Kodak / sodium metaborate

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snusmumriken

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At some stage long ago, I made a note of Kodak advice that in place of 10g Kodalk (sodium metaborate) one could use 1.5g sodium hydroxide plus 7g borax. So this is what I have been using in bath B of Barry Thornton's two-bath developer (so 1.8g NaOH plus 8.4g borax in 1 litre of solution), and it seems to work very nicely.

What I'm not clear about is whether this mixture generates sodium metaborate chemically in solution, or whether it is simply a substitute. Can anyone explain the chemistry to me, please?
 

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Borax and Sodium Metaborate are in the same kind of relationship as Sodium Bicarbonate and Sodium Carbonate. You can interpret the Borax as a mixture of Sodium Metaborate and Boric Acid. If you add Lye to this mixture, you get Sodium Metaborate.

BTW if you store Lye for prolonged periods of time, it will acquire aerial moisture and Carbon Dioxide. As a result, each grain of Lye will contain some amount of Sodium Carbonate, and it will be less active per gram than suggested by the NaOH formula of the pure compound. Pat Gainer posted something in order to address this issue, and Mike Wilde was kind enough to preserve this info for us here on photrio.
 
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Preparing a concentrated metaborate stock solution from borax and sodium hydroxide works and is convenient. I'm not sure if the alkalinity isn't high enough (pH >11 @ 10% w/v) that storage in PET plastic bottles might be a problem. Polyethylene should be OK, but is gas permeable, so carbon dioxide could diffuse into the solution and lower the pH. I store stock solutions in glass bottles and haven't noticed them attacking the glass.

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.

Alkali borates have many hydration states and crystalline structures, though in the end we're interested how much boron in the correct ionic form ends up in our recipes. The concentrated stock solution gets around that problem by avoiding hydration water altogether (and the variations in hydroxide strength can be dealt with qualitatively by "titrating" with borax to neutralization.

I personally like having and using solid reagents wherever possible, so I prepare kodalk as a solid. The preparation comes from US2886425, which has a nice summary of the stoichiometry of the reaction between borax and sodium hydroxide, and US1976299, which incidentally is an Eastman Kodak developer patent, but outlines the preparation of metaborate (although that form would have a degree of hydration between the 4-mol and the 8-mol species):

69.15g of borax (decahydrate) and 15.20g sodium hydroxide (purity 99%, 5% excess) are mixed in a plastic beaker as dry powders and 17.0ml of ice-cold DI water (5% excess) are added to the powder with strong manual stirring (a sturdy plastic spatula or spoon work well). The water is quickly absorbed and within a minute, the whole mass goes through a thick (molasses), thin (syrup), and crystalline (wet sugar) phase, releasing substantial heat. Stirring is maintained as the mixture thickens and almost solidifies, so that the mass is broken up into granules in size between rough sand and rice. If the mixture isn't stirred with sufficient enthusiasm, it will solidify into a rock (which i fact would happily destroy coffee grinders and blenders..). Once the mass cools to about 30C (80-ish F), it can be spread out to fully cool and equilibriate, and is then transferred for storage. This yields approximately 100g of sodium metaborate octahydrate. The excess of hydroxide accounts for carbonate and water content (addendum: the amount can vary from the stoichiometric 14.50g to +1-5% without reflecting on the buffering capacity of the final product, but some unreacted borax will remain dispersed in the solid), and the additional water makes up any amount that evaporates during the reaction. In any event, the final product might vary within a few percent, but is photographically viable and the preparation can be scaled up so that a single run will yield years' supply of Kodalk. Plastic utensils are used throughout to prevent metal contamination.
Please bear in mind this is dangerous, lye is corrosive and the reaction produces substantial heat. Wear appropriate PPE and follow safety practices. That said, the preparation is convenient and affords a stable product.

I use AR purity hydroxide, because I can source it cheaply. I believe food grade hydroxide is good enough, because it is specified for low heavy metals content. Iron contamination doesn't exceed 0.005%, which contributes less than 8ppm iron in the final metaborate. addendum: dissolving the hydroxide in the water and adding the solution to borax also works, but results in more mechanical losses and is overall more diffcult)
 
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Alan Johnson

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At some stage long ago, I made a note of Kodak advice that in place of 10g Kodalk (sodium metaborate) one could use 1.5g sodium hydroxide plus 7g borax. So this is what I have been using in bath B of Barry Thornton's two-bath developer (so 1.8g NaOH plus 8.4g borax in 1 litre of solution), and it seems to work very nicely.

What I'm not clear about is whether this mixture generates sodium metaborate chemically in solution, or whether it is simply a substitute. Can anyone explain the chemistry to me, please?
It generates sodium metaborate tetrahydrate which is Kodalk ,you are correct. They are of course partly ionized in solution.
http://web.archive.org/web/20050307010427/http://silvergrain.org/Photo-Tech/chemistry-misnomers.html
 
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snusmumriken

snusmumriken

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An odd thing I noticed is that my 1958 edition of the Ilford Manual of Photography mentions sodium metaborate in "certain formulae" only briefly (commercial pique?), and goes on to say that "identical results can be obtained by employing equal parts of sodium hydroxide and borax". Any thoughts about that?
 
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snusmumriken

snusmumriken

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About the deterioration of solid NaOH in storage...my wife suggested making it into a molar solution in water as soon as it was delivered, which is what I did. Then one has to do the maths, but you can easily work out how much to add to substitute for the pure solid form.
 

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About the deterioration of solid NaOH in storage...my wife suggested making it into a molar solution in water as soon as it was delivered, which is what I did. Then one has to do the maths, but you can easily work out how much to add to substitute for the pure solid form.

Good idea. It would absorb some CO2 if the bottle were opened frequently. It's actually so soluble that it could be made 10Molar or more. That might help its stability perhaps. Bear in mind that it generates much heat as it dissolves and is dangerous, so on second thoughts maybe not such a good idea.
 
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OK, neat. I'm going to have to try this. I just got borax and sodium hydroxide. I was going to do the laundry and make pretzels with it, but I think instead I'll make photographic developer.
 
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About the deterioration of solid NaOH in storage...my wife suggested making it into a molar solution in water as soon as it was delivered, which is what I did. Then one has to do the maths, but you can easily work out how much to add to substitute for the pure solid form.
Dry storage in a tightly-sealed container should keep the hydroxide stable for a long time. The usual trouble is how the chemicals were stored prior to purchase (a thick HDPE bank with a seal is a great barrier, but a heat-sealed PE bag offers less "protection").

You can dissolve sodium hydroxide up to 50% by weight in water. Large manufacturers will often use the aq. solution in their processes. Be careful with storage, though, as the solution is corrosive enough to etch glass and hydrolyze PET over time. Sigma sells hydroxide solutions in HDPE bottles, so if it's good enough for them...Concentrated solutions experience salt creep and bottles get crusty after a time, wiping the neck and thread of the bottle after use prevents this somewhat.

I'm not sure what the Ilford manual tried to imply. Metaborate was/is historically more popular in the US, probably due to availability. Equal parts of borax and lye would result in a far too alkaline mix of borate and hydroxide
 

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Dry storage in a tightly-sealed container should keep the hydroxide stable for a long time.
What also helps (perhaps) - I usually get my NaOH as drain cleaner pellets. The pellets don't easily absorb aerial moisture - and they're of course packaged in a properly sealed plastic container.

I've seen people ridicule the use of drain cleaner NaOH for photography purposes. It's OK - they probably never tried. The only drawback is that the pellets don't dissolve as easily as flakes or powder. The advantage, though, is that this also makes them much more safe to handle!
 
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What also helps (perhaps) - I usually get my NaOH as drain cleaner pellets. The pellets don't easily absorb aerial moisture - and they're of course packaged in a properly sealed plastic container.

I've seen people ridicule the use of drain cleaner NaOH for photography purposes. It's OK - they probably never tried. The only drawback is that the pellets don't dissolve as easily as flakes or powder. The advantage, though, is that this also makes them much more safe to handle!

Pellets are what I use. I wonder if the process described by @Nikola Dulgiarov will work with pellets as well or does it strictly need powdered NaOH?
 
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Pellets are what I use. I wonder if the process described by @Nikola Dulgiarov will work with pellets as well or does it strictly need powdered NaOH?

Raghu, yes, the preparation works well with granules, although i have noticed that drain cleaner lye is coarser than AR grade, both are uniformly spherical particles. The AR grade is finer and contains less absorbed moisture/CO2, so much so that it is a challenge to weigh it out accurately, the tiny pellets fly off due to electrostatic forces.

Sometimes pure NaOH is supplied as flakes. One could potentially pulverize them, but I wouldn't recommend it. It would then be better to dissolve the lye in the specified amt of water and add it to the borax powder under very vigorous stirring.

I wouldn't trust drain cleaner hydroxide for developers, unless I can verify its impurities. Iron, aluminum, lead, mercury, copper might be present at photographically significant amounts. YMMV. Use appropriate chelators (NTA + HEDPA, DTPA, etc) for anything long-term storage.
 
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Raghu, if your pellets are the same grade as the ones on the website, I think you'll have a hard time with the dry preparation. Dissolve the hydroxide in the water and after it cools down to 30-40C, add it to the borax with strong manual stirring.
 
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Raghu, if your pellets are the same grade as the ones on the website, I think you'll have a hard time with the dry preparation. Dissolve the hydroxide in the water and after it cools down to 30-40C, add it to the borax with strong manual stirring.

Ok, will try this. Thanks.
 
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Raghu, if your pellets are the same grade as the ones on the website, I think you'll have a hard time with the dry preparation. Dissolve the hydroxide in the water and after it cools down to 30-40C, add it to the borax with strong manual stirring.

Nikola, I tried this. Unfortunately, I ended up with a slurry that hasn't crystallized yet. I used exactly the same volume of water and same weight of Borax (decahydrate) and Lye as mentioned in your earlier post. How long did it take for crystallization to happen in your case?
 
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Raghu, the crystallization should begin once the mixture cools below say 40-50C. I would suspect that your NaOH probably has a higher water content. You might be able to induce crystallization by sticking the slurry in a freezer until it begins to stiffen. If there is excess water, you can use a desiccator or spread out the slurry in a nonmetal container and air/sun dry it.

You can also go back to the stoichiometric amount of water, or even less, since the hydroxide may contribute a substantial amount. It might change the preparation above to reflect that. My setup was prone to losing water due to the large surface area.
 
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Nikola, I'll try keeping it in the refrigerator and see. Sun drying is not feasible at the moment as it's rainy season here. Yes, I too think reducing the volume of water used to dissolve Lye would have worked better.
 
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Nikola, I'll try keeping it in the refrigerator and see.

This worked. I was afraid that after taking it out of the refrigerator, the solid might thaw into slurry but it seems to hold up. I just need to break it into smaller pieces.
 
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This worked. I was afraid that after taking it out of the refrigerator, the solid might thaw into slurry but it seems to hold up. I just need to break it into smaller pieces.

As the slurry crystallizes, it incorporates the water into the crystal lattice, so the end result should be bone-dry. Any excess water will eventually equilibrate with the surroundings. The solid phase transition occurs around 50C. Breaking it up is a hassle, but I'd put the mass into a strong plastic bag and apply a hammer enthusiastically.
 
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Breaking it up is a hassle, but I'd put the mass into a strong plastic bag and apply a hammer enthusiastically.

It wasn't that bad as I didn't attempt to grind it. It broke up into small pieces and should be fine for my purposes. Next time I'll try to make small pellets from the slurry itself.

Thanks for your help. Most useful.
 
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