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  1. #1
    Ian Grant's Avatar
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    Modern Rodinal Substitutes Part II

    Apologies for having to start a new thread but I can't read or even access the first to reply to posts.

    So with a bit of telepathy

    Quote Originally Posted by Kirk Keyes View Post
    Well, there's a problem there, as it's really hard to measure pH accurately when it gets much above 12.5 or so. You have to start getting special electrodes and the like.

    But for MSDS work, it doesn't have to be too precise.
    __________________
    Kirk

    A point that's being missed is that A&O give a figure of 2.7% Potassium Hydroxide not 3% in older Agfa MSDS.

    The pH is around 14 sure, but the actual requirement is the pH of the working dilute solution rather than the concentrate which is given elsewhere as pH 11.55, which I commented on in the first post of the thread.

    Way back Ron (PE) mentioned adjustments to Rodinal before bottling, the question we need to ask is are they adjusting on the basis of the concentrate, or also doing some tests on a dilute sample, as this will be a far more accurate indicator.

    Can someone please post a link to this continuation on the original post.

    Ian

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    BTW, Guys going through all this posts, I also tried to mix some Rodinal.

    I used this recipe:
    Sol A:
    water 500ml
    p-aminophenol 50g
    potassium metabisulfite 150g

    Sol B:
    water 300ml
    Sodium hydroxide 100g

    Sol C:
    water 50ml
    Potassium Bromide 5g
    Sodium benzenesulfonate 0.3g

    This recipe comes from Soviet Union the most known book, and states this as Foma R09 Rodinal recipe. The only difference - the formula asks for p-aminophenol hydrochloride or hydrosulfate), but looking at your discussion this is definitely the mistake. It must be the base.

    The principle is almost the same as usual - slowly add Sol B into Sol A, until precipitate almost dissolved.
    The add Sol C, and water to make 1l.
    Sodium benzenesolfonate is used to prevent oxigen diffusion into the solution. Greatly extends it life. Has no effect on the developer.

    Looks it is very similar in it's activity and properties to Agfa modern Rodinal, what is different - the color, it is very light when fresh.

  3. #252
    Ian Grant's Avatar
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    Of course pH goes up like that. But you're entirely missing the point.

    Right from day one when Agfa began making Rodinal (until the major shift in 1964) the important part of manufacture of it or the substitutes was that there was just enough Hydroxide to convert the metabisulphite into Sulphite and react with the p-Aminophenol. See the 1910 "Agfa" Book & remember who wrote Agfa's German handbooks - Dr Momme Andresen, who discovered p-Aminophol and designed Rodinal. To quote "Agfa-Rodinal contains only an alkaline salt of Paramidophenol, but no excess of caustic alkali". Later when they manufactured with Potassium Sulphite the level of Hydroxide dropped substantially as would be expected due to the reactions taking place.

    Whether there's a trace of excess Hydroxide in Calbe R09 or not is immaterial what's important is that the bulk of the hydroxide has reacted to form that "alkaline salt of p-Aminophenol, that itself will increase the pH.

    What's certain is that the pH is significantly lower than it should be from the amount of Hydroxide in the formula.

    Ian

  4. #253
    Ian Grant's Avatar
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    Yes your right it's the same basic Andresen formula, I THINK there's not enough Hydroxide though to convert all the Metabisuphite into Sulphite, I'd have to go back & find the calculations which I have somewhere. If not all the Metabisulpte is converted it'll have far better keeping properties as there will definitely be no free Hydroxide.


    It's the fact that there's the Sodium benzenesulfonate is used that's interesting and needs checking out.


    Ian


    Quote Originally Posted by pavelt2tk0 View Post
    BTW, Guys going through all this posts, I also tried to mix some Rodinal.


    I used this recipe:
    Sol A:
    water 500ml
    p-aminophenol 50g
    potassium metabisulfite 150g


    Sol B:
    water 300ml
    Sodium hydroxide 100g


    Sol C:
    water 50ml
    Potassium Bromide 5g
    Sodium benzenesulfonate 0.3g


    This recipe comes from Soviet Union the most known book, and states this as Foma R09 Rodinal recipe. The only difference - the formula asks for p-aminophenol hydrochloride or hydrosulfate), but looking at your discussion this is definitely the mistake. It must be the base.


    The principle is almost the same as usual - slowly add Sol B into Sol A, until precipitate almost dissolved.
    The add Sol C, and water to make 1l.
    Sodium benzenesolfonate is used to prevent oxigen diffusion into the solution. Greatly extends it life. Has no effect on the developer.

    Looks it is very similar in it's activity and properties to Agfa modern Rodinal, what is different - the color, it is very light when fresh.

  5. #254
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    Correct me if I'm wrong, but I seem to remember learning that pH=14 does not necessarilly mean that the solvent that is causing that pH is saturated. In the case of strong alkalis, pH=14 may occur far below saturation, but cannot increase as more alkali is added. An acid-base reaction may occur in a strong solution of KOH and go to completion, leaving the pH at 14, with capacity remaining for more such reactions.

    What happens to pH when we add just enough KOH to an amount of paraminophenol to form the potassium paraminophenolate? It seems to me that pH>7 implies that more than enough KOH was added, but even pH=14 does not tell us how much more.
    Gadget Gainer

  6. #255
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    Ian;

    What is certain is that KOH + pAPH = KpAP + HOH which is a neutralization.

    But, KpAP + HOH is an equillibrium reforming KOH + pAPH which is present as K + OH. Also, if you look at the molar equivalents used above, 100 g of NaOH in this case is over 2 moles of hydroxide and less than 1 mole of pAP. Even if it were the sulfate the pAP would be overwhelmed by the caustic. The Metabisulfite contributes little to this reaction in terms of OH, merely introducing the SO3= ion.

    As a result, regardless of what is said, if the pH is above 7, the solution is alkaline and contains OH ions. This is fundamental chemistry. If it were acidic, then there would be H+ ions. At 7.0, there would be equal numbers of H+ and OH-. Thats fundamentally just water. That is the only place on the pH scale where there is no excess of acid or base, and that is called neutrality.

    The caustic may even be equimolar to pAP or its salt, but the equillibrium causes an excess of OH- to form in the solution and that is a chemical fact. That is why the pH is so high, due to an excess of OH-. Dr Andresen may have been in error or trying to mislead people, IDK, but his statement is certainly misleading in the face of the formulas and pH values I have seen.

    PE

  7. #256
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    Quote Originally Posted by gainer View Post
    Correct me if I'm wrong, but I seem to remember learning that pH=14 does not necessarilly mean that the solvent that is causing that pH is saturated. In the case of strong alkalis, pH=14 may occur far below saturation, but cannot increase as more alkali is added. An acid-base reaction may occur in a strong solution of KOH and go to completion, leaving the pH at 14, with capacity remaining for more such reactions.

    What happens to pH when we add just enough KOH to an amount of paraminophenol to form the potassium paraminophenolate? It seems to me that pH>7 implies that more than enough KOH was added, but even pH=14 does not tell us how much more.
    Patrick;

    You are quite right. It also tells us though that an alkaline solution has so many moles / liter of hydroxide ion present.

    PE

  8. #257
    Ian Grant's Avatar
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    Quote Originally Posted by gainer View Post
    Correct me if I'm wrong, but I seem to remember learning that pH=14 does not necessarilly mean that the solvent that is causing that pH is saturated. In the case of strong alkalis, pH=14 may occur far below saturation, but cannot increase as more alkali is added. An acid-base reaction may occur in a strong solution of KOH and go to completion, leaving the pH at 14, with capacity remaining for more such reactions.

    What happens to pH when we add just enough KOH to an amount of paraminophenol to form the potassium paraminophenolate? It seems to me that pH>7 implies that more than enough KOH was added, but even pH=14 does not tell us how much more.
    Spot on Patrick, you understand what I'm getting at.

    It's the fact that the "potassium paraminophenolate" in a high concentration Potassium Sulphite solution has a pH of around 11.8 and when we have excess of hydroxide as in the more modern Rodinal formula we go to pH 14

    pH 14 is in fact listed as being reached by 5.6% KOH solution, the MSDS's for A&O Rodinal show the KOH is only 2.7%. But 0.5% KOH is pH 13 and the Sulphite is pH 9-10 anyway so every thing there seems as expected.

    Ian

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    Ian;

    When you say that Potassium Sulfite solution is alkaline, what you are really saying though is that there is an excess of OH- created when you add Potassium Sulfite to water. Again, the alkalinity comes from the equillibrium which causes OH- to break off from water and form an excess of hydroxide (or alkali) and thus, KOH is present in solutions of Potassium Sulfite.

    PE

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    Quote Originally Posted by Ian Grant View Post
    Yes your right it's the same basic Andresen formula, I THINK there's not enough Hydroxide though to convert all the Metabisuphite into Sulphite, I'd have to go back & find the calculations which I have somewhere. If not all the Metabisulpte is converted it'll have far better keeping properties as there will definitely be no free Hydroxide.


    It's the fact that there's the Sodium benzenesulfonate is used that's interesting and needs checking out.


    Ian
    BTW, I have no electronic pH meter, but used indicator paper, it shows pH about 11,5-12.
    And the thing - I just took the bottle of original Agfa Rodinal (produced 2006-2007) - it has large (5-10mm) transparent crystals in the bottle. I tried to mix rodinal many times, but I always had only very small crystals (less than 0,5mm).... And one more thing I can't understand - if I add more NaOH, crystals will dissolve, yes, pH will reach 14, but where are the crystals, which are in Agfa's developer?

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    The crystals dissolve when more alkali is added. The pAP is a weak acid and needs a large amount of "excess" hydroxide to force the salt to dissolve by forming the Phenolate.

    PE



 

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