. Chromic acid may also refer to the molecular species, H2CrO4 of which the trioxide is the anhydride. Chromic acid features chromium in an oxidation state of +6 (or VI). It is a strong and corrosive oxidising agent.
Source hxxp://en.wikipedia.org/wiki/Chromic_acid

I wish I had more refs to post and all that to prove that I've been searching and reading, but none of them give me the most basic answer, how do I make it, even theoretically. It's very frustrating because I have this idea that is all my own at this point but the hard part is hunting down the refs to put together the pieces I need to actually do the reaction. I have no problem spending a month or more doing something like this especially when it's my own idea. That does a lot for a newbie's confidence level. But, it gets tiresome searching day after day and the refs are just not there, yet I know they have to be somewhere, chromic acid was once upon a time a very common cleaning agent. The chemicals I have for this sythesis weren't exactly cheap, so I don't fancy blind experimentation, although I feel myself moving closer to that.

I know some of you feel telling me anything is spoon feeding me. This simply isn't true. Once I get this acid I have other things to find/synthesize before I can even test my idea which may not even work. I'm busting my ass here trying to not ask for hand outs, but I'm stuck. What would even be preferable to an answer is pointing me in the direction of an information source that I could lean on when I do have questions like this.

Any help is greatly appreciated and I am willing to conform to any standard of behavior necessary to get help from you guys. I have a ton of respect for some of you and to be taught by you is an honor and one that I very much appreciate.
« Last Edit: July 19, 2011, 10:36:15 PM by reDEEMed »
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Sedit

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Re: Synthesis of chromic acid
« Reply #1 on: July 19, 2011, 10:48:44 PM »
Its the hydrolysis product of CrO3, very very nasty stuff I would advise against at all cost.

http://en.wikipedia.org/wiki/Chromium_trioxide

Death from cyanide is quick, this will let you know you where exposed 20 years from now when cancers and other health issues wreak havoc on your body.
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akcom

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Re: Synthesis of chromic acid
« Reply #2 on: July 19, 2011, 10:53:38 PM »
Quote
Chromic acid (H2CrO4) is produced by two or three methods. In one, 2 parts (by measure) of a cold saturated solution of bichromate of potassia are mixed with 3 parts of sulphuric acid: on cooling, the chromic acid is deposited in crystals
this must be from an old article because the language is pretty out there.  bichromate of potassia = potassium dichromate.  Usually they refer to parts as by weight.*  This is a pretty useful oxidizing agent and not particularly dangerous considering its made and used in orgo1 labs in universities around the US.  As with any other reagent, take the necessary precautions with handling and don't be dumb. 

edit: *my mistake, "by measure" means by volume.  I'd prepare the the cold saturated solution by preparing a saturated RT solution, then chilling and scratching the flask to precipitate out the excess, then decant the liquid for measurement.
« Last Edit: July 20, 2011, 01:56:14 AM by Enkidu »

reDEEMed

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Re: Synthesis of chromic acid
« Reply #3 on: July 19, 2011, 11:57:49 PM »
akom, the language seemed pretty 19th century to me too, which is what put me off about it. I have no direct experience to draw from, so my agreement about handling safely and not being dumb is strictly by gut feeling, but I do tend to think that this once common acid can synthesized and handled safely. Especially in the small quantities I'll be working with.

Sedit, is it the finished product, the acid, you are concerned about or the chromium trioxide? Perhaps there is another way to my eureka, infact, I know there is, but I already have the K2Cr2O7 and H2SO4.

Perhaps I will look into other oxidizers. But, I still would like to follow through here if at all possible if nothing else, I will learn something. I may already have the stuff to go an alternate route, that's what sucks about just learning.

Thanks for the replies.
"Ego is a structure that is erected by a neurotic individual who is a member of a neurotic culture against the facts of the matter. And culture, which we put on like an overcoat, is the collectivized consensus about what sort of neurotic behaviors are acceptable."
— Terence McKenna

akcom

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Re: Synthesis of chromic acid
« Reply #4 on: July 20, 2011, 12:24:51 AM »
If you can tell us what you're using it for, maybe we can help figure out the best way to circumvent the use of chromic acid.  Be aware that it is a very strong acid and corrosive to boot.  If you have a fume hood, use it.  Anything you drop this on will corrode.  If you get it on your gloves, change them immediately.

reDEEMed

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Re: Synthesis of chromic acid
« Reply #5 on: July 20, 2011, 01:38:55 AM »
akom, I deleted my reply because I think I found the info I need. I'm interested in the oxidation of aldehydes and ketones.

I found a pretty good paper about this, best one yet actually. That lead me to start looking at Jone's reagent. Is this what you had in mind Sedit? In case you guys are interested in seeing what I read, here's the link
http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/aldket1.htm

This term, Jone's reagent is what I've been looking for. I think I have my answer. This is what pisses me off. I know what I'm looking for is rather common knowledge to you guys I just have no idea how to search for it or ask about it.

This is most promising find yet, laughable to you guys I bet.
Quote
Jones Reagent

The Jones Reagent is a solution of chromium trioxide in diluted sulfuric acid that can be used safely for oxidations of organic substrates in acetone. The reagent can also be prepared from sodium dichromate and potassium dichromate. Jones Reagent is especially suitable for the oxidation of secondary alcohols to ketones and of primary alcohols to carboxylic acids and in a few cases to aldehydes (Jones Oxidation). Some alternative chromium reagents allow the selective preparation of aldehydes, such as PCC and PDC.
Source http://www.organic-chemistry.org/chemicals/oxidations/jones-reagent.shtm

PS So, those links will be automatically anonimized?
« Last Edit: July 20, 2011, 01:47:54 AM by reDEEMed »
"Ego is a structure that is erected by a neurotic individual who is a member of a neurotic culture against the facts of the matter. And culture, which we put on like an overcoat, is the collectivized consensus about what sort of neurotic behaviors are acceptable."
— Terence McKenna

Sedit

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Re: Synthesis of chromic acid
« Reply #6 on: July 20, 2011, 01:50:24 AM »
Yes, im not a fan of Hexavalance Chromium compounds, perhaps its due to working in the welding industry for so long and that every new site makes us watch safety videos including the dangers of Chromium but I avoid it at all cost.

Something about volatile toxic compounds rubs me the wrong way. Especially when I won't know if I have been exposed until years later sometimes. Just working with it would foul my nerves up with worry so bad it just wouldn't be worth it to me.
There once were some bees and you took all there stuff!
You pissed off the wasp now enough is enough!!!

reDEEMed

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Re: Synthesis of chromic acid
« Reply #7 on: July 20, 2011, 02:05:55 AM »
Well, I do appreciate being reminded of specific hazards, thanks.

If it's any consolation, I have found that googling "oxidation of aldehydes and ketones filetype:pdf" to be my lucky query. Narrowing it down to pdf's only has done wonders (so it seems at this point). Figures I would bang my head against the wall and do fruitless search after fruitless search, then break down and ask here only to find a good hit right after. However, I'm not so sure I would have found it had you not brought up chromium trioxide, which in a round about sort of way lead me to where I am now.

One thing I notice, and enjoy, about this chemistry hobby so far is that you are forever looking for a work around. I do enjoy the challenge. In fact this whole quest is a work around. Now it looks like I'm going to be working around my work around lol.

Thanks for the input, guys. I think I might actually have a specific question about the next time I post about it.
"Ego is a structure that is erected by a neurotic individual who is a member of a neurotic culture against the facts of the matter. And culture, which we put on like an overcoat, is the collectivized consensus about what sort of neurotic behaviors are acceptable."
— Terence McKenna

reDEEMed

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Re: Synthesis of chromic acid
« Reply #8 on: July 20, 2011, 02:36:15 AM »
Okay, specific question already. I know I will know my answer after I read more but I would like to not waste time by thinking something is one way when I got it all wrong. What confused me from the start about using a dichromate and dilute sulfuric acid to oxidize aldehydes and ketones was I couldn't find any clue as to how much of these things I was using. I finally think I get it and just wanted to hear someone say I did get it or I'm off.

Someone else did throw me a bone yesterday and told me that the oxidizer power of potassium dichromate is K2Cr2O7 --> K2O + Cr2O3 + 3 O:  and that means that every mole of  K2Cr2O7 can oxidize 3 moles of whatever. That may not be the right way to say it, but bear with me please. So that gives me my amount for the K2Cr2O7, it would be 1:3 K2Cr2O7/ketone or aldehyde. Next problem is the acid, how much to use there. I could find no reference to a target Ph or any kind of amount really. Just now I was reading one of the pdfs I found and saw the H3O was listed as a hydrogen source and R source. Funny as it sounds I didn't know what H3O was, so I google that. Knowing what that is now my thinking tells me that H2SO4 can break down into two H3O for every molecule (even though apparently it doesn't) I should be able to go 1:2 water/H2SO4. What I'm reading though says the second dissociation of H3O is not complete usually. So I would have to use an excess of acid. Can I use too much? I dunno, something about that last part I just aint feelin' it. I think I got something mixed up somewhere.
"Ego is a structure that is erected by a neurotic individual who is a member of a neurotic culture against the facts of the matter. And culture, which we put on like an overcoat, is the collectivized consensus about what sort of neurotic behaviors are acceptable."
— Terence McKenna

Enkidu

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Re: Synthesis of chromic acid
« Reply #9 on: July 20, 2011, 02:45:00 AM »
If you're looking for the preparation of an inorganic compound, always check these books, which are available around the 'net.

Handbook of Preparative Inorganic Chemistry Vol 1 & 2- Brauer (1963)
(In your case) Inorganic and Theoretical Chemisty Chromium Compounds - Mellor
Inorganic Laboratory Preparations - Schlessinger (1962)
Inorganic Preparations - Henderson Fernelius
Inorganic Preparations - Walton
Laboratory Manual of Inorganic Preparations - Vulte and Neustadt (1895)
Laboratory Methods of Inorganic Chemistry - Biltz & Biltz (1928)
Modern Inorganic Chemistry - Butterworths (1975)
Practical Inorganic Chemistry - K. M. Dunaeva (1987)

Most of them have the preparation of CrO3.

===

using a dichromate and dilute sulfuric acid to oxidize aldehydes and ketones was I couldn't find any clue as to how much of these things I was using

As far as looking for the preparation of a carboxylic acid from an aldehyde, look through books like the following for various methods. As your interests branch out, your O. Chem. folder will be filled with books covering many specialized topics. When you want to start discussing oxidation of an organic compound using chromic acid or anhydride, please open a new thread. If you want to continue discussing the number of moles of O available, that's fine here. Jones related oxidize secondary alcohols to ketones, but AFAIK, no further.

*Comprehensive Organic Transformations. A guide to functional group preparations - Larock R.C. (1999)
Practical Methods of Organic Chemistry - Gatterman (1909)
Practical Organic Chemistry - Vogel (1974)
Practical Organic Chemistry, 5th Ed - Vogel (1989)
Synthetic Organic Chemistry - Wagner & Zook (1953)
Oxidations in Organic Chemistry - Hudlicky [1990]
Reductions in Organic Chemistry - Hudlicky [1984]
Laboratory Methods of Organic Chemistry - Gatterman (1937)
Edit: of course, March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, Sixth Edition
*My workhorse.
« Last Edit: July 20, 2011, 08:23:28 PM by Enkidu »