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Author: Subject: Sodium Ferrocyanide
chemkid
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Sodium Ferrocyanide

I think i found an OTC source for sodium ferrocyanide. Yellow prussiate of soda is the traditional name for sodium ferrocyanide. Kosher salt contains sodium ferrocyanide and salt (NaCl) and costs about a 1.50 a box (which is rather large). By dissolving this in denatured ethanol (or if you've got the money straight ethanol) i would think that the insoluble sodium ferrocyanide would precipitate and NaCl dissolve.

This is only speculation so far. I will try it in the morning.

I know sodium ferrocyanide can be used as an iron indicator. How exactly would such a test be performed?

Chemkid

[Edited on 30-12-2007 by chemkid]

pantone159
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I'd be kind of surprised if there was enough ferrocyanide to make it worth the trouble, but hey, give it a shot.

If you mix a solution of ferrocyanide with a solution of ferric Fe(III) ion, you get a very vivid, dark blue precipitate, "Prussian Blue". Although this is a solid, it often forms very fine particles that stay suspended in the liquid, and pass through filter paper.
garage chemist
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Since when does NaCl dissolve in ethanol? You obviously havent tried that out, because it doesnt work.
Also, the amount of ferrocyanide in salt is really very small.

Add some iron(III)salt solution to a solution of some of your salt in water, and if it doesnt instantly become nearly black with prussian blue then there is no concentration worth extracting in there. The prussian blue reaction is very sensitive.

On the other hand, making prussian blue is a good way to precipitate ferrocyanide ions from solution. If there was a worthwhile aount of ferrocyanide in any product, then precipitation as prussian blue would be the way to extract it.

I think trying to get ferrocyanide from salt is a really dumb idea. Some OTC "sources" of chemicals are damn stupid because of low concentration and/or simply ridiculous, like getting red P from matchbook strikers.

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evil_lurker
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The problem is the ferrocyanide is added like .01% as an anti caking agent... its pretty much worthless as a source as there is very little to extract.

Not all chemicals are bad. Without chemicals such as hydrogen and oxygen, for example, there would be no way to make water, a vital ingredient in beer.
not_important
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Besides that, not all Kosher salt has sodium ferrocyanide added:

http://www.copia.org/content/node/231
pantone159
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'Normal' table salt probably has as much ferrocyanide as any other kind. IIRC, this is where the Morton's salt slogan 'If it rains, it pours' comes from: Even if it is very humid, the salt doesn't clump up, due to the anti-caking effect of ferrocyanide.

I once read somewhere that Kosher salt was more pure than regular salt, maybe this is the lack of iodide though.
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Not all table salt uses ferrocyanide, various silicates and magnesium carbonate are common too. Drop some salt into enough water to dissolve it, if there is a milkiness then it's likely a silicate anticaking agent was used.
chemkid
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I tried it out this morning, and obviously it didn't work, because NaCl is very sparingly soluble in ethanol (stupid Internet). But from the affordability of the salt, it wouldn't be that ridiculous to do and if you have a distillation setup you can recover the solvent you use. I used Morton kosher salt because it was uniodized, and had only salt (and impurities of the salt) and sodium ferrocyanide. Just because somethings is there in low concentrations doesn't make its extraction pointless. Try Marie curie and radium, well i guess were not discovering anything new, but so what.

Chemkid

PS I thought extracting red phosphorus from match boxes sounded like great fun.

[Edited on 31-12-2007 by chemkid]

[Edited on 31-12-2007 by chemkid]

[Edited on 31-12-2007 by chemkid]

evil_lurker
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 Quote: Originally posted by chemkid I tried it out this morning, and obviously it didn't work, because NaCl is very sparingly soluble in ethanol (stupid Internet). But from the affordability of the salt, it wouldn't be that ridiculous to do and if you have a distillation setup you can recover the solvent you use. I used Morton kosher salt because it was uniodized, and had only salt (and impurities of the salt) and sodium ferrocyanide. Just because somethings is there in low concentrations doesn't make its extraction pointless. Try Marie curie and radium, well i guess were not discovering anything new, but so what. Chemkid PS I thought extracting red phosphorus from match boxes sounded like great fun.

Well you can't exactly go buy radium for $30 (or less) a pound either, can you? Not all chemicals are bad. Without chemicals such as hydrogen and oxygen, for example, there would be no way to make water, a vital ingredient in beer. MagicJigPipe International Hazard Posts: 1554 Registered: 19-9-2007 Location: USA Member Is Offline Mood: Suspicious Red P from matchbook strikers is only viable if (a) you are a tweaker and can stay up for a week scraping them or dissolving in acetone (works better but wastes acetone and recycling is even more time consuming) (b) if you only need small, impure quantities, like a couple of grams. I have done it before and it is, most certainly, not fun. I think I got like .2g per box (just an estimate, it was a long time ago) which includes all impurities such as silica. Also, I use Kosher salt for some reactions/washings because it claims to contain only salt and no iodides. It dissolves clear. I hope it doesn't contain ferrocyanides. [Edited on 1-1-2008 by MagicJigPipe] [Edited on 1-1-2008 by MagicJigPipe] "There must be no barriers to freedom of inquiry ... There is no place for dogma in science. The scientist is free, and must be free to ask any question, to doubt any assertion, to seek for any evidence, to correct any errors. ... We know that the only way to avoid error is to detect it and that the only way to detect it is to be free to inquire. And we know that as long as men are free to ask what they must, free to say what they think, free to think what they will, freedom can never be lost, and science can never regress." -J. Robert Oppenheimer chemkid National Hazard Posts: 269 Registered: 5-4-2007 Location: Suburban Hell Member Is Offline Mood: polarized as states before, it depends on you brand. I was really looking to purify the salt from the sodium ferrocyanide when i thought i discovered a means for removing it. So far i am yet to find a solvent in which NaCl is soluble and Na ferrocyanide is not or vise versa. Chemkid garage chemist chemical wizard Posts: 1803 Registered: 16-8-2004 Location: Germany Member Is Offline Mood: No Mood You can purify NaCl from almost any contaminants by dissolving in water, filtering until you have a clear solution, and gassing with HCl. The solubility of NaCl decreases strongly with increasing HCl concentration, and the purified salt precipitates. This removes sodium ferrocyanide completely. This process is used in industry to prepare high-purity NaCl for various uses. [Edited on 1-1-2008 by garage chemist] www.versuchschemie.de Das aktivste deutsche Chemieforum! Tinton Harmless Posts: 15 Registered: 16-12-2007 Member Is Offline Mood: homework laden Perhaps if you mixed an acid strong enought to create HCN, but not strong enought to create HCL, to the ferrocyanide, the cyanide ion could be liberated from kosher salt. And then bubbled through NaOH for NaCN... [Edited on 3-1-2008 by Tinton] chemkid National Hazard Posts: 269 Registered: 5-4-2007 Location: Suburban Hell Member Is Offline Mood: polarized I e-mailed the company and found out what everyone already pointed out .0013 concentration of pottasium ferrocyanide. Should be pure enough for me. Thats morton kosher salt for all who want to know. @tinton Not so eager to work with hydrogen cyanide Xenoid International Hazard Posts: 775 Registered: 14-6-2007 Location: Springs Junction, New Zealand Member Is Offline Mood: Comfortably Numb @ chemkid If you are so desperate for sodium ferrocyanide you are prepared to extract it from salt, why don't you try the "old fashioned way". ""When nitrogenous refuse (blood, horns, leather scraps, etc.) is charred, and the black mass is ignited with potash and iron filings, something is formed which passes into solution when the mass is lixivated with water. The aqueous solution, on evaporation gives yellow crystals of potassium ferrocyanide (K4Fe(CN)6.3H2O)."" ""...prepared it by melting dried blood with potash salts and treating the aqueous extract of the mass with ferrous sulphate."" ""...animal flesh... and other animal substances could be used instead of blood."" To make Na ferrocyanide, use sodium carbonate instead of potash, though Na ferrocyanide is less soluble than K ferrocyanide! I've always wanted to try this but I've never had the guts (literally)... Could be a bit smelly, if your'e in an urban area! This could be a fitting end for the family "moggy" if he/she/it gets hit by a car; converted into yellow sodium ferrocyanide crystals and put in a jar on a shelf! If you require more, find a dead cow or a friendly butcher! [Edited on 3-1-2008 by Xenoid] evil_lurker International Hazard Posts: 767 Registered: 12-3-2005 Location: United States of Elbonia Member Is Offline Mood: On the wagon again. www.chemsavers.com has potassium ferrocyanide on sale, 2 Kgs for$25, shipped ORM-D.

Not all chemicals are bad. Without chemicals such as hydrogen and oxygen, for example, there would be no way to make water, a vital ingredient in beer.
len1
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 Quote: Originally posted by garage chemist You can purify NaCl from almost any contaminants by dissolving in water, filtering until you have a clear solution, and gassing with HCl. The solubility of NaCl decreases strongly with increasing HCl concentration, and the purified salt precipitates. This removes sodium ferrocyanide completely. This process is used in industry to prepare high-purity NaCl for various uses.

145 gms NaCl were dissolved in 500ml H2O giving a 5mol/L solution (about saturation). To half of this 80ml of 32% w/vol HCl was added giving a 10% w/vol HCl solution.

No NaCl precipitated out. Any stronger acid and you should start liberating cyanide.
garage chemist
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I said *gasssing* with HCl, not adding hydrochloric acid. Adding hydrochloric acid introduces water as well.

However, you can do without the gassing if you slowly add the NaCl solution to the HCl and not the other way round.
Also, you need more HCl in proportion to the NaCl solution- try using equal volumes of HCl and NaCl solutions, or 2/1 HCl/NaCl by volume.

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len1
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Yes I noticed the gassing - that means you want to achieve soubilities of the order of saturation of HCl - that will precipitate out some NaCl.

But thats just the common-garden common ion effect. Theres nothing special about HCl and NaCl and the effect is rather weak, its certainly no way to eliminate NaCl from solution. Just a way to precipitate out a small amount of chloride salt.

PS If theres ferrocyanide in solution the extremely high H+ concentration will be hazardous.

When dealing with concentrations of 1mol/L or above one should really use activity coefficients - thermodynamics becomes non-linear since the ions no longer form a dilute gas. However the effects can be demostrated in the linear approximation.

The solubility of NaCl at 30C is 6mol/L. Therefore

[Na][Cl]=36(mol/l)^2 is its solubility product - the excess precipitates.

The maximum strength of HCl which can be dissolved in solution is 10 mol/L (though in saline solutions it is less - NaCl has the same effect on it).

x(x+10) = 36 is the amount of NaCl which will dissolve in 37% HCl, we get x ~ 3 mol/L predicting this method will precipitate about half the NaCl in solution.

I did a preliminary investigation and it precipitates a bit more than this due to non-linear effects.

Lets repeat that with the experiment I did above. Equal volumes of 6mol/L NaCl and 10mol/L HCl solution are mixed.

The sodium concetration now is ~ 3 mol/L since the volume ~ doubles

The chlorine concentration now is ~ (10+6)/2 = 8 mol/L, where division by 2 since volume ~ doubled

The solubility product is 8*3 = 24 (mol/L)^2

so nothing precipitates as I observed.

This can be repeated with Na2SO4 and H2SO4 etc..

[Edited on 4-1-2008 by len1]
woelen

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I think there is more to this, when the HCl is highly concentrated. In 15% HCl quite some table salt can be dissolved, but in 37% HCl it is virtually insoluble. Try it yourself. If you want to heat the solution, then keep it in a closed (pressure withstanding) vessel, otherwise you'll drive off much HCl and then the experiment is not honest anymore.

I think that this has to do with the effect of non-ionized HCl in solution, which makes the solution less suitable for purely ionic compounds. This, combined with the already high concentration of chloride probably results in low solubility of NaCl.

A similar effect exists for water, to which some ethanol or propanol is added. The solubility of NaCl rapidly drops with increasing concentration of the alcohol.

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len1
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Yeah OK, although I dont know why you mention heating - the solubility of NaCl hardly varies with T and for HCl it decreases.

I think that rather than trying to dissolve salt in 37% HCl equilibrium is more quickly reached by adding a small amount of solution of known concentration to a much larger volume of HCl solution, filtering and weighing. (There is no reason for using HCl gas to test this that I can see).

I have done a preliminary test (without using the analytical ballance) and it seems 1/4 salt remained in solution, where my simple theory predicted 1/2.

However if your hypothesis about the change in the ionic nature of high concentration hydrochloric acid is correct, then this is not the common ion effect, and the results should apply to HCl and any other ionic salt. i.e. adding a small amount of saturated solution of any salt to 37% HCl will precipitate that salt. Len

[Edited on 4-1-2008 by len1]
woelen

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Your last remark is not correct. Indeed, a precipitate can be formed, but this usually is the metal chloride. E.g. when you add NaBr to concentrated HCl, then it also dissolves with difficulty, but most likely because it becomes covered with a crust of NaCl. If you drip in highly concentrated NaBr solution in concentrated HCl, then you get NaCl as solid precipitate.

The same effect is present with KCl and KBr. Both dissolve with great difficulty in concentrated HCl.

Not all metal salts suffer from low solubility in conc. HCl, or in solutions with ethanol or acetone. Some salts dissolve well in less-polar solvents also. An example is CuCl2.2H2O. This dissolves in acetone very well, also in ethanol, and in conc. HCl.

Yet another reason, why things may turn out different is complex formation. If copper sulfate is added to concentrated HCl, then it quickly dissolves, giving H2SO4 and a copper complex anion, CuCl4(2-).

Summarizing, there are many different effects, which may have opposite effects on solubility. What the net outcome will be remains a matter of experimentation.

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len1
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If you are correct regarding the changed nature of the HCl solution then the key test is that a precipitate, on adding a saturated solution of another salt (obviously excluding coordination compounds) will form. You are not correct to say the salt will definitely be a chloride - it depends on the relative solubilities of the chloride vs whatever other ion you have introduced in product with the relevant concentrations. That is not however what we are interested in here - which is to differentiate what you have mentioned from the common ion effect. Len
chemkid
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That last post was dismissing any attempt at extracting the ferrocyanide. That's pure enough for me referred to the salt Just in case there was any misunderstanding there. I'm not crazy or desperate enough to extract such an extremely low concentration.

the idea using animal parts does sound interesting.

Chemkid

len1
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A saturated solution of NaCl in 30C H2O was formed by dissolving 35gms NaCl in 100mls. 5mls of this solution were added to 55ml of 34% HCl (giving a final HCl concentration of 31%). A precipitate of NaCl formed immediately, the solution was shaken and allowed to stand. It was subsequently rapidly filtered (to allay the possibility of HCl evaporating during filtration) the filter paper was removed, soaked in conc HCl to remove any adhering precipitate and liquids combined. The solution was evaporated and yielded 1.2 gms of NaCl.

This forms 1.2/1.75 ~ 68% of salt in solution precipitated. This compares with 0.5 from the linear analysis from my two posts above, which is reasonably good agreement.

A conc. solution of KNO3 added to conc HCl in the same way produced no precipitate.

This seems to demonstrate

1) What we are looking at here is the common ion effect
2) Theres nothing special about HCl solutions - in particular the polarity of the solution does not alter at high HCl concentrations
3) The effect is good at precipitating high percentages 60-80% of relatively pure chlorides out of solution - other salts do not precipitate

[Edited on 6-1-2008 by len1]
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