Is anybody making their own Ferric Ammonium Citrate

[Bruce6666]

Hello all, is anybody making their own (Green) Ferric Ammonium Citrate ?, if so would you mind sharing your process please ?
I have been trying to make some of my own, but not very successful.

 

[koraks]

Welcome aboard @Bruce6666 !

I'm not aware of anyone doing this, mostly because it's fairly easy to get hold of in most places. I do appreciate the fact that Australia is sometimes a little different in terms of availability of materials. Is there any particular problem getting FAC where you live? Surely, people are doing cyanotypes etc. in Australia as well?

 

[Maris]

I note that Gold Street Studios in Victoria sell (Green!) Ferric Ammonium Citrate and a whole lot of other photographic chemicals. Even stuff I've never heard of.

 

[Bruce6666]

Welcome aboard @Bruce6666 !

I'm not aware of anyone doing this, mostly because it's fairly easy to get hold of in most places. I do appreciate the fact that Australia is sometimes a little different in terms of availability of materials. Is there any particular problem getting FAC where you live? Surely, people are doing cyanotypes etc. in Australia as well?

Hi, FAC is available here , but its not easy for me to travel there, and postage is a killer, being a very amateur home chemist I have all the chemicals in the shed and wanted to give it a try again, had a try at it about 25 years ago and had some success but could not "fix" my pictures. So this time I wanted some FAC to try some new ideas, I've had a look at a few patents etc but just looking for a simple process for FAC.

 

[Bruce6666]

I note that Gold Street Studios in Victoria sell (Green!) Ferric Ammonium Citrate and a whole lot of other photographic chemicals. Even stuff I've never heard of.

Thanks, yes I will probably end up getting some from there.

 

[koraks]

OK, gotcha. Maybe @fgorga has some input on this, but I'd just stick with the store bought material. Even if you can get a synthesis going, the question is how well you'll be able to purify the product. And yields can be very low in DIY settings.

 

[BJ68]

You can have a look at this patent: https://www.freepatentsonline.com/2644828.pdf

Found a few others:
a) https://patents.google.com/patent/FR2200236A1/en
b) https://patents.google.com/patent/CN108059596A/en

and long time ago I made a trial for it, which was no real success:
https://illumina-chemie.org/viewtopic.php?p=56845#p56845 (in German).

The "Hagers Handbuch der pharmazeutischen Praxis " which is mentioned in the text is free to get from archive.org:
Part 1: https://archive.org/details/HagersHandbuchDerPharmazeutischenPraxisBand21919
Part 2: https://archive.org/details/HagersHandbuchDerPharmazeutischenPraxisBand11919

Other years: https://archive.org/search?query=Hagers+Handbuch+der+pharmazeutischen+Praxis+

But is all in German...


bj68

 

[nmp]

Hello all, is anybody making their own (Green) Ferric Ammonium Citrate ?, if so would you mind sharing your process please ?
I have been trying to make some of my own, but not very successful.

Look up Mike Ware's "Simple" cyanotype which essentially involves making FAC in situ using Fe nitrate, citric acid and ammonia.

:Niranjan.

 

[Bruce6666]

You can have a look at this patent: https://www.freepatentsonline.com/2644828.pdf

Found a few others:
a) https://patents.google.com/patent/FR2200236A1/en
b) https://patents.google.com/patent/CN108059596A/en

and long time ago I made a trial for it, which was no real success:
https://illumina-chemie.org/viewtopic.php?p=56845#p56845 (in German).

The "Hagers Handbuch der pharmazeutischen Praxis " which is mentioned in the text is free to get from archive.org:
Part 1: https://archive.org/details/HagersHandbuchDerPharmazeutischenPraxisBand21919
Part 2: https://archive.org/details/HagersHandbuchDerPharmazeutischenPraxisBand11919

Other years: https://archive.org/search?query=Hagers+Handbuch+der+pharmazeutischen+Praxis+

But is all in German...


bj68

Thank you for looking up that information

 

[Bruce6666]

Look up Mike Ware's "Simple" cyanotype which essentially involves making FAC in situ using Fe nitrate, citric acid and ammonia.

:Niranjan.

Thank you, will check it out

 

[revdoc]

You can buy FAC at Gold Street and Vanbar (though they only have brown FAC at the moment). You can also buy a Jacquard cyanotype kit from a lot of art stores.

I've made ferric citrate. The hard part is usually making the ferric hydroxide. This can use ferric nitrate or ferric chloride; it's a bit messy. Ian Leake's page on making ferric oxalate is a good step-by-step, up to the addition of oxalic acid. You'd just add citric acid instead. You can also buy ferric hydroxide granules from aquarium supply stores and pulverise them.

Ammonia might be harder to source. Clear ammonia hasn't been widely available in Australia for years. You can get it a specialist cleaning supplies store, but you might have to buy 10 litres.

 

[Bruce6666]

You can buy FAC at Gold Street and Vanbar (though they only have brown FAC at the moment). You can also buy a Jacquard cyanotype kit from a lot of art stores.

I've made ferric citrate. The hard part is usually making the ferric hydroxide. This can use ferric nitrate or ferric chloride; it's a bit messy. Ian Leake's page on making ferric oxalate is a good step-by-step, up to the addition of oxalic acid. You'd just add citric acid instead. You can also buy ferric hydroxide granules from aquarium supply stores and pulverise them.

Ammonia might be harder to source. Clear ammonia hasn't been widely available in Australia for years. You can get it a specialist cleaning supplies store, but you might have to buy 10 litres.

Thanks for those tips, will have a look at Ian Leake's page.

 

[nmp]

You can also buy ferric hydroxide granules from aquarium supply stores and pulverise them.

What you buy as ferric hydroxide is actually hydrated ferric oxide which ferric hydroxide converts to as it dries. This is very impervious to reaction with oxalic acid - it takes months or years (I have tried) to get any ferric oxalate (but it does work.) That's why the standard process is to react the ferric hydroxide soon as it is formed in the colloidal form before it dries.

My first choice would be to buy from Gold Street as others have recommended. I don't think it is worth messing around with making your own. If OP still wants to tinker in the lab, Simple cyanotype is really simple - it has other advantages as well like stability and contrast control by dialing in various quantities of ammonia in the formula.

:Niranjan.

 

[Bruce6666]

What you buy as ferric hydroxide is actually hydrated ferric oxide which ferric hydroxide converts to as it dries. This is very impervious to reaction with oxalic acid - it takes months or years (I have tried) to get any ferric oxalate (but it does work.) That's why the standard process is to react the ferric hydroxide soon as it is formed in the colloidal form before it dries.

My first choice would be to buy from Gold Street as others have recommended. I don't think it is worth messing around with making your own. If OP still wants to tinker in the lab, Simple cyanotype is really simple - it has other advantages as well like stability and contrast control by dialing in various quantities of ammonia in the formula.

:Niranjan.

Thanks for your reply and info

 

[PGum]

Once upon a time I used to make my own FAC. It was economical on materials but expensive on time. Starting materials were water, ferric chloride, ammonium bicarbonate, citric acid, sodium hydroxide.

Precip the ferric chloride with the sodium hydroxide, producing a ferric hydrate mud. Wash multiple times by decant and cloth filtering, than add to a heated strong solution of ammonium citrate and citric acid made from above materials. Over the course of 15 minutes of stirring, the solution will turn a dark emerald green. Add two aspirin and it will never mold in solution. Do a final filtering.

15 years out, I still have 1/2 full 500ml bottle and it works as new. I have synthesis qtys in my notes but as mentioned, there are better, safer alternatives. I have been purchasing mine for years. But, it can be done!

 

[Bruce6666]

Once upon a time I used to make my own FAC. It was economical on materials but expensive on time. Starting materials were water, ferric chloride, ammonium bicarbonate, citric acid, sodium hydroxide.

Precip the ferric chloride with the sodium hydroxide, producing a ferric hydrate mud. Wash multiple times by decant and cloth filtering, than add to a heated strong solution of ammonium citrate and citric acid made from above materials. Over the course of 15 minutes of stirring, the solution will turn a dark emerald green. Add two aspirin and it will never mold in solution. Do a final filtering.

15 years out, I still have 1/2 full 500ml bottle and it works as new. I have synthesis qtys in my notes but as mentioned, there are better, safer alternatives. I have been purchasing mine for years. But, it can be done!

Hello PGum thanks very much for your reply, could you please tell me the amounts of each chemical that you used to make your FAC ?, and I will try your process, any tips to get a good result ?, Thank you

 

[PGum]

I used:

100 ml ferric chloride etchant solution 42 deg baume to 1 litre water
45g sodium hydroxide (lye) to 1 litre water

Add lye water to precip the ferric hydrate - add til ph 6-7
Wash mud well to remove salt and squeeze down til it cakes.

100g citric acid (CA)
50g ammonium bicarbonate (AB)

Add the AB first to the ferric mud in a SS pot, mix well, slowly add citric acid til fizzing stops. Heat to up to 90 c stirring well - may take 15- 20 mins to go completely green ( even a low boil will not harm it). If you add the citric acid first, you will not get green FAC! Final yield should be around 250ml of a 50% w/v solution but will depend on how much water was left in the mud.

Sodium carbonate is a safer alt to lye which is quite hazardous. Good ventillation and/or particle mask is wise, and gloves, goggles if using lye!

Peter

 

[Bruce6666]

I used:

100 ml ferric chloride etchant solution 42 deg baume to 1 litre water
45g sodium hydroxide (lye) to 1 litre water

Add lye water to precip the ferric hydrate - add til ph 6-7
Wash mud well to remove salt and squeeze down til it cakes.

100g citric acid (CA)
50g ammonium bicarbonate (AB)

Add the AB first to the ferric mud in a SS pot, mix well, slowly add citric acid til fizzing stops. Heat to up to 90 c stirring well - may take 15- 20 mins to go completely green ( even a low boil will not harm it). If you add the citric acid first, you will not get green FAC! Final yield should be around 250ml of a 50% w/v solution but will depend on how much water was left in the mud.

Sodium carbonate is a safer alt to lye which is quite hazardous. Good ventillation and/or particle mask is wise, and gloves, goggles if using lye!

Peter

Thanks Peter, very much appreciated, will give it a try, Thank you

 

[Cor]

Perhaps of interest:

A bit along the same lines as above, but seems to yield the brown variant.

Would take more precautions than shown, ammonia hydroxide is not nice to inhale for instance !

Best,

Cor

BTW does anybody know what the percentage is of a saturated solution of FAC at room temperature ?

 

[Bruce6666]

Perhaps of interest:

A bit along the same lines as above, but seems to yield the brown variant.

Would take more precautions than shown, ammonia hydroxide is not nice to inhale for instance !

Best,

Cor

BTW does anybody know what the percentage is of a saturated solution of FAC at room temperature ?

Thanks for the video

 

[PGum]

Cor,

It is difficult to crystallize. Most forms won’t. As it dries, it will just get tackier eventually forming a glassy amorphous structure.

 

[fgorga]

BTW does anybody know what the percentage is of a saturated solution of FAC at room temperature ?

1200 g /L according to Sigma-Aldrich (https://www.sigmaaldrich.com/US/en/product/mm/103762); temperature unspecified, but probably near room temperature.

 

[Bruce6666]

I used:

100 ml ferric chloride etchant solution 42 deg baume to 1 litre water
45g sodium hydroxide (lye) to 1 litre water

Add lye water to precip the ferric hydrate - add til ph 6-7
Wash mud well to remove salt and squeeze down til it cakes.

100g citric acid (CA)
50g ammonium bicarbonate (AB)

Add the AB first to the ferric mud in a SS pot, mix well, slowly add citric acid til fizzing stops. Heat to up to 90 c stirring well - may take 15- 20 mins to go completely green ( even a low boil will not harm it). If you add the citric acid first, you will not get green FAC! Final yield should be around 250ml of a 50% w/v solution but will depend on how much water was left in the mud.

Sodium carbonate is a safer alt to lye which is quite hazardous. Good ventillation and/or particle mask is wise, and gloves, goggles if using lye!

Peter

Peter would it be possible to use normal household ammonia which is a strength of 20g / lt instead of the ammonium bicarbonate ?, if so how much would you suggest ?, thanks

 

[Cor]

1200 g /L according to Sigma-Aldrich (https://www.sigmaaldrich.com/US/en/product/mm/103762); temperature unspecified, but probably near room temperature.

Thanks ! that is a lot ! Reason for asking is that my stock of AFC is glazed over for lack of a better description. It has become one compact block with a glassy appearance, although I kept the brown glass bottle tightly closed and in the dark. I was planning to throw it out, but I gave it a try anyway. Chipped of a piece with a hammer and a screwdriver, and used it for Cyanotype: still works perfectly.

So I thought why not add water on top, let it stand overnight, mix and wait a bit more, and take off this solution and assume it to be saturated at 1.2g per ml and dilute it as needed.

best,

Cor

 

[PGum]

Peter would it be possible to use normal household ammonia which is a strength of 20g / lt instead of the ammonium bicarbonate ?, if so how much would you suggest ?, thanks

That would complicate things. Assuming there are no additives in the HH Am and it is truly 20g/litre strength, you would need:

Ammonia in 50g ammonium bicarbonate= 0.215 x 50 = 10.75 g
Therefore, you would need 537ml of the HH Am for the earlier noted amounts to react together giving a 15-16% FAC solution strength. Would need to evaporate that down a bit.

Process change: first neutralize your ammonia with about 1/2 the citric acid mentioned above - get to neutral then, add it to the mud, warm on stove and stir, slowly adding the remaining citric acid.

If you don‘t have a proper setup for ventilation, you should consider a cartridge respirator until the ammonia is neutralized. Ammonia is damaging to the lungs as you are probably aware. That is why I use the bicarbonate - it still emits some fumes when opened but not like the liquid form.

When going wayward like this, I suggest scaling down to 1/10 amts as a test run!