Fixer formula using these two chemicals

Discussion in 'B&W: Film, Paper, Chemistry' started by wildbill, Mar 10, 2012.

  1. wildbill

    wildbill Member

    Messages:
    2,827
    Joined:
    Nov 28, 2004
    Location:
    Grand Rapids
    Shooter:
    Multi Format
    I've been using Arista oderless fixer for several years in liquid form. Now that I'm no longer in los angeles, the xtra shipping charges are $$$$$ and I'd rather mix my own anyway. It contains
    Ammonium thiosulfate
    Sodium bisulfite

    Who's got a formula for me that uses these chemicals?
    Here's the msds
     

    Attached Files:

  2. Bruce Osgood

    Bruce Osgood Membership Council

    Messages:
    2,600
    Joined:
    Sep 9, 2002
    Location:
    Brooklyn, N.
    Shooter:
    Multi Format
    This is the formula from The Darkroom Cookbook for TF-3:

    Ammonium thiosulfate (57-60%)..... 800 mL
    Sodium sulfite.............................. 60 g.
    Sodium metaborate....................... 5 g.
    Add water to 1 Ltr.

    Dilute 1:4 (1+3). Fix film 3 min, paper 1 min, followed by 1 min continuous wash.

    Not to be used with an acid stop bath and there is no need for a Hypo wash.

    I have not used this yet but I will be getting the metaborate Monday. I've been using TF-4 which I believe is TF-3 in an already liquid form.
     
  3. Rudeofus

    Rudeofus Member

    Messages:
    2,395
    Joined:
    Aug 13, 2009
    Shooter:
    Medium Format
    Bruce, your formula makes an alkaline fixer while wildbill's ingredients make a rather acidic fixer. Sodium bisulfite by itself is quite acidic and it is usually used together with sodium sulfite. Look here for a popular recipe. Since sodium sulfite is not overly toxic there is a chance it doesn't show up on your msds.

    If you are absolutely determined to make it work without sodium sulfite, think of two things:
    • If your pH drops too low, the thiosulfate will decompose and becomes ineffective. Stay above pH 4.5 at all times
    • The main reason why folks throw sulfite/bisulfite into the fixer is that it acts as preservative. If you use too little bisulfite, your fixer won't last for long (in terms of time, not capacity).
    Combining these two might put you between a rock and a hard place, so I'd at least think about the recipe I linked to above.
     
  4. ruilourosa

    ruilourosa Member

    Messages:
    324
    Joined:
    Apr 13, 2003
    Location:
    Portugal
    Shooter:
    Multi Format
    just put 200 ml of ammonium thiosulfate + 20 gr of bisulfite, to 1 liter, it will be acidic but if you add another 20 gr of borax it will be almost neutral, if you add more borax it will smell like ammonia and become alkaline. borax can be substituted by a smaller amount of sodium carbonate, if PH is a concern you can buy test strips in some drugstore or internet sites.
     
  5. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,516
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    It's quite possible that Arista fixer contains other chemicals but below the level where they need to be listed in an MSDS.

    Actually Sodium Metabisulphite has often been used in fixers with no other sulphite present but it will only be mildly acidic in an Ammonium Thiosulphate based fixer, something stronger like Acetic acid needs to be used for true acid fixers - also some form of acid buffering when a fixer's possible going to be used with a hardener.

    Ian
     
  6. nworth

    nworth Subscriber

    Messages:
    2,157
    Joined:
    Aug 27, 2005
    Location:
    Los Alamos,
    Shooter:
    Multi Format
    There are a good many fixers like you suggest. One is:

    C-41 Fixer
    Water 700 ml
    Ammonium thiosulfate (58%) 189 ml
    Sodium EDTA 1.5 g
    Sodium bisulfite 15 g
    WTM 1 l
    pH = 6.5
    Ref: Photo techniques, Nov/Dec 2000, pg. 20

    The EDTA isn't really needed for black and white.

    Another is:

    GAF 203 Non-hardening fixer
    Water 740 ml
    Sodium thiosulfate 475 g (use 429 ml of Ammonium thiosulfate)
    Potassium metabisulfite 67.5 g
    WTM 1 l
    Dilute 1:1 for use. Fix 5 to 10 minutes at 20C. Do not use above 21C or in conjunction with solutions containing hydrogen peroxide, like Kodak HE-1.

    or:

    Metabisulfite fixer (non-hardening)
    Sodium thiosulfate (penta) 400 g (use 360 ml of ammonium thiosulfate)
    Potassium metabisulfite 25 g
    WTM 1 l

    As noted, these are not compatible with alum hardeners or hydrogen peroxide.

    Usually, both sodium sulfite and bisulfite are used:

    Kodak F-24 fixer (non-hardening)
    Sodium thiosulfate (penta) 240 g (use 216 ml of ammonium thiosulfate)
    Sodium bisulfate 25 g
    Sodium sulfite (anh) 10 g

    or:

    Kodak F-34 non-hardening fixer
    Water 700 ml
    Ammonium thiosulfate (58%) 185 ml
    Sodium sulfite 10 g
    Sodium bisulfate 8.4 g
    WTM 1 l
    pH=6.5 at 27C; sp.gr. 1.08.
    Fix 5247 (color negative) film 2 minutes at 100F.

    The conversions given are molar equivalents of ammonium thiosulfate (58%) for sodium thiosulfate pentahydrate. Usually only about 86 percent of the molar equivalent of the ammonium thiosulfate is used, but it is not critical.
     
    Last edited by a moderator: Mar 11, 2012
  7. Rudeofus

    Rudeofus Member

    Messages:
    2,395
    Joined:
    Aug 13, 2009
    Shooter:
    Medium Format
    Is there one credible reason why we should use potassium metabisulfite instead of sodium metabisulfite? To my best knowledge potassium ions do not exactly help fixer activity either, quite to the contrary. Also, the amount of thiosulfate is almost doubled for no apparent reason. I have seen that recipe posted over and over again but really doubt anyone would mix it like this.
     
  8. wildbill

    wildbill Member

    Messages:
    2,827
    Joined:
    Nov 28, 2004
    Location:
    Grand Rapids
    Shooter:
    Multi Format
    what's the dilution of the recipe you linked to?

    and for any others you guys have posted?
     
  9. Rudeofus

    Rudeofus Member

    Messages:
    2,395
    Joined:
    Aug 13, 2009
    Shooter:
    Medium Format
    Ryuji states 1 liter and he seems to use it at this strength. Since ammonium thiosulfate is outrageously expensive here compared to sodium thiosulfate, I will probably try Ole's quick fixer OF-1 in the next few weeks.
     
  10. wildbill

    wildbill Member

    Messages:
    2,827
    Joined:
    Nov 28, 2004
    Location:
    Grand Rapids
    Shooter:
    Multi Format
    Yeah, undiluted, I think it would cost me more than the arista stuff including shipping.
     
  11. Worker 11811

    Worker 11811 Member

    Messages:
    1,629
    Joined:
    Jan 29, 2010
    Location:
    Pennsylvania
    Shooter:
    Multi Format
    I know this isn't the formula the OP was looking for. However, I think this might be a good time to share something.

    I have a 36-page booklet entitled, "Agfa Formulas for Photographic Use."
    It contains a whole bunch of formulas for developers, fixers, hardeners and all sorts of other stuff.

    Here is an excerpt from that booklet:[HR][/HR]
    AGFA 203
    NON-HARDENING METABISULPHITE FIXER
    This fixing bath is recommended for use when hardening is not desired. It is highly desirable for accuracy of registration in color work with Reprolith Film.
    Stock Solution
    Hypo ... 1900 grams (4 lb.)
    Agfa Potassium Metabisulphite ... 270 grams (9 oz.)
    Water to make ... 4 liters (1 gal.)

    The Metabisulphite should be added only when the Hypo solution is cool.
    For use, dilute one part stock solution with one part water. Normal fixing time 5 to 10 minutes at 68º F. (20º C.).
    [HR][/HR]
    This booklet was published in 1941 and it contains no formal declaration of copyright. (e.g. "Copyright © 19xx - John Smith - All rights reserved.) So, according to what I understand, this publication is in public domain for two reasons: The copyright is expired, plus there is no formal declaration of copyright.

    Therefore, if anybody is interested in reading this booklet, send me an e-mail or a P.M. and I'll reply with a link where you can download a PDF copy of the book.

    One word of warning: This booklet contains formulas for things that are toxic and very dangerous such as Monckhoven's Intensifier and other formulas that contain substances like mercuric chloride and potassium cyanide. This is the main reason why I'm not publishing the link in the clear. While there are many useful formulas in the booklet and it makes interesting reading on an academic level, I want everybody to understand that they follow the directions contained therein at their own risk.

    Again, if you're interested to read this book, send me a message...
     
  12. nworth

    nworth Subscriber

    Messages:
    2,157
    Joined:
    Aug 27, 2005
    Location:
    Los Alamos,
    Shooter:
    Multi Format
    None that I can tell. I just copied the formula from refernce material.
     
  13. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,516
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    Kodak and Agfa both used Potassium Metabisulphite in commercial fixers and all companies used Potassium Alum in their hardeners. It seems to be high levels of Potassium ions that's important not so much their presence at relatively low levels. So you don't use Potassium Thiosulphate as the fixing agent.

    Ian
     
  14. Sponsored Ad
  15. Rudeofus

    Rudeofus Member

    Messages:
    2,395
    Joined:
    Aug 13, 2009
    Shooter:
    Medium Format
    Ian: if you look at recipes calling for metabisulfite, 99% of them use the sodium version (which is the most easy to get version anyway), except for this one recipe which I happen to see posted all over the place. Since potassium doesn't improve the action of thiosulfate, I didn't understand the motivation for using potassium metabisulfite. As it turns out, the poster doesn't know the reasons for K[SUB]2[/SUB]S[SUB]2[/SUB]O[SUB]5[/SUB] either, he just copied the recipe off somewhere for our convenience.

    willbill: Ammonium thiosulfate makes great fixers and it has become very popular once it became affordable. Unluckily, we live in a time now where the economy of scale does no longer work for ammonium thiosulfate, at least not in home brew quantities. If you bought it by the metric ton, it would be still cheap, so you will find rapid fixer cheaper than if you buy the raw chems. One of my home brew projects (on back burner right now) is mixing, testing and optimizing sodium thiosulfate based fixers, and Ole's quick fix will be my starting point.
     
  16. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,516
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    Rudeofus, I've a very large collection of published formulae of all types and Potassium Metabisulphite was used with Ammonium Thiosulphate in some commercial formulae, I don't bother collecting home made recipes.

    Sometimes there's exaggerated claims made that fixers should be Potassium free after all it's still used in some commercial fixers.

    I'd clarify that the formula posted by Worker 11811 is not actually an Agfa formula rather it's the Agfa Ansco/GAF 203 Fixer, unfortunately numbers and formulae don't match between the two companies.

    Ian
     
  17. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,516
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    I'd add that one commercial fixer contains Ammonium Thiosulphate, Potassium Sulphite and Potassium Metabisulphite and taht's from one of the top 4 manufacturers (Kodak, Agfa, Ilford & Fuji).

    Ian
     
  18. wildbill

    wildbill Member

    Messages:
    2,827
    Joined:
    Nov 28, 2004
    Location:
    Grand Rapids
    Shooter:
    Multi Format
    yeah, I'm looking for something that does the job for both film/paper, doesn't stink, and lasts a long time in concentrated form. The Arista Oderless does that. I've searched this stuff over and over the last couple years and now I actually need to get it done. You guys are too smart for me.
     
  19. jochen

    jochen Member

    Messages:
    352
    Joined:
    May 13, 2008
    Location:
    Germany
    Shooter:
    35mm
    Hello,
    the most popular AGFA fixer formula was AGFA 300. In some sources you read potassiummetabisulfite (K2S2O5), in others sodium metabisulfite in the same concentration and some cases "Natriumbisulfit Lauge" which is a aqueous solution of sodiumhydrogensulfite (is widely used in the paper and cellulose industry). These substances are interchangeable. Sodiummetabisulfite as well as potassiummetabisulfite are commercially available as a preservative for food and wine. Potassiumsulfite is available as a liquid solution sometimes under the trade name Thiosol (I think it is 45 %) e.g. from BASF and together with potassiumhydroxide is an essential ingredient of Rodinal. Ammoniumthiosulfate is mostly used as a liquid solution (58 - 60 %) as it easier to handle. Solid Ammoniumthiosulfate is more expensive and very hygroscopic and gets hard like a stone when it attracts moisture.
     
  20. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,516
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    Jochen, my two post WWII German Agfa books of formulae show Agfa 300 as having Potassium Metabisulphite

    Agfa 304 is a rapid fixer based on Sodium Thiosulphate and Ammonium Chloride (which forms ammonium Thiosulphate) and this also contains Potassium Metabisulphite.

    So substituting Ammonium Thiosulpate for the Sodium Thiosulpate and Ammonium Chloride and adding Potassium or Sodium Metabisulphte would give a fixer close to the MSDS the OP has shown.

    Incidentally all Kodaks fixers in one official Kodak Research Formulary contain Potassium salts, thats F5, F16, F52, F53, F54 and F54a these are all bublished in other Kodak publications.

    Ian
     
  21. Rudeofus

    Rudeofus Member

    Messages:
    2,395
    Joined:
    Aug 13, 2009
    Shooter:
    Medium Format
    Can we agree that some recipes which included potassium were posted some decades ago but that who ever created them may have had special reasons which may or may not apply to us? Some potassium salts are vastly better soluble than their sodium counter parts which would certainly help in creating a concentrate, so a fixer with potassium may be the more viable commercial product despite its (slightly) poorer fixing.

    The big "problem" is that commercially available rapid fixer is so cheap and good that barely anyone mixes his own stuff, which leads to endless repetition of untested (by the poster) recipes all over the place.
     
  22. nworth

    nworth Subscriber

    Messages:
    2,157
    Joined:
    Aug 27, 2005
    Location:
    Los Alamos,
    Shooter:
    Multi Format
    Agfa went through a phase where they called for potassium salts in just about everything. Maybe they had a supplier that could give them some business advantage. In any case, I don't know of any noticeable advantage except solubility, and that only sometimes. If anyone has some sound chemical knowledge on the subject, please sound off.
     
  23. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,516
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    Commercial fixers containing Potassium are still being made today and the formulae aren't necessarily decades old as they've been updated and tweaked to suit modern materials.

    There seems to be a lot of confusion over whether Potassium has a detrimental effects on fixing, if it did then major companies wouldn't use Potassium salts like Potassium Sulphite and Potassium Metabisulphite in fixers. However ther has been a move away from using Potassium Alum as a hardener in fixers to plain Aluminium Sulphate and hardenining fixers tend to use buffered Acetic acid instead of Metabisulpite anyway to maintain a re more stable acidic pH.

    I do mix my own fixers and it's a lot cheaper if you get your Thiosulphate in bulk.

    Ian
     
  24. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,516
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    Agfa were using Potassium Metabisulphite to manufacture Rodinal, with the addition of Hydroxide this splits to form Potassium Sulphite. It was supplied as a concentrated solution.

    Ian
     
  25. wildbill

    wildbill Member

    Messages:
    2,827
    Joined:
    Nov 28, 2004
    Location:
    Grand Rapids
    Shooter:
    Multi Format
    hey!
    anyone care to answer my questions and get the thread back on track? I'm not concerned with agfa.
     
  26. Ian Grant

    Ian Grant Subscriber

    Messages:
    17,516
    Joined:
    Aug 2, 2004
    Location:
    West Midland
    Shooter:
    Multi Format
    If you want simple and effective then use 200g Ammonium Thiosulphate and 20g Potassium or Sodium Metabisulphite, alternately use the Agfa 304 formula which is

    Agfa 304 Rapid Fixer

    Sodium Thiosulphate 200g
    Ammonium Chloride 50g
    Potassium Metabisulphite 20g
    Water to 1 litre

    For films and papers.

    (Note this is an Agfa /Orwo formula and not Agfa Ansco/GAF)

    Ian