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dokko

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I work with sodium hydroxide very often and I fail to see what the problem is.

well, it's no problem if you handle it properly, but it can lead to very nasty damage if there's one moment of lack of attention, which is not something that is the case with 99% other other chemicals we usually use as photochemistry.

for those who don't mind, it's worth to at least pointing out the risks. from wikipedia:

"Like other corrosive acids and alkalis, a few drops of sodium hydroxide solutions can readily decompose proteins and lipids in living tissues via amide hydrolysis and ester hydrolysis, which consequently cause chemical burns and may induce permanent blindness upon contact with eyes.[1][2] Solid alkali can also express its corrosive nature if there is water, such as water vapor. Thus, protective equipment, like rubber gloves, safety clothing and eye protection, should always be used when handling this chemical or its solutions. The standard first aid measures for alkali spills on the skin is, as for other corrosives, irrigation with large quantities of water. Washing is continued for at least ten to fifteen minutes.

Moreover, dissolution of sodium hydroxide is highly exothermic, and the resulting heat may cause heat burns or ignite flammables. It also produces heat when reacted with acids."

Sodium_hydroxide_burn.png



PS: I handled quite a bit of Sodium Hydroxide when necessary for special purposes, but using it to synthesise Sodium Metaborate only to save a few bucks is not appealing to me to say the least.
And the fact that it's sold as a drain cleaner without proper warning seems crazy to me, even more so considering that it's probably stored where kids can easily reach it.
 
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koraks

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for those who don't mind, it's worth to at least pointing out the risks.

Yes. At the same time, it's also not necessary to create a panic.
That hand with chemical burns, which is bad enough, is neigh impossible to replicate when handling the quantities of NaOH used in photographic formulae.

I could also show pictures of drowning victims and argue that it's dangerous to use acquaeuous solutions. One could drown in a tray of developer!

I respect your decision to not handle certain chemicals. We all draw the line somewhere; I'd be hard pressed to undertake uranium toning, for instance. But let's not create more FUD than necessary.
 

dokko

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sure, to get your hand severely burnt you'll have to be really careless, so that's not the real danger. I added the image not to spread Fear, uncertainty and doubt but rather make people realize that it's worth handling carefully.
specially contact with the eyes could be really bad.
 

Alain Deloc

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sensitive to iron impurities like CD3

I know that ECN2 formula has Kodak Anti-Cal #4 Dequest 2006 in it (or ATMP - Amino Trimethylene Phosphonic Acid Pentasodium Salt) which is probably doing a similar job as DTPA but at a higher temperature and higher pH (41.1 Celsius and 10.25). I mixed ECN2 many times with only Calgon-photo (just anti-calcium) and demineralized/distilled water, reusing it for months and never had a problem. But also I don't know if CD3 is that crazy as sodium ascorbate.
 
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Alan Johnson

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Now the real question is : will DTPA (or DTPA-Na5 salt) manage to protect the Xtol-patent formula from sudden failure?
It is pretty well established by now that DTPA works well with proprietary Xtol.
However, (1) The Film Developing Cookbook 2020 p 63 notes potential problems come down to impurities in water and source chemicals.
The difference between proprietary Xtol and that made up from the patent is probably insignificant, certainly in terms of the DTPA:ascorbate ratio.
So it is to be expected that DTPA will almost always protect the Xtol patent formula as well, subject still to (1).
 

koraks

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specially contact with the eyes could be really bad.

Yes, I agree, this is to be avoided at all cost. Preferably also contact with other mucous membranes.

But also I don't know if CD3 is that crazy as sodium ascorbate.

I suspect it isn't quite that temperamental, but a Fuji chemical engineer warned me about its sensitivity to iron ions, specifically. And its light sensitivity, too, but that's a different matter.
 

Alain Deloc

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It is pretty well established by now that DTPA works well with proprietary Xtol.
However, (1) The Film Developing Cookbook 2020 p 63 notes potential problems come down to impurities in water and source chemicals.
The difference between proprietary Xtol and that made up from the patent is probably insignificant, certainly in terms of the DTPA:ascorbate ratio.
So it is to be expected that DTPA will almost always protect the Xtol patent formula as well, subject still to (1).

So if the iron impurities found in water and chemicals exceed the removal capacity of the chelating agent (DTPA in our case) then the failures will appear. Thanks! I will mix the simplified formula and see how it behaves.
 
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albada

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The XTOL patent specifies the pentasodium salt of DTPA, and not the free form. I apologize for that omission in the OP.

Mark
 
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albada

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I looked in my notes, and checked with Photographer's Formulary, to clear up the confusion about 4 mol vs 8 mol sodium metaborate.
The XTOL patent specifies 8 mol.​
The s. metaborate sold by Photographer's Formulary is 8 mol. I checked the molecular weight (137.86) and CAS# (10555-76-7) in their SDS.​

In the old days, 8 mol was octahydrate, but it is now called tetrahydrate due to renaming based on its molecular structure. The result is confusion to this day. I was confused for a while, writing 4 mol in formulas which should have been 8 mol.

BTW, DTPA*Na5 is also sold by BASF as Trilon C.

Mark
 

Alain Deloc

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he s. metaborate sold by Photographer's Formulary is 8 mol. I checked the molecular weight (137.86) and CAS# (10555-76-7) in their SDS.

Can you post the chemical formula of whatever it's named metaborate 8mol? I used @Nikola Dulgiarov substitution formula found here
https://www.photrio.com/forum/threads/kodak-sodium-metaborate.186175/post-2456701
"The 7g Na2B407.10H20 (borax) +1.5g NaOH (sodium hydroxide, lye) is approximately correct and will give the equivalent of 10g NaBO2.4H2O (or Na2B2O4.8H2O), i.e. sodium metaborate octahydrate, or sodium metaborate 8-mol, or Kodalk. If a formula calls for the tetrahydrate (also called 4-mol or dihydrate when represented as NaBO2.2H2O), the conversion factor is 1.00g tetrahydrate = 1.35g octahydrate" --> 7gr. borax + 1.5 NaOH = 10gr sodium metaborate 8mol
He is preparing metaborate as a solid reagent, using high amount of borax and NaOH with 17ml. of cold water, but I just will just dissolve the little amount needed of borax and sodium hydroxide in the 800ml. of water solution just to make the substitution, I don't need solid metaborate.

The XTOL patent specifies the pentasodium salt of DTPA, and not the free form. I apologize for that omission in the OP.
https://www.photrio.com/forum/threads/kodak-sodium-metaborate.186175/post-2456701
Mark

I will redo the math for this one.
 
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Alain Deloc

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I think you calculated the substitution of metaborate by borax and the substitution of sodium ascorbate by ascorbic acid correctly. But the DTPA. 5Na needs to be recalculated and this will affect NaOH as well.

Yes, I am on it right now. Also, it's important to know, if the formula is asking for DTPA-Na5 1gram and not DTPA free acid as I thought at the beginning, maybe it's in fact DTPA-Na5 40% solution? @albada maybe can tell us more.
 

Alain Deloc

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Alain Deloc

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I think you calculated the substitution of metaborate by borax and the substitution of sodium ascorbate by ascorbic acid correctly. But the DTPA. 5Na needs to be recalculated and this will affect NaOH as well.

So I am attaching here a sheet that shows how the substitutions are made

Sodium sulfite​
85 g​
Sodium sulfite​
(85+4.65) g​
89.65 g​
DTPA -Na5​
1 g​
DTPA -Na5​
1 g​
1 g​
Sodium metaborate (8 mol)​
4 g​
<==>​
Borax 2.8 g + 0.6 gr NaOH​
Borax​
2.8 g​
2.8 g​
Sodium isoascorbate​
12 g​
<==>​
10.668 gr ascorbic acid + 2.42 gr NaOH​
Sodium Hydroxide​
(0.6+2.42-1.43) g​
1.59 g​
Ascorbic acid​
10.668 g​
10.67 g​
Dimezone S​
0.2 g​
Dimezone S​
0.2 g​
0.2 g​
Sodium metabisulfite​
3.5 g​
<==>​
3.5gr sodium metabisulfite = 4.65gr sodium sulfite - 1.43gr NaOH​

At the end, I got this formula

Water ........................... 750ml
Sodium sulfite ........ 89.65 g
DTPA-Na5 ......................... 1 g
Borax ............................... 2.8 g
Sodium Hydroxide .. 1.59 g
Ascorbic acid .......... 10.67 g
Dimezone-S ................. 0.2 g
Water to 1L

And because my DTPA agent came directly diluted as a 40% solution, I am going to mix the following


Water ........................... 750ml
Sodium sulfite ........ 89.65 g
DTPA-Na5 40% sol .... 2.5 g
Borax ............................... 2.8 g
Sodium Hydroxide .. 1.59 g
Ascorbic acid .......... 10.67 g
Dimezone-S ................. 0.2 g
Water to 1L
 
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Alain Deloc

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My calculations agree with those in the box except for insignificant variations in the second decimal place.
Here is the old German data sheet that also has times for Xtol 1+2 and 1+3:
Hope to hear the result of your developing a film.

Thanks! This datasheet is really good. One question, though.. Here in Bucharest, sodium metabisulfite lab-grade is 6 euro per kilogram. For some reason, sodium sulfite is 12 euro per kilogram. Is there any reason for that the formula can't be mixed with 67.23gr sodium metabisulfite + 27.79gr NaOH instead of 89.65 g of sodium sulfite?
 

Alain Deloc

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Sorry for ignorance BUT What IS 'DTPA' ?

Diethylene Triamine Penta Acetic acid (DTPA) is a metal complexing (chelating) compound part of the Aminocarboxylic acid (ethylenediamine-based) group. Other members of this group are Ethylene Diamine Tetra Acetic acid (EDTA) and Hydroxy Ethylene Diamine Tetra Acetic acid (HEDTA).
Diethylene Triamine Penta Acetic Pentasodium Salt (DTPA-Na5) is a salt of the above described acid and it is widely used to dissolve metallic impurities.
 

Alan Johnson

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I get this, assuming high purity of the ingredients:
Sodium metabisulfite + 2x Sodium hydroxide <-> ........ 2x Sodium Sulfite................. + Water
Na2S2O5.........................................2x NaOH...................................................2x Na2SO3.....................H2O
190.1..............................................2x40 =80.....................................2x 126.04 = 252.1........................18
67.62..........................................................28.44............................................................89.65

Another dangerous reaction where you need all the gear.
 
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Alain Deloc

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I get this, assuming high purity of the ingredients:
Sodium metabisulfite + 2x Sodium hydroxide <-> ........ 2x Sodium Sulfite................. + Water
Na2S2O5.........................................2x NaOH...................................................2x Na2SO3.....................H2O
190.1..............................................2x40 =80.....................................2x 126.04 = 252.1........................18
67.62..........................................................28.44............................................................89.65

Another dangerous reaction where you need all the gear.

Oh, I think I trimmed the decimals too much, I have just redone the calculation and I get the same values as yours.

Another dangerous reaction where you need all the gear.
Oh, what should I expect to happen? Is it going to boil or something?
 

Rudeofus

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Diethylene Triamine Penta Acetic acid (DTPA) is a metal complexing (chelating) compound part of the Aminocarboxylic acid (ethylenediamine-based) group. Other members of this group are Ethylene Diamine Tetra Acetic acid (EDTA) and Hydroxy Ethylene Diamine Tetra Acetic acid (HEDTA).
Diethylene Triamine Penta Acetic Pentasodium Salt (DTPA-Na5) is a salt of the above described acid and it is widely used to dissolve metallic impurities.

These aminopolycarboxylic acids and their salts differ widely in their ability to bind iron and copper. Typically those compounds with more carboxylic ends bind more tightly, and so do compounds in which the carboxylic ends are closer together. DTPA > EDTA > NTA, and EDTA > PDTA. Only DTPA is rather easily available (means: after some whining to our favorite chem suppliers and at greatly inflated prices, but at least we get our hands on this stuff after all is said and done) AND binds iron/copper strong enough to prevent Fenton reaction. EDTA has been reported to actually accelerate the Fenton reaction, so don't try to use EDTA instead "because it looks so similar".
 

pentaxpete

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Diethylene Triamine Penta Acetic acid (DTPA) is a metal complexing (chelating) compound part of the Aminocarboxylic acid (ethylenediamine-based) group. Other members of this group are Ethylene Diamine Tetra Acetic acid (EDTA) and Hydroxy Ethylene Diamine Tetra Acetic acid (HEDTA).
Diethylene Triamine Penta Acetic Pentasodium Salt (DTPA-Na5) is a salt of the above described acid and it is widely used to dissolve metallic impurities.

Many Thanks for quick reply -- I know about EDTA but that DTPA was 'new' to me and I do not have any !
 
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